JPH09235377A - Production of siloxane copolymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To simply and inexpensively obtain a siloxane copolymer excellent in flame retardancy, moldability, mold releasability and surface smoothness with a low level of discoloration and useful as a container by allowing a polycarbonate to react with a specific silicon compound in the presence of a cobalt compound. SOLUTION: In the presence of an esterification catalyst or an ester- interchange catalyst (A), a cobalt compound (B) such as cobalt acetate, cobalt carbonate or cobalt benzoate, a polycarbonate or diol dicarbonate (C), as necessary, (D) a dicarboxylic diester, (E) a silicon compound of formula I [R<1> -R<4> , X, Y are each H, a (substituted) organic group; (a) is 0-5,000] or formula II [(b) is 3-20] are allowed to react with each other. In a preferred embodiment, the component B is used in an amount of 0.00001-1 pts.wt. per 100 pts.wt. of the copolymer to be produced.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a siloxane-based copolymer.

[0002]

BACKGROUND OF THE INVENTION Thermoplastic polymers are industrially useful molding materials generally used for plastic containers, films, fibers, adhesives, extruded sheets and the like. In particular, a polyester carbonate resin containing terephthalic acid and / or isophthalic acid, a carbonate component and 2,2-bis (4-hydroxyphenyl) propane (also known as bisphenol A) as main units, and terephthalic acid and / or
Alternatively, a polyester resin containing isophthalic acid and bisphenol A as main units has excellent mechanical properties, electrical properties, heat resistance, dimensional stability, and transparency, and molded products thereof are widely used.

However, thermoplastic polymers generally have the drawback that they are easily combustible and, when burned, produce harmful gases. Therefore, when a thermoplastic polymer is used in an application requiring flame retardancy, the above-mentioned disadvantage of being flammable is usually compensated for by adding a flame retardant represented by halogen compounds and phosphorus compounds. ing.
However, such a flame retardant is not preferable from the viewpoint of environmental problems because it produces a harmful gas at the time of combustion, and further the physical properties (for example, mechanical properties, electrical properties, heat resistance, weather resistance) are reduced depending on the added amount. It causes a problem.

A method of adding a siloxane compound to a thermoplastic polymer has been proposed as one of means for improving the flame retardancy and moldability of the thermoplastic polymer. However, in this method, when the compatibility between the siloxane compound and the thermoplastic polymer is low, there are problems that flame retardancy and moldability are not sufficiently improved, and that the siloxane compound bleeds on the surface. .

[0005] As means for solving such problems,
A technique for copolymerizing polysiloxane with a thermoplastic polymer has been proposed. For example, JP-A-2-196823, JP-A-3-106937, and JP-A-7-
2999 proposes a method for producing a polyester carbonate-siloxane copolymer by an interfacial polycondensation method using bisphenols, dicarboxylic acid dichloride, phosgene, and phenol-terminated dimethylpolysiloxane. Further, in JP-A-5-222173 as well, a polyester carbonate prepared by an interfacial polycondensation method using a phenol-terminated dimethylpolysiloxane is used.
A method for producing a siloxane copolymer has been proposed. However, in the interfacial polycondensation method, it is difficult to obtain phosgene and acid chloride as raw materials, and halogen compounds such as methylene chloride are used, which is environmentally unfavorable.

As one of means for solving the problems in the interfacial polycondensation method, Japanese Patent Laid-Open No. 4-91125 discloses a polyester prepared by melt polycondensation method using dicarboxylic acid diester, diol, and phenol-terminated dimethylpolysiloxane. -Methods for producing siloxane block copolymers have been proposed. However, even in this method, since an expensive and special silicon compound is used, the production cost is high, and since it is a block copolymer, increasing the introduction amount of the siloxane unit causes deterioration of physical properties due to phase separation. There is a problem.

On the other hand, Curry et al. Reported a method for synthesizing a siloxane copolymer obtained from a diol and bis (anilino) diphenylsilane (J. Appl. Polym.
Sci., 9 , 295 (1965)). In this method, since the polymer produced is an alternating copolymer, the amount of siloxane introduced can be increased. However, in this method, since an expensive special silicon compound is used, there are problems that the manufacturing cost is high and the reaction takes a long time.

[0008]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned conventional problems, and its object is to overcome the drawbacks of the conventional methods for producing a siloxane-based copolymer. However, not only a siloxane-based copolymer having excellent flame retardancy and moldability can be obtained, but also a halogen-containing substance and a solvent are not used, which can be produced at low cost and has a low degree of coloring. It is an object of the present invention to provide a commercially advantageous production method by which a copolymer can be obtained.

[0009]

DISCLOSURE OF THE INVENTION As a result of intensive studies, the present inventors have found that in the presence of an esterification or transesterification catalyst, at least one polycarbonate and / or dicarbonate of a diol, and optionally a dicarbonate. A method for producing a siloxane-based copolymer, which comprises reacting at least one diester of dicarboxylic acid with a specific silicon compound, wherein the cobalt-based compound is added to the reaction mixture. The inventors have found that they can be solved and completed the present invention. The manufacturing method of the present invention is novel, and thereby the above-mentioned object is achieved.

