CN111499819A - Polyurethane sponge material and preparation method thereof - Google Patents
Polyurethane sponge material and preparation method thereof Download PDFInfo
- Publication number
- CN111499819A CN111499819A CN202010372269.8A CN202010372269A CN111499819A CN 111499819 A CN111499819 A CN 111499819A CN 202010372269 A CN202010372269 A CN 202010372269A CN 111499819 A CN111499819 A CN 111499819A
- Authority
- CN
- China
- Prior art keywords
- raw material
- surfactant
- polyurethane sponge
- mixture
- mixing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
- C08G18/4812—Mixtures of polyetherdiols with polyetherpolyols having at least three hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
- C08G18/6677—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6688—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3271
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2101/00—Manufacture of cellular products
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention provides a polyurethane sponge and a preparation method thereof. The preparation method of the polyurethane sponge material comprises the following steps: s100, mixing and uniformly stirring water, an alkaline catalyst and a cross-linking agent to prepare a first raw material; s200, preparing a second raw material by adopting dehydrated polyether polyol, isophorone diisocyanate, a metal catalyst, a surfactant and zinc oxide; s300, mixing the first raw material, the second raw material and the uvioresistant agent, and foaming and curing to obtain the polyurethane sponge material. The polyurethane sponge of the invention has excellent properties, and is particularly not prone to yellowing.
Description
Technical Field
The invention relates to the field of plastic product manufacturing, in particular to a polyurethane sponge material and a preparation method thereof.
Background
The polyurethane sponge is one kind of polyurethane foam plastic, belongs to soft polyurethane foam plastic, and is widely applied to the fields of clothing, packaging, automobiles, aviation, furniture and the like due to the advantages of low density, good elasticity, good air permeability, good water resistance, easily available raw materials and the like. At present, most sponge manufacturers still use aromatic isocyanates such as Toluene Diisocyanate (TDI) and diphenylmethane diisocyanate (MDI) as raw materials, and because the isocyanate groups in the TDI and the MDI are directly connected with benzene rings, yellowing and reduction of physical and mechanical properties are easily caused after long-term exposure to the environment of illumination and nitrogen oxides.
At present, two methods are mainly used for improving the light resistance and the aging resistance of the polyurethane sponge. Firstly, a large amount of antioxidant, light stabilizer, whitening agent and the like are added, the method cannot solve the problem of yellowing fundamentally, the existence of a large amount of auxiliary agent can harm the health of people to a certain extent, and in addition, the antioxidant is easy to migrate, and finally the cloth is yellow. And secondly, the aliphatic isocyanate is adopted to replace aromatic isocyanate, and the aliphatic isocyanate does not contain benzene ring, so that the problem of yellowing of the polyurethane sponge can be fundamentally solved. However, this method also has disadvantages in that aliphatic isocyanates are much less reactive than aromatic isocyanates, and a large amount of catalyst needs to be added to the formulation.
Chinese patent CN104974326A discloses a preparation method of non-yellowing soft polyurethane foam, which adopts a semi-prepolymer method to mix polyether polyol, a foaming agent, a surfactant and a catalyst with aliphatic polyurethane prepolymer to prepare polyurethane sponge at 30-40 ℃, in order to improve the reaction activity of the system, the polyether polyol with high terminal hydroxyl group content is used, the limitation to raw materials is more, and simultaneously a large amount of metal catalysts or even organic tin catalysts are used, and the catalysts have certain toxicity.
Chinese patent CN102336885A discloses a method for preparing polyurethane sponge with excellent environmental tolerance, which adopts a one-step method to prepare foam, needs to use a large amount of catalyst, and needs to add hindered phenol antioxidants and hindered amine light stabilizers in the formula, but antioxidants and stabilizers are easy to migrate, which can cause yellowing of the sponge and have certain influence on human body. In addition, the formulation uses physical blowing agents which may be toxic or harmful to the ozone layer.
Disclosure of Invention
The present invention is directed to solving at least one of the above problems.
Therefore, the first purpose of the invention is to provide a preparation method of the polyurethane sponge material.
The second purpose of the invention is to provide a polyurethane sponge material.
In order to achieve the first object of the present invention, an embodiment of the present invention provides a preparation method of a polyurethane sponge material, including the following steps:
s100, according to water: basic catalyst: crosslinking agent ═ (15-25): (50-70): (15-25) mixing and uniformly stirring water, an alkaline catalyst and a cross-linking agent to prepare a first raw material;
s200, according to the polyether polyol: isophorone diisocyanate: metal catalyst: surfactant (b): zinc oxide 45: (40-45): 5: (4-8): (1-2) preparing a second raw material by adopting dehydrated polyether polyol, isophorone diisocyanate, a metal catalyst, a surfactant and zinc oxide according to the mass ratio;
s300, according to a first raw material: a second raw material: anti-ultraviolet agent ═ (10-20): (70-85): (5-10), mixing the first raw material, the second raw material and the anti-ultraviolet agent, foaming and curing to obtain the polyurethane sponge material.
In addition, the technical solution provided by the above embodiment of the present invention may further have the following additional technical features:
in the above technical solution, in the step S100: the cross-linking agent comprises one or more of 1, 4-butanediol, ethylene glycol, 1, 3-butanediol, trimethylolpropane, diethanolamine, triethanolamine and methyldiethanolamine; and/or the basic catalyst comprises one or more combinations of dimethylethanolamine, dimethylaminoethoxyethanol, trimethylhydroxyethylethylenediamine, N, N, N '-trimethyl-N' -hydroxyethylbisaminoethyl ether, N, N-bis (dimethylaminopropyl) isopropanolamine, N, N, N ', N' -tetramethyldipropylenetriamine, bis (dimethylamino) -2-propanol, 1, 8-diazabicycloundec-7-ene or the weak acid salts thereof.
In any of the above technical solutions, in the step S200, the metal catalyst includes one or more combinations of organic bismuth, zinc isobutyrate, zinc octoate, and zirconium acetylacetonate, and/or the surfactant includes one or more combinations of Y-10366 surfactant, L-580 surfactant, L-680 surfactant, B-8715 surfactant, DC-193 surfactant, DC-2525 surfactant, DC-6070 surfactant, DC-540 surfactant, and B-8681 surfactant.
In any of the above technical solutions, the step S200 specifically includes:
s210, dehydrating the polyether polyol for 2 to 3 hours under the vacuum condition of-0.5 to-0.1 MPa and the temperature condition of 110 to 120 ℃ until the moisture content of the polyether polyol is lower than 0.1 wt%;
s220, stirring the polyether polyol obtained in the step S210 at a stirring speed of 90r/min to 100r/min and a stirring temperature of 70 ℃ to 80 ℃, and adding the metal catalyst in the stirring process and timing, wherein the adding amount of the metal catalyst is 0.05 to 0.1 percent of that of the polyether polyol obtained in the step S210;
step S230, timing for 1min to 2min, adding the isophorone diisocyanate and the zinc oxide into the polyether polyol obtained in the step S220, uniformly stirring, and reacting for 2h to 4h at 70 ℃ to 80 ℃ until the content of the isocyanate is 10% to 15%;
step S240, cooling the product obtained in the step S230 to 20 +/-5 ℃, discharging the product into a container, filling nitrogen into the container, and sealing and storing the container to obtain a prepolymer;
and S250, mixing the prepolymer obtained in the step S240 with a surfactant to obtain the second raw material.
In any of the above embodiments, in step S220, the polyether polyol is composed of 70 to 90 parts by weight of the triol and 10 to 30 parts by weight of the diol, based on 100 parts by weight of the polyol.
In any of the above technical solutions, in the step S220, the average molecular weight of the triol is 2000-8000, and the hydroxyl value is 20-85 mgKOH/g; the average molecular weight of the dihydric alcohol is 2000-6000, and the hydroxyl value is 20-60 mgKOH/g.
In any of the above technical solutions, the step S300 specifically includes:
s310, uniformly mixing the first raw material, the second raw material and the uvioresistant agent at the temperature of 20-30 ℃;
and S320, pouring the mixture obtained in the step S310 into a mold with the temperature of 30-40 ℃, foaming at normal temperature, and curing to obtain the polyurethane sponge material.
In any of the above technical solutions, the step S310 specifically includes:
step S312, according to mannitol: glutamic acid: anti-ultraviolet agent: a first raw material: water ═ 1-2: (5-10): (5-10): (5-10): (40-45): (40-45) mixing mannitol, glutamic acid, an anti-ultraviolet agent, a first raw material and water in a mass ratio to obtain a first mixture;
step S314, according to ethyl acetate: polylactic acid-glycolic acid copolymer: second raw material ═ (5-15): (20-40): (45-55) mixing ethyl acetate, polylactic acid-glycolic acid copolymer and a second raw material in a mass ratio to obtain a second mixture;
step S316, pressing (50-55): (45-50) mixing the first mixture obtained through the step S312 and the second mixture through the step S314 at a mass ratio, and performing ultrasonic emulsification.
In any of the above technical solutions, the anti-ultraviolet agent is prepared by the following steps:
step S410, according to monomers: initiator: butyl acetate solvent 35: 5: 60, heating a butyl acetate solvent to 95-98 ℃, introducing nitrogen, gradually dropwise adding a monomer and an initiator into the butyl acetate solvent, preserving heat for 2 hours after dropwise adding, and distilling the solvent to obtain a third mixture;
step S430, according to a third mixture: water ═ 20-30: (70-80) mixing the third mixture with water, gradually adding an ammonium bicarbonate solution and stirring until the third mixture is dissolved to obtain a third mixture solution;
step S440, according to titanium dioxide: third mixture solution: water ═ 10-15: (10-15): (70-75) adding titanium dioxide and water to the third mixture solution obtained in the step S430, and uniformly mixing to obtain an anti-ultraviolet agent slurry;
and S450, gradually adding cation exchange resin into the uvioresistant agent slurry obtained in the S440, stirring, adjusting the pH value to 4-5, and then filtering, washing and drying to obtain the uvioresistant agent.
To achieve the second object of the present invention, embodiments of the present invention provide a polyurethane sponge material, which is obtained by the preparation method of the polyurethane sponge material according to any one of the embodiments of the present invention.
The invention has the beneficial effects that:
1. according to the invention, isophorone diisocyanate is used to replace aromatic isocyanate, so that the sponge has excellent anti-illumination and anti-aging properties;
2. the polyurethane sponge is prepared by a prepolymer method, the gel reaction of the system is carried out in advance, the phenomena of foam collapse, uneven foam holes and the like caused by unbalanced foaming reaction and gel reaction of the system are avoided, the using amount of a catalyst, particularly a metal catalyst, is greatly reduced, the harm to a human body is reduced, and the pollution to the environment is reduced;
3. the method replaces a one-step method with a prepolymer method to produce the polyurethane sponge, releases the reaction heat in two steps, avoids the phenomenon of sponge 'heartburn' possibly caused by the one-step method, and basically omits a post-curing process and simplifies the process because the gel reaction is carried out in advance;
4. the alkaline catalyst used in the invention is a reaction type catalyst, and can meet the requirements of products on odor and Volatile Organic Compounds (VOC);
5. the composite material can be foamed at normal temperature in an open mold, compression molding is not needed, the production requirement of large block foam can be met, and the requirement on equipment is reduced.
6. The polyurethane sponge material disclosed by the invention has excellent performance, is not easy to yellow and has excellent antibacterial performance.
Detailed Description
In order that the above objects, features and advantages of the present invention can be more clearly understood, the present invention will be described in further detail with reference to specific embodiments. It should be noted that the embodiments and features of the embodiments of the present application may be combined with each other without conflict.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, however, the present invention may be practiced in other ways than those specifically described herein, and therefore the scope of the present invention is not limited by the specific embodiments disclosed below.
The embodiment of the invention provides a preparation method of a polyurethane sponge material, which comprises the following steps:
s100, according to water: basic catalyst: crosslinking agent ═ (15-25): (50-70): (15-25) mixing and uniformly stirring water, an alkaline catalyst and a cross-linking agent to prepare a first raw material;
s200, according to the polyether polyol: isophorone diisocyanate: metal catalyst: surfactant (b): zinc oxide 45: (40-45): 5: (4-8): (1-2) preparing a second raw material by adopting dehydrated polyether polyol, isophorone diisocyanate, a metal catalyst, a surfactant and zinc oxide according to the mass ratio;
s300, according to a first raw material: a second raw material: anti-ultraviolet agent ═ (10-20): (70-85): (5-10), mixing the first raw material, the second raw material and the anti-ultraviolet agent, foaming and curing to obtain the polyurethane sponge material.
In some embodiments of the present invention, in step S100:
the cross-linking agent comprises one or more of 1, 4-butanediol, ethylene glycol, 1, 3-butanediol, trimethylolpropane, diethanolamine, triethanolamine and methyldiethanolamine; and/or
The alkaline catalyst comprises one or more of dimethylethanolamine, dimethylaminoethoxyethanol, trimethylhydroxyethylethylenediamine, N, N, N '-trimethyl-N' -hydroxyethylbisaminoethyl ether, N, N-bis (dimethylaminopropyl) isopropanolamine, N, N, N ', N' -tetramethyldipropylenetriamine, bis (dimethylamino) -2-propanol, 1, 8-diazabicycloundec-7-ene or weak acid salts thereof.
In some embodiments of the present invention, in step S200:
the metal catalyst comprises one or more of organic bismuth, zinc isobutyrate, zinc octoate and zirconium acetylacetonate, and/or the surfactant comprises one or more of Y-10366 surfactant, L-580 surfactant, L-680 surfactant, B-8715 surfactant, DC-193 surfactant, DC-2525 surfactant, DC-6070 surfactant, DC-540 surfactant and B-8681 surfactant.
In some embodiments of the present invention, the step S200 specifically includes:
s210, dehydrating the polyether polyol for 2 to 3 hours under the vacuum condition of-0.5 to-0.1 MPa and the temperature condition of 110 to 120 ℃ until the moisture content of the polyether polyol is lower than 0.1 wt%;
s220, stirring the polyether polyol obtained in the step S210 at a stirring speed of 90r/min to 100r/min and a stirring temperature of 70 ℃ to 80 ℃, and adding the metal catalyst in the stirring process and timing, wherein the adding amount of the metal catalyst is 0.05 to 0.1 percent of that of the polyether polyol obtained in the step S210;
step S230, timing for 1min to 2min, adding the isophorone diisocyanate and the zinc oxide into the polyether polyol obtained in the step S220, uniformly stirring, and reacting for 2h to 4h at 70 ℃ to 80 ℃ until the content of the isocyanate is 10% to 15%;
step S240, cooling the product obtained in the step S230 to 20 +/-5 ℃, discharging the product into a container, filling nitrogen into the container, and sealing and storing the container to obtain a prepolymer;
and S250, mixing the prepolymer obtained in the step S240 with a surfactant to obtain the second raw material.
In some embodiments of the present invention, in step S220, the polyether polyol is composed of 70 to 90 parts by weight of a triol and 10 to 30 parts by weight of a diol, based on 100 parts of the polyol.
In some embodiments of the present invention, in step S220, the triol has an average molecular weight of 2000-8000 and a hydroxyl value of 20-85 mgKOH/g; the average molecular weight of the dihydric alcohol is 2000-6000, and the hydroxyl value is 20-60 mgKOH/g.
In some embodiments of the present invention, the step S300 specifically includes:
s310, uniformly mixing the first raw material, the second raw material and the uvioresistant agent at the temperature of 20-30 ℃;
and S320, pouring the mixture obtained in the step S310 into a mold with the temperature of 30-40 ℃, foaming at normal temperature, and curing to obtain the polyurethane sponge material.
In some embodiments of the present invention, the step S310 specifically includes:
step S312, according to mannitol: glutamic acid: anti-ultraviolet agent: a first raw material: water ═ 1-2: (5-10): (5-10): (5-10): (40-45): (40-45) mixing mannitol, glutamic acid, an anti-ultraviolet agent, a first raw material and water in a mass ratio to obtain a first mixture;
step S314, according to ethyl acetate: polylactic acid-glycolic acid copolymer: second raw material ═ (5-15): (20-40): (45-55) mixing ethyl acetate, polylactic acid-glycolic acid copolymer and a second raw material in a mass ratio to obtain a second mixture;
step S316, pressing (50-55): (45-50) mixing the first mixture obtained through the step S312 and the second mixture through the step S314 at a mass ratio, and performing ultrasonic emulsification.
In step S310, after mixing an organic solvent including the second raw material and the polylactic acid-glycolic acid copolymer and an inorganic organic co-solvent including the first raw material and the anti-ultraviolet agent with each other, ultrasonic emulsification is performed. In this step, a PH adjusting agent comprising mannitol and glutamic acid was added. In this embodiment, the first raw material and the anti-uv agent are mixed in water, the organic additive is added, and finally the inorganic organic cosolvent including the first raw material and the anti-uv agent is mixed with the oil phase organic solvent including the second raw material and the polylactic acid-glycolic acid copolymer, and the mixture is ultrasonically emulsified, so that an emulsion of the first raw material and the second raw material can be obtained, and thus, the dispersibility, the uniformity and the surface energy of the first raw material and the second raw material in the solvent can be improved. Therefore, the polyurethane sponge material of the embodiment has uniform and stable performance, the ultraviolet resistant agent is uniformly dispersed in the polyurethane sponge material, and the polyurethane sponge material of the embodiment is not easy to yellow.
In some embodiments of the present invention, the anti-uv agent is prepared by:
step S410, according to monomers: initiator: butyl acetate solvent 35: 5: 60, heating a butyl acetate solvent to 95-98 ℃, introducing nitrogen, gradually dropwise adding a monomer and an initiator into the butyl acetate solvent, preserving heat for 2 hours after dropwise adding, and distilling the solvent to obtain a third mixture;
step S430, according to a third mixture: water ═ 20-30: (70-80) mixing the third mixture with water, gradually adding an ammonium bicarbonate solution and stirring until the third mixture is dissolved to obtain a third mixture solution;
step S440, according to titanium dioxide: third mixture solution: water ═ 10-15: (10-15): (70-75) adding titanium dioxide and water to the third mixture solution obtained in the step S430, and uniformly mixing to obtain an anti-ultraviolet agent slurry;
and S450, gradually adding cation exchange resin into the uvioresistant agent slurry obtained in the S440, stirring, adjusting the pH value to 4-5, and then filtering, washing and drying to obtain the uvioresistant agent.
In order to reduce the surface energy of the anti-ultraviolet agent and improve the dispersion stability of the anti-ultraviolet agent in an organic system, the surface of the titanium dioxide anti-ultraviolet agent is coated with an organic treating agent in the embodiment. Specifically, in this embodiment, a monomer, an initiator and a butyl acetate solvent are used to prepare a third mixture, the third mixture is completely dissolved in deionized water in an alkaline environment, then, a slurry containing titanium dioxide of the third mixture is prepared, finally, a cation exchange resin is used to replace the nano-ions of the slurry, as the nano-ions in the slurry are replaced, the PH of the slurry decreases, and the third mixture with low surface energy gradually precipitates on the surface of the titanium dioxide, thereby forming an organic coating film layer. Because the surface energy of the ultraviolet resistant agent in this embodiment is low, the ultraviolet resistant agent can be uniformly and stably distributed in the polyurethane sponge material, and the third mixture forms an organic protective layer on the surface of the titanium dioxide, so that the polyurethane sponge material of this embodiment has excellent ultraviolet resistance and is not easy to yellow.
The monomers of the embodiment sequentially comprise the following components in a mass ratio of (10-40): (10-20): (50-70) methacrylic acid, methyl methacrylate and styrene; the initiator is prepared from (12-15) by mass: (85-87) a mixed solution of 1, 1-dimethylethyl octanedionate and butyl acetate. Cation exchange resins are known materials and are available directly on the market, such as: IRN120NA type cation exchange resin from Rohm and Haas company, USA.
The embodiment of the invention provides a polyurethane sponge material, which is obtained by adopting the preparation method of the polyurethane sponge material.
The first embodiment is as follows:
the polyurethane sponge comprises the following formula components in parts by mass: 10 parts of material A and 150 parts of material B.
The material A is prepared by the following method: and mixing water, an alkaline catalyst and a cross-linking agent, and uniformly stirring to obtain the material A. Wherein, 10 parts of water, 6 parts of alkaline catalyst and 15 parts of cross-linking agent. The alkaline catalyst is one or more of dimethylethanolamine, dimethylaminoethoxyethanol, trimethylhydroxyethylethylenediamine, N, N, N '-trimethyl-N' -hydroxyethyl-bis-aminoethyl ether, N, N-bis (dimethylaminopropyl) isopropanolamine, N, N, N ', N' -tetramethyldipropylenetriamine, bis (dimethylamino) -2-propanol, 1, 8-diazabicycloundec-7-ene or a weak acid salt thereof, and the crosslinking agent is one or more of 1, 4-butanediol, ethylene glycol, 1, 3-butanediol, trimethylolpropane, diethanolamine, triethanolamine and methyldiethanolamine.
The material B is prepared by the following method:
(1) taking TMN-305080 parts and ED-2820 parts, uniformly mixing, dehydrating for 2h under-0.1 MPa in a vacuum state, wherein the dehydration temperature is 110 ℃, until the water content of the mixed polyether is lower than 0.1 wt%;
(2) taking 100 parts of dehydrated mixed polyether, stirring at the stirring speed of 90r/min and the stirring temperature of 60 ℃, adding a metal catalyst in an amount of 0.1 percent of the weight of the dehydrated polyether during stirring and timing, wherein the metal catalyst is one or a combination of more of organic bismuth, zinc isobutyrate, zinc octoate and zirconium acetylacetonate;
(3) timing for 1min, adding 56 parts of IPDI, stirring uniformly, and reacting at 60 ℃ for 2-4h until the content of isocyanate is determined to be 11.2%;
(4) cooling to 20 +/-5 ℃, discharging to a container, filling nitrogen into the container to isolate air, and sealing and storing to obtain a prepolymer;
(5) and mixing the prepolymer and the surfactant according to the mass ratio of 60:1 to obtain a material B.
Respectively controlling the material A and the material B at 25 ℃, mixing and stirring for 20s at the stirring speed of 2000r/min, pouring into a mold at the temperature of 30 ℃, foaming and curing to obtain the non-yellowing polyurethane sponge.
Wherein the molecular weight of the TMN-3050 is 3000, the hydroxyl value is 54.5-57.5mgKOH/g, provided by Tianjin petrochemical Co., Ltd, the molecular weight of the ED-28 is 4000, the hydroxyl value is 26.5-29.5mgKOH/g, provided by Lanxingdong Dai Co., Ltd.
Example two:
the polyurethane sponge comprises the following formula components in parts by mass: 10 parts of material A and 140 parts of material B.
The material A is prepared by the following method: and mixing water, an alkaline catalyst and a cross-linking agent, and uniformly stirring to obtain the material A. Wherein, 10 parts of water, 20 parts of alkaline catalyst and 10 parts of cross-linking agent. The alkaline catalyst is one or more of dimethylethanolamine, dimethylaminoethoxyethanol, trimethylhydroxyethylethylenediamine, N, N, N '-trimethyl-N' -hydroxyethyl-bis-aminoethyl ether, N, N-bis (dimethylaminopropyl) isopropanolamine, N, N, N ', N' -tetramethyldipropylenetriamine, bis (dimethylamino) -2-propanol, 1, 8-diazabicycloundec-7-ene or a weak acid salt thereof, and the crosslinking agent is one or more of 1, 4-butanediol, ethylene glycol, 1, 3-butanediol, trimethylolpropane, diethanolamine, triethanolamine and methyldiethanolamine.
The material B is prepared by the following method:
(1) 4801E 90 parts and Voranol 222-05610 parts are taken and uniformly mixed, and are dehydrated for 2.5 hours under the vacuum state of-0.1 MPa, the dehydration temperature is 120 ℃, until the moisture content of the mixed polyether is lower than 0.1 wt%;
(2) taking 200 parts of dehydrated polyether, stirring at the stirring speed of 100r/min and the stirring temperature of 70 ℃, adding a metal catalyst in an amount of 0.05 percent of the weight of the dehydrated polyether during stirring and timing, wherein the metal catalyst is one or a combination of more of organic bismuth, zinc isobutyrate, zinc octoate and zirconium acetylacetonate;
(3) timing for 1min, adding 127 parts of IPDI, stirring uniformly, and reacting for 3h at 70 ℃ until the content of isocyanate is determined to be 13.0%;
(4) cooling to 20 +/-5 ℃, discharging to a container, filling nitrogen into the container to isolate air, and sealing and storing to obtain a prepolymer;
(5) and (3) mixing the prepolymer and the surfactant according to the mass part ratio of 109:1 to obtain a material B.
Respectively preheating the material A and the material B to 35 ℃, mixing, stirring for 20s at the stirring speed of 1950r/min, pouring into a mold at the temperature of 35 ℃, foaming at normal temperature, and curing to obtain the polyurethane sponge for the gasket.
Wherein, the molecular weight of 4801E is 4800, the hydroxyl value is 32-36mgKOH/g, provided by Kyoho chemical industry (Kunshan) Co., Ltd., Voranol 222-056 has a molecular weight of 2000, the hydroxyl value is 54.5-57.5mgKOH/g, provided by Dow chemical company in USA.
Example three:
the polyurethane sponge comprises the following formula components in parts by mass: 10 parts of material A and 125 parts of material B.
The material A is prepared by the following method: and mixing water, an alkaline catalyst and a cross-linking agent, and uniformly stirring to obtain the material A. Wherein, 10 parts of water, 16.5 parts of alkaline catalyst and 13 parts of cross-linking agent. The alkaline catalyst is one or more of dimethylethanolamine, dimethylaminoethoxyethanol, trimethylhydroxyethylethylenediamine, N, N, N '-trimethyl-N' -hydroxyethyl-bis-aminoethyl ether, N, N-bis (dimethylaminopropyl) isopropanolamine, N, N, N ', N' -tetramethyldipropylenetriamine, bis (dimethylamino) -2-propanol, 1, 8-diazabicycloundec-7-ene or a weak acid salt thereof, and the crosslinking agent is one or more of 1, 4-butanediol, ethylene glycol, 1, 3-butanediol, trimethylolpropane, diethanolamine, triethanolamine and methyldiethanolamine.
The material B is prepared by the following method:
(1) mixing GY-6000EH 85 parts and ED-2815 parts uniformly, and dehydrating for 3h under-0.1 MPa in a vacuum state at the dehydration temperature of 120 ℃ until the water content of the mixed polyether is lower than 0.1 wt%;
(2) taking 100 parts of dehydrated polyether, stirring at the stirring speed of 100r/min and the stirring temperature of 80 ℃, adding a metal catalyst in an amount of 0.05 percent of the weight of the dehydrated polyether during stirring and timing, wherein the metal catalyst is one or a combination of more of organic bismuth, zinc isobutyrate, zinc octoate and zirconium acetylacetonate;
(3) after timing for 1min, adding 50 parts of IPDI, stirring uniformly, and reacting for 3h at 80 ℃ until the content of isocyanate is determined to be 11.2%;
(4) cooling to 20 +/-5 ℃, discharging to a container, filling nitrogen into the container to isolate air, and sealing and storing to obtain a prepolymer;
(5) the prepolymer and the surfactant are mixed according to the mass part ratio of 60:1, mixing to obtain material B.
Respectively controlling the material A and the material B at 25 ℃, mixing, stirring for 30s at the stirring speed of 2000r/min, pouring into a mold at the temperature of 40 ℃, foaming, and curing to obtain the non-yellowing polyurethane sponge.
Wherein, the molecular weight of the GY-6000EH is 6000, the hydroxyl value is 26-30mgKOH/g, and is provided by Kyoho chemical engineering (Kunshan) Co., Ltd, and the molecular weight of the ED-28 is 4000, the hydroxyl value is 26.5-29.5mgKOH/g, and is provided by Lanxingdong Co., Ltd.
Example four:
the polyurethane sponge of the present example was obtained by the following steps:
s100, according to water: dimethylethanolamine: 1, 4-butanediol ═ 15: 70: 15, mixing water, dimethylethanolamine and 1, 4-butanediol and uniformly stirring to prepare a first raw material;
s210, dehydrating the polyether polyol for 2 hours under the vacuum condition of-0.5 MPa and the temperature condition of 110 ℃ until the moisture content of the polyether polyol is lower than 0.1 wt%;
s220, stirring the polyether polyol obtained in the S210 at a stirring speed of 90r/min and a stirring temperature of 70 ℃, adding the zinc isobutyrate during stirring and timing, wherein the adding amount of the zinc isobutyrate is 0.05-0.1% of that of the polyether polyol obtained in the S210;
step S230, after timing for 1min, adding the isophorone diisocyanate and the zinc oxide into the polyether polyol obtained in the step S220, uniformly stirring, and reacting for 2h at 70 ℃ until the content of the isocyanate is 10 percent;
step S240, cooling the product obtained in the step S230 to 20 ℃, discharging the product into a container, filling nitrogen into the container, and sealing and storing the container to obtain a prepolymer;
and S250, mixing the prepolymer obtained in the step S240 with a surfactant to obtain the second raw material.
Step S312, according to mannitol: glutamic acid: anti-ultraviolet agent: a first raw material: water 2: 6: 6: 6: 40: 40 of mannitol, glutamic acid, an anti-ultraviolet agent, a first raw material and water to obtain a first mixture;
step S314, according to ethyl acetate: polylactic acid-glycolic acid copolymer: the second raw material is 5: 40: 55 of ethyl acetate, a polylactic acid-glycolic acid copolymer and a second raw material are mixed to obtain a second mixture;
step S316, according to 50: 50 the first mixture obtained by the step S312 and the second mixture by the step S314 are mixed at a mass ratio, and ultrasonic emulsification is performed.
Wherein the anti-ultraviolet agent is prepared by the following steps:
step S410, according to monomers: initiator: butyl acetate solvent 35: 5: 60, heating a butyl acetate solvent to 95 ℃, introducing nitrogen, gradually dropwise adding a monomer and an initiator into the butyl acetate solvent, preserving heat for 2 hours after dropwise adding, and distilling the solvent to obtain a third mixture;
step S430, according to a third mixture: 20 parts of water: 80, mixing the third mixture with water, gradually adding the ammonium bicarbonate solution and stirring until the third mixture is dissolved to obtain a third mixture solution;
step S440, according to titanium dioxide: third mixture solution: water 10: 15: 75, adding titanium dioxide and water into the third mixture solution obtained in the step S430, and uniformly mixing to obtain an anti-ultraviolet agent slurry;
and S450, gradually adding cation exchange resin into the uvioresistant agent slurry obtained in the S440, stirring, adjusting the pH value to 4, filtering, washing and drying to obtain the uvioresistant agent.
Wherein, the monomers sequentially comprise the following components in a mass ratio of 10: 20: 70 of methacrylic acid, methyl methacrylate and styrene; the initiator is prepared from the following components in a mass ratio of 13: 87, a mixed solution of 1, 1-dimethylethyl octaperoxy acid and butyl acetate.
Example five:
the polyurethane sponge of the present example was obtained by the following steps:
s100, according to water: dimethylethanolamine: 1, 4-butanediol ═ 25: 50: 25, mixing water, dimethylethanolamine and 1, 4-butanediol and uniformly stirring to prepare a first raw material;
s210, dehydrating the polyether polyol for 3 hours under the vacuum condition of-0.1 MPa and the temperature condition of 120 ℃ until the moisture content of the polyether polyol is lower than 0.1 wt%;
s220, stirring the polyether polyol obtained in the S210 at a stirring speed of 100r/min and a stirring temperature of 80 ℃, adding the zinc isobutyrate during stirring and timing, wherein the adding amount of the zinc isobutyrate is 0.05-0.1% of that of the polyether polyol obtained in the S210;
step S230, after timing for 2min, adding the isophorone diisocyanate and the zinc oxide into the polyether polyol obtained in the step S220, uniformly stirring, and reacting for 4h at 80 ℃ until the content of the isocyanate is determined to be 15%;
step S240, cooling the product obtained in the step S230 to 20 ℃, discharging the product into a container, filling nitrogen into the container, and sealing and storing the container to obtain a prepolymer;
and S250, mixing the prepolymer obtained in the step S240 with a surfactant to obtain the second raw material.
Step S312, according to mannitol: glutamic acid: anti-ultraviolet agent: a first raw material: water 1: 9: 5: 5: 40: 40 of mannitol, glutamic acid, an anti-ultraviolet agent, a first raw material and water to obtain a first mixture;
step S314, according to ethyl acetate: polylactic acid-glycolic acid copolymer: the second raw material is 15: 35: mixing ethyl acetate, polylactic acid-glycolic acid copolymer and a second raw material according to the mass ratio of 50 to obtain a second mixture;
step S316, pressing 55: 45 the first mixture obtained by the step S312 and the second mixture by the step S314 are mixed and subjected to ultrasonic emulsification.
Wherein the anti-ultraviolet agent is prepared by the following steps:
step S410, according to monomers: initiator: butyl acetate solvent 35: 5: 60, heating a butyl acetate solvent to 98 ℃, introducing nitrogen, gradually dropwise adding a monomer and an initiator into the butyl acetate solvent, preserving heat for 2 hours after dropwise adding, and distilling the solvent to obtain a third mixture;
step S430, according to a third mixture: water 30: 70, mixing the third mixture with water, gradually adding an ammonium bicarbonate solution and stirring until the third mixture is dissolved to obtain a third mixture solution;
step S440, according to titanium dioxide: third mixture solution: water 15: 15: 70, adding titanium dioxide and water into the third mixture solution obtained in the step S430, and uniformly mixing to obtain an anti-ultraviolet agent slurry;
and S450, gradually adding cation exchange resin into the uvioresistant agent slurry obtained in the S440, stirring, adjusting the pH value to 5, and then filtering, washing and drying to obtain the uvioresistant agent.
Wherein, the monomer comprises the following components in sequence by mass ratio of 40: 10: 50 of methacrylic acid, methyl methacrylate and styrene; the initiator is prepared from the following components in percentage by mass: 85 of a mixed solution of 1, 1-dimethylethyl octaperoxy acid and butyl acetate.
Performance testing
In the description herein, the description of the terms "one embodiment," "some embodiments," "specific embodiments," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The preparation method of the polyurethane sponge material is characterized by comprising the following steps:
s100, according to water: basic catalyst: crosslinking agent ═ (15-25): (50-70): (15-25) mixing and uniformly stirring water, an alkaline catalyst and a cross-linking agent to prepare a first raw material;
s200, according to the polyether polyol: isophorone diisocyanate: metal catalyst: surfactant (b): zinc oxide 45: (40-45): 5: (4-8): (1-2) preparing a second raw material by adopting dehydrated polyether polyol, isophorone diisocyanate, a metal catalyst, a surfactant and zinc oxide according to the mass ratio;
s300, according to a first raw material: a second raw material: anti-ultraviolet agent ═ (10-20): (70-85): (5-10), mixing the first raw material, the second raw material and the anti-ultraviolet agent, foaming and curing to obtain the polyurethane sponge material.
2. The method for preparing polyurethane sponge according to claim 1, wherein in step S100:
the cross-linking agent comprises one or more of 1, 4-butanediol, ethylene glycol, 1, 3-butanediol, trimethylolpropane, diethanolamine, triethanolamine and methyldiethanolamine; and/or
The alkaline catalyst comprises one or more of dimethylethanolamine, dimethylaminoethoxyethanol, trimethylhydroxyethylethylenediamine, N, N, N '-trimethyl-N' -hydroxyethylbisaminoethyl ether, N, N-bis (dimethylaminopropyl) isopropanolamine, N, N, N ', N' -tetramethyldipropylenetriamine, bis (dimethylamino) -2-propanol, 1, 8-diazabicycloundec-7-ene or weak acid salts thereof.
3. The method for preparing polyurethane sponge according to claim 1, wherein in step S200:
the metal catalyst comprises one or more of organic bismuth, zinc isobutyrate, zinc octoate and zirconium acetylacetonate; and/or
The surfactant comprises one or more of Y-10366 surfactant, L-580 surfactant, L-680 surfactant, B-8715 surfactant, DC-193 surfactant, DC-2525 surfactant, DC-6070 surfactant, DC-540 surfactant and B-8681 surfactant.
4. The method for preparing a polyurethane sponge material as claimed in claim 1, wherein the step S200 specifically comprises:
s210, dehydrating the polyether polyol for 2 to 3 hours under the vacuum condition of-0.5 to-0.1 MPa and the temperature condition of 110 to 120 ℃ until the moisture content of the polyether polyol is lower than 0.1 wt%;
s220, stirring the polyether polyol obtained in the step S210 at a stirring speed of 90r/min to 100r/min and a stirring temperature of 70 ℃ to 80 ℃, and adding the metal catalyst in the stirring process and timing, wherein the adding amount of the metal catalyst is 0.05 to 0.1 percent of that of the polyether polyol obtained in the step S210;
step S230, timing for 1min to 2min, adding the isophorone diisocyanate and the zinc oxide into the polyether polyol obtained in the step S220, uniformly stirring, and reacting for 2h to 4h at 70 ℃ to 80 ℃ until the content of the isocyanate is 10% to 15%;
step S240, cooling the product obtained in the step S230 to 20 +/-5 ℃, discharging the product into a container, filling nitrogen into the container, and sealing and storing the container to obtain a prepolymer;
and S250, mixing the prepolymer obtained in the step S240 with a surfactant to obtain the second raw material.
5. The method for preparing polyurethane sponge according to claim 4, wherein in step S220, the polyether polyol is composed of 70-90 parts by weight of the triol and 10-30 parts by weight of the diol, based on 100 parts of the polyol.
6. The method as claimed in claim 5, wherein in step S220, the average molecular weight of the triol is 2000-8000, and the hydroxyl value is 20-85 mgKOH/g; the average molecular weight of the dihydric alcohol is 2000-6000, and the hydroxyl value is 20-60 mgKOH/g.
7. The method for preparing a polyurethane sponge material as claimed in any one of claims 1 to 6, wherein the step S300 specifically comprises:
s310, uniformly mixing the first raw material, the second raw material and the uvioresistant agent at the temperature of 20-30 ℃;
and S320, pouring the mixture obtained in the step S310 into a mold with the temperature of 30-40 ℃, foaming at normal temperature, and curing to obtain the polyurethane sponge material.
8. The method for preparing a polyurethane sponge material as claimed in claim 7, wherein the step S310 specifically comprises:
step S312, according to mannitol: glutamic acid: anti-ultraviolet agent: a first raw material: water ═ 1-2: (5-10): (5-10): (5-10): (40-45): (40-45) mixing mannitol, glutamic acid, an anti-ultraviolet agent, a first raw material and water in a mass ratio to obtain a first mixture;
step S314, according to ethyl acetate: polylactic acid-glycolic acid copolymer: second raw material ═ (5-15): (20-40): (45-55) mixing ethyl acetate, polylactic acid-glycolic acid copolymer and a second raw material in a mass ratio to obtain a second mixture;
step S316, pressing (50-55): (45-50) mixing the first mixture obtained through the step S312 and the second mixture through the step S314 at a mass ratio, and performing ultrasonic emulsification.
9. The preparation method of the polyurethane sponge material as claimed in claim 8, wherein the anti-ultraviolet agent is prepared by the following steps:
step S410, according to monomers: initiator: butyl acetate solvent 35: 5: 60, heating a butyl acetate solvent to 95-98 ℃, introducing nitrogen, gradually dropwise adding a monomer and an initiator into the butyl acetate solvent, preserving heat for 2 hours after dropwise adding, and distilling the solvent to obtain a third mixture;
step S430, according to a third mixture: water ═ 20-30: (70-80) mixing the third mixture with water, gradually adding an ammonium bicarbonate solution and stirring until the third mixture is dissolved to obtain a third mixture solution;
step S440, according to titanium dioxide: third mixture solution: water ═ 10-15: (10-15): (70-75) adding titanium dioxide and water to the third mixture solution obtained in the step S430, and uniformly mixing to obtain an anti-ultraviolet agent slurry;
and S450, gradually adding cation exchange resin into the uvioresistant agent slurry obtained in the S440, stirring, adjusting the pH value to 4-5, and then filtering, washing and drying to obtain the uvioresistant agent.
10. A polyurethane sponge material, characterized in that it is obtained by the process for the preparation of a polyurethane sponge material according to any one of claims 1 to 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010372269.8A CN111499819A (en) | 2020-05-06 | 2020-05-06 | Polyurethane sponge material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010372269.8A CN111499819A (en) | 2020-05-06 | 2020-05-06 | Polyurethane sponge material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111499819A true CN111499819A (en) | 2020-08-07 |
Family
ID=71871619
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010372269.8A Pending CN111499819A (en) | 2020-05-06 | 2020-05-06 | Polyurethane sponge material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111499819A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114160089A (en) * | 2021-11-05 | 2022-03-11 | 上海船舶工艺研究所(中国船舶工业集团公司第十一研究所) | VOCs adsorbing material of titanium tricarboxide composite titanium dioxide and preparation method thereof |
| CN114277680A (en) * | 2021-08-16 | 2022-04-05 | 宁波路宝科技实业集团有限公司 | Composite resin concrete steel bridge deck pavement structure and construction method thereof |
| CN114315229A (en) * | 2021-08-16 | 2022-04-12 | 宁波路宝科技实业集团有限公司 | Resin concrete and preparation method thereof, steel bridge deck pavement structure and construction method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105399924A (en) * | 2015-12-01 | 2016-03-16 | 常州市顺祥新材料科技有限公司 | Method for preparing no-yellowing polyurethane sponge capable of being foamed at normal temperature |
| CN107384019A (en) * | 2017-07-14 | 2017-11-24 | 西藏亚吐克工贸有限公司 | The special titanium dioxide process of ink |
| CN109260173A (en) * | 2018-11-15 | 2019-01-25 | 朗天药业(湖北)有限公司 | A kind of thymalfasin pharmaceutical composition and preparation method thereof |
| CN109535382A (en) * | 2018-10-18 | 2019-03-29 | 青岛中和聚氨酯材料有限公司 | A kind of non yellowing polyurethane sponge and preparation method thereof |
-
2020
- 2020-05-06 CN CN202010372269.8A patent/CN111499819A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105399924A (en) * | 2015-12-01 | 2016-03-16 | 常州市顺祥新材料科技有限公司 | Method for preparing no-yellowing polyurethane sponge capable of being foamed at normal temperature |
| CN107384019A (en) * | 2017-07-14 | 2017-11-24 | 西藏亚吐克工贸有限公司 | The special titanium dioxide process of ink |
| CN109535382A (en) * | 2018-10-18 | 2019-03-29 | 青岛中和聚氨酯材料有限公司 | A kind of non yellowing polyurethane sponge and preparation method thereof |
| CN109260173A (en) * | 2018-11-15 | 2019-01-25 | 朗天药业(湖北)有限公司 | A kind of thymalfasin pharmaceutical composition and preparation method thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114277680A (en) * | 2021-08-16 | 2022-04-05 | 宁波路宝科技实业集团有限公司 | Composite resin concrete steel bridge deck pavement structure and construction method thereof |
| CN114315229A (en) * | 2021-08-16 | 2022-04-12 | 宁波路宝科技实业集团有限公司 | Resin concrete and preparation method thereof, steel bridge deck pavement structure and construction method thereof |
| CN114160089A (en) * | 2021-11-05 | 2022-03-11 | 上海船舶工艺研究所(中国船舶工业集团公司第十一研究所) | VOCs adsorbing material of titanium tricarboxide composite titanium dioxide and preparation method thereof |
| CN114160089B (en) * | 2021-11-05 | 2024-04-05 | 上海船舶工艺研究所(中国船舶集团有限公司第十一研究所) | VOCs adsorption material of titanium carbide composite titanium dioxide and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111499819A (en) | Polyurethane sponge material and preparation method thereof | |
| US3516950A (en) | Foamed polymers | |
| CN110305289B (en) | Non-yellowing polyurethane memory cotton and preparation method thereof | |
| US4182827A (en) | Polyurethane hydrogels having enhanced wetting rates | |
| CN110105525B (en) | NDI-based polyurethane microporous elastomer resistant to damp-heat aging and preparation method thereof | |
| DE2624046A1 (en) | PROCESS FOR THE PRODUCTION OF CELL-SHAPED URETHANE POLYMERISATES | |
| EP0379246A2 (en) | A method for preparing and applying a sprayable, light stable polyurethane | |
| JPH0562610B2 (en) | ||
| CN106700029B (en) | Polyurethane resin for shoe sole and preparation method and application thereof | |
| DE2359606B2 (en) | Process for the production of inorganic-organic polymer-polysilicic acid gel composite material in the form of colloidal xerosal | |
| CN105440243B (en) | Urethane composition and preparation method thereof for vehicle dormer window cushion pad | |
| US3676402A (en) | Low-temperature curable blocked isocyanate compositions containing a stannoxane catalyst | |
| WO2021103376A1 (en) | Non-ionic waterborne polyurethane, preparation method therefor and application thereof | |
| CN110964173A (en) | Polyurethane composition for honeycomb composite material, preparation method of polyurethane composition, polyurethane foam and application of polyurethane foam | |
| CN106866922A (en) | The preparation method of microporous polyurethane elastomer | |
| US3119792A (en) | Metal and metal compound catalysts for polyurethane plastics | |
| CN106243321A (en) | A kind of functional urethane elastomeric material and preparation method thereof | |
| CN115074073A (en) | Flame-retardant polyurethane sealant and preparation method thereof | |
| CN109535382A (en) | A kind of non yellowing polyurethane sponge and preparation method thereof | |
| CN108034039A (en) | A kind of aqueous polyurethane emulsion of color inhibition and preparation method thereof | |
| CN110382579B (en) | Composite elastic polyurethane skin | |
| DE3507374A1 (en) | METHOD OF UNFOAMED MOLDED BODIES | |
| JP2018528314A (en) | Storage-stable activated prepolymer composition | |
| JPH04185627A (en) | Flexible polyurethane form | |
| CN106810668B (en) | Polyurethane resin for shoe sole and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200807 |