CN106674437A - Polyurethane-acrylate hybrid emulsion and preparation method thereof - Google Patents
Polyurethane-acrylate hybrid emulsion and preparation method thereof Download PDFInfo
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- CN106674437A CN106674437A CN201611268024.0A CN201611268024A CN106674437A CN 106674437 A CN106674437 A CN 106674437A CN 201611268024 A CN201611268024 A CN 201611268024A CN 106674437 A CN106674437 A CN 106674437A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
- C09D5/1662—Synthetic film-forming substance
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Abstract
The invention discloses a polyurethane-acrylate hybrid emulsion which comprises the following components in parts by mass: 40-60 parts of deionized water, 5-10 parts of styrene, 3-5 parts of alkyl methacrylate, 30-50 parts of alkyl acrylate, 1-5 parts of methacrylic acid, 0.5-3 parts of acrylic acid functional monomer, 5-20 parts of water-based polyurethane, 0.5-3 parts of anionic emulsifier and 0.1-0.5 part of initiator. The polyurethane-acrylate hybrid emulsion has excellent adhesion, fouling resistance and water resistance.
Description
Technical field
The present invention relates to a kind of manufacture field of building coating, specifically a kind of polyurethane-acrylate hybridisation emulsion
And preparation method thereof.
Background technology
With the continuous reinforcement of people's environmental consciousness, the environmental-protecting performance of building coating requires also more and more higher, particularly right
The control that the organic solvent of coating is used, it has also become vast coating user focus of attention.Aqueous polyurethane coating is with water
The emerging macromolecular material that organic solvent grows up as decentralized medium is substituted, because it will not have been produced in use
Machine dissolvent residual, the phenomenon such as disengage, so deep favored by user.Because aqueous polyurethane has special molecular structure and aggregation
State, thus it has the advantages that excellent erosion resistant, pliability, adhesive force, chemicals-resistant corrode.But aqueous polyurethane itself
There is the shortcomings of solid content is relatively low, film water resistance is poor, coating film gloss degree is relatively low.Acrylic acid ester emulsion is building coating
One kind of emulsion, exists and wears no resistance with excellent water resistance and physical and mechanical properties, but acrylic acid ester emulsion itself
Defect.Therefore, how to prepare it is a kind of the performance of aqueous polyurethane and acrylate can be combined, formed stabilization
System and the mixed type emulsion for keeping its excellent hydrophilic ability, are one technical barriers of current building coating industry.
The content of the invention
It is an object of the invention to overcome the deficiencies in the prior art, there is provided a kind of with excellent adhesive force, stain resistant
With the polyurethane-acrylate hybridisation emulsion of water proofing property.
It is another object of the present invention to overcome the deficiencies in the prior art, there is provided it is a kind of with excellent ductility, it is low
The polyurethane-acrylate hybridisation emulsion of warm extensibility.
Another goal of the invention of the invention be provide a kind of reaction stability it is strong prepare above-mentioned polyurethane-acrylate
The method of ester hybridisation emulsion.
What goal of the invention of the invention was realized in：A kind of polyurethane-acrylate hybridisation emulsion, it is characterised in that：
The polyurethane-acrylate hybridisation emulsion include deionized water, styrene, alkyl methacrylate, alkyl acrylate,
Methacrylic acid, functional acrylic monomer, aqueous polyurethane, anion emulsifier and initiator, above-mentioned component press mass fraction
It is respectively：Deionized water 40-60 parts, styrene 5-10 parts, alkyl methacrylate 3-5 parts, alkyl acrylate 30-50
Part, methacrylic acid 1-5 parts, functional acrylic monomer 0.5-3 parts, aqueous polyurethane 5-20 parts, anion emulsifier 0.5-3
Part, initiator 0.1-0.5 parts.
The functional acrylic monomer includes trimethylol-propane trimethacrylate, methyl propenoic acid glycidyl
One kind in ester, GDMA is mixed with arbitrary proportion.
