JPS60123530A - Glycidyl ester-epihalohydrin-ethylenic epoxide copolymer - Google Patents

Abstract

PURPOSE:To produce a rubbery solid copolymer giving a crosslinked product having high oil resistance and freeze resistance, and a useful functional membrane, etc., by polymerizing a carboxylic acid glycidyl ester, an epihalohydrin and an ethylenic epoxide in the presence of an organotin-phosphoric acid ester catalyst. CONSTITUTION:The objective rubbery solid copolymer is a polyether having a reduced viscosity of >=0.5 measured as 0.1% monochlorobenzene solution at 80 deg.C, and composed of the structure units of formula I - formula III (R is 1-4C alkyl R<1> is H or methyl; X is halogen), wherein the composition of the polyether is 35-90mol% glycidyl ester of a 2-5C saturated aliphatic carboxylic acid, 5-60% epihalohydrin and >=5% ethylenic epoxide in terms of monomer units. The copolymerization is carried out in the presence of a catalyst obtained by the thermal condensation of an organotin compound with an alkyl ester of orthophosphoric acid or poly phosphoric acid.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to glycidyl goster-epihalohydrin-ethylenic epoxide copolymers. In this specification, the term "-tyrenic epoxide" is used to mean "nidylene oxide" or "pyrene oxide."

Although many techniques have been disclosed regarding the ring-opening polymerization of three-membered epoxides, there are few examples of high polymerization of heptamers having functional groups other than epoxides. Among them, it is known that organoaluminium-based catalysts and organotin-phosphate ester-based catalysts are particularly capable of high polymerization of a wide range of epoxides. However, although glycidyl carboxylate, which is an epoxide having an ester group, has various useful chemical and physical properties due to its polymer structure, so far no C high polymer has been produced. There is no C obtained.

Generally, it is difficult to obtain a high polymer of glycidyl ester using an organoaluminium-based catalyst due to the reactivity of its ester group. An example of glycidyl ester being used as a comonomer in copolymerization is the copolymerization of epichlorohydrin and glycidyl methacrylate using an organoaluminum catalyst (US Pat. No. 3,285,87).
No. 0), but the composition ratio of these glycidyl esters is extremely small, and the molecular weight of the obtained copolymer is also low. Furthermore, as the ratio of glycidyl ester increases, the molecular weight decreases significantly.

There have also been reports on the ring-opening polymerization of glycidyl acetate-1 with boron fluoride etherate (Mak
romol Chem 71.150 (1964)), only a low molecular weight polymer in the form of an oil was obtained.

No. 1-377369 related to the applicant's application
Although there is a general statement in part of No. 4 that glycidyl esters can be polymerized using a tin-phosphoric acid ester catalyst, the details of the polymerization reaction and the high polymer obtained by this are not disclosed. No disclosure has been made.

The present inventors have developed a homopolymer of carboxylic acid glycidyl ester using this organotin-phosphate ester catalyst, a carboxyl glycidyl ester-allylglycidyl r-thyl copolymer, and a carboxylic acid glycidyl ester-pihalohydrin copolymer. I filed a C patent application regarding the combination (Japanese Patent Application Nos. 119921-1982, 119922-1980, and 1199-1198).
Furthermore, using the same catalyst, a high molecular weight copolymer of glycidyl carboxylate, evihalohydrin and ethylenic epoxide was successfully synthesized, and the resulting copolymer had extremely useful rubbery properties and was used in various The present invention was completed based on the knowledge that it has promising applications.

In other words, the composition ratio of the wood invention in monomer terms is 2 to 2 carbon atoms.
5 saturated aliphatic carboxylic acid glycidyl ester 35~
90 mol%, (1) Bihalohydrin 5-60 mol% Ethylene epoxide 5 mol% or more, and the main chain structure is substantially composed of structural units represented by the following formulas (I) to (I), It is a rubbery solid glycidyl ester-epihalohydrin-ethylenic epoxide copolymer having a reduced viscosity of 0.5 or more as measured in a 0.1% monochlorobenzene solution at J5 at 80°C. In addition(
I) ~ (l [) formula is 1000H2-CI-1-0-+- CH20COR(I> (in the formula, R represents a C1-C4 alkyl group) → CH2
-CH-0← R1<'K) (In the formula, R1 represents hydrogen or a methyl group) -G-C
H2-Cf-1-0→-(TII) H2X (in the formula, X represents halogen).

The copolymer of the present invention is a carboxylic acid glycidyl ester represented by the following formula NV) (where R is the same as (P) in formula (I)), that is, glycidyl acetate-1, glycidyl propionate. ,
One or more types of glycidyl butyrate, etc., shrimp halohydrin, i.e., "-pichlorohydrin and/or epihalohydrin, and monotyrenic epoxide, i.e., ethylene A oxide and/or pyrene oxide, are combined with <A> an organotin compound and < B) It is produced by ring-opening copolymerization using a thermal condensation product of an alkyl ester of orthophosphoric acid or polyphosphoric acids as a catalyst.

Details of the catalyst (A) and (B) components are explained in the above-mentioned US Pat. No. 3,773,694. (A)
[3) Component is adjusted so that the ratio of tin atoms to phosphorus atoms that are normally included is in the range of 1:10 to 10:1, and the (A) component is removed at about 100 to 300°C] 3) Component Alternatively, C is produced by mixing and heating component (Δ) and a combination of component compounds capable of forming component (B). A solvent may be used if necessary. In the catalytic reaction product obtained by this catalytic reaction, various relatively simple substances are generated and eliminated through a synthesis reaction depending on the type of components. The condensates obtained exhibit the desired activity at various stages of the degree of condensation.

Polymerization reactions using these catalysts are usually carried out in the temperature range of 0 to 80° C. in the presence or absence of a solvent. Catalyst is 0.01 to 5.0 per 100g of monomer
A range of g is appropriate. It is desirable to keep the water content in the polymerization reaction system as low as possible. In order to obtain a homogeneous polymer, measures such as IRJ'l' or shaking are applied as usual.

The polymer copolymer of the present invention produced in this manner is a rubbery solid random copolymer C.

In the above composition ratio, carbonic acid cricidyl ester is 3
If it is less than 55 mol %, the properties as an oil-resistant rubber will deteriorate and the heat resistance will also decrease. If it exceeds 90 mol%, cold resistance will be insufficient for practical purposes. Furthermore, if the epiherohydrin content is less than 5 mol%, the crosslinking function will decrease, and if it exceeds 60 mol%, the corrosive effects of halogens will likely appear, and the oil resistance characteristics of glycidyl ester will disappear. If the ethylenic epoxide content is less than 5 mol%, the cold resistance will decrease.

The polymer copolymer of the present invention has a halogen in the side chain, and the conventional halogen-containing crosslinking agent for rubber, such as polyamine J:
The resulting crosslinked product has a high degree of oil resistance against various oils, and is often resistant to conventional oil-resistant rubbers. Compared to conventional epichlorohydrin, which is known as oil-resistant rubber, it has greatly improved oil resistance and metal corrosion resistance. The copolymer of the present invention is also expected to be useful as a water-soluble polymer intermediate or an intermediate for various polymer reactions, and also as a functional film or coating film forming material.

Example 1 10.0 of Schifdel tin oxide and 1-23.40 of tributyl tin oxide were placed in a flask equipped with a thermometer and a distillation column, and heated to a temperature of 26 (1℃"c15) with stirring.
After heating for a minute, the mixture was cooled for 90 minutes to obtain a solid polymerization catalyst. The IC6 polymerization reaction was carried out in a 20 g stainless steel reactor equipped with a stirrer, a thermometer, a sample F31 inlet, and a nitrogen inlet. After replacing the inside of the reactor with nitrogen, glycidyl acetate 500
(] (4.31 mol), 154 g of epichlorohydrin (
After adding in order:
The above polymerization catalyst 6.0! II was added and reacted at 24°C with stirring, and at 4 and 6 hours after the start of the reaction, 47 (1 (1,07 mol)) and 2 ethylene oxide were added, respectively.
7 g (0.16 mol) was added and reacted for 8 hours.

