CN102690404A - Nonionic waterborne polyurethane dispersoid and preparation method thereof - Google Patents
Nonionic waterborne polyurethane dispersoid and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a nonionic waterborne polyurethane dispersoid and a preparation method thereof. The dispersoid is mainly made from raw materials of A) diisocyanate, B) one or more than two polyols containing at least two hydroxy groups, wherein number average molecular weight of the polyols is 1000-4000, C) a small molecule chain extender and/or a small molecule cross-linking agent, D) methoxy polyethylene glycol with medium-low molecular weight, and E) one or more than one polyamines with number average molecular weight smaller than 500. According to the invention, the prepared dispersoid is with a small particle size, has long storage time and has great stabilities of acid tolerance, alkali tolerance and salt tolerance, and the like.
Description
Technical field
The invention belongs to the polyurethane material field, be specifically related to a kind of non-ionic water polyurethane dispersion and preparation method thereof.
Background technology
Aqueous pu dispersions is because of adopting the dispersion medium of water as dispersion-s; Only there is moisture evaporation to get into atmosphere in the use; Environment is had no adverse effects, simultaneously nonpoisonous and tasteless because of adopting water to make that as dispersion medium water-based polyurethane dispersion also has, the characteristics of safety such as do not fire, not quick-fried.Aqueous pu dispersions is as a kind of green material, and its production and application present ascendant trend year by year.
At present; No matter be patent documentation report or commercially available commercialization aqueous pu dispersions; Be the aqueous pu dispersions of ionic mostly; Wherein anion-type water-thinned polyurethane occupies the majority, and has introduced a kind of back chain extension process method of negatively charged ion aromatic waterborne polyurethane resin like ZL200310112680.8; ZL200410025340.6 has introduced the preparation method of the compound water emulsion of a kind of nanometer anionic polyurethane; ZL200610044039.9 has introduced a kind of self-emulsifying water-thinned anion polyurethane emulsion and preparation method thereof; ZL200810028099.0 has introduced a kind of preparation method of high-performance anion aqueous polyurethane disperse; ZL200810156783.7 has introduced a kind of preparation method of ambient self-crosslinking negatively charged ion water-based polyurethane dispersion; ZL200910078499.7 has introduced a kind of anion aqueous polyurethane disperse and preparation method thereof etc.; Few part is a cation-type water-thinned polyurethane, has introduced a kind of back chain extension process method of cationic aromatic waterborne polyurethane resin like ZL200310112681.2; ZL200810014667.1 has introduced a kind of cation aqueous polyurethane emulsion and preparation method thereof; ZL02159275.6 has introduced a kind of cation aqueous polyurethane dispersion liquid and preparation method thereof; ZL200810014668.6 has introduced a kind of cation aqueous polyurethane acrylate composite emulsion and preparation method thereof etc.Far away from non-ion aqueous polyurethane, this has greatly limited their application to the ionic aqueous pu dispersions aspect potential resistance to electrolyte contamination stability, low-temperature fluidity and strong shearing force stability.The more important thing is; At some special application field such as general aseptic coating, coated metal with chromium-free passivation liquid, the liquid of anti-fingerprint the etc.; Because of necessarily requiring system to have slightly acidic, it faint corrosion of metallic matrix is played chemical rightenning and film forming firmly acts on to reach; Require to add the corrosion-resistant additive of various salts simultaneously, this moment, common ionic aqueous pu dispersions can't meet the demands because of its resistance to acids and bases, freeze thaw stability difference.
Relevant non-ion aqueous polyurethane dispersion liquid preparing method's patent documentation report is less relatively; (referring to that performed polymer chains does not contain hydrophilic radical to generally comprise self-emulsification (referring on the performed polymer chain to introduce wetting ability polyoxyethylene group) and outer emulsion process; Only when disperseing, use emulsifying agent to carry out forced emulsification): ZL01809451.1 and ZL00808012.7 all disclose a kind of non-ionic polyurethane film, and related polyurethane dispersing liquid is by vulcabond and nonionic such as the material preparation that contains active hydrogen.At first use polymer diol and di-isocyanate reaction to form performed polymer, in the presence of one or more ASs (for example X 2073), make performed polymer emulsification then.Because of tensio-active agent is not participated in prepolymerization reaction, and must in the presence of tensio-active agent, just to make performed polymer emulsification be aqueous dispersions, so method still belongs to outer emulsion process in essence.
