CN116903829A - Quick curing agent for epoxy resin and preparation method thereof - Google Patents

Quick curing agent for epoxy resin and preparation method thereof Download PDF

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Publication number
CN116903829A
CN116903829A CN202310901519.6A CN202310901519A CN116903829A CN 116903829 A CN116903829 A CN 116903829A CN 202310901519 A CN202310901519 A CN 202310901519A CN 116903829 A CN116903829 A CN 116903829A
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CN
China
Prior art keywords
curing agent
epoxy resin
triethylene tetramine
modified compound
aminoethyl
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Pending
Application number
CN202310901519.6A
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Chinese (zh)
Inventor
陈杰
伊良文
王永刚
薛同妹
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Feirongda Technology Jiangsu Co ltd
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Feirongda Technology Jiangsu Co ltd
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Priority to CN202310901519.6A priority Critical patent/CN116903829A/en
Publication of CN116903829A publication Critical patent/CN116903829A/en
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00Polycondensates 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
    • C08G59/18Macromolecules 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
    • C08G59/40Macromolecules 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
    • C08G59/50Amines
    • C08G59/5006Amines aliphatic
    • C08G59/502Polyalkylene polyamines
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00Polycondensates 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
    • C08G59/18Macromolecules 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
    • C08G59/40Macromolecules 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
    • C08G59/50Amines
    • C08G59/5006Amines aliphatic
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00Polycondensates 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
    • C08G59/18Macromolecules 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
    • C08G59/40Macromolecules 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
    • C08G59/50Amines
    • C08G59/5046Amines heterocyclic
    • C08G59/5053Amines heterocyclic containing only nitrogen as a heteroatom
    • C08G59/5073Amines heterocyclic containing only nitrogen as a heteroatom having two nitrogen atoms in the ring
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00Polycondensates 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
    • C08G59/18Macromolecules 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
    • C08G59/68Macromolecules 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 catalysts used
    • C08G59/686Macromolecules 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 catalysts used containing nitrogen

Abstract

The invention relates to the technical field of epoxy resin curing agents, in particular to a rapid curing agent for epoxy resin and a preparation method thereof; comprises triethylene tetramine, diethylene triamine, N-aminoethylpiperazine and a curing agent modified compound; the quick curing agent can be uniformly mixed with epoxy resin, and then can realize quick curing in a mold, the curing time can be shortened to 2 minutes or less, and the impact strength of the cured product is improved compared with the prior art. According to the invention, the 1, 4-piperazine diethylamine is added into triethylene tetramine, so that the curing speed of the triethylene tetramine can be improved, and the main chain of the molecular chain of the triethylene tetramine contains cyclic molecules, so that the structure is stable, and cracks caused by internal stress can be prevented in the rapid curing process of epoxy resin. And the 1, 4-piperazine diethylamine is completely compatible with the N, N-di (2-aminoethyl) -1, 2-ethylenediamine, is favorable for uniformly dispersing and mixing the 1, 4-piperazine diethylamine in triethylene tetramine, and can further fully play a promoting role.

