CN110028887A - The waterborne epoxy modified polyurethane coating of high rigidity - Google Patents

The waterborne epoxy modified polyurethane coating of high rigidity Download PDF

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Publication number
CN110028887A
CN110028887A CN201910091689.6A CN201910091689A CN110028887A CN 110028887 A CN110028887 A CN 110028887A CN 201910091689 A CN201910091689 A CN 201910091689A CN 110028887 A CN110028887 A CN 110028887A
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modified polyurethane
epoxy modified
high rigidity
reaction
agent
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CN110028887B (en
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王荣克
黄玉真
谢煌
韩菲桐
杨海景
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Zhongjiya (Shandong) New Materials Co., Ltd.
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Heze Fine New Material Technology Co Ltd
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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
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    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
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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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
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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
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    • C08G18/30—Low-molecular-weight compounds
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    • C08G18/348—Hydroxycarboxylic acids
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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
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    • C08G18/58—Epoxy resins
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/83—Chemically modified polymers
    • C08G18/833—Chemically modified polymers by nitrogen containing compounds
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    • 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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
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    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/18—Fireproof paints including high temperature resistant paints
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    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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    • C09D7/47—Levelling agents
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    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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    • C09D7/65—Additives macromolecular
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
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    • C08L2201/00—Properties
    • C08L2201/10—Transparent films; Clear coatings; Transparent materials
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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  • Polyurethanes Or Polyureas (AREA)

Abstract

The present invention provides the waterborne epoxy modified polyurethane coatings of high rigidity, the waterborne epoxy modified polyurethane coating of high rigidity, according to weight ratio, including following component: epoxy modified polyurethane aqueous dispersions: 95~97%, antiwear assistant: 0.1~1%, levelling agent: 0.1~1%, defoaming agent: 0.5~1.5%, hydrolysis stabilizer: 0.1~1%, macromolecule aligns agent: 0.5~1.5%, the waterborne epoxy modified polyurethane coating is using water as decentralized medium, it is not volatile, smell is small, energy conservation and environmental protection, it is big to form three-dimensional-structure polyurethane hardness, adhesive force is strong, heat resistance is good, toughness is very big, high temperature resistant and chemical-resistance are strong, and transparency is high.

Description

The waterborne epoxy modified polyurethane coating of high rigidity
Technical field
The present invention relates to polyurethane industrial fields, and in particular to the waterborne epoxy modified polyurethane paint of high rigidity.
Background technique
Coating is to be covered on to be protected or by decorating objects surface, and can form the continuous thin of firm attachment with coated article Film adds or does not add pigment, filler, then glued with what organic solvent or water were formulated usually based on resin, oil or lotion Thick liquid, most common coating is paint in finishing, and the organic solvent steam in paint can stimulate eyes to draw tears from sb, with skin Physiological function is interfered after contact, leads to chapped skin, and the blood cell, marrow and respiratory system etc. of human body can be destroyed when serious, oil Contain formaldehyde in paint, formaldehyde can be absorbed through respiratory tract, and the time, which has been grown, can cause the serious diseases such as nasopharyngeal carcinoma, larynx cancer, polyurethane Because of the features such as its film forming is tough, and gloss is plentiful, and adhesive force is strong, water proof and wearable, corrosion resistance, adjustability is strong, purposes is more and more wider It is general, but the characteristics such as polyurethane hardness is inadequate, thermal stability is poor, is prone to wear limit use scope of the polyurethane as coating.
A kind of polyurethane/epoxy is disclosed in the patent application document that Chinese patent literature number is CN103524703A The preparation method of resin is mainly obtained by component A and B component mixing, and component A is base polyurethane prepolymer for use as, by polyether polyol N210 and methyl diphenylene diisocyanate MDI-50 is synthesized under certain condition to be made, and B component is the ring of binary arylamine sealing end Oxygen resin, by disulfide group toluenediamine or 2, under 4- diamino -3,5- dimethyl sulphur-based chlorobenzene and epoxy resin E-44 certain condition Reaction is made, and component A and B component react curing molding after mixing according to a certain percentage under normal temperature conditions, and having prepared has Performance preferably gluing agent material, however, the purpose of the technical solution is mainly for the preparation of adhesive for polyurethane material, hardness It is low, and molding mode is normal temperature cure, the cured later time is long, low efficiency, and heat resistance is poor.