ZL200410002551.8 provides a kind of water base block polyurethane and preparation method thereof; It is characterized in that it contains the non-ionic water polyurethane that in water, is continued to react gained by the reaction product of (A) group component that is used to form soft section phase and the formed prepolymer of reaction product that is used to form hard section (B) group component mutually, various aspects of performance is all fine.But it be by soft section phase A and hard section mutually B mix and system, and soft section phase A and hard section mutually B need preparation separately, this itself needs the reaction times that grow very much.
(the research of the synthetic and high stability polyaminoester emulsion of ion/non-ionic composite hydrophilic monomer such as the deer Xiushan Mountain, Hao Guangjie; The polymer journal; 2001 (3): 368-371) disclose a kind of method, it is to use pyromellitic dianhydride and polyoxyethylene glycol reaction a kind of nonionic hydrophilic monomer of preparation earlier, re-uses this monomer and prepares the non-ionic water polyurethane emulsion by ordinary method; Though this method is feasible, too loaded down with trivial details and raw material is not easy to obtain.
The manufacturing technology of existing aqueous polyurethane neutralizes to performed polymer mostly earlier, increases its wetting ability, and then emulsification makes in water.But this ionic aqueous polyurethane emulsion acid and alkali-resistance and electrolyte-resistant poor performance, and be not suitable for the field that some has particular requirement.And existing non-ion aqueous polyurethane manufacturing technology is used outer emulsion process mostly or used the special chainextender that has non-ionic hydrophilic group: the former made emulsion property is not good, and latter's raw material is difficult to obtain and preparation technology is loaded down with trivial details.
Summary of the invention
The purpose of this invention is to provide a kind of new non-ionic type aqueous pu dispersions, to solve shortcomings such as existing non-ion aqueous polyurethane dispersion-s resistance to acids and bases difference and freeze thaw stability difference.In addition, the present invention also provides the preparation method of this polyurethane dispersions.
The present invention provides a kind of non-ionic water polyurethane dispersion, it is characterized in that: this polyurethane dispersions contains following component,
Component A according to the invention), B component), component C), component D) and component E) percentage composition to participate in each component gross weight of reaction, each component gross weight percentage composition is 100 weight %.
Component A) be tolylene diisocyanate (TDI), ditan-4,4 '-vulcabond (MDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI) and dicyclohexyl methane diisocyanate (H
12MDI) one or both mixture in.Preferred MDI and/or TDI; The mixture of TDI and MDI more preferably is as component A) when being the mixture of TDI and MDI, wherein the MDI weight percentage is 10%～30 weight %; The TDI weight percentage is 70%～90 weight %; Being more preferably the MDI weight percentage is 20%～50 weight %, and the TDI weight percentage is 50%～80 weight %, in TDI and MDI mixture total weight amount.Wherein TDI is preferably and has 80 weight %2,4-isomer and 20 weight %2, and the isomeric distribution of 6-isomer (being T80) also can be used the TDI with other isomeric distribution certainly, and like T65, T 100 etc., but cost is higher.
B component) comprising two hydroxyls and number-average molecular weight (Mn) is 1000～4000 for minimum, better is one or more mixture in 2000～3000 the polymer polyatomic alcohol.Polymer polyatomic alcohol is polyester polyvalent alcohol or polyether alcohol.Wherein polyether glycol can be propylene oxide, the oxyethane polyvalent alcohol through the ring-opening reaction preparation; Or be the polyvalent alcohol that uses a kind of preparation of epoxides separately; Or be the polyvalent alcohol of two kinds of epoxide random block preparations, or be the polyvalent alcohol of two kinds of orderly block preparations of epoxide; Polyester polyvalent alcohol preferred polyester class divalent alcohol; The preferred hydroxyl value scope of said polyester diol is 50～125mgKOH/g; Like polyethylene glycol adipate glycol (PEA), gather hexanodioic acid glycol ether esterdiol (PDA), gather hexanodioic acid-1; 4-butanediol ester glycol (PBA) or gather carbonic acid-1,6-pinakon esterdiol (PHC) etc.
Component C) for containing the mixture of the small molecules divalent alcohol of carboxyl or two keys, special small molecules divalent alcohol and small molecules linking agent.The small molecules divalent alcohol that wherein contains carboxyl or two keys can select 2 for use, 2-dimethylol propionic acid, N, and N-amido acid, amino acid, diaminobenzoic acid and 2-sodium sulfonate-1, the mixture of one or more in the 4-butyleneglycol, preferred 2, the 2-dimethylol propionic acid; The optional spent glycol of special small molecules divalent alcohol, 1; 2-Ucar 35,1; 4-butyleneglycol, 2; 3-butyleneglycol, 1, the mixture of one or more in 6-pinakon, glycol ether, quinhydrones-two (beta-hydroxyethyl) ether and Resorcinol-two (beta-hydroxyethyl) ether, one or more mixtures in preferred terepthaloyl moietie, glycol ether, quinhydrones-two (beta-hydroxyethyl) ether and Resorcinol-two (beta-hydroxyethyl) ether; The small molecules linking agent can be selected trivalent alcohol or tetravalent alcohols such as TriMethylolPropane(TMP), trolamine, tetramethylolmethane, glycerine for use, preferred TriMethylolPropane(TMP).
Component D) be a kind of in low-molecular-weight poly glycol monomethyl ether, preferred molecular weight is 1000～6000 poly glycol monomethyl ether.
Component E) is lower than 500 polyamine for one or more number-average molecular weights (Mn); Be preferably the mixture of quadrol and diethylenetriamine; When selecting the mixture of quadrol and diethylenetriamine for use, the mol ratio of quadrol and diethylenetriamine is 2～4: 1, better is 3: 1.
Non-ionic water polyurethane dispersion according to the invention also contains one or more materials in skimmer, film coalescence aid, flow agent and the sterilant as required.
The present invention also provides a kind of preparation method of non-ionic water polyurethane dispersion according to the invention, it is characterized in that comprising the steps:
I) make B component) mix with organic solvent, then with component A) mix, add component C successively according to sequencing again) and component D), to carry out prepolymerization reaction and form performed polymer, the prepolymerization reaction temperature is 50 ℃～100 ℃, preferred 70 ℃～100 ℃;
Ii) with step I) performed polymer of preparation is cooled to 10 ℃～25 ℃, is distributed in the deionized water, after treating to disperse fully, adds component E) carry out chain extension, the chain extending reaction temperature is 50～80 ℃;
Add one or more material of skimmer, film coalescence aid, flow agent and sterilant after iii), steam organic solvent and promptly get non-ionic water polyurethane dispersion.
Said organic solvent is acetone, butanone, N-N-methyl-2-2-pyrrolidone N-, vinyl acetic monomer or THF.
Aqueous polyurethane emulsion provided by the present invention is had many uses, and can be re-dubbed the polymkeric substance of inierpeneirating network structure with acrylic ester emulsion or organosilicon crylic acid latex like it, and uses as the finish of leather article and industrial fiber, textile fibres; Can be used as of the application of wear-resisting, shock-resistant, anti-stress cracking like it, also can be used as the coating material of macromolecule material products such as nylon, ABS, polyester with concrete floor, steel framed structure, main equipment, highway bridge guardrail etc.; It also can be used as the bonding etc. of wrapping material, plastics, timber, metal, macromolecular material, circuit card.
Compared with prior art, aqueous polyurethane emulsion provided by the invention can be used as main film forming substance and more is applicable to some special dimension, as can be used as the main ingredient of coated metal with passivating solution, the liquid of anti-fingerprint the etc.Usually these systems all require sour environment and need to add a large amount of inorganic salts inhibiter; And the aqueous polyurethane emulsion that prior art can provide; Because of containing ionic hydrophilic group group mostly, thus emulsion electrolyte-resistant ability a little less than, and do not meet above-mentioned special system requirement.In addition the advantage of aqueous pu dispersions provided by the invention be with in low-molecular-weight poly glycol monomethyl ether to performed polymer-the NCO group carries out partially end-blocked; Generate the performed polymer structure of similar emulsifying agent; Wetting ability when having increased performed polymer emulsification, but still belong to internal emulsification in essence.Therefore aqueous polyurethane emulsion provided by the present invention has extremely strong acid and alkali-resistance, electrolyte-resistant ability, under the situation of acid system and the adding of a large amount of inorganic salt, still can keep high stability of emulsion.It is little that non-ionic water polyurethane dispersion provided by the invention in addition has a particle diameter, and the characteristics of good stability (shelf lives is more than a year) are good with other filler compatibilities, and transparent, water-fast, the anti-solvent of emulsion institute film forming.
Embodiment
Specify the present invention with specific embodiment below, but embodiment does not limit the scope of the invention.
Embodiment 1:
174 grams are gathered hexanodioic acid glycol ether esterdiol (molecular weight is about 2000), 48 gram polyethylene oxide ether divalent alcohol (molecular weight is about 1500) adding four-hole boiling flasks; And add 60 the gram methylethylketones; Feed drying nitrogen afterwards, begin to stir and be warmed up to 55 ℃～70 ℃ gradually; By the time after solid dissolves fully, drip TDI 164.8 grams, be warmed up to 85 ℃-100 ℃ after adding with fast speeds; After the adding proper catalyst reaction 1～2 hour; Add 31.04 grams 2, the 2-dimethylol propionic acid continues reaction and began cooling in 30～45 minutes afterwards; By the time when temperature drops to 70 ℃～80 ℃, add 24.8 gram glycol ether chain extensions; After reacting 1 hour, add 52 gram poly glycol monomethyl ethers (molecular weight is about 2800) and 11 gram TriMethylolPropane(TMP)s simultaneously and continue chain extensions (in the chain extension process, change add acetone or methylethylketone viscosity reduction at any time according to viscosity), react again and began in 1 hour to lower the temperature.By the time the performed polymer temperature is reduced to 10 ℃～25 ℃; Using the high-shear dispersion machine under quick stirring condition, to add deionized water 1040 grams disperses; Rate of dispersion is 2000rpm, treat that the performed polymer whole milk melts after, add soluble in water 18 the gram diethylenetriamines.Acetone is removed in last underpressure distillation or butanone obtains the stabilized aqueous polyurethane dispersions.
Embodiment 2:
108.8 grams are gathered hexanodioic acid-1; 4-butanediol ester glycol (molecular weight is about 3000), 15 gram polypropyleneoxide ether divalent alcohol (molecular weight is about 2000) add four-hole boiling flask; And add 180 gram acetone, and feed drying nitrogen afterwards, begin to stir and be warmed up to 55 ℃～70 ℃ gradually; By the time after solid dissolves fully; Drip TDI and MDI mixture 67.9 grams (amount of substance 2: 1) with fast speeds; Be warmed up to 80 ℃-95 ℃ after adding, after reacting 1～2 hour, add 13.4 grams 2; The 2-dimethylol propionic acid continues the mixture chain extension that reaction added 20.1 gram quinhydrones-two (beta-hydroxyethyl) ethers and glycol ether in 30～45 minutes afterwards; After reacting 1 hour, add 5 gram TriMethylolPropane(TMP)s and continue chain extension (in the chain extension process, variation adds the solvent viscosity reduction at any time according to viscosity), reacted again 1 hour, add 40 gram poly glycol monomethyl ethers (molecular weight is about 3500), react cooling after 45 minutes.By the time the performed polymer temperature is reduced to 10 ℃～25 ℃; Using the high-shear dispersion machine under quick stirring condition, to add deionized water disperses; Rate of dispersion is 2200rpm; After treating that the performed polymer whole milk melts, add 14 gram quadrols soluble in water and diethylenetriamine mixture and react remaining isocyano.Last underpressure distillation removes to desolvate and obtains the stabilized aqueous polyurethane dispersions.
Embodiment 3:
With 174 gram polyethylene glycol adipate glycol (molecular weight is about 2000), 48 gram polyethylene oxide ether divalent alcohol (molecular weight is about 2000), MDI208.2 gram, 21.44 grams 2; 2-dimethylol propionic acid and 24.8 gram glycol ethers add four-hole boiling flask jointly; And add 60 gram acetone, and feed drying nitrogen afterwards, begin to stir and slowly be warmed up to 85 ℃; Add the proper catalyst reaction and added 4 gram TriMethylolPropane(TMP)s continuation chain extensions in 4～5 hours (in the chain extension process; Change according to viscosity and to add the solvent viscosity reduction at any time), react and add 32 gram poly glycol monomethyl ethers (molecular weight is about 3000) after 30 minutes, react again and began in one hour to lower the temperature.By the time the performed polymer temperature reduces to 10 ℃～25 ℃, use the high-shear dispersion machine under stirring condition fast, to add deionized water and disperse, rate of dispersion is 1500rpm, treat that the performed polymer whole milk melts after, add 4.8 gram diethylenetriamines soluble in water.Last underpressure distillation removes to desolvate and obtains the stabilized aqueous polyurethane dispersions.
Embodiment 4:
70 grams are gathered carbonic acid-1; 6-pinakon esterdiol (molecular weight is about 1800), 26 gram polypropyleneoxide ether divalent alcohol (molecular weight is about 2000) add four-hole boiling flask; And add 140 gram butanone, and feed drying nitrogen afterwards, begin to stir and be warmed up to 55 ℃～70 ℃ gradually; By the time after solid dissolves fully; The mixture that drips MDI and TDI with fast speeds totally 164 restrains (amount of substance 2: 1); Be warmed up to 75 ℃～85 ℃ after adding, add after the catalyst reaction 1～2 hour, add 18.7 grams 2; The 2-dimethylol propionic acid continues reaction and added 21.7 terepthaloyl moietie and Resorcinol-two (beta-hydroxyethyl) ether mixture chain extension in 30～45 minutes afterwards; After reacting 1 hour, add 3.5 gram TriMethylolPropane(TMP)s and continue chain extension (in the chain extension process, variation adds the solvent viscosity reduction at any time according to viscosity), reacted again 1 hour, add 28 gram poly glycol monomethyl ethers (molecular weight is about 4000), react cooling after 45 minutes.Treat that the performed polymer temperature reduces to 10 ℃～25 ℃; Using the high-shear dispersion machine under quick stirring condition, to add deionized water disperses; Rate of dispersion is 2500rpm; By the time after the performed polymer whole milk melts, add 14 gram triethylene tetramines soluble in water and quadrol mixture and react remaining isocyano.Last underpressure distillation removes to desolvate and obtains the stabilized aqueous polyurethane dispersions.
Embodiment 5:
210 gram polyethylene glycol adipate glycol (molecular weight is about 2200), 78 gram polyethylene oxide ether divalent alcohol (molecular weight is about 1000) are added four-hole boiling flask; And add 420 the gram methylethylketones; Feed drying nitrogen afterwards, begin to stir and be warmed up to 55 ℃-70 ℃ gradually; By the time after solid dissolves fully; The mixture that drips MDI and TDI with fast speeds totally 368 restrains (amount of substance 3: 1); Be warmed up to 75 ℃～85 ℃ after adding, add after the catalyst reaction 1～2 hour, add 55.7 grams 2; The 2-dimethylol propionic acid continues reaction and added 87 gram Resorcinol-two (beta-hydroxyethyl) ether mixture chain extensions in 30～45 minutes afterwards; After reacting 1 hour, add 10.5 gram TriMethylolPropane(TMP)s and continue chain extension (in the chain extension process, variation adds the solvent viscosity reduction at any time according to viscosity), reacted again 1 hour, add 84 gram poly glycol monomethyl ethers (molecular weight is about 2000), react cooling after 45 minutes.Treat that the performed polymer temperature reduces to 10 ℃～25 ℃; Using the high-shear dispersion machine under quick stirring condition, to add deionized water disperses; Rate of dispersion is 2500rpm; By the time after the performed polymer whole milk melts, add 42 gram triethylene tetramines soluble in water and quadrol mixture and react remaining isocyano.Last underpressure distillation removes to desolvate and obtains the stabilized aqueous polyurethane dispersions.
Embodiment 6:
174 grams are gathered hexanodioic acid-1; 4-butanediol ester glycol (molecular weight is about 2000), 48 gram polypropyleneoxide ether divalent alcohol (molecular weight is about 1500), 114.8 gram TDI, 21.44 grams 2,2-dimethylol propionic acid and 24.8 gram glycol ethers add four-hole boiling flask jointly, and add 60 gram acetone; Feed drying nitrogen afterwards; Begin to stir and slowly be warmed up to 85 ℃, the reaction of adding proper catalyst added 4 gram TriMethylolPropane(TMP)s in 4～5 hours and continues chain extension (in the chain extension process, variation adds the solvent viscosity reduction at any time according to viscosity); React after 30 minutes and to add 32 gram poly glycol monomethyl ethers (molecular weight is about 3000), react again and began cooling in one hour.By the time the performed polymer temperature reduces to 10 ℃～25 ℃, use the high-shear dispersion machine under stirring condition fast, to add deionized water and disperse, rate of dispersion is 1500rpm, treat that the performed polymer whole milk melts after, add 4.8 gram diethylenetriamines soluble in water.Last underpressure distillation removes to desolvate and obtains the stabilized aqueous polyurethane dispersions.
Embodiment 7:
152 grams are gathered carbonic acid-1; 6-pinakon esterdiol (molecular weight is about 1800), 31 gram polypropyleneoxide ether divalent alcohol (molecular weight is about 2000) add four-hole boiling flask; And add 100 gram acetone, and feed drying nitrogen afterwards, begin to stir and be warmed up to 55 ℃-70 ℃ gradually; By the time after solid dissolves fully; Drip TDI and MDI mixture 167.9 grams (amount of substance 1: 1) with fast speeds; Be warmed up to 80 ℃-95 ℃ after adding, after reacting 1～2 hour, add 13.4 grams 2; The 2-dimethylol propionic acid continues the mixture chain extension that reaction added 20.1 gram quinhydrones-two (beta-hydroxyethyl) ethers and glycol ether in 30～45 minutes afterwards; After reacting 1 hour, add 5 gram TriMethylolPropane(TMP)s and continue chain extension (in the chain extension process, variation adds the solvent viscosity reduction at any time according to viscosity), reacted again 1 hour, add 40 gram poly glycol monomethyl ethers (molecular weight is about 3000), react cooling after 45 minutes.By the time the performed polymer temperature is reduced to 10 ℃～25 ℃; Using the high-shear dispersion machine under quick stirring condition, to add deionized water disperses; Rate of dispersion is 2200rpm; After treating that the performed polymer whole milk melts, add 14 gram quadrols soluble in water and diethylenetriamine mixture and react remaining isocyano.Last underpressure distillation removes to desolvate and obtains the stabilized aqueous polyurethane dispersions.
Claims (23)
1. non-ionic water polyurethane dispersion, it is characterized in that: this polyurethane dispersions contains following component,
Component A according to the invention), B component), component C), component D) and component E) percentage composition to participate in each component gross weight of reaction, each component gross weight percentage composition is 100 weight %.
2. non-ionic water polyurethane dispersion according to claim 1; It is characterized in that: said component A) be tolylene diisocyanate, ditan-4; 4 '-vulcabond, hexamethylene diisocyanate, isophorone diisocyanate and dicyclohexyl methane diisocyanate in one or both mixture.
3. non-ionic water polyurethane dispersion according to claim 1 and 2 is characterized in that: said component A) for ditan-4,4 '-vulcabond and/or tolylene diisocyanate,
4. non-ionic water polyurethane dispersion according to claim 1 and 2; It is characterized in that: said component A) for ditan-4,4 '-mixture of vulcabond and tolylene diisocyanate, ditan-4; 4 '-the vulcabond weight percentage is 10～30 weight %; The tolylene diisocyanate weight percentage is 70～90 weight %, with ditan-4,4 '-vulcabond and tolylene diisocyanate mixture total weight amount meter.
5. non-ionic water polyurethane dispersion according to claim 4; It is characterized in that: said component A) for ditan-4,4 '-mixture of vulcabond and tolylene diisocyanate, ditan-4; 4 '-the vulcabond weight percentage is 20～50 weight %; The tolylene diisocyanate weight percentage is 50～80 weight %, with ditan-4,4 '-vulcabond and tolylene diisocyanate mixture total weight amount meter.
6. non-ionic water polyurethane dispersion according to claim 2 is characterized in that: said tolylene diisocyanate is T80, T65 or T100.
7. non-ionic water polyurethane dispersion according to claim 6 is characterized in that: said tolylene diisocyanate is T80.
8. non-ionic water polyurethane dispersion according to claim 1; It is characterized in that: said B component) for minimum two hydroxyls and the number-average molecular weight of comprising is one or more mixture in 1000～4000 the polymer polyatomic alcohol, wherein polymer polyatomic alcohol is polyester polyvalent alcohol or polyether alcohol.
9. non-ionic water polyurethane dispersion according to claim 8 is characterized in that: said polyester polyvalent alcohol is the polyester divalent alcohol, and the hydroxyl value scope of polyester divalent alcohol is 50～125mgKOH/g.
10. non-ionic water polyurethane dispersion according to claim 9; It is characterized in that: said polyester divalent alcohol is the polyethylene glycol adipate glycol, gathers hexanodioic acid glycol ether esterdiol, gathers hexanodioic acid-1; 4-butanediol ester glycol or gather carbonic acid-1,6-pinakon esterdiol.
11. non-ionic water polyurethane dispersion according to claim 1; It is characterized in that: said component C) for containing the mixture of the small molecules divalent alcohol of carboxyl or two keys, special small molecules divalent alcohol and small molecules linking agent; The small molecules divalent alcohol that wherein contains carboxyl or two keys is 2; 2-dimethylol propionic acid, N, N-amido acid, amino acid, diaminobenzoic acid and 2-sodium sulfonate-1, the mixture of one or more in the 4-butyleneglycol; Special small molecules divalent alcohol is a terepthaloyl moietie, 1; 2-Ucar 35,1; 4-butyleneglycol, 2; 3-butyleneglycol, 1, the mixture of one or more in 6-pinakon, glycol ether, quinhydrones-two (beta-hydroxyethyl) ether and Resorcinol-two (beta-hydroxyethyl) ether, the small molecules linking agent is trivalent alcohol or tetravalent alcohols such as TriMethylolPropane(TMP), trolamine, tetramethylolmethane, glycerine.
12. non-ionic water polyurethane dispersion according to claim 11 is characterized in that: said special small molecules divalent alcohol is one or more mixtures in terepthaloyl moietie, glycol ether, quinhydrones-two (beta-hydroxyethyl) ether and Resorcinol-two (beta-hydroxyethyl) ether.
13. non-ionic water polyurethane dispersion according to claim 11 is characterized in that: the said small molecules divalent alcohol that contains carboxyl or two keys is 2, the 2-dimethylol propionic acid.
14. non-ionic water polyurethane dispersion according to claim 11 is characterized in that: said small molecules linking agent is a TriMethylolPropane(TMP).
15. non-ionic water polyurethane dispersion according to claim 1 is characterized in that: be that a kind of molecular weight is 1000～6000 poly glycol monomethyl ether said component D).
16. non-ionic water polyurethane dispersion according to claim 1 is characterized in that: said component E) be lower than 500 polyamine for one or more number-average molecular weights.
17. according to claim 1 or 16 described non-ionic water polyurethane dispersions, it is characterized in that: said component E) be the mixture of quadrol and diethylenetriamine, the mol ratio of quadrol and diethylenetriamine is 2～4: 1.
18. non-ionic water polyurethane dispersion according to claim 17 is characterized in that: said component E) be the mixture of quadrol and diethylenetriamine, the mol ratio of quadrol and diethylenetriamine is 3: 1.
19. non-ionic water polyurethane dispersion according to claim 1 is characterized in that: this non-ionic water polyurethane dispersion also contains one or more materials in skimmer, film coalescence aid, flow agent and the sterilant.
20. a method for preparing the said non-ionic water polyurethane dispersion of claim 1 is characterized in that: this preparation method is:
I) make B component) mix with organic solvent, then with component A) mix, add component C successively according to sequencing again) and component D), to carry out prepolymerization reaction and form performed polymer, the prepolymerization reaction temperature is 50 ℃～100 ℃;
Ii) with step I) performed polymer of preparation is cooled to 10 ℃～25 ℃, is distributed in the deionized water, after treating to disperse fully, adds component E) carry out chain extension, the chain extending reaction temperature is 50～80 ℃;
Add one or more material of skimmer, film coalescence aid, flow agent and sterilant after iii), steam organic solvent and promptly get non-ionic water polyurethane dispersion.
21. preparation method according to claim 20 is characterized in that: said prepolymerization reaction temperature is 70～100 ℃.
22. preparation method according to claim 20 is characterized in that: said organic solvent is acetone, butanone, N-N-methyl-2-2-pyrrolidone N-, vinyl acetic monomer or THF.
23. according to claim 20 or 22 described preparing methods, it is characterized in that: said organic solvent is acetone or butanone.
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Cited By (28)
| Publication number | Priority date | Publication date | Assignee | Title |
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