CN110894352B - Polyurethane material composition, polyurethane shoe material and preparation method thereof - Google Patents
Polyurethane material composition, polyurethane shoe material and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
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- A—HUMAN NECESSITIES
- A43—FOOTWEAR
- A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
- A43B13/00—Soles; Sole-and-heel integral units
- A43B13/02—Soles; Sole-and-heel integral units characterised by the material
- A43B13/04—Plastics, rubber or vulcanised fibre
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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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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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
- C08G18/44—Polycarbonates
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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
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0083—Foam properties prepared using water as the sole blowing agent
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/04—Antistatic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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Abstract
The invention relates to a polyurethane material composition, a polyurethane shoe material and a preparation method thereof, wherein the polyurethane material composition is prepared from a raw material A and a raw material B, and the raw material A comprises the following components in parts by weight: 85-105 parts of polyol, 3-5 parts of quaternary ammonium salt modified fluorocarbon finishing agent, 2-3 parts of antistatic agent, 1-2 parts of chain extender, 1.5-2.0 parts of catalyst, 0.05-0.1 part of foaming agent and 0.05-0.1 part of foam stabilizer; the raw material B comprises 110-115 parts of isocyanate. The polyurethane shoe material has the functions of dirt suppression, easy decontamination and static prevention, and can simultaneously maintain the functions of dirt suppression, easy decontamination and static prevention and increase the cleanliness of the static prevention shoe; and the cleaning performance in the use process is greatly improved, and the anti-static shoe and the anti-static boot are used for preparing an anti-static shoe and an anti-static clothes assembly sleeve and used as a tool in the working environment of a clean room.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a polyurethane material composition, a polyurethane shoe material and a preparation method thereof.
Background
The antistatic dust-free shoes can be used in cleaning workshops or dust-free rooms, and are suitable for enterprises with higher requirements on cleaning levels, such as microelectronics, medicine, aerospace, precision machinery and the like. Antistatic clothing in the cleaning shop is processed by chemical fiber filament, and staff in the working process, the body and clothing friction can produce a lot of static charges, and these static charges need to pass through the mode of ground connection with the antistatic shoes that the antistatic clothing links to each other, go out the static charge release that produces, otherwise will cause very big damage to electronic components.
The sole base material of the antistatic shoes is polyurethane or PVC, the PVC sole is low in price and poor in wear resistance and easy to fall crumbs, the antistatic shoes are generally used for processing dust-free shoes used in low-end clean rooms, the wear resistance of the polyurethane soles is 5 times that of PVC, and the antistatic shoes can be used from sole shoes used in the low-end clean rooms to boot soles used in high-end clean rooms. According to the requirement of clean environment in a clean room, the anti-static shoes not only need to have an anti-static function, but also need to have low dust generation property so as to reduce dust generated in the working process. The floor skin of the clean room is generally epoxy floor paint of rubber, a large amount of pollutants cannot be adhered to the floor for a long time, and the sole is more easily polluted as a material directly contacting the pollutants; meanwhile, the polyurethane material belongs to a three-dimensional reticular porous hydrophobic substance, and has strong adsorbability and lipophilicity, and is more easily polluted and difficult to clean. In order to maintain cleanliness, the cleaning frequency is consistent with that of antistatic clothing, and a clean room with a high grade is cleaned once and a clean room with a low grade is cleaned two to three times per week. The cleaning frequency is far higher than that of civil shoes, the dirt restraining and soil easily removing functions are added on the anti-static polyurethane soles, and the cleaning device has great significance for keeping the cleanliness of the anti-static shoes and reducing secondary sole pollution.
From the current research and market antistatic shoe products, the antistatic polyurethane sole with the soil release function is rarely seen, even if the antistatic performance alone has some problems. At present, the resistance of the polyurethane material sole is reduced by adding quaternary ammonium salt or conductive graphite carbon black with a small molecular structure as an antistatic material. Patent CN107523039A discloses a polyurethane sole, which is made into antistatic shoes by adding small molecular quaternary ammonium salt; patent CN104277200A discloses an antistatic polyurethane sole material and a preparation method thereof, the polyurethane material is added with conductive graphite to make antistatic shoes, and patent No. CN102504519A discloses an antistatic shoes method by adding conductive carbon fiber powder and micromolecular quaternary ammonium salt antistatic agent to the polyurethane material. The antistatic agent is added with a small molecular antistatic quaternary ammonium salt antistatic agent, and the antistatic agent gradually migrates and dissolves in water with the increase of the washing times, so that the antistatic effect is lost; the addition of the conductive carbon black material can keep a lasting antistatic effect, but the carbon black particle material independently exists in the polyurethane material, can fall off a black ground and cause secondary dust pollution in the wearing and using friction process, and is unfavorable for the clean room environment.
Disclosure of Invention
Therefore, a polyurethane material composition is needed, and the polyurethane material has the functions of inhibiting and easily removing dirt, and simultaneously can maintain the functions of inhibiting and easily removing dirt, so that the cleanliness of the anti-static shoe is increased; and the antistatic performance is durable, and the cleaning performance in the use process is greatly improved.
A polyurethane material composition is prepared from a raw material A and a raw material B, wherein the raw material A comprises the following components in parts by weight: 85-105 parts of polyol, 3-5 parts of quaternary ammonium salt modified fluorocarbon finishing agent, 2-3 parts of antistatic agent and 1-2 parts of chain extender; the raw material B comprises 110-115 parts of isocyanate.
In one embodiment, the quaternary ammonium salt modified fluoroalkane finishing agent is a quaternary ammonium salt modified fluoroalkane polyacrylate, which has the following structural formula:
n is1：n2：n3：n4(30-40): (20-30): (3-5): 1; preferably, the molecular weight of the quaternary ammonium salt modified fluoroalkyl polyacrylate is 2-3 ten thousand.
