DE3007837A1 - FLAME-RESISTANT POLYMER MATERIAL AND PRODUCTS CONTAINING THEM - Google Patents

Description

DR.-ING. WALTER ABITZ DR, DIETER F. MORF DIPL.-PHYS. M. GRITSCHNEDER Munich,

February 29th 3

OK «t; iT> script / Postal Address Fofat compartment 86O1O9. 8OOO

~ Ί

Pienzenauerstrafle

Telephone SS 3222

Telegrams: Chemlndus Munich

Telex: {O} 523992

RK 96

Raychem Limited, London, England

Flame-retardant polymer mass and containing it Products

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3QP7837

The invention relates to new flame retardant polymers Compounds containing a vinyl ester copolymer in which at least some of the ester groups of the copolymer have at least three carbon atoms. The new masses of the invention show a low flammability, while they are characterized by a remarkable balance of physical properties.

In many technical applications of polymers, the requirements for non-flammability are becoming increasingly strict, especially in relation to the field of electrical insulation, e.g. in the case of wiring and cable sheaths, in cable harnesses, in the construction industry, e.g. in panel and cladding materials, and also in terms of dimensions recoverable, in particular heat recoverable products. As a result, a large number of became flame retardant acting agents developed for application in the polymeric materials normally used in such industries can be used. It is generally recognized, however, that even in the rare case that such polymeric materials can be given sufficient flame retardancy at the expense of other properties got to. For example, with regard to the release of corrosive and / or toxic gases, are under pyrolysis conditions high levels of organohalogen or organophosphorus flame retardants often unacceptable. In the case of inorganic flame retardants, many polymer materials cannot meet the high requirements Loads that are necessary for a satisfactory flame resistance, without significant disadvantages in terms of withstand their physical properties, e.g. tensile strength or elongation at break.

030037/0774

The invention is based on the finding that a certain A class of polymers that have not previously been used in applications where flame retardancy problems arose offer an exceptionally high degree of flexibility, wunn they together with Fl ακαπναχ hesitate rn to be applied, and able to meet the stringent flame resistance requirements while maintaining a satisfactory balance of physical Show properties. Such a flame retardancy indicates the standard flammability test, e.g. according to ASTMD-2 86 3, even at temperatures as high as 300 ° C or above.

According to the invention, a polymer made flame-retardant

or cross-linked mass proposed, dxe a non-cross-linked, unsubstituted

ated or substituted vinyl ester copolymer, of which at least some of the ester groups of the polymer contain at least three carbon atoms, and therein incorporating an effective amount of a flame retardant, with the proviso that - when the composition is not crosslinked - every copolymer of vinyl propionate with ethylene contains more than 20 mol% vinyl propionate.

The term "copolymer" used here is used in the broadest sense and refers to any polymer which at least contains two different monomer species; he closes Terpolymer seeds and the like.

Many of the vinyl ester copolymers within the scope of the invention are not commercially available. They can be produced in a manner known per se, e.g. from im Commercially available vinyl ester copolymers by ester

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exchange, for example in US-PSS 2,558,547 and 2 558 548 Loschriobon.

The vinyl monomers of interest in the inventions copolymers used are those of the formula I,

Il

in each of which, independently of one another, R ₁ , R- and R-. Hydrogen or a substituted or unsubstituted Cj-C - ^ - hydrocarbon, for example C .. -C, alkyl, and R. is a substituted or unsubstituted C ^ -CQ hydrocarbon, where in particular R ₁ , R "and R _n , are each independently hydrogen or C ^ -CG alkyl, and a group or all of the radicals R, R 'and R ₃ also can mean phenyl or benzyl, and R is a C' -C ~ _n alkyl, alkenyl, alkoxyalkyl or alkoxyalkenyl , Aryl or aralkyl, for example phenyl, naphthyl or benzyl, or C ₁ -C.-alkyl- or -alkoxyphenyl or -benzyl, and in particular when R. is a C ^ -C ₁₇ -, preferably C ^ -C ₁ ^ -Alkyl, or phenyl or benzyl.

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Π "ispiele for VinylosLer-Monoraere of interest in the copolymers of the invention are sowed vinyl propionate, vinyl hexanoate, vinyl versatate, vinyl stearate, vinyl laurate, vinylmethoxy, vinyl trimethylacetate, vinyl isobutyrate, vinyl tert.pentoat, vinyl lactate, vinyl caprylate _r Vinylpelargonat, vinyl myristate, vinyl oleate, Vinyllinoleat, Vinyl benzoate, vinyl (Cj-C ₄ ) alkoxybenzoate, vinyl octyl phthalate, vinyl β-phenyl butyrate, vinyl β-naphthoate, vinyl ethyl phthalate and vinyl phenyl acetate Literature reference to be disclosed.

