CN102241810B - Polylactic acid block copolymer and preparation method thereof - Google Patents

Abstract

The invention relates to a polylactic acid block copolymer and a preparation method thereof. The existing method is difficult to prepare the polylactic acid block copolymer of the high-melting point polyester. The polylactic acid block copolymer of the invention is a diblock copolymer represented by A-bB, A is a single-end hydroxyl aromatic polyester block, and B is a polylactic acid block. The invention adopts a solution polymerization method, takes an organic solvent capable of dissolving reactants of single-end hydroxyl aromatic polyester and lactide as a reaction medium, takes tin salt as a catalyst and takes the single-end hydroxyl aromatic polyester as an initiator to initiate the ring opening polymerization of the lactide, and a polylactic acid block can be effectively introduced by the method. The method can control the polymerization temperature within the range that polylactic acid and lactide can not be degraded or even can not be racemized, effectively inhibits the occurrence of ester exchange reaction, and ensures the chainThe block copolymer of polyester including aromatic polyester with high melting point and polylactic acid is successfully prepared by the regularity of the blocks.

Description

A kind of polylactic acid block copolymer and preparation method thereof

technical field

The invention belongs to the technical field of polymer materials, and relates to a polylactic acid block copolymer, and also relates to a preparation method of the polylactic acid block copolymer.

technical background

Polylactic acid (PLA) has attracted people's attention because of its raw material lactic acid's biomass source and biodegradability, and has similar processing performance and mechanical physical properties to general-purpose plastics such as polypropylene and polyethylene. It has a wide range of uses and huge market potential, but compared with aromatic polyesters such as polyethylene terephthalate (PET), polylactic acid is obviously brittle and has poor impact resistance, which to a certain extent This limits its wider application.

It is hoped to improve the performance of polylactic acid through various methods, such as melt polycondensation or melt coupling with aromatic polyester, hoping to combine the performance of aromatic polyester and polylactic acid. However, since the melt polycondensation needs to be carried out under high temperature and high vacuum conditions, the reaction time is long, and the transesterification reaction is prone to occur. The arrangement of the segments in the obtained copolymer is irregular. At the same time, the lactic acid often undergoes a racemization reaction. It exists in an amorphous state, and the content of polylactic acid can only reach 30% at most, which directly affects the biodegradation characteristics of the material (Licheng Tan et al., J Therm Anal Calorim, 2010 99:269-275; Journal of Applied Polymer Science , 2008 108:2171-2179). Chinese patent CN101338025A first introduces long-chain aliphatic dihydric alcohols into the PET chain to obtain a modified PET with a low melting point, and then uses isocyanate to couple the modified PET and The method of hydroxyl-terminated polylactic acid oligomers has produced a series of multi-block copolymers containing polylactic acid segments, but because it is carried out under the conditions of melt coupling, some mixtures are obtained, which are difficult to separate and cannot A well-defined block copolymer is obtained.

In addition, Chinese patent CN101134807A reacts at a temperature range of 110-180°C by melt polymerization, and uses various low-melting-point hydroxyl-terminated polymers as initiators to initiate ring-opening of lactide to synthesize hydroxyl-terminated polymers. Segmented polylactic acid block copolymers. We noticed that the initiators in this patent are all low-melting polymers, such as polybutylene succinate, polyethylene succinate, polybutylene adipate and other aliphatic Polyester and polybutylene terephthalate, polybutylene terephthalate adipate, polybutylene phthalate, polybutylene isophthalate Some low-melting aromatic polyesters such as alcohol esters, so the melt polymerization reaction can be carried out at a lower temperature. It is well known that lactide and polylactic acid undergo racemization and degradation at higher temperatures. If melt polymerization is used, polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT) and polybutylene terephthalate with a melting point higher than 220°C are used (PBT) These initiators, to initiate the ring-opening polymerization of lactide, in addition to serious transesterification reactions, will inevitably bring about the racemization and degradation of the raw material lactide and the reaction product polylactic acid. The method of ring polymerization is difficult to prepare polylactic acid block copolymers containing PET, PTT, PBT these high melting point polyesters.

Contents of the invention

The first object of the present invention is to provide a kind of polylactic acid block copolymer aiming at the above technical status.

The polylactic acid block copolymer of the present invention is a two-block copolymer, expressed as A- b -B, and b represents a block.

A is a single-end hydroxyl aromatic polyester block, the structural formula is:

、

、

、

中的一种或多种，当为多种时，其配比为任意比；R₂为(CH₂)₂、(CH₂)₃、(CH₂)₄、(CH₂)₆、

中的一种或多种，当为多种时，其配比为任意比；R₃为烷基、含有碳碳双键的不饱和取代基、含有碳碳叁键的不饱和取代基或含有苯环的不饱和取代基。 Where: _R1 is

,

,

,

One or more of them, when there are more than one, the ratio is arbitrary; R ₂ is (CH ₂ ) ₂ , (CH ₂ ) ₃ , (CH ₂ ) ₄ , (CH ₂ ) ₆ ,

One or more of them, when multiple, the ratio is any ratio; _R3 is an alkyl group, an unsaturated substituent containing a carbon-carbon double bond, an unsaturated substituent containing a carbon-carbon triple bond, or an unsaturated substituent containing a carbon-carbon triple bond Unsaturated substituents of benzene rings.

B is a polylactic acid block, and its structural formula is:

The polylactic acid block is one or more of a left-handed polylactic acid block, a right-handed polylactic acid block, and a racemic polylactic acid block, and when there are more than one, the ratio is arbitrary.

The second object of the present invention is to provide the preparation method of this polylactic acid block copolymer. The principle that the present invention can prepare the polylactic acid block copolymer is: use the organic solvent capable of dissolving the reactant single-end hydroxyl aromatic polyester and lactide as the reaction medium, use tin salt as the catalyst, and the single-end hydroxyl aromatic poly The ester is used as the initiator to initiate the ring-opening polymerization of lactide, and the polylactic acid segment can be effectively introduced by this method.

The present invention provides a method for preparing a block copolymer comprising polylactic acid of a single configuration, a block copolymer comprising polylactic acid of two configurations or a block copolymer comprising polylactic acid of three configurations, such as preparing a polylactic acid containing a single configuration The block copolymer of polylactic acid of a kind of configuration adopts steps (1)～(3), adopts steps (1)～(5) as preparing the block copolymer containing polylactic acid of two kinds of configurations, as preparing the block copolymer containing three kinds of configurations The block copolymer of type polylactic acid adopts steps (1)～(7); Its concrete steps are:

Step (1). Preparation of single-end hydroxyl aromatic polyester: under nitrogen protection, dissolve the cyclic aromatic polyester oligomer, monohydric alcohol and tin salt catalyst in the first type of organic solvent treated with anhydrous and oxygen-free During the reaction, GPC (gel permeation chromatography) was used to monitor the reaction process, and the reaction was stopped after the signal peak of the cyclic aromatic polyester oligomer disappeared; after the reaction was completed, it was cooled to room temperature , since the product is insoluble in the reaction solvent at room temperature, the desired single-terminated hydroxyl aromatic polyester was obtained by filtration. The reaction uses a tin salt catalyst and a monohydric alcohol as an initiator to initiate the ring-opening polymerization of a cyclic aromatic polyester oligomer to obtain the corresponding single-end hydroxyl aromatic polyester.

Described cyclic aromatic polyester oligomer is cyclic polyethylene terephthalate, cyclic polytrimethylene terephthalate, cyclic polybutylene terephthalate, cyclic poly Hexamethylene terephthalate, cyclic poly-1,4-cyclohexanedimethyl terephthalate, cyclic polyethylene-1,4-naphthalate, cyclic poly-1,4- Trimethylene naphthalate, Cyclic polybutylene naphthalate, Cyclic polyhexamethylene 1,4-naphthalate, Cyclic poly 1,4-naphthalene dicarboxylate-1,4 -Cyclohexane dimethyl ester, Cyclic polyethylene 1,5-naphthalate, Cyclic polytrimethylene 1,5-naphthalate, Cyclic polybutylene 1,5-naphthalate , Cyclic Polyethylene Naphthalate 1,5-Naphthalate, Cyclic Polyethylene 1,5-Naphthalate-1,4-cyclohexanedimethyl, Cyclic Polyethylene 2,6-Naphthalate Alcohol ester, cyclic polytrimethylene 2,6-naphthalate, cyclic polybutylene 2,6-naphthalate, cyclic polyhexamethylene 2,6-naphthalate, cyclic poly-2 , one or more of 1,4-cyclohexanedimethyl 6-naphthalene dicarboxylate; when there are more than one, the ratio is arbitrary.

The first type of organic solvent is one or more of o-dichlorobenzene, tetrachloroethane, nitrobenzene, and 1,2,4-trichlorobenzene. When there are multiple types, the proportioning ratio is Any ratio.

The concentration of the dissolved cyclic aromatic polyester oligomer is 0.2-2Kg/L, the concentration of the dissolved monohydric alcohol is less than or equal to 200g/L, and the mass of the catalyst added is the reactant cyclic aromatic polyester oligomerization 0.01 to 1% of the total mass of substances and monohydric alcohols.

Step (2). Vacuum-dry the single-ended hydroxyaromatic polyester so that its moisture content is less than or equal to 20ppm, and dry the dried single-ended hydroxyaromatic polyester and the first type of lactide at 60-130°C Dissolve it in the first type of organic solvent that has been treated with anhydrous and oxygen free, then add tin salt catalyst, and react at 60-150°C; during the reaction, GPC (gel permeation chromatography) is used to monitor the reaction process, in the first type After the signal peak of lactide disappeared, the reaction was stopped; after the reaction was completed, it was cooled to normal temperature, and filtered to obtain the first type of crude product.

This reaction is in an organic solvent, at a relatively low reaction temperature, using a tin salt as a catalyst and a single-end hydroxyl aromatic polyester as an initiator to initiate the ring-opening polymerization of the first type of lactide to obtain the corresponding polylactic acid block copolymers.

The first type of lactide is L-lactide, D-lactide or D,L-lactide.

The concentration of the dissolved single-end hydroxy aromatic polyester is less than or equal to 100g/L, the concentration of the first type of lactide is less than or equal to 2Kg/L, and the mass of the added tin salt catalyst is the single-end hydroxy aromatic polyester and the first 0.01-1% of the total mass of lactide.

Step (3) dissolving the first type of crude product obtained in step (2) in the second type of organic solvent, and then using 3 to 5 times the volume of methanol of the second type of organic solvent for sedimentation, filtering and drying to obtain the first type product. The first type of product is a block copolymer comprising polylactic acid of a single configuration.

The second type of organic solvent is one of chloroform and trifluoroacetic acid or a mixture of both, and the concentration of the dissolved first type of crude product is 50-200 g/L.

Step (4) Dissolve the first type of product and the second type of lactide in the third type of organic solvent that has been treated anhydrous and oxygen-free, then add a tin salt catalyst, and react at 30-140 ° C. During the reaction, use GPC (gel permeation chromatography) monitors the reaction process, and stops the reaction after the signal peak of the second type of lactide disappears; after the reaction is completed, cool to room temperature and filter to obtain the second type of crude product.

This reaction is catalyzed by a tin salt catalyst, and the first type of product is used as an initiator to initiate the ring-opening polymerization of the second type of lactide to obtain an aromatic polyester containing two configurations of polylactic acid and polylactic acid. segment copolymers.

The second type of lactide is L-lactide, D-lactide or D,L-lactide, and is different from the first type of lactide.

The third type of organic solvent is one or more of dichloromethane, chloroform, carbon tetrachloride, toluene, tetrahydrofuran, o-dichlorobenzene, and tetrachloroethane. for any ratio.

The concentration of the first type of product after dissolution is less than or equal to 300g/L, the concentration of the second type of lactide is less than or equal to 2Kg/L, and the mass of the added tin salt catalyst is the total mass of the first type of product and the second type of lactide 0.01 to 1% of that.

Step (5) dissolves the second type of crude product obtained in step (4) in chloroform so that the concentration of the second type of crude product is 50 to 100 g/L, and then settles with methanol of 3 to 5 times the volume of chloroform, The second type of product is obtained by filtering and drying; the second type of product is a block copolymer containing polylactic acid with two configurations.

Step (6) Dissolve the second type of product and the third type of lactide in the third type of organic solvent that has been treated anhydrous and oxygen-free, then add a tin salt catalyst, and react at 30-140 ° C. During the reaction, use GPC (gel permeation chromatography) monitors the reaction process, and stops the reaction after the signal peak of the third type of lactide disappears; after the reaction is completed, cool to room temperature and filter to obtain the third type of crude product.

This reaction is under the catalysis of the tin salt catalyst, using the second type of product as the initiator to initiate the ring-opening polymerization of the third type of lactide to obtain aromatic polyesters containing three configurations of polylactic acid and polylactic acid. block copolymers.

The third type of lactide is L-lactide, D-lactide or D,L-lactide, and is different from the first type of lactide and the second type of lactide.

The concentration of the dissolved second-type product is less than or equal to 300g/L, the concentration of the third-type lactide is less than or equal to 2Kg/L, and the mass of the added tin salt catalyst is the total mass of the second-type product and the third-type lactide 0.01 to 1% of that.

Step (7) Dissolve the third type of crude product obtained in step (6) in chloroform so that the concentration of the third type of crude product is 50 to 100 g/L, then settle with 3 to 5 times the volume of methanol in chloroform, and filter The third type of product is obtained by drying; the third type of product is a block copolymer containing polylactic acid with three configurations.

The tin salt catalyst described in steps (1), (2), (4) and (6) is one of Sn(Oct) ₂ , SnCl ₂ , SnCl ₄ , and SnBr ₂ .

What the present invention adopts is the method of solution polymerization, namely first dissolves single-end hydroxy aromatic polyester and lactide in a certain amount of organic solvent, then adds a catalyst, and uses single-end hydroxy aromatic polyester as an initiator to initiate lactide. Ring-opening of lactide to obtain a block copolymer of aromatic polyester and polylactic acid. Through this method, the polymerization temperature can be controlled within the range where polylactic acid and lactide will not degrade or even racemize, effectively inhibiting the occurrence of transesterification, ensuring the regularity of the chain segment, and successfully preparing Block copolymers of polyesters including high melting point aromatic polyesters and polylactic acid are obtained.

Detailed ways

Below in conjunction with embodiment the present invention is described in further detail.

Example 1

Synthesis of block copolymers of polybutylene terephthalate (PBT) and polylactic acid (PLA).

Step (1). Ethanol triggers ring-opening polymerization of cyclic polybutylene terephthalate (CBT) to obtain single-end hydroxyl polybutylene terephthalate

Under nitrogen protection, put 10gCBT, 0.5g ethanol and 0.105g Sn(Oct) ₂ into a 100ml reaction flask that has been baked over fire and cooled with nitrogen protection. Add 5ml of o-dichlorobenzene treated with anhydrous and anaerobic by syringe, so that the concentration of CBT is 2Kg/L, and the concentration of ethanol is 100g/L. The reaction was carried out at 180°C. After 10 minutes, the reaction was over (GPC monitoring showed no signal peak of CBT), cooled and filtered, and the reaction product was washed with anhydrous chloroform to wash away traces of unreacted CBT monomer. Vacuum at 80°C drying.

Step (2). Single-terminal hydroxyl PBT initiates lactide polymerization. The 50ml reaction bottle was anhydrous and oxygen-free, cooled under nitrogen atmosphere, and then under the protection of nitrogen, add 0.06g single-terminal hydroxyl PBT and 4gL-lactide, and add 2ml tetrachloroethane with a syringe, so that the concentration of PBT The concentration of lactide is 30g/L, the concentration of lactide is 2Kg/L, and the temperature is raised to 120°C. At this temperature, the reaction solution is in the state of a uniform and transparent solution _. The reaction was monitored by GPC. After 6 hours, the signal peak of lactide disappeared, and the reaction was stopped. After cooling, it was filtered to obtain a white crude product.

Step (3). Get the crude product of step (2) gained, be dissolved in 5ml chloroform, make crude product concentration be 200 g/L, settle with 40ml methanol, filter and dry to obtain product, yield 95.8%, do GPC, ¹ H-NMR, ¹³ C-NMR, DSC various characterizations.

data:

GPC: Use chloroform as the mobile phase, flow rate 1.0ml/min, PS as the standard sample, where the spectrum presents a normal distribution, measured M _n =10.1K, M _w =15.2K, PDI=1.51

¹ H-NMR: 8.1ppm (the hydrogen on the benzene ring of the PBT block), 4.5ppm (the hydrogen of the two methylenes connected to the oxygen on the PBT block), 2.0ppm (the hydrogen connected to the carbon on the PBT block Hydrogen on the two methylene groups), 5.1ppm (hydrogen on the methine on the PLA block), 1.6ppm (hydrogen on the methyl group on the PLA block); no other peaks caused by transesterification were seen, and m was obtained from the integrated area _PBT : _mPLA =1:65

¹³ C-NMR: 170.0ppm (the carbonyl carbon on the PLA block), 69.2ppm (the methine carbon on the PLA block), 15.7ppm (the carbon on the methyl group of the PLA block); 167.0ppm (the carbon on the PBT block carbonyl carbon), 133.2ppm (the 1,4-position carbon on the PBT block benzene ring), 129.3ppm (the 2,3,5,6-position carbon on the PBT block benzene ring), 65.4ppm (the PBT block Carbons on the 1 and 4 methylene groups in the butylene structure), 24.6ppm (carbons on the 2 and 3 methylene groups in the butylene structure on the PBT block), and no other peaks caused by transesterification .

DSC: Tm ( ₂₁₅ °C) corresponds to the PBT block, Tm (160°C) _corresponds to the PLA block.

The GPC spectrum is a single peak, and the NMR spectrum has no peaks generated by transesterification, indicating that the obtained block copolymer is obtained. In addition, the DSC curve has two melting points of different blocks, which also shows from the side that the obtained block copolymer .

,R₂为(CH₂)₄，R₃为C₂H₅-,B段为左旋聚乳酸嵌段。 Therefore, what this embodiment obtains is a block copolymer of polybutylene terephthalate and L-polylactic acid. In the general formula, the R _of the A segment structural formula is

, R ₂ is (CH ₂ ) ₄ , R ₃ is C ₂ H ₅ -, block B is a L-polylactic acid block.

Example 2

Synthesis of block copolymers of polytrimethylene terephthalate (PTT) and polylactic acid (PLA).

Step (1). Methanol initiates ring-opening polymerization of cyclic polytrimethylene terephthalate (CTT) to obtain single-end hydroxyl polytrimethylene terephthalate

Under the protection of nitrogen, put 10g of CTT, 1.0g of methanol and _0.0011g of SnCl into a 100ml reaction flask that has been roasted and cooled with nitrogen. Add 5ml of tetrachloroethane treated with anhydrous and anaerobic by syringe, so that the concentration of CTT is 2Kg/L, and the concentration of methanol is 200g/L. The reaction was carried out at 180°C. After 5 minutes, the reaction was over (GPC monitoring showed no signal peak of CTT), cooled and filtered, and the reaction product was washed with anhydrous chloroform to wash away traces of unreacted CTT monomer. Vacuum at 60°C drying.

