CN1926164A - Flexible polyurethane foams prepared using modified vegetable oil-based polyols - Google Patents

Flexible polyurethane foams prepared using modified vegetable oil-based polyols Download PDF

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CN1926164A
CN1926164A CN 200480034513 CN200480034513A CN1926164A CN 1926164 A CN1926164 A CN 1926164A CN 200480034513 CN200480034513 CN 200480034513 CN 200480034513 A CN200480034513 A CN 200480034513A CN 1926164 A CN1926164 A CN 1926164A
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vegetable oil
based polyols
reaction mixture
oil
polyurethane foams
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R·赫林顿
J·马尔萨姆
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Cargill Inc
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Cargill Inc
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Abstract

A flexible polyurethane foam prepared by reacting, in the presence of a blowing agent, a polyisocyanate with an active hydrogen-containing composition that includes a modified vegetable oil-based polyol. The foams exhibit good load-bearing properties, relatively high sag factors, and/or good color retention upon exposure to light.

Description

Flexible polyurethane foams with the modified vegetable oil-based polyols preparation
Prioity claim
The application requires to enjoy the provisional application sequence number (SN) 60/507,298 that the title of submitting on September 30th, 2003 is " flexible polyurethane foams with good load-carrying properties " and the title of submitting on June 25th, 2004 is the right of priority of " with the flexible polyurethane foams of modified vegetable oil-based polyols preparation " U.S. Patent application sequence number (SN) 10/877834.These patent applications are incorporated into this paper by reference.
Technical field
The present invention relates to prepare flexible polyurethane foams.
Background technology
Flexible polyurethane foams is usually by petroleum base polyvalent alcohol or polyhydric alcohol composition and organic multiple isocyanate prepared in reaction in the presence of catalyzer, whipping agent and other optional components.Since generation nineteen sixty, flexible polyurethane foams provides damping, carrying and comfortable parts as in automobile, transportation means and other seat designs always.Be the various requirement of the variation of satisfying various seat designs, the manufacturer of commercialization flexible foam material must have can convenience and the technology that changes the hardness of the flexible foam material of making economically.
Hardness and carrying are that two terms that use are often exchanged in flexible foam material industry.Should understand the physical property that these two terms all relate to the identical weight support of flexible polyurethane foams.
Flexible polyurethane foams is accepted and the ability of support weight is normally defined its supporting capacity.According to standard method guide such as ASTM D 3574, Test B1 can carry out quantitatively this performance in (blunt pin) indentation force deflection (Indentation ForceDeflection) (IFD) is tested.
There are many kinds to change the method for foam materials hardness.Wherein the most frequently used method relates to the density that changes foam materials, isocyanate index, and/or the use of polyvalent alcohol functionality and copolymer polyols, and copolymer polyols is the most effective.Copolymer polyols is usually by forming as millions of polyether glycols that generally contain the carrier fluid of the rare nitrile molecule of vinylbenzene/third.The molecule of special additive and processing step are essential to preparing stable particle dispersion.In final polyurethane foamed material, these particulate effects of adding are as conventional filler, and are to regulate the hardness of flexible foam material or a kind of method easily of supporting capacity.
Though copolymer polyols can change the hardness of foam materials, there are many defectives in they.These defectives comprise the variation of the weight percentage of suspended solids, the viscosity variation of clean product and the colour-change of product.When using copolymer polyols in production environment, the variation of these characteristics causes the performance difference between every batch of product.In addition, using the industrial common issue with that runs into of copolymer polyols is the obstruction that is positioned at the strainer of foam production device key position.Strainer be used for catching normally transport with processing treatment in the refuse that produces.Even copolymer polyols is pointed out to have the particle of 1 predetermined micron granularity scope, any specific product transported also can stop up 100 microns even larger sized strainer usually.
Summary of the invention
Flexible polyurethane foams prepares by following mode, and polyisocyanates and the composition that contains active hydrogen (that is, comprise can with the composition of the reactant of the hydrogen atoms group of isocyanic ester radical reaction) be reacted in the presence of whipping agent.And the composition that contains active hydrogen comprises the vegetable oil-based polyols of modification.Herein, " vegetable oil-based polyols of modification " refers to the polyvalent alcohol that non-natural exists, and obtains polyvalent alcohol by the chemical structure of vegetables oil being handled to change vegetables oil.Preferably, two keys of relating to vegetables oil of described processing carry out modification.
The hydroxyl of the vegetable oil-based polyols of modification and isocyanate group chemical reaction form amino-formate bond.Therefore, the polyvalent alcohol Chemical bond is in polyether polyols with reduced unsaturation.Employing BVT reactivity test is estimated the level of response between hydroxyl and the isocyanate group, and this test will describe in detail below.Preferably, scheme according to the formulation of BVT reactivity test, the feature of polyvalent alcohol is, when it mixes with catalyzer and tolylene diisocyanate when forming reaction mixture, after forming reaction mixture, to measure 600 seconds the time, the viscosity of this reaction mixture is at least 5,000mPa.s (better be at least 10,000mPa.s, preferably be at least 20,000mPa.s).
These foam materialss provide many advantages.For example, in some embodiments, foam materials has good supporting capacity under relatively low polyvalent alcohol feeding quantity, show as the load efficiency numbers and (be generally at least 4 newton/part modified vegetable oil-based polyols, in some embodiment, be at least 7 or be at least the vegetable oil-based polyols of 10 newton/part modification).The load efficiency numbers, is used from the carrying data of 65% indentation force deflection and is calculated in method described in the WO 02/10247 according to Van Heumen etc.Preferably, the load efficiency numbers with the urethane made from the vegetable oil-based polyols of the alternative modification of equivalent copolymer polyols is the same high at least for the load efficiency numbers of foam materials.The hardness value of foam materials is greater than the hardness value of the contrast foam materials made from the composition that contains active hydrogen of the vegetable oil-based polyols that does not have modification preferably.
The composition that contains active hydrogen that is used for preparing foam materials comprises the combination of the vegetable oil-based polyols of modification and polyether-based polyvalent alcohol, polyester based polyvalent alcohol, or with the combination of polyether-based polyvalent alcohol and polyester based polyvalent alcohol combination, this composition has and helps the suitable low viscosity processing and handle.The viscosity that contains the composition of active hydrogen better is lower than the comparable viscosity that contains the active hydrogen composition that copolymer polyols has substituted modified vegetable oil-based polyols.
The composition that contains active hydrogen still is transparent, rather than opaque.For example, 1-49 weight part modified vegetable oil-based polyols and 99-51 weight part hydroxyl value form stable liquid (that is being transparent liquid to visual inspection) at 23 ℃ during less than the combination of 120 polyether-based polyvalent alcohol.In addition, the composition that contains active hydrogen more fortunately 23 ℃ keep stable for a long time.And this composition that contains active hydrogen does not better contain granularity greater than 0.1 micron particle.
The useful characteristic of another of foam materials is its colour fastness, the ability of the white when colour fastness can keep making when referring to be exposed to the light of envrionment conditions for a long time.Measure according to the scheme described in the following embodiment, preferably, foam materials is not containing under the ultra-violet stabilizer condition, be exposed to 6 weeks in the light of envrionment conditions, has the color that the mirror surface (reflectance specular) that characterizes with following value comprises: (L) value of at least 70 units, be not more than (b) value of 25 units, better be not more than (a) value of 4 units.In addition, foam materials during fabrication, its (L), (a) and (b) value better satisfy the value of enumerating, do not change substantially when these values are exposed to light under these conditions.Specifically be, (L) and (b) variation of value is not more than 14 units, and (a) variation of value is not more than 5 units.
If the smell of this foam materials is unlike the use copolymer polyols, rather than the foam materials of equal value of the vegetable oil-based polyols of modification preparation is better, the same with it at least good.In addition, this foam materials is environmentally friendly, because modified vegetable oil-based polyols derives from reproducible natural origin, rather than the oil source.
Details of one or more embodiments of the invention have been enumerated in accompanying drawing and the following description.By these descriptions and accompanying drawing and claims, other features, objects and advantages of the present invention will be conspicuous.
The accompanying drawing summary
Shown in Figure 1 is to petroleum base polyvalent alcohol (Arcol LHT-240) BVT reactivity test result's figure.
Shown in Figure 2 is soya-based polyvalent alcohol (SoyOyl to prior art GC5N and SoyOyl P38N) and petroleum base polyvalent alcohol (Arcol LHT-240) BVT reactivity test result's figure.
Shown in Figure 3 is to three kinds of modified vegetable oil-based polyols of the present invention (polyol E, polyvalent alcohol F and polyvalent alcohol G), the soya-based polyvalent alcohol (SoyOyl of two kinds of prior aries GC5N and SoyOyl P38N) and petroleum base polyvalent alcohol (Arcol LHT-240) BVT reactivity test result's figure.
Detailed Description Of The Invention
Flexible polyurethane foams can prepare by polyisocyanates and the reactive hydrogen composition react that contains that comprises the vegetable oil-based polyols of modification. The vegetable oil-based polyols that can comprise more than one modification in the said composition. In addition, composition can contain the polyalcohol of one or more non-plant oil bases, such as copolymer polyols, polyether-based polyalcohol, polyester-based polyalcohol etc., and dendritic macromole. Reaction can be carried out in the presence of blowing agent and optional catalyst.
The content that contains modified vegetable oil-based polyols in the reactive hydrogen composition can be selected according to the desired Performance Characteristics of foamed material. Generally, to the application of the bearing capacity that requires to improve foamed material, per 100 weight portions contain active hydrogen substance and contain 0.5-50 weight portion modified vegetable oil-based polyols in the composition. Per 100 weight portions in the useful composition of carrying purpose are contained active hydrogen substance contain the 1-40 weight portion, or the modified vegetable oil-based polyols of 2-30 weight portion.
Useful modified vegetable oil-based polyols comprises the polyalcohol that can prepare by the following method: form epoxidized vegetable oil (described epoxidized vegetable oil can prepare by the reaction of peroxy acid and vegetable oil), then epoxidized vegetable oil is mixed the formation polyalcohol with alcohol, catalytic amount fluoboric acid and optional water. What this polyalcohol contained all is secondary hydroxyl. All two keys can be by epoxidation basically in the vegetable oil. This preparation method's example is at the United States Patent (USP) 6,686,435,6,107 such as Petrovic etc., explanation in 433,6,573,354 and 6,433,121, and these patents are by with reference to being incorporated into this paper. Perhaps, epoxidation reaction can be carried out producing under the condition with residual double bonds.
These polyalcohols can directly be used for preparing polyurethane foamed material. Perhaps, these polyalcohols can react in the presence of fluoboric acid catalyst and optional water with above-mentioned epoxidized vegetable oil, form the polyalcohol that is applicable to prepare polyurethane foamed material.
Suitable polyalcohol also has the modified vegetable oil-based polyols by the hydroformylation process preparation. In this method, vegetable oil and carbon monoxide and hydrogen react in the presence of VIII family metallic catalyst (such as rhodium catalyst), form the hydroformylation vegetable oil. Then, the hydrogenation of hydroformylation vegetable oil forms the vegetable oil-based polyols of modification. What the polyalcohol of this method preparation contained all is primary hydroxyl. These polyalcohols can directly be used for preparing polyurethane foamed material. Perhaps, these polyalcohols can with above-mentioned epoxidized vegetable oil in the presence of fluoboric acid catalyst and optional water, formation is applicable to prepare the polyalcohol of polyurethane foamed material.
The example of suitable vegetable oil comprises: soya-bean oil, safflower oil, Linseed oil, corn oil, sunflower oil, olive oil, Tower rape oil, sesame oil, cottonseed oil, palm oil, rapeseed oil, tung oil, fish oil, peanut oil, and the combination of above-mentioned vegetable oil. The vegetable oil of partially hydrogenated vegetable oil and gene modification be can also use, high oleic safflower oil, high oleic acid soya-bean oil, high oleic acid peanut oil, high oleic sunflower oil and high erucic acid rape seed oil (Crambe abyssinica (crambe) oil) comprised.
Useful polyisocyanates average per molecule has at least about 2.0 NCOs. Can use aliphatic series and aromatic polyisocyanate. Suitable aliphatic polyisocyanate example comprises: 1,4-fourth vulcabond, 1,6-hexamethylene diisocyanate, 1,12-dodecane vulcabond, cyclobutane-1,3-vulcabond, cyclohexane-1,3-and Isosorbide-5-Nitrae-vulcabond, 1,5-two isocyanato-s-3,3,5-trimethyl-cyclohexane, hydrogenation 2,4-and/or 4,4 '-methyl diphenylene diisocyanate (H12MDI), IPDI etc. The example of suitable aromatic polyisocyanate comprises: 2,4-toluene di-isocyanate(TDI) (TDI), 2,6-toluene di-isocyanate(TDI) (TDI) and their mixture, 1,3-and 1,4-phenylene diisocyanate, 4,4 '-methyl diphenylene diisocyanate (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 such as amido-containing acid ester, carbodiimide, allophanate, isocyanuric acid ester, acidylate urea, biuret, ester and similar those of group.
