JP2002256102A - Process for regeneration of crosslinked polyolefin - Google Patents
Process for regeneration of crosslinked polyolefinInfo
- Publication number
- JP2002256102A JP2002256102A JP2001057353A JP2001057353A JP2002256102A JP 2002256102 A JP2002256102 A JP 2002256102A JP 2001057353 A JP2001057353 A JP 2001057353A JP 2001057353 A JP2001057353 A JP 2001057353A JP 2002256102 A JP2002256102 A JP 2002256102A
- Authority
- JP
- Japan
- Prior art keywords
- polyolefin
- crosslinked
- coal powder
- molecular weight
- crosslinked 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.)
- Withdrawn
Links
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 60
- 238000000034 method Methods 0.000 title claims abstract description 17
- 230000008929 regeneration Effects 0.000 title abstract 3
- 238000011069 regeneration method Methods 0.000 title abstract 3
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000003245 coal Substances 0.000 claims abstract description 29
- 239000000843 powder Substances 0.000 claims abstract description 28
- 230000001172 regenerating effect Effects 0.000 claims description 9
- -1 polypropylene Polymers 0.000 abstract description 11
- 239000004743 Polypropylene Substances 0.000 abstract description 7
- 229920003020 cross-linked polyethylene Polymers 0.000 abstract description 7
- 239000004703 cross-linked polyethylene Substances 0.000 abstract description 7
- 229920001155 polypropylene Polymers 0.000 abstract description 7
- 238000004132 cross linking Methods 0.000 description 14
- 239000007787 solid Substances 0.000 description 12
- 238000009826 distribution Methods 0.000 description 6
- 229920003023 plastic Polymers 0.000 description 6
- 239000004033 plastic Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 239000004698 Polyethylene Substances 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 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 description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Natural products CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 2
- 238000010494 dissociation reaction Methods 0.000 description 2
- 230000005593 dissociations Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000003077 lignite Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 238000009529 body temperature measurement Methods 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000010791 domestic waste Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
Landscapes
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、電線・ケーブルの
絶縁材料などとして使用されている架橋ポリオレフィ
ン、例えば架橋ポリエチレン、架橋ポリプロピレンなど
を、再利用可能な未架橋のポリオレフィン、例えばポリ
エチレン、ポリプロピレンなどに再生する方法に関す
る。The present invention relates to a method for converting a crosslinked polyolefin, such as a crosslinked polyethylene or a crosslinked polypropylene, used as an insulating material for electric wires or cables, into a non-crosslinkable polyolefin such as a polyethylene or polypropylene which can be reused. How to play.
【０００２】[0002]
【従来の技術】大量に出される産業・家庭廃棄物の処理
が社会問題になっている中、これらの廃棄物中に含まれ
るプラスチックを回収して資源（プラスチック原料）と
して再利用するための研究が盛んに行われており、一部
のプラスチックの中には既に実用化に向けて進んでいる
ものもある。2. Description of the Related Art As the disposal of large quantities of industrial and domestic waste has become a social problem, research has been conducted to recover plastics contained in these wastes and reuse them as resources (plastic raw materials). , And some plastics are already being put into practical use.
【０００３】しかしながら、その多くは未だ十分な再生
技術が確立されておらず、なかでも、その優れた絶縁特
性から、電線・ケーブルの絶縁材料などとして広く用い
られている架橋ポリエチレンや架橋ポリプロピレンなど
の架橋ポリオレフィンについては、架橋されていること
が逆に難点となり、プラスチック原料として再生するこ
とは困難であると考えられてきた。[0003] However, many of them have not yet established a sufficient recycling technology, and among them, due to their excellent insulation properties, such as cross-linked polyethylene and cross-linked polypropylene, which are widely used as insulation materials for electric wires and cables. Conversely, it has been considered that crosslinked polyolefins are difficult to regenerate as plastic raw materials because of the fact that they are crosslinked.
【０００４】しかしながら、架橋ポリエチレンや架橋ポ
リプロピレンなどの架橋ポリオレフィンをプラスチック
原料に再生する技術を確立することは、廃棄物処理の問
題のみならず、資源の有効利用の面からも重要であり、
特に、架橋ポリオレフィンを、架橋前のポリオレフィン
に戻すことができれば、そのままプラスチック材料とし
て使用することができることから、再生技術として非常
に有用である。However, establishing a technology for regenerating a cross-linked polyolefin such as cross-linked polyethylene or cross-linked polypropylene into a plastic raw material is important not only in terms of waste disposal but also in terms of effective use of resources.
