CS205490B1 - Thermooxidative stable polyethylene mixture suitable especially for cable making purposes and method of manufacture of the said mixture - Google Patents
Thermooxidative stable polyethylene mixture suitable especially for cable making purposes and method of manufacture of the said mixture Download PDFInfo
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- -1 polyethylene Polymers 0.000 title claims description 30
- 239000004698 Polyethylene Substances 0.000 title claims description 27
- 229920000573 polyethylene Polymers 0.000 title claims description 27
- 239000000203 mixture Substances 0.000 title claims description 16
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 238000000034 method Methods 0.000 title claims description 5
- 229920000642 polymer Polymers 0.000 claims description 17
- 239000003963 antioxidant agent Substances 0.000 claims description 13
- 230000003078 antioxidant effect Effects 0.000 claims description 11
- 150000002978 peroxides Chemical class 0.000 claims description 10
- 239000000945 filler Substances 0.000 claims description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000003381 stabilizer Substances 0.000 claims description 4
- 239000006229 carbon black Substances 0.000 claims description 3
- 239000002530 phenolic antioxidant Substances 0.000 claims 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 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- UDBVWWVWSXSLAX-UHFFFAOYSA-N 4-[2,3-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butyl]-2-tert-butyl-5-methylphenol Chemical compound C=1C(C(C)(C)C)=C(O)C=C(C)C=1C(C)C(C=1C(=CC(O)=C(C=1)C(C)(C)C)C)CC1=CC(C(C)(C)C)=C(O)C=C1C UDBVWWVWSXSLAX-UHFFFAOYSA-N 0.000 claims 2
- ASLNDVUAZOHADR-UHFFFAOYSA-N 2-butyl-3-methylphenol Chemical compound CCCCC1=C(C)C=CC=C1O ASLNDVUAZOHADR-UHFFFAOYSA-N 0.000 claims 1
- HXIQYSLFEXIOAV-UHFFFAOYSA-N 2-tert-butyl-4-(5-tert-butyl-4-hydroxy-2-methylphenyl)sulfanyl-5-methylphenol Chemical compound CC1=CC(O)=C(C(C)(C)C)C=C1SC1=CC(C(C)(C)C)=C(O)C=C1C HXIQYSLFEXIOAV-UHFFFAOYSA-N 0.000 claims 1
- 235000006708 antioxidants Nutrition 0.000 description 10
- 230000006698 induction Effects 0.000 description 5
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000001273 butane Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000000087 stabilizing effect Effects 0.000 description 3
- 239000000654 additive Substances 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- RMSGQZDGSZOJMU-UHFFFAOYSA-N 1-butyl-2-phenylbenzene Chemical group CCCCC1=CC=CC=C1C1=CC=CC=C1 RMSGQZDGSZOJMU-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 102100029459 Apelin Human genes 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- 241000736839 Chara Species 0.000 description 1
- 101000771523 Homo sapiens Apelin Proteins 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000016383 Zea mays subsp huehuetenangensis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- MKUXAQIIEYXACX-UHFFFAOYSA-N aciclovir Chemical compound N1C(N)=NC(=O)C2=C1N(COCCO)C=N2 MKUXAQIIEYXACX-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000013538 functional additive Substances 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 235000009973 maize Nutrition 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000003359 percent control normalization Methods 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
Vynález sa týká antioxidantmi fenolického - typu stabilizovartého ' mattriálu na·' báze po^6^1^^ ktorý je vhodný najm^ pre kábelárske a e^ktrotechnícW účely. Óčelom ri.eáenia je umooniť efektOvym a nenákladným spdsobom výrobu a uplatněna takého to mateiálu u kterého nedochádza k migrácii a^tLoxidantu - a dosahuje sa dlhodobá, zvýšená termooxidačná stabilita při jeho použití v praxi.The invention relates to phenolic antioxidant - type stabilizovartého 'mattriálu · the' base of the ^ 6 ^ ^^ 1 which is H | Ný Najm ^ p re s Bel and the RSKE e ^ y ktrotechnícW purpose. The purpose of this invention is to make the effect and the inexpensive production and use of such a material free of migration and oxidant - and to achieve long-term, increased thermo-oxidative stability when used in practice.
