CN110964474A - Preparation method of graphene modified polyurethane adhesive - Google Patents
Preparation method of graphene modified polyurethane adhesive Download PDFInfo
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/06—Polyurethanes from polyesters
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3225—Polyamines
- C08G18/3228—Polyamines acyclic
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- C08G18/65—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
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- C08G18/6648—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6651—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
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Abstract
The invention discloses a preparation method of a graphene modified polyurethane adhesive, which comprises the following steps of uniformly dispersing 0.5-1 part of graphene oxide in 10 parts of absolute ethyl alcohol by weight, and reacting with 20 parts of polyisocyanate to prepare a polyisocyanate-graphene oxide mixed solution; 25 parts of triethanolamine, 30 parts of sodium hydroxyethyl sulfonate, 33 parts of n-decane and 0.5 part of metal sodium are reacted to obtain sulfonated dihydric alcohol; adding 8 parts of absolute ethyl alcohol for dissolving, and then carrying out reduced pressure distillation to obtain dihydric alcohol containing sulfonic groups; 60 parts of polyester polyol and 10 parts of dihydric alcohol containing sulfonic groups are subjected to reduced pressure distillation and then react with polyisocyanate-graphene oxide mixed solution, and a thickening agent and a defoaming agent are added into a reactant after chain extension to obtain the graphene modified polyurethane aqueous adhesive. The adhesive has high graphene content, good dispersibility, difficult agglomeration, environmental protection and antibiosis, and greatly improves the service performance and storage stability of the adhesive.
Description
Technical Field
The invention relates to the field of polyurethane adhesives, in particular to a preparation method of a graphene modified polyurethane adhesive.
Background
The polyurethane adhesive has the advantages of adjustable hardness, low temperature resistance, good flexibility, high bonding strength and the like, can bond various materials such as metal, nonmetal and the like, and has wider and wider application. Polyurethane adhesives include solvent-borne polyurethane adhesives and waterborne polyurethane adhesives.
With the enhancement of awareness of safety and environmental protection, the research on the aqueous polyurethane adhesive is rapidly developed. The water-based polyurethane adhesive is formed by dissolving or dispersing polyurethane in water, and has the advantages of no solvent, no pollution, good film forming property, easy mixing with other polymers, especially emulsion polymers, and the like, compared with a solvent type adhesive. After 90 s, the adhesive has been gradually applied to the aspects of automobile inner decoration, kitchen article manufacturing, composite film manufacturing, sole and upper adhesion, garment processing and the like. However, there are many disadvantages such as easy degumming, low solid content, and the need for various modifications to improve the functions.
Graphene is a polymer made of carbon atoms in sp2The hybrid tracks form a hexagonal honeycomb lattice two-dimensional carbon nanomaterial. Has excellent optical, electrical and mechanical properties, and has important application prospect in the aspects of materials science, micro-nano processing, energy, biomedicine, drug delivery and the like. The graphene is used in the polyurethane adhesive, so that the adhesive property, the structural strength and the antibacterial property of the polyurethane adhesive can be greatly improved. However, the current domestic research on the type of adhesive has less literature, and the Chinese patent application CN106189988A discloses a graphene modified adhesive solution and a preparation method and application thereof, wherein the obtained graphene modified water-based polyurethane adhesive is mainly used for non-woven fabrics, the prepared adhesive solution has low graphene content, graphene in the adhesive solution is easy to agglomerate, the property of the adhesive solution is unstable, and the adhesive solution is not suitable for polyurethane adhesives for other applications, such as polyurethane adhesives for bonding soles and uppers.
