CN106810657A - The preparation method of environment-friendly package material - Google Patents
The preparation method of environment-friendly package material Download PDFInfo
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- CN106810657A CN106810657A CN201510865708.8A CN201510865708A CN106810657A CN 106810657 A CN106810657 A CN 106810657A CN 201510865708 A CN201510865708 A CN 201510865708A CN 106810657 A CN106810657 A CN 106810657A
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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
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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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6685—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
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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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
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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
- C08G18/70—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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- 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
- C09D175/08—Polyurethanes from polyethers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
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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
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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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
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- 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
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- Chemical Kinetics & Catalysis (AREA)
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
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- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses the preparation method of environment-friendly package material, including following operation：1）At room temperature to toluene di-isocyanate(TDI) etc. is added in the first reactor, primary product is obtained；2）To dihydromethyl propionic acid is added in primary product, triethylamine is added, aromatic waterborne polyurethane emulsion is obtained；3）At room temperature to Ludox and aromatic waterborne polyurethane emulsion is added in the 3rd reactor, mixed emulsion is obtained, it is standby；4）To appropriate acrylic acid copolymer sodium salt etc. is added in mixed emulsion, crude product is obtained；5）To talcum powder is added in crude product, environment-friendly package material is obtained.Production technology of the invention has the advantages that easy to operate, production efficiency is high, and effective temporary enclosed protection can be carried out to protected object using the obtained packaging material of the present invention.
Description
Technical field
The present invention relates to decorating field, more particularly, to the preparation method of environment-friendly package material.
Background technology
To prevent material or half product under the atmospheric environment to be contaminated, corrode and damage, and increase the service life, it will usually there is the coating of good protective and strippable property in their surface smear it is carried out effective and interim to seal protection up for safekeeping.In this way, can both isolate air, salt fog, the invasion of microorganism in the external world, antiseptic effect is reached；The effect of decontamination can be cleaned to reach by adsorbing pollutant again.For compared with solvent-borne type protective coating, aqueous protective coating has more security and the feature of environmental protection, thus is widely used in the decorating field of product.But, existing aqueous protective coating still has the shortcomings that coating strength is low, strippable property is poor and barrier propterty is single.
The content of the invention
The purpose of the present invention is the defect for overcoming above-mentioned prior art, there is provided the preparation method of environment-friendly package material, has the advantages that easy to operate, production efficiency is high, and effective temporary enclosed protection can be carried out to protected object using the obtained packaging material of the present invention.
The purpose of the present invention is achieved through the following technical solutions：
The preparation method of environment-friendly package material, including following operation：
1）At room temperature to addition toluene di-isocyanate(TDI), polypropylene glycol, dibutyl tin laurate, triethylamine and butanone in the first reactor, temperature is risen to 58 ~ 70 DEG C again, their-NCO% values in hybrid reaction to system in the first reactor is no longer changed, obtain primary product, it is standby；
2）By temperature control at 80 DEG C, to operation 1）Dihydromethyl propionic acid is added in the primary product of gained and 100 ~ 130min is reacted, 38 ~ 43 DEG C are cooled the temperature to, triethylamine is added, again by temperature control at 68 ~ 70 DEG C, pressure is controlled in -0.095 ~ -0.085 MPa, carries out vacuum distillation, until solid content reaches 80 ~ 95%, secondary product is obtained；To adding secondary product in the second reactor for filling distilled water and secondary product is scattered in distilled water, ethylenediamine solution is added, aromatic waterborne polyurethane emulsion is obtained, it is standby；
3）At room temperature to addition Ludox and operation 2 in the 3rd reactor）The aromatic waterborne polyurethane emulsion of gained, by the rotating speed stirring 50 ~ 70min of mixing of 200 ~ 300r/min, obtains mixed emulsion, standby；
4）To operation 3）Acrylate copolymer ammonium salt solution, acrylic acid copolymer sodium salt, alkali soluble is swollen acrylic thickener, organic silicon modified by polyether, silicone emulsion and polyether polyester azo polyether polyeste are added in the mixed emulsion of gained, by the 4 ~ 10min of rotating speed stirring mixing of 400 ~ 600r/min；Add triethylamine and pH value is adjusted to 8 ~ 9, obtain crude product, it is standby；
5）To operation 4）Talcum powder is added in the crude product of gained, by the 35 ~ 42min of rotating speed stirring mixing of 1500 ~ 1800r/min；Organic silicon modified by polyether and distilled water are added, by the rotating speed stirring 15 ~ 30min of mixing of 400 ~ 600r/min, environment-friendly package material is obtained；
The aromatic waterborne polyurethane emulsion is obtained by the raw material of following quality proportioning：40 ~ 80 parts of toluene di-isocyanate(TDI), 40 ~ 80 parts of polypropylene glycol, 3 ~ 10 parts of dihydromethyl propionic acid, 50 ~ 80 parts of butanone, 5 ~ 12 parts of ethylenediamine, 3 ~ 11 parts of triethylamine, 1 ~ 3 part of dibutyl tin laurate, 40 ~ 80 parts of distilled water；The environment-friendly package material is obtained by the raw material of following mass fraction：Aromatic waterborne polyurethane emulsion 60 ~ 80%, Ludox 5 ~ 10%, talcum powder 3 ~ 8%, silicone emulsion 1 ~ 3%, acrylate copolymer ammonium salt solution 0.1 ~ 0.5%, alkali soluble is swollen acrylic thickener 0.5 ~ 1%, polyether polyester azo polyether polyeste 0.3 ~ 0.6%, acrylic acid copolymer sodium salt 0.1 ~ 0.5%, organic silicon modified by polyether 0.1 ~ 0.5%, balance of distilled water.
The present invention first adds various auxiliary agents to make their uniform mixing during environment-friendly package material is prepared in mixed emulsion, and adding filler carries out high speed dispersion.In the preparation process of aromatic waterborne polyurethane emulsion, by operation 2）Vacuum distillation can remove butanone solvent, and remaining solvent is used as cosolvent, the aromatic waterborne polyurethane emulsion for so being formed more security and the feature of environmental protection.Aqueous protective coating is mainly made up of film forming matter, filler, auxiliary agent and solvent.Wherein, film forming matter is the nucleus of protective coating, and the present invention, as film forming matter, can improve stability, strippable property, mechanical strength and the tolerance to acid-base salt solution of coating from aromatic waterborne polyurethane emulsion and Ludox compounding.The following raw material is selected in the preparation of aromatic waterborne polyurethane emulsion：The reaction of isocyanate groups and hydroxyl is carried out from toluene di-isocyanate(TDI) and polypropylene glycol, can so assign coating film excellent mechanical property and barrier propterty.In the reaction, butanone is added to reduce the viscosity of primary product.Because when the temperature of the reaction is higher than 70 DEG C, though the content of-NCO can be rapidly reached theoretical value, now side reaction is more, so easily makes unstable product quality；And when reaction is less than 58 DEG C, production efficiency can be influenceed because reaction speed is relatively slow again.Therefore, by reaction temperature control at 58 ~ 70 DEG C.Relatively it is used alone for dibutyl tin laurate, reaction rate can be significantly improved as catalyst from dibutyl tin laurate and triethylamine compounding, offsets the adverse effect of solvent effect.From ethylenediamine as chain extender, it can carry out chain extension to secondary product, can so improve the tensile strength of coating film.The addition of Ludox can make in the nano-silica filled film to coating, and the segment of silica can constitute the network-like structure for mutually running through with the organic high molecular polymer in coating and talcum powder, so, the pliability of organic polymer can be improved, meanwhile, coating film bulk strength and hardness can also be improved.Because the permeability of Ludox is fabulous, it can be penetrated into inside protected base material so that coating film is securely attached on base material.Ludox can also improve the consistency of coating film, can so prevent moisture and other media from invading, and then improve the corrosion resistance of film.
Filler is indispensable part in formulation for coating material, and filling effect is played in coating.From talcum powder as filler, paint coatings can be prevented to be cracked, improve levelability, washability, water resistance of coating etc..Alkali soluble is swollen, and acrylic thickener can improve the viscosity of dispersion, be conducive to dispersion of the talcum powder in system, prevent talcum powder from sinking to luming；The denseness of coating can also be increased simultaneously, the stability of coating is improved.The base material adhesive force of adjusting coating film is capable of in the use of silicone emulsion, film is had preferable peeling effect.Used as wetting agent, it can reduce the surface tension of coating film to acrylate copolymer ammonium salt solution, coating film cissing phenomenon is occurred, is prevented from making application uneven because protected object is unclean with soaking base material, reduction well.Because filler all has hydrophobicity, thus their less stables in water, easily reunite and sink.And pass through to add acrylic acid copolymer sodium salt, then can keep dispersiveness of the filler in water.Polyether polyester azo polyether polyeste is used as levelling agent, it is possible to decrease the interfacial tension between coating and ground, improves the phenomenons such as coating is bad to shrinkage cavity that by the wetability of ground, reduction causes by ground, adhesive force.Coating is required for various artificial and mechanically actuateds in production, storage and work progress, foam is so easily caused to produce, and foam can hinder the dispersion of talcum powder, and film coated surface is caused to form pin hole and shrinkage cavity, so as to influence the outward appearance of coating film, anti-corrosive properties and weatherability.And add the organic silicon modified by polyether can be then effectively improved above mentioned problem.
