JP2001323022A - Method for regenerating crosslinked olefin - Google Patents
Method for regenerating crosslinked olefinInfo
- Publication number
- JP2001323022A JP2001323022A JP2001067474A JP2001067474A JP2001323022A JP 2001323022 A JP2001323022 A JP 2001323022A JP 2001067474 A JP2001067474 A JP 2001067474A JP 2001067474 A JP2001067474 A JP 2001067474A JP 2001323022 A JP2001323022 A JP 2001323022A
- Authority
- JP
- Japan
- Prior art keywords
- polyolefin
- crosslinked
- reaction
- crosslinked polyolefin
- uncrosslinked
- 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- Withdrawn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
- 238000000034 method Methods 0.000 title claims description 12
- 230000001172 regenerating effect Effects 0.000 title claims description 7
- 150000001336 alkenes Chemical class 0.000 title 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title 1
- 229920000098 polyolefin Polymers 0.000 claims abstract description 54
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000007810 chemical reaction solvent Substances 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 39
- 229920001684 low density polyethylene Polymers 0.000 claims description 3
- 239000004702 low-density polyethylene Substances 0.000 claims description 3
- 230000008929 regeneration Effects 0.000 claims description 3
- 238000011069 regeneration method Methods 0.000 claims description 3
- -1 polypropylene Polymers 0.000 abstract description 18
- 239000004743 Polypropylene Substances 0.000 abstract description 9
- 229920003020 cross-linked polyethylene Polymers 0.000 abstract description 9
- 239000004703 cross-linked polyethylene Substances 0.000 abstract description 9
- 229920001155 polypropylene Polymers 0.000 abstract description 9
- 239000007787 solid Substances 0.000 description 10
- 238000004132 cross linking Methods 0.000 description 9
- 229920003023 plastic Polymers 0.000 description 9
- 239000004033 plastic Substances 0.000 description 9
- 239000004698 Polyethylene Substances 0.000 description 8
- 229920000573 polyethylene Polymers 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229920000642 polymer 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
- 229920001577 copolymer Polymers 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Natural products CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000001816 cooling Methods 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
- 238000005516 engineering process Methods 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 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 1
- 102100031005 Epididymal sperm-binding protein 1 Human genes 0.000 description 1
- 101001063556 Homo sapiens Epididymal sperm-binding protein 1 Proteins 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
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000010791 domestic waste Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000011521 glass Substances 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
- 238000002156 mixing Methods 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 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)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (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 cross-linked polyolefins are difficult to regenerate as plastic raw materials because they are cross-linked.
【０００４】[0004]
【発明が解決しようとする課題】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
からも極めて重要であり、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 crosslinked polyolefin such as crosslinked polyethylene or crosslinked polypropylene into a plastic raw material is not only a problem of waste disposal but also an effective use of resources. This is extremely important. 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】なお、回収した架橋ポリオレフィンを油化
あるいは微粉化して燃料として利用する技術はこれまで
にも多く検討されている。しかしながら、用途や費用な
どの課題が未だ多く残されており、実用化までには至っ
ていないのが実状である。[0005] In addition, many techniques have been studied so far in which the recovered crosslinked polyolefin is converted into oil or pulverized and used as fuel. However, there are still many problems such as applications and costs, and the actual situation is that it has not been put to practical use.
【０００６】本発明はこのような従来の事情に鑑みなさ
れたもので、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、プラスチック材料として再
利用可能な未架橋のポリオレフィンに再生することがで
きる方法を提供することを目的とする。The present invention has been made in view of such conventional circumstances, and provides a method capable of regenerating a crosslinked polyolefin such as a crosslinked polyethylene or a crosslinked polypropylene into an uncrosslinked polyolefin that can be reused as a plastic material. The purpose is to do.
【０００７】[0007]
【課題を解決するための手段】本発明者は、上記の目的
を達成するため鋭意研究を重ねた結果、架橋ポリオレフ
ィンを超臨界水または亜臨界水を反応溶媒として適当な
反応条件の下、分解させることにより、上記目的を達成
できることを見出し本発明を完成したものである。Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventor has found that a crosslinked polyolefin is decomposed under a suitable reaction condition using supercritical water or subcritical water as a reaction solvent. It has been found that the above objects can be achieved by doing so, and the present invention has been completed.
