CN101550224A - Cation polyurethane/inorganic nanometer material organic-inorganic hybrid coating agent - Google Patents
Cation polyurethane/inorganic nanometer material organic-inorganic hybrid coating agent Download PDFInfo
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- CN101550224A CN101550224A CNA2009100592018A CN200910059201A CN101550224A CN 101550224 A CN101550224 A CN 101550224A CN A2009100592018 A CNA2009100592018 A CN A2009100592018A CN 200910059201 A CN200910059201 A CN 200910059201A CN 101550224 A CN101550224 A CN 101550224A
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Abstract
The invention provides a cation polyurethane/inorganic nanometre material organic-inorganic hybrid coating agent and preparation method thereof. The coating agent comprises main components counted by mass percentage as follows: 20-50% of nanometre structure polyurethane and 50-80% of deionized water. The preparation method comprises steps as follows: preparing polyurethane pre-polymer by using dibastic alcohol and diisocyanate; adding chain extender and inorganic nanometre particle to chain-extend the prepared polyurethane pre-polymer; neutralising, emulsifying and solvent-removing the polyurethane pre-polymer. The invention prepares the organic-inorganic hybrid coating agent by using in-situ polymerization method, wherein any precursor is not used in the preparation process, so the invention solves the problem basically that the prior sol-gel method uses the precursor having expensive price, larger toxicity and serous environmental pollution, at the same time the invention solves the problem that the blending method has uneven dispersion and easy agglomeration between the inorganic nanometre particle and polyurethane, the prepared coating agent has excellent applying property and convenient construction and operation.
Description
Technical field:
The present invention relates to a kind of cation polyurethane nanometer finishing agent, particularly relate to aqueous polyurethane/inorganic nanometer material organic-inorganic hybrid coating agent and preparation method thereof, finishing agent can be applicable to fields such as natural leather and synthetic leather covering with paint.
Technical background:
Polyurethane coating is owing to its chemical resistant properties, wear-resisting, good decorative property, excellent properties such as strong adhesion, be widely used in the application of products such as capital construction, furniture, vehicle, leather, present widely used solvent borne polyurethane produces a large amount of organic volatiles (VOC) in production and construction process, the serious harm health of people is destroyed the environment and the eubiosis.The combustion of aqueous polyurethane coating difficulty, nontoxic, low pollution, easily storage, easy to use, has the over-all properties that solvent borne polyurethane compares favourably, fields such as leather finish, paper coating, chemical building material, painting dressing automobiles successfully have been applied in recent years, the development trend that progressively replaces solvent borne polyurethane is arranged, become the important directions of urethane research and development.
Traditional hide finishes overwhelming majority is an anionic property, and crust leather is also most of electronegative before covering with paint, lacquer, colour wash, etc., and is rare or do not have nature avidity, finishing agent can only rely on adhesive power to adhere on the leather between coating and decorating material and the crust leather; The Cationic Finish agent then can borrow the sucking action of yin, yang electric charge to strengthen adhering to of finishing agent and leather, and clinging power is better, and coating effect is excellent more.The iso-electric point of cation polyurethane and leather fiber is close, the skin base that chrome tanning, vegetable tanning and resin-bonded are tanned all has good penetration and associativity, can be applied in " sandwich " Finish System, " full positively charged ion " Finish System, " semication " Finish System, can hide grain surface disability, filling and even surface effectively, give the soft nature of leather, level and smooth careful feel, further improve the quality of leather, create higher marketable value.
Mono-component aqueous urethane does not all reach the level of solvent-borne type or two component polyurethane in hardness, water tolerance, solvent resistance, glossiness etc., has limited its further application, and adopting compound with inorganic nano material is the effective way that promotes its over-all properties.Inorganic nano material has small-size effect, specific surface is big, surface energy is high and characteristic such as surface coordination deficiency, make its be easy to urethane in oxygen play bonding action, improve molecular linkage and make a concerted effort; Be easy to simultaneously be distributed in the space of macromolecular chain, intensity, toughness, ductility, water tolerance that can make material etc. is greatly enhanced; And the quantum size of nano material and macro quanta tunnel effect make it produce the effect of oozing of becoming silted up, can be deep near the unsaturated link(age) of polyurethane molecular chain, and and the electronic cloud of unsaturated link(age) have an effect, thereby improve thermostability, light stability and the chemical stability of polyurethane material, reach purposes such as the ageing resistance that improves product and chemical resistant properties.
Between the preparation nano-polyurethane matrix material blending method commonly used, inorganic nano material and urethane only is that simple physics is mixed, has the problem of the inhomogeneous and easy reunion of inorganic particulate dispersion; And the used precursor of sol-gel method costs an arm and a leg and toxicity is bigger, can cause serious environmental to pollute.Along with economic technology development and people's environmental consciousness is strengthened, the technology of existing preparation nano-polyurethane, can not provide the polyurethane finishing agent that meets modern environmental requirement product for people, the nano-polyurethane technology of preparing that practice needs scientific and technical personnel to develop to make new advances meets the polyurethane finishing agent product that environment " Sustainable development " requires to provide.
Summary of the invention:
Present situation at the polyurethane finishing agent prior art, purpose of the present invention aims to provide a kind of inorganic particulate and is uniformly dispersed, prepares cation polyurethane/inorganic nanometer material organic-inorganic hybrid coating agent that need not any presoma and preparation method thereof, prepare the inorganic particulate that prior art exists and disperse easily to reunite inhomogeneous to solve the nano-polyurethane finishing agent, used precursor cost an arm and a leg and toxicity bigger, environment is easily caused problems such as severe contamination.
Basic thought of the present invention is to adopt the situ aggregation method of having gathered physical blending and Chemical Crosslinking Methods advantage to prepare the hybrid inorganic-organic finishing agent.Adopt situ aggregation method that nanoparticle is dispersed in the polyurethane matrix, between nano material and polyurethane matrix, can produce effective hybrid inorganic-organic at the interface, and,, meet modern environmental protection requirement to reduce production costs without any need for precursor.
Basic ideas of the present invention, polyurethane preformed polymer at first, adopt situ aggregation method to insert nano material then, introduce the cationic hydrophilic group by chain extension, last in and the obtained cation polyurethane/inorganic nanometer material organic-inorganic hybrid coating agent of emulsification.
Cation polyurethane/inorganic nanometer material organic-inorganic hybrid coating agent provided by the invention, it is mainly formed, and is by percentage to the quality: the urethane 20～50% shown in the following structural formula (I), deionized water 50～80%,
In the structural formula (I): i=1～2,
Be inorganic nano-particle, R
1Be the polyurethane prepolymer shown in the said structure formula (II), R
2For molecular weight less than 300 dibasic alcohol or polyvalent alcohol, R
3Be tertiary amine groups oxy-compound, H
+X
-Be salt forming agent, R in the structural formula (II)
4Be vulcabond, R
5Be the dibasic alcohol between the molecular weight 600～4000.
In above-mentioned finishing agent technical scheme, described inorganic nano-particle material is optional to be the nanometer SiO of 10nm-100nm from average particle diameter
2, nano-TiO
2, nano-ZnO, nanometer CaCO
3, nanometer AlO
3, nano imvite and nano clay etc.Can select a kind of in them for use, also can select in them two or more for use.
In above-mentioned finishing agent technical scheme, described tertiary amine groups oxy-compound (is the R in the structural formula (I)
3) can be selected from diethanolamine, trolamine, N methyldiethanol amine (MDEA), N-ethyldiethanolamine (N-EDEA), N-propyl group diethanolamine (N-PDEA), N-benzyl diethanolamine (N-BDEA), tertiary butyl diethanolamine (t-BuDEAt), dimethylethanolamine, two (2-hydroxyethyl) benzylanilines (BHBA) and two (2-hydroxypropyl) aniline (BHPA) etc.Be generally and select a kind of in them for use.
In above-mentioned finishing agent technical scheme, described salt forming agent (H
+X
-) optional from organic acid, mineral acid and alkylating reagent.Be generally and select a kind of in them for use.The preferred hydrochloric acid of mineral acid wherein, the preferred CH of organic acid
3Acids such as COOH, the preferred CH of alkylating reagent
3I alkylating reagent and epoxy chloropropane alkylating reagent.
In above-mentioned finishing agent technical scheme, described vulcabond (is the R in the structural formula (II)
4) can be selected from aromatic diisocyanate, aliphatic diisocyanate and alicyclic diisocyanate.Be generally and select a kind of in them for use.Preferred tolylene diisocyanate (TDI), diphenylmethanediisocyanate (MDI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), dicyclohexyl methane diisocyanate (HMDI) etc.
In above-mentioned finishing agent technical scheme, the dibasic alcohol between the described molecular weight 600～4000 (is the R in the structural formula (II)
5) optional from polyethers dibasic alcohol, the pure and mild polycarbonate diol of polyester binary.Can select a kind of in them for use, also can select the above mixture in two or three in them for use.Preferred polyoxypropyleneglycol (PPG), polytetrahydrofuran diol (PTG), polycaprolactone glycol (PCL), polycarbonate diol (PCDL) etc.Molecular weight can be selected from 1 less than 300 dibasic alcohol or polyvalent alcohol, 4-butyleneglycol, glycol ether, neopentyl glycol, ethylene glycol, 1,2 propylene glycol, 1,6 hexylene glycol, TriMethylolPropane(TMP), glycerine and tetramethylolmethane etc.Can select in them one or more for use.Preferred glycol ether, neopentyl glycol and TriMethylolPropane(TMP).
The present invention also provides the preparation method of above-mentioned cation polyurethane/inorganic nanometer material organic-inorganic hybrid coating agent, and the preparation method specifically comprises and is prepared as follows step:
(1) molecular weight is 600～4000 dibasic alcohol in 110～130 ℃ of vacuum tightness 0.05～0.1MPa, temperature down behind dehydration 30～60min, is cooled to not to be higher than 40 ℃ of room temperatures, in molar ratio n
NCO/ n
OH=2～4 add vulcabond, the catalyzer that adds vulcabond quality 0.3%～1.0%, under nitrogen protection, react in 60 ℃～90 ℃, fully be cooled to after the reaction and be not higher than 40 ℃ of room temperatures, promptly make the polyurethane prepolymer shown in the structural formula (II);
(2) the polyurethane prepolymer adding dibasic alcohol that makes and the solvent of vulcabond quality total amount 5～15%, 2～10% inorganic nano-particle material, 2～10% chainextenders and 2～10% tertiary amine groups oxy-compound, under nitrogen protection, carry out chain extending reaction in 50 ℃～80 ℃, fully be cooled to 30～55 ℃ after the reaction;
(3) polyurethane prepolymer behind the chain extension is pressed degree of neutralization 80%～100% adding salt forming agent, through fully being distributed in the deionized water behind the mixing, filter the back and remove solvent, promptly make the cation polyurethane/inorganic nanometer material organic-inorganic hybrid coating agent shown in the structural formula (I) in 60～80 ℃ of temperature, vacuum tightness 0.05～0.1MPa underpressure distillation.
In the preparation method of above-mentioned hybrid inorganic-organic finishing agent, described catalyzer can be selected from tertiary amine catalyst and organic tin catalyzer, and described solvent is selected from organic solvent of ketone.
In the preparation method of above-mentioned hybrid inorganic-organic finishing agent, the add-on of inorganic nano-particle material, chainextender and tertiary amine groups oxy-compound is relevant with the prescription of dibasic alcohol and vulcabond, and the change with prescription changes greatly, and their add-on is advisable with the scope that is controlled at dibasic alcohol and vulcabond quality total amount 5～10%.The adding mode of inorganic nano material, chainextender, tertiary amine groups oxy-compound preferably makes them mix in solvent earlier, utilize ultrasonic dispersing evenly after, join in the mode of gradation again and carry out chain extending reaction in the polyurethane prepolymer.
The present invention adopts the original position filling technique, at first with inorganic nano material and chainextender, the tertiary amine groups oxy-compound mixes, utilize ultrasonic dispersing evenly to insert polyurethane molecular in the back, prepare the cation polyurethane/inorganic nanometer material organic-inorganic hybrid coating agent, the toxicity that preparation process does not need sol-gel method and used is very big, expensive precursor, also can make nano material particle hybrid inorganic-organic in polymkeric substance, and the reunion of nanoparticle can not take place as blending method, the nanometer attribute that can keep particle has effectively improved the hardness of matrix material, intensity, mechanics such as second-order transition temperature, thermomechanical property and magnetics, optics, ageing-resistant performance.
The cation polyurethane/inorganic nanometer material organic-inorganic hybrid coating agent that the present invention makes is translucent emulsion, solid content 20%～50%, pH5.5～7.0, the room temperature storage time can reach 1 year, this finishing agent is used for the covering with paint of leather, with respect to negatively charged ion finishing agent commonly used, can strengthen adhering to of finishing agent and leather by the attraction of yin, yang electric charge, coating and leather fiber have better clinging power, and good consistency is arranged with the negatively charged ion finishing agent, can be applied to " sandwich " Finish System together; With respect to single component polyurethane/cationic ester paint, then can improve performances such as water-fast, the anti-solvent of finished leather, fast light, intensity, hardness, have good penetration and tack, leather softness after the covering with paint is careful, surface filming as thin as a wafer and nature, good hand feeling can improve the performance of finished leather greatly.
Cation polyurethane/inorganic nanometer material organic-inorganic hybrid coating agent and preparation process thereof that the present invention makes, have nontoxic, lowly pollute, energy-efficient characteristics, meet modern environmental protection requirement, this application of paints performance is good, the constructing operation environment friendly convenient has the prospect of being widely used in the leather finish field.
Embodiment
To closing embodiment the present invention is specifically described below, so that personnel's the understanding of the present invention of affiliated technical field.Be necessary what this particularly pointed out to be; embodiment is used for just that the present invention will be further described; can not be interpreted as limiting the scope of the invention; affiliated art skilled person; to improvement and adjustment that the present invention makes non-intrinsically safe, still belong to protection scope of the present invention according to the invention described above content.
In following each embodiment, involved amounts of components per-cent or umber are mass percent or mass fraction except that specifying.
Embodiment 1:
(1) preparation base polyurethane prepolymer for use as:
The PPG that adds molecular weight 2000 in the reactor that stirring, temperature control and air extractor are housed about control vacuum tightness 0.06MPa, after about 130 ℃ dehydrations of temperature 30 approximately minute, is cooled to about 30 ℃, feed the about 30min of nitrogen after, n in molar ratio under the whipped state
NCO/ n
OHAdd IPDI at=3: 1, and drip the dibutyl tin laurate of IPDI quality 0.7%, is warming up to about 80 ℃ to be cooled to about 30 ℃ behind the about 90min of reaction.
(2) add chainextender and nano material
Under the nitrogen protection state, gradation adds the acetone of PPG and IPDI quality total amount 6%, the nanometer SiO of original position dispersive 3%
2, 3% glycol ether and 3% N methyldiethanol amine, be warming up to the about 4h of reaction about 70 ℃, sampling and measuring NCO% is cooled to about 50 ℃ after reaching below 4%.
