JPS6197304A - Production of reactive polymer - Google Patents

Abstract

PURPOSE:To obtain efficiently the title polymer which has excellent water resistance and does not discolor even under a severe condition, by reacting a specified polymer with an unsaturated aziridine compound and compound such as a monoisocyanate. CONSTITUTION:A polymer (A) having 0.01-5meq/g (acid equivalent) of free carboxyl groups is reacted with 0.05-1.2mol, per mol of the carboxyl groups in component A, of an unsaturated aziridiene compound (B) having one basic aziridine group and at least one radical-polymerizable unsaturated group [e.g., compound of the formula (wherein R1-4 are each H, a 1-4C alkyl and R5 is H or CH3)] and 0.8-1.2mol, per mol of component B, at least one compound (C) selected from among a mono(thio)isocyanate [e.g., methyl (thio)isocyanate] and a ketene (dimer) [e.g., methyl ketene (dimer)] 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 carboxyl group with an aziridine compound having an unsaturated group.

As used herein, the term "reactive polymer" refers to a reactive 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. means a polymer having groups. Conventionally, 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 carboxyl 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 with an unsaturated glycidyl compound. A method using a reaction with an unsaturated carboxylic acid compound is known.

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 one 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 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 groups of the polymer and the unsaturated compound □i'
It is difficult to selectively react each of the hydroxyl groups of the diincyanate compound and the isocyanate groups of the other side, and in order to increase the selectivity of the reaction, it is necessary to react in multiple steps sequentially. This method has the disadvantage of complicating manufacturing process.

The present inventors investigated to solve the drawbacks of such conventionally known methods, and as a result, the free carboxyl groups in the polymer containing free carboxyl groups and a specific unsaturated aziridine compound (unsaturated basic aziridine compound) It was discovered that a reactive polymer could be obtained by reacting the aziridine groups in the compound, and an application was filed earlier.

However, in the esterification reaction between the free carboxyl group in the free carboxyl group-containing polymer and the aziridine group in the unsaturated basic aziridine compound, the carboxyl group and the aziridine group once form a salt in the reaction process. Then, as the esterification reaction progresses, basic amine groups are generated, so unless an acid such as hydrochloric acid or acetic acid is separately added, the generated basic amino groups will form an inner salt with other carboxyl groups in the polymer. However, as a result of the esterification reaction from this inner salt not proceeding, the theoretical value of the esterification reaction remains at 50 degrees. Therefore, the reactive polymer obtained by this reaction has an amine salt of carboxylic acid in the polymer, which may cause discoloration of the cured product or problems with water resistance under harsh conditions depending on the application. gender is predicted.

The present invention solves the drawbacks of conventionally known methods and also eliminates at once the above-mentioned disadvantages related to the reactive polymer obtained by reacting a free carboxyl group-containing polymer with an unsaturated basic aziridine compound. .

That is, the present invention comprises a polymer (4) containing free carboxyl groups at an acid equivalent ratio of 0.01 to 5 milliequivalents/g, one basic aziridine group in one molecule, and at least one radically polymerizable an unsaturated basic aziridine compound (B) having an unsaturated group; and at least one compound selected from the group consisting of monoisocyanates, monothioisocyanates, ketenes, and ketene dimers (reacting C1 with The present invention relates to a method for producing characteristic reactive polymers.

The free carboxyl group-containing polymer (3) used in the present invention has a weight of 0.01 to 5 meq/g. Preferably it is a polymer having free carboxyl groups in an acid equivalent proportion of 0.02 to 3 meq/g. Such polymers (
As for 3), for example, free carboxyl group-containing polymerizable monomers such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, etc. alone or in mixtures thereof and copolymerizable with these monomers are used. A copolymer obtained by polymerizing an unsaturated monomer according to a conventionally known method; a homopolymer obtained by polymerizing an unsaturated monomer that produces a carboxyl group by hydrolysis according to a conventionally known method; A polymer that contains free carboxyl groups by hydrolyzing a copolymer; contains free carboxyl groups that are introduced using known polymerization initiators, chain transfer agents, polymerization terminators, etc. that contain free carboxyl groups. Examples include polymers.

