DE2164560A1 - Process for deforming and vulcanizing a vulcanizable material - Google Patents

Description

Process for deforming and vulcanizing a vulcanizing

material

The invention relates SiOH to a novel method for forming and vulcanizing rubbers or synthetic resins, which are mixed with an organic peroxide (this G _e is mixed referred to as "vulcanizable material denote ^. The invention is especially an excellent method for the manufacture of accessible elongated Formkb'rpern of a vulcanizable material, * ¹ the material through a deforming and vulcanizing effecting long-land die flow path (long-land die) in de is performed.

Z.3 is a common method of producing elongated objects from vulcanized material by pressing the vulcanized material through a nozzle with a short flow path (shortland die) (which only serves to deform the material) and the extrudate obtained through it an elongated vulcanization chamber filled with high-pressure steam.

It 7 / urde bfsreita proposed a method for producing vulcanized elongated molded bodies, such as vulcanized rods, pipes or insulating cables with a vulcanized layer, in which a vulcanizable material, such as a vulcanizing agent-containing __ ₂

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Polyethylene is extruded and vulcanized by heating it to the vulcanization temperature of the material Long flow path nozzle is pressed. This method is hereinafter referred to as vulcanization in a nozzle with a long flow path (long-land the vulcanization)

It is believed that vulcanization in a nozzle with a long flow path has the following advantages over the conventional one Method of steam vulcanization comprises:

1) The vulcanizate has exact dimensions and points in the longitudinal direction Uniform dimensions because the material in the nozzle has a long flow path during the entire deformation and Vulcanization stage is firmly enclosed »

2) The outer surface of the vulcanizate thus obtained is glossy and smooth, because during vulcanization the surface of the product does not come into contact with water droplets, which often adversely affect the surfaces of the product.

3) When the vulcanization temperature during steam vulcanization is increased, the vulcanization pressure also increases. It is therefore difficult to steam vulcanize at one temperature of more than 200 ° C, because a vulcanization chamber must be designed so that it is considerable withstands high pressures at these high temperatures. In contrast, vulcanization can be done with the help of a nozzle with a long flow path, the vulcanization at high temperature, for example at 250 ° C., is carried out in a simple manner because the vulcanization temperature is set independently of the vulcanization pressure. The duration of vulcanization can therefore be shortened considerably.

4) The deforming and vulcanizing device can be remarkable designed to be small and simple.

Despite the expected, described advantages, vulcanization with the aid of a nozzle with a long flow path was not possible used industrially. One of the difficulties that the industrial application of vulcanization in a nozzle with

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long flow path is the difficulty in smoothly passing the molded product through a long flow path nozzle respectively.

In order to overcome these problems, numerous proposals have been made made to allow the smooth passage of the molded product through a closed narrow channel. It became the Proposed use of a channel whose inner wall is provided with a polished surface · Another proposal consisted in the use of a passage or channel, the inner wall of which was covered with a thin layer of a perfluorocarbon resin is covered. Another option was to mix in a molding aid such as chlorinated ones Hydrocarbon lubricants, silicone oil or other lubricants to the vulcanizable compound (US Pat. No. 2,972,780). Another suggestion should be a liquid lubricant, such as oil, can be applied to the inner surface of the passageway (U.S. Patent 3,054,142) "Das liquid lubricant acts as a release agent and prevents the molded product from sticking to the nozzle surface, and also serves as a lubricant that facilitates the passage of the molded product.

However, it has been found that even when using a long flow path nozzle having a polished surface, only vulcanized products can be obtained which have rough or cracked surfaces. It also has demonstrated that the problem was not solved by using a perfluorocarbon resin coated long-path nozzle can be solved because the coating layer after a short process time easily damaged. It has also been found that when lubricants or molding aids are used, the usual Used for shaping plastics and rubber, such as silicone oil and other oils, aur vulcanization in a nozzle with a long flow path, the surface of the vulcanizate within a relatively short time after the start of the process became rough or cracked even though the molding aid

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has been continuously fed onto the surface of the product. It has been found that, surprisingly, this phenomenon is caused by the loss of the lubricating and separating properties of the molding aid caused by Gelatinization is caused by the action of the organic peroxide that comes out of the vulcanizable material » The resulting G-el sticks to the surface of the molded Product or penetrates into the molded product, creating a rough or cracked surface.

The invention is based on the discovery that, through the use of a distinct class of molding tools With specific, critical physical properties, the possibility of deformation is given for the first time and vulcanizing in a long flow path nozzle in a continuous industrial process.

The invention is a method for deforming and vulcanizing a vulcanizable material, in which a Mixture of a vulcanizable with the help of organic peroxide Polymer and an organic peroxide is passed through a nozzle with a long flow path, which is a molding zone and having a subsequent vulcanization zone while simultaneously applying a molding aid to the inner surface of the nozzle is supplied with a long flow path, which has the following features:

a) A viscosity of at least 0.5 centistokes and not more than 3000 centistokes at 235 ° C,

b) an absorption ratio to the polymer of less than 100 mg / cm at 150 ° C for 45 hours,

c) it does not gelatinize even in contact with the organic peroxide in the course of vulcanization and

d) it does not boil during vulcanization;

wherein the molding aid is supplied such that an uninterrupted film is between the inner surface the nozzle and the polymer product is maintained.

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In the practical implementation of the process according to the invention does the molding aid have the effect of making the inner upper \ area of the nozzle with a long flow path and the molded product, whose chemical and physical properties change during the vulcanization with the help of the mixed in organic peroxide constantly change, separate from each other. The form help s means provided on the inner surface of the long flow path nozzle and thus the nozzle of the deformed product separates, should be distributed over the entire interface and an uninterrupted film educate »that. The molding aid transferred to the surface of the molded product should not be absent at any point while the molded product moves through the nozzle.

The molding aid used for the purposes of the invention must have a viscosity of at least 0 "5 Gentistokes at 235 ° C, preferably more than 1.1 oentistokes, preferably more than 5 centistokes, exhibit.

When the viscosity of the molding aid is less than 0.5 Centistokes, the shape aid tends to be local Flow, and it is difficult to spread the molding aid evenly over the entire interface between the inner surface of the long-travel nozzle and the surface of the molded product to be # ± 3? ü: en - so that not easily an uninterrupted Film is formed. A viscosity of 3000 centistokes is a practical upper limit. When the viscosity of the molding aid is greater than 3000 Gentistokes, the molding aid may be a nozzle with a long flow path not easily fed. In addition, the molding aid used for the purposes of the invention must be in view of an absorption ratio on the vulcanizable material to be used of less than 100 mg / cm, preferably less

2
less than 30 mg / cm. The absorption ratio is determined for the period of the invention in the following way: A vulcanized sheet (30 mm 30 mm 1 mm) made of vulcanizable material to be used is 45 hours

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at a temperature of 150 ° C in the molding aid to be used immersed “The plate is weighed before and after immersion. The difference in weight divided by the The total surface area of the plate before immersion gives the absorption ratio.

When the absorption ratio of the molding aid is too high is, it is also difficult to form and maintain an uninterrupted film of the molding aid " In general, a distribution of the layer of molding aid not expected in a uniform thickness, especially if the long-travel nozzle is set horizontally, the molding aid tends to be predominantly in the upper region the interface to flow. If, therefore, a molding aid is used with an absorption ratio that is too high, the molding aid is used in the area in which there is relatively little flow s agent absorbed by the molded product, which leads to a partial drying of the molding aid. This partially Drying out is not eliminated even if the supply of the molding aid is increased because that additional molding aid does not come into the dried-up area, but predominantly enters the area in which the flow of the molding aid takes place more easily ο In addition tends to excess mold tool that the area in which flow occurs more easily, tends to discolor the surface of the molded product.

The absorption ratio of some molding aid increases as a result of the chemical changes under the conditions of deformation and vulcanization to values of more than 100 mg / cm <These molding aids cannot be used for the purposes of the invention even if the original absorption ratio is within the required limits. In addition, the molding aid to be used for the invention may do not gelatinize in the course of a continuous process.

