JPS626586B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a polymer solution which has particularly excellent casting properties and is suitable for use in various coating films, separation films, insulating films, primers for painting, and the like.

A polymer of 1-butene or 4-methyl-1-pentene is known as a material with excellent transparency and heat resistance. The present inventors investigated methods for forming various films from these polymers and found that a wet casting method could be used. Furthermore, by selecting cyclohexene as the solvent, particularly excellent film forming properties were obtained. The present invention has been completed based on the discovery that the solution can be obtained using the following methods.

That is, the present invention relates to a polymer of 1-butene and a 1-butene polymer graft-modified with a vinyl monomer having a polymerizable carbon-carbon double bond in the molecule or degraded with an organic peroxide or air.
The present invention relates to a polymer solution characterized by dissolving a polymer selected from the group of butene or 4-methyl-1-pentene polymers in a solvent containing cyclohexene as a main component.

The polymers used in the present invention include polymers of 1-butene and 1-butene or 4-methyl-1-
It is a modified product of pentene polymer. Polymers of 1-butene or modified products thereof include poly-1-butene, copolymers of 1-butene and small amounts of other 1-olefins, and polymers that can be polymerized into at least a portion of these in molecules. There are modified polymers obtained by graft copolymerizing vinyl monomers having carbon-carbon double bonds, and polymers obtained by degrading the polymers with organic peroxides or air.

Polymers of 4-methyl-1-pentene include poly-4-methyl-1-pentene, 4-methyl-1-pentene,
Pentene and other 1-olefins, especially those with 5 carbon atoms
Copolymers with 1 to 18 1-olefins are exemplified, and the modified product used in the present invention is a modified product obtained by graft copolymerizing a vinyl monomer having a polymerizable carbon-carbon double bond in the molecule to at least a part of these copolymers. These are polymers and modified polymers obtained by degrading the polymers with organic peroxides or air.

The physical properties of these polymers, etc. affect the solubility in cyclohexene, the strength, hardness, heat resistance, solvent resistance, etc. of membranes and films obtained from this solution, so they should be selected depending on the purpose and use. However, regarding the molecular weight of the polymer, it is preferable that the reduced specific viscosity (RSV) (solvent decalin, temperature 135°C) is in the range of about 0.2 to 10 for 1-butene polymers, and 4-methyl-1- For modified pentene polymers, reduced specific viscosity (RSV) (solvent decalin, temperature
135° C.) is in the range of about 0.3 to 20, and the hardness of the polymer is preferably 40 or more in Shore D hardness.

When using these polymers, it is preferable to degrade them by heating in advance in the presence of an organic peroxide or air, or to graft-modify them with the vinyl monomers described below.

Vinyl monomers used as graft monomers include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, and itaconic acid, and derivatives of these unsaturated carboxylic acids include acid anhydrides, esters, Amides, imides, metal salts, ammonium salts, etc. can be used. For example, maleic anhydride, citraconic anhydride, itaconic anhydride, hymic anhydride (5-norbornene-2,3-dicarboxylic anhydride), tetrahydrophthalic anhydride, methyl acrylate, ethyl acrylate, methyl methacrylate, acrylic acid Butyl, glycidyl acrylate, glycidyl methacrylate, 2-hydroxyethyl acrylate,
2-hydroxypropyl acrylate 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, N・N'-dimethylaminoethyl methacrylate, acrylamide, sodium acrylate, monoethyl maleate, diethyl maleate, acrylamide , maleic acid monoamide, maleic acid diamide, maleic acid-N-monoethylamide, maleic acid-
N/N-diethylamide, maleic acid-N-monobutylamide, maleic acid-N/N-dibutylamide, fumaric acid monoamide, fumaric acid diamide,
Fumaric acid-N-monoethylamide, fumaric acid-
Examples include N.N-diethylamide, fumaric acid-N-monobutylamide, fumaric acid-N.N-dibutylamide, maleimide, N-butylmaleimide, and N-phenylmaleimide. Examples of other vinyl monomers include, but are not limited to, the monomers exemplified here, such as acrylonitrile, 4-vinylpyridine, styrene, vinyl acetate, vinylene carbonate, allyl glycidyl ether, etc. Compounds having bonds can be used. These may be used alone or in combination of two or more. In the present invention, it is particularly preferable to use maleic anhydride.

Various known methods can be used to modify the polymer with the above monomer. For example, there is a method in which a polymer and a monomer are reacted in the presence of a solvent, or a method in which they are mixed under heating using an extruder. In this case, a radical initiator such as an organic peroxide may be added, or by heating without adding, the monomer can be graft copolymerized to part or all of the raw material polymer. .

The graft ratio in these polymers can take various values, but it is particularly preferably 20% by weight or less, with the optimum range being 5% by weight or less.

When the grafting ratio exceeds 20% by weight, the solubility in cyclohexene increases, but the solvent resistance and heat resistance of the resulting membrane or film become insufficient.

The concentration of the 1-butene polymer or 4-methyl-1-pentene polymer in the cyclohexene solution of the present invention is 30% by weight or less, particularly about 0.5 to 5% by weight.
is preferable, and the workability of casting film formation is good.

The cyclohexene solution of the present invention is cast into a film by a known film forming method. For example, roll coating,
Films are formed using methods such as bar coater coating, knife coater coating, spray coating, and spin coating. The coating temperature is not particularly limited, but by selecting the coating temperature generally from 0 to 60°C, preferably from 5 to 30°C, a smooth coating film with excellent homogeneity and thickness accuracy and no pinholes can be obtained. After film formation, it is desirable to heat the film at 50 to 220°C for the purpose of completely removing the solvent.

Various additives may be added to the cyclohexene solution of the present invention as necessary. For example, antioxidants,
These include antistatic agents, ultraviolet absorbers, flame retardants, dyes, process oils, plasticizers, lubricating oils, and fillers.

In addition, in order to obtain a polymer porous membrane, it is necessary to
(A) and a substance (B) that has a common solvent with (A) and is well soluble in the poor solvent of (A) are blended into the cyclohexene solution of the present invention.

Examples of such substances (B) include ethylene glycol, propylene glycol alone or a copolymer, polyvinylpyrrolidone, polyvinylpyridine, polyacrylamide, polyamine hydrochloride polyacrylic acid, α-olefin-unsaturated carboxylic acid copolymer , α-olefin-unsaturated carboxylic acid ester copolymer, α-olefin-unsaturated alcohol carboxylic acid ester copolymer, polystyrene, polyurethane, polyalkylene oxide,
Examples include polymethyl methacrylate and polycarbonate. These are the membrane pore size,
In order to adjust the number of pores, etc., one or more types may be blended as necessary. The blending amount affects the porosity of the membrane obtained, but it is usually 50% by weight or less based on the polymer.

Among these substances (B), the shape of the pores can be easily adjusted by using a substance that is compatible with the substance (A), such as polymethyl methacrylate.

The cyclohexene solution of the present invention can be used for coating various substrates, filters, separation membranes, condenser membranes, etc.

Examples are shown below.

Example 1 Modified product in which 1.5% by weight of maleic anhydride was grafted onto 4-methyl-1-pentene polymer (reduced specific viscosity
1.9) is dissolved in cyclohexene at 5.0% by weight in the same manner as in Example 1. The temperature of this solution is lowered to 15°C. Even in this state, the polymer did not precipitate and became a homogeneous solution.

In this solution, 0.2% by weight of polymethyl methacrylate (trade name: Acrypet) was dissolved and stirred at 25°C. After that, it was casted on a glass plate at 25℃, and
Dry for 20 min at °C, then cool. This coating film was immersed in acetone at 25°C for 10 minutes, and then dried at 80°C for 30 minutes. This coating has turned white, and when observed under a microscope, it forms a film having homogeneous pores of about 5 μΦ.

Example 2 A polymer (reduced specific viscosity 1.2) obtained by decomposing and modifying 4-methyl-1-pentene polymer using an organic peroxide (dicumyl peroxide) was added to cyclohexene by 6 weight in the same manner as in Example 1. % dissolved. Even if this solution is cooled to 10°C, it remains a homogeneous solution.
This solution was cast onto a glass plate at 25°C and then dried at 100°C, resulting in a good coating.

Example 3 Maleic anhydride 1.3 to poly-1-butene polymer
A 2% by weight grafted modified product (reduced specific viscosity 1.01) is dissolved in cyclohexene in the same manner as in Example 1. The temperature of this solution is lowered to 25°C. Even in this state, the polymer did not precipitate and became a homogeneous solution. This solution was cast onto a glass plate at 25°C, and
After drying at ℃ for 20 minutes, an excellent coating was obtained.

Claims (1)

[Claims] 1 Polymers of 1-butene and 1-butene or 4 graft-modified with vinyl monomers having polymerizable carbon-carbon double bonds in the molecule or degraded with organic peroxides or air.
- A polymer solution comprising a polymer selected from the group of methyl-1-pentene polymers dissolved in a solvent containing cyclohexene as a main component.