CN115304816A - Polyurethane foam sheet for simulated printing and preparation method thereof - Google Patents
Polyurethane foam sheet for simulated printing and preparation method thereof Download PDFInfo
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- CN115304816A CN115304816A CN202211114586.5A CN202211114586A CN115304816A CN 115304816 A CN115304816 A CN 115304816A CN 202211114586 A CN202211114586 A CN 202211114586A CN 115304816 A CN115304816 A CN 115304816A
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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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- 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
- C08G18/42—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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- 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
- C08G18/6633—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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- 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
- C08J9/0066—Use of inorganic compounding ingredients
-
- 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
-
- 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
- C08J9/04—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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- 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
- 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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- 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
- 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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- 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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2497/00—Characterised by the use of lignin-containing materials
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- 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
- C08K2003/2296—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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to a polyurethane foam sheet for simulated printing and a preparation method thereof, belonging to the technical field of polyurethane. The foaming sheet is formed by foaming a prepolymer, a white material and a hydrogen peroxide solution, wherein the white material is mixed with an antibacterial foaming agent, a porous spongy zinc oxide material is used as a carrier, oxalic acid is dispersed in a sodium lignosulfonate solution and dropwise added, the oxalic acid is chelated with zinc-containing micro powder, the oxalic acid is attached to the surface of zinc oxide, sodium lignosulfonate is separated out under an acidic condition, a complex of the oxalic acid and the zinc oxide is used as a nucleating material and attached to the surface of the oxalic acid and the zinc oxide, during the foaming process, the hydrogen peroxide and the oxalic acid loaded on the surface react to generate carbon dioxide and water, the carbon dioxide forms primary pores, the water in the hydrogen peroxide and the water generated by the reaction react with an isocyanate group to generate carbon dioxide pores, and the foaming sheet is matched with a two-stage foaming process, so that the foaming process is easy to control, the pores are fine and uniform, and the foaming degree is high and the mechanical property is good when the foaming sheet is applied to a vamp.
Description
Technical Field
The invention belongs to the technical field of polyurethane, and particularly relates to a polyurethane foam sheet for simulated printing and a preparation method thereof.
Background
Traditional vamp is made by the surface fabric concatenation 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, has gradually made up a emulation stamp formula vamp among the prior art, for example chinese patent CN114474812A discloses the preparation method of emulation stamp vamp, and it adopts polyurethane foam piece as the raw materials, through emulation stamp preparation waterproof vamp.
The traditional polyurethane foaming sheet is prepared by reacting polyester or polyether polyol with organic isocyanate to generate a prepolymer with a terminal isocyanate group, adding various metered additives 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 type foaming agent and a chemical type foaming agent, the foaming principle of the physical type foaming agent is that materials which are easy to vaporize are introduced, the foaming agent vaporizes to form air holes in the foaming process, and the foaming materials are uneven in foaming and difficult to control in foaming degree; the chemical foaming agent is most commonly water, and water reacts with isocyanate groups to generate carbon dioxide to form air holes, the forming 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 good, and the foaming material is difficult to apply to vamp materials for hot pressing.
Disclosure of Invention
In order to solve the technical problems mentioned in the background art, the invention aims to provide a polyurethane foam sheet for simulated printing and a preparation method thereof.
The purpose of the invention can be realized by the following technical scheme:
a preparation method of a polyurethane foaming sheet for simulated printing comprises the following steps:
step S1: taking a reactor provided with a thermometer and a stirrer, adding poly (1, 4-butanediol adipate) glycol, placing the reactor in an oil bath kettle at 110 ℃ for constant-temperature heating, then vacuumizing to 5mmHg, maintaining pressure and dehydrating for 2 hours, and finishing the dehydration treatment of the poly (1, 4-butanediol adipate) glycol;
step S2: taking a polymerization kettle provided with a reflux condenser, cleaning the polymerization kettle by using dry nitrogen, adding dehydrated 1, 4-butanediol adipate and tetrahydrofuran, stirring and dissolving, adding isophorone diisocyanate, stirring and mixing, heating to 58-65 ℃, reacting for 75-85min, and preparing a prepolymer;
and step S3: adding an antibacterial foaming agent, 1, 4-butanediol, dibutyltin dilaurate and methyl silicone oil into a stirrer, and uniformly mixing to prepare a white material;
and step S4: mixing the prepolymer and the white material, adding the mixture into a polymerization kettle, heating to 75-80 ℃, stirring for reaction for 3-4h, adding a hydrogen peroxide solution, stirring at a high speed for 5min, transferring the mixture into a die cavity for foaming, and then sequentially drying and cutting to prepare a foamed sheet.
