JPH01101338A - Heating process for organic polymer - Google Patents
Heating process for organic polymerInfo
- Publication number
- JPH01101338A JPH01101338A JP25935387A JP25935387A JPH01101338A JP H01101338 A JPH01101338 A JP H01101338A JP 25935387 A JP25935387 A JP 25935387A JP 25935387 A JP25935387 A JP 25935387A JP H01101338 A JPH01101338 A JP H01101338A
- Authority
- JP
- Japan
- Prior art keywords
- organic polymer
- organic
- heat treatment
- crosslinking agent
- oxygen
- 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
- 229920000620 organic polymer Polymers 0.000 title claims abstract description 30
- 238000010438 heat treatment Methods 0.000 title claims abstract description 28
- 150000001451 organic peroxides Chemical class 0.000 claims abstract description 24
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 23
- 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 claims abstract description 10
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 10
- -1 polyethylene Polymers 0.000 claims abstract description 7
- 239000004698 Polyethylene Substances 0.000 claims abstract description 5
- 229920000573 polyethylene Polymers 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 6
- 239000002530 phenolic antioxidant Substances 0.000 claims description 5
- 239000011247 coating layer Substances 0.000 claims description 3
- 239000000470 constituent Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 12
- 239000003963 antioxidant agent Substances 0.000 abstract description 9
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 abstract description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 4
- 230000003078 antioxidant effect Effects 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 10
- 239000001301 oxygen Substances 0.000 description 10
- 229910052760 oxygen Inorganic materials 0.000 description 10
- 238000004132 cross linking Methods 0.000 description 9
- 238000006297 dehydration reaction Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- OIGWAXDAPKFNCQ-UHFFFAOYSA-N 4-isopropylbenzyl alcohol Chemical compound CC(C)C1=CC=C(CO)C=C1 OIGWAXDAPKFNCQ-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 238000009413 insulation Methods 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 4
- 238000010292 electrical insulation Methods 0.000 description 4
- 229920001684 low density polyethylene Polymers 0.000 description 4
- 239000004702 low-density polyethylene Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- LZHCVNIARUXHAL-UHFFFAOYSA-N 2-tert-butyl-4-ethylphenol Chemical compound CCC1=CC=C(O)C(C(C)(C)C)=C1 LZHCVNIARUXHAL-UHFFFAOYSA-N 0.000 description 2
- XOUQAVYLRNOXDO-UHFFFAOYSA-N 2-tert-butyl-5-methylphenol Chemical compound CC1=CC=C(C(C)(C)C)C(O)=C1 XOUQAVYLRNOXDO-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 150000003509 tertiary alcohols Chemical class 0.000 description 2
- OPLCSTZDXXUYDU-UHFFFAOYSA-N 2,4-dimethyl-6-tert-butylphenol Chemical compound CC1=CC(C)=C(O)C(C(C)(C)C)=C1 OPLCSTZDXXUYDU-UHFFFAOYSA-N 0.000 description 1
- LKWVKJXZKSOZIW-UHFFFAOYSA-N 2,5-dibutylbenzene-1,4-diol Chemical compound CCCCC1=CC(O)=C(CCCC)C=C1O LKWVKJXZKSOZIW-UHFFFAOYSA-N 0.000 description 1
- ASLNDVUAZOHADR-UHFFFAOYSA-N 2-butyl-3-methylphenol Chemical compound CCCCC1=C(C)C=CC=C1O ASLNDVUAZOHADR-UHFFFAOYSA-N 0.000 description 1
- IKEHOXWJQXIQAG-UHFFFAOYSA-N 2-tert-butyl-4-methylphenol Chemical compound CC1=CC=C(O)C(C(C)(C)C)=C1 IKEHOXWJQXIQAG-UHFFFAOYSA-N 0.000 description 1
- BVCOHOSEBKQIQD-UHFFFAOYSA-N 2-tert-butyl-6-methoxyphenol Chemical compound COC1=CC=CC(C(C)(C)C)=C1O BVCOHOSEBKQIQD-UHFFFAOYSA-N 0.000 description 1
- BKZXZGWHTRCFPX-UHFFFAOYSA-N 2-tert-butyl-6-methylphenol Chemical compound CC1=CC=CC(C(C)(C)C)=C1O BKZXZGWHTRCFPX-UHFFFAOYSA-N 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 240000005572 Syzygium cordatum Species 0.000 description 1
- 235000006650 Syzygium cordatum Nutrition 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 229920006244 ethylene-ethyl acrylate Polymers 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
Abstract
Description
【発明の詳細な説明】
崖1上凶剋朋分亙
本発明は有機過酸化物または有機過酸化物分解残渣を含
有する有機高分子、たとえば架橋性ポリエチレン組成物
などの新規な加熱処理方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel heat treatment method for organic polymers, such as crosslinkable polyethylene compositions, containing organic peroxides or organic peroxide decomposition residues. .