That is, according to the present invention, in the presence of an esterification or transesterification catalyst, at least one polycarbonate and / or diol dicarbonate, and if necessary at least one dicarboxylic acid diester, and a silicon compound are used. In the method of producing a siloxane-based copolymer, wherein the silicon compound is at least one selected from the group consisting of compounds represented by the following general formulas (I) and / or (II). Yes, and a cobalt-based compound is added to the reaction mixture with respect to the manufacturing method:

[0011]

[Chemical 6]

[0012]

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In the formula, R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom or a substituted or unsubstituted organic group; X and Y are independently hydrogen. An atom or a substituted or unsubstituted organic group; a is
Is an integer from 0 to 5000; and b is an integer from 3 to 20.

In a preferred embodiment, the cobalt compound is at least one selected from the group consisting of cobalt acetate, cobalt carbonate and cobalt benzoate.

In a preferred embodiment, the cobalt-based compound is the siloxane-based copolymer 100 produced above.
0.0001 to 1 part by weight is added to the parts by weight.

In a preferred embodiment, the cobalt compound is added at the start of polymerization.

In a preferred embodiment, the polycarbonate is represented by the following general formula (III):

[0018]

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In the formula, R ⁵ is a divalent hydrocarbon group having 1 to 20 carbon atoms; at least a part of hydrogen atoms of the hydrocarbon group is a halogen atom, a hydrocarbon group, an alkoxy group, and phenoxy. A divalent hydrocarbon group having 1 to 20 carbon atoms, which is substituted with at least one selected from the group consisting of groups; or a R ⁶ -Z-R ⁷ group (wherein R ⁶ and R ⁷ Is a divalent aromatic hydrocarbon group,
Each hydrogen atom of the aromatic ring may be independently substituted with a halogen atom, a hydrocarbon group, an alkoxy group or a phenoxy group, and Z is a single bond, -O-,-
S -, - SO -, - SO 2 -, - CO-, and is selected from the group consisting of a hydrocarbon radical having from 1 to 20 carbon atoms)
And c is an integer from 1 to 5000.

In a preferred embodiment, the diol dicarbonate is represented by the following general formula (IV):

[0021]

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In the formula, R ⁸ is a divalent hydrocarbon group having 1 to 20 carbon atoms; at least a part of hydrogen atoms of the hydrocarbon group is a halogen atom, a hydrocarbon group, an alkoxy group, and phenoxy. A divalent hydrocarbon group having 1 to 20 carbon atoms, which is substituted with at least one selected from the group consisting of groups; or a R ¹⁰ -Z-R ¹¹ group (wherein R ¹⁰ and R ¹¹ Is a divalent aromatic hydrocarbon group, each hydrogen atom of the aromatic ring may be independently substituted with a halogen atom, a hydrocarbon group, an alkoxy group, or a phenoxy group, and Z is , Single bond, -O
-, - S -, - SO -, - SO 2 -, - CO-, and 1-20 is selected from the group consisting of hydrocarbon groups having a carbon atom) in there; and R ⁹ is 1 It is a hydrocarbon group having 20 carbon atoms.

In a preferred embodiment, the diester of dicarboxylic acid is represented by the following general formula (V):

[0024]

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In the formula, R ¹² is a divalent hydrocarbon group having 1 to 20 carbon atoms; or at least a part of hydrogen atoms of the hydrocarbon group is a halogen atom, a hydrocarbon group, an alkoxy group, and A divalent hydrocarbon group having 1 to 20 carbon atoms substituted with at least one selected from the group consisting of phenoxy groups; and R ¹³ is
It is a hydrocarbon group having 1 to 20 carbon atoms.

In a preferred embodiment, the silicon compound is selected from the group consisting of dimethylpolysiloxane, methylphenylpolysiloxane, dimethoxydimethylsilane, dimethoxydiphenylsilane, octamethylcyclotetrasiloxane and octaphenylcyclotetrasiloxane.

In a preferred embodiment, the polycarbonate is 2,2-bis (4-hydroxyphenyl).
Propane polycarbonate.

In a preferred embodiment, the diol dicarbonate is 2,2-bis (4-hydroxyphenyl) propane bis (methyl carbonate) or 2,2-bis (4-hydroxyphenyl) propane biscarbonate. (Phenyl carbonate).

In a preferred embodiment, the diester of dicarboxylic acid is selected from the group consisting of dimethyl terephthalate, dimethyl isophthalate, and dimethyl naphthalene-2,6-dicarboxylate.

In a preferred embodiment, the esterification or transesterification catalyst is a tin compound.

In a preferred embodiment, the esterification or transesterification catalyst is lithium, sodium,
A metal selected from the group consisting of potassium, magnesium, calcium, barium, strontium, zinc, cadmium, titanium, zirconium, tin, antimony, lead, manganese, and cobalt, acetate, carbonate, borate,
It is at least one selected from the group consisting of oxides, hydroxides, hydrides, alcoholates, and phenolates.

In a preferred embodiment, the esterification or transesterification catalyst is used in an amount of 0.0001 to 1 part by weight based on 100 parts by weight of the siloxane copolymer produced.

[0033]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.

