JPH06184293A - Terminal-modified polycarbonate resin and its production - Google Patents

Abstract

PURPOSE:To obtain the subject resin containing a specific constituent unit, terminal-stopped with cinnamoyl group, having a viscosity-average molecular weight falling within a specific range, exhibiting terminal reaction activity and useful e.g. as a raw material for the production of a block copolymer with other resins. CONSTITUTION:This resin is a polycarbonate having a viscosity-average molecular weight of 10,000-100,000, containing constituent unit of formula I [R1 to R8 are H, halogen, (substituted)alkyl or aryl; X is S, O, SO2 or (CH2)a ((a) is integer of >=1)] and having terminal groups stopped with cinnamoyl group of formula II. Preferably, this resin is produced by using a molecular weight modifier consisting of a polycarbonate oligomer having a viscosity-average molecular weight of <10,000, containing the constituent unit of formula III and having a terminal terminated with a phenolic hydroxyl group of formula IV and the other terminal terminated with cinnamoyl group of formula II.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel end-modified polycarbonate resin and a method for producing the same. The terminal-modified polycarbonate resin of the present invention is a polycarbonate resin having cinnamoyl groups at both ends and having reaction activity at the terminals, and by utilizing the terminal reaction activity, a raw material for producing a block copolymer with another resin, a reaction type It is preferably used for various purposes such as the resin modifier and the film material.

[0002]

2. Description of the Related Art Monovalent phenols, monovalent carboxylic acids, acid chlorides and the like are known as end-capping agents or molecular weight regulators for polycarbonates, and various modifications of polycarbonates have been carried out using these ( For example, JP-A-63-258922). As a polycarbonate having a terminal reaction activity, there is a vinyl-terminated polycarbonate (JP-A-63-3023). Also, as a terminal reactive polycarbonate, there is one having a phenolic hydroxyl group at the terminal (JP-A-58-164548). Among such reaction-active groups, the cinnamoyl group terminal having an internal olefin can be expected to have an activity different from that of a vinyl group, but it is the cheapest as a terminal terminator used for introducing a cinnamoyl group in the solution method. It was found that when cinnamic acid was used, the cinnamoyl group was only half-terminated even though the molecular weight could be controlled.

[0003]

As a result of intensive studies to solve the conventional problems, the inventors of the present invention have found that a polycarbonate using cinnamic acid as a molecular weight regulator at the both ends of a polycarbonate produced by a solution method. A polycarbonate having a phenolic hydroxyl group on one side and a cinnamoyl group on the other side and having different reaction activities at both ends,
It has been found that a cinnamoyl-terminated modified polycarbonate resin can be easily produced by using this polycarbonate oligomer as a molecular weight modifier, and the present invention has been completed based on this finding.

That is, the present invention is a polycarbonate having a constitutional unit represented by the following general formula (1), the terminal group of which is terminated with the following cinnamoyl group, and having a viscosity average molecular weight of 10,000 to 100,000: A modified polycarbonate resin and a method for producing the same are provided.

[0005]

[Chemical 5] (In the formula, each of R _{1 to} R ₈ represents hydrogen, halogen or an alkyl group or aryl group which may have a substituent.
X is

[0006]

[Chemical 6] Wherein R ₁₀ and R ₁₁ each represent hydrogen, halogen or an alkyl group or aryl group which may have a substituent, or R ₁₀ and R ₁₁ are bonded together to form a carbocycle or heterocycle. It represents a group forming a ring, and a and b represent an integer of 1 or more. )

The method for producing the polycarbonate resin of the present invention is as follows:
Phenol having a constitutional unit represented by the following general formula (2) as a molecular weight modifier or a terminal terminator, and one of the terminal groups of which is represented by (A), as compared with a conventional method for producing a polycarbonate resin. Viscosity average molecular weight of which one is a hydroxyl group and the other is terminated with a cinnamoyl group represented by (B)
Using less than 10,000 polycarbonate oligomers, it can be obtained in the same manner as in conventional polycarbonate resin production methods.

[0008]

[Chemical 7] (In the formula, (A) and (B) are respectively

(Margins below)

[Chemical 8] And R _{1 to} R ₈ and X are the same as in the general formula (1). )

That is, in the interfacial polymerization method, after reacting the dihydric phenol compound with phosgene in the presence of a reaction-inert organic solvent and an aqueous alkali solution, the oligomer of the general formula (2) and the tertiary amine or In the method of polymerizing by adding a polymerization catalyst such as a quaternary ammonium salt, in the pyridine method, a dihydric phenol compound and an oligomer of the general formula (2) are dissolved in pyridine or a mixed solution of pyridine and an inert solvent, and phosgene is blown into the solution. Is a method of directly obtaining a polycarbonate resin. In the interfacial polymerization method, a method of adding the oligomer of the general formula (2) at the time of reacting the dihydric phenol compound with phosgene may be used.

In the present invention, specific examples of the dihydric phenol compound include bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) sulfone and bis (4). -Hydroxyphenyl) sulfoxide, bis (4-
Hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) ketone, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A; BPA), 2, 2-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) cyclohexane (bisphenol Z; BPZ
), 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane, 2,2-bis (4-hydroxy-3) -
Bromophenyl) propane, 2,2-bis (4-hydroxy-3-chlorophenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-
Hydroxy-3,5-dimethylphenyl) propane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, bis (4-hydroxyphenyl) diphenylmethane, α,
ω-bis [3- (O-hydroxyphenyl) propyl]
Examples thereof include polydimethylsiloxane. It is also possible to use two or more of the above dihydric phenol compounds in combination.

The amount of the oligomer of the general formula (2) used as a molecular weight regulator is 100 to 0.5 mol, preferably 10 to 2 mol, based on 100 mol of the dihydric phenol compound.

Solvents inert to the reaction used in the present invention include dichloromethane, 1,2-dichloroethane,
Chlorinated hydrocarbons such as 1,1,2,2-tetrachloroethane, chloroform, 1,1,1-trichloroethane, carbon tetrachloride, monochlorobenzene and dichlorobenzene; aromatic carbonization such as benzene, toluene, xylene and ethylbenzene hydrogen;
An ether compound such as diethyl ether may be mentioned, and two or more kinds of these organic solvents may be mixed and used. In addition, if desired, solvents other than the above, such as ethers, ketones, esters, and nitriles, which have an affinity for water may be used within the limit that the mixed solvent system is not completely compatible with water.

As the polymerization catalyst, trimethylamine, triethylamine, tributylamine, tripropylamine, trihexylamine, tridecylamine, N,
Tertiary amines such as N-dimethylcyclohexylamine, pyridine, quinoline, dimethylaniline; quaternary ammonium salts such as trimethylbenzylammonium chloride, tetramethylammonium chloride, triethylbenzylammonium chloride and the like.

Further, a branching agent is used in an amount of 0.01 to 3 mol%, particularly 0.1 to 1.0 mol%, based on the above dihydric phenol compound.
Can be used in combination as a branched polycarbonate, and as the branching agent, phloroglucin, 2,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptene-
3,4,6-Dimethyl-2,4,6-tri (4-hydroxyphenyl) heptene-2,1,3,5-tri (2-hydroxyphenyl) benzol, 1,1,1-tri (4- Hydroxyphenyl) ethane, 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenol, α, α ′, α ″ -tri (4-hydroxyphenyl) -1,3,5-triisopropyl Polyhydroxy compounds exemplified by benzene and the like, and
Examples include 3,3-bis (4-hydroxyphenyl) oxindole (= isatin bisphenol) and the like.

The polycarbonate resin produced by the method of the present invention has cinnamoyl groups at both ends and has a reaction activity, and therefore is useful as a raw material for copolymerization with another polymer. For example, a raw material for a block copolymer such as polystyrene-polycarbonate. Is suitable as In addition, it is suitable for production of a composition with resins that have not been useful compositions because they are not easily compatible with conventional polycarbonates by melt mixing with other polymers that easily react with internal olefins. Used alone or in combination with a usual polycarbonate resin.

[0017]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples.

Example 1 580% of 8.8% (w / v) sodium hydroxide aqueous solution (NaOH)
To the l, 91.2 g of bisphenol A (BPA) and 0.1 g of hydrosulfite were added and dissolved. To this, 360 ml of methylene chloride was added, and 16.92 g of cinnamic acid was added while stirring at 15 ° C., and then 52 g of phosgene was introduced over 60 minutes. After the completion of the introduction, 50 ml of NaOH was added, and the mixture was vigorously stirred to emulsify the reaction solution. After emulsification, 0.2 ml of triethylamine was added, and the mixture was stirred for about 1 hour for polymerization. The polymerization liquid is separated into an aqueous phase and an organic phase, the organic phase is neutralized with phosphoric acid, and the pH of the washing liquid is
After repeating washing with water until it became neutral, 470 ml of isopropanol was added to precipitate a polymer. The precipitate was filtered and then dried to obtain a white powdery terminal-modified polycarbonate resin. The measurement results of this polycarbonate are shown in Table 1.

Example 2 Example 1 was repeated except that 47 g of the oligomer of Example 1 was used in place of cinnamic acid and the amount of methylene chloride was 400 ml.
I went the same way.

Comparative Example 1 Except that 13.94 g of benzoic acid was used instead of cinnamic acid,
The same procedure as in Example 1 was performed.

Comparative Example 2 Instead of the oligomer of Example 1, the oligomer of Comparative Example 1
Example 2 was repeated except that 38.7 g was used.

[0022]

[Table 1] Note that the items in the table are explained on the vase. BPA: 2,2-bis (4-hydroxyphenyl) propane KS: cinnamic acid AS: benzoic acid MHO: oligomer of Example 1 MAO: oligomer of Comparative Example 1

Intrinsic viscosity [η] (dl / g) was measured in a Mv: 20 ° C. dichloromethane solvent, and the viscosity average molecular weight was determined from the following conversion formula. [η] = 1.23 × 10 ⁻⁴ M ^0.83 IR: From the infrared absorption spectrum, the ester bond end (C =
The presence or absence of stretching vibration of (O) was examined. OH: Titanium tetrachloride-The amount of hydroxyl groups (OH) was determined by absorptiometry (546 nm). Theoretical OH: It was calculated by assuming that all the one ends of the polycarbonate synthesized using cinnamic acid became OH.

[0024]

According to the present invention, a polycarbonate resin modified with cinnamoyl groups at both ends can be obtained in the same manner as in the usual method for producing an aromatic polycarbonate resin. This terminal-modified polycarbonate resin is excellent in stability, and by utilizing a cinnamoyl group, as a blend material with a resin which could not be obtained a useful composition due to poor compatibility etc. by a conventional simple mixing method. It is also useful as a raw material for block-copolymers.

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[Procedure amendment]

[Submission date] February 23, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0011

[Correction method] Change

[Correction content]

In the present invention, specific examples of the dihydric phenol compound include bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) sulfone and bis (4). -Hydroxyphenyl) sulfoxide, bis (4-
Hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) ketone, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A; BPA), 2, 2-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) cyclohexane (bisphenol Z; BPZ
), 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane, 2,2-bis (4-hydroxy-3) -
Bromophenyl) propane, 2,2-bis (4-hydroxy-3-chlorophenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-
Hydroxy-3,5-dimethylphenyl) propane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, bis (4-hydroxyphenyl) diphenylmethane, α,
ω-bis [3- ( p -hydroxyphenyl) propyl]
Examples thereof include polydimethylsiloxane. It is also possible to use two or more of the above dihydric phenol compounds in combination.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Name of item to be corrected] 0022

[Correction method] Change

[Correction content]

[0022]

[Table 1] The items described in the table are explained below . BPA: 2,2'-bis (4-hydroxyphenyl) propane KS: cinnamic acid AS: benzoic acid MHO: oligomer of Example 1 MAO: oligomer of Comparative Example 1

Claims (2)

[Claims] 1. A polycarbonate having a constitutional unit represented by the following general formula (1), the terminal group of which is terminated with the following cinnamoyl group, and having a viscosity average molecular weight of 10,000 to
A terminal modified polycarbonate resin that is 100,000. [Chemical 1] (In the formula, each of R _{1 to} R ₈ represents hydrogen, halogen or an alkyl group or aryl group which may have a substituent.
X is Wherein R ₁₀ and R ₁₁ each represent hydrogen, halogen or an alkyl group or aryl group which may have a substituent, or R ₁₀ and R ₁₁ are bonded together to form a carbocycle or heterocycle. It represents a group forming a ring, and a and b represent an integer of 1 or more. ) 2. A method for producing a polycarbonate resin by a solution method, comprising a structural unit represented by the following general formula (2), one of the terminal groups of which is a phenolic hydroxyl group represented by (A) and the other of which is The method for producing a terminal-modified polycarbonate resin according to claim 1, wherein a polycarbonate oligomer having a viscosity average molecular weight of less than 10,000, which is end-capped with a cinnamoyl group represented by (B), is used as a molecular weight modifier. [Chemical 3] (In the formula, (A) and (B) are respectively represented by: And R _{1 to} R ₈ and X are the same as in the general formula (1). )