DE1915061C - - Google Patents

Description

The _invention relates to the use of a mixture of

a) 50 to 36 percent by weight isotactic poly-

butene-1, _u . ,

b) "> 3 to 29 percent by weight amorphous and / or atactic thermoplastic material as well

c) 27 to 35 percent by weight of a conductivity black as a conductive plastic compound door the cable sector.

* f 'Zsclmh 1325442 and 3264 2531 Ver-heitet one now polybutene-1 having the erforder-Y μ "S to _S oerhält." ie to expect a ^Μ ^ ^^ ^ ^ gt bel and highly resistant to breakage

-VnPiIHe is Tried., «. N, not crystalline substances anlalhg is. vertuen ^ _Ermedn .

^ add. «« E ^ fJJ « ⁵ ^ _istotactic poly-sy.en proposed -rden ^ utsch ^ interpretation

™haben ^^ _{η da} ß when replacing H). 20, 30 and ScewichtsJ'rozeni of the crystalline component m one consisting of isoctic polybutene-1 and 24 percent by weight conductivity black and adjusted to a specific contact resistance below \ m \ "> cm, for example 200 U cm

_(At ¥ t, _S ches polybutene-1, alaktisches polypropylene. Äthvlcn-propylene Kautscliuk, polyisobutylene) a significant, ie far öhung about 100011cm hmausgehend ^ _Ern the specific Durchgangswidcrstandes _{occurs F} i _n lifting the soot component in turn has _{a renewed} decrease of the obtained Flexibi itat ^ in order _{to find} a solution on this basis

does not appear to be given.

voltage peaks and glow discharges at the border - only for the production of surfaces. It is also desirable to use a lower mentioned molecular weight d «such a mass in combination with isotactic butene-1 and the ^ PJ E polybutene-1 as the outer cable sheath, so as not to solve the here, ^b ^

Discharge external currents, for example contribute to the grounding ₅₅ , the broad g ^enann ^ ⁿ te.l

_ΤοΙ ^

^the 7th

With

äSn ^ lv ^^ rmiSSr % Ä SJS »

In the 70 D federal states, these are only unsuitable because they are made of polybutene! to

they under current load for stress cracking 6 ₅ expected good Vertg

tend and, especially with polybutene-1 that is particularly resistant to stress cracking, finally ^ oghchen wu ^ d.e ^

Insulating materials, such as the, in this respect, well-known E.genschaftend.eses polymer the

draws usable polybutene-1, not or only to make the cable sector more accessible.

I 915 06!

This task is accomplished through the use of a mixture

a) 50 to .U) percent by weight of istotactic polybutene! .

b) 23 to 29 percent by weight amorphous and / or niakiischcm thermoplastic material as well

el 27 and ¹ percent by weight of dissolved O a conductivity carbon black as a conductive plastics material for the cable industry.

Usable isotactic Pohbutenes-1 are partially crystalline and have _{/ riJ} values *) \ on 2 to 6 and densities according to DIN 53479 from 0.4 (K) to 0.930. They are manufactured according to the Ziegler-Natta process using complex Katahsatorysleme, such as the contact

AKCJU) ₁ CI (3TiCI., -AICl ₁ )

Atactic polybutene-1 that can be used is dropped according to the same polymerization process as an ether-soluble fraction up to about 20 percent by weight. Ls does not need to be separated for the present case, but must be added when the further required amounts of atactic or amorphous phase with regard to the (established limits must be taken into account. The; / ". ,, - values of the ataclical Materials and the same also apply to that obtained during the polymerization of isotactic polypropylene ataktis.he polypropylene material are between 0.3 and 0.9, preferably 0.5 to 0.7.

Suitable ethylene-propylene chewing chews, which are made as amorphous copolymers using complex catalyst systems such as VCl ₄ , VCl ₃ or VOCl ₃ and aluminum alkyls or aluminum alkyl halides, e.g. B. aluminum sesquichloride, are produced at temperatures above 0 C, preferably between 20 and 60 ⁰ C, have molecular weights between 70,000 and 250,000 with a proportion of propylene or ethylene of 20 to 80 percent by weight.

Polyisobutylenes which can be obtained by cationic polymerization, for example with the aid of BF _r complexes as initiators in more liquid ethylene at about -100 ° C., are those with molecular densities between 400,000 and 5,000,000.

