CN110819289A - Polyurethane adhesive and preparation method thereof - Google Patents
Polyurethane adhesive and preparation method thereof Download PDFInfo
- Publication number
- CN110819289A CN110819289A CN201911108546.8A CN201911108546A CN110819289A CN 110819289 A CN110819289 A CN 110819289A CN 201911108546 A CN201911108546 A CN 201911108546A CN 110819289 A CN110819289 A CN 110819289A
- Authority
- CN
- China
- Prior art keywords
- polyurethane adhesive
- zinc oxide
- nano zinc
- parts
- polyurethane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- 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
- C09J175/08—Polyurethanes from polyethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
-
- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention provides a polyurethane adhesive and a preparation method thereof, relating to the technical field of polyurethane preparation and comprising the following steps: modifying the nano zinc oxide by using a silane coupling agent to obtain silane modified nano zinc oxide particles; carrying out reduced pressure distillation on polyether polyol to obtain anhydrous polyol; mixing and dispersing silane modified nano zinc oxide particles, anhydrous polyhydric alcohol and an antioxidant to obtain a dispersion liquid; under the conditions of nitrogen atmosphere and stirring, heating the dispersion to 60-80 ℃, adding diphenylmethane diisocyanate, and reacting to obtain a polyurethane prepolymer; and cooling the polyurethane prepolymer to 60-65 ℃, adding a chain extender, and reacting to obtain the polyurethane adhesive. According to the preparation method of the polyurethane adhesive, the polyurethane adhesive is modified by adding the silane modified nano zinc oxide particles and the antioxidant, so that the aging resistance and the weather resistance of the polyurethane adhesive are improved.
Description
Technical Field
The invention relates to the technical field of polyurethane preparation, in particular to a polyurethane adhesive and a preparation method thereof.
Background
Because impurities such as catalysts and low-bond-energy chemical bonds such as C-H and the like exist in the Polyurethane (PU) adhesive, the polyurethane adhesive is sensitive to light, heat, oxygen and the like, and can age in the processes of storage and use to influence the comprehensive performance of the PU adhesive; especially for outdoor use, when the PU adhesive is used as a curing agent of automobile windshields, the performance of the polyurethane adhesive is easily influenced due to aging; therefore, the aging resistance modification of the polyurethane adhesive is particularly important.
Disclosure of Invention
The invention solves the problem of how to improve the aging resistance of the polyurethane adhesive.
In order to solve the problems, the invention provides a preparation method of a polyurethane adhesive, which comprises the following steps:
s1: modifying the nano zinc oxide by using a silane coupling agent to obtain silane modified nano zinc oxide particles;
s2: carrying out reduced pressure distillation on polyether polyol to obtain anhydrous polyol;
s3: mixing and dispersing the silane modified nano zinc oxide particles, the anhydrous polyhydric alcohol and the antioxidant to obtain a dispersion liquid;
s4: heating the dispersion to 60-80 ℃ under the nitrogen atmosphere and stirring conditions, adding diphenylmethane diisocyanate, and reacting to obtain a polyurethane prepolymer;
s5: and cooling the polyurethane prepolymer to 60-65 ℃, adding a chain extender, and reacting to obtain the polyurethane adhesive.
Optionally, the silane coupling agent comprises gamma-aminopropyltriethoxysilane.
Optionally, step S1 includes: weighing 80-100 parts by weight of anhydrous toluene, heating to 80 ℃, respectively adding 3-8 parts by weight of nano zinc oxide and 1-5 parts by weight of silane coupling agent, stirring for 5 hours, then carrying out centrifugal separation, and carrying out vacuum drying on the precipitate after centrifugal separation at 50 ℃ for 24 hours to obtain the silane modified nano zinc oxide particles.
Optionally, the polyether polyol in step S2 includes at least one of polytetrahydrofuran ether glycol and polycaprolactone glycol; the pressure of the reduced pressure distillation is-0.1 MPa, the temperature range is 110-150 ℃, and the time range of the reduced pressure distillation is 2-4 h.
Alternatively, the antioxidant described in step S3 comprises 3, 9-bis- {1, 1-dimethyl-2 [ b- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy ] ethyl } -2,4,8, 10-tetraoxaaspirin [5,5] undecane.
Optionally, in the step S3, the silane-modified nano zinc oxide particles are added in an amount of 0.2 to 5 parts by weight, the anhydrous polyol is added in an amount of 50 to 100 parts by weight, and the antioxidant is added in an amount of 0.05 to 2 parts by weight.
Alternatively, the mixing and dispersing process described in step S3 includes: the mixture is treated by ultrasonic waves for 3 to 10 minutes under the power of 500 to 1000 watts.
Optionally, the amount of the diphenylmethane diisocyanate added in the step S4 is 10 to 40 parts by weight; the reaction time in the step S4 is 1.5-3 h.
Optionally, the chain extender described in step S5 includes diethanolamine; the addition amount of the chain extender is 3-10 parts by weight; the reaction time in step S5 is 5 to 20 minutes.
Another object of the present invention is to provide a polyurethane adhesive, which is prepared by the method for preparing a polyurethane adhesive according to any one of claims 1 to 9.
