CN114349912B - Modified waterborne polyurethane acrylate composite emulsion and preparation method and application thereof - Google Patents
Modified waterborne polyurethane acrylate composite emulsion and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a modified waterborne polyurethane acrylate composite emulsion, a preparation method and application thereof. The modified aqueous polyurethane acrylate composite emulsion comprises the following components: 10-30 parts of multilayer graphene oxide modified polyurethane acrylate oligomer, 10-30 parts of polyurethane acrylate oligomer, 20-40 parts of acrylate monomer, 3-5 parts of photoinitiator, 0.2-0.5 part of flatting agent and 30-50 parts of water. The preparation method comprises the steps of uniformly mixing the multilayer graphene oxide modified polyurethane acrylate oligomer, the acrylate monomer and water, heating, stirring by a stirrer, and naturally cooling to room temperature; and sequentially adding a photoinitiator and a flatting agent, stirring uniformly at normal temperature, standing for defoaming, and preserving in a dark place to obtain the modified aqueous polyurethane acrylate composite emulsion. The invention can be used for adhesives and as paint on the surfaces of metal, plastic or timber, and is especially suitable for metal corrosion prevention.
Description
Technical Field
The invention relates to the field of composite materials, in particular to a modified waterborne polyurethane acrylate composite emulsion, a preparation method and application thereof.
Background
At present, the waterborne polyurethane acrylate resin is a novel safe and environment-friendly green resin which is developed rapidly in recent years, and along with the enhancement of environmental awareness and the trend of environmental protection policy, the low-VOC environment-friendly material waterborne polyurethane acrylate resin has wide development prospect and is widely applied to the fields of paint, adhesives, printing ink, wind power and the like. However, the water resistance, mechanical strength, heat resistance and barrier property of the aqueous polyurethane acrylate resin are poor, and the modification of enhancement or conductivity is carried out by adopting graphene or graphene oxide at present, but how to fully exert the dispersion of the aqueous polyurethane acrylate resin in a matrix and how to realize the compatibility or grafting property between polyurethane acrylate and graphene or graphene oxide so as to fully exert the modification effect of the aqueous polyurethane acrylate resin are hot spots studied in the field.
Disclosure of Invention
The invention aims to provide a modified aqueous polyurethane acrylate composite emulsion and a preparation method thereof, which fully utilize the existing graphite to conduct intercalation stripping to obtain multi-layer graphene oxide, and then conduct an original intercalation method, so that the interlayer spacing and dispersibility are increased, the compatibility between the modified aqueous polyurethane acrylate composite emulsion and polyurethane acrylate is improved, the grafting rate is improved, and the modified polyurethane acrylate composite material has excellent performances of water resistance, mechanical strength, heat resistance, gas barrier property, conductivity and the like.
