STABILISER FOR POLYOLEFIN-IN-POLYETHER POLYOL DISPERSIONS

Abstract

Stabiliser, comprising the reaction product of at least one macromer with at least one C.sub.4-30-alkyl(meth)acrylate in at least one polyether polyol 1 in the presence of at least one free radical polymerisation catalyst and optionally at least one chain transfer agent, the at least one macromer being at least one molecule which comprises in its structure one or more polymerisable double bonds, able to copolymerise with C.sub.4-30-alkyl(meth)acrylates and which furthermore comprises in its structure one or more hydroxyl-terminated polyether chains.

Claims

1-26. (canceled)

27. A stabiliser, comprising a reaction product of at least one macromer with at least one C.sub.4-30-alkyl(meth)acrylate in at least one polyether polyol 1 in the presence of at least one free radical polymerisation catalyst and optionally at least one chain transfer agent, the at least one macromer being at least one molecule which comprises in its structure at least one polymerisable double bond, able to copolymerise with a C.sub.4-30-alkyl(meth)acrylate and which furthermore comprises in its structure at least one hydroxyl-terminated polyether chain, wherein a weight ratio of the reaction product of the at least one macromer with the at least one C.sub.4-30-alkyl(meth)acrylate to the at least one polyether polyol 1 is in a range of from 20:80 to 80:20, and the stabiliser has a particle size DSO smaller than 0.5 m as determined by static laser diffraction, using a Mastersizer 2000 (Malvern Instruments Ltd), of a sample comprising the stabiliser and diluted with isopropanol in order to obtain an optical concentration suitable for the static laser diffraction.

28. The stabiliser of claim 27, wherein the weight ratio of the reaction product of the at least one macromer with the at least one C.sub.4-30-alkyl(meth)acrylate to the at least one polyether polyol 1 is in a range of from 50:50 to 70:30.

29. The stabiliser of claim 27, wherein an amount of the at least one C.sub.4-30-alkyl(meth)acrylate is 5 to 50 wt %, based on a total amount of the stabiliser, which is 100 wt %.

30. The stabiliser of claim 27, wherein the at least one C.sub.4-30-alkyl(meth)acrylate is employed together with acrylonitrile, styrene, or a mixture thereof.

31. The stabiliser of claim 27, wherein the reaction product of the at least one macromer with the at least one C.sub.4-30-alkyl(meth)acrylate is free from polymerised acrylonitrile and styrene units.

32. The stabiliser of claim 27, wherein the at least one macromer is obtained by reacting at least one polyether polyol 2 with an organic compound comprising a polymerisable double bond able to copolymerise with a C.sub.4-30-alkyl(meth)acrylate and a carboxyl, anhydride, isocyanate, epoxy or other functional group able to react with an active hydrogen-containing group, wherein a molar ratio of polymerisable double bonds to hydroxyl groups of the polyether polyol 2 to be reacted is in a range of from 0.03 to 0.30.

33. The stabiliser of claim 32, wherein the organic compound comprising the polymerisable double bond able to copolymerise with the C.sub.4-30-alkyl(meth)acrylate and the carboxyl, anhydride, isocyanate, epoxy or other functional group able to react with the active hydrogen-containing group is selected from the group consisting of isocyanate ethyl methyl acrylate (IEM), 1,1-dimethyl meta-isopropenyl benzyl isocyanate (TMI) and mixtures thereof.

34. The stabiliser of claim 32, wherein the at least one polyether polyol 1 and the at least one polyether polyol 2 are each independently a two- to eight-functional polyether polyol with a molecular weight (M.sub.n) of from 500 to 30,000 g/mol.

35. The stabiliser of claim 34, wherein the at least one polyether polyol 1 and the at least one polyether polyol 2 are the same.

36. The stabiliser of claim 34, wherein the at least one polyether polyol 2 is a six-functional polyether polyol and the at least one polyether polyol 1 is a three-functional polyether polyol.

