BIO-containing polyisocyanate prepolymers for increasing overall BIO-content in polyurethane products

Abstract

An isocyanate-containing prepolymer which is a reaction product of a polyisocyanate with at least 20 wt. % of a bio-based polyol is disclosed. Also disclosed is a polyurethane system, containing an isocyanate prepolymer which is the reaction product of a polyisocyanate with at least 20 wt. % of a bio-based polyol; and an isocyanate reactive component. Also disclosed is a polyurethane foam system comprising an A side isocyanate comprising ≤ 20 wt. %; of a first bio-containing polyol, and a B side polyol comprising 30-50 wt. % of a second bio-containing polyol.

Description

[0001] TITLE OF THE INVENTION

[0002] BIO-CONTAINING POLYISOCYANATE PREPOLYMERS FOR INCREASING OVERALL BIO-CONTENT IN POLYURETHANE PRODUCTS

[0003] BACKGROUND OF THE INVENTION

[0004] FIELD OF THE INVENTION

[0005] The invention relates to polyisocyanate prepolymers for the preparation of polyurethane resins and to a polyurethane forming system.

[0006] DESCRIPTION OF RELATED ART

[0007] There is a global trend is to decrease reliance on conventional (oil derived) materials and to increase use of materials derived from bio-based feedstock. The major bio-based components in polyurethane systems has been replacing conventional polyols with castor oil or soy oil. The amount of castor or soy that can be included in the material is limited due to the 2-component nature of polyurethane materials; there is a limit to the amount of biocontent that can be added in just one component, achieved through replacing the conventional polyol in the resin blend. Such replacement can be limited by mix volume, but also by the compromise necessary with respect to reactivity and mechanical properties of the final product with high bio-content. Typically, bio-content is in this way limited to about 30% of the total formulation. Total bio-content of commercial PU systems is typically limited to -30%.

[0008] EP 2527381 discloses a method for producing high resilient flexible polyurethane foam material comprises mixing (a) isocyanate prepolymer, (b) polymeric compounds with isocyanate reactive groups, (c) castor oil, (d) optionally chain extender and / or crosslinking agent, (e) catalysts, (f) blowing agents and optionally, (g) additives to form a reaction mixture and reacting to produce flexible polyurethane foam material, where the castor oil (c) of more than 5 wt.%, based on the total weight of components (b) to (g) is used and the isocyanate prepolymer (a) is obtained by mixing diphenylmethane diisocyanate (al) and polyol 1 (a2).

[0009] U.S. 20120302652 discloses a method for producing polyurethane foams having a density of less than 100 g / 1 and a resilience of greater than 40%, comprises mixing (a) isocyanate prepolymer, (b) polymeric compounds having isocyanate-reactive groups, (c) castor oil, (d) optionally, chain-extending and / or crosslinking agents, (e) catalysts, (f) blowing agents, and optionally, (g) additives, to form a reaction mixture and reacting to form the flexible polyurethane foam.

[0010] WO 2011132490 discloses a two-component curable foam polyurethane resin composition contains main agent containing isocyanate group-terminal urethane prepolymer (A) and curing agent containing isocyanate group-reactive compound (B), water (C) and catalyst (D). The components (A) and (B) are obtained using polyol component containing castor oil polyol (bl) having 1 .5-2.3 average number of functional groups, polyol (b2) obtained by addition polymerization of lactone and polytetramethylene glycol, and / or polytetramethylene glycol (b3). The content of castor oil polyol is 10-45 %mass.

[0011] CN 114249873 discloses preparing polyurethane soft foam involves first mixing the first vegetable oil polyol with isocyanate to obtain prepolymer, the mol ratio of -OH on the first vegetable oil polyol and -NCO on the isocyanate is 1 : 6 to 17, mixing second vegetable oil polyol, polyether polyol, foam stabilizer and foaming agent catalyst to obtain the premix, mixing pre- polymer and premix, foaming and obtaining the polyurethane soft foam. The mass ratio of the first vegetable oil polyol, the second vegetable oil polyol and polyurethane soft foam is (50-70): (95.8-143.5).

[0012] WO 2000023491 discloses polyurethane production by reacting a polyisocyanate with a polyol, reaction is carried out in the presence of soya oil.

