TW201226416A - Phosphorus-containing diol monomer and flame retardant polyester copolymer thereof - Google Patents

Abstract

A phosphorus-containing diol monomer and a flame retardant phosphorus-containing polyester copolymer thereof are disclosed. The flame retardant phosphorus-containing polyester copolymer is prepared by polymerization of a diol monomer (I) and an ester monomer. The phosphorus amount of the flame retardant phosphorus-containing polyester copolymer is 0.5-3.0 wt%.

Description

201226416 VI. Description of the invention: [Technical field to which the invention pertains] The invention is related to a dish-type diol monomer and a flame-retardant polyester copolymer thereof, and particularly relates to a phosphorus-based diol as a constituent monomer The flame retardant phosphorus is a self-assembled copolymer. [Prior Art] Polyester is an important plastic material with good mechanical and chemical properties and is widely used in synthetic fibers, fabrics, films and other related industries. Since the poly-g-polymer is widely used in the industry of people's livelihood, the flame-resistant properties of synthetic fibers have gradually received attention. In order to achieve a flame retardant effect on the polyester polymer, a flame retardant may be added by using a blending method or the finished fiber may be treated to attach the flame retardant to the surface of the fiber. However, it is convenient to blend a polyester polymer with a flame retardant, but there is often a case where the compatibility is poor and the flame retardant migration causes a decrease in flame retardancy. Further, when the number of washings is increased by the number of washings treated with the flame retardant, the flame retardancy of the fabric is lowered. On the other hand, it is possible to bond a flame retardant to a polymer chain by means of a COp〇lymer method. This method uses a chemical bond to introduce a flame retardant into the polymer chain to migrate to the polymer chain without being affected by the processing procedure. surface. The prior literature proposes transesterification of bis(hydroxyethyl)naphthalate; BHEN and bis(hydroxybutyl)phthalate (BHBN) in a copolymerized manner with a phosphorus compound having a diol structure. A polyester polymer having flame retardant properties is obtained. (Wang CS; Lin, 201226416 CH " Synthesis and properties of phosphorus-containing PEN and PBN copolyesters" Polymer, 1999, 40, 747.) [Invention] Therefore, one aspect of the present invention is to provide a phosphorus system. The diol, which is a constituent monomer of the polyester copolymer, provides the flame retardant properties of the polyester copolymer. According to one or more embodiments of the present invention, the diol-filling monomer has the following formula (I) Structure:

〇ch2choh

X wherein X is hydrogen or a methyl group, and R is a hydrogen atom, a phenyl group, a C1_C10 alkyl group, a C3-C10 cycloalkyl group or a halogen atom. One aspect of the present invention provides a method of preparing a phosphorus-based diol monomer represented by the formula (1). Including the use of a phosphorus compound (a), a compound of formula (b) φ and a base catalyst, wherein the base catalyst is CsF, KF, KI, CsCh KC1, K2C〇3, NasCO3, K0H or NaOH, and the alkali contact The amount of the medium used is 0·1 wt% to 1〇wt〇/ of the amount of the scaly compound (a). :

(b) A phosphorus-based polyester represented by the formula (I) In one aspect of the invention, a flame-retardant phosphorus-based polyester copolymer comprising a sterol as a constituent monomer is provided. 201226416 According to an embodiment of the present invention, the flame-retardant phosphorus-based polyester copolymer has a structure represented by the following formula (II):

(II) wherein 'X is hydrogen or methyl, R is a gas atom, phenyl, Cl-C10 alkyl, C3-C10 cycloalkyl or halogen atom, n=2-8, and the content of the copolymer is 〇5_3 〇 _ weight percentage. According to another embodiment of the present invention, the flame-retardant packing copolymer has a structure represented by the following formula (III):

