Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – From phenol – phenol ether – or inorganic phenolate
Reexamination Certificate
2001-06-27
2003-01-28
Dawson, Robert (Department: 1712)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
From phenol, phenol ether, or inorganic phenolate
C502S155000, C502S167000, C502S171000, C528S094000, C528S416000
Reexamination Certificate
active
06512074
ABSTRACT:
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to polymerization catalysts which are suitable for preparing polymers of oxirane compounds such as ethylene oxide, epichlorohydrin and allyl glycidyl ether by suspension precipitation polymerization and to a process for preparing polymers of oxirane compounds using the polymerization catalysts.
2. Description of the Prior Art
Since polymers of oxirane compounds having various properties can be obtained by using a variety of oxirane compounds as a starting material, the polymers are used in very wide fields such as rubber parts for automobiles, rubber members for electrical and electronic equipments, polymers for various plastics blending and solid polyelectolytes.
Industrial processes for preparing the polymers of oxirane compounds are exemplified by solution polymerization wherein the oxirane compounds are polymerized in an organic solvent which can dissolve monomers and the polymers and by suspension precipitation polymerization wherein the oxirane compounds are polymerized in an organic solvent which cannot dissolve the polymers to precipitate granular polymers. The latter polymerization process has advantages in that concentrations of the monomers can be raised during polymerization, and the polymers can be readily separated from the solvents after polymerization, while specific catalysts and solvents must be selected.
Catalysts which can polymerize the oxirane compounds are exemplified by catalysts having actions of Lewis acids such as boron fluoride, aluminum chloride, tin chloride and iron chloride. When polymerization is carried out by using these catalysts, relatively low-molecular weight (for example, molecular weight of several thousand to around fifty thousand) polymers are obtained.
It is known to use reaction products of alkylzinc with water, reaction products of organotin compounds with phosphates, reaction products of alkylaluminum with water, reaction products of alkylaluminum with phosphoric acid compounds or the like as catalysts in order to obtain high-molecular weight polymers which are useful in specific fields such as rubber industry. In particular, as the catalysts containing alkylaluminum, catalysts prepared by adding, to the reaction products of alkylaluminum with water, further chelating agents such as acetylacetone (for example, see J. Polym. Sci. A-1, 7, 525 (1969)), catalysts prepared by adding, to the reaction products of alkylaluminum with the phosphoric acid compounds, further the third component(s) consisting of amine compounds, organophosphorus compounds and/or organoarsenic compounds (see Japanese Examined Patent Publication No. 27534/1971), catalysts prepared by adding N-substituted morpholine such as N-ethylmorpholine to the reaction products of alkylaluminum with the phosphoric acid compounds (see Japanese Examined Patent Publication No. 8852/1981) and catalysts prepared by adding 1, 8-diazabicyclo[5.4.0]-7-undecene to the above-mentioned reaction products (see Japanese Examined Patent Publication No. 51171/1981) were proposed as excellent catalysts to obtain high-molecular weight polymers of the oxirane compounds.
However, most of the above-mentioned prior arts using the alkylaluminum catalysts relate to solution polymerization. Suspension precipitation polymerization of the oxirane compounds in the presence of these catalysts caused problems that the high-molecular weight polymers sometimes are not obtained, reaction mixture cannot be stirred in a reaction apparatus and the formed polymers cannot be taken out of the reaction apparatus since the polymers does not become granular but solid.
SUMMARY OF THE INVENTION
In view of the above-mentioned various problems, objects of the present invention are to provide catalysts which exhibit excellent activities on suspension precipitation polymerization and to provide a method wherein high-molecular weight polymers of oxirane compounds can be prepared effectively in high yields in the presence of the catalysts.
Studying variously in order to solve the above-mentioned problems, the present inventors found that in catalysts prepared by adding, to reaction products of alkylaluminum compounds with oxoacid compounds of phosphorus, further the third components, only the third components having specific structure and properties give catalysts for the suspension precipitation polymerization which exhibit excellent activities to obtain the high-molecular weight polymers of the oxirane compounds, and completed the present invention.
The polymerization catalysts of the oxirane compounds according to the present invention are catalysts which are suitable to carry out the suspension precipitation polymerization of the oxirane compounds in an organic solvent which cannot dissolve the polymers and are characterized by comprising a reaction product of (A) an alkylaluminum compound, (B) an oxoacid compound of phosphorus having at least one OH group in its molecule and (C) a nitrogen-containing cyclic compound having pKa of 6 to 8.
The process for preparing the polymers of the oxirane compounds according to the present invention is a process wherein the monomeric oxirane compounds are subjected to the suspension precipitation polymerization in the organic solvent which cannot dissolve the polymers in the presence of the catalysts having the above-mentioned characteristics to prepare the polymers of the oxirane compounds.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The present invention is described in detail hereinafter.
The alkylaluminum compounds to be used in the catalysts according to the present invention are represented by the general formula:
(R
7
)
p
AlX
3−p
wherein R
7
is lower alkyl such as alkyl having one to six carbon atoms, X is halogen or hydrogen, and p is 1, 1.5, 2 or 3.
Examples of the alkylaluminum compound are triethylaluminum, diethylaluminum chloride, ethylaluminum sesquichloride [Et
3
Al
2
Cl
3
], triisobutylaluminum, diisobutylaluminum hydride, tri-n-butylaluminum, tri-n-propylaluminum and the like. These compounds can be used solely or in combination depending on the monomeric oxirane compounds to be used.
The oxoacid compounds of phosphorus to be used in the catalysts according to the present invention have at least one OH group in their molecules. Examples of the oxoacid compound of phosphorus are inorganic phosphoric acids such as phosphorous acid, diphosphorous acid, hypophosphorous acid, metaphosphoric acid, pyrophosphoric acid, orthophosphoric acid and polyphosphoric acid; organic phosphoric acids such as nitrilotris(methylenephosphoric acid) and 1-hydroxyethane-1, 1-diphosphonic acid; acidic phosphates, which are partially esterified products of alcohols with phosphoric acid; and the like. The acidic phosphates are represented by the general formula:
O═P(OR
8
)
q
(OH)
3−q
wherein R
8
is lower alkyl such as alkyl having one to six carbon atoms, and q is 1 or 2, and they can be exemplified by acidic methyl phosphate, acidic ethyl phosphate, acidic propyl phosphate, acidic isopropyl phosphate and acidic butyl phosphate. Further, it is preferable to use, as the oxoacid compound of phosphorus, phosphoric acid or a mixture of polyphosphoric acids represented by the following general formula [II] and having a corresponding H
3
PO
4
content of 90 to 110% by weight (compounds having a corresponding H
3
PO
4
content of higher than 100% by weight are usually called condensed phosphoric acids), since polymerization activities of the obtained catalysts on the oxirane compounds are raised,
wherein n is an integer of 2 to 10.
Even if the phosphoric acid or the mixture contains a small amount of moisture, it does not cause any problems, but a large amount of moisture in the phosphoric acid or the mixture inhibits catalytic reactions, and the polymerization activities tend to be lowered. Accordingly, it is preferable to use the phosphoric acid or the mixture having a corresponding H
3
PO4 content of 90% by weight or higher.
The nitrogen-containing cyclic com
Miura Katsuhito
Shimizu Yasumi
Shoji Shigeru
Armstrong Westerman & Hattori, LLP
Aylward D.
Daiso Co. Ltd.
Dawson Robert
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