The silicon compound used in the present invention is preferably represented by the above general formula (I) and / or (II). Here, R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom or a substituted or unsubstituted organic group; X and Y are each independently a hydrogen atom,
Alternatively, it is a substituted or unsubstituted organic group; a is 0 to
Is an integer of 5000; and b is an integer of 3-20. The substituted or unsubstituted organic group is a hydrocarbon group having 1 to 20 carbon atoms (wherein at least some of the hydrogen atoms of the hydrocarbon group are each independently a hydroxyl group, a halogen atom, an alkoxy group). , Phenoxy group, amino group, group containing ammonium salt, alkylamino group, carboxyl group, ester group, polyether group, epoxy group, vinyl group, vinyl ether group, vinyl ester group,
Allyl group, acrylic group, methacrylic group, mercapto group,
At least one selected from the group consisting of isocyanate groups
It may be substituted with certain groups. ), Hydroxyl group, halogen atom, alkoxy group, phenoxy group, amino group, group containing ammonium salt, alkylamino group, carboxyl group, ester group, polyether group, epoxy group, vinyl group, vinyl ether group, vinyl ester group, allyl Base,
Acrylic base. Examples thereof include a methacryl group, a mercapto group and an isocyanate group.

Specific examples of the silicon compound include the following. For example, dimethoxydimethylsilane, diethoxydimethylsilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, octadecylmethyldimethoxysilane, vinylmethyldiethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 5-hexenyltrimethoxysilane,
Methylphenyldimethoxysilane, methylphenyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, cyclohexylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxy Alkoxysilanes such as silane, 3-aminopropyltriethoxysilane, 3-chloropropylmethyldimethoxysilane, (3-glycidoxypropyl) methyldiethoxysilane, and 3-methacryloxypropylmethyldimethoxysilane, diphenylsilane, diphenylsilane Phenylsilanes such as diols, hexamethylcyclotrisiloxane, hexaphenylcyclotrisiloxane, octamethylcyclotetrasiloxane, octa E cycloalkenyl cyclotetrasiloxane,
Cyclic siloxanes such as 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7-tetravinyltetramethylcyclotetrasiloxane and decamethylcyclopentasiloxane, hexamethyldisiloxane,
Octamethyltrisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane, tetradecamethylhexasiloxane, hexadecamethylheptasiloxane, octadecamethyloctasiloxane, eicosamethyleniasiloxane, docosamethyldecasiloxane,
3,3-diphenylhexamethyltrisiloxane, siloxane oligomers, dimethylpolysiloxane, methylphenylpolysiloxane, diphenylpolysiloxane,
Alkyl modified polysiloxane, methacryl modified polysiloxane, chloroalkyl modified polysiloxane, fluorine modified polysiloxane, polyether modified polysiloxane,
Examples thereof include alcohol-modified polysiloxane, amino-modified polysiloxane, epoxy-modified polysiloxane, phenol-modified polysiloxane, carboxy-modified polysiloxane, and mercapto-modified polysiloxane. These silicon compounds may be used alone or in combination.

Of these, dimethylpolysiloxane,
Methylphenylpolysiloxane, dimethoxydimethylsilane, dimethoxydiphenylsilane, octamethylcyclotetrasiloxane and octaphenylcyclotetrasiloxane are preferred.

The polycarbonate used in the present invention is
It is preferably represented by the general formula (III). here,
R ⁵ is a divalent hydrocarbon group having 1 to 20 carbon atoms; at least a part of hydrogen atoms of the hydrocarbon group is selected from the group consisting of a halogen atom, a hydrocarbon group, an alkoxy group, and a phenoxy group. A divalent hydrocarbon group having 1 to 20 carbon atoms substituted with at least one of the following: or an R ⁶ -Z-R ⁷ group (wherein R ⁶ and R
⁷ is a divalent aromatic hydrocarbon group, each hydrogen atom of the aromatic ring may be independently substituted with a halogen atom, a hydrocarbon group, an alkoxy group or a phenoxy group, and Z Is a single bond, -O-, -S-, -SO-,
Is selected from the group consisting of —SO ₂ —, —CO—, and hydrocarbon groups having 1 to 20 carbon atoms); and c is an integer from 1 to 5000.

Specific examples of the above polycarbonate include:
The polycarbonate derived from the diol shown below is mentioned. For example, 2,2-bis (4-hydroxyphenyl) propane (also known as bisphenol A), bis (4-
Hydroxyphenyl) methane, bis (4-hydroxy-)
3,5-dimethylphenyl) methane, bis (4-hydroxy-3,5-dichlorophenyl) methane, 1,1-bis (4-hydroxyphenyl) cyclohexylmethane,
1,1-bis (4-hydroxyphenyl) ethane, 1,
1-bis (4-hydroxyphenyl) -1-phenylethane, 1,1-bis (4-hydroxyphenyl) -3,
3,5-Trimethylcyclohexane (also known as bisphenol TMC), 4,4'-dihydroxydiphenyl ether, bis (4-hydroxy-3,5-dimethylphenyl) ether, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxy) -3,5-dimethylphenyl) sulfone, 4,4'-dihydroxybenzophenone, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, tetrabromobisphenol A,
Tetrachlorobisphenol A, dihydroxydiphenyl, hydroquinone, resorcinol, dihydroxynaphthalene, dihydroxyanthracene, phenolphthalein, fluorescein, 2,2'-dihydroxy-
Polycarbonates derived from aromatic diols such as 1,1-dinaphthylmethane and 4,4′-dihydroxydinaphthyl, and ethylene glycol, propylene glycol, tetramethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, 1,3- For aliphatic diols such as propanediol, 1,2-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 1,6-hexanediol, and 1,10-decanediol. Examples include polycarbonates derived from them. These polycarbonates may be used alone or in combination.

Among the polycarbonates used in the present invention, the polycarbonate derived from bisphenol A is preferable.

The dicarbonate of diol used in the present invention is preferably represented by the above general formula (IV). Here, R ⁸ is a divalent hydrocarbon group having 1 to 20 carbon atoms; at least a part of hydrogen atoms of the hydrocarbon group is
A divalent hydrocarbon group having 1 to 20 carbon atoms substituted with at least one selected from the group consisting of a halogen atom, a hydrocarbon group, an alkoxy group, and a phenoxy group; or R ¹⁰ -Z- R ¹¹ group (wherein R ¹⁰ and R ¹¹ are divalent aromatic hydrocarbon groups, and the hydrogen atoms of the aromatic ring are each independently a halogen atom, a hydrocarbon group, an alkoxy group, or a phenoxy group). Optionally substituted with a group, and Z is a single bond, -O-, -S-, -SO.
_{-, - SO 2 -, -} CO-, and 1-20 is selected from the group consisting of hydrocarbon groups having a carbon atom) in there; and R ⁹ is carbonized having 1 to 20 carbon atoms It is a hydrogen group.

Specific examples of the dicarbonate of the above-mentioned diol include those shown below. For example, 2,2
-Bis (4-hydroxyphenyl) propane (also known as bisphenol A), bis (4-hydroxyphenyl) methane, bis (4-hydroxy-3,5-dimethylphenyl) methane, bis (4-hydroxy-3,5-) Dichlorophenyl) methane, 1,1-bis (4-hydroxyphenyl) cyclohexylmethane, 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 1, 1-bis (4
-Hydroxyphenyl) -3,3,5-trimethylcyclohexane, 4,4'-dihydroxydiphenyl ether, bis (4-hydroxy-3,5-dimethylphenyl) ether, bis (4-hydroxyphenyl) sulfone, bis (4-) Hydroxy-3,5-dimethylphenyl) sulfone, 4,4′-dihydroxybenzophenone, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, tetrabromobisphenol A,
Tetrachlorobisphenol A, dihydroxydiphenyl, hydroquinone, resorcinol, dihydroxynaphthalene, dihydroxyanthracene, phenolphthalein, fluorescein, 2,2'-dihydroxy-
Aromatic diols such as 1,1-dinaphthylmethane and 4,4′-dihydroxydinaphthyl, or ethylene glycol, propylene glycol, tetramethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, 1,3-propanediol, 1 Of aliphatic diols such as 1,2-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 1,6-hexanediol and 1,10-decanediol, bis (methyl) Carbonate, bis (ethyl carbonate), bis (propyl carbonate), bis (butyl carbonate), bis (cyclohexyl carbonate) and bis (phenyl carbonate). The dicarbonates of these diols may be used alone or in combination.

Of the diol dicarbonates used in the present invention, bisphenol A bis (methyl carbonate) and bisphenol A bis (phenyl carbonate) are preferred.

The diester of dicarboxylic acid used in the present invention is preferably represented by the above general formula (V). Here, R ¹² is a divalent hydrocarbon group having 1 to 20 carbon atoms; or at least a part of hydrogen atoms of the hydrocarbon group is a halogen atom, a hydrocarbon group, an alkoxy group, or a phenoxy group. 2 having 1 to 20 carbon atoms substituted with at least one selected from the group consisting of
Is a valent hydrocarbon group; and R ¹³ is a hydrocarbon group having 1 to 20 carbon atoms.

Specific examples of the above-mentioned dicarboxylic acid diester include those shown below. For example, terephthalic acid, methoxyterephthalic acid, ethoxyterephthalic acid, fluoroterephthalic acid, chloroterephthalic acid, methylterephthalic acid, isophthalic acid, phthalic acid, methoxyisophthalic acid, methylisophthalic acid, diphenylmethane-
4,4'-dicarboxylic acid, diphenylmethane-3,3 '
-Dicarboxylic acid, diphenyl ether-4,4'-dicarboxylic acid, diphenyl-4,4'-dicarboxylic acid, naphthalene-1,4-dicarboxylic acid, naphthalene-1,5-
Aromatic dicarboxylic acids such as dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, 3-methylazelein Aliphatic dicarboxylic acids such as acids, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3
-Dimethyl ester, diethyl ester such as alicyclic dicarboxylic acid such as cyclopentanedicarboxylic acid, 1,5-decahydronaphthalene dicarboxylic acid, 2,6-decahydronaphthalene dicarboxylic acid, and 2,7-decahydronaphthalene dicarboxylic acid , Dipropyl ester, dibutyl ester, dicyclohexyl ester, and diphenyl ester. These dicarboxylic acid diesters may be used alone or in combination.

Among the dicarboxylic acid diesters used in the present invention, dimethyl terephthalate, dimethyl isophthalate and dimethyl naphthalene-2,6-dicarboxylate are preferred.

As the catalyst used in the present invention, known esterification or transesterification catalysts can be used. As these catalysts, alkali metals such as lithium, sodium and potassium, alkaline earth metals such as magnesium, calcium, barium and strontium, zinc,
Examples thereof include acetates, carbonates, borates, oxides, hydroxides, hydrides, alcoholates, and phenolates of metals such as cadmium, titanium, zirconium, tin, antimony, lead, manganese, and cobalt. These esterification or transesterification catalysts may be used alone or in combination.

Of these, tin compounds are preferable,
For example, stannous acyl, stannous tetraacyl tin, dibutyltin oxide, dibutyltin diacetate, dibutyltin laurate, dimethyltin maleate, tin dioctanoate, tin tetraacetate, stannous chloride,
Stannic chloride, stannous acetate, trichlorobutyltin,
Examples include dichlorodibutyltin, stannous oxide, and stannic oxide.

The amount of these catalysts used is not particularly limited, but is preferably 0.0001 to 1.0 part by weight, more preferably 0.0005 to 100 parts by weight based on 100 parts by weight of the siloxane copolymer produced. 0.1 part by weight is used. When the amount of the catalyst used is less than 0.0001 part by weight, the reaction does not proceed sufficiently, and when it is more than 1.0 part by weight, the resulting polymer is severely colored and the physical properties such as hydrolysis resistance are deteriorated. .

The present invention is characterized by adding a cobalt compound to these reaction mixtures.

Specific examples of the above cobalt compound include:
Cobalt acetate, cobalt carbonate, cobalt benzoate, cobalt phenate, cobalt sulfate, cobalt 4-cyclohexylbutyrate, cobalt 2-ethylhexanoate, cobalt gluconate, cobalt naphthenate, cobalt formate, cobalt oleate, cobalt stearate, shu Examples thereof include cobalt acid.

The cobalt-based compound used in the present invention is
Cobalt acetate, cobalt carbonate, and cobalt benzoate are preferred.

The amount of the cobalt compound added is not particularly limited, but is preferably 0.0001 to 1 part by weight, based on 100 parts by weight of the siloxane copolymer produced.
More preferably 0.001 to 0.05 part by weight is added. If the amount of the cobalt compound added is less than 0.00011 parts by weight, the effect of reducing the coloring of the produced polymer is insufficient, and if it is more than 1 part by weight, the physical properties of the produced polymer (for example, mechanical properties, heat resistance, Not only the hydrolysis resistance) decreases, but also the coloration increases.

The timing of adding the cobalt compound is not particularly limited, and may be before the initiation of polymerization, during the polymerization, or after the completion of the polymerization. The cobalt compound is preferably added at the start of polymerization. On the other hand, for example, when the cobalt compound is added after completion of the polymerization, the addition can be performed by melt-kneading the siloxane-based copolymer product obtained by the polymerization and the cobalt-based compound using, for example, an extruder. .

In the present invention, it is preferable to carry out the reaction by a two-step process at different temperatures. In the first step, heating is carried out under normal pressure, preferably 150 to 300 ° C, more preferably 200 to 300 ° C. In the second step, preferably 200 to 400 ° C, more preferably 250 to 35 ° C.
The reaction is carried out under heating at 0 ° C. and under reduced pressure (0.05 to 1.0 torr). However, the present invention is not limited to the reaction in the above-mentioned two-step process, and the reaction may be carried out at multi-step temperature and reduced pressure, or may be carried out under the same temperature condition throughout the reaction.

In the present invention, when polycarbonate is used as a starting material, in the first step, depolymerization and transesterification reaction between the polycarbonate and the diester of the dicarboxylic acid and the silicon compound occur to form a siloxane-based oligomer. In the second step, transesterification further proceeds under reduced pressure to obtain a high molecular weight siloxane-based copolymer.

When a diol dicarbonate is used as a starting material instead of the polycarbonate, the diol dicarbonate and the dicarboxylic acid diester are transesterified in the first step, and at the same time, the product and the silicon compound are reacted. A transesterification reaction is performed to generate a siloxane-based oligomer. Further, by reducing the pressure in the second step, a high molecular weight siloxane-based copolymer is obtained.

Further, when the diester of dicarboxylic acid is not used, transesterification reaction between the dicarbonate of polycarbonate and / or diol and the silicon compound occurs in the first step, and the reduced pressure is used in the second step. A high molecular weight siloxane-based copolymer is obtained.

In the production method of the present invention, the amount of each reaction component used and the reaction conditions are adjusted appropriately,
Various siloxane-based copolymers can be produced.
That is, in the production method of the present invention, when diester of dicarboxylic acid is used, polycarbonate and / or
Or (repeating unit) of dicarbonate of diol 1
When the diester of dicarboxylic acid and the silicon compound are used in a total amount of 1 mol or more per mol, the carbonate part completely reacts, and as a result, the carbonate part disappears and a polyester-siloxane copolymer is formed. . On the other hand, when the total amount of the diester of dicarboxylic acid and the silicon compound is less than 1 mol per 1 mol of the (repeating unit) of the dicarbonate of the polycarbonate and / or the diol, the carbonate moiety is not completely reacted. However, as a result, the carbonate portion remains, so that a polyester carbonate-siloxane copolymer is formed. Furthermore, when diesters of dicarboxylic acids are not used, (repeating units) of polycarbonates and / or dicarbonates of diols are used.
When 1 mol or more of the silicon compound is used with respect to 1 mol, the carbonate part completely reacts, and as a result, the carbonate part disappears and a polyol-siloxane copolymer is produced. On the other hand, if the silicon compound is used in a proportion of less than 1 mol per 1 mol (repeating unit) of the polycarbonate and / or dicarbonate of the diol, the carbonate part does not react completely, and as a result, the carbonate part remains. Therefore, a polycarbonate-siloxane-based copolymer is generated.

In the present invention, suitable cosolvents such as diphenyl ether, biphenyl, substituted cyclohexane, decahydronaphthalene, 1,2,4,5-
Tetramethylbenzene may be used. Alternatively, a non-solvent that is not compatible with the resulting polymer may be used, such as poly (fluorinated alkylene oxide).

The siloxane copolymer obtained by the production method of the present invention may be formed into pellets (chips) and then formed, or may be formed into a desired shape using an extruder or the like.

Further, the siloxane copolymer obtained by the production method of the present invention can be blended with other known resins, and additives may be added if necessary.

Examples of the other known resin include known thermoplastic resins, thermosetting resins, elastomers, and the like. Examples thereof include polyethylene, polypropylene, polystyrene, polymethylmethacrylate, polyamide, polycarbonate, polyester, polyphenylene oxide,
Examples include polysulfone.

As the above additives, in addition to the above catalysts,
Stabilizer, pigment, dye, optical brightener, nucleating agent, polymerization accelerator,
It is also possible to add a filler, a reinforcing material (for example, glass fiber, carbon fiber) or the like during the polymerization or to the produced polymer.

Furthermore, the copolymer obtained by the production method of the present invention is used as a main component of a flame-retardant resin composition or as a flame retardant for improving the flame retardancy of other known resins. be able to. When the copolymer obtained by the production method of the present invention is used as the main component of the flame-retardant resin composition, the high molecular weight copolymer obtained by the production method of the present invention (weight average molecular weight of 1000
(Preferably about 0 to 300,000) is preferable. On the other hand, when the copolymer of the present invention is used as a flame retardant, 1% by weight of a low molecular weight copolymer obtained by the production method of the present invention (preferably about 2000 to 20000 as a weight average molecular weight) is contained in the composition. To less than 30% by weight. The molecular weight of the copolymer obtained by the production method of the present invention can be adjusted by a known method such as the amount of catalyst.

The siloxane-based copolymer obtained by the production method of the present invention is excellent in flame retardancy, moldability, mold releasability and surface lubricity, and is flame retardant while maintaining other excellent properties. Especially excellent in sex.

The siloxane copolymer obtained by the production method of the present invention can be widely used for producing shaped articles, fibers, filaments, films and the like. The siloxane-based copolymer obtained by the production method of the present invention has excellent flame retardancy, molding processability, and
It is suitable for articles that utilize mold releasability and surface lubricity and require higher heat resistance, toughness, hydrolysis resistance, creep resistance and the like. For example, it is particularly suitable for articles in the fields of home appliances, lighting, and automobiles.

[0067]

The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited to the following examples, but various modifications can be made without departing from the scope of the invention. .

The properties of the polymer were measured according to the methods described below.

(1) Weight average molecular weight (Mw) of polymer Measured by gel permeation chromatography (GPC) method. Chloroform was used as a mobile phase and a polymer concentration was 2 m using a Waters 510 type GPC system.
It was measured in g / ml at a column temperature of 35 ° C. Weight average molecular weight was calculated using polystyrene as a standard sample.

(2) Silicon (Si) Atom Content of Polymer After heating the polymer with sulfuric acid, sodium carbonate and calcium carbonate were added, and after heat treatment in an electric furnace, IC
It was quantified by P (Inductively Coupled Plasma) emission spectroscopy.

(3) Coloring degree of polymer Using a Z-Σ80 color difference meter manufactured by Nippon Denshoku Industries Co., Ltd., JIS
Based on K7103, the yellowness index (YI) was measured by the transmission method. As the test piece, a molded product having a thickness of 1/8 inch was used.

(Example 1) A stainless steel reactor having an internal volume of 14 L equipped with a stirring blade, a nitrogen inlet, a cooling pipe, and a distillation outlet was filled with polycarbonate (Panlite L-1250W, Mv, Teijin Kasei Co., Ltd.). = 25000) 1271g
(Repeating unit: 5.0 mol), Dimethyl terephthalate 291 g (1.5 mol), Dimethyl isophthalate 29
1 g (1.5 mol), dimethylpolysiloxane (manufactured by Shin-Etsu Chemical Co., Ltd., KF968, 100 cs) 222 g (repeating unit 3.0 mol), dibutyltin diacetate.
585 g (1.67 mmol), cobalt acetate 0.25 g
Was charged, and after nitrogen substitution, 280 in the state of nitrogen flow
Heated to ° C. The contents were melted by keeping the temperature for 1 hour. Then, the rotation of the stirring blade was started, and the dimethyl carbonate produced at the same temperature was refluxed for 60 minutes. Subsequently, the temperature was raised to 300 ° C., and dimethyl carbonate was removed from the distillation port over 2 hours. The pressure of the reaction system was gradually reduced (1 torr in 30 minutes), and at the same time, the temperature was raised to 320 ° C. and kept for 2 hours.
After the stirring was stopped, the pressure was returned to atmospheric pressure with nitrogen, and then the reaction mixture was taken out to obtain a polymer. The obtained polymer was dissolved in methylene chloride and poured into a large amount of hexane to reprecipitate the polymer for purification.