Wherein X is hydrogen or methyl, R is a hydrogen atom, a strepyl group, a CKci 、, a C3 - C10 cycloalkyl group or a _ atom, and n = 2_8, and the content is a weight percent of the copolymer. · It is understood that the embodiment of the present invention replaces the conventional method by using a phosphorus atom to introduce a method for the introduction of a poly-molecular molecule into a poly-molecular group, which can be used in a small amount of difficult-to-consistence and has a good flame retardant effect and is difficult to maintain. It is durable and stable. ^Original (four) (4) 'Making flame retardant effect 【Embodiment】 201226416 (I) Synthesis of phosphorus-based diol monomer The phosphorus-based diol of the embodiment of the present invention has a structure as shown in formula (1) As a constituent monomer of the polyester copolymer, it can be transesterified with a monool ester monomer to form a phosphorus-based flame retardant polyester copolymer via a polycondensation reaction.

Synthesis Example 1: Phosphorus-based diol monomer DMP-EC DMP-EC is obtained by reacting a bisphenol monomer DMP with ethylene carbonate (EC) under a catalytic catalyst. Wherein the biguanide monomer DMP is represented by the above formula (a), and R is a methyl group. Phosphorus diol monomer DMP-EC • The synthesis procedure is as follows: In a 0.5 liter three-neck reactor equipped with a temperature indicating device, 42.81 g (0.1 mol) of DMP and 26.4 g of ethylene carbonate (0.3 mol) were added. The base catalyst is 30.34 g (0.22 mol) of potassium carbonate, and the solvent is DMAc. The reaction temperature was raised to 120 ° C, the reaction system temperature was maintained at 120 ° C and reacted for 12 hours, and then dropped into water to be stirred and precipitated, and the filter cake after suction filtration was washed with a large amount of deionized water. The cake separated by filtration was vacuum dried at 11 ° C to give a product (1 )' yield of 78%. The molecular weight of the product was identified by a high resolution mass spectrometer φ instrument.

Figure 1 is a 1H NMR spectrum of the product (1). The results of the spectral analysis revealed that the product (1) was DMP-EC, the molecular formula was c30H29O6P, and the molecular weight was 516.1698. 201226416 (II) Synthesis of broken flame-retardant polymer copolymer According to an embodiment of the present invention, the flame-retardant phosphorus-based polyester copolymer can be polycondensed by using the above-mentioned diol monomer and terephthalic acid ester. The reaction is obtained, and the reaction formula is as shown in Fig. 2, and the structure shown in the formula (11) can be synthesized:

(II) Synthesis Example 2: Synthesis of phosphorus-based flame retardant polyester copolymer having a phosphorus content of 1.5 wt% 21.77 g (42.18 mmol) of product (1), 90 g (354 mmol) of ethyl p-benzoate ( Bis(hydroxyethyl) terephthalate; BHET), catalyst Ti(OBu)4 and cobalt acetate were placed in a 500 ml three-neck reactor. After the temperature was raised to 270 ° C for 80 minutes, the pressure in the reactor was lowered to 1-3 mmHg, and the temperature was maintained at about 280 ° C for polycondensation reaction to obtain a phosphorus content of 1.5 wt% phosphorus. Burning polyester copolymer peh s. The synthesized PET-1.5 has properties including an ultimate viscosity of 58.58 dl/g, and the ultimate viscosity can reflect the hydrodynamic size of the polymer in solution. The actual phosphorus content calculated using the 4 NMR integrated area was 1.47 wt%, which was close to the expected value. The glass transition temperature was measured at 85 ° C using a Dynamic Mechanical Analyzer (DMA) and at the UL-94 vertical burning property test. Synthesis Example 3: Synthesis of PET-1.8 having a phosphorus content of 1.8% by weight 27.69 g (53.65 mmol) of product (1), 90 g (354 mmol) of 201226416 of ethyl acenamate, catalyst Ti(OBu)4 and acetic acid Cobalt was placed in a 500 ml three-neck reactor. After the temperature was raised to 270 ° C for 80 minutes, the pressure in the reactor was lowered to 1-3 mmHg, and the temperature was maintained at about 280 DC to carry out a polycondensation reaction to obtain a phosphorus-based flame retardant polymer having a filling content of 1.8 wt%. Ester copolymer PET-1.8. The synthesized PET-1.5 has properties including an ultimate viscosity of 0.56 dl/g and an actual phosphorus content of 1.76 wt% 'close to the expected value. The DMA measured a glass transition temperature of 90 ° C and achieved a v 〇 rating on the UL-94 test. Synthesis Example 4: Synthesis of PBT-1.8 having a phosphorus content of 1.8% by weight 10.40 g (20.15 mmol) of product (1), 90 g (290 mmol) of bis(hydroxybutyl) terephthalate; BHBT, catalyst Ti(OBu)4 and cobalt acetate were placed in a 500 ml three-neck reactor. After the temperature was raised to 270 ° C for 80 minutes, the pressure in the reactor was reduced to 1-3 mmHg, and the temperature was maintained at about 260 ° C for polycondensation reaction to obtain a phosphorus-based flame retardant polymer with a filling content of 1.8 wt%. Ester copolymer ΡΒτ_ 1.8. The synthesized PBT-1.8' properties include: an ultimate viscosity of 0.55 dl/g and an actual phosphorus content of 1.76 wt% 'close to the expected value. The glass transition temperature measured by DMA was 65 °C, and the v-1 rating was achieved on the UL-94 test. Synthesis Example 5: Synthesis of PBT-2.3 having a phosphorus content of 2.3 wt% 14.63 g (28.34 mmol) of product (1), 9 〇g (290 mmol) of butyl benzoate, catalyst Ti(OBu) 4 and Cobalt acetate was placed in a 500 ml three-neck reactor. After the temperature was raised to 260 ° C for 80 minutes, the pressure in the reactor was lowered to 1-3 mmHg ' and the temperature was maintained at about 26 ° C to carry out polycondensation 201226416 reaction to obtain a phosphorus content of 2.3 wt ° / 〇 Phosphorus-based flame retardant polyester copolymer PBT-2.3. The synthesized PBT-2.3 has properties including: ultimate viscosity of 0.53 dl/g and actual phosphorus content of 1.76 wt% 'close to the estimated value. The glass transition temperature measured by DMA was 72 °C, and the V0 rating was achieved on the UL-94 test. According to another embodiment of the present invention, the flame-retardant phosphorus-based polyester copolymer can be obtained by a polycondensation reaction of the above-mentioned phosphorus-based diol monomer with 2,6-naphthalene dinonanoate, and the reaction form is as follows. As shown in Fig. 3, it is possible to synthesize the structure of φ as shown in the formula (hi)··

(III) Synthesis Example 6: Synthesis of PBN-0.5 having a male content of 0.5 wt% 6.69 g (12.96111111〇1) of the product (1), 9 (^(25〇111111〇1) of p-naphthalene dinonanoate (bis ( hydroxyethyl ) naphthalate ; BHEN), Ti(0Bu) 4 and cobalt acetate, placed in a 500 ml three-display reactor. After the temperature was raised to 260 ° C for 80 minutes, the pressure in the reactor was reduced to 1 -3 mmHg' and maintaining the temperature at about 265 ° C for polycondensation reaction to obtain a phosphorus-based flame retardant polyester copolymer 5 having a phosphorus content of 0.5 wt%. The synthesized PBN-0.5 has properties including: ultimate viscosity is 〇56 m/g, the actual phosphorus content is 0.48 wt%, which is close to the estimated value. The glass transition temperature measured by 〇^^^ is 126 °C, and the UL-94 test reaches v〇胄 level. : Synthesis of PBN-1.0 with a phosphorus content of 1.0 wt% 201226416 Take 13.03 g (12.96 mmol) of product (1), 90 g (250 mmol) of p-naphthyl phthalate (BHEN), Ti(OBu)4 and cobalt acetate were placed in a 5 〇〇 ml three-neck reactor. After the temperature was raised to 260 ° C for 8 〇 minutes, the pressure in the reactor was reduced to 1-3 mtnHg ' The temperature was maintained at about 265〇c polycondensation reaction was performed to obtain a phosphorus content of 1.0 wt% of the phosphorus-based flame retardant polyester copolymer pBN-l.O.

