JPH01108A - Alkenyl ether-maleic anhydride copolymer - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a novel copolymer of polyoxyalkylene polyol monoalkenyl ether and maleic anhydride.

[Conventional technology]

A copolymer of polyoxyalkylene/glycol monoallyl ether and a maleic acid monocap is disclosed in JP-A-59-17.
It is disclosed in Japanese Patent No. 6312, etc., and is used as an anti-school agent, a chelating agent, a dispersant, etc.

(Problems to be Solved by the Invention) E. The copolymer disclosed in the above-mentioned publication is obtained by copolymerizing polycamexyalkylene glycol monoallyl ether and maleic acid or maleic anhydride in an aqueous solution. According to the example, lumonoalkenyl ether (
The purpose is to produce a copolymer of alkenyl ether (hereinafter simply referred to as alkenyl ether) and maleic anhydride, and a relatively high molecular weight copolymer can be obtained.

[Means for solving problems]

The present invention is a copolymer of an alkenyl ether represented by formula (I) and maleic anhydride, optionally with other monomers, and a copolymer of an alkenyl ether and maleic anhydride. Molar ratio of acid to other monomers is 5 to 60:4
It is a copolymer with a ratio of 0 to 70:0 to 4o.

R1O(AO)nlζ2 ・・・・・・・・・−・
・－・・・・・・・・・・・・・・・ (I) (However, A
O is one or a mixture of two or more oxyalkylene groups having 2 to 18 carbon atoms, and when there are two or more, they may be added in a block or random manner.
is an alkenyl group having 4 to 5 carbon atoms, B2 is an alkyl group having 1 to 3 carbon atoms or a saturated acyl group, and n is the average number of added moles of an oxyalkylene group, which is 1 to 1,000. ) In this case, the ratio of the total number of moles of alkenyl ether and other monomers to the number of moles of maleic anhydride is 30-60 or 0-40.

In the general formula (I), the alkenyl group having 4 to 5 carbon atoms represented by Hl includes a methallyl group, 1. Examples include l-dimethyl-2-gropenyl group and 3-methyl-3-butenyl group.

The oxyalkylene group having 2 to 18 carbon atoms represented by AO includes oxyethylene group, oxyethylene group, oxybutylene group, oxytetramenalene group, oxystyrene group, oxyalkylene group, oxytetradecylene group, and oxyhexane group. Examples include decylene group and oxyoctadecylene group.

The alkyl groups of carbon Aa1 to Aa3 represented by R2 include methyl, ethyl, glovyl, and inglovyl groups, and the saturated acyl groups include acyl groups derived from acetic acid, glopionic acid, and the like.

The alkenyl ether of general formula (I) used in the present invention can be produced by various methods, some of which are shown below.

(a) Charcoal A in alkenyl alcohol having 4 to 5 carbon atoms
An addition reaction is performed on alkylene oxides having numbers 2 to 18. Next, an alkyl halide, a carboxylic acid, a carboxylic acid halide, etc. in which KR'' is an alkyl group or an !aI acyl group are reacted.

(b) An alkylene oxide having 2 to 18 carbon atoms is added to an alcohol or carboxylic acid in which R'' is an alkyl group or a saturated acyl group, and then a halogenated alkenyl having 4 to 5 carbon atoms is reacted.

The other monomers are vinyl type monomers copolymerizable with the alkenyl ether of general formula (I) and maleic anhydride,
Acrylic acid, methacrylic acid, itaconic acid, crotonic acid,
Maleic acid, divalent metal salts, ammonium salts, organic amine salts, esters with alcohols having 1 to 24 carbon atoms, aromatic vinyl compounds such as styrene and methylstyrene, vinyl chloride, Examples include halogenated vinyl compounds such as vinylidene chloride, olefins such as inbutylene and diisobutylene, vinyl acetate, acrylonitrile, and acrylamide.

The comonomer of the present invention is prepared by bulk polymerizing the alkenyl ether of the general formula (I) and maleic anhydride, adding other monomers if necessary, in the presence of a polymerization initiator, and then polymerizing the alkenyl ether of the general formula (I) with maleic anhydride in the presence of a polymerization initiator. Polymerization initiators include organic peroxides such as benzoyl peroxide, lauroyl peroxide, and di-t-butyl peroxide; There are compounds etc.

Solvents used for solution polymerization include benzene, toluene,
Aromatic hydrocarbons such as xylene W%, aliphatic hydrocarbons such as n-hexane and cyclohexane, ketones such as acetone and methyl ether ketone, ethers such as dimethyl ether, diethyl ether, tetrahydro-7rane, dioxane, chloroform, carbon tetrachloride, etc. There are halogenated hydrocarbons, etc.

Although the weight semiuniform molecular line of the copolymer of the present invention is not limited,
It is 500 or more, especially 1000 or more.

The comonomer of the present invention can be produced in various properties such as liquid, gel, or solid, hydrophilic or hydrophobic, depending on the selection of the alknyl ether of the general formula (I) and the selection of the benzene in the polymerization reaction. Get the ip for that one.

〔Effect of the invention〕

The present invention uses the alkenyl ether and maleic anhydride of (I) as essential components, so that it can be used in any form of relatively high molecular weight, liquid, gel, solid, hydrophilic or hydrophobic. can be obtained freely. Therefore, the alkenyl ether-maleic U copolymer, which has hitherto been used only in a very limited range as a scale inhibitor, can now be used in water-absorbing polymer compositions, reactive coating materials, and the like.

〔Example〕

The following is a description of alkenyl ether production examples, examples, and comparative example V.

Production example 1 3-methyl-3-butenyl alcohol 86% in a pressurized reactor
An addition reaction was carried out with 2 and potassium hydroxide IIIF under nitrogen gas atmosphere at 100 to 110 DEG C. and a pressure of 0.5 to 4 kg/d (gauge pressure) while gradually pressurizing propylene oxide 1276j"i.

After reaction route r, sodium methyl chloride (651 Ft) was added and treated at 115-125° C. for 4 Fk# in bulk for 10-30 days. Next, nitrogen gas was added to the pressure at 0.5/- (cage pressure), and 70f of methyl chloride was added at 15 to 125°C, 0.
．． When the reaction was carried out at 5 to 4 ky/t:tA (gauge pressure), the alkalinity of the reaction mixture decreased in 4 hours and reached a nearly constant value, so it was diluted with hydrochloric acid to remove the by-produced salt. The alkenyl ether was obtained by filtration.

Production example 2 Methanol 329 and sodium meter in a pressurized reactor)
1.1F, 130-140℃ under nitrogen gas atmosphere
, ethylene oxide 3 at 0,5-3 plum/- (gauge pressure)
96v was added. After the reaction, add sodium hydroxide 752 and heat at 110-120℃, 10-30■Hg.
I was dehydrated. Next, after pressurizing with nitrogen gas to 1 kf/cd (gauge pressure), 120 t of methallyl chloride was gradually added at 110 to 120°C to carry out the reaction, and the alkalinity of the reaction mixture decreased in 4 hours. When the value became almost constant, neutralize with hydrochloric acid, filter out the by-product salt, and remove the alkenyl ether.

Production Example 3 In a pressurized reactor, 60 t of n-gropanol, 5 f of boron trifluoride-ether complex, and 441 t of nat-2hydrofuran were added.
2 was taken and heated under a nitrogen gas atmosphere at 45 to 50°C and a pressure of 0.
Ethylene oxide 26 at 5-3 kr/cd (gauge pressure)
Addition reaction was carried out by gradually pressurizing 9f. After the reaction was completed, the catalyst, boron trisulfide, was mixed with sodium carbonate, and the by-product salt was removed by filtration. Nine products obtained 720
Add 70f of sodium hydroxide to f and heat to 115-125℃
, 1O ~ 30 mHg. Next, 0.5 kg
After pressurizing with nitrogen gas to /d (gauge pressure), 115
The reaction was carried out by gradually adding methallyl chloride 1201 at ~125°C. After 4 hours, the alkalinity of the reaction mixture decreased to a nearly constant value, so it was neutralized with hydrochloric acid.
The alkenyl ether was obtained by removing the by-product salt.

Production Example 4 In a pressurized reactor, 72 t of methallyl alcohol and 5.62 t of potassium hydroxide were added to 9, under nitrogen gas atmosphere, 100 to 110
An addition reaction was carried out by gradually pressurizing ethylene oxide 3522 at a temperature of 0.5 to 3 cm/- (gauge pressure). Then, 464 t of propylene oxide was subjected to an addition reaction in the same manner. After the reaction was completed, potassium hydroxide was neutralized with hydrochloric acid, and by-produced potassium chloride was removed by filtration. Next, the obtained product 8001 and acetic anhydride 2041 were heated to 100 to 110°C under a nitrogen gas stream in a four-necked flask and reacted for 4 hours. After the reaction, by-produced acetic acid was removed by washing with water, and dehydration was performed under reduced pressure at 100-110°C and 10-30 μHg to obtain alkenyl ether t? Also.

Production Example 5 To a pressurized reactor, 469 ml of ethanol and 7.62 ml of sodium metal were added little by little and dissolved. Next, under nitrogen gas atmosphere, 140±lθ℃, pressure 0°5~5 kf/c
An addition reaction was carried out by gradually pressurizing 7590 f of ethylene oxide at a pressure of 100 g (gauge pressure).

After the reaction was completed, potassium hydroxide 801F was added and 'i11
Under elementary gas atmosphere, 110±10℃, pressure 0.5-5K
110f of methallyl chloride was introduced under pressure at 1/- (gauge pressure) and reacted. After 4 hours, the alkalinity in the reaction mixture reached a nearly constant value, so it was neutralized with hydrochloric acid, and the by-produced salt was filtered. Separation gave alkenyl ether.

Table 1 shows the structures and analysis results of the alkenyl ethers obtained in Production Examples 1 to 5.

Example 1 Alkenyl ether of Production Example 2 4821F (1 mol) Maleic anhydride 981F (1 mol) Benzoyl peroxide 6? (monomer 1111t4) Toluene 580? (Same weight as the monomer) The above components were placed in a four-loaf flask equipped with a cooling tube, nitrogen gas blowing tube, thermometer, and stirring device, and the temperature was raised to 80°C under a nitrogen gas atmosphere to carry out the co-merization reaction. I did it. The mixed liquid became gel-like in about 5 minutes after the temperature was raised. Stop stirring 8
After holding at 0°C for 3 hours, toluene was added to 100°C under reduced pressure.
Distilled at 1: and remembered the common A basin of 498.

The obtained comonomer was in the form of a transparent elastic gel and did not dissolve in the 6-layer solvent.

Elemental analysis values C: 55.834 (calculated value 55.85 points) H: 8.33 points (calculated value 8.33 points) The infrared absorption spectrum of the saponified 1iff+190.3 copolymer is shown in FIG.

Comparative example 1 CH2=CHCH2(QC2H4), OH454f (
1 mol) Maleic acid 116r (1 mol)
6 units of benzoyl peroxide (1 unit weight of the monomer) Toluene 5701 units (same weight as the monomer) The above ingredients were placed in a four-hole flask equipped with a cooling tube, nitrogen gas blowing, an A1 thermometer, and a stirring device. The temperature was raised to 80° C. under a nitrogen gas atmosphere, and a copolymerization reaction was carried out for 4 hours. Then, the toluene was distilled off at 100°C under reduced pressure to remove the 5252 compound (primary).

The resulting comonomer was a viscous liquid.

Elemental analysis value C: 52.57 = 4 (calculated 1st shift 52.62%) 1 (: 8.13% (calculated value 8.12) Saponification value 198.4 Kinematic viscosity (100°C) 35.7cst Weight Average molecule!
(Gel Vermutation Chromatography) 1
800 Example 1 and Comparative Example 1 show that the alkenyl ether-maleic anhydride copolymer of the present invention has a larger molecular weight than the alkenyl nityl-maleic acid copolymer.

Examples 2 to 9 In the same manner as in Example 1, the copolymers of the present invention shown in Table 3 were obtained using the monomers of coating 2 and the polymerization conditions.

In addition, when using a solvent, it is the same as the total amount of monomers.
was used.

In addition, the amount of polymerization initiator used is I based on the total amount of monomers.
Expressed with L cover. In Examples 2.4 and 8, half of the polymerization initiator was first added and the reaction was carried out at a predetermined temperature for 2 hours, then cooled to room temperature, the remaining half of the polymerization initiator was added, and then the reaction was carried out at a predetermined temperature. The reaction was continued for an additional 3 hours. In Example 1, as in Example 1, the entire amount of polymerization initiator was added from the beginning.

From the results in Table 3, it can be seen that the alkenyl ether-maleic anhydride copolymer of the present invention can be in any form of freeness, hydrophobicity, liquid, gel, or solid.

[Brief explanation of drawings]

FIG. 1 is an infrared absorption spectrum diagram of the alkenyl ether-maleic anhydride copolymer obtained in Example 1. Patent marriage ceremony Nihon Yushi Kyuniansha

Claims (1)

[Scope of Claims] 1. A copolymer of an alkenyl ether represented by the general formula (I) and maleic anhydride, which is a copolymer with other monomers if necessary, and an alkenyl ether and maleic anhydride. Molar ratio of acid and other monomers is 5 to 60:40 to 7
A copolymer having a ratio of 0:0 to 40. R^1O(AO)_nR^2...(I) (However, AO is one type or a mixture of two or more types of oxyalkylene groups having 2 to 18 carbon atoms, and when two or more types are used, they are added in a block form. R^1 is an alkenyl group having 4 to 5 carbon atoms, R^2 is an alkyl group or saturated acyl group having 1 to 3 carbon atoms, and n is an oxyalkylene group. The average number of added moles is 1 to 1000.)