Dithiocarbonate containing polyols as polymer polyol stabilizers

Patent metadata

Field	Value
Publication number	US-11149145-B2
Application number	US-201916687755-A
Country	US
Kind code	B2
Filing date	Nov 19, 2019
Priority date	Dec 20, 2017
Publication date	Oct 19, 2021
Grant date	Oct 19, 2021

Abstract

This invention relates to novel macromers containing dithiocarbonate (or xanthate) groups, novel preformed stabilizers comprising macromers, and novel polymer polyols comprising the novel macromers and/or novel preformed stabilizers. This invention also relates to processes for the preparation of these materials. Other aspects of this invention include foams comprising the novel polymer polyols and a process for preparing foam comprising the novel polymer polyols.

First claim

What is claimed is:

1. A polymer polyol comprising the in-situ, free-radical polymerization product of:
(A) a base polyol;
(B) a component comprising at least one of:
(1) a macromer containing dithiocarbonate functionality that comprises the reaction product of: (a) a polyether dithiocarbonate polyol having an equivalent weight of 230 Da to 5600 Da, and functionality of 1 to 8, having a dithiocarbonate content of from 0.05% to 20% by weight, and which comprises the copolymerization product of a reaction mixture comprising (i) one or more starter polyether polyols having an equivalent weight less than 1000 Da, an OH number greater than 56 mg KOH/g polyol, and a functionality of 1 to 8, (ii) an alkylene oxide, and (iii) carbon disulfide, in the presence of (iv) an alkoxylation catalyst; optionally, with (b) an ethylenically unsaturated compound containing hydroxyl reactive groups; optionally, in the presence of (c) a catalyst;
and
(2) a preformed stabilizer that comprises the free-radical polymerization product of: (1) a macromer which comprises the reaction product of: (a) a polyether dithiocarbonate polyol having an equivalent weight of 230 Da to 5600 Da, and functionality of 1 to 8, having a dithiocarbonate content of 0.05% to 20% by weight, and which comprises the copolymerization product of a reaction mixture comprising (i) one or more starter polyether polyols having an equivalent weight less than 1000 Da, an OH number greater than 56 mg KOH/g polyol, and a functionality of 1 to 8, (ii) an alkylene oxide, and (iii) carbon disulfide, in the presence of (iv) an alkoxylation catalyst; with, optionally, (b) an ethylenically unsaturated compound containing hydroxyl reactive groups; optionally, in the presence of (c) a catalyst; with (2) at least one ethylenically unsaturated monomer, in the presence of (3) a free-radical polymerization initiator, and, optionally, (4) a liquid diluent, and, optionally (5) a polymer control agent;

and
(C) at least one ethylenically unsaturated monomer;
in the presence of
(D) a free-radical polymerization initiator;
and, optionally,
(E) a polymer control agent.

2. A process of preparing the polymer polyol of claim 1 , comprising
(I) free-radically polymerizing:
(A) a base polyol;
(B) a component comprising at least one of:
(1) a macromer containing dithiocarbonate functionality that comprises the reaction product of: (a) a polyether dithiocarbonate polyol having an equivalent weight of 230 Da to 5600 Da, and functionality of 1 to 8, having a dithiocarbonate content of from 0.05% to 20% by weight, and which comprises the copolymerization product of a reaction mixture comprising (i) one or more starter polyether polyols having an equivalent weight less than 1000 Da, an OH number greater than 56 mg KOH/g polyol, and a functionality of 1 to 8, (ii) an alkylene oxide, and (iii) carbon disulfide, in the presence of (iv) an alkoxylation catalyst; optionally, with (b) an ethylenically unsaturated compound containing hydroxyl reactive groups; optionally, in the presence of (c) a catalyst;
and
(2) a preformed stabilizer that comprises the free-radical polymerization product of: (1) a macromer which comprises the reaction product of: (a) a polyether dithiocarbonate polyol having an equivalent weight of 230 Da to 5600 Da, and functionality of 1 to 8, having a dithiocarbonate content of 0.05% to 20% by weight, and which comprises the copolymerization product of a reaction mixture comprising (i) one or more starter polyether polyols having an equivalent weight less than 1000 Da, an OH number greater than 56 mg KOH/g polyol, and a functionality of 1 to 8, (ii) an alkylene oxide, and (iii) carbon disulfide, in the presence of (iv) an alkoxylation catalyst; with, optionally, (b) an ethylenically unsaturated compound containing hydroxyl reactive groups; optionally, in the presence of (c) a catalyst; with (2) at least one ethylenically unsaturated monomer, in the presence of (3) a free-radical polymerization initiator, and, optionally, (4) a liquid diluent, and, optionally (5) a polymer control agent;

