CN110903454B - Modified polyurethane foam material and preparation method and application thereof - Google Patents
Modified polyurethane foam material and preparation method and application thereof Download PDFInfo
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- CN110903454B CN110903454B CN201911280814.4A CN201911280814A CN110903454B CN 110903454 B CN110903454 B CN 110903454B CN 201911280814 A CN201911280814 A CN 201911280814A CN 110903454 B CN110903454 B CN 110903454B
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- 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
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- 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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
- C08J9/102—Azo-compounds
- C08J9/103—Azodicarbonamide
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
- C08J9/141—Hydrocarbons
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
- C08J9/143—Halogen containing compounds
- C08J9/144—Halogen containing compounds containing carbon, halogen and hydrogen only
- C08J9/145—Halogen containing compounds containing carbon, halogen and hydrogen only only chlorine as halogen atoms
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
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- C08K7/00—Use of ingredients characterised by shape
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/28—Glass
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- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound
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- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
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- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
- C08J2203/142—Halogenated saturated hydrocarbons, e.g. H3C-CF3
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- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/18—Binary blends of expanding agents
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/06—Polyurethanes from polyesters
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- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
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- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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Abstract
The invention provides a modified polyurethane foam material and a preparation method and application thereof, belonging to the technical field of polyurethane materials. The modified polyurethane foam material provided by the invention is prepared from the following components in parts by mass: 100-140 parts of a polyol; 200-240 parts of polyisocyanate; 6-18 parts of a flame retardant; 7-18 parts of a reinforcing agent; 9-15 parts of a foaming agent; 1.8-2.2 parts of a surfactant; 3-4 parts of a catalyst. The modified polyurethane foaming material prepared by using the polyol and the polyisocyanate as main bodies and matching with the flame retardant and the reinforcing agent under the combined action of the foaming agent, the surfactant and the catalyst not only retains the advantages of high porosity, low density, air permeability, heat preservation and large volume of polyurethane foam, but also has excellent mechanical property, flame retardant property and bonding property.
Description
Technical Field
The invention relates to the technical field of polyurethane materials, in particular to a modified polyurethane foam material and a preparation method and application thereof.
Background
The rigid polyurethane foam has the advantages of excellent mechanical property, small density, light weight, good porous structure and convenient preparation. Conventional polyurethane foams are prepared by foaming reaction using chlorofluorocarbon compounds (CFCs) as a blowing agent, but CFCs seriously damage the earth's ozone layer structure, cause greenhouse effect, destroy the living environment of human beings, and are banned all over the world. Meanwhile, the use of polyurethane foam in large quantities greatly consumes increasingly exhausted petroleum resources, and causes 'white pollution' due to the fact that the polyurethane foam cannot be degraded after being discarded.
The traditional rigid polyurethane foam mainly comprises a hydrocarbon chain segment, so that the rigid polyurethane foam is extremely easy to burn, the Limiting Oxygen Index (LOI) of the rigid polyurethane foam is only 18.1%, and a large amount of black smoke is released in the burning process, so that great hidden danger is brought to fire safety.
Disclosure of Invention
The invention aims to provide a modified polyurethane foam material, a preparation method and application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a modified polyurethane foam material which is prepared from the following components in parts by mass:
100-140 parts of a polyol;
200-240 parts of polyisocyanate;
6-18 parts of a flame retardant;
7-18 parts of a reinforcing agent;
9-15 parts of a foaming agent;
1.8-2.2 parts of a surfactant;
3-4 parts of a catalyst.
Preferably, the polymeric polyol comprises a polyether polyol or a polyester polyol;
the polyisocyanate comprises one or more of diphenylmethane diisocyanate, toluene diisocyanate, polymethylene polyphenyl polyisocyanate and hexamethylene diisocyanate.
Preferably, the flame retardant comprises one or more of hybrid silicon, tris (2-chloroethyl) phosphate, melamine, aluminum hydroxide and borate;
the reinforcing agent comprises one or more of lignin, calcium carbonate, hollow glass beads and carbon fibers;
the surfactant comprises one or more of dimethyl silicone oil, polysiloxane, epoxidized soybean oil and vinyl silicone oil.
Preferably, the catalyst is an organometallic catalyst and a tertiary amine catalyst.