In order to achieve the above purpose, the invention provides a modified aqueous polyurethane acrylate composite emulsion, which comprises the following components:
further, the preparation method of the multilayer graphene oxide modified polyurethane acrylate oligomer comprises the following steps: (1) Putting graphite into a mixed solution of potassium persulfate and concentrated sulfuric acid, uniformly stirring, heating to 60-70 ℃, reacting for 20-30min, carrying out suction filtration, soaking and washing with deionized water at 60-80 ℃, and drying to obtain oxidized expanded graphite; (2) Placing oxidized expanded graphite into triethanolamine water solution, stirring uniformly, heating to 50-60 ℃, grinding and stripping for 10-20min, suction filtering, soaking and washing with deionized water at 60-80 ℃, and drying to obtain primarily intercalated multilayer graphene oxide; (3) Weighing 10-20 parts of primarily intercalated multilayer graphene oxide by mass, dispersing in 50 parts of water, adding 2-4 parts of dodecyl trimethyl ammonium chloride, stirring in a stirrer, heating for 1-2 hours at the rotating speed of 500-800r/min, carrying out suction filtration at the temperature of 70-80 ℃, washing with deionized water, and drying to obtain primarily intercalated modified multilayer graphene oxide; (4) Dispersing the primary intercalation modified multilayer graphene oxide in 50 parts of water, adding 6-8 parts of methacryloxyethyl trimethyl ammonium chloride according to parts by weight, stirring and heating in a stirrer for 1-2 hours at a rotating speed of 500-800r/min, performing suction filtration at a temperature of 60-70 ℃, washing with deionized water, and drying to obtain secondary intercalation modified multilayer graphene oxide; (5) Dispersing the secondary intercalation graphene oxide in 50 parts of aqueous solution of polyvinyl alcohol with the concentration of 6wt%, stirring in a stirrer, heating for 2-3 hours at the rotating speed of 100-200 r/min and the temperature of 50-60 ℃, carrying out suction filtration, washing with deionized water, and drying to obtain the functional multilayer graphene oxide; (6) 10 parts of the functional multilayer graphene oxide is added into 20 parts of first-batch diisocyanate, the temperature is heated to 50-90 ℃, dihydric alcohol with the mole ratio of 1:1 with the first-batch diisocyanate and 0.05-0.1 part of catalyst are added after 1-2 hours, 20 parts of second-batch diisocyanate are continuously added, and finally the functional multilayer graphene oxide is blocked by hydroxy acrylic ester, wherein the mole ratio of the hydroxy acrylic ester to the total amount of diisocyanate is 0.5-0.55:1, a step of; and heating the reaction system to 80-100 ℃, reacting for 5-7h, washing and drying to obtain the multilayer graphene modified polyurethane acrylate oligomer.
Further, the diisocyanate is one or a combination of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate and hexamethylene diisocyanate.
Further, the dihydric alcohol is one or a combination of butanediol, neopentyl glycol, hexanediol, 3-methyl-1, 5-pentanediol and polycaprolactone diol.
Further, the catalyst is triethanolamine.
Further, the acrylate monomer is one or a combination of amino acrylate, organosilicon acrylate, 2-hydroxy acrylate, tripropylene glycol diacrylate, triethylene glycol dimethacrylate, trimethylolpropane triacrylate and sulfobetaine methacrylate.
Further, the photoinitiator is one or a combination of 1-hydroxy-cyclohexyl benzophenone, 2,4, 6-trimethyl benzoyl-diphenyl phosphine oxide, diphenyl ketone and 2, 2-diethoxy phenyl ethyl ketone.
Further, the leveling agent is any one of BYK373, BYK325 or BYK 331.
The invention also provides a preparation method of the modified aqueous polyurethane acrylate composite emulsion, which comprises the following steps: uniformly mixing the multilayer graphene oxide modified polyurethane acrylate oligomer, the acrylate monomer and water, heating to 60-65 ℃, stirring for 30min at 500-800r/min by a stirrer, and naturally cooling to room temperature; and sequentially adding a photoinitiator and a flatting agent, stirring uniformly at normal temperature, standing for defoaming, and preserving in a dark place to obtain the modified aqueous polyurethane acrylate composite emulsion.
The invention also provides application of the modified aqueous polyurethane acrylate composite emulsion, which can be used for adhesives, can be used as a coating for surfaces of metals, plastics or timbers, and is particularly suitable for metal corrosion prevention.
The beneficial effects of the invention are as follows:
1. according to the preparation method, the multilayer graphene oxide is prepared by utilizing graphite, triethanolamine is introduced in the preparation process for preliminary intercalation, dodecyl trimethyl ammonium chloride is used for intercalating the graphene oxide, the interlayer spacing is preliminarily enlarged, then methacryloyl oxyethyl trimethyl ammonium chloride is further intercalated, the interlayer spacing is further enlarged, the polarity degree of an interlayer microenvironment is further adjusted, finally polyvinyl alcohol is intercalated, and the reactive group-hydroxyl of the graphene oxide is increased. Then taking modified graphene oxide as a template for in-situ polymerization, adding diisocyanate, performing grafting reaction on a group-NCO of the diisocyanate and hydroxyl on the surface of the organically modified graphene oxide, sequentially adding dihydric alcohol and diisocyanate for chain extension, and finally capping the hydroxyl acrylate to prepare the polyurethane acrylate with fully compatible and grafted modified multi-layer graphene oxide.