High rigidity epoxy modified polyurethane is disclosed in the patent application document that application publication number is CN106397706A The preparation method of composite material weighs 130~140 parts of component A, 2.4~15.2 parts of B component, preheats respectively；It then will be preheated Component A and B component be added in the closed container of vacuum-pumping and mix, carry out vacuum defoamation while stirring, purified to bubble After take out, be poured into corresponding mould, then carry out low-temperature setting, demould, reheat vulcanization, it is epoxy-modified poly- that high rigidity is made Urethane composite material；The component A is the mixture of isocyanate terminated performed polymer and epoxy resin；So B component is chain extender With the mixture of catalyst, the epoxy modified polyurethane composite material toughness prepared by the method is high, reaction speed is controllable, at This reduction, but compared with other preparation methods, the hardness of epoxy modified polyurethane composite material is difficult to be obviously improved, cannot Meet the requirement of certain applications, this epoxy modified polyurethane composite material meets water and is easy to be cured reaction, therefore It can only disperse to use in organic solvent when use, organic solvent is inflammable and explosive, volatile, smell is big, toxicity is big, causes interior The pollution of air, and the heat resistance of epoxy modified polyurethane composite material is insufficient, it is difficult to meet hot water in Working Life, meal Tool, destruction of the cigarette butt to film, therefore use environment is limited.
Summary of the invention
To solve problems of the prior art, the waterborne epoxy modified polyurethane that the present invention provides a kind of high rigidity applies Material, the coating is not volatile, smell is small, energy conservation and environmental protection using water as decentralized medium, and it is big, attached to form three-dimensional-structure polyurethane hardness Put forth effort that strong, heat resistance is good.
In order to achieve the above objectives, the technical scheme is that the waterborne epoxy modified polyurethane paint of high rigidity, according to Weight ratio, including following component:
Epoxy modified polyurethane aqueous dispersions: 95~97%
Antiwear assistant: 0.1~1%
Levelling agent: 0.1~1%
Defoaming agent: 0.5~1.5%
Hydrolysis stabilizer: 0.1~1%
Macromolecule aligns agent: 0.5~1.5%
Wherein, epoxy modified polyurethane aqueous dispersions preparation the following steps are included:
Step 1: preparing epoxy resin modification base polyurethane prepolymer for use as；
S1: dimerization ester alcohol chloropropionic acid benzene between 1.5mol2,4-TDI, 1mol is placed in reflux condenser and blender Three-necked flask in, under nitrogen protection, be heated to 50~70 DEG C, react 2~4h；
S2: 2mol ethylene phenol aldehyde type epoxy resin being added into product obtained in step S1, and temperature rises to 70~80 DEG C, 2~4h is reacted, epoxy modified polyurethane performed polymer is made.
S3: it is 15%~20% that concentration is added in epoxy resin modification base polyurethane prepolymer for use as obtained into step S2 Concentrated sodium hydroxide alcoholic solution is heated to 50~70 DEG C, reacts 3~5h, obtains the epoxy containing acrylic acid groups after elimination reaction Resin modified base polyurethane prepolymer for use as；
Step 2: preparing epoxy modified polyurethane aqueous dispersions, epoxy resin modification obtained in the 1mol first step is gathered Urethane performed polymer is heated to TaAfter 65~75 DEG C, 0.6mol small molecule chain extender is added, reacts taAfter 0.5~1h, it is added 0.8mol hydrophilic chain extender vacuumizes, inflated with nitrogen, Tb60~75 DEG C of sealing reactions react t into chain extension and cross-linking reactionb5~ End-capping reagent is added in the case where logical nitrogen in 10h, carries out end capping reaction, uses di-n-butylamine method titrimetry-NCO content Variation, until after adding 0.05mol radical initiator and 10ml anhydrous dimethyl sulphoxide, being filled after-NCO is blocked completely Nitrogen, sealing reaction, carries out polymerization and further cross-linking reaction, after reacting 5h, is cooled to TcAfter 30~45 DEG C, three second are added dropwise Amine neutralizes, and reacts tcAfter 10~15min, water dispersion is added, obtains the end-sealed type epoxy modified polyurethane moisture of stable and uniform Dispersion liquid.