【０００８】すなわち、本発明の架橋ポリオレフィンの
再生方法は、請求項１に記載したように、架橋ポリオレ
フィンを、超臨界水または亜臨界水を反応溶媒として分
解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。That is, in the method for regenerating a crosslinked polyolefin of the present invention, an uncrosslinked polyolefin is produced by decomposing the crosslinked polyolefin using supercritical water or subcritical water as a reaction solvent. It is characterized by.
【０００９】本発明によれば、架橋ポリオレフィンを再
利用可能な未架橋のポリオレフィンに再生することがで
きるため、プラスチック原料として再利用することが可
能となる。なお、架橋ポリオレフィンを、超臨界水また
は亜臨界水を反応溶媒として分解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、超臨界水ま
たは亜臨界水によって、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より小さいこ
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。According to the present invention, since the crosslinked polyolefin can be regenerated into a recyclable uncrosslinked polyolefin, it can be reused as a plastic raw material. In addition, by decomposing the crosslinked polyolefin using supercritical water or subcritical water as a reaction solvent,
It is considered that the uncrosslinked polyolefin is generated because the cross-linking point in the cross-linked polyolefin is preferentially cut by supercritical water or subcritical water, and the cross-linking point is preferentially cut in this way. The reason is that the dissociation energy of the C—C bond at the crosslinking point is smaller than the dissociation energy of the C—C bond in the polyolefin molecule main chain. It is thought that the molecular kinetic energy of the polymer chain is increased by melting, and thus the polymer chain is distorted, and particularly, the crosslinked portion is greatly distorted.
【００１０】本発明においては、架橋ポリオレフィン
は、請求項２に記載したように、体積が0.025cm3〜1cm3
の粗粒からなることが望ましい。体積が前記範囲より小
さいと、反応のコントロールが難しくなり、ポリマが低
分子量化してしまうおそれがあり、また、体積が前記範
囲より大きいと、架橋ポリオレフィンが未架橋のポリオ
レフィンにまで十分に分解されないおそれがあるまた、
本発明においては、請求項３に記載したように、架橋ポ
リオレフィンが、低密度ポリエチレンの架橋体であるこ
とが望ましい。In the present invention, the crosslinked polyolefin has a volume of 0.025 cm 3 to 1 cm 3 as described in claim 2.
It is desirable to be composed of coarse particles. If the volume is smaller than the above range, it becomes difficult to control the reaction, and the polymer may be reduced in molecular weight.If the volume is larger than the above range, the crosslinked polyolefin may not be sufficiently decomposed into an uncrosslinked polyolefin. There is also
In the present invention, as described in claim 3, the crosslinked polyolefin is preferably a low-density polyethylene crosslinked product.
【００１１】さらに、請求項４に記載したように、反応
温度を200℃〜1000℃とし、かつ、反応圧力を1MPa〜100
MPa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、架橋体が十分に分解
されなかったり、逆に分解が進みすぎてポリマが低分子
量化し、そのままプラスチック材料として使用可能な未
架橋ポリオレフィンの収率が低下するおそれがある。Further, as set forth in claim 4, the reaction temperature is 200 ° C. to 1000 ° C., and the reaction pressure is 1 MPa to 100 MPa.
It is preferably set to MPa. If any of the reaction temperature and reaction pressure is out of the above range, the crosslinked product is not sufficiently decomposed, or the decomposition proceeds too much to lower the molecular weight of the polymer, and the yield of uncrosslinked polyolefin that can be used as a plastic material as it is is obtained. The rate may decrease.
【００１２】[0012]
【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.
【００１３】本発明において使用される超臨界水は、臨
界温度および臨界圧力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 and a critical pressure. In the present invention, subcritical water may be used instead of supercritical water.
【００１４】本発明においては、このような超臨界水ま
たは亜臨界水を反応溶媒として架橋ポリオレフィンを分
解させるが、その際の反応温度および反応圧力は、本発
明の効果に大きく影響する。本発明においては、反応温
度および反応圧力を、それぞれ200℃〜1000℃および1MP
a〜100MPaの範囲で調整することが好ましく、反応温度
が200℃未満では分解が不十分となり、逆に温度が1000
℃を越えると架橋点だけでなく分子主鎖の切断が進み、
得られる未架橋ポリオレフィンが低分子量となる。ま
た、反応圧力が1MPa未満では分解が不十分となり、逆に
圧力が100MPaを越えると、得られる未架橋ポリオレフィ
ンの分子量分布の幅が広くなる（低分子量の分子が増加
する。）。より好ましい範囲は、反応温度が250℃〜550
℃、反応圧力が2MPa〜80MPaの範囲であり、反応温度を3
50℃〜450℃、反応圧力を5MPa〜50MPaの範囲とするとさ
らに好ましい。In the present invention, the crosslinked polyolefin is decomposed by using such supercritical water or subcritical water as a reaction solvent, and the reaction temperature and reaction pressure at that time greatly affect the effects of the present invention. In the present invention, the reaction temperature and the reaction pressure, 200 ° C ~ 1000 ° C and 1MP, respectively
It is preferable to adjust within the range of a to 100 MPa.If the reaction temperature is less than 200 ° C., the decomposition becomes insufficient, and
If the temperature exceeds ℃, not only the crosslinking point but also the cleavage of the molecular main chain proceeds,
The resulting uncrosslinked polyolefin has a low molecular weight. On the other hand, if the reaction pressure is less than 1 MPa, the decomposition becomes insufficient, while if the pressure exceeds 100 MPa, the width of the molecular weight distribution of the obtained uncrosslinked polyolefin becomes wide (the number of low molecular weight molecules increases). A more preferred range is that the reaction temperature is from 250 ° C to 550 ° C.
℃, the reaction pressure is in the range of 2MPa ~ 80MPa, the reaction temperature is 3MPa
More preferably, the reaction pressure is in the range of 50C to 450C and the reaction pressure is in the range of 5MPa to 50MPa.
【００１５】また、反応時間および昇温時間は、それぞ
れ通常0分間〜1分間および10分間〜90分間とすることが
好ましく、これらの時間があまり長すぎると、得られる
未架橋ポリオレフィンの低分子量化が進み、逆にあまり
短いと未架橋化が不十分となるおそれがある。さらに、
降温（冷却）時間についても、あまり長すぎると、得ら
れる未架橋ポリオレフィンの低分子量化が進むため、通
常30分以内に200℃以下まで降温させることが好まし
い。It is preferable that the reaction time and the heating time are usually 0 minutes to 1 minute and 10 minutes to 90 minutes, respectively. If these times are too long, the resulting uncrosslinked polyolefin has a low molecular weight. On the contrary, if it is too short, uncrosslinking may be insufficient. further,
If the cooling (cooling) time is too long, the resulting uncrosslinked polyolefin will have a lower molecular weight. Therefore, it is usually preferable to lower the temperature to 200 ° C. or lower within 30 minutes.
【００１６】ちなみに架橋ポリエチレンを用いた再生実
験によれば、反応温度250℃〜550℃、反応圧力5MPa〜80
MPa、反応時間1分、昇温時間0分〜90分としたとき、ゲ
ル分率（JIS C 3005、以下同じ）0％、赤外吸収ピーク
強度比（910cm-1／1380cm-1）0.1以上、重量平均分子量
（Ｍｗ）が架橋前のポリエチレンの分子量の1/4以上の
未架橋ポリエチレンが得られた。また、反応温度350℃
〜450℃、反応圧力10MPa〜50MPa、反応時間1分、昇温時
間30分〜60分としたとき、ゲル分率0％、赤外吸収ピー
ク強度比（910cm-1／1380cm-1）0.2以上、重量平均分子
量（Ｍｗ）が架橋前のポリエチレンの分子量の1/3以上
の未架橋ポリエチレンが得られた。ここで、910cm-1に
おける赤外吸収ピークは不飽和結合に起因するピーク、
1380cm-1における赤外吸収ピークはポリエチレン分子鎖
に起因するピークである。Incidentally, according to a regeneration experiment using crosslinked polyethylene, the reaction temperature was 250 ° C. to 550 ° C., and the reaction pressure was 5 MPa to 80 MPa.
