CN116813917B - Curing agent for ultralow-temperature epoxy sealant and sealant prepared from curing agent - Google Patents
Curing agent for ultralow-temperature epoxy sealant and sealant prepared from curing agent Download PDFInfo
- Publication number
- CN116813917B CN116813917B CN202211348293.3A CN202211348293A CN116813917B CN 116813917 B CN116813917 B CN 116813917B CN 202211348293 A CN202211348293 A CN 202211348293A CN 116813917 B CN116813917 B CN 116813917B
- Authority
- CN
- China
- Prior art keywords
- curing agent
- epoxy resin
- parts
- temperature
- sealant
- 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.)
- Active
Links
- 239000000565 sealant Substances 0.000 title claims abstract description 47
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 43
- 239000004593 Epoxy Substances 0.000 title claims abstract description 16
- 239000003822 epoxy resin Substances 0.000 claims abstract description 37
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 37
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 28
- 229920000570 polyether Polymers 0.000 claims abstract description 28
- 229920002121 Hydroxyl-terminated polybutadiene Polymers 0.000 claims abstract description 17
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 13
- 239000010703 silicon Substances 0.000 claims abstract description 13
- 239000007822 coupling agent Substances 0.000 claims abstract description 7
- 239000002608 ionic liquid Substances 0.000 claims description 17
- 238000002360 preparation method Methods 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- 239000004842 bisphenol F epoxy resin Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 150000003376 silicon Chemical class 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 230000009471 action Effects 0.000 claims description 4
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 150000004985 diamines Chemical class 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 3
- 230000002431 foraging effect Effects 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 239000004848 polyfunctional curative Substances 0.000 claims 2
- 238000007142 ring opening reaction Methods 0.000 claims 1
- 230000009477 glass transition Effects 0.000 abstract description 8
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 abstract description 6
- 150000001768 cations Chemical class 0.000 abstract description 4
- 229920000642 polymer Polymers 0.000 abstract description 4
- 150000001450 anions Chemical class 0.000 abstract description 2
- 230000001737 promoting effect Effects 0.000 abstract description 2
- 125000004185 ester group Chemical group 0.000 abstract 1
- 230000001070 adhesive effect Effects 0.000 description 20
- 239000000853 adhesive Substances 0.000 description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 239000004677 Nylon Substances 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 description 2
- 230000007123 defense Effects 0.000 description 2
- 229920006332 epoxy adhesive Polymers 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 230000008595 infiltration Effects 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 150000008040 ionic compounds Chemical class 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920002755 poly(epichlorohydrin) Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000010125 resin casting Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- 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
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
-
- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/504—Amines containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen
-
- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/5046—Amines heterocyclic
- C08G59/5053—Amines heterocyclic containing only nitrogen as a heteroatom
- C08G59/5073—Amines heterocyclic containing only nitrogen as a heteroatom having two nitrogen atoms in the ring
-
- 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
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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)
- Epoxy Resins (AREA)
- Sealing Material Composition (AREA)
Abstract
The invention belongs to the field of sealants, and particularly relates to a curing agent for ultralow-temperature epoxy sealants and a sealant prepared from the curing agent. The curing agent is a diamino-terminated polyether ionic curing agent, and the flexibility of chain segments is improved by introducing macromolecular polyether and ester functional groups into the main chain structure of the curing agent; meanwhile, the curing agent consists of anions and cations, the glass transition temperature is minus 90 ℃, the glass transition temperature of the polymer formed after curing is lower, the low temperature resistance is better, and the curing temperature is low; the imidazole type cation also has a promoting effect on curing, so that the curing speed is increased. The prepared sealant consists of 100 parts of epoxy resin, 3-7 parts of hydroxyl-terminated polybutadiene, 12-28 parts of curing agent, 1-3 parts of coupling agent and 12-24 parts of silicon micropowder. The sealant prepared by the invention can also keep higher strength at-196 ℃, and is more suitable for being used in ultralow temperature environment.
Description
Technical Field
The invention belongs to the technical field of sealants, and particularly relates to an ultralow-temperature epoxy sealant and a preparation method thereof.
