JPH07179593A - Polycarbonate block copolymer and its production - Google Patents

Abstract

PURPOSE:To provide a novel copolymer excellent in heat resistance and impact resistance and useful for mechanical parts, electric or electronic parts, automotive parts, optical parts, etc. CONSTITUTION:A polycarbonate block copolymer having a viscosity-average mol.wt. of 15000-40000 comprises (A) a polycarbonate block I having one or more of carbonate structural units I of formula I (each of X groups is independently halogen, 1-8C alkyl, 6-20C aryl; m, n are independently an integer of 0-4), and (B) a polycarbonate block II having two or more of carbonate structural units II of formula II (each of Y groups is independently halogen, 1-8C alkyl, 6-20C aryl; p, q are independently integers of 0-4; A is single bond, 1-20C alkylene, etc.,). The polycarbonate block copolymer is obtained by copolymerizing an oligomer containing 9,9-bis(4-hydroxyphenyl) fluorene (hereinafter referred to as BPFL) with an oligomer not containing the BPFL by an interfacial condensation method.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polycarbonate block copolymer and a method for producing the same. More specifically, it is possible to efficiently obtain a polycarbonate block copolymer having excellent heat resistance and impact resistance, which is suitably used for mechanical parts, electric / electronic parts, automobile parts, optical parts, etc., and the copolymer. The present invention relates to a manufacturing method.

[0002]

2. Prior Art and Problems to be Solved by the Invention
-Bis (4-hydroxyphenyl) fluorene (hereinafter,
It may be abbreviated as BPFL. It is known that the polycarbonate copolymer containing) has high heat resistance (US Pat. No. 3,546,165). But 9,
A polycarbonate containing 9-bis (4-hydroxyphenyl) fluorene has a drawback that it is difficult to be powdered using a kneader or the like because it is difficult to crystallize. Regarding this drawback, our group has already
It has been found that, by mixing a copolymer containing PFL and a polycarbonate not containing BPFL to obtain a desired content of BPFL, crystallization is accelerated and powdering is possible, and an improved technique is developed. Has been successful (Japanese Patent Application No. 5-173877). However, regarding the above-mentioned improved technique, a copolymer containing BPFL and BPF
The L-free polycarbonate must be produced simultaneously in separate equipment, which is somewhat problematic for efficient production.

[0003]

In view of the above points, the present inventor has conducted diligent research in order to solve the above problems of the related art and obtain a polycarbonate copolymer having excellent heat resistance and impact resistance. It was As a result, they have found that a block copolymer having a main chain of a polymer block containing BPFL and a polymer block not containing BPFL has desired properties. It was also found that the block copolymer can be efficiently obtained by copolymerizing an oligomer containing BPFL and an oligomer not containing BPFL by an interfacial polycondensation method. The present invention has been completed based on such findings. That is,
In the present invention, the main chain is (A) general formula (I)

[0004]

[Chemical 4]

[In the formula, X represents a halogen atom, an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 20 carbon atoms, and when there are a plurality of X, each X is the same or different. May be. m and n are 0 to
It is an integer of 4. ] The carbonate structural unit I represented by
Polycarbonate block I and (B) having two or more
General formula (II)

[0006]

[Chemical 5]

[In the formula, Y represents a halogen atom, an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 20 carbon atoms, and when there are a plurality of Y, each Y is the same or different. May be. p and q are 0 to 0, respectively.
It is an integer of 4. A is a single bond, an alkylene group having 1 to 20 carbon atoms or an alkylidene group, a cycloalkylene group having 5 to 20 carbon atoms or a cycloalkylidene group, and having 6 to 20 carbon atoms
Arylene group or arylalkylene group, -O-,-
CO -, - S -, - SO -, - SO 2 - bond or the formula (III)

[0008]

[Chemical 6]

The bond represented by ] A polycarbonate block II having two or more carbonate structural units II represented by the following formula and having a viscosity average molecular weight of 15,000 to
The present invention provides a polycarbonate block copolymer, which is characterized in that it is 40,000. Further, the present invention provides a polycarbonate oligomer I having two or more carbonate structural units I represented by the general formula (I) and a general formula (I
The present invention provides a method for producing a polycarbonate block copolymer, which comprises copolymerizing a polycarbonate oligomer II having two or more carbonate structural units represented by I) by an interfacial polycondensation method.

