CN105504781A - Polyurethane asphalt composite emulsion and use method thereof - Google Patents
Polyurethane asphalt composite emulsion and use method thereof Download PDFInfo
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- CN105504781A CN105504781A CN201610067582.4A CN201610067582A CN105504781A CN 105504781 A CN105504781 A CN 105504781A CN 201610067582 A CN201610067582 A CN 201610067582A CN 105504781 A CN105504781 A CN 105504781A
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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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2495/00—Bituminous materials, e.g. asphalt, tar or pitch
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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
- C08L2201/00—Properties
- C08L2201/56—Non-aqueous solutions or dispersions
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Paints Or Removers (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to the field of preparation and application of composite materials, in particular to polyurethane asphalt composite emulsion and a use method thereof. The polyurethane asphalt composite emulsion is prepared from components A, B and C; the component A is polyurethane prepolymer emulsion; the component B is mixed emulsion of petroleum asphalt, fatty acid ethyl ester, carbodiimide, triethylene diamine, light calcium carbonate and a plasticizer; the component C is a mixed solution of a quaternary ammonium salt surfactant and low mass molecule alcohol. In the preparation and implementation processes, no organic solvents are used; meanwhile, the petroleum asphalt is low in toxicity and has small influence on the environment and the health of human; furthermore, the composite emulsion disclosed by the invention and a construction method thereof are higher in applicability to a base material, have a low requirement on the drying performance of the base material, and can be used in irregular surfaces. The method can promote rapid breakage of the composite emulsion, quick precipitation of particles and generation of crosslinking solidification, so that a composite coating film with high intensity, high low-temperature toughness and high watertightness can be obtained.
Description
Technical field
The present invention relates to the preparation and application field of matrix material, specifically a kind of polyurethane asphalt composite emulsion and using method thereof.
Background technology
In recent years, water-borne coatings, owing to having good environment friendly, surperficial adaptability and working security etc., more and more comes into one's own in paint field.Double-component polyurethane coating as the one of water-borne coatings, its film-forming temperature is low, sticking power compared with strong, wear resistance is better, hardness is large, chemical resistant properties and weathering resistance better, become an important development direction of water-borne coatings.But the curing speed of aqueous polyurethane coating is comparatively slow, its surface drying and the time of doing solid work longer, operating efficiency is reduced, and the duration is longer, and shaping before be easily damaged.Therefore, improve de-emulsification speed and the rate of crosslinking of polyaminoester emulsion, shorten its surface drying and do solid work the time, making it form the film of high strength, high-flexibility and high watertightness fast, become the research direction that has very large practical significance.
Creaming of emulsion has following method usually:
(1) temperature variation breakdown of emulsion is utilized, as carried out heating and cooling repeatedly to emulsion.Heating energy changes the solubility property of tensio-active agent, makes emulsion loss of stability and breakdown of emulsion.
(2) External Force Acting breakdown of emulsion is utilized, as applied centrifugal force to emulsion.Centrifugal force is formed and collides and shear between emulsified particle, promotes the layering of particle and coalescent and breakdown of emulsion.
(3) impressed voltage breakdown of emulsion is utilized, as applied direct current or voltage of alternating current to emulsion.Under voltage effect, emulsion generation electrophoretic action, emulsified particle can adhere to electrode and breakdown of emulsion occur.
(4) by adding emulsion splitter breakdown of emulsion, as added ionogen to emulsion.In the charged particle energy that ionogen ionization produces and emulsion particle surface electrical, destroy double electrical layers, particle because repulsive force reduces near and coalescent, finally cause breakdown of emulsion.
Visible, normal temperature and without external force when, polyaminoester emulsion can by add emulsion splitter realize fast emulsion breaking, there is crosslinked action simultaneously, flocculate and be deposited in substrate surface, become the film with certain use properties.
Summary of the invention
The object of the invention is, for above-mentioned technology Problems existing, to provide a kind of rapid hardening method of polyurethane asphalt composite emulsion.
