JPS6011969B2 - Crosslinking treatment method for ethylene/α-olefin copolymer-vinyl chloride graft copolymer - Google Patents
Crosslinking treatment method for ethylene/α-olefin copolymer-vinyl chloride graft copolymerInfo
- Publication number
- JPS6011969B2 JPS6011969B2 JP5810181A JP5810181A JPS6011969B2 JP S6011969 B2 JPS6011969 B2 JP S6011969B2 JP 5810181 A JP5810181 A JP 5810181A JP 5810181 A JP5810181 A JP 5810181A JP S6011969 B2 JPS6011969 B2 JP S6011969B2
- Authority
- JP
- Japan
- Prior art keywords
- ethylene
- copolymer
- vinyl chloride
- graft copolymer
- olefin
- 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
- 229920000578 graft copolymer Polymers 0.000 title claims description 16
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims description 15
- 239000005977 Ethylene Substances 0.000 title claims description 15
- 238000000034 method Methods 0.000 title claims description 10
- 238000004132 cross linking Methods 0.000 title claims description 8
- 239000004711 α-olefin Substances 0.000 title claims 5
- -1 silane compound Chemical class 0.000 claims description 13
- 229910000077 silane Inorganic materials 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 7
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims description 6
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 5
- 238000009833 condensation Methods 0.000 claims description 5
- 230000005494 condensation Effects 0.000 claims description 5
- 150000003254 radicals Chemical class 0.000 claims description 5
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 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 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 150000001451 organic peroxides Chemical class 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-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
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-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
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical class [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 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
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 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
- 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
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-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
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- NBJODVYWAQLZOC-UHFFFAOYSA-L [dibutyl(octanoyloxy)stannyl] octanoate Chemical compound CCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCC NBJODVYWAQLZOC-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000002252 acyl 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
- 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
- 238000007796 conventional method Methods 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
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 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
- 238000001125 extrusion Methods 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
- 238000010438 heat treatment Methods 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
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 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
- 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
- 125000000962 organic group Chemical group 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 150000002976 peresters Chemical class 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical class OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 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
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 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
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 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
- JNXDCMUUZNIWPQ-UHFFFAOYSA-N trioctyl benzene-1,2,4-tricarboxylate Chemical compound CCCCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCCC)C(C(=O)OCCCCCCCC)=C1 JNXDCMUUZNIWPQ-UHFFFAOYSA-N 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
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Graft Or Block Polymers (AREA)
Description
【発明の詳細な説明】
本発明はエチレン・Ｑオレフィン共重合体を基体としこ
れに塩化ビニルをグラフト集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 having an ethylene/Q olefin copolymer as a base material and vinyl chloride grafted onto the copolymer.
エチレン・Ｑオレフィン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・Ｑオレフィン
−塩化ビニルグラフト共重合体は、グラフトする塩化ピ
ニルの量によって種々の柔軟度のものが得られ、概して
耐衝撃性、耐寒性、物理特性に優れた特徴を持つ樹脂で
ある。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。しかし放
射線照射による方法では厚肉、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。Ethylene/Q olefin-vinyl chloride graft copolymers, which are made by graft copolymerizing vinyl chloride onto an ethylene/Q olefin copolymer as a base, can be obtained with various degrees of flexibility depending on the amount of pinyl chloride grafted. Generally speaking, it is a resin with excellent impact resistance, cold resistance, and physical properties. 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. However, methods using 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、前記した従釆技術の問題点を解
消し、簡単に架橋化エチレン・Ｑオレフィン共重合体−
塩化ピ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, the so-called chemical crosslinking method using organic peroxides requires heating and pressurization, so there is a problem in that it cannot be applied to, for example, irregularly shaped products, pipes, tubes, etc. because the shape cannot be maintained. The purpose of the present invention is to solve the problems of the conventional techniques described above and to easily produce a crosslinked ethylene/Q olefin copolymer.
An object of the present invention is to provide a method for crosslinking a pinyl chloride graft copolymer.
すなわち、本発明の要旨とするところは、エチレン・Ｑ
オレフイン共重合体を基体としこれに塩化ビニルグラフ
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なうことである。That is, the gist of the present invention is that ethylene/Q
A silane compound and a free radical generator are added to a graft copolymer made of an olefin copolymer as a base and vinyl chloride graft copolymerized, and the silane compound is added to the graft copolymer. The crosslinking process is carried out using a silanol condensation catalyst in the presence of a silanol condensation catalyst.
本発明の方法により努守喬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プロピレン、ブテン
−１などのＱオレフインとの共重合体が用いられる。In the graft copolymer that can be treated by the method of the present invention, a copolymer of ethylene and a Q olefin such as propylene or butene-1 is used as a graft base.
本発明において、エチレン・Ｑオレフィンー塩化ビニル
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・Ｑオレフイ
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。In the present invention, it is naturally possible to appropriately mix and use polymers such as polyvinyl chloride, chlorinated polyethylene, polyethylene, and ethylene/Q olefin copolymers that are compatible with the ethylene/Q olefin-vinyl chloride graft copolymer. It's a range of things.
シラン化合物としては一般式ＦＲ′ＳｉＹ２で示される
ものであり、ここでＲは例えばビニル基、アクル基、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 FR'SiY2, where R represents an unsaturated hydrocarbon group or hydrocarbonoxy group such as a vinyl group, an acyl group, a butynyl group, or a cyclohexenyl group, and Y represents a hydrocarbonoxy 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、ピニルトリアセトキシシラン等であ
る。また遊離ラジカル発生剤としては、有機過酸化物及
びパーヱステル例えば過酸化ペンゾィル、過酸化ジクロ
ベンゾィル、ジクミルパーオキサィド、２・５−ジ（ベ
ルオキシベンゾヱート）へキシンー３、１．３ピス（ｔ
ブチルーベルオキシイソプロピル）ベンゼン、過酸化ラ
ウロイル、ｔブチルベルアセテート、２・５−ジメチル
−２・５−ジ（ｔブチルベルオキシ）へキシンー３、２
・５−ジメチル−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
えばアゾビスーィソプ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
サイドが最も好ましい。Preferably, the silane contains three hydrolyzable organic groups, such as vinyltrimethoxysilane, vinyltriethoxysilane, pinyltriacetoxysilane, and the like. Free radical generators include organic peroxides and peresters such as penzoyl peroxide, dichlobenzoyl peroxide, dicumyl peroxide, 2,5-di(beroxybenzoate)hexyne-3, 1.3 Piss (t
butylberoxyisopropyl)benzene, lauroyl peroxide, t-butylberacetate, 2,5-dimethyl-2,5-di(t-butylberoxy)hexyne-3,2
5-dimethyl-2,5-di(t-butylberoxy)hexane and t-butylberbenzoate, azo compounds such as azobisisoptylonitrile and dimethylazoisobutyrate, dicumyl peroxide is most preferred.
シラノール縮合触媒としては、例えばジプチル錫ジラウ
レート、酢酸第一錫、オクタン酸第一錫、ナフテン酸鉛
、カブリル酸亜鉛、Ｑ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
びビス（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。Silanol condensation catalysts include, for example, carboxylates, titanate esters and chelates such as diptyltin dilaurate, stannous acetate, stannous octoate, lead naphthenate, zinc cabrylate, iron Q-ethylhexanoate, cobalt naphthenate. Organometallic compounds such as compounds such as tetrabutyl ester, tetranonyl titanate and bis(acetylacetonitrile) diisopropyltitanate, organic bases such as ethylamine, hexylamine, dibutylamine and pyridine, acids such as inorganic acids and fatty acids. It will be done.
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
エートである。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
えても良いし、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。Suitable catalysts are organotin compounds such as dibutyltin dilaurate, dibutyltin diacetate and dibutyltin dioctoate. The silanol condensation catalyst can be added initially to the graft copolymer together with the silane compound and free radical generator, or it can be added at any point, or it can be applied to the surface upon contact with water, or it can be added to the graft copolymer at the time of contact with water or in water. There is no problem even if it is dispersed and used.
また実用的な組成物を作るために、フタル酸ェステル、
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類、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、柴外線安定剤、金属筈劣化防止剤
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・プロピレン共重合体に塩化ビ
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
た組成物帆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。このコンパ
ウンド１０の重量部に対し、前記Ｗ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、内径２仇倣、外径３仇奴のチュ
ーブを押出成型した。In order to make practical compositions, phthalate esters,
Plasticizers such as adipate ester, trimellitate ester, polyester, epoxy plasticizer, chlorinated paraffin, stabilizers such as lead stabilizer, epoxy stabilizer, organotin compound, metal fatty acid salt, clay, talc Fillers such as calcium carbonate, aluminum hydroxide, magnesium hydroxide, and carbon black, blowing agents, colorants, antioxidants, lubricants, ray stabilizers, metal deterioration inhibitors, etc. are used to achieve the intended effect in the composition. It is naturally within the scope of the present invention to blend them in any suitable ratio so as to provide the following. Next, specific examples of the present invention will be described. 1 part by weight of trioctyl trimellitate, 5 parts by weight of tribasic lead sulfate, 1 part by weight of lead stearate to 10 parts by weight of graft copolymer obtained by graft copolymerizing vinyl chloride to ethylene propylene copolymer. The composition containing the following was kneaded and then made into pellets. Add 2.5% vinyltrimethoxysilane to this beret. A liquid material in which 0.15 parts by weight of dicumyl peroxide was dissolved in advance was absorbed into parts by weight of , and this was kneaded in an extruder to obtain a compound in which a silane compound was graft copolymerized. To 10 parts by weight of this compound, 5 parts by weight of a catalyst masterbatch made by adding dibutyltin dilarate to the above W was added and charged into an extruder, and a tube with an inner diameter of 2 mm and an outer diameter of 3 mm was extruded. did.
これを６０ｑｏの温水中に６時間浸潰して架橋処理した
。こね押出成型チューブの７０ｑ０テトラヒドロフラン
中２脚時間浸薄後のゲル分率は６０％であり、完全に架
橋化されていることを認めた。This was soaked in 60 qo warm water for 6 hours to perform crosslinking treatment. The gel fraction of the kneaded extrusion molded tube after being diluted in 70q0 tetrahydrofuran for two hours was 60%, indicating that it was completely crosslinked.
このチューブの２５ｏｏにおける引張強ごは１．７ｋ９
／柵で、伸びは２８０％で、耐寒性は−３５℃以下であ
つた。The tensile strength of this tube at 25oo is 1.7k9
/ fence, the elongation was 280%, and the cold resistance was -35°C or lower.
本発明の架橋処理方法によって得られるエチレン・Ｑオ
レフイン共重合体−塩化ビニルグラフト共重合体は、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 ethylene/Q olefin copolymer-vinyl chloride graft copolymer obtained by the crosslinking treatment method of the present invention can be used for irregular shaped products, insulators and protective sheaths for electric wires and cables, sheets,
It can be applied to films, foams, etc.
本発明はエチレン・Ｑオレフィン共重合体−塩化ビニル
グラフト共重合体の簡単な架橋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 crosslinking an ethylene/Q olefin copolymer-vinyl chloride graft copolymer, and has extremely great industrial value.
Claims (1)
に塩化ビニルをグラフト共重合させたエチレン・αオレ
フイン共重合体−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・αオレフイン共重合体−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・αオレフイン共重合体
−塩化ビニルグラフト共重合体の架橋処理方法。1 Based on ethylene/α-olefin copolymer, an ethylene/α-olefin copolymer-vinyl chloride graft copolymer obtained by graft copolymerizing vinyl chloride with an unsaturated group-containing silane compound and a free radical generator. The ethylene/α-olefin is further heated to graft-copolymerize a silane compound onto the ethylene/α-olefin copolymer-vinyl chloride graft copolymer, and then exposed to moisture in the presence of a silanol condensation catalyst. A method for crosslinking a copolymer-vinyl chloride graft copolymer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5810181A JPS6011969B2 (en) | 1981-04-17 | 1981-04-17 | Crosslinking treatment method for ethylene/α-olefin copolymer-vinyl chloride graft copolymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5810181A JPS6011969B2 (en) | 1981-04-17 | 1981-04-17 | Crosslinking treatment method for ethylene/α-olefin copolymer-vinyl chloride graft copolymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS57172913A JPS57172913A (en) | 1982-10-25 |
| JPS6011969B2 true JPS6011969B2 (en) | 1985-03-29 |
Family
ID=13074562
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5810181A Expired JPS6011969B2 (en) | 1981-04-17 | 1981-04-17 | Crosslinking treatment method for ethylene/α-olefin copolymer-vinyl chloride graft copolymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6011969B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10132678A1 (en) * | 2000-07-26 | 2002-02-07 | Henkel Kgaa | Binding agent useful in surface coating agents, foams or adhesives contains at least graft polymer having at least two alkylsilyl groups, with graft branches |
-
1981
- 1981-04-17 JP JP5810181A patent/JPS6011969B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS57172913A (en) | 1982-10-25 |
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