Compared with the prior art, the preparation method of the polyurethane adhesive provided by the invention has the following advantages:
the preparation method of the polyurethane adhesive provided by the invention modifies the polyurethane adhesive by adding the silane modified nano zinc oxide particles and the antioxidant in the preparation process of the polyurethane, which is not only beneficial to uniformly distributing the silane modified nano zinc oxide particles and the antioxidant in the polyurethane adhesive and improving the uniformity and stability of the performance distribution of the polyurethane adhesive, but also beneficial to organically combining the silane modified nano zinc oxide particles and the antioxidant with a polyurethane adhesive matrix and slowing down the consumption of the silane modified nano zinc oxide particles and the antioxidant in the storage and use processes of the polyurethane adhesive, thereby being more beneficial to improving the stability of the performance of the polyurethane adhesive and further improving the aging resistance and the weather resistance of the polyurethane adhesive.
Drawings
FIG. 1 is a tensile shear strength curve of polyurethane adhesive prepared by silane modified zinc oxide nanoparticles with different addition amounts according to the present invention;
FIG. 2 is a graph of the tensile shear strength of unmodified polyurethane adhesives and modified polyurethane adhesives of the present invention after thermo-oxidative aging;
FIG. 3 is a scanning electron microscope image of the modified polyurethane adhesive of the present invention;
FIG. 4 is a scanning electron microscope image of the modified polyurethane adhesive of the present invention aged for 400 h;
FIG. 5 is a scanning electron microscope image of the modified polyurethane adhesive of the present invention aged for 1000 h;
FIG. 6 is a scanning electron micrograph of an unmodified polyurethane adhesive according to the present invention;
FIG. 7 is a scanning electron microscope image of an unmodified polyurethane adhesive of the present invention aged 400 hours;
FIG. 8 is a scanning electron microscope image of an unmodified polyurethane adhesive of the present invention aged 1000 h.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in detail below.
In order to improve the aging resistance of the polyurethane adhesive, the invention provides a preparation method of the polyurethane adhesive, which comprises the following steps:
s1: modifying the nano zinc oxide by using a silane coupling agent to obtain silane modified nano zinc oxide particles;
s2: carrying out reduced pressure distillation on polyether polyol to obtain anhydrous polyol;
s3: mixing and dispersing silane modified nano zinc oxide particles, anhydrous polyhydric alcohol and an antioxidant to obtain a dispersion liquid;
s4: under the conditions of nitrogen atmosphere and stirring, heating the dispersion to 60-80 ℃, adding diphenylmethane diisocyanate, and reacting to obtain a polyurethane prepolymer;
s5: and cooling the polyurethane prepolymer to 60-65 ℃, adding a chain extender, and reacting to obtain the polyurethane adhesive.
The nano zinc oxide is widely applied to polymer materials because of excellent light stability and filling enhancement performance, and in order to increase the dispersibility of the nano zinc oxide in matrix resin, the silane coupling agent is firstly used for modifying the nano zinc oxide to obtain silane modified nano zinc oxide particles, so that the silane modified nano zinc oxide particles are convenient to improve the uniformity of the silane modified nano zinc oxide in the matrix while achieving the light stability and the filling enhancement performance of the nano zinc oxide, thereby ensuring the uniform and stable performance of the product; the preferred particle size range of the nano zinc oxide is 20 nm-50 nm.
Because the polyurethane adhesive is prepared by the reaction of diphenylmethane diisocyanate (MDI), MDI is easy to react with water, and therefore, in order to avoid the influence on the yield of the reaction caused by the consumption of MDI due to the existence of moisture in a reaction system, the polyether polyol is subjected to reduced pressure distillation to remove water molecules in the polyether polyol, and the smooth proceeding of the subsequent reaction is ensured.
In addition, the existence of water molecules can generate bubbles in the reaction process, so that the generated polyurethane adhesive product has bubbles, and the product quality is influenced; the water molecules are removed by reduced pressure distillation, which is also beneficial to improving the quality of the product.
Mixing silane-modified nano zinc oxide particles, anhydrous polyhydric alcohol obtained by reduced pressure distillation and dehydration and an antioxidant to obtain a dispersion liquid; by utilizing the characteristics of the antioxidant that the antioxidant has the function of resisting thermal oxidation aging and has good compatibility with the polyurethane adhesive, the antioxidant is added to further modify the function of resisting thermal oxidation aging of the polyurethane adhesive so that the antioxidant and the silane-modified nano zinc oxide particles act together, so that the prepared polyurethane adhesive has excellent photo-oxidation aging resistance and thermal oxidation aging resistance, and the purpose of improving the aging resistance of the polyurethane adhesive is realized.
In the preparation process of the polyurethane adhesive, because MDI has high reaction activity, in order to reduce the occurrence of side reactions and improve the conversion rate of reaction raw material MDI, the invention firstly heats the dispersion liquid to the reaction temperature, namely 60-80 ℃, then MDI is added, and the added MDI reacts with the anhydrous polyhydric alcohol to generate the polyurethane prepolymer; after the reaction is finished, cooling the polyurethane prepolymer generated by the reaction to 60-65 ℃, adding a chain extender to increase the molecular chain of the polyurethane prepolymer, and curing and molding the resin to obtain the polyurethane adhesive.
Because the polyurethane adhesive is generated by the reaction of the anhydrous polyalcohol and MDI, the generated polyurethane adhesive is blocked by the isocyanate group, and the isocyanate group is easy to react with water for curing, the curing mode of the polyurethane adhesive prepared by the invention is room temperature moisture curing.
The room temperature moisture curing mode can greatly reduce the use difficulty of the polyurethane adhesive and improve the use experience of users.
The preparation method of the polyurethane adhesive provided by the invention modifies the polyurethane adhesive by adding the silane modified nano zinc oxide particles and the antioxidant in the preparation process of the polyurethane, which is not only beneficial to uniformly distributing the silane modified nano zinc oxide particles and the antioxidant in the polyurethane adhesive and improving the uniformity and stability of the performance distribution of the polyurethane adhesive, but also beneficial to organically combining the silane modified nano zinc oxide particles and the antioxidant with a polyurethane adhesive matrix and slowing down the consumption of the silane modified nano zinc oxide particles and the antioxidant in the storage and use processes of the polyurethane adhesive, thereby being more beneficial to improving the stability of the performance of the polyurethane adhesive and further improving the aging resistance and the weather resistance of the polyurethane adhesive.
In addition, the preparation method of the polyurethane adhesive provided by the invention does not introduce a solvent and a catalyst in the process of generating the polyurethane prepolymer by reacting the anhydrous polyhydric alcohol with MDI and the process of increasing the polyurethane molecular chain through the chain extender, so that the use of the solvent and the catalyst can be reduced while the prepared polyurethane adhesive has excellent aging resistance and weather resistance, the secondary pollution to the environment is avoided, the purity of the polyurethane adhesive is favorably improved, and the influence on the performance of the polyurethane adhesive due to the existence of impurities is avoided.
The silane coupling agent in the invention comprises a silane coupling agent gamma-aminopropyl triethoxysilane.
The principle of the gamma-aminopropyltriethoxysilane modified nano zinc oxide particles is shown as the following formula:
the gamma-aminopropyl triethoxysilane is combined with the hydroxyl adsorbed on the surface of the nano zinc oxide to generate a chemical bond, thereby realizing the modification of the nano zinc oxide particles.
The gamma-aminopropyltriethoxysilane is used for modifying the nano zinc oxide, so that the dispersibility of nano zinc oxide particles in the polyurethane adhesive is improved, and the modified nano zinc oxide particles are provided with amino groups on the surfaces, so that the amino groups can further react with isocyanic acid radicals on a polyurethane main chain in the reaction process, the strength of the polyurethane adhesive is improved, and the performance stability of the polyurethane adhesive is improved.
Specifically, step S1 includes: weighing 80-100 parts by weight of anhydrous toluene, heating to 80 ℃, respectively adding 3-8 parts by weight of nano zinc oxide and 1-5 parts by weight of silane coupling agent, stirring for 5 hours, then carrying out centrifugal separation, and carrying out vacuum drying on the precipitate after centrifugal separation at 50 ℃ for 24 hours to obtain silane modified nano zinc oxide particles.
The nanometer zinc oxide particles are modified through the process, and the silane modified nanometer zinc oxide particles are used as a modifier of the polyurethane adhesive, so that the photooxidation aging resistance of the polyurethane adhesive is improved, and meanwhile, the dispersibility of the nanometer zinc oxide particles in a matrix and the strength of the polyurethane adhesive can be improved.
The polyether polyol in step S2 of the invention comprises at least one of polytetrahydrofuran ether glycol and polycaprolactone glycol; the pressure of the reduced pressure distillation is-0.1 MPa, the temperature range is 110-150 ℃, and the time range of the reduced pressure distillation is 2-4 h.
Through setting parameters of reduced pressure distillation, on one hand, moisture in polyether polyol is guaranteed to be removed, and on the other hand, the efficiency of reduced pressure distillation can be guaranteed.
In order to ensure the stability of the anti-aging performance of the polyurethane adhesive, the antioxidant in step S3 of the invention comprises 3, 9-bis- {1, 1-dimethyl-2 [ b- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy ] ethyl } -2,4,8, 10-tetraoxaaspirin [5,5] undecane.
The 3, 9-bis- {1, 1-dimethyl-2 [ b- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy ] ethyl } -2,4,8, 10-tetraoxaaspirin [5,5] undecane antioxidant, namely, the asymmetric hindered phenol antioxidant AO-80 containing a spiro structure, has better compatibility with a polyurethane adhesive, and simultaneously has larger molecular weight, and is not easy to be consumed due to phenomena of volatilization, extraction, migration and the like in the storage and use processes of the polyurethane adhesive, thereby being beneficial to ensuring the performance stability of the polyurethane adhesive and improving the weather resistance of the polyurethane adhesive.
In order to ensure the ageing resistance of the polyurethane adhesive and avoid unnecessary waste caused by improper addition of raw materials, the silane-modified nano zinc oxide particles are added in the step S3 in an amount of 0.2-5 parts by weight, the anhydrous polyhydric alcohol is added in an amount of 50-100 parts by weight, and the antioxidant is added in an amount of 0.05-2 parts by weight.
