CN107964104A - Solvent-free aqueous polyurethane dispersion and its preparation method and application - Google Patents
Solvent-free aqueous polyurethane dispersion and its preparation method and application Download PDFInfo
- Publication number
- CN107964104A CN107964104A CN201711049515.0A CN201711049515A CN107964104A CN 107964104 A CN107964104 A CN 107964104A CN 201711049515 A CN201711049515 A CN 201711049515A CN 107964104 A CN107964104 A CN 107964104A
- Authority
- CN
- China
- Prior art keywords
- glycol
- aqueous polyurethane
- polyurethane dispersion
- alcohol
- section
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
-
- 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
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
-
- 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
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
-
- 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
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
-
- 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
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
-
- 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
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 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
- C08G18/70—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
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
-
- 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
- C08G18/70—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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/06—Polyurethanes from polyesters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/08—Polyurethanes from polyethers
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The present invention provides a kind of solvent-free aqueous polyurethane dispersion and its preparation method and application, preparation method includes the following steps：(1) by polymer diatomic alcohol, diisocyanate, small molecule dihydric alcohol, two terminal hydroxy group Y-shaped pendant hydrophilic chain extender of low melting point and catalyst, preheat respectively, be input in double-screw reactor and react, obtain polyurethane melt；(2) it is injected into shear pump, at the same the water injection shear pump shearing with surfactant is scattered；(3) decrease temperature and pressure, stirring, obtains the solvent-free aqueous polyurethane dispersion.The present invention solves the stability process difficulties such as synthesize, disperse, emulsifying, improving production efficiency and product batches of high viscosity aqueous polyurethane melt；Without using expensive hydrophilic chain extender, it can be used in synthetic leather, adhesive, coating, fabric coating, finishing agent, base fabric bottom material resin, surface layer resin, tie layer resins, intermediate layer resin or foaming layer resin.
Description
Technical field
The present invention relates to the production method of aqueous polyurethane dispersion.
Background technology
Aqueous polyurethane dispersion is using water as decentralized medium, and only water is volatized into air in use, to ring
Border has no adverse effects.It is nontoxic make it that aqueous polyurethane dispersion also has as decentralized medium using water at the same time, it is tasteless, it is non-ignitable,
The characteristics of not quick-fried safe.Aqueous polyurethane dispersion is as a kind of Environmentally-friepolymer polymer material using extremely wide, replacement oil
Property polyurethane resin is also trend of the times, at present widespread adoption in every field such as synthetic leather, adhesive, building coatings.
Aqueous polyurethane from the end of the sixties in last century industrialize since develop it is extremely rapid, but its production technology or between
Method of having a rest and semi-continuous process, all refer to pre-polymerization in reaction kettle.The problem of maximum during pre-polymerization is that reaction kettle is generally difficult to handle height
Viscous systems, therefore pre- collecting process usually requires addition organic solvent reduction polymerization system viscosity or the molecular weight by prepolymer
It is controlled in extremely low level.After prepolymerization reaction, material is transferred to Scattered Kettle and is neutralized and is disperseed, then is carried out in precipitation kettle
Except solvent.Aqueous polyurethane dispersion prepared by this kind of technique often occurs or molecular weight is low, poor performance, batch are unstable
It is fixed, or the substantial amounts of solvent participation of production process needs, and cannot still participate in polymerizeing after the simple recovery purifying of these solvents
Journey, causes manufacture cost to greatly increase, while while emulsifying is very high to equipment requirement, inefficiency is mass produced, generally from throwing
When expecting that discharging needs 12-16 small.
A kind of new aqueous polyurethane preparation process have developed to this many industry pioneer, i.e., from aggressiveness method work
Skill, also known as " pellet method " technique.Its core thinking prepares polyurethane from interpolymer particles with double-screw reactor, then should be from poly-
Body removes solvent after dissolving in a solvent, obtains large arch dam aqueous polyurethane dispersion.Since the process uses solvent-free participation
Bulk technique and reactionless participation emulsifying process, therefore the molecular weight of dispersion can be greatly improved to be lifted and stablized
Performance, but realize solvent be not required to purifying it is i.e. recyclable, greatly reduce the production cost of water-borne dispersions.Both at home and abroad
There is substantial amounts of worker once or still carry out substantial amounts of research work in this respect now.
Patent CN 102336881A are disclosed with polyester polyol, diisocyanate, small molecule chain extender and hydrophilic list
Body, has also prepared aqueous polyurethane using double screw extruder or casting machine and has been used for Aqueous Polyurethane Adhesives from aggressiveness, and
Achieve good effect；Patent CN 102633971A carried out simple pre-polymerization in advance before raw material enters double-screw reactor
Or DMPA is dissolved with pyrrolidones (NMP), to realize the accurate measurement of DMPA, high temperature and pressure emulsifying technology was produced with reducing
The usage amount of solvent in journey, substantially increases the production efficiency of aqueous polyurethane and reduces environmental pollution, but and unresolved few
Measure operation difficult problem caused by the prepolymer viscosity transient rise under solvent.
