JPS59221304A - Preparation of reactive polymer - Google Patents

Abstract

PURPOSE:To obtain a novel reactive polymer useful as a chain extender, blocking agent, etc., having improved performances by a simple process easily, by reacting a polymer containing a free carboxylic acid group with a specific unsaturated aziridine compound in a specified ration. CONSTITUTION:(A) A polymer (e.g., copolymer consisting of polymerizable monomer containing free carboxylic acid group, such as acrylic acid, etc.) containing 0,01-5miliequivalent/g calculated as acid equivalent of free carboxylic acid group is reacted with (B) an unsaturated aziridine compound [preferably 2-(1-aziridinyl) ethyl methacrylate, etc. ] shown by the formula (R1 is H, or methyl; R2-R5 are H, or 1-4C alkyl) in such a way that the amount of the component B is 0.05-1mol based on 1mol free carboxylic acid group of the component A, to give the desired polymer. The reaction is carried out preferably at 40-110 deg.C.

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.

As used herein, the term "reactive polymer" refers to a polymer capable of causing or participating in a so-called "radical reaction" under the action of heat, ultraviolet light, electron beams, free radical generating agents, etc. Refers to a polymer having a reactive group.Several proposals have been made for the production of such reactive polymers.One of them utilizes the so-called esterification reaction, for example, A method utilizing a reaction between a polymer containing a carboxylic acid group and an unsaturated hydroxyl compound or an unsaturated glycidyl compound, or a reaction between a polymer containing a hydroxyl group or a glycidyl group and an unsaturated carboxylic acid compound is known. Yes. 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, methods such as adding a large amount of polymerization inhibitor to the reaction system, introducing oxygen, and easing the reaction conditions by using an esterification reaction catalyst are known, but the resulting reaction Polymers often contain excessive amounts of polymerization inhibitors and catalyst residues, which can cause coloring and reaction delays depending on the intended use, 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 group of the polymer and the hydroxyl group of the unsaturated compound, and the isocyanate group 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, a plurality of reaction steps must be performed sequentially, which has the disadvantage of complicating production.

As a result of intensive research to solve the drawbacks of certain 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 The present invention was completed based on the finding that a reactive polymer can be obtained by reacting the following in a specific ratio.

Accordingly, it is an object of the present invention to provide a reactive polymer having a reactive group capable of causing or participating in a radical reaction, and a method for producing the same.

That is, the present invention combines an unsaturated aziridine compound (B) represented by the following general formula into a polymer containing free carboxylic acid groups at an acid equivalent ratio of 0.01 to 5 mm/t/g. A process for producing a reactive polymer, which comprises reacting the unsaturated aziridine compound (B) at a ratio of 0.05 to 1.0 mol per 1.0 mol of free carboxylic acid groups of Al. It is.

(Note) 1 6 (In the formula, l't+ is hydrogen or a methyl group, R
g 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 having ylI free carboxylic acid groups at an acid equivalent ratio of 0.01 to 5 mm/t/g. Such polymers (Al includes free carboxylic acid group-containing polymerizable monomers such as acrylic acid, methacrylic acid, phosphoric acid, itaconic acid, maleic acid, fumaric acid, etc.) or mixtures thereof; A copolymer obtained by polymerizing a copolymerizable unsaturated monomer with a copolymerizable unsaturated monomer according to a conventionally known method; The obtained homopolymer or
5- A polymer obtained by hydrolyzing a copolymer to contain a free carboxylic acid group; a free carboxylic acid group introduced using a known polymerization initiator, chain transfer agent, polymerization terminator, etc. containing a free carboxylic acid group Polymers containing acid groups; polyesters obtained by the polycondensation reaction of polycarboxylic acids such as phthalic anhydride, maleic anhydride, and terephthalic acid with polyhydric alcohols such as ethylene glycol and propylene glycol; Examples include alkyd polycarboxylic acids obtained by polycondensation reactions with polycarboxylic acids and fatty acids; maleated petroleum resins; starches and celluloses containing carboxylic acid groups; polyethylene glycol dicarboxylic acids.

Examples of unsaturated monomers copolymerizable with the free carboxylic acid group-containing polymerizable monomers include methyl esters, ethyl esters of unsaturated basic acids such as acrylic acid and methacrylic acid,
Esters such as propyl ester, butyl ester, 2-ethylhexyl ester, hydroxyethyl ester, human tetraxypropyl ester; acrylamide, methacryl 6-amide, their N-[converted acrylamide and methacrylamide]; maleic acid, itaconic acid, etc. Mono- and diesters of unsaturated dibasic acids with lower alkyl alcohols such as methyl alcohol, ethyl alcohol, and propyl alcohol; acrylonitrile, methacrylonitrile, vinyl acetate, vinyl chloride im vinylidene, styrene,
One or more unsaturated monomers such as ethylene and phtadiene can be used.

The amount of free carboxylic acid groups contained in the polymer (A) is 0
．． 01 Mi! If it is less than J equivalent/g, the polymer (
It is not possible to introduce a substantially effective amount of reactive unsaturated groups into A). In addition, if it is more than 5 milliequivalents/g,
The cured product derived from the resulting reactive polymer becomes extremely hard and brittle, which is undesirable.

Unsaturated aziridine compound (B
) is represented by the above general formula.

Such an unsaturated aziridine compound (as Bl, 2
-(1-aziridinyl)ethyl acrylate, 2-(1
-aziridinyl)ethyl methacrylate, 2-(1-(
2-methylaziridinyl)]ethyl methacrylate 2-
(1-(2-methylaziridinyl)]ethyl methacrylate, 2-(1-(2゜2-dimethylaziridinyl)
] Ethyl methacrylate 2- (1-(2,2-dimethylaziridinyl)) Ethyl methacrylate, 2-(1-
(2-ethylaziridinyl)]ethyl methacrylate 2
-[1-(2-ethylaziridinyl)]ethyl methacrylate, etc., and 1 m or 2 or more of these can be effectively used. Especially preferred tight MZ
-11”).

The method for producing the reactive polymer in the present invention is based on an aminoesterification reaction between the free carboxylic acid group of the polymer (A) and the aziridine group of the unsaturated aziridine compound (B). but,
In this reaction system, it is predicted that not only such an aminoesterification reaction but also a ring-opening polymerization reaction between aziridine groups will proceed competitively. Simultaneous ring-opening polymerization reactions between aziridine groups reduce the rate of addition of the unsaturated aziridine compound CB) to the free carboxylic acid groups of the polymer (A), which in turn leads to a decrease in the rate of addition of the unsaturated aziridine compound CB) to the free carboxylic acid groups of the polymer (A), which in turn leads to a decrease in the rate of addition of the unsaturated aziridine compound CB) to the free carboxylic acid groups of the polymer (A). The yield of reactive polymer is significantly lower.

The present inventors conducted studies to solve this problem, and the present invention was achieved as a result.

In the present invention, free carboxylic acid group 1 of aggregate (A)
．． 0.0 mole of unsaturated aziridine compound (B).
It must be reacted in proportions ranging from 0.05 to 1.0 mol. Unsaturated aziridine compound (if Bl is less than 005 mol per 1.0 mol of the free carboxylic acid group,
The concentration of reactive polymer in the resulting reactive polymer is low;
Not practical. Furthermore, when an unsaturated aziridine compound (Bl) is reacted in an amount exceeding equimolar to the free carboxylic acid group, the ring-opening polymerization reaction between aziridine rings increases in parallel with the aminoesterification reaction, as described above. , a useful reactive polymer cannot be obtained. In the production method of the present invention, a more preferable method is when the unsaturated aziridine compound (B) is This is the case when the reaction is carried out in a ratio ranging from 0.1 to 0.5 mol.

In the production method of the present invention, the aminoesterification reaction proceeds even at room temperature, that is, at a low temperature of about 20°C, but at about 40°C.
In the following, a ring-opening reaction between aziridine groups is also observed.

Therefore, in order to prioritize the aminoesterification reaction in the production method of the present invention, it is preferable to carry out the reaction at a temperature of about 40°C or higher. The upper limit temperature of the reaction depends on the polymer used,
Although it cannot be determined depending on the type and amount of the polymerization inhibitor and the oxygen concentration of the reaction atmosphere, the stability of the polymerizable unsaturated group of the unsaturated aziridine compound (B) and the stability and coloring of the resulting reactive polymer are important. If you also take into account the temperature, it is 150°C. Therefore, the preferred temperature range is 40 to 150°C, more preferably 40 to 110°C.

During the reaction, when the fluidity of the polymer (A) is low or in order to facilitate the addition of the unsaturated aziridine compound (B) added to the reaction system, the polymer (A) and/or the aziridine compound described in Section 10 below. Applying a diluent to (B) is a preferred method. The diluent is a polymerizable compound capable of dissolving or dispersing both Al and the unsaturated aziridine compound (B). Examples include aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene, and dioxin. Polymerizable monomers such as styrene, acrylonitrile, vinyl acetate, acrylic esters, and methacrylic esters can also be used.

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

The reactive polymer obtained by carrying out the present invention in this way is
It is used as a chain lengthening agent, blocking agent, grafting agent, and crosslinking agent in various fields such as adhesives, coatings, fillers, and molding materials, and exhibits excellent performance.

Hereinafter, the present invention will be explained in more detail with reference to Examples.

In the examples, "1 part" refers to parts by weight.

Example 1 A reactor equipped with a stirrer, a condenser, a thermometer and a dropping funnel was charged with Nl5SO-PB-C-1000 (free carboxylic acid group content 1.48 mm!J equivalent/g1 liquid polybutadiene).
Add 250 parts of dicarboxylic acid (manufactured by Nippon Soda) and stir for 6 hours.
The temperature was adjusted to 0°C. Next, 31.6 parts of “
Chemitite MZ-11'' (2-(1-aziridinyl)ethyl methacrylate, Nippon Shokubai Kagaku M) was continuously added dropwise over 3 hours, kept at the same temperature for another 3 hours, and cooled to obtain a product. As a result of carboxylic acid group concentration analysis by titration, 48% of free carboxylic acid groups in the raw material
It was a liquid polybutadiene that had been converted into unsaturated groups.

Example 2 Two volumes each of NlSO-PB-C-1000 and toluene were added to a reactor equipped with a stirrer, a condenser, a thermometer, and a dropping funnel.
50 parts were added, the contents were dissolved under stirring, and the temperature was adjusted to 70°C. Then, at the same temperature, 26.0 parts of 2-(
1-Aziridinyl)ethyl acrylate was continuously added dropwise over 3 hours, and the mixture was kept at the same temperature for 3 hours. After cooling, the contents were taken out and toluene was removed using an evaporator to obtain a product. As a result of carboxylic acid group concentration analysis by titration, this product was found to contain 49% of the free carboxylic acid groups in the raw material.
It was a liquid polybutadiene which had been converted into an unsaturated group.

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 (weight ratio) containing free carboxylic acid groups. The amount is 1.16 mi! 500 parts of a 50% by weight toluene solution of a copolymer of J equivalent/g was added, and the internal temperature was adjusted to 90° C. while stirring. Then from the dropping funnel “
22.5 parts of 45 parts of a 50% toluene solution of Chemitite MZ-11" was added in the first hour, and the remaining 2 parts in the next 2 hours.
After continuously dropping 25 parts of each mixture, the mixture was kept at the same temperature for 2 hours and cooled.

Toluene was removed from the contents taken out using an evaporator to obtain a product. As a result of unsaturation concentration analysis using the HBr method, the product contained 0.51 mmol/reactive unsaturated group.
It contained g.

Example 4 Free carboxylic acid group contents obtained from glycerin, phthalic anhydride and fatty acids in a conventional manner in a reactor equipped with a stirrer, a condenser, a thermometer and a dropping funnel are i, o mi! J
500 parts of a xylene solution containing 40% by weight of alkyd resin (equivalent/g) was added, and the contents were adjusted to 70° C. with stirring.

Next, 6.4 parts of "Chemitai" MZ-1 was added from the dropping funnel.
1" was continuously added dropwise over 1.5 hours, and kept at roughly the same temperature for 4 hours. After cooling, a product containing 41% by weight of resin was obtained. The resin content in the product was determined by titration of the carboxylic acid. As a result of group concentration analysis, 2 of the free carboxylic acid groups in the raw material
0% was converted to reactive unsaturated groups.

Example 5 A 14-meter reactor equipped with a stirrer, a condenser, a thermometer, and a dropping funnel had a free carboxylic acid group content of 0.714 st lung/g.
N1pol-'1072B (carboxylated acrylonitrile-butazine rubber, manufactured by Nippon Zeon) 85L 415 parts of methyl methacrylate and 0.00 phenothiazine
After charging 1 part and allowing the rubber to swell day and night, under stirring, 9
The rubber was dissolved at 0°C. Thereafter, the contents were adjusted to 70'C, and 46.8 parts of a methyl methacrylate solution containing 10% by weight of "Chemitite MZ-11" was added from the dropping funnel to 23.4 parts in the first hour, and the remaining amount in the next 2 hours. 23.4
Each portion was continuously added dropwise, kept at the same temperature for 3 hours, and cooled to obtain a methyl methacrylate solution having a resin content of 16.5%. Regarding the resin content in the solution, the carboxylic acid group concentration analysis by titration revealed that approximately 45% of the free carboxylic acid groups in the raw rubber had been converted to reactive unsaturated groups.

Example 6 A reactor equipped with a stirrer, a cooler, a thermometer, and a dropping funnel was prepared using a known emulsion polymerization method, and the monomer composition was acrylonitrile/butyl acrylate/acrylic acid=13.
5/81.5 200 parts of a 50 weight 5 aqueous dispersion of a resin having a free katonic acid group content of 0.69 mmIJ equivalent/g (weight ratio) was added, and the contents were heated to 70° C. while stirring. Adjusted to. Next, 5.4 parts of "Chemitite MZ" was added from the dropping funnel.
-11'' was continuously added dropwise 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.The resin content was determined by titration of carboxylic acid. As a result of group concentration analysis, approximately 37% of the free carboxylic acid groups in the raw material were converted to reactive unsaturated groups.

Claims (1)

[Claims] 1. 0.01 to 5 milliliter of free carboxylic acid group
/g of the unsaturated aziridine compound (A) and the unsaturated aziridine compound (B) represented by the following general formula per 1.0 mol of free carboxylic acid groups in the polymer. 1. A method for producing a reactive polymer, which comprises reacting compound (B) at a ratio ranging from 0.05 to 1.0 mol. (Note) (In the formula, R+ is hydrogen or a methyl group, and R1-
R5 is selected from the group consisting of hydrogen and an alkyl group having 1 to 4 carbon atoms, and may be the same or different. )