CN106188457A - Cross-linking type castor oil-base aqueous polyurethane emulsion and preparation method thereof in a kind of - Google Patents

Cross-linking type castor oil-base aqueous polyurethane emulsion and preparation method thereof in a kind of Download PDF

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Publication number
CN106188457A
CN106188457A CN201610554553.0A CN201610554553A CN106188457A CN 106188457 A CN106188457 A CN 106188457A CN 201610554553 A CN201610554553 A CN 201610554553A CN 106188457 A CN106188457 A CN 106188457A
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castor oil
aqueous polyurethane
base aqueous
linking type
interior cross
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Inventor
易英
张延飞
周宏伟
蒋文远
王丽
王洲洲
徐云超
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Wuhan University of Technology WUT
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Wuhan University of Technology WUT
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Abstract

The present invention relates to cross-linking type castor oil-base aqueous polyurethane emulsion and preparation method thereof in one.A kind of preparation method of interior cross-linking type castor oil-base aqueous polyurethane emulsion, it is characterized in that comprising the steps: that polymer polyatomic alcohol, Oleum Ricini, diisocyanate, catalyst and small molecule chain extender are added in reactor by (1) reacts, and obtains castor oil-base aqueous polyurethane oligomer；(2) react after adding hydrophilic chain extender and multi-functional internal crosslinker in above-mentioned castor oil-base aqueous polyurethane oligomer, add butanone regulation viscosity to 16.5mPa s, obtain interior cross-linking type castor oil-base aqueous polyurethane；(3) in above-mentioned interior cross-linking type castor oil-base aqueous polyurethane, add nertralizer, be added thereto to deionized water after reaction and carry out high speed shear emulsifying, after steaming butanone, obtain interior cross-linking type castor oil-base aqueous polyurethane emulsion.The method technological process is simple, substantially increase cross-linking efficiency, and product mechanical property is strong.

Description

Cross-linking type castor oil-base aqueous polyurethane emulsion and preparation method thereof in a kind of
Technical field
The present invention relates to cross-linking type castor oil-base aqueous polyurethane emulsion and preparation method thereof in one, belong to fine high score Sub-material and preparation field thereof.
Background technology
Aqueous polyurethane (WPU) is the one in high molecular synthetic material, the resistance to high/low warm nature of its film, wearability, resistance to The performance such as corrosivity and pliability is more excellent, is mainly used in light textile, leather processing, coating, timber processing, building materials, papermaking and glue The industries such as stick, it is using water as disperse medium, has the advantages such as nontoxic, environmental protection and not combustion.
Aqueous polyurethane is affected by self structure and disperse medium, and in film forming procedure, surface spreading is poor, drying time Long, film forming is compound with base material poor, and mechanical property is relatively low, and hardness is low, poor water resistance and hygroscopic.Accordingly, it would be desirable to it is changed Property, in the study on the modification of aqueous polyurethane, increasing its crosslink density is one of effective means of enhancing product performance, by crosslinking Modification can make the molecular weight of WPU increase, and physical and chemical performance is improved.WPU is carried out cross-linked modification method and mainly includes interior friendship Connection method and external crosslinking method, interior cross-linking method refers to introduce cross-linking agent during WPU is polymerized, and makes WPU macromole produce crosslinking. Traditional low degree of functionality little molecule cross-linking agents activity is relatively low, and cross-linking efficiency is not ideal enough.
Utilize trishydroxymethylaminomethane (THAM) to carry out cross-linking modified, be different from polyhydric glycerol and season penta 4 Alcohol, containing 3-OH and 1 activity-NH in THAM molecular structure2.The reactivity of amino and-NCO be significantly larger than-OH with- The reactivity of NCO, the urea bond polarity of generation is stronger than amino-formate bond, causes molecule hydrogen bond action to strengthen, the most just Property segment the most easily assemble formation hard section phase, microphase separation degree strengthens, so that polyurethane heat stability and hot strength increase.