Patent CN103382253B substitutes DMPA with glycerine list maleic anhydride ester and glycerine monobutane diacid ester, to realize parent
Dissolving of the water chain extender in small molecule dihydric alcohol, to realize its accurate measurement, so as to smoothly stably prepare aqueous poly- ammonia
After ester disperses from aggressiveness, then in acetone in dissolving, triethylamine neutralization, water, aqueous polyurethane of the acetone up to 30-60% is removed
Dispersion, and the technique is particularly suitable for preparing MDI base high-performance aqueous polyurethane dispersion, can be widely applied to water-based poly- ammonia
The fields such as Lipase absobed leather, adhesive.
The above work employs twin screw techniques to prepare polyurethane melt, successively dissolving, into salt, scattered, de-
The technique such as molten prepares aqueous polyurethane dispersion, and solvent is not purified to reuse.
These above-mentioned techniques solve the simple recycling of the defects of aqueous polyurethane dispersion molecular weight is less than normal and solvent, but
Be without reference to how by urea groups structural response into polyurethane, and can not still be broken away to solvent in scattered, emulsion process
Dependence, can not really prepare not only environmental protection but also have an aqueous polyurethane dispersion of high-performance, high added value.
The content of the invention
The object of the present invention is to provide solvent-free aqueous polyurethane dispersion of a kind of continous way and its preparation method and application,
To overcome defect existing in the prior art.
The method of the present invention, includes the following steps：
(1) by polymer diatomic alcohol, diisocyanate, small molecule dihydric alcohol, two terminal hydroxy group Y-shaped pendant hydrophilic of low melting point
Chain extender and catalyst, are preheated to 60-100 DEG C respectively, after being then input to mixer disperses mixing, are input to twin-screw reaction
Reacted in device, acquisition number-average molecular weight is 30000-200000 polyurethane melts；
The structurally and operationally parameter of the double-screw reactor, it is desirable to which material can axially and radially having very in screw rod
Big shearing divergent function, is overcome measurement deviation on the different time caused by measuring equipment pulse, and inventor has found,
Using 16≤L/D≤56, the double screw extruder of more than rotating speed 200-300rpm, can get a desired effect；
Wherein：L represents spiro rod length, and D represents screw diameter；
In the double-screw reactor, reaction temperature is divided into 7 sections, and first segment is 80-130 DEG C, second segment 100-130
DEG C, the 3rd section is 130-140 DEG C, and the 4th section is 140-150 DEG C, and the 5th section is 150-170 DEG C, and the 6th section is 150-200 DEG C, the
Seven sections are 205-230 DEG C, and residence time of the material in twin-screw is 0.5-3min；
The polymer diatomic alcohol is polyether Glycols, polyester diol, one kind or more in polycarbonate glycol
Kind mixture；
The polyether Glycols use 2 terminal hydroxy groups, and number-average molecular weight is the various structural polyether oligomerisations of 200-10000
Thing, including be not limited to：PolyTHF dihydric alcohol (PTMEG), Polyoxypropylene diol (PPG), polyoxyethylene glycol
(PEG) and polypropylene oxide ethylene oxide copolymerization dihydric alcohol (PEPG) one or more mixtures, mixed proportion is unlimited；
The polyester diol is to contain 2 oligomers of the terminal hydroxy group containing polyester construction, range of number-average molecular weight 200-
4000, including be not limited to：Polyadipate -1,4- butyl glycol ester diols (PBA), polyethylene glycol adipate glycol (PEA), gather oneself
Two acid propylene glycol ester glycol (PPA), the hexylene glycol of polyadipate -1,6 esterdiol (PHA), polyneopentyl glycol adipate glycol
(PNA), polyadipate ethylene glycol butyl glycol ester diol (PEBA), polyadipate ethylene glycol propylene glycol ester glycol (PEPA), gather oneself
Diacid hexylene glycol neopentyl glycol esterdiol (PHNA), polybutyleneadipate hexylene glycol esterdiol (PBHA), polyadipate fourth two
Alcohol neopentyl glycol esterdiol (PBNA), the one or more mixing for gathering own Inner esterdiols, mixed proportion are unlimited；
The polycarbonate glycol uses the oligomer containing 2 terminal hydroxy group carbonate-containing structures, number-average molecular weight
Scope is 200-4000, is exchanged and synthesized with binary alcohol esters by carbonic diester, including is not limited to：Poly- carbonic acid hexylene glycol esterdiol, gathers
One or more mixtures of neopentyl glycol carbonate esterdiol, polytetramethylene carbonate diol glycol, poly (propylene carbonate) glycol etc.；
The diisocyanate be selected from 4,4- '-diphenylmethane diisocyanates (MDI), toluene di-isocyanate(TDI) (TDI),
Tolylene diisocyanate (XDI), 1,5- how diisocyanate (NDI), paraphenylene diisocyanate (PPDI), hexa-methylene two
One in isocyanates (HDI), different Buddhist diisocyanates (IPDI), hydrogenation 4,4- '-diphenylmethane diisocyanates (HMDI)
The mixture of kind or any combination；
The small molecule dihydric alcohol is selected from ethylene glycol, 1,2- propane diols, 1,3- propane diols, 1,4- butanediols, 1,3- fourths
Glycol, 1,5- pentanediols, neopentyl glycol, 1,6-HD, 1,8- ethohexadiols, hydroquinone hydroxyethyl ether (HQEE), cyclohexyl diformazan
Alcohol, 2- methyl isophthalic acids, ammediol, 2- methyl isophthalic acids, one or more kinds of mixtures in 3- butanediols, mixed proportion are unlimited；
