JPH03290413A - Acrylonitrile copolymer - Google Patents

Abstract

PURPOSE:To provide the subject copolymer containing acrylonitrile monomer and a fluoroalkyl (meth)acrylate monomer at a specific ratio, having a specific intrinsic viscosity and excellent oil-repellency, water-repellency, weather resistance, chemical resistance, moist heat resistance, etc., and suitable for fiber, etc. CONSTITUTION:Acrylonitrile monomer and a fluoroalkyl (meth)acrylate (e.g. 1H,1H,2H,2H-heptadecafluorodecyl methacrylate) are dissolved in a solvent and charged in a reactor fitted with a stirrer and a reflux condenser and thermally polymerized in the presence of a radical polymerization initiator (e.g. azobisisobutyronitrile) in nitrogen stream to obtain the objective acrylonitrile copolymer containing >=70wt.% of acrylonitrile monomer unit and 0.1-30wt.% of a fluoroalkyl (meth)acrylate monomer unit and having an intrinsic viscosity of 0.8-10.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to an acrylonitrile (IJ) copolymer having excellent oil repellency, water repellency, weather resistance, chemical resistance, and heat and humidity resistance.

[Conventional technology]

In order to improve the performance of conventional acrylonitrile (IJ) polymers, attempts have been made to modify them with various copolymers. Furthermore, many types of fluorine-based resins, including polytetrafluoroethylene, have been disclosed. However, in order to impart water repellency, oil repellency, etc. to an acrylonitrile polymer, it is common to treat the product with a fluorine resin, and many fluoropolymer compositions have been disclosed as treatment agents for textile products. For example, JP-A-53-
22547= publication, at least 40 polymerizable compounds having a perfluoroalkyl group having 4 to 16 carbon atoms
A water and oil repellent agent comprising a copolymer containing 10 to 60% by weight of vinylidene chloride is disclosed. JP-A-51-133511 discloses that at least 35% by weight of a polymerizable compound having a perfluoroalkyl group having 3 to 20 carbon atoms, 35 to 60% by weight of vinylidene chloride and N
A composition for paper treatment comprising a copolymer containing 0.5 to 5% by weight of methylol-methacrylic T-sod or N-methylol-methacrylic ester is disclosed. Also, JP-A-62
Publication No. 179517 discloses a water-repellent and oil-repellent solid containing 40 to 75% by weight of perfluoroalkylethyl acrylate monomer, 10 to 35% by weight of vinylidene chloride, and 10 to 25% by weight of alkyl acrylate or alkyl methacrylate monomer. Fluoropolymers are disclosed.

On the other hand, Japanese Patent Publication No. 1-58204 discloses a fluoroalkyl (meth)acrylate polymer with excellent heat resistance consisting of 70% by weight or more of fluoroalkyl methacrylate or fluoroalkyl acrylate and 30% by weight or less of vinyl monomer. A manufacturing method is disclosed.

[Problem to be solved by the invention]

In order to impart the functions of a fluorine-based resin to an acrylonitrile polymer as described above, it is common to treat acrylonitrile-based fiber products with a fluorine-based resin. in this case,
The resin can be applied by spraying an aqueous latex or organic solvent solution of the resin onto the object to be treated, or by immersing the object in the resin liquid and dehydrating it, followed by dry heat treatment. Means for forming a film on the fiber surface are commonly used. However, with this method, processing spots are likely to occur, and increasing the amount of adhesion causes processing problems. There are also problems with the durability of fluorine performance, for example as shown in wash resistance. In addition, for fluorine-based resins, especially tetrafluoroethylene resins, high-pressure extrusion, emulsion shaping,
Currently, processing such as sintering is difficult and costs are high. In order to solve these problems, the present inventors conducted intensive studies on the structure of the polymer itself, and as a result, created a completely new acrylonitrile-based copolymer and arrived at the present invention.

[Means to solve the problem]

The present invention is a copolymer containing 70% by weight or more of an acrylonitrile monomer and 0.1 to 30% by weight of a fluoroalkyl methacrylate or fluoroalkyl acrylate monomer, the copolymer having an intrinsic viscosity of It is an acrylonitrile copolymer having a molecular weight of 0.8 to 10.

The acrylonitrile copolymer of the present invention must contain 70% by weight or more of acrylonitrile monomer, and 70% by weight or more of acrylonitrile monomer.
If it is less than 0% by weight, the properties of the acrylonitrile polymer will be lost. In addition, fluoroalkyl methacrylate or fluoroalkyl acrylate monomer is added from 0.1 to
If the content is less than 0.1% by weight, the performance of the fluorine-based resin will not be exhibited, and if it exceeds 30% by weight, the properties of the fluorine-based polymer will be lost and at the same time the properties of the fluorine-based resin will be lost. However, the problem of solubility in solvents also arises.

The copolymer of the present invention can also contain less than 30% by weight of other copolymerizable monomers. Examples of other copolymerizable monomers include methacrylic acid such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, hexyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, and propyl acrylate, esters of acrylic acid, vinyl chloride,
Vinyl halides such as vinyl bromide and vinylidene chloride,
Methacrylic acid, acrylic acid, itaconic acid, crotonic acid,
Examples include acids such as vinylsulfonic acid and their salts, maleimide, phenylmaleimide, acrylamide, methacrylamide, styrene, α-methylstyrene, and vinyl acetate. These monomers may be used alone or in combination of two or more.

The copolymer of the present invention has an intrinsic viscosity of 0.8 to 10. If the intrinsic viscosity is less than 0.8, the excipient will not have sufficient flexibility and will become brittle. Moreover, when it exceeds 10, the formability becomes very poor.

The copolymer of the present invention comprises acryloni) IJ and (meth)
It can be produced by copolymerizing fluoroalkyl acrylate.

For example, the following compounds are used as the fluoroalkyl (meth)acrylate. 2.2.2-Trifluoroethyl (meth)acrylate, I H, LH, 5H-octafluoropentyl (meth)acrylate, I H, I
H,2H,2H-hebutadecafluorodecyl (meth)acrylate.

(Meth) The amount of fluoroalkyl acrylate used is 0.1 to 30 parts by weight per 70 to 99.9 parts by weight of acrylonitrile.
Parts by weight are preferred.

This reaction is carried out in the presence of a polymerization initiator.

As the polymerization initiator, radical polymerization initiators such as azobisisobutyronitrile, 2,2'-azobis(2,4
-dimethylvaleronitrile), aliphatic diacyl peroxides, organic peroxides such as peroxy esters, persulfates, and redox initiators in which these are combined with a reducing agent. The amount of the polymerization initiator to be used needs to be adjusted as appropriate from the viewpoints of degree of polymerization, polymerization stability, initiator efficiency, and the like.

Examples of the polymerization method include emulsion polymerization, suspension polymerization, solution polymerization, and bulk polymerization, but emulsion polymerization, suspension polymerization, and solution polymerization are preferred from the viewpoint of controllability of the polymerization reaction temperature, etc. of the polymerization system. Suspension polymerization can be carried out not only in an aqueous system but also in a mixed medium of water and an organic solvent.

In addition to the properties of polyacrylonitrile, the fibers, films, and other bottom-shaped objects formed from the copolymer of the present invention have water repellency,
Demonstrates oil repellency, stain resistance, weather resistance, heat and humidity resistance, optical properties, dielectric properties, biocompatibility, etc.

Examples will be specifically described below. Part and % of the following side
means weight, and the intrinsic viscosity is dimethylformamide (D
These are the measured values at 25°C when MF) was used as a solvent.

Example 1 Acrylonitrile (
AN) 90 copies, L H, IH, 2H.

10 parts of 2H-hebutadecafluorodecyl methacrylate (hereinafter 17FM), 400 parts of water, 200 parts of dimethylacetamide (hereinafter DMAc) and 0.1 part of azobisisobutyronitrile were charged, AN, 17 parts M, water and DMA.
In each case, c was subjected to nitrogen bubbling for 1 hour.

These were polymerized at 60° C. for 3 hours under a nitrogen stream.

The yield of the obtained polymer was 52%. The composition of the polymer calculated from elemental analysis of fluorine in the obtained polymer is:
ΔN was 82% and 17 parts M was 12%. The intrinsic viscosity is 2
．． It was 80.

Example 2 95 parts of AN, 17 parts of M5 parts, 600 parts of DMAc and 2°2-azobis(4-
Methoxy-2,4-dimethylvaleroni) IJru) 0
．． 1 part of AN, 17 parts of M, and DMAc were each treated with nitrogen bubbles for 1 hour. 5 of these
Polymerization was carried out at 0° C. for 3 hours under a nitrogen stream. The yield of the obtained polymer was 49%. The composition of the obtained polymer calculated from elemental fluorine analysis was 92% AN and 17 parts M8%. The intrinsic viscosity was 2.22.

Example 3 In a reactor equipped with a stirrer and a reflux condenser, 95 parts of AN, 17 parts of M5B, 600 parts of water, (NH4) zs2[]5O17
5 parts, NaH3O53,0'7 parts, H,S[1,0,2
5 parts and 0.4 to monomer as p e 2 +
ppm, and AN, 17 parts M, and water were each subjected to nitrogen bubbling for 1 hour. these at 50℃
Polymerization was carried out for 3 hours under a nitrogen stream. The yield of the obtained polymer was 83%. The composition in the polymer calculated from the elemental analysis of fluorine in the obtained polymer was 93% AN and 17% AN.
Part M was 7%.

The intrinsic viscosity was 1.87.

Example 4 AN90iY, IH in a reactor equipped with a stirrer and a reflux condenser
, IH, 10 parts of 5H-octafluoropentyl methacrylate (hereinafter referred to as 8FM), 400 parts of water, 200 parts of DMAc, 0, 1 B of 2,2-azobis(4-methoxy-2,4-dimethylvaleronitrile), AN, 8FM,
Water and DMAC were each treated with nitrogen bubbles for 1 hour. These were polymerized at 50° C. for 3 hours under a nitrogen stream. The yield of the obtained polymer was 62%. The composition of the obtained polymer calculated from elemental fluorine analysis was 85% AN and 15% 8FM. The intrinsic viscosity was 2.75.

Example 5 75 parts of AN, 8FM in a reactor equipped with a stirrer and a reflux condenser
25 parts, 600 parts of DMAc and 2.2-azobis(4-
methoxy-2,4-dimethylvaleronitrile) 0.1
AN, 8FM and DMAc were each treated with nitrogen bubbles for 1 hour. These were polymerized at 50° C. for 3 hours under a nitrogen stream. The yield of the obtained polymer was 61%. The composition in the polymer calculated from the elemental analysis of fluorine in the obtained polymer was 71% AN and 8FM.
It was 29%. The intrinsic viscosity was 2.71.

Example 6 AN90 in a reactor equipped with a stirrer and a reflux condenser! , 2.2
．． 2-) Lifluoroethyl acrylate (hereinafter referred to as 3FA
) 10 parts, 400 parts of water, 200 parts of DMAc and 2.2-
Add azobis(4-methoxy-2,4-dimethylvaleronitrile) 0°IN, AN, 3FA, water and DM.
Ac used was obtained by performing nitrogen bubbles for 1 hour.

These were polymerized at 50° C. for 3 hours under a nitrogen stream. The yield of the obtained polymer was 67%.

The composition of the obtained polymer calculated from fluorine elemental analysis was 82% AN and 18% 3FA. This was also confirmed by NMR measurements. Intrinsic viscosity is 2.65
Met.

Example 7 90 parts of AN and IH were added to a reactor equipped with a stirrer and a reflux condenser.
, LH, IH, I H-hebutadecafluorodecyl acrylate (hereinafter referred to as 17FA) 10 parts, water 400 parts, DM
200 parts of F and 2,2-azobis(4-methoxy-2
, 0.1 part of 4-dimethylvaleronitrile),
AN, 17FA, water, and DMF were each treated with nitrogen bubbles for 1 hour. These were heated at 50℃ for 3 hours,
Polymerization was carried out under a nitrogen stream. The yield of the obtained polymer was 64
Warm in %. The composition in the polymer calculated from the elemental analysis of fluorine in the obtained polymer was 84% AN and 16% A17 parts.
Met. The intrinsic viscosity was 2.79.

Comparative Example 1 75 parts of AN and 3FA in a reactor equipped with a stirrer and a reflux condenser
25 parts of water, 400 parts of water, 200 parts of DMAc, and 1 part of 2.2-azobis(4-methoxy-2,4 dimethylvaleronitrile) were prepared, and AN, 3FA, water, and DMAc were each subjected to nitrogen bubbling for 1 hour. was used. These were polymerized at 50° C. for 3 hours under a nitrogen stream. The yield of the obtained polymer was 87%. The composition in the polymer calculated from elemental analysis of fluorine in the obtained polymer was ANT1.
% and 3FA 29%. The intrinsic viscosity was 0.08. Wet spinning of this polymer was attempted, but it did not have spinnability and could not be spun.

Comparative Example 2 50 parts of AN, 17 in a reactor equipped with a stirrer and a reflux condenser
50 parts of FM, 400 parts of water, 200 parts of DMAc and 2.2 parts
0.1 part of -azobis(4-methoxy-2,4-dimethylvaleronitrile) was charged, and AN, 17 parts M, water, and DMAc were each used after nitrogen bubbling for 1 hour.

These were polymerized at 50° C. for 3 hours under a nitrogen stream. The yield of the obtained polymer was 49%.

The composition of the obtained polymer calculated from elemental fluorine analysis was 42% AN and 17 parts M58%.

The intrinsic viscosity was 2.03.

In order to spin this polymer, an attempt was made to dissolve it in DMF, but the polymer could not be dissolved.

Sender: Mitsubishi Rayon Co., Ltd. Representative Patent Attorney Atsushi Takahashi

Claims (1)

[Claims] A copolymer containing 70% by weight or more of an acrylonitrile monomer and 0.1 to 30% by weight of a fluoroalkyl methacrylate or fluoroalkyl acrylate monomer, the copolymer having an intrinsic viscosity of 0.8 to 10% by weight. Acrylonitrile copolymer.