JPH03231919A - Polycarbonate, production thereof and polycarbonate resin composition - Google Patents

Abstract

PURPOSE:To obtain a polycarbonate containing a specific chromanyl group at the end and excellent impact strength in spite of low molecular weight by polymerizing an aromatic organic bihydroxyl group compound with a carbonic acid diester in molten state by using an end blocking agent. CONSTITUTION:An aromatic organic bihydroxyl group compound [preferably 2,2-bis(4-hydroxyphenyl)propane] is polymerized in a molten state with a carbonic acid diester (preferably diphenyl carbonate) using one or more chromanyl group-containing chromane compounds [preferably 2,2,4-trimethyl-4-(4- hydroxyphenyl)chromane shown by formula I, formula II or formula III (R1 to R6 are H or 1-9C alkyl] as an end blocking agent to give a polycarbonate containing one or more of chromanyl group shown by formula I, formula II or formula III bonded to 5-99mol% molecular end. Addition of a phosphorus based antioxidant to the polycarbonate yields a composition capable of preventing thermal deterioration during molding.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a polycarbonate, a method for producing the same, and a polycarbonate resin composition. In particular, it maintains mechanical properties such as excellent impact resistance even at a low molecular weight. We also offer polycarbonates that retain their mechanical properties, such as excellent impact resistance, over long periods of time in both high and low temperature environments, and polycarbonates that have these benefits but also have improved water resistance and transparency. The present invention relates to a method for producing polycarbonate that can be efficiently obtained, and a polycarbonate resin composition containing the above polycarbonate and having an excellent balance of various physical properties.

Polycarbonate Taka It has excellent mechanical properties such as impact resistance, heat resistance, and transparency, so it is widely used for various purposes.

Various attempts have been made to improve the performance of polycarbonate depending on the use of such polycarbonate.

Analogous phenoxy group, p-cumylphenoxy &
Attempts have been made to maintain impact resistance, especially in low molecular weight grades, by using terminal capping agents such as p-tert-phenoxy groups (see JP-A-1-245016, etc.).

However, even with such conventional attempts, there is a problem in that it is difficult to maintain sufficient impact resistance when the molecular weight is as low as that of disk grade.

The inventors of the present invention conducted extensive studies to solve the above problems, and found that polycarbonate, in which a specific chromanyl group is bonded at a specific ratio at the end of the molecule, has sufficient impact resistance even with a molecular weight as low as that of disc grade. It also maintains mechanical properties such as excellent impact resistance over a long period of time in both high and low temperature environments. When producing polycarbonate by polycondensation, it can be produced efficiently by a specific method using a chroman compound as an end-capping agent,
The resulting polycarbonate has further improved water resistance, transparency, and fluidity, and a specific polycarbonate resin composition containing polycarbonate having the above-mentioned excellent properties has improved impact resistance, fluidity, etc. Having completed the present invention by discovering that the balance of various physical properties is excellent, the method of capping the molecular ends of polycarbonate with chromanyl groups was disclosed in US Pat. No. 3,697.4.
It has already been disclosed in No. 81.

As a result of studying polycarbonate end-capped with chromanyl groups, the present inventor found that the properties differ depending on the type of chromanyl group and the end-capping rate. For example, simply increasing the end-capping rate with chromanyl groups It is often difficult to obtain a polycarbonate with the desired properties just by doing so, and the properties of the polycarbonate tend to vary depending on the type of chromanyl group introduced at the end of the molecule.

The present invention is an attempt to solve the problems associated with the conventional technology as described above, and has a structure that maintains sufficient impact resistance even with a low molecular weight and has excellent resistance in high-temperature and low-temperature environments. A polycarbonate that retains mechanical properties such as impact resistance for a long period of time, a method for producing polycarbonate that can efficiently obtain a polycarbonate that has these advantages, and a polycarbonate that contains a polycarbonate that has the above advantages and has a balance of various physical properties. The purpose of the present invention is to provide a polycarbonate resin composition with excellent properties.

and plate A nose 1 The first polycarbonate according to the present invention has the following formula [Ico,
It is characterized in that at least one chromanyl group selected from the group consisting of [■ and [III] is bonded.

...[r] ...[II] 5 ...[IIIl However, in the above formulas [I], [II] and [IIIl, R1 to R8 are each independently hydrogen or carbon atom number 1- 9 is an alkyl group, and R5 to R8 may be further substituted with a halogen atom.

Moreover, the second polycarbonate according to the present invention has a polycarbonate of 5 to 9
At least one type of chromanyl group selected from the group consisting of the above formulas [■], [II] and [IIIl is bonded to the molecular terminal of 9 mol% of polycarbonate molecules, and 1 to 95 mol% of polycarbonate molecules p-cumylphenoxy M, p-tert-
It is characterized in that a group selected from the group consisting of a butylphenoxy group and a phenoxy group is bonded.

In addition, the first method for producing polycarbonate according to the present invention uses an aromatic organic dihydroxyl group compound and a carbonic acid diester as terminal capping agents of the above formulas [I], [II] and [I
It is characterized in that melt polycondensation is carried out using at least one type of chroman compound capable of introducing a chromanyl group selected from the group consisting of IIl.

Furthermore, the second method for producing polycarbonate according to the present invention comprises using an aromatic organic dihydroxyl group compound and a carbonic acid diester as an end capping agent from the group consisting of the above formulas [i], [III] and [III]. At least one kind of chroman compound capable of introducing a selected chromanyl group and p-
It is characterized by carrying out melt polycondensation using a compound capable of introducing a group selected from the group consisting of a cumylphenoxy-5p-tert-butylphenoxy group and a phenoxy group.

Further, the polycarbonate resin composition according to the present invention comprises the above polycarbonate and the polycarbonate 10.
It is characterized by containing 0.01 to 0.13 parts by weight of a phosphorous antioxidant per 0 parts by weight.

The polycarbonate of the present invention has sufficient impact resistance even at a low molecular weight because the molecular ends are capped with a specific chromanyl group, and this property is also good in both high-temperature and low-temperature environments. Retained.

First, the first polycarbonate according to the present invention will be specifically explained below.

The first polycarbonate according to the present invention has a structure in which a specific chromanyl group is bonded to the molecular terminal of a polycarbonate molecule.

The polycarbonate of the present invention usually has a main chain consisting of repeating units represented by the following formula.

OH3...[■] Polycarbonate having the above-mentioned main chain generally has an OH group at the end of its molecule. The polycarbonate of the present invention is a polycarbonate in which 5 to 99 mol% of the OH groups are specific chromanyl groups as shown below.

In the present invention, the chromanyl group introduced into the polycarbonate has the following formulas [■], [+1] and [III
].

16- ...[■] ...[IIco5 ...[IIIcoHowever, in the above formulas [■co, [■co] and [III], R1-R8 are each independently hydrogen or a carbon atom It is an alkyl group of number 1 to 9, and these alkyl groups may be linear or branched. Furthermore, among these substituents, the hydrogen atoms constituting these groups may be substituted with a halogen atom, and the polycarbonate of the present invention may be substituted with a halogen atom such as a bromine atom or a chlorine atom. Also included are polycarbonates to which chromanyl groups and the like are bonded. Further, RI + R8 is independent in each formula, and can also be varied independently in the mutual relationship in the groups represented by the formulas [Ico, [II] and [III].

Such a polycarbonate may be prepared using the following formula [
It can be produced by melt polycondensation using at least one chroman compound capable of introducing a chromanyl group selected from the group consisting of [r], [II] and [III].

In the present invention, specific examples of chroman compounds capable of introducing a chromanyl group represented by the above formula [I] into the molecular terminal of polycarbonate include 2,2.4-)dimethyl-4- (4-hydroxyphenyl)chroman, 2,2.4.6-titramethyl-4-(3,5-dimethyl-4-hydroxyphenyl)chroman, 2,3.4-)dimethyl-2-ethyl-4-(3 -nonyl-4-hydroxyphenyl)-7-nitylchroman, 2,2,4-)dimethyl-4-(3,5-diethyl-4-hydroxyphenyl)-6-nitylchroman,
2,2.4.6.8-pentamethyl-4-(3,5-dimethyl-4-hydroxyphenyl)chroman, 2,2.4-triethyl-3-methyl-4-(4-hydroxyphenyl)chroman, 2,2,4-trimethyl-4-(3-bromo-4-hydroxyphenyl)chroman, 2,2,4-trimethyl-4-(3-bromo-4-hydroxyphenyl)-6-bromochroman, 2,2 .4-) dimethyl-4-(3,5-dibromo-
4- and draw) xyphenyl)-6-bromochroman, and 2,2,4-) dimethyl-4-(3,5-dibromo-
Mention may be made of 4-hydroxyphenyl)-6,8-dibromochroman.

Among these, in particular 2.2.4-) dimethyl-4
-(4-hydroxyphenyl)chroman is preferred.

Further, as examples of chroman compounds into which a chromanyl group represented by the above formula [IIl can be introduced, specifically, 2,4,4-trimethyl-2-(2-hydroxyphenyl)chroman, 2, 4.4.6-titramethyl-2-(3,5-dimethyl-2-hydroxyphenyl)chroman, 2,3.4-)dimethyl-4-ethyl-2-(3,5
-dimethyl-2-hydroxyphenyl)-7-tunilouchroman, 2,4.4-trimethyl-2-(3,5-dimethyl-2-hydroxyphenyl)-6-nithylchroman, 2,4.4.6 .8-pentamethyl-2-(3,5
-dimethyl-2-hydroxyphenyl)-6-nitylchroman, 12,4.4-trimethyl-2-(3-bromo-2-hydroxyphenyl)chroman, 2,4.4-trimethyl-2-(3-bromo -2-hydroxyphenyl) -6-bromochroman, 2,4.4-)dimethyl-2-(3,5-dibromo-2
-hydroxyphenyl)-6-bromochroman and 2,4,4-)dimethyl-2-(3,5-dibromo-
Mention may be made of 2-hydroxyphenyl)-6,8-dibromochroman.

Among these, in particular 2.2.4-)dimethyl-2
(2-hydroxyphenyl)chroman is preferred.

Further, specific examples of chroman compounds into which a chromanyl group represented by the above formula [III] can be introduced include 2,4.4-)dimethyl-2-(4-hydroxyphenyl)chroman, 2,4.4.6-Titramethyl-2-(3,5-dimethyl-4-hydroxyphenyl)chroman, 2,4.4-)diethyl-2-(4-hydroxyphenyl)chroman, 2,3.4- ) dimethyl-4-ethyl-2-(3,5
-dimethyl-4-hydroxyphenyl)-7-nitylchroman, 2,4.4-trimethyl-2-(3,5-diethyl-4-hydroxyphenyl)-6-nitylchroman, 2,4.4. 6.8-pentamethyl-2-(3
5-dimethyl-4hydroxyphenyl)-6-nitylchroman, 2,4.4-)dimethyl-2-(3-bromo-
4-hydroxyphenyl)chroman, 2,4.4-trimethyl-2-(3-bromo-4-hydroxyphenyl)-6-bromochroman, 2,4.4-)dimethyl-2-(3,5-dibromo-
4-hydroxyphenyl)-6-bromochroman, and 2,4,4-)dimethyl-2-(3,5-dibromo-
Mention may be made of 4-hydroxyphenyl)-6,8-dibromochroman.

Among these, in particular 24.4-)dimethyl-2-(
4-hydroxyphenyl)chroman is preferred.

The above chroman compounds can be used alone or in combination.

The polycarbonate of the present invention has the above formula [I], formula [II]
] and a chromanyl group car represented by formula [III] 5 to 99 mol%, preferably 10 to 95 mol% at the molecular terminal
, more preferably in a proportion of 20 to 90 mol %. Polycarbonate end-capped with chromanyl groups has excellent impact resistance even if it has a low molecular weight, and also has excellent mechanical properties such as impact resistance in high-temperature and low-temperature environments. Furthermore, by setting this proportion within the range of 20 to 85 mol %, the impact resistance of the low molecular weight polycarbonate and mechanical properties such as impact resistance in high temperature and low temperature environments are further improved.

As understood from the above formula [■], one polycarbonate molecule has at least two molecular terminals, and therefore (at least) 2 moles of chroman compound can be bonded to 1 mole of polycarbonate. be. In the present invention, for example, when 5 to 99 mol% of chromanyl groups are introduced at the end of the molecule, it means that 5 to 99 mol% of the chromanyl group that can be introduced at the end of the molecule is bonded to the end of the molecule. means.

Since the first polycarbonate according to the present invention has the above-mentioned features, it maintains sufficient impact resistance even with a low molecular weight, and also has mechanical properties such as excellent impact resistance even in high-temperature and low-temperature environments. can be maintained for a long period of time.

The polycarbonate according to the present invention has a polycarbonate of 5 to 9 as described above.
The 9 mol% molecular terminal C is end-capped with a Romanyl group as described above, and the remainder of the molecule end may be an OH group or may be capped with another inert group. .

In particular, it is preferable that the polycarbonate of the present invention is not capped with a chromanyl group but is capped with a molecular terminal force and a specific aromatic group.

That is, the second polycarbonate according to the present invention is
To the molecular end of 5-99 mol% polycarbonate molecules
At least one type of chromatomanyl group selected from the group consisting of the above formulas [r], [II] and [III] is bonded, and 1 to 95 mol% of the polycarbonate molecules have Milphenoxy is a polycarbonate to which a group selected from the group consisting of p-tert-butylphenoxy and phenoxy groups is bonded.

Such a polycarbonate is prepared by combining an aromatic organic dihydroxyl group compound and a carbonic acid diester with at least one compound capable of introducing a chromanyl group selected from the group consisting of the above formulas [r], [II] and [III] as an end-capping agent. One type of chroman compound and p-cumylphenoxy group, p-
It can be produced by melt polycondensation using a compound capable of introducing a group selected from the group consisting of a tert-butylphenoxy group and a phenoxy group.

And a compound capable of introducing a chromanyl group represented by the above formulas [I], [II] and [[[I] (terminal capping agent)
Examples include the compounds listed in the description of the first polycarbonate according to the present invention and carbonate compounds having groups thereof.

In the present invention, the p-cumylphenoxy group forming the molecular terminal can be represented by the following formula [V].

...[V] In the present invention, examples of compounds used to introduce the p-cumylphenoxy group represented by the above formula [vl include p-cumylphenol, p-cumylphenyl Mention may be made of phenyl carbonate and di-cumylphenyl carbonate.

Note that such compounds may have an inert substituent on the aromatic ring.

In the present invention, the p-tert-butylphenoxy group forming the molecular terminal can be represented by the following formula [VI].

... [VI] And in the present invention, p- represented by the above formula [V7]
As examples of compounds used to introduce tert-butylphenoxy groups, mention may be made of p-tert-butylphenol, p-tert-butylphenylphenyl carbonate and di-p-tert-butylphenyl carbonate.

Note that such a compound may have an inert substituent on the aromatic ring.

In the present invention, the phenoxy group forming the molecular terminal is
It can be expressed by the following formula [■].

... [■] In the present invention, examples of compounds used to introduce the phenoxy group represented by the above formula [■] include phenol and diphenyl carbonate.

Note that such compounds include, for example, an aromatic ring F may have an inert substituent.

These compounds capable of introducing terminal groups other than chromanyl groups can be used alone or in combination.

In the polycarbonate of the present invention, the terminal groups other than the above-mentioned chromanyl group are usually bonded to the molecular terminals of the polycarbonate in a proportion of 1 to 95 mol%, preferably 1 to 90 mol%, and more preferably 1 to 80 mol%. These constitute the polycarbonate of the present invention.

The polycarbonates of the present invention include all polycarbonates in which chromanyl groups and p-cumylphenoxy, p-tert-butylphenoxy, and phenoxy groups are bonded in the above-mentioned proportions.

That is, for example, during melt polycondensation, the above specific chroman compound and p-cumylphenoxy5p-tert
- Using a combination of a butylphenoxy group and a compound into which a phenoxy group can be introduced, a chromanyl group and a p-cumylphenoxy group,
It may be a polycarbonate into which either a p-tert-butylphenoxy group or a phenoxy group is introduced, or a polycarbonate (a) whose both ends are capped with a chromanyl group,
p-cumylphenoxy group p-tertbutylphenoxy group and polycarbonate (b) whose end is capped with one of the phenoxy groups are prepared separately in advance and mixed in a predetermined ratio. It may also be one prepared by.

The proportion of chromanyl groups represented by the above formula [I] bonded to the terminal positions of such polycarbonate is 20 to 20.
85 mol% and p- bonded at the terminal position.
Cumylphenoxy M, the proportion of p-tert-butylphenoxy group and/or phenoxy group is 15 to 80
Mol% polycarbonate has particularly good impact resistance at low molecular weights, and further improves mechanical properties such as impact resistance in high and low temperature environments.

Next, the first method for producing polycarbonate according to the present invention will be explained.

The polycarbonate according to the present invention can be produced by using a chroman compound as an end-capping agent when producing polycarbonate by melt polycondensation of an aromatic organic dihydroxy compound and a carbonic acid diester.

The aromatic organic dihydroxy compound used in the present invention is
A compound represented by the following formula is used.

However, in the above formula, 1 -SO- or -S○2-, R1 and R2 are hydrogen atoms or monovalent hydrocarbon groups, and R3 is a divalent hydrocarbon group. Further, the aromatic nucleus may have a monovalent hydrocarbon group.

Specific examples of such aromatic organic dihydroxy compounds include bis(4-hydroxyphenyl)methane, 1,1-his(4-bitroxyphenyl)ethane, and 2,2-bis(4-bis(4-hydroxyphenyl)methane).
-hydroxyphenyl)propane, 2,2-bis(4-
hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)octane, bis(4-hydroxyphenyl)phenylmethane, 2,2-bis(4-hydroxy-1-methylphenyl)propane 1,1-bis( 4-hydroxy-t-butylphenyl)
Propane, 2,2-bis(4-hydroxy-3-bromophenyl)
Bis(hydroxyaryl)alkanes such as propane, 1.1-bis(4-hydroxyphenyl)cyclopentane, 1.1-bis(4-hydroxyphenyl)cyclohexane, etc., 4.4 Dihydroxy aryl ethers such as '-dihydroxydiphenyl ether, 4.4'-dihydroxy-3,3'-dimethylphenyl, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxy-3,3' -dihydroxydiaryl sulfides such as dimethyldiphenyl sulfide, 4.4'-dihydroxydiphenyl sulfoxide, 4.
Dihydroxydiaryl sulfoxides such as 4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide, 4.4'-dihydroxydiphenyl sulfone, 4.4°
Dihydroxydiarylsulfones such as -dihydroxy-3,3°-dimethyldiphenylsulfone can be mentioned.

Among these, 2,2-bis(4-hydroxyphenyl)propane is particularly preferred.

Also, as an example of carbonic acid diester, specifically, diphenyl carbonate, ditriyl carbonate, Bis(chlorophenyl) carbonate, 4 and m-cresyl carbonate, dinaphthyl carbonate, bis(diphenyl) carbonate, diethyl carbonate, dimethyl carbonate, dibutyl carbonate, Mention may be made of dicyclohexyl carbonate.

Among these, diphenyl carbonate is particularly preferred.

Note that these diester carbonates may contain dicarboxylic acid or dicarboxylic acid ester. There is no particular restriction on the number of carbon atoms in the group constituting the ester group of such dicarboxylic acid or dicarboxylic acid ester, and specific examples include terephthalic acid, isophthalic acid, diphenyl terephthalate, and diphenyl isophthalate.

As mentioned above, a polyester polycarbonate can be obtained by using a carboxylic acid or a dicarboxylic acid ester as a carbonic acid diester.The polycarbonate of the present invention also includes a polyester polycarbonate obtained as described above.

When producing polycarbonate in the present invention, the above-mentioned carbonic acid diester compound is usually used in an amount of 1.01 to 1.30 mol, preferably 1.02 to 1.20 mol, per 1 mol of the aromatic organic dihydroxy compound. used in amounts of

In the first method for producing polycarbonate according to the present invention, a chroman compound is used as an end-capping agent when polycarbonate is produced by melt polycondensation of an aromatic organic dihydroxy compound and a carbonic acid diester.

In the method of the present invention, the amount of such a roman compound to be used is such that a chromanyl group can be introduced into the molecular terminal of the resulting polycarbonate at the above ratio.
For example, per mole of the aromatic organic dihydroxyl compound as described above, it is usually 0.01 to 0.30 mole, preferably 0.02 to 0.25 mole, and more preferably 0.01 to 0.30 mole.
It is used at a ratio of 0.02 to 0.20 tomol.

If the ratio of the chroman compound used is less than 0.01 mol per 1 mol of the aromatic organic dihydroxy compound, the ends of the obtained polycarbonate will not be sealed with the chromanyl group at a predetermined ratio, and the durability of the low molecular weight polycarbonate will deteriorate. Impact resistance, impact resistance in high-temperature environments and low-temperature environments, etc. may not be sufficiently improved. On the other hand, if the chroman compound is used in an amount exceeding 0.30 mol, not only is it impossible to expect an improvement in the end-capping rate corresponding to the amount of the chroman compound used, but the polymerization rate itself tends to decrease significantly.

In addition, the amount of the end-capping agent other than the above-mentioned chroman compound to be used is such that it is possible to introduce p-cumylphenoxy or p-tert-butylphenoxy groups or phenoxy groups into the molecular terminals of the resulting polycarbonate in the proportions described above. For example, usually 0.01 to 0.30 mol,
It is preferably used in a proportion of 0.02 to 0.25 mol, more preferably 0.02 to 0.20 mol.

) If these compounds are used in a proportion exceeding 0.30 mol per 1 mol of the aromatic organic dihydroxy compound, the amount of terminal capping agent corresponding to the amount of these terminal capping agents used will be Not only is it impossible to expect an improvement in the termination rate, but the polymerization rate itself tends to decrease significantly.

In the melt polycondensation of the aromatic organic dihydroxy compound and the carbonic acid diester as described above, it is preferable to use a compound as described below as a catalyst.

That is, the preferred catalyst used in the present invention is (a)
10-4 per mole of aromatic organic dihydroxy compound
1 per mole of a catalyst comprising a molar amount or less of an alkali metal compound or an alkaline earth metal compound or (a) an aromatic organic dihydroxyl group compound.
A catalyst consisting of an alkali metal compound or alkaline earth metal compound in an amount of 0-4 mol or less and (b) a nitrogen-containing basic compound (a) 10 moles of aromatic organic dihydroxyl group compound - 1 mole of an alkali metal compound or alkaline earth metal compound and (c) boric acid or boric acid ester per mole of (a) aromatic organic dihydroxy compound;
0-' molar amount or less of an alkali metal compound or alkaline earth metal compound, (b) a nitrogen-containing basic compound, and (c
) A catalyst consisting of boric acid or boric acid ester.

Specific examples of alkali metal compounds include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, lithium hydrogen carbonate, sodium carbonate, potassium carbonate, lithium carbonate, sodium acetate, and acetic acid. Potassium, lithium acetate, sodium stearate, potassium stearate, lithium stearate, sodium borohydride, lithium borohydride, sodium borohydride, sodium benzoate, potassium benzoate, lithium benzoate, disodium hydrogen phosphate, Mention may be made of dipotassium hydrogen phosphate and dilithium hydrogen phosphate; the disodium, dipotassium and dilithium salts of bisphenol A; and the sodium, potassium and lithium salts of phenol.

In addition, as a specific example of alkaline earth metal compounds,
Calcium hydroxide, barium hydroxide, magnesium hydroxide, strontium hydroxide, calcium bicarbonate, barium bicarbonate, magnesium bicarbonate, strontium bicarbonate, calcium carbonate, barium carbonate, magnesium carbonate, strontium carbonate, calcium acetate, barium acetate, Mention may be made of magnesium acetate, strontium acetate, calcium stearate, barium stearate, magnesium stearate and strontium stearate.

The above-mentioned alkali metal compound or alkaline earth metal compound is usually used in an amount of 1O"4 mol or less, preferably 10"8 to 10
-5 mol, particularly preferably 10-7 to 10-5 mol.

The amount of the alkali metal compound or alkaline earth metal compound (total amount when both are used together) is 10-"-10-' per mole of the aromatic organic dihydroxy compound.
A molar amount is preferable because the polymerization activity can be increased and a polycarbonate having excellent impact resistance, transparency, fluidity, heat resistance, and water resistance can be obtained.

Specific examples of nitrogen-containing basic compounds include tetramethylammonium hydroxide (MetNOH), tetraethylammonium hydroxide (E ta N
OH), tetrabutylammonium hydroxide (B uj N
ammonium hydroxides having alkyl, aryl or aralyl groups such as trimethylbenzylammonium hydroxide; tertiary amines such as trimethylamine, triethylamine, dimethylbenzylamine and triphenylamine; is an alkyl group such as methyl, ethyl, or an aryl group such as phenyl or tolyl); Primary amines represented by RNH2 (R is the same as above); and ammonia, tetramethylammonium. Borohydride (M ea N B H4), Tetrabutylammonium borohydride (B u4 N B H4), Tetrabutylammonium tetraphenylborate
(B ua N B P ha ), and tetramethylammonium tetraphenylborate (M
Basic salts such as ea N B P ha ) can be mentioned.

Among these, tetraalkylammonium Droxides are particularly preferred.

Nitrogen-containing basic compound (b) as mentioned above is used in a ratio of 10<-6> to 10<-2> moles, preferably 10<4 >to 10<-2> moles, per 1 mole of the aromatic organic dihydroxy compound.

(b) By using the nitrogen-containing basic compound in an amount of 10-6 to 10-1 mol per 1 mol of the aromatic organic dihydroxy compound, the transesterification reaction and polymerization reaction can be carried out at a sufficient rate. This process is preferable because a polycarbonate having excellent impact resistance, transparency, fluidity, heat resistance, and water resistance can be obtained.

(c) As boric acid or boric acid ester, boric acid or formula B (OR) , (OH) sn (in the formula R+4
Boric acid esters such as alkyl such as methyl and ethyl, aryl such as phenyl, and n is 1.2 or 3 are used.

Specific examples of boric acid esters used herein include trimethyl borate, triethyl borate, tributyl borate, trihexyl borate, triheptyl borate, triphenyl borate, tritolyl borate, and trinaphthyl borate. be able to.

(c) Boric acid or boric acid ester as mentioned above is 10-8 to 1 per mole of the aromatic organic dihydroxy compound.
It is used in amounts of 0-1 mol, preferably from 10-7 to 10-2 mol, particularly preferably from 10''e to 10-4 mol.

(c) When the amount of boric acid or boric acid ester is 10-1 to 10-1 mol per 1 mol of the aromatic organic dihydroxy compound, the molecular weight after heat aging is less likely to decrease;
Furthermore, it is preferable because a polycarbonate having excellent impact resistance, transparency, fluidity, heat resistance, and water resistance can be obtained.

In the method for producing polycarbonate according to the present invention as described above, by controlling the total chlorine content contained in the starting materials as described above to 20 ppm or less, more preferably 10 ppm or less, the transparency is particularly unlikely to decrease. Polycarbonate can be obtained.

Chlorine content and LL as used herein refers to the content of chlorine present in acids such as hydrochloric acid or salts such as sodium chloride and potassium chloride, or in organic compounds such as phenyl chloroformate and methylene chloride. death,
It can be measured by analysis using ion chromatography or the like.

The total chlorine content in the starting materials as above is 20 pp
If it is less than m, a polycarbonate with particularly good hue can be obtained, so it is preferable.

The total chlorine content in the starting materials as above is 20pp.
In order to reduce the amount to less than m, use the analogy f1 to reduce these raw materials to p
H value is 6.0-9.0, preferably pH value is 7.0-8
．． 5. More preferably, the pH value is 7.0 to 8.0, and the temperature is 78 to 105°C, preferably 80 to 100°C,
More preferably, it may be washed at a temperature of 80 to 90°C or with a weakly basic aqueous solution.

Weakly basic aqueous solutions used to wash raw materials such as those mentioned above include, for example, sodium hydroxide, potassium hydroxide, lithium hydroxide, carbonic acid (sodium hydroxide, potassium carbonate, ammonium hydroxide, sodium hydrogen carbonate, carbonate An aqueous solution is used in which basic compounds such as potassium hydrogen and tetramethylammonium hydroxide are dissolved in water to exhibit a predetermined pH value. Among these, sodium hydrogen carbonate, sodium carbonate,
It is particularly preferred to use an aqueous solution of potassium hydrogen carbonate, potassium carbonate, sodium hydrogen carbonate or potassium hydrogen carbonate.

Further, it is preferable to wash the raw material, especially the carbonic acid diester, with hot water as described above, and then further distill it before use.

Further, in the present invention, the total sodium ion content contained in the above starting materials is preferably 1.0 pp.
By controlling the amount to be less than m, more preferably less than 0.5 ppm, it is possible to obtain a polycarbonate that is further free from coloration.

The sodium ion content contained in the starting material is
Determined by atomic absorption spectrometry and inductively coupled plasma emission spectrometry.

(In order to reduce the sodium ion content in the starting material to below the above value, distillation, recrystallization,
A purification method such as an adduct method with phenol may be used.

In the present invention, the polycondensation reaction If of an aromatic organic dihydroxy compound and a carbonic acid diester can be carried out under the same conditions as the polycondensation reaction conditions in conventionally known polycarbonate production methods.

Specifically, the first stage reaction is carried out at 80 to 250°C, preferably 100 to 230°C, more preferably 120 to 1
at a temperature of 90°C for 0 to 5 hours, preferably 0 to 4 hours,
More preferably, it is carried out for 0.25 to 3 hours at normal pressure. Next, the reaction temperature was increased while reducing the pressure of the reaction system, and the reaction was further carried out.
A polycondensation reaction between an aromatic organic dihydroxy compound and a carbonic acid diester is carried out at a temperature of 0 to 320°C.

The polycondensation reaction as described above may be carried out continuously or batchwise. In addition, the reaction apparatus used in carrying out the above polycondensation reaction may be of type type, tube wall, or column wall.
Generally, a crosstalk device is used.

The polycarbonate of the present invention obtained as described above has an intrinsic viscosity [η]8 measured in methylene chloride at 20°C, usually 0.1 to 1.0 dl/i, preferably 0.
It is a polycarbonate with a 2 to 0.7 dl/g.

Next, the polycarbonate resin composition according to the present invention will be explained.

The polycarbonate resin composition according to the present invention is a polycarbonate obtained as described above, that is, a polycarbonate whose molecular terminals are capped with chromanyl groups in a specific proportion, or a polycarbonate containing p-cumylphenoxy &
A resin composition can be prepared by blending a specific amount of a phosphorous antioxidant with the polycarbonate of the present invention, which is a polycarbonate whose molecular terminals are capped with a p-tert-butylphenoxy group or a phenoxy group.

Phosphorous antioxidants used here include fL, for example, 11← tri(nonylphenyl) phosphite, 2-ethylhexydiphenyl phosphite, and other alkyl phosphites [e.g., trimethyl phosphite, triethyl phosphite, tributyl phosphite, trioctyl phosphite, distearyl pentaerythrityl diphosphite, tris(2-chloroethyl) phosphite, etc.], triarylphosphites [e.g., triphenyl phosphite, tricresyl phosphite, tris(hydroxy) phenyl) phosphite, tris(nonylphenyl) phosphite, etc.], tricycloalkyl phosphites [e.g. tricycloalkyl phosphite], tricycloalkyl phosphites [e.g. stearyl pentaerythrityl phosphate, tris(2-chloroethyl) phosphate, etc.]
, and triaryl phosphates [e.g. triphenyl phosphate, tricresyl phosphate, tris(
nonylphenyl) phosphate, etc.].

These phosphorus antioxidants can be used alone or in combination.

Such phosphorus-based antioxidants are polycarbonate 10
It is blended in an amount of 0.01 to 0.133 parts by weight, preferably 0.02 to 0.10 parts by weight. By blending the phosphorous antioxidant in such a proportion, it is possible to effectively prevent thermal deterioration of polycarbonate during molding, and the transparency of polycarbonate can be maintained over time even when such polycarbonate is used for a long period of time. There is less chance of a decline in sexual performance. On the other hand, even if it is used in an amount exceeding 0.13 parts by weight, not only is it not possible to expect an antioxidant effect corresponding to the amount blended, but also transparency may be reduced due to the added phosphorus-based polycarbonate resin composition.

In addition, in the polycarbonate resin composition of the present invention, in addition to the above-mentioned phosphorus oxide, commonly used stabilizers such as phenol-based stabilizers, sulfur-based stabilizers, and hindered amine-based stabilizers are used in combination. be able to.

Further, the polycarbonate resin composition of the present invention may optionally contain, for example, a lubricating agent, an inorganic filler, a lubricating agent, a flame retardant, a coloring agent, etc., in addition to the above-mentioned phosphorus antioxidant.

Furthermore, the polycarbonate according to the present invention has a specific chroman group bonded to the terminal position in a specific ratio, so it has sufficient impact resistance even with a molecular weight as low as that of disk grade, and can withstand high temperatures. Mechanical properties such as excellent impact resistance do not deteriorate over a long period of time in environmental and low-temperature environments.

In the method for producing polycarbonate according to the present invention, a specific compound is used as a sealant, so it maintains sufficient impact resistance even with a molecular weight as low as that of disk grade, and also has excellent impact resistance in high-temperature and low-temperature environments. Mechanical properties such as transparency, fluidity, heat resistance and water resistance (hydrolysis resistance) do not deteriorate over a long period of time.
It is possible to efficiently produce polycarbonate with further improved properties.

In the first polycarbonate resin composition according to the present invention,
Since the first polycarbonate according to the present invention, which has the above-mentioned advantages, and a specific antioxidant are contained in a specific ratio, it has particularly excellent mechanical properties such as impact resistance, and has excellent transparency. , has a good balance of various physical properties such as fluidity, heat resistance, and water resistance (hydrolysis resistance).

Moreover, in the polycarbonate resin composition according to the present invention,
Since the polycarbonate according to the present invention, which has the above-mentioned advantages, and a specific antioxidant are contained in a specific ratio, it has particularly excellent mechanical properties such as impact resistance, and has excellent transparency and fluidity. , has a good balance of various physical properties such as heat resistance and water resistance (hydrolysis resistance).

The present invention will be described above with reference to Examples.The present invention is not limited to these Examples.

In addition, the physical properties of the polycarbonate obtained in the following examples are based on the intrinsic viscosity (IV) measured as follows.
End group structure determined using an Ubbelohde viscometer in methylene chloride (0.5 dl/g) at 20°C: 0.4 g of sample was dissolved in 3 ml of chloroform and at 40°C:
Izot impact strength measured using 13 cm NMR (manufactured by JEOL Ltd., GX-270); 63.5 x 12.7 x 1 m (rear notch) injection test in accordance with ASTM D256 Sodium content in the polymer measured using a piece: 20g of polymer was incinerated and atomic absorption (newly manufactured by Hitachi Seisakusho: Hitachi 180-80)
) Hue measured up to the limit value 0,05 ppm (y-tech): The Lab value of a 1 m thick press sheet was measured using Nippon Denshoku Kogyo's Co1or and Co1or Defe.
Yellowness index (YI) was calculated by transmission method using RenceMeter ND-1001DP -71,53a+178.82b YI=00X (1,2'17X-1,0602) Chlorine content in polymer: 50rng Schoriger polymer
It is gasified into an aqueous solution by a method and then subjected to ion chromatography (manufactured by Dionex: Ion Chromatograph 2).
Diphenyl carbonate (Bayer diphenyl carbonate was washed twice with warm water at 80°C and pH 7.0 and distilled with a yield of 90%; Na content 0.05 ppm or less, chlorine content 0, O5 ppm or less) 0.453 kg-mol, and bisphenol A (manufactured by Japan GE Plastics, Na content 0.05 ppm or less, chlorine content 0.05
ppm or less) 0.44℃g-mol and 2,2.4-)
Limethyl-4-(4-hydroxyphenyl)chroman (
Chroman I) 0.022 kg-mol was charged into a 250-liter stirring tank j1. ．． 140 after nitrogen substitution
The solution was then heated to 180'L, and 0.0011 g-mol of boric acid was added thereto, stirred for 30 minutes, and then 0.11 g-mol of tetramethylammonium hydroxide was added as a catalyst. - mol and add 0.00044 g-mol of sodium hydroxide and lower the temperature to 240
℃, and at the same time gradually lowered the pressure to 20 mmHg.The temperature and pressure were kept constant and the amount of distilled phenol was measured.When there was no more distilled phenol, the pressure was returned to atmospheric pressure with nitrogen. The reaction time was 2 hours, and the intrinsic viscosity [IV] of the obtained reaction product was 0.14 d.
Next, this reactant was pressurized using a gear pump and sent to a centrifugal thin film evaporator to proceed with the reaction.The temperature and pressure of the thin film evaporator were controlled to 290°C and 2 mmHg, respectively. The prepolymer extracted from the bottom with a gear pump is passed through a die and made into a strand in a nitrogen atmosphere, cut with a cutter and made into pellets.The intrinsic viscosity [rv] of this prepolymer is 0.32 dl/g. Using an extruder, 40 tons of the polymer were fed into a twin-shaft horizontal stirring polymerization tank (L/D=6, rotating diameter of the stirring blade 150, internal volume 40 liters) controlled at 295°C, o, and 21 Hg for 17 hours, and the residence time was 30. Polymerization was carried out in minutes. Intrinsic viscosity [IV] of the obtained polymer c0.
42dJ/g'T"Ara f.

The results are shown in Table 1.

In Example 1, Chroman 1 was used as the terminal capping agent.
022kg-% Runi Substitute Te 2.4.4-Trimethyl 2-
(4-hydroxyphenyl)chroman (chroman m)0
．． Polycarbonate was obtained in the same manner as in Example 1 except that 0.022 kg-mol was used.
Table 1 shows the results.

A polycarbonate was obtained in the same manner as in Example 1, except that the amount of clothier used in Example 1 was changed to the amount shown in Table 1 and the polymerization temperature was adjusted. Table 1 shows the results.

IV 0.4 manufactured by GE, in which the terminal groups of the polycarbonate are capped with 100 mol% p-cumylphenoxy groups.
50 parts by weight of 2di/g Novolicarbonate and the polycarbonate produced in Example 1) and Irgafuos 168 (phosphorous antioxidant manufactured by Ciba Geigy)
0.05 parts by weight of 8 steel 40 steps≠-280 in a screw extruder
In Example 1, the use of diphenyl carbonate i was changed to 0.453 kg-f-Lucara 0.457 kg-mol, and the terminal capping agent Chroman ■ was not used. Polycarbonate was obtained in the same manner as in Example 1, except that the polycarbonate had an IV of 0.43 di/
Table 1 shows the results.

In Comparative Example 1, the amount of diphenyl carbonate used was varied from [0,453 m-mol] to [0,498 kg].
A polycarbonate was obtained in the same manner as in Comparative Example 1 except that the polycarbonate was changed to IV
The p-cumylphenol group-capped GE used in Example 6 was 0.36 di/g.
Various physical properties were measured using polycarbonate manufactured by Co., Ltd. The results are shown in Table 1.

\ and others

Claims (7)

[Claims] (1) At least one type of chromanyl group selected from the group consisting of the following formulas [I], [II] and [III] is bonded to the molecular terminal of 5 to 99 mol% of polycarbonate molecules. ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・[I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・[II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・[III ] (However, in the above formulas [I], [II] and [III], R^1 to R^8 are each independently hydrogen or an alkyl group having 1 to 9 carbon atoms, and R^5 to R^ 8) It may be further substituted with a halogen atom). (2) At least one type of chromanyl group selected from the group consisting of the following formulas [I], [II] and [III] is bonded to the molecular terminal of 5 to 99 mol% of polycarbonate molecules, and 1 to A polycarbonate characterized in that a group selected from the group consisting of p-cumylphenoxy group, p-tert-butylphenoxy group, and phenoxy group is bonded to the molecular terminal of 95 mol% of polycarbonate molecules; ▲Mathematical formula, chemical formula, There are tables, etc. ▼...[I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼...[II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼...[III] (However, the above formula [I ], [II] and [III], R^1 to R^8 are each independently hydrogen or an alkyl group having 1 to 9 carbon atoms, and R^5 to R^8 are further halogen atoms. (may be replaced). (3) Polycarbonate (A) having the above-mentioned chromanyl group bonded to the molecular end, and polycarbonate (A) having a group selected from the group consisting of p-cumylphenoxy group, p-tert-butylphenoxy group, and phenoxy group bonded to the molecular end ( B) A polycarbonate comprising: (4) An aromatic organic dihydroxy compound and a carbonic acid diester are used as terminal capping agents according to the following formulas [I], [II] and [II].
A method for producing polycarbonate characterized by melt polycondensation using at least one chroman compound capable of introducing a chromanyl group selected from the group consisting of ▲Mathematical formulas, chemical formulas, tables, etc.▼...・[I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼...[II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼...[III] (However, the above formulas [I], [II] and [ III], R^1 to R^8 are each independently hydrogen or an alkyl group having 1 to 9 carbon atoms, and R^5 to R^8 may be further substituted with a halogen atom) . (5) An aromatic organic dihydroxy compound and a carbonic acid diester are used as terminal capping agents according to the following formulas [I], [II] and [II].
I] At least one type of chroman compound capable of introducing a chromanyl group selected from the group consisting of A method for producing polycarbonate characterized by melt polycondensation using at least one possible compound; ▼...[II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼...[III] (However, in the above formulas [I], [II] and [III], R^1 to R^8 are Each independently represents hydrogen or an alkyl group having 1 to 9 carbon atoms, and R^5 to R^8 may be further substituted with a halogen atom). (6) As a catalyst during the melt polycondensation of an aromatic organic dihydroxy compound and a carbonic acid diester, (a) 1 mole of the aromatic organic dihydroxy compound,
A catalyst consisting of an alkali metal compound or an alkaline earth metal compound in an amount of 0^-^4 moles or less, or (a) 1 per mole of an aromatic organic dihydroxyl group compound.
It is characterized by using a catalyst consisting of an alkali metal compound or alkaline earth metal compound in an amount of 0^-^4 or less and (b) a nitrogen-containing basic compound and/or (c) boric acid or a boric acid ester. A method for producing polycarbonate. (7) The polycarbonate according to any one of claims 1 to 3, and 0.01 to 0.13 parts by weight of a phosphorous antioxidant based on 100 parts by weight of the polycarbonate. Characteristic polycarbonate resin composition.