JP2009001630A - POLYMER COMPOUND, PROCESS FOR PRODUCING THE SAME, AND COMPOSITION FOR MOLDED ARTICLE - Google Patents

Abstract

[PROBLEMS] To provide a material for manufacturing various molded articles that is excellent in physical characteristics such as mechanical strength, chemical characteristics, and processing characteristics, and that can suppress thermal decomposition in a manufacturing process, is stable, and can be obtained by a simple manufacturing method. A polymer compound suitable for the above is provided. Moreover, the manufacturing method of the high molecular compound which does not require severe conditions in a manufacturing process, suppresses thermal decomposition of the said high molecular compound, and is obtained easily is provided. In addition, by using the above-mentioned polymer compound, it has excellent physical properties such as mechanical strength, chemical properties, and processing properties, has stability in which thermal decomposition is suppressed, and is obtained by an easy manufacturing method. Provided is a molded article composition suitable for use in the manufacture of articles.
A polymer compound having a specific polyester group in which an ester group is bonded to a furan ring or a specific polyamide group in which an amide group is bonded to a furan ring, which are bonded by a specific siloxane group.
[Selection figure] None

Description

  The present invention relates to a polymer compound in which a polyester block segment or a polyamide block segment is bonded by a silicon atom, a production method thereof, and a molded product composition useful as various molded product materials using the polymer compound.

  Resins are being replaced one after another by existing materials such as metal, glass, wood and paper due to their molding processability, high productivity, light weight, flexibility, and excellent mechanical and electrical properties. Its range of use is wide and covers a wide range of components such as building materials, electrical and electronic products, structural parts and functional parts, automobiles, vehicles, aircraft, exterior and interior parts of ships, daily goods, and packaging materials. There is a great demand for improvement in resin properties from these various markets, and in order to meet these demands, alloying of different resins and compounding with other materials are actively performed. For example, for improving mechanical properties, heat resistance, dimensional stability, and the like, organic-inorganic composite materials in which inorganic materials such as glass fibers and carbon fibers are blended with resins have been developed.

  In particular, polyester is excellent in physical properties such as mechanical strength and chemical properties, and is excellent in processing properties such as injection molding and extrusion molding, so it can be used in all fields. Various engineering plastics and inorganic materials Development is underway as a special material combined with.

  Polyester production methods include esterification methods of dicarboxylic acid and glycol, and ester exchange methods in which glycol ester is obtained by transesterification of alkyl ester of dicarboxylic acid and glycol, and this is polycondensed widely. It has been adopted. In order to use it as an engineering plastic, it is necessary to have excellent mechanical properties such as strength, and for that purpose, a high degree of polymerization is essential. When producing polyester by transesterification, since polycondensation of glycol ester is heated and stirred under high vacuum, it is necessary to maintain high vacuum for a long time in order to obtain highly polymerized polyester. Is requested.

  As an improvement of the method for producing a highly polymerized polyester, specifically, a method of performing a polycondensation reaction at a very high vacuum of 0.005 to 0.1 mmHg has been reported (Patent Document 1). In addition, a method has been reported in which a trifunctional oxycarboxylic acid or a tetrafunctional oxycarboxylic acid is added as a crosslinking agent to make the structure of the polyester a crosslinked structure (Patent Document 2).

However, since the method described in Patent Document 1 requires a long production time, there is a risk of thermal decomposition or coloring of the polymer being produced. In addition, in the method described in Patent Document 2, by introducing trifunctional or tetrafunctional oxycarboxylic acid in the obtained polyester, the polymer terminal concentration having an activity such as a hydroxyl group or a carboxyl group is increased, There is a tendency for stability to decrease.
JP-A-5-310898 Japanese Patent Laid-Open No. 5-170885

  The object of the present invention is excellent in physical properties such as mechanical strength, chemical properties, and processing properties, can suppress thermal decomposition in the manufacturing process, is stable, can be obtained by a simple manufacturing method, and can be variously molded products. An object of the present invention is to provide a polymer compound suitable for a production material.

  Another object of the present invention is to provide a method for producing a polymer compound that does not require harsh conditions in the production process and can be easily obtained by suppressing thermal decomposition of the polymer compound. In addition, by using the above-mentioned polymer compound, it has excellent physical properties such as mechanical strength, chemical properties, and processing properties, has stability in which thermal decomposition is suppressed, and is obtained by an easy manufacturing method. An object of the present invention is to provide a molded article composition suitable for use in the manufacture of articles.

