CN111808563A - Multifunctional heat-resistant high-performance adhesive and preparation method and application thereof - Google Patents
Multifunctional heat-resistant high-performance adhesive and preparation method and application thereof Download PDFInfo
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- CN111808563A CN111808563A CN202010760112.2A CN202010760112A CN111808563A CN 111808563 A CN111808563 A CN 111808563A CN 202010760112 A CN202010760112 A CN 202010760112A CN 111808563 A CN111808563 A CN 111808563A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
- B32B37/1284—Application of adhesive
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses a multifunctional heat-resistant high-performance adhesive, a preparation method and application thereof, relates to a resin matrix adhesive, and a preparation method and application thereof, and aims to solve the problem that the existing adhesive does not have an adhesive integrating excellent performance, wide curing temperature range, convenience in use and no solvent. The multifunctional heat-resistant high-performance adhesive is prepared by modifying resin, a curing agent and a toughening agent; the modified resin is resin a and resin b, the toughening agent is carboxyl nitrile rubber, and the modified curing agent is modified amine series curing agent and m-diazocene curing agent. The multifunctional heat-resistant high-performance adhesive has the characteristics of excellent bonding performance, wide curing temperature range, convenience in use, no solvent and the like, can reduce environmental pollution, and can be used for bonding composite materials/composite materials, metals/metals and dissimilar materials. The preparation and application methods of the invention are simple, and the prepared adhesive has excellent performance and can be used in the high-tech and civil fields of aerospace and the like.
Description
Technical Field
The invention relates to a resin matrix adhesive and a preparation method and application thereof.
Background
The existing adhesive generally contains volatile solvents such as ethyl acetate or acetone and the like or solvents with high toxicity such as toluene, xylene and the like, when the adhesive is used, the solvents contained in the adhesive of the bonding surface need to be aired or heated to volatilize, and then the bonding is carried out, so that the environmental pollution and the health hazard are caused, and the using method is complex. The curing temperature of the adhesive can be selected only one or two, the curing temperature range is narrow, so the curing temperature can not be selected according to the material of the adhesive piece, and the use is limited.
In short, the existing adhesive has the problems that no adhesive which integrates excellent performance, wide curing temperature range, convenient use and no solvent is available.
Disclosure of Invention
The invention provides a multifunctional heat-resistant high-performance adhesive and a preparation method and application thereof, aiming at solving the problem that the existing adhesive has no adhesive integrating excellent performance, wide curing temperature range, convenient use and no solvent.
The multifunctional heat-resistant high-performance adhesive is prepared by modifying modified resin, a modified curing agent and a toughening agent, wherein the modified resin is resin a and resin b, the toughening agent is carboxyl nitrile rubber, the modified curing agent is a modified amine series curing agent and a m-diazenyl curing agent, and the auxiliary material is a silicon dioxide inorganic filler;
the resin a is TDE85 resin, the resin B is F51 resin, the modified amine series curing agent comprises modified amine A and modified amine B, the modified amine A is AF curing agent, and the modified amine B is GY051 curing agent;
the weight ratio of the resin a to the resin B to the toughening agent to the modified amine A to the m-diazenyl curing agent to the modified amine B to the silicon dioxide is 100: 1-89: 0-89.
The multifunctional heat-resistant high-performance adhesive has the characteristics of excellent bonding performance, wide curing temperature range, convenience in use, no solvent and the like, and can reduce environmental pollution.
The preparation method of the multifunctional heat-resistant high-performance adhesive is realized according to the following steps:
and uniformly mixing and stirring the resin a, the resin B, the flexibilizer, the modified amine A, the m-diazenyl curing agent, the modified amine B and the silica inorganic filler according to the weight ratio of 100: 1-89: 0-89 to obtain the multifunctional heat-resistant high-performance adhesive.
The multifunctional heat-resistant high-performance adhesive disclosed by the invention is excellent in bonding performance, simple in preparation and application methods, capable of reducing the production cost and improving the production efficiency, wide in application range and capable of being used in the high-tech and civil fields of aerospace and the like.
The bonding method applying the multifunctional heat-resistant high-performance adhesive is realized according to the following steps:
coating a multifunctional heat-resistant high-performance adhesive (abbreviated as glue) on a clean bonding surface of a piece to be bonded, and attaching and compacting the bonding piece to obtain a bonding piece containing the glue;
and secondly, carrying out gradient heating solidification on the adhesive piece containing the glue according to a solidification temperature program, and then naturally cooling to obtain the adhesive piece.
