CN107840937A - Solvent-free aqueous polyurethane dispersion of extrusion molding and its preparation method and application - Google Patents
Solvent-free aqueous polyurethane dispersion of extrusion molding and its preparation method and application Download PDFInfo
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- CN107840937A CN107840937A CN201711045561.3A CN201711045561A CN107840937A CN 107840937 A CN107840937 A CN 107840937A CN 201711045561 A CN201711045561 A CN 201711045561A CN 107840937 A CN107840937 A CN 107840937A
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- C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
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Abstract
The invention provides solvent-free aqueous polyurethane dispersion of a kind of extrusion molding and its preparation method and application, preparation method, comprise the following steps：(1) by polymer diatomic alcohol, diisocyanate, small molecule dihydric alcohol, the terminal hydroxy group Y-shaped pendant hydrophilic chain extender of low melting point two and catalyst, preheat respectively, after being then input to mixer disperses mixing, it is input in double-screw reactor and reacts, obtains polyurethane melt；(2) it is injected into shear pump, while the water with nertralizer is injected into shear pump, and disperses in 120 200 DEG C of high temperature and 0.2 1.5Mpa down cuts；(3) decrease temperature and pressure, rear chain extender is added, stirring reaction, obtains the solvent-free aqueous polyurethane dispersion.The method of the present invention, it is green, the cohesive energy of product is significantly lifted, production process is efficient, can greatly improve the performance of aqueous polyurethane.
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 simultaneously, 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 reactor.The problem of maximum during pre-polymerization is that reactor is generally difficult to handle height
Viscous systems, therefore pre- collecting process usually requires to add organic solvent reduction polymerization system viscosity or the molecular weight by prepolymer
It is controlled in extremely low level.After prepolymerization reaction terminates, 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 can not still participate in polymerizeing after the simple recovery purifying of these solvents
Very high to equipment requirement when journey, causing manufacturing cost to greatly increase, while emulsifying, large-scale production efficiency is low, typically from throwing
Expect that discharging needs 12-16 hours.
A kind of new aqueous polyurethane preparation technology 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.Because 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 stably
Performance, realize again 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 PEPA, diisocyanate, small molecule chain extender and hydrophilic list
Body, aqueous polyurethane is also prepared 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 DMPA accurate measurement, HTHP emulsifying technology was produced with reducing
The usage amount of solvent in journey, substantially increase the production efficiency of aqueous polyurethane and reduce environmental pollution, but it is 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, the aqueous polyurethane that acetone produces 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 recovery 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
It is an object of the invention to provide solvent-free aqueous polyurethane dispersion of a kind of continous way and its preparation method and application,
The defects of to overcome prior art to exist.
The method of the present invention, comprises the following steps：
(1) by polymer diatomic alcohol, diisocyanate, small molecule dihydric alcohol, the terminal hydroxy group Y-shaped pendant hydrophilic of low melting point two
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 described double-screw reactor, it is desirable to which material can axially and radially having very in screw rod
Big shearing divergent function, it is overcome measurement deviation on the different time caused by measuring equipment pulse, inventor has found,
Using 16≤L/D≤56, more than rotating speed 200-300rpm double screw extruder, can get a desired effect；
Wherein：L represents spiro rod length, and D represents screw diameter；
In described double-screw reactor, reaction temperature is divided into 7 sections, and first paragraph 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；
Described polymer diatomic alcohol is polyether Glycols, polyester diol, one kind or more in PCDL
Kind mixture；
Described polyether Glycols use 2 terminal hydroxy groups, and number-average molecular weight is 200-10000 various structural polyether oligomerisations
Thing, including be not limited to：PolyTHF dihydric alcohol (PTMEG), Polyoxypropylene diol (PPG), polyoxyethylene glycol
(PEG) and PPOX ethylene oxide is copolymerized one or more mixtures of dihydric alcohol (PEPG), and mixed proportion is unlimited；