  The present inventors have found that a polymer compound in which a polyester or polyamide is bonded to a silicon atom or siloxane can be easily obtained by reacting a polyester or polyamide with an organoalkoxysiloxane. Although this polymer compound has a high degree of polymerization and has excellent physical properties such as mechanical strength, chemical characteristics, and processing characteristics due to polyester and polyamide, it is a severe polymer for achieving a high degree of polymerization. It has been found that manufacturing conditions are not required. For this reason, it has been found that this polymer compound can suppress thermal decomposition in the production process and has a small content of the functional group at the terminal and has stability, and based on this knowledge, the present invention has been completed.

  The present invention relates to a polymer compound represented by the formula (1)

[Wherein X represents formula (2) or formula (3);

(In formula (2), R ¹ represents an optionally substituted aromatic hydrocarbon group or an optionally substituted aliphatic hydrocarbon group.)

(In formula (3), R ² represents an optionally substituted aromatic hydrocarbon group or an optionally substituted aliphatic hydrocarbon group.)
Y represents formula (2), formula (3), or formula (4).

(Wherein Z represents Y)].

  Moreover, this invention is a manufacturing method of the said high molecular compound, Comprising: Polyester represented by Formula (5) or polyamide represented by Formula (6) is melted, and hydrolysis of organoalkoxysilane or organoalkoxysilane is carried out. A method for producing a polymer compound, comprising adding a reaction product

(Formula (5), R ¹ represents an optionally substituted aromatic hydrocarbon group or an optionally substituted aliphatic hydrocarbon group.)

(In formula (6), R ² represents an optionally substituted aromatic hydrocarbon group or an optionally substituted aliphatic hydrocarbon group).

  Moreover, this invention relates to the composition for molded articles containing the said high molecular compound.

  The polymer compound of the present invention is excellent in physical properties such as mechanical strength, chemical properties, and processing properties, can suppress thermal decomposition in the production process, is stable, and is obtained by a simple production method. It is suitable as a product manufacturing material.

  The method for producing a polymer compound of the present invention does not require severe conditions in the production process, and can be easily obtained by suppressing thermal decomposition of the polymer compound.

  The composition for molded articles of the present invention is excellent in physical properties such as mechanical strength, chemical properties, and processing properties, has no coloration with suppressed thermal decomposition, and is obtained by a simple manufacturing method. And is suitable for manufacturing various molded products.

  The polymer compound of the present invention has the formula (1)

In the formula, the formula (2)

Or formula (3)

By having X which shows, it has a polyester block segment or a polyamide block segment. These polyester block segments or polyamide block segments in one polymer compound represented by the formula (1) are not limited to the same type and may be different types. Moreover, the polyester block segment and the polyamide segment may be simultaneously contained in one polymer compound represented by the formula (1).

  These polyester block segment or polyamide block segment is composed of a repeating unit having a furan ring directly bonded to an ester bond or an amide bond, and imparts high strength to a molded product obtained by using the repeating unit. A monomer having a furan ring constituting the repeating unit of these block segments can be obtained as an extract from a biomass-derived raw material such as cellulose, glucose, fructose, mucous acid, or a conversion product thereof, which reduces the environmental burden. It is preferable from the point. The ester bond or amide bond bonded to the furan ring may be bonded to any position of the furan ring, for example, the 2,5-position, 2,4-position, 3,4-position, etc. However, the 2nd and 5th positions are preferable. The polyester or polyamide having a bonding position of 2,5 is preferable because it can be obtained using 2,5-furandicarboxylic acid obtained directly from the biomass and can further reduce the influence on the environment.

R ¹ in the formula (2), R ² in the formula (3), respectively, an aromatic hydrocarbon group, a linear or cyclic aliphatic hydrocarbon group, which may have a substituent . Examples of the aromatic hydrocarbon group include a benzene ring, a biphenyl ring and a bis (phenyl) alkane, a condensed ring such as a naphthalene ring, an indene ring, an anthracene ring and a phenanthrene ring, and a divalent group of a heterocyclic ring. Can do. Examples of the bis (phenyl) alkane include bis (2-hydroxyphenyl) methane and 2,2′-bis (hydroxyphenyl) propane. On the other hand, examples of the heterocyclic ring include the following. 5-membered ring such as furan, thiophene, pyrrole, oxazole, thiazole, imidazole. Six-membered rings such as pyran, pyridine, pyridazine, pyrimidine, pyrazine. Condensed rings such as indole, carbazole, coumarin, quinoline, isoquinoline, acridine, benzothiazole, quinolixan, and purine.

  Examples of the linear aliphatic hydrocarbon group include an ethylene group, a propylene group, an n-butylene group, an n-pentylene group, an n-hexylene group, and an n-heptylene group. Among these, an ethylene group, a propylene group, and a linear alkylene group having 2 to 4 carbon atoms of an n-butylene group are preferable, and an n-butylene group can be particularly preferable.