MPa, reaction time 1 minute, heating time 0 minute to 90 minutes, gel fraction (JIS C 3005, the same applies hereinafter) 0%, infrared absorption peak intensity ratio (910 cm -1 / 1380 cm -1 ) 0.1 or more An uncrosslinked polyethylene having a weight average molecular weight (Mw) of 1/4 or more of the molecular weight of the polyethylene before crosslinking was obtained. The reaction temperature is 350 ℃
~ 450 ° C, reaction pressure 10MPa ~ 50MPa, reaction time 1min, heating time 30min ~ 60min, gel fraction 0%, infrared absorption peak intensity ratio (910cm - 1 / 1380cm- 1 ) 0.2 or more An uncrosslinked polyethylene having a weight average molecular weight (Mw) of 1/3 or more of the molecular weight of the polyethylene before crosslinking was obtained. Here, the infrared absorption peak at 910 cm −1 is a peak due to an unsaturated bond,
The infrared absorption peak at 1380 cm -1 is a peak due to a polyethylene molecular chain.
【００１７】本発明においては、被分解物である架橋ポ
リオレフィンの大きさも、本発明の効果に大きく影響す
る。すなわち、本発明においては、体積が0.025cm3〜1c
m3の粗粒状とした架橋ポリオレフィンを用いることが望
ましく、このような粗粒状の架橋ポリオレフィンを用い
ることにより、より容易に、また、より確実に未架橋の
ポリオレフィンに分解再生することが可能となる。In the present invention, the size of the crosslinked polyolefin, which is the substance to be decomposed, also greatly affects the effects of the present invention. That is, in the present invention, the volume is 0.025 cm 3 to 1 c
It is desirable to use a crosslinked polyolefin as a crude granular m 3, by using the crosslinked polyolefin such coarse-grained, more easily, also it is possible to decompose play polyolefin reliably uncrosslinked .
【００１８】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.
【００１９】本発明により得られる未架橋のポリオレフ
ィンは、そのまま成形材料として用いることができる
他、架橋ポリオレフィンの原料として用いることができ
る。特に、本発明により再生されて得られる未架橋のポ
リオレフィンは、通常の方法で製造される未架橋ポリオ
レフィンに比べ、分子鎖中に多くの不飽和結合が含まれ
ているため、架橋の際にラジカルを発生しやすく、容易
に架橋させることができる。The uncrosslinked polyolefin obtained by the present invention can be used as it is as a molding material or as a raw material for a crosslinked polyolefin. In particular, the uncrosslinked polyolefin obtained by regeneration according to the present invention contains a large number of unsaturated bonds in the molecular chain as compared with the uncrosslinked polyolefin produced by an ordinary method. Are easily generated and can be easily crosslinked.
【００２０】[0020]
【実施例】次に、本発明を実施例によりさらに詳細に説
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。 実施例１ 電線・ケーブル用架橋ポリエチレン（ゲル分率70％、化
学架橋）からなるシートから１cm×１cm×１mmの試料を
切り出し、この試料を純水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内圧をそれぞれ40
0℃、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。得られた固形分の収率は約100％であった。Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Example 1 A sample of 1 cm × 1 cm × 1 mm was cut out from a sheet made of crosslinked polyethylene for electric wires and cables (gel fraction 70%, chemically crosslinked), and this sample was put into a pressure-resistant reaction vessel (capacity: 50 cc) together with 20 cc of pure water. did. Next, the reaction vessel is sealed and heated to reduce the temperature and the internal pressure of the reaction vessel to 40, respectively.
Raise the temperature and pressure to 0 ° C and 40MPa over 30 minutes,
(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. The yield of the resulting solid was about 100%.
【００２１】次いで、得られた固形分について、ゲル分
率および融点を測定した。結果を、試料の構成や超臨界
水による反応条件などとともに表1に示す。Next, the gel fraction and the melting point of the obtained solid content were measured. The results are shown in Table 1, together with the composition of the sample and the reaction conditions using supercritical water.
