JPH10139824A - Composition for producing polyacrylic ester and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition capable of producing a high molecular weight material under an always regulated mild condition safely for human bodies and the environment and stably in air or oxygen. SOLUTION: This composition for producing polyacrylic ester consists of (A) a platinum compound, e.g. chloroplatinic acid, a platinumolefin complex, a platinum-phosphine complex, a platinum-phosphite complex, a platinum acetylacetonate complex, a platinumvinylsiloxane complex, etc., (B) a silicon compound having >=1 hydrogen atoms as substituents on Si and (C) an acrylic acid ester monomer and contains the component A in preferably 10<-8> -10<-1> mole based on 1 mole of the component C and the component B in >= equivalence of the component A and <=10mole equivalence of the component C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a composition for producing polyacrylates and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, azo radical polymerization initiators such as azobisisobutyronitrile and azobisvaleronitrile, and peroxides such as benzoyl peroxide and lauryl peroxide have been used as catalysts for polymerizing acrylic esters. A system radical polymerization initiator is generally used. However, these polymerization initiators require careful handling, not only adversely affecting the human body and the environment, but also may cause explosion in some cases. Further, the polymerization by these polymerization initiators is difficult to control, and there is a risk that the reaction will run away. That is, the conventional acrylate polymerization method has a problem in terms of safety. Furthermore, in the conventional method for polymerizing acrylic esters, when the method is carried out in air, the polymerization does not proceed stably, and it has been difficult to obtain a high molecular weight product.

[0003]

DISCLOSURE OF THE INVENTION The present invention avoids the dangers of conventional acrylate polymerization methods, uses a safe catalyst, and gently polymerizes polyacrylates under controlled conditions at all times. To provide compositions and methods. It is another object of the present invention to provide a composition and a method for stably polymerizing high molecular weight polyacrylates in air or oxygen.

[0004]

The present inventors have conducted studies to solve the above-mentioned problems, and as a result, have found that a combination of a platinum compound and a certain silicon compound is effective for polymerization of acrylic esters. Thus, the present invention has been completed. The present invention is a composition comprising a platinum compound, a silicon compound having at least one hydrogen atom as a substituent on silicon, and an acrylate monomer (claim 1), wherein the platinum compound is chloroplatinic acid, platinum -Olefin complex, platinum-phosphine complex, platinum-phosphite complex,
The composition for producing polyacrylates according to claim 1, which is selected from the group consisting of platinum acetylacetonate (claim 2), wherein the silicon compound is dialkoxysilane. The composition for producing a polyacrylate according to claim 1, wherein the monomer of the acrylate is selected from the group consisting of methyl methacrylate, methyl acrylate, and butyl acrylate. The composition for producing a polyacrylate according to claim 1, wherein the platinum compound is a platinum-vinylsiloxane complex, the silicon compound is dimethoxysilane, And / or diethoxysilane, and the acrylate monomer is methyl methacrylate Wherein a composition for the preparation of polyacrylic acid esters according to claim 1 (claim 5), platinum compounds are platinum - vinylsiloxane complex,
2. The silicon compound is dimethoxysilane and / or diethoxysilane, and the acrylate monomer is butyl acrylate.
(Claim 6), a acrylate monomer in the presence of a platinum compound and a silicon compound having at least one hydrogen atom as a substituent on silicon. Method for producing polyacrylic esters characterized by polymerizing (claim 7)
Wherein the platinum compound is chloroplatinic acid, a platinum-olefin complex, a platinum-phosphine complex, a platinum-phosphite complex,
The method for producing polyacrylates according to claim 7, wherein the silicon compound is dialkoxysilane, wherein the method is selected from the group consisting of platinum acetylacetonate. The method for producing a polyacrylate according to claim 7, wherein the acrylate monomer is selected from the group consisting of methyl methacrylate, methyl acrylate, and butyl acrylate. The method for producing polyacrylates according to claim 7, wherein the platinum compound is a platinum compound.
The polyacrylate according to claim 7, wherein the polyacrylate is a vinylsiloxane complex, the silicon compound is dimethoxysilane and / or diethoxysilane, and the acrylate monomer is methyl methacrylate. The method (claim 11), wherein the platinum compound is a platinum-vinylsiloxane complex, the silicon compound is dimethoxysilane and / or diethoxysilane, and the acrylate monomer is butyl acrylate. A method for producing a polyacrylate according to claim 7 (claim 12).