  Examples of the cyclic aliphatic hydrocarbon group include divalent groups of cycloalkane and cycloalkene. Examples of the cycloalkane group include a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, a cyclooctylene group, a cyclononylene group, and a cyclodecylene group. Examples of the cycloalkene group include a cyclobutenylene group, a cyclopentenylene group, a cyclohexenylene group, a cycloheptenylene group, and a cyclooctenylene group.

Examples of the substituent in the aromatic hydrocarbon group and the aliphatic hydrocarbon group represented by R ¹ and R ² include hydrocarbon groups such as alkyl groups and heteroatoms such as oxygen atoms, nitrogen atoms, silicon atoms, and halogen atoms. The group containing can be mentioned. Specific examples of the group containing a hetero atom include an alkoxy group, a siloxy group, an amino group, a nitro group, a cyano group, a silyl group, and a halogeno group. As an alkoxy group, the following can be illustrated, for example. Methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, octyloxy group, cyclohexylmethoxy group, trimethylsiloxyhexyloxy group, chloroethoxy group, methoxybutyloxy group, dimethylaminomethoxy group. Butenyloxy group, octenyloxy group, phenoxy group. These substituents may be included in all of R ¹ and R ² , but may be included in a part thereof, and these substituents include one kind or two or more kinds. May be.

  N in the formula (2) and m in the formula (3) indicate the degree of polymerization, and each preferably represents an integer of 5 or more and 600 or less. The polyester block segment or polyamide block segment having such a polymerization degree can impart excellent mechanical properties, chemical properties, and processing properties to the polymer compound represented by the formula (1).

  Y in the formula (1) represents the above formula (2), the formula (3), or the formula (4).

In formula (4), Z represents Y. Three Y in Formula (1) may be the same or different.

As the polymer compound, a compound having a polyester group in which R ¹ represents an n-butylene group in the formula (2) is particularly preferable because of excellent mechanical properties such as strength and easy molding.

  The molecular weight of the polymer compound is a peak top molecular weight measured by gel permeation chromatography (GPC) dissolved in 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP). Is preferably 4000 to 600000. Those having such a molecular weight exhibit excellent mechanical properties and facilitate molding.

  The method for producing a polymer compound according to the present invention is a method for producing the polymer compound, wherein the formula (5)

Or polyester represented by formula (6)

A polyamide represented by the formula (1) is melted, and an organoalkoxysilane or a hydrolyzate of an organoalkoxysilane is added and reacted.

The polyester represented by the formula (5) used in the production method of the polymer compound of the present invention includes the polyester block segment of the above formula (2). In the formula (5), R ¹ and n are the formulas The same as R ¹ and n in (2) are shown. The polyamide represented by the formula (6) includes the polyamide block segment of the above formula (3). In the formula (6), R ² and m are respectively R ² and m in the formula (3). Indicates the same thing. In the polyester represented by the formula (5) and the polyamide represented by the formula (6), the furan ring directly bonded to the ester bond or the amide bond is specifically, The same thing as a ring can be illustrated concretely.

  In order to synthesize the polyester represented by the formula (5), it can be obtained by polycondensating furandicarboxylic acid or its ester by a known method in an excess of polyhydric alcohol.

  Specific examples of the flange carboxylic acid to be used include 2,5-furandicarboxylic acid, 2,4-furandicarboxylic acid, and 3,4-furandicarboxylic acid. These can also be used 1 type or in combination of 2 or more types. Examples of the ester of furandicarboxylic acid include methyl ester and ethyl ester.

  Moreover, as a polyhydric alcohol, what is shown to Formula (7) can be mentioned.

R ^3- (OH) _a (7)
In the formula (7), a may be an integer of 2 or more, but in order to obtain the polyester of the formula (5), 2 is preferably shown. In the formula, R ³ specifically includes a group represented by R ¹ in the above formula (2) and a group represented by R ¹ having the same substituent as the substituent specifically exemplified as the substituent. be able to.

  Specific examples of such divalent alcohols include the following. As a chain or cyclic aliphatic diol, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,4-cyclohexanedimethanol. 1,3-dihydroxybenzene and 1,4 dihydroxybenzene as dihydroxybenzene. Bis (2-hydroxyphenyl) methane, 2,2′-bis (hydroxyphenyl) propane, 2,2′-bis (4-hydroxyphenyl) -sulfone as bisphenol. Glycerin, trimethylolpropane, pentaerythrose, sorbitol, sugars. Oxycarboxylic acids such as ether diol and hydroxybenzoic acid obtained from intermolecular dehydration of diols. You may use these in combination suitably.

  Of these, 1,3-propanediol and 1,4-butanedioldiol are preferred.