Description

Quick curing agent for epoxy resin and preparation method thereof
Technical Field
The invention relates to the technical field of epoxy resin curing agents, in particular to a rapid curing agent for epoxy resin and a preparation method thereof.
Background
The rapid development of epoxy resins benefits on the one hand from its own excellent properties and on the other hand from its characteristic process diversity (coating, dipping, pouring, spraying, injection, moulding, etc.) and product diversity (versatility). The epoxy resin is applied by a compounding technology, except equipment and technology, the most important is the formula design, and the realization of perfect formula design requires the selection and combination of the epoxy resin, the curing agent and the related additives; in particular, the curing agent, once the epoxy resin is determined, plays a decisive role in the manufacturability of the epoxy resin composition and in the final properties of the cured product (product).
In recent years, in some application fields with a relatively high front, higher requirements are put on curing agents, such as HP-RTM process (High Pressure Resin Transfer Molding, high-pressure resin transfer molding process), and short-cycle (mass) and high-quality production is required. Although epoxy cure systems have been reduced from the initial cure time of 8 minutes to 5 minutes to the current 3 minute cure, it is desirable to have faster processing without affecting other properties of the cured product, particularly toughness. Because faster curing speeds tend to bring about faster curing shrinkage, faster physical changes in cooling shrinkage produce more internal stress, and when the internal stress exceeds the strength of the cured product, cracks are generated inside the cured product, resulting in a significant decrease in the mechanical strength, particularly toughness, of the product.
Therefore, a compounding technology of a curing system needs to be developed, so that the production process can be fast, and the service performance of the product can be not influenced or even improved.
Disclosure of Invention
The purpose of the invention is that: a fast curing agent for epoxy resins is provided for solving at least one of the above-mentioned technical problems.
In order to solve the technical problems, the invention adopts the following technical scheme:
the quick curing agent for the epoxy resin comprises the following components in parts by mass:
100 parts of triethylene tetramine, 30-50 parts of diethylenetriamine, 0.5-1 part of N-aminoethylpiperazine and 5-10 parts of curing agent modified compound, wherein the curing agent modified compound comprises N, N-di (2-aminoethyl) -1, 2-ethylenediamine and 1, 4-piperazine diethylamine.
Further, the mass ratio of the N, N-di (2-aminoethyl) -1, 2-ethylenediamine to the 1, 4-piperazine diethylamine in the curing agent modified compound is 1:1-2.
Another object of the invention is: a method for preparing a fast curing agent for epoxy resin is provided for solving at least one of the above technical problems.
In order to solve the technical problems, the invention adopts the following technical scheme:
a method of preparing a rapid curing agent for an epoxy resin, the method comprising the steps of:
s1, preparation of a curing agent modified compound: uniformly mixing N, N-di (2-aminoethyl) -1, 2-ethylenediamine and 1, 4-piperazine diethylamine to form a curing agent modified compound;
s2, preparation of an epoxy resin curing agent: uniformly mixing triethylene tetramine, diethylene triamine, N-aminoethylpiperazine and the curing agent modified compound prepared in the step S1 to prepare an epoxy resin rapid curing agent;
wherein the weight portions of the components are as follows: 100 parts of triethylene tetramine, 30-50 parts of diethylene triamine, 0.5-1 part of N-aminoethylpiperazine and 5-10 parts of curing agent modified compound.
Further, the stirring temperature in the step S2 is 10-40 ℃, and the stirring speed is 50-120 r/min.
Further, in the step S1, the mass ratio of the N, N-di (2-aminoethyl) -1, 2-ethylenediamine to the 1, 4-piperazine diethylamine is 1:1-2.
Further, the preparation of the curing agent modified compound in the step S1 comprises the following steps: n, N-di (2-aminoethyl) -1, 2-ethylenediamine and 1, 4-piperazine diethylamine are put into a stirring device and stirred uniformly at the speed of 50r/min-120r/min at 50 ℃ to prepare the curing agent modified compound.
The technical scheme of the invention has the beneficial effects that:
the quick curing agent can be uniformly mixed with epoxy resin, and then can realize quick curing in a mold, the curing time can be shortened to within 2 minutes, and the impact strength of the cured product is improved compared with the prior product.
The invention adopts the mixture of N, N-di (2-aminoethyl) -1, 2-ethylenediamine and 1, 4-piperazine diethylamine as the curing agent modification compound, wherein the 1, 4-piperazine diethylamine is not only an amine curing agent, but also an amine curing agent accelerator, and the curing speed of triethylene tetramine can be improved by adding the 1, 4-piperazine diethylamine into the triethylene tetramine. In addition, the molecular chain main chain of the 1, 4-piperazine diethylamine contains cyclic molecules, has stable structure and can prevent internal stress from generating cracks in the process of rapidly curing the epoxy resin. And the 1, 4-piperazine diethylamine is completely compatible with the N, N-di (2-aminoethyl) -1, 2-ethylenediamine, which is favorable for uniformly dispersing and mixing the 1, 4-piperazine diethylamine in triethylene tetramine, and the compatibility problem among all components is not worried, so that the promotion effect of the 1, 4-piperazine diethylamine can be further fully exerted. N, N-bis (2-aminoethyl) -1, 2-ethylenediamine is also an amine curing agent, and its molecular structure contains long flexible branched molecules, which can improve the toughness of the cured product. Therefore, the N, N-di (2-aminoethyl) -1, 2-ethylenediamine and 1, 4-piperazine diethylamine are used together, so that the curing speed can be improved in terms of technology, and the impact strength can be improved in terms of performance.
Detailed Description
