CN119192519A - A kind of viscoelastic polyurethane foam and its preparation method and application - Google Patents
A kind of viscoelastic polyurethane foam and its preparation method and application Download PDFInfo
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- CN119192519A CN119192519A CN202411686235.0A CN202411686235A CN119192519A CN 119192519 A CN119192519 A CN 119192519A CN 202411686235 A CN202411686235 A CN 202411686235A CN 119192519 A CN119192519 A CN 119192519A
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- China
- Prior art keywords
- polyether polyol
- isocyanate
- polyurethane foam
- ethylene oxide
- viscoelastic polyurethane
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- 229920005830 Polyurethane Foam Polymers 0.000 title claims abstract description 57
- 239000011496 polyurethane foam Substances 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title abstract description 19
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 86
- 229920000570 polyether Polymers 0.000 claims abstract description 86
- 229920005862 polyol Polymers 0.000 claims abstract description 82
- 150000003077 polyols Chemical class 0.000 claims abstract description 82
- 239000012948 isocyanate Substances 0.000 claims abstract description 48
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 48
- 239000004088 foaming agent Substances 0.000 claims abstract description 22
- 239000000203 mixture Substances 0.000 claims abstract description 22
- 238000004519 manufacturing process Methods 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 19
- 238000009413 insulation Methods 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 69
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 67
- 239000000178 monomer Substances 0.000 claims description 54
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 33
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 30
- 239000003054 catalyst Substances 0.000 claims description 20
- 239000003999 initiator Substances 0.000 claims description 18
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 claims description 12
- 229920001228 polyisocyanate Polymers 0.000 claims description 12
- 239000005056 polyisocyanate Substances 0.000 claims description 12
- 238000006116 polymerization reaction Methods 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 12
- 238000005187 foaming Methods 0.000 claims description 11
- -1 alcohol compound Chemical class 0.000 claims description 10
- 239000004094 surface-active agent Substances 0.000 claims description 10
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 4
- 150000001298 alcohols Chemical class 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 4
- 125000002524 organometallic group Chemical group 0.000 claims description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000006260 foam Substances 0.000 abstract description 10
- 230000000704 physical effect Effects 0.000 abstract description 3
- 238000012360 testing method Methods 0.000 description 10
- 239000004604 Blowing Agent Substances 0.000 description 9
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 239000006261 foam material Substances 0.000 description 5
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- IUNMPGNGSSIWFP-UHFFFAOYSA-N dimethylaminopropylamine Chemical compound CN(C)CCCN IUNMPGNGSSIWFP-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- FRCHKSNAZZFGCA-UHFFFAOYSA-N 1,1-dichloro-1-fluoroethane Chemical compound CC(F)(Cl)Cl FRCHKSNAZZFGCA-UHFFFAOYSA-N 0.000 description 2
- OVWMLAPGHWXVDA-UHFFFAOYSA-N CC(C(CCCN(C)C)CCCN(C)C)(N)O Chemical compound CC(C(CCCN(C)C)CCCN(C)C)(N)O OVWMLAPGHWXVDA-UHFFFAOYSA-N 0.000 description 2
- 235000009499 Vanilla fragrans Nutrition 0.000 description 2
- 235000012036 Vanilla tahitensis Nutrition 0.000 description 2
- 239000001273 butane Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N isopropyl alcohol Natural products CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- BXYVQNNEFZOBOZ-UHFFFAOYSA-N n-[3-(dimethylamino)propyl]-n',n'-dimethylpropane-1,3-diamine Chemical compound CN(C)CCCNCCCN(C)C BXYVQNNEFZOBOZ-UHFFFAOYSA-N 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- NVSXSBBVEDNGPY-UHFFFAOYSA-N 1,1,1,2,2-pentafluorobutane Chemical compound CCC(F)(F)C(F)(F)F NVSXSBBVEDNGPY-UHFFFAOYSA-N 0.000 description 1
- GTEXIOINCJRBIO-UHFFFAOYSA-N 2-[2-(dimethylamino)ethoxy]-n,n-dimethylethanamine Chemical compound CN(C)CCOCCN(C)C GTEXIOINCJRBIO-UHFFFAOYSA-N 0.000 description 1
- MEMHRGDJOQLBJI-UHFFFAOYSA-N 4,6-diaminohexan-2-ol Chemical compound CC(O)CC(N)CCN MEMHRGDJOQLBJI-UHFFFAOYSA-N 0.000 description 1
- 229920000604 Polyethylene Glycol 200 Polymers 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 244000290333 Vanilla fragrans Species 0.000 description 1
- 244000263375 Vanilla tahitensis Species 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000002666 chemical blowing agent Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 229960002887 deanol Drugs 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 239000012972 dimethylethanolamine Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- MSSNHSVIGIHOJA-UHFFFAOYSA-N pentafluoropropane Chemical compound FC(F)CC(F)(F)F MSSNHSVIGIHOJA-UHFFFAOYSA-N 0.000 description 1
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
- C08G18/4816—Two or more polyethers of different physical or chemical nature mixtures of two or more polyetherpolyols having at least three hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
- C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
- C08G18/4841—Polyethers containing oxyethylene units and other oxyalkylene units containing oxyethylene end groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2101/00—Manufacture of cellular products
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0083—Foam properties prepared using water as the sole blowing agent
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to the technical field of polyurethane foam materials, provides a viscoelastic polyurethane foam, a preparation method and application thereof, the preparation method is adopted to prepare the viscoelastic polyurethane foam, the method has the characteristics of quick curing and high production efficiency, can obtain the viscoelastic polyurethane foam with low density and good physical properties, and can meet the technical requirements of the automobile sound insulation pad foam. The preparation method comprises the steps of reacting materials comprising isocyanate reactive components and isocyanate to obtain the viscoelastic polyurethane foam, wherein the isocyanate reactive components comprise polyether polyol compositions and foaming agents, the polyether polyol compositions comprise polyether polyol A1 and polyether polyol A2, the amount of the polyether polyol A1 is 25-65 parts by mass, the amount of the polyether polyol A2 is 30-70 parts by mass, and the amount of the foaming agents is 3-6 parts by mass.
