JPS6368610A - Production of copolymer - Google Patents
Production of copolymerInfo
- Publication number
- JPS6368610A JPS6368610A JP21258386A JP21258386A JPS6368610A JP S6368610 A JPS6368610 A JP S6368610A JP 21258386 A JP21258386 A JP 21258386A JP 21258386 A JP21258386 A JP 21258386A JP S6368610 A JPS6368610 A JP S6368610A
- Authority
- JP
- Japan
- Prior art keywords
- copolymer
- monomer mixture
- vinyl chloride
- vinylidene chloride
- chloride
- 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 43
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 239000000178 monomer Substances 0.000 claims abstract description 39
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000000203 mixture Substances 0.000 claims abstract description 21
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 claims abstract description 18
- GSQMUEGXIDQJES-UHFFFAOYSA-N 1,1-dichloro-2-methylprop-1-ene Chemical group CC(C)=C(Cl)Cl GSQMUEGXIDQJES-UHFFFAOYSA-N 0.000 claims description 4
- 238000010526 radical polymerization reaction Methods 0.000 claims description 3
- 239000002904 solvent Substances 0.000 abstract description 15
- 239000011230 binding agent Substances 0.000 abstract description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 abstract description 2
- 239000011248 coating agent Substances 0.000 abstract description 2
- 238000007639 printing Methods 0.000 abstract description 2
- 238000006116 polymerization reaction Methods 0.000 description 18
- 239000004014 plasticizer Substances 0.000 description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 238000000465 moulding Methods 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 5
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000003973 paint Substances 0.000 description 5
- 230000009257 reactivity Effects 0.000 description 5
- 230000007423 decrease Effects 0.000 description 4
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 4
- 239000006247 magnetic powder Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000010557 suspension polymerization reaction Methods 0.000 description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000007720 emulsion polymerization reaction Methods 0.000 description 3
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000375 suspending agent Substances 0.000 description 3
- 238000005979 thermal decomposition reaction Methods 0.000 description 3
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 235000010582 Pisum sativum Nutrition 0.000 description 2
- 240000004713 Pisum sativum Species 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- KZIKDWMVGLXOTB-UHFFFAOYSA-N chloranylethene Chemical compound ClC=C.ClC=C KZIKDWMVGLXOTB-UHFFFAOYSA-N 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- -1 phthalate ester Chemical class 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 2
- 229920002959 polymer blend Polymers 0.000 description 2
- 238000007127 saponification reaction Methods 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- BEQKKZICTDFVMG-UHFFFAOYSA-N 1,2,3,4,6-pentaoxepane-5,7-dione Chemical compound O=C1OOOOC(=O)O1 BEQKKZICTDFVMG-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- OHXAOPZTJOUYKM-UHFFFAOYSA-N 3-Chloro-2-methylpropene Chemical compound CC(=C)CCl OHXAOPZTJOUYKM-UHFFFAOYSA-N 0.000 description 1
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-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
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- UUPWEGAONCOIFJ-UHFFFAOYSA-N CCCCC(CC)COC(=O)OOC(O)=O Chemical compound CCCCC(CC)COC(=O)OOC(O)=O UUPWEGAONCOIFJ-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000004803 Di-2ethylhexylphthalate Substances 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000004831 Hot glue Substances 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- RVGRUAULSDPKGF-UHFFFAOYSA-N Poloxamer Chemical compound C1CO1.CC1CO1 RVGRUAULSDPKGF-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 108090000951 RNA polymerase sigma 70 Proteins 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 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
- 239000000853 adhesive Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- DHZSIQDUYCWNSB-UHFFFAOYSA-N chloroethene;1,1-dichloroethene Chemical compound ClC=C.ClC(Cl)=C DHZSIQDUYCWNSB-UHFFFAOYSA-N 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- ZJXZSIYSNXKHEA-UHFFFAOYSA-N ethyl dihydrogen phosphate Chemical compound CCOP(O)(O)=O ZJXZSIYSNXKHEA-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- WHJNQEHPYYGWGL-UHFFFAOYSA-N n-(1-hydroxy-2-methylpropan-2-yl)prop-2-enamide Chemical compound OCC(C)(C)NC(=O)C=C WHJNQEHPYYGWGL-UHFFFAOYSA-N 0.000 description 1
- AJCDFVKYMIUXCR-UHFFFAOYSA-N oxobarium;oxo(oxoferriooxy)iron Chemical compound [Ba]=O.O=[Fe]O[Fe]=O.O=[Fe]O[Fe]=O.O=[Fe]O[Fe]=O.O=[Fe]O[Fe]=O.O=[Fe]O[Fe]=O.O=[Fe]O[Fe]=O AJCDFVKYMIUXCR-UHFFFAOYSA-N 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【発明の詳細な説明】
(イ)発明の目的
〔産業上の利用分野〕
本発明は高度の熱安定性を有し、安価な溶剤或いは可塑
剤に可溶な塩化ビニルと塩化ビニリデンとの共重合体の
製法に関するものであり、これにより得られる共重合体
は、磁性塗料用基材、顔料分散用樹脂或いは粘着助剤用
の樹脂などとして利用出来る。Detailed Description of the Invention (a) Purpose of the Invention [Field of Industrial Application] The present invention is a combination of vinyl chloride and vinylidene chloride that has a high degree of thermal stability and is soluble in inexpensive solvents or plasticizers. This invention relates to a method for producing a polymer, and the copolymer obtained thereby can be used as a base material for magnetic paint, a resin for dispersing pigments, a resin for adhesion aid, etc.