2. According to the invention, different properties of the intercalating agent are creatively combined, the interlayer spacing of the graphene oxide is enlarged, then conditions are provided for intercalation of the polyvinyl alcohol, and experiments show that the methacryloyloxyethyl trimethyl ammonium chloride can also improve the intercalation amount of the polyvinyl alcohol in the graphene oxide, and the interlayer spacing of the multi-layer graphene oxide is increased, so that the multi-layer graphene oxide has more graftable reaction base points-hydroxyl groups.
3. The modified graphene oxide is used as an in-situ polymerization template to obtain the polyurethane acrylate oligomer grafted and modified by the layered graphene oxide, and the polyurethane acrylate oligomer participates in subsequent polymerization reaction, so that the sea-island effect of the layered graphene oxide in matrix resin is fully exerted, the mechanical strength is improved, the oxygen and moisture barrier effect of the layered graphene oxide is fully exerted, and the water resistance, gas isolation, heat resistance and conductivity of the polyurethane acrylate are further improved.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following detailed description of the present invention will provide further details in order to make the above-mentioned objects, features and advantages of the present invention more comprehensible.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways other than those described herein, and persons skilled in the art will readily appreciate that the present invention is not limited to the specific embodiments disclosed below.
The modified aqueous polyurethane acrylate composite emulsion comprises the following components:
the preparation method of the multilayer graphene oxide modified polyurethane acrylate oligomer comprises the following steps: (1) Putting graphite into a mixed solution of potassium persulfate and concentrated sulfuric acid, uniformly stirring, heating to 60-70 ℃, reacting for 20-30min, carrying out suction filtration, soaking and washing with deionized water at 60-80 ℃, and drying to obtain oxidized expanded graphite; (2) Placing oxidized expanded graphite into triethanolamine water solution, stirring uniformly, heating to 50-60 ℃, grinding and stripping for 10-20min, suction filtering, soaking and washing with deionized water at 60-80 ℃, and drying to obtain primarily intercalated multilayer graphene oxide; (3) Weighing 10-20 parts of primarily intercalated multilayer graphene oxide by mass, dispersing in 50 parts of water, adding 2-4 parts of dodecyl trimethyl ammonium chloride, stirring in a stirrer, heating for 1-2 hours at the rotating speed of 500-800r/min, carrying out suction filtration at the temperature of 70-80 ℃, washing with deionized water, and drying to obtain primarily intercalated modified multilayer graphene oxide; (4) Dispersing the primary intercalation modified multilayer graphene oxide in 50 parts of water, adding 6-8 parts of methacryloxyethyl trimethyl ammonium chloride according to parts by weight, stirring and heating in a stirrer for 1-2 hours at a rotating speed of 500-800r/min, performing suction filtration at a temperature of 60-70 ℃, washing with deionized water, and drying to obtain secondary intercalation modified multilayer graphene oxide; (5) Dispersing the secondary intercalation graphene oxide in 50 parts of aqueous solution of polyvinyl alcohol with the concentration of 6wt%, stirring in a stirrer, heating for 2-3 hours at the rotating speed of 100-200 r/min and the temperature of 50-60 ℃, carrying out suction filtration, washing with deionized water, and drying to obtain the functional multilayer graphene oxide; (6) 10 parts of the functional multilayer graphene oxide is added into 20 parts of first-batch diisocyanate, the temperature is heated to 50-90 ℃, dihydric alcohol with the mole ratio of 1:1 with the first-batch diisocyanate and 0.05-0.1 part of catalyst are added after 1-2 hours, 20 parts of second-batch diisocyanate are continuously added, and finally the functional multilayer graphene oxide is blocked by hydroxy acrylic ester, wherein the mole ratio of the hydroxy acrylic ester to the total amount of diisocyanate is 0.5-0.55:1, a step of; and heating the reaction system to 80-100 ℃, reacting for 5-7h, washing and drying to obtain the multilayer graphene modified polyurethane acrylate oligomer.
