CN105732940A - Preparation method of waterborne polyurethane-silicon dioxide nano composite emulsion - Google Patents

Preparation method of waterborne polyurethane-silicon dioxide nano composite emulsion Download PDF

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CN105732940A
CN105732940A CN201610309310.0A CN201610309310A CN105732940A CN 105732940 A CN105732940 A CN 105732940A CN 201610309310 A CN201610309310 A CN 201610309310A CN 105732940 A CN105732940 A CN 105732940A
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preparation
aqueous polyurethane
complex emulsions
silica nanometer
silicon dioxide
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张胜文
宋小宝
王亚东
范强颍
白绘宇
刘晓亚
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Jiangnan University
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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
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • 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
    • C08G18/08—Processes
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
    • 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
    • C08G18/348—Hydroxycarboxylic acids
    • 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
    • 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
    • C08G18/65—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
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6659—Compounds of group C08G18/42 with compounds of group C08G18/34
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

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  • Polymers & Plastics (AREA)
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  • Inorganic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The invention specifically relates to a preparation method of waterborne polyurethane-silicon dioxide nano composite emulsion. According to the preparation method, an oligomer namely dibasic alcohol is used as a soft section, an isocyanate compound is used as a hard section, and nano silicon dioxide is introduced into an emulsification process so as to prepare nano silicon dioxide based modified waterborne polyurethane emulsion. The introduction of the nano silicon dioxide effectively improves the tensile strength and modulus of a waterborne polyurethane latex film, so that the surface hydrophobicity of the film is enhanced, the water absorption rate is reduced, and the film is relatively high in transparency. The waterborne polyurethane nano composite emulsion prepared by the method can be widely applied to the fields of high-performance coating materials, adhesives, printing ink, surfactants, sealants and the like.