To ensure isocyanate group-NCO and being smoothed out that the hydroxyl-OH reacts, further, the mol ratio of the isocyanate group-NCO and hydroxyl-OH is 2.2 ~ 3.6 in the raw material of the aromatic waterborne polyurethane emulsion:1.As-NCO/-OH ＜ 2.2, the viscosity of product can be increased, and be difficult dispersion；And as-NCO/-OH ＞ 3.6, the easy gel of aromatic waterborne polyurethane emulsion reduces storage period.
To reach good neutralization, further, the addition of the triethylamine and the dihydromethyl propionic acid equimolar amounts.
It is that balance is reached between adhesive force and peel strength, further, the Ludox is 1 with the mass ratio of the aromatic waterborne polyurethane emulsion:4.The consumption of Ludox directly affects the combination property and production cost of coating.Specifically, when the addition of Ludox is excessive, not only result in film and become fragile, film adhesive is excessive, be unfavorable for peeling off；The stability of coating system can be also influenceed, increases the production cost of coating.And Ludox consumption it is very few when, active force of the nano-particle in coating is weaker, so causes the performance improvement effect of coating unobvious.Therefore consumption of the Ludox in coating must be rationally appropriate.When the present invention is from the ratio, may be such that the tensile strength and elongation at break of coating film is strengthened, while moderate peel strength is also maintained, good acid and alkali-resistance salt performance.
To improve stability of the filler in system, further, the addition of the acrylic acid copolymer sodium salt is the 2 ~ 4% of the talcum powder addition.
Further, the operation 1）The temperature control of middle hybrid reaction is at 68 ~ 70 DEG C, and the hybrid reaction time is 50 ~ 75min..Because the reactivity of toluene di-isocyanate(TDI) is higher, thus operation 1）Reaction temperature can be controlled in 68 ~ 70 DEG C.
Effectively to control operation 1）In reaction-reaction rate of NCO group, further, the operation 1）In also comprise the following steps：During hybrid reaction, every 3 ~ 5min measurements once in first reactor-NCO group accounts for the weight/mass percentage composition of system.
The invention has the advantages that：Production technology of the invention has the advantages that easy to operate, production efficiency is high, and effective closing protection can be carried out to protected object using the obtained environment-friendly package material of the present invention, prevents protected object to be contaminated, corrode and damages.Specifically, mechanical strength, strippable property and the tolerance to acid-base salt solution of coating can be improved as film forming matter from aromatic waterborne polyurethane emulsion and Ludox compounding.From talcum powder as filler, the performances such as hardness, intensity, wearability and the base material adhesive force of coating film can be improved.The viscosity of dispersion can be improved from the swollen acrylic thickener of alkali soluble, increases the denseness of coating, improve the stability of coating.From silicone emulsion as remover, the base material adhesive force of energy adjusting coating film improves the rippability of film.From acrylate copolymer ammonium salt solution as wetting agent, coating can be enable film cissing phenomenon occur with soaking base material, reduction well.From acrylic acid copolymer sodium salt as dispersant, dispersiveness of the filler in water can be kept.From polyether polyester azo polyether polyeste as levelling agent, it is possible to decrease the interfacial tension between coating and ground, coating is improved to by the wetability of ground.From organic silicon modified by polyether as defoamer, the generation of foam can be reduced, so as to improve the outward appearance of coating film, anti-corrosive properties and weatherability.
Specific embodiment
With reference to embodiment, the present invention is described in further detail, but embodiments of the present invention not limited to this.
