Morpholino-modified polysiloxane-polyoxyalkylene copolymers and their use as foam stabilizers in polyurethanes

• US 4,018,723 A
• Filed: 02/25/1975
• Issued: 04/19/1977
• Est. Priority Date: 02/25/1975
• Status: Expired due to Term

• Current Assignee: OSI Specialties, Inc. (MPM Holdings, Inc.)
• Original Assignee: Union Carbide Corporation (Dow, Inc.)
• Inventors: Kanner, Bernard, Prokai, Bela
• Primary Examiner(s): Czaja, Donald E.
• Assistant Examiner(s): Fletcher, H. H.
• Application Number:
  US05/552,996
• Time in Patent Office: 784 Days
• Field of Search: 260/247.7 L, 260/46.5 E, 260/2.5 AH, 260/824 R
• US Class Current: 521/107
• CPC Class Codes: C08G 18/4241 from dicarboxylic acids and dialcohols in combination with polycarboxylic acids and/or polyhydroxy compounds which are at least trifunctional
• CPC Class Codes: C08G 2110/0008 flexible
• CPC Class Codes: C08G 2110/0083 prepared using water as the sole blowing agent
• CPC Class Codes: C08G 77/46 containing polyether sequences
• CPC Class Codes: C08J 2375/04 Polyurethanes
• CPC Class Codes: C08J 2483/00 Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
• CPC Class Codes: C08J 9/0061 characterized by the use of several polymeric components
• CPC Class Codes: Y10S 521/906 Polyurethane cellular product containing unreacted flame-retardant material

Abstract

Organosilicone compositions are provided which comprise polysiloxane-polyoxyalkylene copolymers containing monofunctional siloxy units (M_o) and difunctional siloxy units (D_o), an average of between about 2 and about 100 silicon-bonded morpholino-bearing groups (Q) for every two moles of M_o and an average of between 2 and about 30 silicon-bonded, organic-capped polyoxyalkylene blocks (E) for every two moles of M_o, the monofunctional units encompassed by M_o having at least two alkyls bonded to the respective silicon atoms thereof and the difunctional units encompassed by D_o having at least one alkyl bonded to the respective silicon atoms thereof, the remaining organic group bonded to silicon of said monofunctional and difunctional siloxy units being alkyl, Q or E. The polymers of the invention find particular application in the manufacture of cellular urethane products including flame-retarded urethane foam.

Claims

1. An organosilicone composition which comprises a polysiloxane-polyoxyalkylene copolymer containing monofunctional siloxy units and difunctional siloxy units, an average of between about 2 and about 30 silicon-bonded polyoxyalkylene blocks for every two moles of monofunctional units, and an average of from about 2 to about 100 silicon-bonded morpholino-bearing groups for every two moles of monofunctional units, wherein:

i. said polyoxyalkylene blocks have the average composition,

space="preserve" listing-type="equation">--(R°

).sub.r-- (OC.sub.a H.sub.2a).sub.b-- OG

3. An organosilicone composition as defined in claim 1 in which the polysiloxane-polyoxyalkylene copolymer contains, for every two moles of monofunctional units, an average of up to about 200 moles of said difunctional siloxy units wherein the remaining organic group bonded to the respective silicon atoms thereof is said alkyl of one to ten carbon atoms.

5. An organosilicone composition as defined in claim 3 in which the said copolymer contains an average of from about 20 to about 100 of said dialkylsiloxy units, an average of from about 2 to about 30 of said difunctional morpholino-bearing alkylsiloxy units and an average of from about 2 to about 10 of said difunctional siloxy units having the unit formula, (R)(E)SiO_2/2.

7. An organosilicone composition as defined in claim 5 in which the said copolymer contains an average of no more than about 10 of said dialkylsiloxy units, an average of no more than about 10 of said difunctional morpholino-bearing alkylsiloxy units, and an average of no more than about 15 of said difunctional siloxy units having the unit formula, (R)(E)SiO_2/2.

