CN109942781A - A kind of UV solidification castor oil-base aqueous polyurethane dispersion and the preparation method and application thereof - Google Patents
A kind of UV solidification castor oil-base aqueous polyurethane dispersion and the preparation method and application thereof Download PDFInfo
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Abstract
The present invention provides a kind of UV solidification castor oil-base aqueous polyurethane dispersion and the preparation method and application thereof, belong to aqueous polyurethane dispersion technical field.The present invention is fed intake 2,2- dihydromethyl propionic acid prior to castor oil using the synthesis technology that feeds intake step by step, and linear condensation polymerization occurs with diisocyanate;Castor oil is added into system again, three-dimensional polycondensation has occurred in system at this time;This addition sequence is beneficial to form stable water-borne dispersions when later period emulsification.The molar ratio of-OH and-NCO is 0.91 in entire formula, improves the partial size and dispersion moisture evaporation speed at room temperature of dispersion.The addition of pentaerythritol triacrylate, make to contain active terminal double bond in product molecule, under suitable photoinitiator and UV irradiation, double bond is reacted rapidly, the crosslink density of castor oil-base waterborne polyurethane resin greatly improved, and then improve mechanical property and water resistance that UV solidifies castor oil-base aqueous polyurethane dispersion.
Description
Technical field
The present invention relates to aqueous polyurethane dispersion technical fields more particularly to a kind of UV to solidify the aqueous poly- ammonia of castor oil-base
Ester dispersion and the preparation method and application thereof.
Background technique
Recently as fossil resources it is increasingly exhausted and therefrom caused by Heavy environmental pollution, people turn to sight
Inexhaustible, nexhaustible, biodegradable, environment amenable natural reproducible resource.Castor oil is a kind of reproducible
Natural inedible materials, the hydroxyl containing there are many can replace conventional polyol, directly form figure with di-isocyanate reaction
Highly -branched polyurethane molecular, this makes material not only good toughness, easily biological-degradable and biocompatibility, also with higher
Intensity, hardness and good water resistance.
But in aqueous polyurethane system, excessively high castor-oil plant oil content will cause slow curing rate, poor water resistance and power
The problem for learning performance difference, is unfavorable for the extensive use of material.
Summary of the invention
In view of this, the purpose of the present invention is to provide a kind of UV solidification castor oil-base aqueous polyurethane dispersion and its systems
Preparation Method and application have excellent although castor oil of the dispersion made from preparation method provided by the invention containing high-content
Different curing rate, water resistance and mechanical property.
In order to achieve the above-mentioned object of the invention, the present invention the following technical schemes are provided:
The present invention provides a kind of UV preparation method for solidifying castor oil-base aqueous polyurethane dispersion, comprising the following steps:
(1) by 2,2- dihydromethyl propionic acid, diisocyanate, glycol chain extender, dibutyl tin dilaurate and first
Butanone mixing, after carrying out first stage addition reaction;Castor oil and the second butanone is added, carries out second stage addition reaction;Add
Enter pentaerythritol triacrylate, continues phase III addition reaction, obtain reaction solution;
(2) alkali is added in the reaction solution, carries out neutralization reaction, obtains performed polymer;
(3) by the performed polymer and water mixing and emulsifying, and butanone is removed, obtains castor oil-base aqueous polyurethane;
(4) the castor oil-base aqueous polyurethane is mixed with photoinitiator, it is aqueous obtains the UV solidification castor oil-base
Dispersions of polyurethanes;
The molar ratio of-OH and-NCO is 0.91 in W-response body.
Preferably, the diisocyanate includes that isophorone diisocyanate, isophorone diisocyanate and six are sub-
One of methyl diisocyanate mixture, isophorone diisocyanate and '-diphenylmethane diisocyanate mixture.
Preferably, the glycol chain extender includes in 1,4-butanediol, ethylene glycol, 1,2-PD and 1,3-PD
One or more.
Preferably, the quality of the castor oil is 2,2- dihydromethyl propionic acid, diisocyanate, glycol chain extender, castor
The 50% of sesame oil, pentaerythritol triacrylate and alkali gross mass.
Preferably, the quality of 2, the 2- dihydromethyl propionic acid is 2,2- dihydromethyl propionic acid, diisocyanate, dihydric alcohol
Chain extender, castor oil, pentaerythritol triacrylate and alkali gross mass 5~7%.
