DK144513B - PROCEDURE FOR THE PREPARATION OF CROSS-BONDED FORMATED SUBSTANCES BASED ON CROSS-BONDABLE OLEPHINE POLYMERS OR VINYL CHLORIDE POLYMER MATERIALS - Google Patents
PROCEDURE FOR THE PREPARATION OF CROSS-BONDED FORMATED SUBSTANCES BASED ON CROSS-BONDABLE OLEPHINE POLYMERS OR VINYL CHLORIDE POLYMER MATERIALS Download PDFInfo
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- DK144513B DK144513B DK536374AA DK536374A DK144513B DK 144513 B DK144513 B DK 144513B DK 536374A A DK536374A A DK 536374AA DK 536374 A DK536374 A DK 536374A DK 144513 B DK144513 B DK 144513B
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- crosslinking
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- peroxide
- vinyl chloride
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
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- Compositions Of Macromolecular Compounds (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
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Description
(19) DANMARK · ) §\Ά&/(19) DENMARK ·) § \ Ά & /
(12) FREMLÆGGELSESSKRIFT ου 144513 B(12) PRESENTATION WRITING ου 144513 B
DIREKTORATET FOR PATENT- OG VAREMÆRKEVÆSENETDIRECTORATE OF THE PATENT AND TRADEMARKET SYSTEM
(21) Ansøgning nr. 55^5/74 (51) lnt.CI.3 B 29 C 25/00 (22) Indleveringsdag 14. okt. 1974 C 08 J 7/00 (24) Løbedag 14. okt. 1974 (41) Aim. tilgængelig 1 6. apr. 1975 (44) Fremlagt 22. mar. 1982 (86) International ansøgning nr. - (86) International indleveringsdag - (85) Videreførelsesdag - (62) Stamansøgning nr. -(21) Application No. 55 ^ 5/74 (51) lnt.CI.3 B 29 C 25/00 (22) Filing date 14 Oct. 1974 C 08 J 7/00 (24) Running day 14 Oct. 1974 (41) Aim. available 1 Apr 6 1975 (44) Submitted Mar 22 1982 (86) International application # - (86) International filing day - (85) Continuation day - (62) Master application no -
(30) Prioritet 15. okt. 1975, 47995/75, GB(30) Priority Oct 15 1975, 47995/75, GB
(71) Ansøger AKTIESELSKABET NORDISKE KABEL- OG TRAADFABRIKER, København F, DK.(71) Applicant to the SHARE COMPANY NORDIC CABLE AND WIRE FACTORIES, Copenhagen F, DK.
(72) Opfinder Peter Carstens en, DK: Francesco Paolo Procida, DK:(72) Inventor Peter Carstens and, DK: Francesco Paolo Procida, DK:
Svend Sandholm Pedersen, DK.Svend Sandholm Pedersen, DK.
(74) Fuldmægtig Ingeniørfirmaet Hofman-Bang & Boutard.(74) Associate Engineer Hofman-Bang & Boutard.
(54) Fremgangsmåde til fremstilling af tværbundne formede emner på basis af tværbindingsdygtige olefinpoly= mere eller vinylchloridpolymere materialer.(54) Process for preparing cross-linked molded articles on the basis of cross-linkable olefin polymer or vinyl chloride polymeric materials.
Den foreliggende opfindelse angår en fremgangsmåde til fremstilling af tværbundne formede emner hvis dimension i mindst én retning betydeligt overstiger dimensionen i den eller de andre retninger, på basis af tværbindingsdygtige olefinpolymere eller vinylchlorid-The present invention relates to a process for producing crosslinked shaped articles whose dimension in at least one direction significantly exceeds the dimension in one or the other direction, on the basis of crosslinkable olefin polymers or vinyl chloride.
OQOQ
polymere materialer, fortrinsvis HD-polyethylen, hvorved materialet rOpolymeric materials, preferably HD polyethylene, whereby the material rO
varmformes til det ønskede emne, som derefter behandles med et organisk peroxid under varmepåvirkning.heat-formed to the desired item, which is then treated with an organic peroxide under heat.
=3r= 3r
Som eksempler på formede emner hvis dimension i mindst én retning ^ betydeligt overstiger dimensionen i den eller de andre retninger ® kan nævnes rør, kabler, plader og profiler. Opfindelsen er således ikke begrænset til emner fremstillet for eksempel ved sprøjtestøbning, presning eller sprøjtepresning, men omfatter også alle øvrige 2 144513 gængse fremstillingsmetoder for polymere materialer, såsom extru-dering, kalandrering, laminering, støbning, blæsning, etc.Examples of shaped items whose dimension in at least one direction ^ significantly exceeds the dimension in the other direction (s) may be mentioned pipes, cables, sheets and profiles. Thus, the invention is not limited to items made, for example, by injection molding, pressing, or injection molding, but also includes all other conventional manufacturing methods for polymeric materials such as extrusion, calendering, lamination, casting, blowing, etc.
De formede emner behøver ikke udelukkende at bestå af polymert materiale. Por det første kan de polymere naturligvis indeholde gængse fyldstoffer og øvrige tilsætningsmidler, men de kan også indeholde forstærkningsstoffer, og der kan specielt være tale om kabler med en metalkerne overtrukket med isolerende og/eller halvledende lag af polymere materialer.The shaped blanks need not consist solely of polymeric material. Of course, the polymers can of course contain conventional fillers and other additives, but they can also contain reinforcing agents, and in particular, they can be cables with a metal core coated with insulating and / or semiconducting layers of polymeric materials.
Adskillige millioner tons syntetiske polymere materialer anvendes årligt til forskellige formål, og det synes derfor unødvendigt at forsøge at forbedre disse materialers egenskaber. Imidlertid vil visse begrænsninger i disse materialers fysiske egenskaber bevirke, at de ikke benyttes på en række områder, hvor deres øvrige egenskaber gør deres anvendelse ideel. Por for eksempel polyethylen kan følgende egenskaber, som trænger til forbedringer, nævnes: (1) Modstandsevne mod krybning (plastic flow) ved stuetemperatur og forhøjede temperaturer.Several million tonnes of synthetic polymeric materials are used annually for various purposes, and it therefore seems unnecessary to try to improve the properties of these materials. However, certain restrictions on the physical properties of these materials will prevent them from being used in a number of areas where their other properties make their use ideal. Pores, for example, polyethylene, may need to be mentioned the following properties which need improvement: (1) Resistance to plastic flow at room temperature and elevated temperatures.
(2) Modstandsdygtighed over for opløsningsmidler ved forhøjede temperaturer.(2) Resistance to solvents at elevated temperatures.
(3) Modstandsdygtighed over for spændingsrevnedannelse.(3) Resistance to voltage cracking.
(4) Modstandsdygtighed mod sprøde brud, der optræder ved ikke-tværbundne PE-rør efter langtidstrykafprøvning ved forhøjet temperatur.(4) Resistance to brittle fractures occurring in non-cross-linked PE pipes after long-term pressure testing at elevated temperature.
Fremkomsten af polyethylen med høj densitet (eller høj massefylde) (HD-PE) er et godt skridt på vejen til at løse disse problemer, men tværbinding af HD-PE, en proces, som svarer til vulkanisering af gummi, giver endnu større forbedringer af disse egenskaber.The emergence of high density (or high density) polyethylene (HD-PE) is a good step on the road to solving these problems, but cross-linking of HD-PE, a process similar to rubber vulcanization, provides even greater improvements in these properties.
Ved fremkaldelse af tværbinding i tværbindingsdygtige polymere materialer er det en kendt teknik at anvende fri-radikal-dannere, som regel organiske peroxider, til ad kemisk vej ved en termisk behandling og/eller i forbindelse med acceleratorer, aktivatorer og/eller coagenter at fremkalde tværbinding. Ved de fleste kendte metoder 3 U4513 til fremstilling af formgivne tværbundne emner af tværbindingsdygtige polymere materialer kræves det, at fri-radikal-danneren er iblandet eller indarbejdet i den polymere inden formgivningen.In developing crosslinking in crosslinkable polymeric materials, it is a known technique to use free radical generators, usually organic peroxides, to chemically by thermal treatment and / or to induce crosslinking in connection with accelerators, activators and / or coagents. . In most known methods 3 U4513 for the manufacture of shaped crosslinked blanks of crosslinkable polymeric materials, the free radical generator is required to be blended or incorporated into the polymer prior to shaping.