Disclosure of Invention
In order to solve the above problems, the present invention provides a method for preparing a graphene-modified polyurethane adhesive, comprising the following steps:
1. the preparation method of the graphene modified polyurethane adhesive is characterized by comprising the following steps:
s1, uniformly dispersing 0.5-1 part of graphene oxide in 10 parts of absolute ethyl alcohol in parts by weight;
s2, uniformly mixing 20 parts of polyisocyanate and the graphene oxide dispersion liquid obtained in the step S1 in parts by weight, pouring the mixture into a three-neck flask, and stirring and reacting the mixture for 24 hours in a constant-temperature water bath at the temperature of 80-85 ℃ to obtain polyisocyanate-graphene oxide mixed liquid;
s3, dispersing 25 parts of triethanolamine and 30 parts of sodium hydroxyethyl sulfonate by 33 parts of n-decane, uniformly stirring, pouring into a three-neck flask, putting into 200-plus 210 ℃ constant temperature oil bath, starting stirring, and rotating at the speed of 1000 rpm; adding 0.5 part of sodium metal into a three-neck flask, reacting for 4.5 hours at the temperature of 200 ℃ and 210 ℃, and cooling to 25 ℃ after the reaction is finished to obtain sulfonated dihydric alcohol; adding 8 parts of absolute ethyl alcohol into a three-neck flask, dissolving sulfonated dihydric alcohol, and then carrying out reduced pressure distillation to obtain dihydric alcohol containing sulfonic groups;
s4, weighing 60 parts by weight of polyester polyol and 10 parts by weight of the dihydric alcohol containing sulfonic groups obtained in the step S1, pouring the weighed polyester polyol and the dihydric alcohol into a three-neck flask, and putting the three-neck flask into a constant-temperature water bath at 65-70 ℃ after reduced pressure distillation;
s5, pouring the polyisocyanate-graphene oxide mixed solution obtained in the step S1 into the three-neck flask obtained in the step S4, adding 0.03 part by weight of dibutyltin dilaurate, and stirring at the constant temperature of 80-85 ℃ for 3 hours;
s6, weighing 70 parts of acetone and 1 part of 1, 4-butanediol by weight, pouring into the three-neck flask in the step S5, and stirring and reacting at 80-85 ℃ for 2 hours;
s7, weighing 100 parts of water by weight, adding the water into the three-neck flask obtained in the step S6, adjusting the stirring speed to 6000 r/min, and stirring for 20 minutes to obtain an emulsion;
s8, weighing 1 part of ethylenediamine by weight, adding the ethylenediamine into the emulsion obtained in the step S7, and stirring and reacting for 2 hours at room temperature, wherein the stirring speed is 1000 rpm;
s9, distilling the emulsion after the reaction in the step S8 under reduced pressure;
s10, weighing 0.5-1 part of thickening agent by weight, and adding into the reduced pressure distillation emulsion obtained in the step S9;
s11, adding 0.1-0.3 of defoaming agent by weight to obtain the graphene modified polyurethane adhesive.
Preferably, the vacuum degree of the reduced pressure distillation in the step S3 is-0.1 MPa, the temperature is 140 ℃ and 150 ℃, and the distillation time is 1 hour.
Preferably, the polyester polyol in step S4 is adipic acid and 1, 6-hexanediol; the vacuum degree of the reduced pressure distillation water removal in the step S4 is set to-0.1 MPa, the temperature is 100 ℃ and 110 ℃, and the time is 1 h.
Preferably, the vacuum degree of the reduced pressure distillation in the step S9 is-0.1 MPa, the temperature is 70-75 ℃, and the distillation time is 1 hour.
Preferably, the thickener in step S10 is sodium alginate.
Preferably, the defoaming agent in step S11 is a silicone defoaming agent.
Compared with the prior art, the graphene modified polyurethane adhesive provided by the invention has the following advantages:
1. the graphene has good dispersibility in the adhesive emulsion and is not easy to agglomerate;
2. the graphene content is high, so that the structural strength of the adhesive is greatly improved;
3. environmental protection and antibiosis, improves the capability of resisting microbial degradation, and increases the storage time of the adhesive.