The multifunctional heat-resistant high-performance adhesive, the preparation method and the application thereof comprise the following beneficial effects:
1. the multifunctional heat-resistant high-performance adhesive has wide curing temperature range, is convenient to use, and can select the curing temperature according to the heat-resistant temperature of the material of the bonded piece, so that the material of the bonded piece can be protected from the reduction of the material performance caused by heat aging generated by unnecessary high-temperature curing. The adhesive can be cured at room temperature of 60 ℃ or less, can be cured at room temperature to medium temperature, and can be cured at room temperature to medium temperature to high temperature, so that the optional curing temperature range of the adhesive is wide, and the adhesive can resist thermal aging of high-temperature curing, wherein the room temperature curing refers to room temperature of 60 ℃, the medium temperature refers to 61-130 ℃, and the high temperature refers to more than 130 ℃. Proved by verification, the tensile strength of the adhesive can reach 42MPa and the tensile modulus can reach 2.6GPa no matter which curing temperature program is adopted to cure the adhesive, and the adhesive prepared by the invention has the property of wide curing temperature range. The verification test adopts the adhesive casting body made of the adhesive with the same proportion, and adopts different curing temperature programs, namely the adhesive casting body is respectively cured under the conditions of room temperature to less than or equal to 60 ℃, room temperature to medium temperature, and room temperature to medium temperature to high temperature, thereby eliminating the influence of other factors such as the material of a bonding piece, the thickness of an adhesive layer and the like on the mechanical property of the adhesive, and the method can be used for proving whether the adhesive has the property of wide curing temperature range by measuring the mechanical property of the adhesive. According to the GB/T2568-1995 standard, the tensile property of the adhesive casting body cured at different curing temperature programs is measured, and the adhesive cured at room temperature to less than or equal to 60 ℃ is measured by adopting the curing temperature program, the tensile strength of the adhesive is more than or equal to 42MPa, and the tensile modulus is more than or equal to 2.6 GPa; adopting an adhesive with a curing temperature program from room temperature to medium temperature to high temperature, wherein the tensile strength of the adhesive is more than or equal to 43MPa, and the tensile modulus is more than or equal to 2.8 GPa; the adhesive cured at room temperature to medium temperature in the curing temperature program is adopted, the tensile strength of the adhesive is more than or equal to 48MPa, and the tensile modulus is more than or equal to 2.6Gpa, which shows that the adhesive prepared by the invention has the property of wide curing temperature range;
2. the multifunctional heat-resistant high-performance adhesive does not contain a solvent, so that the step of drying or heating and volatilizing the solvent contained in the adhesive for the bonding surface is saved, the environmental pollution is reduced, the using method is simple, and the efficiency is high;
3. the multifunctional heat-resistant high-performance adhesive can be used for bonding composite materials/composite materials and metals/metals and can also be used for bonding different materials. When the same material is bonded: according to GB/T7124-2008 standard, the tensile shear strength of the metal/metal bonding piece and the tensile shear strength of the composite material/composite material bonding piece are measured, and the metal/metal tensile shear strength is not less than 18Mpa through measurement; the tensile shear strength of the composite material/wet composite material is more than or equal to 21 MPa;
when bonding dissimilar materials: according to the GB/T7124-2008 standard, the tensile shear strength of the metal/wet composite material bonding piece is determined, and the tensile shear strength of the metal/wet composite material is determined to be more than or equal to 12 MPa;
4. the multifunctional heat-resistant high-performance adhesive disclosed by the invention has heat resistance and high performance, a metal/metal bonding piece is prepared by adopting the adhesive with the same proportion under the conditions of the same process and the same curing temperature program, and the tensile shear strength of the metal/metal bonding piece at room temperature and different temperatures is measured by referring to the GB/T7124-. Through determination, the tensile shear strength of the metal/metal at room temperature is more than or equal to 18MPa, the tensile shear strength at 100 ℃ is more than or equal to 15MPa, and the tensile shear strength at 120 ℃ is more than or equal to 15 MPa. The adhesive prepared by the invention has heat resistance and high performance;
5. in conclusion, the adhesive has the advantages of multifunction, heat resistance and high performance, simple preparation method and application method, wide curing temperature range, reduction of production cost, reduction of environmental pollution, improvement of production efficiency and excellent comprehensive performance.