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The platinum compound of the present invention is generally known as a catalyst for hydrosilylation. Examples of such platinum compounds include complexes of platinum, alumina, silica, those in which solid platinum is supported on a simple substance such as carbon black, chloroplatinic acid, complexes of chloroplatinic acid with alcohols, aldehydes and ketones, Platinum acetylacetonate, platinum-olefin complex (for example,
Pt (CH2 = CH2) 2 (PPh3) 2, Pt (CH2 = C
H2) 2Cl2); platinum-vinylsiloxane complex (for example, Ptn ((CH2 = CH-) Me2SiOSiMe2)
(-CH = CH2)) m, Pt [(Me (CH2 = CH
-) SiO) 4] m), a platinum-phosphine complex (for example,
Pt (PPh3) 4, Pt (PBu) 4), platinum-phosphite complex (for example, Pt [P (OPh) 3] 4) (where Me is a methyl group, Bu is a butyl group, and Ph is a phenyl group). And m and n represent integers), dicarbonyldichloroplatinum, and platinum-hydrocarbon complexes described in Ashby U.S. Pat. Nos. 3,159,601 and 3,159,662; Lamoreaux) U.S. Pat. No. 3,220,972.
Also disclosed are platinum alcoholate catalysts described in the publication. In addition, Modic US Patent No. 3
The platinum chloride-olefin complex described in 516946 is also useful in the present invention. These catalysts may be used alone or in combination of two or more. From the viewpoint of catalytic activity, chloroplatinic acid, a platinum-olefin complex, a platinum-vinylsiloxane complex, and platinum acetylacetonate are preferred, and a platinum-vinylsiloxane complex is particularly preferred. The amount of the platinum compound used is not particularly limited, but 1 mol of the acrylate monomer
It is preferably used in the range of 10 <-8> to 10 <-1> mol, and particularly preferably in the range of 10 <-6> to 10 <-3> mol with respect to 1 mol of the acrylate monomer.

As the silicon compound in the present invention, any silicon compound having at least one hydrogen atom as a substituent on silicon can be used. As such a silicon compound, for example, the general formula (1)

[0007]

Embedded image

(Wherein R is the same or different and is a substituted or unsubstituted monovalent hydrocarbon group, alkoxy group, acyloxy group, silyl group, siloxy group, hydroxyl group, thiohydroxyl group,
An amino group, a silylamino group, and / or a halogen,
n is an integer from 1 to 4). Specifically, trimethoxysilane, dimethoxysilane, methoxysilane, triethoxysilane, diethoxysilane, ethoxysilane, trichlorosilane, dichlorosilane, chlorosilane, methyldichlorosilane, phenyldichlorosilane, methyldimethoxysilane, phenyldiethoxysilane , Methyldiethoxysilane, phenyldiethoxysilane, trimethylsilane, dimethylsilane, methylsilane, triethylsilane, diethylsilane, ethylsilane, triphenylsilane, diphenylsilane, phenylsilane, triacetoxysilane, diacetoxysilane, acetoxysilane, etc. But
However, it is not limited to these. Also, 1,1,3,
3-tetramethyldisiloxane, 1,1,3,3-tetraethyldisiloxane, 1,1,3,3-tetraphenyldisiloxane, 1,3-dimethyl-1,3-diphenyldisiloxane, 1,1, 3,3-tetramethoxydisiloxane, 1,1,3,3-tetrachlorodisiloxane, 1,1,2,2-tetramethyldisilane, 1,1,
2,2-tetraethyldisilane, 1,1,2,2-tetraphenyldisilane, 1,1,3,3-tetramethyldisilazane, 1,3,5-trimethylcyclotrisiloxane, 1,3,5,7 Compounds containing two or more silicon atoms, such as tetramethylcyclotetrasiloxane, can also be used. Furthermore, polysiloxane having one or more silicon-hydrogen bonds in the molecule, such as polymethyl hydrogen siloxane, polydimethylsiloxane having terminal Si-H, and polysil having one or more silicon-hydrogen bonds in the molecule Sesquioxane, polycarbosilane having one or more silicon-hydrogen bonds in the molecule, 1 in the molecule
Polysilazane having more than one silicon-hydrogen bond, JP-A-3-200807 and JP-A-3-9526
It is also possible to use a silicon-hydrogen bond-containing compound having an organic skeleton as described in JP-A-6-1994. These silicon compounds may be used alone or in combination of two or more. Alkoxysilanes are preferred in terms of reactivity, and dialkoxysilanes such as dimethoxysilane and diethoxysilane are particularly preferred. The amount of the silicon compound used is not particularly limited, but is preferably equal to or more than the equivalent of the catalyst.
It is preferable to use 0 equivalent or less.

