WO2001023478A1

WO2001023478A1 - Improved prepolymer formulations

Info

Publication number: WO2001023478A1
Application number: PCT/US2000/026772
Authority: WO
Inventors: David R. Macfarland; Brian Fogg; Robert G. Sawitski, Jr.; Trent A. Shidaker
Original assignee: Huntsman International Llc
Priority date: 1999-09-29
Filing date: 2000-09-28
Publication date: 2001-04-05
Also published as: AU7838500A

Abstract

The invention relates to improved prepolymer formulations which include isocyanate terminated polyurethane prepolymers and process oil. A compatibilizing agent is included in the prepolymer formulation in an effective amount to increase the solubility of the process oil in the polyurethane prepolymer.

Description

TITLE OF THE INVENTION

Improved Prepolymer Formulations

TECHNICAL FIELD The invention relates to improved polyurethane formulations, especially to polyurethane prepolymer formulations which have improved compatibility with process oils .

BACKGROUND ART

During manufacture of polyurethane prepolymers such as those for bonding flexible polyurethane foam crumb, a process oil such as naphthenic oil is included in the prepolymer formulation in amounts of about 5 to 50% by weight to lower the surface tension of the prepolymer, as well as to achieve a prepolymer that has a room temperature viscosity of about 300 to about 4000 cP.

The viscosity of the polyurethane prepolymer depends upon variables such as polyol functionality, polyol molecular weight, isocyanate functionality, isocyanate type, and isocyanate value of the prepolymer. The use of a process oil as a diluent provides an additional mechanism for managing the viscosity of these prepolymers.

The re-bonding of flexible polyurethane foam crumbs has traditionally been accomplished by mixing the crumbs with an isocyanate terminated prepolymer adhesive containing a process oil. The prepolymer is typically made from the reaction of an MDI or a TDI isocyanate with a flexible polyol. The flexible polyols typically have molecular weights of between 300 and 8000, more commonly between 1000 and 6000. The flexible polyols are most commonly polyether triols (having a nominal hydroxyl functionality of 3) . The flexible polyols in these prepolymers contribute essential flexibility to the adhesive bond. The technology for making flexible polyols and derived isocyanate terminated prepolymers is well known in the art. Process oils which have been added to these polyurethane prepolymer formulations include naphthenic, paraffinic, and aromatic oils. Aromatic oils have been the industry standard; aromatic oils, however, suffer the disadvantage of being labeled as possible carcinogens. Naphthenic and paraffinic oils, however, exhibit much lower solubilities in polyurethane prepolymer formulations than aromatic oils. As a result, prepolymer formulations which employ naphthenic and paraffinic oils tend to be less stable, with regard to physical separation of the oil, than formulations which employ aromatic oils .

A need therefore exists for polyurethane prepolymer formulations which have improved compatibility and/or solubility of oils such as naphthenic and paraffinic oils.

DISCLOSURE OF THE INVENTION

The invention relates to improved prepolymer formulations which include isocyanate terminated polyurethane prepolymers containing process oil and a compatibilizing agent provided in an effective amount to increase the compatibility of the oil in the polyurethane prepolymer. The improved prepolymer formulations are useful, for example, as binder material for polyurethane flexible foam crumb.

The improved prepolymer formulations may be prepared according to a process which includes the steps of:

(a) providing an isocyanate terminated polyurethane prepolymer;

(b) providing a process oil;

(c) providing a compatibilizing agent in an effective amount to increase the process oil's compatibility in the polyurethane prepolymer; and

(d) combining together the polyurethane prepolymer, process oil and compatibilizing agent.

BEST MODES FOR CARRYING OUT THE INVENTION Glossary:

1. Arcol F 3022 is a 3000 molecular weight polyether triol with a hydroxyl number of 56.0 and a nominal functionality of

3 from Lyondell Chemical Company;

2. Calsol 804 is a naphthenic oil from Calumet Lubricants Company with an aniline point of 63.3 C;

3. Calsol 806 is a naphthenic oil from Calumet Lubricants Company with an aniline point of 69.4C ;

4. Calsol 810 is a naphthenic oil from Calumet Lubricants Company with an aniline point of 72.2 C;

5. Calsol 850 is a naphthenic oil from Calumet Lubricants Company with an aniline point of 80.0 C;

6. Calsol 8240 is a naphthenic oil from Calument Lubricants Company with an aniline point of 85.6 C;

7. Compatibilizing Agent means any additive material which will increase a process oil's compatibility in a polyurethane prepolymer, relative to what it would have been without the compatibilizing agent. Process oil compatibility in prepolymers, and quantification thereof, is defined in detail in the specification (below) ; 8. Corn oil is a mixture of triglycerides based on 10% palmitic acid, 5% stearic acid, 45% oleic, and 38% linoleic acid;

