Polymer polyols with ultra-high solids contents

• US 7,759,423 B2
• Filed: 08/02/2004
• Issued: 07/20/2010
• Est. Priority Date: 08/02/2004
• Status: Active Grant

• Current Assignee: Covestro LLC (Covestro AG)
• Original Assignee: Bayer Materialscience LLC (Covestro AG)
• Inventors: Chauk, Shriniwas S.
• Primary Examiner(s): COONEY, JOHN M
• Application Number:
  US10/909,493
• Publication Number:
  US 20060025492A1
• Time in Patent Office: 2,178 Days
• Field of Search: 528/75, 525/123, 524/762, 524/765, 524/769, 524/773, 252/182.24
• US Class Current: 524/762
• CPC Class Codes: C08F 283/06 on to polyethers, polyoxymethylenes or polyacetals C08F283/004 takes precedence
• CPC Class Codes: C08F 290/062 Polyethers
• CPC Class Codes: C08G 18/48 Polyethers
• CPC Class Codes: C08G 18/632 onto polyethers
• CPC Class Codes: C08G 18/636 characterised by the presence of a dispersion-stabiliser
• CPC Class Codes: C08G 18/672 Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
• CPC Class Codes: C08G 18/68 Unsaturated polyesters
• CPC Class Codes: C08G 18/702 Isocyanates or isothiocyanates containing compounds having carbon-to-carbon double bonds; Telomers thereof
• CPC Class Codes: C08G 2110/0008 flexible
• CPC Class Codes: C08G 2110/005 < 50kg/m3
• CPC Class Codes: C08G 2110/0083 prepared using water as the sole blowing agent

Abstract

The present invention relates to ultra-high solids content polymer polyols which have good filterability while maintaining a reasonable viscosity, and to a process for the preparation of these ultra-high solids contents polymer polyols. These polymer polyols comprise the free-radical polymerization product of (A) a base polyol, (B) a pre-formed stabilizer, (C) at least one ethylenically unsaturated monomer, (D) at least one free-radical polymerization initiator, and (E) at least one chain transfer agent. The solids contents varies from 60% to about 85% by weight.

Claims

1. A, stable, ultra-high solids polymer polyol composition, comprising the reaction product of:

(A) a base polyol;

(B) from 7.5% to 35% by weight, based on 100% by weight of the polymer polyol, of a high potency preformed stabilizer which comprises

(1) a macromer or precursor which comprises an adduct of an alcohol corresponding to the average formula;

A(OROX)<sub>≧

1</sub>,

wherein;

A represents a polyvalent organic moiety which has a free valence ≧

1,

R represents the divalent residue comprising an alkylene oxide moiety,

and

X represents one or more of an organic moiety containing reactive unsaturation which is copolymerizable with A and hydrogen and one of such X is the organic moiety containing reactive unsaturation and the remaining X'"'"'s are hydrogen;

(2) at least one free-radically polymerizable ethylenically unsaturated monomer,

(3) a free-radical initiator,

and

(4) a liquid diluent comprising a monol;

and

(C) at least one ethylenically unsaturated monomer;

in the presence of

(D) at least one free-radical polymerization initiator;

and

(E) a chain transfer agent;

wherein the polymer polyol has a solids content greater than 60% by weight, and the polymer polyol has a kinematic viscosity less than or equal to (X e<sup>[−

4.5×

LN(1−

(Y/100))]</sup>) wherein;

X;

represents the kinematic viscosity of the base polyol,

Y;

represents the total solids content expressed as weight percent,

LN;

represents the logarithm to natural base,

and the polymer polyol has product stability such that essentially 100% passes through a 150 mesh screen and at least about 99% passes through a 700 mesh screen.

2. The polymer polyol of claim 1, wherein the solids content ranges from greater than 60 to about 85% by weight.

3. The polymer polyol of claim 1, wherein the solids content is from greater than 60 to about 82% by weight.

4. The polymer polyol of claim 1, wherein the product stability is such that at least 99.5% passes through a 700 mesh screen.

5. The polymer polyol of claim 1, wherein (D) said free-radical initiator is selected from the group consisting of peroxide initiators, azo initiators and mixtures thereof.

6. The polymer polyol of claim 5, wherein (D) said free-radical initiator is a peroxide initiator selected from the group consisting of:

tert-amyl peroxypivalate, tert-butyl peroxypivalate, tert-butyl peroxydiethylacetate, dilauroyl peroxide, dioctanoyl peroxide, didecanoyl peroxide, didodecanoyl peroxide, 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane, tert-amyl peroxy-2-ethyl hexanoate, tert-butyl peroxy-2-ethyl hexanoate, dibenzoyl peroxide, 1,1,3,3-tetramethylbutyl peroxypivalate, di(3,5,5-trimethylhexanoyl)peroxide, 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, 1,1-dimethyl-3-hydroxybutyl peroxy-2-ethylhexanoate and mixtures thereof.

