JPH085953B2 - Terminal amino group-containing polycarbonate and method for producing the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a novel terminal amino group-containing polycarbonate and a method for producing the same. More specifically, the present invention has a reactive amino group at the terminal, and by reacting the resin with other resin or filler capable of reacting with this amino group, the amino group is contained in a compatible manner. And a terminal amino group-containing polycarbonate useful as a raw material of a block copolymer, and a method for efficiently producing the same.

[Prior Art] In recent years, polycarbonate has been used as an engineering plastic excellent in heat resistance, impact resistance, transparency, and the like.
Widely used in many fields. As a method for producing this polycarbonate, for example, 2,2-bis (4
-Hydroxyphenyl) propane (bisphenol A)
Interfacial polymerization method of reacting phosgene with phosgene (phosgene method),
Also, a transesterification method of reacting bisphenol A with diphenyl carbonate is known as a typical production method.

In the method for producing a polycarbonate by the interfacial polymerization method, usually, first, phosgene is introduced into a mixed solution of an alkali hydroxide aqueous solution of an aromatic dihydroxy compound and an organic solvent to form an oligomer of the polycarbonate, and then the polycarbonate The organic phase containing the oligomer is brought into contact with an aqueous alkali hydroxide solution of an aromatic dihydroxy compound to generate a high molecular weight polycarbonate, and then the polymerization terminated liquid is subjected to washing treatment such as alkali washing treatment, acid washing treatment and water washing treatment. A method is used in which, after sequential application, the polycarbonate is recovered from the obtained organic phase.

In such a method for producing a polycarbonate,
In order to adjust the molecular weight of the polycarbonate, a molecular weight modifier is usually used when the organic phase containing the polycarbonate oligomer and the alkali hydroxide aqueous solution of the aromatic dihydroxy compound are brought into contact with each other to bring the high molecular weight polycarbonate into contact.

As the molecular weight regulator, it has been known that monohydric phenols such as pt-butylphenol and phenol are used, and long-chain alkylphenols are used for improving fluidity.

However, the polycarbonate produced by such a conventional molecular weight regulator is essentially inactive at the polymer end because the molecular chain end is closed, and therefore, the composition with other resins and other fillers is low. In the case of modification such as a product, since it is a simple mixing type, it has a drawback that the partner resin and the filler are unavoidable.

On the other hand, it has been attempted to produce a polycarbonate having a reactive group introduced at its terminal and modify the polycarbonate by utilizing this reactive group. For example, using a monovalent unsaturated hydroxy compound such as allyl alcohol or allyl phenol as a molecular weight regulator to obtain a terminal unsaturated polycarbonate, a polycarbonate block copolymer formed by addition-polymerizing a vinyl compound is disclosed. (Japanese Patent Publication No. 48-25076). However, in the terminal-unsaturated polycarbonate, the unsaturated group to be introduced has insufficient heat resistance when it is an aliphatic type such as an allyloxy group, whereas it is a vinyl group when it is an aromatic type such as an allylphenoxy group. Since it has extremely high reactivity, there is a problem in stability such as easy gelation during the reaction.

Further, as a molecular weight modifier, a polycarbonate having an isopropenylphenoxy group at the end, which is produced by using isopropenylphenol, is disclosed (JP-A-63-63).
-3023). However, in this vinyl-terminated polycarbonate, although the isopropenylphenoxy group is more stable than the above-mentioned allylphenoxy group, there is a drawback that the resin reactive with the vinyl group is limited.

[Problems to be Solved by the Invention] Under these circumstances, the present invention is directed to reacting a functional group at the terminal with another resin or filler capable of reacting with the functional group and the functional group. By doing so, it is possible to provide a composition having excellent properties containing them in a compatible manner,
The purpose of the present invention is to provide a terminal functional group-containing polycarbonate which has excellent characteristics such as easy modification using the terminal functional group and good stability.

[Means for Solving the Problem] The inventors of the present invention have conducted extensive studies to develop a terminal functional group-containing polycarbonate having the above-mentioned excellent characteristics, and as a result, used specific aminophenols as a molecular weight regulator. It was found that the object can be achieved by reacting a specific aromatic dihydroxy compound and a carbonate ester-forming derivative in a liquid medium, and the present invention has been completed based on this finding.