Detailed Description
Example 1:
the specific technical scheme is that the preparation method of the graphene modified polyurethane adhesive comprises the following steps:
s1, dispersing 0.5 part of graphene oxide in 10 parts of absolute ethyl alcohol uniformly in parts by weight;
s2, uniformly mixing 20 parts of polyisocyanate and the graphene oxide dispersion liquid obtained in the step S1 in parts by weight, pouring the mixture into a three-neck flask, and stirring and reacting the mixture for 24 hours in a constant-temperature water bath at the temperature of 80-85 ℃ to obtain polyisocyanate-graphene oxide mixed liquid;
s3, dispersing 25 parts of triethanolamine and 30 parts of sodium hydroxyethyl sulfonate by 33 parts of n-decane, uniformly stirring, pouring into a three-neck flask, putting into 200-plus 210 ℃ constant temperature oil bath, starting stirring, and rotating at the speed of 1000 rpm; adding 0.5 part of sodium metal into a three-neck flask, reacting for 4.5 hours at the temperature of 200 ℃ and 210 ℃, and cooling to 25 ℃ after the reaction is finished to obtain sulfonated dihydric alcohol; adding 8 parts of absolute ethyl alcohol into a three-neck flask, dissolving sulfonated dihydric alcohol, and then carrying out reduced pressure distillation to obtain dihydric alcohol containing sulfonic groups;
s4, weighing 60 parts by weight of polyester polyol and 10 parts by weight of the dihydric alcohol containing sulfonic groups obtained in the step S1, pouring the weighed polyester polyol and the dihydric alcohol into a three-neck flask, and putting the three-neck flask into a constant-temperature water bath at 65-70 ℃ after reduced pressure distillation;
s5, pouring the polyisocyanate-graphene oxide mixed solution obtained in the step S1 into the three-neck flask obtained in the step S4, adding 0.03 part by weight of dibutyltin dilaurate, and stirring at the constant temperature of 80-85 ℃ for 3 hours;
s6, weighing 70 parts of acetone and 1 part of 1, 4-butanediol by weight, pouring into the three-neck flask in the step S5, and stirring and reacting at 80-85 ℃ for 2 hours;
s7, weighing 100 parts of water by weight, adding the water into the three-neck flask obtained in the step S6, adjusting the stirring speed to 6000 r/min, and stirring for 20 minutes to obtain an emulsion;
s8, weighing 1 part of ethylenediamine by weight, adding the ethylenediamine into the emulsion obtained in the step S7, and stirring and reacting for 2 hours at room temperature, wherein the stirring speed is 1000 rpm;
s9, distilling the emulsion after the reaction in the step S8 under reduced pressure;
s10, weighing 0.5 part of thickener sodium alginate in parts by weight, and adding the thickener sodium alginate into the reduced pressure distillation emulsion obtained in the step S9;
s11, adding a defoaming agent, namely an organic silicon defoaming agent, of which the weight is 0.1 to obtain the graphene modified polyurethane adhesive.
Preferably, the vacuum degree of the reduced pressure distillation in the step S3 is-0.1 MPa, the temperature is 140 ℃ and 150 ℃, and the distillation time is 1 hour.
Preferably, the polyester polyol in step S4 is adipic acid and 1, 6-hexanediol; the vacuum degree of the reduced pressure distillation water removal in the step S4 is set to-0.1 MPa, the temperature is 100 ℃ and 110 ℃, and the time is 1 h.
Preferably, the vacuum degree of the reduced pressure distillation in the step S9 is-0.1 MPa, the temperature is 70-75 ℃, and the distillation time is 1 hour.