En sådan indarbejdning af fri-radikal-dannere foretages som regel på konventionelle blandingsapparaturer. For for eksempel polyethylen med lav densitet (LD-PE) kan to-valseværker eller Banbury-mixere anvendes. Blandingsapparaturet opvarmes til ca. 110°C, og polyethylen, som kan indeholde fyldstoffer, antioxidanter og coagenter, tilsættes og behandles en passende tid, indtil materialet er homogent smeltet. Herefter tilsættes fri-radikal-danneren, hvorefter en yderligere blandetid på 2 - 5 minutter sædvanligvis er tilstrækkelig. Temperaturen må som regel efter tilsætning af fri-radikal-danneren ikke overstige 120°C. Når blandingsprocessen er tilendebragt, granuleres materialet på kendt måde og er herefter klart til at tilføres extrudere eller formstøbemaskiner, hvor de færdige emner formgives ved så lave temperaturer, at for tidlig tværbinding eller scorch undgås.Such incorporation of free-radical generators is usually done on conventional mixing apparatus. For example, low density polyethylene (LD-PE), two-roll mills or Banbury mixers can be used. The mixing apparatus is heated to approx. 110 ° C and polyethylene, which may contain fillers, antioxidants and coagents, are added and treated for an appropriate time until the material is homogeneously melted. Then the free-radical generator is added, after which an additional mixing time of 2 - 5 minutes is usually sufficient. The temperature should usually not exceed 120 ° C after the addition of the free-radical generator. When the mixing process is complete, the material is granulated in a known manner and is then ready to be applied to extruders or molding machines where the finished blanks are molded at such low temperatures as to avoid premature crosslinking or scorch.
Den varmebehandling, som herefter er nødvendig til at fremkalde tværbindinger i de nu færdigformede emner, kan foretages på en række måder:The heat treatment, which is then necessary to induce crosslinking in the now finished articles, can be carried out in a number of ways:
For extruderede emner kan varmen i princip tilføres i kontinuerlige processer fra vanddamp /1 CV-(continuous vulcanization) eller CCV-(catenary (dvs. kædelinie) CV) anlæg?, fra saltbade og fra fluidi-serede lejer eller i form af infrarødt lys eller mikrobølgeenergi.For extruded workpieces, the heat can in principle be applied in continuous processes from water vapor / 1 CV (continuous vulcanization) or CCV (catenary (ie chain line) CV) systems, from salt baths and from fluidized beds or in the form of infrared light. or microwave energy.
De fire først nævnte varmekilder har den ulempe, at de alle kræver, at emnet, som ønskes tværbundet, på en eller anden måde skal være understøttet for ikke at deformeres ved de høje temperaturer, som tværbindingen foregår ved, og hvor det ikke-tværbundne materiale ville være i smeltet tilstand. Derfor har disse metoder ikke fundet anvendelse ved for eksempel fremstilling af profiler eller rør af tværbundne polymere materialer, men kun ved fremstilling af kabler, hvor lederen er i stand til at holde materialet på plads under vulkaniseringen. Den femte metode (mikrobølgeenergi) til at tilføre den nødvendige varme til de færdige emner er begrænset til polymere materialer, som i sig selv har store dielektriske tabsfaktorer (tg $), eller som ved compoundering er tilført fyldstof, f.eks. carbon black, som giver anledning til store dielektriske tab.The four first mentioned heat sources have the disadvantage that they all require that the article which is desired to be cross-linked must be supported in some way or other than to deform at the high temperatures at which the cross-linking takes place and where the non-cross-linked material would be in the molten state. Therefore, these methods have not been used, for example, in the production of profiles or pipes of cross-linked polymeric materials, but only in the manufacture of cables where the conductor is able to hold the material in place during the vulcanization. The fifth method (microwave energy) to supply the required heat to the finished workpieces is limited to polymeric materials which themselves have large dielectric loss factors (tg $) or which are added to filler by compounding, e.g. carbon black, which gives rise to large dielectric losses.
\ 1ΛΛ513 I stedet for disse meget komplekse metoder til varmeover'føring, som ovenfor omtalt,har den direkte metode, hvor granulatet, som indeholder fri-radikal-danneren, extruderes ud gennem extruderhovedet eller et specialværktøj, samtidig med at der tilføres tilstrækkeligt meget varme til at fremkalde tværbinding i materialet, den ulempe, at det tværbundne materiale let tilstopper extruderen, og at det extruderede emne bliver deformeret og ofte revet i stykker, og en glat overflade opnås ikke.Instead of these very complex heat transfer methods, as mentioned above, the direct method has the extrusion of the granule containing the free radical generator extruded through the extruder head or a special tool while providing sufficient heat to cause cross-linking in the material, the disadvantage that the cross-linked material readily clogs the extruder and that the extruded blank is deformed and often torn, and a smooth surface is not obtained.
De ovennævnte metoder til tværbinding af tværbindingsdygtige polymere materialer, hvor fri-radikal-danneren er tilsat inden formgivningen af de færdige emner, kan for eksempel ikke anvendes på HD-PE, da HD-PE kræver så høje bearbejdningstemperaturer, både under indblandingen af fri-radikal-danneren og under formgivningen, at for tidlig tværbinding eller scorch ikke kan undgås.For example, the aforementioned methods for crosslinking crosslinkable polymeric materials where the free radical generator is added prior to shaping the finished blanks cannot be applied to HD-PE, since HD-PE requires such high processing temperatures, both during the mixing of the free radicals. radical-forming and during shaping that premature cross-linking or scorch cannot be avoided.
En anden kendt metode, som kan anvendes til fremstilling af tværbundne extruderede emner af HD-PE, foregår i princippet ved, at pulverformet HD-PE blandes med peroxid og diverse hjælpestoffer i en blandesnegl, som føder en hydraulisk presse, som under højt tryk føder et opvarmet værktøj udformet i den profil, det færdige emne skal have. Denne metode har to væsentlige ulemper: (1) Processen kan kim udføres i specialudformede maskiner; (2) processen er uegnet til fremstilling af tværbundne emner af HD-PE, som indeholder fyldstof.Another known method which can be used to prepare cross-linked extruded HD-PE blanks is in principle by mixing powdered HD-PE with peroxide and various auxiliaries in a mixing auger which feeds a high pressure hydraulic press a heated tool designed in the profile the finished item should have. This method has two major drawbacks: (1) The process can be performed in specially designed machines; (2) the process is unsuitable for producing cross-linked HD-PE blanks containing filler.
Yed formning af emner af tværbundet polymert materiale efter de kendte metoder til sprøjtestøbning, presning eller sprøjtepresning er det nødvendigt at indarbejde eller iblande fri-radikal-danneren, inden materialet tilføres formningsmaskinen. Dette bevirker, at formningsbetingelseme bliver ugunstige, da for tidlig tværbinding eller scorch kun kan hindres ved lave bearbejdningstemperaturer, og endvidere må selve tværbindingsprocessen foregå i det værktøj, emnet formgives i. Dette medfører, at materialet ikke får optimale egenskaber, og emnernes lange opholdstid i det formgivende værktøj bliver den produktionsbegrænsende faktor, som for langt de fleste produkter gør processen urentabel.In order to mold items of cross-linked polymeric material according to the known methods of injection molding, pressing or injection molding, it is necessary to incorporate or mix the free radical former before the material is supplied to the forming machine. This causes the molding conditions to become unfavorable, since premature cross-linking or scorch can only be prevented at low machining temperatures, and furthermore, the actual cross-linking process must take place in the tool in which the workpiece is designed. This means that the material does not get optimum properties, and the long residence time of the workpieces. the design tool becomes the production limiting factor which, for most products, makes the process unprofitable.
c U4513 5c U4513 5
For at undgå disse ulemper har man fremstillet emnerne af polymere materialer uden tilsætning af tværbindingsmidler og så udnyttet ioniserende stråling til at fremkalde tværbindingen. Imidlertid er sådanne processer begrænset til anvendelse på emner med små tværsnit. Endvidere kræves der et omfattende kostbart udstyr og et stort energiforbrug.To avoid these drawbacks, the blanks have been made of polymeric materials without the addition of crosslinking agents and then ionizing radiation has been utilized to induce the crosslinking. However, such processes are limited to applications on small cross-sectional items. Furthermore, extensive expensive equipment and large energy consumption are required.