The polycarbonate block copolymer of the present invention (hereinafter sometimes abbreviated as PC block copolymer).
Is a polycarbonate block I whose main chain has a carbonate structural unit I represented by the general formula (I) of the component (A) (hereinafter sometimes abbreviated as PC block I) and a general formula of the component (B). Polycarbonate block II having a carbonate structural unit II represented by (II) (hereinafter referred to as PC
Sometimes abbreviated as Block II. ) Consists of.
The PC block I of the component (A) that constitutes the PC block copolymer has two or more, preferably 2 to 50, carbonate structural units I represented by the general formula (I). In addition, the PC block II of the component (B) has the general formula (I
It has 2 or more, preferably 2 to 50, carbonate structural units II represented by I). In this PC block copolymer, if either one of the carbonate structural unit I and the carbonate structural unit II is less than 2, crystallinity and powderability are deteriorated, which is not preferable. Here, X in the carbonate structural unit I represented by the general formula (I) that constitutes the PC block I of the component (A) is a halogen atom (for example, chlorine, bromine, fluorine, iodine), a carbon number of 1 to 1 8 alkyl groups (eg, methyl group, ethyl group, propyl group, n-butyl group,
Isobutyl group, amyl group, isoamyl group, pentyl group,
Hexyl group, heptyl group, octyl group, etc. or aryl group having 6 to 20 carbon atoms, preferably 6 to 15 carbon atoms (eg,
(Phenyl group, tolyl group, xylyl group, naphthyl group, etc.)
When there are a plurality of Xs, each X may be the same or different. m and n are 0 to
It is an integer of 4.

Further, Y in the carbonate structural unit II represented by the general formula (II) constituting the PC block II of the component (B) is a halogen atom (for example, chlorine, bromine, fluorine, iodine), carbon number. 1-8 alkyl groups (eg, methyl groups,
Ethyl group, propyl group, n-butyl group, isobutyl group,
Amyl group, isoamyl group, pentyl group, hexyl group, heptyl group, octyl group) or an aryl group having 6 to 20 carbon atoms, preferably 6 to 15 carbon atoms (eg, phenyl group, methylphenyl group, tolyl group, xylyl group, A naphthyl group) and there are a plurality of Ys, each Y may be the same or different. p and q are integers of 0 to 4, respectively. A is a single bond and has 1 to 1 carbon atoms.
20, preferably 1 to 15 alkylene group or alkylidene group (for example, methylene group, ethylene group, propylene group, butylene group, pentylene group, venterylene group, hexylene group, ethylidene group, isopropylidene group, etc.),
A cycloalkylene group or a cycloalkylidene group having 5 to 20 carbon atoms, preferably 5 to 15 carbon atoms (for example, a cyclopentylene group, a cyclohexylene group, a cyclopentylidene group,
Cyclohexylidene group, 3,3,5-trimethylcyclohexylidene group, etc.), having 6 to 20 carbon atoms, preferably 6
To 15 arylene groups or arylalkylene groups (eg, phenylene group, naphthylene group, xylylene group, phenylethylidene group, etc.), or —O—, —CO—, —S
-, - SO -, - SO 2 - bond or the formula (III)

[0012]

[Chemical 7]

The bond represented by The main chain of the PC block copolymer of the present invention is the PC block I and the PC block.
Consisting of block II and having a viscosity average molecular weight of 15,000
It is from 0 to 40,000, preferably from 15,000 to 3,000,000. In this PC block copolymer, the ratio of the carbonate structural unit I is 1 to 9 with respect to the total amount of the carbonate structural unit I and the carbonate structural unit II.
It is 9 mol%, preferably 2 to 50 mol%, more preferably 5 to 25 mol%. Here, the viscosity average molecular weight is 15,
If it is less than 000, the impact resistance will be reduced, and it will be 40,000.
If it exceeds, fluidity is deteriorated, which is not preferable. Further, when the proportion of the carbonate structural unit I is less than 1 mol%, the heat resistance is lowered, and when it exceeds 99 mol%, the impact resistance is lowered, which is not preferable.