The polyisocyanates amount preferably can be enough to provide about 60-120, better about 70-110 isocyanate index, at the high water content prescription (namely, in the prescription per 100 weight portions other contain active hydrogen substance and contain water at least about 5 weight portions) situation, the polyisocyanates amount is for providing the isocyanate index of about 70-90. " isocyanate index " refers to NCO and reactive hydrogen base ratio * 100 in the reactant mixture.
Whipping agent produces gas under the reaction conditions of polyvalent alcohol and polyisocyanates.Suitable whipping agent comprises water, liquid carbon dioxide, acetone and pentane, preferably water.
Foaming agent consumption is for being enough to provide the foam densities of requirement.For example, when making water as unique whipping agent, its consumption is, in the prescription per 100 weight parts other contain active hydrogen substance and be about 0.5-10, better about 1-8, better about 2-6 weight part.
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.
Useful tensio-active agent example comprises silicone surfactant and fatty acid alkali metal salt.Preferred silicone surfactant, as the segmented copolymer of epoxy alkane and dimethyl siloxane, the silicone surfactant of preferred " ground fog " level especially.
The useful catalysts example 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 in the prescription per 100 weight parts and contains active hydrogen substance and be about the 0.01-5 weight part, better is about the 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 is about the 0.001-1.0 weight part in the prescription.
Can also use mixture of catalysts.
In some situation, in preparation foam materials time prescription, can comprise the electrostatic dissipation agent or the electrostatic dissipation agent is used for the foam materials of making is handled.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.What arouse attention especially is, 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.
Can adopt free-rise (block material) and molding technique to prepare foam materials.In bulk material method, reactant mixes and is poured on the transport tape, and reaction mixture is resisted it and sent out and solidify from restarting on transport tape.In method of moulding, be distributed in the mould after reactant mixes and react, fill this mould, and present the shape of die cavity.
Often require to make foam materials carry out after fixing afterwards to reach optimum physical properties beginning foaming (molded foam materials situation is the demoulding).After fixing can carry out about 12 hours to 7 days under envrionment conditions, or carries out under elevated temperature about 10 minutes to 3 hours.
Under some situation, require to open the cell wall of foam materials with mechanical means.The most convenient method of opening cell wall is any known flattening (crushing) method.
Under some situation, the zone that the foam materials of requirement preparation has two or more different hardness values.Can comprise above-mentioned flexible polyurethane foams in one or two zone by the modified vegetable oil-based polyols preparation.
The foam materials product has good mechanical property, comprises density, tensile strength, tear strength and extension at break.In general, the density of foam materials is at 8-160kg/m 3Scope is preferably 12-128kg/m 3, better be about 16-80kg/m 3Concrete density value can be selected according to the foam materials intended purpose.
Foam materials can be used for various uses.For example, foam materials can join in the seat part (having as, seat cushion, backrest or two kinds) of motor vehicle or furniture.When being used for the seat part of motor vehicle, many hardness foam materials is particularly useful.Other example of foam materials purposes comprises the foam materials and the flexible package foam materials of carpet lining, mat.
Embodiment
Abbreviation
Use following abbreviation below in the part:
The pre-composition of B-side masterbatch-polyvalent alcohol, tensio-active agent, linking agent, catalyzer, additive and whipping agent, the back will be mixed with required polyisocyanates, begins to form the foamy reaction.
BVT-is the abbreviation of Brookfield viscosity test.This test is the short-cut method of the gelling reaction characteristic of more various polyvalent alcohols and polyisocyanates.
CPP-is the abbreviation of copolymer polyols.
CS-is the abbreviation of compressive set.
Foam materials smell-, after the demoulding and manual the flattening, estimate the odor property of each foam materials at once in some situation.Normal level refers to that the smell of foam materials is not different from the common smell of foam materials that adopts ordinary method just to prepare.In other Example formulations, foam materials has tangible smell sometimes, and this smell can be pursued the polyvalent alcohol of concrete use.Medium grade refers to that foam materials has obvious different odor but do not reach horrible level.Strong grade shows the different and smell to make most of viewer's dislike levels exist of smell.
Other situation, the foam materials smell is estimated according to SAE J1351 scheme, " smell test " part explanation below of this scheme.
The subjective assessment of immediately closed pore and the perforate situation of foam materials outward appearance being carried out after foam tightness-foam materials is molded.Can infer that closely the closed pore of foam materials is more than perforate.The closed pore of foam materials is many more, and foam materials is tight more, and this also hints to tear easy degree and need great compression pressure to come machinery to flatten when the demoulding and open the foamy abscess, the contraction when being avoided the foam materials cooling.
HACS-is the abbreviation of deterioration with moisture compressive set.
Also repeat back and forth up and down to knock this foam materials on the display surface of the manual foam cushions that flattens-hand is placed on the firm demoulding, make the physical action that all closed pore windows are damaged in the foam cushions.On the whole surface of pad, repeat this effect, to guarantee the homogeneity on the each several part of pad.
Load efficiency numbers-, help to determine that any alternative approach adjusting foam materials hardness is more effective according to the number that WO 02/10247 calculates.The load strongthener that newton number/weight part that the foam materials hardness that is defined as the load level of efficiency improves adds.Must carry out suitable rating calculation with reference to the basic components or the control formula that do not contain the Load Regulation additive.
The comprehensive term of bearer properties-A is used to refer to the result when the supporting capacity of test flexible foam material.The routine data of report comprises 25 and 65% indentation force deflection value.
Sag factor (sag factor)-according to the numerical value of the ratio calculation of 65% indentation force deflection value and 25% indentation force deflection value.
Material
Use following material in an embodiment:
Arcol The polyether triol of a F-3022-petroleum-based nominal molecular weight 3000 is 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 480mPa.s.This material has the distinctive smell as mild as a dove of polyether glycol.This material can be buied from Bayer Corporation.
Arcol The polyether triol of a LHT-240-petroleum-based nominal molecular weight 700 makes by propylene oxide is added in the 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 238,25 ℃ viscosity be 250mPa.s.This material has the distinctive smell as mild as a dove of polyether glycol.This material can be buied from Bayer Corporation.
The solvent base mold release compositions that Chem-Trend PRC-7166-is proprietary can be buied from Chem-TrendCorporation.
Dabco BL-11-catalyzer Industrial products can be buied from Air Products Corporation, comprise the dipropylene glycol solution of 70 weight % two (dimethyl aminoethyl) ethers.Usually in foamable reaction, be used as catalyzer.
Dabco DC-5169-tensio-active agent Industrial products are buied from Air Products Corporation.
Dabco 33-LV-catalyzer Industrial products are buied from Air Products Corporation, comprise the dipropylene glycol solution of the triethylenediamine of 33 weight %.Usually as polyreaction or agglomerative catalyzer.
The DEOA-diethanolamine.Use is from the diethanolamine of the technical pure level of the Huntsman linking agent as stable foam material in this invention work.
Hyperlite E-848 polyvalent alcohol-petroleum base high functionality type polyether glycol, reach intermediate molecular weight by propylene oxide being added special-purpose initiator compounds, use ethylene oxide-cappedly then, make final product owing to having increased functionality and have primary hydroxyl to improve reactivity.The characteristic feature of this material comprises: very light yellow, functionality are 3.8, and viscosity was 1100mPa.s when hydroxyl value was about 31.5,25 ℃.This material can be buied from Bayer Corporation.
Hyperlite E-849 polyvalent alcohol-petroleum base polyether glycol contains nominal 41 weight % and is dispersed with the stable copolymer pellet that contains styrene/acrylonitrile.The characteristic feature of this material comprises: viscosity was 6500mPa.s when canescence, hydroxyl value were about 18,25 ℃.This material has the distinctive smell as mild as a dove of copolymer polyols.This material can be buied from Bayer Corporation.
Niax D-19-tinbase gelation catalyst, but GE Silicones-OSI Specialties, Inc. obtains.
Niax Y-10184-silicone base tensio-active agent, from GE Silicones-OSI Specialties, Inc. obtains.This product is specified and is used to prepare the flexible molding polyurethane foamed material.
Polyvalent alcohol A-is to the following examples, and this material is Hyperlite The E-849 copolymer polyols.
Polyvalent alcohol B-is to following embodiment, and this material is Arcol The LHT-240 polyvalent alcohol.
Polyvalent alcohol C-is to following embodiment, and this material is SoyOyl The GC5N polyvalent alcohol.
Polyvalent alcohol D-is to following embodiment, and this material is a SoyOyl  P38N polyvalent alcohol.
Polyol E-modified soyabean oil-polylol, according at United States Patent (USP) 6,433,121 embodiment 6 described methods preparations.The characteristic feature of this product comprises: with the positive reactivity of isocyanate compound, be essentially the terminal hydroxy group of secondary hydroxyl, hydroxy functionality is 3.8, and viscosity was 12000mPa.s when hydroxyl value was 200,25 ℃.This product is very light yellow, has distinctive smell as mild as a dove.
Polyvalent alcohol F-modified soyabean oil polylol is according to following preparation.This polyvalent alcohol contains unreacted pair of key.The characteristic feature of this product comprises: with the positive reactivity of isocyanate compound, be essentially the terminal hydroxy group of secondary hydroxyl, viscosity was 5500mPa.s when hydroxyl value was 192,25 ℃.This product is very light yellow, has distinctive smell as mild as a dove.
Polyvalent alcohol G-modified soyabean oil polylol is according to following preparation.The characteristic feature of this product comprises: with the positive reactivity of isocyanate compound, be essentially the terminal hydroxy group of primary hydroxyl, hydroxy functionality is 4.5, and viscosity was 14000mPa.s when hydroxyl value was 220,25 ℃.This product is very light color and luster, has distinctive smell as mild as a dove.
Polyvalent alcohol H-modified soyabean oil polylol is according to following preparation.The characteristic feature of this product comprises: with the positive reactivity of isocyanate compound, be the terminal hydroxy group of secondary hydroxyl in fact entirely, viscosity was 2300mPa.s when hydroxyl value was 89,25 ℃.This product is very light yellow, has distinctive smell as mild as a dove.
SoyOyl The GC5N-biopolyol is designed for medium-soft matter and hard foam purposes, is sold by Urethane Soy Systems Company.This product typical characteristics of report comprises: functionality is 3, and viscosity was 2700mPa.s when hydroxyl value was 275,25 ℃.Point out that this product contains glycerine and sucrose that significant quantity adds.Be amber under this material room temperature, and have hint and be the overpowering odor of soya-bean oil.
SoyOyl The P38N-biopolyol is designed for the flexible foam material purposes, is sold by Urethane SoySystems Company.This product characteristic feature of report comprises: functionality is 2, and viscosity was 2800mPa.s when hydroxyl value was 53,25 ℃.Be amber under this material room temperature, and have hint and be the overpowering odor of soya-bean oil.
Tegostab B-2370-is designed for conventional plate (slabstock) foam materials purposes from the surfactant product that Degussa AG sells.
Tegostab The ground fog level tensio-active agent that B-4690 LF-buys from Degussa AG.
Tolylene diisocyanate-in work of the present invention uses 2 of commercially available 80/20 tolylene diisocyanate, 4-and 2,6-isomer mixture.This mixture can obtain from Bayer Corporation, and product are called Mondur The A level of TD-80 product.
The commercially available distilled water of water-use is as indirect whipping agent.
Polyvalent alcohol is synthetic
1. polyvalent alcohol F
Preparation modified soyabean oil polylol F uses the testing installation of 2 liter of three neck round-bottomed flask that temperature control, feed hopper, reflux exchanger and agitator are housed to be prepared.Add the soya-bean oil of 500 grams (2.5 moles of two keys) in this reactor assembly, this soya-bean oil is the RBD level of being sold by Archer Daniels Midland Company, and iodine number is 127 milligrams of I 2/ 100 grams, viscosity is 60mPa s.
75 gram glacial acetic acids (1.25 moles) and 6.36 gram 50% aqueous sulfuric acids (0.0325 mole) have also been added in the reactor.Thoroughly mix these components, the reactor assembly temperature is increased to 70 ℃ simultaneously.After reaching this temperature set-point, in 30 minutes, (Aldrich catalognumber 34 988-7), keeps above-mentioned design temperature simultaneously and carries out vigorous stirring to add 243 grams, 35% aqueous hydrogen peroxide solution through dropping funnel.After reacting 4.5 hours again, the content of this reactor assembly is moved on in 2 liters of separating funnels, make it cooling, cooling period, water and the thick epoxidised soya-bean oil of part are divided into two-layer.