Polyurethane intensity in the present invention using polyesterols preparation is big, and heat resistance is strong, and adhesive force is good, not easily to fall off, uses Above-mentioned preparation method, by the reaction of S3 step, so that being eliminated in chloropropionic acid group in dimerization ester alcohol chloropropionic acid benzene between original Reaction produces a large amount of double bonds after dehydrochlorination, in second step reaction process, in epoxy modified polyurethane performed polymer chain extension and While crosslinking, the double bond in double bond and former ethylene phenol aldehyde type epoxy resin that dimerization ester alcohol chloropropionic acid benzene generates between original occurs total Single poly- reaction occurs itself for poly- reaction, cooperates with epoxy modified polyurethane performed polymer chain extension and cross-linking reaction, makes the ring generated Oxygen resin modified polyurethane becomes three-dimensional-structure from linear structure, compared to the prior art a kind of system of polyurethane/epoxy resin The preparation method of Preparation Method and high rigidity epoxy modified polyurethane composite material, the high rigidity prepared through the invention it is aqueous Epoxy-modified polyurethane paint hardness is high, and toughness is big, and high temperature resistant and chemical-resistance are strong, and transparency is high, is used for product surface When, can effective protection product be not damaged, while impact resistance and impact capacity enhance, will not influence product quality, significantly Polyurethane is improved in the application in glassware field；It prepares in the raw material of epoxy resin modification base polyurethane prepolymer for use as containing parent The carboxyl (- COOH) and hydrophilic chain extender of aqueous group make the polyurethane generated have good hydrophily, while using sealing end Agent first in polyurethane-after NCO group blocks, it is no longer sensitive to water, reaction will not be cured after contacting water, can It is dispersed in water well, forms homogeneous aqueous dispersions, epoxy modified polyurethane aqueous dispersions obtained, with organic solvent conduct The polyurethane coating of decentralized medium is compared, have it is non-ignitable, smell is small, free from environmental pollution, energy conservation and environmental protection, it is easy to operate, using model Enclose wide advantage；There is thermal stability and electrical insulation capability, so that preparing epoxy modified polyurethane tool in phenol aldehyde type epoxy resin There are good thermal stability and electrical insulating property, contain benzene ring structure simultaneously, there is phenol aldehyde type epoxy resin than general epoxy Resin higher modulus and hardness also contain phenyl ring base, benzene as dimerization ester alcohol chloropropionic acid benzene, 2,4-TDI between reaction raw materials Ring group has stronger hardness and chemical-resistance, further improves the hardness, intensity and chemically-resistant of epoxy modified polyurethane Property.
The selection of the epoxy resin ring-opening reaction curing agent and catalyst that use in compared to the prior art, is all inclined to use Amine curing agent participates in epoxy ring opening reaction, and the overwhelming majority has using diamine (MOCA) chain extender and ring when curing reaction Oxygen resin occur ring-opening reaction, formed amido sealing end epoxy resin after, then with base polyurethane prepolymer for use as participation react, using the technology Scheme is when preparing high hardness material, due to the high reaction activity of amido, can generate that reaction speed is fast, the problem of craftsmanship difference, Coating spontaneous curing at normal temperature containing epoxy modified polyurethane aqueous dispersions in the present invention, curing rate is moderate, has sufficiently Time carries out painting membrane operations, is appropriate for the casting of larger product area；Levelling agent can promote coating during the drying and film forming process A smooth, smooth, uniform film is formed, coating surface tension is effectively reduced, improves its levelability and uniformity, can improve The permeability of coating, increases spreadability at a possibility that spot and spot are generated when can reduce brushing, make film forming uniformly, it is natural；It is resistance to Milling aid improves the mechanical performance of polyurethane coating, and wear-resisting property may be significantly raising, improves wear resistance, Abrasion is reduced, effectively prevent scraping and uses up bits etc.；Macromolecule, which aligns agent, to be had the function of controlling molecular orientation arrangement, molecule side To consistent, the directed flow of coating is improved, flowing velocity and directionality are improved, keeps film more bright careful smooth, Meanwhile improving surface slip, promote the resistance to marring and smoothness of film；Defoaming agent, can be in the reduction in coating process Its surface tension inhibits foam to generate or eliminate the foam that has generated, improves the transparency of coating, flatness, compactness and steady It is qualitative；Hydrolysis stabilizer improves the stability of epoxy modified polyurethane in aqueous solution, avoids the generation of hydrolysis, prevents from solidifying Excessive velocities；The compatibility of epoxy modified polyurethane aqueous dispersions is good, can be miscible well with various auxiliary agents, and formation mixes Liquid is not in the phenomenon of layering or particle unevenness.