The two terminal hydroxy group Y-shaped pendant hydrophilic chain extender of low melting point is selected from the 2- that number-average molecular weight is 500-2000 and gathers
A kind of or mixture, mixed proportion are unlimited in glycol monoethyl ether -1,4-butanediol；
The catalyst is stannous octoate, dibutyl tin laurate, organic zinc, one kind in organo-bismuth or mixing
Thing；
(2) by the polyurethane melt of acquisition, it is continuously injected into shear pump, while the water with surfactant is injected
Shear pump, and disperse in 120-200 DEG C of high temperature and 0.2-1.5Mpa down cuts；
The surfactant is sodium hexadecyl sulfate, neopelex, three ethanol of dodecyl benzene sulfonic acid
One or more mixtures in amine salt, triethanolamine lauryl base sulfate；
(3) by step (2) obtained by product, be cooled to 30-50 DEG C, and be depressured, be sent into the storage tank with stirring, stirring
5~15min, obtains the solvent-free aqueous polyurethane dispersion that weight solid content is 30-50%；
The solvent-free aqueous polyurethane dispersion, includes the component of following mass percent：
Preferably, the solvent-free aqueous polyurethane dispersion, includes the component of following mass percent：
The above-mentioned aqueous polyurethane dispersion viscosity prepared based on combined type double screw reactor is in 100-2000mpas
(20 DEG C), preferably 200-1000mpas (20 DEG C).
The molecular weight of the aqueous polyurethane dispersion is between 30,000-200,000, to meet institute in practical application
The high anti-tensile requirement of high molecular weight, big cohesive energy, low modulus needed；
Aqueous polyurethane dispersion obtained by this method, can be widely applied to synthetic leather, adhesive, coating, fabric and applies
The every field such as layer, finishing agent, as synthetic leather resin, can be applied to base fabric bottom material resin, surface layer resin, tie layer resins,
The fields such as intermediate layer resin, foaming layer resin.
The present invention is a kind of continous way that aqueous polyurethane dispersion is prepared based on double-screw reactor and shear at high temperature pump
Each raw material of solvent-free production process, i.e. aqueous polyurethane dispersion is realized in double-screw reactor in the short time aggregates into high score
The polymer melt of son amount, during which carries out in the shear pump of high temperature and pressure and and dispersion and emulsion, then after cooling decompression
Into aqueous polyurethane dispersion.The technology utilization twin-screw technique realizes the high molecular weight of aqueous polyurethane, high cohesion energy and height
Performance, and the hydrogen bond of polyurethane is dissociated using high temperature make to slide between strand to substitute traditional solvolysis hydrogen bond
Move, recycle high speed shear pump can be in very short time internal emulsification, so that urea groups is contour instead of high speed dispersor emulsifying process
The advantages that cohesive energy group can be implanted into aqueous polyurethane molecular structure by rear chain extension technique, realize high cohesion energy and heat resistance.
The technique realizes serialization, high performance and the solvent free of aqueous polyurethane dispersion preparation in a word, greatly promotes water-based
The performance and production efficiency of polyurethane, realize the perfect unity of aqueous polyurethane high-performance and low cost.
Compared with existing twin-screw prepares aqueous polyurethane dispersion technique and the water-based technique of traditional acetone prepolymer method, this
Technique can realize following technique effect：
What twin-screw and high speed shear pump can solve high viscosity aqueous polyurethane melt the technique hardly possible such as synthesizes, disperses, emulsify
Topic, process are participated in without solvent, really realize the pure green environmental requirement of aqueous polyurethane；By means of making for high speed shear pump
With additional emulsifying agent, can be prepared non-ionic polyurethane dispersion if necessary, and product quality and lot stability are good；Work
Skill is simple, efficient, and 30-60min is only needed from output is dosed into, and can realize full continuous automatic production requirement, improves life
Produce the stability of efficiency and product batches；The technique reduces production cost, carries without using expensive hydrophilic chain extender
The high competitiveness of product in market.
Embodiment
By specific examples below, the present invention is described in detail, but the scope that the present invention is protected is not limited to this
A little embodiments, further include formula adjustment and the process modifications of the non-intrinsically safe done according to the content of the invention.
Pass through the basic performance of dispersions of polyurethanes in the following test method characterization present invention：
The measure of solid content：Weighed up with electronic balance and show that the quality of clean surface plate is M1；2-3g lotions are taken to be placed in
Its quality is referred to as M in surface plate2；Surface plate quality is weighed after when placement 1 is small in 120 DEG C of convection ovens, continues to be put into baking oven,
Until alleged constant mass writes down M3。
Solid content：C=(M3-M1)/(M2-M1) × 100%
Tensile strength：Refer to the stress that material produces maximum uniform plastic deformation.In tension test, sample is until be fractured into
Only suffered maximum tensile stress is tensile strength, can be calculated by maximum load divided by specimen cross section product.