In addition, in order to ensure that the silane-modified nano zinc oxide particles, the anhydrous polyhydric alcohol and the antioxidant can be fully mixed and dispersed, the mixing and dispersing process in the step S3 comprises the following steps: the mixture is treated by ultrasonic waves for 3 to 10 minutes under the power of 500 to 1000 watts.
In order to ensure that the anhydrous polyhydric alcohol and MDI react sufficiently to generate the polyurethane prepolymer, the adding amount of the diphenylmethane diisocyanate in the step S4 is 10-40 parts by weight; the reaction time in the step S4 is 1.5-3 h.
Similarly, in order to ensure the growth of the polyurethane molecular chain, the chain extender in step S5 of the present invention includes diethanolamine; the addition amount of the chain extender is 3-10 parts by weight; the reaction time in step S5 is 5 to 20 minutes.
Another object of the present invention is to provide a polyurethane adhesive prepared by the above method.
The polyurethane adhesive provided by the invention has excellent aging resistance and weather resistance, and the curing mode is room temperature moisture curing, so that the polyurethane adhesive is convenient to use.
Example 1
The embodiment provides a preparation method of a polyurethane adhesive, which comprises the following specific steps:
s1: adding 80 parts of anhydrous toluene into a three-neck flask, heating to 80 ℃, adding 3 parts of nano zinc oxide, adding 2 parts of gamma-aminopropyltriethoxysilane, mechanically stirring for 5 hours, then performing centrifugal separation, and performing vacuum drying at 50 ℃ for 24 hours to obtain silane modified nano zinc oxide particles;
s2: carrying out reduced pressure distillation on polytetrahydrofuran ether glycol for 2h at 120 ℃ and-0.1 MPa to obtain anhydrous polyalcohol;
s3: adding 0.33 part of silane modified nano zinc oxide particles, 0.6 part of AO-80 antioxidant and 60 parts of anhydrous polyalcohol into a three-neck flask, and treating for 5 minutes by ultrasonic waves at the power of 800 watts for full dispersion to obtain a dispersion liquid;
s4: building a polymerization device, introducing nitrogen into a bottle to discharge air, starting electric stirring, adding 18 parts of diphenylmethane diisocyanate (MDI) when a water bath kettle is heated to 70 ℃, slowly stirring, and reacting for 2 hours to obtain a polyurethane prepolymer;
s5: and cooling the polyurethane prepolymer to 60 ℃, adding 3 parts of diethanolamine, and reacting for 5min to obtain the polyurethane adhesive.
In this example, the amount of silane-modified nano zinc oxide added was 0.4% (mass%), and the prepared polyurethane adhesive was tested.
The tensile shear strength of the polyurethane adhesive was measured and the results are shown in FIG. 1.
The polyurethane adhesive prepared in this example was subjected to a 120 ℃ thermo-oxidative aging test, and the tensile shear strength of the polyurethane adhesive was measured for different thermo-oxidative aging times, the results of which are shown in fig. 2; as seen from FIG. 2, the tensile shear strength of the polyurethane adhesive decreased slowly with the increase of the thermo-oxidative aging time, thus demonstrating that the polyurethane adhesive prepared in this example has excellent thermo-oxidative aging resistance.
Referring to fig. 3, after scanning the prepared polyurethane adhesive by an electron microscope, the prepared polyurethane adhesive was subjected to an artificial aging test in the following manner: an Xeno Test Chamber of Xeno Model Xe-1 type of Q-Sun in the United states is used, and an indoor glass mode is adopted; circulation conditions are as follows: ultraviolet light with a wavelength of 420nm and an irradiance of 1.10W/m2At a temperature of 63 ℃ for 3.8h, and then at a temperature of 43 ℃ for 1h in the dark; after one cycle is finished, the next cycle is carried out again according to the conditions, and the artificial aging experiment is carried out on the prepared modified PU adhesive according to the accumulated time.
Fig. 4 and 5 are scanning electron microscope pictures of the polyurethane adhesive aged for 400 hours and 1000 hours respectively, and according to fig. 3 to 5, the surface appearances of the polyurethane adhesive aged for different aging times are observed, which shows that the polyurethane adhesive prepared by the embodiment has better photooxidation aging resistance.
Through the above tests, the tensile shear strength of the polyurethane adhesive prepared in this example gradually increases with the addition amount of the silane-modified nano zinc oxide particles, and the polyurethane adhesive prepared in this example has excellent thermal-oxidative aging resistance and photo-oxidative aging resistance.
Example 2
S1: adding 80 parts of anhydrous toluene into a three-neck flask, heating to 80 ℃, adding 3 parts of nano zinc oxide, adding 1 part of gamma-aminopropyltriethoxysilane, mechanically stirring for 5 hours, then performing centrifugal separation, and performing vacuum drying at 50 ℃ for 24 hours to obtain silane modified nano zinc oxide particles;
s2: carrying out reduced pressure distillation on polytetrahydrofuran ether glycol for 4h at 110 ℃ and-0.1 MPa to obtain anhydrous polyalcohol;
s3: adding 0.16 part of silane modified nano zinc oxide particles, 0.6 part of AO-80 antioxidant and 60 parts of anhydrous polyalcohol into a three-neck flask, and treating for 5 minutes by ultrasonic waves at the power of 800 watts for full dispersion to obtain a dispersion liquid;
s4: building a polymerization device, introducing nitrogen into a bottle to discharge air, starting electric stirring, adding 18 parts of diphenylmethane diisocyanate (MDI) when a water bath kettle is heated to 70 ℃, slowly stirring, and reacting for 2 hours to obtain a polyurethane prepolymer;
s5: and cooling the polyurethane prepolymer to 60 ℃, adding 3 parts of diethanolamine, and reacting for 5min to obtain the polyurethane adhesive.
In this example, the amount of silane-modified nano zinc oxide added was 0.2% (mass%), and the prepared polyurethane adhesive was tested.
The tensile shear strength of the polyurethane adhesive was measured and the results are shown in FIG. 1.
The thermal-oxidative-aging-resistant test and the photo-oxidative-aging-resistant test process of the prepared polyurethane adhesive are described in the first embodiment, and are not repeated herein.
Through the above tests, the tensile shear strength of the polyurethane adhesive prepared in this example gradually increases with the addition amount of the silane-modified nano zinc oxide particles, and the polyurethane adhesive prepared in this example has excellent thermal-oxidative aging resistance and photo-oxidative aging resistance.
Example 3
S1: adding 100 parts of anhydrous toluene into a three-neck flask, heating to 80 ℃, adding 8 parts of nano zinc oxide, adding 5 parts of gamma-aminopropyltriethoxysilane, mechanically stirring for 5 hours, then performing centrifugal separation, and performing vacuum drying at 50 ℃ for 24 hours to obtain silane modified nano zinc oxide particles;
s2: carrying out reduced pressure distillation on polycaprolactone diol at 150 ℃ and-0.1 MPa for 4h to obtain anhydrous polyol;
s3: adding 0.5 part of silane modified nano zinc oxide particles, 0.6 part of AO-80 antioxidant and 60 parts of anhydrous polyalcohol into a three-neck flask, and treating for 5 minutes by ultrasonic waves at the power of 800 watts for full dispersion to obtain a dispersion liquid;
s4: building a polymerization device, introducing nitrogen into a bottle to discharge air, starting electric stirring, adding 18 parts of diphenylmethane diisocyanate (MDI) when a water bath kettle is heated to 70 ℃, slowly stirring, and reacting for 2 hours to obtain a polyurethane prepolymer;
s5: and cooling the polyurethane prepolymer to 60 ℃, adding 3 parts of diethanolamine, and reacting for 5min to obtain the polyurethane adhesive.
In this example, the amount of silane-modified nano zinc oxide added was 0.6% (by mass), and the prepared polyurethane adhesive was tested.
The tensile shear strength of the polyurethane adhesive was measured and the results are shown in FIG. 1.
The thermal-oxidative-aging-resistant test and the photo-oxidative-aging-resistant test process of the prepared polyurethane adhesive are described in the first embodiment, and are not repeated herein.
Through the above tests, the tensile shear strength of the polyurethane adhesive prepared in this example gradually increases with the addition amount of the silane-modified nano zinc oxide particles, and the polyurethane adhesive prepared in this example has excellent thermal-oxidative aging resistance and photo-oxidative aging resistance.
Example 4
S1: adding 85 parts of anhydrous toluene into a three-neck flask, heating to 80 ℃, adding 6 parts of nano zinc oxide, adding 3 parts of gamma-aminopropyltriethoxysilane, mechanically stirring for 5 hours, then performing centrifugal separation, and performing vacuum drying at 50 ℃ for 24 hours to obtain silane modified nano zinc oxide particles;
s2: carrying out reduced pressure distillation on polytetrahydrofuran ether glycol for 3h at 130 ℃ and-0.1 MPa to obtain anhydrous polyalcohol;
s3: adding 0.66 part of silane modified nano zinc oxide particles, 0.6 part of AO-80 antioxidant and 60 parts of anhydrous polyalcohol into a three-neck flask, and treating for 5 minutes by ultrasonic waves at the power of 800 watts for full dispersion to obtain a dispersion liquid;
s4: building a polymerization device, introducing nitrogen into a bottle to discharge air, starting electric stirring, adding 18 parts of diphenylmethane diisocyanate (MDI) when a water bath kettle is heated to 70 ℃, slowly stirring, and reacting for 2 hours to obtain a polyurethane prepolymer;
s5: and cooling the polyurethane prepolymer to 60 ℃, adding 3 parts of diethanolamine, and reacting for 5min to obtain the polyurethane adhesive.
In this example, the amount of silane-modified nano zinc oxide added was 0.8% (mass%), and the prepared polyurethane adhesive was tested.
The tensile shear strength of the polyurethane adhesive was measured and the results are shown in FIG. 1.
The thermal-oxidative-aging-resistant test and the photo-oxidative-aging-resistant test process of the prepared polyurethane adhesive are described in the first embodiment, and are not repeated herein.
Through the above tests, the tensile shear strength of the polyurethane adhesive prepared in this example gradually increases with the addition amount of the silane-modified nano zinc oxide particles, and the polyurethane adhesive prepared in this example has excellent thermal-oxidative aging resistance and photo-oxidative aging resistance.
Example 5
S1: adding 95 parts of anhydrous toluene into a three-neck flask, heating to 80 ℃, adding 7 parts of nano zinc oxide, adding 4 parts of gamma-aminopropyltriethoxysilane, mechanically stirring for 5 hours, then performing centrifugal separation, and performing vacuum drying at 50 ℃ for 24 hours to obtain silane modified nano zinc oxide particles;
s2: carrying out reduced pressure distillation on polytetrahydrofuran ether glycol for 2h at 120 ℃ and-0.1 MPa to obtain anhydrous polyalcohol;
s3: adding 0.83 part of silane modified nano zinc oxide particles, 0.6 part of AO-80 antioxidant and 60 parts of anhydrous polyalcohol into a three-neck flask, and treating for 5 minutes by ultrasonic waves at the power of 800 watts for full dispersion to obtain a dispersion liquid;
s4: building a polymerization device, introducing nitrogen into a bottle to discharge air, starting electric stirring, adding 18 parts of diphenylmethane diisocyanate (MDI) when a water bath kettle is heated to 70 ℃, slowly stirring, and reacting for 2 hours to obtain a polyurethane prepolymer;
s5: and cooling the polyurethane prepolymer to 60 ℃, adding 3 parts of diethanolamine, and reacting for 5min to obtain the polyurethane adhesive.
In this example, the amount of silane-modified nano zinc oxide added was 1.0% (by mass), and the prepared polyurethane adhesive was tested.
The tensile shear strength of the polyurethane adhesive was measured and the results are shown in FIG. 1.
The thermal-oxidative-aging-resistant test and the photo-oxidative-aging-resistant test process of the prepared polyurethane adhesive are described in the first embodiment, and are not repeated herein.
Through the above tests, the tensile shear strength of the polyurethane adhesive prepared in this example gradually increases with the addition amount of the silane-modified nano zinc oxide particles, and the polyurethane adhesive prepared in this example has excellent thermal-oxidative aging resistance and photo-oxidative aging resistance.
Examples 6 to 8
In examples 6 to 8, the addition amounts of the silane-modified nano zinc oxide, the antioxidant, the anhydrous polyol, the MDI, and the chain extender in parts by weight are shown in table 1 below:
TABLE 1
| Nano zinc oxide | Antioxidant agent | Anhydrous polyols | MDI | Chain extender | |
| Example 6 | 0.2 |
2 portions of | 100 portions of | 40 portions of | 10 portions of |
| Example 7 | 2.5 parts of | 1 part of | 75 portions of | 25 portions of | 6.5 parts of |
| Example 8 | 5 portions of | 0.05 part | 50 portions of | 10 portions of | 3 portions of |
The specific procedure, reaction conditions and amounts of other materials added were the same as in example 1.
The polyurethane adhesives prepared in the embodiments 6 to 8 are respectively detected, and the specific detection process refers to relevant parts in the embodiment 1, which are not described herein again.
Through the above tests, the tensile shear strength of the polyurethane adhesive prepared in this example gradually increases with the addition amount of the silane-modified nano zinc oxide particles, and the polyurethane adhesive prepared in this example has excellent thermal-oxidative aging resistance and photo-oxidative aging resistance.
Comparative example 1
S1: carrying out reduced pressure distillation on polytetrahydrofuran ether glycol for 2h at 120 ℃ and-0.1 MPa to obtain anhydrous polyalcohol;
s2: adding 60 parts of anhydrous polyalcohol into a three-neck flask, and treating for 5 minutes by ultrasonic waves under the power of 800 watts for full dispersion to obtain a dispersion liquid;
s3: building a polymerization device, introducing nitrogen into a bottle to discharge air, starting electric stirring, adding 18 parts of diphenylmethane diisocyanate (MDI) when a water bath kettle is heated to 70 ℃, slowly stirring, and reacting for 2 hours to obtain a polyurethane prepolymer;
s5: and (3) cooling the polyurethane prepolymer to 60 ℃, adding 3 parts of diethanolamine, and reacting for 5min to obtain the unmodified polyurethane adhesive.
The preparation process provided by the comparative example does not add silane modified nano zinc oxide and antioxidant, and the unmodified polyurethane adhesive prepared by the comparative example is detected to compare the performance of the unmodified polyurethane adhesive with that of the polyurethane adhesive prepared in the above example.
The unmodified polyurethane adhesive prepared by the comparative example is subjected to a 120 ℃ thermal oxidation aging experiment, and the tensile shear strength of the polyurethane adhesive with different thermal oxidation aging time is detected, and the result is shown in figure 2; as seen from FIG. 2, with the increase of the thermal oxidation aging time, the tensile shear strength of the unmodified polyurethane adhesive and the modified polyurethane adhesive is reduced, but compared with the unmodified polyurethane adhesive, the tensile shear strength of the modified polyurethane adhesive is reduced obviously and slowly, so that the preparation method of the polyurethane adhesive provided by the invention is proved that the thermal oxidation aging resistance of the polyurethane adhesive is improved by adding the silane modified nano zinc oxide particles and the antioxidant as modifiers.