盗】舒1え■
電気絶縁性が要求される架橋有機高分子、たとえば絶縁
ケーブルの絶縁被覆の構成材料に於いてはできるだけ水
分含有量が少ないことが必要である。その理由は、水分
含有量が多いと絶縁被覆中にボイドが発生し、送電時な
どの電圧印加状態において水ツリーと称される現象が生
じて電気特性特に絶縁破壊強度が大幅に低下してしまう
からである。Cross-linked organic polymers that require electrical insulation properties, such as the constituent materials of the insulation coating of insulated cables, need to have as little water content as possible. The reason for this is that when the moisture content is high, voids occur in the insulation coating, and a phenomenon called water tree occurs when voltage is applied during power transmission, resulting in a significant decrease in electrical properties, especially dielectric breakdown strength. It is from.
絶縁ケーブルの絶縁被覆層は、耐熱性を向上させるため
に、通常はその構成材料を架橋して使用する。現在、該
絶縁被覆層構成材料の架橋方法として高圧絶縁ケーブル
の製造に最も広く採用されているのは有機過酸化物架橋
剤を用いた化学架橋方法であるが、本発明者らは先に有
機過酸化物架橋剤を配合した有機高分子を酸素の存在下
で加熱すると、あるいは有機過酸化物架橋剤の分解残渣
を含んだ有機高分子を酸素の存在下で加熱すると多量の
水分が発生し、それが有機高分子中に残存することを知
った。The insulating coating layer of an insulated cable is usually used by crosslinking its constituent materials in order to improve heat resistance. Currently, the chemical crosslinking method using an organic peroxide crosslinking agent is the most widely used crosslinking method for the material constituting the insulation coating layer in the production of high voltage insulated cables. When an organic polymer containing a peroxide crosslinking agent is heated in the presence of oxygen, or an organic polymer containing the decomposition residue of an organic peroxide crosslinking agent is heated in the presence of oxygen, a large amount of water is generated. , I learned that it remains in organic polymers.
本発明者らの研究によれば、水分の発生は、有機過酸化
物架橋剤から生成したアルコールが酸素存在下では該酸
素の触媒作用により分子内脱水反応を起こすことに起因
する。たとえば有機過酸化物架橋剤がジクミルパーオキ
サイドの場合、分解生成物の1種たるキュミルアルコー
ルからα−メチルスチレンが生成する際に水が生成する
。一般にこの種の脱水反応は、150℃以上で容易に進
行し、その結果架橋高分子中に水が生成することになり
、水と高分子との相客性の点から水は凝集し、ボイドの
発生につながるのである。According to the research conducted by the present inventors, the generation of water is caused by the fact that the alcohol produced from the organic peroxide crosslinking agent undergoes an intramolecular dehydration reaction in the presence of oxygen due to the catalytic action of the oxygen. For example, when the organic peroxide crosslinking agent is dicumyl peroxide, water is produced when α-methylstyrene is produced from cumyl alcohol, which is one of the decomposition products. In general, this type of dehydration reaction easily proceeds at temperatures above 150°C, and as a result, water is generated in the crosslinked polymer, and due to the compatibility between water and the polymer, the water aggregates and voids are formed. This leads to the occurrence of
さらに、ポリエチレンなどの有機過酸化物架橋剤架橋性
有機裔分子には、通常、4.4′−チオビス(6−t−
ブチル−3−メチル−フェノール)のような酸化条件下
で容易にプロトンを放出して共鳴安定下する酸化防止剤
が配合されているが、かかる種類の酸化防止剤は上記し
た分子内脱水反応を、而して水分生成反応を促進する作
用のあることも判明した。Furthermore, organic peroxide crosslinkers such as polyethylene and crosslinkable organic progeny molecules are usually used with 4,4'-thiobis(6-t-
Antioxidants such as (butyl-3-methyl-phenol) that easily release protons under oxidizing conditions to stabilize the resonance are included, but these types of antioxidants do not react well with the above-mentioned intramolecular dehydration reaction. It was also found that it has the effect of promoting the water production reaction.