Polyolefíny sú značné náchylné na oxidáciu ui vzhTadom na svoju uhlovodíková átruktúru, a preto ich spracovanie a aplikácia vyiadujú vhodnú termooxidačnú stabilizáciu. Táto_sa v súčasnooti dosahuje rozličnými ochrannými přísadami, z ktorých- najčastejSie sa - používájú stéricky tienené aromatické aminy a fenoly vo funkci! takzvaných terminátorov reťazca. VzhTadom na značnú štruktúinu odlišnost od polymérnej maarice tieto látky sú však- v polyetyléne vjšeobecne zle robustné. Pri zvýšenej teplote, například 288 °C možno u tr^i^í^-22mety1-4-hydroχy-5-terc.butylfeiyl/ butánu pozorovali ui po niekoTkých hodinách skoro 20 percentný úbytok, u 4,4'- tio-bis-/6-eecc.žuty--m-kreiolž/ úbytok výše 50 percent a 2,6-diterc·butyl-4-metyl-fenol dokonca za - takúto krátku -dobu vyprchá . Áplne. Táto - skutočnosť-sa velmi - meškán tne - prejavuje aj při niiší^ch teplotách v prtpafc 4>4z-tio-bit-/6-teIc·bžtyl m-krezolu/ východis^vé 10“* ^otnostný^ ^e^v, poklesne napr^].^ pri bežnej oo^i^É^t^^θ<j teplote za ^ekolko rokov na hodnotu radové 10-4 tomonostnýtó (die^v. Uvedeným Údajem odpovedá aj atabilizačný účinok tohto tntioxidtitu posudzovaný podlá indukčnej peri205 490Polyolefins are highly susceptible to oxidation due to their hydrocarbon structure and therefore their processing and application require suitable thermo-oxidative stabilization. This is currently achieved by various preservatives, the most common of which are the use of sterically shielded aromatic amines and phenols in function. so-called string terminators. However, due to their considerable structure, the difference from the polymer matrix is generally poorly robust in polyethylene. At elevated temperature, for example288 ° C possible22-methyl-4-hydroxy-5-tert-butylphenyl / butane showed a decrease of almost 20 percent in a few hours, in the case of 4,4 ' 2,6-di-tert-butyl-4-methylphenol even evaporates in the short term. APLN. This - fact-sa very- delayed tne- also manifests when niiwiths^ ch teplaboutitCh in prtpafc 4> 4from-Tiobit-/6-teIc ·bžtyl m-cresol / starting material10“* ^ Turnable ^ ^ e ^ v,pwill drop eg ^]. ^ atbefromnej oo ^andThe temperature has been over the last few years athaboutDnotu raDs10-4 tomonostnýtó (die ^ v.UinDThe data also corresponds to the stabilizing effect of this antioxidant assessed by induction peri
205 490 ódy oxidácie při - teplote 200 0C, už po uplynuti 72 hodin od přípravy - vzorky možno zaznamenat pokles na polovičnú'hodnotu.205,490 ode oxidation at - a temperature of 200 0 C, after only seven hours of preparation 2 - the sample to be recorded fall polovičnú'hodnotu.
Určité zlepšenie sa dosahuje použitím antioxidantov s vyššou molekulovou - hmotnosťou, teda přísad so zníženou difúznou schopnoatou a úmmerne a ňou aj s obmedzenou migráciou týchto z polyméru. Hoci prchavosť týchto zlúčenín z polyetylénu je už nižšia, pře ich zvýšenú neznádanlivosť s polymérom sa nedosahuje taký - stabilizačný účinok ako v případe použitia nízkomolekulových antioxidantov. ĎaTéou nevýhodou je aj obmedzený výběr stabilizátorov uvedeného - typu, ich - poi^u^ilterno^’!?, ako aj ich vy^ía cena.Some improvement is achieved by the use of higher molecular weight antioxidants, i.e., additives with reduced diffusion capability and proportionally and with limited migration of these from the polymer. Although the volatility of these polyethylene compounds is already lower, despite their increased polymer non-polymerization, such a stabilizing effect as in the case of the use of low molecular weight antioxidants is not achieved. A further disadvantage is the limited choice of stabilizers of said type, their type, as well as their higher cost.
