CN108102349A - The preparation method of organobentonite/epoxy resin composite modified water polyurethane emulsion - Google Patents
The preparation method of organobentonite/epoxy resin composite modified water polyurethane emulsion Download PDFInfo
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- CN108102349A CN108102349A CN201810060746.XA CN201810060746A CN108102349A CN 108102349 A CN108102349 A CN 108102349A CN 201810060746 A CN201810060746 A CN 201810060746A CN 108102349 A CN108102349 A CN 108102349A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/08—Polyurethanes from polyethers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
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Abstract
The invention discloses a kind of preparation methods of organobentonite/epoxy resin composite modified water polyurethane emulsion.The method first reacts oligomer dihydric alcohol and diisocyanate under catalyst action, then chain extending reaction is carried out with chain extender, small molecule dihydric alcohol, crosslinking agent successively, add in organobentonite and epoxy resin, neutralization reaction is carried out with neutralizer, then organobentonite/epoxy resin composite modified water polyurethane emulsion is made in emulsification pretreatment.The present invention passes through organobentonite and the composite modified aqueous polyurethane of epoxy resin, there is excellent mechanical property after emulsion film forming, tensile strength can reach 66.72MPa, adhesive force can reach 0 grade, emulsion intercalation method is greatly improved, and can store 9 months or more, comprehensive performance is improved significantly, and the type aqueous polyurethane emulsion reduces the pollution to environment and ensures the health of worker without organic solvent.
Description
Technical field
The invention belongs to aqueous polyurethane synthesis technical fields, and it is composite modified to be related to a kind of organobentonite/epoxy resin
The preparation method of aqueous polyurethane emulsion.
Background technology
Aqueous polyurethane is using water organic solvent to be replaced to gather as the polyurethane system of decentralized medium with traditional solvent-borne type
Urethane is compared, and aqueous polyurethane has the characteristics that nontoxic, nonflammable, environmentally friendly, and aqueous polyurethane structure-performance
Controllability makes it have the property of elastomer and plastics and excellent wearability and adhesive force etc. simultaneously, is widely used in skin
Leather/synthetic leather finishing agent, fabric coating and finishing agent, coating, adhesive, sheet surface treating agent and fiber surface treatment agent etc.
Field has a vast market prospect.But the water resistance of aqueous polyurethane, solvent resistance, heat resistance, physical mechanical property compared with
Difference limits the application of aqueous polyurethane to a certain extent.Meanwhile with the continuous development of science and technology, people are to material
Physical and mechanical properties requirement it is also higher and higher, in order to improve the comprehensive performance of aqueous polyurethane, expand use scope, need
It is modified.
Epoxy resin has that intensity is high, shrinks small and good chemical stability, can be with its modified aqueous polyurethane
Enhance coating machinery performance, improve the comprehensive performances such as water-fast, heat-resisting and solvent resistant.Jia Q M et al. epoxy resin modification water
Property polyurethane, bad (Jia Q M, et al.Effects of montmorillonite the on hydrogen of stability of emulsion
bonding,free volume and glass transition temperature of epoxy resin/
polyurethane interpenetrating polymer networks[J].European Polymer Journal,
2007,43(1):35-42.).Organobentonite has the advantages that oxidative resistance and low surface energy, with its modified polyurethane, can make
Film has good hydrophobicity, excellent low-temperature flexibility and high-temperature stability.Jihuai Wu et al. organobentonites change
Property aqueous polyurethane, emulsion film drying time is long, poor adhesive force (Jihuai Wu, et al.Study on starch-
graft-acrylamide/mineral powder super absorbent composite[J].Polymer,2003
(44):6513-6520)。
The content of the invention
The shortcomings of for current aqueous polyurethane emulsion drying time length, poor water resistance, bad heat resistance, the present invention provide
A kind of preparation method of organobentonite/epoxy resin composite modified water polyurethane emulsion.
Technical scheme is as follows:
The preparation method of organobentonite/epoxy resin composite modified water polyurethane emulsion, includes the following steps:
Step 1, prepared by bentonite:Bentonite with water is mixed, is stirred evenly, extracts suspension, adds in burnt phosphorus
Sour sodium dispersant, standing sedimentation, the dilute hydrochloric acid for adding in 0.5mol/L~1mol/L elutes, and at 60~90 DEG C, adds in mass fraction
It is sirred and separated for 10%~15% Fluorinse, at 70~90 DEG C, adds in the reagent/dilute hydrochloric acid mixed liquor that organises, filter
It is dry, obtain organobentonite;
Step 2, the preparation of organobentonite/epoxy resin composite modified water polyurethane emulsion:
(A) it is 1200~2600 in mass ratio by oligomer dihydric alcohol and diisocyanate:500~1500 are uniformly mixed,
Catalyst is added in, speed of agitator is 200~300r/min, is to slowly warm up to 80~90 DEG C, the first intermediate is obtained by the reaction;
(B) the first intermediate is cooled to 70~80 DEG C, adds in dry multi-hydroxy carboxy acid, reacts 2~3h, obtains in second
Mesosome;
(C) the second intermediate is warming up to 80~90 DEG C, adds in small molecule glycol monomer, reacts 1~2h, obtains in the 3rd
Mesosome;
(D) it is 80~90 DEG C that the 3rd intermediate, which keeps temperature, adds in trimethylolpropane crosslinking agent, reacts 2~3h, obtain
4th intermediate;
(E) the 4th intermediate keep temperature be 80~90 DEG C, with oligomer dihydric alcohol, diisocyanate, multi-hydroxy carboxy acid,
The gross mass of small molecule glycol monomer and trimethylolpropane crosslinking agent is total amount, by organobentonite and the mass ratio of total amount
For 3~5:100, the mass ratio of epoxy resin and total amount is 2~5:100, add in organobentonite and epoxy resin E-44, reaction
2~3h obtains the 5th intermediate;
(F) the 5th intermediate is cooled to 20~30 DEG C, and triethylamine is added under stirring and is neutralized into salt, during which adds in third
It is in colourless that ketone, which reduces viscosity to solution, when reaction 0.5~1 is small, obtains the 6th intermediate;
(G) the 6th intermediate adds water high speed shearing emulsification, and shear velocity control is in 1800~2000r/min, holding temperature
For 20~30 DEG C, be sufficiently stirred 0.5~1 it is small when, obtain the 7th intermediate;
(H) the 7th intermediate is evaporated under reduced pressure 1 under conditions of temperature is 35~45 DEG C, vacuum degree is 0.04~0.08MPa
~2h removes acetone, filters and pack to get the composite modified aqueous polyurethane emulsion of organobentonite/epoxy resin.