ンを すべき口 占
本発明は、酸化防止剤を配合した有機高分子を架橋、あ
るいはそのたの目的で加熱処理しても水分生成の問題の
少ない加熱処理方法を提供しようとするものである。SUMMARY OF THE INVENTION The present invention aims to provide a heat treatment method that reduces the problem of moisture generation even when heat-treated organic polymers containing antioxidants for crosslinking or other purposes. .
−占を2するための
本発明は、有機過酸化物架橋剤または有機過酸化物架橋
剤の分解残渣を含有する架橋しうるまたは架橋された有
機高分子を加熱処理する際に、該有機高分子中にヒンダ
ードフェノール系酸化防止剤の存在下でしかも酸素フリ
ーの状態で加熱することを特徴とする有機高分子の加熱
処理方法である。- The present invention for increasing the number of organic peroxide cross-linking agents or organic peroxide cross-linking agents when heat treating a cross-linkable or cross-linked organic polymer containing an organic peroxide cross-linking agent or a decomposition residue of the organic peroxide cross-linking agent. This is a method for heat treatment of organic polymers, which is characterized by heating in the presence of a hindered phenolic antioxidant in the molecule and in an oxygen-free state.
作用−
本発明においては、有機過酸化物架橋剤または有機過酸
化物架橋剤の分解残渣を含有する有機高分子を酸素フリ
ーの状態で加熱するので上記した有機過酸化物架橋剤か
ら生成したアルコールの分子内脱水反応が生じないか、
または軽度で済む。Effect - In the present invention, since the organic peroxide crosslinking agent or the organic polymer containing the decomposition residue of the organic peroxide crosslinking agent is heated in an oxygen-free state, the alcohol generated from the organic peroxide crosslinking agent described above is heated. Is there an intramolecular dehydration reaction?
Or only mild.
一方、有機高分子は一般に酸化防止剤が配合された状態
で使用されるが、本発明においては、かかる酸化防止剤
として酸化条件下でもプロトンを放出し難いヒンダード
フェノール系のもの用いるので、たとえアルコールの分
子内脱水反応が生じることがあってもその反応を促進す
るようなことがない、したがって本発明の加熱処理方法
を実施した場合は、有機高分子中の水分含有量は従来の
加熱処理方法と比較して極めて低度に維持され、この結
果、加熱処理後の有機高分子の電気特性に何等悪影響を
及ぼさないという長所がある。On the other hand, organic polymers are generally used with antioxidants mixed in, but in the present invention, hindered phenol-based antioxidants that are difficult to release protons even under oxidizing conditions are used. Even if an intramolecular dehydration reaction of alcohol occurs, the reaction will not be accelerated. Therefore, when the heat treatment method of the present invention is carried out, the water content in the organic polymer will be lower than that of conventional heat treatment. This method has the advantage that the temperature is maintained at an extremely low level compared to the heat treatment method, and as a result, there is no adverse effect on the electrical properties of the organic polymer after the heat treatment.
の な
本発明の加熱処理方法が対象とする有機高分子は、後記
するヒンダードフェノール系酸化防止剤の他、有機過酸
化物架橋剤および/またはその分解残渣を含有する未架
橋もしくは架橋法のものである。The organic polymers targeted by the heat treatment method of the present invention are uncrosslinked or crosslinked containing an organic peroxide crosslinking agent and/or its decomposition residue, in addition to the hindered phenolic antioxidant described below. It is something.
有機高分子としては有機過酸化物架橋剤を用いて架橋さ
れるもので、特に電気絶縁性を有するものがあげられ、
たとえばポリオレフィンなどにおいてと(に存用である
。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、エチレン−酢酸ビニル共重合体、エ
チレン−エチルアクリレート共重合体などがあげられ、
それらのうち密度が0.88〜0.95のポリエチレン
にとくに顕著な効果を奏する。Examples of organic polymers include those that are crosslinked using an organic peroxide crosslinking agent, and in particular those that have electrical insulation properties.
For example, it is used in polyolefins, etc. Polyolefins include polyethylene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, etc.
Among them, polyethylene having a density of 0.88 to 0.95 has a particularly remarkable effect.
