CN101313001A - Polyurethane foams comprising oligomeric polyols - Google Patents

Abstract

The invention relates to polyurethane foams comprising oligomeric polyols. In embodiments of the invention, the polyurethane foams comprise the reaction product of: (a) a polyisocyanate; and (b) an active-hydrogen containing composition comprising an oligomeric polyol having a hydroxyl number of about 45 to about 65 mg KOH/g, a number average hydroxyl functionality (Fn) of less than about 2.7, and about 40% weight or greater oligomers. The polyurethane foams of the invention may be slabstock foams or molded foams. Also disclosed are low odor polyols and polyurethane compositions.

Description

The urethane foam that comprises oligomeric polyols

Cross-reference to related applications

The application requires following U.S. Provisional Application No.: No. the 60/674879th, the U.S. Provisional Application series number of " the combining the foams of low functionality polyvalent alcohol " by name of submitting on April 25th, 2005; No. the 60/677272nd, the U.S. Provisional Application series number of " the combining the foams of low functionality polyvalent alcohol " by name of submitting on May 2nd, 2005; No. the 60/741123rd, the U.S. Provisional Application series number of " urethane foam that comprises oligomeric modified vegetable oil-based polyols " by name submitted on December 1st, 2005; And No. the 60/786594th, the U.S. Provisional Application series number on March 27th, 2006 " being derived from the oligomeric polyols and the polyurethane composition prepared therefrom of palm base oil " by name of submitting to; These documents all are incorporated by reference into herein in full.

Technical field

The present invention relates to comprise the urethane foam of oligomeric polyols.

Background technology

Flexible polyurethane foam is polyvalent alcohol or polyhydric alcohol composition and the organic multiple isocyanate prepared in reaction in the presence of catalyzer, whipping agent and other optional components by being derived from oil usually.Since the sixties in 20th century, flexible polyurethane foam is used as the parts of damping in automobile, bedclothes (bedding) and the transportation means, carrying and raising comfort level always.

In the preparation of flexible polyurethane foam, some character of used polyvalent alcohol or polyhydric alcohol composition are very important for the flexible foam that preparation has desired characteristic.A kind of important polyvalent alcohol character is the number average hydroxy functionality of polyvalent alcohol.Usually in order to form flexible polyurethane foam, need the number average hydroxy functionality to be about 3 polyvalent alcohol with desired characteristic.Be readily appreciated that when the number average hydroxyl reduced from this required scope, the quality of polyether polyols with reduced unsaturation network can suffer a loss, the characteristic of foams can reduce fast.In case the number-average is equal to or less than 3.0, expection will can not form stable open-cell foam body, if perhaps can form, its physical properties can be very poor, make and can't use.

Can measure the character of urethane foam by the whole bag of tricks.Usually, can measure tensile strength, tear strength, hardness, elongation property, compression property and other character of foams.The relative importance of these character can change along with the purposes of foams expection.

The polyvalent alcohol that is derived from oil is widely used in the production of foams.But people are increasing the interest of using renewable resources to produce foams.This makes people research and develop to be used for the vegetable oil-based polyols that foams are produced.

Other investigator once attempted preparing flexible foam by biopolyol.How WO2004/096883A1 and WO2004/09882A1 have reported by biopolyol formulation preparation TDI-base conventional plate (slabstock) foams, and provide suitable physical properties for the foams that make.The number average hydroxy functionality of the biopolyol of being reported is greater than 2.8.

Summary of the invention

The present invention relates to comprise the urethane foam of oligomeric polyols.In some embodiments, described urethane foam is the plate foams, for example is flexible sheet strand foam body.In other embodiments, described urethane foam is the foams of molding.

In one aspect, the invention provides the urethane foam of the reaction product that comprises following component: (a) polyisocyanates; (b) comprise the composition of reactive hydrogen, it comprises oligomeric polyols, and the hydroxyl value of described oligomeric polyols is about 45-65 milligram KOH/ gram, and number average hydroxy functionality (Fn) comprises the oligopolymer that is equal to or greater than weight % approximately less than 2.7.

In some embodiments, described oligomeric polyols has the open loop characteristic and the oligomeric characteristic of epoxidation natural oil to a certain degree, and the balance of required character is provided for oligomeric polyols.That is to say that open loop and oligomeric degree are controlled, so that the oligomeric polyols of distance of having between required hydroxyl (OH) value, number average hydroxy functionality (Fn), epoxide group oxygen level (EOC), viscosity, molecular weight, the activity hydroxy etc. to be provided.For example, in some embodiments, the open loop of described epoxidised natural oil part is about the oligomeric polyols of 0.01-5.5% so that residual epoxy group oxygen level (EOC) to be provided.In some embodiments, oligomeric degree to polyvalent alcohol is controlled, make described oligomeric polyols comprise to approximate or, for example comprise the oligopolymer of about 55-65 weight % that described oligopolymer comprises dimer, tripolymer, the tetramer and high-grade oligopolymer more greater than the oligopolymer of 40 weight %.For example, described oligomeric polyols can comprise the dimer of about 8-12 weight %, the tripolymer of about 5-10 weight %, and approximate or greater than the tetramer of 35 weight % and high-grade oligopolymer more.In some embodiments, the hydroxyl value of described oligomeric polyols is about 45-65 milligram KOH/ gram.

In some embodiments, use oligomeric polyols to replace in the polyurethane foam body preparation at least a portion in one or more polyvalent alcohols that are derived from oil.For example, in flexible plate urethane foam preparation, described oligomeric polyols can replace at least a portion to be derived from the polyvalent alcohol of oil, and for example molecular weight is about 3000 gram/moles, and hydroxyl value is about the trivalent alcohol that is derived from oil of 56 milligrams of KOH/ grams.Therefore, in some embodiments, the described composition that comprises reactive hydrogen comprises oligomeric polyols and is derived from the polyvalent alcohol of oil.Usually the described composition that comprises reactive hydrogen comprises the oligomeric polyols of about 10-60 weight % and the trivalent alcohol that is derived from oil of about 40-90 weight %, the polyvalent alcohol that is derived from oil of the oligomeric polyols of perhaps about 15 weight % and about 60-85 weight %.

Preferably, observed when the compound that comprises reactive hydrogen comprises oligomeric polyols and is derived from the polyvalent alcohol of oil, can control the supporting factor (support factor) of gained flexible sheet strand foam body by amount that changes oligomeric polyols and the amount that is derived from the polyvalent alcohol of oil, and not influence the density of foams.Specifically, for the foams of constant density, along with the increase of the amount of oligomeric polyols, the supporting factor also can increase.

In many embodiments, described oligomeric polyols has low number average hydroxy functionality, for example is approximately equal to or less than 2.7.Although the polyvalent alcohol of known low hydroxy functionality can may cause some physical propertiess (for example tensile strength, tear strength etc.) variation of flexible polyurethane foam owing to single tube energy material as chain terminator, the physical properties of urethane foam of the present invention is better than comprising the character of the foams that hang down number average hydroxy functionality polyvalent alcohol.

In some embodiments, the crust density of urethane foam of the present invention is lower than the crust density that comprises based on the urethane foam of the reference preparation of the trivalent alcohol that is derived from oil.In some embodiments, compare with reference preparation, the crust density of described urethane foam has reduced about 0.25 pound/foot ³Or it is more.In some embodiments, compare with reference preparation, the density of described crust has reduced about 0.50 pound/foot 3 or more, perhaps about 0.75 pound/foot ³Or more, perhaps about 1.0 pounds/foot ³Or it is more.

In some embodiments, compare with the urethane foam with the reference preparation that does not contain oligomeric polyols, urethane foam of the present invention has improved feel.Feel can be by for example 5%IFD, surface roughness and average cell size tolerance.In some embodiments, compare with the IFD of reference preparation, described 5%IFD is about 2% or higher.

In some embodiments, compare with the urethane foam with the reference preparation that does not contain oligomeric polyols, urethane foam of the present invention has improved flame retardant resistance.For example, " " (in March, 2000) records, and urethane foam can have improved char length to being used to requirement, test procedure and equipment (Requirements; Test Procedure and Apparatus for Testing the Flame Retardanceof Resilient Filling Materials Used in Upholstered Furniture) with the flame retardant resistance test of the elastic filling material of the addition polymerization of cushion by Technical Bulletin117.

In some embodiments, the compounds content of the generation peculiar smell of described oligomeric polyols is very low, makes the urethane foam with low peculiar smell.Peculiar smell can record by for example measuring the compound (for example compound hexanal, aldehyde C-9 and capraldehyde) that produces peculiar smell.Therefore, in one aspect of the method, the invention provides the oligomeric polyols of low peculiar smell and by its urethane foam that makes.In some embodiments, described oligomeric polyols or urethane foam comprise the hexanal that is approximately equal to or less than 30ppm.In some embodiments, described oligomeric polyols or urethane foam comprise the aldehyde C-9 that is approximately equal to or less than 30ppm.In some embodiments, described oligomeric polyols or urethane foam comprise the capraldehyde that is approximately equal to or less than 20ppm.In some embodiments, the total amount of hexanal, aldehyde C-9 and capraldehyde is approximately equal to or less than 80ppm in described oligomeric polyols or the urethane foam.

Other advantage of urethane foam of the present invention described herein comprises for example improved water-repellancy, colour fastness and IFD gradient.

In this article, " polyvalent alcohol " represents on average to comprise in each molecule the molecule that surpasses 1.0 hydroxyls.It can comprise other functional group.

In this article, " oligomeric polyols " expression forms oligopolymer by epoxidised natural oil (for example plant based oil or animal tallow) open loop in some way wholly or in part, thus the polyvalent alcohol that the non-natural of preparation generates.

In this article, " oligopolymer " expression is by mutual chemically combined two or more triglyceride level bases of epoxy addition reaction.Oligopolymer comprises dimer, tripolymer, the tetramer and high-grade oligopolymer more.

In this article, two triglyceride level base monomers of mutual chemical bonding are reacted in " dimer " expression by epoxy addition.

In this article, three triglyceride level base monomers of mutual chemical bonding are reacted in " tripolymer " expression by epoxy addition.

In this article, four triglyceride level base monomers of mutual chemical bonding are reacted in " tetramer " expression by epoxy addition.

In this article, the urethane foam that " plate " expression prepares by following process: reactant is mixed, it is assigned on the carrier, they freely swell (rise) and solidify on carrier, form the successive block material or the block (bun) of the urethane foam of the rectangular cross section that has nominal usually.Comprise flexible plate urethane foam in the plate urethane foam.

In this article, " molding " represents the urethane foam of preparation in the following manner: reactant is mixed, it is assigned in the mould, they react in mould, fill this mould, present the shape of mould cavity.

In this article, " composition that comprises reactive hydrogen " represents a kind of composition, and said composition comprises some reactants, these reactants have can with the group that comprises hydrogen atom of isocyanic ester radical reaction.Example comprises alcohol (for example polyvalent alcohol) and amine (for example polyamines).

In this article, the polyvalent alcohol produced by petroleum of the expression that " is derived from the polyvalent alcohol of oil ".

In this article, " reference preparation " represents a kind of polyurethane formulation, and wherein oligomeric polyols replaces with the trivalent alcohol that is derived from oil (for example trivalent alcohol that is derived from oil of 3000 gram/moles) of equivalent.

Embodiment

The present invention relates to comprise the urethane foam (for example flexible plate urethane foam) of oligomeric polyols.

The preparation of oligomeric polyols

The oligomeric polyols that can be used for urethane foam of the present invention can be by the open loop preparation of epoxidation natural oil.In many embodiments, open loop is to be undertaken by the reaction mixture that use comprises following component: (1) epoxidised natural oil, (2) open loop acid catalyst, and (3) ring opening agent (ring-opener).These materials will be described in more detail below.Also can use the vegetable oil-based polyols of the modification of WO 2006/012344A1 (Pai Zhuoweiqi (Petrovic) etc.) report in some embodiments of urethane foam of the present invention.

Epoxidised natural oil

First component is epoxidised natural oil.Epoxidised natural oil comprises for example epoxidised plant based oil (for example epoxidised vegetables oil) and epoxidised animal tallow.Described epoxidised natural oil is epoxidation partially or completely.The epoxidised natural oil of part can comprise the two keys that contain in the oil original bulk at least about 10%, at least about 20%, at least about 25%, at least about 30%, at least about 35%, at least about 40% or more.The natural oil of described partial oxidation can comprise original bulk the highest about 90% of the two keys that contain in the described oil, and is the highest about 80%, the highest about 75%, the highest about 70%, the highest about 65%, the highest about 60%, or still less.Complete epoxidised natural oil can comprise the highest about 10% of two key initial content of containing in the oil, and is the highest about 5%, the highest about 2%, the highest about 1%, or still less.

The example of natural oil comprises plant based oil (for example vegetables oil) and animal tallow.The example of plant based oil comprises soybean oil, Thistle oil, Toenol 1140, Semen Maydis oil, Trisun Oil R 80, sweet oil, Tower rape oil, sesame oil, Oleum Gossypii semen, palm base oil, rapeseed oil, tung oil, peanut oil and their combination.Also can use animal tallow, for example fish oil, lard and butter.Plant based oil can be crude vegetal or gene plant oil, high oleic safflower oil for example, high oleic acid soybean oil, high oleic acid peanut oil, high oleic sunflower oil, and high oleic acid rapeseed oil (Crambe oil).The double key number amount that each molecule comprises in the natural oil can be quantitative with the iodine number (IV) of oil.For example, each molecule vegetables oil of comprising two keys is about 28 corresponding to iodine number.Soybean oil each molecule usually comprises about 4.6 two keys, and its iodine number is about 127-140.Canola Oil each molecule usually comprises 4.1 two keys, and iodine number is about 115.Usually the iodine number of vegetables oil is about 40-240.In some embodiments, use iodine number approximately greater than 80, approximately greater than 100 or approximately greater than 110 vegetables oil.In some embodiments, use iodine number approximately less than 240, approximately less than 200 or approximately less than 180 vegetables oil.

Available natural oil comprises triglyceride.Described lipid acid can be saturated or unsaturated, and chain length is about C ₁₂-C ₂₄Unsaturated fatty acids comprises single unsaturated and polyunsaturated fatty acid.Conventional unsaturated fatty acids comprises lauric acid (dodecylic acid), tetradecanoic acid (tetradecanoic acid), palmitinic acid (hexadecanoic acid), stearic acid (octadecanoic acid), eicosanoic acid (arachic acid), and lignoceric acid (Lignoceric acid).Conventional monounsaturated fatty acids comprises Zoomeric acid (C16 unsaturated acid) and oleic acid (C18 unsaturated acid).Conventional polyunsaturated fatty acid comprises linolic acid (C18 two unsaturated acid), linolenic acid (C18 three unsaturated acid), and arachidonic acid (C20 four unsaturated acid).Described triglyceride oil is made up of the ester of the lipid acid that is provided with at random on three sites on the trifunctional glycerol molecule.In the different vegetables oil, these lipid acid have different ratios.The ratio of lipid acid also will be according to following factors vary in the specified plant oil, plant growth ground for example, crop ripening degree, the weather in the season of growth etc.Provide concrete or unique composition owing to be difficult to any specific plant, it forms common form report with the statistical average result.For example, soybean oil comprises ratio and is about 15: 24: 50: the mixture of 11 stearic acid, oleic acid, linoleic acid plus linolenic acid.Be equivalent to molecular-weight average and be about 800-860 gram/mole, average double key number amount is about 4.4-4.7/triglyceride level, and iodine number is about 120-140.

In an exemplary embodiment, epoxidised natural oil is complete epoxidised soybean oil.Although without wanting to be limited by theory, it is believed that, use the saturated epoxidized vegetable oil that comprises remaining epoxide group can obtain having the oligomeric polyols of good oxidation stability.Should also be understood that with respect to the product that uses the preparation of inclusion epoxidized vegetable oil, use unsaturated epoxidized vegetable oil will obtain having more low viscous oligomeric polyols.

In another illustrative embodiments, described natural oil is the palm base oil.In this article, " palm base oil " expression is by the mesocarp of the fruit of oil palm tree and/or oil or the oil ingredient that nuclear makes.The palm base oil comprises plam oil, palm olein, palm stearines, palm-kernel oil, palm-kernel olein, palm nuclear tristearin, and their mixture.The palm base oil can be crude oil, refining oil, degummed oil, bleached oil, remove tar, distillate oil or crystal oil.In many embodiments, described palm base oil is refining, bleaching and de-odorised (i.e. " RBD " oil).

Plam oil represents to be derived from the oil of oil palm fruit mesocarp.Plam oil is at room temperature normally semi-solid, comprises about 50% saturated fatty acid and about 50% unsaturated fatty acids.Plam oil mainly comprises triglyceride usually, but also can comprise a spot of monoglyceride and triglyceride.The chain length of lipid acid is about C12-C20 usually.Representational saturated fatty acid comprises for example C12:0, C14:0, C16:0, C18:0 and C20:0 saturated fatty acid.Representational unsaturated fatty acids comprises for example C16:1, C18:1, C18:2 and C18:3 unsaturated fatty acids.The representational scope of palmitinic acid is listed in Table A.