The measure of tensile strength：Dispersions of polyurethanes in the present invention is uniformly coated in polytetrafluoroethylene (PTFE) pallet,
After room temperature dries film forming, the dry 1hr in 120 DEG C of convection ovens, then after 50 DEG C of baking ovens place 8hr, then in test environment
After placing 24hr, its tensile strength is tested with the rate of extension of 100mm/min.
Elongation at break：Refer to shift value of the sample in tension failure and former long ratio, as a percentage (%).
100% modulus：Refer to tensile strength when elongation is 100%.
Embodiment 1
Formula：(mass percent)
Preparation method：
By polytetrahydrofuran diol (Mn=2000), 2- poly glycol monomethyl ether -1,4- butanediols (Mn=1000), 2- first
Base -1,3-BDO is mixed and heated to 80 DEG C, adds octoate catalyst stannous, and 4,4- '-diphenylmethane diisocyanates (MDI) rise
For temperature to 80 DEG C, both of the above is respectively 250rpm, L/D=by injecting rotating speed after mixing head through gear wheel metering pump, flowmeter
45th, temperature is respectively 120 DEG C, 130 DEG C, 140 DEG C, 150 DEG C, 150 DEG C, 160 DEG C, 210 DEG C of double-screw reactor reaction, is stopped
Time is 0.5min；
Be 150 DEG C through smelt gear pump implantation temperature, rotating speed be that while temperature is 150 DEG C, pressure in 1500rpm shear pumps
Power is 0.5Mpa, concentration is 0.5%wt sodium hexadecyl sulfates solution also in shear pump, shears 4min；
It is collected into after heat exchanger is cooled to 30 DEG C, is depressured normal pressure in stainless steel storage tank, 15min is stirred after collecting completely,
The aqueous polyurethane dispersion, solid content 30.0%wt can be obtained.
Product characters are observed, without undissolved White Flocculus, emulsion-stabilizing is homogeneous, and the aqueous polyurethane dispersion is quiet
After putting one month, without white precipitate.
Embodiment 2
Formula：(mass percent)
Preparation method：
Polytetrahydrofuran diol (Mn=4000), polyoxyethylene glycol (Mn=1000), 1,4- butanediols are mixed
60 DEG C are heated to, adds octoate catalyst stannous, toluene di-isocyanate(TDI) (TDI) is warming up to 60 DEG C, and both of the above is respectively through tooth
Take turns metering pump, flowmeter, by injecting rotating speed after mixing head for 200rpm, L/D=56, temperature be respectively 80 DEG C, 100 DEG C, 130
DEG C, 140 DEG C, 150 DEG C, 170 DEG C, the reaction of 215 DEG C of double-screw reactor, residence time 2min；
Be 120 DEG C through smelt gear pump implantation temperature, rotating speed be that while temperature is 120 DEG C, pressure in 2500rpm shear pumps
Power is 0.2Mpa, concentration is that 2%wt sodium hexadecyl sulfate solution is also injected into shear pump, shears 5min；
Be cooled to 50 DEG C through heat exchanger, be depressurized to normal pressure and be collected into stainless steel storage tank, collect it is full after stir 15min,
The aqueous polyurethane dispersion, solid content 37.0%wt can be obtained.Product characters are observed, without undissolved white
Floccule, emulsion-stabilizing is homogeneous, after which stands one month, without white precipitate.
Embodiment 3
Formula：(mass percent)
Preparation method：
By polyadipate -1,4- butyl glycol ester diols (Mn=4000), 2- poly glycol monomethyl ether -1,4- butanediols (Mn
=2000), ethylene glycol is mixed and heated to 100 DEG C, adds catalyst dibutyltin dilaurylate, molar ratio 1:2 different Fo Er
Ketone diisocyanate (IPDI) and hydrogenation 4,4- '-diphenylmethane diisocyanates (HMDI) are warming up to 100 DEG C, both of the above difference
By injecting rotating speed after mixing head for 250rpm, L/D=50, temperature it is respectively 100 DEG C, 120 through gear wheel metering pump, flowmeter
DEG C, 130 DEG C, 140 DEG C, 170 DEG C, 200 DEG C, the reaction of 230 DEG C of double-screw reactor, residence time 1.5min；
Be 200 DEG C through smelt gear pump implantation temperature, rotating speed be that while temperature is 200 DEG C, pressure in 1500rpm shear pumps
Power is 1.5Mpa, concentration be 1%wt neopelexes solution also with 150kg/h flow shear pumps, shear 3min；
Be cooled to 30 DEG C through heat exchanger, be depressurized to normal pressure and be collected into stainless steel storage tank, collect it is full after stir 10min,
The aqueous polyurethane dispersion, solid content 50.0%wt can be obtained.Product characters are observed, without undissolved white
Floccule, emulsion-stabilizing is homogeneous, after which stands one month, without white precipitate.