By discharging first water layer, use the epoxidised soya-bean oil layer of the thick part of distilled water wash three times of 1 premium on currency five equilibrium then, progressively obtain product continuously.Part epoxidized soybean oil through washing separates once more, adds 40 gram deacidites (Lewatite MP-64 is from Bayer).Stirred this mixture 2 hours, the acid of all remnants that neutralize.
Then product is filtered, the deionizing exchange resin is removed remaining water under rough vacuum.The final part epoxidized soybean oil product that obtains, its iodine number is 25.6 milligrams of I 2The oxygen level of/100 grams and epoxy is 5.4%.
Continue preparation modified soyabean oil polylol F with above-mentioned same reactor assembly but through cleaning with after setting again.In this reactor, add 330 gram (10.33 moles) methyl alcohol, 83 gram (4.59 moles) water and 6.731 gram Tetrafluoroboric acids (be 48% mixture with water, can 20, the 793-4 catalog number obtains from Aldrich).
These components are thoroughly mixed, and reactor assembly is warming up to boiling point simultaneously.The part epoxidized soybean oil that 510 grams (1.72 moles of epoxy group(ing)) are prepared above adds rapidly in the fierce reactor that stirs then.
After reacting 60 minutes again, add 100 gram deacidites (Lewatite MP-64 is from Bayer) with neutralizing acid.Stir this mixture 1 hour, and made it cooling.By crossing the filtering solid ion-exchange resin and removing residual water and the continuous product that reclaims of alcohol by vacuum distilling.The final modified soyabean oil polylol that obtains is faint yellow, and hydroxyl value is 192mg KOH/g, and 25 ℃ viscosity is 5,500mPa s.
2. polyvalent alcohol G
Preparation modified soyabean oil polylol G is prepared with the testing installation of 500 milliliters of stainless steel high-pressure reactors.This reactor is equipped with temperature regulator, adds gas port and agitator.Add the soya-bean oil of 100 grams (0.512 mole of two key) in this reactor assembly, this soya-bean oil is the RBD level of being sold by Archer Daniels Midland Company, and iodine number is 127 milligrams of I 2/ 100 grams, viscosity is 60mPa s.
In reactor, add 0.129 gram (0.0005 mole) dicarbonyl rhodium acetylacetonate and 0.66 gram (0.0025 mole) triphenylphosphine again.Close this reactor, thoroughly mix these components, simultaneously reactor with three volumes etc. the hydrogen of mol ratio and the syngas mixture flushing that carbon monoxide is formed.Then, with same gas composition reactor is forced into 13.4mPa.
Continue to stir 25 minutes, reactor is warming up to 90 ℃ during this period.Reactor kept 2 hours in these conditions again.Then, temperature of reactor drops to 70 ℃, release of gas pressure, and reactor washes with the pure hydrogen of three volumes once more.
Reactor again with pressurized with hydrogen to 3.4mPa, reactor is sealed, stirs, is heated to 130 ℃, kept 30 minutes in these conditions, make rhodium-catalyst based inactivation.
After reactor cooling to 30 ℃ and the release of gas pressure, open this reactor, in reactor, add 9 gram Raney nickel and 50 milliliters of Virahols.This reactor assembly seals once more, with the flushing of three volumes hydrogen, then with pressurized with hydrogen to 4.1mPa.Begin to stir, temperature rises to 110 ℃.Keeping hydrogen pressure is that 3-5mPa reacted down lasting 5 hours.
Then, reactor cooling is to room temperature, release of gas pressure.The product recovery comprises by diatomite Celite filtration reactor content and by vacuum distilling removes residual solvent.The final modified soyabean oil polylol that reclaims is light brown liquid, and hydroxyl value is 220mg KOH/g, and 25 ℃ viscosity is 14,000mPa s.
3. polyvalent alcohol H
Preparation modified soyabean oil polylol H uses the testing installation of 5 liter of three neck round-bottomed flask that temperature control, feed hopper, reflux exchanger and agitator are housed to be prepared.Add 1500 gram soya-bean oil in this reactor assembly, this soya-bean oil is buied with the RBD level from Archer Daniels Midland Company, and its iodine number is 131 milligrams of I 2/ 100 grams, viscosity is 62mPa s.
225 gram glacial acetic acids and 19 grams, 50% aqueous sulfuric acid have also been added in the reactor.Thoroughly mix these components, the reactor assembly temperature is increased to 70 ℃ simultaneously.After reaching this temperature set-point, in 30 minutes, (Aldrich catalog number 34 988-7), keeps above-mentioned design temperature simultaneously and carries out vigorous stirring to add 729 grams, 35% aqueous hydrogen peroxide solution through dropping funnel.After reacting 45 minutes again, the content of this reactor assembly is moved on in 3 liters of separating funnels, make it cooling, cooling period, water and the thick epoxidised soya-bean oil of part are divided into two-layer.
By discharging first water layer, use the epoxidised soya-bean oil layer of the thick part of distilled water wash three times of 1 premium on currency five equilibrium then, progressively continue to obtain product.Part epoxidized soybean oil through washing separates once more, adds 100 gram deacidites (Lewatite MP-64 is from Bayer).Stirred this mixture 2 hours, the acid of all remnants that neutralize.Then product is filtered, the deionizing exchange resin is removed remaining water under rough vacuum.The final part epoxidized soybean oil product that obtains, its iodine number is 88 milligrams of I 2The oxygen level of/100 grams and epoxy is 1.89%.
Continue to prepare modified soyabean oil polylol H with the testing installation of 1 liter of three neck round-bottomed flask that temperature control, feed hopper, reflux exchanger and agitator are housed.In this reactor, add 63 and restrain the modified soyabean oil polylol that adopts the hydroformylation process preparation that is similar to above-mentioned preparation polyvalent alcohol G.To concrete hydroformylation type polyvalent alcohol as used herein, can react according to polyvalent alcohol G method fully, substituted dicarbonyl rhodium acetylacetonate except using cobalt-carbonyl as catalyzer.Also add 0.5 gram Tetrafluoroboric acid (being 48% mixture) in the reactor with water.
These components of thorough mixing, reaction system is warming up to 100 ℃ simultaneously.The part epoxidized soybean oil that is used for synthetic polyvalent alcohol H that 150 grams are prepared above adds the reactor of vigorous stirring fast then.
After reacting 40 minutes again, reactive system is cooled to 50 ℃, adds 10 gram deacidites (Lewatite MP-64 is from Bayer) and comes neutralizing acid.Stir this mixture 1 hour, and removed by filter ion exchange resin.Remove residual water by vacuum distilling and continue to reclaim product.The final modified soyabean oil polylol that reclaims, for faint yellow, hydroxyl value is 89mg KOH/g, 25 ℃ viscosity is 2300mPa s.
The gelling reaction of polyvalent alcohol
Adopt the BVT reactivity test to test polyvalent alcohol potential gelling reaction.This simple viscosity increases test be more various polyvalent alcohols with the method a kind of commonly used of the reactive characteristic of tolylene diisocyanate in the model gelling reaction.Be to determine a kind of gelling reaction characteristic of polyvalent alcohol, the polyvalent alcohol sample (common 100 grams) of Commonly Used Size is placed in one 125 milliliters the wide-mouth vial.The Dabco that in this vial, adds 0.25 milliliter with accurate glass syringe The 33-LV catalyzer.Then, with Jiffy Mixer board is housed, any laboratory electricity consumption agitator of LM type mixing oar stirred this vial content 30 seconds.
After in catalyzer, stirring, add the tolylene diisocyanate of the 105 exponential amounts that are equivalent to, with above-mentioned identical agitator on stirred this vial once more 30 seconds, mix after 30 seconds, take out this vial from agitator, be placed on the viscometer, record viscosity increases in 20 minute cycle.With suitable exsiccant sample, do not form foam materials, suppose the situation that this test mensuration is relevant with polymer formation or gelling reaction.With any computer tabulation software or cartographic programme collection time and viscosity data are drawn, obtain fingerprint (fingerprint) BVT responsiveness curve the polyvalent alcohol of test.The principal element that influences the position of responsiveness curve and shape comprises the molecular weight and the functionality of polyvalent alcohol, the secondary hydroxyl of existence/or primary hydroxyl, and the negative impact that causes of impurity such as acid traces or alkali.
The preparation of molded flexible foam material
(a) preparation masterbatch
The first step as the molded flexible foam material of listing among the preparation embodiment is a preparation B-side masterbatch, and method is each component that adds the foam materials prescription that requires in 1 gallon wide-mouth plastics pot.At first polyvalent alcohol is added in this plastics pot, be placed on then on the electric mixing tank of using in the laboratory, this mixing tank is equipped with Jiffy Mixer board, HS-2 type mixing oar.Begin to mix, add all other components of prescription, simultaneously the mixing tank continued running.After adding last recipe ingredient, continue again to mix 15 minutes.From this mixing tank, take out masterbatch, and get 1000 milliliters of wide-mouth vial samples and carry out viscosimetric analysis and observe color and transparency.All the other masterbatch are added a cover and are left standstill, and finish other operation of making foam materials simultaneously.
After the temperature regulation to 25 ℃, with the viscosity of traditional rotary-type Brookfield board viscometer determining masterbatch.
(b) test block module and preparation thereof
For determining that foaming essential property and acquisition carry out the sample pad of foam materials physical properties test, in 38.1 * 38.1 * 11.4 centimetres electrically heated aluminium-making mould, prepare foam materials.The electronically controlled die temperature is at 66 ℃ (± 1 ℃).This mould is equipped with high-strength anchor clamps on hinge lid, three sides and five traditional venting holes.The venting hole diameter is 0.31 centimetre.Pour before each foam materials spraying one deck Chem-Trend PRC-7166 release agent coating on the mould into.
(c) method of blending ingredients and manufacturing foam materials
The preparation method of foam materials promptly adds the prescription B-side masterbatch of aequum from following steps one 33 ounces polymkeric substance cup (model DMC-33 obtains from International Paper Company).Strict control B-side masterbatch and tolylene diisocyanate pour weight into, make nominal filling in the mould, making molded back density is 32Kg/m 3Foam cushions.
The foam materials for preparing all molded examples with 100 toluene diisocyanate indexs.To each prescription, the tolylene diisocyanate that carefully takes by weighing calculated amount is put into three-material filling (pour) plastic beaker of one 400 milliliters, and put aside near hybrid position.
Generate the foamy reaction for causing, the beaker that will contain B-side masterbatch is placed on the mixing device, and this installs by Delta ShopMaster board, the DP-200 type, the workshop rig structure of 10-inch is furnished with Conn MixersCompany, the ConnBlade board, ITC type, the mixing oar that diameter is 3 inches.This mixing tank is set at the 1100RPM rotating speed and operated altogether 30 seconds, and this mixing tank can be controlled by electronic timer.Start mixing by push-switch.During the timing register countdown, take out the tolylene diisocyanate beaker, when also having 6 seconds mixing times, with very fast this beaker of adding of tolylene diisocyanate.
At the mixing period terminal point, the content that mixes in the beaker to be poured in the mould fast, mould is in nominal material filling then and there (spot pour) pattern.The closing molding lid, locking made foam curing 6 minutes.Setting up period, the center die venting hole of close observation mould, a time of the concrete prescription of record.
At the curing cycle terminal point, open mould lid, take out foam cushions, and use hand flat at once.Foam cushions is repaired, weighs, is labelled, and leaves standstill 7 days under 25 ℃ and 50% relative humidity, tests physicals afterwards.
Preparation flexible sheet strand foam material
The flexible sheet strand foam material that uses in embodiment 26 and 27 adopts and above-mentioned the described method of molded flexible foam material is prepared, and except use is 105 isocyanate index, and makes the foam materials free-rise, solidifies in the paper container of open-top.
The physicals test
Measure the physicals of flexible foam material according to the method for listing among the ASTM D 3574.In the test of deterioration with moisture compressive set, the deterioration with moisture condition is the Test J in ASTM D 3574, the condition that Procedure J1 lists.
Be the load reinforced effects of more various candidate's polyvalent alcohols, " load efficient " evaluation system that employing Van Heumen etc. disclose at WO02/10247.In the document, newton number/weight part that the load definitions of efficiency improves for foam materials hardness joins the load strongthener of basic foam material prescription or control formula.Requirement has this higher numerical value, and makes the manufacturers of foam materials select best portative power according to the dollar that newton changed of each increase in conjunction with the cost data of additive technology.In the following examples, adopt the carrying data of 65% foam materials indentation force deflection to calculate.
