JPS6348882B2 - - 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 carboxyl 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 cause or participate in a so-called radical reaction" under the action of heat, ultraviolet light, electron beams, free radical generating agents, etc. 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, since the esterification reaction generally involves subjecting the reactants to harsh temperature conditions for a relatively long period of time, 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 and catalyst residues, which can cause coloration 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 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, a plurality of reaction steps must be performed sequentially, which has the disadvantage of complicating production. 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 polymer, 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 will soon form a salt during the reaction process. After formation, basic amino groups are generated as the esterification reaction progresses, so unless an acid such as hydrochloric acid or acetic acid is separately added, the generated basic amino groups will not form an inner salt with other carboxyl groups in the polymer. As a result, the esterification reaction from this inner salt does not proceed.
The esterification reaction remains at 50% of the theoretical value. 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 water resistance under severe conditions depending on the application. The risk of causing inconvenience is foreseen. 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 has a free carboxyl group of 0.01 to 5
A polymer (A) containing an acid equivalent ratio of milliequivalent/g and an unsaturated basic aziridine compound (B) having one basic aziridine group and at least one radically polymerizable unsaturated group in one molecule. ) and at least one compound (C) selected from the group consisting of monoisocyanates, monothioisocyanates, ketenes, and ketene dimers. It is. The polymer (A) containing free carboxyl groups used in the present invention has a weight of 0.01 to 5 milliequivalents/g,
Preferred are polymers having free carboxyl groups at an acid equivalent proportion of 0.02 to 3 meq/g. Such polymers (A) include, 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 these monomers. A copolymer obtained by polymerizing an unsaturated monomer copolymerizable with an unsaturated monomer according to a conventionally known method; A polymer obtained by hydrolyzing a homopolymer or copolymer containing free carboxyl groups; introduced using a known polymerization initiator, chain transfer agent, polymerization terminator, etc. containing free carboxyl groups. Examples include polymers containing free carboxyl groups. Examples of unsaturated monomers copolymerizable with the free carboxyl 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, hydroxypropyl ester; acrylamide,
Methacrylamide, their N-substituted acrylamides and methacrylamides; mono- and diesters of unsaturated dibasic acids such as maleic acid and itaconic acid with lower alkyl alcohols such as methyl alcohol, ethyl alcohol and propyl alcohol; acrylonitrile and methacrylamide; Examples include unsaturated monomers such as nitrile, vinyl acetate, vinyl chloride, vinylidene chloride, styrene, ethylene, butadiene, and one or more of these can be used. Other examples of the polymer (A) include phthalic anhydride, maleic anhydride, terephthalic acid, trimellitic acid,
Polyester polycarboxylic acid obtained by a polycondensation reaction between a polycarboxylic acid such as pyromellitic acid and a polyhydric alcohol such as ethylene glycol or propylene glycol; a polycondensation reaction between a polyhydric alcohol such as glycerin and a polycarboxylic acid or fatty acid. Alkyd polycarboxylic acids obtained by polycondensation of polyamines such as ethylene diamine and phenylene diamine with polyhydric carboxylic acids; Maleated petroleum resins; Starch and cellulose containing carboxyl groups; Polyethylene glycols Dicarboxylic acids and the like can be mentioned. When the amount of free carboxyl 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). In addition, if it exceeds 5 milliequivalents/g, the polymerization system may gel depending on the introduction of the reactive unsaturated group, making it difficult to stably produce a reactive polymer. This is not preferred because the cured product derived from the polymer is limited to hard and brittle products. The unsaturated basic aziridine compound (B) used in the present invention is one of the 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 therein is basic. A typical unsaturated aziridine compound has the general formula () (However, in the formula, A is CH ₂ = CH-, CH ₂ = C
One group selected from the group consisting of (CH ₃ )- and CH ₂ =CH-CH ₂ -, m is an integer of 1 to 3, n is 0 or 1, and R ₁ to R ₄ is one selected from the group consisting of hydrogen and an alkyl group having 1 to 4 carbon atoms, and may be the same or different, and (m+
1) Q, which is a valent bonding group, is a hydrocarbon bond, a carboxylic acid ester bond, a sulfonic acid ester bond,
It may contain an ether bond, a urethane bond, a urea bond, an amide bond, a thioamide bond, a carbonyl group, a sulfonyl group, and the like. ) is a compound represented by A typical example of the unsaturated basic aziridine compound (B) is a compound having the general formula (). (However, in the formula, R ₁ to R ₄ are as described above, and R ₅ is hydrogen or a methyl group.) Among them, 2-(1-aziridinyl) is preferable.
It is ethyl methacrylate. Among the unsaturated aziridine compounds represented by the general formula (), specific examples of the unsaturated basic aziridine compound (B) are as follows. In the present invention, it is preferable that 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 (A). When the amount of the unsaturated basic aziridine compound (B) is less than 0.05 mol per 1.0 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, the free carboxyl group
If the amount of the unsaturated basic aziridine compound (B) exceeds 1.2 mol per 1.0 mol, ring-opening polymerization between aziridine rings increases in parallel with the esterification reaction, making it difficult to obtain a useful reactive polymer. . Therefore, in a more preferred embodiment of the production method of the present invention, polymer (A)
The amount of the unsaturated basic aziridine compound (B) per 1.0 mol of free carboxyl groups is 0.05 to 1.2 mol, more preferably 0.1 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 amino groups generated by the reaction with the polymer. The purpose of the present invention is to provide a method for improving the resulting drawbacks, but when reacting a free carboxyl group-containing polymer (A) with an unsaturated basic aziridine compound (B), monoisocyanates, monothioisocyanates, ketene This object can be achieved by using in combination at least one compound (C) selected from the group consisting of ketene dimers and ketene dimers. This compound (C) is 0.8 to 1.2 mol, particularly 0.9 to 1.1 mol, per 1.0 mol of the unsaturated basic aziridine compound (B).
It is preferred to react in ratios in the molar range.
The polymer (A) and the unsaturated basic aziridine compound (B)
If the above compound (C) is used in combination with the reaction with the former two, the reaction rate of the former two will not be reduced, and moreover, the basic amino group generated by the reaction of the former two will react with the compound (C). The basic amino groups in the system are reduced or completely eliminated, so that the reaction between the free carboxyl groups in the polymer (A) and the aziridine groups of the unsaturated basic aziridine compound (B) proceeds without inhibition, The coloration of the resulting reactive polymers is also significantly improved. As the compound (C), monoisocyanates
R ₁ −NCO, monothioisocyanates R′ ₁ −
NCS, ketenes, R ₂ R' ₂ C=C=O and ketene dimers

[Formula] (R ₁ and R' ₁ are an alkyl group, a cycloalkyl group, or a phenyl group having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms,
In addition, R ₂ and R′ ₂ are hydrogen, carbon atoms 1 to 8,
Preferred are 1 to 6 alkyl groups, cycloalkyl groups, and phenyl groups. ), preferably monoisocyanates and ketenes. Representative monoisocyanates include methyl isocyanate, ethyl isocyanate, propyl isocyanate, isopropylisocyanate, butyl isocyanate, sec-butyl isocyanate,
These include octyl isocyanates, cyclohexyl isocyanate, phenyl isocyanate, and the like.
Representative monothioisocyanates include methylthioisocyanate, ethylthioisocyanate,
Propylthioisocyanate, isopropylthioisocyanate, butylthioisocyanate,
These include sec-butylthioisocyanate, octylthioisocyanates, cyclohexylthioisocyanate, phenylthioisocyanate, and the like.
Representative ketenes include ketene, methylketene, ethylketene, propylketene, butylketene, octylketene, dimethylketene, diethylketene, dipropylketene, dibutylketene, methylethylketene, methylpropylketene, cyclohexylketene, phenylketene, and the like. Typical ketene dimers include ketene dimer, methyl ketene dimer, ethyl ketene dimer, propyl ketene dimer, butyl ketene dimer, dimethyl ketene dimer, diethyl ketene dimer,
These include methyl ethyl ketene dimer, cyclohexyl ketene dimer, phenyl ketene dimer, etc. The reaction in the present invention is carried out at room temperature, i.e. about 20°C.
However, at temperatures below 40°C, a ring-opening reaction between aziridine groups is observed. 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 is
Although it cannot be specified due to the polymer (A) used, the type and amount of polymerization inhibitor, the oxygen concentration of the reactive atmosphere, etc., the stability and reactivity of the polymerizable unsaturated group possessed by the unsaturated basic aziridine compound (B) can be determined. Considering the stability and coloring of the polymer, the temperature is 150°C. Therefore, the preferred temperature range is 40° to 110°C. During the reaction, polymers containing free carboxyl groups
When the fluidity of (A) is low or in order to facilitate the addition of the unsaturated basic aziridine compound (B) or compound (C) added to the reaction system, the polymer (A) and/or the unsaturated base It is a preferred method to apply a diluent to the aziridine compound (B) or compound (C). The diluent is a compound capable of dissolving or dispersing the polymer (A), the unsaturated basic aziridine compound (B), and the compound (C). Typical diluents are benzene,
Aromatic hydrocarbons such as toluene, xylene, cloabenzene; dioxane, methyl ethyl ketone,
Ketones such as acetone and methyl isobutyl ketone; esters such as ethyl acetate and butyl acetate; glycol ethers; carbitols; alcohols; water and the like. Furthermore, polymerizable monomers such as styrene, acrylonitrile, methacrylonitrile, acrylamide, 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 can be used as a chain lengthening agent, blocking agent, etc. in various fields such as adhesives, coating agents, fillers, and molding materials.
It is used as a grafting agent and crosslinking agent 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 carboxyl group content 1.48 meq/g, liquid polybutadiene carboxylic acid, manufactured by Nippon Soda) 250 was placed in a reactor equipped with a stirrer, a cooler, a thermometer, and a dropping funnel. Insert the section,
The temperature was adjusted to 60°C while stirring. Then from the dropping funnel
A mixed mixture of 57.4 parts of "Chemitite MZ-11" (2-(1-aziridinyl)ethyl methacrylate, manufactured by Nippon Shokubai Chemical Co., Ltd.) and 31.5 parts of n-propylisocyanate was continuously added dropwise over 1 hour, and further at the same temperature. The product was kept for 5 hours and cooled.
As a result of quantitative analysis of carboxyl groups and amino groups, this product was found to contain 98% of the free carboxyl groups in the raw material.
% was liquid polybutadiene 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 n-propylisocyanate 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 A product was obtained in exactly the same manner as in Example 1, except that 31.5 parts of n-propylisocyanate in Example 1 was replaced with 15.6 parts of ketene dimer. As a result of unsaturated group concentration analysis, this product was liquid polybutadiene in which 98% of the free carboxyl groups in the raw material had been converted to unsaturated groups. Example 3 A reactor equipped with a stirrer, a cooler, a thermometer, and a dropping funnel was charged with a monomer composition of methyl methacrylate/butyl acrylate/methacrylic acid = 10/80/10 (by weight) obtained by a conventional method. Add 500 parts of a 50% by weight toluene solution of a copolymer with a free carboxyl group content of 1.16 meq/g (ratio), and bring the internal temperature to 90% while stirring.
The temperature was adjusted to ℃. Next, a mixture of 45 parts of "Chemitite MZ-11" and 36.3 parts of cyclohexyl isocyanate was added from the dropping funnel, 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/g of reactive unsaturated groups. Example 4 Nipol-1072B (carboxylated acrylonitrile-butadiene rubber, manufactured by Nippon Zeon) with a free carboxyl group content of 0.71 meq/g was placed in a reactor equipped with a stirrer, a condenser, a thermometer, and a dropping funnel.
After adding 85 parts, 100 parts of methyl methacrylate and 0.001 part of phenothiazine to swell the membrane for one day,
The rubber was dissolved at 90°C with stirring. Then add the contents to 70
7.4 parts of “Chemitite” from the dropping funnel adjusted to ℃
A mixture of MZ-11" and 4.1 parts of n-propylisocyanate was added, 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 Approximately 77% of the free carboxyl groups had been converted to reactive unsaturated groups.

Claims (1)

[Claims] 1. 0.01 to 5 milliequivalents/g of free carboxyl groups
Polymer (A) containing an acid equivalent ratio of 1 in one molecule
selected from the group consisting of an unsaturated basic aziridine compound (B) having at least one basic aziridine group and at least one radically polymerizable unsaturated group, and monoisocyanates, monothioisocyanates, ketenes, and ketene dimers. 1. A method for producing a reactive polymer, which comprises reacting at least one compound (C) that has been prepared. 2 The amount of the unsaturated basic aziridine compound (B) is 0.05 per 1.0 mole of free carboxyl groups of the polymer (A).
~1.2 mol and the unsaturated basic aziridine compound
2. The method according to claim 1, wherein said compound (C) is present in a ratio ranging from 0.8 to 1.2 mol to 1.0 mol of (B).