Step (2). Single-terminal hydroxyl PTT initiates lactide polymerization. The 100ml reaction bottle was treated with anhydrous and oxygen-free treatment, cooled under nitrogen atmosphere, and then under the protection of nitrogen, 0.06g single-terminal hydroxyl PTT and 1gD-lactide were added, and then 2ml o-dichlorobenzene was added with a syringe, so that the PTT The concentration is 30g/L, the concentration of lactide is 0.5Kg/L, and the temperature is raised to 60°C. At this temperature, the reaction solution is in a uniform and transparent solution state, and then 0.0106g SnCl ₂ is added with a syringe, and the reaction is carried out at 60°C. Monitored by GPC, the signal peak of lactide disappeared after 24 hours, the reaction was stopped, cooled and filtered to obtain a white crude product.

Step (3). Get the crude product of step (2) gained, be dissolved in 20ml chloroform, make crude product concentration be 50 g/L, settle with 60ml methanol, filter and dry to obtain final product, yield 96.0%, do GPC, ¹ H-NMR, ¹³ C-NMR, DSC various characterizations.

data:

GPC: Use chloroform as mobile phase, flow rate 1.0ml/min, PS as standard sample, where the spectrum shows normal distribution, measured M _n =8.9K, M _w =12.7K, PDI=1.43

¹ H-NMR: 8.19ppm (hydrogen on the benzene ring of the PTT block), 4.7ppm (PTT block 1, 3-propylene structure 1, hydrogen of two methylenes at the 3-position), 2.46ppm (PTT block 1, 3 propylene structure middle methylene hydrogen), 5.1ppm (hydrogen on the PLA block methine), 1.6ppm (PLA block hydrogen on the methyl group); no other peaks caused by transesterification , get m _PTT from the integral area: m _PLA =1:16

¹³ C-NMR: 170.0ppm (carbonyl carbon on the PLA block), 69.2ppm (methine carbon on the PLA block), 15.7ppm (carbon on the methyl group of the PLA block); 168.6ppm (on the PTT block carbonyl carbon), 133.2ppm (the carbons at positions 1 and 4 on the PTT block benzene ring), 129.4ppm (the carbons at the 2, 3, 5, and 6 positions on the PTT block benzene ring), 63.0ppm (the Segment 1, the carbon on the 1, 3-position methylene in the 3-propylene structure), 26.8ppm (PTT block 1, the carbon of the 2-position methylene in the 3-propylene structure), the rest is not seen by transesterification generated peaks.

DSC: T _m (173°C) corresponds to PLA block, T _m (212°C) corresponds to PTT block

The GPC spectrum is a single peak, and there is no peak generated by transesterification in the NMR spectrum, which means that what is obtained is a block copolymer

Therefore, what this embodiment obtains is a block copolymer of poly(trimethylene terephthalate) and dextrorotatory polylactic acid. In the general formula, R in the structural formula of section A _is , R ₂ is (CH ₂ ) ₃ , R ₃ is CH ₃ -, block B is a D-polylactic acid block.

Example 3

Synthesis of block copolymers of polyethylene terephthalate (PET) and polylactic acid (PLA).

Step (1). 1-propanol initiates ring-opening polymerization of cyclic polyethylene terephthalate (CET) to obtain single-end hydroxyl polyethylene terephthalate

Under the protection of nitrogen, put 10g of CET, 0.1g of 1-propanol and 0.0101 g of SnBr ₂ into a 100ml reaction flask that has been roasted and cooled with nitrogen protection. Add 50ml of anhydrous and anaerobic treated nitrobenzene with a syringe, so that the concentration of CET is 0.2Kg/L, and the concentration of 1-propanol is 2g/L. The reaction was carried out at 120°C. After 60 minutes, the reaction was over (GPC monitoring had no signal peak of CET), cooled and filtered, and the reaction product was washed with anhydrous chloroform to wash away traces of unreacted CET monomers, and vacuumed at 80°C. drying.

Step (2). Single-end hydroxyl PET initiates lactide polymerization. The 100ml reaction bottle was treated anhydrous and oxygen-free, cooled under a nitrogen atmosphere, and then under the protection of nitrogen, 0.06g of single-end hydroxyl PET and 1g of D-lactide were added, and then 2ml _{of V tetrachloroethane} : V _{o Dichlorobenzene} = 1:1 mixed solvent, so that the concentration of PET is 30g/L, the concentration of lactide is 0.5Kg/L, and the temperature is raised to 120°C. At this temperature, the reaction solution is in a uniform and transparent solution state. Then add 0.0106g SnBr ₂ with a syringe, react at 130°C, and monitor by GPC. After 5 hours, the signal peak of lactide disappears, stop the reaction, cool and filter to obtain a white crude product.

Step (3). Add 20ml of chloroform to the crude product so that the concentration of the crude product is 50g/L, settle with 100ml of methanol, filter and dry to obtain the final product, 96.2%, do GPC, ¹ H-NMR, ¹³ C-NMR, Various characterizations of DSC.

data

GPC: Use chloroform as the mobile phase, flow rate 1.0ml/min, PS as the standard sample, where the spectrum shows a normal distribution, measured M _n =23.1K, M _w =31.4K, PDI=1.36

¹ H-NMR: 7.97ppm (hydrogen on the benzene ring of the PET block), 4.67ppm (hydrogen on the ethylene group of the PET block), 5.42ppm (hydrogen on the methine of the PLA block), 1.68ppm (the hydrogen on the PLA block The hydrogen on the methyl segment); no other peaks produced by transesterification were seen, and m _PET was obtained from the integrated area: m _PLA = 1:16.

¹³ C-NMR: 170.0ppm (carbonyl carbon on the PLA block), 69.2ppm (methine carbon on the PLA block), 15.7ppm (carbon on the methyl group of the PLA block); 168.4ppm (on the PET block carbonyl), 133.0ppm (the carbon connected to the carbonyl on the benzene ring of the PET block), 129.5ppm (the carbons at the 2, 3, 4, and 5 positions of the benzene ring on the PET block), 63.6ppm (the ethylene structure of the PET block carbons on the two methylene groups attached to the oxygen), the remaining peaks due to transesterification were not seen

DSC: T _m (160°C) corresponds to PLA block, T _m (245°C) corresponds to PET block

The GPC spectrum is a single peak, and the NMR spectrum has no peaks generated by transesterification, which means that what is obtained is a block copolymer.

,R₂为(CH₂)₂,R₃为C₃H₇-,B段为右旋聚乳酸嵌段。 So what this embodiment obtains is the block copolymer of polyethylene terephthalate and polylactic acid, and in the general formula, the _R of the A section structural formula is

, R ₂ is (CH ₂ ) ₂ , R ₃ is C ₃ H ₇ -, block B is a D-polylactic acid block.

Example 4

Synthesis of Poly(Hexylene-2,6-Naphthalate) (PHN) and Polylactic Acid (PLA) Block Copolymers.

Step (1). Ring-opening polymerization of cyclic poly(2,6-naphthalene dicarboxylate) (CHN) initiated by 1-butanol to obtain single-terminal hydroxyl poly(2,6-naphthalene dicarboxylate)

Under the protection of nitrogen, put 10g of CHN, 0.1g of 1-butanol and 0.0101 g of SnCl ₄ into a 100ml reaction flask that has been roasted and cooled with nitrogen protection. Add 40ml of 1,2,4-trichlorobenzene treated with anhydrous and anaerobic by syringe, so that the concentration of CHN is 0.25Kg/L, and the concentration of 1-butanol is 2.5g/L. The reaction was carried out at 150°C. After 30 minutes, the reaction was completed (GPC monitoring had no signal peak of CHN), cooled and filtered, and the reaction product was washed with anhydrous chloroform to wash away traces of unreacted CHN monomers, and vacuumed at 80°C. drying.

Step (2). Single-terminal hydroxyl PHN initiates lactide polymerization. The 100ml reaction bottle was anhydrous and oxygen-free, cooled under nitrogen atmosphere, and then added 0.1g single-terminal hydroxyl PHN and 2g D,L-lactide under the protection of nitrogen, and then added 10ml1,2,4- Trichlorobenzene, so that the concentration of PHN is 10g/L, the concentration of lactide is 0.2Kg/L, and the temperature is raised to 130°C. At this temperature, the reaction solution is in a uniform and transparent solution state, and then 0.003g SnCl is added with a syringe. _4. React at 150°C and monitor with GPC. After 2 hours, the signal peak of lactide disappears, stop the reaction, cool and filter to obtain a white crude product.

Step (3). Take the crude product obtained in step (2), add 40ml of chloroform to make the crude product concentration 50g/L, settle with 120ml of methanol, filter and dry to obtain the final product, the yield is 97.1%, and do GPC, ¹ H- Various characterizations by NMR, ¹³ C-NMR, and DSC.

data:

GPC: Use chloroform as mobile phase, flow rate 1.0ml/min, PS as standard sample, where the spectrum shows normal distribution, measured M _n =65.1K, M _w =101.56K, PDI=1.56

¹ H-NMR: 8.85ppm (hydrogen at positions 1 and 5 on the PHN block naphthalene ring), 8.15ppm (hydrogen at positions 3, 4, 7, and 8 on the PHN block naphthalene ring), 4.5ppm (hydrogen at positions 3, 4, 7, and 8 on the PHN block naphthalene ring) 1, 6 hydrogen on the two methylene groups), 1.7ppm (the hydrogen on the 3, 4-position two methylene groups in the PHN block hexamethylene group), 2.05ppm (2, 5-position two in the PHN block hexamethylene group Hydrogen on the methylene), 5.1ppm (hydrogen on the methine of the PLA block), 1.6ppm (hydrogen on the methyl group of the PLA block); no other peaks caused by transesterification were seen, and m _PHN was obtained from the integrated area: _mPLA =1:19.

¹³ C-NMR: 167.0ppm (the carbonyl carbon on the PHN block), 131.2 ppm (the carbon on the 1st and 5th positions of the naphthalene ring on the PHN block), 132.4 ppm (the 2nd and 6th positions on the naphthalene ring on the PHN block carbon on the PHN block), 130.0 ppm (the carbon on the 3rd and 7th positions of the naphthalene ring on the PHN block), 130.0 ppm (the carbon on the 4th and 8th position of the naphthalene ring on the PHN block), 61.2 ppm (the carbon on the 8th position of the naphthalene ring on the PHN block), 61.2 ppm (the 1, 6 carbons on the two methylene groups in the hexyl group), 25.2 (the carbons on the 2 and 5 methylene groups in the PHN block hexylene group), 20.6 (the 3 and 4 positions in the PHN block hexylene group carbons on two methylene groups), 170.0ppm (carbonyl carbon on PLA block), 69.2ppm (methine carbon on PLA block), 15.7ppm (carbon on methyl group of PLA block); rest not seen Peaks resulting from transesterification

DSC: T _m (205°C) corresponds to the PHN block, and the melting endothermic peak of the PLA block is not seen because the racemic polylactic acid is generated.

The GPC spectrum is a single peak, and the NMR spectrum has no peaks generated by transesterification, which means that what is obtained is a block copolymer.

,R₂为(CH₂)₆，R₃为C₄H₉-,B段为外消旋聚乳酸嵌段。 What is obtained in this embodiment is a block copolymer of poly(2,6-hexanediol naphthalate) (PHN) and polylactic acid. In the general formula, _the R of the A segment structural formula is

, R ₂ is (CH ₂ ) ₆ , R ₃ is C ₄ H ₉ -, segment B is a racemic polylactic acid block.

Example 5

Synthesis of block copolymers of poly-1,4-cyclohexanedimethyl-2,6-naphthalate (PCN) and polylactic acid (PLA).

Step (1). Ring-opening polymerization of cyclic poly-2,6-naphthalene dicarboxylate-1,4-cyclohexanedimethylester (CCN) initiated by 1-nonanol to obtain single-terminal hydroxyl poly-2,6-naphthalene dicarboxylate 1,4-cyclohexanedimethyl formate.

Under the protection of nitrogen, put 10g of CCN, 0.1g of 1-nonanol and 0.0101 g of Sn(Oct) ₂ into a 100ml reaction flask which has been roasted and cooled with nitrogen. Add 10ml of V _{tetrachloroethane} :V _{o-dichlorobenzene} =1:1 mixed solvent through anhydrous and anaerobic treatment with a syringe, so that the concentration of CCN is 1.0Kg/L, and the concentration of 1-nonanol is 10g/L . The reaction was carried out at 170°C. After 10 minutes, the reaction was completed (GPC monitored no signal peak of CCN), cooled and filtered, and the reaction product was washed with anhydrous chloroform to wash away traces of unreacted CCN monomer. Vacuum at 80°C drying.

Step (2). Single-terminal hydroxyl PCN initiates lactide polymerization. The 100ml reaction bottle was treated with anhydrous and oxygen-free treatment, cooled under nitrogen atmosphere, and then under the protection of nitrogen, add 0.1g of single-terminal hydroxyl PCN and 2g of D-lactide obtained in step (1), and then add 10ml of nitric acid with a syringe benzene, so that the concentration of PCN is 10g/L, the concentration of lactide is 0.2Kg/L, and the temperature is raised to 100°C. At this temperature, the reaction solution is in a uniform and transparent solution state, and then 0.003g Sn ( Oct) ₂ , reacted at 120°C, monitored by GPC, the signal peak of lactide disappeared after 3 hours, the reaction was stopped, cooled and filtered to obtain a white crude product.

Step (3). Get the crude product obtained in step (2), add 40ml chloroform, make the crude product concentration be 52g/L, settle with 150ml methanol, filter and dry to obtain the final product, yield 97.7%, do GPC, ¹ H - Various characterizations by NMR, ¹³ C-NMR, and DSC.

data:

GPC: Use chloroform as the mobile phase, flow rate 1.0ml/min, PS as the standard sample, where the spectrum shows a normal distribution, measured M _n =21.1K, M _w =34.42K, PDI=1.49

¹ H-NMR: 8.82ppm (hydrogen at positions 1 and 5 on the naphthalene ring), 8.11ppm (hydrogen at positions 3, 4, 7, and 8 on the naphthalene ring), 4.4ppm (hydrogen at positions 3, 4, 7, and 8 on the naphthalene ring), 4.4ppm (hydrogen in the PCN block and cyclohexylene 1, the hydrogen on the two methylene groups connected at the 4-position), 1.3~2.2ppm (the hydrogen on the PCN block cyclohexylene), 5.1ppm (the hydrogen on the PLA block methine), 1.6ppm (the PLA block methyl Hydrogen on the top); no other peaks produced by transesterification were seen, and m _PCN was obtained from the integrated area: m _PLA =1:19

¹³ C-NMR: 168.2ppm (the carbonyl carbon on the PCN block), 131.1 ppm (the carbon on the 1st and 5th positions of the naphthalene ring on the PCN block), 132.3 ppm (the 2nd and 6th positions on the naphthalene ring on the PCN block carbon on the PCN block), 130.1 ppm (the carbon on the 3rd and 7th positions of the naphthalene ring on the PCN block), 130.4 ppm (the carbon on the 4th and 8th position of the naphthalene ring on the PCN block), 136.1 ppm (the carbon on the 8th position on the naphthalene ring on the PCN block 9, 10 carbons on the naphthalene ring), 61.2ppm (the carbons on the two methylenes connected to the 1, 4 positions in the PCN block cyclohexylene), 25.2 ppm (the 1, 4 two times in the PCN block cyclohexylene carbon on the methyl group), 18.6 ppm (carbons on the 2, 3, 5, and 6 methylene groups in the PCN block cyclohexylene), 170.0 ppm (the carbonyl carbon on the PLA block), 69.2 ppm (the PLA block methine carbon on the PLA block), 15.7ppm (carbon on the methyl group of the PLA block); no remaining peaks from transesterification were seen.

DSC: T _m (168°C) corresponds to PLA block, T _m (320°C) corresponds to PCN block

The GPC spectrum is a single peak, and the NMR spectrum has no peaks generated by transesterification, which means that what is obtained is a block copolymer.

,R₂为，R₃为C₉H₁₉-,B段为右旋聚乳酸嵌段。 What is obtained in this example is a block copolymer of poly-2,6-naphthalene dicarboxylate-1,4-cyclohexanedimethylester (PCN) and polylactic acid. In the general formula, R ₁ of the structural formula of section A for

, R ₂ is , R ₃ is C ₉ H ₁₉ -, block B is a D-polylactic acid block.

Example 6

Synthesis of block copolymers of polyethylene 1,4-naphthalate and polylactic acid (PLA).

Step (1). Allyl alcohol initiates ring-opening polymerization of cyclic polyethylene 1,4-naphthalate to obtain single-terminal hydroxyl polyethylene 1,4-naphthalate.

Under the protection of nitrogen, put 10g of cyclic polyethylene 1,4-naphthalate, 0.3g of allyl alcohol and 0.0103g of Sn(Oct) ₂ into the reaction of 100ml that has been cooled by fire roasting and nitrogen protection bottle. Add 10ml of V _{tetrachloroethane} : V _{o-dichlorobenzene} : V _{trichlorobenzene} = 1:1:1 mixed solvent through anhydrous and anaerobic treatment with a syringe, so that the cyclic polyethylene 1,4-naphthalene dicarboxylate The concentration of alcohol ester is 1.0Kg/L, and the concentration of allyl alcohol is 30g/L. The reaction was carried out at 160°C. After 15 minutes, the reaction was completed (GPC monitored the signal peak of no monomer), cooled and filtered, and the reaction product was washed with anhydrous chloroform to wash away traces of unreacted monomers. Vacuum at 60°C drying.

Step (2). Single-terminal hydroxyl polyethylene 1,4-naphthalene dicarboxylate initiates lactide polymerization. The 100ml reaction bottle was anhydrous and oxygen-free, cooled under a nitrogen atmosphere, and then added 1g of the single-terminal hydroxyl polyethylene 1,4-naphthalene dicarboxylate obtained in step (1) and 3g of D- Lactide, then add 20ml V _{tetrachloroethane} : V _{o-dichlorobenzene} : V _nitrobenzene = 1:1:1 mixed solvent with a syringe, so that the concentration of polyethylene 1,4-naphthalene dicarboxylate The concentration of lactide is 50g/L, the concentration of lactide is 0.15Kg/L _, and the temperature is raised to 120°C. At this temperature, the reaction liquid is in the state of a uniform and transparent solution. The reaction was monitored by GPC. After 5 hours, the signal peak of lactide disappeared, the reaction was stopped, and the white crude product was obtained by filtration after cooling.

Step (3). Get the crude product of step (2) gained, add 20ml trifluoroacetic acid, make crude product concentration 200g/L, settle with 100ml methanol, filter and dry to obtain final product, yield 98.1%, do GPC, ¹ Various characterizations by H-NMR, ¹³ C-NMR, and DSC.

data:

GPC: Due to the large content of polyethylene 1,4-naphthalate block in the copolymer, the solubility in chloroform is not very ideal, so first use o-chlorophenol as the solvent to make 10mg/mL, Then dilute to 1mg/mL with chloroform, use the mixed solvent with the volume ratio of chloroform and o-chlorophenol as 10 as the mobile phase, flow rate 1.0ml/min, take PS as the standard sample, _wherein the spectrum shows a normal distribution, and the measured Mn =54.1K, M _w =85.48K, PDI=1.58

¹ H-NMR: 8.75ppm (hydrogen at positions 2 and 3 on the naphthalene ring), 8.05ppm (hydrogen at positions 6 and 7 on the naphthalene ring), 8.55ppm (hydrogen at positions 5 and 8 on the naphthalene ring) 4.70 ppm (hydrogen on the two methylene groups in polyethylene 1,4-naphthalate), 5.1ppm (hydrogen on the methine in the PLA block), 1.6ppm (hydrogen on the methyl group in the PLA block); No other peaks caused by transesterification were seen, and m _{polyethylene 1,4-naphthalene dicarboxylate} was obtained from the integrated area: m _PLA = 1:3.

