JPH0625227B2 - Copolymer and method for producing the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a linear copolymer of α-olefin, maleic anhydride and maleic imide or an N-substituted derivative, and a method for producing the same. More specifically, it relates to a linear copolymer of α-olefin having an ethylbenzene residue at the terminal of a molecule, maleic anhydride and maleic imide or an N-substituted derivative thereof, and a method for producing the copolymer in good yield.

[Conventional technology]

Conventionally, a copolymer of α-olefin and maleic anhydride is reacted with a basic substance to form an aqueous solution, and an adhesive, a binder, a coating agent, a paper additive, a pigment dispersant,
It is used as a scale inhibitor for cooling water, protective colloid for emulsion or latex, surfactant, vehicle for ink or paint, etc. However, water resistance is often required for these applications, and improvement thereof has been desired. As one of the improved methods, a copolymer of α-olefin and maleic anhydride is treated with ammonia or amine to convert an acid anhydride group based on maleic anhydride into an amide ammonium salt or an amide amine salt. A modified copolymer converted to an imide ring by a treatment such as post-heating, that is, α-olefin-maleic anhydride-
Maleic acid imide or N-substituted maleic acid imide (these may be collectively referred to as maleic acid imides)
Copolymers are known.

However, the above-mentioned modified copolymer is turbid when dissolved in an aqueous solution containing a basic substance, because the imide group is not uniformly introduced into the molecule because of a solid / gas or solid / liquid heterophasic reaction. , Often thickens. Therefore, in many cases, the effect of improving water resistance is not sufficiently exhibited when used for the above-mentioned applications. As a method of obtaining an α-olefin-maleic anhydride-maleic acid imide copolymer, a two-step treatment is carried out by treating the α-olefin-maleic anhydride copolymer with ammonia or an amine as described above, and then forming an imide ring. In addition to the three-step production method, a direct method of copolymerizing α-olefin, maleic anhydride and maleic imides is also conceivable, but no industrial production method thereof is known.

By the way, a polar solvent such as dimethylformamide is known as a solvent for the copolymer of α-olefin and maleic anhydride. However, such a polar solvent is extremely difficult to recover and cannot be an appropriate polymerization solvent in industrial production. Therefore, the copolymer of α-olefin and maleic anhydride is produced by precipitation polymerization in industrial production. As a solvent for carrying out the precipitation polymerization, it is necessary to dissolve the monomers to be copolymerized and not to dissolve the copolymer produced by the polymerization. Conventionally, when the α-olefin and maleic anhydride are polymerized, A known mixed solvent of ethyl acetate and tertiary butanol is known (see Japanese Patent Publication No. Sho 49-6382). If this mixed solvent is used, precipitation polymerization will be carried out smoothly,
Copolymer powder having a good shape can be obtained by removing the solvent by filtration and centrifugation and then drying.

[Problems to be solved by the invention]

However, when maleic imides are introduced as the third monomer to be copolymerized, even if the above mixed solvent is used, the block-like polymer adheres to the reactor wall or the stirring blade, and the smooth precipitation polymerization does not take place. However, since a considerable part of the produced copolymer is dissolved in the solvent, the yield of the copolymer is low and it is not suitable for industrial production. Further, as the solvent used in the precipitation polymerization, use of benzene, toluene, xylene, various esters, various ketones or various alcohols can be considered, and they have good solubility in the monomer, but the copolymer formed is partially formed. Melts and cannot form uniform particles. Therefore, like the above mixed solvent, it is not suitable as a polymerization solvent for industrial production.

A first object of the present invention is that α-olefin, maleic anhydride and maleic acid are easily and uniformly dissolved in an aqueous solution in which a basic substance is present, have no turbidity, do not thicken, and have excellent water resistance. It is to provide a linear copolymer of imide or an N-substituted derivative thereof.

