Polymeric blends containing a monoorganic polysiloxane resin

• US 4,265,801 A
• Filed: 07/17/1978
• Issued: 05/05/1981
• Est. Priority Date: 07/27/1977
• Status: Expired due to Term

• Current Assignee: Raychem Limited Rolls House
• Original Assignee: Raychem Limited (TE Connectivity Limited)
• Inventors: Penneck, Richard J., Moody, Anthony G.
• Primary Examiner(s): BRIGGS SR, WILBERT
• Application Number:
  US05/925,238
• Time in Patent Office: 1,023 Days
• Field of Search: 260/824 R, 260/40, 260/37 SB, 260/42.26, 525/100, 525/446, 525/105, 525/106, 525/409, 525/431, 525/453, 525/474
• US Class Current: 524/430
• CPC Class Codes: H01B 3/46 silicones
• CPC Class Codes: Y10T 428/31663 As siloxane, silicone or silane

Abstract

The invention relates to novel melt processable polymer compositions which comprise a blend of non-silicone polymer and a monoorganic polysiloxane resin. Such compositions are useful inter alia as flameproof and moisture resistant coating compositions and in the product of heat shrinkable silicone elastomer compositions.

Claims

1. A flame retarded, melt processable polymer composition, comprising a blend of (a) non-silicone polymer that is an elastomer or a thermoplastic polymer, (b) solid, non-elastomeric, monoorganic polysiloxane resin comprising at least 80% by weight of polymerized units of the formula RSiO₁.5 where R is hydrogen or an organic group, at least 85% of the R groups being organic groups, the non-silicone polymer and the monorganic siloxane resin being present in a weight ratio of from 10:

1 to 1;

1, wherein the monoorganic polysiloxane resin has a number average molecular weight in the range of from 2000 to 6000 and a hydroxyl content of less than 2% by weight, and (c) an effective amount of filler providing enhanced fire retardant properties.

2. The composition of claim 1, having an oxygen index greater than 25 as measured by the method of ASTM D2863-76.

3. The composition of claim 1, having a maximum specific optical density of less than 250 (non-flaming condition) as measured by the method of ASTM FO7.06 Draft No. 3.

4. The composition of claim 1, having a maximum specific optical density of less than 150 (flaming condition) as measured by the method of ASTM FO7.06 Draft No. 3.

5. The composition of claim 1, in which the polymer and the resin are substantially free of halogen substituents.

6. The composition of claim 1, in which the non-silicone polymer comprises a thermoplastic polymer comprising a polyolefin, a polyester, a polyamide, or a copolymer of an olefin and an unsaturated ester containing less then 35% by weight of the unsaturated ester.

7. The composition of claim 6, in which the thermoplastic polymer comprises a segmented copolyester polymer consisting essentially of recurring intralinear long chain ester units and short chain ester units randomly joined head-to-tail through ester linkages, said long chain ester units being represented by the formula:

##STR5## and said short chain ester units being represented by the formula;

##STR6## where G is a divalent radical remaining after the removal of terminal hydroxyl groups from at least one long chain glycol having a molecular weight of from 600 to 6000;

R is a divalent radical remaining after removal of carboxyl groups from at least one dicarboxylic acid having a molecular weight of less than 300; and

D is a divalent radical remaining after removal of hydroxyl groups from at least one low molecular weight diol having a molecular weight of less than 250.

8. The composition of claim 7, in which the thermoplastic polymer comprises a segmented polyether ester copolymer derived from terephthalic acid, polytetramethylene ether glycol and 1,4-butanediol, having the repeating units ##STR7## in which n=6 to 40.

9. The composition of claim 1, in which the monoorganic polysiloxane resin has a softening point in excess of 50°

C. as measured by thermomechanical analysis.

10. The composition of claim 1, in which the monoorgano polysiloxane resin comprises units of the formula R₁ R₂ R₃ SiO₀.5 wherein R₁, R₂ and R₃ are hydrogen, or organic groups which may be the same or different, at least two of the groups R₁, R₂ and R₃ in each R₁ R₂ R₃ SiO₀.5 unit being organic groups, and in which the ratio of RSiO₁.5 units to R₁ R₂ R₃ SiO₀.5 units is from 1:

0.005 to 1;

0.03 on a molar basis.

11. The composition of claim 10, in which R is a hydrocarbon group or a substituted hydrocarbon group.

12. The composition of claim 11, in which R is a methyl or phenyl group.

13. The composition of claim 10 in which R₁, R₂ and R₃ are unsubstituted or substituted hydrocarbon groups.

14. The composition of claim 13, in which R₁, R₂ and R₃ are each a methyl or a phenyl group.

15. The composition of claim 10, in which up to 80% of the groups R are phenyl groups, with the remainder being methyl groups.

16. The composition of claim 12, in which the ratio of methyl to phenyl groups on a molar basis is from 1:

3 to 3.1.

17. The composition of claim 1, in which the monoorgano siloxane resin comprises units of the formula CH₃ SiO₁.5 and (CH₃)₂ SiO in the molar ratio of from 8:

1 to 9.5;

1.

18. The composition of claim 1, in which the filler comprises a metal oxide, hydroxide or salt, or a mixture thereof.

19. The composition of claim 1, in which the filler comprises a hydrate of alumina.

20. The composition of claim 19, in which the filler comprises α

-alumina trihydrate.

21. The composition of claim 1, in which the filler has a specific surface area of at least 1 m² /g.

22. The composition of claim 1, in which the filler has a surface area of from 1 to 80 m² /g.

23. The composition of claim 1, in which the filler is present in an amount of from 10 to 400 parts by weight per 100 parts by weight of non-silicone polymer.

24. The composition of claim 1, in which the filler is present in an amount of from 80 to 120 parts by weight per 100 parts by weight of non-silicone polymer.

25. The composition of claim 1, that has been crosslinked.

26. The composition of claim 1, in which the monoorgano polysiloxane resin comprises substituents comprising olefinically unsaturated groups capable of undergoing crosslinking reactions.

27. The composition of claim 25, in which the crosslinking has been carried out by irradiation.

28. Electrical insulation comprising a polymer composition of claim 1.

29. An article which is heat recoverable, which can be rendered heat recoverable, or which is heat recovered, which comprises the polymer composition of claim 1.

30. Electrical wire or cable provided with the insulation of claim 28.

31. The composition of claim 1, in which the non-silicone polymer is an elastomer selected from the group consisting of a polyolefin, an olefin copolymer, and a higher olefin polymer.

32. The composition of claim 1, in which the non-silicone polymer is an elastomer selected from the group consisting of an ethylene/acrylic ester polymer containing at least 3.6 moles of ethylene per 1000 gms of polymer and an ethylene vinyl acetate polymer, containing at least 3.6 moles of ethylene per 1000 gms of polymer.

33. The composition of claim 32, in which the elastomer is selected from:

(a) an ethylene/alkyl acrylate or ethylene/alkyl methacrylate copolymer wherein the alkyl group has 1 to 4 carbon atoms, the proportion of the acrylic ester being equivalent to from 2.4 to 8.0 moles of ester groups per 1000 gms of the copolymer;

(b) a terpolymer of ethylene with an alkyl acrylate or methacrylate wherein the alkyl group has from 1 to 4 carbon atoms, and a third copolymerizable monomer selected from;

(i) a C₁ -C₁₂ alkyl monoester or diester of a butenedioic acid

(ii) acrylic acid

(iii) methacrylic acid

(iv) carbon monoxide

(v) acrylonitrile

(vi) a vinyl ester

(vii) an alkyl or alkyl methacrylate, the alkyl group having at least 5 carbon atoms

(viii) maleic anhydride the proportion of the acrylic ester being equivalent to from 2.5 to 8.0 moles of ester groups per 1000 gms of the polymer, and the proportion of the third monomer being not higher than 10 weight percent of the polymer, and

(c) an ethylene/vinyl acetate copolymer containing at least 35% by weight vinyl acetate.

34. The composition of claim 33, in which the elastomer comprises a terpolymer or ethylene, methyl acrylate and cure-site monomer comprising carboxyl groups.