Background
With the development of aerospace, superconducting technology, national defense industry and the like, the demand for adhesives used in ultra-low temperature environments is continuously increasing. In the aerospace and national defense industries, part of precision devices need to work at liquid helium temperature and obtain good sealing performance through bonding, but the devices cannot be heated due to the limitations of bonding materials, size, precision, process conditions and the like, and need to be cured at room temperature, so that new demands are put forward on ultra-low temperature adhesives. The sealant has obvious difference from an adhesive, the sealant has good bonding strength to bonding base materials, particularly, the sealant is required to have good infiltration and low curing shrinkage rate to the base materials, and for the sealant used in an ultralow temperature environment, the sealant is likely to crack due to shrinkage of a high polymer material in a cooling process, freezing and embrittling of chain segments at low temperature and the like, so that the stress of the ultralow temperature sealant is higher due to shrinkage, temperature drop and the like, and part of the chain segments capable of moving are required to be needed in the ultralow temperature environment, so that the molecular chains are prevented from being in a frozen stiff state, otherwise, the sealant is likely to crack or peel off once being subjected to stress or temperature change and loses tightness.
At present, ultra-low temperature adhesives are more studied, DW series adhesives, NHJ-44 nylon modified epoxy adhesives, HC-02 tetrahydrofuran polyether epoxy adhesives and the like are widely applied, and the adhesives are mainly polyurethane modified epoxy, nylon modified epoxy, modified polyurethane and other types of adhesives, and most of the low temperature adhesives are mainly limited to liquid nitrogen temperature in use, so that the adhesives can be really applied to a cryogenic environment. Most of the adhesives need high-temperature curing or high-temperature post-treatment, so that curing and crosslinking are more sufficient to obtain excellent bonding performance, and the low-temperature adhesives which can be partially cured at room temperature are high in viscosity and difficult to realize good infiltration on bonding interfaces, so that the sealing performance is not ideal; in addition, the low-temperature adhesive with room temperature curing and moderate viscosity can be partially cured at room temperature, the room temperature curing time is longer, and the practical value is lower.
The epoxy resin adhesive has excellent mechanical property, electrical insulation property, excellent adhesive property, good technological processing property, chemical corrosion resistance and other properties, and is widely applied to the fields of electronics, electrics, machinery, construction, aerospace and the like. At present, the research of low-temperature adhesives at home and abroad mainly uses epoxy resin adhesives, the epoxy resin adhesives have the problems of brittleness, low toughness, poor shock resistance and the like at normal temperature, and at ultralow temperature, the molecular chain motion of the conventional high polymer is completely frozen, the high polymer becomes brittle, the crack expansion resistance is greatly reduced, and the epoxy resin adhesives show larger brittleness at low temperature, so that the adhesive property, the sealing property and the like are influenced.
Disclosure of Invention
In order to solve the defects in the prior art, the invention provides a novel ultralow temperature resistant epoxy resin sealant, which comprises the following components in parts by weight: 100 parts of epoxy resin, 3-7 parts of hydroxyl-terminated polybutadiene, 12-28 parts of curing agent, 1-3 parts of coupling agent and 12-24 parts of silicon micropowder;
The curing agent has the structure as follows:
wherein, Representing an epoxy resin body.
The curing agent is a diamino-terminated polyether ionic curing agent, and the flexibility of chain segments is improved by introducing macromolecular polyether and ester functional groups into the main chain structure of the curing agent; meanwhile, the curing agent consists of anions and cations, the glass transition temperature is minus 90 ℃, the glass transition temperature of the polymer formed after curing is lower, the low temperature resistance is better, and the curing temperature is low; the imidazole type cation also has a promoting effect on curing, so that the curing speed is increased.
The preparation of the curing agent mainly comprises the following two steps:
And reacting the carboxyl-terminated polyether ionic liquid with epoxy resin under the action of a quaternary ammonium salt catalyst to generate epoxy-terminated polyether ionic liquid, and then reacting the epoxy-terminated polyether ionic liquid with diamine to generate the amino-terminated polyether ionic curing agent.
The epoxy resin is at least one of bisphenol F epoxy resin or bisphenol A epoxy resin;
The average molecular weight of the hydroxyl-terminated polybutadiene is 2800-3600, and the hydroxyl value is 0.47-0.53mmo l/g;
The coupling agent is a silane coupling agent and comprises at least one of vinyl triethoxysilane, vinyl trimethoxysilane and gamma-aminopropyl triethoxysilane;
the silicon micropowder is nano-grade silicon micropowder, and the particle size range is 50-200nm.
