CN104530372A - Water-based polyurethane and preparation method thereof, and composite film with water-based polyurethane - Google Patents
Water-based polyurethane and preparation method thereof, and composite film with water-based polyurethane Download PDFInfo
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- 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
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
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- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
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- 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
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6648—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6651—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
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- 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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- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
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- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/06—Polyurethanes from polyesters
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Abstract
The invention provides a water-based polyurethane and a preparation method thereof, and a composite film with the water-based polyurethane. The water-based polyurethane is prepared by reacting the following raw materials in parts by weight: 35-70 parts of aliphatic polycarbonate polyalcohol with the molecular weight of 1000-2000, 20-50 parts of polyisocyanate, 4-8 parts of hydrophilic chain extender, 0.5-10 parts of polyalcohol chain extender, 4-8 parts of neutralizer and 0.01-0.3 part of catalyst. The 20-50 parts of polyisocyanate and 35-70 parts of aliphatic polycarbonate polyalcohol with the molecular weight of 1000-2000 react to generate the polyurethane structure, and the carbamate and urea structure have high polarity and higher hydrolysis resistance than ester bond, so the prepared polyurethane coating has higher surface energy.
Description
Technical field
The present invention relates to water-base polyurethane material field, in particular to a kind of aqueous polyurethane, its preparation method and the composite membrane with it.
Background technology
In existing data and document, mostly the preparation of PET film is to be realized by the corona of the films such as PP, PET, Chinese patent application as application number 201010201239.7 discloses a kind of manufacture craft of multilayer PET protective membrane, this technique uses the corona treatment of PET, but the stability of its product compares poor, receive obvious restriction duration of service; And for example application number be 201220463550.3 Chinese patent application disclose a kind of light face printing silver color PET film, the coating of its urethane used processes pet sheet face, but the technology stability of product also exists factor leading to social instability.
As can be seen here, there is obvious restriction the pot life of the PET film prepared by prior art, be generally the time of 3-6 month, and under the empty G&W effect in the environment of polar group after its corona, obvious minimizing, cause the PP of corona, PET film surface energy significantly declines, affect the quality of yield and product; And when carrying out surface treatment by polyester coatings, the ester bond anti-hydrolytic performance in urethane is poor, makes the weathering resistance of its product and the persistence of sticking power and stability deviation, cause the usage period of its product partially short, affect the quality of related products in back segment product chain.
Summary of the invention
Main purpose of the present invention is the composite membrane providing a kind of aqueous polyurethane, its preparation method and have it, with the problem that the polyurethane coating surface energy solving water-base polyurethane material of the prior art formation is low.
To achieve these goals, according to an aspect of the present invention, provide a kind of aqueous polyurethane, aqueous polyurethane is obtained by the raw material reaction comprising following weight part: the molecular weight of 35 ~ 70 weight parts is the aliphatic polycarbonate polybasic alcohol of 1000 ~ 2000; The polyisocyanates of 20 ~ 50 weight parts; The hydrophilic chain extender of 4 ~ 8 weight parts; The polyvalent alcohol chainextender of 0.5 ~ 10 weight part, the neutralizing agent of 4 ~ 8 weight parts; The catalyzer of 0.01 ~ 0.3 weight part.
Further, above-mentioned polyvalent alcohol chainextender be molecular weight 80 ~ 200 polyvalent alcohol, be preferably in BDO, glycol ether, 1,5-PD, TriMethylolPropane(TMP) one or more.
Further, above-mentioned polyisocyanates is aliphatic isocyanates or aromatic isocyanate, preferred hexamethylene diisocyanate or isophorone diisocyanate; Hydrophilic chain extender is the ionic hydrophilic compounds containing active hydrogen or the non-ionic hydrophilic compound containing active hydrogen, ionic hydrophilic compounds thing is preferably carboxyl type hydrophilic compounds, sulfonic acid fundamental mode hydrophilic compounds, phosphoric acid fundamental mode hydrophilic compounds or quaternary hydrophilic compounds, preferably 2,2-dimethylol propionic acid or 2,2 dimethylolpropionic acids; Neutralizing agent is basic cpd, preferred organic bases, further preferred triethylamine; Catalyzer is organotin, organo-bismuth or titanic acid ester, preferred dibutyl tin laurate or stannous octoate.
Further, above-mentioned raw materials also comprises the polyhydric amine compounds that weight part is 0.5 ~ 3, is preferably polyamines, hydramine, hydrazine or hydrazides, more preferably quadrol or diethylenetriamine.
Further, above-mentioned raw materials reacts in organic solvent, and organic solvent is preferably ketones solvent or esters solvent, more preferably acetone or butanone.
To achieve these goals, according to an aspect of the present invention, provide a kind of composite membrane, comprise matrix and be attached to the layer of polyurethane on matrix, the urethane in this layer of polyurethane is above-mentioned aqueous polyurethane.
Further, above-mentioned layer of polyurethane is single or multiple lift, and the aqueous polyurethane in each layer layer of polyurethane is coated with the glue spread of 0.01 ~ 0.5g/m2, and preferred glue spread is 0.05 ~ 0.2g/m2.
Further, the material of above-mentioned matrix is polyethylene, polyvinyl chloride, polypropylene, polystyrene or polymeric amide.
