CN101328383A - Production method for liner gloves aqueous polyurethane coating connection material - Google Patents
Production method for liner gloves aqueous polyurethane coating connection material Download PDFInfo
- Publication number
- CN101328383A CN101328383A CNA2008100213252A CN200810021325A CN101328383A CN 101328383 A CN101328383 A CN 101328383A CN A2008100213252 A CNA2008100213252 A CN A2008100213252A CN 200810021325 A CN200810021325 A CN 200810021325A CN 101328383 A CN101328383 A CN 101328383A
- Authority
- CN
- China
- Prior art keywords
- glycol
- chainextender
- alcohol
- gloves
- solvent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Abstract
The invention discloses a production method for insert gloves water-based polyurethane coating bonding materials. The method comprises the following steps of: under the protection of dry nitrogen, adding polyether glycols (including polyether diatomic alcohol and/or polyether triatomic alcohol) having undergone vacuum dewatering and isocyanate into a reaction vessel; heating the mixture up to between 80 and 100 DEG C for reaction after even mixing; then adding a hydrophilic chain extender such as dihydromethyl propionic acid (DMPA) and a catalyst for reaction at a temperature of between 80 and 100 DEG C; finally adding the chain extender and a solvent into the mixture for reaction at a temperature of between 55 and 65 DEG C until the NCO content of the isocyanate group does not change; discharging the reactant after temperature reduction to obtain an ionomer; neutralizing a preformed polymer with triethylamine or diethanolamine or triethanolamine and then adding water the mixed solution for emulsification to obtain water-based polyurethane latex; and carrying out reduced pressure distillation to remove the solvent and obtain the product. The synthesized water-based polyurethane resin which serves as a gloves coating has the advantages of good air and moisture permeability, excellent mechanical performance, solvent resistance, ageing resistance, resistance to corrosion caused by chemical mediators, oil resistance, resistance to hooking, cutting and piercing, excellent abrasion resistance, odorlessness, innocuous and nondestructive for contacting with skin, etc.
Description
Technical field
The invention belongs to a kind of preparation of macromolecular material, specifically is a kind of production method that is used for liner gloves aqueous polyurethane coating connection material.
Background technology
From the angle of safety in production, hand, especially finger is the highest position of human body injury rate.International associated mechanisms statistics shows that if according to the injury work accident is classified, in all kinds of work accidents, the hand injury accident accounts for 25%.The industry troop of China is very huge, and advanced production unit, the means of labour are not also popularized, and the hand injury accident is corresponding also can be more.In the production practice, can not get for the moment under the basic situation about improving, use hand protection articles for use, particularly protective gloves just to become the important assist measure of prevention hand injury in labor condition.
Nearly all work gloves all is to use cotton or artificial silk or synthon sewn glove lining earlier, covers with paint, lacquer, colour wash, etc. various latexes, polymer emulsion, oligopolymer etc. then thereon, and the form of processing with Dipping is the main insert gloves of producing.These woven lining gloves, raw material type and article shape according to dipping, covering with paint are used for agricultural, fishery, civil construction, chemical plant, machine works etc., become the indispensable sample of these production departments.This gloves are poor compared with pure Rubber gloves feel, wear easily but take off, and also Energy and comfort is used in not boiling.In addition because the woven lining reinforcement arranged, better anti-cutting, cut, pierce through etc., so the comprehensive strength height of gloves.
Two, connection material relative merits in the market:
1. natural rubber latex
Natural rubber latex also contains 5% the nonrubber material of having an appointment except rubber hydrocarbon and water, wherein protein accounts for 1%～2% of latex.Because the natural rubber latex gloves have natural elastic, can anti-mild wear, antiacid, alkali, salt, alcohol, dilute aqueous solution functional.Ketones solvent is had limited chemical resistance, and skin friction force is bigger, is suitable for grasping sharp-pointed object, and is low temperature resistant, industrial or civilianly all can.
But a little less than anti-grease of natural rubber and the organic solvent properties, easily decompose and wear out, anti-cutting, pierce through with the wear resistance performance poorly, coating is ventilative, water vapour permeability is bad, and physical strength is lower, can not contact strong oxidizers such as nitric acid.In recent years, the irritated incident of natural rubber latex gloves frequently takes place, the research of U.S. John Huo Jinsi institute is pointed out, the ratio that the personnel of use natural rubber latex gloves infect allergy is 12.5%, wherein 2.5% has allergic symptom, 10% finds antibody in blood, contain allergen protein mainly due to natural rubber latex.
2. nitrile rubber
Nitrile rubber mainly (provides glued membrane to have intensity by divinyl (provide glued membrane to have elasticity and flexibility and the two keys that can build bridge etc.), vinyl cyanide, oil-proofness, mechanical properties etc.), carboxylic acid (improves the glued membrane tensile strength, hardness, solvent resistance) copolymerization forms, and is the very high chemical products of a kind of scientific and technological content.Anti-cutting, pierce through the gloves that are better than other materials with wear resistance, alkali, oils, fuel oil, grease and animal tallow are had good chemical resistance, and very strong antiacid, benzene, aldehyde, amine performance are arranged again.Compare with the PVC emgloves with natural rubber, the nitrile rubber industrial gloves does not contain allergen, no allergic stimulated, defense against bacterial virus infiltration are strong, this product has characteristics such as soft ductility is good, the more comfortable safety of wearing, therefore become more welcome articles for use in industry such as chemical industry and the family life, use range is very wide, and very big development space is arranged in the international market.Its ideal application field is a food, pharmaceutical industries, and semi-conductor industry, check and chemical mix, and oil fields etc. are the desirable protective gloves that is used for harsher operation.
But the butyronitrile emulsion coating ventilative, water vapour permeability is very poor, swelling can not take place and influence its physicals in as ketone, aromatic series and chlorinated solvent (benzene, methylene dichloride, trieline) at some solvent the solvent based protective is good, reduce protection function, and the butyronitrile latex taste of coating is heavier, in the making processes of gloves, bring harm for operator and environment on every side.
3. chloroprene rubber
Chloroprene rubber not only has the better physical mechanical property, and because the chlorine atom that is positioned on the position of double bond in the sovprene molecular chain is sterically hindered bigger, shielded the unsaturated double-bond in the polymer chain, unpaired electron is arranged in addition and demonstrate the very strong chlorine atom of electronegativity and attracting electronic cloud on two key keys, thereby chemical stability is higher.Compare with the natural rubber latex coating, its caoutchouc elasticity and physical and mechanical properties are similar, and have performances such as good heat-resisting, weather-proof, anti-ozone, the corrosion of fire-retardant, resistant to chemical media and grease resistance.Polychloroprene latex film forming and processing characteristics are also better, can be used as the work box gloves or as the protective articles of contact acid, alkali, oil and common solvent operation with its gloves that make.But anti-hook breaks, cuts, pierces through, wear resistance is not as paracril or natural rubber, when fragrant family of contact aromatic series and chlorinated solvent (benzene, methylene dichloride, trieline), protection function reduces a greater part of, and chloroprene rubber and skin contact, can injured skin.
4. isoprene-isobutylene rubber
This protective gloves has good protection effect to organic compound strong acid, and the weathering resistance ability is strong, and gas is had good especially barrier propterty, multiple compound all there is good chemical resistance, polar organic matter particularly, as ethylene glycol, ether,, anti-hook breaks, cuts, pierces through, wear resistance is good, but not as paracril or chloroprene rubber, the process for processing difficulty, coating ventilative, water vapour permeability is very poor, and oil, fat are had protective effect hardly, resistance toheat is poor, is not suitable for carbohydrate.
5. polyvinyl alcohol
On the one hand, to aliphatics, aromatic series, chlorinated solvent, ethers and most of ketone, except the acetone, chemical resistance is good, higher erosion resistance, physical property is good, comprise anti-hook break, cut and pierce through, wear-resisting.On the other hand, moulding property is good, meet water, low-purity alcohol or dilute aqueous solution and promptly can dissolve, and material is harder, and processing is inconvenient.
6.PVC
Wear resistance is good, to a large amount of water-soluble chemical materials, has good chemical resistance as strong acid, highly basic, inorganic salt solution, group water solution and alcohol.But can not protective solvent etc. organic substance because many solvents can make softening agent stripping wherein, not only can pollute, but also can reduce the barrier function of gloves greatly.Ventilative, the water vapour permeability of coating, flexibility uses feel all very poor, and low temperature hardens, and anti-tortuosity is poor, and intensity difference is cut or is punctured easily, is not proposed to be used in ketone and multiple organic solvent.