Chinese patent 201210449429.X is prepared for end hydroxy butadiene by the method that multi-epoxy is cross-linking modified and changes Property aqueous polyurethane emulsion, patent US552299 uses JEFFAMNEJ-403 (trimethylolpropane and polycyclic oxypropylene triamine Product) be prepared for aqueous polyurethane dispersing liquid.Patent US5922805 discloses a kind of with polyether triol as three-functionality-degree Monomer prepares the method for aqueous polyurethane emulsion.Patent 201310114832.1 is prepared by the method that polyfunctionality is cross-linking modified A kind of polyfunctionality polyurethane acrylic ester water UV resin, first it prepare carboxylic base polyurethane prepolymer for use as, then In above-mentioned performed polymer, drip (methyl) crylic acid hydroxy ester dissolved with polymerization inhibitor, after reaction a period of time, be added thereto to little point Sub-monohydric alcohol blocks, and obtains the polyurethane acrylate prepolymer of unsaturated acrylate ended, finally to above-mentioned system Middle addition tertiary amine carries out into emulsifying salt and obtains polyfunctionality polyurethane acrylic ester water UV resin with deionized water.
Summary of the invention
It is an object of the invention to provide cross-linking type castor oil-base aqueous polyurethane emulsion and preparation method thereof, the party in one Method technological process is simple, substantially increase cross-linking efficiency.
For achieving the above object, the technical solution used in the present invention is, a kind of interior cross-linking type poly-ammonia of castor oil-base aqueous Ester emulsion, it is characterised in that obtained by following steps:
(1) polymer polyatomic alcohol, Oleum Ricini, diisocyanate, catalyst and small molecule chain extender are added in reactor React, obtain castor oil-base aqueous polyurethane oligomer；
(2) in above-mentioned castor oil-base aqueous polyurethane oligomer, hydrophilic chain extender and multi-functional interior crosslinking are added React after agent, add butanone regulation viscosity to 16.5mPa s, obtain interior cross-linking type castor oil-base aqueous polyurethane；
(3) in above-mentioned interior cross-linking type castor oil-base aqueous polyurethane add nertralizer, be added thereto to after reaction from Sub-water carries out high speed shear emulsifying, obtains interior cross-linking type castor oil-base aqueous polyurethane emulsion after steaming butanone.
The preparation method of a kind of interior cross-linking type castor oil-base aqueous polyurethane emulsion, it is characterised in that comprise the steps:
(1) polymer polyatomic alcohol, Oleum Ricini, diisocyanate, catalyst and small molecule chain extender are added in reactor React, obtain castor oil-base aqueous polyurethane oligomer；
(2) in above-mentioned castor oil-base aqueous polyurethane oligomer (or claiming castor oil-base aqueous polyurethane), hydrophilic is added React after chain extender, add butanone regulation viscosity to 16.0mPa s-30.8mPa s, obtain interior cross-linking type castor oil-base water Property polyurethane；
(3) in above-mentioned interior cross-linking type castor oil-base aqueous polyurethane add nertralizer, be added thereto to after reaction from Sub-water carries out high speed shear emulsifying, obtains interior cross-linking type castor oil-base aqueous polyurethane emulsion after steaming butanone.
In above-mentioned preparation method, the described reaction of step (1) needs to carry out Oleum Ricini and polymer polyatomic alcohol except water in advance Process (reduced vacuum removes water 1.5h at 120 DEG C), course of reaction needs inert gas shielding (such as nitrogen or argon).
Step (1) described reaction temperature is 60 DEG C～80 DEG C, concretely 70 DEG C or 80 DEG C；Response time be 2.0h～ 3.5h, concretely 2.0h or 3.0h.
In step (1), polymer polyatomic alcohol, Oleum Ricini, diisocyanate, catalyst, the mass ratio of small molecule chain extender For 12g-15g:5g-12g:13.7g-17.9g:0.012g-0.016g:1.4g-2.4g.
Described polymer polyatomic alcohol is 1 with the amount ratio of the material of diisocyanate: (1.5～7.5), concretely 1: 1.5, 1: 2.5,1: 3.5,1: 4,1: 5,1: 6 and 1: 7.
Step adds phosphoric acid in (1), is that 12g:0.016g-0.0213g (phosphorates by the mass ratio of polymer polyatomic alcohol with phosphoric acid Acid is to reduce side reaction, needs to add), add phosphoric acid.
In above-mentioned preparation method, the number-average molecular weight of step (1) described polymer polyatomic alcohol be 800～4000 (such as 800, 1600,2000 or 2600), described polymer polyatomic alcohol be in PEPA and/or polyether polyol one or more by Arbitrarily (described any proportioning refers to: the lower limit value of mass percent shared by raw material is more than 0%, upper limit value in the mixing of proportioning Less than 100%, the most identical)；Described PEPA is polyhydroxyalkanoate, poly-epsilon-caprolactone, polyadipate ethylene glycol One or more in ester, PCDL are by the mixing of any proportioning, and described polyether polyol is PTMG A kind of in glycol, fatty alcohol-polyoxyethylene ether or two kinds are by the mixing of any proportioning.
Described diisocyanate be in aliphatic diisocyanate and/or aromatic diisocyanate one or more by The arbitrarily mixing of proportioning；Described aliphatic diisocyanate is dicyclohexyl methyl hydride-4,4-diisocyanate, 2,2,4-trimethyls One or more in hexamethylene diisocyanate, isophorone diisocyanate are by the mixing of any proportioning, and described aromatic series two is different Cyanate be 2,4 toluene diisocyanate, diphenylmethane diisocyanate fat, 2, one in 6-toluene di-isocyanate(TDI) or Several mixing by any proportioning.
In above-mentioned preparation method, catalyst described in step (1) is dibutyl tin dilaurate (that is, tin dilaurate two fourth Ji Xi), the one in stannous octoate or triethylene diamine；Described small molecule chain extender is dihydromethyl propionic acid or dihydroxymethyl fourth One in acid.
In above-mentioned preparation method, in step (2), by the mass ratio of polymer polyatomic alcohol, hydrophilic chain extender be " 12g: 1.3g-2.4g, chooses hydrophilic chain extender.
In above-mentioned preparation method, in step (2), it is additionally added multi-functional internal crosslinker, by polymer polyatomic alcohol, many officials The mass ratio of the internal crosslinker that can roll into a ball is that " 12g:0.24g-0.72g chooses multi-functional internal crosslinker.
In above-mentioned preparation method, (hydrophilic chain extender accounts for the total matter of performed polymer to the mass fraction of step (2) described hydrophilic chain extender The ratio of amount) it is 3.0%～6.0%, concretely 3.0%, 3.5%, 4.0%, 5.0% or 6.0%；Hand in described polyfunctionality The mass fraction ratio of performed polymer gross mass (hydrophilic chain extender account for) of connection agent is 0%～2.0%, concretely 0.3%, 0.8%, 1.2% or 1.6%.
Step (2) described hydrophilic chain extender is BDO, dihydromethyl propionic acid, 1,2-PD-3-sodium sulfonate, gathers One or more in ethylene oxide glycol are by the mixing of any proportioning；Described polyfunctional group internal crosslinker is trihydroxy methyl amino Methane (THAM).
In above-mentioned preparation method, step (2) described reaction temperature is 70 DEG C～90 DEG C (concretely 70 DEG C, 80 DEG C or 85 ℃)；Response time is 1.0h～2.0h (concretely 1.0h, 1.5h or 2.0h).
In step (3), it is 12g:1.5g-1.81g by polymer polyatomic alcohol, nertralizer, the mass ratio of deionized water: 130g, chooses nertralizer and deionized water.
In above-mentioned preparation method, step (3) described nertralizer is triethylamine.
In above-mentioned preparation method, it is 1.0h～2.0h that step (3) add deionized water to carry out time of high speed shear emulsifying (concretely 1.0h or 1.5h).
The present invention provide said method prepare cross-linking type castor oil-base aqueous polyurethane emulsion (or claim THAM tetra- Crosslinkable functionality's modified castor oil base water polyurethane emulsion)；The solid content of emulsion is 25%～40%, concretely 25%, 30% or 35%.