Examples of unsaturated monomers copolymerizable with the free carboxyl group-containing polymerizable monomers include methyl esters, ethyl esters, flobyl esters, and methyl esters of unsaturated basic acids such as acrylic acid and methacrylic acid. , 2-ethylhexyl ester, hydroxyethyl ester, hydroxypropyl ester and other esters; acrylamide, methacrylamide, their N-substituted acrylamides and methacrylamide; methyl alcohol and ethyl of unsaturated dibasic acids such as maleic acid and itaconic acid. Alcohol, mono- and diesters with lower alkyl alcohols such as flobyl alcohol; acrylonitrile, methacrylaterile, vinyl acetate, vinyl chloride, vinylidene chloride,
Examples include unsaturated monomers such as styrene, ethylene, butadiene, and one or more of these can be used.

Other examples of the polymer (3) include polyhydric carboxylic acids such as phthalic anhydride, maleic anhydride, terephthalic acid, trimellitic acid, and pyromellitic acid, and polyhydric alcohols such as ethylene glycol and fluoropylene gellicol. Polyester polycarboxylic acid obtained by the condensation reaction of polyester polycarboxylic acid; Alkyd polycarboxylic acid obtained by the condensation reaction of polyhydric alcohol such as glycerin with polyhydric carboxylic acid or fatty acid; Polyamine and polyhydric carboxylic acid such as ethylenediamine and phenylenediamine Examples include polyamide polycarboxylic acid obtained by condensation polymerization with polyamide, maleated petroleum resin, starch and cellulose containing carboxyl groups, and polyethylene glycol dicarboxylic acid.

When the amount of free carboxyl groups contained in the polymer (3) is less than 0.01 mmIJ equivalent/1, the polymer (3)
3) It is not possible to introduce a substantially effective amount of reactive unsaturated groups. In addition, if it exceeds 5 mm/g, the polymerization system may gel depending on the introduction of the reactive unsaturated group, making it difficult to stably produce a reactive polymer, and furthermore, the resulting reaction This is not preferred because the cured product derived from the polymer is limited to being hard and brittle.

The unsaturated basic aziridine compound (Bl) used in the present invention is an unsaturated basic aziridine compound (Bl) among unsaturated aziridine compounds having one aziridine group and at least one radically polymerizable unsaturated group in one molecule. The nitrogen atom of the aziridine group is basic.

A typical unsaturated aziridine compound has the general formula (1
) (However, in the formula, A is CH, =CH-1CH2=C(C
H3) is one group selected from the group consisting of - and CH, =CH-CH, -, m is an integer from 1 to 3,
R is 0 or 1, and R1 to R4 are hydrogen and 1 to
Q is a bonding group selected from the group consisting of alkyl groups having 4 carbon atoms, which may be the same or different, and has a (77L+1) valence,
Hydrocarbon bond, carboxylic acid ester bond, sulfonic acid ester bond, ether bond, urethane bond, urea bond,
It may contain an amide bond, a thioamide bond, a carbonyl group, a sulfonyl group, etc. ). A typical example of the unsaturated basic aziridine compound (B) is a compound having the general formula (■).

(However, in the formula, R1 to R4 are as described above, and R3 is hydrogen or a methyl group.) Among these, 2-(1-aziridinyl)ethyl methacrylate is preferred.

Among the unsaturated aziridine compounds represented by the general formula (11), specific examples of unsaturated basic aziridine compounds (Bl) are as follows.

N.J.C.H.

CH,=CH-C00-CH,CH! -NJCH.

CH,=C(CH,)-COO-CH,CH,-<C,
H.

CH,=CH-COO-CH,CH,-JC,H.

CH,=C(CH3) -COO-CH,CH,-NC
H,=C)(-COO-CH(CHl)-C)I,-N
, 1CHz=C(CHs)-000-CH(CHs)-
CHt -<CH, =CH-Coo+CH, CH, 0 production, CH, -N-cut CH, =C(CH,)-Coo+CM
2CH, O CH, CH, -<CH2=CH-COO+
cH2CH204CO-CH2C1-12-u3CH,
=C(CH,)-COO+CH,CH,0揄Co-CH
Box-NgCH, -CH,0-CO-CH=CH.

CM -CH, 0-COCH, -CH, -N/:jiC
H2-CH, 0-Co-CH=CH.

CH, -CH, 0-Co-C(CH3)=CH.

CH-CH, 0-COCH, -0H2-n3C12-C
H,0-Co-C(CH3)=CH.

