CN104774339B - A kind of polyether type aqueous polyurethane emulsion and preparation method thereof - Google Patents
A kind of polyether type aqueous polyurethane emulsion and preparation method thereof Download PDFInfo
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- CN104774339B CN104774339B CN201510155101.0A CN201510155101A CN104774339B CN 104774339 B CN104774339 B CN 104774339B CN 201510155101 A CN201510155101 A CN 201510155101A CN 104774339 B CN104774339 B CN 104774339B
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Abstract
The invention discloses a kind of polyether type aqueous polyurethane emulsion and preparation method thereof.It comprises the following steps：1) in an inert atmosphere, chain extender is mixed with diisocyanate, and reaction obtains mixture I；2) in an inert atmosphere, mixture I is mixed with PPG and hydrophilic chain extender, reaction obtains mixture II；3) mixture II is mixed with hydroxy acryl acid ester, reaction obtains base polyurethane prepolymer for use as；4) alkali is added to neutralize base polyurethane prepolymer for use as, then add water emulsification, then crosslinking by radiation is to obtain polyether type aqueous polyurethane emulsion.The present invention uses small molecule glycol and diisocyanate prepolymer, and the segment formed after being reacted with polyether segment phase reversal difficulty in emulsification is easy compared with the emulsification of polyethers performed polymer, and emulsion process is readily accomplished when molecular weight is relatively low；Use Co‑60The emulsion that gamma-rays is obtained to base polyurethane prepolymer for use as carries out cross-linking radiation, can effectively improve the molecular weight of aqueous polyurethane, aqueous polyurethane emulsion is had original text solid content and preferably mechanical performance.
Description
Technical field
The present invention relates to a kind of polyether type aqueous polyurethane emulsion and preparation method thereof, belong to fine polymer material and its
Preparation field.
Background technology
Aqueous polyurethane (WPU) is a family macromolecule synthetic material, and it has wear-resisting, corrosion-resistant, low temperature flexibility good, resistance to
Tired the advantages of, it can be used as adhesive for shoe use, coating, fabric coating, adhesive of various packing articles etc., its using water as
Decentralized medium, has the advantages that non-ignitable, environmentally friendly, small to human body excitant.Using PPG and PEPA as soft segment
Aqueous polyurethane occupies the overwhelming majority in aqueous polyurethane, wherein, the aqueous polyurethane using PPG as soft segment exists
Had a wide range of applications in fabric coating, the leather substance with flexible touch.
It is different from the WPU using PEPA as soft segment, PPG for soft segment strand in contain a large amount of ehter bonds,
Its speed when occurring phase reversal is the WPU of soft segment considerably slower than PEPA, simultaneously because contain hydrophilic radical in segment,
This causes polyether-type WPU solid content to be difficult to improve, and general polyether-type WPU solid contents are not higher than 40%, and its synthesis technique is also determined
Determined WPU molecular weight be difficult to reach it is very high, meanwhile, in traditional preparation method, isocyanates is significantly excessive before emulsification
, general value ([NCO]/[OH]) is more than 1.3, because the isocyanates of residual can continue to carry out reaction until consumption is entirely
Only, this causes WPU to also need to long period emulsion property after emulsifying and could stablize, in this process the performance of WPU emulsion
It is lasting change.The not enough application to polyether-type WPU of the above generates adverse effect.
When preparing WPU, molecular weight is higher, and viscosity is bigger before emulsification, and emulsification difficulty is bigger, and WPU molecular weight is low is more easy to
In the emulsion for preparing high solids content, but the mechanical property of now high-solid content water-based polyurethane is poor.
Existing solid content is low at present for polyether-type WPU, poor mechanical property the problem of, emulsified with two amido sulfonate types
Agent substitutes dihydromethyl propionic acid and prepares high solids content WPU, the sulfamic acid salt form chain extender system that such as CN201310694240 is used
The Gao Gu that the WPU of standby high solids content, patent CN201110100592 also disclose that a kind of use sulfonate chain extender and prepared
Content WPU, but generally, synthesis difficulty is prepared greatly using sulfamate, two amido sulfonate are easy when emulsifying chain extension
Gel is produced, the water resistance of product is not also good.WPU crosslinkings is improved WPU physical and chemical performances using crosslinking agent, but closing
Into also easily making WPU crosslinkings be also easy to produce gel, stability of emulsion is influenceed, and water dispersible multi isohydrocyanic ether is added when WPU is used
Adhesive prepared by external crosslinking method has preferably combination property, but need make WPU with the dispersible crosslinking agent of water when using
With preceding mixing, operate more loaded down with trivial details, be unfavorable for construction.