In some of these embodiments, the antistatic agent is a long-chain polyaromatic antistatic agent; preferably, the antistatic agent is poly N-vinyl-N-butylimidazolium bromide or a copolymer thereof, and more preferably, the copolymer is prepared by polymerizing N-vinyl-N-butylimidazolium bromide by itself or copolymerizing N-vinyl-N-butylimidazolium bromide with alkenes.
In some embodiments, the polybrominated N-vinyl-N-butyl-imidazolium has the structure shown in formula (I), and the polybrominated N-vinyl-N-butyl-imidazolium copolymer is an N-vinyl-N-butyl-imidazolium bromide-N-vinylimidazole copolymer or an N-vinyl-N-butyl-imidazolium bromide-ethyl acrylate copolymer; the structural formula of the brominated N-vinyl-N-butylimidazolium-N-vinylimidazole copolymer is shown in a formula (II), and the structural formula of the brominated N-vinyl-N-butylimidazolium-ethyl acrylate copolymer is shown in a formula (III);
the 0< a < b; preferably, the molecular weight of the polybrominated N-vinyl-N-butylimidazolium or the copolymer thereof is 3000-5000.
In some embodiments, the polyol is at least one of polyester polyol, polyether polyol and polycarbonate polyol, preferably, the polyester polyol is difunctional carbonate diol and adipic polyester diol; the polyether glycol is bifunctional polyether glycol; more preferably, the adipic acid-based polyester diol is polyethylene adipate, polyethylene propylene adipate, polybutylene adipate, or polyethylene glycol adipate.
In some of these embodiments, the isocyanate is selected from polyfunctional aliphatic, aromatic, and cycloaliphatic polyisocyanates, preferably the isocyanate is at least one of difunctional diphenylmethane diisocyanate, hexamethylene diisocyanate, toluene diisocyanate; and/or the presence of a catalyst in the reaction mixture,
the chain extender is at least one of ethylene glycol, propylene glycol, diethylene glycol, 1,4 butanediol and 1,6 hexanediol.
In some embodiments, the raw material a further comprises, in parts by weight: 1.5-2.0 parts of a catalyst; and/or 0.05-0.1 part of foaming agent; and/or 0.05-0.1 part of foam stabilizer.
In some embodiments, the catalyst is at least one of an organic tin compound and an organic amine mixture, preferably, the catalyst is a composition compound of butyl tin laurate, stannous octoate, triethylene diamine and diethylenetriamine; and/or the presence of a catalyst in the reaction mixture,
the foaming agent is water; and/or the presence of a catalyst in the reaction mixture,
the foam stabilizer is an organosilicone surfactant, and preferably, the foam stabilizer is a polysiloxane-oxyalkylene block copolymer.
Furthermore, the invention also provides a polyurethane shoe material which is prepared from the polyurethane material composition.
In some of these embodiments, the polyurethane material is a sole.
Furthermore, the invention provides a preparation method of the polyurethane shoe material, which comprises the following steps:
1) drying 85-105 parts by weight of polyol and 110-115 parts by weight of isocyanate for later use;
2) drying 2-3 parts by weight of antistatic agent, and then adding polyol to mix uniformly;
3) sequentially adding 3-5 parts by weight of quaternary ammonium salt modified fluorocarbon finishing agent, 1.5-2.0 parts by weight of catalyst, 1-2 parts by weight of chain extender, 0.05-0.1 part by weight of foaming agent and 0.05-0.1 part by weight of foam stabilizer, and uniformly mixing to form a material A;
4) and taking the dried antistatic agent as a material B, and pouring the material A and the material B into a shoe material mold through a casting machine for molding to obtain the polyurethane shoe material.
In the preparation process of the polyurethane shoe material, the cationic quaternary ammonium salt modified fluorine finishing agent is added, and the finishing agent has quaternary ammonium salt groups, so that the easy-to-clean finishing agent has antistatic property, and is matched with the antistatic agent in the polyurethane material, and the two antistatic agents generate a synergistic antistatic effect, so that the antistatic property of the sole is further improved, the addition of the antistatic agent can be reduced, and the good help is provided for maintaining the physical and mechanical properties of the sole of the polyurethane material; the finishing agent contains alcoholic hydroxyl groups, can perform oxidation-reduction reaction with isocyanate groups to perform chemical bond combination, and is durable in washing resistance to improvement of antistatic and easy-to-remove performance. The cationic quaternary ammonium salt modified fluorine finishing agent is combined with the polyurethane sole material by limiting the content ratio of each component, so that the polyurethane sole material has good soil release performance and certain oil repellency, and the cleaning performance of the manufactured antistatic shoe in the wearing process is greatly improved; the carbon black particle pollution of the carbon black antistatic shoes can not occur, the color can not be faded, and the dust generation performance of the working clothes of the workers can be well reduced.
Detailed Description
In order that the invention may be more fully understood, a more particular description of the invention will now be rendered by reference to specific embodiments thereof that are illustrated in the appended drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The polyurethane material composition of one embodiment can be used for preparing antistatic shoe materials with lasting dirt inhibition, easy decontamination and static resistance. Specifically, the polyurethane material composition is prepared from a raw material A and a raw material B, wherein the raw material A comprises the following components in parts by weight: 85-105 parts of polyol, 3-5 parts of quaternary ammonium salt modified fluorocarbon finishing agent, 2-3 parts of antistatic agent and 1-2 parts of chain extender; the raw material B comprises 110-115 parts of isocyanate.
