CN110041485A - A kind of aqueous acid and alkali-resistance polyurethane resin and its preparation method and application method - Google Patents

A kind of aqueous acid and alkali-resistance polyurethane resin and its preparation method and application method Download PDF

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CN110041485A
CN110041485A CN201910260893.6A CN201910260893A CN110041485A CN 110041485 A CN110041485 A CN 110041485A CN 201910260893 A CN201910260893 A CN 201910260893A CN 110041485 A CN110041485 A CN 110041485A
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alkali
polyurethane resin
aqueous acid
parts
resistance
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鲁明友
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Zhejiang Chengxun New Materials Co Ltd
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Zhejiang Chengxun New Materials Co Ltd
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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    • 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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    • C08G18/30—Low-molecular-weight compounds
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    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
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    • C08G18/3234—Polyamines cycloaliphatic
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    • C08G18/30—Low-molecular-weight compounds
    • C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
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    • C08G18/48—Polyethers
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    • 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
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
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    • 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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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
    • D06N3/0061—Organic fillers or organic fibrous fillers, e.g. ground leather waste, wood bark, cork powder, vegetable flour; Other organic compounding ingredients; Post-treatment with organic compounds
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    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
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    • D06N3/0063—Inorganic compounding ingredients, e.g. metals, carbon fibres, Na2CO3, metal layers; Post-treatment with inorganic compounds
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    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
    • D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
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Abstract

The invention discloses a kind of aqueous acid and alkali-resistance polyurethane resin and its preparation method and application methods.Aqueous acid and alkali-resistance polyurethane resin includes following components: polyalcohol, polyisocyanates, acetone, amine chain extender, hydrophilic chain extender, glycol chain extender, catalyst, deionized water, levelling agent, thickener；Hydrophilic chain extender is made of chain extender, crosslinking agent and the hydroxy silicon oil that mass ratio is 1:0.6-0.9:0.3-0.6；Chain extender is one of dihydromethyl propionic acid, dimethylolpropionic acid or dihydroxy half ester；Crosslinking agent is one of glycerol or trimethylolpropane.Preparation method are as follows: S1, performed polymer synthesis；S2, chain extending reaction；S3, water dispersion；S4, viscosity adjustment.Aqueous acid and alkali-resistance polyurethane resin of the invention can be used for preparing synthetic leather and artificial leather, have the advantages that water resistance, acid-proof alkaline and good mechanical performance.

Description

A kind of aqueous acid and alkali-resistance polyurethane resin and its preparation method and application method
Technical field
The present invention relates to polyurethane resin technical fields, more specifically, it relates to a kind of aqueous acid and alkali-resistance polyurethane tree Rouge and its preparation method and application method.
Background technique
Polyurethane (PU) refers to the high polymer polyurethane for containing a large amount of carbamate groups (- NHCOO-) on main chain The abbreviation of ester (Polyurethane).Because it shows excellent physical and chemical performance, it is widely used in synthetic leather, artificial Industry is removed from office, is a kind of multifunctional polymer material, becomes indispensable one kind high molecular material in socio-economic development.
Use for synthetic leather polyurethane resin is divided into oiliness polyurethane resin and waterborne polyurethane resin.Oiliness polyurethane resin is High polymer polyurethanes is dissolved in the organic solvents such as dimethylformamide (DMF), toluene and is obtained.Waterborne polyurethane resin is High polymer polyurethanes is dispersed in water and is made.In current synthetic leather enterprise, 95% or more still using oil Property polyurethane resin producer fabricate-leather, synthetic leather, use waterborne polyurethane resin system small-scale only less than 5% enterprise Make synthetic leather.
The preparation method of existing aqueous polyurethane is that oligomer polyol and diisocyanate is anti-at a certain temperature Base polyurethane prepolymer for use as should be made；Then small molecule chain extender is added and carries out chain extending reaction；Adding hydrophilic chain extender makes pre-polymerization Body becomes hydrophilic prepolymer body；Neutralization reaction is carried out with salt-forming reagent again, there is base polyurethane prepolymer for use as ionic；This is had Ionic base polyurethane prepolymer for use as adds water dispersion to emulsify；Chain extending reaction after small molecule chain extender carries out in water is added, water is made Property polyurethane dispersing liquid.
On the one hand since aqueous polyurethane itself contains hydrophilic radical, lead to its poor water resistance, it is on the other hand aqueous poly- There are still a certain distance for the acid and alkali-resistance and mechanical property and solvent borne polyurethane of urethane, therefore develop a kind of water resistance, resistance to Acid-base property and the water soluble polyurethane resin of good mechanical performance are problems to be solved.
Summary of the invention
In view of the deficienciess of the prior art, the first purpose of this invention is to provide a kind of aqueous acid and alkali-resistance polyurethane Resin has the advantages that water resistance, acid-proof alkaline and good mechanical performance.
Second object of the present invention is to provide a kind of preparation method of aqueous acid and alkali-resistance polyurethane resin have behaviour The advantages of work is simple, production technology safety and environmental protection.
Third object of the present invention is to provide a kind of application method of aqueous acid and alkali-resistance polyurethane resin have behaviour The advantages of making simple, production technology safety and environmental protection, and leather peculiar smell can be adsorbed.
To realize above-mentioned first purpose, the present invention provides the following technical scheme that a kind of aqueous acid and alkali-resistance polyurethane tree Rouge comprises the following components in parts by weight: 25-30 parts of polyalcohols, 13-19 parts of polyisocyanates, 40-50 parts of acetone, 2-5 parts of amines Chain extender, 1.5-2.0 part hydrophilic chain extender, 14-18 parts of glycol chain extenders, 0.5-0.8 parts of catalyst, 70-100 parts go from Sub- water；
The hydrophilic chain extender is made of chain extender, crosslinking agent and the hydroxy silicon oil that mass ratio is 1:0.6-0.9:0.3-0.6；
The chain extender is one of dihydromethyl propionic acid, dimethylolpropionic acid or dihydroxy half ester；
The crosslinking agent is one of glycerol or trimethylolpropane.
By using above-mentioned technical proposal, obtained due to carrying out polymerization reaction using polyalcohol and polyisocyanates in synthesis Performed polymer, preparation principle are as follows: polyisocyanates and macromolecular polyol reaction generate base polyurethane prepolymer for use as, then and hydrophilic chain extender Reaction generates the performed polymer containing hydrophilic radical chain link, is reacted with it with acetone, and hydrophilic radical is transformed into corresponding salt ion, Water-wetness is more preferable；Polyurethane macromolecular is wrapped up, is dispersed in water by high speed dispersion again, hydrophilic radical ion, forms lotion Form, amine chain extension reagent activity with higher is diffused into emulsion colloidal, further after being added in the lotion to be formed It is reacted with the isocyanate groups of polyurethane end position, molecular weight further increases, and can be made aqueous poly- after finally removing diluent Urethane resin.