USA patentskrift nr. 5.198.868 og det tilsvarende britiske patentskrift nr. 940.876 beskriver en fremgangsmåde til vulkanisering af formede emner ved imprægnering med et vulkaniseringsmiddel. I praksis foretages en neddypning af det afkølede emne i et bad ved 30 - 50°C indeholdende et organisk peroxid opløst i et organisk opløsningsmiddel, såsom acetone eller alkohol. Efter en opholdstid på fra 1 time til nogle dage udtages emnet, og absorberet opløsningsmiddel afdampes i vakuum ved lav temperatur, hvorpå emnet varmebehandles ved 100 - 220°C i en autoklav og senere eventuelt i en presse til opnåelse af vulkaniseringen.U.S. Patent No. 5,198,868 and the corresponding British Patent No. 940,876 disclose a method of vulcanizing molded articles by impregnating with a vulcanizing agent. In practice, the cooled item is immersed in a bath at 30 - 50 ° C containing an organic peroxide dissolved in an organic solvent such as acetone or alcohol. After a residence time of 1 hour to a few days, the blank is removed and the absorbed solvent is evaporated in vacuo at low temperature, whereupon the blank is heat treated at 100 - 220 ° C in an autoclave and later optionally in a press to obtain the vulcanization.
Denne fremgangsmåde er kompliceret, idet den indebærer en række behandlingstrin, og den har videre den ulempe, at den er begrænset til elastomere materialer, såsom gummi, styrengummi, butylgummi og siliconegummi, men især lineære amorfe copolymere af ethylen med a-olefiner, især propylen. Fremgangsmåden er mindre anvendelig til behandling af emner af olefin-homopolymere, frem for alt polyethylen, især fordi det ikke er muligt at opnå en indtrængning af peroxid-vulkaniseringsmidlet. Hvis man ønsker at fremstille emner af polyethylen eller højkrystallinsk polypropylen, er det nødvendigt at blande de homopolymere med lineære ethylen-propylencopolymere for at sikre optagelse af peroxid-tværbindingsmidlet.This process is complicated in that it involves a number of treatment steps and further has the disadvantage of being limited to elastomeric materials such as rubber, styrene rubber, butyl rubber and silicone rubber, but in particular linear amorphous copolymers of ethylene with α-olefins, especially propylene. . The process is less useful for treating olefin homopolymer blanks, especially polyethylene, especially because it is not possible to penetrate the peroxide vulcanizing agent. If one wishes to prepare blanks of polyethylene or high crystalline polypropylene, it is necessary to mix the homopolymers with linear ethylene-propylene copolymers to ensure uptake of the peroxide crosslinking agent.
Tysk fremlæggelsesskrift nr. 1.056.822 beskriver en fremgangsmåde til overfladeforædling af polyethylen fremstillet ved lavtryksmetoden ved påsprøjtning af et tværbindingsmiddel, især organiske peroxider, i form af en finfordelt opløsning på det endnu thermo-plastiske emne. Neddypning af emner af polyethylen fremstillet ved højtryksmetoden i en opløsning indeholdende tværbindingsmiddel eller i flydende tværbindingsmiddel er omtalt som kendt teknik. Ved fremgangsmåden ifølge fremlæggelsesskriftet opnås der kun en overfladetværbinding, og indtrængningen er betinget af en opkvældning af overfladen. Det er ikke nødvendigt at foretage en efterfølgende 6 144513 varmebehandling under tryk.German Patent Specification No. 1,056,822 discloses a process for surface refining of polyethylene made by the low pressure method by spraying a crosslinking agent, especially organic peroxides, in the form of a finely divided solution on the still thermoplastic blank. Immersion of polyethylene blanks made by the high pressure method in a solution containing crosslinking agent or in liquid crosslinking agent is disclosed as known in the art. In the method according to the present disclosure, only one surface crosslink is obtained and the penetration is conditional on a swelling of the surface. It is not necessary to perform a subsequent heat treatment under pressure.
Tysk patent nr. 1.072.803 omhandler en fremgangsmåde til tværbinding af formlegemer af polyethylen ved behandling med dicarboxylsyredi-chlorider, eventuelt i nærvær af kvældningsmidler, såsom carbon-hydrider. Anvendelsen af disse syrechlorider kræver imidlertid, at der arbejdes i et absolut vandfrit miljø, og syrechloriderne er iøvrigt både vanskeligt tilgængelige og vanskeligt håndterbare.German Patent No. 1,072,803 discloses a process for cross-linking moldings of polyethylene by treatment with dicarboxylic acid dichlorides, optionally in the presence of swelling agents such as hydrocarbons. However, the use of these acid chlorides requires working in an absolutely anhydrous environment, and the acid chlorides are otherwise both easily accessible and difficult to handle.
Fransk patentskrift nr. 2.068.882 omhandler en tværbinding af emner af specielle vinylchlorid-copolymere, idet tværbindingen er betinget af, at der i polymermolekylkæderne er inkorporeret nærmere angivne silaner. Tværbindingen fremkaldes ved behandling i surt miljø ved 0 - 150°C, og fremgangsmåden tager særligt sigte på folier og fibre, der dannes i det sure miljø og udtrækkes herfra under samtidig tværbinding.French Patent No. 2,068,882 discloses a crosslinking of blanks of special vinyl chloride copolymers, the crosslinking being conditional on the incorporation of specified silanes into the polymer molecular chains. The crosslinking is elicited by treatment in an acidic environment at 0 - 150 ° C, and the process is particularly aimed at films and fibers formed in the acidic environment and extracted therefrom during simultaneous crosslinking.
Tysk offentliggørelsesskrift nr. 2.204.655 beskriver en fremgangsmåde til fremstilling af elektriske kabler med overtræk og/eller isolering af tværbundet polyethylen, hvor utværbundet polyethylen indeholdende peroxid extruderes sammen med kabelkoren, der understøtter polyethylenet under den efterfølgende tværbinding under varmepåvirkning. Metoden er begrænset til polyethylen med massefylder på 0,935 eller derunder og forudsætter som nævnt, at tværbindingsmidlet er indarbejdet inden extruderingen.German Patent Specification No. 2,204,655 describes a method of making electric cables with coating and / or insulating crosslinked polyethylene, wherein crosslinked polyethylene containing peroxide is extruded together with the cable core supporting the polyethylene during the subsequent crosslinking under heat effect. The method is limited to polyethylene having a density of 0.935 or less and, as mentioned, assumes that the crosslinking agent is incorporated prior to extrusion.
Tysk offentliggørelsesskrift nr. 2.204.658 beskriver en lignende metode under anvendelse af polyethylen med massefylder på 0,935 eller derover. Også her er tværbindingsmidlet fortrinsvis indarbejdet i polyethylen under extruderingen, men man kan også foretage indføringen ved behandling af det formede emne med peroxid i gasfase og påfølgende varmebehandling ved 250°C i et saltbad. Metoden forudsætter tilstedeværelse af en kabelkore til understøtning af polyethylenet under tværbindingen.German Publication No. 2,204,658 discloses a similar method using polyethylene having a density of 0.935 or greater. Here, too, the cross-linking agent is preferably incorporated into polyethylene during extrusion, but the introduction can also be made by treating the molded blank with gas phase peroxide and subsequent heat treatment at 250 ° C in a salt bath. The method assumes the presence of a cable core to support the polyethylene during the cross-linking.
USA patentskrift nr. 3.705-257 beskriver kabler opbygget af flere lag, hvor et eller flere af lagene er tværbundet. Det inderste isolationslag består fortrinsvis af tværbundet PE, der extruderes indeholdende tværbindingsmiddel og tværbindes i et påfølgende vulkaniseringskammer. Efter extrudering af det ydre halvledende lag tvær 1U513 7 bindes de ydre dele af dette lag ved behandling fortrinsvis ved påsprøjtning af dicumylperoxid opløst i acetone eller i smeltet form. Efter påføring overføres kablet med laget af påført tværbindings-middel til et særligt hærdningskammer, hvor tværbinding fremkaldes ved opvarmning. Også den her beskrevne metode er begrænset til fremstilling af kabler.U.S. Patent No. 3,705-257 describes cables made up of multiple layers, with one or more of the layers being cross-linked. The innermost insulating layer preferably consists of cross-linked PE which is extruded containing cross-linking agent and cross-linked in a subsequent vulcanization chamber. After extrusion of the outer semiconducting layer crosses the outer portions of this layer by bonding preferably by spraying dicumyl peroxide dissolved in acetone or in molten form. After application, the cable with the layer of crosslinking agent applied is transferred to a special curing chamber where crosslinking is induced by heating. Also, the method described herein is limited to the manufacture of cables.
I tysk offentliggørelsesskrift nr. 2.214.628 er beskrevet en fremgangsmåde til fremstilling af opskummede, tværbundne polymerpartikler, hvorved polymerpartiklerne (granulatet) suspenderes i en vandig emulsion indeholdende tværbindingsmiddel og opvarmes, til tværbindingen har fundet sted. Først herefter foretages opskumningen og formgivningen. Opskumningsmidlet kan tilsættes til partiklerne enten efter eller samtidigt med tværbindingen.German Publication No. 2,214,628 discloses a process for preparing foamed cross-linked polymer particles, whereby the polymer particles (granules) are suspended in an aqueous emulsion containing crosslinking agent and heated until the crosslinking has taken place. Only then is the foaming and shaping done. The foaming agent can be added to the particles either after or simultaneously with the crosslinking.
