JPS59213701A - Reactive acrylic polymer composition - Google Patents

Abstract

PURPOSE:To obtain titled composition easy to regulate its own molecular weight and functional group, useful for graft polymer production, by polymerizing, in an organic solvent, a polymerizable monomer in the presence of an azo initiator and tertiary amine followed by the reaction with an oxirane bond-carrying polymerizable compound. CONSTITUTION:(A) An alpha,beta-ethylenic unsaturated monomer free from oxirane ring and/or carboxyl group (e.g., an acrylate such as methyl acrylate) is polymerized, in an organic solvent, pref. at 80-130 deg.C, in the presence of (B) a carboxyl group-contg. azo initiator [e.g., 4,4'-azobis (4-cyanovaleric acid)] and (C) a tertiary amine (e.g., pyridine) followed by the reaction, pref. at 80-150 deg.C, with (D) a compound containing both alpha,beta-ethylenic unsaturated bond and oxirane bond (e.g., glycidyl methacrylate), thus obtaining the objective composition.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a reactive acrylic polymer composition, and more particularly to a reactive acrylic polymer composition whose functional groups and molecular weight can be extremely easily adjusted and which is useful in the production of polymers from Graph 1. It is something.

In the production of acrylic graph 1 polymers, organic solutions of oligomers having reactive α,β-ethylenically saturated bonds at their terminals are extremely useful.

Conventionally, such reactive acrylic oligomers, so-called macromer solutions, are prepared by using an α,β-ethylenically inert saturated monomer initiator and a chain transfer agent such as thioglycolic acid to obtain an oligomer having a terminal carboxyl group, and then glycidyl (meth) ) to react with acrylate (British Patent No. 1.09)
6,912), a method of obtaining an oligomer having a terminal hydroxyl group using mercaptoethanol together with an initiator, converting it to sardine 1-1 with tolylene diisocyanate, etc., and then converting it into a macromer with 2-hydroxyethyl methacrylate, etc. (U.S. Pat. No. 6,912). 3.689.593) was used. However, in all of these methods, since an initiator and a chain transfer agent coexist, oligomers containing no terminal carboxyl groups or hydroxyl groups are produced when the polymerization rate is high or C conversion is carried out, and macromers inevitably contain chain It contains a C-5-C bond derived from a transfer agent, and this bond has poor photostability and is easily cleaved when exposed to sunlight, causing deterioration of the polymer.

In addition, styrene etc. are ionically polymerized with butyllithium,
A method is also known in which ethylene oxide is reacted and then alkyl acid halide is reacted, but such ionic polymerization is not common because the types of monomers that can be used are limited.

The present inventors aimed to obtain an organic solution of a reactive acrylic oligomer useful for grafting, which is easy to control the molecular weight and has no problems such as photostability, from a wide range of monomers having various functional groups. As a result of various studies, it has been found that if a reactive intermediate having no oxirane ring or carboxyl group is polymerized in an organic solvent in the presence of an azo starter and a tertiary amine that has a carboxyl group, it is easy to achieve a high polymerization rate. The present inventors realized that an acrylic oligomer solution having a terminal carboxyl group was obtained, and that the desired reactive acrylic oligomer could be derived from this very easily, leading to the completion of the present invention.

According to the present invention, at least one α,β-ethylenically unsaturated monomer having no oxirane ring and/or carboxyl group is mixed with an azo initiator having a carboxyl group in a body solvent. A reactive acrylic polymer composition obtained by polymerizing in the presence of a 37th amine and then reacting with a compound having an α,β-ethylenically unsaturated bonded xylan ring is provided.

As is clear from the above, the acrylic polymer composition of the present invention is intended to be a relatively low molecular weight oligomer composition having an average molecular weight of about 20,000 or less.

α,β-ethylenically unsaturated saturated monomer having no oxirane ring and/or carboxyl group used in the production of the polymer composition of the present invention. Known as a monomer for ordinary acrylic or vinyl polymers. It can be any compound that does not have the above-mentioned functional group. Typical examples include (1) non-functional monomers such as methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, cyclo Acrylates such as xyl acrylate, benzyl acrylate, n-ocdyl acrylate 1 and dodecyl acrylate; Corresponding methacrylates; Fatty acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl acetate, and vinyl stearate; styrene; Aromatic heptano-A-refins such as chlorstyrene, α-methylstyrene, vinyl-1-luene (2)
Functional monomers, such as hydroxyalkyl acrylates such as 2-hydroxybutyl acrylate, 2-hydroxypropyl acrylate, 3-human[1-xypropyl acrylate, 4-hydroxybutyl acrylate]; corresponding methacrylates;
Classes 1 to 1: Aminoalkyl (meth)acrylates represented by the general formula (wherein R1 is hydrogen or a medyl group, R2 and R3 are each an alkyl group having 1 to 6 carbon atoms, and 11 is an integer of 1 to 6); 4
-vinylpyridine, 2-vinylpyridine, 2-methyl-
Vinylpyridines such as 5-vinylpyridine; N,N-disubstituted-acrylamides and methacramides, di-N-
Methylolated, N,N-dimedylolated (meth)acrylamides; examples include acrylonitrile, methacrylatetrile, and the like.

The azo initiator having a carboxyl group used in the present invention is, for example, 4,4'-azobis(4-cyanoarchae 1),
7.7'-Azobis(7-Diatscabryl II),
6.6'-azobis(6-cya-6-cyclohexylcaproic acid), 2.2'-azobis(2-methylpropionic acid), 2.2'-azobis(2-ethyl-4-methoxyvaleric acid) , 2.2'-Azobis(2-benzylpropionic acid), and other azo-based initiators known as azocarboxylic acids having a carboxyl group can be suitably used.

Tertiary amines include pyridine, isoquinoline, quinoline, N,N-dimethylcyclohexylamine, α-picoline, benzyldimethylamine, toso-11-butylamine, triethylamine, N-■thylmorpholine, N,N
Any known tertiary amine can be used, such as -dimethylaniline, N-edyru-3,5-dimethylmorpholine, etc.

In the present invention, at least one of the above ethylenically unsaturated monomers is polymerized in an organic solvent in the presence of the above azo initiator having a carboxyl group and a tertiary amine to form an acrylic resin having a terminal carboxyl group. Oligomers are produced.

Organic solvents include alcohols (e.g. ethanol, propatool, isopropyl, butanol, ethyl cellosolve, methyl cellosolve, etc.), ketones (methyl ethyl ketone, methyl isobutyl ketone, methyl ethyl ketone, cyclohexanone, etc.), and esters (e.g. ethyl acetate). , propyl acetate, butyl acetate, amyl acetate, 2-ethoxyethyl acetate-1-, 2-methoxyethyl acetate, etc.), hydrocarbons, (e.g. toluene, xylene, Tsurupez 100 (Esso, registered trademark), Tsurupez 1
50 (Esso), etc.), or a mixture thereof can be suitably used.

The reaction is usually carried out by adding 0.5 parts of an azo initiator having a carboxyl group to 100 parts (parts by weight, the same applies hereinafter) of the monomer to be polymerized.
~40 parts, preferably 1 to 25 parts, of a tertiary amine sufficient to substantially neutralize the carboxyl group of the azo initiator, in fact acid equivalent/amine equivalent = 110.5 to 1/2, preferably It is carried out by heating in the presence of 110°8 to 1/1.5.

Heating is usually 60-150°C, preferably 80-130°C
It is sufficient to perform the song for several hours within the range of
It can be changed as appropriate depending on the object etc.

The above reaction yields a solution of an acrylic oligomer having a carboxyl group at its terminal.

It has been known that α,β-ethylenically unsaturated monomers can be polymerized using an azo initiator having a carboxyl group, such as azobiscyanovaleric acid, in an organic solvent, but mainly due to the solubility of the initiator, For example, 0.
Since it is used only at a low concentration of 2 to 0.3%, the polymerization rate is low, and relatively low-molecular oligomers with an average molecular weight of about 600 to 20°OOO, which is the purpose of the present invention, have not been obtained. Attempts have been made to greatly increase the initiator concentration by using special organic solvents such as dimethyl sulfoxide, but these cannot be used for varnish purposes due to the odor of the solvent. Therefore, the use of a chain transfer agent was considered, but the disadvantages of using a chain transfer agent are as already mentioned.

However, as in the present invention, by using a tertiary amine together with an azo initiator, it is possible to increase the initiator concentration by as much as 11", and an acrylic oligomer with a desired molecular weight range can be easily obtained without using a chain transfer agent. It will be done. Furthermore, since this initiator is present at the end of the acrylic oligomer, an oligomer having a terminal carboxyl end can be obtained.

If the purpose is simply to make the azo initiator soluble in an organic solvent by neutralizing the amine, the amine is not limited to a tertiary amine, and may be either a primary amine or a secondary amine. In fact, an acrylic oligomer solution with terminal carboxyl groups is thereby obtained. However, in J3 of the present invention, the oxirane ring is then reacted with a compound having a polymerizable unsaturated group, for example, a compound represented by the formula (in the formula, R1 and R2 are hydrogen or methyl groups), and the carboxyl group and the oxirane are reacted. An ester bond is created in the reaction, but primary amines and secondary amines cause side reactions and inhibit the above reaction.

On the other hand, tertiary amines have a catalytic effect that not only does not have an adverse effect on the above reaction, but also promotes the reaction. Therefore, in the present invention, a tertiary amine is selectively used as a neutralizing agent for the azo initiator. Of course, this is not a preferred embodiment, but instead of the tertiary amine, primary and secondary amines are used to prepare an acrylic oligomer having a terminal carboxyl group, and then exchanged with the tertiary amine, and then the oxirane ring and the polymerizable unsaturated group are exchanged. It should be understood that it is also possible to react with a compound having the following, and therefore the present invention also encompasses such embodiments.

