CN115304816B - Polyurethane foaming sheet for simulated printing and preparation method thereof - Google Patents
Polyurethane foaming sheet for simulated printing and preparation method thereof Download PDFInfo
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- CN115304816B CN115304816B CN202211114586.5A CN202211114586A CN115304816B CN 115304816 B CN115304816 B CN 115304816B CN 202211114586 A CN202211114586 A CN 202211114586A CN 115304816 B CN115304816 B CN 115304816B
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- 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
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- A—HUMAN NECESSITIES
- A43—FOOTWEAR
- A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
- A43B1/00—Footwear characterised by the material
- A43B1/0009—Footwear characterised by the material made at least partially of alveolar or honeycomb material
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- A—HUMAN NECESSITIES
- A43—FOOTWEAR
- A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
- A43B1/00—Footwear characterised by the material
- A43B1/14—Footwear characterised by the material made of plastics
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- 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
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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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
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
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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
- C08G18/65—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
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0066—Use of inorganic compounding ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/02—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by the reacting monomers or modifying agents during the preparation or modification of macromolecules
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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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
- C08J9/08—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 carbon dioxide
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- 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
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- 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
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0041—Foam properties having specified density
- C08G2110/0066—≥ 150kg/m3
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/02—CO2-releasing, e.g. NaHCO3 and citric acid
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- C—CHEMISTRY; METALLURGY
- 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J2497/00—Characterised by the use of lignin-containing materials
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- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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Abstract
The invention relates to a polyurethane foaming sheet for simulated printing and a preparation method thereof, and belongs to the technical field of polyurethane. The foaming sheet is formed by foaming a prepolymer, white materials and a hydrogen peroxide solution, wherein the white materials are mixed with an antibacterial foaming agent, the antibacterial foaming agent is formed by taking a porous sponge zinc oxide material as a carrier, dispersing the porous sponge zinc oxide material in a sodium lignin sulfonate solution, dropwise adding oxalic acid, chelating the oxalic acid with zinc-containing micro powder, enabling the oxalic acid to be attached to the surface of the zinc oxide, separating out the sodium lignin sulfonate under an acidic condition, enabling a complex of the oxalic acid and the zinc oxide to be attached to the surface of the zinc oxide, reacting hydrogen peroxide with the oxalic acid loaded on the surface to generate carbon dioxide and water in the foaming process, reacting the water in the hydrogen peroxide with isocyanate groups to generate carbon dioxide pores, and matching with a two-stage foaming process, so that the foaming is easy to control, the foam pores are fine and uniform, and the foaming sheet is applied to shoe uppers, has high simulation degree and good mechanical property.
Description
Technical Field
The invention belongs to the technical field of polyurethane, and particularly relates to a polyurethane foaming sheet for simulated printing and a preparation method thereof.
Background
The traditional vamp is made by the concatenation of the surface fabric of different feel, colour, and this kind of vamp has the sewing that runs through for the vamp does not have waterproof nature, and in addition, the cut-parts of vamp material, concatenation and sewing degree of difficulty are big, and product quality uniformity is poor, and the prior art is rising a emulation stamp vamp gradually, and like chinese patent CN114474812a discloses the preparation method of emulation stamp vamp, and it adopts polyurethane foam sheet as the raw materials, prepares waterproof vamp through emulation stamp.
The traditional polyurethane foaming sheet is prepared by reacting polyester or polyether polyol with organic isocyanate to generate a prepolymer with terminal isocyanate groups, adding various metered auxiliary agents into the prepolymer for reaction to generate urea bonds for chain extension reaction, and simultaneously carrying out foaming reaction to prepare a foaming material; the foaming agent comprises a physical foaming agent and a chemical foaming agent, the foaming principle of the physical foaming agent is that materials which are easy to vaporize are introduced, the foaming agent is vaporized to form pores in the foaming process, and the foaming materials are uneven in foaming and the foaming degree is not easy to control; the chemical foaming agent is most commonly water, the water reacts with isocyanate groups to generate carbon dioxide to form air holes, the molding process of the foaming material is easy to control, but the mechanical property of the foaming material obtained after foaming by doping a large amount of water is not very good, and the foaming material is difficult to be applied to vamp materials for hot pressing.
Disclosure of Invention
In order to solve the technical problems in the background art, the invention aims to provide a polyurethane foaming sheet for simulation printing and a preparation method thereof.
