JPS62185706A - Production of radiation-resistant polymer composition - Google Patents
Production of radiation-resistant polymer compositionInfo
- Publication number
- JPS62185706A JPS62185706A JP2601886A JP2601886A JPS62185706A JP S62185706 A JPS62185706 A JP S62185706A JP 2601886 A JP2601886 A JP 2601886A JP 2601886 A JP2601886 A JP 2601886A JP S62185706 A JPS62185706 A JP S62185706A
- Authority
- JP
- Japan
- Prior art keywords
- indene
- polymeric material
- mixture
- oligomer
- coumarone
- 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.)
- Pending
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 23
- 230000005855 radiation Effects 0.000 title claims abstract description 22
- 229920000642 polymer Polymers 0.000 title claims abstract description 6
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- 239000000463 material Substances 0.000 claims abstract description 20
- 150000002469 indenes Chemical class 0.000 claims description 6
- 150000003254 radicals Chemical class 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 3
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 abstract description 39
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 abstract description 25
- 238000010894 electron beam technology Methods 0.000 abstract description 4
- 238000010438 heat treatment Methods 0.000 abstract description 4
- 230000005865 ionizing radiation Effects 0.000 abstract description 4
- 239000000654 additive Substances 0.000 abstract description 3
- 150000001451 organic peroxides Chemical class 0.000 abstract description 2
- KPAPHODVWOVUJL-UHFFFAOYSA-N 1-benzofuran;1h-indene Chemical compound C1=CC=C2CC=CC2=C1.C1=CC=C2OC=CC2=C1 KPAPHODVWOVUJL-UHFFFAOYSA-N 0.000 abstract 1
- 229920001577 copolymer Polymers 0.000 description 10
- 239000002861 polymer material Substances 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 6
- -1 polyethylene Polymers 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 229920002681 hypalon Polymers 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000005038 ethylene vinyl acetate Substances 0.000 description 3
- 239000003063 flame retardant Substances 0.000 description 3
- 230000005251 gamma ray Effects 0.000 description 3
- 230000001678 irradiating effect Effects 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000004709 Chlorinated polyethylene Substances 0.000 description 2
- GUTLYIVDDKVIGB-OUBTZVSYSA-N Cobalt-60 Chemical compound [60Co] GUTLYIVDDKVIGB-OUBTZVSYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- UBRWPVTUQDJKCC-UHFFFAOYSA-N 1,3-bis(2-tert-butylperoxypropan-2-yl)benzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC(C(C)(C)OOC(C)(C)C)=C1 UBRWPVTUQDJKCC-UHFFFAOYSA-N 0.000 description 1
- PAOHAQSLJSMLAT-UHFFFAOYSA-N 1-butylperoxybutane Chemical compound CCCCOOCCCC PAOHAQSLJSMLAT-UHFFFAOYSA-N 0.000 description 1
- LRTOHSLOFCWHRF-UHFFFAOYSA-N 1-methyl-1h-indene Chemical compound C1=CC=C2C(C)C=CC2=C1 LRTOHSLOFCWHRF-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 description 1
- 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
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 1
- 125000004054 acenaphthylenyl group Chemical group C1(=CC2=CC=CC3=CC=CC1=C23)* 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 150000001907 coumarones Chemical class 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- QHZOMAXECYYXGP-UHFFFAOYSA-N ethene;prop-2-enoic acid Chemical compound C=C.OC(=O)C=C QHZOMAXECYYXGP-UHFFFAOYSA-N 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 229920006226 ethylene-acrylic acid Polymers 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000010559 graft polymerization reaction Methods 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 230000002747 voluntary effect Effects 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
- BOXSVZNGTQTENJ-UHFFFAOYSA-L zinc dibutyldithiocarbamate Chemical compound [Zn+2].CCCCN(C([S-])=S)CCCC.CCCCN(C([S-])=S)CCCC BOXSVZNGTQTENJ-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Graft Or Block Polymers (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、放射線環境下で使用するのに適するよう改質
された耐放射線高分子組成物の製造方法に関するもので
ある。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a method for producing a radiation-resistant polymer composition modified to be suitable for use in a radiation environment.