To achieve these goals, according to an aspect of the present invention, provide a kind of preparation method of above-mentioned aqueous polyurethane, this preparation method comprises: step S1, is dewatered by polycarbonate polyol, forms dehydration polycarbonate polyol; Step S2, the polycarbonate polyol that will dewater, polyisocyanates, hydrophilic chain extender, polyvalent alcohol chainextender and catalyst mix form mixed system, and make mixed system carry out polyreaction, obtain performed polymer system; And step S3, performed polymer system is neutralized, disperseed, forms aqueous polyurethane.
Further, the mixed system in above-mentioned steps S2 reacts 4 ~ 6h and obtains performed polymer system at 50 ~ 100 DEG C.
Further, above-mentioned steps S2 comprises: dehydration polycarbonate polyol, polyisocyanates and catalyzer are mixed, and forms the first mixed system; Make the first mixed system react 2 ~ 3h at 50 ~ 100 DEG C, form the first reaction system; Hydrophilic chain extender and polyvalent alcohol chainextender are added in the first reaction system, forms the second reaction system; Make the second reaction system react 2 ~ 3h at 50 ~ 100 DEG C, obtain performed polymer system.
Further, above-mentioned steps S2 adopts organic solvent to control the viscosity of performed polymer system.
Further, above-mentioned steps S1 100 ~ 140 DEG C, make aliphatic polycarbonate polybasic alcohol carry out dehydration 2 ~ 3h under the negative pressure of 0.07 ~ 0.09MPa, obtain the polycarbonate polyol that dewaters.
Further, above-mentioned steps S3 comprises: after performed polymer system is cooled to 30 ~ 60 DEG C, add in performed polymer system neutralizing agent carry out in and 0.5 ~ 1h, in formation and system; To in and add deionized water in system and in being distributed to by deionized water with the rotating speed of 1000 ~ 5000r/min and in system, form aqueous polyurethane.
Further, above-mentioned steps S3 also comprise adopt polyhydric amine compounds in and performed polymer in system carry out the process of amine chain extension.
Further, above-mentioned steps S3 neutralizes performed polymer system, disperse after, be also included in the step of solvent removed by vacuum under 30 ~ 60 DEG C of conditions.
Apply technical scheme of the present invention, the aliphatic polycarbonate polybasic alcohol being 1000 ~ 2000 by the molecular weight of the polyisocyanates of 20 ~ 50 weight parts and 35 ~ 70 weight parts in the present invention reacts and generates polyurethane structural, carbamate wherein and urea structure have high polarity and comparatively ester bond have better anti-hydrolytic performance, thus make the polyurethane coating prepared thus have higher surface energy.
Embodiment
It should be noted that, when not conflicting, the embodiment in the application and the feature in embodiment can combine mutually.The present invention is described in detail below in conjunction with embodiment.
Introduce as background technology part, in prior art, there is the problem of the water tolerance of water-base polyurethane material, sticking power and poor stability.In order to address this problem, inventor provides a kind of aqueous polyurethane, and aqueous polyurethane of the present invention is obtained by the raw material reaction comprising following weight part: the molecular weight of 35 ~ 70 weight parts be 1000 ~ 2000 aliphatic polycarbonate polybasic alcohol (preferably 40 ~ 70 weight parts), the polyisocyanates of 20 ~ 50 weight parts, the hydrophilic chain extender of 4 ~ 8 weight parts, the polyvalent alcohol chainextender of 0.5 ~ 10 weight part, the neutralizing agent of 4 ~ 8 weight parts and 0.01 ~ 0.3 weight part catalyzer.
Apply technical scheme of the present invention, a kind of waterborne polyurethane resin of high surface energy can be obtained.The aliphatic polycarbonate polybasic alcohol being 1000 ~ 2000 by the molecular weight of the polyisocyanates of 20 ~ 50 weight parts and 35 ~ 70 weight parts in the present invention reacts and generates polyurethane structural, carbamate wherein and urea structure have the polarity higher compared with ester bond, thus make the polyurethane coating prepared thus have higher surface energy.
And the molecular weight of aliphatic polycarbonate polybasic alcohol is restricted to 1000 ~ 2000, other good over-all propertieies can be possessed under the prerequisite obtaining good surface energy simultaneously, because if the molecular weight of aliphatic polycarbonate polybasic alcohol is greater than 2000, alkylidene group on its main chain and the density of carbonate group less, cause the polarity of the final urethane obtained less, surface energy is less; And when the molecular weight of aliphatic polycarbonate polybasic alcohol is less than 1000, the alkylidene group on main chain and the density of carbonate group excessive, cause the urethane rigidity that finally obtains comparatively large, easy brittle failure.Further, the hydrophilic chain extender of 4 ~ 8 weight parts mainly in order to introduce hydrophilic radical on aqueous polyurethane macromolecular main chain, the function monomer used in aqueous polyurethane preparation, the water-soluble size that the setting of its weight part then mainly needs according to final aqueous polyurethane and determining; The polyvalent alcohol chainextender of 0.5 ~ 10 weight part, mainly adjust the ratio of soft, the hard section of aqueous polyurethane, make final aqueous polyurethane possess good toughness and intensity, while there is higher surface energy, take into account the over-all propertieies such as toughness, intensity, temperature tolerance; The neutralizing agent of 4 ~ 8 weight parts is then that carboxyl, sulfonic group or other the hydrophilic radical generation neutralization reaction introduced with hydrophilic chain extender generates salt, aqueous polyurethane is presented water-soluble.The catalyzer of 0.01 ~ 0.3 weight part is then the efficiency in order to improve whole reaction.
