GB1588485A - Polymeric compositions containing brominated flame retardants - Google Patents

Polymeric compositions containing brominated flame retardants Download PDF

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Publication number
GB1588485A
GB1588485A GB24964/78A GB2496478A GB1588485A GB 1588485 A GB1588485 A GB 1588485A GB 24964/78 A GB24964/78 A GB 24964/78A GB 2496478 A GB2496478 A GB 2496478A GB 1588485 A GB1588485 A GB 1588485A
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composition
weight
flame retardant
peroxide
cross
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GB24964/78A
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Raychem Corp
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Raychem Corp
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Priority claimed from US05/828,731 external-priority patent/US4129616A/en
Application filed by Raychem Corp filed Critical Raychem Corp
Publication of GB1588485A publication Critical patent/GB1588485A/en
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F255/00Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • C08F255/02Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/01Hydrocarbons
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/02Halogenated hydrocarbons
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/04Oxygen-containing compounds
    • C08K5/14Peroxides

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Insulated Conductors (AREA)
  • Graft Or Block Polymers (AREA)
  • Organic Insulating Materials (AREA)

Description

(54) POLYMERIC COMPOSITIONS CONTAINING BROMINATED FLAME RETARDANTS (71) We, RAYCHEM CORPORATION, a Corporation organised according to the laws of the State of California, United States of America, of 300 Constitution Drive, Menlo Park, California 94025, United States of America, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed to be particularly described in and by the following statement: This invention relates to polymeric compositions comprising bromine-containing flame retardants, and to their use, especially for insulating electrical components, particularly wire and cable.
It is known to provide electrical wire and cable with an electrically insulating covering by coating the wire or cable with a polymeric composition which contains a chlorinated flame retardant, and an unsaturated compound which promotes cross-linking (a "co-agent"), and then cross-linking the coating by heat. While brominated flame retardants are also known, they have not been used in compositions which are cross-linked by peroxides, because the resulting cross-linked compositions have absorbed water too rapidly and therefore have unsatisfactory electrical characteristics.
This invention is based on the surprising discovery that by increasing the amount of co-agent and reducing the amount of peroxide in cross-linkable polymeric compositions containing bromine-containing organic flame retardants, a very significant reduction in the water absorption of the resulting cross-linked compositions is obtained, and in particular that compositions meeting the accepted industry standards can readily be obtained.
In its first aspect, the invention provides a composition which can be cross-linked by heating and which comprises (a) a polymer which can be cross-linked with the aid of an organic peroxide and which is present in an amount of at least 40% by weight of the composition; (b) an organic peroxide; (c) a compound which contains carbon-carbon unsaturation and which co-operates with said peroxide, when the composition is heated, to promote cross-linking of said polymer; and (d) a bromine-containing organic flame retardant which is present in an amount of up to 35% by weight of the composition; the ratio by weight of the unsaturated compound (c) to the peroxide (b) being at least 1.2:1.
In its second aspect, the invention provides a process for the production of a shaped article of a cross-linked polymer composition, which process comprises (1) melt-shaping a composition as defined above under conditions such that crosslinking of said composition is substantially prevented; and (2) heating said melt-shaped composition to effect cross-linking of the polymer; the absolute and relative amounts of said peroxide (b) and said compound (c) preferably being such that the shaped article has an M!()(j value of at least 40 and an IPCEA water absorption (i.e. a change in capacitance over 14 days in the IPCEA Test No. S-66-524, NEMA WC 7, paragraph 6.6) of less than 3%.
In its third aspect the invention provides an article having a coating thereon of a composition comprising at least 40% by weight of a polymer which has been cross-linked with the aid of an organic peroxide and a compound which contains carbon-carbon unsaturation; the residues of said peroxide and said compound containing carbon-carbon unsaturation, in amounts corresponding to a ratio by weight of the unsaturated compound to the peroxide of at least 1.2 1; and up to 35% by weight of a bromine-containing organic flame retardant, said coating having an IPCEA water absorption (as defined above) of less than 3%.
The polymers which can be used in the present invention include polymers of one or more olefins; polymers of one or more olefins with one or more copolymerisable ethylenically unsaturated monomers containing functional groups, such polymers preferably containing at least 50%, especially at least 80%, by weight of units derived from one or more olefins; and polymers of one or more ethylenically unsaturated monomers containing functional groups; and blends of one or more such polymers, such blends preferably containing at least 50%, especially at least 80%, by weight, of units derived from one or more olefins. Particularly suitable olefins are a-mono-olefins, especially ethylene.
Functional groups which may be present on ethylenically unsaturated monomers include acid groups e.g., carboxyl groups and carboxylate salt groups, ester groups, e.g., alkoxy carbonyl groups, alkyl carbonyloxy groups, and halogen atoms. The choice of polymer will, of course, depend upon the end use of the composition. When the composition is used to produce insulation on electrical wire or cable by extrusion coating, preferred compositions comprise a blend of a low density polyethylene and an ethylene/vinylester copolymer, e.g. an ethylene/vinyl acetate copolymer, preferably containing 10 to 30% by weight of units derived from vinyl acetate, in a ratio by weight of polyethylene to copolymer of at least 30:70, e.g., 40:60 to 60:40. Particularly good results are obtained using a blend of about equal parts of a low density polyethylene and an ethylene/vinyl acetate copolymer. The compositions of the invention will contain at least 40%, preferably at least 50%, especially 50 to 80%, e.g. about 60%, by weight of the polymer.
The bromine-containing organic fire retardants used in this invention are preferably aromatic but may be aliphatic. The fire retardant should, of course, be one which will be effective even after the composition has been shaped and cross-linked by heating.
Particularly good results have been obtained using decabromo-diphenylether. This and other brominated compounds are known in the art as flame retardants. The flame retardant may be one which becomes at least in part chemically bonded to the polymer during the cross-linking. Especially when the bromine-containing organic fire retardant is the sole fire retardant, the amount thereof will generally be at least 10%, preferably at least 15%, particularly at least 20%, by weight of the composition. Since excessive amounts of the fire retardant can cause poor physical properties, amounts in excess of 35% are avoided.
The compositions may contain other flame-retardants, for example, inorganic fire retardants, which may be present in substantial amount, e.g. up to 20%, preferably 5 to 15%, by weight of the composition. Especially useful are flame retardants which are known to demonstrate a synergistic effect with halogenated flame retardants, e.g. antimony compounds, especially Sb203. Chlorinated fire retardants may also be present, but the brominated fire retardant preferably provides 50 to 100% especially 80 to 100%, of the total weight of organic fire retardants in the composition and is usually present in an amount at least 5% by weight of the composition.
The compositions may also contain other ingredients such as fillers, processing aids and stabilisers, for example acid scavengers such as lead fumarate (e.g., "Lectro 78") and free radical scavengers such as aromatic secondary amines (e.g., "Agerite Resin D"). The amount of such other ingredients will generally not exceed 10%, preferably 5%, by weight of compositions to be used for extrusion-coating as insulation onto wire or cable.
The organic peroxides used in this invention are those conventionally used in the art, the choice of peroxide being dependent inter alia on the temperature at which the composition is to be shaped (at which decomposition of the peroxide should be sufficiently slow not to interfere with the shaping operation) and the temperature (and, especially in a continuous process, the time) of the subsequent cross-linking step, during which rapid decomposition of the peroxide is desirable. The peroxides which can be used include dicumyl peroxide and 2,5-dimethyl-2,5-di-t-butylperoxyhexane.
The compounds (c) which contain carbon-carbon unsaturation and which cooperate with the peroxides to promote cross-linking are referred to herein as co-agents. The co-agents which can be used are the compounds which have been widely used to promote cross-linking in irradiation cross-linking procedures. Generally they contain at least two ethylenic double bonds. Examples of suitable compounds are triallyl isocyanurate, pentaerythritol triacrylate and pentaerythritol tetraacrylate.
The higher the ratio of the co-agent to the peroxide. the less the water absorption of the cross-linked composition. The ratio by weight is at least 1.2:1, preferably at least 1.5:1, especially at least 1.5:1. This ratio is preferably not more than 10:1 especially not more than 7.5:1, in order to ensure an adequate amount of peroxide.
The total amount of peroxide and co-agent preferably employed is dependent on the cross-linking conditions and the degree of cross-linking required. This amount is generally 1 to 8%, preferably 2 to 5%, by weight of the composition.
The ingredients of the composition are thoroughly mixed together by any convenient method, taking care not to activate the peroxide. The composition is then shaped prior to being cross-linked. Shaping is preferably effected by melt extrusion or other melt-shaping method at a temperature at which decomposition of the peroxide is sufficiently slow that any cross-linking that takes place does not interfere with the shaping operation.
Cross-linking is then effected, generally by raising the temperature. The temperatures employed in these steps will depend upon the polymer and the peroxide. In a preferred procedure, the composition is continuously melt-extruded through a cross-head die onto a wire, and is continuously cross-linked by passing the coated wire through an oven.
Generally, the wire size is 1000 MCM to 20 AWG, preferably 2/0 to 16 AWG, and the coating has a thickness of 15-75 mils, preferably 20-50 mils. Especially for such use, the cross-linking should be effective to increase the M100 modulus (measured as described below) of the composition to at least 30, generally at least 50, preferably at least 70, especially at least 80. On the other hand, the M100 modulus will generally not exceed 200, since this can result in undesirably low elongations.
The invention is illustrated in the following Examples, in which parts are by weight.
Example 1 In each of the Examples, the ingredients shown in the Table below were thoroughly mixed together by blending all the ingredients except the peroxide (B) and the co-agent (C) in a Banbury mixer at 290"F (143"C). In Examples 1-6 the peroxide (B) and the co-agent (C) were thoroughly mixed together with the other previously blended ingredients on a 3 inch two roller mill at 2500F (120 C). In Examples 7-10 the peroxide (B) and the co-agent (C) were thoroughly mixed together with the other previously blended ingredients in a Banbury mixer at 250"F (120"C).
In Examples 1 - 6, the mixture was pressed into a slab at 2500F (120"C), and the slab heated at 390"F (200"C) for 1 minute. The M100 value of the cured slab material was measured using a 1/8 inch (0.3cm) wide strip cut from the slab. The water absorption of the cured slab material was also measured, using a disc cut from the slab. The results are shown in the Table.
In Examples 7 - 10, the mixture was extruded over a wire and then cured at 3900F (200"C) for 1 minute. The water absorption, capacitance change, stability factor and M100 value of the coated wire were measured, and the results are shown in the Table.
In the Table, the Examples marked with an asterisk (*) are comparative Examples, and the various ingredients are as identified below: A(1) is a low density polyethylene ("DYNH") A(2) is an ethylene/vinylacetate (18%) copolymer (EVA 3170) B(1) is dicumyl peroxide supported on CaCO3 (40% peroxide) ("Di-Cup" 40C) ("Di-Cup is a Registered Trade Mark) B(2) is 2,5-dimethyl-2,5-di-t-butylperoxyhexane ("Varox") (50% peroxide) (C) is triallylisocyanurate (TAIC) (D) is decabromodiphenylether ("DE 83") (E) is Sb2O3 F) is lead fumarate ("Lectro 78") (G) is an aromatic secondary amine ("Agerite Resin D") "Ratio", is the ratio of (C) to the peroxide content of (B).
The various properties given in the Table for the cured compositions were measured as follows: Mloo The test specimen is suspended in a chamber maintained at 1200C + 2"C and after it has equilibrated load is applied incrementally until the specimen has elongated 100%. The static modulus, M100, is the slope of a plot of load vs. elongation at 100% elongation and is expressed in psi.
Abs(1) Dicks cut from the cured slabs of Examples 1-6 were weighed dry cut from the cured slabs of Examples 1-6 were weighed dry. They were then immersed in water at 700C for 65 hours, wiped dry and weighed again. The percent weight change was calculated and is reported as Abs (1) Abs (2) The weight increase of samples of the coated wires prepared in Examples 7-10 on exposure to water for seven days was measured by the procedure of IPCEA Publication. No.
S-19-81 NEMA WC3, paragraph 6.9;3 and is reported as Abs(2) in mg/sq, inch. cap 1-14, cap 7-14 and Stab The. change in capacitance on exposure to water of samples of the wires prepared in Examples 7-10 was; measured in accordance with the procedure of IPCEA Publication No.
S-66-524, NEMA WC7, paragraph; 6.6. The percent change after 14 days, based' on the capacitance after one day,. is reported as Cap 1-14, and the percent change between the seventh and fourteenth days, based on the capacitance after seven days, is reported as Cap 7-14. The. stability factor was also calculated and is reported as Stab.
TABLE Example Ingredients (parts by weight) Properties of Cured Composition No. A(1) A(2) B(1) B(2) C D E F G Ratio M100 Abs(1) Abs(2) Cap(1-14) Cap(7-14) Stab *1 30 30 3 0.4 25 10 1 1 0.33 55 0.44 *2 30 30 3 0.4 25 10 1 1 0.27 57 3 30 30 2 1.4 25 10 1 1 1.75 97 0.26 4 30 30 2 1.4 25 10 1 1 1.4 76 *5 30 30 2 0.4 25 10 1 1 0.5 43 6 30 30 1 2.4 25 10 1 1 6.0 91 0.065 *7 29.8 29.8 3 0.4 25 10 1 1 0.33 64 - 12.5 4.9 1.7 0.8 *8 29.8 29.8 3 0.4 25 10 1 1 0.26 71 - 10.0 2.7 1.2 1.1 9 30 30 1 2.0 25 10 1 1 5.0 78 - 3.9 0.4 0.6 0.2 10 30 30 1 2.0 25 10 1 1 4.0 78 - 3.7 1.2 0.7 0.2

Claims (27)

WHAT WE CLAIM IS:
1. A composition which can be cross-linked by heating, and which comprises: (a) a polymer which can be cross-linked with the aid of an organic peroxide and which is present in an amount of at least 40% by weight of the composition; (b) an organic peroxide; (c) a compound which contains carbon-carbon unsaturation and which cooperates with said peroxide, when the composition is heated, to promote cross-linking of said polymer; and (d) a bromine-containing organic flame retardant which is present in an amount of up to 35% by weight of the composition; the ratio by weight of the unsaturated compcund (c) to the peroxide (b) being at least 1.2:1.
2. A composition according to Claim 1 wherein said flame retardant (d) is an aromatic compound.
3. A composition according to Claim 1 wherein said flame retardant (d) provides 50 to 100% of the total weight of organic fire retardants in the composition.
4. A composition according to Claim 3 wherein the ratio by weight of the unsaturated compound (c) to the peroxide (b) is at least 1.5:1.
5. A composition according to Claim 4 wherein said ratio is at least 2.5:1.
6. A composition according to Claim 1 which also contains an inorganic flame retardant.
7. A composition according to Claim 1 wherein at least 80% by weight of the polymer consists of units derived from an a-monoolefin.
8. A composition according to Claim 1 which can be melt-shaped and subsequently cross-linked by heating and which comprises: (a) a polymer which can be cross-linked with the aid of an organic peroxide and at least 80% by weight of which consists of units derived from an a-monoolefin; (b) an organic peroxide; (c) a compound which contains at least two ethylenic double bonds and which cooperates with said peroxide, when the composition is heated, to promote cross-linking of said polymer; (d) a bromine-containing organic flame retardant; and (e) an inorganic flame retardant; said polymer (a) being present in amount 50 to 80% by weight of the composition; the total amount of said peroxide (b) and said unsaturated compound (c) being 1 to 8% by weight of the composition; the ratio by weight of said compound (c) to said peroxide (b) being from
1.5:1 to 7.5:1; said bromine-containing organic flame retardant (d) being present in amount 10 to 35 % by weight of the composition and said inorganic flame retardant (e) being present in amount 5 to 15 % by weight of the composition.
9. A composition according to Claim 8 wherein said polymer is selected from the group consisting of low density polyethylene and blends of low density polyethylene and ethylene/vinyl ester copolymers.
10. A composition according to Claim 9 wherein said unsaturated compound (c) is triallyl isocyanurate.
11. A composition according to Claim 9 wherein said bromine-containing flame retardant (d) is decabromo-diphenyl ether.
12. A composition according to Claim 9, wherein said inorganic flame retardant (e) is Sb,O.
13. A composition according to Claim 1 substantially as described in any one of Examples 3, 4, 6, 9 and 10.
14. A process for the production of a shaped article of a cross-linked polymer composition, which process comprises: (I) melt-shaping a composition as claimed in any one of claims 1 to 13 under conditions such that cross-linking of said composition is substantially prevented; and (2) heating said melt-shaped composition to effect cross-linking of the polymer.
15. A process according to Claim 14, wherein the absolute and relative amounts of said peroxide (b) and said compound (c) are such that the shaped article has an IPCEA water absorption of less than 3% and an M1(( value of at least 40.
16. A process according to claim 15, wherein the shaped article has an Moo,, value of at least 50.
17. A process according to any one of claims 14 to 16, wherein step (I) comprises melt-extruding said composition around an electrical wire or cable to form an electrically insulating coating thereon.
18. A process according to claim 14 substantially as described in any one of Examples 3, 4, 6, 9 and 10.
19. A shaped article produced by a process as claimed in any one of claims 14 to 18.
20. An article having a coating thereon of a composition comprising at least 40% by weight of a polymer which has been cross linked with the aid of an organic peroxide and a compound which contains carbon-carbon unsaturation; and residues of said peroxide and said compound containing carbon-carbon unsaturation, in amounts corresponding to a ratio by weight of the unsaturated compound to the peroxide of at least 1.2:1; and up to 35% by weight of a bromine-containing organic flame retardant; said coating having an IPCEA water absorption of less than 3%.
21. An article according to Claim 20 which is an electrical component which is electrically insulated by said coating and wherein said coating has an M100 value of at least 50.
22. An article according to claim 21 which is an electrical wire or cable.
23. An article according to any one of claims 20 to 22 wherein said coating has an M value of at most 200.
24. An article according to any one of claims 20 to 23 wherein the coating also contains an inorganic flame retardant.
25. An article according to any one of claims 20 to 24, wherein the coating contains 10 to 35% by weight of the coating of the bromine-containing flame retardant and 5 to 15% by weight of an inorganic flame retardant.
26. An article according to claim 25, wherein the bromine-containing flame retardant is decabromo diphenyl ether and the inorganic flame retardant is Sb203.
27. An article as claimed in claim 20, substantially as described in Examples 9 or 10 herein.
GB24964/78A 1977-06-15 1978-05-31 Polymeric compositions containing brominated flame retardants Expired GB1588485A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US80667677A 1977-06-15 1977-06-15
US05/828,731 US4129616A (en) 1977-06-15 1977-08-29 Polymeric compositions containing brominated flame retardants

Publications (1)

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GB1588485A true GB1588485A (en) 1981-04-23

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JP (1) JPS5416550A (en)
BR (1) BR7803815A (en)
CA (1) CA1108791A (en)
DE (1) DE2825995A1 (en)
ES (1) ES470731A1 (en)
FR (1) FR2394573A1 (en)
GB (1) GB1588485A (en)
IT (1) IT1096683B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2153832A (en) * 1984-02-09 1985-08-29 Chisso Corp Flame retardant polyolefin compositions

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0376737A (en) * 1989-08-17 1991-04-02 Mitsubishi Cable Ind Ltd Water running-preventive composition and water running-preventive cable manufactured therewith

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL299621A (en) * 1962-12-05 1900-01-01
US3806555A (en) * 1971-03-25 1974-04-23 Wako Pure Chem Ind Ltd Process for crosslinking olefin polymers
US3816564A (en) * 1972-02-02 1974-06-11 Itt Insulation coating compositions
US3856890A (en) * 1973-05-23 1974-12-24 Nat Distillers Chem Corp Flame retardant compositions
US3974132A (en) * 1975-05-15 1976-08-10 Borg-Warner Corporation Process for curing olefin polymers

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2153832A (en) * 1984-02-09 1985-08-29 Chisso Corp Flame retardant polyolefin compositions

Also Published As

Publication number Publication date
CA1108791A (en) 1981-09-08
FR2394573A1 (en) 1979-01-12
BR7803815A (en) 1979-01-16
ES470731A1 (en) 1979-01-16
DE2825995A1 (en) 1979-01-11
JPS5416550A (en) 1979-02-07
IT7824561A0 (en) 1978-06-14
IT1096683B (en) 1985-08-26

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PS Patent sealed [section 19, patents act 1949]
PCNP Patent ceased through non-payment of renewal fee