Nevýhody doterajšieho stavu odstraňuje riešenie podl’a vynálezu, podl'a ktorého termooxidačne stabilízovená polyetylénová zmea, vhodná najmá pre kábelárske účely, kde stabblizátorom je fenolický antioxidant, táto zmes obsahuje v pomere na 100 hmoonostných dielov polyetylénu poddel 0,05-1,00 hmotnoatných dielov nízkomolekulového trtitxiitrtu typu viacjademého fenolu s terciárym alkylsžbstižuentom, výhodné 4,4-tit-bis/6-teгc.bžtyl m-krezolu/, alebo tria-2-metyl-4- hУlгooχ-5-tteá♦búžylfenol/ butánu, ktorý je na polyetyléne fixovaný chemickou vázbou, vytvořenou rozpadem peroxidu. Koorkáeiiiciou je tu alternativa, kde v pomere na 100 hmoonostných dielov polyetylénu v zmesi táto obsahuje aj podiel 1-100 hmoonostných dielov plniva na báze uhLičitanov, kremčitanov alebo sadzi. Obrněnou daného-. - riešenia je SlaSia alternativa, podl'a ktorej poddel nízkorolekulového ^ti^oxidantu typu viacjadrovéht fenolu s terciárnym alk^^le^ubst^iLueeiio^m v zmmei je v pomere hmoonostných dielov 1:10-10:1 kombinovaný a antioxidimtom typu esterov kyseliny ditioprtpitrtvej, výhodné dilaurylesteáž. Vhodným výrobným postupem, ktorým ва realizuje áieierie podfa vynálezu je spčs^ charakteritovarý tým, že do polymrnej ^veniny sa pri ^plota 11°-130 0C disperguje ako zmesný poddel nízkomolekulový antioxidant typu-viacjaderného fenolu s terciárnym alkylsubstižuentom, výhodné 4,4*-tit-bis/6-teáč.bžtyl m-kkáeio/, a^to tris - /2-metyl4-tydrotχ-5-ttrá.bužylfenrl/ bután v moostve 0,05 - 1,00 hmoonostných dielov na 100 hmoonostných dielov polyetylénu, ako aj podiel suba^um)varného terciárneho alky^eroxidu, výhodné dikumypprosidu, v molárnom pomere 1:10-50:1 k min o štvu antitxiiantu a zmeané iltžky včítane případného podielu aj plniva sa potom ithrievajú po dobu 0,1-80 minút pri teplote -150-400 0C.Disadvantages of the prior art are eliminated by the solution according to the invention, in which the thermo-oxidatively stabilized polyethylene composition, suitable in particular for cable use, wherein the stabilizer is a phenolic antioxidant, contains in a proportion of 100 parts by weight of polyethylene, 0.05 to 1.00 parts by weight. parts of low molecular weight phenol viacjademého trtitxiitrtu type of tertiary alkylsžbstižuentom, preferably 4,4-bis-sub / 6-m-cresol teгc.bžtyl / or trio-2-methyl-4- hУl гo oχ-5-tteá ♦ búžylfenol / butane, which is fixed to the polyethylene by a chemical bond formed by the breakdown of peroxide. Correlation is an alternative where, in proportion to 100 parts by weight of polyethylene in the mixture, it also contains a proportion of 1-100 parts by weight of a carbonate, silicate or carbon black filler. Armored-given. - the solution is a weaker alternative, according to which the low molecular weight phenol of a multinucleate phenol with tertiary alkali is mixed in a ratio of 1: 10-10: 1 by weight and an antioxidant of the acid ester type ditioprtpitrtvej, preferred dilaurylesážáž. A suitable manufacturing process, which ва carried áieierie the invention is SPCS ^ chara the teritovarý the z e the poly m rnej ^ Venina at ^ fence 11 ° - 1 30 0 C is dispersed as mixed to give in a low molecular weight type antioxidant-multinucleated phenol tertiary al the ylsubstižuentom, preferably 4,4 - b it-bis- / 6-m-teáč.bžtyl kkáei a /, ^, and a t r i a - /2-metyl4-tydrotχ-5-ttrá.bužylfenrl/ butane in moostve 0 , 05-1.00 parts by weight per 100 parts by weight of polyethylene, as well as a proportion of the submerged boiling tertiary alkyl eroxide, preferably dicumypproside, in a molar ratio of 1: 10-50: 1 to min of antitxiiant sieve and mildness of the ingredients, including optional Both the filler and filler are then heated for 0.1-80 minutes at -150-400 ° C.