Palm olein represents that plam oil after the crystallization, carries out the liquid fraction that fractionation makes to it under the temperature of control.With respect to plam oil, the content of unsaturated fatty acids is higher in the palm olein, for example comprises more C18:1 and C18:2 lipid acid, and has higher iodine number.In some embodiments, described palm olein multiple fractionation makes and has than high unsaturated fatty acid (C18:1, C18:2) content and palm olein with higher iodine number.In some cases, the palm olein of multiple fractionation can be described as super palm olein.The representational compositing range of palm olein is listed in Table A.The representative example of commercially available plam oil and palm olein comprises the commercially available product with following trade(brand)name: available from IOI branch of Luo De clo Crane company (Loders Croklaan IOIGroup) " loose this pass this 25 (SANS TRANS 25) ", " loose this pass this-39 (SANS TRANS-39) " and " tongued bell Kai Kesi NT100 (DURKEX NT100) "; And " the super olein of purified palm olein IV 62-(FULLY REFINED PALM OLEIN IV 62-SUPEROLEIN) fully " (available from card gill (Cargill) company limited).

Palm stearines is represented plam oil under the temperature of control after the crystallization, the solid-state cut that makes by fractionation.With respect to plam oil, palm stearines comprises more saturated fatty acid, has high melt point.The representational composition of palm stearines is listed in Table A.

Table A

Lipid acid	Plam oil (weight %)	Palm oil (weight %)	Palm stearines (weight %)
				C12:0	＜1％	＜1％	＜1％
C14:0	＜2％	＜2％	＜2％
				C16:0	40-50％	35-45％	45-75％
C16:1	＜1％	＜1％	＜1％
				C18:0	3-6％	3-5％	4-6％
C18:1	35-45％	40-47％	10-40％
				C18:2	8-12％	10-15％	2-10％
C18:3	＜1％	＜1％	＜1％
				C20:0	＜1％	＜1％	＜1％
Iodine number (IV)	50-65	55-62	20-50

Can prepare part epoxidation or complete epoxidised natural oil by the method that may further comprise the steps: a part or all two keys are converted under the condition of epoxide group in can be with oil, make natural oil and mistake acid-respons.

The example of peracid comprises peroxyformic acid, Peracetic Acid, trifluoro Peracetic Acid, benzyloxy peroxyformic acid, 3,5-dinitrobenzene benzoyl hydroperoxide, metachloroperbenzoic acid, and their combination.In some embodiments, use peroxyformic acid or Peracetic Acid.These peracid can directly add in the reaction mixture, perhaps can form in position with corresponding acid (for example formic acid, phenylformic acid, lipid acid (for example oleic acid) or acetate) reaction by hydroperoxide.The example of spendable hydroperoxide comprises hydrogen peroxide, t-butyl hydroperoxide, hydroperoxidation triphenyl silyl, Cumene Hydroperoxide 80 base and their combination.In an exemplary embodiment, use hydrogen peroxide.Usually, the consumption that is used for forming the acid of peracid is about the two keys in 0.25-1.0 equimolar acid/mole vegetables oil, is more preferably the two keys in 0.45-0.5 acid/mole vegetables oil.The amount that is generally used for forming the hydroperoxide of peracid is about the two keys in 0.5-1.5 moles of hydrogen superoxide/mole vegetables oil, is more preferably the two keys in 0.8-1.2 moles of hydrogen superoxide/mole vegetables oil.

Usually also comprise other acid constituents in the reaction mixture.These other acid comprise sulfuric acid, toluenesulphonic acids, fluoroboric acid, Lewis acid, acid clay or acidic ion exchange resin.

Can randomly in reaction, add solvent.The available solvent comprises unreactiveness solvent, for example aprotic solvent.These solvents do not contain nucleophile, can not with acid-respons.The hydrophobic solvent of special aromatic hydrocarbons and aliphatic hydrocrbon and so on.The representative example of suitable solvent comprises benzene,toluene,xylene, hexane, isohexane, pentane, heptane and chlorinated solvent (for example tetracol phenixin).In an exemplary embodiment, use toluene as solvent.Also can use solvent to come slowed down reaction speed, perhaps reduce the quantity of side reaction.Generally, the solvent viscosity that also can be used as the composition that makes reduces agent.

After the epoxidation reaction, can neutralize to reaction product.Can add neutralizing agent with any remaining acidic components in the neutralization reaction product.Suitable neutralizing agent comprises weak base, alkali metal bicarbonate salt or ion exchange resin.The example of spendable neutralizing agent comprises ammonia, lime carbonate, sodium bicarbonate, magnesiumcarbonate, ammonia and resin, and the aqueous solution of neutralizing agent.Common described neutralizing agent can be an anionite-exchange resin.The example of suitable weak-base ion-exchange resin is the product of commodity " Le Wote MP-64 (LEWATIT MP-64) " (available from Baeyer (Bayer)) by name.If use solid-state neutralizing agent (for example ion exchange resin), then can solid-state neutralizing agent be removed from epoxidised vegetables oil by filtering.Perhaps, by described reaction mixture is neutralized to this mixture by the neutralization bed that comprises resin or other material.Perhaps, can wash repeatedly, from product, to separate and to remove acidic components described reaction product.In addition, when reaction product is carried out neutral, can be with one or more method applied in any combination.For example, can wash,, filter then with the resin material neutralization to product.

After epoxidation reaction, can from reaction product (being complete epoxidised vegetables oil), remove excessive solvent.Excessive solvent comprises the product that reaction obtains, and perhaps adds the solvent in the reaction.Described excessive solvent can be removed by separation, vacuum method or other method.Preferably, the removal of described excessive solvent can be finished by applying vacuum.

The complete epoxidised soybean oil of available comprises the commercially available prod with following trade(brand)name: Ai Puke Sol 7-4 (EPOXOL 7-4) (available from american chemical system house (American Chemical Systems)) and Fu Laike Sol ESO (FLEXOL ESO) (available from Dao Er chemical company limited (Dow ChemicalCo.)).

The open loop acid catalyst

In many embodiments, ring-opening reaction is carried out in the presence of the open loop acid catalyst.The representative example of open loop acid catalyst comprises Lewis acid or Bronsted acid.The example of Bronsted acid comprises hydrofluoboric acid (hydrofluoroboric acid) (HBF ₄), trifluoromethanesulfonic acid, sulfuric acid, hydrochloric acid, phosphoric acid, phosphorous acid, Hypophosporous Acid, 50, boric acid, sulfonic acid (for example tosic acid, methylsulfonic acid and trifluoromethanesulfonic acid), and carboxylic acid (for example formic acid and acetate).Lewis acidic example comprises phosphorus trichloride and halogenation boron (for example boron trifluoride).Also can use the ion exchange resin of proton form.In an exemplary embodiment, ring opening catalyst is fluorine boron hydracid (HBF ₄).Gross weight in reaction mixture is a benchmark, and the content of described ring opening catalyst is about 0.01-0.3 weight % usually, is more preferably 0.05-0.15%.

Ring opening agent

The 3rd component of described reaction mixture is a ring opening agent.Can use various ring opening agents, it comprises alcohol, water (water that comprises residual volume), and other compound that comprises one or more nucleophilic groups.Can use the combination of ring opening agent.In some embodiments, described ring opening agent is a monohydroxy-alcohol.Representational example comprises methyl alcohol, ethanol, propyl alcohol (comprising n-propyl alcohol and Virahol), and the monoalky lether (for example methylcyclohexane, ethylene glycol butyl ether etc.) of butanols (comprising propyl carbinol and isopropylcarbinol) and ethylene glycol.In an exemplary embodiment, described alcohol is methyl alcohol.In some embodiments, described ring opening agent is a polyvalent alcohol.For the application in flexible foam, usually preferred each molecule that uses comprises two or the polyvalent alcohol of hydroxyl still less.The polyvalent alcohol ring opening agent that can be used to prepare the oligomeric polyols that is used for flexible foam comprises for example ethylene glycol, propylene glycol, 1, ammediol, butyleneglycol, 1,4-butyleneglycol, 1,5-pentanediol, 1,6-hexylene glycol, polyoxyethylene glycol and polypropylene glycol.Also can use vegetable oil-based polyols.

Ring-opening reaction

When carrying out ring-opening reaction, the ratio of ring opening agent and epoxide is less than stoichiometric ratio, oligomeric with the open loop polyvalent alcohol that promotes to make.In an exemplary embodiment,, complete epoxidised soybean oil (ESBO) and methyl alcohol are reacted prepare oligomeric polyols by in the presence of the ring opening catalyst of for example fluoroboric acid and so on.Usually, the mol ratio of methyl alcohol and complete epoxidised soybean oil is about 0.5-3.0, is more preferably 1.0-2.0.In an exemplary embodiment, the mol ratio of described methyl alcohol and epoxidised soybean oil is about 1.3-1.7.

Usually, in reaction at first, complete epoxidised soybean oil epoxide oxygen level (EOC) is about 6.8-7.4%.Ring-opening reaction preferably stopped before all oxirane ring open loops.For some ring opening catalysts, in the process of ring-opening reaction, activity of such catalysts can reduce in time.Therefore, the speed that can control adds ring opening catalyst in the activated mixture, makes that be reflected near required terminal point EOC place (or) stops.Can use known technology monitoring ring-opening reaction, for example can adopt hydroxyl value titration (ASTM El 899-02), EOC titration (AOCS Cd9-57 method) or monitoring thermopositive reaction liberated heat.

Usually, if use the soybean oil of loopful oxidation, when residual epoxy base oxygen level (EOC) when being about 0.01-6.0%, for example its content is about 0.5-5.5%, is about 1-5.0%, is about 2-4.8%, be about 3-4.6%, or be about 3.5-4.5%, stop ring-opening reaction.When using other epoxidation natural oil, the residual epoxy base oxygen level (EOC) of polyvalent alcohol can be different.For example, for plam oil, remaining EOC is about 0.01-3.5%, for example is about 0.2-3.0%, is about 0.5-2.0%, or is about 0.8-1.5%.In this article, the weight percentage of the oxygen of epoxide in " epoxy oxygen content " or " EOC " the expression molecule.

In the ring-opening reaction process, the epoxide group reaction that comprises on other molecule in some hydroxyls of open loop polyvalent alcohol and the reaction mixture (for example unreacted complete epoxidised soybean oil molecule or comprise the polyvalent alcohol molecule of unreacted epoxy groups group) generates polyvalent alcohol oligomeric (promptly generate dimer, tripolymer, the tetramer and more high-grade oligopolymer).Oligomeric degree has influence to the required character of oligomeric polyols, and these character comprise for example distance between number average hydroxy functionality, viscosity and the activity hydroxy.Described oligomeric polyols comprises about 40 weight % or more oligopolymer (comprising dimer, tripolymer and high-grade oligopolymer more).In some embodiments, described oligomeric polyols comprises the monomer polyvalent alcohol of about 35-45 weight % and the oligopolymer of about 55-65 weight % (for example dimer, tripolymer, the tetramer and more high-grade oligopolymer).For example, in some embodiments, described oligomeric polyols comprises the monomer polyvalent alcohol of about 35-45 weight %, two polyvalent alcohols of about 8-12 weight %, three polyvalent alcohols of about 5-10 weight %, and about 35 weight % or more higher oligomer.

Can be by the control of the stirring extent in for example catalyst concn, reactant stoichiometric ratio and open loop process oligomerization.Oligomerization takes place with higher degree easily, for example carries out under the situation of the ring opening agent (for example methyl alcohol) of catalyzer that uses higher concentration or low concentration.When ring-opening reaction is finished, remove any unreacted methanol by for example vacuum distilling usually.Unreacted methanol is undesirable in the oligomeric polyols, and this is because it is a monofunctional species, may be to polyisocyanate blocked.Remove after any excessive methyl alcohol, usually the polyvalent alcohol that obtains is filtered, for example use 50 microns pocket filter to filter, to remove any solid impurity.

The character of oligomeric polyols

In some embodiments, oligomeric polyols has low number average hydroxy functionality.The number-average represents the mean number of the pendant hydroxyl group (for example primary hydroxyl, secondary hydroxyl or tert-hydroxyl) that comprises on the polyvalent alcohol molecule.In some embodiments, the number average hydroxy functionality (Fn) of oligomeric polyols is approximately equal to or less than 2.7, for example is approximately equal to or less than 2.6, be approximately equal to or less than 2.5, be approximately equal to or less than 2.4, be approximately equal to or less than 2.3, be approximately equal to or less than 2.2, be approximately equal to or less than 2.1, be approximately equal to or less than 2.0, be approximately equal to or less than 1.9, be approximately equal to or less than 1.8, be approximately equal to or less than 1.7, be approximately equal to or less than 1.6, be approximately equal to or less than 1.5, perhaps be approximately equal to or less than 1.4.Common described number average hydroxy functionality is about 1.5-2.4, or is about 1.7-2.2.

In some embodiments, the hydroxyl value of described oligomeric polyols is about 45-65 milligram KOH/ gram, or is about 55-65 milligram KOH/ gram.Hydroxyl value represents to carry out the quantity of reactive activity hydroxyl.It is expressed as with a gram sample in the milligram number of the suitable potassium hydroxide of hydroxy radical content.Wish that hydroxyl value is about 45-65 milligram KOH/ gram, because this helps the application of oligomeric polyols oligomeric polyols in flexible plate polyurethane formulation, described oligomeric polyols has replaced being generally used at least a portion of the trivalent alcohol that is derived from oil of these preparations.For example, in some embodiments, described oligomeric polyols has replaced molecular weight to be about at least a portion that 3000 gram/moles, hydroxyl value are about 56 the trivalent alcohol that is derived from oil.

In some embodiments, described oligomeric polyols has low acid number.During acid number equals and the milligram number (promptly milligram KOH/ restrains) of the sour required potassium hydroxide (KOH) in the 1 gram polyvalent alcohol sample.People do not wish high acid number, and this is because acid possibility neutralizing amine catalyzer causes expansion rate to slow down.In some embodiments, the acid number of described oligomeric polyols is approximately less than 5 (milligram KOH/ grams), for example approximately less than 4 (milligram KOH/ restrains), approximately less than 3 (milligram KOH/ grams), approximately less than 2 (milligram KOH/ grams), or approximately less than 1 (milligram KOH/ restrains).In exemplary embodiment, acid number for example approximately less than 0.5 (milligram KOH/ gram), or is about 0.2-0.5 (milligram KOH/ gram) approximately less than 1 (milligram KOH/ gram).

In some embodiments, the number-average molecular weight of oligomeric polyols (being Mn) approximates or greater than 1000 gram/moles, for example approximate or greater than 1100 gram/moles, approximate or greater than 1200 gram/moles, approximate or greater than 1300 gram/moles, approximate or greater than 1400 gram/moles, or approximate or greater than 1500 gram/moles.In some embodiments, Mn is approximately less than 5000 gram/moles, for example approximately less than 4000 gram/moles, and approximately less than 3000 gram/moles, or approximately less than 2000 gram/moles.In some embodiments, Mn is about 1000-5000 gram/mole, for example is about 1200-3000 gram/mole, is about 1300-2000 gram/mole, is about 1700-1900 gram/mole, or about 1500-1800 gram/mole.Can be by following commercial measurement number-average molecular weight: for example scattering of light, water vapour penetration platen press, terminal group titration and colligative property method.

In some embodiments, the weight-average molecular weight of oligomeric polyols (being Mw) approximates or greater than 5000 gram/moles, for example approximates or greater than 6000 gram/moles, approximates or greater than 7000 gram/moles, perhaps approximates or greater than 8000 gram/moles.In some embodiments, Mw is approximately less than 50,000 gram/moles, for example approximately less than 40,000 gram/moles, approximately less than 30,000 gram/moles, perhaps approximately less than 20,000 gram/moles.In some embodiments, Mw is about 5000-50, and 000 gram/mole for example is about 5000-20, and 000 gram/mole perhaps is about 6000-15,000 gram/mole.Weight-average molecular weight can be measured by the following method, for example: light scattering method, small-angle neutron scattering (SANS), X-ray scattering, and sedimentation velocity method.

Usually the polymolecularity (Mw/Mn) of oligomeric polyols is about 3-15, for example is about 4-12, or is about 5-10.

In some embodiments, oligomeric polyols is about 0.5-10 handkerchief second 25 ℃ viscosity.When using soybean oil, the viscosity of oligomeric polyols is about 2-8 handkerchief second usually, or is about 3-7 handkerchief second.When using the palm base oil, the viscosity of oligomeric polyols was approximately equal to or less than for 4 handkerchief seconds usually, for example was approximately equal to or less than for 3 handkerchief seconds, was approximately equal to or less than for 2 handkerchief seconds, was approximately equal to or less than for 1 handkerchief second, perhaps was approximately equal to or less than for 0.7 handkerchief second.In some embodiments, be about 0.5-2 handkerchief second by the viscosity of the oligomeric polyols of palm base oil preparation.

In some embodiments, even described oligomeric polyols comprises residual double bonds, its content is also minimum.When described oligomeric polyols is particularly like this by complete epoxidised soybean oil preparation the time.A kind of tolerance of the content of two keys is its iodine number (IV) in the material.The iodine number of compound is the amount with the iodine of sample material reaction, with the iodine (I of every gram material consumption ₂) the centigram numerical table show (centigram I ₂/ gram).In some embodiments, the iodine number of described oligomeric polyols is approximately less than 50, for example approximately less than 40, and approximately less than 30, approximately less than 20, approximately less than 10, or approximately less than 5.

Urethane foam

The invention provides the polyurethane composition that can be used to prepare urethane foam (for example plate urethane foam or molded polyurethane foam body).In some embodiments, described urethane foam comprises the reaction product of following material:

(a) polyisocyanates;

(b) comprise the composition of reactive hydrogen, said composition comprises oligomeric polyols, and the hydroxyl value of this polyvalent alcohol is about 45-65 milligram KOH/ gram, and the number average hydroxy functionality comprises the oligopolymer that is equal to or greater than 40 weight % approximately less than 2.7.