The ultimate viscosity is 0.53 dl/g, and the actual phosphorus content calculated using the 1H NMR integrated area is 0.98 wt%, which is close to the estimated value. The glass transition temperature measured by DMA φ was 92. (:, V0 grade can be achieved on UL-94 test. Synthetic PBN-0.5, its properties include: ultimate viscosity is 0.53

Dl / g, the actual phosphorus content is 0.98 wt ° / Q, close to the estimated value. The glass transition temperature measured by DMA was 126 ° C, and the V0 rating was achieved on the UL_94 test. According to the embodiment of the present invention, the embodiment of the present invention introduces a phosphorus atom to replace a conventionally toxic phosphatide diol olefinic single-body composite copolymerization method into a poly-bulk polymer, which can be used in a small amount. The flame retardant can have a good flame retardant effect in the presence of the flame retardant, and maintain the original characteristics of the flame retardant to make the flame retardant effect lasting and stable. The phosphorus-based flame retardant polyester copolymer of the embodiment of the invention can be applied to the fields of flame retardant fibers, flame retardant fabrics, flame retardant fabrics, flame retardant films, flame retardant swords and flame retardant plastics. While the invention has been described above in terms of the embodiments of the present invention, it is not intended to limit the scope of the invention, and The features, advantages and embodiments are more apparent and the description of the drawings is as follows: Figure 1 is a 1H NMR spectrum of the product (1). Fig. 2 is a flow chart showing the reaction of synthesizing a flame retardant phosphorus-based polyester copolymer (Π) according to an embodiment of the present invention. Fig. 3 is a flow chart showing the reaction of synthesizing a flame retardant phosphorus-based polyester copolymer (III) according to an embodiment of the present invention. [Main component symbol description] No component symbol

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Claims (1)

201226416 VII. Patent application scope: 1. One (four) diol monomer having the structure shown by the following formula (1) hohch2co X /-〇ch2choh " IX (I) C3-C10 wherein X is hydrogen or fluorenyl 'R is a hydrogen atom, phenyl, C1(10) alkyl, cycloalkyl or a tooth atom β: 2. - Preparation as requested The method of the phosphorus-based diol monomer shown in the above is carried out by reacting a compound (a) with a compound of the formula (1) and a test catalyst to synthesize a compound having the formula (I). 〇〇Μ Fork (a) X (b) 3. A method for preparing a phosphorus-based diol monomer according to claim 2, wherein the test medium is CsF, KF, KI, CsCl, κα, K2C03, Na2C03, KOH Or NaOH. 4. The method for producing a phosphorus-based diol monomer according to claim 2, wherein the alkali catalyst is used in an amount of from 0.1% by weight to 1% by weight based on the amount of the phosphorus-based compound (1). 13 201226416 5. A flame-retardant phosphorus-based polyester copolymer ‘includes a phosphorus-based diol monomer represented by claim 1. 6. The flame-retardant phosphorus-based polyester copolymer ′ according to claim 5 has a structure represented by the following formula (II). (II) wherein X is hydrogen or a fluorenyl group, R is a hydrogen atom, a phenyl group, a C1-C10 alkyl group, a C3-C10 bad alkyl group or a tooth atom, and n = 2-8. 7. The flame-retardant phosphorus-based polyester copolymer as described in claim 5 has a structure represented by the following formula (III): (III) wherein X is hydrogen or a fluorenyl group, R is a hydrogen atom, a phenyl group, a C1-C10 alkyl group, a C3-C10 polar group or a halogen atom, and n = 2-8. 8. The flame-retardant phosphorus-based polyester copolymer according to claim 5, wherein the non-flammable phosphorus-based polyester copolymer has a phosphorus content of from 55 to 3.0% by weight of the copolymer.