37. A process for preparing the stabiliser of claim 27, the process comprising reacting the at least one macromer with at least one C.sub.4-30-alkyl(meth)acrylate in at least one polyether polyol 1 in the presence of a free radical polymerisation catalyst and optionally at least one chain transfer agent.

38. A process for preparing a dispersion of at least one polyolefin in at least one polyol 3, the process comprising a melt emulsification of the at least one polyolefin, the at least one polyol 3 and at least one stabiliser of claim 27.

39. The process of claim 38, wherein the at least one polyolefin is selected from the group consisting of a polyethylene, a polypropylene, a polybutylene, a polyisobutylene, a polybutadiene and mixtures thereof.

40. The process of claim 38, wherein the at least one polyol 3 comprises a two- to eight-functional polyol with a molecular weight (M.sub.n) of from 500 to 30,000 g/mol and may be the same as the at least one polyether polyol 1.

41. The process of claim 38, wherein the at least one polyol 3 is selected from the group consisting of a polyetherol; a polyesterol; a polycarbonate polyol; a polyether amine; a hydroxyl-functionalised fatty acid derivative of a polyetherol, polyesterol, polycarbonate polyol or polyether amine; an alkoxylation product of a polyetherol, polyesterol, polycarbonate polyol or polyether amine; and mixtures thereof.

42. The process of claim 38, wherein the dispersion comprises 5 to 20 wt % of the at least one stabiliser and 10 to 60 wt % of the at least one polyolefin, based on a total amount of the dispersion, which is 100 wt %.

43. The process of claim 38, wherein the melt emulsification is performed in an extruder at a temperature in a range of from 140 to 240 C. or in a kneader at a temperature in a range of from 180 to 260 C.

44. A process for preparing a polyurethane, the process comprising: preparing a dispersion of at least one polyolefin in at least one polyol 3, the dispersion comprising at least one stabiliser of claim 27, the melt emulsification of the at least one polyolefin, the at least one polyol 3 and the least one stabiliser, mixing the dispersion with a polyisocyanate and, if appropriate, at least one further compound having hydrogen atoms which are reactive towards an isocyanate, a chain extender and/or crosslinker, a catalyst, a blowing agent and a further additive, and reacting the mixture to form the polyurethane.

45. The process of claim 44, wherein the polyurethane is a polyurethane foam and the mixture comprises a blowing agent.

46. The process of claim 44, wherein the polyurethane is a compact polyurethane material.

Description

EXAMPLES

[0085] In the following sections, some experimental examples are given in order to illustrate some aspects of the present invention.

Example 1

Preformed Stabiliser

[0086] A three litre reactor was charged with a polyol mixture of polyol Lupranol 2095 (trifunctional polyetherol with primary OH endgroups based on glycerol with MW 5000 by BASF SE) and a six functional polyetherol modified with 3-isopropenyl-,-dimethylbenzene isocyanate (1 mol per mole polyetherol). The mass ratio of the polyetherols was 29:47.5. Furthermore, 22.5 wt % behenyl acrylate, 0.5 wt % dodecanthiol and 0.5 wt % dimethyl-2,2-azobis(2-methylpropionate) were added to this solution. The solution was heated to 70 C. and stirred for 20 h.

Example 2

[0087] Dispersion of Polyisobutylene MW 1,000 g/mol (Laboratory Batch Process)

[0088] A 700 mL glass reactor is charged with 250 g polyol Lupranol 2095 (trifunctional polyetherol with primary OH endgroups based on glycerol with MW 5000 by BASF SE), 50 g preformed stabiliser and 200 g polyisobutylene with molecular weight 1,000 g/mol (Glissopal 1000 by BASF). The reaction mixture was heated to 240 C. and stirred at 600 rpm for 2 h. A white viscous solution was yielded. The viscosity of the product was 6630 mPas (1/50 1/s at 25 C.) and a particle diameter of D[3,2] 1.566 m was determined. The product was phase stable for at least several weeks.