Preferably, the alkali and 2, the molar ratio of 2- dihydromethyl propionic acid are 1:1.
Preferably, the gross mass of first butanone and the second butanone is 2- dihydromethyl propionic acid, diisocyanate, binary
Alcohol chain extender, castor oil, pentaerythritol triacrylate and alkali gross mass 150%.
Preferably, the photoinitiator includes DAROCURE TPO, 2100 IRGACURE or IRGACURE 819.
The UV solidification castor oil-base being prepared the present invention also provides preparation method described in above-mentioned technical proposal is aqueous poly-
Urethane dispersion, the theoretical solid content that the UV solidifies castor oil-base aqueous polyurethane dispersion is 25%.
The present invention also provides the solidification castor oil-base aqueous polyurethane dispersion of UV described in above-mentioned technical proposal to lead in coating
Application in domain.
The present invention provides a kind of UV preparation method for solidifying castor oil-base aqueous polyurethane dispersion, comprising the following steps:
(1) 2,2- dihydromethyl propionic acid, diisocyanate, glycol chain extender, dibutyl tin dilaurate and the first butanone are mixed,
After carrying out first stage addition reaction;Castor oil and the second butanone is added, carries out second stage addition reaction;Pentaerythrite is added
Triacrylate continues phase III addition reaction, obtains reaction solution;(2) alkali is added in the reaction solution, in progress
And reaction, obtain performed polymer;(3) by the performed polymer and water mixing and emulsifying, and butanone is removed, obtains the aqueous poly- ammonia of castor oil-base
Ester;(4) the castor oil-base aqueous polyurethane is mixed with photoinitiator, obtains the UV solidification castor oil-base aqueous polyurethane
Dispersion;The molar ratio of-OH and-NCO is 0.91 in W-response body.
The present invention is using the synthesis technology that feeds intake step by step, and by hydrophily dihydric alcohol 2,2- dihydromethyl propionic acid (DMPA) is prior to castor
Sesame oil feeds intake, and linear condensation polymerization occurs with diisocyanate, is introduced into polyurethane molecular;Linear polycondensation carries out a period of time
Afterwards, then into system castor oil is added, since the hydroxy functionality of castor oil is greater than 2, three-dimensional polycondensation, shape is had occurred in system at this time
At the figure polyurethane molecular of highly branched crosslinking;Since hydrophily DMPA monomer has had been introduced into poly- ammonia in previous stage
In ester molecular structure, thus hydrophilic radical can be uniformly distributed in such highly cross-linked figure molecule, after being beneficial to
Phase forms stable water-borne dispersions when emulsifying.The molar ratio of entire formula-OH and-NCO is 0.91, makes entire reaction process
In-NCO be all it is slight excess of, make-the OH contained in system react to form-HNCOO- with-NCO completely;Simultaneously as-NCO
Slightly excessive, remaining-NCO can react in emulsion process with water generates slightly solubility urea groups, and the presence of one side urea groups improves
The partial size of dispersion, another aspect urea groups improve the mechanical property of dispersion by forming hydrogen bond crosslinks network, also improve
Dispersion moisture evaporation speed at room temperature.In addition, using pentaerythritol triacrylate as end-capping reagent, make product molecule
In containing a large amount of active terminal double bond, these active terminal double bonds, under suitable photoinitiator and UV irradiation, double bond is anti-rapidly
It answers, the crosslink density of castor oil-base waterborne polyurethane resin greatly improved, improve the curing rate of dispersion, and then improve
UV solidifies the mechanical property and water resistance of castor oil-base aqueous polyurethane dispersion.Embodiment statistics indicate that: gained UV solidification
37~81.8nm of partial size of castor oil-base aqueous polyurethane dispersion, water absorption rate are 21.1~33.2%, pencil hardness H, bullet
Property 211.36~245.154MPa of modulus, elongation at break 80.222~276.385%, tensile strength 9.181~
15.105MPa, 4.917~7.061MPa of yield strength.
