CN112920366A - High-heat-elasticity-resistance waterborne polyurethane dispersion, adhesive and preparation method thereof - Google Patents
High-heat-elasticity-resistance waterborne polyurethane dispersion, adhesive and preparation method thereof Download PDFInfo
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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
- C08G18/6625—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/34
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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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
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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
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
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- 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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- 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
- C09J175/08—Polyurethanes from polyethers
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
The invention discloses a high-thermal-elasticity-resistance boiled water polyurethane dispersion, an adhesive and a preparation method thereof, wherein the high-thermal-elasticity-resistance boiled water polyurethane dispersion is prepared from the following raw materials in parts by weight: 160-180 parts of polyester polyol, 5-10 parts of polyether polyol, 2-5 parts of hydrophilic compound, 20-30 parts of isocyanate, 0.1-0.8 part of alcohol chain extender, 0.1-0.8 part of amine chain extender, 0.1-0.5 part of internal crosslinking agent, 0.02-0.04 part of catalyst, 0-3 parts of neutralizer and 190-300 parts of water. The high-heat-resistance pop-up waterborne polyurethane adhesive comprises a main adhesive and a waterborne isocyanate curing agent, wherein the main adhesive and the waterborne isocyanate curing agent are used in a matched manner according to the weight ratio of 100: 2-10; the main adhesive is prepared from the high-heat-resistance elastic waterborne polyurethane dispersion. The invention is not only environment-friendly, nontoxic, low in VOC and low in odor, but also has excellent bonding strength, and the heat-resisting flicking resistance is obviously improved.
Description
Technical Field
The invention relates to the field of aqueous polyurethane dispersions and adhesives, in particular to a high-heat-elasticity-resistance aqueous polyurethane dispersion, an adhesive and a preparation method thereof.
Background
At present, common adhesives in the fields of automobiles, high-speed rails, furniture, shoemaking, textiles and the like are classified into oil adhesives and water adhesives. The oily adhesive has large smell and is not environment-friendly, thereby not only affecting the health of workers, but also enabling the gluing part to continuously emit toxic and harmful substances to affect the body health of users. The aqueous adhesive is environment-friendly, non-toxic, low in VOC (volatile organic compounds) and low in odor, and can avoid the defects of an oily adhesive. The waterborne polyurethane adhesive has outstanding environmental protection and bonding performance, and is also one of important types of waterborne adhesives. The waterborne polyurethane adhesive consists of a waterborne polyurethane dispersion, other waterborne emulsion and an auxiliary agent. Since water is used as a solvent and the volatilization speed of water is lower than that of organic solvents such as toluene, acetone and the like, if the thermal pop-up resistance of the aqueous polyurethane dispersion is not good enough, the thermal pop-up resistance of the aqueous polyurethane adhesive is poor. When the adhesive with poor heat-resistant flicking performance is used, under the scene that the base material needs to be covered or the base material has high tension, serious bonding quality accidents such as bulging, covered flicking and the like easily occur, the bonded piece is scrapped, and serious economic loss is brought.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides the high-heat-resistant elastic waterborne polyurethane dispersion, the adhesive and the preparation method thereof, so that the dispersion is environment-friendly, non-toxic, low in VOC and low in smell, has excellent bonding strength, remarkably improves the heat-resistant elastic opening performance, avoids serious bonding quality accidents such as bulging, edge-covering elastic opening and the like easily occurring in the scene of edge covering or large base material tension, brings good economic benefits, and can be widely applied to the fields of automobiles, high-speed rails, furniture, shoe making, textile and the like.
The purpose of the invention is realized by the following technical scheme:
the high-heat-resistance elastic waterborne polyurethane dispersion is prepared from the following raw materials in parts by weight:
a preparation method of a high-heat-elasticity-resistance waterborne polyurethane dispersion comprises the following steps:
step 1, adding 160-180 parts by weight of polyester polyol, 5-10 parts by weight of polyether polyol and 0-5 parts by weight of hydrophilic compound into a reaction device, dehydrating for 0.5-4 hours at 90-120 ℃ and under the environment of vacuum degree of-0.08-0.1 MPa, cooling to 65-80 ℃, adding 20-30 parts by weight of isocyanate, 0.1-0.8 part by weight of alcohol chain extender, 0-0.5 part by weight of internal cross-linking agent and 0.02-0.04 part by weight of catalyst, reacting for 3-5 hours at 65-80 ℃ until the content of-NCO reaches 0.8% -2%, and obtaining a first intermediate;
step 2, cooling the first intermediate to 35-55 ℃, adding 250-350 parts by weight of acetone into the first intermediate to adjust the viscosity of the prepolymer, controlling the temperature to 35-55 ℃, adding 0-3 parts by weight of a neutralizing agent to perform neutralization reaction for 20 min-1.5 h, and adding 190-300 parts by weight of deionized water to perform emulsification to obtain a second intermediate;
step 3, controlling the temperature of the second intermediate to be 35-55 ℃, adding 0.1-0.8 part by weight of amine chain extender, 0-5 parts by weight of hydrophilic compound and 0-0.5 part by weight of internal cross-linking agent into the second intermediate, stirring for 20 min-1.5 h, removing acetone under reduced pressure, filtering and discharging after the solid content reaches 48.5-51.5%, thereby obtaining the high heat-resistant elastic aqueous polyurethane dispersion;
wherein the sum of the amounts of the hydrophilic compound in the step 1 and the hydrophilic compound in the step 3 is 2-5 parts by weight; the total amount of the internal cross-linking agent in the step 1 and the internal cross-linking agent in the step 3 is 0.1-0.5 parts by weight.