The preparation method of the ultralow-temperature sealant comprises the following steps:
(4) Mixing epoxy resin and hydroxyl-terminated polybutadiene according to a mass ratio, and stirring at a high speed to obtain hydroxyl-terminated polybutadiene modified epoxy resin;
(5) Mixing the silicon micro powder and the coupling agent according to the mass ratio, adding the mixture into a grinder for grinding for 2-3 hours, then placing the mixture into an oven for aging for 6-8 hours at 60-70 ℃, and cooling to obtain modified silicon micro powder;
(6) Sequentially adding the modified epoxy resin prepared in the step (1) and the modified silicon micropowder prepared in the step (2) into a reaction kettle, stirring at a high speed, vacuum defoaming for 1-2h at 68-90 ℃, then cooling to room temperature, adding a curing agent, stirring vigorously for 2-3h under vacuum, and discharging to obtain the ultralow-temperature epoxy sealant.
The ultralow-temperature epoxy sealant adopts hydroxyl-terminated polybutadiene to modify epoxy resin, so that the viscosity of the epoxy resin is effectively reduced, the processing performance is improved, and the glass transition temperature of the sealant is reduced; the silicon micropowder can be well adhered to an epoxy network after being modified by a silane coupling agent, so that the adhesive strength is improved; the sealant prepared by the invention adopts a macromolecular diamino-terminated polyether ionic compound, so that the glass transition temperature of the sealant is further reduced, and the sealant prepared by the invention is more suitable for use in low-temperature environments.
Drawings
FIG. 1 is an infrared spectrum of a curing agent.
Detailed Description
The invention is further described below in connection with embodiments, which are only a few of the embodiments of the invention. Based on the embodiments of the present invention, those skilled in the art may make equivalent substitutions or modifications without making any inventive effort, which are within the scope of the present invention.
1. Preparation of curing agent
The structural general formula of the curing agent is as follows:
The carboxyl-terminated polyether ionic liquid is reacted with epoxy resin under the action of a quaternary ammonium salt catalyst to generate epoxy-terminated polyether ionic liquid, and then the epoxy-terminated polyether ionic liquid is reacted with diamine to generate an amino-terminated polyether ionic curing agent, wherein the specific synthetic route is as follows:
(1) The carboxyl-terminated polyether ionic liquid is prepared by a laboratory: adding carboxyl-terminated polyepichlorohydrin and N-methylimidazole into a three-mouth bottle according to the mol ratio of 1:1, reacting for 24 hours at the constant temperature of 80 ℃, washing with ethyl acetate, and drying in vacuum to obtain the carboxyl-terminated polyether ionic liquid.
(2) Under the protection of nitrogen, adding metered E-51 epoxy resin and benzyl triethyl ammonium chloride into a reaction kettle, raising the temperature to 100 ℃, slowly dripping carboxyl-terminated polyether ionic liquid, slowly raising the temperature to 115 ℃ after dripping, and carrying out heat preservation reaction for 2-3h to obtain epoxy-terminated polyether ionic liquid after the reaction is finished;
(3) And (3) under the protection of nitrogen, adding excessive ethanol solution of hexamethylenediamine into a reaction kettle, raising the temperature to 50 ℃, then dropwise adding the epoxy-terminated polyether ionic liquid prepared in the step (2), carrying out heat preservation reaction for 3-4h after the dropwise adding is finished, removing ethanol by reduced pressure distillation after the reaction is finished, washing with ethyl acetate for 3 times, and carrying out vacuum drying to obtain the diamino-terminated polyether ionic liquid curing agent.
The prepared curing agent is characterized by adopting infrared spectrum, and the result is shown in figure 1.
Example 1
The embodiment provides a novel ultralow temperature resistant epoxy resin sealant, which comprises the following components in parts by weight: 100 parts of bisphenol F epoxy resin, 3 parts of hydroxyl-terminated polybutadiene (molecular weight 2800, hydroxyl value 0.53 mmo/g), 13 parts of curing agent, 1 part of vinyl triethoxysilane and 12 parts of silica micropowder (average particle diameter 110 nm);
The preparation method of the ultralow-temperature sealant comprises the following steps:
(1) Mixing 500g of epoxy resin and 15g of hydroxyl-terminated polybutadiene according to a mass ratio, and stirring at a high speed to obtain hydroxyl-terminated polybutadiene modified epoxy resin;
(2) Mixing 60g of silicon micropowder and 5g of vinyl triethoxysilane according to a mass ratio, adding into a grinder for grinding for 2-3h, putting into an oven for aging for 6-8h at 60-70 ℃, and cooling to obtain modified silicon micropowder;
(3) Sequentially adding the modified epoxy resin prepared in the step (1) and the modified silicon micropowder prepared in the step (2) into a reaction kettle, stirring at a high speed, vacuum defoaming for 1-2h at 68-90 ℃, then cooling to room temperature, adding 65g of a curing agent, stirring vigorously for 2-3h under vacuum, and discharging to obtain the ultralow-temperature epoxy sealant.