Pozitivny účinok riešenia podTa ' vynálezu je ddsledkom takého - átxuikturálneho usporiadaniá zložiek v maaeeiáii, kde anlmidant je na polyetylénových reťazcoch naátepený s vytvořením stálej - eheauckej vazby, ktorou sa fixuje ochranná - přísada na polymri a zabraňuje sa jej úbytku pri aplikácii i po aplikácii zmesi. Rozpad peroxidy prd daných podmenkach výroby substitučnou reakciou vytvára radikály - polyetylénu aj artdtxiiartu, ktoré vzájemnou rekombbnáciou posVtujú trvalé chemické vazby s konečným efektom naátepenia an-t^xi— dantu - na polymer. Takto naviazaný antioxidant je už z polyméru neextrahovateTný a prejavuje sa výrazné zvýšeným účinkoom txvalej termooxidačnej stability mateei&u. Daný výrobný postup je výhodný aj tým, že pri pouužtí vfčáieho mnostva peroxidu sa s nastepením aitioxidantu na polyetylén súčasne dosahuje i iosieeerie polymeru, - spojené so zvýšením jeho eeraomeshetn.ekej odoOnotSi. Calšou výhodou je tu motnrtSL plrenit polyméru do pomerne vy3The positive effect of the present invention is due to such an xuiktural arrangement of the components in the maize, where the antimidant is cleaved on the polyethylene chains to form a stable eheactive bond, which fixes the protective additive to the polymer and prevents application loss when applied. The disintegration of peroxides given by the substitution reaction forms radicals, both polyethylene and artdtartii, which, by mutual recombination, provide permanent chemical bonds with the ultimate effect of an antioxidant cleavage to the polymer. The antioxidant thus bonded is no longer extractable from the polymer and exhibits a markedly enhanced effect of the thermooxidative stability of the material. The production process is also advantageous in that, when a larger amount of peroxide is used, at the same time, the polymerization of the polymer is achieved by the addition of the aitioxidant to the polyethylene, which is associated with an increase in its elasticity. A further advantage here is the motnrtSL to bring the polymer to a relatively high 3
205 490 so^<ého etupňa, t.j. až 100 hmotnostech dielov plniva na 100 hmotnostech dielov polyetylénu v zmeei.205 490 of the second stage, i. up to 100 parts by weight of filler per 100 parts by weight of polyethylene in the mixture.
U itabiliovvaného materiálu a výrobkov, získaných uplatněním riešenia podl'a vynálezu, neprejavujú ia obvyklé nepriaznivé vplyvy, spojené a degradáciou póvodrných fyzikairych vlastností v porovnaní i neitabilíovanem Riešenie umoOňuje technicky a ekonomicky velmi výhodem spSsobom výrobu produktov aj dlhodobe vyataveech vyšším teplotm a obzviašť aj v takých prípadoch, keá ia okrem nárokov na termooxidačnú stabilitu vyžaduje aj zvýšena termomeehanicka odolnoot.The itabiliated material and products obtained by the application of the invention do not exhibit the usual adverse effects associated with the degradation of the original physical properties compared to the non-stabilized solution. This solution provides a technically and economically very advantageous way of producing products even at long-term higher temperatures and particularly at such temperatures. in cases where, in addition to the requirements for thermo-oxidative stability, it also requires increased thermo-thermal resistance.
h Vyuuiiie vynálezu prichadza do úvahy hlavně při výrobe nízkonapěťových a vysokonapaťových kablov a izolozvaných vodičov, kde ia dosiahne zvýšenie životnosti ai o 15 rokov v porovnaní i doteraj.ším itavom resp. aj v iný^ch odboroch, například při výrobe rúr na rozvod teplej vody pre najrozličnejšie účely pouuítia. Pri produkcii takýchto výrobkov kontinuálnou technologiou vyOlačovania, nie je přitom ani potřebné před 8pracovaním.maatriaiu zviašť připravovat zmes obsahujúcu funkčně prýsady, stabilizator i peroxidom, ale tieto možno priamo davkovať do spracovatelského extrúdera kontinuálryrm navaiovaním.The use of the invention can be used mainly in the production of low-voltage and high-voltage cables and insulated conductors, where ia achieves an increase in the service life of up to 15 years compared to the current ITV resp. also in other fields, for example in the production of hot water distribution pipes for a wide variety of applications. In the production of such products by a continuous extrusion process, it is not even necessary to prepare a mixture containing functional additives, a stabilizer and peroxide, but it can be directly fed into the processing extruder by continuous rolling.