The aim of the invention can be achieved by the following technical scheme:
the preparation method of the polyurethane foaming sheet for the simulated printing comprises the following steps:
step S1: taking a reactor with a thermometer and a stirrer, adding polyadipic acid-1, 4-butanediol ester diol, heating the reactor at a constant temperature in an oil bath at 110 ℃, and then vacuumizing to 5mmHg, maintaining pressure and dehydrating for 2 hours to finish the dehydration treatment of polyadipic acid-1, 4-butanediol ester diol;
step S2: taking a polymerization kettle provided with a reflux condenser, cleaning the polymerization kettle by using dry nitrogen, adding dehydrated poly (1, 4-butanediol adipate) glycol and tetrahydrofuran, stirring and dissolving, adding isophorone diisocyanate, stirring and mixing, heating to 58-65 ℃ and reacting for 75-85min, and preparing a prepolymer;
step S3: taking an antibacterial foaming agent, 1, 4-butanediol, dibutyl tin dilaurate and methyl silicone oil, adding the antibacterial foaming agent, the 1, 4-butanediol, the dibutyl tin dilaurate and the methyl silicone oil into a stirrer, and uniformly mixing to prepare white materials;
step S4: mixing the prepolymer with the white material, adding the mixture into a polymerization kettle, heating to 75-80 ℃ for stirring reaction for 3-4h, adding hydrogen peroxide solution, stirring and mixing for 5min at high speed, transferring into a mold cavity for foaming treatment, and sequentially drying and cutting to prepare the foaming sheet.
Further, the dosage ratio of the polyadipic acid-1, 4-butanediol ester diol, tetrahydrofuran and isophorone diisocyanate is 30-35g:110-150mL:17-22g.
Further, the dosage ratio of the antibacterial foaming agent, 1, 4-butanediol, dibutyl tin dilaurate and methyl silicone oil is 5-8g:40-50mL:0.5-1g:10-15mL.
Further, the ratio of the amount of the prepolymer, the white material and the hydrogen peroxide solution is 90-110g:55-68g:12-15g, the concentration of hydrogen peroxide solution is 60%.
Further, the specific process of the foaming treatment comprises the following steps:
and (3) pressurizing, curing and foaming: introducing water vapor to boost the pressure to 5-6bar, wherein the temperature is 120-130 ℃, and foaming for 55-80min;
homogenizing and foaming at constant temperature: transferring to a constant temperature and humidity box, setting the temperature to 60 ℃, standing and foaming for 3-5h at the humidity of 90%.
The antibacterial foaming agent is prepared by the following method:
step A1: dissolving zinc acetate in ethanol solution, dropwise adding ammonia water in an ultrasonic dispersion state, standing for 5h after dropwise adding, centrifuging, taking out lower jelly, performing rotary evaporation drying, and then transferring into an oxidation furnace for roasting to prepare zinc-containing micropowder;
further, the dosage ratio of zinc acetate, ethanol solution and ammonia water is 10g:80-100mL:9-14mL, the concentration of the ethanol solution is 20-30%, and the concentration of the ammonia water is 10-15%.
Further, the oxygen content in the oxidation furnace is 50-80%, the roasting temperature is 820-950 ℃, and the roasting time is 2-3h.
Step A2: dissolving sodium lignin sulfonate in water to prepare dispersion liquid, adding zinc-containing micropowder into the dispersion liquid for ultrasonic dispersion, then dripping oxalic acid dissolution liquid under stirring, chelating oxalic acid with the zinc-containing micropowder, enabling oxalic acid to be attached to the surface of the zinc-containing micropowder, separating out sodium lignin sulfonate under acidic condition, attaching a complex of oxalic acid and the zinc-containing micropowder on the surface of the complex by using the complex as a nucleation material, centrifuging to separate out a lower layer, and carrying out vacuum drying to prepare the antibacterial foaming agent.
Further, the mass fraction of sodium lignin sulfonate in the dispersion liquid is 5.8-7.5%, and the dosage ratio of the dispersion liquid, zinc-containing micro powder and oxalic acid is 30-50mL:6-8g:2-5mL.
The invention has the beneficial effects that:
according to the invention, an antibacterial foaming agent and a hydrogen peroxide solution are adopted for synergistic foaming, zinc acetate and ammonia water react to generate zinc-containing complex gel, and then the zinc-containing complex gel is subjected to oxidative roasting molding, so that the prepared zinc-containing micropowder is a porous spongy zinc oxide material, the specific surface area is high, the zinc-containing micropowder has good loading property, oxalic acid is dropwise added into a sodium lignin sulfonate solution, the oxalic acid is chelated with the zinc-containing micropowder, the oxalic acid is attached to the surface of the zinc-containing micropowder, sodium lignin sulfonate is separated out under an acidic condition, a complex of the oxalic acid and the zinc-containing micropowder is attached to the surface of the zinc-containing micropowder, in the foaming process, the hydrogen peroxide reacts with the oxalic acid loaded on the surface to generate carbon dioxide and water, wherein the carbon dioxide forms primary pores, and the water generated by the reaction reacts with isocyanate groups to generate carbon dioxide pores, and the two-stage foaming process is matched with the two-stage foaming process, compared with the existing physical foaming process, the foaming process is mild in foaming process, the foaming process is easy to control, the foaming process is uniformly foamed from the inside of the foaming material, the foaming is more compact and uniform, the simulation degree is facilitated to be improved, a large number of foam cells are generated under the condition that the complex foaming agent is formed into a large number of uniform foam cells, and the problem of mechanical property is avoided due to the fact that the problem of lowering of the water content is reduced due to the doping of a large number of foam cells; meanwhile, zinc oxide is used as a load material, so that the foamed sheet has a certain antibacterial effect, and is suitable for vamp materials.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The preparation of the antibacterial foaming agent in this example is carried out as follows:
step A1: dissolving zinc acetate in ethanol solution, dropwise adding ammonia water in an ultrasonic dispersion state, standing for 5h after dropwise adding, centrifuging, taking a lower jelly, performing rotary evaporation drying, and then transferring into an oxidation furnace for roasting to prepare zinc-containing micro powder, wherein the dosage ratio of the zinc acetate to the ethanol solution to the ammonia water is 10g:80mL:9mL, the ultrasonic dispersion frequency is 28kHz, the concentration of ethanol solution is 20%, the concentration of ammonia water is 15%, oxygen is introduced into an oxidation furnace to adjust the oxygen content of the atmosphere in the furnace to 50%, the roasting temperature is set to 820 ℃, and the roasting time is set to 3h;
step A2: stirring and mixing sodium lignin sulfonate and water to prepare a dispersion liquid with the mass fraction of 5.8%, adding zinc-containing micro powder into the dispersion liquid, performing ultrasonic dispersion, dissolving oxalic acid into water, setting the stirring speed to be 180rpm, dripping oxalic acid solution into a dispersion system of the zinc-containing micro powder, continuously precipitating precipitate after dripping, transferring the reaction liquid into a centrifugal machine, centrifuging for 10min, taking a lower layer, and performing vacuum drying to prepare an antibacterial foaming agent, wherein the dosage ratio of the dispersion liquid, the zinc-containing micro powder and the oxalic acid is 30mL:6g:2mL.
Example 2
The preparation of the antibacterial foaming agent in this example is carried out as follows:
step A1: dissolving zinc acetate in ethanol solution, dropwise adding ammonia water in an ultrasonic dispersion state, standing for 5h after dropwise adding, centrifuging, taking a lower jelly, performing rotary evaporation drying, and then transferring into an oxidation furnace for roasting to prepare zinc-containing micro powder, wherein the dosage ratio of the zinc acetate to the ethanol solution to the ammonia water is 10g:90mL:12mL, the ultrasonic dispersion frequency is 28kHz, the concentration of ethanol solution is 25%, the concentration of ammonia water is 10%, oxygen is introduced into an oxidation furnace to adjust the oxygen content of the atmosphere in the furnace to 60%, the roasting temperature is 880 ℃, and the roasting time is 2.5h;
step A2: stirring and mixing sodium lignin sulfonate and water to prepare a dispersion liquid with the mass fraction of 6.8%, adding zinc-containing micro powder into the dispersion liquid, performing ultrasonic dispersion, dissolving oxalic acid into water, setting the stirring speed to be 180rpm, dripping oxalic acid solution into a dispersion system of the zinc-containing micro powder, continuously precipitating precipitate after dripping, transferring the reaction liquid into a centrifugal machine, centrifuging for 10min, taking a lower layer, and performing vacuum drying to prepare an antibacterial foaming agent, wherein the dosage ratio of the dispersion liquid, the zinc-containing micro powder and the oxalic acid is 40mL:7g:4mL.
Example 3
The preparation of the antibacterial foaming agent in this example is carried out as follows:
step A1: dissolving zinc acetate in ethanol solution, dropwise adding ammonia water in an ultrasonic dispersion state, standing for 5h after dropwise adding, centrifuging, taking a lower jelly, performing rotary evaporation drying, and then transferring into an oxidation furnace for roasting to prepare zinc-containing micro powder, wherein the dosage ratio of the zinc acetate to the ethanol solution to the ammonia water is 10g:100mL:14mL, the ultrasonic dispersion frequency is 28kHz, the concentration of ethanol solution is 30%, the concentration of ammonia water is 10%, oxygen is introduced into an oxidation furnace to adjust the oxygen content of the atmosphere in the furnace to 80%, the roasting temperature is set to 950 ℃, and the roasting time is set to 2 hours;
step A2: stirring and mixing sodium lignin sulfonate and water to prepare a dispersion liquid with the mass fraction of 7.5%, adding zinc-containing micro powder into the dispersion liquid, performing ultrasonic dispersion, dissolving oxalic acid into water, setting the stirring speed to be 180rpm, dripping oxalic acid solution into a dispersion system of the zinc-containing micro powder, continuously precipitating precipitate after dripping, transferring the reaction liquid into a centrifugal machine, centrifuging for 10min, taking a lower layer, and performing vacuum drying to prepare the antibacterial foaming agent, wherein the dosage ratio of the dispersion liquid, the zinc-containing micro powder and the oxalic acid is 50mL:8g:5mL.
Example 4
The polyurethane foaming sheet for simulated printing is prepared by the implementation process as follows:
step S1: taking a reactor with a thermometer and a stirrer, adding polyadipic acid-1, 4-butanediol ester diol, heating the reactor at a constant temperature in an oil bath at 110 ℃, and then vacuumizing to 5mmHg, maintaining pressure and dehydrating for 2 hours to prepare dehydrated polyadipic acid-1, 4-butanediol ester diol;
step S2: taking a polymerization kettle provided with a reflux condenser, cleaning the polymerization kettle by using dry nitrogen, adding dehydrated polyadipic acid-1, 4-butanediol ester glycol and tetrahydrofuran, stirring and dissolving, adding isophorone diisocyanate, stirring and mixing, heating to 58 ℃ for reacting for 85min, and preparing a prepolymer, wherein the dosage ratio of polyadipic acid-1, 4-butanediol ester glycol, tetrahydrofuran and isophorone diisocyanate is 30g:110mL:17g;
step S3: the antibacterial foaming agent, 1, 4-butanediol, dibutyl tin dilaurate and methyl silicone oil prepared in the embodiment 1 are taken and added into a stirrer to be uniformly mixed to prepare white materials, wherein the dosage ratio of the antibacterial foaming agent, 1, 4-butanediol, dibutyl tin dilaurate and methyl silicone oil is 5g:40mL:0.5g:10mL;
step S4: mixing the prepolymer and the white material, then adding the mixture into a polymerization kettle, heating to 75 ℃, stirring and reacting for 4 hours, and then adding hydrogen peroxide solution, stirring and mixing for 5 minutes at a high speed, wherein the dosage ratio of the prepolymer to the white material to the hydrogen peroxide solution is 90g:55g:12g, namely, transferring the hydrogen peroxide solution with the concentration of 60% into a die cavity for strickling, controlling the thickness to be 1.8+/-0.3 mm, introducing steam after die assembly, pressurizing to 5bar, heating to 120 ℃, pressurizing, curing and foaming for 80min, demolding, transferring the foam into a constant temperature and humidity box, setting the temperature to 60 ℃ and the humidity to 90%, homogenizing and foaming for 3h at constant temperature, cooling, drying and cutting to prepare the foaming sheet.
Example 5
The polyurethane foaming sheet for simulated printing is prepared by the implementation process as follows:
step S1: taking a reactor with a thermometer and a stirrer, adding polyadipic acid-1, 4-butanediol ester diol, heating the reactor at a constant temperature in an oil bath at 110 ℃, and then vacuumizing to 5mmHg, maintaining pressure and dehydrating for 2 hours to prepare dehydrated polyadipic acid-1, 4-butanediol ester diol;
step S2: taking a polymerization kettle provided with a reflux condenser, cleaning the polymerization kettle by using dry nitrogen, adding dehydrated polyadipic acid-1, 4-butanediol ester glycol and tetrahydrofuran, stirring and dissolving, adding isophorone diisocyanate, stirring and mixing, heating to 62 ℃ for reacting for 80min, and preparing a prepolymer, wherein the dosage ratio of polyadipic acid-1, 4-butanediol ester glycol, tetrahydrofuran and isophorone diisocyanate is 30g:130mL:20g;
step S3: the antibacterial foaming agent, 1, 4-butanediol, dibutyl tin dilaurate and methyl silicone oil prepared in the embodiment 2 are taken and added into a stirrer to be uniformly mixed to prepare white materials, wherein the dosage ratio of the antibacterial foaming agent, 1, 4-butanediol, dibutyl tin dilaurate and methyl silicone oil is 7g:45mL:0.8g:12mL;
step S4: mixing the prepolymer and the white material, then adding the mixture into a polymerization kettle, heating to 80 ℃ and stirring for reaction for 3.5 hours, and then adding hydrogen peroxide solution, stirring and mixing at a high speed for 5 minutes, wherein the dosage ratio of the prepolymer to the white material to the hydrogen peroxide solution is 100g:62g:14g, namely, transferring the hydrogen peroxide solution with the concentration of 60% into a die cavity for strickling, controlling the thickness to be 1.8+/-0.3 mm, introducing steam after die assembly, pressurizing to 6bar, heating to 120 ℃, pressurizing, curing and foaming for 68min, demolding, transferring the foam into a constant temperature and humidity box, setting the temperature to 60 ℃ and the humidity to 90%, homogenizing and foaming for 4h at constant temperature, cooling, drying and cutting to prepare the foaming sheet.
Example 6
The polyurethane foaming sheet for simulated printing is prepared by the implementation process as follows:
step S1: taking a reactor with a thermometer and a stirrer, adding polyadipic acid-1, 4-butanediol ester diol, heating the reactor at a constant temperature in an oil bath at 110 ℃, and then vacuumizing to 5mmHg, maintaining pressure and dehydrating for 2 hours to prepare dehydrated polyadipic acid-1, 4-butanediol ester diol;
step S2: taking a polymerization kettle provided with a reflux condenser, cleaning the polymerization kettle by using dry nitrogen, adding dehydrated polyadipic acid-1, 4-butanediol ester glycol and tetrahydrofuran, stirring and dissolving, adding isophorone diisocyanate, stirring and mixing, heating to 65 ℃ for reacting for 75min, and preparing a prepolymer, wherein the dosage ratio of polyadipic acid-1, 4-butanediol ester glycol, tetrahydrofuran and isophorone diisocyanate is 35g:150mL:22g;
step S3: the antibacterial foaming agent, 1, 4-butanediol, dibutyl tin dilaurate and methyl silicone oil prepared in the embodiment 3 are taken and added into a stirrer to be uniformly mixed to prepare white materials, wherein the dosage ratio of the antibacterial foaming agent, 1, 4-butanediol, dibutyl tin dilaurate and methyl silicone oil is 8g:50mL:1g:15mL;
step S4: mixing the prepolymer and the white material, then adding the mixture into a polymerization kettle, heating to 80 ℃ and stirring for reaction for 3 hours, and then adding hydrogen peroxide solution, stirring and mixing at a high speed for 5 minutes, wherein the dosage ratio of the prepolymer to the white material to the hydrogen peroxide solution is 110g:68g:15g, namely, the concentration of the hydrogen peroxide solution is 60%, the mixture is transferred into a die cavity for strickling, the thickness is controlled to be 1.8+/-0.3 mm, water vapor is introduced into the die cavity for pressurizing to 6bar after die assembly, the temperature is raised to 130 ℃, the pressure maintenance and foaming are carried out for 55min, then the die cavity is demolded and transferred into a constant temperature and humidity box, the temperature is set to be 60 ℃, the humidity is 90%, the constant temperature and homogenization foaming are carried out for 3h, and the foam sheet is manufactured after cooling, drying and cutting.
Comparative example 1
The comparative example uses methylene dichloride and water as foaming agents to replace the antibacterial foaming agent and the hydrogen peroxide solution foaming system in the example 5, and the specific implementation process is as follows:
step S1: dehydrated poly (1, 4-butylene adipate) glycol was prepared by the same method as in example 5;
step S2: a prepolymer was prepared in the same manner as in example 5;
step S3: adding dichloromethane, water, 1, 4-butanediol, dibutyl tin dilaurate and methyl silicone oil into a stirrer, and uniformly mixing to prepare a white material, wherein the dosage proportion of the dichloromethane, the water, the 1, 4-butanediol, the dibutyl tin dilaurate and the methyl silicone oil is adjusted to be 5.5mL:10mL:45mL:0.8g:12mL;
step S4: mixing the prepolymer and the white material, adding the mixture into a polymerization kettle, mixing for 5min, transferring the mixture into a die cavity, scraping the mixture, controlling the thickness to be 1.8+/-0.3 mm, sequentially pressurizing, curing and foaming the mixture, homogenizing and foaming the mixture at a constant temperature, drying the mixture, and cutting the mixture to prepare the foaming sheet.
The following performance tests were performed on the foamed sheets prepared in examples 4 to 6 and comparative example 1, and the specific test data are shown in table 1:
TABLE 1
As can be seen from the data in Table 1, the density of the foamed sheet prepared by the present invention is 0.632-0.671g/cm 3 The porous light foaming material has the characteristics of porous light foaming material, the tensile strength of 4.07-4.32MPa, the elongation at break of 394-425%, good tensile property, the tearing strength of 16.57-17.31kN/m, the maximum puncture force of 22.3-25.5N, and good anti-damage property, and is suitable for vamp materials.
To verify the suitability of the foamed sheets prepared in examples 4 to 6 and comparative example 1 for vamp embossing, 3 specimens were taken for each group, stepped silica gel compression molds were prepared, the compression amounts were 0.2mm, 0.5mm and 1mm, respectively, the specimens were laminated on the silica gel molds, and the lamination pressure was set to 5kg/cm 2 High-frequency hot pressing, observing the surface state after embossing, detecting the flatness and the lamination error before and after embossing, and the specific data are shown in table 2:
TABLE 2
As can be seen from the data in Table 2, the foaming sheet prepared by the invention has good surface state, keeps the surface smooth after high-frequency hot-pressing printing, has a lamination error of only 0.013-0.017mm, and has high simulation degree when used for vamp printing.
The foam sheets prepared in examples 4 to 6 and comparative example 1 were used, and specific test data are shown in Table 3 with reference to GB/T15979-2002 standard bacteriostasis test:
TABLE 3 Table 3
As can be seen from the data in Table 3, the foaming sheet prepared by the invention has a certain antibacterial effect, and can play a role in antibacterial and deodorizing when applied to vamp materials.
In the description of the present specification, the descriptions of the terms "one embodiment," "example," "specific example," and the like, mean 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 present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. 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 foregoing is merely illustrative and explanatory of the invention, as various modifications and additions may be made to the particular embodiments described, or in a similar manner, by those skilled in the art, without departing from the scope of the invention or exceeding the scope of the invention as defined in the claims.
Claims (7)
1. The polyurethane foaming sheet for the simulated printing is characterized by being formed by foaming a prepolymer, white materials and a hydrogen peroxide solution, wherein the white materials are mixed with an antibacterial foaming agent;
the antibacterial foaming agent is prepared by the following method:
step A1: dissolving zinc acetate in ethanol solution, dropwise adding ammonia water in an ultrasonic dispersion state, standing for 5h after dropwise adding, centrifuging, taking a lower jelly, performing rotary evaporation drying, and then transferring into an oxidation furnace for roasting to prepare zinc-containing micro powder, wherein the dosage ratio of the zinc acetate to the ethanol solution to the ammonia water is 10g:80-100mL:9-14mL, wherein the concentration of the ethanol solution is 20-30%, and the concentration of the ammonia water is 10-15%;
step A2: dissolving sodium lignin sulfonate in water to prepare a dispersion liquid, adding zinc-containing micro powder, performing ultrasonic dispersion, then dropwise adding oxalic acid solution in a stirring state, centrifuging to separate out a lower layer, and performing vacuum drying to prepare the antibacterial foaming agent, wherein the dosage ratio of the dispersion liquid, the zinc-containing micro powder and oxalic acid is 30-50mL:6-8g:2-5mL, and the mass fraction of sodium lignin sulfonate in the dispersion liquid is 5.8-7.5%.
2. The polyurethane foam sheet for simulated printing as claimed in claim 1, wherein the oxygen content in the oxidation oven is 50-80%, the firing temperature is 820-950 ℃ and the firing time is 2-3h.
3. The method for preparing the polyurethane foam sheet for simulated printing as claimed in claim 1, comprising the following steps:
step S1: heating the poly (1, 4-butanediol adipate) glycol to 110 ℃, vacuumizing to 5mmHg, maintaining the pressure and dehydrating for 2 hours, and finishing the dehydration treatment of the poly (1, 4-butanediol adipate) glycol;
step S2: cleaning a polymerization kettle with dry nitrogen, adding dehydrated poly (1, 4-butanediol adipate) glycol and tetrahydrofuran, stirring for dissolving, adding isophorone diisocyanate, stirring for mixing, heating to 58-65 ℃ for reacting for 75-85min, and preparing a prepolymer;
step S3: taking an antibacterial foaming agent, 1, 4-butanediol, dibutyl tin dilaurate and methyl silicone oil, adding the antibacterial foaming agent, the 1, 4-butanediol, the dibutyl tin dilaurate and the methyl silicone oil into a stirrer, and uniformly mixing to prepare white materials;
step S4: mixing the prepolymer with the white material, adding the mixture into a polymerization kettle, heating to 75-80 ℃ for stirring reaction for 3-4h, adding hydrogen peroxide solution, stirring and mixing for 5min, transferring into a mold cavity for foaming treatment, and sequentially drying and cutting to prepare the foaming sheet.
4. The process for producing a polyurethane foam sheet for simulated printing as claimed in claim 3, wherein the ratio of the amount of poly (1, 4-butylene adipate) glycol, tetrahydrofuran and isophorone diisocyanate is 30 to 35g:110-150mL:17-22g.
5. The method for preparing polyurethane foam sheets for simulated printing according to claim 3, wherein the dosage ratio of the antibacterial foaming agent, 1, 4-butanediol, dibutyltin dilaurate and methyl silicone oil is 5-8g:40-50mL:0.5-1g:10-15mL.
6. The method for producing a polyurethane foam sheet for simulated printing as claimed in claim 3, wherein the ratio of the amount of the prepolymer, the white material and the hydrogen peroxide solution is 90-110g:55-68g:12-15g, the concentration of hydrogen peroxide solution is 60%.
7. A method for producing a polyurethane foam sheet for simulated printing as claimed in claim 3, wherein the foaming treatment comprises, in order:
and (3) pressurizing, curing and foaming: introducing water vapor to boost the pressure to 5-6bar, wherein the temperature is 120-130 ℃, and foaming for 55-80min;
homogenizing and foaming at constant temperature: transferring to a constant temperature and humidity box, setting the temperature to 60 ℃, standing and foaming for 3-5h at the humidity of 90%.
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| CN1166841A (en) * | 1995-09-01 | 1997-12-03 | 松下电器产业株式会社 | Heat-insulating foam, process for producing the same, and heat-insulating box |
| CN102203158A (en) * | 2008-11-06 | 2011-09-28 | 旭有机材工业株式会社 | Expandable composition for polyurethane foam, and polyurethane foam |
| CN107151303A (en) * | 2016-03-03 | 2017-09-12 | 中国石油化工股份有限公司 | A kind of tung oil base RPUF and preparation method thereof |
| CN110527281A (en) * | 2019-08-22 | 2019-12-03 | 白中华 | A kind of sound insulation resistance to compression aerosil polyurethane composite thermal insulation wallboard |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1166841A (en) * | 1995-09-01 | 1997-12-03 | 松下电器产业株式会社 | Heat-insulating foam, process for producing the same, and heat-insulating box |
| CN102203158A (en) * | 2008-11-06 | 2011-09-28 | 旭有机材工业株式会社 | Expandable composition for polyurethane foam, and polyurethane foam |
| CN107151303A (en) * | 2016-03-03 | 2017-09-12 | 中国石油化工股份有限公司 | A kind of tung oil base RPUF and preparation method thereof |
| CN110527281A (en) * | 2019-08-22 | 2019-12-03 | 白中华 | A kind of sound insulation resistance to compression aerosil polyurethane composite thermal insulation wallboard |
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