(3) neutralization, emulsification, desolventizing
About 50 ℃ of temperature controls, apparent viscosity is added proper amount of acetone, press the acetic acid that degree of neutralization 90% adds specified amount, after mixing, add deionized water emulsification and disperse about 40min, leave standstill and treat the lather collapse after-filtration, extract acetone under 70 ℃, 0.05MPa left and right sides vacuum tightness, product performance and state are observed in the discharging sampling.
Embodiment 2:
(1) preparation base polyurethane prepolymer for use as:
In the reactor that stirring, temperature control and air extractor are housed, add molecular weight and be 2000 PTG, about control vacuum tightness 0.06MPa, be cooled to about 30 ℃ behind about 110 ℃ about 50min of dehydration of temperature, behind the about 40min of feeding nitrogen, n in molar ratio under the whipped state
NCO/ n
OHAdd TDI at=3.5: 1, and drip the triethylenediamine of TDI quality 0.5%, is warming up to about 70 ℃ to be cooled to about 30 ℃ behind the about 100min of reaction.
(2) add chainextender and nano material
Under the nitrogen protection state, gradation adds the acetone of PTG and TDI quality total amount 8%, the nanometer Ti O of original position dispersive 4%
2, 3% neopentyl glycol and 3.5% N-ethyldiethanolamine, be warming up to the about 3h of reaction about 60 ℃, sampling and measuring NCO% progressively is cooled to about 50 ℃ after reaching below 3%.
(3) neutralization, emulsification, desolventizing
About 40 ℃ of temperature controls, apparent viscosity is added proper amount of acetone, press the acetic acid that degree of neutralization 100% adds specified amount, after mixing, add deionized water emulsification and disperse about 30min, leave standstill and treat the lather collapse after-filtration, extract acetone under 70 ℃, 0.08MPa left and right sides vacuum tightness, product performance and state are observed in the discharging sampling.
Embodiment 3:
(1) preparation base polyurethane prepolymer for use as:
In the reactor that stirring, temperature control and air extractor are housed, add molecular weight and be 1500 PCL, about control vacuum tightness 0.08MPa, be cooled to about 25 ℃ behind about 120 ℃ about 40min of dehydration of temperature, behind the about 40min of feeding nitrogen, n in molar ratio under the whipped state
NCO/ n
OHAdd MDI at=4: 1, and drip the stannous octoate of MDI quality 0.5%, progressively is warming up to about 75 ℃ to be cooled to about 25 ℃ behind the reaction month 120min.
(2) add chainextender and nano material
Under the nitrogen protection state; gradation adds the acetone of PCL and MDI quality total amount 8%; the nano imvite of original position dispersive 5%, 4% glycol ether, 0.5% TriMethylolPropane(TMP), 4% N-propyl group diethanolamine; be warming up to the about 3h of reaction about 60 ℃, sampling and measuring NCO% progressively is cooled to about 40 ℃ after reaching below 3%.
(3) neutralization, emulsification, desolventizing
About 40 ℃ of temperature controls, apparent viscosity is added proper amount of acetone, press the acetic acid that degree of neutralization 80% adds specified amount, after mixing, add deionized water emulsification and disperse about 30min, leave standstill and treat the lather collapse after-filtration, extract acetone under about 70 ℃, 0.05MP left and right sides vacuum tightness, product performance and state are observed in the discharging sampling.
Claims (10)
1, a kind of cation polyurethane/inorganic nanometer material organic-inorganic hybrid coating agent is characterized in that finishing agent mainly forms, and is by percentage to the quality: urethane 20～50% shown in the following structural formula (I), and deionized water 50～80%,
In the structural formula (I): i=1～2,
Be inorganic nano-particle, R
1Be polyurethane prepolymer shown in the said structure formula (II), R
2For molecular weight less than 300 dibasic alcohol or polyvalent alcohol, R
3Be tertiary amine groups oxy-compound, H
+X
-Be salt forming agent, R in the structural formula (II)
4Be vulcabond, R
5Be the dibasic alcohol between the molecular weight 600～4000.
2, cation polyurethane/inorganic nanometer material organic-inorganic hybrid coating agent according to claim 1 is characterized in that described inorganic nano-particle is selected from the nanometer SiO that median size is 10nm-100nm
2, nano-TiO
2, nano-ZnO, nanometer CaCO
3, nanometer AlO
3, nano imvite and nano clay.
3, cation polyurethane/inorganic nanometer material organic-inorganic hybrid coating agent according to claim 1 is characterized in that described tertiary amine groups oxy-compound is selected from diethanolamine, trolamine, N methyldiethanol amine, N-ethyldiethanolamine, N-propyl group diethanolamine, N-benzyl diethanolamine, tertiary butyl diethanolamine, dimethylethanolamine, two (2-hydroxyethyl) benzylaniline and two (2-hydroxypropyl) aniline.
4, cation polyurethane/inorganic nanometer material organic-inorganic hybrid coating agent according to claim 1 is characterized in that described salt forming agent H
+X
-Be selected from organic acid, mineral acid and alkylating reagent.
5, cation polyurethane/inorganic nanometer material organic-inorganic hybrid coating agent according to claim 1 is characterized in that described vulcabond is selected from aromatic diisocyanate, aliphatic diisocyanate and alicyclic diisocyanate.
6, cation polyurethane/inorganic nanometer material organic-inorganic hybrid coating agent according to claim 1 is characterized in that the dibasic alcohol between the described molecular weight 600～4000 is selected from polyether Glycols, the pure and mild polycarbonate diol of polyester binary.
7, the preparation method of the described cation polyurethane/inorganic nanometer material organic-inorganic hybrid coating agent of each claim in the claim 1～6 is characterized in that comprising being prepared as follows step:
(1) molecular weight is 600～4000 dibasic alcohol in 110～130 ℃ of vacuum tightness 0.05～0.1MPa, temperature down behind dehydration 30～60min, is cooled to not to be higher than 40 ℃ of room temperatures, in molar ratio n
NCO/ n
OH=2～4 add vulcabond, the catalyzer that adds vulcabond quality 0.3%～1.0%, under nitrogen protection, react in 60 ℃～90 ℃, fully be cooled to after the reaction and be not higher than 40 ℃ of room temperatures, promptly make the polyurethane prepolymer shown in the structural formula (II);
(2) the polyurethane prepolymer adding dibasic alcohol of producing and the solvent of vulcabond quality total amount 5～15%, 2～10% inorganic nano-particle material, 2～10% chainextenders and 2～10% tertiary amine groups oxy-compound, under nitrogen protection, carry out chain extending reaction in 50 ℃～80 ℃, fully be cooled to 30～55 ℃ after the reaction;
(3) polyurethane prepolymer behind the chain extension is pressed degree of neutralization 80%～100% adding salt forming agent, through fully being distributed in the deionized water behind the mixing, filter the back and remove solvent, promptly make the cation polyurethane/inorganic nanometer material organic-inorganic hybrid coating agent shown in the structural formula (I) in 60～80 ℃ of temperature, vacuum tightness 0.05～0.1MPa underpressure distillation.
8, the preparation method of cation polyurethane/inorganic nanometer material organic-inorganic hybrid coating agent according to claim 7 is characterized in that described catalyzer is selected from tertiary amine catalyst and organic tin catalyzer.
9, the preparation method of cation polyurethane/inorganic nanometer material organic-inorganic hybrid coating agent according to claim 7 is characterized in that described solvent is selected from organic solvent of ketone.
10, the preparation method of cation polyurethane/inorganic nanometer material organic-inorganic hybrid coating agent according to claim 7, it is characterized in that inorganic nano material, chainextender and tertiary amine groups oxy-compound mix earlier in solvent, after utilizing ultrasonic dispersing evenly, join in the mode of gradation and to carry out chain extending reaction in the polyurethane prepolymer.
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