Koonkreizácia ri^ešenia podlá vynálezu je dand v příkladech, ktoré ia uvádzajú v dalšom. Příklad 1The co-creping of the solution according to the invention is dand in the examples which are set forth below. Example 1
Po roztavení 100 hmot, dielov polyetylénu i hustotou 0,92 a indexom toku taveniny g/10 rnnút v miešacej komoře Bratendero^o plastograíu ia pri tepote 125 °C pri.dalo do taveniny polymSru 0,1 hmoOnnotech dielov 4,4 * -tio-bis-Ze terc^^y! m-kkezolu/ a 0,2 hmotnostech dielov dikumypeeroxidu. Zmes sa pri uvedenej teplote miešala 5 · minút * a po jej tvarovaní na dostihu, sa táto v li.se pod ^akom 30 ДОа zohrievala 20 rnnút pri ^plote 175 °C. Za týchto podmienok sa 8 hodinovou sMtou extratoie iz^ropylalkoholom pri ^plo^ 70 °C zlatilo UV spektroskopiou 78% naviazanie antioxidantu na polyetylén. Indukčné perioda oxidáeie, meraná na tejto vzorke a^sorpci.ou kyslýka pri 180 °C, vylcazovala ^airái.té po jej príprove hodnotu 620 minút a t^o sa nezmePla ani po 9° dňovom ^stavení ^pote 70 °C, kým u polyméru stabilioovaného týmto m^ožstvom antioxidantu, avšak bez spolupf aobenia peroxidu, došlo po vystavení vzorky rovnakým podmienkam k poklesu tejto hodnoty na 65 minút. Obdobné nedošlo tu ani k zmenúm elektrických a dielektr^kych vlastnootí zmesi, ktora vykazovala hodnoty straOového činitele 3·10”\ peermiiivity 2,3 a elektrictoj pevnooti 35 kV/mm. ^mes sa aplikovala na izoia^u vysokofrekvenčech vodičov.After melting of 100 wt. Parts of the polyethylene density of 0.92 and a melt index of g / 10 àñòü in the mixing chamber of the plastograíu Bratendero ^ p i r i a temperature between approximately 12 5 DEG C to melt ri.dalo polymSru hmoOnnotech 0.1 parts of 4, 4 * -thio-bis-Ze tert -butyl; and 0.2 parts by weight of dicumypeeroxide. The mixture was stirred at the same temperature for 5 min · *, and after forming the race, in this clip li.se ^ 30 to which heated ДОа 20 àñòü p r i ^ fence 175 ° C. In those circumstances, the 8-hour SMTO extratoie referred ropylalkoholom p ^ r ^ i ^ Flat 7 0 C gilded UV spectroscopy, 78% of the binding of an anti-oxidant to polyethylene. Oxidáeie induction period, measured in this model of e and ^ yk sorpci.ou of YSL and at 180 DEG C., vylcazovala ^ airái.té after príprove h alue 620 minutes at O is an IP nezmePla the 9-day ^ ° ^ houses sweat 7 0 ° C, while in polymer stabilioovaného this m ^ ožstvom antioxidant, but without spolupf aobenia peroxide, occurred after exposure of the sample to the same conditions to decrease this value to 65 minutes. A similar there are also no zmenúm of Electrical and Dielectric ^ kych vlastnootí composition, which showed a value of y straOov eh factor 3 · 10 "\ peer ivity and y 2, p 3 and elektrictoj evnooti 35 kV / mm. It was applied to the isolation of high-frequency conductors.
Prýklad 2Example 2
Pri prýprave vzoriek a ich skúSaní sa použili rovnaké suroviny a rovnOcý postup ako v prýklade 1, len s tým rozdielom, že 4,4 *-eio-bls-/6eeri.butyl m-krezoiu sa do polyetylénu přidalo 0,2 hmoOnnotech dielov na 100 hmotnotteih dielov polymru. ' Určen obsah an^ox^antu nav^zen^o na polyetylén bol 80 % a kd^M periOda oxidacie pri 180 °C, ktora sa ani po 90 dňovej sxjpooíííí pri ^plote 70 °C nezmenHa, ’ mmla hodnotu 950 · minút. Taktiež nedošlo k zmene pdvodnej charakteristiky u elektrickej pevncoii, straOového činitetela a perrniiivity.The same raw materials and the same procedure as in Example 1 were used in the preparation and testing of the samples, except that 4,4% -eio-bls / 6-butylbutyl m-cresol was added to polyethylene 0.2 parts by weight per sample. 100 parts by weight of polymer. 'DETERMINATION n ^ ox ^ antu nav ^ zen ^ of the p olyety treatment n b ol, 80% and K ^ M p er iodine and sulfur, and the CIE L T and 180 DEG C., the tor, and is not p 90 day sxjpooíííí the fence 7 ^ 0 C nezmenHa, "mmla alue h 0 · 95 min. Bars of no changes in electrical characteristics pdvodnej pevncoii, straOového činitetela and perrniiivity.
