JPH02281013A - Diketone compound copolymer - Google Patents
Diketone compound copolymerInfo
- Publication number
- JPH02281013A JPH02281013A JP10166789A JP10166789A JPH02281013A JP H02281013 A JPH02281013 A JP H02281013A JP 10166789 A JP10166789 A JP 10166789A JP 10166789 A JP10166789 A JP 10166789A JP H02281013 A JPH02281013 A JP H02281013A
- Authority
- JP
- Japan
- Prior art keywords
- methylene
- diketone compound
- substituted
- copolymer
- vinyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920001577 copolymer Polymers 0.000 title claims abstract description 29
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 17
- 239000000178 monomer Substances 0.000 claims abstract description 15
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 14
- -1 methylenediketone compound Chemical group 0.000 claims abstract description 13
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 8
- 125000003118 aryl group Chemical group 0.000 claims abstract description 8
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 4
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 6
- 125000003107 substituted aryl group Chemical group 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims 1
- XQRUGGDFXXFONZ-UHFFFAOYSA-N 2-methylidene-1,3-diphenylpropane-1,3-dione Chemical compound C=1C=CC=CC=1C(=O)C(=C)C(=O)C1=CC=CC=C1 XQRUGGDFXXFONZ-UHFFFAOYSA-N 0.000 abstract description 9
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 abstract description 7
- 239000000853 adhesive Substances 0.000 abstract description 4
- 230000001070 adhesive effect Effects 0.000 abstract description 4
- 239000003973 paint Substances 0.000 abstract description 4
- 239000012209 synthetic fiber Substances 0.000 abstract description 4
- 229920002994 synthetic fiber Polymers 0.000 abstract description 4
- 229920003002 synthetic resin Polymers 0.000 abstract description 4
- 239000000057 synthetic resin Substances 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract 1
- 239000005977 Ethylene Substances 0.000 abstract 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 7
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000007870 radical polymerization initiator Substances 0.000 description 3
- UAJRSHJHFRVGMG-UHFFFAOYSA-N 1-ethenyl-4-methoxybenzene Chemical compound COC1=CC=C(C=C)C=C1 UAJRSHJHFRVGMG-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical compound C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- ZQMIGQNCOMNODD-UHFFFAOYSA-N diacetyl peroxide Chemical compound CC(=O)OOC(C)=O ZQMIGQNCOMNODD-UHFFFAOYSA-N 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- JMYZLRSSLFFUQN-UHFFFAOYSA-N (2-chlorobenzoyl) 2-chlorobenzenecarboperoxoate Chemical compound ClC1=CC=CC=C1C(=O)OOC(=O)C1=CC=CC=C1Cl JMYZLRSSLFFUQN-UHFFFAOYSA-N 0.000 description 1
- CBZMQWPBAUBAPO-UHFFFAOYSA-N 4-ethenyl-n,n-diethylaniline Chemical compound CCN(CC)C1=CC=C(C=C)C=C1 CBZMQWPBAUBAPO-UHFFFAOYSA-N 0.000 description 1
- KHBQMWCZKVMBLN-UHFFFAOYSA-N Benzenesulfonamide Chemical compound NS(=O)(=O)C1=CC=CC=C1 KHBQMWCZKVMBLN-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008360 acrylonitriles Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- NZZIMKJIVMHWJC-UHFFFAOYSA-N dibenzoylmethane Chemical compound C=1C=CC=CC=1C(=O)CC(=O)C1=CC=CC=C1 NZZIMKJIVMHWJC-UHFFFAOYSA-N 0.000 description 1
- GKCPCPKXFGQXGS-UHFFFAOYSA-N ditert-butyldiazene Chemical compound CC(C)(C)N=NC(C)(C)C GKCPCPKXFGQXGS-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- XJELOQYISYPGDX-UHFFFAOYSA-N ethenyl 2-chloroacetate Chemical compound ClCC(=O)OC=C XJELOQYISYPGDX-UHFFFAOYSA-N 0.000 description 1
- LJYCJYJAOWYANE-UHFFFAOYSA-N ethyl 2-benzoylprop-2-enoate Chemical compound CCOC(=O)C(=C)C(=O)C1=CC=CC=C1 LJYCJYJAOWYANE-UHFFFAOYSA-N 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000012690 ionic polymerization Methods 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000004809 thin layer chromatography Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 229920006163 vinyl copolymer Polymers 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F216/36—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by a ketonic radical
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明は、ジケトン化合物系共重合体に関し、更に詳細
には2−メチレン−1,3−ジケトン化合物単位と、ビ
ニル糸上ツマー単位とを含み、合成樹脂、合成繊維、塗
料又は接着剤等の改質材として利用可能な新規なジケト
ン化合物系共重合体に関する。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.
