CN102206410A - Preparation method of high-solid-content aqueous polyurethane for leather - Google Patents
Preparation method of high-solid-content aqueous polyurethane for leather Download PDFInfo
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Abstract
The invention relates to the field of synthetic leather material polyurethane, in particular to a preparation method of high-solid-content aqueous polyurethane for leather. The method comprises the process steps of: prepolymerization reaction: reacting polyol, a hydrophilic chain extender and isocyanate monomer; monomer modification: adding polyhydroxy monomer to be modified together with polyurethane prepolymer; salt formation by neutralization: adding a neutralizing agent so that an emulsion forms salt ion groups; and chain extension subsequent to emulsification: dissolving an external emulsifying agent and a sulfonic acid chain extender in water to obtain a solution and adding the solution to the system for performing emulsification. In the invention, the emulsification property of the emulsion is improved by using carboxylic acid type and sulfonic acid type chain extenders, so that polyurethane and water are fully emulsified; simultaneously, due to the employment of the method in which self emulsification and external emulsification are combined, not only the stable emulsion can be synthesized, but also the solid content can be increased; in addition, the use of water as the solvent in emulsification is consistent with the requirement of clean production process; and the finally-synthesized emulsion has good film forming performance, high drying speed, no yellowing, excellent mechanical properties and short process flow, is suitable for the synthesis of leather substrates or surface materials, and can take the place of solvent-type products.
Description
Technical field
The present invention relates to synthetic leather material polyurethane field, relate in particular to a kind of preparation method who removes from office with high-solid content water-based polyurethane.
Background technology
Current urethane as the development of synthetic leather material rapidly, synthetic leather is that the non-woven fabrics made from the empty stamen fiber with lotus root shape section structure is a base, polyurethane solution (slurry) dip-coating, wet method through excellent property are solidified, handle a kind of synthetic materials of making again like the natural leather structure through a series of ornamentings such as intaglio, embossing.Synthetic leather product major part in the market is a solvent borne polyurethane, such resin all by how with toluene, dimethylbenzene, acetone, butanone (MEK), ethyl acetate and dimethyl formamide (DMF) etc. as primary solvent.And the harm that solvent causes human body is many-sided.It is much lower that leather use urethane is compared the solvent-borne type cost, and the feature of environmental protection is good, but present domestic water-based PU product solid content is many between 25-40%, has increased time of drying and transportation cost.Therefore domestic leather is active day by day with the research and development of high-solid content water-based polyurethane.
Chinese patent CN101613455A has introduced a kind of self-emulsification height and has contained leather use production of polyurethane method admittedly: after being the synthetic performed polymer of raw material with polyoxyethylene glycol butyleneglycol adipic acid esterdiol, polytetrahydrofuran diol and tolylene diisocyanate, before small molecules diamine chain extension, add encapsulant, thereby molecular weight is reduced, but emulsion viscosity still is 5000mPa
.S/25 ℃, coating property is poor, and the tolylene diisocyanate oxidation-resistance is poor in addition, applies the rear oxidation xanthochromia on synthetic leather, influences outward appearance.
Chinese patent CN101328253A adopts self-emulsification, with polyvalent alcohol, isocyanic ester, the synthetic performed polymer of the disposable adding of chainextender, the cooling back adds the sulfonic acid chainextender, adding emulsifying water again disperses, obtain the emulsion of 50% left and right sides solid content, can be used for leather, but mechanical property (tensile strength, elongation at break and modulus etc.) is poor behind the emulsion film forming, is not suitable for leather substrate or skin-material.
Summary of the invention
At above-mentioned the deficiencies in the prior art, the present invention has introduced a kind of preparation method who removes from office with high solid aquosity urethane.Mainly be with polyvalent alcohol, the multi-hydroxy carboxy acid is that main raw material and polyisocyanates reaction generate performed polymer, in and salify after, behind the question response certain hour, sulfonic acid type chainextender and outer emulsifying agent is water-soluble, join in the system high-speed stirring, dripping proper quantity of defoaming agent, is oyster white blueing light emulsion after the discharging.
Operational path of the present invention mainly comprises four parts: (1) prepolymerization reaction: with polyvalent alcohol, and hydrophilic chain extender and isocyanate-monomer reaction; (2) monomer modified, add polyhydric monomer and polyurethane prepolymer and carry out modification; (3) in and salify, add neutralizing agent, make emulsion be formed into the salt ion group; (4) chain extension after the emulsification, outer emulsifying agent and sulfonic acid chainextender is soluble in water, emulsification in the adding system.
The leather of the present invention preparation method of high solid aquosity urethane, carry out according to following step:
(1) prepolymerization reaction: with carboxylic monomer and hydrophilic chain extender under 80～100 ℃, 1-3h dewaters under the 0.08-0.1Mpa vacuum tightness, regulate the pre-polymerization temperature to 70-90 ℃, the isocyanate-monomer, small molecule chain extender and the catalyzer that add metering, reaction 2.0-4.0h; Control R value is 1.05-2.0 in the prepolymerization reaction process, and the NCO content of infrared tracing detection question response no longer changes and carries out the next step again; By adding the viscosity that a small amount of solvent is regulated prepolymer, wherein R is meant the mol ratio of total NCO/OH in the reaction process;
(2) monomer modified: be the water vapour permeability behind the increase emulsion film forming, add polyoxyethylene glycol (PEG) and carry out modification that its molecular weight is 400-2000, its quality accounts for the 1%-15% of total solids; Add organosilicon and Tegin 55G again,
(3) in and salify: on above-mentioned reaction basis, water-bath is cooled to 25-60 ℃, adds in the neutralizing agent and salify 0.5h, and the neutralizing agent consumption is to be that 80-120% adds according to degree of neutralization; Wherein said degree of neutralization is meant the ratio of neutralizing agent and the molar weight of hydrophilic chain extender;
(4) chain extension after the emulsification: sulfonic acid type chainextender and outer emulsifying agent is soluble in water, regulate solid content 50～60%, add emulsification 0.5h under the high-speed stirring, drip proper quantity of defoaming agent, discharging is milky white colour band blue light emulsion.
Wherein the carboxylic monomer described in the step (1) comprises that molecular weight is 500-3000 polyester polyol or polyester polyethers polyol blend etc.; Be preferable over polytetrahydrofuran diol, polyethylene glycol adipate, polyneopentyl glycol adipate, acrylate polyvalent alcohol, polyethylene glycol adipate glycol, poly-hexanodioic acid-1,6-hexylene glycol esterdiol, poly-hexanodioic acid-1,4-butanediol ester glycol, poly-ε-caprolactone diol or polycarbonate-1,6-hexylene glycol esterdiol; More preferably in polytetrahydrofuran diol, polyethylene glycol adipate, polyneopentyl glycol adipate, polyethylene glycol adipate glycol, poly-hexanodioic acid-1,4-butanediol ester glycol etc., most preferably in one or more mixing of polytetrahydrofuran diol, polyethylene glycol adipate, polyneopentyl glycol adipate, it accounts for 20% ~ 65% of reaction total solids quality.
Wherein the hydrophilic chain extender described in the step (1) comprises the small molecules polyvalent alcohol that contains carboxyl, sulfonic acid (salt) group, be preferable over 2,2-dimethylol propionic acid (DMPA), quadrol base ethyl sulfonic acid sodium, 1,4-butyleneglycol-2-sodium sulfonate and derivative thereof, be preferable over 2,2-dimethylol propionic acid (DMPA), dimethylolpropionic acid, dihydroxyl half ester, it accounts for 0.5% ~ 8% of reaction total solids quality.
Wherein the isocyanate-monomer described in the step (1) is isophorone diisocyanate (IPDI), hexamethylene diisocyanate aliphatics, alicyclic diisocyanates such as (HDI).The preferred isophorone diisocyanate of the present invention (IPDI), hexamethylene diisocyanate (HDI) or IPDI and HDI mixture, its quality account for 15% ~ 35% of reaction total solids quality.