Description
Technical Field
The invention relates to the technical field of polyurethane foam materials, in particular to a viscoelastic polyurethane foam and a preparation method and application thereof.
Background
Polyurethane foams are currently widely used in vehicles such as automobiles, high-speed rails, and airplanes. The modified polyurethane foam is generally used for preparing parts such as automobile carpets, front walls, hat racks, spare tire mats and the like, plays a role in decoration of automobile interiors, has the effects of sound absorption, noise reduction, vibration reduction and the like, and improves the comfort of the interior of an automobile. Along with the development needs of light weight, intelligence, comfort and safety and environmental protection in the automobile industry, the traditional high-resilience polyurethane sponge can not meet the current comfort requirement, and the viscoelastic polyurethane foam has better effects of energy absorption, shock absorption and sound absorption, and can greatly improve the comfort of the automobile.
Chinese patent CN1257203C discloses a viscoelastic polyurethane foam which uses polyether a with 3 functionality, EO content of 75% wt, hydroxyl value of 42mgKOH/g, polyether B with 3 functionality, EO content of 28% wt, hydroxyl value of 28mgKOH/g and PEG-200 as main raw materials, and the prepared foam has obvious disadvantages such as high density, low tear strength and low tensile strength.
Chinese patent application CN116239746A discloses a preparation method of viscoelastic polyurethane foam, which shows that the viscoelastic polyurethane foam has obvious advantages in terms of sound absorption performance compared with high-resilience polyurethane foam, but the preparation process also has obvious defects of slow curing, so that the production efficiency is low, the cost is increased, and meanwhile, the specific performance of the prepared foam is not pointed out.
Chinese patent CN1175020C discloses a method for preparing viscoelastic polyurethane foam, wherein the prepared foam can meet the requirements of automobile parts only when the density is above 65kg/m 3, and the tensile strength and tear strength of the foam can not meet the actual production requirements, and the production cost is greatly increased.
Chinese patent application CN115803355A discloses polyurethane foam with improved acoustic performance, but the foam density is less than 25kg/m 3, and the tensile strength and the elongation at break of the foam are very low, which obviously belongs to semi-rigid polyurethane foam, and the technical requirement of an automobile sound insulation pad can not be met far.
Therefore, development of a technology for preparing a viscoelastic polyurethane foam is desired to be able to simultaneously satisfy the technical requirements (for example, tensile strength of 90kPa or more, elongation at break of 90% or more, tear strength of 1.7N/cm or more, etc.) of automobile parts such as an automobile sound insulation mat foam and the requirements for a short curing time to improve production efficiency.
Disclosure of Invention
Aiming at least one defect in the prior art, the invention provides the viscoelastic polyurethane foam, the preparation method and the application thereof, and the viscoelastic polyurethane foam prepared by the preparation method has the characteristics of quick curing and high production efficiency, can obtain the viscoelastic polyurethane foam with low density and good physical properties, and can meet the technical requirements of the automobile sound insulation pad foam.
