JPH03247640A - Production of crosslinked polyolefin material - Google Patents
Production of crosslinked polyolefin materialInfo
- Publication number
- JPH03247640A JPH03247640A JP4249190A JP4249190A JPH03247640A JP H03247640 A JPH03247640 A JP H03247640A JP 4249190 A JP4249190 A JP 4249190A JP 4249190 A JP4249190 A JP 4249190A JP H03247640 A JPH03247640 A JP H03247640A
- Authority
- JP
- Japan
- Prior art keywords
- antioxidant
- polyolefin
- crosslinked polyolefin
- organic peroxide
- component
- 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
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 46
- 239000000463 material Substances 0.000 title claims abstract description 36
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 37
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 31
- 150000001451 organic peroxides Chemical class 0.000 claims abstract description 26
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 239000008188 pellet Substances 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- -1 polyethylene Polymers 0.000 claims abstract description 7
- 150000002978 peroxides Chemical class 0.000 claims abstract description 6
- 239000004698 Polyethylene Substances 0.000 claims abstract description 5
- 238000002844 melting Methods 0.000 claims abstract description 5
- 230000008018 melting Effects 0.000 claims abstract description 5
- 229920000573 polyethylene Polymers 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims abstract description 4
- VWGKEVWFBOUAND-UHFFFAOYSA-N 4,4'-thiodiphenol Chemical group C1=CC(O)=CC=C1SC1=CC=C(O)C=C1 VWGKEVWFBOUAND-UHFFFAOYSA-N 0.000 claims description 3
- 238000005470 impregnation Methods 0.000 claims 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 abstract description 6
- HXIQYSLFEXIOAV-UHFFFAOYSA-N 2-tert-butyl-4-(5-tert-butyl-4-hydroxy-2-methylphenyl)sulfanyl-5-methylphenol Chemical compound CC1=CC(O)=C(C(C)(C)C)C=C1SC1=CC(C(C)(C)C)=C(O)C=C1C HXIQYSLFEXIOAV-UHFFFAOYSA-N 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 238000001125 extrusion Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 4
- 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 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 239000012212 insulator Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229920003020 cross-linked polyethylene Polymers 0.000 description 2
- 239000004703 cross-linked polyethylene Substances 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- FEXBEKLLSUWSIM-UHFFFAOYSA-N 2-Butyl-4-methylphenol Chemical compound CCCCC1=CC(C)=CC=C1O FEXBEKLLSUWSIM-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 239000011243 crosslinked material Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229920001179 medium density polyethylene Polymers 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- XKIVKIIBCJIWNU-UHFFFAOYSA-N o-[3-pentadecanethioyloxy-2,2-bis(pentadecanethioyloxymethyl)propyl] pentadecanethioate Chemical compound CCCCCCCCCCCCCCC(=S)OCC(COC(=S)CCCCCCCCCCCCCC)(COC(=S)CCCCCCCCCCCCCC)COC(=S)CCCCCCCCCCCCCC XKIVKIIBCJIWNU-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 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
- 230000000704 physical effect Effects 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
Landscapes
- Organic Insulating Materials (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、高圧電カケ−プルの絶縁体などに用いられる
架橋ポリオレフィン材料において、酸化防止剤のブルー
ミング現象の生しにくい材料を容易に提供しうる、架橋
ポリオレフィン材料の製造方法の改良に関するものであ
る。Detailed Description of the Invention (Field of Industrial Application) The present invention easily provides a crosslinked polyolefin material that is used as an insulator for high-voltage electric cables and is less prone to the blooming phenomenon of antioxidants. The present invention relates to an improvement in a method for producing a crosslinked polyolefin material.
（従来の技術）
架橋ポリオレフィン材料、特に架橋ポリエチレン材料は
、良好な電気性能、高温での耐変形性。(Prior Art) Cross-linked polyolefin materials, especially cross-linked polyethylene materials, have good electrical performance and deformation resistance at high temperatures.