A high-heat-resistance pop-up waterborne polyurethane adhesive comprises a main adhesive and a waterborne isocyanate curing agent, wherein the main adhesive and the waterborne isocyanate curing agent are used in a matched manner according to the weight ratio of 100: 2-10; the main rubber is prepared from the following raw materials in parts by weight: 70-90 parts of the high-heat-resistance elastic waterborne polyurethane dispersion, 10-30 parts of waterborne epoxy resin, 0.1-0.5 part of waterborne thickener, 1-3 parts of fumed silica, 0.1-0.5 part of coupling agent, 0.1-0.5 part of wetting agent and 0.1-0.5 part of defoaming agent.
A preparation method of a high heat-resistant pop-up waterborne polyurethane adhesive comprises the following steps: according to the weight parts, 70-90 parts of the high heat-resistant elastic water-borne polyurethane dispersion, 10-30 parts of aqueous epoxy resin, 1-3 parts of fumed silica, 0.1-0.5 part of coupling agent, 0.1-0.5 part of wetting agent and 0.1-0.5 part of defoaming agent are mixed, stirred at the rotating speed of 500-600 r/min for 10-20 min, then 0.1-0.5 part of aqueous thickening agent is added, and then the mixture is continuously stirred at the rotating speed of 700-800 r/min for 30-60 min until the viscosity reaches 3000-7000 mPa.s, and the stirring is stopped, and after the filtration, the main adhesive is obtained; the main adhesive and the water-based isocyanate curing agent are used in a matching manner according to the weight ratio of 100: 2-10, so that the high-heat-resistance flicking water-based polyurethane adhesive is obtained.
A method for testing the heat-resisting flicking performance of an adhesive comprises the steps of mixing a main adhesive and a water-based isocyanate curing agent in the high heat-resisting flicking water-based polyurethane adhesive according to the weight ratio of 100: 2-10 in a constant temperature room at 25 ℃, and stirring for 10-20 min at the rotating speed of 500-600 r/min to obtain a premixed adhesive(ii) a Taking an ABS plastic plate and leather with the width of 2.5cm as base materials, taking the premixed glue, and taking the premixed glue at the ratio of 100-120 g/m2The two base materials are glued, then the two base materials are placed in an oven and activated for 5-7 min at the temperature of 60-70 ℃, then the activated leather and the activated ABS plastic plate are quickly coated and bonded, a 1kg weight is used for hanging the leather to be heavy, the falling distance of the weight within 1min is tested, and the heat-resistant flicking performance of the adhesive is evaluated according to the distance.
According to the technical scheme provided by the invention, the main adhesive of the high-heat-resistant flicking aqueous polyurethane adhesive is prepared by organically combining the high-heat-resistant flicking aqueous polyurethane dispersoid with the aqueous epoxy resin, the aqueous thickening agent, the fumed silica, the coupling agent, the wetting agent and the defoaming agent, so that the VOC (volatile organic compound) emission after the film formation of the adhesive can be obviously reduced, the smell of an adhesive film is reduced, and the environmental quality of a production workshop is improved.
Detailed Description
The technical solutions in the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without making any creative effort, shall fall within the protection scope of the present invention.
The high heat-elasticity resistant waterborne polyurethane dispersion, the adhesive and the preparation method thereof provided by the invention are described in detail below. Details not described in the present invention are well known to those skilled in the art.
High-heat-elasticity-resistance waterborne polyurethane dispersion and preparation method thereof
The high-heat-resistance elastic waterborne polyurethane dispersion is prepared from the following raw materials in parts by weight:
specifically, the preparation method of the high heat-resistant elastic waterborne polyurethane dispersion can comprise the following steps:
step 1, adding 160-180 parts by weight of polyester polyol, 5-10 parts by weight of polyether polyol and 0-5 parts by weight of hydrophilic compound into a reaction device, dehydrating for 0.5-4 hours at 90-120 ℃ and under the environment of vacuum degree of-0.08-0.1 MPa, cooling to 65-80 ℃, adding 20-30 parts by weight of isocyanate, 0.1-0.8 part by weight of alcohol chain extender, 0-0.5 part by weight of internal cross-linking agent and 0.02-0.04 part by weight of catalyst, reacting for 3-5 hours at 65-80 ℃ until the content of-NCO reaches 0.8% -2%, and obtaining a first intermediate.