In step 1, the mass ratio of the bentonite and water is 1:4~9.
In step 1, the reagent that organises is selected from cetyl trimethylammonium bromide, cetyl trimethyl chlorination
Ammonium, octadecyl dimethyl benzyl ammonium chloride, dioctadecyl dimethyl ammonium chloride or double octadecyl dimethyl benzyl chlorinations
Ammonium, the molar ratio of described organise reagent and dilute hydrochloric acid is 1:1.
In step 2 (A), the oligomer dihydric alcohol is polyether Glycols or polyester diol.
The polyether Glycols use molecular weight for 1000~3000 polypropylene glycol, polyethylene glycol and PolyTHF
Combination more than one or both of glycol, the polyester diol use molecular weight to gather for 1000~4000 adipic acid
One or more in ester dihydric alcohol, polyhexamethylene adipate glycol, polycarbonate glycol, polycaprolactone diols.
In step 2 (A), the diisocyanate is norbornene alkyl diisocyanate, tetramethyl m-phenylenedimethylim- two
Isocyanates, dicyclohexyl methyl hydride diisocyanate, dimethyl diphenyl diisocyanate, diphenyl-methane -4,4 '-diisocyanate
One or more in ester.
In step 2 (A), the catalyst is dibutyl tin laurate, stannous octoate, the one of dibutyltin diacetate
Kind is a variety of.
In step 2 (B), the multi-hydroxy carboxy acid is dihydromethyl propionic acid (DMPA), in dimethylolpropionic acid (DMBA)
One or more.
In step 2 (C), the small molecule glycol monomer is selected from 1,4-butanediol, diglycol, trimethyl penta
Glycol, methyl propanediol, the one or more of 1,6- hexylene glycols or neopentyl glycol.
Compared with prior art, the present invention has the following advantages:
The present invention has excellent by organobentonite and the composite modified aqueous polyurethane of epoxy resin, after emulsion film forming
Mechanical property, tensile strength can reach 66.72MPa, and adhesive force can reach 0 grade, and emulsion intercalation method is greatly carried
Height can store 9 months or more, and comprehensive performance is improved significantly, and the type aqueous polyurethane emulsion subtracts without organic solvent
The health of pollution to environment and guarantee worker less.
Specific embodiment
For a further understanding of the present invention, with reference to embodiment, the invention will be further described.
Comparative example 1:Unmodified aqueous polyurethane
(1) 24.04g PolyTHFs are added in the 500mL three-necked flasks that agitating device, thermometer are housed at one successively
(molecular weight 1000), 16.26g norbornene alkyl diisocyanates, then add in 0.2g dibutyl tin laurates, and speed of agitator is
300r/min is to slowly warm up to 90 DEG C, reacts 2h;
(2) 70 DEG C are cooled to, adds 3g dimethylolpropionic acids, reacts 2h;
(3) 80 DEG C are warming up to, adds in 1.39g diglycols, reacts 1h;
(4) it is 80 DEG C to keep temperature, adds in the pentaerythrite of 2g, reacts 2h;
(5) 25 DEG C are cooled to, adds in 3.11g triethylamines, during which adding in 15ml acetone reduces viscosity, stirs 1h, obtains pre-
Polymers;
(6) 150g deionized waters are added in, agitator speed is adjusted into 1800r/min, keep temperature stabilization at 25 DEG C, fully
Stir 1h;
(7) 1h is evaporated under reduced pressure under conditions of temperature is 45 DEG C, vacuum degree is 0.06MPa, acetone is removed, filters and wrap
Dress is to get unmodified aqueous polyurethane emulsion.
Comparative example 2:The aqueous polyurethane that organobentonite is modified
1. prepared by bentonite
(1) 20g bentonites are added in 180g water in beaker and stirred evenly, top suspension is extracted after staticly settling 2h,
Into suspension add in 25g sodium pyrophosphate dispersants, stir 1.5h after, standing sedimentation 3h, add in 30ml 0.5mol/L it is dilute
Hydrochloric acid elutes, and filters, the calcium-base bentonite suspension purified;
(2) the calcium-base bentonite suspension and water that are obtained in step (1) are added in beaker, adding mass fraction is
Then 15% sodium fluoride, high-speed stirred 2h at 80 DEG C of water-bath separate, wash, is dry, obtaining sodium bentonite suspension.