[0013] U.S. 20050176839 discloses a rigid polyurethane foam is made by using a prepolymer that is the reaction product of polyisocyanate component(s), hydroxyfunctional acrylate component(s), and polyol component(s). The prepolymer is then reacted at specified volume ratios and isocyanate indices with polyol component s) that includes polyol(s) that is a biopolymer, including castor oil and / or soybean oil. The foam is made in the presence blowing agent(s) and catalyst(s).

[0014] US 8,133,419 discloses that headliners are used in the passenger compartments of various types of vehicles. They provide an aesthetically pleasing appearance, acoustical and vibrational damping, and in some cases incorporate energy-absorbing components intended to reduce risk of injury in a collision or other accident. The headliner may also provide a certain amount of structural reinforcement to the vehicle. To achieve these things, the headliner in many cases includes a structural polymer foam component.

[0015] In addition, incorporation of bio-derived polyols into polyurethane systems can present certain challenges in terms of mechanical properties. One application is in the area of acoustic PU foams used in automotive headliners and carpet backing. Providing mechanical properties comparable with conventional materials in terms of post cure shrinkage has been difficult to obtain.

[0016] Applicant has discovered that the total bio-content can be increased beyond this limit to even greater than 60% of the total formulation by including bio-containing polyol in the isocyanate component, in addition to the resin component. Mechanical properties can be acceptable, and reactivity can be similar to the conventional PU system.

[0017] Applicant has also discovered that a polyurethane foam system comprising an A side isocyanate comprising bio-containing polyol, and a B side polyol comprising bio-containing polyol as having good mechanical properties.

[0018] BRIEF SUMMARY OF THE INVENTION

[0019] This and other objects have been achieved by the present invention the first embodiment of which includes an isocyanate-containing prepolymer comprising at least 20 wt. % of a biocontaining polyol.

[0020] According to another aspect of the invention is a polyurethane system comprising an isocyanate prepolymer comprising at least 20 wt. % of a bio-containing polyol and an isocyanate reactive component. According to another aspect of the invention is a polyurethane foam system comprising an A side isocyanate comprising a first bio-containing polyol, and a B side polyol comprising a second bio-containing polyol.

[0021] According to another aspect of the invention is a process for preparing a molded polyurethane foam by reacting a polyurethane foam system.

[0022] Applicant has also discovered that a polyurethane foam system comprising an A side isocyanate comprising < 20 wt. %; of a first bio-containing polyol, and a B side polyol comprising 30-50 wt % of a second bio-containing polyol can provide for good mechanical performance in terms of shrinkage and acoustic performance.

[0023] DETAILED DESCRIPTION OF THE INVENTION

[0024] The isocyanate-containing prepolymer comprising at least 20 wt. % of a bio-containing polyol according to the inventive polyurethane system may be obtained by reacting a polyisocyanate with a bio-containing polyol.

[0025] Suitable polyisocyanates may include ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1 ,12-dodecane diisocyanate, cyclobutane-l ,3-diisocyanate, cyclohexane- 1,3 -and -1,4-diisocyanate, l-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl- cyclohexane ("isophorone diisocyanate"), 2,4- and 2,6-hexahydrotoluene diisocyanate, dicyclohexylmethane-4,4'-diisocyanate ("hydrogenated MDI", or "HMDI"), 1,3- and 1,4- phenylene diisocyanate, 2,4- and 2,6-toluene diisocyanate ("TDI"), diphenylmethane-2,4'- and / or -4,4'-diisocyanate ("MDI"), naphthylene-l,5-diisocyanate, triphenyl-methane-4,4',4"- triisocyanate, polyphenyl-polymethylene-polyisocyanates ("crude MDI"), norbornane diisocyanates, m- and p-isocyanatophenyl sulfonylisocyanates, perchlorinated aryl polyisocyanates, carbodiimide-modified polyisocyanates, urethane-modified polyisocyanates, allophanate-modified polyisocyanates, isocyanurate-modified polyisocyanates, urea-modified poly isocyanates, biuret-containing polyisocyanates. Preferably the polyisocyanate is 4,4’-MDI, modified 4,4’-MDI, mixtures of 4,4’-MDI and 2,4’-MDI, polymeric MDI (2,4’-MDI, 4,4’-MDI, 3-ring and higher structures).

[0026] The polyisocyanate preferably has a functionality of 2-5, preferably 2-3. Suitable bio-containing polyols are not particularly limited and include vegetable and plant oils, such as castor oil soybean oil palm oil, rapeseed oil, tall oil, algae oil or any combinations thereof.