The emulsion of the present invention can be applicable in water paint and adhesive.
The invention have the advantages that
(1) THAM of four-functional group is used to be greatly improved cross-linking efficiency as cross-linking agent.
(2) use containing-NH2With the trishydroxymethylaminomethane (THAM) of-OH as chain extender, simplify technique stream Journey, reduces highly energy-consuming and the complex steps of the reaction of alcoholysis Oleum Ricini simultaneously.
(3) promoting the microphase-separated of WPU hard segment, the performance making product is more excellent, and mechanical property is strong, and (stretching is strong Degree, elongation at break are high).
Detailed description of the invention
Below in conjunction with embodiment, the present invention done further detailed description, but embodiments of the present invention are not limited to this.
Experimental technique used in following embodiment if no special instructions, is conventional method.
Material used in following embodiment, reagent etc. if no special instructions, the most commercially obtain.
Embodiment 1, the preparation of interior cross-linking type castor oil-base aqueous polyurethane emulsion
PTMG (PTMG-2000) 12g, Oleum Ricini (CO) 12g are added in reaction response device (wherein, The mass ratio of PTMG-2000 and CO is 1: 1), at 120 DEG C, reduced vacuum removes water 1.5h, adds when system temperature is down to 70 DEG C Entering isophorone diisocyanate (IPDI) 17.6g and 0.0192g phosphoric acid, R value is 1.2, in 80 DEG C under drying nitrogen is protected Reaction 2h；System is suitably lowered the temperature (such as: be cooled to 75 DEG C), add dihydromethyl propionic acid (DMPA, small molecule chain extender) 2.2g With 0.0144g dibutyl tin laurate (DBTDL, catalyst), continue at reaction about 1.5h under 80 DEG C of constant temperature.
It is warmed up to 85 DEG C, adds BDO (BDO) 2.2g, react certain time, when-NCO base content reaches to set Stopping after value, the present embodiment setting value is 7.71% (this mass fraction is drawn by acetone-di-n-butylamine titration measuring), adds 4.6g butanone (MEK) regulation viscosity (viscosity 30.8mPa s).
When temperature is down to 35～45 DEG C, adds 1.5g triethylamine (TEA) and neutralize reaction 0.5h, add 130g deionization Water, high speed shear emulsifying 1h, after decompression distillation removing butanone (MEK), obtain interior cross-linking type castor oil-base aqueous polyurethane emulsion (or claim: THAM tetra-crosslinkable functionality's modified version castor oil-base aqueous polyurethane emulsion), solid content is 25% (quality, following phase With).
By products obtained therefrom plastic film mulch, the hot strength of gained film is 9.56MPa, and elongation at break is 154.81%.
Embodiment 2, the preparation of interior cross-linking type castor oil-base aqueous polyurethane emulsion
PCDL (PCDL-2000) 12g, Oleum Ricini (CO) 12g are added in reaction response device (wherein, The mass ratio of PCDL-2000 and CO is 1: 1), at 120 DEG C, reduced vacuum removes water 1.5h, adds when system temperature is down to 70 DEG C Entering isophorone diisocyanate (IPDI) 17.7g and 0.016g phosphoric acid, R value is 1.2, anti-in 85 DEG C under drying nitrogen is protected Answer 2h.System is suitably lowered the temperature (such as: be cooled to 75 DEG C), add dihydromethyl propionic acid (DMPA) 2.4g and 0.012g tin dilaurate Dibutyl tin (DBTDL), continues at reaction about 1.5h under 80 DEG C of constant temperature.
It is warmed up to 85 DEG C, adds BDO (BDO) 1.9g and trishydroxymethylaminomethane (THAM) 0.24g and (account for total The 0.5% of performed polymer quality), react certain time, add 4.0g butanone (MEK) regulation viscosity (viscosity 30.2mPa s).
When temperature is down to 35～45 DEG C, adds 1.5g triethylamine (TEA) and neutralize reaction 0.5h, add 130g deionization Water, high speed shear emulsifying 1h, after decompression is distilled off butanone (MEK), obtain THAM tetra-crosslinkable functionality's modified version castor oil-base Aqueous polyurethane emulsion, solid content is 25%.
By products obtained therefrom plastic film mulch, the hot strength of gained film is 12.78MPa, and elongation at break is 124.24%.
Embodiment 3, the preparation of interior cross-linking type castor oil-base aqueous polyurethane emulsion
PCDL (PCDL-2000) 12g, Oleum Ricini (CO) 12g are added in reaction response device (wherein, The mass ratio of PCDL-2000 and CO is 1: 1), at 120 DEG C, reduced vacuum removes water 1.5h, adds when system temperature is down to 70 DEG C Entering isophorone diisocyanate (IPDI) 17.7g and 0.0192g phosphoric acid, R value is 1.2, in 80 DEG C under drying nitrogen is protected Reaction 2h.System is suitably lowered the temperature (such as: be cooled to 75 DEG C), add dihydromethyl propionic acid (DMPA) 2.4g and 0.0144g February Dilaurylate (DBTDL), continues at reaction about 1.5h under 80 DEG C of constant temperature.
It is warmed up to 85 DEG C, adds BDO (BDO) 1.7g and trishydroxymethylaminomethane (THAM) 0.36g and (account for total The 0.75% of performed polymer quality), react certain time, add 3.5g butanone (MEK) regulation viscosity (viscosity 28.7mPa s).
When temperature is down to 35～45 DEG C, adds 1.5g triethylamine (TEA) and neutralize reaction 0.5h, add 130g deionization Water, high speed shear emulsifying 1.5h, after decompression is distilled off MEK, obtain THAM tetra-crosslinkable functionality's modified version castor oil-base aqueous Polyaminoester emulsion, solid content is 30%.
By products obtained therefrom plastic film mulch, the hot strength of gained film is 13.17MPa, and elongation at break is 122.79%.
Embodiment 4, the preparation of interior cross-linking type castor oil-base aqueous polyurethane emulsion
PCDL (PCDL-2000) 12g, Oleum Ricini (CO) 12g are added in reaction response device (wherein, The mass ratio of PCDL-2000 and CO is 1: 1), at 120 DEG C, reduced vacuum removes water 1.5h, adds when system temperature is down to 75 DEG C Entering isophorone diisocyanate (IPDI) 17.8g and 0.0192g phosphoric acid, R value is 1.2, in 85 DEG C under drying nitrogen is protected Reaction 2h.System is suitably lowered the temperature, adds dihydromethyl propionic acid (DMPA) 2.4g and 0.0144g dibutyl tin laurate (DBTDL) reaction about 1.5h under 85 DEG C of constant temperature, is continued at.
It is warmed up to 85 DEG C, adds BDO (BDO) 1.56g and trishydroxymethylaminomethane (THAM) 0.48g and (account for total The 1% of performed polymer quality), react certain time, add 3.0g butanone (MEK) regulation viscosity (viscosity 21.4mPa s).
When temperature is down to 35～45 DEG C, adds 1.5g triethylamine (TEA) and neutralize reaction 0.5h, add 130g deionization Water, high speed shear emulsifying 1.5h, after decompression is distilled off MEK, obtain THAM tetra-crosslinkable functionality's modified version castor oil-base aqueous Polyaminoester emulsion, solid content is 30%.
By products obtained therefrom plastic film mulch, the hot strength of gained film is 14.32MPa, and elongation at break is 96.13%.
Embodiment 5, the preparation of interior cross-linking type castor oil-base aqueous polyurethane emulsion
PCDL (PCDL-2000) 12g, Oleum Ricini (CO) 12g are added in reaction response device (wherein, The mass ratio of PCDL-2000 and CO is 1: 1), at 120 DEG C, reduced vacuum removes water 1.5h, adds when system temperature is down to 75 DEG C Entering isophorone diisocyanate (IPDI) 17.8g and 0.0213g phosphoric acid, R value is 1.2, in 80 DEG C under drying nitrogen is protected Reaction 2h.System is suitably lowered the temperature, adds dihydromethyl propionic acid (DMPA) 2.4g and 0.016g dibutyl tin laurate (DBTDL) reaction about 1.5h under 80 DEG C of constant temperature, is continued at.