(3) the sodium bentonite suspension and water that are obtained in step (2) are added in beaker, it is quick to stir, it has added
20ml cetyl trimethylammonium bromides/dilute hydrochloric acid mixed liquor, 85 DEG C of heating water bath stir 1h, stand 48h and then filter, wash
It washs, is dried in vacuo at 90 DEG C, obtains organobentonite.
2. the aqueous polyurethane that organobentonite is modified
(1) 23.46g PolyTHFs are added in the 500mL three-necked flasks that agitating device, thermometer are housed at one successively
(molecular weight 1000), 14.69g norbornene alkyl diisocyanates, then add in 0.2g dibutyl tin laurates, and speed of agitator is
300r/min is to slowly warm up to 90 DEG C, reacts 2h;
(2) 70 DEG C are cooled to, adds in 3g dimethylolpropionic acids, reacts 2h;
(3) 80 DEG C are warming up to, adds in 1.54g diglycols, reacts 1h;
(4) it is 80 DEG C to keep temperature, adds in the pentaerythrite of 2g, reacts 2h;
(5) it is 80 DEG C to keep temperature, adds in 2g organobentonites reaction 2h;
(6) 25 DEG C are cooled to, adds in 3.11g triethylamines, during which adding in 15ml acetone reduces viscosity, stirs 1h, obtains pre-
Polymers;
(7) 150g deionized waters are added in, agitator speed is adjusted into 1800r/min, keep temperature stabilization at 25 DEG C, fully
Stir 1h;
(8) 1h is evaporated under reduced pressure under conditions of temperature is 45 DEG C, vacuum degree is 0.06MPa, acetone is removed, filters and wrap
Fill the aqueous polyurethane emulsion being modified to get organobentonite.
Comparative example 3:The aqueous polyurethane emulsion that epoxy resin E-44 is modified
(1) 22.82g PolyTHFs are added in the 500mL three-necked flasks that agitating device, thermometer are housed at one successively
(molecular weight 1000), 15.84g norbornene alkyl diisocyanates, then add in 0.2g dibutyl tin laurates, and speed of agitator is
300r/min is to slowly warm up to 90 DEG C, reacts 2h;
(2) 70 DEG C are cooled to, adds in 3g dimethylolpropionic acids, reacts 2h;
(3) 80 DEG C are warming up to, adds in 1.73g diglycols, reacts 1h;
(4) it is 80 DEG C to keep temperature, adds in the pentaerythrite of 2g, reacts 2h;
(5) it is 80 DEG C to keep temperature, adds in 1.5g epoxy resin E-44s, reacts 2h;
(6) 25 DEG C are cooled to, adds in 3.11g triethylamines, during which adding in 15ml acetone reduces viscosity, stirs 1h, obtains pre-
Polymers;
(7) 150g deionized waters are added in, agitator speed is adjusted into 1800r/min, keep temperature stabilization at 25 DEG C, fully
Stir 1h;
(8) 1h is evaporated under reduced pressure under conditions of temperature is 45 DEG C, vacuum degree is 0.06MPa, acetone is removed, filters and wrap
Fill the aqueous polyurethane emulsion being modified to get epoxy resin E-44.
Comparative example 4:The aqueous polyurethane emulsion of organobentonite/composite modified epoxy resin E-39
1. prepared by bentonite
(1) 20g bentonites are added in 180g water in beaker and stirred evenly, top suspension is extracted after staticly settling 2h,
Into suspension add in 25g sodium pyrophosphate dispersants, stir 1.5h after, standing sedimentation 3h, add in 30ml 0.5mol/L it is dilute
Hydrochloric acid elutes, and filters, the calcium-base bentonite suspension purified;
(2) the calcium-base bentonite suspension and water that are obtained in step (1) are added in beaker, adding mass fraction is
Then 15% sodium fluoride, high-speed stirred 2h at 80 DEG C of water-bath separate, wash, is dry, obtaining sodium bentonite suspension.
(3) the sodium bentonite suspension and water that are obtained in step (2) are added in beaker, it is quick to stir, it has added
20ml cetyl trimethylammonium bromides/dilute hydrochloric acid mixed liquor, 85 DEG C of heating water bath stir 1h, stand 48h and then filter, wash
It washs, is dried in vacuo at 90 DEG C, obtains organobentonite.
2. organobentonite/composite modified epoxy resin E-39 aqueous polyurethane emulsion
(1) 23.21g PolyTHFs are added in the 500mL three-necked flasks that agitating device, thermometer are housed at one successively
Then (molecular weight 1000), 13.56g norbornene alkyl diisocyanate g add in 0.2g dibutyl tin laurates, speed of agitator
For 300r/min, 90 DEG C are to slowly warm up to, reacts 2h;
(2) 70 DEG C are cooled to, adds in 3g dimethylolpropionic acids, reacts 2h;
(3) 80 DEG C are warming up to, adds in 1.42g diglycols, reacts 1h;
(4) it is 80 DEG C to keep temperature, adds in the pentaerythrite of 2g, reacts 2h;
(5) it is 80 DEG C to keep temperature, adds in 2g organobentonites and 1.5g epoxy resin E-39, reacts 2h;
(6) 25 DEG C are cooled to, adds in 3.11g triethylamines, during which adding in 15ml acetone reduces viscosity, stirs 1h, obtains pre-
Polymers;
(7) 150g deionized waters are added in, agitator speed is adjusted into 1800r/min, keep temperature stabilization at 25 DEG C, fully
Stir 1h;
(8) 1h is evaporated under reduced pressure under conditions of temperature is 45 DEG C, vacuum degree is 0.06MPa, acetone is removed, filters and wrap
Fill the aqueous polyurethane emulsion to get organobentonite/composite modified epoxy resin E-39.