The anion emulsifier includes dioctyl sulfo-succinic acid vinegar, alkyl diphenyl base oxide disulfonate, alkyl
One kind in polyoxyethylene ether sulfate, alkyl sulfate is mixed with arbitrary proportion.
The initiator is including one or more composition in ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate with arbitrary proportion
Mixing.
The preparation method of the polyurethane-acrylate hybridisation emulsion is comprised the following steps：
a）The preparation of bed material liquid A：Under normal temperature and pressure under state, to agitator, condenser, constant flow pump feeding device reaction
In device, 30-50%, the 2-10% of emulsifying agent gross mass of deionized water gross mass are added, heating while stirring makes temperature in reactor
Degree is warming up to 80-90 DEG C；
b）The preparation of emulsion B：Under normal temperature and pressure state, to 20-30%, initiator that deionized water gross mass is added in beaker
The 70-80% of gross mass, surplus emulsifying agent, alkyl methacrylate, alkyl acrylate, methacrylic acid, acrylate functional
Monomer, aqueous polyurethane, and with dispersion machine stir 20-40 minutes it is standby；
c）The preparation of initiator solution C：Under normal temperature and pressure state, by surplus initiator addition balance deionized water, stirring is extremely
It is completely dissolved；
d）The reactor temperature of a steps is kept for 80-90 DEG C, and it is interior newborn to being added in reactor while stirring toward bed material liquid A
Change the 2-10% and initiator solution C of liquid B gross masses, reaction time 20-50 minutes；
e）By constant flow pump to reactor dropwise addition surplus emulsion B, time for adding 220-260 minutes in Step d；
f）Keep reactor temperature at 85-90 DEG C, be incubated 1-3 hours, then cool to 40-50 DEG C, adjust pH value to 7-9,
And stir 10-30 minutes, can obtain the polyurethane-acrylate hybridisation emulsion after filtering and discharging.
The present invention has advantages below：
1st, in polyurethane-acrylate hybridisation emulsion of the invention, the compounding reaction of acrylate and aqueous polyurethane is employed
System.Crosslinking, the polymerization of short and small type strand are produced in reaction system by acrylate and aqueous polyurethane, makes acrylic acid
Ester and aqueous polyurethane form organic whole, and the organic whole also has in addition to possessing preferable water resistance, elongation percentage and intensity
There is excellent low temperature elongation percentage and cryogenic mechanical performance.
2nd, in polyurethane-acrylate hybridisation emulsion of the invention, functional acrylic monomer is employed as whole reaction
The crosslinking of system, polymerization basic point.First, there is extremely outstanding compatibility between functional acrylic monomer and acrylic resin,
And to be crosslinked basic point in the way of and acrylic resin between fully it is miscible, so as to improve between acrylic resin and aqueous polyurethane
The stability of crosslinking.Secondly, functional acrylic monomer itself possesses more active group, in the course of the polymerization process except Yi Yushui
Property polyurethane crosslink reaction and formed outside IPN cross-linked network strand, can also with acrylic resin occur grafting, it is embedding
Section cross reaction and form cross-polymerization network molecule chain.The cooperation of above two molecular chain structure, can greatly improve emulsion
Crosslink density, make emulsion formed densification short molecular chain type paint film, so as to improve the tensile strength of emulsion system.
3rd, in polyurethane-acrylate hybridisation emulsion of the invention, friendship of the aqueous polyurethane as acrylate is employed
Connection compounding object.First, aqueous polyurethane itself possesses excellent cryogenic property and cryogenic mechanical intensity, and its addition can be solved really
The certainly problem of acrylate low temperature ductility extreme difference.Secondly, aqueous polyurethane has fabulous with other waterborne polymerics compatible
Property, and activity of cross-linking reaction higher is carried in reaction system, so that acrylate can be reduced and aqueous polyurethane is handed over
Join the difficulty of reaction.Finally, aqueous polyurethane has outstanding stain resistant performance, its with it is acrylate cross linked after the performance can be with complete
All risk insurance is stayed, and the stain resistant ability of emulsion system greatly improved.