The PC block copolymer of the present invention as described above is produced by various methods, but preferably, for example, the carbonate structural unit I is 2 or more, and preferably 2 or more.
Polycarbonate Oligomer I (hereinafter P
Abbreviated as C oligomer I. ) And a polycarbonate oligomer II having two or more, preferably 2 to 50, carbonate structural units II (hereinafter abbreviated as PC oligomer II) by an interfacial polycondensation method. In the method for producing a PC block copolymer, the PC oligomer I constitutes the PC block I of the component (A) of the main chain, and the PC oligomer II of the component (B) of the main chain. It serves to construct the PC block II. This PC oligomer I has the general formula (IV) corresponding to the carbonate structural unit I.

[0015]

[Chemical 8]

[In the formula, X, m and n are the same as defined above. ] Bisphenol (i) represented by
The oligomer II has the general formula (V) corresponding to the carbonate structural unit II.

[0017]

[Chemical 9]

[In the formula, Y, A, p and q are the same as defined above. ] The bisphenol (ii) represented by the following method, which is commonly used in the production of polycarbonate, that is, phosgene in the presence of a known acid acceptor and monohydric phenol (end terminator) in an organic solvent such as methylene chloride. Or an interfacial polycondensation method (solvent method) by reaction with a carbonate precursor such as a phosgene derivative, or a transesterification method (melting method) by transesterification reaction with a carbonic acid diester (for example, a carbonate precursor such as diphenyl carbonate) And the like. Of these, the interfacial polycondensation method is preferred.

There are various bisphenols (i) corresponding to the carbonate structural unit I.
Specifically, 9,9-bis (4-hydroxyphenyl)
Fluorene; 9,9-bis (4-hydroxy-3,5-
Examples thereof include dimethylphenyl) fluorene and its derivatives. Among these bisphenols (i),
9,9-bis (4-hydroxyphenyl) fluorene is preferably used. These bisphenols may be used alone or in combination of two or more.

There are various bisphenols (ii) corresponding to the carbonate structural unit II. For example, bis (4-hydroxyphenyl) methane; bis (3
-Methyl-4-hydroxyphenyl) methane; bis (3
-Chloro-4-hydroxyphenyl) methane; bis (3,5-dibromo-4-hydroxyphenyl) methane; 1,1-bis (4-hydroxyphenyl) ethane;
1,1-bis (2-t-butyl-4-hydroxy-3-
Methylphenyl) ethane; 1-phenyl-1,1-bis (2-fluoro-4-hydroxy-3-methylphenyl) ethane; 2,2-bis (4-hydroxyphenyl)
Propane (commonly called bisphenol A: BPA); 2,2-
Bis (3-methyl-4-hydroxyphenyl) propane; 2,2-bis (2-methyl-4-hydroxyphenyl) propane; 2,2-bis (3,5-dimethyl-4-)
Hydroxyphenyl) propane; 1,1-bis (2-t
-Butyl-4-hydroxy-5-methylphenyl) propane; 2,2-bis (3-chloro-4-hydroxyphenyl) propane; 2,2-bis (3-fluoro-4-hydroxyphenyl) propane; 2, 2-bis (3-bromo-4-hydroxyphenyl) propane; 2,2-bis (3,5-difluoro-4-hydroxyphenyl) propane; 2,2-bis (3,5-dichloro-4-hydroxyphenyl) ) Propane; 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane; 2,2-bis (4-hydroxyphenyl) butane; 2,2-bis (4
-Hydroxyphenyl) octane; bis (4-hydroxyphenyl) phenylmethane; 1,1-bis (4-hydroxy-t-butylphenyl) propane; 2,2-bis (3-bromo-4-hydroxy-5-chlorophenyl) )
Propane: 2,2-bis (3-phenyl-4-hydroxyphenyl) propane; 2,2-bis (3-methyl-4)
-Hydroxyphenyl) butane; 1,1-bis (2-butyl-4-hydroxy-5-methylphenyl) butane;
1,1-bis (2-t-butyl-4-hydroxy-5-
Methylphenyl) butane; 1,1-bis (2-t-butyl-4-hydroxy-5-methylphenyl) isobutane; 1,1-bis (2-t-amyl-4-hydroxy-)
5-methylphenyl) butane; 2,2-bis (3,5-
Dichloro-4-hydroxyphenyl) butane; 2,2-
Bis (3,5-dibromo-4-hydroxyphenyl) butane; 4,4-bis (4-hydroxyphenyl) heptane; 1,1-bis (2-t-butyl-4-hydroxy-)
Bis (hydroxyaryl) alkanes such as 5-methylphenyl) heptane; 1,1-bis (4-hydroxyphenyl) cyclopentane; 1,1-bis (4-hydroxyphenyl) cyclohexane; 1,1-bis (3 -Methyl-4-hydroxyphenyl) cyclohexane; 1,
1-bis (3-cyclohexyl-4-hydroxyphenyl) cyclohexane; 1,1-bis (3-phenyl-4)
-Hydroxyphenyl) cyclohexane; 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane and other bis (hydroxyaryl) cycloalkanes; bis (4-hydroxyphenyl) ether; bis (4- Bis (hydroxyaryl) ethers such as hydroxy-3-methylphenyl) ether; bis (4-hydroxyphenyl) sulfide; bis (3-
Bis (hydroxyaryl) sulfides such as methyl-4-hydroxyphenyl) sulfide; bis (4-hydroxyphenyl) sulfoxide; bis (3-methyl-)
4-hydroxyphenyl) sulfoxide; bis (hydroxyaryl) sulfoxides such as bis (3-phenyl-4-hydroxyphenyl) sulfoxide; bis (4
Hydroxyphenyl) sulfone; bis (3-methyl-4)
-Hydroxyphenyl) sulfone; bis (hydroxyaryl) sulfones such as bis (3-phenyl-4-hydroxyphenyl) sulfone, 4,4'-dihydroxybiphenyl;4,4'-dihydroxy-2,2'-dimethylbiphenyl4,4'-dihydroxy-3,3'-
Dimethylbiphenyl; 4,4'-dihydroxy-3,
3′-dicyclohexylbiphenyl; dihydroxybiphenyls such as 3,3′-difluoro-4,4′-dihydroxybiphenyl and the like. Among these,
In particular, 2,2-bis (4-hydroxyphenyl) propane [bisphenol A] is preferably used. And
These bisphenols (ii) can be used alone or in combination of two or more.