It is warmed up to 85 DEG C, adds BDO (BDO) 1.4g and trishydroxymethylaminomethane (THAM) 0.6g and (account for total pre- The 1.25% of aggressiveness quality), react certain time, add 2.7g butanone (MEK) regulation viscosity (viscosity 16.5mPa s).
When temperature is down to 35～45 DEG C, adds 1.5g triethylamine (TEA) and neutralize reaction 0.5h, add 130g deionization Water, high speed shear emulsifying 1h, after decompression is distilled off MEK, obtains THAM tetra-crosslinkable functionality's modified version castor oil-base aqueous and gather Urethane emulsion, solid content is 35%.
By products obtained therefrom plastic film mulch, the hot strength of gained film is 16.31MPa, and elongation at break is 92.09%.
Embodiment 6, the preparation of interior cross-linking type castor oil-base aqueous polyurethane emulsion
PTMG (PTMG-2000) 15g, Oleum Ricini (CO) 5g are added in reaction response device (wherein, The mass ratio of PTMG-2000 and CO is 3: 1), at 120 DEG C, reduced vacuum removes water 1.5h, adds when system temperature is down to 70 DEG C Entering isophorone diisocyanate (IPDI) 13.7g and 0.0192g phosphoric acid, R value is 1.3, in 80 DEG C under drying nitrogen is protected Reaction 2h.System is suitably lowered the temperature, adds dihydromethyl propionic acid (DMPA) 2.4g and 0.0144g dibutyl tin laurate (DBTDL) reaction about 1.5h under 80 DEG C of constant temperature, is continued at.
Being warmed up to 85 DEG C, add BDO (BDO) 1.3g, reaction certain time, (-NCO base content reached setting value Rear stopping), add 2.5g butanone (MEK) regulation viscosity (viscosity 16.4mPa s).
When temperature is down to 35～45 DEG C, adds 1.8g triethylamine (TEA) and neutralize reaction 0.5h, add 130g deionization Water, high speed shear emulsifying 1.5h, after decompression distillation removing MEK, obtain THAM tetra-crosslinkable functionality's modified version castor oil-base aqueous Polyaminoester emulsion, solid content is 25%.
By products obtained therefrom plastic film mulch, the hot strength of gained film is 15.42MPa, and elongation at break is 94.23%.
Embodiment 7, the preparation of interior cross-linking type castor oil-base aqueous polyurethane emulsion
PCDL (PCDL-2000) 12g, Oleum Ricini (CO) 12g are added in reaction response device (wherein, The mass ratio of PCDL-2000 and CO is 1: 1), at 120 DEG C, reduced vacuum removes water 1.5h, adds when system temperature is down to 75 DEG C Entering isophorone diisocyanate (IPDI) 17.9g and 0.0192g phosphoric acid, R value is 1.2, in 80 DEG C under drying nitrogen is protected Reaction 2h.System is suitably lowered the temperature, adds dihydromethyl propionic acid (DMPA) 2.4g and 0.0144g dibutyl tin laurate (DBTDL) reaction about 1.5h under 80 DEG C of constant temperature, is continued at.
It is warmed up to 85 DEG C, adds BDO (BDO) 1.2g and trishydroxymethylaminomethane (THAM) 0.72g and (account for total The 1.5% of performed polymer quality), react certain time, add 2.0g butanone (MEK) regulation viscosity (viscosity 16.0mPa s).
When temperature is down to 35～45 DEG C, adds 1.5g triethylamine (TEA) and neutralize reaction 0.5h, add 130g deionization Water, high speed shear emulsifying 1h, after decompression is distilled off MEK, obtains THAM tetra-crosslinkable functionality's modified version castor oil-base aqueous and gather Urethane emulsion, solid content is 30%.
By products obtained therefrom plastic film mulch, the hot strength of gained film is 10.30MPa, and elongation at break is 37.96%.
Each raw material cited by the present invention, and the bound of each raw material of the present invention, interval value, and technological parameter The bound of (such as temperature, time etc.), interval value can realize the present invention, embodiment numerous to list herein.

Claims (10)

1. cross-linking type castor oil-base aqueous polyurethane emulsion in a kind, it is characterised in that obtained by following steps:
(1) will polymer polyatomic alcohol, Oleum Ricini, diisocyanate, catalyst and small molecule chain extender addition reactor be carried out Reaction, obtains castor oil-base aqueous polyurethane oligomer；
(2) react after adding hydrophilic chain extender in above-mentioned castor oil-base aqueous polyurethane oligomer, add butanone regulation Viscosity, to 16.0mPa s-30.8mPa s, obtains interior cross-linking type castor oil-base aqueous polyurethane；
(3) in above-mentioned interior cross-linking type castor oil-base aqueous polyurethane, add nertralizer, after reaction, be added thereto to deionized water Carry out high speed shear emulsifying, after steaming butanone, obtain interior cross-linking type castor oil-base aqueous polyurethane emulsion.
2. the preparation method of cross-linking type castor oil-base aqueous polyurethane emulsion in a kind, it is characterised in that comprise the steps:
(1) will polymer polyatomic alcohol, Oleum Ricini, diisocyanate, catalyst and small molecule chain extender addition reactor be carried out Reaction, obtains castor oil-base aqueous polyurethane oligomer；
(2) after adding hydrophilic chain extender and multi-functional internal crosslinker in above-mentioned castor oil-base aqueous polyurethane oligomer React, add butanone regulation viscosity to 16.5mPa s, obtain interior cross-linking type castor oil-base aqueous polyurethane；
(3) in above-mentioned interior cross-linking type castor oil-base aqueous polyurethane, add nertralizer, after reaction, be added thereto to deionized water Carry out emulsification pretreatment, after steaming butanone, obtain interior cross-linking type castor oil-base aqueous polyurethane emulsion.
The preparation method of a kind of interior cross-linking type castor oil-base aqueous polyurethane emulsion the most according to claim 2, its feature It is: the described reaction of step (1) needs to carry out Oleum Ricini and polymer polyatomic alcohol in advance except water processes, and at 120 DEG C, decompression is true Empty except water 1.5h；Course of reaction needs inert gas shielding.
The preparation method of a kind of interior cross-linking type castor oil-base aqueous polyurethane emulsion the most according to claim 2, its feature It is: step (1) described reaction temperature is 60 DEG C～80 DEG C；Response time is 2.0h～3.5h.
The preparation method of a kind of interior cross-linking type castor oil-base aqueous polyurethane emulsion the most according to claim 2, its feature Being: in step (1), polymer polyatomic alcohol, Oleum Ricini, diisocyanate, catalyst, the mass ratio of small molecule chain extender are 12g-15g:5g-12g:13.7g-17.9g:0.012g-0.016g:1.4g-2.4g.
The preparation method of a kind of interior cross-linking type castor oil-base aqueous polyurethane emulsion the most according to claim 2, its feature It is: step adds phosphoric acid in (1), is 12g:0.016g-0.0213g by the mass ratio of polymer polyatomic alcohol Yu phosphoric acid.
The preparation method of a kind of interior cross-linking type castor oil-base aqueous polyurethane emulsion the most according to claim 2, its feature Being: the number-average molecular weight of step (1) described polymer polyatomic alcohol is 800～4000, described polymer polyatomic alcohol is that polyester is many One or more in unit's alcohol and/or polyether polyol are by the mixing of any proportioning；Described PEPA is poly-hydroxy aliphatic One or more in acid esters, poly-epsilon-caprolactone, 10PE27, PCDL mixing by any proportioning Closing, described polyether polyol is that the one in PTMG, fatty alcohol-polyoxyethylene ether or two kinds are by any proportioning Mixing；
Described diisocyanate is that one or more in aliphatic diisocyanate and/or aromatic diisocyanate are by arbitrarily The mixing of proportioning；Described aliphatic diisocyanate is dicyclohexyl methyl hydride-4,4-diisocyanate, 2,2,4-trimethyls oneself two One or more in isocyanates, isophorone diisocyanate are by the mixing of any proportioning, described aromatic diisocyanates Ester be 2,4 toluene diisocyanate, diphenylmethane diisocyanate fat, 2, one or more in 6-toluene di-isocyanate(TDI) Mixing by any proportioning；
Described in step (1), catalyst is the one in dibutyl tin dilaurate, stannous octoate or triethylene diamine；
Described small molecule chain extender is the one in dihydromethyl propionic acid or dimethylolpropionic acid.
