JPS60188407A - Production of tertiary amino group-containing vinyl polymer - Google Patents

Abstract

PURPOSE:To produce a tert. amino group-containing vinyl polymer free of an amine odor and coloration, by reacting a carboxylic acid anhydride group-containing vinyl polymer with a specified tert. amino group-containing compound, and heating the product. CONSTITUTION:A compound having one prim. amino group and one tert. amino group in the molecule (e.g., N,N-dialkyl-1,3-propylenediamine) is reacted with a carboxylic acid anhydride group-containing vinyl polymer (e.g., alkyl acrylate/ styrene/maleic anhydride copolymer) in an amount to provide about 0.5-3mol of the prim. amino group per equivalent of the acid anhydride group of the vinyl polymer for about 0.5-3hr at about room temperature -120 deg.C, and the obtained adduct is heated at about 70-150 deg.C for about 1-20hr to effect dehydrative condensation and formation of imide rings.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel and useful method for producing a vinyl polymer containing a 6th class amine group.

Conventionally, K for preparing vinyl polymers containing a quinary amino group has been used to prepare a vinyl polymer containing a tertiary amine group (meth) such as N,N-dialkylaminoalkyl (meth)acrylate.
Although the method of (co)polymerizing acrylate as one of the monomers has been adopted, the polymer obtained by this method has an amine odor and is also significantly colored, so epoxy One drawback is that when a resin is blended to form a cured coating film, the coating film is markedly colored, impairing its commercial value.

However, in view of the above-mentioned drawbacks in the prior art, the present inventors first reacted a vinyl polymer containing a carboxylic anhydride group with at least one carboxylic anhydride group in each molecule. A room temperature curable resin composition comprising a vinyl polymer having both a carboxyl group and a 6th class amine group obtained by reacting a compound having both a group having an active hydrogen and a tertiary amino group, and a VolJ epoxy compound. The patent application No. 57-166795 and Japanese Patent Application No. 58-17192 have been filed for the resin composition, respectively, but both of these resin compositions have overcome the drawbacks of the prior art as described above. However, the common drawback of these cured products is that they have insufficient stain resistance and alkali resistance.

In view of the existence of these drawbacks, the present inventors conducted extensive research and found that the carboxylic acid anhydride group-containing vinyl polymer has the following properties:
When a specific 3R amino group-containing compound is reacted, it is possible to obtain a tertiary amino group-containing vinyl polymer that is free from the drawbacks mentioned above, namely, amine odor and coloring. The present invention was completed based on the discovery that a resin composition consisting of a polyepoxy compound and a polyepoxy compound provides a cured product that is free from coloration and has excellent stain resistance, alkali resistance, and weather resistance. Ta.

That is, the present invention provides a vinyl polymer (a-1) containing a carboxylic acid anhydride group, and a compound (a-2) containing one primary amine group and one tertiary amino group in each molecule.
), followed by dehydration condensation and imide cyclization, to provide a novel and useful method for producing a vinyl-based monomer containing a tertiary amino group.

Here, the above-mentioned vinyl polymer (a-1) containing a carboxylic anhydride group refers to a monomer having an acid anhydride group such as maleic anhydride or itaconic anhydride, and a monomer having copolymerizability with these. This is a copolymer obtained by copolymerizing other vinyl monomers with
Typical examples of other vinyl monomers having such copolymerizability include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, and 111o-butyl. (meth)acrylate), tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate
(meth)acrylic acid esters such as acrylate, cyclohexyl (meth)acrylate or benzyl (meth)acrylate; dialkyl esters of unsaturated dibasic acids such as itaconic acid, maleic acid or fumaric acid; (
Containing hydroxyl groups such as meth)acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, itaconic acid monoalkyl ester, maleic acid monoalkyl ester, hafumaric acid monoalkyl ester, or β-hydroxyethyl (meth)acrylate. Mutants having carboxyl groups such as adducts of vinyl monomers and acid anhydrides such as succinic anhydride or trimellitic anhydride;
Aromatic unsaturated hydrocarbons such as styrene, α-methylstyrene or vinyltoluene; or vinyl acetate, (
Examples include meth)acrylonitrile, (meth)acrylamide, diacetone acrylamide, N,N-dimethyl(meth)acrylamide, N-vinylpyrrolidone, vinyl chloride, or phosphate ester of β-hydroxyethyl (meth)acrylate.

The amount of the monomer having an acid anhydride group to be used is preferably within the range of 1 to 20% by weight in terms of the curability of the obtained polymer and the alkali resistance and stain resistance of the cured product. .

In this case, although the desired effect of the present invention can be achieved without using the above-mentioned monomer having a carboxyl group, there are cases where it is necessary to shorten the reaction time when carrying out the method of the present invention. In this case, it is preferable to copolymerize so that it is present in the carboxylic anhydride group-containing vinyl polymer (a-1) in an amount of 01 to 15% by weight.

The polymer (a-1
) can be prepared by any known and commonly used method, but the solution radical 1h method is most preferable, and in this case aromatic hydrocarbons such as toluene and xylene; hexane, pentane, (Cyclic) aliphatic hydrocarbons such as cyclohexane; ester solvents such as ethyl acetate, butyl acetate, and ethylene glycol monomethyl ether acetate; and solvents such as acetone, methyl ethyl ketone, methi-1-so-butyl ketone, and ketone solvents such as cyclohexanone. The polymerization may be carried out by a conventional method using a known and commonly used polymerization initiator such as , azo type or peroxide type.

Additionally, polymerization can be carried out using a molecular weight regulator such as mercaptans such as tert-dodecyl mercaptan, lauryl mercaptan, thioglycolic acid alkyl ester, and β-mercaptopropionic acid, and α-methylstyrene dimer.

Next, representative compounds (a-2) each containing one primary amine group and one tertiary amine group in one molecule include N,N-dimethylethylenediamine, N,N- N,N-dialkylethylenediamines such as diethylethylenediamine, N,N-dipropylethylenediamine; N,N-dimethyl-1,3-propylenediamine, N,N-diethyl-1,3-propylenediamine, N,N- N,N-dialkyl-1,6-propylene diamines such as digzolo-1,3-propylene diamine; N,N-dimethyl-1,4-tetramethylenediamine, N,N-diethyl-1,4-tetra N,N-dialkyl-1,4-tetramethylenediamines such as methylenediamine; such as N,N-dimethyl-1,6-hexamethylenediamine, N,N-diethyl-1,6-hexamethylenediamine N,N-dialkyl-1,6-
Hexamethylene diamines: N-(2-aminoethyl)
Morpholine, N-(3-aminopropyl)morpholine,
N-aminoalkylmorpholines such as N-(4-aminobutyl)morpholine, N-(6-aminohexyl)morpholine; N-(2-aminoethyl)pyrrolidine, N-
Examples include N-aminoalkylpyrrolidines such as (3-aminopropyl)pyrrolidine, N-aminoalkylpiperidines such as N-(2-aminoethyl)piperidine, N-(3-aminopropyl)piperidine, etc. However, from the viewpoint of economy, it is preferable to use N,N-dialkyl-1,3-propylene diamines.

In carrying out the method of the present invention, first, the primary amine in the compound (a-2) as listed above is added to the equivalent of the acid anhydride group in the polymer (a-1) as listed above. Group is 0.5
These two components are mixed in such a proportion that the color is 3 molar equivalents, and the mixture is reacted at a temperature from room temperature to about 120 DEG C. for about 5 to 5 hours to obtain an adduct.

Furthermore, the adduct obtained in this way was heated to 1
By heating for about 20 hours, dehydration condensation and imide cyclization are carried out to obtain the objective vinyl polymer containing a tertiary amine group having an imide ring.

Now, as an example, a maleic anhydride copolymer is used as the polymer (a-1), and N,N-dimethylamino-1,3-propylenediamine is used as the compound (a-2). The reaction in this case is shown in the following reaction formula.

As described above, condensation water is produced when obtaining the objective vinyl polymer according to the method of the present invention, but depending on the application, the objective 1 polymer may be used as it is without removing such condensation water at all. However, if it is necessary to remove it, during the dehydration condensation reaction or after the completion of the reaction,
Dehydration can also be carried out by adding a known and commonly used desiccant or dehydrating agent or by azeotropically distilling the mixture with a solvent.

The vinyl polymer containing a 6th-class amino group obtained by the method of the present invention can be used as a coating resin by using a suitable crosslinking agent such as a polyepoxy compound, and can also be used as a sealant or adhesive. It can also be used as.

Next, the present invention will be specifically explained with reference to Examples and Comparative Examples, and unless otherwise specified, all parts and percentages are based on weight.

Example 1 700 parts of toluene was charged into a reactor equipped with a thermometer, a stirrer, a dropping funnel, a nitrogen introduction pipe and a condenser, and the temperature was raised to 110°C in a nitrogen atmosphere, and then styrene was added thereto. 300 parts of methyl methacrylate, 300 parts of n-butyl methacrylate, and 150 parts of n-butyl acrylate.

70 parts of maleic anhydride, 10 parts of azobisisobutyronitrile (AIBN), 10 parts of tart-butylperoxyoctoate (TBPO), 5 parts of tart-butylperoxybenzoate) (TBPB). and 300 parts of toluene were added dropwise over 3 hours and then maintained at the same temperature for 15 hours to continue the reaction, with a non-volatile content (NY) of 50% and a number average molecule #(
A bath liquid of a vinyl polymer (a-1) having an acid anhydride group with Mn) of 2000 was obtained. Hereinafter, this will be abbreviated as vinyl polymer (a-11).

Next, the temperature of this polymer solution was lowered to 100°C, and 72% of N,N-dimethyl-1,3-propylene diamine was added.
．． After 9 parts of toluene were charged and held at the same temperature for 12 hours to cause dehydration and ring closure, 100 parts of toluene was distilled off under reduced pressure to remove condensed water.

Then, 100 parts of toluene and 296 parts of n-butanol were added to obtain a solution of the objective vinyl polymer having a Gardner color of 1 or less and a NY content of 45%.

Below, 13- This is abbreviated as vinyl polymer (A-1).

The solid acid value of the thus obtained polymer (A-1) was 4.
0, and an absorption of 1,700 m-' due to the diimide ring was confirmed by IR spectrum analysis. The ring closure rate to the imide ring calculated from this acid value was 89%.

Example 2 The same procedure as in Example 1 was carried out, except that 70 parts of the monomers to be copolymerized and 20 parts of maleic anhydride were replaced with acrylic acid, with 50% NY and 9% wig. An acid anhydride group-containing vinyl polymer (a-1) of 100 was obtained.

Hereinafter, this will be abbreviated as vinyl polymer (a-1-2).

Next, the temperature of this polymer solution was lowered to 100°C, and 52% of N,N-dimethyl-1,3-propylene diamine
After adding 100 parts of toluene and holding at the same temperature for 3 hours to cause dehydration and ring closure, 100 parts of toluene was distilled off under reduced pressure to remove condensed water.

After that, 100 parts of toluene and 275 parts of n-butanol were added to obtain a solution of the desired vinyl polymer having a Gardner color of 1 or less and an NV of 45%.

Hereinafter, this will be abbreviated as vinyl polymer (A-2),
The solid acid value of the polymer (A-2) is 16.3,
The ring closure rate to the imide ring calculated from this value was 94%.

Example 6 The monomer composition to be copolymerized was 200 parts of styrene, 300 parts of methyl methacrylate, 300 parts of n-butyl methacrylate, 120 parts of n-butyl acrylate,
An acid anhydride group-containing vinyl polymer (a
-1) Bath solution was obtained. Hereinafter, this will be referred to as vinyl polymer (a
-1-5).

Next, the temperature of this polymer solution was lowered to 100'C, and 4 of N,N-dimethyl-1,3-propylene diamine was
1.6 parts of toluene was added thereto and the mixture was maintained at the same temperature for 3 hours to cause dehydration and ring closure.100 parts of toluene was then distilled off under reduced pressure to remove condensed water.