The carbon blacks are, on the one hand, carbon blacks obtained by thermal decomposition of acetylene gas (acetylene carbon blacks) with average particle sizes of 30 to 60, preferably 35 to 57 πΐμ, determined by electron microscopy, and specific surface areas of 95 to 53, preferably 90, calculated from this up to 56 m ² / g and contents of volatile constituents not more than 1 percent by weight, on the other hand to furnace carbon blacks obtained by the process of incomplete combustion of liquid hydrocarbons (oils) with average particle sizes determined by electron microscopy of 20 to 29, preferably 22 to 28 Γημ, and correspondence

*) i _{/ ri} , _r value: The reduced viscosity
the form!

is calculated according to

c Vo

where c = concentration (c = 0.1 in p-xylene at 110 ° C); »;,. = dynamic Viscosity of the solution; ij, = dynamic toughness of the Solvent.

specific surface areas from 140 to 85, preferably 120 to K9 rrr / g with a content of volatile constituents not more than 2, usually between 1 and 2 percent by weight, Ls is s in both cases are highly structured carbon blacks, with the Acetylene blacks have a structural index (see Rubber Age 55, p. 475. No. 5 August 1944) around 300, the Iurnace black have one around 130. The smaller the diameter the Ruli particles and the larger the specific The surface, the better the conductivity in general, the greater the general rule also the degree of flexibility of the resulting mixture. There is considerable Γ -influence in every rope the proportion of volatile matter, inasmuch as higher

The volatile content of the conductivity strong / ti affect ability.

Conductive plastic compounds made from these components meet the requirements if, with a kiss dosage of 26 to 35 percent by weight, the proportion of atactic and / or amorphous phase in the total mixture does not fall below 23 percent by weight and does not exceed 29 percent by weight on the other. If the proportion of carbon black is greater than 35 percent by weight or the proportion of atactic and / or amorphous material is less than 23 percent by weight, the result is masses that are too brittle for the intended purpose. If the proportion of soot is less than 27 percent by weight or the proportion of atactic and / or amorphous phase is greater than 29 percent by weight, the specific volume resistance is well over 1000 μl , sometimes even a power of ten higher. Lowering the crystalline proportion of the mixture below 36 percent by weight also results in too great a loss of strength.

For the purpose of stabilization, antioxidants such as Jonol = (2-, 6-di-t.-butyl-p-cresol), 2- «- methylcyclohexyl-4, -6-dimethylphenol, N-stearyl are expediently added to the masses -p-aminophenol or 4-, 4'-thio-bis- (C-1.-butyl-3-methylphenol), optionally together with sulfur-containing compounds such as dilauryl thiodipropionate in a concentration of 0.03 to 0.5 percent by weight. Furthermore, you can add lubricants such as calcium, sodium or zinc stearate (0.1 to 0.6 percent by weight), lubricants such as graphite (1 to 5 percent by weight) and - brought in by the isotactic material, so to speak - crystallization and conversion accelerators for a faster transition from the modification II obtained from the melt da isotaklisclvn polybutene I into the stable modification F (J. Polymer Sci. B 62, S7d | 19h2 |. / Ii. Amyli "" at. //-Chlni.iaphth.ilin and l'liciuLithcr also known from PVC ester plasticizers, such as dioctyl phthalate, optionally also in combination with the latter at the expense of the crystalline polybutene-1 component of the mixture, botactic polypropylene or substances known as viscous genes in the form of aromatic, partially aromatic or aliphatic hydrocarbons.

The manufacture of the masses for which a protection However, it is not desired, can be easiest using a heated to about 120 to 160 ° C To accomplish this, for example, in the one presented on this roller, to a case

plasticized, partially crystalline pelybutene-1 atactic and / or amorphous material, carbon black and other additives such as antioxidants, lubricants, etc. incorporated. One makes use of it in a particularly advantageous manner

5 6

But there are also parts of alactic polybutene-1 heated to 140 to ISOC. 30 (> c \ WLhtsieile \ ce! \ -

Kneader and brings the plastic Icn-Ruü uiiil 45 (jcwichlsteiie isotakusches PoU-

Misehunji on a butene-1 heated to about HH) up to 120 ° C. which the stabilization and development

Whale / e. pulls out / u a lall. which are contained in strips and aids, one after the other. Man

cuts, which lel / .lere a mill or also: · take out the mixture afterwards? Minutes mixed / cit.

