JPS5825694B2 - Oysters - Google Patents
OystersInfo
- Publication number
- JPS5825694B2 JPS5825694B2 JP13330275A JP13330275A JPS5825694B2 JP S5825694 B2 JPS5825694 B2 JP S5825694B2 JP 13330275 A JP13330275 A JP 13330275A JP 13330275 A JP13330275 A JP 13330275A JP S5825694 B2 JPS5825694 B2 JP S5825694B2
- Authority
- JP
- Japan
- Prior art keywords
- silicone
- crosslinking
- polyethylene
- grafted
- polyolefin
- 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
- 241000237502 Ostreidae Species 0.000 title 1
- 235000020636 oyster Nutrition 0.000 title 1
- 239000000203 mixture Substances 0.000 claims description 11
- 229920001296 polysiloxane Polymers 0.000 claims description 10
- 229920001112 grafted polyolefin Polymers 0.000 claims description 9
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 238000009833 condensation Methods 0.000 claims description 4
- 230000005494 condensation Effects 0.000 claims description 4
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 4
- JJLKTTCRRLHVGL-UHFFFAOYSA-L [acetyloxy(dibutyl)stannyl] acetate Chemical compound CC([O-])=O.CC([O-])=O.CCCC[Sn+2]CCCC JJLKTTCRRLHVGL-UHFFFAOYSA-L 0.000 claims description 2
- UQLDLKMNUJERMK-UHFFFAOYSA-L di(octadecanoyloxy)lead Chemical compound [Pb+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O UQLDLKMNUJERMK-UHFFFAOYSA-L 0.000 claims description 2
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 2
- 239000000463 material Substances 0.000 claims 1
- -1 polyethylene Polymers 0.000 description 17
- 238000004132 cross linking Methods 0.000 description 16
- 239000004698 Polyethylene Substances 0.000 description 13
- 229920000573 polyethylene Polymers 0.000 description 13
- 229920000098 polyolefin Polymers 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 5
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 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
- 150000003254 radicals Chemical class 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229920003020 cross-linked polyethylene Polymers 0.000 description 1
- 239000004703 cross-linked polyethylene Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000004611 light stabiliser Substances 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
- 238000000465 moulding Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 238000007342 radical addition reaction Methods 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Description
【発明の詳細な説明】
本発明は比較的低温において迅速かつ安全に架橋される
架橋性シリコーングラフト化ポリオレフィン組成物に関
する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to crosslinkable silicone grafted polyolefin compositions that are rapidly and safely crosslinked at relatively low temperatures.
従来、架橋ポリエチレン等の架橋ポリオレフィンの製造
は、ポリオレフィンに架橋剤としてジクミルペルオキシ
ドの如きペルオキシドを配合し押出機等により加熱下に
押出成形し、しかる後更に比較的高温に加熱して架橋さ
せることが行なわれている。Conventionally, in the production of crosslinked polyolefins such as crosslinked polyethylene, a peroxide such as dicumyl peroxide is blended with polyolefin as a crosslinking agent, extrusion molded under heat using an extruder, etc., and then further heated to a relatively high temperature for crosslinking. is being carried out.
しかるにかかる架橋ポリオレフィン成形品の製造におい
てはポリオレフィンに、架橋剤あるいは更に滑剤、老化
防止剤、光安定剤などを混合し押出機等で成形するに際
し、成形される以前の工程中に架橋が進行しいわゆるス
コーチ（焼け）を生じしばしば製品が不良となり甚だし
い場合には加工の進行を不可能ならしめるという難点が
あった。However, in the production of such crosslinked polyolefin molded products, when polyolefin is mixed with a crosslinking agent, a lubricant, an anti-aging agent, a light stabilizer, etc. and molded using an extruder, etc., crosslinking progresses during the process before molding. There is a problem in that so-called scorch (burning) occurs, which often results in defective products and, in severe cases, makes it impossible to proceed with processing.
従ってこのようなスコーチを生ずることなくしかも架橋
が迅速に進行する架橋性ポリオレフィン組成物が強く要
望されていた。Therefore, there has been a strong demand for a crosslinkable polyolefin composition that does not cause such scorch and can rapidly undergo crosslinking.
近時、従来の化学架橋ポリオレフィンに代るものとして
シリコーングラフト化ポリオレフィンが開発された。Recently, silicone grafted polyolefins have been developed as an alternative to conventional chemically crosslinked polyolefins.
このシリコーングラフト化ポリオレフィンは水を存在さ
せることにより比較的低温例えば常温ないし１００℃以
下の温度において架橋反応が進行し化学架橋の際必要と
する厖大な架橋設備が不要となるところから架橋成形品
例えば電線被覆等への適用が検討されている。In this silicone grafted polyolefin, the crosslinking reaction proceeds at a relatively low temperature, for example, room temperature to 100°C or lower, by the presence of water, and the huge crosslinking equipment required for chemical crosslinking is not required, so it can be used for crosslinked molded products such as Application to electric wire coatings, etc. is being considered.
シリコーングラフト化ポリオレフィンは水の実質的な不
存在下では架橋が進行せず水の存在によりはじめて架橋
が進行するものであるので、架橋がきわめて遅くシリコ
ーングラフト化ポリオレフィンの架橋速度を更に改善す
ることが望まれていた。Crosslinking of silicone-grafted polyolefins does not proceed in the substantial absence of water, and crosslinking occurs only in the presence of water. Therefore, crosslinking is extremely slow and it is possible to further improve the crosslinking rate of silicone-grafted polyolefins. It was wanted.
本発明はこのような要望に応えたものであって、シリコ
ーン縮合触媒としてジブチルチンジラウレートおよびジ
ブチルチンアセテートから選ばれた少なくとも一つとス
テアリン酸亜鉛およびステアリン酸鉛から選ばれた少な
くとも一つとを添加してなるシリコーングラフト化ポリ
オレフィンを母体とする架橋性組成物である。The present invention meets these demands, and includes the addition of at least one selected from dibutyltin dilaurate and dibutyltin acetate and at least one selected from zinc stearate and lead stearate as silicone condensation catalysts. This is a crosslinkable composition based on silicone-grafted polyolefin.
本発明におけるシリコーングラフト化ポリオレフィンと
しては例えばシリコーングラフト化ポリエチレンを使用
する。As the silicone-grafted polyolefin in the present invention, for example, silicone-grafted polyethylene is used.
架橋可能なシリコーングラフト化ポリエチレンは、ポリ
エチレンに約２００℃でジクミルペルオキシド（ＤＣＰ
）とビニルトリメトオキシシラン（ＶＴＭＯ８）とを反
応させてつくられる。Crosslinkable silicone-grafted polyethylene is prepared by adding dicumyl peroxide (DCP) to polyethylene at about 200°C.
) and vinyltrimethoxysilane (VTMO8).
このフリーラジカルによるポリエチレン鎖からのＨ原子
の引き抜き
フリーラジカルを持つポリエチレン鎖へのＶＴＭＯ８の
付加
このラジカルによる他のポリエチレン鎖からのＨ原子の
引抜き（この反応の継続）
全てのＶＴＭＯ８がに）型の反応をした時反応は終了、
架橋可能なシリコーングラフト化ポリエチレンが得られ
る。Abstraction of H atoms from polyethylene chains by this free radical Addition of VTMO8 to polyethylene chains with free radicals Abstraction of H atoms from other polyethylene chains by this radical (continuation of this reaction) All VTMO8 of the type When a reaction occurs, the reaction ends,
A crosslinkable silicone-grafted polyethylene is obtained.
得られた架橋可能なシリコーングラフト化ポリエチレン
は、シリコーン縮合触媒例えば、公知のジブチルチンジ
ラウレート（ＤＢＴＤＬ）を混合すると水の存在におい
て架橋される。The resulting crosslinkable silicone-grafted polyethylene is crosslinked in the presence of water upon admixture with a silicone condensation catalyst, such as the known dibutyltin dilaurate (DBTDL).
即ち架橋に必要なＨ２Ｏの存在により５ｉ−０−８ｉ結
合よりなるポリエチレン鎖の架橋網目を生ずる。That is, the presence of H2O necessary for crosslinking produces a crosslinked network of polyethylene chains consisting of 5i-0-8i bonds.
次に実施例につき記載する。Next, examples will be described.
実施例
ポリエチレン１００重量部にＤＣＰｏ、２重量部とＶＴ
ＭＯ８２重量とを混合して１８０°Ｃに約２分間加熱し
シリコーングラフト化ポリエチレンを生成させる。Example 100 parts by weight of polyethylene, 2 parts by weight of DCPo, and VT
MO82 weight and heated to 180° C. for about 2 minutes to form silicone grafted polyethylene.