ヒンダードフェノール系酸化防止剤としては分子中に少
なくとも1個以上のフェノール性水酸基を有し、さらに
その水酸基のうちの少なくとも1個以上がその隣接位(
すなわちオルソ位)に第3個(Lert−)ブチル基を
有する構造を有するものが用いられ、具体例としては2
.6−ジーt−ブチル−p−クレゾール、2,4−ジメ
チル−6−t−ブチルフェノール、4,4°−チオビス
(3−メチル−6−t−ブチルフェノール)、2.2’
−メチレンビス(4−メチル−6−t−ブチルフェノー
ル)、4,4゛−ブチリデンビス(3−メチル−6−t
−ブチルフェノール)、テトラキス〔メチレン−3(3
,5−ジ−t−ブチル−4−ヒドロキシフヱニルブロビ
オネート〕メタン、1.1.3− )リス(2−メチル
−4−ヒドロキシ−5−t−ブチルフェニル)ブタン、
t−ブチルヒドロキシアニソールなどがあげられる。Hindered phenolic antioxidants have at least one phenolic hydroxyl group in the molecule, and at least one of the hydroxyl groups is located at the adjacent position (
In other words, those having a structure having a tertiary (Lert-)butyl group at the ortho position) are used, and specific examples include 2
.. 6-di-t-butyl-p-cresol, 2,4-dimethyl-6-t-butylphenol, 4,4°-thiobis(3-methyl-6-t-butylphenol), 2.2'
-methylenebis(4-methyl-6-t-butylphenol), 4,4゛-butylidenebis(3-methyl-6-t-butylphenol),
-butylphenol), tetrakis[methylene-3 (3
, 5-di-t-butyl-4-hydroxyphenylbrobionate]methane, 1.1.3-)lis(2-methyl-4-hydroxy-5-t-butylphenyl)butane,
Examples include t-butylhydroxyanisole.
ヒンダードフェノール系酸化防止剤の配合量は有機高分
子100重盪部あたり0.1〜10重量部、特に0.5
〜5重量部程度が好ましい。The blending amount of the hindered phenolic antioxidant is 0.1 to 10 parts by weight, especially 0.5 parts by weight per 100 parts by weight of the organic polymer.
About 5 parts by weight is preferable.
有機過酸化物架橋剤としては、分解により前記した脱水
反応を生起する分解生成物を生ぜしめるものがあげられ
、たとえば分解して第3級アルコールを生ずるクミルパ
ーオキサイドやジクミルパーオキサイドなど、就中ジク
ミルパーオキサイドがあげられる0本発明においては、
加熱処理される有機高分子中に含まれる有機過酸化物架
橋剤またはその分解残渣の含有量が10重量%以上の高
濃度であっても本発明の方法は効果がある。しかし、そ
れらの濃度は通常0.1〜5重盪%程度であって、本発
明は勿論そのような濃度範囲において特に顕著な効果が
得られる。Examples of organic peroxide crosslinking agents include those that produce decomposition products that cause the dehydration reaction described above, such as cumyl peroxide and dicumyl peroxide, which decompose to produce tertiary alcohols. In the present invention, dicumyl peroxide can be mentioned.
The method of the present invention is effective even when the content of the organic peroxide crosslinking agent or its decomposition residue contained in the organic polymer to be heat treated is as high as 10% by weight or more. However, their concentration is usually about 0.1 to 5% by weight, and the present invention can of course obtain particularly remarkable effects within such a concentration range.
本発明の方法は、前記脱水反応を可能な限り生起させな
いために、酸素フリーの状態で有機高分子を加熱処理、
たとえば架橋することに特徴がある。酸素フリーの状態
としては、酸素の存在量ができるだけ少ない雰囲気が例
示される。その場合、該雰囲気の酸素含有量が5%(容
量%、以下同様)以下、好ましくは2%以下、特に0.
5%以下とするのかよい、雰囲気ガスとしては、たと
えば、NtSHes CO□、計、SF4などの不活性
ガス中が例示されるが、それ以外のガスでもよい。かか
る酸素フリーの雰囲気ガス下で加熱処理するためにはた
とえばそのようなガスを加熱処理を行う個所に常時送風
する、加熱処理個所を適当なケースなどで囲み、その内
部を上記ガスで置換するなどの方法を採用することがで
きる。The method of the present invention involves heating an organic polymer in an oxygen-free state in order to prevent the dehydration reaction from occurring as much as possible.
For example, it is characterized by crosslinking. An example of an oxygen-free state is an atmosphere in which the amount of oxygen present is as small as possible. In that case, the oxygen content of the atmosphere is 5% (volume %, the same applies hereinafter) or less, preferably 2% or less, especially 0.
Examples of the atmospheric gas containing 5% or less include inert gases such as NtSHes CO□, SF4, etc., but other gases may also be used. In order to carry out heat treatment under such an oxygen-free atmospheric gas, for example, such a gas may be constantly blown onto the area to be heat treated, or the area to be heated may be surrounded by a suitable case, and the inside of the area may be replaced with the above gas. method can be adopted.
酸素フリーの他の状態としては、被加熱処理体が気体不
透過性の材料で気体が入らないように密着カバーされて
いる場合がある。この場合、気体不透過性の材料、たと
えば鉛などの金属のテープやナイロン、ポリフッ化ビニ
リデンなどの梼脂テープを被加熱処理体部分に棒巻して
酸素との接触を断つ方法や、加熱される部分にぴったり
合う金型を用いるなどの方法がある。As another oxygen-free state, the object to be heated may be tightly covered with a gas-impermeable material to prevent gas from entering. In this case, gas-impermeable material such as metal tape such as lead, resin tape such as nylon or polyvinylidene fluoride may be wrapped around the part of the object to be heated to cut off contact with oxygen; There are methods such as using a mold that fits exactly into the area.
本発明の加熱処理方法が効果を奏しうる加熱処理温度は
、対象とする有機高分子、架橋剤残渣として存在する第
3級アルコールの種類などによって異なるが、通常10
0℃以上または有機高分子の融点以上である。The heat treatment temperature at which the heat treatment method of the present invention is effective varies depending on the target organic polymer, the type of tertiary alcohol present as a crosslinking agent residue, etc., but is usually 10
The temperature is 0°C or higher or the melting point of the organic polymer.
四乗
本発明の加熱処理方法は、未架橋の有機高分子組成物成
形体、たとえば高圧絶縁ケーブルの加熱架橋、架橋済の
有機高分子成形体の加熱処理などに適用できる。特につ
ぎに述べる架橋済絶縁ケーブル同士の接続作業に適用し
て顕著な効果が得られる。The heat treatment method of the fourth power invention can be applied to heat crosslinking of uncrosslinked organic polymer composition molded bodies, such as high-voltage insulated cables, heat treatment of crosslinked organic polymer composition molded bodies, and the like. In particular, remarkable effects can be obtained when applied to the connection work between cross-linked insulated cables, which will be described below.
絶縁ケーブルの接続においては、通常まず接続すべきケ
ーブルの端部の絶縁被覆を剥ぎとり、絶縁被覆端部をペ
ンシリングする。ついで導体同士を接!し、最後にペン
シリングした部分に有機過酸化物架橋剤を含む補強用の
有機高分子絶縁物を施し、加熱された金型により加圧し
て絶縁被覆部および補強部両者を一体に架橋接合する。When connecting insulated cables, the insulation coating is usually first stripped off from the ends of the cables to be connected, and the insulation coating ends are penciled. Then connect the conductors! Finally, a reinforcing organic polymer insulator containing an organic peroxide cross-linking agent is applied to the penciled part, and pressure is applied using a heated mold to cross-link both the insulating coating and the reinforcing part together. .
従来はこの接続時の加熱により水分が多量に生成して接
続部の電気絶縁不良がしばしばみられたが、本発明の方
法により水分の生成が抑えられて電気絶縁不良の事故発
生率が激減する。Conventionally, a large amount of moisture was generated due to the heating during this connection, often resulting in poor electrical insulation at the connection part, but the method of the present invention suppresses the generation of moisture and dramatically reduces the incidence of electrical insulation defects. .
裏旌班
以下、実施例および比較例により本発明を一層詳細に説
明する。Below, the present invention will be explained in more detail with reference to Examples and Comparative Examples.