Thereafter, 100 parts of toluene and 264 parts of n-butanol were added to obtain a solution of the objective vinyl polymer having a Gardner color of 1 or less and an NV of 45%. Hereinafter, this will be abbreviated as vinyl polymer (A-3), but the solid acid value of this polymer (A-3) is 26, and the ring closure rate to the imide ring calculated from this value is It was 96%.

Example 4 2,000 ml of the polymer (a-1-2) obtained in Example 2
The temperature was raised to 100°C, and N,N-diethyl-1,
66.3 parts of 3-propylene diamine was charged and kept at the same temperature for 3 hours to cause dehydration and ring closure, and then 100 parts of toluene was distilled off under reduced pressure to remove condensed water.

After that, toluene i o os and n-
292 parts of butanol was added to obtain a solution of the desired vinyl-based complex having a Gardner color of 1 or less and an NV of 45%. Hereinafter, this will be abbreviated as vinyl polymer (A-4), but the solid acid value of this polymer (A-4) is 16, and the ring closure rate to the imide ring calculated from this value is 95. %Met.

Comparative Example 1 2,000% of the polymer (a-1-1) obtained in Example 1
The temperature was raised to 50°C, and N,N-dimethyl-1,3
- Add 72.9 parts of propylene diamine and hold at the same temperature for 30 minutes, then add 311 parts of n-butanol to obtain a Gardner color of 1 or less and an NV of 45%. A solution of a vinyl polymer containing an uncontained 6th-class amino group was obtained.

Hereinafter, this will be abbreviated as vinyl polymer (A'-1), and the solid acid value of this polymer was 37.

Application Examples 1 to 4 and Comparative Application Example 1 Each polymer solution obtained in each Example and Comparative Example was used as a base resin component, and the pwc was 40% at the blending composition ratio shown in Table 1. A white paint was prepared.

Next, each paint was mixed with xylene/toluene/n-butanol/cellosolve acetate = 30/40/20
The mixture was diluted to a spray viscosity of 1/10 (weight ratio) and sprayed onto a slate board, and then dried and cured at room temperature for 7 days.

Performance evaluation was performed on each cured coating film thus obtained, and the results shown in the table were obtained.

18- As is clear from the results in the same table, it is known that the vinyl polymer obtained by the method of the present invention provides a cured product (cured coating film) with excellent alkali resistance, stain resistance, and weather resistance. .

Ministry of Procedure and Amendments March 7, 1985 1, Indication of the case 1988 Patent Application No. 42828 2, Name of the invention Process for producing tertiary amino group-containing vinyl-based monomer 3, Person making the amendment Related Patent Applicant: 3-35-58 Sakashita, Itabashi-ku, Tokyo (288) Dainippon Ink Chemical Industry Co., Ltd. Representative: Shigekuni Yomura 4 Agent: Dainippon Ink, 3-7-20, Nihonbashi, Chuo-ku, Tokyo 103 Chemical Industry Co., Ltd. Telephone Tokyo (03) 272=4511 (main representative) (88
76) Patent Attorney Katsutoshi Takahashi 5, date of amendment order Voluntary 6 Contents of the amendment in column 7 “Detailed explanation of the invention” of the specification subject to the amendment (1) Statement from lines 2 to 7 on page 11 of the specification Correct (reaction formula) as follows.

``The reaction when used is shown in the reaction formula as follows.

In this way, the objective vinyl polymer can be produced according to the method of the present invention.'' (2) ``Table 1'' on page 20 of the specification is corrected as follows.

(2)

Claims (1)

[Claims] t A vinyl polymer containing a carboxylic anhydride group (a-
1) and a compound (a-2) each containing one primary amino group and one tertiary amino group in one molecule are subjected to an addition reaction, followed by dehydration condensation and imide cyclization, A method for producing a vinyl polymer containing a 6th class amine group. 2. Vinyl polymer containing the above carboxylic acid anhydride group (
The method according to claim 1, wherein a-1) has a carboxylic anhydride group and also has a carboxyl group. 3. The above-mentioned compound (a-2) containing one primary amine group and one tertiary amino group in each molecule is N,
A process according to claim 1 or claim 2, characterized in that N-dialkyl-1,3-propylene diamine is used.