PROCEDURE FOR THE PRODUCTION OF FORMKORPERN

Thermoplastic polyolefins find due to their good meehanischen and electrical characteristics within many ranges of the technology application. In many cases the used plastics do not meet however any longer the increased requirements. For some years it is possible, for Äthylenhomeund - copolymers such as ethylen vinyl acetate (EH), to interlace ethylen propylene india rubber (EPM) or ethyl propylene Terpolymeren (EPDM) by appropriate measures more or less strongly. With this networking go above all an increasing thermostability, a decrease of the solubility in organic solvents and an increase of the ruggedness against mechanical loads. The partly protruding dielectric characteristics are not only insignificantly impaired by the networking or. These improvements of the characteristics caused by networking open already new technical application possibilities to these materials. It is well-known, polyolefins by effect of radiation high-energy for example 6, ¥ - or X-ray to interlace. Radiation sources are hiebei electron accelerators, x-ray units, radioactive isotopes and nuclear reactors. On a technically sufficient networking of e.g. PL of low density (LDPE) a dose from 200 to 300 is to be spent kJ/kg (-20 to 30 billion). Since now however the energy (kJ/kg), which can be spent, as a to a considerable degree tolerant factor into the economy calculation each with which radiation cross-linking of developed, technical procedure deals, is one anxious, the dose necessary for technically sufficient networking by additional measures to lower. In accordance with the DE-OS 1544804 and 1544805 polyfunctional olefinisch insatiated, monomers connections, which work as Vernetzungsoder vulcanizing accelerator, is used. Are used above all polyfunctional insatiated monomers, which the class of the Diacrylund Dimethaerylc acid ester of the mono, DL, Triund Tetraäthylenglycols to belong, as well as their Vinylund allyl ester. The further Divinylverbindungen such as Divinylbenzol or Diäthylenglycoldivinyläther, then Diallylester e.g. the maleic acid, the malonic acid, the Diallylverbindung of the Pentaerythrits, the tri allyl cyanogen urate and also this close homologous one or mixtures the same. Even if by addition of such Coagentien to that polymers before the networking a lowering can be caused for a technically sufficient networking necessary doses, then adhere to this procedure nevertheless a multiplicity of partly substantial disadvantages. The causes for these disadvantages are to be looked for in particular in the chemical nature of these Coagentien. Several times olefinisch insatiated monomers stated above are throughout polar substances. They are to a large extent insoluble in the nonpolar developed polyolefins, and they show therefore the tendency to migrate with the time from the still unvernetzten federation to the Polymeroberfläehe. This effect of the Ausschwitzens is already few hours visible after the shaping and even with Coagens concentrations under t% and comes with increasing content of Coagens more and more to light. This is all the more important, to be familiar is that with increasing content of Coagens the dose necessary for the sufficient networking becomes smaller. The consequence of it is that a still unvernetzter molded article, which was manufactured e.g. by injection moulding or by extruding of one also according to stabilized mixture from polyolefin with several times olefinisch insatiated monomers as Coagens up to the networking with jets high-energy has an only small shelf-life. This circumstance proves above all as extremely unfavorable if the networking takes place temporally separately from the shaping, how it is given in an intermittent working procedure. During this storage time the mixing proportion and concomitantly the energy necessary for the radiation cross-linking change by current reduction of the Coagens concentration in the polyolefin. This leads to not predictable networking results. In the long run the generally used also liquid or firm Coagentien is usually strike-attractive and partly poisonous substances. This impairs in particular the handling of the unvernetzten shaped parts. It was found that the descriptive disadvantages can be avoided with the production of high-energy molded articles from polyolefins in presence of networking amplifier rkenden Coagentien, unvernetzbaren by jets, to a large extent, if according to invention the mixture from polyolefin and Coagens with 0,01 to 1.0 Gew. - %, preferably 0.05 to 0.5 Gew. - %, related to the weight of the polyolefin, of at least an organically polymere-active Radikalbildner, this mixture Nr.343890 is shifted under shaping over the decay temperature of the organically polymere-active Radikalhilduers up to its large decay is heated up and afterwards with jets high-energy is treated. The necessary temperature depends on the kind and thus the thermal stability of the used organically polymere-active Radikalbilduers. The polyolefins know apart from the networking-strengthening Coagentien and the small quantities of organically polymere-active Radikalbildnern still ageing protecting agents, like Antioxydantien or metal the activators, softening oil or other low-molecular additives, mineral fillers, soot or also Farbpigmente to contain. The migration of the Coagens is completely prevented by the additive according to invention of organically polymere-active Radikalbildnern in high concentrations from the Olefin, and the dose necessary for a technically sufficient networking can be lowered importantly. The shaping can take place via extruding, injection moulding or transfer moldings as usual, whereby the finished shaped part or figuration rank is brought then afterwards on the appropriate temperature necessary for the thermal decay of the used organically polymere-active Radikalbildners, is if at processing temperatures is worked, at which the used organic polymere-active Radikalbildner is not subject yet to the thermal decay. When particularly favourably has it proven to accomplish the shaping at a processing temperature which ensures a large ZerfaU of the assigned organically polymere-active Radikalbildners in the given working time. With production of molded articles from mixture of polyolefins, Coagentien and organically polymere-active Radikalbilduern in accordance with invention enters Oligomerisation added polyfunctional insatiated Coagentien, but no networking polyolefin, whereby the processing of these mixtures is ensured at temperatures, at which the organically polymere-active Radikalbildner already disintegrates. This is substantially differently of of a peroxide organic from the FR-PS Nr.1.424.016 2s admitted networking of PL and ethylen copolymers in presence, whereby peroxide leads directly to the partial networking of the polyolefin. Partly interlaced polyolefins are not processable any longer. In addition in accordance with the procedure of the FR-PS first with radiation high-energy one treats and one after-hardens then with 160°C. Suitable ones organic polymere-active Radikalbildner are e.g. Diarylperoxyde, like Dicumylperoxyd. When in particular regarding the good Extrüsion desired at process engineering favorable temperatures alkene aryl peroxides, in particular 1,3-Bis (tert.butylperoxisopropyl) were particularly suitable - benzene and dialkyl peroxides, in particular Di-tert. Butylperoxyd, proved. Suitable ones by jets high-energy interlacable Olefinpolymeren are e.g. Olefinhomopolymeren, like e.g. PL, polypropylene and Polybuten, Oleflncopolymeren, like e.g. thylen-Propylen3s india rubber, Athylen vinyl acetate and Olefin Terpolymeren, like e.g. ethyl propylene serving polymers (EPDM Kautsehuk) and their mixtures. Suitable ones networking-strengthening Coagentien are several times olefinisch insatiated connections, for example allyl esters, like e.g. Decan-diearbonsäure-l.10-diallylester, oleic acid more diallylester; Allyl ether, like e.g. D allylidenpentaerythrit, Novolak Allyläther; Acrylates and/or Methycrylate, for example those of the mono, Di, Triund Tetraäthylenglycols, the more zweioder multi-valued alcohols such as 1,6-Hexandiol or Trimethylolpropan. Furthermore tri allyl cyanogen urate, tri allyl ISO cyanogen urate and their Monound until diallylcyanurate, like e.g. Stearylamidodiallylcyanurat or Diamino hexane to diallylcyanurat, N, N-Diallylmelamin or Dimaleinimide, like e.g. Dodecan dimaleininmid. The outstanding advantage, according to invention the molded article 4S manufactured in the procedure consists of that the migration of Coagentien from molded articles is completely prevented still before the networking with energiereiehen jets. The use of Coagentien in polyolefins on broad basis with following, interlacable by radiation, in addition, temporally and locally separated networking step with jets high-energy becomes possible. So according to invention manufactured still unvernetzte shaped parts up to the radiation cross-linking will be void so shelf stable and the impairments of the handling of these shaped parts specified above. The Coagenskonzentration in the structure of mixture does not decrease any longer constantly, which led during the radiation cross-linking to not predictable and insufficient networking results. In addition by the additive