高度の耐薬品性などの優秀な特性を有しており、高圧電
カケ−プルの絶縁体などに使用されている。It has excellent properties such as high chemical resistance, and is used as an insulator for high-voltage electrical cables.
この材料は、ポリオレフィン、酸化防止剤及び架橋剤と
を主要構成分として含み、通常これらの成分が混合され
たペレットなどの形態で供給される。This material contains a polyolefin, an antioxidant, and a crosslinking agent as main components, and is usually supplied in the form of a pellet or the like in which these components are mixed.
（発明が解決しようとする課Ｂ）
このようなペレットは、混合後に即座に成形加工される
場合にはよいが、そうでない場合に酸化防止剤がペレッ
トの表面に析出する、いわゆるブルーミング現象を生し
、その表面に酸化防止剤の粉末をまぶしたような状態と
なる。(Problem B to be solved by the invention) Such pellets are good if they are molded immediately after mixing, but if this is not the case, the so-called blooming phenomenon occurs in which the antioxidant precipitates on the surface of the pellets. However, the surface looks like it has been sprinkled with antioxidant powder.
この粉末は容易にペレットなどの表面から取れ、押出機
の材料供給部分などに付着しあるいは材料中に入ること
で局部的な酸化防止剤の過少あるいは過多を引き起こす
。This powder is easily removed from the surface of pellets, etc., and adheres to the material supply part of the extruder or enters the material, causing local under- or over-consumption of the antioxidant.
そのために、材料混合後の使用までの時間を制限したり
、ブルーミング現象が生しにくいように低温度でペレッ
トなどを保管したりするといったような対策が用いられ
ている場合があるが、管理が煩雑であるとの問題があっ
た。To this end, countermeasures are sometimes taken, such as limiting the time between mixing materials and using them, and storing pellets and other materials at low temperatures to prevent blooming. There was a problem that it was complicated.
（課題を解決するための手段）
本発明者らは、上記の課題を解決するために鋭意検討し
た結果、ポリオレフィンと酸化防止剤などの混合時に、
予め少量の有機過酸化物を添加、反応させて、酸化防止
剤をポリオレフィンの分子鎖に化学的に結合させること
により、酸化防止剤がブルーミング現象しにくくなるこ
とを見出し、本発明を完成するに至った。(Means for Solving the Problems) As a result of intensive studies to solve the above problems, the present inventors found that when mixing polyolefins, antioxidants, etc.
It was discovered that by adding and reacting a small amount of organic peroxide in advance to chemically bond the antioxidant to the molecular chain of the polyolefin, the antioxidant becomes less susceptible to the blooming phenomenon, and in order to complete the present invention. It's arrived.
すなわち、本発明は；
■ ポリオレフィンと酸化防止剤と架橋剤とを主要構成
分として含む架橋ポリオレフィン材料の各構成分の混合
時に、予めポリオレフィンと酸化防止剤と少量の有機過
酸化物とを酸化防止剤の融点以上でかつ該有機過酸化物
の反応温度以上の温度で混合し、該少量の有機過酸化物
を反応せしめた後、架橋剤を混合ないし含浸などの方法
により添加することを特徴とする、架橋ポリオレフィン
材料の製造方法を提供し、かつ、
■ ポリオレフィンとしてポリエチレンを用いる点に、
また
■ 有機過酸化物として過酸化ジアルキルを用いる点に
、また
■ 酸化防止剤としてチオビスフェノール系を用いる点
に、また
■ 架橋ポリオレフィン材料がペレットの形態で供給さ
れる点にも特徴を有する。That is, the present invention: (1) When mixing the components of a crosslinked polyolefin material containing a polyolefin, an antioxidant, and a crosslinking agent as main components, the polyolefin, the antioxidant, and a small amount of organic peroxide are preliminarily prevented from oxidizing. The crosslinking agent is mixed at a temperature higher than the melting point of the agent and higher than the reaction temperature of the organic peroxide to react with a small amount of the organic peroxide, and then the crosslinking agent is added by a method such as mixing or impregnation. The present invention provides a method for producing a crosslinked polyolefin material, and ■ uses polyethylene as the polyolefin.
