SYNTHESIS OF POLYMER POLYOLS IN UNSATURATED POLYOLS, POLYMER POLYOLS AND THEIR USE

Abstract

The present invention relates to the synthesis of polymer polyols in unsaturated polyols as liquid phase, polymer polyols and their use.

Claims

1. A process for making a polymer polyol, comprising mixing at least one melted thermoplastic styrene-acrylonitrile-copolymer (TP) with at least one polyol (P) in the presence of at least one stabilizer (S), comprising from 10 to 70% by weight, based on the sum of all components, of at least one polyol P2, and at least one polyol CSP which comprises the reaction product of at least one macromer M, styrene and acrylonitrile in polyol P2, optionally with an initiator and/or a chain transfer agent, wherein the content of macromer M of the stabilizer (S) is between 30-70 wt %, based on the sum of all components, and/or wherein the polyol CSP is optionally comb-structured, wherein the polyol (P) comprises at least one unsaturated carbon-carbon bond per molecule, and wherein the macromere M is defined as a molecule which comprises one or more polymerizable double bonds able to copolymerize with vinylic monomers and which comprises one or more hydroxyl-terminated polyether chains.

2. The process according to claim 1, wherein the process is a continuous process.

3. The process according to claim 1, wherein the process is a semi-batch process.

4. The process according to claim 1, wherein the polyol (P) comprises at least one polybutadiene diol.

5. The process according to claim 1, wherein the polyol (P) comprises at least one natural oil with an at least one OH functional group per molecule.

6. The process according to claim 1, wherein the polyol (P) consists of castor oil.

7. The process according to claim 1, wherein the polyol (P) on average has at least two double bonds per molecule.

8. The process according to claim 1, wherein the polyol (P) consists of a polybutadiene polyol.

9. The process according to claim 1, wherein the polyol (P) consists of a polybutadiene polyol and wherein the polyol (P) on average has at least 2 double bonds per molecule.

10. The process according to claim 1, wherein the stabilizer S consists of one or two polyols P2 and one or two polyols CSP which comprise the reaction product of at least one macromer M, styrene and acrylonitrile in P2, optionally with an initiator selected from the group consisting of azo initiators and peroxide initiators, and/or a chain transfer agent selected from the group consisting of dodecane thiol, isopropanol and 2-butanol.

11. The process according to claim 1, wherein the stabilizer S consists of one or two polyols P2 and one or two polyols CSP which consist of the reaction product of a macromer M, styrene and acrylonitrile in P2.

12. The process according to claim 1, wherein the macromer M has an average molecular weight M.sub.w of from 1000 to 50000 g/mol.

13. The process according to claim 1, wherein the macromer M has from 0.2 to 1.2 polymerizable ethylenically unsaturated groups per molecule in average and/or from 2 to 8 hydroxyl groups per molecule.

14. The process according to claim 1, wherein the macromer M is obtained by reacting TMI with a polyether polyol PM, optionally in the presence of a Lewis acid catalyst.

15. The process according to claim 14, wherein the polyether polyol PM used in the production of the macromer M is selected from the group consisting of three- and sixfunctional polyether polyols.

16. The process according to claim 1, wherein the ratio of styrene to acrylonitrile in the stabilizer (S) is greater than 1:1.

17. The process according to claim 1, wherein the viscosity of the stabilizer is between 1000 and 100000 mPas at 25° C., determined according to DIN EN ISO 3219 and a shear rate of 100 1/s.

18. The process according to claim 1, wherein the overall content of styrene of the stabilizer (S) is between 0.5 and 20 wt %, and/or the overall content of acrylonitrile of the stabilizer (S) is between 0.5 and 15 wt %, and/or the overall content of the polyol P2 of the stabilizer (S) is between 20 and 70 wt %.

19. The process according to claim 1, wherein the stabilizer (S) comprises no additional solvent.

20. The process according to claim 1, wherein the stabilizer (S) is produced by free radical polymerization of styrene, acrylonitrile and at least one macromer M in the presence of at least one polyol P2.

21. The process according to claim 20, wherein at least one chain transfer agent is used in the production of stabilizer (S).

22. The process according to claim 21, wherein at least one chain transfer agent is selected from the group consisting of dodecane thiol, isopropanol and 2-butanol.

23. The process according to claim 21, wherein less than 5% by weight of the chain transfer agents are used in sum, relative to the weight of the entire reaction mixture.

24. The process according to claim 20, wherein the reaction temperature during the production of the stabilizer (S) is between 80° and 150° C. and/or the reaction takes between 10 min and 300 min.

25. The process according to claim 20, wherein at least one initiator is used in the production of the stabilizer (S).

26. The process according to claim 20, wherein less than 1% by weight of the initiators are used in sum in the production of the stabilizer (S), relative to the weight of the entire reaction mixture.

27. The process according to claim 1, wherein the polyol P2 contained in the stabilizer S is selected from the group consisting of polyether polyols.

28. The process according to claim 1, wherein, in a first step (1), TP, P and S are fed into an extruder (E) to form an initial dispersion, and the initial dispersion obtained from the extruder is then fed, in a second step (2), into at least one rotor-stator device (RS) comprising at least one rotor-stator combination, and subsequently (3) the dispersion is cooled below the T.sub.g of the thermoplastic styrene-acrylonitrile-copolymer (TP) to obtain the final polymer polyol.

29. The process according to claim 28, wherein the extruder (E) is divided into at least two separate process zones.

30. The process according to claim 29, wherein TP is fed into the first process zone Z1 of the extruder E, S is fed into the second process zone Z2 or a later process zone, and P is fed into one of the process zones following the process zone of addition of S, wherein the terms “first” and “second” refer to the flow direction of the reaction mixture in the extruder E.

31. The process according to claim 28, wherein there is at least one process zone of the extruder E with no addition of components between the addition of the stabilizer S and the addition of the polyol P.

32. The process according to claim 28, wherein P is fed into at least two different process zones of the extruder E.

33. The process according to claim 29, wherein the extruder (E) is operated at a barrel temperature in the range of between 160° to 250° C. in at least one of the process zones.

34. The process according to claim 28, wherein the extruder (E) has a rotation speed in the range of 400 to 1200 rpm.

35. The process according to claim 28, wherein a stripping column or stripping-vessel is used after the rotor-stator device to remove volatile material.

36. The process according to claim 28, wherein at least one of the at least one-level rotor-stator devices (RS) are operated at a set temperature in the range of between 160° to 250° C.

37. The process according to claim 28, wherein at least one of the rotor-stator devices (RS) have a circumferential speed in the range of 10 to 60 s.sup.−1.

38. The process according to claim 28, wherein at least one of the rotor-stator devices comprise at least two rotor-stator combinations.

39. The process according to claim 38, wherein single rotor-stator combinations have differing teeth.

40. The process according to claim 28, wherein the polyol (P) is added to the extruder (E) at a temperature of above 100° C.

41. The process according to claim 28, wherein the stabilizer (S) is added to the extruder (E) at a temperature of above 100° C.

42. A polymer polyol obtained by the process of claim 1.

43-44. (canceled)

Description

EXAMPLE 1: USE OF STABILIZER 2 WITH CASTOR OIL

[0072] A round bottom-flasked equipped with a stirrer and a nitrogen inlet was charged with 280 g of Luran® VLR and 70 g of the stabilizer 1 and heated to 240° C. under nitrogen atmosphere. The mixture was stirred for 20 minutes at this temperature. 350 g castor oil was heated to 240° C. and added with vigorous stirring. The mixture was stirred for additional 60 minutes after addition and then cooled to RT. The particle size was determined by light scattering as described before. The particle size is used as an indicator for the efficiency of the stabilizer system.

Viscosity: 5680 mPas

OH-value: 84.55 mg KOH/g

[0073] Particle size D10: 0.95 μm
Particle size D50: 2.54 μm
Particle size D90: 5.21 μm

EXAMPLE 2: USE OF STABILIZER 1 WITH CASTOR OIL

[0074] A round bottom-flasked equipped with a stirrer and a nitrogen inlet was charged with 280 g of Luran® VLR and 70 g of the stabilizer 2 and heated to 240° C. under nitrogen atmosphere. The mixture was stirred for 20 minutes at this temperature. 350 g castor oil was heated to 240° C. and added with vigorous stirring. The mixture was stirred for additional 60 minutes after addition and then cooled to RT. The particle size was determined by light scattering as described before. The particle size is used as an indicator for the efficiency of the stabilizer system.

Viscosity: 5340 mPas

OH-value: 84.7 mg KOH/g

[0075] Particle size D10: 0.91 μm
Particle size D50: 1.91 μm
Particle size D90: 3.82 μm

COMPARATIVE EXAMPLE 2: RADICAL POLYMERIZATION USING POLYBD R20 AS CARRIER POLYOL

[0076] 714.9 g PolyBD R20, 4.5 g macromere B (6-functional polyetherol having a hydroxyl number of 18.4 mg KOH/g, reacted with meta TMI (1-2-isocyanatopropan-2-yl)-3-(prop-1-en-2-yl)benzene)) were charged in a stirred reactor and purged with nitrogen. The mixture was heated to 125° C. A mixture of 333.3 g acrylonitrile, 10.5 g 1-dodecanthiol, 666.7 g styrene as well as 4.7 g Vazo 64 dissolved in 714.9 g PolyBD R20 were added to the reaction mixture in 2 separate streams over 150 min. Stirring could not be continued due to an significant increase of viscosity. At the end of this reaction the mixture was allowed to react for another 15 min. The resulting product was stripped under vacuum and finally cooled to room temperature. Instead of a dispersion a solid, rubber like material was formed.

EXAMPLE 3: USE OF STABILIZER 1 WITH POLYBD R20 AS CARRIER POLYOL

[0077] A round bottom-flasked equipped with a stirrer and a nitrogen inlet was charged with 200 g of Luran® VLR and 50 g of the stabilizer 1 and heated to 240° C. under nitrogen atmosphere. The mixture was stirred for 20 minutes at this temperature. 300 g PolyBD R20 was heated to 240° C. and added with vigorous stirring. The mixture was stirred for additional 60 minutes after addition and then cooled to RT. The particle size was determined by light scattering as described before. The particle size is used as an indicator for the efficiency of the stabilizer system.

Viscosity: 17300 mPas

OH-value: 48.64 mg KOH/g

[0078] Particle size D10: 1.11 μm
Particle size D50: 2.61 μm
Particle size D90: 34.91 μm

EXAMPLE 4: USE OF STABILIZER 2 WITH POLYBD R20 AS CARRIER POLYOL

[0079] A round bottom-flasked equipped with a stirrer and a nitrogen inlet was charged with 200 g of Luran® VLR and 50 g of the stabilizer 1 and heated to 240° C. under nitrogen atmosphere. The mixture was stirred for 20 minutes at this temperature. 300 g PolyBD R20 was heated to 240° C. and added with vigorous stirring. The mixture was stirred for additional 60 minutes after addition and then cooled to RT. The particle size was determined by light scattering as described before. The particle size is used as an indicator for the efficiency of the stabilizer system.

Viscosity: 17800 mPas

OH-value: 48.42 mg KOH/g

[0080] Particle size D10: 1.12 μm
Particle size D50: 5.07 μm
Particle size D90: 40.10 μm

[0081] The experimental data show that the inventive process leads, on average, to smaller particles compared to the standard radical polymerization process. In addition, it can be seen that the polymer polyol dispersions produced by the inventive process are, on average, more homogeneous than the products obtained by the standard process.

[0082] The polymer polyol products obtainable by the inventive process usually have OH numbers of less than 300 mg KOH/g, preferably less than 200 mg KOH/g.

[0083] The polymer polyols produced by the inventive process may be used to manufacture polyurethanes. In addition, elastomers (for example cast elastomers) may be produced.

[0084] The resultant cast elastomers are suitable for industrial applications that require durable physical and mechanical properties in the final elastomers. Industrial rolls such as paper mill rolls, industrial wheels for example.

[0085] Possible applications include roller coatings, electrical encapsulation, pipeline pigs, knives, wheels, rollers, screens. Furthermore, the cast elastomers may be used for the production of formed parts as adhesives or sealants.

[0086] Line segments coated with polyurethane in the sense of this invention do not only include clas-sically coated tube coatings, but also welding areas of tubes coated with polyurethane (so-called “field joints”) and objects coated with polyurethane connected with tubes, for example muffles, drill hole connections, Xmas trees (“Eruptionskreuze”), tube collectors, pumps and buoys.

[0087] In a preferred embodiment of this invention, the inventive line segment coated with polyurethane is a tube of an off-shore pipeline coated with polyurethane, for example for the extraction of crude oil.

[0088] Examples of embodiments of the present invention also include specific elastomer coating and sealing applications, like wheels and tires, drum coatings, spring elements and absorbers, sieves, sealing elements, for example gasket rings, doctor blades, and isolators and switches in anticorrosive coatings.