Description

A kind of preparation method of aqueous polyurethane-silica nanometer complex emulsions
Technical field
The present invention relates to the preparation method of a kind of aqueous polyurethane-silica nanometer complex emulsions, Particularly to aqueous silica dispersion and the system of aqueous polyurethane emulsion nano-composite emulsion Preparation Method.
Background technology
Aqueous polyurethane (WPU) with water as disperse medium, have high molecular, low viscosity, The advantages such as environmental protection, safety, health, in coating, adhesive, ink, sealant and surface The fields such as reason agent obtain increasingly extensive application.But the mechanical property of aqueous polyurethane latex film The aspect such as (intensity, modulus), adhesion, resistance to water can't be with traditional poly-ammonia of solvent-borne type Ester compares favourably, and therefore limits the most extensively application of aqueous polyurethane.By inorganic nano material Expect can be effectively improved as nano silicon, clay, CNT etc. introduce WPU system The mechanical property of system, but system resistance to water and hydrophobic properties of the surface improve inconspicuous even under Fall.It is strong, flexible that polydimethylsiloxane (PDMS) has low surface free energy, hydrophobicity Etc. advantage, PDMS modification WPU can be effectively improved resistance to water and the surface hydrophobic of system, But the raising of system mechanical property is inconspicuous even to be declined.Amino silicone is introduced WPU body System obtains self-crosslinking WPU emulsion, and the mechanical property of polyurethane film and resistance to water etc. are improved, But the micro structure of the colloidal stability of emulsion and film is less susceptible to control.For the most effectively carrying The mechanical property of high polyurethane film and resistance to water, the present invention prepares surface by sol-gel process The nano silicon aqueous dispersion of functionalization, draws at aqueous polyurethane emulsion process situ Enter nano silicon aqueous dispersion, prepare aqueous polyurethane-silica nanometer Composite Milk Liquid, utilizes the nano silicon of functionalisation of surfaces in aqueous polyurethane emulsion water volatilization process Self-crosslinking and polyurethane between cross-linking reaction can be effectively improved aqueous polyurethane latex film Mechanical property, resistance to water and surface hydrophobic.This dispersion can be applicable to high-performance coating, glues The field of functional materials such as mixture, sealant, ink and surface conditioning agent.
Summary of the invention
It is an object of the present invention to provide the preparation side of a kind of aqueous polyurethane-silica nanometer complex emulsions Method.Aqueous polyurethane prepared by the present invention introduces silicon dioxide emulsion in emulsion process.Aqueous The stretching that the introducing of Nano silicon dioxide dispersion is effectively increased aqueous polyurethane latex film is strong Degree and modulus, film surface hydrophobic strengthens, and water absorption rate reduces and film has relatively high transparent. Technical scheme:
(1) synthesis of nano silicon dispersion liquid: by proportioning by emulsifying agent and catalyst dissolution Form aqueous phase in deionized water mix homogeneously, additionally by proportioning, organosilicone compounds is delayed Slowly it is added drop-wise in aqueous phase component, at 25 DEG C, reacts 24h, prepare nano silicon dispersion liquid；
(2) synthesis of aqueous polyurethane-silica nanometer complex emulsions: different two by proportioning In cyanate esters, dropping oligomer polyol and catalyst, at 50 DEG C after dropping Reaction 1-2h, is then gradually heating to 65 DEG C, adds hydrophilic monomer multi-hydroxy carboxy acid's compound Powder, carries out at this temperature reacting 4-5h, measures by toluene-di-n-butylamine method and generate pre-polymerization NCO (NCO) content of body, when close to NCO theoretical value, drops reaction temperature Low to 30 DEG C, dropping aminated compounds reaction 1h, in emulsion process, then introduce nanometer two Silicon oxide dispersion liquid, is eventually adding amine chain extender and expands base polyurethane prepolymer for use as in aqueous phase Chain prepares aqueous polyurethane-silica nanometer complex emulsions；
Described siloxanyl monomers selects methacryloxypropyl trimethoxy silane, methyl Acryloxypropyl triethoxysilane, VTES, vinyl trimethoxy Base silane, tetramethoxy-silicane, tetraethoxysilane, MTMS, methyl three Ethoxysilane, 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 3- Aminopropyltriethoxy dimethoxysilane, 3-aminopropyltriethoxy diethoxy silane, 3-(+)-2,3-Epoxy-1-propanol Ether epoxide propyl trimethoxy silicane, 3-glycydoxy methyldiethoxysilane, One of 3-glycydoxy triethoxysilane is planted or two kinds；
Described emulsifying agent selects dodecyl sodium sulfate, sodium cetanesulfonate, lauryl sulphate acid Sodium, sodium hexadecyl sulfate, Dodecyl trimethyl ammonium chloride, cetyl pyridinium bromide, Cetyl trimethylammonium bromide, lauryl ammonium chloride, the one of polyvinyl alcohol or two kinds；
Described catalyst selects ammonia, hydrochloric acid, acetic acid.
2, a kind of aqueous polyurethane-silica nanometer complex emulsions according to claim 1 Preparation method, it is characterised in that: described oligomer polyol select Polyethylene Glycol, poly-third Glycol, polytetrahydrofuran diol, polycaprolactone polyol, PCDL, polyoxyethylene -polyoxypropylene polyoxyethylene glycol, 10PE27 glycol, polybutyleneadipate Esterdiol, polyethylene terephthalate glycol, polybutylene terephthalate (PBT) glycol, α, alpha, omega-dihydroxy polydimethyl siloxane, dihydroxy polydiphenylsiloxane, the poly-trifluoro of dihydroxy One or more of propylmethylsiloxane, its molecular weight ranges is 400-10000.
3, a kind of aqueous polyurethane-silica nanometer complex emulsions according to claim 1 Preparation method, it is characterised in that: described diisocyanate cpd selects 2,4-toluene Diisocyanate, 2,6-toluene di-isocyanate(TDI), isophorone diisocyanate, methyl cyclohexane One of group diisocyanate, 2,2,4-trimethyl hexamethylene diisocyanate are planted.
4, a kind of aqueous polyurethane-silica nanometer complex emulsions according to claim 1 Preparation method, it is characterised in that: described hydrophilic monomer selects dihydromethyl propionic acid, dihydroxy Methylbutanoic acid, one of 1,2-dihydroxy-3-N-morpholinopropanesulfonic acid sodium is planted.
5, a kind of aqueous polyurethane-silica nanometer complex emulsions according to claim 1 Preparation method, it is characterised in that: described aminated compounds select triethylamine, triethanolamine, N, one of the different monooctyl ester of N dimethylamine base para Toluic Acid, ammonia are planted.
6, a kind of aqueous polyurethane-silica nanometer complex emulsions according to claim 1 Preparation method, it is characterised in that: described amine chain extender select ethylenediamine, hexamethylene diamine, two One of ethylene triamine, isophorone diamine, 2 methyl pentamethylenediamine are planted.
Accompanying drawing explanation
The tensile property of Fig. 1 aqueous polyurethane-silica nanometer composite membrane
The water contact angle of Fig. 2 aqueous polyurethane-silica nanometer composite membrane
Detailed description of the invention
In order to preferably explain the present invention, below in conjunction with specific embodiment, the present invention is entered one Step explains in detail.
Embodiment 1
Polysiloxanes microsphere emulsion: weigh 0.2g dodecyl sodium sulfate by proportioning, 0.1g gathers Vinylpyrrolidone and 0.1g ammonia solvent form water in 40.0g deionized water mix homogeneously Phase, and join in 250mL four-neck flask.Additionally weigh 9.0g vinyl front three by proportioning TMOS monomer and 1.0g tetraethyl orthosilicate mix and are uniformly dispersed formation oil phase, by oil phase Component is added drop-wise in aqueous phase component, dropping limit, limit stirring and emulsifying, at room temperature polyreaction 24h, Prepare poly-silicon dioxide emulsion
Embodiment 2
Prepare aqueous polyurethane film: equipped with agitator, thermometer and reflux condensing tube In 250mL four-neck flask add 17.4g isophorone diisocyanate (IPDI), room temperature next Limit stirring is while dripping 57.1g polycarbonate polyol (PCD2000) and 0.05g with Dropping funnel Catalyst dibutyltin dilaurylate (DBTDL), rate of addition controls in 1.5h, dropping After 45 ± 5 DEG C react 1-2h；Then heat to 60 DEG C, add 3.75g dihydroxymethyl Propanoic acid (DMPA), reacts 3-4h, measures the extent of reaction by toluene-di-n-butylamine back titration method, Until measuring NCO group content to reach theoretical value；Then in resin, add the three of 2.83g Ethamine, reacts 0.5-1h；The deionized water dripping 198.3g in system carries out emulsifying；Finally Prepare aqueous polyurethane film.
Embodiment 3
Prepare the emulsion modified aqueous polyurethane-organosilicon membrane of polysiloxanes microsphere: equipped with stirring The 250mL four-neck flask of device, thermometer and reflux condensing tube adds 17.4g isophorone two Isocyanates (IPDI), stirs under room temperature and drips the poly-carbonic acid of 51.3g with Dropping funnel Ester polyol (PCD2000) and 0.05g catalyst dibutyltin dilaurylate (DBTDL), drip Acceleration Control, in 1.5h, reacts 1-2h at 45 ± 5 DEG C after dropping；It is added thereto to 6.85g organo-silicon compound (PDMS), react 0.5-1h；Then heat to 60 DEG C, add 3.75g dihydromethyl propionic acid (DMPA), reacts 3-4h, by toluene-di-n-butylamine back titration Method measures the extent of reaction, until measuring NCO group content to reach theoretical value；Then to resin The triethylamine of middle addition 2.83g, reacts 0.5-1h；Add the poly-silicon dioxide emulsion of 14.91g, Reaction 0.5-1h；The deionized water dripping 198.3g in system carries out emulsifying；Finally prepare poly- Silica modified aqueous polyurethane film.

Claims (6)

1. a preparation method for aqueous polyurethane-silica nanometer complex emulsions, its It is characterised by that composition includes: the oligomer polyol of 30wt%-50wt%, 20wt%-40wt% Diisocyanate cpd, the hydrophilic monomer of 3wt%-7wt%, the amine of 2wt%-5wt% Compounds, the amine chain extender of 1wt%-5wt%, the nanometer titanium dioxide of 5wt%-20wt% Silicon, concrete preparation method is as follows:
(1) synthesis of nano silicon dispersion liquid: by proportioning by emulsifying agent and catalyst dissolution Form aqueous phase in deionized water mix homogeneously, additionally by proportioning, organosilicone compounds is delayed Slowly it is added drop-wise in aqueous phase component, at 25 DEG C, reacts 24h, prepare nano silicon dispersion liquid；
(2) synthesis of aqueous polyurethane-silica nanometer complex emulsions: different two by proportioning In cyanate esters, dropping oligomer polyol and catalyst, at 50 DEG C after dropping Reaction 1-2h, is then gradually heating to 65 DEG C, adds hydrophilic monomer multi-hydroxy carboxy acid's compound Powder, carries out at this temperature reacting 4-5h, measures by toluene-di-n-butylamine method and generate pre-polymerization NCO (NCO) content of body, when close to NCO theoretical value, drops reaction temperature Low to 30 DEG C, dropping aminated compounds reaction 1h, in emulsion process, then introduce nanometer two Silicon oxide dispersion liquid, is eventually adding amine chain extender and expands base polyurethane prepolymer for use as in aqueous phase Chain prepares aqueous polyurethane-silica nanometer complex emulsions；
Described siloxanyl monomers selects methacryloxypropyl trimethoxy silane, methyl Acryloxypropyl triethoxysilane, VTES, vinyl trimethoxy Base silane, tetramethoxy-silicane, tetraethoxysilane, MTMS, methyl three Ethoxysilane, 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 3- Aminopropyltriethoxy dimethoxysilane, 3-aminopropyltriethoxy diethoxy silane, 3-(+)-2,3-Epoxy-1-propanol Ether epoxide propyl trimethoxy silicane, 3-glycydoxy methyldiethoxysilane, One of 3-glycydoxy triethoxysilane is planted or two kinds；
Described emulsifying agent selects dodecyl sodium sulfate, sodium cetanesulfonate, dodecyl Sodium sulfate, sodium hexadecyl sulfate, Dodecyl trimethyl ammonium chloride, cetyl bromination pyrrole Pyridine, cetyl trimethylammonium bromide, lauryl ammonium chloride, the one of polyvinyl alcohol or two Kind；
Described catalyst selects ammonia, hydrochloric acid, acetic acid.
A kind of aqueous polyurethane-silica nanometer complex emulsions Preparation method, it is characterised in that: described oligomer polyol select Polyethylene Glycol, poly-third Glycol, polytetrahydrofuran diol, polycaprolactone polyol, PCDL, polyoxyethylene -polyoxypropylene polyoxyethylene glycol, 10PE27 glycol, polybutyleneadipate Esterdiol, polyethylene terephthalate glycol, polybutylene terephthalate (PBT) glycol, α, alpha, omega-dihydroxy polydimethyl siloxane, dihydroxy polydiphenylsiloxane, the poly-trifluoro of dihydroxy One or more of propylmethylsiloxane, its molecular weight ranges is 400-10000.
A kind of aqueous polyurethane-silica nanometer complex emulsions Preparation method, it is characterised in that: described diisocyanate cpd selects 2,4-toluene Diisocyanate, 2,6-toluene di-isocyanate(TDI), isophorone diisocyanate, methyl cyclohexane One of group diisocyanate, 2,2,4-trimethyl hexamethylene diisocyanate are planted.
A kind of aqueous polyurethane-silica nanometer complex emulsions Preparation method, it is characterised in that: described hydrophilic monomer selects dihydromethyl propionic acid, dihydroxy Methylbutanoic acid, one of 1,2-dihydroxy-3-N-morpholinopropanesulfonic acid sodium is planted.
A kind of aqueous polyurethane-silica nanometer complex emulsions Preparation method, it is characterised in that: described aminated compounds select triethylamine, triethanolamine, N, one of the different monooctyl ester of N dimethylamine base para Toluic Acid, ammonia are planted.
A kind of aqueous polyurethane-silica nanometer complex emulsions Preparation method, it is characterised in that: described amine chain extender select ethylenediamine, hexamethylene diamine, two One of ethylene triamine, isophorone diamine, 2 methyl pentamethylenediamine are planted.
CN201610309310.0A 2016-05-11 2016-05-11 Preparation method of waterborne polyurethane-silicon dioxide nano composite emulsion Pending CN105732940A (en)

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