China is populous, and peasant and the basic unit's workman's number of being engaged in unskilled labour account for 80% of number of employees, produce and working process in, the hand injury accident often occurs.In the production practice, can not get for the moment under the basic situation about improving, use hand protection articles for use, particularly protective gloves just to become the important assist measure of prevention hand injury in labor condition.The product of protective gloves, according to the environment difference of operation separately, also different to the performance requriements of gloves.But no matter its operation under which kind of environment, generally speaking, gloves not only will stand the effect of corrosive medium, but also need bear mechanical load.The material of preparation gloves should anti-ly pierce through, anti tear and other physical abuses.And the various emulsion polymers of existing protective gloves, the shortcoming of gloves is all very big separately, and superior performance is not fine.Therefore, present protective gloves requires to have high ventilation, water vapour permeability, etc. performance, nontoxic with skin contact, not damaged, and it is simple to have manufacture craft, dresses characteristics such as comfortable.
Summary of the invention
The purpose of this invention is to provide a kind of production method that is used for liner gloves aqueous polyurethane coating connection material, adopt the synthetic waterborne polyurethane resin of acetone method and prepolymer method technology, as glove coating, have ventilatively, water vapour permeability is good, have very good mechanical properties, anti-solvent, ageing-resistant,, resistant to chemical media corrosion and grease resistance, anti-hook breaks, cuts, pierces through, the wear resisting property excellence, odorlessness, nontoxic with skin contact, advantages such as not damaged.
Technical scheme of the present invention is as follows:
Be used for the production method of liner gloves aqueous polyurethane coating connection material, it is characterized in that: adopt acetone method, may further comprise the steps:
Under the drying nitrogen protection; with the oligomer polyol after the vacuum hydro-extraction; and isocyanic ester adds in the reaction vessel; be warming up to 80-100 ℃ of reaction 1-3 hour after mixing; add wetting ability chainextender and catalyzer again at 80-100 ℃ of reaction 1-3h; adding chainextender and solvent at last reacts to isocyanate group NCO content at 55-65 ℃ and no longer changes; cooling back discharging must be from aggressiveness; will from aggressiveness with neutralizing agent in and after add water and carry out emulsification and obtain aqueous polyurethane emulsion, underpressure distillation slough solvent both product.
The described production method that is used for liner gloves aqueous polyurethane coating connection material is characterized in that:
The charging capacity of each component is:
The massfraction of isocyanic ester in polyurethane ionomers is 20-60%;
The massfraction of oligomer polyol in polyurethane ionomers is 0%-79%;
Chainextender is 0～50% at the massfraction in polyurethane ionomers;
Oligomer polyol and chainextender massfraction can not be 0 simultaneously; And can satisfy in the isocyanic ester, the NCO/OH mol ratio between 0.5-8, in the prescription reactant, contain can with isocyanate reaction all-OH functional group all should calculate in the NCO/OH mol ratio;
The massfraction of wetting ability chainextender in polyurethane ionomers is 0.01%-50%;
The catalyzer add-on is 0.3～0.5% of a polyurethane ionomers quality;
Solvent adding amount is 10～200% of a polyurethane ionomers quality;
The neutralizing agent add-on is 75～110% of a wetting ability chainextender mole number;
Isocyanic ester be selected from following one or more: tolylene diisocyanate (TDI), 4,4-diphenylmethanediisocyanate aromatic isocyanates such as (MDI), and isophorone diisocyanate (IPDI), hexamethylene-diisocyanate (HDI), 1,12-dodecane vulcabond (C
12Aliphatics such as DDI), alicyclic isocyanate;
Oligomer polyol be selected from following one or more: polyether glycol and polyester glycol are arranged, polycarbonate diol, polycaprolactone glycol, polybutadiene diol, acrylate polyvalent alcohol; It is the polyoxypropyleneglycol or the polyoxytrimethylene triol of 400 to 5000 different model that the oligomer polyol that adopts has molecular weight, polyoxytrimethylene-castor oil polyhydric alcohol, polytetrahydrofuran diol, tetrahydrofuran (THF)-polyether alcohol such as propylene oxide copolymerization glycol, and polycarbonate diol, polycaprolactone glycol, the polyethylene glycol adipate glycol, poly-adipate glycol-propylene glycol ester glycol, poly-hexanodioic acid glycol ether, poly-adipate glycol-glycol ether, poly-hexanodioic acid-1,4-butanediol ester glycol, poly-adipate glycol-1,4-butanediol ester glycol, poly-hexanodioic acid neopentyl glycol-1,6-hexylene glycol esterdiol, poly-hexanodioic acid Viscotrol C ester polyol, polyoxyethylene glycol, poly-carbonic acid 1,6-hexylene glycol esterdiol, poly-hexanodioic acid hexylene glycol esterdiol, siliceous polyvalent alcohol, fluorine-containing polyvalent alcohol, ester class polyvalent alcohols such as acrylate polyvalent alcohol, and Polybutadiene-acrylonitrile copolymerization glycol, polyvalent alcohols such as Resins, epoxy;
Chainextender comprises alcohols chainextender, amine chain extender, be selected from following one or more:
The alcohols chainextender: 1,4-butyleneglycol, 2,3-butyleneglycol, glycol ether, 1,6-hexylene glycol, glycerine, TriMethylolPropane(TMP), glycol ether, sorbyl alcohol, siliceous dibasic alcohol, Fluorinated dihydric alcohol;
Amine chain extender: 3,3 '-two chloro-4, MOCA of 4 '-diamino-ditan and the liquid that obtains by the formaldehyde modification thereof etc., 1, the polytetrahydrofuran dibasic alcohol of 4-hydroxymethyl-cyclohexane, hydroquinone two hydroxy ethyl ether, 1,3 butylene glycol, neopentyl alcohol, lower molecular weight (about 250), dihydroxyphenyl propane dihydroxyethyl ether; Siliceous diamine, fluorine-containing diamine; Isophorone diamine, 1, the two aminophenyl ethylene dithiol ethers, 2 of 2-, 4-diamino-3,5-diethyl toluene, glutaryl-are two, two (right-N, N '-Ding amino-phenyl) methane of popular name Unilink, piperazine;
The wetting ability chainextender be selected from following one or more: sulfonic group or secondary amine wetting ability chainextender, sulfonic group wetting ability chainextender have second diamino esilate, second dihydroxyl esilate and dihydroxyl polyoxygenated polyvalent alcohol sulfonate, diamino polyoxygenated polyvalent alcohol sulfonate; Dimethylol propionic acid (DMPA), dimethylolpropionic acid (DMBA), dicarboxyl half ester, amino acid, diaminobenzoic acid, maleic anhydride etc.;
Catalyzer be selected from following one or more: 1. tertiary amine catalyst: triethylamine, morphine quinoline, pyridine, triethylene diamine; 2. organometallic compound class catalyzer: stannous octoate, dibutyl tin dilaurate;
Solvent is selected from acetone, butanone, ethyl acetate, methylethylketone, N, N-dimethylformamide, N-Methyl pyrrolidone;
Neutralizing agent is selected from triethylamine, dimethylethanolamine, diethanolamine, organic amines such as trolamine.
The described production method that is used for liner gloves aqueous polyurethane coating connection material is characterized in that: the mol ratio of NCO/OH is 2-6; Catalyzer is the mixed catalyst of tertiary amines such as organic carboxyl acid salts such as stannous octoate and triethylene diamine.
The described production method that is used for liner gloves aqueous polyurethane coating connection material is characterized in that: described oligomer polyol is selected from polyether glycol, comprises polyether Glycols and/or polyether-tribasic alcohol; The NCO/OH mol ratio is 1.1-1.2.
The described production method that is used for liner gloves aqueous polyurethane coating connection material is characterized in that:
The charging capacity of each component is:
The massfraction of isocyanic ester in polyurethane ionomers is 20-40%;
The massfraction of oligomer polyol in polyurethane ionomers is 55%-75%;
The massfraction of chainextender in polyurethane ionomers is 3%-10%;
The massfraction of wetting ability chainextender in polyurethane ionomers is 2%-3.5%;
Solvent adding amount is the 50%-100% of polyurethane ionomers quality.
The described production method that is used for liner gloves aqueous polyurethane coating connection material is characterized in that:
Isocyanic ester is selected tolylene diisocyanate, hexamethylene-diisocyanate (HDI), isophorone diisocyanate (IPDI) or its mixture for use;
Oligomer polyol is selected polyoxypropyleneglycol (N-220), polyoxytrimethylene triol (N-330), polyoxyethylene glycol (PPG-1000) or its mixture for use;
Chainextender is selected siliceous dibasic alcohol, Fluorinated dihydric alcohol or isophorone diamine for use;
The wetting ability chainextender is selected dimethylol propionic acid (DMPA), dimethylolpropionic acid (DMBA) or its mixture for use;
Solvent is selected acetone for use;
Neutralizing agent is selected triethylamine for use, dimethylethanolamine, diethanolamine or trolamine.
Described polyurethane ionomers is meant solid content in aggressiveness, is the reaction mass summation that does not comprise solvent and catalyzer.
Raw materials pretreatment among the preparation method:
Oligomer polyol, chainextender, Viscotrol C dewatered 4 hours in 120 ℃ of vacuum drying ovens; DMPA, TMP are dry before use; Before using, triethylamine, acetone soaks fortnight with the 4A molecular sieve.
Preparation urethane oligomer polyol commonly used mainly contains polyether glycol and polyester glycol.Other polycarbonate diol, polycaprolactone glycol, polybutadiene diol, acrylate polyvalent alcohol etc. are arranged.Polyether-type has kindliness preferably because ether easily rotates, and superior low-temperature performance is arranged.And ether is facile hydrolysis not, and hydrolytic resistance is better than polyester type.But the α carbon of ehter bond is easily oxidized, is easy to generate a series of oxidative degradations.Polyester type intensity height, the good but hydrolysis not of bonding force.The polyolefine oxygen-free can not form hydrogen bond with carbamate, its prepared material degree maximum that is separated.Because price, domestic main at present employing polyether glycol prepares aqueous polyurethane.
The low molecule polyfunctionality compound of hydroxyl or primary/secondary amino group and isocyanic ester play a part crosslinked and chain extension when using jointly, promptly so-called chainextender.Their relative molecular mass is generally between 40～300.Usually, functionality is 2 the chainextender that is called; Functionality more than or equal to 3 then can be called linking agent.They roughly can be divided into two types of the amino and terminal hydroxy group of end according to the type of reactive group in the molecule.The relation of chain extender affects segmented polyurethane and soft section, and directly influence the performance of polyurethane products, therefore the use of chainextender is very crucial in the prescription.Chainextender can also with excess isocyanate generation secondary reaction, thereby generate allophanate or biuret structure takes place crosslinked.
The protective gloves aqueous polyurethane coating connection material uses:
The protective gloves aqueous polyurethane emulsion that the present invention is prepared, field of employment difference according to protective gloves, add different auxiliary agents, needing to add basic auxiliary dosage is respectively: thickening material 0.5%～5%, stablizer 2%～20%, linking agent 0.5%～5%, peptizer: nitrocalcite 0.5%～15%, methyl alcohol 50%～100%, acetic acid 0.1%～10%, softening agent 0.2%～10%, anti-aging agent: 0.1%～2%, release agent 0.2%～8%, coupling agent 0.2%～8%, hydrolysis stabilizer 0.3%～5%, etc.
Connect the technology that material is used to make gloves: ceramic former is heated to about about 60 degree, the woven lining gloves are put fingerprint, in the solution of peptizer, flood 5～10s, throw away unnecessary peptizer (40～50s), 10s makes model become vertical state (90s) before impregnation, immerses the aqueous polyurethane coating connection material 20～30s that adds auxiliary agent, after drying slightly, by 26 meters baking ovens about 110 degree, oven dry is taken out.
Coupling agent: KH-570 silane coupling agent, KH-580 silane coupling agent, γ thiopropyl triethoxyl silane, KH-570 silane coupling agent, KH-590 silane coupling agent, G-407 organo silane coupling agent, anilino Union carbide A-162 etc.
The ratio that these auxiliary agents account in the system of performed polymer is 0～20%.
Thickening material: the mechanism of action of aqueous polyurethane thickening mainly is thixotropic charge theory, and promptly the electric charge on polyurethane particles surface makes the particle ordered arrangement in the dispersion system.Degree of alignment difference, the thixotropic intensity of system are also different.Aqueous polyurethane thickener commonly used has 1. inorganic thickening agent of four classes, as flaky silicic acid salt, aerosil etc.; 2. natural organic thickening agent is as cellulose ethers; 3. synthetic organic thickening agent, as polyacrylate(s), polyvinylpyrrolidone.4. associative thickener is as WT-105A etc.
The ratio that these auxiliary agents account in the system of performed polymer is 0.5%～10%.
Outside cross-linking agent: the urethane of alkoxide melamine/formaldehyde, polyfunctionality cyano group acid amides, tolyl cyano group acid amides/three-glycidyl fat, polyfunctionality aziridine, methoxy methanolizing melamine, urea resin, alkylation diimine, polyisocyanates, sealing isocyano, carnauba wax, chloromethane are for oxygen phenyl ring, multi-functional 1-azepine propane, aminoresin, epoxy type linking agent etc.
The ratio that these auxiliary agents account in the system of performed polymer is 0.5%～5%.
Defoamer: the defoamer that is usually used in aqueous polyurethane has mineral oils, silicone based, polar organic compounds class 3 big classes.Alcohols is (as isooctyl alcohol, lower alcohol generally all has broken bubble ability, but press down a little less than the bubble ability, volatile), phosphoric acid ester (as tributyl phosphate, triphenylphosphate, tricresyl phosphate butoxyethyl acetate etc.), lipid acid and ester class thereof (as stearic acid, single lauryl butyl stearate), polysiloxane-based (as dimethyl silicone oil, froth breaking spirit, silicone cream), metallic soap class (as calcium stearate, aluminum stearate, potassium oleate, lanolin), and paraffin, sulphonate etc.
The ratio that these auxiliary agents account in the system of performed polymer is 0.1%～5%.
Softening agent: softening agent mainly contains following two classes: 1. derivative of fatty acid class, and as high fatty alcohol and higher fatty acid and high-grade aliphatic ester.2. organosilicon oils is as polydimethylsiloxane (methyl-silicone oil), poly-methyl hydrogen-containing siloxane (containing hydrogen silicone oil), poly-methyl hydroxyl siloxanes (hydroxy silicon oil) with contain modified organic silicons such as oxyethane, polyethers and amino.
The ratio that these auxiliary agents account in the system of performed polymer is 0.2%～10%.
Anti-aging agent: 2,6 ditertiary butyl p cresol (anti-aging agent-264), 4-, 4 '-two uncle's octyl diphenylamines, tetramethylene-β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid pentaerythritol ester (antioxidant 1010) etc.
Tinting material: inorganic colourant has: titanium dioxide, magnesium oxide, chromic oxide, Cadmium Sulfide, magnesium aluminate, dim etc.Pigment dyestuff has: azo/diazonium based dye, phthalocyanine etc.
The ratio that these auxiliary agents account in the system of performed polymer is 0.1%～2%.
Release agent: natural cured nonionic emulsifier, LH-633 water-based release agent etc.
Suds-stabilizing agent: dimethyl dodecyl amine oxide etc.
PH stablizer: 2-amino-2-methyl-1-propanol etc.
Hydrolysis stabilizer: the most frequently used hydrolysis stabilizer has carbodiimide and derivative and epoxide.
The ratio that these auxiliary agents account in system is 0.3%～5%
Peptizer: the methanol solution of the ethanolic soln of calcium halide, calcium acetate, barium acetate, nitrocalcite, acetic acid hexanaphthene, aluminum sulfate aqueous solution, zinc nitrate aqueous solution.
The ratio that these auxiliary agents account in system is 0.3%～20%.
The present invention adopts acetone method and the synthetic waterborne polyurethane resin of prepolymer method technology, as glove coating, have ventilative, water vapour permeability is good, have very good mechanical properties, anti-solvent, ageing-resistant,, resistant to chemical media corrosion and grease resistance, anti-hook breaks, cuts, pierces through, the wear resisting property excellence, odorlessness, nontoxic with skin contact, advantages such as not damaged.