Example 3

[0089] Dispersion of Polyisobutylene MW 1,000 g/mol (Large-Scale Melt Emulsification)

[0090] A dispersion of 40 wt % polyisobutylene (MW 1000 g/mol) in 50 wt % polyetherol GEP330NY by Gaoqiao Sinopec (trifunctional polyetherol with primary OH endgroups based on glycerol with MW 5000) was prepared by melt emulsification process. Preformed stabiliser (10 wt %) was added during the process. The extruder zones were heated to following temperatures: 25 C. (zone 1), 180 C. (zone 2-10) and the head of the extruder was heated to 180 C. The speed of the extruder was adjusted to 800 rpm and the material was fed into zone 2 with 60 kg/h. A rotor-stator was attached to the extruder head (4,000 rpm). A viscosity of 4175 mPas and mean particle size of 5.276 m was determined for the phase-stable product and the product was stable for at least several weeks.

Example 4

[0091] Dispersion of Polyisobutylene MW 2.300 g/mol (Laboratory Batch Process)

[0092] A 700 mL glass reactor is precharged with 50 g preformed stabiliser and 200 g polyisobutylene with molecular weight 2,300 g/mol (Glissopal 2300 by BASF). The reaction mixture was heated to 240 C. and stirred at 600 rpm. 250 g polyol Lupranol 2095 (trifunctional polyetherol with primary OH endgroups based on glycerol with MW 5000 by BASF SE) was slowly added to the reaction mixture followed by 1 h stirring at reaction temperature. A white viscous solution was yielded. The viscosity of the product was 654 mPas (1/50 1/s at 75 C.) and a particle diameter of D[3,2] 2.667 m was determined. The product was phase stable for at least several weeks.

Example 5

[0093] Dispersion of Polyisobutylene MW 2,300 g/mol (Large-Scale Melt Emulsification)

[0094] A dispersion of 40 wt % polyisobutylene (MW 2300 g/mol) in 50 wt % polyetherol GEP330NY by Gaoqiao Sinopec (trifunctional polyetherol with primary OH endgroups based on glycerol with MW 5000) was prepared by melt emulsification process. Preformed stabiliser (10 wt %) was added during the process. The extruder zones were heated to following temperatures: 25 C. (zone 1), 170 C. (zone 2-10) and the head of the extruder was heated to 170 C. The speed of the extruder was adjusted to 800 rpm and the material was fed into zone 2 with 60 kg/h. A rotor-stator was attached to the extruder head (8,000 rpm). A viscosity of 3049 mPas and mean particle size of 4.507 m was determined for the phase-stable product and the product was stable for at least several weeks.

Example 6

[0095] Dispersion of Polyisobutylene MW 20,000 g/mol (Laboratory Batch Process)

[0096] A 700 mL glass reactor is precharged with 50 g preformed stabiliser and 200 g polyisobutylene with molecular weight 20,000 g/mol (Oppanol B10 by BASF). The reaction mixture was heated to 240 C. and stirred at 600 rpm. 250 g polyol Lupranol 2095 (trifunctional polyetherol with primary OH endgroups based on glycerol with MW 5000 by BASF SE) was slowly added to the reaction mixture followed by 1 h stirring at reaction temperature. A white dispersion was yielded.

[0097] The viscosity of the product was 10590 mPas (1/50 1/s at 25 C.) and a particle diameter of D[3,2] 2.284 m was determined. The product was phase stable for at least several weeks.

Example 7

[0098] Dispersion of Polypropylene MW 20,000 g/mol (Laboratory Batch Process)

[0099] A 700 mL glass reactor is charged with 160 g bifunctional polyetherol polyol Lupranol 1100 (bifunctional polyetherol with secondary OH endgroups with MW 1000 by BASF SE), 80 g preformed stabiliser and 160 g polypropylene with molecular weight 20,000 g/mol by Sigma Aldrich. The reaction mixture was heated to 240 C. and stirred at 400 rpm for 1 h. A white viscous solution was yielded. The viscosity of the product was 6853 mPas (1/100 1/s at 75 C.) and a particle diameter of D[3,2] 2.643 m was determined. The product was phase stable.