4th, polyurethane-acrylate hybridisation emulsion of the invention, technique is continuously added dropwise using pre-emulsification and is prepared.It is first
First, relatively stable reaction environment is constituted using emulsion B and initiator solution C, enables follow-up emulsion reaction relatively mild
Carried out under environment.Secondly, subsequent chemical reaction is carried out using substep dripping method, effectively extends the reaction time of function monomer,
And ensure each component can be fully crosslinked in reaction system, be grafted, the polymerisation such as block, be greatly reduced side reaction and
The appearance of accessory substance, so as to improve the output capacity of emulsion.
Specific embodiment
Polyurethane-acrylate hybridisation emulsion of the invention include deionized water, styrene, alkyl methacrylate,
Alkyl acrylate, methacrylic acid, functional acrylic monomer, aqueous polyurethane, anion emulsifier and initiator, above-mentioned group
Part is respectively by mass fraction：Deionized water 40-60 parts, styrene 5-10 parts, alkyl methacrylate 3-5 parts, propylene
Acid alkyl ester 30-50 parts, methacrylic acid 1-5 parts, functional acrylic monomer 0.5-3 parts, aqueous polyurethane 5-20 parts, anion
Emulsifying agent 0.5-3 parts, initiator 0.1-0.5 parts.By acrylate and the compounding of aqueous polyurethane, short and small type strand is formed
Crosslinking, polymerization reaction system, improve the water resistance of emulsion system, extensibility, low temperature elongation percentage and cryogenic mechanical performance.
The functional acrylic monomer of polyurethane-acrylate hybridisation emulsion of the invention uses trimethylol propane trimethyl
One kind in acrylate, GMA, GDMA is mixed with arbitrary proportion.It is first
First, said components are respectively provided with stronger cross-linking reaction performance, it is possible to increase the molecular weight of emulsion polymer, make polyurethane-acrylate
Emulsion has preferable water resistance, elongation percentage and intensity.Secondly, trimethylol-propane trimethacrylate has ternary active
Group, its molecular chain structure that spatial network connection can be formed in cross-linking reaction；GMA then has
Chain type active group, its length that strand end can be effectively increased when hinge reacts, so that cross linked molecular structures tend to
Stable state；And GDMA has chain type both-end active group, it can form straight chain when hinge reacts
Formula cross-linked structure.Exclusive use or compounding use by said components, can effectively lift emulsion cross-linked transmission network molecule chain
Stability and compactness, so as to improve the tensile strength of emulsion system.
The anion emulsifier of polyurethane-acrylate hybridisation emulsion of the invention using dioctyl sulfo-succinic acid vinegar,
Alkyl diphenyl base oxide disulfonate, alkyl polyoxyethylene ether sulfate, one kind of alkyl sulfate or mixed with arbitrary proportion
Close.Wherein dioctyl sulfo-succinic acid vinegar has extremely strong surface-active, and it can quickly reduce the surface between two liquid phases
Power, and two liquid phases is fully dissolved each other.Alkyl diphenyl base oxide disulfonate then has high adsorption capacity, good dispersion, company
Connect ability it is strong the advantages of, and possess stronger chemical stability in emulsification system.And alkyl polyoxyethylene ether sulfuric acid is except tool
Have outside stronger surface-active, can also enable what polyaminoester emulsion stablized to be present in aqueous phase emulsion, and possess excellent
Stability in hard water, outstanding dissolubility and the advantages of there is no excitant.Alkyl sulfate then have relatively mild surface-active, its
Can play a part of to adjust emulsifying rate in emulsification system.
The initiator of polyurethane-acrylate hybridisation emulsion of the invention uses sodium peroxydisulfate, potassium peroxydisulfate, ammonium persulfate
In one kind or mentioned component with arbitrary proportion mix.The Main Function of persulfate is to provide free radical in the reaction, is made
It can produce the reaction such as free radical grafting, crosslinking in reaction system with activated double bonds, make monomer be combined into certain space knot
The macromolecular of structure, to meet the mechanical property needed for coating.