Prýklad3Prýklad3
205 490205 490
I tu ca použili rovnaké suroviny a rovnaký postup ako v příklade 1, avšak do polyetylénu aa přidalo 0/25 hmotnostuních dielov antioxidantu a 1,85 hmotnootiných dielov peroxidu ná 100 hmo^o^ch dielov polymru· Zistené množivo antioxidantu naviazaného na polyetylén bolo 89% a indukčná perioda oxiWcie při 190°C vykazovala hodnotu 340 minút· Stálost stabilizačného účinku a^iti^oxidantu za týchto podmcnok sáčasného eieťovania polytóru dokažme akutočnosť, ie východisková ťainosť polyetylénu 520% a elektrické a dielektrioké charakteristiky sa ^akUcty nezmenši ani po 40 dňovom namtturní pri teplot 15° °C· Tieto vzorky vykazovali aj zvýšeni! t^e^imom^c^liíu^i.ckú odolnost, ktorá sa prejavila iba 60% deformáciou - sk^obných tcliesok zatažený^ 20 N/cm^ při teplote 200 °C· Zmas- ca apHlcovala na izoláciu silových káblov 22 kV.Here again the same raw materials and the same procedure as in Example 1 were used, but 0/25 parts by weight of antioxidant and 1.85 parts by weight of peroxide per 100 parts by weight of polymer were added to polyethylene aa. % and induction, and the period oxiWcie at 19 0 C showed h alue 340 minutes · Stability stabilizing effect and ^ iti ^ oxidant to compare podmcnok sáčasného eieťovania polytóru Let us prove akutočnosť, ie the starting Elongation polyethylene 520%, and the electrical and dielectric characteristics of the ^ akUcty neither reduce p 0 of 4-day namtturní at temperatures 15 ° C · These samples showed also increase! t ^ e ^ c ^ ^ imom Liia ^ i.ckú resistance could be detected with only 60% strain - en obných ^ ^ tclieso load is 20 N / cm ^ of that of L Lote 200 ° C · Zmas- CA apHlcovala to isolate the power 22 kV cables.
Příklad 4Example 4
Do polyetylénu s indexom toku taveniny 0,1 g/10 mnút aa prirnešalo 0,65 hmoOnootných diclov 2t 2'-tio 2dictylbis-£3-2/3l5-ditcrc.buty1242hiydroxyfenrl/2propionátuji 1,1’ hmOnostných dielov 1l4-diterc·butyPpeto:yr-di-Zoюrtppylonbenzéou na 100 hmoOnnotiných diclov polyméru a rovneký— postupom ako v prcdchádzajúcich príkladoch sa připravili a testovali ckúšobné vzorky· V tomto případe sa zistili následovně charakteristiky’ stability polyméru: nev^azame antioxidantu na polymr 65%, východisková indukčná perioda oxidácie při l80 °C 730 mnút a . po 90 tóovom pteobení teploty 70 °C 680 mnút· U vzoriek vystavených 40, dfovému pósobeniu tepoty -. 150 °C ta^os^ e^atoty Čin^el’, pemntivita a elektrická pcvnoeť- si zachovali pdvodnd hodnotu, obdobné ako . v predchádzajúcom příklade·Příklad 5Add the polyethylene having a melt index 0.1 g / 10 minutes to complete aa prirnešalo 0.65 hmoOnootných dicle 2 t 2 "thio 2dictyl Bis- £ 3 2 / 3l5- d itcrc. Tue 1242 h y d roxy iy f a y rl / r a 2propionátu 1,1' hmOnostných parts · 1l4-di-tert butyPpeto: yr-di-Zoюrtppylonbenzéou 100 hmoOnnotiných dicle polymer rovneký- prcdchádzajúcich to that in the Examples were prepared and tested ckúšobné sample · In this case, the following characteristics have found the stability of the polymer: nev ^ Azam antioxidant to the polymerization of 65%, initial induction period of the oxidation of l 80 C 73 0 and a softening. p 90 To's pteobení temperature of 70 ° C 680 Softening · The pattern and exposed to the e 40, DFOV action of temperature between approximately -. 1 50 ° C the person ^ ^ e ^ Atoto Cin ^ el ', pemntivita e l EC Trická pcvnoeť- maintain pdvodnd value, similar to that. in the previous example · Example 5