In particular, if the crosslinked polyolefin can be returned to the polyolefin before crosslinking, it can be used as it is as a plastic material, which is very useful as a recycling technique.
【０００５】そこで、本発明者らはかかる技術を開発す
べく鋭意研究を重ねた結果、架橋ポリオレフィンを超臨
界状態または亜臨界状態の水と接触、反応させることに
より未架橋のポリオレフィンに改質しうることを見出
し、先に出願した。Accordingly, the present inventors have conducted intensive studies to develop such a technique. As a result, the crosslinked polyolefin was modified into an uncrosslinked polyolefin by contacting and reacting with supercritical or subcritical water. I found that I had filed earlier.
【０００６】[0006]
【発明が解決しようとする課題】しかしながら、この方
法は反応の制御が難しく、得られる未架橋のポリオレフ
ィンは、架橋前のものより低分子量化されやすく、ま
た、そのために収率も低くなるという問題があった。However, in this method, it is difficult to control the reaction, and the resulting uncrosslinked polyolefin is liable to have a lower molecular weight than that before crosslinking, and the yield is also reduced. was there.
【０００７】本発明はこのような問題を解決するために
なされたもので、超臨界水または亜臨界水を利用して、
架橋ポリエチレンや架橋ポリプロピレンなどの架橋ポリ
オレフィンを、架橋前のものに近い分子量を持った未架
橋ポリオレフィンに再生することができ、また、収率も
向上させることができる方法を提供することを目的とす
る。The present invention has been made to solve such a problem, and utilizes supercritical water or subcritical water to provide
It is an object of the present invention to provide a method capable of regenerating a crosslinked polyolefin such as a crosslinked polyethylene or a crosslinked polypropylene into an uncrosslinked polyolefin having a molecular weight close to that before crosslinking, and also improving the yield. .
【０００８】[0008]
【課題を解決するための手段】上記の目的を達成するた
め、本願の請求項１記載の発明の架橋ポリオレフィンの
再生方法は、架橋ポリオレフィンを石炭粉末とともに反
応容器内で超臨界水または亜臨界水と接触、反応させて
未架橋のポリオレフィンを生成することを特徴としてい
る。In order to achieve the above-mentioned object, a method for regenerating a crosslinked polyolefin according to the first aspect of the present invention comprises a method for regenerating a crosslinked polyolefin together with coal powder in a supercritical water or subcritical water in a reaction vessel. And reacting with it to produce an uncrosslinked polyolefin.
【０００９】上記構成によれば、架橋ポリオレフィンと
ともに石炭粉末を投入したことにより、架橋ポリオレフ
ィンを、架橋前のポリオレフィンに近い分子量を持った
未架橋ポリオレフィンに再生することができ、また、収
率を実質的に向上させることができる。[0009] According to the above configuration, by adding coal powder together with the crosslinked polyolefin, the crosslinked polyolefin can be regenerated into an uncrosslinked polyolefin having a molecular weight close to that of the polyolefin before crosslinking, and the yield can be substantially reduced. Can be improved.
【００１０】これは、次のような理由によると考えられ
る。架橋ポリオレフィンを超臨界水または亜臨界水と接
触、反応させることによって、未架橋のポリオレフィン
が生成されるのは、架橋ポリオレフィンにおける架橋点
が優先的に切断されるからと考えられ、また、このよう
に架橋点が優先的に切断されるのは、架橋点におけるＣ
−Ｃ結合の解離エネルギーが、ポリオレフィン分子主鎖
におけるＣ−Ｃ結合の解離エネルギーが小さいこと、超
（亜）臨界水中ではポリオレフィンの非晶部や結晶部が
部分的に溶融して高分子鎖の分子運動エネルギーが大き
くなっており、そのため高分子鎖に歪みがかかり、特に
架橋部分に大きな歪みがかかることなどによると考えら
れる。しかしながら、架橋点のみを選択的に切断するに
は、反応条件を厳密に設定、調整する必要があり、架橋
部分が残らないようにするためには、どうしても分子主
鎖のＣ−Ｃ結合の切断による低分子量化は避けられな
い。石炭粉末を配合することによって、このような架橋
ポリオレフィンの分子主鎖のＣ−Ｃ結合の切断が抑制さ
れ、あるいは、切断されたとしても、そこに再び分子鎖
（ポリオレフィンから切断された低分子量の分子や石炭
粉末が超臨界水または亜臨界水によって分解されて生じ
た炭化水素の分子）が結合し、その結果、低分子量化が
防止され、架橋前のポリオレフィンに近い分子量を持っ
た未架橋ポリオレフィンが得られると考えられる。This is considered to be due to the following reasons. The reason that the uncrosslinked polyolefin is produced by contacting and reacting the crosslinked polyolefin with supercritical water or subcritical water is considered that the crosslinking point in the crosslinked polyolefin is preferentially cleaved. Is preferentially cleaved at the crosslinking point
The dissociation energy of the -C bond is that the dissociation energy of the C-C bond in the polyolefin molecule main chain is small, and in super (sub) critical water, the amorphous part and the crystal part of the polyolefin are partially melted and the It is considered that the molecular kinetic energy is large, so that the polymer chain is distorted, and particularly the crosslinked portion is distorted. However, in order to selectively cut only the crosslinking points, it is necessary to strictly set and adjust the reaction conditions. In order to prevent the crosslinked portion from remaining, it is absolutely necessary to cut the C—C bond of the molecular main chain. It is unavoidable to reduce the molecular weight by the method. By blending the coal powder, the breaking of the CC bond of the molecular main chain of such a cross-linked polyolefin is suppressed, or even if it is broken, the molecular chain (the low molecular weight cut from the polyolefin, Molecules and coal powder are decomposed by supercritical water or subcritical water, resulting in the binding of hydrocarbon molecules), resulting in lower molecular weight reduction and an uncrosslinked polyolefin with a molecular weight close to that of the uncrosslinked polyolefin. Is considered to be obtained.
【００１１】上記発明の架橋ポリオレフィンの再生方法
においては、請求項２に記載したように、架橋ポリオレ
フィンに対し10重量％〜40重量％の石炭粉末を反応容器
内へ投入することが好ましい。石炭粉末の量が前記範囲
より少ないと、得られる未架橋ポリオレフィンの低分子
量化を十分に抑制することができず、また、石炭粉末の
量が前記範囲より多くなると、石炭粉末は十分に分解さ
れるが、架橋ポリオレフィンが十分に脱架橋されなくな
る。In the method for regenerating a crosslinked polyolefin according to the present invention, as described in claim 2, it is preferable that 10 to 40% by weight of coal powder based on the crosslinked polyolefin is charged into the reaction vessel. If the amount of the coal powder is less than the above range, it is not possible to sufficiently suppress the reduction of the molecular weight of the obtained uncrosslinked polyolefin, and if the amount of the coal powder is more than the above range, the coal powder is sufficiently decomposed. However, the crosslinked polyolefin is not sufficiently decrosslinked.
【００１２】また、上記発明の架橋ポリオレフィンの再
生方法においては、請求項３に記載したように、反応温
度を200℃〜1000℃とし、かつ、反応圧力を2MPa〜100MP
aとすることが好ましい。反応温度および反応圧力のい
ずれかでも前記範囲を外れると、架橋体が十分に脱架橋
されなかったり、石炭粉末による低分子量化抑制効果が
十分に得られないおそれがある。Further, in the method for regenerating a crosslinked polyolefin of the present invention, the reaction temperature is set to 200 ° C. to 1000 ° C. and the reaction pressure is set to 2 MPa to 100 MPa.
a is preferred. If any of the reaction temperature and the reaction pressure is out of the above range, the crosslinked product may not be sufficiently decrosslinked, or the effect of reducing the molecular weight by the coal powder may not be sufficiently obtained.
【００１３】[0013]
【発明の実施の形態】以下、本発明の実施の形態を説明
する。Embodiments of the present invention will be described below.
【００１４】本発明において使用される超臨界水は、臨
界温度（374℃）および臨界圧力（22.1MPa）を超えた非
凝縮性高密度水である。本発明においては、超臨界水で
なく亜臨界水を用いてもよい。The supercritical water used in the present invention is a non-condensable high-density water exceeding a critical temperature (374 ° C.) and a critical pressure (22.1 MPa). In the present invention, subcritical water may be used instead of supercritical water.
【００１５】本発明においては、架橋ポリオレフィンを
石炭粉末とともに反応容器内で上記のような超臨界水ま
たは亜臨界水と接触、反応させる。In the present invention, the crosslinked polyolefin is brought into contact with and reacted with supercritical water or subcritical water as described above in a reaction vessel together with coal powder.