In a preferred embodiment in the present invention, above-mentioned polyvalent alcohol chainextender be molecular weight 80 ~ 200 polyvalent alcohol, be preferably in BDO, glycol ether, 1,5-PD, TriMethylolPropane(TMP) one or more.By limiting the molecular weight of polyvalent alcohol thus determining to introduce the density of hydrophilic radical, when the molecular weight of polyvalent alcohol is greater than 200, in contrast on the polyvalent alcohol chainextender introduced, the density of hydrophilic radical is larger, the phenomenon that a part of hydrophilic radical intermeshes can be made to a certain extent, finally cause hydrophilic radical and neutralizing agent to react the alkali generated to intermesh, likely can be unfavorable for the dispersiveness of aqueous polyurethane in water, and when the molecular weight of polyvalent alcohol is less than 80, the hydrophilic radical then introduced is very few, and then it is also just relative less with the salt that neutralizing agent generates, there is the phenomenon water-soluble on the low side of aqurous ployurethane in result.Preferably water-soluble and dispersed three factors of BDO, glycol ether, 1,5-PD, the TriMethylolPropane(TMP) production cost that has been then choosing comprehensively, aqurous ployurethane.
Each component in above-mentioned raw materials all can adopt material conventional in prior art, the application considers on the basis of reactivity worth and cost, preferred above-mentioned polyisocyanates is aliphatic isocyanates or aromatic isocyanate, further preferred hexamethylene diisocyanate or isophorone diisocyanate; Preferred hydrophilic chainextender is the ionic hydrophilic compounds containing active hydrogen or the non-ionic hydrophilic compound containing active hydrogen, further preferred ion type hydrophilic compounds thing is preferably carboxyl type hydrophilic compounds, sulfonic acid fundamental mode hydrophilic compounds, phosphoric acid fundamental mode hydrophilic compounds or quaternary hydrophilic compounds, most preferably 2,2-dimethylol propionic acid or 2,2 dimethylolpropionic acids; Preferred neutralizing agent is basic cpd, preferred organic bases, further preferred triethylamine; Preferred catalyst is organotin, organo-bismuth or titanic acid ester, further preferred dibutyl tin laurate or stannous octoate.
In order to improve the surface energy of the coating that aqueous polyurethane is formed further, preferred above-mentioned raw materials also comprises the polyhydric amine compounds that weight part is 0.5 ~ 3, be preferably polyamines, hydramine, hydrazine or hydrazides, more preferably quadrol or diethylenetriamine, utilize the polyhydric amine compounds of above-mentioned weight part to carry out further chain extension as polyamine chain extender, improve surface energy further.
React fast to make above-mentioned raw materials, preferred above-mentioned raw materials reacts in organic solvent, described organic solvent is preferably ketones solvent or esters solvent, more preferably acetone or butanone, above-mentioned organic solvent has the good dissolving power of base polyurethane prepolymer for use as, and boiling point is lower, nontoxic or low toxicity, the reaction later stage can remove than being easier to.
In the another kind of typical embodiment of the present invention, provide a kind of composite membrane, this composite membrane comprises matrix and is attached to the layer of polyurethane on this matrix, and the urethane in layer of polyurethane is above-mentioned aqueous polyurethane.Layer of polyurethane containing above-mentioned aqueous polyurethane has higher surface energy, and therefore, the composite membrane with it shows few paint film defect, obviously promotes the yield in production process; Demonstrate persistence and the stability of excellent sticking power and sticking power thereof between layer of polyurethane and matrix, improving product quality simultaneously.
In order to give full play to the advantage of layer of polyurethane, preferred above-mentioned layer of polyurethane is single or multiple lift, and the aqueous polyurethane in each layer layer of polyurethane is with 0.01 ~ 0.5g/m
2glue spread coating, above-mentioned glue spread is 0.05 ~ 0.2g/m
2.The surface energy of above-mentioned layer of polyurethane at more than 46mN/m even more than 50mN/m.
Above-mentioned layer of polyurethane can adopt the mode of coating to be arranged on matrix, can be such as online coating, also can be off-line coating, preferred online coating.The coating fluid used, the reason operationally, on operating environment, in safety is set out, and the desirably aqueous solution or aqueous dispersions, mainly using water as medium, also can contain organic solvent.Coating method for coated polyester film can be Kohler coater, Meyer rod coater, knife coater, extrusion coating machine, Die Coater, reverse coater, forward roller coating machine, gravure coater, contact roller coating machine, spraying machine, curtain-type curtain coater, calender courter, extrusion coated machine etc., and preferred coating method is Meyer rod coater, gravure coater, Die Coater etc.
In another typical embodiment of the present invention, additionally provide a kind of preparation method of above-mentioned aqueous polyurethane, this preparation method comprises: step S1, is dewatered by aliphatic polycarbonate polybasic alcohol, forms dehydration polycarbonate polyol; Step S2, the polycarbonate polyol that will dewater, polyisocyanates, hydrophilic chain extender, polyvalent alcohol chainextender and catalyst mix form mixed system, and make mixed system carry out polyreaction, obtain performed polymer system; And step S3, performed polymer system is neutralized, disperseed, forms aqueous polyurethane.
Above-mentioned preparation method, first carries out processed to aliphatic polycarbonate polybasic alcohol, and this is that isocyanic ester in the water and raw material existed in polycarbonate polyol reacts, thus produces negative reaction, affects the finished product performance; Then polyreaction is carried out by after dehydration polycarbonate polyol, polyisocyanates, hydrophilic chain extender, polyvalent alcohol chainextender and catalyst mix, polyisocyanates wherein and aliphatic polycarbonate polybasic alcohol react and generate polyurethane structural, carbamate wherein and urea structure have high polarity and comparatively ester bond have better anti-hydrolytic performance, thus make the polyurethane coating prepared thus have higher surface energy; Further, the effect of above-mentioned each component can with reference to foregoing teachings.
In order to control the polymerization degree of obtained performed polymer, the mixed system in preferred above-mentioned steps S2 reacts 4 ~ 6h and obtains performed polymer system at 50 ~ 100 DEG C.
In a kind of preferred embodiment of the present invention, preferred above-mentioned steps S2 comprises: dehydration polycarbonate polyol, polyisocyanates and catalyzer are mixed, and forms the first mixed system; Make the first mixed system react 2 ~ 3h at 50 ~ 100 DEG C, form the first reaction system; Hydrophilic chain extender and polyvalent alcohol chainextender are added in the first reaction system, forms the second reaction system; Make the second reaction system react 2 ~ 3h at 50 ~ 100 DEG C, obtain performed polymer system.
To utilize the order of addition of each feed composition that step S2 is carried out proceed step by step, dehydration polycarbonate polyol, polyisocyanates and catalyzer are carried out fully, and in subsequent step, the katalysis of catalyzer gives full play to, and improves reaction efficiency; Carry out chain extension more on this basis, thus PCDL molecule is distributed in base polyurethane prepolymer for use as equably, carbamate wherein and urea structure have the polarity higher compared with ester bond, thus make the polyurethane coating prepared thus have higher surface energy.
When carrying out the step S2 of above-mentioned preparation method, in order to ensure neutralization, the dispersion effect of subsequent step S3, preferred above-mentioned steps S2 adopts organic solvent to control the viscosity of performed polymer system.
In order to obtain good dehydrating effect, preferred above-mentioned steps S1 100 ~ 140 DEG C, make aliphatic polycarbonate polybasic alcohol carry out dehydration 2 ~ 3h under the negative pressure of 0.07 ~ 0.09MPa, obtain the polycarbonate polyol that dewaters.
Neutralization in step S3 of the present invention and dispersion process can be carried out with reference to prior art, and preferred above-mentioned steps S3 comprises: after performed polymer system is cooled to 30 ~ 60 DEG C, add in performed polymer system neutralizing agent carry out in and 0.5 ~ 1h, in formation and system; To in and add deionized water in system and in being distributed to by deionized water with the rotating speed of 1000 ~ 5000r/min and in system, form aqueous polyurethane.In completing and prerequisite under dewater, in making performed polymer System forming water-soluble and system, and then can rate of dispersion be accelerated when disperseing again, and optimize dispersion effect.
Certainly, if those skilled in the art think the molecular weight of the performed polymer in the performed polymer system that step S1 and step S2 obtains, do not meet the service requirements of object product, preferred above-mentioned steps S3 also comprise adopt polyhydric amine compounds in and performed polymer in system carry out the process of amine chain extension.
The solvent used in step S2 causes disadvantageous effect when using the finished product, preferred above-mentioned steps S3 neutralizes performed polymer system, disperse after, be also included in the step of solvent removed by vacuum under 30 ~ 60 DEG C of conditions.
Below with reference to embodiment and comparative example, further illustrate beneficial effect of the present invention.
Embodiment 1
Agitator is being housed, thermometer, return line, in the four-hole boiling flask of nitrogen ingress pipe, load 40 parts of polycarbonate diols based on hexylene glycol dewatered (molecular-weight average 2000), 40 parts of IPDI (isophorone diisocyanate), 6 part 2, 2-dimethylol propionic acid (DMPA), 0.5 part of TriMethylolPropane(TMP) (TMP), 8 part 1, 4-butyleneglycol (BDO), instill 0.05 part of dibutyl tin laurate (DBTDL is as catalyzer), react 6 hours at 75 DEG C, by acetone hierarchy of control viscosity, whipping appts can be stirred smoothly, when question response to isocyanate content (NCO%) no longer changes, this reaction solution is cooled to 40 DEG C, with in 4.5 parts of triethylamines (TEA) and after 0.5h, slowly add appropriate deionized water and carry out water-dispersion, add 1 part of quadrol (EDA) again and carry out chain extension, finally de-acetone obtains the aqueous polyurethane emulsion that solid content is about 30%.
The reaction conditions of embodiment 2-6 and technique are all consistent with embodiment 1, and concrete synthesizing formula is in table 1.
Embodiment 7
Agitator is being housed, thermometer, return line, in the four-hole boiling flask of nitrogen ingress pipe, load 45 parts of polycarbonate diols based on butyleneglycol dewatered (molecular-weight average 1000), 25 parts of IPDI (isophorone diisocyanate), 10 parts of HDI (hexamethylene diisocyanate), 5, 5 part 2, 2-dimethylol propionic acid (DMPA), 1 part of TriMethylolPropane(TMP), 6 part 1, 4-butyleneglycol (BDO), instill 0.12 part of stannous octoate (catalyzer), react 6 hours at 75 DEG C, by acetone hierarchy of control viscosity, when question response to isocyanate content (NCO%) no longer changes, this reaction solution is cooled to 40 DEG C, with in 4.1 parts of triethylamines (TEA) and after 0.5h, slowly add appropriate deionized water and carry out water-dispersion, add 1.2 parts of quadrols (EDA) again and carry out chain extension, finally de-acetone obtains the aqueous polyurethane emulsion that solid content is about 30%.
Embodiment 8
Agitator is being housed, thermometer, return line, in the four-hole boiling flask of nitrogen ingress pipe, load 50 parts of polycarbonate diols (molecular-weight average 1000) based on hexylene glycol and butyleneglycol mixed type dewatered, 35 parts of IPDI (isophorone diisocyanate), , 5 part 2, 2-dimethylol propionic acid (DMPA), 1.2 parts of TriMethylolPropane(TMP)s, 4 part 1, 4-butyleneglycol, instill 0.08 part of stannous octoate (catalyzer), react 6 hours at 75 DEG C, by acetone hierarchy of control viscosity, when question response to isocyanate content (NCO%) no longer changes, this reaction solution is cooled to 40 DEG C, with in 3.7 parts of triethylamines (TEA) and after 0.5h, slowly add appropriate deionized water and carry out water-dispersion, add 1.5 parts of quadrols (EDA) again and carry out chain extension, finally de-acetone obtains the aqueous polyurethane emulsion that solid content is about 30%.
Embodiment 9
In the four-hole boiling flask that agitator, thermometer, return line, nitrogen ingress pipe are housed, load 55 parts dewatered carry out being mixed to form the first mixed system based on hexylene glycol and the polycarbonate diol (molecular-weight average 2000) of butyleneglycol mixed type, 38 parts of IPDI (isophorone diisocyanate) and 0.08 part of dibutyl tin laurate (catalyzer), first mixed system is reacted 2 hours at 75 DEG C, forms the first reaction system; 6 part of 2,2-dimethylol propionic acid (DMPA), 1 part of TriMethylolPropane(TMP) (TMP), 5 parts of BDOs (BDO) are instilled in the first reaction system, forms the second reaction system; Second reaction system is reacted 3 hours at 75 DEG C, by acetone hierarchy of control viscosity, when question response to isocyanate content (NCO%) no longer changes, this reaction solution is cooled to 40 DEG C, with in 4.5 parts of triethylamines (TEA) and after 0.5h, slowly add appropriate deionized water and disperse with the rotating speed of 3000r/min, then adding 1 part of quadrol (EDA) and carry out chain extension, finally de-acetone obtains the aqueous polyurethane emulsion that solid content is about 30%.
Embodiment 10
In the four-hole boiling flask that agitator, thermometer, return line, nitrogen ingress pipe are housed, load 48 parts of polycarbonate diols based on butyleneglycol dewatered (molecular-weight average 1000), 30 parts of IPDI (isophorone diisocyanate), 12 parts of HDI (hexamethylene diisocyanate) and 0.05 part of dibutyl tin laurate (DBTDL, as catalyzer)) carry out being mixed to form the first mixed system, first mixed system is reacted 3 hours at 50 DEG C, forms the first reaction system; 5 part of 2,2-dimethylol propionic acid (DMPA), 1.5 parts of TriMethylolPropane(TMP)s, 4.5 parts of BDOs (BDO) are instilled in the first reaction system, forms the second reaction system; Second reaction system is reacted 2 hours at 100 DEG C, by acetone hierarchy of control viscosity, when question response to isocyanate content (NCO%) no longer changes, this reaction solution is cooled to 40 DEG C, with in 3.7 parts of triethylamines (TEA) and after 0.5h, slowly add appropriate deionized water and disperse with the rotating speed of 5000r/min, then adding 1.8 parts of quadrols (EDA) and carry out chain extension, finally de-acetone obtains the aqueous polyurethane emulsion that solid content is about 30%.
Embodiment 11
In the four-hole boiling flask that agitator, thermometer, return line, nitrogen ingress pipe are housed, load 58 parts of polycarbonate diols based on hexylene glycol dewatered (molecular-weight average 1000), 40 parts of IPDI (isophorone diisocyanate) and 0.12 part of dibutyl tin laurate (catalyzer) to carry out being mixed to form the first mixed system, first mixed system is reacted 3 hours at 50 DEG C, forms the first reaction system; 5.5 part of 2,2-dimethylol propionic acid (DMPA), 2 parts of TriMethylolPropane(TMP)s, 6 parts of BDOs (BDO) are instilled in the first reaction system, forms the second reaction system; Second reaction system is reacted 2 hours at 100 DEG C, by acetone hierarchy of control viscosity, when question response to isocyanate content (NCO%) no longer changes, this reaction solution is cooled to 40 DEG C, with in 4.5 parts of triethylamines (TEA) and after 0.5h, slowly add appropriate deionized water and disperse with the rotating speed of 5000r/min, finally de-acetone obtains the aqueous polyurethane emulsion that solid content is about 30%.