9. An organosilicone composition as defined in claim 7 in which x of said copolymer has an average value of at least about 10, and the average polyoxyalkylene content of --(OC_a H_2a)_b -- is constituted of from about 20 to about 65 weight percent of oxyethylene.

10. An organosilicone composition as defined in claim 7 in which x of said copolymer is a positive number having an average value of no more than about 20, y has an average value of no more than about 20, b has an average value no more than about 30, and the polyoxyalkylene content of --(OC_a H_2a)_b -- is constituted on the average of at least 75 weight percent oxyethylene.

11. An organosilicone composition as defined in claim 7 in which the R groups of said copolymer are methyl.

12. An organosilicone composition as defined in claim 7 in which r of said copolymer is zero.

13. An organosilicone composition as defined in claim 7 in which r of said copolymer is one and e has a value of no more than four.

14. An organosilicone composition as defined in claim 7 in which p of said copolymer is one.

15. An organosilicone composition as defined in claim 7 in which p of said copolymer is zero.

16. An organosilicone composition as defined in claim 7 in which G of said copolymer is a monovalent hydrocarbon group having from 1 to 12 carbon atoms.

17. A composition as defined in claim 15 in which G is alkyl of one to four carbon atoms.

18. A composition as defined in claim 15 in which G is aryl.

19. A composition as defined in claim 15 in which G is aralkyl.

20. An organosilicone composition as defined in claim 7 in which G is R°

°

C(O)-- where R°

°

is a monovalent hydrocarbon group having from 1 to 12 carbon atoms.

21. An organosilicone composition as defined in claim 7 in which G is R°

°

NHC (O)-- where R°

°

is a monovalent hydrocarbon group having from 1 to 12 carbon atoms.

2. where r is zero or one, R°

comprises a bivalent alkylene group a carbon atom of which is bonded to silicon, --(OC_a H_2a)_b-- is a polyoxyalkylene chain where a has a value from 2 to 4 and b has an average value from about 3 to about 100, and G is an organic cap;

ii. said morpholino-bearing groups have the formula, ##STR38## wherein p is zero or has an average value from about one to about four, q is zero or one provided q is one when p has a value of more than one, R'"'"' is bivalent alkylene having from two to four carbon atoms, R" is bivalent alkylene having from two to six carbon atoms, and R¹, R², R³ and R⁴ are independently hydrogen or alkyl of one to four carbon atoms; and

iii. the monofunctional units of the copolymer have at least two alkyls of one to ten carbon atoms bonded to the respective silicon atoms thereof and the difunctional units have at least one alkyl of one to ten carbon atoms bonded to the respective silicon atoms thereof, the remaining organic group bonded to silicon of the respective monofunctional and difunctional siloxy units being alkyl of one to ten carbon atoms, said morpholino-bearing group or said polyoxyalkylene block, provided the average number of said morpholino-bearing groups and said polyoxyalkylene blocks contained in the copolymer is as aforesaid.

4. An organosilicone composition which comprises a polysiloxane-polyoxyalkylene copolymer containing monofunctional trialkylsiloxy units, (R)₃ SiO_1/2, where R has from one to ten carbon atoms, and, for every two moles of monofunctional units, an average of from about 10 to about 200 dialkylsiloxy units having the unit formula, (R)₂ SiO_2/2, where R has from one to ten carbon atoms, an average of from about 2 to about 100 difunctional morpholino-bearing alkylsiloxy units having the unit formula, ##STR39## where R is alkyl of one to ten carbon atoms, p is zero or has an average value from about one to about four, q is zero or one provided q is one when p has a value of more than one, c has a value from two to four and d has a value from two to six.

and an average of from about 2 to about 30 difunctional siloxy units having the unit formula, (R)(E)SiO.sub. 2/2, where R is alkyl of one to ten carbon atoms and E is a polyoxyalkylene block having the average composition,