Comparative example 5:The aqueous polyurethane emulsion of organobentonite/composite modified epoxy resin E-51
1. prepared by bentonite
(1) 20g bentonites are added in 180g water in beaker and stirred evenly, top suspension is extracted after staticly settling 2h,
Into suspension add in 25g sodium pyrophosphate dispersants, stir 1.5h after, standing sedimentation 3h, add in 30ml 0.5mol/L it is dilute
Hydrochloric acid elutes, and filters, the calcium-base bentonite suspension purified;
(2) the calcium-base bentonite suspension and water that are obtained in step (1) are added in beaker, adding mass fraction is
Then 15% sodium fluoride, high-speed stirred 2h at 80 DEG C of water-bath separate, wash, is dry, obtaining sodium bentonite suspension.
(3) the sodium bentonite suspension and water that are obtained in step (2) are added in beaker, it is quick to stir, it has added
20ml cetyl trimethylammonium bromides/dilute hydrochloric acid mixed liquor, 85 DEG C of heating water bath stir 1h, stand 48h and then filter, wash
It washs, is dried in vacuo at 90 DEG C, obtains organobentonite.
2. organobentonite/composite modified epoxy resin E-51 aqueous polyurethane emulsion
(1) 21.98g PolyTHFs are added in the 500mL three-necked flasks that agitating device, thermometer are housed at one successively
In (molecular weight 1000), 14.57g norbornene alkyl diisocyanates, 0.2g dibutyl tin laurates, speed of agitator are then added in
For 300r/min, 90 DEG C are to slowly warm up to, reacts 2h;
(2) 70 DEG C are cooled to, adds in 3g dimethylolpropionic acids, reacts 2h;
(3) 80 DEG C are warming up to, adds in 1.64g diglycols, reacts 1h;
(4) it is 80 DEG C to keep temperature, adds in the pentaerythrite of 2g, reacts 2h;
(5) it is 80 DEG C to keep temperature, adds in 2g organobentonites and 1.5g epoxy resin E-51, reacts 2h;
(6) 25 DEG C are cooled to, adds in 3.11g triethylamines, during which adding in 15ml acetone reduces viscosity, stirs 1h, obtains pre-
Polymers;
(7) 150g deionized waters are added in, agitator speed is adjusted into 1800r/min, keep temperature stabilization at 25 DEG C, fully
Stir 1h;
(8) 1h is evaporated under reduced pressure under conditions of temperature is 45 DEG C, vacuum degree is 0.06MPa, acetone is removed, filters and wrap
Fill the aqueous polyurethane emulsion to get organobentonite/composite modified epoxy resin E-51.
Comparative example 6:The composite modified aqueous polyurethane emulsion of organobentonite/epoxy resin E-44
1. prepared by bentonite
(1) 20g bentonites are added in 180g water in beaker and stirred evenly, top suspension is extracted after staticly settling 2h,
Into suspension add in 25g sodium pyrophosphate dispersants, stir 1.5h after, standing sedimentation 3h, add in 30ml 0.5mol/L it is dilute
Hydrochloric acid elutes, and filters, the calcium-base bentonite suspension purified;
(2) the calcium-base bentonite suspension and water that are obtained in step (1) are added in beaker, adding mass fraction is
Then 15% sodium fluoride, high-speed stirred 2h at 80 DEG C of water-bath separate, wash, is dry, obtaining sodium bentonite suspension.
(3) the sodium bentonite suspension and water that are obtained in step (2) are added in beaker, it is quick to stir, it has added
20ml cetyl trimethylammonium bromides/dilute hydrochloric acid mixed liquor, 85 DEG C of heating water bath stir 1h, stand 48h and then filter, wash
It washs, is dried in vacuo at 90 DEG C, obtains organobentonite.
2. the composite modified aqueous polyurethane emulsion of organobentonite/epoxy resin E-44
(1) 22.10g PolyTHFs are added in the 500mL three-necked flasks that agitating device, thermometer are housed at one successively
(molecular weight 1000), 14.94g norbornene alkyl diisocyanates, then add in 0.2g dibutyl tin laurates, and speed of agitator is
300r/min is to slowly warm up to 90 DEG C, reacts 2h;
(2) 70 DEG C are cooled to, adds in 3g dimethylolpropionic acids, reacts 2h;
(3) 80 DEG C are warming up to, adds in 1.35g diglycols, reacts 1h;
(4) it is 80 DEG C to keep temperature, adds in the pentaerythrite of 2g, reacts 2h;
(5) it is 80 DEG C to keep temperature, adds in 1g organobentonites and 0.5g epoxy resin E-44s, reacts 2h;
(6) 25 DEG C are cooled to, adds in 3.11g triethylamines, during which adding in 15ml acetone reduces viscosity, stirs 1h, obtains pre-
Polymers;
(7) 150g deionized waters are added in, agitator speed is adjusted into 1800r/min, keep temperature stabilization at 25 DEG C, fully
Stir 1h;
(8) 1h is evaporated under reduced pressure under conditions of temperature is 45 DEG C, vacuum degree is 0.06MPa, acetone is removed, filters and wrap
Dress is to get the composite modified aqueous polyurethane emulsion of organobentonite/epoxy resin E-44.
