CN109456449A - Epoxy modified aqueous polyurethane of a kind of colour copoly type and preparation method thereof - Google Patents
Epoxy modified aqueous polyurethane of a kind of colour copoly type and preparation method thereof Download PDFInfo
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- CN109456449A CN109456449A CN201811303379.8A CN201811303379A CN109456449A CN 109456449 A CN109456449 A CN 109456449A CN 201811303379 A CN201811303379 A CN 201811303379A CN 109456449 A CN109456449 A CN 109456449A
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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
- C08F283/008—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00 on to unsaturated polymers
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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
- C08G18/28—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
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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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
- C08G18/28—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
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
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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
- C08G18/28—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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
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- C—CHEMISTRY; METALLURGY
- 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
- C08G18/28—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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
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- C—CHEMISTRY; METALLURGY
- 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
- C08G18/28—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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/46—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen
- C08G18/4676—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen containing sulfur
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- C—CHEMISTRY; METALLURGY
- 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
- C08G18/28—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
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
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- C—CHEMISTRY; METALLURGY
- 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
- C08G18/28—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
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
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- C—CHEMISTRY; METALLURGY
- 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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
Abstract
The invention discloses epoxy modified aqueous polyurethane of a kind of colored copoly type and preparation method thereof, are related to technical field of polymer materials.The present invention includes following composition by weight by weight percentage: the glycidyl methacrylate of the macromolecule dihydric alcohol of 0.1-70%, 0.1-70% terminal hydroxy group sulfonate polyester glycol, the diisocyanate of 15-50%, the glycol chain extender of 1.5-11%, the colored small molecule dihydric alcohol of 0.1-11%, the dibutyl tin dilaurate of 0.01-0.08%, the end-capping reagent of 0.2-6%, the polymerization inhibitor of 0.01-0.5%, the initiator of 0.01-0.8% and 0.1-12%.Epoxy group in the epoxy modified aqueous polyurethane of the copoly type that preparation method of the present invention is synthetically prepared can be stable in the presence of in molecular structure, lotion can long term storage, stability is good；Terminal hydroxy group sulfonate polyester glycol is used in raw material simultaneously, reduces the use of solvent.
Description
Technical field
The invention belongs to technical field of polymer materials, more particularly to a kind of epoxy modified aqueous poly- ammonia of colored copoly type
Ester and preparation method thereof.
Background technique
Aqueous polyurethane replaces the organic solvent in conventional urethane by decentralized medium of water, is green, environmentally friendly, pollution-free
New polyurethane material.Aqueous polyurethane, in recent years, with the increasing of state treatment environmental protection dynamics, have good mechanics and
The water-base polyurethane material of mechanical performance is widely used in coating, ink, adhesive, fabric coating and finishing agent, leather applies
Adorn the fields such as agent, sheet surface treating agent and fiber surface treatment agent.But current most of aqueous PU are mainly by self-emulsification
Preparation, with the PU containing hydrophilic radical for main cure component, if hydrophilic component cannot effectively enter crosslinking when dried coating film
In network, the dry film formed is met water and is easily swollen.In addition it lacks as the getable crosslinking of two part solvent type PU film
Density and high relative molecular mass, thus the water resistance of these aqueous dispersion films, solvent resistance, heat resistance and glossiness compared with
Difference seriously limits its range used.
Epoxy resin has the characteristics such as cementitiousness strong, high mechanical strength and chemicals-resistant corrosivity is strong, and in its structure
Containing hydroxyl, it can directly react and be grafted in aqueous polyurethane segment with isocyanates, to improve aqueous polyurethane
Water-fast, solvent resistant and tensile strength etc., while resin can be increased to the adhesive force of substrate.But existing epoxy group in the reaction
It participates in reacting with hydroxyl, there is also the ring-opening reaction of carbamate and epoxy group, epoxy group is difficult to be retained in aqueous poly- ammonia
In ester, also easily make the storage stability of aqueous polyurethane emulsion bad, this greatly limits epoxy modified aqueous polyurethane materials
The application field of material.
Currently, the products such as water paint, water-based ink are all that small molecule pigment/dye is in the presence of dispersing aid and poly-
Object lotion is closed as obtained from physical blending, but since the compatibility between pigments or dyes and polymer is bad, causes to produce
There is phenomena such as sedimentation, gelatinization during storage in product.In addition in film forming procedure, pigments or dyes have transport phenomena, product
When dispersing uneven, color floats on surface of the paint film, leads to surface of the paint film floating, and moves to the pigment/dye pair on surface
Human body and environment also have great harm.According to aqueous polyurethane Molecular Design and performance basic principle, by dyes/pigments
Molecule is connected available macromolecular aqueous polyurethane dye with polyurethane backbone, and will increase improves photochromic fastness, resistance to moves
Shifting property and bio-toxicity etc..On the other hand, it needs to have using a large amount of organic solvent in the synthesis process of existing polyurethane
The problems such as use of solvent will cause environmental pollution.
Summary of the invention
The purpose of the present invention is to provide epoxy modified aqueous polyurethane of a kind of colored copoly type and preparation method thereof, this hairs
Epoxy group in the epoxy modified aqueous polyurethane of the copoly type that bright preparation method is synthetically prepared can be stable in the presence of molecular structure
In, lotion can long term storage, stability is good；And terminal hydroxy group sulfonate polyester glycol is used in raw material, organic solvent can be reduced
It uses.
In order to solve the above technical problems, the present invention is achieved by the following technical solutions:
The present invention is a kind of epoxy modified aqueous polyurethane of colored copoly type, by weight percentage includes following weight group
Part: the macromolecule dihydric alcohol of 0.1-70%, 0.1-70% terminal hydroxy group sulfonate polyester glycol, 15-50% diisocyanate,
The glycol chain extender of 1.5-11%, the colored small molecule dihydric alcohol of 0.1-11%, 0.01-0.08% di lauric dibutyl
Tin (DBTDL), the end-capping reagent of 0.2-6%, the polymerization inhibitor of 0.01-0.5%, the initiator of 0.01-0.8% and 0.1-12%
Glycidyl methacrylate.
It further, by weight percentage further include the trihydroxylic alcohol crosslinking agent of 0.1-2%, the trihydroxylic alcohol crosslinking agent choosing
From in trimethylolpropane (TMP), triethanolamine (NTA), triisopropanolamine (TIPA) any one or it is any a variety of.
Further, the macromolecule dihydric alcohol is selected from polytetrahydrofuran ether glycol (PTMG), polypropylene glycol (PPG), gathers
Ethylene glycol adipate dihydric alcohol (PEA), polyadipate -1,4- butanediol ester dihydric alcohol (PBA), polyadipate-neopentyl glycol
Ester dihydric alcohol (PMA), polycaprolactone diols (PCL), any one in polycarbonate glycol (PCDL) or any a variety of.
Further, the diisocyanate is selected from isophorone diisocyanate (IPDI), toluene di-isocyanate(TDI)
(TDI), hexamethylene diisocyanate (HDI), methyl diphenylene diisocyanate (MDI), 4,4 '-dicyclohexyl methyl hydrides two are different
In cyanate (HMDI) any one or it is any a variety of.
Further, the terminal hydroxy group sulfonate polyester glycol is the production of one hundred source Chemical Co., Ltd. of Beijing, model
BY3301, BY3305 or BY3306 any one or it is any two kinds mixing.
Further, the response type small molecule dyes be selected from selected from one of following structural formula DYE1-DYE9 or
Several combinations, structural formula are as follows:
Further, the initiator is selected from persulfate initiator, water-soluble azo initiator and Redox Initiator
At least one of agent；The initiator is selected from ammonium persulfate (APS), potassium peroxydisulfate (KPS), azo dicyano valeric acid, over cure
In sour ammonium/sodium hydrogensulfite any one or it is any a variety of.
Further, the glycol chain extender of stating is selected from ethylene glycol (EG), 1,2-PD (MPD), 1,4-butanediol
(BDO), neopentyl glycol (NPG), 1,6-HD (HDO), in diglycol (DEG) any one or it is any a variety of mixed
It closes；
The end-capping reagent is selected from hydroxy-ethyl acrylate (HEA), hydroxyethyl methacrylate (HEMA), hydroxypropyl acrylate
(HPA), any one in hydroxy propyl methacrylate (HPMA) or any a variety of；
The polymerization inhibitor is in DBPC 2,6 ditertiary butyl p cresol (BHT), 1,4- benzoquinones (BQ), 1,4- benzenediol (HQ)
Any one is any a variety of.
A kind of preparation method of the epoxy modified aqueous polyurethane of colour copoly type, includes the following steps:
Step 1, take macromolecule dihydric alcohol and terminal hydroxy group sulfonate polyester glycol 100-120 DEG C dehydration 0.5-1.5 hours；
Diisocyanate is added after step 2, dehydration, in 80-90 DEG C of addition glycol chain extender, coloured silk after reaction 2-4 hours
Color small molecule dihydric alcohol, dibutyl tin dilaurate (DBTDL) and solvent, 70-80 DEG C reaction 1-4 hours；
End-capping reagent and polymerization inhibitor is added in step 3, obtains end group polyurethane containing double bonds within reaction 2-4 hours at 60-80 DEG C
Performed polymer, and initiator and reaction 2-4 hours of 60-75 DEG C of glycidyl methacrylate are added into the product of acquisition；
Step 4 is cooled to 0-40 DEG C, and the water of 2-4 times of material component weight is added under high shear agitation, and stirring is anti-
Solvent is removed under 40-50 DEG C, 0.01MPa vacuum condition after answering 5-30 minutes, obtains the epoxy-modified anion of colored copoly type
Type aqueous polyurethane emulsion.
Further, trihydroxylic alcohol crosslinking agent is additionally added while glycol chain extender is put into the step 2.
Further, the solvent butanone or acetone, the amount of solvent are the 20-50% of material component weight.
The invention has the following advantages:
1, the epoxy group in the epoxy modified aqueous polyurethane of copoly type that preparation method of the present invention is synthetically prepared can be stablized
Be present in molecular structure, lotion can long term storage, stability is good；PUD synthesized by the present invention is non-carboxylic acid type anion
PUD does not need the amines neutralizers such as addition triethylamine before emulsification, avoid epoxy group and open loop occurs under organic amine effect,
And then react with carboxyl, hydroxyl, amino group, cause molecular weight increase, lotion unstable；
2, the epoxy group in the present invention is gathered by what methyl propenoic acid glycidyl ether ester and acrylic double bond blocked
Urethane prepolymer is copolymerized and is typed into strand, and content can carry out any adjustment according to demand；
3, the epoxy-modified anion-type water-thinned polyurethane of the method for the present invention synthesis, the epoxy group in strand is normal
It can be stabilized under temperature, can be used as macromolecular curing agent, dressing agent, utilize epoxy group therein and amino, carboxylic acid, halogen etc.
Nucleopilic reagent reaction, processability are strong；
4, for the present invention using the sulfonate type polyester diol of the terminal hydroxy group of different molecular weight, soft segment is containing sodium sulfonate group
Hydrophilic radical, when pre-polymerization, just connect on polyurethane resin macromolecular chain, can avoid a large amount of uses of organic solvent；Simultaneously in water
When dispersion carries out phase reversal, modest viscosity, the hydroxyl aqueous polyurethane resin viscosity of preparation is low, contains height admittedly；Meanwhile by
In using terminal hydroxy group sulfonate polyester, rather than in acetone/butanone solvent dissolubility difference hydrophilic monomer dihydroxymethyl third
Acid, therefore can not have to add toxic, heavy-polluted N-Methyl pyrrolidone (NMP) when synthesis of polyurethane prepolymer, to make
Preparation process is more environmentally-friendly；
5, the aqueous polyurethane emulsion itself of the application synthesis has various colors, helps without additional face/dyestuff and dispersion
Agent, can directly or with after different colours lotion physical mixed be used for water colour paint, water-based ink, aqueous leather and textile dyeing
Equal fields, enormously simplify the technological process of production, save production cost, and gained colour glue film has photochromic fastness high, steady
Qualitative good advantage.
Certainly, it implements any of the products of the present invention and does not necessarily require achieving all the advantages described above at the same time.
