US20050182228A1 - Plastic material - Google Patents
Plastic material Download PDFInfo
- Publication number
- US20050182228A1 US20050182228A1 US11/108,368 US10836805A US2005182228A1 US 20050182228 A1 US20050182228 A1 US 20050182228A1 US 10836805 A US10836805 A US 10836805A US 2005182228 A1 US2005182228 A1 US 2005182228A1
- Authority
- US
- United States
- Prior art keywords
- elastomer
- catalyst
- diisocyanate
- cross
- oil
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0014—Use of organic additives
- C08J9/0023—Use of organic additives containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/36—Hydroxylated esters of higher fatty acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0008—Foam properties flexible
Definitions
- plastic foams and elastomers have found wide use in a multitude of industrial and consumer applications.
- urethane foams and elastomers have been found to be well suited for many applications.
- Automobiles for instance, contain a number of components, such as cabin interior parts, that are comprised of urethane foams and elastomers.
- urethane foams are typically categorized as flexible, semi-rigid, or rigid foams with flexible foams generally being softer, less dense, more pliable, and more subject to structural rebound subsequent to loading than rigid foams.
- Urethanes are formed when isocyanate (NCO) groups react with hydroxyl (OH) groups.
- OH hydroxyl
- the most common method of urethane production is via the reaction of a polyol and an isocyanate which forms the backbone urethane group.
- a cross-linking agent may also be added.
- the precise formulation may be varied. Variables in the formulation include the type and amounts of each of the reactants.
- a blowing agent is added to cause gas or vapor to be evolved during the reaction.
- the blowing agent creates the void cells in the final foam, and commonly is a solvent with a relatively low boiling point or water. A low boiling solvent evaporates as heat is produced during the exothermic isocyanate/polyol reaction to form vapor bubbles.
- water is used as a blowing agent, a reaction occurs between the water and the isocyanate group to form an amine and carbon dioxide (CO 2 ) gas in the form of bubbles. In either case, as the reaction proceeds and the material solidifies, the vapor or gas bubbles are locked into place to form void cells.
- Final urethane foam density and rigidity may be controlled by varying the amount or type of blowing agent used.
- a cross-linking agent is often used to promote chemical cross-linking to result in a structured final urethane product.
- the particular type and amount of cross-linking agent used will determine final urethane properties such as elongation, tensile strength, tightness of cell structure, tear resistance, and hardness.
- final urethane properties such as elongation, tensile strength, tightness of cell structure, tear resistance, and hardness.
- the degree of cross-linking that occurs correlates to the flexibility of the final foam product.
- Relatively low molecular weight compounds with greater than single functionality are found to be useful as cross-linking agents.
- Catalysts may also be added to control reaction times and to effect final product qualities.
- the effects of catalysts generally include the speed of the reaction. In this respect, the catalyst interplays with the blowing agent to effect the final product density.
- the reaction should proceed at a rate such that maximum gas or vapor evolution coincides with the hardening of the reaction mass.
- the effect of a catalyst may include a faster curing time so that a urethane foam may be produced in a matter of minutes instead of hours.
- Polyester polyols and polyether polyols being the most common polyols used in urethanes production.
- polyester or polyether polyols with molecular weights greater than 6,000, are generally used.
- polyester or polyether polyols with molecular weights of 3,000 to 6,000 are generally used, while for flexible foams, shorter chain polyols with molecular weight of 600 to 4,000 are generally used.
- polyester and polyether polyols available for use, with particular polyols being used to engineer and produce a particular urethane elastomer or foam having desired particular final toughness, durability, density, flexibility, compression set ratios and modulus, and hardness qualities.
- higher molecular weight polyols and lower functionality polyols tend to produce more flexible foams than do lighter polyols and higher functionality polyols.
- petrochemicals such as polyester or polyether polyols
- petrochemicals are ultimately derived from petroleum, they are a non-renewable resource.
- the production of a polyol requires a great deal of energy, as oil must be drilled, extracted from the ground, transported to refineries, refined, and otherwise processed to yield the polyol.
- These required efforts add to the cost of polyols and to the disadvantageous environmental effects of its production.
- the price of polyols tends to be somewhat unpredictable as it tends to fluctuate based on the fluctuating price of petroleum.
- Plastics and foams made using fatty acid triglycerides derived from vegetables have been developed, including soybeans derivatives. Because soybeans are a renewable, relatively inexpensive, versatile, and environmentally friendly, they are desirable as ingredients for plastics manufacture. Soybeans may be processed to yield fatty acid triglyceride rich soy oil and protein rich soy flour.
- soy protein based formulations have been developed.
- U.S. Pat. No. 5,710,190 discloses the use of soy protein in the preparation of a thermoplastic foam.
- Such plastics are not suitable for use in applications that call for the particular properties of urethanes. Since urethanes don't utilize proteins in their formulations, soy proteins are not relevant to the manufacture of urethanes.
- Epoxidized soy oils, in combination with polyols, have also been used to formulate plastics and plastic foams, including urethanes.
- U.S. Pat. No. 5,482,980 teaches using an epoxidized soy oil in combination with a polyol to produce a urethane foam.
- a polyester or polyether polyol remains in the formulation, however. Also, as the epoxidation processing of the soy oil requires energy, material and time, use of an unmodified soy oil would be more advantageous.
- U.S. Pat. Nos. 2,787,601 and 2,833,730 disclose a rigid cellular plastic material that may be prepared using any of several vegetable oils, including soy oil as a prepolymer component only.
- the foam disclosed in these patents is made from a multistep process requiring the initial preparation of a prepolymer.
- relatively low cross-linker concentrations are urged, resulting in questionable product stability.
- use of a particular isocyanate, namely toluene diisocyanate is disclosed, which is disadvantageous due to its relatively high toxicity.
- One embodiment of the present invention includes an elastomer that includes the reaction product of an A-side that includes an isocyanate and a B-side that includes a blown vegetable oil, a cross-linking agent including a multi-functional alcohol, and a catalyst.
- Yet another embodiment of the present invention includes an elastomer that includes the reaction product of an A-side that includes a diisocyanate and a B-side that includes a blown soy oil, a multi-functional alcohol, and a catalyst.
- Another embodiment of the present invention includes an elastomer that includes the reaction product of an A-side that includes an isocyanate and a B-side that includes a blown soy oil, a multi-functional alcohol, a polyol derived from petroleum, and a catalyst.
- urethanes are well known in the art. They are generally produced by the reaction of petro-chemical polyols, either polyester or polyether, with isocyanates. The flexibility or rigidity of the foam is dependent on the molecular weight and functionality of the polyol and isocyanate used.
- Petrochemical polyol-based polyurethanes can be prepared in a one step or a two step process.
- A-side reactant is combined with what is known as a B-side reactant.
- the A-side is generally considered to comprise an isocyanate or a mixture of diisocyanate.
- the diisocyanates typically used are diphenylmethane diisocyanate (MDI) or toluylenediisocyanate (TDI).
- MDI diphenylmethane diisocyanate
- TDI toluylenediisocyanate
- the particular isocyanate chosen will depend on the particular final qualities desired in the urethane.
- the B-side material is generally a solution of a petroleum-based polyester or polyether polyol, cross-linking agent, and blowing agent.
- a catalyst is also generally added to the B-side to control reaction speed and effect final product qualities.
- a petrochemical such as a polyester or polyether polyol is undesirable for a number of reasons.
- flexible urethane foams of a high quality can be prepared by substituting the petroleum-based polyol in the B-side preparation with a vegetable oil in the presence of a multi-functional alcohol cross-linking agent.
- the molar ratio of the hydroxyl (OH) groups of the cross-linking agent hydroxyl (OH) groups to the vegetable oil is preferably at least 0.7:1, and most preferably between about 0.7 and 1.2:1.
- the replacement is made on a substantially 1:1 weight ratio of vegetable oil for replaced petroleum-based polyol.
- a blend of petroleum-based polyol and vegetable oil may be used.
- the process of producing the urethane does not change significantly with the petroleum-based polyol replaced by the vegetable oil with all other components and general methods as are generally known in the art.
- the qualities of the final flexible, semi-rigid, or rigid urethane foam produced using the vegetable oil are consistent with those produced using a high grade, expensive polyol.
- urethane foams of varying and selectable final qualities can be made by varying only the primary reactants. It would be difficult, if not impossible, to create such varied final foams using a single petroleum-based polyester or polyether polyol with the same variations in the remaining reactants. Instead, different petroleum-based polyols would be required to produce such varied results.
- Vegetable oils are abundant, renewable, and easily processed commodities, as opposed to polyols, which petroleum derivatives and which entail significant associated processing costs. As such, they may currently be acquired for a cost of approximately half that of average grade petroleum-based polyurea, polyester or polyether polyols, and approximately one quarter the cost of high grade petroleum-based polyester or polyether polyols. Also, as polyols derived from petroleum, they are not renewable and carry a certain environmental cost with them. There is a distinct marketing advantage to marketing products that are based on environmentally friendly, renewable resources such as vegetable oils.
- the A-side isocyanate reactant of the urethane of the invention is preferably comprised of an isocyanate chosen from a number of suitable isocyanates as are generally known in the art. Different isocyanates may be selected to create different properties in the final product.
- the A-side reactant of the urethane of the invention comprises diisocyanate; 4,4′ diphenylmethane diisocyanate; 2,4-diphenylmethane diisocyanate; and modified diphenylmethane diisocyanate.
- a modified diphenylmethane diisocyanate is used. It should be understood that mixtures of different isocyanates may also be used.
- the A-side of the reaction may also be a prepolymer isocyanate.
- the prepolymer isocyanate is typically the reaction product of an isocyanate, preferably a diisocyanate, and most preferably some form of diphenylmethane diisocyanate and a vegetable oil.
- the vegetable oil can be soy oil, rapeseed oil, cottonseed oil, or palm oil, or any other oil having a suitable number of reactive hydroxyl (OH) groups.
- the most preferred vegetable oil is soy oil.
- the vegetable oil and isocyanate are mixed in a 1:1 ratio for 10-15 seconds every 10-15 minutes for a total of 4 hours or until the reaction has ended.
- isocyanate (NCO) groups there will still be unreacted isocyanate (NCO) groups in the prepolymer.
- the prepolymer reaction reduces the cost of the A-side component by decreasing the amount of isocyanate required and utilizes a greater amount of inexpensive, environmentally friendly soy oil.
- additional isocyanate must be added to elevate the isocyanate (NCO) level to an acceptable level.
- the B-side reactant of the urethane reaction includes at least vegetable oil and a cross-linking agent. Typically, a blowing agent and a catalyst are also included in the B-side. It is believed that the isocyanate reacts with the fatty acids of the vegetable oil to produce the polymeric backbone of the urethane.
- the vegetable oils that are suitable for use tend to be those that are relatively high in triglyceride concentration and that are available at a relatively low cost.
- the preferred vegetable oil is soy oil, although it is contemplated that other vegetable oils, such as rapeseed oil (also known as canola oil), cottonseed oil, and palm oil can be used in accordance with the present invention. Except for the preliminary blowing step where air is passed through the oil to remove impurities and to thicken it, the soy oil is otherwise unmodified. It does not require esterification as is required for some urethane products of the prior art.
- the preferred blown soy oil has the following composition: 100% Pure Soybean Oil Air Oxidized Moisture 1.15% Free Fatty Acid 5.92% as OLEIC Phosphorous 55.5 ppm Peroxide Value 137.22 Meq/Kg Iron 6.5 ppm Hydroxyl Number 212 mgKOH/g Acid Value 12.46 mgKOH/g Sulfur 200 ppm Tin ⁇ .5 ppm
- preferred blowing agents for the invention are those that are likewise known in the art and may be chosen from the group comprising 134A HCFC, a hydrochloroflurocarbon refrigerant available from Dow Chemical Co., Midland Mich.; methyl isobutyl ketone (MIBK); acetone; a hydroflurocarbon; and methylene chloride. These preferred blowing agents create vapor bubbles in the reacting mass. Should other blowing agents be used that react chemically, such as water reacting with the isocyanate (NCO) groups, to produce a gaseous product, concentrations of other reactants may be adjusted to accommodate the reaction.
- NCO isocyanate
- the cross-linking agents of the foam of the present invention are also those that are well known in the art. They must be at least di-functional (a diol).
- the preferred cross-linking agents for the foam of the invention are ethylene glycol and 1,4 butanediol; however, other diols may be used. It has been found that a mixture of ethylene glycol and 1,4 butanediol is particularly advantageous in the practice of the present invention. Ethylene glycol tends to offer a shorter chain molecular structure with many “dead end” sites, tending to create a firmer final foam resistant to tearing or “unzipping,” while 1,4 butanediol offers a longer chain molecular structure, tending to create a softer foam. Proper mixture of the two can create engineered foams of almost any desired structural characteristics.
- one or more catalyst may be present.
- the preferred catalysts for the urethanes of the present invention are those that are generally known in the art and are most preferably tertiary amines chosen from the group comprising DABCO 33-LV® comprised of 33% 1,4 diaza-bicyclco-octane (triethylenediamine) and 67% dipropylene glycol, a gel catalyst available from the Air Products Corporation; DABCO® BL-22 blowing catalyst available from the Air Products Corporation; and POLYCAT® 41 trimerization catalyst available from the Air Products Corporation.
- the B-side reactant may further comprise a silicone surfactant which functions to influence liquid surface tension and thereby influence the size of the bubbles formed and ultimately the size of the hardened void cells in the final foam product.
- a silicone surfactant which functions to influence liquid surface tension and thereby influence the size of the bubbles formed and ultimately the size of the hardened void cells in the final foam product. This can effect foam density and foam rebound (index of elasticity of foam).
- the surfactant may function as a cell opening agent to cause larger cells to be formed in the foam. This results in uniform foam density, increased rebound, and a softer foam.
- a molecular sieve may further be present to absorb excess water from the reaction mixture.
- the preferred molecular sieve of the present invention is available under the trade name L-pasteTM.
- the flexible and semi-rigid foams of the invention will have greater than approximately 60% open cells.
- the preferred flexible foam of the invention will also have a density of from 1 lb. to 45 lb. per cubic foot and a hardness of durometer between 20 and 70 Shore “A.”
- the urethane foam of the present invention is produced by combining the A-side reactant with the B-side reactant in the same manner as is generally known in the art.
- use of the vegetable oil to replace the petroleum-based polyol does not require significant changes in the method of performing the reaction procedure.
- an exothermic reaction ensues that may reach completion in anywhere from several minutes to several hours depending on the particular reactants and concentrations used.
- the reaction is carried out in a mold so that the foam expands to fill the mold, thereby creating a final foam product in the shape of the mold.
- the preferred flexible foam of the invention B-side mixture when using the preferred components, is prepared with the following general weight ratios: Blown soy oil 100 parts Cross-linking agent 8-15 parts Blowing agent 8-15 parts Catalyst 1-12 parts
- a petroleum based polyol such as polyether polyol, polyester polyol, or polyurea polyol may be substituted for some of the blown soy oil in the B-side of the reaction, however, this is not necessary.
- This preferred B-side formulation is then combined with the A-side to produce a foam.
- the preferred A-side as discussed previously, is comprised of MDI or a prepolymer comprised of MDI and a vegetable oil, preferably soy oil.
- the A-side and B-side are typically, and preferably in an approximate ratio of about 35 parts to about 85 parts A-side to 100 parts B-side.
- Flexible urethane foams may be produced with differing final qualities using the same vegetable oil by varying the particular other reactants chosen. For instance, it is expected that the use of relatively high molecular weight and high functionality isocyanates will result in a less flexible foam than will use of a lower molecular weight and lower functionality isocyanate when used with the same vegetable oil. Similarly, it is expected that lower molecular weight and lower functionality cross-linkers will result in a more flexible foam than will higher molecular weight and higher functionality cross-linkers when used with the same vegetable oil. Also, a ethylene glycol cross-linker will result in shorter final chains and a firmer foam, while use of a butanediol cross-linker results in longer chains and a softer foam. Moreover, it has been contemplated that chain extenders may also be employed in the present invention. Butanediol, in addition to acting as a cross-linker, may act as a chain extender.
- Urethane elastomers can be produced in much the same manner as urethane foams, except that a blowing agent is not present to create void cells in the material. It has been discovered that useful urethane elastomers may be prepared using a vegetable oil to replace a petroleum-based polyester or polyether polyol.
- the preferred elastomer of the invention is produced using diphenylmethane diisocyanate (MDI); 1,4 butanediol cross-linking agent; and a vegetable oil, preferably soy oil.
- a catalyst may be added to the reaction composition to decelerate the speed of the reaction.
- the preferred elastomer of the invention is prepared by combining the reactants. An exothermic reaction occurs that creates the elastomer.
- the preferred elastomer has an approximate density of 65 lb. to 75 lb. per cubic foot.
- the following examples of preparation of foams and elastomers of the invention summarized in Table A will illustrate various embodiments of the invention.
- the B-Side silica
- the A-side material in the following examples is comprised of modified diphenylmethane diisocyanate (MDI).
- MDI modified diphenylmethane diisocyanate
- the prepolymer A-side material in the following examples is the reaction product of a vegetable oil, preferably soy oil, and a modified diphenylmethane diisocyanate (MDI).
- MDI materials There are four different MDI materials specified in the following examples; all are modified monomeric or polymeric diphenylmethane diisocyanates available from the Bayer Corp., Polymers Division, Rosemont Ill.: “Mondur® MA-2901” (Bayer Product Code No. C-1464); “Mondur®-448” (Bayer Product Code No. G-448), “Mondur® MRS-20”, and “Mondur®-PF”.
- cure in the following examples refers to the final, cured foam taken from the mold.
- the soy oil used in the following examples is blown soy oil obtained from Cargill, in Chicago, Ill.
- Catalysts used include “DABCO 33-LV®,” comprised of 33% 1,4-diaza-bicyclo-octane and 67% dipropylene glycol available from the Air Products Urethanes Division; “DABCO® BL-22,” a tertiary amine blowing catalyst also available from the Air Products Urethanes Division; and “POLYCAT® 41” (n, n′, n′′, dimethylamino-propyl-hexahydrotriazine tertiary amine) also available from the Air Products Urethanes Division.
- Catalysts in the following Examples may be referred to as “front end,” “back end,” and “blowing”. Front end catalysts tend to speed the early portion of the reaction, while back end catalysts tend to speed the later, curing portion of the reaction.
- a blowing catalyst effects the timing of the activation of the blowing agent.
- Some of the Examples include “L-pasteTM,” which is a trade name for a molecular sieve for absorbing water. Some also contain “DABCO® DC-5160,” a silicone surfactant available from Air Products Urethane Division.
- the B-side material was prepared as follows: 50 g Soy Oil 5 g Ethylene Glycol (cross-linker) 1 g Front end catalyst (DABCO 33-LV ®; 33% triethylenediamine and 67% dipropylene glycol) 1 g Blow catalyst (DABCO ® BL-22; a tertiary amine catalyst) 4 g Methyl Isobutyl Ketone (blowing agent)
- Blown soy oil has a molecular weight of about 278, while the ethylene glycol has a molecular weight of about 62.
- the molar ratio of ethylene glycol to blown soy oil is 0.22:1. Since the ethylene glycol has two hydroxyl (OH) groups with which to cross-link the constituent fatty acids of the blown soy oil, the molar ratio of the hydroxyl (OH) groups of the ethylene glycol to soy oil is about 0.45:1.