The isocyanate group generation chemical reaction of the hydroxyl of described oligomeric polyols and described polyisocyanates forms carbamic acid ester chain in the urethane foam that makes.Make that like this oligomeric polyols is incorporated in the polyether polyols with reduced unsaturation by chemical bonded refractory.

The content of oligomeric polyols can be selected according to required foam performance in the described composition that comprises reactive hydrogen.For example, in some embodiments, the composition that comprises reactive hydrogen can comprise the oligomeric polyols of about 10-90 weight %, the oligomeric polyols of for example about 10-60 weight %, the oligomeric polyols of perhaps about 15-40 weight %.

In some embodiments, the described composition that comprises reactive hydrogen comprises oligomeric polyols and the polyvalent alcohol that is derived from oil.For example in some embodiments, the described composition that comprises reactive hydrogen comprises the oligomeric polyols of about 10-90 weight % and the polyvalent alcohol that is derived from oil of about 10-90 weight %.In some embodiments, the described composition that comprises reactive hydrogen comprises the oligomeric polyols of about 10-60% weight and the polyvalent alcohol that is derived from oil of about 40-90 weight %.In other embodiment, the described composition that comprises reactive hydrogen comprises the oligomeric polyols of about 15-40 weight % and the polyvalent alcohol that is derived from oil of about 60-85 weight %.

In some embodiments, the described polyvalent alcohol that is derived from oil is a trivalent alcohol.In this article, term " trivalent alcohol " represents that each molecule on average comprises the polyvalent alcohol of about 2.7-3.1 hydroxyl.In an embodiment, the weight-average molecular weight of described trivalent alcohol (Mw) is about 3000-3500 gram/mole.The representative example of the commercially available trivalent alcohol that is derived from oil comprises the product with following trade(brand)name: peace jade-like stone that F3040 (ARCOLF3040), peace jade-like stone that F3022 (ARCOL F3022) and peace jade-like stone that 3222 (ARCOL 3222) (available from Baeyers), general Lu Lakeer 1385 (PLURACOL 1385) and general Lu Lakeer 1388 (PLURACOL1388) (available from BASF), Walla Nore 3322 (VORANOL 3322), Walla Nore 3010 (VORANOL 3010), Walla Nore 3136 (VORANOL 3136) and Walla Nore 3512A (VORANOL 3512A) (available from Dao Er (Dow)).

Polyisocyanates

The representational example of useful polyisocyanates comprises that average per molecule has those polyisocyanates at least about 2.0 isocyanate group.Can use aliphatic series and aromatic polyisocyanate.The example of suitable aliphatic polyisocyanate comprises: 1,4-fourth vulcabond, hexamethylene diisocyanate, 1,12-dodecane vulcabond, tetramethylene-1,3-vulcabond, hexanaphthene-1,3-and 1,4-vulcabond, 1,5-two isocyanato-s-3,3,5-trimethyl-cyclohexane, hydrogenation 2,4-and/or 4,4 '-diphenylmethanediisocyanate (H ₁₂MDI), isophorone diisocyanate etc.The example of suitable aromatic polyisocyanate comprises: 2,4-tolylene diisocyanate (TDI), 2,6-tolylene diisocyanate (TDI) and their mixture, 1,3-and 1,4-phenylene diisocyanate, 4,4 '-diphenylmethanediisocyanate (comprises and a small amount of 2,4 '-mixture of isomers) (MDI), 1,5-naphthalene diisocyanate, triphenyl methane-4,4 ', 4 " triisocyanate, polyphenyl polymethylene polyisocyanates (PMDI) etc.The derivative of above-mentioned polyisocyanates and prepolymer are as amido-containing acid ester, carbodiimide, allophanate, isocyanuric acid ester, acidylate urea, biuret, ester with similarly those derivatives and the prepolymer of group also can use.

The amount of polyisocyanates is preferably can be enough to provide about 60-120, better about 70-110 isocyanate index, the high water content prescription (that is, and in the prescription per 100 weight parts other contain active hydrogen substance and contain water at least about 5 weight parts) situation in, isocyanate index is about 70-90.In this article, " isocyanate index " is the stoichiometric ratio equilibrated that is used for measuring between the total yield number of the equivalents of used isocyanic ester and water, polyvalent alcohol and other reactants.Index 100 is meant isocyanic ester that provides enough and the reaction compound that all contain reactive hydrogen atom.

Catalysts for polyurethanes

The example of useful catalysts for polyurethanes comprises: tertiary amine compound and organometallic compound.The object lesson of useful tertiary amine compound comprises: triethylenediamine, N-methylmorpholine, N-ethylmorpholine, diethylethanolamine, N-cocoyl morpholine, 1-methyl-4-dimethyl aminoethyl piperazine, 3-methoxyl group-N-dimethyl propylamine, N, N-diethyl-3-diethyl amino propylamine, dimethyl benzylamine, two (2-dimethyl aminoethyl) ether etc.The tertiary amine catalyst consumption is preferably the about 0.01-5 weight part of per 100 weight part hydrogenous materials use in the preparation, better about 0.05-2 weight part.

The object lesson of useful organo-metallic catalyst comprises metal, as the organic salt of tin, bismuth, iron, zinc etc., and preferred organotin catalysts.Suitable organotin catalysts comprises dimethyl two lauric acid tin, dibutyl tin dilaurate, stannous octoate etc.Other appropriate catalyst is disclosed in for example United States Patent (USP) 2,846,408, and this patent reference is incorporated into this paper.The consumption of organo-metallic catalyst is preferably, and per 100 weight parts contain the organo-metallic catalyst that active hydrogen substance uses about 0.001-1.0 weight part in the preparation.Can also use mixture of catalysts.

Whipping agent

Whipping agent produces gas under the reaction conditions of active hydrogen compounds and polyisocyanates.Suitable whipping agent comprises water, liquid carbon dioxide, acetone and pentane, preferably water.

The consumption of whipping agent wants can be enough to provide the density foam of requirement.For example, when making water as unique whipping agent, its consumption is, in the preparation per 100 weight parts other contain active hydrogen substance and use about 0.5-10 weight part, better about 1-8 weight part, better about 2-6 weight part.

Other additive

Other additive that can comprise in the prescription comprises: tensio-active agent, catalyzer, cell size control agent, cavity expansion foam agent, tinting material, antioxidant, sanitas, electrostatic dissipation agent, softening agent, linking agent, fire retardant etc.

The example of useful tensio-active agent comprises an alkali metal salt of silicone surfactant and lipid acid.Preferred silicone surfactant, as the segmented copolymer of epoxy alkane and dimethyl siloxane, the silicone surfactant of preferred " ground fog " level especially.

In some situation, when the preparation foams, can comprise the electrostatic dissipation agent in the preparation, or the foams of making be handled with the electrostatic dissipation agent.Useful example comprises: non-volatile ionogenic metal-salt, optional combine with the toughener compound, and as United States Patent (USP) 4,806,571,4,618,630 and 4,617, described in 325.Attractively especially be tetraphenyl boron sodium or have the consumption of sodium salt of the perfluorination aliphatic carboxylic acid of 8 carbon atoms to be about 3 weight % at most at most approximately.

The production of urethane foam

Can use the known technology that is used for preparing conventional plate (being freely to swell) foams and molded foam to produce urethane foam of the present invention.In plate technology, the polyurethane reaction thing is mixed, be poured on the conveyer, reaction mixture is resisted himself on this conveyer weight swells, and solidify to form the plate with nominal square-section.The plate block of gained can be cut into required shape, to adapt to final application.In the moulded foam body technology, reactant is mixed, be distributed in the mould, they react in mould, fill mould, present the shape of cavity body of mould.After the foams of molding solidify, open mould, take out the polyurethane product of molding.

The plate urethane foam can use conventional plate foaming machine manufacturing, for example use commercially available box foaming machine, high pressure or low pressure continuous foam maker, crown material method, rectangular block material method (De Lake (Draka) for example, send column foot (Petzetakis) now, Heng Nike (Hennecke), pula Niblock (Planiblock), Ai Kennuofomu (EconoFoam) and Mike Si Fomu (Maxfoam) technology) or vertical foaming process.In some embodiments, described plate foams prepare under reduced pressure.For example, in variable pressure foaming (VPF) method, the whole conveyer part of foaming machine all is positioned at the gastight shell.By this technology can control foam density, produce the foams of the grade that otherwise may be difficult to produce." flexible polyurethane foam (Flexible Polyurethane Foams) " (second edition that the details of these plate foamings can be write referring to for example Herrington and Hock, 1997, Dao Er chemical company (Dow ChemicalCompany)), chapter 5.

In some cases, need afterwards, carry out after fixing initial be shaped (, also will carry out the demoulding), to produce best physical properties for molded foam to foams.After fixing can carry out under envrionment conditions for example about 12 hours to 7 days; Perhaps carry out for example about 10 minutes at elevated temperatures to a few hours.

Described foams can be used for various uses.For example, foams can be joined the seat part used on motor vehicle or the furniture (as, seat cushion, backrest or handrail etc.) in.

The character of urethane foam

Plate urethane foam of the present invention has many required character, these character comprise for example adjustable supporting factor, the skin thickness that reduces, improved colour fastness, low peculiar smell, improved feel, the density distribution that reduces, the IFD that reduces distributes, improved flame retardant resistance, and the improved comfort level that records by pressure.

-anti-opening property, tearing property and extensibility

In the industry of plate foams, known in the plate foams, the polyvalent alcohol that use has low number average hydroxy functionality or comprises the monofunctional species of significant quantity can cause the chain termination of polyether polyols with reduced unsaturation, and this can reduce the plate foams that make anti-ly opens a property, tear character, elongation property and weather resistance.It is shocking that plate urethane foam of the present invention only causes moderate character to descend owing to comprising low number average hydroxy functionality material.

In some embodiments, urethane foam of the present invention comprises the composition that contains hydrogen, and said composition comprises the oligomeric polyols of 10PPH at least, when utilizing ASTM3574 (will change minimum three days set time into) to be about 1.5 pounds/foot in density ³, 25%IFD is about 23 Ns/323 centimetres ²The plate foams on when measuring, the tensile strength of described urethane foam reduces the percentage ratio degree that reduces of reference preparation (promptly with respect to) and is equal to or less than the numerical value that is calculated by following formula;

The % tensile strength reduces=m * (PPH of oligomeric polyols)

In some embodiments, m=0.89.In other embodiment, m=1.0 or 1.1.

In some embodiments, urethane foam of the present invention comprises the composition that contains reactive hydrogen, and said composition comprises the oligomeric polyols of at least 10 PPH, when utilizing ASTM 3574 (changing minimum 3 days set time into) to be about 1.5 pounds/foot in density ³, 25%IFD is about 23 Ns/323 centimetres ²The plate foams on when measuring tear strength, the tear strength of this urethane foam reduces the percentage ratio degree that reduces of reference preparation (promptly with respect to) and is equal to or less than the numerical value that is calculated by following formula:

The % tear strength reduces=and 1.40 * (PPH of oligomeric polyols).

In some embodiments, urethane foam of the present invention comprises the composition that contains reactive hydrogen, and said composition comprises the oligomeric polyols of at least 10 PPH, when utilizing ASTM 3574 (changing minimum 3 days set time into) to be about 1.5 pounds/foot in density ³, 25%IFD is about 23 Ns/323 centimetres ²The plate foams on when measuring elongation, the elongation of this urethane foam reduces the percentage ratio degree that reduces of reference preparation (promptly with respect to) and is equal to or less than the numerical value that is calculated by following formula:

% elongation reduces=and 1.36 * (PPH of oligomeric polyols).

In some embodiments, described urethane foam comprises the composition that contains reactive hydrogen, and said composition comprises the oligomeric polyols of at least 10 PPH, and the number average hydroxy functionality of this oligomeric polyols is approximately less than 2.7, and density is about 1.5 pounds/foot ³The tensile strength of urethane foam be at least about 85kPa.

-supporting the factor

In some embodiments, compare with the reference preparation that does not contain oligomeric polyols, plate urethane foam of the present invention shows the supporting factor of increase.In this article, term " supporting the factor " is meant the ratio of 65%IFD and 25%IFD of the plate foam sample of following formulate.The supporting factor sometimes is also referred to as " press and fall into the factor " or " modulus ", is used for illustrating the shock-absorption quality of plate foams.Along with the increase of the supporting factor, foams have higher resistance to reducing as far as possible.

The supporting factor=(in the soundness of 65%IFD)/(in the soundness of 25%IFD)

In this formula, " IFD " expression " recessed pressure reactive force deflection value (indentation force deflectionvalue) ", it is the tolerance of the load-bearing quality of foams.IFD is typically expressed as (ox/323 centimetre of the newton number on per 323 square centimeters under the specific flexure percentage of foams ²).Reactive force is big more, and the plate foams are firm more.In order to obtain IFD, 323 square centimeters circular slabs are pressed into the end face of foam sample, stop at specific deflection value, on balance, read reactive force.For example, 25%IFD=150 means that it is 150 Ns/323 centimetres of 75 millimeters needs that foam sheets with 100 mm thick is compressed to thickness ²Reactive force.

In some embodiments, the supporting factor of plate urethane foam of the present invention can be controlled by the amount that changes the oligomeric polyols that comprises in the plate foams.Preferably, the supporting factor of described plate foams can be independent of the grade of plate foams and control.By increasing the amount of oligomeric polyols, the supporting factor also can increase.This allows foam manufacturers to control the supporting factor by oligomeric polyols in the adjusting preparation with the amount that is derived from the polyvalent alcohol of oil.In embodiments of the present invention, the supporting factor can be equal to or greater than 1.5, for example is equal to or greater than 1.6, is equal to or greater than 1.7, be equal to or greater than 1.8, be equal to or greater than 1.9, be equal to or greater than 2.0, be equal to or greater than 2.1, be equal to or greater than 2.2, be equal to or greater than 2.3.In some embodiments, the described supporting factor is about 1.7-2.2.

When the described composition that comprises reactive hydrogen comprises oligomeric polyols and is derived from the polyvalent alcohol of oil, can control the supporting factor of described polyurethane polyol by control oligomeric polyols and the amount that is derived from the polyvalent alcohol of oil.For example, in some embodiments, the amount of oligomeric polyols is about 10-90 weight %, and the amount that is derived from the polyvalent alcohol of oil is about 10-90 weight %.In other embodiments, the amount of oligomeric polyols is about 10-60 weight %, and the amount that is derived from oil is about 40-90% weight.In other embodiment, the amount of oligomeric polyols is about 15-40 weight %, and the amount that is derived from the polyvalent alcohol of oil is about 60-85 weight %.

-skin thickness

In some embodiments, flexible plate urethane foam of the present invention has thin or low-density crust.In this article, term " crust " expression is formed at the high-density skin on the plate foam block.Usually the exodermis with block cuts, and discards as waste material or refuse.Minimize by thickness or density with crust, can improve the productive rate of foams, this is because of the foams that can cut so still less.Can measure the density of crust by the density of for example measuring outer certain part of foam block.

In some embodiments, compare with the reference preparation that does not contain oligomeric polyols, the crust density that comprises the foam block of oligomeric polyols (is that foams outside 1 inch (density of 1 ")) have reduced about 20% or more.In some embodiments, compare with the reference preparation that does not contain oligomeric polyols, the crust density that comprises the foam block of oligomeric polyols has reduced about 0.25 pound/foot ³Or it is more.In other embodiments, compare with the reference preparation that does not contain oligomeric polyols, crust density is gradually little about 0.50 pound/foot ³Or more, perhaps about 0.75 pound/foot ³Or more, even about 1.0 pounds/foot ³Or it is more.

-colour fastness

The another kind of useful characteristic of foams is their colour fastness, and colour fastness represents that they place the ability of the white when keeping it just to make when being subjected to illumination under the envrionment conditions.Preferably, described foams are subjected under envrionment conditions after 6 weeks of illumination under the condition that does not contain UV stabilizer, and the specular reflectance that characterizes with (L) value is at least 70 units, and (b) value is not more than 25 units, and preferably (a) value is not more than 4 units.After these foams are made, preferably have (L) of listed numerical value above satisfying, (a) and (b), and when being subjected to illumination under these conditions, these numerical value can not change substantially.Specifically, (L) value can not surpass 14 units with the variation that (b) is worth, and (a) the value variation can not surpass 5 units.

Peculiar smell

In some embodiments, urethane foam of the present invention has faint peculiar smell, and its peculiar smell degree is derived from the polyvalent alcohol of oil with use at least but not the peculiar smell degree of the reference foam body that oligomeric polyols prepares is identical, perhaps is better than the reference foam body.Described faint peculiar smell make these foams be industrial foams production can accept.Peculiar smell can be by for example using artificial Testing Team or measuring the content that some that may comprise in the oligomeric polyols produce the compound of peculiar smell and measure.The example that produces the compound of peculiar smell comprises the lipid oxidation product, it typically is aldehyde compound, for example hexanal, aldehyde C-9 and capraldehyde.In some embodiments, hexanal content in described oligomeric polyols or the urethane foam is approximately equal to or less than 30ppm, for example be approximately equal to or less than 25ppm, be approximately equal to or less than 20ppm, be approximately equal to or less than 15ppm, be approximately equal to or less than 10ppm, be approximately equal to or less than 5ppm, perhaps be approximately equal to or less than 1ppm.In some embodiments, the aldehyde C-9 content in described oligomeric polyols or the urethane foam is approximately equal to or less than 30ppm, for example is approximately equal to or less than 25ppm, be approximately equal to or less than 15ppm, be approximately equal to or less than 10ppm, be approximately equal to or less than 5ppm, perhaps be approximately equal to or less than 1ppm.In some embodiments, the capraldehyde content in described oligomeric polyols or the urethane foam is approximately equal to or less than 20ppm, for example is approximately equal to or less than 15ppm, is approximately equal to or less than 10ppm, is approximately equal to or less than 5ppm, perhaps is approximately equal to or less than 1ppm.In some embodiments, the total amount of hexanal, aldehyde C-9 and capraldehyde is approximately equal to or less than 80ppm in described oligomeric polyols or the urethane foam, for example be approximately equal to or less than 70ppm, be approximately equal to or less than 60ppm, be approximately equal to or less than 50ppm, be approximately equal to or less than 40ppm, be approximately equal to or less than 30ppm, be approximately equal to or less than 20ppm, be approximately equal to or less than 10ppm, be approximately equal to or less than 5ppm, perhaps be approximately equal to or less than 3ppm.

Feel

In some embodiments, compare with the reference preparation that does not contain described oligomeric polyols, foams of the present invention have improved feel.Sensation when in this article, term " feel " expression staff rubs on the polyurethane foam surface gently.If it is stiff or coarse that foams are felt, then describe it and have " feel of difference ".If level and smooth or velutinate sensation is arranged, then be described as having " good hand feeling ".Although feel is a character qualitatively, observed the 5%IFD that records in improved feel and the identical plate urethane foam sample reduce good relevant.That is to say that along with reducing of the 5%IFD of sample, feel obtains to improve.

In embodiments of the present invention, compare with the reference preparation that does not contain oligomeric polyols, flexible plate urethane foam has the 5%IFD that reduces.For example, compare with reference preparation, 5%IFD may reduce about 2% or more.In other embodiment, compare with reference preparation, 5%IFD may reduce 5% or more.

Feel also may be relevant with the surface roughness of flexible plate urethane foam.From microcosmic, the surface of foam sample is made up of a series of high or low points.Profile meter (perthometer) but the center line average of high or low point (" Ra ") on the quantitative measurment foam surface.High Ra value representation is corresponding to the uneven surface of the feel of difference.Low Ra value representation is corresponding to the smooth-flat-surface of improved feel.For example can use available from front yard, German Guo, a state in the Zhou Dynasty root (

) Ma Gemu than the Ra of the profile instrumentation template material urethane foam of (Mahr GmbH).

Feel also can be relevant with the average perforation size (for example mean pore size) of urethane foam.Along with reducing of average perforation size, foams show improved feel.Average perforation size can be measured by the following method, the micro-image of manual measurement foams for example, the perforation size in the software measurement micro-image that perhaps uses a computer.

Flame retardant resistance

In some embodiments, compare with the reference preparation that does not contain oligomeric polyols, foams of the present invention have improved flame retardant resistance.Flame retardant resistance can be according to for example Technical Bulletin 117, " " (in March, 2000) measures to being used to requirement, test procedure and equipment (Requirements, TestProcedure and Apparatus for Testing the Flame Retardance of Resilient FillingMaterials Used in Upholstered Furniture) with the flame retardant resistance test of the elastic filling material of the addition polymerization of cushion.Usually by adding one or more fire retardants, for example halophosphate, aluminum phosphate, hibbsite or trimeric cyanamide improve flame retardant resistance.Usually the amount that adds these fire retardants of polyurethane composition is: the halophosphate of about 6-10 weight %, the perhaps hibbsite of the highest about 50 weight % or trimeric cyanamide.

IFD gradient in the-plate block

The production block of flexible sheet strand foam body is normally very big, and is for example wide about 7 feet, high about 4 ', be about 300 feet.In order to make furniture liner, hardness (for example measuring) and variable density minimum in the preferred described plate foam block with 25%IFD with required stability property.Observe with respect to the reference preparation that does not contain oligomeric polyols, the variation of the 25%IFD of urethane foam of the present invention reduces.

Water-repellancy

In some embodiments, compare with the reference preparation that does not contain oligomeric polyols, plate urethane foam of the present invention shows the hydrophobicity of improved water-repellancy or raising.For example for open air application and marine use, improved water-repellancy is very important.For example, the water of measured quantity can be placed on the foams, measure the time in the vesicular structure that water is absorbed into foams, the water-repellancy or the hydrophobicity of coming assay plate strand foam body thus.Have long soak time and represent that foams have the water-repellancy or the hydrophobicity of raising.In some embodiments, compare with the reference foam body that does not contain oligomeric polyols, the absorbent time of foams of the present invention has increased about 20% or more, and for example about 30% or more, about 40% or more, perhaps about 50% or more.

-flexible touch

In some embodiments, compare with the reference preparation that does not contain oligomeric polyols, urethane foam of the present invention has lower 5%IFD, can keep approximately identical 25%IFD simultaneously.The 5%IFD of this needs and the balance of 25%IFD can allow to reduce the amount of polyester (PET) fiber that uses in the furniture liner by urethane foam manufacturing of the present invention.Specifically, low 5%IFD provides softer sense of touch for foams, and up to now, this effect all provides by coating urethane foam with the softish trevira.

Further illustrate the present invention with reference to following examples, these embodiment still can not be construed as limiting it with helping understand the present invention.

Embodiment

Abbreviation

Acid number (AV)-also claim acid number, and unit is (a milligram KOH/ gram polyvalent alcohol)

The tolerance of double bond content in iodine number (FV)-material is expressed as the iodine (I with a gram substance reaction ₂) the centigram number.

Hydroxyl value (OH value)-hydroxyl value, unit is a milligram KOH/ gram polyvalent alcohol

Fn-number average hydroxy functionality is expressed as the hydroxyl value that comprises in each molecule.Fn uses following formula to calculate Fn=(OH#/56) * (Mn/1000), and Mn is measured by the water vapour penetration platen press in the formula.

EOC-epoxide oxygen level (from the oxygen % of epoxide)

Mn (GPC)-according to the number-average molecular weight that GPC records, unit is (a gram/mole).

Mn (LS)-according to the number-average molecular weight that scattering of light records, unit is (a gram/mole).

The number-average molecular weight (gram/mole) of Mn (VPO)-record according to the water vapour penetration platen press.

The hydroxyl equivalent that EW-calculates according to (Mn/Fn)

The weight-average molecular weight (gram/mole) of Mw (LS)-record by scattering of light.

Monomeric weight percentage in monomer (Mon)-polyvalent alcohol.

Dimeric weight percentage in dimer (Dim)-polyvalent alcohol.

Trimerical weight percentage in tripolymer (Trim)-polyvalent alcohol.

The tetramer ⁺(Tetr ⁺The weight percentage of the tetramer and higher oligomer in the)-polyvalent alcohol.

The overall weight percent of % oligopolymer-all dimers, tripolymer, the tetramer and higher oligomer.

The hydrodynamic diameter of the polyvalent alcohol that g ' M-records by GPC is used for characterizing the scope of oligopolymer with respect to the vinylbenzene standard specimen.Along with the increase of oligomerization, g ' M reduces.

Viscosity-in the viscosity of 25 ℃ of materials that record, its unit is handkerchief second.

The compression permanentset that CS=represents with percentage ratio.

The superoxide numerical value that PV=records by AOCS method Cd 8b-90, unit are (milliequivalent/1000 gram samples).

The premixture of B-side plate material-polyvalent alcohol, tensio-active agent, linking agent, catalyzer, additive and whipping agent will mix with required polyisocyanates later on, produces the foamy reaction to cause.

The foams peculiar smell-in some cases, after just preparing foams, the peculiar smell feature of each foams.Foams are chosen as normal level show, the peculiar smell of these foams with use routine techniques just the foams of preparation compare do not have different.In other embodiments, foams sometimes have significant peculiar smell, and this may be because the special polyol that uses causes.Foams are chosen as show when slight, but these foams have remarkable difference can not make the peculiar smell of people's discomfort.Be rated and show that strongly peculiar smell is different, its degree makes that most of viewers feel to detest.

Foams tightness-to the hole of foams is sealing or the unlimited subjective assessment of being carried out.Blind hole is more than the hole of opening wide in the sealing explanation foams.

The term of bearer properties-a kind of communality is used for being illustrated in the result who obtains in the supporting capacity test of test flexible foam.Usually the data of report comprise 25% and 65% recessed pressure reactive force deflection value.

MDI-methylene-bis (phenyl isocyanate).

Press to fall into the numerical value that the ratio of the factor-calculating 65% recessed pressure reactive force deflection value and 25% recessed pressure reactive force deflection value obtains.

The TDI-tolylene diisocyanate.

Material

In embodiment 1-14, use following material:

An Keer F-3022 (Arcol

F-3022)-a kind of petroleum-based nominal molecular weight is 3000 polyether triol, by making in propylene oxide and the oxyethane adding glyceryl initiator compounds.The characteristic feature of commercially available prod comprises: water white, in fact all be terminal hydroxy group, the hydroxyl value of secondary hydroxyl when being about 56,25 ℃ viscosity be 480 milli handkerchief seconds.This material has the distinctive smell of very slight polyether glycol.This material can be buied from Bayer Corp (Bayer Corporation).

Soybean oil-when mentioning soybean oil in this patent, represent the soybean oil of commercially available refining, bleaching and deodorizing level (RBD).

Rec Sol not

(Flexol

)-a kind of epoxidised soybean oil available from carbide of calcium affiliated company (UnionCarbide), perhaps is the epoxidised soybean oil of other commercially available brand.Commercially available epoxidised soybean oil has following character usually:

Specification	Restriction	Method
			Oxyethane, %	6.8 it is minimum	AOCS Cd 9-57 or ACS PER-OXI Rev.000
Acid number (milligram KOH/ gram)	0.3 it is maximum	AOCS Cd 3d-63 or equivalent method
			Iodine number	1.5 it is maximum	AOCS Cd 1-25
Add the nail (unit of length) color	1.0 it is maximum	AOCS Td 1a-64

Reach Bick BL-11 (Dabco BL-11)-and a kind of catalyzer Industrial products, can buy from air products company limited (Air Products Corporation), comprise the dipropylene glycol solution of 70 weight % two (dimethyl aminoethyl) ethers.Usually in foamable reaction, be used as catalyzer.

Reach Bick

DC-5169 (Dabco

DC-5169)-and a kind of tensio-active agent Industrial products, company limited buys from air products.

Reach Bick

33-LV (Dabco

33-LV)-and a kind of catalyzer Industrial products, company limited buys from air products, comprises the dipropylene glycol solution of the triethylenediamine of 33 weight %.Usually be used as the catalyzer of polyreaction or gelatinization process.

DEOA-is as the technical grade diethanolamine of foams stabilization linking agent.

Ni Yakesi

D-19 (Niax

D-19)-and the tinbase gelation catalyst, can be from GE silicone-OSI special product company limited (GE Silicones-OSI Specialties, Inc.) acquisition.

Ni Yakesi

Y-10184 (Niax

Y-10184)-and the silicone base tensio-active agent, can obtain from GE silicone-OSI special product company limited.This product is specified and is used to prepare the flexible molding polyurethane foamed material.

Te Gusitebu

B-2370 (Tegostab

B-2370)-from the surfactant product that De Gusa A sells, be designed for conventional plate (slabstock) foam materials.

Te Gusitebu

B-4690LF (Tegostab

B-4690LF)-the ground fog level tensio-active agent buied from De Gusa AG (Degussa AG).

2 of tolylene diisocyanate-tolylene diisocyanate, 4-and 2,80/20 mixture of 6-isomer, this mixture can obtain from Bayer Corp, the product moral of covering by name

TD-80 (Mondur

TD-80) product, the A level.

The commercially available distilled water of water-use is as indirect whipping agent.

The epoxidised soybean oil A of embodiment 1-part

Prepared the epoxidised soybean oil of part by following steps:

On 5 liters three neck round-bottomed flasks, temperature control unit, addition funnel, reflux exchanger and whipping appts have been installed.Add to this reactive system: 1500 gram soybean oil (RBD level, iodine number are 131, and viscosity was 62 milli handkerchief seconds, available from Archer Daniels Midland company (Archer Daniels Midland)); 225 gram Glacial acetic acid (available from Brigit Fischer (Schmidt)); And 19 the gram vitriolic 50% aqueous solution (available from Alder auspicious red (Aldrich)).Reactor assembly is warming up in 70 ℃ the process, with these component thorough mixing.When arriving design temperature, in 30 fens clock times, add the aqueous sodium hydroxide solution (auspicious red) of 729 grams 35%, keep 70 ℃ design temperature simultaneously, and keep vigorous stirring available from Alder from addition funnel.

After reacting again 60 minutes, the material in the reaction system transferred in 3 liters the separating funnel, make its cooling.During cooling, the epoxidised thick soya-bean oil of water and part is divided into two-layer.Obtain product by discharging this first water layer, with distilled water the epoxidised thick soya-bean oil layer of part is washed three times then, use 1 liter of distilled water at every turn.The epoxidised soybean oil of part after the washing is separated once more, it is added Erlenmeyer flask, add 100 gram deacidites (deriving from Baeyer).Then this mixture was stirred 2 hours, with any remaining acid that neutralizes.Filtration product deionizing exchange resin applies rough vacuum to remove remaining water to it then.

Make the epoxidised soybean oil product of part, its iodine number is 83, and epoxy oxygen content (EOC) is 2.74%.Method therefor and gained values summarized are in table 1.1.

Table 1.1: the epoxidised vegetables oil of part

Sample

Soybean oil (gram)

Acetate (gram)

H 2SO 4(gram)

Temperature (℃) (preheating/rxn)

H 2O 235% (gram)

DB∶AA∶ H 2O 2Ratio

Time (minute)

Ion exchange resin (gram)

EOC (％)

Iodine number

Viscosity (25 ℃ handkerchief seconds)

Embodiment 1

1500

225

19

70/70

729

1∶0.5∶1

60

100

2.74

83

--

The epoxidised soybean oil B of embodiment 2-part

Prepared the epoxidised soybean oil of part according to embodiment 1, its difference is, the amount and the time of the reactant that embodiment 2 these ranks go out in the use table 2.1.Make the final part epoxidised soybean oil product of feature with table 2.1 demonstration.

Table 2.1

Sample	Soybean oil (gram)	Acetate (gram)	H 2SO 4(gram)	Temperature (℃) (preheating/rxn)	H 2O 235% (gram)	DB∶AA∶ H 2O 2Ratio	Time (minute)	Ion exchange resin (gram)	EOC (％)	Iodine number	Viscosity (25 ℃ handkerchief seconds)
												Embodiment 2	500	75	6.3	70/70	147	1∶0.5∶0.6	60	40	2.65	83	--

The epoxidised soybean oil C of embodiment 3-part

Prepared the epoxidised soybean oil of part according to embodiment 1, its difference is, the amount and the time of the reactant that embodiment 3 these ranks go out in the use table 3.1.In addition, hydrogen peroxide adds by peristaltic pump, rather than added by dropping funnel in 30 minutes with the speed of 7.5 ml/min.Make the final part epoxidised soybean oil product of feature with table 3.1 demonstration.

Table 3.1

Sample	Soybean oil (gram)	Acetate (gram)	H 2SO 4(gram)	Temperature (℃) (preheating/rxn)	H 2O 235% (gram)	DB∶AA∶ H 2O 2Ratio	Time (minute)	Ion exchange resin (gram)	EOC (％)	Iodine number	Viscosity (25 ℃ handkerchief seconds)
												Embodiment 3	1500	225	9	65/70	600	1∶0.5∶0.73	3	75	3.56	71	0.16

Embodiment 4-polyvalent alcohol A

At first, 1 liter of three neck round-bottomed flask experimental installation that temperature control unit, addition funnel, condensation reflux device and whipping appts are housed used in the preparation of polyvalent alcohol.In this reaction system, add 80 gram methyl alcohol and 0.7 gram fluoroboric acid (as with 48% mixture of water, auspicious red available from Alder).Reactor system being heated to ebullient simultaneously, with these component thorough mixing.To add fast in the reactor of vigorous stirring according to the epoxidised soybean oil of 250 gram parts of embodiment 1 preparation then.

After reacting in addition 40 minutes, this mixture is cooled to 50-60 ℃, the deacidite (available from the Le Weitaite MP-64 of Baeyer) that adds about 15 grams is with neutralizing acid again.This mixture stirred 1 hour, made its cooling.By solids removed by filtration ion exchange resin, remaining water and alcohol are removed in vacuum distilling, continue to reclaim product.The technology of using and the amount of reactant are listed in " embodiment 4 " of table 4.1.The character of the oligomeric polyols that makes is listed in table 4.2 " embodiment 4 ".

Table 4.1. vegetable oil-based polyols

Sample	Methyl alcohol (gram)	Unsaturated epoxidised soybean oil (gram)	Edible oil	Catalyzer (48% HBF 4) (gram)	AMC (gram)	Methyl alcohol: the ratio of epoxide group	Ion exchange resin (gram)
								Embodiment 4	80	250	Embodiment 1	0.7	0	6∶1	15
Embodiment 5	--	250	Embodiment 4	--	2.5	--	--
								Embodiment 6	164	500	Embodiment 2	1.4	0.5	6∶1	20
Embodiment 7	454	1500	Embodiment 3	4.1	1.5	6∶1	60

Table 4.2: the character of vegetable oil-based polyols

Sample	OH value (milligram KOH/ gram)	EOC (％)	Iodine number	Acid number (milligram KOH/ gram)	25 ℃ viscosity (handkerchief second)	Water (%)	Color	Fn	The ratio of oligopolymer/monomer
										Embodiment 4	98	0.01	77	2.4	0.4	--	Yellow	--	21∶79
Embodiment 5	100	0.01	67	2.5	0.43	0.027	Deep yellow	--	20∶80
										Embodiment 6	94	0.013	79	0.334	0.26	--	Yellow	1.93	16∶84
Embodiment 7	88	0.005	90	0.714	0.22	0.038	--	1.8	14∶86

Embodiment 5-polyvalent alcohol B

Temperature control unit, addition funnel, condensation reflux device and whipping appts are installed on 1 liter erlenmeyer flask.Polyvalent alcohol and the 2.5 gram volatile salts of 250 grams according to embodiment 4 preparations are added in this flask.Reactor system is being heated in 60-70 ℃, with these component thorough mixing.

After stirring 15 minutes, the material in the reactor system transferred in 1 liter the separating funnel, make its cooling.In process of cooling, water and thick polyvalent alcohol are divided into two-layer.Discharge first water layer, with distilled water thick polyvalent alcohol layer is washed five times then, use 500 ml distilled waters at every turn, thus product is proceeded to handle.Then product is applied rough vacuum, to remove remaining water.Summary can see Table 4.1 " embodiment 5 ".The final oligomeric polyols that reclaims has the character shown in " embodiment 5 " of table 4.2.

Embodiment 6-polyvalent alcohol C

According to embodiment 4 and 5, prepare polyvalent alcohol by following steps, its difference is, uses the amount and the time of " embodiment 6 " in the table 4.1 listed reactant.The final oligomeric polyols that reclaims has " embodiment 6 " listed character of table 4.2.

Embodiment 7-polyvalent alcohol D

Step according to embodiment 4 and 5 prepares polyvalent alcohol, and its difference is, listed reactant consumption and the time in " embodiment 7 " of use table 4.1.The final oligomeric polyols that obtains that reclaims has the character of " embodiment 7 " of table 4.2.

Embodiment 8-polyol E

The preparation of polyol E uses the 2 liter of three neck round-bottomed flask experimental installation that is equipped with temperature control unit, addition funnel, condensation reflux device and whipping appts to carry out.In this reactor system, add 35.5 gram methyl alcohol (being accredited as A.C.S.) and 1.12 available from Brigit Fischer (Schmidt) (Fisher) restrain fluoroboric acid (as with 48% mixture of water, auspicious red available from Alder).Reactor system is being heated in 50 ℃, with these component thorough mixing.Reach after the design temperature, in reactor, add 400 gram epoxidised soybean oil (" Fu Laike Sol (Flexol), " available from carbide of calcium affiliated company).Continue vigorous stirring, temperature of reactor is elevated to 90 ℃.After reacting under these conditions 30 minutes, add 100 gram epoxidised soybean oil (" Fu Laike Sol ") again in reactor, reaction is proceeded 3 hours again.

After 3 hours,, add 15 gram deacidites (Le Wote MP-64 is available from Baeyer) with reactor cooling to 60 ℃.This mixture was stirred 1 hour, with any remaining acid that neutralizes.Filtration product then, the deionizing exchange resin applies rough vacuum, to remove remaining water and solvent.In addition, under gpc analysis, this polyvalent alcohol shows following composition: 47% monomer; 12% dimer; 8% tripolymer; And 33% the tetramer and high-grade oligopolymer more.The character of the final polyvalent alcohol that makes is listed in table 8.1 " embodiment 8 ".In embodiment 10, make and use some other a large amount of polyol Es (seeing Table 10.1).

Table 8.1: polyvalent alcohol character

Embodiment 9-polyvalent alcohol F

Prepared a series of polyvalent alcohols according to embodiment 8, its difference is, uses the catalyzer of 33 gram methyl alcohol and 0.05%.Identical condition has repeated four times to prepare four kinds of different samples.The polyvalent alcohol of gained has embodiment 9-1 in slight soybean oil peculiar smell and the table 9.1, embodiment 9-2, the character shown in embodiment 9-3 and the embodiment 9-4.

Table 9.1: polyvalent alcohol character

Sample	OH value (milligram KOH/ gram)	EOC (％)	Acid number (milligram KOH/ gram)	25 ℃ viscosity (handkerchief second)	Water (%)	Mn (GP C) (gram/mole)	EW	Fn	Oligopolymer (%)
										Embodiment 9-1	53.77	4.23	0.33	4.0	0.06	1668	1044	1.6	54.73
Embodiment 9-2	60.43	4.09	0.29	5.1	0.07	1758	929	1.89	56.9
										Embodiment 9-3	57.23	3.95	0.29	5.4	0.066	1777	980.4	1.81	58.67
Embodiment 9-4	57.46	4.17	0.33	4.72	0	1759	976.5	1.8	56.94

Embodiment 10-uses the foams of polyol E preparation

The preparation of flexible foam

(a) preparation of plate

As the first step of preparation listed molding flexible foam among the embodiment, add by various components in 1 gallon the wide-mouth plastics kettle required foams preparation, prepared B-side plate material.At first polyvalent alcohol is added in this kettle, place then on the electronic laboratory work mixing tank that Ji Fu (Jiff) board HS-2 type mixing paddle is housed.Begin to mix, in the mixing tank continuous firing, other formulation component adds successively with all.Add after last a kind of formulation component, continue again to mix 15 minutes.Then this plate is shifted out from mixing tank, get 1000 milliliters of wide-mouth vial sample measurement viscosity, observe color and transparency.Remaining plate is covered, leave standstill, finish the preparation of other foams simultaneously.

With after the temperature regulation to 25 ℃, use conventional rotary-type Brookfield (Brookfield) board viscometer to measure the viscosity of plate.

(b) step of blending ingredients and preparation foams

By the B-side plate material of aequum being added the poly cup (the DMC-33 type is available from international paper (International Paper) company) of 33-ounce, the preparation of beginning foams.The embodiment foams of all moldings all prepare under toluene diisocyanate index is 105 condition.For various preparations, carefully take by weighing the tolylene diisocyanate of calculated amount, add in 400 milliliters three mouths (tripour) plastic beaker, place and mix the next door, position.

In order to cause the foams preparation feedback, the cup that will comprise B-side plate material places on the mixing equipment, and this equipment is to mix 3 inches mixing paddles by the 10-inch workshop drilling machine of triangle Xiao Pu Masite (Delta ShopMaster) board DP-200 type (to examine En Mikesi (Conn Mixers) company; Kao Enbu Randt (ConnBlade) board, ITC type, 3 inches of diameters) and build.This mixing tank is set under the rotating speed of 1100rpm and moves 30 seconds altogether, and working time is by the control of electronics countdown timing register.Start mixing process by push-switch.In the time of the timing register countdown, pick up the beaker that tolylene diisocyanate is housed, in 6 seconds mixing times of residue, tolylene diisocyanate is added in the cup fast.

When mixing period finished, the material that allows to mix in the cup swelled.During curing, swelling the time of particular formulations noted at the center of close observation cup.

When curing cycle finishes, scumming body in the cup.To foam sample revise, weigh, mark, make it under 25 ℃ and 50% relative humidity, leave standstill a couple of days, test physical properties then.

The physical properties test

Measure the physical properties of flexible foam according to the step of listing among the ASTM D 3574.Note in some cases, before full 7 day set time of recommending, foams are tested.

Data have been shown with the lower section by the conventional plate foams of different oligomeric polyols formulation preparation.The feature that each oligomeric polyols has is that they have low number average hydroxy functionality.Yet when having the polyvalent alcohol of required number average hydroxy functionality according to original expection employing, the physical properties of the foams that make is unexpectedly good.

Use polyol E to prepare the sample of foams according to above step.Following table has shown foam formulation (table 10.2) and the physical property data (table 10.3) with the foams of two kinds of different tensio-active agent preparations.

Table 10.1: the characteristic of polyol E

Polyvalent alcohol	OH value (milligram KOH/ gram)	Water (%)	Acid number (milligram KOH/ gram)	250 ℃ viscosity (handkerchief second)	EOC(％)
						E-1	74.89	0.051	0.42	7.23	3.41
E-2	71.88	0.045	0.55	5.44	3.53
						E-3	73.67	0.041	0.51	5.43	3.46

Table 10.2: polyurethane formulation

Component	10-1	10-2	10-3	10-4	10-5	10-6	Reference 1	Reference 2
									Polyvalent alcohol F-3022	60	60	60	60	60	60	100	100
E-1	40	40	0	0	0	0	0	0
									E-2	0	0	40	40	0	0	0	0
E-3	0	0	0	0	40	40	0	0
									B-8221 (silicone surfactant)	1	0	1	0	1	0	1	0
EP-H-140 (silicone surfactant)	0	1	0	1	0	1	0	1
									BL-11 (amine)	0.23	0.23	0.23	0.23	0.265	0.265	0.265	0.265
K-29 (tin catalyst)	0.14	0.14	0.14	0.14	0.14	0.155	0.155	0.155

Embodiment 11-uses the foams of polyvalent alcohol F preparation

Following table has shown the physical properties of the conventional plate foams of the polyvalent alcohol F that combines different levels.As before the foams component, mixed the polyvalent alcohol of short run.The feature of polyvalent alcohol is listed in table 11.1.Polyurethane formulations is listed in table 11.2 and table 11.3.The urethane physical properties is listed in table 11.4.

Table 11.1: the feature of polyvalent alcohol

Polyvalent alcohol	OH value (milligram KOH/ gram)	Water (%)	Acid number (milligram KOH/ gram)	Viscosity under 25 ℃ (handkerchief second)	EOC (％)	Peculiar smell
							F-1	53.77	0.064	0.33	4	4.23	Slight soybean flavor
F-2	57.46	0.001	0.33	4.72	4.17	Slight soybean flavor
							F-3022	55.30	0.02	0.03	--	--	--

Table 11.2: polyurethane formulations

Component	11-1	11-2	11-3	11-4	11-5	11-6	11-7	11-8	11-9	Reference
											Polyvalent alcohol F-3022	90	80	70	60	50	40	40	40	40	100
F-1	10	20	30	40	50	60	60	60	60	0
											EP-H-140 (silicone surfactant)	1.0	1.0	1.0	1.0	1.0	1.0	1.0	1.0	1.0	1.0
BL-11 (amine)	0.16	0.16	0.16	0.16	0.16	0.16	0.36	0.38	0.38	0.16
											K-29 (tin catalyst)	0.217	0.217	0.217	0.217	0.217	0.217	0.21	0.21	0.21	0.22
Water	3.976	3.971	3.967	3.962	3.958	3.954	3.954	3.954	3.954	3.98
											The TDI index	105	105	105	105	105	105	105	105	105	105
TDI(PPH)	49.59	49.56	49.54	49.51	49.49	49.47	49.47	49.47	49.47	49.61
											The TDI temperature (℃)	23.2	23.2	23.2	23.2	23.2	23.2	21.9	21.9	21.9	21.6
Batch temperature (℃)	17.9	18.4	18.4	18.4	18.4	18.4	17.6	17.3	17.5	19.1
											Reaction (℃)	19.6	19.9	19.9	19.9	19.9	19.9	19.0	18.8	18.9	19.9
The mixed time (second)	25	25	25	25	25	25	25	25	25	25
											The emulsifiable paste time (Cream Time) (second)	11	14	15	17	18	20	16	12	12	10
The cup top time (Top of Cup Time) (second)	45	47	53	57	65	69	45	41	40	42
											Swell the time (second)	87	89	96	104	115	123	87	79	81	84

Table 11.3: polyurethane formulations

Component	11-10	11-11	11-12	11-13	11-14	Reference
							Polyvalent alcohol F-3022	90	80	70	60	50	100
F-2	10	20	30	40	50	0
							EP-H-140 (silicone surfactant)	1.0	1.0	1.0	1.0	1.0	1.0
BL-11 (amine)	0.16	0.16	0.16	0.16	0.16	0.16
							K-29 (tin catalyst)	0.217	0.217	0.217	0.217	0.217	0.22
Water	3.982	3.984	3.986	3.988	3.99	3.98
							The TDI index	105	105	105	105	105	105
TDI(PPH)	49.65	49.68	49.72	49.76	49.79	49.61
							The TDI temperature (℃)	22.6	22.6	22.6	22.6	22.6	21.6
Batch temperature (℃)	17.6	17.5	17.5	17.6	17.6	19.1
							Reaction (℃)	19.2	19.1	19.1	19.2	19.2	19.9
The mixed time (second)	25	25	25	25	25	25
							The emulsifiable paste time (second)	11	13	15	17	19	10
The cup top time (second)	45	46	51	57	61	42
							Swell the time (second)	84	87	93	101	111	84

Embodiment 12-uses the foams of polyvalent alcohol C preparation

Below data presentation use the conventional plate foams physical properties of the foams that conventional polyvalent alcohol that is derived from oil (peace jade-like stone you F-3022) and polyvalent alcohol C prepare.Polyurethane formulations is listed in table 12.1.The polyurethane foam volume property is listed in table 12.2.

Table 12.1: polyurethane formulations

Component	12-1	12-2	12-3	12-4
					Polyvalent alcohol F-3022	80.0	60.0	40.0	20.0
Polyvalent alcohol C	20.0	40.0	60.0	80.0
					BF-2370	1.0	1.0	1.0	1.0
BL-11	0.235	0.235	0.235	0.270
					K-29	0.230	0.230	0.230	0.180
TDI-80	50.80	52.04	53.28	54.51
					Water	4.0	4.0	4.0	4.0
The TDI index	105.0	105.0	105.0	105.0
					The TDI temperature (℃)	21.9	21.9	21.9	22.3
Batch temperature (℃)	25.0	26.10	26.0	25.2
					The emulsifiable paste time (second)	11.0	12.0	13.0	14.0
The cup top time (second)	30.0	34.0	39.0	46.0
					Swell the time (second)	64.0	71.0	78.0	80.0
The polyvalent alcohol peculiar smell	Well	Well	Well	Well
					Tackiness	Outstanding	Well	Good	--

Embodiment 13-uses the foams of polyvalent alcohol D preparation

Below data presentation use the conventional plate foams physical properties of the foams that conventional polyvalent alcohol that is derived from oil (peace jade-like stone you F-3022) and polyvalent alcohol D prepare.Polyurethane formulations is listed in table 13.1.The polyurethane foam volume property is listed in table 13.2.

Table 13.1: polyurethane formulations

Component	13-1
		Polyvalent alcohol F-3022	60.0
Polyvalent alcohol D	40.0
		BF-2370	1.0
BL-11	0.235
		K-29	0.230
TDI-80	52.60
		Water	4.0
The TDI index	105.0
		The TDI temperature (℃)	20.8
Batch temperature (℃)	25.7
		The emulsifiable paste time (second)	12.0
The cup top time (second)	34.0
		Swell the time (second)	71.0
The polyvalent alcohol peculiar smell	Difference
		Tackyness	Glutinous

Embodiment 14: use the foams of polyvalent alcohol F preparation, colour fastness

The colour fastness test procedure

According to following steps the foams that make are carried out the colour fastness test.

1. foam sample was applied for 6 all environment illumination, perhaps 8 hours full suns.

2. after the exposure, with the color and the reference comparison of the foams after the exposure.

3. foam sample is before colour fastness test and be stored in afterwards in the black plastic bag.

The super scanning XE of Korea Spro Te Laibu (the HunterLab Ultrascan XE) spectrocolorimeter that employing has 6 inches integrating spheres carries out color measurenent.According to ASTM E308, comprise the reflection of minute surface and do not comprise the reflection of minute surface with 10 ° of observing angles and light source D65.Probe inlet is circular, and diameter is 1 inch, and viewing angle is 8 °, and beam diameter is 1 inch.Every 10nm gets spectroscopic data in the 375-750nm wavelength region, by the decline of these data computation data.Colour scale is L, a, b.

According to foregoing step, use the prescription of table 14.1, prepared a series of urethane foams.

Table 14.1

Component	Weight fraction
		Polyvalent alcohol F-3022	100-X
Polyvalent alcohol F	X
		Water	4.0
Silicone surfactant	1.0
		Kicker	0.1
Foaming and gelation catalyst	0.2
		Tin catalyst	0.25
80/20 TDI index	105

Change the content of polyvalent alcohol F in the prescription, obtain a series of polyvalent alcohols.Reference comprises 100 parts oil polyvalent alcohol and 0 part polyol E.Other prescription comprises 10 parts, and 20 parts, 30 parts, the polyol E of 50 parts and 60 parts.Do not adding UV light stabilizing agent in the foams preparation arbitrarily.

Be exposed to 6 weeks of surround lighting by the foams that this is a series of then, measure colour fastness.The RSEX test result is the spectrophotometer test result, but does not comprise specular reflection, and the RSIN test result comprises specular reflection.The results are shown in table 14.2.

Table 14.2

Polyvalent alcohol F mark	RSEX (L *)	RSIN (L *)
			0 (reference)	82	822
10	84	84
			20	86	86
30	88	88
			40	89.4	88.9
50	90	90.4
			60	90.8	91.4

L ^*Value is the reflected light that records, and scope is from maximum value L ^*=100 to minimum value L ^*=0, perhaps complete black.Therefore, L ^*Be worth highly more, sample is bright more.Can see, compare, significantly improve colour fastness by the amount that increases oligomeric polyols in the flexible polyurethane foam with the flexible polyurethane foam that is derived from oil of not using the UV stablizer.When exposure under envrionment conditions in the time of 6 weeks, use the flexible polyurethane foam of polyol E to keep their initial white better than foams by the polyether polyol preparation that is derived from oil.In addition, when directly being subjected to sun-exposed the time, use the flexible polyurethane foam of polyol E preparation also to keep their initial white better than foams by the polyether polyol preparation that is derived from oil.

The component tabulation of embodiment 15-24

Peace jade-like stone that F-3020: the nominal molecular weight that is derived from oil is 3000 trivalent alcohol, and its hydroxyl value is a 54.5-57.5 milligram KOH/ gram, and acid number is 0.02 milligram of KOH/ gram (available from Baeyer).

B-2130: be derived from the end capped graft polyether type of the primary hydroxyl trivalent alcohol of oil, its hydroxyl value is 23.0-26.0, comprises about 31% co polystyrene and vinyl cyanide solid.

Reach and to detain BL-11 (DABCO BL-11): the kicker of forming by 70% pair (dimethyl aminoethyl) and 30% dipropylene glycol (available from air products (Air Products)).

Reach and to detain BL-13 (DABCO BL-13): the kicker (available from air products) that two (dimethyl aminoethyl) ethers by 23% and 77% dipropylene glycol are formed.

CP-2: three (1,3-two chloro-2-propyl group)-phosphate flame retardants (available from consolidating that Blanc De Sen company limited (Gulbrandsen Co.)).

DOP: dioctyl phthalate (DOP)

Ai Puke Sol 7-4: complete epoxidised soybean oil (available from american chemical system house).

Filler: lime carbonate

FR-550: phosphorus-bromine flame retardant (available from big lake chemical company (Great Lakes Chemical))

K-29: stannous octoate catalyst (available from De Gusa)

L-650: the silicone surfactant (available from GE silicone (GESilicones)) that is used for the flame retardant resistance foams

L-5770: silicone surfactant (available from the GE silicone)

Trimeric cyanamide: fire retardant (available from BASF)

P-945: molecular weight is 4800 trivalent alcohol (available from BASF)

P-4600: the end capped graft polyether type of secondary hydroxyl triol, its hydroxyl value is 27.1-30.1, comprises the vinylbenzene and the vinyl cyanide of the copolymerization of about 42 solid %.

T-9: stannous octoate (available from air products).

TD-33: the amine catalyst of forming by the triethylenediamine of 33% in 67% the dipropylene glycol (available from air products)

TDI: tolylene diisocyanate

RC-6366: the amine catalyst (available from Rui Ximi (RheinChemie)) that comprises 70% 2 (2-decil) ether and 30% dipropylene glycol.

Water: distilled water.

Embodiment 15:

The preparation of oligomeric polyols (12 liters of equipment)

12 liters 5 neck flasks are equipped with mechanical stirrer, thermopair, heating mantles/controller, cooling worm, peristaltic pump and nitrogen inlet.Add 7000 gram epoxidised soybean oil (Ai Puke Sol 7-4) and 280 gram methyl alcohol to this flask.In container independently, by with 7.62 gram HBF ₄(48% the aqueous solution) gets up with 35.0 gram methanol mixed, has prepared catalyst solution.Flow through at water under the situation of condenser, the material of reaction mixture is heated to 55 ℃, high-speed stirring.Use syringe pump with the speed of 0.138 ml/min with HBF ₄Catalyst solution adds in the flask, and the total catalyst joining day is about 6 hours.Add pipe by catalyzer catalyzer is added in the reaction mixture, described catalyzer adds pipe and places near the propeller-blade of bottom.When temperature began to raise, water cycle was by cooling worm, and the temperature of reaction mixture is remained on 55 ℃ ± 2 ℃.Per hour monitor this reaction by measuring EOC.When EOC reaches 3.35-4.40%, stop to add catalyzer.Add pipe with about 2-3 ml methanol flushing catalyzer then, will add pipe and take out from flask.Monitor this reaction with 15 minutes interval, keep constant until catalyzer EOC.The target of final product is 4.25%EOC.The product of gained about 80 ℃ and≤4 the holder conditions under distill, remove any unreacted methanol.The character of oligomeric polyols is listed in table 15.1.

Table 15.1.

Polyvalent alcohol	The OH value	Acid number	Water (%)	Mn (gram/mole) (VPO)	Fn (VPO)	Mn (gram/mole) (LS)	Mw (LS) (gram/mole)	Mw/Mn
									15-1	58.03	0.42	0.09	1763	1.84	--	--	--
15-2	62.56	0.44	0.09	1844	2.06	3206	32180	10.04
									15-3	66.19	0.56	0.07	1687	1.99	--	--	--
15-4	63.42	0.43	0.08	1771	2.03	--	--	--
									15-5	59.80	0.42	0.05	1686	1.80	4537	54670	12.05
15-6	54.16	0.43	0.09	1880	1.81	5396	72420	13.42
									15-7	62.88	0.45	0.03	2057	2.31	7247	475400	65.60
15-8	57.75	0.24	0.05	1954	2.01	1546	7883	5.10
									15-9	59.53	0.26	0.04	2007	2.13	1519	8338	5.49
15-10	62.17	0.33	0.03	1972	2.18	2089	13340	6.39
									15-11	55.63	0.30	0.03	1695	1.68	1611	6928	4.30
15-12	58.81	0.28	0.04	1784	1.87	1567	9294	5.93
									15-13	62.56	0.44	0.09	1844	2.06	3206	32180	10.04

Table 15.1 (continuing)

Polyvalent alcohol	g’M	Viscosity	PV	Monomer	Dimer	Tripolymer	The tetramer	BOC (％)	% is oligomeric
										15-1	--	3.80	--	43.4	11.8	7.3	37.5	4.21	56.6
15-2	0.53	4.65	3.9	41.7	11.5	7.5	39.3	4.22	58.3
										15-3	--	4.71	--	40.6	11.4	7.3	40.8	4.13	59.4
15-4	--	4.04	--	42.9	12.0	7.7	37.4	4.21	57.1
										15-5	0.33	4.48	--	41.8	11.5	7.4	39.3	4.29	58.2
15-6	0.31	9.78	0.8	36.8	9.3	6.5	47.4	4.29	63.2
										15-7	0.06	6.85	1.4	39.5	11.4	7.6	41.5	4.04	60.5
15-8	1.29	3.84	3.8	42.0	11.1	7.6	38.7	4.25	58.0
										15-9	1.23	4.11	1.5	41.2	11.8	7.7	39.3	4.23	58.9
15-10	1.05	5.87	1.5	37.8	10.6	7.0	44.6	4.07	62.2
										15-11	1.27	3.28	1.5	43.9	11.7	7.9	36.5	4.38	56.1
15-12	1.11	4.73	1.9	39.9	11.2	7.3	41.6	4.21	60.1
										15-13	0.53	4.65	3.9	41.7	11.5	7.5	39.3	4.22	58.3

Embodiment 16:

The preparation of oligomeric polyols

Extensive reaction unit comprises 6000 gallons continuous stirred tank reactor (CSTR), and it is equipped with the glycol cooling jacket and has the pump of heat exchanger around the loop.Before adding reactant, the tank reactor with nitrogen purging stirs makes steam head space be inertia.Epoxidised soybean oil with the amount shown in the table 16.1 adds in the described reactor then.After this, the methyl alcohol with the amount shown in the table 16.1 adds in the reactor.In reactor, epoxidised soybean oil and methyl alcohol are carried out thorough mixing, the partial concn gradient being reduced to minimum, with the mixture heating up of gained to about 55 ℃.In addition, by with 1 part of HBF ₄The aqueous solution (aqueous solution of 48 weight %) gets up with 4.6 parts of methanol mixed, has prepared aqueous catalyst solution.In about 5.5 hours, about 218 pounds catalyst solution is added in the tank reactor that stirs.By making the cooling glycol cycle through cooling jacket, remove heat of reaction.In about peak value heat release, by pump take out reaction mixture by pump around loop/heat exchanger, to remove unnecessary heat.After adding all catalyst solutions, reactor kept under temperature about 30 minutes.In reaction process, the variation of monitoring EOC.When reaction finishes, remove remaining methyl alcohol by coupling vacuum stripping.Then by the oligomeric polyols that makes being regulated with nitrogen jet.The character of oligomeric polyols is listed in table 16.2.

Table 16.1

Table 16.2

Polyvalent alcohol	The OH value	Acid number	Water %	Mn (gram/mole) (VPO)	Fn (VPO)	Mn (gram/mole) (LS)	Mw (gram/mole) (LS)	Mw/Mn
									16-1	59.52	0.30	0.07	1864	1.98	1674	8345	4.98
16-2	59.52	0.30	0.07	1864	1.98	1674	8345	4.98
									16-3	59.52	0.30	0.07	1864	1.98	1674	8345	4.98

Table 16.2 (continuing)

Polyvalent alcohol	g’M	Viscosity	PV	Monomer	Dimer	Tripolymer	The tetramer	BOC (％)	% is oligomeric
										16-1	1.17	2.95	2.2	41.4	11.4	7.5	39.7	4.49	58.6
16-2	1.17	2.95	2.2	41.4	11.4	7.5	39.7	4.49	58.6
										16-3	1.17	2.95	2.2	41.4	11.4	7.5	39.7	4.49	58.6

Embodiment 17:

The preparation of flexible sheet strand foam body

Step 1: the step that is used for preparing the B-side

Placing 400 milliliters plastic beaker on the electricity balance to take by weighing the listed polyvalent alcohol of table 17.1.Then, silicone surfactant and the amine catalyst with the preparation aequum adds in the beaker.Next, stannous octoate and the water with the preparation requirement adds in the batch of material.Temperature to the B-side is regulated, and makes with the polyisocyanates blended time, and the temperature of the mixture of blending is 19.2 ℃ ± 0.3 ℃.Diameter 2 is equipped with in use " the electronic laboratory work mixing tank (triangle Xiao Pu Masite board, DP-200 type, 10 inches workshop drilling machines) of mixing paddle (Kao Enbu Randt board; ITC type ;) available from examining En Mikesi company under the rotating speed of 2340rpm, batch of material was mixed 19 seconds.In addition, take by weighing the TDI of preparation aequum, add in 50 milliliters the plastic beaker, place and mix near the site.Then TDI is added in the polyol blends, mixed 6 seconds.Then, this mixture poured in 83 ounces the cup, it is freely swelled.During freely swelling, note the emulsifiable paste time (promptly steeping the time that cup, swells to cream) separately from adding TDI, cup top swells the time (promptly arriving time on cup top to the foam top from adding TDI), and always swells the time (promptly from adding TDI to lather collapse or time of no longer swelling).Then foams and cup are inserted in 100 ℃ the temperature control oven and solidify.When curing oven finishes, make the foams solidify overnight.After the solidify overnight, foams are regulated 72 hours under the condition of 25 ℃ and 50% relative humidity, test its physical properties then.The physical properties that records is listed in table 17.2-17.4.

Table 17.1

Component	30% in conjunction with (PPH)	40% in conjunction with (PPH)	50% in conjunction with (PPH)
				Polyvalent alcohol F-3022	70	60	50
Oligomeric polyols (see Table 15.1 and table 16.2)	30	40	50
				Water	4	4	4
TDI	105 indexes *	105 indexes *	105 indexes *
				L-5770 (silicone surfactant)	1	1	1
BL-11 (amine catalyst)	0.16	0.16	0.16
				K-29 (stannous octoate)	0.22	0.22	0.22

^*The consumption of TDI is based on the hydroxyl value of whole water and polyvalent alcohol and calculates, and 105 index is provided.

Table 17.2 (30% combination)

Polyvalent alcohol	Peculiar smell	The emulsifiable paste time (second)	The cup top swells the time (second)	Always swell the time (second)	Density (pound/foot 3)	Resilience (%)	25% IFD (ox/323 centimetre 2)	65% IFD (ox/323 centimetre 2)	The supporting factor
										15-1	-	13	53	105	1.5	36	25	48	1.88
15-2	-	13	56	110	1.5	36	23	42	1.83
										15-3	-	12	55	108	1.4	35	21	38	1.81
15-4	-	13	50	101	1.5	35	25	46	1.81
										15-5	+	14	52	94	1.5	35	24	43	1.81
15-6	++	13	52	93	1.5	35	24	43	1.75
										15-7	+	14	52	95	1.5	35	25	44	1.74
15-8	++	14	54	104	1.5	36	24	44	1.84
										15-9	++	15	51	96	1.5	35	24	45	1.84
15-10	++	14	49	95	1.5	35	23	41	1.81
										15-11	++	14	51	101	1.5	37	23	42	1.86
15-12	++	12	47	92	1.5	36	23	42	1.81
										15-13	-	13	56	110	1.5	36	23	42	1.83

Table 17.2 (continuing)

Polyvalent alcohol	Tensile strength (kPa)	Elongation (%)	Tearing toughness (ox/rice)	Air-flow (foot 3/ minute)	90%CS (% loss)
						15-1	90	118	296	4.0	11.8
15-2	86	135	276	3.8	8.6
						15-3	81	132	261	4.1	7.9
15-4	96	146	296	4.1	11.3
						15-5	97	140	279	4.0	19.8
15-6	88	133	245	3.9	15.7
						15-7	91	142	283	3.8	38.3
15-8	96	138	281	3.6	11
						15-9	93	143	291	3.6	15.2
15-10	100	137	264	3.9	14.2
						15-11	101	142	298	3.8	11.9
15-12	94	144	286	4.2	12.5
						15-13	86	135	276	3.8	8.6

Table 17.3 (40% combination)

Polyvalent alcohol	Peculiar smell	The emulsifiable paste time (second)	The cup top swells the time (second)	Always swell the time (second)	Density (pound/foot 3)	(%) rebounds	25% IFD (ox/323 centimetre 2)	65% IFD (ox/323 centimetre 2)	The supporting factor
										15-1	-	14	58	122	1.5	32	25	52	2.04
15-2	-	15	63	124	1.5	33	23	43	1.91
										15-3	-	12	61	122	1.4	32	21	41	1.95
15-4	-	14	57	109	1.5	33	26	48	1.87
										15-5	+	17	57	102	1.5	33	24	45	1.92
15-6	+	16	57	102	1.5	33	25	46	1.81
										15-7	+	17	57	103	1.5	33	27	48	1.82
15-8	+	16	60	119	1.6	33	24	48	1.96
										15-9	+	15	56	110	1.5	32	25	47	1.91
15-10	+	15	53	109	1.5	32	24	46	1.91
										15-11	+	15	55	104	1.5	33	22	42	1.89
15-12	++	14	52	100	1.5	33	24	44	1.87
										15-13	-	15	63	124	1.5	33	23	43	1.91

Table 17.3 (continuing)

Polyvalent alcohol	Tensile strength (kPa)	Elongation (%)	Tearing toughness (ox/rice)	Air-flow (foot 3/ minute)	90%CS (% loss)
						15-1	77		215	2.9	13.9
15-2	65	91	201	2.8	9.5
						15-3	57	81	189	2.9	9.6
15-4	87	122	215	3.2	11.3
						15-5	82	108	225	3.0	26.7
15-6	78	104	200	2.8	20.2
						15-7	86	111	218	2.9	39.1
15-8	81	104	194	3.0	11.8
						15-9	82	113	223	2.9	13.2
15-10	76	91	184	3.0	12.3
						15-11	77	100	211	3.1	12.0
15-12	76	101	208	2.6	12.0
						15-13	65	91	201	2.8	9.5

Table 17.4 (50% combination)

Polyvalent alcohol	Peculiar smell	The emulsifiable paste time (second)	The cup top swells the time (second)	Always swell the time (second)	Density (pound/foot 3)	Resilience (%)	25% IFD (ox/323 centimetre 2)	65% IFD (ox/323 centimetre 2)	The supporting factor
										15-1	-	13	67	140	--	--	--	--	--
15-2	-	16	72	136	--	--	--	--	--
										15～3	Do not record	16	71	141	--	--	--	--	--
15-4	-	16	65	125	1.6	30	23	49	2.12
										15-5	+	18	66	117	1.5	31	23	43	1.90
15-6	+	18	65	131	1.6	30	26	51	1.98
										15-7	+	17	63	111	1.5	31	28	52	1.88
15-8	+	16	68	130	--	--	--	--	--
										15-9	+	16	58	111	1.5	31	23	46	2.02
15-10	Do not record	16	60	--	--	--	--	--	--
										15-11	Do not record	16	52	--	--	--	--	--	--
15-12	++	15	58	121	1.4	31	19	41	2.19
										15-13	-	16	72	136	--	--	--	--	--
16-1	++	15	62	117	1.5	31	22	45	2.01
										16-2	++	15	63	119	1.5	32	22	46	2.10
16-3	++	15	62	116	1.5	31	23	46	2.05

Table 17.4 (continuing)

Polyvalent alcohol	Tensile strength (kPa)	Elongation (%)	Tearing toughness (ox/rice)	Air-flow (foot 3/ minute)	90%CS (% loss)
						15-1	--	--	--	--	--
15-2	--	--	--	--	--
						15-3	--	--	--	--	--
15-4	64	83	156	2.4	13.6
						15-5	79	93	163	2.9	18.8
15-6	65	81	131	2.4	14.8
						15-7	77	88	169	2.2	56.4
15-8	--	--	--	--	--
						15-9	64	81	168	2.3	15.3
15-10	--	--	--	--	--
						15-11	--	--	--	--	--
15-12	52	70	--	2.1	14.5
						15-13	--	--	--	--	--
16-1	70	84	156	2.2	15.8
						16-2	65	82	158	2.4	15.6
16-3	66	79	159	2.3	14.9

Embodiment 18

Use has prepared flexible sheet strand foam block available from the full-scale conventional plate foams lining of Mike Si Fomu.This foam block uses the listed formulation of table 18.1-18.4.According to technology described below each foam block is carried out the crust density measurement.