Further, the using ratio of the poly 1, 4-butanediol adipate glycol to the tetrahydrofuran to the isophorone diisocyanate is 30-35g:110-150mL:17-22g.
Further, 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.
Furthermore, the dosage ratio of the prepolymer, the white material and the hydrogen peroxide solution is 90-110g:55-68g:12-15g, the concentration of the hydrogen peroxide solution is 60%.
Further, the specific process of the foaming treatment comprises the following steps:
pressure curing and foaming: introducing steam, pressurizing to 5-6bar at 120-130 deg.C, and foaming for 55-80min;
homogenizing and foaming at constant temperature: transferring into a constant temperature and humidity box, setting the temperature at 60 deg.C and humidity at 90%, standing and foaming for 3-5h.
The antibacterial foaming agent is prepared by the following method:
step A1: dissolving zinc acetate in ethanol solution, dropwise adding ammonia water under ultrasonic dispersion state, standing for 5h, centrifuging to obtain lower layer jelly, drying by rotary evaporation, and calcining in an oxidation furnace to obtain zinc-containing micro powder;
furthermore, the dosage ratio of the zinc acetate, the ethanol solution and the 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%.
Furthermore, 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 lignosulfonate in water to prepare a dispersion liquid, adding zinc-containing micro powder into the dispersion liquid for ultrasonic dispersion, dropwise adding an oxalic acid dissolving liquid under a stirring state, chelating oxalic acid with the zinc-containing micro powder, attaching the oxalic acid to the surface of the zinc-containing micro powder, precipitating sodium lignosulfonate under an acidic condition, attaching a complex of the oxalic acid and the zinc-containing micro powder as a nucleating material to the surface of the zinc-containing micro powder, centrifuging, separating out a lower layer, and drying in vacuum to prepare the antibacterial foaming agent.
Further, the mass fraction of the sodium lignin sulfonate in the dispersion liquid is 5.8-7.5%, and the dosage ratio of the dispersion liquid, the zinc-containing micro powder and the oxalic acid is 30-50mL:6-8g:2-5mL.
The invention has the beneficial effects that:
the invention adopts an antibacterial foaming agent and a hydrogen peroxide solution for synergistic foaming, the antibacterial foaming agent is formed by the reaction of zinc acetate and ammonia water to generate a zinc-containing complex gel, and then the gel is formed by oxidizing roasting, the prepared zinc-containing micro powder is a porous spongy zinc oxide material which has high specific surface area and good loading property, the zinc-containing micro powder is dispersed in a sodium lignosulfonate solution, oxalic acid is dropwise added into the zinc-containing micro powder, the oxalic acid is chelated with the zinc-containing micro powder, the oxalic acid is attached to the surface of the zinc-containing micro powder, sodium lignosulfonate is separated out under an acidic condition, and the complex of the oxalic acid and the zinc-containing micro powder is taken as a nucleating material to be attached to the surface of the oxalic acid; meanwhile, the invention takes zinc oxide as a load material, has certain antibacterial effect, and makes the foamed sheet suitable for vamp materials.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The embodiment of the preparation of the antibacterial foaming agent comprises the following specific implementation processes:
step A1: dissolving zinc acetate in an ethanol solution, dropwise adding ammonia water under an ultrasonic dispersion state, standing for 5h after dropwise adding, centrifuging, taking a lower layer jelly, drying by rotary evaporation, and roasting in an oxidation furnace 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 of: 9mL, ultrasonic dispersion frequency of 28kHz, ethanol solution concentration of 20 percent, ammonia concentration of 15 percent, oxygen introduced into an oxidation furnace to adjust the oxygen content in the atmosphere of the furnace to be 50 percent, roasting temperature of 820 ℃ and roasting time of 3 hours;
step A2: stirring and mixing sodium lignosulfonate and water to prepare a dispersion liquid with the mass fraction of 5.8%, adding zinc-containing micro powder into the dispersion liquid for ultrasonic dispersion, dissolving oxalic acid in water, setting the stirring speed to be 180rpm, dropwise adding the oxalic acid solution into a dispersion system of the zinc-containing micro powder, continuously precipitating precipitates after dropwise adding, transferring the reaction liquid into a centrifuge for centrifugation for 10min, and carrying out vacuum drying on a lower layer to prepare the 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 embodiment of the preparation of the antibacterial foaming agent comprises the following specific implementation processes:
