JPS62115025A - Glycidyl methacrylate homopolymer - Google Patents

Abstract

PURPOSE:To obtain a high-polymerization degree glycidyl methacrylate useful as a functional polymeric material, obtained by polymerizing glycidyl methacrylate by bonding through its epoxy groups. CONSTITUTION:A high-polymerization degree glycidyl methacrylate homopolymer whose main chain is substantially represented by the structure of the formula and which has a reduced viscosity as measured in a 0.1% benzene solution at 40 deg.C>=0.1. This homopolymer can be obtained by ring-opening polymerization of glycidyl methacrylate by using a thermal condensation product of an organotin compound with an alkyl orthophosphate or polyphosphate alkyl ester.

Description

DETAILED DESCRIPTION OF THE INVENTION (Technical Field of the Invention) The present invention relates to a novel polymer useful as a functional polymer material produced by polymerization of glycidyl methacrylate via an epoxy group.

(Prior art) Glycidyl methacrylate polymer, which is produced by ring-opening polymerization of the epoxy groups of glycidyl methacrylate, has a chemically highly active methacryloyl group in its side chain and is expected to be a reactive or functional polymer material. However, this homopolymer, moreover, a high polymer, has not been known so far.

U.S. Pat. No. 3,158,591 and U.S. Pat. No. 3,285,870 disclose the preparation of highly polymerized glycidyl methacrylate-shrimp chlorohydrin copolymers using alkylaluminium-acetylacetone-water catalysts. Although a method has been disclosed, the composition ratio of glycidyl methacrylate in the obtained copolymer was extremely low. A method for producing a glycidyl ester-propylene oxide copolymer with a high degree of polymerization using a similar catalyst has also been disclosed (Ind, Eng, Chem, Prod.
, Res. Develop, 3.195 (1964)
), but there was no mention of glycidyl methacrylate, and the composition of the copolymer was mainly propylene oxide.

Alkylaluminum-water based catalysts are disclosed in U.S. Patent No. 3.2.
80.045@ As described in the specification, glycidyl esters are not suitable as ring-opening polymerization catalysts, especially when used alone, due to the reactivity of the catalyst toward ester groups.

There has also been a report on the ring-opening polymerization of glycidyl methacrylate using a boron fluoride etherate catalyst (
Otsu et al., Polymer Chemistry 21.703 (1964), Otsu et al., Makromol, Chem, 71.150
(1964)), but there is no description of data related to the molecular weight of the polymer.

Generally, in the production of high polymers by ring-opening polymerization reaction of epoxides, coordination methods such as alkylaluminum-acetylacetone-water system, alkylzinc-water system, iron chloride-propylene oxide system, or organotin-phosphate ester condensate system are used. Only polymerization-type catalysts are thought to be effective;
Cationic polymerization using a Lewis acid, such as boron fluoride etherate, does not yield a sufficient polymer. Furthermore, according to the report by Otsu et al., the obtained polymer has extremely high hygroscopicity and has been identified as a polymer with one molecule of water added per glycidyl methacrylate unit, which is also different from the homopolymer of the present invention. There is.

U.S. Patent No. 3,773,694 filed by the present applicant generally states that ring-opening polymerization of glycidyl esters is possible using an organotin-phosphate ester condensate catalyst. However, there is only a general description of glycidyl methacrylate as a glycidyl ester, but the details of the polymerization reaction and the high polymer obtained thereby are not disclosed.

In addition, many reports and patent publications regarding glycidyl methacrylate polymers have been provided, but all of them are polymers using vinyl groups, and as in the present invention, the degree of polymerization is high due to polymerization reaction via epoxy groups. There is no disclosure of polyether homopolymers.

(Objective of the Invention) An object of the present invention is to provide a highly polymerized homopolymer produced by a polymerization reaction of glycidyl methacrylate via an epoxy group, which is useful as a functional polymer material.

(Structure of the Invention) The present invention is directed to a highly polymerized polymer having a reduced viscosity of 0.1 or more as measured in a 9.1% benzene solution at 40'C and a main chain structure substantially represented by the following formula (1). It is coated with glycidyl methacrylate homopolymer.