The content of the invention
It is an object of the invention to provide a kind of polyether type aqueous polyurethane emulsion and preparation method thereof, the method comprises the steps of firstly, preparing
The relatively low base polyurethane prepolymer for use as of molecular weight, then prepares the polyether type aqueous polyurethane of high solids content using the method for crosslinking with radiation
Emulsion.
The preparation method for the polyether type aqueous polyurethane emulsion that the present invention is provided, comprises the following steps：1) in inert atmosphere
In, chain extender is mixed with diisocyanate, reaction obtains mixture I, the chain extender is dihydric alcohol；
2) in the inert atmosphere, the mixture I is mixed with PPG and hydrophilic chain extender, reaction is obtained
Mixture II；
3) mixture II is mixed with hydroxy acryl acid ester, reaction obtains base polyurethane prepolymer for use as；
4) in the base polyurethane prepolymer for use as alkali will be added to neutralize, then add water emulsification, then crosslinking by radiation is to obtain described poly-
Ether type aqueous polyurethane emulsion.
In above-mentioned method, the dihydric alcohol can be at least one of ethylene glycol, BDO and diglycol；
The diisocyanate can be aliphatic diisocyanate or aromatic diisocyanate, the isocyanide of aliphatic two
Acid esters can be at least one in 1, hexamethylene-diisocyanate, IPDI and dicyclohexyl methyl hydride diisocyanate
Kind, the aromatic diisocyanate can be 2,4- toluene di-isocyanate(TDI)s, 2,6- toluene di-isocyanate(TDI)s or 4,4 '-hexichol first
Alkane diisocyanate；
The inert gas can be nitrogen or argon gas；
The mass ratio of the chain extender and the diisocyanate can be 1：2~8, concretely 1：3.70、1：4.27、1：
4.79、1：4.93、1：5.43、1：5.98 or 1：3.70~5.98.
In above-mentioned method, the PPG is polypropylene glycol, polytetrahydrofuran diol and polyoxypropyleneglycol
At least one of, the molecular weight of the PPG can be 600~4000, concretely 1000,2000 or 1000~2000；
The hydrophilic chain extender can be carboxylic acid type dihydric alcohol or sulfonic acid sodium form chain extender, and the carboxylic acid type dihydric alcohol can be two
Hydroxymethyl propionic acid, dimethylolpropionic acid or dihydroxy half ester, the sulfonic acid sodium form chain extender can for ethylenediamine base ethyl sulfonic acid sodium or
Second dihydroxy b sodium salt；
The mass ratio of the PPG and the diisocyanate can be 1~3：1, concretely 1.28：1、1.50：
1、1.54：1、1.57：1、1.59：1、1.64：1 or 1.28~1.64：1；
The mass ratio of the hydrophilic chain extender and the diisocyanate can be 1：5~15, concretely 1：5.85、1：
7.71、1：8.20、1：8.89、1：10.67、1：11.75 or 1：5.85~11.75.
In above-mentioned method, the hydroxy acryl acid ester can be hydroxy-ethyl acrylate, hydroxypropyl acrylate, metering system
In sour hydroxyl ethyl ester, trimethylolpropane diacrylate, pentaerythritol diacrylate and pentaerythritol triacrylate at least
In a kind of present invention；
The mass ratio of the hydroxy acryl acid ester and the isocyanates is 1：5~30, concretely 1：8.89、1：
15.11、1：16.63、1：18.28、1：20.14、1：21.34 or 1：8.89~21.34；
The alkali is triethylamine, the triethylamine and the carboxylate radical forming salt in hydrophilic chain extender, improves emulsion droplet
Stability；
The radiation is Co-60- gamma-rays irradiates.