Embodiment 4
Formula：(mass percent)
Preparation method：
By polypropylene oxide ethylene oxide copolymerization dihydric alcohol (Mn=2000), polyethylene glycol adipate glycol (Mn=
2000), 2- poly glycol monomethyl ethers -1,4-butanediol (Mn=500), 1,4-butanediol are mixed and heated to 90 DEG C, addition catalysis
Agent dibutyl tin laurate, 4,4- '-diphenylmethane diisocyanates (MDI) are warming up to 90 DEG C, and both of the above is respectively through gear meter
Amount pump, flowmeter by injecting rotating speed after mixing head for 300rpm, L/D=45, temperature are respectively 120 DEG C, 130 DEG C, 140 DEG C,
150 DEG C, 150 DEG C, 160 DEG C, 210 DEG C of double-screw reactor reaction, residence time 3min；
Be 180 DEG C through smelt gear pump implantation temperature, rotating speed be that while temperature is 180 DEG C, pressure in 1500rpm shear pumps
Power is 1.3Mpa, concentration is that 1.5%wt dodecyl benzene sulfonic acid triethanolamine salting liquids are also injected into shear pump, shears 3min；
Be cooled to 40 DEG C through heat exchanger, be depressurized to normal pressure and be collected into stainless steel storage tank, collect it is full after stir 5min, i.e.,
The aqueous polyurethane dispersion, solid content 40.0%wt can be obtained.Product characters are observed, are wadded a quilt with cotton without undissolved white
Shape thing, emulsion-stabilizing is homogeneous, after which stands one month, without white precipitate.
Embodiment 5
Formula：(mass percent)
Preparation method：
By poly- ethylene carbonate esterdiol (Mn=2000), -1,4 butanediol of 2- poly glycol monomethyl ethers (Mn=1000),
Neopentyl glycol is mixed and heated to 100 DEG C, adds octoate catalyst stannous, and 4,4- '-diphenylmethane diisocyanates (MDI) are warming up to
100 DEG C, both of the above is respectively through gear wheel metering pump, flowmeter, by injecting rotating speed after syncephalon for 300rpm, L/D=16, temperature
Respectively 130 DEG C, 130 DEG C, 140 DEG C, 150 DEG C, 150 DEG C, 150 DEG C, the reaction of 205 DEG C of double-screw reactor, residence time be
2.5min；
Be 150 DEG C through smelt gear pump implantation temperature, rotating speed be that while temperature is 150 DEG C, pressure in 2000rpm shear pumps
The molar ratio that power is 0.5Mpa, concentration is 2%wt is 1:1 triethanolamine lauryl base sulfate and neopelex is molten
Liquid is also injected into shear pump, shears 4min；
Be cooled to 30 DEG C through heat exchanger, be depressurized to normal pressure and be collected into stainless steel storage tank, collect it is full after stir 15min,
The aqueous polyurethane dispersion, solid content 45.6%wt can be obtained.Product characters are observed, without undissolved white
Floccule, emulsion-stabilizing is homogeneous, after which stands one month, without white precipitate.
Embodiment 6
Formula：(mass percent)
Preparation method：
By polyoxyethylene glycol (Mn=2000), -1,4 butanediol of 2- poly glycol monomethyl ethers (Mn=1000), new
Pentanediol is mixed and heated to 80 DEG C, adds octoate catalyst stannous, and toluene di-isocyanate(TDI) (TDI) is warming up to 80 DEG C, the above two
Person is respectively respectively 120 by injecting rotating speed after mixing head for 300rpm, L/D=30, temperature through gear wheel metering pump, flowmeter
DEG C, 120 DEG C, 130 DEG C, 140 DEG C, 150 DEG C, 170 DEG C, the reaction of 215 DEG C of double-screw reactor, residence time 1min；
Be 120 DEG C through smelt gear pump implantation temperature, rotating speed be in 2500rpm shear pumps, while temperature be 120 DEG C, it is dense
Spend and be also injected into for 4%wt neopelex solution in shear pump, shear 5min；
Be cooled to 40 DEG C through heat exchanger, be depressurized to normal pressure and be collected into stainless steel storage tank, collect it is full after stir 15min,
The aqueous polyurethane dispersion, solid content 37.9%wt can be obtained.Product characters are observed, without undissolved white
Floccule, emulsion-stabilizing is homogeneous, after which stands one month, without white precipitate.
Comparative example 1
Formula：(mass percent)
Preparation method：
By polytetrahydrofuran diol (Mn=2000), 2- poly glycol monomethyl ether -1,4- butanediols (Mn=1000), 2- first
Base -1,3-BDO is mixed and heated to 80 DEG C, adds octoate catalyst stannous, and 4,4- '-diphenylmethane diisocyanates (MDI) rise
For temperature to 80 DEG C, both of the above is respectively 250rpm, L/D=by injecting rotating speed after mixing head through gear wheel metering pump, flowmeter
70th, temperature is respectively 120 DEG C, 130 DEG C, 140 DEG C, 150 DEG C, 150 DEG C, 160 DEG C, 210 DEG C of double-screw reactor reaction, is stopped
Time is 1min；
Be 150 DEG C through smelt gear pump implantation temperature, rotating speed be that while temperature is 150 DEG C, pressure in 1500rpm shear pumps
Power is 0.5Mpa, concentration is that 0.5%wt sodium hexadecyl sulfate solution is also injected into shear pump, shears 4min；
It is collected into after heat exchanger is cooled to 30 DEG C, is depressured normal pressure in stainless steel storage tank, 15min is stirred after collecting completely；
Aqueous polyurethane dispersion, solid content 30.0%wt can be obtained.
Observation product characters find there are a large amount of undissolved White Flocculus, can not obtain the lotion of stable uniform.
Comparative example 2
Formula：(mass percent)
Preparation method：
By polyoxyethylene glycol (Mn=2000), -1,4 butanediol of 2- poly glycol monomethyl ethers (Mn=1000), new
Pentanediol is mixed to 80 DEG C of heating, adds octoate catalyst stannous, and toluene di-isocyanate(TDI) (TDI) is warming up to 80 DEG C, the above two
Person is respectively respectively 120 by injecting rotating speed after mixing head for 300rpm, L/D=10, temperature through gear wheel metering pump, flowmeter
DEG C, 120 DEG C, 130 DEG C, 140 DEG C, 150 DEG C, 170 DEG C, the reaction of 215 DEG C of double-screw reactor, residence time 3min；
Be 120 DEG C through smelt gear pump implantation temperature, rotating speed be in 2500rpm shear pumps, while temperature be 120 DEG C, it is dense
It is 4%wt neopelexes solution also with 220kg/h flow shear pumps to spend, and shears 5min；
Be cooled to 40 DEG C through heat exchanger, be depressurized to normal pressure and be collected into stainless steel storage tank, collect it is full after stir 15min,
A kind of aqueous polyurethane dispersion, solid content 37.9%wt can be obtained.
The product stability is bad, stands two days later, a large amount of white precipitates occurs.
The physical property of aqueous polyurethane dispersion obtained by embodiment 1-6 is as follows：
| Embodiment | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 |
| Solid content | 30.0%wt | 37%wt | 50.0%wt | 40.0%wt | 45.6%wt | 37.9%wt |
| Emulsion viscosity (20 DEG C) | 200cp | 350cp | 840cp | 530cp | 480cp | 320cp |
| 100% modulus | 1.2 | 2.1 | 3.4 | 1.5 | 1.7 | 1.1 |
| Tensile strength (Mpa) | 24 | 37 | 46 | 29 | 26 | 22 |
| Elongation at break % | 900 | 840 | 730 | 950 | 800 | 970 |
By the testing result of embodiment and comparative example as it can be seen that due to the present invention double-screw reactor used it is special
Draw ratio, suitable temperature and time, reduce the hair of side reaction as far as possible again ensureing raw material while the reaction was complete
Raw, the WTPUD lotion storage stabilities being prepared are good, performance stablize it is excellent, can be widely applied to synthetic leather, adhesive,
The every field such as coating, fabric coating, finishing agent, particularly as synthetic leather resin, can be applied to base fabric bottom material resin, surface layer
The fields such as resin, tie layer resins, intermediate layer resin, foaming layer resin.
Claims (10)
1. the preparation method of solvent-free aqueous polyurethane dispersion, it is characterised in that include the following steps：
(1) by polymer diatomic alcohol, diisocyanate, small molecule dihydric alcohol, two terminal hydroxy group Y-shaped pendant hydrophilic chain extension of low melting point
Agent and catalyst, preheat respectively, after being then input to mixer disperses mixing, are input in double-screw reactor and react, obtain
Polyurethane melt；
(2) by the polyurethane melt of acquisition, it is continuously injected into shear pump, while the water with surfactant is injected into shearing
Pump shearing is scattered；
(3) by step (2) obtained by product, decrease temperature and pressure, stirring, obtains the solvent-free aqueous polyurethane dispersion.
2. according to the method described in claim 1, it is characterized in that, the surfactant is sodium hexadecyl sulfate, 12
One or more in sodium alkyl benzene sulfonate, dodecyl benzene sulfonic acid triethanolamine salt, triethanolamine lauryl base sulfate.
3. according to the method described in claim 1, it is characterized in that, using 16≤L/D≤56, more than rotating speed 200-300rpm
Double screw extruder, wherein：L represents spiro rod length, and D represents screw diameter, in the double-screw reactor, reaction temperature point
For 7 sections, first segment is 80-130 DEG C, and second segment is 100-130 DEG C, and the 3rd section is 130-140 DEG C, and the 4th section is 140-150 DEG C,
5th section is 150-170 DEG C, and the 6th section is 150-200 DEG C, and the 7th section is 205-230 DEG C, during stop of the material in twin-screw
Between be 0.5-3min.
4. according to the method described in claim 2, it is characterized in that, using 16≤L/D≤56, more than rotating speed 200-300rpm
Double screw extruder, wherein：L represents spiro rod length, and D represents screw diameter, in the double-screw reactor, reaction temperature point
For 7 sections, first segment is 80-130 DEG C, and second segment is 100-130 DEG C, and the 3rd section is 130-140 DEG C, and the 4th section is 140-150 DEG C,
5th section is 150-170 DEG C, and the 6th section is 150-200 DEG C, and the 7th section is 205-230 DEG C, during stop of the material in twin-screw
Between be 1-3min.
5. according to Claims 1 to 4 any one of them method, it is characterised in that the polymer diatomic alcohol is polyethers two
First alcohol, polyester diol, the one or more in polycarbonate glycol；
The polyether Glycols use 2 terminal hydroxy groups, and number-average molecular weight is the various structural polyether oligomers of 200-10000, is wrapped
Include and be not limited to：PolyTHF dihydric alcohol (PTMEG), Polyoxypropylene diol (PPG), polyoxyethylene glycol (PEG)
With the one or more of polypropylene oxide ethylene oxide copolymerization dihydric alcohol (PEPG)；
The polyester diol is to contain 2 oligomers of the terminal hydroxy group containing polyester construction, range of number-average molecular weight 200-4000,
Including being not limited to：Polyadipate -1,4- butyl glycol ester diols (PBA), polyethylene glycol adipate glycol (PEA), polyadipate
Propylene glycol ester glycol (PPA), the hexylene glycol of polyadipate -1,6 esterdiol (PHA), polyneopentyl glycol adipate glycol (PNA),
Polyadipate ethylene glycol butyl glycol ester diol (PEBA), polyadipate ethylene glycol propylene glycol ester glycol (PEPA), polyadipate oneself
Glycol neopentyl glycol esterdiol (PHNA), polybutyleneadipate hexylene glycol esterdiol (PBHA), polybutyleneadipate new penta
Glycol esterdiol (PBNA), the one or more for gathering own Inner esterdiols；
The polycarbonate glycol uses the oligomer containing 2 terminal hydroxy group carbonate-containing structures, range of number-average molecular weight
For 200-4000, exchanged and synthesized with binary alcohol esters by carbonic diester, including be not limited to：Poly- carbonic acid hexylene glycol esterdiol, poly- carbonic acid
One or more mixtures of pentadiol ester glycol, polytetramethylene carbonate diol glycol, poly (propylene carbonate) glycol etc.；
It is sub- that the diisocyanate is selected from 4,4- '-diphenylmethane diisocyanates (MDI), toluene di-isocyanate(TDI) (TDI), benzene
Methyl diisocyanate (XDI), 1,5- how diisocyanate (NDI), paraphenylene diisocyanate (PPDI), two isocyanide of hexa-methylene
In acid esters (HDI), different Buddhist diisocyanates (IPDI), hydrogenation 4,4- '-diphenylmethane diisocyanates (HMDI) it is a kind of with
On.
6. the method according to right wants 5, it is characterised in that the small molecule dihydric alcohol is selected from ethylene glycol, 1,2- the third two
Alcohol, 1,3- propane diols, 1,4- butanediols, 1,3 butylene glycol, 1,5- pentanediols, neopentyl glycol, 1,6-HD, 1,8- pungent two
Alcohol, hydroquinone hydroxyethyl ether (HQEE), cyclohexane dimethanol, 2- methyl-1,3-propanediols, 2- methyl isophthalic acids, one in 3- butanediols
Kind is a variety of；
The two terminal hydroxy group Y-shaped pendant hydrophilic chain extender of low melting point is selected from the poly- second two of 2- that number-average molecular weight is 500-2000
More than one in alcohol monomethyl ether -1,4- butanediols.
7. the method according to right wants 6, it is characterised in that the catalyst is stannous octoate, di lauric dibutyl
One or more of tin, organic zinc, organo-bismuth.
8. the method according to right wants 5, it is characterised in that the solvent-free aqueous polyurethane dispersion, including it is as follows
The component of mass percent：
9. the aqueous polyurethane dispersion prepared according to any one of claim 1~8 the method.
10. the application of aqueous polyurethane dispersion according to claim 9, it is characterised in that for synthetic leather, gluing
Agent, coating, fabric coating, finishing agent, base fabric bottom material resin, surface layer resin, tie layer resins, intermediate layer resin or foaming layer tree
Fat.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711049515.0A CN107964104B (en) | 2017-10-31 | 2017-10-31 | Solvent-free aqueous polyurethane dispersion, and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711049515.0A CN107964104B (en) | 2017-10-31 | 2017-10-31 | Solvent-free aqueous polyurethane dispersion, and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107964104A true CN107964104A (en) | 2018-04-27 |
| CN107964104B CN107964104B (en) | 2021-05-11 |
Family
ID=61999911
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711049515.0A Active CN107964104B (en) | 2017-10-31 | 2017-10-31 | Solvent-free aqueous polyurethane dispersion, and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107964104B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109535377A (en) * | 2018-12-04 | 2019-03-29 | 山东天庆科技发展有限公司 | A kind of aqueous polyurethane and the preparation method and application thereof with from foam stabilizing function |
| CN110698631A (en) * | 2019-10-11 | 2020-01-17 | 合肥科天水性科技有限责任公司 | Waterborne polyurethane emulsion and preparation method and application thereof |
| CN112321795A (en) * | 2020-11-19 | 2021-02-05 | 明新孟诺卡(江苏)新材料有限公司 | Solvent-free waterborne polyurethane capable of being continuously produced and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102633971A (en) * | 2012-04-19 | 2012-08-15 | 王武生 | Double-screw reactor design based continuous production process of aqueous polyurethane dispersion |
| WO2013176257A1 (en) * | 2012-05-25 | 2013-11-28 | トーヨーポリマー株式会社 | Aqueous polyurethane dispersing element, film-molded body obtained therefrom, and glove |
| CN107099015A (en) * | 2017-03-24 | 2017-08-29 | 广东科茂林产化工股份有限公司 | A kind of modified aqueous polyurethane dispersoid and preparation method thereof |
-
2017
- 2017-10-31 CN CN201711049515.0A patent/CN107964104B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102633971A (en) * | 2012-04-19 | 2012-08-15 | 王武生 | Double-screw reactor design based continuous production process of aqueous polyurethane dispersion |
| WO2013176257A1 (en) * | 2012-05-25 | 2013-11-28 | トーヨーポリマー株式会社 | Aqueous polyurethane dispersing element, film-molded body obtained therefrom, and glove |
| CN107099015A (en) * | 2017-03-24 | 2017-08-29 | 广东科茂林产化工股份有限公司 | A kind of modified aqueous polyurethane dispersoid and preparation method thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109535377A (en) * | 2018-12-04 | 2019-03-29 | 山东天庆科技发展有限公司 | A kind of aqueous polyurethane and the preparation method and application thereof with from foam stabilizing function |
| CN109535377B (en) * | 2018-12-04 | 2021-04-23 | 山东天庆科技发展有限公司 | Waterborne polyurethane with self-foam stabilizing function and preparation method and application thereof |
| CN110698631A (en) * | 2019-10-11 | 2020-01-17 | 合肥科天水性科技有限责任公司 | Waterborne polyurethane emulsion and preparation method and application thereof |
| CN110698631B (en) * | 2019-10-11 | 2021-11-02 | 合肥科天水性科技有限责任公司 | Waterborne polyurethane emulsion and preparation method and application thereof |
| CN112321795A (en) * | 2020-11-19 | 2021-02-05 | 明新孟诺卡(江苏)新材料有限公司 | Solvent-free waterborne polyurethane capable of being continuously produced and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107964104B (en) | 2021-05-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107840937A (en) | Solvent-free aqueous polyurethane dispersion of extrusion molding and its preparation method and application | |
| CN107903377A (en) | Solvent-free sulfonate aqueous polyurethane dispersion of continous way and preparation method thereof | |
| CN107903376A (en) | Solvent-free aqueous polyurethane dispersion of continous way and its preparation method and application | |
| CN100489004C (en) | Polyurethane dispersions (PUD) with improved isopropanol resistance, flexibility and softness | |
| CN102532463B (en) | Aqueous polyurethane and preparation method thereof | |
| CN101585903B (en) | Water-borne polyurethane and preparation method thereof | |
| CN105440240B (en) | Prepare the continuous production method of aqueous polyurethane ionomer and its dispersion | |
| CN103382253B (en) | A kind of high-performance water-based polyurethane dispersoid and preparation method thereof | |
| CN107022297A (en) | A kind of water-fast aqueous polyurethane coating with bi component and preparation method thereof | |
| DE19942393C2 (en) | Soft, elastic polyurethane films, process for their production and their use | |
| CN107964104A (en) | Solvent-free aqueous polyurethane dispersion and its preparation method and application | |
| CN108097194B (en) | Continuous production system for preparing aqueous polyurethane dispersion, continuous production process for aqueous polyurethane dispersion and application | |
| CN109942781B (en) | UV-cured castor oil-based aqueous polyurethane dispersion and preparation method and application thereof | |
| CN108264622B (en) | Waterborne polyurethane, preparation intermediate and preparation method thereof | |
| CN102858847B (en) | Polyether polyols and urethane resin and containing these coating agent | |
| CN106978126A (en) | A kind of quick-setting single-component polyurethane adhesive of normal temperature and preparation method thereof | |
| CN108034349A (en) | The preparation method of the eight modified bi-component aqueous polyaminoester emulsions of nitro silsesquioxane | |
| US20220282022A1 (en) | Method for producing thermoplastically processable polyurethane polymers | |
| EP2185618A1 (en) | Process for the production of hyperbranched, dendritic polyurethanes by means of reactive extrusion | |
| JP4976249B2 (en) | Method for producing aqueous polyurethane resin | |
| CN105980431A (en) | Aqueous urethane-urea resin composition and production method, and, reactive emulsifier and emulsification method | |
| CN106750117B (en) | A kind of aqueous polyurethane continuous synthesis method based on impingement mix and continuous emulsification | |
| TWI819291B (en) | Waterborne polyurethane | |
| CN109265648A (en) | A kind of Diamond Search aqueous polyurethane dispersion and preparation method | |
| CN112500550B (en) | Method for preparing aqueous polyurethane dispersion without organic solvent |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |