Method of producing elastomeric silicone foam

• US 4,608,396 A
• Filed: 02/03/1986
• Issued: 08/26/1986
• Est. Priority Date: 10/16/1985
• Status: Expired due to Term

• Current Assignee: Dow, Inc.
• Original Assignee: Dow, Inc.
• Inventors: Lee, Chi-Long, Rabe, James A., Bauman, Therese M.
• Primary Examiner(s): Foelak, Morton
• Application Number:
  US06/825,494
• Time in Patent Office: 204 Days
• Field of Search: 528/15, 528/31, 528/32, 521/82, 521/88, 521/99, 521/117, 521/91, 521/110, 521/111, 521/134, 521/154
• US Class Current: 521/99
• CPC Class Codes: C08J 2383/04 Polysiloxanes
• CPC Class Codes: C08J 9/02 using blowing gases generated by the reacting monomers or modifying agents during the preparation or modification of macromolecules

Abstract

A method of producing elastomeric silicone foams from a two-part system is disclosed. The method mixes the ingredients then allows a froth to form and cure at ambient temperature to an elastomeric silicone foam. The method mixes a vinyl-containing polydiorganosiloxane (1), a hydroxylated polydiorganosiloxane (2), a platinum catalyst (3), an organohydrogensiloxane (4) and a profoamer (5). The profoamer is a resinous, benzene-soluble organosiloxane copolymer consisting essentially of SiO_4/2 units, silicone bonded hydroxyl groups, (CH₃)₃ SiO_1/2 units, and fluorine-containing units. An embodiment of the method includes a liquified blowing agent and stores the mixture under superatmospheric pressure, forming a foam by releasing the mixture to atmospheric pressure. Another embodiment includes an alcohol in the mixture to provide a foam of lower density. when lauryl alcohol is used and the alcohol is mixed with (1), (3), and (5) before (2) is admixed, the foam has a Bashore resiliency of less than 20.

Claims

1. A foamable silicone composition comprising a composition obtained by mixing

(1) a vinyl containing polydiorganosiloxane having at least an average of about 2 vinyl radicals per molecule, the organic radicals being selected from the group consisting of alkyl radicals having from 1 to 6 carbon atoms per radical, phenyl, and vinyl,

(2) a hydroxylated polydiorganosiloxane having an average of from greater than 1 to 2.5 silicon-bonded hydroxyl radicals per molecule and having an average of at least one organic radical per silicon atom selected from the group consisting of alkyl radicals having from 1 to 6 carbon atoms per radical and phenyl,

(3) a platinum catalyst in an amount sufficient to give from 5 to 200 parts by weight platinum per one million parts by weight total mixture,

(4) an organohydrogensiloxane having an average of at least 3 silicon-bonded hydrogen atoms per molecule, an average of no more than one silicon-bonded hydrogen atom per silicon atom and organic radicals selected from the group consisting of alkyl radicals having from 1 to 6 carbon atoms per radical and phenyl,

(5) a profoamer consisting essentially of a resinous, benzene-soluble organosiloxane copolymer consisting essentially of SiO_4/2 units, silicon-bonded hydroxyl groups, (CH₃)₃ SiO_1/2 units and fluorine-containing units selected from the group consisting of R_a R'"'"'_b SiO.sub.(4-a-b)/2 and R"[Si(R'"'"')_b O.sub.(3-b)/2 ]₂ and mixtures thereof, where R is a monovalent organic radical containing at least four perfluorinated carbon atoms and is bonded to the silicon atom of said fluorine-containing units by a sequence of at least two methylene units or by an oxygen atom that is, in turn, bonded to a sequence of at least two methylene units, R'"'"' is an alkyl radical containing from 1 to 3 carbon atoms, and R" is a divalent organic radical containing at least four perfluorinated carbon atoms and is bonded to the silicon atom of said fluorine-containing units by means of a carbon or oxygen atom, a is 1 or 2, b is 0, 1 or 2 and the sum of a and b is 3 or less with the provision that when R and R" represent fluorine-containing units bonded to silicon via an oxygen atom the organosiloxane copolymer optionally contains repeating units of the formula GSiO_3/2 where G represents the residue obtained by removal of the hydrogen atom from a hydroxyl group of a linear organic polymer containing an average of at least one terminal hydroxyl group per molecule and selected from the group consisting of polyethers, polyoxyalkylene glycols, homopolymers of ethylenically unsaturated alcohols and copolymers of ethylenically unsaturated alcohols with ethylenically unsaturated hydrocarbons;

the molar ratio of all units other than hydroxyl and SiO_4/2 units to SiO_4/2 units is from 0.7;