Comparative example 7:The composite modified aqueous polyurethane emulsion of organobentonite/epoxy resin E-44
1. prepared by bentonite
(1) 20g bentonites are added in 180g water in beaker and stirred evenly, top suspension is extracted after staticly settling 2h,
Into suspension add in 25g sodium pyrophosphate dispersants, stir 1.5h after, standing sedimentation 3h, add in 30ml 0.5mol/L it is dilute
Hydrochloric acid elutes, and filters, the calcium-base bentonite suspension purified;
(2) the calcium-base bentonite suspension and water that are obtained in step (1) are added in beaker, adding mass fraction is
Then 15% sodium fluoride, high-speed stirred 2h at 80 DEG C of water-bath separate, wash, is dry, obtaining sodium bentonite suspension.
(3) the sodium bentonite suspension and water that are obtained in step (2) are added in beaker, it is quick to stir, it has added
20ml cetyl trimethylammonium bromides/dilute hydrochloric acid mixed liquor, 85 DEG C of heating water bath stir 1h, stand 48h and then filter, wash
It washs, is dried in vacuo at 90 DEG C, obtains organobentonite.
2. the composite modified aqueous polyurethane emulsion of organobentonite/epoxy resin E-44
(1) 22.10g PolyTHFs are added in the 500mL three-necked flasks that agitating device, thermometer are housed at one successively
(molecular weight 1000), 14.94g norbornene alkyl diisocyanates, then add in 0.2g dibutyl tin laurates, and speed of agitator is
300r/min is to slowly warm up to 90 DEG C, reacts 2h;
(2) 70 DEG C are cooled to, adds in 3g dimethylolpropionic acids, reacts 2h;
(3) 80 DEG C are warming up to, adds in 1.35g diglycols, reacts 1h;
(4) it is 80 DEG C to keep temperature, adds in the pentaerythrite of 2g, reacts 2h;
(5) it is 80 DEG C to keep temperature, adds in 3g organobentonites and 3g epoxy resin E-44s, reacts 2h;
(6) 25 DEG C are cooled to, adds in 3.11g triethylamines, during which adding in 15ml acetone reduces viscosity, stirs 1h, obtains pre-
Polymers;
(7) 150g deionized waters are added in, agitator speed is adjusted into 1800r/min, keep temperature stabilization at 25 DEG C, fully
Stir 1h;
(8) 1h is evaporated under reduced pressure under conditions of temperature is 45 DEG C, vacuum degree is 0.06MPa, acetone is removed, filters and wrap
Dress is to get the composite modified aqueous polyurethane emulsion of organobentonite/epoxy resin E-44.
Embodiment 1:The composite modified aqueous polyurethane emulsion of organobentonite/epoxy resin E-44
1. prepared by bentonite
(1) 20g bentonites are added in 180g water in beaker and stirred evenly, top suspension is extracted after staticly settling 2h,
Into suspension add in 25g sodium pyrophosphate dispersants, stir 1.5h after, standing sedimentation 3h, add in 30ml 0.5mol/L it is dilute
Hydrochloric acid elutes, and filters, the calcium-base bentonite suspension purified;
(2) the calcium-base bentonite suspension and water that are obtained in step (1) are added in beaker, adding mass fraction is
Then 15% sodium fluoride, high-speed stirred 2h at 80 DEG C of water-bath separate, wash, is dry, obtaining sodium bentonite suspension.
(3) the sodium bentonite suspension and water that are obtained in step (2) are added in beaker, it is quick to stir, it has added
20ml cetyl trimethylammonium bromides/dilute hydrochloric acid mixed liquor, 85 DEG C of heating water bath stir 1h, stand 48h and then filter, wash
It washs, is dried in vacuo at 90 DEG C, obtains organobentonite.
2. the composite modified aqueous polyurethane emulsion of organobentonite/epoxy resin E-44
(1) 22.10g PolyTHFs are added in the 500mL three-necked flasks that agitating device, thermometer are housed at one successively
(molecular weight 1000), 14.94g norbornene alkyl diisocyanates, then add in 0.2g dibutyl tin laurates, and speed of agitator is
300r/min is to slowly warm up to 90 DEG C, reacts 2h;
(2) 70 DEG C are cooled to, adds in 3g dimethylolpropionic acids, reacts 2h;
(3) 80 DEG C are warming up to, adds in 1.35g diglycols, reacts 1h;
(4) it is 80 DEG C to keep temperature, adds in the pentaerythrite of 2g, reacts 2h;
(5) it is 80 DEG C to keep temperature, adds in 1.5g organobentonites and 1g epoxy resin E-44s, reacts 2h;
(6) 25 DEG C are cooled to, adds in 3.11g triethylamines, during which adding in 15ml acetone reduces viscosity, stirs 1h, obtains pre-
Polymers;
(7) 150g deionized waters are added in, agitator speed is adjusted into 1800r/min, keep temperature stabilization at 25 DEG C, fully
Stir 1h;
(8) 1h is evaporated under reduced pressure under conditions of temperature is 45 DEG C, vacuum degree is 0.06MPa, acetone is removed, filters and wrap
Dress is to get the composite modified aqueous polyurethane emulsion of organobentonite/epoxy resin E-44.
Embodiment 2:The composite modified aqueous polyurethane emulsion of organobentonite/epoxy resin E-44
1. prepared by bentonite
(1) 20g bentonites are added in 180g water in beaker and stirred evenly, top suspension is extracted after staticly settling 2h,
Into suspension add in 25g sodium pyrophosphate dispersants, stir 1.5h after, standing sedimentation 3h, add in 30ml 0.5mol/L it is dilute
Hydrochloric acid elutes, and filters, the calcium-base bentonite suspension purified;
(2) the calcium-base bentonite suspension and water that are obtained in step (1) are added in beaker, adding mass fraction is
Then 15% sodium fluoride, high-speed stirred 2h at 80 DEG C of water-bath separate, wash, is dry, obtaining sodium bentonite suspension.
(3) the sodium bentonite suspension and water that are obtained in step (2) are added in beaker, it is quick to stir, it has added
20ml cetyl trimethylammonium bromides/dilute hydrochloric acid mixed liquor, 85 DEG C of heating water bath stir 1h, stand 48h and then filter, wash
It washs, is dried in vacuo at 90 DEG C, obtains organobentonite.
2. the composite modified aqueous polyurethane emulsion of organobentonite/epoxy resin E-44
(1) 22.10g PolyTHFs are added in the 500mL three-necked flasks that agitating device, thermometer are housed at one successively
Then (molecular weight 1000), 14.94g norbornene alkyl diisocyanate g add in 0.2g dibutyl tin laurates, speed of agitator
For 300r/min, 90 DEG C are to slowly warm up to, reacts 2h;
(2) 70 DEG C are cooled to, adds in 3g dimethylolpropionic acids, reacts 2h;
(3) 80 DEG C are warming up to, adds in 1.35g diglycols, reacts 1h;
(4) it is 80 DEG C to keep temperature, adds in the pentaerythrite of 2g, reacts 2h;
(5) it is 80 DEG C to keep temperature, adds in 2g organobentonites and 1.5g epoxy resin E-44s, reacts 2h;
(6) 25 DEG C are cooled to, adds in 3.11g triethylamines, during which adding in 15ml acetone reduces viscosity, stirs 1h, obtains pre-
Polymers;
(7) 150g deionized waters are added in, agitator speed is adjusted into 1800r/min, keep temperature stabilization at 25 DEG C, fully
Stir 1h;
(8) 1h is evaporated under reduced pressure under conditions of temperature is 45 DEG C, vacuum degree is 0.06MPa, acetone is removed, filters and wrap
Dress is to get the composite modified aqueous polyurethane emulsion of organobentonite/epoxy resin E-44.
Embodiment 3:The composite modified aqueous polyurethane emulsion of organobentonite/epoxy resin E-44
1. prepared by bentonite
(1) 20g bentonites are added in 180g water in beaker and stirred evenly, top suspension is extracted after staticly settling 2h,
Into suspension add in 25g sodium pyrophosphate dispersants, stir 1.5h after, standing sedimentation 3h, add in 30ml 0.5mol/L it is dilute
Hydrochloric acid elutes, and filters, the calcium-base bentonite suspension purified;
(2) the calcium-base bentonite suspension and water that are obtained in step (1) are added in beaker, adding mass fraction is
Then 15% sodium fluoride, high-speed stirred 2h at 80 DEG C of water-bath separate, wash, is dry, obtaining sodium bentonite suspension.
(3) the sodium bentonite suspension and water that are obtained in step (2) are added in beaker, it is quick to stir, it has added
20ml cetyl trimethylammonium bromides/dilute hydrochloric acid mixed liquor, 85 DEG C of heating water bath stir 1h, stand 48h and then filter, wash
It washs, is dried in vacuo at 90 DEG C, obtains organobentonite.
2. the composite modified aqueous polyurethane emulsion of organobentonite/epoxy resin E-44
(1) 22.10g PolyTHFs are added in the 500mL three-necked flasks that agitating device, thermometer are housed at one successively
Then (molecular weight 1000), 14.94g norbornene alkyl diisocyanate g add in 0.2g dibutyl tin laurates, speed of agitator
For 300r/min, 90 DEG C are to slowly warm up to, reacts 2h;
(2) 70 DEG C are cooled to, adds in 3g dimethylolpropionic acids, reacts 2h;
(3) 80 DEG C are warming up to, adds in 1.35g diglycols, reacts 1h;
(4) it is 80 DEG C to keep temperature, adds in the pentaerythrite of 2g, reacts 2h;
(5) it is 80 DEG C to keep temperature, adds in 2.5g organobentonites and 1.5g epoxy resin E-44s, reacts 2h;
(6) 25 DEG C are cooled to, adds in 3.11g triethylamines, during which adding in 15ml acetone reduces viscosity, stirs 1h, obtains pre-
Polymers;
(7) 150g deionized waters are added in, agitator speed is adjusted into 1800r/min, keep temperature stabilization at 25 DEG C, fully
Stir 1h;
(8) 1h is evaporated under reduced pressure under conditions of temperature is 45 DEG C, vacuum degree is 0.06MPa, acetone is removed, filters and wrap
Dress is to get the composite modified aqueous polyurethane emulsion of organobentonite/epoxy resin E-44.