6. An organosilicone composition which comprises a polysiloxane-polyoxyalkylene copolymer containing monofunctional trialkylsiloxy units, (R)₃ SiO_1/2, where R has from one to ten carbon atoms, and, for every two moles of monofunctional units, zero or an average of up to about 20 dialkylsiloxy units having the unit formula, (R)₂ SiO_2/2, where R has from one to ten carbon atoms, an average of from about 2 to about 20 difunctional morpholino-bearing alkylsiloxy units having the unit formula, ##STR40## where R is alkyl of one to ten carbon atoms, p is zero or has an average value from about one to about four, q is zero or one provided q is one when p has a value of more than one, c has a value from two to four and d has a value from two to six,

and an average of from about 2 to about 30 difunctional siloxy units having the unit formula, (R)(E)SiO_2/2, where R is alkyl of one to ten carbon atoms and E is a polyoxyalkylene block having the average composition,

8. An organosilicone composition which comprises a polysiloxane-polyoxyalkylene copolymer having the average composition, ##STR41## wherein:

R is alkyl of one to four carbon atoms;

G is an organic cap;

p is zero or one;

c has a value from two to four;

d has a value from two to six;

r is zero or one;

e has a value from two to six;

b has an average value from about 3 to about 100;

a has a value from two to four provided at least 20 weight percent of --(OC_a H_2a)_b-- is constituted of oxyethylene;

x is zero or a positive number having an average value of up to about 200;

y has an average value from about 2 to about 100; and

z has an average value from about 2 to about 30.

22. An organosilicone composition which comprises a polysiloxane-polyoxyalkylene copolymer having the average composition, ##STR42## wherein:

Me is methyl;

G is an organic cap;

e has a value from 2 to 6;

d has a value from 2 to 6;

x has an average value from about 10 to about 200;

y has an average value from about 2 to about 100;

z has an average value from about 2 to about 30;

a has a value from two to four provided an average of from about 20 to about 75 weight percent of --(OC_a H_2a)_b -- is constituted of oxyethylene units; and

b has an average value such that the average molecular weight of --(OC_a H_2a)_b -- is from about 1000 to about 6000.

24. A composition as defined in claim 22 in which R°

°

of said copolymer is alkyl of one to four carbon atoms.

23. An organosilicone composition which comprises a polysiloxane-polyoxyalkylene copolymer having the average composition, ##STR43## wherein:

Me is methyl;

R°

°

is a monovalent hydrocarbon group having one to twelve carbon atoms;

x has an average value from about 20 to about 100;

y has an average value from about 2 to about 30;

z has an average value from about 2 to about 10; and

m and n are positive numbers the average values of which are such that the average molecular weight of the chain, --(OC₂ H₄)_n (OC₃ H₆)_m --, is from about 1000 to about 6000 and the average oxyethylene content of said chain is from about 20 to about 65 weight percent.

25. A composition as defined in claim 23 in which R°

°

is methyl.

26. An organosilicone composition which comprises a polysiloxane-polyoxyalkylene copolymer having the average composition, ##STR44## wherein:

Me is methyl;

G is an organic cap;

e has a value from 2 to 6;

d has a value from 2 to 6;

x is zero or a positive number having an average value no more than about 20;

y has an average value from about 2 to about 20;

z has an average value from about 2 to about 30;

b has an average value from about 3 to about 30; and

a has a value from 2 to 4 provided an average of at least 75 weight percent of the polyoxyalkylene chain, --(OC_a H_2a)_b --, is constituted of oxyethylene units.

28. An organosilicone composition as defined in claim 26 in which x of said copolymer is a positive number.

29. An organosilicone composition as defined in claim 26 in which x is zero.

30. An organosilicone composition as defined in claim 26 in which R°

°

of said copolymer is alkyl of one to four carbon atoms.

31. An organosilicone composition as defined in claim 29 in which R°

°

is methyl.

27. An organosilicone composition which comprises a polysiloxane-polyoxyalkylene copolymer having the average composition, ##STR45## wherein:

Me is methyl;

R°

°

is a monovalent hydrocarbon group having from one to twelve carbon atoms;

x is zero or a positive number having an average value no more than about 10;

y has an average value from about 2 to about 10;

z has an average value from about 2 to about 15; and

b has an average value from about 4 to about 15.