Catalyst can promote fully reacting to carry out, especially reaction temperature is low and the lower situation of polyisocyanic acid ester content Under, accelerate fully reacting to carry out, provides the hydrophilic radical of molecular resin using hydrophilic chain extender, carry out chain extending reaction, so that Aqueous structure is more stable, using one of dihydromethyl propionic acid, dimethylolpropionic acid or dihydroxy half ester as hydrophily chain extension The main component of agent, the glycerol or trimethylolpropane and hydroxy silicon oil of addition, polysiloxanes and pre-polymerization with active end group Organic silicon modified polyurethane copolymer is made by addition polymerization and chain extending reaction in body, overcomes organosiloxane and polyurethane phase The very poor problem of capacitive, by organic-silicon-modified waterborne polyurethane resin, so that single performed polymer is in acidproof potassium, heat-resisting quantity Etc. get a promotion, weatherability is preferable, satisfactory mechanical property.
Further, the polyalcohol is one of polytetrahydrofuran diol, polyethylene glycol, polypropylene glycol or a variety of Composition.
Further, the polyisocyanates be selected from isophorone diisocyanate, Toluene-2,4-diisocyanate, 4- diisocyanate, 1, The composition of one or more of 6- hexamethylene diisocyanate.
Further, the amine chain extender is ethylenediamine, triethylene tetramine, 2- methyl-1,5- pentanediamine, isophorone One of diamines, hexamethylene diamine, 1,3- butanediamine, diethylenetriamine.
Further, the glycol chain extender is one of 1,4-butanediol, ethylene glycol, propylene glycol.
Further, the catalyst is one of stannous octoate, dibutyl tin dilaurate.
To realize above-mentioned second purpose, the present invention provides the following technical scheme that a kind of aqueous acid and alkali-resistance polyurethane tree The preparation method of rouge, comprising the following steps:
S1, performed polymer synthesis: polyalcohol and polyisocyanates are added in reaction kettle, be added catalyst, glycol chain extender and 2/3 amine chain extender, under vacuum conditions, control reaction temperature are 108-112 DEG C, react 1-2h, are cooled to 80-85 DEG C, 2-3h is reacted, performed polymer is made；
S2, chain extending reaction: hydrophilic chain extender being added into performed polymer, reacts 3-4h at 65-85 DEG C, is cooled to 25-45 DEG C, adds Enter acetone dilution, until nco value is down to 1.2-2.2% (weight), organic silicon modified polyurethane performed polymer is made；
S3, water dispersion: adjusting temperature of reaction kettle is 0-20 DEG C, and deionized water is added, and is turning for 1400-1800r/min in revolving speed Under speed, disperse 30-40min, the amine chain extender of surplus is then added, and in 50-60 DEG C, -0.04 to -0.08MPa item It is evaporated under reduced pressure 4-5h under part, aqueous polyurethane emulsion is made；
S4, viscosity adjustment: being added thickener and levelling agent in hydrotropism's polyaminoester emulsion, adjustment viscosity is 2000-4000cps/ 20℃。
By using above-mentioned technical proposal, by polyalcohol and polyisocyanates in comfortable DEG C of 108-112 reaction 1-2 hours, The reaction time is appropriately extended, keeps active hydrogen of the NCO group of polyisocyanates sufficiently and in polyalcohol, hydrophilic chain extender anti- It answers, reduces the amount for the NCO group that emulsification Shi Yushui reacts, the biggish aqueous polyurethane of butterfly molecular weight；
Organic silicon modified polyurethane performed polymer and water are subjected to high-speed stirred, dispersion and emulsion, and are down to 1.2-2.2% in nco value Hydrophilic chain extender is added before (weight), and reduces temperature, advantageously reduces the reactivity of NCO group and water, makes NCO base Chain extending reaction after group preferably occurs with amine chain extender, and since amine chain extender is with active hydrogen, at high temperature with NCO base Group's reactivity is high, and reaction acutely, is conducive to control reaction at low temperature；Extend vacuum distillation the time, be conducive to NCO group with Amine chain extender is sufficiently reacted, and the amount of free state isocyano in lotion is reduced, to improve the stability of polyaminoester emulsion.
To realize above-mentioned third purpose, the present invention provides the following technical scheme that a kind of aqueous acid and alkali-resistance polyurethane tree Application method of the rouge in synthetic leather and artificial leather industry.
Further, specifically includes the following steps:
(1) in the base fabric for handling by base fabric and plating through ironing roller, aqueous acid and alkali-resistance polyurethane tree is coated using knife coating Rouge internal layer slurry, coated weight 300-600g/m2, at 120-150 DEG C, linear speed is dried under conditions of being 3-5m/min, obtains water Property Synthetic Leather bass；
The aqueous acid and alkali-resistance polyurethane resin internal layer slurry is prepared from following methods: 60-70 parts being added into reaction kettle 0.1-0.8 parts of dispersing agents, 5-10 parts of polypropylene powders and 1-10 parts of talcums are added in aqueous acid and alkali-resistance polyurethane resin while stirring Powder is dispersed with stirring 30-40min under conditions of 1000-1300r/min, and 1-3 parts of thickeners, 5-10 parts of carbon fibers and 1-3 is added Part foam stabilizer, stirs 5-10min under conditions of 600-1000r/min, aqueous acid and alkali-resistance polyurethane resin internal layer slurry is made；
(2) aqueous acid and alkali-resistance polyurethane resin surface layer slurry is coated using knife coating on water-soluble polyurethane leather beth again, Coated weight is 30-50g/m2, it is dry under conditions of 150-180 DEG C, with the smooth processing of felt wrapped roll, then successively by cutting out, examining It tests and winding process, synthetic leather or artificial leather is made；
Aqueous acid and alkali-resistance polyurethane resin surface layer slurry is made of following methods: taking 80-100 parts of aqueous acid and alkali-resistance polyurethane resins Be added reaction kettle in, while stirring be added 3-5 parts of levelling agents, 0.1-0.3 parts of organic silicon defoamers, 0.2-0.6 parts of wetting agents, 0.5-1.1 parts of active carbons, 1-5 parts of basic zirconium phosphates carry silver powder, 2-4 parts of nano zine oxides, 0.5-1.5 parts of tourmaline powders, then in 600- 1-3 parts of thickeners, 1-5 parts of lavender extracting solutions are added under the revolving speed of 1200r/min, so that viscosity is 2500-3500mpa.s.
