JPS5925817A - Preparation of polycarbonate resin - Google Patents

Abstract

PURPOSE:To provide the titled resin having a free radical initiating group in the main chain, and suitable for the preparation of a block copolymer, by reacting a dihydric phenolic compound with a carbonate precursor in the presence of a specific bifunctional compound. CONSTITUTION:The objective resin can be prepared by reacting (A) a dihydric phenolic compound (preferably bisphenol A, etc.) with (B) a carbonate precursor (e.g. phosgene) in the presence of (C) a bifunctional compound having -N=N- group or -O-O- group (preferably an azo compound such as azobiscyanovalerianic acid). The amount of the component (C) is preferably 0.01-0.1mol per 1mol of the component (A). EFFECT:A block copolymer containing a block having arbitrary desired length can be prepared without producing a vinyl homopolymer nor producing the gel of e.g. graft polymer.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a polycarbonate-based resin, and more particularly to a method for producing a polycarbonate-based resin having mainly free radical initiation groups that can be used for producing a polycarbonate-based block copolymer.

Polycarbonate resin has excellent mechanical properties.

Because it has electrical properties, it has been used in many fields as an engineering resin.

Furthermore, in order to expand the field of use of polycarbonate resins, it has recently been proposed to graft copolymerize polycarbonate resins with polymerizable monomers. For example, (1) a method of grafting vinyl monomers onto polycarbonate in the presence of a free radical initiator (Japanese Patent Publication No. 47-7S751
No.), ■ A method of obtaining a terminally unsaturated polycarbonate using a -valent unsaturated compound as a molecular weight modifier, and addition-polymerizing this with G-vinyl monow-1 (Japanese Patent Publication No. 4B-25076, Japanese Patent Application Laid-open No. 1986-55- 50009), a copolymer with a compound having a Miwokoazo group on the ■ side (method of graft polymerizing a vinyl monomer (Makromol, Ohem, 1)
80, pp. 609-614 (1979)).

However, method (1) has the disadvantage that the grafting rate is low, and methods (2) and (3) tend to cause gelation. Moreover, all of the conventional proposals relate to graft copolymers of polycarbonate resins, and block copolymers cannot be obtained. However, the prior art has a major drawback in that a homopolymer of vinyl monomer is inevitably produced together with the graft copolymer.

An object of the present invention is to provide a method for producing a polycarbonate resin that can be used for producing a polycarbonate block copolymer.

In other words, the present invention provides a method for producing a polycarbonate resin from a dihydric phenol compound and a carbonate precursor, in which a bifunctional compound having an -N=N- group or a 10-0- group in the molecular main chain is used. The present invention relates to a method for producing a polycarbonate resin having a free radical initiating group in its main chain, which is characterized by adding a free radical initiating group to the main chain.

Here, the dihydric phenol compound is usually of the general formula [where n' is a substituted or unsubstituted alkylene group having 1 to 5 prime numbers, -o-, -s-, -5o2- or -
00-, Y and Y2 are hydrogen, an A/mer group or a halogen atom, and a and b are integers of 1 to 4.

] We can list the following expressions. Examples of the dihydric phenol compounds represented by the above general formula (I) or (Company) include 4,4'-dihydroxydiphenyl; 2,2-bis-(4-hydroxyphenyl)-propane (bisphenol A); 2+4-bis-(4-hydroxyphenyl)-2-methylbutane; +, 1-bis-
(4-hydroxyphenyl)-cyclohexane; α, α
'-Bis-(4-hydroxyphenyl)-p-diisopropylbenzene: 2.2-bis-(5-methyl-4-hydroxyphenyl)-propane; 2.2-bis-(3-
Chloro-4-hydroxyphenyl)-propane; bis-
(6,5-dimethyl-4-human112xyphenyl)-
Methane; 2,2-bis-(5,5-dimethyl-4-hydroxyphenyl)propane; Bis-(4-hydroxyphenyl) sulfone; Bis-(5,s-dimethyl-4-hydroxyphenyl) sulfone: 2I 4 -bis-(5,
5-dimethyl-4-hydroxyphenyl)-2-methylbutane; 1,1-bis-(5,5-dimethyl-4-hydroxyphenyl)-cyclohexane; α, α′-bis-
(!1,5-dimethyl-4-hydrodiphenyl)-p
-diisozolobylbenzene; 2,2-bis-(5,5-
dichloro-4-hydroxyphenyl)-propane and 2,2-bis-(5,5-dibromo-4-hydroxyphenyl)-propane. % (Example of this preferred dihydric phenol u2,2-bis-(4-hydroxyphenyl)
-Propane; 2,2-bis-(6,5-dimethyl-4-
Hydroxyphenyl)-propane: 2,2-bis-(5
゜5-dichloro-4-hydroxyphenyl)-propane; with 2,2-bis-(3,5-dibromo-4=hydroxyphenyl)-propane and 1,1-bis-(4-hydroxyphenyl)-cyclohexane be.