¹³ C-NMR: 168.6.0ppm (carbonyl carbon on polyethylene 1,4-naphthalene dicarboxylate block), 132.7 ppm (naphthalene ring on polyethylene 1,4-naphthalene dicarboxylate block 1,4-position carbon), 126.9ppm (2,3-position carbon of the naphthalene ring on the polyethylene 1,4-naphthalene dicarboxylate block), 131.4 ppm (poly-1,4-naphthalene dicarboxylic acid The carbon on the 5th and 8th position of the naphthalene ring on the ethylene glycol ester block), 127.9ppm (the 6th, 7th carbon on the naphthalene ring on the polyethylene 1,4-naphthalene dicarboxylate block), 135.1 ppm (the carbon on the 9th and 10th positions of the naphthalene ring on the polyethylene 1,4-naphthalene dicarboxylate block), 66.7ppm (the two ethylene groups in the polyethylene 1,4-naphthalene dicarboxylate block carbon on the methylene), 170.0ppm (carbonyl carbon on the PLA block), 69.2ppm (methine carbon on the PLA block), 15.7ppm (carbon on the methyl group of the PLA block); Exchange generated peaks.

DSC: T _m (230℃) corresponds to polyethylene-1,4-naphthalate block, T _m (160℃) corresponds to the melting peak of polylactic acid

The GPC spectrum is a single peak, and the NMR spectrum has no peaks generated by transesterification, which means that what is obtained is a block copolymer.

,R₂为(CH₂)₂，R₃为

,B段为右旋聚乳酸嵌段。 Obtained in this embodiment is the block copolymer of polyethylene 1,4-naphthalate and polylactic acid, and in the general formula, the _R of the A section structural formula is

, R ₂ is (CH ₂ ) ₂ , R ₃ is

, Block B is a D-polylactic acid block.

Example 7

Synthesis of block copolymers of polyethylene 1,5-naphthalate and polylactic acid (PLA).

Step (1). Benzyl alcohol initiates ring-opening polymerization of cyclic polyethylene 1,5-naphthalate to obtain single-terminal hydroxyl polyethylene 1,5-naphthalate.

Under the protection of nitrogen, put 10g of cyclic polyethylene 1,5-naphthalate, 0.3g of benzyl alcohol and 0.0103g of Sn(Oct) ₂ into the reaction of 100ml which has been cooled by the protection of nitrogen. bottle. Add 10ml of V _{tetrachloroethane} through anhydrous and oxygen-free treatment with a syringe: V _{o-dichlorobenzene} : V _{trichlorobenzene} : V _{1,2,4 Trichlorobenzene} =1:1:1:1 mixed solvent, making The concentration of cyclic polyethylene 1,5-naphthalate was 1.0 Kg/L, and the concentration of benzyl alcohol was 30 g/L. The reaction was carried out at 150°C. After 20 minutes, the reaction was completed (GPC monitored the signal peak of no monomer), cooled and filtered, and the reaction product was washed with anhydrous chloroform to wash away traces of unreacted monomers. Vacuum at 60°C drying.

Step (2). Single-terminal hydroxyl polyethylene 1,5-naphthalene dicarboxylate initiates lactide polymerization. The 100ml reaction bottle was anhydrous and oxygen-free, cooled under a nitrogen atmosphere, and then added 1g of the single-terminal hydroxyl polyethylene 1,5-naphthalene dicarboxylate obtained in step (1) and 1g of D , L-lactide, then add 20ml V _{tetrachloroethane} : V _{o-dichlorobenzene} : V _nitrobenzene : V _{1, 2, 4 trichlorobenzene} = 1:1:1:1 mixed solvent with a syringe, so that The concentration of polyethylene 1,5-naphthalate is 50g/L, the concentration of lactide is 0.05Kg/L, and the temperature is raised to 130°C. At this temperature, the reaction liquid is in a uniform and transparent solution state. Add 0.02g Sn(Oct) ₂ with a syringe, react at 150°C, and monitor with GPC. After 3 hours, the signal peak of lactide disappears, stop the reaction, cool and filter to obtain a white crude product.

Step (3). Get the crude product of step (2) gained, add 20ml trifluoroacetic acid, make crude product concentration 100g/L, settle with 90ml methanol, filter and dry to obtain final product, yield 98.5%, do GPC, ¹ Various characterizations by H-NMR, ¹³ C-NMR, and DSC.

data:

GPC: Due to the large content of polyethylene 1,5-naphthalate block in the copolymer, the solubility in chloroform is not very ideal, so first use o-chlorophenol as the solvent to make 10mg/mL, Then dilute to 1 mg/mL with chloroform, use a mixed solvent with a volume ratio of chloroform and o-chlorophenol of 10 as the mobile phase, flow rate 1.0ml/min, take PS as the standard sample, wherein the spectrum shows a normal distribution, and the measured M _n =65.6K, M _w =106.1K, PDI=1.62

¹ H-NMR: 8.75ppm (hydrogen at positions 4 and 8 on the naphthalene ring), 8.05ppm (hydrogen at positions 2, 3, 6, and 7 on the naphthalene ring), 4.71ppm (poly-1,5-naphthalene dicarboxylic acid Hydrogen on the two methylene groups in ethylene glycol ester), 5.1ppm (hydrogen on the methine in the PLA block), 1.6ppm (hydrogen on the methyl group in the PLA block); no other peaks caused by transesterification, Obtain m _{polyethylene naphthalate} from the integral area: m _PLA =1:1

¹³ C-NMR: 171.0ppm (carbonyl carbon on polyethylene 1,5-naphthalene dicarboxylate block), 126.9 ppm (naphthalene ring 1,5 on polyethylene 1,5-naphthalene dicarboxylate carbon at position), 132.7 ppm (carbon at 2,6 position of naphthalene ring on polyethylene 1,5-naphthalene dicarboxylate block), 131.4 ppm (carbon at position 6 of polyethylene 1,5-naphthalene dicarboxylate 3,7-position carbon of the naphthalene ring on the ester block), 129.6 ppm (4,8-position carbon of the naphthalene ring on the polyethylene 1,5-naphthalene dicarboxylate block), 134.1 ppm (polyethylene naphthalate 1,5-naphthalene dicarboxylate block on the naphthalene ring 9, carbon on the 10th position), 66.7ppm (two methylene groups in polyethylene 1,5-naphthalene dicarboxylate block carbon on the PLA block), 170.0ppm (carbonyl carbon on the PLA block), 69.2ppm (methine carbon on the PLA block), 15.7ppm (carbon on the methyl group of the PLA block); peak.

DSC: T _m (262°C) corresponds to the block of polyethylene 1,5-naphthalate. Since the block of racemic polylactic acid is formed, there is no melting peak of polylactic acid.

The GPC spectrum is a single peak, and the NMR spectrum has no peaks generated by transesterification, which means that what is obtained is a block copolymer.

,R₂为(CH₂)₂，R₃为

,B段为外消旋聚乳酸嵌段。 Obtained in this embodiment is the block copolymer of polyethylene 1,5-naphthalate and polylactic acid, and in the general formula, the _R of the A section structural formula is

, R ₂ is (CH ₂ ) ₂ , R ₃ is

, Block B is a racemic polylactic acid block.

Example 8

Synthesis of block copolymers of poly(2,6-naphthalene dicarboxylate-ethylene glycol-hexanediol) (P(EN ₉₀ -HN ₁₀ )) and polylactic acid (PLA). Where P (EN ₉₀ -HN ₁₀ ) means that the copolyester segment contains 90% mole fraction of PEN and 10% mole fraction of PHN

Step (1). Benzyl alcohol initiates ring-opening polymerization of cyclic polyethylene 2,6-naphthalene dicarboxylate and cyclic polyethylene 2,6-naphthalene dicarboxylate to obtain single-ended hydroxyl poly(2,6- Naphthalene dicarboxylic acid-ethylene glycol-hexanediol ester.

Under nitrogen protection, 10 g of cyclic polyethylene 2,6-naphthalene dicarboxylate and cyclic polyethylene 2,6-naphthalene dicarboxylate with a molar ratio of 9, 0.2 g of benzyl alcohol and 0.0102 g Sn(Oct) ₂ was put into a 100ml reaction flask which had been roasted and cooled with nitrogen gas. 10ml of tetrachloroethane treated with anhydrous and anaerobic was added with a syringe, so that the total concentration of the reaction monomer was 1.0Kg/L, and the concentration of benzyl alcohol was 20g/L. The reaction was carried out at 180°C. After 5 minutes, the reaction was completed (GPC monitored the signal peak of no monomer), cooled and filtered, and the reaction product was washed with anhydrous chloroform to wash away traces of unreacted monomers. Vacuum at 60°C drying.

Step (2). The P (EN ₉₀ -HN ₁₀ ) of the single-terminal hydroxyl group initiates lactide polymerization. The 100ml reaction bottle was anhydrous and oxygen-free, cooled under nitrogen atmosphere, and then added 1g of the single-terminal hydroxyl P (EN ₉₀ -HN ₁₀ ) obtained in step (1) and 3g of D, L-lactate under the protection of nitrogen ester, and then add 10ml of tetrachloroethane with a syringe, so that the concentration of P (EN ₉₀ -HN ₁₀ ) is 100g/L, and the concentration of lactide is 0.3Kg/L. Dissolve at 120°C. At this temperature, the reaction The liquid is in the state of a uniform and transparent solution, then add 0.0004g Sn(Oct) ₂ with a syringe, react at 120°C, monitor with GPC, the signal peak of lactide disappears after 3 hours, stop the reaction, filter after cooling to obtain a white crude product .

Step (3). Get the crude product of step (2) gained, add 40ml trifluoroacetic acid, make crude product concentration 100g/L, settle with 150ml methanol, filter and dry to obtain final product, yield 97.5%, do GPC, ¹ Various characterizations by H-NMR, ¹³ C-NMR, and DSC.

data:

GPC: Due to the large content of P (EN ₉₀ -HN ₁₀ ) blocks in the copolymer, the solubility in chloroform is not very ideal, so first use o-chlorophenol as a solvent to prepare 10mg/mL, and then dilute with chloroform to 1 mg/mL, using a mixed solvent with a volume ratio of chloroform and o-chlorophenol of 10 as the mobile phase, a flow rate of 1.0ml/min, and PS as a standard sample, where the spectrum presents a normal distribution, and the measured M _n =25.1K , M _w =39.1K, PDI=1.56

¹ H-NMR: 8.85ppm (hydrogen at the 1,5 position on the P(EN ₉₀ -HN ₁₀ ) block naphthalene ring), 8.15ppm (3,4,7,8 positions on the P(EN ₉₀ -HN ₁₀ ) block naphthalene ring hydrogen on), 4.5ppm (hydrogen on the 1, 6 two methylene groups in P(EN ₉₀ -HN ₁₀ ) block hexamethylene), 1.7ppm (P(EN ₉₀ -HN ₁₀ ) block hexamethylene Hydrogen on the two methylene groups in the 3 and 4 positions), 2.05ppm (P (EN ₉₀ -HN ₁₀ ) block block hexamethylene 2, the hydrogen on the two methylene groups in the 5 position), 4.67ppm (P (EN ₉₀ -HN ₁₀ ) Hydrogen on two methylene groups in block ethylene), 5.1ppm (hydrogen on PLA block methine), 1.6ppm (hydrogen on PLA block methyl group); The peak generated by the exchange of 2,6-naphthalene dicarboxylic acid-ethylene glycol-hexanediol ester with polylactic acid ester, m _{P (EN90-HN10)} obtained from the integrated area: m _PLA =1:2.8

¹³ C-NMR: 171.0ppm (carbonyl carbon on the P (EN ₉₀ -HN ₁₀ ) block), 126.9 ppm (carbon on the 1st and 5th positions of the naphthalene ring on the P (EN ₉₀ -HN ₁₀ ) block), 132.7 ppm (carbons at the 2nd and 6th positions of the naphthalene ring on the P (EN ₉₀ -HN ₁₀ ) block), 131.4 ppm (carbons at the 3rd and 7th positions of the naphthalene ring on the P (EN ₉₀ -HN ₁₀ ) block ), 129.6 ppm (the carbon on the 4th and 8th position of the naphthalene ring on the P (EN ₉₀ -HN ₁₀ ) block), 66.7 ppm (the carbon on the two methylene groups in the P (EN ₉₀ -HN ₁₀ ) block ethylene carbon), 131.2 ppm (carbon on the 1st, 5th position of the naphthalene ring on the P (EN 90 -HN ₁₀ ) block), 132.4 ppm (2 _, 6th position on the naphthalene ring on the P (EN ₉₀ -HN ₁₀ ) block carbon on the P(EN ₉₀ -HN ₁₀ ) block), 130.0 ppm (the carbon on the naphthalene ring 3,7 position on the P(EN 90 -HN 10 ) block), 130.0 ppm (the naphthalene ring 4 on the P(EN ₉₀ -HN ₁₀ ) block, 8-position carbon), 61.2ppm (carbons on the 1 and 6 methylene groups in P(EN ₉₀ -HN ₁₀ ) block hexamethylene), 25.2 (P(EN ₉₀ -HN ₁₀ ) block hexamethylene 2, 5 carbons on the two methylene groups), 20.6 (carbons on the 3, 4 methylene groups in the P (EN ₉₀ -HN ₁₀ ) block hexamethylene), 170.0ppm (on the PLA block carbonyl carbon), 69.2ppm (methine carbon on the PLA block), 15.7ppm (carbon on the methyl group of the PLA block); Peaks generated by polylactate exchange.

DSC: T _m (220°C) corresponds to the P (EN ₉₀ -HN ₁₀ ) block, and there is no melting peak of PLA due to the generated racemic polylactic acid block.

The GPC spectrum is a single peak, and the NMR spectrum has no peaks generated by transesterification, which means that what is obtained is a block copolymer.

,R₂为(CH₂)₂和(CH₂)₆，其中(CH₂)₂和(CH₂)₆的摩尔比为90:10，R₃为

，B段为外消旋聚乳酸嵌段。 Obtained in this embodiment is the block copolymer of poly-2,6-naphthalene dicarboxylic acid-ethylene glycol-hexanediol ester and polylactic acid, and in general formula, the _R of A section structural formula is

, R ₂ is (CH ₂ ) ₂ and (CH ₂ ) ₆ , wherein the molar ratio of (CH ₂ ) ₂ and (CH ₂ ) ₆ is 90:10, and R ₃ is

, Block B is a racemic polylactic acid block.

Example 9

Polyethylene terephthalate - ethylene glycol _{80 -} propylene glycol ₁₀ - butanediol ₁₀ ester (referred to as PE ₈₀ T ₁₀ B ₁₀ T, the subscript is expressed as a mole percentage, and the subscript of diol indicates the binary Alcohol accounts for the mole percentage of total alcohol) and the synthesis of polylactic acid block copolymer.

Step (1). 1-pentanol initiates ring-opening polymerization of cyclic polyethylene terephthalate, cyclic polytrimethylene terephthalate, and cyclic polybutylene terephthalate to obtain single-ended Hydroxypoly-2,6-naphthalene-dicarboxylate-ethylene glycol-hexanediol ester.

Under nitrogen protection, cyclic polyethylene terephthalate, cyclic polytrimethylene terephthalate, cyclic polybutylene terephthalate, 0.4g of 1-pentanol and 0.0104g of Sn(Oct) ₂ were put into a 100ml reaction flask which had been roasted and cooled with nitrogen gas protection. 5ml of tetrachloroethane treated with anhydrous and anaerobic treatment was added with a syringe, so that the total concentration of the reaction monomer was 2.0Kg/L, and the concentration of 1-pentanol was 20g/L. The reaction was carried out at 170°C. After 10 minutes, the reaction was completed (GPC monitored the signal peak of no monomer), cooled and filtered, and the reaction product was washed with anhydrous chloroform to wash away traces of unreacted monomers. Vacuum at 60°C drying.

Step (2). Single-end hydroxyl PE ₈₀ T ₁₀ B ₁₀ T initiates lactide polymerization. The 100ml reaction bottle was anhydrous and oxygen-free, cooled under a nitrogen atmosphere, and then added 1g of the single-end hydroxyl PE ₈₀ T ₁₀ B ₁₀ T obtained in step (1) and 3g of D, L-lactide under the protection of nitrogen , and then add 10ml of tetrachloroethane with a syringe, so that the concentration of PPE ₈₀ T ₁₀ B ₁₀ T is 100g/L, the concentration of lactide is 0.3Kg/L, and the temperature is raised to 120°C. At this temperature, the reaction solution is In a uniform and transparent solution state, add 0.04g Sn(Oct) ₂ with a syringe, react at 120°C, and monitor with GPC. After 3 hours, the signal peak of lactide disappears, stop the reaction, cool and filter to obtain a white crude product.

Step (3). Get the crude product of step (2) gained, add 20ml trifluoroacetic acid, make crude product concentration 200g/L, settle with 100ml methanol, filter and dry to obtain final product, yield 93.5%, do GPC, ¹ Various characterizations by H-NMR, ¹³ C-NMR, and DSC.

data:

GPC: Due to the large content of aromatic copolyester blocks in the copolymer, the solubility in chloroform is not very ideal, so first use o-chlorophenol as the solvent to make 10mg/mL, and then dilute to 1 mg with chloroform /mL, the mixed solvent with the volume ratio of chloroform and o-chlorophenol as 10 is the mobile phase, the _flow rate is 1.0ml/min, and PS is used as the _standard sample . =42.02K, PDI=1.36

¹ H-NMR: ¹ H-NMR: 8.1ppm (hydrogen on the benzene ring of the PBT block), 4.65ppm (hydrogen on the two methylene groups connected to oxygen on the aromatic polyester block), 2.0ppm ( Hydrogen on the 2,3 positions of 1,4-butylene on the aromatic polyester block), 2.46ppm (hydrogen on the methylene in the middle of the 1,3-propylene structure of the aromatic polyester block), 5.14ppm ( Hydrogen on the methine of the PLA block), 1.67ppm (hydrogen on the methyl group of the PLA block); no remaining peaks due to transesterification

¹³ C-NMR: 170.0ppm (carbonyl carbon on the PLA block), 69.2ppm (methine carbon on the PLA block), 15.7ppm (carbon on the methyl group of the PLA block); 168.0ppm (aromatic polyester block carbonyl carbon on the block), 133.2ppm (carbons on the 1,4 positions on the benzene ring of the aromatic polyester block), 129.3ppm (on the 2,3,5,6 positions of the aromatic polyester block benzene ring carbon), 65.4ppm (1, 4 carbons on the two methylene groups on the aromatic polyester block), 63.0ppm (1,3 propylene structure on the aromatic polyester block, 1, Carbon on the 3-position methylene and carbon on the ethylene structure), 26.8ppm (aromatic polyester block 1, carbon on the 2-position methylene in the 3-propylene structure) 24.6ppm (aromatic polyester 2, 3 carbons on the two methylene groups in the butylene structure on the block), and no other peaks produced by transesterification were seen.