[0027] Bio-based linear polyester polyols using bio-su cmic acid, bio-adipic acid and bio- sebacic- acid as the aliphatic diacids and bio-based polyols such as diethylene glycol, 1,3 -propanediol and 1,4-butanediol or glycerol, sorbitol, and xylitol, to produce polyester polyols may be

[0028] Aromatic polyols from lignin and / or Biobased Mannich polyols synthesized from aromatic limonene derivatives or cashew nutshell liquid (CNSL) may also be used. Preferably Castor oil, modified castor oil (e.g., Sovermol™ materials), modified soy oils (e g., BiOH resins from Cargill), liquified and modified lignin are used as the bio-containing polyol.

[0029] The polyisocyanate and bio-containing polyol may be suitably reacted in a weight ratio of polyisocyanate to bio-containing polyol of 5: 1, preferably 4: 1, more preferably 3: 1, even more preferably 2: 1, and most preferably 1 : 1.

[0030] The poly isocyanate and bio-containing polyol may be suitably reacted in an amount of at least 20 wt. %, preferably at least 30 wt. %, more preferably at least 40 wt. %, more preferably at least 50 wt. %, even more preferably at least 60 wt. % of bio-containing polyol relative to poly isocyanate, the sum of reactants adding to 100 wt. %. Preferably the amount of bio-containing polyol is less than 70 wt. %, more preferably less than 65 wt. %.

[0031] The isocyanate-containing prepolymer comprising at least 20 wt. % of a bio-containing polyol preferably has a number average molecular weight of from 250 to 1,000 g / mol, preferably 500 to 900 g / mol, more preferably 600 to 800 g / mol.

[0032] The isocyanate-containing prepolymer comprising at least 20 wt. % of a bio-containing polyol preferably has an NCO content of from 10-25 wt. %, preferably 15-23 wt. %, more preferably 18-20 wt. %.

[0033] The reaction of poly isocyanate and bio-containing polymer may be conducted under conditions known to one of ordinary skill in the art, without undue experimentation. According to another aspect of the invention is a polyurethane system comprising an isocyanate-containing prepolymer comprising at least 20 wt. % of a bio-containing polyol and an isocyanate reactive component.

[0034] The isocyanate reactive component is not particularly limited and may be selected from polyols, polyethers, polyesters, polyacetals, polycarbonates, polyester ethers, polyester carbonates, polythioethers, polyamides, polyester amides, polysiloxanes, polybutadienes and polyacetones. Preferably the isocyanate reactive component is a bio-based polyol.

[0035] Formulations with higher bio-content may be achieved by including bio-containing polyol as prepolymer in the isocyanate component, in addition to or separately from, including biocontent in the resin blend.

[0036] Another embodiment of is a polyurethane foam system comprising an A side isocyanate comprising bio-containing polyol, and a B side polyol comprising bio-containing polyol. The polyurethane foam system is distinct from the polyurethane system described above.

[0037] A side isocyanate comprising bio-containing polyol

[0038] The A side isocyanate comprising bio-containing polyol comprises a reaction product of a polyisocyanate and a first bio-containing polyol in an amount of < 20 wt. %, preferably 5-20 wt. %, more preferably 7-15%, even more preferably 8-12 wt. % of a first bio-containing polyol in the A side isocyanate comprising bio-containing polyol.

[0039] The first bio-containing polyol component of the A side isocyanate comprising biocontaining polyol has a functionality > 2.2. preferably > 2.4, more preferably > 2.6.

[0040] Suitable first bio-containing polyols are not particularly limited and include vegetable and plant oils, such as castor oil soybean oil palm oil, rapeseed oil, tall oil, algae oil or any combinations thereof, preferably the bio-containing polyol is castor oil.

[0041] The first bio-containing polyol has a Mw (weight average molecular weight) of < 2,000, preferably < 1,5000, more preferably < 1,000. The Mw is also preferably > 250, more preferably > 500, even more preferably > 600. The A side isocyanate comprising bio-containing polyol of the polyurethane foam system is reacted with a B side polyol comprising a second bio-containing polyol.

[0042] B side polyol comprising bio-containing polyol

[0043] B-side second bio-containing polyol

[0044] B side polyol comprises a second bio-containing polyol in an amount of 30-50 wt. %, preferably 35-45 wt. %, more preferably 37-43 wt. % of the B side polyol.

