JPS62253608A - Polyolefin composition - Google Patents
Polyolefin compositionInfo
- Publication number
- JPS62253608A JPS62253608A JP9762586A JP9762586A JPS62253608A JP S62253608 A JPS62253608 A JP S62253608A JP 9762586 A JP9762586 A JP 9762586A JP 9762586 A JP9762586 A JP 9762586A JP S62253608 A JPS62253608 A JP S62253608A
- Authority
- JP
- Japan
- Prior art keywords
- polyolefin
- silane
- hydrophilic polymer
- composition
- peroxide
- 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.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 17
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 15
- 229920001477 hydrophilic polymer Polymers 0.000 claims abstract description 11
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 4
- 150000001451 organic peroxides Chemical class 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 15
- -1 polyethylene, ethylene-propylene copolymer Polymers 0.000 abstract description 6
- 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 abstract description 4
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 abstract description 4
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 abstract description 3
- 239000004342 Benzoyl peroxide Substances 0.000 abstract description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 abstract description 2
- 239000002202 Polyethylene glycol Substances 0.000 abstract description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 abstract description 2
- 229920001223 polyethylene glycol Polymers 0.000 abstract description 2
- 229920002689 polyvinyl acetate Polymers 0.000 abstract description 2
- 239000011118 polyvinyl acetate Substances 0.000 abstract description 2
- 239000011810 insulating material Substances 0.000 abstract 1
- 238000004132 cross linking Methods 0.000 description 12
- 239000012212 insulator Substances 0.000 description 11
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 7
- 229910000077 silane Inorganic materials 0.000 description 7
- 230000035515 penetration Effects 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- CHILLBMGESTNSK-UHFFFAOYSA-N 1-butylperoxy-2,3-di(propan-2-yl)benzene Chemical group CCCCOOC1=CC=CC(C(C)C)=C1C(C)C CHILLBMGESTNSK-UHFFFAOYSA-N 0.000 description 1
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 1
- 239000004604 Blowing Agent Substances 0.000 description 1
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 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
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Graft Or Block Polymers (AREA)
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明は、シラン架橋のポリオレフィン組成物に係り、
特に、組成物が肉厚であっても架橋速度の向上を図るこ
とができ、例えば、電線・ケーブルの絶縁体等に用いて
有用なポリオレフィン組成物に関する。[Detailed Description of the Invention] <Industrial Application Field> The present invention relates to a silane-crosslinked polyolefin composition,
In particular, the present invention relates to a polyolefin composition that can improve the crosslinking rate even if the composition is thick, and is useful for, for example, insulators for electric wires and cables.
〈従来の技術〉
ポリオレフィン、特に、ポリエチレンのシラン架橋は、
現在広く行われており、よく絶縁電線・ケーブルの絶縁
体に用いられている。<Prior art> Silane crosslinking of polyolefin, especially polyethylene,
It is currently widely used and is often used as an insulator for insulated wires and cables.
この際の絶縁体の製造においては、先ず、ポリエチレン
に過酸化物（例えば、ジキュミルバーオキサイド：ＤＣ
Ｐ）とシランカップリング剤（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、ビニルトリス
（β−メトキシエトキシ）シラン等）を配合し、２００
℃程度の高温で混練してシラングシフト化ポリエチレン
を得、次に、このシランブラット化ポリエチレンを絶縁
体として押出し被覆し、これを大気中或いは温水中に浸
漬し、このときの水の浸透によって水架橋を進行させ、
シラン架橋絶縁電線・ケーブルを得ている。In manufacturing the insulator at this time, first, peroxide (for example, dicumyl peroxide: DC
P) and a silane coupling agent (e.g., vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(β-methoxyethoxy)silane, etc.), and
Silang-shifted polyethylene is obtained by kneading at a high temperature of about ℃, and then this silang-blatted polyethylene is extruded and coated as an insulator, and this is immersed in the air or warm water, and water crosslinking occurs due to water penetration at this time. proceed with
We have obtained silane cross-linked insulated wires and cables.
このとき、架橋を促進させるため、触媒（例えば、ジブ
チル錫ジラウレート）を併用することが多い。At this time, a catalyst (for example, dibutyltin dilaurate) is often used in combination to promote crosslinking.
〈発明が解決しようとする問題点〉
ところが、シラン架橋は基本的には、水との反応による
水架橋であるため、触媒を用いる場合でも、組成物への
水の浸透速度が律速となる。<Problems to be Solved by the Invention> However, since silane crosslinking is basically water crosslinking due to reaction with water, the rate of water permeation into the composition is rate-determining even when a catalyst is used.
特に、電線・ケーブルの絶縁体のように肉厚の場合、水
の浸透が内部に達するのに長時間を要するため、製造効
率が悪いという問題があった。In particular, in the case of thick insulators such as those used in electric wires and cables, it takes a long time for water to penetrate inside, resulting in poor manufacturing efficiency.
本発明は、このような従来の問題点に鑑みてなされたも
ので、シラン架橋組成物の絶縁体を得る際、組成物への
水の浸透を速やかに行わせて、架橋速度の向上を図ろう
とするものである。The present invention has been made in view of these conventional problems, and aims to improve the crosslinking speed by allowing water to quickly penetrate into the composition when obtaining an insulator made of a silane crosslinked composition. It is something that we try to do.
〈問題点を解決するための手段及びその作用〉か−る本
発明の特徴とする点は、親水性ポリマーの添加に着目し
、この特定量、即ち０．１〜１５重量部と、シランカッ
プリング剤、及び有機過酸化物をポリオレフィン１００
重量部に添加したポリオレフィン組成物にある。<Means for Solving the Problems and Their Effects> The characteristic feature of the present invention is that it focuses on the addition of a hydrophilic polymer, and adds a specific amount of the hydrophilic polymer, that is, 0.1 to 15 parts by weight, and a silane cup. ring agent and organic peroxide to polyolefin 100
Parts by weight are added to the polyolefin composition.
この親水性ポリマーの添加により、ポリオレフィンへの
水の浸透が促進され、シラン架橋の架橋速度が向上され
る。The addition of this hydrophilic polymer promotes water penetration into the polyolefin and increases the rate of silane crosslinking.
ここで、親水性ポリマーとしては、−ＯＨ基、−ＣＯＯ
Ｈ基、−（ＯＣＨｚ ＣＨり−−基、−ＯＨ基、−ＣＯ
ＮＨ基、−ＯＲ基、−０ＣＯＲ基、−ＣＯＯＲ基、−ｃ
Ｈｚ ＯＲ基（但し、上記Ｒはアルキル基）を有するポ
リマーが好ましく、中でも、ポリオレフィンとの混練性
を考慮すると、ポリエチレングリコール、ポリビニルア
ルコール、ポリ酢酸ビニル、エチレン−ビニルアルコー
ル共重合体が有用である。 −
そして、その添加量を０．１〜１５重量部としたのは、
０．１未満では、水の浸透速度の促進効果が殆ど得られ
ず、又１５重量部を越えると、水による膨潤現象が生ず
るようになるからである。Here, as the hydrophilic polymer, -OH group, -COO
H group, -(OCHz CHri-- group, -OH group, -CO
NH group, -OR group, -0COR group, -COOR group, -c
Hz Polymers having an OR group (wherein R is an alkyl group) are preferred; among them, polyethylene glycol, polyvinyl alcohol, polyvinyl acetate, and ethylene-vinyl alcohol copolymers are useful in consideration of kneadability with polyolefins. . - And the reason why the amount added was 0.1 to 15 parts by weight was
If it is less than 0.1, little effect of promoting the water penetration rate will be obtained, and if it exceeds 15 parts by weight, a swelling phenomenon due to water will occur.
そして、特に、この組成物を電線・ケーブルに使用する
場合、吸水量が大きくなり過ぎて絶縁特性を低下させる
等の問題が生ずるからである。In particular, when this composition is used for electric wires and cables, problems such as excessive water absorption and deterioration of insulation properties occur.
又、本発明で用いられるポリオレフィンとしては、ポリ
エチレン、エチレン−プロピレン共重合体、ポリプロピ
レン、ポリブテン−１、ポリ−４−メチルペンテン−１
等が挙げられる。Further, as the polyolefin used in the present invention, polyethylene, ethylene-propylene copolymer, polypropylene, polybutene-1, poly-4-methylpentene-1
etc.
又、本発明で使用されるシランカップリング剤としては
、一般式ＲＲ’ Ｓ ｉ ＹｔやＲ’ＳｆＹ。Further, the silane coupling agent used in the present invention has the general formula RR' S i Yt and R'SfY.
で表されるものがあり、具体的には、ビニルトリメトキ
シシラン（ＶＴＭＳ）、ビニルトリエトキシシラン（Ｖ
ＴＥＳ） 、ビニルトリス（β−メトキシエトキシ）シ
ラン等を用いるとよく、その添加量は０．５〜４重量部
とするのが好ましい。Specifically, vinyltrimethoxysilane (VTMS), vinyltriethoxysilane (V
TES), vinyltris(β-methoxyethoxy)silane, etc. may be used, and the amount added is preferably 0.5 to 4 parts by weight.
更に、有機過酸化物としては、ジクミルパーオキサイド
（ＤＣＰ） 、過酸化ベンゾイル、ジターシャリブチル
パーオキシ・ジイソプロピルベンゼン等が用いられ、そ
の添加量は０．０１〜０．５重量部とすることが好まし
い。Further, as the organic peroxide, dicumyl peroxide (DCP), benzoyl peroxide, ditertiary butylperoxy diisopropylbenzene, etc. are used, and the amount added is 0.01 to 0.5 parts by weight. is preferred.
又、前記組成物には、老化防止剤、充填剤、発泡剤、滑
剤、安定剤、着色剤等の添加剤が適宜添加できる。Further, additives such as anti-aging agents, fillers, blowing agents, lubricants, stabilizers, colorants, etc. can be added to the composition as appropriate.
〈実施例〉
第１表に示した配合の組成物を得、これを２００℃の温
度でケーブル絶縁体として押出した（実施例■〜■）。<Example> A composition having the formulation shown in Table 1 was obtained, and this was extruded as a cable insulator at a temperature of 200°C (Examples 1 to 2).
このとき、ケーブルの導体断面積は２５０ｍｍ”、絶縁
体厚は４ｍｍとした。At this time, the conductor cross-sectional area of the cable was 250 mm'', and the insulator thickness was 4 mm.
尚、比較のため、親水性ポリマーを添加しないもの、親
水性ポリマーの添加量が本発明条件を満たしていないも
のを上記と同様ケーブル絶縁体として押出した（比較例
■〜■）。又、表中の配合量は重量部数を示す。For comparison, cable insulators to which no hydrophilic polymer was added and those in which the amount of hydrophilic polymer added did not satisfy the conditions of the present invention were extruded as cable insulators in the same manner as above (Comparative Examples 1 to 2). Further, the blending amounts in the table indicate parts by weight.
これらの各ケーブル試料（実施例■〜■、比較例■〜■
）を８０℃の温水に浸漬し、その１２０℃における加熱
変形率が３０％となる所要時間及びその誘電正接（ｔａ
ｎδ）を求めた。その結果は第１表の通りであった。Each of these cable samples (Examples ■~■, Comparative Examples ■~■
) is immersed in 80°C hot water, and the time required for the heating deformation rate to reach 30% at 120°C and its dielectric loss tangent (ta
nδ) was calculated. The results were as shown in Table 1.
前記第１表に示したように所定量の親水性ポリマーを添
加すると、架橋促進効率が向上されるため、短時間で所
望の加熱変形率が得られることが分かる。As shown in Table 1 above, it can be seen that when a predetermined amount of hydrophilic polymer is added, the crosslinking promotion efficiency is improved, so that the desired heat deformation rate can be obtained in a short time.
〈発明の効果〉
以上の説明から明らかなように本発明によれば、通常の
組成からなるシラン架橋ポリオレフィン組成物に特定量
の親水性ポリマーを添加するため、水の浸透が極めて良
好に行われ、短時間での架橋が可能となり、架橋時間の
大幅な短縮を図ることができる。従って、本発明組成物
を電線・ケーブルの絶縁体等として用いた場合、架橋時
間の短縮と共に良好な電気的特性の両者を満足させるこ
とができ、電線・ケーブルへの適用が十分可能である他
、その他のシラン架橋物製品、特に肉厚製品への適用も
可能である。<Effects of the Invention> As is clear from the above description, according to the present invention, a specific amount of hydrophilic polymer is added to a silane-crosslinked polyolefin composition having a normal composition, so that water penetration is extremely good. , crosslinking can be carried out in a short time, and the crosslinking time can be significantly shortened. Therefore, when the composition of the present invention is used as an insulator for electric wires and cables, it can satisfy both shortening of crosslinking time and good electrical properties, and is fully applicable to electric wires and cables. It is also possible to apply this method to other silane crosslinked products, especially thick-walled products.
Claims (1)
有機過酸化物、及び親水性ポリマー０．１〜１５重量部
を添加したことを特徴とするポリオレフィン組成物。100 parts by weight of polyolefin, silane coupling agent,
A polyolefin composition comprising an organic peroxide and 0.1 to 15 parts by weight of a hydrophilic polymer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61097625A JPH0730136B2 (en) | 1986-04-26 | 1986-04-26 | Polyolefin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61097625A JPH0730136B2 (en) | 1986-04-26 | 1986-04-26 | Polyolefin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62253608A true JPS62253608A (en) | 1987-11-05 |
| JPH0730136B2 JPH0730136B2 (en) | 1995-04-05 |
Family
ID=14197370
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61097625A Expired - Lifetime JPH0730136B2 (en) | 1986-04-26 | 1986-04-26 | Polyolefin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0730136B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0413744A (en) * | 1990-05-08 | 1992-01-17 | Ube Ind Ltd | Bonding polyethylene resin composition |
| CN117165023A (en) * | 2023-09-12 | 2023-12-05 | 广东东大科技有限公司 | Silane crosslinked TPE cable material for charging pile and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5339341A (en) * | 1976-09-24 | 1978-04-11 | Sumitomo Bakelite Co Ltd | Polyethylene resin composition |
-
1986
- 1986-04-26 JP JP61097625A patent/JPH0730136B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5339341A (en) * | 1976-09-24 | 1978-04-11 | Sumitomo Bakelite Co Ltd | Polyethylene resin composition |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0413744A (en) * | 1990-05-08 | 1992-01-17 | Ube Ind Ltd | Bonding polyethylene resin composition |
| CN117165023A (en) * | 2023-09-12 | 2023-12-05 | 广东东大科技有限公司 | Silane crosslinked TPE cable material for charging pile and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0730136B2 (en) | 1995-04-05 |
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