  Examples of the polycondensation method of the dihydric alcohol and furandicarboxylic acid include a method of directly polycondensing them, a method of synthesizing an ester of a dihydric alcohol and furancarboxylic acid, and then a polycondensation method thereof. . Examples of the method for directly condensation polymerization of the dihydric alcohol and furandicarboxylic acid include solution polymerization, bulk polymerization, suspension polymerization, emulsion polymerization, and the like, and may be appropriately selected according to the molded product to be molded. it can. A polymerization temperature, a polymerization catalyst, a medium such as a solvent, and the like can be appropriately selected depending on each polymerization method.

  The polycondensation method of the dihydric alcohol and furandicarboxylic acid is preferably based on an esterification step and a subsequent polycondensation step of the ester compound.

  In the esterification step, the furan carboxylic acid, the dihydric alcohol, and the catalyst are gradually heated to 110 ° C. to 200 ° C. with stirring, and preferably heated to 150 ° C. to 180 ° C. to obtain an ester compound.

  As usage-amounts of furandicarboxylic acid and dihydric alcohol, it is preferable that dihydric alcohol is 1 time-3 times mole number with respect to furancarboxylic acid. By using dihydric alcohol in excess with respect to furandicarboxylic acid, an ester having an alcohol bonded to the terminal and excellent in reactivity with organoalkoxysilane can be obtained.

The reaction proceeds even if the catalyst is not added due to the autocatalytic action of the dicarboxylic acid, but is preferably added because the concentration of the dicarboxylic acid decreases as the reaction proceeds. As the catalyst to be used, metal oxides and salts, organometallic compounds such as tin, lead and titanium, and tetravalent hafnium compounds such as hafnium chloride (IV) and hafnium chloride (IV) · (THF) ₂ are preferable.

  The end point of this esterification step is the time when the reaction mixture becomes transparent and can be easily confirmed.

  In the subsequent polycondensation step, the temperature of the reaction system is heated to 180 ° C. to 280 ° C., more preferably in the range of 180 ° C. to 230 ° C. to initiate the polycondensation reaction. The polycondensation reaction is preferably performed under vacuum. Specific examples of the catalyst suitable for this polycondensation include the following examples. Acetates and carbonates such as lead, zinc, manganese, calcium, cobalt, and magnesium, or metal oxides such as magnesium, zinc, lead, and antimony, and organometallic compounds such as tin, lead, and titanium. Moreover, titanium alkoxide can also be used as a catalyst effective in both processes. The catalyst may be added separately in the esterification step and the polycondensation step, or the catalyst in the polycondensation step may be added from the beginning. In addition to the catalyst, furan carboxylic acid and dihydric alcohol may be heated as necessary, or may be added in multiple portions.

  In the polycondensation reaction following esterification, the polycondensation reaction is promoted by removing from the reaction system excess dihydric alcohol that has not been consumed in the esterification step or divalent alcohol produced as a by-product. Can do. Removal of the dihydric alcohol can be carried out by removing the reaction system by depressurizing or removing it from the reaction system by a method such as azeotropic distillation with another solvent. Moreover, after obtaining a polymer by polycondensation reaction, solid phase polymerization can also be performed by a known method.

  The degree of polymerization of the polyester represented by the formula (5) obtained in such a polycondensation step, n is preferably 5 or more and 600 or less. The molecular weight was measured by gel permeation chromatography (GPC) dissolved in 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP), and the peak top molecular weight was 1000 to 140000. Can be mentioned.

  The polyamide represented by the formula (6) can be obtained by polycondensing the same furan carboxylic acid or its ester as described above by a known method in an excess of polyvalent amine. As the usage-amount of furan carboxylic acid or its ester, and a polyvalent amine, it is preferable that a polyvalent amine is 1.01-1.10 mol with respect to 1 mol of furan carboxylic acid or its ester. By using polyvalent amine in excess relative to furandicarboxylic acid, a polyamide having an amine bonded to the terminal can be obtained, and an amino group having an amino group excellent in reactivity with organoalkoxysilane can be obtained.

  As a polycondensation method of polyamide, a melt polycondensation method, an interfacial polycondensation method, a solution polycondensation method and the like can be selected. In order to synthesize polyamides directly from the reaction of carboxylic acid and amine, a melt condensation method can be selected so that carboxylic acid and amine are reacted and melted at high temperature without solvent.