according to invention the mechanical stressability of to a large extent unvernetzten thermoplastic material is increased, which above all is of advantage if from verarbeitungstechnlschen reasons such a demand is not to exclude and/or be gone around from the beginning not. s the networking in accordance with the procedure according to invention of the invention takes place with a dose from 1 to 200 kJ/kg, preferably 10 to 100 kJ/kg. Thus the networking on mild irradiation conditions is accomplished, whereby it is insignificant depending upon dose rate whether in atmospheric environment or under inert gas is illuminated. So the danger of the unwanted dismantling of the Äthylen= homo and copolymers can be decreased and the extremely an unfavorable effect having radiation damage by additives, like oxidation stabilizers and metal the activators, be lowered. The procedure according to invention is for the production of arbitrary molded articles and semi-finished material, like e.g. Pipes, profiles or casings by extruding, injection moulding or transfer moldings suitably. With special advantage it is used for electric insulations, in particular for cables and lines, where e.g. by repeated turning back the LS electron acceleration plant the primarily still unvernetzte isolation high mechanical loads is exposed to the vein under the radiation window, which can be interlaced. The invention is more near described by the following examples. For networking 750 kV-Kaskadenelektronenbeschleuniger with an electron-beam achievement from 4 KW stood to the order as radiation source. The irradiation were accomplished without exception in atmospheric environment and with ambient temperature. Due to the selected absorbed dose rates (0.3 to 1.1 kJ/kg s) are the irradiation on short time conditions in accordance with DIN 53751 (draft August 1973) to be called. In the following the specified dose values are indicated in NIrd. It corresponds to 1 billion = 10 kJ/kg. Example 1: 5a) Of commercial high pressure PL (LPDE, D = 0.918 g/cm3, MFI190 /2 = 0.2) with 180°C/3 min 1 mm strong Preßplatten of the dimensions 70 x 120 mm was made and interlaced with an absorbed dose of 6, 10 and 20 billion. The proportional networking amounts to 4996, 61% and 7296. The proportional networking determined as measure for the networking degree of the polyolefin one receives as follows: About 0.3 g of the interlaced polyolefin are extracted afterwards in the form of sample test specimens with approximately 1 mm in diameter in stabilized xylene for 12 h with boiling temperature and the not soluble portion (gel portion) is getroeknet under vacuum during 12 h with 110°C. The value of the proportional networking is calculated then as follows: Weight of the extracted sample × 100% proportional networking = weight of the output sample the plates are homogeneous interlaced and indicate with samples taken in different places of the plates practically the same networking degrees. b) 100 Gew. - the LD-PL designated under a) with 150°C in a heatable laboratory interior kneading machine, shifted with 1,7 thread parts Triallyleyanurat (TAC) are plastifiziert and homogenized for 3 min at this temperature. With 180°C/3 min is then converted the mixture to approximately 1 mm of strong Preßplatten and some of it with 6,10 and 20 billion to a proportional networking is interlaced of 60%, 699 and 7. c) To the mixture described under b) in a 2.Arbeitsgang with 150°C kneading machine temperature still additionally 0.1 thread parts of Dicumylperoxyd (DCP, 96 - industrial union) are added and the whole is homogenized for one minute. A part of the 1 mm plates pressed from it with 180°C/3 min again with 6,10 and 20 billion were illuminated. The proportional networking is clearly more highly with 714, 77und 8396. d) In a 3.Arbeitsgang becomes into the mixture described under b) similar to c) now however 0.2 Gew. - Parts of Dicumylperoxyd trained. The irradiation of one with 180°C/3 min manufactured Preßplatten with 10 billion leads here already to one across 80%-igen networking. Apart from this obvious promotion of the networking the small quantity of peroxide prevents the Ausschwitzen of the Coagens from the still unirradiated plates c) and d). While from the still unvernetzten plates worked according to b) already after few hours of the Coagens tri allyl cyanogen urate out-migrates and collects themselves in drops at the surface, c) and d) do not emigrate after weeks of the storage of the networking amplifiers from the likewise still unirradiated plates; the plates remain drying. B e i s p i e 1 2: One as in example 1 proceeded” only that in place of 1,7 Gew. - Parts (TAC) the double quantity (3.4 Gew. - One used parts) at tri allyl cyanogen urate. It showed sees that the Ausschwitzerscheinung increases in the still unirradiated plates of the mixture without peroxide with increasing Coagens concentration. At the likewise not radiation cross-linked plates of the mixtures with a small quantity of Dicumylperoxyd this migration feature is omitted completely. Besides are the plates illuminated with 6 billion (180°C/3 min) of the mixture with 0,2 Gew. - Interlaces parts Dicumylperoxyd to almost 80B, whereas those show a networking of 6 without peroxide only. Example 3: a) In 100 Gew. - Parts of a LD-PL (D = 0.918 g/cm3; MFI190 /2 = 0.2) become with 150°C at a laboratory kneading machine 0.2 Gew. - Parts recognized of the good oxidation stabilizer Agerite purely D trained, in accordance with example 1 with 180°C/3 min Proheplatten pressed and these with billion interlaces. This furnishes a proportional networking of 54%. b) In a second processing step still 1.7 Gew become the mixture described under a) with 150°C kneading machine temperature. - Parts tri allyl cyanogen urate added and these for 3 min homogenizes. A part of the plates manufactured from it with 180°C/3 min is illuminated with 10 billion. They are homogeneous interlaced to 65%. c) In a further processing step still additionally 0.2 Gew become the mixture b). - Parts of Dicumylperoxyd in accordance with example 1 trained and the networking degrees of the plates pressed from it with '180°C/3 min according to irradiation with 10 billion determines. They are already interlaced to 79% homogeneous. It could be proven again that the still unirradiated Preßplatten of the mixture c), even to storage of several weeks no Aussehwitzerscheinung to point, whereas from the plates of the Coagens likewise pressed after mixture b) unirradiated out-migrates and after short time already strongly. B e i s p i e 1 4: The mixture production took place as with example 1 b) to d), whereby however instead of tri allyl cyanogen urate 4 Gew. - One used parts of the networking amplifier TrJmethylolpropantrimethacrylat (TRIM). The networking degree with 180°C/3 of the min pressed and with 10 I, Ird illuminated plates is to the mixtures without peroxide addition about 62 became 0.1 and/or 0.2 Gew. - Admitted, then the irradiation of the Preßplatten (180°C/3 min) with 10 billion leads parts of Dicumylperoxyd to a proportional networking of 64 3s and/or 65 prevents the addition of a small quantity of peroxide also here to the mixture from LDPF. and Trimethylolpropantrimethaerylat the migration of the Coagens from the still unirradiated molded article. B e i s p i e 1 5: The mixture production took place as with example 4, whereby however instead of Trimethylolpropantrimethacrylat 2.2 thread - parts of the networking amplifier Diallylidenpentaerythrit (DAPE) was admitted. The networking degree with 180°C/3 min pressed and with 10 billion of the illuminated plates is without peroxide addition 70B. The irradiation similar to manufactured plates of the mixtures with 0,1 and/or. 0.2 Gew. - Leads parts Dicumylperoxyd already with 10 billion to 80? 5-igen and/or 81%-igen networking. Diallylidenpentaerythrit emigrates few days after Forrngebung from the unirradiated plates of the mixture without organic peroxide increasingly. The migration from the molded articles is prevented by Zumisehen of a small quantity of Dicumylperoxyd perfectly. B e i s p i e 1 6: One proceeded as in example 1, only that as polyolefin a commercial low pressure PL (HDPE, D = 0.945 g/oma MFI190 /2 = 0” 2) was used and as Coagens 3.4 Gew. - Parts tri allyl cyanogen urate on 100 Gew. - Parts of HDP£. The irradiation of the appropriate Preßplatten (180°C/3 min) with 10 billion leads with the base material without TAC to 44%o, by addition of 3,4 Gew. - Parts tri allyl CAN urate to 7 ö and after further addition of 0,2 Gew. - Parts of Dicumylperoxyd already to 84% networking. Additionally the clear migration of the Coagens from the nonpolar PL more highly crystalline opposite LDPE is completely prevented. With s p IE I 7: a) 100 Gew. - Parts commercial EH copolymers (D = 0.980 g/cmS; 45% vinyl acetate; Y [FI190/2 = 2-5) become with 150°C in a heatable laboratory kneading machine with 3,4 Gew. - Parts tri allyl cyanogen urate in 3 min and from this mixture with 180°C/3 min homogenizes 1 mm strong Preßplatten manufactured. The plates are strongly sticky, point however to the irradiation with 6 and 10 billion a homogeneous networking of 51% and 63%. b) In a second processing step still additionally 0.2 Gew become the mixture a) with 150°C kneading temperature. - Parts of Dicumylperoxyd trained. The Preßplatten manufactured out (180°C/3 min) are from importantly smaller tackness, show a higher mechanical firmness and are homogeneous and besides substantially more highly interlaces, i.e. after irradiation with 6 and 10 Ylrd to 85 and/or 88%. The improvement becomes still more obvious, if one compares in contrast to this the proportional networking of the EH material without each additives after irradiation with the above-mentioned dose values: 52 and 71%. B e i s p i e 1 8: Similarly to example 7 2 mixtures were manufactured, whereby instead of ethylen vinyl acetate a commercial ethylen propylene india rubber (EPFI with 45% propylene portion, D = 0.87 g/cms ML (1+4) 125°C = 35) as basis polyolefin was used. The Preßplatten (180°C/3 min) of the mixture from 100 Gew. - Parts of EPM + 3.4 Gew. - Teflen tri allyl cyanogen urate can be interlaced with 10 billion to 64%, whereas the sample test specimens of the mixture with additionally 0.2 Gew. - Teflen Dicumylperoxyd with 10 billion to 7 o are interlaced already. The irradiation of the pure basis polyolefin furnishes only 46%. The admixture of the small Menga at Dicumylperoxyd prevents the migration of the Coagens also here and increases the mechanical firmness of the still unirradiated sample test specimens. B e i s p i e 1 9: Similarly to example 7 2 mixtures were manufactured, whereby as basis polyolefin a commercial ethyl propylene Terpolymeres (EPDM with 45% propylene portion, D = 0.87 g/cm3, 5% Dicylopentadien as Terkomponente and lVIL (1+4) 125°C = 50) was used. The Preßplatten (180°C/3 min) of the mixture from 100 Gew. - Parts of EPDM and 3.5 Gew. - Are interlacable parts tri allyl cyanogen urate with 10 billion to 6, whereas the sample test specimens of the mixture with additionally 0.2 Gew. - Are interlaced already parts of Dicumylperoxyd with this dose to 75%. In contrast to it the irradiation of the basis polyolefin with 1 {} billion leads to a 69%-igen networking. The admixture of the small quantity of organic peroxide effectuation beyond that a clearly higher mechanical firmness of the still unirradiated molded articles, decreases its tackness and favours thereby its handling. B e i s p i e 1 10: It proceeded as in example 2, only instead of Dicumylperoxyd as organically polymere-active Radikalbildner 0.1 Gew. - One used parts of 1,3-Bis (tert.butylperoxisopropyl) - benzene (969ö-ig). The Coagens tri allyl cyanogen urate does not migrate to this mixture from the still unirradiated test plates (180°C/3 min) out, contrary to homogenously manufactured Preßplatten of the mixture without 1,3-Bis (tert.butylperoxisopropyl) - benzene where the Coagens already after few hours out-sweats. Besides the plates of the mixture with 0, I Gew leave themselves. - Tel] EN 1,3-Bis (tert.butylperoxisopropyl) - benzene by irradiation with 10 billion too over 80% interlace, while those show a networking of 69% without indicated peroxide only. B e i s p i e l [...]: 100 Gew. - Parts of a commercial high pressure PL (D = 0.918 g/cm3; YlFII90/2 = 0.2) become TromInelmi in for 12 h with 3,4 Gew. - Parts of Trialiylcyanurat and 0.2 Gew. - Parts of 1,3-Bis (tert.butylperoxisopropyl) - henzol (96%-ig) at a temperature of 60°C intimately mixes. A part of in such a way received mixture is homogenized at a mass temperature by 180°C over a mixture extrusion and squirted to a strand. From this molded article the Coagens does not even emigrate after storage of several weeks. In a second processing step the other part of the aufgetrommelten mixture becomes in the same way, but with only 130°C homogenized and the strand after cooling, withdrawing from mixture extrusion, granulates. Already after few hours the granulates is wet and sticky by emigrated Coageus. Nr.343890 B e i s p i e 1 12: I00 Gew. - Tefle high pressure PL (D = 0.918 g/cm3; MFI190 /2 = 0.2) become in a Trommelmischer with 60°C during one period of 12 h with 3,4 Gew. - Teflen Triallyleyanurat intimately blends. This mixture is squirted over a 90D-Extruder at a mass temperature by 180°C around a S a Kupferlelter with a cross section by 1,5 mm2. During the extruding procedure directly at extrusion over dosing equipment continuously Di-tert.butylperoxyd it is such admitted that in the extruded mixture 0.2 Gew. - Parts related to the weight of the PL are contained. In such a way received homogeneous isolation (isolation wall thickness 0.8 mm), from which even after storage of several weeks the Coagens does not decay, can afterwards by electron-beams be interlaced. RST in contrast to this begins from that in the same way, but extruded at a mass temperature of 130°C isolation after few hours the Coagens to already emigrate.