【００１６】石炭粉末としては、特に限定されるもので
はないが、褐炭や非粘結炭などの、水素化されやすく揮
発分を多く含む石炭の粉末が、超臨界水または亜臨界水
中での油状物の生成量が多いことから、好ましく使用さ
れる。また、この石炭粉末のの反応容器への投入量は、
架橋ポリオレフィンの10〜40重量％の範囲が好ましく、
20〜35重量％の範囲がより好ましい。石炭粉末の投入量
が架橋ポリオレフィンの10重量％未満では、得られる未
架橋ポリオレフィンの低分子量化を十分に抑制すること
ができず、また、40重量％を越えると、石炭粉末は十分
に分解されるが、架橋ポリオレフィンが十分に脱架橋さ
れなくなる。The coal powder is not particularly limited, but coal powder which is easily hydrogenated and contains many volatile components, such as lignite or non-coking coal, is used in supercritical water or subcritical water. It is preferably used because it produces a large amount of products. In addition, the amount of this coal powder charged into the reaction vessel is:
Preferably in the range of 10 to 40% by weight of the crosslinked polyolefin,
A range of 20 to 35% by weight is more preferred. If the input amount of coal powder is less than 10% by weight of the crosslinked polyolefin, the resulting uncrosslinked polyolefin cannot be sufficiently reduced in molecular weight, and if it exceeds 40% by weight, the coal powder is sufficiently decomposed. However, the crosslinked polyolefin is not sufficiently decrosslinked.
【００１７】また、反応温度および反応圧力は、それぞ
れ200℃〜1000℃および2MPa〜100MPaの範囲で調整する
ことが好ましく、反応温度および反応圧力のいずれかで
も前記範囲を外れると、架橋体が十分に脱架橋されなか
ったり、石炭粉末による低分子量化抑制効果が十分に得
られないおそれがある。より好ましい範囲は、反応温度
が300℃〜800℃、反応圧力が5MPa〜80MPaの範囲であ
り、反応温度を300℃〜600℃、反応圧力を10MPa〜60MPa
の範囲とするとさらに好ましい。さらに、反応時間は、
通常、1〜30分程度とすることが好ましい。The reaction temperature and the reaction pressure are preferably adjusted in the range of 200 ° C. to 1000 ° C. and 2 MPa to 100 MPa, respectively. There is a possibility that the cross-linking may not be carried out, or the effect of reducing the molecular weight by the coal powder may not be sufficiently obtained. A more preferred range is a reaction temperature of 300 ° C. to 800 ° C., a reaction pressure of 5 MPa to 80 MPa, a reaction temperature of 300 ° C. to 600 ° C., and a reaction pressure of 10 MPa to 60 MPa.
It is more preferable to set the range as follows. Furthermore, the reaction time is
Usually, it is preferable to set it for about 1 to 30 minutes.
【００１８】本発明においては、架橋ポリオレフィンが
超臨界水または亜臨界水と反応して未架橋化される際の
低分子量化が石炭粉末によって抑制されるため、架橋前
のポリオレフィンに近い分子量を持った未架橋ポリオレ
フィンを得ることができる。したがって、例えば電線・
ケーブルの廃棄物から回収した架橋ポリオレフィンは、
そのまま再び架橋して電線・ケーブル用材料として使用
することができる。また、低分子量化が抑制されること
によって、実質的に収率を高めることができる。In the present invention, since the reduction of the molecular weight when the crosslinked polyolefin reacts with supercritical water or subcritical water and is not crosslinked is suppressed by the coal powder, it has a molecular weight close to that of the polyolefin before crosslinking. An uncrosslinked polyolefin can be obtained. Therefore, for example,
Crosslinked polyolefin recovered from cable waste
It can be crosslinked again and used as a material for electric wires and cables. Further, by suppressing the reduction of the molecular weight, the yield can be substantially increased.
【００１９】なお、本発明で再生することのできる架橋
ポリオレフィンとしては、ポリエチレン、ポリプロピレ
ン、ポリイソブチレン、エチレン・酢酸エチル共重合
体、エチレン・酢酸メチル共重合体、エチレン・酢酸ビ
ニル共重合体などの各架橋体があげられるが、特にこれ
らに限定されるものではない。また、この架橋ポリオレ
フィンには、充填剤、老化防止剤、反応助剤などの各種
添加剤が配合されていてもよく、また、架橋ポリオレフ
ィン以外の他の熱可塑性樹脂や熱硬化性樹脂が混合され
ていてもよい。さらに、架橋度や架橋方法についても特
に限定されるものではない。The crosslinked polyolefin that can be regenerated in the present invention includes polyethylene, polypropylene, polyisobutylene, ethylene / ethyl acetate copolymer, ethylene / methyl acetate copolymer, ethylene / vinyl acetate copolymer and the like. Although each crosslinked body is mentioned, it is not particularly limited to these. The cross-linked polyolefin may contain various additives such as a filler, an antioxidant, and a reaction aid, and a thermoplastic resin or a thermosetting resin other than the cross-linked polyolefin may be mixed. May be. Further, the degree of crosslinking and the method of crosslinking are not particularly limited.