In the polyurethane material composition, the cationic quaternary ammonium salt modified fluorine finishing agent is added, and the finishing agent has a quaternary ammonium salt group, so that the easy-cleaning finishing agent has antistatic property, and the two antistatic agents are matched with the antistatic agent in the polyurethane material to generate a synergistic antistatic effect, so that the antistatic property of the sole is further improved, the addition amount of the antistatic agent can be reduced, and the good help is provided for maintaining the physical and mechanical properties of the sole of the polyurethane material; and the finishing agent can carry out redox reaction with isocyanate groups in the raw material B to carry out chemical bond combination, so that the finishing agent has lasting washing fastness for improving the antistatic and easy-to-clean performance. The cationic quaternary ammonium salt modified fluorine finishing agent is combined with the polyurethane sole material by limiting the content ratio of each component, so that the polyurethane sole material has good soil release performance and certain oil repellency, and the cleaning performance of the manufactured antistatic shoe in the wearing process is greatly improved; the carbon black particle pollution of the carbon black antistatic shoes can not occur, the color can not be faded, and the dust generation performance of the working clothes of the workers can be well reduced.
The polyol is used as a raw material for preparing the polyurethane material, and different polyols have great influence on the performance of the prepared polyurethane material, and specifically, the polyol comprises at least one of polyester polyol, polyether polyol and polycarbonate polyol; further, the polyol is polyester polyol and/or polyether polyol with the molecular weight of 1500-2500; furthermore, the polyester polyol is difunctional carbonate dihydric alcohol and adipic acid polyester dihydric alcohol; the adipic acid polyester diol is polyethylene glycol adipate, polybutylene glycol adipate or polyethylene glycol adipate; the polyester polyol may contain a polyester diol, a polyamide polyester diol, or the like obtained by using a carboxylic acid, a diol, a diamine, or the like other than those described above. The polyether glycol is bifunctional polyether glycol; examples of the polycarbonate polyol include polyols obtained by esterification of carbonic acid with an aliphatic polyol. Specific examples thereof include reaction products of diols such as 1, 3-propanediol, 1, 4-butanediol, 1, 6-hexanediol, diethylene glycol, polyethylene glycol, polypropylene glycol, and polytetramethylene glycol (PTMG), dimethyl carbonate, diphenyl carbonate, and phosgene. These may be used alone or in combination of 2 or more. In some embodiments, the content of the polyol is 85-105 parts by weight, which is helpful for ensuring that the polyol and the preparation raw materials of the polyurethane material are fully reacted to form the polyurethane shoe material with excellent performance. In one specific embodiment, the polyol is present in an amount of 90 parts by weight.
Quaternary ammonium groups in the quaternary ammonium salt modified fluorocarbon finishing agent bring antistatic property, fluorocarbon chain segments bring water repellency, oil repellency, antifouling property and easy detergency, and the prepared polyurethane shoe material can be endowed with antistatic, water repellency, oil repellency, antifouling and decontamination functions by adding the quaternary ammonium salt modified fluorocarbon finishing agent into a polyurethane material preparation raw material, so that the cleaning performance of the manufactured antistatic shoe material in the using and wearing process is greatly improved; the carbon black particle pollution of the carbon black antistatic shoes can not occur, the color can not be faded, and the dust generation performance of the working clothes of the workers can be well reduced. Specifically, the quaternary ammonium salt modified fluorocarbon finishing agent is quaternary ammonium salt modified fluoroalkyl polyacrylate (FBDH), and the structural formula of the quaternary ammonium salt modified fluoroalkyl polyacrylate (FBDH) is as follows:
wherein n is1：n2：n3：n4＝(30～40): (20-30): (3-5): 1; preferably, the molecular weight of the FBDH finishing agent is 2-3 ten thousand, the FBDH finishing agent selected within the molecular weight range has better antistatic, water-repellent, oil-repellent, antifouling and stain removal functions, and simultaneously has better antistatic synergistic effect with the double-long-chain antistatic agent. Specifically, the quaternary ammonium salt-modified fluoroalkyl polyacrylate (FBDH) may be n1：n2：n3：n430: 20: 3: 1 FBDH finish, or n1：n2：n3：n440: 30: 5: 1 FBDH finishing agent, may also be n1：n2：n3：n430: 30: 3: 1 FBDH finish.
The preparation method of the quaternary ammonium salt modified fluoroalkyl polyacrylate (FBDH) is prepared by adopting the prior art-Master thesis synthesis and application of soil release type fluorine-containing polyacrylate water-repellent and oil-repellent finishing agent, and the preparation method comprises the following steps:
1) preparation of the Pre-emulsion
Mixing dimethyl diallyl ammonium chloride, hydroxyethyl methacrylate, an emulsifier and distilled water according to a certain proportion, shearing, dispersing and emulsifying at a high speed for 5min at room temperature, adding hexafluorobutyl methacrylate and butyl acrylate, and continuing to shear and emulsify for a period of time to obtain a milky pre-emulsion;
2) emulsion polymerization
And adding a small amount of distilled water serving as a base solution into a four-neck flask provided with a stirrer, a condenser pipe, a thermometer and a dropping funnel, heating to 70 ℃, adding 1/4 pre-emulsion and 1/3 initiator, starting to dropwise add the rest 3/4 pre-emulsion and 2/3 initiator after the emulsion turns blue, controlling the dropwise adding speed within 1.5-2 h, keeping the temperature for reacting for a certain time, cooling to room temperature, and adjusting the pH to be acidic to obtain the quaternary ammonium salt modified fluoroalkyl polyacrylate (FBDH).