Detailed Description
The first embodiment is as follows: the multifunctional heat-resistant high-performance adhesive is prepared by modifying modified resin, a modified curing agent and a toughening agent, wherein the modified resin is resin a and resin b, the toughening agent is carboxyl nitrile rubber, the modified curing agent is a modified amine series curing agent and a m-dinitrogen cyclopentadiene curing agent, and the auxiliary material is a silicon dioxide inorganic filler;
the resin a is TDE85 resin, the resin B is F51 resin, the modified amine series curing agent comprises modified amine A and modified amine B, the modified amine A is AF curing agent, and the modified amine B is GY051 curing agent;
the weight ratio of the resin a to the resin B to the toughening agent to the modified amine A to the m-diazenyl curing agent to the modified amine B to the silicon dioxide is 100: 1-89: 0-89.
The silicon dioxide auxiliary material in the multifunctional heat-resistant high-performance adhesive in the embodiment can be not added, and the silicon dioxide mainly plays a role of a thixotropic agent. The multifunctional heat-resistant high-performance adhesive has excellent performance and wide application range, and can be used in the fields of high technologies such as aerospace and civil use.
The main reason for the excellent comprehensive performance of the adhesive is that the adhesive formula is reasonable in design, and the purposes of adhesive formula design and modification are achieved through a series of beneficial chemical modification, toughening modification and material properties of resin, a curing agent and a toughening agent, so that the adhesive with excellent performance is generated; and meanwhile, the resin and the curing agent are toughened and modified by adopting the rubber containing carboxyl, the carboxyl nitrile rubber has good compatibility with the resin and the curing agent, and the carboxyl can also have chemical crosslinking reaction with the resin and the curing agent, so that the toughness of the adhesive is improved. Through a series of chemical modification reactions between the resin, the curing agent and the carboxyl nitrile rubber molecules, the macromolecular of the adhesive polymer is blocked with a molecular chain segment of the resin and the curing agent and a molecular chain segment of the tough rubber, and the molecular chain segment of the resin and the curing agent which have the functions of strength and heat resistance is blocked in the molecular chain segment of the tough rubber, the molecular chain segments and the functional groups which play different roles are mutually interwoven and intertwined to generate chemical crosslinking reaction to form chemical bonds and functional groups which are beneficial to improving the performance of the adhesive, the adhesive contains polar carboxyl functional groups and other functional groups, and the polar functional groups are favorable for the adhesive to bond various materials.
The second embodiment is as follows: the difference between the embodiment and the specific embodiment is that the weight ratio of the resin a to the resin B to the toughening agent to the modified amine A to the m-diazenyl curing agent to the modified amine B to the silicon dioxide is 100 to (30-75) to (1-26) to (0-36).
The third concrete implementation mode: the present embodiment is different from the first or second embodiment in that the m-diazeniumene-based curing agent is 2-ethyl-4-methylimidazole.
The fourth concrete implementation mode: this embodiment is different from the first to third embodiments in that the silica is fumed silica.
The fifth concrete implementation mode: the preparation method of the multifunctional heat-resistant high-performance adhesive is implemented according to the following steps:
and uniformly mixing and stirring the resin a, the resin B, the flexibilizer, the modified amine A, the m-diazenyl curing agent, the modified amine B and the silica inorganic filler according to the weight ratio of 100: 1-89: 0-89 to obtain the multifunctional heat-resistant high-performance adhesive.
The sixth specific implementation mode: the bonding method applying the multifunctional heat-resistant high-performance adhesive is realized according to the following steps:
coating a multifunctional heat-resistant high-performance adhesive (abbreviated as glue) on a clean bonding surface of a piece to be bonded, and attaching and compacting the bonding piece to obtain a bonding piece containing the glue;
and secondly, carrying out gradient heating solidification on the adhesive piece containing the glue according to a solidification temperature program, and then naturally cooling to obtain the adhesive piece.
The seventh embodiment: the sixth difference between this embodiment and the sixth embodiment is that the step two of performing the gradient temperature-raising curing process according to the curing temperature program is as follows: at room temperature/3-6 h → gradient is increased to 48-60 ℃/6-16 h.
The specific implementation mode is eight: the sixth difference between this embodiment and the sixth embodiment is that the step two of performing the gradient temperature-raising curing process according to the curing temperature program is as follows: at room temperature/3-6 h → gradient is raised to 61-130 ℃/6-10 h.
The specific implementation method nine: the sixth difference between this embodiment and the sixth embodiment is that the step two of performing the gradient temperature-raising curing process according to the curing temperature program is as follows: at room temperature/3-6 h → gradient is increased to 131-155 ℃/5-10 h.
The first embodiment is as follows:
the present embodiment is used to verify whether the adhesive has a wide curing temperature range. The multifunctional heat-resistant high-performance adhesive is prepared by uniformly mixing and stirring resin a, resin B, a toughening agent, modified amine A, a m-diazeniumne curing agent and modified amine B according to the weight ratio of 100: 68: 39: 34: 6: 4, and respectively curing at room temperature to 55 ℃, 116 ℃ and 152 ℃ by adopting curing temperature programs.