Preferably, the blowing agent comprises a chemical blowing agent and a physical blowing agent;
the chemical foaming agent comprises water, azodicarbonamide, isopropyl azodicarbonamide or 4,4' -oxybis-benzenesulfonylhydrazide;
the physical foaming agent comprises one or more of dichloromethane, n-hexane, petroleum ether, liquid carbon dioxide and trichlorofluoromethane.
The invention provides a preparation method of the modified polyurethane foam material in the technical scheme, which comprises the following steps:
mixing the polyol, the reinforcing agent, the flame retardant, the foaming agent, the surfactant, the catalyst and the polyisocyanate, and sequentially foaming, maintaining and curing to obtain the modified polyurethane foam material.
Preferably, the foaming temperature is 0-30 ℃, and the time is 10-30 min.
Preferably, the curing temperature is 40-70 ℃, and the curing time is 2-20 h.
Preferably, the curing temperature is 5-40 ℃ and the curing time is 2-30 h.
The invention also provides the application of the modified polyurethane foam material prepared by the technical scheme or the modified polyurethane foam material prepared by the preparation method in the technical scheme in a thermal insulation material.
The invention provides a modified polyurethane foam material which is prepared from the following components in parts by mass: 100-140 parts of a polyol; 200-240 parts of polyisocyanate; 6-18 parts of a flame retardant; 7-18 parts of a reinforcing agent; 9-15 parts of a foaming agent; 1.8-2.2 parts of a surfactant; 3-4 parts of a catalyst. According to the invention, the polyol and the polyisocyanate are used as framework materials of the modified polyurethane foam material, the flame retardant and the reinforcing agent are used in a matched manner, and under the combined action of the foaming agent, the surfactant and the catalyst, the obtained modified polyurethane foam material not only retains the advantages of porosity, low density, air permeability, heat preservation and large volume of polyurethane foam plastic, but also retains the excellent performances of the isocyanate and the polyol, has good adhesive properties on various base materials such as glass, metal, plastic, wood, steel and the like, and has the advantages that other kinds of foam materials do not have; and the mechanical property and the flame retardant property are excellent. As shown in the results of the examples, the tensile strength of the modified polyurethane foam material provided by the invention is as high as 1.21 MPa.
The preparation method provided by the invention is simple to operate and suitable for industrial production.
Detailed Description
The invention provides a modified polyurethane foam material which is prepared from the following components in parts by mass:
100-140 parts of a polyol;
200-240 parts of polyisocyanate;
6-18 parts of a flame retardant;
7-18 parts of a reinforcing agent;
9-15 parts of a foaming agent;
1.8-2.2 parts of a surfactant;
3-4 parts of a catalyst.
In the present invention, all the raw material components are commercially available products well known to those skilled in the art unless otherwise specified.
In the invention, the raw materials for preparing the modified polyurethane foam material comprise, by weight, 100-140 parts of polyol, preferably 110-130 parts, and more preferably 120 parts. In the present invention, the polyester polyol preferably includes polyether polyol or polyester polyol. In the present invention, the polyether polyol preferably includes one or more of polyoxypropylene diol, polyoxypropylene triol, polytetrahydrofuran diol and polyether polyol 4110 b. In the present invention, the polyester polyol is preferably obtained by esterification of a carboxyl group-containing raw material and a polyol raw material; the carboxyl-containing material preferably comprises a dibasic acid, anhydride or ester; the dibasic acids preferably include phthalic acid, phthalic anhydride or phthalate, adipic acid, halophthalic acid; the polyhydric alcohol preferably comprises one or more of ethylene glycol, propylene glycol, diethylene glycol, trimethylolpropane and pentaerythritol.
In the invention, the raw materials for preparing the modified polyurethane foaming material comprise 200-240 parts of polyisocyanate, preferably 210-230 parts of polyisocyanate, and more preferably 220 parts of polyisocyanate by weight parts of the polymeric polyol. In the present invention, the polyisocyanate preferably includes one or more of diphenylmethane diisocyanate, toluene diisocyanate, polymethylene polyphenyl polyisocyanate and hexamethylene diisocyanate. In the invention, the polymeric polyol and the polyisocyanate form a framework material for preparing the modified polyurethane foam material, the ratio of the two dosage has great influence on the performance of the modified polyurethane foam material, and when the dosage of the polymeric polyol is excessive, the modified polyurethane foam material is easy to crack or collapse; if the using amount is too small, the modified polyurethane foaming material is hard, the elasticity is reduced, and the hand feeling is not good; when the amount of the polyisocyanate is too much, the modified polyurethane foam material can form macropores and closed pores, the hardness is increased, and the curing time is long, so that the modified polyurethane foam material is burnt; if the using amount is too small, the modified polyurethane foaming material has foam cracks, poor rebound resilience, poor strength, increased compression set and the like; according to the invention, the use amounts of the polyol and the polyisocyanate are controlled within the above range (100-140 parts of polyol and 200-240 parts of polyisocyanate), so that the foaming performance, the mechanical property and the bonding property of the modified polyurethane foaming material can be improved.