【００２２】実施例２〜１１、比較例１〜４ 試料および反応条件を表１に示すように変えた以外は、
実施例1と同様にして反応させ、固体、ワックス状、ま
たは液状の反応生成物を得た（収率はいずれも約100
％）。Examples 2 to 11, Comparative Examples 1 to 4 Except that the samples and reaction conditions were changed as shown in Table 1,
The reaction was performed in the same manner as in Example 1 to obtain a solid, waxy, or liquid reaction product (the yield was about 100%).
%).
【００２３】次いで、得られた反応生成物のうち固体の
ものについて、実施例1と同様にしてゲル分率および融
点を測定した。結果を、表1および表２に併せ示す。Next, the gel fraction and the melting point of the solid of the obtained reaction products were measured in the same manner as in Example 1. The results are shown in Tables 1 and 2.
【００２４】[0024]
【表１】 [Table 1]
【表２】 表1および表２からも明らかなように、本発明に係る実
施例では、架橋ポリエチレンあるいは架橋ポリプロピレ
ンがいずれも未架橋ポリエチレンあるいは未架橋ポリプ
ロピレンに変わっていることが確認された。[Table 2] As is clear from Tables 1 and 2, it was confirmed that in the examples according to the present invention, both the crosslinked polyethylene and the crosslinked polypropylene were changed to uncrosslinked polyethylene or uncrosslinked polypropylene.
【００２５】実施例１２ 重量平均分子量（Ｍｗ）86000、多分散度（Ｍｗ／Ｍ
ｎ）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）を用いてゲル分率が80％の
架橋ポリエチレンシートを作製した。このシートから１
cm×１cm×１mmの試料を切り出し、純水とともに耐圧反
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内圧をそれぞ
れ400℃、40MPaまで40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 12 Weight average molecular weight (Mw) 86000, polydispersity (Mw / M
n) DCP as a crosslinking agent for 5.7 low density polyethylene
(Dicumyl peroxide) was used to prepare a crosslinked polyethylene sheet having a gel fraction of 80%. 1 from this sheet
A sample of cm × 1 cm × 1 mm was cut out and put into a pressure-resistant reaction vessel (capacity: 50 cc) together with pure water. Next, the reaction vessel was sealed and heated to raise the temperature and the internal pressure of the reaction vessel to 400 ° C. and 40 MPa, respectively, over 40 minutes, and then 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.
【００２６】得られた固形分について、ゲル分率を測定
するとともに、ＧＰＣ（ゲル浸透クロマトグラフィ）分
析を行い、分子量（Ｍｗ）および多分散度（Ｍｗ／Ｍ
ｎ）を求めた。また、赤外分光光度計により吸収ピーク
強度比（910cm-1／1380cm-1）を求めた。結果を、試料
の構成や反応条件などとともに表３に示す。The solid content was measured for gel fraction and analyzed by GPC (gel permeation chromatography) to determine the molecular weight (Mw) and polydispersity (Mw / M
n) was determined. Further, an absorption peak intensity ratio (910 cm −1 / 1380 cm −1 ) was determined by an infrared spectrophotometer. Table 3 shows the results together with the composition of the sample and the reaction conditions.
【００２７】一方、同様にして得た固形分約3ｇを破砕
機により破砕して平均粒径約1mm以下とし、ＤＣＰを5重
量％混合した後、ガラス容器に入れ密封した。次いで、
この容器に対しミキシングと恒温槽による加熱（60℃）
を繰返し、ＤＣＰの液状物が外から確認されなくなった
ところで、容器から内容物1.5ｇを量り取り、加熱プレ
ス成型（150℃×30分、200kg/cm2）してシートを作製し
た。このシートのゲル分率を測定したところ85％であっ
た。On the other hand, about 3 g of the solid content obtained in the same manner was crushed by a crusher to reduce the average particle size to about 1 mm or less, mixed with 5% by weight of DCP, and sealed in a glass container. Then
Mixing of this container and heating in a thermostat (60 ℃)
When the liquid substance of DCP was no longer confirmed from the outside, 1.5 g of the content was weighed from the container, and heated and press-molded (150 ° C. × 30 minutes, 200 kg / cm 2 ) to produce a sheet. The gel fraction of this sheet was measured to be 85%.