- the resulting B-side was then combined with an A-side material in a ratio of 50 parts A-side to 100 parts B-side.
- the A-side material is comprised of Mondur® 448, a modified monomeric diphenylmethane diisocyanate (pMDI). The cure was acceptable; however, the cellular material remained tacky at the surface for 20 minutes.
- the B-side is the same as that of Example 1.
- the A-side is comprised of MA-2901, a modified diphenylmethane diisocyanate.
- the B-side was combined with the A-side in a ratio of 52 parts A-side to 100 parts B-side. The cure was acceptable, although the cellular material remained tacky for 12 minutes.
- the A-side was the same as Example 2.
- the B-side was again the same as that of Example 1, except that 1.5 parts of methanol were added as additional blowing agent.
- the ratio was 52 parts A-side to 100 parts B-side.
- the sample cured in 1 hour. It was not a favorable result in that the cellular material foamed and then fell back to solid and rose again. The methanol apparently had an adverse affect.
- the A-side was the same as Example 2.
- the materials were reacted in a ratio of 50 parts A-side to 100 parts B-side.
- the results were a good foam, but weak in tensile strength.
- Example 4 The B-side and A-side are the same as in Example 4. However, the materials were reacted in a ratio of 52 parts A-side to 100 parts B-side. The results were essentially the same as in Example 4 with a little better tensile strength.
- B-Side 103 g Soy Oil 10 g Ethylene Glycol (cross-linker) 11 g Acetone (Blowing agent) 2.5 g Front end catalyst (DABCO 33-LV ®; 33% 1,4-diaza-bicyclo-octane and 67% dipropylene glycol) 2.5 g Blow catalyst (DABCO ® BL-22; a tertiary amine catalyst)
- the molar ratio of ethylene glycol to blown soy oil is 0.44:1. With two hydroxyl (OH) groups with which to cross-link the constituent fatty acids of the blown soy oil, the molar ratio of the hydroxyl (OH) groups of the ethylene glycol to soy oil is about 0.90:1.
- the A-side comprises 52 parts MA-2901, a modified monomeric diphenylmethane diisocyanate, to 100 parts B-side. The resulting foam was hard and its cell size large. It fell back to a solid, largely due to too much blowing agent.
- B-side 100 g Soy Oil 8 g Ethylene Glycol (cross-linker) 5 g Acetone (Blowing agent) 2.5 g Front end catalyst (DABCO 33-LV ®; 33% 1,4-diaza-bicyclo-octane and 67% dipropylene glycol) 2.5 g Blow catalyst (DABCO ® BL-22; a tertiary amine catalyst)
- the molar ratio of ethylene glycol to blown soy oil is 0.35 to 1. With two hydroxyl (OH) groups with which to cross-link the constituent fatty acids of the blown soy oil, the molar ratio of the hydroxyl (OH) groups of the ethylene glycol to soy oil is about 0.70:1.
- the A-side comprises MA-2901, a modified monomeric diphenylmethane diisocyanate, and is present in 51 parts A-side to 100 parts B-side.
- the resulting foam is generally a good foam, having low tensile strength but a better density range.
- the B-side is the same as that of Example 7.
- the A-side also comprises MA-2901, a modified monomeric diphenylmethane diisocyanate, as in Example 7.
- the A-side is present in a ratio of 45 parts A-side to 100 parts B-side.
- A-side and B-side are the same as in Example 7. However, 72 parts A-side were reacted with 100 parts B-side. The resulting foam fell back and did not cure after 1 hour, indicating an overcharge of A-side.
- the molar ratio of ethylene glycol to blown soy oil is 0.49:1. With two hydroxyl (OH) groups with which to cross-link the constituent fatty acids of the blown soy oil, the molar ratio of the hydroxyl (OH) groups of the ethylene glycol to soy oil is about 0.99:1.
- the A-side comprised MA-2901, a modified monomeric diphenylmethane diisocyanate. The A-side was reacted with the B-side in a ratio of 50 parts A-side to 100 parts B-side. The resulting foam had a 15-minute cure and a very slow recovery. However, the final cure was insufficient because it did not occur for 72 hours.
- the B-side is as in Example 10.
- the A-side comprises Mondur® 448, a modified monomeric diphenylmethane diisocyanate, in a ratio of 50 parts A-side to 100 parts B-side.
- the resulting foam cures in 15 minutes, but is very crumbly.
- the B-side is as in Example 10.
- the A-side comprised 76 parts MA-2901, a modified monomeric diphenylmethane diisocyanate, to 100 parts B-side.
- the resulting foam cures in 30 minutes, but has a very fast, complete fall back.
- Ethylene glycol has a molecular weight of about 62 and 1,4 butanediol has a molecular weight of about 90.
- the molar ratio of the ethylene glycol to blown soy oil is 0.22:1 and the molar ratio of the 1,4 butanediol to blown soy oil is 0.15:1.
- the molar ratio of the hydroxyl (OH) groups of the 50/50 ethylene glycol/1,4 butanediol cross-linker mixture to the blown soy oil is about 0.75:1.
- the A-side was reacted at 74 parts MA-2901, a modified monomeric diphenylmethane diisocyanate to 100 parts B-side.
- the resulting foam cured to the touch within 3 minutes and fully cured within 15 minutes. It has good properties.
- the A-side was reacted at 74 parts, a modified MDI, MA-2901, to 100 parts B-side.
- the resulting foam cured to the touch within 3 minutes and exhibited slightly better initial strength than the foam of Example 13. It fully cured within 15 minutes with good properties.
- the molar ratio of the ethylene glycol to blown soy oil is 0.15:1 and the molar ratio of the 1,4 butanediol to blown soy oil is 0.24:1. Since each of the ethylene glycol and 1,4 butanediol have two hydroxyl (OH) groups with which to cross-link the constituent fatty acids of the blown soy oil, the molar ratio of the hydroxyl (OH) groups of the 50/50 ethylene glycol/1,4 butanediol cross-linker mixture to blown soy oil is about 0.80:1.
- the A-side was reacted at 74 parts, a modified MDI, MA-2901 to 100 parts B-side.
- the resulting foam had very good qualities.
- the foam exhibited good elastomeric and fast cure (tack-free after 90 seconds) properties and was soft with good elastomeric properties after 1 hour.
- the B-side is the same blend as Example 15.
- the A-side comprises, a modified MDI, Mondur® 448.
- the A-side was reacted at 74 parts A-side to 100 parts B-side.
- the reaction time was good and the resulting foam was a stiff flexible foam with good elastomeric properties.
- the foam continued to exhibit good elastomeric properties after 1 hour.
- the molar ratio of the hydroxyl (OH) groups of the 50/50 ethylene glycol/1,4 butanediol cross-linker mixture to soy oil is again about 0.75:1.
- the A-side comprises a 50/50 blend of, a modified MDI, MA-2901 and a modified pMDI, Mondur® 448.
- the A-side was reacted with the B-side at 74 parts A-side to 100 parts B-side.
- the resulting foam is a good foam with good flexibility, high density, but still needs tensile improvements.
- the molar ratio of the hydroxyl (OH) groups of the 5/21 ethylene glycol/1,4 butanediol mixture to blown soy oil is about 0.85:1.
- the A-side comprises a 50/50 blend of a modified MDI, MA-2901 and a modified pMDI, Mondur® 448.
- the A-side was reacted with the B-side at 74 parts A-side to 100 parts B-side.
- the resulting foam is very similar to that of Example 17 and is a good foam with good flexibility, high density, but still needs tensile improvements.
- the molar ratio of the hydroxyl (OH) groups of the 22/4 ethylene glycol/1,4 butanediol mixture to blown soy oil is about 1.10:1.
- the A-side comprises a modified MDI, MA-290.
- the A-side and the B-side were reacted at 74 parts A-side to 100 parts B-side.
- the resulting foam demonstrated very good properties. It is almost a solid elastomer with good rebound.
- the molar ratio of the hydroxyl (OH) groups of the 22/4 ethylene glycol/1,4 butanediol mixture to blown soy oil is again about 1.10:1.
- the A-side comprises a modified MDI, MA-2901, and was reacted at 74 parts A-side to 100 parts B-side.
- the resulting foam was a very good foam having uniform cell size, good flex, moderate density, good rebound and higher tensile strength.
- the molar ratio of the hydroxyl (OH) groups of the 22/4 ethylene glycol/1,4 butanediol mixture to blown soy oil is again about 1.10:1.
- the A-side comprises a modified MDI, MA-2901, and was reacted at 81 parts A-side to 100 parts B-side.
- the molar ratio of the hydroxyl (OH) groups of the 22/4 ethylene glycol/1,4 butanediol mixture to blown soy oil is again about 1.10:1.
- the A-side comprises a modified MDI, MA-2901.
- the A-side and the B-side were reacted at 80 parts A-side to 100 parts B-side.
- the resulting foam was a good foam. It was a stiffer flexible foam with good cell size, good uniformity, and low to moderate density.
- the molar ratio of the hydroxyl (OH) groups of the 35/15 ethylene glycol/1,4 butanediol mixture to blown soy oil is about 1.00:1.
- the A-side comprises a modified MDI, MA-2901, and was reacted at 74 parts A-side to 100 parts B-side.
- the resulting foam is low in density with poor tensile strength.
- the molar ratio of the hydroxyl (OH) groups of the 25/6 ethylene glycol/1,4 butanediol mixture to soy oil is about 1.50:1.
- the A-side comprises a 2,4′ rich polymeric MDI, Mondur® MRS-20, and was reacted at 70 parts to 100 parts B-side. The resulting reaction had no foaming and no real reaction.
- Example 24 is repeated with A-side comprising Mondur®-PF, a modified MDI. Again, no foaming and not a good reaction.
- Example 24 is again repeated, with the A-side this time comprising a 50/50 mixture of a modified MDI, MA-2901, and a modified pMDI, Mondur® 448. It is reacted at 70 parts to 100 parts B-side.
- the A-side comprises a modified MDI, MA-2901.
- the B-side comprises the following: B-side 100 g Soy Oil 7 g Dipropylene-glycol (cross-linker) 2 g Front end catalyst (DABCO 33-LV ®; 33% triethylenediamine and 67% dipropylene glycol) 2 g Back end catalyst (DABCO ® 8154; an amine salt)
- the A-side and B-side reactions were mixed in a ratio of 60 parts A-side to 100 parts B-side.
- the resultant foam exhibited excellent properties.
- the A-side and B-side reactions were mixed in a ratio of 60 parts A-side to 100 parts B-side.
- the resultant reaction produced a foam exhibiting excellent properties.
- the A-side and B-side components are identical to those in Example 28.
- the A-side was reacted with the B-side in a ratio of 68 parts A-side and 100 parts B-side.
- the foam produced by the reaction had excellent properties.
- the A-side comprises a mix of a modified MDI, MA-2901, and a modified pMDI, Mondur® 448.
- the B-side comprises the following: B-side 100 g Soy Oil 3 g Tripropylene glycol (cross-linker) 3 g Dipropylene glycol (cross-linker) 2 g Front end catalyst (DABCO 33-LV ®; 33% triethylenediamine and 67% dipropylene glycol) 2 g Back end catalyst (DABCO ® 8154; an amine salt)
- the A-side and B-side were mixed in a ratio of 60 parts A-side to 100 parts B-side.
- the resultant foam was a rigid foam exhibiting excellent properties.
- the A-side was identical to the A-side of Example 30 and the B-side is identical to Example 30 except for the fact that 6% butanediol was added to the B-side.
- the A-side and B-side were mixed in a ratio of 60 parts A-side to 100 parts B-side.
- the resultant foam was a rigid foam exhibiting excellent properties.
- the addition of the butanediol increased the speed of the reaction compared to Example 30.
- the A-side comprises polymeric MDI.
- the B-side comprises the following: B-side 200 g Soy Oil 30 g Ethylene glycol cross-linker) 15 g Butanediol (cross-linker) 5 g Aliphatic amine tetrol (CL-485; cross-linker) 25 g Molecular sieve (L-paste TM) 8 g Front end catalyst (DABCO 33-LV ®; 33% triethylenediamine and 67% dipropylene glycol) 5 g Back end catalyst (DABCO ® 1854; an amine salt)
- the A-side and B-side were mixed in a 1:1 ratio.
- the foam resulting from the chemical reaction was a rigid foam with good properties.
- the A-side and B-side were mixed in a ratio of 35 parts A-side to 100 parts B-side.
- the resulting foam was very good after about 15 minutes.
- the A-side comprises either MDI or pMDI.
- the B-side comprised the following: B-side 200 g Soy Oil 200 g Polyurea polyol 48 g Aliphatic amine tetrol (cross-linker) 30 g Ethylene glycol (cross-linker) 3 g Front end catalyst (DABCO 33-LV ®; 33% triethylenediamine and 67% dipropylene glycol) 3 g Back end catalyst (Polycat 41 ®; n, n′, n′′, dimethylamino-propyl- hexahydrotriazine tertiary amine) 3 g Tertiary amine catalyst (DABCO ® BL-22) 7 g Molecular sieve (L-paste TM)
- the A-side and B-side were combined in a ratio of 50 parts A-side to 100 parts B-side.
- the result reaction occurred very fast and the resultant elastomer exhibited good properties.
- Combining the A-side and the B-side in a ratio of 68 parts A-side to 100 parts B-side also results in an elastomer with good properties.
- the A-side was blended with the B-side in a ratio of 40 parts A-side to 100 parts B-side.
- the resultant foam had good properties, but was slightly hard.
- the A-side and B-side are identical to Example 35, however, 5% methylene chloride and 1% of a stabilizing anti-oxidant, Stabaxol® were added to the B-side.
- the A-side and the B-side were mixed in a ratio of 32 parts A-side to 100 parts B-side and a ratio of 36.5 parts A-side to 100 parts B-side. Both resulting foams were good, soft foams.
- the addition of the methylene chloride as a blowing agent greatly assisted the reaction without pulling out water thereby allowing the foam to stay soft.
- the A-side comprises a 50/50 mixture of modified MDI and modified pMDI.
- the B-side comprises the following: B-side 400 g Soy Oil 400 g Polyurea polyol (petroleum based polyol) 96 g Aliphatic amine tetrol (cross-linker; amine salt) 60 g Ethylene glycol (cross-linker) 6 g Front end catalyst (DABCO 33-LV ®; 33% triethylenediamine and 67% dipropylene glycol) 3 g Back end catalyst (tertiary amine catalyst) 6 g Blow catalyst (DABCO ® BL-22)
- the A-side was combined with the B-side in a ratio of 50 parts A-side to 100 parts B-side.
- the resultant foam exhibited good overall properties.
- the A-side comprises a polymeric MDI, Mondur® MR light.
- the B-side comprises the following: B-side 50 g Soy Oil 50 g Sucrose polyol (Bayer 4035) 10 g Ethylene glycol (cross-linker) 2.5 g Dipropylene glycol (cross-linker) 3.0 g Front end catalyst 2.0 g Back end catalyst (tertiary block amine catalyst)
- the A-side was mixed with the B-side at the following ratios: A-side B-side 50 100 70 100 80 100 90 100 100 100
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Emergency Medicine (AREA)
- Polyurethanes Or Polyureas (AREA)
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Materials For Medical Uses (AREA)
- Massaging Devices (AREA)
Abstract
An elastomer that includes the reaction product of an A-side that includes an isocyanate and a B-side that includes a blown vegetable oil, a cross-linking agent including a multi-functional alcohol, and a catalyst.
Description
- This application is a continuation of and claims the benefit of U.S. patent application Ser. No. 10/639,109, filed on Aug. 12, 2003, which is a division of U.S. patent application Ser. No. 10/253,252, filed on Sep. 24, 2002, which has now issued as U.S. Pat. No. 6,624,244, which is a continuation of U.S. patent application Ser. No. 09/646,356, which has now issued as U.S. Pat. No. 6,465,569, which is based upon and claims the benefit of PCT Application No. WO 00/15684, filed on Sep. 17, 1999, which is a continuation-in-part and claims the benefit of U.S. patent application Ser. No. 09/154,340, which has now issued as U.S. Pat. No. 6,180,686.
- Because of their widely ranging mechanical properties and their ability to be relatively easily machined and formed, plastic foams and elastomers have found wide use in a multitude of industrial and consumer applications. In particular, urethane foams and elastomers have been found to be well suited for many applications. Automobiles, for instance, contain a number of components, such as cabin interior parts, that are comprised of urethane foams and elastomers. Such urethane foams are typically categorized as flexible, semi-rigid, or rigid foams with flexible foams generally being softer, less dense, more pliable, and more subject to structural rebound subsequent to loading than rigid foams.
- The production of urethane foams and elastomers are well known in the art. Urethanes are formed when isocyanate (NCO) groups react with hydroxyl (OH) groups. The most common method of urethane production is via the reaction of a polyol and an isocyanate which forms the backbone urethane group. A cross-linking agent may also be added. Depending on the desired qualities of the final urethane product, the precise formulation may be varied. Variables in the formulation include the type and amounts of each of the reactants.
- In the case of a urethane foam, a blowing agent is added to cause gas or vapor to be evolved during the reaction. The blowing agent creates the void cells in the final foam, and commonly is a solvent with a relatively low boiling point or water. A low boiling solvent evaporates as heat is produced during the exothermic isocyanate/polyol reaction to form vapor bubbles. If water is used as a blowing agent, a reaction occurs between the water and the isocyanate group to form an amine and carbon dioxide (CO2) gas in the form of bubbles. In either case, as the reaction proceeds and the material solidifies, the vapor or gas bubbles are locked into place to form void cells. Final urethane foam density and rigidity may be controlled by varying the amount or type of blowing agent used.
- A cross-linking agent is often used to promote chemical cross-linking to result in a structured final urethane product. The particular type and amount of cross-linking agent used will determine final urethane properties such as elongation, tensile strength, tightness of cell structure, tear resistance, and hardness. Generally, the degree of cross-linking that occurs correlates to the flexibility of the final foam product. Relatively low molecular weight compounds with greater than single functionality are found to be useful as cross-linking agents.
- Catalysts may also be added to control reaction times and to effect final product qualities. The effects of catalysts generally include the speed of the reaction. In this respect, the catalyst interplays with the blowing agent to effect the final product density. The reaction should proceed at a rate such that maximum gas or vapor evolution coincides with the hardening of the reaction mass. Also, the effect of a catalyst may include a faster curing time so that a urethane foam may be produced in a matter of minutes instead of hours.
- Polyols used in the production of urethanes are petrochemicals. Polyester polyols and polyether polyols being the most common polyols used in urethanes production. For rigid foams, polyester or polyether polyols with molecular weights greater than 6,000, are generally used. For semi-rigid foams, polyester or polyether polyols with molecular weights of 3,000 to 6,000 are generally used, while for flexible foams, shorter chain polyols with molecular weight of 600 to 4,000 are generally used. There is a very wide variety of polyester and polyether polyols available for use, with particular polyols being used to engineer and produce a particular urethane elastomer or foam having desired particular final toughness, durability, density, flexibility, compression set ratios and modulus, and hardness qualities. Generally, higher molecular weight polyols and lower functionality polyols tend to produce more flexible foams than do lighter polyols and higher functionality polyols. In order to eliminate the need to produce, store, and use different polyols, it would be advantageous to have a single versatile component that was capable of being used to create final urethane foams of widely varying qualities.
