CN1321142C - Prepn of dihydroxy dialkyl siloxane polymer modified water-base polyurethane - Google Patents
Prepn of dihydroxy dialkyl siloxane polymer modified water-base polyurethane Download PDFInfo
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- CN1321142C CN1321142C CNB2005100197805A CN200510019780A CN1321142C CN 1321142 C CN1321142 C CN 1321142C CN B2005100197805 A CNB2005100197805 A CN B2005100197805A CN 200510019780 A CN200510019780 A CN 200510019780A CN 1321142 C CN1321142 C CN 1321142C
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- dialkyl siloxane
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- aqueous polyurethane
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Abstract
The present invention relates to a preparation method of dihydroxy poly-dialkyl siloxane modified aqueous polyurethane. In the present invention, dihydroxy poly-dialkyl siloxane is directly used for replacing part of polyester or polyether dihydric alcohol, isophorone diisocyanate or toluene diisocynate or 4, 4 '-diphenyl methanediisocyanate, dihydroxymethylpropionic acid, and glycerol or trimethylol propane or 1, 4-butanediol; dibutyltin dilaurate is used as a catalyst to obtain a prepolymer of the dihydroxy poly-dialkyl siloxane modified aqueous polyurethane by solvents-N-formyl pentazane ketone, propanone or butanone or ethyl acetate; the prepolymer of the dihydroxy poly-dialkyl siloxane modified aqueous polyurethane is neutralized by base, and water is added to shear and emulsify; ethylenediamine is added to expand a chain to obtain polyurethane emulsion with the solid content of 30 wt% to 40 wt%. The obtained aqueous polyurethane emulsion has high solid content, good adhesive force, weatherability, water resistance and brightness and excellent abrasion resistance. The aqueous polyurethane emulsion is suitable for being used as a fabric, a plastic and the ink of leather, etc. The aqueous polyurethane emulsion can be used for the paint field by properly regulating hardness.
Description
Technical field:
The present invention is a kind of dihydroxy dialkyl siloxane polymer modified Synthesis of Waterborne Polyurethane method, particularly directly uses the method that dihydroxy dialkyl siloxane polymer replacement part polyester or polyether Glycols and aliphatic diisocyanate or aromatic diisocyanate are prepared into aqueous polyurethane emulsion.This emulsion is mainly used in makes printing ink, coating, tackiness agent.
Background technology:
Aqueous polyurethane is the macromolecular material that RECENT DEVELOPMENTS is got up, and because of being dispersion medium with water, compares with solvent borne polyurethane, and price is low, and is safe in utilization, and therefore non-environmental-pollution is widely used in industries such as printing, coating, papermaking, leather finish.
When aqueous polyurethane liquid is used for leather finish, its good leveling property, film forming properties is good, strong covering power, bonding is firm, and coating is cold-resistant, heat-resisting, wear-resisting, high resilience.Be used for the fabric coating finish polyurethane coating and have thin, the good springiness of coating, feel is soft, advantages such as anti-solvent, low temperature resistant, wear-resisting, Waterproof Breathable.
The tackiness agent aqueous polyurethane mainly is used as the bonding of wood working, fabric and flocking, laminated film.
Aqueous polyurethane coating be in the coating variety except as furniture lacquer, outside electrocoating paint, electrocoating paint, building coating, paper coating, the glass fiber coating, also can be used as the special tailor-(made) coating of departments such as space flight and aviation, naval vessel, optical fiber, military project.
Synthetic for aqueous polyurethane mainly is as Eur.Pat.Appl.EP 1241199 A1 18 Sep 2002 with isocyanuric acid and polyester diol, polyether Glycols, PCDL, 14 pp.PCTInt.Appl.WO2002012407 A1,14 Feb 2002,59pp, Eur.Pat.Appl.EP 117,238,9A1 16 Jan 2002, mainly be to make aqueous polyurethane coating in the 7 pp patents with polyester diol and poly--2-butylene dibasic alcohol; Ger.Offen.DE 10112390 A1 2 Oct 2002, it is by different Buddhist ketone vulcabond and polyvalent alcohol that 10 pp. use acrylic modified waterborne urethane, the dispersion liquid that effects such as acrylic acid derivative obtain is used to make the coating of the high film of hardness, and its solid content is 30%.
CN 2001-115056 20 Jun 2001. prepared acrylic acid epoxy modified aqueous polyurethanes are by tolylene diisocyanate, different Buddhist ketone vulcabond and polyvalent alcohol, and the dispersion liquid that Resins, epoxy, acrylic acid derivative effect obtain is as the base-material of coating.
A.Anand Prabu, and M.Anagar (Progress in organiccoating, 2004,29,236-243), reported to use after the synthesizing epoxy modified waterborne polyurethane and contained amino siloxanes chain extension, in order to improve the mechanical property of aqueous polyurethane (PU).
Summary of the invention:
The purpose of this invention is to provide a kind of dihydroxy dialkyl siloxane polymer modified Synthesis of Waterborne Polyurethane method.The dihydroxy dialkyl siloxane polymer modified aqueous polyurethane of this method preparation can be used for printing ink; Coating and tackiness agent.
Siloxane bond has hardness and the wettability and the low-temperature fluidity of good weathering resistance, film forming properties, raising film.
The present invention uses directly to add isocyanic ester replacement partly polyester or polyether glycol in the preparation aqueous polyurethane, and method routinely prepares the dialkyl polydimethylsiloxane modified waterborne polyurethane emulsion of solid content 30wt%-40wt% then.
Dihydroxy dialkyl siloxane polymer modified Synthesis of Waterborne Polyurethane step of the present invention is: the 1st, adopt isophorone diisocyanate or hexamethylene diisocyanate or tolylene diisocyanate, dihydroxy dialkyl siloxane polymer or polyester diol or polyether glycol or PCDL, and dimethylol propionic acid, at solvent n-formyl sarcolysine base pyrrolidone, under the existence of acetone or butanone or ethyl acetate, make catalyzer with dibutyl tin laurate, heating is reacted, until detecting free isocyanato mass content＜0.5%, prepolymer is cooled to 40 ± 2 ℃, get dihydroxy dialkyl siloxane polymer modified aqueous polyurethane performed polymer;
2nd, the dihydroxy dialkyl siloxane polymer modified aqueous polyurethane performed polymer that obtains with triethylamine neutralization procedure 1;
3rd, in the dihydroxy dialkyl siloxane polymer modified base polyurethane prepolymer for use as after step 2 is finished, add its performed polymer quality 1-1.2 deionized water doubly and carry out emulsification pretreatment;
4th, in the dihydroxy dialkyl siloxane polymer modified polyurethane aqueous dispersions behind step 3 emulsification pretreatment, the quadrol chainextender that adds its dispersion quality 0.4%-1.0%, promptly obtain a kind of anion salt, its solid content is the dihydroxy dialkyl siloxane polymer modified aqueous polyurethane of the water dispersion of 30%-40%;
In its pre-polymerization, the mol ratio of isocyanate group and hydroxyl is 1.3/1-1.6/1, the mol ratio of dimethylol propionic acid and polyvalent alcohol is 1.0/1-2.0/1, the content of dialkyl polydimethylsiloxane is the 5wt%-30wt% of all dibasic alcohol, reaction times is 4-8 hour, and temperature of reaction is 55 ℃-80 ℃.
The used dialkyl polydimethylsiloxane of the present invention has following structural:
N wherein is 3-50, and R is C
1-C
4Aliphatic alkyl or undersaturated carbon-carbon double bond.Molecular weight Mw is between 300-3000.
Polyester diol of the present invention is polyester adipate glycol, poly-epsilon-caprolactone glycol or PCDL.
Polyether glycol of the present invention is polyoxypropyleneglycol, polyoxyethylene enediol, polyoxybutylene glycol, polytetrahydrofuran or polytetrahydrofuran-propylene oxide glycol.
The optimum condition of dihydroxy dialkyl siloxane polymer modified Synthesis of Waterborne Polyurethane method of the present invention is: the prepolymerization reaction temperature is 56 ± 1 ℃, 6.5 ± 0.2 hours reaction times.
The dihydroxy dialkyl siloxane polymer modified aqueous polyurethane dispersing liquid of present method preparation and a kind of resin of water polyacrylic acid class, or a kind of aqueous epoxy resins, or a kind of resin alloy of waterborne epoxy modified polyacrylate(s), constitute water-borne coatings, or water color ink.
Specific embodiments:
Embodiment 1
At 250ml thermometer is housed, reflux condensing tube, stir, in the four-hole boiling flask of dropping funnel, add isophorone diisocyanate 16g, dialkyl polydimethylsiloxane (Mn=800) 5g, polycarbonate diol (Mn=1000), 17g, polyester adipate glycol (Mn=2000) 3g, dimethylol propionic acid 3g, N-Methyl pyrrolidone 5g and catalyzer 0.2g, acetone 5g until detecting free isocyanato content＜wt0.5%, obtains base polyurethane prepolymer for use as 70 ℃ of reactions, this performed polymer is cooled to 40 ℃, add the neutralization of 2.8g triethylamine, add deionized water 60g, after the shearing, add quadrol 1.2g chain extension, decompression is at last taken out volatile matter and is got the polyaminoester emulsion of solid content at 40wt%.
Embodiment 2
Be equipped with in the four-hole boiling flask of thermometer, reflux condensing tube, dropping funnel at 250ml, add tolylene diisocyanate (TDI) 17g, dialkyl polydimethylsiloxane (Mn=800) 5g, polycarbonate diol (Mn=1000) 16g, polyester adipate glycol (Mn=2000) 3g, dimethylol propionic acid 3.3g, N-Methyl pyrrolidone 5g and catalyzer 0.2g, acetone 10g, 56 ℃ of reactions until detecting free isocyanato content＜wt0.5%, cooling is cooled to 40 ℃, and the neutralization of 2.8g triethylamine obtains the PU performed polymer.Add deionized water 60g, after the shearing, add quadrol 1.5g chain extension, decompression is at last taken out volatile matter and is got the polyaminoester emulsion of solid content at 38wt%.
Embodiment 3 is replaced the polycarbonate diol in the scheme 1 by polyoxypropyleneglycol, polyoxypropyleneglycol (Mn=1000) 16g.
Embodiment 4 is replaced the polycarbonate diol in the scheme 1 by the polyoxyethylene enediol, polyoxyethylene enediol (Mn=1000) 18g, and dialkyl polydimethylsiloxane (Mn=800) 5g changes dialkyl polydimethylsiloxane (Mn=2000) 3g into.
Embodiment 5 is replaced polytetrahydrofuran (Mn=2000) 20g entirely with polycarbonate diol in the scheme 1 and polyester adipate glycol by polytetrahydrofuran.
The solid content that is added the polyurethane aqueous dispersion body of dialkyl polydimethylsiloxane modification gained by the present invention's process can reach more than 38%, outside its sticking power, weathering resistance, water tolerance, glossiness were identical with unmodified aqueous polyurethane, its wear resisting property, resistance toheat, hardness all were higher than unmodified aqueous polyurethane.This dispersion can spray, brushing, roller coat; The ink printing that can be used for leather, fabric, plastics etc.
Claims (5)
1, a kind of dihydroxy dialkyl siloxane polymer modified Synthesis of Waterborne Polyurethane method is characterized in that step is:
1st, adopt isophorone diisocyanate or hexamethylene diisocyanate or tolylene diisocyanate, dihydroxy dialkyl siloxane polymer or polyester diol or polyether glycol or PCDL, and dimethylol propionic acid, in the presence of solvent n-formyl sarcolysine base pyrrolidone, acetone or butanone or ethyl acetate, make catalyzer with dibutyl tin laurate, heating is reacted, until detecting free isocyanato mass content＜0.5%, prepolymer is cooled to 40 ± 2 ℃, get dihydroxy dialkyl siloxane polymer modified aqueous polyurethane performed polymer;
2nd, the dihydroxy dialkyl siloxane polymer modified aqueous polyurethane performed polymer that obtains with triethylamine neutralization procedure 1;
3rd, in the dihydroxy dialkyl siloxane polymer modified base polyurethane prepolymer for use as after step 2 is finished, add its performed polymer quality 1-1.2 deionized water doubly and carry out emulsification pretreatment;
4th, in the dihydroxy dialkyl siloxane polymer modified polyurethane aqueous dispersions behind step 3 emulsification pretreatment, add the quadrol chainextender of its dispersion quality 0.4%-1.0%, promptly get dihydroxy dialkyl siloxane polymer modified aqueous polyurethane;
In its pre-polymerization, the mol ratio of isocyanate group and hydroxyl is 1.3/1～～1.6/1, the mol ratio of dimethylol propionic acid and polyvalent alcohol is 1.0/1～～2.0/1, the content of dialkyl polydimethylsiloxane be all dibasic alcohol 5wt%～～30wt%, reaction times is 4～～8 hours, and temperature of reaction is 55 ℃～～80 ℃.
2, dihydroxy dialkyl siloxane polymer modified Synthesis of Waterborne Polyurethane method as claimed in claim 1 is characterized in that described dihydroxy dialkyl siloxane polymer has following structural:
N wherein is 3-50, and R is C
1-C
4Aliphatic alkyl or undersaturated carbon-carbon double bond, molecular weight Mw is between 300-3000.
3, dihydroxy dialkyl siloxane polymer modified Synthesis of Waterborne Polyurethane method as claimed in claim 1 is characterized in that described polyester diol is polyester adipate dibasic alcohol, poly-epsilon-caprolactone glycol or PCDL.
4, dihydroxy dialkyl siloxane polymer modified Synthesis of Waterborne Polyurethane method as claimed in claim 1 is characterized in that described polyether glycol is polyoxypropyleneglycol, polyoxyethylene enediol, polyoxybutylene glycol, polytetrahydrofuran or polytetrahydrofuran-propylene oxide glycol.
5, dihydroxy dialkyl siloxane polymer modified Synthesis of Waterborne Polyurethane method as claimed in claim 1, the prepolymerization reaction temperature that it is characterized in that step (1) is 56 ± 1 ℃, 6.5 ± 0.2 hours reaction times.
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Cited By (1)
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| CN101168633B (en) * | 2007-11-08 | 2010-04-21 | 华明扬 | Method for preparing polyurethane linking agent used for environment-friendly ink |
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