JP2621345B2 - Alkenyl ether-maleic anhydride copolymer - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a novel copolymer of a polyoxyalkylene polyol monoalkenyl ether containing a carboxyl group in a molecule and maleic anhydride, and a reactive coating. It can be used as a material or a protein modifier.

[Conventional technology]

Copolymers of polyoxyalkylene glycol monoallyl ether and maleic acid monomer are disclosed in JP-A-59-1763.
No. 12, disclosed in scales, scale inhibitors, chelating agents,
Used as a dispersant and the like.

[Problems to be solved by the invention]

The copolymer disclosed in the above publication is obtained by copolymerizing polyoxyalkylene glycol monoallyl ether and maleic acid or maleic anhydride in an aqueous solution. According to the example, the number average molecular weight is 950. ~ 1250
And low. Further, since the terminal of the polyoxyalkylene glycol chain in the copolymer was a hydroxyl group, the content of the carboxyl group in the copolymer was low. Therefore, it has not been possible to sufficiently modify proteins and the like using carboxyl groups in the copolymer.

The present invention is directed to a copolymer of a polyoxyalkylene polyol monoalkenyl ether containing a specific alkenyl group and a carboxyl group (hereinafter, simply referred to as an alkenyl ether) and maleic anhydride, and has a higher molecular weight and It is a copolymer having a high carboxyl group content.

[Means for solving the problem]

The present invention relates to a copolymer of the alkenyl ether represented by the general formula (1) and maleic anhydride, and if necessary, a copolymer of another monomer, and alkenyl ether, maleic anhydride and another monomer. The molar ratio with the monomer is 5 to 60:40 to 70:
40 is the copolymer.

(However, B is a residue of a compound having 2 to 8 hydroxyl groups, AO
Is one or a mixture of two or more oxyalkylene groups having 2 to 18 carbon atoms. When two or more oxyalkylene groups are used, they may be added in a block or random manner, and X represents 2 carbon atoms. ~
An alkenyl group of 5; Y represents an acyl group of a dicarboxylic acid or a tricarboxylic acid, or an alkylene group having 1 to 3 carbon atoms; R represents a hydrocarbon group having 1 to 24 carbon atoms; 1 ≦ a ≦ 7,0 ≦ b ≦
6,0 ≦ c ≦ 6 and 1 ≦ a + b + c ≦ 7, and k, l, m, and n are 0 to 10 each of the average number of added oxyalkylene groups.
00, and k + al + bm + cn = 1 to 3000, p is 1 or 2. In the general formula (1), as the compound having 2 to 8 hydroxyl groups represented by B, ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, styrene glycol, alkylene glycol having 8 to 18 carbon atoms, Glycols such as pentyl glycol, glycerin, trimethylolethane, trimethylolpropane, 1,3,5-pentanetriol, erythritol, pentaerythritol, dipentaerythritol,
Sorbitol, sorbitan, sorbide, condensate of sorbitol and glycerin, adonitol, arabitol,
Polyhydric alcohols such as xylitol and mannitol,
Or sugars such as partially etherified or esterified products thereof, xylose, arabinose, ribose, rhamnose, glucose, fructose, galactose, mannose, sorbose, cellobiose, maltose, isomaltose, trehalose, sucrose, raffinose, gentianose, and merezitose; Phenols such as partially etherified or esterified products, catechol, resorcinol, hydroquinone, and phloroglucin. Examples of the oxyalkylene group having 2 to 18 carbon atoms represented by AO include an oxyethylene group, an oxypropylene group, an oxybutylene group, an oxytetramethylene group, an oxystyrene group, an oxydecylene group, an oxytetradecylene group, an oxyhexaene group. Examples include a decylene group and an oxyoctadecylene group. Examples of the alkenyl group having 2 to 5 carbon atoms represented by X include vinyl group, allyl group, methallyl group, 1,1-dimethyl-2-propenyl group, 3
-Methyl-3-butenyl group and the like. The dicarboxylic acid or tricarboxylic acid having Y as an acyl residue in the general formula (1) includes oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanoic acid , Dodecane, brassic, tetradecane, pentadecane, tapsic, heptadecani, octadecani, nonadecani, and icosanoic acids, such as maleic, fumaric, itaconic, citraconic, mesacon Acids, unsaturated dicarboxylic acids such as cisglutaconic acid, transglutaconic acid, α-dihydromuconic acid, β-dihydromuconic acid, tricarboxylic acids such as tricarballylic acid and citric acid, hydroxycarboxylic acids such as malic acid and tartaric acid, phthalic acid, Isophthalic acid, terephthalic acid Benzenedicarboxylic acids such as, 3-methylphthalic acid, 4-methylphthalic acid, 2-methylisophthalic acid, 4-methylisophthalic acid, methylterephthalic acid, hemimellitic acid,
Benzenetricarboxylic acids such as trimellitic acid and trimesic acid; When Y represents an alkylene group having 1 to 3 carbon atoms, examples thereof include a methylene group, an ethylene group, an ethylidene group, a propylidene group and an isopropylidene group. Examples of the hydrocarbon group having 1 to 24 carbon atoms represented by R include a methyl group, an ethyl group, an allyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tertiary butyl group, an amyl group, an isoamyl group, and a hexyl group. , Heptyl, 2-ethylhexyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, hexadecyl, isohexadecyl, octadecyl, isooctadecyl, oleyl, octyldodecyl Group, behenyl group, decyltetradecyl group,
Benzyl, cresyl, butylphenyl, dibutylphenyl, octylphenyl, nonylphenyl,
A dodecylphenyl group, a dioctylphenyl group, a dinonylphenyl group, a styrenated phenyl group and the like.

The alkenyl ether of the general formula (1) used in the present invention can be produced by various methods. Representative examples are shown below.

(A) A polyhydric alcohol, a polyhydric phenol or a saccharide having B as a residue is subjected to an addition reaction of an alkylene oxide having 2 to 18 carbon atoms, followed by a reaction with an alkenyl halide having 2 to 5 carbon atoms. Then, if necessary, an alkyl halide is reacted, and then a dicarboxylic acid or a tricarboxylic acid or an acid anhydride thereof is reacted to obtain an esterified product or an alkyl carboxylic acid represented by the following general formula (2). An etherified product is obtained by performing a Williamson synthesis reaction with a monohalogen-substituted product.

Z—R ₂ —COOH (2) (where Z is a chlorine atom or a bromine atom, and R ₂ is the same as when Y in formula (1) represents an alkylene group having 1 to 3 carbon atoms) (B) Addition reaction of alkylene oxide having 2 to 18 carbon atoms to alkenyl alcohol having 2 to 5 carbon atoms. Then, a dicarboxylic acid or a tricarboxylic acid or an acid anhydride thereof is reacted to obtain an esterified product, or a Williamson synthesis reaction with a monohalogen-substituted alkylcarboxylic acid represented by the general formula (2) is carried out. It is etherified.

(C) After adding glycidol to an alkenyl alcohol having 2 to 5 carbon atoms, an addition reaction is performed with an alkylene oxide having 2 to 18 carbon atoms. Next, if necessary, an alkyl halide is reacted, and then a dicarboxylic acid or a tricarboxylic acid or an acid anhydride thereof is reacted to obtain an esterified product, or a monocarboxylic acid of the alkylcarboxylic acid represented by the general formula (2). By conducting a Williamson synthesis reaction with the halogenated product, an ether compound is obtained.

(D) After adding glycidol to an alcohol having 1 to 24 carbon atoms, an addition reaction is performed with an alkylene oxide having 2 to 18 carbon atoms. Then, after reaction with an alkyl halide, a dicarboxylic acid or a tricarboxylic acid or an acid anhydride thereof is reacted to form an esterified product, or a monohalogen-substituted alkylcarboxylic acid represented by the general formula (2). An etherified product is obtained by performing Willamson synthesis.

The other monomer is a vinyl monomer copolymerizable with the alkenyl ether of the general formula (1) and maleic anhydride, such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, and maleic acid. Divalent or divalent metal salt, ammonium salt, organic ammonium salt, having 1 to 1 carbon atoms
24 esterified with alcohol, and also styrene,
Examples thereof include aromatic vinyl compounds such as methylstyrene, vinyl halide compounds such as vinyl chloride and vinylidene chloride, olefins such as isobutylene and diisobutylene, vinyl acetate, acrylonitrile, and acrylamide.

The copolymer of the present invention is prepared by subjecting the alkenyl ether of the general formula (1) and maleic anhydride to other monomers, if necessary, in the presence of a polymerization initiator by a method such as bulk polymerization or solution polymerization. Obtained by polymerization.

Examples of the polymerization initiator include organic peroxides such as benzoyl peroxide, lauroyl peroxide and ditert-butyl peroxide, and azo compounds such as azobisisobutyronitrile.

Solvents used for solution polymerization include aromatic hydrocarbons such as benzene, toluene and xylene, aliphatic hydrocarbons such as n-hexane and cyclohexane, ketones such as acetone and methyl ethyl ketone, ethers such as dimethyl ether, diethyl ether, tetrahydrofuran and dioxane. , Chloroform, halogenated hydrocarbons such as carbon tetrachloride and the like.

The copolymer of the present invention can be of various properties, such as liquid, gel or solid, or hydrophilic or hydrophobic, depending on the selection of the alkenyl ether of the general formula (1), the selection of the solvent in the polymerization, and the like. It is possible to obtain as.

For example, in solution polymerization, 5
If the alkenyl ether contains no or very few oxyethylene groups and uses a solvent having a molecular weight of 2,000 or more, a liquid copolymer can be obtained, and the alkenyl group has a methallyl group. If a polymer having a molecular weight of 2000 or less is used, a gel copolymer can be obtained. When an alkenyl ether having a molecular weight of 2,000 or more in which the polyoxyalkylene group is a polyoxyethylene group is used, a solid copolymer can be obtained. When an alkenyl ether having a large oxyethylene group content is used, a hydrophilic copolymer is obtained, and when an alkenyl ether having a small oxyethylene group content is used, a hydrophobic copolymer is obtained.

〔The invention's effect〕

According to the present invention, a copolymer having a relatively high molecular weight and a high carboxyl group content can be obtained by using an alkenyl ether having a carboxyl group in a molecule of the general formula (1) and maleic anhydride as essential components. , A gel, a solid, or any of hydrophilic and hydrophobic properties can be freely obtained. For this reason, it is possible to use alkenyl ether-maleic acid copolymers, which have only a very limited use range such as scale inhibitors, as adhesives, reactive coating materials, modifiers, and the like.

〔Example〕

Hereinafter, the present invention will be described with reference to Production Examples and Examples of alkenyl ethers.

Production Example 1 Allyl alcohol 58g and potassium hydroxide 5 in a pressure reactor
g under nitrogen atmosphere, 110 ~ 120 ℃, pressure 0.5 ~ 3Kg / cm ²
(Gauge pressure, the same applies hereinafter.) 1550 g of propylene oxide
Was gradually added while the addition reaction was carried out. After completion of the reaction, potassium hydroxide was neutralized with hydrochloric acid, and salts produced as by-products were removed by filtration. The hydroxyl value of the obtained polyoxypropylene glycol monoallyl ether was 40.1.

700 g of the obtained product and 57 g of monochloroacetic acid were placed in a pressure reactor, heated to 100 to 110 ° C. under a nitrogen atmosphere, and 100 ml of a 9N aqueous sodium hydroxide solution was gradually injected. After injection, the temperature was controlled at 120-140 ° C and the reaction was carried out for 5 hours.
Then, 150 ml of a 9N aqueous hydrochloric acid solution was added thereto, and the mixture was treated at 90 to 110 ° C. for 1 hour, and then washed five times with a saturated saline solution. 110 ± 1
After dehydration at 0 ° C. under reduced pressure of 10 to 30 mm / Hg, the resulting salt was removed by filtration to obtain 550 g of alkenyl ether. The etherification rate was 95.1%.

Production Example 2 In a pressurized reactor, 72 g of methallyl alcohol and 5.6 g of potassium hydroxide were put, and at a temperature of 100 to 120 ° C. and a pressure of 0.5 to 3 K under a nitrogen atmosphere.
g / cm ² at 925 g ethylene oxide and 122 propylene oxide
The addition reaction was performed while gradually introducing 0 g of the mixture.
After completion of the reaction, potassium hydroxide was neutralized with hydrochloric acid, and salts produced as by-products were removed by filtration. The hydroxyl value of the obtained polyoxyethylene polyoxypropylene glycol monomethallyl ether was 29.5.

950 g of the obtained product, 52.5 g of succinic anhydride and 50.6 g of triethylamine were refluxed, a nitrogen gas blowing tube was used,
Put in a four-necked flask equipped with a thermometer and a stirrer,
The mixture was stirred at 100 ± 5 ° C for 3 hours under a nitrogen stream. Then, triethylamine was removed at 130 ± 5 ° C. under a reduced pressure of 2 to 5 mm / Hg, and 960 g of monosuccinic acid ester of polyoxyethylene polyoxypropylene glycol monomethallyl ether was removed.
I got The esterification rate was 92.2%.

Production Example 3 132 g of isopropylidene glycerol and 2 g of potassium hydroxide were placed in a pressurized reactor, and an addition reaction was carried out under a nitrogen atmosphere at 120 to 130 ° C. and a pressure of 0.5 to 3 kg / cm ² while gradually injecting 450 g of ethylene oxide. Was. After the completion of the reaction, add 60 g of potassium hydroxide, and in a nitrogen atmosphere, at 110-120 ° C and at a pressure of 0.5-3 kg.
90 g of allyl chloride at / cm ²
After a lapse of 4 hours, the alkalinity of the reaction mixture was reduced to a substantially constant value, and the reaction was stopped. After 600 g of toluene was added, washing was performed three times with 400 g of ion-exchanged water. Then, the pH was adjusted to 2 or less with a 2N hydrochloric acid aqueous solution, and nitrogen bubbling was performed at 80 ° C. for 1 hour. Then, the pH was adjusted to 7 with a 2N aqueous sodium hydroxide solution, and dehydration under reduced pressure was performed at 110 ± 10 ° C and 20 to 50 mmHg for 2 hours. The generated salt was removed by filtration to obtain polyoxyethylene glycol monoallyl monoglycerol ether. The hydroxyl value was 196.5.

343.2 g of this product and 28 g of metallic sodium were placed in a pressure reactor, and a 50% by weight aqueous solution of sodium monochloroacetate was added.
Under a nitrogen atmosphere, the pressure was gradually increased in a temperature range of 110 ± 10 ° C. After injecting the whole amount, the reaction was further continued at 120 ± 10 ° C. for 4 hours. After the completion of the reaction, the pH was adjusted to 1 with a 5N aqueous hydrochloric acid solution, and 700 g of toluene was added thereto, followed by stirring until the mixture became homogeneous. Then, using 300 g of ion-exchanged water, washing was performed three times, and 110 ±
Dehydration and detoluene removal were performed at 10 ° C. and 20-50 mmHg for 3 hours. The formed salt was removed by filtration to obtain 220 g of allyl ether. The etherification rate was 45.1%.

Thereafter, allyl ethers of Production Examples 4 to 7 were obtained in the same manner as in Production Examples 1 to 3.

Table 1 shows the structures and analysis results of the alkenyl ethers obtained in Production Examples 1 to 7.

The polymer of the present invention was produced using the alkenyl ether of the general formula (1). The weight average molecular weight was determined by gel permeation chromatography.

Example 1 The following components were placed in a four-necked flask equipped with a cooling pipe, a nitrogen gas blowing pipe, a thermometer and a stirrer, heated to 80 ° C. under a nitrogen stream, and stirred for 4 hours to copolymerize. The reaction took place.

469.3 g (0.3 mol) of alkenyl ether of Production Example 1 29.4 g (0.3 mol) of maleic anhydride 5 g of benzoyl peroxide (1% by weight of monomer) 499 g of toluene (the same weight as the monomer) Then, 5 g of benzoyl peroxide was added, the temperature was raised again to 80 ° C., and the polymerization reaction (post-polymerization) was performed for 4 hours. After the reaction is completed, reduce the pressure to about 10 mmHg.
The toluene was distilled off at 110 ° C. to obtain 490 g of a transparent viscous liquid copolymer.

Analytical value of copolymer Elemental analysis C: (actual value) 60.52% (measured value) 60.55% H: (actual value) 9.66% (measured value) 9.68% Saponification value (actual value) 100.2 (calculated value) 101.1 Viscosity (100 ° C.) 260.4 cSt Weight average molecular weight 12000 FIG. 1 shows an infrared absorption spectrum of the copolymer.

Examples 2 to 9 In the same manner as in Example 1, the alkenyl ether of the general formula (1), maleic anhydride, and other monomers obtained in Production Examples were polymerized under the composition and polymerization conditions shown in Table 2. Got it. When a solvent was used, the same weight as the total weight of the monomers was used. The amount of the polymerization initiator used was represented by% by weight based on the total weight of the monomers.

 Table 3 shows the analysis results of the obtained copolymer.

These results show that the alkenyl ether-maleic anhydride copolymer of the present invention has various molecular weights.

[Brief description of the drawings]

FIG. 1 is an infrared absorption spectrum of the copolymer of Example 1.

──────────────────────────────────────────────────の Continuation of the front page (51) Int.Cl. ⁶ Identification number Agency reference number FI Technical indication location C09D 155/00 PGZ C09D 155/00 PGZ (C08F 222/06 216: 14)

Claims (1)

(57) [Claims] 1. A copolymer of an alkenyl ether represented by the general formula (1) and maleic anhydride, and if necessary, a copolymer with another monomer. The molar ratio with the monomer is 5 to 60:40 to 7
An alkenyl ether-maleic anhydride copolymer having 0: 0 to 40. (However, B is a residue of a compound having 2 to 8 hydroxyl groups, AO
Is one or a mixture of two or more oxyalkylene groups having 2 to 18 carbon atoms. When two or more oxyalkylene groups are used, they may be added in blocks or in random form, and X represents 2 carbon atoms. ~
An alkenyl group of 5; Y represents an acyl group of a dicarboxylic acid or a tricarboxylic acid; or an alkylene group having 1 to 3 carbon atoms; R represents a hydrocarbon group having 1 to 24 carbon atoms; 1 ≦ a ≦ 7,0 ≦ b ≦
6,0 ≦ c ≦ 6 and 1 ≦ a + b + c ≦ 7, and k, l, m, and n are 0 to 10 each of the average number of added oxyalkylene groups.
00, and k + al + bm + cn = 1 to 3000, p is 1 or 2. )