The adhesive in this example has the same ratio, and the adhesive casting is cured by temperature gradient according to different curing temperature programs, and the tensile property of the adhesive is determined according to GB/T2568-.
The determination shows that the adhesive cured at room temperature to 55 ℃ by adopting the curing temperature program has the tensile strength of 42.8MPa and the tensile modulus of 2.6 GPa.
The adhesive cured at room temperature to medium temperature to high temperature 152 ℃ is adopted, and the tensile strength is 43.6MPa and the tensile modulus is 2.8 GPa.
The adhesive cured at room temperature to medium temperature of 116 ℃ is adopted, and the tensile strength of the adhesive is 48.4MPa and the tensile modulus is 2.6 GPa.
The verification shows that the tensile strength of the adhesive can reach more than or equal to 42MPa and the tensile modulus can reach more than or equal to 2.6GMa no matter which curing temperature program is adopted to cure the adhesive, and the adhesive prepared by the invention has the property of wide curing temperature range.
Example two:
the method for bonding the metal/metal by the multifunctional heat-resistant high-performance adhesive comprises the following steps:
firstly, coating an adhesive (abbreviated as glue) on the clean bonding surface of a piece to be bonded, and attaching and compacting the bonding piece to obtain a bonding piece containing the glue;
and secondly, carrying out gradient temperature rise solidification on the glue-containing bonding piece obtained in the step one according to a solidification temperature program, and then naturally cooling to obtain the heat-resistant high-performance bonding piece.
The adhesive prepared by the embodiment is used for bonding metal/metal and is used for verifying whether the adhesive can bond the same material. According to GB/T7124-2008 standard, the tensile shear strength of metal/metal of the adhesive piece is measured, and the tensile shear strength of metal/metal is 18.3 MPa. It can be proved that the adhesive can be used for bonding the same material and has high performance.
Example three:
the material of the bonding member in this embodiment is a composite material/wet composite material.
The adhesive bonding composite material/wet composite material prepared in the embodiment is determined by referring to the GB/T7124-2008 standard, and the tensile shear strength of the bonding piece composite material/wet composite material is determined to be 21.1MPa, so that the adhesive can be used for bonding the composite material/composite material and has high performance.
Example four:
the bonding piece of the embodiment is made of a metal/wet composite material and is used for verifying whether the adhesive can be used for bonding dissimilar materials.
The metal/wet composite material bonded by the multifunctional heat-resistant high-performance adhesive prepared in the embodiment is determined by referring to the GB/T7124-2008 standard, and the tensile shear strength of the metal/wet composite material of the bonding piece is determined to be 12.8MPa, so that the adhesive can be used for bonding dissimilar materials and has high performance.
Example five:
the present example is used to verify whether the adhesive has heat resistance and high performance.
The multifunctional heat-resistant high-performance adhesive is prepared by uniformly mixing and stirring resin a, resin B, a toughening agent, modified amine A, a m-diazeniumne curing agent, modified amine B and gas-phase silica according to the weight ratio of 100: 64: 45: 40: 6: 22.
The method for bonding metal/metal by using the multifunctional heat-resistant high-performance adhesive comprises the following steps:
coating an adhesive (abbreviated as glue) on a clean bonding surface of a piece to be bonded, and attaching and compacting the bonding piece to obtain a bonding piece containing the glue;
and secondly, carrying out gradient temperature rise solidification on the glue-containing bonding piece obtained in the step one according to a solidification temperature program, and then naturally cooling to obtain the heat-resistant high-performance bonding piece.
The adhesive prepared by the embodiment is used for bonding the metal/metal bonding piece, the adhesive with the same proportion is prepared at the same curing temperature, and the tensile shear strength of the metal/metal bonding piece at different temperatures is tested to verify whether the adhesive has heat resistance and high performance. And the tensile shear strength of the metal/metal adhesive piece at different temperatures is measured by referring to the GB/T7124-2008 standard. The determination shows that the metal/metal room temperature tensile shear strength is 18.5MPa, the 100 ℃ tensile shear strength is 15.8MPa, and the 120 ℃ tensile shear strength is 15.6MPa, which indicates that the adhesive prepared by the invention has heat resistance and high performance.