比較例1
低密度ポリエチレン100重量部、およびジクミルパー
オキサイド2.0重量部とからなる架橋性組成物を18
0℃で20分間プレス架橋して厚さl am、1X2a
s角の架橋シートを得た。ついでこの架橋シートを18
0℃の空気中で40分間加熱した。Comparative Example 1 A crosslinkable composition consisting of 100 parts by weight of low density polyethylene and 2.0 parts by weight of dicumyl peroxide was
Press cross-linked at 0℃ for 20 minutes to a thickness of lam, 1x2a
A crosslinked sheet with an s-angle was obtained. Next, this crosslinked sheet was
Heated in air at 0°C for 40 minutes.
比較例2
低密度ポリエチレン100重量部およびジクミルパーオ
キサイド2.0重量部とからなる架橋性組成物を180
℃で20分間プレス架橋して厚さ1鶴、lX2CJ角の
架橋シートを得た。ついで、この架橋シートを180℃
に加熱保持された酸素濃度が4容量%の窒素雰囲気中で
40分間加熱した。Comparative Example 2 A crosslinkable composition consisting of 100 parts by weight of low density polyethylene and 2.0 parts by weight of dicumyl peroxide was
Press crosslinking was carried out at ℃ for 20 minutes to obtain a crosslinked sheet with a thickness of 1 square and a size of 1×2CJ square. Next, this crosslinked sheet was heated to 180°C.
The sample was heated for 40 minutes in a nitrogen atmosphere with an oxygen concentration of 4% by volume.
比較例3
低密度ポリエチレン100重量部、ジクミルパーオキサ
イド2.0重量部、および4.4”−チオビス(6−t
−ブチル−1,3−メチルフェノール)0.3重量部と
からなる架橋性組成物を用いた以外は比較例1と同様に
して架橋並びに空気中での加熱を行った。Comparative Example 3 100 parts by weight of low density polyethylene, 2.0 parts by weight of dicumyl peroxide, and 4.4”-thiobis(6-t
Crosslinking and heating in air were carried out in the same manner as in Comparative Example 1, except that a crosslinkable composition consisting of 0.3 parts by weight of (butyl-1,3-methylphenol) was used.
比較例4
比較例3で得た架橋シートを180℃に加熱保持された
酸素濃度が4容量%の窒素雰囲気中で40分間加熱した
。Comparative Example 4 The crosslinked sheet obtained in Comparative Example 3 was heated for 40 minutes in a nitrogen atmosphere with an oxygen concentration of 4% by volume and maintained at 180°C.
実施例1
低密度ポリエチレン100重量部およびジクミルパーオ
キサイド2.0重量部、および2.2”−メチレンビス
(4−エチル−6−t−ブチルフェノール)0.3重層
部とからなる架橋性組成物を180℃で20分間プレス
架橋して厚さ1mm、lX2am角の架橋シートを得た
。ついでこの架橋シートを180℃に加熱保持された酸
素濃度が4容量%の窒素雰囲気中で40分間加熱した。Example 1 Crosslinkable composition consisting of 100 parts by weight of low density polyethylene, 2.0 parts by weight of dicumyl peroxide, and 0.3 parts by weight of 2.2''-methylenebis(4-ethyl-6-t-butylphenol) was press-crosslinked at 180°C for 20 minutes to obtain a crosslinked sheet with a thickness of 1 mm and a square size of 1 x 2 am.Then, this crosslinked sheet was heated at 180°C for 40 minutes in a nitrogen atmosphere with an oxygen concentration of 4% by volume. .
実施例2
2.2゛−メチレンビス(4−エチル−6−t−ブチル
フェノール)に代わって2,2°−メチレンビス(4−
メチル−6−t−ブチルフェノール)を用いた以外は実
施例1と同様の架橋性組成物を用い、実施例1と同様に
して架橋並びに4容量%の窒素雰囲気中での加熱を行っ
た。Example 2 2,2°-methylenebis(4-
The same crosslinkable composition as in Example 1 was used except that methyl-6-t-butylphenol) was used, and crosslinking and heating in a 4% by volume nitrogen atmosphere were carried out in the same manner as in Example 1.
実施例3
2.2°−メチレンビス(4−エチル−6−t−ブチル
フェノール)に代わって2,5−ジーL−ブチルハイド
ロキノンを用いた以外は実施例1と同様の架橋性組成物
を用い、実施例1と同様にして架橋並びに4容量%の窒
素雰囲気中での加熱を行った。Example 3 The same crosslinkable composition as in Example 1 was used except that 2,5-di-L-butylhydroquinone was used instead of 2.2°-methylenebis(4-ethyl-6-t-butylphenol), Crosslinking and heating in a 4% by volume nitrogen atmosphere were carried out in the same manner as in Example 1.
