JPH02281013A - Diketone compound copolymer - Google Patents

Abstract

PURPOSE:To provide the subject copolymer composed of a methylenediketone compound unit and a vinyl monomer unit at a specific ratio, having a specific molecular weight and useful as a modifying material for synthetic resin, synthetic fiber, paint, adhesive, etc. CONSTITUTION:The objective copolymer has a molecular weight of 500 to 1,000,000 (preferably 2,000 to 200,000) and contains 0.1 to 50mol% of a 2- methylene-1,3-diketone compound unit of formula [X is (substituted) alkyl or (substituted) aryl: Y is (substituted) alkyl, (substituted) aryl or alkoxy] (e.g. 2-methylene-1,3-diphenyl-1,3-propanedione) and 99.9 to 50mol% of a vinyl monomer unit (e.g. ethylene or vinyl acetate).

Description

Detailed Description of the Invention <Industrial Application Field> The present invention relates to a diketone compound-based copolymer, and more specifically, a copolymer comprising a 2-methylene-1,3-diketone compound unit and a vinyl thread unit. The present invention relates to a novel diketone compound-based copolymer that can be used as a modifying material for synthetic resins, synthetic fibers, paints, adhesives, etc.

<Prior Art> Conventionally, in order to improve the properties of vinyl copolymers, various studies have been conducted on polymers obtained by copolymerizing various compounds and vinyl monomers.

In addition, the following general formula (n) -X / (wherein, The 2-methylene-1,3-diketone compound represented by the following is already known.

However, at present, nothing is known about a copolymer obtained using the 2-methylene-1,3-diketone compound and a vinyl monomer.

<Problems to be Solved by the Invention> An object of the present invention is to provide a novel diketone compound-based copolymer that has superior flexibility, mechanical strength, water resistance, etc. compared to conventional vinyl polymers. .

Another object of the present invention is to provide a novel diketone compound-based copolymer that can be used as a modifier for synthetic resins, synthetic fibers, paints, adhesives, and the like.

<Means for Solving the Problems> According to the present invention, the following general formula (I) (wherein X represents an alkyl group, a substituted alkyl group, an aryl group, or a substituted aryl group, and Y represents an alkyl group or a substituted alkyl group) , aryl group, substituted aryl group or alkoxy group) and 99.9 to 50 mol% of vinyl monomer units. Molecular weight 500-1000
000 diketone compound-based copolymers are provided.

The present invention will be explained in more detail below.

The diketone compound copolymer of the present invention is characterized by containing a specific 2-methylene-1,3-diketone compound unit and a vinyl monomer unit.

In the present invention, the 2-methylene-1,3-diketone compound unit can be represented by the following general formula (I), where X represents an alkyl group, a substituted alkyl group, an aryl group, or a substituted aryl group. , Y represents an alkyl group, substituted alkyl group, aryl group, substituted aryl group or alkoxy group). 2-methylene- represented by the above general formula (I)
2-methylene- constituting the 1,3-diketone compound unit
Examples of the 1,3-diketone compound include 2-methylene-1,3-diphenyl-1,3-propanedione, 2-
Methylene-1,3-di-p-chlorophenyl-1,3-
Propanedione, 2-methylene-1-phenyl-1,3
Preferred examples include -butanedione, 2-methylene-1-phenyl-3-ethoxy-1,3-propanedione, and the like, which can be used alone or as a mixture.

The 2-methylene-1,3-diketone compound can be prepared by a known method.

In the present invention, examples of vinyl monomers constituting the vinyl monomer unit include styrene derivatives such as styrene, p-methoxystyrene, and p-diethylaminostyrene; vinyl ethers such as butyl vinyl ether; vinyl such as vinyl acetate and vinyl chloroacetate. Esters; acrylonitrile, methacrylatetrile, 2-ethyl-3
Preferred examples include (meth)acrylonitrile derivatives such as -methylacrylonitrile, and methacrylic acid ester derivatives such as methyl methacrylate and ethyl methacrylate, which may be used alone or as a mixture.