【００２８】実施例１３〜１７ 試料および反応条件を表３に示すように変えた以外は、
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。Examples 13-17 Except that the samples and reaction conditions were changed as shown in Table 3,
The reaction was carried out in the same manner as in Example 1, and a solid content was separated and recovered from the reaction solution.
【００２９】次いで、得られた固形分について、実施例
1２と同様にして、ゲル分率、分子量（Ｍｗ）および多
分散度（Ｍｗ／Ｍｎ）、赤外吸収ピーク強度比（910cm
-1／1380cm-1）を求めた。また、その結果、ゲル分率が
0％であったものについて、実施例1３と同様にして、再
架橋させ、得られたシートについてゲル分率を測定し
た。これらの結果を表３に併せ示す。Next, the obtained solid content was measured in Examples
12, the gel fraction, the molecular weight (Mw) and the polydispersity (Mw / Mn), and the infrared absorption peak intensity ratio (910 cm
-1 / 1380cm -1) was determined. As a result, the gel fraction
Those having 0% were recrosslinked in the same manner as in Example 13, and the gel fraction of the obtained sheet was measured. The results are shown in Table 3.
【００３０】[0030]
【表３】 [Table 3]
【００３１】[0031]
【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超臨界水または亜臨界水を反応溶
媒として分解することにより、再利用可能な未架橋のポ
リオレフィンに再生することができる。As described above, according to the present invention,
By decomposing the crosslinked polyolefin using supercritical water or subcritical water as a reaction solvent, it is possible to regenerate a recyclable uncrosslinked polyolefin.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 内田 克己 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 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 会田 二三夫 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 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 AA13 AC01 AD01 AD02 BA21 BF19 BF31 4J100 AA02P AA03P AA06P AG04Q CA01 CA04 CA31 EA05 FA30 HA51 HE12 HE32 HE35 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Katsumi Uchida 20-1 Kitakanyama, Odaka-cho, Midori-ku, Nagoya-shi, Aichi Prefecture Inside Electric Power Research Laboratory, Chubu Electric Power Co., Inc. (72) Inventor Kiyoji Furumura Midori, Nagoya-shi, Aichi 20-1 Kitakanyama, Otaka-cho, Ward Chubu Electric Power Co., Inc. Electric Power Research Laboratory (72) Inventor Fumio Aida 2-1-1 Oda Sakae, Kawasaki-ku, Kawasaki City, Kanagawa Prefecture Showa Electric Cable Co., Ltd. (72) Invention Person Susumu Hirai 2-1-1 Oda Sakae, Kawasaki-ku, Kawasaki City, Kanagawa Prefecture Inside Showa Electric Wire & Cable Co., Ltd. F term (reference) 4F301 AA13 AC01 AD01 AD02 BA21 BF19 BF31 4J100 AA02P AA03P AA06P AG04Q CA01 CA04 CA31 EA05 FA30 HA51 HE12 HE32 HE35
Claims (4)
亜臨界水を反応溶媒として分解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 decomposing a crosslinked polyolefin using supercritical water or subcritical water as a reaction solvent to produce an uncrosslinked polyolefin.
5cm3〜1cm3の粗粒からな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. The crosslinked polyolefin has a volume of 0.02.
The method of regeneration crosslinked polyolefin according to claim 1, characterized in that it consists of coarse grains of 5 cm 3 1 cm 3.
エチレンの架橋体であ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. The method for regenerating a crosslinked polyolefin according to claim 1, wherein the crosslinked polyolefin is a crosslinked product of low density polyethylene.
反応圧力を1MPa〜100MPaとすることを特徴とする請求項
１乃至３のいずれか１項記載の架橋ポリオレフィンの再
生方法。4. A reaction temperature of 200 ° C. to 1000 ° C., and
The method for regenerating a crosslinked polyolefin according to any one of claims 1 to 3, wherein the reaction pressure is 1 MPa to 100 MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001067474A JP2001323022A (en) | 2000-03-10 | 2001-03-09 | Method for regenerating crosslinked olefin |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000-67812 | 2000-03-10 | ||
| JP2000067812 | 2000-03-10 | ||
| JP2001067474A JP2001323022A (en) | 2000-03-10 | 2001-03-09 | Method for regenerating crosslinked olefin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2001323022A true JP2001323022A (en) | 2001-11-20 |
Family
ID=26587258
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2001067474A Withdrawn JP2001323022A (en) | 2000-03-10 | 2001-03-09 | Method for regenerating crosslinked olefin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2001323022A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7629419B2 (en) | 2001-10-16 | 2009-12-08 | Sekisui Chemical Co., Ltd. | Process for producing modified polymer, apparatus for producing modified polymer, and modified polymer |
| KR101139475B1 (en) | 2009-09-07 | 2012-04-30 | 한국과학기술연구원 | Method of recycling crosslinked waste pipes of high density polyethylene |
| CN110326128A (en) * | 2018-01-31 | 2019-10-11 | 株式会社Lg化学 | Diaphragm includes the lithium secondary battery of diaphragm and its manufacturing method |
| WO2022124015A1 (en) * | 2020-12-07 | 2022-06-16 | 東洋製罐グループホールディングス株式会社 | Method for removing impurities from plastic |
-
2001
- 2001-03-09 JP JP2001067474A patent/JP2001323022A/en not_active Withdrawn
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7629419B2 (en) | 2001-10-16 | 2009-12-08 | Sekisui Chemical Co., Ltd. | Process for producing modified polymer, apparatus for producing modified polymer, and modified polymer |
| KR101139475B1 (en) | 2009-09-07 | 2012-04-30 | 한국과학기술연구원 | Method of recycling crosslinked waste pipes of high density polyethylene |
| CN110326128A (en) * | 2018-01-31 | 2019-10-11 | 株式会社Lg化学 | Diaphragm includes the lithium secondary battery of diaphragm and its manufacturing method |
| WO2022124015A1 (en) * | 2020-12-07 | 2022-06-16 | 東洋製罐グループホールディングス株式会社 | Method for removing impurities from plastic |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Maris et al. | Mechanical recycling: Compatibilization of mixed thermoplastic wastes | |
| AU2007333019B2 (en) | Devulcanized rubber and methods | |
| US3852046A (en) | Method for recycling waste plastics and products thereof | |
| CN102448994B (en) | Process for production of bimodal hdpe with wax recovery | |
| EP1863620A2 (en) | Method and system for processing waste materials | |
| JPH1024274A (en) | Method for decomposing and recycling thermosetting resin | |
| Papaspyrides et al. | A model recycling process for low density polyethylene | |
| WO2022074462A1 (en) | Styrene-assisted depolymerization of polyolefins | |
| JP2001323022A (en) | Method for regenerating crosslinked olefin | |
| CN101117403B (en) | Method for recycling a cross-linked polymer | |
| US20090102081A1 (en) | Process of using cross linked plastics as recovery material or modifier | |
| KR101848775B1 (en) | Manufacturing method of micronized thermoplastic waste fluoropolymer resin | |
| KR101296011B1 (en) | Fuel pellets using sludge | |
| CN1951654A (en) | Waste natural fiber thermoplastic composite plate reclamation and regeneration method | |
| KR101723424B1 (en) | Manufacturing Method of Pellet for Mudguard of Vehicle Using Recycling Beverage Bottle Cap | |
| JP2002256103A (en) | Process for regeneration of crosslinked polyolefin | |
| Baurova et al. | Utilization methods for machine parts made of polymer-composite materials | |
| CA2207441C (en) | Method for processing composite materials to enable recycling thereof | |
| JP4534395B2 (en) | Method for producing material recycled from cross-linked polymer | |
| CN112940767A (en) | Harmless high-carbon conversion method for non-meal domestic garbage, product and application thereof | |
| Saleem et al. | Development of Polymeric Aerogel using Plastic Wastes for Oil Cleanup from Wastewater | |
| JPH10287766A (en) | Decomposing and recycling methods for thermosetting resin | |
| JP3421316B2 (en) | Method and apparatus for manufacturing a molded product mainly composed of woody material | |
| KR101629245B1 (en) | Hybrid composite material for hybrid rubber and waste plastic and manufacturing method thereof | |
| JP4400596B2 (en) | How to recycle alcohol |
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 |