For achieving the above object, the technical solution used in the present invention is: a kind of polyurethane asphalt composite emulsion, is prepared from by A, B and component C, and described component A is polyurethane prepolymer precursor emulsion; Described B component is the mixed emulsion of petroleum pitch, fatty-acid ethyl ester, carbodiimide, triethylene diamine, light calcium carbonate and softening agent; Described component C is the mixing solutions of quaternary ammonium salt cationic surfactant and low mass molecule alcohol.
Further, in described component A, the massfraction of base polyurethane prepolymer for use as is 30 ~ 50%; In described B component, the massfraction of pitch is 40 ~ 60%; The massfraction of fatty-acid ethyl ester is 5 ~ 10%; The massfraction of carbodiimide is 5 ~ 10%; Light calcium carbonate massfraction is 10 ~ 15%; The massfraction of softening agent is 5 ~ 15%; The massfraction of triethylene diamine is 5 ~ 8%; The massfraction of water is 5 ~ 10%; In described component C, the massfraction of quaternary ammonium salt is 40 ~ 60%; The massfraction of low mass molecule alcohol is 20 ~ 30%.
Further, described polyurethane prepolymer precursor emulsion is carboxylic acid type urethane; The particle dia of described petroleum pitch emulsion is not more than 5 μm, and solid content is 30 ~ 50%; Described fatty-acid ethyl ester is the long chain fatty acid ester class that carbonatoms is not less than 6, and the solid content of described carbodiimide emulsion is 30 ~ 60%, and pH value is 9 ~ 11; Described softening agent is polyvinyl butyral acetal or liquid polyisoprene; Described quaternary ammonium salt cationic surfactant is that tetradecyl trimethyl ammonium chloride is or/and Timbercote 2000; Described low mass molecule alcohol is water-soluble alcohol.
Further, described long chain fatty acid ester is that ethyl hexanoate is or/and ethyl propyl ethyl acetate.
Further, described water-soluble alcohol is that methyl alcohol, ethanol are or/and propyl alcohol.
Another object of the present invention is to provide a kind of using method of polyurethane asphalt composite emulsion, prepares A, B respectively and component C is for subsequent use; B component and component A obtain mixed solution for 3:1 ~ 2:1 in mass ratio; Then deposit mixed solution in a rifle, in another rifle, deposit component C, adopt rush-harvesting and rush-planting spraying method coating thickness to be about 5mm.
Further, during described spraying, the spray volume of component C is 5 ~ 10% of composite emulsion quality.
Further, time prepared by described B component, stirring velocity is 30 ~ 50r/min, time 20 ~ 40min.
Further, time prepared by described mixed solution, stirring velocity is 10 ~ 30r/min.
Side of the present invention separates: in view of promoting the breakdown of emulsion of aqueous polyurethane coating and being cross-linked, shorten its molding time and have major and immediate significance, the present invention adopts the mixing solutions of quaternary ammonium salt surface active agent and low mass molecule alcohol as combinational demulsifier, and various ingredients is added in system, to promote its breakdown of emulsion, to be cross-linked, and the physicals of General Promotion film.The present invention adopts carboxylic acid type polyurethane prepolymer emulsion, its emulsion particle surface electronegative.After quaternary ammonium salt dissolves, produce and strong strive water effect, and ionization produces cationic species, in energy and the negative electricity of particle surface, destroy electrostatic double layer, close to each other and coalescent due to the reduction of electric repulsion between particle.And the existence of low mass molecule alcohol, can change phase polarity, oil phase polarity is increased, aqueous phase polarity reduces, and destroys emulsion intercalation method further, promotes breakdown of emulsion.Add asphalt component in polyaminoester emulsion, rely on the effect of fatty-acid ethyl ester to form uniform and stable mixed emulsion, the water resistance of film can be promoted.The mobility adding raising emulsion of softening agent, reduces second-order transition temperature, obtains the good film of elasticity after making it ambient temperature curing.The existence of carbodiimide, namely crosslinking reaction occurs after making particle breakdown of emulsion, base polyurethane prepolymer for use as is polymerized further, solidifies and precipitates film forming.Triethylene diamine promotes solidification, and reduces the consumption of carbodiimide.Through above-mentioned breakdown of emulsion, cross-linking process, the base polyurethane prepolymer for use as in urethane/pitch composite emulsion is polymerized further and is cross-linked to form the good film of physical and mechanical properties, and asphalt component is uniform and stable distribution in film.And adding of light calcium carbonate, both can reduce costs, improve liquidity and thixotropy, also can serve as body frame material and improve film-forming properties and resistance to blade coating.Visible, the method that the present invention uses, can not only promote the breakdown of emulsion of urethane/pitch composite emulsion greatly, shortens its surface drying and does solid work the time, and obtained compelx coating has good over-all properties, and use value is higher.
Advantageous Effects of the present invention is:
(1) preparation of the present invention and implementation process, not with an organic solvent, and petroleum pitch toxicity is little, to environment and Human health effects little, and composite emulsion of the present invention and constructional method thereof are to the adaptability of base material better, less demanding to the drying property of base material, and can be used for irregularity surface.
(2) the method applied in the present invention, can make fast emulsion breaking under composite emulsion normal temperature, be cross-linked and film forming of flocculating, and substantially reduce the surface drying time of water-borne coatings and do solid work the time, operating efficiency improves greatly.
(3) pitch itself is not containing active group, and do not participate in the curing reaction of urethane, make the molecular structure after curing of coating more regular, physicochemical property are more stable.And pitch can stop the hydrophilic radical in urethane to be hydrolyzed, thus make the compelx coating water tolerance that obtains better, working life increases.After tested, compelx coating is applied to the pressure of 0.3MPa, effect 120min, waterproof.
(4) compelx coating that obtains of the present invention, second-order transition temperature is low, is still in elastomeric state under low temperature, and low-temperature bending is better.After tested, at-35 DEG C, film flawless, seam dynamic deformation tests 10000 times, film flawless.
(5) compelx coating that obtains of the present invention, have good comprehensive physical mechanical property, the most high energy of tensile strength reaches 6.8MPa, and tear strength is the highest close to 26N/mm, and elongation at break is more than 450%.
Embodiment
Below in conjunction with the embodiment of the present invention, be clearly and completely described the technical scheme in the embodiment of the present invention, obviously, described embodiment is only the present invention's part embodiment, instead of whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art, not making the every other embodiment obtained under creative work prerequisite, belong to the scope of protection of the invention.
Embodiment 1
First the preparation of B component is carried out: petroleum pitch, light calcium carbonate and polyvinyl butyral acetal are mixed in proportion, add ethyl hexanoate, carbodiimide and triethylene diamine simultaneously, stir 30min with the speed of 40r/min, form uniform and stable mixed emulsion.The massfraction of each component shared by B component is: pitch 60%; Ethyl hexanoate 10%; Carbodiimide 5%; Light calcium carbonate 10%; Polyvinyl butyral acetal 5%; Triethylene diamine 5%; Water 5%.
Then carry out the preparation of component C: the massfraction of tetradecyl trimethyl ammonium chloride is 60%, the massfraction of propyl alcohol is 30%.
Carry out the preparation of urethane/pitch composite emulsion before construction: by solid content be 40% component A and B component in mass ratio 2:1 mix, and stir 15min with the speed of 20r/min, for spraying.
Spraying application: adopt rush-harvesting and rush-planting spraying method, the spray volume of component C is 10% of composite emulsion quality, and coating thickness is about 5mm.
Embodiment 2
First the preparation of B component is carried out: petroleum pitch, light calcium carbonate and polyvinyl butyral acetal are mixed in proportion, add ethyl hexanoate, carbodiimide and triethylene diamine simultaneously, stir 30min with the speed of 40r/min, form uniform and stable mixed emulsion.The massfraction of each component shared by B component is: pitch 50%; Ethyl hexanoate 5%; Carbodiimide 5%; Light calcium carbonate 15%; Polyvinyl butyral acetal 15%; Triethylene diamine 5%; Water 5%.
Then carry out the preparation of component C: the massfraction of tetradecyl trimethyl ammonium chloride is 50%, the massfraction of propyl alcohol is 25%.
Carry out the preparation of urethane/pitch composite emulsion before construction: by solid content be 40% component A and B component in mass ratio 3:1 mix, and stir 15min with the speed of 20r/min, for spraying.
Spraying application: adopt rush-harvesting and rush-planting spraying method, the spray volume of component C is 10% of composite emulsion quality, and coating thickness is about 5mm.
Embodiment 3
First the preparation of B component is carried out: petroleum pitch, light calcium carbonate and polyvinyl butyral acetal are mixed in proportion, add ethyl hexanoate, carbodiimide and triethylene diamine simultaneously, stir 30min with the speed of 40r/min, form uniform and stable mixed emulsion.The massfraction of each component shared by B component is: pitch 55%; Ethyl hexanoate 10%; Carbodiimide 10%; Light calcium carbonate 10%; Polyvinyl butyral acetal 5%; Triethylene diamine 5%; Water 5%.
Then carry out the preparation of component C: the massfraction of tetradecyl trimethyl ammonium chloride is 40%, the massfraction of propyl alcohol is 20%.
Carry out the preparation of urethane/pitch composite emulsion before construction: by solid content be 40% component A and B component in mass ratio 5:2 mix, and stir 15min with the speed of 20r/min, for spraying.
Spraying application: adopt rush-harvesting and rush-planting spraying method, the spray volume of component C is 10% of composite emulsion quality, and coating thickness is about 5mm.
Embodiment 4
First the preparation of B component is carried out: petroleum pitch, light calcium carbonate and polyvinyl butyral acetal are mixed in proportion, add ethyl hexanoate, carbodiimide and triethylene diamine simultaneously, stir 30min with the speed of 40r/min, form uniform and stable mixed emulsion.The massfraction of each component shared by B component is: pitch 50%; Ethyl hexanoate 10%; Carbodiimide 10%; Light calcium carbonate 12%; Polyvinyl butyral acetal 5%; Triethylene diamine 8%; Water 5%.
Then carry out the preparation of component C: the massfraction of tetradecyl trimethyl ammonium chloride is 55%, the massfraction of propyl alcohol is 27.5%.
Carry out the preparation of urethane/pitch composite emulsion before construction: by solid content be 40% component A and B component in mass ratio 2:1 mix, and stir 15min with the speed of 20r/min, for spraying.
Spraying application: adopt rush-harvesting and rush-planting spraying method, the spray volume of component C is 10% of composite emulsion quality, and coating thickness is about 5mm.
Embodiment 5
First the preparation of B component is carried out: petroleum pitch, light calcium carbonate and polyvinyl butyral acetal are mixed in proportion, add ethyl hexanoate, carbodiimide and triethylene diamine simultaneously, stir 30min with the speed of 40r/min, form uniform and stable mixed emulsion.The massfraction of each component shared by B component is: pitch 45%; Ethyl hexanoate 10%; Carbodiimide 10%; Light calcium carbonate 15%; Polyvinyl butyral acetal 10%; Triethylene diamine 5%; Water 5%.
Then carry out the preparation of component C: the massfraction of tetradecyl trimethyl ammonium chloride is 45%, the massfraction of propyl alcohol is 22.5%.
Carry out the preparation of urethane/pitch composite emulsion before construction: by solid content be 40% component A and B component in mass ratio 3:1 mix, and stir 15min with the speed of 20r/min, for spraying.
Spraying application: adopt rush-harvesting and rush-planting spraying method, the spray volume of component C is 10% of composite emulsion quality, and coating thickness is about 5mm.
The rapid hardening effect recorded in conjunction with specific examples (substrate temperature is 25 DEG C) as shown in table 1.
The rapid hardening time of table 1. urethane/pitch composite emulsion
The painting film dynamic performance recorded in conjunction with specific examples is as shown in table 2.
The mechanical property of table 2. urethane/pitch compelx coating
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (9)
1. polyurethane asphalt composite emulsion, is prepared from by A, B and component C, it is characterized in that, described component A is polyurethane prepolymer precursor emulsion; Described B component is the mixed emulsion of petroleum pitch, fatty-acid ethyl ester, carbodiimide, triethylene diamine, light calcium carbonate and softening agent; Described component C is the mixing solutions of quaternary ammonium salt cationic surfactant and low mass molecule alcohol.
2. polyurethane asphalt composite emulsion according to claim 1, it is characterized in that: in described component A, the massfraction of base polyurethane prepolymer for use as is 30 ~ 50%; In described B component, the massfraction of pitch is 40 ~ 60%; The massfraction of fatty-acid ethyl ester is 5 ~ 10%; The massfraction of carbodiimide is 5 ~ 10%; Light calcium carbonate massfraction is 10 ~ 15%; The massfraction of softening agent is 5 ~ 15%; The massfraction of triethylene diamine is 5 ~ 8%; The massfraction of water is 5 ~ 10%; In described component C, the massfraction of quaternary ammonium salt is 40 ~ 60%; The massfraction of low mass molecule alcohol is 20 ~ 30%.
3. polyurethane asphalt composite emulsion according to claim 1, is characterized in that: described polyurethane prepolymer precursor emulsion is carboxylic acid type urethane; The particle dia of described petroleum pitch emulsion is not more than 5 μm, and solid content is 30 ~ 50%; Described fatty-acid ethyl ester is the long chain fatty acid ester class that carbonatoms is not less than 6, and the solid content of described carbodiimide emulsion is 30 ~ 60%, and pH value is 9 ~ 11; Described softening agent is polyvinyl butyral acetal or liquid polyisoprene; Described quaternary ammonium salt cationic surfactant is that tetradecyl trimethyl ammonium chloride is or/and Timbercote 2000; Described low mass molecule alcohol is water-soluble alcohol.
4. polyurethane asphalt composite emulsion according to claim 3, is characterized in that: described long chain fatty acid ester is that ethyl hexanoate is or/and ethyl propyl ethyl acetate.
5. polyurethane asphalt composite emulsion according to claim 3, is characterized in that: described water-soluble alcohol is that methyl alcohol, ethanol are or/and propyl alcohol.
6. the using method of polyurethane asphalt composite emulsion according to any one of claim 1-5, is characterized in that, prepares A, B respectively and component C is for subsequent use; B component and component A obtain mixed solution for 3:1 ~ 2:1 in mass ratio; Then deposit mixed solution in a rifle, in another rifle, deposit component C, adopt rush-harvesting and rush-planting spraying method coating thickness to be about 5mm.
7. the using method of polyurethane asphalt composite emulsion according to claim 6, it is characterized in that, during described spraying, the spray volume of component C is 5 ~ 10% of composite emulsion quality.
8. the using method of polyurethane asphalt composite emulsion according to claim 6, it is characterized in that, time prepared by described B component, stirring velocity is 30 ~ 50r/min, time 20 ~ 40min.
9. the using method of polyurethane asphalt composite emulsion according to claim 6, it is characterized in that, time prepared by described mixed solution, stirring velocity is 10 ~ 30r/min.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610067582.4A CN105504781A (en) | 2016-01-29 | 2016-01-29 | Polyurethane asphalt composite emulsion and use method thereof |
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| CN201610067582.4A CN105504781A (en) | 2016-01-29 | 2016-01-29 | Polyurethane asphalt composite emulsion and use method thereof |
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Cited By (2)
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| CN113956646A (en) * | 2021-11-17 | 2022-01-21 | 厦门凯纳石墨烯技术股份有限公司 | Polyurethane master batch and preparation method thereof |
| CN115703945A (en) * | 2021-08-16 | 2023-02-17 | 长春理工大学 | Method for preparing adhesive coating based on demulsification induction rapid curing technology |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115703945A (en) * | 2021-08-16 | 2023-02-17 | 长春理工大学 | Method for preparing adhesive coating based on demulsification induction rapid curing technology |
| CN113956646A (en) * | 2021-11-17 | 2022-01-21 | 厦门凯纳石墨烯技术股份有限公司 | Polyurethane master batch and preparation method thereof |
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