JPS6146007B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing a polycarbonate copolymer, and more specifically, the present invention relates to a method for producing a polycarbonate copolymer, and more specifically, by reacting a polycarbonate having a specific terminal group with polyphenylene oxide in the presence of a free radical generating means, the polycarbonate copolymer has heat resistance,
The present invention relates to a method for efficiently producing a polycarbonate copolymer having excellent chemical resistance, film formability, moldability, etc., at a desired copolymerization ratio. Traditionally, polycarbonate resin has been well known as an engineering resin due to its excellent mechanical, thermal, and electrical properties, especially its impact resistance.
It is often used for mechanical parts, electrical parts, etc. However, polycarbonate resin has the inherent disadvantage that it whitens and crazes when it comes into contact with acetone, heptane, carbon tetrachloride, etc., and also cracks under stress.
Although this resin has excellent properties, its use and application fields have been severely limited. Furthermore, this polycarbonate resin has disadvantages such as insufficient compatibility when blended with other thermoplastic resins such as polystyrene resins. In order to eliminate these drawbacks, a method of mechanically mixing polyphenylene oxide with polycarbonate resin or a method of mixing it as a solution has been proposed (Japanese Patent Publication No. 15782/1982). However, this method involves mere physical mixing, and there are problems in that compatibility is insufficient and the resulting composition is opaque and has poor uniformity. In order to overcome these drawbacks of the prior art, the present inventors have already succeeded in developing a block copolymer consisting of polycarbonate and polyphenylene oxide and a method for producing the same (Japanese Patent Application No. 56-66556).
No. Specification). The present inventors have conducted extensive research in order to develop a method that can more efficiently produce a copolymer of polycarbonate and polyphenylene oxide at a desired copolymerization ratio. As a result, they discovered that the object could be achieved by using polycarbonate having a specific functional group at the end and reacting it with polyphenylene oxide, leading to the completion of the present invention. That is, the present invention has the general formula [In the formula, R represents hydrogen or a desired substituent,
R ₁ and R ₂ each represent an alkyl group or an aryl group. ] A method for producing a polycarbonate copolymer is provided, which comprises reacting a polycarbonate having a terminal group represented by the following with polyphenylene oxide through the intervention of a free radical generating means. As mentioned above, the polycarbonate used in the method of the present invention must have a functional group represented by the general formula () at its terminal end. In the formula, R is not particularly limited and may be a hydrogen atom or a desired substituent, but is usually appropriately selected from a hydrogen atom, a halogen atom, or an alkyl group. In addition, R ₁ and R ₂ are each an alkyl group such as a methyl group, an ethyl group, a propyl group, or an aryl group, but especially R ₁ ,
Most commonly, both R ₂ are methyl groups. Various types of polycarbonate bodies having terminal groups as described above can be considered, and those obtained by reacting various diphenol compounds with phosgene or diphenyl carbonate are used. Here, the diphenol compound usually has the general formula Or general formula [In the formula, R' is a substituted or unsubstituted alkylene group having 1 to 5 carbon atoms, -O-, -S-, _-SO2- , or -CO-, and _Y1 and _Y2 are hydrogen or halogen atoms, a and b are integers of 1-4. ] We can list the following expressions. Examples of the diphenol compounds represented by the above general formula () or () include 4,4'-dihydroxydiphenyl; 2,2-bis-(4-hydroxyphenyl)-propane (bisphenol A); , 4-bis-(4-hydroxyphenyl)-2-methylbutane; 1,1-bis-(4-hydroxyphenyl)-cyclohexane; α, α′-
Bis-(4-hydroxyphenyl)-p-diisopropylbenzene; 2,2-bis-(3-methyl-
4-hydroxyphenyl)-propane; 2,2-
Bis-(3-chloro-4-hydroxyphenyl)-
Propane; bis-(3,5-dimethyl-4-hydroxyphenyl)-methane; 2,2-bis-(3,
5-dimethyl-4-hydroxyphenyl)propane; bis-(4-hydroxyphenyl)sulfone; bis-(3,5-dimethyl-4-hydroxyphenyl)sulfone; 2,4-bis-(3,5 −
dimethyl-4-hydroxyphenyl)-2-methylbutane; 1,1-bis-(3,5-dimethyl-
4-hydroxyphenyl)-cyclohexane;
α,α′-bis-(3,5-dimethyl-4-hydroxyphenyl)-p-diisopropylbenzene;
2,2-bis-(3,5-dichloro-4-hydroxyphenyl)-propane and 2,2-bis-
(3,5-dibromo-4-hydroxyphenyl)-
It's propane. A particularly preferred example of diphenol is 2,2-bis-(4-hydroxyphenyl)-
Propane; 2,2-bis-(3,5-dimethyl-
4-hydroxyphenyl)-propane; 2,2-
Bis-(3,5-dichloro-4-hydroxyphenyl)-propane; 2,2-bis-(3,5-dibromo-4-hydroxyphenyl)-propane and 1,1-bis-(4-hydroxy phenyl)-cyclohexane. These diphenols can be used not only alone but also in the form of a mixture. The main body of the polycarbonate used in the method of the present invention is polycarbonate obtained by the reaction of various dienol compounds as described above with phosgene or diphenyl carbonate, etc., but also various copolymers of polycarbonate, such as dioxydiaryl alkane. Mutual copolycarbonates, copolycarbonates of dioxydiarylalkane and other aromatic dioxy compounds, copolycarbonates of dioxydiarylalkane and aliphatic dioxy compounds, copolycarbonates of aromatic dioxy compounds other than dioxydiarylalkane , homobond copolymers such as copolycarbonates of aromatic dioxy compounds other than dioxydiarylalkane and aliphatic dioxy compounds, polycarbonates with ester bonds, polycarbonates with urethane bonds, and other heterobond copolymers. be able to. In the method of the present invention, a polycarbonate having a functional group represented by the general formula () bonded to the terminal position, particularly at both terminal positions, is used as a reaction raw material. This polycarbonate having a specific functional group at its terminal can be produced by various methods. For example, in the interfacial polycondensation method, in the reaction of diphenols dissolved in an alkaline aqueous solution and phosgene in the presence of an inert organic solvent, the general formula [In the formula, R, R ₁ and R ₂ are the same as above. ] It can be obtained by adding a substituted phenol represented by the following and further carrying out a polycondensation reaction in the presence of a tertiary amine as a polymerization catalyst. Here the general formula ()
Examples of substituted phenols represented by include p-isopropylphenol and m-isopropylphenol. At this time, the substituted phenol represented by the above general formula () acts as a molecular weight regulator for polycarbonate, and as a result,
A polycarbonate or an oligomer thereof having a specific functional group at the end and a desired degree of polymerization can be obtained. Here, for example, if a diphenol compound represented by the general formula () and a polycarbonate or its oligomer made from phosgene are used, and this is reacted with a substituted phenol represented by the general formula (), the resulting specific terminal group is Polycarbonate has the general formula It will be expressed as. In the formula, R, R ₁ , R ₂ ,
R′, Y ₁ , Y ₂ , a, b are the same as above,
Further, m indicates the degree of polymerization. The degree of polymerization m is not particularly limited and may be appropriately selected depending on the purpose of use of the polycarbonate copolymer finally obtained, but generally m = 2 to 100, preferably m = 4 to 100.
The range is 60. Next, there are various types of polyphenylene oxide to be reacted with the polycarbonate having the above-mentioned specific end groups, but usually it has the general formula [In the formula, R ₃ , R ₄ , R ₅ and R ₆ are hydrogen, halogen, substituted or unsubstituted hydrocarbon group, and R ₃
~R ₆ may be the same or different, but at least one is a methyl group. ] It is expressed as. The polyphenylene oxide represented by this general formula () has the following general formula [In the formula, R ₃ , R ₄ , R ₅ , and R ₆ are the same as above. ] It can be obtained by polymerization of phenols represented by the following. Examples of these phenols include 2,6-dimethylphenol, 2-methyl-6-ethylphenol, 2,6-diethylphenol, 2,6-diphenylphenol, 2-methyl-6-phenylphenol, 2- Methyl-6
-Chlorphenol, 2-ethyl-6-n-propylphenol, 2-methyl-6-bromophenol, 2-methyl-6-isopropylphenol, 2-methyl-6-methoxyphenol, 2-
Examples include methyl-6-n-butylphenol and 2-ethyl-6-chlorophenol. The polymerization of these phenols is carried out in the presence of an amino compound having at least one primary, secondary, or tertiary amino group in one molecule and a metal salt such as cuprous chloride as an oxidative polymerization catalyst. This is done by reacting phenols with oxygen. Aromatic or aliphatic hydrocarbons can be used as polymerization medium in this case. In the method of the present invention, this polymer, that is, polyphenylene oxide represented by the general formula (), is used as a reaction raw material and is reacted with the polycarbonate having the above-mentioned specific terminal group. Here, the degree of polymerization n in the general formula () representing polyphenylene oxide is generally n=
Although n=2 to 200, more preferably n=4 to 120. In the method of the present invention, it is necessary to react a polycarbonate having a specific terminal group as described above with polyphenylene oxide in the presence of a free radical generating means. There are various ways to generate free radicals, but usually include the presence of a free radical initiator in the reaction system, treatment with ozone or oxygen, or irradiation with ionizing radiation. Free radical initiators include, for example, benzoyl peroxide, lauryl peroxide, azobisisobutyronitrile,
Dicumyl peroxide, t-butyl hydroperoxide and the like are preferably used. Ionizing radiation may include α rays, β rays, γ rays, ultraviolet rays, X rays, etc. When irradiated with these, free radicals are generated in the reaction system and radical reactions proceed. For the reaction, add a polycarbonate with a specific end group, polyphenylene oxide, and a free radical initiator such as peroxide to the reaction system, or
This may be heated in a solvent or without a solvent while being treated with oxygen or ozone or irradiated with ultraviolet rays or the like. There is no particular restriction on the ratio of the reaction raw materials added to the reaction system, but usually polycarbonate having a specific end group and polyphenylene oxide are used, the former: the latter = 5 to 95: 95 to 5 (weight ratio), preferably 10-90:90-10 (weight ratio), and when using a free radical initiator, 0.001 part by weight or more per 100 parts by weight of both of the above reaction materials,
It should preferably be added in a proportion of 0.01 to 5 parts by weight. The reaction can be carried out in various ways such as a solution method or a solvent method. For example, when using a solution method,
It is sufficient to react at 70 to 200℃ for 1 minute to 2 hours.
On the other hand, when using the melting method, the reaction may proceed at a temperature of 180 to 300°C. If the reaction is carried out under the above-mentioned conditions, the functional group represented by the general formula () present at the end of the polycarbonate will be

[Production of isopropylphenol-terminated polycarbonate]

A polycarbonate oligomer containing a terminal chloroformate group was placed in one reaction vessel having a baffle plate.
100 g, 450 ml of methylene chloride solution containing 1.6 g of p-isopropylphenol, 2 of bisphenol A
150 ml of a normal aqueous sodium hydroxide solution and 50 mg of triethylamine were charged, and the reaction was carried out for 50 minutes while stirring at a rotation speed of 500 rpm. After the reaction was completed, the reaction mixture was diluted with 1 part of methylene chloride, 1.5 parts of water was added, and the mixture was stirred. After separating and removing the aqueous phase, washing was performed in the order of hydrochloric acid, water, aqueous caustic soda solution, and water. Thereafter, the organic phase was separated and methylene chloride was distilled off to obtain a self-colored powdery isopropylphenol-terminated polycarbonate. The reduced viscosity (ηSP/C) of this product is 0.59
(Chloroform 0.5g/dl at 30°C). Reference example 2 [Manufacture of polyphenylene oxide (a)] 10 2,6-dimethylphenol in a reaction vessel
1000 g, toluene 1700 ml, methanol 2500 ml, cuprous chloride 19 g and pyridine 190 ml were charged, and the reaction was carried out at room temperature for 3 hours while blowing oxygen gas at 1.5/min. After the reaction, the generated precipitate was separated into three parts and washed with methanol containing a small amount of hydrochloric acid.
It was dried to obtain polyphenyl oxide (a). The yield of this polymer was 87% and the number average molecular weight was 4800 (40 mer). Reference example 3 [Production of polyphenylene oxide (b)] 2,6-dimethylphenol 500g, toluene
According to Reference Example 2, polyphenylene oxide (b) was obtained using 2,000 ml of methanol, 1,000 ml of methanol, 30 g of cuprous chloride, and 300 ml of pyridine. Polymer yield 84
%, and the number average molecular weight was 7700 (64-mer). Example 1 15 g of isopropylphenol-terminated polycarbonate obtained in Reference Example 1, 5 g of polyphenylene oxide (a) obtained in Reference Example 2, 400 mg of dicumyl peroxide, and 200 ml of toluene were placed in an autoclave and heated at 135°C for 45 minutes. The reaction was carried out. After the reaction was completed, the mixture was precipitated in methanol, and the precipitate was collected and dried to obtain 15.5 g of a polycarbonate copolymer. The reduced viscosity (ηSP/C) of this product is 0.69
(30°C, chloroform 0.5 g/dl), and the polyphenylene oxide content was 26.7% by weight (NMR measurement). Note that 2 g of the produced polymer was dissolved in 30 ml of methylene chloride and left to stand for 6 hours, but no precipitate was found, confirming that there was no polyphenylene oxide homopolymer in the produced polymer. Example 2 15 g of isopropylphenol-terminated polycarbonate obtained in Reference Example 1, 4 g of polyphenylene oxide (B) obtained in Reference Example 3, 600 mg of dicumyl peroxide, and 200 ml of toluene were charged into an autoclave and heated at 140°C for 20 minutes. A heating reaction was carried out.
Polycarbonate copolymer 17.1 according to Example 1
I got g. The reduced viscosity (ηSP/C) of this material is
0.70 (30°C, chloroform 0.5 g/dl), and the polyphenylene oxide content was 22% by weight (NMR measurement). Note that no polyphenylene oxide homopolymer was observed in the produced polymer. Example 3 Using the polycarbonate copolymers obtained in Examples 1 and 2, 300μ
cast film was manufactured. This film was folded and immersed in acetone at room temperature, but no whitening occurred, and the film slightly whitened after 3 hours. On the other hand, when polycarbonate was similarly immersed, cracks appeared instantly.

Claims (1)

[Claims] 1. General formula [In the formula, R represents hydrogen or a desired substituent,
R ₁ and R ₂ each represent an alkyl group or an aryl group. ] A method for producing a polycarbonate copolymer, which comprises reacting a polycarbonate having a terminal group represented by the following with polyphenylene oxide through the intervention of a free radical generating means. 2 Polyphenylene oxide has the general formula [In the formula, R ₃ , R ₄ , R ₅ and R ₆ are hydrogen, a halogen-substituted or unsubstituted hydrocarbon group, and R ₃ -
R ₆ may be the same or different, but at least one is a methyl group. ] The manufacturing method according to claim 1, which is represented by: 3. The method according to claim 1, wherein the free radical generating means is the presence of a free radical initiator in the reaction system. 4. The method according to claim 1, wherein the free radical generating means uses ozone or oxygen. 5. The method according to claim 1, wherein the free radical generating means is irradiation with ionizing radiation.