（従来の技術）
原子力発電所、各種廃棄物処理施設、あるいはイオン化
放射線発生器設置室などの放射線環境下において使用さ
れる高分子材料は、常に多量の放射線を被曝することに
なり優れた耐放射線性を具備していることが必要である
。(Prior art) Polymer materials used in radiation environments such as nuclear power plants, various waste treatment facilities, or rooms where ionizing radiation generators are installed are constantly exposed to large amounts of radiation, so they do not have excellent radiation resistance. It is necessary that the person possesses a certain gender.
しかしながら、広範囲の用途及び使用態様で使われてい
る汎用樹脂材料の多くは概ね耐放射線性が低く、比較的
短時間で可撓性などの物性が低下することが多い。まｔ
コ、耐放射線性が特に優れた樹脂、例えばポリイミドや
ポリエーテルエーテルケトン等は高価であり、特性上可
撓性にも劣るので利用範囲に制約があるなど汎用樹脂と
して使用しにくい。However, most of the general-purpose resin materials used in a wide range of applications and usage modes generally have low radiation resistance, and physical properties such as flexibility often deteriorate in a relatively short period of time. Yes
Second, resins with particularly excellent radiation resistance, such as polyimide and polyetheretherketone, are expensive and have poor flexibility, so they are difficult to use as general-purpose resins because of their limited range of use.
そこで汎用ＩＩＭＩＩＮの物性や経済性を損わず、他方
、耐放射線性を改善する手段として、芳香族系化合物を
添加する方法が一般に知られている。Therefore, as a means of improving the radiation resistance without impairing the physical properties or economic efficiency of general-purpose IIMIIN, a method of adding an aromatic compound is generally known.
（発明が解決しようとする問題点）
しかしこれら芳香族系化合物は一般的な高分子材料との
相溶性が低く、長期間使用後のブルーム発生によりその
効果が著しく低下する等の問題があった。他方かかるブ
ルーム発生を防止するため、例えば特開昭５５−１０６
２２８号発明の如く、例えばハロゲン化アセナフチレン
のような高分子材料と化学反応をする物質を使用する手
段もある。(Problems to be solved by the invention) However, these aromatic compounds have low compatibility with general polymer materials, and there are problems such as blooming after long-term use, which significantly reduces their effectiveness. . On the other hand, in order to prevent the occurrence of such bloom, for example, Japanese Patent Laid-Open No. 55-106
There is also a means of using a substance that chemically reacts with a polymeric material, such as halogenated acenaphthylene, as in the No. 228 invention.
しかしこのような反応性物質を大量に添加した場合これ
ら反応性物質を完全に高分子材料と反応させることは難
しく、未反応物の残留やこれら化合物同士の反応なども
起ることがあり、結果的には添加する物質、化合物のブ
ルームを完全に防止できるものではなかった。However, when large amounts of such reactive substances are added, it is difficult to completely react these reactive substances with the polymer material, and unreacted substances may remain or reactions between these compounds may occur, resulting in However, it has not been possible to completely prevent blooming of added substances and compounds.
（問題点を解決するための手段）
ここに本発明者らはかかる高分子材料に於ける添加物の
ブルーム発生を殆んど起さず優れた耐放射線性を付与す
ることのできる添加材料に関して鋭意検討を行った結果
、クマロン−インデンオリゴマーが優れた性能を持って
いることを見出しこの発明を完成したものである。(Means for Solving the Problems) The present inventors have hereby proposed an additive material that can impart excellent radiation resistance to polymeric materials with almost no additive blooming. As a result of extensive research, it was discovered that coumaron-indene oligomer had excellent performance, and this invention was completed.
即ちこの発明は高分子材料に対して、クマロン類とイン
デン類とを共重合させて得られたクマロン−インデンオ
リゴマーを加えた後、この混和物に遊離基発生処理を施
し該クマロン−インデンオリゴマーを高分子材料中で重
合させることを特徴とする耐放射線高分子組成物の製造
方法である。That is, in this invention, a coumaron-indene oligomer obtained by copolymerizing coumarons and indenes is added to a polymer material, and then this mixture is subjected to a free radical generation treatment to generate the coumaron-indene oligomer. This is a method for producing a radiation-resistant polymer composition, which is characterized by polymerization in a polymer material.