Embodiment
Example 1
Under the drying nitrogen protection; with 200 parts of the polyoxypropyleneglycols after the vacuum hydro-extraction (N-220); 200 parts of polyoxytrimethylene triols (N-330); 130 parts of tolylene diisocyanates (TDI) are by being metered in the there-necked flask; be warming up to after mixing about 85 ℃ and react 1h; add anionic hydrophilic chainextender DMPA20 part again and add several tertiary amine catalyst catalyzer and react 1h for about 85 ℃; add 36 parts of chainextender DEG at last; 20 parts of Fluorinated dihydric alcohols and acetone react to NCO content and no longer change for an amount of 60 ℃, are cooled to 45 ℃ of dischargings.Performed polymer is added water after with 20 parts of neutralizations of triethylamine carries out emulsify at a high speed, obtain the WPU emulsion, underpressure distillation slough solvent both product.
Example 2
Under the drying nitrogen protection; with 200 parts of the polyoxypropyleneglycols after the vacuum hydro-extraction (N-220); 200 parts of polyoxypropyleneglycols (N-240); 200 parts of polyoxyethylene glycol (PPG-1000); 240 parts of tolylene diisocyanates (TDI) are by being metered in the there-necked flask; be warming up to after mixing about 85 ℃ and react 1h; add 30 parts of an amount of anionic hydrophilic chainextender DMPA again; and add several tertiary amine catalyst catalyzer and react 1h for about 85 ℃; add 64 parts of chainextender DEG at last; 20 parts of siliceous dibasic alcohol and acetone react to NCO content and no longer change for an amount of 60 ℃, are cooled to 45 ℃ of dischargings.Performed polymer is added water after with 2 parts of neutralizations of triethylamine carries out emulsify at a high speed, obtain the WPU emulsion, underpressure distillation slough solvent both product.
Example 3
Under the drying nitrogen protection; with 200 parts of the polyoxypropyleneglycols after the vacuum hydro-extraction (N-220); 400 parts of polyoxypropyleneglycols (N-240); 300 parts of polyoxyethylene glycol (PPG-1000); 170 parts of hexamethylene-diisocyanates (HDI); 220 parts of isophorone diisocyanates (IPDI) are by being metered in the there-necked flask; be warming up to after mixing about 85 ℃ and react 1h; add 47 parts of anionic hydrophilic chainextender DMPA again; and add several catalyzer and react 1h for about 85 ℃; add 15 parts of chainextender DEG at last; 8 parts of linking agent TMP; 10 parts of siliceous dibasic alcohol; 10 parts of Fluorinated dihydric alcohols and acetone react to NCO content and no longer change for an amount of 60 ℃, are cooled to 40 ℃ of dischargings.Performed polymer is added water after with 2.5 parts of neutralizations of triethylamine carries out emulsify at a high speed, drip 60 parts of isophorone diamines, obtain the WPU emulsion, underpressure distillation slough solvent both product.
Example 4
Under the drying nitrogen protection; with 600 parts of the polyoxypropyleneglycols after the vacuum hydro-extraction (N-240); 200 parts of polyoxytrimethylene triols (N-330); 220 parts of isophorone diisocyanates (IPDI) are by being metered in the there-necked flask; be warming up to after mixing about 85 ℃ and react 1h; add 27 parts of anionic hydrophilic chainextender DMPA again and add several stannous octoate catalysts and react 1h for about 85 ℃; add chainextender DEG35 part at last; 15 parts of siliceous dibasic alcohol; 15 parts of Fluorinated dihydric alcohols and acetone react to NCO content and no longer change for an amount of 60 ℃, are cooled to 40 ℃ of dischargings.Performed polymer is added water after with 30 parts of neutralizations of triethylamine carries out emulsify at a high speed, and drip 28 parts of quadrols and divinyl three obtains the WPU emulsion by 15 parts, underpressure distillation slough solvent both product.
Example 5
Under the drying nitrogen protection; with 600 parts of the polyoxypropyleneglycols after the vacuum hydro-extraction (N-240); 100 parts of polyoxypropyleneglycols (N-210); 100 parts of polyoxytrimethylene triols (N-330); 230 parts of isophorone diisocyanates (IPDI) are by being metered in the there-necked flask; be warming up to after mixing about 85 ℃ and react 1h; add 30 parts of an amount of anionic hydrophilic chainextender DMPA again; and add several catalyzer and react 1h for about 85 ℃; add 10 parts of chainextender DEG at last; 15 parts of siliceous dibasic alcohol; 20 parts of Fluorinated dihydric alcohols and acetone react to NCO content and no longer change for an amount of 60 ℃, are cooled to 40 ℃ of dischargings.Performed polymer is added water after with 35 parts of neutralizations of triethylamine carries out emulsify at a high speed, and drip quadrol and obtain the WPU emulsion for 15 parts, underpressure distillation slough solvent both product.
Example 6
Under the drying nitrogen protection; with 200 parts of the polyoxypropyleneglycols after the vacuum hydro-extraction (N-220); 68 parts of tolylene diisocyanates (TDI) are by being metered in the there-necked flask; be warming up to after mixing about 85 ℃ and react 1h; add 9 parts of anionic hydrophilic chainextender DMPA again and add several catalyzer and react 1h for about 85 ℃; add chainextender DEG14 part at last; 3 parts of linking agent TMP; 3 parts of siliceous dibasic alcohol; 2 parts of Fluorinated dihydric alcohols and acetone react to NCO content and no longer change for an amount of 60 ℃, are cooled to 45 ℃ of dischargings.Performed polymer is added water after with 10 parts of neutralizations of triethylamine carries out emulsify at a high speed, obtain the WPU emulsion, underpressure distillation slough solvent both product.
Table 1 protective gloves aqueous polyurethane coating connection material typical technology index
| Test subject | Test result |
| Tensile strength | 3MPa～50MPa |
| Elongation | 550％～1900％ |
| Water-intake rate (48h) | 1％～3％ |
| Oil resistant | Excellent |
| Acidproof | Excellent |
| Alkaline-resisting | Excellent |
| Smell | Do not have |
| Toxicity | Do not have |
| Elasticity | Excellent (slow resilience-Gao resilience) |
| Wear-resistant | Excellent |
| Anti-thorn | Excellent |
| Grasping (doing) | Excellent |
| Grasping (wetting) | Excellent |
| Ageing-resistant | Excellent |
| Anti-solvent | Excellent |
| Saturating wet (25 ℃) | 2000～5700g/(m 2.d) |
| Film formation time | 17min～68min |
| Bonding strength | 13～18MPa |
| Hardness (Shao A) | 15～35 |
| Use temperature | -10℃～60℃ |
Claims (6)
1, be used for the production method of liner gloves aqueous polyurethane coating connection material, it is characterized in that: adopt acetone method, may further comprise the steps:
Under the drying nitrogen protection; with the oligomer polyol after the vacuum hydro-extraction; and isocyanic ester adds in the reaction vessel; be warming up to 80-100 ℃ of reaction 1-3 hour after mixing; add wetting ability chainextender and catalyzer again at 80-100 ℃ of reaction 1-3h; adding chainextender and solvent at last reacts to isocyanate group NCO content at 55-65 ℃ and no longer changes; cooling back discharging must be from aggressiveness; will from aggressiveness with neutralizing agent in and after add water and carry out emulsification and obtain aqueous polyurethane emulsion, underpressure distillation slough solvent both product.