Om partiklerne anføres det i skriftet, at der kan være tale om en hvilken som helst partikelform med en dimension på 1 - 10 mm og mere alment, der er ikke nogen begrænsning på partiklernes form og størrelse, der dog skal afpasses efter anvendelsesformålet. Da partiklerne senere skal opskummes i forholdet 5 - 30 gange partikelstørrelsen i en form, er der dog ret snævre grænser for partiklernes form og størrelse, og fagmandens tanker ledes ikke umiddelbart hen på emner, hvis dimension i mindst en retning betydeligt overstiger dimensionen i den eller de andre retninger, såsom rør og kabler.About the particles, it is stated in the document that it can be any particle shape with a dimension of 1 - 10 mm and more generally, there is no restriction on the shape and size of the particles, which must however be adapted to the purpose of use. However, since the particles are later to be foamed in the ratio of 5 to 30 times the size of the particle in a mold, however, there are quite narrow limits to the shape and size of the particles, and the skilled artisan's thoughts are not immediately directed to subjects whose dimension in at least one direction significantly exceeds the dimension of the particle. the other directions, such as pipes and cables.
Ved fremgangsmåden ifølge offentliggørelsesskriftet anvendes der obligatorisk et uopløseligt uorganisk metalsalt som dispergerings-middel for partiklerne for at modvirke sammenklæbning af disse, ligesom der endvidere tilsættes et overfladeaktivt middel for at opløse eller dispergere tværbindingsmidlet homogent og lette penetreringen i polymerpartiklerne.In the process of the disclosure disclosure, an insoluble inorganic metal salt is used as the dispersant for the particles to counteract their adhesion, and a surfactant is also added to dissolve or disperse the homogeneous crosslinking agent and facilitate penetration into the polymer particles.
Hvad angår de anvendelige polymere materialer, er der ganske vist opregnet et stort antal polymere, men de angivne eksempler er alle baseret på den ikke nærmere karakteriserede højtryks-(LD)-polyethylen "Mirason-9" og undtagelsesfrit i en partikeldiameter på 3 “ 4 mm.Regarding the useful polymeric materials, a large number of polymers have been listed, but the examples given are all based on the unspecified high-pressure (LD) polyethylene "Mirason-9" and exceptionally in a particle diameter of 3 "4 mm.
De Ønskede gelprocenter er angivet som ca. 10 - 70$, idet det anføres, at højere gelprocenter vanskeliggør opskumningen. Imidlertid er der 144513 intet i teksten, der sandsynliggør, at disse "uønskede" højere gel-procenter overhovedet vil kunne opnås, idet der i eksemplerne ikke opnås over 12.%.The desired gel percentages are indicated as approx. $ 10 - $ 70, stating that higher gel percentages make foaming difficult. However, there is nothing in the text which makes it probable that these "undesirable" higher gel percentages can be obtained at all, in the examples not exceeding 12%.
Hvis derfor gennemsnitsfagmanden, der havde erkendt de ovenfor angivne ulemper ved den kendte teknik og ønskede at tilvejebringe en metode til fremstilling af homogent tværbundne formede emner, hvis dimension i mindst en retning betydeligt overstiger dimensionen i den anden eller de andre retninger, med høje gelprocenter uden risiko for deformering, skulle vurdere, om den i offentliggørelsesskriftet omhandlede fremgangsmåde kunne tillempes hertil/ ville han komme til det resultat, at der skulle overvindes betydelige fordomme, navnlig hvis han ønskede at arbejde med HD-PE.Therefore, if the average skilled person who had recognized the above-mentioned disadvantages of the prior art and wanted to provide a method for producing homogeneously cross-linked shaped articles whose dimension in at least one direction significantly exceeds the dimension in the other or other directions, with high gel percentages without risk of deformity, should assess whether the method described in the disclosure could be applied to this / would he come to the conclusion that significant prejudice would be overcome, especially if he wanted to work with HD-PE.
Hvad han med sikkerhed kunne vide fra offentliggørelsesskriftet var, at partikler af størrelsesordenen 3 - 4 mm lader sig tværbinde til gelprocenter på op til 70# uden sammenklæbning, hvis de opvarmes i et vandigt medium, hvori der er dispergeret peroxid ved hjælp af et overfladeaktivt middel, og hvori der endvidere findes et uopløseligt uorganisk metalsalt.What he could know for sure from the disclosure was that particles of the order of 3 - 4 mm can be crosslinked to gel percentages of up to 70 # without bonding if heated in an aqueous medium containing dispersed peroxide by a surfactant. , and further comprising an insoluble inorganic metal salt.
Om formstabiliteten ved processen og om muligheden for en højere gelprocent, specielt ved emner af godstykkelse på over nogle få mm, ville han intet kunne udlede med sikkerhed.About the stability of the mold in the process and about the possibility of a higher gel percentage, especially for items of thickness of more than a few mm, he could not deduce anything with certainty.
Derimod ville han ikke kunne frigøre sig for den fordom, der er udtrykt i ovennævnte USA patent nr. 3 198 868, der beskriver vulkanisering af formede emner, såsom kabler, rør og lignende, af elastomere materialer, og hvor det udtrykkeligt angives, at tværbinding af ethylen-homopolymere er umulig, med mindre der inkorporeres EP-copolymere.In contrast, he would not be able to escape the prejudice expressed in the aforementioned United States Patent No. 3,198,868, which describes the vulcanization of molded articles, such as cables, tubes and the like, of elastomeric materials, and where it is expressly stated that crosslinking of ethylene homopolymers is impossible unless EP copolymers are incorporated.
Selv om tysk offentliggørelsesskrift 2 214 628 modbeviser denne påstand, når talen er om ikke nærmere karakteriserede LD-PE partikler af små dimensioner, må fordommen fra USA patentet dog veje tungt, da der er tale om emner af samme art som i ansøgningen, ikke mindst når talen er om HD-polyethylen, hvis molekylstruktur på ingen måde kunne tilsige en lettere penetrering end for LD-PE.However, even though German disclosure 2 214 628 disproves this claim when the speech is about unspecified LD-PE particles of small dimensions, the prejudice of the United States patent must weigh heavily, since these are subjects of the same kind as in the application, not least when talking about HD polyethylene, whose molecular structure could in no way imply easier penetration than for LD-PE.
Formålet med den foreliggende opfindelse er at tilvejebringe en 144513 9 fremgangsmåde af den i krav l's indledning anførte art, der ikke er behæftet med de kendte metoders begrænsninger i fremstillelige emner og i materialevalg, og som især er velegnet til fremstilling af emner af HD-polyethylen uden deformering.The object of the present invention is to provide a process of the kind set out in the preamble of claim 1 which is not subject to the limitations of known methods in workable items and in material selection, and which is particularly suitable for the production of HD polyethylene parts. without deformation.
Dette opnås ifølge opfindelsen ved, at gå frem som anført i krav l’s kendetegnende del, hvilket må anses for overraskende på basis af ovennævnte analyse af kendt teknik, især tysk offentliggørelsesskrift nr. 2.214.628.This is achieved in accordance with the invention by proceeding as set forth in claim 1, which is considered surprising on the basis of the above-mentioned analysis of the prior art, in particular German Publication No. 2,214,628.
Især måtte man anse gennemførelsen af fremgangsmåden ifølge opfindelsen for umulig, hvis man ikke vil finde sig i at emnerne klæber sammen og tværbindes uregelmæssigt, al den stund der ikke tilsættes uopløselige uorganiske metalsalte, men som vist i eksemplerne tværtimod polyvinylalkohol, der er vist som værende utilstrækkelig i tysk offentliggørelsesskrift nr. 2.214.628.In particular, the implementation of the process according to the invention had to be considered impossible if it would not be found that the articles adhere together and cross-link irregularly, while no insoluble inorganic metal salts are added, but as shown in the examples, on the contrary, polyvinyl alcohol shown as present. insufficient in German Publication No. 2,214,628.