Vinyl ester copolymers of interest include mixed vinyl ester copolymers, for example copolymers of vinyl esters containing at least three ester carbon atoms with vinyl acetate or higher vinyl esters, as well as copolymers with comonomers other than vinyl esters. Such other comonomers include unsaturated hydrocarbons, such as olefins, e.g. ethylene, propylene and C ₄ -C ₁₂ oC-unsaturated olefins, such as but-1-en and oct-1-en, styrene, other unsubstituted or substituted esters than vinyl esters, e.g. C ₄ -C ₁ _- (meth) acrylates, and other vinyl monomers, for example vinyl chloride.

030037/0774

When copolymers with other coinonate than vinyl star with at least 3 ester carbon atoms are used, then the vinyl ester monomer (s) is (are) preferably at least 5 mol%, more preferably at least 1o mol%, e.g. 2o - 95 mol%, and especially preferably with at least 3o mol% j e.g. 4o - 95 mol%.

In addition, the vinyl ester copolymer can be used as a blend system containing other polymers. Blend polymers of interest are those which are preferably compatible with the vinyl ester polymer, either alone or together with the compatibilizers, and which do not render the compositions unsuitable for the intended purposes. Such polymers include thermoplastic and elastomeric polymers; Examples of these are polyesters, including block copolyesters of the type available from DuPont under the name Hytrel and in Polymer Engineering and Science 1_4, Vol. 12, pp. 849-852, 1974, in
the article "Segmented Polyether Ester Copolymers - a New Generation of High Performance Elastomers"
will; Polyolefins, eg branched low density polyethylene "" On, linear low density polyethylene
(e.g. that in CA-PS 873 828 and GB patent application
7 911 916 described polyethylene) and linear high-density polyethylene, silicone resins and elastomers, (meth) acrylate homopolymers or copolymers, for example terpolymers of ethylene, methyl acrylate and a curable
Carboxy1-containing monomers, such as the terpolymer available commercially from DuPont under the name "Vamac", and analogous polymers which are described in GB-PS 1 5 48 2 32; Ethylene / vinyl acetate copolymers, EPDM
(linear terpolymer based on ethylene, propylene, diene monomer), SBR (styrene / butadiene rubber) and block copolymers made from styrene with butadiene or isoprene.

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If blonds are used then this is vinyl ester polymer preferably in a blend with at least 2o wt .-%, e.g. 3o - 9 9 wt .-%, more preferably with at least 4o wt .-%, e.g. 50-99% by weight.

It is noted here that the compositions of the invention can expediently contain a coupling agent to improve the compatibility of the flame retardant with the polymer in order to improve the physical properties of the masses, especially if inorganic Fillers can be used as flame retardants. To preferred Couplers include organic silicon and titanium derivatives, such as silanes and titanates, although in some cases Processing aids such as stearic acid and stearates, aluminum soaps such as aluminum diisopropoxy diversatate or polyoxocarboxylates, such as polyoxoaluminum stearate, may be particularly suitable.

Examples of silanes that can be mentioned are: dimethyldichlorosilane, Methyltrichlorosilane, vinyltrichlorosilane, Y-methacryloxypropyl-trimethoxysilane, Ν, Ν-bis (ß-hydroxyethyl) -y-aminopropyl-triethoxysilane, X-methacryloxypropyI-trimethoxysilane, Y'-mercaptopropyl-trimethoxysilane, vinyltrimethoxysilane, X-glycidoxypropyl-triinethojjsilan and Vinyl trimethoxyethoxysilane. Further suitable silanes are mentioned by way of example in GB-PS 1 2 84 o82.

Examples of titanates and other organotitanium derivatives that are "suitable as couplers are: Tetraisoocty! Titanate, isopropyl diisostearyl methacrylic titanate, Isopropyl triisostearoyl titanate, isopropyl triacryl titanate, and titanium di (dioctyl pyrophosphate).

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Additional suitable titanium compounds are described in S.J. Monte & G. Sugerman, J. Elastomers & Plastics / Vol. 8 (1976), pp. 3o-49, and in Bulletin KR o376-4 and Ο278-7 "Ken-React Titanate Coupling Agents for Filled Polymers" published by Kenrich Petrochem Inc.

Examples of aluminum soaps and polyoxoaluminum carboxylates are given in GB-PS 825,878.

The weight ratio of coupler or processing aid / if used to flame retardant is preferred in the range of o, oo5: 1 to o, 1: 1, more preferably o, o1: 1 to o, o5: 1.

Flame retardants such as organohalogen, organophosphorus or Boron compounds or inorganic flame retardant fillers can be used. The preferred flame retardants However, the halogen and phosphorus-free compounds are in particular inorganic fillers, such as metallic oxides, e.g. antimony trioxide, tin (IV) oxide and molybdenum trioxide, as well as Fillers that release water when heated. Of particular interest are the inorganic fillers used in Heat release water, especially hydrated aluminum oxides such as Al "O ^ .3H" O, ammonium or sodium dawsonite, hydrated magnesia, hydrated calcium carbonate and hydrated calcium silicate, especially ct-alumina trihydrates.