【００２０】[0020]
【実施例】次に、本発明を実施例によりさらに具体的に
説明するが、本発明はこれらの実施例に限定されるもの
ではない。EXAMPLES Next, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.
【００２１】実施例１ 分子量（Ｍｗ）86000、多分散度（Ｍｗ／Ｍｎ）5.7の低
密度ポリエチレンに架橋剤としてＤＣＰ（ジクミルパー
オキサイド）を用いてゲル分率（JIS S 3005、以下同
じ）が80％、厚さ1mmの架橋ポリエチレンシートを作製
し、これを１cm×１cmの大きさに裁断して試料とした。
この試料10gおよび石炭粉末（黒色褐炭）2gを純水20cc
とともに耐圧反応容器（容量50cc）内に投入した。次い
で、反応容器を密封し、加熱して反応容器内の温度およ
び圧力をそれぞれ400℃、40MPaまで30分間かけて昇温昇
圧させ、そのまま1分間保持した（反応時間：1分）。こ
の後、2時間かけて冷却して常温常圧に戻し、反応液か
ら固形分を分離回収した。Example 1 Gel fraction (JIS S 3005; the same applies hereinafter) using DCP (dicumyl peroxide) as a cross-linking agent for low-density polyethylene having a molecular weight (Mw) of 86000 and a polydispersity (Mw / Mn) of 5.7. A crosslinked polyethylene sheet having a thickness of 80% and a thickness of 1 mm was prepared and cut into a size of 1 cm × 1 cm to obtain a sample.
10 g of this sample and 2 g of coal powder (black lignite) were added to 20 cc of pure water.
At the same time, it was charged into a pressure-resistant reaction vessel (50 cc capacity). Then, the reaction vessel was sealed and heated to raise the temperature and pressure in the reaction vessel to 400 ° C. and 40 MPa, respectively, over 30 minutes, and held for 1 minute (reaction time: 1 minute). Thereafter, the mixture was cooled over 2 hours to return to normal temperature and normal pressure, and a solid content was separated and recovered from the reaction solution.
【００２２】得られた固形分の重量は10ｇであった。ま
た、ゲル分率、並びに、ＧＰＣ（ゲル浸透クロマトグラ
フィ）分析により、分子量（Ｍｗ）および多分散度（Ｍ
ｗ／Ｍｎ）を求めた。結果は、ゲル分率0％、Ｍｗ7000
0、Ｍｗ／Ｍｎ6.3であった。The weight of the obtained solid was 10 g. In addition, the gel fraction and GPC (gel permeation chromatography) analysis showed that the molecular weight (Mw) and polydispersity (M
w / Mn). The results were as follows: gel fraction 0%, Mw7000
0, Mw / Mn6.3.
【００２３】次いで、比較のために、石炭粉末を未投入
とした以外は実施例１と同様にして反応させ、反応液か
ら固形分を分離回収した。（比較例１）。得られた固形
分の重量は9.8ｇであった。また、実施例1と同様にして
ゲル分率、分子量（Ｍｗ）および多分散度（Ｍｗ／Ｍ
ｎ）を求めた。結果は、ゲル分率0％、Ｍｗ30000、 Ｍ
ｗ／Ｍｎ6.0であった。Next, for comparison, a reaction was carried out in the same manner as in Example 1 except that coal powder was not charged, and a solid content was separated and recovered from the reaction solution. (Comparative Example 1). The weight of the obtained solid content was 9.8 g. Further, the gel fraction, molecular weight (Mw) and polydispersity (Mw / M
n) was determined. The results were as follows: gel fraction 0%, Mw 30000, M
w / Mn 6.0.
【００２４】なお、上記実施例1および比較例１で得ら
れた固形分の分子量分布は、いずれも正規分布を示して
いた。このことは、実施例１および比較例１においてと
もに分子量（Ｍｗ）の減少が認められるものの、その変
化は低分子量成分のみの増加によるものではないことを
示している。The molecular weight distributions of the solids obtained in Example 1 and Comparative Example 1 each showed a normal distribution. This indicates that in both Example 1 and Comparative Example 1, a decrease in molecular weight (Mw) was observed, but the change was not due to an increase in only low molecular weight components.
【００２５】以上の結果から、石炭粉末を投入すること
により、より架橋前のものに近い未架橋ポリエチレンを
得ることができ、しかも、収率も実質的に向上させるこ
とができることがわかる。From the above results, it can be seen that by adding coal powder, an uncrosslinked polyethylene closer to that before crosslinking can be obtained, and the yield can be substantially improved.
【００２６】実施例２ 図１に示す装置を用いて、実施例１と同様にして作製し
た架橋ポリエチレンからなる試料の処理を行った。Example 2 Using the apparatus shown in FIG. 1, a sample made of crosslinked polyethylene produced in the same manner as in Example 1 was treated.
【００２７】なお、図１において、１は電気炉１ａを備
えた円筒状の耐圧反応容器（容積約10cc）、２は純水を
収容した溶媒タンク、３は溶媒タンク２から純水を耐圧
反応容器１に送り込むためのポンプ、４は純水を予熱す
るための予熱器、５は耐圧反応容器１から排出される気
体成分を水冷する水冷管、６は水冷により凝縮された液
体を回収するドレンタンク、７はこれらの各機器を接続
する配管である。また、８はラインヒータ、９は流量
計、１０は温度測定用熱電対、１１は温度制御用熱電
対、１２は圧力計、１３は減圧弁である。さらに、１４
は耐圧反応容器１と水冷管５を接続する配管７に介挿さ
れた、石炭粉末の流出を防止するためのフィルタであ
る。In FIG. 1, reference numeral 1 denotes a cylindrical pressure-resistant reaction vessel equipped with an electric furnace 1a (capacity: about 10 cc), 2 denotes a solvent tank containing pure water, and 3 denotes a pressure-resistant reaction of pure water from the solvent tank 2. A pump for feeding into the vessel 1, a preheater 4 for preheating pure water, a water cooling pipe 5 for water-cooling a gas component discharged from the pressure-resistant reaction vessel 1, and a drain 6 for collecting a liquid condensed by water cooling. The tank 7 is a pipe for connecting these devices. 8 is a line heater, 9 is a flow meter, 10 is a thermocouple for temperature measurement, 11 is a thermocouple for temperature control, 12 is a pressure gauge, and 13 is a pressure reducing valve. In addition, 14
Is a filter interposed in a pipe 7 connecting the pressure-resistant reaction vessel 1 and the water cooling pipe 5 for preventing the outflow of coal powder.
【００２８】このような装置を用いて、まず、上記試料
0.5gと実施例1で用いたものと同様の石炭粉末0.1gとを
耐圧反応容器１内に投入した。次いで、系内を脱気した
純水で満たした後、純水の流量を1ml/minに設定し、ま
た、系内の圧力を耐圧反応容器１出口部の圧力調整器
（図示なし）で40MPaに設定した。その後、約40分間か
けて反応容器１内を400℃まで昇温し、そのまま30分間
維持した後、約2時間かけて冷却して常温常圧に戻し、
耐圧反応容器１内の固形分を回収した。Using such an apparatus, first, the sample
0.5 g and 0.1 g of the same coal powder as used in Example 1 were charged into the pressure-resistant reactor 1. Next, after the inside of the system was filled with degassed pure water, the flow rate of the pure water was set to 1 ml / min, and the pressure in the system was adjusted to 40 MPa using a pressure regulator (not shown) at the outlet of the pressure-resistant reaction vessel 1. Set to. Thereafter, the temperature inside the reaction vessel 1 was raised to 400 ° C. over about 40 minutes, and maintained for 30 minutes, and then cooled over about 2 hours to return to normal temperature and normal pressure.
The solid content in the pressure-resistant reaction vessel 1 was recovered.
【００２９】得られた固形分の重量は0.495ｇであっ
た。また、この固形分について、ゲル分率、並びに、Ｇ
ＰＣ分析により分子量（Ｍｗ）および多分散度（Ｍｗ／
Ｍｎ）を求めた。結果は、ゲル分率0％、Ｍｗ75000、Ｍ
ｗ／Ｍｎ9.6で、固形分の分子量分布は正規分布を示し
ていた。The weight of the obtained solid content was 0.495 g. Further, regarding this solid content, the gel fraction and G
The molecular weight (Mw) and polydispersity (Mw /
Mn) was determined. The results were as follows: gel fraction 0%, Mw 75000, M
With a w / Mn of 9.6, the molecular weight distribution of the solid content showed a normal distribution.
【００３０】次いで、比較のために、石炭粉末を未投入
とした以外は実施例１と同様にして処理し、耐圧反応容
器１内の固形分を回収した。Next, for comparison, the same treatment as in Example 1 was carried out except that coal powder was not charged, and the solid content in the pressure-resistant reaction vessel 1 was recovered.
【００３１】得られた固形分の重量は0.425gであった。
また、実施例1と同様にしてゲル分率、分子量（Ｍｗ）
および多分散度（Ｍｗ／Ｍｎ）を求めた。結果は、ゲル
分率0％、Ｍｗ60000、Ｍｗ／Ｍｎ12.2で、固形分の分子
量分布は正規分布を示していた。The weight of the obtained solid content was 0.425 g.
The gel fraction and the molecular weight (Mw) were the same as in Example 1.
And polydispersity (Mw / Mn). As a result, the gel fraction was 0%, Mw was 60,000, and Mw / Mn was 12.2, and the molecular weight distribution of the solid content showed a normal distribution.
【００３２】以上の結果から、図１に示すようなセミバ
ッチ式装置を用いた場合でも、石炭粉末を投入すること
により、より架橋前のものに近い未架橋ポリエチレンが
得ることができ、かつ、収率も実質的に向上させること
ができることがわかる。From the above results, even when a semi-batch type apparatus as shown in FIG. 1 is used, it is possible to obtain an uncrosslinked polyethylene closer to that before crosslinking by adding coal powder, and to improve the yield. It can be seen that the rate can also be substantially improved.
【００３３】[0033]
【発明の効果】以上説明したように、本発明によれば、
架橋ポリオレフィンを石炭粉末とともに反応容器内で超
臨界水または亜臨界水と接触、反応させて未架橋のポリ
オレフィンを生成するようにしたので、架橋前のものに
近い分子量を持った未架橋ポリオレフィンに再生するこ
とができ、また、収率も向上させることができる。As described above, according to the present invention,
The crosslinked polyolefin is brought into contact with supercritical water or subcritical water together with coal powder in the reaction vessel and reacted to produce an uncrosslinked polyolefin, so it is regenerated into an uncrosslinked polyolefin with a molecular weight close to that before crosslinking. And the yield can be improved.
【図１】本発明の実施に使用される装置の一例を概略的
に示す図。FIG. 1 is a diagram schematically showing an example of an apparatus used for carrying out the present invention.
１………耐圧反応容器 ２………溶媒タンク ３………ポンプ ４………予熱器 ５………水冷管 １４………フィルタ DESCRIPTION OF SYMBOLS 1 ... Pressure-resistant reaction vessel 2 ... Solvent tank 3 ... Pump 4 ... Preheater 5 ... Water cooling tube 14 ... Filter
フロントページの続き (72)発明者 古村 清司 愛知県名古屋市緑区大高町字北関山20番地 の１ 中部電力株式会社電力技術研究所内 (72)発明者 平井 進 神奈川県川崎市川崎区小田栄２丁目１番１ 号 昭和電線電纜株式会社内 (72)発明者 森田 広昭 神奈川県川崎市川崎区小田栄２丁目１番１ 号 昭和電線電纜株式会社内 Ｆターム(参考） 4F301 AA12 CA09 CA23 CA33 CA41 CA51 CA72 CA73 Continued on the front page (72) Inventor Kiyoji Furumura 20-1, Kita-Sekiyama, Odaka-cho, Midori-ku, Nagoya-shi, Aichi Prefecture Inside the Electric Power Research Laboratory, Chubu Electric Power Co., Inc. 2-1-1, Showa Electric Wire & Cable Co., Ltd. (72) Inventor Hiroaki Morita 2-1-1, Oda-Ei, Kawasaki-ku, Kawasaki-shi, Kanagawa Prefecture F-Term (Showa Electric Wire & Cable Co., Ltd.) CA51 CA72 CA73
Claims (3)
反応容器内で超臨界水または亜臨界水と接触、反応させ
て未架橋のポリオレフィンを生成することを特徴とする
架橋ポリオレフィンの再生方法。1. A method for regenerating a crosslinked polyolefin, comprising contacting and reacting a crosslinked polyolefin with supercritical water or subcritical water in a reaction vessel together with coal powder to produce an uncrosslinked polyolefin.
重量％の石炭粉末を反応容器内へ投入することを特徴と
する請求項１記載の架橋ポリオレフィンの再生方法。2. A weight percentage of the crosslinked polyolefin of 10 to 40% by weight.
2. The method for regenerating a crosslinked polyolefin according to claim 1, wherein a weight% of coal powder is charged into the reaction vessel.
反応圧力を2MPa〜100MPaとすることを特徴とする請求項
１または２記載の架橋ポリオレフィンの再生方法。3. A reaction temperature of 200 ° C. to 1000 ° C., and
3. The method for regenerating a crosslinked polyolefin according to claim 1, wherein the reaction pressure is 2 MPa to 100 MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001057353A JP2002256102A (en) | 2001-03-01 | 2001-03-01 | Process for regeneration of crosslinked polyolefin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001057353A JP2002256102A (en) | 2001-03-01 | 2001-03-01 | Process for regeneration of crosslinked polyolefin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2002256102A true JP2002256102A (en) | 2002-09-11 |
Family
ID=18917245
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2001057353A Withdrawn JP2002256102A (en) | 2001-03-01 | 2001-03-01 | Process for regeneration of crosslinked polyolefin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2002256102A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20160121658A (en) * | 2015-04-09 | 2016-10-20 | 엘에스전선 주식회사 | Decrosslinked polyolefine resin and resin composition comprising the same |
| EP4053170A4 (en) * | 2019-10-28 | 2023-11-15 | LS Cable & System Ltd. | Decrosslinked polyolefin resin for cable filler and resin composition comprising same |
-
2001
- 2001-03-01 JP JP2001057353A patent/JP2002256102A/en not_active Withdrawn
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20160121658A (en) * | 2015-04-09 | 2016-10-20 | 엘에스전선 주식회사 | Decrosslinked polyolefine resin and resin composition comprising the same |
| KR101721512B1 (en) | 2015-04-09 | 2017-03-31 | 엘에스전선 주식회사 | Decrosslinked polyolefine resin and resin composition comprising the same |
| EP4053170A4 (en) * | 2019-10-28 | 2023-11-15 | LS Cable & System Ltd. | Decrosslinked polyolefin resin for cable filler and resin composition comprising same |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP2784109B1 (en) | Devulcanized rubber and methods | |
| JP5586239B2 (en) | Method for treating a crosslinked polymer having a skeleton composed of carbon-carbon bonds, and a product obtained by the method | |
| JPH10314713A (en) | Method and device for treating mixed waste | |
| JP4674864B2 (en) | Recycling method for crosslinked polymer | |
| JP2002256102A (en) | Process for regeneration of crosslinked polyolefin | |
| Yin et al. | Melt grafting of poly (ethylene‐vinyl acetate) copolymer with maleic anhydride | |
| JPH0832741B2 (en) | Method for producing amorphous poly α-olefin | |
| JP2001192495A (en) | Method for reprocessing cross-linked polyolefin | |
| JP2002256103A (en) | Process for regeneration of crosslinked polyolefin | |
| JP4974924B2 (en) | Recycling method for crosslinked polymer | |
| JPS5830887B2 (en) | Method for purifying highly crystalline polyolefin | |
| JP4044228B2 (en) | Method for devolatilization of residual monomer in resin | |
| Shen et al. | Grafting of maleic anhydride onto polyethylene through a green chemistry approach | |
| CN108690219B (en) | Liquid phase preparation method of reclaimed rubber | |
| JP2846453B2 (en) | Purification method of modified polyolefin | |
| RU2155779C2 (en) | Method of isolation of (co)polymers by coagulation | |
| US20200115315A1 (en) | Process for purification of vinyl acetate for use in polymerization in the presence of ethylene | |
| JPH0892396A (en) | Production of modified polyethylene and molded product | |
| JP2001252636A (en) | Method for regenerating crosslinked polymer material | |
| US4434279A (en) | High swell resins | |
| JP4665907B2 (en) | Recycling method of polymer compounds | |
| CA2635952A1 (en) | Solid state modification of propylene polymers | |
| TW316267B (en) | ||
| JP2001192494A (en) | Method for decomposing high molecular compound | |
| Dontsov et al. | The production of a single steric network by a heterogeneous reaction of elastomers with azodicarbamide |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A711 | Notification of change in applicant |
Free format text: JAPANESE INTERMEDIATE CODE: A712 Effective date: 20060424 |
|
| RD02 | Notification of acceptance of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7422 Effective date: 20060616 |
|
| A300 | Withdrawal of application because of no request for examination |
Free format text: JAPANESE INTERMEDIATE CODE: A300 Effective date: 20080513 |