9. Cyclolube 310 N is a naphthenic oil from Golden Bear with an aniline point of 77.8 C;

10. Calight RPO is naphthenic oil from Calumet Lubricants with an aniline point of 72.2 C;

11. Dabco 120 is a tin catalyst from Air Products, Inc.;

12. Dabco T45 is a PIR (polyisocyanurate) catalyst from Air Product, Inc.;

13. Hyprene V100 (also available as Hyprene H100)is naphthenic oil from Ergon, Inc. with an aniline point of 72.8 C;

14. Linseed oil is a mixture of triglycerides based on 6% palmitic acid, 3% stearic acid, 19% oleic acid, 24% linoleic acid, and 47% linolenic acid;

15. LG-168 is a 1000 molecular weight polyether triol from Lyondell Co . ;

16. Palm kernal oil is a mixture of triglycerides based on 47% lauric acid, 9% palmitic acid, 1% stearic acid, 19% oleic acid, and 1% linoleic acid;

17. PPG425 is a 425 molecular weight polyether diol from Lyondell Co. ; 18. PPG725 is a 725 molecular weight polyether diol from Lyondell Co . ;

19. Rubinol F-456 is a 2000 molecular weight polyether diol with a hydroxyl number of 56 and a nominal functionality of 2 from Huntsman Polyurethanes;

20. Rubinol 455 is a 3,100 molecular weight polyether triol from Huntsman Polyurethanes;

21. Rubinol F-459 is a polyether diol from Huntsman Polyurethanes with a hydroxyl number of 30;

22. Rubinate M is polymeric MDI from Huntsman Polyurethanes with an isocyanate value of 31.5 and a functionality of 2.7;

23. Rubinate 9041, available from Huntsman Polyurethanes, is a blend of 75% Rubinate M and 25% of a blend of 4,4'MDI and 2,4' MDI ;

24. Rubinate 9471, available from Huntsman Polyurethanes, is a blend of 60% Rubinate M and 40% of a blend of 4,4'MDI and 2, 4 'MDI and 0.14% HC1;

25. Shellflex 3251 is naphthenic oil from Shell Oil Products Co. with an aniline point of 85.6 C;

26. Shellflex 6212 is naphthenic oil from Shell Oil Products Co. with an aniline point of 67.8;

27. Soya bean oil is a mixture of triglycerides based on 12% palmitic acid, 4% stearic acid, 21% oleic acid, 53% linoleic acid, and 7% linolenic acids;

28. Sundex 840 is an aromatic oil from Sun Oil Company with an aniline point of 15.7 C;

29. Sunflower oil is a mixture of triglycerides based on 6% palmitic acid, 4% stearic acid, 18% oleic acid, and 72% linoleic acid;

30. Sunpar L 103 is a paraffinic oil from Sun Oil Company with an aniline point of 60.5 C;

31. Sunpar LW104 is a paraffinic oil with an aniline point of 69.0 C;

32. Sunpar L 105 is a paraffinic oil with an aniline point of 77.8 C;

33. Sunpar LW107 is a paraffinic oil with an aniline point of 90.6 C;

34. Sunpar LW110 is a paraffinic oil with an aniline point of 101.7 C;

35. Tegostab B-8240, available from Goldschmidt Co., is a polyether Polysiloxane copolymer surfactant. It has a siloxane to polyether ratio of 1:2-1:4, a molecular weight of polyether chains of 600-5000, and a EO/PO ratio of 1:1 to 1:2.3(50-70% PO by weight of the alkoxide) . The types of end groups on polyethers in Tegostab B-8240 are such that the product has a free OH functionality of less than 2.1 with the remaining Polyethers being blocked/capped by either an ether, ester or urethane group; 36. Voranol 235-048 is a 3,500 molecular weight polyether triol with a hydroxyl number of 48.1 and a nominal functionality of 3 from Dow Chemical Company;

37. Voranol 3512 is a 3,500 molecular weight polyether triol with a hydroxyl number of 48.1 and a nominal functionality of 3 from Dow Chemical Company;

38. Voranol 3512A is polyether polyol with a hydroxyl number of 48.1 and a nominal functionality of 3 from Dow Chemical Company .

39. The viscosities referred to herein are Brookfield viscosities (measured at 25C, and reported in cps) unless otherwise specified. We use a Brookfield LVF viscometer using the appropriate spindle and speed for the viscosity of the material. Viscosity is measured at the indicated temperature and the sample is in a 16 oz . glass jar. The ASTM procedure for Brookfield viscosity is ASTM D 4889. The one exception to the method we use is that we use 16 oz . jars not the quart jar that they mention. Viscosity samples are 400g unless otherwise specified. This is the definition of the term "viscosity" as referred to in the Claims.

Materials:

Isocyanates

Organic monomeric polyisocyanates which are useful as the base isocyanates in making the prepolymer formulations of the invention include aromatic, aliphatic and cycloaliphatic diisocyanates and polyisocyanates and combinations of these types . Aromatic diisocyanates which may be used include 4,4'MDI, 3,3' -dimethy1-4, 4 ' -diphenylenediisocyanate, 3,3' -dimethoxy- 4,4' -bisphenylenediisocyanate, 3,3' -diphenyl-4 , 4 ' - biphenylenediisocyanate, 4 , 4 ' -biphenylene diisocyanate, 4- chloro-1, 3-phenylene diisocyanate, 3 , 3 ' -dichloro-4, 4 ' - biphenylene diisocyanate, toluene diisocyanate, and 1,5- naphthalene diisocyanate. MDI isocyanates are preferred. Polymeric MDI having about 31.5% NCO and about 2.7 functionality is most preferred. Polymeric MDI is a combination of monomeric isocyanates which includes 4 , 4 ' -MDI , lesser amounts of 2 , 4 ' -MDI , minor amounts of 2 , 2 ' -MDI , and a mixture higher functionality polymethylene polyphenyl polyisocyanate oligomers. The preferred polymeric MDI has a number averaged isocyanate functionality of 2.7, due to the presence of the mixed high functionality polymethylene polyphenyl polyisocyanate monomer species. Polymeric MDI is prepared by the phosgenation of mixed aromatic amines obtained from the condensation of aniline with formaldehyde. The preparation of polymeric MDI is well known in the art. It is also within the invention to use blends of polymeric MDI with additional amounts of diphenylmethane diisocyanates, particularly 4, 4' -MDI. These blends will have number averaged isocyanate functionalities of from greater than 2.0 to about 2.7, depending upon the ratio of the diphenylmethane diisocyanates to the polymethylene polyphenyl polyisocyanates in the blend.

Aliphatic isocyanates which may be employed include but are not limited to ethylene diisocyanate, 1, 4-tetramethylene diisocyanate, 1 , 6-hexamethylene diisocyanate (HDI) , 2,4,4-tri- methyl-1, 6-hexamethylene diisocyanate, and 1, 12-dodecane diisocyanate .

Cycloaliphatic isocyanates which may be employed include but are not limited to cyclohexane-1 , 4-diisocyanate, cyclobutane-1 , 3-diisocyanate, cyclohexane-1 , 3-diisocyanate, 1- isocyanato-2-isocyanatomethyl cyclopentane, 1-isocyanato- 3 , 3 , 5-trimethyl-5-isocyanatomethyl cyclohexane (isophorone diisocyanate or IPDI), 2,4'- dicyclohexylmethane diisocyanate, 4, 4 ' -dicyclohexylmethane diisocyanate.

Isocyanate reactive component [Flexible Polyol] :

Suitable organic polyols for use as the isocyanate reactive component in preparing the isocyanate terminated polyurethane prepolymer formulations of the invention include polyether, polyester, and amine terminated polyols. Useful polyols have a molecular weight of about 300 to about 10,000, preferably 400 to about 8000, more preferably 1000 to about 6000; and a nominal functionality of about 1.0 to about 6.0, preferably about 2.0 to about 4.0.

Polyether and polyester polyols which may be employed include primary or secondary hydroxyl groups .

All functionalities and molecular weights described herein with respect to polymeric materials are "number average" . All functionalities and molecular weights described with respect to pure compounds are "absolute" . The term "nominal functionality" refers to the expected functionality of a polyol based upon the known functionalities of the monomers used in its manufacture. In the manufacture of polyoxyalkylene polyether polyols, for example, the nominal functionality is the functionality of the initiator. Nominal functionality ignores side reactions, which may sometimes occur during the manufacture of polyols, that may cause the number averaged functionality of the polyol to differ from the expected value.

Suitable polyether polyols which can be employed as the isocyanate reactive component include those which are prepared by reacting alkylene oxides, halogen-substituted or aromatic- substituted alkylene oxides or mixtures thereof with an active hydrogen-containing initiator compound.

Suitable oxides include, for example, ethylene oxide, propylene oxide, 1,2-butylene oxide, styrene oxide, epichlorohydrin, epibromohydrin, and mixtures thereof.