- Further, use of petrochemicals such as polyester or polyether polyols is disadvantageous for a variety of reasons. As petrochemicals are ultimately derived from petroleum, they are a non-renewable resource. The production of a polyol requires a great deal of energy, as oil must be drilled, extracted from the ground, transported to refineries, refined, and otherwise processed to yield the polyol. These required efforts add to the cost of polyols and to the disadvantageous environmental effects of its production. Also, the price of polyols tends to be somewhat unpredictable as it tends to fluctuate based on the fluctuating price of petroleum.
- Also, as the consuming public becomes more aware of environmental issues, there are distinct marketing disadvantages to petrochemical-based products. Consumer demand for “greener” products continues to grow. As a result, it would be most advantageous to replace polyester or polyether polyols, as used in the production of urethane elastomers and foams, with a more versatile, renewable, less costly, and more environmentally friendly component.
- Efforts have been made to accomplish this. Plastics and foams made using fatty acid triglycerides derived from vegetables have been developed, including soybeans derivatives. Because soybeans are a renewable, relatively inexpensive, versatile, and environmentally friendly, they are desirable as ingredients for plastics manufacture. Soybeans may be processed to yield fatty acid triglyceride rich soy oil and protein rich soy flour.
- Unlike urethanes, many plastics are protein based. For these types of plastics, soy protein based formulations have been developed. U.S. Pat. No. 5,710,190, for instance, discloses the use of soy protein in the preparation of a thermoplastic foam. Such plastics, however, are not suitable for use in applications that call for the particular properties of urethanes. Since urethanes don't utilize proteins in their formulations, soy proteins are not relevant to the manufacture of urethanes.
- Epoxidized soy oils, in combination with polyols, have also been used to formulate plastics and plastic foams, including urethanes. For example, U.S. Pat. No. 5,482,980 teaches using an epoxidized soy oil in combination with a polyol to produce a urethane foam. A polyester or polyether polyol remains in the formulation, however. Also, as the epoxidation processing of the soy oil requires energy, material and time, use of an unmodified soy oil would be more advantageous.
- Efforts have been made to produce a urethane type cellular plastic from unmodified soy oil. U.S. Pat. Nos. 2,787,601 and 2,833,730 disclose a rigid cellular plastic material that may be prepared using any of several vegetable oils, including soy oil as a prepolymer component only. The foam disclosed in these patents is made from a multistep process requiring the initial preparation of a prepolymer. Moreover, in the case of U.S. Pat. No. 2,833,730, relatively low cross-linker concentrations are urged, resulting in questionable product stability. Further, use of a particular isocyanate, namely toluene diisocyanate, is disclosed, which is disadvantageous due to its relatively high toxicity.
- An unresolved need therefore exists in industry for a urethane elastomer, a urethane foam, and a method of producing such materials that are based on a reaction between isocyanates alone or as a prepolymer, in combination with, a vegetable oil or a vegetable oil-polyurea polyol blend, are particularly desirable because they are relatively inexpensive, versatile, renewable, environmentally friendly material such as vegetable oils as a replacement for polyether or polyester polyols typically employed.
- One embodiment of the present invention includes an elastomer that includes the reaction product of an A-side that includes an isocyanate and a B-side that includes a blown vegetable oil, a cross-linking agent including a multi-functional alcohol, and a catalyst.
- Yet another embodiment of the present invention includes an elastomer that includes the reaction product of an A-side that includes a diisocyanate and a B-side that includes a blown soy oil, a multi-functional alcohol, and a catalyst.
- Another embodiment of the present invention includes an elastomer that includes the reaction product of an A-side that includes an isocyanate and a B-side that includes a blown soy oil, a multi-functional alcohol, a polyol derived from petroleum, and a catalyst.
- These and other features, advantages and objects of the present invention will be further understood and appreciated by those skilled in the art by reference to the following specification and claims.
- The preparation of urethanes is well known in the art. They are generally produced by the reaction of petro-chemical polyols, either polyester or polyether, with isocyanates. The flexibility or rigidity of the foam is dependent on the molecular weight and functionality of the polyol and isocyanate used.
- Petrochemical polyol-based polyurethanes can be prepared in a one step or a two step process. In the one step process, what is known in the art as an A-side reactant is combined with what is known as a B-side reactant. The A-side is generally considered to comprise an isocyanate or a mixture of diisocyanate. The diisocyanates typically used are diphenylmethane diisocyanate (MDI) or toluylenediisocyanate (TDI). The particular isocyanate chosen will depend on the particular final qualities desired in the urethane.
- The B-side material is generally a solution of a petroleum-based polyester or polyether polyol, cross-linking agent, and blowing agent. A catalyst is also generally added to the B-side to control reaction speed and effect final product qualities. As discussed infra, the use of a petrochemical such as a polyester or polyether polyol is undesirable for a number of reasons.
- It has been discovered, however, that flexible urethane foams of a high quality can be prepared by substituting the petroleum-based polyol in the B-side preparation with a vegetable oil in the presence of a multi-functional alcohol cross-linking agent. The molar ratio of the hydroxyl (OH) groups of the cross-linking agent hydroxyl (OH) groups to the vegetable oil is preferably at least 0.7:1, and most preferably between about 0.7 and 1.2:1. The replacement is made on a substantially 1:1 weight ratio of vegetable oil for replaced petroleum-based polyol. Alternatively, a blend of petroleum-based polyol and vegetable oil may be used. The process of producing the urethane does not change significantly with the petroleum-based polyol replaced by the vegetable oil with all other components and general methods as are generally known in the art. The qualities of the final flexible, semi-rigid, or rigid urethane foam produced using the vegetable oil are consistent with those produced using a high grade, expensive polyol.
- Further, using a single vegetable oil, urethane foams of varying and selectable final qualities, including differing flexibility, density, and hardness, can be made by varying only the primary reactants. It would be difficult, if not impossible, to create such varied final foams using a single petroleum-based polyester or polyether polyol with the same variations in the remaining reactants. Instead, different petroleum-based polyols would be required to produce such varied results.
- The use of vegetable oil in the urethane forming reaction also realizes a significant cost savings. Vegetable oils are abundant, renewable, and easily processed commodities, as opposed to polyols, which petroleum derivatives and which entail significant associated processing costs. As such, they may currently be acquired for a cost of approximately half that of average grade petroleum-based polyurea, polyester or polyether polyols, and approximately one quarter the cost of high grade petroleum-based polyester or polyether polyols. Also, as polyols derived from petroleum, they are not renewable and carry a certain environmental cost with them. There is a distinct marketing advantage to marketing products that are based on environmentally friendly, renewable resources such as vegetable oils.
- The A-side isocyanate reactant of the urethane of the invention is preferably comprised of an isocyanate chosen from a number of suitable isocyanates as are generally known in the art. Different isocyanates may be selected to create different properties in the final product. The A-side reactant of the urethane of the invention comprises diisocyanate; 4,4′ diphenylmethane diisocyanate; 2,4-diphenylmethane diisocyanate; and modified diphenylmethane diisocyanate. Preferably, a modified diphenylmethane diisocyanate is used. It should be understood that mixtures of different isocyanates may also be used.
- The A-side of the reaction may also be a prepolymer isocyanate. The prepolymer isocyanate is typically the reaction product of an isocyanate, preferably a diisocyanate, and most preferably some form of diphenylmethane diisocyanate and a vegetable oil. The vegetable oil can be soy oil, rapeseed oil, cottonseed oil, or palm oil, or any other oil having a suitable number of reactive hydroxyl (OH) groups. The most preferred vegetable oil is soy oil. To create the prepolymer diisocyanate, the vegetable oil and isocyanate are mixed in a 1:1 ratio for 10-15 seconds every 10-15 minutes for a total of 4 hours or until the reaction has ended. There will still be unreacted isocyanate (NCO) groups in the prepolymer. However, the total amount of active A-side material has increased through this process. The prepolymer reaction reduces the cost of the A-side component by decreasing the amount of isocyanate required and utilizes a greater amount of inexpensive, environmentally friendly soy oil. In order to permit the prepolymer diisocyanate A-side to react with the B-side, additional isocyanate must be added to elevate the isocyanate (NCO) level to an acceptable level.
- The B-side reactant of the urethane reaction includes at least vegetable oil and a cross-linking agent. Typically, a blowing agent and a catalyst are also included in the B-side. It is believed that the isocyanate reacts with the fatty acids of the vegetable oil to produce the polymeric backbone of the urethane.
- The vegetable oils that are suitable for use tend to be those that are relatively high in triglyceride concentration and that are available at a relatively low cost. The preferred vegetable oil is soy oil, although it is contemplated that other vegetable oils, such as rapeseed oil (also known as canola oil), cottonseed oil, and palm oil can be used in accordance with the present invention. Except for the preliminary blowing step where air is passed through the oil to remove impurities and to thicken it, the soy oil is otherwise unmodified. It does not require esterification as is required for some urethane products of the prior art. The preferred blown soy oil has the following composition:
100% Pure Soybean Oil Air Oxidized Moisture 1.15% Free Fatty Acid 5.92% as OLEIC Phosphorous 55.5 ppm Peroxide Value 137.22 Meq/Kg Iron 6.5 ppm Hydroxyl Number 212 mgKOH/g Acid Value 12.46 mgKOH/g Sulfur 200 ppm Tin <.5 ppm - Except for the use of the preferred unmodified, blown soy oil replacing the polyol, the preferred B-side reactants used to produce the foam of the invention are generally known in the art. Accordingly, preferred blowing agents for the invention are those that are likewise known in the art and may be chosen from the group comprising 134A HCFC, a hydrochloroflurocarbon refrigerant available from Dow Chemical Co., Midland Mich.; methyl isobutyl ketone (MIBK); acetone; a hydroflurocarbon; and methylene chloride. These preferred blowing agents create vapor bubbles in the reacting mass. Should other blowing agents be used that react chemically, such as water reacting with the isocyanate (NCO) groups, to produce a gaseous product, concentrations of other reactants may be adjusted to accommodate the reaction.
- The cross-linking agents of the foam of the present invention are also those that are well known in the art. They must be at least di-functional (a diol). The preferred cross-linking agents for the foam of the invention are ethylene glycol and 1,4 butanediol; however, other diols may be used. It has been found that a mixture of ethylene glycol and 1,4 butanediol is particularly advantageous in the practice of the present invention. Ethylene glycol tends to offer a shorter chain molecular structure with many “dead end” sites, tending to create a firmer final foam resistant to tearing or “unzipping,” while 1,4 butanediol offers a longer chain molecular structure, tending to create a softer foam. Proper mixture of the two can create engineered foams of almost any desired structural characteristics.
- In addition to the B-side's soy oil and blowing agent, one or more catalyst may be present. The preferred catalysts for the urethanes of the present invention are those that are generally known in the art and are most preferably tertiary amines chosen from the group comprising DABCO 33-LV® comprised of 33% 1,4 diaza-bicyclco-octane (triethylenediamine) and 67% dipropylene glycol, a gel catalyst available from the Air Products Corporation; DABCO® BL-22 blowing catalyst available from the Air Products Corporation; and POLYCAT® 41 trimerization catalyst available from the Air Products Corporation.
- Also as known in the art, the B-side reactant may further comprise a silicone surfactant which functions to influence liquid surface tension and thereby influence the size of the bubbles formed and ultimately the size of the hardened void cells in the final foam product. This can effect foam density and foam rebound (index of elasticity of foam). Also, the surfactant may function as a cell opening agent to cause larger cells to be formed in the foam. This results in uniform foam density, increased rebound, and a softer foam.
- A molecular sieve may further be present to absorb excess water from the reaction mixture. The preferred molecular sieve of the present invention is available under the trade name L-paste™.
- The flexible and semi-rigid foams of the invention will have greater than approximately 60% open cells. The preferred flexible foam of the invention will also have a density of from 1 lb. to 45 lb. per cubic foot and a hardness of durometer between 20 and 70 Shore “A.”
- The urethane foam of the present invention is produced by combining the A-side reactant with the B-side reactant in the same manner as is generally known in the art. Advantageously, use of the vegetable oil to replace the petroleum-based polyol does not require significant changes in the method of performing the reaction procedure. Upon combination of the A and B side reactants, an exothermic reaction ensues that may reach completion in anywhere from several minutes to several hours depending on the particular reactants and concentrations used. Typically, the reaction is carried out in a mold so that the foam expands to fill the mold, thereby creating a final foam product in the shape of the mold.
- The components may be combined in differing amounts to yield differing results, as will be shown in the Examples presented in the detailed description below. Generally, however, the preferred flexible foam of the invention B-side mixture, when using the preferred components, is prepared with the following general weight ratios:
Blown soy oil 100 parts Cross-linking agent 8-15 parts Blowing agent 8-15 parts Catalyst 1-12 parts - A petroleum based polyol such as polyether polyol, polyester polyol, or polyurea polyol may be substituted for some of the blown soy oil in the B-side of the reaction, however, this is not necessary. This preferred B-side formulation is then combined with the A-side to produce a foam. The preferred A-side, as discussed previously, is comprised of MDI or a prepolymer comprised of MDI and a vegetable oil, preferably soy oil. The A-side and B-side are typically, and preferably in an approximate ratio of about 35 parts to about 85 parts A-side to 100 parts B-side.
- Flexible urethane foams may be produced with differing final qualities using the same vegetable oil by varying the particular other reactants chosen. For instance, it is expected that the use of relatively high molecular weight and high functionality isocyanates will result in a less flexible foam than will use of a lower molecular weight and lower functionality isocyanate when used with the same vegetable oil. Similarly, it is expected that lower molecular weight and lower functionality cross-linkers will result in a more flexible foam than will higher molecular weight and higher functionality cross-linkers when used with the same vegetable oil. Also, a ethylene glycol cross-linker will result in shorter final chains and a firmer foam, while use of a butanediol cross-linker results in longer chains and a softer foam. Moreover, it has been contemplated that chain extenders may also be employed in the present invention. Butanediol, in addition to acting as a cross-linker, may act as a chain extender.
- Urethane elastomers can be produced in much the same manner as urethane foams, except that a blowing agent is not present to create void cells in the material. It has been discovered that useful urethane elastomers may be prepared using a vegetable oil to replace a petroleum-based polyester or polyether polyol. The preferred elastomer of the invention is produced using diphenylmethane diisocyanate (MDI); 1,4 butanediol cross-linking agent; and a vegetable oil, preferably soy oil. A catalyst may be added to the reaction composition to decelerate the speed of the reaction. The preferred elastomer of the invention is prepared by combining the reactants. An exothermic reaction occurs that creates the elastomer. The preferred elastomer has an approximate density of 65 lb. to 75 lb. per cubic foot.
- The following examples of preparation of foams and elastomers of the invention summarized in Table A will illustrate various embodiments of the invention. In the Examples, the B-Side (soy oil and other components), once blended, has a shelf life of several months. The A-side material in the following examples is comprised of modified diphenylmethane diisocyanate (MDI). The prepolymer A-side material in the following examples is the reaction product of a vegetable oil, preferably soy oil, and a modified diphenylmethane diisocyanate (MDI). There are four different MDI materials specified in the following examples; all are modified monomeric or polymeric diphenylmethane diisocyanates available from the Bayer Corp., Polymers Division, Rosemont Ill.: “Mondur® MA-2901” (Bayer Product Code No. C-1464); “Mondur®-448” (Bayer Product Code No. G-448), “Mondur® MRS-20”, and “Mondur®-PF”.
- Also, “cure” in the following examples refers to the final, cured foam taken from the mold. The soy oil used in the following examples is blown soy oil obtained from Cargill, in Chicago, Ill. Catalysts used include “DABCO 33-LV®,” comprised of 33% 1,4-diaza-bicyclo-octane and 67% dipropylene glycol available from the Air Products Urethanes Division; “DABCO® BL-22,” a tertiary amine blowing catalyst also available from the Air Products Urethanes Division; and “POLYCAT® 41” (n, n′, n″, dimethylamino-propyl-hexahydrotriazine tertiary amine) also available from the Air Products Urethanes Division.
- Catalysts in the following Examples may be referred to as “front end,” “back end,” and “blowing”. Front end catalysts tend to speed the early portion of the reaction, while back end catalysts tend to speed the later, curing portion of the reaction. A blowing catalyst effects the timing of the activation of the blowing agent. Some of the Examples include “L-paste™,” which is a trade name for a molecular sieve for absorbing water. Some also contain “DABCO® DC-5160,” a silicone surfactant available from Air Products Urethane Division.
- The B-side material was prepared as follows:
50 g Soy Oil 5 g Ethylene Glycol (cross-linker) 1 g Front end catalyst (DABCO 33-LV ®; 33% triethylenediamine and 67% dipropylene glycol) 1 g Blow catalyst (DABCO ® BL-22; a tertiary amine catalyst) 4 g Methyl Isobutyl Ketone (blowing agent) - Blown soy oil has a molecular weight of about 278, while the ethylene glycol has a molecular weight of about 62. Thus, the molar ratio of ethylene glycol to blown soy oil is 0.22:1. Since the ethylene glycol has two hydroxyl (OH) groups with which to cross-link the constituent fatty acids of the blown soy oil, the molar ratio of the hydroxyl (OH) groups of the ethylene glycol to soy oil is about 0.45:1. The resulting B-side was then combined with an A-side material in a ratio of 50 parts A-side to 100 parts B-side. The A-side material is comprised of Mondur® 448, a modified monomeric diphenylmethane diisocyanate (pMDI). The cure was acceptable; however, the cellular material remained tacky at the surface for 20 minutes.
- The B-side is the same as that of Example 1. The A-side is comprised of MA-2901, a modified diphenylmethane diisocyanate. The B-side was combined with the A-side in a ratio of 52 parts A-side to 100 parts B-side. The cure was acceptable, although the cellular material remained tacky for 12 minutes.
- The A-side was the same as Example 2. The B-side was again the same as that of Example 1, except that 1.5 parts of methanol were added as additional blowing agent. The ratio was 52 parts A-side to 100 parts B-side. The sample cured in 1 hour. It was not a favorable result in that the cellular material foamed and then fell back to solid and rose again. The methanol apparently had an adverse affect.
-
B-side: 100 g Soy Oil 5 g Ethylene Glycol (cross-linker) 2.5 g Front end catalyst (DABCO 33-LV ®; 33% 1,4-diaza-bicyclo-octane and 67% dipropylene glycol) 2.5 g Blow catalyst (DABCO ® BL-22; a tertiary amine catalyst) 4 g Methyl Isobutyl Ketone (MIBK) - The A-side was the same as Example 2. The materials were reacted in a ratio of 50 parts A-side to 100 parts B-side. The results were a good foam, but weak in tensile strength.
- The B-side and A-side are the same as in Example 4. However, the materials were reacted in a ratio of 52 parts A-side to 100 parts B-side. The results were essentially the same as in Example 4 with a little better tensile strength.
-
B-Side: 103 g Soy Oil 10 g Ethylene Glycol (cross-linker) 11 g Acetone (Blowing agent) 2.5 g Front end catalyst (DABCO 33-LV ®; 33% 1,4-diaza-bicyclo-octane and 67% dipropylene glycol) 2.5 g Blow catalyst (DABCO ® BL-22; a tertiary amine catalyst) - The molar ratio of ethylene glycol to blown soy oil is 0.44:1. With two hydroxyl (OH) groups with which to cross-link the constituent fatty acids of the blown soy oil, the molar ratio of the hydroxyl (OH) groups of the ethylene glycol to soy oil is about 0.90:1. The A-side comprises 52 parts MA-2901, a modified monomeric diphenylmethane diisocyanate, to 100 parts B-side. The resulting foam was hard and its cell size large. It fell back to a solid, largely due to too much blowing agent.