Described polyester diol is to contain 2 oligomers of the terminal hydroxy group containing polyester construction, range of number-average molecular weight 200-
10000, including be not limited to：The butyl glycol ester diol of polyadipate -1,4 (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；
Described PCDL uses the oligomer containing 2 terminal hydroxy group carbonate-containing structures, number-average molecular weight
Scope is 200-10000, is exchanged and synthesized with binary alcohol esters by carbonic diester, including is not limited to：Poly- carbonic acid hexylene glycol esterdiol, gather
One or more mixtures of neopentyl glycol carbonate esterdiol, polytetramethylene carbonate diol glycol, poly (propylene carbonate) glycol etc.；
Described diisocyanate be selected from 4,4- '-diphenylmethane diisocyanates (MDI), toluene di-isocyanate(TDI) (TDI),
Tolylene diisocyanate (XDI), 1,5- how diisocyanate (NDI), PPDI (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；
Described 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, one or more kinds of mixtures in ammediol, mixed proportion are unlimited；
The described terminal hydroxy group Y-shaped pendant hydrophilic chain extender of low melting point two is selected from dihydromethyl propionic acid and dimethylolpropionic acid
In one kind or mixture, mixed proportion it is unlimited；
Described 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 nertralizer is injected into shearing
Pump, and disperse in 120-200 DEG C of high temperature and 0.2-1.5Mpa down cuts；
Described nertralizer is the one or more in triethylamine, dimethylethanolamine, methyl diethanolamine, triethanolamine
Mixture；
(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, add
Rear chain extender, 5~15min of stirring reaction, obtain the solvent-free aqueous polyurethane dispersion that mass content is 30-50%；
Described rear chain extender is selected from ethylenediamine, propane diamine, butanediamine, 1,6- hexamethylene diamines, second diaminourea ethyl sulfonic acid sodium, second
One or more of diaminourea propanesulfonate；
Described solvent-free aqueous polyurethane dispersion, include the component of following mass percent：
Preferably, described solvent-free aqueous polyurethane dispersion, the component of following mass percent is included：
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 described aqueous polyurethane dispersion is between 30,000-200,000, to meet institute in practical application
The high anti-tensile requirement of the HMW that needs, big cohesive energy, low modulus；
Aqueous polyurethane dispersion obtained by this method, it can be widely applied to synthetic leather, adhesive, coating, fabric and apply
The every field such as layer, finishing agent, as synthetic leather resin, can be applied to base fabric bed 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 the melt is carried out in the shear pump of HTHP and and dispersion and emulsion, then after cooling decompression
Into aqueous polyurethane dispersion.The technology utilization twin-screw technique realizes the HMW 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 to replace high speed dispersor emulsifying process can be in very short time internal emulsification, and then make it that urea groups is contour
Cohesive energy group can be implanted into aqueous polyurethane molecular structure by rear chain extension technique, realize high cohesion can and the advantages that 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：
Twin-screw and high speed shear pump can solve high viscosity aqueous polyurethane melt the technique such as to synthesize, disperse, emulsifying difficult
Topic, process participate in without solvent, really realize the pure green environmental requirement of aqueous polyurethane；Because emulsion process is in shear pump
Moment completes, therefore most of isocyanate functional group can remain, and participate in the rear chain extending reaction of amino, realize water-based
Urea groups structure is implanted into polyurethane structural, significantly lifts the cohesive energy of product；Production process is efficient, is only needed from output is dosed into
30-60min, and full continuous automatic production requirement can be realized；Chain extension implementation cost is relatively low afterwards, is hardly increasing cost
In the case of greatly improve the performance of aqueous polyurethane.
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, in addition to the formula adjustment of the non-intrinsically safe done according to the content of the invention and process modifications.
The basic performance of dispersions of polyurethanes in the present invention is characterized by following test method：
The measure of solid content：Weighed up with electronic balance and show that the quality of clean surface plate is M1；2-3g emulsions are taken to be placed in
Its quality is referred to as M in surface plate2；Surface plate quality is weighed after being placed 1 hour 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, 1hr is dried 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 100mm/min rate of extension.
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：
(1) polytetrahydrofuran diol (Mn=2000), dimethylolpropionic acid, BDO are mixed and heated to 80 DEG C,
Octoate catalyst stannous is added, 4,4- '-diphenylmethane diisocyanates (MDI) are warming up to 80 DEG C, and both of the above is respectively through gear meter
Measure pump, flowmeter, by injected after mixing head rotating speed be 250rpm, L/D=45, temperature be 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 0.5min；
(2) be 150 DEG C through smelt gear pump implantation temperature, rotating speed be in 1500rpm shear pumps, while temperature be 150 DEG C,
Pressure is that 0.5Mpa concentration is that 2.6%wt triethylamine aqueous solutions are also injected into shear pump, shears 4min；
(3) 30 DEG C are cooled to through heat exchanger, are depressurized to normal pressure and are collected into stainless steel storage tank, while 50% second diamino
Base ethyl sulfonic acid sodium water solution is also added in collecting tank with 3.6kg/h flows, stirs 15min, you can water-based poly- described in obtaining
Urethane dispersion, solid content 41.5%wt.Product characters are observed, it is homogeneous without undissolved White Flocculus, emulsion-stabilizing
, after the aqueous polyurethane dispersion stands one month, without white precipitate
Embodiment 2
Formula：(mass percent)
Preparation method：
(1) butyl glycol ester diol of polyadipate 1,4 (Mn=2000), dimethylolpropionic acid, 1,4- butanediols are mixed and added
Heat adds octoate catalyst stannous to 100 DEG C, and hydrogenation 4,4- '-diphenylmethane diisocyanates (HMDI) are warming up to 100 DEG C, the above
Both through gear wheel metering pump, flowmeter, are respectively respectively for 250rpm, L/D=30, temperature by injecting rotating speed after mixing head
120 DEG C, 120 DEG C, 130 DEG C, 140 DEG C, 150 DEG C, 170 DEG C, 215 DEG C of double-screw reactor reaction, residence time 2min；
(2) be 100 DEG C through smelt gear pump implantation temperature, rotating speed be in 1000rpm shear pumps, while temperature be 100 DEG C,
Pressure is 0.2Mpa, concentration is that the 2.3%wt methyl diethanolamine aqueous solution is also injected into shear pump, shears 5min；
(3) through heat exchanger be cooled to 50 DEG C, decompression be pooled in stainless steel storage tank, weight concentration be 50% second diamino
Base ethyl sulfonic acid sodium water solution is also added in collecting tank, stirs 30min, you can described aqueous polyurethane dispersion is obtained, Gu
Content is 40.0%wt.Product characters are observed, without undissolved White Flocculus, emulsion-stabilizing is homogeneous, the water-based poly- ammonia
After ester dispersion stands one month, without white precipitate
Embodiment 3
Formula：(mass percent)
Preparation method：
(1) by polytetrahydrofuran diol (Mn=2000), polyadipate 1,4- butyl glycol ester diols (Mn=2000), dihydroxy
Methylbutanoic acid, 2- methyl isophthalic acids, ammediol are mixed and heated to 60 DEG C, add octoate catalyst stannous, hydrogenate 4,4- diphenyl-methanes
Diisocyanate (HMDI) is warming up to 60 DEG C, and both of the above through gear wheel metering pump, flowmeter, is turned by being injected after mixing head respectively
Speed is 200rpm, L/D=56, temperature is respectively 80 DEG C, 100 DEG C, 130 DEG C, 140 DEG C, 150 DEG C, 170 DEG C, 215 DEG C of twin-screw
Reactor reaction, residence time 1min；
(2) be 200 DEG C through smelt gear pump implantation temperature, rotating speed be in 2500rpm shear pumps, while temperature be 200 DEG C,
Pressure is that 0.2Mpa concentration is that the 3.1%wt triethanolamine aqueous solution is also injected into shear pump, shears 3min；
(3) 40 DEG C are cooled to through heat exchanger, are depressurized to normal pressure and are collected into stainless steel storage tank, while weight concentration is
20% ethylenediamine solution is also added in collecting tank, stirs 10min, you can described aqueous polyurethane dispersion is obtained,
Solid content is 43.1%wt.Product characters are observed, without undissolved White Flocculus, emulsion-stabilizing is homogeneous, and this is water-based poly-
After urethane dispersion stands one month, without white precipitate
Embodiment 4
Formula：(mass percent)
Preparation method：
(1) PPOX ethylene oxide is copolymerized into dihydric alcohol (Mn=2000), dihydromethyl propionic acid, 1,3 butylene glycol to mix
Conjunction is heated to 90 DEG C, adds catalyst dibutyltin dilaurylate, and toluene di-isocyanate(TDI) (TDI) is warming up to 90 DEG C, the above two
Person is respectively respectively 130 by injecting rotating speed after mixing head for 300rpm, L/D=16, temperature through gear wheel metering pump, flowmeter