〈従来の技術〉
従来、ビニル系共重合体の特性を改善するために、種々
の化合物とビニル系モノマーとを共重合させた重合体が
種々検討されている。<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.
また、下記一般式(n)
−X
/
(式中Xはアルキル基、置換アルキル基、アリール基又
は置換アリール基を示し、Yはアルキル基、置換アルキ
ル基、アリール基、置換アリール基又はアルコキシ基を
示す)で表わされる2−メチレン−1,3−ジケトン化
合物は、すでに公知である。In addition, the following general formula (n) -X / (wherein, The 2-methylene-1,3-diketone compound represented by the following is already known.
しかしながら、前記2−メチレン−1,3−ジケトン化
合物と、ビニル系モノマーとを用いて得られる共重合体
については全く知られていないのが現状である。However, at present, nothing is known about a copolymer obtained using the 2-methylene-1,3-diketone compound and a vinyl monomer.
〈発明が解決しようとする課題〉
本発明の目的は、従来のビニルポリマーに比して柔軟性
、機械的強度、耐水性等に優れた新規なジケトン化合物
系共重合体を提供することにある。<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. .
本発明の別の目的は合成樹脂、合成繊維、塗料又は接着
剤等の改質材として利用できる新規なジケトン化合物系
共重合体を提供することにある。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.
〈課題を解決するための手段〉
本発明によれば、下記一般式(I)
(式中Xはアルキル基、置換アルキル基、アリール基又
は置換アリール基を示し、Yはアルキル基、置換アルキ
ル基、アリール基、置換アリール基又はアルコキシ基を
示す)で表わされる2−メチレン−1,3−ジケトン化
合物単位0.1〜50モル%と、ビニル系モノマー単位
99.9〜50モル%とを含む分子量500〜1000
000のジケトン化合物系共重合体が提供される。<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.
以下本発明を更に詳細に説明する。The present invention will be explained in more detail below.
本発明のジケトン化合物系共重合体は、特定の2−メチ
レン−1,3−ジケトン化合物単位と、ビニル系モノマ
ー単位とを含むことを特徴とする。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.
本発明において、2−メチレン−1,3−ジケトン化合
物単位は、下記一般式(I)で表わすことができ、
♂
(式中Xはアルキル基、置換アルキル基、アリール基又
は置換アリール基を示し、Yはアルキル基、置換アルキ
ル基、アリール基、置換アリール基又はアルコキシ基を
示す)。前記一般式(I)で表わされる2−メチレン−
1,3−ジケトン化合物単位を構成する2−メチレン−
1,3−ジケトン化合物としては、例えば2−メチレン
−1,3−ジフェニル−1,3−プロパンジオン、2−
メチレン−1,3−ジ−p−クロルフェニル−1,3−
プロパンジオン、2−メチレン−1−フェニル−1,3
−ブタンジオン、2−メチレン−1−フェニル−3−エ
トキシ−1,3−プロパンジオン等を好ましく挙げるこ
とができ、使用に際しては、単独若しくは混合物として
用いることができる。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.
前記2−メチレン−1,3−ジケトン化合物は、公知の
方法により調製することができる。The 2-methylene-1,3-diketone compound can be prepared by a known method.
本発明において、ビニル系モノマー単位を構成するビニ
ル系モノマーとしては1例えばスチレン、p−メトキシ
スチレン、p−ジエチルアミノスチレン等のスチレン誘
導体;ブチルビニルエーテル等のビニルエーテル類;酢
酸ビニル、クロロ酢酸ビニル等のビニルエステル類;ア
クリロニトリル、メタクリレートリル、2−エチル−3
−メチルアクリロニトリル等の(メタ)アクリロニトリ
ル誘導体、メチルメタクリレート、エチルメタクリレー
ト等のメタクリル酸エステル誘導体等を好ましく挙げる
ことができ、使用に際しては、単独若しくは混合物とし
て用いることができる。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.
本発明において、前記2−メチレン−1,3−ジケトン
化合物単位と、ビニル系モノマー単位との含有割合は、
2−メチレン−1,3−ジケトン化合物単位0.1〜5
0モル%、ビニル系モノマー単位99.9〜50モル%
である。前記2−メチレン−1,3−ジケトン化合物単
位の含有割合が0.1モル%未満の場合には、既存ビニ
ルポリマーの改質が不充分であり、また50モル%を超
えると未反応の2−メチレン−1,3−ジケトン化合物
が、得られる共重合体に混入するので前記含有割合とす
る必要がある。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.
また本発明のジケトン化合物系共重合体の分子量は50
0〜1oooooo、特に好ましくは2000〜200
000である。前記分子量が500未満の場合には耐熱
性、機械的強度が不充分であり、また10000000
を超えると柔軟性に欠け、且つ溶媒への溶解性が低下す
る。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.
本発明のジケトン化合物系共重合体を製造するには、前
記各モノマーを例えば有機過酸化物系。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.
アゾ化合物又はその他のラジカル重合開始剤の存在下、
塊状重合法、溶液重合法、懸濁重合法又は乳化重合法等
の公知のラジカル重合法により共重合させることにより
得ることができる。前記ラジカル重合開始剤としては、
例えば過酸化アセチル、過酸化−t−ブチル、過酸化ベ
ンゾイル、過酸化−2−クロロベンゾイル等の過酸化物
;2,2’−アゾビスイソブタン、1,1′−アゾ(メ
チルエチル)ジアセテート、2,2′−アゾビスイソブ
チロニトリル、1,1′−アゾビス−1−フェニルエタ
ン等のアゾ化合物、1,4−ビス(ペンタメチレン)−
2−テトラゼン、1.4−ジメトキシカルボニル−1,
4−ジフェニル−2−テトラゼン、ベンゼンスルホニル
アミド等を好ましく挙げることができる。前記ラジカル
重合開始剤の使用量は、特に限定されるものではないが
、全モノマー100重量部に対して0.5〜10重量部
であるのが好ましく、特に経済的には2重量部程度であ
るのが望ましい。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.
また前記共重合する際の重合温度は20〜150℃程度
であるのが好ましい。この際前記重合温度範囲外でも重
合反応は進行するが、150℃を超えると副反応を制御
するのが困難であるので好ましくなく、経済的に40〜
80℃程度が最も望ましい、一方反応時間は1重合部度
により異なるが、通常0.5〜120時間の範囲である
のが好ましい。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.
更に前記共重合反応は、無溶媒又は溶媒の存在下行うこ
とができる。前記溶媒としては、例えばメチルアルコー
ル、エチルアルコール等のアルコール類、塩化メチレン
、四塩化炭素、クロロベンゼン等のハロゲン化炭化水素
、トルエン、ベンゼン、キシレン等の炭化水素類等を挙
げることができ、溶媒の使用量は特に限定されないが、
経済的には全モノマー100重量部に対して、0−10
00重量部の範囲であるのが好ましい。また重合の際に
酢酸等のイオン重合禁止剤を使用することもできる。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.
〈発明の効果〉
本発明のジケトン化合物系共重合体は、特定の2−メチ
レン−1,3−ジケトン化合物単位を有するので、従来
のビニルポリマーに比して、柔軟性、機械的強度、耐水
性等に優れており、例えば合成樹脂、合成繊維、塗料及
び接着剤等の改質材として有用である。<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.
〈実施例〉
以下本発明を参考例及び実施例により更に詳細に説明す
るが、本発明はこれらに限定されるものではない。<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.
豊1目1L
(2−メチレン−1,3−ジフェニル−1,3−プロパ
ンジオンの合成法)
パラホルムアルデヒド6.1g(200モル%)。Toyoichime 1L (Synthesis method of 2-methylene-1,3-diphenyl-1,3-propanedione) 6.1 g (200 mol%) of paraformaldehyde.
酢酸銅0.4g(5モル%)、酢酸カリ0.2g(5モ
ル%)の酢酸溶液20mQを攪拌しながら60℃に加熱
した。次いでジベンゾイルメタン22.4gのトルエン
溶液50mQを滴下した後、80℃に加熱し、攪拌を続
けた。薄層クロマグラフィーにより反応の終了を確認し
た後、減圧下。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.
溶媒を除去し、減圧蒸留で精製し、2−メチレン−1,
3−ジフェニル−1,3−プロパンジオンを調製した。The solvent was removed and purified by vacuum distillation to give 2-methylene-1,
3-diphenyl-1,3-propanedione was prepared.
