JPS581664B2 - Crosslinking method for organic polymers - Google Patents
Crosslinking method for organic polymersInfo
- Publication number
- JPS581664B2 JPS581664B2 JP53061211A JP6121178A JPS581664B2 JP S581664 B2 JPS581664 B2 JP S581664B2 JP 53061211 A JP53061211 A JP 53061211A JP 6121178 A JP6121178 A JP 6121178A JP S581664 B2 JPS581664 B2 JP S581664B2
- Authority
- JP
- Japan
- Prior art keywords
- extruder
- silyl
- hopper
- polymer
- supplied
- 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.)
- Expired
Links
- 229920000620 organic polymer Polymers 0.000 title claims description 18
- 238000000034 method Methods 0.000 title claims description 16
- 238000004132 cross linking Methods 0.000 title claims description 9
- 239000003707 silyl modified polymer Substances 0.000 claims description 17
- 239000003054 catalyst Substances 0.000 claims description 13
- 238000009833 condensation Methods 0.000 claims description 13
- 230000005494 condensation Effects 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 12
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 10
- 230000003712 anti-aging effect Effects 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 6
- 238000002347 injection Methods 0.000 claims description 4
- 239000007924 injection Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000011347 resin Substances 0.000 claims description 4
- 229920005989 resin Polymers 0.000 claims description 4
- 238000004581 coalescence Methods 0.000 claims 1
- 238000007796 conventional method Methods 0.000 claims 1
- 229920000098 polyolefin Polymers 0.000 claims 1
- 239000008188 pellet Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 6
- 239000004020 conductor Substances 0.000 description 6
- -1 polyethylene Polymers 0.000 description 6
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 6
- 238000001125 extrusion Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 229920001684 low density polyethylene Polymers 0.000 description 3
- 239000004702 low-density polyethylene Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 2
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-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
- 239000000654 additive Substances 0.000 description 1
- 230000003679 aging effect Effects 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 150000001734 carboxylic acid salts Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- 229920006228 ethylene acrylate copolymer Polymers 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/375—Plasticisers, homogenisers or feeders comprising two or more stages
- B29C48/38—Plasticisers, homogenisers or feeders comprising two or more stages using two or more serially arranged screws in the same barrel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/05—Filamentary, e.g. strands
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/06—Rod-shaped
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
- Processes Specially Adapted For Manufacturing Cables (AREA)
Description
【発明の詳細な説明】 本発明は有機重合体の架橋方法の改良に関する。[Detailed description of the invention] The present invention relates to improvements in methods for crosslinking organic polymers.
近時、加水分解可能な有機基を有するシリル基を含む化
合物で変性されたシリル変性重合体を、シロキサン縮合
触媒の存在下に水分と接触させることにより、架橋結合
した有機重合体から成る成形品を得る技術が開発された
。Recently, a silyl-modified polymer modified with a compound containing a silyl group having a hydrolyzable organic group is brought into contact with moisture in the presence of a siloxane condensation catalyst to create a molded product made of a cross-linked organic polymer. A technology has been developed to obtain
一般にこのような架橋方法の実施にあたっては、一旦、
加熱によりシリル変性重合体を形成する配合組成物をス
クリュー押出機に供給して反応させ、シリル変性有機重
合体のペレットを得、これとは別に、シロキサン縮合触
媒と有機重合体とを別工程でスクリュー押出機に供給し
て、シロキサン縮合触媒を含有する有機重合体ペレット
を製造し、これらのペレットを所定の比率でブレンドし
たものを更に他の押出機に供給して成形品を得、これを
水分と接触させてシリル変成重合体を架橋させる方法が
採られている。Generally, when implementing such a crosslinking method,
A blended composition that forms a silyl-modified polymer by heating is fed to a screw extruder and reacted to obtain pellets of a silyl-modified organic polymer. A screw extruder is fed to produce organic polymer pellets containing a siloxane condensation catalyst, and a blend of these pellets at a predetermined ratio is further fed to another extruder to obtain a molded product. A method of crosslinking a silyl-modified polymer by contacting it with moisture has been adopted.