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030037 / 077A

The use of a blend retarder different particle sizes can be advantageous, for example to reduce the melt viscosity of the Dimensions.

If necessary, the flame retardant can be treated chemically to improve its compatibility with the polymeric material, for example by treatment with one of the coupling agents mentioned above, or in the case of hydrated inorganic flame retardants, such as alumina trihydrate, with a processing aid such as stearic acid or stearates, e.g. calcium stearate.

The flame retardant is preferably used in an amount by weight of 10 to 400 parts per 100 parts of polymer, more preferred 50 to 200 parts per 100 parts of polymers are used. Notable results are when using a lot from 80 to 150 parts by weight of flame retardant per 100 parts Polymer.

In addition to the flame retardant, the inventive Masses of other additives, for example fillers, stabilizers, such as ultraviolet stabilizers, antioxidants, Acid acceptors and antihydrolysis stabilizers, foaming agents and colorants and processing aids such as Contain plasticizers.

It is preferred that the compositions contain less than 5% by weight of halogen or phosphorus in the composition as a whole and more preferably contain less than 2% by weight halogen or phosphorus; they preferably contain no halogen and no phosphorus.

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030037/0774

AS

For most purposes it is preferred that the invention Masses are essentially networked.

The degree of crosslinking of the masses can be determined with the help of the gel content (ANSI / ASTM D2765-68) of the crosslinked polymer mass, i.e. excluding any existing non-polymeric additives. The gel content of the crosslinked mass is preferably at least 10%, more preferably at least 2o%, e.g. at least 3o% and most preferably at least 4o%.

The compositions of the invention are made in a conventional manner produced, for example, by homogeneously mixing together the components of the mass in a Banbury mixer.

They can then be formed into shaped objects, for example by extrusion or molding, and optionally be networked simultaneously or subsequently. Molded articles produced in this way also form part of the present invention.

The polymeric components of the composition can be prepared either by incorporating a crosslinking agent or by acting be networked by high-energy radiation. Suitable crosslinking agents are free radical initiators, such as Peroxides, for example dicumyl peroxide, 2,5-bis (t ^ -butylperoxy) -2, 5-dimethylhexane, 2,5-bis (t-butylperoxy) -2,5-dimethylhexyne-3 and oi, oc-bis (t_-butylperoxy) diisopropylbenzene. Other examples For suitable crosslinking agents, see C.S. Sheppard and V.R. Kamath, Polymer Engineering and ScifVgce IjJ./ No. 9, 597-606, 1979; mentioned in the article "The Selection and Use of Free Radical Initiators"; they are going through here Reference disclosed. In a typical chemical

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crosslinkable mass are about 0.5 to 5 wt .-% crosslinking agent, based on the weight of the polymer blend. The crosslinking agent can be used alone or in conjunction with a co-curing agent such as a polyfunctional one Vinyl or allyl compound, e.g. triallyl cyanurate, triallyl isocyanurate or pentaerythritol tetramethacrylate can be used.

Radiation crosslinking can be carried out by exposure to high-energy radiation such as an electron beam or ^ rays. Radiation doses in the range of 2 to 8o Mrad, preferably 2 to 50 Mrad, e.g. 2 to 2o Mrad and especially 4 to 12 Mrads, are generally useful.

For the purpose of promoting networking during irradiation are preferably o, 2 to 5 percent by weight of a Prorad component, such as a polyfunctional vinyl or allyl compound, for example triallyl cyanurate, triallyl isocyanurate or pentyerythritol tetramethacrylate incorporated in the mass before irradiation.

The compositions according to the invention in uncrosslinked form which incorporate an effective amount of a crosslinking agent or a Prorad component also form part of the present invention. In such a form , the compositions can also be used as adhesives or adhesives.

The compositions of the invention are particularly suitable for electrical insulation applications where the flammability requirements are strict, for example in limited

RK96

Areas, such as in airplanes, ships, pits, or subways .

The manufacture of electrical insulating material can done by means of conventional techniques, for example by extrusion of the non-crosslinked mass as an insulator on a electrical device, such as a copper conductor as primary insulation or a bundle of primarily insulated Copper wires as cable sheath, and simultaneous or subsequent networking of the applied insulation. Alternatively the material can be extruded and crosslinked separately and then used as an insulating filler in a cable construction will.

The compositions of the invention are also suitable for use as laminating and panel materials, as well as fire blocks, for example for cable entries, particularly the sector of transportation of persons, for example in airplanes, trains and ships _f for oil towers and in the construction industry. For such applications, the materials can be used in any desired shape, such as that produced by thermoforming.