2, the production method that is used for liner gloves aqueous polyurethane coating connection material according to claim 1 is characterized in that:
The charging capacity of each component is:
The massfraction of isocyanic ester in polyurethane ionomers is 20-60%;
The massfraction of oligomer polyol in polyurethane ionomers is 0%-79%;
Chainextender is 0～50% at the massfraction in polyurethane ionomers;
Oligomer polyol and chainextender massfraction can not be 0 simultaneously; And can satisfy in the isocyanic ester, the NCO/OH mol ratio between 0.5-8, in the prescription reactant, contain can with isocyanate reaction all-OH functional group all should calculate in the NCO/OH mol ratio;
The massfraction of wetting ability chainextender in polyurethane ionomers is 0.01%-50%;
The catalyzer add-on is 0.3～0.5% of a polyurethane ionomers quality;
Solvent adding amount is 10～200% of a polyurethane ionomers quality;
The neutralizing agent add-on is 75～110% of a wetting ability chainextender mole number;
Isocyanic ester be selected from following one or more: tolylene diisocyanate (TDI), 4,4-diphenylmethanediisocyanate aromatic isocyanates such as (MDI), and isophorone diisocyanate (IPDI), hexamethylene-diisocyanate (HDI), 1,12-dodecane vulcabond (C
12Aliphatics such as DDI), alicyclic isocyanate;
Oligomer polyol be selected from following one or more: polyether glycol and polyester glycol are arranged, polycarbonate diol, polycaprolactone glycol, polybutadiene diol, acrylate polyvalent alcohol; It is the polyoxypropyleneglycol or the polyoxytrimethylene triol of 400 to 5000 different model that the oligomer polyol that adopts has molecular weight, polyoxytrimethylene-castor oil polyhydric alcohol, polytetrahydrofuran diol, tetrahydrofuran (THF)-polyether alcohol such as propylene oxide copolymerization glycol, and polycarbonate diol, polycaprolactone glycol, the polyethylene glycol adipate glycol, poly-adipate glycol-propylene glycol ester glycol, poly-hexanodioic acid glycol ether, poly-adipate glycol-glycol ether, poly-hexanodioic acid-1,4-butanediol ester glycol, poly-adipate glycol-1,4-butanediol ester glycol, poly-hexanodioic acid neopentyl glycol-1,6-hexylene glycol esterdiol, poly-hexanodioic acid Viscotrol C ester polyol, polyoxyethylene glycol, poly-carbonic acid 1,6-hexylene glycol esterdiol, poly-hexanodioic acid hexylene glycol esterdiol, siliceous polyvalent alcohol, fluorine-containing polyvalent alcohol, ester class polyvalent alcohols such as acrylate polyvalent alcohol, and Polybutadiene-acrylonitrile copolymerization glycol, polyvalent alcohols such as Resins, epoxy;
Chainextender comprises alcohols chainextender, amine chain extender, be selected from following one or more:
The alcohols chainextender: 1,4-butyleneglycol, 2,3-butyleneglycol, glycol ether, 1,6-hexylene glycol, glycerine, TriMethylolPropane(TMP), glycol ether, sorbyl alcohol, siliceous dibasic alcohol, Fluorinated dihydric alcohol;
Amine chain extender: 3,3 '-two chloro-4, MOCA of 4 '-diamino-ditan and the liquid that obtains by the formaldehyde modification thereof etc., 1, the polytetrahydrofuran dibasic alcohol of 4-hydroxymethyl-cyclohexane, hydroquinone two hydroxy ethyl ether, 1,3 butylene glycol, neopentyl alcohol, lower molecular weight (about 250), dihydroxyphenyl propane dihydroxyethyl ether; Siliceous diamine, fluorine-containing diamine; Isophorone diamine, 1, the two aminophenyl ethylene dithiol ethers, 2 of 2-, 4-diamino-3,5-diethyl toluene, glutaryl-are two, two (right-N, N '-Ding amino-phenyl) methane of popular name Unilink, piperazine;
The wetting ability chainextender be selected from following one or more: sulfonic group or secondary amine wetting ability chainextender, sulfonic group wetting ability chainextender have second diamino esilate, second dihydroxyl esilate and dihydroxyl polyoxygenated polyvalent alcohol sulfonate, diamino polyoxygenated polyvalent alcohol sulfonate; Dimethylol propionic acid (DMPA), dimethylolpropionic acid (DMBA), dicarboxyl half ester, amino acid, diaminobenzoic acid, maleic anhydride etc.;
Catalyzer be selected from following one or more: 1. tertiary amine catalyst: triethylamine, morphine quinoline, pyridine, triethylene diamine; 2. organometallic compound class catalyzer: stannous octoate, dibutyl tin dilaurate;
Solvent is selected from acetone, butanone, ethyl acetate, methylethylketone, N, N-dimethylformamide, N-Methyl pyrrolidone;
Neutralizing agent is selected from triethylamine, dimethylethanolamine, diethanolamine, organic amines such as trolamine.
3, the production method that is used for liner gloves aqueous polyurethane coating connection material according to claim 1 is characterized in that: the mol ratio of NCO/OH is 2-6; Catalyzer is the mixed catalyst of tertiary amines such as organic carboxyl acid salts such as stannous octoate and triethylene diamine.
4, the production method that is used for liner gloves aqueous polyurethane coating connection material according to claim 1, it is characterized in that: described oligomer polyol is selected from polyether glycol, comprises polyether Glycols and/or polyether-tribasic alcohol; The NCO/OH mol ratio is 1.1-1.2.
5, the production method that is used for liner gloves aqueous polyurethane coating connection material according to claim 1 is characterized in that:
The charging capacity of each component is:
The massfraction of isocyanic ester in polyurethane ionomers is 20-40%;
The massfraction of oligomer polyol in polyurethane ionomers is 55%-75%;
The massfraction of chainextender in polyurethane ionomers is 3%-10%;
The massfraction of wetting ability chainextender in polyurethane ionomers is 2%-3.5%;
Solvent adding amount is the 50%-100% of polyurethane ionomers quality.
6, the production method that is used for liner gloves aqueous polyurethane coating connection material according to claim 1 is characterized in that:
Isocyanic ester is selected tolylene diisocyanate, hexamethylene-diisocyanate (HDI), isophorone diisocyanate (IPDI) or its mixture for use;
Oligomer polyol is selected polyoxypropyleneglycol (N-220), polyoxytrimethylene triol (N-330), polyoxyethylene glycol (PPG-1000) or its mixture for use;
Chainextender is selected siliceous dibasic alcohol, Fluorinated dihydric alcohol or isophorone diamine for use;
The wetting ability chainextender is selected dimethylol propionic acid (DMPA), dimethylolpropionic acid (DMBA) or its mixture for use;
Solvent is selected acetone for use;
Neutralizing agent is selected triethylamine for use, dimethylethanolamine, diethanolamine or trolamine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008100213252A CN101328383A (en) | 2008-07-17 | 2008-07-17 | Production method for liner gloves aqueous polyurethane coating connection material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008100213252A CN101328383A (en) | 2008-07-17 | 2008-07-17 | Production method for liner gloves aqueous polyurethane coating connection material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101328383A true CN101328383A (en) | 2008-12-24 |
Family
ID=40204400
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2008100213252A Pending CN101328383A (en) | 2008-07-17 | 2008-07-17 | Production method for liner gloves aqueous polyurethane coating connection material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101328383A (en) |
Cited By (57)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101845133A (en) * | 2010-04-01 | 2010-09-29 | 陕西科技大学 | Method for preparing natural polyhydroxy compound modified aqueous polyurethane emulsion |
| CN101845269A (en) * | 2010-05-31 | 2010-09-29 | 淄博永麒化工技术开发有限公司 | Waterborne polyurethane finishing agent for PVC (Polyvinyl Chloride) protective gloves and preparation method thereof |
| CN101885830A (en) * | 2010-06-24 | 2010-11-17 | 同济大学 | Synthesis method of waterborne polyurethane emulsion |
| CN101942255A (en) * | 2010-08-09 | 2011-01-12 | 上海瑞鹏化工材料科技有限公司 | Preparation and application process of polyurethane-modified acrylate thick film type elastic coating material capable of being rapidly solidified at ordinary temperature |
| CN102040724A (en) * | 2010-11-01 | 2011-05-04 | 江苏东邦科技有限公司 | Non-yellowing polyurethane resin for waterproof coating and preparation method thereof |
| CN102050935A (en) * | 2010-12-08 | 2011-05-11 | 肇庆千江高新材料科技有限公司 | Water-soluble polyurethane curing agent and preparation method thereof |
| CN102161861A (en) * | 2010-12-29 | 2011-08-24 | 上海东升新材料有限公司 | Modified polyurethane emulsion for paint |
| CN102174165A (en) * | 2010-12-28 | 2011-09-07 | 东莞市英科水墨有限公司 | Waterborne polyurethane binder and preparation method thereof |
| CN102516745A (en) * | 2011-11-23 | 2012-06-27 | 王曦 | Oil bag manufacturing method of automatic die mold demolding impermeabilisation test machine |
| CN102585150A (en) * | 2012-02-01 | 2012-07-18 | 嘉兴学院 | Preparation method of anionic aqueous polyurethane dispersoid for fabric coating and decoration |
| CN102786654A (en) * | 2012-08-23 | 2012-11-21 | 蚌埠金黄山凹版印刷有限公司 | Nano waterborne ink binder and preparation method thereof |
| CN102786651A (en) * | 2012-08-23 | 2012-11-21 | 深圳市科彩印务有限公司 | Waterborne polyurethane binder, waterborne polyurethane composite binder and preparation method of waterborne polyurethane binder and waterborne polyurethane composite binder |
| CN103130977A (en) * | 2013-01-08 | 2013-06-05 | 厦门大学 | Polyol polyurethane dispersions of two-component waterborne wood lacquer and preparation method thereof |
| CN103360570A (en) * | 2013-07-31 | 2013-10-23 | 常德市武陵金德镭射科技有限公司 | Waterborne polyurethane, preparation method therefor and waterborne transfer painting |
| CN103360934A (en) * | 2013-07-31 | 2013-10-23 | 常德市武陵金德镭射科技有限公司 | Waterborne matte silver transfer painting and preparation method therefor |
| CN103450442A (en) * | 2013-09-03 | 2013-12-18 | 山东天庆科技发展有限公司 | Waterborne polyurethane resin and synthetic method thereof |
| CN103450440A (en) * | 2013-09-03 | 2013-12-18 | 山东天庆科技发展有限公司 | Waterborne polyurethane resin and preparation method thereof |
| CN103666234A (en) * | 2013-12-12 | 2014-03-26 | 青岛海洋新材料科技有限公司 | Preparation method of titanium nanometer organic anticorrosive paint |
| CN103694940A (en) * | 2013-12-15 | 2014-04-02 | 山西省应用化学研究所 | Method for preparing fast curing one-component water-based polyurethane adhesive |
| CN103740259A (en) * | 2014-01-15 | 2014-04-23 | 许建琴 | Polyurethane waterproof paint and preparation method thereof |
| CN103865250A (en) * | 2014-04-03 | 2014-06-18 | 昆山金有利新材料科技有限公司 | Fireproof polyurethane film and preparation method thereof |
| CN103992461A (en) * | 2014-04-05 | 2014-08-20 | 秦皇岛出入境检验检疫局煤炭检测技术中心 | Aqueous polyurethane phase change energy storage material |
| CN104479613A (en) * | 2014-12-17 | 2015-04-01 | 广东菲安妮皮具股份有限公司 | Environment-friendly leather adhesive |
| CN104497952A (en) * | 2014-12-17 | 2015-04-08 | 广东菲安妮皮具股份有限公司 | High-water-resistance leather adhesive |
| CN104974472A (en) * | 2015-07-20 | 2015-10-14 | 湖北省交通运输厅黄黄高速公路管理处 | Preparation method of high-strength organic grouting material for roads |
| CN105199593A (en) * | 2015-11-02 | 2015-12-30 | 淄博夸克医药技术有限公司 | Modified polyurethane fireproof coating with wear resistance |
| CN105332287A (en) * | 2015-10-14 | 2016-02-17 | 安徽中恩化工有限公司 | Coating resin used for high temperature resistant high adhesive force wet hand wearable PVC gloves, and preparation method thereof |
| CN105462479A (en) * | 2015-12-21 | 2016-04-06 | 潍坊市宏源防水材料有限公司 | Environment-friendly weather-proof self-stratifying one-component waterproof paint and preparation method thereof |
| CN105639777A (en) * | 2016-01-29 | 2016-06-08 | 山东星宇手套有限公司 | Wear-resistant flannelette nitrile gloves and preparation technology thereof |
| CN105916947A (en) * | 2014-01-17 | 2016-08-31 | 巴斯夫欧洲公司 | Lamination printing ink comprising an aqueous dispersion comprising polyurethane |
| CN106432678A (en) * | 2016-11-17 | 2017-02-22 | 无锡市长安曙光手套厂 | Medical glove material |
| CN106832883A (en) * | 2017-01-17 | 2017-06-13 | 南通强生安全防护科技股份有限公司 | Aqueous PU composite mortars of Graphene and its production and use |
| CN107226897A (en) * | 2017-07-21 | 2017-10-03 | 蓝帆医疗股份有限公司 | One kind can breathe surgical glove waterborne polyurethane resin material and preparation method thereof |
| CN107236110A (en) * | 2017-05-23 | 2017-10-10 | 兰州科天健康科技股份有限公司 | A kind of medical gloves polyaminoester emulsion and preparation method thereof |
| CN107400190A (en) * | 2017-07-21 | 2017-11-28 | 蓝帆医疗股份有限公司 | One kind can breathe surgical glove and preparation method thereof |
| CN107573717A (en) * | 2017-09-13 | 2018-01-12 | 杨磊 | The formula and preparation technology of a kind of polyurethane |
| CN107983264A (en) * | 2017-10-30 | 2018-05-04 | 珠海市金团化学品有限公司 | A kind of environment-friendly type Water/oil dual-purpose macromolecule dispersing agent and preparation method thereof |
| CN108250399A (en) * | 2017-12-01 | 2018-07-06 | 上海汇得科技股份有限公司 | A kind of high demoulding, excellent wear resistance safety and industrial gloves wet polyurethane resin and preparation method |
| CN108636103A (en) * | 2018-05-05 | 2018-10-12 | 安徽乐金环境科技有限公司 | A kind of room air composite purifying agent |
| CN108671745A (en) * | 2018-05-05 | 2018-10-19 | 安徽乐金环境科技有限公司 | A kind of preparation method of room air composite purifying agent |
| CN108722013A (en) * | 2018-05-05 | 2018-11-02 | 安徽乐金环境科技有限公司 | A kind of room air composite purification strainer and preparation method thereof |
| CN108774304A (en) * | 2018-06-26 | 2018-11-09 | 扬州工业职业技术学院 | Modified Nano TiO2The preparation method of/epoxy-polyurethane trielement composite material |
| CN108912302A (en) * | 2018-05-25 | 2018-11-30 | 南京工业大学 | A kind of aqueous polyurethane and its preparation method and application |
| CN109196050A (en) * | 2016-06-01 | 2019-01-11 | Dic株式会社 | The manufacturing method of coagulum |
| CN110498899A (en) * | 2019-08-29 | 2019-11-26 | 山东一诺威聚氨酯股份有限公司 | Hydrophobic solvent resistant corrosion TPU material and preparation method thereof |
| CN110685159A (en) * | 2019-09-03 | 2020-01-14 | 清远市齐力合成革有限公司 | Production method of water-based microfiber synthetic leather |
| CN111212869A (en) * | 2017-10-10 | 2020-05-29 | 巴斯夫欧洲公司 | Elastic film |
| CN112012240A (en) * | 2020-08-26 | 2020-12-01 | 瑞洲建设集团有限公司 | Waterproof basement bottom plate that row combination is prevented to cavity |
| CN112694593A (en) * | 2021-01-14 | 2021-04-23 | 浙江大邦聚氨酯有限公司 | Production method of polyurethane resin |
| CN112746138A (en) * | 2019-05-16 | 2021-05-04 | 烟台大学 | Manufacturing process of antifouling, ultralow-total-carbon-emission and wear-resistant cowhide automobile cushion leather |
| CN112812261A (en) * | 2020-12-30 | 2021-05-18 | 广东金发科技有限公司 | Waterborne polyurethane emulsion, nitrile rubber-polyurethane composite glove and preparation method thereof |
| WO2021128870A1 (en) * | 2019-12-27 | 2021-07-01 | 红宝丽集团股份有限公司 | Solvent-free polyurethane dispersion with controllable particle size and aqueous polyurethane coating solution |
| TWI746755B (en) * | 2017-01-11 | 2021-11-21 | 義大利商胡伯集團義大利公司 | Polyurethane being suitable as binder for a modular printing ink system |
| CN113845641A (en) * | 2021-10-22 | 2021-12-28 | 旭川化学（苏州）有限公司 | Large-particle-size waterborne polyurethane emulsion, preparation method and application thereof in impregnated gloves |
| CN114381048A (en) * | 2021-12-08 | 2022-04-22 | 淮安新坤安防科技有限公司 | Cutting-resistant polyurethane dipped latex protective glove and preparation process thereof |
| CN115404037A (en) * | 2022-09-29 | 2022-11-29 | 东莞市纳百川电子科技有限公司 | Metal hand die weld joint filling material, preparation method and weld joint treatment process |
| CN116285637A (en) * | 2023-04-10 | 2023-06-23 | 齐鲁工业大学(山东省科学院) | High-strength anticorrosion aqueous polyurethane, anticorrosion material and application |
-
2008
- 2008-07-17 CN CNA2008100213252A patent/CN101328383A/en active Pending
Cited By (78)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101845133B (en) * | 2010-04-01 | 2011-12-28 | 陕西科技大学 | Method for preparing natural polyhydroxy compound modified aqueous polyurethane emulsion |
| CN101845133A (en) * | 2010-04-01 | 2010-09-29 | 陕西科技大学 | Method for preparing natural polyhydroxy compound modified aqueous polyurethane emulsion |
| CN101845269A (en) * | 2010-05-31 | 2010-09-29 | 淄博永麒化工技术开发有限公司 | Waterborne polyurethane finishing agent for PVC (Polyvinyl Chloride) protective gloves and preparation method thereof |
| CN101885830A (en) * | 2010-06-24 | 2010-11-17 | 同济大学 | Synthesis method of waterborne polyurethane emulsion |
| CN101885830B (en) * | 2010-06-24 | 2012-01-25 | 同济大学 | Synthesis method of waterborne polyurethane emulsion |
| CN101942255A (en) * | 2010-08-09 | 2011-01-12 | 上海瑞鹏化工材料科技有限公司 | Preparation and application process of polyurethane-modified acrylate thick film type elastic coating material capable of being rapidly solidified at ordinary temperature |
| CN101942255B (en) * | 2010-08-09 | 2012-07-04 | 上海瑞鹏化工材料科技有限公司 | Preparation and application process of polyurethane-modified acrylate thick film type elastic coating material capable of being rapidly solidified at ordinary temperature |
| CN102040724A (en) * | 2010-11-01 | 2011-05-04 | 江苏东邦科技有限公司 | Non-yellowing polyurethane resin for waterproof coating and preparation method thereof |
| CN102050935A (en) * | 2010-12-08 | 2011-05-11 | 肇庆千江高新材料科技有限公司 | Water-soluble polyurethane curing agent and preparation method thereof |
| CN102174165A (en) * | 2010-12-28 | 2011-09-07 | 东莞市英科水墨有限公司 | Waterborne polyurethane binder and preparation method thereof |
| CN102174165B (en) * | 2010-12-28 | 2012-09-26 | 东莞市英科水墨有限公司 | Waterborne polyurethane binder and preparation method thereof |
| CN102161861A (en) * | 2010-12-29 | 2011-08-24 | 上海东升新材料有限公司 | Modified polyurethane emulsion for paint |
| CN102161861B (en) * | 2010-12-29 | 2014-08-06 | 上海东升新材料有限公司 | Modified polyurethane emulsion for paint |
| CN102516745A (en) * | 2011-11-23 | 2012-06-27 | 王曦 | Oil bag manufacturing method of automatic die mold demolding impermeabilisation test machine |
| CN102585150B (en) * | 2012-02-01 | 2013-09-04 | 嘉兴学院 | Preparation method of anionic aqueous polyurethane dispersoid for fabric coating and decoration |
| CN102585150A (en) * | 2012-02-01 | 2012-07-18 | 嘉兴学院 | Preparation method of anionic aqueous polyurethane dispersoid for fabric coating and decoration |
| CN102786654A (en) * | 2012-08-23 | 2012-11-21 | 蚌埠金黄山凹版印刷有限公司 | Nano waterborne ink binder and preparation method thereof |
| CN102786651A (en) * | 2012-08-23 | 2012-11-21 | 深圳市科彩印务有限公司 | Waterborne polyurethane binder, waterborne polyurethane composite binder and preparation method of waterborne polyurethane binder and waterborne polyurethane composite binder |
| CN102786651B (en) * | 2012-08-23 | 2013-12-11 | 深圳市科彩印务有限公司 | Waterborne polyurethane binder, waterborne polyurethane composite binder and preparation method of waterborne polyurethane binder and waterborne polyurethane composite binder |
| CN102786654B (en) * | 2012-08-23 | 2014-06-11 | 蚌埠金黄山凹版印刷有限公司 | Nano waterborne ink binder and preparation method thereof |
| CN103130977A (en) * | 2013-01-08 | 2013-06-05 | 厦门大学 | Polyol polyurethane dispersions of two-component waterborne wood lacquer and preparation method thereof |
| CN103130977B (en) * | 2013-01-08 | 2016-04-06 | 厦门大学 | Polyurethane polyol dispersion of a kind of aqueous wood lacquer with double components and preparation method thereof |
| CN103360934B (en) * | 2013-07-31 | 2016-04-13 | 常德市武陵金德镭射科技有限公司 | Mute silver-colored transfer coatings of a kind of water-based and preparation method thereof |
| CN103360934A (en) * | 2013-07-31 | 2013-10-23 | 常德市武陵金德镭射科技有限公司 | Waterborne matte silver transfer painting and preparation method therefor |
| CN103360570A (en) * | 2013-07-31 | 2013-10-23 | 常德市武陵金德镭射科技有限公司 | Waterborne polyurethane, preparation method therefor and waterborne transfer painting |
| CN103450440A (en) * | 2013-09-03 | 2013-12-18 | 山东天庆科技发展有限公司 | Waterborne polyurethane resin and preparation method thereof |
| CN103450442A (en) * | 2013-09-03 | 2013-12-18 | 山东天庆科技发展有限公司 | Waterborne polyurethane resin and synthetic method thereof |
| CN103450440B (en) * | 2013-09-03 | 2015-06-10 | 山东天庆科技发展有限公司 | Waterborne polyurethane resin and preparation method thereof |
| CN103450442B (en) * | 2013-09-03 | 2015-06-17 | 山东天庆科技发展有限公司 | Waterborne polyurethane resin and synthetic method thereof |
| CN103666234A (en) * | 2013-12-12 | 2014-03-26 | 青岛海洋新材料科技有限公司 | Preparation method of titanium nanometer organic anticorrosive paint |
| CN103694940A (en) * | 2013-12-15 | 2014-04-02 | 山西省应用化学研究所 | Method for preparing fast curing one-component water-based polyurethane adhesive |
| CN103740259A (en) * | 2014-01-15 | 2014-04-23 | 许建琴 | Polyurethane waterproof paint and preparation method thereof |
| CN105916947A (en) * | 2014-01-17 | 2016-08-31 | 巴斯夫欧洲公司 | Lamination printing ink comprising an aqueous dispersion comprising polyurethane |
| CN103865250A (en) * | 2014-04-03 | 2014-06-18 | 昆山金有利新材料科技有限公司 | Fireproof polyurethane film and preparation method thereof |
| CN103992461A (en) * | 2014-04-05 | 2014-08-20 | 秦皇岛出入境检验检疫局煤炭检测技术中心 | Aqueous polyurethane phase change energy storage material |
| CN104497952A (en) * | 2014-12-17 | 2015-04-08 | 广东菲安妮皮具股份有限公司 | High-water-resistance leather adhesive |
| CN104479613A (en) * | 2014-12-17 | 2015-04-01 | 广东菲安妮皮具股份有限公司 | Environment-friendly leather adhesive |
| CN104974472A (en) * | 2015-07-20 | 2015-10-14 | 湖北省交通运输厅黄黄高速公路管理处 | Preparation method of high-strength organic grouting material for roads |
| CN105332287A (en) * | 2015-10-14 | 2016-02-17 | 安徽中恩化工有限公司 | Coating resin used for high temperature resistant high adhesive force wet hand wearable PVC gloves, and preparation method thereof |
| CN105199593A (en) * | 2015-11-02 | 2015-12-30 | 淄博夸克医药技术有限公司 | Modified polyurethane fireproof coating with wear resistance |
| CN105462479A (en) * | 2015-12-21 | 2016-04-06 | 潍坊市宏源防水材料有限公司 | Environment-friendly weather-proof self-stratifying one-component waterproof paint and preparation method thereof |
| CN105639777B (en) * | 2016-01-29 | 2017-10-03 | 山东星宇手套有限公司 | A kind of wear-resisting flannelette butyronitrile gloves and its preparation technology |
| CN105639777A (en) * | 2016-01-29 | 2016-06-08 | 山东星宇手套有限公司 | Wear-resistant flannelette nitrile gloves and preparation technology thereof |
| CN109196050A (en) * | 2016-06-01 | 2019-01-11 | Dic株式会社 | The manufacturing method of coagulum |
| CN109196050B (en) * | 2016-06-01 | 2021-09-21 | Dic株式会社 | Method for producing solidified product |
| CN106432678A (en) * | 2016-11-17 | 2017-02-22 | 无锡市长安曙光手套厂 | Medical glove material |
| US11466116B2 (en) | 2017-01-11 | 2022-10-11 | Hubergroup Italia | Polyurethane being suitable as binder for a modular printing ink system |