[0045] The B side second bio-containing polyol has an OH number in the range of 50 to 175. The B side second polyol comprising bio-containing polyol has a functionality of 1.7 to 3.0, and Mw 500 to 2500 g / mol.

[0046] Suitable B-side second bio-containing polyols are not particularly limited and include vegetable and plant oils, such as castor oil soybean oil palm oil, rapeseed oil, tall oil, algae oil or any combinations thereof, preferably the bio-containing polyol is castor oil.

[0047] In addition to the B-side second bio-containing polyol, the remaining B-side polyols are conventionally known in the area of polyurethane foams and used in an amount of 50-70 wt. %, preferably 55-65 wt. %, more preferably 57-63 wt. % of the B-side. Suitable B-side polyols have a reactive group selected from the hydroxy group, the amino groups, the mercapto group and the carboxylic acid group. Preference is given here to the hydroxy group and very particular preference is given here to primary hydroxy groups. It is particularly preferable that the isocyanate-reactive compound (b) is selected from the group of polyesterols, polyetherols and polycarbonatediols, these also being covered by the term “polyols”.

[0048] Suitable polymers of the remaining B-side polyol are homopolymers, for example polyetherols, polyesterols, polycarbonatediols, polycarbonates, polysiloxanediols, polybutadienediols, and also block copolymers, and also hybrid polyols, e.g. poly(ester / amide). Preferred polyetherols in the invention are polyethylene glycols, polypropylene glycols, polytetramethylene glycol (PTHF), polytrimethylene glycol. Preferred polyester polyols are polyadipates, polysuccinic esters and polycaprolactones. In another embodiment, the present invention also provides a thermoplastic polyurethane as described above where the polyol composition comprises a polyol selected from the group consisting of polyetherols, polyesterols, polycaprolactones and polycarbonates.

[0049] Examples of suitable block copolymers are those having ether and ester blocks, for example polycaprolactone having polyethylene oxide or polypropylene oxide end blocks, and also polyethers having polycaprolactone end blocks. Preferred polyetherols in the invention are polyethylene glycols, polypropylene glycols, polytetramethylene glycol (PTHF) and polytrimethylene glycol. Preference is further given to polycaprolactone.

[0050] In a particularly preferred embodiment, the molar mass Mn of the polyol used is in the range from 500 g / mol to 4000 g / mol, preferably in the range from 500 g / mol to 3000 g / mol.

[0051] Another embodiment of the present invention accordingly provides a thermoplastic polyurethane as described above where the molar mass Mn of at least one polyol comprised in the polyol composition is in the range from 500 g / mol to 4000 g / mol.

[0052] It is also possible in the invention to use mixtures of various polyols.

[0053] An embodiment of the present invention uses, for the production of the thermoplastic polyurethane, at least one polyol composition comprising at least polytetrahydrofuran. The polyol composition in the invention can also comprise other polyols alongside polytetrahydrofuran.

[0054] Materials suitable by way of example as other polyols in the invention are polyethers, and also polyesters, block copolymers, and also hybrid polyols, e.g. poly(ester / amide). Examples of suitable block copolymers are those having ether and ester blocks, for example polycaprolactone having polyethylene oxide or polypropylene oxide end blocks, and also polyethers having polycaprolactone end blocks. Preferred polyetherols in the invention are polyethylene glycols and polypropylene glycols. Preference is further given to poly caprolactone as other polyol.

[0055] Examples of suitable remaining B side polyols are polyetherols such as polytrimethylene oxide and polytetramethylene oxide.

[0056] Another embodiment of the present invention accordingly provides a thermoplastic polyurethane as described above where the remaining B side polyols comprises at least one polytetrahydrofuran and at least one other polyol selected from the group consisting of another polytetramethylene oxide (PTHF), polyethylene glycol, polypropylene glycol and polycaprolactone.

[0057] In a particularly preferred embodiment, the remaining B side polyols have a number-average molar mass Mn of the polytetrahydrofuran is in the range from 500 g / mol to 5000 g / mol, more preferably in the range from 550 to 2500 g / mol, particularly preferably in the range from 650 to 2000 g / mol and very preferably in the range from 650 to 1400 g / mol.

[0058] The A side isocyanate comprising bio-containing polyol and B-side polyol are reacted at an index of 80-110, depending on the application. For carpet backing, the iso index is generally from 80-85. For headliner applications, the iso index is 100-110, preferably 105.