Specific embodiment
Embodiment 1:
By 10.0 grams of PTMG (Mn=1000) and 60.0 grams of BY3305 (Mn=2000) small in 100-120 DEG C of dehydration 0.5-1.5
When, 35.0 grams of IPDI is added, 10.0 grams of BDO, 0.89 gram of DYE1 are added after reacting 2 hours at 90 DEG C, it is small in 70 DEG C of reactions 2
When, add 0.094 gram of HQ and 0.851 gram of HEMA keep reaction to react at 60 DEG C to obtain within 1.5 hours end group containing double bonds poly-
Urethane performed polymer；Then 0.09 gram of AIBN, 6.2 grams of glycidyl methacrylate is added, 100mL acetone is added, in high speed
Shearing is lower to be added 285mL water, and reaction product was sloughed solvent acetone after 30 minutes by stirring under 40 DEG C, 0.01MPa vacuum condition,
It obtains admittedly containing being 30wt%, glycidyl methacrylate content is the block anion-type water-thinned polyurethane of 5.08wt%
Lotion Epoxy-WPU1.
Wherein, DYE1 structural formula are as follows:
Embodiment 2:
By 5.0 grams of PCL (Mn=1000) and 55.0 grams of BY3301 (Mn=2000) small in 100-120 DEG C of dehydration 0.5-1.5
When, 23.51 grams of TDI is added, 9.5 grams of DEG, 0.2 gram of TMP, 0.89 gram of DYE4 are added after reacting 2 hours at 80 DEG C, 70
DEG C reaction 2 hours, add 0.09 gram of BHT and 1.532 gram of HEMA keep reaction reacted at 60 DEG C obtain within 1 hour end group contain it is double
The base polyurethane prepolymer for use as of key；Then 0.07 gram of AIBN, 3.0 grams of glycidyl methacrylate is added, 110mL acetone is added,
228mL water is added under high speed shear, stirring sloughs reaction product after 30 minutes molten under 40 DEG C, 0.01MPa vacuum condition
Agent acetone is to get to solid, containing being 30wt%, glycidyl methacrylate content is the block anionic water of 3.07wt%
Property polyaminoester emulsion Epoxy-WPU2.
Wherein, DYE4 structural formula is
Embodiment 3:
By 50.0 grams of PPG (Mn=2000), 6.0 grams of BY3306 (Mn=550 ± 30, effective content 70% ± 2) and 10.0 grams
BY3301(Mn=2000) 100-120 DEG C dehydration 0.5-1.5 hours, add 30.1 grams of IPDI, 80 DEG C react 2 hours
5.1 grams of EG, 0.89 gram of DYE2,0.15 gram of TIPA are added afterwards, is reacted 2 hours at 70 DEG C, adds 0.06 gram of BQ and 1.01 gram of HPA
It keeps reaction to react 1 hour at 60 DEG C and obtains end group base polyurethane prepolymer for use as containing double bonds；Then 0.08 gram of AIBN, 6.0 are added
130mL acetone is added in gram glycidyl methacrylate, and 254mL water is added under high speed shear, will be anti-after stirring 30 minutes
It answers product to slough solvent acetone under 40 DEG C, 0.01MPa vacuum condition to contain to get to solid for 30wt%, Glycidyl methacrylate
Glyceride content is the block Anionic Water-borne Polyurethane Emulsion Epoxy-WPU3 of 5.51wt%.
Wherein, the structural formula of DYE2 is
If other conditions of embodiment 3 are constant, and change PPG into PCDL, PEA, PBA, PMA or PCDL, can be obtained steady
Fixed block Anionic Water-borne Polyurethane Emulsion.
If other conditions of embodiment 3 are constant, and change IPDI into HDI, MDI or HMDI, stable block can also be obtained
Anionic Water-borne Polyurethane Emulsion.
If other conditions of embodiment 3 are constant, and change EG into MPO, NPG or HDO, can also obtain stable block yin from
Subtype aqueous polyurethane emulsion.
If other conditions of embodiment 3 are constant, and will and by DYE2 change into DYE1, DYE3, DYE4, DYE5, DYE6,
The one or more combination of DYE7, DYE8 or DYE9 can also obtain stable block Anionic Water-borne Polyurethane Emulsion.
If other conditions of embodiment 3 are constant, and change HPA into HEMA or HPMA, can also obtain stable block yin from
Subtype aqueous polyurethane emulsion.
If other conditions of embodiment 3 are constant, and change TIPA into NTA, stable block anionic water can be obtained
Property polyaminoester emulsion.
If other conditions of embodiment 3 are constant, and change KPS into azo dicyano valeric acid or ammonium persulfate/bisulfite
Sodium can obtain stable block Anionic Water-borne Polyurethane Emulsion.
If other conditions of embodiment 3 are constant, water is added under high speed shear, while EDA or IPDA is added, it is available
Stable block Anionic Water-borne Polyurethane Emulsion.
If other conditions of embodiment 3 are constant, raw material proportioning is adjusted, glycidyl methacrylate difference can be obtained and contain
Measure the block Anionic Water-borne Polyurethane Emulsion of (0.1-10wt%).
In the description of this specification, the description of reference term " one embodiment ", " example ", " specific example " etc. means
Particular features, structures, materials, or characteristics described in conjunction with this embodiment or example are contained at least one embodiment of the present invention
Or in example.In the present specification, schematic expression of the above terms may not refer to the same embodiment or example.And
And the particular features, structures, materials, or characteristics of description can be in any one or more of the embodiments or examples with suitable
Mode combines.
Present invention disclosed above preferred embodiment is only intended to help to illustrate the present invention.There is no detailed for preferred embodiment
All details are described, are not limited the invention to the specific embodiments described.Obviously, according to the content of this specification,
It can make many modifications and variations.These embodiments are chosen and specifically described to this specification, is in order to better explain the present invention
Principle and practical application, so that skilled artisan be enable to better understand and utilize the present invention.The present invention is only
It is limited by claims and its full scope and equivalent.
Claims (10)
1. a kind of epoxy modified aqueous polyurethane of colour copoly type, which is characterized in that by weight percentage include following weight
Component: the macromolecule dihydric alcohol of 0.1-70%, 0.1-70% terminal hydroxy group sulfonate polyester glycol, 15-50% diisocyanate,
The glycol chain extender of 1.5-11%, the colored small molecule dihydric alcohol of 0.1-11%, 0.01-0.08% di lauric dibutyl
Tin (DBTDL), the end-capping reagent of 0.2-6%, the polymerization inhibitor of 0.01-0.5%, the initiator of 0.01-0.8% and 0.1-12%
Glycidyl methacrylate.
2. a kind of epoxy modified aqueous polyurethane of colored copoly type according to claim 1, which is characterized in that with weight hundred
Divide the trihydroxylic alcohol crosslinking agent for comparing that meter further includes 0.1-2%, the trihydroxylic alcohol crosslinking agent is selected from trimethylolpropane (TMP), three second
In hydramine (NTA), triisopropanolamine (TIPA) any one or it is any a variety of.
3. a kind of epoxy modified aqueous polyurethane of colored copoly type according to claim 1, which is characterized in that described big point
Sub- dihydric alcohol be selected from polytetrahydrofuran ether glycol (PTMG), polypropylene glycol (PPG), polyethylene glycol adipate dihydric alcohol (PEA),
Polyadipate -1,4- butanediol ester dihydric alcohol (PBA), polyadipate-neopentyl glycol ester dihydric alcohol (PMA), polycaprolactone binary
Any one in alcohol (PCL), polycarbonate glycol (PCDL) is any a variety of.
4. a kind of epoxy modified aqueous polyurethane of colored copoly type according to claim 1, which is characterized in that described two is different
Cyanate is selected from isophorone diisocyanate (IPDI), toluene di-isocyanate(TDI) (TDI), hexamethylene diisocyanate
(HDI), methyl diphenylene diisocyanate (MDI), any one in 4,4'-Dicyclohexylmethane diisocyanate (HMDI)
Or it is any a variety of.
5. a kind of epoxy modified aqueous polyurethane of colored copoly type according to claim 1, which is characterized in that the reaction
Type small molecule dyes are selected from one of following structural formula DYE1-DYE9 or several combinations, structural formula are as follows:
6. a kind of epoxy modified aqueous polyurethane of colored copoly type according to claim 1, which is characterized in that the initiation
Agent is selected from least one of persulfate initiator, water-soluble azo initiator and redox initiator；The initiator
It is any one in ammonium persulfate (APS), potassium peroxydisulfate (KPS), azo dicyano valeric acid, ammonium persulfate/sodium hydrogensulfite
Kind is any a variety of.
7. a kind of epoxy modified aqueous polyurethane of colored copoly type according to claim 1, which is characterized in that described to state two
First alcohol chain extender be selected from ethylene glycol (EG), 1,2- propylene glycol (MPD), 1,4- butanediol (BDO), neopentyl glycol (NPG), 1,6- oneself
Any one in glycol (HDO), diglycol (DEG) or any a variety of mixing；
The end-capping reagent be selected from hydroxy-ethyl acrylate (HEA), hydroxyethyl methacrylate (HEMA), hydroxypropyl acrylate (HPA),
In hydroxy propyl methacrylate (HPMA) any one or it is any a variety of；
The polymerization inhibitor is any in DBPC 2,6 ditertiary butyl p cresol (BHT), 1,4- benzoquinones (BQ), 1,4- benzenediol (HQ)
It is a kind of or any a variety of.
8. a kind of a kind of preparation side of the epoxy modified aqueous polyurethane of colored copoly type as described in claim 1-7 is any one
Method, which comprises the steps of:
Step 1, take macromolecule dihydric alcohol and terminal hydroxy group sulfonate polyester glycol 100-120 DEG C dehydration 0.5-1.5 hours；
Diisocyanate is added after step 2, dehydration, it is small in 80-90 DEG C of glycol chain extender of addition after reaction 2-4 hour, colour
Molecule dihydric alcohol, dibutyl tin dilaurate (DBTDL) and solvent, 70-80 DEG C reaction 1-4 hours；
End-capping reagent and polymerization inhibitor is added in step 3, obtains end group polyurethane prepolymer containing double bonds within reaction 2-4 hours at 60-80 DEG C
Body, and initiator and reaction 2-4 hours of 60-75 DEG C of glycidyl methacrylate are added into the product of acquisition；
Step 4 is cooled to 0-40 DEG C, and the water of 2-4 times of material component weight is added under high shear agitation, is stirred to react 5-
Solvent is removed under 40-50 DEG C, 0.01MPa vacuum condition after 30 minutes, obtains the epoxy-modified anionic water of colored copoly type
Property polyaminoester emulsion.
9. a kind of preparation method of the epoxy modified aqueous polyurethane of colored copoly type according to claim 8, feature exist
In, in the step 2 put into glycol chain extender while be additionally added trihydroxylic alcohol crosslinking agent.
10. a kind of preparation method of the epoxy modified aqueous polyurethane of colored copoly type according to claim 8, feature exist
In the solvent butanone or acetone, the amount of solvent are the 20-50% of material component weight.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109970935A (en) * | 2019-04-04 | 2019-07-05 | 北京材华科技有限公司 | A kind of preparation method of stimuli responsive type enhanced water resistance aqueous polyurethane emulsion |
| CN111234165A (en) * | 2020-03-31 | 2020-06-05 | 浙江材华科技有限公司 | Macromolecular polymer color clay and preparation method thereof |
| CN111253547A (en) * | 2020-01-21 | 2020-06-09 | 武汉工程大学 | Sulfonate type ultraviolet-curing waterborne polyurethane and preparation method thereof |
| CN111500172A (en) * | 2020-03-27 | 2020-08-07 | 江苏华彩化学科技有限公司 | Water-based environment-friendly anti-cracking interior wall coating for building and preparation method thereof |
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2018
- 2018-11-02 CN CN201811303379.8A patent/CN109456449A/en not_active Withdrawn
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109970935A (en) * | 2019-04-04 | 2019-07-05 | 北京材华科技有限公司 | A kind of preparation method of stimuli responsive type enhanced water resistance aqueous polyurethane emulsion |
| CN111253547A (en) * | 2020-01-21 | 2020-06-09 | 武汉工程大学 | Sulfonate type ultraviolet-curing waterborne polyurethane and preparation method thereof |
| CN111500172A (en) * | 2020-03-27 | 2020-08-07 | 江苏华彩化学科技有限公司 | Water-based environment-friendly anti-cracking interior wall coating for building and preparation method thereof |
| CN111234165A (en) * | 2020-03-31 | 2020-06-05 | 浙江材华科技有限公司 | Macromolecular polymer color clay and preparation method thereof |
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