Table 18.1-prescription 1

	Prescription 1 (reference)	Prescription 1 (25%)
			Foam properties
Density (pound/foot 3)	1.8	1.8
			Hardness (pound)	28	28
Cal 117	Be	Be
			Component	(PPH)	(PPH)
F-3022	93.5	68.5
			Oligomeric polyols	0	25.0
Filler	3.25	3.25
			Trimeric cyanamide	6.5	6.5
P-945	6.5	6.5
			TDI	45.42	45.42
Water	3.34	3.34
			L-650	0.97	0.97
T-9	0.24	0.24
			TD-33	0.04	0.04
RC-6366	0.29	0.29
			Acetone	2.45	2.45
CP-2	13.0	13.0

Table 18.2-prescription 2

	Prescription 2 (references)	Prescription 2 (15%)	Prescription 2 (25%)
				Foam properties
Density (pound/foot 3)	1.45	1.45	1.45
				Hardness (pound)	31	31	31
Cal 117 preparations	Not	Not	Not
				Component	(PPH)	(PPH)	(PPH)
F-3020	93.95	78.95	62.45
				Oligomeric polyols	0	15.0	25.0
Filler	6	6	6
				Trimeric cyanamide	3.25	3.25	3.25
P-945	3.25	3.25	3.25
				B-2130	2.80	2.80	2.80
TDI	51.10	51.18	51.27
				Water	3.93	3.93	3.93
L-5770	0.96	0.96	0.96
				K-29	0.23	0.23	0.23
RC-6366	0.19	0.19	0.19
				Acetone	2.60	2.60	2.60

Table 18.3-prescription 3

Component	Prescription 3-reference	Prescription 3 (25%)
			Foam properties
Density (pound/foot 3)	1.8	1.8
			Hardness (pound)	25	25
Cal 117 preparations	Be	Be
			Component	(PPH)	(PPH)
F-3022	94.0	69.0
			Oligomeric polyols	0	25.0
Filler	4.5	4.5
			Trimeric cyanamide	6.0	6.0
P-945	6.0	6.0
			TDI	40.76	41.93
Water	3.04	3.04
			L-650	1.0	1.0
T-9	0.32	0.32
			TD-33	0.06	0.06
RC-6366	0.245	0.265
			Acetone	4.40	4.40
CP-2	11.5	11.5

Table 18.4: prescription 4

	Prescription 4 (references)	Prescription 4 (25%)
			Foam properties
Density (pound/foot 3)	1.45	1.45
			Hardness (pound)	46	46
Cal 117 preparations	Be	Be
			Component	(PPH)	(PPH)
F-3020	78.5	53.5
			Oligomeric polyols	0	25.0
P-4600	16	16
			Trimeric cyanamide	5.5	5.5
P-945	5.5	5.5
			TDI	62.25	63.5
Water	4.79	4.79
			L-650	0.9	0.9
T-9	0.185	0.185
			TD-33	0.026	0.026
RC-6366	0.175	0.175
			FR-550	12	12

The crust density measurement:

The representative plate foam block that has the full-scale conventional plate foams lining preparation of table 18.1-18.4 listed polyurethane formulations from utilization downcuts 12 " x12 " x～1 " crust small pieces (promptly being positioned at the foams of block outside), measure the density of crust.Measure and note height, width and the weight of each sample.With slide calliper rule to the thickness measurement of each sample 5-9 time.The measuring position is distributed in the representational mean value position of sample.The position of measuring on each sample is consistent.Use surface-area, mean thickness and quality measured values to calculate the mean density of each foams crust sample.Lower mean density interpret sample has more low-density crust.This shows to have thin crust, causes plate foams crust to have higher main foams productive rate.The results are shown in table 18.5.

Table 18.5

The embodiment numbering	Prescription	Density (pound/foot 3)	The crust position
				Comparative example 18-A	Prescription 1 (reference)	3.36	The top
Embodiment 18-1	Prescription 1 (25%)	2.60	The top
				Comparative example 18-B	Prescription 1 (reference)	3.26	The bottom
Embodiment 18-2	Prescription 1 (25%)	3.14	The bottom
				Embodiment 18-3	Prescription 1 (25%)	3.36	The bottom
Embodiment 18-4	Prescription 1 (25%)	3.10	The bottom
				Embodiment 18-5	Prescription 1 (25%)	2.93	The bottom
Comparative example 18-C	Prescription 2 (references)	3.94	The bottom
				Embodiment 18-6	Prescription 2 (15%)	2.99	The bottom
Embodiment 18-7	Prescription 2 (15%)	2.91	The bottom
				Embodiment 18-8	Prescription 2 (25%)	3.04	The bottom
Embodiment 18-9	Prescription 2 (25%)	2.95	The bottom
				Embodiment 18-10	Prescription 2 (25%)	3.10	The bottom
Embodiment 18-11	Prescription 2 (25%)	2.93	The bottom
				Comparative example 18-D	Prescription 3 (references)	3.43	The top
Embodiment 18-12	Prescription 3 (25%)	3.08	The top
				Embodiment 18-13	Prescription 3 (25%)	2.67	The top
Embodiment 18-14	Prescription 3 (25%)	2.80	The top
				Embodiment 18-15	Prescription 3 (25%)	2.34	The top
Comparative example 18-E	Prescription 3 (references)	2.98	The bottom
				Embodiment 18-16	Prescription 3 (25%)	2.69	The bottom
Comparative example 18-F	Prescription 4 (references)	2.69	The top
				Embodiment 18-17	Prescription 4 (25%)	2.59	The top

Embodiment 19 IFD and density distribution

Use full-size board strand foam body lining to prepare the block of 1.45/31 step strand foam body.The prescription of these foams is listed in table 18.2.(be of a size of 15 " * 15 " * 4 ") from 11 test blocks of cross section cutting-out of each block.To test block numbering and mark, be designated as " M " (in the middle of expression block) or " S " (expression block side).Each test block is tested, to measure 25% and 65%IFD and density.Use ASTM test procedure D3574, difference is that this test is carried out after block prepares 24 hours.The results are shown in table 19.1.

Table 19.1

Prescription 2	Reference	15％	15％	15％	25％	25％	25％	25％	25％	15％
											Character	Middle	Middle	Side	Side	Middle	Side	Side	Middle	Side	Side
25％IFD	32.49	30.76	30.65	30.92	29.52	28.75	28.68	29.60	29.08	29.21
											65％IFD	59.87	57.78	57.60	57.70	54.70	54.00	54.70	57.10	55.10	57.10
25％RT	22.05	20.90	21.20	21.20	19.30	19.10	19.10	19.50	19.10	19.40
IFD distributes	4.20	2.67	1.96	1.67	3.15	2.08	2.27	2.82	1.45	1.67
											The average Ov-of S-is whole		2.10		1.82	2.50		2.18	1.98		1.56
Density	1.46	1.43	1.42	1.43	1.39	1.39	1.39	1.40	1.40	1.40
Density distribution	0.09	0.06	0.06	0.05	0.05	0.06	0.03	0.05	0.02	0.05
Modulus	1.84	1.84	1.80	1.81	1.82	1.80	1.82	1.92	1.84	1.90
Air-flow	5.2	4.8	4.8	4.8	5.0	4.9	5.1	4.9	5.1	4.9
Resilience	46	41	40	42	38	39	40	40	39	40
											Lag behind	67.0	66.3	66.5	66.7	64.1	63.6	63.7	65.4	63.7	64.6

Embodiment 20

Use full-size board strand foam body lining to prepare the block of flexible sheet strand foam body.The prescription of foams is listed in table 18.1-18.4.Use the 5%IFD of ASTM D3574 (improvement is used for 5% recessed pressure) test foams.The results are shown in table 20.2-20.4.

Table 20.2

	Prescription 2 (15%)	Prescription 2 (15%)	Prescription 2 (25%)	Prescription 2 (25%)	Prescription 2 (25%)	Prescription 2-reference	Prescription 2 (25%)	Prescription 2-reference
									5％ IFD	20.09	18.93	18.54	18.08	18.60	20.79	17.82	19.37
	21.04	20.35	20.05	19.71	19.90	21.40	19.55	21.77
										21.13	20.68	20.28	19.84	20.04	22.00	19.87	21.81
	21.04	20.93	20.27	20.07	19.90	22.24	19.60	22.13
										21.08	20.61	19.97	19.98	19.81	22.09	19.30	22.00
	20.71	20.49	20.05	19.99	19.76	22.09	19.30	22.31
										20.63	20.50	19.92	20.08	19.68	21.86	19.38	21.90
	20.38	20.68	20.13	20.22	19.80	21.67	19.45	22.04
										20.52	20.87	20.04	20.03	19.99	21.72	19.78	22.07
	19.55	20.05	19.92	19.96	19.77	21.75	19.61	21.87
										--	--	18.61	18.54	18.98	21.02	18.72	20.66
5% IFD is average	20.62	20.41	19.80	19.68	19.66	21.69	19.31	21.63
									5% IFD distributes	1.58	2.00	1.74	2.14	1.44	1.45	2.05	2.94

The average 5%IFD=19.91 of prescription 2

The average 5%IFD=21.66 of prescription 2 (references)

Change %=8.08%

Table 20.3

	Prescription 4 (25%)	Prescription 4 (25%)	Prescription 4 (25%)	Prescription 4-reference	Prescription 3-(25%)	Prescription 3-(25%)	3 references of filling a prescription	Prescription 3-reference
									5％ IFD	27.56	29.13	27.02	28.68	16.33	16.08	16.40	16.18
	27.68	29.52	27.96	29.46	17.31	16.83	17.15	17.08
										29.50	31.03	29.91	31.38	17.39	17.06	17.46	17.42
	30.79	31.98	31.06	31.76	17.38	17.16	17.34	17.43
										31.34	32.95	31.21	31.54	17.22	16.97	17.28	17.33
	30.94	32.36	31.65	31.76	17.01	16.98	17.22	17.27
										30.21	32.24	30.82	31.21	16.75	16.60	17.09	17.17
	29.81	32.47	30.68	31.69	16.55	16.13	16.68	16.78
										29.19	31.82	29.82	31.77	15.79	15.66	16.48	16.27
	28.20	30.53	28.88	31.09	15.09	14.87	15.03	15.25
										26.80	28.41	27.46	28.80
5% IIFD is average	29.28	31.13	29.68	30.83	16.68	16.44	16.81	16.82
									5% IFD distributes	4.53	4.54	4.63	3.09	2.30	2.29	2.43	2.18

The average 5%IFD=29.84 of prescription 4

The average 5%IFD=30.98 of prescription 4 (references)

Change %=4.85%

The average 5%IFD=16.56 of prescription 3

The average 5%IFD=16.81 of prescription 3-reference

Change %=1.52%

Table 20.4

The average 5%IFD=18.63 of prescription 1

The average 5%IFD=19.76 of prescription 1-reference

Change %=5.71%

Embodiment 21: the supporting factor

The listed polyvalent alcohol preparation of use table 21.2 has the flexible plate urethane foam of the listed prescription of table 21.1.According to ASTM D3574 the foam sample that makes is tested, 25%IFD and 65%IFD numerical value are provided.The supporting factor by 25% and 65%IFD calculate, list in table 21.3.

Table 21.1

Component	30％ (PPH)	40％ (PPH)	50％ (PPH)
				The 3000Mw triol	70	60	50
Oligomeric polyols (seeing Table 21.2)	30	40	50
				Water	4	4	4
TDI	105 indexes *	105 indexes *	105 indexes *
				Tensio-active agent	1	1	1
BL-11 (amine catalyst)	0.16	0.16	0.16
				K-29 (stannous octoate)	0.22	0.22	0.22

^*The consumption of TDI is based on the hydroxyl value of whole water and polyvalent alcohol and calculates, and 105 index is provided.

Table 21.2

Polyvalent alcohol	The OH value	Acid number	Water (%)	Mn (VPO) (gram/mole)	Fn (VPO)	Mn (LS) (gram/mole)	Mw (LS) (gram/mole)	Mw/Mn
									21-1	55.63	0.30	0.03	1695	1.68	1611	6928	4.30
21-2	58.81	0.28	0.04	1784	1.87	1567	9294	5.93
									21-3	62.56	0.44	0.09	1844	2.06	3206	32180	10.04
21-4	63.23	0.44	0.08	1730	1.95	2887	26530	9.19
									21-5	59.61	0.42	0.09	1664	1.77	2663	25570	9.60
21-6	58.97	0.43	0.05	1664	1.75	3300	42710	13.00
									21-7	61.18	0.46	0.05	1822	1.99	3916	37820	10.59
21-8	65.85	0.43	0.07	1931	2.27	1864	11100	6.60
									21-9	62.07	0.42	0.07	1744	1.93	3662	43920	12.00
21-10	65.12	0.43	0.06	1889	2.19	4502	51880	11.52
									21-11	64.76	0.47	0.06	1981	2.29	1739	13110	7.54
21-12	63.51	0.32	0.06	1691	1.91	1760	6649	3.78
									21-13	55.81	0.26	0.07	1897	1.89	1501	8251	5.50
21-14	54.50	0.25	0.05	1971	1.91	1433	7763	5.42
									21-15	59.52	0.30	0.07	1864	1.98	1674	8345	4.98
21-16	59.28	0.32	0.05	1980	2.09	1670	12130	7.27
									21-17	60.94	0.22	0.05	1857	2.02	1623	11440	7.05
21～18	57.99	0.27	0.05	1704	1.76	1615	8055	4.99
									21-19	56.91	0.30	0.04	1596	1.62	1442	7412	5.14
21-20	56.43	0.26	0.04	1670	1.68	1512	7799	5.13
									21-21	60.18	0.42	0.05	1828	1.96	1405	8373	5.96
21-22	57.45	0.34	0.05	1728	1.77	1710	8626	5.04

Table 21.2 (continuing)

Polyvalent alcohol	g’M	Viscosity (handkerchief second).	PV (％)	Monomer (GPC)	Dimer	Tripolymer	The tetramer+	EOC (％)	Oligopolymer (weight %)
										21-1	1.27	3.28	1.5	43.9	11.7	7.9	36.5	4.38	56.1
21-2	1.11	4.73	1.9	39.9	11.2	7.3	41.6	4.21	60.1
										21-3	0.53	4.65	3.9	41.7	11.5	7.5	39.3	4.22	58.3
21-4	0.58	5.42	2.5	39.8	11.7	7.7	40.8	4.13	60.2
										21-5	0.52	4.03	2.7	43.3	11.9	7.6	37.2	4.31	56.7
21-6	0.37	4.99	2.7	45.1	11.5	7.4	35.4	4.18	54.9
										21-7	0.45	6.18	2.2	38.9	11.2	7.3	42.4	3.98	61.1
21-8	1.01	4.03	2.7	39.0	11.5	7.4	42.1	4.20	61.0
										21-9	0.39	4.94	2.8	41.8	11.2	7.4	39.6	4.03	58.2
21-10	0.37	7.59	3.5	38.6	10.6	6.8	44.0	4.05	61.4
										21-11	0.93	6.56	3.3	37.8	11.3	7.0	43.9	3.96	62.2
21-12	1.37	3.41	2.2	43.8	12.2	8.1	35.9	4.08	56.2
										21-13	1.49	3.33	2.3	43.7	10.7	6.7	38.9	4.27	56.4
21-14	1.26	3.13	2.5	43.7	11.1	7.3	37.9	4.46	56.3
										21-15	1.17	2.95	2.2	41.4	11.4	7.5	39.7	4.49	58.6
21-16	0.98	5.25	2.3	40.2	10.5	6.8	42.4	4.39	59.8
										21-17	1.03	5.22	2.0	40.1	10.9	7.2	41.8	4.14	59.9
21-18	1.24	3.73	1.9	42.3	11.0	7.73	39.0	4.37	57.7
										21-19	1.22	3.51	1.7	44.2	11.0	7.44	37.9	4.37	55.8
21-20	1.25	3.46	2.0	43.8	10.8	7.12	38.3	4.40	56.2
										21-21	1.25	4.00	2.5	41.2	11.4	7.5	39.8	4.25	58.8
21-22	1.26	3.57	2.0	42.3	11.2	7.5	39.0	4.33	57.7

Table 21.3:30%, the supporting factor of 40% and 50% binding capacity

Sample (polyvalent alcohol numbering)	30% o'clock the supporting factor	40% o'clock the supporting factor	50% o'clock the supporting factor
				21-1	1.86	1.89	--
21-2	1.81	1.865	2.19
				21-3	1.83	1.91	--
21-4	1.81	1.98	1.98
				21-5	1.83	1.94	--
21-6	1.82	1.815	--
				21-7	1.76	1.985	1.99
21-8	1.96	2.015	2.02
				21-9	1.79	1.865	--
21-10	1.80	2.15	2.15
				21-11	1.80	2.075	2.08
21-12	1.85	1.945	1.95
				21-13	1.84	1.86	2.18
21-14	1.77	1.85	--
				21-15	1.82	1.99	1.99
21-16	1.80	1.92	1.95
				21-17	1.79	1.9	1.95
21-18	1.80	1.91	2.14
				21-19	1.82	1.84	2.06
21-20	1.845	1.93	2.13
				21-21	1.82	1.85	2.03
21-22	1.84	1.90	2.19
				On average.	1.818	1.927	2.059

Embodiment 22: flame retardant resistance

The plate foam sample of preparation is according to Technical Bulletin 117 in embodiment 18, " to being used to requirement, test procedure and the equipment (Requirements, Test Procedure and Apparatus for Testing the Flame Retardanceof Resilient Filling Materials Used in Upholstered Furniture) with the flame retardant resistance test of the elastic filling material of the addition polymerization of cushion " (in March, 2000) measures flame retardant resistance.The results are shown in table 22.1.

Table 22.1

	Prescription 4-reference	Prescription 4 (25%)	Prescription 3-reference	Prescription 3 (25%)	Prescription 1-reference	Prescription 1 (25%)
							% (on average) glows	99.3	99.3	99.2	98.2	83.6	94.9
Carbonization length (on average)	1.58	1.58	1.88	1.62	1.44	1.34
							Aging carbonization length (on average)	1.54	1.54	1.82	1.64	1.26	0.96

Embodiment 23

Oligomeric polyols carries out fractionation by DPC column operation repeatedly.For each fractionation, use the OH group in the phenyl isocyanate mark cut.Measure the ultraviolet absorptivity of each cut then, to measure hydroxy radical content.By comparing, measure the hydroxyl value and the number average hydroxy functionality (Fn) of each cut with standard specimen.The results are shown in table 23.1.

Table 23.1

Embodiment 24

Analysis has in the oligomeric polyols of feature shown in the table 24.1 whether have lipid oxidation product hexanal, aldehyde C-9 and the capraldehyde that produces peculiar smell.Analytical technology is utilized solid phase micro extraction, carries out gas-chromatography and flame ion then and detects, and to measure the content of oxidation products in the oligomeric polyols, unit is ppm.Use external standard to set up the calibration curve of hexanal, aldehyde C-9 and capraldehyde.The analytical results of the oligomeric polyols of his-and-hers watches 24.1 is listed in table 24.2.

Table 24.1

Character	Numerical value
		Hydroxyl value	57.6
Monomer (%)	41.6
		Dimer (%)	11.5
Tripolymer (%)	7.3
		Four poly-+(%)	39.6
Total oligomeric content (%)	58.4
		Viscosity (handkerchief second)	3.88

Table 24.2

Compound	The amount of compound (ppm)
		Hexanal	10.40
Aldehyde C-9	13.78
		Capraldehyde	1.17
Total amount	25.34

All publications and patent that this paper relates to all are incorporated into herein.Publication disclosed herein and patent all only provide its content.Content wherein can not be interpreted as that all the inventor haves no right the date of any publication and/or patent (comprising any publication and/or patent that this paper quotes) is shifted to an earlier date.

Implement the present invention described herein by understanding this specification sheets or passing through, other embodiment of the present invention is apparent to those skilled in the art.Those skilled in the art can carry out various omissions, improvement and change to principle described herein and embodiment under the prerequisite of true scope of the present invention that does not deviate from the appended claims explanation and spirit.

Claims (84)

1. urethane foam, it comprises the reaction product of following component:

(a) polyisocyanates;

(b) comprise the composition of reactive hydrogen, it comprises oligomeric polyols, and the hydroxyl value of described oligomeric polyols is about 45-65 milligram KOH/ gram, and the number average hydroxy functionality is approximately less than 2.7, comprises to approximate or greater than the oligopolymer of 40 weight %.

2. urethane foam as claimed in claim 1 is characterized in that, described oligomeric polyols comprises the oligopolymer of about 55-65 weight %.

3. urethane foam as claimed in claim 1 is characterized in that, described oligomeric polyols comprises the dimer of about 8-12 weight %, the tripolymer of about 5-10 weight %, and approximate or greater than the more high-grade oligopolymer of 35 weight %.

4. urethane foam as claimed in claim 1 is characterized in that, the number average hydroxy functionality of described oligomeric polyols is approximately less than 2.5.

5. urethane foam as claimed in claim 1 is characterized in that, the number average hydroxy functionality of described oligomeric polyols is approximately less than 2.0.

6. urethane foam as claimed in claim 1 is characterized in that, the acid number of described oligomeric polyols is approximately less than 1.0 milligrams of KOH/ grams.

7. urethane foam as claimed in claim 1 is characterized in that, the number-average molecular weight of described oligomeric polyols (Mn) is about 1000-5000 gram/mole.

8. urethane foam as claimed in claim 1 is characterized in that, the weight-average molecular weight of described oligomeric polyols (Mw) is about 5000-50,000 gram/mole.

9. urethane foam as claimed in claim 1 is characterized in that, described oligomeric polyols is about 0.5-10 handkerchief second 25 ℃ viscosity.

10. urethane foam as claimed in claim 1 is characterized in that, the residual epoxy base oxygen level of described oligomeric polyols is about 0.5-5.0%.

11. urethane foam as claimed in claim 1 is characterized in that, the epoxy oxygen content of described oligomeric polyols is about 0.01-5.0%.

12. urethane foam as claimed in claim 1 is characterized in that, described oligomeric polyols is prepared by epoxidised natural oil.

13. urethane foam as claimed in claim 12, it is characterized in that described natural oil is selected from soybean oil, Thistle oil, Toenol 1140, Semen Maydis oil, Trisun Oil R 80, sweet oil, Tower rape oil, sesame oil, Oleum Gossypii semen, palm base oil, rapeseed oil, tung oil, peanut oil, fish oil, lard, butter and their combination.

14. urethane foam as claimed in claim 13 is characterized in that, described natural oil comprises soybean oil.

15. urethane foam as claimed in claim 13 is characterized in that, described palm base oil comprises palm olein.

16. urethane foam as claimed in claim 1 is characterized in that, the described composition that comprises reactive hydrogen also comprises the polyvalent alcohol that is derived from oil.

17. urethane foam as claimed in claim 16 is characterized in that, the described polyvalent alcohol that is derived from oil is a triol.

18. urethane foam as claimed in claim 16 is characterized in that, the described molecular weight that is derived from the triol of oil is about 3000 gram/moles.

19. urethane foam as claimed in claim 16 is characterized in that, the described composition that comprises reactive hydrogen comprises the polyvalent alcohol that is derived from oil of about 45-90 weight %, and the oligomeric polyols of about 10-60 weight %.

20. urethane foam as claimed in claim 1 is characterized in that, described polyisocyanates be tolylene diisocyanate, 4,4 '-diphenylmethanediisocyanate, polymeric 4,4 '-ditan, or their mixture.

21. urethane foam as claimed in claim 1 is characterized in that, the described composition that comprises reactive hydrogen comprises the oligomeric polyols of about 10-50 weight %.

22. urethane foam as claimed in claim 1 is characterized in that, described urethane foam is the plate foams.

23. urethane foam as claimed in claim 22 is characterized in that, described urethane foam is the plate foams.

24. urethane foam as claimed in claim 1 is characterized in that, described urethane foam is the foams of molding.

25. urethane foam as claimed in claim 1 is characterized in that, the density of described urethane foam is about 0.5-5.0 pound/foot ³

26. urethane foam as claimed in claim 1 is characterized in that, the described composition that comprises reactive hydrogen comprises the oligomeric polyols of 10PPH at least, is about 1.5 pounds/foot in density ³, 25%IFD is about 23 Ns/323 centimetres ²Urethane foam on record, the tensile strength of described urethane foam is equal to or less than the numerical value that is calculated by following formula (I) with respect to the percentage ratio that reduces of reference preparation:

The % tensile strength reduces=and 0.89 * (PPH of oligomeric polyols)

27. urethane foam as claimed in claim 26 is characterized in that, formula (I) is:

The % tensile strength reduces=and 1.0 * (PPH of oligomeric polyols)

(I)

28. urethane foam as claimed in claim 1 is characterized in that, the described composition that comprises reactive hydrogen comprises the oligomeric polyols of 10PPH at least, is about 1.5 pounds/foot in density ³, 25%IFD is centimetre ²Urethane foam on record, the tear strength of described urethane foam is equal to or less than the numerical value that is calculated by following formula (II) with respect to the percentage ratio that reduces of reference preparation:

The % tear strength reduces=and 1.40 * (PPH of oligomeric polyols)

(II)

29. urethane foam as claimed in claim 1 is characterized in that, the described composition that comprises reactive hydrogen comprises the oligomeric polyols of 10PPH at least, is about 1.5 pounds/foot in density ³, 25%IFD is about 23 Ns/323 centimetres ²Urethane foam on record, the percentage ratio that reduces of the elongation of described urethane foam is equal to or less than the numerical value that is calculated by following formula (III):

% elongation reduces=and 1.36 * (PPH of oligomeric polyols)

(III)

30. urethane foam as claimed in claim 1, it is characterized in that, described urethane foam is the form of plate foam block, this block has the high-density exodermis that accounts for outside 1 inch of described foams, and the density of described exodermis is littler by about 20% than the high-density exodermis of the polyurethane foam block that comprises reference preparation at least.

31. urethane foam as claimed in claim 30 is characterized in that, the density of described plate urethane foam is littler about 0.25 pound/foot than the density of the plate foams that comprise reference preparation ³Or it is more.

32. urethane foam as claimed in claim 1 is characterized in that, compares with the urethane foam that comprises reference preparation, described urethane foam has the supporting factor of increase.

33. urethane foam as claimed in claim 32 is characterized in that, the size of the described supporting factor is about 1.7-2.2.

34. urethane foam as claimed in claim 1 is characterized in that, compares with the urethane foam that comprises reference preparation, described urethane foam has improved feel.

35. urethane foam as claimed in claim 34 is characterized in that, compares with reference preparation, the 5%IFD of described urethane foam has reduced about 2% or more.

36. urethane foam as claimed in claim 34 is characterized in that, compares with reference preparation, the 5%IFD of urethane foam has reduced about 5% or more.

37. urethane foam as claimed in claim 1 is characterized in that, compares with the urethane foam that comprises reference preparation, described urethane foam has flame retardant resistance.

38. urethane foam as claimed in claim 37 is characterized in that, compares with reference preparation, described urethane foam has the carbonization length that reduces.

39. urethane foam as claimed in claim 1 is characterized in that, compares with the urethane foam that comprises reference preparation, described urethane foam has improved water-repellancy.

40. urethane foam as claimed in claim 1 is characterized in that, compares with the urethane foam that comprises reference preparation, described urethane foam has the 5%IFD that reduces.

41. urethane foam as claimed in claim 1 is characterized in that, compares with the urethane foam that comprises reference preparation, described urethane foam has 5%IFD and the basic 25%IFD that equates that reduces.

42. urethane foam as claimed in claim 1 is characterized in that, described urethane foam is the plate foams.

43. urethane foam as claimed in claim 1 is characterized in that, described urethane foam is the foams of molding.

44. urethane foam as claimed in claim 1 is characterized in that, described oligomeric polyols is to prepare by the method that may further comprise the steps:

(a) provide epoxidised natural oil;

(b) described epoxidised natural oil is mixed with the ring opening catalyst of the pure and mild catalytic amount of open loop, form described oligomeric polyols.

45. urethane foam as claimed in claim 44 is characterized in that, described open loop alcohol is monohydroxy-alcohol.

46. urethane foam as claimed in claim 45 is characterized in that, described monohydroxy-alcohol is a methyl alcohol.

47. urethane foam as claimed in claim 44 is characterized in that, described open loop alcohol is polyvalent alcohol.

48. urethane foam as claimed in claim 47 is characterized in that, described polyvalent alcohol is ethylene glycol, propylene glycol, 1, ammediol, butyleneglycol, 1,4-butyleneglycol, 1,5-pentanediol, 1,6-hexylene glycol, polyoxyethylene glycol, polypropylene glycol, their mixture.

49. urethane foam as claimed in claim 1 is characterized in that, described oligomeric polyols comprises the hexanal that is approximately equal to or less than 30ppm.

50. urethane foam as claimed in claim 1 is characterized in that, described oligomeric polyols comprises the aldehyde C-9 that is approximately equal to or less than 30ppm.

51. urethane foam as claimed in claim 1 is characterized in that, described oligomeric polyols comprises the capraldehyde that is approximately equal to or less than 30ppm.

52. urethane foam as claimed in claim 1 is characterized in that, described oligomeric polyols comprises hexanal, aldehyde C-9 and the capraldehyde that is approximately equal to or less than 70ppm altogether.

53. a urethane foam, it comprises the reaction product of following component:

Polyisocyanates;

The composition that comprises reactive hydrogen, it comprises the oligomeric polyols of 10PPH at least, and the number average hydroxy functionality of this polyvalent alcohol is approximately less than 2.7, and density is about 1.5 pounds/foot ³The tensile strength of urethane foam be at least about 85 kPas.

54. urethane foam as claimed in claim 53 is characterized in that, the elongation of described foams is at least about 90%.

55. urethane foam as claimed in claim 53 is characterized in that, the tear strength of described foams is at least about 150 Ns/rice.

56. urethane foam as claimed in claim 53 is characterized in that, 90% compression permanentset of described foams is approximately less than 20%.

57. urethane foam as claimed in claim 53 is characterized in that, described foams have the slight peculiar smell of industrial foams production institute's acceptable.

58. urethane foam as claimed in claim 53 is characterized in that, described oligomeric polyols is prepared by epoxidation natural oil.

59. urethane foam as claimed in claim 58, it is characterized in that described natural oil is selected from oil, Thistle oil, Toenol 1140, Semen Maydis oil, Trisun Oil R 80, sweet oil, Tower rape oil, sesame oil, Oleum Gossypii semen, palm base oil, rapeseed oil, tung oil, peanut oil, fish oil, lard, butter and their combination.

60. urethane foam as claimed in claim 59 is characterized in that, described natural oil is soybean oil.

61. urethane foam as claimed in claim 59 is characterized in that, described palm base oil comprises palm olein.

62. urethane foam as claimed in claim 53 is characterized in that, described polyisocyanates comprise tolylene diisocyanate, 4,4 '-diphenylmethanediisocyanate, polymeric 4,4 '-diphenylmethanediisocyanate, or their mixture.

63. urethane foam as claimed in claim 53 is characterized in that, the number average hydroxy functionality that described polyhydric alcohol composition comprises 20PPH at least is approximately less than 2.5 oligomeric polyols.

64. urethane foam as claimed in claim 53 is characterized in that, the hydroxyl value of described oligomeric polyols is about 45-65 milligram KOH/ gram.

65. urethane foam as claimed in claim 53 is characterized in that, the epoxy oxygen content of described oligomeric polyols is about 0.5-5.0%.

66. urethane foam as claimed in claim 53 is characterized in that, the method preparation of described oligomeric polyols by may further comprise the steps:

(a) provide epoxidised natural oil;

(b) described epoxidised natural oil is mixed with the ring opening catalyst of the pure and mild catalytic amount of open loop, form described oligomeric polyols.

67., it is characterized in that described epoxidised natural oil is complete epoxidised vegetables oil as the described urethane foam of claim 66, the EOC of described oligomeric polyols is about 0.5-5.0%.

68. urethane foam as claimed in claim 53 is characterized in that, described foams are plate foams.

69., it is characterized in that described plate foams are flexible as the described urethane foam of claim 68.

70. urethane foam as claimed in claim 53 is characterized in that, described foams are foams of molding.

71. urethane foam as claimed in claim 53 is characterized in that, the peculiar smell of described foams is less than the peculiar smell of the urethane foam that comprises reference preparation.

72. urethane foam as claimed in claim 53 is characterized in that, compares with the urethane foam that comprises reference preparation, described foams have improved colour fastness.

73. urethane foam as claimed in claim 53 is characterized in that, described oligomeric polyols comprises the hexanal that is approximately equal to or less than 30ppm.

74. urethane foam as claimed in claim 53 is characterized in that, described oligomeric polyols comprises the aldehyde C-9 that is approximately equal to or less than 30ppm.

75. urethane foam as claimed in claim 53 is characterized in that, described oligomeric polyols comprises the capraldehyde that is approximately equal to or less than 30ppm.

76. urethane foam as claimed in claim 53 is characterized in that, described oligomeric polyols comprises hexanal, aldehyde C-9 and the capraldehyde that is approximately equal to or less than 70ppm.

77. urethane foam as claimed in claim 53 is characterized in that, described foams have the color that comprises specular reflection after 6 weeks of exposure under the situation that does not contain UV stabilizer, under envrionment conditions, it is characterized in that (L) value is at least 70 units.

78. urethane foam as claimed in claim 53 is characterized in that, described foams have the color that comprises specular reflection after 6 weeks of exposure under the situation that does not contain UV stabilizer, under envrionment conditions, it is characterized in that (L) value is at least 80 units.

79. a method for preparing the urethane foam goods of molding, this method comprises:

(a) polyisocyanates and the composition adding that comprises reactive hydrogen are had in the mould of predetermined shape, the described composition that comprises reactive hydrogen comprises oligomeric polyols, the hydroxyl value of this polyvalent alcohol is about 45-65 milligram KOH/ gram, the number average hydroxy functionality is approximately less than 2.7, also comprises to approximate or greater than the oligopolymer of 40 weight %;

(b) composition that makes described polyisocyanates and comprise reactive hydrogen in the presence of whipping agent is at the mould internal reaction, and preparation comprises the goods of urethane foam.

80. a method for preparing plate urethane foam goods, this method comprises:

(a) on the foams conveying assembly, in the presence of whipping agent, make polyisocyanates and the composition react that comprises reactive hydrogen, the flexible polyisocyanates foams of preparation plate form, described polyhydric alcohol composition comprises oligomeric polyols, the hydroxyl value of this polyvalent alcohol is about 45-65 milligram KOH/ gram, the number average hydroxy functionality is approximately less than 2.7, also comprises to approximate or greater than the oligopolymer of 40 weight %;

(b) described plate foams are formed, form described goods.

81. an oligomeric polyols, it comprises the hexanal that is approximately equal to or less than 30ppm.

82. an oligomeric polyols, it comprises the aldehyde C-9 that is approximately equal to or less than 30ppm.

83. an oligomeric polyols, it comprises the capraldehyde that is approximately equal to or less than 20ppm.

84. an oligomeric polyols, it comprises hexanal, aldehyde C-9 and the capraldehyde that is approximately equal to or less than 80ppm altogether.