得られた生成物の収量は20.9g(収率88%)であ
った。また沸点は220℃70.6s+Hgであった。The yield of the obtained product was 20.9 g (yield 88%). Moreover, the boiling point was 220° C. 70.6 s+Hg.
ス1j12
2−メチレン−1,3−ジフェニル−1,3−プロパン
ジオン0.2363g、スチレン0.115−1酢酸0
.001g及びアゾビスイソブチロニトリル0.006
5gを重合管に仕込み、減圧下。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.
脱気封管した後、60℃の油浴において48時間攪拌し
た0次いで油浴から出し、放冷した後開管し、得られた
共重合体を塩化メチレン1mQに溶解した後、ヘキサン
100mQ中に滴下し、沈殿分離を行った。析出した沈
澱物を濾過し、減圧上乾燥したところ、得られた共重合
体の収量は0.2132gであった。またゲルパーミェ
ーションクロマトグラフ法によりスチレン換算の分子量
を測定したところ4200であり、ジケトン化合物単位
とビニル糸上ツマー単位との組成比を”H−NMRによ
り測定したところ、50 : 50であった。更に核磁
気共鳴スペクトルにより得られた共重合体を同定した。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.
その結果を以下に示す。The results are shown below.
’H−NMR(δ/CDC旦、):
0.967−3.167 (b r、5H)5.667
−8.267 (br、15H)失直■裟
スチレンの代わりにブチルビニルエーテル0.1002
gを用いた以外は実施例1と同様な方法で共重合体を製
造し、同様な測定を行った。'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.
その結果得られた共重合体の収量は0.2315g1分
子量3800であり、また2−メチレン−1,3−ジフ
ェニル−1,3−プロパンジオン単位と、ブチルビニル
エーテル単位との組成比は35 : 65であった。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.
ズ1」」−
2−メチレン−1,3−ジフェニル−1,3−プロパン
ジオン0.4726g、酢酸ビニル0.1722g、酢
酸0.001g及びアゾビスイソブチロニトリル0.0
13gを重合管に仕込んだ以外は、実施例1と同様な方
法で共重合体を製造し、同様な測定を行った。その結果
得られた共重合体の収量は0.4836g、分子量は5
100であり、2−メチレン−1,3−ジフェニル−1
゜3−プロパンジオン単位と、酢酸ビニル単位との組成
比は50 : 50であった。- 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.
災1涯土
酢酸ビニルの代わりにアクリロニトリル0.1061g
を用いた以外は、実施例3と同様に共重合体を製造し、
同様な測定を行った。その結果得られた共重合体の収量
は0.2894g、分子量3200であり、2−メチレ
ン−1,3−ジフェニル−1゜3−プロパンジオン単位
と、アクリロニトリル単位との組成比は30 : 70
であった。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.
叉凰五旦
酢酸ビニルの代わりに4−ビニルピリジン0.2103
gを用いた以外は、実施例3と同様に共重合体を製造し
、同様な測定を行った。その結果得られた共重合体の収
量は0..5046g、分子量6200であり、2−メ
チレン−1,3−ジフェニル−1,3−プロパンジオン
単位と、4−ビニルピリジン単位との組成比は45:5
0であった。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.
ス1目1灸
酢酸ビニルの代わりにメチルメタクリレート0.200
2gを用い、酢酸を使用しない以外は実施例3と同様に
共重合体を製造し、同様な測定を行った。その結果、得
られた共重合体の収量は0.5341g、分子量710
0.2−メチレン−1,3−ジフェニル−1,3−プロ
パンジオン単位と、メチルメタクリレート単位との組成
比は、50 : 50であった。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)
は置換アリール基を示し、Yはアルキル基、置換アルキ
ル基、アリール基、置換アリール基又はアルコキシ基を
示す)で表わされる2−メチレン−1,3−ジケトン化
合物単位0.1〜50モル%と、 ビニル系モノマー単位99.9〜50モル%とを含む分
子量500〜1000000のジケトン化合物系共重合
体。[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%.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP10166789A JPH02281013A (en) | 1989-04-24 | 1989-04-24 | Diketone compound copolymer |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP10166789A JPH02281013A (en) | 1989-04-24 | 1989-04-24 | Diketone compound copolymer |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH02281013A true JPH02281013A (en) | 1990-11-16 |
Family
ID=14306724
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP10166789A Pending JPH02281013A (en) | 1989-04-24 | 1989-04-24 | Diketone compound copolymer |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH02281013A (en) |
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