And 2, cooling the first intermediate to 35-55 ℃, adding 250-350 parts by weight of acetone into the first intermediate to adjust the viscosity of the prepolymer, controlling the temperature to 35-55 ℃, adding 0-3 parts by weight of a neutralizing agent to perform neutralization reaction for 20 min-1.5 h, and adding 190-300 parts by weight of deionized water to perform emulsification, thereby obtaining a second intermediate.
Step 3, controlling the temperature of the second intermediate to be 35-55 ℃, adding 0.1-0.8 part by weight of amine chain extender, 0-5 parts by weight of hydrophilic compound and 0-0.5 part by weight of internal cross-linking agent into the second intermediate, stirring for 20 min-1.5 h, removing acetone under reduced pressure, filtering and discharging after the solid content reaches 48.5-51.5%, thereby obtaining the high heat-resistant elastic aqueous polyurethane dispersion;
wherein the sum of the amounts of the hydrophilic compound in the step 1 and the hydrophilic compound in the step 3 is 2-5 parts by weight; the total amount of the internal cross-linking agent in the step 1 and the internal cross-linking agent in the step 3 is 0.1-0.5 parts by weight.
Further, the high heat resilience aqueous polyurethane dispersion may include the following embodiments:
(1) the number average molecular weight of the polyester polyol is 1000-3000, and the polyester polyol can adopt one or more of polybutylene adipate, polyhexamethylene adipate, octapentanediol adipate, neopentyl glycol adipate, polycaprolactone and polycarbonate polyol.
(2) The number average molecular weight of the polyether polyol is 1000-3000, and the polyether polyol can adopt one or more of polyoxypropylene glycol PPG and polytetrahydrofuran.
(3) The hydrophilic compound is at least one of a carboxylate hydrophilic compound or a sulfonate hydrophilic compound; the carboxylate hydrophilic compound can adopt one or more of dimethylolpropionic acid and dimethylolbutyric acid; the sulfonate hydrophilic compound can adopt one or more of 1, 2-propylene glycol-3-sodium sulfonate, 1, 4-butanediol-2-sodium sulfonate, sulfonate oligomer and ethylene diamino ethane sodium sulfonate.
(4) The isocyanate may be one or more of isophorone diisocyanate (IPDI), Hexamethylene Diisocyanate (HDI), HDI trimer, Toluene Diisocyanate (TDI), 4' -diphenylmethane diisocyanate (MDI), and polyphenyl polymethylene polyisocyanate (PAPI).
(5) The internal cross-linking agent can adopt one or more of trimethylolpropane, glycerol, triethanolamine, diethylenetriamine and triethylene tetramine.
(6) The catalyst can adopt one or more of organic tin catalysts (such as dibutyltin dilaurate), stannous octoate and organic bismuth catalysts.
(7) The neutralizing agent can adopt one or more of triethylamine, dimethylethanolamine, N-methylethanolamine, sodium hydroxide and sodium carbonate.
(8) The alcohol chain extender can adopt one or more of 1, 4-butanediol, 1, 6-hexanediol, neopentyl glycol, octapentanediol, diethanolamine, diethylene glycol, dipropylene glycol, 1, 3-propanediol and 1, 2-propanediol.
(9) The amine chain extender can adopt one or more of ethylenediamine, propylenediamine and isophorone diamine.
(II) high-heat-resistance pop-up waterborne polyurethane adhesive and preparation method thereof
A high-heat-resistance pop-up waterborne polyurethane adhesive comprises a main adhesive and a waterborne isocyanate curing agent, wherein the main adhesive and the waterborne isocyanate curing agent are used in a matched manner according to the weight ratio of 100: 2-10;
the main rubber is prepared from the following raw materials in parts by weight:
specifically, the preparation method of the high heat-resistant pop-up waterborne polyurethane adhesive comprises the following steps: according to the weight parts, 70-90 parts of the high heat-resistant elastic boiled water polyurethane dispersion provided by the invention, 10-30 parts of aqueous epoxy resin, 1-3 parts of fumed silica, 0.1-0.5 part of coupling agent, 0.1-0.5 part of wetting agent and 0.1-0.5 part of defoaming agent are mixed, stirred for 10-20 min at the rotating speed of 500-600 r/min, then 0.1-0.5 part of aqueous thickening agent is diluted by pure water and slowly dripped into the mixed solution, and after the addition, stirring is continued for 30-60 min at the rotating speed of 700-800 r/min until the viscosity reaches 3000-7000 mPa.s, and the stirring is stopped, and a 200-mesh filter screen is used for filtering to obtain a main adhesive; the main adhesive and the water-based isocyanate curing agent are used in a matching manner according to the weight ratio of 100: 2-10, so that the high-heat-resistance flicking water-based polyurethane adhesive is obtained.
Further, the high heat resistant pop-up waterborne polyurethane adhesive may include the following embodiments:
(1) the waterborne epoxy resin can adopt the processes of adico HUX-1029, HUX-830 and the Saisen EPIKOTE in the prior artTM6520 one or more of them.