The IR spectrum of the obtained polymer is shown in FIG.
Shown in The material polycarbonate is 1775 cm
^-1 absorption of C = O stretching vibration derived from a carbonate bond is observed, but such absorption is not observed in the obtained polymer, and instead C = O derived from an ester bond is detected.
Absorption of stretching vibration was confirmed at 1745 cm ^-1 . Also,
At 940 cm ⁻¹ , absorption of Si—O stretching vibration derived from O—Si—R (aromatic) bond was confirmed. In addition, when the polymer obtained by melting the alkali was analyzed by ICP emission spectroscopy, the content of silicon (Si) atoms was 3.3% by weight.
Met. These results showed that the obtained polymer was a polyester-siloxane copolymer.

The obtained polymer was subjected to the above tests (1) to (3) to evaluate the characteristics. The results are shown in Table 1.

Example 2 The same procedure as in Example 1 was carried out except that 0.25 g of cobalt benzoate was used instead of cobalt acetate.

The physical properties of the obtained polymer are shown in Table 1.

Example 3 The same procedure as in Example 1 was carried out except that cobalt acetate was not added at the start of polymerization, and was added after removing dimethyl carbonate under normal pressure for 2 hours.

The physical properties of the obtained polymer are shown in Table 1.

Example 4 Instead of polydimethylsiloxane, dimethoxydimethylsilane (Tokyo Chemical Industry Co., Ltd.) was used.
Example 1 was repeated except that 361 g (3.0 mol) of (produced) was used. The results obtained by the same analysis method showed that the obtained polymer was a polyester-siloxane copolymer.

The physical properties of the obtained polymer are shown in Table 1.

Example 5 The same procedure as in Example 4 was carried out except that 120 g (1.0 mol) of dimethoxydimethylsilane was used.

The IR spectrum of the obtained polymer is shown in FIG.
Shown in The resulting polymer was observed the absorption of C = O stretching vibration derived from the carbonate linkage 1775 cm ^-1, and absorption of C = O stretching vibration derived from the ester bond at 1740 cm ^-1. In addition, absorption of Si—O stretching vibration derived from O—Si—R (aromatic) bond was confirmed at 940 cm ⁻¹ . Further, when the polymer obtained by melting the polymer with an alkali was analyzed by ICP emission spectroscopy, the silicon atom content was 1.7% by weight. From these results, it was shown that the obtained polymer was a polyester carbonate-siloxane copolymer.

The physical properties of the obtained polymer are shown in Table 1.

Example 6 The procedure of Example 1 was repeated, except that 1722 g (5.0 mol) of bis (methyl carbonate) of bisphenol A was used instead of the polycarbonate. According to the results of similar analysis method,
The resulting polymer was shown to be a polyester-siloxane copolymer.

The physical properties of the obtained polymer are shown in Table 1.

Example 7 Except that dimethyl terephthalate and dimethyl isophthalate were not used,
Performed in the same manner as in Example 4.

The IR spectrum of the obtained polymer is shown in FIG.
Shown in The resulting polymer was observed the absorption of C = O stretching vibration derived from the carbonate linkage 1775 cm ^-1, absorption of Si-O stretching vibration derived from the 940cm ^-1 O-Si-R (aromatic) the binding Was confirmed. Further, when the polymer obtained by melting the alkali in the polymer was analyzed by ICP emission spectroscopy, the silicon (Si) atom content was 5.6% by weight. These results showed that the obtained polymer was a polycarbonate-siloxane copolymer.

The physical properties of the obtained polymer are shown in Table 1.

Comparative Example 1 The same procedure as in Example 1 was carried out except that cobalt acetate was not added.

The physical properties of the obtained polymer are shown in Table 1.

Example 8 The same amount of cobalt acetate as in Example 1 was added to the product obtained in Comparative Example 1, an extruder (LABOTEX manufactured by Japan Steel Works Ltd., screw L / D: 25.
5. Resin temperature: 270 ° C.) was used for melt-kneading to obtain a polyester-siloxane copolymer.

The physical properties of the obtained polymer are shown in Table 1.

[0093]

[Table 1]

From the results shown in Table 1 above, it can be seen that the addition of the cobalt compound to the polymer reaction mixture resulted in a lower degree of coloring of the obtained siloxane copolymer than when the cobalt compound was not used.

[0095]

According to the production method of the present invention, a siloxane-based copolymer having a low degree of coloring can be produced simply and inexpensively. The siloxane-based copolymer thus obtained is also excellent in flame retardancy, moldability, mold releasability and surface lubricity.

[Brief description of drawings]

1 is an IR spectrum diagram of a polyester-siloxane copolymer obtained in Example 1. FIG.

2 is an IR spectrum diagram of the polyester carbonate-siloxane copolymer obtained in Example 5. FIG.

3 is an IR spectrum diagram of the polycarbonate-siloxane copolymer obtained in Example 7. FIG.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display location // C08L 83/04 LRY C08L 83/04 LRY

Claims (14)

[Claims] 1. A reaction between at least one polycarbonate and / or diol dicarbonate, if necessary at least one dicarboxylic acid diester, and a silicon compound in the presence of an esterification or transesterification catalyst, A method for producing a siloxane-based copolymer, wherein the silicon compound is at least one selected from the group consisting of compounds represented by the following general formulas (I) and / or (II), and cobalt A manufacturing method in which a system compound is added to the reaction mixture: Embedded image In the formula, R ¹ , R ² , R ³ and R ⁴ are each independently
A hydrogen atom or a substituted or unsubstituted organic group;
X and Y are each independently a hydrogen atom, or
A substituted or unsubstituted organic group; a is 0 to 5000
And b is an integer from 3 to 20. 2. The production method according to claim 1, wherein the cobalt-based compound is at least one selected from the group consisting of cobalt acetate, cobalt carbonate, and cobalt benzoate. 3. The cobalt compound is 0.00 parts with respect to 100 parts by weight of the siloxane copolymer produced.
The manufacturing method according to claim 1 or 2, wherein 001 to 1 part by weight is added. 4. The production method according to claim 1, wherein the cobalt compound is added at the start of polymerization. 5. The production method according to any one of claims 1 to 4, wherein the polycarbonate is represented by the following general formula (III): In the formula, R ⁵ is a divalent hydrocarbon group having 1 to 20 carbon atoms; at least a part of hydrogen atoms of the hydrocarbon group is
A divalent hydrocarbon group having 1 to 20 carbon atoms substituted with at least one selected from the group consisting of a halogen atom, a hydrocarbon group, an alkoxy group, and a phenoxy group; or R ⁶ -Z- R ⁷ group (wherein R ⁶ and R ⁷ are divalent aromatic hydrocarbon groups, and the hydrogen atoms of the aromatic ring are each independently a halogen atom, a hydrocarbon group, an alkoxy group, or a phenoxy group). Optionally substituted with a group, and Z is a single bond, —O—, —S—, —SO—,
Is selected from the group consisting of —SO ₂ —, —CO—, and hydrocarbon groups having 1 to 20 carbon atoms); and c is an integer from 1 to 5000. 6. The production method according to claim 1, wherein the dicarbonate of the diol is represented by the following general formula (IV): In the formula, R ⁸ is a divalent hydrocarbon group having 1 to 20 carbon atoms; at least a part of hydrogen atoms of the hydrocarbon group is
A divalent hydrocarbon group having 1 to 20 carbon atoms substituted with at least one selected from the group consisting of a halogen atom, a hydrocarbon group, an alkoxy group, and a phenoxy group; or R ¹⁰ -Z- R ¹¹ group (wherein R ¹⁰ and R ¹¹ are divalent aromatic hydrocarbon groups, and the hydrogen atoms of the aromatic ring are each independently a halogen atom, a hydrocarbon group, an alkoxy group, or a phenoxy group). Optionally substituted with a group, and Z is a single bond, -O-, -S-, -SO.
_{-, - SO 2 -, -} CO-, and 1-20 is selected from the group consisting of hydrocarbon groups having a carbon atom) in there; and R ⁹ is carbonized having 1 to 20 carbon atoms It is a hydrogen group. 7. The production method according to claim 1, wherein the diester of dicarboxylic acid is represented by the following general formula (V): In the formula, R ¹² is a divalent hydrocarbon group having 1 to 20 carbon atoms; or at least a part of hydrogen atoms of the hydrocarbon group is a halogen atom, a hydrocarbon group, an alkoxy group,
And a divalent hydrocarbon group having 1 to 20 carbon atoms substituted with at least one selected from the group consisting of and phenoxy group; and R ¹³ has 1 to 20 carbon atoms It is a hydrocarbon group. 8. The silicon compound is selected from the group consisting of dimethylpolysiloxane, methylphenylpolysiloxane, dimethoxydimethylsilane, dimethoxydiphenylsilane, octamethylcyclotetrasiloxane, and octaphenylcyclotetrasiloxane. 7. The manufacturing method according to any one of 7. 9. The production method according to claim 1, wherein the polycarbonate is a polycarbonate of 2,2-bis (4-hydroxyphenyl) propane. 10. The dicarbonate of the diol is
The bis (methyl carbonate) of 2,2-bis (4-hydroxyphenyl) propane or the bis (phenyl carbonate) of 2,2-bis (4-hydroxyphenyl) propane. Manufacturing method. 11. The production method according to claim 1, wherein the diester of dicarboxylic acid is selected from the group consisting of dimethyl terephthalate, dimethyl isophthalate, and dimethyl naphthalene-2,6-dicarboxylate. . 12. The production method according to claim 1, wherein the esterification or transesterification catalyst is a tin-based compound. 13. The esterification or transesterification catalyst is lithium, sodium, potassium, magnesium, calcium, barium, strontium, zinc, cadmium, titanium, zirconium, tin, antimony,
At least one selected from the group consisting of acetate, carbonate, borate, oxide, hydroxide, hydride, alcoholate, and phenolate of a metal selected from the group consisting of lead, manganese, and cobalt. The manufacturing method according to claim 1. 14. The method according to claim 1, wherein the esterification or transesterification catalyst is used in an amount of 0.0001 to 1 part by weight based on 100 parts by weight of the siloxane-based copolymer produced. Manufacturing method.