JPH06192412A - Polycarbonate-polyorganosiloxane copolymer - Google Patents

Abstract

PURPOSE:To provide a copolymer excellent in flame retardance, impact resistance, clarity, and releasability by selecting a copolymer comprising specific polycarbonate blocks and a specified polyorganosiloxane block. CONSTITUTION:A copolymer is provided which comprises repeating units (A) of formula I (wherein R<1> and R<2> are each 1-4C alkyl, etc.), repeating units (B) of formula II (wherein R<3> and R<4> are each 1-4C alkyl, etc.; and X<1> to X<4> are each halogen), repeating units (C) of formula III (wherein R<5> to R<8> are each 1-6C alkyl, etc.; R<9> and R<10> are each an org. group contg. an aliph. or arom. group; A is -O-, -NH-, or a single bond; and k is 1-100), and terminal polyhalogenophenoxy groups of formula IV (wherein X<3> is halogen) in ratios of the content of B/(A+B) and C/(A+B+C) of 1-10mol% and 0.01-10wt.%, respectively, and which has a viscosity-average mol.wt. of 10,000-50,000.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polycarbonate-polyorganosiloxane copolymer, more specifically, a novel polycarbonate-polyorganosiloxane copolymer excellent in flame retardancy, impact resistance, transparency and releasability. It is about.

[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. With this method, flame retardancy and impact strength can be imparted at the same time, but as a result of further research, the present inventors succeeded in exhibiting superior flame retardancy and impact resistance. .

[0003]

That is, it has been found that a polycarbonate-polyorganosiloxane copolymer composed of a specific polycarbonate polymer and a specific polyorganosiloxane polymer has a desired property. 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 a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and may be the same or different. ] The repeating units (A) and (b) represented by the general formula (II)

[0007]

[Chemical 6]

[In the formula, R ³ and R ⁴ each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and may be the same or different. Also, X ¹ ~
X ⁴ each represents a halogen atom. ] The repeating units (B) and (c) represented by the general formula (III)

[0009]

[Chemical 7]

[Wherein R^Five~ R⁸Is 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 ⁹And R^TenAre respectively aliphatic or aromatic
Represents an organic residue containing a group, A is -O-, -NH- or
Indicates a single bond. k is an integer of 1 to 100. ]]
Having a structural unit (C) represented by the general formula (IV)

[0011]

[Chemical 8]

[In the formula, X ⁵ represents a halogen atom, and m is an integer of 1 to 5. When m is plural, plural X
Each ⁵ may be the same or different. ] It is a copolymer consisting of the terminal group (D) of the polyhalogenophenoxy group represented by, and the content of the repeating unit (B) in the main chain is the total of the repeating unit (A) and the repeating unit (B). The content of the structural unit (C) is 1 to 10 mol% with respect to the amount, and the content of the structural unit (C) is 0, based on the total amount of the repeating unit (A), the repeating unit (B) and the structural unit (C). The present invention provides a polycarbonate-polyorganosiloxane copolymer characterized by having a viscosity average molecular weight of 01 to 10% by weight and a viscosity average molecular weight of 10,000 to 50,000.

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 polyhalogenophenoxy group represented by the general formula (IV) It is composed of a terminal group (D). Here, R ¹ and R in the repeating unit (A) represented by the general formula (I)
² each represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms (methyl group, ethyl group, propyl group, butyl group). Further, X in the repeating unit (B) represented by the general formula (II)
^{1 to} X ⁴ each represent a halogen atom such as a bromine atom, a chlorine atom, a fluorine atom and an iodine atom. This X ¹ ~ X
^{The four} may be the same or different, but are usually the same in many cases. Further, R ³ and R ⁴ in the general formula (II) are each a hydrogen atom or an alkyl group having 1 to 4 carbon atoms (methyl group, ethyl group, propyl group, butyl group) like R ¹ and R ² above. Indicates. Further, R ^{5 to} R ⁸ in the structural unit (C) represented by the general formula (III) are hydrogen and C 1 to C 6, respectively.
Is an alkyl group or a phenyl group. This R ⁵ ~ R ⁸
May be the same or different. In addition, R ⁹ and R ¹⁰ each represent an organic residue containing aliphatic or aromatic, A represents —O—, —NH— or a single bond, and k is an integer of 1 to 100. And
This PC-PDMS copolymer has a terminal position of the molecule, in particular,
The terminal group (D) represented by the general formula (IV), that is, a polyhalogenophenoxy group is bonded to both terminal positions. X ⁵ in the terminal group (D) represented by the general formula (IV) is also a halogen atom such as a bromine atom, a chlorine atom, a fluorine atom and an iodine atom, as in the case of the above X ^{1 to} X ^4. Is shown and m is an integer of 1-5. In addition, X ^{1 to} X ⁴ in the repeating unit (B) represented by the general formula (II) and the general formula (I
X ⁵ in the terminal group (D) represented by V) may be the same or different. This PC-PDMS copolymer has the repeating units (A) and (B) and the structural unit (C), and has terminal positions (preferably both terminal positions).
A polyhalogenophenoxy group of the terminal group (D) is bonded to the above, and a random copolymer, a block copolymer, an alternating copolymer of these repeating units (A), (B) and structural unit (C) There are various things.

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 2 to
It is 8 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. If the proportion of the structural unit (C) is less than 0.01% by weight, the mechanical strength such as flame retardancy and impact resistance will decrease. Further, if it exceeds 10% by weight, the heat resistance is deteriorated, which is not preferable. And the viscosity average molecular weight is from 10,000 to 50,0
00, preferably 12,000 to 40,000. When the viscosity average molecular weight is less than 10,000, the mechanical strength such as impact resistance decreases. On the other hand, when it exceeds 50,000, the fluidity is lowered and the moldability is deteriorated, which is not preferable. The content of halogen atoms in this PC-PDMS copolymer is usually 4% by weight or more, and preferably 4.5% by weight or more. When the content of halogen atoms is less than 4% by weight, the flame retardancy is lowered, which is not preferable.

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
First, refer to the production flow of the PC-PDMS copolymer), 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):

[0016]

[Chemical 9]

[In the formula, R ¹ and R ² are the same as defined above. ] The bisphenols represented by and phosgene are reacted with each other to cause substantially all of the phosgene in the reaction system to react to produce a polycarbonate oligomer (hereinafter abbreviated as PC oligomer). 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) has phosgene of 110 to 150 with respect to 100 of bisphenols.
Are reacted at a molar ratio of. 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, phosgene is blown into this and the interfacial polycondensation reaction is allowed to proceed for 1 to 3 hours at a reaction temperature of 30 to 70 ° C. At this time, the reaction system generates heat, so it is preferable to cool with water or ice. Also, as the reaction progresses, the reaction system shifts to the acidic side, so pH
While measuring with a meter, add an alkaline compound to adjust the pH to 1
It is preferable to keep it at 0 or more. The PC oligomer thus obtained has an average molecular weight of 2000 or less,
1 to 10-mer.

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

[0019]

[Chemical 10]

[In the formula, R ³ , R ⁴ and X ^{1 to} X ⁴ are the same as defined above. ] An alkaline aqueous solution of tetrahalogenobisphenols represented by the following general formula (VII)

[0021]

[Chemical 11]

[In the formula, X ⁵ and m are the same as defined above. ] An alkaline aqueous solution of polyhalogenophenol represented by the following formula and a catalyst such as triethylamine or 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.
This PC copolymer oligomer is based on 100 bisphenol units in the PC oligomer, tetrahalogenobisphenols 1.2 to 14 and polyhalogenophenol 0.3.
Obtained by reacting at a molar ratio of ˜6.0. The PC copolymer oligomer obtained is a repeating unit (B) represented by the general formula (II) and a repeating unit represented by the general formula (I), which are formed by the reaction with tetrahalogenobisphenols in the above reaction. Having (A). Here, as the bisphenols represented by the general formula (V), for example, 2,2-bis (4-hydroxyphenyl) propane [bisphenol A]; bis (4-hydroxyphenyl) methane [bisphenol F]; 2,2-
Bis (4-hydroxyphenyl) butane [bisphenol B]; 2,2-bis (4-hydroxyphenyl) pentane; 3,3-bis (4-hydroxyphenyl) pentane; 2,2-bis (4-hydroxyphenyl) Hexane; 3,3-bis (4-hydroxyphenyl) hexane and the like can be mentioned, and bisphenol A is particularly preferably used. Examples of the tetrahalogenobisphenols represented by the general formula (VI) include 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 polyhalogenophenol represented by the general formula (VII) include, for example, bromophenol, chlorophenol, fluorophenol, dibromophenol, dichlorophenol, difluorophenol, tribromophenol, trichlorophenol, trifluorophenol, and tetrafluorophenol. Examples include bromophenol, tetrachlorophenol, tetrafluorophenol, pentabromophenol, pentachlorophenol, pentafluorophenol, and the like.
Tribromophenol is preferred. In addition, a part (50 mol% or less) of polyhalogenophenol is added to p-tert-
You may change to monohydric phenols, such as butylphenol and phenol. Further, other examples of the catalyst include tributylamine, tetramethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, trimethylphenylammonium chloride, triethylphenylammonium chloride, tetrabutylammonium bromide, and the like. Triethylamine is preferred. 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 the reaction is completed, the reaction mixture thus obtained is separated into an aqueous phase and an organic phase containing the PC copolymerized oligomer by stationary separation or centrifugation, and the organic phase containing the PC copolymerized oligomer is separated. 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.

[0024]

[Chemical 12]

The PDMS is represented by and is highly reactive.
Here, R ^{5 to} R ⁸ each represent hydrogen, an alkyl group having 1 to 6 carbon atoms, or a phenyl group, and may be the same or different. Further, in one molecule, k R ^{5 s} and k R ^{6 s} may be the same or different. And R ⁹ and R
¹⁰ 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. k is an integer of 1 to 100, preferably 5 to 50. Here, when k exceeds 100, the transparency of the obtained PC-PDMS copolymer decreases. In the production of the PC-PDMS copolymer, the above-mentioned PDMS is the PC copolymer oligomer (solid amount) 10
Weight ratio of 0.01 to 14 with respect to 0, preferably 0.0
The reaction is carried out at a ratio of 2-12. The bisphenols are reacted at a molar ratio of 10 to 30 with respect to 100 bisphenol A units in the PC oligomer. The tetrahalogenobisphenols, polyhalogenophenols, and bisphenols are added as an aqueous alkali solution, and PDMS is added as it is or as a methylene chloride solution, but the order of addition is not particularly limited. However, it is desirable that the bisphenols be added last. The reaction time is 30 minutes to 2 hours, and the reaction temperature is 20 to 40 ° C.

The PC-PDMS copolymer of the present invention has 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 product 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
Lahalogenobisphenol A or polyhalogenofe
A molded product with sufficient flame retardancy can be obtained with a solvent such as knot.
Although it can be used to add even more flame retardancy,
The flame retardant used is a suitable organic or inorganic acid
Potassium metal salt or alkaline earth metal salt, and halogen containing
Organic compounds are mentioned. Where preferred inorganic alkali
Metal salts include sodium salt, potassium salt, lithium
Examples include salt. In addition, with inorganic alkaline earth metal salts
Examples include calcium salts and magnesium salts
It In addition, inorganic alkali metal salts or inorganic alkaline earth
The inorganic acid used to obtain the metal salt is H₃Al
F₆, H₃BF₆, H₃SbF₆, H₂TiF₆, H₂
SiF₆, H₃PO_Four, H₂ZrF ₆, H₂WF₆, H
BF_FourEtc. Preferred inorganic alkali metal salt
Or, as the inorganic alkaline earth metal salt, Na₃Al
F₆, Ca₃(AlF₆)₂Is mentioned. Also, organic al
For obtaining potassium metal salt or organic alkaline earth metal salt
Preferred organic acids that can be used include aliphatic sulfonic acids,
Aromatic sulfonic acid, aromatic carboxylic acid and aliphatic cal
It is boric acid. As a specific example, trifluoromethane-
Sulfonic acid; Perfluorobutane sulfonic acid; Perflu
Orooctane sulfonic acid; dodecane sulfonic acid; benze
Sulfonic acid; 2,4,6-trichlorobenzene sulfo
Acid; benzenedisulfonic acid; naphtholsulfonic acid;
Caprylic acid; Lauric acid; Benzoic acid; Naphtholcarb
Acid; 2,4,6-tribromobenzoic acid and the like can be mentioned.
It Preferred organic alkali metal salt or organic alkaline earth
Examples of the metal salts include potassium perfluorobutane sulfonate.
Um, calcium perfluorobutane sulfonate
To be In addition, various halogen-containing compounds are available.
Can be used. As a typical one,
Low molecular weight containing tetrahalogenobisphenols
Polycarbonate, tetrahalogenobisphenols
Epoxy resin and other halogen-based compounds containing
You can give a fuel. Among them, especially above,
Flame retardants belonging to

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

[0034]

[Chemical 13]

[In the formula, X ^{6 to} X ⁹ represent a halogen atom, R ¹¹ 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

[0036]

[Chemical 14]

[In the formula, R ¹¹ is the same as defined above. ] Q repeating unit (Y) represented by these (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 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 has the general formula

[0039]

[Chemical 15]

[Wherein R ¹¹ is the same as above, R ¹² represents a hydrogen atom, a methyl group, an epoxypropyl group, a phenyl group, a 2-hydroxypropyl group or an oxygen atom, and X ^{10 to} X ¹³ 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, as other halogen-based flame retardants, for example, tetrabromobenzene; tetrachlorobenzene; hexabromobenzene; hexachlorobenzene; hexabromobiphenyl; octabromobiphenyl; 2,
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.

[0042]

The present invention will be further described in detail with reference to production examples, examples and comparative examples. Production Example 1-1 (Production of Polycarbonate Oligomer A) 60 kg of bisphenol A was dissolved in 400 liters of a 5 wt% sodium hydroxide aqueous solution to prepare a sodium hydroxide aqueous solution of bisphenol A. 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. It was introduced, and phosgene was co-currently flown thereinto and blown at a flow rate of 10.7 kg / hour to continuously react 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. Further, the pH of the discharged liquid was adjusted so as to show 10 to 11. 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. Polycarbonate oligomer A (concentration 3
17 g / liter). The degree of polymerization of Polycarbonate Oligomer A obtained here was 2 to 4, and the concentration of the chloroformate group was 0.7N.

Production Example 1-2 (Production of Polycarbonate Oligomer B) 2,275 g (9.96 mol) of bisphenol A was dissolved in 14 liters of 2.0N aqueous sodium hydroxide solution and placed in a vessel equipped with a stirrer having an internal volume of 50 liters. After adding 8.25 liters of methylene chloride and stirring (50 rpm), phosgene was blown at a flow rate of 0.2 mol / min for 70 minutes while cooling to carry out the reaction.
After stopping the blowing of phosgene, stirring was continued for another 30 minutes. Then, tetrabromobisphenol A25
0 g (0.46 mol), tribromophenol 150 g
(0.453 mol) sodium hydroxide (NaOH: 78.
6 g, water: 1.35 liters) was added while continuing stirring, and triethylamine (1.8 cc) was added,
The reaction was carried out at 450 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. Polycarbonate oligomer B (concentration: 500 g / liter,
Chloroformate group concentration: 0.5 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) Polycarbonate Oligomer A was placed in a container equipped with a stirrer and having an internal volume of 50 liters.
10 liters (11.6 mol of bisphenol A unit) and 40 g of reactive PDMS-A were mixed and dissolved,
Tetrabromobisphenol A 330 g (0.61 mol)
And 169 g (0.51 mol) of tribromophenol were added to an aqueous sodium hydroxide solution (NaOH: 110 g, water: 1.35).
1 liter) was mixed, triethylamine (2.9 cc) was added, and the mixture was stirred for 60 minutes at 300 rpm and reacted. After the reaction is completed, bisphenol A5 is added to the above reaction system.
00 g of sodium hydroxide aqueous solution (NaOH: 290
g, water: 3.42 liters) and then mix,
Add 6.1 liters of methylene chloride, 450 rp for 60 minutes
The mixture was stirred and reacted at m. After the reaction, the organic phase and the aqueous phase are separated, and the organic phase is treated with alkali (0.01N-NaOH) and acid (0.
1N-HCl) and water were sequentially washed and separated. A flake-shaped polymer was obtained by removing methylene chloride.

Example 2 (Production of PC-PDMS Copolymer B) A flake polymer was obtained in the same manner as in Example 1 except that 160 g of reactive PDMS-A was used. .

Example 3 (Production of PC-PDMS Copolymer C) A flake polymer was prepared in the same manner as in Example 1 except that 185 g (0.57 mol) of tribromophenol was used. Got

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: 4 liters / hour, TEA: 0.3 liters / hour, and NaOH: 0.23 liters / hour. Pipeline homomixer [made by Tokushu Kika Kogyo Co., Ltd., 2SL type: inner volume 0.3 liter, diameter of first turbine blade 42.5 mm, diameter of second turbine blade 48]
mm], the mixer is 500 rpm, and the reactor is 300
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) In Example 1, except that 40 g of reactive PDMS-A was changed to 20 g,
A flake-shaped polymer was obtained in the same manner as in Example 1.

Example 6 (Production of PC-PDMS Copolymer F) In Example 4, the flow rate of a 5 wt% solution of methylene chloride in reactive PDMS-A, 4 l / hr, was changed to 0.8 l / hr. A flake polymer was obtained in the same manner as in Example 4 except for the above.

Example 7 (Production of PC-PDMS Copolymer G) A flake polymer was obtained in the same manner as in Example 1 except that 40 g of the reactive PDMS-A was changed to 4 g. .

Example 8 (Preparation of PC-PDMS Copolymer H) In Example 1, 40 g of reactive PDMS-A was changed to 8 g and 330 g of tetrabromobisphenol A was changed to 195 g (0.358 mol), A flake-shaped polymer was obtained in the same manner as in Example 1.

Comparative Example 1 (Production of PC-PDMS Copolymer I) Example 1 except that 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, p-tert was used instead of 169 g of tribromophenol.
A flake polymer was obtained in the same manner as in Example 1 except that 77 g of butylphenol was used. Comparative Example 3 (Production of PC-PDMS Copolymer K) In the same manner as in Example 1 except that 370 g of tetrabromobisphenol A was replaced with 38 g and 110 g of sodium hydroxide was replaced with 40 g in Example 1, flakes were formed. A polymer of Comparative Example 4 (Production of PC-PDMS Copolymer L) In Example 1, instead of reactive PDMS-A, reactive PDMS-B was used.
A flake polymer was obtained in the same manner as in Example 1 except that was used. Comparative Example 5 (Production of PC-PDMS Copolymer M) In Example 1, except that 40 g of reactive PDMS-A was changed to 0.2 g,
A flake-shaped polymer was obtained in the same manner as in Example 1.
PC-PD obtained in Examples 1-8 and Comparative Examples 1-5
Each of the MS copolymers A to M was dried at 120 ° C. for one day and then pelletized by an extruder at 280 ° C. and molded at 280 ° C. In addition, when making pellets, PC-PDM
To the S copolymers E, F, G and I, 800 ppm of trisnonylphenyl phosphite was added as an antioxidant.

The PC-PDMS copolymers A to H obtained in Examples 1 to 4 and Comparative Examples 1 to 4 were evaluated for their physical properties by the viscosity average molecular weight and the glass transition temperature (Tg).
Etc. were measured. The results are shown in Table 1.

[0056]

[Table 1]

[0057]

[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 a 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, regarding the polycarbonate-polyorganosiloxane copolymer A obtained in Example 1, ¹
A chart of HNMR (deuterated chloroform solution) is shown in FIG.
And the infrared absorption spectrum (cast film) chart is shown in FIG. In addition, the molded products of the PC-PDMS copolymers A to H obtained in Examples 1 to 4 and Comparative Examples 1 to 4 were measured for flame retardancy, Izod impact strength and haze. The results are shown in Table 2.

[0060]

[Table 3]

Each measurement was performed as follows. * 1: Flame retardancy Flame retardancy test UL-94 1/32 inch (thickness) A vertical flammability test was performed in accordance with Underwriters Laboratory Subject 94. * 2: Izod impact strength (with notch) Using a test piece with a thickness of 1/8 inch, 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.

[0062]

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.

3 is a ¹ H-NMR spectrum diagram of the polycarbonate-polyorganosiloxane copolymer A obtained in Example 1. FIG.

4 is an infrared absorption spectrum chart of the polycarbonate-polyorganosiloxane copolymer A obtained in Example 1. FIG.

Claims (1)

[Claims] 1. The main chain comprises (a) the general formula (I):[In the formula, R¹And R²Are hydrogen atom or carbon respectively
Represents an alkyl group of the numbers 1 to 4, even if they are the same
It may be different. ] The repeating unit represented by
(A), (b) General formula (II)[In the formula, R³And R^FourAre hydrogen atom or carbon respectively
Represents an alkyl group of the numbers 1 to 4, even if they are the same
It may be different. Also, X¹~ X^FourIs that
Is a halogen atom. ] Repeating unit (B)
And (c) the general formula (III):[In the formula, R^Five~ R⁸Are a hydrogen atom and a carbon number of 1 to 1, respectively.
6 alkyl groups or phenyl groups, which are the same for each
Or may be different. Also, R ⁹as well as
R^TenIs an organic residue containing aliphatic or aromatic, respectively.
A represents -O-, -NH- or a single bond. k is
It is an integer of 1 to 100. ] Structural unit (C) represented by
And having the general formula (IV)[In the formula, X^FiveRepresents a halogen atom, m is an integer of 1 to 5
Is. When m is plural, plural X^FiveAre each
It may be the same or different. ]]
A polyhalogenophenoxy group consisting of an end group (D)
Polymer and content of repeating unit (B) in the main chain
Is the total amount of repeating unit (A) and repeating unit (B)
On the other hand, it is 1 to 10 mol% and the structural unit
The content of (C) is the repeating unit (A), the repeating unit
0.01 based on the total amount of (B) and structural unit (C)
10 to 10% by weight and its viscosity average molecular weight is 100,000
Polycarbonate characterized by 0-50,000
To-polyorganosiloxane copolymer.