Embodiment 1
The preparation method of environment-friendly package material, including following operation：
1）At room temperature to addition toluene di-isocyanate(TDI), polypropylene glycol, dibutyl tin laurate, triethylamine and butanone in the first reactor, temperature is risen to 58 ~ 70 DEG C again, their-NCO% values in hybrid reaction to system in the first reactor is no longer changed, obtain primary product, it is standby；
2）By temperature control at 80 DEG C, to operation 1）Dihydromethyl propionic acid is added in the primary product of gained and 100 ~ 130min is reacted, 38 ~ 43 DEG C are cooled the temperature to, triethylamine is added, again by temperature control at 68 ~ 70 DEG C, pressure is controlled in -0.095 ~ -0.085 MPa, carries out vacuum distillation, until solid content reaches 80 ~ 95%, secondary product is obtained；To adding secondary product in the second reactor for filling distilled water and secondary product is scattered in distilled water, ethylenediamine solution is added, aromatic waterborne polyurethane emulsion is obtained, it is standby；
3）At room temperature to addition Ludox and operation 2 in the 3rd reactor）The aromatic waterborne polyurethane emulsion of gained, by the rotating speed stirring 50 ~ 70min of mixing of 200 ~ 300r/min, obtains mixed emulsion, standby；
4）To operation 3）Acrylate copolymer ammonium salt solution, acrylic acid copolymer sodium salt, alkali soluble is swollen acrylic thickener, organic silicon modified by polyether, silicone emulsion and polyether polyester azo polyether polyeste are added in the mixed emulsion of gained, by the 4 ~ 10min of rotating speed stirring mixing of 400 ~ 600r/min；Add triethylamine and pH value is adjusted to 8 ~ 9, obtain crude product, it is standby；
5）To operation 4）Talcum powder is added in the crude product of gained, by the 35 ~ 42min of rotating speed stirring mixing of 1500 ~ 1800r/min；Organic silicon modified by polyether and distilled water are added, by the rotating speed stirring 15 ~ 30min of mixing of 400 ~ 600r/min, environment-friendly package material is obtained；
The aromatic waterborne polyurethane emulsion is obtained by the raw material of following quality proportioning：40 ~ 80 parts of toluene di-isocyanate(TDI), 40 ~ 80 parts of polypropylene glycol, 3 ~ 10 parts of dihydromethyl propionic acid, 50 ~ 80 parts of butanone, 5 ~ 12 parts of ethylenediamine, 3 ~ 11 parts of triethylamine, 1 ~ 3 part of dibutyl tin laurate, 40 ~ 80 parts of distilled water；The environment-friendly package material is obtained by the raw material of following mass fraction：Aromatic waterborne polyurethane emulsion 60 ~ 80%, Ludox 5 ~ 10%, talcum powder 3 ~ 8%, silicone emulsion 1 ~ 3%, acrylate copolymer ammonium salt solution 0.1 ~ 0.5%, alkali soluble is swollen acrylic thickener 0.5 ~ 1%, polyether polyester azo polyether polyeste 0.3 ~ 0.6%, acrylic acid copolymer sodium salt 0.1 ~ 0.5%, organic silicon modified by polyether 0.1 ~ 0.5%, balance of distilled water.
The present invention first adds various auxiliary agents to make their uniform mixing during environment-friendly package material is prepared in mixed emulsion, and adding filler carries out high speed dispersion.In the preparation process of aromatic waterborne polyurethane emulsion, by operation 2）Vacuum distillation can remove butanone solvent, and remaining solvent is used as cosolvent, the aromatic waterborne polyurethane emulsion for so being formed more security and the feature of environmental protection.Aqueous protective coating is mainly made up of film forming matter, filler, auxiliary agent and solvent.Wherein, film forming matter is the nucleus of protective coating, and the present invention, as film forming matter, can improve stability, strippable property, mechanical strength and the tolerance to acid-base salt solution of coating from aromatic waterborne polyurethane emulsion and Ludox compounding.The following raw material is selected in the preparation of aromatic waterborne polyurethane emulsion：The reaction of isocyanate groups and hydroxyl is carried out from toluene di-isocyanate(TDI) and polypropylene glycol, can so assign coating film excellent mechanical property and barrier propterty.In the reaction, butanone is added to reduce the viscosity of primary product.Because when the temperature of the reaction is higher than 70 DEG C, though the content of-NCO can be rapidly reached theoretical value, now side reaction is more, so easily makes unstable product quality；And when reaction is less than 58 DEG C, production efficiency can be influenceed because reaction speed is relatively slow again.Therefore, by reaction temperature control at 58 ~ 70 DEG C.Relatively it is used alone for dibutyl tin laurate, reaction rate can be significantly improved as catalyst from dibutyl tin laurate and triethylamine compounding, offsets the adverse effect of solvent effect.From ethylenediamine as chain extender, it can carry out chain extension to secondary product, can so improve the tensile strength of coating film.The addition of Ludox can make in the nano-silica filled film to coating, and the segment of silica can constitute the network-like structure for mutually running through with the organic high molecular polymer in coating and talcum powder, so, the pliability of organic polymer can be improved, meanwhile, coating film bulk strength and hardness can also be improved.Because the permeability of Ludox is fabulous, it can be penetrated into inside protected base material so that coating film is securely attached on base material.Ludox can also improve the consistency of coating film, can so prevent moisture and other media from invading, and then improve the corrosion resistance of film.
Filler is indispensable part in formulation for coating material, and filling effect is played in coating.From talcum powder as filler, paint coatings can be prevented to be cracked, improve levelability, washability, water resistance of coating etc..Alkali soluble is swollen, and acrylic thickener can improve the viscosity of dispersion, be conducive to dispersion of the talcum powder in system, prevent talcum powder from sinking to luming；The denseness of coating can also be increased simultaneously, the stability of coating is improved.The base material adhesive force of adjusting coating film is capable of in the use of silicone emulsion, film is had preferable peeling effect.Used as wetting agent, it can reduce the surface tension of coating film to acrylate copolymer ammonium salt solution, coating film cissing phenomenon is occurred, is prevented from making application uneven because protected object is unclean with soaking base material, reduction well.Because filler all has hydrophobicity, thus their less stables in water, easily reunite and sink.And pass through to add acrylic acid copolymer sodium salt, then can keep dispersiveness of the filler in water.Polyether polyester azo polyether polyeste is used as levelling agent, it is possible to decrease the interfacial tension between coating and ground, improves the phenomenons such as coating is bad to shrinkage cavity that by the wetability of ground, reduction causes by ground, adhesive force.Coating is required for various artificial and mechanically actuateds in production, storage and work progress, foam is so easily caused to produce, and foam can hinder the dispersion of talcum powder, and film coated surface is caused to form pin hole and shrinkage cavity, so as to influence the outward appearance of coating film, anti-corrosive properties and weatherability.And add the organic silicon modified by polyether can be then effectively improved above mentioned problem.
To ensure isocyanate group-NCO and being smoothed out that the hydroxyl-OH reacts, it is preferable that the mol ratio of the isocyanate group-NCO and hydroxyl-OH is 2.2 ~ 3.6 in the raw material of the aromatic waterborne polyurethane emulsion:1.As-NCO/-OH ＜ 2.2, the viscosity of product can be increased, and be difficult dispersion；And as-NCO/-OH ＞ 3.6, the easy gel of aromatic waterborne polyurethane emulsion reduces storage period.
To reach good neutralization, it is preferable that the addition of the triethylamine and the dihydromethyl propionic acid equimolar amounts.
It is that balance is reached between adhesive force and peel strength, it is preferable that the Ludox is 1 with the mass ratio of the aromatic waterborne polyurethane emulsion:4.The consumption of Ludox directly affects the combination property and production cost of coating.Specifically, when the addition of Ludox is excessive, not only result in film and become fragile, film adhesive is excessive, be unfavorable for peeling off；The stability of coating system can be also influenceed, increases the production cost of coating.And Ludox consumption it is very few when, active force of the nano-particle in coating is weaker, so causes the performance improvement effect of coating unobvious.Therefore consumption of the Ludox in coating must be rationally appropriate.When the present invention is from the ratio, may be such that the tensile strength and elongation at break of coating film is strengthened, while moderate peel strength is also maintained, good acid and alkali-resistance salt performance.
To improve stability of the filler in system, it is preferable that the addition of the acrylic acid copolymer sodium salt is the 2 ~ 4% of the talcum powder addition.
Preferably, the operation 1）The temperature control of middle hybrid reaction is at 68 ~ 70 DEG C, and the hybrid reaction time is 50 ~ 75min..Because the reactivity of toluene di-isocyanate(TDI) is higher, thus operation 1）Reaction temperature can be controlled in 68 ~ 70 DEG C.
Effectively to control operation 1）In reaction-reaction rate of NCO group, it is preferable that the operation 1）In also comprise the following steps：During hybrid reaction, every 3 ~ 5min measurements once in first reactor-NCO group accounts for the weight/mass percentage composition of system.
Above content is to combine the further description that specific preferred embodiment is made to the present invention, it is impossible to assert that specific embodiment of the invention is confined to these explanations.For general technical staff of the technical field of the invention, the other embodiment drawn in the case where technical scheme is not departed from should be included within the scope of the present invention.
Claims (7)
1. the preparation method of environment-friendly package material, it is characterised in that：
Including following operation：
1）At room temperature to addition toluene di-isocyanate(TDI), polypropylene glycol, dibutyl tin laurate, triethylamine and butanone in the first reactor, temperature is risen to 58 ~ 70 DEG C again, their-NCO% values in hybrid reaction to system in the first reactor is no longer changed, obtain primary product, it is standby；
2）By temperature control at 80 DEG C, to operation 1）Dihydromethyl propionic acid is added in the primary product of gained and 100 ~ 130min is reacted, 38 ~ 43 DEG C are cooled the temperature to, triethylamine is added, again by temperature control at 68 ~ 70 DEG C, pressure is controlled in -0.095 ~ -0.085 MPa, carries out vacuum distillation, until solid content reaches 80 ~ 95%, secondary product is obtained；To adding secondary product in the second reactor for filling distilled water and secondary product is scattered in distilled water, ethylenediamine solution is added, aromatic waterborne polyurethane emulsion is obtained, it is standby；
3）At room temperature to addition Ludox and operation 2 in the 3rd reactor）The aromatic waterborne polyurethane emulsion of gained, by the rotating speed stirring 50 ~ 70min of mixing of 200 ~ 300r/min, obtains mixed emulsion, standby；
4）To operation 3）Added in the mixed emulsion of gained acrylate copolymer ammonium salt solution,
Acrylic thickener that acrylic acid copolymer sodium salt, alkali soluble are swollen, organic silicon modified by polyether, silicone emulsion and polyether polyester azo polyether polyeste, by the 4 ~ 10min of rotating speed stirring mixing of 400 ~ 600r/min；Add triethylamine and pH value is adjusted to 8 ~ 9, obtain crude product, it is standby；
5）To operation 4）Talcum powder is added in the crude product of gained, by the 35 ~ 42min of rotating speed stirring mixing of 1500 ~ 1800r/min；Organic silicon modified by polyether and distilled water are added, by the rotating speed stirring 15 ~ 30min of mixing of 400 ~ 600r/min, environment-friendly package material is obtained；
The aromatic waterborne polyurethane emulsion is obtained by the raw material of following quality proportioning：40 ~ 80 parts of toluene di-isocyanate(TDI), 40 ~ 80 parts of polypropylene glycol, 3 ~ 10 parts of dihydromethyl propionic acid, 50 ~ 80 parts of butanone, 5 ~ 12 parts of ethylenediamine, 3 ~ 11 parts of triethylamine, 1 ~ 3 part of dibutyl tin laurate, 40 ~ 80 parts of distilled water；The environment-friendly package material is obtained by the raw material of following mass fraction：Aromatic waterborne polyurethane emulsion 60 ~ 80%, Ludox 5 ~ 10%, talcum powder 3 ~ 8%, silicone emulsion 1 ~ 3%, acrylate copolymer ammonium salt solution 0.1 ~ 0.5%, alkali soluble is swollen acrylic thickener 0.5 ~ 1%, polyether polyester azo polyether polyeste 0.3 ~ 0.6%, acrylic acid copolymer sodium salt 0.1 ~ 0.5%, organic silicon modified by polyether 0.1 ~ 0.5%, balance of distilled water.
2. the preparation method of environment-friendly package material according to claim 1, it is characterised in that：The mol ratio of the isocyanate group-NCO and hydroxyl-OH is 2.2 ~ 3.6 in the raw material of the aromatic waterborne polyurethane emulsion:1.
3. the preparation method of environment-friendly package material according to claim 1, it is characterised in that：The addition of the triethylamine and the dihydromethyl propionic acid equimolar amounts.
4. the preparation method of environment-friendly package material according to claim 1, it is characterised in that：The Ludox is 1 with the mass ratio of the aromatic waterborne polyurethane emulsion:4.
5. the preparation method of environment-friendly package material according to claim 1, it is characterised in that：The addition of the acrylic acid copolymer sodium salt is the 2 ~ 4% of the talcum powder addition.
6. the preparation method of the environment-friendly package material according to any one in claim 1 ~ 5, it is characterised in that：The operation 1）The temperature control of middle hybrid reaction is at 68 ~ 70 DEG C, and the hybrid reaction time is 50 ~ 75min.
7. the preparation method of environment-friendly package material according to claim 6, it is characterised in that：The operation 1）In also comprise the following steps：During hybrid reaction, every 3 ~ 5min measurements once in first reactor-NCO group accounts for the weight/mass percentage composition of system.
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Application publication date: 20170609 |