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The gelatinization of the molding aid under normal process conditions is determined by the following test: A mixture of 10 parts by weight of a molding aid and 1 part by weight of an organic peroxide is heated in a closed vessel equipped with a stirrer at a rate of about 10 ° C. per minute up to 235 ° C. Maintained at this temperature for 5 minutes, the viscosity ( Ϊ) *) of the resulting liquid is then measured at 235 ° C. The initial viscosity (^ ₀₎ of the molding aid even at 235 ° C is also measured · When the molding auxiliary has a ratio of ^ -j / ^ o ^{of Weni} S ^{it a} l ^s 30, so it will not be for the purposes of the invention considered gelatinous and it is

to be expected that there would be no gelatinized in a continuous process carried out for at least several hours Film forms on the inner surface of a nozzle with a long flow path. If that used organic peroxide is not volatile, the heat treatment can be carried out in an open vessel »in the test described it is not always necessary to add the organic percjcyd use that is actually mixed with the vulcanizable material. Other typical peroxides, for example dicumyl peroxide, can be used without causing an error in the determination.

In addition, the molding aid used for the purposes of the invention should not be used under vulcanization conditions boil.

When the molding aid boils, pockmarks caused by blistering appear on the surface of the vulcanized product. When heavy boiling occurs, the lubricating and releasing properties of the molding aid are lost and the surface of the vulcanized product therefore becomes rough and, in extreme cases, cracking occurs. However, a mildly boiling molding aid can be tolerated because gentle boiling does not significantly affect the surface of the product.
The following classes of are available for use as molding aids

Suitable and exemplary connections:

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1) Polyoxyalkylenes and their derivatives, random, block or graft copolymers of two or more alkylene oxides and their derivatives, the molecular weight of which is more than "120 and less than 100,000,

2) polyhydric alcohols (including the corresponding dehydrate products) with 4 to 50 carbon atoms, their alkyl esters or ethers,

3) fatty acid alcohol amides with a total of more than 8 carbon atoms, obtained from fatty acids with 2 to 30 carbon atoms and alcohol amines with 1 to 30 carbon atoms became,

4) fatty acid amides with 8 to 90 carbon atoms,

5) fatty acids with 8 to 30 carbon atoms and their metal salts,

6) esters of polycarboxylic acids with 6 to 22 carbon atoms and monoalcohols with 1 to 20 carbon atoms,

7) phosphoric acid esters of alkyl alcohols with 3 to 30 carbon atoms,

8) polyester with a molecular weight of more than 200 and less than 30,000,

9) metal nitrates and metal halides,

10) Polysiloxane masses whose molecular weight is more than 2,000 and less than 100,000, and G-elatinization inhibitors (which will be described in detail later),

11) masses of polysiloxanes, the molecular weight of which is more than 2,000 and less than 100,000, and an alkali or Alkaline earth metal hydroxide or oxide »

These compounds are selected on the basis of their physical, rather than their chemical properties, on the basis of their ability to meet the strict physical requirements described. Below are detailed! typical examples of these compounds are mentioned: 1) polyoxyalkylenes and their derivatives, random, block or graft copolymers of two or more alkylene oxides and their derivatives, the molecular weight of which is more than 120 and less than 100,000; _Q

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of the alkyl ether type, such as polyethylene glycol lauryl ether,
Alkylaryl ethers, such as polyoxyethylene nonylphenyl ethers,
Alkyl thioethers, such as polyethylene glycol stearyl thioether, alkyl esters, such as polyoxyethylene talol esters, polyoxyethylene rosin esters, sorbitan alkyl esters such as polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan products, such as amethylenesorbitan with
Polyoxyethylene stearylamide, polyoxyethylene nonylbenzenesulfonamide, and the like}.

2) polyhydric alcohols (including their dehydration products) with 4 to 50 carbon atoms and their alkyl esters or ether;

polyhydric alcohols such as sorbitan and saccharides,
Alkyl esters or ethers of polyhydric alcohols (including their dehydration products), such as dehydrated sorbitan palmitate, esters of polyhydric
Alcohols and fatty acids such as mono- or diglyceride
of linear fatty acids such as palmitic acid, stearic acid or resin acids such as rhodic acid, uaphthenic acid, caproic acid esters of pentaerythritol and alkyl esters of
Sucrose, myristyl galactose ether and the like;

3) fatty acid alcohol amides with a total of more than 8 carbon atoms, those formed from fatty acids with 2 to 30 carbon atoms and alcohols with 1 to 30 carbon atoms are;

Laurylethanolamide, stearylmethylolamide, Palmityloxyjiiüthyläthanolamid, and the same;

4) Fet:; acid amides with 8 to 90 carbon atoms, such as

Stearic acid amide, oleic acid amide and the like; ^; Fatty acids having from 8 to 30 and their iCohlenstoffatomen _{l (ifj} fc * 11:., Al 2 above, .vie

Fatty acids, such as oleic acid, oleic acid, palmitic acid
unl the ^ LuiO; en, lletall ^ alze of ..'- fatty acids, such as

u ure, ula acid, raLuitic acid, lauric acid _t __ ^ q

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12-hydroxystearic acid and uaphthenic acid and one Metal such as Li, Cu, Be, Mg, Ga, Sr, Ba, Zn, Cd, Al, Ce, Ti, Zr, Pb, Cr, Mn, Co, ili, Fe, Hg, Ag, 21, Sn and the same;

6) Esters of polycarboxylic acids containing 6 to 22 carbon atoms and monoalcohols with 1 to 20 carbon atoms, such as dibutyl phthalate, di-2-ethylhexyl phthalate, dinonyl phthalate, Di-n-octyl phthalate, dibutyl sebacate, di-2-ethylhexyl adipate, Tri-n-butyltrate, tri-2-ethylhexyl trimellitate, Tri-n-octyl trimellitate, tetra-2-ethylhexylpyroLiellitat and the same;

7) phosphoric acid esters of alkyl alcohols with 3 to 30 carbon atoms, how

Tributyl phosphate, tri-2-ethylhexyl phosphate and the like;

8) Polyesters with a molecular weight of more than 200 and less than 30000 how

Polyethylene succinate, polypropylene adipate, polyethylene azelate, poly (I _f 3-butanediol) sebacate, poly (diethylene glycol) adipate, poly (1,6-hexanediol) adipate, polypropylene phthalate and the like;

9) metal nitrates and metal halides, such as

BiCl ₃ , BiBr ₃ , AgUO ₃ , TlITO ₃ , mixtures of NaNO ₃ , KNO ₃ and Ca (IIO ₃ ) ₂ and the like;

10) Mixtures of polysiloxanes, the molecular weight of which is more than 2,000 and less than 100,000, and gelatinization inhibitors (to be described in detail below) how

a composition of matter consisting of liquid Organopolysiloxane, such as polydimethylsiloxane, polymethylphenylsiloxane, and an inhibitor. If polysiloxane is used alone as a molding aid, so the gelatinization of the polysiloxane occurs during the vulcanization in a short time, polysiloxane can however, used as a satisfactory molding aid if an inhibitor is added to it that reacts with the organic peroxide and --11-

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the crosslinking of the polysiloxane by the peroxide prevents «Examples of these inhibitors include phenols and amines, such as dt-naphthol, ß-itfaphthol, Pyrogallol, catechol, 4,4'-thio-bis (6-t-butyl-mcresol), 1,2-dihydro-2,2,4-trimethylquinoline (and its polymerization products), bis (2-hydroxy-3-tbutyl-5-methylphenyl) methane, Dinaphthyl-p-phenylenediamine Hydroquinone and the like. The amount of the inhibitor to be added to the polysiloxane is generally wide in the range from 5 to 30 parts by weight, preferably 10 to 20 parts by weight, for 100 parts by weight of the

Polysiloxane _o
11) compositions of matter consisting of polysiloxanes with a molecular weight of more than 2,000 and less than 100,000 and an alkali or alkaline earth metal hydroxide or oxide, such as

a mixture of polysiloxane and a metal oxide, such as calcium oxide, or metal hydroxides, such as potassium hydroxide, ITodium hydroxide, lithium hydroxide and the like The metal hydroxide or -oxide has the function of reducing the degree of polymerization of the polysiloxane by hydrolysis. To this The increase in the degree of polymerization brought about by crosslinking under the action of the organic peroxide is wise compensated by polysiloxane. Such a composition of matter can be satisfactory can be used as molding aids for the purposes of the invention. The amount of to be added to the polysiloxane Metal hydroxide or oxide is generally in the range from 1 to 10 parts by weight, preferably from 3 to 7 parts by weight, per 100 parts by weight of the polysiloxane.

