JPS6224009B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to glycidyl ester-allyl glycidyl ether-ethylenic epoxide copolymers. In this specification, ethylenic epoxide is used to mean ethylene oxide and propylene oxide. Although many techniques have been disclosed regarding ring-opening polymerization of three-membered epoxides, there are few examples of highly polymerizing monomers having functional groups other than epoxides. Among them, it is known that organoaluminum catalysts and organotin-phosphate ester catalysts are particularly capable of high polymerization of a wide range of epoxides. However, although glycidyl carboxylate, which is an epoxide with an ester group, is expected to have various useful chemical and physical properties due to its polymer structure, no high polymer has been obtained to date. do not have. 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. 3,285,870), but the composition ratio of these glycidyl esters is extremely small, and the molecular weight of the obtained copolymer is also low. Furthermore, when the ratio of glycidyl ester increases, the molecular weight further decreases significantly. There has also been a report on the ring-opening polymerization of glycidyl acetate using boron fluoride etherate (Makromol Chem 71.150 (1964)), but it was not possible to obtain an oily low molecular weight polymer (with a reduced viscosity of less than 0.1). It's just that. U.S. Patent No. 3773694 filed by the applicant
Although there is a general statement in part of the issue that glycidyl esters can be polymerized using organotin-phosphate ester catalysts, there is no disclosure of the details of the polymerization reaction or the high polymers obtained by this process. Not done. The present inventors have patented a homopolymer of carboxylic acid glycidyl ester, a carboxylic acid glycidyl ester-allyl glycidyl ether copolymer, and a carboxylic acid glycidyl ester-epihalohydrin copolymer using this organotin-phosphate ester catalyst. I filed an application (patent application 1982-
119921, 119922, 119923), and also succeeded in synthesizing a high molecular weight copolymer of glycidyl carboxylate, allyl glycidyl ether, and ethylenic epoxide using the same catalyst, and the resulting copolymer is extremely useful. The present invention was completed based on the knowledge that it has rubber-like properties and can be expected to have various uses. That is, in the present invention, the composition ratio in terms of monomers is 35 to 90 mol% of saturated aliphatic carboxylic acid glycidyl ester having 2 to 5 carbon atoms, 1 to 20 mol% of allyl glycidyl ether, 5 mol% or more of ethylenic epoxide, and the main chain The structure is substantially as follows () ~ ()
A rubbery solid glycidyl ester-allyl glycidyl ether-ethylenic epoxide, which is a polyether consisting of units represented by the formula and has a reduced viscosity of 0.5 to 3.5 as measured in a 0.1% monochlorobenzene solution at 80°C. It is a copolymer. Note that formulas () to () are (In the formula, R represents a C ₁ to C ₄ alkyl group) (In the formula, R ¹ represents hydrogen or methyl group) It is. The copolymer of the present invention has the following formula () (However, R in the formula is the same as R in the formula ()) One or more glycidyl esters of saturated aliphatic carboxylic acids, i.e., glycidyl acetate, glycidyl propionate, glycidyl butyrate, etc.; allyl glycidyl ether and an ethylenic epoxide, i.e. ethylene oxide and/or propylene oxide.
It is produced by ring-opening copolymerization using a thermal condensation product of (A) an organotin compound and (B) 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. Component (A) and component (B) are 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.
At 100 to 300℃, component (A) and component (B), or component (A) and
It is produced by mixing and heating a combination of component compounds that can form component (B). A solvent may be used if necessary. In the catalyst reaction product obtained by this catalyst production reaction, various relatively simple substances are generated and eliminated by a condensation reaction depending on the type of components. The resulting condensate exhibits 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 per 100g of monomer
A range of 0.01 to 5.0 g is suitable. It is desirable to keep the water content in the polymerization reaction system as low as possible. In order to obtain a homogeneous polymer, conventional means such as stirring or shaking are applied. The polymer copolymer of the present invention produced in this manner is a rubbery solid random copolymer. If the carboxylic acid glycidyl ester is less than 35 mol % in the above composition ratio, the properties as an oil-resistant rubber will deteriorate and the heat resistance will also decrease. If it exceeds 90 mol%, cold resistance is insufficient for practical purposes. Furthermore, if the content of allyl glycidyl ether is less than 1 mol %, the crosslinking function will be reduced, and if it exceeds 20 mol %, the oil resistance and heat resistance will be significantly reduced. Moreover, if the ethylenic epoxide content is less than 5 mol %, cold resistance will decrease. Since the polymer copolymer of the present invention has an allyl group in the side chain, it is easily vulcanized using a normal vulcanization system for unsaturated rubbers such as sulfur, various sulfur compounds, and peroxides, and is vulcanized for various oils. It exhibits an extremely high degree of oil resistance, and also overcomes various problems that conventional oil-resistant rubbers have, such as cold resistance, ozone resistance,
It exhibits excellent effects in improving the corrosion resistance of halogen-containing polymers. 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 as a coating film forming material. Example 1 10.0 g of dibutyltin oxide and 23.4 g of tributyl phosphate were placed in a flask equipped with a thermometer and a distillation column, heated at 260°C for 15 minutes with stirring, and then cooled to obtain a solid polymerization catalyst. Ta. The polymerization reaction was carried out in a 20-capacity stainless steel reactor equipped with a stirrer, a thermometer, a sample introduction section, and a nitrogen introduction section. After replacing the inside of the reactor with nitrogen, 500 g (4.31 mol) of glycidyl acetate and allyl glycidyl ether were added.
After sequentially adding 31.4 g (0.275 mol), 6300 g of hexane, and 70 g (1.60 mol) of ethylene oxide, 6.0 g of the above catalyst was added and reacted at 24° C. for 6 hours with stirring. After adding 100 g of water to the reaction mixture to stop the reaction, the solution part was decanted, the polymer was repeatedly washed with water, and then further washed with ether.
Finally, 2,2'-methylenebis(4-methyl-6-
Ether 500 containing 0.5g (tert-butylphenol)
After overnight soaking in ml, remove the ether and evaporate under reduced pressure.
It was dried at 60°C for 24 hours to obtain 87g of rubber polymer. Examples 2 to 4 Copolymers containing glycidyl acetate, glycidyl propionate, or glycidyl butyrate as the first component and propylene oxide and allyl glycidyl ether as the second and third components were obtained in the same manner as in Example 1. Ta. Table 1 below shows Examples 1-
4 shows the polymerization reaction conditions and characteristics of the isolated copolymer.