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 2.5min；
(2) be 180 DEG C through smelt gear pump implantation temperature, rotating speed be in 3000rpm shear pumps, while temperature be 180 DEG C,
Pressure is 1.3Mpa, concentration is that 4.0%wt triethylamine aqueous solutions are also injected into shear pump, shears 5min；
(3) 50 DEG C are cooled to through heat exchanger, are depressurized to normal pressure and are collected into stainless steel storage tank, while weight concentration is
30% mol ratio is 1:1 ethylenediamine and 1,6- the hexamethylene diamine aqueous solution is also added in collecting tank, stirs 10min, you can obtain
Obtain described aqueous polyurethane dispersion, solid content 50.0%wt.Product characters are observed, without undissolved white flock
Thing, emulsion-stabilizing is homogeneous, after the aqueous polyurethane dispersion stands one month, without white precipitate
Embodiment 5
Formula：(mass percent)
Preparation method：
Poly- ethylene carbonate esterdiol (Mn=2000), dimethylolpropionic acid, neopentyl glycol are mixed and heated to 100 DEG C,
Octoate catalyst stannous is added, 4,4- '-diphenylmethane diisocyanates (MDI) are warming up to 100 DEG C, and both of the above is respectively through gear
Measuring pump, flowmeter, by mixing head inject rotating speed be 250rpm, L/D=50, temperature be respectively 100 DEG C, 120 DEG C, 130 DEG C,
140 DEG C, 170 DEG C, 200 DEG C, 230 DEG C of double-screw reactor reaction, residence time 1.5min；
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
Power is 0.5Mpa, concentration be 1.6%wt triethylamine aqueous solutions also with 280kg/h flow shear pumps, handed over after shearing 5min through heat
Parallel operation, which is cooled to 50 DEG C, is depressurized to normal pressure is collected into stainless steel storage tank, while weight concentration is 20% 1,6- hexamethylene diamine water
Solution is also added in collecting tank, stirs 10min, you can obtains described aqueous polyurethane dispersion, solid content 30.0%
wt.Product characters are observed, without undissolved White Flocculus, emulsion-stabilizing is homogeneous, and the aqueous polyurethane dispersion is stood
After one month, without white precipitate
Embodiment 6
Formula：(mass percent)
Preparation method：
Polytetrahydrofuran diol (Mn=2000), dimethylolpropionic acid, ethylene glycol are mixed and heated to 80 DEG C, addition catalysis
Agent stannous octoate, 4,4- '-diphenylmethane diisocyanates (MDI) are warming up to 80 DEG C, and both of the above is respectively through gear wheel metering pump, stream
Gauge, by mixing head inject rotating speed be 300rpm, L/D=20, temperature be 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 3min；
Be 120 DEG C through smelt gear pump implantation temperature, rotating speed be that while temperature is 120 DEG C, pressure in 1500rpm shear pumps
Power is that 0.2Mpa concentration is that 2.9%wt triethylamine aqueous solutions are also injected into shear pump, shears 5min；
50 DEG C are cooled to through heat exchanger, normal pressure is depressurized to and is collected into stainless steel storage tank, while weight concentration is 20%
Ethylenediamine solution be also added in collecting tank, stir 5min, you can obtain described aqueous polyurethane dispersion, solid content
For 45.1%wt.Product characters are observed, without undissolved White Flocculus, emulsion-stabilizing is homogeneous, the aqueous polyurethane point
After granular media stands one month, without white precipitate
Embodiment 7
Formula：(mass percent)
Preparation method：
PPOX ethylene oxide copolymerization dihydric alcohol (Mn=2000), dimethylolpropionic acid, 1,3 butylene glycol are mixed
90 DEG C are heated to, adds catalyst dibutyltin dilaurylate, toluene di-isocyanate(TDI) (TDI) is warming up to 90 DEG C, both of the above
Respectively through gear wheel metering pump, flowmeter, by injecting rotating speed after mixing head be 300rpm, L/D=30, temperature is respectively 130 DEG C,
130 DEG C, 140 DEG C, 150 DEG C, 150 DEG C, 150 DEG C, 205 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 3000rpm shear pumps
Power is 1.3Mpa, concentration is that 4.0%wt triethylamine aqueous solutions are also injected into shear pump, shears 5min；
50 DEG C are cooled to through heat exchanger, normal pressure is depressurized to and is collected into stainless steel storage tank, while weight concentration is 20%
Ethylenediamine solution be also added in collecting tank, stir 15min, you can obtain described aqueous polyurethane dispersion, admittedly contain
Measure as 50.6%wt.
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.