7. The polymer polyol of claim 5, wherein (D) said free-radical initiator is an azo initiator selected from the group consisting of:

2,2-azobis(isobutyronitrile), 2,2′

-azobis(2-methylbutyronitrile) and mixtures thereof.

8. The polymer polyol of claim 1, wherein (C) said ethylenically unsaturated monomer is selected from the group consisting of acrylonitrile, styrene, dibromostyrene, vinylidene chloride and mixtures thereof.

9. The polymer polyol of claim 8, wherein said ethylenically unsaturated monomers comprise styrene and acrylonitrile in a weight ratio of from 100:

0 to 40;

60.

10. The polymer polyol of claim 1, wherein (B) (1) said macromer or precursor which comprises an adduct of an alcohol is further reacted with an organic polyisocyanate.

11. The polymer polyol of claim 1, wherein the total amount of (E) chain transfer agents ranges from about 0.1% to 30% by weight, based on the weight of the polymer polyol.

12. The polymer polyol of claim 1, wherein said base polyol has an OH number of from 10 to 1,000 and a functionality of from 2 to 8.

13. A process for preparing a stable, ultra-high solids polymer polyol, comprising:

(1) free-radically polymerizing;

(A) a base polyol,

(B) from 7.5% to 35% by weight, based on 100% by weight of the polymer polyol, of a high potency preformed stabilizer which comprises

(1) a macromer or precursor which comprises an adduct of an alcohol corresponding to the average formula;

A(OROX)<sub>≧

1</sub>,

wherein;

A represents a polyvalent organic moiety which has a free valence ≧

1,

R represents the divalent residue comprising an alkylene oxide moiety,

and

X represents one or more of an organic moiety containing reactive unsaturation which is copolymerizable with A and hydrogen and one of such X is the organic moiety containing reactive unsaturation and the remaining X'"'"'s are hydrogen;

(2) at least one free-radically polymerizable ethylenically unsaturated monomer,

(3) a free-radical initiator,

and

(4) a liquid diluent comprising a monol;

and

(C) at least one ethylenically unsaturated monomer, in the presence of;

(D) at least one free-radical polymerization initiator,

and

(E) a chain transfer agent;

wherein the polymer polyol has a solids content greater than 60% by weight, and the polymer polyol has a kinematic viscosity less than or equal to (X e<sup>[−

4.5×

LN(1−

Y/100))]</sup>) wherein;

X;

represents the kinematic viscosity of the base polyol,

Y;

represents the total solids content expressed as weight percent,

LN;

represents the logarithm to natural base,

and the polymer polyol has product stability such that essentially 100% passes through a 150 mesh screen and at least about 99% passes through a 700 mesh screen.

14. The process of claim 13, wherein the solids content ranges from greater than 60% to about 85% by weight.

15. The process of claim 13, wherein the solids content ranges from greater than 60% to about 82% by weight.

16. The process of claim 13, wherein the product stability is such that at least 99.5% passes through a 700 mesh screen.

17. The process of claim 13, wherein (D) said free-radical initiator is selected from the group consisting of peroxide initiators, azo initiators, and mixtures thereof.

18. The process of claim 17, wherein (D) said free-radical initiator is a peroxide initiator selected from the group consisting of:

tert-amyl peroxypivalate, tert-butyl peroxypivalate, tert-butyl peroxydiethylacetate, dilauroyl peroxide, dioctanoyl peroxide, didecanoyl peroxide, didodecanoyl peroxide, 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane, tert-amyl peroxy-2-ethyl hexanoate, tert-butyl peroxy-2-ethyl hexanoate, dibenzoyl peroxide, 1,1,3,3-tetramethylbutyl peroxypivalate, di(3,5,5-trimethylhexanoyl)peroxide, 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, 1,1-dimethyl-3-hydroxybutyl peroxy-2-ethylhexanoate and mixtures thereof.

19. The process of claim 17, wherein (D) said free-radical initiator is an azo initiator selected from the group consisting of:

2,2-azobis(isobutyronitrile), 2,2′

-azobis(2-methylbutyronitrile) and mixtures thereof.

20. The process of claim 13, wherein (C) said ethylenically unsaturated monomer is selected from the group consisting of acrylonitrile, styrene, dibromostyrene, vinylidene chloride and mixtures thereof.

21. The process of claim 20, wherein said ethylenically unsaturated monomers comprise styrene and acrylonitrile in a weight ratio of from 100:

0 to 40;

60.

22. The process of claim 13, wherein (B) (1) said macromer or precursor which comprises an adduct of an alcohol is further reacted with an organic polyisocyanate.

23. The process of claim 13, wherein the total amount of (E) chain transfer agents ranges from about 0.1% to 30% by weight, based on the weight of the polymer polyol.

24. The process of claim 13, wherein said base polyol has a functionality of 2 to 8 and an OH number of from 10 to 1,000.

25. The process of claim 13, wherein the polymerization is at a temperature of 80 to 150°

C.