Suitable initiator compounds include water, ethylene glycol, propylene glycol, butanediol, hexanediol, glycerine, trimethylol propane, pentaerythritol , hexanetriol, sorbitol, sucrose, hydroquinone , resorcinol, catechol, bisphenols, novolac resins, phosphoric acid and mixtures thereof. Suitable initiators further include, for example, ammonia, ethylenediamine, diaminopropanes, diaminobutanes , diaminopentanes , dia inohexanes , diethylenetriamine, triethylenetetramine , tetraethylenepentamine, pentamethylenehexamine, ethanolamine, aminoethylethanolamine, aniline, 2 , 4-toluenediamine, 2 , 6-toluenediamine, 2,4'- diaminodiphenylmethane , 4,4' -diaminodiphenylmethane , 1,3- phenylenediamine, 1 , 4-phenylenediamine, naphthylene-1, 5- diamine, triphenylmethane 4 , 4 ' , 4 " -triamine, 4,4'- di (methylamino) diphenylmethane, 1, 3-diethyl-2 , 4- diaminobenzene, 2 , 4-diaminomesitylene, l-methyl-3 , 5-diethyl- 2 , 4-diaminobenzene, l-methyl-3 , 5-diethyl-2 , 6-diaminobenzene, 1 , 3 , 5-triethyl-2 , 6-diaminobenzene, 3,5,3', 5 ' -tetra-ethyl- 4 , 4 ' -diamino-diphenylmethane, and amine aldehyde condensation products such as the polyphenylpolymethylene polyamines produced from aniline and formaldehyde and mixtures thereof.

Polyester polyols which may be employed include, for example, those prepared by reacting a polycarboxylic acid or anhydride with a polyhydric alcohol . The polycarboxylic acids may be aliphatic, cycloaliphatic, aromatic and/or heterocyclic and may optionally be substituted (e.g., with halogen atoms) and/or unsaturated. Examples of suitable carboxylic acids and anhydrides include succinic acid; adipic acid; suberic acid; azelaic acid; sebacic acid; phthalic acid; isophthalic acid; terephthalic acid; trimellitic acid; phthalic acid anhydride; tetrahydrophthalic acid anhydride; hexahydrophthalic acid anhydride; tetrachlorophthalic acid anhydride; endomethylene tetrahydrophtalic acid anhydride; glutaric acid anhydride; maleic acid; maleic acid anhydride; fumaric acid; dimeric and trimeric fatty acids, such as those of oleic acid, which may be in admixture with mono eric fatty acids. Simple esters of polycarboxylic acids may also be used as starting materials for polyester polyols , such as terephthalic acid dimethyl ester, terephthalic acid bisglycol ester and mixtures thereof. Preferably, polyether nominal triols or polyester nominal triols which have a molecular weight of about 3,000 to about 3,500 are used. Blends of these polyols also may be employed. Polyether polyols are more preferred. The most preferred polyether polyols are based on propylene oxide, optionally in combination with minor amounts of ethylene oxide. Examples of these most preferred types of polyether polyols include Arcol 3022 and Voranol 3512. Examples of amine terminated polyols which may be employed include but are not limited to Jeffamine amine terminated polyether polyols from Huntsman Corp.

Compatibilizing Agent

Any material that is capable of increasing the compatibility of the oil in the polyurethane prepolymer can be used. Preferably, the compatibilizing agent is a silicone containing or silicone-based material. Silicone-based surfactants are particularly preferred. Most preferable are polysiloxane surfactants.

A single polysiloxane surfactant is preferred. Preferred polysiloxane surfactants are polysiloxane-polyether copolymers. In an alternative embodiment, blends of polysiloxane surfactants and blends of polysiloxane surfactant (s ) with non-polysiloxane surfactants may be used. Tegostab B-8240 from Goldschmidt is the most preferred polysiloxane surfactant.

Process oil

The process oil may be any suitable oil. For example, suitable oils can be selected from the group consisting of naphthenic oils, aliphatic oils, paraffinic oils, natural oils and mixtures thereof. The process oils employed in the prepolymer formulations of the invention typically have a lower viscosity than the viscosity of the polyurethane prepolymer itself.

Naphthenic, paraffinic, aliphatic and natural oils are well known in the art. In addition, there are no apparent carcinogenic concerns linked to natural oils, naphthenic oils or paraffinic oils. Thus, these oils are particularly attractive as replacements for aromatic oils.

Polyurethane Prepolymer Manufacture

The isocyanate and isocyanate reactive components may be reacted over a wide stoichiometric range to produce prepolymers having reactive isocyanate groups. During manufacture of the polyurethane prepolymers of the invention, process oil can be added to the polyurethane prepolymer formulation in amounts of about 5% to about 50% based on the weight of the prepolymer formulation. Preferably, the final prepolymer formulation has 20% to 35% by wt . process oil, relative to the total weight of the final prepolymer composition [including the prepolymer itself, the process oil, and compatibilizing agent] .

The amount of compatibilizing agent in the polyurethane prepolymer formulations may vary, so long as it is provided in an effective amount to increase the oil compatibility in the prepolymer relative to what it would be without the compatibilizing agent present. Generally, the amount of compatibilizing agent may vary from about 0.01% to about 10% by weight of the final polyurethane prepolymer formulation [including the prepolymer itself, the process oil, and the compatibilizing agent]. Preferably, about 0.10 wt . % by weight to about 10% by wt . of compatibilizing agent based on the weight of the final polyurethane prepolymer formulation is used. The most preferred compatibilizing agent is the commercial silicone surfactant "Tegostab B-8240" (available from Th. Goldschmidt & Co . ) . The most preferred range of concentrations for this compatibilizing agent is 0.2% to 2% by wt . of the final prepolymer. The compatibilizing agent may be added to any of the components of the prepolymer. For example, the compatibilizing agent may be added to the isocyanate, the polyol, the process oil, as well as to the isocyanate terminated prepolymer itself after it is formed.

The term "final prepolymer" as used herein refers to the prepolymer with the desired amount of process oil and with the compatibilizing agent included. All percentages by weight quoted herein are relative to the final prepolymer. The term

"prepolymer itself" as used herein refers to the prepolymer without any process oil or compatibilizing agent.

The order in which the ingredients of the final prepolymer (i.e. the organic monomeric base isocyanate; the flexible polyol; the process oil; and the compatibilizing agent) are combined is not particularly important. The order of addition of ingredients may be adjusted to suit the available processing equipment used to make the final prepolymer composition. For example; the process oil and the compatibilizing agent may, if desired, be combined with the polyol or the monomeric base polyisocyanate before the prepolymer reaction is performed. Alternatively; the reaction of the monomeric based isocyanate and the polyol may be completed first, followed by introduction of the process oil and compatibilizing agent. In yet another alternative; the compatibilizing agent may be combined with either the polyol or the monomeric base isocyanate before the prepolymer reaction is performed, and the process oil may be added after the prepolymer reaction is completed. Other suitable variations will be apparent to those skilled in the art.

The process oil is said to be compatible with the prepolymer to the extent that it does not separate during storage under a fixed set of conditions. The compatibility of course depends upon the final prepolymer composition. A prepolymer composition is said to be compatible if it does not show visible oil separation on storage for three days at ambient temperature (typically 30 C) under dry air without agitation. Comparisons of relative compatibility of different formulations may be made for shorter storage times, provided of course that the storage times and conditions are the same.

Compatibility is resistance to bulk separation, and is not necessarily synonymous with solubility. Preferably the process oil has higher compatibility in the final prepolymer than it does with the monomeric base polyisocyanate composition. Preferably the process oil has an aromatic hydrocarbon concentration of less than 50% by wt . , and more preferably less than 40% by wt . The preferred process oils are selected from the group consisting of oils not listed as suspect carcinogens (or as carcinogens).

The invention will now be illustrated by reference to the following non-limiting examples. In these examples the process oil is added to the polyurethane prepolymer formulation that includes isocyanate, isocyanate reactive component (flexible polyol), and the compatibilizing agent. All amounts of ingredients quoted in the examples are in percent by weight, unless indicated otherwise in the tables. The isocyanate and polyol components are mixed together and reacted at 45 C for 15 hours. In order to reproduce the simple method of prepolymer preparation used in the foam re-bond industry, the prepolymer samples were mixed in bulk at the appropriate weight ratios in glass jars under dry air. The prepolymer samples were prepared on a 400g scale in 16 ounce glass jars, unless otherwise indicated. The reaction mixture was then immediately agitated by vigorous manual shaking for about 30 sec. The jars were then placed in a convective oven set at

45C for 15 hours. The conversion of the reactive ingredients to urethane prepolymer was then determined to be complete by measurement of residual free isocyanate content (wt. %NCO concentration), which agreed with the predicted values. The % oil compatibility is shown in the tables. The percent oil compatibility is measured after three days storage without agitation at 30C, unless indicated otherwise in the tables.

