JPS58101112A - Manufacture of polycarbonate copolymer - Google Patents

Abstract

PURPOSE:To obtain efficiently and in any desired composition titled copolymer of high heat and chemical resistance and mechanical strength, by the reaction, in the presence of a free radical-generating action, between a specific polymer 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 formula (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 polymer having a tertiary carbon atom (e.g. polystyrene) in a weight ratio A/B of 20-95/80-5, and in the presence of a free radical-generating action, e.g. a free radical initiator (e.g. dicumyl peroxide).

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, a polycarbonate having a specific terminal group and a polymer having a tertiary carbon atom such as polystyrene are combined with a free radical generating means. Heat resistance, by reacting with the intervention of
The present invention relates to a method for efficiently producing a polycarbonate copolymer having excellent chemical resistance, mechanical strength, etc., as well as good moldability, transparency, 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, this polycarbonate resin has inherent drawbacks such as being relatively expensive, having poor moldability, insufficient solvent resistance, and being prone to cracking under stress. Although it is a resin that has properties, its utilization.

The field of application was severely limited. For this reason, attempts have been made to modify the material by blending it with other thermoplastic resins, but
Since the compatibility with polyzolopyrene, polystyrene, polymethyl acrylate, etc. is insufficient, the resulting blend is unsatisfactory, with loss of transparency and low mechanical strength.

In order to eliminate these drawbacks, a method for producing a graft copolymer has been proposed in which vinyl polymer units are grafted onto polycarbonate resin (Tokuko Show acrylic acid esters,
This method uses styrene monomer, which has major disadvantages in that it is complicated to operate and cannot be applied to other resins.

The purpose of the present invention is to overcome the drawbacks of the above-mentioned conventional techniques and to develop a method that can efficiently produce polycarbonate copolymers with excellent various physical properties and at desired copolymerization ratios. It has the following structure: [wherein R is hydrogen or a desired substituent, Ro and 8 each represent an alkyl group or an aryl group. ] This is a method for producing a polycarbonate copolymer, which comprises reacting a polycarbonate having a terminal group represented by the following with a polymer having a tertiary carbon atom through the intervention of a free radical generating means.

The polycarbonate used in the method of the present invention is as described above.
It must have a functional group represented by the general formula (1) at its lower 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. Further, R1 and R2 are each an alkyl group such as a methyl group, an ethyl group, or a propyl group, or an aryl group, and it is most common that R, R2 are both 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 % formula % (2) general formula (Yl) (Y2) b [wherein R' is a substituted or unsubstituted alkylene group with carbon number/~S, -〇 -, -s -, -5o2- or -C○
-, Yl and Y2 are hydrogen or ).rodene atoms, and a and b are integers of /~. ] can be given. Examples of the diphenol compounds represented by the above general formula (II) or (2) include <z, +'-dihydroxydiphenyl;2.
, l-bis-(couhydroxyphenyl)-f-ropanes
'(Bisphenol A): 2゜9-bis-(4'-hydroxyphenyl)-J-methylbutane; /, /-bis-
(4'-hydroxyphenyl)-cyclohexane; α,
α'-bis-(terhydroxyphenyl)-P-diisozolobylbenzene; 2-bis-(3-methyl-9-
hydroxyphenyl)-propane; 2,2-bis-<3
-Chloroder-hydroxyphenyl)-propane; bis-(3,S-dimethyl-derhydroxyphenyl)-methane; 2-bis-(3,s-dimethyl-q-hydroxyphenyl)propane; bis=(4t-hydroxyphenyl) ) sulfone; bis-(3,S-dimethyl-q-hydroxyphenyl)sulfone; x, p-bis-(3,5
-dimethyl-9-hydroxyphenyl)-11methylbutane; /, /-bis-(3,S-dimethyl-guhydroxyphenyl)-cyclohexane; α, α′-bis-(
3,S-dimethyl-guhydroxyphenyl)-P-diisozolobylbenzene:X,,2-bis-(3,!;-
dichloro-q-hydroxyphenyl)-propane and co-1,2-bis#(3+!;-Schiff').

mogu hydroxyphenyl)-furopane.

An example of a particularly preferable diphenol is Kotsu 2-bis-(q
-hydroxyphenyl)-propane; 2. ．． 2-bis-C3,! ;-dimethyl-derhydroxyphenyl)-
Propane; Co, Corbis-(3,S-cyclorhoda-hydroxyphenyl)-propane; Kot 2-bis-(3,
S-dibromo-q-hydroxyphenyl)-propane and H/,/-bis-(terhydroxyphenyl)-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 genol 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 Homobond copolymers such as copolycarbonates of other aromatic dioxy compounds and aliphatic dioxy compounds, or polycarbonates having ester bonds.

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 (1) 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 presence of an inert organic solvent, in the reaction of diphenols dissolved in an alkaline aqueous solution with phosgene, the general formula [wherein R, R1, and R2 are Same as. 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. Examples of the substituted phenol represented by the general formula (2) include p-inopropylphenol and 9m-isozorobylphenol. At this time, the substituted phenol represented by the general formula N 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 (II) and a polycarbonate or its oricamer made from phosgene are used and this is reacted with a substituted phenol represented by the general formula (■), the resulting specific terminal The polycarbonate having groups is represented by the general formula. In the formula, R, R1, R2, R'
.

Yl, Y2, a, and b are the same as above, and m determines the degree of polymerization. This 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 in general, m=
a~100. Preferably m is in the range of 9-40.

Next, the polymer to be reacted with the polycarbonate having the above specific end group is not particularly limited as long as it has a tertiary carbon atom in the molecule, and is determined as appropriate depending on the use of the copolymer to be produced. That's fine.

Suitable examples of polymers having tertiary carbon atoms include polystyrene and polymethyl acrylate.

Ethyl polyacrylate, butyl polyacrylate.

Examples include vinyl polymers such as polyacrylonitrile, polypropylene, acrylonitrile-styrene copolymer, styrene-butadiene block copolymer, acrylonitrile-butadiene-styrene copolymer, and styrene-butadiene rubber.

In the method of the present invention, this polymer, that is, a polymer having a tertiary carbon atom, is used as a reaction raw material and is reacted with a polycarbonate having the above-mentioned specific end group. In this case, it is necessary to cause the two to react with the intervention of a free radical generating means. There are various means for generating free radicals, but usually these 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. In addition, ionizing radiation includes alpha rays and beta rays.

Possible sources include γ-rays, ultraviolet rays, and X-rays, and when these are irradiated, free radicals are generated in the reaction system and the radical reaction proceeds.

During the reaction, a polycarbonate with a specific end group, a polymer with a tertiary carbon atom, and a free radical initiator such as peroxide are added to the reaction system, or the reaction system is treated with oxygen or ozone, or irradiated with ultraviolet light, etc. However, it may be heated in a solvent or without a solvent. 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 a polymer having a tertiary carbon atom are mixed into the former: -20 to 9 g of the latter.
O~S (weight ratio), preferably qO~90:Iri θ~1
0 (weight ratio), and if a free radical initiator is used, it should be added at a ratio of 0.007 parts by weight or more, preferably 0.07 to 5 parts by weight, per 100 parts by weight of both reaction materials. be.

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 temperature is 70 to 200°C.
The reaction may be carried out at a temperature of 7 gO to 300° C. for a time period of from 7 gO to 300° C. when the melting method is used. Further, in the case of a solution method, the reaction may be carried out using a monomer of this polymer instead of a polymer having a tertiary carbon atom.

If the reaction is carried out under the above-mentioned conditions, the polymer having the functional 2 carbon atoms represented by the general formula (1) present at the terminals of the polycarbonate is bonded from an appropriate position, and the polycarbonate and the polymer having the tertiary carbon atom are formed. A block copolymer or a graft copolymer/copolymer with the polymer can be obtained.

The above-mentioned reaction for producing a copolymer of polycarbonate and a polymer having a tertiary carbon atom involves introducing a specific functional group into the terminal end of the polycarbonate, and is carried out with the intervention of a free radical generating means. The process proceeds very smoothly, and 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 general formula (as shown in Therefore, if the degree of polymerization m of the polycarbonate having a specific terminal group, which is a reaction raw material, is appropriately selected, a copolymer of each component polymer with a desired degree of polymerization can be obtained. can be obtained freely.

The thus obtained polycarbonate copolymer of the present invention retains the excellent properties of polycarbonate resins, improves solvent resistance and alkali resistance, which are the essential drawbacks of polycarbonate resins, and has improved compatibility with other resins. It improves solubility. Furthermore, as well as improving heat resistance and mechanical strength, it also has good fluidity, excellent moldability, and high transparency, so it can be used as an additive for improving electrical products, 2 mechanical parts, daily miscellaneous goods, and even different polymer blends. It can be effectively used in an extremely wide range of fields.

Next, the present invention will be explained in more detail with reference to Examples.

Reference Example/[Manufacture of inopropylphenol-terminated polycarbonate] Polycarbonate oligomer 1009 containing terminal chloroformate groups was placed in a -e capacity reaction vessel equipped with a baffle plate.
-Methylene chloride solution containing inzolobylphenol-
! ;Om1. Bisphenol A aqueous solution of caustic soda/! ; Charge Oml and triethylamine SO~, and increase the rotation speed to goor.

p. m. The reaction was carried out for a minute with stirring under SO.

Dilute with water/. S! was added and stirred. After separating and removing the aqueous phase, the mixture was washed with water, a caustic soda aqueous solution, and water in this order. Thereafter, the organic phase was separated and methylene chloride was distilled off to obtain a white powdery isozolobyl phenol-terminated polycarbonate. Reduced viscosity of this material (ηsp/C
) is 0. ! ; 9 (30℃ chloroform 0.!;
g/d swamp).

10 g of isopropylphenol-terminated polycarbonate obtained in Example/Reference Example/, 1 GP polystyrene (M engineering 4t)
09.Pour dicumyl peroxide oom9 and 200 ml of toluene into an autoclave and heat at 730°C.
A thermal reaction was carried out for qs minutes. After the reaction is completed, it is precipitated in methanol, the precipitate is collected, and cyclohexane is added. After thorough washing with water to remove unreacted polystyrene, drying was performed to obtain a polycarbonate copolymer/0.79. The reduced viscosity (ηsp/c) of this product is 0. g3
(30℃, chloroform, 0!; 9/d43
), polystyrene content (wt%) (NMR measurement)
Met. Using this copolymer, 230℃, 700℃
/Cm2 for 70 minutes, a sheet with good transparency was obtained.

Example = Isopropylphenol-terminated polycarbonate obtained in Reference Example/! ;9, Gp polystyrene (MIII)
, 2S9, dicumyl peroxide Oomy, and 200 ml of toluene were placed in an autoclave, and a heating reaction was carried out at 730° C. for 0 minutes. The following operations are carried out according to Examples/Polycarbonate copolymer! ;． 3 g was obtained. The reduced viscosity (ηsp/C) of this material is 0.92 (
30°C1 chloroform, 0,! ;9/aA),
The polystyrene content was 9.3% by weight (NMR measurement). When this copolymer was press-molded in the same manner, a sheet with good transparency was obtained.

Example 3 Isozologylphenol-terminated polycarbonate obtained in Reference Example/), tg, HI polystyrene (Ml.2
) 5 g of dicumyl peroxide and 200 ml of toluene were placed in an autoclave.
A heating reaction was carried out at 0°C for 10 minutes. The following operations were carried out in accordance with Example 1 to prepare polycarbonate copolymer g. / 9
I got it. The HI polystyrene content of this is 72
．． It was 2% by weight (NMR measurement).

Using this copolymer, 250'C%/00
Press molding was carried out under the conditions of ky/cwr2 and 10 minutes to obtain a film with a thickness of 220μ. The tensile strength at break of this product was SgOkg/cm2. If a film with the same thickness as above is made of polycarbonate, its tensile strength at break is 1.3 kg/cm2, which is HI.
When it was made of polystyrene, it was 35θkg/cm2.

Reference Example [Production of isopropylphenol-terminated polyester polycarbonate] Bis7E/-/l/A/! ; 9 (0.05 g mol) in a standard NaOH aqueous solution/θQ
ml and isophthalic acid chloride'l 9
(0.039'I mol), terephthalic acid chloride'I g (0.039'I mol)
)2! ; O Ill dissolved in methylene chloride was mixed and reacted at 20° C. for about 30 seconds. The above reaction mixture contains polycarbonate oligomer containing a terminal chloroformate group and 0.9% of isozolobylphenol! ;
A methylene chloride solution containing Q was added, and somy triethylamine was further added, stirred vigorously, and reacted at 2g°C for 7 hours. The reaction mixture was then diluted with 10θrul of methylene chloride, washed with water/, S1.0.0/normal hydrochloric acid, and the organic layer was concentrated and reprecipitated in acetone to obtain white flaky isozorobyl phenol-terminated polyester polycarbonate. I got it. Reduced viscosity (ηsp
/C) 0-'I 1s (3θ℃, chloroform 0.!
; g/a 廓) and the ester/carbonate ratio is! ;0/! ; It was 0.

Example q 10 g of isozorogylphenol-terminated polyester polycarbonate obtained in the above reference example, 10 g of GP-polystyrene (MIII), 0.69 g of dicumyl peroxide
was added to xylene 2SOd and heated to 130% in an autoclave.
The mixture was heated and stirred at ℃ for 50 minutes. After the reaction was completed, it was precipitated with methanol. Next, the precipitated polymer was purified with P and thoroughly washed with cyclohexane/-e to remove unreacted polystyrene to obtain a polyester polycarbonate copolymer. The polystyrene content of the kernel is /q, θ weight To (NMR measurement)
Met.

Example S Inglovirphenol-terminated polycarbonate Sg obtained in Reference Example/200ml of styrene monomer. Pour dicumyl peroxide 3009 into an autoclave/
A heating reaction was carried out at 3S°C for 25 minutes with stirring. The reaction mixture was precipitated in methanol, and the precipitate was dissolved in 39 mt of dry methylene chloride, followed by cyclohexane! 001f
The polycarginate copolymer 27 is reprecipitated in Ll and dried.
．． I got 39. Reduced viscosity of this material (ηsp/C) /
/i0. ! ; / (30°C1 chloroform, 0.!
; 9/a13), g IJ styrene content 36.7
% by weight (NMR measurement).

Patent applicant: Idemitsu Kosan Co., Ltd. Agent: Patent attorney Fujibe Kubota

Claims (1)

[Claims] 1. General formula [wherein R represents hydrogen or a desired substituent, and R2 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 a polymer having a tertiary carbon atom through the intervention of a free radical generating means. 2. The polymer having a tertiary carbon atom is polystyrene,
Polymethyl acrylate, polyethyl acrylate, polymethyl acrylate, polyacrylonitrile, polyprogylene, acrylonitrile-styrene copolymer, styrene
The method according to claim 1, which is a butadiene block copolymer, an acrylonitrile-butadiene-styrene copolymer, or a styrene-butadiene rubber. 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.