feeds to an <ir.mul.itor for shredding

lieruestellien granules can then easily over a jelly and compressed this to 2. 3 and

a lxi rudder for 4 mm thick plates from the lin filling funnel / ur nozzle, to about HM) to 2 (H) C unites "-s! ..-! lten! emneratures closed

Leitlahiüen sheath masses are processed. The result of the exams

The following examples should include the Irlindunii \ er, ...,, .. u, ι ...,., „ι -im.,, · ■

, · Λ ■ "Specific Durchnangswkicistand JHiLiLi.ι

ual. , '<■ 1 1 w> l

.... . .... (irenzhieuesnannunii I -κ. Κ

de

! . . ....,. . Ciren / bending stress

For an objective comparison ....,. *. >, ..

CIlV

Without breaking any further

/ u / ulassen. always flowing substances emueset / t: - ^. , ■

, ι, i> Γ ι ι ■ "■ .ι lmrchhieuunn:

sotactic polybute · '.-. from its atactic is, ·, r, "■ _u - ι ·,, ■",, n,., .. ,,

.. ,, ·· ι ι, "'u r ι. iv u kerbschlau / ahigkeit οηικϋιικί;

a soluble phase and with a density "," ·,,. ν ₍

.... ,,, ..-- ,, - ,,>, χι, - ■ ac Bniilcness-Temperatur ■■ ■■> ^l

üemal.t I) IN. "> 3479 of 0.91 \ a /, .. ,, of 4.5, ...,., -. _{M tl} u, ι

■,, vi ^. ,,, """JSchweil.Makior" · ' ^{| Ί! Ν} '

corresponding to an average MKd of 2,200 (XX).

one! (iren / hot voltage measured on from 4-mm- li.in i.insat / vi> n atakti.schem PoKpropvlen on see

Press plates punched Noimkleinsübcn gcmÄÜ ze de.i> aUiklischen Polvbuteivl i'iihrte / u practical

DIN 53452 of 240 kgf / cm ² , results similar to notch impact.

Toughness test according to DIN 53453 "without break"

and a Brittleness temperature according to ASVM D 746 comparative example 1 b)

Atactic polybutene-1 from the i _{/ r i} .j value 0.6, corresponds 25 <·) With an arctic from 25 Gewichtslcilen speaking about an average molecular weight of polybutene-1, 37 parts by weight of acetylene black and 3 (K) OOO. 38 parts by weight of isotactic polybutene-1 according to

Stabilizing and processing aids are, la) existing mixture is referred to as in the above to 100 parts by weight of the total mixture, previous example! proceeded.

0.4 parts by weight 4-, 4'-thio-bis- (6-t.-butyl-, 3-methyl- 30 The following data result - phenol) 0.3 parts by weight of dilauryl thiodipropionate specific passage and 0.4 parts by weight calcium stearate. resistance 170 Q cm

Acetylene black with a mean particle size limit bending stress Y YYYYYYYY 150 kp / cm ²

(determined by electron microscopy) of 35 ma, a MtR hh 't

specific surface of 90 m ² / g and a content of 35 p. ■■ ·

of volatile constituents less than 0.6% notch impact strength 2 cmkp'cm ²

hurnace carbon black with a mean particle size. Brittleness temperature + 18 C

23 ma. A specific surface area of 93 nr / g and sweat factor. 0.6 to 0.8

a volatile component of 2%.

Polyisobutylene with a molecular weight of 4,700,000. 40 The increase in susceptibility to breakage compared to

Ethylene-propylene rubber with a medium mixture 1 a) is unmistakable.

Molecular weight of 100,000 for a propylene , 1) If the carbon black dosage is reduced to a proportion of 50 percent by weight. retention of the atactic weight proportion of

The test method used is mixture I a) increased to 25 parts by weight and d

, · / ·. r- »ι. j j 45 crystalline component corresponding to 50 ge

the volume resistivity, measured ·. ,, ·, Un rv.t """.- il c _rm u": ,, ".

-1 ni .. u iMMcninMnrmn- important point, the following results are obtained.

on 2 mm plates according to DIN 53482 / VDE 030j,

Part 3, Specific Passage

the limit bending stress according to DIN 53452, resistance 9000 U cm

the notched impact strength test, corresponding to the limit bending stress 80 kp / cm ²

DIN 53453, carried out on 3 mm plates, ⁵ ° without break at further Brittleness temperature according to ASTM D 746.

