CN111607061A - Flame retardant-free high-flame-retardance low-odor full-water self-skinning polyurethane foam and preparation method thereof - Google Patents
Flame retardant-free high-flame-retardance low-odor full-water self-skinning polyurethane foam and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a flame retardant-free high-flame-retardance low-odor full-water integral skin polyurethane foam and a preparation method thereof, wherein the raw material consists of A, B two components in parts by mass: wherein the component A comprises: 150-70 parts of polyether polyol; 0-20 parts of polymer polyol; 3-10 parts of Mannich polyether polyol; 10-30 parts of PIPA polyol; 5-12 parts of chain extender; 1.5-3.5 of a reaction type catalyst; non-volatile catalyst 0.01-0.2; 0.1-1.0% of water; 0.5-2 parts of foam stabilizer; wherein polyether polyol 1+ polymer polyol + mannich polyether polyol + PIPA polyol is 100; the component B is a modified full MDI system isocyanate prepolymer with NCO content of 23-31 wt%; the polyether polyol 1 is high-activity polyether polyol which is initiated by glycerol, has three functionality degrees, has the molecular weight of 3000-10000 and has the content of terminal primary hydroxyl groups of more than 70 percent. A. The component B is prepared from the polyurethane foam with the leather by a molding method or a free foaming method, the foam still shows good flame retardance and better environmental protection without using a flame retardant, the oxygen index of the foam is more than or equal to 26 percent, and the odor is less than or equal to grade 3.
Description
Technical Field
The invention belongs to the field of polyurethane semi-rigid foam, and particularly belongs to the field of self-skinning polyurethane foam.
Technical Field
Polyurethane semi-rigid foam (semi-rigid foam for short) is one of several large varieties of polyurethane. It is a foam with the performance between that of polyurethane soft foam and that of polyurethane hard foam, and features high compression load value and high density, and its cross-linking density is far higher than that of soft foam and second to that of hard foam. The semi-hard bubble can quickly convert kinetic energy into energy in other forms when the automobile is impacted, thereby playing a role in buffering and protecting the safety of passengers.
Polyurethane integral skin foams belong to the category of semi-rigid foams, and are the third generation products of polyurethane foam processing developed according to the rapid development of the automotive industry. The compact skin and foam core of the polyurethane self-skinning foam, also known as integral skin foam, are prepared from the same two-component material at one time. The compact surface skin can form different patterns according to different moulds, thereby being beautiful and having protection effect; the foam of the core reduces both the density and the elasticity of the article. Because of the advantages, the polyurethane self-skinning foam is widely used for manufacturing automobile steering wheels, armrests, headrests and the like. The product is mainly applied to energy absorption and buffering parts such as automobile armrests, bumpers and the like, and can be used for preparing polyurethane self-skinning foam as a substitute of CFC (chlorofluorocarbon), including HCFC (HCFC), pentane, Hydrofluorocarbon (HFC) and water in the existing self-skinning foam. HCFC-141b, the mainstream product of polyurethane blowing agents, will also be banned from use. Compared with the foaming agents, the water has the advantages of low cost, easy obtainment, no toxicity, no flammability and explosion and zero ODP value.
In recent years, the water-blown self-skinned polyurethane technology is becoming a trend. Related art is set forth in U.S. Pat. nos. 5,166,183, 5,216,035, 5,234,961, 5,236,960, 5,236,961, 5,266,234, 5,284,880, 5,338,820, 5,514,723, and 5,658,959.
In recent years, odor and smoke in the air environment inside the vehicle, particularly in the vehicle body, have been listed as a new criterion for judging comfort or not. At present, with the coming out of the national standard GB/T27630-2011 'guide for evaluating air quality in a passenger car', the environmental performance requirements on the steering wheel and the handrail for the car are higher. The polyurethane semi-rigid foam used for the steering wheel and the handrail of the automobile can generate amine odor in a small environment in the automobile due to the tertiary amine catalyst adopted in the production, and can volatilize when the temperature in the automobile is higher, and part of volatile matters are condensed on the glass of a vehicle window to make the glass fuzzy (namely atomized). Therefore, avoiding the volatile migration of residual catalyst is the most effective way to reduce foam odor and fogging in the vehicle.
Meanwhile, the new national standard GB38262-2019 of the passenger car redefines the flame retardance of the passenger car. Wherein, the horizontal burning of the passenger car handrail and the steering wheel is required to be less than or equal to 50mm/min, and the oxygen index is more than or equal to 24 percent. This requires that the automotive self-skinning material not only be flame retardant, but also be environmentally friendly.
For example, in patent document CN101597370A, a low VOC self-skinning foam with a dense skin layer, good abrasion resistance and low volatility is obtained by synthesizing a high functionality polyether with a hydroxyl value of 40-180mgKOH/g and using it in combination with a non-volatile or reactive catalyst. However, the flame retardancy of such foams is not satisfactory.
CN103641979A relates to a mining polyurethane self-skinning composition. The flame-retardant self-skinning foam is prepared by adopting flame-retardant polymer polyol, a flame retardant and an antistatic agent, and the oxygen index can reach 28%. The invention solves the flame retardant property and antistatic property of the self-skinning foam, and the prepared mining polyurethane self-skinning composition has smooth surface, high flame retardance and antistatic property, thereby providing guarantee for the safety of mining self-skinning polyurethane. However, the self-skinning does not reach the foam VOC and odor standard due to the use of the flame retardant.
Patent document CN105601873A relates to a polyurethane self-skinning composite material for an automobile steering wheel and a preparation method thereof, the catalyst adopts one or more of a low-fog catalyst, a delayed catalyst or a reactive catalyst, and the mixed isocyanate is modified, so that the prepared automobile steering wheel has the advantages of low density, beautiful surface, good physical and mechanical properties, low odor, environmental protection and wide applicable temperature. The flame retardancy of such foams is not satisfactory.
Patent document CN108047422A uses a reactive catalyst and a solid nano flame retardant material to prepare a steering wheel with good environmental protection and a certain flame retardant effect, but the added solid flame retardant is easy to delaminate and inconvenient to use.
In other foam formulations, a reaction type catalyst and a reaction type flame retardant are used, so that low odor and certain flame retardance can be achieved, but the reaction type flame retardant has poor storage stability in a combined material, influences the foaming speed, needs to be added at present and is inconvenient to use.
In view of the above, there is a need to provide a self-skinning composite material which has excellent comprehensive properties, high flame retardancy, low odor, and simple and easy use without layering of the stock solution, and which meets the continuously increasing requirements of the passenger car industry.
Disclosure of Invention
The first purpose of the invention is to provide high-flame-retardant low-odor full-water integral skin polyurethane foam with excellent performance, which still shows good flame retardance and better environmental protection without using flame retardant, and the oxygen index of the foam is more than or equal to 26 percent, and the odor is less than or equal to grade 3.
It is a second object of the present invention to provide a process for the preparation of highly flame retardant low odor all water blown polyurethane foams.
In order to solve the first technical problem, the invention provides a flame retardant-free high-flame-retardant low-odor full-water self-skinning polyurethane foam, which comprises A, B parts by mass of raw materials:
the component A comprises:
polyether polyol 1: 50-70;
polymer polyol: 0 to 20;
mannich polyether polyol: 3-10;
PIPA polyol: 10-30;
chain extender: 5-12;
reaction type catalyst: 1.5 to 3.5
Non-volatile catalyst: 0.01 to 0.2;
water: 0.1 to 1.0;
foam stabilizer: 0.5 to 2;
wherein polyether polyol 1+ polymer polyol + mannich polyether polyol + PIPA polyol is 100;
the component B is a modified full MDI system isocyanate prepolymer with isocyanate (NCO) content of 23-31 wt%. The MDI system isocyanate comprises a mixture of two or more than two of diphenylmethane diisocyanate (MDI) monomer, carbamate modified MDI, carbodiimide modified MDI and the like, and the functionality is 2.0-2.7, preferably 2.1-2.4.
The component A and the component B are used together according to the mass ratio of 100: 40-100.
The polyether polyol 1 is high-activity polyether polyol which is initiated by glycerol, has three functionality degrees, has the molecular weight of 3000-10000 and has the content of terminal primary hydroxyl groups of more than 70 percent.
The polymer polyol is high-activity polymer polyol which is grafted by styrene and acrylonitrile and has three functionality degrees and a solid content of 25-45%.
The Mannich polyether polyol disclosed by the invention preferably has a functionality of 4-5 and a hydroxyl value of 300-550 mgKOH/g.