DSC: T _m (240°C) corresponds to the PE ₈₀ T ₁₀ B ₁₀ T block, and the melting peak of PLA is not seen because the racemic polylactic acid block is generated.

The GPC spectrum is a single peak, and the NMR spectrum has no peaks generated by transesterification, which means that what is obtained is a block copolymer.

Obtained in this embodiment is the block copolymer of polyethylene terephthalate-ethylene glycol _- propylene glycol-butylene glycol ester and polylactic acid, in general formula, the _R of A section structural formula is , R ₂ is (CH ₂ ) ₂ , (CH ₂ ) ₃ and (CH ₂ ) ₄ , wherein the molar ratio of (CH ₂ ) ₂ , (CH ₂ ) ₃ and (CH ₂ ) ₄ is 90:10:10, R ₃ is C ₅ H ₁₁ -, and the B block is a racemic polylactic acid block.

Example 10

Synthesis of block copolymers of polyhexamethylene terephthalate (PHT) and polylactic acid (PLA).

Step (1). Benzyl alcohol initiates ring-opening polymerization of cyclic poly(ethylene terephthalate) to obtain single-end hydroxyl poly(ethylene terephthalate).

Under the protection of nitrogen, 10g of cyclic polyethylene terephthalate, 0.3g of benzyl alcohol and 0.0103g of Sn(Oct) ₂ were put into a 100ml reaction flask which had been roasted and cooled with nitrogen protection. Add 10ml of V _{tetrachloroethane} through anhydrous anaerobic treatment with syringe: V _{o-dichlorobenzene} =1:1: The mixed solvent makes the concentration of cyclic polyethylene terephthalate be 1.0Kg/L , the concentration of benzyl alcohol is 30g/L. The reaction was carried out at 150°C. After 20 minutes, the reaction was completed (GPC monitored the signal peak of no monomer), cooled and filtered, and the reaction product was washed with anhydrous chloroform to wash away traces of unreacted monomers. Vacuum at 60°C drying.

Step (2). Single-terminal hydroxyl PHT initiates lactide polymerization. The 100ml reaction bottle was treated with anhydrous and oxygen-free treatment, cooled under nitrogen atmosphere, and then under the protection of nitrogen, add 1g of single-terminal hydroxyl PHT and 1g of L-lactide obtained in step (1), and then add 20ml of tetrachloride Ethane, so that the concentration of PHT is 50g/L, the concentration of lactide is 0.05Kg/L, and the temperature is raised to 80°C. At this temperature, the reaction solution is in a uniform and transparent solution state, and then 0.02g Sn ( Oct) ₂ , reacted at 130°C, and monitored by GPC. After 5 hours, the signal peak of lactide disappeared, and the reaction was stopped. After cooling, it was filtered to obtain a white crude product.

Step (3). Add 40ml of mixed solvent of V _chloroform /V _{trifluoroacetic acid} =2:1 to the crude product obtained in step (2), so that the concentration of the crude product is 50g/L, settle with 200ml of methanol, filter and dry The final product was obtained with a yield of 94.8%, which was characterized by GPC, ¹ H-NMR, ¹³ C-NMR and DSC.

data:

GPC: Due to the large content of aromatic copolyester blocks in the copolymer, the solubility in chloroform is not very ideal, so first use o-chlorophenol as the solvent to make 10mg/mL, and then dilute to 1 mg with chloroform /mL, the mixed solvent with the volume ratio of chloroform and o-chlorophenol as 10 is the mobile phase, the _flow rate is 1.0ml/min, and PS is used as the _standard sample . =25.7K, PDI=1.36

¹ H-NMR: 8.05ppm (hydrogen on the benzene ring in the PHT block), 4.41ppm (hydrogen on the 1 and 6 methylene groups in the PHT block hexylene), 1.7ppm (the hydrogen in the PHT block hexylene 3, 4 hydrogens on two methylenes), 2.05ppm (PHT block hexamethylene 2, 5 hydrogens on two methylenes), 4.67ppm (two oxygens on PHT block Hydrogen on the methyl group), 1.55ppm (hydrogen on the 3, 4 methylene groups in the PHT block hexamethylene group), 1.75ppm (hydrogens on the 2, 5 methylene groups in the PHT block hexamethylene group) , 5.42ppm (hydrogen on the methine of the PLA block), 1.68ppm (hydrogen on the methyl group of the PLA block); there is no peak generated by the transesterification of PHN and PLA, and m _PHN is obtained from the integrated area: m _PLA =1:1

¹³ C-NMR: 170.0ppm (the carbonyl carbon on the PLA block), 69.2ppm (the methine carbon on the PLA block), 15.7ppm (the carbon on the methyl group of the PLA block); 168.4ppm (the carbon on the PHT block carbonyl), 133.0ppm (the carbon connected to the carbonyl on the benzene ring of the PHT block), 129.5ppm (the carbons at the 2, 3, 4, and 5 positions of the benzene ring on the PHT block), 63.6ppm (the hexylene group of the PHT block Carbons on the two methylene groups that are structurally bonded to oxygen), 25.2ppm (2, 5 carbons on the two methylene groups in the PHT block hexamethylene group), 20.6 ppm (3, 4 in the PHT block hexamethylene group carbons on two methylene groups), no peaks generated by the exchange of PHT blocks with polylactate were observed.

DSC: Tm (155°C) corresponds to the PLA block, Tm ₍ 145°C) _corresponds to the PHT block.

，R₂为CH₂)₆，R₃为，B段为左旋聚乳酸嵌段。 Obtained in this embodiment is polyethylene terephthalate and polylactic acid block copolymer, in general formula, the _R of A section structural formula is

, R ₂ is CH ₂ ) ₆ , R ₃ is , Block B is a L-polylactic acid block.

Example 11

Synthesis of poly-1,4-cyclohexanedimethyl terephthalate (PCT) and polylactic acid (PLA) block copolymers containing polylactic acid with two different configurations.

Step (1). Benzyl alcohol initiates ring-opening polymerization of cyclic poly(1,4-cyclohexane dimethyl terephthalate (CCT)) to obtain single-end hydroxyl poly(1,4-cyclohexane terephthalate) Dimethyl ester.

Under the protection of nitrogen, put 10g of cyclic poly-1,4-cyclohexanedimethyl terephthalate, 0.1g of benzyl alcohol and 0.0101 g of Sn(Oct) ₂ into the oven which has been roasted and cooled under the protection of nitrogen. 100ml reaction vial. Add 10ml of o-dichlorobenzene that has been treated with anhydrous and anaerobic treatment with a syringe, so that the concentration of cyclic poly-1,4-cyclohexane dimethyl terephthalate is 1.0Kg/L, and the concentration of benzyl alcohol is 10g/L. The reaction was carried out at 120°C. After 60 minutes, the reaction was completed (GPC monitored the signal peak of no monomer), cooled and filtered, and the reaction product was washed with anhydrous chloroform to wash away traces of unreacted monomers. Vacuum at 60°C drying.

Step (2). Single-terminal hydroxyl PCT initiates lactide polymerization. The 100ml reaction bottle was treated with anhydrous and oxygen-free treatment, cooled under a nitrogen atmosphere, and then under the protection of nitrogen, add 1g of the single-terminal hydroxyl PCT and 1g of D-lactide obtained in step (1), and then add 20ml of tetrachloride with a syringe Ethane, so that the concentration of PCT is 50g/L, the concentration of lactide is 0.05Kg/L, and the temperature is raised to 80°C. At this temperature, the reaction solution is in a uniform and transparent solution state, and then 0.02g Sn( Oct) ₂ , reacted at 130°C, and monitored by GPC. After 5 hours, the signal peak of lactide disappeared, and the reaction was stopped. After cooling, it was filtered to obtain a white crude product.

Step (3). Add 40ml of mixed solvent of V _chloroform /V _{trifluoroacetic acid} =2:1 to the crude product obtained in step (2), so that the concentration of the crude product is 50g/L, settle with 200ml of methanol, filter and dry

Step (4). The 100ml reaction bottle was also treated with anhydrous and oxygen-free treatment, cooled under a nitrogen atmosphere, and then under the protection of nitrogen, 1g of the product obtained in step (3) and 1g of D,L-lactide were added, and then used Add 10ml o-dichlorobenzene to the syringe so that the concentration of the polylactic acid block copolymer is 100g/L, the concentration of lactide is 0.1Kg/L, and the temperature is raised to 80°C. At this temperature, the reaction solution is a uniform and transparent solution. Then add 0.003g SnBr ₂ with a syringe, react at 140°C, and monitor with GPC. After 5 hours, the signal peak of lactide disappears, stop the reaction, cool and filter to obtain a white crude product.

Step (5). Add 40ml of chloroform to the crude product so that the concentration of the crude product is 50g/L, settle with 200ml of methanol, filter and dry to obtain the final product, the yield is 98.2%, and do GPC, ¹ H-NMR, ¹³ C- Various characterizations by NMR and DSC.

data:

GPC: Use chloroform as the mobile phase, flow rate 1.0ml/min, PS as the standard sample, where the spectrum shows a normal distribution, measured M _n =31.1K, M _w =42.3K, PDI=1.36

¹ H-NMR: 8.25ppm (hydrogen on the benzene ring of the PCT block), 4.37 ppm (hydrogen on the two methylene groups connected to the oxygen in the PCT block), 1.68-2.18 ppm (the hydrogen on the cyclohexane of the PCT block Hydrogen); 5.42ppm (hydrogen on the methine of the PLA block), 1.68ppm (hydrogen on the methyl group of the PLA block); no other peaks produced by transesterification were seen, and m _PCT was obtained from the integrated area: m _PLA =1: 30

¹³ C-NMR: 170.5ppm (carbonyl carbon on the PLA block), 69.3ppm (methine carbon on the PLA block), 15.8ppm (carbon on the methyl group of the PLA block); 168.9ppm (carbon on the PCT block carbonyl), 134.4ppm (the carbon connected to the carbonyl on the benzene ring of the PCT block), 130.5ppm (the carbons at the 2, 3, 4, and 5 positions of the benzene ring on the PCT block), 73.1ppm (the carbon connected to the carbonyl on the PCT block Oxygen-linked carbon on the two methylene groups), 29.1ppm (carbon on the methine group of the PCT block), 35.0ppm (methylene carbon in the cyclohexyl group of the PCT block), no PCT block and polyemulsion Peaks generated by transesterification.

DSC: T _m (175°C) corresponds to the PLA block, and the melting point of the PCT block is not seen due to too little content.

The GPC spectrum is a single peak, and the NMR spectrum has no peaks generated by transesterification, which means that what is obtained is a block copolymer.

，R₃为

，B段由两种聚乳酸嵌段组成，表示为B₂-B₁-，其中B₁为右旋聚乳酸嵌段、B₂为外消旋聚乳酸嵌段 So what this embodiment obtains is the block copolymer of poly-1,4-cyclohexane dimethyl terephthalate and polylactic acid. In the general formula, the _R of the A segment structural formula is , R ₂ is

, _R3 is

, Block B is composed of two polylactic acid blocks, expressed as B ₂ -B ₁ -, where B ₁ is a dextrorotatory polylactic acid block, B ₂ is a racemic polylactic acid block

Example 12

Synthesis of block copolymers of polyethylene 2,6-naphthalate (PEN) and polylactic acid (PLA) containing two configurations of polylactic acid.

Step (1). Benzyl alcohol initiates ring-opening polymerization of cyclic polyethylene 2,6-naphthalene dicarboxylate (CEN) to obtain single-terminal hydroxyl poly(ethylene glycol 2,6-naphthalate).

Under nitrogen protection, 10gCEN, 0.2g cyclopentanol and 0.0102g Sn(Oct) ₂ were put into a 100ml reaction flask which had been roasted and cooled with nitrogen protection. Add 10ml of tetrachloroethane treated with anhydrous and anaerobic by syringe, so that the concentration of CEN is 1.0Kg/L, and the concentration of cyclopentanol is 20g/L. The reaction was carried out at 180°C. After 3 minutes, the reaction was completed (GPC monitored the signal peak of no monomer), cooled and filtered, and the reaction product was washed with anhydrous chloroform to wash away traces of unreacted monomers. Vacuum at 60°C drying.

Step (2). PEN with a single hydroxyl group initiates lactide polymerization. The 100ml reaction bottle has been anhydrous and oxygen-free, cooled under nitrogen atmosphere, and then under the protection of nitrogen, add 1g of the single-terminal hydroxyl PEN obtained in step (1) and 3g of D, L-lactide, and then add 10ml with a syringe Tetrachloroethane, so that the concentration of PEN is 100g/L, the concentration of lactide is 0.3Kg/L, dissolve at 120°C, at this temperature, the reaction solution is in a uniform and transparent solution state, and then add 0.0004g with a syringe Sn(Oct) ₂ , reacted at 120°C, monitored by GPC, the signal peak of lactide disappeared after 3 hours, the reaction was stopped, cooled and filtered to obtain a white crude product.

Step (3). Get the crude product obtained in step (2), add 40ml trifluoroacetic acid to make the crude product concentration 100g/L, settle with 150ml methanol, filter and dry to obtain the product

Step (4). The product obtained in step (3) initiates lactide polymerization. The 100ml reaction flask was treated with anhydrous and oxygen-free treatment, cooled under a nitrogen atmosphere, then under the protection of nitrogen, add the product of 1g step (3) gained and 1g L-lactide, then add 10ml toluene with a syringe, so that the step ( 3) The concentration of the obtained product is 100g/L, the concentration of lactide is 0.1Kg/L, and the temperature is raised to 80°C. At this temperature, the reaction solution is in a uniform and transparent solution state, and then 0.01g SnCl ₄ is added with a syringe , reacted at 110°C, monitored by GPC for 6 hours, the signal peak of lactide disappeared, the reaction was stopped, and the white crude product was obtained by filtration after cooling.

Step (5). Add 40ml chloroform to the crude product obtained in (4) in the step, so that the crude product concentration is 50g/L, settle with 160ml methanol, filter and dry to obtain the final product, yield 95.2%, do GPC, Various characterizations by ¹ H-NMR, ¹³ C-NMR, and DSC.

data:

GPC: Using chloroform as the mobile phase, the flow rate is 1.0ml/min, and PS is used as the standard sample, where the spectrum presents a normal distribution, the flow rate is 1.0ml/min, and the measured M _n =35.1K, M _w =53.71K, PDI=1.53

¹ H-NMR: 8.85ppm (hydrogen at positions 1 and 5 on the PEN block naphthalene ring), 8.15ppm (hydrogen at positions 3, 4, 7, and 8 on the PEN block naphthalene ring), 4.8ppm (hydrogen at the ethylene position on the PEN block ), 5.15ppm (hydrogen on the methine of the PLA block), 1.63ppm (hydrogen on the methyl group of the PLA block); there is no peak generated by the transesterification of PEN and PLA, and m _PEN is obtained from the integrated area: m _PLA =1 :7.

¹³ C-NMR: 168.0ppm (carbonyl carbon on the PEN block), 131.2 ppm (carbon on the 1st, 5th position of the naphthalene ring on the PEN block), 132.5ppm (2, 6th position of the naphthalene ring on the PEN block carbon on the PEN block), 130.0 ppm (the carbon on the 3rd and 7th positions of the naphthalene ring on the PEN block), 131.0 ppm (the carbon on the 4th and 8th position of the naphthalene ring on the PEN block), 66.2 ppm (the carbon on the 8th position of the naphthalene ring on the PEN block), 66.2 ppm (the carbon on the ethylene carbon on two methylene groups in the PLA block), 170.0ppm (carbonyl carbon on the PLA block), 69.2ppm (methine carbon on the PLA block), 15.7ppm (carbon on the methyl group of the PLA block); not seen The rest of the peaks generated by transesterification

DSC: T _m (280℃) corresponds to PEN block, T _m (160℃) corresponds to PLA block

The GPC spectrum is a single peak, and the NMR spectrum has no peaks generated by transesterification, which means that what is obtained is a block copolymer.

,R₂为(CH₂)₂，R₃为环-C₅H₉-, B由两种聚乳酸嵌段组成，表示为B₂-B₁-，其中B₁为外消旋聚乳酸嵌段、B₂为左旋聚乳酸嵌段。 Obtained in this embodiment is the block copolymer of PEN and PLA, and in general formula, the _R of A section structural formula is

, R ₂ is (CH ₂ ) ₂ , R ₃ is ring -C ₅ H ₉ -, B is composed of two polylactic acid blocks, expressed as B ₂ -B ₁ -, where B ₁ is a racemic polylactic acid block Segment, B ₂ is L-polylactic acid block.

Example 13

Synthesis of block copolymers of polytrimethylene 2,6-naphthalate (PTN) and polylactic acid (PLA) containing two configurations of polylactic acid.

Step (1). Benzyl alcohol initiates ring-opening polymerization of cyclic polytrimethylene 2,6-naphthalate (CTN) to obtain single-end hydroxyl polytrimethylene 2,6-naphthalate.

Under the protection of nitrogen, put 10g CTN, 1.0g cyclopentanol and 0.0011g Sn(Oct) ₂ into a 100ml reaction flask which has been cooled by fire and protected by nitrogen. Add 5ml of tetrachloroethane that has been treated with anhydrous and anaerobic treatment with a syringe, so that the concentration of CTN is 2.0Kg/L, and the concentration of cyclopentanol is 200g/L. The reaction was carried out at 180°C. After 3 minutes, the reaction was completed (GPC monitored the signal peak of no monomer), cooled and filtered, and the reaction product was washed with anhydrous chloroform to wash away traces of unreacted monomers. Vacuum at 60°C drying.

Step (2). Single-terminal hydroxyl PTN initiates lactide polymerization. The 50ml reaction bottle was anhydrous and oxygen-free, cooled under nitrogen atmosphere, and then under the protection of nitrogen, add 0.06g of single-terminal hydroxyl PTN and 1gL-lactide obtained in step (1), and add 2ml of tetrachloroethylene with a syringe alkane so that the concentration of PTN is 30g/L, the concentration of lactide is 0.5Kg/L, and the temperature is raised to 120°C. At this temperature, the reaction solution is in a uniform and transparent solution state, and then 0.0106 g Sn(Oct ) ₂ , reacted at 120°C, monitored by GPC, the signal peak of lactide disappeared after 6 hours, the reaction was stopped, and the white crude product was obtained by filtration after cooling.

Step (3). Get the crude product of step (2) gained, be dissolved in 10ml chloroform, make the crude product concentration be 100 g/L, settle with 40ml methanol, filter and dry to obtain product

Step (4). The product obtained in step (3) initiates lactide polymerization. The 100ml reaction bottle was treated anhydrous and oxygen-free, cooled under nitrogen atmosphere, then under the protection of nitrogen, add 1g of the product obtained in step (2) and 8g D-lactide, then add 10ml tetrachloroethane with a syringe, The concentration of the product obtained in step (2) is 100g/L, the concentration of lactide is 0.8Kg/L, and the temperature is raised to 50°C. At this temperature, the reaction solution is in a uniform and transparent solution state, and then 0.0009 g Sn(Oct) ₂ , reacted at 110°C, and monitored by GPC for 6 hours, the signal peak of lactide disappeared, the reaction was stopped, and the white crude product was obtained by filtration after cooling.