Among the numerous molding aids used in the present invention are preferably polyoxyalkylenes and their derivatives, random, block or graft copolymers of 2 or

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several alkylene oxides and their derivatives, and aliphatic Polyester.

A molding aid, which is a solid or a highly viscous liquid, can be in the form of the melt or in form, a Mixtures with a suitable liquid, for example alkylbenzene, can be used. Such a mixture must naturally meet the aforementioned physical requirements for the molding aid.

Synthetic resins suitable for the purposes of the invention are addition polymers such as homo- or copolymers of olefins, diolefins, vinyl esters, vinyl ethers, vinyl ketones and other vinyl or vinylidene monomers. Further examples of synthetic resins are polyamides, thermoplastic polyesters and polyorganosiloxanes. Particularly suitable polymers are _r such as polyethylene, ethylene-propylene Öopolymere, ethylene-propylene-diene terpolymers, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate-Oopolymeres, styrene-butadiene-Copolynieres, PoIycis-1,4-isoprene, polychloroprene, Polybutadiene, polydimethylsiloxane or polyphenylmethylsiloxane. To carry out the method according to the invention, however, any synthetic resin can be used which, with the aid of an orga-

"niche peroxide can be vulcanized»

Examples of suitable organic peroxides are dialkyl peroxide, such as dimethyl peroxide, methylethyl peroxide and diethyl peroxide. 1,1-Dihydroxydiethyl peroxide, ethylcyclohexyl peroxide, propylhexyl peroxide, di-tert-butyl peroxide, di-n-butyl peroxide, tert-butyl-tert-amyl peroxide, tert-butyl-phenyl-methyl peroxide, tert-butyl vinyl peroxide, tert-butyl vinyl peroxide, Butylcumyl peroxide, dichloro-tert-butyl peroxide, di-tert-pentyl peroxide, tert _o -P _p ntyl-tert-hexyl peroxide, üi-n-hexyl peroxide, J) i-tert.-hexyl peroxide, dicyclohexyl peroxide, di-n-heptyl peroxide, ]) iphenyl-m - ■: thyl-yxanthenylperox ^^ d, dicumyl peroxide, 1,1 '-diterto-butylporoxyethane, 2,2-bis (terto-butylp'! "oxy) butane, 1,4-bis (cum, vlpero> r ^) -butane, 1,10-Ms (cumylperoxy) de can, 2 , b-Dim ^ thyl-'J, b-di (terf .-

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butylperoxy) hexane, 2,5-dimethyl ~ 2,5-di (tert-butylperoxy _o) -3-hexyne, 1,3-bis (tert-butylperoxy) diisopropylbenzene, 1,4-bis- (cert. ~ butylperoxy ) diisopropylbenzene and the like, hydroperoxides, ie 2,5-dimethylhexane-2,5-dihydroperoxide, 2,5-diraethylhexyne-2,5-dihydroperoxide and the like; Peroxyacids and their acids, such as terto-butylperoxybenzoate, di-tert-butyldiperoxyphthulate, 2,5-di (benzoylperoxy) he; can and the like.

iei the process according to the invention, mixtures of the mentioned organic peroxides are used.

The specified organic peroxides can preferably be added to the vulcanizable material in an amount of about 0.05 to 10 parts by weight per 100 parts by weight of the synthetic base resin. The materials that can be vulcanized for the process according to the invention can contain various ΔΊ ^ Ι-itZi} , such as / mtioxidants, vulcanization .jec-jchl-iuni yir, vulcanization inhibitors, other vulcanization auxiliaries, voltage stabilizers, / eichra-ioher, color pigments, huss or dyes. Examples of τ i-.veiidbare -intioxidants are 4,4'-bis (3-methyl-6-, eruc-buüylphenol), ii, iT ^l -di-2-naphthyl-p-phenylenediamine. Examples of suitable vuUcnisution accelerators are p, p'-liib ^ nzuylquinone dioxime, tetramethylthiuram disulfide. Examples i'lli ¹ 7-ii :: anioHtionsveradgerer are 2,6-di-tert-butyl-pkri. Jul, hibhalsic anhydride. Examples of other vulcanization: jr: il t'r.miötei oind i'riallyl isooyanurate, diallyl phthalate »At -.- ipiülö for tension stabilizers aind 9,10-dibromanthracene, i , 'LL-juj iairi'ilfid, ιί, ϊ /' - Dialkyl copper dithiocarbamate.

lAXaI u '; 3jeren understanding of the method according to the invention, oil yes the b ^ lLi.'j .'- iöMen Zelchnun en serve the schematic. ·· :; töilun, -.n.} - _: > hz ± h11: v Auüf '-. hrun jsf ormeti of the invention represent-

n mean en

/ 'i nc 1 -jir / LHng.'j:; chnifct einer Vor. \ riohtuxig zum Manufacture ..

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-H-

an electrical cable with a vulcanized insulation layer

FIG. 2 shows a longitudinal section of a device for manufacturing

a tube made of vulcanized polymer.

In FIG. 1, a nozzle 3 with a long flow path is shown which with the aid of a nozzle holding device 7 with the cross spray head 1 of an extruder is connected, and which consists of the nozzle parts 31, 32 and 33, which by flanges in a Row are connected to each other and can therefore be disassembled into individual parts.

The flange 4, which is screwed onto the .jtide of the nozzle part 31 is, forms an annular recess 47 and a annular projection 46. This annular recess 47 results in a step 4β. In this recess 47 is a porous Tube 41 inserted. The inner diameters of the nozzle part 31> of the gate projection 46 and of the porous tube 4 1 are the same. One annular chamber 42 surrounds the porous tube 41 β this chamber

42 is connected to a Johrung 44 in the flange .4- and the "hole 44 int via a connection part / with a line

43 connected.

ώίη flange 4 'ie & uüsentslls 32 is with the help of Bolaen 49 and ochr & ubenmut btirn 50 hermetically attached to the flange 4 » The molding aid is through the line 43 and the bore

44 from a Fo in the ihilfsmitt · =! - Keep .. · (which is not shown iafc) with the help of a high pressure pump (not shown), v / ie an I. multiple piston pump, especially a Bosch-type pump, in the Kammar 42 introduces.

The chamber 42 serves as a storage container for the Formhill'smictel, Daa FortiihiLfamitte L _1, which is filled into the Kanuaor 42, seeps out of the porous tube 41. The form aid benefits from the Inuonflache of the porous tube 41 on the entire inner surface of the α following part the Langv.ojdüse and facilitates the flat passage of a shaped

through the canal (U, -r nozzle with long irlieY / eg 3 · _ .ic

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.- 15 -

The molding aid is fed to the inner surface of the nozzle in the area of the entry into the nozzle channel, preferably it is fed within 1 m of the entry into the nozzle channel. The inlet area of the nozzle channel of the nozzle with a long flow path is maintained mperature at a T _e, which is so high that is melted to be deformed, vulcanizable material • which is so low but "that the premature vulcanization of the material is avoided ( The following area of the long flow path nozzle is maintained at a temperature high enough to vulcanize the material. This zone is heated by means of a belt heater surrounding the long path nozzle (This area is hereinafter referred to as vulcanizing zone.) The length of the deformation zone is not subject to any restriction, but it is preferably less than 1 m. The deformation zone may be restricted to the actual entry of the nozzle channel of the nozzle with a long flow path.