The welding factor (heated mirror butt weld) notched impact strength without breakage

is determined from the tensile strength with reference to the Brittleness temperature - 12; C

the weld-free test specimens (= 100%) in a 55 welding factor 0.9 to 1

Temperature range from 180 to 240 C at a Zwai corresponds in this case to the mechanical

Contact pressure on the mirror of 0.5 kp / cm ² and a property profile that of a conductor smoothing compound for welding pressure of 1 and 2 kp / cm ² . requirements. The specific through

The term "ladder smoothing compound" includes a contact resistance which is more than one

"Semiconducting flexible-soft plastic compound", the 60 power of ten too high, in this specification, of course, everywhere

can be used where it is a question of comparative example Ic)

Discharge currents, for example for grounding

of a telephone cable as an outer cable sheath. n) Put into the Werner & Pfleiderer kneader

. . 65 20 parts by weight of ataclical polybutene-1, 30 parts

U e; ä ρ 1 e 1 la) parts by weight of acetylene black and 50 parts by weight of iso-

Introduce tactical polybutene-1 heated to 130 ° C and proceed as in

2-1 kneader (Werfer & Pfleiderer system) 25 weight example 1 a).

The test specimens produced from the press plates show the following values:

Specific volume resistance 180 Ll cm

Limit bending stress 140 kp / cm ²

With a break in another
Deflection:

Notched impact strength 1.5 cmkp / cm ²

Brittleness temperature + 10 ⁰ C

Welding factor 0.9 to 1

(i) Test specimens containing 30 parts by weight of acetylene black, 30 parts by weight of atactic and 40 parts by weight of isotactic polybutene-1, give the following results:

Specific volume resistance 1500 il cm

Limit bending stress 90 kp / cm ²

Without breaking any further
Deflection:

Notched impact strength without breakage

Brittleness temperature - 12 ^U C

Welding factor 0.9 to 1

The comparative examples 1 c), a) and 1 c), β) make it clear what a great influence the atactic material has on the electrical and mechanical behavior and how narrow the range is in which satisfactory compounds are obtained for smoothing conductors or cable sheathing will

Example 2

The atactic polybutene-1 in the formulation according to Example 1 a) is exchanged on the one hand for polyisobutylene and on the other hand against ethylene-propylene rubber and otherwise proceeds as there described.

The following property values are found in the case of polyisobutylene:

Specific volume resistance 1801'cn ^

Limit bending stress 70 kp / cm ²

Without breaking any further
Deflection:

Notched impact strength without breakage

Brittleness temperature - 15 C

Welding factor 0.9 to 1

In the case of ethylene propylene rubber:

Specific passage resistance · 70 Il cm ^

Limit bending stress 80 kp / cm

Without breakage in the event of further deflection:

Notched impact strength without breakage Brittleness temperature -25'C Welding factor 0.9 to 1 Example 3

Instead of the acetylene black in Example 1 a), a furnace carbon black is used instead of the aactic one Polybutene-1 an equal amount of polyisobutylene.

The dates are:

Specific volume resistance 15011 cm ₂

Limit bending stress 50 kp / cm

Without breaking any further

Deflection:

Notched impact strength without breakage

Brittleness temperature -32 ° C

Welding factor 0.9 to 1

Example 4

Using a tandem extrusion line, consisting of a) a Troester 60 extruder with Short compression screw (20 D, compression ratio 1: 3.5) and a pressure spray head, right-angled to the extrusion axis, for the purpose of applying the conductor smoothing [recipe according to Example 1 a)] to the Metal loaders and b) from a 150 Troester extruder with a short compression screw with the same compression ratio as above and one for Extrusion axis inclined by 60 ° for the coating with the insulating layer isotactic polybutene-1 of those taken under la) Specification, you put several hundred meters to build a three-core 30 kV cable under the following specified processing conditions:

To a) conductor smoothing:

Temperature agitation .... 14O / 185 / 17O / 17O / 180 ° C (from the feed hopper

to the nozzle)

Melt temperature - about 180 ⁰ C

Current consumption 24 A

Screw speed .... 23 rpm

Under these conditions, the conductor smoothing layer is 1 mm thick.

To b) core insulation:

Temperature control ...

(from the feed hopper

to the nozzle)

Melt temperature

Power consumption

Screw speed ...
Take-off speed
water bath

(about 30 m long) ...

155/155/165/150/156 C

about 205 ⁰ C
160A
25rpm
3.2 m / min

temperature

at the entrance 40 "C.

at the output 20 ° C

The thickness of the core insulation is 18 mm.
Loss factor measurements according to DIN 53483 / VDE 0303. Part 4. with between inner and outer conductor. η that

so finished cable voltages applied between 8-46 kV and more than 270 hours at 500 Hz and 10 kV after 14 hours storage of the test lengths at room temperature (the latter test is as Zeitraffnethode so too wide. that dei results determined at 500 Hz and 270 Stunder that at 50 Hz and 2700 hours corresponds) confirm the expected result of a largely constant, ie independence de;

Loss angle λ of voltage and time. If one replaces the acetylene rule in example la)

by the Fumace carbon black of Example 3, then yields a of 38 percent by weight isotactic, 28 percent by weight atactic polybutene-5 and 34 percent nothing percent Fumace carbon black existing mixture comparable results. The same applies to example 2. whom

instead of 25 percent by weight ethylene-propylene Rubber. 45 percent by weight of isotactic poly-butene-1 and 30 percent by weight of acetylene black now 23 percent by weight ethylene propylene rubber

30 ° Λ34 43i

3393

49 percent by weight isotactic polybutene-1 and 28 percent by weight furnace carbon black are used. Finally, in Example 3, the polyisobutylene is replaced by an ethylene-propylene rubber of MW 120,000 with a proportion of 40 percent by weight propylene on the one hand and through the atactic Material according to Example 1 for the other half, values comparable to Example 3 also result.

Even when using polyisobutylene with molecular weights of 2,700,000 or 1,300,000 instead of a polyisobutylene with a MW of 4,700,000 according to Example 3 or when replacing the partially crystalline poly-u-butylene in these examples with a higher or low molecular weight product (' ireä = 3.0 or 5.5), no deviations worth mentioning are obtained.

Claims (1)

Claims: Using a mixture of Pole> - hl 2 S () bis36 (; - ^: cluspro / eni is.uaklischcm bulcn-1. 2 to 2 ^l Kiewichlspr. '/ Cnl amorphous or and ataktisclvm thermop., Secure material as well. , ο ei ^ 7 to .VSCiew ^ htspro / ent cr.es conductivity ruthless as a conductive plastic compound for the cable, ector. ι Use according to claim 1. thereby gekcnn / cichncl. that the component b, an atak- .s livches l'olybutene-1 is>. 3. Use according to claim 1, characterized in that component b) an atak ^l t VeÄu ':: ¹ according to' claim 1, characterized in that component b) is an ethylene-propylene rubber 5. Use according to claim 1, characterized in that that component b) is a polyiso- butylenist. _llAA u 6. Use according to claim 1, characterized in that component c) is an acetylene ^RU 7 ^ß Use according to claim 1 to 5, characterized ^ indicates that component c) is a furnace carbon black. very imperfectly spared, «as ^ ™haben win-'frcics functioning of the KaKl cmc mIW ^ttallja 'Vnnu-seVung represents understandable \« ^dUsC p; "T _ulcn ., _llK isoliermantd ^ "'""The ζΰΐαπΐοη, it is obviously necessary auXem" leitfahiges material ^. ^' ^ '^ T to a specific nut Purchgangswidersund Heiner than CHD) U cm / u create. _{Hi there,} cn Ruli / usat /. nuc c ^ - , r, ι TCT TiI iinil der ueuiseiicn i \ usi; SA.-Paienlschnft 3 257JM unu Uli ,, , _hrifl ! 226 782 door part krista Ιπκ I οΙ>ο1ϋι> κ „ _round; , atzlieh is known. Here one er.ia t. Jl. ^ ArI and amount of rulks and 1 ^^^ aliem be. higher ^^, '^ pXn ^ chrifl 1 4454 «,:. ^ ^a ^ ⁿ ™ _f ^ HlV Nne associated with , u ι Ik-U is sought through networking going 1 uch gko such ' ^ _{man M1} " or ^^^^^ "^ iene bc-nmnr. n.ederer