| TWI746755B (en) * | 2017-01-11 | 2021-11-21 | 義大利商胡伯集團義大利公司 | Polyurethane being suitable as binder for a modular printing ink system |
| CN106832883A (en) * | 2017-01-17 | 2017-06-13 | 南通强生安全防护科技股份有限公司 | Aqueous PU composite mortars of Graphene and its production and use |
| CN107236110A (en) * | 2017-05-23 | 2017-10-10 | 兰州科天健康科技股份有限公司 | A kind of medical gloves polyaminoester emulsion and preparation method thereof |
| CN107226897A (en) * | 2017-07-21 | 2017-10-03 | 蓝帆医疗股份有限公司 | One kind can breathe surgical glove waterborne polyurethane resin material and preparation method thereof |
| CN107400190A (en) * | 2017-07-21 | 2017-11-28 | 蓝帆医疗股份有限公司 | One kind can breathe surgical glove and preparation method thereof |
| CN107573717A (en) * | 2017-09-13 | 2018-01-12 | 杨磊 | The formula and preparation technology of a kind of polyurethane |
| CN111212869B (en) * | 2017-10-10 | 2023-09-29 | 巴斯夫欧洲公司 | Elastic film |
| CN111212869A (en) * | 2017-10-10 | 2020-05-29 | 巴斯夫欧洲公司 | Elastic film |
| CN107983264A (en) * | 2017-10-30 | 2018-05-04 | 珠海市金团化学品有限公司 | A kind of environment-friendly type Water/oil dual-purpose macromolecule dispersing agent and preparation method thereof |
| CN107983264B (en) * | 2017-10-30 | 2020-03-17 | 珠海市金团化学品有限公司 | Environment-friendly water-oil dual-purpose polymer dispersant and preparation method thereof |
| CN108250399B (en) * | 2017-12-01 | 2020-07-07 | 上海汇得科技股份有限公司 | Wet polyurethane resin for labor protection gloves with high demolding performance and good wear resistance and preparation method thereof |
| CN108250399A (en) * | 2017-12-01 | 2018-07-06 | 上海汇得科技股份有限公司 | A kind of high demoulding, excellent wear resistance safety and industrial gloves wet polyurethane resin and preparation method |
| CN108671745A (en) * | 2018-05-05 | 2018-10-19 | 安徽乐金环境科技有限公司 | A kind of preparation method of room air composite purifying agent |
| CN108636103A (en) * | 2018-05-05 | 2018-10-12 | 安徽乐金环境科技有限公司 | A kind of room air composite purifying agent |
| CN108722013A (en) * | 2018-05-05 | 2018-11-02 | 安徽乐金环境科技有限公司 | A kind of room air composite purification strainer and preparation method thereof |
| CN108912302A (en) * | 2018-05-25 | 2018-11-30 | 南京工业大学 | A kind of aqueous polyurethane and its preparation method and application |
| CN108774304A (en) * | 2018-06-26 | 2018-11-09 | 扬州工业职业技术学院 | Modified Nano TiO2The preparation method of/epoxy-polyurethane trielement composite material |
| CN112746138A (en) * | 2019-05-16 | 2021-05-04 | 烟台大学 | Manufacturing process of antifouling, ultralow-total-carbon-emission and wear-resistant cowhide automobile cushion leather |
| CN112746138B (en) * | 2019-05-16 | 2022-01-21 | 烟台大学 | Antifouling ultralow-total-carbon-emission wear-resistant smoke-inhibiting material for cowhide automobile cushion leather |
| CN110498899A (en) * | 2019-08-29 | 2019-11-26 | 山东一诺威聚氨酯股份有限公司 | Hydrophobic solvent resistant corrosion TPU material and preparation method thereof |
| CN110685159A (en) * | 2019-09-03 | 2020-01-14 | 清远市齐力合成革有限公司 | Production method of water-based microfiber synthetic leather |
| WO2021128870A1 (en) * | 2019-12-27 | 2021-07-01 | 红宝丽集团股份有限公司 | Solvent-free polyurethane dispersion with controllable particle size and aqueous polyurethane coating solution |
| CN112012240A (en) * | 2020-08-26 | 2020-12-01 | 瑞洲建设集团有限公司 | Waterproof basement bottom plate that row combination is prevented to cavity |
| CN112812261A (en) * | 2020-12-30 | 2021-05-18 | 广东金发科技有限公司 | Waterborne polyurethane emulsion, nitrile rubber-polyurethane composite glove and preparation method thereof |
| CN112694593A (en) * | 2021-01-14 | 2021-04-23 | 浙江大邦聚氨酯有限公司 | Production method of polyurethane resin |
| CN113845641A (en) * | 2021-10-22 | 2021-12-28 | 旭川化学（苏州）有限公司 | Large-particle-size waterborne polyurethane emulsion, preparation method and application thereof in impregnated gloves |
| CN114381048A (en) * | 2021-12-08 | 2022-04-22 | 淮安新坤安防科技有限公司 | Cutting-resistant polyurethane dipped latex protective glove and preparation process thereof |
| CN115404037A (en) * | 2022-09-29 | 2022-11-29 | 东莞市纳百川电子科技有限公司 | Metal hand die weld joint filling material, preparation method and weld joint treatment process |
| CN115404037B (en) * | 2022-09-29 | 2023-08-15 | 东莞市纳百川电子科技有限公司 | Metal hand die weld joint filling material, preparation method and weld joint treatment process |
| CN116285637A (en) * | 2023-04-10 | 2023-06-23 | 齐鲁工业大学(山东省科学院) | High-strength anticorrosion aqueous polyurethane, anticorrosion material and application |
| CN116285637B (en) * | 2023-04-10 | 2024-01-16 | 齐鲁工业大学(山东省科学院) | High-strength anticorrosion aqueous polyurethane, anticorrosion material and application |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101328383A (en) | Production method for liner gloves aqueous polyurethane coating connection material | |
| CN102618204B (en) | Hot-melt adhesive for bonding layer of artificial leather and preparation method as well as application thereof | |
| CN104231209B (en) | Preparation method for high-hardness waterborne polyurethane dispersion | |
| CN103087286B (en) | Waterborne polyurethane elastic dispersion and preparation method thereof | |
| CN102532463B (en) | Aqueous polyurethane and preparation method thereof | |
| CN110835401B (en) | Waterborne polyurethane surface layer resin and preparation method thereof | |
| CN109160994B (en) | Polyurethane dispersion for dry coating primer, and preparation method and application thereof | |
| CN101824294B (en) | Preparation method of tetrabasic copolymerized waterborne polyurethane automotive interior adhesive | |
| CN107141434B (en) | Waterborne polyurethane resin for synthetic leather fabric and preparation method thereof | |
| CN106220817B (en) | A kind of no-solvent type interior leather for automobiles middle layer polyurethane resin and preparation method thereof | |
| CN107586510B (en) | Preparation method of corrosion-resistant polyurethane modified epoxy resin emulsion | |
| CN107033321B (en) | Waterborne polyurethane resin and preparation method thereof | |
| CN112694591A (en) | Preparation method of silane coupling agent modified solvent-free waterborne polyurethane | |
| CN101235129A (en) | Method for preparing polybutadiene-base water polyurethane and modified emulsion thereof | |
| CN101717487A (en) | Polyurethane emulsion and coating agent used for aquosity coating agent of knitted lining glove as well as preparation method and coating method thereof | |
| CN102746818B (en) | Waterborne polyurethane material and preparation method thereof | |
| CN101182406A (en) | Method for preparing multiple modified self-crosslinking aqueous polyurethane adhesive agent | |
| CN115181232B (en) | Polyurethane material and preparation method and application thereof | |
| CN107974156A (en) | A kind of environment-friendly water-based stripping lacquer of automobile using and its preparation method and application | |
| CN108314770B (en) | Carbon dioxide-based aqueous polyurethane dispersion, preparation method thereof and carbon dioxide-based aqueous polyurethane pressure-sensitive adhesive | |
| WO2021103376A1 (en) | Non-ionic waterborne polyurethane, preparation method therefor and application thereof | |
| CN110835398A (en) | Preparation method of rosin-based waterborne polyurethane emulsion | |
| CN114149737B (en) | Polyurethane coating and application thereof | |
| CN107936802A (en) | A kind of preparation method of anti-corrosion polyurea elastomer coating | |
| CN113637140B (en) | Hydrophilic isocyanate crosslinking agent and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Open date: 20081224 |