JPS5839170B2 - Method for manufacturing flame-retardant crosslinked molded products - Google Patents
Method for manufacturing flame-retardant crosslinked molded productsInfo
- Publication number
- JPS5839170B2 JPS5839170B2 JP53008017A JP801778A JPS5839170B2 JP S5839170 B2 JPS5839170 B2 JP S5839170B2 JP 53008017 A JP53008017 A JP 53008017A JP 801778 A JP801778 A JP 801778A JP S5839170 B2 JPS5839170 B2 JP S5839170B2
- Authority
- JP
- Japan
- Prior art keywords
- polyolefin
- flame retardant
- grafted
- silane
- retardant
- 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
- 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 title claims description 36
- 239000003063 flame retardant Substances 0.000 title claims description 22
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 238000000034 method Methods 0.000 title 1
- 229920000098 polyolefin Polymers 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 13
- 229920001112 grafted polyolefin Polymers 0.000 claims description 12
- 150000004756 silanes Chemical class 0.000 claims description 9
- 150000003254 radicals Chemical class 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 6
- 238000009833 condensation Methods 0.000 claims description 6
- 230000005494 condensation Effects 0.000 claims description 6
- -1 polyethylene Polymers 0.000 claims description 6
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 claims description 6
- 125000000962 organic group Chemical group 0.000 claims description 5
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 4
- 238000004132 cross linking Methods 0.000 claims description 4
- 229910000077 silane Inorganic materials 0.000 claims description 4
- 238000001125 extrusion Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims 1
- 229920000573 polyethylene Polymers 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000008188 pellet Substances 0.000 description 6
- 239000004594 Masterbatch (MB) Substances 0.000 description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 239000012975 dibutyltin dilaurate Substances 0.000 description 3
- GVYLCNUFSHDAAW-UHFFFAOYSA-N mirex Chemical compound ClC12C(Cl)(Cl)C3(Cl)C4(Cl)C1(Cl)C1(Cl)C2(Cl)C3(Cl)C4(Cl)C1(Cl)Cl GVYLCNUFSHDAAW-UHFFFAOYSA-N 0.000 description 3
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 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
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000000694 effects Effects 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
- 239000005038 ethylene vinyl acetate Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 2
- YAOMHRRYSRRRKP-UHFFFAOYSA-N 1,2-dichloropropyl 2,3-dichloropropyl 3,3-dichloropropyl phosphate Chemical compound ClC(Cl)CCOP(=O)(OC(Cl)C(Cl)C)OCC(Cl)CCl YAOMHRRYSRRRKP-UHFFFAOYSA-N 0.000 description 1
- ANHAEBWRQNIPEV-UHFFFAOYSA-N 2-chloroethyl dihydrogen phosphate Chemical compound OP(O)(=O)OCCCl ANHAEBWRQNIPEV-UHFFFAOYSA-N 0.000 description 1
- QTHRIIFWIHUMFH-UHFFFAOYSA-N 3-chloropropyl dihydrogen phosphate Chemical compound OP(O)(=O)OCCCCl QTHRIIFWIHUMFH-UHFFFAOYSA-N 0.000 description 1
- YNHKPNMBYSPACL-UHFFFAOYSA-N Br.Br.Br.Br.CCCC Chemical compound Br.Br.Br.Br.CCCC YNHKPNMBYSPACL-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical class CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical class CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 1
- PQYJRMFWJJONBO-UHFFFAOYSA-N Tris(2,3-dibromopropyl) phosphate Chemical compound BrCC(Br)COP(=O)(OCC(Br)CBr)OCC(Br)CBr PQYJRMFWJJONBO-UHFFFAOYSA-N 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- SYKNUAWMBRIEKB-UHFFFAOYSA-N [Cl].[Br] Chemical compound [Cl].[Br] SYKNUAWMBRIEKB-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- DDTBPAQBQHZRDW-UHFFFAOYSA-N cyclododecane Chemical class C1CCCCCCCCCCC1 DDTBPAQBQHZRDW-UHFFFAOYSA-N 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
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- UJSSNDKVUQJEGE-UHFFFAOYSA-N dichloro propyl phosphate Chemical compound CCCOP(=O)(OCl)OCl UJSSNDKVUQJEGE-UHFFFAOYSA-N 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 229920006244 ethylene-ethyl acrylate Polymers 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 229920001179 medium density polyethylene Polymers 0.000 description 1
- 239000004701 medium-density polyethylene Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical class CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N phthalic anhydride Chemical class C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- AUHHYELHRWCWEZ-UHFFFAOYSA-N tetrachlorophthalic anhydride Chemical compound ClC1=C(Cl)C(Cl)=C2C(=O)OC(=O)C2=C1Cl AUHHYELHRWCWEZ-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
Description
【発明の詳細な説明】
本発明は、難燃性架橋成形品の製造方法に係わり、特Ｇ
こシラン架橋されたポリオレフィンベースの難燃性架橋
成形品の製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing flame-retardant crosslinked molded products, and
This invention relates to a method for producing flame-retardant crosslinked molded products based on silane crosslinked polyolefin.