The homopolymer of the present invention is produced by ring-opening polymerization of glycidyl methacrylate using a thermal condensation product of (A) an organotin compound and (B) an alkyl ester of orthophosphoric acid or polyphosphoric acid as a catalyst. This catalyst (A>, (B
) For details of each component, see the aforementioned U.S. Pat. No. 3,773.
It is described in the specification of No. 694. The catalyst contains (A>component and (B) component) in a ratio of tin atoms to phosphorus atoms which are usually included.
: Adjust to be in the range of 10 to 10:1, about 100
At ~300'C, (△) component and (B) component or (A>
It is produced by mixing and heating the component and a combination of component compounds capable of forming component (B). A solvent may be used if necessary. In this catalyst production reaction, various relatively simple substances are produced and eliminated by condensation reactions depending on the types of components. The resulting condensate exhibits the desired activity at various stages of the degree of condensation. The optimal degree of condensation is (A>component and (B)
Depending on the type and proportion of ingredients, they can be determined experimentally. The condensate is generally soluble in a solvent such as hexane or benzene in the initial stage, but becomes insolubilized as the condensation reaction progresses.

By using the above soluble or insoluble condensate as a catalyst, a high polymerization reaction of glycidyl methacrylate can be carried out. The polymerization reaction can be carried out by bringing the above-mentioned catalyst substance into contact with glycidyl methacrylate at a temperature usually in the range of 10 to 80°C in the presence or absence of a solvent. Solvents include hexane, heptane, and cyclohexane.

Hydrocarbons such as benzene and toluene, chloroform,
Examples include halogenated hydrocarbons such as methylene chloride, ethers such as diethyl ether, and tetrahydrofuran.

The amount of catalyst used is 0.01 to 1 per 100g of nanatsuma.
, og is appropriate. It is desirable to keep the water content in the polymerization reaction system as low as possible. Further, the reaction is usually carried out under conditions such as stirring or shaking.

(Effects of the Invention) The homopolymer of the present invention is useful as a polymer material such as a reactive polymer intermediate, a photo- or thermosetting material, or a coating material.

(Example) Example 1 Tributyltin chloride 16.2 (] and tributyl phosphate 26.6!11 were placed in a flask equipped with a thermometer and a distillation tower, heated at 250°C for 20 minutes with stirring, and then cooled. A solid polymerization catalyst was obtained.

Replace the inside of the glass ampoule with an internal capacity of 50 d with nitrogen gas 1
Wheat, 68 mg of the above catalyst, and 30 ml of glycidyl methacrylate dried with molecular sieve 4A were added and an ampoule was melt-sealed. The bond amble reacted at 40°C for 4 days was opened, the jqed solid was thoroughly washed with methanol, and then dried at 40°C under reduced pressure to obtain 1q of 27.8 CI polymer (yield: 88.8%). .

The following results were obtained for the resulting polymer.

Reduced viscosity (0.1% benzene solution, 40'C) 0.
4 Glass transition temperature -23℃ Double bond gold fraction (calculated from bromine number) 105% Elemental analysis value Carbon: 58.61%, Hydrogen: 6.59% ((C710
Theoretical value as 1003>n Carbon: 59.13%, hydrogen nia: 10%] The infrared absorption spectrum of the obtained polymer is shown in FIG.

Example 2 A solid polymerization catalyst was obtained in the same manner except that dibutyltin oxide 12.5 ( ) was used instead of tributyltin chloride 16.2 ( ).

A polymer of 24.5 CI was obtained in the same manner as in Example 1 except that 102 mg of the above catalyst was used and the reaction was carried out at 50'C for 24 hours (yield 78.3%). The reduced viscosity (0.1% benzene solution, 40°C) of the obtained polymer was 0.60.

[Brief explanation of drawings]

FIG. 1 is an infrared absorption spectrum of the chrycidyl methacrylate homopolymer obtained in Example 1.

Claims (1)

[Claims] The reduced viscosity measured in a 0.1% benzene solution at 40°C is 0.1 or more, and the main chain structure is substantially as follows (
I) A glycidyl methacrylate homopolymer with a high degree of polymerization represented by the formula. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I)