JPH01252640A - Aromatic polyamide/polycarbonate block copolymer - Google Patents

Abstract

PURPOSE:To obtain the title copolymer which is thermoplastic and is excellent in heat resistance, light resistance, hydrolysis resistance, oil resistance, etc., by reacting a specified aliphatic polycarbonate having a carboxyl group on each end with a specified dicarboxylic acid and a specified aromatic diisocyanate. CONSTITUTION:An aliphatic polycarbonate having a carboxyl group on each end, represented by formula III (wherein i is 0-10) and obtained by reacting an aliphatic polycarbonate having a hydroxyl group on each end of formula I (wherein R1 is a 1-12C aliphatic glycol residue, and n is 4-100) with a dicarboxylic acid (derivative) of formula II (wherein R2 is a 2-12C aliphotic or aromatic dicarboxylic acid residue), and a dicarboxylic acid of formula IV (wherein R3 is R2) are used in a specified ratio, and these components are reacted with an aromatic diisocyanate of formula V (wherein Ar is an aromatic group) in the presence of, optionally, a catalyst and a solvent to obtain the title copolymer having repeating units of formulas VI and VII, a weight ratio of units of formula VI to units of formula VII in the range of 95/5-10/90 and an average MW in the range of 10000-500000.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a novel aromatic polyamide/polycarbonate block copolymer, which has excellent heat resistance, light resistance, hydrolysis resistance, oil resistance, etc. , and as a thermoplastic polymer having diostomeric properties, automotive parts,
Useful for general equipment parts, air parts, etc.

[Conventional technology]

Block copolymers, which have a hard segment of aromatic polyamide and a soft segment of aliphatic polyester or aliphatic polyether in their molecular chains, are known as thermoplastic polymers with high heat resistance and diistomeric properties. . For example, US Pat. No. 4,129,715 discloses an aromatic polyamide-based block copolymer in which the soft segment is an aliphatic polyester or an aliphatic polyether ester. However, when the soft segment is an aliphatic polyester,
It has drawbacks such as poor hydrolysis resistance, and when a molded product is exposed to a moist heat environment for a long time, mechanical properties deteriorate. Furthermore, when soft segment aliphatic polyether is used as the main component, there are drawbacks such as light resistance, and there are problems when used outdoors.

[Problem that the invention seeks to solve]

An object of the present invention is to provide a novel aromatic polyamide block copolymer that has heat resistance, hydrolysis resistance, light resistance, etc.

[Means for solving problems]

It is an aromatic polyamide/polycarbonate block copolymer having repeating units of , and having an average molecular weight in the range of 10,000 to 500,000.

The copolymer of the present invention has excellent heat resistance, light resistance, hydrolysis resistance, etc., and is thermoplastic, so it can be molded using the same molding method as ordinary plastics.

In the present invention, specific examples of Ro include ethylene glycol, glopyrin glycol, 1,4-phthanediol, 1,5-bentanediol, 1,6-hexanediol, 1.7-bentanediol, 1.8- Octanediol, 1,9-nonanediol, 1,1O-decanediol, neopentyl glycol, 3-methyl-1,5
-bentanediol, 2-methyl-4,(-dimethyl-
1,6-hexanediol, 2. 2 or more carbon atoms such as z-dimethyl-4-methyl-1,6-hexanediol, dihydroxycyclohexane, cyclohexane dimetatool, etc.
There are 12 aliphatic glycol residues. These may be used alone or in combination of two or more.

Specific examples of the present invention include aliphatic or aromatic acids such as succinic acid, adipic acid, azelaic acid, pimelic acid, glutaric acid, sebacic acid, decanedionic acid, brazilic acid, terephthalic acid, inphthalic acid, and phthalic acid. Examples include group dicarboxylic acid residues.

The number of carbon atoms in this bird and ordinary bird is 2 to 12. These are-
Rice or a combination of two or more species is possible.

Specific examples of Ar in the present invention include diphenylmethane-4,4'-diisocyanate, diphenyl ether-4,4'-diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, etc. aromatic diisocyanate residues. These may be used alone or in combination of two or more.

In the present invention, n ranges from 4 to 100.

If it is less than 4, the physical properties of the obtained copolymer will be insufficient. Also, if it is larger than Zoo, the general formula (1
It becomes difficult to obtain a copolymer consisting of 1 and (m).

In the present invention, i is in the range of 0 to 10, and when it is larger than 10, mass sales may occur due to poor hydrolysis resistance.

The molecular weight of the copolymer of the present invention is in the range of 10,000 to 500,000, preferably in the range of 20,000 to 200,000. The molecular weight here refers to the weight average molecular weight in terms of styrene measured by GPC.

In the present invention, the ratio of general formula (I) and (addition) is in the range of 9515 to 10/90 in terms of weight ratio, preferably in the range of 90/10 to 20780.

The method for producing the copolymer of the present invention is a gentle method. One example is a method of reacting with an aromatic diisocyanate represented by OCNArNCO------(v) (Ar is the same as in the general formulas (I) and (II)).In this case, a catalyst is used. An example of a catalyst is
1-phenyl-3-methyl-2-phosphosine-1-oxide, 1-phenyl-3-methyl-2-phosphosine-
1-sulfide, 1,3-dimethyl-2-phosphosine-
Phosphorous compounds such as 1-oxide; tertiary amines such as triethylenediamine; alkali metal alcoholades such as lithium methylate, sodium methylate, potassium-1-butyrate; alkali metal lactamates such as sodium proviolatamate, etc. can give. The reaction temperature is in the range of 100°C to 280°C, and a solvent may or may not be used. When a solvent is used, sulfolane, diphenyl sulfone, etc. are preferred.

7'CO, the aliphatic polycarbonate with carboxyl groups at both ends of the general formula (2) has the general formula (to) HO(-RaOCO+-RIOH------M(R1*
n is the same as in general formula (1)) Dicarboxylic acid or its derivative (acid anhydride or acid halide) (& is the same as in general formula (I)) ) can be obtained by reacting with

Various oxidation stabilizers, heat stabilizers, light stabilizers, pigments, inorganic fillers, glass fibers and other reinforcing agents can be added to the copolymer of the present invention, if necessary.

〔Effect of the invention〕

The block copolymer of the present invention has excellent heat resistance, light resistance, hydrolysis resistance, oil resistance, etc., and is thermoplastic, so it has extremely great practical value. The block copolymer of the present invention can be applied to a wide range of applications such as automobile parts, general equipment parts, and electrical parts.

〔Example〕

Examples will be described below, but the present invention is not limited thereto.

Example 1 (1) Synthesis stirrer for aliphatic polycarbonate diol,
In a reactor equipped with a thermometer and a fractionating tube, 236 g of 1,6-hexanediol and 1,5-bentanediol zos
Add 0.9211 g of metallic sodium at 70-80℃
was added under stirring. After the sodium has completely reacted,
23611 diethyl carbonate was introduced. When the reaction temperature was raised to 95-100°C, ethanol began to distill out. The temperature was gradually raised to 160° C. over about 6 hours, during which time ethanol containing a small amount of diethyl carbonate was distilled out. Thereafter, the pressure in the reactor was further reduced to 10-10-10,000 ml,
The reaction was carried out at 200° C. for 4 hours with strong stirring while extracting ethanol. After cooling, the generated polymer was dissolved in dichloromethane, neutralized with dilute acid, and washed with water several times.
After dehydration with anhydrous sodium sulfate, the solvent was distilled off, and 2 to 31 g of the product was further dried at 140° C. for several hours. The number average molecular weight determined from the hydroxyl value of the obtained copolycarbonate diol was 2.100.

In a reactor equipped with a nasal stirrer and a temperature needle, 200 g of the polycarbonate diol described above were charged with 19.1/i of succinic anhydride.
After the system was replaced with N2, the temperature was heated to 130° with stirring.
The temperature was gradually raised to C and the reaction was continued for 2 hours.

The obtained polymer was a liquid, and when analyzed by GPC,
No unreacted succinic anhydride was observed.

Moreover, it was confirmed by C15-NMR that all the terminals of the polymer were carboxyl groups and no hydroxyl groups remained. The carboxylic acid equivalent according to the neutralization titration button is 1,1
It was 50.

In a reactor equipped with a stirrer and a thermometer, 8.7 g of the polycarbonate with carboxyl groups at both ends obtained in (2) above, 4011 adipic acid, and 2301 g of sulfolanic acid. and as a catalyst, 1-phenyl-3-methyl-2-phosphosine-1
After 0.16 p of -oxide was charged and the temperature was raised to 165° C. with N, 19.2 g of diphenylmethane-4 (easy isocyaner) was gradually added while stirring, and the mixture was reacted for 3 hours. The obtained polymer solution was poured into a large amount of water and solidified. After the coagulated polymer was cut into pieces, it was washed in methanol under reflux. The molecular weight of the polymer obtained after vacuum drying was 60,000 in terms of styrene by GPC. The weight ratio of the repeating units corresponding to general formula (1) and (nl) is about 70/30 based on the charging ratio.

The obtained polymer was pressed at 210°C to obtain a sheet with a thickness of 21 m. The sheet has elastomer-like elasticity, and in measurements based on JIS-6301,
Hardness (JIS A) was 90.

When dynamic viscoelasticity was measured using this sheet, the inflection point at which the storage modulus suddenly decreased was 195°C, indicating high heat resistance.

In addition, the tensile strength of dumbbells punched from this sheet was measured using a weather meter, and carbon arc was heated at 63℃ and 15℃.
When comparing before and after time irradiation, the retention rate was 99%, and almost no deterioration in physical properties was observed due to the irradiation test.

In addition, after immersing a part of this sheet in hot water at 100°C for 15 hours, the molecular weight in terms of styrene by GPC was 59.0.
00, and almost no decrease in molecular weight was observed due to pressing and hot water treatment.

Patent applicant: Asahi Kasei Industries, Ltd.

Claims (1)

[Claims] General formulas (I) and (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(II) (R_1 is , represents an aliphatic glycol residue having 2 to 12 carbon atoms. R_2 and R_3 are aliphatic or aromatic dilboxylic acid residues, and the number of carbon atoms in R_2 and R_3 is 212.
It is. Ar represents aromatic diisocyanate residue. R_1, R_2, R_3, and Ar are each one type or a combination of two or more types. n is a number ranging from 4 to 100 on average, and i is a number ranging from 0 to 10 on average. ) repeating unit, and an aromatic polyamide polycarbonate block copolymer characterized by having an average molecular weight in the range of 10,000 to 50.