この発明で用い°られる高分子材料としては、具体的に
はポリエチレン、塩素化ポリエチレン、ポリプロピレン
、ポリブテン、エチレンプロピレン共重合体、エチレン
プロピレンジエン共重合体、エチレン酢酸ビニル共重合
体、エチレンアクリル酸エステル共重合体、ポリ塩化ビ
ニル、エチレン酢酸ビニルグラフト塩化ビニル共重合体
、エチレンアクリル酸グラフト塩化ビニル共重合体、エ
チレンプロピレングラフト塩化ビニル共重合体、塩素化
ポリエチレングラフト塩化ビニル共重合体、天然ゴム、
ブチルゴム、クロロプレンゴム、クロロスルフォン化ホ
リエチレン、シリコーンゴム、スチレンブタジェンゴム
、スチレンアクリロニトリル共重合体、スチレン−ブタ
ジェンアクリロニトリル共重合体、ポリエステルエーテ
ルエラストマー、ポリウレタン、ポリエステル、アクリ
ル樹脂、ニトリルゴムなどの可撓性を有する材料が挙げ
られる。Specifically, the polymer materials used in this invention include polyethylene, chlorinated polyethylene, polypropylene, polybutene, ethylene propylene copolymer, ethylene propylene diene copolymer, ethylene vinyl acetate copolymer, and ethylene acrylate ester. Copolymer, polyvinyl chloride, ethylene vinyl acetate grafted vinyl chloride copolymer, ethylene acrylic acid grafted vinyl chloride copolymer, ethylene propylene grafted vinyl chloride copolymer, chlorinated polyethylene grafted vinyl chloride copolymer, natural rubber,
Butyl rubber, chloroprene rubber, chlorosulfonated polyethylene, silicone rubber, styrene-butadiene rubber, styrene-acrylonitrile copolymer, styrene-butadiene-acrylonitrile copolymer, polyester ether elastomer, polyurethane, polyester, acrylic resin, nitrile rubber, etc. Examples include materials that have flexibility.
次にクマロンインデンオリゴマーは、高分子材料との混
練性、相溶性が著しく良くブルームしないことに特徴が
ある。そしてこの発明において、使用するクマロン−イ
ンデンオリゴマーは、クマロン類とインデン類を共重合
させて得られるオリゴマー、好ましくは２〜１０量体の
オリゴマーであり、末端に重合可能な不飽和基を有する
ものである。クマロン類、インデン類とはクマロン、イ
ンデン自体およびこれらのアルキル置換体、アルコキシ
置換体、アルキルエステル置換体をさす。Next, coumaron indene oligomer is characterized by extremely good kneadability and compatibility with polymeric materials and no blooming. In this invention, the coumaron-indene oligomer used is an oligomer obtained by copolymerizing coumarons and indenes, preferably a dimer to decamer oligomer, and has a polymerizable unsaturated group at the terminal. It is. Coumarones and indenes refer to coumaron, indene itself, and alkyl-substituted products, alkoxy-substituted products, and alkyl ester-substituted products thereof.
アルキル基、アルコキシ基又はアルキルエステル基とし
ては低級アルキル基、低級アルコ１シ基又は低級アルキ
ルエステル基が好ましい。これらの置換基は０〜４個結
合することができるが０〜２個が好ましい。クマロン−
インデンオリゴマーは、クマロン類とインデン類とをク
マロンＭ１モルに対しインデン類１〜１０モル、好まし
くは１〜５モルの割合で、場合によってはこれらとスチ
レン類とを酸性触媒、例えばＢＦ３触媒、硫酸−リン酸
触媒等の存在下で共重合させることによす得られる。The alkyl group, alkoxy group or alkyl ester group is preferably a lower alkyl group, a lower alkyl group or a lower alkyl ester group. Although 0 to 4 of these substituents can be bonded, 0 to 2 of these substituents are preferable. Kumaron-
Indene oligomers are prepared by combining coumarons and indenes in a ratio of 1 to 10 moles, preferably 1 to 5 moles of indenes per mole of coumaron M, and in some cases, these and styrenes are mixed with an acidic catalyst, such as a BF3 catalyst, or sulfuric acid. - Obtained by copolymerization in the presence of a phosphoric acid catalyst or the like.