In the present invention, the hydroxy acryl acid ester is the mixed of hydroxyethyl methacrylate and pentaerythritol triacrylate
Compound, the mass ratio of the hydroxyethyl methacrylate and pentaerythritol triacrylate can be 1：0.35~1.6, concretely
1：0.5、2：0.7、1：1、1：1.5 or 3：2.5.
In above-mentioned method, step 1) in the temperature of reaction can be 60~80 DEG C, concretely 60 DEG C or 65 DEG C, the time is
0.5~1h, concretely 0.5h, 40min or 1h；
Step 2) in reaction temperature can be 75~85 DEG C, concretely 75 DEG C or 85 DEG C, the time be 2.5~4h, specifically
Can be 3h or 4h；
Step 3) in reaction temperature can be 50~75 DEG C, concretely 50 DEG C, 60 DEG C, 65 DEG C or 75 DEG C, the time be 3~
5h, concretely 3h or 4h；
Step 4) described in the mol ratio of alkali and the hydrophilic chain extender can be 0.9~1：1, i.e., the degree of neutralization of described neutralization
Can be 90~100%, concretely 90%, 95%, 98% or 100%, the dosage of the crosslinking with radiation can be 2~10kGy, tool
Body can be 2kGy, 3kGy, 4kGy, 6kGy or 2~6kGy, the time can be 15~180min, concretely 40min, 50min,
60min or 40~60min.
In above-mentioned method, step 1) and 2) in also include the chain extender, the diisocyanate, the polyethers is more
First alcohol and the hydrophilic chain extender using preceding by dewater treatment, using adding molecular sieve dehydration or vacuum dehydration；
In step 4) the step of also include before the neutralization that dilution dilution agent will be added in the base polyurethane prepolymer for use as, plus
Enter the diluent to reduce or substitute lower boiling solvent, so that the solid content of the polyether type aqueous polyurethane emulsion increases
Plus.
In above-mentioned method, the diluent can be at least one in organic solvent, propylene acid esters and polyurethane propylene acid esters
Kind；
The organic solvent is acetone or butanone, and the propylene acid esters is methyl acrylate, butyl acrylate and methyl-prop
At least one of e pioic acid methyl ester；
In the present invention, the polyurethane propylene acid esters can be that PPG and diisocyanate and hydroxy acrylate are anti-
The double bond containing urethane acrylate that should be formed, wherein diisocyanate are 2 with PPG mol ratio：1, hydroxy
The ratio of acid esters and diisocyanate is 1：1.
Present invention also offers polyether type aqueous polyurethane emulsion prepared by above-mentioned method.
In above-mentioned polyether type aqueous polyurethane emulsion, the solid content of the polyether type aqueous polyurethane emulsion can for 48~
55%, concretely 48%, 50%, 51%, 53% or 48~53%.
In the present invention solid content refer to emulsion or coating dry under prescribed conditions after remainder account for the quality of total amount
Percentage.
In the present invention, chain extender and excessive di-isocyanate reaction obtain the isocyanates of amido-containing acid ester segment
Blocked prepolymer, mixture I is the isocyanate-terminated prepolymer and unreacted diisocyanate of amido-containing acid ester segment；
Then hydrophilic chain extender and PPG are added into mixture I, then adds hydroxy acryl acid ester thereto, low point is obtained
The base polyurethane prepolymer for use as of son amount, the stirring that then adds water forms emulsion；The aqueous polyurethane emulsion of small-molecular-weight is radiated again
Crosslinking, that is, obtain the big polyether type aqueous polyurethane emulsion of molecular weight, its solid content is higher.
The present invention has advantages below：
(1) small molecule glycol and diisocyanate prepolymer are used, the segment formed after being reacted with polyether segment is in emulsification
Phase reversal difficulty is easy compared with the emulsification of polyethers performed polymer, is more easy to prepare the polyether type aqueous polyurethane of high solids content.
(2) emulsion process is completed when base polyurethane prepolymer for use as molecular weight is relatively low, shifts to an earlier date phase change location during emulsification, it is easy to
Prepare the aqueous polyurethane emulsion of high solids content.
(3) Co is used-60The emulsion that-gamma-rays is obtained to base polyurethane prepolymer for use as carries out irradiation and realizes base polyurethane prepolymer for use as
Crosslinking, can effectively improve the molecular weight of aqueous polyurethane, the aqueous polyurethane emulsion is had preferably mechanical performance.
(4) acrylate and urethane acrylate are used as diluent, can be reduced or without using low boiling point solvent, energy
Enough improve the effective solid content of emulsion.
Embodiment
Experimental method used in following embodiments is conventional method unless otherwise specified.
Material, reagent used etc., unless otherwise specified, are commercially obtained in following embodiments.
The tensile strength of aqueous polyurethane film and elongation percentage method of testing are carried out according to GB13022-91 in following embodiments
Measurement.
The preparation of embodiment 1, polyether type aqueous polyurethane emulsion
Under nitrogen atmosphere, the 6.5g BDOs and the isocyanide of 32.06g isophorones two of water will be removed with molecular sieve
(1,4 butanediols and PIDI mass ratio are 1 to acid esters (IPDI):4.93) mix, in after reaction 1h at 60 DEG C；Under nitrogen atmosphere,
(N-220, molecular weight is 2000 to the 41g polyoxypropyleneglycols added after vacuum dehydration, the matter of PPG and isocyanates
Amount is than being 1.28:1), dihydromethyl propionic acid (DMPA) 3g (DMPA and IPDI mass ratioes 1：10.67) it is, anti-in continuing at 85 DEG C
Answer 3h；Then 50 DEG C are cooled to and adds 1g hydroxyethyl methacrylates and 0.5g pentaerythritol triacrylates (hydroxyl propylene
Acid esters and IPDI quality parts ratio 1:21.34), add the dilution of 20g butanone using reduce viscosity (butanone and IPDI mass ratio as
1：1.6) nertralizer triethylamine, and after sustained response 5h is slowly added dropwise in performed polymer, degree of neutralization 90%, then in high-speed stirred
Lower addition 85g water is emulsified, and obtains milky aqueous polyurethane emulsion, solvent is sloughed in distillation, by obtained aqueous polyurethane
Emulsion is fitted into glass container, uses Co-60Gamma-rays is irradiated to emulsion, and dose of radiation 2kGy, radiated time is 40min；
Obtain the polyether type aqueous polyurethane emulsion that solid content is 50%.
The tensile strength that film is made in the polyether type aqueous polyurethane emulsion that solid content of the present invention is 50% is 6.95MPa, is prolonged
It is 900% to stretch rate.
The preparation of embodiment 2, aqueous polyurethane emulsion
Under nitrogen atmosphere, the BDO 13.34g and the isocyanide of 49.36g isophorones two of water will be removed with molecular sieve
(1,4 butanediols and PIDI quality parts ratio are 1 to acid esters (IPDI):3.70) mix, in after reaction 30min at 80 DEG C；In nitrogen
Under atmosphere, 77.90g polyoxypropyleneglycols (N-220, molecular weight 2000, PPG and the isocyanide added after vacuum dehydration
The mass ratio of acid esters is 1.57:1), 4.2g dihydromethyl propionic acids (abbreviation DMPA, DMPA and IPDI quality parts ratio 1:
11.75), in sustained response 4h at 75 DEG C, 60 DEG C is then cooled to and adds 2g hydroxyethyl methacrylates and 0.7g pentaerythrites
Triacrylate (hydroxy acryl acid ester and IPDI quality parts ratio 1:18.28) dilution of 30g butanone, is added to reduce viscosity
(butanone and IPDI quality parts ratio are 1:1.64) base polyurethane prepolymer for use as, and after sustained response 4h is obtained, neutralization is slowly added dropwise
Agent triethylamine is in base polyurethane prepolymer for use as, degree of neutralization 95%, and then 148g water is emulsified under high velocity agitation, obtains milky
Solvent is sloughed in aqueous polyurethane emulsion, distillation, and obtained aqueous polyurethane emulsion is fitted into glass container, Co is used-60γ is penetrated
Line is irradiated to emulsion, and dose of radiation 2kGy, radiated time is 40min；Obtain solid content for 50% it is polyether type aqueous poly-
Urethane emulsion.
The tensile strength that film is made in the polyether type aqueous polyurethane emulsion that solid content of the present invention is 50% is 7.79MPa, is prolonged
It is 810% to stretch rate.
The preparation of embodiment 3, polyether type aqueous polyurethane emulsion
Under nitrogen atmosphere, the BDO 8.34g and the isocyanide of 49.89g isophorones two of water will be removed with molecular sieve
(1,4 butanediols and PIDI quality parts ratio are 1 to acid esters (IPDI):5.98) mix, in after reaction 40min at 65 DEG C；In nitrogen
Under atmosphere, polyoxypropyleneglycol (N-220, molecular weight 2000) 75.0g (PPG and the isocyanide added after vacuum dehydration
The mass ratio of acid esters is 1.50:1), 8.53g dihydromethyl propionic acids (abbreviation DMPA, DMPA and IPDI mass ratio 1：5.85), in
Sustained response 3h at 75 DEG C, is then cooled to 60 DEG C and adds 1.5g hydroxyethyl methacrylates and the acrylic acid of 1.5g pentaerythrites three
Ester (hydroxy acryl acid ester and IPDI mass ratio 1:16.63) dilution of 30g butanone, is added to reduce viscosity (butanone and IPDI
Quality parts ratio be 1:1.66), and sustained response is slowly added dropwise nertralizer triethylamine after 4 hours, degree of neutralization 100%, then
156g water is added under high velocity agitation to be emulsified, and obtains milky aqueous polyurethane emulsion, solvent is sloughed in distillation, by what is obtained
Aqueous polyurethane emulsion is fitted into glass container, uses Co-60Gamma-rays is irradiated to emulsion, dose of radiation 3kGy, during radiation
Between be 50min；Obtain the polyether type aqueous polyurethane emulsion that solid content is 48%.
The tensile strength that film is made in the polyether type aqueous polyurethane emulsion of the present invention 48% is 9.35MPa, and elongation percentage is
720%.
The preparation of embodiment 4, polyether type aqueous polyurethane emulsion
Under nitrogen atmosphere, it is the diglycol 10.6g and 45.33g isophorones two that water was removed with molecular sieve is different
(diglycol and PIDI mass ratio are 1 to cyanate (IPDI):4.27) mix, in after reaction 40min at 65 DEG C；In nitrogen
Under atmosphere, polyoxypropyleneglycol (N-220, molecular weight 2000) 70.0g (PPG and the isocyanide added after vacuum dehydration
The mass ratio of acid esters is 1.54:1), dihydromethyl propionic acid (DMPA) 5.53g (DMPA and IPDI quality parts ratios 1:8.20),
In sustained response 3h at 75 DEG C；Then 65 DEG C are cooled to and adds 1.5g hydroxyethyl methacrylates and the propylene of 1.5g pentaerythrites three
Acid esters (hydroxy acryl acid ester and IPDI quality parts ratio 1:15.11) dilution of 45.33g butanone, is added to reduce viscosity (fourth
Ketone and IPDI quality parts ratio are 1:1), and sustained response is slowly added dropwise nertralizer triethylamine after 4 hours, degree of neutralization 95%,
Then 140g water is added under high velocity agitation to be emulsified, and obtains milky aqueous polyurethane emulsion, solvent is sloughed in distillation, will
To aqueous polyurethane emulsion be fitted into glass container, use Co-60Gamma-rays is irradiated to emulsion, dose of radiation 4kGy, spoke
The time is penetrated for 60min；Obtain the polyether type aqueous polyurethane emulsion that solid content is 50%.
The tensile strength that film is made in the polyether type aqueous polyurethane emulsion that solid content of the present invention is 50% is 9.67MPa, is prolonged
It is 750% to stretch rate.
The preparation of embodiment 5, polyether type aqueous polyurethane emulsion
Under nitrogen atmosphere, it is the diglycol 10.51g and 50.36g isophorones two that water was removed with molecular sieve is different
(diglycol and IPDI quality parts ratio are 1 to cyanate (IPDI):4.79) mix, at 65 DEG C react 40min after,
Under nitrogen atmosphere, add vacuum dehydration after polyoxypropyleneglycol (N-220, molecular weight 2000) 80.0g (PPG with
The mass ratio of isocyanates is 1.59:1), dihydromethyl propionic acid 6.53g (DMPA and IPDI quality parts ratios 1：7.71), in
Sustained response 3h at 75 DEG C, then adds 1g hydroxyethyl methacrylates and 1.5g pentaerythritol triacrylates (hydroxyl third
Olefin(e) acid ester and IPDI quality parts ratio 1:20.14) 30g ethyl acrylates, are added to reduce viscosity (ethyl acrylate and IPDI
Quality parts ratio be 1:1.68), and in sustained response 2 hours at 60 DEG C, nertralizer triethylamine, degree of neutralization is then slowly added dropwise
100%, 159g water is then added under high velocity agitation and is emulsified, and milky aqueous polyurethane emulsion is obtained, by obtained water
Property polyaminoester emulsion is fitted into glass container, uses Co-60Gamma-rays is irradiated to emulsion, dose of radiation 4kGy, radiated time
For 50min；Obtain the polyether type aqueous polyurethane emulsion that solid content is 53%.
The tensile strength that film is made in the polyether type aqueous polyurethane emulsion that solid content of the present invention is 53% is 8.33MPa, is prolonged
It is 820% to stretch rate.
The preparation of embodiment 6, aqueous polyurethane emulsion
Under nitrogen atmosphere, the BDO 9.0g and 48.9g isophorone diisocyanates of water will be removed with molecular sieve
Ester (IPDI) and hexamethylene diisocyanate (HDI) composition mixture in (wherein IPDI 33.3g, HDI 15.6g) (1,
The quality parts ratio of 4- butanediols and diisocyanate is 1:5.43) mix, in after reaction 0.5h at 60 DEG C；Under nitrogen atmosphere,
Polytetrahydrofuran diol (PTMG-1000, molecular weight 1000) 80.0g (PPG and two isocyanides added after vacuum dehydration
The total mass ratio of acid esters is 1.64:1), dihydromethyl propionic acid 5.50g (the gross mass portion rates 1 of DMPA and diisocyanate：
8.89), in sustained response 3h at 75 DEG C, 60 DEG C is then cooled to and adds 3.0g hydroxyethyl methacrylates and 2.5g pentaerythrites
Triacrylate (the gross mass portion rate 1 of hydroxy acryl acid ester and diisocyanate:8.89) 27g ethyl acrylates, are added
To reduce viscosity, (the gross mass portion rate of ethyl acrylate and isocyanates is 1:1.81) it is, and small in sustained response 4 at 60 DEG C
When, then it is slowly added dropwise nertralizer triethylamine, degree of neutralization 98%, then 170g water under high velocity agitation, is emulsified, obtains breast
White water-borne polyaminoester emulsion, obtained aqueous polyurethane emulsion is fitted into glass container, Co is used-60Gamma-rays is to emulsion
Irradiated, dose of radiation 6kGy, radiated time is 60min；Obtain the polyether type aqueous polyurethane emulsion that solid content is 51%.
Solid content of the present invention is 51% polyether type aqueous polyurethane emulsion plastic film mulch, and the tensile strength of gained film is
7.41MPa, elongation percentage is 660%.
Claims (3)
1. a kind of preparation method of polyether type aqueous polyurethane emulsion, comprises the following steps：
1) in an inert atmosphere, chain extender is mixed with diisocyanate, and reaction obtains mixture I, and the chain extender is dihydric alcohol；
The dihydric alcohol is at least one of ethylene glycol, BDO and diglycol；
The diisocyanate is aliphatic diisocyanate or aromatic diisocyanate, and the aliphatic diisocyanate is
1, at least one of hexamethylene-diisocyanate, IPDI and dicyclohexyl methyl hydride diisocyanate, the virtue
Fragrant (cyclo) aliphatic diisocyanates are 2,4- toluene di-isocyanate(TDI)s, 2,6- toluene di-isocyanate(TDI)s or 4,4 '-diphenylmethane diisocyanates
Ester；
The inert gas is nitrogen or argon gas；
The mass ratio of the chain extender and the diisocyanate is 1：2~8；
The temperature of the reaction is 60~80 DEG C, and the time is 0.5~1h；
2) in the inert atmosphere, the mixture I is mixed with PPG and hydrophilic chain extender, reaction is mixed
Thing II；
The PPG is at least one of polypropylene glycol, polytetrahydrofuran diol and polyoxypropyleneglycol, described poly-
The molecular weight of ethoxylated polyhydric alcohol is 600~4000；
The hydrophilic chain extender is carboxylic acid type dihydric alcohol or sulfonic acid sodium form chain extender, and the carboxylic acid type dihydric alcohol is dihydroxymethyl third
Acid, dimethylolpropionic acid or dihydroxy half ester, the sulfonic acid sodium form chain extender are ethylenediamine base ethyl sulfonic acid sodium or second dihydroxy second
Sulfonate sodium；
The mass ratio of the PPG and the diisocyanate is 1~3：1,
The mass ratio of the hydrophilic chain extender and the diisocyanate is 1：5~15；
The temperature of the reaction is 75~85 DEG C, and the time is 2.5~4h；
3) mixture II is mixed with hydroxy acryl acid ester, reaction obtains base polyurethane prepolymer for use as；
The hydroxy acryl acid ester is hydroxy-ethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, trihydroxy methyl third
At least one of alkane diacrylate, pentaerythritol diacrylate and pentaerythritol triacrylate；
The mass ratio of the hydroxy acryl acid ester and the isocyanates is 1：5~30；
The temperature of the reaction is 50~75 DEG C, and the time is 3~5h；
4) alkali is added to neutralize the base polyurethane prepolymer for use as, then add water emulsification, then crosslinking by radiation is to obtain the polyether-type water
Property polyaminoester emulsion；
The alkali is triethylamine, and the mol ratio of the alkali and the hydrophilic chain extender is 0.9~1：1；
The radiation is Co-60- gamma-rays irradiates；
The dosage of the crosslinking with radiation is 2~10kGy, and the time is 15~180min；
2. according to the method described in claim 1, it is characterised in that：Step 1) and 2) in also include the chain extender, described
Diisocyanate, the PPG and the hydrophilic chain extender are passing through dewater treatment before；
In step 4) the step of also include before the neutralization that dilution dilution agent will be added in the base polyurethane prepolymer for use as；
The diluent is at least one of organic solvent, propylene acid esters and polyurethane propylene acid esters；
The organic solvent is acetone or butanone, and the propylene acid esters is methyl acrylate, butyl acrylate and methacrylic acid
At least one of methyl esters.
3. polyether type aqueous polyurethane emulsion prepared by claim 1 or the method described in 2；
The solid content of the polyether type aqueous polyurethane emulsion is 48~55%.
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| CN111718469A (en) * | 2020-06-17 | 2020-09-29 | 北京华腾新材料股份有限公司 | Waterborne polyurethane, preparation method thereof and heat-sealing adhesive |
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| CN1656134A (en) * | 2002-04-19 | 2005-08-17 | Ppg工业俄亥俄公司 | Coating compositions containing polyurethane dispersions and highly crosslinked polymer particles |
| CN101328253A (en) * | 2008-07-17 | 2008-12-24 | 安徽大学 | Method for preparing high solid content aqueous polyurethane emulsion by continuous process |
| CN101429417A (en) * | 2008-12-08 | 2009-05-13 | 广州市科霖水性材料有限公司 | High-adhesive property watersoluble polyurethane adhesion agent and method of producing the same |
| CN102190803A (en) * | 2011-03-22 | 2011-09-21 | 北京市射线应用研究中心 | Internal-crosslinking aqueous polyurethane emulsion and preparation method thereof |
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2015
- 2015-04-02 CN CN201510155101.0A patent/CN104774339B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1656134A (en) * | 2002-04-19 | 2005-08-17 | Ppg工业俄亥俄公司 | Coating compositions containing polyurethane dispersions and highly crosslinked polymer particles |
| CN101328253A (en) * | 2008-07-17 | 2008-12-24 | 安徽大学 | Method for preparing high solid content aqueous polyurethane emulsion by continuous process |
| CN101429417A (en) * | 2008-12-08 | 2009-05-13 | 广州市科霖水性材料有限公司 | High-adhesive property watersoluble polyurethane adhesion agent and method of producing the same |
| CN102190803A (en) * | 2011-03-22 | 2011-09-21 | 北京市射线应用研究中心 | Internal-crosslinking aqueous polyurethane emulsion and preparation method thereof |
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