Examples of the acrylate monomers in the present invention include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate,
Examples include, but are not limited to, butyl acrylate, butyl methacrylate, vinyl acrylate, vinyl methacrylate, allyl acrylate, allyl methacrylate, phenyl acrylate, phenyl methacrylate, and the like. These acrylate monomers may be used alone or in combination of two or more. Further, a vinyl compound copolymerizable with these acrylic acid ester monomers may be allowed to coexist. Specific examples of such a vinyl compound include, but are not limited to, ethylene, propylene, 1-butene, isobutylene, butadiene, vinyl chloride, isoprene, chloroprene, vinyl acetate, and styrene. These vinyl compounds may be used alone,
Two or more kinds may be used in combination.

The method for producing polyacrylic esters according to the second invention of the present invention can be carried out either in a solvent-free system or in the presence of a solvent. Solvents that can be used in the present invention are not particularly limited as long as they are solvents other than those that cause hydrolysis of silicon-hydrogen bonds.
Toluene, xylene, hexane, heptane, octane,
Hydrocarbon solvents such as cyclohexane; ether solvents such as tetrahydrofuran, 1,4-dioxane and diethyl ether; ketone solvents such as acetone and methyl ethyl ketone; chloroform; methylene chloride;
-A halogen-based solvent such as dichloroethane can be used. A silicon compound to be subjected to the reaction, and / or
Alternatively, acrylates can be used as the solvent. These solvents may be used alone or as a mixed solvent of two or more types. Among these solvents, tetrahydrofuran, chloroform and toluene are preferred. The amount of solvent used is not particularly limited,
0 to 50 mL per 1 g of acrylic ester used
Is preferably used in the range of 0 to 10 mL, more preferably in the range of 0 to 5 mL.

Although the reaction temperature in the present invention is not particularly limited, the catalyst activity is lowered at -50 ° C or lower, and the catalyst is deactivated by heat at 200 ° C or higher.
A range of 200 ° C is preferred, and a range of 0 ° C to 150 ° C is particularly preferred. The platinum compound used in the present invention acts as a polymerization catalyst for acrylates by acting with the silicon compound.However, in the case where the reaction runs away, by rapidly adding a coordinating catalyst deactivator, the platinum compound is rapidly used. It is possible to stop the reaction. Examples of such a catalyst deactivator include a compound containing an aliphatic unsaturated bond, an organic phosphorus compound, an organic sulfur compound, a nitrogen-containing compound, and a tin compound. As a compound containing an aliphatic unsaturated bond,
Examples include propargyl alcohol, ene-yne compounds, and maleic esters. As organic phosphorus compounds,
Triorganophosphine, diorganophosphine,
Organophosphones, triorganophosphites and the like are exemplified. Examples of the organic sulfur compound include organomercaptan, diorganosulfide, hydrogen sulfide, benzothiazole, and benzothiazole disulfite. As the nitrogen-containing compound, ammonia, 1
Examples thereof include a tertiary alkylamine, an arylamine, urea, and hydrazine. Examples of the tin compound include stannous halide dihydrate, stannous carboxylate, and the like. Of these catalyst deactivators, maleic esters are preferred, and dimethyl maleate is particularly preferred. The catalyst deactivator is used in an amount of 0 to 1 mol of the platinum compound used.
It is preferably used in a range of 1000 mol,
More preferably, it is used in the range of 0 mol,
It is particularly preferred to use it in the range of 0 mol.

To prepare the composition for producing polyacrylates of the present invention, a platinum compound, a silicon compound having at least one hydrogen atom as a substituent on silicon, and an acrylate monomer are simply mixed. Is fine.
The mixing method and order are not limited, and the essential components can be prepared by contacting each other. The mixture need not be homogeneous, but may be heterogeneous. When preparing the composition for producing polyacrylates of the present invention, a solvent may or may not be used. When a solvent is used, a solvent that does not decompose silicon-hydrogen bonds is used.
A catalyst deactivator and the like can be added according to the purpose or as necessary.

The method for producing polyacrylates of the present invention is carried out by mixing a platinum compound, a silicon compound having at least one hydrogen atom as a substituent on silicon, and an acrylate monomer. The method and order of mixing are not limited, and a solvent may or may not be used. When a solvent is used, a solvent that does not decompose silicon-hydrogen bonds is used. The amount of the solvent to be used is not particularly limited, but it is preferable to use the solvent in an amount of 0 to 50 mL per 1 g of the acrylate used.
More preferably used in the range of 10 mL, 0-5 m
It is particularly preferable to use in the range of L.

The reaction temperature in the present invention is not particularly limited. However, at -50 ° C or lower, the catalytic activity decreases, and at 200 ° C or higher, the catalyst is deactivated by heat.
The range of 200 ° C. is preferred, and the range of 0 ° C. to 100 ° C. is particularly preferred. The method for producing polyacrylates of the present invention may be carried out by a gas phase reaction or a liquid phase reaction. The reaction may be a homogeneous reaction,
It may be a heterogeneous reaction. About the reaction atmosphere,
There is no particular limitation as long as the atmosphere does not decompose silicon-hydrogen bonds, and it can be carried out in an atmosphere of an inert gas such as nitrogen, argon, helium or the like, as well as in an atmosphere of air, oxygen or hydrogen.

[0015]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto. (Example 1) 1.01 g (10.1 mmol) of methyl methacrylate was weighed and placed in a 20 mL two-necked flask, and a reflux condenser and a septum were attached to replace with nitrogen. Xylene solution of platinum-vinylsiloxane complex (9.71 × 10 −5 mol /
g) 10 mg (9.7.times.10@-4 mmol) was added and the mixture was stirred at room temperature. The dimethoxysilane (H2Si (OM
e) 2) When 0.4811 g (5.220 mmol) was added, foaming occurred and a little heat was generated. After stirring at room temperature for 2 hours and standing for 23 hours, the viscosity of the reaction mixture slightly increased, and NMR and GPC measurements confirmed that methyl methacrylate was polymerized. Further, when left at room temperature for 4 days, a glassy solid was obtained. GP
As a result of the C measurement, Mw / Mn = 161000/11800
It was 0. (Example 2) 30 mL 2 equipped with a reflux condenser and a septum
The flask was replaced with nitrogen, and methyl methacrylate 0.7
313 g (7.304 mmol) of a xylene solution of a platinum-vinylsiloxane complex (9.60 × 10 −7 mol / g)
8.68 mg (8.33 × 10 −6 mmol), and THF
2.0 mL was charged. This solution was stirred while being heated to 50 ° C., and dimethoxysilane (H 2 Si (OMe) 2)
0.445 g (4.82 mmol) of a THF solution (3.0 m
L) was added dropwise. After heating and stirring at 50 ° C. for 3.8 hours, the solution was allowed to stand at room temperature for 65 hours, and an increase in the viscosity of the solution was observed. As a result of NMR and GPC measurement, polymethyl methacrylate (Mw / Mn = 125000/103)
000) was confirmed. (Example 3) The reaction was performed in an air atmosphere. In a 20 mL two-necked flask equipped with a reflux condenser and a septum, 0.5601 g (5.594 mmol) of methyl methacrylate and a xylene solution of a platinum-vinylsiloxane complex (9.60 × 1) were added.
9.9 mg (9.5.times.10@-6 mmol) were added. While stirring this solution at room temperature, 0.680 g (7.38 m) of dimethoxysilane (H2Si (OMe) 2) was added.
mol) was added. When stirring was continued at room temperature for 30 hours, a colorless, transparent, highly viscous liquid was obtained. As a result of NMR and GPC measurement, polymethyl methacrylate (Mw / Mn = 13
4000/110000) was confirmed. (Example 4) As a reaction apparatus, an autoclave (made of stainless steel, TVS-1 type, 10 mL) manufactured by pressure glass industry and having a glass inner cylinder (GI-10) set was used. In a nitrogen-purged autoclave, 0.5161 g (5.155 mmol) of methyl methacrylate, a xylene solution of a platinum-vinylsiloxane complex (9.60 × 10 −7).
mol / g) 9.0 mg (8.6.times.10@-6 mmol), 0.697 g of dimethoxysilane (H2Si (OMe) 2)
(7.56 mmol) was added and sealed immediately. After heating at 100 ° C. for 12 hours, the mixture was allowed to cool at room temperature for 9 hours, and NMR measurement revealed that polymerization of methyl methacrylate was confirmed. When left at room temperature for 5 days, it became a glassy solid. (Example 5) As a reaction apparatus, an apparatus in which a glass inner cylinder (GI-10) was set in an autoclave (made of stainless steel, TVS-1 type, 10 mL) manufactured by Pressure Glass Corporation was used. In a nitrogen-purged autoclave, 0.5049 g (5.043 mmol) of methyl methacrylate, a xylene solution of a platinum-vinylsiloxane complex (9.60 × 10 −7).
(mol / g) 8.7 mg (8.4.times.10@-6 mmol) and THF 1.0 mL. Dimethoxysilane (H2
0.732 g (7.94 mmol) of Si (OMe) 2) was added, the mixture was immediately sealed, heated at 100 ° C for 12 hours, and allowed to cool at room temperature for 9 hours. As a result of NMR and GPC measurement, polymethyl methacrylate (Mw / Mn = 146000 /
132000) was confirmed. (Example 6) As a reaction apparatus, an autoclave (manufactured by stainless steel, TVS-1 type, 10 mL) manufactured by pressure glass industry and having a glass inner cylinder (GI-10) set was used. The autoclave was purged with nitrogen, and 0.5058 g (5.052 mmol) of methyl methacrylate and a xylene solution of a platinum-vinylsiloxane complex (9.60 × 10 −7 mol /
g) 9.7 mg (9.3.times.10@-6 mmol) and 1.0 mL of toluene were charged. Dimethoxysilane (H2Si
(OMe) 2) 0.687 g (7.46 mmol) was added, the mixture was sealed, heated at 100 ° C for 12 hours, and then allowed to cool at room temperature for 10 hours. NMR and GPC Measurement Results Polymethylmethacrylate (Mw / Mn = 142000/127)
000) was confirmed. (Example 7) 20 mL 2 equipped with a reflux condenser and a septum
The flask was replaced with nitrogen and butyl acrylate 1.05
g (8.19 mmol) and 10 mg of a xylene solution of a platinum-vinylsiloxane complex (9.71 × 10 −5 mol / g)
(9.7.times.10@-4 mmol). 0.387 dimethoxysilane (H2Si (OMe) 2) while stirring at room temperature
g (4.20 mmol) was added and a slight exotherm occurred. After stirring at room temperature for 24 hours, a colorless, transparent, and highly viscous liquid was obtained. From the result of NMR measurement, formation of polybutyl acrylate was confirmed. (Example 8) As a reaction apparatus, an autoclave (made of stainless steel, TVS-1 type, 10 mL) manufactured by pressure glass industry and having a glass inner cylinder (GI-10) set was used. In a nitrogen-purged autoclave, 0.3117 g (2.432 mmol) of butyl acrylate and a xylene solution of a platinum-vinylsiloxane complex (9.60 × 10 −7 mol /
g) 94.9 mg (9.11 * 10 <-5> mmol) and 0.229 g of dimethoxysilane (H2Si (OMe) 2)
(2.48 mmol) and sealed. After heating at 100 ° C. for 89 hours, the mixture was allowed to cool at room temperature for 7 hours, and NMR and GP
C measurement was performed. Polybutyl acrylate (Mw / Mn
= 310,000 / 280,000). (Comparative Example 1) 0.505 g (5.04 mmol) of methyl methacrylate and 0.687 g (7.46 mmol) of dimethoxysilane (H2Si (OMe) 2) were placed in a 10 mL eggplant type flask.
l) was weighed out and replaced with nitrogen by attaching a reflux condenser. After standing at room temperature for 20 days, 100% of methyl methacrylate monomer remained and polymerization of methyl methacrylate was not observed. (Comparative Example 2) In a 10-mL eggplant type flask, 0.3520 g (3.516 mmol) of methyl methacrylate and a xylene solution of a platinum-vinylsiloxane complex (9.60 x 10-7 mol)
8.96 mg (8.60 × 10 −6 mmol) of l / g) were weighed out, and the atmosphere was replaced with nitrogen by attaching a reflux condenser. Left at room temperature for 20 days, but 100% methyl methacrylate monomer
It remained and polymerization of methyl methacrylate was not recognized.

[0016]

According to the composition for producing polyacrylates and the method for producing polyacrylates of the present invention, polyacrylates can be produced safely under mild conditions. Furthermore, high molecular weight polyacrylates can be produced in air or oxygen.

Claims (12)

[Claims] 1. A composition for producing polyacrylates, comprising a platinum compound, a silicon compound having at least one hydrogen atom as a substituent on silicon, and an acrylate monomer. 2. The platinum compound according to claim 1, wherein the platinum compound is selected from the group consisting of chloroplatinic acid, platinum-olefin complex, platinum-phosphine complex, platinum-phosphite complex, and platinum acetylacetonate. The composition for producing polyacrylates according to the above. 3. The composition according to claim 1, wherein the silicon compound is a dialkoxysilane. 4. The composition for producing a polyacrylate according to claim 1, wherein the acrylate monomer is selected from the group consisting of methyl methacrylate, methyl acrylate, and butyl acrylate. . 5. The platinum compound is a platinum-vinylsiloxane complex, and the silicon compound is dimethoxysilane, and / or
The composition for producing a polyacrylate according to claim 1, wherein the composition is a diethoxysilane, and the acrylate monomer is methyl methacrylate. 6. The platinum compound is a platinum-vinylsiloxane complex, and the silicon compound is dimethoxysilane, and / or
The composition for producing a polyacrylate according to claim 1, wherein the composition is a diethoxysilane, and the acrylate monomer is butyl acrylate. 7. A method for producing polyacrylates, comprising polymerizing acrylate monomers in the presence of a platinum compound and a silicon compound having at least one hydrogen atom as a substituent on silicon. 8. The method according to claim 7, wherein the platinum compound is selected from the group consisting of chloroplatinic acid, platinum-olefin complex, platinum-phosphine complex, platinum-phosphite complex, and platinum acetylacetonate. The method for producing polyacrylates according to the above. 9. The method for producing polyacrylates according to claim 7, wherein the silicon compound is dialkoxysilane. 10. The method for producing a polyacrylate according to claim 7, wherein the acrylate monomer is selected from the group consisting of methyl methacrylate, methyl acrylate, and butyl acrylate. 11. The method according to claim 7, wherein the platinum compound is a platinum-vinylsiloxane complex, the silicon compound is dimethoxysilane and / or diethoxysilane, and the acrylate monomer is methyl methacrylate. The method for producing polyacrylates according to the above. 12. The method according to claim 7, wherein the platinum compound is a platinum-vinylsiloxane complex, the silicon compound is dimethoxysilane and / or diethoxysilane, and the acrylate monomer is butyl acrylate. The method for producing polyacrylates according to the above.