Embodiment 4:The composite modified aqueous polyurethane emulsion of organobentonite/epoxy resin E-44
1. prepared by bentonite
(1) 20g bentonites are added in 180g water in beaker and stirred evenly, top suspension is extracted after staticly settling 2h,
Into suspension add in 25g sodium pyrophosphate dispersants, stir 1.5h after, standing sedimentation 3h, add in 30ml 0.5mol/L it is dilute
Hydrochloric acid elutes, and filters, the calcium-base bentonite suspension purified;
(2) the calcium-base bentonite suspension and water that are obtained in step (1) are added in beaker, adding mass fraction is
Then 15% sodium fluoride, high-speed stirred 2h at 80 DEG C of water-bath separate, wash, is dry, obtaining sodium bentonite suspension.
(3) the sodium bentonite suspension and water that are obtained in step (2) are added in beaker, it is quick to stir, it has added
20ml cetyl trimethylammonium bromides/dilute hydrochloric acid mixed liquor, 85 DEG C of heating water bath stir 1h, stand 48h and then filter, wash
It washs, is dried in vacuo at 90 DEG C, obtains organobentonite.
2. the composite modified aqueous polyurethane emulsion of organobentonite/epoxy resin E-44
(1) 22.10g PolyTHFs are added in the 500mL three-necked flasks that agitating device, thermometer are housed at one successively
Then (molecular weight 1000), 14.94g norbornene alkyl diisocyanate g add in 0.2g dibutyl tin laurates, speed of agitator
For 300r/min, 90 DEG C are to slowly warm up to, reacts 2h;
(2) 70 DEG C are cooled to, adds in 3g dimethylolpropionic acids, reacts 2h;
(3) 80 DEG C are warming up to, adds in 1.35g diglycols, reacts 1h;
(4) it is 80 DEG C to keep temperature, adds in the pentaerythrite of 2g, reacts 2h;
(5) it is 80 DEG C to keep temperature, adds in 2.5g organobentonites and 2.5g epoxy resin E-44s, reacts 2h;
(6) 25 DEG C are cooled to, adds in 3.11g triethylamines, during which adding in 15ml acetone reduces viscosity, stirs 1h, obtains pre-
Polymers;
(7) 150g deionized waters are added in, agitator speed is adjusted into 1800r/min, keep temperature stabilization at 25 DEG C, fully
Stir 1h;
(8) 1h is evaporated under reduced pressure under conditions of temperature is 45 DEG C, vacuum degree is 0.06MPa, acetone is removed, filters and wrap
Dress is to get the composite modified aqueous polyurethane emulsion of organobentonite/epoxy resin E-44.
The performance of aqueous polyurethane emulsion is as shown in the table made from above-mentioned each comparative example and embodiment.Tensile strength connects
Feeler and pencil hardness be take a certain amount of lotion form a film on polyfluortetraethylene plate after test obtained by, table medium viscosity is to water
The test value of property polyaminoester emulsion.
Table 1:The performance test table of each comparative example and embodiment
As can be seen from the above table, have after the composite modified aqueous polyurethane film forming of organobentonite/epoxy resin E-44
Excellent mechanical property, tensile strength can reach 66.72MPa, and hardness and viscosity are larger, are easy to form a film and preserve, and adhesive force is most
Height can reach 0 grade, and emulsion intercalation method is greatly improved, and can store 9 months or more, comprehensive performance is substantially carried
Height, and the type aqueous polyurethane emulsion can reduce the pollution to environment and ensure the health of worker without organic solvent.
Claims (9)
1. the preparation method of organobentonite/epoxy resin composite modified water polyurethane emulsion, which is characterized in that including as follows
Step:
Step 1, prepared by bentonite:Bentonite with water is mixed, is stirred evenly, extracts suspension, adds in sodium pyrophosphate
Dispersant, standing sedimentation, the dilute hydrochloric acid for adding in 0.5mol/L~1mol/L elutes, and at 60~90 DEG C, adding in mass fraction is
10%~15% Fluorinse is sirred and separated, and at 70~90 DEG C, adds in the reagent/dilute hydrochloric acid mixed liquor that organises, and is filtered dry
It is dry, obtain organobentonite;
Step 2, the preparation of organobentonite/epoxy resin composite modified water polyurethane emulsion:
(A) it is 1200~2600 in mass ratio by oligomer dihydric alcohol and diisocyanate:500~1500 are uniformly mixed, and add in
Catalyst, speed of agitator are 200~300r/min, are to slowly warm up to 80~90 DEG C, the first intermediate is obtained by the reaction;
(B) the first intermediate is cooled to 70~80 DEG C, adds in dry multi-hydroxy carboxy acid, reacts 2~3h, obtains among second
Body;
(C) the second intermediate is warming up to 80~90 DEG C, adds in small molecule glycol monomer, reacts 1~2h, obtains among the 3rd
Body;
(D) it is 80~90 DEG C that the 3rd intermediate, which keeps temperature, adds in trimethylolpropane crosslinking agent, reacts 2~3h, obtain the 4th
Intermediate;
(E) the 4th intermediate keep temperature be 80~90 DEG C, with oligomer dihydric alcohol, diisocyanate, multi-hydroxy carboxy acid, small point
The gross mass of sub- glycol monomer and trimethylolpropane crosslinking agent is total amount, is 3 by organobentonite and the mass ratio of total amount
~5:100, the mass ratio of epoxy resin and total amount is 2~5:100, add in organobentonite and epoxy resin E-44, reaction 2~
3h obtains the 5th intermediate;
(F) the 5th intermediate is cooled to 20~30 DEG C, and triethylamine is added under stirring and is neutralized into salt, during which adds in acetone drop
Low viscosity to solution is in colourless, when reaction 0.5~1 is small, obtains the 6th intermediate;
(G) the 6th intermediate adds water high speed shearing emulsification, and shear velocity control is 20 in 1800~2000r/min, holding temperature
~30 DEG C, be sufficiently stirred 0.5~1 it is small when, obtain the 7th intermediate;
(H) the 7th intermediate is evaporated under reduced pressure 1~2h under conditions of temperature is 35~45 DEG C, vacuum degree is 0.04~0.08MPa,
Acetone is removed, filters and packs to get the composite modified aqueous polyurethane emulsion of organobentonite/epoxy resin.