Claims (9)
1. The multifunctional heat-resistant high-performance adhesive is characterized by being prepared by modifying modified resin, a modified curing agent and a toughening agent, wherein the modified resin is resin a and resin b, the toughening agent is carboxyl nitrile rubber, the modified curing agent is a modified amine series curing agent and a m-dinitrogen cyclopentadiene curing agent, and the auxiliary material is a silicon dioxide inorganic filler;
the resin a is TDE85 resin, the resin B is F51 resin, the modified amine series curing agent comprises modified amine A and modified amine B, the modified amine A is AF curing agent, and the modified amine B is GY051 curing agent;
the weight ratio of the resin a to the resin B to the toughening agent to the modified amine A to the m-diazenyl curing agent to the modified amine B to the silicon dioxide is 100: 1-89: 0-89.
2. The multifunctional heat-resistant high-performance adhesive as claimed in claim 1, wherein the weight ratio of the resin a to the resin B to the toughening agent to the modified amine A to the m-diazocene curing agent to the modified amine B to the silicon dioxide is 100 to (30 to 75) to (1 to 26) to (0 to 36).
3. The multifunctional heat-resistant high-performance adhesive according to claim 1, wherein the m-diazeniumene curing agent is 2-ethyl-4-methylimidazole.
4. The multifunctional heat resistant high performance adhesive of claim 1 wherein the silica is fumed silica.
5. The preparation method of the multifunctional heat-resistant high-performance adhesive is characterized by comprising the following steps:
and uniformly mixing and stirring the resin a, the resin B, the flexibilizer, the modified amine A, the m-diazenyl curing agent, the modified amine B and the silica inorganic filler according to the weight ratio of 100: 1-89: 0-89 to obtain the multifunctional heat-resistant high-performance adhesive.
6. The bonding method of the multifunctional heat-resistant high-performance adhesive according to claim 1 is characterized by comprising the following steps:
coating a multifunctional heat-resistant high-performance adhesive on the bonding surface of a piece to be bonded, and attaching and compacting the bonding piece to obtain a bonding piece containing glue;
and secondly, carrying out gradient heating solidification on the adhesive piece containing the glue according to a solidification temperature program, and then naturally cooling to obtain the adhesive piece.
7. The bonding method using the multifunctional heat-resistant high-performance adhesive according to claim 6, wherein the step two is performed by a gradient temperature-raising curing process according to a curing temperature program as follows: at room temperature/3-6 h → gradient is increased to 48-60 ℃/6-16 h.
8. The bonding method using the multifunctional heat-resistant high-performance adhesive according to claim 6, wherein the step two is performed by a gradient temperature-raising curing process according to a curing temperature program as follows: at room temperature/3-6 h → gradient is raised to 61-130 ℃/6-10 h.
9. The bonding method using the multifunctional heat-resistant high-performance adhesive according to claim 6, wherein the step two is performed by a gradient temperature-raising curing process according to a curing temperature program as follows: at room temperature/3-6 h → gradient is increased to 131-155 ℃/5-10 h.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113845755A (en) * | 2021-10-13 | 2021-12-28 | 哈尔滨玻璃钢研究院有限公司 | Environment-friendly high-performance multifunctional resin matrix and preparation method of composite material thereof |
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| CN107556954A (en) * | 2017-09-12 | 2018-01-09 | 四川力通复合材料科技有限公司 | A kind of aramid fiber cellular composite material epoxy structural rubber and preparation method thereof |
| CN110643150A (en) * | 2019-09-30 | 2020-01-03 | 哈尔滨玻璃钢研究院有限公司 | High-strength heat-resistant resin matrix and method for efficiently preparing high-performance composite material by using same |
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2020
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1197098A (en) * | 1997-04-24 | 1998-10-28 | 中国科学院低温技术实验中心 | Low temp. adhesive and firming agent used for low temp. adhesive |
| CN106753132A (en) * | 2016-12-29 | 2017-05-31 | 南通高盟新材料有限公司 | A kind of halogen-free flame-resistant high-temperature-resistant tough epoxy adhesive and preparation method thereof |
| CN107556954A (en) * | 2017-09-12 | 2018-01-09 | 四川力通复合材料科技有限公司 | A kind of aramid fiber cellular composite material epoxy structural rubber and preparation method thereof |
| CN110643150A (en) * | 2019-09-30 | 2020-01-03 | 哈尔滨玻璃钢研究院有限公司 | High-strength heat-resistant resin matrix and method for efficiently preparing high-performance composite material by using same |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113845755A (en) * | 2021-10-13 | 2021-12-28 | 哈尔滨玻璃钢研究院有限公司 | Environment-friendly high-performance multifunctional resin matrix and preparation method of composite material thereof |
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