Wherein the small molecule chain extender described in the step (1) is preferred 1,4-butyleneglycol, 2,3-butyleneglycol, glycol ether, 1,6-hexylene glycol, glycerine, trihydroxy-propane, ethylene glycol.More preferably 1,4-butyleneglycol, 2,3-butyleneglycol, glycol ether, ethylene glycol, most preferably 1, one or more of 4-butyleneglycol, glycol ether, ethylene glycol mix, and it accounts for 1% ~ 6% of reaction total solids quality
Wherein the catalyzer described in the step (1) is organic tin or tertiary amines, specifically comprise dibutyl tin laurate, stannous octoate, triethylamine, triethylene diamine, dimethyl cetylamine, two dimethyl amine benzyl ethyl ether, nitrogen Ethylmorphine quinoline, trolamine, thanomin, pyridine or N, N'-lutidine etc., preferred dibutyl tin laurate, triethylene diamine, catalyst levels account for 0.1% ~ 0.5 % of reaction total solids quality.
Wherein organosilicon is organosilane monomer or organopolysiloxane described in the step (2); Preferred alkyl organoalkoxysilane, octadecyloxy phenyl TMOS, alkyl chlorosilane, terminal hydroxy group siloxanes, hydroxy-terminated polysiloxane, dimethyl cyclosiloxane, tetramethylphenyl dichlorosilane, methacrylic acid trialkoxy silane, methyl polysiloxane; More preferably terminal hydroxy group siloxanes, hydroxy-terminated polysiloxane, its quality accounts for the 0.1%-10% of total solids.
The wherein sour fat of the preferred single stearic acid glycerine lipoprotein of mono-glycerides described in the step (2), tetramethylolmethane fat, esterified rosin, tetraethoxy, more preferably one or both of single stearic acid glycerine lipoprotein, the sour fat of tetramethylolmethane fat mix, and its quality accounts for the 0.1%-10% of total solids.
Wherein described in the step (3) in and salt forming agent be triethylamine, tripropyl amine, trolamine, diethylenetriamine, methylamine, ammoniacal liquor, sodium hydroxide, potassium hydroxide, be preferable over triethylamine, potassium hydroxide.
Wherein the sulfonic acid type chainextender described in the step (4) be H2N (CH2) nNH (CH2) mSO3Na (n=1-12, m=1-12), quadrol base ethyl sulfonic acid sodium, 1,4-butyleneglycol-2-sodium sulfonate and derivative thereof, preferred H2N (CH2)
3NH (CH2)
5SO3Na(X506), quadrol base ethyl sulfonic acid sodium or H2N (CH2)
3NH (CH2)
5SO3Na(X506) and the mixture of quadrol base ethyl sulfonic acid sodium, its quality accounts for the 1.0%-10% of total solids.
Wherein the outer emulsifying agent described in the step (4) is non-ionic type or anionic emulsifier, and nonionic emulsifier is: alkylphenol polyoxyethylene, fatty alcohol-polyoxyethylene ether, cithrol etc.; Cloudy release emulsification is for having: alkylbenzene sulfonate, ɑ-alkene sulfonate, alkylsulfonate etc., and preferred alkyl phenol polyethenoxy ether (OP-10) or sodium lauryl sulphate (sps), its quality accounts for the 0.5%-6% of total solids.
Wherein defoamer is the waterborne organic silicon defoamer described in the step (4), and its quality accounts for the 0.02%-1% of total emulsion quality.
The solid content of present technique synthetic leather use urethane is 50%～60%, and product viscosity is less than 1000mPas, and its rate of drying is similar to the usual vehicle type polyurethane under 50 ℃ of left and right sides drying temperatures, and various aspects of performance can compare favourably with solvent-borne type.
The present invention uses two kinds of (carboxylic acid type and sulfonic acid type) chainextenders, improved the emulsifying property of emulsion, make urethane and water fully emulsified, the method that adopts self-emulsifying and outer emulsification to combine simultaneously, emulsion that can synthesizing stable can improve solid content again, be solvent with water during emulsification, meet the needs of process for cleanly preparing; Final synthetic emulsion film forming performance is good, rate of drying soon, xanthochromia, mechanical property excellence, technical process are short, are applicable to synthetic leather basic unit or skin-material, can replace the solvent-borne type product.
Embodiment
The following example is used to illustrate the present invention, but never limits the scope of the invention.
Comparative Examples: 1.5kg polyethylene glycol adipate and 0.035kg dihydroxypropionic acid (DMPA) added to mix in the reactor stir, put into 90 ℃ of water-baths, treat that solid particulate dissolves fully after, vacuumize dehydration 1.0h in vacuum tightness under-the 0.095Mpa.Cool to 80 ℃, add a small amount of 1-Methyl-2-Pyrrolidone (NMP), be 1.5 to add IPDI, 0.05kg glycol ether (DEG) and 0.3% catalyzer, react 2h and get prepolymer by OH/NCO mol ratio (R value); Be cooled to 50 ℃, use the small amount of acetone viscosity reduction earlier, press degree of neutralization 100% then and add in the triethylamine and salify 0.5h; Be cooled to again and slowly add sulfonic acid type chainextender X506 (0.131kg) and 0.068kg alkylphenol polyoxyethylene and the 0.012kg sodium lauryl sulphate that is dissolved in the water after 30 ℃, the control solid content is 55%, emulsify at a high speed 0.5h, drip proper quantity of defoaming agent, acetone is removed in underpressure distillation, obtains milky white colour band blue light emulsion at last.
Embodiment 1: under the Comparative Examples operational condition, replace part polyethylene glycol adipate (its OH mole number summation is identical with Comparative Examples) with the 0.4kg polyneopentyl glycol adipate, HDI replaces the IPDI (NCO mole number) of half, the prepolymerization reaction time is 3h, all the other conditions are identical with Comparative Examples, obtain the emulsion of white semi-transparent zone blue light at last, solid content is 50%.
Embodiment 2: under the Comparative Examples operational condition, use 1.0kg, polytetrahydrofuran diol and 0.255kg polyoxyethylene glycol (M=1000) are replaced polyethylene glycol adipate, the prepolymerization reaction time is 2.5h, degree of neutralization is 90%, all the other conditions are identical with Comparative Examples, obtain the emulsion of white semi-transparent zone blue light at last, and solid content is 52%.
Embodiment 3: under the Comparative Examples operational condition, replace part polyethylene glycol adipate (its OH mole number summation is identical with Comparative Examples) with the 0.5kg polytetrahydrofuran diol, adding the IPDI prepolymerization reaction time by R=1.3 is 2.5h, all the other conditions are identical with Comparative Examples, obtain the emulsion of white semi-transparent zone blue light at last, solid content is 57%.
Embodiment 4: under the Comparative Examples operational condition, replace polyethylene glycol adipate with 1.475kg polytetrahydrofuran diol and 0.025kg organosilicon 8427 (terminal hydroxy group siloxanes), the prepolymerization reaction time is 3.5h, all the other conditions are identical with Comparative Examples, obtain the emulsion of white semi-transparent zone blue light at last, solid content is 51%.
Embodiment 5: under the Comparative Examples operational condition, press R=1.8 and add IPDI, with 1, the 4-butyleneglycol is replaced glycol ether, consumption with the sulfonic acid chainextender increases to 0.137kg simultaneously, and degree of neutralization is 95%, and all the other conditions are identical with Comparative Examples, obtain being with the translucent emulsion of blue light white at last, solid content is 59%.
Embodiment 6: under the Comparative Examples operational condition, replace whole polyethylene glycol adipates with 1.4kg polytetrahydrofuran diol and 0.018kg single stearic acid glycerine lipoprotein, the prepolymerization reaction time is 4.0h, degree of neutralization is 110%, all the other conditions are identical with Comparative Examples, obtain white translucent emulsion at last, solid content is 53%.
Experiment one
Testing method:
Viscosity: in temperature is under the condition of (25 ± 0.5) ℃, tests with the NDJ-7 rotary viscometer of Shanghai instrument (group) supply and marketing company.
Storage period: by GB/T 14732-2006(timber industry tackiness agent with urea aldehyde, phenolic aldehyde, terpolycyantoamino-formaldehyde resin) emulsion sealed normal temperature is preserved the observation layering and situation is solidified in thickening, be expired to liquid layering or curing.
Solid content: by the mensuration of GB/T2793-1995(tackiness agent non-volatile content) tests.
Mechanical property: press GB/T1040-2006(plastic tensile method for testing performance), speed 50mm/min, gauge length 25mm.
The leather of the foregoing description products obtained therefrom and import is listed in the table below with the salient features of high solid content emulsion:
Claims (9)
1. remove from office preparation method, it is characterized in that carrying out according to following step with high solid aquosity urethane:
(1) prepolymerization reaction: with carboxylic monomer and hydrophilic chain extender under 80～100 ℃, 1-3h dewaters under the 0.08-0.1Mpa vacuum tightness, regulate the pre-polymerization temperature to 70-90 ℃, the isocyanate-monomer, small molecule chain extender and the catalyzer that add metering, reaction 2.0-4.0h; Control R value is 1.05-2.0 in the prepolymerization reaction process, and the NCO content of infrared tracing detection question response no longer changes and carries out the next step again; By adding the viscosity that a small amount of solvent is regulated prepolymer, wherein R is meant the mol ratio of total NCO/OH in the reaction process;
(2) monomer modified: be the water vapour permeability behind the increase emulsion film forming, add polyoxyethylene glycol and carry out modification that its molecular weight is 400-2000, its quality accounts for the 1%-15% of total solids; Add organosilicon and Tegin 55G again;
(3) in and salify: on above-mentioned reaction basis, water-bath is cooled to 25-60 ℃, adds in the neutralizing agent and salify 0.5h, and the neutralizing agent consumption is to be that 80-120% adds according to degree of neutralization; Wherein said degree of neutralization is meant the ratio of neutralizing agent and the molar weight of hydrophilic chain extender;
(4) chain extension after the emulsification: sulfonic acid type chainextender and outer emulsifying agent is soluble in water, regulate solid content 50～60%, add emulsification 0.5h under the high-speed stirring, drip proper quantity of defoaming agent, discharging is milky white colour band blue light emulsion.
2. the leather according to claim 1 preparation method of high solid aquosity urethane, it is characterized in that wherein the carboxylic monomer described in the step (1) comprises that molecular weight is 500-3000 polyester polyol or polyester polyethers polyol blend, it accounts for 20% ~ 65% of reaction total solids quality;
Wherein the hydrophilic chain extender described in the step (1) is for containing the small molecules polyvalent alcohol of carboxyl, sulfonic acid (salt) group, and it accounts for 0.5% ~ 8% of reaction total solids quality;
Wherein the isocyanate-monomer described in the step (1) is aliphatics, alicyclic diisocyanate, and its quality accounts for 15% ~ 35% of reaction total solids quality;
Wherein the small molecule chain extender described in the step (1) is 1,4-butyleneglycol, 2, and 3-butyleneglycol, glycol ether, 1,6-hexylene glycol, glycerine, trihydroxy-propane or ethylene glycol, it accounts for 1% ~ 6% of reaction total solids quality,
Wherein the catalyzer described in the step (1) is organic tin or tertiary amines, and catalyst levels accounts for 0.1% ~ 0.5 % of reaction total solids quality.
3. leather according to claim 1 is characterized in that with the preparation method of high solid aquosity urethane wherein organosilicon described in the step (2) is organosilane monomer or organopolysiloxane, and its quality accounts for the 0.1%-10% of total solids;
Wherein mono-glycerides described in the step (2) is single stearic acid glycerine lipoprotein, the sour fat of tetramethylolmethane fat, esterified rosin, tetraethoxy, and its quality accounts for the 0.1%-10% of total solids.
4. leather according to claim 1 is with the preparation method of high solid aquosity urethane, it is characterized in that wherein described in the step (3) in and salt forming agent be triethylamine, tripropyl amine, trolamine, diethylenetriamine, methylamine, ammoniacal liquor, sodium hydroxide or potassium hydroxide.
5. leather according to claim 1 is characterized in that with the preparation method of high solid aquosity urethane wherein the sulfonic acid type chainextender described in the step (4) is H2N (CH2) nNH (CH2) mSO3Na, n=1-12 wherein, m=1-12; Quadrol base ethyl sulfonic acid sodium, 1,4-butyleneglycol-2-sodium sulfonate and derivative thereof, its quality accounts for the 1.0%-10% of total solids;
Wherein the outer emulsifying agent described in the step (4) is non-ionic type or anionic emulsifier, and its quality accounts for the 0.5%-6% of total solids;
Wherein defoamer is the waterborne organic silicon defoamer described in the step (4), and its quality accounts for the 0.02%-1% of total emulsion quality.
6. the leather according to claim 2 preparation method of high solid aquosity urethane, it is characterized in that wherein the carboxylic monomer described in the step (1) is polytetrahydrofuran diol, polyethylene glycol adipate, polyneopentyl glycol adipate, acrylate polyvalent alcohol, polyethylene glycol adipate glycol, poly-hexanodioic acid-1,6-hexylene glycol esterdiol, poly-hexanodioic acid-1,4-butanediol ester glycol, poly-ε-caprolactone diol or polycarbonate-1,6-hexylene glycol esterdiol;
Wherein the hydrophilic chain extender described in the step (1) is 2,2-dimethylol propionic acid, quadrol base ethyl sulfonic acid sodium, 1,4-butyleneglycol-2-sodium sulfonate and derivative thereof;
Wherein the isocyanate-monomer described in the step (1) is isophorone diisocyanate, hexamethylene diisocyanate or its mixture;
Wherein the small molecule chain extender described in the step (1) is 1, one or more mixing of 4-butyleneglycol, glycol ether, ethylene glycol;
Wherein the catalyzer described in the step (1) is dibutyl tin laurate, stannous octoate, triethylamine, triethylene diamine, dimethyl cetylamine, two dimethyl amine benzyl ethyl ether, nitrogen Ethylmorphine quinoline, trolamine, thanomin, pyridine or N, the N'-lutidine.
7. leather according to claim 2 is characterized in that with the preparation method of high solid aquosity urethane wherein organosilicon described in the step (2) is alkylalkoxy silane, octadecyloxy phenyl TMOS, alkyl chlorosilane, terminal hydroxy group siloxanes, hydroxy-terminated polysiloxane, dimethyl cyclosiloxane, tetramethylphenyl dichlorosilane, methacrylic acid trialkoxy silane, methyl polysiloxane; Wherein mono-glycerides described in the step (2) is one or both mixing of single stearic acid glycerine lipoprotein, the sour fat of tetramethylolmethane fat.
8. leather according to claim 2 is with the preparation method of high solid aquosity urethane, it is characterized in that wherein described in the step (3) in and salt forming agent be triethylamine, potassium hydroxide.
9. leather according to claim 2 is characterized in that with the preparation method of high solid aquosity urethane wherein the sulfonic acid type chainextender described in the step (4) is H2N (CH2)
3NH (CH2)
5SO3Na, quadrol base ethyl sulfonic acid sodium or H2N (CH2)
3NH (CH2)
5The mixture of SO3Na and quadrol base ethyl sulfonic acid sodium;
Wherein the nonionic emulsifier described in the step (4) is: alkylphenol polyoxyethylene, fatty alcohol-polyoxyethylene ether, cithrol; Cloudy release emulsification is: alkylbenzene sulfonate, ɑ-alkene sulfonate, alkylsulfonate.
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