  Various diamines can be used depending on the polyamide to be produced. For example, aliphatic or alicyclic diamines can be used, and preferred examples thereof are given below. Ethylenediamine, 1,3-propylenediamine, 1,2-propylenediamine, 1,4-butanediamine, 2,2-dimethyl-1,3-propylenediamine, hexamethylenediamine, 1,4-cyclohexanediamine, 3-methoxy Hexamethylenediamine. Decamethylenediamine, bis (3-aminopropyl) sulfide, bis (4-aminocyclohexyl) methane, piperazine. Moreover, when aromatic diamine is used, polyamide with high heat resistance can be produced, and preferred examples thereof are given below. m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone. 4,4′-diaminodiphenyl sulfide, benzidine, 4,4′-diaminodiphenyl ether, 1,5-diaminonaphthalene, m-toluidine, 3,3′-dimethylbenzidine, 3,3′-dimethoxybenzidine, 3, 4'-diaminodiphenyl ether. 3,3'-dimethoxybenzidine, o-toluidine sulfone, phenylindanediamine, 1,1,1,3,3,3-hexafluoro-2,2-bis (4-aminophenyl) propane. 1,1,1,3,3,3-hexafluoro-2,2-bis (4-aminophenoxyphenyl) propane, bis (4-aminophenoxyphenyl) sulfone, 1,4-bis (4-aminophenoxy) benzene. 1,3-bis (4-aminophenoxy) benzene, 9.9-bis (4-aminophenyl) fluorene, 4,4′-diaminobenzanilide, bis (4-β-amino-t-butylphenyl) ether, Metaxylylenediamine.

In the polycondensation step, the temperature of the reaction system is heated to 180 ° C. to 330 ° C., more preferably in the range of 180 ° C. to 310 ° C. to initiate the polycondensation reaction. The polycondensation reaction is preferably performed under vacuum. As needed, alkali metal compounds such as sodium hydroxide and sodium acetate, phosphorus compounds such as hypophosphorous acid, sodium hypophosphite, phenylphosphonic acid, and phosphorous acid are used for the purpose of inhibiting thermal decomposition or polycondensation. It can also be added as a catalyst. The residual amount of these additives is preferably in the range of about 0.5 × 10 ⁻⁶ to about 50 × 10 ⁻⁶ mole per gram of polyamide.

  The degree of polymerization of the polyamide represented by the formula (6) obtained in such a polycondensation step, m is preferably 5 to 600. The molecular weight was measured by gel permeation chromatography (GPC) dissolved in 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP), and the peak top molecular weight was 1000 to 140000. Can be mentioned.

  Next, a method for producing the polymer compound of the present invention by adding an organoalkoxysilane or a hydrolyzate of an organoalkoxysilane to the polyester of formula (5) or the polyamide of formula (6) will be described.

  As the organoalkoxysilane to be reacted with the polyester of the above formula (5) or the polyamide of the formula (6), those represented by the formula (8) are preferable.

SiR ⁴ _4-b (OR ⁵ ) _b (8)
In the formula, R ⁴ is substituted with an alkyl group substituted with an aromatic group such as a phenyl group or a benzyl group, an amino group, a pyridyl group, an imidazolyl group, a glycidyl group, a hydroxyl group, a vinyl group, or a mercapto group. The C1-C10 alkyl group which may be sufficient is shown. R ⁵ represents an alkyl group substituted with an alkyl group having 1 to 10 carbon atoms or an aromatic group such as a phenyl group or a benzyl group. b represents an integer of 1 to 4.

  Specific examples of the organoalkoxysilane in which b is 4 in the formula (8) include the following. Tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetrabutoxysilane, tetraphenoxysilane.