Detailed description of the invention
Fig. 1 is the grading curve of 1 gained castor oil-base aqueous polyurethane of Examples 1 to 2 and comparative example;
Fig. 2 is that UV obtained by Examples 1 to 2 solidifies castor oil-base aqueous polyurethane dispersion and 1 gained castor oil of comparative example
The stress-strain diagram of base water polyurethane.
Specific embodiment
The present invention provides a kind of UV preparation method for solidifying castor oil-base aqueous polyurethane dispersion, comprising the following steps:
(1) by 2,2- dihydromethyl propionic acid, diisocyanate, glycol chain extender, dibutyl tin dilaurate and first
Butanone mixing, after carrying out first stage addition reaction;Castor oil and the second butanone is added, carries out second stage addition reaction;Add
Enter pentaerythritol triacrylate, continues phase III addition reaction, obtain reaction solution;
(2) alkali is added in the reaction solution, carries out neutralization reaction, obtains performed polymer;
(3) by the performed polymer and water mixing and emulsifying, and butanone is removed, obtains castor oil-base aqueous polyurethane;
(4) the castor oil-base aqueous polyurethane is mixed with photoinitiator, it is aqueous obtains the UV solidification castor oil-base
Dispersions of polyurethanes;
The molar ratio of-OH and-NCO is 0.91 in W-response body.
The present invention is by 2,2- dihydromethyl propionic acid, diisocyanate, glycol chain extender, dibutyl tin dilaurate and
One butanone mixing, after carrying out first stage addition reaction;Castor oil and the second butanone is added, carries out second stage addition reaction;
Pentaerythritol triacrylate is added, continues phase III addition reaction, obtains reaction solution.
The present invention is by 2,2- dihydromethyl propionic acid, diisocyanate, glycol chain extender, dibutyl tin dilaurate and
The mixing of one butanone, carries out first stage addition reaction.
In the present invention, the diisocyanate preferably includes isophorone diisocyanate (IPDI), isophorone two
Isocyanates (IPDI) and hexamethylene diisocyanate (HDI) mixture, isophorone diisocyanate (IPDI) and hexichol
One of methane diisocyanate (MDI) mixture, further preferably IPDI.In the present invention, the isophorone two
The mass ratio of IPDI and HDI is preferably 1:1 in isocyanates (IPDI) and hexamethylene diisocyanate (HDI) mixture.?
In the present invention, in the isophorone diisocyanate (IPDI) and '-diphenylmethane diisocyanate (MDI) mixture IPDI and
The mass ratio of MDI is preferably 1:1.In the present invention, it has to include IPDI in the diisocyanate, this is because IPDI points
The reactivity of two isocyanate groups in son differs greatly, thus avoids and implode occurs in synthesis process, molecular weight
Excessive, viscosity increases severely and gel occurs, and guarantees the formation of target product.
In the present invention, the glycol chain extender preferably includes 1,4-butanediol, ethylene glycol, 1,2-PD and 1,3-
One or more of propylene glycol;When the glycol chain extender is mixture, weight of the present invention to substance each in mixture
Amount ratio is not specifically limited, any weight ratio.In the present invention, the effect of the glycol chain extender is that consumption is excessive
Isocyanate groups make-OH/-NCO value reach setting value 0.91;The present invention does not also do the dosage of the glycol chain extender
It is specific to limit, as long as the control of-OH/-NCO value can be made in reasonable interval.
The present invention is to the 2,2- dihydromethyl propionic acid (DMPA), diisocyanate, glycol chain extender, tin dilaurate two
The addition sequence of butyl tin and the first butanone is not specifically limited.
In the present invention, the temperature of the first stage addition reaction is preferably 80 DEG C;The first stage addition reaction
Time be preferably 1.5h.In the present invention, the first stage addition reaction preferably carries out in the case of stirring, described to stir
The revolving speed mixed is preferably 500~750r/min.
After first stage addition reaction, castor oil and the second butanone is added in the present invention, and it is anti-to carry out second stage addition
It answers.
In the present invention, after the adding manner of the castor oil and the second butanone preferably drips castor oil again plus the
Two butanone, the time that the castor oil is added dropwise is preferably 30min, and the second butanone can all be added immediately.The present invention is added second
The main purpose of butanone is the dropping funel that castor oil is added dropwise in rinse, guarantees that castor oil fully enters system and participates in reaction.This hair
The bright mass ratio to first butanone and the second butanone is not specifically limited, and preferably the amount of the first butanone is greater than the second butanone
Amount;More preferably the mass ratio of the first butanone and the second butanone is 4:1.The present invention is since most of butanone to be added in advance
Into system, the viscosity of system is reduced, reacts-the OH in system completely with-NCO, improves reaction efficiency.
In the present invention, the temperature of the second stage addition reaction is identical as the temperature of first stage addition reaction, excellent
It is selected as 80 DEG C.In the present invention, the time of the second stage addition reaction is preferably 4h;After second stage addition reaction 4h,
It is preferred that reaching reaction theory value by the amount of di-n-butylamine method measurement-NCO to determine.In the present invention, the second stage adds
At reaction preferably carry out under stirring conditions, the revolving speed of the stirring preferably as the revolving speed of first stage addition reaction,
Details are not described herein.
After second stage addition reaction, pentaerythritol triacrylate is added in the present invention, continues phase III addition
Reaction, obtains reaction solution.
In the present invention, the temperature of the phase III addition reaction preferably with first stage addition reaction, second stage
The temperature of addition reaction is identical, and preferably 80 DEG C;The time of the phase III addition reaction is preferably 2h.In the present invention,
The phase III addition reaction preferably carries out under stirring conditions, and the revolving speed of the stirring is preferably anti-with first stage addition
The revolving speed answered is the same, and details are not described herein.
After phase III addition reaction, phase III addition reaction liquid is preferably cooled to 40 DEG C by the present invention, is obtained
The reaction solution.
After obtaining reaction solution, alkali is added in the present invention in the reaction solution, is carried out neutralization reaction, is obtained performed polymer.At this
In invention, the alkali preferably includes triethylamine (TEA) or sodium hydroxide, further preferably triethylamine (TEA).In the present invention
In, the temperature of the neutralization reaction is preferably 40 DEG C, and the time of the neutralization reaction is preferably 15~30min.
In the present invention, the quality of 2, the 2- dihydromethyl propionic acid (DMPA) is preferably DMPA, diisocyanate, binary
Alcohol chain extender, castor oil, pentaerythritol triacrylate (PETA) and alkali gross mass 5~7%;The amount of substance of the alkali is preferred
Identical as the amount of substance of the DMPA, i.e., the molar ratio of alkali and DMPA is 1:1.In the present invention, the castor oil is quality
It is selected as DMPA, diisocyanate, glycol chain extender, castor oil, pentaerythritol triacrylate (PETA) and alkali gross mass
50%.In the present invention, since PETA content is higher, activity double key content also can be higher in molecule, final resin film
Chemical crosslinking density also can be higher, and water resistance and mechanical strength can be increased with the raising of PETA content, therefore, the present invention
The quality of the PETA is not specifically limited, those skilled in the art select according to actual needs.In the present invention
In, the gross mass of first butanone and the second butanone is preferably DMPA, diisocyanate, glycol chain extender, castor oil, season
The 150% of penta tetrol triacrylate (PETA) and alkali gross mass.In the present invention, in whole system-OH and-NCO mole
Than being 0.91.The present invention is not specifically limited the dosage of glycol chain extender, diisocyanate, as long as glycol chain extender,
Diisocyanate makes the molar ratio 0.91 of the-OH and-NCO in system together with other materials.In the present invention, institute
The quality for stating dibutyl tin dilaurate is preferably DMPA, diisocyanate, glycol chain extender, castor oil, pentaerythrite three
The 0.16% of acrylate (PETA) and alkali gross mass.
After obtaining performed polymer, the performed polymer and water mixing and emulsifying are removed butanone by the present invention, obtain castor oil-base water
Property polyurethane.
In the present invention, the additional amount of the water is preferably DMPA, diisocyanate, glycol chain extender, castor oil, season
The 300% of penta tetrol triacrylate (PETA) and alkali gross mass, i.e., the theoretical solid content of the described castor oil-base aqueous polyurethane
It is 25%.In the present invention, the revolving speed of the mixing and emulsifying is preferably 2000r/min;The time of the mixing and emulsifying is preferably
45min.In the present invention, the device for carrying out the mixing and emulsifying is preferably Multi-functional dispersion sand mill.In the present invention, it is related to
When device, the operation of the mixing and emulsifying is preferred are as follows: first performed polymer is placed in Multi-functional dispersion sand mill, in certain revolving speed
Under, distilled water is added dropwise, about dropwise addition 15min, then proceedes to disperse 30min under same rotational speed.The present invention is to described multi-functional
The revolving speed of dispersion sand mill does not require specifically.
