JPS61141710A - Polymerization process - Google Patents

Abstract

PURPOSE:To cure rapidly a polymerizable composition based on methyl methacrylate at room temperature or below, by polymerizing this composition in the presence of an organic peroxide, an organic amine, a mercaptan and a soluble metal salt. CONSTITUTION:100pts.wt. methyl methacrylate-based polymerizable composition comprising 50-100wt% methyl methacrylate and (meth)acrylate ester in which 0-50wt% polymer of methyl methcrylate or the like is dissolved, wherein the total amount of methyl methacrylate units in the form of polymer and/or monomer accounts for 50wt% of the polymerizable composition is polymerized at a temperature <= room temperature in the presence of 0.1-15pts.wt. organic peroxide (e.g., benzoyl peroxide), 0.01-10pts.wt. amine (e.g., triethanolamine), 0.001-2pts.wt. mercaptan (e.g., 2-mercaptoethanol) and 0.00001-0.1pt.wt. soluble metal salt (e.g., FeCl2).

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a method for polymerizing a polymerizable composition containing methyl methacrylate as a main component, and more specifically to a method for polymerizing a polymerizable composition using an improved redox catalyst. It is something.

[Conventional technology]

Conventionally, a method for polymerizing a polymerizable composition containing methyl methacrylate as a main component using a redox catalyst is known. However, for example, the method described in Japanese Patent Publication No. 41-21037 is a method used at a relatively high temperature of 40°C or 60°C, and requires a long time for polymerization and curing at room temperature or below room temperature. However, it has no practical meaning for polymerization at room temperature. In addition, the special public
Although the method described in No. 262 is effective in terms of polymerization at room temperature, it has problems such as the production of methacrylic acid ester peroxide and the measurement of active oxygen, etc. It has drawbacks such as requiring a relatively long time for curing.

[Problem that the invention seeks to solve]

The present inventor conducted various studies with the aim of conducting short-time polymerization at room temperature or below room temperature, and found that a polymerization catalyst system consisting of an organic peroxide, an organic amine, a soluble metal salt, and a mercaptan is effective. The present invention was achieved by discovering that.

[Means for solving problems]

That is, according to the present invention, 0.00 parts by weight is added to 100 parts by weight of a polymerizable composition containing methyl methacrylate as a main component. 1 to 15 parts by weight of organic peroxide, 0.01 to 10 parts by weight of organic amine,
0.001 to 2 parts by weight of mercaptan and 0.0000
This is a polymerization method characterized by polymerization in the coexistence of 1 to 0.1 parts by weight of a soluble metal salt.

The organic peroxides used in the present invention include hydroperoxides such as 1-butyl hydroperoxide, diacyl peroxides such as pen/silver oxide, and peroxides such as t-butylperoxymaleic acid. Various organic peroxides such as esters or chemical peroxides such as cyclohexanone peroxide can be used. The amount of these organic peroxides to be added is preferably 0.1 to 15 parts by weight per 100 parts by weight of the polymerizable composition containing methyl methacrylate as a main component.
It is appropriate to use 3 parts by weight to 3 parts by weight.

The amount added is 0.1. ! If the curing temperature is less than 100° C., the time required for curing is too long, making it difficult to carry out the short-time polymerization that is the object of the present invention. Furthermore, if the amount added exceeds 15 parts by weight, the time required for curing cannot be shortened even if the amount added is increased.
Moreover, it is not preferable because it may adversely affect the coloring of the cured product.

The amines may be organic amines as long as they are soluble in the polymerizable composition, and a wide range of aliphatic or aromatic primary, secondary or tertiary amines or amine salts can be used.

The amount of amines added is usually 0.01 parts by weight to 100 parts by weight of the polymerizable composition containing methyl methacrylate as the main component.
The amount is 10 parts by weight, preferably 5 parts by weight of O,OS. If the amount added is less than 0.01 parts by weight, no substantial polymerization promoting effect can be obtained, and if it is more than 10 parts by weight, there will be adverse effects such as noticeable discoloration of the cured product, which is not preferable.

Examples of mercaptans include compounds with a thiol group or compounds that take the thiol form due to tautomerism, such as:
Butyl mercaptan, lauryl mercaptan, thiophenol, benzyl mercaptan, thioglycolic acid, 2
-Mercaptoethanol, 2-mercaptoethylamine, mercaptopenzimidazole, ethylenethiourea, acetylthiourea, diethylthiofrea, etc. can be used. The amount of mercaptans added is usually 0.001 parts by weight to 2 parts by weight, preferably 0.001 parts by weight, per 100 parts by weight of the polymerizable composition containing methyl methacrylate as a main component.
0.01 part by weight to 0.5 part by weight is suitable. The amount added is o,
If the amount is less than ooi parts by weight or more than 2 parts by weight, the effect on polymerization promotion will be small or not observed.

Examples of soluble metal salts include metal salts that are soluble in polymerizable compositions containing methyl methacrylate as a main component, or metals that become soluble in polymerizable compositions that contain methyl methacrylate as a main component by using some means. It may be in any form of salt, but it must contain a soluble base of at least one metal selected from iron, tin, cobalt, vanadium, or manganese as a soluble metal salt. The appropriate amount of the soluble metal salt added is 0.00001 to 0.1 part by weight, preferably 0.0001 to 0.01 part by weight, per 100 parts by weight of the polymerizable composition containing methyl methacrylate as a main component.

The polymerizable composition mainly composed of methyl methacrylate as used in the present invention contains a polymer of 0 to 50% by weight and 1% by weight of a polymer of 50 to 100%.
% by weight of a polymerizable monomer, the sum of the methyl methacrylate units in polymeric and/or monomeric form accounting for 50% by weight or more of the polymerizable composition; 50% by weight;
Those containing copolymerizable monomer units within a range not exceeding .

Examples of such copolymerizable monomers include (meth)
Acrylic acid, acrylic ester having an alkyl group having 1 to 12 carbon atoms, methacrylic ester having a furkyl group having 2 to 12 carbon atoms, (meth)acrylic 7mide, N-
Examples include monomers such as substituted (meth)acrylics, monomers, de-styrenes, nuclear-substituted styrenes, and mixtures thereof. Examples of the polymer include polymers of the above monomers or copolymers of mixtures of the above monomers, and/or polybutadiene, styrene/butadiene rubber, acriminitrile/butadiene rubber, polychloro I=7'lene, and aaa Examples include elastomers such as sulfonated polyethylene. In addition to the above-mentioned monomers, examples of monomers that can be added to a polymerizable composition containing methyl methacrylate as a main component include compounds having a plurality of polymerizable double bonds in one molecule, such as: Ethylene glycol di(meth)acrylate, 1.3
- Dilene glycol di(meth)acrylate.

Diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)7 acrylate, polyethylene glycol di(meth)7 acrylate, trimethylolbg Huntli(meth)acrylate pentaerythritol tetra(meth)acrylate, divinylbenzene, epoxy(meth) 7 Acrylate, Frethane (Meta) 7
Examples include acrylate, oligoester (meth)acrylate, etc. When at least one of these is selected as a crosslinking agent, 20% by weight based on the total amount of the polymerizable composition
It can be used within the range not exceeding.

The above polymerizable composition containing methyl methacrylate as a main component may further contain inorganic or organic reinforcing agents, cassifying agents, plasticizers, colorants, antioxidants, polymerization inhibitors, etc. as necessary. [Example] The following is an example. In addition, the polymerization in the examples is as follows:
Unless otherwise noted, use nominal 30n+jr test tubes,
The test was carried out at room temperature of 23°C. In addition, all indications are weight %.

Example 1 Monomer mixture K consisting of methyl methacrylate 30F and 2-ethylhexyl 7-acrylate 12.5JI.