The invention provides the following technical scheme for achieving the purpose:
The invention provides a preparation method of viscoelastic polyurethane foam, which is obtained by reacting materials comprising isocyanate reactive components and isocyanate, wherein the isocyanate reactive components comprise polyether polyol composition and foaming agent;
The polyether polyol composition comprises polyether polyol A1 and polyether polyol A2;
The hydroxyl values of the polyether polyol A1 and the polyether polyol A2 are 24-42 mgKOH/g respectively, and the content of primary hydroxyl groups is more than or equal to 80wt% based on the total amount of the primary hydroxyl groups and the secondary hydroxyl groups;
The average functionality of the polyether polyol A1 is 3-4, and the polyether polyol takes propylene oxide and ethylene oxide as polymerization monomers and is capped by ethylene oxide, and the ratio of the ethylene oxide monomers is 50-90wt% based on the total amount of the ethylene oxide and the propylene oxide monomers;
the average functionality of the polyether polyol A2 is 3-4, the polyether polyol takes propylene oxide and ethylene oxide as polymerization monomers and is capped by ethylene oxide, and the ethylene oxide monomer accounts for 20-50wt% based on the total amount of the ethylene oxide and the propylene oxide monomers;
In the isocyanate-reactive component, the amount of the polyether polyol A1 is 25-65 parts by mass, the amount of the polyether polyol A2 is 30-70 parts by mass, and the amount of the foaming agent is 3-6 parts by mass.
Preferably, the hydroxyl value of the polyether polyol A1 is 28-42 mgKOH/g, the ratio of ethylene oxide monomers is 70-90 wt% based on the total amount of ethylene oxide and propylene oxide monomers, and the content of primary hydroxyl groups is more than or equal to 85wt% based on the total amount of primary hydroxyl groups and secondary hydroxyl groups;
The hydroxyl value of the polyether polyol A2 is 24-35 mgKOH/g, the ratio of the ethylene oxide monomer is 20-40 wt% based on the total amount of the ethylene oxide and the propylene oxide monomers, and the content of the primary hydroxyl groups is more than or equal to 85wt% based on the total amount of the primary hydroxyl groups and the secondary hydroxyl groups.
Preferably, the polyether polyol A1 takes one or more of an alcohol compound with a functionality of 3 and an alcohol compound with a functionality of 4 as an initiator.
And/or, the polyether polyol A2 takes one or more of alcohol compounds with the functionality of 3 and alcohol compounds with the functionality of 4 as an initiator.
Preferably, the initiator of the polyether polyol A1 is one or more of glycerol, trimethylolpropane or quaternary tetrapentanol;
And/or the initiator of the polyether polyol A2 is one or more of glycerol, trimethylolpropane or quaternary tetrapentanol.
Preferably, in the isocyanate-reactive component, the amount of polyether polyol A1 is 30 to 60 parts by mass, the amount of polyether polyol A2 is 40 to 65 parts by mass, and the amount of foaming agent is 3.5 to 5.5 parts by mass.
Preferably, the isocyanate-reactive component further comprises 0.1-1.5 parts by mass of a catalyst and 0.2-1.5 parts by mass of a surfactant;
and/or the mass ratio of the isocyanate reactive component to the isocyanate is 100:30-70;
And/or the NCO content of the isocyanate is 24-32wt%.
In some embodiments, the isocyanate is selected from one or more of a diphenylmethane polyisocyanate, a2, 4-diphenylmethane diisocyanate, a 4, 4-diphenylmethane diisocyanate, and a polyol-modified isocyanate prepolymer;
and/or the foaming agent is selected from one or more of water, CO 2, alkane foaming agents, chlorine-containing foaming agents and fluorine-containing foaming agents;
and/or the catalyst is selected from one or more of amine catalysts and organometallic catalysts.
Further, the preparation step of the viscoelastic polyurethane foam comprises the following steps:
Uniformly mixing all raw materials of the isocyanate-reactive component to obtain a first mixed material, mixing the first mixed material with the isocyanate to obtain a second mixed material, and transferring the second mixed material into a mold for foaming reaction;
preferably, the first mixed material and the isocyanate are mixed at 20-40 ℃;
preferably, the foaming reaction time is 60-100s;
preferably, the temperature of the mold is 50-80 ℃.
The present invention also provides a viscoelastic polyurethane foam produced by the above-described production method.
The invention also provides the use of the viscoelastic polyurethane foam described above for the preparation of automotive parts, including automotive sound insulation mats;
or the automobile parts comprise one or more of an automobile carpet, a front wall, a wheel cover, a hat rack and a spare tire pad.
The technical scheme provided by the invention has the following beneficial effects:
The viscoelastic polyurethane foam prepared by the method has the characteristic of quick curing, and can be used for obtaining the viscoelastic polyurethane foam which has good comprehensive properties and is particularly suitable for producing the automobile sound insulation pad, and the obtained foam material can be used for obtaining the viscoelastic polyurethane foam which has good tensile strength, elongation at break, tear strength and loss factor, for example, the density is 50-80 kg/m 3, the tensile strength is more than or equal to 90kPa, the elongation is more than or equal to 90%, the tear strength is more than or equal to 1.7N/cm and the loss factor is 0.25-0.7.
Detailed Description
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The term "and/or" as may be used herein includes any and all combinations of one or more of the associated listed items.