2. preparation method according to claim 1, which is characterized in that in step 1, the mass ratio of the bentonite and water
For 1:4~9.
3. preparation method according to claim 1, which is characterized in that in step 1, the reagent that organises is selected from 16
Alkyl trimethyl ammonium bromide, hexadecyltrimethylammonium chloride, octadecyl dimethyl benzyl ammonium chloride, double hexadecyldimethylamines
Ammonium chloride or double stearyl dimethyl benzyl ammonium chlorides, the molar ratio of described organise reagent and dilute hydrochloric acid is 1:1.
4. preparation method according to claim 1, which is characterized in that in step 2 (A), the oligomer dihydric alcohol is
Polyether Glycols or polyester diol.
5. preparation method according to claim 4, which is characterized in that the polyether Glycols use molecular weight as 1000
Combination more than one or both of~3000 polypropylene glycol, polyethylene glycol and polytetrahydrofuran diol, the polyester
Dihydric alcohol use molecular weight for 1000~4000 adipate polyester dihydric alcohol, polyhexamethylene adipate glycol, makrolon
One or more in dihydric alcohol, polycaprolactone diols.
6. preparation method according to claim 1, which is characterized in that in step 2 (A), the diisocyanate is drop
Bornylane diisocyanate, tetramethyl m-xylylene diisocyanate, dicyclohexyl methyl hydride diisocyanate, dimethyl two
Phenyl diisocyanate, diphenyl-methane -4, the one or more in 4 '-diisocyanate.
7. preparation method according to claim 1, which is characterized in that in step 2 (A), the catalyst is two bays
Sour dibutyl tin, stannous octoate, the one or more of dibutyltin diacetate.
8. preparation method according to claim 1, which is characterized in that in step 2 (B), the multi-hydroxy carboxy acid is two
One or more in hydroxymethyl propionic acid (DMPA), dimethylolpropionic acid (DMBA).
9. preparation method according to claim 1, which is characterized in that in step 2 (C), the small molecule dihydric alcohol list
Body is selected from 1,4-butanediol, diglycol, trimethylpentanediol, methyl propanediol, 1,6- hexylene glycols or neopentyl glycol
It is one or more.
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Cited By (2)
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CN109135530A (en) * | 2018-07-03 | 2019-01-04 | 南京理工大学 | DAPBI modified aqueous polyurethane coating and preparation method thereof |
CN114213959A (en) * | 2021-08-05 | 2022-03-22 | 武汉思诺富宏科技有限公司 | Antistatic coating liquid and preparation method and application thereof |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6162863A (en) * | 1997-12-04 | 2000-12-19 | Henkel Kommanditgesellschaft Auf Aktien | Waterborne polyurethanes with urea-urethane linkages |
CN105367743A (en) * | 2015-12-21 | 2016-03-02 | 中国科学院山西煤炭化学研究所 | Synthetic method of waterborne polyurethane emulsion |
CN105820735A (en) * | 2016-04-28 | 2016-08-03 | 宿州市众力保温节能材料有限公司 | Water-based polyurethane modified epoxy resin environment-friendly paint and preparation method thereof |
CN106634282A (en) * | 2016-12-28 | 2017-05-10 | 郑州圣莱特空心微珠新材料有限公司 | Heat preservation energy-saving coating applied to interior walls and preparation method thereof |
-
2018
- 2018-01-22 CN CN201810060746.XA patent/CN108102349B/en active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6162863A (en) * | 1997-12-04 | 2000-12-19 | Henkel Kommanditgesellschaft Auf Aktien | Waterborne polyurethanes with urea-urethane linkages |
CN105367743A (en) * | 2015-12-21 | 2016-03-02 | 中国科学院山西煤炭化学研究所 | Synthetic method of waterborne polyurethane emulsion |
CN105820735A (en) * | 2016-04-28 | 2016-08-03 | 宿州市众力保温节能材料有限公司 | Water-based polyurethane modified epoxy resin environment-friendly paint and preparation method thereof |
CN106634282A (en) * | 2016-12-28 | 2017-05-10 | 郑州圣莱特空心微珠新材料有限公司 | Heat preservation energy-saving coating applied to interior walls and preparation method thereof |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109135530A (en) * | 2018-07-03 | 2019-01-04 | 南京理工大学 | DAPBI modified aqueous polyurethane coating and preparation method thereof |
CN109135530B (en) * | 2018-07-03 | 2020-06-19 | 南京理工大学 | DAPBI modified waterborne polyurethane coating and preparation method thereof |
CN114213959A (en) * | 2021-08-05 | 2022-03-22 | 武汉思诺富宏科技有限公司 | Antistatic coating liquid and preparation method and application thereof |
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