1 to 1.1;

1, inclusive, and the concentration of said fluorine-containing units and any GSiO_3/2 units is sufficient to

(a) impart a surface tension of less than 2.2×

10^-4 newtons per centimeter at 25°

C. to a 10 percent by weight solution of (5) in a hydroxyl endblocked polydimethylsiloxane exhibiting a viscosity of 0.08 Pa.s at 25°

C., and

(b) require the addition of from 0 to 100 percent by weight of xylene to said 10 percent by weight solution to achieve optical clarity and

(6) optionally, an amount of liquified blowing agent sufficient to form a foam following the release of a mixture containing said liquified blowing agent into an area under atmospheric pressure, the mixture containing this liquified blowing agent being confined under superatmospheric pressure, and

(7) optionally, an alcohol having from 1 to 12 carbon atoms, and

(8) optionally, flame retardant additives consisting essentially of non-flammable fibers and sulfur-free carbon black,

there being sufficient organohydrogen present to provide a molar ratio of silicon-bonded hydrogen atoms to the sum of vinyl radicals, silicone- bonded hydroxyl radicals, and carbon bonded hydroxyl radicals of 0.5;

1 to 40;

1 the mixture having a viscosity of less than 100 Pa'"'"'s at 25°

C.

2. The composition of claim 1 in which the profoamer (5) is present in an amount of from 1 to 20 percent by weight of the composition.

3. The composition of claim 2 in which the fluorine-containing units of (5) are of the formula R_a R_b^'"'"' SiO.sub.(4-a-b)/2 where R is F(C_n F_2n) (CH₂)₂ O_c ;

R'"'"' is methyl;

a is 1;

b is 0, 1, or 2;

c is 0 or 1 and and wherein each of said fluorine-containing units n represents an integer that is the same or different with respect to the value of n in other fluorine-containing units of (5), the average value of n being from 4 to 20 inclusive.

4. The composition of claim 3 in which d is 0 and (5) is the reaction product of an organosiloxane copolymer consisting essentially of (CH₃)₃ SiO_1/2 units, SiO_4/2 units and from 0.2 to about 4 percent by weight of silicon-bonded hydroxyl groups with a mixture of homologous silanes of the formula F(CF₂)_n CH₂ CH₂ Si(CH₃)_b Cl_3-b, where n varies amoung the silanes and represents an integer from 4 to 14 inclusive.

5. The composition of claim 3 in which d is 1 and (5) is the reaction product of an organosiloxane copolymer consisting essentially of (CH₃)₃ SiO_1/2 units, SiO_4/2 units, and from 0.2 to about 4 percent by weight of silicon-bonded hydroxyl groups with a mixture of homologous fluorine-containing alcohols of the general formula F(CF₂)_n (CH₂)₂ OH, wherein each molecule of said alcohols, n represents an even integer from 4 to 14 inclusive.

10. The composition of claim 2 in which from 1 to 10 percent by weight of (7) an alcohol having from 1 to 12 carbon atoms is also present.

11. The composition of claim 2 in which from 2 to 10 percent by weight of (8) flame retardant additives consisting essentially of non-flammable fibers and sulphur free carbon black are also present.