A prepolymer is considered to be compatible if a sample (as defined below) appears homogeneous to the naked eye (i.e. there is no visible separation of layers) after three days under the following test conditions:

A dry 16mm X 150mm test tube is filled with 20g of a freshly prepared prepolymer containing process oil. The tube is immediately capped (typically with a polyethylene stopper) .

Such samples, to be evaluated and compared, are placed in a test tube rack and the rack is placed in a 30C constant temperature water bath for three days, with no agitation of the samples . After three days the samples are removed from the water bath and examined for separation. If no visible separation is observed, the sample is said to be compatible. If separation is observed (the oil usually rises to the top of the sample) the excess oil which has separated may be removed from the sample by pipette. The sample is weighed before and after pipetting in order to measure the amount of oil which has separated. The degree of oil compatibility for that sample is then calculated by using the following formula (I) :

(I) Oil-Compatibility = 100% {M (Oil-Added) - M(Oil- Separated) }/{M (Total) - M (Oil-Separated}

Wherein :

M(Oil-Added) = Mass of process oil added to make sample, M(Oil-Separated) = Mass of process oil pipetted off (separated) ,

M (Total) = Initial sample mass (prepolymer + oil + any optional compatibilizer) .

Clearly, if there is no visible oil separation after the three days storage then no oil is pipetted off, and the oil compatibility is equal to the percentage by weight of process oil used in making the original sample. This formula was used in determining the oil compatibility values shown in the examples below. The compatibility values quoted in these examples are after 3 days storage at 30C (as defined above) , unless otherwise specifically indicated. EXAMPLES :

All %NCO values quoted in the Tables below were theoretically calculated based on the final prepolymers (with all ingredients present, exactly as shown in the formulations given in the Tables) .

Table I

Comparison Example I :

Example 7 in Table I shows the extent of Naphthenic oil separation when Tegostab B8240 is not employed in manufacture of polyurethane prepolymer. In this example, a prepolymer is made by reacting 7. Og Rubinate 9041, 4.7g Voranol 3512 and 6.7g Hyprene V100 for 16 hours at 50 C. The resulting prepolymer has a %NCO content of 11.2%. One day after forming the prepolymer, 5. lg of Hyprene V100 separated to the top of the mixture, resulting in a maximum oil solubility of approximately 12%. Constant agitation is required to prevent this naphthenic process oil from separating from the prepolymer .

Addition of Tegostab B8240 to Prepolymer: The following six examples show addition of naphthenic process oil to isocyanate prepolymer and addition of Tegostab B8240 to the prepolymer. Example 14A:

A prepolymer is made by reacting Rubinate 9041 in an amount of 40.53% with Arcol 3022 in an amount of 33.97% and heating for 24 hours at 50C. The %NC0 content of the prepolymer is 11.50%.

Hyprene V100 in an amount of 25% and Tegostab B8240 in an amount of 0.5% then are added to the prepolymer, all amounts based to total weight of Rubinate 9041, Arcol 3022, Hyprene 100 and Tegostab B8240.

No oil separation was observed at 3 days after formation of the prepolymer.

Example 14B: A prepolymer is made by reacting Rubinate 9041 in an amount of 40.7% with Rubinol F-456 in an amount of 34.1% and heating for 24 hours at 50C. Hyprene H-100 in an amount of 25% and Tegostab B8240 in an amount of 0.2% then are added to the prepolymer, all amounts based to total weight of Rubinate 9041, Rubinol F-456, Hyprene 100 and Tegostab B8240. No oil separation was observed at 3 days after formation of the prepolymer.

Example 14C:

A prepolymer is made by reacting Rubinate 9041 in an amount of 39.98% with Rubinol F456 in an amount of 29.82% and heating for 24 hours at 50 C.

Hyprene Hi00 in an amount of 30% and Tegostab B8240 in an amount of 0.2% then are added to the prepolymer, all amounts being based on the total weight of Rubinate 9041, Rubinol F456, Hyprene H100, and Tegostab B8240. No oil separation is observed at 3 days after formation of the prepolymer.

Example 14D:

A prepolymer is made by reacting Rubinate 9041 in an amount of 39.4% with Rubinol F456 in an amount of 25.4% and heating for 24 hours at 50 C. Hyprene H100 in an amount of 35% and Tegostab B8240 in an amount of 0.2% then are added to the prepolymer, all amounts being based on the total weight of Rubinate 9041, Rubinol F456, Hyprene H100, and Tegostab B8240. No oil separation is observed at 3 days after formation of the prepolymer. Example 14E:

A prepolymer is made by reacting Rubinate 9041 in an amount of 39.96% with Arcol F3022 in an amount of 29.84% and heating for 24 hours at 50 C.