Step (5). Add 90ml chloroform to the crude product obtained in (4) in the step, so that the crude product concentration is 100g/L, settle with 360ml methanol, filter and dry to obtain the final product, yield 99.1%, do GPC, Various characterizations by ¹ H-NMR, ¹³ C-NMR, and DSC

data

GPC: Use chloroform as the mobile phase, flow rate 1.0ml/min, PS as the standard sample, where the spectrum shows a normal distribution, measured M _n =60.1K, M _w =87.0K, PDI=1.45

¹ H-NMR: 8.65ppm (hydrogen at positions 1 and 5 on the PTN block naphthalene ring), 8.05ppm (hydrogen at positions 3, 4, 7, and 8 on the PTN block naphthalene ring), 4.65ppm (the PTN block is connected to oxygen Hydrogen on the methylene), 2.35ppm (hydrogen on the methylene of the PTN block and the non-oxygen group), 5.15ppm (hydrogen on the methine of the PLA block), 1.63ppm (hydrogen on the methyl group of the PLA block) ; The rest of the peaks produced by transesterification were not seen, and the mass ratio of PLA:PTN was 120:1 obtained from the integrated area

¹³ C-NMR: 168.6ppm (the carbonyl carbon on the PTN block), 131.6 ppm (the carbon on the 1, 5-position of the naphthalene ring on the PTN block), 132.5ppm (the 2, 6-position of the naphthalene ring on the PTN block 130.0 ppm (the carbon on the 3rd and 7th positions of the naphthalene ring on the PTN block), 131.0 ppm (the 4th and 8th carbon on the naphthalene ring on the PTN block), 66.2 ppm (the carbon on the 8th position of the PTN block The carbon on the two methylene groups in the 1 and 3 positions of the propyl group), 27.2ppm (the carbon on the middle methylene group of the PTN block propylene), 170.0ppm (the carbonyl carbon on the PLA block), 69.1ppm ( methine carbons on the PLA block), 15.8 ppm (carbons on the methyl groups of the PLA block); no remaining peaks from transesterification were seen

DSC: T _m (220°C) corresponds to the stereocomplex formed by two configurations of polylactic acid blocks, T _m (160°C) corresponds to the PLA block, and its melting point is not seen due to too little PTN content

The GPC spectrum is a single peak, and the NMR spectrum has no peaks generated by transesterification, indicating that the obtained block copolymer

, R₂为(CH₂)₃ ，R₃为环-C₅H₉-； B由两种聚乳酸嵌段组成，表示为B₂-B₁-，其中B₁为左旋聚乳酸嵌段、B₂为右旋聚乳酸嵌段。 Obtained in this embodiment is polytrimethylene naphthalate and polylactic acid block copolymer containing two configurations of polylactic acid. In the general formula, the R _of the A segment structural formula is

, R ₂ is (CH ₂ ) ₃ , R ₃ is ring -C ₅ H ₉ -; B is composed of two polylactic acid blocks, expressed as B ₂ -B ₁ -, wherein B ₁ is a left-handed polylactic acid block, _B2 is a D-polylactic acid block.

Example 14

Synthesis of block copolymers of polybutylene-2,6-naphthalate (PBN) and polylactic acid containing three configurations of polylactic acid.

Step (1). Methanol initiates the ring-opening polymerization of cyclic polybutylene-2,6-naphthalate (CBN) to obtain single-end hydroxyl polybutylene-2,6-naphthalate

Under the protection of nitrogen, put 10g of CBN, 1.0g of propargyl alcohol and 0.011g of SnCl ₄ into a 100ml reaction flask that has been roasted and cooled with nitrogen protection. Add 5ml of tetrachloroethane treated with anhydrous and anaerobic by syringe, so that the concentration of CBN is 2Kg/L, and the concentration of propargyl alcohol is 200g/L. The reaction was carried out at 180°C. After 5 minutes, the reaction was over (GPC monitoring had no signal peak of CBN), cooled and filtered, and the reaction product was washed with anhydrous chloroform to wash away traces of unreacted CBN monomers, and vacuumed at 60°C drying.

Step (2). Single-terminal hydroxyl PBN initiates lactide polymerization. The 100ml reaction bottle was anhydrous and oxygen-free, cooled under a nitrogen atmosphere, and then under the protection of nitrogen, add 0.06g of the single-terminal hydroxyl PTT and 1g of D-lactide obtained in step (1), and then add 2ml of o-di Chlorobenzene, so that the concentration of PBN is 30g/L, the concentration of lactide is 0.5Kg/L, and the temperature is raised to 60°C. At this temperature, the reaction solution is in a uniform and transparent solution state, and then 0.0106g SnCl ₂ is added with a syringe , reacted at 60°C, and monitored by GPC. After 24 hours, the signal peak of lactide disappeared, and the reaction was stopped. After cooling, it was filtered to obtain a white crude product.

Step (3). Get the crude product of step (2) gained, be dissolved in 20ml chloroform, make the crude product concentration be 50 g/L, settle with 60ml methanol, filter and dry

Step (4). The product obtained in step (3) initiates lactide polymerization. The 100ml reaction bottle was treated anhydrous and oxygen-free, cooled under a nitrogen atmosphere, then under the protection of nitrogen, add 1g of the product obtained in step (3) and 20g L-lactide, and then add 10ml of chloroform with a syringe, so that The concentration of the product obtained in step (3) is 100g/L, the concentration of lactide is 2Kg/L, and the temperature is raised to 50°C. At this temperature, the reaction solution is in a uniform and transparent solution state, and then 0.21g SnCl is added with a syringe _2. React at 50°C. After monitoring by GPC for 24 hours, the signal peak of lactide disappears, stop the reaction, and filter to obtain a white crude product after cooling.

Step (5). Add 210ml chloroform to the crude product gained in step (4), so that the crude product concentration is 100g/L, settle with 630ml methanol, filter and dry

Step (6). The product obtained in step (5) initiates lactide polymerization. The 100ml reaction bottle was treated anhydrous and oxygen-free, cooled under a nitrogen atmosphere, and then under the protection of nitrogen, add 1g of the product obtained in step (5) and 1g of D,L-lactide, and then add 5ml of V _{trichloro Methane} : the mixed solvent of V _{dichloromethane} =1:1, make the concentration of the product of step (5) gained be 200g/L, the concentration of lactide is 0.2Kg/L, be warming up to 30 ℃, at this temperature, The reaction solution was in the state of a uniform and transparent solution. Add 0.004g Sn(Oct) ₂ with a syringe, react at 80°C, and monitor with GPC. After 20 hours, the signal peak of lactide disappeared, and the reaction was stopped. After cooling, it was filtered to obtain a white crude product.

Step (7). 20ml chloroform is added to the crude product gained in step (6), so that the crude product concentration is 100g/L, settle with 100ml methanol, filter and dry to obtain the final product, yield 91.2%, do GPC, Various characterizations by ¹ H-NMR, ¹³ C-NMR, and DSC

data

GPC: Use chloroform as the mobile phase, flow rate 1.0ml/min, PS as the standard sample, where the spectrum shows a normal distribution, measured M _n =54.9K, M _w =85.10K, PDI=1.55

¹ H-NMR: 8.698ppm (hydrogen at positions 1 and 5 on the PBN block naphthalene ring), 8.05ppm (hydrogen at positions 3, 4, 7, and 8 on the PBN block naphthalene ring), 4.68ppm (the PBN block is connected to oxygen Hydrogen on the methylene), 2.11ppm (hydrogen on the methylene of the PBN block and the non-oxygen group), 5.18ppm (hydrogen on the methine of the PLA block), 1.65ppm (hydrogen on the methyl group of the PLA block) ; Do not see the rest of the peaks produced by transesterification, m _PBN obtained by the integrated area: m _PLA =1:350

¹³ C-NMR: 168.7ppm (the carbonyl carbon on the PBN block), 131.6 ppm (the carbon at the 1,5 position of the naphthalene ring on the PBN block), 132.5ppm (the 2,6 position of the naphthalene ring on the PBN block 130.1 ppm (carbon on the 3rd and 7th positions of the naphthalene ring on the PBN block), 131.1 ppm (the carbon on the 4th and 8th position of the naphthalene ring on the PBN block), 66.2 ppm (the carbon on the 8th position of the naphthalene ring on the PBN block), 66.2 ppm (the carbon on the 1, 4 carbons on the two methylene groups in the group), 27.2ppm (the carbon on the middle methylene group of the PBN block butylene), 170.1ppm (the carbonyl carbon on the PLA block), 69.6ppm (the PLA block methine carbon on the PLA block), 15.9 ppm (carbon on the methyl group of the PLA block); no remaining peaks from transesterification were seen

DSC: T _m (173°C) corresponds to the PLA block, T _m (220°C) corresponds to the stereocomplex formed by the two configurations of the polylactic acid block, because the content of PBN is too small, no PBN block is seen melting point

The GPC spectrum is a single peak, and there is no peak generated by transesterification in the NMR spectrum, which means that what is obtained is a block copolymer

,R₂为(CH₂)₄，R₃为

; B由三种聚乳酸嵌段组成，表示为B₃-B₂-B₁-，其中B₁为右旋聚乳酸嵌段、B₂为左旋聚乳酸嵌段,B₃为外消旋聚乳酸嵌段。 Obtained in this embodiment is the block copolymer that contains poly(butylene 2,6-naphthalate) of polylactic acid of three configurations and polylactic acid, in general formula, _the R of A section structural formula is

, R ₂ is (CH ₂ ) ₄ , R ₃ is

; B consists of three polylactic acid blocks, expressed as B ₃ -B ₂ -B ₁ -, where B ₁ is a right-handed polylactic acid block, B ₂ is a left-handed polylactic acid block, and B ₃ is a racemic polylactic acid block. Lactic acid block.

Example 15

Synthesis of Block Copolymers of Polytrimethylene Naphthalate and Polylactic Acid (PLA) Containing Three Configurations of Polylactic Acid.

Step (1). Allyl alcohol initiates ring-opening polymerization of cyclic poly(trimethylene naphthalate) 1,4-naphthalate to obtain single-terminal hydroxyl poly(ethylene glycol 1,4-naphthalate).

Under the protection of nitrogen, put 10g of cyclic polytrimethylene 1,4-naphthalate, 0.3g of allyl alcohol and 0.0103g of Sn(Oct) ₂ into a 100ml reaction flask that has been roasted and cooled with nitrogen. Add 10ml of V _{tetrachloroethane} : V _{o-dichlorobenzene} : V _{trichlorobenzene} = 1:1:1 mixed solvent through anhydrous and anaerobic treatment with a syringe, so that the cyclic polyethylene 1,4-naphthalene dicarboxylate The concentration of alcohol ester is 1.0Kg/L, and the concentration of allyl alcohol is 30g/L. The reaction was carried out at 130°C. After 30 minutes, the reaction was completed (GPC monitored the signal peak of no monomer), cooled and filtered, and the reaction product was washed with anhydrous chloroform to wash away traces of unreacted monomers. Vacuum at 60°C drying.

Step (2). Single-end hydroxyl poly(trimethylene naphthalate) initiates lactide polymerization. The 100ml reaction bottle was anhydrous and oxygen-free, cooled under a nitrogen atmosphere, and then added 0.1g of single-terminal hydroxyl poly(1,4-trimethylene naphthalate) and 2g of D,L-lactide under the protection of nitrogen, and then Add 10ml of 1,2,4-trichlorobenzene with a syringe so that the concentration of polytrimethylene naphthalate is 10g/L and the concentration of lactide is 0.2Kg/L, and the temperature is raised to 130°C. The reaction liquid was in the state of a uniform and transparent solution, then added 0.003g SnCl ₄ with a syringe, reacted at 150°C, and monitored by GPC. After 2 hours, the signal peak of lactide disappeared, and the reaction was stopped. After cooling, it was filtered to obtain a white crude product .

Step (3). Get the crude product obtained in step (2), add 40ml chloroform to make the crude product concentration 50g/L, settle with 120ml methanol, filter and dry

Step (4). The product obtained in step (3) initiates lactide polymerization. The 100ml reaction bottle was treated with anhydrous and oxygen-free treatment, cooled under nitrogen atmosphere, then under the protection of nitrogen, add 1g of the product obtained in step (3) and 20g L-lactide, and then add 10ml of dichloromethane with a syringe, so that The concentration of the product obtained in step (3) is 100g/L, the concentration of lactide is 2Kg/L, and the temperature is raised to 30°C. At this temperature, the reaction solution is in a uniform and transparent solution state, and then 0.21g SnCl is added with a syringe _2. React at 30°C. After monitoring by GPC for 24 hours, the signal peak of lactide disappears, stop the reaction, and filter to obtain a white crude product after cooling.

Step (5). Add 210ml chloroform to the crude product gained in step (4), so that the crude product concentration is 100g/L, settle with 840ml methanol, filter and dry

Step (6). The product obtained in step (5) initiates lactide polymerization. The 100ml reaction flask was treated through anhydrous and oxygen-free treatment, cooled under nitrogen atmosphere, then under the protection of nitrogen, add the product of 1g step (5) gained and 1g D-lactide, then add 5ml V _{trichloromethane} with syringe: V _{carbon tetrachloride} : V _{carbon tetrachloride} =1:1:1, make the concentration of the product of step (5) gained be 200g/L, the concentration of lactide is 0.2Kg/L, be warming up to 30 ℃, in At this temperature, the reaction solution is in the state of a uniform and transparent solution. Add 0.004g Sn(Oct) ₂ with a syringe, react at 80°C, and monitor with GPC. After 20 hours, the signal peak of lactide disappears, stop the reaction, and filter after cooling. A white crude product was obtained.

Step (7). 20ml chloroform is added to the crude product gained in step (6), so that the crude product concentration is 100g/L, settle with 100ml methanol, filter and dry to obtain the final product, yield 91.2%, do GPC, Various characterizations by ¹ H-NMR, ¹³ C-NMR, and DSC

data:

GPC: Use chloroform as the mobile phase, flow rate 1.0ml/min, PS as the standard sample, where the spectrum presents a normal distribution, measured M _n =83.8K, M _w =121.51K, PDI=1.45

¹ H-NMR: 8.75ppm (hydrogen at positions 2 and 3 on the naphthalene ring), 8.05ppm (hydrogen at positions 6 and 7 on the naphthalene ring), 8.55ppm (hydrogen at positions 5 and 8 on the naphthalene ring) 4.70 ppm (hydrogen on two methylene groups in polytrimethylene 1,4-naphthalate), 5.1ppm (hydrogen on methine in PLA block), 1.6ppm (hydrogen on methyl in PLA block); not seen For the rest of the peaks produced by transesterification, m _{poly(trimethylene 1,4-naphthalate)} is obtained from the integrated area: m _PLA =1:35

¹³ C-NMR: 168.6ppm (the carbonyl carbon on the polytrimethylene naphthalate block), 132.7 ppm (on the 1,4 position of the naphthalene ring on the polytrimethylene naphthalate block carbon), 126.9ppm (carbons at the 2 and 3 positions of the naphthalene ring on the polytrimethylene naphthalate block), 131.4 ppm (the naphthalene on the polytrimethylene naphthalate block ring 5, carbon at the 8th position), 127.9ppm (the carbon at the 6th and 7th position of the naphthalene ring on the polytrimethylene 1,4-naphthalate block), 135.1ppm (the carbon at the polytrimethylene 1,4-naphthalate The carbon on the naphthalene ring 9 and 10 on the ester block), 26.7ppm (the carbon on the middle methylene of the propyl group of the poly(1,4-trimethylene naphthalate block), 66.7ppm (the carbon on the poly(1,4-naphthalene dicarboxylate) propylene glycol formate block propyl group connected to oxygen on methylene carbon), 170.2ppm (carbonyl carbon on PLA block), 69.2ppm (methine carbon on PLA block), 15.8ppm (methylene carbon on PLA block carbon); no remaining peaks due to transesterification were seen.

DSC: T _m (185°C) corresponds to the polytrimethylene naphthalate block, T _m (155°C) corresponds to the PLA block, T _m (205°C) corresponds to the stand-alone formed by different configurations of PLA structural complex

The GPC spectrum is a single peak, and there is no peak generated by transesterification in the NMR spectrum, which means that what is obtained is a block copolymer

,R₂为(CH₂)₃，R₃为

；B由三种聚乳酸嵌段组成，表示为B₃-B₂-B₁-，其中B₁为外消旋聚乳酸嵌段、B₂为左旋聚乳酸嵌段, ,B₃为右旋聚乳酸嵌段。 Obtained in this embodiment is the polytrimethylene naphthalate containing three kinds of configuration polylactic acid and the block copolymer of polylactic acid, in the general formula, the R _of A section structural formula is

, R ₂ is (CH ₂ ) ₃ , R ₃ is

; B is composed of three polylactic acid blocks, expressed as B ₃ -B ₂ -B ₁ -, where B ₁ is a racemic polylactic acid block, B ₂ is a left-handed polylactic acid block, and B ₃ is a right-handed polylactic acid block. polylactic acid blocks.

Example 16

Synthesis of Poly(1,4-Naphthalate-1,4-cyclohexanedimethyl) and Polylactic Acid (PLA) Block Copolymer Containing Three Configurations of Polylactic Acid.

Step (1). Ring-opening polymerization of cyclic poly-1,4-naphthalene dicarboxylic acid-1,4-cyclohexanedimethyl ester initiated by 1-nonanol to obtain single-terminal hydroxyl poly-2,6-naphthalene dicarboxylic acid-1 , 4-cyclohexane dimethyl ester.

Under the protection of nitrogen, put 10g of cyclic poly-1,4-naphthalene dicarboxylate-1,4-cyclohexanedimethyl ester, 0.1g of 1-nonanol and 0.0101 g of Sn(Oct) ₂ into Cooled 100ml reaction vial. Add 10ml of V _{tetrachloroethane} : V _{o-dichlorobenzene} = 1:1 mixed solvent through anhydrous and anaerobic treatment with a syringe, so that the cyclic poly-1,4-naphthalene dicarboxylic acid-1,4-cyclohexane di The concentration of methyl ester is 1.0Kg/L, and the concentration of 1-nonanol is 10g/L. The reaction was carried out at 170°C. After 10 minutes, the reaction was completed (GPC monitored the signal peak of the acyclic monomer), cooled and filtered, and the reaction product was washed with chloroform that had also been treated with anhydrous to wash away a small amount of unreacted monomer. 80 °C vacuum drying.

Step (2). Single-terminal hydroxyl poly-1,4-naphthalene dicarboxylate-1,4-cyclohexanedimethyl ester initiates lactide polymerization. The 100ml reaction bottle was anhydrous and oxygen-free, cooled under a nitrogen atmosphere, and then under the protection of nitrogen, add 0.1g of the product obtained in step (1) and 2g of D-lactide, and then add 10ml of nitrobenzene with a syringe, Make the concentration of the product obtained in the addition step (1) 10g/L, the concentration of lactide 0.2Kg/L, raise the temperature to 100°C, at this temperature, the reaction solution is in a uniform and transparent solution state, and then add 0.003 g Sn(Oct) ₂ , reacted at 120°C, monitored by GPC, the signal peak of lactide disappeared after 3 hours, the reaction was stopped, cooled and filtered to obtain a white crude product.