The compositions of the invention are also particularly useful in crosslinked form for making dimensionally recoverable Articles, i.e. articles, the dimensional configuration can be changed significantly if they are one appropriate treatment. Of particular interest are heat retrievable articles, the dimensional configuration of which can be substantially changed if they are be subjected to a heat treatment. Heat recoverable products can be made by deforming a dimensionally heat-stable configuration to a heat-unstable con-

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figuration, in which case the object has a tendency to assume the original heat-stable configuration with the sole application of heat. However, as disclosed in U.S. Patent No. 2,027,962, the original dimensionally thermostable configuration may be a transitional shape in an ongoing process in which, for example, an extruded tube is expanded while hot to a dimensionally thermally unstable shape. Alternatively, a preformed dimensionally thermally stable article can be deformed into a dimensionally thermally unstable shape in a separate step. In the manufacture of dimensionally recoverable objects, the mass can be crosslinked at any stage of the manufacturing process, which imparts the desired dimensional recoverability, following the shaping of the dimensionally unstable configuration. One production method for a heat-recoverable object comprises shaping the pre-crosslinked mass to the desired heat-stable shape, subsequent crosslinking of the mass, heating the object to a temperature above the crystalline melting point or, in the case of amorphous materials, the softening point, as can be the case with the polymer . Deforming the object and cooling the object while it is in the deformed state so that the deformed shape of the object is maintained. In Gebraucn ^EWiR application of heat, since the deformed state of the article is heat unstable, that the article to assume its original heat-stable shape. Such dimensionally recoverable objects can be used to cover and / or seal splices and endpoints in electrical conductors, for the surrounding sealing of damaged areas or connections in public supply systems, e.g. in gas or water pipes, district heating and heating systems, ventilation and agitation lines and plumbing lines or pipes that lead Abrats out of the house or industrial sector. Such items can be in the form of

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Tapes, foils or sheets, sleeves or castings are present. In addition, and under certain circumstances, it may be desired be at least a portion of the surface of the heat retrievable object with a sealant or adhesive to be coated, e.g. a heat-activatable pressure-sensitive or contact hot-cut adhesive or a Putty, in particular with a hot melt adhesive, as described in DE-OS 2 723 116, which is here by reference is revealed.

For heat-recoverable applications, it is preferred that the composition contains a blend of the vinyl ester copolymer with at least one thermoplastic polymer. The weight ratio of vinyl ester copolymer to thermoplastic polymer can, for example, be in the range from 1: 0.2 to 4, for example 1: 0.2 to 1.5, preferably 1: 0.2 to 0.55. Preferred thermoplastic blend polymers for heat recoverable applications are thermoplastic alkene homopolymers and copolymers. Polyalkene homopolymers are preferably derived from a C1-C4 alkene, in particular an α-unsaturated alkene such as ethylene, 1-propylene and 1-butene, and in particular ethylene. Polyalkene copolymers are preferably C ₂ -C _ß alkene / C "to C ₁₂ alkene copolymers, particularly ethylene copolymers with C ^ -C- ~ ₂ alkenes, especially oQ-unsaturated C ₃ -C _1" alkenes such as n -Propyl-1-en, n-but-1-en, n-pent-1-en and n-hex-1-en, and vinyl alkene esters, for example ethylene / vinyl acetate copolymers. Particularly preferred ethylene copolymers contain more than 50% by weight, for example more than 60% by weight, more preferably more than 70% by weight, for example more than 85% by weight, ethylene. Of particular interest are the so-called linear ethylene copolymers of low density with a density in the range from 0.910 to 0.94 g / cm at 25 ° C., which are described in GB patent application 7,911,916 and CA-PS 873 828 and here are incorporated by reference.

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030037 / 077A

The invention is illustrated by the following examples, in which parts and percentages are based on weight, unless otherwise stated. Temperatures are given in ° C.

Examples 1 to 9

The compositions given in the following examples were heated to a temperature of 12o - 14o ° C on a two-roll laboratory grinder, cast into test plates at 19o C and irradiated with a 5.8 MeV electron beam up to a total dose of 6 Mrad Oxygen Index = LOI) was measured according to the ASTM D-2863 method; In addition, the Limiting Oxygen Indices and Critical Temperature Indices were obtained by the AF Routley method (ERA. Symposium "Flammability and Smoke Testing Materials", London 1974), the details of which were obtained from JP Redfern (Technical Information Sheet No. 24 "Critical Oxygen Index in Temperature Studies "available from Stanton Redcroft, a division ₍ of L. Oerting Ltd.) _;

example 1

The composition, produced from equal weights of a copolymer of vinyl versatate ^X (25%) and vinyl acetate (75%), hereinafter referred to as W / VA, and alumina trihydrate (ALTH), showed the following oxygen index values at the specified test temperatures. The alumina trihydrate is known as Hydral 705 (Alcoa Corporation) and has been silane-coated with 1.5% vinyltrimethoxyethoxysilane.

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030037/0774

Temperature, ° C

23 3oo 34α 37o

LQI

58.5 25, ο 19.5 16, ο

Vinyl versatate is the vinyl ester of Versatic acid,
a mixture of C _q , C. ..- acids available from Shell Ltd.)

By extrapolating these results, the critical temperature index (CTI) , the temperature at which LOI equals 20, B%, was determined to be 335 ° C.

Example 2

A composition analogous to that of Example 1 was
but the percentage ratio of W / VA was 40% in this example. The following flammability was found: ■

Temperature, ⁰ C

23 3oo 34o 37o

CTI = 36o

LOI

29.5 23.5 2o, o

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Example 3

A VV / VA, silane-coated alumina trihydrate and Hytrel

Compound 4056 (a polyester resin from DuPont) / was prepared. That

Weight ratio of the components was accordingly 36, 6o and 4%. It showed an LGI value of 78, ο at 23 C.

Example 4

A composition similar to that of Example 3 was made. The weight ratio of the components was W / VA = 32%, Hytrel 4056 = 8% and silane treated ALTH = 6o%. It showed a LOI value of 73, ο at 23 C.

Example 5

A mass was produced similar to that of Example 4 with the following components: W / VA = 28%, Hytrel 4056 = 12% and silane-treated ALTH = ßo %. It showed an LOI of 70.0 at 23 ° C.

Example 6

A mass which contained 50% W / VA and 50% hydrated magnesia was produced in a manner analogous to that in Example 1. It showed an LOI value of 31.5 at 23 ° C.

Example 7

A composition containing 50% W / VA, 25% hydrated magnesia and 25% ALTH was prepared in a manner analogous to that in Example 1 manufactured. It showed an LOI value of 38.5 at 23 ° C.

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Example 8

A composition containing 50% W / VA, 33% ALTH and T7% ^: Firebrake (zinc borate from USBorax Corp.) was prepared. It showed a LOI of 41, ο at 23 C.

Example 9

For comparison, a sample made from W / VA alone was made and tested. It showed a LOI of 2o> 5 at 23 ° C; '■. ■

Examples 1o to

In a manner analogous to that described above, the compositions given in Tables I, II and III below were produced and subjected to the LOI test. The following abbreviations are used in the tables:
1

W / VA * ¹

Silicone elastomer

Silicone resin

a copolymer of 25%, vinyl versatate (see above) _i and 75% vinyl acetate

a copolymer of 78% vinyl versatate / 22% vinyl acetate

a copolymer of 5o% vinyl laurate / 5o% vinyl acetate

a linear low density polyethylene, Sclair 11-D-l from DuPont

a branched low density polyethylene, DYNH-3 from Union Carbide Corporation

a commercially available polydimethylsiloxane rubber, which contains 25% silica reinforcing filler

a thermoplastic monoorganopolysiloxane prepared according to the method of Example 3 of FR patent application 7,822,138 by

Hydrolyze 166.4 moles of phenyltrichlorosiloxane and 93.7 moles of methyltrichlorosilane

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Continued

Al O ₃ .3H ₂ O silane coated

VA / VV / E

VA / E
Hytrel

VA / VPA / E VA / VPA / E '

VA / VP / E

VA / VS / E VA / VS / E VA / VB / E VA / VH / E VA / VL / E VPA / E

and end-capping with 9.2 moles of trimethylchlorosilane. The resin obtained has a TMA softening point of 119 ° C

a linear terpolymer based on Ethylene, propylene, diene monomer available from Exxon Corp. under the name Vistalon 37o4

Alumina trihydrate, coated with 1.5% of the same with trimethoxyethoxysilane

a terpolymer of 85% vinyl acetate / 10% vinyl versatate / 5% ethylene

a copolymer of 6o% vinyl acetate / 4o% ethylene

a thermoplastic elastomeric polyester derived from dimethyl terephthalate, a Polyglycol and a short chain diol available from DuPont, Grade 4056

a terpolymer made of 19 mol% vinyl acetate /

14 mol% vinylphenyl acetate / 6 7 mol% ethylene

a terpolymer made of 4 mol% vinyl acetate /

7.3 mol% vinylphenyl acetate, 88.7 mol% ethylene

a terpolymer made of 25 mol% vinyl acetate / 8 mole percent vinyl palmitate / 67 mole percent ethylene

a terpolymer of 3 mol% vinyl acetate /

15 mole percent vinyl stearate / 82 mole percent ethylene

a terpolymer of 2.7 mol% vinyl acetate / 8.6 mol% vinyl stearate / 88.7 mol% ethylene

a terpolymer of 2.7 mol% vinyl acetate / 8.6 mol% vinyl benzoate / 88.7 mol% ethylene

a terpolymer of 4.7 mol% vinyl acetate / 6.6 mol% vinyl hexanoate / 88.7 mol% ethylene

a terpolymer made of 1.9 mol% vinyl acetate /

9.4 mol% vinyl laurate / 88.7 mol% ethylene

Copolymer of 18 mol% vinylphenyl acetate / 82 mol% ethylene

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Components TABEL I. 10 Π 12th 13th 14th 15th 16 17th 18th 19th 20th 21 22nd 23 24 25th 26th I. 30th r W / VA ¹ 74.5 74.5 74.5 75 75 75 75 74.5 36 32 28 20th 10 r
C ""
30th VV / VA ² 40 10 VL / VA 75 70 65 10 LLQPE 15th 15th 15th BLDPE ¹ SILICONE ELASTOMER 117 C.
Approx ι SILICONE RESIN 4th 8th 12th 20th C.
C. j FPDM · ■ 5 10 ** i
«Ml \ Al ₄ O ₃ . 3H ₂ O Examples, no. 60 60 60 60 AlJ ₁ O ^ 3Hρ0
SILANE -coated. 37 37 37 74.5 60 210 210 210 6th Al ₂ O ₃ . H ₂ O 74.5 37 37 61.5
I. 6th ! Ig (OH) ₂ 70.0 37. 37 71.1 Cc (OH) ₂ 74.5 37 FLECTRON BEAM
DOS. Mrad 6th 6th 6th 6th 7.5 7.5 7.5 7.5 6th 6th 6th 6th 12th 12th 12th 12th LOI 9 23 ° 31.6 25.6 22.1 29.6 32.0 30.0 28.5 34.0 69 93 94 94 33 65.5 61.5 63.5

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CD CO

-4

28 29 30th 31 • 210 32 example 34 No. 36 37 38 39 40 i 24 36 41 {
1
II IM «' j 240 Components 10 12th 33 ¹ 35 96 84 108 96 84 j « i !
I · 12 i
Ϊ W / VA ¹ 30th 30th 70 60 72.5 45 50 108 I.
I. ^:
I. I.
42.5
> VL / VA 50 180 j
! VA / VV / E 30th 45 15th 180 130 Π 60 VA / E 25th 12th ^[ HYTREL 15th 15th β! 8th LLDPE 20th 10 15th 24 36 72.9 68.5 SILICONE ELASTOMER 5 12th EPDM 180 180 180 Al ₂ O ₃ . 3H ₂ O 157 155 210 210 210 180 180 Al ₂ O ₃ . 3H ₂ O
SILAN-coated 6th 6th 12th 12th 210 . 12th 8th 8th 8th 12th ELECTRON BEAM
DOS .Mrads 97.0 99.7 70.0 60.5 12th 87.5 8th 81.5 88.7
< 77.9 31.0
1 LOI (3 23 ° 75.5 99.7

"S.

co

\ CD O -J

CX)

co

co O O approx

to

Components Example no. 43 44 45 46 · ■ - 47 48 ' 49 50 51 52 53 - 60 VA / VPA / E ¹ 40 30th 60 12th VA / VPA / E ² 40 12th 27.0 VA / VP / E 40 34.5 30th VA / VS / E ¹ 40 VA / VS / E ² 40 VA / VB / E 40 VA / VH / E 40 VA / VL / E 40 V PA / E 40 Al ₂ O ₃ . 3H ₂ O 60 60 70 70 60 60 60 60 60 ELECTRON BEAM
DOS Mrads 12th 12th 12th 12th 12th 12th 12th 12th 12th LOI β 23 ° 35.0 29.0 49.0 49.5 25.5
i 28.5 29.0 26.6
I. 28.1

(D I- "µ-j (D

M M H

In the above examples, LOI values are in the range

from 25 to 35, accompanied by a remarkable balance of physical properties, measured for example based on the tensile strength (MPa) and elongation at break (%) at 23 ° C (according to BS9o3 part A2). Such properties make such materials for heat retrievable applications or for processing by thermoforming techniques suitable for, for example, lamination and cladding. In the previous examples where higher LOI values were obtained e.g. greater than 35, and depending on the particular application, it is desirable to balance the physical Change properties; this can be achieved by changing the filler content and / or blending with one suitable polymers, while still achieving high LOI values.

Examples 5 4 to 5 7

In a manner analogous to that described above, the compositions given in Tab. IV were prepared and the LOI test and subjected to physical property test. In the The following abbreviations are used in tables. Further abbreviations are already earlier in Examples 1o to 53 has been defined.

VA / VH / E ... a terpolymer made of 28 mol% vinyl acetate /

5 mole percent vinyl hexanoate / 67 mole percent ethylene

VA / VS / E ... terpolymer made of 27 mol% vinyl acetate /

6 mole percent vinyl stearate / 67 mole percent ethylene

VA / VH ... copolymer of 78 mol% vinyl hexanoate /

22 mole percent vinyl acetate

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Table IV

Components 54 /
/ 56 57 VA / VH / E ² 32 55 VA / VS / E ³ 40 40 VA / VH 24 Al ₂ O ₃ . 3H ₂ O
Silane-coated 68 60 60 Silicone elastomer 60 16 Electron beam
DOS. (Mrad) 12th 12th 12th LOI β 23 ⁰ C 54.5 12th 36.2 60.2 Tensile strength (MPa)
@ 23 "C (via BS7O3
part A2) 11.1 38.0 6.36 - % Elongation at break
Ρ 23 ° (via BS703
part A2) 63 • - 86 - -

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^5a 3007S37

Be i_s_g i_e 1 58

Example 1 is repeated, the following copolymers being used in each case instead of the VVE / VA.

