DE1694352A1 - Polymeric blends of non-polar polyolefin, chlorinated polyolefin and polyvinyl chloride and processes for their preparation - Google Patents

Description

General Electric Company, 1 River Road, Schenectady, N.Y., USA

Polymer mixtures of non-polar polyols Hn, chlorinated Polyolefin and polyvinyl chloride and processes su their

Manufacturing

Virtually non-polar polyolefins such as polyethylene are normally incompatible with polyvinyl chloride. The known addition of chlorinated polyolefins, such as polyethylene, in amounts of about 5 to 10 percent by weight bu mixtures of non-polar polyolefin and polyvinyl chloride allow production

109810/2067

a Misehivßg, this lsi; S & doah as insulating mates ¹ ! ¹ ,! ·, Jt ü:; - wire and cable unsuitable, »In addition, you can <3oi; ⁱ iAr "5, ga mixtures na« .: r after h ^ Wir.rai'lichen procedures haxvps'P-sju.k be.

According to the present invention there is provided a hardenable composition proposed, which is suitable as an insulating material for a wire or a cable and consists of a) 20 to 60 percent by weight, preferably 30 to 5 percent by weight, based on the total mixture of practically non-polar polyolefin consists of a chlorinated poly oil and polyvinyl chloride in a ratio of about 1: 3 to 3: 1 »preferably 1: 2 to 2: 1, and also of one Stabilizer for the chlorinated polymers and c) a peroxide curing agent. After hardening, they have Masses have a high cut-through resistance, low indentability, low penetration), which is essential is above that of networked products that consist of a Component or a combination of any two components of the three components of the invention polymer mass, or that of an uncured product of one of the three components. Bs was found that such masses are prepared in conventional catfish can be made by first creating a basal ridge that part of the bulk used becomes practical

BATH ORIGINAL 109810/206 7

lei'Xrui srt ^ ibtUt. 7.u this "Ui becomes gutm un ^ :; ¹ Rüekfliiß'at'cltagungen gradually there '- the rest of the nichfcpclsv *. When the mixture is intimately mixed, a Kifx'tos oil, or a suitable peroxide, is added. Then the mixture is processed, for example an electrical conductor is through

öschioht

Overmoulding old an XsoXa1?: LcnI provided, which then hardened wlx-6 * md e3.se öurch ΗΙ ^, ^ β hardened or crosslinked Iso-'t π 1.1 det.

O5.e nachro;> ac: .ö uses.su Esgreiffe "wire" and "cable" are used as a synonym i'üi 'si.r.i · - «insulated conductor.

The polymer?. " Components of the mixture according to the invention are well known and lei «b <; available. The practically non-polar olefinic constituent includes homopolymers of <* -olafinane such as ethylene, propylene and isobutylene; Copolymers of two or more such * 0 -olefins as ethylene-ethylene xmd stylsn-propylene and copolymers; and copolymers of a cc . olefin with etder @ n monomers such as vinyl acetate and ethyl acrylate; at least 50 weight percent and preferably 75 to 90 weight percent of the copolymer !! consist of <* j - olefin. Polyvinyl chloride, which is used in the mixture according to the invention, comprises the suspension **

109810/2067

PoXynisre, the <cmulsilon ^^ iyms ^ i & iLer ^ Poly mere and that in the mass po. '. Yius ^ .if'.ie ^ Polymers \ xn & bat; sweckm & iigc rpfidssi sin high Moiekul & ^ gewlcht. The FoXyvln ^ Xchloria can with b; »? 10 percent by weight of monomers are copolymerized, for example with vinyl acetate, vinyl stearate, vinyl chloride, acrylonitrix and acrylate acrylate. The chlorinated polyoxefin is preferably chlorinated polyethylene * which contains 35 to 50 percentages of chlorine.

According to a preferred example of the the Masee is made of a polymer mixture of polyethylene, chlorinated polyethylene and polyvinyl chloride manufactured; and the invention shall hereinafter be considered with reference to FIG this embodiment will be explained.

In applications where the insulated wire or cable should be extremely flame retardant, the polymer Mixture desirably from about 20 to 35 weight percent chlorine, and preferably no less than 25 percent Percentage by weight included.

A particularly preferred polymeric blend comprises about JJO weight percent polyethylene, 30 weight percent chlorinated Polyethylene and 30 percent by weight polyvinyl chloride.

! O _9810/2067

In order to improve the solution of the polyrase, a stabilizer is added to the hardenable mass during the misting, which is supposed to neutralize any free acid formed and thus prevent a chain-like reaction which leads to the destruction of the polymer . Stabilizers contain, for example, lead oxide or black lead, basic lead silicate sulfate, basic lead silicate and magnesium oxide. The amount of the stabilizer used depends on the amount of chlorinated polymers present and sshrank ·· ¹ ; between 5 and 10, preferably 10 and 35, parts based on 100 parts of the polymeric mixture. Quantities of more than 5 parts are not sufficient to ensure the desired networking, and using quantities of more than 1Q parts is generally useless

Additional Ingredient Desirably In The Bulk present and mixed therewith include, for example, an antioxidant such as polymerized Trimethyldihydroquinoline, a lubricant like calcium stearate, that is to prevent the hate from sticking during processing, and a small amount of pigment or Coloring agents such as carbon black. Antimony oxide can also be added to the mass in order to improve the flame-retardant effect. If non-flammable additives such as antimony oxide are present in the mass, this can be responsible for the flame-retardant effect

109810/2067

öhlorankeiX hsyabgesetzv warden, unS bai production of the » polymer mixture can be a i« sfc3ps * sc5hS2 reduced Msngs ehlorlert.es polyethylene uml / aiies »polyvinyl chloride vsi '

The peroxide curing agent (proxide) preferably includes tertiary peroxide with at least one structural unit

C. ti 1
ö ι ι c-c-o-ö-ü-e C.

welehes at alner Temps ^ avur van over 130 ⁰ C s ^ Use of this Perorydhärtunssmättel zuk V polymsrsr connections was in the US-Pafeentan 3,019 and 2,886 '^ 2k beachxd. ^ an »Anders sweolanäölge rlfi includes & n those in deia Ü.S ^ -Pasent 3 4 acetylene diperoxy compounds.

The amount of peroxide hardener used depends largely on the mechanical properties that the cured product should have, for example hot tensile strength. An amount in the range of 0.5 to 10 divisions Peroxide per 100 parts of the total polymer content Fabrics meet almost all requirements; the usual amount of peroxide is 3 to 4 parts by weight. At a

Peroxide typical manufacturing process with tertiary I as hardener

BATH ORIGINAL 109810/2067

fc (ltff tfennisehune at sisisr TGiapeiPatmr

unglttu * 3LCO ⁰ G and IJO ^C 0 ₅ preferably each & osh s 3.30 ⁰ C nn & VdO ° C. Ksaa d «ß mixing b © & e liner

fc, die ciasentliah fifcss »asm angogebeiisTS Maximum Xiogt, se-rcti ^ sfe dac Fei ^T ei: yd and leads su? Preliminary curing at least e.inps parts of the polymeric connections. Consequently, the Verarbeifcung the mixture is made more difficult, and has Rmüprudukt, άβτΜ fiSregelrnößlge or roughened surface. The Mishung obtained is then belnpie% wa5..ae by molding processes ₉ a Isoliej "SCHS '? Ht for wires or cables form below. The finished product was then used as a stand. As often as possible, using the conventional Daijtpfhärtungsverfahren at about 20 * 1 ⁰ G ( ¹ JOO ⁰ F) to 2 10 ⁰ C {HO ⁰ P) and IT, 5 kg / era ² (250 paig).

A basic smell is used in the manufacture of the pug manufactured, the ohloriert.es polyethylene and polyvinyl chloride in the right proportions, as well as one Part of the total Polyäthylen® used in the mixture. Preferably no more than about one Third of the total polyethylene used in the mixture is added to the basic mixture tends to soften or plasticize the other polymeric components involved in the reaction, so that the polymers can be mixed uniformly.

109810/2067

At least part of the stabilizer is added to the basic mixture, the amount of which, however, depends primarily on the type of stabilizer used and can easily be determined by experimentation. Certain _stabilizers> such as basic lead silicate make dry the mixture and stiff when they are added in amounts au Groften; consequently the mixture crumbles and ISAt is extremely difficult to process or plasticize. For this reason it can be desirable to add only part of the stabilizer to the basic mixture. Generally, more than half of the stabilizer is added to each base mix and the remainder of the stabilizer is incorporated into the mix during the second stage of mixing (described below). With many stabilizers, however, the entire amount to be used in the mass can be incorporated in the same way as the basic mixture. The basic mixture is produced at an elevated temperature; however, the temperature must not be so high that the polyvinyl chloride and / or the chlorinated polyethylene decomposes or is broken down. The mixing can, for example, *> erature be from about 15 * ⁰ C (310 ⁰ P) to I63 ° C (325 ⁰ P) in a Banbury mixer at a Tt. Di · Zumieohung 1 is then t about 93 ⁰ C (200 ° P) bit 121 ⁰ C (250 ⁰ P) is ground. If the full amount of stabilizer, e.g. basic silica gel, is added during this stage, it is particularly desirable to be

109810/2067 8AO

sines · Tempora ^ ujsu wed, dia near bsi des? higher temperature »

The remaining stabilizer of the örundmisehung is added to the second mixing stage of this process. When mixing begins at flow temperature, the remaining polyethylene is gradually added to the mixture. This second mixing stage is carried out at lower temperatures than the first; the temperatures for the second mixing stage are usually not above 275 ^° C. If the mixture gets too hot, it becomes sticky and difficult to process. The hardener is then incorporated into the substantially uniform mixture.

A typical method of making isolated Wires or cables, the final mixture is tabletted and stored for later use.

example 1

A basic mixture of 32 weight percent chlorinated polyethylene (which contains 45 weight percent chlorine), 32 weight percent polyvinyl chloride and 7.29 weight percent polyethylene with 21.86 weight percent basic lead silicate as a stabilizer, 5.16 weight percent ONCOR-23A (50 % antimony oxide, which is formed with silica and from the National Lead Company

109810/2067 ORIGINAL BATHROOM

- ίο -

was prepared), 1.28 weight percent Polytriraethyldihydrochinolin as Antioxyaditionßmittel and 0.4l Gewiehto percent carbon black as a pigment was at about 154.4 ⁰ C (310 ⁰ F) to 163 ⁰ C (325 ⁰ P) in a Banbury mixer for Flow heated and gave a virtually uniform mixture. The mixture was placed on the rolls (P 210 ⁰⁾ and were adjusted back to 93 ⁰ C (200 ⁰ P) at the front to 99 ⁰ C. The mixture was then removed from the rollers as a film and placed back in the Banbury mixer for remixing. During this second phase, 6.36 percent by weight of basic lead silicate (remaining stabilizer for the mixture) and 0.73 percent by weight of calcium stearate were added as a lubricant, be-ro? the mixing process began. 22.5 percent by weight polyethylene, ie the rest of polyethylene, the mixture was added gradually, which was boiled in the Banbury mixer at reflux until the temperature of about 127 ⁰ C (260 ⁰ F) to 132 ⁰ C (270 ⁰ F) had achieved. After the mass became uniform and dl · temperature was not controlled more than about 107 ° C (225 ⁰ F), were 2.51. Percent by weight /)j~<*.-eumylperoxide (90 Si active) added and incorporated into the mixture. The mixed mass was then taken out of the apparatus, cooled to room temperature, granulated into conventional catfish, placed in a conventional extruder and processed into insulation material for wires.

109810/2067 BAD original

Hit the finished mix was a solid copper conductor Ho.12 AWQ reconditioned; the wall thickness of the insulation material was

mm (1/32 inch); the finished product was cured in a niner steam (100 ⁰ P).

Chamber under ciroa 17.5 kg / era "(250 peig) pressure and 204 C

This product was made with two commercially available insulating .... compared the wires, hereinafter referred to as Norm A and Norm B; will. Norm A was a wire insulated with polyvinyl chloride; the wire was massive Head No. 12 AWQ, that of a 0.794 mn (1/32 inch) thick Isolation layer was surrounded. Norm B was a clay-filled networked Polyäthylenisdatlonsmatorial, also in 0.794 mm (1/32 inch) thickness around a solid conductor No. 12th AWQ had been splashed around. The composition of this insulation material is listed below:

Ingredient polyethylene Chlorinated polyethylene

Aluminum silicate (pretreated with Aluminum oleate)

Smoking lead glide (lead oxide) antimony oxide

Polyethyldihydroohinolln

(Antioxidant) CaIc1urnetoarat (lubricant) Thermal carbon black pigment dye di- * - oumyl peroxide (90% active)

109810/2067

Qewichtstelle " 25th 38 62 ü 50 3 10 5 ΐ < 1 0, 5,

512

Samples of the Kass® finders and the two H were tested. The. The test results listed in Table X include the superior »cutting strength, the ingenuity * Dimension © ο J & ä» SQhnlttlefsigkeit ie6 particularly important in applications where the wires are used in control devices and control devices * where the wires are used in wiring harnesses are bundled and di © tightly bound yarn dasu n @ ig n © _s Diss HCsolierwEig to

Lt
eresßi Table 1
1 ■ "IH.ι ι jMwrfci- rmm } $ ®η® & product Since nittfestkei
örgin & laußenduri after sr 3.8l mm C5JO mils) Penetrability 5 minutes lowering Q s 3556 mm (1 * 1 rails) U.Lo test with right flame foestestandη

3,683 fm 3 _{8 8 8} mm

Ci * 55 rails) (152

0.7112 mm 0.533 ¹ I mm (2Π alia) (21 mils}

passed passed

During the cut resistance test, © in wire was 0.1016 <* m (0.040 ineh) under the foot of a Randall-Stlokney measuring garate ^ placed. (This meter was used by the ASTM Thermal Deformat ion tests used). A weight of 2.2680 kg (5 pounds) was placed on top of the shaft of the device «

109810/2067

BATH ORIGINAL

After measurements of the outside of the wire brace to be tested, the probe was placed under the wire with 0.3.016 em CO ₃ OiJO ineh) Durehm © BS © r and at a right angle. After a five minute load of 2.2680 kg (5 pounds), the outside diameter was measured again. The difference in mm (mils) between the two determined outer diameter knives was referred to as the compressibility. A look at the data in Table I shows Λ Α & the Solmt ^ festlgkeit the © rflndtmgsgemäßen mass higher than di @ # © r two standards was. In this way, sufficient insulation is also guaranteed under ungüsxstägen ¥ © rdrahtungs ¥ s ^ hfiltniss @ n «

The vertical plane was carried out according to the regulations of the Underwriters' Laboratories "Standard for Safety, Thermoplastle-Xnsulated Wires" ¹ (safety standard for cables insulated with thermoplastic materials) UL 83, pages 17-19> 3 * edition 19 ^ 8. Correspondingly According to this test, an insulation material has satisfactory flame-retardant properties if it does not transmit a flame and does not continue to burn for more than a minute after 15 seconds of exposure to a standard test flame, which is applied at intervals of 15 seconds. The results of this test show that the invention Mm ··· dl · ·· had passed the exam.

109810/2067 _BAD ORIGINAL

Example 2

A grandmix was prepared as in Example 1. Then a first mixture was prepared from 10 parts by weight of base mud, 19.31 parts by weight of chlorinated polyethylene, 19.31 parts by weight of polyvinyl chloride, 13 parts by weight of basic lead silicate, 3.11 parts by weight of ONCOR-23 A, 0, 77 parts by weight of poly trima thy! Dihydroquinoline 0.25 weight points of carbon black and 14 weight points of polyethylene (only part of the total amount of polyethylene used). The mixture wunte t "w 5 Hinuten at einar temperature of etwü .J", 78 ⁰ C (325 ⁰ P) brought sun flow (fluxed). 6.57 parts by weight of basic lead silicate (the remaining stabilizer) and 0.71 parts by weight of calcium carbonate were added to this mixture nnl d @? Gasetst the process in progress. 12.95 weight polyethylene point were slowly added to the mixture in the Banburynischer added while the mixture (275 ⁰ F) was heated to flow about an additional 5 minutes at 135 ⁰ C. The temperature was then adjusted to not more than 107.22 ⁰ C (225 ⁰ P), and 2.57 weight parts Qi - ^ - cumylperoxyd (90% active) of the mixture were zugesetst "The mass thus obtained was then processed and 0.794 mm C1 / 32 inch) thickness applied to a solid conductor No, 12 AVG. It was subjected to the same tests as in Example 1 and excellent properties were also obtained. .

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BAD ORtGfNAL

Claims (1)

re mass, characterized by the fact that it consists of a polymeric mixture of polyvinyl chloride, ice thorn free * _Ä w *% i.i3rt: en polyolefin and 20 to 60 weight oprosentj, based on the total mixture of practically non-polar polyolefin a stabilizer for the chlorinated polymers and a curing agent, wherein the Gewichtsverhälfoids of chlorinated polyolefin to polyvinyl chloride in B 's eieh of 1: 3 to 3' 1. 2. Curable Maooe according to claim 1, characterized in that the stabilizer consists of basic lead silicate and is present in an amount of 5 to HO parts per 100 quarts of the polymeric mixture. 3. Curable composition according to claim 1 or 2, characterized in that the non-polar polyolefin is polyethylene. H ο hardenable mass according to one of claims 1 to 3, characterized in that the chlorinated polyolefin is chlorinated polyethylene. BAD ORIGINAL 109810/2067 ^ÖAU - ιβ - 5. Process for making a curable polymeric mixture from a practically non-polar polyolefin, a chlorinated polyolefin and polyvinyl chloride, characterized in that that So that a substantially uniform mixture is formed is 1 mixture) a mixture of the chlorinated polyolefin, the polyvinyl chloride and a portion of the non-polar polyolefin used in the blend as well as a stabilizer for chlorinated polymers to form a basic brought sun flow, 2.) The mixture thus obtained is added with further stabilizer and then the remaining non-polar polyolefin is gradually added to the mixture while the mixture is allowed to flow, so as to result in an intimate mixture and 3.) then a Härtemitjfcel is added to the intimately mixed mass thus obtained. 6. Electrical · cable, consisting of an electrical conductor and an insulating cover attached to the conductor, which consists of a material which has been produced by hardening the hardenable mass according to one of claims 1 to Ί . 109810/2067 bad ofi, _eiNA L