CN115975576A - High-temperature-resistant polyurethane adhesive and preparation method thereof - Google Patents
High-temperature-resistant polyurethane adhesive and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the field of C09J175/04, in particular to a high-temperature-resistant polyurethane adhesive and a preparation method thereof, wherein the high-temperature-resistant polyurethane adhesive comprises a main agent and a curing agent, and the preparation raw materials of the main agent at least comprise the following components in parts by weight: 45-60 parts of polymer polyol, 2-5 parts of aromatic diol chain extender, 1-6 parts of oxazolidine compounds, 25-40 parts of filler and 8-15 parts of auxiliary agent, wherein the provided high-temperature-resistant polyurethane adhesive has excellent high-temperature resistance by adopting specific polymer polyol and matching with the aromatic diol chain extender under the condition of the existence of other raw materials, so that the problems of foaming, hollowing and degumming caused by high water content of a base material are effectively solved while the adhesive property and the adhesive strength of the polyurethane adhesive are ensured.
Description
Technical Field
The invention relates to the field of C09J175/04, in particular to a high-temperature-resistant polyurethane adhesive and a preparation method thereof.
Background
The sandwich materials in fire doors are typically cement mortar and honeycomb panels. The honeycomb plate comprises a paper honeycomb plate and an aluminum honeycomb plate. And after the fireproof door is made, baking finish in a baking room. When baking varnish, the baking varnish needs to be heated to 220 ℃ for 20-30min. During the baking finish process, the bonding material cannot be degummed and cannot be embrittled. The adhesive needs to be bonded with a galvanized plate and a sandwich material, and is more difficult to be bonded with the galvanized plate particularly when the sandwich material of the fireproof door is a paper honeycomb plate. The paper honeycomb board has moisture and can be brittle after being baked with varnish. The water content of the paper honeycomb board is generally 8-12%. When the water content of the base material is higher, the adhesive can be foamed to cause hollowing and separation, so that the high-temperature-resistant polyurethane adhesive is provided, the problems existing when the existing polyurethane adhesive is applied to the adhesion of the sandwich material of the fireproof door core plate are solved, and the polyurethane adhesive is an important direction for the research of the field of polyurethane adhesives.
Chinese patent CN 109628051B discloses a high temperature resistant three-component polyurethane adhesive and a preparation method thereof, wherein the high temperature resistant polyurethane adhesive is prepared by adopting high temperature resistant aliphatic polyester polyol and aliphatic diisocyanate under the condition of a high temperature resistant auxiliary agent, but the high temperature resistant polyurethane adhesive can not resist the high temperature of 220 ℃ and can not fall off and become crisp when being practically applied to baking finish of a fireproof door. Chinese patent CN105085858B discloses a preparation method of a biological modified high temperature resistant polyurethane glue, wherein wheat straw particles and cellulase after treatment are introduced into a polyurethane system, so that the provided polyurethane adhesive has good adhesion performance at 200-250 ℃, but the adhesive system cannot effectively solve the problems of foaming, hollowing and degumming caused by high water content of a base material.
Therefore, the high-temperature-resistant polyurethane adhesive provided by the invention has excellent high-temperature resistance by adopting the specific polymer polyol and matching with the aromatic diol chain extender under the condition of the existence of other raw materials, ensures the bonding property and bonding strength of the polyurethane adhesive, and effectively solves the problems of foaming, hollowing and degumming caused by high water content of the base material.
Disclosure of Invention
The invention provides a high-temperature-resistant polyurethane adhesive, which comprises a main agent and a curing agent, wherein the main agent at least comprises the following preparation raw materials in parts by weight: 45-60 parts of polymer polyol, 2-5 parts of aromatic diol chain extender, 1-6 parts of oxazolidine compounds, 25-40 parts of filler and 8-15 parts of auxiliary agent.
As a preferred technical solution, the polymer polyol is selected from at least one of polyester polyol, polyether polyol, vegetable oil polyol, polyolefin polyol; preferably, the polymer polyol is a mixture of polyester polyol and vegetable oil polyol, and the mass ratio of the polyester polyol to the vegetable oil polyol is (6-10): (1-3);
as a preferable technical scheme, the vegetable oil polyalcohol is trifunctional castor oil modified polyalcohol with a hydroxyl value of 160-188 mgKOH/g;
the tri-functionality castor oil modified polyol is URIC F-135, and is purchased from Beijing Senchangtai and science and technology Limited liability company.