The present invention is not limited to the following embodiments, and those skilled in the art can implement the present invention in various other embodiments according to the present invention, or simply change or modify the design structure and thought of the present invention, which fall within the protection scope of the present invention. It should be noted that, without conflict, the embodiments of the present invention and features of the embodiments may be combined with each other.
The sources of the raw materials in the invention are as follows:
triethylene tetramine, D100059, shanghai aladine Biochemical technologies Co., ltd;
diethylenetriamine, D301794, shanghai aladine Biochemical technologies Co., ltd;
n-aminoethylpiperazine, A101279, shanghai Ala Biochemical technologies Co., ltd;
n, N-bis (2-aminoethyl) -1, 2-ethylenediamine, T106669, shanghai Ala Di Biochemical technologies Co., ltd;
1, 4-piperazine diethylamine, D589798, shanghai aladine Biochemical technologies Co., ltd;
epoxy resin, E-51, from the chemical Co., ltd.
The structural formula of the 1, 4-piperazine diethylamine is
The structural formula of the N, N-di (2-aminoethyl) -1, 2-ethylenediamine is
The quick curing agent for the epoxy resin comprises the following components in parts by mass:
100 parts of triethylene tetramine, 30-50 parts of diethylenetriamine, 0.5-1 part of N-aminoethylpiperazine and 5-10 parts of curing agent modified compound, wherein the curing agent modified compound comprises N, N-di (2-aminoethyl) -1, 2-ethylenediamine and 1, 4-piperazine diethylamine.
The principle of the compound modification of the curing agent in the invention is as follows: the 1, 4-piperazine diethylamine is not only an amine curing agent, but also can be used as an amine curing agent accelerator, and after being added into triethylene tetramine, the curing speed of the triethylene tetramine can be improved. In addition, the main chain of the molecular chain contains cyclic molecules, so that the structure is stable, and the internal stress can be prevented from generating cracks in the rapid curing process of the epoxy resin. And the 1, 4-piperazine diethylamine is completely compatible with the N, N-di (2-aminoethyl) -1, 2-ethylenediamine, which is favorable for uniformly dispersing and mixing the 1, 4-piperazine diethylamine in triethylene tetramine, and can further fully play the promotion effect of the 1, 4-piperazine diethylamine. N, N-bis (2-aminoethyl) -1, 2-ethylenediamine is also an amine curing agent, and its molecular structure contains long flexible branched molecules, which can improve the toughness of the cured product. Therefore, the N, N-di (2-aminoethyl) -1, 2-ethylenediamine and 1, 4-piperazine diethylamine are used together, so that the curing speed can be improved in terms of technology, and the impact strength can be improved in terms of performance.
Example 1:
preparing a curing agent modified compound: 3 g of N, N-bis (2-aminoethyl) -1, 2-ethylenediamine and 3 g of 1, 4-piperazine diethylamine were mixed and stirred at 120r/min at 50℃for 0.5 hour.
Preparing a rapid curing agent: 100 g of triethylene tetramine, 30 g of diethylenetriamine, 0.5 g of N-aminoethylpiperazine and 6 g of curing agent modification compound are mixed and stirred at room temperature (25 ℃) for 0.5 hours at 120r/min.
Preparing epoxy resin cured sample bars: 100 g of epoxy resin and 20 g of quick curing agent are uniformly mixed, injected into a mold and cured at 80 ℃ to prepare a resin matrix sample, and the relevant performance is tested, and the results are shown in table 1.
Example 2:
preparing a curing agent modified compound: 3 g of N, N-bis (2-aminoethyl) -1, 2-ethylenediamine and 6 g of 1, 4-piperazine diethylamine were mixed and stirred at 120r/min at 50℃for 0.5 hour.
Preparing a rapid curing agent: 100 g of triethylene tetramine, 30 g of diethylenetriamine, 1 g of N-aminoethylpiperazine and 9 g of curing agent modification compound are mixed and stirred at room temperature (25 ℃) for 0.5 hour at 120r/min.
Preparing epoxy resin cured sample bars: 100 g of epoxy resin and 20 g of quick curing agent are uniformly mixed, injected into a mold and cured at 80 ℃ to prepare a resin matrix sample, and the relevant performance is tested, and the results are shown in table 1.
Example 3:
preparing a curing agent modified compound: 5 g of N, N-bis (2-aminoethyl) -1, 2-ethylenediamine and 5 g of 1, 4-piperazine diethylamine were mixed and stirred at 120r/min at 50℃for 0.5 hours.
Preparing a rapid curing agent: 100 g of triethylene tetramine, 50 g of diethylenetriamine, 1 g of N-aminoethylpiperazine and 10 g of curing agent modified compound are mixed and stirred at room temperature and 120r/min for 0.5 hour.
Preparing epoxy resin cured sample bars: 100 g of epoxy resin and 20 g of quick curing agent are uniformly mixed, injected into a mold and cured at 80 ℃ to prepare a resin matrix sample, and the relevant performance is tested, and the results are shown in table 1.
Comparative example 1:
preparing a curing agent: 100 g of triethylene tetramine, 30 g of diethylenetriamine and 1 g of N-aminoethylpiperazine are mixed and stirred at room temperature and 120r/min for 0.5 hour.
Preparing epoxy resin cured sample bars: 100 g of epoxy resin and 20 g of quick curing agent are uniformly mixed, injected into a mold and cured at 80 ℃ to prepare a resin matrix sample, and the relevant performance is tested, and the results are shown in table 1.
Comparative example 2:
preparing a curing agent: 100 g of triethylene tetramine, 30 g of diethylenetriamine, 1 g of N-aminoethylpiperazine and 3 g of N, N-di (2-aminoethyl) -1, 2-ethylenediamine are mixed and stirred at room temperature for 0.5 hour at 120r/min.
Preparing epoxy resin cured sample bars: 100 g of epoxy resin and 20 g of quick curing agent are uniformly mixed, injected into a mold and cured at 80 ℃ to prepare a resin matrix sample, and the relevant performance is tested, and the results are shown in table 1.
Comparative example 3:
preparing a curing agent: 100 g of triethylene tetramine, 30 g of diethylenetriamine, 1 g of N-aminoethylpiperazine and 3 g of 1, 4-piperazine diethylamine were mixed and stirred at room temperature for 0.5 hour at 120r/min.
Preparing epoxy resin cured sample bars: 100 g of epoxy resin and 20 g of quick curing agent are uniformly mixed, injected into a mold and cured at 80 ℃ to prepare a resin matrix sample, the resin matrix sample is subjected to test related performance, the curing time is in accordance with standard GB/T22314, the unnotched impact strength is in accordance with standard GB/T1043, and the results are shown in Table 1.
Table 1 test items and test results
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made to the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention.