Embodiment 12
In the four-hole boiling flask that agitator, thermometer, return line, nitrogen ingress pipe are housed, load 50 parts of polycarbonate diols based on butyleneglycol dewatered (molecular-weight average 2000), 20 parts of IPDI (isophorone diisocyanate), 12 parts of HDI (hexamethylene diisocyanate) and 01. part of dibutyl tin laurate (catalyzer) carry out being mixed to form the first mixed system, first mixed system is reacted 3 hours at 50 DEG C, forms the first reaction system; 6 part of 2,2-dimethylol propionic acid (DMPA), 1.3 parts of TriMethylolPropane(TMP)s, 4 parts of BDOs (BDO) are instilled in the first reaction system, forms the second reaction system; Second reaction system is reacted 2 hours at 100 DEG C, by acetone hierarchy of control viscosity, when question response to isocyanate content (NCO%) no longer changes, this reaction solution is cooled to 40 DEG C, with in 4.5 parts of triethylamines (TEA) and after 0.5h, slowly add appropriate deionized water and disperse with the rotating speed of 5000r/min, add 1.1 parts of quadrols (EDA) again and carry out chain extension, last under 30 ~ 60 DEG C of conditions, solvent removed by vacuum is carried out to this aqueous polyurethane emulsion, thus obtains the aqueous polyurethane emulsion of solvent-free 30% solid content.
Embodiment 13
Vacuum hydro-extraction step is carried out to the polycarbonate diol (molecular-weight average 2000) based on hexylene glycol, obtain the polycarbonate diol based on hexylene glycol (molecular-weight average 2000) dewatered, agitator is being housed, thermometer, return line, in the four-hole boiling flask of nitrogen ingress pipe, load 52 parts of polycarbonate diols based on hexylene glycol dewatered (molecular-weight average 1000), 35 parts of IPDI (isophorone diisocyanate) and 0.1 part of dibutyl tin laurate carry out being mixed to form the first mixed system, first mixed system is reacted 3 hours at 50 DEG C, form the first reaction system, 4.5 part of 2,2-dimethylol propionic acid (DMPA), 2 parts of TriMethylolPropane(TMP)s, 5.5 parts of BDOs (BDO) are instilled in the first reaction system, forms the second reaction system, second reaction system is reacted 2 hours at 100 DEG C, by acetone hierarchy of control viscosity, when question response to isocyanate content (NCO%) no longer changes, this reaction solution is cooled to 40 DEG C, with in 3.5 parts of triethylamines (TEA) and after 0.5h, slowly add appropriate deionized water and disperse with the rotating speed of 5000r/min, then adding 1.5 parts of quadrols (EDA) and carry out chain extension, finally de-acetone obtains the aqueous polyurethane emulsion that solid content is about 30%.
The reaction conditions of comparative example 1 to 3 and technique are all consistent with embodiment 1, and concrete synthesizing formula is in table 1.
The water-base resin of comparative example 4 is the waterborne polyurethane resin being numbered 50325-W-33 that Changxing Chemical Industry Co Ltd manufactures.
Comparative example 5 adopt instrumentization east beautiful production corona PET film as a comparison case 4 PET film.
Table 1
| IPDI | HDI | Polyvalent alcohol (molecular weight; Number) | DMPA | BDO | TMP | TEA | EDA | Catalyzer | |
| Embodiment 1 | 40 | ____ | Poly-carbon 2000; 40 | 6 | 8 | 0.5 | 4.5 | 1 | 0.05 |
| Embodiment 2 | 45 | —— | Poly-carbon 2000; 40 | 6 | 8 | 1.5 | 4.5 | 1.7 | 0.1 |
| Embodiment 3 | 20 | 10 | Poly-carbon 2000; 50 | 5 | 7 | —— | 3.7 | —— | 0.1 |
| Embodiment 4 | 21 | —— | Poly-carbon 2000; 70 | 5 | 1.5 | —— | 3.7 | —— | 0.1 |
| Embodiment 5 | 45 | —— | Poly-carbon 1000; 40 | 4.5 | 7 | 1 | 3.4 | 2 | 0.05 |
| Embodiment 6 | 30 | —— | Poly-carbon 1000; 60 | 5 | —— | 1.5 | 3.7 | 1 | 0.05 |
| Embodiment 7 | 25 | 10 | Poly-carbon 1000; 45 | 5.5 | 6 | 1 | 4.1 | 1.2 | 0.12 |
| Embodiment 8 | 35 | ____ | Poly-carbon 1000; 50 | 5 | 4 | 1.2 | 3.7 | 1.5 | 0.08 |
| Embodiment 9 | 38 | ____ | Poly-carbon 2000; 55 | 6 | 5 | 1 | 4.5 | 1 | 0.08 |
| Embodiment 10 | 30 | __12_ | Poly-carbon 1000; 48 | 5 | 4.5 | 1.5 | 3.7 | 1.8 | 0.05 |
| Embodiment 11 | 40 | ____ | Poly-carbon 1000; 58 | 5.5 | 6 | 2 | 4.1 | 1.5 | 0.12 |
| Embodiment 12 | 20 | __15_ | Poly-carbon 2000; 50 | 6 | 4 | 1.3 | 4.5 | 1.1 | 0.1 |
| Embodiment 13 | 35 | ____ | Poly-carbon 1000; 52 | 4.5 | 5.5 | 2 | 3.5 | 1.5 | 0.1 |
| Comparative example 1 | 45 | —— | PBA2000；35 | 6 | 8 | 1.5 | 4.5 | 1.7 | 0.1 |
| Comparative example 2 | 45 | —— | PPG2000；35 | 6 | 8 | 1.5 | 4.5 | 1.7 | 0.1 |
| Comparative example 3 | 45 | —— | Poly-carbon 2000; 75 | 6 | 10 | 1.5 | 4.5 | 1.7 | 0.2 |
Note: PBA butyl polyacrylate; PPG: polyether glycol.
The solid content prepared respectively by the aqueous polyurethane emulsion of embodiment and comparative example is the diluent of 5%, adding is coated in PET film relative to the defoamer AD01 (Air Product) of the solidifying agent XP 2706 (Bayer) of gross weight 2%, the wetting agent VXW 6503 (Cytec) and 0.05% of 0.05%, and obtaining glue spread is 0.07 ~ 0.10g/m
2the PET film of coating layer, and each PET film to be tested, the results are shown in Table 2.
Testing method is as follows:
Adopt the method for regulation in GB/T14216 " plastic film and sheet wetting tension test method " can measure coatingsurface.
Hundred lattice tests:
According to Japanese Industrial Standards (JIS), be divided into 1 ~ 5 grade, progression is higher, requires stricter, requires when being the 5th grade in the middle of customer Canonical, represents can not have completely to come off.
Cross-cut tester, edge of a knife width is about 10mm ~ 12mm, every 1mm ~ 1.2mm is interval, have 10 lattice, straight line draw under time there will be the identical straight line tool marks in 10 intervals, draw down in the vertical position of straight line tool marks, just the square of 100 lattice of 10*10 is become, should cut time cross-cut tester is drawn down and see ground, can not only cut on coating, otherwise test is just false.After cross-cut tester has been drawn, also can or can not must come off with adhesive tape test, first, along the light brush of hundred lattice diagonals 5 times, then be affixed on hundred cases with adhesive tape to put, and roll 3 times back and forth with soft rubber wheel, adhesive tape is closely attached, firmly torn by adhesive tape with the angle of 90 °, whether coating has comes off in range estimation (or with magnifying glass) again.In addition, adhesive tape not careless one can, with JIS standard, label and model must be specified.The Transparent Tape 600 of such as 3M, this kind of tape width is 3/4inch, and length has 1296inch and 2592inch two kinds.Judging criterion is as follows:
5B: the edge of otch is completely smooth, and grid edge is without any peeling off;
4B: have small pieces to peel off in the intersection of otch, actual spoilage≤5% in Hua Ge district;
3B: the edge of otch and/or intersection have is peeled off, and its area is greater than 5% ~ 15%;
2B: have part to peel off or whole sheet peels off along notching edge, or partial grid is peeled off by full wafer, the area peeled off is more than 15% ~ 35%;
1B: notching edge sheet peels off/or some grid Part or all peel off, its area is greater than 35% ~ 65% of Hua Ge district;
0B: have peeling paint in blocks at the edge of line and point of crossing place, and the total area that comes off is greater than 65%.
Test should be carried out in temperature 23 ± 2 DEG C and relative humidity 50 ± 5%.
Hydrothermal aging and sticking power/adherence test thereof:
Multilayer film print is placed on temperature 65 DEG C, 500h under the environment of relative humidity 95%, then carries out operating and testing according to hundred lattice testing method.
Sticking power/adherence test:
On the coating layer of polyester film, be coated with UV curable resin composition as follows, making it solidify rear thickness is 10 ± 2 μm, is 650mj/cm at irradiation energy
2condition under be cured, obtain the multilayer film of the structure being called polyester film/layer of polyurethane/UV resin layer.
UV curable resin composition: the composition containing 70 weight part KAYARAD DPHA (Japanese chemical drug company produces), 30 weight part KAYARAD R128H (Japanese chemical drug company produces), 5 weight part IRGACURE651 (Ciba Special Chemicals produces).
Table 2
| Surface energy | Hundred lattice | Hundred lattice after aging | |
| Embodiment 1 | 50 | 5B | 5B |
| Embodiment 2 | 50 | 5B | 5B |
| Embodiment 3 | 48 | 5B | 5B |
| Embodiment 4 | 56 | 5B | 5B |
| Embodiment 5 | 54 | 5B | 5B |
| Embodiment 6 | 50 | 5B | 5B |
| Embodiment 7 | 50 | 5B | 5B |
| Embodiment 8 | 49 | 5B | 5B |
| Embodiment 9 | 48 | 5B | 5B |
| Embodiment 10 | 50 | 5B | 5B |
| Embodiment 11 | 50 | 5B | 4B |
| Embodiment 12 | 49 | 5B | 5B |
| Embodiment 13 | 50 | 5B | 5B |
| Comparative example 1 | 44 | 5B | 3B |
| Comparative example 2 | 40 | 4B | 1B |
| Comparative example 3 | 54 | 4B | 2B |
| Comparative example 4 | 56 | 5B | 2B |
| Comparative example 5 | 52 | 3B | 0B |
The test result of table 2 can draw, the waterborne polyurethane resin that the embodiment of the present invention obtains has higher surface energy, and when as surface-treated layer or articulamentum, has persistence and the stability of excellent sticking power and sticking power simultaneously.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, for a person skilled in the art, the present invention can have various modifications and variations.Within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (16)
1. an aqueous polyurethane, is characterized in that, described aqueous polyurethane is obtained by the raw material reaction comprising following weight part:
The molecular weight of 35 ~ 70 weight parts is the aliphatic polycarbonate polybasic alcohol of 1000 ~ 2000; The polyisocyanates of 20 ~ 50 weight parts; The hydrophilic chain extender of 4 ~ 8 weight parts; The polyvalent alcohol chainextender of 0.5 ~ 10 weight part, the neutralizing agent of 4 ~ 8 weight parts; The catalyzer of 0.01 ~ 0.3 weight part.