By using above-mentioned technical proposal, there is no any organic solvent during preparing synthetic leather or artificial leather, nothing has Solvent pollution and residual, and aqueous acid and alkali-resistance polyurethane resin internal layer slurry is dispersed using dispersing agent, make to be coated in Internal layer slurry in base fabric is more uniform, at the same inside the carbon fiber added special ultrafine micropore structure make it have it is powerful Adsorption capacity can adsorb bacterium, peculiar smell etc., and adsorption effect is good, effectively antibacterial, can adsorb synthetic leather or artificial leather manufactured Cheng Zhong, the peculiar smell that aqueous acid and alkali-resistance polyurethane resin volatilizes；Because aqueous acid and alkali-resistance polyurethane resin surface layer slurry is coated with Meeting and human contact, addition has the active carbon of adsorption function in the slurry of surface layer, can adsorb aqueous acid and alkali-resistance polyurethane tree The peculiar smell of rouge, and lavender extracting solution has special fragrance, is coated on water-soluble polyurethane leather beth, can make to synthesize Leather or artificial leather have good smell, avoid synthetic leather or artificial leather when producing, volatilize pungent smell, the stream of addition Flat agent can increase the finish and flatness of leather surface, leather quality be improved, while active carbon can adsorb, because of active carbon Content it is higher than the content of lavender extracting solution, therefore the smell that Herba Lysimachiae foenumgraeci extract volatilizes will not be inhaled by active carbon completely It is attached, and active carbon is first added and is stirred, active carbon first adsorbs the peculiar smell that aqueous acid and alkali-resistance polyurethane resin volatilizes, and adds When Herba Lysimachiae foenumgraeci extract, the fragrance of Herba Lysimachiae foenumgraeci extract will not be tightly held by activated carbon completely；Tourmaline powder can generate anion, Air can be purified, avoid the smell that thick air is pungent, zinc oxide and basic zirconium phosphate carry silver powder can sterilizing, avoid leather Upper growth bacterium.
Further, the thickener is one of alkali swelling type acrylic thickener or polyurethane associative thickener Or two kinds of composition.
By using above-mentioned technical proposal, alkali swelling type acrylic type thickener and polyurethane associative thickener have height The thickening efficiency of effect can improve the mobility and flow leveling of internal layer slurry and outer layer slurry, improve internal layer slurry and outer layer The anti-splash of slurry.
In conclusion the invention has the following advantages:
The first, since the present invention is using the modification for being used for polyurethane using organosilicon, because the Si-O-Si key in strand has There is biggish cohesive energy and there are the excellent performances such as high temperature resistant, hydrolysis, and the chain belongs to flexible chain, there is low-temperature flexibility Well, the advantages that low surface tension, good biocompatibility, it can be improved the mechanical performance of aqueous polyurethane, use with dihydroxymethyl One of propionic acid, dimethylolpropionic acid or dihydroxy half ester be hydrophilic chain extender in main component, and add glycerol or Trimethylolpropane and hydroxy silicon oil, polysiloxanes with active end group and performed polymer are by polymerize and chain extending reaction is obtained has Machine silicon modified polyurethane copolymer overcomes organosiloxane and the very poor problem of polyurethane compatibility, to improve aqueous poly- The mechanical performance of urethane resin, water resistance and weatherability；Acetone dilution is added before emulsification, for reducing in synthesis process and before cream The viscosity of performed polymer, amine chain extender can further increase the molecular weight of resin, improve resin mechanical performance.
The second, decentralized medium is done using water due to the present invention, is not necessarily to organic solvent in process, no pollution to the environment, To operator without health hazard, waterborne polyurethane resin smell is small, nonflammable, and resistance to acid and alkali is good, good mechanical performance, phase Capacitive is good, and process is safe and reliable, and makes aqueous polyurethane system viscosity unrelated with polyurethane resin molecular weight, and than solid The identical solvent borne polyurethane solution viscosity of content is low, and processing is more convenient, easy to operate.
It is compounded in third, the present invention using thickener and levelling agent, so that waterborne polyurethane resin reaches use for synthetic leather and gathers The performance requirement of urethane uses thickener that the charge on polyurethane particles surface can be made to make particle ordered arrangement, and degree of alignment is not Together, the thixotropic intensity of system is also different, and the branch of thickener molecule is mutually wound with polyurethane molecular, crosslinks reaction And network structure is generated, so that the phenomenon that improving the viscosity of polyurethane, preventing sagging and penetrate into, mutually compounds with levelling agent It uses, the surface tension of aqueous polyurethane emulsion can be reduced, improve mobility.
4th, using carbon fiber and aqueous acid and alkali-resistance polyurethane resin prepare internal layer slurry in the present invention, using active carbon, Herba Lysimachiae foenumgraeci extract makes surface layer slurry, can make synthetic leather and the non-volatile pungent smell of artificial leather obtained, and smoke clothing The fragrance of grass, while the tourmaline powder added in the slurry of surface layer has the function of that the anion that volatilizees, anion can purify sky Gas, eliminates the sharp aroma of leather surface, zinc oxide and basic zirconium phosphate carry silver powder can sterilizing, avoid artificial leather or synthetic leather Breed bacterium.
Specific embodiment
Invention is further described in detail with reference to embodiments.
The preparation example 1-3 of aqueous acid and alkali-resistance polyurethane resin internal layer slurry
Alkali swelling type acrylic type thickener is selected from the article No. that sanda chemical industry (Nantong) Co., Ltd sells in preparation example 1-3 TT-935 alkali swelling type acrylic type thickener, polyurethane associative thickener are selected from Guangzhou Guan Zhi new material Science and Technology Ltd. The article No. of sale is the polyurethane associative thickener of OS-8W, and dispersing agent is selected from five colored stone new material (Hangzhou) Co., Ltds and goes out The dispersing agent of the model WSS-190 sold, carbon fiber are selected from the article No. that Shanghai Li Shuo composite material Science and Technology Ltd. sells and are 017 carbon fiber, foam stabilizer are selected from the FM-550 type foam stabilizer that one hundred deep new material Co., Ltd sells, and polypropylene powder is selected from Suzhou The trade mark that the emerging plasticizing trade Co., Ltd of reputation inscription sells is H-HD-300.Polypropylene powder, talcum powder be selected from Hebei capital Hangzhoupro mineral products The article No. that product Co., Ltd sells is the talcum powder of HS-1250.
Preparation example 1: the aqueous acid and alkali-resistance polyurethane resin of 60kg being added into reaction kettle, and 0.1kg dispersion is added while stirring Agent, 5kg polypropylene powder and 1kg talcum powder are dispersed with stirring 30min under conditions of 1000r/min, and 1kg thickener, 5kg is added Carbon fiber and 1kg foam stabilizer, stir 5min under conditions of 600r/min, and aqueous acid and alkali-resistance polyurethane resin internal layer slurry is made Material.
Preparation example 2: the aqueous acid and alkali-resistance polyurethane resin of 65kg being added into reaction kettle, and 0.4kg dispersion is added while stirring Agent, 8kg polypropylene powder and 5kg talcum powder are dispersed with stirring 35min under conditions of 1200r/min, and 2kg thickener, 8kg is added Carbon fiber and 2kg foam stabilizer, stir 8min under conditions of 800r/min, and aqueous acid and alkali-resistance polyurethane resin internal layer slurry is made Material.
Preparation example 3: the aqueous acid and alkali-resistance polyurethane resin of 70kg being added into reaction kettle, and 0.8kg dispersion is added while stirring Agent, 10kg polypropylene powder and 10kg talcum powder, are dispersed with stirring 40min under conditions of 1300r/min, be added 3kg thickener, 10kg carbon fiber and 3kg foam stabilizer, stir 10min under conditions of 1000r/min, are made in aqueous acid and alkali-resistance polyurethane resin Layer slurry.
The preparation example 4-6 of aqueous acid and alkali-resistance polyurethane resin surface layer slurry
Levelling agent is selected from the levelling agent for the model SP-934 that Dongguan City Bo Cheng Chemical Co., Ltd. sells in preparation example 4-6, has Machine silicon defoaming agent is selected from the organic silicon defoamer for the model Z-3724 that ten thousand new material Co., Ltd of Shanghai Guangdong sells, wetting agent choosing The wetting agent of the model CF-10 sold from Jitian Chemical Co., Ltd., Shenzhen, tourmaline powder are selected from Shijiazhuang nation, China mineral products The article No. that product Co., Ltd sells is the tourmaline powder of hb-dqs, and lavender extracting solution is selected from Guangzhou Wen Ling trade Co., Ltd and goes out The lavender extracting solution that the article No. sold is 0366, alkali swelling type acrylic type thickener are selected from sanda chemical industry (Nantong) Co., Ltd The article No. of sale is TT-935 alkali swelling type acrylic type thickener, and polyurethane associative thickener is selected from Guangzhou and is preced with will new material The article No. that Science and Technology Ltd. sells is the polyurethane associative thickener of OS-8W.
Preparation example 4: taking the aqueous acid and alkali-resistance polyurethane resin of 80kg to be added in reaction kettle, be added while stirring 3kg levelling agent, 0.1kg organic silicon defoamer, 0.2kg wetting agent, 0.5kg active carbon, 1kg basic zirconium phosphate carry silver powder, 2kg nano zine oxide, 0.5kg Tourmaline powder, then 1kg thickener, 1kg lavender extracting solution are added under the revolving speed of 600r/min, so that viscosity is The partial size that 2500mpa.s, active carbon and basic zirconium phosphate carry silver powder is 5 μm, and the partial size of nano zine oxide is 10nm.
Preparation example 5: taking the aqueous acid and alkali-resistance polyurethane resin of 90kg to be added in reaction kettle, be added while stirring 4kg levelling agent, 0.2kg organic silicon defoamer, 0.4kg wetting agent, 0.8kg active carbon, 3kg basic zirconium phosphate carry silver powder, 3kg nano zine oxide, 1.0kg Tourmaline powder, then 2kg thickener, 3kg lavender extracting solution are added under the revolving speed of 800r/min, so that viscosity is The partial size that 3000mpa.s, active carbon and basic zirconium phosphate carry silver powder is 8 μm, and the partial size of nano zine oxide is 15nm.
Preparation example 6: it takes the aqueous acid and alkali-resistance polyurethane resin of 100kg to be added in reaction kettle, 5kg levelling is added while stirring Agent, 0.3kg organic silicon defoamer, 0.6kg wetting agent, 1.1kg active carbon, 5kg basic zirconium phosphate carry silver powder, 4kg nano zine oxide, 1.5kg tourmaline powder, then 3kg thickener, 5kg lavender extracting solution are added under the revolving speed of 1200r/min, so that viscosity is The partial size that 3500mpa.s, active carbon and basic zirconium phosphate carry silver powder is 10 μm, and the partial size of nano zine oxide is 20nm.
Embodiment
It is organic to be selected from the WNS-9502 type that this Industrial Co., Ltd. of Guangdong China sodium sells for organic siliconresin in following embodiment Silicone resin, dibutyl tin dilaurate are selected from the dibutyl tin osmanthus that the article No. that Hai Yuan Chemical Co., Ltd. in Jinan sells is T12 Sour tin, cellulose ether are selected from the QH6011 fiber type element ether that Shanghai is admired and Chemical Co., Ltd. sells, the choosing of butyl acetate cellulose From the butyl acetate cellulose for being 381-2 along the article No. that industrial chemicals business department sells selected from Jize County China, polyvinylpyrrolidine Ketone is selected from the polyvinylpyrrolidone for the model PVPK30 that Yue Mei Chemical Co., Ltd. in Guangdong sells, and nitrocellulose is selected from Guangzhou The nitrocellulose that the article No. that Ying Hong Chemical Co., Ltd., city sells is 1994, it is limited that hydroxy silicon oil is selected from Jiashan Jiangnan textile material The JF-203 type hydroxy silicon oil that company sells, trimethylolpropane are selected from the article No. that 100,000 Chemical Co., Ltd. of Shandong sells and are The trimethylolpropane of 77-99-6.
Embodiment 1: a kind of aqueous acid and alkali-resistance polyurethane resin, raw material proportioning is as shown in table 1, preparation method include with Lower step:
S1, performed polymer synthesis: 25kg polytetrahydrofuran diol and 13kg isophorone diisocyanate are added in reaction kettle, added Enter 0.5kg stannous octoate, 14kg1,4- butanediol and 1.3kg ethylenediamine, under vacuum conditions, control reaction temperature is 108 DEG C, 1h is reacted, is cooled to 80 DEG C, reacts 2h, performed polymer is made；
S2, chain extending reaction: 1.5kg hydrophilic chain extender being added into performed polymer, reacts 3h at 65 DEG C, is cooled to 25 DEG C, is added Organic silicon modified polyurethane performed polymer is made until nco value is down to 1.2% (weight) in the dilution of 40kg acetone；
Wherein dihydromethyl propionic acid, trimethylolpropane and hydroxy silicon oil group that hydrophilic chain extender is 1:0.6:0.3 by mass ratio At,
S3, water dispersion: adjusting temperature of reaction kettle is 0 DEG C, and 70kg deionized water is added, in the case where revolving speed is the revolving speed of 1400r/min, Disperse 30min, 0.7kg ethylenediamine is then added, and be evaporated under reduced pressure 4h under conditions of 50 DEG C, -0.04MPa, is made aqueous poly- Urethane lotion；
S4, viscosity adjustment: being added 1kg thickener and 3kg levelling agent in hydrotropism's polyaminoester emulsion, adjustment viscosity is 2000cps/ 20 DEG C, wherein levelling agent is polyacrylate, and thickener is cellulose ether.
The application method of above-mentioned aqueous acid and alkali-resistance polyurethane resin is as follows:
(1) in the base fabric for handling by base fabric and plating through ironing roller, aqueous acid and alkali-resistance polyurethane tree is coated using knife coating Rouge internal layer slurry, coated weight 300g/m2, at 120 DEG C, linear speed is dried under conditions of being 3m/min, obtains aqueous polyurethane conjunction Finished leather bass, aqueous acid and alkali-resistance polyurethane resin internal layer slurry are prepared by preparation example 1；
(2) aqueous acid and alkali-resistance polyurethane resin surface layer slurry is coated using knife coating on water-soluble polyurethane leather beth again, Coated weight is 30g/m2, it is dry under conditions of 150 DEG C, with the smooth processing of felt wrapped roll, then successively by cutting out, examining and winding Technique, is made synthetic leather or artificial leather, aqueous acid and alkali-resistance polyurethane resin surface layer slurry are prepared by preparation example 4.
The raw material proportioning of aqueous acid and alkali-resistance polyurethane resin in 1 embodiment 1-4 of table
Embodiment 2: a kind of aqueous acid and alkali-resistance polyurethane resin, raw material proportioning is as shown in table 1, and preparation method includes following step It is rapid:
S1, performed polymer synthesis: by 26kg polyethylene glycol and 15kg Toluene-2,4-diisocyanate, 4- diisocyanate is added in reaction kettle, is added 0.6kg dibutyl tin dilaurate, 14kg ethylene glycol and 2kg triethylene tetramine, under vacuum conditions, control reaction temperature is 110 DEG C, 1.4h is reacted, is cooled to 82 DEG C, reacts 2.4h, performed polymer is made；
S2, chain extending reaction: 1.6kg hydrophilic chain extender is added into performed polymer, reacts 3.4h at 75 DEG C, is cooled to 35 DEG C, adds Enter the dilution of 43kg acetone, until nco value is down to 1.8% (weight), organic silicon modified polyurethane performed polymer is made；
Wherein dimethylolpropionic acid, trimethylolpropane and hydroxy silicon oil group that hydrophilic chain extender is 1:0.7:0.4 by mass ratio At,
S3, water dispersion: adjusting temperature of reaction kettle is 10 DEG C, and 80kg deionized water is added, in the revolving speed that revolving speed is 1500r/min Under, disperse 34min, 1kg triethylene tetramine is then added, and be evaporated under reduced pressure 4.4h under conditions of 54 DEG C, -0.06MPa, is made Aqueous polyurethane emulsion；
S4, viscosity adjustment: being added 1.5kg thickener and 3kg levelling agent in hydrotropism's polyaminoester emulsion, adjustment viscosity is 2500cps/20 DEG C, wherein levelling agent is organic siliconresin, and thickener is cellulose ether.
The application method of above-mentioned aqueous acid and alkali-resistance polyurethane resin is as follows:
(1) in the base fabric for handling by base fabric and plating through ironing roller, aqueous acid and alkali-resistance polyurethane tree is coated using knife coating Rouge internal layer slurry, coated weight 400g/m2, at 130 DEG C, linear speed is dried under conditions of being 4m/min, obtains aqueous polyurethane conjunction Finished leather bass, aqueous acid and alkali-resistance polyurethane resin internal layer slurry are prepared by preparation example 2；
(2) aqueous acid and alkali-resistance polyurethane resin surface layer slurry is coated using knife coating on water-soluble polyurethane leather beth again, Coated weight is 40g/m2, it is dry under conditions of 160 DEG C, with the smooth processing of felt wrapped roll, then successively by cutting out, examining and winding Technique, is made synthetic leather or artificial leather, aqueous acid and alkali-resistance polyurethane resin surface layer slurry are prepared by preparation example 5.
Embodiment 3: a kind of aqueous acid and alkali-resistance polyurethane resin, raw material proportioning is as shown in table 1, preparation method include with Lower step:
S1, performed polymer synthesis: by 28kg polypropylene glycol and 17kg1,6- hexamethylene diisocyanate is added in reaction kettle, is added 0.7kg stannous octoate, 17kg propylene glycol and 2.6kg2- methyl-1,5- pentanediamine, under vacuum conditions, control reaction temperature is 111 DEG C, 1.7h is reacted, is cooled to 84 DEG C, reacts 2.4h, performed polymer is made；
S2, chain extending reaction: 1.8kg hydrophilic chain extender is added into performed polymer, reacts 3.7h at 70 DEG C, is cooled to 40 DEG C, adds Enter the dilution of 46kg acetone, until nco value is down to 2.0% (weight), organic silicon modified polyurethane performed polymer is made；
Wherein hydrophilic chain extender is made of dihydroxy half ester, glycerol and the hydroxy silicon oil that mass ratio is 1:0.8:0.5,
S3, adjusting temperature of reaction kettle are 15 DEG C, and 90kg deionized water is added, in the case where revolving speed is the revolving speed of 1600r/min, dispersion Then 37min is added 1.4kg2- methyl-1,5- pentanediamine, and is evaporated under reduced pressure 4.7h under conditions of 57 DEG C, -0.07MPa, make Obtain aqueous polyurethane emulsion；
S4, viscosity adjustment: being added 2kg thickener and 4kg levelling agent in hydrotropism's polyaminoester emulsion, adjustment viscosity is 2800cps/ 20 DEG C, wherein levelling agent is butyl acetate cellulose, and thickener is polyvinylpyrrolidone.
The application method of above-mentioned aqueous acid and alkali-resistance polyurethane resin is as follows:
(1) in the base fabric for handling by base fabric and plating through ironing roller, aqueous acid and alkali-resistance polyurethane tree is coated using knife coating Rouge internal layer slurry, coated weight 500g/m2, at 140 DEG C, linear speed is dried under conditions of being 5m/min, obtains aqueous polyurethane conjunction Finished leather bass, aqueous acid and alkali-resistance polyurethane resin internal layer slurry are prepared by preparation example 3；
(2) aqueous acid and alkali-resistance polyurethane resin surface layer slurry is coated using knife coating on water-soluble polyurethane leather beth again, Coated weight is 50g/m2, it is dry under conditions of 170 DEG C, with the smooth processing of felt wrapped roll, then successively by cutting out, examining and winding Technique, is made synthetic leather or artificial leather, aqueous acid and alkali-resistance polyurethane resin surface layer slurry are prepared by preparation example 6.
Embodiment 4: a kind of aqueous acid and alkali-resistance polyurethane resin, raw material proportioning is as shown in table 1, preparation method include with Lower step:
S1, performed polymer synthesis: 30kg polytetrahydrofuran diol and 19kg isophorone diisocyanate are added in reaction kettle, added Enter 0.8kg stannous octoate, 18kg1,4- butanediol and 3.3kg isophorone diamine, under vacuum conditions, control reaction temperature is 112 DEG C, 2h is reacted, is cooled to 85 DEG C, reacts 3h, performed polymer is made；
S2, chain extending reaction: 2kg hydrophilic chain extender being added into performed polymer, reacts 4h at 85 DEG C, is cooled to 45 DEG C, is added Organic silicon modified polyurethane performed polymer is made until nco value is down to 2.2% (weight) in the dilution of 60kg acetone；
Wherein hydrophilic chain extender is made of dihydromethyl propionic acid, glycerol and the hydroxy silicon oil that mass ratio is 1:0.9:0.6,
S3, water dispersion: adjusting temperature of reaction kettle is 20 DEG C, and 100kg deionized water is added, in the revolving speed that revolving speed is 1800r/min Under, disperse 40min, 1.7kg isophorone diamine is then added, and be evaporated under reduced pressure 5h under conditions of 60 DEG C, -0.08MPa, makes Obtain aqueous polyurethane emulsion；
S4, viscosity adjustment: being added 3kg thickener and 5kg levelling agent in hydrotropism's polyaminoester emulsion, adjustment viscosity is 4000cps/ 20 DEG C, wherein levelling agent is the nitrocellulose and polyacrylate that mass ratio is 1:1, and thickener is the fiber that mass ratio is 1:2 Plain ether and polyvinylpyrrolidone.
The application method of above-mentioned aqueous acid and alkali-resistance polyurethane resin is as follows:
(1) in the base fabric for handling by base fabric and plating through ironing roller, aqueous acid and alkali-resistance polyurethane tree is coated using knife coating Rouge internal layer slurry, coated weight 600g/m2, at 150 DEG C, linear speed is dried under conditions of being 5m/min, obtains aqueous polyurethane conjunction Finished leather bass, aqueous acid and alkali-resistance polyurethane resin internal layer slurry are prepared by preparation example 3；
(2) aqueous acid and alkali-resistance polyurethane resin surface layer slurry is coated using knife coating on water-soluble polyurethane leather beth again, Coated weight is 50g/m2, it is dry under conditions of 180 DEG C, with the smooth processing of felt wrapped roll, then successively by cutting out, examining and winding Technique, is made synthetic leather or artificial leather, aqueous acid and alkali-resistance polyurethane resin surface layer slurry are prepared by preparation example 6.
Comparative example
Comparative example 1: a kind of aqueous acid and alkali-resistance polyurethane resin, the difference from embodiment 1 is that, it is not added in hydrophilic chain extender Dihydromethyl propionic acid.
Comparative example 2: a kind of aqueous acid and alkali-resistance polyurethane resin, the difference from embodiment 1 is that, in hydrophilic chain extender not Add trimethylolpropane.
Comparative example 3: a kind of aqueous acid and alkali-resistance polyurethane resin, the difference from embodiment 1 is that, in hydrophilic chain extender not Add hydroxy silicon oil.
Comparative example 4: a kind of aqueous acid and alkali-resistance polyurethane resin, the difference from embodiment 1 is that, two are not added in hydrophily Hydroxymethyl propionic acid and trimethylolpropane.
Comparative example 5: a kind of aqueous acid and alkali-resistance polyurethane resin, the difference from embodiment 1 is that, two are not added in hydrophily Hydroxymethyl propionic acid and hydroxy silicon oil.
Comparative example 6: a kind of aqueous acid and alkali-resistance polyurethane resin, the difference from embodiment 1 is that, three are not added in hydrophily Hydroxymethyl-propane and hydroxy silicon oil.
Performance detection test
One, the Mechanics Performance Testing of aqueous acid and alkali-resistance polyurethane resin: according to the method system in embodiment 1-4 and comparative example 1-6 Standby aqueous acid and alkali-resistance polyurethane resin, it is referring to the method in GB/T1727-1992 " general preparation method of paint film " that resin is newborn Liquid is coated on tinplate, is placed in 60 DEG C of baking oven and is toasted film forming, 24 hours dry, glue film of tearing, and is carried out such as to it Lower test, test result are as shown in table 2:
1, it pencil hardness: is tested according to GB/T6739-2006 " paint and varnish pencil method measures hardness of paint film "；
2, it wearability: is tested according to GB/T23988-2009 " coating wearability measures knockout method "；
3, it glossiness: is tested according to GB/T1743-1979 " gloss of film measuring method "；
4, it storage stability: is tested referring to GB/T67533-1986 " coating storage stability test method "；
5, it breaking strength: is carried out according to GB/T13022-1991 " test method of stretched plastic film performance "
6, it tearing strength: is tested according to GB/T529-1999 " measurement of vulcanized rubber or thermoplastic elastomer tearing strength ":
7, it elongation: is tested according to GB/T528-1992 " measurement of vulcanized rubber and thermoplastic elastomer tensile property ":
The test result of aqueous acid and alkali-resistance polyurethane resin made from each embodiment of table 2 and each comparative example
According to the resistance to pencil hardness of aqueous acid and alkali-resistance polyurethane resin made from embodiment 1-4 it can be seen from data in table 2 Height, and wearability is preferable, glossiness is good, and storage time is long, good mechanical performance.
Comparative example 1 because being not added with dihydromethyl propionic acid in hydrophilic chain extender, the polyurethane resin as made from comparative example 1 Hardness and wearability are poor compared with Example 1, and occur stale flavor in 6 months, and retention cycle is shorter, breaking strength, Extensibility and tearing strength differ larger compared with Example 1, illustrate that dihydromethyl propionic acid can be improved the poly- ammonia of aqueous acid and alkali-resistance The mechanical property and retention cycle of ester resin.
Comparative example 2 is because being not added with trimethylolpropane in hydrophilic chain extender, by comparing it can be seen from data in table 2 The properties of aqueous acid and alkali-resistance polyurethane resin made from example 2 are poor compared with Example 1, illustrate trimethylolpropane energy Enough improve mechanical property, pencil hardness, glossiness and the retention cycle of aqueous acid and alkali-resistance polyurethane resin.
Comparative example 3 because being not added with hydroxy silicon oil in hydrophilic chain extender, the waterborne polyurethane resin as made from comparative example 3 Pencil hardness, glossiness and wearability are greatly different larger compared with Example 1, and keep having within 6 months stale flavor, mechanical property compared with Difference, when illustrating that hydroxy silicon oil can be improved mechanical property, wear-resisting property, glossiness and the storage of aqueous acid and alkali-resistance polyurethane resin Between.
Comparative example 4 is because being not added with dihydromethyl propionic acid and trimethylolpropane simultaneously in hydrophilic chain extender, by comparative example 4 The properties of waterborne polyurethane resin obtained are poor compared with embodiment 1, comparative example 1 and comparative example 2, illustrate simultaneously Use dihydromethyl propionic acid and trimethylolpropane as hydrophilic chain extender, can be improved aqueous acid and alkali-resistance polyurethane resin Pencil hardness, wearability, storage time and mechanical property.
Comparative example 5 is made because being not added with dihydromethyl propionic acid and hydroxy silicon oil simultaneously in hydrophilic chain extender by comparative example 5 Aqueous acid and alkali-resistance polyurethane resin aqueous acid and alkali-resistance polyurethane resin obtained compared with embodiment 1, comparative example 1 and comparative example 3 It compares, either pencil hardness, wear-resisting property, breaking strength, elongation and tearing strength, it is poor, illustrate while using two Hydroxymethyl propionic acid and hydroxy silicon oil as hydrophilic chain extender, can be improved aqueous acid and alkali-resistance polyurethane resin pencil hardness, Wearability, mechanical property and storage time.
Comparative example 6 is aqueous made from comparative example 6 because being not added with trimethylolpropane and hydroxy silicon oil in hydrophilic chain extender The properties of acid and alkali-resistance polyurethane resin are poor compared with Example 1, and with it is aqueous made from comparative example 2 and comparative example 3 Acid and alkali-resistance polyurethane resin is compared, and properties are also not as good as aqueous acid and alkali-resistance polyurethane tree made from comparative example 2 and comparative example 3 Rouge illustrates while using trimethylolpropane and hydroxy silicon oil, and mechanical property, the pencil that can be improved waterborne polyurethane resin are hard Degree, wearability, glossiness and storage time.
Two, aqueous acid and alkali-resistance polyurethane resin water resistance and acid-proof alkaline test: according to embodiment 1-4 and comparative example 1- Method in 6 prepares aqueous acid and alkali-resistance polyurethane resin, referring to the side in GB/T1727-1992 " general preparation method of paint film " Resin emulsion is coated on tinplate by method, is placed in 60 DEG C of baking oven and is toasted film forming, 24 hours dry, glue film of tearing, and It is tested as follows, test result is as shown in table 3:
1, it water absorption rate: weighs after dry glue film is sheared according to 2cm × 2cm, is denoted as m1 (g), be put into tap water and impregnate 24 It is taken out after hour, weighs after drying the water on surface, be denoted as m2 (g), according to the calculating water absorption rate of formula once: (m2-m1)/m1 × 100%；
2, it alkali resistance: is put into after dry glue film is sheared by 2cm × 2cm at room temperature in the aqueous slkali that weight fraction is 10% Impregnate 24 hours after observation observation specimen surface whether crack, dusting；
3, it acid resistance: is put into after dry glue film is sheared by 2cm × 2cm at room temperature in the acid solution that weight fraction is 10% Impregnate 24 hours after observation observation specimen surface whether crack, dusting；
4, it resistance to toluene: weighs m3 (g) after dry glue film is sheared by 2cm × 2cm, is put into after being impregnated 24 hours in pure toluene and takes Out, it weighs m4 (g) after drying the toluene on surface, is calculated using formula and inhale toluene rate are as follows: (m4-m3)/m3 × 100%；
5, it ethanol-tolerant: weighs m5 (g) after dry glue film is sheared by 2cm × 2cm, is put into 95% alcohol and impregnates 24 hours After take out, dry and weigh m6 (g) after the alcohol on surface, utilize formula to calculate and inhale alcohol rate are as follows: (m6-m5)/m5 × 100%.
The acid and alkali-resistance and water resistance of waterborne polyurethane resin made from each embodiment of table 3 and each comparative example detect
Have well it can be seen from data in table 3 according to aqueous acid and alkali-resistance polyurethane resin made from method in embodiment 1-4 Water absorption rate be 5.3% hereinafter, and impregnate and will not cracking within 24 hours and dusting in lye and acid solution, soaked in toluene and alcohol After bubble, quality increase it is less, illustrate the aqueous acid and alkali-resistance polyurethane resin as made from embodiment 1-4 with good water resistance, The ability of resistance to acid and alkali, resistance to toluene and ethanol-tolerant.
Comparative example 1 because being not added with dihydromethyl propionic acid in hydrophilic chain extender, the polyurethane resin as made from comparative example 1 Water absorption rate increases 6.1% compared with Example 1, and occurs cracking after impregnating 24 hours in acid solution and lye and dusting, says Bright dihydromethyl propionic acid can be improved the water resistance and acid-proof alkaline of aqueous acid and alkali-resistance polyurethane resin.
Comparative example 2 is because being not added with trimethylolpropane in hydrophilic chain extender, by comparing it can be seen from data in table 3 The water resistance of aqueous acid and alkali-resistance polyurethane resin, acid-proof alkaline made from example 2 are poor compared with Example 1, illustrate three hydroxyls Methylpropane can be improved water resistance, acid resistance, the alkali resistance of aqueous acid and alkali-resistance polyurethane resin.
Because being not added with hydroxy silicon oil in hydrophilic chain extender, the waterborne polyurethane resin as made from comparative example 3 exists comparative example 3 After impregnating in water, water absorption rate is larger, and after impregnating in acid solution and lye, occurs cracking and dusting, resistance to toluene and alcohol resistance Can be poor, illustrate that hydroxy silicon oil can be improved the water resistance and acid-proof alkaline of aqueous acid and alkali-resistance polyurethane resin.
Comparative example 4 is because being not added with dihydromethyl propionic acid and trimethylolpropane simultaneously in hydrophilic chain extender, by comparative example 4 The water resistance of waterborne polyurethane resin obtained, acid-proof alkaline are poor compared with embodiment 1, comparative example 1 and comparative example 2, Illustrate while using dihydromethyl propionic acid and trimethylolpropane as hydrophilic chain extender, can be improved the poly- ammonia of aqueous acid and alkali-resistance The water resistance and acid-proof alkaline of ester resin.
Comparative example 5 is made because being not added with dihydromethyl propionic acid and hydroxy silicon oil simultaneously in hydrophilic chain extender by comparative example 5 Aqueous acid and alkali-resistance polyurethane resin aqueous acid and alkali-resistance polyurethane resin obtained compared with embodiment 1, comparative example 1 and comparative example 3 It compares, either water absorption rate, acid resistance, alkali resistance, resistance to toluene and alcohol resistance energy, it is poor, illustrate while using dihydroxy first Base propionic acid and hydroxy silicon oil can be improved water resistance, the acid and alkali-resistance of aqueous acid and alkali-resistance polyurethane resin as hydrophilic chain extender The ability of property and resistance to toluene, alcohol.
Comparative example 6 is aqueous made from comparative example 6 because being not added with trimethylolpropane and hydroxy silicon oil in hydrophilic chain extender The water absorption rate of acid and alkali-resistance polyurethane resin significantly increases compared with Example 1, and water absorption rate and comparative example 2 and comparative example 3 are made Aqueous acid and alkali-resistance polyurethane resin compare, also significantly increase very much, illustrate while using trimethylolpropane and hydroxy silicon oil, It can be improved the resistance to acid and alkali and water resistance of waterborne polyurethane resin.
Three, application examples:
1, the preparation of application examples: 1.1, preparing synthetic leather according to the method in embodiment 1, is denoted as sample 1；1.2, according to embodiment Method in 1 prepares synthetic leather, the difference from embodiment 1 is that, add in non-hydrotropism's acid and alkali-resistance polyurethane resin internal layer slurry Add carbon fiber, is denoted as sample 2；1.3, prepare synthetic leather according to the method in embodiment 1, the difference from embodiment 1 is that, not to Active carbon is added in the slurry of aqueous acid and alkali-resistance polyurethane resin surface layer, is denoted as sample 3；1.4, according to the method system in embodiment 1 Standby synthetic leather, the difference from embodiment 1 is that, lavender is added in the slurry of non-hydrotropism's acid and alkali-resistance polyurethane resin surface layer extracts Liquid is denoted as sample 4；
2, the detection of application examples: randomly selecting 40 volunteers, is divided into 4 groups, and every group of 10 people volatilize sample 1-4 After smell is evaluated, evaluation result is as shown in table 4.
The applicating evaluating of the aqueous acid and alkali-resistance polyurethane resin of table 4
There is the fragrance of lavender according to synthetic leather made from method in embodiment 1 it can be seen from data in table 4, and without it His peculiar smell, illustrates carbon fiber, active carbon and smokes clothing extracting solution that peculiar smell in synthetic leather can be adsorbed, and synthetic leather is made to have lavender Peat-reek, without add carbon fiber aqueous acid and alkali-resistance polyurethane resin in slurry sample 2, although there is the perfume (or spice) of lavender Taste, but have thin peculiar smell, illustrate that carbon fiber can adsorb the peculiar smell in synthetic leather；Because of aqueous acid and alkali-resistance polyurethane in sample 3 It is not added with active carbon in resin surface layer slurry, although synthetic leather has the fragrance of lavender, is all to have thin peculiar smell, illustrates to live Property charcoal can adsorb the peculiar smell in synthetic leather；Clothing is smoked because being not added in the slurry of aqueous acid and alkali-resistance polyurethane resin surface layer in sample 4 Careless extracting solution, fragrance of the sample 4 without lavender, and have thin peculiar smell, illustrate that lavender can cover the different of synthetic leather volatilization Taste, the fragrance for making synthetic leather obtained have lavender special.
