JPS6291508A - Production of methacrylate polymer - Google Patents

Abstract

PURPOSE:To obtain the titled polymer excellent in strength, etc., and suitable for lenses, etc., at a high polymerization rate, by polymerizing a methacrylate of a 2-25C alcohol or of a phenol in the presence of a specified redox polymerization initiator. CONSTITUTION:A methacrylate of a 2-25C alcohol or of a phenol (e.g., ethylene glycol dimethacrylate) or an unsaturated monomer based thereon is prepared. The titled polymer is obtained by polymerizing 100pts.wt. this monomer in the presence of 0.1-5pts.wt. radical polymerization initiator (e.g., t-butyl peroxyacetate) and 0.005-1pt.wt. chlorine-containing compound selected from a hydrochloride or quat. ammonium chloride salt of an amine (e.g., laurylamine), 0.1-0.8ppm (in terms of copper), based on the weight of the monomer, of a copper salt or copper-containing complex of an organic acid and a sulfur compound having a plurality of SH groups in an amount satisfying the equation.

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention is directed to the rapid polymerization of methacrylic acid ester or an unsaturated monomer containing it as a main component using a specific polymerization initiator and other accelerators. The present invention relates to a method for producing a methacrylic acid ester polymer with excellent physical properties.

(Prior Art) West German Patent Application Publication No. 1146254 describes compounds containing halogen atoms such as alkylacyl peroxides and amine hydrochlorides, compounds containing one or two SH groups, and heavy metal compounds as optional components. A method for polymerizing methacrylic acid ester and the like using a catalyst is described.

(Problems to be Solved by the Invention) In the above-mentioned conventional methods, the polymerization rate and the physical properties, particularly the strength, of the resulting polymer are not necessarily sufficient.

1 (Means for resolving the problem) The present invention is directed to a methacrylic acid ester of an alcohol or phenol having 2 to 25 carbon atoms, an unsaturated monomer containing this as a main component, or a polymer thereof. Said monomer 10
Sulfur containing 0 parts by weight, 0.1 to 5 parts by weight of a radical polymerization initiator, and 0.005 to 1 or more of at least one chlorine-containing compound found from A1's hydrochloride or quaternary ammonium chloride. This is a method for producing a methacrylic acid ester polymer, which is characterized by polymerizing a compound in an amount satisfying the following formula.

The methacrylic esters of alcohols or phenols having 2 to 25 carbon atoms used in the present invention include, for example, ethyl methacrylate, purvyl methacrylate, butyl methacrylate, hexyl methacrylate, octyl methacrylate, dodecyl methacrylate, Examples include one or more of stearyl methacrylate, cyclohexyl methacrylate, 4-methylcyclohexyl methacrylate, isofornyl methacrylate, dicyclopentanyl methacrylate, dicyclopentenyl methacrylate, benzyl methacrylate, and phenyl methacrylate. .

These methacrylic esters can be used alone, but in order to modify the polymer, other monofunctional unsaturated monomers copolymerizable with the methacrylic esters can be used in combination. Examples of these monomers include alkrylic acid esters such as methyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, isopropyl acrylate, and cyclohexyl acrylate, styrene, p-methylstyrene, α-methylstyrene, Examples include acrylic acid, methacrylic acid, maleic anhydride, and acrylonitrile.

These monofunctional unsaturated monomers are used in less than 50% by weight. If the amount is more than this, the original transparency and weather resistance of the methacrylic resin will be adversely affected.

Although it is possible to use the monomer as it is, in terms of polymerization activity and ease of handling, it is preferable to use it as a monomer containing a part of the polymer, which is usually called syrup. .

The syrup can be obtained by dissolving the polymer in its monomer at a concentration of 1 to 40% by weight, or by partially polymerizing the monomer in the presence of a radical polymerization initiator or the like.

In the method of the present invention, it is also possible to use a polyfunctional unsaturated monomer containing two or more functional groups copolymerizable with the methacrylic ester.

The use of polyfunctional monomers has the effect of increasing the strength of the polymer and at the same time increasing the polymerization rate. The use of polyfunctional unsaturated monomers may cause partial gel inside the polymer and make the polymer heterogeneous in normal relatively slow polymerization, but the rapid polymerization of the present invention In this case, no such gel is formed and a uniform polymer is obtained.

Examples of polyfunctional unsaturated monomers containing two or more functional groups copolymerizable with methyl methacrylate used in the present invention include ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, and diethylene glycol dimethacrylate. Acrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, nonaethylene glycol diacrylate, nonaethylene glycol dimethacrylate, tetradecaethylene glycol diacrylate, tetradeca Ethylene glycol dimethacrylate, etc., in which both terminal hydroxyl groups of ethylene glycol or its oligomer are esterified with acrylic acid or methacrylic acid; neopentane glycol diacrylate, neopentane glycol dimethacrylate, hexanediol diacrylate, hexanediol dimethacrylate Acrylate, butanediol diacrylate, butanediol dimethacrylate, and other dihydric alcohols whose hydroxyl groups are esterified with acrylic acid or methacrylic acid; the terminal hydroxyl groups of bisphenol A or alkylene oxide adducts of bisphenol A are esterified with acrylic acid. or esterified with methacrylic acid; polyhydric alcohols such as trimethylolpropane and pentaerythritol esterified with acrylic acid or methacrylic acid; and glycidyl acrylate or esterified with the terminal hydroxyl group of these divalent or polyhydric alcohols. Ring-opening additions of glycidyl methacrylate groups; succinic acid, adipic acid, terephthalic acid,
Those obtained by ring-opening addition of an epoxy group of glycidyl acrylate or glycidyl methacrylate to a dibasic acid such as phthalic acid; aryl methacrylate, divinylbenzene, etc. are used. When a polyfunctional unsaturated monomer is used in combination, it is preferably 0.5 to 26 parts by weight per 10 parts by weight of methyl methacrylate, a monofunctional unsaturated monomer mainly composed of methyl methacrylate, or a syrup thereof IL. is 1~10mf
f1 part is used.

If the amount is less than 0.5 parts by weight, little effect of improving strength or promoting polymerization can be expected, and if it is more than 25 parts by weight, the strength will decrease.

As the radical effect initiator, peroxides are preferred, and peroxides and hydroperoxides are particularly preferred because of their high polymerization activity. Examples of peracid esters include t-butylperoxy-8,5°5-trimethylhexanoate,
T-butylperoxyacetate, t-butylperoxybenzoate, etc. are used. Hydroperoxides include t-butyl hydroperoxide, kiemene hydroperoxide, diisopropylbenzene hydroperoxide, p-menthane hydroperoxide, 2,5-dimethylhexane-2,5-cybidrobaroxide, 1. 3. Ni-1-tetramethylbutyl hydroperoxide and the like are used. The amount used is monomer or syrup to O! 0 for ffi part
, 1 to 5 parts by weight. If the amount is less than 0.1 part by weight, polymerization will not be carried out sufficiently and a large amount of monomer will remain in the resulting polymer, which is not preferable. On the other hand, if the amount is more than 5 parts by weight, it is difficult to control the polymerization and the weather resistance and heat resistance of the obtained polymer decreases, which is not preferable.

Examples of the amine hydrochloride or quaternary ammonium chloride used in the present invention include n-amylamine, n-hexylamine, n-octylamine, n-decylamine, laurylamine, palmitylamine, dibutylamine, tributylamine, N,N-dimethylbenzylamine, N,N-dimethylnyl-toluidine, phenethyldibutylamine, N,N,NI,N-1tetramethylhexamethylenediamine, N.

Hydrochlorides of amines such as N, N', N'-tetramethylpropylenediamine, N,N-diethylbenzylamine, N,N-dibutylbenzylamine, phenethyldiethylane, tetramethylammonium chloride, benzyltrimethylammonium chloride, benzyl Examples include triethylammonium chloride, benzyltributylammonium chloride, trioctylmethylammonium chloride, β-phenethyldibutylethoxycarbonylmethylammonium chloride, and the like.

The amount of these compounds used is 100 il of monomer or syrup.
0.005 to 1 part by weight, preferably 0.005 to 1 part by weight based on part tjt.
01 to 0.5 parts by weight is used. 5tt - The organic acid copper salt or copper-containing complex used in the present invention acts as a decomposition catalyst for the polymerization initiator. Examples of these include copper naphthenate and copper acetylate. If the amount is less than ppm, the polymerization rate is slow and the polymerization time is shortened. It is not constant, and if it is more than 0.8 ppm, the polymerization rate will be rather slow, which is not preferable.

The compound containing two or more SH groups used in the present invention serves as a reducing agent that forms a redox system with a radical polymerization initiator.

Compounds containing SH groups are excellent as reducing agents, but they also serve as chain transfer agents. Therefore, if a large amount is added, the molecular weight of the polymer will decrease and only a polymer with very weak strength will be produced. A compound containing two or more SH groups in its molecule has the same performance as a reducing agent as compared to a compound containing one SH group in its molecule, but its performance as a chain transfer agent is lower, and the same (molar) When comparing the number of SH groups), there is no difference in the polymerization rate, but the molecular weight of the obtained polymer is higher when a compound containing two or more SH groups is used, and the strength is stronger.

Examples of such compounds containing two or more SH groups include one or more of glycol dimercaptoacetate, trimethylolpropane trimercaptoacetate, pentaerythritol tetramercaptoacetate, and the like.

These sulfur compounds are used with the formula: number of moles of the sulfur compound x number of SH groups, number of moles of the copper compound x number of copper atoms, in the range of 5,000 to so, ooo.

If this value is less than 5,000, the polymerization rate will be extremely slow, and if it is more than so or ooo, the strength of the polymer will decrease.

The polymerization of the present invention is carried out by a bulk polymerization method, and a radical polymerization initiator, a reducing substance containing sulfur in the molecule, and a copper-containing compound are added to a monomer such as methacrylic acid ester or a monomer containing a polymer thereof. A liquid composition in which a hydrogen halide salt of a specific 8th class amine or a quaternary ammonium halide is dissolved is poured into a mold and polymerized. At this time, each component may be added individually and polymerized, but in this case, uniform mixing and uniform reaction are difficult because the polymerization reactivity is extremely high.

For this reason, the radical polymerization initiator, the reducing substance, and the copper-containing compound are separately dissolved in advance in a monomer or a part of the monomer including its polymer, and the predetermined amounts of each are mixed immediately before polymerization. It is preferable to polymerize by

Although the method of the present invention can be carried out at room temperature, it is preferably carried out at a temperature of 50°C or higher to promote polymerization. A monomer or a monomer containing a polymer thereof, a polymerization initiator, etc. may be placed in a mold and the mold may be heated to a temperature of 50°C or higher to polymerize, or the temperature of the mold ring may be adjusted in advance. The mixture may be strained at a predetermined temperature of 50° C. or higher and then polymerized with a polymerization initiator and the like in a mold insert Q.

The formwork used in the method of the present invention is preferably made of metal in terms of strength, ease of heat removal, and the like.

1. The method of the present invention can be applied to the production of all molded articles of methacrylic acid ester polymers.

That is, in the method of the present invention in which polymerization is carried out within a mold, molded products of various insert shapes can be obtained by changing the mold. This method is particularly suitable for producing optical materials because the internal strain of the wind-coated material is very small. This optical material includes general-purpose lenses, Fresnel lenses, optical discs,
Prisms, mirrors, etc., and this method is especially suitable for manufacturing Fresnel lenses, which require a more precise shape, because it is easy to precisely transfer the mold surface.

In addition, this method is easy to manufacture large molded products, so it is suitable for molding car parts such as front windows, sunroofs, side windows, rear windows, nurseries, water tanks, bathtubs, etc.

Example 1.2, Comparative Example 1.2 In a 2e glass flask, 2.
2'-Azobisisobutyronitrile o, o4y was added and polymerized at 80°C. When the liquid in the flask reached about 2 poise, the polymerization was stopped by cooling to obtain a syrup containing a copolymer of dicyclopentenyl methacrylate and methacrylate.

11. Dissolved in 100 y of the above syrup to a concentration of t-butylpeio %. Silver naphthenate (Cu containing ff11O
%) dissolved to 1% by weight in methyl methacrylate, 0.04f, gly, and coldimercaptoacetate were added in the amounts shown in Table 1, and placed in a 160 x 160 x 3 m stainless steel mold in a water bath at 85°C. The polymerization was carried out, the curing time was measured, and the bending strength of the obtained polymer was measured, and the results are shown in Table 1.

Table-1 *1. GDMA nigericol dimercaptoacetate*
2. SH/Cu = number of moles of sulfur compound x number of SH groups/number of moles of copper compound x number of copper atoms *8 The polymer of Comparative Example 1 cracked when cooled after completion of polymerization.

Example 8 1 cyclohexyl methacrylate in 81 glass flask
．． After adding and dissolving 20Of, methyl methacrylate 800f, and azobisisobutyronitrile 0.51, 85°
Polymerization was carried out by stirring gently at C. As soon as the viscosity of the internal solution reached 2 poise, the reaction was stopped by cooling to obtain a syrup containing a copolymer of cyclohexyl methacrylate and methyl methacrylate.