2. aqueous polyurethane according to claim 1, is characterized in that, described polyvalent alcohol chainextender be molecular weight 80 ~ 200 polyvalent alcohol, be preferably in BDO, glycol ether, 1,5-PD, TriMethylolPropane(TMP) one or more.
3. aqueous polyurethane according to claim 1, is characterized in that, described polyisocyanates is aliphatic isocyanates or aromatic isocyanate, preferred hexamethylene diisocyanate or isophorone diisocyanate; Described hydrophilic chain extender is the ionic hydrophilic compounds containing active hydrogen or the non-ionic hydrophilic compound containing active hydrogen, described ionic hydrophilic compounds thing is preferably carboxyl type hydrophilic compounds, sulfonic acid fundamental mode hydrophilic compounds, phosphoric acid fundamental mode hydrophilic compounds or quaternary hydrophilic compounds, preferably 2,2-dimethylol propionic acid or 2,2 dimethylolpropionic acids; Described neutralizing agent is basic cpd, preferred organic bases, further preferred triethylamine; Described catalyzer is organotin, organo-bismuth or titanic acid ester, preferred dibutyl tin laurate or stannous octoate.
4. aqueous polyurethane according to claim 1, is characterized in that, described raw material also comprises the polyhydric amine compounds that weight part is 0.5 ~ 3, is preferably polyamines, hydramine, hydrazine or hydrazides, more preferably quadrol or diethylenetriamine.
5. aqueous polyurethane according to claim 1, is characterized in that, described raw material reacts in organic solvent, and described organic solvent is preferably ketones solvent or esters solvent, more preferably acetone or butanone.
6. a composite membrane, comprises matrix and attachment layer of polyurethane on the matrix, it is characterized in that, the aqueous polyurethane of the urethane in described layer of polyurethane according to any one of claim 1 to 5.
7. composite membrane according to claim 6, is characterized in that, described layer of polyurethane is single or multiple lift, and the described aqueous polyurethane in the described layer of polyurethane of each layer is with 0.01 ~ 0.5g/m
2glue spread coating, preferred described glue spread is 0.05 ~ 0.2g/m
2.
8. composite membrane according to claim 6, is characterized in that, the material of described matrix is polyethylene, polyvinyl chloride, polypropylene, polystyrene or polymeric amide.
9. a preparation method for the aqueous polyurethane according to any one of claim 1 to 5, is characterized in that, described preparation method comprises:
Step S1, dewaters polycarbonate polyol, forms dehydration polycarbonate polyol;
Step S2, forms mixed system by described dehydration polycarbonate polyol, polyisocyanates, hydrophilic chain extender, polyvalent alcohol chainextender and catalyst mix, and makes described mixed system carry out polyreaction, obtain performed polymer system; And
Step S3, neutralizes described performed polymer system, disperses, form described aqueous polyurethane.
10. preparation method according to claim 9, is characterized in that, the mixed system in described step S2 reacts 4 ~ 6h and obtains described performed polymer system at 50 ~ 100 DEG C.
11. preparation methods according to claim 9, is characterized in that, described step S2 comprises:
Described dehydration polycarbonate polyol, described polyisocyanates and described catalyzer are mixed, forms the first mixed system;
Make described first mixed system react 2 ~ 3h at 50 ~ 100 DEG C, form the first reaction system;
Described hydrophilic chain extender and described polyvalent alcohol chainextender are added in described first reaction system, forms the second reaction system;
Make described second reaction system react 2 ~ 3h at 50 ~ 100 DEG C, obtain described performed polymer system.
12. preparation methods according to claim 9, is characterized in that, described step S2 adopts organic solvent to control the viscosity of described performed polymer system.
13. preparation methods according to claim 9, is characterized in that, described step S1 100 ~ 140 DEG C, make described aliphatic polycarbonate polybasic alcohol carry out dehydration 2 ~ 3h under the negative pressure of 0.07 ~ 0.09MPa, obtain described dehydration polycarbonate polyol.
14. preparation methods according to claim 9, is characterized in that, described step S3 comprises:
After described performed polymer system is cooled to 30 ~ 60 DEG C, add in described performed polymer system neutralizing agent carry out in and 0.5 ~ 1h, in formation and system;
To add deionized water in described and in system and with the rotating speed of 1000 ~ 5000r/min described deionized water is distributed to described in and in system, form described aqueous polyurethane.
15. preparation methods according to claim 14, is characterized in that, described step S3 also comprises and adopts polyhydric amine compounds to carry out the process of amine chain extension to the performed polymer in described and in system.
16. preparation methods according to claim 14, is characterized in that, described step S3 neutralizes described performed polymer system, disperse after, be also included in the step of solvent removed by vacuum under 30 ~ 60 DEG C of conditions.
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