Step (3). Get the crude product obtained in step (2), add 40ml chloroform to make the crude product concentration 52g/L, settle with 150ml methanol, filter and dry to obtain the product

Step (4). The product obtained in step (3) initiates lactide polymerization. The 100ml reaction bottle was treated anhydrous and oxygen-free, cooled under a nitrogen atmosphere, and then under the protection of nitrogen, add 1.5g of the product obtained in step (3) and 3g of D, L-lactide, and then add 5ml of tetrachloride with a syringe Carbon, so that the concentration of the product obtained in step (3) is 300g/L, the concentration of lactide is 0.6Kg/L, and the temperature is raised to 50°C. At this temperature, the reaction solution is in a uniform and transparent solution state. Add 0.0045g of SnCl ₂ , react at 110°C, monitor with GPC for 14 hours and then the lactide signal peak disappears, stop the reaction, cool and filter to obtain a white crude product.

Step (5). Add 45ml chloroform to the crude product gained in step (4), so that the crude product concentration is 100g/L, settle with 150ml methanol, filter and dry

Step (6). The product obtained in step (5) initiates lactide polymerization. The 100ml reaction flask was treated with anhydrous and oxygen-free treatment, cooled under a nitrogen atmosphere, then under the protection of nitrogen, the product obtained in 1g step (5) and 1g L-lactide were added, and 5ml tetrahydrofuran was added with a syringe, so that the step ( 5) The concentration of the obtained product is 200g/L, the concentration of lactide is 0.2Kg/L, and the temperature is raised to 30°C. At this temperature, the reaction solution is in a uniform and transparent solution state, and then 0.0002g Sn ( Oct) ₂ , reacted at 80°C, and monitored by GPC. After 20 hours, the signal peak of lactide disappeared, and the reaction was stopped. After cooling, the white crude product was filtered out.

Step (7). 20ml chloroform is added to the crude product gained in step (6), so that the crude product concentration is 100g/L, settle with 100ml methanol, filter and dry to obtain the final product, yield 91.2%, do GPC, Various characterizations by ¹ H-NMR, ¹³ C-NMR, and DSC

data:

GPC: Use chloroform as the mobile phase, flow rate 1.0ml/min, PS as the standard sample, where the spectrum shows a normal distribution, measured M _n =65.4K, M _w =101.4K, PDI=1.55

¹ H-NMR: 8.75ppm (hydrogen at positions 2 and 3 on the naphthalene ring), 8.05ppm (hydrogen at positions 6 and 7 on the naphthalene ring), 8.55ppm (hydrogen at positions 5 and 8 on the naphthalene ring), 4.4ppm (hydrogen on the two methylene groups connected to the 1, 4 positions of the cyclohexylene in the poly-1,4-naphthalene dicarboxylic acid-1,4-cyclohexanedimethylester block), 1.3～2.2ppm ( Poly-1,4-naphthalene dicarboxylate-1,4-cyclohexanedimethylene hydrogen on the cyclohexylene block), 5.1ppm (hydrogen on the PLA block methine), 1.6ppm (hydrogen on the PLA block methyl ); no other peaks produced by transesterification were seen, and m _{poly-1,4-naphthalene dicarboxylate-1,4-cyclohexanedimethyl} was obtained from the integrated area: m _PLA =1:65.

¹³ C-NMR: 168.6.0ppm (the carbonyl carbon of poly-1,4-naphthalene dicarboxylate-1,4-cyclohexane dimethyl ester), 132.7 ppm (the carbon on the 1st and 4th positions of the naphthalene ring), 126.9ppm ( 2, 3 carbons on the naphthalene ring), 131.4 ppm (5, 8 carbons on the naphthalene ring), 127.9 ppm (6, 7 carbons on the naphthalene ring), 135.1 ppm (9, 10 carbons on the naphthalene ring carbon), 61.2ppm (the carbons on the two methylene groups connected at the 1 and 4 positions in the block cyclohexylene of poly-1,4-naphthalene dicarboxylate-1,4-cyclohexanedimethylene), 25.2 ppm (poly-1 , 4-naphthalene dicarboxylic acid-1,4-cyclohexane dimethyl ester segment cyclohexylene carbon on the 1,4 two methine groups), 18.6 ppm (poly-1,4-naphthalene dicarboxylic acid-1,4-cyclo 2,3,5,6 carbons on the four methylene groups in the cyclohexylene group of the hexane dimethyl ester block), 170.0ppm (the carbonyl carbon on the PLA block), 69.2ppm (the methine carbon on the PLA block ), 15.7 ppm (the carbon on the methyl group of the PLA block); the remaining peaks resulting from transesterification were not seen.

DSC: T _m (168°C) corresponds to the PLA block, T _m (208°C) corresponds to the stereocomplex formed by different configurations of PLA, due to poly-1,4-naphthalene dicarboxylic acid-1,4-cyclohexane The dimethyl ester block content is too small, and its melting point is not seen

The GPC spectrum is a single peak, and there is no peak generated by transesterification in the NMR spectrum, which means that what is obtained is a block copolymer

,R₂为

，R₃为

；B由三种聚乳酸嵌段组成，表示为B₃-B₂-B₁-，其中B₁为右旋聚乳酸嵌段、B₂为外消旋聚乳酸嵌段，B₃为左旋聚乳酸嵌段。 What is obtained in this embodiment is the block copolymer of poly-1,4-naphthalene dicarboxylate-1,4-cyclohexane dimethyl containing polylactic acid of three different configurations and polylactic acid, in the general formula, R ₁ of the structural formula of section A is

, R ₂ is

, _R3 is

; B is composed of three polylactic acid blocks, expressed as B ₃ -B ₂ -B ₁ -, wherein B ₁ is a right-handed polylactic acid block, B ₂ is a racemic polylactic acid block, and B ₃ is a left-handed polylactic acid block. Lactic acid block.

Example 17

Synthesis of block copolymers of polybutylene-1,4-naphthalate and polylactic acid (PLA) containing three configurations of polylactic acid.

Step (1). 1-nonanol initiates ring-opening polymerization of cyclic polybutylene-1,4-naphthalate to obtain single-end hydroxyl polybutylene-1,4-naphthalate.

Under the protection of nitrogen, put 10g of cyclic polybutylene-1,4-naphthalate, 0.1g of 1-decanol and 0.0101 g of Sn(Oct) ₂ into a 100ml reaction flask that has been roasted and cooled with nitrogen. . Add 10ml of V _{tetrachloroethane} :V _{o-dichlorobenzene} =1:1 mixed solvent through anhydrous and anaerobic treatment with a syringe, so that the concentration of cyclic polybutylene naphthalate is 1.0Kg /L, the concentration of 1-decanol is 10g/L. The reaction was carried out at 160°C. After 20 minutes, the reaction was completed (the signal peak of the acyclic monomer was monitored by GPC), cooled and filtered, and the reaction product was washed with anhydrous chloroform to wash away a small amount of unreacted monomer. 80 °C vacuum drying.

Step (2). Single-terminal hydroxyl polyethylene 1,4-naphthalene dicarboxylate initiates lactide polymerization. The 100ml reaction bottle was anhydrous and oxygen-free, cooled under a nitrogen atmosphere, and then under the protection of nitrogen, 1g of the single-terminal hydroxyl polybutylene-1,4-naphthalate obtained in step (1) and 3g of D- Lactide, then add 20ml of V _{tetrachloroethane} with a syringe: V _{o-dichlorobenzene} : V _nitrobenzene = 1:1:1 mixed solvent, so that the concentration of polybutylene naphthalate The concentration of lactide is 50g/L, the concentration of lactide is 0.15Kg/L _, and the temperature is raised to 120°C. At this temperature, the reaction liquid is in the state of a uniform and transparent solution. The reaction was monitored by GPC. After 5 hours, the signal peak of lactide disappeared, the reaction was stopped, and the white crude product was obtained by filtration after cooling.

Step (3). Get the crude product obtained in step (2), add 20ml trifluoroacetic acid, make the crude product concentration 200g/L, settle with 100ml methanol, filter and dry

Step (4). The product obtained in step (3) initiates lactide polymerization. The 100ml reaction bottle was treated with anhydrous and oxygen-free treatment, cooled under a nitrogen atmosphere, and then under the protection of nitrogen, 1g of the product obtained in step (3) and 10g of D, L-lactide were added, and 5ml of tetrahydrofuran was added with a syringe to make the step (3) The concentration of the obtained product is 200g/L, the concentration of lactide is 2.0Kg/L, and the temperature is raised to 30°C. At this temperature, the reaction solution is in a uniform and transparent solution state, and then 0.0011g of SnCl is added with a syringe _2. React at 80°C and monitor with GPC. After 20 hours, the signal peak of lactide disappears, stop the reaction, and filter to obtain a white crude product after cooling.

Step (5). Add 110ml chloroform to the crude product obtained in step (4), so that the crude product concentration is 100g/L, settle with 400ml methanol, filter and dry

Step (6). The product obtained in step (5) initiates lactide polymerization. The 100ml reaction flask was treated anhydrous and oxygen-free, cooled under nitrogen atmosphere, then under the protection of nitrogen, add the product of 1.5g step (5) gained and 3gL-lactide, then add 5ml carbon tetrachloride with syringe, The concentration of the product obtained in step (5) is 300g/L, the concentration of lactide is 0.6Kg/L, and the temperature is raised to 50°C. At this temperature, the reaction solution is in a uniform and transparent solution state, and then 0.0045 g SnCl ₂ , reacted at 110°C, and monitored by GPC for 14 hours, the signal peak of lactide disappeared, the reaction was stopped, and the white crude product was obtained by filtration after cooling.

Step (7). Add 90ml chloroform to the crude product obtained in (6) in the step, so that the crude product concentration is 50g/L, settle with 180ml methanol, filter and dry to obtain the final product, yield 95.2%, do GPC, Various characterizations by ¹ H-NMR, ¹³ C-NMR, and DSC

data

GPC: Use chloroform as the mobile phase, flow rate 1.0ml/min, PS as the standard sample, where the spectrum shows a normal distribution, measured M _n =161.4K, M _w =243.7K, PDI=1.51

¹ H-NMR: 8.75ppm (hydrogen at positions 2 and 3 on the naphthalene ring), 8.05ppm (hydrogen at positions 6 and 7 on the naphthalene ring), 8.55ppm (hydrogen at positions 5 and 8 on the naphthalene ring), 4.70ppm (hydrogens on two methylene groups connected to oxygen in polybutylene 1,4-naphthalate), 2.55ppm (two hydrogens not connected to oxygen in polybutylene 1,4-naphthalate) Hydrogen on the methylene), 5.1ppm (hydrogen on the methine of the PLA block), 1.6ppm (hydrogen on the methyl group of the PLA block); no other peaks produced by transesterification were seen, and the mpoly was obtained from the integrated _{area 1,4-butylene naphthalate} : m _PLA =1:40.

¹³ C-NMR: 168.6.0ppm (the carbonyl carbon on the polybutylene 1,4-naphthalate block), 132.7 ppm (the carbon on the 1st and 4th positions of the naphthalene ring), 126.9ppm (the 2nd naphthalene ring, 3-position carbon), 131.4 ppm (naphthalene ring 5, carbon at 8-position), 127.9 ppm (naphthalene ring 6, carbon at 7-position), 135.1 ppm (naphthalene ring 9, carbon at 10-position), 63.7 ppm (the carbon on the two methylene groups connected to the oxygen in the polybutylene-1,4-naphthalate block), 26.3 ppm (the polybutylene-1,4-naphthalate block The carbon on the two methylene groups that are not connected to the oxygen), 170.0ppm (the carbonyl carbon on the PLA block), 69.2ppm (the methine carbon on the PLA block), 15.7ppm (the methyl group on the PLA block carbon); no remaining peaks due to transesterification were seen.

DSC: T _m (158°C) corresponds to the melting peak of polylactic acid. Due to the low content of polybutylene naphthalate block, no melting peak is seen.

The GPC spectrum is a single peak, and the NMR spectrum has no peaks generated by transesterification, which means that what is obtained is a block copolymer.

, R₂为(CH₂)₄，R₃为C₁₀H₂₁-;B由三种聚乳酸嵌段组成，表示为B₃-B₂-B₁-，其中B₁为右旋聚乳酸嵌段、B₂为外消旋聚乳酸嵌段，B₃为左旋聚乳酸嵌段，。 Obtained in this embodiment is the block copolymer that contains the polybutylene 1,4-naphthalate of polylactic acid of three kinds of different configurations and polylactic acid, in general formula, the R _of A section structural formula is

, R ₂ is (CH ₂ ) ₄ , R ₃ is C ₁₀ H ₂₁ -; B consists of three polylactic acid blocks, represented as B ₃ -B ₂ -B ₁ -, where B ₁ is a dextrorotary polylactic acid block Section, _B2 is racemic polylactic acid block, _B3 is L-polylactic acid block,.

Example 18

Synthesis of Block Copolymers of Poly(1,4-Naphthalate) and Polylactic Acid (PLA) Containing Three Different Configurations of Polylactic Acid.

Step (1). 1-nonanol initiates ring-opening polymerization of cyclic poly(1,4-ethylene naphthalate) to obtain single-terminal hydroxyl poly(1,4-(1)-naphthalene dicarboxylate).

Under the protection of nitrogen, put 10g of cyclic polyhexamethylene-1,4-naphthalate, 0.1g of 1-nonanol and 0.0101 g of Sn(Oct) ₂ into a 100ml reaction flask that has been roasted and cooled with nitrogen. . Add 10ml of V _{tetrachloroethane} through anhydrous and anaerobic treatment with a syringe: the mixed solvent of V _{o-dichlorobenzene} =1:1, so that the concentration of the reaction monomer cyclic poly(1,4-hexanediol naphthalate) is 1.0Kg/L, and the concentration of 1-nonanol is 10g/L. The reaction was carried out at 160°C. After 20 minutes, the reaction was completed (the signal peak of the acyclic monomer was monitored by GPC), cooled and filtered, and the reaction product was washed with anhydrous chloroform to wash away a small amount of unreacted monomer. 80 °C vacuum drying.

Step (2). Polyethylene glycol 1,4-naphthalate with a single terminal hydroxyl group initiates lactide polymerization. The 50ml reaction bottle was anhydrous and oxygen-free, cooled under nitrogen atmosphere, and then added 0.06g of single-terminal hydroxyl poly(1,4-naphthalene dicarboxylate) obtained in step (1) and 1g of D- For lactide, add 2ml of tetrachloroethane with a syringe, so that the concentration of single-ended hydroxyl poly(1,4-naphthalene dicarboxylate) is 30g/L, the concentration of lactide is 0.5Kg/L, and the temperature is raised to 120 ℃, at this temperature, the reaction liquid is in the state of a uniform and transparent solution, then add 0.0106 g Sn(Oct) ₂ with a syringe, react at 120 ℃, monitor with GPC, the signal peak of lactide disappears after 6 hours, stop Reacted, cooled and filtered to obtain a white crude product.

Step (3). Get the crude product of step (2) gained, be dissolved in 10ml chloroform, make crude product concentration be 100 g/L, settle with 40ml methanol, filter and dry to obtain product,

Step (4). The 100ml reaction bottle was also treated anhydrous and oxygen-free, cooled under a nitrogen atmosphere, and then under the protection of nitrogen, 1g of the product obtained in step (3) and 1g of D,L-lactide were added, and then Add 10ml V _{tetrachloroethane} with syringe: the mixed solvent of V _{o-dichlorobenzene} V _{carbon tetrachloride} =1:1:1, make the product concentration that step (3) obtains be 100g/L, the concentration of lactide 0.1Kg/L, heated up to 140°C, at this temperature, the reaction liquid was in a uniform and transparent solution state, and then added 0.003g SnBr ₂ with a syringe, reacted at 140°C, monitored by GPC, and the lactide concentration after 5 hours The signal peak disappeared, the reaction was stopped, and the white crude product was obtained by filtration after cooling.

Step (5). Add 40ml of chloroform to the crude product, so that the concentration of the crude product is 50g/L, settle with 200ml of methanol, filter and dry to obtain the product,

Step (6). The product obtained in step (5) initiates lactide polymerization. The 100ml reaction bottle was also treated anhydrous and oxygen-free, cooled under a nitrogen atmosphere, and then under the protection of nitrogen, add 3g of the product obtained in step (5) and 1g of L-lactide, and then add 10ml of o-dichloro Benzene, so that the concentration of polylactic acid block copolymer is 300g/L, the concentration of lactide is 0.1Kg/L, and the temperature is raised to 140°C. At this temperature, the reaction solution is in a uniform and transparent solution state, and then added with a syringe 0.004g of SnBr ₂ was reacted at 140°C and monitored by GPC. After 3 hours, the signal peak of lactide disappeared, and the reaction was stopped. After cooling, it was filtered to obtain a white crude product.

Step (7). Add 80ml chloroform to the crude product obtained in step (6), so that the crude product concentration is 50g/L, settle with 260ml methanol, filter and dry to obtain the final product, yield 97.2%, do GPC, ¹ Various characterizations by H-NMR, ¹³ C-NMR, and DSC.

data

GPC: Use chloroform as the mobile phase, flow rate 1.0ml/min, PS as the standard sample, where the spectrum presents a normal distribution, measured M _n =31.1K, M _w =45.1K, PDI=1.45

¹ H-NMR: 8.75ppm (hydrogen at positions 2 and 3 on the naphthalene ring), 8.05ppm (hydrogen at positions 6 and 7 on the naphthalene ring), 8.55ppm (hydrogen at positions 5 and 8 on the naphthalene ring), 4.70ppm (hydrogen on the two methylene groups connected to oxygen in polyhexamethylene 1,4-naphthalene dicarboxylate), 2.55ppm (2, hydrogen on two methylene groups at position 5), 2.05 ppm (hydrogen on two methylene groups at positions 3 and 4 in the structure of polyhexamethylene dicarboxylate) 5.1 ppm (PLA Hydrogen on the methine block), 1.6ppm (hydrogen on the methyl group of the PLA block); no other peaks caused by transesterification were seen, and m _{poly(1,4-naphthalene dicarboxylate)} was obtained from the integrated area: m _PLA =1:40.

¹³ C-NMR: 168.6.0ppm (the carbonyl carbon on the polyhexamethylene 1,4-naphthalene dicarboxylate block), 132.7 ppm (the carbon on the 1st and 4th positions of the naphthalene ring), 126.9ppm (the 2nd naphthalene ring, 3-position carbon), 131.4 ppm (naphthalene ring 5, carbon at 8-position), 127.9 ppm (naphthalene ring 6, carbon at 7-position), 135.1 ppm (naphthalene ring 9, carbon at 10-position), 63.7 ppm (the carbon on the two methylene groups connected to the oxygen in the hexamethylene group of poly-1,4-naphthalene dicarboxylate block), 26.3 ppm (the Carbons at positions 2 and 5 in the hexyl group), 21.3 ppm (carbons at positions 3 and 4 in the hexylene group of poly-1,4-naphthalene dicarboxylate block) 170.0 ppm (carbonyl carbon on the PLA block) , 69.2ppm (methine carbon on the PLA block), 15.7ppm (carbon on the methyl group of the PLA block); the remaining peaks due to transesterification were not seen.

DSC: T _m (175°C) corresponds to the PLA block, T _m (215°C) corresponds to the stereocomplex formed by two PLA blocks with different configurations, and poly-1,4-naphthalene is not seen due to the low content Hexylene glycol diformate block melting point

The GPC spectrum is a single peak, and the NMR spectrum has no peaks generated by transesterification, which means that what is obtained is a block copolymer.