As the carbonic acid diester, a carbonic acid diaryl compound, a carbonic acid dialkyl compound or a carbonic acid alkylaryl compound can be used. Here, examples of the diaryl carbonate compound include diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, dinaphthyl carbonate, and bisphenol A bisphenyl carbonate. Examples of the dialkyl carbonate compound include diethyl carbonate, dimethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, bisphenol A bismethyl carbonate and the like. And as the alkyl aryl carbonate compound, for example,
Methyl phenyl carbonate, ethyl phenyl carbonate, butyl phenyl carbonate, cyclohexyl phenyl carbonate, bisphenol A methyl phenyl carbonate, etc. are mentioned.

When the PC oligomer I or PC oligomer II is produced by a solvent method, ie, an interfacial polycondensation method, which is a preferable production method, the bisphenol (i) or bisphenol (ii) is reacted with phosgene to prepare a reaction mixture in the reaction system. It can be obtained by reacting substantially all of the phosgene. The PC oligomer I obtained here is
In the polycondensation reaction, it has a carbonate structural unit I represented by the general formula (I) formed by the reaction of bisphenol (i) and phosgene. Further, the PC oligomer II has a carbonate structural unit II represented by the general formula (II) which is formed by the reaction of bisphenol (ii) and phosgene. Such PC oligomer I or PC
To synthesize the oligomer II, first, the bisphenol (i) or bisphenol (ii) is dissolved in an aqueous solution of an alkali metal hydroxide to prepare an alkaline aqueous solution of bisphenol. Then, phosgene or a phosgene derivative is introduced into a mixed solution of the alkaline aqueous solution and an inert organic solvent to prepare a bisphenol (i) or bisphenol (ii) P
C oligomer I or PC oligomer II is synthesized. At this time, the alkali concentration of the alkaline aqueous solution is 1 to 15 wt%.
Is preferable, and the volume ratio of the organic phase to the aqueous phase is 5:
It is desirable to be in the range of 1 to 1: 7, preferably 2: 1 to 1: 4. The reaction temperature is water bath cooling, usually 0 to 50 ° C,
It is preferably selected in the range of 5 to 40 ° C. and the reaction time is 15
Minutes to 4 hours, preferably about 30 minutes to 2 hours. The degree of polymerization of the PC oligomer thus obtained is usually 50 or less, preferably about 2 to 20.