-
B-side: 100 g Soy Oil 8 g Ethylene Glycol (cross-linker) 5 g Acetone (Blowing agent) 2.5 g Front end catalyst (DABCO 33-LV ®; 33% 1,4-diaza-bicyclo-octane and 67% dipropylene glycol) 2.5 g Blow catalyst (DABCO ® BL-22; a tertiary amine catalyst) - The molar ratio of ethylene glycol to blown soy oil is 0.35 to 1. With two hydroxyl (OH) groups with which to cross-link the constituent fatty acids of the blown soy oil, the molar ratio of the hydroxyl (OH) groups of the ethylene glycol to soy oil is about 0.70:1. The A-side comprises MA-2901, a modified monomeric diphenylmethane diisocyanate, and is present in 51 parts A-side to 100 parts B-side. The resulting foam is generally a good foam, having low tensile strength but a better density range.
- The B-side is the same as that of Example 7. The A-side also comprises MA-2901, a modified monomeric diphenylmethane diisocyanate, as in Example 7. The A-side is present in a ratio of 45 parts A-side to 100 parts B-side.
- The A-side and B-side are the same as in Example 7. However, 72 parts A-side were reacted with 100 parts B-side. The resulting foam fell back and did not cure after 1 hour, indicating an overcharge of A-side.
-
B-side 100 g Soy Oil 11 g Ethylene Glycol (cross-linker) 4 g Methyl Isobutyl Ketone (MIBK) 3 g Front end catalyst (DABCO 33-LV ®; 33% 1,4-diaza-bicyclo-octane and 67% dipropylene glycol) 3 g Blow catalyst (DABCO ® BL-22; a tertiary amine catalyst) - The molar ratio of ethylene glycol to blown soy oil is 0.49:1. With two hydroxyl (OH) groups with which to cross-link the constituent fatty acids of the blown soy oil, the molar ratio of the hydroxyl (OH) groups of the ethylene glycol to soy oil is about 0.99:1. The A-side comprised MA-2901, a modified monomeric diphenylmethane diisocyanate. The A-side was reacted with the B-side in a ratio of 50 parts A-side to 100 parts B-side. The resulting foam had a 15-minute cure and a very slow recovery. However, the final cure was insufficient because it did not occur for 72 hours.
-
B-side 100 g Soy Oil 11 g Ethylene Glycol (cross-linker) 4 g Methyl Isobutyl Ketone (MIBK) 3 g Front end catalyst (DABCO 33-LV ®; 33% 1,4-diaza-bicyclo-octane and 67% dipropylene glycol) 3 g Blow catalyst (DABCO ® BL-22; a tertiary amine catalyst) - The B-side is as in Example 10. The A-side comprises Mondur® 448, a modified monomeric diphenylmethane diisocyanate, in a ratio of 50 parts A-side to 100 parts B-side. The resulting foam cures in 15 minutes, but is very crumbly.
-
B-side 100 g Soy Oil 11 g Ethylene Glycol (cross-linker) 4 g Methyl Isobutyl Ketone (MIBK) 3 g front end catalyst (DABCO 33-LV ®; 33% diaza-bicyclo-octane and 67% dipropylene glycol) 3 g Blow catalyst (DABCO ® BL-22; a tertiary amine catalyst) - The B-side is as in Example 10. The A-side comprised 76 parts MA-2901, a modified monomeric diphenylmethane diisocyanate, to 100 parts B-side. The resulting foam cures in 30 minutes, but has a very fast, complete fall back.
-
B-side 100 g Soy Oil 5 g Ethylene Glycol (cross-linker) 5 g 1,4 butanediol (cross-linker) 4 g Methyl Isobutyl Ketone (MIBK) 2.5 g Front end catalyst (DABCO 33-LV ®; 33% 1,4-diaza-bicyclo-octane and 67% dipropylene glycol) 2.5 g Blow catalyst (DABCO ® BL-22; a tertiary amine catalyst) - Ethylene glycol has a molecular weight of about 62 and 1,4 butanediol has a molecular weight of about 90. Thus, the molar ratio of the ethylene glycol to blown soy oil is 0.22:1 and the molar ratio of the 1,4 butanediol to blown soy oil is 0.15:1. Since each of the ethylene glycol and 1,4 butanediol have two hydroxyl (OH) groups with which to cross-link the constituent fatty acids of the blown soy oil, the molar ratio of the hydroxyl (OH) groups of the 50/50 ethylene glycol/1,4 butanediol cross-linker mixture to the blown soy oil is about 0.75:1. The A-side was reacted at 74 parts MA-2901, a modified monomeric diphenylmethane diisocyanate to 100 parts B-side. The resulting foam cured to the touch within 3 minutes and fully cured within 15 minutes. It has good properties.
-
B-side 100 g Soy Oil 5 g Ethylene Glycol (cross-linker) 5 g 1,4 butanediol (cross-linker) 4 g Methyl Isobutyl Ketone (MIBK) 2.5 g Front end catalyst (DABCO 33-LV ®; 33% 1,4-diaza-bicyclo-octane and 67% dipropylene glycol) 2.5 g Back end catalyst (POLYCAT ® 41; n, n′, n″, dimethylamino-propyl- hexahydrotriazine tertiary amine) 2 g Blow catalyst (DABCO ® BL-22; a tertiary amine catalyst) - The A-side was reacted at 74 parts, a modified MDI, MA-2901, to 100 parts B-side. The resulting foam cured to the touch within 3 minutes and exhibited slightly better initial strength than the foam of Example 13. It fully cured within 15 minutes with good properties.
-
B-side 200 g Soy Oil 7 g Ethylene Glycol (cross-linker) 16 g 1,4 butanediol (cross linker) 2.5 g Front end catalyst (DABCO 33-LV ®; 33% 1,4-diaza-bicyclo-octane and 67% dipropylene glycol) 2.5 g Blow catalyst (DABCO ® BL-22′ a tertiary amine catalyst) 2 g Back end catalyst (POLYCAT ® 41; n, n′, n″, dimethylamino-propyl- hexahydrotriazine tertiary amine) - The molar ratio of the ethylene glycol to blown soy oil is 0.15:1 and the molar ratio of the 1,4 butanediol to blown soy oil is 0.24:1. Since each of the ethylene glycol and 1,4 butanediol have two hydroxyl (OH) groups with which to cross-link the constituent fatty acids of the blown soy oil, the molar ratio of the hydroxyl (OH) groups of the 50/50 ethylene glycol/1,4 butanediol cross-linker mixture to blown soy oil is about 0.80:1.
- The A-side was reacted at 74 parts, a modified MDI, MA-2901 to 100 parts B-side. The resulting foam had very good qualities. The foam exhibited good elastomeric and fast cure (tack-free after 90 seconds) properties and was soft with good elastomeric properties after 1 hour.
- The B-side is the same blend as Example 15. The A-side comprises, a modified MDI, Mondur® 448. The A-side was reacted at 74 parts A-side to 100 parts B-side. The reaction time was good and the resulting foam was a stiff flexible foam with good elastomeric properties. The foam continued to exhibit good elastomeric properties after 1 hour.
-
B-side 100 g Soy Oil 5 g Ethylene Glycol (cross-linker) 5 g 1,4 butanediol (cross-linker) 2.5 g Front end catalyst (DABCO 33-LV ®; 33% 1,4-diaza-bicyclo-octane and 67% dipropylene glycol) 2 g Blow catalyst (DABCO ® BL-22; a tertiary amine catalyst) 2 g Back end catalyst (POLYCAT ® 41; n, n′, n″, dimethylamino-propyl- hexahydrotriazine tertiary amine) 2 g Molecular sieve (L-paste ™) - The molar ratio of the hydroxyl (OH) groups of the 50/50 ethylene glycol/1,4 butanediol cross-linker mixture to soy oil is again about 0.75:1.
- The A-side comprises a 50/50 blend of, a modified MDI, MA-2901 and a modified pMDI, Mondur® 448. The A-side was reacted with the B-side at 74 parts A-side to 100 parts B-side. The resulting foam is a good foam with good flexibility, high density, but still needs tensile improvements.
-
B-side 200 g Soy Oil 5 g Ethylene Glycol (cross-linker) 21 g 1,4 butanediol (cross-linker) 5 g Front end catalyst (DABCO 33-LV ®; 33% 1,4-diaza-bicyclo-octane and 67% dipropylene glycol) 5 g Blow catalyst (DABCO ® BL-22; a tertiary amine catalyst) 2 g Back end catalyst (POLYCAT ® 41; n, n′, n″, dimethylamino-propyl- hexahydrotriazine tertiary amine) 6 g Molecular sieve (L-paste ™) - The molar ratio of the hydroxyl (OH) groups of the 5/21 ethylene glycol/1,4 butanediol mixture to blown soy oil is about 0.85:1.
- The A-side comprises a 50/50 blend of a modified MDI, MA-2901 and a modified pMDI, Mondur® 448. The A-side was reacted with the B-side at 74 parts A-side to 100 parts B-side. The resulting foam is very similar to that of Example 17 and is a good foam with good flexibility, high density, but still needs tensile improvements.
-
B-side 200 g Soy Oil 22 g Ethylene Glycol (cross-linker) 4 g 1,4 butanediol (cross-linker) 2.5 g Front end catalyst (DABCO 33-LV ®; 33% 1,4-diaza-bicyclo-octane and 67% dipropylene glycol) 2.5 g Blow catalyst (DABCO ® BL-22; a tertiary amine catalyst) 5 g Back end catalyst (POLYCAT 41 ®; n, n′, n″, dimethylamino-propyl- hexahydrotriazine tertiary amine) 16 g Molecular sieve (L-paste ™) 4 g Silicone surfactants (DABCO ® DC-5160) - The molar ratio of the hydroxyl (OH) groups of the 22/4 ethylene glycol/1,4 butanediol mixture to blown soy oil is about 1.10:1. The A-side comprises a modified MDI, MA-290. The A-side and the B-side were reacted at 74 parts A-side to 100 parts B-side. The resulting foam demonstrated very good properties. It is almost a solid elastomer with good rebound.
-
B-side 200 g Soy Oil 22 g Ethylene Glycol (cross-linker) 4 g 1,4 butanediol (cross-linker) 10 g Methylene Chloride (blowing agent) 2.5 g Front end catalyst (DABCO 33-LV ®; 33% 1,4-diaza-bicyclo-octane and 67% dipropylene glycol) 2.5 g Blow catalyst (DABCO ® BL-22; a tertiary amine catalyst) 5 g Back end catalyst (POLYCAT ® 41; n, n′, n″, dimethylamino-propyl- hexahydrotriazine tertiary amine) 16 g Molecular sieve (L-paste ™) 4 g Silicone surfactants (DABCO ® DC-5160) - The molar ratio of the hydroxyl (OH) groups of the 22/4 ethylene glycol/1,4 butanediol mixture to blown soy oil is again about 1.10:1. The A-side comprises a modified MDI, MA-2901, and was reacted at 74 parts A-side to 100 parts B-side. The resulting foam was a very good foam having uniform cell size, good flex, moderate density, good rebound and higher tensile strength.
-
B-side 200 g Soy Oil 22 g Ethylene Glycol (cross-linker) 4 g 1,4 butanediol (cross-linker) 10 g Methylene Chloride (blowing agent) 2.5 g Front end catalyst (DABCO 33-LV ®; 33% 1,4-diaza-bicyclo-octane and 67% dipropylene glycol) 2.5 g Blow catalyst (DABCO ® BL-22; a tertiary amine catalyst) 5 g Back end catalyst (POLYCAT 41 ®; n, n′, n″, dimethylamino-propyl- hexahydrotriazine tertiary amine) 16 g Molecular sieve (L-paste ™) 4 g Silicone surfactants (DABCO ® DC-5160) 2 g Green pigment - The molar ratio of the hydroxyl (OH) groups of the 22/4 ethylene glycol/1,4 butanediol mixture to blown soy oil is again about 1.10:1. The A-side comprises a modified MDI, MA-2901, and was reacted at 81 parts A-side to 100 parts B-side.
-
B-side 200 g Soy Oil 22 g Ethylene Glycol (cross-linker) 4 g 1,4 butanediol (cross-linker) 12 g Methylene Chloride (blowing agent 2.5 g Front end catalyst (DABCO 33-LV ®; 33% 1,4-diaza-bicyclo-octane and 67% dipropylene glycol) 2.5 g Blow catalyst (DABCO ® BL-22; a tertiary amine catalyst) 5 g Back end catalyst (POLYCAT 41 ®; n, n′, n″, dimethylamino-propyl- hexahydrotriazine tertiary amine) 16 g Molecular sieve (L-paste ™) 4 g Silicone surfactants (DABCO ® DC-5160) 2 g Green pigment - The molar ratio of the hydroxyl (OH) groups of the 22/4 ethylene glycol/1,4 butanediol mixture to blown soy oil is again about 1.10:1. The A-side comprises a modified MDI, MA-2901. The A-side and the B-side were reacted at 80 parts A-side to 100 parts B-side. The resulting foam was a good foam. It was a stiffer flexible foam with good cell size, good uniformity, and low to moderate density.
-
B-side 400 g Soy Oil 35 g Ethylene Glycol (cross-linker) 15 g 1,4 butanediol (cross-linker) 24 g Methylene Chloride (blowing agent) 5 g Front end catalyst (DABCO 33-LV ®; 33% 1,4-diaza-bicyclo-octane and 67% dipropylene glycol) 5 g Blow catalyst (DABCO ®BL-22; a tertiary amine catalyst) 9 g Back end catalyst (POLYCAT ® 41; n, n′, n″, dimethylamino-propyl- hexahydrotriazine tertiary amine) 32 g Molecular sieve (L-paste ™) 12.5 g Silicone surfactants (DABCO ® DC-5160) 4 g Green pigment - The molar ratio of the hydroxyl (OH) groups of the 35/15 ethylene glycol/1,4 butanediol mixture to blown soy oil is about 1.00:1. The A-side comprises a modified MDI, MA-2901, and was reacted at 74 parts A-side to 100 parts B-side. The resulting foam is low in density with poor tensile strength.
-
B-side 235 g Soy Oil 25 g Ethylene Glycol (cross-linker) 6 g 1,4 butanediol (cross-linker) 12 g Methylene Chloride (blowing agent) 2 g Front end catalyst (DABCO 33-LV ®; 33% 1,4-diaza-bicyclo-octane and 67% dipropylene glycol) 2 g Blow catalyst (DABCO ®BL-22; a tertiary amine catalyst) 1.75 g Back end catalyst (POLYCAT 41 ®; n, n′, n″, dimethylamino-propyl- hexahydrotriazine tertiary amine) 25 g Molecular sieve (L-paste ™) - The molar ratio of the hydroxyl (OH) groups of the 25/6 ethylene glycol/1,4 butanediol mixture to soy oil is about 1.50:1. The A-side comprises a 2,4′ rich polymeric MDI, Mondur® MRS-20, and was reacted at 70 parts to 100 parts B-side. The resulting reaction had no foaming and no real reaction.
- Example 24 is repeated with A-side comprising Mondur®-PF, a modified MDI. Again, no foaming and not a good reaction.
- Example 24 is again repeated, with the A-side this time comprising a 50/50 mixture of a modified MDI, MA-2901, and a modified pMDI, Mondur® 448. It is reacted at 70 parts to 100 parts B-side.
- The A-side comprises a modified MDI, MA-2901. The B-side comprises the following:
B-side 100 g Soy Oil 7 g Dipropylene-glycol (cross-linker) 2 g Front end catalyst (DABCO 33-LV ®; 33% triethylenediamine and 67% dipropylene glycol) 2 g Back end catalyst (DABCO ® 8154; an amine salt) - The A-side and B-side reactions were mixed in a ratio of 60 parts A-side to 100 parts B-side. The resultant foam exhibited excellent properties.
-
B-side 100 g Soy Oil 3 g Dipropylene glycol (cross-linker) 2 g Surfactant 2 g Front end catalyst (DABCO 33-LV ®; 33% triethylenediamine and 67% dipropylene glycol) 2 g Back end catalyst (DABCO ® 8154; an amine salt) - The A-side and B-side reactions were mixed in a ratio of 60 parts A-side to 100 parts B-side. The resultant reaction produced a foam exhibiting excellent properties.
- The A-side and B-side components are identical to those in Example 28. The A-side was reacted with the B-side in a ratio of 68 parts A-side and 100 parts B-side. Once again, the foam produced by the reaction had excellent properties.
- The A-side comprises a mix of a modified MDI, MA-2901, and a modified pMDI, Mondur® 448. The B-side comprises the following:
B-side 100 g Soy Oil 3 g Tripropylene glycol (cross-linker) 3 g Dipropylene glycol (cross-linker) 2 g Front end catalyst (DABCO 33-LV ®; 33% triethylenediamine and 67% dipropylene glycol) 2 g Back end catalyst (DABCO ® 8154; an amine salt) - The A-side and B-side were mixed in a ratio of 60 parts A-side to 100 parts B-side. The resultant foam was a rigid foam exhibiting excellent properties.
- In this example, the A-side was identical to the A-side of Example 30 and the B-side is identical to Example 30 except for the fact that 6% butanediol was added to the B-side. The A-side and B-side were mixed in a ratio of 60 parts A-side to 100 parts B-side. The resultant foam was a rigid foam exhibiting excellent properties. The addition of the butanediol increased the speed of the reaction compared to Example 30.
- The A-side comprises polymeric MDI. The B-side comprises the following:
B-side 200 g Soy Oil 30 g Ethylene glycol cross-linker) 15 g Butanediol (cross-linker) 5 g Aliphatic amine tetrol (CL-485; cross-linker) 25 g Molecular sieve (L-paste ™) 8 g Front end catalyst (DABCO 33-LV ®; 33% triethylenediamine and 67% dipropylene glycol) 5 g Back end catalyst (DABCO ® 1854; an amine salt) - The A-side and B-side were mixed in a 1:1 ratio. The foam resulting from the chemical reaction was a rigid foam with good properties.
-
B-side 100 g Soy Oil 10 g Butanediol (cross-linker) 6.4 g Ethylene glycol (cross-linker) 3 g Aliphatic amine tetrol (cross-linker) 3.2 g Front end catalyst (DABCO 33-LV ®; 33% triethylenediamine and 67% dipropylene glycol) 3.0 g Back end catalyst (DABCO ® 1854; an amine salt) 5% Molecular sieve (L-paste ™) - The A-side and B-side were mixed in a ratio of 35 parts A-side to 100 parts B-side. The resulting foam was very good after about 15 minutes.
- The A-side comprises either MDI or pMDI. The B-side comprised the following:
B-side 200 g Soy Oil 200 g Polyurea polyol 48 g Aliphatic amine tetrol (cross-linker) 30 g Ethylene glycol (cross-linker) 3 g Front end catalyst (DABCO 33-LV ®; 33% triethylenediamine and 67% dipropylene glycol) 3 g Back end catalyst (Polycat 41 ®; n, n′, n″, dimethylamino-propyl- hexahydrotriazine tertiary amine) 3 g Tertiary amine catalyst (DABCO ® BL-22) 7 g Molecular sieve (L-paste ™) - The A-side and B-side were combined in a ratio of 50 parts A-side to 100 parts B-side. The result reaction occurred very fast and the resultant elastomer exhibited good properties. Combining the A-side and the B-side in a ratio of 68 parts A-side to 100 parts B-side also results in an elastomer with good properties.