比較例1〜4、および実施例1〜3で加熱処理された各
試料につきガスクロマトグラフィーにより各試料中に残
存するクミルアルコールの量およびα−メチルスチレン
の量を測定し、(α−メチルスチレン)/〔クミルアル
コール〕のモル比をを調べた。結果を第1表に示す。For each sample heat-treated in Comparative Examples 1 to 4 and Examples 1 to 3, the amount of cumyl alcohol and the amount of α-methylstyrene remaining in each sample were measured by gas chromatography. The molar ratio of styrene/cumyl alcohol was investigated. The results are shown in Table 1.
なお、該モル比が大きくなることはクミルアルコールが
脱水反応を起こし、α−メチルスチレンとの水の生成が
大きくなることを意味している。Incidentally, an increase in the molar ratio means that cumyl alcohol undergoes a dehydration reaction, and the production of water with α-methylstyrene increases.
同表よりプロトンを放出し易い酸化防止剤たる4゜4゛
−チオビス(6−t−ブチル−1,3−メチルフェノー
ル)を使用した場合には、クミルアルコールの脱水反応
に大きな促進作用がみられるが、各実施例からの試料の
〔α−メチルスチレン)/〔クミルアルコール〕のモル
比は、酸化防止剤が配合されたものであるにもかかわら
ず橿めて小さく、水分の生成に実質促進作用を示さない
ことを示している。From the same table, when 4゜4゛-thiobis (6-t-butyl-1,3-methylphenol), which is an antioxidant that easily releases protons, is used, it has a large accelerating effect on the dehydration reaction of cumyl alcohol. However, the molar ratio of [α-methylstyrene]/[cumyl alcohol] in the samples from each example was relatively small despite the fact that they contained antioxidants, indicating that water production It has been shown that there is no real promoting effect on
第1表 特許出願人 三菱電線工業株式会社 Table 1 Patent applicant: Mitsubishi Cable Industries, Ltd.
Claims (1)
解残渣を含有する架橋しうるまたは架橋された有機高分
子を加熱処理する際に、該有機高分子中にヒンダードフ
ェノール系酸化防止剤の存在下でしかも酸素フリーの状
態で加熱することを特徴とする有機高分子の加熱処理方
法。 2、有機高分子が電気絶縁性のものである特許請求の範
囲第1項に記載の加熱処理方法。 3、有機高分子が絶縁ケーブルの絶縁被覆層の構成材料
である特許請求の範囲第2項に記載の加熱処理方法。 4、有機高分子がポリエチレンである特許請求の範囲第
1項乃至第3項のいずれかに記載の加熱処理方法。 5、有機過酸化物架橋剤がジクミルパーオキサイドであ
る特許請求の範囲第1項乃至第4項のいずれかに記載の
加熱処理方法。[Claims] 1. When heat treating a crosslinkable or crosslinked organic polymer containing an organic peroxide crosslinking agent or a decomposition residue of the organic peroxide crosslinking agent, A method for heat treatment of organic polymers, characterized by heating in the presence of a hindered phenolic antioxidant and in an oxygen-free state. 2. The heat treatment method according to claim 1, wherein the organic polymer is electrically insulating. 3. The heat treatment method according to claim 2, wherein the organic polymer is a constituent material of the insulating coating layer of the insulated cable. 4. The heat treatment method according to any one of claims 1 to 3, wherein the organic polymer is polyethylene. 5. The heat treatment method according to any one of claims 1 to 4, wherein the organic peroxide crosslinking agent is dicumyl peroxide.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP25935387A JPH01101338A (en) | 1987-10-14 | 1987-10-14 | Heating process for organic polymer |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP25935387A JPH01101338A (en) | 1987-10-14 | 1987-10-14 | Heating process for organic polymer |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH01101338A true JPH01101338A (en) | 1989-04-19 |
JPH0511752B2 JPH0511752B2 (en) | 1993-02-16 |
Family
ID=17332930
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP25935387A Granted JPH01101338A (en) | 1987-10-14 | 1987-10-14 | Heating process for organic polymer |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH01101338A (en) |
-
1987
- 1987-10-14 JP JP25935387A patent/JPH01101338A/en active Granted
Also Published As
Publication number | Publication date |
---|---|
JPH0511752B2 (en) | 1993-02-16 |
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