In the invention, the polymeric polyol and the polyisocyanate form the framework of the modified polyurethane foam material. Generally, the higher the percentage content of the polyisocyanate or the derivative thereof is, the higher the surface tension of the adhesive layer is, the better the adhesive strength can be matched with the base materials such as metal and the like, but if the NCO content is too high, the hard segment content is too high, and the activity and the diffusion capability of the polymer chain segment can be restrained due to too much polar group content, so that the adhesive strength is reduced; the invention controls the mass ratio of the isocyanate and the hydroxyl within the range, can ensure that the molar ratio of the isocyanate and the hydroxyl, namely the isocyanate index R ═ n-NCO/n-OH is within the range of 1.2-1.8, improves the bonding performance of the polyurethane foam material, and the modified polyurethane foam material obtained under the combined action of other raw materials has good connectivity to various base materials such as glass, metal, plastic, wood, steel and the like.
In the invention, the raw materials for preparing the modified polyurethane foaming material comprise 6-18 parts of flame retardant, preferably 8-16 parts of flame retardant, and more preferably 10-12 parts of flame retardant based on the weight parts of the polymeric polyol. In the present invention, the flame retardant preferably comprises one or more of hybrid silicon, tris (2-chloroethyl) phosphate (TCEP), melamine and aluminum hydroxide, borate, more preferably hybrid silicon, tris (2-chloroethyl) phosphate (TCEP), melamine, aluminum hydroxide or borate, and most preferably hybrid silicon. In the invention, the too much consumption of the flame retardant can cause the elasticity of the modified polyurethane foam material to be gradually poor, namely the hardness is increased, and the structure of the modified polyurethane foam material is looser and looser along with the increase of the consumption of the flame retardant, and finally the modified polyurethane foam material can not be obtained after being crushed; according to the invention, the dosage of the flame retardant is controlled within the range, so that the mechanical property and the flame retardant property of the modified polyurethane foam material can be improved.
In the present invention, the preparation method of the hybrid silicon preferably comprises the following steps: and soaking the waste foam in a sodium silicate solution, and then sequentially drying, crushing and calcining to obtain the hybrid silicon. In the invention, the mass concentration of the sodium silicate solution is preferably 5-20%, more preferably 10-15%; the amount of the sodium silicate solution is not particularly limited, and the waste foam can be immersed. In the invention, after the waste foam is soaked in the sodium silicate solution, the sodium silicate can cover and permeate into the foam pores of the waste foam, thereby improving the strength and the flame retardant property of the waste foam.
In the invention, the soaking time is preferably 2-24 h, more preferably 12-24 h, and most preferably 20-24 h.
In the present invention, the drying preferably includes forced air drying and vacuum drying which are sequentially performed. In the invention, the temperature of the forced air drying is preferably 50-120 ℃, more preferably 70-100 ℃, and most preferably 90 ℃; the time is preferably 0.5-3 h, and more preferably 1 h; the forced air drying is preferably carried out in an electrically heated forced air drying oven. In the invention, the temperature of the vacuum drying is preferably 90-110 ℃, and more preferably 100 ℃; the time is preferably 0.5-3 h, and more preferably 1 h; the pressure is preferably 0.1-0.6 MPa, and more preferably 0.2-0.4 MPa; the vacuum drying is preferably carried out in a vacuum drying oven.
In the present invention, the crushing is preferably performed by grinding. In the invention, the granularity of the powder obtained after crushing is preferably 50-100 meshes, and more preferably 70-80 meshes.
In the present invention, the calcination is preferably carried out in a tube furnace; the temperature rise rate of the tubular furnace is preferably 2-12 ℃/min, more preferably 4-10 ℃/min, and most preferably 5 ℃/min. In the invention, the calcination temperature is preferably 800-1000 ℃, more preferably 850-950 ℃, and most preferably 900 ℃; the calcination time is preferably 3-15 h, more preferably 8-14 h, and most preferably 12 h.
After the calcination is completed, the present invention preferably further comprises reducing the temperature of the resulting system to room temperature to obtain hybrid silicon.
In the invention, the hybrid silicon contains at least one of Si-Si bond, Si-C bond and Si-P bond, and is physically mixed in the foaming material to form an inorganic oxygen-isolating and heat-insulating protective layer during combustion, namely the hybrid silicon improves the flame-retardant and smoke-inhibiting effects mainly by improving the molecular structure of polyurethane, improving the relative molecular mass and blending of polyurethane, and improves the carbon formation, processing and mechanical properties of a matrix material, so that the modified polyurethane foaming material has excellent flame-retardant property and mechanical property; and the hybrid silicon takes waste foam as a raw material, has wide source, and greatly reduces the flame retardant cost of the modified polyurethane foam material.
In the invention, the flame retardant mechanism of the hybrid silicon flame retardant is a condensed phase flame retardant mechanism, namely, a cracked carbon layer is formed and the oxidation resistance of the carbon layer is improved, after the hybrid silicon flame retardant is added into a polymer material, the hybrid silicon flame retardant migrates to the surface of the material to form a polymer gradient material with a flame retardant enrichment layer, once the hybrid silicon flame retardant is combusted, an inorganic oxygen-insulating and heat-insulating protective layer containing Si-Si and/or Si-C bonds generated in the combustion process is generated, so that the escape of combustion decomposition products is prevented, the thermal decomposition of a high polymer material is inhibited, and the purposes of preventing smoke, retarding flame and reducing toxicity are achieved. According to the invention, the hybrid silicon is prepared by taking the waste foam and the sodium silicate as raw materials, and then the hybrid silicon is taken as a flame retardant of the polyurethane foam material, so that on one hand, the waste foam solid waste is secondarily utilized, the environment is protected, and on the other hand, the flame retardant property of the polyurethane foam material can be obviously improved.
The modification provided by the invention improves the flame retardance according to the condensed phase flame retardant principle, the added hybrid silicon is a substance formed by hybridizing silicon-containing organic matters and inorganic matters, and the silicon-containing groups have higher hydrophobicity, thermal stability, oxidation stability and good flexibility, so that the polyurethane foam has the flame retardant and heat resistant performances, and once the polyurethane foam is burnt, an inorganic oxygen-insulating and heat-insulating protective layer which is peculiar to polysiloxane and contains Si-Si and/or Si-C bonds is generated, so that the flame retardance is improved.
In the invention, the raw materials for preparing the modified polyurethane foaming material comprise 7-18 parts of reinforcing agent, preferably 12-16 parts of reinforcing agent, and more preferably 12-14 parts of polyatomic alcohol by weight. In the invention, the reinforcing agent preferably comprises one or more of lignin, calcium carbonate, hollow glass beads and carbon fibers, and more preferably comprises lignin, calcium carbonate, hollow glass beads or carbon fibers. In the invention, the reinforcing agent is used for replacing part of the polyol raw material, so that the mechanical property of the polyurethane foam material is improved, the production cost is reduced, and the polyurethane foam material is environment-friendly. In the invention, the excessive using amount of the reinforcing agent can reduce the compressibility of the modified polyurethane foaming material; the crosslinking degree of the modified polyurethane foam material is increased and the mechanical property is deteriorated due to the too small using amount; according to the invention, the dosage of the reinforcing agent is controlled within the range, so that the mechanical property of the modified polyurethane foam material can be improved.
In the invention, the raw materials for preparing the modified polyurethane foaming material comprise 9-15 parts of foaming agent, preferably 10-14 parts of foaming agent, and more preferably 11-12 parts of foaming agent by weight of the polymeric polyol. In the present invention, the foaming agent preferably includes a chemical foaming agent and a physical foaming agent. In the present invention, the chemical blowing agent preferably comprises water, azodicarbonamide, isopropyl azodicarbonamide, or 4,4' -oxybis-benzenesulfonylhydrazide. In the present invention, the physical blowing agent preferably includes one or more of dichloromethane, n-hexane, petroleum ether, liquid carbon dioxide and trichlorofluoromethane. In the present invention, the mass ratio of the chemical foaming agent to the physical foaming agent is preferably (0.1 to 0.3): 1, more preferably 0.2: 1. In the invention, the excessive using amount of the foaming agent is easy to cause the reduction of the apparent density and the increase of the hardness of the modified polyurethane foaming material, and simultaneously, the struts of foam holes become small and weak, thereby reducing the bearing capacity, being easy to collapse and crack, and simultaneously causing the increase of the amount of the consumed polyisocyanate, more heat release and easy burning; the foaming of the modified polyurethane foaming material is incomplete easily caused by too little using amount; according to the invention, the amount of the foaming agent is controlled within the range, so that the foaming density of the modified polyurethane foaming material can be improved, and the mechanical property of the modified polyurethane foaming material can be improved.
In the invention, the raw materials for preparing the modified polyurethane foaming material comprise 1.8-2.2 parts of surfactant, preferably 1.8-2.0 parts, and more preferably 1.8 parts by weight of the polyhydric alcohol. In the present invention, the surfactant preferably includes one or more of dimethicone, polysiloxane, epoxidized soybean oil, and vinyl silicone oil, and more preferably includes dimethicone, polysiloxane, epoxidized soybean oil, or vinyl silicone oil. In the invention, the excessive dosage of the surfactant causes the elasticity of the foam wall to be increased in the later period, the foam wall is not easy to break, and the cells are fine to cause closed cells; too little dosage leads to insufficient stability of the foam holes, causes serious foam merging, thick and uneven foam holes and even foam collapse; the invention controls the dosage of the surfactant in the range, can play a role in stabilizing cells, and can control the cell structure and uniformity of the modified polyurethane foam material.
In the invention, the raw materials for preparing the modified polyurethane foaming material comprise 3-4 parts of catalyst, preferably 3.2-3.8 parts, and more preferably 3.4-3.6 parts by weight of the polyhydric alcohol. In the present invention, the catalyst is preferably an organometallic catalyst and a tertiary amine catalyst. In the present invention, the organometallic catalyst preferably includes one or more of dibutyltin dilaurate, dibutyltin diacetate, dioctyltin and dibutyltin. In the present invention, the tertiary amine catalyst preferably includes one or more of triethanolamine, triethylenediamine, dimethylaminoethoxyethanol, and dimethylethanolamine. In the present invention, the mass ratio of the organometallic catalyst to the tertiary amine catalyst is preferably (4 to 5): 1, more preferably (4 to 4.5): 1. in the invention, the hollow cracking of the modified polyurethane foam material is easily caused by the excessive use amount of the catalyst; if the using amount is too small, the modified polyurethane foam material shrinks seriously; the invention controls the dosage of the catalyst within the range, and can improve the mechanical property of the modified polyurethane foam material.
The invention provides a preparation method of the modified polyurethane foam material in the technical scheme, which comprises the following steps:
mixing the polyol, the reinforcing agent, the flame retardant, the chemical foaming agent, the surfactant, the catalyst, the physical foaming agent and the polyisocyanate, and sequentially foaming, maintaining and curing to obtain the modified polyurethane foaming material.
In the present invention, the order of mixing the polymeric polyol, the reinforcing agent, the flame retardant, the chemical blowing agent, the surfactant, the catalyst, the physical blowing agent, and the polyisocyanate is preferably a first mixing of the polymeric polyol, the reinforcing agent, the flame retardant, the chemical blowing agent, the surfactant, the catalyst, and the physical blowing agent, and then a second mixing by adding the polyisocyanate. In the present invention, the first mixing and the second mixing are preferably performed by stirring; the speed of the first mixing and the second mixing is preferably 200-400 r/min independently, and more preferably 300 r/min; the first mixing time is not specially limited, and the raw materials can be uniformly mixed; the time for the second mixing is not particularly limited, and the stirring is carried out until the milky white appears, namely the milky white time is reached, specifically 1-20 s.
In the invention, the foaming temperature is preferably 0-30 ℃, more preferably 20-30 ℃, and the time is 10-30 min, more preferably 10-20 min. In the present invention, when water is used as the chemical blowing agent, the polyisocyanate reacts with water during the foaming process to generate amine through the intermediate product and generate carbon dioxide gas, i.e. the foaming reaction occurs, and the reaction formula is as follows: r to NCO + H-O-H →toR to NHCOOH → RHNH + CO-O; the polyisocyanate group reacts with the hydroxyl group of the polyol to form a urethane group with the release of heat, i.e., a gelling reaction, according to the following reaction formula: R-NCO + HO-R '→ -R-NHCOO-R', wherein R-NCO represents an isocyanate group contained in the polyisocyanate group.
In the invention, the curing temperature is preferably 40-70 ℃, more preferably 50-60 ℃, and the time is preferably 2-20 hours, more preferably 10-12 hours; the curing method is preferably static curing. In the present invention, the reaction occurring during the curing process is a gel reaction, i.e., the reaction of the residual isocyanate with the unreacted polyol and the polyamine is promoted to complete the synthesis reaction of the polyurethane and polyurea.
In the invention, the curing temperature is preferably 5-40 ℃, more preferably 25-35 ℃, and the time is preferably 2-30 hours, more preferably 15-20 hours. In the present invention, the amine formed during the foaming process during the curing process reacts quickly with excess isocyanate to form urea according to the following reaction scheme: r to NCO + HNH to R →toR to NHCONH to R ~; the isocyanate reacts with the hydrogen on the urethane nitrogen atom to form an allophanate, the reaction formula is as follows: and the curing temperature is controlled to accelerate the reaction process and prevent the modified polyurethane foaming material from deforming.
The modified polyurethane foaming material prepared by the invention generates urethane bonds and urea bonds with higher cohesive energy when foaming, and can be gathered on a bonding surface under certain conditions to form a high surface tension adhesive layer; the base material such as wood and the like is composed of fibers, the fibers have certain moisture absorption rate and often contain polar bonds such as ether bonds, ester bonds, amido bonds and the like, carboxyl groups, hydroxyl groups and the like, water and the hydroxyl groups are easy to react with-NCO groups in the modified polyurethane foaming material to form chemical bonds such as firm urethane bonds and urea bonds, hydrogen bonds are formed between the polar groups in the fibers and the polar groups in polyisocyanate, and polyisocyanate glue water molecules are easy to permeate into the fibers, so that firm bonding can be generally formed for the materials; during foaming, the polyhydric alcohol and the polyisocyanate generate carbamido or biuret, and during curing, the isocyanate can generate self-polymerization to form a cross-linked structure and form a polymer cross-linked interpenetrating network (IPI) with a rubber molecule cross-linked network; therefore, the modified polyurethane foam material prepared by the invention has excellent bonding performance on glass, metal, plastic, wood and steel, which is an advantage that other kinds of foam materials do not have. The modified polyurethane foam material prepared by the invention has excellent mechanical property and flame retardant property. The preparation method provided by the invention is simple to operate and suitable for industrial production.
The invention also provides the application of the modified polyurethane foam material prepared by the technical scheme or the modified polyurethane foam material prepared by the preparation method in the technical scheme in a thermal insulation material.
In the invention, the modified polyurethane foam material is preferably sprayed when the thermal insulation material is applied and constructed. The polyurethane sprayed on the hard foam body is a high-molecular thermosetting polymer, and a local heat bridge is often caused by permanent mechanical anchoring, temporary fixing and fixing of attachments on a wall-penetrating pipeline or an outer wall.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Preparing raw materials: 12g of polyether polyol, 1.2g of hybrid silicon, 1.8g of lignin, 0.2g of distilled water, 1g of dichloromethane, 0.18g of simethicone, 0.068g of triethanolamine, 0.28g of dibutyltin dilaurate and 22g of dimethyl alkyl diisocyanate.
Immersing waste foam into a sodium silicate solution for soaking for 24h, then placing the soaked waste foam in an electric heating blast drying oven for drying for 1h at 90 ℃, then placing the waste foam in a vacuum drying oven for drying for 2h at 100 ℃ and 0.3MPa, grinding the obtained dried material into powder, placing the obtained powder in a tubular furnace, raising the temperature to 900 ℃ at the heating rate of 5 ℃/min, calcining for 12h, and cooling to room temperature to obtain the hybrid silicon.
Putting polyether polyol, lignin, hybrid silicon, distilled water, dimethyl silicon oil, triethanolamine, dibutyltin dilaurate and dichloromethane into a beaker, uniformly stirring and mixing, adding dimethyl diisocyanate into the obtained mixed solution, stirring for 20s at 300r/min, then starting to present milky color, pouring the obtained mixed solution into a mold, allowing the mixed solution to foam for 10min automatically, standing and curing the obtained material at 55 ℃ for 10h, curing at 25 ℃ for 18h, and removing the mold to obtain the modified polyurethane foam material.
Examples 2 to 9
The modified polyurethane foam was prepared according to the method of example 1, except that the amounts of hybrid silicon, lignin and dimethicone were different from those of example 1. The amounts of hybrid silicon, lignin and dimethicone used in examples 1-9 are shown in Table 1.
TABLE 1 EXAMPLES 1 TO 9 Each raw material amount
Example 10
Preparing raw materials: 12g of polyester polyol, 0.6g of tris (2-chloroethyl) phosphate (TCEP), 1.2g of calcium carbonate, 0.2g of azodicarbonic acid Amine (ADC), 1g of n-hexane, 0.20g of polysiloxane, 0.068g of triethylenediamine (1-6), 0.28g of dibutyltin diacetate and 22g of toluene diisocyanate.
Placing polyester polyol, calcium carbonate, tris (2-chloroethyl) phosphate (TCEP), azodicarbonic acid Amine (ADC), polysiloxane, triethylene diamine (1-6), dibutyltin diacetate and n-hexane in a beaker, stirring and mixing uniformly, adding toluene diisocyanate into the obtained mixed solution, stirring for 20s at the speed of 300r/min, enabling the mixed solution to be milky, pouring the obtained mixed solution into a mold to enable the mixed solution to foam for 10min, standing and curing the obtained material at the temperature of 55 ℃ for 10h, curing at the temperature of 25 ℃ for 18h, and removing the mold to obtain the modified polyurethane foam material.
Example 11
Preparing raw materials: 12g of polyether polyol, 1.8g of melamine, 1.2g of hollow glass microsphere, 0.2g of diisopropyl azodicarboxylate, 1g of petroleum ether, 0.20g of epoxidized soybean oil, 0.068g of dimethylaminoethoxyethanol, 0.28g of dioctyltin and 22g of polymethylene polyphenyl polyisocyanate (PAPI).
Putting polyether polyol, hollow glass beads, melamine, azodicarbonic acid Amine (ADC), polysiloxane, dimethylaminoethoxyethanol, dioctyltin and petroleum ether into a beaker, stirring and mixing uniformly, adding polymethylene polyphenyl polyisocyanate (PAPI) into the obtained mixed solution, stirring for 20s at the speed of 300r/min, then starting to present milky color, pouring the obtained mixed solution into a mould to enable the mixed solution to foam for 10min automatically, standing and maintaining the obtained material at the temperature of 55 ℃ for 10h, curing for 18h at the temperature of 25 ℃, and removing the mould to obtain the modified polyurethane foam material.
Example 12
Preparing raw materials: 12g of polyester polyol, 1.2g of aluminum hydroxide, 1.2g of carbon fiber, 0.2g of 4,4' -oxybis-benzenesulfonylhydrazide (OBSH), 1g of liquid carbon dioxide, 0.22g of vinyl silicone oil, 0.068g of dimethylethanolamine (1-11), 0.28g of dibutyltin and 22g of Hexamethylene Diisocyanate (HDI).
Placing polyester polyol, carbon fiber, aluminum hydroxide, 4' -oxybis-benzenesulfonylhydrazide (OBSH), vinyl silicone oil, dimethylethanolamine (1-11), dibutyltin and liquid carbon dioxide in a beaker, uniformly stirring and mixing, adding Hexamethylene Diisocyanate (HDI) into the obtained mixed solution, stirring for 20s at 300r/min, enabling the mixed solution to be milky, pouring the obtained mixed solution into a mold, enabling the mixed solution to foam for 10min, standing and maintaining the obtained material at 55 ℃ for 10h, curing at 25 ℃ for 18h, and removing the mold to obtain the modified polyurethane foam material.
Test example
1. Tensile strength
A test piece is manufactured according to the national standard GB/T9641-1988, the size is 5cm multiplied by 1cm multiplied by 5mm, a universal mechanical testing machine is used for carrying out tensile test within the range of 100-2000 mm/min until the sample is broken, and the test results are shown in Table 2.
2. Oxygen index
The oxygen index of the samples was tested according to the national standard GB/T2406-93, and the test results are shown in Table 2.
3. Cell uniformity
The foam cell morphology was observed by SEM and the test results are shown in table 2.
4. Density of
The dimensions of the samples were measured according to the national standard GB/T6342-1996, and the apparent density was determined according to the national standard GB/T6343-2009/IS 0845:2006, with the test results shown in Table 2.
5. Compression set
According to the national standard GB/T6669-2008, the section test is carried out on the cross section of a representative extruded or moulded sample of known area, each sample having a length of 50mm and a thickness of not less than 3 mmn. The upper and lower surfaces of the test specimen should be parallel, and the test results are shown in table 2.
TABLE 2 Performance test results of modified polyurethane foams
As can be seen from Table 2, the oxygen index of the modified material prepared by the method reaches the flame retardancy, most of the modified material reaches the grade B1, and the density is 45-60 g/cm3Within the range. The modified polyurethane foaming material prepared by the invention has excellent mechanical property and flame retardant property.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (8)
1. The modified polyurethane foam material is characterized by being prepared from the following components in parts by mass:
100-140 parts of a polyol;
200-240 parts of polyisocyanate;
6-18 parts of a flame retardant;
7-18 parts of a reinforcing agent;
9-15 parts of a foaming agent;
1.8-2.2 parts of a surfactant;
3-4 parts of a catalyst;
the flame retardant is hybrid silicon; the preparation method of the hybrid silicon comprises the following steps: soaking the waste foam in a sodium silicate solution, and then sequentially drying, crushing and calcining to obtain hybrid silicon; the mass concentration of the sodium silicate solution is 5-20%; the soaking time is 2-24 hours; the calcining temperature is 800-1000 ℃, and the time is 3-15 h;
the reinforcing agent comprises one or more of lignin, calcium carbonate, hollow glass beads and carbon fibers;
the preparation method of the modified polyurethane foam material comprises the following steps:
mixing the polyol, the reinforcing agent, the flame retardant, the foaming agent, the surfactant, the catalyst and the polyisocyanate, and sequentially foaming, maintaining and curing to obtain the modified polyurethane foam material;
the curing temperature is 40-70 ℃, and the curing time is 10-20 hours;
the curing temperature is 5-40 ℃, and the curing time is 15-30 h.
2. The modified polyurethane foam according to claim 1, wherein the polyester polyol comprises a polyether polyol or a polyester polyol;
the polyisocyanate comprises one or more of diphenylmethane diisocyanate, toluene diisocyanate, polymethylene polyphenyl polyisocyanate and hexamethylene diisocyanate.
3. The modified polyurethane foam material as claimed in claim 1, wherein the surfactant comprises one or more of dimethicone, polysiloxane, epoxidized soybean oil and vinyl silicone oil.
4. The modified polyurethane foam according to claim 1, wherein the catalyst is an organometallic catalyst and a tertiary amine catalyst.
5. The modified polyurethane foam material as claimed in claim 1, wherein the foaming agent comprises a chemical foaming agent and a physical foaming agent;
the chemical foaming agent comprises water, azodicarbonamide, isopropyl azodicarbonamide or 4,4' -oxybis-benzenesulfonylhydrazide;
the physical foaming agent comprises one or more of dichloromethane, n-hexane, petroleum ether, liquid carbon dioxide and trichlorofluoromethane.
6. The preparation method of the modified polyurethane foam material as claimed in any one of claims 1 to 5, which is characterized by comprising the following steps:
mixing the polyol, the reinforcing agent, the flame retardant, the foaming agent, the surfactant, the catalyst and the polyisocyanate, and sequentially foaming, maintaining and curing to obtain the modified polyurethane foam material;
the curing temperature is 40-70 ℃, and the curing time is 10-20 hours;
the curing temperature is 5-40 ℃, and the curing time is 15-30 h.
7. The method according to claim 6, wherein the foaming temperature is0 to 30 ℃ and the time is 10 to 30 min.
8. Use of the modified polyurethane foam material of any one of claims 1 to 5 or the modified polyurethane foam material prepared by the preparation method of any one of claims 6 to 7 in thermal insulation materials.
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| CN111961180A (en) * | 2020-08-30 | 2020-11-20 | 宁波耀众模塑科技有限公司 | Production formula of polyurethane foaming product based on polyether raw material |
| CN111961327A (en) * | 2020-08-30 | 2020-11-20 | 宁波耀众模塑科技有限公司 | Flame-retardant polyurea material for polyurethane foaming product |
| CN112143213A (en) * | 2020-09-30 | 2020-12-29 | 苏州思德新材料科技有限公司 | Flame-retardant polyurethane foam material catalyst and preparation method thereof |
| CN117855669B (en) * | 2023-12-26 | 2024-06-04 | 惠州市冠宝新材料有限公司 | High noise reduction type PET composite material for computer battery and preparation method thereof |
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