The terms "first," "second," and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.
In one aspect, the present invention provides a method of preparing a viscoelastic polyurethane foam by reacting a material comprising an isocyanate-reactive component and an isocyanate, wherein the isocyanate-reactive component comprises a polyether polyol composition and a blowing agent;
The polyether polyol composition comprises polyether polyol A1 and polyether polyol A2;
The hydroxyl values of the polyether polyol A1 and the polyether polyol A2 are 24-42 mgKOH/g respectively, and the content of primary hydroxyl groups in the polyether polyol A1 and the polyether polyol A2 is more than or equal to 80wt% based on the total amount of primary hydroxyl groups and secondary hydroxyl groups;
the average functionality of the polyether polyol A1 is 3-4, and the polyether polyol takes Propylene Oxide (PO) and Ethylene Oxide (EO) as polymerization monomers and is capped by ethylene oxide, and the ratio of the ethylene oxide monomers is 50-90wt% based on the total amount of the ethylene oxide and the propylene oxide monomers;
The average functionality of the polyether polyol A2 is 3-4, and the polyether polyol takes propylene oxide and ethylene oxide as polymerization monomers and is capped by ethylene oxide, and the ratio of the ethylene oxide monomers is 20-50wt% based on the total amount of the ethylene oxide and the propylene oxide monomers;
In the isocyanate-reactive component, the amount of the polyether polyol A1 is 25-65 parts by mass, the amount of the polyether polyol A2 is 30-70 parts by mass, and the amount of the foaming agent is 3-6 parts by mass.
The invention adopts polyether polyol A1, polyether polyol A2 and foaming agent with the dosage range as isocyanate reactive components to react with isocyanate to prepare the viscoelastic polyurethane foam, has quick curing characteristic, and the obtained viscoelastic polyurethane foam has low density and good physical and mechanical properties, can meet the production requirements of sound insulation pads such as automobile front wall, carpets and the like, and improves the production efficiency and reduces the cost.
In a preferred embodiment, the hydroxyl value of the polyether polyol A1 is 28-42 mgKOH/g, the ethylene oxide monomer accounts for 70-90% based on the total amount of ethylene oxide and propylene oxide monomers, and the content of primary hydroxyl groups is more than or equal to 85% based on the total amount of primary hydroxyl groups and secondary hydroxyl groups;
The hydroxyl value of the polyether polyol A2 is 24-35 mgKOH/g, the ratio of ethylene oxide monomers is 20-40% based on the total amount of ethylene oxide and propylene oxide monomers, and the content of primary hydroxyl groups is more than or equal to 85% based on the total amount of primary hydroxyl groups and secondary hydroxyl groups.
Preferably, the polyether polyol A1 takes one or more of an alcohol compound with a functionality of 3 and an alcohol compound with a functionality of 4 as an initiator, and preferably, the polyether polyol A2 takes one or more of an alcohol compound with a functionality of 3 and an alcohol compound with a functionality of 4 as an initiator. Further preferably, the initiator of the polyether polyol A1 is one or more of glycerol, trimethylolpropane or quaternary tetrapentanol, and the initiator of the polyether polyol A2 is one or more of glycerol, trimethylolpropane or quaternary tetrapentanol. The polyether polyols A1, A2 may be prepared using commercially available materials known in the art to meet the above requirements or may be prepared using polyether preparation techniques known in the art.
In a preferred embodiment, the amount of the polyether polyol A1 in the isocyanate-reactive component is 30 to 60 parts by mass, the amount of the polyether polyol A2 in the isocyanate-reactive component is 40 to 65 parts by mass, and the amount of the foaming agent in the isocyanate-reactive component is 3.5 to 5.5 parts by mass. The adoption of the preferable dosage range is beneficial to better considering the faster curing efficiency and the better comprehensive performance of the foam material, for example, the foam material with the density of 50-80 kg/m 3, the tensile strength of more than or equal to 100 kPa, the elongation at break of more than or equal to 100%, the tearing strength of more than or equal to 1.8N/cm and the loss factor of 0.3-0.7 can be obtained.
Further, the isocyanate-reactive component further comprises 0.1-1.5 parts by mass of a catalyst and 0.2-1.5 parts by mass of a surfactant, preferably, the catalyst is used in an amount of 0.2-1.0 parts by mass, and the surfactant is used in an amount of 0.3-1.0 parts by mass.
In some embodiments, the mass ratio of the isocyanate-reactive component to the isocyanate is 100:30 to 70, preferably 100:45 to 65. Further, the ratio of the number of equivalents of NCO groups of the isocyanate to the number of equivalents of reactive groups in the isocyanate-reactive component (i.e., the isocyanate index) is from 60 to 82.