It is also characterized by (1) using dialkyl peroxide as the organic peroxide, (2) using thiobisphenol as the antioxidant, and (3) supplying the crosslinked polyolefin material in the form of pellets.
さらに、本発明を具体的に説明する。Furthermore, the present invention will be specifically explained.
本発明に使用する酸化防止剤としては、例えば４．４゛
−チオビス（６−ｔ−ブチル−３−メチルフェノール）
、
２．２゛−メチレンビス（６−ｔ〜ブチル−４メチルフ
エノール）、
ジラウリル−３，３−チオジプロピオネート、ジステア
リル−３，３−チオジプロピオネート、テトラキス〔メ
チレン−３−（３’ ５’ −ジｔ−フチルー４°
−ヒドロキシフェニル）フロビオ名−ト〕メタン、
ペンタエリスリトールテトラキス（β−ラウリルチオプ
ロピオネート）、
ｎ−オクタデシル−３−（３° ５゛−ジーｔブチル
ー４゛−ヒドロキシフェニル）プロピオネートなどを単
独であるいは２種以上を混合して用いることができる。Examples of antioxidants used in the present invention include 4.4'-thiobis(6-t-butyl-3-methylphenol)
, 2.2'-methylenebis(6-t~butyl-4methylphenol), dilauryl-3,3-thiodipropionate, distearyl-3,3-thiodipropionate, tetrakis[methylene-3-(3 '5'-dit-phthyru 4°
-Hydroxyphenyl) flobion name - [methane], pentaerythritol tetrakis (β-laurylthiopropionate), n-octadecyl-3-(3°5゛-di-t-butyl-4゛-hydroxyphenyl)propionate, etc. alone. Alternatively, two or more types can be used in combination.
好ましくはチオビスフェノール系酸化防止剤、特に好ま
しくは４．４“−チオビス（６−ｔ−ブチル−３−メチ
ルフェノール）を挙げることができる。Preferred are thiobisphenol antioxidants, particularly preferably 4.4"-thiobis(6-t-butyl-3-methylphenol).
上記酸化防止剤の添加量は、ポリオレフィンを酸化防止
するのに充分な量であれば特に制限されないが、一般に
、ポリオレフィン１００重量部に対して０．０５〜５重
量部を用いることができる、また、少量で使用される有
機過酸化物としては、例えばジクミルパーオキサイド、
ｔ−ブチルパーオキサイド、
２．５−ジメチル−２，５−ジ（ｔ−ブチルパーオキシ
）ヘキサン、
２．５−ジメチル−２，５−ジ（ｔ−ブチルパーオキシ
）ヘキシン−３、
α、α゛−ビスｔ−ブチルパーオキシ−ｍ−イソプロピ
ル）ベンゼンなどを用いることができるが、好ましくは
過酸化ジアルキル、特に好ましくはジクミルパーオキシ
ドを挙げることができる。The amount of the antioxidant added is not particularly limited as long as it is sufficient to prevent oxidation of the polyolefin, but generally, 0.05 to 5 parts by weight can be used with respect to 100 parts by weight of the polyolefin. Examples of organic peroxides used in small amounts include dicumyl peroxide, t-butyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, and 2,5-dimethyl. -2,5-di(t-butylperoxy)hexyne-3, α,α゛-bis-t-butylperoxy-m-isopropyl)benzene, etc. can be used, but dialkyl peroxide is particularly preferred. can include dicumyl peroxide.