塩化ビニルと塩化ビニリデンとの共重合体は、その特徴
とする性質即ち、ガスバリヤ−性、柔軟性、或いは接着
性を生かして、多くの方面での使用が検討されてきた。Copolymers of vinyl chloride and vinylidene chloride have been studied for use in many fields, taking advantage of their characteristic properties, ie, gas barrier properties, flexibility, and adhesive properties.
しかしながら、この共重合体の加熱による著しい分解性
及び低床な溶剤への溶解力の不足、さ6には重合反応性
の不均一による共重合体の生産性の不良などの理由によ
り、その実際の用途は著しく限定されていた。However, due to the remarkable decomposition of this copolymer by heating, the lack of solubility in low-grade solvents, and the poor productivity of the copolymer due to non-uniformity of polymerization reactivity, there are many reasons why this copolymer is not practical. Its uses were extremely limited.
これに対して、特開昭59−164514号公報におい
て、塩化ビニル単量体と塩化ビニリデン単量体とを主成
分とし、アリルクロライド単量体又はメタリルクロライ
ド単量体を含有してなる単量体混合物をラジカル重合す
ることにより、熱安定性が改良され、しかも安価な芳香
族炭化水素系の溶剤に可溶な、塩化ビニル−塩化ビニI
Jデン系共重合体を得る方法が提案されているが、斯か
る共重合体にしても、例えば磁性塗料用基材として用い
るには一般的に耐熱分解性がなお今−歩であった。On the other hand, in JP-A No. 59-164514, a monomer mainly composed of vinyl chloride monomer and vinylidene chloride monomer and containing allyl chloride monomer or methallyl chloride monomer is disclosed. Vinyl chloride-vinyl chloride I, which has improved thermal stability and is soluble in inexpensive aromatic hydrocarbon solvents, is produced by radical polymerization of a polymer mixture.
Although methods for obtaining J-density copolymers have been proposed, such copolymers generally still have poor thermal decomposition resistance for use as base materials for magnetic paints, for example.
又、電子線硬化塗料用基材は最近注目を浴びておりその
基材としてアクリロイル基を導入した塩化ビニル−塩化
ビニリゾy系共重合体を用いることが提唱されているが
、この共重合体を製造するために用いられる塩化ビニル
−塩化ビニリデン系共重合体は、アクリロイル基を導入
するための反応時に加熱を要するため、従来よりもさら
に高度な耐熱分解性が求められているのが現状である。In addition, the base material for electron beam-curable paints has recently been attracting attention, and it has been proposed to use a vinyl chloride-vinyl chloride y-based copolymer into which an acryloyl group has been introduced as the base material. The vinyl chloride-vinylidene chloride copolymer used for production requires heating during the reaction to introduce the acryloyl group, so there is currently a need for even higher heat decomposition resistance than before. .
さらに、前記特開昭59−1154314号公報に記載
の塩化ビニル−塩化ビニリデン系共重合体は、ジオクチ
ルフタレート又はジブチルフタレート等の安価な可塑剤
への溶解性が不十分なために、ペースト塩ビゾルの顔料
分散用助剤及び接着剤としての使用において制限を有し
ていた。Furthermore, the vinyl chloride-vinylidene chloride copolymer described in JP-A-59-1154314 has insufficient solubility in inexpensive plasticizers such as dioctyl phthalate or dibutyl phthalate, It had limitations in its use as a pigment dispersion aid and adhesive.
本発明においては、塩化ビニル−塩化ビニリデン系共重
合体の耐熱分解性と可塑剤への溶解性とを向上させるこ
とを技術的課題とする。The technical objective of the present invention is to improve the heat decomposition resistance and solubility in plasticizers of a vinyl chloride-vinylidene chloride copolymer.
(ロ)発明の構成
〔問題点を解決する為の手段〕
本発明者等は前記問題点について鋭意検討した結果、本
発明を完成した。(B) Structure of the Invention [Means for Solving the Problems] The present inventors have completed the present invention as a result of intensive study on the above-mentioned problems.
即ち、本発明は、塩化ビニル、塩化ビニリデン及びr、
r’ジクロロイソブチレン及び所望により、他のラジカ
ル重合性単量体からなる単量体混合物であって、r、ビ
ジクロロイソブチレンを上記必須単量体混合物中0.1
〜20重量%含有し、かつ塩化ビニルと塩化ビニリデン
の合計量が全単量体混合物中の主成分を占める前記単量
体混合物を、ラジカル重合することを特徴とする共重合
体の製造方法である。That is, the present invention provides vinyl chloride, vinylidene chloride and r,
A monomer mixture consisting of r'dichloroisobutylene and optionally other radically polymerizable monomers, wherein 0.1 of r,bidichloroisobutylene is present in the above essential monomer mixture.
A method for producing a copolymer, characterized in that the monomer mixture containing ~20% by weight and in which the total amount of vinyl chloride and vinylidene chloride constitutes the main component in the entire monomer mixture is subjected to radical polymerization. be.
上記方法により、本発明者等は、塩化ビニル単量体単位
と塩化ビニリデン単量体単位との合計量を主成分としな
がらも、高度の熱安定性及び安価な芳香族炭化水素を主
体とする溶剤或いはジオクチルフタレート或いはジブチ
ルフタレートなどの可塑剤に可溶な塩化ビニル−塩化ビ
ニリデン系共重合体の製造を可能とした。By the above method, the present inventors have succeeded in producing a compound containing mainly a highly thermally stable and inexpensive aromatic hydrocarbon, while containing the total amount of vinyl chloride monomer units and vinylidene chloride monomer units as the main component. It has become possible to produce vinyl chloride-vinylidene chloride copolymers that are soluble in solvents or plasticizers such as dioctyl phthalate or dibutyl phthalate.
次に本発明方法の構成要件を順次説明する。Next, the constituent elements of the method of the present invention will be sequentially explained.
塩化ビニルと塩化ビニリデンは、その合計量が全単量体
混合物中の主成分であることが必要であり、又塩化ビニ
ルと塩化ビニリデンは各々4〜95重量%含有すること
が望しい。It is necessary that the total amount of vinyl chloride and vinylidene chloride be the main components in the entire monomer mixture, and it is desirable that the content of each of vinyl chloride and vinylidene chloride is 4 to 95% by weight.
塩化ビニルと塩化ビニリデンの合計量が全単量体混合物
中主成分でない場合は、塩化ビニル−塩化ビニIJデン
系共重合体のもつ特性、即ち柔軟性、接着性、成型時の
流動性、耐熱分解性、芳香族炭化水素を主体とする溶剤
或いはフタル酸エステル系の可塑剤に対して溶解性等が
不良となる。If the total amount of vinyl chloride and vinylidene chloride is not the main component in the total monomer mixture, the characteristics of the vinyl chloride-vinylidene chloride IJ-density copolymer, such as flexibility, adhesiveness, fluidity during molding, and heat resistance. Degradability and solubility in aromatic hydrocarbon-based solvents or phthalate ester plasticizers are poor.
塩化ビニルが4重量%を満さない場合は共重合体の柔軟
性、接着性、或いは成型時の流動性が不良となると同時
に耐熱分解性及び単量体混合物の重合反応性の低下を来
たしやすい。また95重量を越えると共重合体の柔軟性
、接着性、或いは成型時の流動性が不良となると同時に
芳香族炭化水素を主体とする溶剤或いは7タル酸エステ
ル系可塑剤への溶解性及び単量体混合物の重合反応性の
低下を来たしやすい。If the vinyl chloride content is less than 4% by weight, the flexibility, adhesion, or fluidity during molding of the copolymer will be poor, and at the same time, the thermal decomposition resistance and polymerization reactivity of the monomer mixture will likely decrease. . If the weight exceeds 95%, the copolymer's flexibility, adhesion, or fluidity during molding will be poor, and at the same time, its solubility in aromatic hydrocarbon-based solvents or heptatalic acid ester plasticizers will deteriorate. This tends to cause a decrease in the polymerization reactivity of the polymer mixture.
塩化ビニIJデンが4重量%満さない場合は共重合体の
柔軟性、接着性、又は加熱成型時の流動性が不良となる
と同時な芳香族炭化水素を主体とする溶剤或いはフタル
酸エステル系可塑剤への溶解性及び単量体混合物の重合
反応性の低下を来たしやすい。また95重f%を越える
と芳香族炭化水素を主体とする溶剤或いはフタル酸エス
テル系可塑剤への溶解性乃至成型時の流動性が不良とな
る。If the vinyl chloride IJ density is less than 4% by weight, the copolymer's flexibility, adhesion, or fluidity during heat molding will be poor. The solubility in plasticizers and the polymerization reactivity of the monomer mixture tend to decrease. If it exceeds 95% by weight, the solubility in solvents mainly composed of aromatic hydrocarbons or phthalate plasticizers and fluidity during molding will be poor.
次にr、 r’ジクロロインブチレンは、必須単量体混
合物中α1〜20重量%配合することが必要である。α
1重量%を満さないときは耐熱分解性或いは耐候性が著
しく不良であると同時に、柔軟性、接着性或いは成型時
の流動性の不良を来たす他、芳香族炭化水素を主体とす
る溶剤或いはフタル酸エステル系可塑剤への溶解性が低
下する。また20重量%な趙えると、重合反応性が著し
く低下すると共に得られた共重合体の機械的強度の低下
が著しい。Next, it is necessary to mix r, r' dichloroin butylene in an amount of α1 to 20% by weight in the essential monomer mixture. α
If the amount is less than 1% by weight, the thermal decomposition resistance or weather resistance will be extremely poor, and at the same time, the flexibility, adhesion, or fluidity during molding will be poor. Solubility in phthalate plasticizers decreases. Moreover, when the content is 20% by weight, the polymerization reactivity is significantly reduced and the mechanical strength of the obtained copolymer is also significantly reduced.
上記3種の単量体以外の他のラジカル重合性単量体も用
途に応じ使用することが出来る。その他のラジカル重合
性単量体の内、例えばさらに溶剤或いは可塑剤への溶解
性、成型時の流動性を増すことを目的として使用するこ
とができる単量体としては、ビニルエステル、ビニルエ
ーテル、メタリルクロライドが、又接着性成いは磁性粉
に対する分散性をさらに高めるのに使用することができ
る単量体としては、アクリル酸、ヒドロキシエチルアク
リレート、無水マレイン酸、N−メチロールアクリルア
マイド、グリシジルメタクリレート、2−アクリルアミ
ド−2−メチルプロパン子ルホン酸、アクリル酸−2−
リン酸エチルなどが、それぞれ挙げられる。斯る単量体
は単独で又は2種併用して使用することが出来る。これ
らの所望により共重合される単量体の使用量は、上記必
須単量体混合物に対し0〜40重量%に保持することが
望しい。40重量%を越えると、上記に示した本発明の
目的とする共重合体の特性が発揮し難くなる。Radically polymerizable monomers other than the above three types of monomers can also be used depending on the purpose. Among other radically polymerizable monomers, examples of monomers that can be used for the purpose of further increasing solubility in solvents or plasticizers and fluidity during molding include vinyl esters, vinyl ethers, and methane. Monomers that can be used to further enhance the adhesive properties or dispersibility of lyl chloride in magnetic powders include acrylic acid, hydroxyethyl acrylate, maleic anhydride, N-methylol acrylamide, glycidyl methacrylate. , 2-acrylamido-2-methylpropanol sulfonic acid, acrylic acid-2-
Examples include ethyl phosphate and the like. Such monomers can be used alone or in combination. The amount of these optionally copolymerized monomers to be used is desirably maintained at 0 to 40% by weight based on the above-mentioned essential monomer mixture. If it exceeds 40% by weight, it becomes difficult for the copolymer to exhibit the above-mentioned properties targeted by the present invention.
本発明で用いる単量体のさらに好しい配合割合は、塩化
ビニル15〜70重i−チ、塩化ビニリデン15〜70
重量%、γ、γ′ ジクロロイソブチレフ1〜10重量
%であり、他のラジカル ゛重合性単量体は必須単量
体混合物に対して0〜15重量%である。A more preferable blending ratio of the monomers used in the present invention is vinyl chloride 15 to 70% vinylidene chloride, vinylidene chloride 15 to 70%
% by weight, γ, γ' dichloroisobutyleph, 1 to 10% by weight, and other radically polymerizable monomers, based on the essential monomer mixture, 0 to 15% by weight.
本発明に於いて、その他の重合反応条件は常法により適
宜、種々の条件が採用され得るが、工業的には重合温度
40〜70℃、重合時間7〜20Hrが望ましい。In the present invention, various other polymerization reaction conditions may be suitably employed according to conventional methods, but industrially preferred are a polymerization temperature of 40 to 70°C and a polymerization time of 7 to 20 hours.
重合方法は懸濁重合法、乳化重合法及び溶液重合法のい
ずれも採用することが出来る。As the polymerization method, any of suspension polymerization, emulsion polymerization, and solution polymerization can be employed.
例えば最も簡便な懸濁重合法を採用する場合は、懸濁剤
として部分ケン化PVA、メチルセルロース、エチレン
オキサイドとプロピレンオキサイドの共重合体或いは酢
酸ビニルとマレイン酸との共重合体を用いることが出来
、又ラジカル発生型触媒としてはベンゾイルパーオキサ
イド、ラウロイルパーオキサイド、ジターエチルヘキシ
ルパーオキシジカーボネート、α、α′−ジメチルバレ
ロニトリルなどが用いられる。For example, when using the simplest suspension polymerization method, partially saponified PVA, methyl cellulose, a copolymer of ethylene oxide and propylene oxide, or a copolymer of vinyl acetate and maleic acid can be used as the suspending agent. As the radical-generating catalyst, benzoyl peroxide, lauroyl peroxide, diterethylhexyl peroxydicarbonate, α,α'-dimethylvaleronitrile, etc. are used.
又乳化重合法或いは溶液重合法を採用するときは、水溶
性触媒、或いは油溶性触媒、乳化剤、汎用性の各種溶媒
を適宜使用し、本発明の目的を達成することが出来る。When emulsion polymerization or solution polymerization is employed, the objects of the present invention can be achieved by appropriately using water-soluble catalysts, oil-soluble catalysts, emulsifiers, and various general-purpose solvents.
なお、本発明における重合は、懸濁重合法、乳化重合法
或いは溶液重合法において、これら重合法で使用する媒
体中に脂肪族系のポリカーボネート、芳香族系のポリエ
ステル或いはコポリアミドを共存させて行なうことも可
能であり、斯る重合により得られる共重合体は、グラフ
ト共重合体を部分的に含有しており、磁性粉の分散剤及
びホットメルト接着剤として用いることができる。The polymerization in the present invention is carried out in suspension polymerization, emulsion polymerization, or solution polymerization in the presence of aliphatic polycarbonate, aromatic polyester, or copolyamide in the medium used in these polymerization methods. The copolymer obtained by such polymerization partially contains a graft copolymer and can be used as a dispersant for magnetic powder and a hot melt adhesive.
本発明の目的が達成せられるのは本質的には、塩化ビニ
ル、塩化ビニリデン及びγ、γ′ジクロルイソブチレン
との三元共重合体の特異な物性とその三元共重合性に帰
因するものである。The achievement of the object of the present invention is essentially attributable to the unique physical properties of the terpolymer of vinyl chloride, vinylidene chloride, and γ, γ′ dichloroisobutylene and its terpolymerizability. It is something.
以下、実施例及び比較例を挙げて、本発明をさらに具体
的に説明する。EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples.
尚、各側で得られた重合体の各特性は次の方法により測
定した。In addition, each characteristic of the polymer obtained on each side was measured by the following method.
a)熱安定性:
熱安定剤を添加せず80℃で1ケ月間ギヤーオーブン中
に維持してその変色状態を目視により観察した。a) Thermal stability: The sample was kept in a gear oven at 80° C. for one month without adding a heat stabilizer, and the state of discoloration was visually observed.
b)トルエン/メチルエチルケトン(80fEfチ/2
0重量ts)からなる混合溶媒(以下、単にトルエン系
溶剤と称す)に対する溶解性:トルエン系溶剤70重量
部に共重合体30重量部を加え、室温で2時間攪拌した
後、溶液の濁りの有無を観察した。b) Toluene/methyl ethyl ketone (80fEf/2
Solubility in a mixed solvent (hereinafter simply referred to as toluene solvent) consisting of 0 weight ts): 30 parts by weight of the copolymer was added to 70 parts by weight of toluene solvent, and after stirring at room temperature for 2 hours, the solution became cloudy. The presence or absence was observed.
C)ジー2−エチルへキシルフタレート(以下、DOP
と記す)K対する溶解性:
DOP80重量部に共重合体20重量部を加え、150
℃で2時間攪拌した後、室温に戻し、溶液の濁りの有無
を観察した。C) Di-2-ethylhexyl phthalate (hereinafter referred to as DOP)
) Solubility in K: Add 20 parts by weight of copolymer to 80 parts by weight of DOP,
After stirring at °C for 2 hours, the temperature was returned to room temperature and the presence or absence of turbidity of the solution was observed.
d)密着性試験:
共重合体の20重i%のテトラヒドロフラン溶液を調整
し、該溶液を軟鋼板に室温下で塗布した後乾燥成膜を行
い、JISK−6744のエリクセン試験法により剥離
の有無を観察した。d) Adhesion test: A 20wt% tetrahydrofuran solution of the copolymer was prepared, and the solution was applied to a mild steel plate at room temperature, followed by dry film formation, and the presence or absence of peeling was determined using the Erichsen test method of JISK-6744. observed.
e)磁性粉の分散性
バリウムフェライト微粉末12gr、 共重合体1.
4gr、ウレタン重合体にツボラン2604、日本ポリ
ウレタン■製)α6grsメチルエチルケトン16gr
、)ルエン16gr及びガラスピーズ80grよりなる
配合物を10時間ペイントコンディジ冒ナナ−振とう后
、ガラスピーズな濾過して得た溶液を直ちにポリエステ
ルフィルム上に100μの厚さとなるようにドクターブ
レードにて塗布して60℃で10時間加熱后、日本電色
工業+11製シグマ80カラーメジャーリングシステム
(Σ80COLORMEA*5URING SYST
EM)により60° の反射率を測定した。反射率が高
い根分散性のよいことを示す。e) Dispersibility of magnetic powder Barium ferrite fine powder 12 gr, copolymer 1.
4gr, urethane polymer with Tuboran 2604, Nippon Polyurethane) α6grs methyl ethyl ketone 16gr
,) A formulation consisting of 16 gr of luene and 80 gr of glass peas was shaken in a paint conditioner for 10 hours, and the solution obtained by filtering the glass peas was immediately applied to a polyester film with a doctor blade to a thickness of 100 μm. After coating and heating at 60℃ for 10 hours, the Nippon Denshoku Kogyo +11 Sigma 80 Color Measuring System (Σ80COLORMEA*5URING SYST) was applied.
The reflectance at 60° was measured by EM). High reflectance indicates good root dispersion.
f)平均重合度:
JISK−6721の粘度法に拠り塩化ビニル単独重合
体に換算した数値を求めた。f) Average degree of polymerization: A value converted to a vinyl chloride homopolymer was determined according to the viscosity method of JISK-6721.
実施例t 5−eオートクレーブに塩化ビニル10105O。Example t 5-e Vinyl chloride 10105O in autoclave.
塩化ビニリデン390gr、 r、 r’ジクロロイン
ブチレン60gr、懸濁剤として0KS−7514(ケ
ン化度40モル−0部分ケン化PVA、日本合成化学工
業■製)7.5gr及びエバン485(酸化エチレンと
酸化プロピレンとのプロ、り共重合体、第一工業製薬■
製)15gr、ラジカル発生型触媒として2−エチルへ
キシルパーオキシジカーボネート5gr並びに純水30
00grを仕込み、500rpm の攪拌下にて60
℃で13時間懸濁重合を行った。遠心脱水分離層、乾燥
し、その結果、重合収率は83重M%で粉末共重合体を
得た。この共重合体の特性を評価し、その結果を表−1
に示した。390 gr of vinylidene chloride, 60 gr of r, r' dichloroin butylene, 7.5 gr of 0KS-7514 (saponification degree 40 mol - 0 partially saponified PVA, manufactured by Nippon Gosei Kagaku Kogyo ■) as a suspending agent, and Evan 485 (with ethylene oxide). Pro-copolymer with propylene oxide, Daiichi Kogyo Seiyaku ■
) 15gr, 5gr of 2-ethylhexyl peroxydicarbonate as a radical-generating catalyst, and 30gr of pure water.
00 gr and stirred at 500 rpm.
Suspension polymerization was carried out at ℃ for 13 hours. The centrifugal dehydration separation layer was dried, and as a result, a powder copolymer was obtained with a polymerization yield of 83% by weight. The properties of this copolymer were evaluated and the results are shown in Table 1.
It was shown to.
実施例2〜M及び比較例1〜3
実施例1に於いて、単量体組成を変更し、他の重合条件
は同一にして重合を行ない、得られた共重合体の特性を
評価し、その結果を表−1実施例9
52オートクレーブに塩化ビニル900gr。Examples 2 to M and Comparative Examples 1 to 3 In Example 1, polymerization was carried out by changing the monomer composition and keeping the other polymerization conditions the same, and the properties of the obtained copolymers were evaluated. The results are shown in Table 1. Example 9 52 900 gr of vinyl chloride was placed in an autoclave.
塩化ビニリデン495 gr、無水マレイン酸45gr
、γ、γ′−ジクロロイソブチレン45gr。Vinylidene chloride 495 gr, maleic anhydride 45 gr
, γ, γ'-dichloroisobutylene 45 gr.
懸濁剤としてe)KS−7514(ケン化度45モルチ
の部分ケン化ポリビニルアルコール、日本合成化学工業
■製)7.5gr及びエパン485(酸化エチレンと酸
化プロピレンとのブロック共重合体、第一工業製薬■製
) 15 gr、ラジカル発生触媒として2−エチルへ
キシルバーオキシジカーボネー)5 gr並びに純水5
000 grを仕込み、500 rpmの攪拌に60℃
で13時間懸濁重合を行なった。遠心脱水分離後、乾燥
し粉末状の共重合体を得た。As a suspending agent e) 7.5 gr of KS-7514 (partially saponified polyvinyl alcohol with a degree of saponification of 45 molar, manufactured by Nippon Gosei Kagaku Kogyo ■) and Epan 485 (a block copolymer of ethylene oxide and propylene oxide, the first (manufactured by Kogyo Seiyaku ■) 15 gr, 2-ethylhexyl silver oxydicarbonate (2-ethylhexyloxydicarbonate) 5 gr as a radical generating catalyst, and pure water 5 gr.
000 gr and stirred at 500 rpm at 60°C.
Suspension polymerization was carried out for 13 hours. After centrifugal dehydration, the copolymer was dried to obtain a powdery copolymer.
比較例4
実施例参にて用いたγ、γ′−ジクロロイソブチレンに
代えてメタクリルクロライドをそれと同じ量使用し、そ
の他の原料の仕込み割合及び重合条件は実施例4と同じ
にして重合することにより、粉末状の共重合体を得た。Comparative Example 4 By using the same amount of methacrylic chloride in place of γ,γ'-dichloroisobutylene used in Example 4, and using the same charging ratios of other raw materials and polymerization conditions as in Example 4, polymerization was carried out. , a powdery copolymer was obtained.
いて、数平均分子量、各種溶剤への溶解性及び加熱溶融
性を評価し、その結果を表−2に示した。The number average molecular weight, solubility in various solvents, and heat meltability were evaluated, and the results are shown in Table 2.
なお、上記の特性の評価方法は次に示すとおりである。Note that the evaluation method for the above characteristics is as follows.
O数平均分子量
ケルパーミェーションクロマトグラフィー法に拠り、ポ
リスチレン換算の数平均分子量で示した。O number average molecular weight: Based on Kel permeation chromatography method, the number average molecular weight is expressed as a polystyrene equivalent.
0溶解性
溶剤に対し固形分濃度が601f%となるように共重合
体を添加し、室温で60分間攪拌した後、液の状態を目
視により評価した。The copolymer was added so that the solid content concentration was 601f% with respect to the 0-solubility solvent, and after stirring at room temperature for 60 minutes, the state of the liquid was visually evaluated.
0加熱溶融性
共重合体を粉同志が重ならないように薄い鉄板上圧分散
させ、これを130℃のオープンに3分間入れた後、外
に取り出し粉の溶融状態を目視により評価した。完全に
溶融したものを良好と、つぶが少し残っているものをや
や不良とそれぞれ判定した。The copolymer that melts under zero heat was dispersed under pressure on a thin iron plate so that the powders would not overlap, and after being placed in an open oven at 130°C for 3 minutes, the powder was taken out and the melting state of the powder was visually evaluated. Those that were completely melted were judged as good, and those that had some lumps remaining were judged as somewhat poor.
表−2
〔注〕1)トルエンとメチルエチルケトンとを1=1(
重量比)の比率で混合してなる溶剤を示す。Table 2 [Note] 1) Toluene and methyl ethyl ketone are 1=1 (
This indicates a solvent mixed in a ratio of (weight ratio).
実施例9および比較例4より、γ、γ′−ジクロロイン
ブテンを共重合してなる塩化ビニル−塩化ビニリデン系
共重合体の方がメタクリルクロライドを共重合してなる
塩化ビニル−塩化ビニリデン系共重合体に比べて、溶剤
に対する溶解性及び加熱溶融性において優れることが分
る。From Example 9 and Comparative Example 4, the vinyl chloride-vinylidene chloride copolymer obtained by copolymerizing γ, γ'-dichloroinbutene is better than the vinyl chloride-vinylidene chloride copolymer obtained by copolymerizing methacrylic chloride. It can be seen that it is superior in solubility in solvents and heat-melting properties compared to polymers.
また、r、γ′−ジクロロイソブチンは消防法にいう第
二石油類に属し、メタクリルクロライドは第−石油類に
属するので、取扱い易さの面においてもγ r/−ジク
ロロイソブチンの方が好ましいのである。In addition, r,γ'-dichloroisobutyne belongs to the second petroleum class under the Fire Service Act, and methacrylic chloride belongs to the class petroleum class, so γ r/-dichloroisobutyne is easier to handle. It is preferable.
(ハ)発明の効果
本発明によって得られる共重合体は、熱安定性、溶剤に
対する溶解性、密着性及び磁性粉又は顔料に対する分散
性に優れているので、種々の分野で使用することができ
、例えばコンクリート、金属材料及び合成樹脂への各種
コーティング剤の塗布前に使用するプライマー、磁気記
録媒体のバインダー、印刷インキ用バインダー、ペイン
ト用ビヒクル、粉体塗装用樹脂、ガスバリヤ−性包装材
料、磁性粉を含有するシーラー、並びにペースト塩ビゾ
ルの顔料分散剤等として好適である。(c) Effects of the invention The copolymer obtained by the invention has excellent thermal stability, solubility in solvents, adhesion, and dispersibility in magnetic powder or pigments, so it can be used in various fields. For example, primers used before applying various coatings to concrete, metal materials and synthetic resins, binders for magnetic recording media, binders for printing inks, vehicles for paint, resins for powder coatings, gas barrier packaging materials, magnetic It is suitable as a sealer containing powder, a pigment dispersant for paste vinyl chloride sol, etc.
Claims (1)
イソブチレン及び所望により他のラジカル重合性単量体
からなる単量体混合物であって、γ、γ′ジクロロイソ
ブチレンを上記必須単量体混合物中0.1〜20重量%
含有し、かつ塩化ビニルと塩化ビニリデンの合計量が全
単量体混合物中の主成分を占める前記単量体混合物を、
ラジカル重合することを特徴とする共重合体の製造方法
。1. A monomer mixture consisting of vinyl chloride, vinylidene chloride, γ, γ' dichloroisobutylene, and optionally other radically polymerizable monomers, wherein γ, γ' dichloroisobutylene is present in the above essential monomer mixture. .1-20% by weight
and the total amount of vinyl chloride and vinylidene chloride accounts for the main component in the entire monomer mixture,
A method for producing a copolymer characterized by radical polymerization.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP21258386A JPS6368610A (en) | 1986-09-11 | 1986-09-11 | Production of copolymer |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP21258386A JPS6368610A (en) | 1986-09-11 | 1986-09-11 | Production of copolymer |
Publications (1)
Publication Number | Publication Date |
---|---|
JPS6368610A true JPS6368610A (en) | 1988-03-28 |
Family
ID=16625103
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP21258386A Pending JPS6368610A (en) | 1986-09-11 | 1986-09-11 | Production of copolymer |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS6368610A (en) |
-
1986
- 1986-09-11 JP JP21258386A patent/JPS6368610A/en active Pending
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