In the present invention, the unsaturated basic aziridine compound (B) is reacted at a ratio of 0.05 to 1.2 mol per 1.0 mol of free carboxyl groups of the free carboxyl group-containing polymer. @Japanese basic aziridine compound (B)
When the amount is less than 0.05 mol per 1.0 mol of the free carboxyl group, the concentration of reactive unsaturated groups in the resulting reactive polymer is too low to be practical. On the other hand, if the amount of the unsaturated basic aziridine compound +B) exceeds 1.2 mol per 1.0 mol of the free carboxyl group, ring-opening polymerization between aziridine rings increases in parallel with the esterification reaction, which is useful. It is difficult to obtain reactive polymers. Therefore, in a more preferred embodiment of the production method of the present invention, the amount of unsaturated basic aziridine compound iB) is 0.05 to 1.2 mol, more preferably 0. It is 1 to 1.0 mol.

As mentioned above, an object of the present invention is to take advantage of the advantage of the unsaturated basic aziridine compound (B) in its favorable reactivity with the polymer (A), and to utilize the basic amine group generated by the reaction with the polymer. The purpose is to provide a method to improve the resulting shortcomings.

When reacting the free carboxyl group-containing polymer (3) with the unsaturated basic aziridine compound (B).

This object is achieved by the combined use of at least one compound (C) selected from the group consisting of monoisocyanates, monothioisocyanates, ketenes and ketene dimers.

This compound (C1 is an unsaturated basic aziridine compound (
B) 0.8 to 1.2 mol per 1.0 mol, especially 0
．． It is preferred to carry out the reaction in a ratio ranging from 9 to 1.1 mol. The polymer matrix and the unsaturated basic aziridine compound (
If the compound (C) is used in combination with the reaction with B), the reaction rate of the former two is not reduced, and the basic amino group generated by the reaction of the former two reacts with the compound (C). As a result, the basic amino groups in the system are reduced or completely eliminated, so that the reaction between the free carboxyl groups in the polymer (4) and the aziridine groups of the unsaturated basic aziridine compound (B) proceeds without being inhibited. Furthermore, the coloring of the resulting reactive polymer is also significantly improved.

The compound (C) includes monoisocyanates R,
-NGO, monothioincyanates R', -NC8.

Ketenes R, R', c = c = o and ketene dimer -C-0 1 to 12, preferably 1 to 8 alkyl groups, cycloalkyl groups, phenyl groups; Hydrogen, an alkyl group having 1 to 8 carbon atoms, preferably 1 to 6 carbon atoms, a cycloalkyl group, and a phenyl group. ), preferably monoisocyanates and ketenes. Representative monoisocyanates include methyl isocyanate, ethyl isocyanate, propyl isocyanate, isopropylisocyanate, butyl isocyanate), 5ee-butyl isocyanate, octyl isocyanates, cyclohexyl isocyanate, phenyl isocyanate, and the like. Representative monothioisocyanates include methylthioisocyanate, ethylthioisocyanate, propylthioisocyanate, isopropylthioisocyanate, butylthioisocyanate,
These include 5ec-prolthioisocyanate, octylthioisocyanates, cyclohexylthioisocyanate, phenylthioisocyanate, and the like. Typical ketenes include ketene, methyl ketene, ethyl ketene, propyl ketene, butyl ketene, octyl ketene, dimethyl ketene, diethyl ketene, dipropyl ketene, dibutyl ketene, methyl ethyl ketene, methyl propyl ketene, cyclohexyl ketene, phenyl, ketene, etc. be. Typical ketene dimers include ketene dimer, methyl ketene dimer, ethyl ketene dimer, propyl ketene dimer, butyl ketene dimer, dimethyl ketene dimer,
These include dimethyl ketene dimer, methyl ethyl ketene timer, cyclohexyl ketene dimer, phenyl ketene dimer, etc.

The reaction in the present invention proceeds even at room temperature, ie, at a low temperature of about 20°C, but a ring-opening reaction between aziridine groups is observed at temperatures below 40°C. Therefore, in this case, it is preferable to carry out the reaction at a temperature of 40°C or higher. The upper limit temperature of the reaction cannot be specified depending on the type and amount of the polymerization inhibitor used in polymer (4)1, the oxygen concentration of the reactive atmosphere, etc.
Considering the stability of the polymerizable unsaturated group of No. 1 and the stability and coloring of the reactive polymer, the temperature is 150°C. Therefore, the preferred temperature range is 40'' to 110<0>C.

During the reaction, if the free carboxyl group-containing polymer (5) has low fluidity or to facilitate the addition of the unsaturated basic aziridine compound (Bl or compound (C)) to the reaction system, the polymer ( 4) and/or an unsaturated basic aziridine compound (Bl or -compound (C1'') is a preferred method. (B)
, is a compound capable of dissolving or dispersing the king of compound (C). Typical diluents C: Aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene; Ketones such as dioxane, methyl ethyl ketone, acetone, and methyl isobutyl ketone; Esters such as ethyl acetate and butyl acetate; Glycol ethers; Calpitols; alcohols; water, etc.

Furthermore, polymerizable monomers such as styrene, acrylonitrile, methacrylonitrile, ticrylamide, 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, oxygen may be introduced into the reaction system, and hydroquinone may be added before or after the reaction 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, coating materials, fillers, and molding materials, 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 A reactor equipped with a stirrer, a condenser, a thermometer and a dropping funnel was charged with NlSO-PB-C-1000 (free carboxyl group content 1.48 meq/I% liquid polybutadiene dicarboxylic acid, Japan). Add 250 parts of Soda (manufactured by Soda) and stir for 6 hours.
The temperature was adjusted to 0°C. Next: □ 5 from the dropping funnel
A mixture of 7.4 parts of "Chemitite MZ-11" (2-(1-aziridinyl)ethyl methacrylate, manufactured by Nippon Shokubai Chemical Co., Ltd.) and 31.5 parts of leupropylisocyanate was added to 1
The mixture was continuously added dropwise over a period of time, kept at the same temperature for 5 hours, and cooled to obtain a product. This product is the result of quantitative analysis of carboxyl groups and amine groups.

The raw material was liquid polybutadiene in which 98% of the free carboxyl groups were converted to unsaturated groups.

Comparative Example 1 A product was obtained in exactly the same manner as in Example 1, except that 31.5 parts of leupropyl isocyanate was not used in Example 1. As a result of unsaturated group concentration analysis, this product was liquid polybutadiene in which 47% of the free carboxyl groups in the raw material had been converted to unsaturated groups.

Example 2 The product was obtained in exactly the same manner as in Example 1, except that 31.5 parts of leupropyl isocyanate in Example 1 was replaced by 15.6 parts of stingy/dimer. As a result of unsaturated group concentration analysis, this product was a liquid polybutadiene in which 98% of the free carboxyl groups in the raw material were converted to unsaturated groups.

Example 3 A reactor equipped with a stirrer, a cooler, a thermometer, and a dropping funnel was prepared using a conventional method.The monomer composition was methyl methacrylate/butyl acrylate/methacrylic acid = 10/8.
50 weights of a copolymer with a free carboxyl group content of 1.16 milliequivalents/1 (weight ratio) 81)
500 parts of toluene solution was added, and the internal temperature was adjusted to 90° C. while stirring. Then from the dropping funnel 45 parts of 1 chem tie) M
A mixture of Z-11n and 36.3 parts of cyclohexyl isocyanate was added, kept at the same temperature for 3 hours, and then cooled. Toluene was removed from the contents taken out using an evaporator to obtain a product. As a result of analysis of the concentration of unsaturated groups by the HBr method, the product contained 1.11 mmol/I of reactive unsaturated groups.

Example 4 A reactor equipped with a stirrer, a condenser, a thermometer and a dropping funnel was charged with a free carboxyl group content of 0.71 mEq.
1/N1pol-1072B (carboxylated acrylonitrile-butadiene rubber.

After adding 85 parts (manufactured by Nippon Zeon), 100 parts of methyl methacrylate, and o and oor parts of phenothiazine to swell the rubber overnight, the rubber was dissolved at 90°C with stirring. Thereafter, the contents were adjusted to 70 DEG C., and a mixture of 7.4 parts of 1 Chemitite MZ-11'' and 4.1 parts of lupropyl incyanate was added from the dropping funnel, and the mixture was kept at the same temperature for 4 hours and then cooled.

As a result of carboxyl group concentration analysis of the resin content in the reaction solution, it was found that about 7% of the free carboxyl groups in the raw material rubber.
7 had been converted to reactive unsaturated groups.

Claims (1)

[Scope of Claims] 1. A polymer (A) containing free carboxyl groups at an acid equivalent ratio of 0.01 to 5 milliequivalents/g, and one basic aziridine group and at least one per molecule. Unsaturated basic aziridine compound having a radically polymerizable unsaturated group (
A method for producing a reactive polymer, which comprises reacting B) and at least one compound (C) selected from the group consisting of monoisocyanates, monothioisocyanates, ketenes, and ketene dimers. 2. The unsaturated basic aziridine compound (B) is 0.0 mole of free carboxyl group of the polymer (A).
5 to 1.2 mol and the unsaturated basic aziridine compound (
B) The amount of the compound (C) is 0.8 to 1.0 mole.
2. A method according to claim 1, wherein the ratio is in the range of 2 molar.