加水分解し得る有機基をもつ不飽和シランをグラフト化
させたシラングラフト化ポリオレフィンは、常温におい
てもシラノール縮合触媒の存在下で加水架橋するところ
から、従来架橋ポリオレフィンの使用されていた多くの
分野で多用されつつある。Silane-grafted polyolefins, which are made by grafting unsaturated silanes with hydrolyzable organic groups, can be hydrolyzed and crosslinked in the presence of silanol condensation catalysts even at room temperature, making them useful in many fields where crosslinked polyolefins have traditionally been used. It is becoming widely used.
一般に、原子炉その他の重要な装置へ架橋ポリオレフィ
ンが、例えばケーブル絶縁として使用される場合には、
従来から難燃剤を配合して難燃化することが行なわれて
おり、この場合、臭素系又は臭素系と塩素系を併用した
難燃剤が、特にポリオレフィンに対する難燃効果が優れ
たものとして、かつまた、ノンドリップ性を付与する難
燃剤として賞用されている。Generally, when crosslinked polyolefins are used in nuclear reactors or other critical equipment, for example as cable insulation,
Conventionally, flame retardants have been blended to make flame retardant, and in this case, bromine-based or bromine- and chlorine-based flame retardants have been considered to have particularly excellent flame retardant effects on polyolefins, and It is also prized as a flame retardant that imparts non-drip properties.
しかるに、かかる臭素系の難燃剤は、グラフト化に先立
ってシラングラフト化すべきポリオレフィン混合物に配
合した場合、グラフト化反応を阻害して架橋度を低下さ
せるという難点があった。However, when such brominated flame retardants are added to a polyolefin mixture to be grafted with silane prior to grafting, they inhibit the grafting reaction and reduce the degree of crosslinking.
また、グラフト化反応終了後配合することも考えられる
が、例えばマスターバッチの形態で配合した場合、有効
量の臭素系難燃剤を配合するには、マスターバッチの添
加量を多くする必要があり、シラン架橋ポリオレフィン
がマスターバッチのベスのポリオレフィンに稀釈されて
架橋度が低下するという難点があった。It is also possible to mix it after the completion of the grafting reaction, but if it is mixed in the form of a masterbatch, for example, in order to mix an effective amount of brominated flame retardant, it is necessary to increase the amount of masterbatch added. There was a problem in that the silane crosslinked polyolefin was diluted with the base polyolefin of the masterbatch, reducing the degree of crosslinking.
本発明者等は、かかる難点を解消すべく研究をすすめた
結果、臭素系難燃剤は、グラフト化反応過程で分解し易
く、有離ラジカル発生剤を消費して不飽和シランのグラ
フト化反応を阻害するが、塩素系難燃剤では、このよう
なグラフト化反応の阻害反応は殆んど見られず、したが
って塩素系難燃剤をシラングラフト化すべきポリオレフ
ィンベスの混合物中に予じめ配合しておき、グラフト化
反応後補助的に臭素系難燃剤を添加することにより、充
分な難燃性を具備するシラン架橋されたポリオレフィン
ベースの架橋成形品が得られることを見出した。The present inventors carried out research to resolve these difficulties and found that brominated flame retardants are easily decomposed during the grafting reaction process, consuming free radical generators and inhibiting the grafting reaction of unsaturated silanes. However, with chlorine-based flame retardants, this kind of inhibition reaction of grafting reaction is hardly observed. It has been found that by supplementarily adding a brominated flame retardant after the grafting reaction, a silane-crosslinked polyolefin-based crosslinked molded article having sufficient flame retardancy can be obtained.