The PIPA polyol is a suspension dispersion generated by the reaction of polyalcohol amine and isocyanate in polyether polyol 1, and has the solid content of 10-20% and the viscosity of 3000-6000 mPa.s. The specific synthesis method comprises the following steps: adding polyether polyol 1, polyalcohol amine and a dispersing agent into a reactor according to the mass ratio of 100/4-10/5-10, and mixing; adding a mixture of polyether polyol 1 and isocyanate in a mass ratio of 2/1-1/2, and reacting for 1-3 hours at 30-50 ℃ to obtain the product. Wherein the polyalcohol amine is preferably triethanolamine, the dispersant is preferably polyethylene glycol 200 or polyethylene glycol 400, and the isocyanate is preferably toluene diisocyanate or diphenylmethane diisocyanate and modified substances thereof. The ratio of NCO groups in isocyanate to the amount of hydroxyl groups in the polyalcohol amine is the alcohol amine index, and is generally selected from 0.9 to 1.1. Solid content is (polyalcohol amine mass + polyisocyanate mass)/total mass.
The chain extender of the present invention is preferably at least one of ethylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 6-hexanediol, diethylene glycol, and the like.
The reactive catalyst of the present invention is preferably a compound having a structure containing a reactive hydroxyl group or an amino group, such as at least one of N ' N-dimethylethanolamine, trimethylhydroxyethylethylenediamine, trimethylhydroxyethylpropylenediamine, tetramethyldipropylenetriamine, 2- (2-dimethylamino-ethoxy) -ethanol, N, N, N ' -trimethyl-N ' -hydroxyethylbisaminoethyl ether, bis (dimethylamino) -2-propanol, or the like.
In the present invention, the non-volatile catalyst is preferably at least one of a metal salt, an organic basic compound, a quaternary ammonium salt, and the like of an aliphatic carboxylic acid.
The foam stabilizer is a commonly used foam stabilizer for semi-rigid foam and high-resilience foam, and the foam stabilizer contains silicone oil with Si-C bonds, and the using amount of the silicone oil is 0.5-2%, preferably 0.5-1.5% of the total amount of the polyether component. The variety with higher activity is preferred, and suitable foam stabilizers include, but are not limited to, B8715 and B8736 of Germany winning and creating industry group, DC2525 and DC6070 of American gas and chemical company, and L-3629 and L-3640 of American Mediterranean high-tech materials group.
The synthesis method of the modified full MDI system isocyanate prepolymer comprises the following steps: adding MDI system isocyanate into a reactor, heating to 50 ℃, adding dehydrated polyether glycol 2, and reacting for 4 hours at 60-80 ℃ to obtain the modified full MDI system isocyanate with the isocyanate (NCO) content of 23-31 wt%. The MDI system isocyanate is preferably a mixture of carbodiimide modified liquefied MDI and MDI-50, wherein the mass ratio of the carbodiimide modified liquefied MDI to the MDI-50 is 50/50-95/5, preferably 50/50-80/20. Wherein the carbodiimide modified MDI is preferably MM103C from BASF company or CD-C product from Cordson corporation; MDI-50 is 4, 4 '-diphenylmethane diisocyanate (4, 4' -MDI): 2, 4 '-diphenylmethane diisocyanate (2, 4' -MDI) is 50: 50 pure MDI, such as 0129 from Coresi Corp. Polyether polyol 2 is a difunctional all-propylene-oxide polyether polyol having a molecular weight of 500-10000.
The self-skinning polyurethane foam of the present invention can be prepared by a molding process or a free-bubble process. And (3) mixing the raw materials of the component A according to the weight ratio to form the component A, and carrying out prepolymerization to obtain isocyanate as the component B. Controlling the temperature of A, B components at 20-40 deg.C (preferably 30 + -5 deg.C), rapidly stirring and mixing A component and B component at a certain proportion, pouring into a mold or cup, curing for 1.5-3min, and taking out from the mold or cup to obtain the final product. The foam can be widely applied to products such as steering wheels, armrests, airport chair cushions, bathtub headrests and the like.
The method is simple and practical, the Shore A hardness of the obtained polyurethane foam molding material is 50-85, and the overall density is 300-600Kg/m3The oxygen index is more than or equal to 26 percent, the horizontal burning is less than D50mm/min, and the odor is less than or equal to grade 3. The product not only has high flame retardance, but also has good environmental protection performance, overcomes the defect that the self-skinning foam in the prior art can not be simultaneously taken into consideration, and meets the requirement of new passenger car standards on the self-skinning for vehicles.
Detailed Description
The following examples are provided to better illustrate the effects of the present invention, but the present invention is not limited to the examples.
"MDI" is an abbreviation for "diphenylmethane diisocyanate", such as 2, 4-MDI for 2, 4-diphenylmethane diisocyanate and 4, 4 '-MDI for 4, 4' -diphenylmethane diisocyanate; "NCO" is an abbreviation for "isocyanato"; the term "functionality" refers to the number of functional groups that a monomer molecule is capable of participating in a condensation polymerization reaction during polymerization. The "parts" referred to herein mean "parts by mass" unless otherwise specified; the percentage contents are all mass percentages unless otherwise specified.
The oxygen index is the minimum oxygen concentration required for the foam to sustain combustion, and the magnitude of the oxygen index directly reflects whether the foam is easily combusted; the horizontal burning is a test method in which one end of a material sample is horizontally held, and the free end is exposed to flame of a predetermined gas, and the linear burning rate is measured to evaluate the burning performance.
And (3) odor test: cutting the sample into 5cm × 5cm × 2cm, putting the sample into a clean glass bottle with the volume of 1L prepared in advance, and screwing the bottle cap; after the foam is placed in an oven at the temperature of (80 +/-2) DEG C for 2 hours, the bottle cap is opened, and 5 appraisers judge the odor grade of the foam through the gas escaping from the bottle mouth. And (3) identification standard: the odor evaluation standard is divided into 1-6 grades, and meanwhile, the odor grade of the foam is the arithmetic average of the test values of 5 appraisers.
Score 1 no odor
Score 2 smells, but no interfering smells
Score 3 had a clear odor, but no interfering odor
Score 4 interfering odor
Score 5 strongly interfering odor
Score 6 has an intolerable odor
Examples the raw materials used in the formulation:
polyether polyol 1: glycerol initiated, trifunctional, propylene oxide grafted, ethylene oxide capped polyols, polyoxypropylene ether triols having a hydroxyl value of 30-35mgKOH/g and a primary hydroxyl end group content of greater than 70%;
polymer polyol: glycerin-initiated, trifunctional, hydroxyl value 18-22mgKOH/g, solid content 45%, styrene, acrylonitrile grafted, high activity polymer polyol;
mannich polyol: tetrafunctionality, hydroxyl number 330 mgKOH/g;
PIPA polyol: 500g of TEP-551c (Tianjin Tripetrochemicals), 35g of triethanolamine and 50g of PEG-400 are mixed and added into a three-neck flask, and the mixture is stirred for 10 min. And slowly adding 124g of a mixture of TEP-551c and TDI with an alcohol amine index of 1.0 into a three-neck flask, and reacting at 30-50 ℃ for 1-3 h to obtain the PIPA polyol with the solid content of 13.7%.
Chain extender: ethylene glycol, diethylene glycol;
foaming agent: water;
reaction type catalyst: the reaction type catalyst may be PC-17, DABCO T product of US gas company, DPA, ZR-70 product of Hensman company.
Non-volatile catalyst: (2-hydroxypropyl) trimethyl ammonium formate (TMR-2);
foam stabilizer: DC2525 product from american gas company;
flame retardant: tris (2-chloropropyl) phosphate (TCPP);
carbodiimide-modified liquefied MDI: MM103C product from BASF corporation or CD-C product from Coresta corporation;
polyether polyol 2: DL-4000 (difunctional, hydroxyl number 28mgKOH/g, fully propylene oxide-grafted polyether polyol).
Component B1: the isocyanate prepolymer with the NCO content of 28.0 percent is prepared by the following steps: adding the liquefied MDI600g and 400g of MDI-50 into a reactor in sequence, heating to 50 ℃, then adding 100g of polyether polyol DL-4000 into the reactor, and reacting for 4 hours at the temperature of 60-80 ℃ to obtain the modified full MDI system isocyanic acid with the content of isocyanic acid radical (NCO) of 28 percent.
And B, component 2: the isocyanate prepolymer with NCO content of 26.5 percent is prepared by the following steps: adding the liquefied MDI600g and 400g of MDI-50 into a three-neck flask in sequence, heating to 50 ℃, then adding 157g of polyether polyol DL-4000 into a reactor, and reacting for 4 hours at 60-80 ℃ to obtain the modified full MDI system isocyanic acid with the content of isocyanic acid radical (NCO) of 26.5 percent.
