JPS6079023A - Novel method of polymerization - Google Patents

Abstract

PURPOSE:To produce a polymer of good heat stability without the need of any complicated aftertreatment step, by irradiating a reaction system in which a trunk polymer and a vinyl monomer are present with ultrasonics. CONSTITUTION:A polymer is formed by irradiating a reaction system (preferably a solid/liquid system or a solid/gas system) comprising a trunk polymer (e.g., polyvinyl alcohol resin or polyacrylonitrile resin prepared by bulk or suspension polymerization) and a vinyl monomer (preferably, one having a b.p. <= a about 50 deg.C, e.g., ethylene, vinyl chloride, methyl methacrylate or vinyl acetate) with ultrasonics at about 0-100 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION More specifically, the present invention relates to a method of obtaining a polymer by irradiating ultrasonic waves in the coexistence of a high molecular compound (hereinafter referred to as a backbone polymer) and a vinyl monomer.

A block copolymerization method is known as a polymerization method using ultrasonic irradiation, and the known method is a method in which a backbone polymer is dissolved in a solvent or the like and then polymerized. In order to obtain a block copolymer using this method, it is necessary to remove unnecessary solvents by reprecipitation, fractional distillation, etc., which is extremely disadvantageous from an industrial perspective.

The inventors of the present invention have conducted extensive research to improve these drawbacks, and as a result, they have solved the above drawbacks by irradiating ultrasonic waves to a reaction system in which a backbone polymer and a vinyl monomer coexist to spread the polymer. The inventors discovered that the present invention was completed by discovering that the present invention was completed.◇ The main polymer used in the present invention includes polybutadiene, polybutadiene,
Known rubbers such as polyisoprene, polychloroprene, ethylene-butypyrene-butadiene terpolymer, NBR, natural rubber, acrylic synthetic rubber, ABEI resin,
MBS resin, AS resin, PVO (polyvinyl chloride) resin, MMA resin, polystyrene resin, matrix time≠PP resin, urethane resin, PAIJ (polyacrylonitrile)! Examples include known thermoplastic resins such as resins, polyester resins, and known thermosetting resins such as epoxy resins, urea resins, unsaturated polyester resins, and phenolic resins.

Among these backbone polymers, PvO-based resins obtained by ordinary bulk polymerization methods or suspension polymerization methods, PvO-based resins, etc.
It is preferable to use AN resin. Since these polymers are obtained by precipitation polymerization (polymerization in which the polymer is not dissolved in a polymer), they result in polymer particles having porosity.

Therefore, if this is used as the backbone polymer, the porosity will be filled with the polymerized vinyl monomer. That is, it is preferable because the vinyl monomer has a large contact area with the beef trunk polymer and the conversion rate increases. In the present invention, these polymers can be used alone or in combination as the backbone polymer.◎ The vinyl monomer used in the present invention has the general formula: (wherein A is a hydrogen atom, a halogen atom, OH3-0-0
-, B is a hydrogen atom, a halogen atom, Atom, -0-OR (in the formula, lG1 is the same as above),
Phenyl group, -〇miN, -SO3Na, OHm
Examples of the vinyl monomers represented by the above general formula include ethylene, propylene, vinyl chloride, vinylidene chloride, butadiene, 1-butene, and on
Prene, methyl methacrylate, methyl acrylate,
Examples include ethyl methacrylate, ethyl acrylate, octyl acrylate, octyl methacrylate, vinyl ether, allyl chloride, styrene, a-methylstyrene, acrylonitrile, methacrytetranitrile, vinyl acetate, sodium allylsulfonate, etc.◇These may be used alone or in combination of two or more. You may mix and use it in arbitrary ratios.

Furthermore, in the present invention, the boiling point of vinyl mo/Y- to be polymerized is 5
If the boiling point is below 0°0, preferably below 0°O,
Since unreacted vinyl monomers can be easily recovered by stripping, a system that does not use industrial solvents is preferred.

More preferably, it is a solid-liquid or solid-gas heterogeneous system of a solid backbone polymer and a liquid or gaseous monomer. This is because unreacted vinyl monomers can be easily removed during the polymerization reaction by passing through, stripping, or the like.

However, a solvent such as water that does not dissolve the backbone polymer may be used in the reaction system used in the present invention. When water is present as a solvent, there are advantages such as removal of reaction heat and easy stirring.

The reaction temperature in the present invention is not particularly limited, but the commonly used conditions are about 0 to 100°O. In the polymer produced by the present invention, the newly polymerized portion starts polymerization. Thermal stability is good because no additives are used. Further, the polymer that can be used in the method of the present invention can be formed by conventional molding methods such as extrusion molding, injection molding, f-rendering, etc.
It can be formed into products such as pipes, plates, films, sheets, electric wires, containers, etc. by molding methods, vacuum forming methods, blow molding methods, etc.

Next, the method of the present invention will be explained based on examples.
The present invention is not limited to these.

In addition, although the amount of the final polymer produced is described in the examples, this value also includes the backbone polymer. Example 1 Polyvinyl chloride resin ( Average particle diameter 150 μm 1 Degree of polymerization 1700
) 2so, + and 1500 g of styrene were kept at 60°0 with stirring, under a N2 gas stream,
Ultrasonic waves of 28 KHz and 210 W were irradiated for a certain period of time. Thereafter, unreacted styrene monomer was removed from the reaction system by filtration. The amount of polymer produced was as follows.

Example 2 Polyacrylonitrile resin (average particle diameter 200 μm, degree of polymerization 2000
)2oop, degassed, maintained at 60°0, introduced gaseous vinyl chloride into the reaction vessel so that the pressure inside the vessel was below the saturation pressure of vinyl chloride, and heated to 28KH while stirring.
z, irradiated with 21 GW of ultrasound for 5 hours (solid-
Gas reaction system) 0After the reaction is completed, collect the vinyl chloride gas,
222 g of polymer was obtained.

Example 3 Polystyrene resin (average particle size 0) was placed in the reaction vessel of Example 2.
．． 5 mm, molecular weight 200,000), and 500 g of vinyl chloride, and heated to 28
KHz.

Ultrasonic waves of 210 W were irradiated for 5 hours. After the reaction was completed, vinyl chloride was recovered to obtain 229 g of polymer.

Example 4 After completing the same polymerization reaction as in Example 3, 0.2% was added to the reaction vessel.
An aqueous solution 11 containing a surfactant was added. Thereafter, vinyl chloride was recovered. The slurry in the reaction vessel was then dehydrated to obtain 229 g of polymer beads. This polymer was easy to handle because it was in the form of beads. Example 5 Two sops of polyvinyl chloride resin (average particle size: 150 μm, degree of polymerization: 110), 509 grams of methyl methacrylate, and 11 grams of water were placed in the reaction vessel of Example 1. The reaction system was maintained at 8,060 ℃, and 28 KHz% 210 W ultrasonic waves were irradiated for 5 hours under a N2 gas stream. The reaction solution was passed through to obtain 268 g of polymer.

Example 6 Polyethylene resin (average particle size 1
mm, MI 5 ) 2509 and styrene 5009, and heated at 60°0 with stirring under a N2 gas stream.
KHz.

Ultrasonic waves of 210 W were irradiated for 1 hour. The reaction solution was filtered through styrene monomer Tt to obtain 275 g of polymer.

Patent applicant Kanebuchi Chemical Industry Co., Ltd. Representative patent attorney Asahi Na Sota 1', Hi',
”::3:il,'11yo:LS

Claims (1)

[Claims] 1. A polymerization method characterized by irradiating ultrasonic waves to a reaction system in which a polymer compound and a vinyl monomer coexist. 2. The polymerization method according to claim 1, wherein the reaction system is a solid-liquid or solid-gas system. 6. The polymerization method according to claim 2, characterized in that a polyvinyl chloride resin and (' or) polyacrylonitrile resin are used as the polymer compound. 4. The vinyl monomer has a boiling point of 5080 or less. The polymerization method according to claim 1, characterized in that a vinyl monomer of: 5. Polymerization method 0 according to claim 4, characterized in that a vinyl monomer having a boiling point of 0°0 or less is used as the vinyl monomer.