JPS6315286B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is a novel polymer comprising an olefinically unsaturated nitrile, another monovinyl component, and maleic anhydride, which has a high heat deflection temperature, good gas shear properties, and low creep properties. Concerning the manufacturing method.

The process for producing the novel polymers of the present invention consists of polymerizing a large amount of an olefinically unsaturated nitrile, such as acrylonitrile, and a small amount of another monovinyl monomer component, which necessarily contains maleic anhydride.

That is, the present invention provides (A) structural formula 60-90% by weight of at least one nitrile (wherein R is hydrogen, a lower alkyl group having 1 to 4 carbon atoms, or a halogen)
(B) 1 to 30% by weight of maleic anhydride; (C)(i) styrene or α-methylstyrene; and (ii) structural formula (However, R ₁ is hydrogen, an alkyl group having 1 to 4 carbon atoms, or a halogen,
R ₂ is an alkyl group having 1 to 6 carbon atoms); % is (A) and (B)
The present invention relates to a method for producing a high nitrile resin containing maleic anhydride, which comprises polymerizing (C) (based on the total weight).

The olefinically unsaturated nitriles useful in the present invention have the structural formula (wherein R is hydrogen, a lower alkyl group having 1 to 4 carbon atoms, or a halogen). Such compounds include acrylonitrile, α-
Includes chloroacrylonitrile, α-fluoroacrylonitrile, methacrylonitrile, ethacrylonitrile, etc. The most preferred olefinically unsaturated nitrile is acrylonitrile.

Other monovinyl monomer components copolymerizable with the olefinically unsaturated nitrile useful in the present invention include one or more of vinyl aromatic monomers, esters of olefinically unsaturated carboxylic acids, and the like.

The vinyl aromatic monomers include styrene and alpha-methylstyrene.

The olefinic unsaturated carboxylic acid ester has the structural formula (However, R ₁ is hydrogen, an alkyl group having 1 to 4 carbon atoms, or a halogen, and R ₂ is 1
an alkyl group having ~6 carbon atoms). Compounds of this type include methyl acrylate, ethyl acrylate, propyl acrylates, butyl acrylates, amyl acrylates,
Contains hexyl acrylates, methyl methacrylate, ethyl methacrylate, propyl methacrylates, butyl methacrylates, amyl methacrylates, hexyl methacrylates, methyl α-chloroacrylate, ethyl α-chloroacrylate, and the like.
The most preferred in the present invention is methyl acrylate,
They are ethyl acrylate, methyl methacrylate, and ethyl methacrylate.

Maleic anhydride is an essential component of the resin obtained by the production method of the present invention.

The present invention can be prepared by batch, continuous, or intermittent addition of monomers and other ingredients by any of the known common polymerization methods, including bulk polymerization, solution polymerization, emulsion or suspension polymerization methods. The method for producing the polymer of the invention can be carried out. A preferred method is to use a polymerization method in the presence of a suitable solvent and a free radical generating initiator to
It is a solution polymerization in the substantial absence of molecular oxygen at temperatures in the range of °C.

The new polymers produced by this method can be thermoformed into a wide variety of useful articles by any of the conventional methods used for known thermoplastics, such as extrusion, kneading, molding, drawing, injection, etc. It is a thermoplastic material that can be easily processed. The polymer product obtained by the method of the invention has excellent solvent resistance,
It is useful in the packaging industry because of its impact strength and low permeability to gases and vapors, and is particularly useful in the manufacture of bottles, films, sheets, pipes, and other types of containers for liquids and solids.

In the following examples, unless otherwise specified, component amounts are expressed in parts by weight.

Example 1 (A) 75 parts of acrylonitrile, 3 parts of styrene, and 75 parts of methyl ethyl ketone were added to a polymerization reactor.
Acrylonitrile-styrene copolymers were made that were outside the scope of the present invention. The mixture was stirred to 76°C under nitrogen atmosphere. Feeds of 22 parts of styrene, 25 parts of methyl ethyl ketone, and 0.3 parts of azobisisobutyronitrile were added continuously and uniformly over 4.5 hours. Heat the final reaction mixture to 76-78 °C
I kept it there for another hour. The total conversion of monomer to polymer was 6.8% of theory.

The reactor contents were poured into a stirred mixture of 1:1 volume of benzene and petroleum ether. The solid polymer was isolated and dried under reduced pressure at 45-60°C for 48 hours. This resin has an ASTM heat deflection temperature of 84-94℃ and a bending strength of 1.202× ¹⁰³ Kg/ ^cm2 (17.1
×10 ³ psi), flexural modulus 3.867 × 10 ⁴ Kg/cm ² (5.50
×10 ⁵ psi), tensile strength 9.912 × 10 ² Kg/cm ² (14.1 ×
10 ³ psi), oxygen transmission rate 3.5 cc - mils/100 square inches/24 hours/atmosphere, water vapor transmission rate 8.0 g -
mils/100 square inches/24 hours/atmosphere.

(B) An acrylonitrile-styrene-maleic anhydride terpolymer within the scope of the invention was prepared by the procedure of Example (A), except that the continuous feeds were 5 parts maleic anhydride, 17 parts styrene, and 25 parts methyl ethyl ketone. part, 0.3 parts of azobisisobutyronitrile, and 5 parts of continuous feed.
Added uniformly over time. The total conversion of monomer to polymer was 80% of theory. The resin produced in this way has an ASTM heat deflection temperature of 102°C.
Bending strength 1.315×10 ³ Kg/cm ² (18.7×10 ³ psi), flexural modulus 4.244×10 ⁵ Kg/cm ² (6.06×10 ⁵ psi), tensile strength 1.069×10 ³ Kg/cm ² ( 15.2×10 ³ psi), an oxygen transmission rate of 4.6 cc-mils/100 square inches/24 hours/atmosphere, and a water vapor transmission rate of 0.9 g-mils/100 square inches/24 hours/atmosphere.

Example 2 The procedure of Example 1(A) was followed except that the initial reactor charge was 70 parts acrylonitrile, styrene.
2.8 parts, 75 parts of methyl ethyl ketone, and the continuous feed was 5 parts of maleic anhydride, 22.2 parts of styrene.
1 part, 25 parts of methyl ethyl ketone, and 0.3 parts of azobisisobutyronitrile. Continuous feed was added evenly over 6 hours. The total conversion of monomer to polymer was 81% of theory. The resulting resinous polymer has an ASTM heat deflection temperature of 104°C, a bending strength of 1.329×10 ³ Kg/cm ² (18.9×10 ³ psi), and a flexural modulus of elasticity of
4.309×10 ⁴ Kg/cm ² (6.13×10 ⁵ psi), tensile strength 9.983
×10 ² Kg/cm ² (14.2 × 10 ³ psi).

Example 3 Initial reaction charge of 70 parts acrylonitrile, 2.8 parts styrene, 75 parts methyl ethyl ketone and 10 parts maleic anhydride, 17.8 parts styrene, 25 parts methyl ethyl ketone, 0.3 parts azobisisobutyronitrile.
The polymer was prepared by the procedure described in Example 2 using a continuous feed consisting of The resin produced is
ASTM heating deflection temperature 107℃, flexural modulus 4.239
×10 ⁴ Kg/cm ² (6.03 × 10 ⁵ psi), oxygen permeation rate 2.7cc
- Mil / 100 square inches / 24 hours / atmospheric pressure, water vapor transmission rate 5.4 g - Mil / 100 square inches / 24 hours /
It turns out that it has atmospheric pressure.

Example 4 (A) In a polymerization reactor, 75 parts of acrylonitrile, 25 parts of methyl acrylate, 100 parts of methyl ethyl ketone,
By adding 0.1 part of azobisisobutyronitrile, a copolymer of acrylonitrile and methyl acrylate outside the scope of the present invention was made.
The polymerization reaction was carried out at 77° C. for 2 hours with stirring under a nitrogen atmosphere. The polymer was isolated by coagulation with a 1:1 volume mixture of benzene and petroleum ether. The dry resinous polymer has an ASTM heat deflection temperature of 76°C, flexural strength (21.4 x ¹⁰³ psi), and flexural modulus.
4.612×10 ⁴ Kg/cm ² (6.56×10 ⁵ psi), tensile strength
7.452Kg/cm ² (10.6×10 ³ psi), oxygen transmission rate 0.35
cc-mil/100 square inches/24 hours/atmospheric pressure, water vapor transmission rate 4.3 g-mil/100 square inches/24
I found out that it has time/atmospheric pressure.

(B) The procedure of Example (A) was followed except that the components of the polymerization mixture were 70 parts of acrylonitrile, 20 parts of methyl acrylate, 10 parts of maleic anhydride, 100 parts of methyl ethyl ketone, and 0.1 part of azobisisobutyronitrile. It was hot. The resulting polymer has an ASTM heating deflection temperature of 83°C and a bending strength of 1.793×10 ³ Kg/cm ²
(25.5×10 ³ psi), flexural modulus 5.265×10 ³ Kg/cm ²
(0.75×10 ⁵ psi), tensile strength 9.420×10 ² Kg/cm ²
(13.4×10 ³ psi), oxygen transmission rate 0.24cc-mil/
It was found to have a water vapor transmission rate of 3.2 g-mils/100 square inches/24 hours/atmosphere.

Example 5 The procedure of Example 4 (A) was repeated, except that the components of the polymerization mixture were 60 parts of acrylonitrile, 20 parts of methyl acrylate, 20 parts of maleic anhydride, 100 parts of methyl ethyl ketone, and 0.1 part of azobisisobutyronitrile.
It was hot at the club. The resulting polymer has an ASTM heat deflection temperature of 79℃ and a bending strength of 1.526×10 ³ Kg/cm ² (21.7×
10 ³ psi), flexural modulus 4.562×10 ⁴ Kg/cm ² (6.49×
10 ⁵ psi), tensile strength 1.139×10 ³ Kg/cm ² (16.2×
¹⁰³ psi).

Claims (1)

[Claims] 1 (A) Structural formula 60-90% by weight of at least one nitrile (wherein R is hydrogen, a lower alkyl group having 1 to 4 carbon atoms, or a halogen)
(B) 1 to 30% by weight of maleic anhydride; (C)(i) styrene or α-methylstyrene; and (ii) structural formula (However, R ₁ is hydrogen, an alkyl group having 1 to 4 carbon atoms, or a halogen,
R ₂ is an alkyl group having 1 to 6 carbon atoms); % is (A) and (B)
A method for producing a high nitrile resin containing maleic anhydride, comprising polymerizing (C) (based on the total weight). 2. The method of claim 1, wherein the polymerization of (A), (B) and (C) is carried out in an aqueous medium in the presence of a free radical initiator and in the substantial absence of molecular oxygen. Production method. 3. The manufacturing method according to claim 1, wherein (A) is acrylonitrile. 4. The manufacturing method according to claim 1, wherein (C) is styrene. 5. The manufacturing method according to claim 1, wherein (C) is methyl acrylate.