CN106366823B - A kind of composite energy storage latex modified urethane acrylate water-repellent paint and preparation method thereof - Google Patents
A kind of composite energy storage latex modified urethane acrylate water-repellent paint and preparation method thereof Download PDFInfo
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Abstract
The present invention discloses a kind of energy storage compounded latex modified urethane acrylate water-repellent paint and preparation method thereof, after being mixed by the nano particle paraffin stable as emulsifier, polymer monomer emulsion components with polyurethane-acrylate emulsion component, polymerization obtains Organic-inorganic composite emulsion-type waterproof material, using the emulsion technology of water dispersible, non-volatility organic solvent adds in preparation process, environmentally protective nontoxic；It selects the preferable urethane acrylate of comprehensive performance as main film forming substance, utilizes Nano-meter SiO_22Paraffin is coated on SiO as particle emulsifying agents2In/polymeric shell layer, improve waterproof performance, mechanical performance and the binding characteristic with matrix of urethane acrylate coating；The paraffin of latex kernel can carry out storage-release of energy by the phase transition of solid-liquid, to realize the adjusting of environment temperature, reinforce the efficient utilization to natural energy source.
Description
Technical field
It is anti-with the modified polyurethane for integrating waterproof, energy storage and decorative multi-function that the present invention relates to a kind of building surfaces
Water paint and preparation method thereof belongs to architectural engineering waterproof coating Material Field
Background technique
Architectural waterproof material is the important component of construction material, and property belongs to functional material in construction material
Why material, building and structures will be for moisture-proof, antiseepage, leakproof using waterproof material main purpose, and China is being built
Investment in terms of engineering waterproofing material is in increasing trend every year.Polyurethane-acrylic ester emulsion water-repellent paint, can by compound
Both comprehensive advantage, has that environmental-friendly, filming performance is good, adhesion-tight, and coating is cold-resistant, heat-resisting, wear-resisting, high resilience, light
Damp degree is good, waterproof performance is excellent, the performances such as weather-proof, becomes very promising coating variety.But due to raw material kind
Class is limited, can no longer meet actual use and development in science and technology by compound its performance of resulting water-repellent paint of simple lotion
Demand, especially there is also urgent problems to be solved in terms of mechanical strength, to substrate wetting ability and high waterproof performance.Before
Phase researcher mostly being introduced into inorganic nano-particle in urethane acrylate joint product, provides for the improvement of material property
One new way.
There is researcher to be prepared for aqueous polyurethane propylene acid esters and Nano-meter SiO_2 using sol-gal process2Composite material, adopt
Nano-meter SiO_2 is added in sol-gal process hydrotropism's polyurethane propylene acid esters2, ultra-violet curing film forming is then carried out, is finally obtained
Polymer glue film with inierpeneirating network structure.Research shows that the thermal stability of polymer, mechanical property and water resistance mention
It is high.Patent CN102533088A discloses a kind of water cure environment-protecting polyurethane Nano waterproof paint and preparation method thereof, utilizes
TiO2Nanoparticle and montmorillonite are modified polyurethane water-proof paint, obtain uvioresistant ability and the equal friend of mechanical performance is mentioned
High water-repellent paint.There are many method that nano particle is modified aqueous polyurethane propylene acid esters, but these inorganic particles
Due in fact special nano effect and surface characteristic, it is difficult to be dispersed in performed polymer or polymer, in addition tradition addition
Inorganic nano-particle content added by mode is more, improves coating cost, reduces practical value and economic benefit, and
It is functional relatively single.Therefore a kind of excellent combination property, excellent storage stability are studied, environmentally protective inorganic nanoparticles change
Property polyurethane-acrylate new waterproof coating will have good market application prospect, to guidance polyurethane-acrylate
Developing direction has a very important significance.
Summary of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of composite energy storage latex modified polyurethane propylene
Acid esters water-repellent paint and its preparation method and application, be used to prepare with waterproof, energy storage, decoration functions, in conjunction with substrate it is good
Good, good mechanical property the composite water-proof coating material for being suitable for building inside and outside wall and building interior component.
Technical purpose of the invention is achieved by following technical proposals:
Composite energy storage latex modified urethane acrylate water-repellent paint and preparation method thereof, is made as steps described below
It is standby:
Step 1, it prepares polymer first emulsion component and (is known as " polymer monomer emulsion components ", or " polymer is multiple
Close latex ")
Nano-silicon dioxide particle is dispersed in distilled water, uniformly rear regulation system pH is 4-4.5 formation to ultrasonic disperse
Then paraffin, styrene, divinylbenzene, butyl acrylate and initiator are formed oily phase, by water phase by water phase after mixing
High speed shear is carried out after mutually being mixed with oil, ultrasonic disperse is then added to, obtains with particle emulsifying agents SiO2Stable water packet
Water emulsion (i.e. polymer first emulsion component), the parts by weight of each raw material, which match, is
The parts by weight proportion of each raw material is preferred are as follows:
High speed shear speed is 5000-10000 turns per minute, and the time is 3-10min.
After ultrasonic disperse is uniform, using the hydrochloride aqueous solution or aqueous acetic acid of 0.1-1mol/L by system pH tune
Section is 4-4.5.
Initiator selects oil-soluble initiator, preferably azodiisobutyronitrile, two formyl of azo or benzoyl peroxide.
Paraffin selection can be dissolved or be divided in the mixture of styrene, divinylbenzene and butyl acrylate
It dissipates, selects the paraffin of single fusing point or the blended wax of different melting points, such as 50-52 DEG C of fusing point 25 DEG C of paraffin, fusing point stones
Wax.
Nano-meter SiO_22Particle is particle of the diameter in 10-100nm, and carries out hydrophobically modified to it using silane coupling agent:
By Nano-meter SiO_22Particle ultrasonic disperse reacts 8-12 hours under 70-80 degrees Celsius in the ethanol solution of silane coupling agent,
Nano-meter SiO_22The ratio of the volume (ml) of the quality (g) and silane coupling agent of particle is 2:(0.8-2), ethyl alcohol is entire reaction
Solvent environment is provided, the silane coupling agent of selection is KH-550, KH-560 or KH-570.After the reaction, centrifugation is washed
40 DEG C of vacuum drying 12h silane coupler modified SiO derived above after washing2Nano particle.
As shown in Fig. 1, SiO2Nano particle utilizes KH-550 rear infared spectrum before modified: curve 1 is SiO before modified2It receives
The infared spectrum of rice grain, curve 2 are SiO before modified2The infared spectrum of nano particle.Compare two curves, it is modified
The weak absorbing peak that 2972cm-1,2843cm-1 nearby occur is-CH in silane coupling agent2It is introduced, it is right to draw outer 3461cm-1 institute
Answer γ-Al2O3The O-H stretching vibration that surface adsorption water hydroxylating obtains is weakened after modification, illustrates part in modifying process
The alkoxy of O-H and silane coupling agent has carried out dehydrating condensation, illustrates successfully to be modified, KH-550 is introduced into SiO2Nanometer
Particle surface improves its hydrophobic property.By morphology observation, as shown in Fig. 2, latex surface arrangement compact silicon dioxide layer.
Step 2, polymer second emulsion component (i.e. " urethane acrylate multiple emulsion ") is prepared
Polypropylene glycol is warming up to 60-65 DEG C with diphenyl diisocyanate after mixing and reacts 1-2h, thereto
1,4- butanediol, dihydromethyl propionic acid and dibutyl tin dilaurate is added and is warming up to 80-90 DEG C of reactions 2-after mixing
4h continues addition triethylamine thereto and is neutralized, obtains low-viscosity polyurethane；By low-viscosity polyurethane and esters of acrylic acid list
Body is mixed into oily phase, forms water phase after emulsifier, initiator are dissolved in distilled water；It is carried out after water phase is mutually mixed with oil
High speed shearing emulsification obtains urethane acrylate multiple emulsion, the parts by weight proportion of each raw material are as follows:
The parts by weight proportion of each raw material is preferred are as follows:
High speed shear speed is 5000-10000 turns per minute, and the time is 3-10min.
Initiator selects water soluble starter, preferably ammonium persulfate, potassium peroxydisulfate or azo-bis-isobutyrate hydrochloride.
Emulsifier is compounded by anionic emulsifier and nonionic emulsifier, anionic emulsifier preferably 12
Sodium alkyl sulfate, neopelex, nonionic emulsifier preferred emulsifier OP-10 (alkyl phenol polyoxyethylene ether),
Emulsifier Tween-80 (sorbitan monooleate polyoxyethylene ether), anionic emulsifier and nonionic emulsifier matter
Amount is than being (1~10): 1, preferably (3-5): 1.
Polypropylene glycol number-average molecular weight is in 2000 ± 500, preferably polyether Glycols type polypropylene glycol.
Acrylic ester monomer is by three kinds of methyl methacrylate, butyl acrylate and acrylic acid monomer compositions, quality
Than for methyl methacrylate: butyl acrylate: acrylic acid is (1~1.5): (1~4): (1~3), preferably methyl methacrylate
Ester: butyl acrylate: the mass ratio of acrylic acid is (1-1.5): (2-4): (1-2).
Step 3, after polymer first emulsion component and polymer second emulsion component being mixed, it is equal that defoaming agent mixing is added
After even, 70-80 DEG C of 2-5h of reaction are warming up to, composite energy storage latex modified urethane acrylate water-repellent paint can be obtained,
The wherein parts by weight proportion of each component are as follows:
Defoaming agent is mainly used for inhibiting and eliminating bubble formed in two kinds of lotion mixing and polymerization process, preferably organic
Silicon class defoaming agent dimethyl silicone polymer, ethylene glycol siloxanes.
As shown in Fig. 3, coating of the invention has stronger stability.The poly- ammonia of composite energy storage latex modified of the invention
Application of the ester acrylate waterproof paint in raw-soil waterproof coating, using the mode of coating or spin coating or brushing, in life
Soil structure surface forms uniform waterproof coating layer, and waterproof coating layer is with a thickness of 100 microns or more, and preferably 500 microns -1000
Micron.
In the inventive solutions, the SiO of appropriate hydrophobically modified2Its surface property of particle is suitable for as particle cream
Agent and replace conventional emulsifier, to stabilised oil-in-water lotion, SiO2Particle is in water phase and an oil phase interface distributions；Interior oil phase
For the mixture of paraffin, monomer and polyfunctionality cross-linkable monomer, monomer is mutually capable of forming uniform mixed phase with oil, rises after emulsification
Temperature polymerization, with monomer polymerization, molecular weight is gradually increased to be reduced oil-soluble initiator with paraffin compatibility, and generation mutually separates, and gathers
Object is closed gradually to interfacial migration, while the driving force that the water soluble starter in water phase causes polymer to grow to water phase migration,
So that polymer and SiO2Particle combines more closely, forms polymer and SiO2Compound parietal layer, paraffin are coated on multiple particle jointly
It combines harmoniously within layer, i.e., composite phase-change microcapsule structure of the present invention.
SiO of the present invention with phase-change accumulation energy characteristic2/ paraffin/polymer compounded latex is to polyurethane acroleic acid
Ester composite emulsion is modified, the fine and close modified Nano SiO of latex surface covering2Stratum granulosum, special micro nano structure can
Further promote the waterproof effect and mechanical performance of urethane acrylate multiple emulsion；Inside cladding paraffin can be suitable for
Solid-liquid phase-state change is realized under phase transition temperature, storage-release of energy is carried out, so as to adjust environment to a certain extent
Temperature.The invention is able to solve the problem of inorganic nanoparticles dispersion, because being fixed in compounded latex surface, increases it effectively
Active area reduces the additive amount of inorganic nano-particle simultaneously, and the multi-functional waterproof composite material of low-cost and high-performance can be obtained,
For improving existing urethane acrylate waterproof performance, mechanical performance, the deficiency of functional characteristic, there is certain theoretical direction
Meaning and economic value.
Compared with prior art, a kind of energy storage compounded latex modified urethane acrylate waterproof coating of the invention has
Advantages and beneficial effects are as follows: (1) waterproof performance is good, effect is good in conjunction with substrate: film forming matter film forming selected by the present invention
Can be good, it can be in the protective film of one layer of compact and firm of building or the formation of building element surface；SiO simultaneously2/ paraffin/polyphenyl second
Surface covers a large amount of SiO in alkene compounded latex2Nanoparticle, the hydroxyl and function group on surface can be with inorganic matrix such as coagulations
The generations such as soil, raw-soil interaction, improves adhesion characteristic；(2) with energy storage and waterproof multifunctional: urethane acrylate
Multiple emulsion itself is provided with good waterproof effect, and introduces the SiO with special micro-nano structure2/ paraffin/polystyrene is multiple
It closes latex and further promotes its waterproof effect.In addition, internal in compounded latex be coated with phase change paraffin, energy can be carried out by phase transformation
The storage and release of amount, thus realize intelligent thermoregulating, energy conservation and environmental protection；(3) green non-poisonous, it is environment friendly and pollution-free: preparation of the invention
The organic solvent with toxic is not used in process, has synthesized the composite waterproof emulsion of water dispersible, has environmental-friendly characteristic,
It is free from environmental pollution not to be detrimental to health；(4) low production cost, preparation process and construction method are simple: original used in the present invention
Material source is extensive, and main material is even more cheap, lower production costs, less investment, and the works such as brushing or spraying can be used
Skill operation, construction method are simple.
Detailed description of the invention
Fig. 1 is SiO2Nano particle utilizes KH-550 rear infared spectrum before modified.
Fig. 2 is the SEM microscopic appearance figure of compounded latex containing paraffin in the present invention (polymer first emulsion component), wherein A
It is compounded latex entirety pattern；B is latex surface enlarged drawing.
Fig. 3 is the photo of coating prepared by the present invention, and wherein A is freshly prepared multiple emulsion；B is the height through 3000r/min
Multiple emulsion after fast cutter high speed shear 20min；C is the multiple emulsion after placing 2 months.
Specific embodiment
Technical solution of the present invention is further illustrated combined with specific embodiments below.Paraffin selects 52# paraffin (fusing point 50-
52 DEG C, Shanghai Shen Hua paraffin Co., Ltd)；0.8mL Silane coupling reagent KH-570 is dissolved in 20mL ethyl alcohol, surface is had
Can reactive hydroxyl groups 2g SiO2Nano particle ultrasonic disperse is in the ethanol solution of above-mentioned KH-570.70 DEG C or more are condensed back to
Flow 8h or more.The modified SiO of 40 DEG C of vacuum drying 12h KH-570 derived above after centrifuge washing2Nano particle；Polypropylene glycol is preferred
For polyether Glycols type polypropylene glycol N220, number-average molecular weight 2000.Use " emulsion components A " i.e. poly- in embodiment below
Close object first emulsion component, " emulsion components B " i.e. polymer second emulsion component.
Embodiment 1: compounded latex modified urethane acrylate waterproof coating
(1) emulsion components A: by 0.5g KH-570 modified Nano SiO2Particle dispersion is added into 100g distilled water, ultrasound
Acidity-basicity ph=4~4.5, which are adjusted, with the hydrochloric acid of 0.1mol/L after dispersion forms water phase；4g paraffin (fusing point: 50-52 DEG C), 3g benzene
Ethylene (St), 0.5g divinylbenzene (DVB), 0.5g butyl acrylate (BA), 0.3g azodiisobutyronitrile (AIBN) mixing are equal
The oily phase of even formation, obtains with particle emulsifying agents SiO for 10000r/min high speed shear 5 minutes after water phase and an oil phase is mixed2Stable
Emulsion oil-in-water component A.
(2) emulsion components B: after mixing by the 30g polypropylene glycol of vacuum dehydration and 15g MDI, 65 DEG C are warming up to instead
Answer 1h；6g BDO, 6g DMPA and 0.02g DBTDL is added, heats up 80 DEG C after reacting 2h, is added after 2.4g TEA is neutralized and obtains
Low-viscosity polyurethane.Above-mentioned gained polyurethane is mixed into oily phase with 7.5g MMA, 20g BA and 10g AA, by 1.25g
SDS, 0.5g OP-10 emulsifier, 1.0g KSP are dissolved in after 100g distilled water mixed with composite oil phase after, with 10000r/min speed
Degree high speed shearing emulsification obtains polyurethane-acrylate emulsion B.
(3) after mixing above-mentioned made latex A and lotion B according to the ratio of A:B=1:5,0.5g poly dimethyl silicon is added
Oxygen alkane defoaming agent is warming up to 80 DEG C of reaction 2h, the SiO with phase change energy storage function can be obtained2/ paraffin/polystyrene is compound
The urethane acrylate water-repellent paint of latex modified.
The formula the data obtained is best, and water-repellent paint stability is good, and waterproofness is functional.
Embodiment 2: compounded latex modified urethane acrylate waterproof coating
(1) emulsion components A: by 0.5g KH-570 modified Nano SiO2Particle dispersion is added into 100g distilled water, ultrasound
Acidity-basicity ph=4~4.5 formation water phases are adjusted with the hydrochloric acid of 0.1mol/L after dispersion；1g paraffin (fusing point: 52 DEG C), 2g St,
0.5g DVB, 1g BA, 0.15g AIBN, which are uniformly mixed, forms oily phase, 10000r/min high speed shear 3 after water phase and an oil phase is mixed
Minute obtains with particle emulsifying agents SiO2Stable emulsion oil-in-water component A.
(2) emulsion components B: after mixing by the 10g polypropylene glycol of vacuum dehydration and 7g MDI, 65 DEG C of reactions are warming up to
1h；3g BDO, 3g DMPA and 0.02g DBTDL is added, heats up 80 DEG C after reacting 2h, addition 1.5g TEA obtains low after neutralizing
Viscosity polyurethane.Above-mentioned gained polyurethane is mixed into oily phase with 7.5g MMA, 15g BA and 7.5g AA, by 1.05g
SDS, 0.45g OP-10,0.6g KSP are mixed after being dissolved in 100g distilled water with composite oil phase, 10000r/min speed high speed shear
Emulsification obtains polyurethane-acrylate emulsion B.
(3) after mixing above-mentioned made latex A and lotion B according to the ratio of A:B=1:10,0.5g poly dimethyl silicon is added
Oxygen alkane defoaming agent is warming up to 80 DEG C of reaction 2h, the SiO with phase change energy storage function can be obtained2/ paraffin/polystyrene is compound
The urethane acrylate water-repellent paint of latex modified.
Composite water-proof paint stability obtained by the formula is good, and waterproofness is functional.
Embodiment 3: compounded latex modified urethane acrylate waterproof coating
(1) emulsion components A: by 0.1g KH-570 modified Nano SiO2Particle dispersion is added into 100g distilled water, ultrasound
After dispersion, acidity-basicity ph=4~4.5 are adjusted with the hydrochloric acid of 0.1mol/L and form water phase；1g paraffin (fusing point: 25 DEG C), 1g St,
0.5g DVB, 0.5g BA, 0.15g benzoyl peroxide (BPO), which are uniformly mixed, forms oily phase, high speed after water phase and an oil phase is mixed
Shearing is obtained with particle emulsifying agents SiO for 5 minutes2Stable emulsion oil-in-water component A.
(2) emulsion components B: after mixing by the 25g polypropylene glycol of vacuum dehydration and 12.5g MDI, 65 DEG C are warming up to
React 1h；2.5g BDO, 2.5g DMPA and 3 drop DBTDL is added, heats up 80 DEG C after reacting 2h, is added after 2.4g TEA is neutralized and obtains
To low-viscosity polyurethane.Above-mentioned gained polyurethane is mixed into oily phase with 5g MMA, 7.5g BA and 7.5g AA, by 1.5g
SDS, 0.15g emulsifier op-10,0.3g KSP, which are dissolved in after 100g distilled water, to be mixed high speed shearing emulsification with composite oil phase and is gathered
Urethane acrylate lotion B.
(3) after mixing above-mentioned made latex A and lotion B according to the ratio of A:B=1:1,0.5g poly dimethyl silicon is added
Oxygen alkane defoaming agent is warming up to 80 DEG C of reaction 2h, the SiO with phase change energy storage function can be obtained2/ paraffin/polystyrene is compound
The urethane acrylate water-repellent paint of latex modified.
Composite water-proof paint stability obtained by the formula is good, and waterproofness is functional.
Embodiment 4: compounded latex modified urethane acrylate waterproof coating
(1) emulsion components A: by 0.1g KH-570 modified Nano SiO2Particle dispersion is added into 100g distilled water, ultrasound
After dispersion, acidity-basicity ph=4~4.5 are adjusted with the hydrochloric acid of 0.1mol/L and form water phase；1g paraffin (fusing point: 25 DEG C), 2g St,
0.5g DVB, 0.1g BA, 0.15g BPO, which are uniformly mixed, forms oily phase, obtains within high speed shear 5 minutes after water phase and an oil phase is mixed
With particle emulsifying agents SiO2Stable emulsion oil-in-water component A.
(2) emulsion components B: after mixing by the 30g polypropylene glycol of vacuum dehydration and 15g MDI, 65 DEG C are warming up to instead
Answer 1h；5g BDO, 5g DMPA and 0.03g DBTDL is added, heats up 80 DEG C after reacting 2h, is added after 2.4g TEA is neutralized and obtains
Low-viscosity polyurethane.Above-mentioned gained polyurethane is mixed into oily phase with 5g MMA, 7.5g BA and 7.5g AA, by 1.5g
SDS, 0.25g emulsifier op-10,0.3g KSP, which are dissolved in after 100g distilled water, to be mixed high speed shearing emulsification with composite oil phase and is gathered
Urethane acrylate lotion B.
(3) after mixing above-mentioned made latex A and lotion B according to the ratio of A:B=1:5,0.3g poly dimethyl silicon is added
Oxygen alkane defoaming agent is warming up to 80 DEG C of reaction 2h, the SiO with phase change energy storage function can be obtained2/ paraffin/polystyrene is compound
The urethane acrylate water-repellent paint of latex modified.
Composite water-proof paint stability obtained by the formula is good, and waterproofness is functional.
Embodiment 5: compounded latex modified urethane acrylate waterproof coating
(1) emulsion components A: by 1g KH-570 modified Nano SiO2Particle dispersion is added into 100g distilled water, ultrasound point
After dissipating, acidity-basicity ph=4~4.5 are adjusted with the hydrochloric acid of 0.1mol/L and form water phase；4.5g paraffin (fusing point: 25 DEG C), 5g St,
1.5g DVB, 1.5g BA, 0.5g BPO be uniformly mixed forms oily phase, obtain within high speed shear 5 minutes after water phase and an oil phase is mixed with
Particle emulsifying agents SiO2Stable emulsion oil-in-water component A.
(2) emulsion components B: after mixing by the 12g polypropylene glycol of vacuum dehydration and 6g MDI, 65 DEG C of reactions are warming up to
1h；3g BDO, 3g DMPA and 0.01g DBTDL is added, heats up 80 DEG C after reacting 2h, addition 1.2g TEA obtains low after neutralizing
Viscosity polyurethane.Above-mentioned gained polyurethane is mixed into oily phase with 7.5g MMA, 5g BA and 5g AA, by 0.5g SDS,
0.25g OP-10,0.05g KSP, which are dissolved in after 100g distilled water, to be mixed high speed shearing emulsification with composite oil phase and obtains polyurethane propylene
Acid esters lotion B.
(3) after mixing above-mentioned made latex A and lotion B according to the ratio of A:B=1:7,0.3g poly dimethyl silicon is added
Oxygen alkane defoaming agent is warming up to 80 DEG C of reaction 2h, the SiO with phase change energy storage function can be obtained2/ paraffin/polystyrene is compound
The urethane acrylate water-repellent paint of latex modified.
Composite water-proof paint stability obtained by the formula is good, and waterproofness is functional.
According to bibliography (Zhang X X, Fan Y F, Tao X M, et al.Fabrication and
properties of microcapsules and nanocapsulescontainingn-octadecane[J]
.MaterChemPhys.2004,88 (2-3): 300-307), it is tested using the thermodynamics that DSC carries out sample, and surveyed using DSC
The melting enthalpy or crystallization enthalpy of the sample obtained can calculate the core material content namely clad ratio of microcapsules:
Or
Wall material content=(1- core material content) × 100%
Wherein Δ Hm0With Δ Hc0The respectively melting enthalpy and crystallization enthalpy of phase-change material, Δ HmWith Δ HcFor obtained phase transformation
The melting enthalpy and crystallization enthalpy of microcapsules.
Utilize bibliography (latest developments [J] physical and chemical inspection of Ding Xiaofeng, Guan Rong, Chen Pei intelligence Contact Angle Measurement Technique
(physics fascicle), 2008,44 (2), 84-89) contact angle of prepared composite coating is tested and calculated, select raw-soil knot
Structure is that base material carries out spin coating, and control measures contact angle with a thickness of (500 ± 50) micron, by using length method, can keep away
Exempt to do the difficulty of tangent line and measurement data is made to generate biggish error.By measuring h and 2r, can be gone out according to following equations
Contact angle.
In formula: r-spherical droplets bottom surface circle radius；
H-drop height.
| Sample | Contact angle/° |
| Example 1 | 122.7 |
| Example 2 | 112.2 |
| Example 3 | 108.4 |
| Example 4 | 105.6 |
| Example 5 | 109.3 |
It is adjusted in the technological parameter that specification Summary limits, can prepare compound painting of the invention
Material, and the performance almost the same with embodiment 1-5 is shown, realize technical purpose of the invention.
Illustrative description has been done to the present invention above, it should explanation, the case where not departing from core of the invention
Under, any simple deformation, modification or other skilled in the art can not spend the equivalent replacement of creative work equal
Fall into protection scope of the present invention.
Claims (10)
1. a kind of composite energy storage latex modified urethane acrylate water-repellent paint, which is characterized in that carry out as steps described below
Preparation:
Step 1, polymer first emulsion component is prepared
Nano-silicon dioxide particle is dispersed in distilled water, uniformly rear regulation system pH is 4-4.5 formation water to ultrasonic disperse
Then paraffin, styrene, divinylbenzene, butyl acrylate and initiator are formed oily phase by phase after mixing, by water phase and
Oil carries out high speed shear after mutually being mixed, then carries out ultrasonic disperse, obtains with particle emulsifying agents SiO2Stable oil-in-water type
Lotion, the parts by weight of each raw material, which match, is
Distilled water 100 ~ 200
Nano-meter SiO_22Particle 0.1~1.5
Paraffin 1 ~ 4.5
Styrene 5~10
Divinylbenzene 0.5~1.5
Butyl acrylate 0.5~1.5
Initiator 0.05~0.5
Initiator selects oil-soluble initiator azodiisobutyronitrile or benzoyl peroxide；Nano-meter SiO_22Particle is diameter in 10-
The particle of 100nm, and hydrophobically modified is carried out to it using silane coupling agent: by Nano-meter SiO_22Particle ultrasonic disperse is silane coupled
It in the ethanol solution of agent, is reacted 8-12 hours under 70-80 degrees Celsius, the silane coupling agent of selection is KH-550, KH-560
Or KH-570；
Step 2, polymer second emulsion component is prepared
Polypropylene glycol is warming up to 60-65 DEG C with diphenyl diisocyanate after mixing and reacts 1-2h, is added thereto
1,4-butanediol, dihydromethyl propionic acid and dibutyl tin dilaurate are warming up to 80-90 DEG C of 2-4h of reaction after mixing, after
The continuous triethylamine that is added thereto is neutralized, and low-viscosity polyurethane is obtained；Low-viscosity polyurethane is mixed with acrylic ester monomer
Oily phase is synthesized, forms water phase after emulsifier, initiator are dissolved in distilled water；High speed is carried out after water phase is mutually mixed with oil
Emulsification pretreatment obtains urethane acrylate multiple emulsion, the parts by weight proportion of each raw material are as follows:
Polypropylene glycol 10 ~ 30
Diphenyl diisocyanate 7 ~ 15
1,4- butanediol 3 ~ 6
Dihydromethyl propionic acid 3 ~ 6
Dibutyl tin dilaurate 0.01-0.08
Triethylamine 1.5 ~ 2.5
Acrylic ester monomer 18~37.5
Distilled water 100 ~ 150
Emulsifier 0.75 ~ 1.75
Initiator 1.2 ~ 1.8
Initiator selects water soluble starter ammonium persulfate, potassium peroxydisulfate or azo-bis-isobutyrate hydrochloride；
Emulsifier is compounded by anionic emulsifier and nonionic emulsifier, and anionic emulsifier is dodecyl sulphur
Sour sodium, neopelex, nonionic emulsifier are emulsifier op-10, emulsifier Tween-80, anionic emulsification
Agent and nonionic emulsifier mass ratio are (1~10): 1；Polypropylene glycol number-average molecular weight is 2000 ± 500；Esters of acrylic acid
Monomer is methyl methacrylate by three kinds of methyl methacrylate, butyl acrylate and acrylic acid monomer compositions, mass ratio:
Butyl acrylate: acrylic acid is (1~1.5): (1~4): (1~3)；
Step 3, after polymer first emulsion component and polymer second emulsion component being mixed, defoaming agent is added and is uniformly mixed
Afterwards, 70-80 DEG C of 2-5h of reaction are warming up to, composite energy storage latex modified urethane acrylate water-repellent paint can be obtained,
In each component parts by weight proportion are as follows:
Polymer first emulsion component 1
Polymer second emulsion component 1-20
Defoaming agent 0.1-0.5
Defoaming agent is organic silicon defoaming agent dimethyl silicone polymer, ethylene glycol siloxanes.
2. a kind of composite energy storage latex modified urethane acrylate water-repellent paint according to claim 1, feature exist
In in step 1, the parts by weight of each raw material are matched are as follows:
Distilled water 150 ~ 180；
Nano-meter SiO_22Particle 1.0~1.5；
Paraffin 2.0 ~ 4.0；
Styrene 5~10；
Divinylbenzene 1.0~1.5；
Butyl acrylate 0.8~1.0；
Initiator 0.1~0.3.
3. a kind of composite energy storage latex modified urethane acrylate water-repellent paint according to claim 1, feature exist
In in step 1, after ultrasonic disperse is uniform, using the hydrochloride aqueous solution or aqueous acetic acid of 0.1-1mol/L by system pH
It is adjusted to 4-4.5；High speed shear speed is 5000-10000 turns per minute, and the time is 3-10min.
4. a kind of composite energy storage latex modified urethane acrylate water-repellent paint according to claim 1, feature exist
In in step 2, the parts by weight of each raw material are matched are as follows:
Polypropylene glycol 15 ~ 20；
Diphenyl diisocyanate 8 ~ 12；
1,4- butanediol 3 ~ 5；
Dihydromethyl propionic acid 4 ~ 6；
Dibutyl tin dilaurate 0.02-0.05；
Triethylamine 1.5 ~ 2.5；
Acrylic ester monomer 20~30；
Distilled water 120 ~ 150；
Emulsifier 1.0 ~ 1.5；
Initiator 1.2 ~ 1.5；
Emulsifier is compounded by anionic emulsifier and nonionic emulsifier, anionic emulsifier and non-ionic cream
Agent mass ratio is (3-5): 1；Polypropylene glycol is polyether Glycols type polypropylene glycol；Acrylic ester monomer is by metering system
Three kinds of sour methyl esters, butyl acrylate and acrylic acid monomer compositions, methyl methacrylate: butyl acrylate: the quality of acrylic acid
Than for (1-1.5): (2-4): (1-2).
5. a kind of composite energy storage latex modified urethane acrylate water-repellent paint according to claim 1, feature exist
In in step 3, the parts by weight proportion of each component is
Polymer first emulsion component 1；
Polymer second emulsion component 10-15；
Defoaming agent 0.3-0.5.
6. a kind of preparation method of composite energy storage latex modified urethane acrylate water-repellent paint, which is characterized in that under
Step is stated to be prepared:
Step 1, polymer first emulsion component is prepared
Nano-silicon dioxide particle is dispersed in distilled water, uniformly rear regulation system pH is 4-4.5 formation water to ultrasonic disperse
Then paraffin, styrene, divinylbenzene, butyl acrylate and initiator are formed oily phase by phase after mixing, by water phase and
Oil carries out high speed shear after mutually being mixed, then carries out ultrasonic disperse, obtains with particle emulsifying agents SiO2Stable oil-in-water type
Lotion, the parts by weight of each raw material, which match, is
Distilled water 100 ~ 200
Nano-meter SiO_22Particle 0.1~1.5
Paraffin 1 ~ 4.5
Styrene 5~10
Divinylbenzene 0.5~1.5
Butyl acrylate 0.5~1.5
Initiator 0.05~0.5
Initiator selects oil-soluble initiator azodiisobutyronitrile or benzoyl peroxide；Nano-meter SiO_22Particle is diameter in 10-
The particle of 100nm, and hydrophobically modified is carried out to it using silane coupling agent: by Nano-meter SiO_22Particle ultrasonic disperse is silane coupled
It in the ethanol solution of agent, is reacted 8-12 hours under 70-80 degrees Celsius, the silane coupling agent of selection is KH-550, KH-560
Or KH-570；
Step 2, polymer second emulsion component is prepared
Polypropylene glycol is warming up to 60-65 DEG C with diphenyl diisocyanate after mixing and reacts 1-2h, is added thereto
1,4-butanediol, dihydromethyl propionic acid and dibutyl tin dilaurate are warming up to 80-90 DEG C of 2-4h of reaction after mixing, after
The continuous triethylamine that is added thereto is neutralized, and low-viscosity polyurethane is obtained；Low-viscosity polyurethane is mixed with acrylic ester monomer
Oily phase is synthesized, forms water phase after emulsifier, initiator are dissolved in distilled water；High speed is carried out after water phase is mutually mixed with oil
Emulsification pretreatment obtains urethane acrylate multiple emulsion, the parts by weight proportion of each raw material are as follows:
Polypropylene glycol 10 ~ 30
Diphenyl diisocyanate 7 ~ 15
1,4- butanediol 3 ~ 6
Dihydromethyl propionic acid 3 ~ 6
Dibutyl tin dilaurate 0.01-0.08
Triethylamine 1.5 ~ 2.5
Acrylic ester monomer 18~37.5
Distilled water 100 ~ 150
Emulsifier 0.75 ~ 1.75
Initiator 1.2 ~ 1.8
Initiator selects water soluble starter for ammonium persulfate, potassium peroxydisulfate or azo-bis-isobutyrate hydrochloride；
Emulsifier is compounded by anionic emulsifier and nonionic emulsifier, and anionic emulsifier is dodecyl sulphur
Sour sodium, neopelex, nonionic emulsifier are emulsifier op-10, emulsifier Tween-80, anionic emulsification
Agent and nonionic emulsifier mass ratio are (1~10): 1；Polypropylene glycol number-average molecular weight is 2000 ± 500；Esters of acrylic acid
Monomer is methyl methacrylate by three kinds of methyl methacrylate, butyl acrylate and acrylic acid monomer compositions, mass ratio:
Butyl acrylate: acrylic acid is (1~1.5): (1~4): (1~3)；
Step 3, after polymer first emulsion component and polymer second emulsion component being mixed, defoaming agent is added and is uniformly mixed
Afterwards, 70-80 DEG C of 2-5h of reaction are warming up to, composite energy storage latex modified urethane acrylate water-repellent paint can be obtained,
In each component parts by weight proportion are as follows:
Polymer first emulsion component 1
Polymer second emulsion component 1-20
Defoaming agent 0.1-0.5
Defoaming agent is organic silicon defoaming agent dimethyl silicone polymer, ethylene glycol siloxanes.
7. a kind of preparation side of composite energy storage latex modified urethane acrylate water-repellent paint according to claim 6
Method, which is characterized in that in step 1, the parts by weight of each raw material are matched are as follows:
Distilled water 150 ~ 180；
Nano-meter SiO_22Particle 1.0~1.5；
Paraffin 2.0 ~ 4.0；
Styrene 5~10；
Divinylbenzene 1.0~1.5；
Butyl acrylate 0.8~1.0；
Initiator 0.1~0.3.
8. a kind of preparation side of composite energy storage latex modified urethane acrylate water-repellent paint according to claim 6
Method, which is characterized in that in step 1, after ultrasonic disperse is uniform, use the hydrochloride aqueous solution or acetic acid water of 0.1-1mol/L
System pH is adjusted to 4-4.5 by solution；High speed shear speed is 5000-10000 turns per minute, and the time is 3-10min.
9. a kind of preparation side of composite energy storage latex modified urethane acrylate water-repellent paint according to claim 6
Method, which is characterized in that in step 2, the parts by weight of each raw material are matched are as follows:
Polypropylene glycol 15 ~ 20；
Diphenyl diisocyanate 8 ~ 12；
1,4- butanediol 3 ~ 5；
Dihydromethyl propionic acid 4 ~ 6；
Dibutyl tin dilaurate 0.02-0.05；
Triethylamine 1.5 ~ 2.5；
Acrylic ester monomer 20~30；
Distilled water 120 ~ 150；
Emulsifier 1.0 ~ 1.5；
Initiator 1.2 ~ 1.5；
Emulsifier is compounded by anionic emulsifier and nonionic emulsifier, anionic emulsifier and non-ionic cream
Agent mass ratio is (3-5): 1；Polypropylene glycol is polyether Glycols type polypropylene glycol；Acrylic ester monomer is by metering system
Three kinds of sour methyl esters, butyl acrylate and acrylic acid monomer compositions, methyl methacrylate: butyl acrylate: the quality of acrylic acid
Than for (1-1.5): (2-4): (1-2).
10. a kind of preparation side of composite energy storage latex modified urethane acrylate water-repellent paint according to claim 6
Method, which is characterized in that in step 3, the parts by weight proportion of each component is
Polymer first emulsion component 1；
Polymer second emulsion component 10-15；
Defoaming agent 0.3-0.5.
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| CN112662300B (en) * | 2020-12-26 | 2023-04-28 | 武汉中科先进材料科技有限公司 | Long-acting wear-resistant slow-release antiviral coating and preparation method thereof |
| CN113564810B (en) * | 2021-08-18 | 2022-07-05 | 深圳市恩裳纺织品有限公司 | High-elasticity warm-keeping fabric and preparation method thereof |
| CN115838568B (en) * | 2022-12-31 | 2023-11-28 | 上海纳米技术及应用国家工程研究中心有限公司 | Transparent heat insulation slurry and preparation method and application thereof |
| CN116240719B (en) * | 2023-01-10 | 2024-06-21 | 武汉纺织大学 | Preparation and application methods of modified paraffin fluoride-free water repellent finishing agent |
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