These dihydric phenols can be used not only alone but also in the form of a mixture.

Next, the carbonate precursor is not particularly limited as long as it can react with the dihydric phenol compound to obtain polycarbonate, and any carbonate precursor can be used depending on the method for producing polycarbonate. Examples of these carbonate precursors include phosgene, chloroformate group-containing dihydric phenol compounds, and oligomers thereof.

The present invention is based on the conventionally known interfacial polymerization method, polyproformate method,
In polycarbonate production methods using solution methods such as the pyridine method, -N-N- groups or
A difunctional compound having a group is added.

For example, in the interfacial polymerization method, when dihydric phenols dissolved in an alkaline aqueous solution are reacted with phosgene in the presence of an inert organic solvent, the difunctional compound is added before or during the reaction, and after the reaction, an amine-based catalyst is added. It can be produced by performing interfacial polycondensation in the presence of. In addition, the difunctional compound may be added before or during the reaction between an organic solvent solution of an oligomer containing a terminal chloroformate group obtained in advance by the reaction of a dihydric phenol compound and phosgene, and an alkaline aqueous solution of a dihydric phenol compound. It can also be produced by carrying out polycondensation. Alternatively, the polycarbonate can be produced directly by dissolving the dihydric phenol compound and the difunctional compound in pyridine or pyridine and an inert organic solvent, and then blowing phosgene into this solution.

The polycarbonate W obtained in the present invention is not limited to the polycarbonate obtained from these dihydric phenols and phosgene, but can also contain different dihydric phenol compounds, dihydric phenols and other aromatic or aliphatic dioxy compounds, etc. It includes copolymers such as homobond copolymers or polyester polycarbonates having ester bonds, polycarbonates having urethane bonds, and polycarbonates having heterobonds.

Next, as a bifunctional compound having a -N-N- group or a 10-0- group in the molecular main chain, a compound having a -N=N- group has the general formula (where X is a hydroxyl group or a carboxyl group). , halogen atom,
It represents an acid halide, and R' and R' represent a lower alkyl group, hydrogen or a nitrile group. ), specific examples include azobiscyanovaleric acid, azobiscyanohebutanoic acid, azobismethylpropionic acid, azobiscaprylic acid, azobispropylhebutane lvl, and halogenated products thereof. [Here, R1 and R2 represent hydrogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted phenyl group, or a substituted or unsubstituted aralkyl group, and M represents hydrogen or a metal.

) and their salts, specifically 2,2'-azobis(2-ethyl-4-methoxyvaleric acid), 2,2'-azobis(2-cyclobutylpropionic acid), 2.2'-azobis(2-phenylacetic acid) and their Na.

There are metal salts such as K.

In addition, examples of compounds having -0-0- groups include dioxymethyl peroxide, di(1-oxyethyl)
Parooxide, (1 -oxyeheptyl) parooxide, (1 -oxydecyl) parooxide, (1 -oxychrohexyl) parooxide, (1 -oxybenzyl) parooxide, ji (1 -o'clock 2.2.2.2- )
dichloroethyl) peroxide, di(1-oxy-1-
There are peroxides such as (methoxycarbonylmethyl) peroxide. Among them, it is preferable to use azo compounds.

The number of additives of these difunctional compounds may be appropriately determined depending on the molecular weight and content per molecule of the polycarbonate resin, but usually [101 to n2 moles, preferably [ It may be added in the range of LQl to 11 moles.

In the present invention, in addition to the above-mentioned components, molecular weight regulators such as phenol, p-tert-butylphenol and isopropylphenol, catalysts such as triethylamine, etc. can be added to the reaction system as appropriate. Further, as the inert organic solvent, methylene chloride, chlorobenzene, tetrachloroethane, etc. are used.

The invention! ! ! ! The polycarbonate resin obtained by this method is a novel polycarbonate having a G-N-N- group or a 10-0- group in the molecular main chain, and one example is as shown in the following formula. .

(Here, R is a substituted or unsubstituted alkylene group having 1 to 5 carbon atoms + −〇v ”' r −00−+(R
) o-, Yl and Y are hydrogen, an alkyl group or a halogen atom, and a and b are integers from 1 to 4,
2 represents a residue of a bifunctional compound containing a -N=N- group or a 10-0- group, m and n are integers of 10 to 200, and p is an integer of 1 to 10. )Moreover, G To be concretely shown, there is one expressed by the following formula.

(Here, m and n are 10 to 200. p is an integer of 1 to 1°.) The polycarbonate resin obtained in the present invention has -N=N- groups or 10-0 in the molecular chain. - group, is easily decomposed by heating, and can be used as a radical initiator in the polymerization of polymerizable monomers. Therefore, for example, in the presence of a vinyl heptamer (heating), a block copolymer in which a vinyl polymer is bonded to the terminal end of a polycarbonate via a free radical initiator residue can be obtained. Compared to conventional manufacturing methods, there is almost no production of vinyl homopolymer, and there is no risk of gelation of grafted poly(Y), and the block length can be adjusted arbitrarily. It has this major feature.