得られたシリコーングラフト化ポリエチレン組成物に対
し、下表に示すシリコーン縮合触媒の各量の夫々をポリ
エチレンによるマスターバッチとして添加した。To the resulting silicone-grafted polyethylene composition, each amount of silicone condensation catalyst shown in the table below was added as a polyethylene masterbatch.
配合量はシリコーングラフトポリエチレン１００重量部
に対する重量部を示す。The blending amount indicates parts by weight based on 100 parts by weight of silicone grafted polyethylene.
かくして得られた実施例■、実施例■並びに比較例（公
知例）による架橋性組成物を大気中に放置しゲル分率を
測定した結果を図に示す。The crosslinkable compositions obtained in Example 1, Example 2, and Comparative Example (known example) thus obtained were left in the air and the gel fraction was measured, and the results are shown in the figure.
なお、曲線Ｉ、ＩＩ、Ｉ［Ｉは夫々実施例■、実施例■
、比較例（公知例）の試験結果を表わす曲線である。Note that curves I, II, and I [I are Example ■ and Example ■, respectively.
, is a curve representing the test results of a comparative example (known example).
試験結果から明らかなように、本発明にかかるシリコー
ングラフト化ポリエチレン架橋性組成物（曲線Ｉおよび
曲線■）は公知の汎用のシリコーングラフト化ポリエチ
レン架橋性組成物（曲線■）に比較して架橋速度が著し
く改善されていることがわかる。As is clear from the test results, the silicone-grafted polyethylene crosslinkable composition according to the present invention (curve I and curve ■) has a higher crosslinking rate than the known general-purpose silicone-grafted polyethylene crosslinkable composition (curve ■). It can be seen that this has been significantly improved.
以上説明したように本発明の架橋性組成物は比較的低温
におけるシリコーングラフト化ポリオレフィンの架橋反
応速度を著しく増大さ、するので成形品の架橋を迅速に
行い生産性を向上し、しかも加工中のスコーチを防止す
ることができるので安全にかつ効率よく架橋ポリオレフ
ィン成形品を製造することができる。As explained above, the crosslinkable composition of the present invention significantly increases the crosslinking reaction rate of silicone-grafted polyolefin at relatively low temperatures, thereby rapidly crosslinking molded products, improving productivity, and reducing the time during processing. Since scorch can be prevented, crosslinked polyolefin molded products can be produced safely and efficiently.
図面は本発明の架橋性組成物の架橋特性を従来のシリコ
ーングラフト化ポリエチレン架橋性組成物と比較して示
す曲線である。
Ｉ、Ｉ・・・・・・本発明による架橋特性曲線、■・・
・・・・従来例による架橋特性曲線。The drawing is a curve showing the crosslinking properties of the crosslinkable composition of the present invention in comparison to a conventional silicone grafted polyethylene crosslinkable composition. I, I...Crosslinking characteristic curve according to the present invention, ■...
...Crosslinking characteristic curve according to conventional example.
Claims (1)
トおよびジブチルチンアセテートから選ばれた少なくと
も一つとステアリン酸亜鉛およびステアリン酸鉛から選
ばれた少なくとも一つとを添加してなるシリコーングラ
フト化ポリオレフィンを母体とする架橋性組成物。1. A crosslinkable composition having a silicone-grafted polyolefin as a base material, to which at least one selected from dibutyltin dilaurate and dibutyltin acetate and at least one selected from zinc stearate and lead stearate are added as a silicone condensation catalyst. .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13330275A JPS5825694B2 (en) | 1975-11-04 | 1975-11-04 | Oysters |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13330275A JPS5825694B2 (en) | 1975-11-04 | 1975-11-04 | Oysters |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5256192A JPS5256192A (en) | 1977-05-09 |
| JPS5825694B2 true JPS5825694B2 (en) | 1983-05-28 |
Family
ID=15101475
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13330275A Expired JPS5825694B2 (en) | 1975-11-04 | 1975-11-04 | Oysters |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5825694B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0730229B2 (en) * | 1985-11-06 | 1995-04-05 | 住友ベ−クライト株式会社 | Method for producing silane-modified ethylene polymer molded article |
| JP5331900B2 (en) * | 2008-12-23 | 2013-10-30 | ダウ グローバル テクノロジーズ エルエルシー | Moisture curing catalyst system for ethylene-vinylsilane copolymer |
-
1975
- 1975-11-04 JP JP13330275A patent/JPS5825694B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5256192A (en) | 1977-05-09 |
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