CN104231209B - Preparation method for high-hardness waterborne polyurethane dispersion - Google Patents
Preparation method for high-hardness waterborne polyurethane dispersion Download PDFInfo
- Publication number
- CN104231209B CN104231209B CN201410498604.3A CN201410498604A CN104231209B CN 104231209 B CN104231209 B CN 104231209B CN 201410498604 A CN201410498604 A CN 201410498604A CN 104231209 B CN104231209 B CN 104231209B
- Authority
- CN
- China
- Prior art keywords
- preparation
- dispersion quality
- quality fraction
- dispersion
- hardness
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/46—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen
- C08G18/4676—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08G18/6659—Compounds of group C08G18/42 with compounds of group C08G18/34
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2206—Oxides; Hydroxides of metals of calcium, strontium or barium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a preparation method for high-hardness waterborne polyurethane dispersion. An inorganic nano material and waterborne polyurethane are grafted through an in-situ polymerization method, so that the hybridization reaction of inorganic materials and the organic materials is realized and complementary advantages are realized. The preparation method comprises the following operation steps: adding polyisocyanate, macromolecule polyol, a catalyst, a chain extender and a silane coupling agent according to certain weight ratio in a flask for reacting to obtain a polyurethane prepolymer; after the reaction is ended, sequentially adding a neutralizer, inorganic nano material dispersion liquid and deionized water under the condition of low-temperature and high-speed stirring; finally, heating under the vacuum condition for removing the solvent to obtain the high-hardness waterborne polyurethane dispersion. Compared with the traditional inorganic and organic blending process, the preparation method has the characteristics that products prepared through the preparation method have the advantages of good stability, excellent water resistance, long-time aging resistance, excellent and high adhesion, high drying speed, high hardness, good fullness, higher light transmittance and the like, and are wide in application range.
Description
Technical field
The invention belongs to water-based industrial paint uses emulsion technology field, more particularly to a kind of high rigidity aqueous polyurethane point
The preparation method of dispersion liquid.
Background technology
From early 1990s, World Developed Countries have just started " Green revolution ", drive paint industry to " green
The big step of the color " line of production is strided forward.It is into 21 century since, further perfect with environmental regulation, to mitigate earth load be
Purpose and the research of the water paint of low VOC emission carried out, just become the emphasis of research and development increasingly.Traditional oiliness industrial paint is big
The discharge Organic substance of amount, on the one hand directly affects the healthy of people；On the other hand it can in atmosphere with other chemicals
There is chemical reaction in matter, form PM2.5, cause atmospheric pollution, and annual solvent based coating is discharged organic in use
The PM2.5 that volatile matter is formed, is only second to the pollution that vehicle exhaust is caused to air.And by contrast, water-based industrial paint has nothing
Poison ring guarantor, odorlessness, volatilizable thing is few, the advantages of do not fire not quick-fried, can effectively solve the formed PM2.5's of solvent based coating
Emission problem, therefore the Water-borne modification of industrial paint will be trend of the times.Aqueous pu dispersions are plentiful, beautiful because of its paint film, tool
Have the advantages that excellent rotproofness, chemical proofing, weatherability, resistance to water, adhesive force are good, but its difference of hardness, easily scratch, it is dry
Dry slow the shortcomings of, significantly limit application of the aqueous pu dispersions in water-based industrial paint.Traditional inorganic material with
Aqueous polyurethane blending method, although can effectively solve the problem that the problem of waterborne polyurethane paint film lower hardness, but also to a great extent
On have impact on the water resistance of waterborne polyurethane paint film, it is impossible to tackle the problem at its root.
The content of the invention
It is an object of the invention to overcome the deficiencies in the prior art, there is provided a kind of system of high rigidity aqueous pu dispersions
Preparation Method, can be on the premise of not affecting paint film water-fast, and effectively solving aqueous pu dispersions hardness of paint film is low, easily draw
Wound, the problem of slow drying speed.
Another object of the present invention is to solve inorganic material in coating production process be difficult to be distributed in water-base resin
Problem, improves the storage stability of coating.