The preparation method of polyurethane-acrylate hybridisation emulsion of the present invention is comprised the following steps：
a）The preparation of bed material liquid A：Under normal temperature and pressure under state, to agitator, condenser, constant flow pump feeding device reaction
In device, 30-50%, the 2-10% of emulsifying agent gross mass of deionized water gross mass are added, heating while stirring makes temperature in reactor
Degree is warming up to 80-90 DEG C；
b）The preparation of emulsion B：Under normal temperature and pressure state, to 20-30%, initiator that deionized water gross mass is added in beaker
The 70-80% of gross mass, surplus emulsifying agent, alkyl methacrylate, alkyl acrylate, methacrylic acid, acrylate functional
Monomer, aqueous polyurethane, and with dispersion machine stir 20-40 minutes it is standby；
c）The preparation of initiator solution C：Under normal temperature and pressure state, by surplus initiator addition balance deionized water, stirring is extremely
It is completely dissolved；
d）The reactor temperature of a steps is kept for 80-90 DEG C, and it is interior newborn to being added in reactor while stirring toward bed material liquid A
Change the 2-10% and initiator solution C of liquid B gross masses, reaction time 20-50 minutes；
e）By constant flow pump to reactor dropwise addition surplus emulsion B, time for adding 220-260 minutes in Step d；
f）Keep reactor temperature at 85-90 DEG C, be incubated 1-3 hours, then cool to 40-50 DEG C, adjust pH value to 7-9,
And stir 10-30 minutes, can obtain the polyurethane-acrylate hybridisation emulsion after filtering and discharging.
According to JG/T 172-2014《Elastic building paint》Standard test, polyurethane-acrylate hydridization breast of the invention
Liquid tensile strength reaches 4-6Mp/S；Elongation percentage is 400-600%；Low temperature elongation percentage is 120-180%；The stained rate of paint film is less than
20%。
It is described in detail with reference to a pair each embodiments of table, but does not therefore limit the invention to the implementation
In the range of example：
Embodiment 1
Polyurethane-acrylate hybridisation emulsion of the invention includes deionized water, styrene, alkyl methacrylate, propylene
Acid alkyl ester, methacrylic acid, trimethylol-propane trimethacrylate, aqueous polyurethane, dioctyl sulfo-succinic acid vinegar,
Ammonium persulfate, above-mentioned component is respectively by mass fraction：40 parts of deionized water, 5 parts of styrene, alkyl methacrylate 3
Part, 30 parts of alkyl acrylate, 1 part of methacrylic acid, 0.5 part of trimethylol-propane trimethacrylate, aqueous polyurethane 5
Part, 0.5 part of dioctyl sulfo-succinic acid vinegar, 0.1 part of ammonium persulfate.
The preparation method of polyurethane-acrylate hybridisation emulsion of the present invention is comprised the following steps：
a）The preparation of bed material liquid A：Under normal temperature and pressure under state, to agitator, condenser, constant flow pump feeding device reaction
In device, 30%, the 2% of emulsifying agent gross mass of deionized water gross mass is added, heating while stirring makes reactor temperature heat up
To 80 DEG C；
b）The preparation of emulsion B：Under normal temperature and pressure state, to 20% of addition deionized water gross mass in beaker, the total matter of initiator
Amount 70%, surplus emulsifying agent, alkyl methacrylate, alkyl acrylate, methacrylic acid, functional acrylic monomer, water
Property polyurethane, and with dispersion machine stir 20 minutes it is standby；
c）The preparation of initiator solution C：Under normal temperature and pressure state, by surplus initiator addition balance deionized water, stirring is extremely
It is completely dissolved；
d）The reactor temperature of a steps is kept for 80 DEG C, and it is interior while stirring to adding emulsion in reactor toward bed material liquid A
2% and initiator solution C of B gross masses, 20 minutes reaction time；
e）Surplus emulsion B, time for adding 220 minutes are added dropwise to reactor in Step d by constant flow pump；
f）Keep reactor temperature at 85 DEG C, be incubated 1 hour, then cool to 40 DEG C, adjust pH value to 9, and stir 10 points
Clock, the polyurethane-acrylate hybridisation emulsion is can obtain after filtering and discharging.
According to JG/T 172-2014《Elastic building paint》Standard test, polyurethane-acrylate hydridization breast of the invention
Liquid tensile strength reaches 4Mp/S；Elongation percentage is 400%；Low temperature elongation percentage is 120%；The stained rate of paint film is 18%.
Embodiment 2
Polyurethane-acrylate hybridisation emulsion of the invention includes deionized water, styrene, alkyl methacrylate, propylene
Acid alkyl ester, methacrylic acid, trimethylol-propane trimethacrylate, GMA, dimethyl propylene
Olefin(e) acid glycol ester, aqueous polyurethane, dioctyl sulfo-succinic acid vinegar, alkyl diphenyl base oxide disulfonate, alkyl polyoxy
Ethene ether sulfate, alkyl sulfate, ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate, it is other that above-mentioned component presses mass fraction point counting
For：60 parts of deionized water, 10 parts of styrene, 5 parts of alkyl methacrylate, 50 parts of alkyl acrylate, methacrylic acid 5
Part, 1 part of trimethylol-propane trimethacrylate, 1 part of GMA, GDMA
1 part, 20 parts of aqueous polyurethane, 1 part of dioctyl sulfo-succinic acid vinegar, 1 part of alkyl diphenyl base oxide disulfonate, alkyl polyoxy
0.5 part of ethene ether sulfate, 0.5 part of alkyl sulfate, 0.1 part of ammonium persulfate, 0.2 part of potassium peroxydisulfate, 0.2 part of sodium peroxydisulfate.
The preparation method of polyurethane-acrylate hybridisation emulsion of the present invention is comprised the following steps：
a）The preparation of bed material liquid A：Under normal temperature and pressure under state, to agitator, condenser, constant flow pump feeding device reaction
In device, 50%, the 10% of emulsifying agent gross mass of deionized water gross mass is added, heating while stirring makes reactor temperature heat up
To 90 DEG C；
b）The preparation of emulsion B：Under normal temperature and pressure state, to 30% of addition deionized water gross mass in beaker, the total matter of initiator
Amount 80%, surplus emulsifying agent, alkyl methacrylate, alkyl acrylate, methacrylic acid, functional acrylic monomer, water
Property polyurethane, and with dispersion machine stir 40 minutes it is standby；
c）The preparation of initiator solution C：Under normal temperature and pressure state, by surplus initiator addition balance deionized water, stirring is extremely
It is completely dissolved；
d）The reactor temperature of a steps is kept for 90 DEG C, and it is interior while stirring to adding emulsion in reactor toward bed material liquid A
10% and initiator solution C of B gross masses, 50 minutes reaction time；
e）Surplus emulsion B, time for adding 260 minutes are added dropwise to reactor in Step d by constant flow pump；
f）Keep reactor temperature at 90 DEG C, be incubated 3 hours, then cool to 50 DEG C, adjust pH value to 7, and stir 30 points
Clock, the polyurethane-acrylate hybridisation emulsion is can obtain after filtering and discharging.
According to JG/T 172-2014《Elastic building paint》Standard test, polyurethane-acrylate hydridization breast of the invention
Liquid tensile strength reaches 6Mp/S；Elongation percentage is 600%；Low temperature elongation percentage is 180%；The stained rate of paint film is 10%.
Embodiment 3
Polyurethane-acrylate hybridisation emulsion of the invention includes deionized water, styrene, alkyl methacrylate, propylene
Acid alkyl ester, methacrylic acid, GMA, aqueous polyurethane, alkyl diphenyl base oxide disulfonate,
Alkyl polyoxyethylene ether sulfate, potassium peroxydisulfate, sodium peroxydisulfate, above-mentioned component are respectively by mass fraction：Deionized water 45
Part, 6 parts of styrene, 3.5 parts of alkyl methacrylate, 35 parts of alkyl acrylate, 2 parts of methacrylic acid, methacrylic acid
1 part of ethylene oxidic ester, 10 parts of aqueous polyurethane, 0.5 part of alkyl diphenyl base oxide disulfonate, alkyl polyoxyethylene ether sulfuric acid
0.5 part of salt, 0.1 part of potassium peroxydisulfate, 0.1 part of sodium peroxydisulfate.
The preparation method of polyurethane-acrylate hybridisation emulsion of the present invention is comprised the following steps：
a）The preparation of bed material liquid A：Under normal temperature and pressure under state, to agitator, condenser, constant flow pump feeding device reaction
In device, 35%, the 4% of emulsifying agent gross mass of deionized water gross mass is added, heating while stirring makes reactor temperature heat up
To 83 DEG C；
b）The preparation of emulsion B：Under normal temperature and pressure state, to 23% of addition deionized water gross mass in beaker, the total matter of initiator
Amount 73%, surplus emulsifying agent, alkyl methacrylate, alkyl acrylate, methacrylic acid, functional acrylic monomer, water
Property polyurethane, and with dispersion machine stir 25 minutes it is standby；
c）The preparation of initiator solution C：Under normal temperature and pressure state, by surplus initiator addition balance deionized water, stirring is extremely
It is completely dissolved；
d）The reactor temperature of a steps is kept for 84 DEG C, and it is interior while stirring to adding emulsion in reactor toward bed material liquid A
4% and initiator solution C of B gross masses, 30 minutes reaction time；
e）Surplus emulsion B, time for adding 230 minutes are added dropwise to reactor in Step d by constant flow pump；
f）Keep reactor temperature at 86 DEG C, be incubated 1.5 hours, then cool to 44 DEG C, regulation pH value is stirred to 8.5
15 minutes, the polyurethane-acrylate hybridisation emulsion is can obtain after filtering and discharging.
According to JG/T 172-2014《Elastic building paint》Standard test, polyurethane-acrylate hydridization breast of the invention
Liquid tensile strength reaches 4.5Mp/S；Elongation percentage is 45%；Low temperature elongation percentage is 135%；The stained rate of paint film is 16%.
Embodiment 4
Polyurethane-acrylate hybridisation emulsion of the invention includes deionized water, styrene, alkyl methacrylate, propylene
Acid alkyl ester, methacrylic acid, trimethylol-propane trimethacrylate, GDMA, aqueous poly- ammonia
Ester, dioctyl sulfo-succinic acid vinegar, alkyl sulfate, ammonium persulfate, sodium peroxydisulfate, it is other that above-mentioned component presses mass fraction point counting
For：50 parts of deionized water, 8 parts of styrene, 4 parts of alkyl methacrylate, 40 parts of alkyl acrylate, 3 parts of methacrylic acid,
1 part of trimethylol-propane trimethacrylate, 1 part of GDMA, 15 parts of aqueous polyurethane, dioctyl sulphur
1 part of base succinic acid vinegar, 0.5 part of alkyl sulfate, 0.1 part of ammonium persulfate, 0.2 part of sodium peroxydisulfate.
The preparation method of polyurethane-acrylate hybridisation emulsion of the present invention is comprised the following steps：
a）The preparation of bed material liquid A：Under normal temperature and pressure under state, to agitator, condenser, constant flow pump feeding device reaction
In device, 40%, the 6% of emulsifying agent gross mass of deionized water gross mass is added, heating while stirring makes reactor temperature heat up
To 86 DEG C；
b）The preparation of emulsion B：Under normal temperature and pressure state, to 26% of addition deionized water gross mass in beaker, the total matter of initiator
Amount 75%, surplus emulsifying agent, alkyl methacrylate, alkyl acrylate, methacrylic acid, functional acrylic monomer, water
Property polyurethane, and with dispersion machine stir 30 minutes it is standby；
c）The preparation of initiator solution C：Under normal temperature and pressure state, by surplus initiator addition balance deionized water, stirring is extremely
It is completely dissolved；
d）The reactor temperature of a steps is kept for 86 DEG C, and it is interior while stirring to adding emulsion in reactor toward bed material liquid A
6% and initiator solution C of B gross masses, 40 minutes reaction time；
e）Surplus emulsion B, time for adding 240 minutes are added dropwise to reactor in Step d by constant flow pump；
f）Keep reactor temperature at 87 DEG C, be incubated 2 hours, then cool to 46 DEG C, adjust pH value to 8, and stir 20 points
Clock, the polyurethane-acrylate hybridisation emulsion is can obtain after filtering and discharging.
According to JG/T 172-2014《Elastic building paint》Standard test, polyurethane-acrylate hydridization breast of the invention
Liquid tensile strength reaches 5Mp/S；Elongation percentage is 500%；Low temperature elongation percentage is 150%；The stained rate of paint film is 14%.
Embodiment 5
Polyurethane-acrylate hybridisation emulsion of the invention includes deionized water, styrene, alkyl methacrylate, propylene
Acid alkyl ester, methacrylic acid, trimethylol-propane trimethacrylate, GMA, dimethyl propylene
Olefin(e) acid glycol ester, aqueous polyurethane, dioctyl sulfo-succinic acid vinegar, alkyl diphenyl base oxide disulfonate, alkyl polyoxy
Ethene ether sulfate, alkyl sulfate, ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate, it is other that above-mentioned component presses mass fraction point counting
For：55 parts of deionized water, 9 parts of styrene, 4.5 parts of alkyl methacrylate, 45 parts of alkyl acrylate, methacrylic acid 4
Part, 1 part of trimethylol-propane trimethacrylate, 1 part of GMA, GDMA
0.5 part, 18 parts of aqueous polyurethane, 0.5 part of dioctyl sulfo-succinic acid vinegar, 0.5 part of alkyl diphenyl base oxide disulfonate, alkane
0.5 part of base polyoxyethylene ether sulfate, 0.5 part of alkyl sulfate, 0.1 part of ammonium persulfate, 0.2 part of potassium peroxydisulfate, sodium peroxydisulfate
0.1 part.
The preparation method of polyurethane-acrylate hybridisation emulsion of the present invention is comprised the following steps：
a）The preparation of bed material liquid A：Under normal temperature and pressure under state, to agitator, condenser, constant flow pump feeding device reaction
In device, 45%, the 8% of emulsifying agent gross mass of deionized water gross mass is added, heating while stirring makes reactor temperature heat up
To 88 DEG C；
b）The preparation of emulsion B：Under normal temperature and pressure state, to 28% of addition deionized water gross mass in beaker, the total matter of initiator
Amount 78%, surplus emulsifying agent, alkyl methacrylate, alkyl acrylate, methacrylic acid, functional acrylic monomer, water
Property polyurethane, and with dispersion machine stir 35 minutes it is standby；
c）The preparation of initiator solution C：Under normal temperature and pressure state, by surplus initiator addition balance deionized water, stirring is extremely
It is completely dissolved；
d）The reactor temperature of a steps is kept for 88 DEG C, and it is interior while stirring to adding emulsion in reactor toward bed material liquid A
8% and initiator solution C of B gross masses, 45 minutes reaction time；
e）Surplus emulsion B, time for adding 250 minutes are added dropwise to reactor in Step d by constant flow pump；
f）Keep reactor temperature at 89 DEG C, be incubated 2.5 hours, then cool to 48 DEG C, regulation pH value is stirred to 7.5
25 minutes, the polyurethane-acrylate hybridisation emulsion is can obtain after filtering and discharging.
According to JG/T 172-2014《Elastic building paint》Standard test, polyurethane-acrylate hydridization breast of the invention
Liquid tensile strength reaches 5.5Mp/S；Elongation percentage is 550%；Low temperature elongation percentage is 165%；The stained rate of paint film is 12%.
Claims (5)
1. a kind of polyurethane-acrylate hybridisation emulsion, it is characterised in that：The polyurethane-acrylate hybridisation emulsion includes
It is deionized water, styrene, alkyl methacrylate, alkyl acrylate, methacrylic acid, functional acrylic monomer, aqueous
Polyurethane, anion emulsifier and initiator, above-mentioned component are respectively by mass fraction：Deionized water 40-60 parts, styrene
5-10 parts, alkyl methacrylate 3-5 parts, alkyl acrylate 30-50 parts, methacrylic acid 1-5 parts, acrylate functional list
Body 0.5-3 parts, aqueous polyurethane 5-20 parts, anion emulsifier 0.5-3 parts, initiator 0.1-0.5 parts.
2. polyurethane-acrylate hybridisation emulsion according to claim 1, it is characterised in that：The functional acrylic monomer
Including in trimethylol-propane trimethacrylate, GMA, GDMA
One kind is mixed with arbitrary proportion.
3. polyurethane-acrylate hybridisation emulsion according to claim 1, it is characterised in that：The anion emulsifier bag
Include dioctyl sulfo-succinic acid vinegar, alkyl diphenyl base oxide disulfonate, alkyl polyoxyethylene ether sulfate, alkyl sulfate
In one kind or with arbitrary proportion mix.
4. polyurethane-acrylate hybridisation emulsion according to claim 1, it is characterised in that：The initiator includes over cure
One or more composition in sour ammonium, potassium peroxydisulfate, sodium peroxydisulfate is mixed with arbitrary proportion.
5. a kind of preparation method of polyurethane-acrylate hybridisation emulsion as claimed in claim 1, it is characterised in that：It is described poly-
The preparation method of urethane-acrylate hybrid emulsion is comprised the following steps：
a）The preparation of bed material liquid A：Under normal temperature and pressure under state, to agitator, condenser, constant flow pump feeding device reaction
In device, 30-50%, the 2-10% of emulsifying agent gross mass of deionized water gross mass are added, heating while stirring makes temperature in reactor
Degree is warming up to 80-90 DEG C；
b）The preparation of emulsion B：Under normal temperature and pressure state, to 20-30%, initiator that deionized water gross mass is added in beaker
The 70-80% of gross mass, surplus emulsifying agent, alkyl methacrylate, alkyl acrylate, methacrylic acid, acrylate functional
Monomer, aqueous polyurethane, and with dispersion machine stir 20-40 minutes it is standby；
c）The preparation of initiator solution C：Under normal temperature and pressure state, by surplus initiator addition balance deionized water, stirring is extremely
It is completely dissolved；
d）The reactor temperature of a steps is kept for 80-90 DEG C, and it is interior newborn to being added in reactor while stirring toward bed material liquid A
Change the 2-10% and initiator solution C of liquid B gross masses, reaction time 20-50 minutes；
e）By constant flow pump to reactor dropwise addition surplus emulsion B, time for adding 220-260 minutes in Step d；
f）Keep reactor temperature at 85-90 DEG C, be incubated 1-3 hours, then cool to 40-50 DEG C, adjust pH value to 7-9,
And stir 10-30 minutes, can obtain the polyurethane-acrylate hybridisation emulsion after filtering and discharging.
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| CN110951041A (en) * | 2019-12-16 | 2020-04-03 | 万华化学集团股份有限公司 | Waterborne polyurethane-acrylate hybrid copolymer and preparation method thereof |
| CN113637119A (en) * | 2021-08-26 | 2021-11-12 | 泰兴市华盛银洋新材料科技有限公司 | Novel halogen-free flame-retardant polyacrylate emulsion and preparation method thereof |
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| CN113637119A (en) * | 2021-08-26 | 2021-11-12 | 泰兴市华盛银洋新材料科技有限公司 | Novel halogen-free flame-retardant polyacrylate emulsion and preparation method thereof |
| CN116200963A (en) * | 2022-12-14 | 2023-06-02 | 广东冠力新材料有限公司 | Waterproof paper bag adhesive and preparation method thereof |
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