Claims (6)

1. A rapid curing agent for epoxy resins, characterized by: the rapid curing agent comprises the following components in parts by mass:
100 parts of triethylene tetramine, 30-50 parts of diethylenetriamine, 0.5-1 part of N-aminoethylpiperazine and 5-10 parts of curing agent modified compound, wherein the curing agent modified compound comprises N, N-di (2-aminoethyl) -1, 2-ethylenediamine and 1, 4-piperazine diethylamine.
2. A rapid curing agent for epoxy resins according to claim 1, characterized in that: the mass ratio of the N, N-di (2-aminoethyl) -1, 2-ethylenediamine to the 1, 4-piperazine diethylamine in the curing agent modified compound is 1:1-2.
3. A preparation method of a rapid curing agent for epoxy resin is characterized by comprising the following steps: the preparation method comprises the following steps:
s1, preparation of a curing agent modified compound: uniformly mixing N, N-di (2-aminoethyl) -1, 2-ethylenediamine and 1, 4-piperazine diethylamine to form a curing agent modified compound;
s2, preparation of an epoxy resin curing agent: uniformly mixing triethylene tetramine, diethylene triamine, N-aminoethylpiperazine and the curing agent modified compound prepared in the step S1 to prepare an epoxy resin rapid curing agent;
wherein the weight portions of the components are as follows: 100 parts of triethylene tetramine, 30-50 parts of diethylene triamine, 0.5-1 part of N-aminoethylpiperazine and 5-10 parts of curing agent modified compound.
4. A method for preparing a rapid curing agent for epoxy resins according to claim 3, characterized in that: the stirring temperature in the step S2 is 10-40 ℃, and the stirring speed is 50-120 r/min.
5. A method for preparing a rapid curing agent for epoxy resins according to claim 3, characterized in that: in the step S1, the mass ratio of the N, N-di (2-aminoethyl) -1, 2-ethylenediamine to the 1, 4-piperazine diethylamine is 1:1-2.
6. A method for preparing a rapid curing agent for epoxy resins according to claim 3, characterized in that: the preparation of the curing agent modified compound in the step S1 comprises the following steps: n, N-di (2-aminoethyl) -1, 2-ethylenediamine and 1, 4-piperazine diethylamine are put into a stirring device and stirred uniformly at the speed of 50r/min-120r/min at 50 ℃ to prepare the curing agent modified compound.
CN202310901519.6A 2023-07-21 2023-07-21 Quick curing agent for epoxy resin and preparation method thereof Pending CN116903829A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202310901519.6A CN116903829A (en) 2023-07-21 2023-07-21 Quick curing agent for epoxy resin and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202310901519.6A CN116903829A (en) 2023-07-21 2023-07-21 Quick curing agent for epoxy resin and preparation method thereof

Publications (1)

Publication Number Publication Date
CN116903829A true CN116903829A (en) 2023-10-20

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Family Applications (1)

Application Number Title Priority Date Filing Date
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Country Status (1)

Country Link
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