Yed fremgangsmåden ifølge opfindelsen fremstilles emnerne på sædvanlig måde ud fra de sædvanlige udgangsmaterialer, idet der ikke tilsættes organisk peroxid, men udgangsmaterialerne kan indeholde fyldstoffer og/eller antioxidanter og/eller eventuelle coagenter for tværbindingen. Valget af et olefinpoly-mert eller vinylchloridpolymert materiale som udgangsmateriale er kim. begrænset af to faktorer, nemlig det færdige produkts egenskaber og de forarbejdningsmaskiner, som står til rådighed. Hvis således der ved forarbejdningen ikke er opnået et spændingsfrit emne, hvilket kan skyldes den konkrete extruder eller anden forarbejdningsmaskine, kan man ifølge opfindelsen med fordel gøre emnet spændings-frit inden opvarmningen i nærværelse af peroxid ved at foretage en mellemliggende spændingsudligning, f.eks. ved en opvarmning af emnet, inden dette indføres i det peroxidholdige medium.In the process of the invention, the blanks are prepared in the usual manner from the usual starting materials, with no organic peroxide added, but the starting materials may contain fillers and / or antioxidants and / or any coagent for the crosslinking. The choice of an olefin polymer or vinyl chloride polymeric starting material is germ. limited by two factors, namely the properties of the finished product and the processing machines available. Thus, if during the processing a voltage-free blank is not obtained, which may be due to the concrete extruder or other processing machine, according to the invention it is advantageous to make the blank tension-free before heating in the presence of peroxide by making an intermediate voltage equalization, e.g. by heating the blank before introducing it into the peroxide-containing medium.
I øvrigt vil man, hvis emnet for eksempel skal være af HD-PE, vælge den HD-PE-type, som giver de optimale kørselsbetingelser, således at produktionen af emner er letløbende og fejlfri, og produkterne får optimale egenskaber. Endvidere er fremgangsmåden ifølge opfindelsen ikke begrænset til emner, fremstillet ved extrudering og sprøjtestøbning, men kan anvendes i forbindelse med alle metoder til fremstilling af emner af polymere materialer.For example, if the item is to be HD-PE, for example, the HD-PE type will be chosen, which gives the optimum driving conditions, so that the production of workpieces is smooth and error-free and the products have optimum properties. Furthermore, the process of the invention is not limited to blanks made by extrusion and injection molding, but can be used in connection with all methods of manufacturing blanks of polymeric materials.
Når emnet er formet ved en af de kendte metoder, indføres et eller 10 m 513 flere af de gængse organiske peroxider, såsom di-tert.-butylperoxid og dieumylperoxid eller organiske hydroperoxider, såsom tert.-butyl-• hydroperoxid. Et særligt foretrukket peroxid er l,l-bis-(tert.-but’ylperoxy)-3,3,5-trimethylcyclohexan, der i særlig ringe grad fremkalder deformation under tværbindingen, idet det fremkalder tværbinding allerede ved ret lave temperaturer (ca. 100°C). Valget af tværbindingsmidlet til et givet system afhænger blandt andet af det olefinpolymere eller vinylchloridpolymere materiale, som skal tværbindes, idet fremgangsmåden principielt kan anvendes på alle tværbindingsdygtige olefinpolymere eller vinylchloridpolymere materialer under forudsætning af, at tværbindingsmidlet eller -midlerne er opløselige i det polymere materiale.When the blank is formed by one of the known methods, one or 10 m 513 more of the usual organic peroxides such as di-tert-butyl peroxide and diumyl peroxide or organic hydroperoxides such as tert-butyl hydroperoxide are introduced. A particularly preferred peroxide is 1,1-bis- (tert-butyl peroxy) -3,3,5-trimethylcyclohexane, which causes particularly deformation during the crosslinking, inducing crosslinking already at fairly low temperatures (ca. 100 ° C). The choice of crosslinking agent for a given system depends, inter alia, on the olefin polymer or vinyl chloride polymeric material to be crosslinked, the process being applicable in principle to all crosslinkable olefin polymer or vinyl chloride polymeric materials provided that the crosslinking agent or agents are soluble in the polymer.
Endelig kan man ved fremgangsmåden ifølge opfindelsen opfylde følgende betingelser, der er af særlig betydning ved fremstilling af emner til specielle formål, enten enkeltvis eller i kombination: (1) Processen kan styres, så man opnår den ønskede tværbindingsgrad, dvs. en tværbinding for for eksempel HD-PE, der er tilstrækkelig høj, men ikke så kraftig, at man opnår en sådan nedgang i massefylden, at der ikke længere er tale om HD-PE.Finally, the process according to the invention can fulfill the following conditions which are of particular importance in the preparation of articles for special purposes, either individually or in combination: (1) The process can be controlled to achieve the desired degree of cross-linking, ie. a cross-linking, for example, HD-PE, which is sufficiently high but not so strong as to achieve such a decrease in density that it is no longer HD-PE.
(2) Processen kan styres således, at emnerne kan udvise en acceptabel lille dimensionsændring.(2) The process can be controlled so that the items can exhibit an acceptable small dimensional change.
(3) Processen kan styres således, at emnerne ikke indeholder per-oxidrester i erkendelig mængde.(3) The process can be controlled so that the blanks do not contain peroxide residues in appreciable amount.
Indføringen af peroxid-tværbindingsmidlet eller -tværbindingsmidlerne kan for eksempel foregå ved, at emnerne neddyppes i en vandig dispersion indeholdende et overfladeaktivt middel og et eller flere peroxider i form af en emulsion fremstillet enten ved en mekanisk bearbejdning, f.eks. i en højtrykshomogenisator, eller under anvendelse af overfladeaktive midler, såsom emulgatorer, beskyttelseskolloider eller lignende.For example, the introduction of the peroxide crosslinking agent or crosslinking agents can be effected by immersing the blanks in an aqueous dispersion containing a surfactant and one or more peroxides in the form of an emulsion prepared either by mechanical processing, e.g. in a high pressure homogenizer, or using surfactants such as emulsifiers, protective colloids or the like.
Det har overraskende vist sig, at peroxidet under de i krav 1 anførte temperaturbetingelser vil fordele sig relativt homogent i emnet, 144513 11 således at der efter tværbindingsprocessen iagttages en tværbinding med en særdeles god indtrængningsdybde.Surprisingly, it has been found that under the temperature conditions set out in claim 1, the peroxide will distribute relatively homogeneously in the blank, so that after the crosslinking process a crosslinking with a very good penetration depth is observed.
Selve tværbindingen af emnet fremkaldes ved·en passende behandling, f.eks. termisk, enten i forbindelse med formgivningen og/eller med indføringen af peroxidet eller peroxiderne eller i et separat procestrin. I første tilfælde kan den til selve formgivningen nødvendige varme helt eller delvis medgå til den efterfølgende tværbindingsproces.The crosslinking of the subject itself is elicited by an appropriate treatment, e.g. thermally, either in the design and / or in the introduction of the peroxide or peroxides or in a separate process step. In the first case, the heat needed for the design itself may be wholly or partially incorporated into the subsequent crosslinking process.
En særlig foretrukken variant af fremgangsmåden ifølge opfindelsen består i, at man gennemfører indføringen af peroxidet eller peroxiderne og tværbindingsprocessen i et og samme vandige medium i et lukket eller tryktæt system. Det vandige medium har fortrinsvis tilnærmelsesvis samme massefylde som det fremstillede emne, hvorved det sikres, at emnet ikke deformeres under varmebehandlingen. Om ønsket kan man derfor korrigere mediets massefylde ved tilsætning af et eller flere salte.A particularly preferred variant of the process according to the invention consists in carrying out the introduction of the peroxide or peroxides and the crosslinking process in one and the same aqueous medium in a closed or pressure-tight system. Preferably, the aqueous medium has approximately the same density as the fabricated article, ensuring that the blank does not deform during the heat treatment. Therefore, if desired, the density of the medium can be corrected by adding one or more salts.
Til opnåelse af en særlig sikker styring af tværbindingsgraden kan det være hensigtsmæssigt efter den del af opvarmningen, hvorunder peroxidet trænger ind i emnet, at udskifte det peroxid-holdige medium med et vandigt medium, der ikke indeholder peroxid, således at der ikke under den efterfølgende opvarmning trænger yderligere peroxid ind.In order to achieve a particularly safe control of the degree of cross-linking, it may be appropriate, after the part of the heating during which the peroxide penetrates into the workpiece, to replace the peroxide-containing medium with an aqueous medium containing no peroxide, so that during the subsequent heating penetrates further peroxide.
Specielt ved fremstilling af kabler kan man for at forebygge en sammenklæbning ved oprulningen af det tværbundne kabel foretage en bevikling af kablet efter indtrængningen af peroxidet, men inden den afsluttende behandling t'il fremkaldelse af tværbindingen.Especially in the manufacture of cables, in order to prevent an adhesion in the winding of the cross-linked cable, a winding of the cable can be carried out after the penetration of the peroxide, but before the final treatment to produce the cross-linking.
