Polyurethane foams containing high levels of silicone-containing surfactant polymer to improve flame retardance and aged K-factors

• US 5,686,499 A
• Filed: 10/27/1995
• Issued: 11/11/1997
• Est. Priority Date: 10/27/1995
• Status: Expired due to Fees

• Current Assignee: BASF Corporation (BASF SE)
• Original Assignee: BASF Corporation (BASF SE)
• Inventors: Fishback, Thomas L.
• Primary Examiner(s): Foelak, Morton
• Application Number:
  US08/549,582
• Time in Patent Office: 746 Days
• Field of Search: 556/439, 556/440, 556/445, 556/449, 521/112, 521/172, 521/131
• US Class Current: 521/112
• CPC Class Codes: C08G 18/4018 Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
• CPC Class Codes: C08G 18/4225 derived from residues obtained from the manufacture of dimethylterephthalate and from polyhydroxy compounds
• CPC Class Codes: C08G 18/5087 Phosphite compounds
• CPC Class Codes: C08G 2110/0025 rigid
• CPC Class Codes: C08G 2110/005 < 50kg/m3
• CPC Class Codes: C08G 2115/02 to isocyanurate groups
• CPC Class Codes: C08J 2375/04 Polyurethanes
• CPC Class Codes: C08J 9/141 Hydrocarbons

Abstract

There is now provided a closed cell rigid polyurethane foam made from a polyol composition containing a polyol having polyester linkages and a number average molecular weight of 400 or more, and at least about 8 php of a silicone-containing surfactant polymer. Either mixed into the polyol composition at the time of foaming, mixed into an isocyanate, or both, is an aliphatic or cycloaliphatic C₄ -C₇ hydrocarbon.

Claims

1. A polyisocyanate based closed cell rigid foam comprising reacting an organic isocyanate and a polyol composition in the presence of a blowing agent comprising an aliphatic or cycloaliphatic C₄ -C₇ hydrocarbon, said polyol composition comprising:

a) a polyol having polyester linkages and a number average molecular weight of 400 or more; and

b) at least about 8 php of a silicone-containing surfactant polymer.

2. The foam of claim 1, wherein the amount of aliphatic or cycloaliphatic C₄ -C₇ hydrocarbon blowing agent is from 4 wt. % to 15 wt. % based on the weight of all foam ingredients.

3. The foam of claim 1, wherein the surfactant contains the moiety --Si(R₂)O--, where the R groups are independently an alkyl radical having 1 to 20 carbon atoms;

an alicyclic, an aryl, an alkaryl or an aralkyl having 1 to 25 carbon atoms in the alkyl group;

an aliphatic ether group;

or a polyester group.

4. The foam of claim 3, wherein the R groups on the --Si(R₂)O-- moiety are independently alkyl radicals having from 1 to 4 carbon atoms.

5. The foam of claim 1, wherein the surfactant comprises an oxyalkylene-silicone polymer terminated with hydrocarbon groups.

6. The foam of claim 1, wherein the surfactant corresponds to the general formula (II):

space="preserve" listing-type="equation">R'"'"'.sub.3 SiO(R.sub.2 SiO).sub.y RO(CnH.sub.2n O).sub.z SiRO!.sub.w SiR.sub.3

wherein w is an integer of at least 1, y is an integer of at least 3 and stands for the number of difunctional siloxane units;

z is an integer of at least 5 and stands for the length of a polyoxyalkylene chain;

n is an integer of 2 to 4 and stands for the number of carbon atoms in an oxyalkylene group;

R'"'"' is a monovalent hydrocarbon group; and

each R group is independently an alkyl group or a trihydrocarbylsilyl group at an end of a siloxane group, and having a polysiloxane chain and a polyoxyalkylene chain bonded with a C--Si bond.

7. The foam of claim 6, wherein the surfactant corresponds to the formula:

##STR13## wherein w, y, z, n, and R are as defined in claim 6;

y and y'"'"' together are as defined such that the sum of y and y'"'"' must be at least 3 and each are at least 1; and

p is an integer from 2 to 17.

8. The foam of claim 7, wherein the surfactant is characterized by containing 5 to 95 percent by weight of polysiloxane units, and 95 to 5 percent by weight of polyoxyalkylene units, and having a molecular weight of 1,000 to 16,000.

9. The foam of claim 7, wherein R and R'"'"' are independently C₁ -C₆ alkyl radicals, and wherein the surfactant has 5 to 50 weight percent polysiloxane units, and 95 to 50 percent by weight of polyoxyalkylene units.

10. The foam of claim 7, characterized by containing more than 95 percent by weight of polysiloxane units and less than 5 percent by weight of polyoxyalkylene units, and having a molecular weight of 500 to 10,000.

11. The foam of claim 1, wherein the surfactant comprises a hydroxyl functional polymer corresponding to the general formula:

##STR14## wherein each of R are independently an alkyl radical having 1 to 20 carbon atoms;

an alicyclic, an aryl, an alkaryl or an aralkyl having 1 to 25 carbon atoms in the alkyl group;

an aliphatic ether group;

or a polyester group; and

wherein a secondary hydroxyl functional group is substituted onto at least one of the R groups;

each of A are independently one or more silicon atoms containing alkyl, alicyclic, cycloalkyl, aryl, alkyloxy, alkaryl, aralkyl, or arylalkoxy have a 1 to 25 carbon atoms in each aliphatic portion;

an organosiloxane;

hydrogen;

or an alkyl having 1 to 25 carbon atoms;

the sum of w+x totals an integer which would correspond to an average hydroxyl equivalent weight ranging from 200 to 4,000.

12. The foam of claim 11, wherein each of R are independently an alkyl having from 1 to 10 carbon atoms, an alkoxy, or an ether having the formula:

##STR15##

13. The foam of claim 12, wherein A is hydrogen, a C₁ -C₄ alkyl, or a siloxane having the formula:

##STR16## wherein n is an integer from 1 to 6, and w+x+y+z totals an integer corresponding to an average hydroxyl equivalent weight of the molecule ranging from 1,250 to 3,000.

14. The foam of claim 1, wherein the silicone polymer comprises a hydroxyl functional polymer represented by the formula:

##STR17## wherein R¹ groups are the same or different and represent alkyl groups with 1 to 4 carbon atoms, phenyl groups, or groups with the formula;

##STR18## R₂ groups can have the same meaning as the R₁ groups, with the proviso that at least one R₂ group is a hydroxyl functional C₁ -C₈ hydrocarbon or one or more oxyalkylene groups terminated with a hydroxyl group;

a has a value of 1 to 1000; and

b has a value of 0 to 10.

15. The foam of claim 14, wherein the silicone polymer comprises a hydroxyl functional silicone polymer corresponding to the formula:

##STR19## wherein each n is independently an integer ranging from 1 to 4, and w+x+y+z totals an integer corresponding to an average hydroxyl equivalent weight of the molecule ranging from 1,250 to 3,000.

16. The foam of claim 1, wherein the blowing agent comprises n-pentane, isopentane, cyclopentane, or mixtures thereof.

17. The foam of claim 16, further comprising water and 2-chloropropane.

18. The foam of claim 1, wherein the polyol comprises an aromatic polyester polyol.

19. The foam of claim 1, comprising a polyol derived from phthalic acid, terephthalic acid, isophthalic acid, dimethyl terephthalate, polyethylene terephthalate, or mixtures thereof.

20. The foam of claim 19, wherein a) comprises an aromatic polyester polyol having an average hydroxyl number of from 30 to 550, and further comprising an organo-phosphorous compound having at least two isocyanate reactive hydrogens.

21. The foam of claim 1, wherein the amount of all blowing agents is from 10 php to 40 php, and further comprising water in an amount 0.25 php to 1.0 php and a phosphite polyol.