[0059] The polyurethane foam system may be crosslinked and / or chain extended used as a chain extender and / or crosslinking agent, selected from the group of the alkanolamines, diols and / or triols having molecular weights of less than 400 g / mol and a functionality between 2 to 3.

[0060] Examples of suitable alkanolamines are mono, di- or tri-Ci-C4-alkanolamines or methyl- Ci- C4— alkanolamines, for example ethanolamine, diethanolamine, triethanolamine, propanolamine, N,N-diethanolpropanamine, butanolamine, N,N-diethanolbutanamine, N- methylethanolamine, N-ethyldiethanolamine, N-methyldiethanolamine, N- methylpropanamine, N-methyl-N-ethanolpropanamine, N-methylbutanamine, N-methyl-N- ethanolbutanamine or mixtures of the alkanolamines mentioned above. Examples of suitable triols are glycerol (molecular weight 92.1 g / mol) and trimethylolpropane (molecular weight 134.2 g / mol).

[0061] Examples of suitable diols are monoethylene glycol, propane- 1,2- and -1,3 -diol, butane- 1,2-, -1,3-, -1,4- and -2,3-diol, pentanediols, hexanediols, diethylene glycol, triethylene glycol, dipropylene glycol and tripropylene glycol.

[0062] Preference is given to diols or alkanolamines having molecular weights of less than 400 g / mol, preferably a molecular weight of 60 to 300 g / mol.

[0063] Very particular preference is given to diols having molecular weights of less than 400 g / mol, preferably a molecular weight of 60 to 300 g / mol, preferably glycerin and ethanolamine in an amount up to 1.0 wt. %.

[0064] Water is used as foaming agent in amount up to 5 wt. %.

[0065] The polyurethane foam system may be preferably used to applications of an automotive headliner and a carpet backing layer, application where properties of low shrinkage and acoustic dampening are beneficial.

[0066]

[0067] Automotive headliners and carpet backing layers may be prepared by conventional methods known to those of ordinary skill in the art. Typically, the polyurethane foam system is a) applied onto a mat of at least one reinforcing fiber to form an impregnated mat, b) molding the impregnated mat at an elevated temperature sufficient to cure the polyurethane composition, to form a molded, fiber-reinforced polyurethane foam, and c) demolding the fiber-reinforced polyurethane foam.,

[0068] The open cell content of the polyurethane foam system is at least 51%, preferably at least 60%, more preferably at least 70% in order to provide for acceptable acoustic sound dampening properties.

[0069] In a headliner application, the elongation is at least 13%, preferably at least 15%, more preferably at least 20%.

[0070] In a headliner application, the foam density is typically 22-30 kg / m3.

[0071] In a headliner application, the compression at 50% is at least 50 Kpa, preferably at least 60 Kpa.

[0072] In a headliner application the tensile strength is at least 100 Kpa, preferably at least 120 Kpa, more preferably at least 150 Kpa, even more preferably at least 180Kpa. Tn a carpet backing application, the elongation is at least 70%, preferably at least 75%, more preferably at least 80%.

[0073] In a carpet backing application, the foam density is typically 55-60 kg / m3.

[0074] In a carpet backing application, the compression at 40% is from 8-13 Kpa, preferably 10-12 Kpa.

[0075] Applications may include any in which PU is useful; flexible foams as typically used in transportation, high density foams as used in shoe production, rigid foams as used in construction, solid materials as used in composites.

[0076] Advantages provided by the invention are an increased total bio-content in final system when used in combination with bio-content in the resin component. Also an improved back-end cure is observed relative to when an equivalent bio-content is provided in the isocyanate reactive component.

[0077] Having generally described this invention, a further understanding can be obtained by reference to certain specific examples which are provided herein for purposes of illustration only and are not intended to be limiting unless otherwise specified.

[0078] EXAMPLES

[0079] Example 1 :

[0080] Prepolymers are prepared at up to 50% pbw bio-content in Lupranate M isocyanate, and up to 40% pbw in Lupranate M20 isocyanate.

