JPS6234912A - Production of copolymer - Google Patents

Abstract

PURPOSE:To obtain a copolymer having excellent thermal stability, solubility in solvent, melt-fluidity, adhesivity and capability to disperse magnetic particles, by the radical polymerization of vinyl chloride, vinylidene chloride and (meth) allyl chloride in the presence of a specific polymer. CONSTITUTION:The objective copolymer can be produced by the radical polymerization of a monomer mixture composed mainly of (A) vinyl chloride and (B) vinylidene chloride and containing (C) 0.5-20wt% (meth)allyl chloride based on the sum of components A and B and, if necessary, (D) other radically polymerizable monomer in the presence of (E) a polyester having a number- average molecular weight of 3,000-200,000. The polymerization is carried out preferably by dissolving the component D in essential monomer mixture, and raising the temperature. The ratios of the essential monomers (A, B and C) are preferably 10-70%, 20-80% and 1-10%, respectively.

Description

Detailed Description of the Invention (1) Purpose of the Invention [Field of Industrial Application] The present invention has a high degree of thermal stability, is soluble in inexpensive solvents mainly composed of aromatic hydrocarbons, and is This article relates to a method for producing a copolymer that has excellent melt flowability at high temperatures, adhesion to various substrates, and high dispersion ability for metal powders or metal oxide powders, etc., and is particularly applicable to cotton, polyester fibers, etc. The present invention relates to a method for producing a functional resin used as a hot-melt adhesive for interlining or a dispersant for magnetic material.

[Conventional technology and its problems]

Vinyl chloride-vinylidene chloride copolymers are inexpensive and have excellent flame retardancy, so they are used in some hot melt adhesives. It is also used as a magnetic tape binder because of its excellent dispersibility with respect to γ-iron oxide.

However, in general, thermal decomposition is high and
The melt flowability at temperatures below 80° C. is poor, and the adhesion ability to fibers, metals, etc. is low. Furthermore, it has been limited as a dispersant for magnetic materials due to its lack of dissolving power in low-friction solvents and the need for solvents with strong pungent odors such as cyclohexanone or tetrahydrofuran.

As a countermeasure to this problem, improvements have been made by lowering the molecular weight of vinyl chloride-vinyldene chloride copolymers, or by creating terpolymer copolymers with monomers such as vinyl acetate and acrylic esters, but these have poor thermal stability. , low volatility of solvents, and tubular lag between films, etc., resulting in limited applications.

For example, JP-A-59-164314 discloses a method for producing a copolymer characterized by cacically polymerizing vinyl chloride, vinylidene chloride, allylchloratetralide, or methallyl chloride. When a polymer was used as an adhesive, the peel adhesive strength was low, the dispersibility of the magnetic powder was poor, and the blocking resistance was also insufficient.

(2) Structure of the Invention [Means for Solving the Problems] The present inventors have completed the present invention as a result of intensive studies on the above-mentioned problems.

That is, the present invention is composed of vinyl chloride, vinylidene chloride, and allyl chloride or methallyl chloride, or these and other radically polymerizable monomers, and is composed of allyl chloride or methallyl chloride (hereinafter collectively referred to as (meth)allyl chloride). ) is 0.5 to 20% by weight based on the total amount of vinyl chloride and vinylidene chloride, and the total amount of vinyl chloride and vinylidene chloride accounts for the main component of all monomers, Number average molecular weight 4000~2
00. This is a method for producing a copolymer, characterized by carrying out radical polymerization in the presence of an OOO polyester.

[Monomer mixture]

The monomer mixture in the present invention consists of vinyl chloride, vinylidene chloride, (meth)allyl chlorophyte, or these and other radically polymerizable monomers.

The proportion of (meth)allyl chloride used must be 0.5 to 20% by weight based on the total amount of essential monomers, ie, vinyl chloride, vinylidene chloride, and (meth)allyl chloride, and is 0.5% by weight. If it is less than 20%, the thermal stability will be extremely poor, and at the same time, the adhesion and melt flowability will be poor. In addition, the solubility in solvents mainly composed of aromatic hydrocarbons decreases.

On the other hand, if the amount exceeds 20% by weight, the polymerization reactivity will be significantly lowered and the mechanical strength of the obtained copolymer will be significantly lowered.

The total amount of vinyl chloride and vinylidene chloride needs to be the main components in the total monomer mixture, and it is preferable that vinyl chloride and vinylidene chloride each contain 4 to 95% by weight in the total monomer mixture. .

If the total amount of vinyl chloride and vinylidene chloride is not the main component in the entire monomer mixture, the properties of vinyl chloride and vinylidene chloride (IJdene), such as adhesiveness, flame retardance, and polymerization reactivity, will be poor.

If the vinyl chloride content is less than 4% by weight, the adhesiveness of the coelectric material,
Alternatively, melt fluidity tends to be poor. the other 95% by weight
If it exceeds this range, the flexibility, adhesiveness, melt fluidity, dispersibility of the magnetic material, and dissolution of the polymer in solvents mainly composed of aromatic hydrocarbons will tend to deteriorate.

Radically polymerizable monomers other than the above three types of monomers can also be used depending on the purpose. As other radically polymerizable monomers, for example, vinyl esters, vinyl ethers, acrylic esters, and vinyl ketones can be used when the purpose is to increase solubility in solvents or melt fluidity, and vinyl esters, vinyl ethers, acrylic esters, and vinyl ketones can be used. In order to improve the dispersibility of the magnetic material, one or two polar group-containing monomers such as acrylic acid, hydroxyethyl acrylate, maleic anhydride, N-methyl-acrylamide, sodium methallylsulfonate, or glycidyl methacrylate are used. More than one species can be used. The amount of such monomer used is desirably maintained at 0 to 30% by weight based on the above-mentioned essential monomer mixture. If it exceeds 30% by weight, it becomes difficult for the copolymer to exhibit the above-mentioned properties targeted by the present invention.

A more preferable blending ratio of the monomers used in the present invention is 10 to 70% by weight of vinyl chloride and 20 to 85% by weight of vinyl chloride.
The amount of (meth)allyl chloride is 1 to 10% by weight, and the amount of other radically polymerizable monomers is 0 to 15% by weight based on the essential monomer mixture.

〔polyester〕

The polyester used in the present invention is produced by a condensation reaction between an organic acid such as phthalic acid, adipic acid, or maleic acid and a hydroxyl group-containing compound such as ethylene glycol, furopylene gellicol, butylene glycol, trimethylolpropane, or pentaerythritol. This is a polymer obtained by

As the organic acid, aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid, and aliphatic dicarboxylic acids such as adipic acid and sebacic acid are preferable, and as the hydroxyl group-containing compound, ethylene glycol, 1,4-butanediol, neopentyl glycol, etc. glycols are preferred. Molecular weight is number average! 1,000-200. Must be ODD. Further, the preferred average molecular weight range is io, oo.

~80,000. If the number average molecular weight is less than 5,000, the volatility of the solvent and the oxidation resistance of the film will be poor. On the other hand, when it exceeds 200,000, the crystallinity increases and the resulting polymer has poor melt flowability, solubility in solvents,
and the dispersibility of the magnetic material becomes poor.

The above number average molecular weight is determined by gel permeation chromatography (G
PC) is the number average molecular weight in terms of polystyrene. The measurement conditions are as follows.

Apparatus: High performance liquid chromatography (e.g., manufactured by Toyo Kyodatsu Kogyo, product name: HLC-801A) Column: Boristyrene gel (e.g., manufactured by Toyo Soda Kogyo, part name: GM)
H') Elution solvent: Tetrahydrofuran Eflux rate: 1. Otd/m Pressure Crab 15kg/d Column temperature: 406C As the polyester used in the present invention, Toagosei Chemical Industry ■ reverse product name PE5-110L, PE5-110H, P
E5-! +20, PH8-330 are preferred.

[Production of copolymer]

In the present invention, the desired copolymer can be obtained by radically polymerizing the monomer mixture in the presence of the polyester.

The ratio of the polyester and the monomer mixture used is preferably 97 to 50 parts by weight of the monomer mixture to 6 to 50 parts by weight of the polyester, and the total monomer mixture is 90 to 50 parts by weight to 10 to 40 parts by weight of the polyester. More preferably, the amount is 60 parts by weight. If the proportion of the monomer mixture used exceeds 97 parts by weight, the effect of polyester will be reduced, and the adhesion, solvent volatility, and scratch resistance of the film will tend to be poor; if the proportion is less than 50 parts by weight, As the content of the monomer mixture decreases, it becomes difficult to carry out a smooth copolymerization reaction.
And the obtained polymer has flame retardancy, reduced dispersibility of magnetic material,
And it tends to be expensive.

As the polymerization method, any of suspension polymerization, emulsion polymerization, and solution polymerization can be employed. However, in these polymerization methods, it is preferable to dissolve the polyester in the above-mentioned essential monomer mixture in advance and then raise the temperature, or to slightly lengthen the heating time after charging the entire amount. Fortunately, polyester is easily soluble in the above-mentioned essential monomer mixture, so it is sufficient if such conditions are used.

For example, when using the simplest suspension polymerization method, the suspending agent may be one of partially saponified PVA, methyl cellulose, a copolymer of ethylene oxide and propylene oxide, or a copolymer of vinyl acetate and maleic acid. Or two or more types can be used. Polymerization temperature is 40-70℃,
The polymerization time is preferably 7 to 20 hours.

As the radical-generating catalyst, benzoyl peroxide, lauroyl peroxide, di-2-ethylhexyl peroxydicarbonate, 2,2'-dimethylvaleronitrile, etc. are used.

Further, when employing an emulsion polymerization method or a solution polymerization method, a water-soluble catalyst or an oil-soluble catalyst, an emulsifier, and various general-purpose solvents can be used as appropriate.

[Examples and comparative examples]

EXAMPLES The present invention will be explained in more detail with reference to Examples and Comparative Examples below.

Note that the parts on each side represent parts by weight, and the properties of the polymer obtained on each side were measured by the following methods.

1) Heat stability Without adding a heat stabilizer, the product was maintained at 80° C. for 2 months with the gear open, and the state of discoloration was observed.

2) Solubility in toluene/methyl ethyl ketone (mixed solvent with a weight ratio of 3/1) Add 20 parts by weight of the copolymer to 80 parts by weight of the above mixed solvent,
The solubility was observed after stirring at 26° C. for 1 hour.

3) Peel adhesion strength Copolymer particles were uniformly scattered on a blended fiber sheet of polyester/cotton (65/35 weight ratio) at a rate of 60y/.l, the same sheet was placed on top of this, and heated at 150°C. X
O, 3ky/mx After pressing for 15 seconds,
Peel strength (180°) at 25°C was measured.

4) 600 parts by weight of magnetic dispersible γ-iron oxide powder, 70 parts of copolymer, urethane polymer and Tuboran 2504. Made by Japan Polyurethane)
After shaking a mixture of 60 parts by weight, 400 parts by weight of methyl ethyl ketone, 1,200 parts by weight of toluene, and 4,000 parts by weight of glass peas in a paint conditioner for 2 hours, the glass peas were passed through an E-filter and immediately placed on a polyester film with a 100 μm doctor. It was coated with a blade and left to stand at room temperature for 30 minutes, and after drying, the 60° reflectance was measured. High reflectance indicates good root dispersion.

5) Professional hekking resistance Combine the coated surfaces obtained in 4) at 40°C and 0.2 kg.
/ad x 24 Hr to observe the degree of pro-co-king and judge whether it was good or bad.

Example 1 In a 5J autoclave, 70 parts of vinyl chloride, 26 parts of vinylidene chloride, 4 parts of methallylchloride, PE5-11O
20 parts of L (polyester with a number average molecular weight of 10,000, manufactured by Toagosei Chemical Industry ■), 0KS-75 as a suspending agent
14 (partially saponified PVA, manufactured by Nippon Gosei Kagaku ■) and 1.0 part of Epan 485 (block copolymer of ethylene oxide and propylene oxide, manufactured by Daiichi Kogyo Seiyaku ■), 0.4 part of 2-ethylhexyl peroxydicarbonate and 200 parts of pure water were charged as a radical-generating catalyst, and suspension polymerization was carried out at 60° C. for 13 hours while stirring at 500 rpm. The centrifugal dehydration layer was dried, and as a result, a powdery polymer was obtained with a polymerization yield of 82% by weight. When this polymer was subjected to a physical property evaluation test, the results were as shown in Table 1.

Examples 2 to 10 and Comparative Examples 1 to 4 Polymerization was carried out in Example 1 by changing the monomer composition, the type of polyester, or the presence or absence of polyester, but keeping the other polymerization conditions the same. As a result, the test results shown in Table 1 were obtained.

(3) A copolymer with excellent effects of the invention and excellent blocking resistance can be easily obtained,
It is industrially useful as a hot melt adhesive, a dispersant for magnetic materials, etc.

Claims (1)

[Claims] 1. Consisting of vinyl chloride, vinylidene chloride and allyl chloride or methallyl chloride, or consisting of these and other radically polymerizable monomers, where allyl chloride or methallyl chloride is based on the total amount of vinyl chloride and vinylidene chloride. The monomer mixture has a number average molecular weight of 3,000 to 20% by weight, and the total amount of vinyl chloride and vinylidene chloride is the main component of all monomers.
A method for producing a copolymer, which comprises radical polymerization in the presence of a polyester of 200,000.