Polymr a peroxid sa použili roanakími c^i^iral^lterifi^tk^imi a v rovnakom mcoitve ako v predchádzajjúcom příklade, pričom ako eotioxidaot tu vystupoval trss//2-metyl-4-tydroxy-5-texc«butylfenyl/bután v mnoitva 0,4 hmot^c^stitych dielov na 100 hmoonnotných dielov polyetylénu· V tomto případe došlo k 73% oaviezeoiu αntisxideotu na polymr, ktorý vykazov^ induWnú period oxidácic pri 180 °C 420 mnút· Táto charatteristita sa po 90 dňovom ^stavení tcplotc 70 °C v prípade spolupósobenia peroxidu ^a^icky zactavtú.a na východickovej hodnotě a obdobné sa zachovali aj východiskové hodnoty elektrických a dielektrických οΙμοτΖ^^ΙοΗ^The polymer and the peroxide were used in the same manner as in the previous example, with trss / 2-methyl-4-thyroxy-5-tert-butylphenyl / butane as the eotioxidaot. 0.4 w ^ C ^ plate parts per 100 parts of polyethylene hmoonnotných · In this case, there was a 73% oaviezeoiu αntisxideotu to the polymerization of exhibiting ^ induWnú period dioxide; Acic at 180 ° C 4 20 m · the nut charatteristita after 90 days ovom building tcplotc 7 ^ 0 C at p D e peroxide interaction of N, N-icky zactavtú.a the východickovej value and the like to preserve the initial values of the electrical and dielectric οΙμοτΖ ^^ ^ ΙοΗ
Příklad 6Example 6
Na přípravu skúšojbpích vzorick sa na 100 hmoonootních dielov polyetylénu s indexom toku taveniny 20 g/10 mnút použilo 50 hmoOnootných dielov povrchovo upravcnej kriedy s priamcrnou vclkosťou častíc 6^Ra, 0,5 hmoOnoottných dielov tris-^-metyl^-tydroxy^tcrc.butylfenyl/buténu, 1,0 hmOnoo^ttoých dielov dileuryltOodipropiooátu a 2,4 hmoonosných diclov dikumrlperoxidu· U skúšobných vzorek připravených z tcjto zmsi nevykazovala východisková ťainosť 500% pri jcj kontrole po - 10 dňovom stárnutí vo vzdušnom termostate pri 150 °C iia^dnu zm^i^u kým u iných sta^l^ovaných vzorick ťatoosť ui po 2 dňoch takého to namáisana jc prakticky - nulová· Taktici sa nczmnóla východisková hodnota stratového či^tc!^ ktorá má ▼ tomto prípadc ho<inotu 2·10“\ hodnota ^rmtivity o velkostiFor the preparation of the test specimens, 50 parts by weight of the surface-treatment chalk with a direct particle size of 6 Ra, 0.5 parts by weight of tris-4-methyl-4-thyroxy-t-trieth were used per 100 parts by weight of polyethylene with a melt index of 20 g / 10 min. butylphenyl / butene, 1.0 parts by hmOnoo ^ ttoých dileuryltOodipropiooátu, 2.4 hmoonosných dicle dikumrlperoxidu · the test sample prepared from the starting tcjto zmsi Elongation showed 500% control of the jcj - 10-day aging in air thermostat at 5 1 0 C II a ^ d not change ^ i ^ u while at the other hundred ^ l ^ ated vzorick tatoos ui p about 2 days, such that namáisana jc virtually - zero · Taktici the nczmnóla baseline Forgotten him or ^ tc! ^ kt or á m á ▼ If p and the d c h a <INOTEL 2 · 10 "\ ^ value of the size rmtivity
205 490 3)2 a elektrickéj pevnosti o hodnotě 35 kV/mm. Přítomnost peroxidu vo v&čáom množstvo zabezpečila iba naviac tejto zmesi aj termomechanickú odolnost nad teplotou tavenia polyméru, charakterizovaná iba 80% deformáciou skúáobných teliesok, zatažených při teplote 200°C 2205 490 3) 2 and electrical strength of 35 kV / mm. The presence of peroxide in large quantities only provided, in addition to this mixture, a thermo-mechanical resistance above the melting point of the polymer, characterized by only 80% deformation of the test bodies, loaded at 200 ° C.
N/cm · Zmes sa aplikovala na silové káble 1 kV·N / cm · The mixture was applied to 1 kV power cables ·
Příklad 7Example 7
V tomto případe sa ako plnivo polyetylénu s indexom toku taveniny 20 g/10 minút použili vodivé retortové sadze, z ktorých sa 25 hmotnostních dielov přidalo do 100 hmotnostních dielov polyméru po jeho roztavení na dvojválci· Táto zmes sa pri teplote 125 °C homogenizovala a 0,5 hmotnostními dielmi 4,4*-tio-bis- /б-terc.butyl m-krezolu/ a 2,5 hmotnostními dielmi dikumylperoxidu. Skúáobné telieska připravené řovnako ako v predchádzajúcich prípadoch vykazovali nasledovné charakteristiky: měrný vnútorný odpor pri teplote 23 °C 5 ohm • cm, indukčná perioda oxidácie pri 180 °C po 100 dňovej expozícii pri teplote 70°C zachovala 8i východisková hodnotu 810 minút a ťažnosť 380 %· Tieto hodnoty ako aj dielektrická a elektrické vlastnosti sa po 10 dňovom stárnutí pri 150 °C nezměnili· Materiál sa aplikoval na výrobu polovodivých zmesi pre elektrotechnické účely·In this case, conductive retort carbon black was used as a polyethylene filler with a melt index of 20 g / 10 minutes, of which 25 parts by weight were added to 100 parts by weight of polymer after melting on a twin cylinder. 5 parts by weight of 4,4 ' -thio-bis- (t-butyl m-cresol) and 2.5 parts by weight of dicumyl peroxide. The test specimens prepared as in the previous cases exhibited the following characteristics: specific resistivity at 23 ° C 5 ohm • cm, induction period of oxidation at 180 ° C after 100 days exposure at 70 ° C maintained the initial value of 810 minutes and elongation 380 % · These values as well as the dielectric and electrical properties did not change after 10 days of aging at 150 ° C · The material was applied to the production of semiconducting mixtures for electrotechnical purposes ·
Claims (3)
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS795273A CS205490B1 (en) | 1979-07-30 | 1979-07-30 | Thermooxidative stable polyethylene mixture suitable especially for cable making purposes and method of manufacture of the said mixture |
| CS622088A CS273080B3 (en) | 1979-07-30 | 1988-09-19 | Thermooksidatively stabilized polyethylene mixture suitable especially for cabling purposes |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS795273A CS205490B1 (en) | 1979-07-30 | 1979-07-30 | Thermooxidative stable polyethylene mixture suitable especially for cable making purposes and method of manufacture of the said mixture |
| CS622088A CS273080B3 (en) | 1979-07-30 | 1988-09-19 | Thermooksidatively stabilized polyethylene mixture suitable especially for cabling purposes |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CS205490B1 true CS205490B1 (en) | 1981-05-29 |
Family
ID=37714668
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CS795273A CS205490B1 (en) | 1979-07-30 | 1979-07-30 | Thermooxidative stable polyethylene mixture suitable especially for cable making purposes and method of manufacture of the said mixture |
| CS622088A CS273080B3 (en) | 1979-07-30 | 1988-09-19 | Thermooksidatively stabilized polyethylene mixture suitable especially for cabling purposes |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CS622088A CS273080B3 (en) | 1979-07-30 | 1988-09-19 | Thermooksidatively stabilized polyethylene mixture suitable especially for cabling purposes |
Country Status (1)
| Country | Link |
|---|---|
| CS (2) | CS205490B1 (en) |
-
1979
- 1979-07-30 CS CS795273A patent/CS205490B1/en unknown
-
1988
- 1988-09-19 CS CS622088A patent/CS273080B3/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| CS622088A1 (en) | 1990-07-12 |
| CS273080B3 (en) | 1991-03-12 |
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