上記有機過酸化物の添加量は、使用した酸化防止剤をポ
リオレフィンの分子鎖にグラフト化など化学的に結合さ
せるのに充分な範囲の少量に留める必要があり、使用し
た酸化防止剤の添加量及びポリオレフィンの種類などに
より必ずしも一定しないが、一般にポリオレフィン１０
０重量部に対して０．０１〜１． ０重量部、好ましく
は０．０５〜０．６重量部である。The amount of the organic peroxide added must be kept within a small enough range to chemically bond the antioxidant to the molecular chain of the polyolefin, such as by grafting. Although not necessarily constant depending on the type of polyolefin, etc., generally polyolefin 10
0.01 to 1.0 parts by weight. 0 parts by weight, preferably 0.05 to 0.6 parts by weight.
この有機過酸化物０．０１重量部以下では酸化防止剤の
プルーム現象抑制効果が見られず、また、１．０重量部
以上ではポリオレフィン自体の架橋反応が進行してしま
い、このポリオレフィン架橋材料を成形、例えば押出成
形した場合の押出外観が悪化する。If the organic peroxide is less than 0.01 part by weight, no effect of inhibiting the plume phenomenon of the antioxidant will be observed, and if it is more than 1.0 part by weight, the crosslinking reaction of the polyolefin itself will proceed, making this polyolefin crosslinked material When molded, for example by extrusion, the appearance of the extrusion deteriorates.
使用するポリオレフィン材料としては、特に制限されな
いが、一般にポリエチレン、ポリプロピレン、ポリブテ
ン−１、ポリメチルペンテン−１などを単独にあるいは
それらの組み合わせを挙げることができる。好ましくは
高密度、中密度、低密度のポリエチレンである。The polyolefin material to be used is not particularly limited, but generally includes polyethylene, polypropylene, polybutene-1, polymethylpentene-1, etc. alone or in combinations thereof. Preferred are high density, medium density and low density polyethylenes.
上記ポリオレフィンと酸化防止剤と少量の有機過酸化物
とを、該酸化防止剤の融点以上でかつ該有機過酸化物の
反応温度以上の温度で混合し、該少量の有ｍ過酸化物を
反応せしめて該酸化防止剤をポリオレフィンにグラフト
化など化学的に結合することに特徴がある。The above polyolefin, antioxidant, and a small amount of organic peroxide are mixed at a temperature higher than the melting point of the antioxidant and higher than the reaction temperature of the organic peroxide, and the small amount of organic peroxide is reacted. At least the antioxidant is chemically bonded to the polyolefin by grafting or the like.
ここで言う有機過酸化物の反応温度とは、１０分間でそ
の有機過酸化物の半量が反応する温度を指す。The reaction temperature of the organic peroxide referred to herein refers to the temperature at which half of the organic peroxide reacts in 10 minutes.
この場合に、この混合・反応温度は、使用した酸化防止
剤の融点及び有ｍ過酸化物の反応温度以上であれば特に
制限されないが、一般に、１６０〜２２０°Ｃ程度で行
うことができる。In this case, the mixing/reaction temperature is not particularly limited as long as it is higher than the melting point of the antioxidant used and the reaction temperature of the peroxide used, but it can generally be carried out at about 160 to 220°C.
次に、このように混合が終了した後に、架橋剤を添加す
る。Next, after the mixing has been completed in this manner, a crosslinking agent is added.
この際に、架橋剤の添加方法としては特に制限されない
が、−船釣に混合あるいは含浸の方法により行うことが
できる。この添加の温度は、架橋剤の架橋反応が余り起
こらない程度の低い温度、例えば４０〜１３０°Ｃ程度
で行うことが好ましい。At this time, the method of adding the crosslinking agent is not particularly limited, but it can be carried out by mixing on a boat or by impregnation. This addition is preferably carried out at a low temperature such that the crosslinking reaction of the crosslinking agent does not occur much, for example, about 40 to 130°C.