Table 1 shows the example and comparative example formulations.
Preparing a high-flame-retardant low-odor integral skin polyurethane foam material: preparing raw materials such as polyether, a foaming agent, silicone oil, a catalyst and the like into a component A according to the mass shown in Table 1, weighing a component B according to the mass, controlling the temperature of the component A, B to be about 25 ℃, pouring isocyanate into the polyether component, stirring at a high speed for 6-8s by using mechanical stirring, quickly pouring materials into an aluminum die with the size of 200mm multiplied by 10mm, curing in the die for 2min, and then demolding to obtain the self-skinning foam product. The foamed article was left to stand for 72 hours and then tested for physical properties. The test was carried out according to the following criteria or methods:
TABLE 1 raw material formulations and foam properties for examples E1-E6 and comparative examples C1-C2
As seen from Table 1, the present invention can satisfy the new requirements of the commercial passenger car industry in terms of environmental protection and flame retardancy.
It is obvious to those skilled in the art that the high flame retardant water blown self-skinned polyurethane of the present invention can be popularized to other applications in similar fields, such as handrails for furniture, airport seats, bath cushions, etc. Therefore, without departing from the spirit of the invention, those skilled in the art can make various changes or modifications to the invention without departing from the spirit of the invention, and the invention also falls into the scope of the invention.
Claims (10)
1. A flame retardant-free high-flame-retardance low-odor full-water self-skinning polyurethane foam is prepared from A, B two components in parts by mass:
the component A comprises:
polyether polyol 1: 50-70 parts of;
polymer polyol: 0 to 20;
mannich polyether polyol: 3-10;
PIPA polyol: 10-30;
chain extender: 5-12;
reaction type catalyst: 1.5 to 3.5
Non-volatile catalyst: 0.01 to 0.2;
water: 0.1 to 1.0;
foam stabilizer: 0.5 to 2;
wherein polyether polyol 1+ polymer polyol + mannich polyether polyol + PIPA polyol is 100;
the component B is a modified full MDI system isocyanate prepolymer with isocyanate (NCO) content of 23-31 wt%;
the polyether polyol 1 is a high-activity polyether polyol which is started by glycerol, has three functionality degrees, has a molecular weight of 3000-10000 and contains more than 70% of terminal primary hydroxyl groups;
the component A and the component B are used together according to the mass ratio of 100: 40-100.
2. The flame retardant-free, high flame retardant, low odor all water integral skin polyurethane foam of claim 1 wherein said polymer polyol is a trifunctional, 25% to 45% solids, styrene, acrylonitrile grafted, high activity polymer polyol; the functionality of the Mannich polyether polyol is 4-5, and the hydroxyl value is 300-550 mgKOH/g; the PIPA polyol is a suspension dispersion generated by reaction of polyalcohol amine and isocyanate in polyether polyol 1, the solid content is 10-20%, and the viscosity is 3000-6000 mPa.s.
3. The flame retardant-free, high flame retardant, low odor, all water blown polyurethane foam of claim 2 wherein said PIPA polyol is prepared by the process of: adding polyether polyol 1, polyalcohol amine and a dispersing agent into a reactor according to the mass ratio of 100/4-10/5-10, and mixing; adding a mixture of polyether polyol 1 and isocyanate in a mass ratio of 2/1-1/2, and reacting for 1-3 hours at 30-50 ℃ to obtain the product.
4. The flame retardant-free, high flame retardant, low odor all water blown polyurethane foam of claim 3 wherein the polyalcohol amine is triethanolamine; the dispersant is polyethylene glycol 200 or polyethylene glycol 400; the isocyanate is toluene diisocyanate or diphenylmethane diisocyanate and modified products thereof.
5. The flame retardant-free high flame retardant low odor all water integral skin polyurethane foam of claim 1, wherein the MDI system isocyanate is a mixture of two or more of diphenylmethane diisocyanate (MDI) monomer, urethane-modified MDI, and carbodiimide-modified MDI, and has a functionality of 2.0 to 2.7.
6. The flame retardant-free high flame retardant low odor full water integral skin polyurethane foam of claim 1, which is characterized in that the modified full MDI system isocyanate prepolymer is prepared by the following method: adding MDI system isocyanate into a reactor, heating to 50 ℃, adding dehydrated polyether glycol 2, and reacting for 4 hours at 60-80 ℃ to obtain modified full MDI system isocyanate with isocyanate (NCO) content of 23-31 wt%; polyether polyol 2 is a difunctional all-propylene oxide, polyether polyol having a molecular weight of 500-10000.
7. The flame retardant-free high-flame-retardance low-odor full-water integral skin polyurethane foam as claimed in claim 6, wherein the MDI system isocyanate is a mixture of carbodiimide modified liquefied MDI and MDI-50, and the mass ratio of the carbodiimide modified liquefied MDI to the MDI-50 is 50/50-95/5.
8. The flame retardant-free high flame retardant low odor all-water integral skin polyurethane foam as claimed in any one of claims 1 to 7, wherein said non-volatile catalyst is selected from the group consisting of metal salts of aliphatic carboxylic acids, organic basic compounds or quaternary ammonium salts and mixtures thereof.
9. The flame retardant-free high flame retardant low odor all water integral skin polyurethane foam of any one of claims 1 to 8, wherein the chain extender is selected from the group consisting of ethylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, 1, 6-hexanediol or diethylene glycol, and mixtures thereof; the reactive catalyst is selected from the group consisting of N ' N-dimethylethanolamine, trimethylhydroxyethylethylenediamine, trimethylhydroxyethylpropylenediamine, tetramethyldipropylenetriamine, 2- (2-dimethylamino-ethoxy) -ethanol, N, N, N ' -trimethyl-N ' -hydroxyethylbisaminoethyl ether or bis (dimethylamino) -2-propanol and mixtures thereof; the foam stabilizer is silicone oil containing Si-C bonds.
10. A process for preparing a flame retardant-free, high flame retardant, low odor, all water integral skin polyurethane foam of any of claims 1 to 9: mixing the raw materials of the component A according to the weight to form the component A, and using isocyanate obtained by prepolymerization as the component B; A. controlling the temperature of the component B at 20-40 deg.C, rapidly stirring A, B components in proportion, pouring into a mold or cup, curing, and taking out from the mold or cup after 1.5-3 min.
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| CN113388084A (en) * | 2021-07-05 | 2021-09-14 | 黎明化工研究设计院有限责任公司 | Environment-friendly composition for PIP (poly-p-phenylene) infusion headrest and preparation method and application thereof |
| CN114716638A (en) * | 2022-04-14 | 2022-07-08 | 佳化化学科技发展（上海）有限公司 | Polyurethane self-skinning foam and preparation method and application thereof |
| CN115141350A (en) * | 2022-08-23 | 2022-10-04 | 安徽大学 | Environment-friendly flame-retardant semi-rigid polyurethane foam plastic for automobile engine hood and preparation method thereof |
| CN116284654A (en) * | 2023-01-02 | 2023-06-23 | 黎明化工研究设计院有限责任公司 | Low-odor and rapid-demolding self-skinning polyurethane foam composition and preparation method thereof |
| CN116789925A (en) * | 2023-07-07 | 2023-09-22 | 江苏米尔化工科技有限公司 | Formaldehyde-free low-odor polyurethane foam material and preparation method thereof |
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| CN113388084B (en) * | 2021-07-05 | 2022-10-14 | 黎明化工研究设计院有限责任公司 | Environment-friendly composition for PIP (poly-p-phenylene-ethylene) foam headrest and preparation method and application thereof |
| CN114716638A (en) * | 2022-04-14 | 2022-07-08 | 佳化化学科技发展（上海）有限公司 | Polyurethane self-skinning foam and preparation method and application thereof |
| CN114716638B (en) * | 2022-04-14 | 2023-12-01 | 佳化化学科技发展（上海）有限公司 | Polyurethane self-skinning foam and preparation method and application thereof |
| CN115141350A (en) * | 2022-08-23 | 2022-10-04 | 安徽大学 | Environment-friendly flame-retardant semi-rigid polyurethane foam plastic for automobile engine hood and preparation method thereof |
| CN116284654A (en) * | 2023-01-02 | 2023-06-23 | 黎明化工研究设计院有限责任公司 | Low-odor and rapid-demolding self-skinning polyurethane foam composition and preparation method thereof |
| CN116789925A (en) * | 2023-07-07 | 2023-09-22 | 江苏米尔化工科技有限公司 | Formaldehyde-free low-odor polyurethane foam material and preparation method thereof |
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