Next, the present invention will be explained by referring to examples.

Example 1 A reaction vessel of 1 volume with baffles (this bisphenol A
and a methylene chloride solution of a chloroformate group-containing polycarbonate oligomer prepared from phosgene.
Lt (concentration + + Of/ /' + number average molecular lid 6o
o), Azobiscyanovaleric acid 2? 2N caustic soda aqueous solution 20it7. ) 25 g of diethylamine was charged and the reaction was carried out at 5°C for 50 minutes with stirring at 400°C.

Next, this reaction mixture was added with 75 il of a 2N aqueous sodium hydroxide solution of 7.931 bisphenol A, 60 d of water and p
-Tertiary-butylphenol 0.5? A methylene chloride solution was added thereto, and the reaction was carried out for 5 minutes under the same reaction conditions.

After the reaction is completed, dilute with +oooIl/methylene chloride,
15Ull+/ of water was added and stirred. After that, after separating the aqueous phase, α01 normal caustic soda aqueous solution, water and α0
Washing was performed in the order of 1N hydrochloric acid aqueous solution.

Next, the organic phase was separated and reprecipitated in acetone to obtain a powdered polycarbonate resin. The resulting polycarbonate resin had a reduced viscosity ηsp/c of 1.27 (viscosity average molecular weight according to polycarbonate: 41,700). Further, the nitrogen content measured by chemiluminescence nitrogen analysis was 5000μ.

This polycarbonate resin was dissolved in chlorobenzene and refluxed for 5 hours to decompose the azo groups in the resin. The reduced viscosity of polycarbonate resin after decomposition is α8
67 (viscosity average molecule according to polycarbonate @276
00). Note that the reduced viscosity is [L5ff/1oo
It was measured under the conditions of WLl methylene chloride and 20''C. From this result, it is clear that the polycarbonate resin contains an azo group.

Example 2 A methylene chloride solution of the polycarbonate oligomer used in Example 1 was prepared using a reaction vessel with a baffle plate and a volume of 450 g.
d, 2N caustic soda aqueous solution of bisphenol A I A8 P 1501! /, 18N caustic soda water Wj liquid +
2wt, p-tert-butylphenol! 14
Prepare 5ψ methylene chloride solution and azobiscyanovaleric acid chloride 41, and incubate 40Q for 50 minutes at 5°C.
The reaction was carried out with stirring at rpH.

After the reaction was completed, washing and reprecipitation were performed in the same manner as in Example 1 and above to obtain a polycarbonate resin. The reduced viscosity of the obtained polycarbonate resin was rL813 (viscosity average molecule @5
51oo). In addition, the nitrogen-containing lid was 4600 kg.

Next, the reduced viscosity of the decomposed polycarbonate resin according to Example 1 was determined to be L48o (viscosity average molecular company + 96oO). From this result, it is clear that the polycarbonate resin contains a G-coazo group.

Reference Example The polycarbonate resin (PO) obtained in Example 2 and styrene (S) were mixed in a potion of po/s = 6/+ 00 (
Unit 1) was prepared and the reaction was carried out at BOoC for 4 hours.

As a result, block copolymer (
Reduced viscosity 1.10! 1, po@臘15%) was obtained. Further, the reduced viscosity of polystyrene after treating the produced block copolymer with KOH to decompose and remove the polycarbonate blocks was [1887]. on the other hand,
The reaction product was extracted with cyclohexane, and the manufacturer of styrene homopoly Y- was investigated, and the extraction rate was 16.7% by weight.

Note that test pieces were prepared by injection molding this block copolymer at a molding temperature of 260°C, and physical properties were measured. In addition, for specific softness, test pieces were obtained by molding polycarbonate (PC), polystyrene (PS), and blends thereof, and their physical properties were measured. The results are shown in Table 1.

As is clear from Table 1, the products of Comparative Example 5 and Reference Example, which are mechanical blends, have significantly superior strength.

Patent applicant: Idemitsu Kosan Co., Ltd. Procedural amendment (voluntary) August 31, 1982 Patent Chief Kazuo Wakasugi 1. Display of incident % Gansho 57156096 2 Name of the invention Manufacturing method of polycarbonate resin & person making corrections Relationship to the case Patent applicant Idemitsu Kosan Co., Ltd. 4. Agent Issue 04 1-1-10 Kyobashi, Chuo-ku, Tokyo 5 Target of correction Detailed description of the invention in the specification 1- 6. Contents of amendment Formula in the middle of page 11 of the specification Correct as follows.

(that's all) 2-

Claims (1)

[Claims] A method for producing a polycarbonate resin from a dihydric phenol compound and a carbonate precursor, characterized by adding a bifunctional compound having -N=N- group or 10-0- group in the molecular main chain. A method for producing a polycarbonate resin having a free radical initiation group in its main chain.