  Specific examples of the organoalkoxysilane in which b is 1 to 3 in the formula (8) include the following. Methyltrimethoxysilane, methyltriethoxysilane, methyltrin-propoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldiisopropoxysilane, trimethylmethoxysilane, trimethylethoxysilane. Trimethylbutoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltrin-propoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldiisopropoxysilane, triethylmethoxysilane. Triethylethoxysilane, triethylbutoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-butyltrimethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, isobutylmethyldimethoxysilane. Phenyltrimethoxysilane, diphenyldiethoxysilane, triphenylmethoxysilane, 1,3-di-n-octyltetraethoxydisiloxane, 1,3-dimethyltetramethoxydisiloxane, dicyclopentyldimethoxysilane. 1,1-diethoxy-1-silacyclopent-3-ene, cyclopentyltrimethoxysilane, (3-cyclopentadienylpropyl) triethoxysilane, cyclohexyltrimethoxysilane, cyclohexylethyldimethoxysilane. Cyclohexylmethyldimethoxysilane, [2- (3-cyclohexenyl) ethyl] triethoxysilane, [2- (3-cyclohexenyl) ethyl] trimethoxysilane, t-butyldiphenylmethoxysilane. Examples of those having an amino group include the following. N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (6-aminohexyl) aminopropyltrimethoxysilane, 4-aminobutyltriethoxysilane, N- (2-aminoethyl) -3- Aminoisobutylmethyldimethoxysilane. 2-aminoethylaminomethylbenzyloxydimethylsilane, (aminoethylaminomethyl) phenethyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 2- (m-aminophenoxy) propyltrimethoxy Silane. m-aminophenyltrimethoxysilane, 3- (3-aminopropoxy) -3,3-dimethyl-1-propenyltrimethoxysilane, aminophenyltrimethoxysilane, 3-aminopropyldiisopropylethoxysilane. 3-aminopropylmethylbis (trimethylsiloxy) silane, 3-aminopropyldimethylethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane. 3-aminopropyltris (methoxyethoxyethoxy) silane, 3-aminopropyltris (trimethylsiloxy) silane, (3-trimethoxysilylpropyl) diethylenetriamine, triphenylaminosilane. N- (trimethoxysilylpropyl) isothiouronium chloride, N-phenylaminopropyltrimethoxysilane, N-methylaminopropyltrimethoxysilane, N-methylaminopropylmethyldimethoxysilane. 3- (2,4-Dinyltophenylamino) propyltriethoxysilane, dimethylaminomethylethoxysilane, (N, N-diethyl-3-aminopropyl) trimethoxysilane, bis [3- (trimethoxysilyl) propyl] Ethylenediamine. Bis (trimethoxysilylpropyl) amine. 2- (trimethoxysilylethyl) pyridine having a pyridyl group, N- (3-triethoxysilylpropyl) -4,5-dihydroimidazole having an imidazolyl group. (3-Glycidoxypropyl) bis (trimethylsiloxy) methylsilane, (3-glycidoxypropyl) dimethylethoxysilane, (3-glycidoxypropyl) methyldiethoxysilane having a glycidyl group. (3-glycidoxypropyl) methyldimethoxysilane, (3-glycidoxypropyl) trimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl Trimethoxysilane. 5,6-epoxyhexyltriethoxysilane, 1,3-divinyltetraethoxydisiloxane, vinylmethyldiethoxysilane having a vinyl group, vinylmethyldimethoxysilane, O- (vinyloxyethyl) -N- (triethoxysilylpropyl) urethane . Vinyloxytrimethylsilane, vinylphenyldiethoxysilane, vinyltri-t-butoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriphenoxysilane, vinyltris (2-methoxyethoxy) silane. Vinylmethyldiacetoxysilane, styrylethyltrimethoxysilane, 3- (N-styrylmethyl-2-aminoethylamino) -propyltrimethoxysilane hydrochloride, (3-acryloxypropyl) dimethylmethoxysilane. 2- (acryloxyethoxy) trimethylsilane, N-3- (acryloxy-2-hydroxypropyl) -3-aminopropyltriethoxysilane, butenyltriethoxysilane. Acetoxysilane having a hydroxyl group, triphenylsilanol, N- (3-triethoxysilylpropyl) gluconamide, N- (3-triethoxysilylpropyl) -4-hydroxybutyramide, sodium methylsiliconate. N- (hydroxyethyl) -N-methylaminopropyltrimethoxysilane. 3-mercaptopropyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane having a mercapto group. 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, mercaptomethyltrimethoxysilane, mercaptomethylmethyldiethoxysilane.

  Among these, tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetrabutoxysilane, and tetraphenoxysilane can be mentioned as preferable examples. These are easy to control the reaction with the polyester represented by the above formula (5) and the polyamide represented by the formula (6).

  The hydrolyzate of the organoalkoxysilane is a product in which an alkoxy group is substituted with a hydroxyl group by hydrolysis of an organoalkoxysilane. The hydrolyzate may be one in which all alkoxy groups of the organoalkoxysilane are substituted with hydroxyl groups, or a part of them may be converted to hydroxyl groups. The hydrolyzate of organoalkoxysilane may be produced by moisture in the reaction system or moisture in the atmosphere.

  The hydrolyzate of organoalkoxysilane may be used by being appropriately mixed with organoalkoxysilane, or all of them may be used as hydrolyzate of organoalkoxysilane instead of organoalkoxysilane.

  The reaction of such an organoalkoxysilane or a hydrolyzate thereof with the polyester of formula (5) or the polyamide of formula (6) melts the polyester of formula (5) or the polyamide of formula (6). An organoalkoxysilane or this hydrolyzate is added and reacted. Specifically, the dealcoholization reaction between the terminal hydroxyl group of the polyester and the alkoxy group of the organoalkoxysilane or the dehydration reaction of the hydrolyzate of the organoalkoxysilane occurs. Thereby, a polyester block segment forms a covalent bond with a silicon atom, and is bridge | crosslinked.

  Further, a deamination reaction between the terminal amino group of the polyamide and the alkoxy group of the organoalkoxysilane, or a dehydration reaction of the hydroxyl group of the hydrolyzate of the organoalkoxysilane occurs. Thereby, a polyamide block segment forms a covalent bond with a silicon atom, and is bridge | crosslinked.

  Silicon forms four covalent bonds, and the amount of addition thereof can control the cross-linking of the polyester block segment or the polyamide block segment. Such a reaction between the organoalkoxysilane and the polyester or polyamide can be carried out easily in a short time, and it is not necessary to carry out the reaction under a vacuum for a long time, and the crosslinking can be formed very easily. Thermal decomposition of the resulting polymer compound can be suppressed. Furthermore, the formation of such a cross-link consumes the hydroxyl group at the polyester terminal and the functional group of the amino group at the polyamide terminal, leading to an improvement in the stability of the resulting polymer compound.

  It is preferable that the usage-amount of organoalkoxysilane and its hydrolyzate is 0.1 to 10 mass% with respect to polyester or polyamide. If the amount of the organoalkoxysilane or its hydrolyzate used is 0.1% by mass or more, sufficient crosslinking can be formed, and if it is 10% by mass or less, excessive crosslinking is suppressed, and the composition for molded articles is reduced. It can suppress that thermoplasticity is inhibited in a thing. A more preferable usage amount is 0.2% by mass or more and 8% by mass or less, and further preferably 0.5% by mass or more and 5% by mass or less.

  As the reaction conditions, organoalkoxysilane or a hydrolyzate thereof is mixed with molten polyester or polyamide at 170 ° C. or higher and 280 ° C. or lower, more preferably 180 ° C. or higher and 230 ° C. or lower. If reaction temperature is 170 degreeC or more, the delay of advancing of reaction can be suppressed, and if it is 280 degrees C or less, thermal decomposition of the polymer compound obtained can be suppressed. The atmosphere at this time is preferably in an inert gas such as nitrogen or argon, or in a vacuum. The mixing of the organoalkoxysilane or the hydrolyzate thereof with the polyester or polyamide can be carried out under a nitrogen gas atmosphere, and after sufficient stirring, the pressure can be reduced. The reaction time is preferably from 30 minutes to 20 hours. If the reaction time is 30 minutes or longer, sufficient crosslinking is obtained, and if it is 20 hours or less, thermal decomposition and deterioration of the resulting polymer compound can be suppressed.

  This reaction can be carried out by mixing and stirring the raw materials in an ordinary polyester polymerization reactor. By mixing and stirring at the time of resin kneading and injection molding, it is possible to obtain a molded article having a high degree of crosslinking using polyester or polyamide having a low degree of crosslinking as a raw material.

  The composition for molded articles of the present invention contains the above polymer compound. Furthermore, the composition for molded articles of the present invention may contain an additive as necessary within the range not impairing the function of the polymer compound. Specific examples include flame retardants, colorants, internal mold release agents, antioxidants, ultraviolet absorbers, and various fillers.

  As a molded product that can be molded using the molded product composition, since it has practically sufficient strength, is colorless and transparent, and has excellent physical properties such as stability, a fiber / film, Examples of the molded products in a wide field such as sheets and various molded products can be given. For example, a container such as a bottle, a pipe, a tube, a sheet, a plate, or a film. Particularly preferable molded articles include constituent materials such as an ink tank of an ink jet printer, an electrophotographic toner container, a packaging resin, a copying machine, a business machine such as a printer, or a camera casing.

  As a molding method of a molded product using the above-described molded product composition, the same method as the thermoplastic resin molding method can be used. For example, compression molding, extrusion molding, injection molding, or the like can be used. it can.

The polymer compound of the present invention will be specifically described in detail, but the technical scope of the present invention is not limited thereto. The following numerical values indicate “% by mass”.
[Example 1]
[Preparation of polybutylene-2,5-furandicarboxylate]
A 1 L four-necked flask equipped with a nitrogen introducing tube, fractionating tube-cooling tube, thermometer, and SUS stirring blade was prepared. In this four-necked flask, 2,5-furandicarboxylic acid (149.9 g), distilled 1,4-butanediol (259.5 g), monobutyltin oxide catalyst (0.059 wt%), titanium dissolved in toluene N-butoxide catalyst (0.059 wt%) was added.

  Stirring was started while introducing nitrogen into the four-necked flask, and the contents were immersed in an oil bath at 150 ° C. to raise the temperature. After the internal temperature reached 150 ° C., the temperature was raised to 170 ° C. over 4 hours.

  Depressurization started at 170 ° C. The reaction was continued for about 390 minutes at 190 ° C. under reduced pressure (5 Pa) under full vacuum (5 Pa) over about one hour. The obtained polymer was dissolved in hexafluoroisopropanol and reprecipitated with methanol, followed by vacuum drying at 60 ° C. for 12 hours.

[Preparation of polymer compound]
A 1 L four-necked flask equipped with a nitrogen introducing tube, fractionating tube-cooling tube, thermometer, and SUS stirring blade was prepared. To this four-necked flask, 200 g of polybutylene-2,5-furandicarboxylate was added.

  While introducing nitrogen into the four-necked flask, the contents were immersed in an oil bath at 170 ° C. to raise the temperature. After the internal temperature reached 170 ° C. and the contents were melted, 10 g of tetraethoxysilane was added and stirred for 30 minutes.

  The pressure was reduced to 5 Pa over about 1 hour, and the reaction was carried out at 170 ° C. for 2 hours. The obtained polymer was dissolved in hexafluoroisopropanol and reprecipitated with methanol, followed by vacuum drying at 60 ° C. for 12 hours.

  The thus obtained polymer compounds had peak top molecular weights of 370000 and 34000. Tm was 167 ° C., Tg was 30 ° C., Tc was 81 ° C., and the thermal decomposition temperature was 344 ° C. Moreover, the FT-IR (Fourier transform infrared spectrophotometry) measurement result of a high molecular compound is shown in FIG. Molecular weight measurement, glass transition temperature (Tg), crystallization temperature (Tc), and melting point (Tm) were measured under the following conditions.

[Molecular weight measurement]
Analytical instrument: Alliance 2695 manufactured by Waters
Detector: Differential refraction detector Eluent: Hexafluoroisopropanol solution with a concentration of 5 mM sodium trifluoroacetate Flow rate: 1.0 ml / min
Column temperature: 40 ° C
Degree of polymerization: The peak top molecular weight was determined using PMMA standards.

[Glass transition temperature (Tg), crystallization temperature (Tc), melting point (Tm)]
Device name: TI Instruments differential scanning calorimetry device Pan: Platinum pan Sample weight: 3 mg
Temperature rising start temperature: 30 ° C
Temperature increase rate: 10 ° C / min
Atmosphere: Nitrogen [FT-IR measurement]
Device name: Spectrum One manufactured by PekinElmer
Measurement range: 4000-400 cm ^-1
[Comparative example]
A polymer compound was prepared in the same manner as in Example except that tetraethoxysilane was not added, and molecular weight measurement, glass transition temperature (Tg), crystallization temperature (Tc), and melting point (Tm) were measured. The peak top molecular weight of the polymer compound was 55000. Tm was 170 ° C., Tg was 37 ° C., Tc was 97 ° C., and the thermal decomposition temperature was 357 ° C. Moreover, the FT-IR measurement result of the polymer is shown in FIG.

  From the obtained results, the polymer compounds shown in Examples showed a high degree of polymerization. On the other hand, it can be seen that the polymer of the comparative example has a low degree of polymerization and a low molecular weight even when reacted for the same time.

It is a figure which shows the spectrum by FT-IR measurement of an example of the high molecular compound of this invention. It is a figure which shows the spectrum by the FT-IR measurement of the high molecular compound of a comparative example.

Claims (5)

The high molecular compound represented by Formula (1).

[Wherein X represents formula (2) or formula (3);

(In formula (2), R ¹ represents an optionally substituted aromatic hydrocarbon group or an optionally substituted aliphatic hydrocarbon group.)

(In formula (3), R ² represents an optionally substituted aromatic hydrocarbon group or an optionally substituted aliphatic hydrocarbon group.)
Y represents formula (2), formula (3), or formula (4).

(In formula (4), Z represents Y.)] The polymer compound according to claim ¹ , wherein R ¹ in the formula (2) represents an n-butylene group. It is a manufacturing method of the high molecular compound of Claim 1 or 2, Comprising: The polyester represented by Formula (5) or the polyamide represented by Formula (6) is melted, and hydrolysis of organoalkoxysilane or organoalkoxysilane is carried out. A method for producing a polymer compound, which comprises reacting a product.

(Formula (5), R ¹ represents an optionally substituted aromatic hydrocarbon group or an optionally substituted aliphatic hydrocarbon group.)

(In formula (6), R ² represents an optionally substituted aromatic hydrocarbon group or an optionally substituted aliphatic hydrocarbon group.) The method for producing a polymer compound according to claim 3, wherein a compound in which R ¹ represents an n-butylene group in formula (5) is used.   A composition for a molded article comprising the polymer compound according to claim 1.

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