, 60 g of the above syrup, 0.6 g of t-butyl peroxybenzoate, glycol dimercaptoacetate SH number of H groups: f), 0057), 0.8 f of a solution of phenethyl dibutylamine hydrochloride dissolved in dimethyl phthalate at 8% by weight, naphthene. Add 0.2F of a solution of acid copper (Cu content 10%) dissolved in methyl methacrylate to 0.1% by weight, mix for 1 minute, and then pour into a 150x150x8gg mold in a hot water bath at 85°C. The polymerization was completed in about 2 minutes. The strength of the obtained polymer is shown in Table 2.

Comparative Example 8 Using the syrup of Example 8, t-dodecylmercaptan t, 16 was added instead of glycol dimercaptoacetate.
1 (Number of moles of this compound x S) Number of 1 group: 0.0057)
Polymerization was carried out in the same manner as in Example 8 except that the polymer was used, and the strength of the polymer was measured. The results are shown in Table 2.

Table 2 Examples 4, 5, Comparative Example 4.6 Cyclohexyl methacrylate syrup 1o of Example 8
of t-butyl peroxybenzoate 0.96N,
Polymerization was carried out in the same manner as in Example 8, except that copper naphthenate was added in the amount shown in Table 8 to 1 g of a solution of phenethyl dibutylamine hydrochloride dissolved at 8% by weight in dimethyl phthalate and 0.6 g of glycol dimercaptoacetate. went.

The results are shown in Table-8.

Table 8 (Effects of the Invention) According to the present invention, methyl methacrylate or an unsaturated monomer containing methyl methacrylate as a main component can be rapidly polymerized to obtain a polymer with excellent physical properties.

Procedural amendment (voluntary) 6 October 13, 1985 Commissioner of the Patent Office Kuro 1) Mr. Yu Akira■, Indication of the case 1985 Patent Application No. 230682 2, Title of invention Process for producing methacrylic acid ester polymer 3. Relationship with the person making the amendment Patent applicant address 5-15 Kitahama, Higashi-ku, Osaka Name (
209) Sumitomo Chemical Co., Ltd. Representative: Hideo Mori 4, Agent address: 5-15 Kitahama, Higashi-ku, Osaka, Japan Claims and contents of amendments (1) The scope of claims in the specification is as shown in the attached sheet. to correct.

(2) "Neopentane glycol diacrylate, neopentane glycol dimethacrylate" on page 6, lines 17 to 19 of the specification is corrected to "neopentyl glycol diacrylate, neopentyl glycol dimethacrylate."

(3) "Methyl methacrylate, methyl methacrylate" on page 7, lines 18 to 19 is corrected to "methacrylic acid ester, methacrylic acid ester."

(4) r2 on page 14, lines 11-12. 2'-
"azobisisobutyronitrile" is corrected to "rN,N'-azobisisobutyronitrile".

(1) The above monomer 1 partially containing a methacrylic acid ester of an alcohol or phenol having 2 to 25 carbon atoms, an unsaturated monomer containing this as a main component, or a polymer thereof.
00 parts by weight, 0.1 to 5 parts by weight of radical polymerization initiator,
0.005 to 1 part by weight of one chlorine-containing compound selected from amine hydrochloride or quaternary ammonium chloride, copper salt of organic acid or copper-containing complex per weight of the monomer in terms of copper. 0.1 to 0.8 ppm, 2 SH groups
1. A method for producing a methacrylic acid ester polymer, which comprises polymerizing a sulfur compound containing at least one sulfur compound in an amount satisfying the following formula.

Formula Number of moles of the above sulfur compound x Number of SH groups thereof Number of moles of the above copper compound x Number of copper atoms = 5000 to 80000

Claims (1)

[Claims] (1) Initiate radical polymerization of 100 parts by weight of the above-mentioned monomer, which partially contains a methacrylic acid ester of alcohol or phenol having 2 to 25 carbon atoms, an unsaturated monomer containing this as a main component, or a polymer thereof. 0.1 to 5 parts by weight of at least one chlorine-containing compound selected from amine hydrochloride or quaternary ammonium chloride,
Polymerize a copper salt of an organic acid or a copper-containing complex in the presence of 0.1 to 0.8 ppm based on the weight of the monomer in terms of copper, and a sulfur compound containing two or more SH groups in an amount satisfying the following formula. A method for producing a methacrylic acid ester polymer, characterized in that: Formula: Number of moles of the above sulfur compound x number of SH groups/number of moles of the copper compound x number of copper atoms = 5000 to 8000