JPS58101111A - Manufacture of polycarbonate copolymer - Google Patents

Abstract

PURPOSE:To obtain efficiently and in any desired composition titled copolymer of high heat and chemical resistance, by the reaction, in the presence of a free radical-generating action, between polyphenylene oxide and a polycarbonate having a specific terminal group. CONSTITUTION:The objective copolymer can be obtained by the reaction, on heating, between (A) a polycarbonate having a terminal group of formulaI(R is H, halogen, alkyl, etc.; R1 and R2 are each alkyl or allyl), prepared by the reaction of a diphenol compound with phosgene or diphenyl carbonate followed by the reaction with a substituted phenol and (B) a polyphenylene oxide of formula II (R3-R6 are each H, halogen, or hydrocarbon; however, at least one of those being methyl), prepared by the polymerization of a phenol compound, in a weight ratio A/B of 5-95/95-5, and in the presence of a free radical- generating action, e.g. a free radical initator.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a polycarbonate copolymer, and more particularly, the present invention relates to a method for producing a polycarbonate copolymer, and more particularly, a polycarbonate copolymer having a specific terminal group and a polyphenylene oxide are reacted in the presence of a free radical generating means to obtain a heat-resistant copolymer.

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.

Polycarbonate resins have traditionally been well known as engineering resins due to their excellent mechanical, thermal, and electrical properties, especially their impact resistance, and are often used in mechanical parts, electrical parts, and the like. However, polycarbonate resin is made of acetone.

Although it is a resin with excellent properties, its use and application fields are limited due to its inherent drawbacks, such as whitening and crazing when it comes into contact with heptane, carbon tetrachloride, etc., and cracking under stress. It was severely restricted. Additionally, this polycarbonate resin had drawbacks such as insufficient compatibility when blended with other thermoplastic resins such as polystyrene resins.To overcome these drawbacks, polyphenylene oxide was mechanically added to the polycarbonate resin. A method of mixing or a method of mixing as a solution has been proposed (Japanese Patent Publication No. 7G2).

However, this method has problems in that it is transparent to mere physical mixing 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 of polycarbonate and polyphenylene oxide and a method for producing the same (Patent Application Sho Sro-bt, SSB No. Specification).

The present inventors have conducted extensive research in order to develop a method that can produce a copolymer of polycarbonate and polyphenylene oxide more efficiently and at a desired copolymerization ratio. As a result, they discovered that the object could be achieved by using a polycarbonate having a specific functional group at the end and reacting it with polyphenylene oxide, thereby completing the present invention. That is, the present invention is based on the general formula [where R represents hydrogen or a desired substituent, and R and R2 each represent an alkyl group or an aryl group. ] Polycarbonate and polycarbonate having a terminal group represented by
The present invention provides a method for producing a polycarbonate copolymer, which is characterized by reacting phenylene oxide with the intervention of a free radical generating means.

As mentioned above, the polycarbonate used in the method of the present invention is
It must have a functional group represented by general formula (I) at its terminal. 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. Also,
R1+R2 are each an alkyl group such as a methyl group, an ethyl group, a propyl group, or an aryl group, but especially R
Most commonly, both 1+R2 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 phosdan or diphenyl carbonate are used. Here, the diphenol compound usually has one general formula (wherein R' is a substituted or unsubstituted alkylene group having carbon number/-4, -o-, -8-, -8o□- or -CO
- and - Ap, yl and Y2 are hydrogen or ).rodene atoms, and a and b are integers of /-1. ] can be given. Examples of the diphenol compounds represented by the above general formula (old or (m)) include '+,4''-dihydroxydiphenyl;>:2゜Hiro-bis-<tt-hydroxophenyl)-2-methylbutane; /, /-bis-(gu-hydroxyphenyl)-cyclohexane; α, α′-his-
(ll-hydroxyphenyl)-p-diisozolopylbenzene;S,2-bis-(3-methyl-q-hydroxyphenyl)-propane:X,X-bis-C3-chloro-
q-hydroxyphenyl)-soropane; bis-(3+3
=dimethyl-q-hydroxyphenyl)-methane;
2-bis-(3,5-dimethyl-guhydroxyphenyl)propane; bis-(4'-hydroxyphenyl)sulfone;bis-C3,!;-dimethyl-derhydroxyphenyl)sulfone;co,lI-bis-(3,S-dimethyl-q-hydroxyphenyl)-comethylbutane;
/,/-bis-(3,S-dimethyl-guhydroxyphenyl)-7chlorohexane;α,α'-bis-C3,3
-dimethyl-q-hydroxyphenyl)-p-diimprogylbenzene; co, 2-bis-<3. ! ;-dichloroq-hyroxyphenyl)-propane and co,2-
Bis-(3,S-dizolomoq-hydroxyphenyl)
-It is propane. Particularly preferred examples of diphenols include 2,2-bis-(4'-hydroxyphenyl)-zolopano:2,2-bis-(3,5-dimethyl-q-hydroxyphenyl)-zoronoden:2,2- Screw (3゜s-
dichloro-Hiro-hydroxyphenyl)-furopane;
2-bis-(3,S-dibromo-q-hydroxyphenyl)-propane and 0:/,/-bis-(4-hydroxyphenyl)-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 co-copolymers of dioxydiarylalkane with each other. Polycarbonate.

Copolycarbonates of dioxydiarylalkane and other aromatic dioxy compounds, copolycarbonates of dioxydiarylalkane and aliphatic dioxy compounds, copolycarbonates of aromatic dioxy compounds other than dioxydiarylalkane, dioxydiarylalkane A homobond copolymer such as a copolycarbonate of an aromatic dioxy compound and an aliphatic dioxy compound, or a polycarbonate having an ethyl bond.

Examples include polycarbonate having urethane bonds and other heterobond copolymers.

In the method of the present invention, the above-mentioned polycarbonate having a functional group represented by the general formula (I) bonded to the terminal position, particularly at both terminal positions, is used as a reaction raw material. Polycarbonate having a specific functional group at its terminal can be produced by various methods. For example, in the interfacial polycondensation method, in the presence of an inert organic solvent, the reaction between diphenols dissolved in an alkaline aqueous solution and phosgene is performed before the reaction.

During the reaction or after the completion of the reaction, the general formula R1 ■ [In the formula * R+ R1r R2 is the same as above. It can be obtained by adding a substituted phenol represented by the following formula and further carrying out a polycondensation reaction in the presence of a tertiary amine as a polymerization catalyst. Here, in the substituted phenol represented by the general formula (I~'), p-isopropylphenol, m-
Examples include isozolobylphenol. In this case, the substituted phenol represented by the above general formula (IV) acts as a molecular weight regulator for the polycarbonate, and as a result, a polycarbonate or an oligomer thereof having a specific functional group at the terminal and a desired degree of polymerization can be obtained. .

Here, for example, when a diphenol compound represented by the general formula (n) and a polycarbonate produced by phosde/hydrolysis or an oligomer thereof are reacted with a substituted phenol represented by the general formula (IV), the obtained Polycarbonates with specific terminal groups are represented by the general formula. In the formula, R+ R1+ R
2r RZYI I Y2 + a, l) is the same as above, and m indicates the degree of polymerization. This degree of polymerization m
is not particularly limited and may be selected appropriately depending on the purpose of use of the polycarbonate copolymer finally obtained.
Generally m = Coco-00, preferably m = 'I''
b In the range of O.

Next, there are various types of polyphenylene oxide to be reacted with the polycarbonate having the above-mentioned specific terminal group, but usually [wherein R3r R4+ R6 and R6 are hydrogen, /
% Op 7° is a substituted or unsubstituted hydrocarbon group,
”a-R.

may be the same or different, but at least one is a methyl group. ].

The polyphenylene oxide represented by this general formula (Vl) has the following general formula [wherein R31R41R51R6 is the same as above. ]
It can be obtained by polymerization of phenols represented by: Examples of these phenols include co,ro-dimethylphenol, 2-methyl-6-ethylphenol, 2,6-ethylphenol, 2,6-diphenylphenol, 2-methyl-6-phenylphenol,
2-Mef-1°-chlorophenol, 2-ethyl-A
-n-7'-pyrphenol, 2-methyl-6-bromophenol, cortacyl-6-isozorobylphenol.

Nimethyl-6-medoxyphenol, 2-methyl-A
-n-7" methylphenol, 2-ethyl-6-chlorophenol, etc. The polymerization of these phenols is carried out using one molecule of primary, secondary, and tertiary amine groups as oxidative polymerization catalysts. This is carried out by reacting phenols with oxygen in the presence of an amino compound having at least 7 molecules and a metal salt such as cuprous chloride.In this case, an aromatic or aliphatic hydrocarbon is used as the polymerization medium. and can be used.

In the method of the present invention, this polymer, that is, polyphenylene oxide represented by general formula (Vl), 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 (Vl) of polyphenylene oxide is generally n=coco-00, but preferably n
= 'I''/20.

In the method of the present invention, it is necessary to react a polycarbonate having a specific end 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, the reaction system is deprived of a free radical initiator, treated with ozone or oxygen, or irradiated with ionizing radiation. Free radical initiators include, for example, benzoyl peroxide, lauryl peroxide, azobisin butyronitrile.

Dicumyl peroxide, t-butyl hydroperoxide and the like are preferably used. Also, as ionizing radiation, α
Radicals, β-rays, γ-rays, ultraviolet rays, X-rays, etc. can be considered, and when these are irradiated, free radicals are generated in the reaction system, and the radical reaction proceeds.

For the reaction, polycarbonate and polyphenylene oxide with specific terminal groups and a free radical initiator such as peroxide are added to the reaction system, or they are treated with oxygen or ozone, or they are placed in a solvent while being irradiated with ultraviolet light, etc. Alternatively, it may be heated without a solvent. There is no particular restriction on the ratio of the reaction raw materials added to the reaction system, but usually polycarbonate and polyphenylene oxide having a specific end group are used: former: latter =! ;-95: 9! ; −
1-(weight ratio), preferably 10-90:9O-1
0 (weight ratio), and if a free radical initiator is used, it should be added at a ratio of 0.001 parts by weight or more, preferably 0.0/-5 parts by weight, per 100 parts by weight of both of the above reaction materials. It is.

The reaction can be carried out in various ways, such as a solution method or a melt method. For example, in the case of a solution method, the reaction temperature
The reaction may be carried out at C for a time of 1 minute to 1 hour; on the other hand, in the case of a melting method, the reaction may be carried out at a temperature of 7g0 to 30,000°C.

When the reaction is carried out under the above-mentioned conditions, the 2-refin oxide represented by the general formula (I) present at the terminal end of the polycarbonate is bonded from an appropriate position to form a block copolymer or graft copolymer of polycarbonate and polyolefin oxide. Combination etc. can be obtained.

The reaction to produce the copolymer of polycarbonate and polyolefin oxide described above proceeds very smoothly because a specific functional group is introduced at the end of the polycarbonate and is carried out with the intervention of a free radical generating means. At the same time, it is possible to freely control the degree of polymerization of each component polymer in the resulting copolymer. This is because the polycarbonate used has a specific functional group at the end as shown in the general formula (V), so there is almost no polymerization between polycarbonates in the above copolymerization reaction, and therefore the degree of polymerization m of the polycarbonate is low. This is because it is maintained unchanged even in the copolymer. Therefore, by appropriately selecting the degree of polymerization m of the polycarbonate having a specific end group as a reaction raw material, a copolymer of each component polymer having a desired degree of polymerization can be freely obtained.

The thus obtained polycarbonate copolymer of the present invention retains the excellent properties of polycarbonate resins and overcomes the essential drawbacks of polycarbonate resins. This improves solvent resistance and alkali resistance, as well as good compatibility with other resins. Furthermore, as well as improving heat resistance and flame resistance, film formability and moldability are significantly improved, and it can be effectively used in an extremely wide range of fields ranging from mechanical parts of electrical products to daily necessities.

Next, the present invention will be explained in more detail using examples.

Reference Example/[Manufacture of isozologylphenol-terminated polycarbonate] A polycarbonate oligomer containing a terminal chloroformate group was placed in a /l reaction vessel equipped with a baffle plate. i
+ To p-inzologylphenol, 1150 ml of methylene chloride solution containing l, g, 30 ml of bisphenol A aqueous solution of normal caustic soda, and 50~ of triethylamine were charged, and the number of revolutions was 50 Or, p, m.
The reaction was carried out for a minute with stirring under SO.

After the reaction is complete, the reaction mixture is diluted with methylene chloride/l,
Water i and st were added and 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 white powdery isopropylphenol-terminated polycarbonate. Reduced viscosity of this material (ηsp/c
) was 0.59<30°C chloroform 0.3g/a').

Reference example [Manufacture of polyphenylene oxide 0] 10t
1000 g of 2,6-dimetherphenol in the reaction vessel,
Toluene/700ml1. ) Tar/- tar 2300m1. Prepare cupric chloride/qg and pyridine/90al, and oxygen is swo/-! ; t/r+n++ tD The reaction was carried out at room temperature for 3 hours while blowing. After the reaction, the resulting precipitate was separated into three parts, washed with methanol containing a small amount of hydrochloric acid, and dried to obtain polyphenyl oxide 0). Yield of this polymer g7%, number average molecular weight 'Ig00 (tI
O-mer).

Reference Example 3 [Production of polyphenylene oxide←] 2.6
-dimethylphenol soog, toluene 2000 m
Polyphenylene oxide ←) was obtained according to Reference Example 1 using 1 + Mep / -L / 000 ml + 30 ml of cuprous chloride and 300 ml of pyridine. Polymer yield gtt%, number average molecular weight? '70 QC6 tetramer).

Isopropylphenol-terminated polycarbonate obtained in Example/Reference Example/! ; g, polyphenylene oxide H) obtained in Reference Example - 5 g, dicumyl peroxide 00
... and 200 ml of toluene were charged into an autoclave, and a heating reaction was carried out at 735° C. for 1 LtS minutes. After the reaction was completed, the mixture was precipitated in methanol, and the precipitate was taken out and dried to obtain 5.5 g' of polycarbonate copolymer. The reduced viscosity (ηSP/C') of this product was 0.69 (30%, chloroform 0.!; ,!i'/sold), and the polyphenylene oxide content was 26.7% by weight (NMR measurement). Note that 2 g of the produced polymer was dissolved in 39 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.

Isopropylphenol-terminated polycarbonate obtained in Example/Reference Example/! ; 9. Polyphenylene oxide obtained in Reference Example 3←H', 9. Dicumyl peroxide Otsu 00
my, and 200 ml of toluene were placed in an autoclave and a heating reaction was carried out at 110°C for 20 minutes. Polycarbonate copolymer according to Example/7. /
I got g. The reduced viscosity (ηSP/C) of this product is 0.7
0 (30°C, chloroform 0,!; g/dll),
The polyphenylene oxide-containing fc was 22% by weight (NMR measurement). Note that no polyphenylene oxide homopolymer was observed in the produced polymer.

Example 3 Using the polycarbonate copolymer obtained in Examples 1 and 2, a 300 μm cast film was produced from a chloroform solution. 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.

Patent applicant: Idemitsu Kosan Co., Ltd. Representative Patent Attorney Kubo 1) Fujibe

Claims (1)

[Claims] l. General formula [wherein R represents hydrogen or a desired substituent, and R1 and R2 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 [in the formula s R3+ R4+ R5 and R6 are hydrogen or halogen. A substituted or unsubstituted hydrocarbon group represented by R3-1 (6 may be the same or different, but at least 7 are methyl groups) 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 is ozone or 5. The method according to claim 1, wherein oxygen is used. 5. The method according to claim 1, wherein the free radical generating means is irradiation with ionizing radiation.