The smell sample
The testing scheme that adopts is SAE J1351.In each embodiment, 31 quart metal tin is added a cover the baking oven 1 hour that places 65 ℃.There is not foam materials in first jar, therefore with comparing.In second jar dried foam materials sample is housed.In the 3rd jar foam materials is housed and adds 2 ml distilled waters.Take out from baking oven, by one group of smell of estimating each jar of 3 people, the tester is the 1-5 grade for each jar scoring.Ranking score is as follows:
1: do not have obvious smell;
2: slight, but unconspicuous smell;
3: certain smell, its undercapacity is with horrible;
4: strong odour nuisance;
5. unusual intensive odour nuisance.
Color measurement
Adopt HunterLab Ultrascan XE, the spectrocolorimeter that has 6 inches integrating spheres carries out color measurement.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.Sample partly is circular, with the sample part of 1 inch of the light beam measurement diameter of 1 inch of 8 ° of viewing angles and diameter.Every 10nm gets spectroscopic data in the 375-750nm wavelength region, is descended by these data computation data.Colour scale is L, a, b.
Embodiment 1-6
The purpose of these embodiment is to come the gelling reaction of more various polyvalent alcohols according to the reactive testing scheme of BVT:
Embodiment 1:Arcol LHT-240 (polyvalent alcohol B);
Embodiment 2:SoyOyl GC5N (polyvalent alcohol C);
Embodiment 3:SoyOyl P38N (polyvalent alcohol D);
Embodiment 4: polyol E;
Embodiment 5: polyvalent alcohol F;
Embodiment 6: polyvalent alcohol G.
The results are shown in Fig. 1-3.These results confirm, what wherein the reactivity of two kinds of modified vegetable oil-based polyols (polyol E and F) and tolylene diisocyanate can be with petroleum base polyvalent alcohol and tolylene diisocyanate is reactive similar, and apparently higher than any of two kinds of SoyOyl polyvalent alcohols.Polyvalent alcohol G is higher than petroleum base polyvalent alcohol and SoyOyl polyvalent alcohol with the reactivity of tolylene diisocyanate.
Measure the viscosity of each reaction mixture after polyvalent alcohol, tolylene diisocyanate and the catalyst mix 600 seconds the time.The results are shown in following table 1.These results confirm, contain the reaction mixture of these three kinds of modified vegetable oil-based polyols (polyol E, F and G), and the viscosity after 600 seconds is greater than 20,000mPa.s.This petroleum base polyvalent alcohol (polyvalent alcohol B) that relatively helps, and confirm reactivity positive between polyvalent alcohol and vulcabond.On the contrary, the reaction mixture viscosity that contains polyvalent alcohol C and D significantly descends, and hint at most also has only seldom reaction between polyvalent alcohol and vulcabond.
Table 1
Polyvalent alcohol Reaction viscosity in the time of 600 seconds, mPa.s
B ＞50000
C ＜1000
D 2500
E 22500
F 22000
G ＞50000
Comparative example 7-9
Comparative example 7 relates to the flexible molding polyurethane foamed material, and this foam materials does not contain for a change the bearer properties of final foam materials and the special component that adds.The component and the performance of foam materials are listed in table 2.The masterbatch appearance transparent of this comparative example preparation is water white.Naked eyes can determine easily that a plurality of components form the time of uniform mixture.This masterbatch viscosity is low.
After the demoulding also used hand flat, new foam materials had the typical smell of this petroleum base polyether foam material.The bearer properties that foam materials has makes this foam materials be evaluated as " soft " usually by those skilled in the art.Because do not regulate the load of the polyvalent alcohol that exists in this prescription, this foam materials is not reported load efficiency calculation value.
Comparative example 8 and 9 relates to two kinds of flexible molding polyurethane foamed materials that use two kinds of different amount copolymer polyols (polyvalent alcohol A).The component of foam materials and performance are also listed in table 2.The masterbatch of making is opaque, is undesirable canescence.These characteristics make the well-mixed time of recipe ingredient of can not determine.The color of masterbatch also is given to final foam materials, makes it to have undesirable canescence.When observing on the monitor station that this foam materials is placed form backlight, especially obviously there is undesirable chromoplastid.In the time of in being added to flexible foam material prescription, copolymer polyols contain the clean effect that the styrene/acrylonitrile particle has the bearer properties that improves final foam materials.
Table 2
Recipe ingredient (part) Comparative example 7 Comparative example 8 Comparative example 9
Hyperlite E-848 100 70 60
Polyvalent alcohol A --- 30 40
Niax Y-10184 1.0 1.0 1.0
Diethanolamine 1.2 1.2 1.2
Dabco BL-11 0.08 0.08 0.08
Dabco 33-LV 0.35 0.35 0.35
Water 4.2 4.2 4.2
80/20 TDI, index 100 100 100
The masterbatch characteristic
Outward appearance Transparent Opaque Opaque
Color Water white Canescence Canescence
25 ℃ of viscosity, mPa s 1520 2550 2860
Foam performance
Molded back density, kg/m 3 32 32 32
Falling-rebounding ball, % 53 45 48
The foam materials smell Normally Normally Normally
The foam materials color White Canescence Canescence
25％IFD，N/323cm 2 91 127 148
65％IFD，N/323cm 2 260 357 448
25%IFD replys, N/323cm 2 74 99 113
Sag factor 2.9 2.8 3.0
% hysteresis loss 19 22 24
Load efficient, newton/part polyvalent alcohol --- 3.2 4.7
Air-flow, scfm 2.5 3.1 2.4
50％CS，％ 13 18 15
50％HACS，％ 20 19 18
Elongation, % 126 133 119
Tear N/M 173 247 243
Tensile strength, kPa 104 156 153
Comparative example 10-12
Comparative example 10 relates to the flexible molding polyurethane foamed material that adopts petroleum base polyether glycol (polyvalent alcohol B) preparation.The component and the performance of foam materials are listed in table 3.The masterbatch outward appearance is a water white and transparent, presents low viscosity.
Comparative example 11 and 12 relates to two kinds of soya-bean oil polylol: SoyOyl with prior art GC5N (polyvalent alcohol C) and SoyOyl The flexible molding polyurethane foamed material of P38N (polyvalent alcohol D) preparation.The component and the performance of foam materials are listed in table 3.These foam materialss are canescence, and have the intensive odour nuisance.The foam materials that comparative example 11 is made does not show the carrying enhancement of usefulness.Attempt to improve the amount of polyvalent alcohol C and polyvalent alcohol D, cause foam materials to destroy.
Table 2
Recipe ingredient (part) Comparative example 10 Comparative example 11 Comparative example 12
Hyperlite E-848 90 90 90
Polyvalent alcohol B 10 -- --
Polyvalent alcohol C -- 10 (surpassing this amount foam materials destroys) --
Niax Y-10184 1.0 1.0 1.0
Diethanolamine 1.2 1.2 1.2
Dabco BL-11 0.08 0.08 0.08
Dabco 33-LV 0.35 0.35 0.35
Water 4.2 4.2 4.2
80/20TDI, index 100 100 100
The masterbatch characteristic
Outward appearance Transparent Opaque Opaque
Color Water white Amber Amber
25 ℃ of viscosity, mPa s 1100 2312 2484
Foam performance
Molded back density, kg/m 3 32 32 Destroy at 10-30 part foam materials
Falling-rebounding ball, % 44 50
The foam materials smell Normally Strongly Strongly
The foam materials color White Beige Beige
25％IFD，N/323cm 2 92 101
65％IFD，N/323cm 2 263 264
25%IFD replys, N/323cm 2 68 82
Sag factor 2.9 2.6
% hysteresis loss 26 19
Load efficient, newton/part polyvalent alcohol 0.3 0.4
Air-flow, scfm 2.5 3.1
50％CS，％ 31 17
50％HACS，％ 41 18
Elongation, % 112 131
Tear N/M 187 195
Tensile strength, kPa 110 129
Embodiment 13-18
These embodiment relate to the flexible molding polyurethane foamed material with modified vegetable oil-based polyols preparation of the present invention.The component and the performance of foam materials are listed in table 4.
Embodiment 13-18 confirms to use the conventional surfactant combination can make good foam materials, and these tensio-active agents are than the Niax that uses among the comparative example 7-12 The Y-10184 activity is much lower, and its function is much concrete.This support modified vegetable oil-based polyols of the present invention show wondrous degree from tensio-active agent, therefore needn't use and be commonly used to prepare the high reactivity high-performance of flexible polyurethane foams and the tensio-active agent of high price.
Among the embodiment 13-15, different weight polyalcohol E have been used during the preparation foam materials.The masterbatch appearance transparent of making, color can be able to be accepted, and has obviously low viscosity.Fill a prescription by each and successfully to make foam cushions, use hand flat easily, obtain unbroken foam cushions and be used to carry out the physicals test.The gentle distinctive smell of the normal smell of the smell of freshly prepd foam materials during during gradually to higher dosage from low consumption.
The bearer properties of embodiment 13-15 demonstration foam materials improves with the increase of polyol E amount.
Among the embodiment 16-18, the polyvalent alcohol F of different amounts has substituted polyol E.The masterbatch outward appearance of making is transparent, and color is very light, and has obviously low viscosity.
Table 4
Recipe ingredient (part) Embodiment 13 Embodiment 14 Embodiment 15 Embodiment 16 Embodiment 17 Embodiment 18
Hyperlite E-848 90 80 70 90 80 70
Polyol E 10 20 30 -- -- --
Polyvalent alcohol F -- -- -- 10 20 30
Tegostab B-4690LF 1.5 1.5 1.5 1.5 1.5 1.5
Dabco DC-5169 0.5 0.5 0.5 0.5 0.5 0.5
Diethanolamine 1.2 1.2 1.2 1.2 1.2 1.2
Dabco BL-11 0.08 0.08 0.08 0.08 0.08 0.08
Dabco 33-LV 0.35 0.35 0.35 0.35 0.35 0.35
Water 4.2 4.2 4.2 4.2 4.2 4.2
80/20TDI, index 100 100 100 100 100 100
The masterbatch characteristic
Outward appearance Transparent Transparent Transparent Transparent Transparent Transparent
Color Water white Faint yellow Faint yellow Faint yellow Faint yellow Faint yellow
25 ℃ of viscosity, mPa s 1670 1820 2270 1650 1760 1984
Foam performance
Molded back density, kg/m 3 32 32 32 32 32 32
Falling-rebounding ball, % 45 38 34 46 38 35
The foam materials smell Normally Gentle Gentle Gentle Gentle Gentle
The foam materials color White White White White White White
25％IFD，N/323cm 2 121 164 214 92 123 169
65％IFD，N/323cm 2 333 465 600 263 349 471
25%IFD replys, N/323cm 2 90 101 108 70 80 94
Sag factor 2.8 2.8 2.8 2.8 2.8 2.8
% hysteresis loss 26 38 50 24 35 44
Load efficient, newton/part polyvalent alcohol 7.3 10.3 11.3 0.3 4.5 7.0
Air-flow, scfm 4.3 3.3 3.1 3.7 3.5 3.1
50％CS，％ 26 53 76 24 42 67
50％HACS，％ 25 62 79 24 54 74
Elongation, % 123 107 85 140 123 96
Tear N/M 260 300 327 233 273 300
Tensile strength, kPa 126 145 153 131 149 155
Embodiment 19-20
These embodiment relate to the flexible molding polyurethane foamed material with the vegetable oil-based polyols preparation of another kind of modification of the present invention.The component and the performance of foam materials are listed in table 5.
In these foam materialss, the consumption of polyvalent alcohol G increases.The masterbatch appearance transparent of making, color can be accepted, and viscosity is low.The smell of newly formed foam materials is normal.
Table 5
Recipe ingredient (part) Embodiment 19 Embodiment 20
Hyperlite E-848 90 80
Polyvalent alcohol G 10 20
Tegostab B-4690LF 1.5 1.5
Dabco DC-5169 0.5 0.5
Diethanolamine 1.2 1.2
Dabco BL-11 0.08 0.08
Dabco 33-LV 0.35 0.35
Water 4.2 4.2
80/20TDI, index 100 100
The masterbatch characteristic
Outward appearance Transparent Transparent
Color Water white Water white
25 ℃ of viscosity, mPa s 1600 1780
Foam performance
Molded back density, kg/m 3 32 32
Falling-rebounding ball, % 42 35
The foam materials smell Normally Normally
The foam materials color White White
25％IFD，N/323cm 2 119 193
65％IFD，N/323cm 2 330 487
25%IFD replys, N/323cm 2 80 105
Sag factor 2.8 2.5
% hysteresis loss 33 46
Load efficient, newton/part polyvalent alcohol 7.0 11.4
Air-flow, scfm 2.7 0.9
50％CS，％ 35 71
50％HACS，％ 35 68
Elongation, % 114 77
Tear N/M 275 320
Tensile strength, kPa 123 133
Embodiment 21-24
Among these embodiment, according to the smell testing scheme of listing above, the smell of assess foam material.Foam sample below using:
Embodiment 21 (comparison): the composition of foam materials is formed identical with comparative example 8 described foam materialss.Polyvalent alcohol is Hyperlite E-848 polyether-based polyvalent alcohol and copolymer polyols (Hyperlite E-849) combination.