In order to achieve the above object, the present invention is employed the following technical solutions, and its step of preparation process is as follows：
1st, macromolecular polyol is added in flask, in temperature 100-140 DEG C, bar of the vacuum in 0.01-0.04MPa
1-3 hours are dehydrated under part, 30-90 DEG C is cooled to；
2nd, will be 1 with macromolecular polyol weight ratio:During the polyisocyanates of 1.5-50 adds flask, lead to nitrogen protection,
1-2 hours are reacted at 60-100 DEG C, adopts di-n-butylamine titrimetry to judge reaction end in course of reaction；
3rd, it is 1 to add in flask with macromolecular polyol weight ratio at 40-70 DEG C:The hydrophilic chain extender of 0.1-0.8,
Small molecule chain extender and account for dispersion quality fraction 0.01-0.1% catalyst that dispersion quality fraction is 0.1-2% are accounted for, then
2-4 hours are reacted at 70-85 DEG C；
4th, 40-70 DEG C is cooled to, addition accounts for dispersion quality fraction 20-80% solvents and reduces system viscosity, continues reaction 1-
2 hours；
5th, 10-40 DEG C is cooled to, addition accounts for the silane coupler of the 0.5-5% of dispersion quality fraction, 10-100 point of reaction
Clock, obtains base polyurethane prepolymer for use as；
6th, it is under low whipping speed is for the stirring condition of 300-1500rpm, described in base polyurethane prepolymer for use as Deca and step (3)
Hydrophilic chain extender material amount ratio be 1:The nertralizer of 0.8-1.2, reacts 1-10 minutes, obtains the polyurethane prepolymer for neutralizing
Body；
7th, under low whipping speed is for the stirring condition of 300-1500rpm, adds in the base polyurethane prepolymer for use as of neutralization and account for point
The nano inorganic material aqueous solution of prose style free from parallelism mass fraction 10-50%, concentration for 10-60wt%, reacts 1-10 minutes；
8th, under low whipping speed is for the stirring condition of 300-1500rpm, continue in above-mentioned base polyurethane prepolymer for use as, slowly
Deca accounts for the deionized water that dispersion quality fraction is 60～70%, finally adds the 0.5-5%'s that accounts for dispersion quality fraction
Rear chain extender reacts 10-60 minutes, forms dispersions of polyurethanes；
9th, under the conditions of vacuum is 0.01-0.04MPa, 20-80 minutes are reacted in 40-80 DEG C, during elimination reaction
The solvent for being added, is just obtained a kind of high rigidity aqueous pu dispersions.
Macromolecular polyol described in step (1) selected from molecular weight be the polyether polyol of 600-5000, PEPA,
One or more amount in sulfonated polyether polyhydric alcohol, sulfonated polyester polyol and reduced branching degree PEPA.
Polyisocyanates described in step (2) selected from toluene di-isocyanate(TDI) (TDI), 4,4 '-diphenyl methane two is different
Cyanate (MDI), 4,4'- dicyclohexyl methyl hydride diisocyanates (HMDI), isophorone diisocyanate (IPDI), six first
In group diisocyanate (HDI), XDI (XDI) and poly methylene poly phenyl poly isocyanate (PAPI)
One or more.
Hydrophilic chain extender described in step (3) is selected from dihydromethyl propionic acid (DMPA), dimethylolpropionic acid (DMBA), second two
One or more in amido ethyl sulfonic acid sodium and 1,4- butanediol -2- sodium sulfonates.
Small molecule chain extender described in step (3) selected from diglycol, 1,4- butanediols, neopentyl glycol, oneself two
One or more in alcohol, trimethylolpropane.
Catalyst described in step (3) be selected from dibutyl tin laurate, stannous octoate, N, mono- dimethyl cyclohexyl amines of N,
One or more in triethylenediamine.
One or more in solvent selected from acetone, butanone or toluene described in step (4).
Silane coupler described in step (5) selected from methacryloxypropyl trimethoxy silane (KH570), γ-
Aminopropyl triethoxysilane (KH550), γ-glycidyl ether oxygen propyl trimethoxy silicane (KH560), anilinomethyl three
One kind in methoxy silane, anilino- triethoxysilane.
The one kind of nertralizer described in step (6) in sodium hydroxide, ammonia, triithylamine.
Nano inorganic material aqueous solution described in step (7) is selected from Ludox, nano silicon aqueous solution, nano-silica
Change the one kind in aluminum water solution, nano-calcium carbonate aqueous solution.
Rear chain extender described in step (8) is selected from ethylenediamine, in diamidogen, diethylenetriamines and isophorone diamine
It is a kind of.
Nano inorganic material and aqueous polyurethane by situ aggregation method, are carried out graft reaction, are utilized by patent of the present invention
The reaction of the isocyano of the hydroxyl of nano inorganic material particle surface and base polyurethane prepolymer for use as in nano inorganic material aqueous solution
Activity, is better than the reactivity of water and the isocyano of base polyurethane prepolymer for use as, gathers so as to nano inorganic material is grafted to aqueouss
The hydridization reaction of inorganic-organic material on urethane strand, is realized well, both ensure that resistance to water and the attachment of paint film
Power, the problems such as efficiently solve low waterborne polyurethane paint film hardness, easy scuffing and slow drying speed again.Because inorganic material with it is organic
The membrane formation mechanism of material is different, and inorganic material is grafted on the strand of organic resin, can effectively improve the dry of water-based industrial paint
Dry speed.Inorganic material has the advantages such as hardness is high, ageing-resistant, chemicals-resistant is good, and organic material has water-tolerant, gloss
Degree is high, the excellent advantage of adhesive force, and the two makes up for each other's deficiencies and learn from each other, and reaches effective performance complement, excellent so as to forming properties
Water-based industrial paint.The present invention makes inorganic material effectively be distributed to aqueouss tree using rationally perfect operating procedure and technological parameter
In fat, the storage stability of coating is improve.
Specific embodiment
The invention is further illustrated by the following examples, but the embodiment is merely to illustrate the present invention rather than restriction
The present invention.
Embodiment 1
The PEPA that molecular weight is 2000 is added in four-neck flask, is 120 DEG C in temperature, vacuum is
Under conditions of 0.02MPa, be dehydrated 2 hours, cool to 60 DEG C it is standby.Toluene di-isocyanate(TDI) (TDI) and PEPA are pressed
Weight compares 1:During 3 dehydrations add four-neck flask, lead to nitrogen protection, react 2 hours at 70 DEG C, be cooled at 60 DEG C and add and polyester
Polyol quality ratio is 1：0.2 dimethylolpropionic acid, 1,4 butanediols for accounting for dispersion quality fraction 4% and account for dispersion quality
The dibutyl tin laurate of fraction 0.05%, then reacts 4 hours at 80 DEG C；60 DEG C are cooled to, addition accounts for dispersion quality
The acetone of fraction 20% reduces system viscosity, reacts 1 hour.Continue to be cooled to 30 DEG C, addition accounts for dispersion quality fraction 1%
KH550, reacts 20 minutes, and it is 1 to be rapidly added under 500rpm stirrings with the amount ratio of the material of dimethylolpropionic acid：1 three second
Ammonia, subsequent low whipping speed are 500rpm, sequentially add and account for dispersion quality fraction 10%, and concentration is 30wt% nano silicons
Aqueous solution and the deionized water that dispersion quality fraction is 70% is accounted for, add the second two for accounting for that dispersion quality fraction is 0.5%
Amine react 10 minutes, formed dispersions of polyurethanes, finally by above-mentioned dispersion vacuum be 0.02MPa, temperature is 60 DEG C
Under the conditions of react 60 minutes, remove acetone, obtain aqueous pu dispersions.It is applied on glass plate, film thickness is 20
Micron, its hardness >=2H, water-fast 120 hours non-whitenings, 15 minutes non-whitenings of resistance to boiling water, alkaline-resisting, resistance to alcohol without exception, painting in 1 hour
Layer light transmittance is unchanged.
Embodiment 2
The sulfonated polyester polyol that molecular weight is 2000 is added in four-neck flask, is 120 DEG C in temperature, vacuum is
Under conditions of 0.02MPa, be dehydrated 2 hours, cool to 60 DEG C it is standby.By methyl diphenylene diisocyanate (MDI) and molecular weight
For 2000 PEPA by weight 1:During 4 dehydrations add four-neck flask, lead to nitrogen protection, react 1 hour at 70 DEG C, drop
It is 1 that temperature is added with sulfonated polyester polyol mass ratio to 60 DEG C：0.1 dimethylolpropionic acid, addition account for dispersion quality fraction and are
2% diglycol and the dibutyl tin laurate that dispersion quality fraction is 0.02% is accounted for, then 4 are reacted at 80 DEG C
Hour；Addition accounts for the acetone that dispersion quality fraction is 45% and reacts 30 minutes, is cooled to 30 DEG C, and addition accounts for dispersion quality point
Number is 2.5% silane coupler KH560, is reacted 30 minutes, and low whipping speed is 1300rpm, is rapidly added and dimethylolpropionic acid
The amount ratio of material is 1：1 triithylamine, it is 20wt% subsequently to sequentially add concentration, accounts for the nanometer two that dispersion quality fraction is 10%
Calcium oxide aqueous solution and account for the deionized water that dispersion quality fraction is 60% and add that to account for dispersion quality fraction be 1.5%
Isophorone diamine, reacts 20 minutes, forms dispersions of polyurethanes, is 0.02MPa in vacuum by above-mentioned dispersion, and temperature is
Under the conditions of 60 DEG C, 30 minutes removing butanone are reacted, aqueous pu dispersions are obtained.It is applied on glass plate, film thickness
For 10 microns, up to >=2H, water-fast 120 hours non-whitenings, 15 minutes non-whitenings of resistance to boiling water, alkaline-resisting, resistance to alcohol are as good as its hardness for 1 hour
Often, coating light transmittance is unchanged.
Claims (1)
1. a kind of preparation method of high rigidity aqueous pu dispersions, it is characterised in that operating procedure is as follows：
The PEPA that molecular weight is 2000 is added in flask, is 120 DEG C in temperature, bar of the vacuum in 0.02MPa
It is dehydrated 2 hours under part, cools to 60 DEG C；
To be 1 with the PEPA weight ratio:During 3 toluene di-isocyanate(TDI) adds flask, lead to nitrogen protection, at 70 DEG C
It is lower reaction 2 hours, be cooled at 60 DEG C add with the PEPA weight ratio be 1:0.2 dimethylolpropionic acid, account for point
The BDO of the 4% of prose style free from parallelism mass fraction and the dibutyl tin laurate for accounting for dispersion quality fraction 0.05%, Ran Hou
React 4 hours at 80 DEG C；
60 DEG C are cooled to, addition accounts for the acetone of dispersion quality fraction 20% and reduces system viscosity, continues reaction 1 hour；
30 DEG C are cooled to, addition accounts for the Silane coupling agent KH550 of the 1% of dispersion quality fraction, are reacted 20 minutes,
Low whipping speed is for, under the stirring condition of 500rpm, Deca is 1 with the amount ratio of the material of dimethylolpropionic acid:1 three second
Amine, under subsequent low whipping speed is for the stirring condition of 500rpm, adds in the base polyurethane prepolymer for use as of neutralization and accounts for dispersion quality
Fraction 10%, concentration for 30wt% nano silicon aqueous solution and account for the deionized water that dispersion quality fraction is 70%, then
Addition accounts for the reacting ethylenediamine 10 minutes that dispersion quality fraction is 0.5%, forms dispersions of polyurethanes；
By the dispersion under the conditions of vacuum is 0.02MPa, react 60 minutes in 60 DEG C, remove acetone, obtain the height
Hardness aqueous pu dispersions.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410498604.3A CN104231209B (en) | 2014-09-26 | 2014-09-26 | Preparation method for high-hardness waterborne polyurethane dispersion |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410498604.3A CN104231209B (en) | 2014-09-26 | 2014-09-26 | Preparation method for high-hardness waterborne polyurethane dispersion |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104231209A CN104231209A (en) | 2014-12-24 |
| CN104231209B true CN104231209B (en) | 2017-04-12 |
Family
ID=52220185
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410498604.3A Active CN104231209B (en) | 2014-09-26 | 2014-09-26 | Preparation method for high-hardness waterborne polyurethane dispersion |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104231209B (en) |
Families Citing this family (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104829811B (en) * | 2015-04-30 | 2017-09-01 | 安吉县广泰化工纸业有限公司 | A kind of preparation technology of waterborne polyurethane resin |
| CN104893536A (en) * | 2015-06-24 | 2015-09-09 | 芜湖市晨曦新型建材科技有限公司 | Single-component room-temperature-cured waterborne polyurethane paint and preparing method thereof |
| CN105482046A (en) * | 2015-12-30 | 2016-04-13 | 江苏日出化工有限公司 | Method for preparing acrylic ester modified inorganic material-waterborne polyurethane emulsion |
| CN105732940A (en) * | 2016-05-11 | 2016-07-06 | 江南大学 | Preparation method of waterborne polyurethane-silicon dioxide nano composite emulsion |
| CN105968306A (en) * | 2016-05-25 | 2016-09-28 | 杭州吉华高分子材料股份有限公司 | Preparation method of nano-silicon-dioxide-modified water-based polyurethane |
| CN106700019A (en) * | 2016-12-30 | 2017-05-24 | 姚东生 | Melamine-modified waterborne polyurethane flame-retarded resin and preparation method thereof |
| CN109021190A (en) * | 2017-06-08 | 2018-12-18 | 重庆韩拓科技有限公司 | A kind of nano modified polyurethane adhesive of high-fire resistance and preparation method thereof |
| CN107903374A (en) * | 2017-11-27 | 2018-04-13 | 湖南辰砾新材料有限公司 | A kind of polyimide modified polyaminoester emulsion of high rigidity and preparation method thereof |
| CN109554102B (en) * | 2018-12-03 | 2021-04-30 | 宁夏银珠蓝箭建材科技有限公司 | Waterproof coating for waterproofing buildings and preparation method thereof |
| CN109627952A (en) * | 2018-12-18 | 2019-04-16 | 浙江大学自贡创新中心 | A kind of preparation method of high-hard, transparent aqueous polyurethane coating |
| CN109593453A (en) * | 2018-12-18 | 2019-04-09 | 浙江大学自贡创新中心 | A kind of preparation method of high-hard, transparent polyurethane coating |
| CN109694456A (en) * | 2018-12-28 | 2019-04-30 | 广东工业大学 | A kind of high rigidity, aqueous polyurethane emulsion of resistance to ethyl alcohol and preparation method thereof |
| CN110317530A (en) * | 2019-07-24 | 2019-10-11 | 重庆绿涂腾科技有限公司 | A kind of anti-stone of graphene oxide aqueous polyurethane hits anticorrosive paint and preparation method thereof |
| CN111441176B (en) * | 2020-03-31 | 2023-04-28 | 福建中裕新材料技术有限公司 | Technological method for manufacturing waterborne polyurethane suede synthetic leather |
| CN111394040B (en) * | 2020-05-29 | 2022-03-18 | 骏能化工（龙南）有限公司 | High-performance bi-component polyurethane adhesive and preparation method thereof |
| CN111793352B (en) * | 2020-07-07 | 2022-10-04 | 惠州大亚湾达志精细化工有限公司 | Waterborne polyurethane powder adhesive, elastic material and preparation method thereof |
| CN112778480B (en) * | 2021-01-28 | 2022-07-26 | 南京优迪新材料科技有限公司 | Solvent-free polyurethane dispersion with good compatibility with butyronitrile latex and emulsion for glove coating |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101481876A (en) * | 2008-01-31 | 2009-07-15 | 东莞市恩典皮具制品有限公司 | Aqueous polyurethane emulsion for synthetic leather and preparation thereof |
| CN102504518A (en) * | 2011-11-09 | 2012-06-20 | 温州大学 | Method for preparing nano silicon dioxide/aqueous polyurethane hybrid material |
| CN103333600A (en) * | 2013-05-30 | 2013-10-02 | 中国科学院合肥物质科学研究院 | Preparation method for one-component waterborne polyurethane transparent heat-insulating coating |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101921379A (en) * | 2010-04-16 | 2010-12-22 | 江苏大学 | Method for preparing aqueous polyurethane/nano titanium dioxide hybrid material |
-
2014
- 2014-09-26 CN CN201410498604.3A patent/CN104231209B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101481876A (en) * | 2008-01-31 | 2009-07-15 | 东莞市恩典皮具制品有限公司 | Aqueous polyurethane emulsion for synthetic leather and preparation thereof |
| CN102504518A (en) * | 2011-11-09 | 2012-06-20 | 温州大学 | Method for preparing nano silicon dioxide/aqueous polyurethane hybrid material |
| CN103333600A (en) * | 2013-05-30 | 2013-10-02 | 中国科学院合肥物质科学研究院 | Preparation method for one-component waterborne polyurethane transparent heat-insulating coating |
Non-Patent Citations (1)
| Title |
|---|
| 水性聚氨酯/纳米SiO2杂化材料的制备及性能研究;沈一丁等;《精细化工》;20100430;第27卷(第4期);第318-322页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104231209A (en) | 2014-12-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104231209B (en) | Preparation method for high-hardness waterborne polyurethane dispersion | |
| CN107141434B (en) | Waterborne polyurethane resin for synthetic leather fabric and preparation method thereof | |
| CN101328383A (en) | Production method for liner gloves aqueous polyurethane coating connection material | |
| CN112694591A (en) | Preparation method of silane coupling agent modified solvent-free waterborne polyurethane | |
| US20200299448A1 (en) | Synthesis method for high weather-resistant red water-based polyurethane emulsion | |
| CN109517513B (en) | Manufacturing method of normal-temperature self-repairing type waterborne polyurethane vehicle cover with self-extinction effect | |
| CN103450438A (en) | Waterborne polyurethane resin with high solid content and synthesis method thereof | |
| CN107759764B (en) | Production process of silicon dioxide loaded high-strength aqueous polyurethane emulsion | |
| CN111423775B (en) | Single-component water-based finishing varnish and preparation method thereof | |
| CN103130977A (en) | Polyol polyurethane dispersions of two-component waterborne wood lacquer and preparation method thereof | |
| CN111410730B (en) | Polyurethane emulsion and anti-reflection coating liquid prepared from same | |
| JP2011506685A5 (en) | ||
| CN102391458A (en) | Methods for preparing aqueous polyurethane, auxiliary agent slurry and aqueous polyurethane finishing agent | |
| CN105732938A (en) | Preparation method of polyester-polyether-type aqueous polyurethane leather finishing agent | |
| CN105504206A (en) | Synthetic method of castor oil based enclosed type waterborne polyurethane | |
| CN107141442A (en) | A kind of method of terminal hydroxy liquid modified rubber aqueous polyurethane matting resin | |
| CN106008895A (en) | Anionic waterborne polyurethane resin for wood lacquer and preparation method of anionic waterborne polyurethane resin | |
| CN116143994B (en) | Aqueous organosilicon modified polyurethane dispersoid, preparation method thereof, synthetic leather surface layer containing aqueous organosilicon modified polyurethane dispersoid and luggage leather | |
| CN104371086A (en) | Preparation method of ultraviolet-curing organosilane acrylic acid polyurethane | |
| CN113831829B (en) | Polyurethane anti-icing paint and preparation method and application thereof | |
| CN113637140B (en) | Hydrophilic isocyanate crosslinking agent and preparation method thereof | |
| CN111647306B (en) | In situ generation of organized SiO 2 Environment-friendly enhanced waterborne polyurethane ink and preparation method thereof | |
| CN110423323B (en) | Water-soluble blocked polyurethane curing agent and preparation method and application thereof | |
| CN114381196A (en) | Preparation method of photochromic waterborne polyurethane coating | |
| CN114921168B (en) | Carbon-silicon nano material modified aqueous polyurethane emulsion, synthesis method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |