CN107857865B - Full-water environment-friendly flame-retardant flatulence memory polyurethane foam for automobile seat and preparation method thereof - Google Patents
Full-water environment-friendly flame-retardant flatulence memory polyurethane foam for automobile seat and preparation method thereof Download PDFInfo
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- C08G2280/00—Compositions for creating shape memory
Abstract
The invention provides full-water environment-friendly flame-retardant type flatulence memory polyurethane foam for an automobile seat and a preparation method thereof. According to the invention, the consumption of each reactive component is reasonably proportioned, the full-water foaming and low-odor reaction type environment-friendly auxiliary agent is adopted, and the proper isocyanate compounded is selected, so that the obtained foam is flame-retardant, no flame retardant is required to be added, the foam odor is low, and the environment-friendly property can be improved when the foam is applied to an automobile seat.
Description
Technical Field
The invention belongs to the field of polyurethane soft foam, and relates to shape memory polyurethane foam for an automobile seat and a preparation method thereof. Specifically, the flexible foam has a shape memory function, and the foam itself is environmentally friendly and flame retardant, and is formed from a composition that does not contain any flame retardant.
Background
At present, the automobile industry develops rapidly, and people have higher and higher requirements on riding comfort. The slow rebound foam is also called memory foam, and has good damping property and good sound absorption and shock absorption functions, so that when the slow rebound foam is used as a seat cushion material, the slow rebound foam can follow the shapes of different parts of a human body and is in contact with the human body, the body pressure is uniformly distributed, the stress is dispersed, the blood circulation of the human body is facilitated, the fatigue feeling of the human body is reduced, and the riding comfort is improved.
When the conventional slow rebound molding foam is prepared, low-molecular-weight low-activity polyether (which is called slow rebound polyether in the market) is mainly mixed in high-activity polyether according to a certain proportion, the prepared slow rebound foam is easy to close pores and cause foam shrinkage deformation, therefore, a certain proportion of pore-opening agent is usually added for opening pores when the foam is prepared, and the foam prepared by the method has the advantages of different pore structure sizes, low strength and poor hand feeling. In order to improve the flame retardance of the foam, a flame retardant is added into the raw materials, so that the foam has a large smell, a large smoke amount during combustion and strong toxicity. Meanwhile, when the foam is prepared, a relatively low isocyanate index is often needed, the reaction between the combined polyol component and the isocyanate component is insufficient, and especially some low molecular weight and low functionality micromolecular substances cannot effectively participate in the reaction, so that the foam has poor pressure-variable property, reduced mechanical property, poor support property and large foam smell, and is not beneficial to popularization and application on automobile seats.
Disclosure of Invention
The invention aims to provide a manufacturing method of an flatulence memory sponge, the foam is designed in an air bag type, has lower dependency on the indexes of low molecular weight polyether and isocyanate, has large formula latitude, good foam hand feeling, sufficient flatulence feeling, good low resilience effect and high mechanical property, and has support property and damping energy absorption property when being applied to an automobile seat, thereby improving the comfort.
The invention aims to reasonably proportion the consumption of each reactive component, adopt full-water foaming and low-odor reaction type environment-friendly auxiliary agent, select proper isocyanate formed by compounding, obtain the foam which is flame-retardant, does not need to add any flame retardant, has low foam odor, and can improve the environment-friendly property when being applied to automobile seats.
In order to achieve the purpose, the invention adopts the technical scheme that:
the full-water environment-friendly flame-retardant flatulence memory polyurethane foam for the automobile seat comprises a component A and a component B, wherein the component A comprises the following components in parts by weight:
the component B is full MDI system isocyanate;
the amount of the component B is determined according to the isocyanate index of 70-110, wherein the isocyanate index is the ratio of NCO groups in the component B to OH or active H groups in polyether polyol in the component A; in practice, the amount of component B used can be determined by the isocyanate index in combination with the total amount of reactive components present in the reaction system;
the polyether polyol A is a ring-opening polymerization copolymer of propylene oxide and ethylene oxide, wherein the small molecular weight polyol compound containing active hydrogen groups is used as an initiator, the end group of the polyether polyol A is ethylene oxide-terminated propylene oxide and ethylene oxide, the polyether functionality is 3, the hydroxyl value is 32-50 mgKOH/g, the content of the propylene oxide is less than 30%, and the content of the ethylene oxide is less than 75%;
the polyether polyol B is synthesized by taking a small molecular weight polyol compound containing an active hydrogen group as an initiator and performing ring-opening polymerization reaction with propylene oxide, wherein the polyether functionality is 3, the hydroxyl value is 105-280 mgKOH/g, and the content of the propylene oxide is more than 90%;
the polyether polyol C is a ring-opening polymerization copolymer of propylene oxide and ethylene oxide, wherein the small molecular weight polyol compound containing active hydrogen groups is used as an initiator, the end group of the polyether polyol C is ethylene oxide-terminated propylene oxide and ethylene oxide, the polyether functionality is 3, the hydroxyl value is 32-40 mgKOH/g, the content of propylene oxide is less than 30%, and the content of ethylene oxide is more than 50%;
the polyether polyol D is formed by grafting copolymerization of polyether polyol and a vinyl monomer under the action of an initiator, and has the functionality of 2.7-3, the hydroxyl value of 20-30 mgKOH/g, the ethylene oxide content of 65-90% and the propylene oxide content of 10-30%; polyether polyol D is a modified polyether polyol, or is called polymer polyol or graft polyether polyol;
the chemical foaming agent is water;
the composite catalyst is tertiary amine catalyst;
the foam stabilizer is a non-hydrolytic low-fogging organic silicon surfactant;
the cross-linking agent in the cross-linking/chain extender is a small molecular weight triol or alcohol amine compound with three or more than three functionalities; the chain extender is hydroxyl diol or ether with two isocyanate-reactive groups, and the weight ratio of the cross-linking agent to the chain extender in the cross-linking/chain extender mixture is 3: 7-7: 3.
The chemical foaming agent is water, has no impurities, is colorless and transparent, replaces the traditional foaming agent which has destructive effect on the atmosphere, and reacts with the modified MDI to generate carbon dioxide gas for controlling the foam density.
Preferably, the initiator of the small molecular weight polyol compound in the polyether polyol A, the polyether polyol B and the polyether polyol C is glycerol or trimethylolpropane. In general, a small molecular weight refers to a molecular weight less than 400 relative to a molecular weight, which is referred to as a small molecular weight.
Preferably, the polyether polyol D is formed by graft copolymerization of polyether polyol and a vinyl monomer under the action of an initiator, wherein the vinyl monomer is one of acrylonitrile, styrene and vinyl acetate.
Preferably, the tertiary amine catalyst is any one or a combination of more than two of innovative diol solution (33LX) with the triethylene diamine content of 33% of American gas chemical company, NA-720 of Oerska materials science and technology company, dimethyl ethanolamine (DMEA), Dimethylaminoethoxyethanol (DMAEE), N, N, N '-trimethyl-N' -hydroxyethyl bisaminoethyl ether (ZF-10), N, N-bis (dimethylaminopropyl) isopropanolamine (ZR-50) in hydroxyl tertiary amine of American Hunsmei company, and NIAXEF-600 of Mimeji materials company.
The composite catalyst is one or more of the catalysts, the catalyst can balance foaming reaction and gel reaction in the reaction process, the formation of polymers and the generation rate of carbon dioxide gas are coordinated, and the foam body has proper strength during the foaming reaction, supports the foam body without collapsing, wraps the gas in the foam body and does not cause foam shrinkage. The trade-off between reaction rate and gel rate depends on the selection or combination of suitable catalysts and their synergistic effects on each other.
Preferably, the foam stabilizer is any one of L-580 or L-3635 from Meigold materials group of America, B-8002 or B-8715LF2 or B-8870 from Woods industries group of Germany, UF-5766 from Osaka materials science and technology (Shanghai), AK-6688LV and AK-6628LV from Nanjing Meissde.
The foam stabilizer can play a role in emulsifying reaction materials, reducing the surface tension of a reaction system, stabilizing foam and adjusting foam holes. The foam stabilizer is a high-activity or medium-low activity non-hydrolytic low-atomization organosilicon surfactant for common polyurethane soft block foam, slow-rebound foam and high-rebound molding foam.
Preferably, the cross-linking agent in the cross-linking/chain-extending agent is one or a combination of two or more of Glycerol (GLY), Trimethylolpropane (TMP), Diethanolamine (DEOA) and Triethanolamine (TEOA).
Preferably, the chain extender in the crosslinking/chain extender is any one or a combination of more than two of 1, 4-Butanediol (BDO), Ethylene Glycol (EG), diethylene glycol (DEG), 1, 3-propanediol (DPG), liquefied hydroquinone-di-beta-hydroxyethyl ether (HQEE-L) and polyethylene glycol with the average molecular weight of at most 250.
The crosslinking/chain extender can increase the supporting strength of foam holes, enhance the stability of a foaming system and avoid the quality problems of foam collapse and the like. Wherein the cross-linking agent has three or more functionalities. The chain extender increases the glass transition temperature of the foam, and it reacts with the isocyanate component to form the polyurethane hard segments in the foam.
Preferably, the component A further comprises one or two of a foam reinforcing agent and an elasticizer.
Preferably, the foam reinforcing agent is modified vegetable oil or vegetable fat, the amount of the foam reinforcing agent is 2-15 parts by weight based on 100 parts by weight of mixed polyether polyol, the foam reinforcing agent increases air circulation of foam, the foam strength and hand feeling are enhanced, and the fingerprint residue is low.
Preferably, the amount of component B is determined according to the isocyanate index of 75-100.
Preferably, the full MDI system isocyanate is a mixture of MDI-50, carbamate modified MDI, carbodiimide modified MDI and polyphenyl polymethylene polyisocyanate, and the average functionality is 2.0-2.2. The three kinds of modified MDI are prepared by reacting diphenylmethane diisocyanate and polyhydroxy compounds.
The preparation method of the full-water environment-friendly flame-retardant flatulence memory polyurethane foam for the automobile seat is characterized by comprising the following steps of:
(1) sequentially putting polyether polyol A, polyether polyol B, polyether polyol C, polyether polyol D, a composite catalyst, a foam stabilizer, water and a crosslinking/chain extender into a stirring kettle according to parts by weight, and fully and uniformly mixing at normal temperature to obtain a component A;
(2) and mixing the component A and the component B according to the weight part at 22-26 ℃, pouring the mixture into a mold for reaction, controlling the mold temperature at 45-55 ℃, curing for 4-5 min, opening the mold, and taking out a sample to obtain the flame-retardant flatulence memory sponge.
Compared with the prior art, the invention has the beneficial effects that:
(1) the polyurethane foam for the automobile seat has a reasonable formula, and the prepared polyurethane foam has sufficient flatulence, good hand feeling, softness and comfort under the condition of not adding a pore-forming agent; according to the formula disclosed by the invention, the prepared polyurethane foam has good flame retardant property under the condition of not adding a flame retardant; therefore, under the condition that no pore-forming agent or flame retardant is added, the low-odor components are used, so that the prepared polyurethane foam is low in odor, environment-friendly and suitable for wide popularization and application, and particularly, the polyurethane foam is applied to automobile seats, is beneficial to physical and psychological health of drivers and passengers, and improves safety and riding comfort.
(2) The isocyanate used in the formula is compounded, has no great dependence on low-index isocyanate, has good wide compatibility, solves the problems of poor mechanical property and poor pressure-variable property caused by insufficient reaction of polyol components and isocyanate components in the prior art, and further can improve the mechanical property of the prepared polyurethane foam.
Detailed Description
The present invention will be described in further detail with reference to examples, but the present invention is not limited to the examples.
The full-water environment-friendly flame-retardant flatulence memory polyurethane foam for the automobile seat comprises the following components:
the polyether polyol A is 3-functionality, the Glycerol (GLY) is used as an initiator, and the polyether polyol A is copolymerized polyol formed by ring-opening polymerization reaction of ethylene oxide and propylene oxide, the hydroxyl value is 42mgKOH/g, and the molecular weight is 4000.
The polyether polyol B is 3-functionality, Glycerol (GLY) is used as an initiator, and the polyether polyol B and propylene oxide are subjected to ring-opening polymerization to form a copolymerized polyol, wherein the hydroxyl value is 225-245 mgKOH/g, and the molecular weight is 700.
The polyether polyol C is 3-functionality, Trimethylolpropane (TMP) is used as an initiator, and is copolymerized with ethylene oxide-propylene oxide through ring-opening polymerization reaction to obtain copolymerized polyol, wherein the ethylene oxide content is greater than 55%, the hydroxyl value is 34mgKOH/g, and the molecular weight is 5000.
The polyether polyol D is polymer polyether polyol, the hydroxyl value is 21-28 mgKOH/g, the molecular weight is 6000, and polymer polyol CHP-H45 with the hydroxyl value of 19-23 mgKOH/g, which is produced by Changhua polyurethane technology Limited, can be adopted.
The foaming agent is water.
Foam stabilizer L-580, non-hydrolyzable polysiloxane-polyoxyethylene copolymer, Michigan Seiko.
Foam stabilizer UF-5766, non-hydrolyzable polysiloxane-polyoxyethylene copolymer, Osaka materials science and technology.
Catalyst ZF-10, reactive tertiary amine blowing catalyst, Hounsfield.
Catalyst NA-720, reactive tertiary amine gel catalyst, Osaka materials science and technology.
Catalyst 33LX, low odor gel/equilibrium catalyst, gas chemicals usa.
The crosslinking/chain extender is a mixture of DEG and TMP, wherein DEG accounts for 60wt% of the crosslinking/chain extender mixture, and TMP accounts for 40 wt%.
The isocyanate is MDI-50, a mixture of urethane modified MDI and P-MDI which are prepared by reacting MDI and polyhydric alcohol, and the NCO content of the obtained modified MDI is 29-30%.
The preparation method of the full-water environment-friendly flame-retardant flatulence memory polyurethane foam for the automobile seat comprises the following steps: according to the weight portion ratio, the component A is prepared from polyether polyol A, polyether polyol B, polyether polyol C, polyether polyol D, foaming agent water, foam stabilizer, catalyst and crosslinking/chain extender. Weighing a certain amount of isocyanate according to a proportion at room temperature, mixing the isocyanate with the component A, quickly stirring for 5-6 s, quickly pouring the foaming material into an aluminum mould with the thickness of 400mm multiplied by 100mm, and curing for 4-5 min at the mold temperature of 52 ℃ to obtain the flame-retardant flatulence memory sponge. The cured product was aged in a clean and ventilated environment for 3 days and tested for various properties under standard test conditions.
The formulations of the components and the ratios of component A to component B in examples 1-6 are shown in Table 1.
TABLE 1 examples 1-6 component formulations and ratios of component A to component B
The mechanical property test results of the products prepared according to the formula proportion are shown in table 2, and the comparative example is a marcopolo memory polyurethane foam product.
TABLE 2 mechanical Property test results of the products prepared in examples 1-6 and comparative examples
The test results in Table 2 show that the properties of tear strength, tensile strength and elongation at break of the inflation memory polyurethane foam prepared by the invention are higher than those of the comparative marcopolo memory polyurethane foam even in a wider isocyanate range, and the foam has stronger inflation feeling.
The environmental protection performance (odor) test results of the products prepared according to the formula proportion are shown in table 3.
TABLE 3 environmental protection Performance (odor) test results for the products prepared in examples 1-6 and comparative examples
In Table 3, the odor test sample piece has the size of 100mm multiplied by 50mm multiplied by 40mm, and the container is a colorless transparent clean ground glass bottle with the volume of 1L, and the test result shows that the odor environmental protection performance of the flatulence memory polyurethane foam prepared by the materials according to the formula proportion is superior to the odor performance of the marcopolo foam product of the comparative example no matter at normal temperature or at the high temperature of 80 ℃, and the foam odor is lower.
The environmental protection performance (volatile matter) test results of the products prepared according to the formula proportion are shown in table 4.
TABLE 4 environmental Performance (volatiles) test results for the products prepared in examples 1-6
The results of the environmental protection performance test in Table 4 show that the atomization value of the flatulence memory polyurethane foam prepared by the material is lower than 2mg, the formaldehyde content is lower than 10mg/Kg, the TVOC content is lower than 50 mu g C/g, the triphenyl content is lower than the detection limit, the volatile content is lower than the standard requirement, and the environmental protection performance is better.
The flame retardant performance test results of the products prepared according to the formula proportion are shown in Table 5.
TABLE 5 flame retardancy test results of the products prepared in examples 1-6 and comparative examples
The results of flame retardant property tests in Table 5 show that the flame retardant property of the flatulence memory polyurethane foam prepared by the invention completely meets the flame retardant requirement of standard JT/T1095-2016 of the traffic and transportation industry of the people's republic of China on elastic cushion materials. And the oxygen index (standard requirement is more than or equal to 22 percent) is higher than that of the marcopolo memory polyurethane foam of the comparative example.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (1)
1. The full-water environment-friendly flame-retardant flatulence memory polyurethane foam for the automobile seat is characterized by comprising a component A and a component B, wherein the component A comprises the following components in parts by weight:
70 portions of polyether polyol A
Polyether polyol B15 parts
Polyether polyol C15 parts
Chemical foaming agent 3.0 parts
1.5 parts of composite catalyst
Foam stabilizer 1.5 parts
1.2 parts of a crosslinking/chain extender;
the component B is full MDI system isocyanate;
wherein the dosage of the component B is determined according to the isocyanate index of 75, and the isocyanate index is the proportion of NCO groups in the component B and OH or active H groups in polyether polyol in the component A;
polyether polyol A is 3 functionality, glycerol is an initiator, and is copolymerized polyol formed by ring-opening polymerization reaction of ethylene oxide and propylene oxide, wherein the hydroxyl value is 42mgKOH/g, and the molecular weight is 4000;
the polyether polyol B is 3-functionality, the glycerol is used as an initiator, and the polyether polyol B and propylene oxide are subjected to ring-opening polymerization to form a copolymerized polyol, wherein the hydroxyl value is 225-245 mgKOH/g, and the molecular weight is 700;
polyether polyol C is 3 functionality, trimethylolpropane is used as an initiator, and is copolymerized with ethylene oxide-propylene oxide through ring-opening polymerization reaction to form copolymerized polyol, wherein the ethylene oxide content is greater than 55%, the hydroxyl value is 34mgKOH/g, and the molecular weight is 5000;
the chemical foaming agent is water;
the composite catalyst is a mixture of ZF-10, NA-720 and 33LX, and specifically comprises 0.1 part of ZF-10, 0.6 part of NA-720 and 0.8 part of 33 LX;
the foam stabilizer is UF-5766;
the cross-linking agent in the cross-linking/chain-extending agent is a mixture of DEG and TMP, wherein DEG accounts for 60wt% of the cross-linking/chain-extending agent mixture, and TMP accounts for 40 wt%;
the full MDI system isocyanate is MDI-50, a mixture of urethane modified MDI and P-MDI which are formed by reacting MDI and polyhydric alcohol, and the NCO content of the obtained modified MDI is 29-30%.
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