Det har overraskende vist sig, at man ved fremgangsmåden ifølge opfindelsen opnår en tværbinding med en overordentlig god indtrængningsdybde og homogenitet, uden at emnerne deformeres. En standardprøve for tværbindingens omfang er bestemmelse af den uopløselige del af det tværbundne polymere materiale ved ekstraktion i kogende stabiliseret opløsningsmiddel. Por HD-PE har man ved ekstraktion i kogende stabiliseret dekalin fundet, at 80 - 100¾ af materialet var uopløseligt efter tværbinding ved fremgangsmåden ifølge opfindelsen.Surprisingly, it has been found that the process according to the invention achieves a crosslinking with an extremely good penetration depth and homogeneity without deforming the blanks. A standard test for the extent of crosslinking is the determination of the insoluble portion of the crosslinked polymeric material by extraction in boiling stabilized solvent. For HD-PE extraction, in boiling stabilized decalin extraction, 80-100¾ of the material was found to be insoluble after crosslinking by the process of the invention.
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Behandlingstiden, både hvad angår indføringen af tværbindingsmidlet eller -midlerne og selve tværbindingsprocessen, afhænger blandt andet af behandlingens temperaturforløb, det anvendte olefin- eller vinylchloridpolymere materiale eller materialer, godstykkelsen, peroxidet eller peroxidernes art og den ønskede tværbindingsgrad, men vil i reglen være fra nogle få timer op til et døgn.The treatment time, both with respect to the introduction of the crosslinking agent (s) and the crosslinking process itself, depends, inter alia, on the temperature course of the treatment, the olefin or vinyl chloride polymeric material or materials used, the thickness, peroxide or peroxides nature and the desired degree of crosslinking, but will usually be from some a few hours up to a day.
tilsvarende betragtninger gælder for behandlingstrykket, idet man både kan arbejde ved atmosfæretryk og ved et større eller mindre overtryk. Generelt kan man variere parametrene temperatur, behandlingstid og tryk inden for særdeles vide grænser. Afgørende for valget er især de ønskede egenskaber ved slutproduktet, f.eks. tværbindingsgrad, dimensionsstabilitet og tilladeligt indhold af peroxidrester. Disse egenskaber samt procesforløbet i øvrigt er også bestemt af det valgte peroxid, hvis egenskaber på sin side sætter bredere eller snævrere grænser for temperatur, tid og tryk.similar considerations apply to the treatment pressure, as one can work both at atmospheric pressure and at a greater or lesser overpressure. In general, the parameters temperature, processing time and pressure can be varied within very wide limits. Crucial to the choice are the desired properties of the final product, e.g. crosslinking degree, dimensional stability and permissible content of peroxide residues. These properties as well as the process process are also determined by the selected peroxide, whose properties in turn impose wider or narrower limits on temperature, time and pressure.
Det kan specielt nævnes, at den blæredannelse, f.eks. forårsaget af flygtige bestanddele fra eventuelle fyldstoffer eller af sønderdelingsprodukter fra tværbindingsmidlerne, som kendes, f.eks. fra den ovenfor beskrevne kontinuerte vulkanisering , undgås ved fremgangsmåden ifølge opfindelsen. Dette opnås ved et passende valg af ovennævnte parametre, idet for eksempel en tilstrækkelig lang behandlingstid giver nedbrydningsprodukteme mulighed for at diffundere ud, mens man også, f.eks. ved en trykforøgelse,helt eller delvis kan undertrykke en sådan blæredannelse.In particular, it can be mentioned that the blistering, e.g. caused by volatile constituents from any fillers or by decomposition products of the crosslinking agents known, e.g. from the continuous vulcanization described above is avoided by the method of the invention. This is achieved by a suitable choice of the above parameters, for example, a sufficiently long processing time allows the degradation products to diffuse out, while also, e.g. by a pressure increase, may fully or partially suppress such blistering.
Yed fremgangsmåden ifølge opfindelsen kan der som nævnt ovenfor også medanvendes coagenter. Disse kan enten indføres under formgivningen af emnet, eller de kan indgå i det anvendte peroxidholdige væskeformige medium. Anvendelige coagenter er flerumættede organiske forbindelser, såsom triallyleyanurat, sorbinsyre og ethylenglycol-dimethacrylat.As mentioned above, coagent agents can also be used in the process according to the invention. These can either be introduced during the shaping of the workpiece or they may be included in the peroxide-containing liquid medium used. Useful coagents are polyunsaturated organic compounds such as triallyley anurate, sorbic acid and ethylene glycol dimethacrylate.
Selve tværbindingen af emnet efter introduktionen af tværbindingsmidlet eller -midlerne kan endvidere i stedet for ved varmebehandling fremkaldes ved behandling af emnet ved en lavere temperatur med aktivatorer eller acceleratorer for peroxiderne.Furthermore, the crosslinking of the workpiece after the introduction of the crosslinking agent or agents can be induced instead of heat treatment by treating the workpiece at a lower temperature with activators or accelerators for the peroxides.
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Fremgangsmåden ifølge opfindelsen illustreres nærmere ved nedenstående eksempler, hvor symbolet 0 betegner et i Danmark registreret varemærke.The process according to the invention is further illustrated by the following examples, where the symbol 0 denotes a trademark registered in Denmark.
EKSEMPEL 1 515 g polyethylen ("Hostalen ® GM 5010", smelteindex MFI 0,3 g/10 min massefylde 0,955 g/cm·^ indeholdende 2,5 - 3,0 i> carbon black) i form af to rør med udvendig diameter på 17,0 mm og godstykkelse 3,0 mm samt en plade med dimensionerne 600 x 65 x 11,3 mm anbringes i en rørautoklav med diameter 80 mm og længde 680 mm.EXAMPLE 1 515 g of polyethylene ("Hostalen® GM 5010", Melt Index MFI 0.3 g / 10 min density 0.955 g / cm · containing 2.5 - 3.0 i carbon black) in the form of two outer diameter tubes of 17.0 mm and a thickness of 3.0 mm and a plate with dimensions 600 x 65 x 11.3 mm are placed in a tube octave with a diameter of 80 mm and a length of 680 mm.
Ler fremstilles en emulsion af 20 g di-tert.-butylperoxid ("Trigonox B" Noury van der Lande) 0,1 g polyvinylalkohol ("Elvanol 7260", du Pont)Clay is prepared an emulsion of 20 g of di-tert-butyl peroxide ("Trigonox B" Noury van der Lande) 0.1 g of polyvinyl alcohol ("Elvanol 7260", du Pont)
2,6 g oliesyre 0,3 g NaOH2.6 g oleic acid 0.3 g NaOH
20 g vandfrit Na2S0^.20 g of anhydrous Na 2 SO 4.
Autoklaven fyldes med destilleret vand og ovennævnte emulsion. Herpå cirkulerer væsken i autoklaven ved hjælp af en stempelpumpe, der samtidig virker som homogenisator.The autoclave is filled with distilled water and the above emulsion. The liquid is then circulated in the autoclave by means of a plunger pump which simultaneously acts as a homogenizer.
I løbet af 2 1/2 time bringes væsketemperaturen op til 120° C og holdes der i 4 timer, hvorpå den hæves til 133° 0 og holdes der i 14 timer.During 2 1/2 hours, the liquid temperature is brought up to 120 ° C and held for 4 hours, then raised to 133 ° 0 and maintained for 14 hours.
Efter den således fremkaldte tværbinding er rørenes udvendige diameter øget fra 17,0 til 17,2 mm, medens deres massefylde er faldet fra 0,955 til 0,925 g/cm^.Following the cross-linking thus developed, the outer diameter of the tubes is increased from 17.0 to 17.2 mm, while their density has decreased from 0.955 to 0.925 g / cm 2.
Ved dekalinekstraktion findes for rørenes vedkommende et gelindhold på 97 i°. Ved udtagning fra autoklaven havde rørene ingen tendens til sammenklæbning.For decalin extraction, a gel content of 97 i ° is found for the tubes. When removed from the autoclave, the tubes had no tendency for adhesion.
For den 113 mm tykke plade måles en gelprocent på 92 i materiale, der ligger op til 1 mm fra overfladen. I materiale, der ligger 3 -4 mm fra overfladen, bestemmes gelindholdet til 80 $.For the 113 mm plate a gel percentage of 92 is measured in material up to 1 mm from the surface. In material that is 3 -4 mm from the surface, the gel content is determined at $ 80.
l4 144513 EKSEMPEL· 2 I den i eksempel 1 omtalte rørautoklav anbringes 495 g polyethylen bestående af 7 stk. polyethylenrør ("Hostalen IS' GM 50IO", MFI 0,3 g/10 min., massefylde 0,955 g/cm , indeholdende 2,5 - 3,0 $ carbon black), 60 - 65 cm lange, udvendig diameter 17,0 mm og godstykkelse 2,8 mm.EXAMPLE · 2 The 495 g polyethylene consisting of 7 pcs. polyethylene tube ("Hostalen IS 'GM 50IO", MFI 0.3 g / 10 min, density 0.955 g / cm, containing 2.5 - 3.0 $ carbon black), 60 - 65 cm long, outer diameter 17.0 mm and thickness of goods 2.8 mm.
Der fremstilles en emulsion af samme sammensætning som nævnt i eksempel 1.An emulsion of the same composition as mentioned in Example 1 is prepared.
Autoklaven fyldes med destilleret vand og ovennævnte medium. Herpå cirkulerer væsken i autoklaven ved hjælp af en tandhjulspumpe med en hastighed på 6 1/min.The autoclave is filled with distilled water and the above medium. Then the liquid circulates in the autoclave by means of a gear pump at a speed of 6 l / min.
I løbet af 2 timer bringes væsketemperaturen op til 115° C og holdes der i 3 timer, hvorpå den hæves til 158° C i løbet af de næste 5 timer og holdes på denne temperatur i yderligere 7 timer.Over 2 hours, the liquid temperature is brought up to 115 ° C and held for 3 hours, then raised to 158 ° C over the next 5 hours and kept at this temperature for an additional 7 hours.
Efter den således fremkaldte tværbinding er rørenes udvendige diameter øget fra 17,0 til 17,1 mm, medens massefylden er faldet fra 0,955 til 0,918 g/cm3.Following the cross-linking thus developed, the outside diameter of the tubes is increased from 17.0 to 17.1 mm, while the density has decreased from 0.955 to 0.918 g / cm 3.
Yed dekalinekstraktion findes en gelprocent på 99 - 100.Yed decalin extraction has a gel percentage of 99 - 100.
Ved udtagning fra autoklaven viser rørene ingen tendens til sammenklæbning.When removed from the autoclave, the tubes show no tendency to adhere.
EKSEMPEL· 3 I den i eksempel 1 omtalte rørautoklav anbringes 475 g polyethylen bestående af en 100 x 70 x 12,5 mm presset polyethylenplade, der ikke indeholder fyldstoffer ("Hostalen® GM 6050, MEI 0,3 g/10 min., massefylde 0,946 g/cm3) samt en extruderet polyethylenplade 600 x 60 x 11,3 mm (Hostalen® GM 5010")EXAMPLE 3 In the stirring autoclave mentioned in Example 1, 475 g of polyethylene consisting of a 100 x 70 x 12.5 mm pressed polyethylene plate containing no fillers is placed ("Hostalen® GM 6050, MEI 0.3 g / 10 min, density"). 0.946 g / cm 3) and an extruded 600 x 60 x 11.3 mm polyethylene sheet (Hostalen® GM 5010 ")
Der fremstilles en emulsion af samme sammensætning som nævnt i eksempel 1.An emulsion of the same composition as mentioned in Example 1 is prepared.
144513 15144513 15
Efter fyldning af autoklaven med ovennævnte emulsion og destilleret vand tværbindes polyethylenet under samme betingelser som omtalt i eksempel 2.After filling the autoclave with the above emulsion and distilled water, the polyethylene is crosslinked under the same conditions as described in Example 2.
Efter den således fremkaldte tværbinding måles i polyethylenpladen af "GM 6050" en gelprocent på 77»4 i· en afstand på ca. 6 mm fra overfladen.After the cross-linking thus developed, a gel percentage of 77 »4 is measured in the polyethylene plate of" GM 6050 "at a distance of approx. 6 mm from the surface.
I polyethylenpladen af "GM 5010" måles en gelprocent på 99,7 i en afstand på maximalt 2,5 mm fra overfladen. I materiale, der ligger 5 - 6 mm fra overfladen er gelprocenten 86,2.In the polyethylene plate of "GM 5010", a gel percentage of 99.7 is measured at a distance of maximum 2.5 mm from the surface. In material 5 to 6 mm from the surface, the gel percentage is 86.2.
EKSEMPEL 4 tværbinding af enublødgjort PVC-profil ca. 1,5 mm tyk.Example 4 crosslinking of enameled PVC profile approx. 1.5 mm thick.
Der fremstilles en emulsion af samme sammensætning som i eksempel 1. Den doseres i en mængde, der svarer til 10 vægtprocent peroxid i forhold til PVC-genstandens vægt, hvorefter den fyldes i en 2 liter rustfri stålautoklav sammen med PVC-genstanden. Temperaturen i autoklaven blev langsomt hævet til 125° 0 (ca. 2 timer), hvorefter denne temperatur blev holdt i 48 timer. Efter denne behandling kunne følgende forandringer iagttages hos PVC-genstanden: (a) Ved en Soxhlet-ekstraktion med tetrahydrofuran konstateredes en uopløselig rest på 25 (mod 0 $ i en ubehandlet reference).An emulsion of the same composition is prepared as in Example 1. It is dosed in an amount equal to 10% by weight of peroxide to the weight of the PVC article and then filled into a 2 liter stainless steel autoclave together with the PVC article. The temperature in the autoclave was slowly raised to 125 ° 0 (about 2 hours), after which this temperature was kept for 48 hours. Following this treatment, the following changes could be observed with the PVC article: (a) At a Soxhlet extraction with tetrahydrofuran, an insoluble residue of 25 (against $ 0 in an untreated reference) was found.
(b) Ved en varmeindtryksprøve (EMKO (10)5 102/71 §15, a) dog 1 time ved 95° C fandtes et indtryk på 2,25 mm (mod 4,00 mm i en ubehandlet reference).(b) In a heat impact test (EMKO (10) 5 102/71 §15, a), however, for 1 hour at 95 ° C an impression of 2.25 mm was found (against 4.00 mm in an untreated reference).
(c) Ved en mekanisk måling i et Instron trækprøveapparat måltes et Young modul på 70 bar/$ (mod ca. 140 barHo i en ubehandlet reference).(c) By a mechanical measurement in an Instron tensile tester, a Young module of 70 bar / $ was measured (versus about 140 barHo in an untreated reference).
l6 144513 EKSEMPEL· 5 I rørautoklaven brugt i eksempel 1 anbringes 569 g polyethylen bestående af 7 polyethylenrør 17 mm x 2,5 mm (diameter ^godstykkelse). De anvendte rør var fremstillet ud fra "Hostalen GM 5010" eller "LupolenvS/ 5261Z" (massefylde 0,950, smelteindex (DIN 55735) ved 21,6 kg belastning; 1,7 - 2,3). Ted nogle af rørene var der anvendt de nedenfor angivne coagenter, og to af rørene var spændings-udlignet.EXAMPLE 5 In the tube autoclave used in Example 1, 569 g of polyethylene consisting of 7 polyethylene tubes are placed 17 mm x 2.5 mm (diameter ^ thickness). The pipes used were made from "Hostalen GM 5010" or "LupolenvS / 5261Z" (density 0.950, melt index (DIN 55735) at 21.6 kg load; 1.7 - 2.3). Ted some of the tubes, the coagents listed below were used and two of the tubes were voltage equalized.
En emulsion fremstilles af 10 g 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexan 30 g 2,5-dimethyl-2,5-di(t-butylpexoxy)hexan 32,6 g oliesyreAn emulsion is prepared from 10 g of 1,1-bis (t-butyl peroxy) -3,3,5-trimethylcyclohexane 30 g of 2,5-dimethyl-2,5-di (t-butylpexoxy) hexane 32.6 g of oleic acid
4,7 g NaOH4.7 g NaOH
1,3 g p o ly viny 1 alko lio 1 50 g Na2S0^ 5 1 udkogt vand.1.3 g p o ly viny 1 alko lio 1 50 g Na2S0 ^ 5 1 boiled water.
Emulsionen påfyldes autoklaven og cirkuleres med en centrifugalpumpe . Temperaturen holdes på 82°C i 7 timer, hvorefter emulsionen udskiftes med udkogt vand indeholdende 50 g Na^SO^.The emulsion is filled with the autoclave and circulated with a centrifugal pump. The temperature is kept at 82 ° C for 7 hours, after which the emulsion is replaced with boiled water containing 50 g of Na 2 SO 2.
Over en periode på 12 timer øges temperaturen fra 105°C til 150°C med 3 - 5°C pr. time, idet temperaturstigningen er mindst ved de laveste temperaturer.Over a period of 12 hours, the temperature increases from 105 ° C to 150 ° C by 3-5 ° C. The temperature rise is at least at the lowest temperatures.
Efter tværbindingen måles følgende massefylder, gelprocent og krympning i rørenes længderetning.After the crosslinking, the following mass fill, gel percentage and shrinkage are measured in the longitudinal direction of the tubes.
17 14451317 144513
Materiale Gelprocent Massefylde Krympning % "Hostalen ® GM 5010" 76 0,947 3,9 "Hostalen ® GM 5010" + 2% ethylen-glyeoldimethacrylat 87 0,946 4,0 "Hostalen ®GM 5010" + 2% sorbinsyre 83 0,946 4,0 "Hostalen ®GM 5010" + 2% triallylcyanurat 85 0,945 2,8 "Hostalen ®GM 5010" varmebehandlet for at fjerne indre spændinger 80 0,946 2,3 "Lupolen ®526l Z" 99 0,931 4,2 "Lupolen ®5261 Z" varmebehandlet 99 0,931 2,7 EKSEMPEL 6 I rørautoklaven fra eksempel 1 anbringes 420 g polyethylen bestående af 8 polyethylenrør 17 mm x 2,5 mm. Rørene^var dels fremstillet af "Lupolen ® 5261Z" og dels af "Rigidex ® Η 02054P" (massefylde 0,954} smelteindex (LIN53735) ved 21,6 kg belastning: 2,0).Material Gel Percent Density Shrinkage% "Hostalen® GM 5010" 76 0.947 3.9 "Hostalen® GM 5010" + 2% Ethylene-Glyole Dimethacrylate 87 0.946 4.0 "Hostalen®GM 5010" + 2% Sorbic Acid 83 0.946 4.0 "Hostalen ® GM 5010 "+ 2% triallyl cyanurate 85 0.945 2.8" Hostal ® GM 5010 "heat treated to remove internal stresses 80 0.946 2.3" Lupolen®526l Z "99 0.931 4.2" Lupolen®5261 Z "heat treated 99 0.931 2.7 EXAMPLE 6 In the tube autoclave of Example 1, 420 g of polyethylene consisting of 8 polyethylene tubes are placed 17 mm x 2.5 mm. The tubes ^ were made partly of "Lupolen ® 5261Z" and partly of "Rigidex ® 20 02054P" (density 0.954} melt index (LIN53735) at 21.6 kg load: 2.0).
En emulsion fremstilles som i eksempel 5, dog med 20 g 1,1-bis(t-butylperoxy)-3}3}5-trimethylcyclohexan som eneste peroxid.An emulsion is prepared as in Example 5, however, with 20 g of 1,1-bis (t-butyl peroxy) -3} 3} 5-trimethylcyclohexane as the sole peroxide.
Emulsionen påfyldes autoklaven og cirkuleres med en centrifugalpumpe.The emulsion is filled with the autoclave and circulated with a centrifugal pump.
Temperaturen holdes på 94° C i 6,5 timer, hvorefter temperaturen i løbet af 9 timer øges til 150° 0} idet temperaturstigningen indtil 110° C begrænses til 2 - 40 C pr. time.The temperature is kept at 94 ° C for 6.5 hours, after which the temperature is increased to 150 ° 0 during 9 hours, with the temperature increase up to 110 ° C being limited to 2 - 40 C per day. hour.
Temperaturen opretholdes på 150° C i 2 timer.The temperature is maintained at 150 ° C for 2 hours.
Efter tværbindingen måles følgende:Following the crosslinking, the following is measured:
Materiale Gelprocent Massefylde Krympning % "Lupolen ® 5261" 97 0,930 3}1 "Rigidex ©HO2054P" 82 0,933 5,8Material Gel Percent Density Shrinkage% "Lupolen ® 5261" 97 0.930 3} 1 "Rigidex © HO2054P" 82 0.933 5.8
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB47993/73A GB1489580A (en) | 1973-10-15 | 1973-10-15 | Manufacturing cross-linked moulded articles from cross-linkable polymeric materials |
GB4799373 | 1973-10-15 |
Publications (3)
Publication Number | Publication Date |
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DK536374A DK536374A (en) | 1975-06-16 |
DK144513B true DK144513B (en) | 1982-03-22 |
DK144513C DK144513C (en) | 1982-10-18 |
Family
ID=10446990
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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DK536374A DK144513C (en) | 1973-10-15 | 1974-10-14 | PROCEDURE FOR THE PREPARATION OF CROSS-BOND FORMED SUBSTANCES BASED ON CROSS-BONDABLE OLEPHINE POLYMERS OR VINYL CHLORIDE POLYMER MATERIALS |
Country Status (7)
Country | Link |
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JP (1) | JPS586736B2 (en) |
DE (1) | DE2448861C2 (en) |
DK (1) | DK144513C (en) |
FI (1) | FI62116C (en) |
GB (1) | GB1489580A (en) |
NO (1) | NO139299C (en) |
SE (1) | SE410194B (en) |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
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NL7908964A (en) * | 1979-12-13 | 1981-07-16 | Akzo Nv | PROCESS FOR PREPARING MASTERBATCHES OF PEROXIDES IN POLYMERS. |
DE3007531A1 (en) * | 1980-02-28 | 1981-10-08 | Dynamit Nobel Ag, 5210 Troisdorf | MOLDED BODY FROM PLASTIC WITH A PEROXYDICALLY CROSSLINKABLE COMPONENT AND METHOD FOR THE PRODUCTION THEREOF |
JPS58121202A (en) * | 1982-01-13 | 1983-07-19 | Nippon Nohyaku Co Ltd | Agricultural and gardening fungicide |
JPS5959725A (en) * | 1982-09-30 | 1984-04-05 | Shin Etsu Chem Co Ltd | Curing of silicone rubber molding |
FR2534260B1 (en) * | 1982-10-08 | 1986-01-10 | Lambert Francois | PROCESS FOR THE POLYMERIZATION OF THERMOSETTING RESINS |
GB8517665D0 (en) * | 1985-07-12 | 1985-08-21 | Ass Elect Ind | Extruded products |
US4873042A (en) * | 1988-03-25 | 1989-10-10 | Union Carbide Chemicals And Plastics Company Inc. | Process for extruding a thermoplastic copolymer |
JPH0280434A (en) * | 1988-09-19 | 1990-03-20 | Regurusu:Kk | Molded resin and production thereof |
US8013093B2 (en) * | 2003-11-14 | 2011-09-06 | Exxonmobil Chemical Patents Inc. | Articles comprising propylene-based elastomers |
JP5219504B2 (en) * | 2005-02-10 | 2013-06-26 | 三井・デュポンポリケミカル株式会社 | Method for producing solar cell encapsulant |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
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DE1084175B (en) * | 1957-11-13 | 1960-06-23 | Hoechst Ag | Process for combining polyolefins with macromolecular substances |
IT612464A (en) * | 1959-07-17 | 1900-01-01 | ||
GB1383924A (en) * | 1971-03-25 | 1974-02-12 | Kanegafuchi Chemical Ind | Method of manufacturing polymer particles having uniform crosslin king and expanded shaped articles formed therefrom |
JPS5438135B2 (en) * | 1971-09-30 | 1979-11-19 | ||
US3705257A (en) * | 1972-03-06 | 1972-12-05 | Anaconda Wire & Cable Co | Electric cable and method of making |
-
1973
- 1973-10-15 GB GB47993/73A patent/GB1489580A/en not_active Expired
-
1974
- 1974-10-11 NO NO743669A patent/NO139299C/en unknown
- 1974-10-14 DE DE2448861A patent/DE2448861C2/en not_active Expired
- 1974-10-14 DK DK536374A patent/DK144513C/en not_active IP Right Cessation
- 1974-10-14 SE SE7412882A patent/SE410194B/en not_active IP Right Cessation
- 1974-10-14 FI FI2989/74A patent/FI62116C/en active
- 1974-10-15 JP JP49118580A patent/JPS586736B2/en not_active Expired
Also Published As
Publication number | Publication date |
---|---|
DK144513C (en) | 1982-10-18 |
FI298974A (en) | 1975-04-16 |
SE7412882L (en) | 1975-04-16 |
NO139299C (en) | 1979-02-07 |
NO743669L (en) | 1975-05-12 |
GB1489580A (en) | 1977-10-19 |
JPS586736B2 (en) | 1983-02-05 |
DE2448861C2 (en) | 1984-12-20 |
DK536374A (en) | 1975-06-16 |
JPS5083476A (en) | 1975-07-05 |
FI62116B (en) | 1982-07-30 |
DE2448861A1 (en) | 1975-04-17 |
FI62116C (en) | 1982-11-10 |
SE410194B (en) | 1979-10-01 |
NO139299B (en) | 1978-10-30 |
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