使用する架橋剤としては、ポリオレフィンを架橋するも
のなら特に制限されないが、好ましくは前記有機過酸化
物を使用する。また、この架橋剤は、前段階で使用した
有機過酸化物と同じであってもなくても良いが、操作の
簡便性及び得られる成形品の物性管理の点からは同し有
機過酸化物の使用が有利である。The crosslinking agent to be used is not particularly limited as long as it crosslinks polyolefins, but the organic peroxides mentioned above are preferably used. In addition, this crosslinking agent may or may not be the same as the organic peroxide used in the previous step, but from the viewpoint of ease of operation and physical property control of the resulting molded product, it is preferable to use the same organic peroxide. The use of is advantageous.
架橋ポリオレフィン材料の形態は、粉末状でも、ベレン
ト状などの予備成形体でも任意の形態でよいが、電線被
覆等の押出被覆品に用いる場合などには、ペレ・７ト状
が好ましい。The form of the crosslinked polyolefin material may be any form, including a powder or a preform such as a belent, but when used for extrusion coated products such as electric wire coatings, pellets or pellets are preferred.
本発明の架橋ポリオレフィン材料には、必要に応して、
他の熱安定剤、紫外線吸収剤、滑剤、難燃剤、充填剤、
着色剤、他のゴム、樹脂などを配合できる。The crosslinked polyolefin material of the present invention may optionally include:
Other heat stabilizers, UV absorbers, lubricants, flame retardants, fillers,
Colorants, other rubbers, resins, etc. can be added.
また、本発明の架橋ポリオレフィン材料は、電線（ケー
ブル）の絶縁体などの押出成形品に限らず、射出成形品
、チューブ、圧縮成形品、発泡成形品など、架橋ポリオ
レフィン材料を要する用途に広く適用できる。In addition, the crosslinked polyolefin material of the present invention is widely applicable not only to extrusion molded products such as insulators for electric wires (cables), but also to injection molded products, tubes, compression molded products, foam molded products, and other applications that require crosslinked polyolefin materials. can.
（作用）
有機過酸化物は、高温下において分解反応を生じてラジ
カルを発生させる。本発明において、このラジカルがポ
リオレフィン、酸化防止剤の双方に働いて酸化防止剤を
ポリオレフィンの分子鎖にグラフト化させる。(Function) Organic peroxides undergo a decomposition reaction at high temperatures and generate radicals. In the present invention, this radical acts on both the polyolefin and the antioxidant to graft the antioxidant onto the molecular chain of the polyolefin.
このグラフト化された酸化防止剤は、ポリオレフィンの
分子鎖に化学的に強固に固定されてしまい、例えば有ｍ
溶剤などで抽出操作をしても容易には抽出されなくなる
。This grafted antioxidant is chemically firmly fixed to the molecular chain of polyolefin, for example,
Even if an extraction operation is performed using a solvent, etc., it will not be extracted easily.
このような作用により、酸化防止剤のブルーミング現象
を抑制することができる。Such action can suppress the blooming phenomenon of antioxidants.
（実施例）
本発明を実施例により具体的に説明するが、これらは本
発明の範囲を限定するものでない。(Examples) The present invention will be specifically explained by Examples, but these are not intended to limit the scope of the present invention.
ポリエチレン（住人化学■製 Ｇ−８０８）１００重量
部に対して、酸化防止剤〔４，４”−チオビス（６−ｔ
−ブチル−３−メチルフェノール）：商品名スミライザ
ー−ＷＸ−Ｆ７ （住人化学■製）〕を００．２重量部
び所定量の有機過酸化物を添加し、１８０°Ｃで１０分
間混合し、下記第１表に示す配合物を作成した。Antioxidant [4,4''-thiobis(6-t
-butyl-3-methylphenol): trade name Sumilizer-WX-F7 (manufactured by Sumitomo Chemical ■)] was added to 00.2 parts by weight and a predetermined amount of organic peroxide, and mixed at 180°C for 10 minutes. The formulations shown in Table 1 below were prepared.