Referring to fig. 6, after scanning the prepared unmodified polyurethane adhesive by an electron microscope, the prepared polyurethane adhesive was subjected to an artificial aging test in the following manner: an Xeno Test Chamber of Xeno Model Xe-1 type of Q-Sun in the United states is used, and an indoor glass mode is adopted; circulation conditions are as follows: ultraviolet light with a wavelength of 420nm and an irradiance of 1.10W/m2At a temperature of 63 ℃ for 3.8h, and then at a temperature of 43 ℃ for 1h in the dark; after one cycle is finished, the next cycle is carried out again according to the conditions, and the artificial aging experiment is carried out on the prepared modified PU adhesive according to the accumulated time.
Fig. 7 and fig. 8 are scanning electron microscope pictures of unmodified polyurethane adhesives aged for 400 hours and 1000 hours respectively, and it can be seen from comparison of fig. 3 to fig. 5 with fig. 6 to fig. 8 that, under the same illumination condition, the surface cracks of the modified polyurethane adhesives are less than those of the unmodified polyurethane adhesives, thereby proving that the preparation method of the polyurethane adhesives provided by the invention improves the light-oxygen aging resistance of the polyurethane adhesives by adding silane-modified nano zinc oxide particles and an antioxidant as modifiers.
Although the present disclosure has been described above, the scope of the present disclosure is not limited thereto. Those skilled in the art can make various changes and modifications without departing from the spirit and scope of the present disclosure, and such changes and modifications will fall within the scope of the present invention.
Claims (10)
1. The preparation method of the polyurethane adhesive is characterized by comprising the following steps:
s1: modifying the nano zinc oxide by using a silane coupling agent to obtain silane modified nano zinc oxide particles;
s2: carrying out reduced pressure distillation on polyether polyol to obtain anhydrous polyol;
s3: mixing and dispersing the silane modified nano zinc oxide particles, the anhydrous polyhydric alcohol and the antioxidant to obtain a dispersion liquid;
s4: heating the dispersion to 60-80 ℃ under the nitrogen atmosphere and stirring conditions, adding diphenylmethane diisocyanate, and reacting to obtain a polyurethane prepolymer;
s5: and cooling the polyurethane prepolymer to 60-65 ℃, adding a chain extender, and reacting to obtain the polyurethane adhesive.
2. The method of preparing a polyurethane adhesive of claim 1, wherein the silane coupling agent comprises gamma-aminopropyltriethoxysilane.
3. The method of preparing the polyurethane adhesive according to claim 2, wherein the step S1 includes: weighing 80-100 parts by weight of anhydrous toluene, heating to 80 ℃, respectively adding 3-8 parts by weight of nano zinc oxide and 1-5 parts by weight of silane coupling agent, stirring for 5 hours, then carrying out centrifugal separation, and carrying out vacuum drying on the precipitate after centrifugal separation at 50 ℃ for 24 hours to obtain the silane modified nano zinc oxide particles.
4. The method of preparing polyurethane adhesive according to claim 1, wherein the polyether polyol in step S2 includes at least one of polytetrahydrofuran ether glycol, polycaprolactone glycol; the pressure of the reduced pressure distillation is-0.1 MPa, the temperature range is 110-150 ℃, and the time range of the reduced pressure distillation is 2-4 h.
5. The process for preparing polyurethane adhesive according to claim 1, wherein the antioxidant in step S3 comprises 3, 9-bis- {1, 1-dimethyl-2 [ b- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy ] ethyl } -2,4,8, 10-tetraoxaaspirin [5,5] undecane.
6. The preparation method of polyurethane adhesive as claimed in claim 5, wherein the silane-modified nano zinc oxide particles are added in the step S3 in an amount of 0.2 to 5 parts by weight, the anhydrous polyhydric alcohol is added in an amount of 50 to 100 parts by weight, and the antioxidant is added in an amount of 0.05 to 2 parts by weight.
7. The method for preparing polyurethane adhesive according to claim 5, wherein the mixing and dispersing process in step S3 includes: the mixture is treated by ultrasonic waves for 3 to 10 minutes under the power of 500 to 1000 watts.
8. The method for preparing polyurethane adhesive according to any one of claims 1 to 7, wherein the amount of the diphenylmethane diisocyanate added in step S4 is 10 to 40 parts by weight; the reaction time in the step S4 is 1.5-3 h.
9. The method of preparing a polyurethane adhesive according to claim 8, wherein the chain extender in step S5 includes diethanolamine; the addition amount of the chain extender is 3-10 parts by weight; the reaction time in step S5 is 5 to 20 minutes.
