JPS5938984B2 - Method for manufacturing silane-modified ethylene polymer molded products - Google Patents
Method for manufacturing silane-modified ethylene polymer molded productsInfo
- Publication number
- JPS5938984B2 JPS5938984B2 JP55097650A JP9765080A JPS5938984B2 JP S5938984 B2 JPS5938984 B2 JP S5938984B2 JP 55097650 A JP55097650 A JP 55097650A JP 9765080 A JP9765080 A JP 9765080A JP S5938984 B2 JPS5938984 B2 JP S5938984B2
- Authority
- JP
- Japan
- Prior art keywords
- ethylene polymer
- silane
- modified ethylene
- carboxylic acid
- molded article
- 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
- 229920000573 polyethylene Polymers 0.000 title claims description 47
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 title claims description 27
- 238000000034 method Methods 0.000 title claims description 11
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 15
- 238000004132 cross linking Methods 0.000 claims description 13
- -1 polyethylene Polymers 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 9
- 238000000465 moulding Methods 0.000 claims description 8
- 239000004698 Polyethylene Substances 0.000 claims description 7
- 238000001125 extrusion Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 5
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims description 2
- 239000004711 α-olefin Substances 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims 2
- 239000003054 catalyst Substances 0.000 description 13
- 239000004594 Masterbatch (MB) Substances 0.000 description 8
- 238000009833 condensation Methods 0.000 description 7
- 230000005494 condensation Effects 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 150000001735 carboxylic acids Chemical class 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910000077 silane Inorganic materials 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 229920001684 low density polyethylene Polymers 0.000 description 3
- 239000004702 low-density polyethylene Substances 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- 229910000831 Steel Inorganic materials 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
- 230000002378 acidificating effect Effects 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 239000012975 dibutyltin dilaurate Substances 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
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 150000003606 tin compounds Chemical class 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-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
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- 239000004709 Chlorinated polyethylene Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical class [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- PNOXNTGLSKTMQO-UHFFFAOYSA-L diacetyloxytin Chemical compound CC(=O)O[Sn]OC(C)=O PNOXNTGLSKTMQO-UHFFFAOYSA-L 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- 229920005648 ethylene methacrylic acid copolymer Polymers 0.000 description 1
- 229920006244 ethylene-ethyl acrylate Polymers 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000012438 extruded product Nutrition 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
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000003348 petrochemical agent Substances 0.000 description 1
- 239000002689 soil Substances 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
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
【発明の詳細な説明】
本発明は、シラン変性エチレン系重合体成形品の製造法
に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a silane-modified ethylene polymer molded article.
更に詳しくは、シラン変性エチレン系重合体を有機錫化
合物の存在下で押出成形することからなる水架橋性のシ
ラン変性エチレン系重合体成形品の製造法に関する。エ
チレン系重合体をシランと反応させて変形し、このシラ
ン変性エチレン系重合体をシラノール縮合触媒の存在下
で押出成形し、成形された成形品を水と接触させること
によつて分子間架橋を生ぜしめ、シラン架橋エチレン系
重合体成形品を製造することは、例えば英国特許第１２
３４０３４号明細書などに記載される如く公知である。More specifically, the present invention relates to a method for producing a water-crosslinkable silane-modified ethylene polymer molded article, which comprises extrusion molding a silane-modified ethylene polymer in the presence of an organotin compound. The ethylene polymer is deformed by reacting with silane, the silane-modified ethylene polymer is extruded in the presence of a silanol condensation catalyst, and the molded product is brought into contact with water to create intermolecular crosslinks. The production of silane-crosslinked ethylene polymer moldings is described, for example, in British Patent No. 12.
It is publicly known as described in the specification of No. 34034 and the like.
このような架橋方法は、従来の有機過酸化物による架橋
方法と比較して設備費が安く、また成形条件についての
制限が少なく、操作し易いことが特徴であり、このため
各種の成形法に適用されている。This type of crosslinking method is characterized by lower equipment costs, fewer restrictions on molding conditions, and easier operation than conventional crosslinking methods using organic peroxides, and is therefore suitable for various molding methods. Applied.
例えば、電力用の架橋ケーブルにおいても、シラン変性
エチレン系重合体を用いれば、従来の有機過酸化物によ
る架橋方法のときの狭い成形温度範囲（１２０〜１４０
℃）という厳しい制限からも解放され、普通の非架橋エ
チレン系重合体と同一の高温度下での成形が可能となり
、工業的にすぐれた方法として利用されるようになりつ
つある。このような架橋方法は、前記電力用ケーブル以
外にも、パイプ、異形押出品、フィルム、シート、中空
成形品、ネット、鋼板、鋼管などの被覆などにも利用で
きる。この電力ケーブルなどの成形品は、シラン変性エ
チレン系重合体とシラノール縮合触媒とを一定の割合で
押出機に供給し、前述の如き被覆物その他の形状に成形
することにより製造される。For example, if a silane-modified ethylene polymer is used in cross-linked power cables, it would be possible to use a narrow molding temperature range (120 to 140
It is freed from the severe limitation of 100°C (°C) and can be molded at the same high temperatures as ordinary non-crosslinked ethylene polymers, and is now being used as an excellent industrial method. Such a crosslinking method can be used for covering pipes, profile extrusions, films, sheets, blow molded products, nets, steel plates, steel pipes, etc., in addition to the above-mentioned power cables. Molded products such as power cables are produced by supplying a silane-modified ethylene polymer and a silanol condensation catalyst to an extruder at a constant ratio and molding them into the above-mentioned coating or other shapes.
シラＪノール縮合触媒としては、カルボン酸の各種金属
塩、有機金属化合物（チタン酸エステル、キレートなど
）、有機塩基（アミン類）および酸類（無機塩、有機脂
肪酸など）が知られており、これらの中で有機錫化合物
が成形後の架橋工程において、実用上十分な架橋速度を
与えるものとして、好んで用いられている。Various metal salts of carboxylic acids, organometallic compounds (titanate esters, chelates, etc.), organic bases (amines), and acids (inorganic salts, organic fatty acids, etc.) are known as Sila J-Nol condensation catalysts. Among these, organic tin compounds are preferably used as they provide a practically sufficient crosslinking rate in the crosslinking step after molding.
しかるに、有機錫化合物のような活性の高い縮合触媒を
用いた場合には、押出加工時に押出機中で早期の縮合反
応が起り、成形品の表面に凹凸が形成される現象を生ず
る。However, when a highly active condensation catalyst such as an organotin compound is used, an early condensation reaction occurs in the extruder during extrusion processing, resulting in the formation of irregularities on the surface of the molded product.
かかる現象は、一般に凸部の形成として観察されること
が多く、「フッ」、「ゲル」、［フイツシユアイ」など
と当業者間で呼ばれている。そして、この現象は、押出
速度が遅い場合、換言すれば押出機中での滞留時間が長
い場合に顕著にみられ、このような現象の発生は電力ケ
ーブルその他の成形品にとつて、製品の致命的な欠陥と
なる。本発明者らは、有機錫化合物の存在下でシラン変
性エチレン系重合体を押出成形するに際してみられるこ
のような問題点を解決すべく種々検討の結果、カルボン
酸を共存させて押出すことにより、押出成形品の表面に
形成される凹凸を効果的に抑制し得ることを見出し、こ
こに本発明を完成するに至つた。Such a phenomenon is generally observed as the formation of convex portions, and is referred to by those skilled in the art as "fluff", "gel", "fish eye", etc. This phenomenon is noticeable when the extrusion speed is slow, or in other words, when the residence time in the extruder is long, and the occurrence of this phenomenon is detrimental to the quality of power cables and other molded products. This is a fatal flaw. The present inventors have conducted various studies in order to solve these problems that occur when extruding a silane-modified ethylene polymer in the presence of an organotin compound. They discovered that it is possible to effectively suppress the unevenness formed on the surface of an extruded product, and have now completed the present invention.
前述の如く、カルボン酸は無機酸などと共にシラノール
縮合触媒として知られており、有機錫化合物に加えてカ
ルボン酸を加えた場合には、縮合反応は更に促進され、
表面凹凸の形成が更に増大することが予想されたのにも
かかわらず、顕著な成形品表面の凹凸形成抑制効果がみ
られ、しかも成形後の水による架橋反応においても、架
橋速度および架橋度の減少が殆んどみられないという効
果を奏する。As mentioned above, carboxylic acid is known as a silanol condensation catalyst along with inorganic acids, and when carboxylic acid is added in addition to an organic tin compound, the condensation reaction is further accelerated.
Although it was expected that the formation of surface irregularities would further increase, a remarkable effect of suppressing the formation of irregularities on the surface of the molded product was observed, and even in the crosslinking reaction with water after molding, the crosslinking rate and degree of crosslinking were significantly reduced. This has the effect that almost no decrease is observed.
本発明で用いられるシラン変性エチレン系重合体は、エ
チレン系重合体にシラン化合物を、好ましくは有機パー
オキサイドなどのフリーラジカル生成化合物の存在下で
、一般に約１４０℃以上の温度に加熱して反応させるこ
とにより得られる。The silane-modified ethylene polymer used in the present invention is prepared by reacting an ethylene polymer with a silane compound, preferably in the presence of a free radical-generating compound such as an organic peroxide, and generally heated to a temperature of about 140°C or higher. It can be obtained by
エチレン系重合体としては、例えば低密度乃至高密度ポ
リエチレン、エチレン一酢酸ビニル共重合体、エチレン
−エチルアクリレート共重合体、塩素化ポリエチレン、
エチレン−プロピレン共重合体、エチレン一１−ブテン
共重合体、エチレン一４−メチル−１−ベンゼン共重合
体およびこれらの混合物などが用いられる。これらのエ
チレン系重合体を変性させるシラン化合物は、一般式Ｒ
Ｒ′ＳｉＹ２（ここで、Ｒは一価の不飽和炭化水素基ま
たはハイドロカーボンオキシ基であり、Ｙは加水分解可
能な有機基であり、そしてＲ′は前記ＲまたはＹと同一
の基である）で表わされ、その代表的な例としてビニル
トリメトキシシプン、ビニルトリエトキシシランなどが
挙げられ、他の化合物についても当業者間で周知である
。シラノール縮合触媒としての有機錫化合物の代表的な
例としては、ジブチル錫ジラウレート、酢酸第一錫、オ
クタン酸第一錫などが挙げられる。Examples of ethylene polymers include low density to high density polyethylene, ethylene monovinyl acetate copolymer, ethylene-ethyl acrylate copolymer, chlorinated polyethylene,
Ethylene-propylene copolymers, ethylene-1-butene copolymers, ethylene-4-methyl-1-benzene copolymers, and mixtures thereof are used. The silane compound that modifies these ethylene polymers has the general formula R
R'SiY2 (wherein R is a monovalent unsaturated hydrocarbon group or hydrocarbonoxy group, Y is a hydrolyzable organic group, and R' is the same group as R or Y above) ), typical examples of which include vinyltrimethoxysilane and vinyltriethoxysilane, and other compounds are well known to those skilled in the art. Typical examples of organotin compounds as silanol condensation catalysts include dibutyltin dilaurate, stannous acetate, stannous octoate, and the like.
これらの有機錫化合物と共に用いられるカルボン酸とし
ては、脂肪族カルボン酸、芳香族カルボン酸、不飽和カ
ルボン酸などの低分子量カルボン酸やその半エステルの
他に、不飽和カルボン酸の重合体または共重合体なども
有効に使用される。具体的には、しゆう酸、クエン酸、
アジピン酸、ステアリン酸、フタル酸、アクリル酸、メ
タクリル酸、エチレン−メタクリル酸共重合体などが挙
げられる。これらのカルボン酸の添加量としては、シラ
ン変性ポリエチレン１０ｋｇに対し約０．００１モル以
下では成形品表面の凹凸形成抑制効果が未だ十分ではな
く、一方約０．１モル以上では成形品を水分で架橋させ
た場合の架橋反応速度を低下させるようになる。Carboxylic acids used with these organotin compounds include low molecular weight carboxylic acids such as aliphatic carboxylic acids, aromatic carboxylic acids, and unsaturated carboxylic acids, as well as their half esters, as well as polymers or copolymers of unsaturated carboxylic acids. Polymers and the like are also effectively used. Specifically, oxalic acid, citric acid,
Examples include adipic acid, stearic acid, phthalic acid, acrylic acid, methacrylic acid, and ethylene-methacrylic acid copolymer. If the amount of these carboxylic acids added is less than about 0.001 mol per 10 kg of silane-modified polyethylene, the effect of suppressing the formation of unevenness on the surface of the molded product will not be sufficient, whereas if it is more than about 0.1 mol, the molded product will not absorb moisture. This reduces the crosslinking reaction rate when crosslinking occurs.
そして、カルボン酸の添加は、シラン変性エチレン系重
合体を押出成形する際でもよいが、予めカルボン酸を含
むマスターバツチを調製して加えた方が作業土好ましく
、実際には有機錫化合物や各種安定剤と共にエチレン系
重合体のマスターバツチの形にして加えられる。本発明
においては、前記のシラン変性エチレン系重合体は、こ
れと相溶性のあるエチレン系重合体とブレンドして用い
ることもできる。Carboxylic acid may be added during extrusion molding of the silane-modified ethylene polymer, but it is preferable to prepare a master batch containing carboxylic acid in advance and add it to the working soil. It is added in the form of a masterbatch of ethylene polymer along with the agent. In the present invention, the silane-modified ethylene polymer can also be used in a blend with an ethylene polymer that is compatible with the silane-modified ethylene polymer.
ブレンドされるエチレン系重合体としては、シラン変性
に用いられたエチレン系重合体と同様の範喘のものが用
いられる。そして、押出成形された成形品が電力ケーブ
ル被覆などの場合には、耐熱性の低下を抑え、また被覆
後の伸びを向上させる意味から、低圧法乃至中圧法によ
つて製造された密度が０．９１０〜０．９４５ＬＡゴの
範囲のポリエチレンまたはエチレン一α−オレフイン共
重合体を用いることが好ましい。ブレンドされるエチレ
ン系重合体は、シラン変性エチレン系重合体約６０〜９
０重量部に対し約４０〜１０重量部の範囲内で用いられ
ることが好ましく、このブレンド比の範囲内では、耐熱
変形性を損うことなく、伸び率を向上させることができ
る。本発明によつて製造されるシラン変性エチレン系重
合体成形品は、水との接触により架橋される。As the ethylene polymer to be blended, those in the same range as the ethylene polymer used for silane modification are used. When the extruded molded product is used to cover power cables, etc., the density of the product manufactured by the low-pressure method to medium-pressure method is 0 to suppress the decrease in heat resistance and improve the elongation after coating. It is preferred to use polyethylene or ethylene-α-olefin copolymers having an LA of .910 to .945. The ethylene polymer to be blended is a silane-modified ethylene polymer of about 60 to 9
It is preferably used in an amount of about 40 to 10 parts by weight relative to 0 parts by weight, and within this blend ratio range, elongation can be improved without impairing heat deformation resistance. The silane-modified ethylene polymer molded article produced according to the present invention is crosslinked by contact with water.
架橋反応は、好ましくは成形品を温水中に浸漬すること
により行われるが、空気中の水分を利用する自然放置に
より架橋させることも可能である。そして、このシラン
変性エチレン系重合体成形品は、水による架橋性を殆ん
ど損うことなく、その表面平滑性を著しく改善させてい
る。次に、実施例について本発明を説明する。The crosslinking reaction is preferably carried out by immersing the molded article in hot water, but it is also possible to carry out the crosslinking reaction by leaving the molded article to stand naturally using moisture in the air. This silane-modified ethylene polymer molded article has significantly improved surface smoothness without substantially impairing crosslinkability with water. Next, the present invention will be explained with reference to examples.
実施例 １
高圧法による低密度ポリエチレン（密度０．９２０９／
０！１１メルト・インデツクス３．３９／１０分）１０
０部（重量、以下同じ）にビニルトリメトキシシラン２
．０部およびジクミルパーオキサイド０．２部を加え、
２２０℃で押出機から押出してシラン変性ポリエチレン
を製造した。Example 1 Low density polyethylene (density 0.9209/
0!11 Melt Index 3.39/10 minutes) 10
0 parts (weight, same below) to vinyltrimethoxysilane 2
．． Add 0 parts and 0.2 parts of dicumyl peroxide,
Silane-modified polyethylene was produced by extrusion from an extruder at 220°C.
これとは別に、前記低密度ポリエチレン１００部にシラ
ノール縮合触媒としてのジブチル錫ジラウレート１．０
部、老化防止剤（日本チバ・ガイギ社製品イルガノツク
ス１０１０）２．０部、銅害防止剤（アデカアーガス社
製品ＭＡＲＫＣＤＡ−１Ｍ）３．０部および後記表１に
示すカルボン酸の所定量を加え、バンバリーミキサ一で
混練して触媒マスターバツチを調製した。Separately, 1.0 parts of dibutyltin dilaurate as a silanol condensation catalyst was added to 100 parts of the low density polyethylene.
1 part, 2.0 parts of an anti-aging agent (Irganox 1010, manufactured by Nippon Ciba-Geigi Co., Ltd.), 3.0 parts of a copper damage inhibitor (MARKCDA-1M, manufactured by Adeka Argus Co., Ltd.), and the specified amount of carboxylic acid shown in Table 1 below were added. A catalyst masterbatch was prepared by kneading in a Banbury mixer.
このシラン変性ポリエチレン９５部および触媒マスター
バツチ５部をタンブラーミキサ一で混合し、混合物を９
０７ｎｍ径の押出機に供給し、温度２００℃、スクリユ
一回転数１３ｒｐＩｎで、外径】４ｍｍ１内径１０ｍｍ
のダイを通して円筒状に押出した。95 parts of this silane-modified polyethylene and 5 parts of the catalyst masterbatch were mixed in a tumbler mixer, and the mixture was mixed with 95 parts of the catalyst masterbatch.
07nm diameter extruder, temperature 200℃, screw rotation speed 13rpIn, outer diameter 4 mm 1 inner diameter 10 mm
It was extruded into a cylindrical shape through a die.
押出成形された円筒体表面の全面に激しく凹凸のあるも
のを評点５、成形品表面に凹凸の存在するものを評点３
、殆んど凹凸のないものを評点１とし、それらの中間と
評価されるものをそれぞれ評点４および２とする５点法
で表示すると、次の表１の如くになる。この結果に示さ
れるように、得られた成形品の表面には、殆んど凹凸が
存在していない。If the entire surface of the extruded cylindrical body is severely uneven, a rating of 5 will be given.If the molded product has irregularities on its surface, a rating of 3 will be given.
When expressed using a 5-point system in which those with almost no unevenness are given a score of 1, and those that are in the middle are given scores of 4 and 2, respectively, the results are as shown in Table 1 below. As shown in the results, there are almost no irregularities on the surface of the obtained molded product.
表１に示された円筒体を、８０℃の温水中で２４時間架
橋処理を行なつた後、１１０℃のキシレン中に２４時間
浸漬し、キシレン不溶分（ゲル分率）を測定したところ
、いずれも７５〜８２％の範囲内にあり、これはカルボ
ン酸を加えないで成形された円筒体について得られた値
の７８０１）とほぼ同じである。The cylindrical bodies shown in Table 1 were crosslinked in warm water at 80°C for 24 hours, then immersed in xylene at 110°C for 24 hours, and the xylene insoluble content (gel fraction) was measured. Both are in the range of 75-82%, which is approximately the same as the value 7801) obtained for the cylinder molded without the addition of carboxylic acid.
実施例 ２
実施例１で用いられた変性シラン変性ポリエチレン９５
部および触媒マスターバツチ５部に、低圧法で製造され
た低密度ポリエチレン（三井石油化学製品ネオゼツクス
ＮＺ−２０１５Ｈ；密度０．９２０９／〜、メルトイン
デツクス１．５９／１０分）５０部を加え、実施例１と
同じ条件で円筒状に押出した。Example 2 Modified silane-modified polyethylene 95 used in Example 1
Add 50 parts of low-density polyethylene (Mitsui Petrochemicals Neozex NZ-2015H; density 0.9209/~, melt index 1.59/10 min) produced by a low-pressure method to 1 part and 5 parts of the catalyst masterbatch, and conduct the experiment. It was extruded into a cylindrical shape under the same conditions as Example 1.
押出成形された円筒体表面の凹凸の存在量は、次の表２
の如くに評価された。この結果に示されるように、ステ
アリン酸添加量が０．１部（シラン変性ポリエチレンが
１９ｋｇのとき、カルボキシル基として３．５×１０−
３モノ（ハ）になると、表面凹凸形成抑制効果の低下が
みられる。表２に示された円筒体について、実施例１の
如くにキシレン不溶分（ゲル分率）を測定したところ、
いずれも５５〜６２％の範囲内にあり、これはカルボン
酸を加えないで成形された円筒体について得られた値の
５７％とほぼ同じである。The amount of unevenness on the surface of the extruded cylinder is shown in Table 2 below.
It was evaluated as follows. As shown in the results, the amount of stearic acid added was 0.1 part (when 19 kg of silane-modified polyethylene was used, 3.5 x 10-
When it comes to 3 monomers (c), a decrease in the effect of suppressing the formation of surface irregularities is observed. Regarding the cylinders shown in Table 2, the xylene insoluble content (gel fraction) was measured as in Example 1.
Both are in the range of 55-62%, which is approximately the same as the value of 57% obtained for cylinders formed without added carboxylic acid.
比較例 １実施例１において、触媒マスターバツチ中に
カルボン酸を加えず、あるいはカルボン酸以外の酸性物
質または他の物質を加え、円筒体を押出成形した。Comparative Example 1 In Example 1, a cylindrical body was extruded without adding carboxylic acid or adding an acidic substance or other substance other than carboxylic acid to the catalyst masterbatch.
結果は、次の表３に示される如く、成形品表面には多く
の凹凸が形されている。比較例 ２
実施例２において、触媒マスターバツチ中にカルボン酸
を加えず、あるいはカルボン酸以外の酸性物質または他
の物質を加え、円筒体を押出成形した。As shown in Table 3 below, the molded product surface had many irregularities. Comparative Example 2 In Example 2, a cylinder was extruded without adding carboxylic acid or adding an acidic substance or other substance other than carboxylic acid to the catalyst masterbatch.
Claims (1)
系重合体を押出成形するに際し、カルボン酸を共存させ
て押出すことを特徴とする水架橋性のシラン変性エチレ
ン系重合体成形品の製造法。 ２ カルボン酸をシラン変性エチレン系重合体１０ｋｇ
当りカルボキシル基として約０．００１〜０．１モルの
割合で添加する特許請求の範囲第１項記載のシラン変性
エチレン系重合体成形品の製造法。 ３ 有機錫化合物の存在下においてシラン変性エチレン
系重合体およびこれと相溶性を有するエチレン系重合体
の混合物を押出成形するに際し、カルボン酸を共存させ
て押出すことを特徴とする水架橋性のシラン変性エチレ
ン系重合体成形品の製造法。 ４ シラン変性エチレン系重合体と相溶性のあるエチレ
ン系重合体が中圧法乃至低圧法により製造された密度０
．９１０〜０．９４５ｇ／ｃｍ＾３のポリエチレンまた
はエチレン−α−オレフィン共重合体である特許請求の
範囲第３項記載のシラン変性エチレン系重合体成形品の
製造法。 ５ カルボン酸をシラン変性エチレン系重合体１０ｋｇ
当りカルボキシル基として約０．００１〜０．１モルの
割合で添加する特許請求の範囲第３項記載のシラン変性
エチレン系重合体成形品の製造法。[Claims] 1. Molding of a water-crosslinkable silane-modified ethylene polymer, characterized in that when extruding the silane-modified ethylene polymer in the presence of an organotin compound, the extrusion is carried out in the presence of a carboxylic acid. method of manufacturing the product. 2 Convert carboxylic acid into 10 kg of silane-modified ethylene polymer.
The method for producing a silane-modified ethylene polymer molded article according to claim 1, wherein the silane-modified ethylene polymer molded article is added in an amount of about 0.001 to 0.1 mole as carboxyl group. 3. A water-crosslinking method characterized by extruding a mixture of a silane-modified ethylene polymer and an ethylene polymer compatible therewith in the presence of an organotin compound, in the presence of a carboxylic acid. A method for producing silane-modified ethylene polymer molded products. 4 An ethylene polymer compatible with the silane-modified ethylene polymer is manufactured by a medium pressure method or a low pressure method and has a density of 0.
．． The method for producing a silane-modified ethylene polymer molded article according to claim 3, which is a polyethylene or ethylene-α-olefin copolymer having a weight of 910 to 0.945 g/cm^3. 5 Convert carboxylic acid into 10 kg of silane-modified ethylene polymer
4. The method for producing a silane-modified ethylene polymer molded article according to claim 3, wherein the silane-modified ethylene polymer molded article is added in an amount of about 0.001 to 0.1 mole as carboxyl group.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP55097650A JPS5938984B2 (en) | 1980-07-18 | 1980-07-18 | Method for manufacturing silane-modified ethylene polymer molded products |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP55097650A JPS5938984B2 (en) | 1980-07-18 | 1980-07-18 | Method for manufacturing silane-modified ethylene polymer molded products |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5723650A JPS5723650A (en) | 1982-02-06 |
| JPS5938984B2 true JPS5938984B2 (en) | 1984-09-20 |
Family
ID=14197963
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP55097650A Expired JPS5938984B2 (en) | 1980-07-18 | 1980-07-18 | Method for manufacturing silane-modified ethylene polymer molded products |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5938984B2 (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59207849A (en) * | 1983-05-07 | 1984-11-26 | Hitachi Cable Ltd | Drawing machine for parent material of optical fiber |
| JPS608345A (en) * | 1983-06-28 | 1985-01-17 | Sekisui Chem Co Ltd | Polyolefin resin composition |
| JPS61127629A (en) * | 1984-11-26 | 1986-06-14 | Furukawa Electric Co Ltd:The | Hot drawing method of glass |
| JPH0730229B2 (en) * | 1985-11-06 | 1995-04-05 | 住友ベ−クライト株式会社 | Method for producing silane-modified ethylene polymer molded article |
| GB8913743D0 (en) * | 1989-06-15 | 1989-08-02 | Bicc Plc | Manufacture of extruded products |
| US5211730A (en) * | 1989-12-15 | 1993-05-18 | Sumitomo Electric Industries, Ltd. | Method for heating glass body |
| MX2010000556A (en) * | 2007-07-13 | 2010-03-15 | Dow Global Technologies Inc | In-situ method of generating through ring-closing dehydration reactions of organic compounds water for moisture crosslinking of polyolefins. |
| JP5609780B2 (en) * | 2011-03-08 | 2014-10-22 | 日立金属株式会社 | Electric wires and cables using silane-crosslinked polyolefin compositions |
| EP2690115B1 (en) * | 2012-07-24 | 2018-02-21 | Borealis AG | Slow partial cross-linking polyolefin composition for improving disinfectant resistance of an article |
-
1980
- 1980-07-18 JP JP55097650A patent/JPS5938984B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5723650A (en) | 1982-02-06 |
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