This specific embodiment is only explanation of the invention, is not limitation of the present invention, those skilled in the art Member can according to need the modification that not creative contribution is made to the present embodiment after reading this specification, but as long as at this All by the protection of Patent Law in the scope of the claims of invention.

Claims (10)

1. a kind of aqueous acid and alkali-resistance polyurethane resin, which is characterized in that comprise the following components in parts by weight: 25-30 parts of polyalcohols, 13-19 parts of polyisocyanates, 40-50 parts of acetone, 2-5 parts of amine chain extenders, 1.5-2.0 parts of hydrophilic chain extenders, 14-18 part two First alcohol chain extender, 0.5-0.8 parts of catalyst, 70-100 parts of deionized waters；
The hydrophilic chain extender is made of chain extender, crosslinking agent and the hydroxy silicon oil that mass ratio is 1:0.6-0.9:0.3-0.6；
The chain extender is one of dihydromethyl propionic acid, dimethylolpropionic acid or dihydroxy half ester；
The crosslinking agent is one of glycerol or trimethylolpropane.
2. aqueous acid and alkali-resistance polyurethane resin according to claim 1, which is characterized in that the polyalcohol is poly- tetrahydro furan It mutters one of glycol, polyethylene glycol, polypropylene glycol or a variety of compositions.
3. aqueous acid and alkali-resistance polyurethane resin according to claim 1, which is characterized in that the polyisocyanates is selected from different Isophorone diisocyanate, Toluene-2,4-diisocyanate, the group of one or more of 4- diisocyanate, 1,6- hexamethylene diisocyanate Close object.
4. aqueous acid and alkali-resistance polyurethane resin according to claim 1, which is characterized in that the amine chain extender is second two Amine, triethylene tetramine, 2- methyl-1,5- pentanediamine, isophorone diamine, hexamethylene diamine, 1,3- butanediamine, in diethylenetriamine It is a kind of.
5. aqueous acid and alkali-resistance polyurethane resin according to claim 1, which is characterized in that the glycol chain extender is 1, One of 4- butanediol, ethylene glycol, propylene glycol.
6. aqueous acid and alkali-resistance polyurethane resin according to claim 1, which is characterized in that the catalyst is that octanoic acid is sub- One of tin, dibutyl tin dilaurate.
7. a kind of preparation method of aqueous acid and alkali-resistance polyurethane resin according to claim 1-6, feature exist In, comprising the following steps:
S1, performed polymer synthesis: polyalcohol and polyisocyanates are added in reaction kettle, be added catalyst, glycol chain extender and 2/3 amine chain extender, under vacuum conditions, control reaction temperature are 108-112 DEG C, react 1-2h, are cooled to 80-85 DEG C, 2-3h is reacted, performed polymer is made；
S2, chain extending reaction: hydrophilic chain extender being added into performed polymer, reacts 3-4h at 65-85 DEG C, is cooled to 25-45 DEG C, adds Enter acetone dilution, until nco value is down to 1.2-2.2%(weight), organic silicon modified polyurethane performed polymer is made；
S3, water dispersion: adjusting temperature of reaction kettle is 0-20 DEG C, and deionized water is added, and is turning for 1400-1800r/min in revolving speed Under speed, disperse 30-40min, the amine chain extender of surplus is then added, and in 50-60 DEG C, -0.04 to -0.08MPa item It is evaporated under reduced pressure 4-5h under part, aqueous polyurethane emulsion is made.
8. a kind of aqueous acid and alkali-resistance polyurethane resin answering in synthetic leather or artificial leather as claimed in any one of claims 1 to 6 Use method.
9. the application method of aqueous acid and alkali-resistance polyurethane resin according to claim 8, which is characterized in that specifically include with Lower step:
(1) in the base fabric for handling by base fabric and plating through ironing roller, aqueous acid and alkali-resistance polyurethane tree is coated using knife coating Rouge internal layer slurry, coated weight 300-600g/m2, at 120-150 DEG C, linear speed is dried under conditions of being 3-5m/min, obtains water Property Synthetic Leather bass；
The aqueous acid and alkali-resistance polyurethane resin internal layer slurry is prepared from following methods: 60-70 parts being added into reaction kettle 0.1-0.8 parts of dispersing agents, 5-10 parts of polypropylene powders and 1-10 parts of talcums are added in aqueous acid and alkali-resistance polyurethane resin while stirring Powder is dispersed with stirring 30-40min under conditions of 1000-1300r/min, and 1-3 parts of thickeners, 5-10 parts of carbon fibers and 1-3 is added Part foam stabilizer, stirs 5-10min under conditions of 600-1000r/min, aqueous acid and alkali-resistance polyurethane resin internal layer slurry is made；
(2) aqueous acid and alkali-resistance polyurethane resin surface layer slurry is coated using knife coating on water-soluble polyurethane leather beth again, Coated weight is 30-50g/m2, dry under conditions of 150-180 DEG C, with the smooth processing of felt wrapped roll, then successively by cutting out, examining It tests and winding process, synthetic leather or artificial leather is made；
Aqueous acid and alkali-resistance polyurethane resin surface layer slurry is made of following methods: taking 80-100 parts of aqueous acid and alkali-resistance polyurethane resins Be added reaction kettle in, while stirring be added 3-5 parts of levelling agents, 0.1-0.3 parts of organic silicon defoamers, 0.2-0.6 parts of wetting agents, 0.5-1.1 parts of active carbons, 1-5 parts of basic zirconium phosphates carry silver powder, 2-4 parts of nano zine oxides, 0.5-1.5 parts of tourmaline powders, then in 600- 1-3 parts of thickeners, 1-5 parts of lavender extracting solutions are added under the revolving speed of 1200r/min, so that viscosity is 2500-3500mpa.s.
10. the application method of aqueous acid and alkali-resistance polyurethane resin according to claim 9, which is characterized in that the thickening Agent is the composition of one or both of alkali swelling type acrylic thickener or polyurethane associative thickener.
CN201910260893.6A 2019-04-02 2019-04-02 A kind of aqueous acid and alkali-resistance polyurethane resin and its preparation method and application method Pending CN110041485A (en)

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CN111117543A (en) * 2019-11-29 2020-05-08 江苏晟宏生态纺织科技有限公司 Hot melt adhesive with far infrared function and preparation method thereof
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CN114149560A (en) * 2021-12-14 2022-03-08 福建汇得新材料有限公司 Wet-process polyurethane resin and preparation method and application thereof

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