【table】

[Table] Example 5 1 part of stearic acid and 1.5 parts of dibenzothiazyl disulfide were added to 100 parts (parts by weight, same hereinafter) of each of the copolymers obtained in Examples 1 and 2.
1 part of sulfur and roll kneading, 160
After vulcanization at ℃ for 20 minutes, simple physical properties were measured. The results are shown in Table 2.

【table】

【table】 [Brief explanation of the drawing]

1 and 2 are infrared absorption spectra of glycidyl acetate-ethylene oxide-allyl glycidyl ether copolymer and glycidyl acetate-propylene oxide-allyl glycidyl ether copolymer according to the present invention, respectively.

Claims (1)

[Scope of Claims] 1 Glycidyl ester of a saturated aliphatic carboxylic acid having 2 to 5 carbon atoms having a composition ratio of 35 to 35 carbon atoms;
90 mol%, allyl glycidyl ether 1 to 20 mol%, ethylenic epoxide 5 mol% or more,
A polyether whose main chain structure is substantially composed of units represented by the following formulas () to (), and whose reduced viscosity is 0.5 to 3.5 when measured with a 0.1% monochlorobenzene solution at 80°C. Solid glycidyl ester-allyl glycidyl ether-ethylenic epoxide copolymer. (In the formula, R represents a C ₁ to C ₄ alkyl group) (In the formula, R ¹ represents hydrogen or methyl group)