The quaternary ammonium salt modified fluoroalkyl polyacrylate (FBDH) is prepared by adopting 2, 2-azobis (2-methylpropylimide) dihydrochloride as an initiator, carrying out quaternary copolymerization on dimethyl diallyl ammonium chloride, hydroxyethyl methacrylate, hexafluorobutyl methacrylate and butyl acrylate according to a certain proportion, and synthesizing the reaction equation as follows:
the FBDH finishing agent contains alcoholic hydroxyl groups, has reaction activity, can perform oxidation-reduction reaction with isocyanate groups in the raw material B, and is chemically bonded, so that the anti-static easy-decontamination performance is improved by lasting washing fastness; meanwhile, the finishing agent is of a polymeric long-chain structure, is matched with a small amount of another long-chain antistatic agent, and generates a synergistic antistatic effect through the double long-chain antistatic agents, so that the antistatic performance of the sole is further improved, the addition amount of the antistatic agent can be reduced, and the finishing agent is good in maintaining of the physical and mechanical properties of the polyurethane material sole. And the carbon atom number of the fluoroalkane carbon chain of the finishing agent is 6, and the finishing agent belongs to a short carbon chain structure, so that the finishing agent is more easily degraded while the performance is maintained, and the environmental pollution is avoided.
In some embodiments, the content of the FBDH finishing agent is 3-5 parts by weight, and the anti-fouling, decontamination and antistatic effects can be realized by adding a small amount of finishing agent, and in a specific embodiment, the content of the FBDH finishing agent is 4 parts by weight.
The addition of the antistatic agent is beneficial to the preparation of the polyurethane shoe material with antistatic performance, specifically, the antistatic agent is a long-chain polyaromatic antistatic agent, and the anti-migration performance of the antistatic agent with the structure is superior to that of a common aliphatic antistatic agent and a small-molecule antistatic agent. The long-chain antistatic agent and the FBDH finishing agent are compounded, a synergistic antistatic effect is generated by the double long-chain antistatic agents, the antistatic performance of the sole is further improved, the addition amount of the antistatic agent can be reduced, the good help is provided for maintaining the physical and mechanical properties of the sole made of the polyurethane material, the antistatic agent is of a polymerized long-chain type and is aromatic-like structure ring, compared with the common aliphatic micromolecular antistatic agent, the antistatic agent has a structure more similar to that of the polyurethane material, is less prone to precipitation and migration, and further improves the antistatic performance and the washing resistance of the sole. Further, the antistatic agent is poly N-vinyl-N-butylimidazolium bromide or a copolymer thereof, and further, the copolymer is formed by polymerizing the N-vinyl-N-butylimidazolium bromide or copolymerizing the N-vinyl-N-butylimidazolium bromide and alkene. Specifically, the antistatic agent is poly N-vinyl-N-butylimidazolium bromide as shown in formula (I), the copolymer is a copolymer of N-vinyl-N-butylimidazolium bromide and ethyl acrylate, wherein the structure of the copolymer of N-vinyl-N-butylimidazolium bromide and ethyl acrylate is shown in formula (II), and the structure of the copolymer of N-vinyl-N-butylimidazolium bromide and ethyl acrylate is shown in formula (III),
wherein, the molar number of the quaternary ammonium salt structural part in the structures in the formula (II) and the formula (III) is more than 50 percent of the total number of the structures, namely b is more than a, and both are more than 0, and the quaternary ammonium salt structural part has higher molar number, so that the antistatic property is good.
The preparation method of the polybrominated N-vinyl-N-butylimidazolium copolymer is realized by adopting the prior art (synthesis, characterization and electrochemical properties [ J ] of the polymer of N-vinyl imidazolium salt, Liouping, Tang-Geng, Malus abrus, Wanghaibo, chemical research, 2008, 19(3): 42-44).
The preparation of brominated N-vinyl-N-butylimidazolium-N-vinylimidazole copolymers was carried out as in the synthesis of brominated N-vinyl-N-butylimidazolium copolymers (QPVI) at 1.2.1, synthesized in the experimental part of the prior art.
The preparation method of the brominated N-vinyl-N-butylimidazolium-ethyl acrylate copolymer is the same as that of the 1.2.2 synthesis of the brominated N-vinyl-N-butylimidazolium-ethyl acrylate copolymer (QVI-EA) in the experimental part of the prior art.
Among them, the preparation method of polybrominated N-vinyl-N-butylimidazolium is substantially the same as that of the brominated N-vinyl-N-butylimidazolium-ethyl acrylate copolymer of the prior art reference, except that ethyl acrylate is not added in the preparation method, but the monomer itself is polymerized in a solvent.
Specifically, the preparation method of the polybrominated N-vinyl-N-butylimidazolium comprises the following steps:
1) adding 25 parts by weight of N-vinylimidazole monomer, 73 parts by weight of bromoethane and 40 parts by weight of absolute ethyl alcohol into a reaction vessel with a reflux condensing device in sequence, stirring and heating to 80 ℃ under the protection of nitrogen, keeping the constant temperature for reaction for 20 hours to obtain a dark red liquid, rotationally evaporating to remove a solvent and raw materials, and drying in vacuum at 80 ℃ for 24 hours to constant weight to obtain dark brown solid N-vinylimidazole-N-butylammonium bromide.
2) And (2) putting 30 parts by weight of the dark brown solid N-vinylimidazole-N-butylammonium bromide, 50 parts by weight of benzene and 0.5 part by weight of a free radical initiator azobisisobutyronitrile AIBN into a reaction vessel with a condensation reflux device, stirring and heating to 65 ℃ under the protection of nitrogen, keeping the temperature for reaction for 20 hours, rotationally evaporating to remove the solvent, dissolving with a proper amount of absolute ethyl alcohol, precipitating a product with ethyl acetate, and drying in vacuum at 80 ℃ for 24 hours to constant weight to obtain the poly-N-vinyl-N-butylamidoammonium bromide.
