JPH0826144B2 - Method for producing polyether copolymer having epoxy group in side chain - Google Patents

Description

The present invention relates to a polyether copolymer having an epoxy group in its side chain, which is useful as an epoxy resin or a rubber material, or as a reaction intermediate, an adhesive or a coating material. Manufacturing method.

(Prior Art) A polymer having a functional group in its side chain is important because various functions can be expected, and therefore, many studies have been conducted on polymerization of a monomer having a functional group. However, in the polymerization or copolymerization of a monomer containing two or more functional groups having similar polymerization reactivity, an insoluble gel is formed because the crosslinking reaction proceeds at the same time, and only one functional group is polymerized and the other functional group is It has generally been difficult to obtain residual, soluble or thermoplastic, at least high molecular weight polymers. However, as an example of synthesizing a polymer having an ethylenically unsaturated group in the side chain by copolymerization of dienes, there is an example such as ethylene-propylene-diene polymer, which is one unsaturated group for a specific catalyst. It uses a diene having a markedly different polymerization reactivity.

The polymer having an epoxy group on the side chain can be obtained only when a monomer having both a vinyl polymerizable functional group and an epoxy group is polymerized by a radical initiator, for example, when glycidyl methacrylate is polymerized with peroxide. Not not.

A polymer having a polyether main chain can be generally synthesized by ring-opening polymerization of an epoxide, but in copolymerization of a monoepoxide and a diepoxide, only one epoxy group of the diepoxide is selectively polymerized and the other epoxy group is polymerized. Up to now, no example has been known in which a soluble polyether is obtained by leaving the polymer as a polymer side chain.

(Object of the Invention) The present invention is a polyether having an epoxy group in the side chain, which has not been described in the conventional literature and can be used for various applications, by polymerizing a specific diepoxide and a monoepoxide using a specific catalyst. It is an object to provide a method for producing a copolymer.

(Structure of the Invention) In the present invention, the main chain structure is substantially the following formula (I): 5 to 95 mol% of the structural unit of and the following (II) formula (However, in the formula (II), R is a hydrogen atom or an atom or a group optionally having a substituent, which is selected from an alkyl group, an alkenyl group, a cycloalkyl group, and an aryl group.) A polyether having an epoxy group in the side chain, which has a reduced viscosity of 0.01 or more as measured with a 0.1% benzene solution at 45 ° C or a 0.1% monochlorobenzene solution at 80 ° C. It is a method for producing a copolymer.

The present invention also relates to 2,3-epoxypropyl-2 ', 3'-
Epoxy-2'-methylpropyl ether and the following general formula (III) (However, in the formula (III), R is a hydrogen atom and an atom or a group optionally having a substituent, which is selected from an alkyl group, an alkenyl group, a cycloalkyl group, and an aryl group.) And the following general formulas (i) to (iv) _Ra SnX _4-a (i) (wherein, in the formula (i), R is an alkyl group having 1 to 12 carbon atoms which may have a substituent, A group selected from an alkenyl group, a cycloalkyl group, an aryl group and an aralkyl group, X is an atom or a group selected from a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group and a partial ester residue of phosphoric acid, and a is It is an integer representing 1 to 4. When a is 2 or more, Rs may be the same or different, and when a is 1 or 2, Xs may be the same or different.) R _b SnO _c (Ii) (However, in equation (ii) Te, R is .b 1 or 2 is the same as R in the formula (i), when b is 1, c is
It is 3/2, and when b is 2, c is 1. Also (ii)
The formula compound may form a complex with the formula compound (i). ) R ¹ R ₂ SnOSnR ₂ R ¹ (iii) (However, in the formula (iii), R is R in the formula (i).
And R ¹ is the same as R or X in the formula (i). Two R ^1's may be the same or different. ) (R ¹ ₃ Sn) _d X ′ (iv) (However, in the formula (iv), R ¹ is R ^{1 in the} formula (iii).
And at least one is a group selected from R in the formula (i). X'is a group selected from a carbonic acid group, a phosphorus oxygen acid group, a phosphoric acid partial ester residue, a polybasic carboxylic acid group, and a polyhydric alcohol residue. d is a number greater than 1 corresponding to the basicity of X '. ) Polymerization in the presence of a catalyst, which is a thermal condensation product of an organotin compound selected from the following, and an alkyl phosphate ester, is a process for producing a polyether copolymer having an epoxy group in the side chain.

This compound can be synthesized, for example, by epoxidizing allylmethallyl ether with hydrogen peroxide, peracid or the like.

When this compound is polymerized with a conventionally well-known ring-opening polymerization catalyst such as organoaluminum-water, a crosslinking reaction proceeds rapidly and a solvent-soluble polymer cannot be obtained. Also, a soluble polymer cannot be obtained by copolymerization with other monoepoxides similar to the present invention.

The present invention provides a thermal condensation product of a specific organotin compound (A) and a phosphoric acid alkyl ester (B) described in Applicant's US Pat. No. 3,773,694 with a specific diepoxide and monoepoxide. It is based on the finding that it selectively acts as a catalyst for ring-opening copolymerization, and that the resulting polymer is also very useful as a functional polymer having an epoxy group in its side chain.

Specific examples of the compound of the general formula (III) which forms the structural unit (II) of the polyether copolymer of the present invention include ethylene oxide, propylene oxide, butadiene monoxide, vinylcyclohexane oxide, styrene oxide and epichlorohydride. Phosphorus, epibromohydrin, allyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, glycidyl acetate,
Examples thereof include glycidyl propionate, glycidyl benzoate, and glycidyl cinnamate. One or more of these compounds can be used as a copolymerization component. That is, the constitutional unit (II) of the polyether copolymer of the present invention may have constitutional units formed from the above-mentioned two or more kinds of monomers in the same polymer chain.

The following can be mentioned as specific examples of the organotin compound (A) of the above formulas (i) to (iv) which is the catalyst component of the present invention.

Examples of the compound belonging to the general formula (i) include (C ₂ H ₅ ) ₄ Sn, (C ₆ H ₅ ) ₄ Sn, (CH ₃ ) ₃ SnF, (C ₄ H ₉ ) ₃ SnCl, (CH ₃ ) _{3 SnBr, (C 8 H 17)} 3 SnCl, (CH 3) 2 SnF 2, (C 4 H 9) 2 SnCl 2, (C 12 H 23) 2 SnBr 2, (cyclo-C 6 H 11) 2 SnI 2 , (C ₄ H ₉ ) SnF ₃ , (C ₈ H ₁₇ ) SnCl ₃ , (C ₄ H ₉ ) ₃ SnOC ₄ H ₉ , _{(C 8 H 17) 3 SnOCOCH} 3, (C 8 H 17) 2 Sn (OCOC 17 H 35) 2, And the like.

Examples of the compound belonging to the general formula (ii) include (CH ₃ ) ₂ SnO, (C ₄ H ₉ ) ₂ SnO, (C ₈ H ₁₇ ) ₂ SnO, (C ₆ H ₅ ) ₂ SnO, CH ₃ SnO _{3 / 2} , C ₄ H ₉ SnO _3/2 , etc., and examples of the complex of the compounds of the general formula (i) and the general formula (ii) include (CH ₃ ) ₂ SnO. (C ₂ H ₅ ) ₂ SnBr _2, and the like _{(CH 3) 2 SnO · (} CH 3) 2 SnCl 2, CH 3 [(CH _{3) 2} SnO] _{2 CH 3 · (CH 3)} 2 SnBr 2.

The compounds belonging to general formula _{(iii), (CH 3)} 3 SnOSn (CH 3) 3, Cl (C 4 H 9) 2 SnOSn (C 4 H 9) Cl, (CH 3 COO) (C 6 H 5 ) Sn (C ₆ H ₅ ) (CH ₃ COO) and the like.

The compounds belonging to general formula (iv), [(CH _{3) 3} Sn] ₂ CO _3, [(C ₄ H _{9) 3} Sn] _{2 CO 3, (C 4 H} 9) 3 SnOP (O) (OC ₈ H _{17) 2,} [(C ₈ H _{17) 3} Sn] _{3 PO 4, (C 4 H} 9) 3 SnOCH 2 CH 2 OSn, (C 4 H 9) 3, (C 4 H 9) 2 (CH ₃ O) Sn-OCOCH ₂ ) _4- OCO-Sn (OCH ₃ ) (C ₄ H ₉ ) ₂ , And the like.

As the phosphoric acid alkyl ester (B) which is another component constituting the catalyst of the present invention, a complete or partial ester of orthophosphoric acid represented by the following general formula (IV) is used.

(R ² O) ₃ P = O (IV) (In the formula (IV), R ² is hydrogen or has 2 carbon atoms.
The above alkyl group, alkenyl group or cycloalkyl group, and at least one of R ² is a group other than a hydrogen atom. ) Specific examples of the above formula (IV) include (C ₂ H ₅ ) ₃ PO ₄ , (C ₃ H ₇ ) ₃ PO ₄ , (C ₄ H ₉ ) ₃ PO ₄ , and (C ₈ H ₁₇ ). ₃ PO ₄ , (CH ₂ = CH-CH ₂ ) ₃ PO ₄ , (C ₆ H ₁₁ ) ₃ PO ₄ , (ClCH ₂ -CH ₂ )) ₃ PO ₄ , (Cl ₂ C ₃ H ₅ ) PO ₄ , _{(C 2 H 5) 2 HPO} 4, (C 4 H 9) 2 HPO 4, and the like _{(C 4 H 9) H 2} PO 4.

The catalyst of the present invention is obtained as a condensation product by heating a mixture of the organotin compound (A) and the phosphoric acid alkyl ester (B) in a temperature range of 150 ° C to 300 ° C. The solvent may be used if necessary. The above-mentioned components (A) and (B) are used so that the ratio of tin atoms and phosphorus atoms usually contained is in the range of 1:10 to 10: 1.

In the catalyst formation reaction, various relatively simple substances are formed and eliminated by the condensation reaction according to the types of the component (A) and the component (B). The obtained condensate exhibits the desired activity at various stages of the degree of condensation. The optimum condensation degree varies depending on the types and ratios of the component (A) and the component (B), but they can be easily determined experimentally. The condensate is generally soluble in a solvent such as hexane or benzene at the initial stage, but becomes insoluble as the condensation reaction proceeds.

In the polyether copolymer of the present invention, 2,3-epoxypropyl-2 ', 3'-epoxy-2'-methylpropyl ether and the above formula (III) compound are usually aliphatic carbonized using the above condensation product as a catalyst. It can be obtained by polymerizing in the presence or absence of a solvent such as hydrogens and aromatic hydrocarbons at 10 to 80 ° C, usually with stirring or shaking. The amount of the catalyst used is appropriately in the range of 0.01 to 1.0 parts by weight based on 100 parts by weight of the total raw material monomers. It is desirable that the water content of the reaction system during the reaction be as low as possible.

The polyether copolymer of the present invention has the formula (I) and the formula (I
The ratio of the constituent units of I) is 5 to 95:95 to 5 mol% and the reduced viscosity measured with a 0.1% benzene solution at 45 ° C or a 0.1% monochlorobenzene solution at 80 ° C is 0.01 or more. , Preferably 0.01 to 5, particularly preferably
The range of 0.05 to 3 has good usability. When used as an epoxy resin, the constituent molar ratio is represented by the formula (I)
Is preferably 30 mol% or more, and when used as a rubber, a compound of the formula (I) having about 5 mol% is preferable. When used as a reaction intermediate, various compositions are conceivable depending on the application.

(Effect of the invention) The polymer of the present invention is a novel polyether copolymer having an epoxy group in the side chain, which is obtained by using a novel specific diepoxide, combining it with a monoepoxide, and polymerizing it using a specific catalyst. It is a polymer and is a high-performance polymer useful for epoxy resins, rubber materials, reactive intermediates, adhesives, paint materials, etc.

(Example) Example 1 In a three-necked flask equipped with a stirrer, a thermometer, and a distillation device, 10.0 g of dibutyltin oxide and 2 parts of tributylphosphate were added.
3.4 g was added, the mixture was heated under a nitrogen stream at 260 ° C. for 15 minutes with stirring to distill off the distillate, and a solid condensed substance was obtained as a residue. The following polymerization was carried out using this as a catalyst.

Replace the inside of a glass ampoule with an internal capacity of 50 ml with nitrogen,
Charge 30 mg of the above condensation substance and 12 g of 2,3-epoxypropyl-2 ′, 3′-epoxy-2′-methylpropyl ether having a water content of 10 ppm or less and 20 g of propylene oxide, seal the tube, and shake at 50 ° C. at 40 ° C. while shaking the ampoule. Reacted for hours. After the reaction, the reaction product was added with 100 ml of methanol (containing 0.5% by weight of 2,2'-methylenebis (4-methyl-6-tert-butylphenol)).
The mixture was placed in the flask and immersed overnight, the methanol was decanted off, and the washing with 100 ml of the above methanol was repeated twice, followed by drying at 100 ° C. for 8 hours under reduced pressure to obtain 29 g of an adhesive rubbery polymer. Table 1 shows the molar ratio of charged monomers, the reaction conditions, and the composition ratio of each component of the produced polymer. The infrared absorption spectrum of the copolymer obtained in this example is shown in FIG. ¹ , and the ¹ H NMR spectrum is shown in FIG.

Examples 2 to 4 Copolymerization was performed using the same catalyst as in Example 1 in the same manner as described above, but with the molar ratio of the charged monomer, the amount of catalyst, and the reaction conditions shown in Table 1, to obtain copolymers. It was The component composition ratio of the obtained copolymer is shown in Table 1. The component composition ratio of the copolymer shown here was determined by ¹ H NMR. The infrared absorption spectra of the copolymers obtained in Examples 2 to 4 are shown in FIGS. 2 to 4, respectively, and the ¹ H NMR spectrum of the copolymers obtained in Example 2 is shown in FIG. .

[Brief description of drawings]

1 to 4 are infrared absorption spectra of the copolymers obtained in Examples 1 to 4, respectively, and FIGS.
FIG. 6 is ¹ H NMR spectra of the copolymers obtained in Examples 1 and 2, respectively.

Claims (2)

[Claims] 1. A compound of general formulas (i) to (i) containing 2,3-epoxypropyl-2 ', 3'-epoxy-2'-methylpropyl ether and a monomer selected from the following general formula (III).
The main chain structure obtained by polymerization in the presence of a catalyst, which is a thermal condensation product of an organotin compound selected from v) and an alkyl phosphate ester, is substantially the following (I).
5 to 95 mol% of the structural unit of the formula and the structural unit 95 of the following formula (II)
A polyether having an epoxy group in the side chain, which has a reduced viscosity of 0.01 or more as measured with a 0.1% benzene solution at 45 ° C or a 0.1% monochlorobenzene solution at 80 ° C. Method for producing copolymer. (In the formulas (II) and (III), R ³ is a hydrogen atom or an atom or a group which may have a substituent and is selected from an alkyl group, an alkenyl group, a cycloalkyl group and an aryl group. , In the formula (III), constitutional units having different R ³ may be present in the same polymer chain.) R _a SnX _4-a (i) (In the formula (i), R is an optionally substituted alkyl group having 1 to 12 carbon atoms, an alkenyl group, a cycloalkyl group, an aryl group and an aralkyl group. A group selected from the above, X is an atom or a group selected from a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group and a partial ester residue of phosphoric acid, and a is an integer of 1 to 4. a is 2 In the above cases, R may be the same or different, and when a is 1 or 2, X may be the same or different.) R _b SnO _c (ii) (However, in the formula (ii), R is the same as R in the formula (i), b is 1 or 2, and when b is 1, c is
It is 3/2, and when b is 2, c is 1. The compound of formula (ii) may form a complex with the compound of formula (i). ) R ¹ R ₂ SnOSnR ₂ R ¹ (iii) (However, in the formula (iii), R is R in the formula (i).
And R ¹ is the same as R or X in the formula (i). Two R ^1's may be the same or different. ) (R ¹ ₃ Sn) _d X ′ (iv) (However, in the formula (iv), R ¹ is R ^{1 in the} formula (iii).
And at least one is a group selected from R in the formula (i). X'is a group selected from a carbonic acid group, a phosphorus oxygen acid group, a phosphoric acid partial ester residue, a polybasic carboxylic acid group, and a polyhydric alcohol residue. d is a number greater than 1 corresponding to the basicity of X '. ) 2. The monomer forming the formula (II) is ethylene oxide, propylene oxide, styrene oxide,
The method for producing the copolymer according to claim 1, which is a monomer selected from epichlorohydrin, epibromohydrin, allyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether and glycidyl acetate.