Further, hardness >=70 Shao D of epoxy-modified polyurethane,
By method made above, the epoxy resin modification polyurethane extreme hardness of the three-dimensional-structure of generation can reach mesh The preceding unapproachable hardness of epoxy polyurethane, can satisfy use in particular circumstances.
Further, hydrolysis stabilizer is epoxide；Levelling agent is polyacrylic acid；Defoaming agent is polyoxypropylene oxidation Ethylene Glycol ether；Antiwear assistant is the macromolecule organic silicon antiwear assistant,
The hardness that can be improved coating while epoxide is as hydrolysis stabilizer is also used as active dilution Agent reduces the viscosity of coating, improves the mobile performance of coating；Polyacrylic acid is innocuous substance, as levelling agent safety It is high；Polyoxypropylene ethylene oxide glycerin ether is food-grade defoaming agent, with the foam inhibition time is long, effect is good, antifoaming speed is fast, heat is steady The features such as qualitative good, highly-safe, improves transparency, thermal stability and the security performance of coating；The macromolecule organic silicon is wear-resisting Auxiliary agent will not reduce the mechanical property of product compared with traditional low molecular weight auxiliary agent, not migrate, product surface non-greasy.
Further, small molecule chain extender is ethylenediamine,
Using ethylenediamine as chain extender, water resistance, solvent-resisting and cohesive strength of aqueous polyurethane etc. can be improved, Water resistance, the solvent-resisting for improving aqueous polyurethane improve the richness and rate of drying of film.
Further, hydrophilic chain extender is dihydromethyl propionic acid,
Dihydromethyl propionic acid is as hydrophilic chain extender, during chain extending reaction, without adding any organic solvent, generates Simple process, performance are stablized, and effect is good, and good using the hydrophilicity after dihydromethyl propionic acid chain extension, can be good with water It is miscible, form homogeneous phase solution.
Further, radical initiator is azodiisobutyronitrile, causes the polymerization of double-strand, stable reaction, without secondary anti- It answers, polymerization series is convenient for control.
Further, end-capping reagent is antifebrin, and antifebrin is higher as the activity of end-capping reagent, locating for carbonyl therein At a hexatomic ring, stable structure is not easy to unseal the H-shaped on N in position and isocyanates.
Specific embodiment
The present invention is described in further details With reference to embodiment.
The waterborne epoxy modified polyurethane paint of high rigidity, preparation method are as follows: it is weight percentage below,
By 95~97% epoxy modified polyurethane aqueous dispersions, 0.1~1% antiwear assistant, 0.1~1% levelling Agent, 0.5~1.5% defoaming agent, 0.1~1% hydrolysis stabilizer, 0.5~1.5% macromolecule align agent be added it is anti- It answers in kettle, is sufficiently stirred, form homogeneous phase solution, the as waterborne epoxy modified polyurethane paint of high rigidity.
The raw material and percentage of each embodiment are as follows:
It is weight percentage above.
In the present invention, it selects epoxide as hydrolysis stabilizer, can be improved while as hydrolysis stabilizer The hardness of coating, is also used as reactive diluent, reduces the viscosity of coating, improves the mobile performance of coating；Selection is poly- Acrylic acid is innocuous substance as levelling agent, highly-safe；Select polyoxypropylene ethylene oxide glycerin ether as defoaming agent, tool Have the features such as foam inhibition time is long, effect is good, antifoaming speed is fast, thermal stability is good, highly-safe, improve coating transparency, Thermal stability and security performance；Antiwear assistant selects the macromolecule organic silicon antiwear assistant, compared with traditional low molecular weight auxiliary agent, The mechanical property that product will not be reduced does not migrate, product surface non-greasy.
Wherein, epoxy modified polyurethane aqueous dispersions preparation the following steps are included:
Step 1: preparing epoxy modified polyurethane performed polymer
S1: dimerization ester alcohol chloropropionic acid benzene between 1.5mol2,4-TDI, 1mol is placed in reflux condenser and blender Three-necked flask in, under nitrogen protection, be heated to 50~70 DEG C, react 2~4h；
Reaction equation is as follows:
S2: 2mol ethylene phenol aldehyde type epoxy resin being added into product obtained in step S1, and temperature rises to 70~80 DEG C, 2~4h is reacted, epoxy modified polyurethane performed polymer is made；
S3: concentrated sodium hydroxide alcoholic solution is added in epoxy resin modification base polyurethane prepolymer for use as obtained into step S2, adds Heat reacts 3~5h, obtains the epoxy resin modification polyurethane prepolymer containing acrylic acid groups after elimination reaction to 50~70 DEG C Body；
S2 reaction equation is as follows:
S3 reaction equation is as follows:
Step 2: preparing epoxy modified polyurethane aqueous dispersions, epoxy resin modification obtained in the 1mol first step is gathered Urethane performed polymer is heated to TaAfter 65~75 DEG C, 0.6mol small molecule chain extender is added, selects ethylenediamine as small in the present invention Molecule chain extender can be improved water resistance, solvent-resisting and cohesive strength of aqueous polyurethane etc., improve aqueous polyurethane Water resistance, solvent-resisting improve the richness and rate of drying of film, react taAfter 0.5~1h, the hydrophilic expansion of 0.8mol is added Chain agent vacuumizes, inflated with nitrogen, Tb60~75 DEG C of sealings reaction, the hydrophilic chain extender into chain extension and cross-linking reaction, in the present invention Methylpropanoic acid is selected, during chain extending reaction, without adding any organic solvent, generates simple process, performance is stablized, effect It is good and good using the hydrophilicity after dihydromethyl propionic acid chain extension, can be miscible well with water, form homogeneous phase solution, reaction tbEnd-capping reagent is added in the case where logical nitrogen in 5~10h, carries out end capping reaction, and the end-capping reagent in the present invention selects acetophenone Amine, antifebrin is higher as the activity of end-capping reagent, and the H-shaped on N in carbonyl present position therein and isocyanates is at one A hexatomic ring, stable structure are not easy to unseal, using the variation of di-n-butylamine method titrimetry-NCO content, until-NCO is complete After being blocked, this technology is the prior art, and details are not described herein, adds 0.05mol radical initiator and 10ml anhydrous two After methyl sulfoxide, inflated with nitrogen, sealing reaction carries out polymerization and further cross-linking reaction, the radical initiator choosing in the present invention With azodiisobutyronitrile, causing the polymerization of double-strand, stable reaction polymerize series and is convenient for control without side reaction, after reacting 5h, It is cooled to TcAfter 30~45 DEG C, triethylamine is added dropwise and neutralizes, reacts tcAfter 10~15min, water dispersion is added, obtains stable and uniform End-sealed type epoxy modified polyurethane aqueous dispersions, pass through method made above, the epoxy resin modification of the three-dimensional-structure of generation Polyurethane extreme hardness, hardness >=70 Shao D can reach the current epoxy-modified unapproachable hardness of polyurethane, can satisfy Use under particular surroundings.
The reaction temperature of each embodiment S1 step and reaction time are as follows:
Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5 Embodiment 6
Temperature/DEG C 65 68 50 70 55 60
Time 2 2.4 2.8 3.2 3.5 4
The reaction temperature of each embodiment S2 step and reaction time are as follows:
Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5 Embodiment 6
Temperature/DEG C 80 74 70 76 72 78
Time 2 2.4 2.8 3.2 3.5 4
The reaction temperature of each embodiment S3 step and reaction time are as follows:
Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5 Embodiment 6
Temperature/DEG C 50 70 55 65 58 60
Time/h 4.5 3.8 3.5 3 5 4
The reaction temperature of each embodiment second step and reaction time are as follows:
Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5 Embodiment 6
Ta/℃ 70 69 65 72 67 75
tc/h 0.5 0.8 0.6 0.7 0.9 1
Tb/℃ 65 70 75 72 63 60
tb/h 8 7 5 10 9 6
Tc/℃ 45 42 35 37 40 30
tc/min 12 14 10 11 15 13
The performance of the waterborne epoxy modified polyurethane paint of the high rigidity prepared in each embodiment is tested, test result As shown in table 1,
1 material properties test result of table
Polyurethane intensity as can be seen from Table 1 in the present invention using polyesterols preparation is big, and hardness is high, hardness (shore D) >=70, shock resistance >=100KJ/m2, while heat resistance is strong, and adhesive force is good, not easily to fall off, using above-mentioned preparation method, By the reaction of S3 step, so that elimination reaction occurs in chloropropionic acid group in dimerization ester alcohol chloropropionic acid benzene between original, chlorination is sloughed A large amount of double bonds are produced after hydrogen, it is former while epoxy modified polyurethane performed polymer chain extension and crosslinking in second step reaction process Between the double bond that generates of dimerization ester alcohol chloropropionic acid benzene be copolymerized with the double bond in original