[0081] The spray polyurethane resin component and isocyanate pre-polymer component described in Table 1 were mixed at a 1 : 1 by volume ratio using a Graco HFR high-pressure proportioning machine with a set temperature of 125°F and a set pressure of 1250psi. The foam was sprayed onto a half-inch OSB wood substrate at a 3-inch pass thickness. Compression strength, core density and R-value were tested following ASTM DI 621, ASTM DI 622, and ASTM C518, respectively. The physical properties are consistent with similar foam sprayed at a single pass thickness of 3-inches.

[0082] Table 1. Spray polyurethane foam formulas with corresponding physical property data Polyol A in the table above contains a ~2-functional polyester polyol with hydroxyl number between 200-300 and a ~2-functional polyol with hydroxyl number between 325-375 and derived from renewable resources in about a 2:3 ratio by weight.

[0083] Polyol B in the table above contains a ~2-functional polyester polyol with hydroxyl number between 200-300 and a ~3-functional polyester polyol with hydroxyl number between 300- 375 and derived from renewable resources in about a 5: 1 ratio by weight. Polyol C in the table above contains a ~4-functional polyether polyol with hydroxyl number between 400-450.

[0084] Additive Package A in the table above contains TCCP, Dabco 2040, Lupragen N 106, bismuth catalyst, and Surfonic N95. Additive Package B in the table above contains TCCP, Lupragen N106, bismuth catalyst.

[0085] Additive Package C in the table above contains PHT 4 Diol, Dabco DC 193, and HFO- 1233ZD in amounts equal or nearly equal to each other across the samples.

[0086] Example 2: The carpet underlay polyurethane B side polyol and A side isocyanate comprising biocontaining polyol described in Table 2 were mixed in a paper cup at using overhead mixer, then the mixture was poured into 12x12x1 inch mold. Tensile and compression properties of resulting blocks were tested following ASTM D3574.

[0087] Table 2. Carpet underlay polyurethane foam formulas with corresponding physical property data

[0088] Polyol D in the table above contains a ~2-functional polyether polyol with hydroxyl number between 20-40.

[0089] Polyol E in the table above contains a ~3 -functional poly ether polyol with hydroxyl number between 40-60.

[0090] Polyol F in the table above contains a ~4-functional polyether polyol with hydroxyl number between 400-500.

[0091] Renewable polyol A in the table above contains a ~3 -functional bio-based polyol with hydroxyl number between 100-200

[0092] Additive Package D in the table above contains Lupranol 3203 / 1, Fomrez UL-28, Jeffcat ZF- 10, Tegostab B 8734 LF2, Lupasol G20, Irgastab PUR70, black repitan 99430.

[0093] Example 3 :

[0094] The headliner polyurethane B side polyol and A side isocyanate comprising bio-containing polyol described in Table 2 were mixed in a paper cup at using overhead mixer, then the mixture was poured into 50x50x50 cm open box. Resulting blocks were sliced into 1-inch thick sheets, which were then tested for tensile and compression properties following ASTM D3574.

[0095] Table 3. Headliner polyurethane foam formulas with corresponding physical property data

[0096] Polyol G in the table above contains a ~3 -functional poly ether polyol with hydroxyl number between 40-60.

[0097] Polyol H in the table above contains a ~3 -functional poly ether polyol with hydroxyl number between 400-500.

[0098] Polyol I in the table above contains a ~3 -functional poly ether polyol with hydroxyl number between 150-200.

[0099] Renewable polyol B in the table above contains a ~2-functional bio-based polyol with hydroxyl number between 40-60

[0100] Additive Package E in the table above contains glycerin, diethylene glycol, Niax catalyst A- 1, DABCO DC 198, Niax silicone L-6915, Lupragen N 201. Numerous modifications and variations on the present invention are possible in light of the above teachings. It is therefore to be understood that within the scope of the appended claims, the invention may be practiced otherwise than as specifically described herein.

Claims

CLAIMS:

1. An isocyanate-containing prepolymer, comprising: the reaction product of a poly isocyanate with at least 20 wt. % of a bio-based polyol.