Example 2:
s1, dispersing 0.8 part of graphene oxide in 10 parts of absolute ethyl alcohol uniformly in parts by weight;
s2, uniformly mixing 20 parts of polyisocyanate and the graphene oxide dispersion liquid obtained in the step S1 in parts by weight, pouring the mixture into a three-neck flask, and stirring and reacting the mixture for 24 hours in a constant-temperature water bath at the temperature of 80-85 ℃ to obtain polyisocyanate-graphene oxide mixed liquid;
s3, dispersing 25 parts of triethanolamine and 30 parts of sodium hydroxyethyl sulfonate by 33 parts of n-decane, uniformly stirring, pouring into a three-neck flask, putting into 200-plus 210 ℃ constant temperature oil bath, starting stirring, and rotating at the speed of 1000 rpm; adding 0.5 part of sodium metal into a three-neck flask, reacting for 4.5 hours at the temperature of 200 ℃ and 210 ℃, and cooling to 25 ℃ after the reaction is finished to obtain sulfonated dihydric alcohol; adding 8 parts of absolute ethyl alcohol into a three-neck flask, dissolving sulfonated dihydric alcohol, and then carrying out reduced pressure distillation to obtain dihydric alcohol containing sulfonic groups;
s4, weighing 60 parts by weight of polyester polyol and 10 parts by weight of the dihydric alcohol containing sulfonic groups obtained in the step S1, pouring the weighed polyester polyol and the dihydric alcohol into a three-neck flask, and putting the three-neck flask into a constant-temperature water bath at 65-70 ℃ after reduced pressure distillation;
s5, pouring the polyisocyanate-graphene oxide mixed solution obtained in the step S1 into the three-neck flask obtained in the step S4, adding 0.03 part by weight of dibutyltin dilaurate, and stirring at the constant temperature of 80-85 ℃ for 3 hours;
s6, weighing 70 parts of acetone and 1 part of 1, 4-butanediol by weight, pouring into the three-neck flask in the step S5, and stirring and reacting at 80-85 ℃ for 2 hours;
s7, weighing 100 parts of water by weight, adding the water into the three-neck flask obtained in the step S6, adjusting the stirring speed to 6000 r/min, and stirring for 20 minutes to obtain an emulsion;
s8, weighing 1 part of ethylenediamine by weight, adding the ethylenediamine into the emulsion obtained in the step S7, and stirring and reacting for 2 hours at room temperature, wherein the stirring speed is 1000 rpm;
s9, distilling the emulsion after the reaction in the step S8 under reduced pressure;
s10, weighing 1 part of thickener sodium alginate in parts by weight, and adding the thickener sodium alginate into the reduced pressure distillation emulsion obtained in the step S9;
s11, adding a defoaming agent, namely an organic silicon defoaming agent, of which the weight is 0.2, and obtaining the graphene modified polyurethane adhesive.
Preferably, the vacuum degree of the reduced pressure distillation in the step S3 is-0.1 MPa, the temperature is 140 ℃ and 150 ℃, and the distillation time is 1 hour.
Preferably, the polyester polyol in step S4 is adipic acid and 1, 6-hexanediol; the vacuum degree of the reduced pressure distillation water removal in the step S4 is set to-0.1 MPa, the temperature is 100 ℃ and 110 ℃, and the time is 1 h.
Preferably, the vacuum degree of the reduced pressure distillation in the step S9 is-0.1 MPa, the temperature is 70-75 ℃, and the distillation time is 1 hour.
Example 3:
s1, uniformly dispersing 1 part of graphene oxide in 10 parts of absolute ethyl alcohol in parts by weight;
s2, uniformly mixing 20 parts of polyisocyanate and the graphene oxide dispersion liquid obtained in the step S1 in parts by weight, pouring the mixture into a three-neck flask, and stirring and reacting the mixture for 24 hours in a constant-temperature water bath at the temperature of 80-85 ℃ to obtain polyisocyanate-graphene oxide mixed liquid;
s3, dispersing 25 parts of triethanolamine and 30 parts of sodium hydroxyethyl sulfonate by 33 parts of n-decane, uniformly stirring, pouring into a three-neck flask, putting into 200-plus 210 ℃ constant temperature oil bath, starting stirring, and rotating at the speed of 1000 rpm; adding 0.5 part of sodium metal into a three-neck flask, reacting for 4.5 hours at the temperature of 200 ℃ and 210 ℃, and cooling to 25 ℃ after the reaction is finished to obtain sulfonated dihydric alcohol; adding 8 parts of absolute ethyl alcohol into a three-neck flask, dissolving sulfonated dihydric alcohol, and then carrying out reduced pressure distillation to obtain dihydric alcohol containing sulfonic groups;
