JPS6011968B2 - Crosslinking treatment method for ethylene/vinyl ester copolymer-vinyl chloride graft copolymer - Google Patents
Crosslinking treatment method for ethylene/vinyl ester copolymer-vinyl chloride graft copolymerInfo
- Publication number
- JPS6011968B2 JPS6011968B2 JP5810081A JP5810081A JPS6011968B2 JP S6011968 B2 JPS6011968 B2 JP S6011968B2 JP 5810081 A JP5810081 A JP 5810081A JP 5810081 A JP5810081 A JP 5810081A JP S6011968 B2 JPS6011968 B2 JP S6011968B2
- Authority
- JP
- Japan
- Prior art keywords
- copolymer
- ethylene
- vinyl
- vinyl chloride
- vinyl ester
- 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.)
- Expired
Links
- 239000005977 Ethylene Substances 0.000 title claims description 15
- 229920000578 graft copolymer Polymers 0.000 title claims description 15
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims description 14
- 229920001567 vinyl ester resin Polymers 0.000 title claims description 11
- 238000000034 method Methods 0.000 title claims description 9
- 238000004132 cross linking Methods 0.000 title claims description 7
- -1 silane compound Chemical class 0.000 claims description 12
- 229910000077 silane Inorganic materials 0.000 claims description 8
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 5
- 150000003254 radicals Chemical class 0.000 claims description 5
- 230000005494 condensation Effects 0.000 claims description 4
- 238000009833 condensation Methods 0.000 claims description 4
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical class [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 150000001451 organic peroxides Chemical class 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- BOOBDAVNHSOIDB-UHFFFAOYSA-N (2,3-dichlorobenzoyl) 2,3-dichlorobenzenecarboperoxoate Chemical compound ClC1=CC=CC(C(=O)OOC(=O)C=2C(=C(Cl)C=CC=2)Cl)=C1Cl BOOBDAVNHSOIDB-UHFFFAOYSA-N 0.000 description 1
- HGTUJZTUQFXBIH-UHFFFAOYSA-N (2,3-dimethyl-3-phenylbutan-2-yl)benzene Chemical group C=1C=CC=CC=1C(C)(C)C(C)(C)C1=CC=CC=C1 HGTUJZTUQFXBIH-UHFFFAOYSA-N 0.000 description 1
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 1
- SMSVUYQRWYTTLI-UHFFFAOYSA-L 2-ethylhexanoate;iron(2+) Chemical compound [Fe+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O SMSVUYQRWYTTLI-UHFFFAOYSA-L 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- OPXYNEYEDHAXOM-UHFFFAOYSA-N 3-oxobutanenitrile Chemical compound CC(=O)CC#N OPXYNEYEDHAXOM-UHFFFAOYSA-N 0.000 description 1
- 239000004604 Blowing Agent Substances 0.000 description 1
- 239000004709 Chlorinated polyethylene Substances 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- NOZAQBYNLKNDRT-UHFFFAOYSA-N [diacetyloxy(ethenyl)silyl] acetate Chemical compound CC(=O)O[Si](OC(C)=O)(OC(C)=O)C=C NOZAQBYNLKNDRT-UHFFFAOYSA-N 0.000 description 1
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical class OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 125000000480 butynyl group Chemical group [*]C#CC([H])([H])C([H])([H])[H] 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 229940125773 compound 10 Drugs 0.000 description 1
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- UQLDLKMNUJERMK-UHFFFAOYSA-L di(octadecanoyloxy)lead Chemical compound [Pb+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O UQLDLKMNUJERMK-UHFFFAOYSA-L 0.000 description 1
- PNOXNTGLSKTMQO-UHFFFAOYSA-L diacetyloxytin Chemical compound CC(=O)O[Sn]OC(C)=O PNOXNTGLSKTMQO-UHFFFAOYSA-L 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- ZLVXBBHTMQJRSX-VMGNSXQWSA-N jdtic Chemical class C1([C@]2(C)CCN(C[C@@H]2C)C[C@H](C(C)C)NC(=O)[C@@H]2NCC3=CC(O)=CC=C3C2)=CC=CC(O)=C1 ZLVXBBHTMQJRSX-VMGNSXQWSA-N 0.000 description 1
- GIWKOZXJDKMGQC-UHFFFAOYSA-L lead(2+);naphthalene-2-carboxylate Chemical compound [Pb+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 GIWKOZXJDKMGQC-UHFFFAOYSA-L 0.000 description 1
- OCWMFVJKFWXKNZ-UHFFFAOYSA-L lead(2+);oxygen(2-);sulfate Chemical compound [O-2].[O-2].[O-2].[Pb+2].[Pb+2].[Pb+2].[Pb+2].[O-]S([O-])(=O)=O OCWMFVJKFWXKNZ-UHFFFAOYSA-L 0.000 description 1
- 239000011344 liquid material Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 125000003544 oxime group Chemical group 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 150000002976 peresters Chemical class 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- 125000005591 trimellitate group Chemical group 0.000 description 1
- 239000000326 ultraviolet stabilizing agent Substances 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- CHJMFFKHPHCQIJ-UHFFFAOYSA-L zinc;octanoate Chemical compound [Zn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O CHJMFFKHPHCQIJ-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Graft Or Block Polymers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
【発明の詳細な説明】
本発明はエチレン・ビニルェステル共重合体を基体とし
、これに塩化ビニルをグラフト共重合させたグラフト共
重合体を架橋処理する方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for crosslinking a graft copolymer prepared by graft copolymerizing vinyl chloride onto an ethylene/vinyl ester copolymer as a base.
エチレン・ビニルェステル共重合体を基体とし、これに
塩化ビニルをグラフト共重合させたエチレン・ピニルェ
ステル共重合体−塩化ピニルグラフト共重合体は、グラ
フトする塩化ビニルの量によって種々の柔軟度のものが
得られる。The ethylene/pinyl ester copolymer-pinyl chloride graft copolymer, which is made by graft copolymerizing vinyl chloride onto an ethylene/vinyl ester copolymer as a base, can have various degrees of flexibility depending on the amount of vinyl chloride grafted. .
そして硬質成形品あるいは欧質成形品にした場合、前者
は耐衝撃性や耐寒性に優れ、後者は可塑剤の非移行性、
耐寒性などの特徴を有する優れた樹脂である。When making hard molded products or European quality molded products, the former has excellent impact resistance and cold resistance, while the latter has good plasticizer non-migration and
It is an excellent resin with features such as cold resistance.
これに加えて、この材料は放射線あるいは有機過酸化物
等の遊離基発生剤の存在下で架橋化が可能であり、これ
によりさらに耐熱性向上が付加される。In addition, the material can be crosslinked in the presence of radiation or free radical generators such as organic peroxides, which adds further heat resistance.
しかし放射線照射に依る方法では厚肉、大サイズ品の製
造に難点があり、また可能であっても極めて大がかりな
設備が必要であり、現実的ではない。However, methods that rely on radiation irradiation have difficulties in manufacturing thick-walled, large-sized products, and even if possible, extremely large-scale equipment is required, making it impractical.
また有機過酸化物等を用いるいわゆる化学架橋法では、
加熱や加圧が必要であるため、例えば異型品やパイプ、
チューブ等では形状保持ができず、応用できない問題が
あった。本発明の目的は、前記した従来技術の問題点を
解消し、簡単に架橋化エチレン・ビニルヱステル共重合
体−塩化ビニルグラフト共重合体の得られる架橋処理方
法を提供することにある。In addition, in the so-called chemical crosslinking method using organic peroxides,
Because heating and pressurization are required, for example, irregularly shaped products, pipes,
There was a problem that tubes and the like could not maintain their shape and could not be applied. An object of the present invention is to solve the problems of the prior art described above and to provide a crosslinking treatment method by which a crosslinked ethylene/vinyl ester copolymer-vinyl chloride graft copolymer can be easily obtained.
すなわち「本発明の要旨とするところは、エチレン・ビ
ニルェステル共重合体を基体とし、これに塩化ビニルを
グラフト共重合させたグラフト共重合体にシラン化合物
と遊離基発生剤を加えて加熱し、グラフト共重合体にシ
ラン化合物を付加せしめた後、水分の存在下においてシ
ラノール縮合触媒を用いて架橋処理を行うことにある。In other words, ``The gist of the present invention is to graft a graft copolymer prepared by graft copolymerizing vinyl chloride onto an ethylene/vinyl ester copolymer, adding a silane compound and a free radical generator, and heating the resulting graft copolymer. After adding a silane compound to a copolymer, a crosslinking treatment is performed using a silanol condensation catalyst in the presence of moisture.
本発明の方法により、架橋処理できるグラフト共重合体
は、グラフト基体としてエチレンとビニルェステル特に
ェステル基に２〜４個の炭素原子をもつもの、具体的に
は酢酸ビニル、アクリル酸エチルとの共重合体等が用い
られる。本発明において、エチレン−ビニルェステル−
塩化ピニルグラフト共重合体と相溶性のあるポリ塩化ビ
ニル、塩素化ポリエチレン、ポリエチレン、エチレン−
酢酸ビニル共重合体、エチレン−Ｑオレフィン共重合体
などのポリマを適宜混合して用いることは当然行ない得
る範囲のものである。Graft copolymers that can be crosslinked by the method of the present invention include copolymers of ethylene and vinyl ester, particularly those having 2 to 4 carbon atoms in the ester group, specifically vinyl acetate and ethyl acrylate as the graft base. Combination etc. are used. In the present invention, ethylene-vinyl ester-
Polyvinyl chloride, chlorinated polyethylene, polyethylene, and ethylene that are compatible with pinyl chloride graft copolymers
It is naturally possible to use a suitable mixture of polymers such as vinyl acetate copolymer and ethylene-Q olefin copolymer.
シラン化合物としては、一般式ＲＲ′ＳｉＹ２で示され
るものであり、ここでＲは例えばビニル基、アリル基、
ブチニル基、シクロヘキセニル基の不飽和な炭化水素基
またはハイドロカーボンオキシ基を表わし、Ｙは例えば
メトキシ基、ェトキシ基のようなアルコキシ基、例えば
ホルミロキシ基、アセトキシ基のようなアシロキシ基、
オキシム基等の任意の加水分解しうる有機基であり、Ｒ
′は基Ｒまたは基Ｙであることができる。The silane compound is represented by the general formula RR'SiY2, where R is, for example, a vinyl group, an allyl group,
It represents an unsaturated hydrocarbon group or hydrocarbonoxy group such as a butynyl group or a cyclohexenyl group, and Y is an alkoxy group such as a methoxy group or an ethoxy group, an acyloxy group such as a formyloxy group or an acetoxy group,
Any hydrolyzable organic group such as an oxime group, R
' can be a group R or a group Y.
シランは３個の加水分解しうる有機基を含有するのが好
適であり、例えばビニルトリメトキシシラン、ビニルト
リエトキシシラン、ビニルトリアセトキシシランなどで
ある。Preferably, the silane contains three hydrolyzable organic groups, such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, and the like.
また遊離基発生剤としては、有機過酸化物及びパーェス
テル例えば過酸化ペンゾィル「過酸化ジクロルベンゾイ
ル、ジクミル／ぐ−オキサイド、２・５ージ（ベルオキ
シベンゾエート）へキシンー３・１・３ビス（ｔプチル
−ベルオキシイソプロピル）ベンゼン、過酸化ラゥロィ
ル、第３ブチルベルアセテート、２１５：−ジメチルー
２・５ージ（ｔブチルベルオキシ）へキシンー３・２・
５ージメチルー２・５ージ（ｔブチルベルオキシ）へキ
サンおよびｔプチルベルベンゾエート、アゾ化合物例え
ばアゾビスーイソブチロニトリルおよびジメチルアゾィ
ソブチレートを挙げることができ、ジクミルパーオキサ
ィドが最も好ましい。Examples of free radical generators include organic peroxides and peresters such as penzoyl peroxide, dichlorobenzoyl peroxide, dicumyl/g-oxide, 2,5-di(beroxybenzoate), hexyne-3,1,3-bis( t-butyl-beroxyisopropyl)benzene, lauroyl peroxide, tert-butylberacetate, 215:-dimethyl-2,5-di(t-butylberoxy)hexyne-3,2.
Mention may be made of 5-dimethyl-2,5-di(t-butylberoxy)hexane and t-butylberbenzoate, azo compounds such as azobi-isobutyronitrile and dimethyl azoisobutyrate, dicumyl peroxide Most preferred.
シラノール縮合触媒としては、例えばジブチル錫ジラウ
レート、酢酸第一錫、オクタン酸第一錫、ナフテン酸鉛
、カプリル酸亜鉛、２ーェチルヘキサン酸鉄、ナフテン
酸コバルトのようなカルボン酸塩、チタン酸ェステルお
よびキレート化合物のような有機金属化合物例えばチタ
ン酸テトラブチルェステル、チタン酸テトラノニルェス
テルおよびピス（アセチルアセトニトリル）ジーイソプ
ロピルチタネート、有機塩基例えばエチルアミン、ヘキ
シルアミン、ジブチルアミンおよびピリジン、酸例えば
無機酸および脂肪酸が挙げられる。Examples of silanol condensation catalysts include carboxylates, titanate esters and chelates such as dibutyltin dilaurate, stannous acetate, stannous octoate, lead naphthenate, zinc caprylate, iron 2-ethylhexanoate, cobalt naphthenate. Organometallic compounds such as titanate tetrabutyl ester, titanate tetranonyl ester and pis(acetylacetonitrile) diisopropyl titanate, organic bases such as ethylamine, hexylamine, dibutylamine and pyridine, acids such as inorganic acids and fatty acids. can be mentioned.
好適な触媒は有機錫化合物例えばジブチル錫ジラウレー
ト、ジブチル錫ジアセテートおよびジブチル錫ジオクト
ェートである。Suitable catalysts are organotin compounds such as dibutyltin dilaurate, dibutyltin diacetate and dibutyltin dioctate.
このシラノール縮合触媒は、シラン化合物や遊離基発生
剤と共にはじめにグラフト共重合体に加えてもよいし、
また任意の時点で加えても、あるいは水に接触させると
きに表面に塗布しても、あるいは水中に分散させて用い
ても何ら差支えない。The silanol condensation catalyst may be initially added to the graft copolymer along with the silane compound and the free radical generator, or
There is no problem in adding it at any time, applying it to the surface when it comes into contact with water, or dispersing it in water.
また実用的な組成物を作るために、フタル酸ヱステル、
アジピン酸ェステル、トリメリット酸ェステル、ポリエ
ステル、ェポキシ系可塑剤、塩化パラフィンなどの可塑
剤、あるいは鉛系安定剤、ェポキシ系安定剤、有機錫化
合物、金属脂肪酸塩などの安定剤頚、クレー、タルク、
炭酸カルシウム、水酸化アルミニウム、水酸化マグネシ
ウム、カーボンブラックのような充填剤、発泡剤、着色
剤、酸化防止剤、滑剤、紫外線安定剤、金属書劣化防止
剤等は、組成物において意図する効果がもたらされるよ
うに任意の適当な量比で配合することは当然本発明の範
囲内に入るものである。次に本発明の具体的実施例につ
いて説明する。エチレン含有量５５％、酢酸ビニル含有
量４５％のエチレン・酢酸ビニル共重合体に対し、塩化
ビニルを４５：５５の重量比でグラフト共重合して成る
グラフト共重合体１０の重量部に、トリオクチルトリメ
リテート１の重量部、三塩基性硫酸鉛５重量部、ステア
リン酸鉛１重量部を配合した組成物凶を混練してからべ
レツト化した。このべレツトに、ビニルトリメトキシシ
ラン２．の重量部中にジクミルパーオキサィド０．１５
重量部を予め溶解した液状物を吸収させ、これを押出機
で混練し、シラン化合物をグラフト共重合させたコンパ
ウンドを得た。In addition, in order to make a practical composition, phthalate ester,
Plasticizers such as adipate esters, trimellitate esters, polyesters, epoxy plasticizers, and chlorinated paraffin, or stabilizers such as lead stabilizers, epoxy stabilizers, organotin compounds, metal fatty acid salts, clay, and talc. ,
Fillers such as calcium carbonate, aluminum hydroxide, magnesium hydroxide, and carbon black, blowing agents, colorants, antioxidants, lubricants, ultraviolet stabilizers, metallurgical deterioration inhibitors, etc., may have the intended effect in the composition. It is, of course, within the scope of the present invention to blend them in any suitable ratio as desired. Next, specific examples of the present invention will be described. To 10 parts by weight of a graft copolymer obtained by graft copolymerizing vinyl chloride at a weight ratio of 45:55 to an ethylene/vinyl acetate copolymer having an ethylene content of 55% and a vinyl acetate content of 45%, A composition containing 1 part by weight of octyl trimellitate, 5 parts by weight of tribasic lead sulfate, and 1 part by weight of lead stearate was kneaded and formed into a pellet. Add 2.5% vinyltrimethoxysilane to this beret. 0.15 parts by weight of dicumyl peroxide
A liquid material in which parts by weight were dissolved in advance was absorbed, and this was kneaded using an extruder to obtain a compound in which a silane compound was graft copolymerized.
このコンパウンド１０の重量部に対し、前記脚に更にジ
ブチル錫ジラゥレートを加えて成る触媒マスターバッチ
５重量部を加えて押出機に投入し、内契２仇舷、外径３
比舷のチューブを押出成型した。これを６０００の温水
中に６時間浸潰して架橋処理した。この押出成型チュー
ブの７０ｑｏテトラヒドロフラン中２０時間浸道後のゲ
ル分率は６０％であり、完全に架橋化されていることを
認めた。このチューブの２５ｑｏにおける引張強さは１
．６５ｋ９／秘で、伸びは３１０％で、耐寒性は−４０
℃以下であった。To the weight of this compound 10, 5 parts by weight of a catalyst masterbatch made by adding dibutyltin dilarate to the leg was added and charged into an extruder.
The comparison tube was extruded. This was soaked in 6,000 °C warm water for 6 hours to perform crosslinking treatment. After immersing this extruded tube in 70 qo tetrahydrofuran for 20 hours, the gel fraction was 60%, indicating that it was completely crosslinked. The tensile strength of this tube at 25qo is 1
．． 65k9/hi, elongation is 310%, cold resistance is -40
It was below ℃.
本発明の架橋処理方法によって得られる架橋化エチレン
・ビニルェステル−塩化ビニルグラフト共重合体は、実
施例のチューブの他に、パイプ、異型品、電線・ケーブ
ルの絶縁体や保護シース、シート、フィルム、発泡体等
への応用が可能である。The crosslinked ethylene vinyl ester-vinyl chloride graft copolymer obtained by the crosslinking treatment method of the present invention can be used in addition to the tubes of Examples, as well as pipes, irregularly shaped products, insulators for electric wires and cables, protective sheaths, sheets, films, etc. It can be applied to foams, etc.
本発明はエチレン・ビニルェステル共重合体一塩化ビニ
ルグラフト共重合体の簡単な努軒喬処理方法を提供する
ものであり、その工業的価値は極めて大なるものがある
。The present invention provides a simple method for treating ethylene vinyl ester copolymer and vinyl monochloride graft copolymer, and its industrial value is extremely large.
Claims (1)
れに塩化ビニルをグラフト共重合体−塩化ビニルグラフ
ト共重合体に、不飽和基含有シラン化合物と遊離ラジカ
ル発生剤を加えて加熱して上記エチレン・ビニルエステ
ル共重合体−塩化ビニルグラフト共重合体にシラン化合
物をグラフト共重合させた後、シラノール縮合触媒の存
在下において水分にさらすことを特徴とするエチレン・
ビニルエステル共重合体−塩化ビニルグラフト共重合体
の架橋処理方法。1 Based on ethylene/vinyl ester copolymer, vinyl chloride is grafted onto this copolymer - vinyl chloride graft copolymer is added with an unsaturated group-containing silane compound and a free radical generator and heated to form the ethylene/vinyl ester copolymer. Ethylene, which is characterized by graft copolymerizing a silane compound onto a vinyl ester copolymer-vinyl chloride graft copolymer and then exposing it to moisture in the presence of a silanol condensation catalyst.
A method for crosslinking a vinyl ester copolymer-vinyl chloride graft copolymer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5810081A JPS6011968B2 (en) | 1981-04-17 | 1981-04-17 | Crosslinking treatment method for ethylene/vinyl ester copolymer-vinyl chloride graft copolymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5810081A JPS6011968B2 (en) | 1981-04-17 | 1981-04-17 | Crosslinking treatment method for ethylene/vinyl ester copolymer-vinyl chloride graft copolymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS57172912A JPS57172912A (en) | 1982-10-25 |
| JPS6011968B2 true JPS6011968B2 (en) | 1985-03-29 |
Family
ID=13074532
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5810081A Expired JPS6011968B2 (en) | 1981-04-17 | 1981-04-17 | Crosslinking treatment method for ethylene/vinyl ester copolymer-vinyl chloride graft copolymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6011968B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03108793U (en) * | 1990-02-22 | 1991-11-08 |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB9725306D0 (en) * | 1997-11-28 | 1998-01-28 | Cableship Ltd | Cable management system |
| US10059814B2 (en) * | 2014-02-13 | 2018-08-28 | Sika Technology Ag | Method for producing ready-to-use soft PVC films or profiles |
-
1981
- 1981-04-17 JP JP5810081A patent/JPS6011968B2/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03108793U (en) * | 1990-02-22 | 1991-11-08 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS57172912A (en) | 1982-10-25 |
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