In the present invention, the mode for removing butanone is preferably evaporated under reduced pressure;The present invention to the parameter of the vacuum distillation not
It is specifically limited, parameter is evaporated under reduced pressure using butanone well known to those skilled in the art.
After obtaining castor oil-base aqueous polyurethane, the present invention mixes the castor oil-base aqueous polyurethane with photoinitiator
It closes, obtains the UV solidification castor oil-base aqueous polyurethane dispersion.
In the present invention, the photoinitiator preferably includes DAROCURE TPO, 2100 IRGACURE, IRGACURE
819.In a specific embodiment of the present invention, due to having used the UV curing apparatus of 395nm wavelength, photoinitiator is more preferably
IRGACURE 819.In the present invention, the dosage of the photoinitiator is preferably the castor oil-base aqueous polyurethane gross mass
3%.In the present invention, the mixed mode is preferably ultrasound;The time of the ultrasound is preferably 3~5min.
The present invention introduces photoinitiator in castor oil-base aqueous polyurethane, obtains UV solidification castor oil-base aqueous polyurethane
Dispersion, the dispersion can be solidified using UV, make dispersion Quick cross-linking, improve UV solidification castor oil-base aqueous polyurethane
The mechanical property and water resistance of dispersion.
The present invention also provides UV made from preparation method described in above-mentioned technical proposal to solidify castor oil-base aqueous polyurethane
Dispersion.In the present invention, the theoretical solid content that the UV solidifies castor oil-base aqueous polyurethane dispersion is preferably 25%.
The present invention also provides the solidification castor oil-base aqueous polyurethane dispersion of UV described in above-mentioned technical proposal to lead in coating
Application in domain.In the present invention, the UV solidification castor oil-base aqueous polyurethane dispersion can be used directly as coating,
With excellent system stability;It can also be used cooperatively with other auxiliary agents.
After UV solidification castor oil-base aqueous polyurethane dispersion of the invention is cured, excellent water resistance and power are achieved
Performance is learned, can be widely applied for paint field.
Castor oil-base aqueous polyurethane dispersion and its preparation side are solidified to UV provided by the invention below with reference to embodiment
Method is described in detail with application, but they cannot be interpreted as limiting the scope of the present invention.
Embodiment 1
(1) in 250mL four-hole boiling flask be added 2.5g DMPA, 17.14g IPDI, 0.93g BDO, 0.08g DBTDL and
Flask after fit on spherical condensation tube, nitrogen inlet, mechanical agitator and dropping funel, is placed in 80 DEG C of thermostatted waters by 60g butanone
1.5h is reacted in bath, and keeps lasting stirring, revolving speed 500r/min;25g is then added dropwise into flask by dropping funel
Castor oil and 15g butanone, about dropwise addition 30min, the reaction was continued 4h, after use di-n-butylamine method titration-nco value, determine
Reach reaction theory value;2.5g PETA is added, keeps the temperature 2h under the same terms, then cools to 40 DEG C, obtain reaction solution;
(2) TEA (1.89g) with amounts of substances such as DMPA is added in reaction solution, keeps the temperature 30min, obtains performed polymer;
(3) performed polymer is placed in the Multi-functional dispersion sand mill of laboratory, and 150g water is added dropwise, keep 2000r/min's
Mixing speed is evaporated under reduced pressure at room temperature after emulsifying 45min, is removed butanone, is obtained castor oil-base aqueous polyurethane, match
- the OH/-NCO of side is 0.91;
(4) photoinitiator (IRGACURE that mass fraction is 3% is added in Xiang Suoshu castor oil-base aqueous polyurethane
819), ultrasonic disperse 3min obtains the UV solidification castor oil-base aqueous polyurethane dispersion.
Particle diameter distribution test: the aqueous poly- ammonia of castor oil-base is measured using Zetapals 0-555 laser particle analyzer (Brooker)
The particle diameter distribution of ester;Gained castor oil-base aqueous polyurethane sample is diluted to 1.25wt% or so (about diluting 20 times), is added
Into quartzy standard colorimetric ware, it is ensured that after bubble-free, tested.It as a result is the partial size of gained castor oil-base aqueous polyurethane
65.9nm。
Pencil hardness test: by castor oil-base aqueous polyurethane uneven finish to template surface, 50 DEG C of oven dryings are placed in
Then 30min is polished to coating surface using sand paper, repeat to cover with paint, lacquer, colour wash, etc. 3 times, obtain paint film.It is measured using QHQ-A type Pencil scratch
The pencil hardness of instrument (Dongguan three and instrument) test paint film.
Water resistance experiment: UV solidification castor oil-base aqueous polyurethane dispersion is poured into 45mm*12mm* respectively
In the Teflon mould of 1mm, at room temperature, moisture evaporation it is complete after (at least 12h), take out film, using UV lamp irradiation 5~
10 seconds, after cooling, film is fitted into sample sack, is sealed, Water Resistance Test is carried out to film.Membranes submerged is being gone
In ionized water, continue 56h, the quality of recording sheet immersion front and back is respectively m0And m1, calculate water absorption rate.Every group of sample test 3
Secondary, final water absorption rate is averaged.The calculation formula of water absorption rate is as follows:
Water absorption rate=(m1-m0)/m0× 100%.
Tension test: UV solidification castor oil-base aqueous polyurethane dispersion is poured into 45mm*12mm*1mm respectively
Teflon mould in, at room temperature, moisture evaporation it is complete after (at least 12h), take out film, use UV lamp irradiation 5~10
Second, after cooling, film is fitted into sample sack, is sealed, tension test is carried out to film.Maneuvering load capacity is 5KN
AL-7000S electronic universal tester (Gotech Testing Machines Inc, Taiwan) to film carry out tension test.
The edge of rectangle sample is wiped out, having a size of 42mm*10mm, tensile speed 10mm/min, every group sample test 3 times, and take
Average value.
Measure the partial size 81.8nm, pencil hardness H of castor oil-base aqueous polyurethane obtained by the present embodiment;UV solidifies castor oil
The water absorption rate of base water polyurethane dispersion is 21.1%, elasticity modulus 211.36MPa, and elongation at break 276.385% stretches
Intensity 15.105MPa, yield strength 7.561MPa.
Embodiment 2
(1) 3.5g DMPA, 16.35g IPDI, 0.015g BDO, 0.08g DBTDL are added in 250mL four-hole boiling flask
With 60g butanone, after fit on spherical condensation tube, nitrogen inlet, mechanical agitator and dropping funel, flask is placed in 80 DEG C of constant temperature
1.5h is reacted in water-bath, and keeps lasting stirring, revolving speed 500r/min;Then it is added dropwise by dropping funel into flask
25g castor oil and 15g butanone, about dropwise addition 30min, the reaction was continued 4h, after use di-n-butylamine method titration-nco value, really
Surely reach reaction theory value;2.5g PETA is added, keeps the temperature 2h under the same terms, then cools to 40 DEG C, obtain reaction solution;
(2) TEA (2.64g) with amounts of substances such as DMPA is added in reaction solution, keeps the temperature 30min, obtains performed polymer;
(3) performed polymer is placed in the Multi-functional dispersion sand mill of laboratory, and 150g water is added dropwise, keep 2000r/
The mixing speed of min is evaporated under reduced pressure at room temperature after emulsifying 45min, is removed butanone, is obtained the aqueous poly- ammonia of castor oil-base
The ester ,-OH/-NCO of formula are 0.91;
(4) photoinitiator (IRGACURE that mass fraction is 3% is added in Xiang Suoshu castor oil-base aqueous polyurethane
819), ultrasonic disperse 3min obtains the UV solidification castor oil-base aqueous polyurethane dispersion.
Using the partial size 37nm of test method test gained castor oil-base aqueous polyurethane same as Example 1, pencil
Hardness H;The water absorption rate that UV solidifies castor oil-base aqueous polyurethane dispersion is 33.2%, elasticity modulus 245.154MPa, fracture
Elongation 80.222%, tensile strength 9.181MPa, yield strength 4.917MPa.
Comparative example 1
(1) in 250mL four-hole boiling flask be added 2.5g DMPA, 18.69g IPDI, 1.93g BDO, 0.08g DBTDL and
Flask after fit on spherical condensation tube, nitrogen inlet, mechanical agitator and dropping funel, is placed in 80 DEG C of thermostatted waters by 60g butanone
1.5h is reacted in bath, and keeps lasting stirring, revolving speed 500r/min;25g is then added dropwise into flask by dropping funel
Castor oil and 15g butanone, about dropwise addition 30min, the reaction was continued 4h, after use di-n-butylamine method titration-nco value, determine
Reach reaction theory value;2h is kept the temperature under the same terms, is then cooled to 40 DEG C, is obtained reaction solution;
(2) TEA (1.89g) with amounts of substances such as DMPA is added in reaction solution, keeps the temperature 30min, obtains performed polymer;
Performed polymer is placed in the Multi-functional dispersion sand mill of laboratory, and 150g water is added dropwise, keeps the stirring of 2000r/min
Speed, after emulsifying 45min;It is evaporated under reduced pressure at room temperature, removes butanone, obtain castor oil-base aqueous polyurethane;Formula-
OH/-NCO is 0.91.
Use the partial size of test method test gained castor oil-base aqueous polyurethane same as Example 1 for 65.9nm,
Water absorption rate is 352.4%, pencil hardness B, elasticity modulus 65.33MPa, elongation at break 297.478%, tensile strength
5.532MPa yield strength 2.771MPa.
Comparative example 2
(1) in 250mL four-hole boiling flask be added 3.5g DMPA, 17.90g IPDI, 0.97g BDO, 0.08g DBTDL and
Flask after fit on spherical condensation tube, nitrogen inlet, mechanical agitator and dropping funel, is placed in 80 DEG C of thermostatted waters by 60g butanone
1.5h is reacted in bath, and keeps lasting stirring, revolving speed 500r/min;25g is then added dropwise into flask by dropping funel
Castor oil and 15g butanone, about dropwise addition 30min, the reaction was continued 4h, after use di-n-butylamine method titration-nco value, determine
Reach reaction theory value;2h is kept the temperature under the same terms, is then cooled to 40 DEG C, is obtained reaction solution;
(2) 2.64g TEA is added in the reaction solution, keeps the temperature 30min, obtains performed polymer;
(3) performed polymer is placed in the Multi-functional dispersion sand mill of laboratory, and 150g water is added dropwise, keep 2000r/
The mixing speed of min is evaporated under reduced pressure at room temperature after emulsifying 45min, is removed butanone, is obtained the aqueous poly- ammonia of castor oil-base
Ester;- the OH/-NCO of formula is 0.91.
Using the partial size 22.8nm of test method test gained castor oil-base aqueous polyurethane same as Example 1, inhale
Water rate is 436.7%, pencil hardness B, elasticity modulus 49.229MPa, elongation at break 324.108%, tensile strength
9.461MPa yield strength 2.752MPa.
Fig. 1 is the grading curve of 1 gained castor oil-base aqueous polyurethane of Examples 1 to 2 and comparative example;It can from Fig. 1
To find out: when DMPA content is identical, the partial size for introducing the castor oil-base aqueous polyurethane of PETA, which is apparently higher than, is not introduced into PETA's
The partial size of conventional castor oil-base aqueous polyurethane;In addition, DMPA content is got in the polyurethane based on castor oil system for being introduced into PETA
Height, particle diameter distribution is narrower, and average grain diameter is smaller.
Fig. 2 is that UV obtained by Examples 1 to 2 solidifies castor oil-base aqueous polyurethane dispersion and 1 gained castor oil of comparative example
The stress-strain diagram of base water polyurethane, as can be seen from Figure 2: compared with conventional castor oil-base aqueous polyurethane, UV solidification
Castor oil-base aqueous polyurethane dispersion obviously has higher tensile strength, Young's modulus and lower elongation at break;?
UV solidifies in castor oil-base aqueous polyurethane dispersion, and DMPA content is higher, and the Young's modulus of UV resin is significantly raised, and fracture is stretched
Long rate is remarkably decreased.
Comparing embodiment 2 and embodiment 1 are it can be seen that DMPA content drops to 5% by 7%, and average grain diameter is by 37nm
It is raised to 81.8nm, water absorption rate drops to 21.1% by 33.2%, and elasticity modulus drops to 211.36MPa by 245.154MPa, breaks
It splits elongation and is increased to 276.385% by 80.222%.It is apparent that castor oil-base aqueous polyurethane cured for UV,
DMPA content is lower, and average grain diameter is bigger, and the state of aggregation stability of lotion is better, and the water resistance of resin film is also more excellent, power
Learning intensity slightly reduces.After comparing embodiment 1 and comparative example 1 are it can be seen that be added PETA, water absorption rate by original 352.4%,
Drop to 21.1%, pencil hardness rises to H by B, and elasticity modulus rises to 211.36MPa, elongation at break by 65.33MPa
Drop to 276.385% by 297.478%, tensile strength rises to 15.105MPa by 5.532MPa, yield strength by
2.771MPa rising to 7.561MPa.Obviously, compared with common cured castor oil-base aqueous polyurethane, the UV for introducing PETA is solid
Changing castor oil-base aqueous polyurethane emulsion obviously has smaller average grain diameter, higher state of aggregation stability, the cured tree of UV
Membrane of lipoprotein has superior water resistance and higher mechanical strength.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. the preparation method that a kind of UV solidifies castor oil-base aqueous polyurethane dispersion, which comprises the following steps:
(1) by 2,2- dihydromethyl propionic acid, diisocyanate, glycol chain extender, dibutyl tin dilaurate and the first butanone
Mixing, after carrying out first stage addition reaction;Castor oil and the second butanone is added, carries out second stage addition reaction;Season is added
Penta tetrol triacrylate, continues phase III addition reaction, obtains reaction solution;
(2) alkali is added in the reaction solution, carries out neutralization reaction, obtains performed polymer;
(3) by the performed polymer and water mixing and emulsifying, and butanone is removed, obtains castor oil-base aqueous polyurethane;
(4) the castor oil-base aqueous polyurethane is mixed with photoinitiator, obtains the UV solidification aqueous poly- ammonia of castor oil-base
Ester dispersion;
The molar ratio of-OH and-NCO is 0.91 in W-response body.
2. preparation method according to claim 1, which is characterized in that the diisocyanate includes two isocyanide of isophorone
Acid esters, isophorone diisocyanate and hexamethylene diisocyanate mixture, isophorone diisocyanate and hexichol first
One of alkane mixtures of diisocyanates.
3. preparation method according to claim 1, which is characterized in that the glycol chain extender include 1,4-butanediol,
One or more of ethylene glycol, 1,2- propylene glycol and 1,3- propylene glycol.
4. preparation method according to claim 1 or 2 or 3, which is characterized in that the quality of the castor oil is 2,2- dihydroxy
Methylpropanoic acid, diisocyanate, glycol chain extender, castor oil, pentaerythritol triacrylate and alkali gross mass 50%.
5. preparation method according to claim 1 or 2 or 3, which is characterized in that the quality of 2, the 2- dihydromethyl propionic acid
For 2,2- dihydromethyl propionic acid, diisocyanate, glycol chain extender, castor oil, pentaerythritol triacrylate and the total matter of alkali
The 5~7% of amount.
6. preparation method according to claim 5, which is characterized in that the alkali and 2, the molar ratio of 2- dihydromethyl propionic acid
For 1:1.
7. preparation method according to claim 1 or 2 or 3, which is characterized in that first butanone and the second butanone it is total
Quality is that 2- dihydromethyl propionic acid, diisocyanate, glycol chain extender, castor oil, pentaerythritol triacrylate and alkali are total
The 150% of quality.
8. preparation method according to claim 1, which is characterized in that the photoinitiator include DAROCURE TPO,
IRGACURE 2100 or IRGACURE 819.
9. the UV solidification castor oil-base aqueous polyurethane dispersion that any one of claim 1~8 preparation method is prepared,
It is characterized in that, the theoretical solid content that the UV solidifies castor oil-base aqueous polyurethane dispersion is 25%.
10. UV as claimed in claim 9 solidifies application of the castor oil-base aqueous polyurethane dispersion in paint field.
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