JPS6346762B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a novel industrially useful reactive polymer. Specifically, the present invention relates to a method for producing a reactive polymer by reacting a polymer containing a free carboxylic acid group with an aziridine compound having an unsaturated group.

"Reactive polymer" as used herein
The term refers to a polymer having a reactive group that "can undergo or participate in a so-called radical reaction" under the action of heat, ultraviolet light, electron beams, free radical generating agents, etc. Heretofore, several proposals have been made as methods for producing such reactive polymers. One of these uses the so-called esterification reaction, for example, the reaction of a polymer containing free carboxylic acid groups with an unsaturated hydroxyl compound or an unsaturated glycidyl compound, or the reaction of a polymer containing a hydroxyl group or a glycidyl group. A method is known that utilizes the reaction between carbon dioxide and an unsaturated carboxylic acid compound. However, in the esterification reaction, the reactants are generally kept under harsh temperature conditions for a relatively long period of time, so side reactions such as polymerization of unsaturated groups are likely to occur during the reaction. As a means to reduce such risks, measures such as adding a large amount of polymerization inhibitor to the reaction system, introducing oxygen, and relaxing reaction conditions by using an esterification reaction catalyst are known, but the resulting reaction Polymers often contain excessive amounts of polymerization inhibitors, catalyst residues, etc., and depending on the intended use, they may cause discoloration or reaction delays, resulting in poor quality evaluations.

Another known method utilizes a urethanization reaction, such as a method in which a polymer having a hydroxyl group and an unsaturated hydroxyl compound are bonded via a diisocyanate compound.

However, in this case as well, in addition to the use of a catalyst, typically an organotin compound, to promote the reaction, the hydroxyl groups of the polymer and the hydroxyl groups of the unsaturated compound, and the isocyanate groups of one of the diisocyanate compounds and the isocyanate group of the other It is difficult to selectively react each of the groups, and in order to increase the selectivity of the reaction, reactions must be carried out in a plurality of steps sequentially, which has the disadvantage of complicating production.

As a result of intensive research to solve the drawbacks of such conventionally known methods, the present inventors discovered that the free carboxylic acid groups in a polymer containing free carboxylic acid groups and the aziridine groups in a specific unsaturated aziridine compound were The present invention was completed by discovering that a reactive polymer can be obtained by reacting at a specific ratio.

Therefore, it is an object of the present invention to provide a reactive polymer having a reactive group "that can cause or participate in a radical reaction" and a method for producing the same.

That is, the present invention comprises a polymer (A) containing free carboxylic acid groups in an acid equivalent ratio of 0.01 to 5 milliequivalents/g and an unsaturated aziridine compound (B) represented by the following general formula.
and 0.05 to 0.05 to 1.0 mol of the unsaturated aziridine compound (B) to 1.0 mol of free carboxylic acid groups of the polymer (A).
The present invention relates to a method for producing a reactive polymer, characterized in that the reaction is carried out at a ratio in the range of 1.2 moles.

(Note) General formula (However, in the formula, R ₁ is hydrogen or a methyl group,
_R2 to _R5 are selected from the group consisting of hydrogen and an alkyl group having 1 to 4 carbon atoms, and may be the same or different. ) The polymer (A) containing free carboxylic acid groups used in the present invention is a polymer containing free carboxylic acid groups at an acid equivalent ratio of 0.01 to 5 meq/g. Such polymers (A) include acrylic acid,
A single or a mixture of polymerizable monomers containing free carboxylic acid groups such as methacrylic acid, crotonic acid, itaconic acid, maleic acid, and fumaric acid, and an unsaturated monomer copolymerizable with these monomers. Copolymers obtained by polymerizing according to conventionally known methods; homopolymers or copolymers obtained by polymerizing unsaturated monomers that produce carboxyl groups by hydrolyzing according to conventionally known methods; Polymers containing free carboxylic acid groups; Polymers containing free carboxylic acid groups introduced using known polymerization initiators, chain transfer agents, polymerization terminators, etc. containing free carboxylic acid groups; Anhydrous Polyhydric carboxylic acids such as phthalic acid, maleic anhydride, and terephthalic acid, and ethylene glycol,
Polyester polycarboxylic acid obtained by polycondensation reaction with polyhydric alcohol such as propylene glycol; Alkyd polycarboxylic acid obtained by polycondensation reaction between glycerin and polyhydric carboxylic acid or fatty acid; Maleated petroleum resin; carboxylic acid group Examples include starch and cellulose containing polyethylene glycol dicarboxylic acid.

Examples of unsaturated monomers copolymerizable with the free carboxylic acid group-containing polymerizable monomers include methyl esters, ethyl esters, propyl esters, butyl esters of unsaturated monobasic acids such as acrylic acid and methacrylic acid; Esters such as 2-ethylhexyl ester, hydroxyethyl ester, and hydroxypropyl ester; acrylamide, methacrylamide, their N-substituted acrylamides and methacrylamide; methyl alcohol and ethyl alcohol of unsaturated dibasic acids such as maleic acid and itaconic acid , mono- and diesters with lower alkyl alcohols such as propyl alcohol; one or more unsaturated monomers such as acrylonitrile, methacrylonitrile, vinyl acetate, vinyl chloride, vinylidene chloride, styrene, ethylene, butadiene, etc. Can be used.

If the amount of free carboxylic acid groups contained in the polymer (A) is less than 0.01 meq/g, the polymer
A substantially effective amount of reactive unsaturated groups cannot be introduced into (A). Moreover, when it is more than 5 milliequivalents/g, the cured product derived from the resulting reactive polymer becomes extremely hard and brittle, which is not preferable.

Unsaturated aziridine compound (B) used in the present invention
is represented by the above general formula. Such unsaturated aziridine compounds (B) include N-acryloylaziridine, N-acryloyl-2-
Methylaziridine, N-acryloyl-2,2-
Dimethylaziridine, N-acryloyl-2-ethylaziridine, N-methacryloylaziridine, N-methacryloyl-2-methylaziridine, N-methacryloyl-2,2-dimethylaziridine, N-methacryloyl-2-ethylaziridine, etc. One or more of these can be effectively used. Among them, preferred are N-acryloylaziridine and N-methacryloylaziridine.

In the present invention, the unsaturated aziridine compound (B) is added to 1.0 mol of free carboxylic acid groups of the polymer (A).
It must be reacted in proportions ranging from 0.05 to 1.2 mol. If the amount of the unsaturated aziridine compound (B) is less than 0.05 mol per 1.0 mol of the free carboxylic acid group, the concentration of reactive unsaturated groups in the resulting reactive polymer will be low, which is not practical. Further, when the unsaturated aziridine compound (B) is reacted in an amount exceeding 1.2 mol with respect to 1.0 mol of the free carboxylic acid group,
Ring-opening polymerization reactions between aziridine compounds increase, making it impossible to obtain a useful reactive polymer.

In the production method of the present invention, it is more preferable that the polymer (A)
This is the case when the unsaturated aziridine compound (B) is reacted in a ratio ranging from 0.05 to 1.0 mol per 1.0 mol of free carboxylic acid groups.

In the production method of the present invention, the amide esterification reaction proceeds even at room temperature, that is, at a low temperature of about 20°C, but if economic efficiency such as shortening of production time is considered, the reaction can be carried out at a temperature of 40°C or higher. It is preferable to do this. The upper limit temperature of the reaction cannot be specified depending on the polymer (A) used, the type and amount of the polymerization inhibitor, the oxygen concentration of the reaction atmosphere, etc., but the Considering the stability of the group and the stability and coloring of the resulting reactive polymer,
The temperature is 150℃. Therefore, the preferred temperature range is 20℃
~150℃, more preferred temperature range is 50℃
~130℃.

During the reaction, if the fluidity of the polymer (A) is low or in order to facilitate the addition of the unsaturated aziridine compound (B) to the reaction system, the polymer (A) and/or the unsaturated aziridine compound (B) may be added to the reaction system. ) is a preferred method. The diluent is a compound capable of dissolving or dispersing both the polymer (A) and the unsaturated aziridine compound (B). Examples include aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene, dioxane, methyl ethyl ketone, ethyl acetate, cellosolves, carbitols, alcohols, and water. In addition, styrene, acrylonitrile, vinyl acetate, acrylic ester,
Polymerizable monomers such as methacrylic acid esters can also be used.

Furthermore, in order to carry out the present invention more safely and obtain a reactive polymer, introducing oxygen into the reaction system,
and hydroquinone, methoquinone, etc. before or after the reaction to ensure long-term stability of the reactive polymer.
It is also a preferred embodiment to add a known polymerization inhibitor such as phenothiazine.

The reactive polymer thus obtained by carrying out the present invention can be used as a chain lengthening agent, blocking agent, grafting agent, crosslinking agent, etc. in various fields such as adhesives, coating agents, fillers, and molding materials. It is used as a material and exhibits excellent performance.

Hereinafter, the present invention will be explained in more detail with reference to Examples. Note that "parts" in the examples represent parts by weight.

Example 1 NISSO-PB・C-1000 (free carboxylic acid group content 1.48 meq/g, liquid polybutadiene dicarboxylic acid, manufactured by Nippon Soda) was placed in a reactor equipped with a stirrer, a cooler, a thermometer, and a dropping funnel. Put 250 copies,
The temperature was adjusted to 60°C while stirring.

Next, 41.0 parts of N-methacryloylaziridine was continuously added dropwise from the dropping funnel over a period of 3 hours, and the mixture was further kept at the same temperature for 3 hours and cooled to obtain a product. As a result of carboxylic acid group concentration analysis by titration, this product was found to contain 95% of the free carboxylic acid groups in the raw material.
was liquid polybutadiene which had been converted into unsaturated groups.

Example 2 250 parts each of NISSO-PB・C-1000 and toluene were placed in a reactor equipped with a stirrer, a cooler, a thermometer, and a dropping funnel, and the contents were dissolved under stirring to a temperature of 70
The temperature was adjusted to ℃.

Next, 35.9 parts of N-acryloyl aziridine was continuously added dropwise from the dropping funnel over 3 hours at the same temperature, and the temperature was maintained for another 3 hours. After cooling, the contents were taken out and the toluene was removed using an evaporator to remove the product. Obtained. As a result of carboxylic acid group concentration analysis by titration, this product was liquid polybutadiene in which 93% of the free carboxylic acid groups in the raw material had been converted to unsaturated groups.

Example 3 In a reactor equipped with a stirrer, a condenser, a thermometer, and a dropping funnel, the monomer composition obtained by a conventional method was butyl acrylate/methacrylic acid = 90/10.
A 50% by weight toluene solution of a copolymer with a free carboxylic acid group content of 1.16 meq/g (weight ratio) 500
of the mixture, and the internal temperature was adjusted to 90°C while stirring. Next, 64.4 parts of a 50% toluene solution of N-methacryloylaziridine was added from the dropping funnel to 32.2 parts in the first hour.
1 part, and the remaining 32.2 parts were continuously added dropwise over the next 2 hours, and the mixture was kept at the same temperature for an additional 2 hours to cool. Toluene was removed from the contents taken out using an evaporator to obtain a product. The product is
As a result of analysis of the concentration of unsaturated groups by HBr method, it was found that it contained 1.1 mmol/g of reactive unsaturated groups.

Example 4 In a reactor equipped with a stirrer, a condenser, a thermometer and a dropping funnel, an alkyd resin having a free carboxylic acid group content of 1.0 meq/g obtained from glycerin, phthalic anhydride and fatty acids by a conventional method was introduced. 500 parts of a xylene solution containing 40% by weight was added, and the contents were adjusted to 90°C while stirring. Then from the dropping funnel
15.5 parts of N-methacryloylaziridine was continuously added dropwise over 1.5 hours, and the mixture was kept at the same temperature for 4 hours to obtain a product containing 41% by weight of resin after cooling. Analysis of the carboxylic acid group concentration by titration of the resin content in the product revealed that 47% of the free carboxylic acid groups in the raw material had been converted to reactive unsaturated groups.

Example 5 In a reactor equipped with a stirrer, a condenser, a thermometer and a dropping funnel, the amount of free carboxylic acid groups was 0.71 meq/
85 parts of Nipol-1072B (carboxylated, acrylonitrile-butadiene rubber, manufactured by Nippon Zeon),
415 parts of methyl methacrylate and phenothiazine
After adding 0.001 part and allowing the rubber to swell overnight,
The rubber was dissolved at 90°C with stirring. Thereafter, the contents were adjusted to the same temperature, and 33.5 parts of a methyl methacrylate solution containing 10% by weight of N-methacryloylaziridine was added to the dropping funnel, 20.0 parts in the first hour, and the remaining 13.5 parts in the next 2 hours. Drip,
The mixture was further kept at the same temperature for 3 hours and cooled to obtain a methyl methacrylate solution having a resin content of 17.3%.
Analysis of the carboxylic acid group concentration by titration of the resin content in the solution revealed that approximately 45% of the free carboxylic acid groups in the raw rubber had been converted to reactive unsaturated groups.

Example 6 A monomer composition obtained by a known emulsion polymerization method in a reactor equipped with a stirrer, a cooler, a thermometer, and a dropping funnel was acrylonitrile/butyl acrylate/acrylic acid = 13.5/81.5/5.0 (by weight). 200 parts of a 50% by weight aqueous dispersion of a resin with a free carboxylic acid group content of 0.69 meq/g (ratio) was added, and the contents were heated at 90°C while stirring.
It was adjusted to

Next, 3.8 parts of N-methacryloylaziridine was continuously added dropwise from the dropping funnel over 1.5 hours, kept at the same temperature for 4 hours, and cooled to obtain an aqueous dispersion containing 51% by weight of resin. As a result of carboxylic acid group concentration analysis of the resin content by titration, approximately 49% of the free carboxylic acid groups in the raw material were converted to reactive unsaturated groups.

Claims (1)

[Scope of Claims] 1. A polymer (A) containing free carboxylic acid groups in an acid equivalent ratio of 0.01 to 5 milliequivalents/g and an unsaturated aziridine compound (B) represented by the following general formula;
1. A method for producing a reactive polymer, which comprises reacting the unsaturated aziridine compound (B) at a ratio of 0.05 to 1.2 moles with respect to 1.0 moles of carboxylic acid groups of (A). (Note) General formula (However, in the formula, R ₁ is hydrogen or a methyl group,
_R2 to _R5 are selected from the group consisting of hydrogen and an alkyl group having 1 to 4 carbon atoms, and may be the same or different. ).