Based on the system, the mass ratio is (6-10): (1-3) the polyester polyol and the vegetable oil polyol, particularly when the vegetable oil polyol is trifunctional castor oil modified polyol with a hydroxyl value of 160-188mgKOH/g, active hydrogen in functional groups of the polyester polyol and the trifunctional castor oil modified polyol reacts with isocyanate (-NCO) to generate polyurethane adhesive with a large number of repeated carbamate (-NHCOO-) segments, and the polyurethane adhesive can generate stronger chemical bond action and hydrogen bond action with active hydrogen in a honeycomb panel material structure, so that the bonding between interfaces is firmer and more durable; under the mass ratio, the trifunctional castor oil modified polyol is compounded and introduced, a microporous structure can be formed in the curing reaction process, so that the volume of the polyurethane adhesive is expanded, the bonding area is increased, the cost is reduced, and the interface bonding strength is improved.
As a preferred technical scheme, the polyester polyol is phthalic anhydride polyester polyol; preferably, the phthalic anhydride polyester polyol is selected from one or a combination of more of diethylene glycol based phthalic anhydride polyester polyol, neopentyl glycol based phthalic anhydride polyester polyol, 1,6-hexanediol based phthalic anhydride polyester polyol, modified diethylene glycol based phthalic anhydride polyester polyol and diethylene glycol phthalic anhydride polyester polyol, and preferably, the viscosity (25 ℃) of the phthalic anhydride polyester polyol is 1500-4300mPa & s; preferably, the viscosity (25 ℃) of the phthalic anhydride polyester polyol is 2300 to 4300mPa & s;
the phthalic anhydride polyester polyol is modified diethylene glycol based phthalic anhydride polyester polyol with the type of
BC-180, available from Su Telin (Nanjing) New Material science and technology, inc.;
from the exploration and research of the thermal degradation mechanism of the polyurethane material, it can be found that the traditional polyurethane material has poor high-temperature resistance, the mechanical property of the traditional polyurethane material is gradually reduced when the traditional polyurethane material is used for a long time at about 100 ℃, when the temperature is continuously increased, the hard segment, the side group and the end group in a high molecular chain start to be pyrolyzed, then the soft segment starts to be pyrolyzed, and finally the high molecular chain segment is completely depolymerized into micromolecules and gas; the invention introduces a rigid structure into a polyurethane adhesive structure by adopting phthalic anhydride polyester polyol, so that the rigidity of a high molecular chain is enhanced, and the high temperature resistance and the mechanical property of the polyurethane adhesive are obviously improved.
As a preferable technical scheme, the oxazolidine compound is one or a combination of more of E1, E2, E3 and E4; the structures of E1, E2, E3 and E4 are as follows in sequence:
preferably, the oxazolidine compound is E3, and the structure is
As a preferred technical scheme, the filler at least comprises organosilicon microsphere powder, silica micropowder and a 3A molecular sieve; preferably, the mass ratio of the organic silicon microsphere powder to the silicon micropowder to the 3A molecular sieve is (0.8-3): (18-25): (5-10).
Preferably, the average particle size of the organosilicon microsphere powder is 0.8-5 μm; preferably, the particle size of the silicon micro powder is 2-4 μm; preferably, the particle size of the 3A molecular sieve is 2-4 μm;
the type of the organic silicon microsphere powder is YGF-102, and the organic silicon microsphere powder is purchased from Jiujiang Youmei New Material science and technology Limited company; the silicon micro powder is purchased from New Dilute metallurgy chemical Co., ltd of Guangzhou city; the 3A molecular sieve was purchased from Jiangxi Xin ceramic science and technology Co.
Based on the system, the oxazolidine compound containing a rigid heterocyclic structure is introduced, particularly when the oxazolidine compound is E3, the heat stability of the polyurethane adhesive is further improved by cooperating with the organic silicon microsphere powder in the system, the problems of adhesive falling, embrittlement and failure caused by overhigh baking temperature in the practical application process are avoided, meanwhile, the reaction of an isocyanate curing agent and water is inhibited under the combined action of the silicon micropowder in the system and a 3A molecular sieve, the problems of foaming, hollowing and degumming of the polyurethane adhesive caused by higher water content of a base material are solved, and the provided polyurethane adhesive meets the bonding requirement of a honeycomb plate in a fireproof door core plate.
As a preferred embodiment, the aromatic diol chain extender is hydroquinone bis hydroxyethyl ether and/or resorcinol bis hydroxyethyl ether. Preferably, the aromatic glycol chain extender is a mixture of hydroquinone dihydroxyethyl ether and resorcinol dihydroxyethyl ether, and the mass ratio of the hydroquinone dihydroxyethyl ether to the resorcinol dihydroxyethyl ether is (2-4): (4-6); the thermal degradation analysis of polyurethane also discovers that the energy required by the fracture of the side chain and the chain segment of the polyurethane adhesive prepared by adopting the aliphatic diol is far lower than the energy required by the fracture of the chain segment bond of a polyurethane macromolecule, so that the initial decomposition stage of the thermal decomposition of the polyurethane structure starts with the degradation of the side chain and the chain segment. However, the inventors found in the actual production process that since the melting point of hydroquinone dihydroxyethyl ether is high and heating to 110 ℃ or higher is required, the workability is not good, and by introducing resorcinol dihydroxyethyl ether, particularly, the mass ratio of hydroquinone dihydroxyethyl ether to resorcinol dihydroxyethyl ether is controlled to (2-4): and (4-6), the processing operation temperature is effectively reduced, and the operation effective time (working life) is prolonged, so that the processing production of the polyurethane adhesive is facilitated.
The hydroquinone bis hydroxyethyl ether and the resorcinol bis hydroxyethyl ether are both purchased from yari chemical ltd, hong kong.
As a preferred technical scheme, the functional auxiliary agent at least comprises a cross-linking agent, an adhesion promoter, a plasticizer and a dispersing agent; preferably, the mass ratio of the cross-linking agent to the adhesion promoter to the plasticizer to the dispersing agent is (1-2): (2-4): (3-6): (1-3).
Preferably, the cross-linking agent is 2,4-diamino-3,5-dimethylthiochlorobenzene;
preferably, the adhesion promoter is benzyl methoxy dimethylsilane;
preferably, the plasticizer is triglyme;
preferably, the dispersant is Coadis BR85, purchased from Kaiyn chemical Co., ltd.
According to the weight portion, stirring and mixing polymer polyol, aromatic diol chain extender, oxazolidine compound, filler and auxiliary agent at 80-90 ℃ for 15-30min, and then carrying out vacuum dehydration to obtain a main agent; the mass ratio of the main agent to the curing agent is (80-100): (15-30), and uniformly mixing the main agent and the curing agent to obtain the adhesive.
As a preferred technical scheme, the curing agent is an isocyanate curing agent; preferably, the isocyanate curing agent is diphenylmethane diisocyanate or polymethylene polyphenyl polyisocyanate.
Advantageous effects
1. The invention provides a high-temperature-resistant polyurethane adhesive, which has excellent high-temperature-resistant performance under the condition that other raw materials exist by adopting specific polymer polyol and matching with an aromatic diol chain extender, ensures the adhesive property and adhesive strength of the polyurethane adhesive, and effectively solves the problems of foaming, hollowing and degumming caused by higher water content of a base material.
2. Based on the system, the mass ratio is (6-10): (1-3), particularly when the vegetable oil polyol is trifunctional castor oil modified polyol with a hydroxyl value of 160-188mgKOH/g, the prepared polyurethane adhesive can generate stronger chemical bond action and hydrogen bond action with active hydrogen in a honeycomb board material structure, so that the bonding between interfaces is firmer and more durable.
3. According to the invention, the phthalic anhydride polyester polyol is adopted, and a rigid structure is introduced into the polyurethane adhesive structure, so that the rigidity of a high molecular chain is enhanced, and the high-temperature resistance and the mechanical property of the polyurethane adhesive are obviously improved.
4. According to the invention, the oxazolidine compound containing a rigid heterocyclic structure is introduced, and particularly when the oxazolidine compound is E3, the organic silicon microsphere powder in the system is cooperated, so that the thermal stability of the polyurethane adhesive is further improved, the problems of falling, embrittlement and failure of the adhesive caused by overhigh baking finish temperature in the actual application process are avoided, meanwhile, the reaction of an isocyanate curing agent and water is inhibited under the combined action of the silicon micropowder and a 3A molecular sieve in the system, and the problems of foaming, hollowing and degumming of the polyurethane adhesive caused by higher water content of a base material are solved.
5. Based on the system, the aromatic diol chain extender, especially the hydroquinone dihydroxyethyl ether with a symmetrical structure, is adopted, so that the aromatic diol chain extender has good compatibility with diphenylmethane diisocyanate, the curing effect is ensured, a rigid structural unit is introduced into a molecular chain of the polyurethane adhesive, and the high-temperature resistance of the polyurethane adhesive is improved.
Detailed Description
Example 1
The embodiment 1 of the invention provides a high-temperature-resistant polyurethane adhesive, which comprises a main agent and a curing agent, wherein the mass ratio of the main agent to the curing agent is 100:20; the preparation raw materials of the main agent comprise the following components in parts by weight: 55 parts of polymer polyol, 4 parts of aromatic diol chain extender, 3 parts of oxazolidine compounds, 30 parts of filler and 12 parts of auxiliary agent.
The polymer polyol is a mixture of polyester polyol and vegetable oil polyol, and the mass ratio of the polyester polyol to the vegetable oil polyol is 8:2;
the vegetable oil polyol is trifunctional castor oil modified polyol with a hydroxyl value of 160 mgKOH/g;
the trifunctional castor oil-modified polyol is of the type URIC F-135 and is purchased from Beijing Sengtai and science and technology Limited liability company.
The polyester polyol is phthalic anhydride polyester polyol; the phthalic anhydride polyester polyol is modified diethylene glycol based phthalic anhydride polyester polyol with the type of
BC-180, available from Su Telin (Nanjing) New Material science and technology, inc.;
the oxazolidine compound is E3 and has the structure
The filler comprises organic silicon microsphere powder, silicon micropowder and a 3A molecular sieve; the mass ratio of the organic silicon microsphere powder to the silicon micropowder to the 3A molecular sieve is 2:20:8.
the average grain diameter of the organosilicon microsphere powder is 2 mu m; the average grain diameter of the silicon micro powder is 2-4 mu m; the average particle size of the 3A molecular sieve is 3 mu m;
the type of the organic silicon microsphere powder is YGF-102, and the organic silicon microsphere powder is purchased from Jiujiang Youmei New Material science and technology Limited company; the silicon micro powder is purchased from New Dilute metallurgy chemical Co., ltd of Guangzhou city; the 3A molecular sieves were purchased from Jiangxin Xin ceramic science and technology Co.
The aromatic diol chain extender is a mixture of hydroquinone dihydroxyethyl ether and resorcinol dihydroxyethyl ether, and the mass ratio of the hydroquinone dihydroxyethyl ether to the resorcinol dihydroxyethyl ether is 3:5.
the hydroquinone bis hydroxyethyl ether and the resorcinol bis hydroxyethyl ether are both purchased from yari chemical ltd, hong kong.
The functional auxiliary agent comprises a cross-linking agent, an adhesion promoter, a plasticizer and a dispersing agent; the mass ratio of the cross-linking agent to the adhesion promoter to the plasticizer to the dispersing agent is 1.5:3.5:5:2.
the cross-linking agent is 2,4-diamino-3,5-dimethylsulfochlorobenzene;
the adhesion promoter is benzyl methoxy dimethyl silane;
the plasticizer is triglyme;
the dispersant is Coadis BR85, purchased from Kyowa Kay chemical Co., ltd.
In another aspect, embodiment 1 of the present invention provides a method for preparing a high temperature resistant polyurethane adhesive, wherein polymer polyol, an aromatic diol chain extender, oxazolidine compounds, a filler, and an auxiliary agent are stirred and mixed at 90 ℃ for 20min, and then subjected to vacuum dehydration to obtain a main agent; the mass ratio of the main agent to the curing agent is (80-100): (15-30), and uniformly mixing the main agent and the curing agent to obtain the curing agent.
The curing agent is isocyanate curing agent; the isocyanate curing agent is diphenylmethane diisocyanate.
Example 2
The embodiment 2 of the invention provides a high-temperature-resistant polyurethane adhesive on the one hand, which comprises a main agent and a curing agent, wherein the mass ratio of the main agent to the curing agent is 100:20; the preparation raw materials of the main agent comprise the following components in parts by weight: 60 parts of polymer polyol, 5 parts of aromatic diol chain extender, 5 parts of oxazolidine compound, 35 parts of filler and 15 parts of auxiliary agent.
The polymer polyol is a mixture of polyester polyol and vegetable oil polyol, and the mass ratio of the polyester polyol to the vegetable oil polyol is 10:3;
the vegetable oil polyol is trifunctional castor oil modified polyol with a hydroxyl value of 160 mgKOH/g;
the trifunctional castor oil-modified polyol is of the type URIC F-135 and is purchased from Beijing Sengtai and science and technology Limited liability company.
The polyester polyol is phthalic anhydride polyester polyol; the phthalic anhydride polyester polyol is modified diethylene glycol based phthalic anhydride polyester polyol with the type of
BC-180, available from Su Telin (Nanjing) New Material science and technology, inc.;
the oxazolidine compound is E3 and has the structure
The filler comprises organic silicon microsphere powder, silicon micropowder and a 3A molecular sieve; the mass ratio of the organic silicon microsphere powder to the silicon micropowder to the 3A molecular sieve is 3:22:10.
the average grain diameter of the organosilicon microsphere powder is 2 μm; the average grain diameter of the silicon micro powder is 2-4 μm; the average particle size of the 3A molecular sieve is 3 mu m;
the type of the organic silicon microsphere powder is YGF-102, and the organic silicon microsphere powder is purchased from Jiujiang Youmei New Material science and technology Limited company; the silicon micro powder is purchased from New Dilute metallurgy chemical Co., ltd, guangzhou city; the 3A molecular sieves were purchased from Jiangxin Xin ceramic science and technology Co.
The aromatic diol chain extender is a mixture of hydroquinone dihydroxyethyl ether and resorcinol dihydroxyethyl ether, and the mass ratio of the hydroquinone dihydroxyethyl ether to the resorcinol dihydroxyethyl ether is 4:6.
the hydroquinone bis hydroxyethyl ether and the resorcinol bis hydroxyethyl ether are both purchased from yari chemical ltd, hong kong.
The functional auxiliary agent comprises a cross-linking agent, an adhesion promoter, a plasticizer and a dispersing agent; the mass ratio of the cross-linking agent to the adhesion promoter to the plasticizer to the dispersing agent is 2:4:6:3.
the cross-linking agent is 2,4-diamino-3,5-dimethylsulfochlorobenzene;
the adhesion promoter is benzyl methoxy dimethylsilane;
the plasticizer is triglyme;
the dispersant is Coadis BR85, purchased from Kyowa Kay chemical Co., ltd.
In another aspect, embodiment 2 of the present invention provides a method for preparing a high temperature resistant polyurethane adhesive, which comprises mixing polymer polyol, aromatic diol chain extender, oxazolidine compound, filler and auxiliary agent in parts by weight at 90 ℃ for 20min, and then performing vacuum dehydration.
The use method of the high-temperature-resistant polyurethane adhesive comprises the following steps: according to the mass ratio of the main agent to the curing agent of 100: and 20, uniformly mixing the main agent and the curing agent to obtain the adhesive. The curing agent is isocyanate curing agent; the isocyanate curing agent is diphenylmethane diisocyanate.
Example 3
The embodiment 3 of the invention provides a high-temperature-resistant polyurethane adhesive, which comprises a main agent and a curing agent, wherein the mass ratio of the main agent to the curing agent is 100:20; the preparation raw materials of the main agent comprise the following components in parts by weight: 50 parts of polymer polyol, 3 parts of aromatic diol chain extender, 2 parts of oxazolidine compound, 25 parts of filler and 10 parts of assistant.
The polymer polyol is a mixture of polyester polyol and vegetable oil polyol, and the mass ratio of the polyester polyol to the vegetable oil polyol is 6:1;
the vegetable oil polyol is trifunctional castor oil modified polyol with a hydroxyl value of 160 mgKOH/g;
the trifunctional castor oil-modified polyol is of the type URIC F-135 and is purchased from Beijing Sengtai and science and technology Limited liability company.
The polyester polyol is phthalic anhydride polyester polyol; the phthalic anhydride polyester polyol is modified diethylene glycol based phthalic anhydride polyester polyol with the type of
BC-180, available from Su Telin (Nanjing) New Material science and technology, inc.;
the oxazolidine compound is E3 and has the structure
The filler comprises organic silicon microsphere powder, silicon micropowder and a 3A molecular sieve; the mass ratio of the organic silicon microsphere powder to the silicon micropowder to the 3A molecular sieve is 2:15:8.
the average grain diameter of the organosilicon microsphere powder is 2 mu m; the average grain diameter of the silicon micro powder is 2-4 mu m; the average particle size of the 3A molecular sieve is 3 mu m;
the type of the organic silicon microsphere powder is YGF-102, and the organic silicon microsphere powder is purchased from Jiujiang Youmei New Material science and technology Limited company; the silicon micro powder is purchased from New Dilute metallurgy chemical Co., ltd, guangzhou city; the 3A molecular sieve was purchased from Jiangxi Xin ceramic science and technology Co.
The aromatic diol chain extender is a mixture of hydroquinone bis-hydroxyethyl ether and resorcinol bis-hydroxyethyl ether, and the mass ratio of the hydroquinone bis-hydroxyethyl ether to the resorcinol bis-hydroxyethyl ether is 2:4.
the hydroquinone bis hydroxyethyl ether and the resorcinol bis hydroxyethyl ether are both purchased from yari chemical ltd, hong kong.
The functional auxiliary agent comprises a cross-linking agent, an adhesion promoter, a plasticizer and a dispersing agent; the mass ratio of the cross-linking agent to the adhesion promoter to the plasticizer to the dispersing agent is 1:3:5:1.
the cross-linking agent is 2,4-diamino-3,5-dimethylthio-chlorobenzene;
the adhesion promoter is benzyl methoxy dimethyl silane;
the plasticizer is triglyme;
the dispersant is Coadis BR85, purchased from Kyowa Kay chemical Co., ltd.
In another aspect, embodiment 3 of the present invention provides a method for preparing a high temperature resistant polyurethane adhesive, wherein polymer polyol, an aromatic diol chain extender, oxazolidine compounds, a filler, and an auxiliary agent are stirred and mixed at 90 ℃ for 20min, and then vacuum dehydration is performed to obtain a main agent; the mass ratio of the main agent to the curing agent is (80-100): (15-30), and uniformly mixing the main agent and the curing agent to obtain the curing agent.
The curing agent is isocyanate curing agent; the isocyanate curing agent is diphenylmethane diisocyanate.
Comparative example 1
Comparative example 1 of the present invention provides a high temperature resistant polyurethane adhesive, which is the same as example 1 except that the mass ratio of the polyester polyol to the vegetable oil polyol is 6:4.
comparative example 2
The invention provides a high-temperature resistant polyurethane adhesive in a comparative example 2, which is the same as the embodiment 1 except that the oxazolidine compound is E2 and the structure is
Comparative example 3
Comparative example 3 of the present invention provides a high temperature resistant polyurethane adhesive, the specific embodiment of which is the same as example 1, except that the aromatic diol chain extender in the raw material for preparing the high temperature resistant polyurethane adhesive is replaced by 1,4-butanediol.
Comparative example 4
Comparative example 4 of the present invention provides a high temperature resistant polyurethane adhesive, which is the same as example 1 except that the polyester polyol is polybutylene adipate.
Comparative example 5
Comparative example 5 of the present invention provides a high temperature resistant polyurethane adhesive, which is the same as example 1 except that the filler is silica micropowder.
Performance test method
The aluminum alloy is used as a bonding test piece, the surface of the aluminum alloy is polished by 0# abrasive paper, surface grease is removed by ultrasonic cleaning for 15min with acetone, the surface is treated by an FPL oxidation method, then the aluminum alloy is washed by deionized water and is placed in a 60 ℃ blast drying oven for drying for later use.
1. High temperature resistance
The high-temperature resistant polyurethane adhesives obtained in the examples and the comparative examples are coated on the surface of the aluminum alloy test piece after the treatment, the temperature is controlled to be 225 ℃, the aluminum alloy test piece is taken out and dried to room temperature after being baked for 30min, if the embrittlement and the falling phenomena of the adhesive layer do not occur, the adhesive layer is marked as qualified, and if the embrittlement and the falling phenomena occur, the adhesive layer is marked as unqualified, and the results are shown in table 1.
2. Tensile shear Strength test
The high temperature resistant polyurethane adhesives obtained in examples and comparative examples were tested for tensile shear strength by reference to the method of GB/T7124-2008, wherein tensile shear strength of 6-7MPa (including 6 MPa) was designated as "excellent", tensile shear strength of 5-6MPa (including 6 MPa) was designated as "good", and tensile shear strength < 5MPa was designated as "poor", and the results are shown in Table 1.
3. Adhesion Performance test
According to the national standard GB/T5210-1985 coating adhesion determination method-pull method, the high-temperature resistant polyurethane adhesive prepared in the examples and the comparative examples is coated on the surface of the aluminum alloy test piece after treatment, and after curing at 60 ℃, the adhesion of the adhesive coating is determined, and the result is shown in Table 1.
4.180 degree peel strength test
Referring to the method for measuring 180-degree peel strength of adhesive (metal-to-metal) in national standard GB/T2790-1985, the high-temperature resistant polyurethane adhesive prepared in the examples and the comparative examples is coated on the surface of the aluminum alloy test piece after being treated, and the 180-degree peel strength of the adhesive coating is measured after the high-temperature resistant polyurethane adhesive is cured at 60 ℃, and the results are shown in Table 1.
Claims (10)
1. The high-temperature-resistant polyurethane adhesive is characterized by comprising a main agent and a curing agent, wherein the main agent at least comprises the following preparation raw materials in parts by weight: 45-60 parts of polymer polyol, 2-5 parts of aromatic diol chain extender, 1-6 parts of oxazolidine compounds, 25-40 parts of filler and 8-15 parts of assistant.
2. The high temperature resistant polyurethane adhesive of claim 1, wherein the polymer polyol is at least one selected from polyester polyol, polyether polyol, vegetable oil polyol, and polyolefin polyol.
3. The high-temperature-resistant polyurethane adhesive as claimed in claim 2, wherein the polymer polyol is a mixture of polyester polyol and vegetable oil polyol, and the mass ratio of the polyester polyol to the vegetable oil polyol is (6-10): (1-3).
4. The high-temperature-resistant polyurethane adhesive as claimed in claim 3, wherein the vegetable oil polyol is a trifunctional castor oil-modified polyol having a hydroxyl value of 160-188 mgKOH/g.
5. The high-temperature-resistant polyurethane adhesive according to claim 3, wherein the polyester polyol is a phthalic anhydride polyester polyol, and the phthalic anhydride polyester polyol is one or a combination of more selected from the group consisting of diethylene glycol phthalic anhydride polyester polyol, neopentyl glycol phthalic anhydride polyester polyol, 1,6-hexanediol phthalic anhydride polyester polyol, modified diethylene glycol phthalic anhydride polyester polyol, and diethylene glycol phthalic anhydride polyester polyol.
6. The high-temperature-resistant polyurethane adhesive as claimed in claim 1, wherein the filler at least comprises silicone microsphere powder, silica micropowder and 3A molecular sieve.
7. The high temperature resistant polyurethane adhesive of claim 1, wherein the aromatic diol chain extender is hydroquinone bis hydroxyethyl ether and/or resorcinol bis hydroxyethyl ether.
8. The high-temperature-resistant polyurethane adhesive as claimed in claim 1, wherein the functional additives include at least a crosslinking agent, an adhesion promoter, a plasticizer, and a dispersant.
9. The high-temperature-resistant polyurethane adhesive as claimed in claim 1, wherein the curing agent is an isocyanate-based curing agent.
10. A method for preparing a high temperature resistant polyurethane adhesive according to any one of claims 1 to 9, wherein the polymer polyol, the aromatic diol chain extender, the oxazolidine compound, the filler and the auxiliary agent are stirred and mixed at 80 to 90 ℃ for 15 to 30min in parts by weight, and then the main agent is obtained by vacuum dehydration; the mass ratio of the main agent to the curing agent is (80-100): (15-30), and uniformly mixing the main agent and the curing agent to obtain the curing agent.
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| CN116987474A (en) * | 2023-08-08 | 2023-11-03 | 韦尔通科技股份有限公司 | Bio-based aging-resistant polyurethane adhesive |
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| CN116987474A (en) * | 2023-08-08 | 2023-11-03 | 韦尔通科技股份有限公司 | Bio-based aging-resistant polyurethane adhesive |
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