The content of each component in the poly (N-vinyl-N-butylimidazolium bromide) prepared in the above is adjusted according to the need, and is not limited to the above ratio.
In some embodiments, the antistatic agent has a molecular weight of 3000-5000, and the poly-brominated N-vinyl-N-butyl imidazole ammonium or the copolymer thereof with the molecular weight in the range is selected to be matched with the FBDH finishing agent, so that the antistatic synergistic effect is better. Specifically, the antistatic agent may be poly-N-vinyl-N-butylimidazolium bromide with a molecular weight of 3000, N-vinyl-N-butylimidazolium bromide-N-vinylimidazole copolymer with a molecular weight of 4000, or N-vinyl-N-butylimidazolium bromide-ethyl acrylate copolymer with a molecular weight of 5000.
In some embodiments, the content of the antistatic agent is 2 to 3 parts by weight, and the addition amount of the antistatic agent can be reduced by compounding two long-chain antistatic agents, that is, the effects of stain resistance and stain removal and antistatic can be realized, and in a specific embodiment, the content of the antistatic agent is 2 parts by weight.
The chain extender is a preparation raw material for preparing the polyurethane material, the chain extender is a chain extender commonly used in the field, specifically, the chain extender is at least one of ethylene glycol, propylene glycol, diethylene glycol, 1,4 butanediol and 1,6 hexanediol, further, the content of the chain extender is 1-2 parts by weight, and the content range of the parts by weight is beneficial to ensuring that the chain extender and the preparation raw material of the polyurethane material are fully reacted to form the polyurethane shoe material with excellent performance. In one specific example, the chain extender is present in an amount of 2 parts by weight.
The isocyanate is multifunctional isocyanate, and the isocyanate group can be subjected to redox reaction with an alcoholic hydroxyl group in the finishing agent to carry out chemical bond combination, so that the anti-static easy-decontamination performance is improved in lasting washing fastness.
The polyfunctional isocyanate refers to a compound having 2 or more isocyanate groups (hereinafter, also referred to as NCO groups) in the molecule, and any of known aliphatic, aromatic, and alicyclic polyisocyanates can be used as the polyisocyanate component, and examples thereof include diphenylmethane diisocyanate, carbodiimide-modified MDI, polymethylene polyphenyl polyisocyanate, carbodiimide-diphenylmethane polyisocyanate, xylene diisocyanate, toluene diisocyanate, Hexamethylene Diisocyanate (HDI), dimer acid diisocyanate, norbornene diisocyanate, lysine diisocyanate, aliphatic polyisocyanates such as tetramethylxylylene diisocyanate, hydrogenated diphenylmethane diisocyanate (hydrogenated MDI), hydrogenated xylylene diisocyanate (hydrogenated XDI), and the like, Alicyclic polyisocyanates such as cyclohexane diisocyanate, dicyclohexylmethane diisocyanate and isophorone diisocyanate are preferably diphenylmethane diisocyanate, hexamethylene diisocyanate or toluene diisocyanate, and the above isocyanates may be used alone or in combination of 2 or more.
The reaction of isocyanate with bifunctionality is easy to control, and the ratio of isocyanate group to hydroxyl group can be ensured to be in a certain range. In the raw materials for preparing the shoe material, the diphenylmethane diisocyanate is selected, the reaction is easy to control, and the generated microporous polyurethane elastomer has good mechanical property and excellent wear resistance and bending resistance. Furthermore, the content of the isocyanate is 110-115 parts by weight, and the content range of the isocyanate is favorable for ensuring that the isocyanate and other raw materials are fully reacted to form the polyurethane shoe material with excellent performance. In one specific embodiment, the isocyanate is present in an amount of 115 parts by weight.
Specifically, the polyurethane material composition further comprises 1.5-2.0 parts by weight of a catalyst, 0.05-0.1 part by weight of a foaming agent and 0.05-0.1 part by weight of a foam stabilizer.
Further, the catalyst used for the synthesis of the polyurethane material composition is not particularly limited, and a known catalyst can be used, and in the present invention, an amine-based catalyst or a derivative thereof used for the preparation of a polyurethane material is generally used, and examples thereof include organic amine compounds such as triethylenediamine, diethylenetriamine, triethylamine, tributylamine, benzyldibutylamine, triethylenediamine, and the like; further, metal-based compounds such as organotin-based compounds, for example, organotin compounds such as butyltin laurate, dibutyltin oxide, dibutyltin dilaurate, tin 2-ethylhexanoate, stannous octoate, tin octoate and dibutyltin dilaurate can be used.
In order to obtain foam with good reactivity balance and stable foaming body, the preferable catalyst is a compound of organic tin and organic amine, for example, the catalyst is a compound consisting of butyl tin laurate, stannous octoate, triethylene diamine and diethylenetriamine; more preferably, the mass ratio of organotin to organoamine is 2: 1;
in the present invention, water is used as the blowing agent. As the blowing agent, a known blowing agent used for foaming in the urethane formation reaction can be used, and examples thereof include small molecular alcohols such as ethanol and propanol, but water is inexpensive and stable, and the addition process can be reduced by using water in other water-containing raw materials as a catalyst. Furthermore, when the content of the water is 0.05 to 0.1 part by weight, the foaming state of the polyurethane material can be improved.
The foam stabilizer plays a role in regulation, so that the foaming is more uniform and stable, and a foam with finer foam is prepared, in the invention, the polysiloxane-oxyalkylene segmented copolymer is used as the foam stabilizer, the foam stabilizer can also use a known organic siloxane surfactant foam stabilizer used in the foaming during the polyurethane reaction, and further, when the content of the foam stabilizer in parts by weight is 0.05-0.1 part by weight, the foaming in the preparation process of the polyurethane material can be more uniform and stable.
The polyurethane shoe material of an embodiment has the functions of permanent antistatic, water repellent, oil repellent, stain repellent and stain removal, and specifically, the raw material for preparing the polyurethane shoe material is prepared from the polyurethane material composition.
In the preparation process of the polyurethane shoe material, the cationic quaternary ammonium salt modified fluorine finishing agent is added, and the finishing agent has quaternary ammonium salt groups, so that the easy-cleaning finishing agent has antistatic property, and meanwhile, the long-chain antistatic agent in the polyurethane material is matched, and the two long-chain antistatic agents generate a synergistic antistatic effect, so that the antistatic property of the sole is further improved, the addition amount of the antistatic agent can be reduced, and meanwhile, the polyurethane shoe material has good help for maintaining the physical and mechanical properties of the sole; the finishing agent contains alcoholic hydroxyl groups, can perform oxidation-reduction reaction with isocyanate groups to perform chemical bond combination, and is durable in washing resistance to improvement of antistatic and easy-to-remove performance. The cationic quaternary ammonium salt modified fluorine finishing agent is combined with the polyurethane sole material by limiting the content ratio of each component, so that the polyurethane sole material has good soil release performance and certain oil repellency, and the cleaning performance of the manufactured antistatic shoe in the wearing process is greatly improved; the carbon black particle pollution of the carbon black antistatic shoes can not occur, the color can not be faded, and the dust generation performance of the working clothes of the workers can be well reduced.
In a specific embodiment, the polyurethane material is a sole, the sole is more easily polluted as the material directly contacting with pollutants, and the traditional polyurethane material for manufacturing the sole has strong adsorbability and lipophilicity, is more easily polluted and is difficult to clean. The cleaning frequency is far higher than that of civil shoes, and the soles prepared by combining the polyurethane material have good soil release performance and certain oil repellency, so that the cleaning performance of the manufactured antistatic shoes in the wearing process is greatly improved; the carbon black particle pollution of the carbon black antistatic shoes can not occur, the color can not be faded, and the dust generation performance of the working clothes of the workers can be well reduced.
The method for preparing a polyurethane shoe material according to the embodiment can prepare a shoe material having lasting antistatic, water repellent, oil repellent, antifouling and stain removal functions. Specifically, the preparation method comprises the following steps:
s1: drying 85-105 parts by weight of polyol and 110-115 parts by weight of isocyanate for later use;
specifically, the drying temperature in step S1 is 70 to 80 ℃, and the moisture of the polyol can be dried at this temperature, and the polyol and isocyanate are relatively stable at this temperature.
S2: drying 2-3 parts by weight of antistatic agent, and then adding polyol to mix uniformly;
specifically, the drying temperature in step S2 is 90 to 100 ℃.
S3: sequentially adding 3-5 parts by weight of quaternary ammonium salt modified fluorocarbon finishing agent, 1.5-2.0 parts by weight of catalyst, 1-2 parts by weight of chain extender, 0.05-0.1 part by weight of foaming agent and 0.05-0.1 part by weight of foam stabilizer, and uniformly mixing to form a material A;
s4: and taking the dried antistatic agent as a material B, and pouring the material A and the material B into a shoe material mold through a casting machine for molding to obtain the polyurethane shoe material.
Specifically, the casting molding, curing, heat curing and demolding steps and the like in step S4 are conventional techniques for manufacturing shoe soles. For example, the material can be cast and molded by heating to 40-45 ℃.
Specifically, the polyol, the antistatic agent, the quaternary ammonium salt modified fluorocarbon finishing agent, the catalyst, the chain extender, the foaming agent and the foam stabilizer adopt the components in the polyurethane material composition.
The polyurethane shoe material prepared by the method has the following advantages:
1) in the polyurethane shoe material, the cationic quaternary ammonium salt modified fluorine finishing agent is added, and the finishing agent has a quaternary ammonium salt group, so that the soil release finishing agent has antistatic property, and meanwhile, the long-chain antistatic agent in the polyurethane material is matched, and the two long-chain antistatic agents generate a synergistic antistatic effect, so that the antistatic property of the sole is further improved, the addition of the antistatic agent can be reduced, and the physical and mechanical properties of the sole made of the polyurethane material can be maintained; the finishing agent contains alcoholic hydroxyl groups, can perform redox reaction with isocyanate groups to perform chemical bond combination, and is durable in washing fastness for improving the antistatic and easy-to-clean performance; compared with the common fat micromolecule antistatic agent, the selected long-chain aromatic antistatic agent has a structure which is more similar to that of a polyurethane material, is less prone to precipitation and migration, and further improves the antistatic performance and the washing resistance of the sole.
2) Traditional polyurethane material anti-static sole does not possess and suppresses dirty easy decontamination function, and current anti-static shoes anti-static effect is not lasting, uses conductive carbon black class material to bring the persistence usually, nevertheless in the wearing and using friction process, can drop and dye the problem that the ground causes secondary dusting pollution simultaneously. The polyurethane shoe material provided by the invention has the advantages that the dirt-inhibiting and soil-releasing functions are realized on the polyurethane anti-static sole, the cleanliness of the anti-static shoe is increased, the carbon black particle pollution of carbon black anti-static shoes is avoided, the color fading is avoided, and the dust generation performance of working clothes of workers is reduced.