これらの配合物を直径約５ｍ、長さ約３ｍｍの円筒状に
ベレット化し、次にこの配合物１００重量部に対して、
１．５重量部の架橋剤としてのジクミルパーオキシドを
含浸させ、供試材料とした。These compounds were pelletized into a cylindrical shape with a diameter of about 5 m and a length of about 3 mm, and then, based on 100 parts by weight of this compound,
It was impregnated with 1.5 parts by weight of dicumyl peroxide as a crosslinking agent to prepare a test material.
これらのペレットを５０゛Ｃの温度下で１０日間放置し
、ペレット表面にブルームしてきた酸化防止剤を測定し
た。These pellets were left at a temperature of 50°C for 10 days, and the amount of antioxidant blooming on the pellet surface was measured.
また、これらの材料を３０ｍｍ押出機で棒状に押出し、
押出された材料の外観を観察した。In addition, these materials are extruded into a rod shape using a 30 mm extruder,
The appearance of the extruded material was observed.
その結果を同様に第１表に示す。The results are also shown in Table 1.
第１表
注１）酸化防止剤：４．４”−チオビス（６−ｔ−ブチ
ル−３−メチルフェノール
有機過酸化物Ａニジクミルパーオキサイド有Ｗ化物Ｂ：
２，５−ジメチル−２，５−ジ（ｔ−ブチルパーオキシ
）ヘキサン
有［ヒ物Ｃ：α、α°−ビス（ｔ−ブチルパーオキシ−
ｍ−イソプロピル）ベンゼン。Table 1 Note 1) Antioxidant: 4.4”-thiobis(6-t-butyl-3-methylphenol organic peroxide A dicumyl peroxide W compound B:
With 2,5-dimethyl-2,5-di(t-butylperoxy)hexane [Hydrogen C: α,α°-bis(t-butylperoxy-
m-isopropyl)benzene.
注２） 押出特性
Ｏ；押出外観が良好
× ：押出外観が不良
実施例１〜３及び比較例１の結果より、本発明の架橋ポ
リエチレン材料は、通常の架橋ポリエチレン材料に比べ
て酸化防止剤のブルーム現象が生し難くなっているのが
判る。Note 2) Extrusion properties O; Extrusion appearance is good. It can be seen that the bloom phenomenon is becoming less likely to occur.
また、実施例１と比較例２との結果より、有機過酸化物
は０．０１重量部以下ではブルーム現象抑制効果がなく
、また、０．０５重量部以上が望ましいことが判る。Further, from the results of Example 1 and Comparative Example 2, it can be seen that if the organic peroxide is 0.01 parts by weight or less, there is no effect of suppressing the bloom phenomenon, and that 0.05 parts by weight or more is desirable.
さらに、実施例３及び比較例３の結果より、有機過酸化
物は、１．０重量部以上では架橋ポリエチレン材料を押
出した場合の押出外観が悪化するために、０．６重量部
以下が望ましいことが判る。Furthermore, from the results of Example 3 and Comparative Example 3, it is desirable that the amount of organic peroxide be 0.6 parts by weight or less because if it is 1.0 parts by weight or more, the extruded appearance of the crosslinked polyethylene material will deteriorate. I understand that.
押出外観が悪化するのは、ポリエチレン自体の架橋反応
が進んでしまうためである。The reason why the extruded appearance deteriorates is that the crosslinking reaction of the polyethylene itself progresses.
なお、実施例４〜５の結果より、ジクミルパーオキシド
以外の過酸化ジアルキルを用いても、同様の効果が得ら
れることが判る。In addition, from the results of Examples 4 and 5, it can be seen that similar effects can be obtained even when dialkyl peroxide other than dicumyl peroxide is used.
（発明の効果）
以上説明したように、本発明の架橋ポリオレフィン材料
の製造方法によると、材料の保管時における酸化防止剤
のブルーミング現象を抑制することが可能となり、ブル
ーミングした酸化防止剤が押出機の材料供給部などに付
着し、また、材料中に入ることで住しる酸化防止剤の局
部的な過多あるいは過少を防ぐことが可能となる。(Effects of the Invention) As explained above, according to the method for producing a crosslinked polyolefin material of the present invention, it is possible to suppress the blooming phenomenon of the antioxidant during storage of the material, and the bloomed antioxidant is transferred to the extruder. This makes it possible to prevent local excess or deficiency of antioxidants, which adhere to the material supply parts of the oxidation agent or enter the material.
Claims (5)
成分として含む架橋ポリオレフィン材料の各構成分の混
合時に、予めポリオレフィンと酸化防止剤と少量の有機
過酸化物とを酸化防止剤の融点以上でかつ該有機過酸化
物の反応温度以上の温度で混合し、該少量の有機過酸化
物を反応せしめた後、架橋剤を混合ないし含浸などの方
法により添加することを特徴とする、架橋ポリオレフィ
ン材料の製造方法。(1) When mixing each component of a crosslinked polyolefin material containing a polyolefin, an antioxidant, and a crosslinking agent as main components, the polyolefin, the antioxidant, and a small amount of organic peroxide are mixed in advance at a temperature higher than the melting point of the antioxidant. and a crosslinked polyolefin characterized in that the crosslinking agent is added by a method such as mixing or impregnation after mixing at a temperature higher than the reaction temperature of the organic peroxide and reacting the small amount of the organic peroxide. Method of manufacturing the material.
とする、請求項（１）記載の架橋ポリオレフィン材料の
製造方法。(2) The method for producing a crosslinked polyolefin material according to claim (1), wherein the polyolefin is polyethylene.
徴とする、請求項（１）〜（２）のいずれかに記載の架
橋ポリオレフィン材料の製造方法。(3) The method for producing a crosslinked polyolefin material according to any one of claims (1) to (2), wherein the organic peroxide is dialkyl peroxide.
特徴とする、請求項（１）〜（３）のいずれかに記載の
架橋ポリオレフィン材料の製造方法。(4) The method for producing a crosslinked polyolefin material according to any one of claims (1) to (3), wherein the antioxidant is thiobisphenol-based.
されることを特徴とする、請求項（１）〜（４）のいず
れかに記載の架橋ポリオレフィン材料の製造方法。(5) The method for producing a crosslinked polyolefin material according to any one of claims (1) to (4), characterized in that the crosslinked polyolefin material is supplied in the form of pellets.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4249190A JP2817320B2 (en) | 1990-02-26 | 1990-02-26 | Method for producing crosslinked polyolefin material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4249190A JP2817320B2 (en) | 1990-02-26 | 1990-02-26 | Method for producing crosslinked polyolefin material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03247640A true JPH03247640A (en) | 1991-11-05 |
| JP2817320B2 JP2817320B2 (en) | 1998-10-30 |
Family
ID=12637531
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4249190A Expired - Lifetime JP2817320B2 (en) | 1990-02-26 | 1990-02-26 | Method for producing crosslinked polyolefin material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2817320B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6869995B2 (en) | 1998-06-16 | 2005-03-22 | Union Carbide Chemicals & Plastics Technology Corporation | Water tree resistant cable |
| JP2017222852A (en) * | 2017-06-07 | 2017-12-21 | ダウ グローバル テクノロジーズ エルエルシー | Crosslinkable polymer composition and method for producing the same, and article produced from the same |
-
1990
- 1990-02-26 JP JP4249190A patent/JP2817320B2/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6869995B2 (en) | 1998-06-16 | 2005-03-22 | Union Carbide Chemicals & Plastics Technology Corporation | Water tree resistant cable |
| JP2017222852A (en) * | 2017-06-07 | 2017-12-21 | ダウ グローバル テクノロジーズ エルエルシー | Crosslinkable polymer composition and method for producing the same, and article produced from the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2817320B2 (en) | 1998-10-30 |
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