A molten vulcanizable material R is with the help of an extruder, not shown, on an electric Conductor W is extruded, which is continuously inserted into a cross-head through a guide member 2, and is under formation deformed of specified dimensions while passing the deformation zone of the nozzle with a long flow path. the molded layer on the electrical conductor W is heated and vulcanized while passing the vulcanizing zone of the nozzle happens with a long flow path, and after exiting the nozzle is passed into a water-cooled device 5, which is directly connected to the nozzle part 33. «There, water is continuously under high pressure, for example of about 30 kg / cm fed and discharged in the direction of the arrow shown in FIG.

It has surprisingly been found that the formation of voids or bubbles in the insulating layer is negligible low-is when a cable insulation after the exit _ ^ g

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the cable out of D ₁ ^ Se with long flow path is immediately cooled in pressurized \ Yasser. It was found that a vulcanizate obtained by steam distillation shows numerous micro voids when observed under a microscope. It was also found that in the conventional steam vulcanization, which is usually a

Pressure between 15 and 20 kg / cm is carried out, a cooling r-

ρ "

Water pressures greater than about 10 kg / cm have little effect on the number of voids that appear in the insulation

\ In contrast, showed that the vulcanizate obtained by the invention has no voids when the cooling at

a pressure of more than 10 kg / cm takes place. All of these observations were made under a differential interference microscope to clearly distinguish cavities from the insulating material »

A void-free insulation that is ideal for high voltage cables was viewed, could by the inventive method can now be realized for the first time.

A device for making a pipe from networked! . Polymer is shown in the accompanying FIG. In FIG. 2, the vulcanizable material R is extruded into the channel of the attachment (adapter) 1 with the aid of an extruder and, after passing through the passages of the branches 7 of the distributor 3, is deformed into a cylindrical shape in the area of the inlet of a nozzle with a long flow path 4. In this stage, the temperature of the vulcanizable material is still below its vulcanization temperature. The vulcanizable material thus formed is then heated and vulcanized as it moves through the annular channel (Vulkanisatic.ozone) enclosed by the long flow path nozzle 4 and the mandrel 5. The molding aid is applied to both the inner surface the nozzle with a long flow path 4 through the porous tube 10 according to the manner described in connection with yi ur 1 as well as on the outer surface of the dome 5 _Λ ^ ₇

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fed through the porous Eohr 11, which is between the manifold 3 and the mandrel 5 is inserted and fastened «This mandrel 5 is screwed onto the distributor 3 and extends up to to the exit of the cooling device 6 »for supplying the molding aid This molding aid is applied to the mandrel 5 through the channel 16 and the bore 17 in the same way as in FIG. 1 in FIG the annular chamber 12 is introduced. The thorn / is with the help the heating cartridge '19 inserted into the mandrel to the vulcanization temperature heated. The heating cartridge 19 is connected to a power source via the lead wires 18. After this the vulcanized tube has emerged from the outlet of the nozzle with a long flow path 4, it is in the cooling device 6, which is directly connected to the nozzle with long flow path 4, cooled under pressure, for example at about 10 kg / cm. Of the up to the exit of the cooling device 6 in the V / iron extending mandrel 5 serves to reduce the deformation to prevent the Hohrs from the pressure of the cooling medium. Bs However, a mandrel 5 can also be used, which extends only to the outlet of the nozzle with a long flow path 4, provided that that the deformation of the vulcanized pipe by the pressurized cooling medium is permissible or that none There is a risk of the pipe being deformed by the pressurized cooling medium. For making one of bubbles or voids-free vulcanized product is a pressure

of the cooling medium from 5 to 50 kg / cm, preferably 5 to 30

2 2

kg / cm and in particular 20 to 30 kg / cm recommended, Bs it is also preferred to use a cooling device 5 which is constructed so that it can be easily moved, for example by using wheels attached to it. With the help of this design, it is more convenient to reduce the number of nozzle parts to decrease or increase or to change the nozzle parts and furthermore the cooling device itself be shifted depending on the thermal expansion of the nozzle with a long flow path 3 due to the temperature changes.

^ s int it can be seen that certain modifications and Teränd®- - 1 8 -

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made ments of the described embodiments of the invention can be without departing from the inventive concept β

In the method according to the invention, depending on the cross-section and size of the desired product, nozzles with a long flow path of different cross-sectional shapes and dimensions are optionally used. It is possible for these nozzles with a long flow path to be composed of two or more nozzle parts which are connected to one another in series in the manner shown in FIG. Materials with good thermal conductivity, such as iron, brass, copper or aluminum, are preferably used as the material for the nozzle with a long flow path. The nozzle with a long flow path can be heated by numerous methods, for example with the help of an electrical heating tape placed around the nozzle, with the help of a jacket around the nozzle heated with hot oil, by direct supply of electrical current to the wall of the nozzle or by induction heating. The long flow path nozzle is usually 1 to 20 meters long, or ¹ longer if necessary.

The term "nozzle with a long flow path" is used for a nozzle with a long nozzle channel, which is called "longland which "is designated.

The method of applying molding aid to the inner surface the nozzle with a long flow path can be freely selected, provided that the molding aid supplied via the entire inner surface of the nozzle with a long flow path or at least over the entire inner surface of its vulcanization zone is distributed. It is believed that the use of a porous tube as shown in Figure 1 is best Possibility of supplying the molding aid; however, another method may also be used, like supplying the molding aid through one in the nozzle with long flow path provided slot.

The molding aid is usually supplied in the -19-

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I 'r 19-

Deformation zone with a long flow path, however, is the deformation zone extremely short, it takes place at the inlet opening of the nozzle with a long flow path <> Additional feeding is also possible. For example, the additional feeding at a predetermined point in the vulcanization zone take place. This additional introduction of molding aids is preferably carried out in the bottom part of the horizontally arranged Nozzle with a long flow path because this area tends to dry out »

With the way - -: \ the form of aid, the G-ize of the molded products and the deformation and vulcanization varies Zuführungarate the form of aid; however, it is usually in the range of about 0.001 to

0004 cnr on 1 cm of the surface of the molded product.

The temperature conditions during deformation and vulcanization and the cooling conditions with regard to the pressure of the cooling medium depend on the vulcanizable materials to be used. For example, when using a compound of low density polyethylene containing dicumyl peroxide the pressure of the cooling medium in the range of about

5 to 50 kg / cm, the temperature of the deformation sz one in the temperature range from about 110 to 140 ° C and the temperature of the Vulcanization zone selected in the range from about 150 to 300 0, In general, the pressure of the cooling medium, the temperature of the Deformation zone and the temperature of the vulcanization zone in the Range from 5 to 50 kg / cm, 100 to 150 C or 140 to 300 ° C.

■ In the method according to the invention, the deformed pro ' Before it enters the vulcanization zone, the product is coated with a layer that does not contain any organic peroxide contains. This can be done by suitable means, for example with the aid of an extruder. The applied layer prevents direct contact of the molding aid with the organic peroxide emerging from the molded product

209831/0930

and therefore reduces the risk of destruction of the molding aid through the organic peroxide

The coating materials used are advantageously polyethylene, compounds based on polyethylene and other thermoplastic resins. To produce an electrical cable with a vulcanized coating layer, this coating layer can be a semiconducting layer _o 'coating layers with a thickness of 0 = 5 to 1 mm are usually sufficient to prevent the molding aid from coming into contact with the organic peroxide.

With the invention, the application of vulcanization with the aid of a nozzle with a long flow path becomes applicable for the first time and it can vulcanized objects with a good surface finish can be produced in a more efficient and economical manner. The invention is also suitable Method particularly good for producing insulated high-voltage cables because the vulcanized insulation produced is free of voids and bubbles.

The process according to the invention is described below with the aid of examples »

example 1

A vulcanizable polyethylene compound, consisting of 100 parts by weight of low-density polyethylene with a density of Ο «920 and a melt index of 0.5 (according to ASTM D 1238-1970, method A, condition E), 2» 0 parts by weight of dicumyl peroxide, 0.5 parts by weight 4, 4'-Ihio-bis (3-niethyl-6-t-butylphenol) and 0.25 parts by weight of diallyl phthalate, was introduced into an electrically heated extruder (cylinder channel: 120 rim, L / D: 14, compression ratio: 2) and extruded onto a cable core, which was fed continuously at a linear speed of 3 _f 5 m / min into the cross-head of the extruder. The cable core had a vulcanizable semiconducting polyethylene layer 1 mm thick

209831/0930

on a strand (diameter 600 mm) of 91 copper wires, the outer diameter was 2 _O 9 A nozzle with a long flow path with a length of 6000 mm and an inner diameter of 69 x 9 mm was attached directly to the exit of the cross-head and the deformation zone (500 mm) was kept at 130 ° C, the vulcanization zone (remaining 5500 mm) was kept at 250 ° C. A feed device for the molding aid was placed 100 mm from the end of the long flow path nozzle which was adjacent to the crosshead. An ethylene oxide-propylene oxide block copolymer (Unilube 50 MB-26X from Iippon Oils & Fats Co., ltdo), which had the following data: density ( γ ) 1.05 at 20 ° C., refractive index (^ ⁰ ): 1.459, viscosity: 5.76 oentistokes at 235 ° C, boiling point: more than 300 ° G, 7-i / * 7o ^{s xm} ^ ^{er 2} > absorption ratio: -0.15 mg / cm (note 1). This molding aid was fed continuously through the feeder at a rate of 1.5 cm / min.

3 2
(0.012 cm to 1 cm of the surface of the extruded product) using a high pressure piston pump. The non-vulcanizable polyethylene compound was extruded onto the cable core and deformed as it passed through the deformation zone, and then heated and vulcanized as it passed through the vulcanization zone. The cable, insulated with vulcanized polyethylene, was after passing through the nozzle with a long flow path with the help of high-pressure cooling water

2
cooled by 25 kg / cm. _{A vulcanized polyethylene-covered cable (thickness 18 mm), which had a glossy surface (grade No. 0-1} (note 2)), was continuously produced on this Y / eiae for a long process time of more than 500 hours. Voids were not found in any area of the cable insulation (Note 3) ο

Remarks:

1. It is assumed that the negative value of the absorption ratio by extraction of certain additives from the Polyethylene compound is caused in the molding aid.

'Λ. The surface of the vulcanizate is in the following way - 22 -

209831/0930

rated:

Rating # 1: Glossy

Ur. 2: Shiny but slightly cloudy

No. 3: Not shiny, but with a smooth handle

No. 4: Honeycomb-shaped fine cracks

3 ο Determining the number of voids in the insulating layer was carried out as follows: A test piece cut from the insulation layer is 30 minutes cooled in liquid nitrogen, then the piece is cut into slices about 10 microns thick using a microtome cut. The number of cavities in the disc is counted under an optical microscope (microscope of the differential interference type, magnification 300 times )O

Examples 2 to 24

The deformation and vulcanization of insulating materials on a cable core was carried out according to the method according to the invention carried out under the conditions shown in Table 1. The number of voids in the insulating layer was determined according to the method of Example 1 (Note 3). Included no voids were found in the cable insulation made according to each example. the Duration of the continuous implementation of the process and the surface quality of the insulating layer of the cable according to each of the examples are given in Table 1.

209831/0930

0860 / L ε8602

Table 1

At -SOi θ! a structure of electrical c2 c5 d e
cst. Pornfc ^ tools X No. ■ b C. f β "h
⁰ C m / r / cnr t Hl / cn? mrn cl

Copper strand (91 / 2.9 au., Diameter rcra.) Covered

with vulcanized SGiiii conductlver

Polyethylene chioht (1 mm thick)

LDPE

(J: 0.920 MI: 0.5)

DCP 2.0 ropes

, 4

(3-methyl ~ 6 t-butylphenol)

0 »5

phthalate

Unilube 5 OMB-168X

5.00 300 <2> -0.1

0.01

dito

18th

LDPE 0.920 TBCP (f: 1.0) 2.5 WED: Parts

4,4'-thiobis

(3-methyl-6-

t-butyl

phcnoi)

0.3 parts p, p'-DL likewise-

yl chinone -

dioxime

0.5 parts

Plonon # 204

8.96 300 < ~ 2> -1.Ό3 0.011

dito

EVA. TBCP (f: 0.93 2 * 5 MI: 3.5 parts

VAc 'salary

14th

4,4'-thiobis

('j-nicthyl-6-

t-butyl

.phenol)

0.3 parts p, p'-Di.bcnzo-

y1chinon-

'dioxira

O.ii parts

Plonon 4-42 300 <2> -1.08 0.015 // 201

■ Ό-

οεεο /

example

No.

Nozzle with a long pleating path

mm min

11

mm.

12 ⁰ C

ml

min

Duration of continuous

ο ρ Implementation of the procedure

cm / min kg / cm hours

Surface condition

2 6000 .69.9 500 130 5500 250 • 35 25th 300 < 1 3 6000 69.9 500 130 5500 250 35 25th 25Ö < CvJ 4th 10,000 69.9 500 125 9500 250 55 25th .25Ο < . 2

0860 / L € 8603

Example structure of the electric cable ^No : from c

Form-help-fsmittal

el

c2

cut .. ⁰ C

gh i

ρ Ο

rar, / err. ' cc / cr / "

, Kupf he stranded

. _ (31/2 .9 πιπί.,
DurcHmeoser;

600 µm)
vulcanized semi-conductive polyethylene layer
(1 mm thick)

18 LDPB, BBPB

(?: 0.920 3.0 MI: 0.5) parts Ν, Ν'-dinaph-nonylethyl-p-phcnyphenyl len-uiamih polyoxy-0.5 part ethylene *

ρ, ρ'-dibenzoylquinone'-dioxime ° · ² parts

1.98 245 <2> 0.35 0.65

(37 / 2.6 mn.,
Diameter:

600 Ent) covered
with vulcanized
s a- more conductive
Polyethylene layer
(1 mm thick)

17 LDPE

(?: 0.920 WED: 0.

TBCP 2.0 3) parts of triallyl isocyanurate 1.0 parts

Phthalic anhydride .: 0.8 parts

Oleic acid amide. ** '

1.17 35O <. 2> 0.J

1.65

dito

dito

ditö ditto

Stearic acid; ***

1.13 36O <2> 0.92 1.86

Kupferstangi.
(19 / 2.6 billion,

Diameter:

100 mm.)

with vulcanized
be more conductive
Polyethylene layer
- (1 mm thick)

16 LDPE BBPB

. (?: 0.920 2.0 MI: 1.0) parts triallyl isocyanurate .: 2.0 Partly

2,6-di-tbutyl-parac're G oil 0.5 part

Polydi-

methyl-

siloxane ..

(2000 cst.

at 30'C.)

100: parts of pyrogallol

20 parts

400 <3.5 1.18

crt σ> ο

Beispi el nozzle with a long flow path no. J k.

rn

mm.

11

well

12th

ml mm.

m2

'C

Duration of the continuous process

. ■ implementation

Surface texture

cm / min kg / cm hours

5 10,000 69.9 500 125 9500 250 55 25th 200 < .3 6th 20000 . 54.2 300 125 19700 250 112 25th 100 < '3 · 7th 20000 54.2 300 • 125 19700 250 114 25th 100 < 3 8th· 10,000 47.0 10 130 9S90 260 61 25th 20 <. 1 '

example

Ut.

Structure of the electric cable a "bc

Molding aid

el

c2

c3

mm.

■ ccji

C.

cc / eil ·.

Copper stain \ £ ng ■ (, 19 / 2.6 mm.,

Diameter:

100 mn ² ,) covered with vulcanized senii-conductive polyethylene layer (1 mm thick)

10

16 LDPB DCP. : 0.920 M: 1.0) parts

Triallyl isoeyanurate. 2.0 parts

yichinondioxirri "0.7 parts

Polydimethyl ~ siloxane.

(2,000 cst. At 30 ⁰ C.)

100 parts of ZOH

5 parts

132 400 <

3.56

(37 / 2.6 niiri., Diameter: 200 mm ^2. ) Covered "

with vulcanized seni-conductive polyethylene layer (1 nan thick)

17 LDPE

0.920

TBCP 2.5

'MI: 0.3) parts

Triallyl icocyanurate ■: 2.0 parts.

Tetramethylthiuram disulfide. 0.7 parts

Poly (I, 6- 12.8 hexane-diol-adipate. :)

6.4

27O <2> 0.78. 0.32

to

CD

O O

KupersTÄing (7 '/ 2.0 mm.,

Diameter:

22 Βΐπή; covered with vulcanized semi-conductive polyethylene layer (i ram thick)

L3

dito

DCP - triallyl iso-2.5 cyanurate parts' 2.0 parts

4,4'-T.liioMs- (3 ~ methyl-6-t-butylphenol) 0'.5 parts

Sorbitan monolaurate ■ ·

2.13 260 <2> 3.62 1.43

example Nozzle la it la: agem Jb-LieJ .-jweg ml
mm. m O Mr.. .
"1 k 1 cm / min. mm. mm 11
mm 12th
⁰ C

Duration of the continuous transit

guide
kg / cm hours.

Surface texture

3 10,000 47.0 • ¹⁰ 130 9990 260 61 25th 25 <. 2 10 3000 54.2 200 125 2800 270 28 22nd 100 < 2 11 3000 33.0 300 130 2700 250 21st 20th 70 < 3

CO CJ O

example

Structure of the electrical! Label

el

c2

mm

Form auxiliaries
efg

cst. ⁰ C

ras / cm cc / cm

pg (7 / 2.0 an.,

Diameter:

22 m'.j covered with vulcanized s e'mi- conductive pol3 ^r äthylons chi cht (1 mi thick)

15 LDPE DCP

(P: 0.920 KI: 0.5) parts

Triallyl iso-

cyanurate

2.0 parts 4 »4'-Thio" bis-

(5-ir.ethyl-6-

t-butyl

phenol)

0.5 'file

Polyoxy-5.62

ethylene sorbitic monolaurate

270 <2> -0.20 0.52

13th dito 15th dito dito dito Lauryl - 1
ethanol -
amide. 26th 26O < 2> 1. 61 0. 69 14th dito 15th dito dito · . dito Tetra-n-1.
octyl
pyromelitat .. 67 25O < 2> 25th .2 0. 73

Example ^ No.

Structure of the electrical cable s'ormliilf smittel.

el

c2

c3

mm. 'cst. ⁰ C ..

.2.

ig / cm., cc / cm.

pxersO ^ ne ^ (19? 2.6 mm., DurcJunesser:

mm?) covered with vulcanized seni-conductive Polyethylene chi cht (1 cm thick)

EPDM DCP (Mitsui Petro-Parts chemical Ind., Ltd.)

Zinc white 5.0 parts'

Poly (2,2,4-

trimethyl-1,2-dihydroquinone ■

1.5 parts' MT KohleriGtoff

12.5 parts "Chemically pretreated

Unilube

50IiB-26X

5.73 300 <2> -0.15 0.012

volume

125 "parts

P-200

Paraffin oil

'2.0 parts minimum

5.0 parts of paraffin wax

5.0 parts

O O

example

No.

Long flow path nozzle

11

well. mm. Rome

12 ⁰ C

m2

Or,

Duration of the continuous ''
'■ detailed

Fahreiisdurchfüh-P tion

hours

cm

/ min,

Surface quality,
Ness

12th 3000 33.0 300 130 2700 250 21st 20th 80 < 2 ' 13th 3000 33.0 300 130 2700 250 21st 20th 100 < 2 14th 3000 33.0 300 130 2700 250 21st 20th 100 < 3 ■. 3000 47.0 200 130 2800 210 48 18th 50 < 1

O CO CO

cn cn ο

Example—— Kr. ^A

Structure of the electric cable

Formiii}. £ medium

.e

el c2

mm.

cst

^J C.

mg / cm

cc / cm.

(19 / 2.6 mm.,

Diameter:

100 ismt) bediclrfc " with 'vulcanized serai-conductive Polyethylene layer (1 mm thick)

16

-No CO to

SBR

DCP <■ r Zirf £ knows 3.0 5.0 parts Parts Poly (2,2,4- trimethyl 1,2-dihydro-
ciiinoii)) l.ü part 2.0 parts MT Darbon ■ 50 parts Dibenzothiazyl disulfide 1.25 'J' ropes Calcium carbonate 37.5 parts Paraffin wax 3.0 parts

Unilube 5-73 300 <2> -3.1S
5 OMB-26X

0.012

to ω ο

cn cn ο

reiSTDiea.

Structure of the electrical cable

Molding aid

cl

c3

cut.

g ·. / c ir. * cc / err ·. "

(19 / 2.6 mm.,
Diameter:

100 Kürt J covered
with vulcanized
s em! ,, c onduktuve r
Po ^ ethylene layer
(1 ma thick)

16 poly

ClO-

1,4-isoprene

DCP zinc white,. 2.0 3.0 parts parts' poly (2,2,4- • - trimethyl-

1,2-dihydro-

chinone

0.75 part stearic acid

1.0 part of N-phenyl-N 'isopropyl-pphenylenediarain

0.75 part lead dimethyl dithiocarbamate 0.3 part

Plonon

# 204

8.96 300 <2> -1.07 0.012

Mixture of. _{7> 1 2go <2>} ι. ₈₃ ' ₀ .36

•O

dito

16 LDPE (P: 0.92 HI: 1.0)

-ditto 4,4 ^I -T'hiobis- (3-methyl-6-t-butylphenol)
0.5 part diallyl phthalate 0.25 part

Glycerin ^
and polypropylene adipate ■

(1: 1)

Example no. J

Long flow path nozzle

11

12th

ml

m2

Duration of continuous
ρ procedural

permeation

Above-

surface area-

Ness

min mm < mm ■ ° C mm ⁰ C cm / min k ^ / cri hours 1 16 3000 47.0 200 130 2800 210 45 18th 45 <. 2 17th 3000 47.0 200 130 2800 210 47 18th 45 < 3 18th 3000 47.0 200 130 2800 210 47 18th 150 <

eispieJL

Structure of the electrical cable

el

c3

cst-

mg / cm cc / cm

Kut) f er strand (19 / 2.6 ma Γ,

Diameter:.

100 cm?). with vulcanized ami- c onductive p olyethylene chi cht (1 ram thick)

16

DCP

(Ρ: 0.92 MIi 1.0) parts

4 »4'-T'hiobis ·

(3-metiiyl-6 "

t-butyl

phono.1).

0.5 part diallyl

phthalate

0.25 part

Mixture of 3.52 25O 2 Unilube

20.5

X ₁ and dioctyl sebacate (1: 1)

dito

16

dito

dito

Mixture of sorbitan monolaurates ·

■ and '
Stearic acid "(1: 1)

1.8 260 <2> 3.3 0.74

dito

16

dito

dito

"O

S σο | 0

80. £ Solution 0.65 255 <2> 35.5 17.6

Oleic acid

araid in ■

Alky! Benzene.

13 cst. At 3ggc .. and

1,487

-P I. • Η Λ CD ο
C, § M.
iS P! ω χ} ω ca fco ι Λ ¹ H. Ö P! Fh O CD φ 3 ω: cd I Λ «QH ( 3) O ο <Η, Q approx Γ. C. M M
U Qi ω O) · Η> ti 3 F-I-H. ω ω-μ, α

CM

S ϋ

Ή H fr

P.

W • Η O

CM

β

H E

CM H

ti

co

210

2800

200

O Ο

CTi

r-l

- 36 -

CM

ir »

CM

CO
H

210

2800

200

O
O
O

CV

CM

co

i-i

C-

210

2800

150

200

O O O

H CM

209831/0930

Example structure of electric cable

el

cat- ⁰ C

mg / cm "cc / c; r»

22nd

(19 / 2.6 r: .n., Diameter:

100 rm ^? ;) covered with vulcanized social ο iidukt i ve r polyethylene layer (1 "nn thick)

16 ID? B DCP (P: 0.92 KI: 1.0) parts

4th, 4'-ThioT3is-One thy 1-6-t-butylphenol) 0.5 parts

Diallyl phthalate 0.25 parts

£ Solution 0.71 250 <2> 11.0 of

Magnesia " stearctü in triamyl araiine

16

dito

dito

Tri-n-butyl citrate

0.68 · 260 <2> 8.31 4-0

Kunfer-rfeit-

- (91 / 2.9 toi., Byine c ser:

600 n: ^ J Covered nit vulkanisie-r-üer s enx- c onduktiv r P οIyäthylenschicht (1.mm thick)

18 LDl-S ditto (P: 0.920 MI: 0.1)

dito

75H-90000

248 32O < 2> -0.08 0.012

CM B

CM

H H

• rs

O • to \ S
O
CM O
O Ö
ω I. \ y
in
CM 1
■ ρ
CO £ CM R.A.M CO
H ir »
CM 5 CO
H ■ 'rain L. . ε
ο 210 O
CM ο
ο 210 2800 O
O
ir \
in ε O
O
00
CM O
H 130 130 200 500 200 O VO 47.0 O
O
O 6000 3000 CM CM CM
CM

209831/0930

216-5-0

Note: The symbols in the table have the following meanings:

LDPE:

EPDMx

BBPB: DDTBH:

Cable core

Thickness of the insulation layer applied to the cable core (mm)

Composition of that to be applied to the cable core vulcanizable material

Synthetic resin. (O: density, MI: melt index (ASTM D 1238-1970, method A, condition E), VAc: vinyl acetate)
Organic peroxide
Other additives
Art

Viscosity (l / _Q ) (Centistokes at 235 ° C) Boiling point ( ⁰ C)

C, 45 hours

the outer surface of the iso-

Absorption ratio at

(mg / cm)

3 '

Feed rate (cm / cm '

layer)

Length of the nozzle channel (mm)

Inside diameter (mm)

Deformation zone

Length (mm)

Temperature (° C)

Vulcanization zone

Length (mm)

Temperature (° C)

Feeding speed of the cable core (cm / min.)

Pressure of cooling water (kg / cm)

Low density polyethylene

Ethylene vinyl acetate copolymer

Ethylene-propylene-diene terpolymer

Dicumyl peroxide

t-butylcumyl peroxide

1,3-3is (t-butylperoxy) diisopropylbenzene 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3

209831/0930

Unilube 50 MB-26 X: ethylene oxide-propylene oxide block copolymer

the NipponOils & Fats Go. Ltd.

1,459)

Unilube 50 MB-168X:

Plonon 204

Plonon 201

New Pol 75H-9OOOO:

(f: 1.05 at 20 ^u C, η
Ethylene oxide-propylene oxide block copolymer

the Nippon Oils & Fats Go. ltd. (^: 1o061 at 20 ° G, n ^ ⁰ : 1.462) Gopolymer in which ethylene oxide is grafted onto polypropylene oxide by graft copolymerization, manufactured by Nippon Oils ΰ: Pats Go. Ltd. (Average molecular weight: 3300) Copolymer in which ethylene oxide is grafted onto polypropylene oxide by graft copolymerization, manufactured by Fippon Oils & Fats Co ₀ Ltd. (average molecular weight 2200)
Ethylene oxide-propylene-oxide block copolymer from Sanyo Chemical Industries Ltd.

( 9 : I0O95 at 20 ° C,

1,466)

* The one at the nozzle end from the interface between the nozzle and product withdrawn molding aid boiled slightly before the cooler connected to the nozzle end became.

** _f *** These molding agents were melted by keeping the feeding devices for the molding agent at 100 ° C, and then fed.

Example 25

A vulcanized cable was produced in the manner described in Example 1, with the modification that polyoxyethylene aitearylamide instead of Unilube 50 MB-26X and di-t-butyl peroxide was used instead of DCP. It was a continuous process for 60 hours is achieved.

- 41 -

209831/0930

Example 26

Bin insulated cable was prepared in the same manner as in Example 11 except that sorbitan was used instead of S _o rbitanmonolaurat. Molten sorbitan was fed by keeping the molding aid feeder at 160 ° C. Continuous process management was achieved for 60 hours with a surface quality of the degree Ur ₀ 3 =

Example 27

3in insulated cable was produced in the same way as in Example 14, with the modification that dibutyl phthalate was used. instead of tetra-n-octylpyromellitate was used »while The process could be carried out continuously for 40 hours, with a surface quality accordingly Degree ur. 3 was received »

Example 28

A 3000 mm long nozzle with a long flow path with an inner diameter of 25.8 mm was connected to the outlet of the longitudinal head (ütraight-head) of a piston extruder The 300 mm long molding zone was kept at 150 ° C. and the subsequent, 2700 mm long vulcanization zone became heated to 200 ° C. A mixture of 1.0 part by weight of 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, 1.0 part by weight of N, lJ'-di-2-naphthyl-p-phenylenediamine and 100 parts by weight of high-density polyethylene (j> ί 0.965, ' Melt index MI: 0.2 (ASTM D 1238-1970, Method A, Condition F)) performed around a vulcanized rod of polyethylene high density with an outer diameter of 25.8 mm at a speed of 33 m / min. Unilube

■ Ζ ρ

50 MB-26 X was at a rate of 0.01 cmvcm of the outer surface of the product supplied. A continuous implementation of the process was guaranteed for 120 hours, being given a grade # 1 finish

Example 29

U _n ter using an apparatus shown in Figure 2, a vulcanizable Polyathylenkompound that hoQhdichtem 100 parts by weight of polyethylene of density of 0.96 and 2 parts by weight of dicumyl peroxide was extruded from the extruder into a die with long flow path 4 (5000 mm long). At the entrance of the nozzle 4, Unilube 50 MB-26X was fed to both the inner surface of the nozzle 4 and the outer surface of the mandrel 5 at a rate of 0.015 cmycm of the surface of the deformed product. While the molded product was moving through the long flow path nozzle 4, it was vulcanized at a temperature of 230.degree. The vulcanized product was then cooled in the cooling device 6 (length 5000 mm) under a pressure of 15 kg / cm. An excellent vulcanized polyethylene pipe was formed, the wall thickness of which was 4 mm and the outer diameter of which was 400 mm.

Comparative Examples 1 to 6

The deformation and vulcanization of insulation materials on cable cores was carried out under the conditions shown in Table 2 carried out. In Comparative Example 1, an insulated cable with good Surface finish (Ur. 1 grade) was preserved, but thereafter the surface of the cable gradually became rough and approx Minutes later with fine cracks. Pieces of gelled film of the molding aid (silicone oil) were on the cracked surface of the product. In Comparative Examples 2 to 6, only products with severely cracked Surfaces achieved.

209831/0930

O CD LD

Comparative example

Table 2

Structure of the electric cable » b

el

c2

Copper wire (19 / 2.0 mm, cross section 60 mm ² ),
covered with vulcanized, semiconducting polyethylene layer
(1 mm thick)

LDPE

(f>: Oo920
HI: 0.5)

TBCP triallyl iso-30 cyanurate
Parts 1.0 part tetra

me thylthiuram-

disulfide

0.5 part

dito

Copper wire (19 / 2.0 mm, cross section 60 mm ² ),
covered with vulcanized, semiconducting polyethylene layer
(1 mm thick)

dito

dito

dito

4th dito 5 dito 6th dito

12th LDPB
(J>; 0.920
WED: 0.5) TBCP
3.0
Parts Triallyl iso-
cyanurate
1.0 part Tetra
me thylthiuram-
disulfide
0.5 part dito dito dito dito dito dito dito dito dito dito dito dito-

Table 2 (continued) '

r - comparison
CN example

•
cst. Molding aid S. H
mg / cm i
ρ
cc / cm d 168.5 f
⁰ C. DO 2.39 1.36 Polydi-
methylsiloxane
(2000 cst.
at 30 ° C) 2.56 400 < 2> 200 30.5 castor oil 0.38 300 < 2> 17th 10.8 Eugenol 25 O <

Water - 100 2> -0.32

Paraffin oil 2.55 300 <51 120

Soap solution - 110 2> 1.8 1.25

(2b%

aqueous solution of potassium soap from soybean oil)

σ \

Pj
HHO

H- c + O

Pj
HH- O

H-c +
O

Sh

Pj H-

Pj Pj

H- H-

c + H-

O O

Pj HH-

H-H-O

pj pj

H- H-

c + c +

O O

Pj HHO

Pi pi

H- H-

c + cf

O O

Pj

H-c + O

Pj H- cf O

Pj H-c + O

Pj H- c + O

Pj HHO

H- et O

VK!

VH VKl

O

O

O

CTi

IV) O O

IV)

vn

till

V> J

O

IV) O O

IV)

vn

p. rv> rv> H- CD co

H-OO O O

tv) ro vn vn O

VKl

VKl

IV) O O

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209831/0930

Comparative example 7

Using the same vulcanizable polyethylene compound, an extruder of the same size and the same cable core as in Example 1, a vulcanized Polyethylene insulated cable using a conventional vertical standing steam vulcanizer with a Speed of O "28 m / min, manufactured The length of the Steam vulcanization chamber was 12 m, the length of the water cooling chamber 11m. The steam had a temperature of 205 ° C and a pressure of 18 kg / cm. The resulting cable had a surface of Ur grade. 4. The number of cavities in the insulating layer was determined according to the method described in Example 1 (Note 3) and there were about 100 Voids greater than 1 micron in diameter

an area-of 170 χ 120 microns in one off the middle layer found the disc removed from the cable insulation.

Comparative example β

A vulcanized cable was made in the manner described in Example 2, except that the Molding aid (Unilube 50 MB-168X) not through a feeder was supplied for the molding aid, but with the low-density polyethylene vulcanizable base material in an amount of "2.0 parts by weight was mixed per 100 parts by weight of the material. However, the extrusion of the vulcanized product was not possible because the material is on the inner surface

the nozzle with a long flow path strongly vulcanized and stuck.

209031/0136

Claims (1)

Claims A method of molding and vulcanizing a vulcanizable material in which a mixture of a by means of of organic peroxide vulcanizable polymers and of an organic peroxide is passed through a nozzle with a long flow path, one forming zone and one subsequent Has vulcanization zone, while at the same time using a molding aid on the inner surface of the nozzle long flow path is applied, characterized in that the molding aid used a) a viscosity of at least ₀ 5 gentistokes and not more than 3000 centistokes at 235 ° C, b) has an absorption ratio in the polymer of less than 100 mg / cm at 150 G for 45 hours, c) in contact with the organic peroxide during the Vulcanization is not gelatinized and d) does not boil during vulcanization, and in that the molding aid is supplied in such a way that an uninterrupted film is between the inner surface the nozzle and the polymer product is maintained. 2. The method according to claim 1, characterized in that the molding aid used has a viscosity of 5 to 3000 Ce _n tistokes at 235 C and an absorption ratio of less than 30 mg / cm for 45 hours at 150 ° C. Process according to Claim 1 or 2, characterized in that one of the following compounds is used as the molding aid is used: 1) Polyoxyalkylenes and their derivatives, random, block or graft copolymers of at least two alkylene oxides or their derivatives, with a molecular weight of more than 120 and less than 100,000, - 47 - 209831/0930 IS 2) polyhydric alcohols, including dehydration products of these compounds, having 4 to 50 carbon atoms and their alkyl esters or ethers, 3) fatty acid alcohol amides with a total of more than 8 carbon atoms, which were obtained from fatty acids with 2 to 30 carbon atoms and alcohols with 1 to 30 carbon atoms, 4) fatty acid amides with 8 to 90 carbon atoms, 5) Fatty acids with 8 to 30 carbon atoms and their. Metal salts, 6) Esters of polycarboxylic acids containing 6 to 22 carbon atoms and monoalcohols with 1 to 20 carbon atoms 7) phosphoric acid esters of alkyl alcohols with 3 to 30 carbon atoms, 8) polyester with a molecular weight of more than 200 and less than 30,000, 9) metal nitrates and metal halides, 10) Mixtures of polysiloxanes with a molecular weight of more than 2,000 and less than 100,000, and G-elatinization inhibitors, 11) Mixtures of polysiloxanes with a molecular weight of more than 2,000 and less than 100,000 and one Alkali metal hydroxide, alkali metal oxide, alkaline earth "metal hydroxide or alkaline earth metal oxide, and that the molding aid used as a continuous film between the inner surface of the nozzle and the Polymer product is placed. 4. The method according to claim 1 or 2, characterized in that polyoxyalkylenes or their derivatives as molding auxiliaries, random, block or graft copolymers of at least two alkylene oxides or their derivatives, their Molecular weight greater than 120 and less than 100,000, or mixtures of these materials, may be used « 5. The method according to claim 1 or 2, characterized in that mixtures of polysiloxanes - 4H - 209831/0930 having a molecular weight of more than 2,000 and less than 100,000 and gelatinization inhibitors can be used. 6β Method according to claim 1 or 2, characterized in that that as molding auxiliaries, mixtures of polysiloxanes with a molecular weight of more than 2000 and less than 100000 and an alkali metal hydroxide, alkali metal oxide, alkaline earth metal hydroxide or Brdalkali metal oxide will,, 7ο method according to claims 1 to 6, characterized in that that the molding aid with the help of one in the nozzle Long flow path arranged porous tube in the area of the entry of the nozzle channel on the inner surface applied to the nozzle o 8 ο / experienced according to claims 1 to 7, characterized in that the vulcanization zone of the nozzle with a long flow path is kept at a temperature between 140 ° 0 and 300 ° C and the vulcanized product is cooled with the aid of cooling water after exiting the nozzle channel, which is kept under a pressure of 5 to 50 kg / cm. ο AV! their claimed in claims 1 to 8, characterized in that the deformed and vulcanized polymer is polyethylene with a melt index of Od to the second 10. The method according to claims 1 to 9 »characterized in that by continuously supplying the molding aid -Un the inner surface of the nozzle with long flow path o in a continuous film of the molding aid between the inner surface of the nozzle and the surface of the polymer proa-.tktrj is trained » 11. The method according to claims 1 to 10, characterized in that that zuii !! create an electrical cable with a Cover "aq - 209831/0930 ^ ₀ original. a) a molten vulcanizable material consisting of one made with the help of organic peroxide vulcanizable polymers and an organic peroxide, continuously on an electrical conductor is extruded, b) the material is deformed and vulcanized by is passed at elevated temperature and pressure through a nozzle with a long flow path, which has a molding zone and a subsequent vulcanization zone, while at the same time applying a molding aid to the inner surface of the nozzle with a long flow path is applied which 1) a viscosity of at least 1.1 centistokes and at most 3000 oentistokes at 235 ° C, 2) an absorption ratio in the polymer wn ο
less than 30 mg / cm for 45 hours Has 150 ° C, 3) does not gelatinize in contact with the organic peroxide during vulcanization and 4) does not boil during vulcanization, and c) the coated conductor after exiting the end the nozzle with a long flow path with the help of under ο
Pressure of 15 to 30 kg / cm of standing cooling water is cooled » 12. The method according to claim 11, characterized in that that the polymer used is polyethylene with a Sohmelzindex from 0o1 to 2.0, the Vulkanisatxonszone the nozzle with a long flow path is kept at a temperature between 200 ° C and 300 ° C and that the Molding auxiliary is selected from the following compounds: polyoxyalkylenes and their derivatives, statistical, Block or graft copolymers of at least 2 alkylene oxides and their derivatives, the molecular weight of which is more than 120 and less than 100,000, or a mixture these materials. - 50 - 209831/0930 216456Q • 13 ο method according to claims 1 to 12, characterized in that that an electrical cable with a uniform, smooth insulating layer made of vulcanized polymer is produced, which is when viewing a specimen 10 microns thick under an optical Microscope with 300x magnification proves to be free of bubbles and cavities. 14. The method according to claim 1, characterized in that the molding aid for producing tubular products on the inner surface of the nozzle and on the outer surface of an inside of the nozzle with a mandrel arranged along a long Pließweg is applied « 15 «, method according to claim 14» characterized in that that the mandrel is arranged so that it extends the entire length of the nozzle and into the cooling zone. 16. The method according to claim 1, characterized in that the vulcanizable material into a tube made of vulcanized Polymerem is deformed. 209831/0930