ethylene phenol aldehyde type epoxy resin or itself Single poly- reaction occurs, cooperates with epoxy modified polyurethane performed polymer chain extension and cross-linking reaction, keeps the epoxy resin modification generated poly- Urethane becomes three-dimensional-structure from linear structure, and a kind of preparation method of polyurethane/epoxy resin and height are hard compared to the prior art The preparation method of epoxy modified polyurethane composite material is spent, the polyurethane extreme hardness prepared through the invention, toughness is very big, High temperature resistant and chemical-resistance are strong, and transparency is high, when being used for product surface, can effective protection product be not damaged, crashworthiness While hitting with impact capacity enhancing, it will not influence product quality, greatly improve polyurethane in the application in glassware field； Prepare the carboxyl (- COOH) and hydrophilic chain extension in the raw material of epoxy resin modification base polyurethane prepolymer for use as containing hydrophilic radical Agent makes the polyurethane generated have a good hydrophily, at the same using end-capping reagent first in polyurethane-NCO group seals It is no longer sensitive to water behind end, it will not be cured reaction after contacting water, can be good at being dispersed in water, form homogeneous moisture Dispersion liquid, using epoxy modified polyurethane aqueous dispersions obtained, compared with organic solvent is as the polyurethane coating of decentralized medium, Have the advantages that non-ignitable, smell is small, free from environmental pollution, energy conservation and environmental protection, it is easy to operate, have a wide range of application, while having preferable Adhesive force, richness, alkali resistance and corrosion resistance, mobility is also preferable, is easy levelling, forms uniform film, and leakproofness Preferably, it therefore uses polyurethane as coating, does not need using priming paint, save the cost, energy conservation and environmental protection；In phenol aldehyde type epoxy resin With thermal stability and electrical insulation capability, so that preparing epoxy modified polyurethane has good thermal stability and electrical insulating property, Contain benzene ring structure simultaneously, there is phenol aldehyde type epoxy resin than general epoxy resin higher modulus and hardness, as reaction Dimerization ester alcohol chloropropionic acid benzene, 2,4-TDI also contain phenyl ring base between raw material, and phenyl ring base has stronger hardness and chemical resistance Can, further improve the hardness, intensity and chemical resistance of epoxy modified polyurethane.
By epoxy modified polyurethane aqueous dispersions, antiwear assistant, levelling agent, defoaming agent, hydrolysis stabilizer, macromolecule orientation It arranges agent to be added in reaction kettle, be sufficiently stirred, form homogeneous phase solution, the as waterborne epoxy modified polyurethane paint of high rigidity, The selection of the epoxy resin ring-opening reaction curing agent and catalyst that use in compared to the prior art, is all inclined to use amine-type cure Agent participates in epoxy ring opening reaction, and the overwhelming majority has using diamine (MOCA) chain extender and epoxy resin when curing reaction Ring-opening reaction, formed amido sealing end epoxy resin after, then with base polyurethane prepolymer for use as participation react, prepared using the technical solution When high hardness material, due to the high reaction activity of amido, it can generate that reaction speed is fast, the problem of craftsmanship difference contains in the present invention There is the coating spontaneous curing at normal temperature of epoxy modified polyurethane aqueous dispersions, curing time is moderate in 40~60min speed, has Sufficient time carries out painting membrane operations, is appropriate for the casting of larger product area；Levelling agent can promote coating in drying and forming-film mistake A smooth, smooth, uniform film is formed in journey, and coating surface tension is effectively reduced, improves its levelability and uniformity, it can The permeability for improving coating, increases spreadability at a possibility that spot and spot are generated when can reduce brushing, make film forming uniformly, from So；Antiwear assistant improves the mechanical performance of polyurethane coating, and wear-resisting property may be significantly raising, improves resistance to Grit reduces abrasion, effectively prevent scraping and uses up bits etc.；Macromolecule, which aligns agent, to be had the function of controlling molecular orientation arrangement, Molecular orientation is consistent, improves the directed flow of coating, improves flowing velocity and directionality, keeps film more bright careful It is smooth, meanwhile, improve surface slip, promotes the resistance to marring and smoothness of film；Defoaming agent, can be in coating process Its surface tension is reduced, inhibits foam to generate or eliminate the foam generated, improves the transparency, flatness, compactness of coating And stability；Hydrolysis stabilizer improves the stability of epoxy modified polyurethane in aqueous solution, avoids the generation of hydrolysis, prevents Curing rate is too fast；The compatibility of epoxy modified polyurethane aqueous dispersions is good, can be miscible well with various auxiliary agents, is formed equal Phase solution is not in the phenomenon of layering or particle unevenness.