and
(C) at least one ethylenically unsaturated monomer,
in the presence of
(D) a one free-radical polymerization initiator,
and, optionally,
(E) a polymer control agent.

3. The polymer polyol of claim 1 , wherein (B)(1)(a) the polyether dithiocarbonate polyol has an equivalent weight of 280 Da to 5400 Da, a functionality of 2 to 7, a dithiocarbonate content of 0.10 to 15% by weight, and comprises the reaction product of (i) one or more starter polyether polyols having an OH number of at least 112 mg KOH/g polyol to 1850 mg KOH/g polyol, and a functionality of 2 to 7; (ii) the alkylene oxide comprises ethylene oxide and/or propylene oxide; and (iv) the alkoxylation catalyst comprises a double metal cyanide complex catalyst.

4. The polymer polyol of claim 1 , wherein (B)(1)(b) the ethylenically unsaturated compound containing hydroxyl reactive groups comprises methyl methacrylate, ethyl methacrylate, maleic anhydride, 3-isopropenyl-α,α-dimethyl benzyl isocyanate, 2-isocyanatoethyl methacrylate, adducts of isophorone diisocyanate and 2-hydroxyethyl methacrylate, adducts of toluene diisocyanate and 2-hydroxylpropyl acrylate, or mixtures thereof.

5. The polymer polyol of claim 1 , wherein (B)(1)(c) the catalyst comprises an organotin catalyst or a bismuth catalyst.

6. The polymer polyol of claim 1 , wherein the preformed stabilizer comprises the free-radical polymerization product of (1) the macromer, with (2) an ethylenically unsaturated monomer, in the presence of (3) a free-radical polymerization initiator, (4) a liquid diluent, and (5) a polymer control agent.

7. The polymer polyol of claim 1 , wherein (B)(2)(2) the ethylenically unsaturated monomer comprises styrene, acrylonitrile or a mixture thereof.

8. The polymer polyol of claim 1 , wherein (B)(2)(3) the free-radical polymerization initiator comprises a peroxide initiator, an azo initiator, or a mixture of a peroxide initiator and an azo initiator.

9. The polymer polyol of claim 1 , wherein (B)(2)(4) the diluent comprises isopropanol, a polyol having an OH number of 20 mg KOH/g polyol to 280 mg KOH/g polyol, or a mixture of a monol and a polyol.

10. The polymer polyol of claim 1 , wherein (B)(2)(5) the polymer control agent comprises isopropanol, toluene, ethylbenzene, dodecylmercaptan, carbon tetrachloride, carbon tetrabromide, chloroform, methylene chloride or a mixture thereof.

Assignees

• Covestro Llc
• Covestro Deutschland Ag

Inventors

• Adkins Rick L
• Reese Jack R
• Müller Thomas Ernst
• Gürtler Christoph
• Rauwald Urs
• Subhani Muhammad Afzal
• Jakoby Verena
• Köhler Burkhard
• Leitner Walter

Classifications

• C08G18/4837 Primary

  and other oxyalkylene units · CPC title

• C08G18/632

  onto polyethers · CPC title

• C08L81/00

  Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers · CPC title

• C08G18/3275

  containing two hydroxy groups · CPC title

• C08J2375/04

  Polyurethanes · CPC title