JP3166804B2 - Polycarbonate-polyorganosiloxane copolymer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

FIELD OF THE INVENTION The present invention relates to a polycarbonate-polyorganosiloxane copolymer. More specifically, the present invention relates to a polycarbonate-polyorganosiloxane copolymer having excellent flame retardancy, impact resistance, transparency, and mold release properties.

[0002]

2. Description of the Related Art Various halogen-containing copolymerized polycarbonates having flame retardancy have heretofore been proposed. For example, JP-B-46-40715 and JP-B-47-24660.
No. [Copolymer of tetrabromobisphenol A (TBA) and bisphenol A (BPA)]
JP-A-123294 [copolymer of tetrabromobisphenolsulfone (TBS) and BPA];
-136796 [Copolymer of statistical mixture of halogenated bisphenol and BPA], JP-A-52-14
0597, JP-A-54-50065 [Copolymer of thiodiphenol (TDP) and BPA, tetrabromobisphenol A (TBA) and bisphenol A]
(BPA) and a copolymer with (BPA))
No. 99226 [Tetrabromothiodiphenol (T
BTDP) and BPA]. These copolymers are obtained by copolymerizing halogenated bisphenols obtained by substituting halogens on benzene nuclei of bisphenols in order to contain a halogen amount necessary for imparting flame retardancy. However, in any case, these halogenated bisphenols must be used in a relatively large amount, and accordingly, there is a problem that the mechanical strength (particularly, impact resistance) of the polycarbonate must be sacrificed. As another halogen-containing polycarbonate, Japanese Patent Publication No. 46-40715 (using a halogenated phenol as a terminal stopper) is also known. However, in this case, neither flame retardancy nor mechanical strength can be provided. As a method for improving the above-mentioned drawbacks, a method in which polyhalogenophenol is used as a terminal terminator and BPA and a halogenated bisphenol are copolymerized (for example, see JP-A-64-79)
No. 227, JP-A-64-79228, JP-A-3-200833, etc.] are known, and these methods can simultaneously impart flame retardancy and impact resistance. As a result of further studies, the present inventors have found that by using a non-halogenophenol containing substantially no halogen as a terminal terminator and copolymerizing BPA, a halogenated bisphenol and a polyorganosiloxane, an excellent difficulty can be obtained. We succeeded in developing flammability and impact resistance.

[0003]

That is, a polycarbonate-polyorganosiloxane copolymer comprising a specific polycarbonate polymer and a specific polyorganosiloxane polymer using a non-halogenophenol as a terminal terminator is intended. It was found that it had characteristics. The present invention has been completed based on such findings.

That is, according to the present invention, the main chain comprises (a) a compound represented by the general formula (I):

[0005]

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[Wherein, R ¹ and R ² each represent an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, which may be the same or different; And n are each an integer of 0 to 4. Z
Is a single bond, an alkylene or alkyldene group having 1 to 6 carbon atoms, a cycloalkylene group having 5 to 20 carbon atoms, a cycloalkylidene group, a fluorenylidene group, or -O-,-
S -, - SO -, - indicating the or -CO- bond - SO _2. And (b) a repeating unit represented by the following general formula (II):

[0007]

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Wherein X ^{1 to} X ⁴ each represent a halogen atom. Y is a single bond, an alkylene group or alkyldene group having 1 to 6 carbon atoms, a cycloalkylene group having 5 to 20 carbon atoms, a cycloalkylidene group, a fluorenylidene group,
Or —O—, —S—, —SO—, —SO ₂ — or —CO
-Indicates binding. And the repeating unit (B) and (c) represented by the general formula (III):

[0009]

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[Wherein, R^Three~ R⁶Is the hydrogen source
Represents an alkyl group having 1 to 6 carbon atoms or a phenyl group.
And they can be the same or different
No. Also, R ⁷And R⁸Are aliphatic or aromatic, respectively
Represents an organic residue containing a group, A represents -O-, -NH- or
Indicates a single bond. j is an integer of 1 to 100. ]
Having the structural unit (C) represented by the general formula (IV)

[0011]

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[Wherein, R ⁹ represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or 7 to 20 carbon atoms.
And k is an integer of 0 to 5. When k is plural, plural R ⁹ may be the same or different. Is a copolymer consisting of a terminal group (D) of a non-halogenophenoxy group represented by the formula (1), and the content of the repeating unit (B) in the main chain is as follows:
The content of the structural unit (C) is 1 to 10 mol% based on the total amount of the repeating unit (A) and the repeating unit (B), and the content of the repeating unit (A), the repeating unit (B) and the structure 0.01 to 10% by weight based on the total amount of the unit (C)
Having a viscosity average molecular weight of 10,000 to 50,000.
The present invention provides a polycarbonate-polyorganosiloxane copolymer characterized by being 0.

The polycarbonate-polyorganosiloxane copolymer (hereinafter abbreviated as PC-PDMS copolymer) of the present invention comprises a repeating unit represented by the general formula (I) in which the main chain is the component (a). The general formula (I) which is a component (A) or (b)
It has a repeating unit (B) represented by I) and a structural unit (C) represented by the general formula (III) as a component (c), and has a non-halogenophenoxy group represented by the general formula (IV) It consists of a terminal group (D). Here, the general formula (I)
R ¹ and R ² in the repeating unit (A) represented by are each an alkyl group having 1 to 6 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, an n-butyl group, an isobutyl group, an amyl group, An isoamyl group, a hexyl group, etc.) or an aryl group having 6 to 12 carbon atoms (eg, a phenyl group, a tolyl group, a xylyl group, a naphthyl group), which may be the same or different; And n are
Each is an integer of 0 to 4. And Z is a single bond,
C1-C6 alkylene group or alkylidene group (for example, methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, ethylidene group, isopropylidene group, etc.), C5-C20 cycloalkylene group or cycloalkylidene group (e.g., a cyclopentylene group, cyclohexylene group, cyclopentylidene group, etc. cyclohexylidene group), fluorenylidene group, or -O -, - S -, - SO -, - SO ₂ - or - Shows a CO-bond. Here, the fluorenylidene group is represented by the formula

[0014]

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## EQU1 ## X ^{1 to} X ⁴ in the repeating unit (B) represented by the general formula (II) each represent a halogen atom such as a bromine atom, a chlorine atom, a fluorine atom, and an iodine atom. X ^{1 to} X ⁴ may be the same or different, but usually are often the same. Y is a single bond, an alkylene group having 1 to 6 carbon atoms or an alkylidene group (for example, a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, an ethylidene group, an isopropylidene group, etc.); To 20 cycloalkylene groups or cycloalkylidene groups (for example, cyclopentylene group, cyclohexylene group, cyclopentylidene group, cyclohexylidene group, etc.), fluorenylidene group, or -O-, -S
—, —SO—, —SO ₂ — or —CO— bond. Further, R ^{3 to} R ⁶ in the structural unit (C) represented by the general formula (III) each represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, an n
-Butyl group, isobutyl group, amyl group, isoamyl group,
Hexyl group) or a phenyl group. This R ³ ~
R ⁶ may be the same or different. R ⁷ and R ⁸ each represent an organic residue containing an aliphatic group or an aromatic group; A represents —O—, —NH— or a single bond; j represents 1 to 100, preferably 5 to 50;
Is an integer. If j exceeds 100, the resulting PC-
The transparency of PDMS copolymerization resistance is undesirably reduced. The PC-PDMS copolymer has a terminal group (D) represented by the general formula (IV), that is, a non-halogenophenoxy group (that is, a halogen atom as a substituent) at the terminal position of the molecule, particularly at both terminal positions. Phenoxy group). R in the terminal group (D) represented by the general formula (IV)
⁹ is an alkyl group having 1 to 20 carbon atoms (e.g., methyl, ethyl, propyl, n-butyl, isobutyl, amyl, isoamyl, hexyl, octyl, nonyl, tert-butyl) , Tert-amyl group, tert
-Octyl group), an aryl group having 6 to 20 carbon atoms (for example, phenyl group, tolyl group, xylyl group, naphthyl group and the like) or an arylalkyl group having 7 to 20 carbon atoms (for example, benzyl group, phenethyl group, 9 -Anthrylmethyl group, α, α-dimethylbenzyl group, etc.), and k is an integer of 0 to 5. In addition, when k is plural, plural R
⁹ may be the same or different. This PC-PDMS copolymer has the repeating units (A) and (B) and the structural unit (C), and has a non-halogenophenoxy group having a terminal group (D) at a terminal position (preferably at both terminal positions). Are bonded, and there are various types such as a random copolymer, a block copolymer and an alternating copolymer of the repeating units (A), (B) and the structural unit (C).

In this PC-PDMS copolymer,
The proportion of the repeating unit (B) represented by the general formula (II), which is the component (b), is defined as the repeating unit (A) and the repeating unit (B)
1 to 10 mol%, preferably 4 to
9 mol%. The proportion of the repeating unit (B) is 1 mol%
If it is less than 10, the effect of improving the flame retardancy is not observed. Also, 10
If it exceeds mol%, mechanical strength such as impact resistance will be reduced. At the same time, the ratio of the structural unit (C) represented by the general formula (III), which is the component (c), is based on the total amount of the repeating unit (A), the repeating unit (B) and the structural unit (C). , 0.01 to 10% by weight, preferably 0.02 to 8% by weight
It is. When the proportion of the structural unit (C) is less than 0.01% by weight, mechanical strength such as impact resistance is reduced, and excellent flame retardancy is not exhibited. If it exceeds 10% by weight,
Heat resistance is undesirably reduced. And its viscosity average molecular weight is from 10,000 to 50,000, preferably 12,000.
~ 40,000. When the viscosity average molecular weight is less than 10,000, mechanical strength such as impact resistance is reduced. Also, 5
If it exceeds 000, the fluidity decreases, and the moldability deteriorates, which is not preferable. The content of halogen atoms in the PC-PDMS copolymer is usually at least 4% by weight, preferably at least 4.5% by weight.

A preferred method for efficiently producing such a PC-PDMS copolymer includes, for example, the following method, but is not limited thereto. (Figure 1
(Refer to the production flow of PC-PDMS copolymers) First, in a solvent such as methylene chloride, if necessary, in the presence of a known acid acceptor and a molecular weight regulator, the following general formula (V)

[0018]

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Wherein R ¹ , R ² , m, n and Z are the same as above. And phosgene in the reaction system to react substantially all of the phosgene in the reaction system to form a polycarbonate oligomer (hereinafter referred to as PC).
Abbreviated as oligomer. ) To manufacture. This PC oligomer has a repeating unit (A) represented by the general formula (I) constituted by a reaction between a bisphenol and phosgene in the above polycondensation reaction. That is, the PC oligomer having the repeating unit (A) represented by the general formula (I) is obtained by adding phosgene 1 to 100 bisphenols.
The reaction is carried out at a molar ratio of 10 to 150. Normally, in this reaction, bisphenols are added in an aqueous alkali solution, and a solvent such as methylene chloride, chlorobenzene, chloroform, carbon tetrachloride and a catalyst such as triethylamine or trimethylbenzylammonium chloride are mixed and mixed at a predetermined ratio if necessary. And inject phosgene into this
It can be manufactured by advancing an interfacial polycondensation reaction at a reaction temperature of 30 to 70 ° C for up to 3 hours. At this time, since the reaction system generates heat, it is preferable to cool with water or ice. Since the reaction system shifts to the acidic side as the reaction proceeds, it is preferable to maintain the pH at 10 or more by adding an alkali compound while measuring with a pH meter. The PC oligomer thus obtained has an average molecular weight of 2
000 or less and 1 to 10 mer.

Then, after substantially reacting phosgene in the reaction system, the PC oligomer having the repeating unit (A) represented by the general formula (I) is reacted with the following general formula (VI)

[0021]

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Wherein X ^{1 to} X ⁴ and Y are the same as above. And an alkali aqueous solution of a tetrahalogenobisphenol represented by the following general formula (VII):

[0023]

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Wherein R ⁹ and k are the same as above. And a catalyst such as triethylamine or trimethylbenzylammonium chloride is mixed and stirred at a predetermined ratio to carry out polymerization to obtain a polycarbonate copolymer oligomer (hereinafter abbreviated as a PC copolymer oligomer). To manufacture.
Here, the non-halogenophenol represented by the general formula (VII) does not contain a halogen atom as a substituent. This PC copolymerized oligomer is composed of tetrahalogenobisphenols 1.2 to 14 and non-halogenophenol 0.1 with respect to 100 bisphenol units in the PC oligomer.
It is obtained by reacting at a molar ratio of 3 to 6.0.
The obtained PC copolymer oligomer is obtained by the above reaction.
It has a repeating unit (B) represented by the general formula (II) and a repeating unit (A) represented by the general formula (I) constituted by a reaction with a tetrahalogenobisphenol.
Here, as the bisphenols represented by the general formula (V), specifically, as bis (4-hydroxyphenyl) alkane, for example, bis (4-hydroxyphenyl) methane [bisphenol F]; 2-bis (4-hydroxyphenyl) phenylmethane; bis (4
-Hydroxyphenyl) naphthylmethane; bis (4-hydroxyphenyl)-(4-isopropylphenyl) methane; bis (3,5-dichloro-4-hydroxyphenyl) methane; bis (3,5-dimethyl-4-hydroxyphenyl) ) Methane; 1,1-bis (4-hydroxyphenyl) ethane; 1-naphthyl-1,1-bis (4-hydroxyphenyl) ethane; 1-phenyl-1,1-bis (4-hydroxyphenyl) ethane; 1,2-bis (4
-Hydroxyphenyl) ethane; 2,2-bis (4-hydroxyphenyl) propane [commonly known as bisphenol A]; 2-methyl-1,1-bis (4-hydroxyphenyl) propane; 2,2-bis (4- 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane; 1-ethyl-1,1-bis (4-hydroxyphenyl) propane; 2,2-hydroxyphenyl-1-methylphenyl) propane; Bis (3,5-dichloro-4-
Hydroxyphenyl) propane; 2,2-bis (3,5
-Dibromo-4-hydroxyphenyl) propane; 2,
2-bis (3-chloro-4-hydroxyphenyl) propane; 2,2-bis (3-methyl-4-hydroxyphenyl) propane; 2,2-bis (3-fluoro-4-hydroxyphenyl) propane; 2 1,2-bis (4-hydroxyphenyl) butane; 1,1-bis (4-hydroxyphenyl) butane; 2,2-bis (4-hydroxyphenyl) butane [bisphenol B]; 1,4-bis (4- Hydroxyphenyl) butane; 2,2-bis (4
-Hydroxyphenyl) pentane; 3,3-bis (4-
(Hydroxyphenyl) pentane; 4-methyl-2,2-
Bis (4-hydroxyphenyl) pentane; 2,2-bis (4-hydroxyphenyl) hexane; 3,3-bis (4-hydroxyphenyl) hexane; 4,4-bis (4-hydroxyphenyl) heptane; 2-bis (4-hydroxyphenyl) octane; 2,2-bis (4-hydroxyphenyl) nonane; and 1,10-bis (4-hydroxyphenyl) decane.

Examples of the bis (4-hydroxyphenyl) cycloalkane include 1,1-bis (4-hydroxyphenyl) cyclohexane; 1,1-bis (3,5-dichloro-4-hydroxyphenyl) cyclohexane And 1,1-bis (4-hydroxyphenyl) cyclodecane. And bis (4-hydroxyphenyl) sulfone; bis (3,5-dimethyl-
4-hydroxyphenyl) sulfone; dihydroxydiarylsulfones such as bis (3-chloro-4-hydroxyphenyl) sulfone; bis (4-hydroxyphenyl) ether; bis (3,5-dimethyl-4-hydroxyphenyl) ether and the like 4,4′-dihydroxybenzophenone;
Dihydroxydiarylketones such as 3,3 ′, 5,5′-tetramethyl-4,4′-dihydroxybenzophenone, bis (4-hydroxyphenyl) sulfide;
Bis (3-methyl-4-hydroxyphenyl) sulfide; dihydroxydiaryl sulfides such as bis (3,5-dimethyl-4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfoxide;
Dihydroxydiarylsulfoxides such as bis (3-methyl-4-hydroxyphenyl) sulfoxide,
Examples include dihydroxydiphenyls such as 4,4'-dihydroxydiphenyl, bisphenolfluorenes such as 9,9-bis (4-hydroxyphenyl) fluorene, thiobisphenol, bisphenol Z, and tetrabromobisphenol A. Among these, bisphenol A is particularly preferably used. These bisphenols may be used alone or in combination of two or more.

The tetrahalogenobisphenols represented by the general formula (VI) include, for example, tetrabromobisphenol A, tetrachlorobisphenol A,
Tetrafluorobisphenol A, tetraiodobisphenol A, tetrabromobisphenol F, tetrachlorobisphenol F, tetrachlorobisphenol B
And the like, and particularly, tetrabromobisphenol A is preferably used. Examples of the non-halogenophenol represented by the general formula (VII) include, for example, phenol, p-tert-butylphenol, p-tert-octylphenol, p-cumylphenol, p-nonylphenol, p-tert-amylphenol And the like. Further, other examples of the above catalyst include tributylamine,
Tetramethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, trimethylphenylammonium chloride,
Examples thereof include triethylphenylammonium chloride and tetrabutylammonium bromide, and the above-mentioned triethylamine is particularly preferable. In addition, as the aqueous alkali solution, an aqueous solution of an alkaline compound such as sodium hydroxide, potassium hydroxide, and sodium carbonate can be used.

After completion of the reaction, the reaction mixture thus obtained is subjected to standing separation or centrifugal separation to separate into an aqueous phase and an organic phase containing the PC copolymerized oligomer. The phase may be taken out or proceed to the next step without phase separation. The PC copolymer oligomer contained in the reaction mixture or the separated organic phase is then converted to a polyorganosiloxane (PDM) corresponding to the structural unit (C) represented by the general formula (III).
The PC-PDMS copolymer can be produced by mixing S) with a compound under the condition that substantially no alkaline compound is present, and further reacting a bisphenol in the presence of the alkaline compound. Here, there are various polyorganosiloxanes corresponding to the structural unit (C).

[0028]

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This is a highly reactive PDMS.
Here, R ^{3 to} R ⁶ each represent hydrogen, an alkyl group having 1 to 6 carbon atoms or a phenyl group, which may be the same or different. In one molecule, j R ³ and j R ⁴ may be the same or different. And R ⁷ and R
⁸ represents an organic residue containing an aliphatic or aromatic group, and Z represents a hydroxyl group, an amino group, a carboxyl group, an acid chloride or a phenolic hydroxyl group. j is an integer of 1 to 100, preferably 5 to 50. Here, when j exceeds 100, the transparency of the obtained PC-PDMS copolymer decreases, which is not preferable. In the production of the PC-PDMS copolymer, the PDMS reacts with the PC copolymer oligomer (solid amount) at a weight ratio of 0.01 to 14, preferably 0.02 to 12, with respect to 100 of the PC copolymer oligomer (solid amount). Let it. The bisphenols are reacted at a molar ratio of 10 to 30 bisphenols per 100 bisphenol units in the PC oligomer. In addition, tetrahalogenobisphenols,
The non-halogenophenol and bisphenols are added in an aqueous alkali solution, and PDMS is added as it is or in a methylene chloride solution, but the order of addition is not particularly limited. However, bisphenols are preferably added last. The reaction time is 30 minutes to 2 hours,
The reaction temperature is 20 to 40 ° C.

The PC-PDMS copolymer of the present invention comprises a PC copolymer oligomer having the above-mentioned repeating units (A) and (B) and the above-mentioned PD corresponding to the above-mentioned structural unit (C).
It is produced by mixing MS with a condition in which substantially no alkaline compound is present, reacting in the presence of an alkaline compound and a catalyst, and then reacting with a bisphenol. That is, in order to produce the PC-PDMS copolymer of the present invention, first, an organic solvent (for example, methylene chloride) is used for the PC copolymer oligomer and PDMS, and substantially no alkaline compound is present in the mixer. Mix under conditions. Here, the mixer is not particularly limited as long as it can mix a fluid, and may be a vertical type or a horizontal type, and may be a dynamic mixer or a static mixer. Further, an orifice or a centrifugal pump may be used. As the dynamic mixer, specifically, for example, a multi-line mixer (manufactured by Satake Chemical Industry Co., Ltd.),
Komatsu through the disintegrator (manufactured by Komatsu Zenoa Co., Ltd.) and pipeline homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). Further, specific examples of the static mixer include a Kenix-type static mixer, a Sulzer-type static mixer, and a Toray-type static mixer.

The mixture of the PC copolymerized oligomer and PDMS mixed in the mixer is then reacted with bisphenols in the presence of an alkaline compound and a catalyst in a reactor to thereby react the PC-PDMS copolymer. The product can be obtained. Alternatively, the mixture of the PC copolymer oligomer and PDMS mixed in the mixer is then reacted in a reactor in the presence of an alkaline compound and a catalyst to produce a PC-PDMS copolymer oligomer. Further, the PC-PDMS copolymer oligomer is reacted with bisphenols in the presence of an alkaline compound and a catalyst to form PC-PDMS.
A reaction product of the PDMS copolymer can also be obtained. Here, bisphenols have a general formula
The tetrahalogenobisphenols represented by (VI) can be used. This PC copolymerized oligomer and PDMS
The reaction product of the PC-PDMS copolymer obtained by the reaction with the PC-PDMS copolymer oligomer in which the PC copolymer oligomer has reacted at both ends of PDMS, since the PC copolymer oligomer is in excess in a molar amount, It is a mixture of PC copolymerized oligomers. Here, the reactor is not particularly limited as long as it can agitate the fluid, and may be a vertical type or a horizontal type. For example, there is a pipeline homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). The reaction temperature in this reactor is 0 to 60 ° C, preferably 10 to 60 ° C.
５０50 ° C. The reaction residence time may be 1 second or more.

The above-mentioned PC-PDMS copolymer or P
Examples of the alkaline compound used to obtain the C-PDMS copolymer oligomer include NaOH and KOH. This alkaline compound has a molar ratio of 1 to 20, preferably 1.1 to 1, with respect to the terminal group of PDMS.
10 are added. If the alkaline compound is less than 1, PC
It is not preferable because the reaction between the copolymer oligomer and PDMS does not completely proceed. Further, when the alkaline compound is 20
When it exceeds, the decomposition of the chloroformate group of the PC copolymer oligomer increases, and the molecular weight of the obtained PC-PDMS copolymer is not improved, which is not preferable.

As the catalyst, a tertiary amine or
Can use a quaternary ammonium salt. concrete
For example, as a tertiary amine, trimethylamido
, Triethylamine, tripropylamine, etc.
It is. Further, as the quaternary ammonium salt, for example,
Trimethylbenzyl ammonium chloride, triethyl
Rubenzylammonium chloride and the like. This
The amount of the catalyst added is determined by the amount of chloropho
1.0 × 10^-Four~ 5.0 × 1
0^-2, Preferably 5.0 × 10^-Four~ 1.0 × 10 ^-2It is.
1.0 × 10^-FourIf it is less than 1, the reaction progresses slowly,
5.0 × 10^-2If the amount exceeds the
No fruit is seen and need not be added beyond this.

Next, a molded article using the PC-PDMS copolymer of the present invention can be obtained by molding the PC-PDMS copolymer alone by an ordinary molding method. Further, for example, it can also be obtained by preparing and molding a PC-PDMS copolymer composition containing PC-PDMS copolymer, glass fiber and polycarbonate resin as main components. That is, in this case,
The PC-PDMS copolymer composition is usually PC-PDM
5 to 95% by weight, preferably 10 to 90% by weight of S copolymer, 5 to 60% by weight, preferably 10 to 55% by weight of glass and 0 to 90% by weight, preferably 0 to 85% by weight of polycarbonate resin Is prepared. Here, this P
Various types or forms of glass can be used as the glass used for preparing the C-PDMS copolymer composition. For example, glass fiber, glass beads, glass flake, glass powder and the like can be used, and these may be used alone or in combination of two or more. Among these, the glass fiber widely used for resin reinforcement may be any of alkali-containing glass, low-alkali glass, and alkali-free glass. Also,
The fiber length is 0.1 to 8 mm, preferably 0.3 to 6 mm, and the fiber diameter is 0.3 to 30 μm, preferably 0.5 to 25 μm.
m. The form of the glass fiber is not particularly limited, and examples thereof include various types such as roving, milled fiber, and chopped strand. These glass fibers may be used alone or in combination of two or more.
Further, these glass materials are surface-treated with a silane coupling agent such as aminosilane, epoxysilane, vinylsilane, methacrylsilane, chromium complex compound, boron compound, etc. in order to enhance the affinity with the resin. May be used.

This PC-PDMS copolymer composition is blended with the above-mentioned components and various additional components used as required, and kneaded. The compounding and kneading are carried out by a method usually used, for example, a method using a ribbon blender, a Henschel mixer, a Banbury mixer, a drum tumbler, a single screw extruder, a twin screw extruder, a co-kneader, a multi-screw extruder and the like. It can be carried out. And the heating temperature at the time of kneading is usually 250 to
It is selected in the range of 300 ° C. PC-P thus obtained
The DMS copolymer composition can be formed by applying various known molding methods, for example, injection molding, hollow molding, extrusion molding, compression molding, calendar molding, rotational molding, etc., in the automotive field such as automotive glass and sunroof. And molded products in the field of home appliances. In addition, various additives, other synthetic resins, elastomers, and the like can be added to the composition as needed. Further, it may be used by mixing with an inorganic filler or the like. For example, various additives include antioxidants such as hindered phenols, phosphites, phosphates, and amines; ultraviolet absorbers such as benzotriazoles and benzophenones; and light absorbers such as hindered amines. Examples include stabilizers, external lubricants such as aliphatic carboxylic acid esters and paraffins, flame retardants, flame retardant aids, release agents, antistatic agents, coloring agents, and the like.

The PC-PDMS copolymer of the present invention is
Sufficient flame retardant due to lahalogenobisphenols
Moldings, but with even more flame retardancy
As the flame retardant used to apply, a suitable organic acid
Or alkali metal salts of inorganic acids or alkaline earth metals
Salts, and halogen-containing compounds. Where good
Preferable inorganic alkali metal salts include sodium salt and potassium.
Lium salts, lithium salts and the like can be mentioned. In addition, inorganic
Calcium salt, magnesium as Lucari earth metal salt
And the like. Also, an inorganic alkali metal salt or
An inorganic acid used for obtaining an inorganic alkaline earth metal salt;
H_ThreeAlF₆, H_ThreeBF₆, H_ThreeSbF₆, H
_TwoTiF₆, H_TwoSiF₆, H_ThreePO_Four, H_TwoZr
F ₆, H_TwoWF₆, HBF_FourAnd the like. preferable
Inorganic alkali metal salt or inorganic alkaline earth metal salt
Na_ThreeAlF₆, Ca_Three(AlF₆)_TwoIs mentioned
You. Also, organic alkali metal salts or organic alkaline earths
Preferred organic acids used in obtaining the metal salt include:
Aliphatic sulfonic acid, aromatic sulfonic acid, aromatic carboxylic acid
Acids and aliphatic carboxylic acids. As a specific example,
Trifluoromethane-sulfonic acid; perfluorobutane
Sulfonic acid; perfluorooctanesulfonic acid; dodecane
Sulfonic acid; benzenesulfonic acid; 2,4,6-tric
Lorobenzenesulfonic acid; benzenedisulfonic acid; naph
Tall sulfonic acid; caprylic acid; lauric acid; benzoic acid
Acid; naphthol carboxylic acid; 2,4,6-tribromo ammonium
And benzoic acid. Preferred organic alkali metal salts
Or organic alkaline earth metal salts such as perfluorobutyrate.
Potassium tansulfonate, perfluorobutanesulfone
Calcium acid. Also, halogen-containing compounds
Various types can be used. Its representative
Typical are the tetrahalogenobisphenols
-Molecular-weight polycarbonate and tetrahalogen containing
Epoxy resin containing nobisphenols
And other halogen-based flame retardants. Sou
In particular, the flame retardants belonging to the above are preferred.

Here, the low-molecular-weight polycarbonate containing the above-mentioned tetrahalogenobisphenols has the general formula

[0038]

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[Wherein X ^{5 to} X ⁸ represent a halogen atom, R ¹⁰ represents an alkylene group having 2 to 8 carbon atoms, and 1 to 9 carbon atoms.
Represents an alkylidene group, a carbonyl group, a sulfone group, a sulfur atom or an oxygen atom. And p general formula (X) represented by the general formula

[0040]

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Wherein R ¹⁰ is the same as above. ] (Where p is an integer of 1 to 30, q is an integer of 0 to 30, p + q = 1 to 50)
(Particularly 3 to 20). And a low molecular weight polycarbonate (polycarbonate oligomer) having a halogen content of 30% by weight or more. Here, as the halogen-containing bisphenol compound constituting the repeating unit (X), 2,2-bis (3,
5-dibromo-4-hydroxyphenyl) propane;
2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane; bis (3,5-dibromo-4-hydroxyphenyl) methane; bis (3,5-dibromo-4-
Hydroxyphenyl) ether; bis (3,5-dibromo-4-hydroxyphenyl) sulfone and the like are used,
In particular, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane [commonly known as tetrabromobisphenol A] is effective. As the bisphenol compound constituting the repeating unit (Y), 2,2-bis (4-
(Hydroxyphenyl) propane; bis (4-hydroxyphenyl) methane; bis (4-hydroxyphenyl) sulfone; bis (4-hydroxyphenyl) ether and the like are used. In particular, 2,2-bis (4-hydroxyphenyl) propane is used. [Commonly known as bisphenol A] is effective.

Next, epoxy resins containing tetrahalogenobisphenols are represented by the general formula

[0043]

Embedded image

Wherein R ¹⁰ is the same as above, R ¹¹ represents a hydrogen atom, a methyl group, an epoxypropyl group, a phenyl group, a 2-hydroxypropyl group or an oxygen atom, and X ^{9 to} X ¹² represent a halogen atom. Represents an atom, and r represents an integer of 1 to 30. And a halogen content of 30% by weight or more.

Other halogen-based flame retardants include, for example, tetrabromobenzene; tetrachlorobenzene; hexabromobenzene; hexachlorobenzene; hexabromobiphenyl; octabromobiphenyl;
2,4'-dibromobiphenyl;2,4'-dichlorobiphenyl;hexabromobiphenyl; triphenyl chloride; tetrachlorophthalic acid; tetrachlorophthalic anhydride; tetrabromophthalic acid; tetrabromophthalic acid Anhydrous; tribromophenol and other known halogenated aromatic compounds, and 2,2-bis (3,5-dichlorophenyl) propane; bis (2-chlorophenyl) methane; bis (2,6-dibromophenyl) Methane; 1,2-bis (2,6-dichlorophenyl) ethane; 1,1-bis (2-chloro-4-methylphenyl) ethane; 1,1-
Bis (3,5-dichlorophenyl) ethane; 2,2-bis (3-phenyl-4-bromophenyl) ethane;
3-bis (4,6-dichloronaphthyl) propane; 2,
2-bis (2,6-dichlorophenyl) pentane; 2,
2-bis (2,6-dichlorophenyl) hexane; bis (4-chlorophenyl) methane; bis (3,5-dichlorophenyl) cyclohexylmethane; bis (3-nitro-4-bromophenyl) ethane; bis (4-hydroxy- 2,6-dichloro-3-methoxyphenyl) methane;
2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane; 2,2-bis (3,5-dibromo-4)
-Hydroxyphenyl) propane; 2,2-bis (3-
Bromo-4-hydroxyphenyl) propane; 2,2-
There are diaromatics such as bis (3,5-dibromo-4-hydroxyphenyl) propane diglycidyl ether. Further, halogenated diphenyl ethers, particularly those containing 2 to 10 halogen atoms, are preferred.
Examples include tribromodiphenyl ether, dibromodiphenyl ether, hexachlorodiphenyl ether, pentachlorodiphenyl ether, tetrachlorodiphenyl ether, trichlorodiphenyl ether, dichlorodiphenyl ether, and the like.

[0046]

EXAMPLES The present invention will be described in more detail with reference to Production Examples, Examples and Comparative Examples. Production Example 1-1 [Production of PC oligomer A] 5% by weight of 400 liters
60 kg of bisphenol A in aqueous sodium hydroxide
Was dissolved to prepare an aqueous sodium hydroxide solution of bisphenol A. Then, the sodium hydroxide aqueous solution of bisphenol A kept at room temperature was passed through an orifice plate at a flow rate of 138 liters / hour and methylene chloride at a flow rate of 69 liters / hour through a tubular reactor having an inner diameter of 10 mm and a length of 10 m. Phosgene was introduced into this
Blowing was performed at a flow rate of 0.7 kg / hour, and the reaction was continuously performed for 3 hours. The tubular reactor used here was a double tube, and the outlet temperature of the reaction solution was kept at 25 ° C. by passing cooling water through the jacket. The pH of the discharged liquid is 10 to 11
Was adjusted as shown. The reaction solution thus obtained was allowed to stand, and the aqueous phase was separated and removed. A methylene chloride phase (220 liters) was collected. 170 liters of methylene chloride was further added thereto, followed by sufficient stirring. This was designated as PC oligomer A (concentration: 317 g / liter). The degree of polymerization of the PC oligomer A obtained here is 2-4.
And the concentration of the chloroformate group was 0.7N.

Production Example 1-2 [Production of PC oligomer B] Bisphenol A2,275
g (9.96 mol) in 2.0 N aqueous sodium hydroxide solution 14
Dissolve in liter, put into a 50 liter container with a stirrer, add 8.25 liter of methylene chloride, stir (50 rpm), and blow phosgene at a flow rate of 0.2 mol / min for 70 minutes while cooling to carry out the reaction. went. After the phosgene blowing was stopped, stirring was continued for another 30 minutes.
Thereafter, 312 g of tetrabromobisphenol A (0.5
74 mol), 68 g of p-tert-butylphenol (0.4 g)
53 mol) with sodium hydroxide (NaOH: 78.6 g,
Water: 1.35 liters) was added while stirring was continued, and 1.8 cc of triethylamine was added.
The reaction was performed at rpm for 60 minutes. After the reaction, the mixture was allowed to stand for about 30 minutes, and the aqueous phase was separated to obtain an organic phase. This was designated as PC oligomer B (concentration: 496 g / l, chloroformate group concentration: 0.48 mol / l).

Production Example 2-1 [Synthesis of Reactive PDMS-A] 1,483 g of octamethylcyclotetrasiloxane, 96 g of 1,1,3,3-tetramethyldisiloxane and 35 g of 86% sulfuric acid were mixed. Stir at room temperature for 17 hours. Then, the oil phase was separated and 25 g
Was added and stirred for 1 hour. After filtration, vacuum distillation was performed at 150 ° C. and 3 torr to remove low-boiling substances to obtain an oil. 60 g of 2-allylphenol and 0.001
At a temperature of 90 ° C., 294 g of the oil obtained above were added to 4 g of a mixture with platinum as platinum chloride-alcoholate complex. The mixture was stirred for 3 hours while maintaining the temperature at 90-115 ° C. The product is extracted with methylene chloride, washed three times with 80% aqueous methanol, and
-Allylphenol was removed. The product was dried over anhydrous sodium sulphate and evaporated in vacuo to a temperature of 115 ° C. The obtained terminal phenol PDMS was analyzed by NMR.
As a result of the measurement, the number of repeating dimethylsilanooxy units was 30.

Production Example 2-2 [Synthesis of Reactive PDMS-B]
The same operation as in Production Example 2-1 was performed, except that the amount of 1,1,3,3-tetramethyldisiloxane was changed to 18.1 g. The obtained terminal phenol PDMS had a repeating dimethylsilanooxy unit of 150 as measured by NMR.

Example 1 [Production of PC-PDMS copolymer A] In a 50-liter container equipped with a stirrer, 10 liters of PC oligomer A (11.6 mol of bisphenol A unit) was reacted with PDMS.
-A 8 g and p-tert-butylphenol 77 g (0.5
1 mol) and a solution prepared by dissolving 413 g (0.76 mol) of tetrabromobisphenol A in an aqueous solution of sodium hydroxide (110 g of NaOH, 1.35 liters of water) were mixed, and 2.9 cc of triethylamine was mixed. Was added thereto, and the mixture was stirred and reacted at 300 rpm for 60 minutes. After completion of the reaction, a solution prepared by dissolving 500 g of bisphenol A in an aqueous solution of sodium hydroxide (NaOH: 290 g, water: 3.42 liters) was mixed with the above reaction system, and methylene chloride 6.1 was added.
One liter was added, and the mixture was stirred and reacted at 450 rpm for 60 minutes. After the reaction, the organic phase and the aqueous phase were separated, and the organic phase was washed and separated in the order of alkali (0.01N-NaOH), acid (0.1N-HCl) and water. Excluding methylene chloride, a flaky polymer was obtained.

Example 2 [Preparation of PC-PDMS copolymer B] In Example 1, 578 g of tetrabromobisphenol A (413 g) was used.
(1.06 mol), except that it was changed to Example 1.
A flaky polymer was obtained.

Example 3 [Production of PC-PDMS copolymer C] In Example 1, 743 g of tetrabromobisphenol was added in an amount of 743 g.
(1.37 mol) and an aqueous sodium hydroxide solution (Na
OH: 220 g, water: 2.70 liters) except that the polymer was dissolved in the same manner as in Example 1 to obtain a flaky polymer.

Example 4 [Production of PC-PDMS copolymer D] PC oligomer B obtained in Production Example 1-2 and reactive PDMS obtained in Production Example 2-1 according to the flow shown in FIG. -A was reacted. That is, PC oligomer B, reactive PDMS-A
A 5% by weight solution of methylene chloride, a 1% by weight aqueous solution of triethylamine (TEA) and a 25% by weight aqueous solution of sodium hydroxide (NaOH) were used. Each flow rate was 13 liters / hour of PC oligomer B, reactive P
DMS-A: 4 liter / hour, TEA: 0.3 liter / hour, NaOH: 0.23 liter / hour. Both mixer and reactor are pipeline homomixers [2SL type, manufactured by Tokushu Kika Kogyo Co., Ltd .: 0.3 liter in inner volume, 42.5 mm in diameter of first turbine blade, 48 in diameter of second turbine blade.
mm], the mixer was 500 rpm, and the reactor was 3,000
Rotated at 0 rpm. The main pipe (PC oligomer line) used had an inner diameter of 16 mm. TE
A was charged 60 cm from the mixer, and NaOH was charged 80 cm from the mixer. Reactor temperature is 25 ~
30 ° C. The obtained reaction product (containing the PC-PDMS copolymer oligomer) was allowed to stand and separated to separate the organic phase 330c.
c was transferred to a 1-liter batch reactor, and 120 cc of methylene chloride and 2.2 g of p-tert-butylphenol were added, followed by stirring to make the mixture uniform. An alkaline aqueous solution of bisphenol A (bisphenol A: 19 g, sodium hydroxide: 11 g, water: 130 cc) was added thereto, and the mixture was mixed at 500 rpm.
For 1 hour. After the reaction, the mixture was transferred to a 7-liter washing tank, and 400 cc of methylene chloride and 400 cc of water were added to separate an organic phase and an aqueous phase. After separation, the organic phase is alkali (0.
01N-NaOH) washing, acid (0.1N-HCl) washing,
After washing with water and then removing methylene chloride, PC-PDMS
A flake of the copolymer was obtained.

Example 5 [Production of PC-PDMS copolymer E] A flake polymer was obtained in the same manner as in Example 1 except that the amount of reactive PDMS-A 8 g was changed to 40 g. .

Example 6 [Preparation of PC-PDMS copolymer F] In Example 1, except that 8 g of reactive PDMS-A was changed to 160 g,
A flaky polymer was obtained in the same manner as in Example 1.

Example 7 [Production of PC-PDMS copolymer G] A flake polymer was obtained in the same manner as in Example 1 except that 8 g of reactive PDMS-A was changed to 4 g. .

Example 8 [Production of PC-PDMS copolymer H] In Example 1, p-tert-butylphenol (77 g) was replaced with p-tert-butylphenol.
-Except for using 115 g (0.51 mol) of cumylphenol, a flaky polymer was obtained in the same manner as in Example 1.

Comparative Example 1 [Production of PC-PDMS copolymer I] Example 1 was repeated except that no reactive PDMS-A was used.
A flake-like polymer was obtained in the same manner as described above. Comparative Example 2 [Production of PC-PDMS Copolymer J] In Example 1, 413 g of tetrabromobisphenol A was 38 g.
(0.07 mol) in the same manner as in Example 1,
A flaky polymer was obtained. Comparative Example 3 [Production of PC-PDMS copolymer K] In Example 1, the reactive PDMS-A was used instead of the reactive PDMS-A.
Except using B, it carried out similarly to Example 1, and obtained the flaky polymer. Comparative Example 4 (Production of PC-PDMS copolymer L) A flake polymer was obtained in the same manner as in Example 1, except that 8 g of reactive PDMS-A was changed to 0.2 g.

The PC-PDMS copolymers A to L obtained in Examples 1 to 8 and Comparative Examples 1 to 4 were each heated to 120 ° C.
After drying all day and night in an extruder at 280 ° C.,
Molded at 80 ° C. In making the pellet,
For the PC-PDMS copolymers A, C, I, and J, trisnonylphenyl phosphite was used as an antioxidant in an amount of 800.
ppm was added.

The physical properties of the PC-PDMS copolymers A to L obtained in Examples 1 to 8 and Comparative Examples 1 to 4 were evaluated as viscosity average molecular weight and glass transition temperature (Tg).
Etc. were measured. Table 1 shows the results.

[0061]

[Table 1]

[0062]

[Table 2]

Each measurement was performed in the following manner. * 1: Determined from the intensity ratio of aromatic H of bisphenol A residue found at 7.1 to 7.3 ppm in TBA ¹ HNMR and TBA residue found at 7.43 ppm. * 2: Aromatic H of bisphenol A residue found at 7.1 to 7.3 ppm in PDMS ¹ HNMR, aromatic H of TBA residue found at 7.43 ppm, and methyl H of PTBP found at 0.11 ppm From the intensity ratio. * 3: Br content (total Br content in the copolymer) This is the result of alkali decomposition of a sample and analysis by the Holhardt method. * 4: Viscosity average molecular weight (Mv) The viscosity of the methylene chloride solution at 20 ° C. was measured with an Ubbelohde type viscosity tube, and the intrinsic viscosity [η] was calculated from this. [Η] = 1.23 × 10 ⁻⁵ × Mv ^0.83 * 5: Measured by Tg DSC (Differential scanning calorimeter).

Examples 1 to 8 and Comparative Examples 1 to 4
As for the molded articles of the PC-PDMS copolymers A to L obtained in the above, flame retardancy, Izod impact strength and haze were measured as quality evaluations. Table 2 shows the results.

[0065]

[Table 3]

Each measurement was performed according to the following. * 1: Flame retardancy flame retardancy test UL-94 1/32 inch (thickness) A vertical flammability test was performed according to Underwriters Laboratory Subject 94. * 2: Izod impact strength (notched) JIS-K-711 using 1/8 inch thick test piece
0 was measured. * 3: Haze A test piece having a thickness of 3 mm was measured in accordance with JIS-K-7105.

[0067]

As described above, the PC-PDMS copolymer of the present invention is excellent in flame retardancy, mechanical properties, transparency and releasability. Therefore, the polycarbonate-polyorganosiloxane copolymer of the present invention is widely and effectively used in various industrial materials, for example, flame-retardant parts such as building materials, home appliances, and OA equipment.

[Brief description of the drawings]

FIG. 1 is a diagram showing a flow of an example of a method for producing a polycarbonate-polyorganosiloxane copolymer of the present invention.

FIG. 2 is a view showing a flow of producing a polycarbonate-polyorganosiloxane copolymer oligomer in Example 4.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C08G 64/00-64/42 CA (STN) REGISTRY (STN)

Claims (1)

(57) [Claims] The main chain is represented by (a) a compound represented by the following general formula (I):[Wherein, R¹And R^TwoIs an alkyl having 1 to 6 carbon atoms
A kill group or an aryl group having 6 to 12 carbon atoms;
They may be the same or different, m and
n is an integer of 0 to 4, respectively. Z is a single bond, charcoal
Alkylene group or alkyldene group having a prime number of 1 to 6, carbon number
5 to 20 cycloalkylene groups, cycloalkylidene
Group, fluorenylidene group, or -O-, -S-, -SO
−, −SO_Two— Or —CO— bond. ]
Repeating units (A) and (b) represented by general formula (II):[Where X¹~ X^FourRepresents a halogen atom.
Y is a single bond, an alkylene group having 1 to 6 carbon atoms or an alkyl group;
Ruden group, cycloalkylene group having 5 to 20 carbon atoms, cycle
A lower alkylidene group, a fluorenylidene group, or -O-,
-S-, -SO-, -SO_Two-Or -CO-
You. And the repeating unit (B) represented by the general formula (I)
II)[Wherein, R^Three~ R⁶Are a hydrogen atom and a carbon number of 1
6 represents the same alkyl group or phenyl group,
Or different. Also, R ⁷as well as
R⁸Represents an organic residue containing an aliphatic or aromatic group, respectively.
A represents -O-, -NH- or a single bond. j is
It is an integer of 1 to 100. ] The structural unit (C) represented by
And having the general formula (IV):[Wherein, R⁹Is an alkyl group having 1 to 20 carbon atoms, 6 carbon atoms
To 20 aryl groups or arylenes having 7 to 20 carbon atoms
Represents a alkyl group, and k is an integer of 0 to 5. Note that k is
When multiple, multiple R⁹Are the same but different
May be used. Nonhalogenofeno represented by
A copolymer comprising a terminal group (D) of a xy group, and
The content of the repeating unit (B) in the main chain is the repeating unit
1 to 1 based on the total amount of (A) and the repeating unit (B)
0 mol%, and the content of the structural unit (C) is
Repeating unit (A), repeating unit (B) and structural unit
0.01 to 10% by weight based on the total amount of (C)
Has a viscosity average molecular weight of 10,000 to 50,000.
Polycarbonate-polyorganosyn
Loxane copolymer.