s4, weighing 60 parts by weight of polyester polyol and 10 parts by weight of the dihydric alcohol containing sulfonic groups obtained in the step S1, pouring the weighed polyester polyol and the dihydric alcohol into a three-neck flask, and putting the three-neck flask into a constant-temperature water bath at 65-70 ℃ after reduced pressure distillation;
s5, pouring the polyisocyanate-graphene oxide mixed solution obtained in the step S1 into the three-neck flask obtained in the step S4, adding 0.03 part by weight of dibutyltin dilaurate, and stirring at the constant temperature of 80-85 ℃ for 3 hours;
s6, weighing 70 parts of acetone and 1 part of 1, 4-butanediol by weight, pouring into the three-neck flask in the step S5, and stirring and reacting at 80-85 ℃ for 2 hours;
s7, weighing 100 parts of water by weight, adding the water into the three-neck flask obtained in the step S6, adjusting the stirring speed to 6000 r/min, and stirring for 20 minutes to obtain an emulsion;
s8, weighing 1 part of ethylenediamine by weight, adding the ethylenediamine into the emulsion obtained in the step S7, and stirring and reacting for 2 hours at room temperature, wherein the stirring speed is 1000 rpm;
s9, distilling the emulsion after the reaction in the step S8 under reduced pressure;
s10, weighing 1 part of thickener sodium alginate in parts by weight, and adding the thickener sodium alginate into the reduced pressure distillation emulsion obtained in the step S9;
s11, adding a defoaming agent, namely an organic silicon defoaming agent, of which the weight is 0.3 to obtain the graphene modified polyurethane adhesive.
Preferably, the vacuum degree of the reduced pressure distillation in the step S3 is-0.1 MPa, the temperature is 140 ℃ and 150 ℃, and the distillation time is 1 hour.
Preferably, the polyester polyol in step S4 is adipic acid and 1, 6-hexanediol; the vacuum degree of the reduced pressure distillation water removal in the step S4 is set to-0.1 MPa, the temperature is 100 ℃ and 110 ℃, and the time is 1 h.
Preferably, the vacuum degree of the reduced pressure distillation in the step S9 is-0.1 MPa, the temperature is 70-75 ℃, and the distillation time is 1 hour.
And (3) performance detection:
100g of the adhesive of example 1, example 2, example 3 and 100g of the adhesive sample containing graphene were weighed out for comparative tests, and the results were as follows:
as can be seen from the above table, the graphene modified polyurethane adhesives obtained in examples 1 to 3 are less prone to agglomeration and sedimentation than the sample, and when the amount of graphene is 0.5 part or 0.8 part, no sedimentation can be achieved within 6 months.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents and are included in the scope of the present invention.
Claims (6)
1. The preparation method of the graphene modified polyurethane adhesive is characterized by comprising the following steps:
s1, uniformly dispersing 0.5-1 part of graphene oxide in 10 parts of absolute ethyl alcohol in parts by weight;
s2, uniformly mixing 20 parts of polyisocyanate and the graphene oxide dispersion liquid obtained in the step S1 in parts by weight, pouring the mixture into a three-neck flask, and stirring and reacting the mixture for 24 hours in a constant-temperature water bath at the temperature of 80-85 ℃ to obtain polyisocyanate-graphene oxide mixed liquid;
s3, dispersing 25 parts of triethanolamine and 30 parts of sodium hydroxyethyl sulfonate by 33 parts of n-decane, uniformly stirring, pouring into a three-neck flask, putting into 200-plus 210 ℃ constant temperature oil bath, starting stirring, and rotating at the speed of 1000 rpm; adding 0.5 part of sodium metal into a three-neck flask, reacting for 4.5 hours at the temperature of 200 ℃ and 210 ℃, and cooling to 25 ℃ after the reaction is finished to obtain sulfonated dihydric alcohol; adding 8 parts of absolute ethyl alcohol into a three-neck flask, dissolving sulfonated dihydric alcohol, and then carrying out reduced pressure distillation to obtain dihydric alcohol containing sulfonic groups;
s4, weighing 60 parts by weight of polyester polyol and 10 parts by weight of the dihydric alcohol containing sulfonic groups obtained in the step S1, pouring the weighed polyester polyol and the dihydric alcohol into a three-neck flask, and putting the three-neck flask into a constant-temperature water bath at 65-70 ℃ after reduced pressure distillation;
s5, pouring the polyisocyanate-graphene oxide mixed solution obtained in the step S1 into the three-neck flask obtained in the step S4, adding 0.03 part by weight of dibutyltin dilaurate, and stirring at the constant temperature of 80-85 ℃ for 3 hours;
s6, weighing 70 parts of acetone and 1 part of 1, 4-butanediol by weight, pouring into the three-neck flask in the step S5, and stirring and reacting at 80-85 ℃ for 2 hours;
s7, weighing 100 parts of water by weight, adding the water into the three-neck flask obtained in the step S6, adjusting the stirring speed to 6000 r/min, and stirring for 20 minutes to obtain an emulsion;
s8, weighing 1 part of ethylenediamine by weight, adding the ethylenediamine into the emulsion obtained in the step S7, and stirring and reacting for 2 hours at room temperature, wherein the stirring speed is 1000 rpm;
s9, distilling the emulsion after the reaction in the step S8 under reduced pressure;
s10, weighing 0.5-1 part of thickening agent by weight, and adding into the reduced pressure distillation emulsion obtained in the step S9;
s11, adding 0.1-0.3 of defoaming agent by weight to obtain the graphene modified polyurethane adhesive.
2. The method of claim 1, wherein the graphene-modified polyurethane adhesive comprises: the vacuum degree of the reduced pressure distillation in the step S3 is-0.1 MPa, the temperature is 140-150 ℃, and the distillation time is 1 hour.
3. The method of claim 1, wherein the graphene-modified polyurethane adhesive comprises: step S4, the polyester polyol is adipic acid and 1, 6-hexanediol; the vacuum degree of the reduced pressure distillation water removal in the step S4 is set to-0.1 MPa, the temperature is 100 ℃ and 110 ℃, and the time is 1 h.
4. The method of claim 1, wherein the graphene-modified polyurethane adhesive comprises: in the step S9, the vacuum degree of the reduced pressure distillation is-0.1 MPa, the temperature is 70-75 ℃, and the distillation time is 1 hour.
5. The method of claim 1, wherein the graphene-modified polyurethane adhesive comprises: in step S10, the thickener is sodium alginate.
6. The method of claim 1, wherein the graphene-modified polyurethane adhesive comprises: the defoaming agent in the step S11 is a silicone defoaming agent.
Priority Applications (1)
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| CN104194707A (en) * | 2014-08-19 | 2014-12-10 | 华南理工大学 | Water-based polyurethane adhesive with high solid content for shoes and preparation method thereof |
| CN106675494A (en) * | 2016-11-24 | 2017-05-17 | 俞明亮 | Water-based polyurethane adhesive for bullet-proof vest composite material and preparation method of water-based polyurethane adhesive |
| CN107779161A (en) * | 2017-11-13 | 2018-03-09 | 盐城市国泰高新防备有限公司 | Graphene is modified adhesive and preparation method thereof |
| CN109554151A (en) * | 2018-10-23 | 2019-04-02 | 厦门韦尔通科技有限公司 | A kind of adhesive and preparation method thereof suitable for electronic device |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104194707A (en) * | 2014-08-19 | 2014-12-10 | 华南理工大学 | Water-based polyurethane adhesive with high solid content for shoes and preparation method thereof |
| CN106675494A (en) * | 2016-11-24 | 2017-05-17 | 俞明亮 | Water-based polyurethane adhesive for bullet-proof vest composite material and preparation method of water-based polyurethane adhesive |
| CN107779161A (en) * | 2017-11-13 | 2018-03-09 | 盐城市国泰高新防备有限公司 | Graphene is modified adhesive and preparation method thereof |
| CN109554151A (en) * | 2018-10-23 | 2019-04-02 | 厦门韦尔通科技有限公司 | A kind of adhesive and preparation method thereof suitable for electronic device |
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