,R₂为(CH₂)₆，R₃为C₉H₁₉-;B段由三种聚乳酸嵌段组成，表示为B₃-B₂-B₁-，其中B₁为右旋聚乳酸嵌段、B₂为外消旋聚乳酸嵌段、B₃ 为左旋聚乳酸嵌段。 So what this embodiment obtains is the block copolymer of poly(1,4-naphthalene dicarboxylate) and polylactic acid containing three different configurations of polylactic acid. In the general formula, the _R of the A segment structural formula is

, R ₂ is (CH ₂ ) ₆ , R ₃ is C ₉ H ₁₉ -; segment B consists of three polylactic acid blocks, expressed as B ₃ -B ₂ -B ₁ -, where B ₁ is D-polylactic acid Block, _B2 is racemic polylactic acid block, _B3 is L-polylactic acid block.

Example 19

Synthesis of block copolymers of poly(1,5-naphthalene dicarboxylate) and poly(lactic acid) containing poly(lactic acid) with three configurations.

Step (1). 2-propanol initiates ring-opening polymerization of cyclic poly(1,5-ethylene naphthalate) to obtain single-terminal hydroxyl poly(1,5-(1)-naphthalene dicarboxylate).

Under the protection of nitrogen, put 10g of cyclic polyhexamethylene-1,5-naphthalate, 0.1g of 2-propanol and 0.0101 g of Sn(Oct) ₂ into a 100ml reaction flask that has been roasted and cooled with nitrogen. . Add 10ml of V _{tetrachloroethane} through anhydrous and anaerobic treatment with a syringe: the mixed solvent of V _{o-dichlorobenzene} =1:1, so that the concentration of the reaction monomer cyclic poly(1,5-ethylene naphthalate) It is 1.0Kg/L, and the concentration of 2-propanol is 10g/L. The reaction was carried out at 160°C. After 20 minutes, the reaction was completed (GPC monitored the signal peak of acyclic monomer), cooled and filtered, and the reaction product was washed with anhydrous chloroform to wash away a small amount of unreacted monomer. 60 °C vacuum drying.

Step (2). Polyethylene glycol 1,5-naphthalene dicarboxylate with a single terminal hydroxyl group initiates lactide polymerization. The 100ml reaction bottle was treated anhydrous and oxygen-free, cooled under a nitrogen atmosphere, and then under the protection of nitrogen, 1g of the single-terminal hydroxyl poly(1,5-naphthalene dicarboxylate) obtained in step (1) and 3g of D were added, L-lactide, then add 10ml tetrachloroethane with a syringe, so that the concentration of single-ended hydroxyl poly(1,5-naphthalene dicarboxylate) is 100g/L, and the concentration of lactide is 0.3Kg/L, Dissolve at 120°C. At this temperature, the reaction liquid is in a uniform and transparent solution state. Then add 0.0004g Sn(Oct) ₂ with a syringe and react at 120°C. Monitored by GPC, the signal peak of lactide disappears after 3 hours , stop the reaction, and filter to obtain a white crude product after cooling.

Step (3). Get the crude product obtained in step (2), add 40ml trifluoroacetic acid to make the crude product concentration 100g/L, settle with 150ml methanol, filter and dry

Step (4). The product obtained in step (3) initiates lactide polymerization. The 100ml reaction bottle was treated with anhydrous and oxygen-free treatment, cooled under a nitrogen atmosphere, then under the protection of nitrogen, add 1g of the product obtained in step (3) and 1g of L-lactide, and then add 10ml of V _{tetrachloroethane} with a syringe : V _{o-dichlorobenzene} =1:1 mixed solvent, the concentration of the product that makes step (3) gained is 100g/L, and the concentration of lactide is 0.1Kg/L, is warming up to 80 ℃, at this temperature, The reaction solution was in the state of a uniform and transparent solution, and then 0.01g of SnCl ₄ was added with a syringe, and reacted at 110°C. After monitoring by GPC for 6 hours, the lactide signal peak disappeared, and the reaction was stopped. After cooling, the white crude product was filtered out.

Step (5). Add 40ml chloroform to the crude product gained in step (4), so that the crude product concentration is 50g/L, settle with 160ml methanol, filter and dry

Step (6). The product obtained in step (5) initiates lactide polymerization. The 100ml reaction flask was treated with anhydrous and oxygen-free treatment, cooled under a nitrogen atmosphere, then under the protection of nitrogen, add the product of 1g step (5) gained and 10g D-lactide, then add 5ml toluene with a syringe, so that the step ( 5) The concentration of the obtained product is 200g/L, the concentration of lactide is 2Kg/L, the temperature is raised to 80°C, at this temperature, the reaction solution is in the state of a uniform and transparent solution, and then 0.11g of SnCl ₄ is added with a syringe, The reaction was carried out at 110° C., and the signal peak of lactide disappeared after monitoring by GPC for 5 hours. The reaction was stopped, and the white crude product was obtained by filtration after cooling.

Step (7). Add 40ml chloroform to the crude product obtained in step (6), so that the crude product concentration is 50g/L, settle with 160ml methanol, filter and dry to obtain the final product, yield 94.2%, do GPC, ¹ Various characterizations of H-NMR, ¹³ C-NMR, and DSC

data:

GPC: Use chloroform as mobile phase, flow rate 1.0ml/min, PS as standard sample, where the spectrum presents a normal distribution, flow rate 1.0ml/min, measured M _n =56.1K, M _w =85.27K, PDI=1.52

¹ H-NMR: 8.75ppm (hydrogen at positions 4 and 8 on the naphthalene ring), 8.05ppm (hydrogen at positions 2, 3, 6, and 7 on the naphthalene ring), 4.71ppm (poly-1,5-naphthalene dicarboxylic acid Hydrogen on two methylene groups connected to oxygen in hexanediol ester), 2.45 ppm (hydrogen on two methylene groups at positions 2 and 5 in the hexamethylene structure of poly-1,5-naphthalene dicarboxylate ), 2.08 ppm (hydrogens on the two methylene groups at positions 3 and 4 in the hexamethylene structure of poly-1,5-naphthalene dicarboxylate), 5.15 ppm (hydrogens on the methine groups in the PLA block), 1.65ppm (hydrogen on the methyl group of the PLA block); there is no peak generated by the exchange of poly(1,5-naphthalene dicarboxylate) and poly(lactic acid ester), and m _{poly(1,5-naphthalene dicarboxylate)} is obtained from the integrated area _{Glycol ester} : m _PLA =1:80

¹³ C-NMR: 171.0ppm (the carbonyl carbon on the block of polyhexanediol 1,5-naphthalene dicarboxylate), 126.9 ppm (the carbon on the 1,5 position of the naphthalene ring), 132.7 ppm (the 2,6 Carbon at position), 131.4 ppm (carbon at 3, 7 position of naphthalene ring), 129.6 ppm (carbon at 4, 8 position of naphthalene ring), 134.1 ppm (carbon at 9, 10 position of naphthalene ring), 66.7 ppm (the carbon on the two methylene groups connected to the oxygen in the block hexylene group of poly-1,5-naphthalene dicarboxylate), 25.3 ppm (the block hexylene group of poly-1,5-naphthalene dicarboxylate Carbons at positions 2 and 5), 21.7 ppm (carbons at positions 3 and 4 in the hexylene group of poly-1,5-naphthalene dicarboxylate block), 170.0 ppm (carbonyl carbon on the PLA block), 69.2ppm (methine carbon on the PLA block), 15.7ppm (carbon on the methyl group of the PLA block); there is no peak generated by the exchange of poly(1,5-hexanediol-naphthalate) with polylactate.

DSC: T _m (175°C) corresponds to the PLA block, T _m (205°C) corresponds to the stereocomplex formed by two PLA blocks with different configurations, and no poly-1,5-naphthalene is seen due to the low content Hexylene glycol diformate block melting point

The GPC spectrum is a single peak, and the NMR spectrum has no peaks generated by transesterification, which means that what is obtained is a block copolymer.

,R₂为 (CH₂)₆， B段由三种聚乳酸嵌段组成，表示为B₃-B₂-B₁-，R₃为

;其中B₁为外消旋聚乳酸嵌段、B₂为左旋聚乳酸嵌段、B₃为右旋聚乳酸嵌段。 Obtained in this embodiment is the block copolymer of polyethylene 1,5-naphthalene dicarboxylate and polylactic acid, in the general formula, the _R of the A section structural formula is

, R ₂ is (CH ₂ ) ₆ , segment B is composed of three polylactic acid blocks, expressed as B ₃ -B ₂ -B ₁ -, R ₃ is

; wherein _B1 is a racemic polylactic acid block, _B2 is a left-handed polylactic acid block, and _B3 is a right-handed polylactic acid block.

Example 20

Synthesis of Block Copolymers of Polybutylene Naphthalate and Polylactic Acid Containing Three Configurations of Polylactic Acid.

Step (1). 1-nonanol initiates ring-opening polymerization of cyclic polybutylene-1,5-naphthalate to obtain single-terminal hydroxyl polybutylene-1,5-naphthalate.

Under the protection of nitrogen, put 10g of cyclic polybutylene-1,5-naphthalate, 0.1g of 1-decanol and 0.0101 g of Sn(Oct) ₂ into a 100ml reaction flask that has been roasted and cooled with nitrogen. . Add 10ml of V _{tetrachloroethane} :V _{o-dichlorobenzene} =1:1 mixed solvent through anhydrous and anaerobic treatment with a syringe, so that the concentration of cyclic polybutylene naphthalate is 1.0Kg /L, the concentration of 1-decanol is 10g/L. The reaction was carried out at 160°C. After 20 minutes, the reaction was completed (the signal peak of the acyclic monomer was monitored by GPC), cooled and filtered, and the reaction product was washed with anhydrous chloroform to wash away a small amount of unreacted monomer. 80 °C vacuum drying.

Step (2). Lactide polymerization is initiated by poly(1,5-butylene naphthalate) with single-terminal hydroxyl group. The 50ml reaction bottle was anhydrous and oxygen-free, cooled under a nitrogen atmosphere, and then under the protection of nitrogen, 0.06g of single-terminal hydroxyl polybutylene-1,5-naphthalate obtained in step (1) and 1gL- For lactide, add 2ml of tetrachloroethane with a syringe, so that the concentration of single-ended hydroxyl polybutylene-1,5-naphthalate is 30g/L, and the concentration of lactide is 0.5Kg/L, and the temperature is raised to 120 ℃, at this temperature, the reaction liquid is in the state of a uniform and transparent solution, then add 0.0106 g Sn(Oct) ₂ with a syringe, react at 120 ℃, monitor with GPC, the signal peak of lactide disappears after 6 hours, stop Reacted, cooled and filtered to obtain a white crude product.

Step (3). Get the crude product obtained in step (2), be dissolved in 10ml chloroform, make the crude product concentration be 100 g/L, settle with 40ml methanol, filter and dry

Step (4). The product obtained in step (3) initiates lactide polymerization. The 100ml reaction flask was treated anhydrous and oxygen-free, cooled under nitrogen atmosphere, then under the protection of nitrogen, add the product of 1g step (3) gained and 8g D-lactide, then add 10ml tetrachloroethane with syringe, The concentration of the product obtained in step (3) is 100g/L, the concentration of lactide is 0.8Kg/L, and the temperature is raised to 50°C. At this temperature, the reaction solution is in a uniform and transparent solution state, and then 0.0009 g Sn(Oct) ₂ , reacted at 110°C, and monitored by GPC for 6 hours, the signal peak of lactide disappeared, the reaction was stopped, and the white crude product was obtained by filtration after cooling.

Step (5). Add 100ml chloroform to the crude product gained in step (4), so that the crude product concentration is 90g/L, settle with 360ml methanol, filter and dry

Step (6). The product obtained in step (5) initiates lactide polymerization. The 100ml reaction bottle was treated anhydrous and oxygen-free, cooled under a nitrogen atmosphere, and then under the protection of nitrogen, add 1g of the product obtained in step (5) and 1g of D, L-lactide, and then add 10ml of tetrachloroethylene with a syringe. alkane so that the concentration of the product obtained in step (5) is 100g/L, the concentration of lactide is 0.1Kg/L, and the temperature is raised to 50°C. At this temperature, the reaction solution is in a uniform and transparent solution state, and then the Add 0.0002g of Sn(Oct) ₂ , react at 110°C, monitor with GPC for 5 hours and then the lactide signal peak disappears, stop the reaction, cool and filter to obtain a white crude product.

Step (7). Add 25ml chloroform to the crude product obtained in (6) in the step, so that the crude product concentration is 80g/L, settle with 120ml methanol, filter and dry to obtain the final product, yield 97.1%, do GPC, Various characterizations by ¹ H-NMR, ¹³ C-NMR, and DSC.

data

GPC: Use chloroform as the mobile phase, flow rate 1.0ml/min, PS as the standard sample, where the spectrum shows a normal distribution, measured M _n =90.1K, M _w =129.7K, PDI=1.44

¹ H-NMR: 8.75ppm (hydrogen at positions 4 and 8 on the naphthalene ring), 8.05ppm (hydrogen at positions 2, 3, 6, and 7 on the naphthalene ring), 4.65ppm (poly-1,5-naphthalene dicarboxylic acid Hydrogen on two methylene groups connected to oxygen in butanediol ester), 2.45 ppm (hydrogen on two methylene groups at positions 2 and 3 in the structure of polybutylene 1,5-naphthalate hexylene ), 5.10ppm (hydrogen on the methyl group of the PLA block), 1.62ppm (hydrogen on the methyl group of the PLA block); no other peaks caused by transesterification were seen, and PLA was obtained from the integrated area: poly 1,5-naphthalene di The mass ratio of butylene glycol formate is 200:1

¹³ C-NMR: 171.1ppm (the carbonyl carbon on the polybutylene naphthalate block), 126.9 ppm (the carbon on the 1,5 position of the naphthalene ring), 132.7 ppm (the 2,6 Carbon at position), 131.4 ppm (carbon at 3, 7 position of naphthalene ring), 129.6 ppm (carbon at 4, 8 position of naphthalene ring), 134.1 ppm (carbon at 9, 10 position of naphthalene ring), 66.7 ppm (the carbon on the two methylene groups connected to oxygen in the polybutylene-1,5-naphthalate block), 25.3 ppm (polybutylene-1,5-naphthalate block-butylene Carbons at positions 2 and 3), 170.1ppm (carbonyl carbon on the PLA block), 69.1ppm (methine carbon on the PLA block), 15.7ppm (carbon on the methyl group of the PLA block); the rest are not seen Peaks resulting from transesterification.

DSC: T _m (220°C) corresponds to the stereocomplex formed by the two configurations of polylactic acid blocks, T _m (160°C) corresponds to the PLA block, due to polybutylene naphthalate Too little ester content, no melting point seen

The GPC spectrum is a single peak, and the NMR spectrum has no peaks generated by transesterification, indicating that the obtained block copolymer

,R₂为(CH₂)₄，R₃为C₁₀H₂₁-；B三两种聚乳酸嵌段组成，表示为B₃-B₂-B₁-，其中B₁为左旋聚乳酸嵌段、B₂为右旋聚乳酸嵌段、B₃为外消旋聚乳酸嵌段。 What is obtained in this embodiment is the block copolymer of poly(butylene naphthalate) and polylactic acid containing three configurations of polylactic acid. In the general formula, the R _of the A segment structural formula is

, R ₂ is (CH ₂ ) ₄ , R ₃ is C ₁₀ H ₂₁ -; B is composed of three or two polylactic acid blocks, expressed as B ₃ -B ₂ -B ₁ -, where B ₁ is a left-handed polylactic acid block , _B2 is a dextrorotatory polylactic acid block, and _B3 is a racemic polylactic acid block.

Example 21

Synthesis of Block Copolymers of Polytrimethylene Naphthalate and Polylactic Acid Containing Three Configurations of Polylactic Acid.

Step (1). 1-octanol initiates ring-opening polymerization of cyclic polybutylene-1,5-naphthalate to obtain single-terminal hydroxyl polybutylene-1,4-naphthalate.

Under the protection of nitrogen, put 10g of cyclic polytrimethylene 1,5-naphthalate, 0.1g of 1-octanol and 0.0101 g of Sn(Oct) ₂ into a 100ml reaction flask which has been roasted and cooled with nitrogen. Add 10ml V _{tetrachloroethane} through anhydrous anaerobic treatment with syringe: the mixed solvent of V _nitrobenzene =1:1, make the concentration of cyclic polytrimethylene naphthalate 1,5-naphthalate be 1.0Kg/L, The concentration of 1-octanol is 10g/L. The reaction was carried out at 160°C. After 20 minutes, the reaction was completed (the signal peak of the acyclic monomer was monitored by GPC), cooled and filtered, and the reaction product was washed with anhydrous chloroform to wash away a small amount of unreacted monomer. 80 °C vacuum drying.

Step (2). Double-terminated hydroxyl poly(1,5-trimethylene naphthalate) initiates lactide polymerization. The 100ml reaction bottle was treated with anhydrous and oxygen-free treatment, cooled under a nitrogen atmosphere, and then under the protection of nitrogen, 0.06g of single-terminal hydroxyl poly(trimethylene naphthalate) obtained in step (1) and 1g of D-lactate were added ester, and then add 2ml o-dichlorobenzene with a syringe, so that the concentration of polytrimethylene naphthalate is 30g/L, the concentration of lactide is 0.5Kg/L, and the temperature is raised to 60°C. , the reaction solution was in the state of a uniform and transparent solution, and then 0.0106g SnCl ₂ was added with a syringe, reacted at 60°C, and monitored by GPC. After 24 hours, the signal peak of lactide disappeared, and the reaction was stopped. After cooling, it was filtered to obtain a white crude product.

Step (3). Get the crude product of step (2) gained, be dissolved in 20ml chloroform, make the crude product concentration be 50 g/L, settle with 60ml methanol, filter and dry

Step (4). The product obtained in step (3) initiates lactide polymerization. The 100ml reaction bottle was treated anhydrous and oxygen-free, cooled under a nitrogen atmosphere, then under the protection of nitrogen, add 1g of the product obtained in step (3) and 20g L-lactide, and then add 10ml of chloroform with a syringe, so that The concentration of the product obtained in step (3) is 100g/L, the concentration of lactide is 2Kg/L, and the temperature is raised to 50°C. At this temperature, the reaction solution is in a uniform and transparent solution state, and then 0.21g SnCl is added with a syringe _2. React at 50°C. After monitoring by GPC for 24 hours, the signal peak of lactide disappears, stop the reaction, and filter to obtain a white crude product after cooling.

Step (5). Add 210ml chloroform to the crude product gained in step (4), so that the crude product concentration is 100g/L, settle with 630ml methanol, filter and dry

Step (6). The product obtained in step (5) initiates lactide polymerization. The 100ml reaction bottle was treated anhydrous and oxygen-free, cooled under a nitrogen atmosphere, and then under the protection of nitrogen, add 3g of the product obtained in step (5) and 1g of D,L-lactide, and then add 10ml of chloroform with a syringe , so that the concentration of the product obtained in step (5) is 300g/L, the concentration of lactide is 0.1Kg/L, and the temperature is raised to 50°C. At this temperature, the reaction solution is in a uniform and transparent solution state, and then added with a syringe 0.04g of SnCl ₂ was reacted at 50°C. After 24 hours of GPC monitoring, the signal peak of lactide disappeared, and the reaction was stopped. After cooling, the white crude product was filtered out.

Step (7). Add 50ml chloroform to the crude product obtained in (6) in the step, so that the crude product concentration is 80g/L, settle with 150ml methanol, filter and dry to obtain the final product, yield 96.2%, do GPC, Various characterizations by ¹ H-NMR, ¹³ C-NMR, and DSC.

data

GPC: Use chloroform as mobile phase, flow rate 1.0ml/min, PS as standard sample, where the spectrum shows normal distribution, measured M _n =63.9K, M _w =100.96K, PDI=1.58

¹ H-NMR: 8.75ppm (hydrogen at positions 4 and 8 on the naphthalene ring), 8.05ppm (hydrogen at positions 2, 3, 6, and 7 on the naphthalene ring), 4.75ppm (poly-1,5-naphthalene dicarboxylic acid Hydrogen on two methylene groups linked to oxygen in propylene glycol ester), 2.55 ppm (hydrogen on two methylene groups on the 2-position in the propylene structure of poly-1,5-trimethylene naphthalate), 5.10 ppm ( Hydrogen on the methine of the PLA block), 1.62ppm (hydrogen on the methyl group of the PLA block); no other peaks generated by transesterification were seen, and m _{1,5-trimethylene naphthalate} was obtained from the integrated area: m _PLA = 1:350

¹³ C-NMR: 171.0ppm (the carbonyl carbon on the polytrimethylene naphthalate block), 126.8 ppm (the carbon on the 1,5 position of the naphthalene ring), 132.8 ppm (the 2,6 position on the naphthalene ring carbon), 131.4 ppm (carbon on naphthalene ring 3, 7), 129.6 ppm (carbon on naphthalene ring 4, 8), 134.1 ppm (carbon on naphthalene ring 9, 10), 66.7 ppm (carbon on poly 1,5-trimethylene naphthalate block propylene glycol, the carbon on the two methylene groups connected to oxygen), 25.3 ppm (the 2-position in the block propylene glycol 1,5-naphthalene dicarboxylate carbon), 170.0ppm (carbonyl carbon on the PLA block), 69.2ppm (methine carbon on the PLA block), 15.6ppm (carbon on the methyl group of the PLA block); no other peaks from transesterification were seen .

DSC: T _m (173°C) corresponds to the PLA block, T _m (220°C) corresponds to the stereocomplex generated by the two configurations of the polylactic acid block, due to the polytrimethylene naphthalate The content is too small, and there is no melting point of polytrimethylene naphthalate block.

The GPC spectrum is a single peak, and the NMR spectrum has no peaks generated by transesterification, which means that what is obtained is a block copolymer.

,R₂为(CH₂)₃ R₃为C₈H₁₇-； B由三种聚乳酸嵌段组成，表示为B₃-B₂-B₁-，其中B₁为右旋聚乳酸嵌段、B₂为左旋聚乳酸嵌段、B₃为外消旋聚乳酸嵌段。 What is obtained in this embodiment is the block copolymer of poly(trimethylene naphthalate) containing three configurations of polylactic acid and polylactic acid. In the general formula, the R _of the A segment structural formula is

, R ₂ is (CH ₂ ) ₃ R ₃ is C ₈ H ₁₇ -; B consists of three polylactic acid blocks, expressed as B ₃ -B ₂ -B ₁ -, where B ₁ is a right-handed polylactic acid block , _B2 is a L-polylactic acid block, and _B3 is a racemic polylactic acid block.

Example 22

Block copolymer of poly(1,5-naphthalene dicarboxylate-1,4-cyclohexane dimethyl ester) containing three configurations of poly(lactic acid) and poly(lactic acid).

Step (1). 1-hexanol initiates ring-opening polymerization of cyclic poly-1,4-cyclohexanedimethylester 1,5-naphthalene dicarboxylate to obtain single-terminal hydroxyl polybutylene-1,4-naphthalene dicarboxylate Alcohol esters.

Under the protection of nitrogen, put 10g of cyclic poly-1,5-naphthalene dicarboxylate-1,4-cyclohexanedimethylester, 0.05g of 1-hexanol and 0.01 g of Sn(Oct) ₂ into Cooled 100ml reaction vials. Add 5ml V _{tetrachloroethane} through anhydrous anaerobic treatment with syringe: V _nitrobenzene : V _{o-dichlorobenzene} =1:1:1 mixed solvent, make cyclic poly-1,5 naphthalene dicarboxylic acid-1, The concentration of 4-cyclohexane dimethyl ester was 2.0 Kg/L, and the concentration of 1-hexanol was 10 g/L. The reaction was carried out at 165°C. After 25 minutes, the reaction was completed (the signal peak of the acyclic monomer was monitored by GPC), cooled and filtered, and the reaction product was washed with anhydrous chloroform to wash away a small amount of unreacted monomer. 80 °C vacuum drying.

Step (2). Single-terminal hydroxyl poly-1,5-naphthalene dicarboxylate-1,4-cyclohexanedimethyl ester initiates lactide polymerization. The 100ml reaction bottle has been anhydrous and oxygen-free, cooled under nitrogen atmosphere, and then added 0.1g of the single-terminal hydroxyl poly-1,5-naphthalene dicarboxylate-1,4-cyclohexane obtained in step (1) under the protection of nitrogen Dimethyl ester and 2g D,L-lactide, then add 10ml 1,2,4-trichlorobenzene with a syringe to make the concentration of poly-1,5 naphthalene dicarboxylic acid-1,4-cyclohexane dimethyl ester The concentration of lactide is 10g/L, the concentration of lactide is 0.2Kg/L, and the temperature is raised to 130°C. At this temperature, the reaction solution is in the state of a uniform and transparent solution. Then add 0.0021g of SnCl ₄ with a syringe and react at 150°C. GPC monitoring showed that the signal peak of lactide disappeared after 2 hours, the reaction was stopped, and the white crude product was obtained by filtration after cooling.

Step (3). Take the crude product obtained in step (2), add 40ml of chloroform to make the concentration of the crude product 50g/L, settle with 120ml of methanol, filter and dry.

Step (4). The product obtained in step (3) initiates lactide polymerization. The 100ml reaction bottle was treated with anhydrous and oxygen-free treatment, cooled under nitrogen atmosphere, then under the protection of nitrogen, add 1g of the product obtained in step (3) and 20g L-lactide, and then add 10ml of dichloromethane with a syringe, so that The concentration of the product obtained in step (3) is 100g/L, the concentration of lactide is 2Kg/L, and the temperature is raised to 30°C. At this temperature, the reaction solution is in a uniform and transparent solution state, and then 0.21g SnCl is added with a syringe _2. React at 30°C. After monitoring by GPC for 24 hours, the signal peak of lactide disappears, stop the reaction, and filter to obtain a white crude product after cooling.

Step (5). Add 210ml of chloroform to the crude product obtained in step (4), so that the concentration of the crude product is 100g/L, settle with 840ml of methanol, filter and dry.

Step (6). The product obtained in step (5) initiates lactide polymerization. The 100ml reaction bottle was treated with anhydrous and oxygen-free treatment, cooled under a nitrogen atmosphere, and then under the protection of nitrogen, 1g of the product obtained in step (5) and 1gD-lactide were added, and 10ml of tetrachloromethane was added with a syringe to make the step (5) The concentration of the obtained product is 100g/L, the concentration of lactide is 1Kg/L, and the temperature is raised to 30°C. At this temperature, the reaction solution is in a uniform and transparent solution state, and then _0.02g of SnCl is added with a syringe. , reacted at 30°C, and monitored by GPC for 24 hours, the signal peak of lactide disappeared, and the reaction was stopped, and the white crude product was obtained by filtration after cooling.

Step (7). Add 20ml chloroform to the crude product obtained in (6) in the step, so that the crude product concentration is 100g/L, settle with 100ml methanol, filter and dry to obtain the final product

data

GPC: Use chloroform as the mobile phase, flow rate 1.0ml/min, PS as the standard sample, where the spectrum shows a normal distribution, measured M _n =103.8K, M _w =150.51K, PDI=1.45

¹ H-NMR: 8.77ppm (hydrogen at positions 4 and 8 on the naphthalene ring), 8.06ppm (hydrogen at positions 2, 3, 6, and 7 on the naphthalene ring), 4.55ppm (poly-1,5-naphthalene dicarboxylic acid -Hydrogen on the two methylene groups connected to the 1,4 positions of the cyclohexylene in the 1,4-cyclohexane dimethyl ester block), 1.3～2.2ppm (poly-1,5-naphthalene dicarboxylic acid-1, 4-cyclohexane dimethyl ester block cyclohexylene), 5.10ppm (hydrogen on the PLA block methine), 1.62ppm (PLA block hydrogen on the methyl group); no other peaks caused by transesterification , get m poly _{-1,5-naphthalene dicarboxylic acid-1,4-cyclohexane dimethyl ester} from integral area: m _PLA =1:60

¹³ C-NMR: 171.0ppm (the carbonyl carbon on the block of poly-1,5-naphthalene dicarboxylate-1,4-cyclohexanedimethylester), 126.8 ppm (the carbon on the 1,5 position of the naphthalene ring), 132.8 ppm (carbon on the 2nd and 6th positions of the naphthalene ring), 131.4 ppm (carbons on the 3rd and 7th positions of the naphthalene ring), 129.6 ppm (carbons on the 4th and 8th positions of the naphthalene ring), 134.1 ppm (9 and 10th positions on the naphthalene ring carbon on the 1,4-cyclohexanedimethylene dicarboxylate block), 61.2ppm (carbons on the two methylene groups connected at the 1,4 positions in the poly-1,5-naphthalene dicarboxylic acid-1,4-cyclohexanedimethylene block cyclohexylene), 25.2 ppm ( Poly-1,5-naphthalene dicarboxylate-1,4-cyclohexanedimethylene carbons on the two methine groups in the cyclohexylene group of 1,4), 18.6 ppm (poly-1,5-naphthalene dicarboxylate-1,4 -Carbons on the four methylene groups of 2, 3, 5, and 6 in the cyclohexylene group of the cyclohexane dimethyl ester block), 170.0ppm (the carbonyl carbon on the PLA block), 68.2ppm (the methine on the PLA block base carbon), 15.85ppm (carbon on the methyl group of the PLA block); no other peaks due to transesterification were seen.

DSC: T _m (205°C) corresponds to poly-1,5-naphthalate-1,4-cyclohexanedimethylester block, T _m (155°C) corresponds to PLA block, T _m (220°C) Corresponding to the stereocomplex formed by left-handed and right-handed polylactic acid blocks.

The GPC spectrum is a single peak, and the NMR spectrum has no peaks generated by transesterification, which means that what is obtained is a block copolymer.

,R₂为

，R₃为C₆H₁₃-;B由三种聚乳酸嵌段组成，表示为B₃-B₂-B₁-，其中B₁为外消旋聚乳酸嵌段、B₂为左旋聚乳酸嵌段、B₃为右旋聚乳酸嵌段。 What is obtained in this example is a block copolymer of poly-1,5-naphthalene dicarboxylate-1,4-cyclohexane dimethyl containing polylactic acid in three configurations and polylactic acid. In the general formula, A R ₁ of the segment structure formula is

, R ₂ is

, R ₃ is C ₆ H ₁₃ -; B is composed of three polylactic acid blocks, expressed as B ₃ -B ₂ -B ₁ -, wherein B ₁ is a racemic polylactic acid block, B ₂ is a left-handed polylactic acid block Block, _B3 is a D-polylactic acid block.

Claims (9)

1. process for polylactic acid block copolymer production, described polylactic-acid block copolymer is a di-block copolymer, is expressed as A- b-B, bThe expression block;

A is an one-ended hydroxy aromatic polyester block, and structural formula is:

R ₁For

,

,

,

In one or more;

R ₂Be (CH ₂) ₂, (CH ₂) ₃, (CH ₂) ₄, (CH ₂) ₆,

In one or more;

R ₃For alkyl, contain carbon-carbon double bond unsaturated substituting group, contain the unsaturated substituting group of carbon-carbon triple bond or contain the unsaturated substituting group of phenyl ring;

B is the POLYACTIC ACID block, and its structural formula is:

It is characterized in that this method may further comprise the steps:

Step (1). the preparation of one-ended hydroxy aromatic polyester: under nitrogen protection; Ring-type aromatic polyester oligopolymer, monohydroxy-alcohol and pink salt catalyzer are dissolved in the first kind organic solvent of handling through anhydrous and oxygen-free; Under 120～180 ℃ of conditions, react; Adopt gel permeation chromatograph monitoring reaction process in the reaction process, stopped reaction after the fignal center of ring-type aromatic polyester oligopolymer disappears; Reaction is cooled to normal temperature after accomplishing, and filters to obtain required one-ended hydroxy aromatic polyester;

Described ring-type aromatic polyester oligopolymer is ring-type polyethylene terephthalate, ring-type PTT, ring-type polybutylene terephthalate, ring-type poly terephthalic acid pinakon ester, ring-type poly terephthalic acid-1, and 4-hexanaphthene dimethyl ester, ring-type polyethylene glycol 1, ring-type gather 1; 4-naphthalic acid propylene glycol ester, ring-type gather 1, and 4-naphthalic acid butanediol ester, ring-type gather 1, and 4-naphthalic acid pinakon ester, ring-type gather 1; 4-naphthalic acid-1,4-hexanaphthene dimethyl ester, ring-type gather 1, and 5-(ethylene naphthalate), ring-type gather 1; 5-naphthalic acid propylene glycol ester, ring-type gather 1, and 5-naphthalic acid butanediol ester, ring-type gather 1, and 5-naphthalic acid pinakon ester, ring-type gather 1; 5-naphthalic acid-1; 4-hexanaphthene dimethyl ester, ring-type polyethylene glycol 2, ring-type gather 2, and 6-naphthalic acid propylene glycol ester, ring-type gather 2; 6-naphthalic acid butanediol ester, ring-type gather 2; 6-naphthalic acid pinakon ester, ring-type gather 2,6-naphthalic acid-1, one or more in the 4-hexanaphthene dimethyl ester;

Step (2). with one-ended hydroxy aromatic polyester process vacuum drying; Make its moisture content smaller or equal to 20ppm; One-ended hydroxy aromatic polyester after the oven dry and first kind rac-Lactide are dissolved in the first kind organic solvent of handling through anhydrous and oxygen-free under 60～130 ℃; Add the pink salt catalyzer again, 60～150 ℃ of reactions down; Adopt gel permeation chromatograph monitoring reaction process in the reaction process, stopped reaction after the fignal center of first kind rac-Lactide disappears; Reaction is accomplished postcooling to normal temperature, filters and obtains first kind crude product;

Described first kind rac-Lactide is L-rac-Lactide, D-rac-Lactide or D, the L-rac-Lactide;

Step (3). the first kind crude product of step (2) gained is dissolved in second type of organic solvent, and the methyl alcohol with 3～5 times of volumes of second type of organic solvent carries out sedimentation again, and filtering drying obtains first kind product;

Step (4). first kind product and second type of rac-Lactide are dissolved in the 3rd type of organic solvent of handling through anhydrous and oxygen-free; Add the pink salt catalyzer again; 30～140 ℃ of reactions down; Adopt gel permeation chromatograph monitoring reaction process in the reaction process, stopped reaction after the fignal center of second type of rac-Lactide disappears; Reaction is accomplished postcooling to normal temperature, filters and obtains second type of crude product;

Described second type of rac-Lactide is L-rac-Lactide, D-rac-Lactide or D, the L-rac-Lactide, and different with first kind rac-Lactide type;

Step (5). second type of crude product of step (4) gained is dissolved in the chloroform, makes that the concentration of second type of crude product is 50～100g/L, the methyl alcohol with 3～5 times of volumes of chloroform carries out sedimentation again, and filtering drying obtains second type of product;

Step (6). second type of product and the 3rd type of rac-Lactide are dissolved in the 3rd type of organic solvent of handling through anhydrous and oxygen-free; Add the pink salt catalyzer again; 30～140 ℃ of reactions down; Adopt gel permeation chromatograph monitoring reaction process in the reaction process, stopped reaction after the fignal center of the 3rd type of rac-Lactide disappears; Reaction is accomplished postcooling to normal temperature, filters and obtains the 3rd type of crude product;

Described the 3rd type of rac-Lactide is L-rac-Lactide, D-rac-Lactide or D, the L-rac-Lactide, and different with the type of first kind rac-Lactide and second type of rac-Lactide;

Step (7). the 3rd type of crude product of step (6) gained is dissolved in the chloroform, makes that the concentration of the 3rd type of crude product is 50～100g/L, use the methyl alcohol sedimentation of 3～5 times of volumes of chloroform again, filtering drying obtains the 3rd type of product; The 3rd type of product is the segmented copolymer that comprises three kinds of configuration POLYACTIC ACIDs.

2. a kind of process for polylactic acid block copolymer production as claimed in claim 1; It is characterized in that: the concentration of the ring-type aromatic polyester oligopolymer in the step (1) after the dissolving is 0.2～2Kg/L; The concentration of the monohydroxy-alcohol after the dissolving is smaller or equal to 200g/L, add catalyzer quality be 0.01～1% of reactant ring-type aromatic polyester oligopolymer and monohydroxy-alcohol total mass.

3. a kind of process for polylactic acid block copolymer production as claimed in claim 1; It is characterized in that: the concentration of the one-ended hydroxy aromatic polyester in the step (2) after the dissolving is smaller or equal to 100g/L; The concentration of first kind rac-Lactide is smaller or equal to 2Kg/L, add the pink salt catalyzer quality be 0.01～1% of one-ended hydroxy aromatic polyester and first kind rac-Lactide total mass.

4. a kind of process for polylactic acid block copolymer production as claimed in claim 1 is characterized in that: the first kind organic solvent described in step (1) and (2) is orthodichlorobenzene, tetrachloroethane, oil of mirbane, 1,2, one or more in the 4-trichlorobenzene.

5. a kind of process for polylactic acid block copolymer production as claimed in claim 1; It is characterized in that: second type of organic solvent described in the step (3) is a kind of in chloroform, the trifluoracetic acid or both mixtures, and the concentration of the first kind crude product after the dissolving is 50～200g/L.

6. a kind of process for polylactic acid block copolymer production as claimed in claim 1 is characterized in that: the 3rd type of organic solvent described in step (4) and (6) is one or more in methylene dichloride, chloroform, tetracol phenixin, toluene, THF, orthodichlorobenzene, the tetrachloroethane.

7. a kind of process for polylactic acid block copolymer production as claimed in claim 1 is characterized in that:

The concentration of the first kind product in the step (4) after the dissolving is smaller or equal to 300g/L, and the concentration of second type of rac-Lactide is smaller or equal to 2Kg/L, add the pink salt catalyzer quality be 0.01～1% of first kind product and second type of rac-Lactide total mass.

8. a kind of process for polylactic acid block copolymer production as claimed in claim 1 is characterized in that:

The concentration of second type of product in the step (6) after the dissolving is smaller or equal to 300g/L, and the concentration of the 3rd type of rac-Lactide is smaller or equal to 2Kg/L, add the pink salt catalyzer quality be 0.01～1% of second type of product and the 3rd type of rac-Lactide total mass.

9. a kind of process for polylactic acid block copolymer production as claimed in claim 1 is characterized in that: the pink salt catalyzer described in step (1), (2), (4) and (6) is Sn (Oct) ₂, SnCl ₂, SnCl ₄, SnBr ₂In a kind of.