Although the second step of the present invention is not an essential requirement, it is carried out in the presence of a conventional polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, etc. It is preferable to cover i in order to retain the reactive unsaturated group. As mentioned above, since the tertiary amine acts as a catalyst, no external catalyst is particularly required, but if desired, a metal salt such as tin A ctylate or zinc acetate may be added as a catalyst.

The second step of the present invention is also usually carried out by heating, and the heating temperature at that time is 50 to 170°C, preferably 80 to 150°C.
It is.

As is clear from the above, in the present invention, a wide variety of α,β-edylenic uncharacteristic saturated monomers having no oxirane ring and carboxyl group are arbitrarily selected. Amine groups and other functional groups can be concentrated or such functional groups m can be controlled.

Furthermore, the molecular weight of the oligomer can be controlled relatively easily by adjusting the initiator concentration, reaction temperature, etc., and various reactive acrylic oligomers can be prepared by tailor-mate depending on the purpose. Moreover, since the target product is obtained as an organic solvent solution, it can be used as it is for producing the Graph 1 polymer. The macromer obtained according to the present invention can be copolymerized with one or a mixture of other polymerizable unsaturated monomers to improve the functionality of the polymer.

For example, in the case of a hydrophobic polymer grafted with hydrophilic groups, i.e., when the branches are methyl methacrylate and the trunk is hydroxyethyl methacrylate, a hydrophilic or hydrophobic surface is formed depending on the environment in which the polymer is placed. The hydrophobic surface is useful for wetting, adhesion, printing, etc., and the hydrophobic surface is useful for water-repellent, oil-repellent, stain-proofing, etc.

The present invention will be explained below with reference to Examples.

Example-1 Dripping funnel A, 82 pieces, cooling pipe, nitrogen introduction pipe, thermometer,
400 parts of butyl acetate and 400 parts of xylene were charged into a reaction vessel equipped with a stirring blade, and the mixture was heated to 120°C to crystallize. 100 parts of styrene monomer, 10 2-ethylhexyl methacrylate
A solution of 45 parts of 4.4'-azobis(4-cyanovaleric acid), 180 parts of butanol, and 33 parts of 1-ethylamine was charged into dropping funnel A. The contents of dropping rows 1 to 8 and B were dropped at a constant speed for 3 hours at 120° C. under a nitrogen atmosphere to cover the contents. After the dropwise addition was completed, the temperature was maintained at 120°C for 30 minutes, and then the solvent was removed at 100°C under reduced pressure to obtain 240 parts of terminal acid oligomer. Next, 240 parts of xylene was added to make a xylene solution of the terminal acid oligomer, and then 27.0 parts of glycidyl methacrylate and 0.5 parts of hydroquinone were added, the temperature was raised to 140°C, and the temperature was maintained at 140°C for 180 minutes to complete the addition reaction.

After cooling, the contents were taken out to obtain a pale yellow macromer solution. The characteristics of the macromer solution are shown in Table 3.

Examples 2 to 5 Macromer solutions were obtained in the same manner as in Example 1 using the formulations shown in Table 1. Table 3 shows the special properties of Mac1'mer solution.
Ru. 143 parts of styrene, 5 parts of dimethylhexyl acrylate
7 parts to dropping funnel A, 50 parts of 7゜7'-azobis(7-diatucaprylic acid), 200 parts of n-butanol, and 41 parts of benzyldimethylamine to dropping funnels 1 to B, and heated at 115°C under nitrogen atmosphere for 3 hours. This is a uniform drip of 1 no. After dropping, hold at 115°C for 30 minutes and add lysidyl methacrylate.
1 part, and 0.5 part of hydroquinone methyl ether were added, and the mixture was kept at 115°C for an additional 240 minutes to complete the addition reaction.

After adding 100 parts of xylene and cooling, the contents were taken out to obtain a macromer solution. The contents of the macromer solution are shown in Table 3.

Examples 7 to 12 Macromer solutions were obtained in the same manner as in Example 6 using the formulations shown in Table 2. The characteristics of the macromer solution are shown in Table 3.
-0 (blank space below) Procedural amendment band May 21, 1980 Commissioner of the Japan Patent Office 3 Relationship with the case of the person making the amendment Patent applicant address 2-1-2 Oyodo Kita, Oyodo-ku, Osaka Name Nippon Paint Co., Ltd. Representative Masao Suzuki 4 Agent address 3-57 Kyobashi, Higashi-ku, Osaka 540 6 Number of inventions to be increased by amendment -7 Subject of amendment
Detailed explanation column 8 of the specification Contents of amendment No. 14 of the specification
Delete the page and attach the attached sheet to Table 1 Example 6

Claims (1)

[Claims] Presence of an azo 171 initiator having a carboxyl group and a tertiary amine in at least one α,β-ethylenically unsaturated saturated monomer solvent having no oxirane ring and/or carboxyl group 1. A reactive acrylic polymer composition obtained by polymerizing the following compounds and then reacting a compound having an α,β-1 dylenically unsaturated bond and an oxirane bond.