Embodiment 22: the composition of foam materials is identical with the composition of embodiment 13 described foam materialss.Polyvalent alcohol is Hyperlite The combination of E-848 polyether-based polyvalent alcohol and polyol E.
Embodiment 23: the composition of foam materials is identical with the composition of embodiment 20 described foam materialss.Polyvalent alcohol is Hyperlite The combination of E-848 polyether-based polyvalent alcohol and polyvalent alcohol G.
Embodiment 24 (comparison): the composition of foam materials is identical with the composition of comparative example 11 described foam materialss.Polyvalent alcohol is Hyperlite E-848 polyether-based polyvalent alcohol and polyvalent alcohol C (SoyOyl The GC5N polyvalent alcohol) combination.
Test result is listed in table 6.These results confirm, use the foam materials of modified vegetable oil-based polyols preparation of the present invention to have acceptable odor properties.
Table 6
Embodiment Group The dry foam material Wet foam material Slack tank
21 1 3 3 1
2 3 3 1
3 3 3 1
Intermediate value 3 3 1
Scope 0 0 1
On average 3 3 1
22 1 3 3 1
2 3 2 1
3 2 3 1
Intermediate value 2 2 1
Scope 1 1 0
On average 3 3 1
23 1 2 2 1
2 2 2 1
3 2 2 1
Intermediate value 2 2 0
Scope 0 0 1
On average 2 2 1
24 1 2 2 1
2 2 2 1
3 2 2 1
Intermediate value 2 2 0
Scope 0 0 0
On average 2 2 1
Embodiment 25
The composition that contains active hydrogen prepares by following mode, and room temperature (about 23 ℃) is with Hyperlite Modified vegetable oil-based polyols (polyol E) that E-848 polyether-based polyvalent alcohol and relative per 100 weight part compositions are 5,10,20 and 30 weight parts or the polyvalent alcohol C (SoyOyl that compares GC5N) mix.Hyperlite The E-848 polyvalent alcohol itself is optically transparent.All keep transparent after adding different weight polyalcohol E.On the contrary, even polyvalent alcohol C add-on is low to moderate 5 parts, contain the active hydrogen composition also for opaque with what polyvalent alcohol C prepared.
To Hyperlite It is optical clear when beginning that E-848 adds the composition that contains active hydrogen that 30 parts of polyol Es of per 100 parts of compositions make, and this optical transparence has kept more than 8 months in room temperature (about 23 ℃).
Embodiment 26-27
The purpose of these embodiment is the colour fastness that the flexible polyurethane foams of different polyvalent alcohols is used in research.The foam materials composition is listed in table 7.These foam materialss do not comprise ultra-violet stabilizer.
Table 7
Recipe ingredient (part) Embodiment 26 Embodiment 27
Arcol F-3022 100 60
Polyvalent alcohol H -- 40
Tegostab B-2370 1.0 1.0
Dabco BL-11 0.1 0.1
Dabco 33-LV 0.2 0.2
Niax D-19 0.25 0.25
Water 4.0 4.0
80/20TDI, index 105 105
Cut next sample from each foam materials, it is wrapped in the aluminium foil, carry out color measurement, obtain result unexposed foam materials (that is, not being exposed to the foam materials of ambient light) according to foregoing color measurement method.Downcut second sample from each foam materials, and be exposed to 6 weeks in the envrionment conditions light, test according to the color measurement method afterwards.The results are shown in table 8 (the colour system number that comprises mirror surface) and table 9 (the colour system number that does not comprise mirror surface).In general, high more and a of L and b value are low more, and foam materials is white more.The result shows that the foam materials that uses modified vegetable oil-based polyols (embodiment 27) preparation keeps its initial white situation only to be better than the situation of the foam materials that is made by polyether-based polyvalent alcohol (embodiment 26 (comparison)).
Table 8
Sample L A B
Embodiment 26 (unexposed) 80.48 -0.43 11.01
Embodiment 26 (exposure) 65.79 4.85 25.01
Embodiment 27 (unexposed) 83.79 -0.80 9.43
Embodiment 27 (exposure) 79.28 -0.39 22.91
Table 9
Sample L A B
Embodiment 26 (unexposed) 80.82 -0.60 10.40
Embodiment 26 (exposure) 65.46 5.10 24.55
Embodiment 27 (unexposed) 84.27 -0.97 8.65
Embodiment 27 (exposure) 78.95 -0.51 23.06
A plurality of embodiment of the present invention has been described.Yet, should understand not departing from the spirit and scope of the invention and can carry out various changes.Therefore, other embodiment is within the scope of claims.

Claims (142)

1. flexible polyurethane foams comprises the reaction product of following component in the presence of whipping agent:
(a) polyisocyanates,
(b) contain the composition of active hydrogen, said composition comprises modified vegetable oil-based polyols,
Wherein, the load efficiency numbers of described foam materials is at least 4 newton/part modified vegetable oil-based polyols.
2. flexible polyurethane foams as claimed in claim 1 is characterized in that, the load efficiency numbers of described foam materials is at least 7 newton/part modified vegetable oil-based polyols.
3. flexible polyurethane foams as claimed in claim 1 is characterized in that, the load efficiency numbers of foam materials is at least 10 newton/part modified vegetable oil-based polyols.
4. flexible polyurethane foams as claimed in claim 1, it is characterized in that the load efficiency numbers of the described foam materials load efficiency numbers with the polyurethane foamed material that is made by the alternative described modified vegetable oil-based polyols of equivalent copolymer polyols at least is the same high.
5. flexible polyurethane foams as claimed in claim 1 is characterized in that, the density of described foam materials is 8-160kg/m 3
6. flexible polyurethane foams as claimed in claim 1 is characterized in that, the density of described foam materials is 12-128kg/m 3
7. flexible polyurethane foams as claimed in claim 1 is characterized in that, the density of described foam materials is 16-80kg/m 3
8. flexible polyurethane foams as claimed in claim 1, it is characterized in that, described foam materials is not being contained under the ultra-violet stabilizer condition, be exposed to 6 time-of-weeks in the light of envrionment conditions, its color that has is worth by (L) of 70 units at least and (b) value of being not more than 25 units characterizes.
9. flexible polyurethane foams as claimed in claim 8 is characterized in that, the color of described foam materials is characterized by (a) value that is not more than 4 units.
10. flexible polyurethane foams as claimed in claim 1, it is characterized in that, the color that the foam materials of making has is worth by (L) of 70 units at least and (b) value of being not more than 25 units characterizes, wherein, when described foam materials is not containing under the ultra-violet stabilizer condition, be exposed to 6 time-of-weeks in the light of envrionment conditions, its (L) value changes and is no more than 14 units, and (b) value variation is no more than 14 units.
11. flexible polyurethane foams as claimed in claim 10, it is characterized in that, (a) value of the foam materials of making is not more than 4 units, wherein, when described foam materials is not containing under the ultra-violet stabilizer condition, be exposed to 6 time-of-weeks in the light of envrionment conditions, its (a) value changes and is no more than 5 units.
12. flexible polyurethane foams as claimed in claim 1, it is characterized in that, the feature of described modified vegetable oil-based polyols is, according to the BVT reactivity test described polyvalent alcohol is mixed the formation reaction mixture with catalyzer and tolylene diisocyanate, the viscosity of the reaction mixture that records 600 seconds the time after forming this reaction mixture is at least 5,000mPa.s.
13. flexible polyurethane foams as claimed in claim 1, it is characterized in that, the feature of described modified vegetable oil-based polyols is, when described polyvalent alcohol being mixed the formation reaction mixture with catalyzer and tolylene diisocyanate according to the BVT reactivity test, the viscosity of the reaction mixture that records 600 seconds the time after forming this reaction mixture is at least 10,000mPa.s.
14. flexible polyurethane foams as claimed in claim 1, it is characterized in that, the feature of described modified vegetable oil-based polyols is, when described polyvalent alcohol being mixed the formation reaction mixture with catalyzer and tolylene diisocyanate according to the BVT reactivity test, the viscosity of the reaction mixture that records 600 seconds the time after forming this reaction mixture is at least 20,000mPa.s.
15. flexible polyurethane foams as claimed in claim 1 is characterized in that, described modified vegetable oil-based polyols comprises the modified soyabean oil polylol.
16. flexible polyurethane foams as claimed in claim 1 is characterized in that, described modified vegetable oil-based polyols is to prepare by the method that comprises one or more pairs of key reactions that make vegetables oil.
17. flexible polyurethane foams as claimed in claim 1 is characterized in that, described modified vegetable oil-based polyols adopts the method preparation that may further comprise the steps:
(a) form epoxidized vegetable oil;
(b) epoxidized vegetable oil is mixed with the fluoroboric acid of pure and mild catalytic amount, form the vegetable oil-based polyols of modification.
18. flexible polyurethane foams as claimed in claim 17 is characterized in that, described epoxidized vegetable oil is the part epoxidized vegetable oil, and described modified vegetable oil-based polyols comprises two keys.
19. flexible polyurethane foams as claimed in claim 1 is characterized in that, described modified vegetable oil-based polyols adopts the method preparation that may further comprise the steps:
(a) vegetables oil and carbon monoxide and hydrogen are reacted in the presence of the group VIII metal catalyst, to form the hydroformylation vegetables oil;
(b) make the hydrogenation of described hydroformylation vegetables oil, to form modified vegetable oil-based polyols.
20. flexible polyurethane foams as claimed in claim 1 is characterized in that, described modified vegetable oil-based polyols adopts the method preparation that may further comprise the steps:
(a) vegetables oil and carbon monoxide and hydrogen are reacted in the presence of the group VIII metal catalyst, to form the hydroformylation vegetables oil;
(b) make the hydrogenation of described hydroformylation vegetables oil, to form modified polyalcohol;
(c) described polyvalent alcohol is mixed with the fluoroboric acid of epoxidized vegetable oil and catalytic amount, to form the vegetable oil-based polyols of modification.
21. flexible polyurethane foams as claimed in claim 20 is characterized in that, described epoxidized vegetable oil is the part epoxidized vegetable oil, and described modified vegetable oil-based polyols comprises two keys.
22. flexible polyurethane foams as claimed in claim 1 is characterized in that, described modified vegetable oil-based polyols comprises secondary hydroxyl.
23. flexible polyurethane foams as claimed in claim 1 is characterized in that, described modified vegetable oil-based polyols comprises primary hydroxyl.
24. flexible polyurethane foams as claimed in claim 1 is characterized in that, described modified vegetable oil-based polyols comprises primary hydroxyl and secondary hydroxyl.
25. flexible polyurethane foams as claimed in claim 1 is characterized in that, the described composition that contains active hydrogen comprises 0.5-50 weight part modified vegetable oil-based polyols/100 weight parts and contains active hydrogen substance.
26. flexible polyurethane foams as claimed in claim 1 is characterized in that, the described composition that contains active hydrogen comprises 1-40 weight part modified vegetable oil-based polyols/100 weight parts and contains active hydrogen substance.
27. flexible polyurethane foams as claimed in claim 1 is characterized in that, the described composition that contains active hydrogen comprises 2-30 weight part modified vegetable oil-based polyols/100 weight parts and contains active hydrogen substance.
28. flexible polyurethane foams as claimed in claim 1 is characterized in that, the described composition that contains active hydrogen also comprises the polyvalent alcohol that is selected from polyether glycol, polyester polyol and their combination.
29. flexible polyurethane foams as claimed in claim 1 is characterized in that, the described composition that contains active hydrogen also comprises copolymer polyols.
30. flexible polyurethane foams as claimed in claim 1 is characterized in that, the described composition that contains active hydrogen also comprises dendritic macromole.
31. flexible polyurethane foams as claimed in claim 1, it is characterized in that, the feature of described modified vegetable oil-based polyols is, when 1-49 weight part polyvalent alcohol and 99-51 weight part hydroxyl value are combined to form the composition that contains active hydrogen less than 120 polyether-based polyvalent alcohol, form stable liquid down at 23 ℃.
32. flexible polyurethane foams as claimed in claim 1, it is characterized in that, the feature of described modified vegetable oil-based polyols is, what comprise modified vegetable oil-based polyols and be selected from polyether glycol, polyester polyol and their combination contains the active hydrogen composition, and the described viscosity that contains the active hydrogen composition is lower than the comparable viscosity that contains the active hydrogen composition that comprises the copolymer polyols that substitutes modified vegetable oil-based polyols.
33. flexible polyurethane foams as claimed in claim 1 is characterized in that, described foam materials is the plate foam materials.
34. flexible polyurethane foams as claimed in claim 1 is characterized in that, described foam materials is molded foam materials.
35. flexible polyurethane foams as claimed in claim 1 is characterized in that, the sag factor of described foam materials is at least 2.5.
36. flexible polyurethane foams as claimed in claim is characterized in that, the sag factor of described foam materials is at least 2.8.
37. flexible polyurethane foams as claimed in claim 1 is characterized in that, the described composition that contains active hydrogen is substantially free of the particle greater than 0.1 micron.
38. a flexible polyurethane foams, it comprises the reaction product of following component in the presence of whipping agent:
(a) polyisocyanates,
(b) contain the composition of active hydrogen, said composition comprises modified vegetable oil-based polyols,
Wherein, described foam materials is not being contained under the ultra-violet stabilizer condition, be exposed to 6 weeks in the light of envrionment conditions, its color that has is worth by (L) of 70 units at least and (b) value of being not more than 25 units characterizes.
39. flexible polyurethane foams as claimed in claim 38 is characterized in that, the color of described foam materials is characterized by (a) value that is not more than 4 units.
40. flexible polyurethane foams as claimed in claim 38, it is characterized in that, the feature of described modified vegetable oil-based polyols is, according to the BVT reactivity test described polyvalent alcohol is mixed the formation reaction mixture with catalyzer and tolylene diisocyanate, the viscosity of the reaction mixture that records 600 seconds the time after forming described reaction mixture is at least 5,000mPa.s.
41. flexible polyurethane foams as claimed in claim 38, it is characterized in that, the feature of described modified vegetable oil-based polyols is, according to the BVT reactivity test described polyvalent alcohol is mixed the formation reaction mixture with catalyzer and tolylene diisocyanate, the viscosity of the reaction mixture that records 600 seconds the time after forming described reaction mixture is at least 10,000mPa.s.
42. flexible polyurethane foams as claimed in claim 38, it is characterized in that, the feature of described modified vegetable oil-based polyols is, according to the BVT reactivity test described polyvalent alcohol is mixed the formation reaction mixture with catalyzer and tolylene diisocyanate, the viscosity of the reaction mixture that records 600 seconds the time after forming described reaction mixture is at least 20,000mPa.s.
43. flexible polyurethane foams as claimed in claim 38 is characterized in that, described modified vegetable oil-based polyols comprises the modified soyabean oil polylol.
44. flexible polyurethane foams as claimed in claim 38 is characterized in that, described modified vegetable oil-based polyols is to prepare by the method that comprises one or more pairs of key reactions that make vegetables oil.
45. flexible polyurethane foams as claimed in claim 38 is characterized in that, described modified vegetable oil-based polyols adopts the method preparation that may further comprise the steps:
(a) form epoxidized vegetable oil;
(b) described epoxidized vegetable oil is mixed with the fluoroboric acid of pure and mild catalytic amount, to form the vegetable oil-based polyols of modification.
46. flexible polyurethane foams as claimed in claim 45 is characterized in that, described epoxidized vegetable oil is the part epoxidized vegetable oil, and described modified vegetable oil-based polyols comprises two keys.
47. flexible polyurethane foams as claimed in claim 38 is characterized in that, described modified vegetable oil-based polyols adopts the method preparation that may further comprise the steps:
(a) vegetables oil and carbon monoxide and hydrogen are reacted in the presence of the group VIII metal catalyst, to form the hydroformylation vegetables oil;
(b) make the hydrogenation of described hydroformylation vegetables oil, to form modified vegetable oil-based polyols.
48. flexible polyurethane foams as claimed in claim 38 is characterized in that, described modified vegetable oil-based polyols adopts the method preparation that may further comprise the steps:
(a) vegetables oil and carbon monoxide and hydrogen are reacted in the presence of the group VIII metal catalyst, to form the hydroformylation vegetables oil;
(b) make the hydrogenation of described hydroformylation vegetables oil, to form polyvalent alcohol;
(c) fluoroboric acid of described polyvalent alcohol with epoxidized vegetable oil and catalytic amount mixed, to form the vegetable oil-based polyols of modification.
49. flexible polyurethane foams as claimed in claim 48 is characterized in that, described epoxidized vegetable oil is the part epoxidized vegetable oil, and described modified vegetable oil-based polyols comprises two keys.
50. a flexible polyurethane foams, it comprises the reaction product of following component in the presence of whipping agent:
(a) polyisocyanates,
(b) contain the composition of active hydrogen, said composition comprises modified vegetable oil-based polyols,
Wherein, the color that the described foam materials of making has is worth by (L) of 70 units at least and (b) value of being not more than 25 units characterizes, and do not containing under the ultra-violet stabilizer condition, be exposed to 6 weeks in the light of envrionment conditions, the variation of its (L) value is no more than 14 units, and (b) variation of value is no more than 14 units.
51. flexible polyurethane foams as claimed in claim 50, it is characterized in that (a) value of the foam materials of making is not more than 4 units, wherein, when being exposed to the light of envrionment conditions under not containing the ultra-violet stabilizer condition, its (a) value variation is no more than 5 units.
52. flexible polyurethane foams as claimed in claim 50, it is characterized in that, the feature of described modified vegetable oil-based polyols is, according to the BVT reactivity test described polyvalent alcohol is mixed the formation reaction mixture with catalyzer and tolylene diisocyanate, the viscosity of the reaction mixture that records 600 seconds the time after forming described reaction mixture is at least 5,000mPa.s.
53. flexible polyurethane foams as claimed in claim 50, it is characterized in that, the feature of described modified vegetable oil-based polyols is, according to the BVT reactivity test described polyvalent alcohol is mixed the formation reaction mixture with catalyzer and tolylene diisocyanate, the viscosity of the reaction mixture that records 600 seconds the time after forming described reaction mixture is at least 10,000mPa.s.
54. flexible polyurethane foams as claimed in claim 50, it is characterized in that, the feature of modified vegetable oil-based polyols is, according to the BVT reactivity test described polyvalent alcohol is mixed the formation reaction mixture with catalyzer and tolylene diisocyanate, the viscosity of the reaction mixture that records 600 seconds the time after forming described reaction mixture is at least 20,000mPa.s.
55. flexible polyurethane foams as claimed in claim 50 is characterized in that, described modified vegetable oil-based polyols comprises the modified soyabean oil polylol.
56. flexible polyurethane foams as claimed in claim 50 is characterized in that, described modified vegetable oil-based polyols is to prepare by the method that comprises one or more pairs of key reactions that make vegetables oil.
57. flexible polyurethane foams as claimed in claim 50 is characterized in that, described modified vegetable oil-based polyols adopts the method preparation that may further comprise the steps:
(a) form epoxidized vegetable oil;
(b) described epoxidized vegetable oil is mixed with the fluoroboric acid of pure and mild catalytic amount, to form the vegetable oil-based polyols of modification.
58. flexible polyurethane foams as claimed in claim 57 is characterized in that, described epoxidized vegetable oil is the part epoxidized vegetable oil, and the vegetable oil-based polyols of described modification comprises two keys.
59. flexible polyurethane foams as claimed in claim 50 is characterized in that, described modified vegetable oil-based polyols adopts the method preparation that may further comprise the steps:
(a) vegetables oil and carbon monoxide and hydrogen are reacted in the presence of the group VIII metal catalyst, to form the hydroformylation vegetables oil;
(b) toilet is stated the hydrogenation of hydroformylation vegetables oil, to form the vegetable oil-based polyols of modification.
60. flexible polyurethane foams as claimed in claim 50 is characterized in that, described modified vegetable oil-based polyols adopts the method preparation that may further comprise the steps:
(a) vegetables oil and carbon monoxide and hydrogen are reacted in the presence of the group VIII metal catalyst, to form the hydroformylation vegetables oil;
(b) make the hydrogenation of described hydroformylation vegetables oil, to form polyvalent alcohol;
(c) described polyvalent alcohol is mixed with the fluoroboric acid of epoxidized vegetable oil and catalytic amount, to form the vegetable oil-based polyols of modification.
61. flexible polyurethane foams as claimed in claim 60 is characterized in that, described epoxidized vegetable oil is the part epoxidized vegetable oil, and the vegetable oil-based polyols of described modification comprises two keys.
62. a composition that contains active hydrogen, it comprises:
(a) polyvalent alcohol, it is selected from polyether glycol, polyester polyol and their combination;
(b) at least 1 part of modified vegetable oil-based polyols/100 part composition,
The wherein said composition that contains active hydrogen is the stabilising liq form down at 23 ℃.
63. the active hydrogen composition that contains as claimed in claim 62 is characterized in that the vegetable oil-based polyols of described modification comprises the modified soyabean oil polylol.
64. the active hydrogen composition that contains as claimed in claim 62, it is characterized in that, the feature of described modified vegetable oil-based polyols is, according to the BVT reactivity test described polyvalent alcohol is mixed the formation reaction mixture with catalyzer and tolylene diisocyanate, the viscosity of the reaction mixture that records 600 seconds the time after forming described reaction mixture is at least 5,000mPa.s.
65. the active hydrogen composition that contains as claimed in claim 62, it is characterized in that, the feature of modified vegetable oil-based polyols is, according to the BVT reactivity test described polyvalent alcohol is mixed the formation reaction mixture with catalyzer and tolylene diisocyanate, the viscosity of the reaction mixture that records 600 seconds the time after forming described reaction mixture is at least 10,000mPa.s.
66. the active hydrogen composition that contains as claimed in claim 62, it is characterized in that, the feature of modified vegetable oil-based polyols is, according to the BVT reactivity test described polyvalent alcohol is mixed the formation reaction mixture with catalyzer and tolylene diisocyanate, the viscosity of the reaction mixture that records 600 seconds the time after forming described reaction mixture is at least 20,000mPa.s.
67. the active hydrogen composition that contains as claimed in claim 62 is characterized in that, described modified vegetable oil-based polyols is to prepare by the method that comprises one or more pairs of key reactions that make vegetables oil.
68. the active hydrogen composition that contains as claimed in claim 62 is characterized in that, described modified vegetable oil-based polyols adopts the method preparation that may further comprise the steps:
(a) provide vegetables oil, to form epoxidized vegetable oil;
(b) mixture of described epoxidized vegetable oil with the fluoroboric acid that comprises pure and mild catalytic amount mixed, to form the vegetable oil-based polyols of modification.
69. as the described active hydrogen composition that contains of claim 68, it is characterized in that described epoxidized vegetable oil is the part epoxidized vegetable oil, and the vegetable oil-based polyols of described modification comprises two keys.
70. the active hydrogen composition that contains as claimed in claim 62 is characterized in that, described modified vegetable oil-based polyols adopts the method preparation that may further comprise the steps:
(a) vegetables oil and carbon monoxide and hydrogen are reacted in the presence of the group VIII metal catalyst, to form the hydroformylation vegetables oil;
(b) make the hydrogenation of described hydroformylation vegetables oil, to form the vegetable oil-based polyols of modification.
71. the active hydrogen composition that contains as claimed in claim 62 is characterized in that, described modified vegetable oil-based polyols adopts the method preparation that may further comprise the steps:
(a) vegetables oil and carbon monoxide and hydrogen are reacted in the presence of the group VIII metal catalyst, to form the hydroformylation vegetables oil;
(b) make the hydrogenation of described hydroformylation vegetables oil, to form polyvalent alcohol;
(c) fluoroboric acid of described polyvalent alcohol with epoxidized vegetable oil and catalytic amount mixed, to form the vegetable oil-based polyols of modification.
72. as the described active hydrogen composition that contains of claim 71, it is characterized in that described epoxidized vegetable oil is the part epoxidized vegetable oil, and the vegetable oil-based polyols of described modification comprises two keys.
73. a composition that contains active hydrogen, it comprises:
(a) polyvalent alcohol, it is selected from polyether glycol, polyester polyol and their combination;
(b) modified vegetable oil-based polyols;
Wherein, the described viscosity that contains the composition of active hydrogen is lower than the comparable viscosity that contains the active hydrogen composition that substitutes the modified vegetable oil-based polyols preparation with copolymer polyols.
74., it is characterized in that described modified vegetable oil-based polyols comprises the modified soyabean oil polylol as the described active hydrogen composition that contains of claim 73.
75. as the described active hydrogen composition that contains of claim 73, it is characterized in that, the feature of described modified vegetable oil-based polyols is, according to the BVT reactivity test described polyvalent alcohol is mixed the formation reaction mixture with catalyzer and tolylene diisocyanate, the viscosity of the reaction mixture that records 600 seconds the time after forming described reaction mixture is at least 5,000mPa.s.
76. as the described active hydrogen composition that contains of claim 73, it is characterized in that, the feature of modified vegetable oil-based polyols is, according to the BVT reactivity test described polyvalent alcohol is mixed the formation reaction mixture with catalyzer and tolylene diisocyanate, the viscosity of the reaction mixture that records 600 seconds the time after forming described reaction mixture is at least 10,000mPa.s.
77. as the described active hydrogen composition that contains of claim 73, it is characterized in that, the feature of modified vegetable oil-based polyols is, according to the BVT reactivity test described polyvalent alcohol is mixed the formation reaction mixture with catalyzer and tolylene diisocyanate, the viscosity of the reaction mixture that records 600 seconds the time after forming described reaction mixture is at least 20,000mPa.s.
78., it is characterized in that described modified vegetable oil-based polyols is to prepare by the method that comprises one or more pairs of key reactions that make vegetables oil as the described active hydrogen composition that contains of claim 73.
79., it is characterized in that described modified vegetable oil-based polyols adopts the method preparation that may further comprise the steps as the described active hydrogen composition that contains of claim 73:
(a) provide vegetables oil, to form epoxidized vegetable oil;
(b) mixture of described epoxidized vegetable oil with the fluoroboric acid that comprises pure and mild catalytic amount mixed, to form the vegetable oil-based polyols of modification.
80. as the described active hydrogen composition that contains of claim 79, it is characterized in that described epoxidized vegetable oil is the part epoxidized vegetable oil, and described modified vegetable oil-based polyols comprises two keys.
81., it is characterized in that described modified vegetable oil-based polyols adopts the method preparation that may further comprise the steps as the described active hydrogen composition that contains of claim 73:
(a) vegetables oil and carbon monoxide and hydrogen are reacted in the presence of the group VIII metal catalyst, to form the hydroformylation vegetables oil;
(b) make the hydrogenation of described hydroformylation vegetables oil, to form the vegetable oil-based polyols of modification.
82., it is characterized in that described modified vegetable oil-based polyols adopts the method preparation that may further comprise the steps as the described active hydrogen composition that contains of claim 73:
(a) vegetables oil and carbon monoxide and hydrogen are reacted in the presence of the group VIII metal catalyst, to form the hydroformylation vegetables oil;
(b) make the hydrogenation of described hydroformylation vegetables oil, to form polyvalent alcohol;
(c) fluoroboric acid of described polyvalent alcohol with epoxidized vegetable oil and catalytic amount mixed, to form the vegetable oil-based polyols of modification.
83. as the described active hydrogen composition that contains of claim 82, it is characterized in that described epoxidized vegetable oil is the part epoxidized vegetable oil, and described modified vegetable oil-based polyols comprises two keys.
84. a composition that contains active hydrogen, it comprises:
(a) polyvalent alcohol, it is selected from polyether glycol, polyester polyol and their combination;
(b) modified vegetable oil-based polyols,
Wherein, the described composition that contains active hydrogen does not contain granularity substantially greater than 0.1 micron particle.
85., it is characterized in that described modified vegetable oil-based polyols comprises the modified soyabean oil polylol as the described active hydrogen composition that contains of claim 84.
86. as the described active hydrogen composition that contains of claim 84, it is characterized in that, the feature of described modified vegetable oil-based polyols is, according to the BVT reactivity test described polyvalent alcohol is mixed the formation reaction mixture with catalyzer and tolylene diisocyanate, the viscosity of the reaction mixture that records 600 seconds the time after forming described reaction mixture is at least 5,000mPa.s.
87. as the described active hydrogen composition that contains of claim 84, it is characterized in that, the feature of modified vegetable oil-based polyols is, according to the BVT reactivity test described polyvalent alcohol is mixed the formation reaction mixture with catalyzer and tolylene diisocyanate, the viscosity of the reaction mixture that records 600 seconds the time after forming described reaction mixture is at least 10,000mPa.s.。
88. as the described active hydrogen composition that contains of claim 84, it is characterized in that, the feature of modified vegetable oil-based polyols is, according to the BVT reactivity test described polyvalent alcohol is mixed the formation reaction mixture with catalyzer and tolylene diisocyanate, the viscosity of the reaction mixture that records 600 seconds the time after forming described reaction mixture is at least 20,000mPa.s.
89., it is characterized in that described modified vegetable oil-based polyols is to prepare by the method that comprises one or more pairs of key reactions that make vegetables oil as the described active hydrogen composition that contains of claim 84.
90., it is characterized in that described modified vegetable oil-based polyols adopts the method preparation that may further comprise the steps as the described active hydrogen composition that contains of claim 84:
(a) provide vegetables oil, to form epoxidized vegetable oil;
(b) mixture of described epoxidized vegetable oil with the fluoroboric acid that comprises pure and mild catalytic amount mixed, to form the vegetable oil-based polyols of modification.
91. as the described active hydrogen composition that contains of claim 90, it is characterized in that described epoxidized vegetable oil is the part epoxidized vegetable oil, and described modified vegetable oil-based polyols comprises two keys.
92., it is characterized in that described modified vegetable oil-based polyols adopts the method preparation that may further comprise the steps as the described active hydrogen composition that contains of claim 84:
(a) vegetables oil and carbon monoxide and hydrogen are reacted in the presence of the group VIII metal catalyst, to form the hydroformylation vegetables oil;
(b) make the hydrogenation of described hydroformylation vegetables oil, to form modified vegetable oil-based polyols.
93., it is characterized in that described modified vegetable oil-based polyols adopts the method preparation that may further comprise the steps as the described active hydrogen composition that contains of claim 84:
(a) vegetables oil and carbon monoxide and hydrogen are reacted in the presence of the group VIII metal catalyst, to form the hydroformylation vegetables oil;
(b) make the hydrogenation of described hydroformylation vegetables oil, to form polyvalent alcohol;
(c) fluoroboric acid of described polyvalent alcohol with epoxidized vegetable oil and catalytic amount mixed, to form modified vegetable oil-based polyols.
94. as the described active hydrogen composition that contains of claim 93, it is characterized in that described epoxidized vegetable oil is the part epoxidized vegetable oil, and the vegetable oil-based polyols of described modification comprises two keys.
95. a flexible polyurethane foams, it comprises the reaction product of following component in the presence of whipping agent:
(a) polyisocyanates,
(b) contain the composition of active hydrogen, described composition comprises modified vegetable oil-based polyols,
Wherein, the feature of described modified vegetable oil-based polyols is, described polyvalent alcohol mixed forming reaction mixture according to the BVT reactivity test with catalyzer and tolylene diisocyanate, and the viscosity of the reaction mixture that records 600 seconds the time after forming described reaction mixture is at least 5,000mPa.s
Wherein, the sag factor of described foam materials is at least 2.5.
96. as the described flexible polyurethane foams of claim 95, it is characterized in that, the feature of modified vegetable oil-based polyols is, according to the BVT reactivity test described polyvalent alcohol is mixed the formation reaction mixture with catalyzer and tolylene diisocyanate, the viscosity of the reaction mixture that records 600 seconds the time after forming described reaction mixture is at least 10,000mPa.s.。
97. as the described flexible polyurethane foams of claim 95, it is characterized in that, the feature of modified vegetable oil-based polyols is, according to the BVT reactivity test described polyvalent alcohol is mixed the formation reaction mixture with catalyzer and tolylene diisocyanate, the viscosity of the reaction mixture that records 600 seconds the time after forming described reaction mixture is at least 20,000mPa.s.
98. a flexible polyurethane foams, it comprises first area with first hardness value and the second area with second hardness value that is different from first hardness value, and wherein at least one zone comprises the reaction product of following component in the presence of whipping agent:
(a) polyisocyanates,
(b) contain the composition of active hydrogen, described composition comprises modified vegetable oil-based polyols;
And the load efficiency numbers in described zone is at least 4 newton/part modified vegetable oil-based polyols.
99., it is characterized in that described modified vegetable oil-based polyols comprises the polyvalent alcohol that is derived from modified soyabean oil as the described flexible polyurethane foams of claim 98.
100. as the described flexible polyurethane foams of claim 98, it is characterized in that, the feature of described modified vegetable oil-based polyols is, according to the BVT reactivity test described polyvalent alcohol is mixed the formation reaction mixture with catalyzer and tolylene diisocyanate, the viscosity of the reaction mixture that records 600 seconds the time after forming described reaction mixture is at least 5,000mPa.s.
101. as the described flexible polyurethane foams of claim 98, it is characterized in that, the feature of modified vegetable oil-based polyols is, according to the BVT reactivity test described polyvalent alcohol is mixed the formation reaction mixture with catalyzer and tolylene diisocyanate, the viscosity of the reaction mixture that records 600 seconds the time after forming described reaction mixture is at least 10,000mPa.s.
102. as the described flexible polyurethane foams of claim 98, it is characterized in that, the feature of modified vegetable oil-based polyols is, according to the BVT reactivity test described polyvalent alcohol is mixed the formation reaction mixture with catalyzer and tolylene diisocyanate, the viscosity of the reaction mixture that records 600 seconds the time after forming described reaction mixture is at least 20,000mPa.s.
103., it is characterized in that described modified vegetable oil-based polyols is to prepare by the method that comprises one or more pairs of key reactions that make vegetables oil as the described flexible polyurethane foams of claim 98.
104. a seat part, it comprises flexible polyurethane foams,
Described polyurethane foamed material comprises the reaction product of following component in the presence of whipping agent:
(a) polyisocyanates,
(b) contain the composition of active hydrogen, described composition comprises modified vegetable oil-based polyols;
Wherein, the load efficiency numbers of described foam materials is at least 4 newton/part modified vegetable oil-based polyols.
105. as the described seat part of claim 104, it is characterized in that, described foam materials is not being contained under the ultra-violet stabilizer condition, be exposed to 6 time-of-weeks in the light of envrionment conditions, its color that has is worth by (L) of 70 units at least and (b) value of being not more than 25 units characterizes.
106., it is characterized in that the color of described foam materials is characterized by (a) value that is not more than 4 units as the described seat part of claim 105.
107. as the described seat part of claim 104, it is characterized in that, the color that the foam materials of making has is worth by (L) of 70 units at least and (b) value of being not more than 25 units characterizes, wherein, do not containing under the ultra-violet stabilizer condition, be exposed to 6 time-of-weeks in the light of envrionment conditions, its (L) value changes and is no more than 14 units, and (b) value variation is no more than 14 units.
108. as the described seat part of claim 107, it is characterized in that, (a) value of the foam materials of making is not more than 4 units, and is exposed to 6 time-of-weeks in the light of envrionment conditions under not containing the ultra-violet stabilizer condition, and the variation of its (a) value is no more than 5 units.
109. as the described seat part of claim 104, it is characterized in that, the feature of described modified vegetable oil-based polyols is, according to the BVT reactivity test described polyvalent alcohol is mixed the formation reaction mixture with catalyzer and tolylene diisocyanate, the viscosity of the reaction mixture that records 600 seconds the time after forming described reaction mixture is at least 5,000mPa.s.
110. as the described seat part of claim 104, it is characterized in that, the feature of described modified vegetable oil-based polyols is, according to the BVT reactivity test described polyvalent alcohol is mixed the formation reaction mixture with catalyzer and tolylene diisocyanate, the viscosity of the reaction mixture that records 600 seconds the time after forming described reaction mixture is at least 10,000mPa.s.
111. as the described seat part of claim 104, it is characterized in that, the feature of described modified vegetable oil-based polyols is, according to the BVT reactivity test described polyvalent alcohol is mixed the formation reaction mixture with catalyzer and tolylene diisocyanate, the viscosity of the reaction mixture that records 600 seconds the time after forming described reaction mixture is at least 20,000mPa.s.
112., it is characterized in that described modified vegetable oil-based polyols comprises the modified soyabean oil polylol as the described seat part of claim 104.
113., it is characterized in that described modified vegetable oil-based polyols is to prepare by the method that comprises one or more pairs of key reactions that make vegetables oil as the described seat part of claim 104.
114., it is characterized in that described modified vegetable oil-based polyols adopts the method preparation that may further comprise the steps as the described seat part of claim 104:
(a) provide epoxidized vegetable oil;
(b) mixture of described epoxidized vegetable oil with the fluoroboric acid that comprises pure and mild catalytic amount mixed, to form the vegetable oil-based polyols of modification.
115., it is characterized in that described epoxidized vegetable oil is the part epoxidized vegetable oil as the described seat part of claim 104, and the vegetable oil-based polyols of described modification comprises two keys.
116., it is characterized in that described modified vegetable oil-based polyols adopts the method preparation that may further comprise the steps as the described seat part of claim 104:
(a) vegetables oil and carbon monoxide and hydrogen are reacted in the presence of the group VIII metal catalyst, to form the hydroformylation vegetables oil;
(b) make the hydrogenation of described hydroformylation vegetables oil, to form modified vegetable oil-based polyols.
117., it is characterized in that described modified vegetable oil-based polyols adopts the method preparation that may further comprise the steps as the described seat part of claim 104:
(a) vegetables oil and carbon monoxide and hydrogen are reacted in the presence of the group VIII metal catalyst, to form the hydroformylation vegetables oil;
(b) make the hydrogenation of described hydroformylation vegetables oil, to form polyvalent alcohol;
(c) described polyvalent alcohol is mixed with the fluoroboric acid of epoxidized vegetable oil and catalytic amount, to form modified vegetable oil-based polyols.
118. the foam materials as the described seat part of claim 117 is characterized in that, described epoxidized vegetable oil is the part epoxidized vegetable oil, and the vegetable oil-based polyols of described modification comprises two keys.
119., it is characterized in that the described active hydrogen composition that contains also comprises the polyvalent alcohol that is selected from polyether glycol, polyester polyol and their combination as the described seat part of claim 104.
120., it is characterized in that described seat part is the seat part that is used for motor vehicle as the described seat part of claim 104.
121. as the described seat part of claim 104, it is characterized in that, described seat part comprises flexible polyurethane foams, described flexible polyurethane foams comprises first area with first hardness value and the second area with second hardness value that is different from first hardness value, and wherein at least one zone comprises the reaction product of following component in the presence of whipping agent:
(a) polyisocyanates,
(b) contain the composition of active hydrogen, described composition comprises modified vegetable oil-based polyols;
And the load efficiency numbers in described zone is at least 4 newton/part modified vegetable oil-based polyols.
122. a carpet lining, it comprises the described flexible polyurethane foams of claim 1.
123. a mat, it comprises the described flexible polyurethane foams of claim 1.
124. a method of making goods, this method comprises:
In the mould of predetermined shape, add (a) polyisocyanates and (b) comprise modified vegetable oil-based polyols contain the active hydrogen composition;
Described polyisocyanates and the described active hydrogen composition that contains are reacted in the presence of whipping agent in mould, and to make the goods that comprise flexible polyurethane foams, the load efficiency numbers of described foam materials is at least 4 newton/part modified vegetable oil-based polyols.
125., it is characterized in that described goods are seat parts as the described method of claim 124.
126. as the described method of claim 124, it is characterized in that, the feature of described modified vegetable oil-based polyols is, according to the BVT reactivity test described polyvalent alcohol is mixed the formation reaction mixture with catalyzer and tolylene diisocyanate, the viscosity of the reaction mixture that records 600 seconds the time after forming described reaction mixture is at least 5,000mPa.s.
127. as the described method of claim 124, it is characterized in that, the feature of modified vegetable oil-based polyols is, according to the BVT reactivity test described polyvalent alcohol is mixed the formation reaction mixture with catalyzer and tolylene diisocyanate, the viscosity of the reaction mixture that records 600 seconds the time after forming described reaction mixture is at least 10,000mPa.s.
128. as the described method of claim 124, it is characterized in that, the feature of modified vegetable oil-based polyols is, according to the BVT reactivity test described polyvalent alcohol is mixed the formation reaction mixture with catalyzer and tolylene diisocyanate, the viscosity of the reaction mixture that records 600 seconds the time after forming described reaction mixture is at least 20,000mPa.s.
129., it is characterized in that described modified vegetable oil-based polyols is to prepare by the method that comprises one or more pairs of key reactions that make vegetables oil as the described method of claim 124.
130. a method of making goods, it comprises:
(a) polyisocyanates and the composition that contains active hydrogen that (b) comprises modified vegetable oil-based polyols are being reacted in the presence of whipping agent on the foam materials transmission assembly, to be made for the flexible polyurethane foams of piece material form, its load efficiency numbers is at least 4 newton/part modified vegetable oil-based polyols;
Described block material is shaped, to form goods.
131. as the described method of claim 130, it is characterized in that, the feature of modified vegetable oil-based polyols is, according to the BVT reactivity test described polyvalent alcohol is mixed the formation reaction mixture with catalyzer and tolylene diisocyanate, the viscosity of the reaction mixture that records 600 seconds the time after forming described reaction mixture is at least 5,000mPa.s.
132. as the described method of claim 130, it is characterized in that, the feature of modified vegetable oil-based polyols is, according to the BVT reactivity test described polyvalent alcohol is mixed the formation reaction mixture with catalyzer and tolylene diisocyanate, the viscosity of the reaction mixture that records 600 seconds the time after forming described reaction mixture is at least 10,000mPa.s.
133. as the described method of claim 130, it is characterized in that, the feature of modified vegetable oil-based polyols is, according to the BVT reactivity test described polyvalent alcohol is mixed the formation reaction mixture with catalyzer and tolylene diisocyanate, the viscosity of the reaction mixture that records 600 seconds the time after forming described reaction mixture is at least 20,000mPa.s.
134., it is characterized in that described modified vegetable oil-based polyols is to prepare by the method that comprises one or more pairs of key reactions that make vegetables oil as the described method of claim 130.
135. a flexible polyurethane foams, it comprises the reaction product of following component in the presence of whipping agent:
(a) polyisocyanates,
(b) contain the composition of active hydrogen, described composition comprises the soya-bean oil polylol and is selected from the polyvalent alcohol of polyether glycol, polyester polyol and their combination,
Wherein, the method preparation of described modified soyabean oil polylol by may further comprise the steps:
(A) provide epoxidized soybean oil, and described epoxidized soybean oil is mixed with the fluoroboric acid of pure and mild catalytic amount, to form the modified soyabean oil polylol;
(B) soya-bean oil and carbon monoxide and hydrogen are reacted in the presence of the group VIII metal catalyst, with formation hydroformylation soya-bean oil, and make the hydrogenation of described hydroformylation soya-bean oil, to form the modified soyabean oil polylol; Or
(C) vegetables oil and carbon monoxide and hydrogen are reacted in the presence of the group VIII metal catalyst; to form the hydroformylation vegetables oil; and make the hydrogenation of described hydroformylation vegetables oil; to form polyvalent alcohol; and described polyvalent alcohol is mixed with the fluoroboric acid of epoxidized vegetable oil and catalytic amount; to form modified vegetable oil-based polyols
Wherein, the load efficiency numbers of described foam materials is at least 4 newton/part modified soyabean oil polylol.
136., it is characterized in that described epoxidized vegetable oil is the part epoxidized vegetable oil as the described flexible polyurethane foams of claim 135, and described modified vegetable oil-based polyols comprises two keys.
137. a seat part that comprises flexible polyurethane foams, described polyurethane foamed material comprise the reaction product of following component in the presence of whipping agent:
(a) polyisocyanates,
(b) contain the composition of active hydrogen, described composition comprises the soya-bean oil polylol and is selected from the polyvalent alcohol of polyether glycol, polyester polyol and their combination,
Wherein, the method preparation of described modified soyabean oil polylol by may further comprise the steps:
(A) provide epoxidized soybean oil, and with described epoxidized soybean oil and the mixture chemical combination that comprises pure and mild catalytic amount fluoroboric acid, to form the modified soyabean oil polylol;
(B) soya-bean oil and carbon monoxide and hydrogen are reacted in the presence of the group VIII metal catalyst, with formation hydroformylation soya-bean oil, and make the hydrogenation of described hydroformylation soya-bean oil, to form the modified soyabean oil polylol; Or
(C) vegetables oil and carbon monoxide and hydrogen are reacted in the presence of the group VIII metal catalyst; to form the hydroformylation vegetables oil; and make the hydrogenation of described hydroformylation vegetables oil; to form polyvalent alcohol; and described polyvalent alcohol is mixed with the fluoroboric acid of epoxidized vegetable oil and catalytic amount; to form modified vegetable oil-based polyols
The load efficiency numbers of described foam materials is at least 4 newton/part modified soyabean oil polylol.
138., it is characterized in that described epoxidized vegetable oil is the part epoxidized vegetable oil as the described flexible polyurethane foams of claim 137, and the vegetable oil-based polyols of described modification comprises two keys.
139. a flexible polyurethane foams, it comprises the reaction product of following component in the presence of whipping agent:
(a) polyisocyanates,
(b) contain the composition of active hydrogen, described composition comprises vegetable oil-based polyols,
Wherein, the feature of described modified vegetable oil-based polyols is, according to the BVT reactivity test described polyvalent alcohol is mixed to form reaction mixture with catalyzer and tolylene diisocyanate, the viscosity of the reaction mixture that records 600 seconds the time after forming described reaction mixture is at least 5,000mPa.s.
140. as the described flexible polyurethane foams of claim 139, it is characterized in that, the feature of modified vegetable oil-based polyols is, according to the BVT reactivity test described polyvalent alcohol is mixed the formation reaction mixture with catalyzer and tolylene diisocyanate, the viscosity of the reaction mixture that records 600 seconds the time after forming described reaction mixture is at least 10,000mPa.s.
141. as the described flexible polyurethane foams of claim 139, it is characterized in that, the feature of modified vegetable oil-based polyols is, according to the BVT reactivity test described polyvalent alcohol is mixed the formation reaction mixture with catalyzer and tolylene diisocyanate, the viscosity of the reaction mixture that records 600 seconds the time after forming described reaction mixture is at least 20,000mPa.s.
142. a flexible polyurethane foams, it comprises the reaction product of following component in the presence of whipping agent:
(a) polyisocyanates,
(b) contain the composition of active hydrogen, described composition comprises modified vegetable oil-based polyols,
Wherein, the hardness value of described foam materials is greater than the hardness value of using the contrast foam materials that contains the active hydrogen preparation of compositions that does not contain described modified vegetable oil-based polyols.
CN 200480034513 2003-09-30 2004-09-30 Flexible polyurethane foams prepared using modified vegetable oil-based polyols Pending CN1926164A (en)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101503571B (en) * 2008-02-08 2013-04-10 赢创戈尔德施米特有限公司 Siloxane compositions
CN101230020B (en) * 2008-02-26 2013-05-22 北京市丰信德科技发展有限公司 Method for synthesizing macromonomer for polymer polyol by plant oil and uses thereof
CN101679587B (en) * 2008-02-01 2014-03-12 陶氏环球技术有限责任公司 Natural oil based copolymer polyols and polyurethane products made therefrom
CN101815736B (en) * 2007-08-21 2014-09-03 李尔公司 Hydroxyl terminated precursor and method of making the same
CN109843960A (en) * 2016-10-28 2019-06-04 科思创德国股份有限公司 The method for manufacturing polyurethane foam molded article
CN112225866A (en) * 2020-10-12 2021-01-15 江南大学 Bio-based polyurethane hard foam material and preparation method thereof
US11168176B2 (en) 2018-09-27 2021-11-09 Lear Corporation Automotive seat made from epoxidized soy oil

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101815736B (en) * 2007-08-21 2014-09-03 李尔公司 Hydroxyl terminated precursor and method of making the same
CN101679587B (en) * 2008-02-01 2014-03-12 陶氏环球技术有限责任公司 Natural oil based copolymer polyols and polyurethane products made therefrom
CN101503571B (en) * 2008-02-08 2013-04-10 赢创戈尔德施米特有限公司 Siloxane compositions
CN101230020B (en) * 2008-02-26 2013-05-22 北京市丰信德科技发展有限公司 Method for synthesizing macromonomer for polymer polyol by plant oil and uses thereof
CN109843960A (en) * 2016-10-28 2019-06-04 科思创德国股份有限公司 The method for manufacturing polyurethane foam molded article
CN109843960B (en) * 2016-10-28 2021-08-10 科思创德国股份有限公司 Process for producing polyurethane foam molded article
US11168176B2 (en) 2018-09-27 2021-11-09 Lear Corporation Automotive seat made from epoxidized soy oil
CN112225866A (en) * 2020-10-12 2021-01-15 江南大学 Bio-based polyurethane hard foam material and preparation method thereof

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