2. The isocyanate-containing prepolymer according to claim 1, wherein said polyisocyanate is at least one selected from the group consisting of ethylene diisocyanate, 1,4- tetramethylene diisocyanate, 1,6-hexam ethylene diisocyanate, 1,12-dodecane diisocyanate, cyclobutane-l,3-diisocyanate, cyclohexane- 1,3 -and -1,4-diisocyanate, l-isocyanato-3,3,5- trimethyl-5-isocyanatomethyl-cyclohexane ("isophorone diisocyanate"), 2,4- and 2,6- hexahydrotoluene diisocyanate, dicyclohexylmethane-4,4'-diisocyanate ("hydrogenated MDI", or "HMDI"), 1,3- and 1,4-phenylene diisocyanate, 2,4- and 2,6-toluene diisocyanate ("TDI"), diphenylmethane-2,4'- and / or -4,4'-diisocyanate ("MDI"), naphthylene- 1,5 -diisocyanate, triphenyl -m ethane-4, 4', 4"-triisocyanate, polyphenyl-polymethylene-polyisocyanates ("crude MDI"), norbornane diisocyanates, m- and p-isocyanatophenyl sulfonylisocyanates, perchlorinated aryl polyisocyanates, carbodiimide-modified polyisocyanates, urethane-modified polyisocyanates, allophanate-modified polyisocyanates, isocyanurate-modified polyisocyanates, urea-modified polyisocyanates, and biuret-containing polyisocyanates.

3. The isocyanate-containing prepolymer according to any one of claims 1-2, wherein said polyisocyanate is at least one selected from the group consisting of 4,4’-MDI, modified 4,4’-MDI, mixtures of 4,4’-MDI and 2,4’-MDI and polymeric MDI.

4. The isocyanate-containing prepolymer according to any one of claims 1-3, wherein said bio-based polyol is at least one polyol selected from the group consisting of castor oil soybean oil palm oil, rapeseed oil, tall oil and a bio-based linear polyester polyols.

5. The isocyanate-containing prepolymer according to any one of claims 1-4, wherein said bio-based polyol is a bio-based linear polyester polyols using bio-succinic acid, bio-adipic acid and bio-sebacic acid as the aliphatic diacids and diethylene glycol, 1,3 -propanediol and 1,4- butanediol or glycerol, sorbitol, and xylitol as polyol.

6. The isocyanate-containing prepolymer according to any one of claims 1-5, wherein said bio-based polyol is at least one selected from the group consisting of castor oil, modified castor oil, a modified soy oils, liquified and modified lignin.

7. The isocyanate-containing prepolymer according to any one of claims 1 -6, comprising8. The isocyanate-containing prepolymer according to any one of claims 1-7, comprising9. The isocyanate-containing prepolymer according to any one of claims 1-8, comprising 50 wt. % of bio-based polyol.

10. A polyurethane system, comprising: an isocyanate prepolymer comprising the reaction product of a polyisocyanate with at least 20 wt. % of a bio-based polyol; and an isocyanate reactive component.

11. The polyurethane system according to claim 10, wherein said isocyanate reactive component is at least one selected from the group consisting of polyols, polyethers, polyesters, polyacetals, polycarbonates, polyester ethers, polyester carbonates, polythioethers, polyamides, polyester amides, polysiloxanes, polybutadienes and polyacetones.

12. The polyurethane system according to claims 10-11, wherein said isocyanate reactive component is a bio-based polyol.

13. The polyurethane system according to claims 10-12, wherein said polyisocyanate is at least one selected from the group consisting of 4,4’-MDI, modified 4,4’-MDI, mixtures of 4,4’-MDI and 2,4’-MDI and polymeric MDI.

14. The polyurethane system according to any one of claims 10-13, wherein said biobased polyol s at least one selected from the group consisting of castor oil, modified castor oil, a modified soy oils, liquified and modified lignin.

15. .A polyurethane foam system, comprising: an A side isocyanate comprising < 20 wt. %; of a first bio-containing polyol; and a B side polyol comprising 30-50 wt % of a second bio-containing polyol.

16. The polyurethane foam system according to claim 15, wherein said first biocontaining polyol is at least one selected from the group consisting of castor oil, modified castor oil, a modified soy oils, liquified and modified lignin.

17. The polyurethane foam system according to claim 15, wherein said second biocontaining polyol is at least one selected from the group consisting of castor oil, modified castor oil, a modified soy oils, liquified and modified lignin.

18. A process for preparing a polyurethane foam comprising reacting a polyurethane foam system, comprising: an A side isocyanate comprising < 20 wt. %; of a first bio-containing polyol; and a B side polyol comprising 30-50 wt % of a second bio-containing polyol.

19. A polyurethane foam prepared according to the process of claim 18.

20. The polyurethane foam according to claim 19, suitable as an automotive headliner.

21. The polyurethane foam according to claim 19, suitable as a carpet backing.

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