10. A polyurethane adhesive, characterized by being prepared by the method for preparing a polyurethane adhesive according to any one of claims 1 to 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911108546.8A CN110819289A (en) | 2019-11-13 | 2019-11-13 | Polyurethane adhesive and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911108546.8A CN110819289A (en) | 2019-11-13 | 2019-11-13 | Polyurethane adhesive and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110819289A true CN110819289A (en) | 2020-02-21 |
Family
ID=69554739
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911108546.8A Pending CN110819289A (en) | 2019-11-13 | 2019-11-13 | Polyurethane adhesive and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110819289A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001172602A (en) * | 1999-10-08 | 2001-06-26 | Takeda Chem Ind Ltd | Solventless two-pack type curable adhesive composition |
| CN101629061A (en) * | 2008-07-14 | 2010-01-20 | 上海新光化工有限公司 | Monocomponent moisture cure urethanes adhesive |
| JP2010100835A (en) * | 2008-09-26 | 2010-05-06 | Asahi Glass Co Ltd | Adherence substance and adhesive sheet |
| CN105153990A (en) * | 2015-09-02 | 2015-12-16 | 太仓顺如成建筑材料有限公司 | Preparation method of nano-modified polyurethane adhesive |
| CN108342181A (en) * | 2018-02-28 | 2018-07-31 | 佛山市三水日邦化工有限公司 | A kind of single-component water-based polyurethane adhesive of water resistant, high temperature resistant and preparation method thereof |
-
2019
- 2019-11-13 CN CN201911108546.8A patent/CN110819289A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001172602A (en) * | 1999-10-08 | 2001-06-26 | Takeda Chem Ind Ltd | Solventless two-pack type curable adhesive composition |
| CN101629061A (en) * | 2008-07-14 | 2010-01-20 | 上海新光化工有限公司 | Monocomponent moisture cure urethanes adhesive |
| JP2010100835A (en) * | 2008-09-26 | 2010-05-06 | Asahi Glass Co Ltd | Adherence substance and adhesive sheet |
| CN105153990A (en) * | 2015-09-02 | 2015-12-16 | 太仓顺如成建筑材料有限公司 | Preparation method of nano-modified polyurethane adhesive |
| CN108342181A (en) * | 2018-02-28 | 2018-07-31 | 佛山市三水日邦化工有限公司 | A kind of single-component water-based polyurethane adhesive of water resistant, high temperature resistant and preparation method thereof |
Non-Patent Citations (6)
| Title |
|---|
| 张虎极: "耐老化性能优异的单组分聚氨酯密封胶粘剂研制", 《研究报告及专论》 * |
| 朵英贤: "《纳米塑料技术》", 30 December 2006, 浙江科学技术出版社 * |
| 李广宇: "《胶接与密封新技术》", 30 January 2006, 国防工业出版社 * |
| 汪多仁: "《精细化工品实用生产技术手册》", 30 August 1999, 科学技术文献出版社 * |
| 王世博: "《氧化锌晶须增强尼龙材料的摩擦学行为研究》", 30 November 2008, 中国矿业大学出版社 * |
| 罗敏等: "改性纳米氧化锌对水性聚氨酯乳液性能的影响 ", 《电镀与涂饰》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111548763B (en) | High-strength high-weather-resistance two-component polyurethane structural adhesive and preparation method thereof | |
| CN109251711B (en) | Preparation method of silane modified polyether sealant | |
| CN106833481B (en) | Environment-friendly organic silicon modified polyether sealant and preparation method thereof | |
| CN107641494A (en) | A kind of coupling agent modified fluid sealant of α isocyanato silanes | |
| CN114940885B (en) | Heat-conducting bi-component polyurethane adhesive and preparation method and application thereof | |
| CN108546543A (en) | Organosilicon sealant and its preparation method and application | |
| CN109762511B (en) | Single-component dealcoholized room temperature vulcanized silicone sealant and preparation method thereof | |
| CN114106769B (en) | Transparent silicone sealant and preparation method thereof | |
| CN109135650B (en) | Single-component silane modified polyether sealant and preparation method thereof | |
| CN114621724B (en) | Double-component organic silicon sealant and preparation method thereof | |
| CN111100590A (en) | Silane modified polyether sealant and preparation method thereof | |
| CN113999531A (en) | Mold glue and preparation method thereof | |
| CN113773790B (en) | High-thixotropy fast-curing silicone sealant and preparation method thereof | |
| CN106883591B (en) | Method for utilizing polyurethane waste material and elastomer | |
| CN116178704A (en) | Preparation method of novel isocyanate silane modified polyether polymer | |
| CN113789148A (en) | Organic silicon foaming pouring sealant and preparation method thereof | |
| CN109666448A (en) | A kind of photovoltaic module dealcoholized type sealant and preparation method thereof | |
| CN110819289A (en) | Polyurethane adhesive and preparation method thereof | |
| CN116606415A (en) | Comb-type silane end-capped polyurethane polymer resin, and preparation method and application thereof | |
| CN111019354A (en) | Silica gel with low permanent deformation at break, and preparation method and use method thereof | |
| CN111394035A (en) | High-strength transparent nail-free glue and preparation method thereof | |
| CN115975586A (en) | Double-component polyurethane structural adhesive and application thereof | |
| CN108003604B (en) | Photothermal effect type self-repairing cable insulating material and preparation method thereof | |
| CN115612149A (en) | Conductive silicone rubber and preparation method thereof | |
| CN115558452A (en) | Bi-component structural adhesive for bonding power battery and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200221 |
|
| RJ01 | Rejection of invention patent application after publication |