step A1: dissolving zinc acetate in an ethanol solution, dropwise adding ammonia water in an ultrasonic dispersion state, standing for 5 hours after dropwise adding, centrifuging to take a lower layer jelly, drying by rotary evaporation, and roasting in an oxidation furnace 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 of: 12mL, the ultrasonic dispersion frequency is 28kHz, the concentration of an ethanol solution is 25%, the concentration of ammonia water is 10%, oxygen is introduced into an oxidation furnace to adjust the oxygen content in the atmosphere of the furnace to be 60%, the roasting temperature is 880 ℃, and the roasting time is 2.5 hours;
step A2: stirring and mixing sodium lignosulfonate and water to prepare a dispersion liquid with the mass fraction of 6.8%, adding zinc-containing micro powder into the dispersion liquid for ultrasonic dispersion, dissolving oxalic acid in water, setting the stirring speed to be 180rpm, dropwise adding the oxalic acid solution into a dispersion system of the zinc-containing micro powder, continuously precipitating precipitates after dropwise adding, transferring the reaction liquid into a centrifuge for centrifugation for 10min, and carrying out vacuum drying on a lower layer to prepare the 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 embodiment of the preparation of the antibacterial foaming agent comprises the following specific implementation processes:
step A1: dissolving zinc acetate in an ethanol solution, dropwise adding ammonia water in an ultrasonic dispersion state, standing for 5 hours after dropwise adding, centrifuging to take a lower layer jelly, drying by rotary evaporation, and roasting in an oxidation furnace 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 of: 14mL, the ultrasonic dispersion frequency is 28kHz, the concentration of an 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 be 80%, the roasting temperature is 950 ℃, and the roasting time is 2 hours;
step A2: stirring and mixing sodium lignosulfonate and water to prepare a dispersion liquid with the mass fraction of 7.5%, adding zinc-containing micro powder into the dispersion liquid for ultrasonic dispersion, dissolving oxalic acid in water, setting the stirring speed to be 180rpm, dropwise adding the oxalic acid solution into a dispersion system of the zinc-containing micro powder, continuously precipitating precipitates after dropwise adding, transferring the reaction liquid into a centrifuge for centrifugation for 10min, and carrying out vacuum drying on a lower layer 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 implementation of preparing the polyurethane foaming sheet for the simulated printing comprises the following specific implementation processes:
step S1: adding poly adipic acid-1, 4-butanediol glycol into a reactor provided with a thermometer and a stirrer, placing the reactor in an oil bath pan at 110 ℃ for heating at constant temperature, vacuumizing to 5mmHg, and performing pressure maintaining dehydration for 2 hours to prepare dehydrated poly adipic acid-1, 4-butanediol glycol;
step S2: taking a polymerization kettle provided with a reflux condenser, cleaning the polymerization kettle by using dry nitrogen, adding dehydrated 1, 4-butanediol adipate glycol and tetrahydrofuran, stirring and dissolving, adding isophorone diisocyanate, stirring and mixing, heating to 58 ℃ and reacting for 85min to prepare a prepolymer, wherein the dosage ratio of the 1, 4-butanediol adipate glycol to the tetrahydrofuran to the isophorone diisocyanate is 30g:110mL:17g of a basic amine;
and step S3: adding the antibacterial foaming agent prepared in the example 1, 4-butanediol, dibutyltin dilaurate and methyl silicone oil into a stirrer, and uniformly mixing to prepare a white material, wherein the dosage ratio of the antibacterial foaming agent, the 1, 4-butanediol, the dibutyltin dilaurate and the methyl silicone oil is 5g:40mL of: 0.5g:10mL;
and step S4: mixing the prepolymer and the white material, adding the mixture into a polymerization kettle, heating the mixture to 75 ℃, stirring the mixture for reaction for 4 hours, adding a hydrogen peroxide solution, stirring the mixture at a high speed for mixing the mixture for 5 minutes, wherein the dosage ratio of the prepolymer to the white material to the hydrogen peroxide solution is 90g:55g:12g, transferring the hydrogen peroxide solution with the concentration of 60% into a die cavity, leveling, controlling the thickness to be 1.8 +/-0.3 mm, filling water vapor after die assembly, pressurizing to 5bar, heating to 120 ℃, pressurizing, curing and foaming for 80min, demoulding, transferring into a constant-temperature and constant-humidity box, setting the temperature to be 60 ℃ and the humidity to be 90%, homogenizing and foaming for 3h at constant temperature, cooling, drying and cutting to obtain the foaming sheet.
Example 5
The implementation of preparing the polyurethane foaming sheet for the simulated printing comprises the following specific implementation processes:
step S1: adding poly adipic acid-1, 4-butanediol glycol into a reactor provided with a thermometer and a stirrer, placing the reactor in an oil bath pan at 110 ℃ for heating at constant temperature, vacuumizing to 5mmHg, and performing pressure maintaining dehydration for 2 hours to prepare dehydrated poly adipic acid-1, 4-butanediol glycol;
step S2: taking a polymerization kettle provided with a reflux condenser, cleaning the polymerization kettle by using dry nitrogen, adding dehydrated 1, 4-butanediol adipate and tetrahydrofuran, stirring and dissolving, adding isophorone diisocyanate, stirring and mixing, heating to 62 ℃, reacting for 80min, and preparing a prepolymer, wherein the dosage ratio of the 1, 4-butanediol adipate to the tetrahydrofuran to the isophorone diisocyanate is 30g:130mL of: 20g of the total weight of the mixture;
and step S3: adding the antibacterial foaming agent prepared in the embodiment 2, 1, 4-butanediol, dibutyltin dilaurate and methyl silicone oil into a stirrer, and uniformly mixing to prepare a white material, wherein the dosage ratio of the antibacterial foaming agent, the 1, 4-butanediol, the dibutyltin dilaurate and the methyl silicone oil is 7g:45mL of: 0.8g:12mL;
and step S4: mixing the prepolymer and the white material, adding the mixture into a polymerization kettle, heating to 80 ℃, stirring for reaction for 3.5 hours, adding a hydrogen peroxide solution, stirring and mixing at a high speed for 5min, wherein the dosage ratio of the prepolymer to the white material to the hydrogen peroxide solution is 100g:62g:14g, transferring the hydrogen peroxide solution with the concentration of 60% into a die cavity, leveling, controlling the thickness to be 1.8 +/-0.3 mm, filling water vapor after die assembly, pressurizing to 6bar, heating to 120 ℃, pressurizing, curing and foaming for 68min, demoulding, transferring into a constant-temperature constant-humidity box, setting the temperature to be 60 ℃, the humidity to be 90%, homogenizing and foaming for 4h at constant temperature, cooling, drying, cutting and preparing into the foaming sheet.