上記クマロンンデンオリゴマーの高分子材料に対する配
合量は特に限定されるものではないが、より高度の耐放
射線性を具備させるためには高分子材料１００重量部に
対して５重量部以上配合することが望ましい。The amount of the coumarondene oligomer to be added to the polymeric material is not particularly limited, but in order to provide a higher degree of radiation resistance, 5 parts by weight or more should be added to 100 parts by weight of the polymeric material. This is desirable.
実際には両者の混線は可及的均一になるように実施する
必要があり、その手段としては、加熱ロール、バンバリ
ーミキサ−、ヘンシェルミキサー、ニーダ−あるいは押
出機などの各種混練機を用いることができる。この場合
上記クマロンインデンオリゴマーの配合量が多いと上記
均一な混和の妨げになることもありその配合量の上限値
が用いる高分子材料や混練によっである程度限定される
こともある。In reality, it is necessary to make the mixing of the two as uniform as possible, and various kneading machines such as heated rolls, Banbury mixers, Henschel mixers, kneaders, or extruders can be used to achieve this. can. In this case, if the amount of the coumaron indene oligomer blended is large, it may interfere with the uniform mixing, and the upper limit of the amount blended may be limited to some extent depending on the polymer material used and kneading.
次にこの発明において、上記両材料混練後に遊離基発生
処理を施す具体的手段として、ジクミルパーオキサイド
、１，３ビス（ｔ−ブチルパーオキシイソプロビル）ベ
ンゼン、２，５ジメチル２，５ジ（１−ブチルパーオキ
シ）ヘキシン−３、ジー上ブチルパーオキサイド等の有
機過酸化物を混合して加熱する手段、或いはβ線、γ線
、電子線等の電離性放射線照射による手段等が実際的で
ある。Next, in this invention, as a specific means for performing free radical generation treatment after kneading the above-mentioned two materials, dicumyl peroxide, 1,3 bis(t-butylperoxyisopropyl)benzene, 2,5 dimethyl 2,5 dimethyl In practice, methods include mixing and heating organic peroxides such as (1-butylperoxy)hexyne-3 and di-butyl peroxide, or irradiating with ionizing radiation such as β rays, γ rays, and electron beams. It is true.
乙の遊離基発生処理により、上記クマロンインデンオリ
ゴマーが高分子材料中で重合するが、ここで重合とはホ
モ重合又はグラフト重合を意味し、これが高分子組成物
の耐放射線性向上に寄与するものである。By the free radical generation treatment (B), the coumaron indene oligomer is polymerized in the polymer material, and polymerization here means homopolymerization or graft polymerization, which contributes to improving the radiation resistance of the polymer composition. It is something.
なお、本発明において、上記組成物に対してトリメチロ
ールプロパントリメタアクリレート、ポリエチレングリ
コールジメタアクリレート、トリアリルシアヌレート等
の多官能性モノマーを併用し上述の遊離基発生処理の効
率を上昇せしめたり、又ハロゲン系難燃剤、三酸化アン
チモン、二酸化モリブデン、水酸化アルミニウム、水酸
化マグネシウム、炭酸カルシウム、リン化合物、亜鉛化
合物等の難燃剤を配合して難燃性を付与すること、及び
充填老化防止剤、充填剤、顔料、滑剤、光安定剤など本
来の特性を低下させない範囲で加えられることは何ら差
し支えない。In addition, in the present invention, a polyfunctional monomer such as trimethylolpropane trimethacrylate, polyethylene glycol dimethacrylate, triallyl cyanurate, etc. is used in combination with the above composition to increase the efficiency of the above-mentioned free radical generation treatment. In addition, flame retardants such as halogenated flame retardants, antimony trioxide, molybdenum dioxide, aluminum hydroxide, magnesium hydroxide, calcium carbonate, phosphorus compounds, and zinc compounds are blended to impart flame retardancy, and to prevent filling aging. There is no problem in adding agents, fillers, pigments, lubricants, light stabilizers, etc. as long as the original properties are not deteriorated.
（作 用）
本発明においては、上記クマロン−インデンオリゴマー
が高分子材料中に均一に混練され、しかもこれらが該高
分子材料中で適切に重合しこれによりブルームを全く発
生せず上述した各種問題を未然に回避するものである。(Function) In the present invention, the coumaron-indene oligomers are uniformly kneaded into the polymeric material, and moreover, they are properly polymerized in the polymeric material, thereby eliminating any blooming and solving the various problems mentioned above. This is to avoid this.
（′Ａ施例） 以下実施例によりこの発明を具体的に説明する。('A example) The present invention will be specifically explained below with reference to Examples.
クマロン−インデンオリゴマーの調整
（１１クマロン１モル／１１メチルインデン３モル／１
及び触媒として、８５％リン酸と９５％硫酸の９： １
混合物を１重量パーセント加え、温度１００〜１１０℃
で１時間反応させた。比重差で分離後、中和、水洗し、
減圧下で蒸発ｆ：４縮して、茶褐色液状のクマロンイン
デンオリゴマーを得た。Preparation of coumaron-indene oligomer (11 coumarone 1 mol/11 methylindene 3 mol/1
and 9:1 of 85% phosphoric acid and 95% sulfuric acid as catalyst.
Add 1% by weight of the mixture and adjust the temperature to 100-110℃
The mixture was reacted for 1 hour. After separation based on the difference in specific gravity, neutralization, washing with water,
Evaporation f:4 condensation was performed under reduced pressure to obtain a brown liquid coumaron indene oligomer.
得られたクマロンインデンオリゴマーは２〜３量体を主
成分とし、粘度５０ボイズ（２５℃）、比ｇ１，０９（
２０℃）臭素化６０ （ｇ／１００ｇンの液体であった
。（以下、この化合物をクマロンインデンオリゴマーＡ
と呼ぶ）
＋２）クマロン１モル／１１インデン３モル／１１触媒
としてＢＦ３エーテルコンプレックス１重量％を加え、
温度６０〜１００℃で２時間反応させた。The obtained coumaron indene oligomer mainly consists of dimers and trimers, has a viscosity of 50 voids (at 25°C), and a ratio of g1.09 (
(20°C) Brominated 60g/100g liquid. (Hereinafter, this compound will be referred to as coumaron indene oligomer A.
+2) 1 mol of coumaron/11 3 mol of indene/11 Add 1% by weight of BF3 ether complex as a catalyst,
The reaction was carried out at a temperature of 60 to 100°C for 2 hours.
次に、水洗によって脱触媒し、水を分ｇｌ後減圧下で蒸
発濃縮して淡黄色固体状のクマロンインデンオリゴマー
を得た。Next, the catalyst was removed by washing with water, and after removing 1 gl of water, it was evaporated and concentrated under reduced pressure to obtain a pale yellow solid coumaron indene oligomer.
得られたクマロンインデンオリゴマーは７〜８量体を主
成分とし、軟化点８０〜１３０℃、比重１．０１臭素化
２５ （ｇ／１００ｇ）の固体であった。The obtained coumaron indene oligomer was a solid containing heptamer to octamer as a main component, a softening point of 80 to 130°C, and a specific gravity of 1.01 and bromination of 25 (g/100g).
（以下、この化合物をクマロンインデンオリゴマーＢと
呼ぶ）
実施例１〜５および比較例１〜３
エチレンプロピレン共重合体に対して表１．およびクロ
ロスルフォン化ポリエチレンに対して表２に各々示す組
成となるよう上記合成りマロンインデンオリゴマー外各
種配合剤を加え、これらを加熱ロールにてよく練和し、
得られた混和物を１６０℃にて３０分間プレス成型して
２ｍｌ１１厚シートを作成した。(Hereinafter, this compound will be referred to as coumaron indene oligomer B) Examples 1 to 5 and Comparative Examples 1 to 3 Table 1. and chlorosulfonated polyethylene, various compounding agents other than the synthetic malonindene oligomer were added to the compositions shown in Table 2, and these were thoroughly kneaded with a heating roll.
The obtained mixture was press-molded at 160° C. for 30 minutes to prepare a 2 ml, 11 thick sheet.
得られたシートおよびそれらにγ線２００Ｍｒａｄ照射
した後のシートをＪＩＳＣ３００４に従っｒ引張り試験
を行ない結果をそれぞれ表１および表２に示した。なお
、γ線照射はコバルト６０ｆｓ源により常温空気中で平
均０．９ Ｍｒａｄ／Ｈ，の線量率下で所定時間実施し
た。The obtained sheets and the sheets after irradiating them with 200 Mrad of gamma rays were subjected to a tensile test according to JISC3004, and the results are shown in Tables 1 and 2, respectively. The γ-ray irradiation was performed using a cobalt 60 fs source in air at room temperature for a predetermined period of time at an average dose rate of 0.9 Mrad/H.
表１及び２の結果によればクマロンインデンオリゴマー
はエチレンプロピレン共重合体、クロロスルフォン化ポ
リエチレンの耐放射線性を著しく改善することが明らか
である。According to the results in Tables 1 and 2, it is clear that coumaron indene oligomer significantly improves the radiation resistance of ethylene propylene copolymer and chlorosulfonated polyethylene.
表 １
※１ 日本合成ゴム社製
ＥＰ−２１（プロピレン結合量４０重量％）※２ 入内
新興化学社製
ツクラック２２４（２，２，４１−リメチル−１，２−
ジヒドロキノリン共重合体）
表 ２
※Ｉ Ｄｕｐｏｎｔ社、商品名ハイパロン４０※２
大部産業社、商品名ケンフレックスＡ※３ 大内新興化
学社、ニッケルジブチルジチオカルバメート
実施例６および比較例４
エチレン酢酸ビニル共重合体に対して次表３に示す組成
となるよう、クマロンインデンオリゴマーＡ外記合剤を
加え、これらをバンバリーミキサ−にてよく練和した。Table 1 *1 EP-21 manufactured by Nippon Synthetic Rubber Co., Ltd. (Propylene bond content: 40% by weight) *2 Tsurac 224 manufactured by Iruuchi Shinko Kagaku Co., Ltd. (2,2,41-limethyl-1,2-
Dihydroquinoline copolymer) Table 2 *I Dupont Co., trade name Hypalon 40 *2
Obe Sangyo Co., Ltd., trade name Kenflex A*3 Ouchi Shinko Kagaku Co., Ltd., nickel dibutyl dithiocarbamate Example 6 and Comparative Example 4 Indene oligomer A external mixture was added, and these were thoroughly kneaded using a Banbury mixer.
得られた混和物を錫メツキ軟銅撚線（外径３．４鴫、断
面！！！２ ａｍ’ ）上に０．８＋ｗ厚に押出被覆し
た。次いでこの絶縁電線に電子線加速器によす１５ Ｍ
ｒａｄの電子線を照射して架橋を施した。The obtained mixture was extrusion coated onto a tin-plated annealed copper stranded wire (outer diameter: 3.4 mm, cross section: 2 am') to a thickness of 0.8+w. Next, this insulated wire was passed through an electron beam accelerator at 15 M.
Crosslinking was performed by irradiation with a rad electron beam.
得られた難燃性絶縁電線のｉ載持性およびγ線１００Ｍ
ｒａｄ照射後の機械特性を測定した結果を同表３にイ井
記した。なお、７゛線照射はコバルト６０線源により常
温空気中で平均０．９ Ｍｒａｄ／Ｈｒの線量率で所定
時間実施した。I loading property and γ-ray 100M of the obtained flame-retardant insulated wire
The results of measuring the mechanical properties after rad irradiation are shown in Table 3. The 7° ray irradiation was carried out for a predetermined period of time using a cobalt-60 radiation source in air at room temperature at an average dose rate of 0.9 Mrad/Hr.
表３の結果によればエチレン酢酸ビニル共重合体は照射
後の伸びが小さく二つ折りにして曲げると容易に破断し
てしまうが、クマロンインデンオリゴマーを配合するこ
とにより破断せず柔軟性を保持しており、耐放射線性が
著しく改善されることが明らかであった。According to the results in Table 3, ethylene vinyl acetate copolymer has low elongation after irradiation and easily breaks when folded in half, but by incorporating coumaron indene oligomer, it does not break and maintains flexibility. It was clear that the radiation resistance was significantly improved.
表 ３
※１ 三井ポリケミカル社製 Ｖ−５，２７−４（酢酸
ビニル結合量１９％）
※２ 表１に同じ
実施例７および比較例５
低密度ポリエチレンを用い同様にして下表４に示す組成
となるよう各種配合剤を加え、これらを加熱ロールにて
よく練和し、得られた組成物を１６０℃、３・０分間プ
レス成型してｌｌｌ１ｌＩ厚シートを作成した。Table 3 *1 V-5,27-4 manufactured by Mitsui Polychemical Co., Ltd. (vinyl acetate bond amount 19%) *2 Same Example 7 and Comparative Example 5 as shown in Table 1 Low density polyethylene was used and shown in Table 4 below Various compounding agents were added to obtain the desired composition, and these were thoroughly kneaded with a heating roll, and the resulting composition was press-molded at 160° C. for 3.0 minutes to produce a llllll thick sheet.
得られたシートおよびそれらにγ線１００ Ｍｒａｄ照
射した後のシートをＪＩＳ Ｃ３００５に従って引張
り試験を行った。結果を同表４に示す。The obtained sheets and the sheets after irradiating them with 100 Mrad of gamma rays were subjected to a tensile test in accordance with JIS C3005. The results are shown in Table 4.
なお、γ線照射はコバルト６０Ｉａ源により常温空気中
で平均０．９Ｍｔａｄ／Ｈｒの１ｓ量率下で所定時間実
施した。The γ-ray irradiation was performed using a cobalt-60Ia source in air at room temperature for a predetermined period of time at an average rate of 0.9 Mtad/Hr for 1 s.
表４の結果によれば上記クマロンインデンオリゴマーは
上述の如くポリエチレンの耐放射線性をも著しく改善す
ることができる。According to the results in Table 4, the coumaron indene oligomer can also significantly improve the radiation resistance of polyethylene as described above.
表 ４
（発明の効果）
本発明により得られた組成物は耐放射線性が著しく優れ
ているので、原子力発電所、廃棄物処理施設、イオン化
放射線発生器などの放射線環境下における電線ケーブル
彼覆材、バッキング等の用途に好適に用いられる等その
工業的利用価値は非常に大きい。Table 4 (Effects of the Invention) The composition obtained by the present invention has extremely excellent radiation resistance, so it can be used as a covering material for electric wires and cables in radiation environments such as nuclear power plants, waste treatment facilities, and ionizing radiation generators. It is suitable for use in applications such as backing, etc., and has great industrial utility value.
手続補正書（自発） 昭和６１年１０月２９日Procedural amendment (voluntary) October 29, 1986
Claims (1)
合させて得られたクマロン−インデンオリゴマーを加え
た後、これに遊離基発生処理を施し該クロマンインデン
オリゴマーを前記高分子材料中で重合させることを特徴
とする耐放射線高分子組成物の製造方法。A coumaron-indene oligomer obtained by copolymerizing coumarons and indenes is added to a polymeric material, and then subjected to a free radical generation treatment to polymerize the chromanindene oligomer in the polymeric material. A method for producing a radiation-resistant polymer composition, the method comprising:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2601886A JPS62185706A (en) | 1986-02-10 | 1986-02-10 | Production of radiation-resistant polymer composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2601886A JPS62185706A (en) | 1986-02-10 | 1986-02-10 | Production of radiation-resistant polymer composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62185706A true JPS62185706A (en) | 1987-08-14 |
Family
ID=12181956
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2601886A Pending JPS62185706A (en) | 1986-02-10 | 1986-02-10 | Production of radiation-resistant polymer composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62185706A (en) |
-
1986
- 1986-02-10 JP JP2601886A patent/JPS62185706A/en active Pending
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