Another object of the present invention is to obtain a linear copolymerization product of powdery α-olefin, maleic anhydride, and maleic imide or its N-substituted derivative in the form of particles having a uniform particle size and an appropriate size. It is to provide a method for producing a coalesced product with a high yield.

[Means for solving problems]

According to the present invention, the above-mentioned first object consists of a unit (A) based on α-olefin, a unit (B) based on maleic anhydride and a unit (C) based on maleic imide or its N-substituted derivative. , A, B and C components are A / (B +
C) and B / C are each 1 / 1-3 / 1 (molar ratio) and 2 / 8-9 / 1 (satisfying the molar ratio), the general formula at least one of the molecular ends -C ₂ H ₄ C ₆ This is achieved by a linear random copolymer having a group represented by H ₅ and having a weight average molecular weight of 1,000 to 200,000. Further, another object is achieved by subjecting .alpha.-olefin (a), maleic anhydride (b) and maleic imide or its N-substituted derivative (c) to precipitation polymerization using ethylbenzene as a polymerization solvent. .

In the present invention, the unit based on α-olefin is represented by the general formula —CH ₂ CR ¹ R ² — (wherein R ¹ and R ² may be the same or different from each other, hydrogen, carbon number 1 to 10 represents an alkyl group or an alkenyl group), and α-olefin as used herein means a linear or branched olefin having a carbon-carbon unsaturated double bond in the α-position. Is. Particularly, olefin having 2 to 12 carbon atoms, particularly 2 to 8 carbon atoms is preferable. Typical examples which can be used are ethylene, propylene, n-butylene, isobutylene,
n-pentene, isoprene, 2-methyl-1-butene,
3-methyl-1-butene, n-hexene, 2-methyl-
1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 2-ethyl-1-butene, 1,3-pentadiene, 1,3-hexadiene, 2,3-dimethylbutadiene, 2,5 -Pentadiene, 1,4-hexadiene, 2,2,4-trimethyl-1-pentene and the like. Of these, isobutylene is particularly preferable. Here, isobutylene also means a mixture containing isobutylene as a main component, for example, return BB. of course,
These olefins may be used alone or in combination of two or more.

In the present invention, the unit (B) based on maleic anhydride is represented by the general formula The maleic anhydride used here is partially maleic acid, maleic acid monoester,
It may be substituted with a maleic anhydride derivative such as maleic acid diester (hereinafter, these may be referred to as maleic anhydrides) or other α, β-dicarboxylic acid.

In the present invention, a unit based on maleic acid imide or an N-substituted derivative thereof, that is, a unit based on maleic acid imides has the general formula (In the formula, R ³ represents hydrogen, an alkyl group, a phenyl group, an alkylphenyl group, an alkoxyphenyl group, or a halogen substituent thereof), and the maleic imide used here is maleic acid. Acid imide, N-
N such as methylmaleimide, N-ethylmaleimide, N-propylmaleimide, Nn-butylmaleimide, Nt-butylmaleimide and N-cyclohexylmaleimide.
-Substituted alkylmaleimide N-phenylmaleimide, N
-Methylphenylmaleimide, N-substituted alkylphenylmaleimides such as N-ethylphenylmaleimide, or N-substituted alkoxyphenylmaleimides such as N-methoxyphenylmaleimide N-ethoxyphenylmaleimide, and further these Preference is given to halides (for example N-chlorophenylmaleimide). Among these, maleimides having a phenyl group at the N position, especially N-phenylmaleimide, are preferable.