Copolymer consisting of 94 qb of methyl methacrylate and 6 qb of methyl 7-acrylate (molecular weight approximately Zoo, 000) 7.51
benzoyl peroxide 0.3JF, hydroxypropyl-p-)luidine Q
, 375II, 2-mercaptoethanol o, os,
p.

Aqueous solution of No. 1 steel chloride 51 dissolved in pure water 10Ii 0.0
1F was added to carry out polymerization.

This system polymerized and cured approximately 12 minutes after catalyst addition.

For comparison, in a system under the same conditions as in Example 1 except that J2-mercaptoethanol was not added, it took about 30 minutes for polymerization and curing.

Example 2 The composition 50f9 shown in Example 1 was added with 1.55+ hydroperoxide, 0.01.9% lauryl mercaptan, and 0.9% ferrous chloride. Polymerization was carried out by adding 0.511 of a solution in which 151 of pure water in which QIJF was dissolved was dissolved in 100 g of triethylenetetramine and 0.0IIi of a solution in which 251 of stannous chloride IN was dissolved in ethylene glycol. This system was polymerized and cured in about 9 minutes after catalyst addition.

In a system used for comparison under exactly the same conditions as in the above example except that lauryl mercaptan was not added, it took about 30 minutes for polymerization and curing.

Example 3 Cumene octide μ peroxide I! was added to methyl methacrylate solution 501 in which 35% of a methyl methacrylate polymer having a molecular weight of about 100.000 was dissolved. , ferrous chloride 0.03g
When 0.81 of a solution of 11 dissolved in 100 Ii of triethylenetetramine and 0.02 F of 2-mercaptoethanol were added, this system was polymerized and cured in about 6 minutes after addition of the catalyst. 2-
In the case of the mercaptoeta system, approximately 10 minutes were required for polymerization and curing.

Example 4 To the same polymerizable composition 50I used in Example 3,
A solution of 0.05 F of monot-styl permaleate, 0.05 F of pentaerythritol tetrakis (3-mercapdobu-bionate), and 0.0 II of stannous chloride in 25 I of propylene glycol. When 0IJl was added, the polymer was cured by atS.

A system used for comparison, which was completely the same as the example except that pentaerythritol tetrakis (3-mercapdobu-bionate) was not added, did not polymerize and harden even after 2 hours.

Example 5 Monomer mixture K consisting of methyl methacrylate 395r,) rimethyl p-pantrimethacrylate 11, copolymer consisting of 94% methyl methacrylate and 6% methyl acrylate (molecular weight approximately 120.000) When 0.0 IJI, an aqueous solution prepared by dissolving 2 g of cumene octium oxide, 71 g of diethyl thiourene, and 5 g of chloride@1 steel in 10 g of pure water, was added to a polymerizable composition prepared by dissolving 1ON, this system polymerized in about 15 minutes. In a system under the same conditions as in the above example except that di-thylthiourea was not added, polymerization and curing did not occur even after 2 hours.

Example 6 A monomer mixture consisting of methyl methacrylate (35Ji, dicyclopentenyloxyethyl methacrylate) (15II) was mixed with benzoyl peroxide (251. Cobalt dimethyl-p-naphthenate (6% active metal) 0.0 IJl,) Luizine 111. When 0.0III and 2-mercaptoethanol were added, this system was polymerized and cured in about 30 minutes.For comparison, a system under exactly the same conditions as in the example except that 2-mercaptoethanol was not added. Approximately 2 hours were required for polymerization and curing.

〔effect〕

The method of the present invention is very effective because it rapidly polymerizes and cures even at or below room temperature.

Claims (1)

[Claims] 1) Polymerizable composition 1 containing methyl methacrylate as a main component
0.1 to 15 parts by weight of organic peroxide, 0.01 to 10 parts by weight of organic amine, 0.001 to 10 parts by weight
A polymerization method characterized in that polymerization is carried out in the coexistence of 2 parts by weight of a mercaptan and 0.00001 to 0.1 parts by weight of a soluble metal salt.