本発明は、かかる知見に基いてなされたもので、加水分
解し得る有機基をもつ不飽和シラン、遊離ラジカル発生
剤および塩素系難燃剤を含むポリオレフィンベースの混
合物を、押出機に供給し、前記押出機中で前記不飽和シ
ランをポリオレフィンへグラフト化させ、更にグラフト
化された前記ポリオレフィンベースの組成物に、更（こ
臭素系難燃剤を添加して押出成形し、しかる後シラノー
ル縮合触媒の存在下で前記グラフト化させたポリオレフ
ィンを、加水架橋せしめることを特徴とする難燃性架橋
成形品の製造方法を提供しようとするものである。The present invention was made based on this knowledge, and involves supplying a polyolefin-based mixture containing an unsaturated silane having a hydrolyzable organic group, a free radical generator, and a chlorinated flame retardant to an extruder, and The unsaturated silane is grafted to a polyolefin in an extruder, and the grafted polyolefin-based composition is further extruded with the addition of a brominated flame retardant, and then in the presence of a silanol condensation catalyst. The present invention aims to provide a method for producing a flame-retardant crosslinked molded article, which comprises subjecting the grafted polyolefin to crosslinking with hydrolysis.
本発明に使用する加水分解し得る有機基をもつ不飽和シ
ラン、遊離ラジカル発生剤およびポリオレフィンとして
は、例えば特公昭４８−１７１１号公報、特公昭５０−
３５９４０号公報、特公昭５１−２０２１０号公報に記
載された不飽和シラン、遊離ラジカル発生剤およびポリ
オレフィンを使用することができる。Examples of the unsaturated silane having a hydrolyzable organic group, the free radical generator, and the polyolefin used in the present invention include Japanese Patent Publication No. 48-1711, Japanese Patent Publication No. 50-1988,
Unsaturated silanes, free radical generators and polyolefins described in Japanese Patent Publication No. 35940 and Japanese Patent Publication No. 51-20210 can be used.
すなわち、本発明に使用される有機基をもつ不飽和シラ
ンとしては、例えばビニルトリメトキシシラン（ＶＴＭ
Ｏ８）、ビニルトリエトキシシラン（ＶＴＲＯ８）等が
あり、また遊離ラジカル発生剤としては、ジクミルパー
オキサイド（ＤＣＰ）、ジ−ｔ−ブチルパーオキサイド
、２・５−ジメチル−２・５−ジ（１−ブチルパーオキ
シ）ヘキシン−３等があり、ポリオレフィンとしては、
高密度、中密度あるいは低密度のポリエチレン、ポリプ
ロピレン、エチレン・プロピレンコポリマーエチレン・
プロピレン・ジエンターポリマー、エチレン・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等
がある。That is, as the unsaturated silane having an organic group used in the present invention, for example, vinyltrimethoxysilane (VTM
O8), vinyltriethoxysilane (VTRO8), etc., and free radical generators include dicumyl peroxide (DCP), di-t-butyl peroxide, 2,5-dimethyl-2,5-di( There are polyolefins such as 1-butylperoxy)hexyne-3,
High density, medium density or low density polyethylene, polypropylene, ethylene/propylene copolymer ethylene/
Examples include propylene-diene terpolymer, ethylene-vinyl acetate copolymer, and ethylene-ethyl acrylate copolymer.
また、シラノール縮合触媒としては、ジブチル錫ジラウ
レート（ＤＢＴＤＬ）、ジブチル錫ジアセテート（ＤＢ
ＴＤＡ）等がある。In addition, as silanol condensation catalysts, dibutyltin dilaurate (DBTDL), dibutyltin diacetate (DB
TDA) etc.