Preferably, the NCO content of the isocyanate is 24-32wt%. The isocyanate may be selected from any known isocyanate, modified isocyanate, isocyanate-based prepolymer or prepolymers. In a preferred embodiment, the isocyanate is preferably selected from one or more of the group consisting of diphenylmethane polyisocyanates, 2, 4-diphenylmethane diisocyanates, 4-diphenylmethane diisocyanates and polyol-modified isocyanate prepolymers. The diphenylmethane polyisocyanates described herein are mixtures of diphenylmethane polyisocyanates having a functionality of 3 or greater. Wherein the polyol-modified isocyanate prepolymer is an NCO-terminated polymer formed by reacting polyether polyol with isocyanate. In some examples, the isocyanate is a mixture of a diphenylmethane polyisocyanate, a2, 4-diphenylmethane diisocyanate, a4, 4-diphenylmethane diisocyanate, and a polyol-modified isocyanate prepolymer, e.g., the mass ratio of the diphenylmethane polyisocyanate, the 2, 4-diphenylmethane diisocyanate, the 4, 4-diphenylmethane diisocyanate, and the polyol-modified isocyanate prepolymer is (20-30): 30-45): 3-10, and commercially available corresponding raw materials such as, but not limited to, one or more of Wanhua WANNATE 8038, WANNATE 8038K, wanhua WANNATE 8019, and the like may be used. In some examples, the isocyanate is a mixture of diphenylmethane polyisocyanate, 2, 4-diphenylmethane diisocyanate and 4, 4-diphenylmethane diisocyanate, e.g., the mass ratio of diphenylmethane polyisocyanate, 2, 4-diphenylmethane diisocyanate and 4, 4-diphenylmethane diisocyanate is (15-20): 30-40): 40-50, and corresponding commercially available raw materials such as, but not limited to, one or more of WANNATE 8122, WANNATE 8120, and the like may be used.
The blowing agent may be a chemical blowing agent and/or a physical blowing agent, in some embodiments, the blowing agent is selected from, but is not limited to, one or more of water, CO 2, alkane blowing agents, chlorine-containing blowing agents, fluorine-containing blowing agents, and the like, examples of which are one or more of butane, n-pentane, cyclopentane, isopentane, and the like, and one or more of chlorine-containing blowing agents, fluorine-containing blowing agents, such as dichlorofluoroethane, pentafluoropropane, pentafluorobutane, methylene chloride, and the like. As a preferred embodiment, the foaming agent is preferably selected from one or more of water, CO 2, dichlorofluoroethane, butane, n-pentane, cyclopentane and isopentane, more preferably the foaming agent is water.
In some embodiments, the catalyst is selected from one or more of an amine-based catalyst and an organometallic-based catalyst. Specifically, the amine catalyst is selected from, for example, but not limited to, one or more of bis (2-dimethylaminoethyl) ether, N ' -trimethyl-N ' -hydroxyethyl-diaminoethyl ether, dimethylaminopropylamine, N ' -dimethylethanolamine, bis (3-dimethylaminopropyl) aminoisopropanol, tetramethyldipropylenetriamine, pentamethyldiethylenetriamine, and triethylenediamine. Specifically, the organometallic-based catalyst is, for example, selected from, but not limited to, one or more of a metal alkyl compound and a metal carboxylate having catalytic activity for the reaction between isocyanate and hydroxyl groups, for example, such a metal includes, but is not limited to, one or more of, for example, lead, tin, titanium, antimony, mercury, and the like, and examples include, but are not limited to, one or more of stannous octoate, dibutyltin dilaurate, dibutyltin diacetate, and the like. In a preferred embodiment, the catalyst is preferably selected from one or more of dimethylaminopropylamine, N, N, N '-trimethyl-N' -hydroxyethyl-diaminoethyl ether, bis (3-dimethylaminopropyl) amino isopropyl alcohol and tetramethyldipropylenetriamine.
The surfactant may be of a type commonly used in the art, and is not particularly limited. The surfactant may be obtained by preparation or commercially. The preparation may be carried out according to methods commonly used by those skilled in the art, examples of commercially available surfactants include, but are not limited to, M-8818LO, M-8805, M-7734LF2, M7771LF2, etc. from Jiangsu Mei De Chemicals, inc., B8870, B8002, B8715, B8734LF2, etc., from Dow chemical, HR-8870, HR8871, etc. The surfactants may be used alone or in combination.
In some embodiments, the viscoelastic polyurethane foam is prepared by uniformly mixing the raw materials of the isocyanate-reactive component to obtain a first mixture, mixing the first mixture with the isocyanate to obtain a second mixture, transferring the second mixture to a mold for a foaming reaction, for example, rapidly injecting the second mixture into the mold for foaming. Preferably, the first mixture and the isocyanate are thoroughly mixed at 20-40 ℃, preferably at 22-35 ℃, to obtain a second mixture. In some embodiments, the foaming reaction time is 60 to 100 seconds, further for example 60 to 80 seconds. Preferably, the temperature of the mold is 50-80 ℃.
In the preparation steps of the invention, specific preparation parameters and conditions such as process, which are not described in detail, can be adopted by those skilled in the art.
The present invention also provides a viscoelastic polyurethane foam produced by the above-described production method. In some examples, the prepared viscoelastic polyurethane foam has a molding density of 50-80 kg/m 3, a tensile strength of more than or equal to 100: 100 kPa, an elongation of more than or equal to 100%, a tear strength of more than or equal to 1.8N/cm, a loss factor of 0.3-0.7, and is suitable for foaming in a mold at 50-80 ℃ and has high production efficiency.
The invention also provides application of the viscoelastic polyurethane foam in preparing automobile parts, and is particularly suitable for preparing automobile sound insulation pads, particularly, one or more of automobile carpets, front walls, wheel covers, hat racks and spare tire pads.
The viscoelastic polyurethane foam prepared by using simple raw material composition has excellent physical properties and damping properties, has low-density and rapid curing characteristics, is suitable for the production process requirements of automobile sound insulation pad parts, and is more beneficial to reducing the production cost of enterprises and improving the comfort of automobiles.
In order that the invention may be readily understood, a further description of the invention will be provided with reference to the following examples. It should be understood that the following examples are only for better understanding of the present invention and are not meant to limit the present invention to the following examples.
Where specific experimental steps or conditions are not noted in the examples, they may be performed according to the operations or conditions of the corresponding conventional experimental steps in the art. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The following examples and comparative examples are given with some of the raw materials:
the polyether polyol A1-1 takes glycerol as an initiator, propylene oxide and ethylene oxide are used as polymerization monomers and ethylene oxide is blocked, the content of the ethylene oxide monomers is 75wt% of the total amount of the ethylene oxide monomers and the propylene oxide monomers, the content of primary hydroxyl groups is 85wt% (based on the total amount of primary hydroxyl groups and secondary hydroxyl groups), the hydroxyl value is 33mgKOH/g, and the average functionality is 3;
Polyether polyol A1-2 takes glycerol as an initiator, propylene oxide and ethylene oxide are used as polymerization monomers and ethylene oxide is blocked, the content of the ethylene oxide monomers is 75wt% of the total amount of the ethylene oxide monomers and the propylene oxide monomers, the content of primary hydroxyl groups is 90wt% (based on the total amount of primary hydroxyl groups and secondary hydroxyl groups), the hydroxyl value is 34mgKOH/g, and the average functionality is 3;
the polyether polyol A1-3 takes trimethylol propane as an initiator, propylene oxide and ethylene oxide are used as polymerization monomers and ethylene oxide is blocked, the content of the ethylene oxide monomers is 80wt% of the total amount of the ethylene oxide monomers and the propylene oxide monomers, the content of primary hydroxyl groups is 85wt% (based on the total amount of primary hydroxyl groups and secondary hydroxyl groups), the hydroxyl value is 28mgKOH/g, and the average functionality is 3;
Polyether polyol A2-1 takes glycerol as an initiator, propylene oxide and ethylene oxide are used as polymerization monomers and ethylene oxide is blocked, the content of ethylene oxide monomers is 25wt% of the total amount of ethylene oxide monomers and propylene oxide monomers, the content of primary hydroxyl groups is 85wt% (based on the total amount of primary hydroxyl groups and secondary hydroxyl groups), the hydroxyl value is 26mgKOH/g, and the average functionality is 3;
Polyether polyol A2-2 takes glycerol as an initiator, propylene oxide and ethylene oxide are used as polymerization monomers and ethylene oxide is blocked, the content of ethylene oxide monomers is 30wt% of the total amount of ethylene oxide monomers and propylene oxide monomers, the content of primary hydroxyl groups is 88wt% (based on the total amount of primary hydroxyl groups and secondary hydroxyl groups), the hydroxyl value is 30mgKOH/g, and the average functionality is 3;
Polyether polyol A2-3 is prepared by taking trimethylolpropane as an initiator, propylene oxide and ethylene oxide as polymerization monomers and ethylene oxide as end caps, wherein the content of ethylene oxide monomers is 40% of the total amount of ethylene oxide monomers and propylene oxide monomers, the content of primary hydroxyl groups is 88% by weight (based on the total amount of primary hydroxyl groups and secondary hydroxyl groups), the hydroxyl value is 33mgKOH/g, and the average functionality is 3;
Catalyst 1, henlsmei, dimethylaminopropylamine;
catalyst 2, henlsmei, bis (3-dimethylaminopropyl) amino isopropanol;
Catalyst 3, henlsmei, N-dimethyl-N, N-bis (2-hydroxypropyl) -1, 3-propanediamine;
catalyst 4 Henschel, N, N, N '-trimethyl-N' -hydroxyethyl-bis-aminoethyl ether;
Surfactant 1, yingchuang B8734LF2;
Surfactant 2, dow chemical HR-8870;
the isocyanate B1 is a mixture of diphenylmethane polyisocyanate, 2, 4-diphenylmethane diisocyanate, 4-diphenylmethane diisocyanate and polyol-modified isocyanate prepolymer, and has an NCO content of 30% by weight and is commercially available in Vanilla WANNATE 8038.
Isocyanate B2-mixture of diphenylmethane polyisocyanate, 2, 4-diphenylmethane diisocyanate, 4-diphenylmethane diisocyanate and polyol-modified isocyanate prepolymer, NCO content 26% by weight, commercially available, vanilla WANNATE 8019.
Isocyanate B3 is a mixture of diphenylmethane polyisocyanate, 2, 4-diphenylmethane diisocyanate and 4, 4-diphenylmethane diisocyanate, and has an NCO content of 32% by weight, commercially available, wanhua WANNATE 8122, etc.
The combined polyether (viscoelastic polyurethane foam) WANEFLEX, 626 system, and WANEFLEX 621E system, commercially available, wanhua.
The detection method comprises the following steps:
Density testing of polyurethane foam the test standard adopted is ISO 845-2006;
tensile strength test and elongation at break test, wherein the adopted test standard is ISO 1798-2008;
the tearing strength is tested by adopting the test standard of ISO 8067-2018;
Young's modulus and loss factor test Young's modulus and loss factor tester using dynamic method, test according to Z-Nr 1 933 613.3 standard.
Examples 1 to 6
The preparation steps for examples 1-6 are as follows:
The raw materials and amounts used in examples 1 to 6 are shown in Table 1.
The materials of the metered component a were uniformly mixed at 25 ℃ and then thoroughly mixed with the metered component B at 25 ℃, and then the mixed materials were injected into a mold having a temperature of 65 ℃ to perform reaction foaming, and curing time (i.e., time of foaming reaction in the mold) of each example is as shown in table 1, and after foaming was completed, the mold was opened to take out the foam, thereby obtaining polyurethane foam.
The amounts of the respective raw materials in table 1 are calculated in parts by mass.
Table 1 raw material ratios and test results of examples
Table 2 comparative examples raw material ratios and test results
Note that polyether polyol WANNOL F3140, EO content 80wt% (based on total EO and PO), primary hydroxyl content 50wt% (based on total primary and secondary hydroxyl) hydroxyl value 42mgKOH/g, polyether polyol WANNOL F3135, EO content 16wt% (based on total EO and PO), primary hydroxyl content 87wt% (based on total primary and secondary hydroxyl) hydroxyl value 35mgKOH/g.
As can be seen from the results of the above examples and comparative examples, the viscoelastic polyurethane foam prepared in the examples of the present invention can obtain a viscoelastic polyurethane foam with a density of 50 to 80 kg/m 3, a tensile strength of not less than 90 kPa, an elongation at break of not less than 90%, a tear strength of not less than 1.7N/cm, and a loss factor of 0.25 to 0.7, which has a good overall performance, under the condition of taking into consideration rapid curing (curing time is within 100s, even within 80 s), and the foam material is particularly suitable for producing automobile sound insulation pad parts. In the comparative examples, a balance between higher curing efficiency and good overall properties cannot be achieved. In the more preferred examples 1-6, the amount of the polyether polyol A1 is 30-60 parts by mass, the amount of the polyether polyol A2 is 40-65 parts by mass, the amount of the foaming agent is 3.5-5.5 parts by mass, and the prepared viscoelastic polyurethane foam not only has higher curing efficiency, but also has better comprehensive properties of the viscoelastic polyurethane foam, and can obtain the foam material with the density of 50-80 kg/m 3, the tensile strength of more than or equal to 100 kPa, the elongation at break of more than or equal to 100%, the tearing strength of more than or equal to 1.8N/cm and the loss factor of 0.3-0.7.
It will be readily appreciated that the above embodiments are merely examples given for clarity of illustration and are not meant to limit the invention thereto. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While still being apparent from variations or modifications that may be made by those skilled in the art are within the scope of the invention.
Claims (10)
1. A method for producing a viscoelastic polyurethane foam, characterized in that the viscoelastic polyurethane foam is obtained by reacting a material comprising an isocyanate-reactive component and an isocyanate, wherein the isocyanate-reactive component comprises a polyether polyol composition and a foaming agent;
The polyether polyol composition comprises polyether polyol A1 and polyether polyol A2;
The hydroxyl values of the polyether polyol A1 and the polyether polyol A2 are 24-42 mgKOH/g respectively, and the content of primary hydroxyl groups is more than or equal to 80wt% based on the total amount of the primary hydroxyl groups and the secondary hydroxyl groups;
The average functionality of the polyether polyol A1 is 3-4, and the polyether polyol takes propylene oxide and ethylene oxide as polymerization monomers and is capped by ethylene oxide, and the ratio of the ethylene oxide monomers is 50-90wt% based on the total amount of the ethylene oxide and the propylene oxide monomers;
the average functionality of the polyether polyol A2 is 3-4, the polyether polyol takes propylene oxide and ethylene oxide as polymerization monomers and is capped by ethylene oxide, and the ethylene oxide monomer accounts for 20-50wt% based on the total amount of the ethylene oxide and the propylene oxide monomers;
In the isocyanate-reactive component, the amount of the polyether polyol A1 is 25-65 parts by mass, the amount of the polyether polyol A2 is 30-70 parts by mass, and the amount of the foaming agent is 3-6 parts by mass.
2. The method for preparing the viscoelastic polyurethane foam according to claim 1, wherein the hydroxyl value of the polyether polyol A1 is 28-42 mgKOH/g, the ratio of ethylene oxide monomers is 70-90 wt% based on the total amount of ethylene oxide and propylene oxide monomers, and the content of primary hydroxyl groups is more than or equal to 85wt% based on the total amount of primary hydroxyl groups and secondary hydroxyl groups;
The hydroxyl value of the polyether polyol A2 is 24-35 mgKOH/g, the ratio of the ethylene oxide monomer is 20-40 wt% based on the total amount of the ethylene oxide and the propylene oxide monomers, and the content of the primary hydroxyl groups is more than or equal to 85wt% based on the total amount of the primary hydroxyl groups and the secondary hydroxyl groups.
3. The method for producing a viscoelastic polyurethane foam according to claim 1, wherein the polyether polyol A1 is one or more of an alcohol compound having a functionality of 3 and an alcohol compound having a functionality of 4 as an initiator;
And/or, the polyether polyol A2 takes one or more of alcohol compounds with the functionality of 3 and alcohol compounds with the functionality of 4 as an initiator.
4. A method of preparing a viscoelastic polyurethane foam as set forth in claim 3 wherein the initiator of the polyether polyol A1 is one or more of glycerol, trimethylolpropane, or quaternary tetrapentanol;
And/or the initiator of the polyether polyol A2 is one or more of glycerol, trimethylolpropane or quaternary tetrapentanol.
5. The method for producing a viscoelastic polyurethane foam according to any one of claims 1 to 4, wherein the amount of polyether polyol A1 in the isocyanate-reactive component is 30 to 60 parts by mass, the amount of polyether polyol A2 is 40 to 65 parts by mass, and the amount of the foaming agent is 3.5 to 5.5 parts by mass.
6. The method for producing a viscoelastic polyurethane foam according to any one of claims 1 to 4, wherein the isocyanate-reactive component further comprises 0.1 to 1.5 parts by mass of a catalyst and 0.2 to 1.5 parts by mass of a surfactant;
and/or the mass ratio of the isocyanate reactive component to the isocyanate is 100:30-70;
And/or the NCO content of the isocyanate is 24-32wt%.
7. The method of preparing a viscoelastic polyurethane foam according to claim 6, wherein the isocyanate is selected from one or more of a diphenylmethane polyisocyanate, a 2, 4-diphenylmethane diisocyanate, a 4, 4-diphenylmethane diisocyanate, and a polyol-modified isocyanate prepolymer;
and/or the foaming agent is selected from one or more of water, CO 2, alkane foaming agents, chlorine-containing foaming agents and fluorine-containing foaming agents;
and/or the catalyst is selected from one or more of amine catalysts and organometallic catalysts.
8. The method for producing a viscoelastic polyurethane foam as set forth in any one of claims 1 to 4, wherein the step of producing a viscoelastic polyurethane foam comprises:
Uniformly mixing all raw materials of the isocyanate-reactive component to obtain a first mixed material, mixing the first mixed material with the isocyanate to obtain a second mixed material, and transferring the second mixed material into a mold for foaming reaction;
the first mixed material and the isocyanate are mixed at 20-40 ℃;
The foaming reaction time is 60-100s;
the temperature of the die is 50-80 ℃.
9. A viscoelastic polyurethane foam produced by the production process according to any one of claims 1 to 8.
10. Use of the viscoelastic polyurethane foam of claim 9 for the manufacture of automotive parts, including automotive sound insulation mats;
or the automobile parts comprise one or more of an automobile carpet, a front wall, a wheel cover, a hat rack and a spare tire pad.
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| WO2024129719A1 (en) * | 2022-12-16 | 2024-06-20 | Dow Global Technologies Llc | Viscoelastic polyurethane foam |
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| CN102504175A (en) * | 2011-11-04 | 2012-06-20 | 北京科聚化工新材料有限公司 | Preparation method for low-density viscoelastic polyurethane foam |
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