12. The foam produced by the composition of claim 1.

6. A silicone composition comprising a vinyl containing polydiorganosiloxane having at least an average of about 2 vinyl radicals per molecule, the organic radicals being selected from the group consisting of alkyl radicals having from 1 to 6 carbon atoms per radical, phenyl, and vinyl, and a profoamer consisting essentially of a resinous, benzene-soluble organosiloxane copolymer consisting essentially of SiO_4/2 units, silicon-bonded hydroxyl groups, (CH₃)₃ SiO_4/2 units and fluorine-containing units selected from the group consisting of R_a R'"'"'_b SiO.sub.(4-a-b)/2 and R"[Si(R'"'"')_b O.sub.(3-b)/2 ]₂ and mixtures thereof, where R is a monovalent organic radical containing at least four perfluorinated carbon atoms and is bonded to the silicon atom of said fluorine-containing units by a sequence of at least two methylene units or by an oxygen atom that is, in turn, bonded to a sequence of at least two methylene units, R'"'"' is an alkyl radical containing from 1 to 3 carbon atoms, and R" is a divalent organic radical containing at least four perfluorinated carbon atoms and is bonded to the silicon atom of said fluorine-containing units by means of a carbon or oxygen atom, a is 1 or 2, b is 0, 1 or 2 and the sum of a and b is 3 or less with the provision that when R and R" represent fluorine-containing units bonded to silicon via an oxygen atom the organosiloxane copolymer optionally contains repeating units of the formula GSiO_3/2 where G represents the residue obtained by removal of the hydrogen atom from a hydroxyl group of a linear organic polymer containing an average of at least one terminal hydroxyl group per molecule and selected from the group consisting of polyethers, polyoxyalkylene glycols, homopolymers of ethylenically unsaturated alcohols and copolymers of ethylenically unsaturated alcohols with ethylenically unsaturated hydrocarbons;

the molar ratio of all units other than hydroxyl and SiO_4/2 units to SiO_4/2 units is from 0.7;

1 to 1.1;

1, inclusive, and the concentration of said fluorine-containing units and any GSiO_3/2 units is sufficient to (a) impart a surface tension of less than 2.2×

10^-4 newtons per centimeter at 25°

C. to a 10 percent by weight solution of (5) in a hydroxyl endblocked polydimethylsiloxane exhibiting a viscosity of 0.08 Pa'"'"'s at 25°

C., and (b) require the addition of from 0 to 100 percent by weight of xylene to said 10 percent by weight solution to achieve optical clarity.

8. The silicone composition of claim 6 in which the composition is confined under superatomspheric pressure for storage and in which there is also an amount of liquified blowing agent sufficient to form a foam following the release of the composition containing said liquified blowing agent into an area under atmospheric pressure.

7. A silicone composition comprising a hydroxylated polydiorganosiloxane having an average of from greater than 1 to 2.5 silicon-bonded hydroxyl radicals per molecule and having an average of at least one organic radical per silicon atom selected from the group consisting of alkyl radicals having from 1 to 6 carbon atoms per radical and phenyl, and a profoamer consisting essentially of a resinous, benzene-soluble organosiloxane copolymer consisting essentially of SiO_4/2 units, silicon-bonded hydroxyl groups, (CH₃)₃ SiO_1/2 units and fluorine-containing units selected from the group consisting of R_a R'"'"'_b SiO.sub.(4-a-b)/2 and R"[Si(R'"'"')_b O.sub.(3-b/2 ]₂ and mixtures thereof, where R is a monovalent organic radical containing at least four perfluorinated carbon atoms and is bonded to the silicon atom of said fluorine-containing units by a sequence of at least two methylene units or by an oxygen atom that is, in turn, bonded to a sequence of at least two methylene units, R'"'"' is an alkyl radical containing from 1 to 3 carbon atoms, and R" is a divalent organic radical containing at least four perfluorinated carbon atoms and is bonded to the silicon atom of said fluorine-containing units by means of a carbon or oxygen atom, a 1 or 2, b is 0, 1 or 2 and the sum of a and b is 3 or less with the provision that when R and R" represent fluorine-containing units bonded to silicon via an oxygen atom the organosiloxane copolymer optionally contains repeating units of the formula GSiO_3/2 where G represents the residue obtained by removal of the hydrogen atom from a hydroxyl group of a linear organic polymer containing an average of at least one terminal hydroxyl group per molecule and selected from group consisting of polyethers, polyoxyalkylene glycols, homopolymers of ethylenically unsaturated alcohols and copolymers of ethylenically unsaturated alcohols with ethylenically unsaturated hydrocarbons;

the molar ratio of all units other than hydroxyl and SiO_4/2 units to SiO_4/2 units is from 0.7;

1 to 1.1;

1, inclusive, and the concentration of said fluorine-containing units and any GSiO_3/2 units is sufficient to (a) impart a surface tension of less than 2.2×

10^-4 newtons per centimeter at 25°

C. to a 10 percent by weight solution of (5) in a hydroxyl endblocked polydimethylsiloxane exhibiting a viscosity of 0.08 Pa'"'"'s at 25°

C., and (b) require the addition of from 0 to 100 percent by weight of xylene to said 10 percent by weight solution to achieve optical clarity.

9. The silicone composition of claim 7 in which the composition is confined under superatomspheric pressure for storage and in which there is also an amount of liquified blowing agent sufficient to form a foam following the release of the composition containing said liquified blowing agent into an area under atmospheric pressure.

13. The elastomeric silicone foam produced by

(A) mixing ingredients consisting essentially of

(1) a vinyl containing polydiorganosiloxane having at least an average of about 2 vinyl radicals per molecule, the organic radicals being selected from the group consisting of alkyl radicals having from 1 to 6 carbon atoms per radical, phenyl, and vinyl,

(2) a hydroxylated polydiorganosiloxane having an average of from greater than 1 to 2.5 silicon-bonded hydroxyl radicals per molecule and having an average of at least one organic radical per silicon atom selected from the group consisting of alkyl radicals having from 1 to 6 carbon atoms per radical and phenyl,

(3) a platinum catalyst in an amount sufficient to give from 5 to 20 parts by weight platinum per one million parts by weight total mixture,

(4) an organohydrogensiloxane having an average or at least 3 silicon-bonded hydrogen atoms per molecule, an average of no more than one silicon-bonded hydrogen atom per silicon atom and organic radicals selected from the group consisting of alkyl radicals having from 1 to 6 carbon atoms per radical and phenyl,

(5) a profoamer consisting essentially of a resinous, benzene-soluble organosiloxane copolymer consisting essentially of SiO_4/2 units, silicon-bonded hydroxyl groups, (CH₃)₃ SiO_1/2 units and fluorine-containing units selected from the group consisting of R_a R'"'"'_b SiO.sub.(4-a-b)/2 and R"[Si(R'"'"')_b O.sub.(3-b)/2 ]₂ and mixtures thereof, where R is a monovalent organic radical containing at least four perfluorinated carbon atoms and is bonded to the silicon atom of said fluorine-containing units by a sequence of at least two methylene units or by an oxygen atom that is, in turn, bonded to a sequence of at least two methylene units, R'"'"' is an alkyl radical containing from 1 to 3 carbon atoms, and R" is a divalent organic radical containing at least four perfluorinated carbon atoms and is bonded to the silicon atom of said fluorine-containing units by means of a carbon or oxygen atom, a is 1 or 2, b is 0, 1 or 2 and the sum of a and b is 3 or less with the provision that when R and R" represent fluorine-containing units bonded to silicon via an oxygen atom the organosiloxane copolymer optionally contains repeating units of the formula GSiO_3/2 where G represents the residue obtained by removal of the hydrogen atom from a hydroxyl group of a linear organic polymer containing an average of at least one terminal hydroxyl group per molecule and selected from the group consisting of polyethers, polyoxyalkylene glycols, homopolymers of ethylenically unsaturated alcohols and copolymers of ethylenically unsaturated alcohols with ethylenically unsaturated hydrocarbons;

the molar ratio of all units other than hydroxyl and SiO_4/2 units to SiO_4/2 units is from 0.7;

1 to 1.1;

1, inclusive, and the concentration of said fluorine-containing units and any GSiO_3/2 units is sufficient to

(a) impart a surface tension of less than 2.2×

10^-4 newtons per centimeter at 25°

C. to a 10 percent by weight solution of (5) in a hydroxyl endblocked polydimethylsiloxane exhibiting a viscosity of 0.08 Pa'"'"'s at 25°

C., and

(b) require the addition of from 0 to 100 percent by weight of xylene to said 10 percent by weight solution to achieve optical clarity and

(6) optionally, an amount of liquified blowing agent sufficient to form a foam following the release of a mixture containing said liquified blowing agent into an area under atmospheric pressure, the mixture containing this liquified blowing agent being confined under superatmospheric pressure, and

(7) optionally, an alcohol having from 1 to 12 carbon atoms, and

(8) optionally, flame retardant additives consisting essentially of non-flammable fibers and sulfur-free carbon black,

there being sufficient organohydrogen present to provide a molar ratio of silicon-bonded hydrogen atoms to the sum of vinyl radicals, silicone-bonded hydroxyl radicals, and carbon bonded hydroxy radicals of 0.5;

1 to 40;

1 the mixture having a viscosity of less than 100 Pa'"'"'s at 25°

C., thereafter,

(B) allowing the mixture to form a froth and cure at ambient temperature to an elastomeric silicone foam.