更に、本発明に使用する塩素系難燃剤としては、例えば
、塩素化パラフィン、パークロロペンタシクロデカン、
四塩化無水フタル酸、トリスクロロエチルホスフェート
、トリス（ジクロロプロピル）ホスフェート、トリスク
ロロプロピルホスフェート、トリスジクロロプロピル・
クロロプロピルホスフェート、ビスクロロプロピル・ジ
クロロプロピルホスフェート、ビスクロロプロピル・ク
ロロエチルホスフェート、ビスクロロエチル・ジクロ等
がある。Furthermore, examples of chlorinated flame retardants used in the present invention include chlorinated paraffin, perchloropentacyclodecane,
Tetrachlorophthalic anhydride, trischloroethyl phosphate, tris (dichloropropyl) phosphate, trischloropropyl phosphate, trisdichloropropyl
Examples include chloropropyl phosphate, bischloropropyl dichloropropyl phosphate, bischloropropyl chloroethyl phosphate, and bischloroethyl dichloro.
更に、本発明に使用する臭素系難燃剤としては、例えば
、含臭素ポリオール、四臭化ビスフェノール、四臭化エ
タン、四臭化ブタン、四臭化プロパン、大奥化ベンゼン
、四臭化ビスフェノール、四臭化無水フタル酸、古臭化
シクロドデカン、トリス（ジブロモプロピル）ホスフェ
ート等がある。Furthermore, examples of the brominated flame retardants used in the present invention include brominated polyols, tetrabrominated bisphenol, tetrabrominated ethane, tetrabrominated butane, tetrabrominated propane, Ookubenzene, tetrabrominated bisphenol, and Examples include brominated phthalic anhydride, old brominated cyclododecane, and tris(dibromopropyl) phosphate.
上記の不飽和シランの配合量は、ポリオレフィン１００
重量部あたり、０．５〜５重量部であることが望ましく
、また遊離ラジカル発生剤の配合量は、ポリオレフィン
１００重量部あたり、０．０５〜０．７５重量部、特に
０．１〜０．５重量部であることが望ましい。The blending amount of the above unsaturated silane is 100% of the polyolefin.
The amount of the free radical generator is preferably 0.5 to 5 parts by weight, and the amount of the free radical generator is 0.05 to 0.75 parts by weight, particularly 0.1 to 0.75 parts by weight, per 100 parts by weight of the polyolefin. The amount is preferably 5 parts by weight.
また本発明に使用する塩素系難燃剤の添加量は、ポリオ
レフィン１００重量部あたり、５〜５０重量部であるこ
とが望ましく、また、臭素系難燃剤の添加量は、５〜２
０重量部が望ましい。Further, the amount of the chlorinated flame retardant used in the present invention is preferably 5 to 50 parts by weight per 100 parts by weight of the polyolefin, and the amount of the brominated flame retardant added is 5 to 2 parts by weight.
0 parts by weight is desirable.
なお、ベースポリオレフィンには、必要に応じて塩素系
難燃剤と共に、三酸化アンチモンその他の金属酸化物か
ら成る難燃助剤を添加してもよい。Incidentally, a flame retardant aid consisting of antimony trioxide or other metal oxide may be added to the base polyolefin together with a chlorine-based flame retardant, if necessary.
難燃助剤の配合量は、ポリオレフィン１００重量部あた
り、５〜２０重量部程度であることが望ましい。The blending amount of the flame retardant aid is preferably about 5 to 20 parts by weight per 100 parts by weight of the polyolefin.
本発明の製造方法を実施するにあたっては、臭素系難燃
剤を除く全成分を、押出機のホッパーへ供給し、１６０
〜２２０℃の温度で混練しつつ押出機内を進行させグラ
フト化反応を行なわせる。In carrying out the production method of the present invention, all components except the brominated flame retardant are fed to the hopper of the extruder,
While kneading at a temperature of ~220°C, the mixture is allowed to proceed through the extruder to carry out the grafting reaction.
なお、上記成分をホッパーへ供給するにあたり、塩素系
難燃剤は、予じめポリオレフィンの一部と混練してペレ
ット状に成形しておくことが望ましい。In addition, when supplying the above-mentioned components to the hopper, it is desirable that the chlorine-based flame retardant be kneaded with a portion of the polyolefin in advance and formed into pellets.
またシラノール縮合触媒は、グラフト化反応前にポリオ
レフィンに添加することなく、臭素系難燃剤と共にグラ
フト化されたポリオレフィンベースの混合物中へ添加す
るようにしてもよい。The silanol condensation catalyst may also be added to the grafted polyolefin-based mixture together with the brominated flame retardant, without being added to the polyolefin before the grafting reaction.
而して、臭素系難燃剤は、そのまま、あるいはマスター
バッチの形態で、押出機のグラフト化ゾーンと押出ヘッ
ドとの間のバレルに設けたホッパーからグラフト化され
たポリオレフィン混合物中へ添加される。The brominated flame retardant is then added neat or in the form of a masterbatch into the grafted polyolefin mixture from a hopper located in the barrel between the grafting zone and the extrusion head of the extruder.
臭素系難燃剤の添加されたシラングラフト化ポリオレフ
イン混合物は、更Ｏこ押出機中で混練された後押出ヘッ
ドから所定の形状に押出され、水分の存在下に常温又は
加温環境下で架橋せしめられる。The silane-grafted polyolefin mixture to which a brominated flame retardant has been added is kneaded in an extruder, extruded into a predetermined shape from an extrusion head, and crosslinked in the presence of moisture at room temperature or in a heated environment. It will be done.
なお、臭素系難燃剤は、必ずしもシラングラフト化ポリ
オレフィンが押出機内にある間に添加される必要はなく
、一旦、塩素系難燃剤の配合されたシラングラフト化ポ
リオレフィンをペレットに成形し、臭素系難燃剤とシラ
ノール縮合触媒とを配合したマスターバッチを前記ペレ
ットと混合し、再度この混合物を押出機へ供給して所定
の形状に押出成形するようにしてもよい。It should be noted that the brominated flame retardant does not necessarily have to be added while the silane-grafted polyolefin is in the extruder; it is necessary to first form the silane-grafted polyolefin containing the chlorinated flame retardant into pellets, and then add the brominated flame retardant to the silane-grafted polyolefin. A masterbatch containing a fuel agent and a silanol condensation catalyst may be mixed with the pellets, and the mixture may be fed to an extruder again to be extruded into a predetermined shape.
以上のようにして得られる成形品は、臭素系難燃剤によ
りグラフト化反応が阻害されていないので高い架橋度に
まで架橋され、かつ塩素系難燃剤と臭素系難燃剤との相
剰効果により高度の難燃性を発揮することができる。The molded product obtained in the above manner is crosslinked to a high degree because the grafting reaction is not inhibited by the brominated flame retardant, and is highly crosslinked due to the mutual effect of the chlorinated flame retardant and the brominated flame retardant. It can exhibit flame retardant properties.
次に実施例（こついて記載する。Next, examples will be described.
実施例
（４）ポリエチレン
塩素系難燃剤
（デクロラン）
ｂ２０３
ＣＰ
ＴＭＯ８
１００重量部
２０／／
１０ 〃
０、１５ ／／
２．３〃
上記混合物を、１８０〜２２０℃の押出機へ供給し、シ
リンダー内を前進させつつ反応させて、シラングラフト
化ポリオレフィンとし、これを紐状に押出して裁断しペ
レットとした。Example (4) Polyethylene chlorine flame retardant (dechlorane) b203 CP TMO8 100 parts by weight 20 // 10 〃 0, 15 // 2.3〃 The above mixture was supplied to an extruder at 180 to 220°C, and the inside of the cylinder was The mixture was reacted while advancing to form a silane-grafted polyolefin, which was extruded into a string shape and cut into pellets.
（Ｂ）ＥＶＡ １００重量部 臭素系難燃剤 □。(B) EVA 100 parts by weight Brominated flame retardant □.
。 ７（匹見１ヒフ゛タン） ＤＢＴＤＬ ０．５ｕ 上記混合物を混練し、ペレットに成形した。. 7 (1 animal seen) DBTDL 0.5u The above mixture was kneaded and formed into pellets.
（４）、（Ｂ）で得たペレットを、それぞれ５：１の割
合で混合して押出機に供給し、撚線導体上へ押出被覆し
、９０℃の温水中で３０分間加熱して架橋させた。The pellets obtained in (4) and (B) were mixed at a ratio of 5:1 and fed to an extruder, extruded and coated onto a stranded wire conductor, and cross-linked by heating in hot water at 90°C for 30 minutes. I let it happen.
得られた被覆の特性は次表の通りであった。The properties of the resulting coating were as shown in the table below.
なお、上表中比較例１はグラフト化反応に先立ってポリ
オレフィン１００重量部あたり、塩素系難燃剤（デクロ
ラン）を２０重量部配合したものであり、比較例２は、
グラフト化反応に先立ってポリオレフィン１００重量部
あたり、臭素系難燃剤（四臭化ブタン）を２０重量部配
合したものであって比較のため（こ掲げたものである。In addition, in Comparative Example 1 in the above table, 20 parts by weight of a chlorinated flame retardant (dechlorane) was blended per 100 parts by weight of polyolefin prior to the grafting reaction, and in Comparative Example 2,
Prior to the grafting reaction, 20 parts by weight of a brominated flame retardant (butane tetrabromide) was blended per 100 parts by weight of polyolefin, and is shown here for comparison.
Claims (1)
ジカル発生剤および塩素系難燃剤を含むポリオレフィン
ベースの混合物を、押出機に供給し、前記押出機中で前
記不飽和シランをポリオレフィンベグラフト化させ、更
にグラフト化された前記ポリオレフィンベースの組成物
に、更に臭素系難燃剤を添加して押出成形し、しかる後
シラノール縮合触媒の存在下で前記グラフト化させたポ
リオレフィンを、加水架橋せしめることを特徴とする難
燃性架橋成形品の製造方法。 ２ ポリオレフィンは、ポリエチレンである特許請求の
範囲第１項記載の難燃性架橋成形品の製造方法。[Scope of Claims] 1. A polyolefin-based mixture containing an unsaturated silane having a hydrolyzable organic group, a free radical generator, and a chlorinated flame retardant is fed to an extruder, in which the unsaturated A silane is grafted to a polyolefin, and a brominated flame retardant is further added to the grafted polyolefin-based composition, extrusion molded, and then the grafted polyolefin is grafted in the presence of a silanol condensation catalyst. A method for producing a flame-retardant crosslinked molded product, which comprises crosslinking with water. 2. The method for producing a flame-retardant crosslinked molded article according to claim 1, wherein the polyolefin is polyethylene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP53008017A JPS5839170B2 (en) | 1978-01-27 | 1978-01-27 | Method for manufacturing flame-retardant crosslinked molded products |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP53008017A JPS5839170B2 (en) | 1978-01-27 | 1978-01-27 | Method for manufacturing flame-retardant crosslinked molded products |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS54101862A JPS54101862A (en) | 1979-08-10 |
| JPS5839170B2 true JPS5839170B2 (en) | 1983-08-27 |
Family
ID=11681566
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP53008017A Expired JPS5839170B2 (en) | 1978-01-27 | 1978-01-27 | Method for manufacturing flame-retardant crosslinked molded products |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5839170B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60152377U (en) * | 1984-03-14 | 1985-10-09 | 有限会社 丸栄竹尾商店 | Teapots |
| JPS6147871U (en) * | 1984-09-01 | 1986-03-31 | 荒木 弘 | teapot |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8400149D0 (en) * | 1984-01-05 | 1984-02-08 | Bp Chem Int Ltd | Polymer composition |
-
1978
- 1978-01-27 JP JP53008017A patent/JPS5839170B2/en not_active Expired
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60152377U (en) * | 1984-03-14 | 1985-10-09 | 有限会社 丸栄竹尾商店 | Teapots |
| JPS6147871U (en) * | 1984-09-01 | 1986-03-31 | 荒木 弘 | teapot |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS54101862A (en) | 1979-08-10 |
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