Calsol 806 in an amount of 30% and Tegostab B8240 in an amount of 0.2% then are added to the prepolymer, all amounts being based on the total weight of Rubinate 9041, Arcol F3022, Calsol 806, and Tegostab B8240. No oil separation is observed at 3 days after formation of the prepolymer. Example 14F :

A prepolymer is made by reacting Rubinate 9041 in an amount of 39.31% with Arcol F3022 in an amount of 25.49% and heating for 24 hours at 50 C.

Calsol 806 in an amount of 35% and Tegostab B8240 in an amount of 0.2% then are added to the prepolymer, all amounts being based on the total weight of Rubinate 9041, Arcol F3022, Calsol 806, and Tegostab B8240. No oil separation is observed at 3 days after formation of the prepolymer.

Examples 15-28:

In examples 15-28 in Table II below, prepolymers are made by reacting Rubinate 9471 with Voranol 3512A in the presence of Hyprene V100 naphthenic process oil and Tegostab B8240. Separation of the process oil from the prepolymer is measured by placing 20 grams of prepolymer in a glass test tube. The test tube with the prepolymer then is placed in a water bath at the indicated temperature. Every 24 hours, any oil that separates is siphoned off the surface of the prepolymer and weighed. The oil solubilities shown in Table 2 are calculated using Formula I above.

Examples 29-31 :

The following three examples show additional examples of utilizing a naphthenic process oil in an isocyanate prepolymer with the addition of Tegostab B8240 to the prepolymer. Example 29:

A prepolymer is made by reacting Rubinate 9041 in an amount of 40.47% with Arcol F 3022 in an amount of 34.33% and heating for 24 hours at 50°C.

Calsol 806 in an amount of 25% and Tegostab B8240 in an amount of 0.2% then are added to the prepolymer, all amounts based on the total weight of Rubinate 9041, Arcol F 3022, Calsol 806 and Tegostab B8240. No oil separation was observed at three days after formation of the prepolymer. Example 30: A prepolymer is made by reacting Rubinate 9041 in an amount of 39.96% with Arcol F 3022 in an amount of 29.84% and heating for 24 hours at 50°C.

Calsol 806 in an amount of 30% and Tegostab B8240 in an amount of 0.2% then are added to the prepolymer, all amounts based on the total weight of Rubinate 9041, Arcol F 3022,

Calsol 806 and Tegostab B8240. No oil separation was observed at three days after formation of the prepolymer. Example 31:

A prepolymer is made by reacting Rubinate 9041 in an amount of 39.31% with Arcol F 3022 in an amount of 25.49% and heating for 24 hours at 50°C.

Calsol 806 in an amount of 35% and Tegostab B8240 in an amount of 0.2% then are added to the prepolymer, all amounts based on the total weight of Rubinate 9041, Arcol F 3022, Calsol 806 and Tegostab B8240. No oil separation was observed at three days after formation of the prepolymer. Examples 32 - 49 and Comparative Examples 32 - 49: These examples, shown in Tables III, IV and V, show the comparative solubilities of naphthenic oils in polyurethane prepolymers. The comparative examples show the solubilities without the addition of Tegostab B-8240. Oil separation was observed at three days after formation of the prepolymer. The examples show that the Tegostab B-8240 significantly increases the oil solubility in the prepolymers.

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o

Examples 50 - 64 and Comparative Examples 50 - 64 These examples, shown in Tables VI, VII and VIII, show the comparative solubilities of paraffinic oils in polyurethane prepolymers . The comparative examples show the solubilities without the addition of Tegostab B-8240. Oil separation was measured after three days after formation of the prepolymer. The examples show that the Tegostab B-8240 significantly increases the oil solubility in the prepolymers,

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Examples 65 -90 :

These examples, shown in Table IX, demonstrate the effect of various silicone-based surfactants on naphthenic oil solubility in the prepolymer.

ADDITIONAL COMPARATIVE EXAMPLES: Base Isocyanate Compatibility:

The following two experiments were conducted in order to determine the natural solubility of a napthenic oil in certain monomeric base isocyanate blends:

i) A blend is made by mixing of 75% by wt . of Rubinate M with 25% by wt . Calsol 806. The blend was stored without agitation for 3 days at 30 C, after which time it was observed to have separated. The separated oil was removed by pipette. The oil compatibility in this base isocyanate was calculated, based on the weight of oil removed, to be 8.57% by wt . relative to the total final weight of the sample.

ii) A blend is made by mixing 75% by wt . of Rubinate 9041 with 25% by wt . Calsol 806. The blend was stored without agitation for 3 days at 30 C, after which time it was observed to have separated. The separated oil was removed by pipette. The oil compatibility in this base isocyanate was calculated, based on the weight of the oil removed, to be 10.69% by wt . relative to the total final weight of the sample.

These two additional comparative Examples show that the natural compatibility of the napthenic oil with the base isocyanate is low (typically around 10% bw wt . or less) .

Claims

We claim :

1. A process for making oil containing prepolymer formulations comprising the steps of: a) providing a polyurethane prepolymer; b) providing a process oil; c) providing a compatibilizing agent in an effective amount to increase the process oil's solubility in the polyurethane prepolymer; and d) combing together the polyurethane prepolymer, the process oil, and the compatibilizing agent to form the oil containing prepolymer .

2. The process of claim 1, wherein the compatibilizing agent comprises a silicone containing material.

3. The process of claim 2, wherein the silicone containing material is silicone-based surfactant.

4. The process of claim 3, wherein the silicone-based surfactant is polysiloxane surfactant.

5. The process of claim 4, wherein the polysiloxane surfactant is polysiloxane-polyether copolymer.

6. The process of claim 4, wherein the polysiloxane surfactant is a blend of polysiloxane surfactants.

7. The process of claim 4, wherein the polysiloxane surfactant is a blend and additionally includes non- polysiloxane surfactant.

8. The process of claim 1, wherein the process oil is selected from the group consisting of naphthenic oils, aliphatic oils, paraffinic oils, natural oils, and mixtures thereof .

9. The process of claim 1, wherein the compatibilizing agent is provided in the amount of from about 0.01 weight percent to about 10 weight percent, based on the total weight of the prepolymer formulation.

10. A polyurethane prepolymer comprising: a) a polyurethane prepolymer; b) a process oil; and c) a compatibilizing agent in an effective amount to increase the process oil's solubility in the polyurethane prepolymer.

11. The polyurethane prepolymer of claim 10, wherein the compatibilizing agent comprises a silicone containing material .

12. The polyurethane prepolymer of claim 11, wherein the silicone containing material is silicone-based surfactant.

13. The polyurethane prepolymer of claim 12, wherein the silicone-based surfactant is polysiloxane surfactant.

14. The polyurethane prepolymer of claim 13, wherein the polysiloxane surfactant is polysiloxane-polyether copolymer.

15. The polyurethane prepolymer of claim 13, wherein the polysiloxane surfactant is a blend of polysiloxane surfactants .

16. The polyurethane prepolymer of claim 13, wherein the polysiloxane surfactant is a blend and additionally includes non-polysiloxane surfactant.

17. The polyurethane prepolymer of claim 10, wherein the process oil is selected from the group consisting of naphthenic oils, aliphatic oils, paraffinic oils, natural oils, and mixtures thereof.

18. The polyurethane prepolymer of claim 10, wherein the compatibilizing agent is present in the amount of from about 0.01 percent by weight to about 10 percent by weight, based upon the total weight of the prepolymer formulation.

19. An isocyanate terminated prepolymer which is liquid at 25 C and has a viscosity at 25 C in the range of 300 to 4000 cps, said prepolymer consisting essentially of the combination of:

A) the reaction product of a flexible polyol, said polyol having a molecular weight between 300 and 8000 and containing between 1.3 and 8 isocyanate reactive groups, with a stoichiometric excess of an organic monomeric base polyisocyanate having a number averaged isocyanate functionality of from 2.2 to 3.0,

B) a process oil in an amount greater than 12% by weight of the final prepolymer composition, and

C) a compatibilizing agent in an amount sufficient to increase the compatibility of the process oil in the final prepolymer, relative to the compatibility of the same process oil in the same prepolymer in the absence of the compatibilizing agent.

20. The prepolymer of claim 19 wherein the process oil comprises greater than 20% by weight of the final prepolymer composition.

21. The prepolymer of claim 20 wherein the process oil remains fully compatible for at least 3 days at 30C in the absence of agitation.

22. The prepolymer of claim 20 wherein the process oil is a napthenic hydrocarbon oil.

23. The prepolymer of claim 22 wherein the organic monomeric polyisocyanate is a mixture of diphenylmethane diisocyanate isomers and higher polymethylene polyphenyl polyisocyanate oligomers of functionality 3 or greater.

24. The prepolymer of claim 20 wherein the compatibility of the process oil with the organic monomeric base polyisocyanate is not greater than 20% by weight after 3 days storage at 30C in the absence of agitation.