(2) The water-based thickener can adopt one or more of TEGO Visco Plus 3000, Acrysol RM2020 of Romen Haas, Acrysol RM8W of Romen Haas, Acrysol RM12W of Romen Haas, Acrysol RM5000 of Romen Haas, HEUR-A of Synfeic, HEUR-B of Synfeic, and Vesmody A801 of VawA chemical, which are won and created in the prior art.
(3) The coupling agent can be one or more of coupling agent KH450, coupling agent KH550, coupling agent KH560, coupling agent KH570 and coupling agent KH602 in the prior art.
(4) The wetting agent can adopt one or more of TEGO WET KL245, BYK345, BYK346, BYK349 and BYK378 won in the prior art.
(5) The defoaming agent can adopt one or more of BASF Foamaster 8034, BYK018, BYK019, BYK093, Kalaien A200, AFCONA 2590, SKC DF942 and DF677 in the prior art.
(6) The waterborne isocyanate curing agent can adopt one or more of Bayer Desmodur DN, Bayer Bayhydur 3100, Tantanorian Aquolin268, Tantanorian Aquolin270 and Tantanorian Aquolin278 in the prior art.
Method for testing heat-resisting flicking performance of adhesive
In order to evaluate the heat-resistant flicking performance of the water-based polyurethane adhesive, the invention provides a method for testing the heat-resistant flicking performance of the adhesive, and the method comprises the steps of mixing a main adhesive and a water-based isocyanate curing agent in the high heat-resistant flicking water-based polyurethane adhesive provided by the invention according to the weight ratio of 100: 2-10 in a constant temperature room at 25 ℃, and stirring for 10-20 min at the rotating speed of 500-600 r/min to obtain a premixed adhesive; taking an ABS plastic plate and leather with the width of 2.5cm as base materials, taking the premixed glue, and taking the premixed glue at the ratio of 100-120 g/m2The two base materials are glued, then the two base materials are placed in an oven and activated for 5-7 min at the temperature of 60-70 ℃, then the activated leather is rapidly bonded on the activated ABS plastic plate, a 1kg weight is used for hanging the leather to be hung, the falling distance of the weight within 1min is tested, and the heat-resistant flicking performance of the adhesive is evaluated according to the distance.
Specifically, the method for testing the heat-resistant flick performance of the adhesive provided by the invention is simple and easy to operate, and can be used for better judging the heat-resistant flick performance of the aqueous polyurethane adhesive.
Through detection: the high heat-resistant flick-resistant waterborne polyurethane adhesive provided by the invention has the bonding strength of 90-130N/5 cm at normal temperature, the tearing force is more than 70N/5cm after the wet heat aging impact of 25 days, the heat-resistant flick test value is about 0.2-0.3cm, and the phenomena of bulging, deformation, flick of covered edges and the like do not exist.
The embodiment of the invention organically combines the high heat-resistant elastic waterborne polyurethane dispersoid with the waterborne epoxy resin, the waterborne thickener, the fumed silica, the coupling agent, the wetting agent and the defoaming agent to prepare the main adhesive of the high heat-resistant elastic waterborne polyurethane adhesive, fully utilizes the high heat-resistant elastic characteristic of the high heat-resistant elastic waterborne polyurethane dispersoid, not only can remarkably reduce the VOC emission after the film formation of the adhesive, reduce the smell of an adhesive film and improve the environmental quality of a production workshop, and the high heat-resistant flicking characteristic of the high heat-resistant flicking aqueous polyurethane dispersoid can be utilized to obviously improve the heat-resistant flicking performance of the adhesive, overcome the defects that the existing aqueous polyurethane adhesive has poor heat-resistant flicking performance, and the edge of an adhesive piece is easy to flick and bulge, and the like, and can be widely applied to the fields of automobiles, high-speed rails, furniture, shoe making, textile, and the like.
Compared with the prior art, the high-heat-resistant elastic waterborne polyurethane dispersion and the adhesive provided by the invention have higher heat-resistant elastic opening performance, overcome the defects that the existing waterborne polyurethane adhesive is poor in heat-resistant elastic opening performance, and an edge of a bonding piece is easy to open and bulge, and the like, and can be widely applied to the fields of automobiles, high-speed rails, furniture, shoe making, textiles and the like.
In conclusion, the embodiment of the invention is environment-friendly, non-toxic, low in VOC (volatile organic compounds), low in odor and excellent in bonding strength, the heat-resisting flicking performance is obviously improved, serious bonding quality accidents such as bulging, flicking of the covered edge and the like easily occurring in the scene of covered edge or large base material tension are avoided, good economic benefits are brought, and the invention can be widely applied to the fields of automobiles, high-speed rails, furniture, shoe making, textiles and the like.
In order to more clearly show the technical scheme and the technical effects provided by the invention, the high heat-resistant elastic waterborne polyurethane dispersion, the adhesive and the preparation method thereof provided by the embodiment of the invention are described in detail by specific embodiments.