That is, the present invention has the general formula (In the formula, R ¹ , R ² , R ³ and R ⁴ are each a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ¹ and R ² are bonded to each other to form a ring. Well, m and n are each an integer of 1 to 4, and when m is 2 or more, R ³ may be the same or different, and when n is 2 or more, R ^{4 is} May be the same as or different from each other) and has a repeating unit represented by (Wherein R is a mere bond, an alkylidene group or an alkylene group having 1 to 8 carbon atoms, X is a hydrogen atom, a halogen atom or an alkyl group having 1 to 4 carbon atoms, p is an integer of 1 to 4, and p is When X is 2 or more, X may be the same or different) and a terminal amino group having an aminophenoxy group represented by the formula (1) and a viscosity average molecular weight of 15,000 or more. A polycarbonate containing material is provided.

According to the present invention, the terminal amino group-containing polycarbonate has the following general formula: (Wherein X, R and p have the same meanings as described above), in the presence of a molecular weight regulator consisting of aminophenols represented by the general formula (Wherein R ¹ , R ² , R ³ , R ⁴ , m and n have the same meanings as defined above) and a carbonic acid ester forming derivative. be able to.

 Hereinafter, the present invention will be described in detail.

The terminal amino group-containing polycarbonate of the present invention has the repeating unit represented by the general formula (I) as its main chain. R ¹ , R ² , R ³ in the general formula (I)
And R ⁴ are each a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group. However, they may be the same or different from each other. Further, R ¹ and R ² may be bonded to each other to form a ring, and for example, those having a structure in which two phenylene groups are bonded via a 1,1-cyclohexylene group are also included in the present invention. Included.
M and n in the general formula (I) are each an integer of 1 to 4, but when m is an integer of 2 or more, R ³ may be the same or different, When n is an integer of 2 or more, R ⁴ may be the same or different.

The polycarbonate of the present invention has a repeating unit represented by the general formula (I) as a main chain, and an aminophenoxy group represented by the general formula (II) bonded to the terminal position thereof. It is a feature. Here, the content of aminophenoxy units in the polycarbonate of the present invention is preferably 0.01 to 20 mol% with respect to the total amount of aromatic di-hydroxy units and aminophenoxy units. R in the general formula (II) is a mere bond,
An alkylidene group or an alkylene group having 1 to 8 carbon atoms, X is a hydrogen atom, a halogen atom or an alkyl group having 1 to 4 carbon atoms, and p is an integer of 1 to 4. Further, when p is an integer of 2 or more, the Xs may be the same or different.

A typical example of such an aminophenoxy group is p
-Aminophenoxy group, m-aminophenoxy group, 4-
Amino-3-methylphenoxy group, 4-amino-3-ethylphenoxy group, 3-amino-4-methylphenoxy group, 3-amino-4-ethylphenoxy group, 4-amino-3-chlorophenoxy group, 3- Amino-4-chlorophenoxy group, 4-amino-3,5-dichlorophenoxy group, 4-amino-3-bromophenoxy group, 3-amino-4-bromophenoxy group, 4-amino-3,5-dibromophenoxy group Group, 4-aminomethylphenoxy group, 3-
Methyl-4-aminomethylphenoxy group, 3-ethyl-
4-aminomethylphenoxy group etc. can be mentioned.

Further, the polycarbonate of the present invention needs to have a viscosity average molecular weight of 15,000 or more. If the viscosity average molecular weight is less than 15,000, impact resistance and the like are insufficient.

As described above, the polycarbonate of the present invention has a structure in which the repeating unit represented by the general formula (I) is a main chain, and the aminophenoxy group represented by the general formula (II) is bonded to the terminal position. However, the repeating unit other than the repeating unit represented by the general formula (II) may be contained in the molecular chain, if necessary, within a range not impairing the object of the present invention.

The polycarbonate of the present invention can be produced by a method which is conventionally used in the production of polycarbonate, but according to the production method of the present invention, efficiently,
Moreover, high quality products can be obtained.

In the method of the present invention, the above-mentioned general formula (II
An aromatic dihydroxy compound represented by I) and a carbonic acid ester forming derivative are used. Examples of the aromatic dihydroxy compound include bis (4-hydroxyphenyl)
Methane, bis (3,5-dimethyl-4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane (usually bisphenol A), 2- Methyl-1,1-bis (4-hydroxyphenyl) propane, 2,2-bis (3,5
-Dimethyl-4-hydroxyphenyl) propane, 1-
Ethyl-1,1-bis (4-hydroxyphenyl) propane, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl)
Butane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) pentane,
2,2-bis (4-hydroxyphenyl) isopentane,
4-methyl-2,2-bis (4-hydroxyphenyl) pentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (4-hydroxyphenyl) hexane, 2,2-bis (4 -Hydroxyphenyl) isohexane, 4,4-bis (4-hydroxyphenyl) heptane and the like can be mentioned. Among these, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) is particularly preferable. . These aromatic dihydroxy compounds may be used alone or in combination of two or more.

In the present invention, other aromatic dihydroxy compounds can be used in combination with the aromatic dihydroxy compound represented by the general formula (III), if desired, within a range not impairing the object of the present invention. Other aromatic dihydroxy compounds include, for example, bis (4-hydroxyphenyl) phenylmethane, bis (4-hydroxyphenyl) naphthylmethane, diphenyl-bis (4-hydroxyphenyl) methane, bis (3,5-dichloro-). 4-hydroxyphenyl) methane, 1-naphthyl-1,1-bis (4-hydroxyphenyl) ethane, 1-phenyl-1,
1-bis (4-hydroxyphenyl) ethane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane, 2 , 2-bis (3-fluoro-4-hydroxyphenyl) propane, 1,1-bis (3,5-dichloro-
4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) cyclododecane, 2,2-bis (4-hydroxyphenyl) nonane, 1,10-bis (4
-Hydroxy) phenyldecane, 1,2-bis (4-hydroxyphenyl) propane, dihydroxyarylalkanes such as 1,4-bis (4-hydroxyphenyl) butane, bis (4-hydroxyphenyl) sulfone, bis (3 Dihydroxyaryl sulfones such as 5,5-dimethyl-4-hydroxyphenyl) sulfone and bis (3-chloro-4-hydroxyphenyl) sulfone, bis (4
-Hydroxyphenyl) ether, dihydroxyaryl ethers such as bis (3,5-dimethyl-4-hydroxyphenyl) ether, 4,4'-dihydroxybenzophenone, 3,3'-5,5'-tetramethyl-4, Dihydroxy aryl ketones such as 4′-dihydroxybenzophenone, bis (4-hydroxyphenyl) sulfide,
Bis (3-methyl-4-hydroxyphenyl) sulfide, bis (3,5-dimethyl-4-hydroxyphenyl)
Dihydroxyaryl sulfides such as sulfides,
Dihydroxyaryl sulfoxides such as bis (4-hydroxyphenyl) sulfoxide, dihydroxydiphenyls such as 4,4′-dihydroxyphenyl, dihydroxybenzenes such as hydroquinone, resorcinol and methylhydroquinone, 1,5-dihydroxynaphthalene, 2,6 -Dihydroxynaphthalene and the like such as dihydroxynaphthalene. These may be used alone or in combination of two or more.

As the carbonic acid ester-forming derivative, phosgene is usually used. In addition to phosgene, various compounds such as bromophosgene, diphenyl carbonate,
It is also possible to use di-p-tolyl carbonate, phenyl-p-tolyl carbonate, di-p-chlorophenyl carbonate, dinaphthyl carbonate and the like.

In the method of the present invention, when a polycarbonate is produced from an aromatic dihydroxy compound represented by the general formula (III) and a carbonic acid ester-forming derivative, the reaction system is represented by the general formula (IV) as a molecular weight regulator. It is necessary to have the aminophenols mentioned.

Examples of the molecular weight regulator include p-aminophenol, m-aminophenol, 4-amino-3-methylphenol, 4-amino-3-ethylphenol and 3-aminophenol.
Amino-4-methylphenol, 3-amino-4-ethylphenol, 4-amino-3-chlorophenol, 3
-Amino-4-chlorophenol, 4-amino-3,5-
Dichlorophenol, 4-amino-3-bromophenol, 3-amino-4-bromophenol, 4-amino-
3,5-dibromophenol, 4-hydroxybenzylamine, 4-hydroxy-2-methylbenzylamine, 2
-Ethyl-4-hydroxybenzylamine or the like can be used.

The amount of these molecular weight regulators used is usually 1 to 200 mol% with respect to the total amount of the aromatic dihydroxy compound used as a raw material and the molecular weight regulator.

The method of the present invention is a method for producing a polycarbonate by allowing a reaction to proceed in a liquid medium. For example, an interfacial polymerization method or a pyridine method can be used, but the interfacial polymerization method is industrially preferable.

Next, one example of a suitable method for producing the terminal amino group-containing polycarbonate of the present invention by this interfacial polymerization method will be described. First, the aromatic dihydroxy compound as a raw material is dissolved in an aqueous solution of an alkali metal hydroxide to give an aromatic compound. After preparing an aqueous alkali hydroxide solution of a dihydroxy compound,
A carbonate ester-forming derivative such as phosgene is introduced into a mixed solution of this aqueous solution and an organic solvent to produce a polycarbonate oligomer, and then an organic phase containing this polycarbonate oligomer and an aqueous alkali hydroxide solution of an aromatic dihydroxy compound, The chloroformate-terminated polycarbonate is produced by contacting in the presence of a catalyst, an antioxidant and the like which are used as desired. Next, to the organic phase containing the chloroformate-terminated polycarbonate, an aqueous solution of alkali hydroxide, a molecular weight modifier, and a catalyst used as desired are added and reacted to obtain a terminal amino group-containing polycarbonate.

Here, the aminophenols as the molecular weight regulator are preferably used in an excess amount with respect to the chloroformate group.

Examples of the organic solvent used in this case include dichloromethane, chloroform, carbon tetrachloride, 1,1-dichloroethane, 1,2-dichloroethane, 1,1,1-trichloroethane, 1,1,2-trichloroethane, 1,1, Examples thereof include chlorinated hydrocarbons such as 1,2-tetrachloroethane, 1,1,2,2-tetrachloroethane, pentachloroethane, hexachloroethane and chlorobenzene, and acetophenone. These solvents may be used alone or in combination of two or more. Examples of the alkali metal hydroxides include sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide and the like. Among these, sodium hydroxide and potassium hydroxide are preferable, and sodium hydroxide is particularly preferable. Is preferred. Further, examples of the catalyst used as desired include a tertiary amine and a quaternary ammonium halogen salt.

In the interfacial polymerization method, the polycarbonate oligomer obtained by reacting phosgene is an oligomer having a hydroxyl group and a chloroformate group (-OCOCl) at the end of the molecule, and the ratio of these two groups is It can be arbitrarily changed by appropriately selecting the introduction method, the concentration of the alkali hydroxide aqueous solution of the aromatic dihydroxy compound, the reaction temperature and the like.

Furthermore, the reaction system is not particularly limited, and may be a batch system or a continuous system. Further, as a reaction apparatus, a tank reactor equipped with a stirrer is usually used in batch reaction, but in continuous reaction, a plurality of tank reactors arranged in series may be used. Alternatively, a tubular reactor may be used.

In this way, the polymerization-terminated liquid obtained by completing the polymerization reaction is an organic phase containing the produced polycarbonate and the like, and an aqueous phase containing the alkali metal hydroxide and the by-produced alkali metal chloride. And a terminal amino group-containing polycarbonate can be recovered by performing a post-treatment that is conventionally used in the interfacial polymerization method.

The terminal amino group-containing polycarbonate thus obtained is an acid anhydride that cannot be obtained as a useful composition due to poor compatibility with the conventional simple mixing method by utilizing the amino group. By reacting with a substance-containing resin or other filler, it is possible to provide a composition containing them in a compatible manner and having excellent properties, and various modifications are possible by utilizing the amino group. , And can also be used as a raw material for block copolymers,
It has excellent characteristics.

EXAMPLES Next, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples.

Example 1 91 g of bisphenol A, 330 ml of methylene chloride and 560 ml of 2.0N aqueous sodium hydroxide solution were placed in a flask with a stirrer having an internal volume of 2 l and stirred, and phosgene was blown into this for 70 minutes while cooling with an ice bath. When the reaction solution thus obtained was allowed to stand at room temperature, a methylene chloride solution of an oligomer was separated and formed in the lower layer. The oligomer solution had an oligomer concentration of 320 g / l, an oligomer number average molecular weight of 850, and a chloroformate group concentration of 0.7 mol / l.

Then, in a flask with a stirrer having an internal volume of 2 l, 280 m of the above-mentioned polycarbonate oligomer in methylene chloride solution
1, 18 g of bisphenol A, 100 ml of 2.0 N sodium hydroxide aqueous solution, and 0.2 g of triethylamine were added and reacted for 1 hour. The obtained reaction solution was washed with water to obtain a methylene chloride solution of a chloroformate-terminated polycarbonate. The chloroformate group-terminated polycarbonate had a chloroformate group content of 1.0 × 10 ⁻⁴ mol / g and a viscosity average molecular weight of 24,000.

Next, in a flask with a stirrer having an internal volume of 2 l, 400 ml of a methylene chloride solution of the chloroformate group-terminated polycarbonate thus obtained (chloroformate group-terminated polycarbonate 80 g, chloroformate group 0.008 mol
l), p-aminophenol 8.7g (0.08mol), 2.0N sodium hydroxide aqueous solution 200ml, triethylamine 0.8g
(0.008 mol) was added and the mixture was reacted for 1 hour. The obtained reaction solution was washed with an alkali, washed with an acid, washed with an alkali and washed with water, and then poured into methanol to obtain a target terminal amino group-containing polycarbonate.

The terminal amino group fraction, viscosity average molecular weight and Tg of this product are shown in Table 1.

Example 2 In Example 1, the amount of bisphenol A used was 16.7.
In the same manner as in Example 1 except that the amount was changed to g, the content of the chloroformate group was 1.4 × 10 ⁻⁴ mol / g, and the viscosity average molecular weight was 16000.
A methylene chloride solution of the chloroformate-terminated polycarbonate of was obtained.

Then, chloroformate-terminated polycarbonate 80
A terminal amino group-containing polycarbonate was obtained in the same manner as in Example 1 except that g and p-aminophenol 12.2 g were used.

The terminal amino group fraction, viscosity average molecular weight and Tg of this product are shown in Table 1.

The terminal amino group fraction is ¹ H-NMR (d ₆ -DMSO: CDCl
₃ = 3: 5).

δ 1.6 s CH ₃ 4.9 s NH ₂ 6.4 to 7.8 mAr-H 9.1 s OH [Effect of the Invention] According to the method of the present invention, by using a specific aminophenol as a molecular weight regulator, a reactive amino group at the terminal can be obtained. A polycarbonate containing a can be easily produced.

This terminal amino group-containing polycarbonate provides a composition having excellent properties containing them in a compatible manner by reacting the other amino group-reactive resin or filler with the amino group. While being able to
The amino group can be used for various modifications, and it can be used as a raw material for a block copolymer.

Claims (2)

[Claims] 1. A general formula (In the formula, R ¹ , R ² , R ³ and R ⁴ are each a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ¹ and R ² are bonded to each other to form a ring. Well, m and n are each an integer of 1 to 4, and when m is 2 or more, R ³ may be the same or different, and when n is 2 or more, R ⁴ is May be the same or different) and has a repeating unit represented by (Wherein R is a mere bond, an alkylidene group or an alkylene group having 1 to 8 carbon atoms, X is a hydrogen atom, a halogen atom or an alkyl group having 1 to 4 carbon atoms, p is an integer of 1 to 4, and p is When X is 2 or more, X may be the same or different) and a terminal amino group having an aminophenoxy group represented by the formula (1) and a viscosity average molecular weight of 15,000 or more. Containing polycarbonate. 2. A liquid having a general formula in the presence of a molecular weight regulator in a liquid medium. (In the formula, R ¹ , R ² , R ³ and R ⁴ are each a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ¹ and R ² are bonded to each other to form a ring. Well, m and n are each an integer of 1 to 4, and when m is 2 or more, R ³ may be the same or different, and when n is 2 or more, R ⁴ is (May be the same or different) In producing a polycarbonate from an aromatic dihydroxy compound represented by (Wherein R is a mere bond, an alkylidene group or an alkylene group having 1 to 8 carbon atoms, X is a hydrogen atom, a halogen atom or an alkyl group having 1 to 4 carbon atoms, p is an integer of 1 to 4, and p is When 2 is 2 or more, X may be the same or different.) The method for producing a terminal amino group-containing polycarbonate according to claim 1, characterized in that .