CN104497258A - Super-elastic wear-resisting waterborne polyurethane resin and composition and application of super-elastic wear-resisting waterborne polyurethane resin and composition - Google Patents
Super-elastic wear-resisting waterborne polyurethane resin and composition and application of super-elastic wear-resisting waterborne polyurethane resin and composition Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6659—Compounds of group C08G18/42 with compounds of group C08G18/34
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
- D06M15/572—Reaction products of isocyanates with polyesters or polyesteramides
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/35—Abrasion, pilling or fibrillation resistance
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Abstract
The invention discloses super-elastic wear-resisting waterborne polyurethane resin which is prepared by polymerizing polyester glycol and polyisocyanates. The invention further discloses a preparation method of the resin. By adopting the super-elastic wear-resisting waterborne polyurethane resin disclosed by the invention, slurry can be prepared to coat the surfaces of knitted gloves, so that the problems that in the prior art, knitted gloves made by using a conventional method are hard in hand feeling, poor in resilience, low in wearing resistance, and the like.
Description
Technical field
The present invention relates to a kind of new resin material, composition and application thereof, particularly relate to a kind of superlastic abrasion-resistance water urethane resin, composition, preparation method by polyester diol and polyisocyanic acid Lipase absobed and be applied to knitted gloves coating.
Background technology
Mainly comprise solvent-borne type and nitrile rubber as knitted working glove coating at present, also have a small amount of nitrile rubber-aqueous polyurethane mixed coating.Solvent-based coating content a large amount of high toxicity solvent dimethyl formamide DMF, no matter take which kind of measure in process of production, in finished product gloves, residual DMF is accomplished fact, the problem that just residual quantity is how many, such these gloves of long-time wearing damage HUMAN HEALTH, respiratory system and pulmonary lesion can be caused time serious, nor meet national development environment protection requirement.Nitrile rubber compares at present and is widely used in knitted working glove coating has developed major step compared to solvent-borne type, but need nitrile rubber sulfidizing in production process, therefore sulphur remaining in gloves also can cause skin damage, for a long time as allergic.Therefore develop aqueous polyurethane and be used for the needs that knitted working glove coating is the needs of social development, people's self-protection and environmental consciousness; aqueous polyurethane take water as dispersion medium; not containing solvent; also do not need sulfidizing, the knitted gloves made has wear-resisting, air-moisture-permeable, ageing-resistant, nontoxic with skin contact.
Current domestic patent has also delivered several sections of making methods about waterborne polyurethane coated safety and industrial gloves, as patent publication No. CN102113717A, " a kind of environment-friendly water-based polyurethane coated glove and preparation method thereof ", but all generally mention and need use urethane resin to allocate, not detailed analysis and the performance index introducing aqueous polyurethane.Because the performance range of waterborne polyurethane resin is more wide in range, hard water-base resin can be applied to wood lacquer, soft waterborne polyurethane resin can as sizing agent, and knitted working glove is higher to coating resin performance requriements, as feel, resilience, wear-resisting (at least >=2000 turns), so be not that any waterborne polyurethane resin can use as coating resin.
Coating material is different, requires also completely different to resin property.Knitted working glove environment for use directly contacts with human skin, and each staff size is totally different, finger meeting tortuous and object friction repeatedly in use procedure, so require that coating has secondary to human non-toxic, soft plentiful (during use skin-proximal, hand just can not feel jerky), rebound resilience will get well (in use procedure, hand just can not feel that acid is swollen) and high-wearing feature (gloves work-ing life just can for a long time).Therefore waterborne polyurethane resin must meet the elongation of 800 ~ 1500% and the breaking tenacity of 20 ~ 40MPa simultaneously, could meet gloves and have soft and full degree and wear-resisting 3 grades (2000 turns) requirements.
The molecular weight of polyester diol and structures shape waterborne polyurethane resin performance, the performance of aqueous polyurethane determines its Application Areas.Therefore to Property of Waterborne Polyurethane, the present invention requires that by regulating the ratio of diprotic acid and dibasic alcohol to synthesize molecular weight be 3000 ~ 6000 polyester diol according to above knitted working glove, solve polyethers on market/unicity and unadjustable property.And above polyester diol is synthesized the aqueous polyurethane obtained and met the elongation of 800 ~ 1500% and the breaking tenacity of 20 ~ 40MPa, the wear-resisting progression of gloves reaches and also reaches 7000 ~ 10000 turns, level Four.
Another aqueous polyurethane is dispersion medium with water, there is no the solvent adding and have malicious paratype as DMF etc., and coating do not need by sulfuration yet in building-up process, ensures that whole link be all controlled to Environmental insults is meet environmental protection theory like this.
Why aqueous polyurethane needs foaming process, because intensive microvesicle coating can the injury of buffering objects opponent on gloves, as broken in heat insulation, anti-snag, anti-cutting and piercing through, or again according to adding special auxiliary agent (as anti-electrostatic, fire-retardant) in special occasions demand coating paste again.
Summary of the invention
The object of the invention is
First, prepare a kind of new polyester diol (Mn=3000 ~ 6000) and polyisocyanates, and utilize its synthesis superlastic abrasion-resistance water urethane resin for knitted working glove coating, replace solvents type and nitrile rubber coating are to the injury of skin; Separately solve that commercially available common polyether polyvalent alcohol and polyester diol synthesis waterborne polyurethane resin make gloves feel is hardened, resilience is poor, the wear-resisting problem such as low.
Object of the present invention can be achieved through the following technical solutions:
A kind of waterborne polyurethane resin, its speciality is that described resin generates prepolymer by polyester diol and polyisocyanates under the existence of ionic compound, and make the content of isocyanic ester in prepolymer be 1.05% ~ 5%, then in adding and salt forming agent, finally add deionized water emulsification, add the reaction of rear chainextender simultaneously and prepare.
Wherein polyester diol, according to weight parts, its composition of raw materials consists of: diprotic acid 50 ~ 80 parts; Dibasic alcohol 15 ~ 45 parts; Catalyzer 0.05 ~ 0.2 part; Antioxidant 0.001 ~ 0.05 part;
Polyester diol preparation method is as follows: under protection of inert gas, the diprotic acid of metering, dibasic alcohol and antioxidant are dropped in reactor and adds, rise to 150 ~ 170 DEG C of reaction 1 ~ 2h, along with steaming of moisture, then 190 ~ 210 DEG C are warming up to, when surveying acid number lower than 30mgKOH/g, add catalyzer, start to vacuumize stage by stage, progressively gas clean-up, general requirement vacuum tightness will reach-0.09MPa, is incubated 6 ~ 8h in the process, acid number drop to 0.4mgKOH/g and hydroxyl value up to standard after, stopped reaction discharging;
Described polyester diol molecular structure is the dibasic alcohol of long chain type, acid number≤0.4mgKOH/g, hydroxyl value 18 ~ 38mgKOH/g, Mn=3000 ~ 6000, and state is incarnadine thickness colloid;
Described diprotic acid is succinic acid, pentanedioic acid, hexanodioic acid, phthalic anhydride or their mixture;
Described dibasic alcohol is ethylene glycol, 1,3-PD, BDO, 1,6-hexylene glycol or their mixture;
Described catalyzer is Dibutyltin oxide, dibutyl tin dilaurate, titanium isopropylate or tetrabutyl titanate;
Described antioxidant is Hypophosporous Acid, 50, triphenylphosphate;
Superlastic abrasion-resistance water urethane resin is by making polyester diol by oneself and polyisocyanates generates prepolymer under the existence of ionic compound, and make the content of isocyanic ester in prepolymer be 1.05% ~ 5%, then neutralizing agent salify is added, finally add deionized water emulsification, add simultaneously rear chainextender reaction system;
Described polyisocyanates preferred aliphat polyisocyanates, such as IPDI (isophorone diisocyanate), H12MDI (4,4 '-dicyclohexyl methane diisocyanate) and HDI (hexamethylene diisocyanate);
The preferred dimethylol propionic acid of described ionic compound (DMPA) and sulfonate diamines, commercially available N-(2-amino-ethyl) taurine sodium, sulfonic group glycol;
In described such as, with the preferred mineral alkali of salt forming agent or organic amine, sodium hydroxide, triethylamine, ammoniacal liquor;
Described rear chainextender is many primary amine compound, such as isophorone-diamines, quadrol, diethylenetriamine, triethylene tetramine.
It is organic fluorine class (Changzhou Ling Da Chemical Company is commercially available) that described water-based takes off acetone agent
Described solvent be acetone, N-Methyl pyrrolidone one or more.
Preparation method is as follows for superlastic abrasion-resistance water urethane resin: in weight in grams, under drying nitrogen protection, by the polyester diol after vacuum hydro-extraction 30 ~ 200 grams, isophorone diisocyanate (IPDI) 32 grams adds in reaction vessel, under mechanical stirring, temperature 85 DEG C ~ 100 DEG C, reaction 2 ~ 3 hours; Reduce temperature of reaction system to 40 DEG C ~ 60 DEG C, add small molecule chain extender dibasic alcohol 2.9 ~ 13.2 grams, linking agent TriMethylolPropane(TMP) (TMP) 0.1 ~ 1.3 gram, solvent acetone 10 ~ 50ml, catalyzer: dibutyl tin laurate (T-12) 0.001 ~ 0.02 gram, stannous octoate (T-9) 0.001 ~ 0.02 gram, under mechanical stirring, temperature 60-70 DEG C reaction 3 ~ 6 hours; Add sulfonic group diamines 1 ~ 10 gram, isocyanate groups (-NCO) content when no longer changing, is cooled in room temperature and salify, obtains urethane resin in performed polymer that question response generates; Under high shear add 250 ~ 500ml water, then add the dispersion of rear chainextender, obtain transparent aqueous polyurethane emulsion; Aqueous polyurethane emulsion is added between 50-60 DEG C water-based and take off acetone agent 0.1 gram ~ 1.0 grams, within 20 ~ 60 minutes, solvent is sloughed again by underpressure distillation, obtain the superlastic abrasion-resistance water urethane resin that solid content is 30 ~ 45%, its breaking tenacity 20 ~ 40MPa, elongation 800 ~ 1500%, soft plentiful.
Preparation method is as follows for knitted working glove coating paste: aqueous polyurethane 50 ~ 70 parts, mill base 0.01 ~ 0.05 part, whipping agent 0.5 ~ 5 part, suds-stabilizing agent 0.5 ~ 5 part, thickening material 1 ~ 10 part and 25 ~ 50 parts, water or 1 ~ 5 part of functional aid (as antistatic agent, fire retardant etc.) are made into slurry;
Described mill base is the assorted mill base (Shanghai Wenhua commercial black aqueous color paste 8501) of water-based;
Described whipping agent is sodium laurylsulfonate, sodium lauryl sulphate, organic silicon modified by polyether (Hangzhou Bao Er get is commercially available);
Described suds-stabilizing agent is organic silicon modified by polyether (Hangzhou Bao Er get is commercially available), lauric acid amide of ethanol, fatty alcohol;
Described thickening material is polyurethane thickener (the commercially available HEUR-A/B of Anhui peace section fine chemistry industry), sodium polyacrylate, acrylic thickener (ASE-60);
Described functional aid is antistatic agent (the commercially available STAT305 of the sharp chemical industry of speeding in Guangzhou), fire retardant (the fire-retardant commercially available YS-B09 of Nantong IELTS).
The application of described obtained glove coating slurry, it is characterized in that, after glove surface being applied peptizer (5 ~ 15% calcium nitrate aqueous solution), by gloves Dipping slurry after dry 2 minutes, then gloves are put into the demoulding after 80 ~ 100 DEG C of baking oven inner drying 1h.
A kind of superlastic abrasion-resistance water of the present invention urethane resin, composition and be applied to knitted gloves coating and have the following advantages:
(1) performance of polyester diol determines waterborne polyurethane resin performance, and homemade polyester diol can need Molecular regulator amount (Mn=3000 ~ 6000) according to gloves elasticity and intensity;
(2) synthesizing aqueous polyurethane take water as dispersion medium, and solvent-free, toxicological harmless meets environmental requirement;
(3) synthesize waterborne polyurethane resin and there is good hand feeling, high resilience (elongation at break 800 ~ 1500%), high breaking tenacity (20 ~ 40MPa);
(4) good, the wear-resisting height of the knitted working glove good hand feeling made, air-moisture-permeable, rebound resilience (7000 ~ 10000 turns, level Four);
(5) meet knitted working glove coating needs and can replace solvent-borne type and nitrile rubber.
Embodiment
Explain further by way of example below and the present invention is described, but the present invention is not limited to following examples.
Embodiment 1
A kind of superlastic abrasion-resistance water urethane resin, composition and be applied to knitted gloves coating production:
(1) polyester diol preparation: under protection of inert gas, by the 500kg succinic acid of metering, 300kg pentanedioic acid, 423kg ethylene glycol and 0.2kg antioxidant drop in reactor and add, rise to 150 ~ 170 DEG C of reaction 1 ~ 2h, along with steaming of moisture, then 190 ~ 210 DEG C are warming up to, when surveying acid number lower than 30mgKOH/g, add 0.8kg catalyzer, start to vacuumize stage by stage, progressively gas clean-up, general requirement vacuum tightness will reach-0.09MPa, be incubated 6 ~ 8h in the process, the hydroxyl value that acid number drops to 0.4mgKOH/g and survey is after 37 ~ 38mgKOH/g (Mn=3000), stopped reaction cooling discharge, obtaining polyester diol under normal temperature is incarnadine thick gel.
(2) superlastic abrasion-resistance water urethane resin preparation: in weight kg, under drying nitrogen protection, make the 108.1kg after vacuum hydro-extraction by oneself polyester diol (hydroxyl value=37.4, Mn=3000), isophorone diisocyanate (IPDI) 32kg adds in reaction vessel, under mechanical stirring, temperature 85 DEG C, reaction 2h; Reduce temperature of reaction system to 40 DEG C, add small molecule chain extender 1,4-butyleneglycol 4.5kg, linking agent TriMethylolPropane(TMP) (TMP) 1kg, 3.07kg dimethylol propionic acid (DMPA) solvent acetone 100kg, catalyzer: dibutyl tin laurate (T-12) 0.075kg, stannous octoate (T-9) 0.075kg, under mechanical stirring, temperature 60 C reaction 3h, when in the performed polymer that question response generates, isocyanate groups (-NCO) content no longer changes, be cooled in room temperature 2.3kg triethylamine and salify, obtain urethane resin; Under high shear add 350kg water, then add 1.03kg quadrol chain extension, obtain aqueous polyurethane; Aqueous polyurethane emulsion is added between 50 DEG C water-based and take off acetone agent 0.01kg, then within 60 minutes, slough solvent by underpressure distillation, obtain the aqueous polyurethane emulsion that solid content is 30%, this emulsion appearance oyster white.
(3) knitted working glove coating paste preparation: aqueous polyurethane 500kg, 0.1kg aqueous black mill base 8501, BD-3071 (Hangzhou Bao Er get) 5kg, sodium laurylsulfonate 2kg, thickening material HEUR-A (Hefei peace section fine chemistry industry) 10kg and water 483kg are made into slurry.
After glove surface being applied peptizer (10% calcium nitrate aqueous solution), by gloves Dipping slurry after dry 2 minutes, again gloves are put into the demoulding after 80 ~ 100 DEG C of baking oven inner drying 1h, obtain the aqueous coating safety and industrial gloves that surface has high-elastic wear-resistant.
Embodiment 2
A kind of superlastic abrasion-resistance water urethane resin, composition and be applied to knitted gloves coating polymerizing preparation method:
(1) polyester diol preparation: under protection of inert gas, by the 647kg hexanodioic acid of metering, 200kg1, 4-butyleneglycol, 300kg1, 6-hexylene glycol and 0.2kg antioxidant drop in reactor and add, rise to 150 ~ 170 DEG C of reaction 1 ~ 2h, along with steaming of moisture, then 190 ~ 210 DEG C are warming up to, when surveying acid number lower than 30mgKOH/g, add 0.8kg catalyzer, start to vacuumize stage by stage, progressively gas clean-up, general requirement vacuum tightness will reach-0.09MPa, be incubated 6 ~ 8h in the process, the hydroxyl value that acid number drops to below 0.4mgKOH/g and survey is after 28.5 ~ 29mgKOH/g (Mn=4000), stopped reaction cooling discharge, obtaining polyester diol under normal temperature is incarnadine thick gel.
(2) superlastic abrasion-resistance water urethane resin preparation: in weight kg, under drying nitrogen protection, make the 144.1kg after vacuum hydro-extraction by oneself polyester diol (hydroxyl value=28, Mn=4000), 4,4 '-dicyclohexyl methane diisocyanate (H12MDI) 37.8kg adds in reaction vessel, under mechanical stirring, temperature 85 DEG C, reaction 2h; Reduce temperature of reaction system to 40 DEG C, add small molecule chain extender glycol ether 4.1kg, linking agent TriMethylolPropane(TMP) (TMP) 1kg, 4.56kg dimethylol propionic acid (DMPA) solvent acetone 100kg, catalyzer: dibutyl tin laurate (T-12) 0.075kg, stannous octoate (T-9) 0.075kg, under mechanical stirring, temperature 60 C reaction 3h, when in the performed polymer that question response generates, isocyanate groups (-NCO) content no longer changes, be cooled in room temperature 3.4kg triethylamine and salify, obtain urethane resin; Under high shear add 290kg water, then add 1.03kg quadrol chain extension, obtain aqueous polyurethane; Aqueous polyurethane emulsion is added between 50 DEG C water-based and take off acetone agent 0.01kg, then within 60 minutes, slough solvent by underpressure distillation, obtain the aqueous polyurethane emulsion that solid content is 40%, the translucent inclined oyster white of this emulsion appearance.
(3) knitted working glove coating paste preparation: aqueous polyurethane 500kg, 0.1kg aqueous black mill base 8501, lauric acid amide of ethanol 5kg, sodium laurylsulfonate 2kg, thickening material HEUR-B (Hefei peace section fine chemistry industry) 10kg and water 483kg are made into slurry.
After glove surface being applied peptizer (10% calcium nitrate aqueous solution), by gloves Dipping slurry after dry 2 minutes, again gloves are put into the demoulding after 80 ~ 100 DEG C of baking oven inner drying 1h, obtain the aqueous coating safety and industrial gloves that surface has high-elastic wear-resistant.
Embodiment 3
A kind of superlastic abrasion-resistance water urethane resin, composition and be applied to knitted gloves coating production:
(1) polyester diol preparation: under protection of inert gas, by the 300kg hexanodioic acid of metering, 300kg succinic acid, 268.7kg1, ammediol, 1391, 6-hexylene glycol and 0.2kg antioxidant drop in reactor and add, rise to 150 ~ 170 DEG C of reaction 1 ~ 2h, along with steaming of moisture, then 190 ~ 210 DEG C are warming up to, when surveying acid number lower than 30mgKOH/g, add 0.8kg catalyzer, start to vacuumize stage by stage, progressively gas clean-up, general requirement vacuum tightness will reach-0.09MPa, be incubated 6 ~ 8h in the process, the hydroxyl value that acid number drops to below 0.4mgKOH/g and survey is after 22 ~ 23mgKOH/g (Mn=5000), stopped reaction cooling discharge, obtaining polyester diol under normal temperature is incarnadine thick gel.
(2) superlastic abrasion-resistance water urethane resin preparation: in weight kg, under drying nitrogen protection, make the 180.1kg after vacuum hydro-extraction by oneself polyester diol (hydroxyl value=22.4, Mn=5000), isophorone diisocyanate (IPDI) 32kg adds in reaction vessel, under mechanical stirring, temperature 85 DEG C, reaction 2h; Reduce temperature of reaction system to 40 DEG C, add small molecule chain extender-diglycol ethylene 3.1kg, linking agent TriMethylolPropane(TMP) (TMP) 1kg, 5.8kg dimethylol propionic acid (DMPA) solvent acetone 100kg, catalyzer: dibutyl tin laurate (T-12) 0.075kg, stannous octoate (T-9) 0.075kg, under mechanical stirring, temperature 60 C reaction 3h, when in the performed polymer that question response generates, isocyanate groups (-NCO) content no longer changes, be cooled in room temperature 4.4kg triethylamine and salify, obtain urethane resin; Under high shear add 412kg water, then add 1.03kg quadrol chain extension, obtain aqueous polyurethane; Aqueous polyurethane emulsion is added between 50 DEG C water-based and take off acetone agent 0.01kg, then within 60 minutes, slough solvent by underpressure distillation, obtain the aqueous polyurethane emulsion that solid content is 35%, the translucent inclined oyster white of this emulsion appearance.
(3) anti-electrostatic knitted working glove coating paste preparation: aqueous polyurethane 500kg, 0.1kg aqueous black mill base 8501, BD-3071 (Hangzhou Bao Er get) 5kg, sodium laurylsulfonate 2kg, sodium polyacrylate 6kg, water 483kg and 5kg antistatic agent STAT305 are made into slurry.
After glove surface being applied peptizer (10% calcium nitrate aqueous solution), by gloves Dipping slurry after dry 2 minutes, again gloves are put into the demoulding after 80 ~ 100 DEG C of baking oven inner drying 1h, obtain the aqueous coating safety and industrial gloves that surface has high-elastic wear-resistant.
According to above-mentioned experiment embodiment and data as follows:
As can be seen from upper table data, along with the increase of polyester diol molecular weight, the wear-resisting progression of gloves is all higher than three grades, but revolution sharply declines after Mn=4000, and the gloves therefore made as polyester diol Mn=4000 in example 2 are wear-resisting and feel is comprehensively optimum.
Claims (10)
1. a superlastic abrasion-resistance water urethane resin, described resin generates prepolymer by polyester diol and polyisocyanates under the existence of ionic compound, and make the content of isocyanic ester in prepolymer be 1.05% ~ 5%, then in adding and salt forming agent, finally add deionized water emulsification, add the reaction of rear chainextender simultaneously and prepare.
2. superlastic abrasion-resistance water urethane resin as claimed in claim 1, wherein said polyester diol, according to weight parts, its composition of raw materials consists of: diprotic acid 50 ~ 80 parts; Dibasic alcohol 15 ~ 45 parts; Catalyzer 0.05 ~ 0.2 part; Antioxidant 0.001 ~ 0.02 part; Described polyisocyanates is aliphatic polyisocyante; Described ionic compound is for containing carboxyl dibasic alcohol, sulfonic group diamines or sulfonic group dibasic alcohol; In described and salt forming agent be mineral alkali or trimethylamine; Described rear chainextender is many primary amines, quadrol, diethylenetriamine, triethylene tetramine etc.; Described polyester diol molecular structure is the dibasic alcohol of long chain type, acid number≤0.4mgKOH/g, hydroxyl value 18 ~ 37mgKOH/g, and molecular weight is 3000 ~ 6000, and state is incarnadine thickness colloid.
3. superlastic abrasion-resistance water urethane resin according to claim 2; it is characterized in that the preparation method of described polyester diol is as follows: under protection of inert gas; the diprotic acid of metering, dibasic alcohol and antioxidant are dropped in reactor and adds; rise to 150 ~ 170 DEG C of reaction 1 ~ 2h; then 190 ~ 210 DEG C are warming up to; when surveying acid number lower than 30mgKOH/g; add catalyzer; start to vacuumize stage by stage; progressively gas clean-up is to-0.09MPa; be incubated 6 ~ 8h in the process, acid number drop to 0.4mgKOH/g and hydroxyl value up to standard after, stopped reaction discharging.
4. superlastic abrasion-resistance water urethane resin according to claim 2, is characterized in that described diprotic acid is succinic acid, pentanedioic acid, hexanodioic acid, phthalic anhydride or their mixture; Described dibasic alcohol is ethylene glycol, 1,3-PD, BDO, 1,6-hexylene glycol or their mixture; Described catalyzer is Dibutyltin oxide, dibutyl tin dilaurate, titanium isopropylate or tetrabutyl titanate; Described antioxidant is Hypophosporous Acid, 50, triphenylphosphate.
5. prepare the method for superlastic abrasion-resistance water urethane resin as claimed in claim 1, it is characterized in that described preparation method comprises the steps: in weight in grams, under drying nitrogen protection, by the polyester diol after vacuum hydro-extraction 30 ~ 200 grams, isophorone diisocyanate (IPDI) 32 grams adds in reaction vessel, under mechanical stirring, temperature 85 DEG C ~ 100 DEG C, reaction 2 ~ 3 hours; Reduce temperature of reaction system to 40 DEG C ~ 60 DEG C, add small molecule chain extender dibasic alcohol 2.9 ~ 13.2 grams, linking agent TriMethylolPropane(TMP) (TMP) 0.1 ~ 1.3 gram, solvent acetone 10 ~ 50ml, catalyzer: dibutyl tin laurate (T-12) 0.001 ~ 0.02 gram, stannous octoate (T-9) 0.001 ~ 0.02 gram, under mechanical stirring, temperature 60-70 DEG C reaction 3 ~ 6 hours; Add sulfonic group diamines 1 ~ 10 gram, isocyanate groups (-NCO) content when no longer changing, is cooled in room temperature and salify, obtains urethane resin in performed polymer that question response generates; Under high shear add 250 ~ 500ml water, then add the dispersion of rear chainextender, obtain transparent aqueous polyurethane emulsion; Aqueous polyurethane emulsion is added between 50-60 DEG C water-based and take off acetone agent 0.1 gram ~ 1.0 grams, within 20 ~ 60 minutes, solvent is sloughed again by underpressure distillation, obtain the superlastic abrasion-resistance water urethane resin that solid content is 30 ~ 45%, its breaking tenacity 20 ~ 40MPa, elongation 800 ~ 1500%, soft plentiful.
6. a composition, described composition contains the described superlastic abrasion-resistance water urethane resin of one of claim 1-5.
7. composition as claimed in claim 6, described composition, by weight, superlastic abrasion-resistance water urethane resin 50 ~ 70 parts, mill base 0.01 ~ 0.05 part, whipping agent 0.5 ~ 5 part, suds-stabilizing agent 0.5 ~ 5 part, thickening material 1 ~ 10 part, 25 ~ 50 parts, water or 1 ~ 5 part of functional aid.
8. composition as claimed in claim 7, wherein, described mill base is aqueous color paste; Described whipping agent is sodium laurylsulfonate, sodium lauryl sulphate, organic silicon modified by polyether; Described suds-stabilizing agent is organic silicon modified by polyether, lauric acid amide of ethanol, fatty alcohol; Described thickening material is polyurethane thickener, sodium polyacrylate, acrylic thickener; Described functional aid is antistatic agent, fire retardant.
9. the purposes of composition as described in one of superlastic abrasion-resistance water urethane and/or claim 6-8 as described in one of claim 1-5, described purposes is for preparing knitted gloves coating.
10. purposes as claimed in claim 9, it is characterized in that, glove surface is applied peptizer, after dry 2 minutes, gloves are flooded described coating, gloves are put into the demoulding after 80 ~ 100 DEG C of baking oven inner drying 1h, described peptizer is 5 ~ 15% calcium nitrate aqueous solutions again.
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