After terminating the reaction by adding water ioog to the reaction mixture, the solution portion was decanted, the polymerized product was washed repeatedly with water, further washed with ether, and finally 2,2'-methylenehis<4-methyl -6-tert-butylphenol)
After impregnating one liquid in ether 5001 containing 0.5 (), the ether was decanted and dried at 60° C. for 24 hours under distilled water to obtain 328 g of a rubbery polymer.

Examples 2 to 4 Glycidyl arechie 1 or glycidylp] bionate as the first component, ethylene oxide or propylene oxide as the second component, and epichlorohydrin or ebibromohydrin as the third component in the same manner as in Example 1. Table 1 below shows the polymerization reaction conditions and properties of the isolated copolymer in Examples 1 to /I. 3w original viscosity measured in solution.

Rice 2 Calculated value from elemental analysis value.

*3 56% of the total amount at reaction time 0, 28% after 4 hours.
%, 16% added after 6 hours.

Example 5 1 each of the copolymers obtained according to Examples 1 and 2
1 part stearic acid per 00 parts (@Okibe, same below),
40 parts of FEF carphone, 5 parts of red lead, 1 part of nickel dibutyl didiocarbamate = 1, and 1.2 parts of 2-mercaptoimidacillin were blended, kneaded with rolls, and mixed at 160°C.
After vulcanization for 0 minutes, simple physical properties were measured.

The results are shown in Table 2.

(Spontaneous writing of Table 2 procedural amendments) August 21, 1982 [] 1. Indication of the case Patent Application No. 231766 of 1982 2
, Title of the invention: Glycidyl ester - Nibihalohydrin-ethylenic epoxide combination 3, Relationship with the amended case: Patent applicant: 4, Agent: Osaka Soda Co., Ltd., 1-10-8 Edobori, Nishi-ku, Osaka 550 Correct contents of each column 6.7m in the company's "Detailed Description of the Invention" (1) Correct fi5a 1+11 of the patent claim for the specification by J3 in the attached sheet.

(2) In the bottom line of page 6 of the same book, ``halohydrin'' is corrected to ``bromohydrin.''

(3) Same book, page 10, line 6 1" 0.16 J to 1'
Correct it to 0.61 J.

(/l) In the same book, page 10, line 7, "reacted" is corrected to "reacted j."

(5) In the same book, page 10, line 13, "liquid" is corrected to "iku".

(6) Same book, page 10, line 14 l 328j to r 715
J Correct.

1JJ Revised Scope of Claims The composition ratio in terms of 7mers is 35 to 90 mol% of saturated aliphatic carboxylic acid glycidyl ester having 2 to 5 carbon atoms, ■ 5 to 60 mol% of bihalohydrin, ■ tyrenic epoxide 5
mol% or more, and the main chain structure is substantially the following (I).
Polyether C consisting of a structural unit represented by the formula (■)
A4 A rubbery solid glycidyl ester-epihalohydrin-ethylenic epoxide copolymer having a reduced viscosity of 0.5 or more as measured in a 0.1% monochlorobenzene solution at 180°C.

-+C1~+2-CHO+ ■ Cl-1200OR(I) (In the formula, R represents an alkyl group of C-+ to C4)-+C
t-12-CI-I -O+ R' (I) (In the formula, R1 represents hydrogen or medyl group) 1,000Cl-
I 2- CH-0+ Ct12X (I [> (wherein, X represents halogen)

Claims (1)

[Scope of Claims] The composition ratio in terms of monomer is 35 to 90 mol% of saturated aliphatic carboxylic acid glycidyl ester having 2 to 5 carbon atoms.]
Nipihalohydrin 5 to 60 mol% Ethylene epoxide 5 mol% or more C, the main chain structure is substantially as follows <I) ~
A polyether represented by the formula (I), which is a rubbery solid glycidyl ester-epihalohydrin-ethylenic epoxide compound having a reduction activity of 0.5 or more as measured in a 0.1% monochlorobenzene solution at 80°C. Polymer. 1,000 R2-CH-0← C+-1200OR(I) (In the formula, R represents a C1 to C4 alkyl group) -CR
2-Cf-1-0← R1(I[) (In the formula, R1 represents hydrogen or a methyl group) -+CH
2-CH-0← (I[) H2X (in the formula, X represents halogen)