Claims (7)

1. the waterborne epoxy modified polyurethane paint of high rigidity, it is characterised in that: according to weight ratio, including following component:
Epoxy modified polyurethane aqueous dispersions: 95~97%
Antiwear assistant: 0.1~1%
Levelling agent: 0.1~1%
Defoaming agent: 0.5~1.5%
Hydrolysis stabilizer: 0.1~1%
Macromolecule aligns agent: 0.5~1.5%
Wherein, epoxy modified polyurethane aqueous dispersions preparation the following steps are included:
Step 1: preparing epoxy resin modification base polyurethane prepolymer for use as
S1: dimerization ester alcohol chloropropionic acid benzene between 1.5mol2,4-TDI, 1mol is placed in three with reflux condenser and blender In mouth flask, under nitrogen protection, 50~70 DEG C is heated to, reacts 2~4h；
S2: 2mol ethylene phenol aldehyde type epoxy resin being added into product obtained in step S1, and temperature rises to 70~80 DEG C, instead 2~4h is answered, epoxy modified polyurethane performed polymer is made；
S3: the dense hydrogen-oxygen that concentration is 15%~20% is added in epoxy resin modification base polyurethane prepolymer for use as obtained into step S2 Change sodium alcoholic solution, be heated to 50~70 DEG C, reacts 3~5h, obtain the epoxy resin containing acrylic acid groups after elimination reaction and change Property base polyurethane prepolymer for use as；
Step 2: epoxy modified polyurethane aqueous dispersions are prepared, by epoxy resin modification polyurethane obtained in the 1mol first step Performed polymer is heated to TaAfter 65~75 DEG C, 0.6mol small molecule chain extender is added, reacts taAfter 0.5~1h, it is hydrophilic that 0.8mol is added Chain extender vacuumizes, inflated with nitrogen, Tb60~75 DEG C of sealing reactions react t into chain extension and cross-linking reactionb5~10h, in logical nitrogen In the case where gas, end-capping reagent is added, carries out end capping reaction, using the variation of di-n-butylamine method titrimetry-NCO content, until- After NCO is blocked completely, after adding 0.05mol radical initiator and 10ml anhydrous dimethyl sulphoxide, inflated with nitrogen, sealing is instead It answers, carries out polymerization and further cross-linking reaction, after reacting 5h, be cooled to TcAfter 30~45 DEG C, triethylamine is added dropwise and neutralizes, reaction tcAfter 10~15min, water dispersion is added, obtains the end-sealed type epoxy modified polyurethane aqueous dispersions of stable and uniform.
2. the waterborne epoxy modified polyurethane paint of high rigidity according to claim 1, it is characterised in that: the epoxy changes Hardness >=70 Shao D of property polyurethane.
3. the waterborne epoxy modified polyurethane paint of high rigidity according to claim 2, it is characterised in that: the hydrolysis is steady Determining agent is epoxide；The levelling agent is polyacrylic acid；The defoaming agent is polyoxypropylene ethylene oxide glycerin ether；It is described Antiwear assistant is the macromolecule organic silicon antiwear assistant.
4. the waterborne epoxy modified polyurethane paint of high rigidity according to claim 2, it is characterised in that: the small molecule Chain extender is ethylenediamine.
5. the waterborne epoxy modified polyurethane paint of high rigidity according to claim 2, it is characterised in that: the hydrophilic expansion Chain agent is dihydromethyl propionic acid.
6. the waterborne epoxy modified polyurethane paint of high rigidity according to claim 2, it is characterised in that: the free radical Initiator is azodiisobutyronitrile.
7. the waterborne epoxy modified polyurethane paint of high rigidity according to claim 2, it is characterised in that: the end-capping reagent For antifebrin.
CN201910091689.6A 2019-01-30 2019-01-30 High-hardness waterborne epoxy modified polyurethane coating Active CN110028887B (en)

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US11479649B2 (en) 2020-12-16 2022-10-25 Changzhou Bemate Home Technology Co., Ltd. Scratch-resistant floor and method for producing same, and floor coating
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