Example 6
The implementation of preparing the polyurethane foaming sheet for the simulated printing comprises the following specific implementation processes:
step S1: adding poly-1, 4-butanediol adipate glycol into a reactor provided with a thermometer and a stirrer, placing the reactor into an oil bath kettle at 110 ℃ for constant temperature heating, then vacuumizing to 5mmHg, maintaining pressure and dehydrating for 2 hours to prepare dehydrated poly-1, 4-butanediol adipate glycol;
step S2: taking a polymerization kettle provided with a reflux condenser, cleaning the polymerization kettle by using dry nitrogen, adding dehydrated 1, 4-butanediol adipate and tetrahydrofuran, stirring and dissolving, adding isophorone diisocyanate, stirring and mixing, heating to 65 ℃, reacting for 75min, and preparing a prepolymer, wherein the dosage ratio of the 1, 4-butanediol adipate to the tetrahydrofuran to the isophorone diisocyanate is 35g:150mL of: 22g of the total weight of the mixture;
and step S3: adding the antibacterial foaming agent prepared in the embodiment 3, 1, 4-butanediol, dibutyltin dilaurate and methyl silicone oil into a stirrer, and uniformly mixing to prepare a white material, wherein the dosage ratio of the antibacterial foaming agent, the 1, 4-butanediol, the dibutyltin dilaurate and the methyl silicone oil is 8g:50mL of: 1g:15mL;
and step S4: mixing the prepolymer and the white material, adding the mixture into a polymerization kettle, heating to 80 ℃, stirring for reaction for 3 hours, adding a hydrogen peroxide solution, stirring at a high speed for 5 minutes, and mixing, wherein the dosage ratio of the prepolymer to the white material to the hydrogen peroxide solution is 110g:68g:15g, transferring the hydrogen peroxide solution with the concentration of 60% into a die cavity, leveling, controlling the thickness to be 1.8 +/-0.3 mm, filling water vapor after die assembly, pressurizing to 6bar, heating to 130 ℃, pressurizing, curing and foaming for 55min, demoulding, transferring into a constant-temperature and constant-humidity box, setting the temperature to be 60 ℃ and the humidity to be 90%, homogenizing and foaming for 3h at constant temperature, cooling, drying and cutting to obtain the foaming sheet.
Comparative example 1
In the comparison, methylene dichloride and water are used as foaming agents to replace the antibacterial foaming agent and the hydrogen peroxide solution foaming system in the embodiment 5, and the specific implementation process is as follows:
step S1: dehydrated poly (1, 4-butylene adipate) glycol was prepared in the same manner as in example 5;
step S2: a prepolymer was prepared in the same manner as in example 5;
and step S3: adding dichloromethane, water, 1, 4-butanediol, dibutyltin dilaurate and methyl silicone oil into a stirrer, and uniformly mixing to prepare a white material, wherein the dosage ratio of the dichloromethane, the water, the 1, 4-butanediol, the dibutyltin dilaurate and the methyl silicone oil is adjusted to 5.5mL:10mL of: 45mL of: 0.8g:12mL;
and 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, leveling, controlling the thickness to be 1.8 +/-0.3 mm, sequentially pressurizing, curing, foaming, homogenizing and foaming at constant temperature, drying and cutting to prepare the foamed sheet.
The following performance tests were performed on the foam 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 foamed sheet prepared according to the present invention has a density of 0.632 to 0.671g/cm 3 The material has the characteristics of porous light foaming material, the tensile strength is 4.07-4.32MPa, the elongation at break is 394-425%, the tensile property is good, the tearing strength is 16.57-17.31kN/m, the maximum puncture force is 22.3-25.5N, the destruction resistance is good, and the material is suitable for vamp materials.
To verify the applicability of the foam sheets prepared in examples 4 to 6 and comparative example 1 to vamp embossing, 3 samples were taken from each group, stepped silica gel press molds were prepared with compression amounts of 0.2mm, 0.5mm and 1mm, respectively, the samples were applied to the silica gel press molds and pressed, and the pressing pressure was set to 5kg/cm 2 The high-frequency hot pressing is used for observing the surface state after embossing, the flatness and the pressing error before and after embossing are detected, and the specific data are shown in a table 2:
TABLE 2
As can be seen from the data in Table 2, the foamed sheet prepared by the invention has good surface state, keeps smooth surface after high-frequency hot-pressing printing, has the pressing error of only 0.013-0.017mm, and has high simulation degree when being used for vamp printing.
The foamed sheets prepared in examples 4 to 6 and comparative example 1 are taken, and the specific test data are shown in Table 3 by referring to the GB/T15979-2002 standard bacteriostasis test:
TABLE 3
As can be seen from the data in Table 3, the foam sheet prepared by the invention has a certain antibacterial effect, and can play an antibacterial and deodorizing effect when being applied to vamp materials.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to 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 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 foregoing is illustrative and explanatory only and is not intended to be exhaustive or to limit the invention to the precise embodiments described, and various modifications, additions, and substitutions may be made by those skilled in the art without departing from the scope of the invention or exceeding the scope of the claims.
Claims (9)
1. A polyurethane foaming sheet for simulated printing is characterized by being formed by foaming a prepolymer, a white material and a hydrogen peroxide solution, wherein the white material is 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 under ultrasonic dispersion state, standing for 5h, centrifuging to obtain lower layer jelly, evaporating to dryness, and calcining in an oxidation furnace to obtain zinc-containing micropowder;
step A2: dissolving sodium lignosulfonate in water to prepare a dispersion solution, adding zinc-containing micro powder, performing ultrasonic dispersion, dripping oxalic acid solution under stirring, centrifuging, separating a lower layer, and performing vacuum drying to prepare the antibacterial foaming agent.
2. The polyurethane foam sheet for simulated printing according to claim 1, wherein the ratio of the zinc acetate, the ethanol solution and the 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%.
3. The polyurethane foam sheet for the simulated printing according to claim 1, wherein the oxygen content in the oxidation furnace is 50-80%, the baking temperature is 820-950 ℃, and the baking time is 2-3h.
4. The polyurethane foam sheet for the simulated printing according to claim 1, wherein the using amount ratio of the dispersion liquid, the zinc-containing micro powder and the oxalic acid is 30-50mL:6-8g:2-5mL, and the mass fraction of the sodium lignin sulfonate in the dispersion liquid is 5.8-7.5%.
5. The method for preparing the polyurethane foam sheet for the simulated printing according to claim 1, which is characterized by comprising the following steps:
step S1: heating poly (1, 4-butanediol adipate) diol to 110 ℃, vacuumizing to 5mmHg, and performing pressure maintaining dehydration for 2 hours to complete the dehydration treatment of the poly (1, 4-butanediol adipate) diol;
step S2: cleaning a polymerization kettle by using dry nitrogen, adding dehydrated poly (1, 4-butylene glycol adipate) diol and tetrahydrofuran, stirring for dissolving, adding isophorone diisocyanate, stirring for mixing, heating to 58-65 ℃, reacting for 75-85min, and preparing a prepolymer;
and step S3: adding an antibacterial foaming agent, 1, 4-butanediol, dibutyltin dilaurate and methyl silicone oil into a stirrer, and uniformly mixing to prepare a white material;
and step S4: mixing the prepolymer and the white material, adding the mixture into a polymerization kettle, heating to 75-80 ℃, stirring for reaction for 3-4h, adding a hydrogen peroxide solution, stirring and mixing for 5min, transferring the mixture into a die cavity for foaming treatment, and then sequentially drying and cutting to prepare a foaming sheet.
6. The method for preparing polyurethane foam sheet for emulation printing according to claim 5, wherein the amount ratio of 1, 4-butanediol adipate, tetrahydrofuran and isophorone diisocyanate is 30-35g:110-150mL:17-22g.
7. The method for preparing a polyurethane foam sheet for a simulated printing as claimed in claim 5, wherein the ratio of the antibacterial foaming agent to the 1, 4-butanediol, dibutyltin dilaurate and methyl silicone oil is 5-8g:40-50mL:0.5-1g:10-15mL.
8. The preparation method of the polyurethane foam sheet for the simulated printing as claimed in claim 5, wherein the dosage ratio of the prepolymer, the white material and the hydrogen peroxide solution is 90-110g:55-68g:12-15g, the concentration of the hydrogen peroxide solution is 60%.
9. The method for preparing the polyurethane foam sheet for the simulated printing according to claim 5, wherein the foaming treatment sequentially comprises the following steps:
pressure curing and foaming: introducing steam, pressurizing to 5-6bar at 120-130 deg.C, and foaming for 55-80min;
homogenizing and foaming at constant temperature: and (4) transferring the mixture into a constant temperature and humidity box, setting the temperature to be 60 ℃ and the humidity to be 90%, and standing and foaming for 3-5 hours.
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| CN116253852A (en) * | 2022-12-22 | 2023-06-13 | 苏州羽燕新材料科技有限公司 | Preparation method of modified thermoplastic polyurethane elastomer |
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