In the present invention, the content ratio of the 2-methylene-1,3-diketone compound unit and vinyl monomer unit is as follows:
2-methylene-1,3-diketone compound unit 0.1-5
0 mol%, vinyl monomer unit 99.9-50 mol%
It is. If the content of the 2-methylene-1,3-diketone compound unit is less than 0.1 mol%, the modification of the existing vinyl polymer is insufficient, and if it exceeds 50 mol%, unreacted 2-methylene-1,3-diketone compound units are present. - Since the methylene-1,3-diketone compound is mixed into the resulting copolymer, it is necessary to maintain the above-mentioned content ratio.

Furthermore, the molecular weight of the diketone compound copolymer of the present invention is 50
0-1oooooo, particularly preferably 2000-200
It is 000. When the molecular weight is less than 500, heat resistance and mechanical strength are insufficient, and when the molecular weight is less than 10000000,
If it exceeds this amount, flexibility will be lacking and solubility in the solvent will decrease.

In order to produce the diketone compound-based copolymer of the present invention, each of the above-mentioned monomers is, for example, an organic peroxide-based monomer.

In the presence of an azo compound or other radical polymerization initiator,
It can be obtained by copolymerization using a known radical polymerization method such as a bulk polymerization method, a solution polymerization method, a suspension polymerization method, or an emulsion polymerization method. As the radical polymerization initiator,
Peroxides such as acetyl peroxide, t-butyl peroxide, benzoyl peroxide, and 2-chlorobenzoyl peroxide; 2,2'-azobisisobutane, 1,1'-azo(methylethyl) diacetate , 2,2'-azobisisobutyronitrile, azo compounds such as 1,1'-azobis-1-phenylethane, 1,4-bis(pentamethylene)-
2-tetrazene, 1,4-dimethoxycarbonyl-1,
Preferred examples include 4-diphenyl-2-tetrazene and benzenesulfonylamide. The amount of the radical polymerization initiator used is not particularly limited, but it is preferably 0.5 to 10 parts by weight based on 100 parts by weight of the total monomers, and particularly economically, about 2 parts by weight. It is desirable to have one.

Further, the polymerization temperature during the copolymerization is preferably about 20 to 150°C. At this time, the polymerization reaction proceeds even outside the above-mentioned polymerization temperature range, but if the temperature exceeds 150°C, it is difficult to control side reactions, so it is not preferable, and economically
The reaction time is most preferably about 80° C., while the reaction time varies depending on the degree of polymerization, but is usually preferably in the range of 0.5 to 120 hours.

Furthermore, the copolymerization reaction can be carried out without a solvent or in the presence of a solvent. Examples of the solvent include alcohols such as methyl alcohol and ethyl alcohol, halogenated hydrocarbons such as methylene chloride, carbon tetrachloride, and chlorobenzene, and hydrocarbons such as toluene, benzene, and xylene. The amount used is not particularly limited, but
Economically, 0-10 parts by weight per 100 parts by weight of all monomers.
A range of 0.00 parts by weight is preferred. Furthermore, an ionic polymerization inhibitor such as acetic acid can also be used during polymerization.

<Effects of the Invention> Since the diketone compound-based copolymer of the present invention has a specific 2-methylene-1,3-diketone compound unit, it has better flexibility, mechanical strength, and water resistance than conventional vinyl polymers. It has excellent properties such as properties and is useful as a modifying material for synthetic resins, synthetic fibers, paints, adhesives, etc.

<Examples> The present invention will be described in more detail below with reference to Reference Examples and Examples, but the present invention is not limited thereto.

Toyoichime 1L (Synthesis method of 2-methylene-1,3-diphenyl-1,3-propanedione) 6.1 g (200 mol%) of paraformaldehyde.

20 mQ of an acetic acid solution containing 0.4 g (5 mol %) of copper acetate and 0.2 g (5 mol %) of potassium acetate was heated to 60° C. with stirring. Next, 50 mQ of a toluene solution containing 22.4 g of dibenzoylmethane was added dropwise, followed by heating to 80° C. and continued stirring. After confirming the completion of the reaction by thin layer chromatography, the reaction was carried out under reduced pressure.

The solvent was removed and purified by vacuum distillation to give 2-methylene-1,
3-diphenyl-1,3-propanedione was prepared.

The yield of the obtained product was 20.9 g (yield 88%). Moreover, the boiling point was 220° C. 70.6 s+Hg.

1j12 2-methylene-1,3-diphenyl-1,3-propanedione 0.2363g, styrene 0.115-1acetic acid 0
．． 001g and azobisisobutyronitrile 0.006
Charge 5g into a polymerization tube and apply under reduced pressure.

After degassing and sealing the tube, the tube was stirred for 48 hours in an oil bath at 60°C.Then, the tube was removed from the oil bath, allowed to cool, and opened. The obtained copolymer was dissolved in 1 mQ of methylene chloride, and then dissolved in 100 mQ of hexane. was added dropwise to perform precipitation separation. When the deposited precipitate was filtered and dried under reduced pressure, the yield of the obtained copolymer was 0.2132 g. Furthermore, the molecular weight in terms of styrene was measured by gel permeation chromatography and was 4200, and the composition ratio of diketone compound units and vinyl thread units was 50:50 by H-NMR. Furthermore, the obtained copolymer was identified by nuclear magnetic resonance spectroscopy.

The results are shown below.

'H-NMR (δ/CDC): 0.967-3.167 (br, 5H) 5.667
-8.267 (br, 15H) butyl vinyl ether 0.1002 instead of styrene
A copolymer was produced in the same manner as in Example 1 except that g was used, and the same measurements were performed.

The yield of the resulting copolymer was 0.2315 g/molecular weight 3800, and the composition ratio of 2-methylene-1,3-diphenyl-1,3-propanedione units and butyl vinyl ether units was 35:65. Met.

- 0.4726 g of 2-methylene-1,3-diphenyl-1,3-propanedione, 0.1722 g of vinyl acetate, 0.001 g of acetic acid, and 0.0 g of azobisisobutyronitrile.
A copolymer was produced in the same manner as in Example 1, except that 13 g was charged into the polymerization tube, and the same measurements were performed. The yield of the resulting copolymer was 0.4836 g, and the molecular weight was 5.
100, 2-methylene-1,3-diphenyl-1
The composition ratio of 3-propanedione units and vinyl acetate units was 50:50.

Acrylonitrile 0.1061g instead of vinyl acetate
A copolymer was produced in the same manner as in Example 3, except that
Similar measurements were made. The yield of the resulting copolymer was 0.2894 g, the molecular weight was 3200, and the composition ratio of 2-methylene-1,3-diphenyl-1°3-propanedione units to acrylonitrile units was 30:70.
Met.

4-vinylpyridine 0.2103 instead of vinyl acetate
A copolymer was produced in the same manner as in Example 3, except that g was used, and the same measurements were performed. The yield of the resulting copolymer was 0. ．． 5046g, molecular weight 6200, and the composition ratio of 2-methylene-1,3-diphenyl-1,3-propanedione units and 4-vinylpyridine units is 45:5.
It was 0.

1 eye 1 moxibustion Methyl methacrylate 0.200 instead of vinyl acetate
A copolymer was produced in the same manner as in Example 3 except that 2 g was used and acetic acid was not used, and the same measurements were performed. As a result, the yield of the obtained copolymer was 0.5341 g, and the molecular weight was 710.
The composition ratio of 0.2-methylene-1,3-diphenyl-1,3-propanedione units and methyl methacrylate units was 50:50.

Claims (1)

[Claims] The following general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼... (I) (In the formula, X represents an alkyl group, a substituted alkyl group, an aryl group, or a substituted aryl group, and Y represents an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, or an alkoxy group), and 0.1 to 50 mol% of 2-methylene-1,3-diketone compound units, and 99.9 mol% of vinyl monomer units. A diketone compound-based copolymer having a molecular weight of 500 to 1,000,000 and containing 50 mol%.