3) The carbon atom number of the fluoroalkane carbon chain of the quaternary ammonium salt modified fluorine finishing agent is 6, the fluoroalkane carbon chain belongs to a short carbon chain structure, the performance is maintained, the fluoroalkane carbon chain is easier to degrade, and no environmental pollution is caused.
As the raw material used in the present invention, a commercially available product can be used, unless otherwise specified.
The invention is further illustrated, but not limited, by the following specific examples.
Examples 1 to 5
The ingredients of the polyurethane sole preparation raw materials described in examples 1 to 5 are shown in Table 1.
The preparation method of the polyurethane sole in the embodiment 1-5 comprises the following steps: firstly, respectively drying the polyol in the raw material A and the isocyanate in the raw material B at 70 ℃ for later use, then drying the antistatic agent at 95 ℃, adding the antistatic agent into the polyol, uniformly stirring, then sequentially adding the quaternary ammonium salt modified fluorine finishing agent, the catalyst, the chain extender, the foaming agent and the foam stabilizer, and uniformly mixing to form a material A; and finally, uniformly mixing the mixed material A and the baked material B through a casting machine, casting the mixture into a sole mold for molding, curing for 3 minutes, and demolding to obtain the easy-decontamination anti-static polyurethane material sole.
TABLE 1
Comparative examples 1 to 6
The ingredients of the polyurethane sole preparation raw materials of comparative examples 1 to 6 are shown in Table 2.
The preparation methods of the polyurethane soles of comparative examples 1 to 6 are substantially the same as those of examples 1 to 5, and the specific methods are as follows: firstly, respectively drying the polyol in the raw material A and the isocyanate in the raw material B at 70 ℃ for later use, then drying the antistatic agent at 95 ℃, adding the antistatic agent into the polyol, uniformly stirring, then sequentially adding the finishing agent, the catalyst, the chain extender, the foaming agent and the foam stabilizer, and uniformly mixing to form a material A; and finally, uniformly mixing the mixed material A and the baked material B through a casting machine, casting the mixture into a sole mold for molding, curing for 3 minutes, and demolding to obtain the easy-decontamination anti-static polyurethane material sole.
The finishing agent and the antistatic agent are added or not added according to the combined components of the comparative example.
TABLE 2
In Table 2 "-" indicates that the corresponding components in the column were not added to the raw materials for producing the polyurethane shoe soles of this comparative example, and that the quaternary ammonium salt-modified fluorocarbon finishing agent FBDH in comparative examples 4 and 6 and the polyN vinyl-N-butylimidazolium bromide in comparative example 5 have the same structures as those in example 1.
Testing
Each performance of the polyurethane soles of examples 1-5 and comparative examples 1-6 was tested. The results are detailed in Table 3.
The performance test method comprises the following steps:
(1) washing test: the washing method is specified by appendix A in national standard GB/T28895-2012 anti-static clothing oil-resistant easy-decontamination anti-static protective clothing.
(2) And (3) testing the soil release performance: the method comprises the steps of making standard oil stains according to appendix B in national standard GB/T28895-2012 anti-oil anti-static clothing easy-decontamination anti-static protective clothing, horizontally placing the cast non-textured flat sole on a table top, dropwise adding about 0.2 ml of standard oil stains on the surface of the sole by using a dropper, and covering glass paper to press the sole for 1 minute under the pressure of 2.5 kilograms. And testing the residual oil stain after drying after washing, and performing rating of 1-5 grade by comparison with a standard card, wherein the higher the grade is, the less the residual is shown, and the lower the grade is, the more the residual is.
(3) And (3) testing antistatic performance: the volume resistance of the sole is tested, and the specific reference is GB/T20991-2007 test method of individual protective equipment shoes, wherein the humidity is 55% RH and the temperature is 27.5 ℃.
(4) And (3) testing the stain inhibition performance: according to the oil repellency test method and rating in GB/T19977-2014 textile oil repellency hydrocarbon resistance test, the non-grain flat sole material after injection is used for replacing the textile, and the rating method is the same as the textile, so that the higher the rating level is, the better the stain resistance is.
(5) Mechanical property test bending resistance and hardness: referring to a bending resistance test in GB/T20991-2007 test method of individual protective equipment shoes, continuously bending and flexing for 30000 times, and testing the length of an incision; the hardness is directly tested by a Shore durometer.
TABLE 3
As can be seen from Table 3, the polyurethane sole prepared by the invention has excellent stain removal, stain inhibition and antistatic properties, and each property is washable and permanent, wherein the effect of example 1 is the best; comparing example 1 with comparative examples 1-3 and 5, it can be seen that in terms of soil release and stain inhibition performance of the polyurethane sole, the method of the present invention can improve the soil release performance of the polyurethane sole of grade 1 to grade 4-4.5, and the stain inhibition performance of the polyurethane sole of grade 3 to grade 6, wherein each grade is improved by grade 3, and the soil release and stain inhibition performance is wash-resistant and permanent. From the test results of the embodiment 1, the comparative example 1 and the comparative examples 4 to 6, in the aspect of antistatic performance, the volume resistance of the antistatic shoe is reduced through the synergistic effect of the antistatic property of the double-long-chain quaternary ammonium salt, and the volume resistance is almost unchanged along with the increase of the washing times, so that the effect of permanent washing resistance is achieved. The sole used antistatic easy-to-clean agent FBDH has quaternary ammonium salt groups in the structure and has antistatic property, so that the resistance of the sole can reach 280 MOmega cm, the antistatic property is kept unchanged along with the increase of the washing times, but the integral resistance is slightly higher due to the structure reason. The volume resistance of the antistatic sole which singly uses the micromolecule antistatic agent is gradually increased along with the increase of the washing times, and when the antistatic sole is washed for 50 times, the volume resistance even reaches 1400 MOmega-cm and exceeds the allowable range value of the antistatic material; the anti-migration performance of the long-chain polyaromatic antistatic agent is greatly improved compared with that of a single small-molecule antistatic agent, but the resistance is increased along with the increase of the use and washing times; although the antistatic property can be maintained by adding the conductive carbon fiber powder and the micromolecule antistatic agent, carbon powder falls off in the experimental process, more carbon powder falls off in the friction experiment, and the bending resistance mechanical property and the hardness are influenced to a certain extent. The quaternary ammonium salt modified fluorocarbon finishing agent FBDH is matched with the small molecular antistatic agent, and the antistatic performance of the small molecular antistatic agent is reduced along with the increase of the washing times; experiments prove that the polyurethane sole prepared by the scheme of the invention has improved decontamination property and antistatic property.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (9)
1. The polyurethane material composition is characterized by being prepared from a raw material A and a raw material B, wherein the raw material A comprises the following components in parts by weight: 85-105 parts of polyol, 3-5 parts of quaternary ammonium salt modified fluorocarbon finishing agent, 2-3 parts of antistatic agent and 1-2 parts of chain extender; the raw material B comprises 110-115 parts of isocyanate;
the quaternary ammonium salt modified fluoroalkyl finishing agent is quaternary ammonium salt modified fluoroalkyl polyacrylate, and the structural formula of the quaternary ammonium salt modified fluoroalkyl polyacrylate is as follows:
n is1：n2：n3：n4＝(30～40)：(20～30)：(3～5)：1；
The antistatic agent is polybrominated N-vinyl-N-butyl imidazole ammonium or a copolymer thereof; the copolymer is prepared by copolymerizing N-vinyl-N-butyl imidazolium bromide and other alkenes.
2. The polyurethane material composition as claimed in claim 1, wherein the quaternary ammonium salt modified fluoroalkyl polyacrylate has a molecular weight of 2 to 3 ten thousand.
3. The polyurethane material composition as claimed in claim 1, wherein the polybrominated N-vinyl-N-butylimidazolium has a structure shown in formula (I), and the polybrominated N-vinyl-N-butylimidazolium copolymer is a polybrominated N-vinyl-N-butylimidazolium-N-vinylimidazole copolymer or a polybrominated N-vinyl-N-butylimidazolium-ethyl acrylate copolymer; the structural formula of the brominated N-vinyl-N-butylimidazolium-N-vinylimidazole copolymer is shown in a formula (II), and the structural formula of the brominated N-vinyl-N-butylimidazolium-ethyl acrylate copolymer is shown in a formula (III);
the molecular weight of the polybrominated N-vinyl-N-butylimidazolium or the copolymer thereof is 3000-5000, and the a is more than 0 and less than b.
4. The polyurethane material composition as claimed in claim 1, wherein the polyol is at least one of polyester polyol, polyether polyol and polycarbonate polyol; and/or the presence of a catalyst in the reaction mixture,
the isocyanate is selected from polyfunctional aliphatic, aromatic and alicyclic polyisocyanates; and/or the presence of a catalyst in the reaction mixture,
the chain extender is at least one of ethylene glycol, propylene glycol, diethylene glycol, 1, 4-butanediol and 1, 6-hexanediol.
5. The polyurethane material composition of claim 1, wherein the raw material A further comprises, in parts by weight:
1.5-2.0 parts of a catalyst; and/or the presence of a catalyst in the reaction mixture,
0.05-0.1 part of foaming agent; and/or the presence of a catalyst in the reaction mixture,
0.05-0.1 part of foam stabilizer.
6. The polyurethane material composition as claimed in claim 5, wherein the foaming agent is water; and/or the presence of a catalyst in the reaction mixture,
the foam stabilizer is an organosilicone surfactant.
7. A polyurethane shoe material, which is produced by using the polyurethane material composition according to any one of claims 1 to 6.
8. The polyurethane footwear according to claim 7, wherein the footwear is a sole.
9. The preparation method of the polyurethane shoe material is characterized by comprising the following steps:
1) drying 85-105 parts by weight of polyol and 110-115 parts by weight of isocyanate for later use;
2) drying 2-3 parts by weight of antistatic agent, and then adding polyol to mix uniformly;
3) sequentially adding 3-5 parts by weight of quaternary ammonium salt modified fluorocarbon finishing agent, 1.5-2.0 parts by weight of catalyst, 1-2 parts by weight of chain extender, 0.05-0.1 part by weight of foaming agent and 0.05-0.1 part by weight of foam stabilizer, and uniformly mixing to form a material A;
4) taking the dried isocyanate as a material B, and pouring the material A and the material B into a shoe material mold through a casting machine for molding to obtain the polyurethane shoe material;
the quaternary ammonium salt modified fluoroalkyl finishing agent is quaternary ammonium salt modified fluoroalkyl polyacrylate, and the structural formula of the quaternary ammonium salt modified fluoroalkyl polyacrylate is as follows:
n is1：n2：n3：n4＝(30～40)：(20～30)：(3～5)：1；
The antistatic agent is polybrominated N-vinyl-N-butyl imidazole ammonium or a copolymer thereof; the copolymer is prepared by copolymerizing N-vinyl-N-butyl imidazolium bromide and other alkenes.
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| CN114349922B (en) * | 2020-10-13 | 2024-01-23 | 浙江华峰新材料有限公司 | Flexible dual-cured resin composition and preparation method of molded body thereof |
| CN114057972A (en) * | 2021-11-24 | 2022-02-18 | 奎克静电防护科技(苏州)有限公司 | Preparation method of polyurethane material for anti-static shoes |
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