CN108467463A - A kind of water proof type aqueous coating polyurethane-polyacrylate composite emulsion and preparation method thereof - Google Patents
A kind of water proof type aqueous coating polyurethane-polyacrylate composite emulsion and preparation method thereof Download PDFInfo
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- CN108467463A CN108467463A CN201810285332.7A CN201810285332A CN108467463A CN 108467463 A CN108467463 A CN 108467463A CN 201810285332 A CN201810285332 A CN 201810285332A CN 108467463 A CN108467463 A CN 108467463A
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- 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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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
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- C08G18/348—Hydroxycarboxylic acids
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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/6505—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6511—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38 compounds of group C08G18/3203
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- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
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- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
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- 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
Abstract
A kind of water proof type aqueous coating urethane acrylate complex emulsions of present invention offer and preparation method thereof, belong to water-repellent paint field.The lotion according to weight fraction meter, including：50~100 parts of polyether polyol, 30~70 parts of polyisocynate monomer, 6~17 parts of polysiloxanes, 30~70 parts of acrylate monomer, 4~10 parts of small molecule chain extender, 5~15 parts of hydrophilic chain extender, 3~10 parts of salt forming agent.The present invention also provides a kind of preparation methods of water proof type aqueous coating polyurethane polyacrylate complex emulsions.Emulsion particle prepared by this method is semi IPN (half network interpenetrating) structure.After the lotion of the present invention covers with paint, lacquer, colour wash, etc. film forming, water-tolerant, film formation at low temp be good, high glaze, water contact angle >=88 °, water absorption rate≤10%, mechanical property is good, excellent combination property, the application that can be used on water-repellent paint.
Description
Technical field
The invention belongs to technical field of coatings, and in particular to a kind of water proof type aqueous coating polyurethane-polyacrylate
Complex emulsions and preparation method thereof.
Background technology
In today's society, people pursue with economy, efficiency, and ecology and the energy develop coatings industry for principle, should safety
The requirement of environmental protection, aqueous polyurethane will gradually replace the application of traditional solvent borne polyurethane.It is poly- compared to traditional solvent type
Urethane, aqueous polyurethane have many advantages, such as nontoxic, nonflammable, low temperature resistant.But aqueous polyurethane also has its inherent defect, such as water-fast
Property is poor, and mechanical property is bad, and light resistance is poor, raw material are relatively expensive etc..And polyacrylate has the advantages that many protrusions,
Such as excellent light resistance, weatherability, resistance to acid and alkali and mechanical property, but its low temperature easily becomes fragile, and high temperature easily becomes sticky.Utilize poly- ammonia
Complementation in ester core polyacrylate performance, is modified polyurethane by acrylate, the excellent poly- ammonia of availability
Ester-Polyacrylate Composites.
The Chinese patent of Publication No. CN105482060 discloses one kind, and by RAFT, (reversible addion-fragmentation chain transfer is poly-
Close) method, it is prepared for the aqueous polyurethane-acrylate copolymer emulsion of chemical bonding nucleocapsid, it can although obtaining nucleocapsid composition
The polyurethane-acrylic ester emulsion of control, but RAFT chain transfer agents may make polymer carry certain color and smell,
And their removal and conversion are also relatively difficult.
Invention content
The invention aims to solve the poor water resistance of existing water-based polyurethane-acrylate emulsion product, low temperature
The problem of film forming difference, and a kind of water proof type aqueous coating polyurethane-polyacrylate composite emulsion and its preparation side are provided
Method.
Present invention firstly provides a kind of water proof type aqueous coating polyurethane-polyacrylate emulsion, the lotion be by
Self-emulsification synthesizes Anionic Water-borne Polyurethane Emulsion, is then distributed to acrylate monomer by preswollen mode
Polymerization obtains in polyurethane system, and prepared emulsion particle is semi-IPN structures；The lotion in parts by weight, is wrapped
It includes as follows：
Preferably, the polyether polyol is selected from polyethylene glycol oxide ether glycol, polytetrahydrofuran ether glycol, polyoxygenated
One or more of propylene glycol.
Preferably, the polyisocyanates monomer is selected from methyl diphenylene diisocyanate, toluene diisocynate
One or more of ester, isophorone diisocyanate or hexamethylene diisocyanate.