Example 1
The preparation method of the high-heat-elasticity-resistance waterborne polyurethane dispersion can comprise the following steps:
step A1, 163g of polybutylene adipate (number average molecular weight 2000), 10g of polyoxypropylene glycol PPG (number average molecular weight 2000), 2g of dimethylolpropionic acid, 2g of 1, 4-butanediol-2-sodium sulfonate were added to a reaction apparatus, dehydration was carried out for 4 hours at 90 ℃ under an environment of a vacuum degree of-0.09 MPa, the temperature was reduced to 70 ℃, 15g of hexamethylene diisocyanate, 5g of isophorone diisocyanate, 0.5g of 1, 4-butanediol, 0.2g of trimethylolpropane and 0.02g of dibutyltin dilaurate were added, and the reaction was carried out for 4 hours at 75 ℃ until the content of-NCO reached 1%, to obtain a first intermediate.
And A2, cooling the first intermediate to 55 ℃, adding 250g of acetone into the first intermediate to adjust the viscosity of the prepolymer, controlling the temperature at 45 ℃, adding 2g of triethylamine to perform neutralization reaction for 40min, and adding 230g of deionized water to perform emulsification to obtain a second intermediate.
And A3, controlling the temperature of the second intermediate at 45 ℃, then adding 0.5g of ethylenediamine into the second intermediate, stirring for 50min, removing acetone under reduced pressure, filtering and discharging after the solid content reaches 50%, thereby obtaining the high-heat-resistance elastic waterborne polyurethane dispersion.
Example 2
The preparation method of the high-heat-elasticity-resistance waterborne polyurethane dispersion can comprise the following steps:
step B1, adding 150g of polybutylene adipate (number average molecular weight 2000), 20g of polybutylene adipate (number average molecular weight 3000), 5g of polytetrahydrofuran (number average molecular weight 2000), 1g of dimethylolpropionic acid, 1g of dimethylolbutyric acid and 2.5g of sodium 1, 2-propanediol-3-sulfonate into a reaction device, dehydrating for 1.5h under the environment of 100 ℃ and-0.1 MPa of vacuum degree, cooling to 75 ℃, adding 14g of 4,4' -diphenylmethane diisocyanate, 7g of polyphenyl polymethylene polyisocyanate, 0.7g of 1, 6-hexanediol, 0.25g of glycerol and 0.03g of dibutyltin dilaurate, and reacting for 4.5 h at 70 ℃ until the content of-NCO reaches 1.05% to obtain a first intermediate.
And step B2, cooling the first intermediate to 50 ℃, adding 260g of acetone into the first intermediate to adjust the viscosity of the prepolymer, controlling the temperature at 50 ℃, adding 2.2g of triethylamine to perform neutralization reaction for 1 hour, and adding 250g of deionized water to perform emulsification to obtain a second intermediate.
And step B3, controlling the temperature of the second intermediate at 40 ℃, then adding 0.5g of propane diamine into the second intermediate, stirring for 50min, removing acetone under reduced pressure, filtering and discharging after the solid content reaches 49%, thereby obtaining the high-heat-resistance elastic waterborne polyurethane dispersion.
Example 3
The preparation method of the high-heat-elasticity-resistance waterborne polyurethane dispersion can comprise the following steps:
step C1, 150g of polybutylene adipate (number average molecular weight 2000), 10g of polybutylene adipate (number average molecular weight 3000), 10g of polyhexamethylene adipate (number average molecular weight 2000), 5g of polyoxypropylene glycol PPG (number average molecular weight 1000), 2.5g of dimethylolpropionic acid and 2.5g of sulfonate oligomer are added into a reaction device, dehydration is carried out for 0.5h under the environment of 120 ℃ and vacuum degree of-0.1 MPa, 19g of hexamethylene diisocyanate, 6g of isophorone diisocyanate, 0.5g of 1, 6-hexanediol, 0.3g of neopentyl glycol and 0.03g of dibutyltin dilaurate are added after the temperature is reduced to 70 ℃, and the reaction is carried out for 4 hours at 75 ℃ until the content of-NCO reaches 1.02% to obtain a first intermediate.
And step C2, cooling the first intermediate to 55 ℃, adding 300g of acetone into the first intermediate to adjust the viscosity of the prepolymer, controlling the temperature at 45 ℃, adding 2.1g of dimethylethanolamine to perform a neutralization reaction for 20min, and adding 260g of deionized water to perform emulsification to obtain a second intermediate.
And step C3, controlling the temperature of the second intermediate at 45 ℃, then adding 0.4g of isophorone diamine and 0.25g of diethylenetriamine into the second intermediate, stirring for 50min, removing acetone under reduced pressure, filtering and discharging after the solid content reaches 50.5%, thereby obtaining the high-heat-resistant elastic waterborne polyurethane dispersion.