Example 2
The embodiment provides a novel ultralow temperature resistant epoxy resin sealant, which comprises the following components in parts by weight: 100 parts of bisphenol F epoxy resin, 5 parts of hydroxyl-terminated polybutadiene (molecular weight 2800, hydroxyl value 0.53 mmo/g), 15 parts of curing agent, 1 part of vinyl triethoxysilane and 18 parts of silicon micropowder (average particle diameter 110 nm);
The preparation method of the ultralow temperature sealant is the same as that of the embodiment 1.
Example 3
The embodiment provides a novel ultralow temperature resistant epoxy resin sealant, which comprises the following components in parts by weight: 100 parts of bisphenol A epoxy resin, 5 parts of hydroxyl-terminated polybutadiene (molecular weight 3300, hydroxyl value 0.47mmo l/g), 20 parts of curing agent, 1 part of vinyl trimethoxy silane and 20 parts of silicon micropowder (average particle diameter 110 nm);
The preparation method of the ultralow temperature sealant is the same as that of the embodiment 1.
Example 4
The embodiment provides a novel ultralow temperature resistant epoxy resin sealant, which comprises the following components in parts by weight: 100 parts of bisphenol A epoxy resin, 6 parts of hydroxyl-terminated polybutadiene (molecular weight 3300, hydroxyl value 0.47 mmo/g), 20 parts of curing agent, 1 part of gamma-aminopropyl triethoxysilane and 20 parts of silica micropowder (average particle diameter 110 nm);
The preparation method of the ultralow temperature sealant is the same as that of the embodiment 1.
Comparative example 1
The comparative example provides an ultralow temperature resistant epoxy resin sealant, which comprises the following components in parts by weight: 100 parts of bisphenol F epoxy resin, 3 parts of hydroxyl-terminated polybutadiene (molecular weight 2800, hydroxyl value 0.53 mmol/g), 13 parts of curing agent, 1 part of vinyl triethoxysilane and 12 parts of silica micropowder (average particle diameter 110 nm); the curing agent is polyetheramine D230.
The preparation method of the epoxy sealant is the same as that of the embodiment 1.
Comparative example 2
The comparative example provides an ultralow temperature resistant epoxy resin sealant, which comprises the following components in parts by weight: 100 parts of bisphenol F epoxy resin, 13 parts of curing agent, 1 part of vinyl triethoxysilane and 12 parts of silica micropowder (average particle diameter 110 nm); the curing agent is polyetheramine D230.
The preparation method of the low-temperature epoxy sealant is the same as that of the embodiment 1, except that the modification of the epoxy resin in the step (1) is not included.
In order to verify the technical effects of the invention, the sealants prepared in examples and comparative examples were cured at 60 ℃ for 10 hours, and then the mechanical properties and the temperature resistance were tested respectively. The mechanical property test is carried out by using GB/T2567-2008 resin casting body performance test method, wherein the ultralow temperature performance is carried out under a liquid nitrogen heat preservation sleeve; the glass transition temperature is tested by adopting a DMA method;
TABLE 1 Performance parameters of Low temperature epoxy sealants
From the data, the glass transition temperature of the sealant prepared by the embodiment of the invention is obviously reduced, the low-temperature tensile strength is obviously improved, and the sealant has better ultralow-temperature resistance.
The foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and scope of the invention are intended to be included within the scope of the invention.
Claims (5)
1. An ultralow-temperature epoxy curing agent is characterized in that carboxyl-terminated polyether ionic liquid reacts with epoxy resin under the action of a quaternary ammonium salt catalyst to generate epoxy-terminated polyether ionic liquid, then reacts with diamine to generate a diamino-terminated polyether ionic curing agent,
The curing agent has the structure as follows:
wherein, Is the residue after the ring opening of the epoxy resin.
2. The ultra-low temperature epoxy hardener of claim 1, wherein the preparation of the hardener essentially comprises the following routes:
And reacting the carboxyl-terminated polyether ionic liquid with epoxy resin under the action of a quaternary ammonium salt catalyst to generate epoxy-terminated polyether ionic liquid, and then reacting the epoxy-terminated polyether ionic liquid with diamine to generate the diamino-terminated polyether ionic curing agent.
3. The novel ultralow temperature resistant epoxy resin sealant is characterized by comprising the following components in parts by weight: 100 parts of epoxy resin, 3-7 parts of hydroxyl-terminated polybutadiene, 12-28 parts of curing agent, 1-3 parts of coupling agent and 12-24 parts of silicon micropowder; the curing agent is the diamino terminated polyether ionic curing agent of claim 1 or 2.
4. The novel ultra-low temperature resistant epoxy resin sealant according to claim 3, wherein the epoxy resin is at least one of bisphenol F epoxy resin or bisphenol a epoxy resin; the average molecular weight of the hydroxyl-terminated polybutadiene is 2800-3600, and the hydroxyl value is 0.47-0.53mmol/g; the coupling agent is at least one of vinyl triethoxysilane, vinyl trimethoxysilane and gamma-aminopropyl triethoxysilane; the silicon micropowder is nano-grade silicon micropowder, and the particle size range is 50-200nm.
5. The method for preparing the ultralow temperature sealant according to claim 3 or 4, comprising the following steps:
(1) Mixing epoxy resin and hydroxyl-terminated polybutadiene according to a mass ratio, and stirring at a high speed to obtain hydroxyl-terminated polybutadiene modified epoxy resin;
(2) Mixing the silicon micro powder and the coupling agent according to the mass ratio, adding the mixture into a grinder for grinding for 2-3 hours, then placing the mixture into an oven for aging for 6-8 hours at 60-70 ℃, and cooling to obtain modified silicon micro powder;
(3) Sequentially adding the modified epoxy resin prepared in the step (1) and the modified silicon micropowder prepared in the step (2) into a reaction kettle, stirring at a high speed, vacuum defoaming for 1-2h at 68-90 ℃, then cooling to room temperature, adding a curing agent, stirring vigorously for 2-3h under vacuum, and discharging to obtain the ultralow-temperature epoxy sealant.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211348293.3A CN116813917B (en) | 2022-10-31 | 2022-10-31 | Curing agent for ultralow-temperature epoxy sealant and sealant prepared from curing agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211348293.3A CN116813917B (en) | 2022-10-31 | 2022-10-31 | Curing agent for ultralow-temperature epoxy sealant and sealant prepared from curing agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116813917A CN116813917A (en) | 2023-09-29 |
| CN116813917B true CN116813917B (en) | 2024-07-09 |
Family
ID=88119024
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211348293.3A Active CN116813917B (en) | 2022-10-31 | 2022-10-31 | Curing agent for ultralow-temperature epoxy sealant and sealant prepared from curing agent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116813917B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN118652676A (en) * | 2024-08-14 | 2024-09-17 | 铜川恒晟科技材料有限公司 | Propping agent and preparation method thereof |
Family Cites Families (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1261480C (en) * | 2003-11-05 | 2006-06-28 | 北京航空航天大学 | Ultra-low temperature adhesive of epoxy resin and preparation thereof |
| DE102006000651A1 (en) * | 2006-01-03 | 2007-07-12 | Degussa Gmbh | Preparation of ionic liquids and resins |
| DE102006000648A1 (en) * | 2006-01-03 | 2007-07-12 | Degussa Gmbh | Ionic liquids contained resins |
| CN102060978B (en) * | 2010-11-29 | 2012-06-13 | 合肥工业大学 | Pyridine polyether ionic liquid toughened epoxy resin and preparation method thereof |
| US9169371B2 (en) * | 2011-06-16 | 2015-10-27 | Sabic Global Technologies B.V. | Compositions having reduced frictional coefficient, method of manufacture thereof and articles comprising the same |
| CN104650026B (en) * | 2014-11-21 | 2017-04-12 | 沈阳工业大学 | Method for preparing propylene carbonate |
| CN108164446A (en) * | 2016-01-26 | 2018-06-15 | 绍兴瑞康生物科技有限公司 | A kind of carboxamides and its preparation method and application |
| CN106040296B (en) * | 2016-06-01 | 2019-03-15 | 沈阳工业大学 | The preparation method of the poly- propyl ether -3- methylimidazole ionic-liquid catalyst of chlorination 1- amino |
| CN107722239B (en) * | 2017-10-24 | 2019-11-15 | 中国科学院长春应用化学研究所 | A kind of epoxide resin material and preparation method thereof |
| CN109721947A (en) * | 2017-10-27 | 2019-05-07 | 财团法人工业技术研究院 | Composition epoxy resin |
| CN109439254B (en) * | 2018-10-31 | 2021-05-04 | 深圳广恒威科技有限公司 | High-reliability filling adhesive capable of being repaired |
| CN111423835B (en) * | 2020-04-15 | 2021-08-17 | 中国科学院过程工程研究所 | COB electronic packaging adhesive and preparation method thereof |
| CN114605616B (en) * | 2020-12-03 | 2023-05-26 | 万华化学集团股份有限公司 | Quick-drying nonionic water-based epoxy curing agent, and preparation method and application thereof |
| CN114106519A (en) * | 2021-12-09 | 2022-03-01 | 中威北化科技有限公司 | Modified epoxy resin matrix material for wide temperature range and preparation method and application thereof |
| CN114656913A (en) * | 2022-04-11 | 2022-06-24 | 嘉兴利贝德新材料科技有限公司 | Epoxy resin pouring sealant containing modified polybutadiene |
-
2022
- 2022-10-31 CN CN202211348293.3A patent/CN116813917B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN116813917A (en) | 2023-09-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103627362B (en) | A kind of reaction type polyurethane hot-melt adhesive and preparation method thereof | |
| CN102827566B (en) | Single-component high/low-temperature-resistant epoxy resin composition | |
| CN116813917B (en) | Curing agent for ultralow-temperature epoxy sealant and sealant prepared from curing agent | |
| CN110951435B (en) | High-strength silane modified polyether sealant with equal proportion and preparation method thereof | |
| CN102532809A (en) | Organosilicon-epoxy resin composition and preparation method thereof | |
| CN104726047A (en) | Room-temperature cured high-temperature-resistant epoxy resin plugging material and preparation method thereof | |
| CN101696263B (en) | Epoxy resin curing agent, method for preparing same and application thereof | |
| CN102838869A (en) | Epoxy resin-polyurethane hybridized high-temperature resisting heat-insulating material and preparation method | |
| CN112341973B (en) | Two-component normal-temperature cured epoxy resin elastomer composition and preparation method thereof | |
| CN104449508A (en) | Flexible epoxy structural adhesive and preparation method thereof | |
| CN112625218B (en) | Epoxy resin for cutting water-resistant silicon rod and preparation method thereof | |
| CN103074020A (en) | Room-temperature cured, low-viscosity and low temperature-resistant adhesive | |
| CN111040715A (en) | Single-component reaction type polyurethane hot melt adhesive and preparation method thereof | |
| CN112980375A (en) | Single-component silane modified polyether sealant and preparation method thereof | |
| CN105061714A (en) | Synthetic method and application of silicon alkane terminated polyurethane prepolymer | |
| CN115160966A (en) | High-strength weather-resistant automobile structure adhesive and preparation method thereof | |
| CN111892902B (en) | Novel double-component modified polyurethane sealant for hollow glass and preparation method thereof | |
| CN110591624A (en) | Mercaptan modified room temperature fast curing epoxy adhesive prepolymer and preparation method thereof | |
| CN110724246A (en) | Free foaming sealing material composite material and preparation method thereof | |
| CN112480865B (en) | New energy automobile coil high-temperature-resistant adhesive | |
| CN114574138A (en) | Halogen-free flame-retardant epoxy resin sealant | |
| CN114181377A (en) | Cyclotriphosphazene-based flame-retardant imidazole curing agent and preparation method and application thereof | |
| CN113683865A (en) | Epoxy composition for encapsulation, encapsulation material and application | |
| CN113278396A (en) | Modified epoxy polyurethane sealant and preparation method thereof | |
| CN113004829A (en) | Electronic adhesive for packaging graphene-based semiconductor chip 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 | ||
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20240612 Address after: 510000 Hua Long Zhen Tang tou Cun Qing Mei Gang, Panyu District, Guangzhou City, Guangdong Province Applicant after: Guangzhou Lianhong Synthetic Material Co.,Ltd. Country or region after: China Address before: 7111, 11th Floor, Unit 7, Building 4, Huajiadi Nanli, Futong East Street, Chaoyang District, Beijing, 100102 Applicant before: Zhang Yan Country or region before: China |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |