JPH06298922A - Polycarbonate-polyorganosiloxane copolymer - Google Patents

Abstract

PURPOSE:To obtain a polycarbonate-polyorganosiloxane copolymer containing a specific amount of a specific recurring unit in the main chain, having a non- halogenophenoxy terminal, exhibiting excellent flame-retardance, impact resistance, transparency and mold releasability and useful as a flame-retarding part of building material, etc. CONSTITUTION:The copolymer is composed of a main chain having (A) a recurring unit of formula I (R<1> and R<2> are 1-6C alkyl or 6-12C aryl; m and n are 0-4; Z is single bond, 1-6C alkylene, etc.), (B) a recurring unit of formula II (X<1> to X<4> are halogen; Y is single bond, 1-6C alkylene, etc.) and (C) a structural unit of formula III (R<3> to R<6> are H, 1-6C alkyl or phenyl; R<7> and R<8> are organic residue containing aliphatic or aromatic group; A is O, NH or single bond; j is 1-100) and contains (D) a non-halogenophenoxy terminal group of formula IV (R<9> is 1-20C alkyl, etc.; k is 0-5). The amount of the component B is 1-10mol% based on A+B and that of the component C is 0.01-10wt.% based on A+B+C. The copolymer has a viscosity-average molecular weight of 10,000-50,000.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a polycarbonate-polyorganosiloxane copolymer. More particularly, it relates to a polycarbonate-polyorganosiloxane copolymer excellent in flame retardancy, impact resistance, transparency and releasability.

[0002]

2. Description of the Related Art Conventionally, various flame-retardant halogen-containing copolycarbonates have been proposed. For example, Japanese Patent Publication No. 46-40715 and Japanese Patent Publication No. 47-24660.
Japanese Patent Publication [Tetrabromobisphenol A (TBA) and Bisphenol A (BPA) Copolymer], JP-A-51
-123294 (copolymer of tetrabromobisphenol sulfone (TBS) and BPA), JP-A-51
No. 136796 [Copolymer of statistical mixture of halogenated bisphenol and BPA], JP-A-52-14
No. 0597, JP-A-54-50065 [Copolymer of thiodiphenol (TDP) and BPA, tetrabromobisphenol A (TBA) and bisphenol A]
Blend with (BPA) Copolymer], JP-A-56-
No. 99226 [Tetrabromothiodiphenol (T
BTDP) and BPA copolymer] and the like are known. These copolymers are obtained by copolymerizing halogenated bisphenols in which the benzene nucleus of bisphenols is substituted with halogen in order to contain the amount of halogen required to impart flame retardancy. However, both of them have a problem that these halogenated bisphenols must be used in a relatively large amount, and accordingly, the mechanical strength (particularly impact resistance strength) of the polycarbonate must be sacrificed. Other halogen-containing polycarbonates are also known in Japanese Examined Patent Publication No. 46-40715 [using halogenated phenols as terminal terminators]. However, also in this case, it is not possible to impart both flame retardancy and mechanical strength. As a method of improving the above-mentioned drawbacks, a method of copolymerizing BPA and a halogenated bisphenol by using polyhalogenophenol as an end terminating agent [eg, JP-A-64-79]
No. 227, Japanese Patent Application Laid-Open No. 64-79228, Japanese Patent Application Laid-Open No. 3-200833, etc. are known, and these methods can simultaneously impart flame retardancy and impact resistance. As a result of further research, the inventors of the present invention used a non-halogenophenol that does not substantially contain halogen as a terminal terminating agent, and copolymerized BPA, a halogenated bisphenol and a polyorganosiloxane, thereby achieving excellent difficulty. 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 an end terminating agent is aimed at. It was found to have characteristics. The present invention has been completed based on such findings.

That is, in the present invention, the main chain is (a) general formula (I)

[0005]

[Chemical 5]

[In the formula, 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, and may be the same or different, m And n are integers of 0 to 4, respectively. Z
Is a single bond, an alkylene group having 1 to 6 carbon atoms or an alkylden group, 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. ] The repeating units (A) and (b) represented by the general formula (II)

[0007]

[Chemical 6]

[In the formula, X ^{1 to} X ⁴ each represent a halogen atom. Y is a single bond, an alkylene group having 1 to 6 carbon atoms or an alkylden group, a cycloalkylene group having 5 to 20 carbon atoms, a cycloalkylidene group, a fluorenylidene group,
Or -O -, - S -, - SO -, - SO 2 - or -CO
-Indicating binding. ] The repeating units (B) and (c) represented by the general formula (III)

[0009]

[Chemical 7]

[Wherein R³~ R⁶Is the hydrogen source
Child, an alkyl group having 1 to 6 carbon atoms or a phenyl group
But they may be the same or different
Yes. Also, R ⁷And R⁸Are respectively aliphatic or aromatic
Represents an organic residue containing a group, A is -O-, -NH- or
Indicates a single bond. j is an integer of 1 to 100. ]]
Having a structural unit (C) represented by the general formula (IV)

[0011]

[Chemical 8]

[Wherein R ⁹ is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or 7 to 20 carbon atoms]
Represents an arylalkyl group, and k is an integer of 0-5. When k is plural, plural R ⁹ may be the same or different. ] It is a copolymer consisting of the terminal group (D) of the non-halogenophenoxy group represented by, and the content of the repeating unit (B) in the main chain is
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 is 0.01 to 10% by weight based on the total amount of the unit (C)
And its viscosity average molecular weight is from 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 has a repeating unit represented by the general formula (I) whose main chain is the component (a). The general formula (I) which is the components (A) and (b)
In addition to having the repeating unit (B) represented by I) and the structural unit (C) represented by the general formula (III) which is the component (c), a non-halogenophenoxy group represented by the general formula (IV) It is composed of a terminal group (D). Here, the general formula (I)
R ¹ and R ² in the repeating unit (A) are each represented by an alkyl group having 1 to 6 carbon atoms (eg, methyl group, ethyl group, propyl group, n-butyl group, isobutyl group, amyl group, Isoamyl group, hexyl group, etc.) or an aryl group having 6 to 12 carbon atoms (eg, phenyl group, tolyl group, xylyl group, naphthyl group, etc.), which may be the same or different, and m And n is
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, penterylene group, hexylene group, ethylidene group, isopropylidene group, etc.), C5-C20 cycloalkylene group Or a cycloalkylidene group (eg, cyclopentylene group, cyclohexylene group, cyclopentylidene group, cyclohexylidene group, etc.), fluorenylidene group, or —O—, —S—, —SO—, —SO ₂ — or — Shows a CO-bond. Here, the fluorenylidene group has the formula

[0014]

[Chemical 9]

It is represented by Further, 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. The X ^{1 to} X ⁴ may be the same or different, but are usually the same in many cases. Y is a single bond, an alkylene group having 1 to 6 carbon atoms or an alkylidene group (for example, methylene group, ethylene group, propylene group, butylene group, penterylene group, hexylene group, ethylidene group, isopropylidene group, etc.), carbon number 5 To 20 cycloalkylene groups or cycloalkylidene groups (eg, cyclopentylene group, cyclohexylene group, cyclopentylidene group, cyclohexylidene group, etc.), fluorenylidene group, or —O—, —S
-, - SO -, - indicating the or -CO- bond - SO _2. Further, R ^{3 to} R ⁶ in the structural unit (C) represented by the general formula (III) are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms (eg, methyl group, ethyl group, propyl group, n
-Butyl group, isobutyl group, amyl group, isoamyl group,
A 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, and j represents 1 to 100, preferably 5 to 50.
Is an integer. When j exceeds 100, the obtained PC-
The transparency of PDMS copolymerization is lowered, which is not preferable. 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 positions of the molecule, particularly at both terminal positions. A phenoxy group that does not contain) is bound. R in the terminal group (D) represented by the general formula (IV)
⁹ is an alkyl group having 1 to 20 carbon atoms (for example, methyl group, ethyl group, propyl group, n-butyl group, isobutyl group, amyl group, isoamyl group, hexyl group, octyl group, nonyl group, tert-butyl group , Tert-amyl group, tert
-Octyl group), an aryl group having 6 to 20 carbon atoms (eg, phenyl group, tolyl group, xylyl group, naphthyl group, etc.) or an arylalkyl group having 7 to 20 carbon atoms (eg, benzyl group, phenethyl group, 9 -Anthrylmethyl group, α, α-dimethylbenzyl group, etc.), and k is an integer of 0 to 5. When k is plural, plural R
Each ⁹ may be the same or different. This PC-PDMS copolymer has the repeating units (A), (B) and the structural unit (C), and has a non-halogenophenoxy group as a terminal group (D) at the terminal position (preferably both terminal positions). There are various structures such as a random copolymer, a block copolymer, 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 such that the repeating unit (A) and the repeating unit (B) are the same.
In the total amount of 1 to 10 mol%, preferably 4 to
It is 9 mol%. The proportion of the repeating unit (B) is 1 mol%
If it is less than the above, the effect of improving flame retardancy is not observed. Also, 10
If it exceeds mol%, the mechanical strength such as impact resistance decreases. At the same time, the ratio of the structural unit (C) represented by the general formula (III), which is the component (c), relative to 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
Is. When the proportion of the structural unit (C) is less than 0.01% by weight, mechanical strength such as impact resistance is lowered and excellent flame retardancy is not exhibited. Further, when it exceeds 10% by weight,
It is not preferable because the heat resistance is lowered. And its viscosity average molecular weight is from 1,000,000 to 5,000,000, preferably 12,000.
~ 40,000. When the viscosity average molecular weight is less than 10,000, the mechanical strength such as impact resistance decreases. Also, 5
When it exceeds 0000, fluidity is lowered and moldability is deteriorated, which is not preferable. The content of halogen atoms in the PC-PDMS copolymer is usually 4% by weight or more, preferably 4.5% by weight or more.

Examples of an efficient and preferable method for producing such a PC-PDMS copolymer include, but are not limited to, the following methods. (Fig. 1
The production flow of the PC-PDMS copolymer is described below) First, in a solvent such as methylene chloride, if necessary, in the presence of a known acid acceptor and a molecular weight modifier, the following general formula (V) is used.

[0018]

[Chemical 10]

[In the formula, R ¹ , R ² , m, n and Z are the same as defined above. ] The bisphenol represented by phosgene is reacted with phosgene in the reaction system to substantially all react to give a polycarbonate oligomer (hereinafter, referred to as PC
Abbreviated as oligomer. ) Is manufactured. This PC oligomer has a repeating unit (A) represented by the general formula (I), which is formed by a reaction between bisphenol and phosgene in the polycondensation reaction. That is, the PC oligomer having the repeating unit (A) represented by the general formula (I) was obtained by adding 1 phosgene to 100 bisphenols.
The reaction is carried out at a molar ratio of 10 to 150. Usually, in this reaction, bisphenols are added in an alkaline aqueous solution, and the mixture is stirred with a solvent such as methylene chloride, chlorobenzene, chloroform, carbon tetrachloride, etc. and, if necessary, a catalyst such as triethylamine or trimethylbenzylammonium chloride at a predetermined ratio. Then blow phosgene on it and
It can be produced by proceeding the interfacial polycondensation reaction at a reaction temperature of 30 to 70 ° C. for 3 hours. At this time, the reaction system generates heat, so it is preferable to cool with water or ice. Moreover, since the reaction system shifts to the acidic side as the reaction progresses, it is preferable to maintain the pH at 10 or more by adding an alkaline compound while measuring with a pH meter. The PC oligomer thus obtained has an average molecular weight of 2
It is less than 000 and is a 1-10-mer.

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

[0021]

[Chemical 11]

[In the formula, X ^{1 to} X ⁴ and Y are the same as defined above. ] An alkaline aqueous solution of tetrahalogenobisphenols represented by the following general formula (VII)

[0023]

[Chemical 12]

[In the formula, R ⁹ and k are the same as defined above. ] A non-halogenophenol alkaline aqueous solution represented by the following formula and a catalyst such as triethylamine and trimethylbenzylammonium chloride are mixed and stirred at a predetermined ratio to perform polymerization, and a polycarbonate copolymer oligomer (hereinafter abbreviated as 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 copolymer oligomer has tetrahalogenobisphenols 1.2 to 14 and non-halogenophenol 0.1 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
It has a repeating unit (B) represented by the general formula (II) and a repeating unit (A) represented by the general formula (I), which are constituted by a reaction with a tetrahalogenobisphenol.
Here, as the bisphenols represented by the general formula (V), specifically, bis (4-hydroxyphenyl) alkanes such as 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 [common name: bisphenol A]; 2-methyl-1,1-bis (4-hydroxyphenyl) propane; 2,2-bis (4- Hydroxyphenyl-1-methylphenyl) propane; 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane; 1-ethyl-1,1-bis (4-hydroxyphenyl) propane; 2,2- 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 , 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; 1,10-bis (4-hydroxyphenyl) decane and the like.

Examples of the bis (4-hydroxyphenyl) cycloalkane include 1,1-bis (4-hydroxyphenyl) cyclohexane; 1,1-bis (3,5-dichloro-4-hydroxyphenyl) cyclohexane. 1,1-bis (4-hydroxyphenyl) cyclodecane and the like can be mentioned. 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, etc. Dihydroxydiaryl ethers, 4,4′-dihydroxybenzophenone;
Dihydroxy diaryl ketones 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;
Dihydroxydiaryl sulfoxides such as bis (3-methyl-4-hydroxyphenyl) sulfoxide,
Examples thereof include dihydroxydiphenyls such as 4,4′-dihydroxydiphenyl, bisphenolfluorene 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) are, for example, tetrabromobisphenol A, tetrachlorobisphenol A,
Tetrafluorobisphenol A, tetraiodobisphenol A, tetrabromobisphenol F, tetrachlorobisphenol F, tetrachlorobisphenol B
Etc., and tetrabromobisphenol A is particularly preferably used. The non-halogenophenol represented by the general formula (VII) includes, for example, phenol, p-tert-butylphenol, p-tert-octylphenol, p-cumylphenol, p-nonylphenol, p-tert-amylphenol. Etc. Further, as another example of the above catalyst, 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. As the alkaline aqueous solution, an aqueous solution of an alkaline compound such as sodium hydroxide, potassium hydroxide or sodium carbonate can be used.

After completion of the reaction, the reaction mixture thus obtained is allowed to stand or separate by centrifugation to separate an aqueous phase and an organic phase containing the PC copolymerized oligomer into an organic phase containing the PC copolymerized oligomer. The phase may be taken out or the next step may be performed without phase separation. The PC copolymer oligomer contained in the above reaction mixture or the separated organic phase is then treated with the 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 S under the condition that substantially no alkaline compound is present, and further reacting with bisphenol in the presence of the alkaline compound. Here, there are various polyorganosiloxanes corresponding to the structural unit (C), but the general formula (VIII) is preferable.

[0028]

[Chemical 13]

It is represented by and is 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, and may be the same or different. Also, 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, amino group, carboxyl group, acid chloride or 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 is lowered, which is not preferable. In the production of the PC-PDMS copolymer, the PDMS is reacted in 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 The bisphenols are reacted at a molar ratio of 10 to 30 with respect to 100 bisphenol units in the PC oligomer. In addition, tetrahalogenobisphenols,
The non-halogenophenol and bisphenols are added in an alkaline aqueous solution, and PDMS is added as it is or in a methylene chloride solution, but the addition order is not particularly limited. However, it is desirable that the bisphenols be 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 the above-mentioned PD corresponding to the PC copolymer oligomer having the repeating units (A) and (B) and the structural unit (C).
It is produced by mixing MS and MS in the presence of substantially no alkaline compound, reacting in the presence of an alkaline compound and a catalyst, and then reacting with bisphenols. That is, in order to produce the PC-PDMS copolymer of the present invention, first, an organic solvent (for example, methylene chloride) is used as 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 fluids, and may be a vertical type or a horizontal type, and may be a dynamic mixer or a static mixer. It may also be an orifice or a centrifugal pump. As the dynamic mixer, specifically, for example, a multi-line mixer [manufactured by Satake Chemical Industry Co., Ltd.],
Examples include Komatsu through the disintegrator [manufactured by Komatsu Zenoa Co., Ltd.] and pipeline homomixer [manufactured by Tokushu Kika Kogyo Co., Ltd.]. 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 PC copolymerized oligomer and PDMS mixed in this mixer is then reacted with bisphenols in the presence of an alkaline compound and a catalyst in the reactor to react the PC-PDMS copolymer. The product can be obtained. Alternatively, the mixture of PC copolymerized oligomer and PDMS mixed in this mixer is then reacted in the reactor in the presence of an alkaline compound and a catalyst to form a PC-PDMS copolymerized oligomer. Furthermore, by reacting this PC-PDMS copolymer oligomer with bisphenol in the presence of an alkaline compound and a catalyst, PC-
It is also possible to obtain a reaction product of a PDMS copolymer. Here, the bisphenols include, as a part thereof, the general formula
Tetrahalogenobisphenols represented by (VI) can be used. This PC copolymer oligomer and PDMS
The reaction product of the PC-PDMS copolymer obtained by the reaction with is because the PC copolymer oligomer is in excess in a molar amount, and therefore, the PC-PDMS copolymer oligomer in which the PC copolymer oligomer is reacted with both terminals of PDMS is used. It is a mixture of PC copolymer oligomers. Here, the reactor is not particularly limited as long as it can stir the fluid, and may be a vertical type or a horizontal type. For example, there is a pipeline homomixer [made by Tokushu Kika Kogyo Co., Ltd.]. The reaction temperature in this reactor is 0 to 60 ° C, preferably 10
~ 50 ° C. The reaction residence time may be 1 second or longer.

The above-mentioned PC-PDMS copolymer or P
Examples of the alkaline compound used to obtain the C-PDMS copolymerized oligomer include NaOH and KOH. This alkaline compound has a molar ratio of 1 to 20, preferably 1.1 to PDMS end groups.
10 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 proceed completely. In addition, the alkaline compound is 20
If it exceeds, the decomposition of the chloroformate group of the PC copolymer oligomer increases, and the molecular weight of the resulting PC-PDMS copolymer does not improve, which is not preferable.

The catalyst may be a tertiary amine or
Can use a quaternary ammonium salt. concrete
Examples of the tertiary amine include trimethylamido.
And triethylamine, tripropylamine, etc.
Be done. Further, as the quaternary ammonium salt, for example,
Trimethylbenzylammonium chloride, triethyl
And rubenzyl ammonium chloride. This
The amount of the catalyst added is equal to that of the PC copolymer oligomer chlorophore.
The molar ratio to the mate group is 1.0 × 10^-Four~ 5.0 x 1
0^-2, Preferably 5.0 × 10^-Four~ 1.0 x 10 ^-2Is.
Addition amount is 1.0 × 10^-FourWhen the value is less than 1, the reaction progresses slowly and
It was 5.0 × 10^-2If it exceeds, the effect will be
No fruit is seen and it is not necessary to add more than 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 a usual 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.
S-copolymer 5 to 95% by weight, preferably 10 to 90% by weight, glass 5 to 60% by weight, preferably 10 to 55% by weight and polycarbonate resin 0 to 90% by weight, preferably 0 to 85% by weight. Is prepared in. Where this P
As the glass used for preparing the C-PDMS copolymer composition, various kinds or forms can be applied. For example, glass fibers, glass beads, glass flakes, glass powder and the like can be used, and these may be used alone or in combination of two or more kinds. Among these, the glass fibers widely used for resin reinforcement may be any of alkali-containing glass, low-alkali glass and non-alkali 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 various forms such as roving, milled fiber, chopped strand, etc. can be mentioned. These glass fibers may be used alone or in combination of two or more kinds.
Further, these glass materials are surface-treated with a silane coupling agent such as aminosilane-based, epoxysilane-based, vinylsilane-based, methacrylsilane-based, a chromium complex compound, a boron compound or the like in order to enhance the affinity with the resin. It may be

This PC-PDMS copolymer composition is blended with the above-mentioned components and various additive components used as necessary, and kneaded. The compounding and kneading are carried out by a commonly used method, 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 or a multi-screw extruder. It can be carried out. The heating temperature during kneading is usually 250 to
It is selected in the range of 300 ° C. PC-P thus obtained
The DMS copolymer composition is a molded article in the field of automobiles such as glass for automobiles, sunroof, etc. by applying various known molding methods such as injection molding, blow molding, extrusion molding, compression molding, calender molding, rotational molding and the like. It is possible to manufacture molded products in the field of home appliances. In addition, various additives, other synthetic resins, elastomers, and the like can be added to this composition, if necessary. Moreover, you may use it, mixing with an inorganic filler. For example, various additives include antioxidants such as hindered phenol-based, phosphite-based, phosphate-based, and amine-based antioxidants, ultraviolet absorbers such as benzotriazole-based and benzophenone-based antioxidants, and hindered amine-based light-absorbing agents. Examples thereof include stabilizers, aliphatic carboxylic acid ester-based and paraffin-based external lubricants, flame retardants, flame retardant aids, release agents, antistatic agents, and colorants.

The PC-PDMS copolymer of the present invention is
Has sufficient flame retardancy due to lahalogenobisphenols
It is possible to obtain molded products that
As a flame retardant used for imparting a suitable organic acid
Or alkali metal salts of inorganic acids or alkaline earth metals
Salts and halogen-containing compounds are mentioned. Where is good
As the preferable inorganic alkali metal salt, sodium salt, potassium salt, etc.
Examples thereof include a lithium salt and a lithium salt. In addition,
Calcium salt, magnesium as the alkaline earth metal salt
Examples include salt. Also, an inorganic alkali metal salt or
With the inorganic acid used to obtain the inorganic alkaline earth metal salt
Then, H₃AlF₆, H₃BF₆, H₃SbF₆, H
₂TiF₆, H₂SiF₆, H₃PO_Four, H₂Zr
F ₆, H₂WF₆, HBF_FourEtc. preferable
Inorganic alkali metal salt or inorganic alkaline earth metal salt
For Na₃AlF₆, Ca₃(AlF₆)₂Is mentioned
It In addition, organic alkali metal salts or organic alkaline earth
As a preferred organic acid used in obtaining the metal salt,
Aliphatic sulfonic acid, aromatic sulfonic acid, aromatic carvone
Acids and aliphatic carboxylic acids. As a specific example,
Lifluoromethane-sulfonic acid; perfluorobutane
Rufonic acid; Perfluorooctane sulfonic acid; Dodecane
Sulfonic acid; benzenesulfonic acid; 2,4,6-tric
Lolobenzenesulfonic acid; benzenedisulfonic acid; naphth
Tallsulfonic acid; Caprylic acid; Lauric acid; Benzo
Acid; naphtholcarboxylic acid; 2,4,6-tribromoammonium
Benzoic acid and the like can be mentioned. Preferred organic alkali metal salts
Or as an organic alkaline earth metal salt,
Potassium tansulfonate, perfluorobutane sulfone
Calcium acid is mentioned. Also, halogen-containing compounds
As the above, various types can be used. Its representative
Tetrahalogenobisphenols
Low molecular weight polycarbonate containing carbon, tetrahalogen
Epoxy resin containing nobisphenols and its
Other halogen-based flame retardants can be mentioned. That
Of these, flame retardants belonging to the above are preferable.

The low molecular weight polycarbonate containing the above tetrahalogenobisphenols has the general formula

[0038]

[Chemical 14]

[In the formula, 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. ] The repeating unit (X) represented by

[0040]

[Chemical 15]

[In the formula, R ¹⁰ is the same as defined above. ] The repeating unit (Y) represented by q pieces [however, p shows the integer of 1-30, q shows the integer of 0-30, p + q = 1-50]
It is an integer of (particularly 3 to 20). ], And is represented by 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 (3,3
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,
Especially, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane [commonly known as tetrabromobisphenol A] is effective. Further, 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, and particularly 2,2-bis (4-hydroxyphenyl) propane. [Common name bisphenol A] is effective.

Next, the epoxy resin containing tetrahalogenobisphenols is represented by the general formula

[0043]

[Chemical 16]

[Wherein R ¹⁰ is the same as defined 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 are halogens. Represents an atom, and r represents an integer of 1 to 30. ] And a halogen content of 30% by weight or more.

Further, 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; 2,
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, especially those containing 2 to 10 halogen atoms are preferable, and examples thereof include decabromodiphenyl ether, octabromodiphenyl ether, hexabromodiphenyl ether, pentabromodiphenyl ether, tetrabromodiphenyl ether,
Examples include tribromodiphenyl ether, dibromodiphenyl ether, hexachlorodiphenyl ether, pentachlorodiphenyl ether, tetrachlorodiphenyl ether, trichlorodiphenyl ether and dichlorodiphenyl ether.

[0046]

The present invention will be further described in 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 sodium hydroxide solution
Was dissolved and a sodium hydroxide aqueous solution of bisphenol A was prepared. Then, the aqueous sodium hydroxide solution of bisphenol A kept at room temperature was passed through the 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 tube length of 10 m. Introduce phosgene into this and co-flow 1
It was blown in at a flow rate of 0.7 kg / hour and continuously reacted for 3 hours. The tubular reactor used here was a double tube, and cooling water was passed through the jacket to keep the discharge temperature of the reaction solution at 25 ° C. The pH of the discharged liquid is 10 to 11
Was adjusted as shown. The reaction liquid thus obtained was allowed to stand still to separate and remove the aqueous phase, and a methylene chloride phase (220 liters) was collected. To this, 170 liters of methylene chloride was further added and sufficiently stirred. This was designated as PC oligomer A (concentration: 317 g / liter). The degree of polymerization of the PC oligomer A obtained here is 2 to 4
And the concentration of the chloroformate group was 0.7N.

Production Example 1-2 [Production of PC Oligomer B] Bisphenol A 2,275
g (9.96 mol) of 2.0 N sodium hydroxide aqueous solution 14
Dissolve in liter, put in a vessel with an internal volume of 50 liter with a stirrer, add 8.25 liter of methylene chloride and stir (50 rpm), and while cooling, blow phosgene at a flow rate of 0.2 mol / min for 70 minutes to carry out the reaction. went. After stopping the blowing of phosgene, stirring was continued for another 30 minutes.
Then, 312 g of tetrabromobisphenol A (0.5
74 mol), 68 g of p-tert-butylphenol (0.4
53 mol of sodium hydroxide (NaOH: 78.6 g,
What was dissolved in water: 1.35 liters) was added while continuing stirring, and 1.8 cc of triethylamine was added, and 450
The reaction was carried out 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 / liter, chloroformate group concentration: 0.48 mol / liter).

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, It was stirred at room temperature for 17 hours. After that, the oil phase is separated and 25g
Of sodium hydrogen carbonate 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 oil. 60 g of 2-allylphenol and 0.001
To a mixture of 4 g of platinum as platinum chloride-alcoholate complex was added 294 g of the oil obtained above at a temperature of 90 ° C. The mixture was stirred for 3 hours while maintaining the temperature of 90 to 115 ° C. The product was extracted with methylene chloride and washed 3 times with 80% aqueous methanol to obtain an excess of 2
-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 is NMR
The number of repeating dimethylsilanooxy units was 30 as determined by.

Production Example 2-2 [Synthesis of Reactive PDMS-B] In Production Example 2-1,
The procedure of Production Example 2-1 was repeated, except that the amount of 1,1,3,3-tetramethyldisiloxane was changed to 18.1 g. In the obtained terminal phenol PDMS, the number of repeating dimethylsilanooxy units was 150 as measured by NMR.

Example 1 [Production of PC-PDMS Copolymer A] In a container with an internal volume of 50 liters equipped with a stirrer, 10 liters of PC oligomer A (bisphenol A unit: 11.6 mol) was reacted with PDMS.
-A8g and p-tert-butylphenol 77g (0.5
1 mol) and tetrabromobisphenol A 413 g (0.76 mol) dissolved in an aqueous sodium hydroxide solution (NaOH: 110 g, water: 1.35 liters) were mixed to obtain triethylamine 2.9 cc. Was added, and the mixture was stirred and reacted at 300 rpm for 60 minutes. After completion of the reaction, 500 g of bisphenol A dissolved in an aqueous sodium hydroxide solution (NaOH: 290 g, water: 3.42 liter) was mixed with the above reaction system, and methylene chloride 6.1 was added.
1 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 order of alkali (0.01N-NaOH), acid (0.1N-HCl) and water. A flake-shaped polymer was obtained by removing methylene chloride.

Example 2 [Production of PC-PDMS Copolymer B] In Example 1, 578 g of tetrabromobisphenol A 413 g
Other than changing the amount to (1.06 mol), in the same manner as in Example 1,
A flake-like polymer was obtained.

Example 3 [Production of PC-PDMS Copolymer C] In Example 1, 143 g of tetrabromobisphenol was replaced with 743 g.
(1.37 mol), sodium hydroxide aqueous solution (Na
A flake polymer was obtained in the same manner as in Example 1 except that the polymer was dissolved in OH: 220 g, water: 2.70 liter.

Example 4 [Production of PC-PDMS Copolymer D] The PC oligomer B obtained in Production Example 1-2 and the reactive PDMS obtained in Production Example 2-1 were subjected to the flow shown in FIG. -A was reacted. PC oligomer B, reactive PDMS-A
5% by weight methylene chloride solution, 1% by weight triethylamine (TEA) aqueous solution and 25% by weight sodium hydroxide (NaOH) aqueous solution were used, respectively. Each flow rate is PC oligomer B: 13 liters / hour, reactive P
DMS-A was 4 liters / hour, TEA was 0.3 liters / hour, and NaOH was 0.23 liters / hour. Pipeline homomixer [made by Tokushu Kika Kogyo Co., Ltd., 2SL type: internal volume 0.3 liter, diameter of first turbine blade 42.5 mm, diameter of second turbine blade 48] for both mixer and reactor
mm], the mixer is 500 rpm, and the reactor is 3,000
It was 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 ~
It was 30 ° C. The obtained reaction product (containing a PC-PDMS copolymer oligomer) was left standing and separated to obtain an organic phase 330c.
c was transferred to a 1-liter batch type reactor, 120 cc of methylene chloride and 2.2 g of p-tert-butylphenol were added, and the mixture was stirred to make it uniform. An alkaline aqueous solution of bisphenol A (bisphenol A: 19 g, sodium hydroxide: 11 g, water: 130 cc) was added to this, and 500 rpm
And reacted for 1 hour. After the reaction, the mixture was transferred to a 7-liter washing tank, 400 cc of methylene chloride and 400 cc of water were added, and the organic phase and the aqueous phase were separated. After separation, the organic phase is alkali (0.
01N-NaOH) washing, acid (0.1N-HCl) washing,
Wash with water, then remove methylene chloride, then PC-PDMS
Flake of 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 8 g of the reactive PDMS-A 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 flake-shaped 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 was replaced with 77 g of p-tert-butylphenol.
A flake polymer was obtained in the same manner as in Example 1 except that 115 g (0.51 mol) of cumylphenol was used.

Comparative Example 1 [Production of PC-PDMS Copolymer I] Example 1 except that the reactive PDMS-A was not used.
A flake-shaped polymer was obtained in the same manner as in. Comparative Example 2 [Production of PC-PDMS Copolymer J] In Example 1, 38 g of tetrabromobisphenol A 413 g was used.
The same procedure as in Example 1 except that the amount was changed to (0.07 mol),
A flake-like polymer was obtained. Comparative Example 3 [Production of PC-PDMS Copolymer K] In Example 1, instead of reactive PDMS-A, reactive PDMS- was used.
A flake polymer was obtained in the same manner as in Example 1 except that B was used. 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 120 ° C.
After drying for 24 hours, pelletize with an extruder at 280 ° C.
Molded at 80 ° C. When making pellets,
PC-PDMS copolymers A, C, I, and J had 800 trisnonylphenyl phosphite as an antioxidant.
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 physical properties such as viscosity average molecular weight and glass transition temperature (Tg).
Etc. were measured. The results are shown in Table 1.

[0061]

[Table 1]

[0062]

[Table 2]

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

Then, Examples 1 to 8 and Comparative Examples 1 to 4
The flame-retardant properties, Izod impact strength and haze of the molded products of the PC-PDMS copolymers A to L obtained in 1. were measured. The results are shown in Table 2.

[0065]

[Table 3]

Each measurement was performed as follows. * 1: Flame retardancy Flame retardance test UL-94 1/32 inch (thickness) A vertical flammability test was performed according to Underwriters Laboratory Subject 94. * 2: Izod impact strength (with notch) Using a 1/8 inch thick test piece, JIS-K-711
It measured based on 0. * 3: Haze A test piece having a thickness of 3 mm was measured according to JIS-K-7105.

[0067]

As described above, the PC-PDMS copolymer of the present invention has excellent flame retardancy, mechanical properties, transparency and releasability. Therefore, the polycarbonate-polyorganosiloxane copolymer of the present invention can be widely and effectively used for various industrial materials such as flame retardant parts such as building materials, household appliances, and office automation equipment.

[Brief description of 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 diagram showing a flow of production of a polycarbonate-polyorganosiloxane copolymer oligomer in Example 4.

Claims (1)

[Claims] 1. The main chain comprises (a) the general formula (I):[In the formula, R¹And R²Are alkanes each having 1 to 6 carbon atoms
A killed group or an aryl group having 6 to 12 carbon atoms, which is
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 alkylden group having a prime number of 1 to 6, carbon number
5-20 cycloalkylene groups, cycloalkylidene
Group, fluorenylidene group, or -O-, -S-, -SO
-,-SO₂-Or -CO- bond is shown. ]]
Repeating unit (A), (b) general formula (II)[In the formula, X¹~ X^FourEach represents 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, shiku
Loalkylidene group, fluorenylidene group, or -O-,
-S-, -SO-, -SO₂Shows a -or -CO- bond
You ] The repeating units (B) and (c) represented by the general formula (I
II) [Chemical 3][In the formula, R³~ R⁶Are hydrogen atom and carbon number 1 to
6 alkyl groups or phenyl groups, which are the same for each
Or may be different. Also, R ⁷as well as
R⁸Is an organic residue containing aliphatic or aromatic, respectively.
A represents -O-, -NH- or a single bond. j is
It is an integer of 1 to 100. ] Structural unit (C) represented by
And having the general formula (IV)[In the formula, R⁹Is an alkyl group having 1 to 20 carbon atoms, 6 carbon atoms
To an aryl group having 20 to 20 carbon atoms or an aryl group having 7 to 20 carbon atoms
Represents a rualkyl group, and k is an integer of 0 to 5. Note that k is
When multiple, multiple R⁹Are the same but different
It may be one. ] Non-halogenopheno represented by
A copolymer composed of an end group (D) of a xy group, and
The content of the repeating unit (B) in the main chain is
1 to 1 with respect to the total amount of (A) and the repeating unit (B)
The content of the structural unit (C) is 0 mol% and
Repeating unit (A), repeating unit (B) and structural unit
0.01 to 10% by weight based on the total amount of (C)
And its viscosity average molecular weight is from 10,000 to 50,000.
Polycarbonate-polyorgano characterized by
Roxane copolymer.