しかるにこのような従来の製法では、ペレット製造のた
めの別工程を必要とするうえに、成形前にシリル変成重
合体が吸湿して変質してしまう虞れがあった。However, such conventional production methods require a separate process for pellet production, and there is a risk that the silyl-modified polymer may absorb moisture and deteriorate in quality before molding.
このような難点を回避するため、シリル変性重合体を製
造する工程において、そのスクリュー押出機の溶融域以
降の部位でシリンダー又はスクリューに設けた液体注入
孔からシロキサン縮合触媒を注入して一工程で成形する
方法（特開昭５０−１３５１３８号公報）や、加熱する
ことによりシリル変性重合体を形成する配合組成物と共
に、所定量のシロキサン縮合触媒をホツパーに供給して
一工程で成形する方法（特開昭５１−８２３６１号公報
）が提案されている。In order to avoid such difficulties, in the process of manufacturing silyl-modified polymers, a siloxane condensation catalyst is injected from the liquid injection hole provided in the cylinder or screw in the part after the melting zone of the screw extruder, and the siloxane condensation catalyst is injected in one step. A molding method (Japanese Unexamined Patent Publication No. 135138/1982), a method of molding in one step by supplying a predetermined amount of a siloxane condensation catalyst to a hopper together with a blended composition that forms a silyl-modified polymer by heating ( Japanese Unexamined Patent Publication No. 51-82361) has been proposed.
しかるにこのような方法では、前者にあっては有機重合
体の量に対してシロキサン縮合触媒の使用量が微量であ
るため混合不充分となり易く、これを回避するためには
、押出機のスクリューのＬ／Ｄを大きくとる必要があり
、構造上の無理が生ずる虞れが生ずる。However, in the former method, the amount of siloxane condensation catalyst used is small relative to the amount of organic polymer, which tends to result in insufficient mixing. To avoid this, it is necessary to adjust the screw of the extruder. It is necessary to take a large L/D, and there is a risk that structural unreasonableness will occur.
更に、熱老化特性改良のために老化防止剤を配合した場
合には、遊離基発生剤の分解により生じた遊離基が老化
防止剤と反応してシリル変成重合体の生成が阻害される
という欠点がある。Furthermore, when an antiaging agent is added to improve heat aging properties, the free radicals generated by decomposition of the free radical generator react with the antiaging agent, inhibiting the formation of silyl-modified polymers. There is.
また、後者にあっては押出機中でシリル変性した有機重
合体とシロキサン縮合触媒とが高温下で長時間混在する
ため、有機重合体の含有水分により架橋反応が進行する
虞れがあり、押出物の外観不良を惹起させる懸念がある
。In addition, in the latter case, since the silyl-modified organic polymer and the siloxane condensation catalyst coexist for a long time at high temperatures in the extruder, there is a risk that the crosslinking reaction will proceed due to the moisture content of the organic polymer. There is a concern that it may cause defects in the appearance of objects.
更に、いずれの場合においても、シリル変性のために必
要な温度は２２０℃程度の高温であり、一方押出最適温
度は、１８０℃以下であるため、一旦上昇した重合体温
度を押出温度にまで低下させるために、更にスクリュー
を長大にする必要があり、この点からも構造的な無理が
生じる虞れが生ずる。Furthermore, in any case, the temperature required for silyl modification is as high as about 220°C, while the optimum extrusion temperature is 180°C or lower, so the polymer temperature, once raised, must be lowered to the extrusion temperature. In order to do so, it is necessary to further increase the length of the screw, and this also poses a risk of structural strain.
本発明は以上のような従来の難点を解消すべく鋭意研究
の結果なされたもので、加熱することによりシリル変性
重合体を形成する配合組成物を常法によりスクリュー押
出機のホツパーに供給し、次いで加熱混合によりシリル
変性重合体を押出す方法において、前記スクリュー押出
機は、ホツパーを備えた第１のスクリュー押出機の先端
を、液体注入口を備えた第２の押出機の後端のシリンダ
ーに穿設した樹脂供給孔に接続させて成り、シリル変性
重合体を形成する配合組成物は、第１の押出機の後端に
形成されたホツパーから供給し、第２の押出機のホツパ
ーからは、シロキサン縮合触媒と老化防止剤とを含有す
る溶液を供給するものとし、かくして得られた押出物を
水分に接触させることを特徴とする有機重合体の架橋方
法に関するものである。The present invention was made as a result of intensive research in order to solve the above-mentioned conventional difficulties, and consists of supplying a blended composition that forms a silyl-modified polymer by heating to a hopper of a screw extruder in a conventional manner, In the method of extruding the silyl-modified polymer by heating and mixing, the screw extruder is configured such that the tip of the first screw extruder equipped with a hopper is connected to the cylinder at the rear end of the second extruder equipped with a liquid inlet. The blended composition forming the silyl-modified polymer is supplied from the hopper formed at the rear end of the first extruder, and is connected to the hopper of the second extruder. relates to a method for crosslinking organic polymers, characterized in that a solution containing a siloxane condensation catalyst and an antiaging agent is supplied, and the extrudate thus obtained is brought into contact with moisture.
本発明に使用する加熱することによりシリル変性重合体
を形成する配合組成物は、有機重合体１００重量部と加
水分解可能な基を有するシリル基を含む化合物の０．５
〜４重量部、遊離基発生剤の０．０３〜０．５重量部好
ましくは０．０５〜０．３重量部から成っている。The composition used in the present invention, which forms a silyl-modified polymer by heating, consists of 100 parts by weight of an organic polymer and 0.5 parts by weight of a compound containing a silyl group having a hydrolyzable group.
~4 parts by weight, 0.03 to 0.5 parts by weight, preferably 0.05 to 0.3 parts by weight of free radical generator.
本発明の対象となる有機重合体としては、例えばポリエ
チレン、ポリプロピレン、エチレンープロピレンコポリ
マー、エチレンープロピレンターポリマー、エチレン−
酢酸ビニル共重合体、エチレンーアクリレート共重合体
、ポリ塩化ビニル、塩化ビニル共重合体等がある。Examples of organic polymers to be used in the present invention include polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-propylene terpolymer, and ethylene-propylene copolymer.
Examples include vinyl acetate copolymer, ethylene-acrylate copolymer, polyvinyl chloride, vinyl chloride copolymer, and the like.
また、加水分解可能な基を有するシリル基を含む化合物
としては、例えばビニルトリメトキシシラン（ＶＴＭＯ
Ｓ）、ビニルトリエトキシシラン（ＶＴＥＯＳ） 等の
ビニルトリアルコキシシラン化合物がある。In addition, as a compound containing a silyl group having a hydrolyzable group, for example, vinyltrimethoxysilane (VTMO
There are vinyltrialkoxysilane compounds such as S) and vinyltriethoxysilane (VTEOS).
また有離基発生剤としては、ジクミルパーオキサイド（
ＤＣＰ）、ペンゾイルパーオキサイド、ジターシャリー
プチルパーオキサイドの如き有機過酸化物、アゾビスイ
ソブチロニトリルの如きアゾ化合物等がある。In addition, dicumyl peroxide (
DCP), organic peroxides such as penzoyl peroxide and ditertiary butyl peroxide, and azo compounds such as azobisisobutyronitrile.
シロキサン縮合触媒としては、ジプチル錫ジラウレート
（ＤＢＴＤＬ’）、オクタン酸第一錫、ナフテン酸コバ
ルト等のカルボン酸塩、エチルアミン、ジプチルアミン
、ヘキシルアミン等の有機塩基、無機酸および脂肪酸等
がある。Examples of the siloxane condensation catalyst include carboxylic acid salts such as diptyltin dilaurate (DBTDL'), stannous octoate, and cobalt naphthenate, organic bases such as ethylamine, diptylamine, and hexylamine, inorganic acids, and fatty acids.
更に、老化防止剤としては、３，５−ジｔ−ブチルー４
ヒドロキシフエニルプ口ピオネート、４，４−チオビス
−３−メチル−６−ｔ−プチルフェノール、１，１．３
−トリスー１，２メチル−４一ヒドロキシ−５−ｔ−プ
チルフエニルーブタン、１，３．５−トリメチル−２．
４．６−トリスー３，５−ジｔ−ブチルー４−ヒドロキ
シベンジルベンゼン等がある。Furthermore, as an anti-aging agent, 3,5-di-t-butyl-4
Hydroxyphenyl pionate, 4,4-thiobis-3-methyl-6-t-butylphenol, 1,1.3
-tris-1,2-methyl-4-hydroxy-5-t-butylphenyl-butane, 1,3,5-trimethyl-2.
Examples include 4,6-tris-3,5-di-t-butyl-4-hydroxybenzylbenzene.
以下、図面につき更に本発明の詳細を説明する。The present invention will be further explained in detail below with reference to the drawings.
Ｌ／Ｄ＝２０の第１のスクリュー押出機１の押出機のシ
リンダーの先端部は、Ｌ／Ｄ＝１４の第２のスクリュー
押出機２のシリンダーの後端に設けた樹脂供給孔３に接
続されており、また第１のスクリュー押出機１の後端部
には、ホッパ−４が設けられており、第２の押出機の後
端には、液体注入口５が設けられている。The tip of the extruder cylinder of the first screw extruder 1 with L/D = 20 is connected to the resin supply hole 3 provided at the rear end of the cylinder of the second screw extruder 2 with L/D = 14. A hopper 4 is provided at the rear end of the first screw extruder 1, and a liquid inlet 5 is provided at the rear end of the second extruder.
また、第１の押出機１のホッパ−４には攪拌羽根６の先
端に注入孔７を有する計量注入器８が挿入されている。Further, a metering injector 8 having an injection hole 7 at the tip of a stirring blade 6 is inserted into the hopper 4 of the first extruder 1 .
而して、このように構成された押出機９により本発明を
実施するにあたっては、第１の押出機１のシリンダーの
供給領域の温度を１６０〜１８０℃に、反応領域の温度
を２１０〜２２０℃に、第２の押出機のシリンダーの温
度を１５０〜１７０℃に設定すると共に、第１の押出機
１のホッパー４に、ポリエチレンの如き有機重合体のペ
レットを供給し、また計量注入器８からは、前記ペレツ
トと所定の比率で、加水分解可能な基を有するシリル基
を含む化合物と有離基発生剤との混合溶液を供給し、ス
クリュー１０を駆動させてこれらの組成物を、反応領域
を経て第２の押出機２の樹脂供給孔３に送入する。Therefore, when carrying out the present invention using the extruder 9 configured as described above, the temperature of the supply area of the cylinder of the first extruder 1 is set to 160 to 180°C, and the temperature of the reaction area is set to 210 to 220°C. ℃, the temperature of the cylinder of the second extruder is set at 150-170℃, and the hopper 4 of the first extruder 1 is fed with organic polymer pellets such as polyethylene, and the metering injector 8 Then, a mixed solution of a compound containing a silyl group having a hydrolyzable group and a free radical generator is supplied in a predetermined ratio to the pellets, and the screw 10 is driven to react these compositions. The resin is fed into the resin supply hole 3 of the second extruder 2 through the area.
而して、これらの組成物は、第１の押出機１の反応領域
を通過する過程でシリル基を含む化合物が有機重合体に
グラフト化反応し、架橋可能なシリル変性重合体となる
。When these compositions pass through the reaction zone of the first extruder 1, the silyl group-containing compound undergoes a grafting reaction with the organic polymer, resulting in a crosslinkable silyl-modified polymer.
第２の押出機２に移送されたシリル変性重合体には、液
体注入口５から所定比率でシラノール縮合触媒に老化防
止剤を冶解させた溶液が注入され、第２の押出機２中を
進行する過程で両者は充分に混練され、この混和物は例
えばクロスヘッド１１を経て連続してクロスヘッド１１
中を通過する導体１２上に円筒状に密接被覆されて絶縁
導体１３が得られる。The silyl-modified polymer transferred to the second extruder 2 is injected with a solution in which the antiaging agent is dissolved in the silanol condensation catalyst at a predetermined ratio from the liquid injection port 5, and the solution is injected into the silyl-modified polymer transferred to the second extruder 2. In the progressing process, both are sufficiently kneaded, and this mixture is continuously passed through the cross head 11, for example.
An insulated conductor 13 is obtained by closely covering the conductor 12 passing therethrough in a cylindrical manner.
このようにして得られた絶縁導体１３は、巻取りボビン
（図示せず）に巻取られた後、例えば温水中に浸漬して
架橋され、架橋絶縁被覆を有する絶線鍛線が得られる。The insulated conductor 13 thus obtained is wound onto a winding bobbin (not shown) and then immersed in, for example, warm water to be crosslinked, thereby obtaining a solid wire forged wire having a crosslinked insulation coating.
以上のような本発明方法によれば、シラノール縮合触媒
と老化防止剤とは、高温の反応印域を有する第１の押出
機と別個の第２の押出機Φで添加されるので、早期架橋
の原因となることがなく、また、シリル変成重合体の生
成反応を阻害するこトともない。According to the method of the present invention as described above, the silanol condensation catalyst and anti-aging agent are added in the first extruder having a high temperature reaction zone and the separate second extruder Φ, so that early crosslinking is prevented. Furthermore, it does not inhibit the production reaction of the silyl-modified polymer.
なお、シラノール縮合触媒と老化防止剤の配合量は、前
者については有機重合体１００重量部あたり０．０１〜
０．３重量部、後者については有機重合体１００重量部
あたり０．０５〜０．３重量部であることが望ましい。The blending amount of the silanol condensation catalyst and anti-aging agent is 0.01 to 100 parts by weight of the organic polymer for the former.
The latter is preferably 0.05 to 0.3 parts by weight per 100 parts by weight of the organic polymer.
次に実施例について記載する。Next, examples will be described.
実施例
低密度ポリエチレンペレットと、ＶＴＭＯＳ ：ＤＣＰ
＝１ ： ０．０５の割合でＶＴＭＯＳにＤＣＰを溶解
させた溶液とを、低密度ポリエチレンペレソト１００重
量部あたり、前記の溶液１．１６重量部ノ割合で、前述
の押出機（Ｌ／Ｄ＝２０） のホッパー４に供給し、ス
クリュー１０を回転させて、第２の押出機（ Ｌ／Ｄ＝
１４）に移送すると共に、第２の押出機２、液体注入口
５から、ＤＢＴＤＬに４，４′−チオビス−３−メチル
−６−ｔ−ブチルフェノールを１：４の割合で溶解させ
た溶液を、第１の押出機の低密度ポリエチレン１００重
量部あたり０．２５重量部の割合で供給し、クロスヘッ
ド１１から、連続して走行する撚線導体上に押出被覆し
た。Example low density polyethylene pellets and VTMOS: DCP
=1: A solution of DCP dissolved in VTMOS at a ratio of 0.05 was added to the extruder (L/D) at a ratio of 1.16 parts by weight of the above solution per 100 parts by weight of low density polyethylene = 20) is supplied to the hopper 4 of the second extruder (L/D=
14), and from the second extruder 2, liquid inlet 5, a solution of 4,4'-thiobis-3-methyl-6-t-butylphenol dissolved in DBTDL at a ratio of 1:4 was added. , was supplied at a rate of 0.25 parts by weight per 100 parts by weight of low-density polyethylene in the first extruder, and extrusion coated onto a continuously running stranded wire conductor from the crosshead 11.
第１の押出機の反応領域の温度 ２２０℃第２の押
出機の温度 １８０℃得られた被覆導体
を、８０℃の温水中で２４時間加熱処理して得た架橋被
覆の特性は次の通りであった。Temperature of the reaction zone of the first extruder: 220°C Temperature of the second extruder: 180°C The properties of the crosslinked coating obtained by heat-treating the obtained coated conductor in 80°C hot water for 24 hours are as follows. Met.
なお、上表中比較例は、実施例と同一配合でポリエチレ
ンペレットと添加剤とを通常の単軸スクリューの押出機
のホツパーに供給してクロスヘッドから、連続して走行
する撚線導体上に押出被覆し、実施例と同一条件で架橋
させた架橋被覆物である。In addition, in the comparative example in the table above, polyethylene pellets and additives were fed into the hopper of an ordinary single-screw extruder with the same composition as in the example, and then passed from the crosshead onto a continuously running stranded conductor. This is a crosslinked coating that was extrusion coated and crosslinked under the same conditions as in the examples.
図面は、本発明の一実施例の説明図である。 The drawings are explanatory diagrams of one embodiment of the present invention.
Claims (1)
合組成物を、常法によりスクリュー押出機のホツパーに
供給し、次いで加熱混合によりシリル変性重合体を押出
す方法において、前記スクリュー押出機は、ホツパーを
備えた第１のスクリュー押出機の先端を液体注入孔を備
えた番２の押出機の後端のシリンダーに穿設した樹脂供
給孔に接続させて成り、シリル変性重合体を形成する配
合組成物は、第１の押出機の後端に形成されたホツパー
から供給し、第２の押出機のホツパーからは、シロキサ
ン縮合触媒と老化防止剤とを含有する溶液を供給するも
のとし、かくして得られた押出物を水分に接触させるこ
とを特徴とする有機重合体の架橋方法。 ２ 有機重合体は、オレフイン系重合体であることを特
徴とする特許請求の範囲第１項記載の有機重合体の架橋
方法。[Scope of Claims] 1. A method in which a blended composition that forms a silyl-modified polymer by heating is supplied to a hopper of a screw extruder by a conventional method, and then the silyl-modified polymer is extruded by heating and mixing, The screw extruder is constructed by connecting the tip of a first screw extruder equipped with a hopper to a resin supply hole bored in a cylinder at the rear end of a second extruder equipped with a liquid injection hole. The blended composition forming the coalescence is supplied from a hopper formed at the rear end of the first extruder, and a solution containing a siloxane condensation catalyst and an antiaging agent is supplied from the hopper of the second extruder. A method for crosslinking organic polymers, characterized in that the extrudate thus obtained is brought into contact with moisture. 2. The method for crosslinking an organic polymer according to claim 1, wherein the organic polymer is an olefin polymer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP53061211A JPS581664B2 (en) | 1978-05-23 | 1978-05-23 | Crosslinking method for organic polymers |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP53061211A JPS581664B2 (en) | 1978-05-23 | 1978-05-23 | Crosslinking method for organic polymers |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS54152064A JPS54152064A (en) | 1979-11-29 |
| JPS581664B2 true JPS581664B2 (en) | 1983-01-12 |
Family
ID=13164629
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP53061211A Expired JPS581664B2 (en) | 1978-05-23 | 1978-05-23 | Crosslinking method for organic polymers |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS581664B2 (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS53629U (en) * | 1976-06-23 | 1978-01-06 | ||
| JPS5314750A (en) * | 1976-07-28 | 1978-02-09 | Furukawa Electric Co Ltd:The | Process of preparing silane-bridged polyolefin moldings |
-
1978
- 1978-05-23 JP JP53061211A patent/JPS581664B2/en not_active Expired
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS53629U (en) * | 1976-06-23 | 1978-01-06 | ||
| JPS5314750A (en) * | 1976-07-28 | 1978-02-09 | Furukawa Electric Co Ltd:The | Process of preparing silane-bridged polyolefin moldings |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS54152064A (en) | 1979-11-29 |
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