In the modified aqueous polyurethane acrylate composite emulsion according to the invention, the diisocyanate is one or a combination of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate and hexamethylene diisocyanate. The dihydric alcohol is one or a combination of butanediol, neopentyl glycol, hexanediol, 3-methyl-1, 5-pentanediol and polycaprolactone diol. The catalyst is triethanolamine. The acrylate monomer is one or a combination of amino acrylate, organic silicon acrylate, 2-hydroxy acrylate, tripropylene glycol diacrylate, triethylene glycol dimethacrylate, trimethylolpropane triacrylate and sulfobetaine methacrylate. The photoinitiator is one or a combination of 1-hydroxy-cyclohexyl benzophenone, 2,4, 6-trimethyl benzoyl-diphenyl phosphine oxide, diphenyl ketone and 2, 2-diethoxy phenyl ethyl ketone. The leveling agent is any one of BYK373, BYK325 or BYK 331.
The preparation method of the modified waterborne polyurethane acrylate composite emulsion comprises the following steps: uniformly mixing the multilayer graphene oxide modified polyurethane acrylate oligomer, the acrylate monomer and water, heating to 60-65 ℃, stirring for 30min at 500-800r/min by a stirrer, and naturally cooling to room temperature; and sequentially adding a photoinitiator and a flatting agent, stirring uniformly at normal temperature, standing for defoaming, and preserving in a dark place to obtain the modified aqueous polyurethane acrylate composite emulsion.
The modified aqueous polyurethane acrylate composite emulsion can be used for adhesives and as a coating for surfaces of metals, plastics or timbers, and is particularly suitable for metal corrosion prevention.
The modified aqueous polyurethane acrylate composite emulsion, the preparation method and the application thereof are specifically described below by referring to specific examples.
Example 1
(one) preparing a multilayer graphene oxide modified polyurethane acrylate oligomer:
(1) Putting graphite into a mixed solution of potassium persulfate and concentrated sulfuric acid, uniformly stirring, heating to the temperature of 60 ℃, reacting for 20min, carrying out suction filtration, soaking and washing with deionized water at the temperature of 60 ℃, and drying to obtain oxidized expanded graphite;
(2) Placing oxidized expanded graphite into triethanolamine aqueous solution, uniformly stirring, heating to the temperature of 50 ℃, grinding and stripping for 10min, carrying out suction filtration, soaking and washing with deionized water at the temperature of 60 ℃, and drying to obtain primarily intercalated multilayer graphene oxide;
(3) Weighing 10 parts of primarily intercalated multilayer graphene oxide in parts by weight, dispersing in 50 parts of water, adding 2 parts of dodecyl trimethyl ammonium chloride, stirring in a stirrer, heating for 1h at the rotating speed of 500r/min and the temperature of 70 ℃, carrying out suction filtration, washing with deionized water, and drying to obtain primary intercalated modified multilayer graphene oxide;
(4) Dispersing the primary intercalation modified multilayer graphene oxide in 50 parts of water, adding 6 parts of methacryloxyethyl trimethyl ammonium chloride according to parts by weight, stirring in a stirrer, heating for 1h, rotating at 500r/min and at 60 ℃, carrying out suction filtration, washing with deionized water, and drying to obtain secondary intercalation modified multilayer graphene oxide;
(5) Dispersing the secondary intercalation graphene oxide in 50 parts of aqueous solution of polyvinyl alcohol with the concentration of 6wt%, stirring and heating in a stirrer for 2 hours at the rotating speed of 100 revolutions per minute, performing suction filtration at the temperature of 50 ℃, washing with deionized water, and drying to obtain functional multilayer graphene oxide;
(6) 10 parts of the functional multilayer graphene oxide is added into 20 parts of first batch diisocyanate, the temperature is heated to 50 ℃, after 1h, butanediol and 0.05 part of triethanolamine are added in a molar ratio of 1:1 with the toluene diisocyanate of the first batch, 20 parts of toluene diisocyanate of a second batch are continuously added, and finally the functional multilayer graphene oxide is blocked by hydroxy acrylic ester, wherein the molar ratio of the hydroxy acrylic ester to the total toluene diisocyanate is 0.5:1, a step of; and heating the reaction system to 80 ℃, reacting for 5 hours, washing and drying to obtain the multilayer graphene modified polyurethane acrylate oligomer.
(II) preparing modified aqueous polyurethane acrylate composite emulsion:
(1) Weighing materials according to parts by weight
(2) Mixing material
Uniformly mixing the multilayer graphene oxide modified polyurethane acrylate oligomer, amino acrylate and water, heating to 60 ℃, stirring for 30min at 500r/min by a stirrer, and naturally cooling to room temperature; and sequentially adding 1-hydroxy-cyclohexyl benzophenone and BYK373, stirring uniformly at normal temperature, standing for defoaming, and preserving in a dark place to obtain the modified waterborne polyurethane acrylate composite emulsion.
Example 2
(one) preparing a multilayer graphene oxide modified polyurethane acrylate oligomer:
(1) Putting graphite into a mixed solution of potassium persulfate and concentrated sulfuric acid, uniformly stirring, heating to 70 ℃, reacting for 30min, carrying out suction filtration, soaking and washing with deionized water at 80 ℃, and drying to obtain oxidized expanded graphite;
(2) Placing oxidized expanded graphite into triethanolamine aqueous solution, uniformly stirring, heating to the temperature of 60 ℃, grinding and stripping for 20min, carrying out suction filtration, soaking and washing with deionized water at the temperature of 80 ℃, and drying to obtain primarily intercalated multilayer graphene oxide;
(3) Weighing 20 parts of primarily intercalated multilayer graphene oxide according to the parts by weight, dispersing in 50 parts of water, adding 4 parts of dodecyl trimethyl ammonium chloride, stirring in a stirrer, heating for 2 hours at the rotating speed of 800r/min, performing suction filtration at the temperature of 80 ℃, washing with deionized water, and drying to obtain primary intercalated modified multilayer graphene oxide;
(4) Dispersing the primary intercalation modified multilayer graphene oxide in 50 parts of water, adding 8 parts of methacryloxyethyl trimethyl ammonium chloride according to parts by weight, stirring in a stirrer, heating for 2 hours at the rotating speed of 800 revolutions per minute and the temperature of 70 ℃, carrying out suction filtration, washing with deionized water, and drying to obtain secondary intercalation modified multilayer graphene oxide;
(5) Dispersing the secondary intercalation graphene oxide in 50 parts of aqueous solution of polyvinyl alcohol with the concentration of 6wt%, stirring and heating for 3 hours in a stirrer, rotating at 200 rpm, carrying out suction filtration at 60 ℃, washing with deionized water, and drying to obtain functional multilayer graphene oxide;
(6) 10 parts of the functional multilayer graphene oxide is added into 20 parts of isophorone diisocyanate of a first batch, the temperature is heated to 90 ℃, neopentyl glycol and 0.1 part of triethanolamine are added in a molar ratio of 1:1 with the isophorone diisocyanate of the first batch after 2 hours, 20 parts of isophorone diisocyanate of a second batch are continuously added, and finally the functional multilayer graphene oxide is blocked by hydroxy acrylate, wherein the molar ratio of the hydroxy acrylate to the total amount of isophorone diisocyanate is 0.55:1, a step of; and heating the reaction system to 100 ℃, reacting for 7 hours, washing and drying to obtain the multilayer graphene modified polyurethane acrylate oligomer.
(II) preparing modified aqueous polyurethane acrylate composite emulsion:
(1) Weighing materials according to parts by weight
(2) Mixing material
Uniformly mixing the multilayer graphene oxide modified polyurethane acrylate oligomer, the organic silicon acrylate and water, heating to 65 ℃, stirring for 30min at 800r/min by a stirrer, and naturally cooling to room temperature; and then sequentially adding benzophenone and BYK325, stirring uniformly at normal temperature, standing for defoaming, and preserving in a dark place to obtain the modified aqueous polyurethane acrylate composite emulsion.
Example 3
(one) preparing a multilayer graphene oxide modified polyurethane acrylate oligomer:
(1) Putting graphite into a mixed solution of potassium persulfate and concentrated sulfuric acid, uniformly stirring, heating to 65 ℃, reacting for 25min, carrying out suction filtration, soaking and washing with deionized water at 70 ℃, and drying to obtain oxidized expanded graphite;
(2) Placing oxidized expanded graphite into triethanolamine aqueous solution, uniformly stirring, heating to 55 ℃, grinding and stripping for 15min, carrying out suction filtration, soaking and washing with deionized water at 70 ℃, and drying to obtain primarily intercalated multilayer graphene oxide;
(3) Weighing 15 parts of primarily intercalated multilayer graphene oxide according to the parts by weight, dispersing in 50 parts of water, adding 3 parts of dodecyl trimethyl ammonium chloride, stirring in a stirrer, heating for 1.5 hours at the rotating speed of 600 turns/min and the temperature of 75 ℃, carrying out suction filtration, washing with deionized water, and drying to obtain the primarily intercalated modified multilayer graphene oxide;
(4) Dispersing the primary intercalation modified multilayer graphene oxide in 50 parts of water, adding 7 parts of methacryloxyethyl trimethyl ammonium chloride according to parts by weight, stirring and heating in a stirrer for 1.5 hours at the rotating speed of 600 revolutions per minute and the temperature of 65 ℃, carrying out suction filtration, washing with deionized water, and drying to obtain secondary intercalation modified multilayer graphene oxide;
(5) Dispersing the secondary intercalation graphene oxide in 50 parts of aqueous solution of polyvinyl alcohol with the concentration of 6wt%, stirring and heating in a stirrer for 2.5 hours at the rotating speed of 150 revolutions per minute and the temperature of 55 ℃, carrying out suction filtration, washing with deionized water, and drying to obtain functional multilayer graphene oxide;
(6) 10 parts of the functional multilayer graphene oxide is added into 20 parts of first-batch hexamethylene diisocyanate, the temperature is heated to 70 ℃, after 1.5 hours, polycaprolactone diol and 0.08 part of triethanolamine are added, the molar ratio of the polycaprolactone diol to the first-batch hexamethylene diisocyanate is 1:1, then 20 parts of second-batch hexamethylene diisocyanate are continuously added, and finally the functional multilayer graphene oxide is blocked by hydroxy acrylate, wherein the molar ratio of the hydroxy acrylate to the total amount of the hexamethylene diisocyanate is 0.55:1, a step of; and heating the reaction system to 90 ℃, reacting for 6 hours, washing and drying to obtain the multilayer graphene modified polyurethane acrylate oligomer.
(II) preparing modified aqueous polyurethane acrylate composite emulsion:
(1) Weighing materials according to parts by weight
(2) Mixing material
Uniformly mixing the multilayer graphene oxide modified polyurethane acrylate oligomer, trimethylolpropane triacrylate and water, heating to 62 ℃, stirring for 30min at 700r/min by a stirrer, and naturally cooling to room temperature; and sequentially adding 2, 2-diethoxyphenyl ethyl ketone and BYK331, stirring uniformly at normal temperature, standing for defoaming, and preserving in a dark place to obtain the modified waterborne polyurethane acrylate composite emulsion.
Comparative example 1
The procedure of example 3 was repeated except that cetyltrimethylammonium bromide was used instead of methacryloyloxyethyl trimethylammonium chloride.
Comparative example 2
The procedure of example 3 was repeated except that polyvinyl alcohol was not used in the preparation of the functional multilayer graphene oxide.
Comparative example 3
The process for producing the functional multilayer graphene oxide was the same as in example 3, except that methacryloyloxyethyl trimethyl ammonium chloride and polyvinyl alcohol were not used.
Comparative example 4
In the process of preparing the functional multilayer graphene oxide, the same procedure as in example 3 was followed except that N, N-dimethylformamide was used instead of triethanolamine.
Performance testing
1. Coating material
(1) Sample of
The components A and B of the examples and the comparative examples are uniformly mixed according to the parts by weight, the foam is removed in vacuum, and then the mixture is coated on a glass sheet subjected to electrostatic dust removal, and ultraviolet light irradiation curing is performed at 45 ℃ to obtain a film sample with the film thickness of 0.3 mm.
(2) Testing
Adhesion force: the hundred method (3M600,3 times);
pencil hardness: mitsubishi pencil (1 KG force);
boiling resistance: soaking the sample at 100 ℃ for 1 hour;
abrasion resistance: testing according to the standard "method for measuring abrasion resistance of paint and varnish by rotating rubber grinding wheel" (GB/T1768-2006);
gas barrier properties: the equipment is a differential pressure gas permeation instrument, and the gas pressure of the high-pressure chamber is 1.0x10 5 Pa; the equipment is a differential pressure gas permeation instrument.
2. Film and method for producing the same
Uniformly mixing the components A and B of each example and comparative example according to the parts by weight, removing bubbles in vacuum, pouring into a mold coated with a release agent, performing ultraviolet irradiation curing at 60 ℃ to obtain a film with the thickness of 1mm, and cutting into dumbbell-shaped sample bars;
tensile strength of film: room temperature, stretching speed is 1m/min;
sheet resistance of film: the sheet resistance of the films was tested using Keithley 2700.
Performance comparison Table
According to the embodiment, the modified aqueous polyurethane acrylate composite emulsion prepared by the invention is used for adhesives or coatings, has higher adhesive force, hardness, boiling resistance and wear resistance compared with unmodified aqueous polyurethane acrylate composite emulsion, and has good gas barrier property and conductivity, so that the corrosion resistance and antistatic property are improved; the composite material can also be used for preparing composite materials, has good mechanical properties, and completely meets the application requirements of industry.
While certain specific embodiments of the invention have been described in detail by way of example, it will be appreciated by those skilled in the art that the above examples are for illustration only and are not intended to limit the scope of the invention. It will be appreciated by those skilled in the art that modifications may be made to the above embodiments without departing from the scope and spirit of the invention. The scope of the invention is defined by the appended claims.
Claims (9)
1. The modified aqueous polyurethane acrylate composite emulsion is characterized by comprising the following components:
the preparation method of the multilayer graphene oxide modified polyurethane acrylate oligomer comprises the following steps:
(1) Putting graphite into a mixed solution of potassium persulfate and concentrated sulfuric acid, uniformly stirring, heating to 60-70 ℃, reacting for 20-30min, carrying out suction filtration, soaking and washing with deionized water at 60-80 ℃, and drying to obtain oxidized expanded graphite;
(2) Placing oxidized expanded graphite into triethanolamine water solution, stirring uniformly, heating to 50-60 ℃, grinding and stripping for 10-20min, suction filtering, soaking and washing with deionized water at 60-80 ℃, and drying to obtain primarily intercalated multilayer graphene oxide;
(3) Weighing 10-20 parts of primarily intercalated multilayer graphene oxide by mass, dispersing in 50 parts of water, adding 2-4 parts of dodecyl trimethyl ammonium chloride, stirring in a stirrer, heating for 1-2 hours at the rotating speed of 500-800r/min, carrying out suction filtration at the temperature of 70-80 ℃, washing with deionized water, and drying to obtain primarily intercalated modified multilayer graphene oxide;
(4) Dispersing the primary intercalation modified multilayer graphene oxide in 50 parts of water, adding 6-8 parts of methacryloxyethyl trimethyl ammonium chloride according to parts by weight, stirring and heating in a stirrer for 1-2 hours at a rotating speed of 500-800r/min, performing suction filtration at a temperature of 60-70 ℃, washing with deionized water, and drying to obtain secondary intercalation modified multilayer graphene oxide;
(5) Dispersing the secondary intercalation graphene oxide in 50 parts of aqueous solution of polyvinyl alcohol with the concentration of 6wt%, stirring in a stirrer, heating for 2-3 hours at the rotating speed of 100-200 r/min and the temperature of 50-60 ℃, carrying out suction filtration, washing with deionized water, and drying to obtain the functional multilayer graphene oxide;
(6) 10 parts of the functional multilayer graphene oxide is added into 20 parts of first-batch diisocyanate, the temperature is heated to 50-90 ℃, dihydric alcohol with the mole ratio of 1:1 with the first-batch diisocyanate and 0.05-0.1 part of catalyst are added after 1-2 hours, 20 parts of second-batch diisocyanate are continuously added, and finally the functional multilayer graphene oxide is blocked by hydroxy acrylic ester, wherein the mole ratio of the hydroxy acrylic ester to the total amount of diisocyanate is 0.5-0.55:1, a step of; and heating the reaction system to 80-100 ℃, reacting for 5-7h, washing and drying to obtain the multilayer graphene modified polyurethane acrylate oligomer.
2. The modified aqueous urethane acrylate composite emulsion according to claim 1, wherein said diisocyanate is one or a combination of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate and hexamethylene diisocyanate.
3. The modified aqueous urethane acrylate composite emulsion according to claim 1, wherein said glycol is one or a combination of butanediol, neopentyl glycol, hexanediol, 3-methyl-1, 5-pentanediol and polycaprolactone diol.
4. The modified aqueous urethane acrylate composite emulsion according to claim 1, wherein said catalyst is triethanolamine.
5. The modified aqueous urethane acrylate composite emulsion according to claim 1, wherein the acrylate monomer is one or a combination of amino acrylate, silicone acrylate, 2-hydroxy acrylate, tripropylene glycol diacrylate, triethylene glycol dimethacrylate, trimethylolpropane triacrylate and sulfobetaine methacrylate.
6. The modified aqueous polyurethane acrylate composite emulsion according to claim 1, wherein the photoinitiator is one or a combination of 1-hydroxy-cyclohexyl benzophenone, 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide, benzophenone, and 2, 2-diethoxyphenyl ethanone.
7. The modified aqueous urethane acrylate composite emulsion according to claim 1, wherein said leveling agent is any one of BYK373, BYK325 or BYK 331.
8. The method for preparing a modified aqueous urethane acrylate composite emulsion according to any one of claims 1 to 7, characterized by comprising the steps of: uniformly mixing the multilayer graphene oxide modified polyurethane acrylate oligomer, the acrylate monomer and water, heating to 60-65 ℃, stirring for 30min at 500-800r/min by a stirrer, and naturally cooling to room temperature; and sequentially adding a photoinitiator and a flatting agent, stirring uniformly at normal temperature, standing for defoaming, and preserving in a dark place to obtain the modified aqueous polyurethane acrylate composite emulsion.
9. Use of the modified aqueous polyurethane acrylate composite emulsion according to any of claims 1 to 7 for adhesives, as coating materials for surfaces of metals, plastics or wood.
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