-
B-side 300 g Soy Oil 300 g Polyurea polyol (petroleum based polyol) 33 g Butanediol (cross-linker) 11.3 g Front end catalyst (DABCO 33-LV ®; 33% triethylenediamine and 67% dipropylene glycol) 7.6 g Back end catalyst (Polycat ® 41; n, n′, n″, dimethylamino-propyl- hexahydrotriazine tertiary amine 5 g Aliphatic amine tetrol (DABCO ® CL-485; cross-linker) - The A-side was blended with the B-side in a ratio of 40 parts A-side to 100 parts B-side. The resultant foam had good properties, but was slightly hard.
- The A-side and B-side are identical to Example 35, however, 5% methylene chloride and 1% of a stabilizing anti-oxidant, Stabaxol® were added to the B-side. The A-side and the B-side were mixed in a ratio of 32 parts A-side to 100 parts B-side and a ratio of 36.5 parts A-side to 100 parts B-side. Both resulting foams were good, soft foams. The addition of the methylene chloride as a blowing agent greatly assisted the reaction without pulling out water thereby allowing the foam to stay soft.
- The A-side comprises a 50/50 mixture of modified MDI and modified pMDI. The B-side comprises the following:
B-side 400 g Soy Oil 400 g Polyurea polyol (petroleum based polyol) 96 g Aliphatic amine tetrol (cross-linker; amine salt) 60 g Ethylene glycol (cross-linker) 6 g Front end catalyst (DABCO 33-LV ®; 33% triethylenediamine and 67% dipropylene glycol) 3 g Back end catalyst (tertiary amine catalyst) 6 g Blow catalyst (DABCO ® BL-22) - The A-side was combined with the B-side in a ratio of 50 parts A-side to 100 parts B-side. The resultant foam exhibited good overall properties.
- The A-side comprises a polymeric MDI, Mondur® MR light. The B-side comprises the following:
B-side 50 g Soy Oil 50 g Sucrose polyol (Bayer 4035) 10 g Ethylene glycol (cross-linker) 2.5 g Dipropylene glycol (cross-linker) 3.0 g Front end catalyst 2.0 g Back end catalyst (tertiary block amine catalyst) - The A-side was mixed with the B-side at the following ratios:
A-side B-side 50 100 70 100 80 100 90 100 100 100 - Each mix ratio in a very fast reacting high-density foam exhibiting good qualities overall.
- The above description is considered that of the preferred embodiments only. Modifications of the invention will occur to those skilled in the art and to those who make or use the invention. Therefore, it is understood that the embodiments shown in the drawings and described above are merely for illustrative purposes and not intended to limit the scope of the invention, which is defined by the following claims as interpreted according to the principles of patent law, including the doctrine equivalents.
Claims (22)
1. An elastomer comprising the reaction product of an A-side comprising an isocyanate and a B-side comprising a blown vegetable oil, a cross-linking agent comprised of a multi-functional alcohol, and a catalyst.
2. The elastomer of claim 1 , wherein the blown vegetable oil comprises at least one blown vegetable oil selected from the group consisting of blown soy oil, blown rapeseed oil, blown cottonseed oil, and blown palm oil.
3. The elastomer of claim 1 , wherein the blown vegetable oil comprises a blown soy oil.
4. The elastomer of claim 1 , wherein the catalyst is a tertiary amine.
5. The elastomer of claim 1 , wherein the multi-functional alcohol is present in a ratio to the vegetable oil such that there are at least 0.7 moles of hydroxyl (OH) groups per mole of vegetable oil.
6. The elastomer of claim 1 , wherein the B-side further comprises a surfactant.
7. The elastomer of claim 1 , wherein the isocyanate comprises a diisocyanate.
8. The elastomer of claim 1 , wherein the isocyanate comprises at least one diisocyanate selected from the group consisting of 2,4′ diisocyanate, 4,4′diphenylmethane diisocyanate, and 2,4′ diphenylmethane diisocyanate.
9. The elastomer of claim 1 , wherein the isocyanate comprises a mixture of at least two diisocyanates.
10. The elastomer of claim 10 , wherein the diisocyanate is a mixture of at least two diisocyanates selected from the group consisting of 2,4′ diisocyanate, 4,4′ diphenylmethane diisocyanate and 2,4′ diphenylmethane diisocyanate.
11. The elastomer of claim 4 , wherein the isocyanate comprises a mixture of at least two isocyanates.
12. The elastomer of claim 1 , wherein the cross-linker is selected from the group consisting of ethylene glycol, 1,4 butanediol, and dipropylene glycol.
13. The elastomer of claim 1 , wherein the cross-linker is a combination of ethylene glycol and 1,4 butanediol.
14. The elastomer of claim 1 , wherein the B-side further comprises a polyol derived from petroleum.
15. The elastomer of claim 14 , wherein the polyol derived from petroleum comprises a polyurea polyol.
16. An elastomer comprising the reaction product of an A-side comprising a diisocyanate and a B-side comprising a blown soy oil, a multi-functional alcohol, and a catalyst.
17. The elastomer of claim 16 , wherein the diisocyanate comprises at least one diisocyanate selected from the group consisting of 2,4′ diisocyanate, 4,4′ diphenylmethane diisocyanate, and 2,4′ diphenylmethane diisocyanate.
18. The elastomer of claim 16 , wherein the diisocyanate comprises a mixture of at least two diisocyanates.
19. The elastomer of claim 16 , wherein the B-side further comprises a polyol derived from petroleum.
20. The elastomer of claim 19 , wherein the polyol derived from petroleum comprises a polyurea polyol.
21. The elastomer of claim 16 wherein the multifunctional alcohol comprises a multi-functional alcohol selected from the group consisting of ethylene glycol, 1,4 butanediol, and dipropylene glycol.
22. An elastomer comprising the reaction product of an A-side comprising an isocyanate and a B-side comprising a blown soy oil, a multi-functional alcohol, a polyol derived from petroleum, and a catalyst.
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US11/108,368 US20050182228A1 (en) | 1998-09-17 | 2005-04-18 | Plastic material |
US11/933,049 US20080051506A1 (en) | 1998-09-17 | 2007-10-31 | Plastic material |
Applications Claiming Priority (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US09/154,340 US6180686B1 (en) | 1998-09-17 | 1998-09-17 | Cellular plastic material |
US09/646,356 US6465569B1 (en) | 1998-09-17 | 1999-09-17 | Plastic material |
PCT/US1999/021511 WO2000015684A1 (en) | 1998-09-17 | 1999-09-17 | Improved cellular plastic material |
US10/253,252 US6624244B2 (en) | 1998-09-17 | 2002-09-24 | Plastic material |
US10/639,109 US6881763B2 (en) | 1998-09-17 | 2003-08-12 | Plastic material |
US11/108,368 US20050182228A1 (en) | 1998-09-17 | 2005-04-18 | Plastic material |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US10/639,109 Continuation US6881763B2 (en) | 1998-09-17 | 2003-08-12 | Plastic material |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US11/933,049 Continuation US20080051506A1 (en) | 1998-09-17 | 2007-10-31 | Plastic material |
Publications (1)
Publication Number | Publication Date |
---|---|
US20050182228A1 true US20050182228A1 (en) | 2005-08-18 |
Family
ID=22550968
Family Applications (8)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US09/154,340 Expired - Lifetime US6180686B1 (en) | 1998-09-17 | 1998-09-17 | Cellular plastic material |
US09/646,356 Expired - Lifetime US6465569B1 (en) | 1998-09-17 | 1999-09-17 | Plastic material |
US10/253,252 Expired - Fee Related US6624244B2 (en) | 1998-09-17 | 2002-09-24 | Plastic material |
US10/634,026 Expired - Fee Related US6864296B2 (en) | 1998-09-17 | 2003-08-04 | Plastic material |
US10/639,303 Expired - Fee Related US6867239B2 (en) | 1998-09-17 | 2003-08-12 | Plastic material |
US10/639,109 Expired - Fee Related US6881763B2 (en) | 1998-09-17 | 2003-08-12 | Plastic material |
US11/108,368 Abandoned US20050182228A1 (en) | 1998-09-17 | 2005-04-18 | Plastic material |
US11/933,049 Abandoned US20080051506A1 (en) | 1998-09-17 | 2007-10-31 | Plastic material |
Family Applications Before (6)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US09/154,340 Expired - Lifetime US6180686B1 (en) | 1998-09-17 | 1998-09-17 | Cellular plastic material |
US09/646,356 Expired - Lifetime US6465569B1 (en) | 1998-09-17 | 1999-09-17 | Plastic material |
US10/253,252 Expired - Fee Related US6624244B2 (en) | 1998-09-17 | 2002-09-24 | Plastic material |
US10/634,026 Expired - Fee Related US6864296B2 (en) | 1998-09-17 | 2003-08-04 | Plastic material |
US10/639,303 Expired - Fee Related US6867239B2 (en) | 1998-09-17 | 2003-08-12 | Plastic material |
US10/639,109 Expired - Fee Related US6881763B2 (en) | 1998-09-17 | 2003-08-12 | Plastic material |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US11/933,049 Abandoned US20080051506A1 (en) | 1998-09-17 | 2007-10-31 | Plastic material |
Country Status (16)
Country | Link |
---|---|
US (8) | US6180686B1 (en) |
EP (1) | EP1127086B2 (en) |
JP (1) | JP2002524627A (en) |
CN (1) | CN1245428C (en) |
AT (1) | ATE286929T1 (en) |
AU (1) | AU766760B2 (en) |
BR (1) | BR9913784B1 (en) |
CA (1) | CA2344378C (en) |
DE (1) | DE69923210T3 (en) |
DK (1) | DK1127086T4 (en) |
ES (1) | ES2235516T5 (en) |
GT (1) | GT200000029A (en) |
MX (1) | MXPA01002680A (en) |
PT (1) | PT1127086E (en) |
TW (1) | TWI257399B (en) |
WO (1) | WO2000015684A1 (en) |
Cited By (22)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20050070620A1 (en) * | 2003-09-30 | 2005-03-31 | Ron Herrington | Flexible polyurethane foams prepared using modified vegetable oil-based polyols |
US20060041157A1 (en) * | 2004-06-25 | 2006-02-23 | Petrovic Zoran S | Modified vegetable oil-based polyols |
US20070275227A1 (en) * | 2002-03-15 | 2007-11-29 | Mashburn Larry E | Carpet backings prepared from hydroxylated vegetable oil-based polyurethanes |
US20080132134A1 (en) * | 2001-03-15 | 2008-06-05 | Mashburn Larry E | Carpet backings prepared from vegetable oil-based polyurethanes |
US20090287007A1 (en) * | 2008-05-13 | 2009-11-19 | Cargill, Incorporated | Partially-hydrogenated, fully-epoxidized vegetable oil derivative |
US7691914B2 (en) | 2005-04-25 | 2010-04-06 | Cargill, Incorporated | Polyurethane foams comprising oligomeric polyols |
US7763341B2 (en) | 2004-01-23 | 2010-07-27 | Century-Board Usa, Llc | Filled polymer composite and synthetic building material compositions |
US7794224B2 (en) | 2004-09-28 | 2010-09-14 | Woodbridge Corporation | Apparatus for the continuous production of plastic composites |
US8138234B2 (en) | 2006-03-24 | 2012-03-20 | Century-Board Usa, Llc | Polyurethane composite materials |
US8846776B2 (en) | 2009-08-14 | 2014-09-30 | Boral Ip Holdings Llc | Filled polyurethane composites and methods of making same |
US8901187B1 (en) | 2008-12-19 | 2014-12-02 | Hickory Springs Manufacturing Company | High resilience flexible polyurethane foam using MDI |
US8906975B1 (en) | 2009-02-09 | 2014-12-09 | Hickory Springs Manufacturing Company | Conventional flexible polyurethane foam using MDI |
US9045581B2 (en) | 2005-03-03 | 2015-06-02 | Rhino Linings Corporation | Polyols derived from a vegetable oil using an oxidation process |
US9481759B2 (en) | 2009-08-14 | 2016-11-01 | Boral Ip Holdings Llc | Polyurethanes derived from highly reactive reactants and coal ash |
US9745224B2 (en) | 2011-10-07 | 2017-08-29 | Boral Ip Holdings (Australia) Pty Limited | Inorganic polymer/organic polymer composites and methods of making same |
US9752015B2 (en) | 2014-08-05 | 2017-09-05 | Boral Ip Holdings (Australia) Pty Limited | Filled polymeric composites including short length fibers |
US9988512B2 (en) | 2015-01-22 | 2018-06-05 | Boral Ip Holdings (Australia) Pty Limited | Highly filled polyurethane composites |
US10030126B2 (en) | 2015-06-05 | 2018-07-24 | Boral Ip Holdings (Australia) Pty Limited | Filled polyurethane composites with lightweight fillers |
US10086542B2 (en) | 2004-06-24 | 2018-10-02 | Century-Board Usa, Llc | Method for molding three-dimensional foam products using a continuous forming apparatus |
US10138341B2 (en) | 2014-07-28 | 2018-11-27 | Boral Ip Holdings (Australia) Pty Limited | Use of evaporative coolants to manufacture filled polyurethane composites |
US10472281B2 (en) | 2015-11-12 | 2019-11-12 | Boral Ip Holdings (Australia) Pty Limited | Polyurethane composites with fillers |
WO2024164058A1 (en) * | 2023-02-07 | 2024-08-15 | Isocare Soluções Ambientais S/A | Liquid base product, liquid formulated product, liquid end product, renewable and biodegradable flexible polymer, process for manufacturing a liquid base product, process for manufacturing a liquid formulated product, process for manufacturing a liquid end product, process for manufacturing a renewable and biodegradable flexible polymer |
Families Citing this family (86)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE69739734D1 (en) * | 1996-11-15 | 2010-02-25 | Cytokine Pharmasciences Inc | GUANYL HYDRAZONE USEFUL FOR THE TREATMENT OF T-CELL ASSOCIATED DISEASES |
US7063877B2 (en) * | 1998-09-17 | 2006-06-20 | Urethane Soy Systems Company, Inc. | Bio-based carpet material |
US20090223620A1 (en) * | 1998-09-17 | 2009-09-10 | Kurth Thomas M | Method of producing a bio-based carpet material |
US6962636B2 (en) * | 1998-09-17 | 2005-11-08 | Urethane Soy Systems Company, Inc. | Method of producing a bio-based carpet material |
US20030191274A1 (en) * | 2001-10-10 | 2003-10-09 | Kurth Thomas M. | Oxylated vegetable-based polyol having increased functionality and urethane material formed using the polyol |
US7595094B2 (en) * | 1998-09-17 | 2009-09-29 | Urethane Soy Systems, Co. | Vegetable oil-based coating and method for application |
US20020058774A1 (en) * | 2000-09-06 | 2002-05-16 | Kurth Thomas M. | Transesterified polyol having selectable and increased functionality and urethane material products formed using the polyol |
US6180686B1 (en) * | 1998-09-17 | 2001-01-30 | Thomas M. Kurth | Cellular plastic material |
US20030083394A1 (en) * | 2001-06-07 | 2003-05-01 | Clatty Jan L. | Polyurethane foams having improved heat sag and a process for their production |
RU2300196C2 (en) * | 2002-01-11 | 2007-06-10 | Родианил | Utilization of zinc sulfide as antitick agent |
US20030143910A1 (en) * | 2002-01-31 | 2003-07-31 | Mashburn Larry E. | Carpet backings prepared from vegetable oil-based polyurethanes |
JP2006524744A (en) * | 2003-04-25 | 2006-11-02 | ダウ グローバル テクノロジーズ インコーポレイティド | Vegetable oil-based polyol and polyurethane produced therefrom |
CA2469986A1 (en) | 2003-06-06 | 2004-12-06 | Hagen, Hans T., Iii | Insulated stud panel and method of making such |
US7168216B2 (en) * | 2003-06-06 | 2007-01-30 | Hans T. Hagen, Jr. | Insulated stud panel and method of making such |
US7211206B2 (en) * | 2004-01-23 | 2007-05-01 | Century-Board Usa Llc | Continuous forming system utilizing up to six endless belts |
US20050176839A1 (en) * | 2004-02-10 | 2005-08-11 | Huzeir Lekovic | Low density acoustic foams based on biopolymers |
US8258198B2 (en) * | 2004-05-28 | 2012-09-04 | Air Products And Chemicals, Inc. | Fast demold/extended cream time polyurethane formulations |
AU2005254944B2 (en) * | 2004-06-10 | 2011-01-27 | Dow Global Technologies Llc | Polyurethane carpet backings made using fatty acid amide polyols |
US20050282921A1 (en) * | 2004-06-18 | 2005-12-22 | Ford Global Technologies, Llc | Automotive grade, flexible polyurethane foam and method for making the same |
US8501828B2 (en) | 2004-08-11 | 2013-08-06 | Huntsman Petrochemical Llc | Cure rebond binder |
US20060073322A1 (en) * | 2004-10-01 | 2006-04-06 | Lear Corporation | Low density spray polyurethane for automobile interior applications |
WO2006047432A1 (en) * | 2004-10-25 | 2006-05-04 | Dow Global Technologies, Inc. | Polyurethane carpet backings made using hydroxymethylated polyester polyols |
WO2006071549A1 (en) * | 2004-12-23 | 2006-07-06 | Dow Global Technologies Inc. | An isocyanate composition comprising a vegetable oil and composites therefrom |
US20060141239A1 (en) * | 2004-12-28 | 2006-06-29 | Gilder Stephen D | Method for making a bonded foam product suitable for use as an underlayment for floor coverings |
US20060222775A1 (en) * | 2005-03-24 | 2006-10-05 | Lear Corporation | System, method and composition for forming composite sprayed polyurethane skins having a low density expanded polyurethane layer |
US20060229375A1 (en) * | 2005-04-06 | 2006-10-12 | Yu-Ling Hsiao | Polyurethane foams made with alkoxylated vegetable oil hydroxylate |
US20060276614A1 (en) * | 2005-04-12 | 2006-12-07 | Niemann Lance K | Bio-based, multipurpose adhesive |
US20060235100A1 (en) * | 2005-04-13 | 2006-10-19 | Kaushiva Bryan D | Polyurethane foams made with vegetable oil hydroxylate, polymer polyol and aliphatic polyhydroxy alcohol |
US20060240194A1 (en) * | 2005-04-26 | 2006-10-26 | Cargill, Incorporated | Polyglycerol fatty acid ester composition and coating |
MX2007013464A (en) * | 2005-04-29 | 2008-01-21 | Dow Global Technologies Inc | Polyester polyols containing secondary alcohol groups and their use in making polyurethanes such as flexible polyurethane foams. |
US7566406B2 (en) * | 2005-05-05 | 2009-07-28 | L&P Property Management Company | Bonded foam product manufactured with vegetable oil polyol and method for manufacturing |
US7700661B2 (en) * | 2005-05-05 | 2010-04-20 | Sleep Innovations, Inc. | Prime foam containing vegetable oil polyol |
KR100950707B1 (en) * | 2005-08-12 | 2010-03-31 | 미쓰이 가가쿠 가부시키가이샤 | Composition for polyurethane foam, polyurethane foam obtained from the composition, and use thereof |
US20070078193A1 (en) * | 2005-08-31 | 2007-04-05 | Gilder Stephen D | Strut-reinforced, reduced VOC polyurethane foam |
US20070066697A1 (en) * | 2005-08-31 | 2007-03-22 | Gilder Stephen D | Strut-reinforced polyurethane foam |
US20100174006A1 (en) * | 2005-09-20 | 2010-07-08 | Sleep Innovations, Inc. | Strut-Reinforced, Reduced VOC Polyurethane Foam |
US20070123597A1 (en) * | 2005-11-29 | 2007-05-31 | Ford Global Technologies, Llc | Encapsulated flexible polyurethane foam and method for making polyol to form foam |
US20070129451A1 (en) * | 2005-12-01 | 2007-06-07 | Niemann Lance K | Bio-based, insulating foam |
US7538236B2 (en) * | 2006-01-04 | 2009-05-26 | Suresh Narine | Bioplastics, monomers thereof, and processes for the preparation thereof from agricultural feedstocks |
DE102006039901A1 (en) * | 2006-08-25 | 2008-02-28 | Renate Marquardt | Novel high-water polyurethanes, processes for their preparation and use |
US7674925B2 (en) * | 2006-09-21 | 2010-03-09 | Athletic Polymer Systems, Inc. | Polyols from plant oils and methods of conversion |
US8575294B2 (en) * | 2006-09-21 | 2013-11-05 | Thomas M. Garrett | High bio content hybrid natural oil polyols and methods therefor |
AU2007301112A1 (en) | 2006-09-27 | 2008-04-03 | Asahi Glass Company, Limited | Method for producing soft polyurethane foam |
US20080185900A1 (en) * | 2006-09-28 | 2008-08-07 | Lee Ellen Cheng-Ch | Use of renewable and biodegradable materials for automotive interiors |
US8901189B2 (en) * | 2006-10-30 | 2014-12-02 | Johnsons Controls Technology Company | Nop foam |
WO2008063613A1 (en) * | 2006-11-16 | 2008-05-29 | Cargill, Incorporated | Viscoelastic polyurethane foams comprising amidated or transesterified oligomeric natural oil polyols |
CN101563386A (en) * | 2006-12-19 | 2009-10-21 | 旭硝子株式会社 | Method for producing soft polyurethane foam |
US20080164730A1 (en) * | 2007-01-05 | 2008-07-10 | Ford Global Technologies, Llc | Insert for vehicle seat head restraint |
EP2126234A1 (en) * | 2007-03-07 | 2009-12-02 | Salvatore Anthony Diloreto | Polyurethane foam batt insulation |
US20090029097A1 (en) * | 2007-06-11 | 2009-01-29 | Riddle Dennis L | Flooring products and methods |
BRPI0813611A2 (en) * | 2007-08-06 | 2019-09-24 | Dow Global Technologies Inc | "composition, polymer, process for preparing a polymer and article" |
US7678936B2 (en) * | 2007-08-21 | 2010-03-16 | Lear Corporation | Isocyanato terminated precursor and method of making the same |
US20090295021A1 (en) * | 2008-05-27 | 2009-12-03 | Century-Board Usa, Llc | Extrusion of polyurethane composite materials |
CN101684171B (en) * | 2008-09-27 | 2012-11-14 | 上海联合气雾制品灌装有限公司 | Single-component polyurethane foam prepared from renewable raw materials |
GB0903717D0 (en) * | 2009-03-04 | 2009-04-15 | Innochem Ltd | Flexible polyurethane foam |
BRPI1010536A2 (en) | 2009-03-06 | 2016-03-15 | Biopolymer Technologies Ltd | protein-containing foams, manufacture and use thereof |
EP2403888B1 (en) | 2009-03-06 | 2021-05-12 | Evertree | Protein-containing emulsions and adhesives, and manufacture and use thereof |
US8476329B2 (en) * | 2009-06-11 | 2013-07-02 | Basf Se | Bioresin composition for use in forming a rigid polyurethane foam article |
JPWO2011043345A1 (en) | 2009-10-05 | 2013-03-04 | 旭硝子株式会社 | Flexible polyurethane foam, method for producing the same, and automobile seat cushion |
US8828269B1 (en) | 2009-11-16 | 2014-09-09 | Thomas M. Garrett | Method for increasing miscibility of natural oil polyol with petroleum-based polyol |
CN101704938B (en) * | 2009-11-27 | 2011-11-30 | 中国科学院青岛生物能源与过程研究所 | Preparation method of bean pulp polyurethane foam plastics |
JP2013513012A (en) | 2009-12-08 | 2013-04-18 | ダウ グローバル テクノロジーズ エルエルシー | Process for preparing open cell foams produced using natural oil-based polyols and poly (propylene oxide) polyols |
US8541536B2 (en) * | 2010-01-07 | 2013-09-24 | Mcpu Polymer Engineering Llc | Coupling method for providing high molecular weight natural oil polyol |
US8822625B2 (en) | 2010-01-07 | 2014-09-02 | MCPU Polymer Engineering, LLC | Method for providing higher molecular weight natural oil polyols without loss of functionality |
US8865854B2 (en) | 2010-01-07 | 2014-10-21 | Thomas M Garrett | Method of synthesizing tuneably high functionality in high molecular weight natural oil polyols |
US8022164B1 (en) * | 2010-03-04 | 2011-09-20 | Microvast, Inc. | Two-component solvent-free polyurethane adhesives |
JP5585175B2 (en) * | 2010-04-08 | 2014-09-10 | 東ソー株式会社 | Method for producing polyurethane resin |
US8933191B1 (en) | 2010-05-19 | 2015-01-13 | Thomas M. Garrett | Method for synthesizing high molecular weight natural oil polyols |
WO2011156380A2 (en) | 2010-06-07 | 2011-12-15 | Biopolymer Technologies, Ltd. | Protein-containing adhesives, and manufacture and use thereof |
JP5627333B2 (en) | 2010-08-12 | 2014-11-19 | 住化バイエルウレタン株式会社 | Polyurethane composition for integral skin foam |
DK2753633T3 (en) | 2011-09-09 | 2017-03-20 | Evertree | PROTEIN-CONTAINING ADHESIVES, THEIR PREPARATION AND APPLICATION THEREOF |
BR112014005502A2 (en) | 2011-09-09 | 2017-04-04 | Biopolymer Tech Ltd | protein-containing adhesives, and manufacture and use thereof |
EP2677030A1 (en) | 2012-06-21 | 2013-12-25 | Latvijas Valsts Koksnes kimijas instituts | Polyurethane rigid and flexible foams as composite obtained from wood origin raw materials and used as support for immobilization of microorganisms that produce ligninolytic enzymes |
EP2880116B1 (en) | 2012-07-30 | 2020-02-05 | Evertree | Protein adhesives containing an anhydride, carboxylic acid, and/or carboxylate salt compound and their use |
US10619001B2 (en) | 2013-03-14 | 2020-04-14 | Lear Corporation | Polyurethane foam forming composition including triglycerides, polyurethane foam made from the composition, and method of making polyurethane foam |
US9932457B2 (en) | 2013-04-12 | 2018-04-03 | Boral Ip Holdings (Australia) Pty Limited | Composites formed from an absorptive filler and a polyurethane |
US9371633B2 (en) * | 2014-11-25 | 2016-06-21 | Dennis R. Salazar | Apparatus and method of freeze protection in fluid systems |
WO2018183440A1 (en) | 2017-03-28 | 2018-10-04 | Ford Global Technologies, Llc | Bio-based polyurethane resin for additive manufacturing |
CN107501516A (en) * | 2017-09-08 | 2017-12-22 | 张家港长泰汽车饰件材料有限公司 | Low aldehyde content polyurethane plate and preparation method thereof |
BR112020008034A2 (en) * | 2017-11-08 | 2020-10-06 | Basf Se | process for preparing polyurethane moldings, polyurethane molding and use of a polyurethane molding |
BR112021003913A2 (en) | 2018-08-30 | 2021-05-18 | Checkerspot, Inc. | hydroformylated triglycerides and their uses |
US11214584B2 (en) * | 2018-12-14 | 2022-01-04 | Nanjing Tech University | Polyols for preparing flexible polyurethane foam, and preparation method and application thereof |
CN110372841B (en) * | 2019-07-24 | 2022-02-11 | 张家港市飞航科技有限公司 | Polyurethane hard foam heat-insulating material and preparation method thereof |
CN115485314B (en) | 2019-12-18 | 2024-03-26 | 格纹蛱蝶公司 | Use of microorganism derived materials in polymer applications |
CN112779100B (en) * | 2021-01-25 | 2023-04-25 | 南京工业大学 | Vegetable oil polyol for removing suspension chain, and preparation method and application thereof |
WO2023102069A1 (en) | 2021-12-01 | 2023-06-08 | Checkerspot, Inc. | Polyols, polyurethane dispersions, and uses thereof |
Citations (96)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1447954A (en) * | 1923-03-06 | pelham manor | ||
US2167266A (en) * | 1938-04-08 | 1939-07-25 | Fuel Dev Corp | Valve for automatic control of supplementary liquids |
US2556336A (en) * | 1946-08-20 | 1951-06-12 | Harvel Res Corp | Copolymerization of styrene with blown unsaturated fatty oils |
US2606890A (en) * | 1949-12-15 | 1952-08-12 | Union Oil Co | Production of high molecular weight carboxylic acids and their derivatives |
US2745855A (en) * | 1951-04-14 | 1956-05-15 | Sinclair Oil & Gas Co | Alkylene oxide condensate of discard palm oil |
US2787601A (en) * | 1953-03-03 | 1957-04-02 | Du Pont | Cellular plastic materials which are condensation products of hydroxy containing fatty acid glycerides and arylene dhsocyanates |
US2833730A (en) * | 1953-09-30 | 1958-05-06 | Du Pont | Arylene diisocyanate-fatty acid triglyceride-polyol cellular materials and process of producing same |
US3396473A (en) * | 1966-08-03 | 1968-08-13 | Dow Chemical Co | Method of desorbing vaporizable liquids from sorptive material |
US3576929A (en) * | 1968-06-21 | 1971-04-27 | Dow Chemical Co | Method for cooling blown polymer films |
US3639312A (en) * | 1969-02-25 | 1972-02-01 | Dow Chemical Co | Olefin polymers containing sugars |
US3752212A (en) * | 1970-07-20 | 1973-08-14 | Thompson E Manuf Co | Method of forming castings of different metals |
US3821130A (en) * | 1972-04-26 | 1974-06-28 | Dow Chemical Co | Air frothed polyurethane foams |
US3862879A (en) * | 1973-03-12 | 1975-01-28 | Dow Chemical Co | Articles coated with air frothed polyurethane foams |
US3963699A (en) * | 1974-01-10 | 1976-06-15 | The Procter & Gamble Company | Synthesis of higher polyol fatty acid polyesters |
US4005035A (en) * | 1974-12-24 | 1977-01-25 | Tecnik International Corporation | Composition for reinforced and filled high density rigid polyurethane foam products and method of making same |
US4022941A (en) * | 1974-06-27 | 1977-05-10 | Union Carbide Corporation | Organosilicone polymers in polyurethane foams for carpet backing |
US4045498A (en) * | 1975-10-15 | 1977-08-30 | Fats And Proteins Research Foundation, Inc. | Method of hydroxylation |
US4076679A (en) * | 1976-01-21 | 1978-02-28 | The Dow Chemical Company | Rapid setting polyurethane elastomers and process of preparation |
US4185146A (en) * | 1978-11-15 | 1980-01-22 | The General Tire & Rubber Company | Polyurethane binder composition containing a rubber extender oil and a finely divided solid soybean derivative |
US4246363A (en) * | 1979-06-18 | 1981-01-20 | The Dow Chemical Company | Reaction injection molded polyurethanes having particular flexural modulus factors and at least two thermal transition temperatures in a particular range |
US4264743A (en) * | 1979-04-23 | 1981-04-28 | Nhk Spring Co., Ltd. | Polyurethane foam sealing material and process for producing the same |
US4278482A (en) * | 1979-06-26 | 1981-07-14 | Custom Coating, Inc. | Apparatus and method for production of polyurethane carpet backing |
US4286003A (en) * | 1978-10-18 | 1981-08-25 | Milliken Research Corporation | Thin polyurethane foam backed rug |
US4314088A (en) * | 1980-11-24 | 1982-02-02 | Exxon Research & Engineering Co. | Hydroxylation of olefins |
US4334061A (en) * | 1979-10-29 | 1982-06-08 | Ethyl Corporation | Process for recovery of polyol fatty acid polyesters |
US4375521A (en) * | 1981-06-01 | 1983-03-01 | Communications Technology Corporation | Vegetable oil extended polyurethane systems |
US4376171A (en) * | 1981-11-09 | 1983-03-08 | Blount David H | Process for the production of polyester resins |
US4390739A (en) * | 1981-10-09 | 1983-06-28 | Exxon Research & Engineering Co. | Hydroxylation of olefins |
US4393253A (en) * | 1980-11-24 | 1983-07-12 | Exxon Research & Engineering Co. | Hydroxylation of olefins |
US4496778A (en) * | 1983-10-03 | 1985-01-29 | Exxon Research & Engineering Co. | Process for the hydroxylation of olefins using molecular oxygen, an osmium containing catalyst, a copper Co-catalyst, and an aromatic amine based promoter |
US4496547A (en) * | 1981-12-25 | 1985-01-29 | Mitsui Toatsu Chemicals, Inc. | Saccharide fatty acid ester for bloat-prevention or bloat-treatment |
US4496779A (en) * | 1984-04-26 | 1985-01-29 | Exxon Research & Engineering Co. | Process for the hydroxylation of olefins using molecular oxygen, an osmium containing catalyst, a copper co-catalyst, and a cycloaliphatic amine based promoter |
US4512831A (en) * | 1979-01-02 | 1985-04-23 | Tillotson John G | Method for forming a layer of blown cellular urethane on a carpet backing |
US4515646A (en) * | 1983-11-22 | 1985-05-07 | Paul Walker | Method for applying polyurethane backing |
US4518772A (en) * | 1983-06-23 | 1985-05-21 | The Proctor & Gamble Company | Synthesis of higher polyol fatty acid polyesters using high soap:polyol ratios |
US4530941A (en) * | 1983-01-26 | 1985-07-23 | The Dow Chemical Company | Reaction injection molded polyurethanes employing high molecular weight polyols |
US4582891A (en) * | 1984-02-09 | 1986-04-15 | Dai-Ichi Kogyo Seiyaku Co., Ltd. | Process for inhibiting corrosion of polyurethane coating |
US4585804A (en) * | 1981-03-25 | 1986-04-29 | The Dow Chemical Company | Rigid foam with improved "K" factor by reacting a polyol, a polyisocyanate and at least one compound having at least one primary aliphatic amine group |
US4595436A (en) * | 1983-11-22 | 1986-06-17 | Paul Walker | Method for applying polyurethane backing |
US4642320A (en) * | 1983-11-02 | 1987-02-10 | The Dow Chemical Company | Reaction injection molded polyureas employing high molecular weight amine-terminated polyethers |
US4657790A (en) * | 1985-07-08 | 1987-04-14 | The Dow Chemical Company | Polyurethane backed carpet |
US4686242A (en) * | 1985-03-25 | 1987-08-11 | The Dow Chemical Company | Polyurea polymers prepared from urea containing prepolymers |
US4687788A (en) * | 1982-10-08 | 1987-08-18 | The Dow Chemical Company | Dimensionally stable urethane elastomers |
US4734455A (en) * | 1986-12-05 | 1988-03-29 | The Dow Chemical Company | Stabilizers for filled polyol compositions |
US4740367A (en) * | 1984-07-19 | 1988-04-26 | Westvaco Corporation | Vegetable oil adducts as emollients in skin and hair care products |
US4745135A (en) * | 1986-06-25 | 1988-05-17 | The Dow Chemical Company | Polyurethanes prepared from liquid crystal-containing polyols |
US4745137A (en) * | 1986-06-25 | 1988-05-17 | The Dow Chemical Company | Polyurethanes prepared from solutions or dispersions of polymers of rigid polyaromatic monomers in polyols |
US4745136A (en) * | 1986-06-25 | 1988-05-17 | The Dow Chemical Company | Polyurethanes prepared from dispersions or solutions of cholesterol or cholestanol-containing polymers in a polyol |
US4798849A (en) * | 1986-06-25 | 1989-01-17 | The Dow Chemical Company | Organic polymers containing dispersed liquid crystalline filler polymers |
US4806632A (en) * | 1986-12-29 | 1989-02-21 | The Procter & Gamble Company | Process for the post-hydrogenation of sucrose polyesters |
US4825004A (en) * | 1987-06-13 | 1989-04-25 | Henkel Kommanditgesellschaft Auf Aktien | Process for the production of alkane polyols |
US4843138A (en) * | 1988-02-08 | 1989-06-27 | The Firestone Tire & Rubber Company | Polyureaurethanes having improved low temperature properties based on high molecular weight polyether intermediates |
US4853280A (en) * | 1986-11-17 | 1989-08-01 | The Dow Chemical Company | Releasable polyurethane backed textiles |
US4853054A (en) * | 1987-09-29 | 1989-08-01 | The Dow Chemical Company | Process for preparing polyurethane carpet backings based on high equivalent weight polyols |
US4861803A (en) * | 1986-06-25 | 1989-08-29 | The Dow Chemical Company | Organic polymers reinforced with rigid rod micro fillers |
US4913958A (en) * | 1989-06-29 | 1990-04-03 | The Dow Chemical Company | Process for preparing polyurethane-backed substrate |
US4931552A (en) * | 1988-06-30 | 1990-06-05 | The Procter & Gamble Company | Production of polyol polyesters having reduced color content |
US4942278A (en) * | 1988-12-05 | 1990-07-17 | The United States Of America As Represented By The United States Department Of Energy | Microwaving of normally opaque and semi-opaque substances |
US4943626A (en) * | 1988-07-29 | 1990-07-24 | The Dow Chemical Company | Primary polyether active hydrogen compounds which are prepared from linked, protectively initiated polyalkyleneoxides |
US4952687A (en) * | 1986-02-19 | 1990-08-28 | Lever Brothers Company | Fatty acid esters of sugars and sugar alcohols |
US5010117A (en) * | 1989-06-16 | 1991-04-23 | Dow Chemical Company | Flexible polyurethane foams prepared using low unsaturation polyether polyols |
US5021256A (en) * | 1987-05-06 | 1991-06-04 | The Procter & Gamble Company | Shortening compositions containing polyol polyesters |
US5032622A (en) * | 1990-07-02 | 1991-07-16 | The Dow Chemical Company | Densifiable and re-expandable polyurethane foam |
US5104910A (en) * | 1991-01-03 | 1992-04-14 | The Dow Chemical Company | Combustion-modified polyurethane foam |
US5104693A (en) * | 1990-12-20 | 1992-04-14 | The Dow Chemical Company | Polyurethane carpet-backing process based on soft segment prepolymers of diphenylmethane diisocyanate (MDI) |
US5106884A (en) * | 1988-10-28 | 1992-04-21 | The Dow Chemical Company | Flexible polyurea foams having controlled load bearing qualities |
US5106874A (en) * | 1989-06-16 | 1992-04-21 | The Dow Chemical Company | Process for preparing elastomeric polyurethane or polyurethane-urea polymers, and polyurethanes so prepared |
US5106967A (en) * | 1988-05-05 | 1992-04-21 | The Procter & Gamble Company | Functional sugar substitutes with reduced calories |
US5126494A (en) * | 1988-01-11 | 1992-06-30 | Massachusetts Institute Of Technology | Methods for catalytic asymmetric dihydroxylation of olefins |
US5194281A (en) * | 1989-10-16 | 1993-03-16 | The Procter & Gamble Company | Polyol fatty acid polyesters with reduced trans double bond levels and process for making |
US5225049A (en) * | 1989-12-21 | 1993-07-06 | Van Den Bergh Foods Co., Division Of Conopco, Inc. | Process for refining organic-solvent containing crude polyol fatty-acid polyester products |
US5231199A (en) * | 1988-06-29 | 1993-07-27 | Van Den Bergh Foods Co., Division Of Conopco, Inc. | Process for the synthesis of polyol fatty acid polyesters |
US5324846A (en) * | 1992-01-30 | 1994-06-28 | Elf Atochem North America, Inc. | Partial esters of epoxy containing compounds |
US5397810A (en) * | 1989-07-19 | 1995-03-14 | Mitsui Toatsu Chemicals, Inc. | Polyol, polyurethane resin and utilization thereof |
US5482980A (en) * | 1994-07-14 | 1996-01-09 | Pmc, Inc. | Methods for preparing flexible, open-celled, polyester and polyether urethane foams and foams prepared thereby |
US5491226A (en) * | 1994-04-06 | 1996-02-13 | Procter & Gamble Company | Process for preparing polyol polyesters having low levels of triglycerides |
US5491174A (en) * | 1992-10-09 | 1996-02-13 | The Dow Chemical Company | Process for preparation of polyurethanes utilizing novel catalysts |
US5496869A (en) * | 1994-05-05 | 1996-03-05 | Stepan Company | Methods and compositions for preparing rigid foams with non-chlorofluorocarbon blowing agents |
US5504202A (en) * | 1994-04-05 | 1996-04-02 | Henkel Corporation | Sucrose polyester useful as fat subtitute and preparation process |
US5627221A (en) * | 1992-08-27 | 1997-05-06 | Stepan Company | Process for production of low density water-blown rigid foams with flow and dimensional stability |
US5629434A (en) * | 1992-12-17 | 1997-05-13 | Exxon Chemical Patents Inc | Functionalization of polymers based on Koch chemistry and derivatives thereof |
US5648483A (en) * | 1995-06-07 | 1997-07-15 | The Procter & Gamble Company | Continuous transesterification method for preparing polyol polyesters |
US5710190A (en) * | 1995-06-07 | 1998-01-20 | Iowa State University Research Foundation, Inc. | Soy protein-based thermoplastic composition for foamed articles |
US5756195A (en) * | 1995-06-07 | 1998-05-26 | Acushnet Company | Gel cushion conprising rubber polymer and oil |
US5766704A (en) * | 1995-10-27 | 1998-06-16 | Acushnet Company | Conforming shoe construction and gel compositions therefor |
US5767257A (en) * | 1996-07-19 | 1998-06-16 | The Procter & Gamble Company | Methods for producing polyol fatty acid polyesters using atmospheric or superatmospheric pressure |
US5869546A (en) * | 1994-04-13 | 1999-02-09 | Bayer Aktiengesellschaft | Mixtures leading to hard polyurethane foamed materials |
US5900496A (en) * | 1990-03-21 | 1999-05-04 | The United States Of America As Represented By The Secretary Of Agriculture | Microbial production of a novel compound 7,10-dihydroxy-8-octadecenoic acid from oleic acid |
US5908701A (en) * | 1996-12-10 | 1999-06-01 | The Dow Chemical Company | Preparation of filled reactive polyurethane carpet backing formulations using an in-line continuous mixing process |
US5922779A (en) * | 1997-10-10 | 1999-07-13 | Stepan Company | Polyol blends for producing hydrocarbon-blown polyurethane and polyisocyanurate foams |
US6015440A (en) * | 1997-10-31 | 2000-01-18 | Board Of Regents Of The University Of Nebraska | Process for producing biodiesel fuel with reduced viscosity and a cloud point below thirty-two (32) degrees fahrenheit |
US6080853A (en) * | 1996-08-08 | 2000-06-27 | The Procter & Gamble Company | Polyol polyester synthesis |
US6174501B1 (en) * | 1997-10-31 | 2001-01-16 | The Board Of Regents Of The University Of Nebraska | System and process for producing biodiesel fuel with reduced viscosity and a cloud point below thirty-two (32) degrees fahrenheit |
US6180686B1 (en) * | 1998-09-17 | 2001-01-30 | Thomas M. Kurth | Cellular plastic material |
US6388002B1 (en) * | 1997-12-04 | 2002-05-14 | Rhodia Limited | Dispersed resins for use in coating compositions |
US6420446B1 (en) * | 2000-03-27 | 2002-07-16 | Ck Witco | Polyurethane prepared from sorbitol-branched polyesters |
Family Cites Families (55)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2569206A (en) | 1951-09-25 | Removing inhibitors from | ||
US449654A (en) * | 1891-04-07 | Bedstead-exhibitor | ||
US3001958A (en) | 1957-02-06 | 1961-09-26 | Spencer Kellogg And Sons Inc | Modifying drying oil |
DE1504093A1 (en) * | 1963-11-14 | 1969-09-25 | Collo Rheincollodium Koeln Gmb | Process for the production of light-core composite panels and light-core composite structures from plastic foam |
US3488394A (en) | 1966-05-11 | 1970-01-06 | Fmc Corp | Oxidation of olefinic compounds to glycols |
US3535156A (en) | 1967-12-11 | 1970-10-20 | Dow Chemical Co | Method of employing aqueous fluorocarbon concentrates in chlorinated solvent application to textiles |
US3778205A (en) | 1970-06-11 | 1973-12-11 | Dow Chemical Co | Apparatus for cooling blown polymer films |
US3755212A (en) | 1971-05-13 | 1973-08-28 | Dow Chemical Co | Air blown polyurethane foams |
US4036789A (en) * | 1973-08-20 | 1977-07-19 | Stauffer Chemical Company | Polyurethane foams prepared from mixed polyalkylene glycol polyphosphorous compounds |
US3985814A (en) | 1975-02-28 | 1976-10-12 | Celanese Corporation | Production of alcohols from carboxylic acids |
US3991126A (en) | 1975-09-11 | 1976-11-09 | Chevron Research Company | Hydroxylation of unsaturated diols to prepare novel tetraols |
US4405393A (en) | 1977-03-30 | 1983-09-20 | Tillotson John G | Method for forming a layer of blown cellular urethane on a carpet backing |
US4171395A (en) | 1977-03-30 | 1979-10-16 | Tillotson John G | Method and apparatus for forming a layer of foam urethane on a carpet backing and product |
FR2420548A1 (en) * | 1978-03-25 | 1979-10-19 | Akzo Nv | POLYURETHANES COATING MASS, ITS PREPARATION PROCESS AND ITS USE |
US4296159A (en) | 1980-09-29 | 1981-10-20 | The Dow Chemical Company | Polyurethane backed carpet |
US4354810A (en) | 1980-11-24 | 1982-10-19 | Polysar Incorporated | Apparatus for distributing a foamed composition on a substrate |
US4483894A (en) | 1981-06-24 | 1984-11-20 | The Dow Chemical Company | Process for applying polyurethane foams to substrates and product made thereby |
DE3316652A1 (en) * | 1983-05-06 | 1984-12-20 | Dr. Alois Stankiewicz Schallschluck GmbH & Co KG, 3101 Adelheidsdorf | Foam material with noise-reducing properties |
US4611044A (en) | 1985-05-28 | 1986-09-09 | The Dow Chemical Company | Polyurethane carpet backing catalyzed with organoiron and organobismuth catalysts |
US5173505A (en) * | 1985-06-20 | 1992-12-22 | University Of Florida | Anti-neoplastic, anti-viral and ribonucleotide reductase activity affecting pharmaceutical compositions and methods of treatment |
US4696849A (en) | 1985-09-16 | 1987-09-29 | The Dow Chemical Company | Process for preparing polyurethane-backed textiles |
NL8601904A (en) | 1986-07-23 | 1988-02-16 | Unilever Nv | PROCESS FOR THE PREPARATION OF POLYOL FATTY ACID POLYESTERS. |
DE3702615A1 (en) | 1987-01-29 | 1988-08-11 | Henkel Kgaa | COATING AND FINISHING AGENT FOR LEATHER |
US4968791A (en) | 1987-07-23 | 1990-11-06 | Lever Brothers Company | Process for the preparation of polyol fatty acid esters |
JPH0762025B2 (en) | 1988-10-05 | 1995-07-05 | 昭和産業株式会社 | Method for stabilizing polyol fatty acid polyester |
US4980388A (en) | 1988-10-17 | 1990-12-25 | The Dow Chemical Company | Use of carbon dioxide adducts as blowing agents in cellular and microcellular polyureas |
US5043438B1 (en) | 1989-02-16 | 1998-04-28 | Lever Brothers Ltd | Process for the synthesis of polyol fatty-acid esters |
FR2658187B1 (en) | 1990-02-15 | 1993-09-17 | Rhone Poulenc Sante | NOVEL ALPHA-HYDROXYLIC ACIDS, PROCESS FOR THEIR PREPARATION AND THEIR USE. |
JPH09506641A (en) * | 1992-06-26 | 1997-06-30 | ミネソタ マイニング アンド マニュファクチャリング カンパニー | Polyurethane / polyurea elastomer |
TW211523B (en) | 1992-06-29 | 1993-08-21 | Amerchol Corp | Hydroxylated milk glycerides |
JP3115458B2 (en) * | 1993-08-30 | 2000-12-04 | トヨタ自動車株式会社 | Transmission control device for automatic transmission |
DE4332292A1 (en) | 1993-09-20 | 1995-03-23 | Brinckmann Harburger Fett | Process for the direct hydroxylation of unsaturated carboxylic acids |
US5440027A (en) | 1993-10-05 | 1995-08-08 | Kraft General Foods, Inc. | Method for preparing saccharide fatty acid polyesters by transesterification |
US5571935A (en) | 1994-01-14 | 1996-11-05 | Cpc International Inc. | Process for producing esterified alkoxylated polyols with improved stability |
EP0672697A1 (en) * | 1994-03-17 | 1995-09-20 | Bayer Ag | Process for the preparation of rigid foams having urethane, urea and biuret groups and their use |
DE4416623A1 (en) * | 1994-04-13 | 1995-10-19 | Bayer Ag | Mixtures leading to hard polyurethane foams |
DE4420310A1 (en) | 1994-06-10 | 1995-12-14 | Henkel Kgaa | Use of dimer diol in polyurethane moldings |
US5447963A (en) | 1994-07-14 | 1995-09-05 | Pmc, Inc. | Method for reducing volatile emissions generated during the preparation of foams and fabrication of foam products |
US5681948A (en) | 1995-03-06 | 1997-10-28 | Kraft Foods, Inc. | Two-stage method for preparing polyol fatty acid polyesters |
WO1997007150A1 (en) | 1995-08-21 | 1997-02-27 | Martin Ernst Stielau | Process for producing new polymers based on oil of cashew-nut shells, and products obtained therefrom |
US5945529A (en) | 1996-07-19 | 1999-08-31 | The Procter & Gamble Company | Synthesis of polyol fatty acid polyesters using column with inert gas stripping |
WO1998007777A1 (en) | 1996-08-20 | 1998-02-26 | Martin Ernst Stielau | Use of cashew nut husk oil in rubber and duroplastics recycling |
DE19634392A1 (en) * | 1996-08-26 | 1998-03-05 | Bayer Ag | Foaming polyurethane formulations with good flow behavior and a process for producing foamed polyurethane moldings |
US6096401A (en) * | 1996-08-28 | 2000-08-01 | The Dow Chemical Company | Carpet backing precoats, laminate coats, and foam coats prepared from polyurethane formulations including fly ash |
DE19643816A1 (en) * | 1996-10-30 | 1998-05-07 | Basf Ag | Polyurethane preparation using an increase in materials |
US6288133B1 (en) * | 1997-09-10 | 2001-09-11 | H. B. Fuller Licensing & Financing Inc. | Foaming urethane composition and methods of using such compositions |
US6121398A (en) | 1997-10-27 | 2000-09-19 | University Of Delaware | High modulus polymers and composites from plant oils |
US7063877B2 (en) * | 1998-09-17 | 2006-06-20 | Urethane Soy Systems Company, Inc. | Bio-based carpet material |
US20030191274A1 (en) * | 2001-10-10 | 2003-10-09 | Kurth Thomas M. | Oxylated vegetable-based polyol having increased functionality and urethane material formed using the polyol |
US6979477B2 (en) * | 2000-09-06 | 2005-12-27 | Urethane Soy Systems Company | Vegetable oil-based coating and method for application |
US6962636B2 (en) * | 1998-09-17 | 2005-11-08 | Urethane Soy Systems Company, Inc. | Method of producing a bio-based carpet material |
US6107433A (en) | 1998-11-06 | 2000-08-22 | Pittsburg State University | Process for the preparation of vegetable oil-based polyols and electroninsulating casting compounds created from vegetable oil-based polyols |
US6133329A (en) * | 1999-03-31 | 2000-10-17 | Oxid L.P. | Aromatic polyester polyols made from a natural oil |
US20030083394A1 (en) * | 2001-06-07 | 2003-05-01 | Clatty Jan L. | Polyurethane foams having improved heat sag and a process for their production |
US7098291B2 (en) * | 2002-06-10 | 2006-08-29 | Rohm And Haas Company | Urethane polymer compositions |
-
1998
- 1998-09-17 US US09/154,340 patent/US6180686B1/en not_active Expired - Lifetime
-
1999
- 1999-09-17 AU AU59268/99A patent/AU766760B2/en not_active Ceased
- 1999-09-17 WO PCT/US1999/021511 patent/WO2000015684A1/en active IP Right Grant
- 1999-09-17 BR BRPI9913784-4A patent/BR9913784B1/en not_active IP Right Cessation
- 1999-09-17 US US09/646,356 patent/US6465569B1/en not_active Expired - Lifetime
- 1999-09-17 DK DK99946975T patent/DK1127086T4/en active
- 1999-09-17 EP EP99946975A patent/EP1127086B2/en not_active Expired - Lifetime
- 1999-09-17 DE DE69923210T patent/DE69923210T3/en not_active Expired - Lifetime
- 1999-09-17 AT AT99946975T patent/ATE286929T1/en active
- 1999-09-17 CN CNB998122742A patent/CN1245428C/en not_active Expired - Fee Related
- 1999-09-17 CA CA2344378A patent/CA2344378C/en not_active Expired - Fee Related
- 1999-09-17 MX MXPA01002680A patent/MXPA01002680A/en not_active IP Right Cessation
- 1999-09-17 ES ES99946975T patent/ES2235516T5/en not_active Expired - Lifetime
- 1999-09-17 PT PT99946975T patent/PT1127086E/en unknown
- 1999-09-17 JP JP2000570219A patent/JP2002524627A/en active Pending
-
2000
- 2000-03-16 GT GT200000029A patent/GT200000029A/en unknown
- 2000-05-15 TW TW089104795A patent/TWI257399B/en not_active IP Right Cessation
-
2002
- 2002-09-24 US US10/253,252 patent/US6624244B2/en not_active Expired - Fee Related
-
2003
- 2003-08-04 US US10/634,026 patent/US6864296B2/en not_active Expired - Fee Related
- 2003-08-12 US US10/639,303 patent/US6867239B2/en not_active Expired - Fee Related
- 2003-08-12 US US10/639,109 patent/US6881763B2/en not_active Expired - Fee Related
-
2005
- 2005-04-18 US US11/108,368 patent/US20050182228A1/en not_active Abandoned
-
2007
- 2007-10-31 US US11/933,049 patent/US20080051506A1/en not_active Abandoned
Patent Citations (100)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1447954A (en) * | 1923-03-06 | pelham manor | ||
US2167266A (en) * | 1938-04-08 | 1939-07-25 | Fuel Dev Corp | Valve for automatic control of supplementary liquids |
US2556336A (en) * | 1946-08-20 | 1951-06-12 | Harvel Res Corp | Copolymerization of styrene with blown unsaturated fatty oils |
US2606890A (en) * | 1949-12-15 | 1952-08-12 | Union Oil Co | Production of high molecular weight carboxylic acids and their derivatives |
US2745855A (en) * | 1951-04-14 | 1956-05-15 | Sinclair Oil & Gas Co | Alkylene oxide condensate of discard palm oil |
US2787601A (en) * | 1953-03-03 | 1957-04-02 | Du Pont | Cellular plastic materials which are condensation products of hydroxy containing fatty acid glycerides and arylene dhsocyanates |
US2833730A (en) * | 1953-09-30 | 1958-05-06 | Du Pont | Arylene diisocyanate-fatty acid triglyceride-polyol cellular materials and process of producing same |
US3396473A (en) * | 1966-08-03 | 1968-08-13 | Dow Chemical Co | Method of desorbing vaporizable liquids from sorptive material |
US3576929A (en) * | 1968-06-21 | 1971-04-27 | Dow Chemical Co | Method for cooling blown polymer films |
US3639312A (en) * | 1969-02-25 | 1972-02-01 | Dow Chemical Co | Olefin polymers containing sugars |
US3752212A (en) * | 1970-07-20 | 1973-08-14 | Thompson E Manuf Co | Method of forming castings of different metals |
US3821130A (en) * | 1972-04-26 | 1974-06-28 | Dow Chemical Co | Air frothed polyurethane foams |
US3862879A (en) * | 1973-03-12 | 1975-01-28 | Dow Chemical Co | Articles coated with air frothed polyurethane foams |
US3963699A (en) * | 1974-01-10 | 1976-06-15 | The Procter & Gamble Company | Synthesis of higher polyol fatty acid polyesters |
US4022941A (en) * | 1974-06-27 | 1977-05-10 | Union Carbide Corporation | Organosilicone polymers in polyurethane foams for carpet backing |
US4005035A (en) * | 1974-12-24 | 1977-01-25 | Tecnik International Corporation | Composition for reinforced and filled high density rigid polyurethane foam products and method of making same |
US4045498A (en) * | 1975-10-15 | 1977-08-30 | Fats And Proteins Research Foundation, Inc. | Method of hydroxylation |
US4076679A (en) * | 1976-01-21 | 1978-02-28 | The Dow Chemical Company | Rapid setting polyurethane elastomers and process of preparation |
US4286003A (en) * | 1978-10-18 | 1981-08-25 | Milliken Research Corporation | Thin polyurethane foam backed rug |
US4185146A (en) * | 1978-11-15 | 1980-01-22 | The General Tire & Rubber Company | Polyurethane binder composition containing a rubber extender oil and a finely divided solid soybean derivative |
US4512831A (en) * | 1979-01-02 | 1985-04-23 | Tillotson John G | Method for forming a layer of blown cellular urethane on a carpet backing |
US4264743A (en) * | 1979-04-23 | 1981-04-28 | Nhk Spring Co., Ltd. | Polyurethane foam sealing material and process for producing the same |
US4246363A (en) * | 1979-06-18 | 1981-01-20 | The Dow Chemical Company | Reaction injection molded polyurethanes having particular flexural modulus factors and at least two thermal transition temperatures in a particular range |
US4278482A (en) * | 1979-06-26 | 1981-07-14 | Custom Coating, Inc. | Apparatus and method for production of polyurethane carpet backing |
US4334061A (en) * | 1979-10-29 | 1982-06-08 | Ethyl Corporation | Process for recovery of polyol fatty acid polyesters |
US4314088A (en) * | 1980-11-24 | 1982-02-02 | Exxon Research & Engineering Co. | Hydroxylation of olefins |
US4393253A (en) * | 1980-11-24 | 1983-07-12 | Exxon Research & Engineering Co. | Hydroxylation of olefins |
US4585804A (en) * | 1981-03-25 | 1986-04-29 | The Dow Chemical Company | Rigid foam with improved "K" factor by reacting a polyol, a polyisocyanate and at least one compound having at least one primary aliphatic amine group |
US4375521A (en) * | 1981-06-01 | 1983-03-01 | Communications Technology Corporation | Vegetable oil extended polyurethane systems |
US4390739A (en) * | 1981-10-09 | 1983-06-28 | Exxon Research & Engineering Co. | Hydroxylation of olefins |
US4376171A (en) * | 1981-11-09 | 1983-03-08 | Blount David H | Process for the production of polyester resins |
US4496547A (en) * | 1981-12-25 | 1985-01-29 | Mitsui Toatsu Chemicals, Inc. | Saccharide fatty acid ester for bloat-prevention or bloat-treatment |
US4687788A (en) * | 1982-10-08 | 1987-08-18 | The Dow Chemical Company | Dimensionally stable urethane elastomers |
US4530941A (en) * | 1983-01-26 | 1985-07-23 | The Dow Chemical Company | Reaction injection molded polyurethanes employing high molecular weight polyols |
US4518772A (en) * | 1983-06-23 | 1985-05-21 | The Proctor & Gamble Company | Synthesis of higher polyol fatty acid polyesters using high soap:polyol ratios |
US4496778A (en) * | 1983-10-03 | 1985-01-29 | Exxon Research & Engineering Co. | Process for the hydroxylation of olefins using molecular oxygen, an osmium containing catalyst, a copper Co-catalyst, and an aromatic amine based promoter |
US4642320A (en) * | 1983-11-02 | 1987-02-10 | The Dow Chemical Company | Reaction injection molded polyureas employing high molecular weight amine-terminated polyethers |
US4515646A (en) * | 1983-11-22 | 1985-05-07 | Paul Walker | Method for applying polyurethane backing |
US4595436A (en) * | 1983-11-22 | 1986-06-17 | Paul Walker | Method for applying polyurethane backing |
US4582891A (en) * | 1984-02-09 | 1986-04-15 | Dai-Ichi Kogyo Seiyaku Co., Ltd. | Process for inhibiting corrosion of polyurethane coating |
US4496779A (en) * | 1984-04-26 | 1985-01-29 | Exxon Research & Engineering Co. | Process for the hydroxylation of olefins using molecular oxygen, an osmium containing catalyst, a copper co-catalyst, and a cycloaliphatic amine based promoter |
US4740367A (en) * | 1984-07-19 | 1988-04-26 | Westvaco Corporation | Vegetable oil adducts as emollients in skin and hair care products |
US4686242A (en) * | 1985-03-25 | 1987-08-11 | The Dow Chemical Company | Polyurea polymers prepared from urea containing prepolymers |
US4657790A (en) * | 1985-07-08 | 1987-04-14 | The Dow Chemical Company | Polyurethane backed carpet |
US4952687A (en) * | 1986-02-19 | 1990-08-28 | Lever Brothers Company | Fatty acid esters of sugars and sugar alcohols |
US4861803A (en) * | 1986-06-25 | 1989-08-29 | The Dow Chemical Company | Organic polymers reinforced with rigid rod micro fillers |
US4745135A (en) * | 1986-06-25 | 1988-05-17 | The Dow Chemical Company | Polyurethanes prepared from liquid crystal-containing polyols |
US4745137A (en) * | 1986-06-25 | 1988-05-17 | The Dow Chemical Company | Polyurethanes prepared from solutions or dispersions of polymers of rigid polyaromatic monomers in polyols |
US4745136A (en) * | 1986-06-25 | 1988-05-17 | The Dow Chemical Company | Polyurethanes prepared from dispersions or solutions of cholesterol or cholestanol-containing polymers in a polyol |
US4798849A (en) * | 1986-06-25 | 1989-01-17 | The Dow Chemical Company | Organic polymers containing dispersed liquid crystalline filler polymers |
US4853280A (en) * | 1986-11-17 | 1989-08-01 | The Dow Chemical Company | Releasable polyurethane backed textiles |
US4734455A (en) * | 1986-12-05 | 1988-03-29 | The Dow Chemical Company | Stabilizers for filled polyol compositions |
US4806632A (en) * | 1986-12-29 | 1989-02-21 | The Procter & Gamble Company | Process for the post-hydrogenation of sucrose polyesters |
US5021256A (en) * | 1987-05-06 | 1991-06-04 | The Procter & Gamble Company | Shortening compositions containing polyol polyesters |
US4825004A (en) * | 1987-06-13 | 1989-04-25 | Henkel Kommanditgesellschaft Auf Aktien | Process for the production of alkane polyols |
US4853054A (en) * | 1987-09-29 | 1989-08-01 | The Dow Chemical Company | Process for preparing polyurethane carpet backings based on high equivalent weight polyols |
US5126494A (en) * | 1988-01-11 | 1992-06-30 | Massachusetts Institute Of Technology | Methods for catalytic asymmetric dihydroxylation of olefins |
US4843138A (en) * | 1988-02-08 | 1989-06-27 | The Firestone Tire & Rubber Company | Polyureaurethanes having improved low temperature properties based on high molecular weight polyether intermediates |
US5106967A (en) * | 1988-05-05 | 1992-04-21 | The Procter & Gamble Company | Functional sugar substitutes with reduced calories |
US5231199B1 (en) * | 1988-06-29 | 1998-08-04 | Bergh Foods Co | Process for the synthesis of polyol fatty acid polyesters |
US5231199A (en) * | 1988-06-29 | 1993-07-27 | Van Den Bergh Foods Co., Division Of Conopco, Inc. | Process for the synthesis of polyol fatty acid polyesters |
US4931552A (en) * | 1988-06-30 | 1990-06-05 | The Procter & Gamble Company | Production of polyol polyesters having reduced color content |
US4943626A (en) * | 1988-07-29 | 1990-07-24 | The Dow Chemical Company | Primary polyether active hydrogen compounds which are prepared from linked, protectively initiated polyalkyleneoxides |
US5106884A (en) * | 1988-10-28 | 1992-04-21 | The Dow Chemical Company | Flexible polyurea foams having controlled load bearing qualities |
US4942278A (en) * | 1988-12-05 | 1990-07-17 | The United States Of America As Represented By The United States Department Of Energy | Microwaving of normally opaque and semi-opaque substances |
US5010117A (en) * | 1989-06-16 | 1991-04-23 | Dow Chemical Company | Flexible polyurethane foams prepared using low unsaturation polyether polyols |
US5106874A (en) * | 1989-06-16 | 1992-04-21 | The Dow Chemical Company | Process for preparing elastomeric polyurethane or polyurethane-urea polymers, and polyurethanes so prepared |
US4913958A (en) * | 1989-06-29 | 1990-04-03 | The Dow Chemical Company | Process for preparing polyurethane-backed substrate |
US5397810A (en) * | 1989-07-19 | 1995-03-14 | Mitsui Toatsu Chemicals, Inc. | Polyol, polyurethane resin and utilization thereof |
US5194281A (en) * | 1989-10-16 | 1993-03-16 | The Procter & Gamble Company | Polyol fatty acid polyesters with reduced trans double bond levels and process for making |
US5225049A (en) * | 1989-12-21 | 1993-07-06 | Van Den Bergh Foods Co., Division Of Conopco, Inc. | Process for refining organic-solvent containing crude polyol fatty-acid polyester products |
US5900496A (en) * | 1990-03-21 | 1999-05-04 | The United States Of America As Represented By The Secretary Of Agriculture | Microbial production of a novel compound 7,10-dihydroxy-8-octadecenoic acid from oleic acid |
US5032622A (en) * | 1990-07-02 | 1991-07-16 | The Dow Chemical Company | Densifiable and re-expandable polyurethane foam |
US5104693A (en) * | 1990-12-20 | 1992-04-14 | The Dow Chemical Company | Polyurethane carpet-backing process based on soft segment prepolymers of diphenylmethane diisocyanate (MDI) |
US5104910A (en) * | 1991-01-03 | 1992-04-14 | The Dow Chemical Company | Combustion-modified polyurethane foam |
US5324846A (en) * | 1992-01-30 | 1994-06-28 | Elf Atochem North America, Inc. | Partial esters of epoxy containing compounds |
US5627221A (en) * | 1992-08-27 | 1997-05-06 | Stepan Company | Process for production of low density water-blown rigid foams with flow and dimensional stability |
US5491174A (en) * | 1992-10-09 | 1996-02-13 | The Dow Chemical Company | Process for preparation of polyurethanes utilizing novel catalysts |
US5629434A (en) * | 1992-12-17 | 1997-05-13 | Exxon Chemical Patents Inc | Functionalization of polymers based on Koch chemistry and derivatives thereof |
US5504202A (en) * | 1994-04-05 | 1996-04-02 | Henkel Corporation | Sucrose polyester useful as fat subtitute and preparation process |
US5491226A (en) * | 1994-04-06 | 1996-02-13 | Procter & Gamble Company | Process for preparing polyol polyesters having low levels of triglycerides |
US5869546A (en) * | 1994-04-13 | 1999-02-09 | Bayer Aktiengesellschaft | Mixtures leading to hard polyurethane foamed materials |
US5496869A (en) * | 1994-05-05 | 1996-03-05 | Stepan Company | Methods and compositions for preparing rigid foams with non-chlorofluorocarbon blowing agents |
US5482980A (en) * | 1994-07-14 | 1996-01-09 | Pmc, Inc. | Methods for preparing flexible, open-celled, polyester and polyether urethane foams and foams prepared thereby |
US5710190A (en) * | 1995-06-07 | 1998-01-20 | Iowa State University Research Foundation, Inc. | Soy protein-based thermoplastic composition for foamed articles |
US5756195A (en) * | 1995-06-07 | 1998-05-26 | Acushnet Company | Gel cushion conprising rubber polymer and oil |
US5648483A (en) * | 1995-06-07 | 1997-07-15 | The Procter & Gamble Company | Continuous transesterification method for preparing polyol polyesters |
US5766704A (en) * | 1995-10-27 | 1998-06-16 | Acushnet Company | Conforming shoe construction and gel compositions therefor |
US5767257A (en) * | 1996-07-19 | 1998-06-16 | The Procter & Gamble Company | Methods for producing polyol fatty acid polyesters using atmospheric or superatmospheric pressure |
US6080853A (en) * | 1996-08-08 | 2000-06-27 | The Procter & Gamble Company | Polyol polyester synthesis |
US5908701A (en) * | 1996-12-10 | 1999-06-01 | The Dow Chemical Company | Preparation of filled reactive polyurethane carpet backing formulations using an in-line continuous mixing process |
US5922779A (en) * | 1997-10-10 | 1999-07-13 | Stepan Company | Polyol blends for producing hydrocarbon-blown polyurethane and polyisocyanurate foams |
US6015440A (en) * | 1997-10-31 | 2000-01-18 | Board Of Regents Of The University Of Nebraska | Process for producing biodiesel fuel with reduced viscosity and a cloud point below thirty-two (32) degrees fahrenheit |
US6174501B1 (en) * | 1997-10-31 | 2001-01-16 | The Board Of Regents Of The University Of Nebraska | System and process for producing biodiesel fuel with reduced viscosity and a cloud point below thirty-two (32) degrees fahrenheit |
US6388002B1 (en) * | 1997-12-04 | 2002-05-14 | Rhodia Limited | Dispersed resins for use in coating compositions |
US6180686B1 (en) * | 1998-09-17 | 2001-01-30 | Thomas M. Kurth | Cellular plastic material |
US6864296B2 (en) * | 1998-09-17 | 2005-03-08 | Urethane Soy Systems Company | Plastic material |
US6867239B2 (en) * | 1998-09-17 | 2005-03-15 | Urethane Soy Systems Company | Plastic material |
US6881763B2 (en) * | 1998-09-17 | 2005-04-19 | Urethane Soy Systems Company | Plastic material |
US6420446B1 (en) * | 2000-03-27 | 2002-07-16 | Ck Witco | Polyurethane prepared from sorbitol-branched polyesters |
Cited By (35)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20080132134A1 (en) * | 2001-03-15 | 2008-06-05 | Mashburn Larry E | Carpet backings prepared from vegetable oil-based polyurethanes |
US20070275227A1 (en) * | 2002-03-15 | 2007-11-29 | Mashburn Larry E | Carpet backings prepared from hydroxylated vegetable oil-based polyurethanes |
US20090325444A1 (en) * | 2002-03-15 | 2009-12-31 | Textile Management Associates, Inc. | Carpet backings prepared from vegetable oil-based polyurethanes |
US20100151226A9 (en) * | 2002-03-15 | 2010-06-17 | Mashburn Larry E | Carpet backings prepared from hydroxylated vegetable oil-based polyurethanes |
US8293808B2 (en) | 2003-09-30 | 2012-10-23 | Cargill, Incorporated | Flexible polyurethane foams prepared using modified vegetable oil-based polyols |
US20050070620A1 (en) * | 2003-09-30 | 2005-03-31 | Ron Herrington | Flexible polyurethane foams prepared using modified vegetable oil-based polyols |
US7794817B2 (en) | 2004-01-23 | 2010-09-14 | Century-Board Usa Llc | Filled polymer composite and synthetic building material compositions |
US7993553B2 (en) | 2004-01-23 | 2011-08-09 | Century-Board Usa Llc | Filled polymer composite and synthetic building material compositions |
US7993552B2 (en) | 2004-01-23 | 2011-08-09 | Century-Board Usa Llc | Filled polymer composite and synthetic building material compositions |
US7763341B2 (en) | 2004-01-23 | 2010-07-27 | Century-Board Usa, Llc | Filled polymer composite and synthetic building material compositions |
US10889035B2 (en) | 2004-06-24 | 2021-01-12 | Century-Board Corporation | Method for molding three-dimensional foam products using a continuous forming apparatus |
US10086542B2 (en) | 2004-06-24 | 2018-10-02 | Century-Board Usa, Llc | Method for molding three-dimensional foam products using a continuous forming apparatus |
US7786239B2 (en) | 2004-06-25 | 2010-08-31 | Pittsburg State University | Modified vegetable oil-based polyols |
US20060041157A1 (en) * | 2004-06-25 | 2006-02-23 | Petrovic Zoran S | Modified vegetable oil-based polyols |
US8153746B2 (en) | 2004-06-25 | 2012-04-10 | Cargill, Incorporated | Modified vegetable oil-based polyols |
US7794224B2 (en) | 2004-09-28 | 2010-09-14 | Woodbridge Corporation | Apparatus for the continuous production of plastic composites |
US9045581B2 (en) | 2005-03-03 | 2015-06-02 | Rhino Linings Corporation | Polyols derived from a vegetable oil using an oxidation process |
US20100184878A1 (en) * | 2005-04-25 | 2010-07-22 | Cargill, Incorporated | Polyurethane foams comprising oligomeric polyols |
US7691914B2 (en) | 2005-04-25 | 2010-04-06 | Cargill, Incorporated | Polyurethane foams comprising oligomeric polyols |
US8138234B2 (en) | 2006-03-24 | 2012-03-20 | Century-Board Usa, Llc | Polyurethane composite materials |
US8299136B2 (en) | 2006-03-24 | 2012-10-30 | Century-Board Usa, Llc | Polyurethane composite materials |
US9512288B2 (en) | 2006-03-24 | 2016-12-06 | Boral Ip Holdings Llc | Polyurethane composite materials |
US9139708B2 (en) | 2006-03-24 | 2015-09-22 | Boral Ip Holdings Llc | Extrusion of polyurethane composite materials |
US20090287007A1 (en) * | 2008-05-13 | 2009-11-19 | Cargill, Incorporated | Partially-hydrogenated, fully-epoxidized vegetable oil derivative |
US8901187B1 (en) | 2008-12-19 | 2014-12-02 | Hickory Springs Manufacturing Company | High resilience flexible polyurethane foam using MDI |
US8906975B1 (en) | 2009-02-09 | 2014-12-09 | Hickory Springs Manufacturing Company | Conventional flexible polyurethane foam using MDI |
US8846776B2 (en) | 2009-08-14 | 2014-09-30 | Boral Ip Holdings Llc | Filled polyurethane composites and methods of making same |
US9481759B2 (en) | 2009-08-14 | 2016-11-01 | Boral Ip Holdings Llc | Polyurethanes derived from highly reactive reactants and coal ash |
US9745224B2 (en) | 2011-10-07 | 2017-08-29 | Boral Ip Holdings (Australia) Pty Limited | Inorganic polymer/organic polymer composites and methods of making same |
US10138341B2 (en) | 2014-07-28 | 2018-11-27 | Boral Ip Holdings (Australia) Pty Limited | Use of evaporative coolants to manufacture filled polyurethane composites |
US9752015B2 (en) | 2014-08-05 | 2017-09-05 | Boral Ip Holdings (Australia) Pty Limited | Filled polymeric composites including short length fibers |
US9988512B2 (en) | 2015-01-22 | 2018-06-05 | Boral Ip Holdings (Australia) Pty Limited | Highly filled polyurethane composites |
US10030126B2 (en) | 2015-06-05 | 2018-07-24 | Boral Ip Holdings (Australia) Pty Limited | Filled polyurethane composites with lightweight fillers |
US10472281B2 (en) | 2015-11-12 | 2019-11-12 | Boral Ip Holdings (Australia) Pty Limited | Polyurethane composites with fillers |
WO2024164058A1 (en) * | 2023-02-07 | 2024-08-15 | Isocare Soluções Ambientais S/A | Liquid base product, liquid formulated product, liquid end product, renewable and biodegradable flexible polymer, process for manufacturing a liquid base product, process for manufacturing a liquid formulated product, process for manufacturing a liquid end product, process for manufacturing a renewable and biodegradable flexible polymer |
Also Published As
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US6624244B2 (en) | Plastic material | |
US7084230B2 (en) | Oxylated vegetable-based polyol having increased functionality and urethane materials formed using the polyol | |
JP2002524627A5 (en) | ||
US7537665B2 (en) | Method for producing a bio-based carpet material | |
US8333905B1 (en) | Transesterified polyol having selectable and increased functionality and urethane material products formed using the polyol | |
US8178591B2 (en) | Carbon dioxide blown low density, flexible microcellular polyurethane elastomers | |
US7063877B2 (en) | Bio-based carpet material | |
FI95141C (en) | Liquid polyisocyanate mixtures, process for their preparation and their use in the manufacture of soft polyurethane foams | |
US20060084710A1 (en) | Flexible foams with low bulk densities and compressive strengths | |
KR20010079916A (en) | Process for Making Microcellular Polyurethane Elastomers | |
US5166115A (en) | Polyurethanes | |
FI66410B (en) | FOER FARING FRAMSTAELLNING AV CELL-POLYURETAN-ELASTOMERER | |
US20090223620A1 (en) | Method of producing a bio-based carpet material | |
MXPA06005972A (en) | Carbon dioxide blown low density, flexible microcellular polyurethane elastomers |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: SOUTH DAKOTA SOYBEAN PROCESSORS, LLC, SOUTH DAKOTA Free format text: SECURITY AGREEMENT;ASSIGNOR:URETHANE SOY SYSTEMS CO.;REEL/FRAME:017492/0985 Effective date: 20050826 |
|
STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION |