JP3364249B2 - Polymerization method of polymerizable vinyl compound - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for polymerizing a polymerizable vinyl compound. Heretofore, radical polymerization, anion polymerization and group transfer polymerization have been known as polymerization methods for polymerizable vinyl compounds. In the radical polymerization method, generally, a radical generator such as an organic peroxide and an azo compound is used as a polymerization initiator.However, these compounds have a risk of explosion and require careful handling. Further, the polymerization reaction had to be performed under relatively high temperature conditions. Similarly, in the case of the anionic polymerization method, there has been a problem that an alkali metal, an organic alkali metal compound, a Grignard reagent, and the like, which require careful handling, must be used as a polymerization initiator. Also, the group transfer polymerization method can be applied only to limited monomers such as methacrylic acid ester, and because of a special process,
There was a problem that mass production and practical use were difficult. For this reason, there has been a demand for a method of performing polymerization under mild conditions using a polymerization initiator that can safely handle a polymerizable vinyl compound. The inventors of the present invention have made intensive studies to solve the above-mentioned problems, and as a result, have found that a polymerizable vinyl compound contains a compound containing a silicon-bonded hydrogen atom and a group VIII of the periodic table. The present inventors have found the surprising fact that a polymerizable vinyl compound can be polymerized at room temperature or lower when a transition metal catalyst is mixed, and reached the present invention. That is, an object of the present invention is to provide a novel polymerization method capable of polymerizing a polymerizable vinyl compound under mild conditions. SUMMARY OF THE INVENTION The present invention relates to (A) a polymerizable vinyl compound, and (B) a silicon atom bond.
Hydrogen atom-containing compound [0.01 to 30% by weight of component (A)]
%] And (C) platinum compound catalyst, palladium compound catalyst
Group consisting of a catalyst, a rhodium-based catalyst and a ruthenium-based catalyst
[0.1 weight p of component (A)
pm or more] to polymerize (A) the polymerizable vinyl compound
And a method for polymerizing a polymerizable vinyl compound. More specifically, the polymerizable vinyl compound (A) used in the present invention is a compound containing a radical-reactive vinyl group. Examples of the vinyl compound include methyl acrylate and acrylic acrylate. Acrylates such as ethyl acrylate and propyl acrylate; methacrylates such as methyl methacrylate, ethyl methacrylate and propyl methacrylate; phenyl-substituted vinyl compounds such as styrene and α-methylstyrene; acrylonitrile and methacrylonitrile And vinyl carboxylates such as vinyl acetate and vinyl propionate. Further, these components (A)
It is also possible to copolymerize by mixing more than one kind. Examples of the compound containing a silicon-bonded hydrogen atom as the component (B) used in the present invention include hydride halogenosilanes such as dimethylchlorosilane, methyldichlorosilane and trichlorosilane; dimethylmethoxysilane, dimethylethoxysilane and dimethylpropoxy. Silane, dimethylisopropoxysilane, methyldiethoxysilane,
Hydride alkoxysilanes such as trimethoxysilane and triethoxysilane; 1,1,1,3,3-pentamethyldisiloxane, 1,1,1,3,3,5,5,7,7,9,9 And organopolysiloxanes containing silicon-bonded hydrogen atoms such as -undecamethylpentasiloxane. Among these, hydridochlorosilanes and hydridoalkoxysilanes are preferable because of their high catalytic activity in the polymerization reaction.
The transition metal catalyst of the component (C) used in the present invention includes :
Platinum compound catalysts such as chloroplatinic acid, alkene complexes of platinum, complexes of platinum with vinyl group-containing siloxanes; palladium compound catalysts such as tetrakis (triphenylphosphine) palladium [0]; rhodium-based catalysts such as Wilkinson complexes; dichlorotris Ruthenium-based catalysts such as (triphenylphosphine) ruthenium [II] and the like can be mentioned. In the method for polymerizing a polymerizable vinyl compound of the present invention ,
Simply makes the components (A), (B) and (C) uniform
The polymerization proceeds by mixing. The target vinyl
In order to obtain a polymer in good yield, the component (A)
Weight ratio of 0.01 to 30% by weight to
Preferably, it is 0.1 to 20% by weight. This is 0.01
If the amount is less than 10% by weight, the polymerization reactivity decreases, and a sufficient conversion rate is obtained.
If not more than 30% by weight, hydride formed as a side reaction
This is because the amount of the rosylation product cannot be ignored.
You. The weight ratio of the component (C) to the component (A) is 0.1.
1 ppm or more. This is heavy at less than 0.1 ppm.
The reactivity decreases and a sufficient conversion cannot be obtained.
It is. In the polymerization method of the present invention, the aforementioned component (A)
The components (B) and (C) can be mixed and polymerized at any temperature, and polymerization can be caused even at room temperature or under low temperature conditions of about -10 ° C. [0008] Next, the present invention will be described with reference to examples. still,
In the examples, MMA represents methyl methacrylate, Me represents a methyl group, Et represents an ethyl group, Pr represents a propyl group, and Mn represents
Indicates a number average molecular weight. Example 1 Methyl methacrylate, a compound containing a silicon-bonded hydrogen atom, and platinum and 1,3-divinyl-1,1,1,
Complexes with 3,3-tetramethyldisiloxane were mixed at the ratio shown in Table 1, and the mixture was subjected to a polymerization reaction at -10 ° C and room temperature for a predetermined time. After the completion of the reaction, the reaction mixture was poured into a large amount of hexane to precipitate a polymer. After the obtained precipitate was dried under reduced pressure, the yield was determined. This precipitate is
Analysis by ¹³ NMR revealed that this was polymethyl methacrylate. The molecular weight of this polymethyl methacrylate was measured by gel permeation chromatography (GPC). Table 1 shows the results of these measurements. [Table 1] Example 2 Methyl methacrylate, dimethylisopropoxysilane, and various transition metal catalysts of Group VIII of the Periodic Table were mixed in the proportions shown in Table 2, and the mixture was subjected to a polymerization reaction at room temperature for a predetermined time. After the completion of the reaction, the reaction mixture was poured into a large amount of hexane to precipitate a polymer. After the obtained precipitate was dried under reduced pressure, the yield was determined. The molecular weight was determined by gel permeation chromatography (GPC). Table 2 shows the results of these measurements. [Table 2] Example 3 Various vinyl monomers, dimethylisopropoxysilane and platinum, and 1,3-divinyl-1,1,3,3
A complex with tetramethyldisiloxane was mixed at a ratio shown in Table 3, and the mixture was subjected to a polymerization reaction at room temperature for a predetermined time. After the completion of the reaction, the reaction mixture was poured into a large amount of hexane to precipitate a polymer. After the obtained precipitate was dried under reduced pressure, the yield was determined. The molecular weight was determined by gel permeation chromatography (GPC). Table 3 shows the results of these measurements. [Table 3] 1) Not measured because it is insoluble in tetrahydrofuran, a solvent for GPC. Comparative Example 1 Methyl methacrylate, a compound containing a silicon-bonded hydrogen atom, platinum and 1,3-divinyl-1,1,3,3
Complexes with tetramethyldisiloxane were mixed at the ratio shown in Table 4 and heated and stirred at 50 ° C. The reaction mixture was sampled at regular intervals. When these samples were put into a large amount of hexane and the presence of a polymer was checked, the results shown in Table 4 were obtained. From this table, it was found that in the polymerization method of the present invention, a combination of a vinyl monomer, a compound containing a silicon-bonded hydrogen atom, and a transition gold catalyst belonging to Group VIII of the periodic table is essential. [Table 4] Comparative Example 2 Polymerization of methyl methacrylate was attempted using various Group VIII transition metal catalysts of the Periodic Table under the same conditions as in Example 2 except that dimethylisopropoxysilane was not added. . As a result, no polymer was obtained. According to the method for polymerizing a polymerizable vinyl compound of the present invention, various polymerizable compounds can be used without using an initiator such as an organic peroxide or an organic alkali metal compound which requires careful handling. Vinyl compound at room temperature or about -10 ° C
Polymerization can be carried out under mild conditions of low temperature .

────────────────────────────────────────────────── ─── Continued on the front page (56) References Japanese Patent Publication No. 40-18861 (JP, B1) Japanese Patent Publication No. 39-6511 (JP, B1) (58) Fields surveyed (Int. Cl. ⁷ , DB name) C08F 2/00-2/50 C08F 4/26

Claims (1)

(57) [Claims] (1) (A) a polymerizable vinyl compound, (B) silicon
Atom-bonded hydrogen atom-containing compound [from component (A) of 0.01 to
30% by weight] and (C) platinum compound catalyst, palladium conversion
Compound catalyst, rhodium catalyst and ruthenium catalyst
A transition metal catalyst selected from the group consisting of
Weight ppm or more], and (A) a polymerizable vinyl compound
A method for polymerizing a polymerizable vinyl compound, comprising polymerizing