(a) vinyl laurate (4o%) / vinyl acetate (6o%)

(b) vinyl stearate (4o%) / vinyl acetate (6o%)

(c) vinyl versatate (4o%) / vinyl acetate (6o%)

(d) vinyl benzoate (4o%) / vinyl acetate (6o%)

(e) vinyl propionate (4o%) / vinyl acetate (6o%)

(f) vinyl versatate (4o%) / vinyl propionate (6o%)

(g) vinyl stearate (4o%) / vinyl propionate (6o%) (h) vinyl benzoate (4o%) / vinyl propionate (6o%)

(i) ethylene (59%) / vinyl acetate (7%) / vinylphenyl acetate (34%) (j) ethylene (56%) / vinyl acetate (11%) / vinyl laurate (33%) (k) ethylene (69%) / vinyl acetate (13%) / vinyl propionate (18%)

Substantial flame retardancy was observed in each case.

Example 59

To illustrate the ability of the polymer systems of the invention to handle high loadings of inorganic fillers a VA / VL copolymer (see above) loaded with 80% silane-coated alumina trihydrate (see above) and crosslinked in a manner analogous to that in Example 1. The obtained material showed the following LOI values at different temperatures while being acceptable Showed balance of physical properties

- 29 -

030037/0774

RK96

3-f

temperature LOI 23 °
250 °
300 °
410 ° 1OO
100
88
45

Examples 6o - 65

Heat shrinkable tapes were made from those given in Tab Approaches generated. The following abbreviations are used in the table; other abbreviations are in the above examples have been defined:

BLDPE EVA

Al ₃ O ₃ .3H ₂ O ..
Stearic acid

a branched low density "polyethylene" available from BXL Limited under the designation PN22o

an ethylene / vinyl acetate copolymer with 18% vinyl acetate

Tgnerde trihydrate,, available, as Hydral 705 from Alcoa Corp. and with 2% stearic acid

overdrawn *

The ingredients of each formulation were placed in a twin roll grinder compounded at 12o to 14o C, cooled and pelletized. The pellets thus produced were put into a conventional Extruder filler given with a tape injection mold, held at 14o C, and made into a tape of 6 mm Width and 2 mm thickness extruded «The tape obtained was subsequently with high-energy electrons up to one Total dose of 8 Mrad irradiated. After irradiation, the tape was kept at 14o C, stretched lengthways, to double its original length, and allowed to cool in this stretched state. After that, that became

- 30 -

130037/0774

007837

Tape with a thin layer (ο.5mm) of hot melt adhesive the composition according to DE-OS 2 723 116, example 3, formulation "0", coated. The physical properties and LOI values of the tapes obtained are given in Tab specified.

The heat shrinkable, adhesive-coated tapes were made used to supply metal air conditioning lines to the 150 mm diameter joints seal, with the line preheated in the area of the connection, the respective band around the line over the Connection region was wound so that successive turns of a respective tape partially overlapped, and the respective tape was heated to a temperature of 145 C with a conventional propane gas torch, whereby a melting of the adhesive occurred and the respective tape shrunk tightly around the joint and a strong one Adhesive tape formed between the respective tape and the line.

- 31 -

Θ30037 / 077Α

3003 * 5 37

Table V

Components For example no. 60 61 62. j 63 90 64 65 120 VL / VA 20th 30th 60 30 j 160 BLDPE ² 10 10 30th I. 366 UAE 20th 10 60 40 I. 350 EVA 40 40 5.8 VA / VH / E ² 160 120 1.5 Al ₂ O ₃ . 3H ₂ O
Stean'ns.äuxe-
.'overdrawn 50 50 160 400 ' 160 0.8 % Elongation at
Break @ 23 ⁰ C 320 340 _400 7400 518 27.0 y § 150 ⁰ C 400 400 400 4.1 400 tensile strenght
(MPa) @ 23 ^U C 3.2 2.3 6.4 0.8 8.3 © 150 ⁰ C 0.9 0.6 0.9 0.35 1.7 100% tangent
Module -Gl 50 ⁰ C
(MPa) 0.4 0.2 0.50 31.5 0.85 LOI 29.5 _n 29.5 30.5 26.0

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630037/0774

RK9 6

Example 66

Components

Parts by weight

LLDPE

UAE

VL / VA

AI2O3. 3H, 0 Silane-coated

50 50 50

150

The above formulation was compounded in a Banbury type internal mixer at a temperature of about 125 ° C. After compounding, the material was processed into a strip on a twin roll grinder, cooled, cut into pellets and lightly talcum coated to prevent the pellets from blocking. The material was then called Cable sheath extruded onto a multi-core cable with an outer diameter of 22.5 mm to form a sheath with a wall thickness 1.2mm using a 8.89cm extruder with a 25.1 L / D ratio screw, at barrel temperatures of 60, 80, Ho, 12o and 13o C and an extruder die temperature profile of 15o, 14o and 1Zo C. The jacketed cable was then irradiated with energetic electrons up to a total dose of 8 Mrad. The coated material had the following properties:

% Elongation at 23 C Tensile Strength (MPa) at 23 C LOI at 23 ° C
CTI

I00 8

31 .5 25o ⁶ C

- 33 -

Θ30037 / 0774

Claims (27)

Claims 1. Flame-retardant polymer composition containing a non-crosslinked and / or crosslinked unsubstituted and / or substituted vinyl ester copolymer with an incorporated effective amount of a flame retardant, wherein at least some of the ester groups of the polymer contain at least three carbon atoms, with the proviso that a non-crosslinked mass a Copolymer of vinyl propionate with ethylene contains more than 2g mol% of vinyl propionate. 2. Composition according to claim 1, wherein the vinyl ester copolymer vinyl ester monomer units of the Formula I ". ^k O - C - contains, in each of which, independently of one another, R .., Rj and R ^ are hydrogen or a substituted or unsubstituted C .- (^ -.- hydrocarbon and R is a substituted or unsubstituted C ₂ -C ₂ _ -hydrocarbon. 3. Composition according to claim 2 _r wherein each un depending on one another, R or C ₁ -C ₆ -AUCyI. R ₂ and R _{3 of} the formula I are hydrogen 0SÖ037 / Ö774 RK96 / j 4. Composition according to claim 3, wherein R-, R ".and R _{3 of} the formula I is in each case hydrogen. 5. mass according to one of claims 2 to 4, where R- the formula IC _? -C “alkyl, alkenyl, alkoxyalkyl or alkoxyalkenyl, aryl, aralkyl or aryl or aralkyl substituted by C, -C -alkyl or -alkoxy. 6. The composition of claim 5, wherein R, the Formula IC _? -C- “alkyl, alkenyl, alkoxyalkyl or alkoxyalkenyl, phenyl, naphthyl, benzyl or with C ₁ . -C.-Alkyl or -alkoxy is substituted phenyl, naplithyl or benzyl. 7. Composition according to claim 6, wherein R. of the formula I Is C ₃ -C ₁₇ alkyl, phenyl or benzyl. 8. mass according to one of claims 1 to 7, wherein the vinyl ester polymer is a copolymer of a vinyl ester as defined with another ester and / or an unsaturated hydrocarbon. 9. Composition according to claim 8, wherein the vinyl ester polymer is a copolymer of a vinyl ester as defined with another vinyl ester whose ester group contains at least two carbon atoms, a C ₃ -C ₁₂ olefin and / or a C ₄ -C ₁₂ (meth) is acrylate. 030037/0774 RK96 & 10. The composition of claim 9, wherein the vinyl ester polymer a copolymer of a vinyl ester is by definition with vinyl acetate and / or ethylene. 11. Composition according to one of the preceding claims 1 to 1O, in which the vinyl ester copolymer is at least 5 mol% of a vinyl ester monomer having at least three ester carbons contains atoms. 12. The composition of claim 11, wherein the vinyl ester copolymer contains 10 to 95 mol% of a vinyl ester monomer having at least three ester carbon atoms. 13. Composition according to one of the preceding claims / from a blend of the vinyl ester copolymer with at least one other polymer. 14. Composition according to claim 13, wherein the blend polymer is a polyethylene, polyester, silicone resin or elastomer, (meth) acrylate homopolymer or copolymer, ethylene / vinyl acetate copolymer, EPDM (ethylene-propylene terpolymer) or SBR (styrene-butadiene Rubber). 15. Composition according to one of claims 13 or 14, with at least 2O wt .-% of the vinyl ester copolymer in the blend. 030037/0774 RK96 ψ 16. Composition according to one of the preceding claims, characterized in that it is in a substantially crosslinked form. 17. The composition of claim 16, having a gel content according to ANSI / ASTM D2765-68 of at least 10% 18. Composition according to one of the preceding claims, wherein the flame retardant is an inorganic flame retardant making agent is. 19. The composition of claim 18, wherein the inorganic flame retardant is hydrated. 20. The mass of claim 19, wherein the hydra- tized inorganic flame retardant alumina trihydrate contains. 21. Composition according to one of the preceding claims, with 10 to 400 parts of flame retardant per 100 parts of the Polymers. 22. Composition according to one of the preceding claims, with a content of halogen or phosphorus less than
Makes up 5% by weight. 030037/0774 RK96 23. Flame-retardant electrical insulation off a mass according to any one of the preceding claims. 24. Wiring or cables with electrical insulation according to claim 23. 25. Flame retardant, recoverable in the warmth Product made from a mass according to one of Claims 1 to 22, in crosslinked and heat-recoverable form. 26. Product according to claim 25 in the form of extruded tapes, foils or sleeves or a molded one Hollow part. 27. Product according to one of claims 25 or 26 containing a thermoplastic polymer. 28 * Product according to claim 27, wherein the thermoplastic polymers an ethylene homopolymer or copolymer. 030037/0774