Example 4
The preparation method of the high-heat-elasticity-resistance waterborne polyurethane dispersion can comprise the following steps:
step D1, adding 165g of polybutylene adipate (number average molecular weight 2000), 5g of polyhexamethylene adipate (number average molecular weight 2000), 5g of neopentyl glycol polyadipate (number average molecular weight 2000) and 7g of polyoxypropylene glycol (number average molecular weight 1000) into a reaction device, dehydrating for 1h under the environment of 110 ℃ and vacuum degree of-0.08 MPa, cooling to 70 ℃, adding 19g of hexamethylene diisocyanate, 6g of isophorone diisocyanate, 0.5g of 1, 6-hexanediol, 0.2g of neopentyl glycol and 0.04g of organic bismuth catalyst, and reacting for 3.5 h at 80 ℃ until the content of-NCO reaches 1.02% to obtain a first intermediate.
And D2, cooling the first intermediate to 50 ℃, adding 320g of acetone into the first intermediate to adjust the viscosity of the prepolymer, controlling the temperature at 45 ℃, and adding 300g of deionized water to emulsify to obtain a second intermediate.
And D3, controlling the temperature of the second intermediate at 40 ℃, then dropwise adding 4g of ethylene diamino ethyl sodium sulfonate, 0.2g of ethylenediamine and 0.15g of triethylene tetramine into the second intermediate, stirring for 1h, removing acetone under reduced pressure, filtering and discharging after the solid content reaches 49.5%, and thus obtaining the high-heat-resistant elastic aqueous polyurethane dispersion.
Example 5
The preparation method of the high-heat-elasticity-resistance waterborne polyurethane dispersion can comprise the following steps:
step E1, 165g of polybutylene adipate (number average molecular weight 2000), 6g of polyhexamethylene adipate (number average molecular weight 2000), 5g of polycarbonate polyol (number average molecular weight 2000), 5g of polyoxypropylene glycol PPG (number average molecular weight 1000) and 2.5g of dimethylolpropionic acid were added to a reaction apparatus, dehydration was carried out at 100 ℃ under a vacuum of-0.1 MPa for 1.5 hours, cooling was carried out to 70 ℃ and 19g of hexamethylene diisocyanate, 6g of isophorone diisocyanate, 0.5g of 1, 6-hexanediol, 0.2g of neopentyl glycol, 0.1g of triethanolamine and 0.04g of dibutyltin dilaurate were added and reacted at 75 ℃ for 4.5 hours until the-NCO content reached 1.02%, thereby obtaining a first intermediate.
And E2, cooling the first intermediate to 55 ℃, adding 300g of acetone into the first intermediate to adjust the viscosity of the prepolymer, controlling the temperature at 40 ℃, adding 2.1g of triethylamine to perform neutralization reaction for 1.5h, and adding 280g of deionized water to perform emulsification to obtain a second intermediate.
And E3, controlling the temperature of the second intermediate at 40 ℃, then dropwise adding 2g of ethylene diamino ethyl sodium sulfonate, 0.2g of ethylenediamine and 0.1g of diethylenetriamine into the second intermediate, stirring for 1h, removing acetone under reduced pressure, filtering and discharging after the solid content reaches 50%, thereby obtaining the high-heat-resistant elastic waterborne polyurethane dispersion.
Example 6
The preparation method of the waterborne polyurethane adhesive comprises the following steps: mixing 70-90 g of aqueous polyurethane dispersoid, 10-30 g of aqueous epoxy resin, 1-3 g of fumed silica, 0.1-0.5 g of coupling agent, 0.1-0.5 g of wetting agent and 0.1-0.5 g of defoaming agent, stirring for 10-20 min at the rotating speed of 500-600 r/min, then diluting 0.1-0.5 g of aqueous thickening agent by 0.15g of pure water, slowly dripping into the mixed solution, continuously stirring for 30-60 min at the rotating speed of 700-800 r/min after finishing the dripping until the viscosity reaches 3000-7000 mPa.s, and filtering by using a 200-mesh filter screen to obtain main adhesive; the main adhesive and the water-based isocyanate curing agent are used in a matching manner according to the weight ratio of 100: 2-10, so that the water-based polyurethane adhesive is obtained.
Example 7
A high heat-resistant elastic waterborne polyurethane adhesive is marked as GMA1, the preparation method is basically the same as that of the embodiment 6 of the invention, but the waterborne polyurethane dispersion is the high heat-resistant elastic waterborne polyurethane dispersion prepared by the embodiment 1 of the invention, and the specific selection and material proportion of other raw materials are shown in the table 1.
Example 8
A high heat-resistant elastic waterborne polyurethane adhesive is marked as GMA2, the preparation method is basically the same as that of the embodiment 6 of the invention, but the waterborne polyurethane dispersion is the high heat-resistant elastic waterborne polyurethane dispersion prepared by the embodiment 2 of the invention, and the specific selection and material proportion of other raw materials are shown in the table 1.
Example 9
A high heat-resistant elastic waterborne polyurethane adhesive is marked as GMA3, the preparation method is basically the same as that of the embodiment 6 of the invention, but the waterborne polyurethane dispersion is the high heat-resistant elastic waterborne polyurethane dispersion prepared by the embodiment 3 of the invention, and the specific selection and material proportion of other raw materials are shown in the table 1.
Example 10
A high heat-resistant elastic waterborne polyurethane adhesive is marked as GMA4, the preparation method is basically the same as that of the embodiment 6 of the invention, but the waterborne polyurethane dispersion is the high heat-resistant elastic waterborne polyurethane dispersion prepared by the embodiment 4 of the invention, and the specific selection and material proportion of other raw materials are shown in Table 1.
Example 11
A high heat-resistant elastic waterborne polyurethane adhesive is marked as GMA5, the preparation method is basically the same as that of the embodiment 6 of the invention, but the waterborne polyurethane dispersion is the high heat-resistant elastic waterborne polyurethane dispersion prepared by the embodiment 5 of the invention, and the specific selection and material proportion of other raw materials are shown in Table 1.
Comparative example 1
An aqueous polyurethane adhesive, designated DB1, was prepared in substantially the same manner as in inventive example 6, except that the aqueous polyurethane dispersion was a commercially available German brand aqueous polyurethane dispersion, and the specific selection and formulation of the other raw materials are shown in Table 1.
Comparative example 2
An aqueous polyurethane adhesive, labeled as DB2, was prepared in substantially the same manner as in example 6 of the present invention, except that the aqueous polyurethane dispersion was a commercially available aqueous polyurethane dispersion of a Chinese brand, and the specific selection and formulation of other raw materials are shown in Table 1.
TABLE 1 (units are g)
Performance detection
The following performance tests were performed on the high heat-resistant pop-up waterborne polyurethane adhesives prepared in examples 7 to 11 of the present invention and the waterborne polyurethane adhesives prepared in comparative examples 1 to 2, respectively:
(1) mixing the main glue and the water-based isocyanate curing agent in the water-based polyurethane adhesive in a constant temperature room at 25 ℃ according to the weight ratio of 100:5, and stirring at the rotating speed of 500-600 r/min for 10-20 min to obtain a premixed glue; taking an ABS plastic plate and leather with the width of 2.5cm as base materials, taking the premixed glue, and taking the premixed glue at the ratio of 100-120 g/m2The two base materials are glued, then the two base materials are placed in an oven and activated for 5-7 min at the temperature of 60-70 ℃, then the activated leather is quickly adhered to the activated ABS plastic plate, a 1kg weight is used for hanging the leather to hang the weight, the falling distance of the weight within 1min is tested, the heat-resistant flicking performance of the adhesive is evaluated according to the distance, and the result is shown in Table 2.
(2) Mixing the main glue and the water-based isocyanate curing agent in the water-based polyurethane adhesive in a constant temperature room at 25 ℃ according to the weight ratio of 100:5, and stirring at the rotating speed of 500-600 r/min for 10-20 min to obtain a premixed glue; taking an ABS plastic plate and leather with the width of 2.5cm as base materials, taking the premixed glue, and taking the premixed glue at the ratio of 100-120 g/m2The two base materials are glued, then the two base materials are placed into an oven and activated for 5-7 min at the temperature of 60-70 ℃, and then the activated leather is quickly bonded on the activated ABS plastic plate to form a bonding piece; the adhesive was cured for 72 hours and then subjected to a bond strength test, and the results are shown in table 2 below.
(3) Mixing the main adhesive and the water-based isocyanate curing agent in the water-based polyurethane adhesive in a constant temperature room at 25 ℃ according to the weight ratio of 100:5, and stirring at the rotating speed of 500-600 r/min for 10-20 min to obtain the premixed polyurethane adhesiveGluing; taking an ABS plastic plate and leather with the width of 2.5cm as base materials, taking the premixed glue, and taking the premixed glue at the ratio of 100-120 g/m2The two base materials are glued, then the two base materials are placed into an oven and activated for 5-7 min at the temperature of 60-70 ℃, and then the activated leather is quickly bonded on the activated ABS plastic plate to form a bonding piece; the adhesive was aged for 72 hours, and then subjected to a bond strength test after 25 days of wet heat aging impact, and the results are shown in table 2 below.
TABLE 2
As can be seen from table 2 above: the high heat-resistant pop-up waterborne polyurethane adhesives GMA 1-GMA 5 prepared by using the high heat-resistant pop-up waterborne polyurethane dispersions in the embodiments 1-5 of the invention have excellent heat-resistant pop-up performance, basically fluctuate between 0.2-0.3cm, the bonding strength tested at normal temperature is 98-115N/5 cm, the bonding strength is more than 75N/5cm after 25-day damp-heat aging impact, and the wrapping edges have no phenomena of pop-up, bulging, deformation and the like. The heat-resistant popping-open performance of the waterborne polyurethane adhesives DB 1-DB 2 prepared in the comparative examples 1-2 is basically over 1cm, wherein the waterborne polyurethane adhesive DB2 prepared by the national brand dispersoid cannot pass the humid heat aging impact for 25 days, and the bound edges of the bonded pieces have the phenomenon of popping-open or bulging.
In conclusion, the embodiment of the invention is environment-friendly, non-toxic, low in VOC (volatile organic compounds), low in odor and excellent in bonding strength, the heat-resisting flicking performance is obviously improved, serious bonding quality accidents such as bulging, flicking of the covered edge and the like easily occurring in the scene of covered edge or large base material tension are avoided, good economic benefits are brought, and the invention can be widely applied to the fields of automobiles, high-speed rails, furniture, shoe making, textiles and the like. Meanwhile, the embodiment of the invention also develops a simple heat-resistant flick test method, which can better judge the heat-resistant flick performance of the waterborne polyurethane adhesive.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (5)
1. The high-heat-resistance elastic waterborne polyurethane dispersion is characterized by being prepared from the following raw materials in parts by weight:
2. a preparation method of a high-heat-elasticity-resistance waterborne polyurethane dispersion is characterized by comprising the following steps of:
step 1, adding 160-180 parts by weight of polyester polyol, 5-10 parts by weight of polyether polyol and 0-5 parts by weight of hydrophilic compound into a reaction device, dehydrating for 0.5-4 hours at 90-120 ℃ and under the environment of vacuum degree of-0.08-0.1 MPa, cooling to 65-80 ℃, adding 20-30 parts by weight of isocyanate, 0.1-0.8 part by weight of alcohol chain extender, 0-0.5 part by weight of internal cross-linking agent and 0.02-0.04 part by weight of catalyst, reacting for 3-5 hours at 65-80 ℃ until the content of-NCO reaches 0.8% -2%, and obtaining a first intermediate;
step 2, cooling the first intermediate to 35-55 ℃, adding 250-350 parts by weight of acetone into the first intermediate to adjust the viscosity of the prepolymer, controlling the temperature to 35-55 ℃, adding 0-3 parts by weight of a neutralizing agent to perform neutralization reaction for 20 min-1.5 h, and adding 190-300 parts by weight of deionized water to perform emulsification to obtain a second intermediate;
step 3, controlling the temperature of the second intermediate to be 35-55 ℃, adding 0.1-0.8 part by weight of amine chain extender, 0-5 parts by weight of hydrophilic compound and 0-0.5 part by weight of internal cross-linking agent into the second intermediate, stirring for 20 min-1.5 h, removing acetone under reduced pressure, filtering and discharging after the solid content reaches 48.5-51.5%, thereby obtaining the high heat-resistant elastic aqueous polyurethane dispersion of claim 1;
wherein the sum of the amounts of the hydrophilic compound in the step 1 and the hydrophilic compound in the step 3 is 2-5 parts by weight; the total amount of the internal cross-linking agent in the step 1 and the internal cross-linking agent in the step 3 is 0.1-0.5 parts by weight.
3. The high-heat-resistance pop-up waterborne polyurethane adhesive is characterized by comprising a main adhesive and a waterborne isocyanate curing agent, wherein the main adhesive and the waterborne isocyanate curing agent are used in a matched manner according to the weight ratio of 100: 2-10;
the main rubber is prepared from the following raw materials in parts by weight:
4. a preparation method of a high heat-resistant pop-up waterborne polyurethane adhesive is characterized by comprising the following steps:
according to parts by weight, 70-90 parts of the high heat-resistant elastic waterborne polyurethane dispersion as described in claim 1, 10-30 parts of waterborne epoxy resin, 1-3 parts of fumed silica, 0.1-0.5 part of coupling agent, 0.1-0.5 part of wetting agent and 0.1-0.5 part of defoaming agent are mixed, stirred at the rotating speed of 500-600 r/min for 10-20 min, then 0.1-0.5 part of waterborne thickener is added, and then stirred at the rotating speed of 700-800 r/min for 30-60 min after the addition is finished until the viscosity reaches 3000-7000 mPa.s, the stirring is stopped, and after filtration, the main adhesive is obtained;
the main adhesive and the water-based isocyanate curing agent are used together according to the weight ratio of 100: 2-10, so that the high heat-resistant elastic water-based polyurethane adhesive as claimed in claim 3 is obtained.
5. A method for testing the heat-resisting spring-open performance of an adhesive is characterized by comprising the following steps:
combining the main adhesive of the high thermal resistant pop-up waterborne polyurethane adhesive of claim 3 with a waterborne isocyanate in a thermostatic chamber at 25 ℃Mixing the curing agents according to the weight ratio of 100: 2-10, and stirring at the rotating speed of 500-600 r/min for 10-20 min to obtain premixed glue; taking an ABS plastic plate and leather with the width of 2.5cm as base materials, taking the premixed glue, and taking the premixed glue at the ratio of 100-120 g/m2The two base materials are glued, then the two base materials are placed in an oven and activated for 5-7 min at the temperature of 60-70 ℃, then the activated leather and the activated ABS plastic plate are quickly coated and bonded, a 1kg weight is used for hanging the leather to be heavy, the falling distance of the weight within 1min is tested, and the heat-resistant flicking performance of the adhesive is evaluated according to the distance.
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