Comparative example 1
Formula：(mass percent)
Preparation method：
Polytetrahydrofuran diol (Mn=2000), dimethylolpropionic acid, BDO are mixed and heated to 80 DEG C, addition
Octoate catalyst stannous, 4,4- '-diphenylmethane diisocyanates (MDI) are warming up to 80 DEG C, and both of the above is respectively through metering gear
Pump, flowmeter, by injected after mixing head rotating speed be 250rpm, L/D=70, temperature be 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 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 that 0.5Mpa concentration is that 2.6%wt triethylamine aqueous solutions are also injected into shear pump, shears 4min；
30 DEG C are cooled to through heat exchanger, normal pressure is depressurized to and is collected into stainless steel storage tank, while weight concentration is 50%
Second diaminourea ethyl sulfonic acid sodium water solution be also added in collecting tank；
Observation product characters find there are a large amount of undissolved White Flocculus, can not obtain the emulsion of stable uniform.
Comparative example 2
Formula：(mass percent)
Preparation method：
The butyl glycol ester diol of polyadipate 1,4 (Mn=2000), dimethylolpropionic acid, 1,4- butanediols are mixed and heated to
100 DEG C, octoate catalyst stannous is added, hydrogenation 4,4- '-diphenylmethane diisocyanates (HMDI) are warming up to 100 DEG C, both of the above
Respectively through gear wheel metering pump, flowmeter, by injecting rotating speed after mixing head be 250rpm, L/D=10, temperature is respectively 120 DEG C,
120 DEG C, 130 DEG C, 140 DEG C, 150 DEG C, 170 DEG C, 215 DEG C of double-screw reactor reaction, residence time 3min；
Be 100 DEG C through smelt gear pump implantation temperature, rotating speed be that while temperature is 100 DEG C, pressure in 1000rpm shear pumps
Power is 0.2Mpa, concentration is that the 2.3%wt methyl diethanolamine aqueous solution is also injected into shear pump, shears 5min；
Through heat exchanger be cooled to 50 DEG C, decompression be pooled in stainless steel storage tank, while weight concentration be 50% second two
Tarine sodium water solution is also added in collecting tank, stirs 30min, you can obtains aqueous polyurethane dispersion, solid content
For 40.0%wt；
The aqueous polyurethane dispersion stability is bad, stands two days later, a large amount of white precipitates occurs.
The physical property of aqueous polyurethane dispersion obtained by embodiment 1-7 is as follows：
| Embodiment | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 |
| Solid content | 41.5%wt | 40.0%wt | 43.1%wt | 50.0%wt | 30.0%wt | 45.1%wt | 50.6%wt |
| Emulsion viscosity (20 DEG C) | 400cp | 320cp | 500cp | 780cp | 250cp | 470cp | 820cp |
| 100% modulus | 3.5 | 4.0 | 1.8 | 1.2 | 2.1 | 2.8 | 2.1 |
| Tensile strength (Mpa) | 45 | 53 | 31 | 25 | 40 | 46 | 34 |
| Elongation at break % | 800 | 720 | 970 | 1140 | 900 | 860 | 970 |
Shown by the testing result of embodiment and contrast, because the double-screw reactor of the present invention has used special major diameter
Than, suitable temperature and time, reduce the generation of side reaction as far as possible again while ensureing that raw material reaction is complete, prepare
Obtained WTPUD emulsion storage stabilities are good, and stable performance is excellent, can be widely applied to synthetic leather, adhesive, coating, knit
The every field such as thing coating, finishing agent, particularly as synthetic leather resin, it can be applied to base fabric bed material resin, surface layer resin, glue
Tie the fields such as layer resin, intermediate layer resin, foaming layer resin.
Claims (10)
1. the preparation method of the solvent-free aqueous polyurethane dispersion of extrusion molding, it is characterised in that comprise the following steps：
(1) by polymer diatomic alcohol, diisocyanate, small molecule dihydric alcohol, the terminal hydroxy group Y-shaped pendant hydrophilic chain extension of low melting point two
Agent and catalyst, are preheated respectively, after being then input to mixer disperses mixing, are input in double-screw reactor and are reacted, obtain
Polyurethane melt；
(2) by the polyurethane melt of acquisition, it is continuously injected into shear pump, while the water with nertralizer is injected into shear pump,
And disperse in 120-200 DEG C of high temperature and 0.2-1.5Mpa down cuts；
(3) by step (2) obtained by product, decrease temperature and pressure, add rear chain extender, stirring reaction, obtain described solvent-free water-based
Dispersions of polyurethanes.
2. according to the method for claim 1, it is characterised 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.
3. according to the method for claim 1, it is characterised in that in described double-screw reactor, reaction temperature is divided into 7
Section, first paragraph are 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, the
Five sections are 150-170 DEG C, and the 6th section is 150-200 DEG C, and the 7th section is 205-230 DEG C, residence time of the material in twin-screw
For 0.5-3min.
4. according to the method for claim 1, it is characterised in that described polymer diatomic alcohol is polyether Glycols, polyester
Dihydric alcohol, the one or more in PCDL；
Described polyether Glycols use 2 terminal hydroxy groups, and number-average molecular weight is 200-10000 various structural polyether oligomers, is wrapped
Include and be not limited to：PolyTHF dihydric alcohol (PTMEG), Polyoxypropylene diol (PPG), polyoxyethylene glycol (PEG)
It is unlimited with one or more mixtures of PPOX ethylene oxide copolymerization dihydric alcohol (PEPG), mixed proportion；
Described polyester diol is to contain 2 oligomers of the terminal hydroxy group containing polyester construction, range of number-average molecular weight 200-
10000, including be not limited to：The butyl glycol ester diol of polyadipate -1,4 (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；
Described PCDL uses the oligomer containing 2 terminal hydroxy group carbonate-containing structures, range of number-average molecular weight
For 200-10000, exchanged and synthesized with binary alcohol esters by carbonic diester, including be not limited to：Poly- carbonic acid hexylene glycol esterdiol, poly- carbonic acid
The one or more of pentadiol ester glycol, polytetramethylene carbonate diol glycol, poly (propylene carbonate) glycol etc..
5. according to the method for claim 1, it is characterised in that it is different that described diisocyanate is selected from 4,4- diphenyl-methanes two
Cyanate (MDI), toluene di-isocyanate(TDI) (TDI), tolylene diisocyanate (XDI), 1,5- how diisocyanate
(NDI), PPDI (PPDI), hexamethylene diisocyanate (HDI), different Buddhist diisocyanates (IPDI),
Hydrogenate the mixture of one kind or any combination in 4,4- '-diphenylmethane diisocyanates (HMDI).
6. according to the method for claim 1, it is characterised in that described small molecule dihydric alcohol is selected from ethylene glycol, 1,2- third
Glycol, 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 isophthalic acids, one or more kinds of mixtures in ammediol, institute
One kind in dihydromethyl propionic acid and dimethylolpropionic acid of the terminal hydroxy group Y-shaped pendant hydrophilic chain extender of low melting point two stated or
Mixture, described catalyst are stannous octoate, dibutyl tin laurate, organic zinc, one kind in organo-bismuth or mixture.
7. according to the method for claim 1, it is characterised in that described rear chain extender is selected from ethylenediamine, propane diamine, fourth two
Amine, 1,6- hexamethylene diamines, one or more of second diaminourea ethyl sulfonic acid sodium, second diaminourea propanesulfonate.
8. according to the method for claim 1, it is characterised in that described solvent-free aqueous polyurethane dispersion, including such as
The component of lower mass percent：
9. aqueous polyurethane dispersion is prepared according to any one of claim 1~8 methods described.
10. the application of aqueous polyurethane dispersion according to claim 9, it is characterised in that applied to synthetic leather, gluing
Agent, coating, fabric coating, finishing agent, base fabric bed material resin, surface layer resin, tie layer resins, intermediate layer resin or foaming layer tree
Fat.
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| CN110066591A (en) * | 2019-05-21 | 2019-07-30 | 东莞市涂芭新材料有限公司 | A kind of aqueous skin sense woodwork coating and preparation method thereof |
| CN110591044A (en) * | 2019-08-28 | 2019-12-20 | 浙江华峰合成树脂有限公司 | High-physical-property low-fogging waterborne surface layer polyurethane resin and preparation method thereof |
| CN110606929A (en) * | 2019-09-18 | 2019-12-24 | 牡丹江师范学院 | Epoxy modified waterborne polyurethane emulsion convenient to store and transport, preparation method and storage method |
| CN110606930A (en) * | 2019-10-29 | 2019-12-24 | 兰州科天水性高分子材料有限公司 | Waterborne polyurethane resin and preparation method and application thereof |
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| CN112341590B (en) * | 2020-11-11 | 2021-09-10 | 中山大学 | Waterborne polyurethane and continuous preparation process thereof |
| CN113279265A (en) * | 2021-02-05 | 2021-08-20 | 山东天庆科技发展有限公司 | Water-based high-solid foaming resin for synthetic leather and preparation method thereof |
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