The preparation method of a kind of interior cross-linking type castor oil-base aqueous polyurethane emulsion the most according to claim 2, its feature It is: in step (2), is 12g:1.3g-2.4g by the mass ratio of polymer polyatomic alcohol, hydrophilic chain extender, chooses hydrophilic Chain extender；
In step (2), it is additionally added multi-functional internal crosslinker, by polymer polyatomic alcohol, the matter of multi-functional internal crosslinker Amount ratio is 12g:0.24g-0.72g, chooses multi-functional internal crosslinker.
Step (2) described hydrophilic chain extender is BDO, dihydromethyl propionic acid, 1,2-PD-3-sodium sulfonate, polyoxygenated One or more in ethylene glycol are by the mixing of any proportioning；
Step (2) described polyfunctional group internal crosslinker is trishydroxymethylaminomethane (THAM).
The preparation method of a kind of interior cross-linking type castor oil-base aqueous polyurethane emulsion the most according to claim 2, its feature It is: step (2) described reaction temperature is 70 DEG C～90 DEG C；Response time is 1.0h～2.0h.
The preparation method of a kind of interior cross-linking type castor oil-base aqueous polyurethane emulsion the most according to claim 2, its feature It is: in step (3), is 12g:1.5g-1.81g:130g by polymer polyatomic alcohol, nertralizer, the mass ratio of deionized water, choosing Take nertralizer and deionized water；
Step (3) described nertralizer is triethylamine；
It is 1.0h～2.0h that step (3) add deionized water to carry out time of emulsification pretreatment.
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CN109651588B (en) * 2018-11-21 2021-09-07 万华化学集团股份有限公司 Castor oil modified cationic self-crosslinking polyurethane polyurea aqueous dispersion, preparation method and application
CN109651588A (en) * 2018-11-21 2019-04-19 万华化学集团股份有限公司 Castor oil modified cation self-crosslinkable polyurethane polyurea water dispersion and preparation method and application
CN109853253A (en) * 2019-02-19 2019-06-07 东莞市喜宝体育用品科技有限公司 A kind of TPU flies to knit vamp
CN109853253B (en) * 2019-02-19 2021-03-16 东莞市喜宝体育用品科技有限公司 TPU flies to knit vamp
CN111662634B (en) * 2020-06-24 2021-12-07 广东达尔新型材料有限公司 Thin-coating type water-based anti-static polyurethane mortar floor coating and preparation method thereof
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CN112876974A (en) * 2021-01-18 2021-06-01 中车青岛四方机车车辆股份有限公司 High-adhesion waterborne polyurethane coating and preparation method and application thereof
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CN112961313A (en) * 2021-03-09 2021-06-15 武汉双虎涂料有限公司 Basic emulsion, preparation method thereof and application thereof in preparation of resin coating
CN112898890A (en) * 2021-03-22 2021-06-04 辽阳康达塑胶树脂有限公司 Preparation process and production line of anticorrosive material
CN115897264A (en) * 2022-12-06 2023-04-04 现代纺织技术创新中心(鉴湖实验室) Preparation method and application of modified bio-based photocuring self-emulsifying waterborne polyurethane composite pigment ink for inkjet printing
CN115897264B (en) * 2022-12-06 2024-04-30 现代纺织技术创新中心(鉴湖实验室) Preparation method and application of modified bio-based photo-curing self-emulsifying aqueous polyurethane composite pigment ink for inkjet printing
CN116253987A (en) * 2023-01-31 2023-06-13 广东金发科技有限公司 Aqueous polyurethane emulsion, biodegradable glove and preparation method and application thereof

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