32. A flame-retarded polyether-based urethane foam which comprises the product formed by simultaneously reacting and foaming a reaction mixture containing:

(a) a polyether polyol reactant containing an average of at least two hydroxyl groups per molecule;

(b) an organic polyisocyanate reactant containing at least two isocyanato groups per molecule;

(c) water as a source of blowing action;

(d) a catalyst comprising a tertiary-amine;

(e) a flame-retarding agent; and

(f) a foam stabilizer comprising a polysiloxane-poly(oxyethylene-oxypropylene) copolymer having the average composition, ##STR46## wherein;

R is alkyl having from one to four carbon atoms;

R'"'"' is bivalent alkylene of 2 to 4 carbon atoms;

R" is bivalent alkylene of 2 to 6 carbon atoms;

R°

comprises a bivalent alkylene group of from 2 to 6 carbon atoms a carbon atom of which is bonded to silicon;

G is an organic cap;

r is zero or one;

p is zero or one;

x has an average value from about 10 to about 200, y has an average value from about 2 to about 100, and z has an average value from about 2 to about 30, provided an average of from about 50 to about 85 weight percent of said copolymer is constituted of said --(R°

)_r (OC₂ H₄)_n (OC₃ H₆)_m OG blocks; and

m and n are numbers such that the average molecular weight of the chain, --(OC₂ H₄)_n (OC₃ H₆)_m --, is from about 1000 to about 6000 and from about 20 to about 65 weight percent of the chain is constituted of oxyethylene.

33. A flame-retarded polyether-based urethane foam which comprises the product formed by simultaneously reacting and foaming a reaction mixture containing:

(a) a polyether polyol reactant containing an average of at least two hydroxyl groups per molecule;

(b) an organic polyisocyanate reactant containing at least two isocyanato groups per molecule;

(c) water as a source of blowing action;

(d) a catalyst comprising a tertiary-amine;

(e) a flame-retarding agent; and

(f) a foam stabilizer comprising polysiloxane-poly(oxyethylene-oxypropylene) copolymers having the average composition, ##STR47## wherein;

Me is methyl, R°

°

is a monovalent hydrocarbon group having from 1 to 12 carbon atoms;

x has an average value from about 20 to about 100, y has an average value from about 2 to about 30, and z has an average value from about 2 to about 10, provided the average weight of said copolymers attributable to said --C₃ H₆ (OC₂ H₄)_n (OC₃ H₆)_m OR°

°

groupings is from about 50 to about 85 weight percent; and

m and n are numbers such that the average molecular weight of the chain, --(OC₂ H₄)_n (OC₃ H₆)_m --, is from about 1000 to about 6000 and from about 20 to about 65 weight percent of said chain is constituted of oxyethylene.

35. A flame-retarded polyester-based urethane foam as defined in claim 33 in which x of said copolymer is a positive number.

37. A process as defined in claim 35 in which said reaction mixture contains a flame-retardant as an additional component thereof.

39. A process as defined in claim 35 in which the flame-retardant contains phosphorus or halogen, both phosphorus and halogen, or phosphorus and nitrogen.

40. A process as defined in claim 35 in which the flame-retardant is present in the reaction mixture in an amount from about 1 to about 30 parts by weight per 100 parts by weight of polyol reactant (a).

34. A flame-retardant polyester-based urethane foam which comprises the product formed by simultaneously reacting and foaming a reaction mixture containing:

(a) a polyester polyol reactant containing an average of at least two hydroxyl groups per molecule;

(b) an organic polyisocyanate reactant containing at least two isocyanato groups per molecule;

(c) water as a source of blowing action;

(d) a catalyst comprising a tertiary-amine;

(e) a flame-retarding agent; and

(f) a foam stabilizer comprising a polysiloxane-polyoxyethylene copolymer having the average composition, ##STR48## wherein;

Me is methyl;

R°

°

is a monovalent hydrocarbon group having from 1 to 12 carbon atoms;

b has an average value from about 3 to about 30;

x is zero or a positive number having an average value up to about 20, y has an average value from about 2 to about 20, and z has an average value from about 2 to about 30, provided the average weight of said copolymer attributable to --C₃ H₆ (OC₂ H₄)_b OR°

°

is from about 50 to about 85 weight percent.

36. A process for producing flexible polyurethane foam which comprises simultaneously reacting and foaming a reaction mixture containing:

(a) a polyether polyol or a polyester polyol reactant having an average of at least two hydroxyl groups per molecule;

(b) a polyisocyanate reactant having at least two isocyanato groups per molecule;

(c) a blowing agent;

(d) a catalyst comprising an amine; and

(e) a foam stabilizer comprising a polysiloxane-polyoxyalkylene copolymer having the average composition, ##STR49## wherein;

R is alkyl having from one to ten carbon atoms;

t, u, v, w, the sum t+u and the sum v+w are independently zero or one, and each of the sums t+w and u+v is independently zero, one or two;

E is a polyoxyalkylene block having the average composition,

space="preserve" listing-type="equation">--(R°

).sub.r --(OC.sub.a H.sub.2a).sub.b --OG

wherein r is zero or one, R°

comprises a bivalent alkylene group a carbon atom of which is bonded to silicon, --(OC_a H_2a)_b -- is a polyoxyalkylene chain where a has a value from 2 to 4 and b has an average value from about 3 to about 100, and G is an organic cap; and

Q is a morpholino-bearing group having the formula, ##STR50## where p is zero or has an average value from about one to about four, q is zero or one provided q is one when p has a value of more than one, R'"'"' is bivalent alkylene having from two to four carbon atoms, R" is bivalent alkylene having from two to six carbon atoms, and R¹, R², R³ and R⁴ are independently hydrogen or alkyl having from one to four carbon atoms;

and, when reactant (a) is a polyether polyol, x has an average value from about 10 to about 200, y has an average value from about 2 to about 100 and z has an average value from about 2 to about 30, provided an average of from about 50 to about 85 weight percent of said copolymer is constituted of E; and

the average polyoxyalkylene content of --(C_a H_2a O)_b -- of E is constituted of from about 20 to about 75 weight percent of oxyethylene; and

when reactant (a) is a polyester polyol, x is zero or a positive number having an average value up to about 20, y has an average value from about 2 to about 20 and z has an average value from about 2 to about 30, provided an average of from about 50 to about 85 weight percent of said copolymer is constituted of E; and

the average polyoxyalkylene content of --(C_a H_2a O)_b -- of E is constituted of at least 75 weight percent of oxyethylene.

38. A flame-retarded flexible polyurethane foam produced by the process of claim 36.

41. A flame-retardant polyester-based urethane foam which comprises the product formed by simultaneously reacting and foaming a reaction mixture containing:

(a) a polyester polyol reactant containing an average of at least two hydroxyl groups per molecule;

(b) an organic polyisocyanate reactant containing at least two isocyanato groups per molecule;

(c) water as a source of blowing action;

(d) a catalyst comprising a tertiary-amine;

(e) a flame-retarding agent; and

(f) a foam stabilizer comprising a polysiloxane-polyoxyethylene copolymer having the average composition, ##STR51## wherein;

R is alkyl having from one to four carbon atoms;

R'"'"' is bivalent alkylene of 2 to 4 carbon atoms;

R" is bivalent alkylene of 2 to 6 carbon atoms;

R°

comprises a bivalent alkylene group of from 2 to 6 carbon atoms a carbon atom of which is bonded to silicon;

G is an organic cap;

r is zero or one;

p is zero or one;

b has an average value from about 3 to about 30;

x is zero or a positive number having an average value up to about 20, y has an average value from about 2 to about 20, and z has an average value from about 2 to about 30, provided the average weight of said copolymer attributable to --(R°

)_r (OC₂ H₄)_b OG is from about 50 to about 85 weight percent.