The PC block copolymer of the present invention can be produced by various methods, but it is preferable to mix PC oligomer I and PC oligomer II previously produced as described above to prepare PC oligomer I and PC oligomer. Oligomer II
If desired, an inert organic solvent that is immiscible with water, such as methylene chloride, is added to the organic phase, and this is contacted with an alkaline aqueous solution containing bisphenol (i) and / or bisphenol (ii) in a predetermined ratio. , Usually 0 to 50 ° C,
Preferably, it can be produced by interfacial polycondensation for about 10 minutes to 6 hours at a temperature in the range of 5 to 40 ° C. At this time, the alkali concentration of the alkaline aqueous solution is preferably 1 to 15% by weight, and the volume ratio of the organic phase to the aqueous phase is 7: 1 to 1: 2, preferably 4: 1 to 1: 1. Is desirable. The ratio of the bisphenols and the oligomer is selected so that the molar ratio of bisphenol / oligomer chloroformate group is usually 0.4 to 0.55, preferably 0.45 to 0.5. Further, the ratio of alkali metal hydroxide to oligomer is such that the molar ratio of alkali metal hydroxide / oligomer chloroformate group is usually 1.0 to 2.0, preferably 1.2 to 1.7. To be chosen. Furthermore, in this reaction, a terminal stopper or a catalyst can be used if desired. The amount of the terminator used is such that the molar ratio of the terminator / oligomer chloroformate group is usually 0.02 to 0.20, preferably 0.04 to 0.02.
Selected to be 17. The amount of catalyst used is usually a catalyst / oligomer chloroformate group molar ratio of 1.
0 × 10 ^{−3 to} 10.0 × 10 ⁻³ , preferably 1.0 × 10 ⁻³
It is chosen to be ~ 5.0 x 10 ^-3 .

There are various types of organic solvents. For example, dichloromethane (methylene chloride); chloroform; 1,1-dichloroethane; 1,2-dichloroethane; 1,1,1-trichloroethane; 1,1,2-
Examples include chlorinated hydrocarbons such as trichloroethane; 1,1,1,2-tetrachloroethane; 1,1,2,2-tetrachloroethane; pentachloroethane and chlorobenzene; and acetophenone. These organic solvents are
They may be used alone or in combination of two or more. Of these, methylene chloride is particularly preferable. Examples of alkali metal hydroxides include sodium hydroxide, potassium hydroxide, lithium hydroxide, and cesium hydroxide. Of these, sodium hydroxide and potassium hydroxide are preferred.
As the catalyst, various kinds can be used. Specifically, it is a quaternary ammonium salt, a quaternary phosphonium salt, a tertiary amine, or the like. Examples of the quaternary ammonium salt include trimethylbenzylammonium chloride, triethylbenzylammonium chloride,
Examples thereof include tributylbenzylammonium chloride, trioctylmethylammonium chloride, tetrabutylammonium chloride and tetrabutylammonium bromide. Further, as the quaternary phosphonium salt, for example, tetrabutylphosphonium chloride,
Such as tetrabutylphosphonium bromide, and
Examples of the tertiary amine include triethylamine, tributylamine, tributylamine, N, N-dimethylcyclohexylamine, pyridine, dimethylaniline and the like. Of these, triethylamine is preferred.

Further, various types of end terminators can be used. Usually, it is used for polymerization of polycarbonate, and monohydric phenol is used. For example, phenol, p-cresol, pt-butylphenol, pt-amylphenol, pt-
Examples thereof include octylphenol, p-cumylphenol, P-bromophenol, tribromophenol, nonylphenol and the like.

In the production of PC block copolymer,
Use of a compound (branching agent) having three or more functional groups in the bisphenol (i) represented by the general formula (IV) and the bisphenol (ii) represented by the general formula (V). it can. Here, as a compound having three or more functional groups, a compound having three or more functional groups such as a hydroxyl group, a carboxyl group, an amino group, an imino group, a formyl group, an acid halide group, and a haloformate group in one compound. Is. For example, phloroglucin, mellitic acid, trimellitic acid, trimellitic acid chloride, trimellitic anhydride, gallic acid, n-propyl gallate, protocatechuic acid, pyromellitic acid, pyromellitic dianhydride, α-resorcinic acid, β
-Resorcinic acid, resorcinaldehyde, trimethyl chloride, trimethyltri-4-chloroformylphthalic anhydride, benzophenone tetracarboxylic acid; 4,6-dimethyl-2,4,6-tri (4'-hydroxyphenyl)
-Heptene-2; 4,6-dimethyl-2,4,6-tri (4'-hydroxyphenyl) -heptane-2; 1,
3,5-tri (4'-hydroxyphenyl) -benzene; 1,1,1-tri- (4'-hydroxyphenyl)
-Ethane; 2,2-bis- [4,4-bis (4'-hydroxyphenyl) cyclohexyl] -propane; 2,6
-Bis- (2'-hydroxy-5'-methylbenzyl)
-4-methylphenol; 2,6-bis- (2'-hydroxy-5'-isopropylbenzyl) -4-isopropylphenol; bis- [2-hydroxy-3- (2 '
-Hydroxy-5'-methylbenzyl) -5-methylphenyl] methane; tetra- (4-hydroxyphenyl)
Methane; tri- (4-hydroxyphenyl) phenylmethane; tris (4'-hydroxyaryl) -amyl-
s-triazine; α, α ', α "-tris (4-hydroxyphenyl) -1,3,5-triisopropylbenzene; 1- [α-methyl-α- (4'-hydroxyphenyl) ethyl-4- [Α ', α'-bis (4 "-hydroxyphenyl) ethyl] benzene; 1- [α-methyl-α
-(4'-Hydroxyphenyl) ethyl] -3-
[Α ′, α′-bis (4 ″ -hydroxyphenyl) ethyl] benzene and the like. Among these, 1,
1,1-tri- (4'-hydroxyphenyl) -ethane is preferred.

The polymer thus produced is subjected to a recovery operation according to a usual method to obtain the P of the present invention.
A C block copolymer can be obtained. In addition to this, PC oligomer I was previously produced from bisphenol (i) and carbonic acid diester, and PC oligomer II was produced from bisphenol (ii) and carbonic acid diester, and the obtained PC oligomer I and PC oligomer II were mixed, Bisphenol (i) and / or bisphenol (ii) as required
Can also be added at a predetermined ratio to produce the compound by the transesterification method. The PC block copolymer has, as the component (A), the PC block I having the carbonate structural unit I represented by the general formula (I) and the component (B).
It is a polycarbonate copolymer having PC block II as a main chain, which has a carbonate structural unit II represented by the general formula (II). This PC block copolymer has a viscosity average molecular weight of 15,000 to 40,000, preferably 15,000.
It is up to 30,000 and is excellent in heat resistance and impact resistance. And in this PC block copolymer,
The ratio of the carbonate structural unit I is 1 to the total amount of the carbonate structural unit I and the carbonate structural unit II.
It is 99 mol%, preferably 2 to 50 mol%, more preferably 5 to 25 mol%.

The PC block copolymer of the present invention is
If necessary, various well-known additives such as plasticizers, pigments, lubricants, mold release agents, stabilizers, UV absorbers, antioxidants, inorganic fillers, etc. may be added within a range that does not impair the object of the present invention. The agent can be blended and used. Further, it can be used in combination with various resins. For example, it can be blended with polyolefin, polystyrene and the like. Especially OH
It is effective when used in combination with a polyphenylene ether, a polyether nitrile, a terminal-modified polysiloxane compound, a modified polybrobylene, a modified polystyrene or the like having a group, a COOH group, an NH ₂ group or the like at the end.

The PC block copolymer of the present invention can be used for various moldings by blending various additives and resins as necessary and kneading. Then, for the compounding and kneading, a method usually used, for example, a ribbon blender, a Henschel mixer, a Banbury mixer, a drum tumbler, a single screw extruder, a twin screw extruder, a co-kneader, a multi-screw extruder, etc. Can be done using. The heating temperature for kneading is usually selected in the range of 250 to 300 ° C. The PC block copolymer thus obtained can be applied with various known molding methods such as injection molding, hollow molding, extrusion molding, compression molding, calender molding, rotational molding, etc. to produce various molded articles. It can be used to do so.

[0030]

The present invention will be further described in detail with reference to Synthesis Examples, Examples and Comparative Examples. Synthesis Example 1 [Synthesis of PC oligomer II] 5% by weight of 400 liters
60 kg of bisphenol A was dissolved in an aqueous sodium hydroxide solution to prepare an aqueous sodium hydroxide solution of bisphenol A. Then, the aqueous sodium hydroxide solution of bisphenol A kept at room temperature was passed through the orifice plate at a flow rate of 138 liters / hour and methylene chloride at a flow rate of 69 liters / hour through a tubular reactor having an inner diameter of 10 mm and a tube length of 10 m. It was introduced and phosgene was flowed in parallel to it.
It was blown in at a flow rate of 7 kg / hour and continuously reacted for 3 hours. The tubular reactor used here is a double tube,
Cooling water was passed through the jacket to keep the reaction solution discharge temperature at 25 ° C. The pH of the discharged liquid is 10 to 11
Was adjusted as shown. The aqueous solution was separated and removed by allowing the reaction solution thus obtained to stand, and 220 liters of a methylene chloride phase was collected to obtain a polycarbonate oligomer II. The PC oligomer II obtained here had a degree of polymerization of 3 to 4 and a concentration of 317 g / liter.

Synthesis Example 2 [Synthesis of PC Oligomer I] The sodium hydroxide aqueous solution of Synthesis Example 1 was changed to a 10 wt% potassium hydroxide aqueous solution, and 9,9-bis (4-hydroxyphenyl) fluorene was used instead of bisphenol A. The same procedure as in Synthesis Example 1 was carried out except that the amount was 55 kg. The degree of polymerization of the PC oligomer I obtained here was 5 to 6.

Example 1 Preparation of solution A 2.6 liters of PC oligomer I and PC oligomer II
7.4 liter of methylene chloride was taken and 10.7 liter of methylene chloride and 80.0 g (0.53 mol) of p-tert-butylphenol were added to prepare a solution A. Preparation of Solution B Solution B was prepared by dissolving 690 g (3.02 mol) of bisphenol A in an aqueous potassium hydroxide solution (390 g of KOH was dissolved in 5 liters of water). To the solution A, 3 ml of triethylamine was added, and the solution B was quickly added while stirring, and the mixture was stirred for 60 minutes. After stirring for 60 minutes, 4 liters of methylene chloride was added, diluted and then centrifuged, and the methylene chloride phase was washed with 0.03 NKOH aqueous solution, 0.1 N hydrochloric acid and water in this order. The washed methylene chloride phase was gradually added to vigorously stirred methanol to precipitate and remove the polymer powder. Then, the polymer powder is heated to 120 ° C.
It was dried under N ₂ gas flow for 2 hours, and further at 120 ° C. for 48 hours.
Vacuum drying was carried out for an hour to obtain a flake polymer. The glass transition temperature of the obtained polymer was measured by DSC. The result is shown in FIG.

Examples 2 to 3 In Example 1, PC oligomer I and PC in solution A were used.
A flake polymer was obtained in the same manner as in Example 1 except that the compounding ratio of the oligomer II was changed as shown in Table 1.

Comparative Example 1 Preparation of Solution C 7 liters of PC oligomer II, 7.5 liters of methylene chloride and p-tert-butylphenol (PTB) were used.
Solution C was prepared by adding 64.4 g (0.43 mol) of P). Preparation of liquid D 9,9-bis (4-hydroxyphenyl) fluorene 7
82 g (2.24 mol) of potassium hydroxide aqueous solution (KOH
448 g was dissolved in 9 liters of water. ), And the liquid D was prepared. Thereafter, the same procedure as in Example 1 was carried out to obtain a flake-shaped polymer.

Comparative Example 2 Preparation of Solution E 9,9-bis (4-hydroxyphenyl) fluorene 5
35 g (1.53 mol) and 162 g of bisphenol A (0.5.
71 mol) was dissolved in an aqueous potassium hydroxide solution (448 g of KOH was dissolved in 9 liters of water) to prepare a solution E. A flake-like polymer was prepared in the same manner as in Comparative Example 1 except that the amount of p-tert-butylphenol was 58.0 g (0.39 mol) and the solution E was used instead of the solution D. Got

With respect to the polymers obtained in Examples 1 to 3 and Comparative Examples 1 and 2, the content of BPFL and the viscosity average molecular weight were measured. Further, the crystallization time was measured, and at the same time, the powdering property was evaluated by a kneader. The result is first
Shown in the table. The measuring method of each quality is as follows. 1) BPFL [9,9-bis (4-hydroxyphenyl)]
Fluorene] content was determined using a high resolution nuclear magnetic resonance apparatus (NMR). 2) Viscosity average molecular weight (Mv) The intrinsic viscosity [η] was measured in methylene chloride at 20 ° C using an Ubbelohde viscosity tube, and the molecular weight was determined by the following relational expression. [Η] = 1.23 × 10 ⁻⁵ Mv ^0.83 3) Crystallization time 1.0 g of the polymer powder was dissolved in 2.3 g of methylene chloride, 2.9 ml of heptane was added and stirred, and the polymer became a powder. The time until precipitation was measured. 4) Kneader powdering A SIKRC kneader manufactured by Kurimoto Steel Co., Ltd. was used to judge whether a stable powder can be obtained by continuously supplying a methylene chloride solution of the polymer. Operating conditions Concentration of polymer in methylene chloride solution 25% by weight Supply amount of polymer in methylene chloride solution 200 g / hour Jacket temperature 75 ° C. Pressure 580 Torr

[0037]

[Table 1]

[0038]

[Table 2]

The flaky polymers obtained in Example 1 and Comparative Example 1 were used as antioxidants.
Irgafos 168 [Ciba Geigy, Tris (2
4-di-t-butylphenyl) phosphite] 800p
pm was added, and the mixture was kneaded using an extruder and pelletized at 300 ° C. The obtained pellet was injection-molded to prepare a test piece. About the obtained test piece, as a quality evaluation,
The impact resistance, heat resistance and total light transmittance were measured. The measurement results are shown in Table 2. In addition, the measurement method of quality evaluation is
It is as follows. 1) Impact resistance Izod impact strength test (based on JIS K-7110)
The breaking strength (1/8 inch in thickness, with notch) was measured. 2) Heat resistance A high load heat distortion temperature (based on JIS K-7207 load deflection temperature test method A method) was measured. 3) Total light transmittance For a test piece having a thickness of 3.2 mm, JIS K-7105
It was measured according to.

[0040]

[Table 3]

From Tables 1 and 2, the PC block copolymer of the present invention has significantly improved crystallinity and powderability while maintaining physical properties as compared with the corresponding random copolymer. It is clear that

As described above, the polycarbonate block copolymer of the present invention has excellent heat resistance and impact resistance, and can be efficiently produced. Therefore, the polycarbonate block copolymer of the present invention can be used for mechanical parts, electric machinery,
It can be suitably used for electronic parts, automobile parts, optical parts and the like.

[Brief description of drawings]

FIG. 1 shows the glass transition temperature measurement results of the polymer obtained in Example 1 by DSC.

Claims (3)

[Claims] 1. The main chain comprises (A) general formula (I): [In the formula, each X represents a halogen atom, an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 20 carbon atoms, and when there are a plurality of X, each X may be the same or different. Good. m and n are integers of 0 to 4, respectively. ] Polycarbonate block I having two or more carbonate structural units I and represented by the general formula (II) [Wherein each Y represents a halogen atom, an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 20 carbon atoms, and when there are a plurality of Ys, each Y may be the same or different. Good. p and q are integers of 0 to 4, respectively. A is a single bond, an alkylene group having 1 to 20 carbon atoms or an alkylidene group, a cycloalkylene group having 5 to 20 carbon atoms or a cycloalkylidene group, an arylene group having 6 to 20 carbon atoms or an arylalkylene group, -O-, -CO. -,-S
-, - SO -, - SO 2 - bond or the formula (III) ## STR3 ## Indicates a bond represented by. ] The polycarbonate block copolymer which consists of the polycarbonate block II which has two or more carbonate structural units II represented by these, and has a viscosity average molecular weight of 15,000-40,000. 2. The polycarbonate block copolymer according to claim 1, wherein the ratio of the carbonate structural unit I is 1 to 99 mol% with respect to the total amount of the carbonate structural unit I and the carbonate structural unit II. 3. A polycarbonate oligomer I having two or more carbonate structural units I and a carbonate structural unit.
A method for producing a polycarbonate block copolymer, which comprises copolymerizing a polycarbonate oligomer II having two or more IIs by an interfacial polycondensation method.