The content ratio of each structural unit in the copolymer of the present invention is such that A / (B + C) is a molar ratio of 1/1 to 3/1 and B / C.
Is preferably in the range of 2/8 to 9/1 in terms of molar ratio. It is desirable that the molar ratio of A / (B + C) be 1/1 or a value close thereto, and in that case, a unit based on α-olefin, that is, a unit represented by —CH ₂ CR ¹ R ² — , A unit based on maleic anhydride, ie Or (In the formula, R ⁴ and R ⁵ may be the same or different from each other and represent hydrogen or an alkyl group), or a unit based on maleic acid imide, It has a structure in which the units represented by are alternately repeated, and at least one of the molecular ends is a copolymer having a group represented by -C ₂ H ₄ C ₆ H ₅ . Further, the B / C molar ratio is preferably in the range of 6/4 to 9/1 from the balance of water resistance and easy solubility in an aqueous solution containing a basic substance. The lengths of the units based on maleic anhydrides or maleic imides and the following same units are almost constant because the reactivity of maleic anhydride and maleic imides with olefins is almost the same. In this respect, it is expected to be different from the imidized product of the copolymer of the present invention and the α-olefin-maleic anhydride copolymer.

In the production method of the present invention, the mixing ratio of .alpha.-olefin, maleic anhydride and maleic imide varies depending on the composition of the target copolymer, but the total molar number of maleic anhydride and maleic imide is 1 It is effective to use 3 to 3 times more moles of α-olefin to increase the reaction rate of maleic anhydrides and maleic imides.

In the production method of the present invention, a linear multi-component copolymer of α-olefin, maleic anhydride and maleic imide is obtained by precipitation polymerization, and ethylbenzene is used as a solvent for such precipitation polymerization. . Ethylbenzene acts as a chain transfer agent at the time of polymerization, and remains in the copolymer as a group represented by the general formula —C ₂ H ₄ C ₆ H ₅ at one terminal of the resulting copolymer. In the present invention, other solvents such as ethylbenzene, benzene derivatives other than ethylbenzene such as benzene, toluene, or xylene, and organic acid esters such as ethyl acetate and isopropyl acetate may be mixed and used as a polymerization solvent. However, since the recovery and purification of the polymerization solvent becomes complicated, and depending on the type of the solvent, the molecular end and the molecular weight of the copolymer that are not obtained may be greatly affected, and therefore the use of a solvent other than ethylbenzene is an object of the present invention. It does not fit in. Considering industrial production, ethylbenzene is preferably used alone.

In the production method of the present invention, a copolymer is obtained by radical polymerization, and the polymerization catalyst used is an azo catalyst such as azobisisobutyronitrile or 1,1-azobiscyclohexane-1-carbonitrile, or a benzene catalyst. Organic peroxide catalysts such as nzoyl peroxide and dicumyl peroxide are preferred. The amount of the polymerization catalyst used is required to be in the range of 0.1 to 5 mol% with respect to maleic anhydrides and maleic imides, but preferably 0.5 to 3 mol%. As a method for adding the polymerization catalyst and the monomer, they may be added all together at the initial stage of the polymerization, but it is preferable to add them successively as the polymerization progresses.

In the production method of the present invention, the molecular weight is controlled mainly by the monomer concentration, the amount of catalyst used, and the polymerization temperature. As a substance for lowering the molecular weight, the periodic table I, II or II is used.
Group I metal salts, hydroxides, Group IV metal halides, amines represented by the general formula N≡, HN =, H ₂ N- or H ₄ N-, nitrogen such as ammonium acetate and urea Compound,
It is also possible to add a mercaptan or the like at the initial stage of the polymerization or during the progress of the polymerization to control the molecular weight of the copolymer. The polymerization temperature is preferably in the range of 40 ° C. to 150 ° C., particularly 60 ° C. to 120 ° C. When the polymerization temperature is too high, the resulting copolymer tends to be blocky and the polymerization pressure becomes significantly high. There are drawbacks. The polymerization time is 1 to 24 hours, preferably 2 to 10 hours. The amount of the polymerization solvent used is such that the concentration of the obtained copolymer is 5 to 40% by weight, preferably 10
It is desirable that the content be ˜30% by weight.

In this way, a copolymer of α-olefin, maleic anhydride and maleic imides is obtained. According to infrared absorption spectrum, nuclear magnetic resonance spectrum, elemental analysis, etc. At least one of the ends of the molecule in the united product has a group represented by the general formula —C ₂ H ₄ C ₆ H ₅ . In addition, according to the light scattering method and the viscosity method, the copolymer is often 1,000 to 200,000 in weight average molecular weight (▲
▼). In the viscosity method, when the intrinsic viscosity ([η]) in dimethylformamide is measured, the intrinsic viscosity is in the range of 0.05 to 1.5. The copolymer is usually obtained in the form of powder having particles of about 16 to 60 mesh.

According to the production method of the present invention, since ethylbenzene is used as a polymerization solvent, which has moderate solubility for the reaction monomer but poor solubility for the copolymer produced.
The resulting copolymer does not adhere to the reactor wall or stirring blade, and precipitation polymerization can be carried out smoothly. Further, the copolymer obtained in the dehydration and drying step is not preferable because of melt fusion and the like. Therefore, the copolymer can be obtained in a high yield which cannot be obtained by the conventional production method. Since the copolymer can be obtained in a larger and more uniform powder form, the fine powder of the product does not scatter, the product is easy to handle, and the product loss due to scattering does not occur, and the working environment does not deteriorate. Of.

The copolymer of the present invention is excellent in water resistance as compared with a conventional α-olefin-maleic anhydride copolymer having no ethylbenzene residue at the molecular end, and is an imidized product from a nuclear copolymer. In comparison, it is excellent in solubility in an aqueous solution containing a basic substance, and the turbidity or the change in thickening observed in the aqueous solution of the imidized product is not observed. Therefore, when it is used as an adhesive, a coating agent, and an additive for paper, the effect of improving the water resistance is found. In addition to these features, it also has the following features.

It has good compatibility with hydrophobic polymer substances and can improve its physical properties as an additive for plastics and films.

Maleic imides cannot be water-soluble groups,
Since it has a large polarity, it acts as a coupling agent between the inorganic substance and the hydrophobic polymer substance.

When made into an aqueous solution in the presence of a basic substance, the surface activity of the aqueous solution becomes large, and the polymer substance functions as an emulsifier and an oil agent. Therefore, by taking advantage of these characteristics, a relatively low molecular weight copolymer having a weight average molecular weight of 1,000 to 200,000 is, for example, a pigment dispersant, a cooling water scale inhibitor emulsion or a latex protective colloid surfactant ink paint. It can be applied to other vehicle binders, etc., and imparts excellent properties to them.

〔Example〕

Hereinafter, the present invention will be described in more detail with reference to Examples.
The present invention is not limited to these.

Example 1 419.1 g of ethylbenzene, 29.4 g of maleic anhydride, N-
34.6 g of phenylmaleimide and 0.67 g of azobisisobutyronitrile were put into 1 autoclave equipped with a stirrer, nitrogen was introduced for 30 minutes, then 30.8 g of isoptylene was put therein, and the liquid in the autoclave was heated to 80 ° C under stirring. did.
Then, the polymerization reaction was carried out for 5 hours while maintaining the internal temperature at 80 ° C. After the completion of the polymerization reaction, the liquid in the autoclave was cooled to room temperature and deaerated, and then the stirring was stopped and the precipitated polymer was taken out and overdried. As a result, it passed through a 100 mesh sieve, had a large particle size and was a pale yellow powder. Copolymer 9
0.6 g was obtained. The polymer yield was as high as 98.5% of the theoretical yield from the charged monomers. When the inside of the autoclave was inspected at the time of taking out the polymer, it was found that there was almost no adhesion of the polymer to the inner wall and the stirring blade, and the removal of the polymerization solvent due to the excess of the precipitated polymer was easy.
The weight average molecular weight of the obtained polymer was about 2 calculated from the intrinsic viscosity ([η]) of 0.253 of the dimethylformamide solution.
The molecular structure was 7,000, and the molecular structure showed that ethylbenzene residue was at one end of the molecule, and isobutylene: maleic anhydride: N-phenylmaleimide was copolymerized at a molar ratio of 5: 3: 2. It was confirmed that When 100 parts by weight of this polymer were mixed with 43.7 parts by weight of 25% ammonia water and 353.5 parts by weight of water, an aqueous solution in which no turbidity was observed was obtained.

Example 2 300 g of ethylbenzene, 19.6 g of maleic anhydride,
37.4 g of N-2-methylphenylmaleimide and 0.3 g of azobisisoptyronitrile were placed in a 1 autoclave equipped with a stirrer, nitrogen was introduced for 30 minutes, and 23.5 g of isobutylene was placed in the autoclave and stirred in the autoclave. The temperature of the liquid was raised to 60 ° C. Next, 62 g of ethylbenzene was added with 0.36 of asobisisobutyronitrile.
Polymerization reaction was carried out at 60 ° C. for 5 hours while successively charging the catalyst solution in which 1 g was dissolved at a rate of 15.5 g per hour.
After the completion of the polymerization reaction, the liquid in the autoclave was cooled to room temperature, deaerated, stirring was stopped, and the precipitated polymer was taken out and overdried to obtain 77.3 g of a pale yellow powdery copolymer. This was a polymer yield of 97.4% of the theoretical yield of polymer. Its intrinsic viscosity ([η]) was 0.637, which was about 91,000 in terms of weight average molecular weight. The composition molar ratio of isobutylene: maleic anhydride: N-2-methylphenylmaleimide was 2: 1: 1.

Example 3 As α-olefin, polymerization was carried out in the same manner as in Example 1 except that a mixture of 26.5 g of isobutylene and 7.05 g of 1-butene was used in place of 30.8 g of isobutylene, and a pale yellow having an intrinsic viscosity of 0.214. A powdery copolymer was obtained with a yield of 96.9%. The molar ratio of isobutylene: 1-ptene: maleic anhydride: N-phenylmaleimide in the obtained copolymer was 4.5: 0.5: 3: 2.

Example 4 419.1 g of ethylbenzene, 29.4 maleic anhydride
g, 34.6 g of N-phenylmaleimide and 1.35 g of azobisisobutyronitrile were placed in a 1 autoclave equipped with a stirrer, and after introducing nitrogen for 30 minutes, C _{5 having the} composition shown in Table 1 was added thereto. Add 50 g of the olefin mixture and raise the temperature of the liquid in the autoclave to 80 ° C with stirring.
The polymerization reaction was carried out for 8 hours while maintaining the temperature at ℃. After completion of the polymerization reaction, the liquid in the autoclave was cooled to room temperature and degassed,
When the stirring was stopped and the precipitated polymer was taken out and over-dried, 94.2 g of a pale yellow powdery copolymer was obtained. This is a yield of 95.2% of the theoretical yield. When the inside of the autoclave was inspected at the time of taking out the polymer, it was found that the polymer did not adhere to the inner wall and the stirring blade, and that the polymerization solvent was easily removed due to the excess of the precipitated polymer. The intrinsic viscosity ([η]) of the dimethylformamide solution of the obtained polymer was 0.137. The molar ratio of C ₅ olefin: maleic anhydride: N-phenylmaleimide in the polymer was 5: 3: 2.

Example 5 A light yellow powdery copolymer having an intrinsic viscosity ([η]) of 0.581 was prepared in the same manner as in Example 2 except that the polymerization catalyst was changed to benzoyl peroxide.
It was obtained at 7.1%. From the NMR measurement results of this polymer, it was confirmed that the molecular structure has an ethylbenzene residue at one end of the molecule and the molar ratio of isobutylene: maleic anhydride: N-2 methylphenylmaleimide is 2: 1: 1. Was done.

Comparative Example 1 300 g of a mixed solvent of ethyl acetate / tert-butanol (mixing weight ratio: 75/25), maleic anhydride 19.
6 g, N-phenylmaleimide 34.6 g and azobisisobutyronitrile 0.66 g were put into a 1 autoclave equipped with a stirrer, nitrogen was introduced for 30 minutes, isobutylene 23.5 g was put therein, and the internal temperature of the autoclave was stirred while stirring. Was heated to 60 ° C., and the polymerization reaction was carried out for 5 hours while maintaining the temperature at 60 ° C. After the completion of the polymerization reaction, the liquid in the autoclave was cooled to room temperature, and after degassing, the stirring was stopped and the inside of the autoclave was inspected. As a result, the precipitated polymer was deposited in the form of a block on the autoclave wall and the stirring blade during the polymerization. These blocks were such that stirring was abnormal during the polymerization reaction. The solvent was removed by decantation and the deposited polymer was scraped out and overdried. Isobutylene:
66.5 g of a pale yellow block copolymer having a molar ratio of maleic anhydride: N-phenylmaleimide of 4: 2: 2 and an intrinsic viscosity ([η]) of 0.889 (theoretical polymer yield of 87). .1%) was obtained. Of the copolymer obtained here
According to the result of measurement by NMR, the molecular end was confirmed to be a decomposition fragment of the polymerization catalyst azohisisobutyronitrile. The block copolymer required further pulverization in order to obtain a powder.

Comparative Examples 2 to 3 Polymerization was carried out in the same manner as in Comparative Example 1 except that methyl isobutyl ketone and isopropyl acetate were used instead of the mixed solvent of ethyl acetate / tert-butanol, respectively. Was obtained only in a low yield of 75-85% of the theoretical polymer yield.

Comparative Example 4 Polymerization was performed in the same manner as in Comparative Example 1 except that toluene was used instead of the mixed solvent of ethyl acetate / tertiary butanol, but the block copolymer was as low as 87% of the theoretical polymer yield. It could only be obtained in yield.

Comparative Example 5 150 g of an isobutylene-maleic anhydride alternating copolymer [Kuraray Isoprene Chemical Co., Ltd., Isoban-04] having a weight average molecular weight of 60,000 was placed in a separable flask equipped with a stirrer (1), and a mixed gas of ammonia / nitrogen ( The mixture volume ratio of 15/85 was blown in and the reaction was carried out while cooling with a water bath until the exotherm stopped (about 1 hour). Then, while heating in an oil bath, pressurize the ammonia / nitrogen mixed gas,
While distilling the produced water out of the system, the temperature was raised to 170 ° C,
The imidization reaction was performed. After completion of the reaction, the reaction product was taken out and dried by heating. The composition of the obtained copolymer was 50 mol% of isobutylene, 25 mol% of maleic anhydride and 25 mol% of maleic imide. This copolymer 10
0 parts by weight was mixed with 43.7 parts by weight of 25% ammonia water and 353.5 parts by weight of water, but turbidity was observed in the obtained aqueous solution.

Example 6 306.8 g of ethylbenzene, 23.8 g of maleic anhydride, N-
22.6 g of phenylmaleimide and 0.5 g of asobisisobutyronitrile were put into a 1 autoclave equipped with a stirrer, and after purging with nitrogen, ethylene was added to the autoclave at an internal pressure of 5
It was charged up to 0 kg / cm ² . The temperature inside the autoclave was raised to 80 ° C. with stirring, and the polymerization reaction was carried out for 5 hours while maintaining the temperature at 80 ° C. After the completion of the polymerization reaction, the internal temperature of the autoclave was cooled to room temperature, degassed, and stirring was stopped. The precipitated copolymer was taken out and dried after filtration. As a result, 54.3 g of a pale yellow powdery copolymer having a large particle size which hardly passed through a 100 mesh sieve was obtained. This is the theoretical yield of 9
The yield was 5.6%. When the inside of the autoclave was inspected at the time of taking out the polymer, it was found that the polymer was hardly attached to the wall of the autoclave and the stirring blade, and the solvent was easily removed by the excess precipitated polymer. The dimethylformamide solution of the obtained copolymer had an intrinsic viscosity ([η]) of 0.481 at 30 ° C., and its molecular structure showed that it had an ethylbenzene residue at one end of the molecule and ethylene. The molar ratio of maleic anhydride: N-phenylmaleimide is approximately 3: 2 :.
It was confirmed that it was a copolymerized product of 1.

Example 7 Ethylene was added to diisobutylene (isobutylene dimer
4,4-trimethylpentene-1,2,4,4-trimethylpentene-2) was used, and the procedure of Example 5 was repeated to obtain a pale yellow powdery copolymer 88. 2 g
Obtained. This was a polymer yield of 97% of theoretical yield. Almost no polymer adhered to the inner wall of the autoclave and the stirring blade, and the intrinsic viscosity ([η]) of the precipitated polymer in dimethylformamide at 30 ° C was 0.583. From the results of high resolution NMR analysis, its molecular structure was It was confirmed that the compound had an ethylbenzene residue at one terminal and was copolymerized with diisobutylene: maleic anhydride: N-phenylmaleimide at a molar ratio of 2: 1: 1.

Use Example 1 50 g of the copolymer obtained in Example 2, 9 g of 25% aqueous ammonia and 107.6 g of distilled water were placed in a 300 cc separable flask equipped with a stirrer and a back-flow condenser, and 90 to 9
While heating to 5 ° C., the mixture was stirred and dissolved for 2 hours to give an aqueous solution.
The aqueous solution was homogeneous without any turbidity. 36.7 g of this aqueous solution, 2.8 g of distilled water, 27.5 g of calcium carbonate and 33 g of styrene-butadiene rubber latex [Sumitomo Nogataku Co., Ltd. 33 g] were sequentially added, and then a white dispersion solution was prepared by stirring. An adhesive composition was obtained by adding 5 g of glyceryl glycidyl ether (WPE145) to this solution.

After applying 200 g / m ^{2 of} this adhesive composition to a hemlock shavings board (thickness: 10 m / m), another hemlock shavings board is layered and cooled at 20 ° C. and 65% RH under a pressure of 10 kg / cm ² for 16 hours. Compressed. The adhesive piece was cured at 20 ° C. and 65% RH for 7 days, cut into test pieces, and the shrink shear adhesive strength was measured according to the method of JIS-K-6852. The results are shown in Table 2.

Comparative Use Example 1 Isobutylene-maleic anhydride alternating copolymer having a weight average molecular weight of 60,000 [Kuraray Isoprene Chemical Co., Ltd., Isoban-04] 50 g, 25% aqueous ammonia 26.5 g,
Distilled water 90.2g 30 equipped with a stirrer and a backflow condenser
The mixture was placed in a 0 cc separable flask and heated with stirring at 90 to 95 ° C. for 2 hours with stirring to form a uniform solution. 30 g of the above aqueous solution instead of 33 g of the aqueous copolymer solution of Use Example 1
The compression shear adhesive strength was measured by the same method as in Use Example 1 except that The results are shown in Table 2.

Comparative Use Example 2 The compression shear adhesive strength was measured in the same manner as in Use Example 1 except that 33 g of the aqueous copolymer solution obtained in Comparative Example 5 was used. The results are shown in Table 2.

Use Example 2 50 g of the copolymer obtained in Example 7, 13.5 g of 25% aqueous ammonia, and 103 g of distilled water were placed in a 300 cc separable flask equipped with a stirrer and a backflow condenser, and the mixture was heated to 90-
While heating to 65 ° C., the mixture was stirred and dissolved for 2 hours. The solution was homogeneous without turbidity. This copolymer aqueous solution 3
6.7 g, distilled water 2.8 g calcium carbonate 27.5 g and styrene-butadiene rubber latex (manufactured by Sumitomo Nogataku Co., Ltd.) 33 g were sequentially added, and then a white dispersion solution was obtained by stirring. 3 g of glycerin diglycidyl ether was added to this solution to obtain an adhesive composition.

This adhesive composition is Lauan plywood (thickness 3m / m3 ply)
Each surface was evenly applied at a rate of 125 g / m ² , and the adhesive surfaces were brought into close contact with each other, and the press was pressed at 115 ° C. hot press 10 kg / cm ² for 3 minutes, followed by curing at room temperature for 24 hours. After curing, the tensile shear adhesive strength was measured according to JAI-5-1978. The results are shown in Table 3.

Comparative Use Example 3 Using the adhesive composition obtained by the same method as in Comparative Use Example 1, and operating in the same manner as in Use Example 2, a test piece for measuring tensile shear adhesive strength was prepared and subjected to a tensile test. Shear adhesion was measured. The results are shown in Table 3.

Use Example 3 50 g of the copolymer obtained in Example 1, 12.2 g of 25% ammonia water and 271.1 g of distilled water were placed in a 500 cc separable flask equipped with a stirrer and a backflow condenser, and
The solution was dissolved for 2 hours with heating and stirring at ˜95 ° C. to form a uniform solution. 33 g of this aqueous solution, 9 g of distilled water and 20 g of vinyl acetate, 300 cc equipped with a constant-speed stirring device and a backflow condenser
It was put in a separable flask, and the internal temperature was raised to 60 ° C. while stirring at a rotation speed of 300 rpm. 30g distilled water
Of 0.39 g of hydrogen peroxide, 1.79 g of Rongalit and 80 g of vinyl acetate dissolved in 30 g of distilled water were added to the above flask at a rate of 15 g of hydrogen peroxide, 15 g of Rongalit aqueous solution, and 40 g of vinyl acetate per hour, respectively. Emulsion polymerization was carried out at 60 ° C. for 2 hours while successively adding. After the completion of the successive addition, the polymerization reaction was completed by further heating and stirring at 60 ° C. for 30 minutes. The emulsion obtained has a viscosity
The content was 1830 cp, pH 5.56, and the dry solid content was 49.2% by weight, and the viscosity stability and freeze stability were excellent.

〔The invention's effect〕

The copolymer of the present invention easily and uniformly dissolves in an aqueous solution in which a basic substance is present, has no turbidity, and does not thicken,
Moreover, it has excellent water resistance. Further, according to the production method of the present invention, a powdery copolymer composed of particles having a uniform particle size and an appropriate size can be obtained in good yield.

Claims (6)

[Claims] 1. A unit consisting of an α-olefin-based unit (A), a maleic anhydride-based unit (B) and a maleic imide or a N-substituted derivative thereof (C), each of A, B and C. Ingredients are A / (B + C) and B
/ C is 1/1 to 3/1 (molar ratio) and 2/8 to 9 respectively
/ 1 satisfied (molar ratio), having a group represented by _-C 2 _H 4 _C 6 _{H 5} at least one end of the molecule, and linear random weight average molecular weight of 1,000 to 200,000 Copolymer. 2. The copolymer according to claim 1, wherein the α-olefin is isobutylene. 3. A maleic imide or an N-substituted derivative thereof is N-phenylmaleimide.
The copolymer according to the item. 4. An α-olefin (a), a maleic anhydride (b) and a maleic imide or an N-substituted derivative (c) thereof are subjected to precipitation polymerization using ethylbenzene as a polymerization catalyst. In each of the components b and c, a / (b + c) and b / c satisfy 1/1 to 3/1 (molar ratio) and 2/8 to 9/1 (molar ratio), respectively, and at least one of the molecular ends. having a group represented by _-C 2 _H 4 _C 6 _{H 5} in and a weight average molecular weight 1,000～200,
A method for producing a linear random copolymer of α-olefin, maleic anhydride and maleic imide or its N-substituted derivative of 000. 5. The production method according to claim 4, wherein the α-olefin is isobutylene. 6. A maleic imide or an N-substituted derivative thereof is N-phenylmaleimide.
The manufacturing method according to item.