Preferably, the polysiloxanes is selected from hydroxy-terminated polysiloxane, hydroxyalkyl terminated polysiloxane or amino
One or more of terminated polysiloxane.
Preferably, the acrylic ester monomer is selected from butyl acrylate, methyl methacrylate, methacrylic acid
One or more of ethyl ester or butyl methacrylate.
Preferably, the small molecule chain extender is selected from ethylene glycol, neopentyl glycol, 1,4-butanediol or 2- methyl-1s,
One or more of 3-propanediol.
Preferably, the hydrophilic chain extender is selected from dihydromethyl propionic acid, dihydroxy half ester, ethylenediamine base ethanesulfonic acid
One or more of sodium, diethylenetriamine or methyl diethanolamine.
Preferably, the one kind of the salt forming agent in triethylamine, ammonium hydroxide or sodium hydroxide.
The present invention also provides a kind of preparation method of water proof type aqueous coating polyurethane-polyacrylate composite emulsion,
Include the following steps：
Step 1：Polyether polyol, polyisocyanates, polysiloxanes, small molecule chain extender, parent are added in the reaction vessel
Water chain extender and catalyst react 2~4 hours at 75~95 DEG C, obtain prepolymer；
Step 2：Temperature in reaction vessel is down to 30~40 DEG C, acetone viscosity reduction is added, the reaction was continued 20~40 minutes,
Then salt forming agent is added, reacts 5~10 minutes, deionized water stirring is added at room temperature, obtains aqueous polyurethane emulsion；
Step 3：It is added acrylic ester monomer in obtained aqueous polyurethane emulsion, pre-swollen 12~24 at 25 DEG C
Hour, while 1/3 emulsifier is added, after waiting for pre-swollen, reaction temperature is risen to 65~80 DEG C, initiator and residue is added
Emulsifier, nitrogen protection are stirred to react 3~7 hours, obtain water proof type aqueous coating polyurethane-polyacrylate Composite Milk
Liquid.
Preferably, the mixing speed of the step three is 250~300 revs/min.
Beneficial effects of the present invention
The present invention provides a kind of water proof type aqueous coating polyurethane-polyacrylate emulsion, due to different using aliphatic
Cyanate is raw material, and prepared lotion has the characteristics that yellowing resistance and stablizes；It is introduced on polyurethane molecular main chain has
Machine silicon segment, reduces film surface energy, improves the water resistance of film；Meanwhile propylene is added by preswollen mode in the present invention
Esters of gallic acid monomer obtains a kind of aqueous polyurethane emulsion of half network blackboard (semi-IPN structures) double modifications, this is special
Structure can be such that film water resistance improves.The waterborne polyurethane-polyacrylate emulsion solid content is 30%~40%, grain size
For 80~140nm, the advantages that storage stability had emulsion viscosity moderate at 6 months or more, homogeneous grain diameter, stability is good.It is real
Test the result shows that：After covering with paint, lacquer, colour wash, etc. film forming, water resistance protrudes, contact angle >=88 °, water absorption rate≤10%, and good mechanical properties are comprehensive
It can be excellent.
The present invention also provides a kind of preparation sides of water proof type aqueous coating polyurethane-polyacrylate composite emulsion
Method, this method are proportionally gradually to be gathered polyisocynate monomer, polyether polyol, hydrophilic chain extender and organosilicon
It closes, prepares prepolymer first, synthesize Anionic Water-borne Polyurethane Emulsion by self-emulsification, then pass through preswollen side
Acrylate monomer is distributed in polyurethane system by formula, continues to polymerize, and prepares double modified aqueous polyurethane emulsions.The party
Emulsion particle prepared by method is semi-IPN (half-network interpenetrating) structure.The preparation method is simple, and raw material is easy to get, and is prepared into
The product arrived has excellent comprehensive performance.
Description of the drawings
Fig. 1 is a kind of water proof type aqueous coating polyurethane-polyacrylate composite emulsion prepared by the embodiment of the present invention 1
The transmission electron microscope picture of particle；
Fig. 2 is a kind of aquosity polyurethane-polyacrylate composite emulsion of water proof type coating prepared by the embodiment of the present invention 1
Water contact angle and water absorption rate figure.
Specific implementation mode
In order to further appreciate that the present invention, the preferred embodiments of the invention are retouched with reference to specific embodiment
It states, it should be appreciated that, these descriptions are only the feature and advantage further illustrated the present invention rather than to patents of the present invention
It is required that limitation.
Present invention firstly provides a kind of water proof type aqueous coating polyurethane-polyacrylate composite emulsion, which is
Synthesize Anionic Water-borne Polyurethane Emulsion by self-emulsification, is then divided acrylate monomer by preswollen mode
It is scattered to what polymerization in polyurethane system obtained, prepared emulsion particle is semi-IPN structures；The lotion is according to parts by weight
Meter, including：
Polyether polyol 50~100, polyisocyanates 30~80,30~70 parts of acrylic ester monomer, polysiloxanes 6~
17 parts, 4~10 parts of small molecule chain extender, 5~15 parts of hydrophilic chain extender, 3~10 parts of salt forming agent.Preferably：Polyether polyol 60
~90, polyisocyanates 40~70,7~15 parts of polysiloxanes, 5~8 parts of small molecule chain extender, 7~10 parts of hydrophilic chain extender, at
7~10 parts of salt agent, 30~60 parts of acrylic ester monomer.
Polyether polyol of the present invention is selected from polyethylene glycol oxide ether glycol, polytetrahydrofuran ether glycol, polyoxygenated third
The number-average molecular weight of one or more of enediol, the polyalcohol is preferably 1000~3000.
Polyisocyanates monomer of the present invention be selected from methyl diphenylene diisocyanate, toluene di-isocyanate(TDI),
One or more of isophorone diisocyanate or hexamethylene diisocyanate, the aliphatic isocyanic acid that the present invention uses
Ester is raw material, and the lotion of preparation has the characteristics that yellowing resistance and stablizes.
Polysiloxanes of the present invention is selected from hydroxy-terminated polysiloxane, hydroxyalkyl terminated polysiloxane or amino-terminated
The number-average molecular weight of one or more of polysiloxanes, the polysiloxanes is preferably 500~2000, in polyurethane molecular
Polysiloxanes is introduced on main chain, reduces the surface property of film, improves the water resistance of film.
Acrylic ester monomer of the present invention is selected from butyl acrylate, methyl methacrylate, methacrylic acid second
The mixture of one or more of ester or butyl methacrylate, preferably methyl methacrylate and butyl acrylate, and
The mass ratio of methyl methacrylate and butyl acrylate is 1:1.The present invention is by preswollen mode by acrylate monomer
It being added in reaction system, this preswollen mode can obtain a kind of half network blackboard (semi-IPN structures),
Semi-IPN structures can assign film excellent water resistance.
Small molecule chain extender of the present invention is selected from ethylene glycol, neopentyl glycol, 1,4- butanediols or 2- methyl-1s, 3- third
One or more of glycol.
Hydrophilic chain extender of the present invention is selected from dihydromethyl propionic acid, dihydroxy half ester, ethylenediamine base ethanesulfonic acid sodium, two
One or more of ethylene triamine or methyl diethanolamine.
The one kind of salt forming agent of the present invention in triethylamine, ammonium hydroxide or sodium hydroxide.
The present invention also provides a kind of preparation method of water proof type aqueous coating polyurethane-polyacrylate composite emulsion,
Including as follows：
Step 1：Polyether polyol, polyisocyanates, polysiloxanes, small molecule chain extender, parent are added in the reaction vessel
Water chain extender and catalyst react 2~4 hours at 75~95 DEG C, obtain prepolymer；
Step 2：Temperature in reaction vessel is down to 30~40 DEG C, acetone viscosity reduction is added, the reaction was continued 20~40 minutes,
Then salt forming agent is added, reacts 5~10 minutes, deionized water stirring is added under room temperature (25 DEG C), obtains aqueous polyurethane breast
Liquid；
Step 3：It is added acrylic ester monomer in obtained aqueous polyurethane emulsion, pre-swollen 12~24 at 25 DEG C
Hour, while 1/3 emulsifier is added, after waiting for pre-swollen, reaction temperature is risen to 65~80 DEG C, initiator and residue is added
Emulsifier, nitrogen protection are stirred to react 3~7 hours, obtain water proof type aqueous coating polyurethane-polyacrylate Composite Milk
Liquid.In step 1 of the present invention：It will first be placed in 80~100 DEG C of vacuum drying oven under vacuum and remove water for the polyether polyol of reaction
1~2 hour, after dehydration material cool down, then by polyisocyanates, polysiloxanes, small molecule chain extender, hydrophilic chain extender and
Catalyst is added in reaction kettle, is opened agitating device and heating device and is reacted 2~4 hours to 75~95 DEG C, mixing speed is excellent
It is selected as 300~400 revs/min, the logical nitrogen protection of whole process, wait for-nco value reaches theoretical value, prepolymer is made；The catalyst
Selected from N, N- dimethyl cyclohexyl amines, N, N- dimethylethanolamines, N, N- lutidines, stannous octoate and di lauric dibutyl
One kind in tin.Catalyst is according to weight fraction meter, preferably 0.01~0.1 part.
In step 2 of the present invention：Temperature in reaction vessel is down to 30~40 DEG C, the acetone drop of 30~60ml is then added
Viscous 20~40 minutes, it is subsequently added into salt forming agent, is reacted 5~10 minutes, adds deionized water, high-speed stirred 30~50 under room temperature
Minute, mixing speed is preferably 1000~2000 revs/min, obtains aqueous polyurethane emulsion.
In step 3 of the present invention：Acrylic ester monomer is added in obtained aqueous polyurethane emulsion, is pre-dissolved at 25 DEG C
Swollen 12~24 hours, i.e., mechanical agitation 12~24 hours under room temperature, preferably pre-swollen time are 14~16 hours, while being added 1/
Reaction temperature is risen to 65~80 DEG C, initiator and residual emulsifier, nitrogen is added by 3 emulsifiers after pre-swollen 14~16 hours
Gas shielded is stirred to react 3~7 hours, and mixing speed is preferably 250~300 revs/min, is removed by way of vacuum distillation
Acetone obtains aquosity polyurethane-polyacrylate composite emulsion.
According to the present invention, reaction temperature, time etc. after step 3 preswollen time and pre-swollen are all control
The key parameter of the reaction, pre-swollen time of the present invention are 12-24h, if the time is too short, monomer is with a kind of big liquid
The form of drop exists, and under mechanical stirring, monomer droplet can be made suitably to become smaller, influence pre-swollen effect；If the time is too long, meeting
Influence the stability of polyurethane aqueous dispersion body system.The reaction temperature is 65-80 DEG C, if temperature is too low, does not reach and draws
The decomposition temperature of agent is sent out, reaction effect is poor, if temperature is excessively high, water section can be made to evaporate, can had an impact to solid content.
The preparation method of the water proof type aqueous coating polyurethane-polyacrylate composite emulsion of the present invention, is first to synthesize
Polyurethane is simultaneously water-dispersible at aqueous polyurethane, then carries out pre-swollen, and monomer is exactly dispersed in entire water by preswollen purpose
Property polyurethane this system in, since acrylic ester monomer itself has certain hydrophobicity, most of monomer swells can be made
It enters in polyurethane adhesive bundle of particle, still there is small part monomer to be still free in water phase.Wait for second part acrylate monomer
Free radical polymerization, after having added initiator, list that most of monomer is polymerize inside PU, and is free in except PU in water phase
The long-chain that body can also be generated with inside continues reaction and forms the network structure to interpenetrate, because it is single not introduce functionalization
Body (such as hydroxyethyl methacrylate HEMA, one end carry-OH, one end carries unsaturated double-bond ,-OH and polyurethane reaction,
Generate with end unsaturated double-bond prepolymer) HEMA can be used as bridge, acrylate monomer is connected on PU chains, in this way
With regard to forming the polyurethane-polyacrylate copolymeric structure with chemical bond.Simultaneously in this system of the present invention, also having added has
The characteristics of machine silicon (polysiloxanes), organosilicon is that surface energy is low, and during emulsion film forming, silicon segment can be moved to film surface
It moves, the surface energy of film surface can be reduced, also allow for the raising of film surface water resistance.Here silicon Mobility of the chain segments can be by the shadow of structure
It rings, it does not have this strong molecular force of chemical bond, strand easily activity and deformation, such silicon segment to be readily migrate into film table
Face so that film surface water resistance improves.
Initiator of the present invention in potassium peroxydisulfate, ammonium persulfate, azo-bis-isobutyl cyanide, benzoyl peroxide one
Kind.The dosage of initiator is the 0.5%~2% of acrylic ester monomer weight, preferably 1%.
Emulsifier of the present invention is selected from lauryl sodium sulfate (SDS), dodecyl sodium sulfate or detergent alkylate
One kind in sodium sulfonate (SDBS).Total dosage of emulsifier is the 1%~4% of acrylic ester monomer weight, preferably 3%.
Further detailed description is done to the present invention with reference to embodiment.
Embodiment 1
It equipped with agitating device, condenser pipe, thermometer and is being connected in the four-hole boiling flask of nitrogen, polytetrahydrofuran ether two is added
Alcohol (number-average molecular weight 2000) 80g vacuumizes dehydration 2 hours at 100 DEG C, isophorone diisocyanate is added later
60g, hydrophilic chain extender dihydromethyl propionic acid 10g, small molecule chain extender 1,4-butanediol 8g, double hydroxy-end capped polydimethylsiloxanes
Alkane (number-average molecular weight 1000) 10g and catalyst dibutyltin dilaurylate 0.1g, whole nitrogen protection, oil bath pot temperature control
For system at 80 DEG C, mixing speed is 380 revs/min, and reaction reaches theoretical value in 3 hours to-NCO, obtains prepolymer；
Reactor temperature is down to 40 degree, 50ml acetone viscosity reduction is added 30 minutes, then cools the temperature to 25 DEG C, is added
Salt forming agent triethylamine 3g reacts 10 minutes, adds deionized water, high-speed stirred 30 minutes under 1200 revs/min of rotating speed
It is emulsified, obtains aqueous polyurethane emulsion；
Mixture 50g (its of methyl methacrylate and butyl acrylate is added in obtained aqueous polyurethane emulsion
Mass ratio is 1:1) 0.5g emulsifier sodium lauryl sulfates (SDS) being added, while, 14 hours (i.e. room temperature of pre-swollen at 25 DEG C
Lower mechanical agitation 14 hours), mixing speed is 300 revs/min, after pre-swollen 14 hours, reaction temperature is risen to 70 DEG C, is added
Enter initiator azo-bis-isobutyl cyanide 0.5g and residual emulsifier 1g, under nitrogen protection, is stirred to react 5 hours, obtains aqueous poly- ammonia
Ester-poly acrylate composite emulsion.
Obtained waterborne polyurethane-polyacrylate emulsion and film are tested and characterized, the results are shown in Table 1.
Fig. 1 is a kind of transmission electron microscope photo of waterborne polyurethane-polyacrylate emulsion prepared by the embodiment of the present invention 1.
From figure 1 it appears that emulsion particle distribution is more uniform, grain size is in reasonable range, and the structure of the particle is semi-
IPN (half-network interpenetrating) structure.
Fig. 2 be the embodiment of the present invention 1 prepare a kind of waterborne polyurethane-polyacrylate emulsion film water imbibition and
Water contact angle is tested, from figure 2 it can be seen that its contact angle reaches 93.1 °, water absorption rate 9.61%, water-resistance property of coating is preferable.
Embodiment 2
It equipped with agitating device, condenser pipe, thermometer and is being connected in the four-hole boiling flask of nitrogen, Polyoxyethylene glycol is added
(number-average molecular weight 1000) 60g vacuumizes dehydration 2 hours at 100 DEG C, and hexamethylene diisocyanate 40g is added later,
Hydrophilic chain extender methyl diethanolamine 8g, small molecule chain extender neopentyl glycol 6g, amino-terminated dimethyl silicone polymer (divide equally by number
Son amount is 1000) 8g and octoate catalyst stannous 0.05g, whole nitrogen protection, and the control of oil bath pot temperature is at 80 DEG C, mixing speed
It it is 380 revs/min, reaction reaches theoretical value in 3 hours to-NCO, obtains prepolymer；
Reactor temperature is down to 40 degree, 30ml acetone viscosity reduction is added 30 minutes, then cools the temperature to 25 DEG C, is added
Salt forming agent triethylamine 2g reacts 10 minutes, adds deionized water, high-speed stirred 30 minutes under 1200 revs/min of rotating speed
It is emulsified, obtains aqueous polyurethane；
Mixture 30g (its of methyl methacrylate and butyl acrylate is added in obtained aqueous polyurethane emulsion
Mass ratio is 1:1) 0.3g emulsifier dodecyl sodium sulfates being added, while, pre-swollen 14 hours is (mechanical i.e. under room temperature at 25 DEG C
Stirring 14 hours), mixing speed is 300 revs/min, after pre-swollen 14 hours, reaction temperature is risen to 70 DEG C, is added and causes
Agent potassium peroxydisulfate 0.3g and residual emulsifier 0.6g under nitrogen protection, is stirred to react 5 hours, obtains aqueous polyurethane-polypropylene
Acid esters complex emulsions.
Obtained waterborne polyurethane-polyacrylate emulsion and film are tested and characterized, the results are shown in Table 1.
Embodiment 3
It equipped with agitating device, condenser pipe, thermometer and is being connected in the four-hole boiling flask of nitrogen, Polyoxyethylene glycol is added
(number-average molecular weight 2000) 100g vacuumizes dehydration 2 hours at 100 DEG C, isophorone diisocyanate is added later
75g, hydrophilic chain extender dimethylolpropionic acid 15g, small molecule chain extender 2- methyl-1s, 3-propanediol 10g, double hydroxy-end capped poly- two
Methylsiloxane (number-average molecular weight 2000) 15g and catalyst dibutyltin dilaurylate 0.1g, whole nitrogen protection, oil bath
At 80 DEG C, mixing speed is 380 revs/min for pot temperature control, and reaction reaches theoretical value in 3 hours to-NCO, obtains prepolymer；
Reactor temperature is down to 40 degree, 60ml acetone viscosity reduction is added 30 minutes, then cools the temperature to 25 DEG C, is added
Salt forming agent triethylamine 4g reacts 10 minutes, adds deionized water, high-speed stirred 30 minutes under 1200 revs/min of rotating speed
It is emulsified, obtains aqueous polyurethane；
Mixture 60g (its of methyl methacrylate and butyl acrylate is added in obtained aqueous polyurethane emulsion
Mass ratio is 1:1) 0.6g emulsifier sodium lauryl sulfates being added, while, pre-swollen 14 hours is (mechanical i.e. under room temperature at 25 DEG C
Stirring 14 hours), mixing speed is 300 revs/min, after pre-swollen 14 hours, reaction temperature is risen to 70 DEG C, is added and causes
Benzoyl peroxide 0.6g and residual emulsifier 1.2g is crossed in agent, under nitrogen protection, is stirred to react 5 hours, is obtained aqueous polyurethane-
Poly acrylate composite emulsion.
Obtained waterborne polyurethane-polyacrylate emulsion and film are tested and characterized, the results are shown in Table 1.
Embodiment 4
It equipped with agitating device, condenser pipe, thermometer and is being connected in the four-hole boiling flask of nitrogen, polytetrahydrofuran ether two is added
Alcohol (number-average molecular weight 2000) 70g vacuumizes dehydration 2 hours at 100 DEG C, isophorone diisocyanate is added later
50g, hydrophilic chain extender dimethylolpropionic acid 9g, small molecule chain extender 1,4-butanediol 7g, hydroxyl endblocked polydimethylsiloxane
(number-average molecular weight 1000) 8g and catalyst dibutyltin dilaurylate 0.1g, whole nitrogen protection, the control of oil bath pot temperature
At 80 DEG C, mixing speed is 380 revs/min, and reaction reaches theoretical value in 3 hours to-NCO, obtains prepolymer；
Reactor temperature is down to 40 degree, 40ml acetone viscosity reduction is added 30 minutes, then cools the temperature to 25 DEG C, is added
Salt forming agent triethylamine 3g reacts 10 minutes, adds deionized water, high-speed stirred 30 minutes under 1200 revs/min of rotating speed
It is emulsified, obtains aqueous polyurethane；
Mixture 40g (its of methyl methacrylate and butyl acrylate is added in obtained aqueous polyurethane emulsion
Mass ratio is 1:1) 0.4g emulsifier sodium lauryl sulfates being added, while, pre-swollen 14 hours is (mechanical i.e. under room temperature at 25 DEG C
Stirring 14 hours), mixing speed is 300 revs/min, after pre-swollen 14 hours, reaction temperature is risen to 70 DEG C, is added and causes
Agent potassium peroxydisulfate 0.4g and residual emulsifier 0.8g under nitrogen protection, is stirred to react 5 hours, obtains aqueous polyurethane-polypropylene
Acid esters complex emulsions.
Obtained waterborne polyurethane-polyacrylate emulsion and film are tested and characterized, the results are shown in Table 1.
Table 1
Claims (10)
1. a kind of water proof type aqueous coating polyurethane-polyacrylate emulsion, which is characterized in that the lotion is by self-emulsifying
Method synthesizes Anionic Water-borne Polyurethane Emulsion, and acrylate monomer is then distributed to polyurethane by preswollen mode
Polymerization obtains in system, and prepared emulsion particle is semi-IPN structures；The lotion in parts by weight, including such as
Under：
。
2. a kind of water proof type aqueous coating polyurethane-polyacrylate emulsion according to claim 1, feature exist
In, the polyether polyol in polyethylene glycol oxide ether glycol, polytetrahydrofuran ether glycol, polyoxypropyleneglycol one
Kind is several.
3. a kind of water proof type aqueous coating polyurethane-polyacrylate emulsion according to claim 1, feature exist
In it is different that the polyisocyanates monomer is selected from methyl diphenylene diisocyanate, toluene di-isocyanate(TDI), isophorone two
One or more of cyanate or hexamethylene diisocyanate.
4. a kind of water proof type aqueous coating polyurethane-polyacrylate emulsion according to claim 1, feature exist
In the polysiloxanes is in hydroxy-terminated polysiloxane, hydroxyalkyl terminated polysiloxane or amino-terminated polysiloxanes
One or more.
5. a kind of water proof type aqueous coating polyurethane-polyacrylate emulsion according to claim 1, feature exist
In the acrylic ester monomer is selected from butyl acrylate, methyl methacrylate, ethyl methacrylate or metering system
One or more of acid butyl ester.
6. a kind of water proof type aqueous coating polyurethane-polyacrylate emulsion according to claim 1, feature exist
It is selected from ethylene glycol, neopentyl glycol, 1,4-butanediol or 2- methyl-1s in, the small molecule chain extender, one in 3-propanediol
Kind is several.
7. a kind of water proof type aqueous coating polyurethane-polyacrylate emulsion according to claim 1, feature exist
In, the hydrophilic chain extender be selected from dihydromethyl propionic acid, dihydroxy half ester, ethylenediamine base ethanesulfonic acid sodium, diethylenetriamine or
One or more of methyl diethanolamine.
8. a kind of water proof type aqueous coating polyurethane-polyacrylate emulsion according to claim 1, feature exist
In the one kind of the salt forming agent in triethylamine, ammonium hydroxide or sodium hydroxide.
9. a kind of preparation of water proof type aqueous coating polyurethane-polyacrylate composite emulsion according to claim 1
Method, which is characterized in that include the following steps：
Step 1：Polyether polyol, polyisocyanates, polysiloxanes, small molecule chain extender, hydrophilic expansion are added in the reaction vessel
Chain agent and catalyst react 2~4 hours at 75~95 DEG C, obtain prepolymer；
Step 2：Temperature in reaction vessel is down to 30~40 DEG C, acetone viscosity reduction is added, the reaction was continued 20~40 minutes, then
Salt forming agent is added, reacts 5~10 minutes, deionized water stirring is added at room temperature, obtains aqueous polyurethane emulsion；
Step 3：It is added acrylic ester monomer in obtained aqueous polyurethane emulsion, pre-swollen 12~24 hours at 25 DEG C,
1/3 emulsifier is added simultaneously, after waiting for pre-swollen, reaction temperature is risen to 65~80 DEG C, initiator and remaining emulsification is added
Agent, nitrogen protection are stirred to react 3~7 hours, obtain water proof type aqueous coating polyurethane-polyacrylate composite emulsion.
10. a kind of preparation of water proof type aqueous coating polyurethane-polyacrylate composite emulsion according to claim 9
Method, which is characterized in that the mixing speed of the step three is 250~300 revs/min.
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| CN112726273A (en) * | 2021-01-30 | 2021-04-30 | 汕头市鑫源化工科技有限公司 | Water-based high-gloss paint and preparation method thereof |
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