CN115385879A - Furyl diamine and synthesis method thereof - Google Patents
Furyl diamine and synthesis method thereof Download PDFInfo
- Publication number
- CN115385879A CN115385879A CN202211116160.3A CN202211116160A CN115385879A CN 115385879 A CN115385879 A CN 115385879A CN 202211116160 A CN202211116160 A CN 202211116160A CN 115385879 A CN115385879 A CN 115385879A
- Authority
- CN
- China
- Prior art keywords
- furan
- furyldiamine
- reaction
- furandicarboxamide
- synthesizing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/66—Nitrogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Furan Compounds (AREA)
Abstract
The invention belongs to the field of chemical synthesis, and discloses furyl diamine and a synthesis method thereof. The molecular structure general formula of the furyl diamine is as follows:
the pendant group being-NH 2 Two at four positions 2,3,4,5 on the furan ring and at the same time at B 1 And B 4 、B 1 And B 3 Or B 2 And B 3 . Dissolving a furan side-based monomer in ammonia water for esterification reaction, dissolving the obtained furan diformamide in a solvent, adding a weak base and an oxidant for reaction, dissolving the obtained furan diformamide ester in a strong alkali water solution for reaction, extracting and drying to obtain the furan diamine. The invention takes furan two-side-group monomer as raw material, adds amino group through acid-base neutralization reaction, rearranges the amino group through Hofmann degradation reaction, and finally utilizes strong baseBreaking the amide group gives the furanyldiamine. The furyl diamine can be applied to the synthesis of high-performance substances such as polyimide and the like.
Description
Technical Field
The invention belongs to the field of chemical synthesis, and particularly relates to furyldiamine and a synthesis method thereof.
Background
Biomass is one of the most abundant renewable resources, considered as a unique and promising candidate resource, and development and research on biomass are hot today. The furan biomass is a large important component of a biomass family, and currently, much attention is paid to 2, 5-furandimethanol (BHF), 5, hydroxymethylfurfural (5-HMF), furfural (HMFA) and 2, 5-furandicarboxylic acid (FDCA), wherein the FDCA is listed as one of 12 chemicals with the highest biomass value increment by the U.S. department of energy, and has a wide application prospect. Modification studies of biomass are currently focused mainly on the localized design of pendant groups, and techniques that have been developed so far, such as reduction of HMFA to tetrahydrofuran, modification of BHF to terephthalic acid (PTA) by suzuki coupling, and the like. Research on the modification of biomass into specialty materials is still rare.
Polyimide, which is one of the most top heat-resistant plastics, has ultralow dielectric loss and excellent chemical stability, is widely applied to the advanced fields of aerospace, high and new electronics and the like, gradually permeates into the field of photoresist, and has huge market demand. However, polyimide has high production cost and high processing difficulty, is in a state of short supply and short demand all the time, and has a high price. Polyimide is generally obtained by the polymerization reaction of dianhydride and diamine, wherein the diamine is widely used at present as p-phenylenediamine (PPD), 4-diaminodiphenyl ether (ODA) and the like, which are petroleum-based chemical products, consume fossil energy, pollute the environment and have higher price.
Disclosure of Invention
In order to solve the defects and shortcomings of the prior art, the invention provides furyldiamine. The furyl diamine is novel biomass diamine, has chemical properties similar to PPD, is prepared from natural biomass as a synthetic raw material, has wide source and little damage to the environment, and is an effective substitute of diamine.
The invention also aims to provide a synthesis method, which is a catalytic conversion route for converting biomass resources into important chemical raw materials, can realize the conversion of biomass furan-di-side-group monomers into furyldiamine, and can be used for synthesizing high-performance polymers such as polyimide and the like.
The purpose of the invention is realized by the following technical scheme:
a furyldiamine, the molecular structure general formula of the furyldiamine is:
the side group is-NH 2 Two at four positions 2,3,4,5 of the furan ring and at the same time at B 1 And B 4 、B 1 And B 3 Or B 2 And B 3 。
The synthetic method of the furyl diamine comprises the following specific steps:
s1, dissolving a furan side-group monomer in ammonia water, carrying out esterification reaction for 2-6 h at 50-70 ℃, and evaporating the solvent to dryness to obtain furan dicarboxamide;
s2, dissolving furandicarboxamide in a solvent, adding a weak base and an oxidant, reacting at 5-70 ℃ for 20 min-24 h, filtering after the reaction is finished, collecting filtrate, and drying to obtain furandicarboxamide ester;
s3, dissolving furandicarboxamide ester in a strong alkali aqueous solution, reacting for 2-6 h at 50-90 ℃, collecting reaction liquid, extracting with ethyl acetate, separating liquid, collecting supernatant, and drying to obtain the furyldiamide.
Preferably, the furan-pendant monomer described in step S1 is 2, 5-furandicarboxylic acid, 2, 4-furandicarboxylic acid, 3, 4-furandicarboxylic acid, 2, 5-furandicarboxaldehyde, 2, 4-furandicarboxaldehyde, or 3, 4-furandicarboxaldehyde.
Preferably, the molar ratio of the furan-pendant-based monomer and the ammonia water in the step S1 is 1 (2-30).
Preferably, the oxidant in step S2 is N-bromosuccinimide or dichlorodimethyl hydantoin; the weak base is sodium methoxide or 1, 8-diazabicycloundec-7-ene; the solvent is methanol, tetrahydrofuran or acetone.
Preferably, the molar ratio of the furandicarboxamide, the oxidant and the weak base in the step S2 is 1 (1-5) to (1-10).
Preferably, the molar ratio of the furandicarboxamide ester to the strong base in the strong base aqueous solution in the step S3 is 1 (1-10).
Preferably, the strong base in step S3 is sodium hydroxide, choline or dodecyltrimethylammonium chloride.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention takes a furan side-group monomer as a raw material, adds amino through acid-base neutralization reaction, rearranges the amino through Hofmann degradation reaction, and finally breaks an amide group with strong base to obtain the furyldiamine.
2. The raw materials used in the invention are biomass materials, the resources are wide and easy to obtain, and the method is environment-friendly.
3. The furyldiamine synthesized by the method can be applied to synthesis of high-performance substances such as polyimide and the like, and has wide prospect.
Drawings
FIG. 1 is a schematic diagram of the structure of furanyldiamine according to the invention;
FIG. 2 is a schematic diagram of the synthetic route of furyldiamine in example 1-2.
FIG. 3 is a schematic diagram of the synthetic route of furyldiamine in example 3.
FIG. 4 is a schematic diagram of the synthetic route of furyldiamine in example 4.
Detailed Description
The following examples are presented to further illustrate the present invention and should not be construed as limiting the invention. Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Example 1
1. Placing 8g of 2, 5-furandicarboxylic acid (FDCA) and 5mL of ammonia water in a three-neck flask, stirring for 4h at 60 ℃, collecting reaction liquid after the reaction is finished, transferring the reaction liquid to a 50 ℃ oven, and drying in vacuum to obtain light yellow powder solid 2, 5-furandicarboxamide.
2. 2g of 2, 5-furandicarboxamide and 10mL of methanol were poured into a beaker, which was placed on a stirring table and transferred to a refrigerator at 8 ℃, to which 2.5g of N-bromosuccinimide (NBS) was added, and the solution was orange-yellow; then 3mL of 1, 8-diazabicycloundecen-7-ene (DBU) is dropwise added into the mixture, the solution gradually becomes orange red, the color fades to be colorless after the DBU is dropwise added, the temperature is kept for reaction for 20 hours after the DBU is added, the mixture is taken out, filtered and collected, and the filtrate is transferred to a 60 ℃ oven to be dried to constant weight, so that viscous light yellow liquid, namely the 2, 5-furandicarboxamide ester, is obtained.
3. 0.22g of sodium hydroxide was dissolved in 5mL of water and heated to 60 ℃ to which 1.07g of 2, 5-furandicarboxamide ester was added, and stirring was started to rapidly dissolve the 2, 5-furandicarboxamide ester, and the temperature was maintained for reaction for 4 hours. After the reaction, 5mL of ethyl acetate was added, the mixture was transferred to a separatory funnel to collect the upper oily liquid, the lower liquid was collected, 5mL of ethyl acetate was added again to the lower liquid, the above extraction and separation were repeated 3 times, the obtained upper oily liquids were collected, and the mixture was dried in an oven at 60 ℃ to a constant weight to obtain 2, 5-diaminofuran.
Example 2
1. Mixing 8g of FDCA and 5mL of ammonia water, stirring for 4h at 60 ℃, collecting reaction liquid after the reaction is finished, and transferring the reaction liquid to a 50 ℃ oven for vacuum drying to obtain light yellow powder solid 2, 5-furandicarboxamide.
2. 2g of 2, 5-furandicarboxamide and 10mL of methanol were mixed, placed on a stirring table and heated to 60 ℃, 3g of dichlorodimethylhydantoin (DCDMH) was added thereto, and the solution was orange-yellow; sodium methoxide was then slowly added thereto (the order of addition of sodium methoxide and DCDMH was not changed, and if the order of addition of sodium methoxide and DCDMH was wrong, the solution solidified after the addition of sodium methoxide, which resulted in the mixture not being uniformly blended), and the solution was pale yellow. After the addition, the temperature is kept for reaction for 30min, the mixture is taken out, filtered and collected, and the filtrate is transferred to a 60 ℃ oven to be dried to constant weight, so that viscous light yellow liquid, namely the 2, 5-furandicarboxamide ester, is obtained.
3. 0.22g of sodium hydroxide is weighed, dissolved in 5mL of water, heated to 60 ℃, 1.07g of 2, 5-furandicarboxamide ester is added, stirring is started, the 2, 5-furandicarboxamide ester is rapidly dissolved, and the temperature is maintained for reaction for 4 hours. After the reaction, 5mL of ethyl acetate was added, the mixture was transferred to a separatory funnel to collect the upper oily liquid and the lower liquid, 5mL of ethyl acetate was added again to the lower liquid, the above extraction and separation operations were repeated 3 times, the obtained upper oily liquids were pooled and dried in an oven at 60 ℃ to constant weight to obtain 2, 5-diaminofuran.
Example 3
1. 8g of 2, 4-furandicarboxylic acid and 10mL of ammonia water are mixed, stirred for 4 hours at 60 ℃, and after the reaction is finished, the reaction solution is collected and transferred to a 50 ℃ oven for vacuum drying to obtain light yellow powder solid 2, 4-furandicarboxamide.
2. Taking 2g of 2, 4-furandicarboxamide, adding 10mL of methanol, placing the mixture on a stirring table, transferring the mixture to a refrigerator at 8 ℃, adding 3g of NBS into the mixture, and enabling the solution to be orange yellow; then 3mL of DBU is added dropwise, the solution gradually becomes orange-red, and the color fades to be colorless after the DBU is added dropwise. After the addition, the temperature is kept for reaction for 20 hours, the mixture is taken out, filtered and collected, and is transferred to a 60 ℃ oven to be dried to constant weight, so that viscous light yellow liquid, namely the 2, 4-furandicarboxamide ester, is obtained.
3. 0.6g of choline was weighed, added to 5mL of water, heated to 60 ℃ and 1.07g of 2, 4-furandicarboxamide ester was added thereto, and stirring was started to rapidly dissolve the 2, 4-furandicarboxamide ester, and the temperature was maintained to react for 4 hours. After the reaction, 5mL of ethyl acetate was added, the mixture was transferred to a separatory funnel to collect the upper oily liquid and the lower liquid, 5mL of ethyl acetate was added again to the lower liquid, the above extraction and separation operations were repeated 3 times, the obtained upper oily liquids were collected and dried in an oven at 60 ℃ to a constant weight, and 2, 4-diaminofuran was obtained.
Example 4
1. Mixing 8g of 3, 4-furandicarboxylic acid with 10mL of ammonia water, stirring at 60 ℃ for 4h, collecting the reaction solution after the reaction is finished, and transferring the reaction solution to a 50 ℃ oven for vacuum drying to obtain light yellow powder solid 3, 4-furandicarboxamide.
2. Taking 2g of 3, 4-furandicarboxamide, adding 10mL of methanol, placing the mixture on a stirring table, transferring the mixture to a refrigerator at 8 ℃, adding 3g of NBS into the mixture, and enabling the solution to be orange yellow; then, 3mL of DBU was added dropwise thereto, the solution gradually became orange-red, and the color faded to be colorless after the addition of DBU was completed. After the addition, the temperature is kept for reaction for 20h, the mixture is taken out, filtered and collected, and the filtrate is transferred to a 60 ℃ oven to be dried to constant weight, so that viscous light yellow liquid, namely the 3, 4-furandicarboxamide ester, is obtained.
3. 0.6g of choline is weighed out and added to 5mL of water and heated to 60 ℃ and 1.07g of 3, 4-furandicarboxamide ester is added thereto and stirring is started to dissolve the 3, 4-furandicarboxamide ester rapidly, and the temperature is maintained for reaction for 4 hours. After the reaction, 5mL of ethyl acetate was added, the mixture was transferred to a separatory funnel to collect the upper oily liquid and the lower liquid, 5mL of ethyl acetate was added again to the lower liquid, the above extraction and separation operations were repeated 3 times, the obtained upper oily liquids were collected and dried in an oven at 60 ℃ to constant weight, and 3, 4-diaminofuran was obtained.
FIG. 1 is a reaction scheme for the conversion of a furan diradical monomer of the present invention to a furyldiamine; as can be seen from FIG. 1, (a) is the structural formula of the monomer with furan di-side group, A x Represents a carboxyl group or an aldehyde group (x = 1-4), the two side groups are located at 2,5 sites or 2,4 sites or 3,4 sites of the furan ring, (B) is a furyldiamine structural formula, B x Represents an amino group (x = 1-4), and the two pendant groups are located at the 2,5 position or the 2,4 position or the 3,4 position of the furan ring and correspond to the two group positions of the furandi-pendant group monomer before conversion.
FIG. 2 is a schematic diagram of the synthetic route of furyldiamine in example 1-2. As can be seen from FIG. 2, 5-furandicarboxylic acid as a furan-bis-side-group monomer is heated in ammonia water to perform esterification reaction to obtain 2, 5-furandicarboxamide, then subjected to Hofmann rearrangement reaction under the catalytic action of an oxidant and a weak base, the positions of carbonyl and amino are exchanged, and finally, amide bond is broken in a strong base solution to obtain 2, 5-diaminofuran.
FIG. 3 is a schematic diagram of the synthetic route of furyldiamine in example 3. As can be seen from FIG. 3, 2, 4-furandicarboxylic acid as a furan side-group monomer is heated in ammonia water to perform esterification reaction to obtain 2, 4-furandicarboxamide, then a Hofmann rearrangement reaction is performed under the catalysis of an oxidant and a weak base, the positions of carbonyl and amino are exchanged, and finally an amido bond is broken in a strong base solution to obtain 2, 4-diaminofuran.
FIG. 4 is a schematic diagram of the synthetic route of furyldiamine in example 4. As can be seen from FIG. 4, 3, 4-furandicarboxylic acid as a furan-bis-side-group monomer is heated in ammonia water to perform esterification reaction to obtain 3, 4-furandicarboxamide, then subjected to Hofmann rearrangement reaction under the catalytic action of an oxidant and a weak base, the positions of carbonyl and amino are exchanged, and finally, amide bond is broken in a strong base solution to obtain 3, 4-diaminofuran.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations and simplifications are intended to be included in the scope of the present invention.
Claims (8)
1. A furyldiamine, characterized in that the molecular structure general formula of the furyldiamine is:
the side group is-NH 2 Two at four positions 2,3,4,5 on the furan ring and at the same time at B 1 And B 4 、B 1 And B 3 Or B 2 And B 3 。
2. The method for synthesizing furyldiamine according to claim 1, comprising the following steps:
s1, dissolving a furan side-group monomer in ammonia water, carrying out esterification reaction for 2-6 h at 50-70 ℃, and evaporating the solvent to dryness to obtain furandicarboxamide;
s2, dissolving furandicarboxamide in a solvent, adding a weak base and an oxidant, reacting at 5-70 ℃ for 20 min-24 h, filtering after the reaction is finished, collecting filtrate, and drying to obtain furandicarboxamide ester;
s3, dissolving furandicarboxamide ester in a strong alkali aqueous solution, reacting for 2-6 h at 50-90 ℃, collecting reaction liquid, extracting with ethyl acetate, separating liquid, collecting supernatant, and drying to obtain the furyldiamide.
3. The method for synthesizing furyldiamine according to claim 2, wherein the furan-side-group monomer in step S1 is 2, 5-furandicarboxylic acid, 2, 4-furandicarboxylic acid, 3, 4-furandicarboxylic acid, 2, 5-furandicarboxaldehyde, 2, 4-furandicarboxaldehyde, or 3, 4-furandicarboxaldehyde.
4. The method for synthesizing furyldiamine according to claim 2, wherein the molar ratio of the furan-pendant monomer and the ammonia water in step S1 is 1 (2-30).
5. The method for synthesizing furyldiamine according to claim 2, wherein the oxidizing agent in step S2 is N-bromosuccinimide or dichlorodimethylhydantoin; the weak base is sodium methoxide or 1, 8-diazabicycloundec-7-ene; the solvent is methanol, tetrahydrofuran or acetone.
6. The method for synthesizing furyldiamine according to claim 2, wherein the molar ratio of the furandicarboxamide, the oxidant and the weak base in step S2 is 1 (1-5) to (1-10).
7. The method for synthesizing furyldiamide according to claim 2, wherein the molar ratio of the furandicarboxamide ester to the strong base in the aqueous solution of the strong base in step S3 is 1 (1-10).
8. The method for synthesizing furyldiamine according to claim 2, wherein the strong base in step S3 is sodium hydroxide, choline or dodecyl trimethyl ammonium chloride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211116160.3A CN115385879A (en) | 2022-09-14 | 2022-09-14 | Furyl diamine and synthesis method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211116160.3A CN115385879A (en) | 2022-09-14 | 2022-09-14 | Furyl diamine and synthesis method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115385879A true CN115385879A (en) | 2022-11-25 |
Family
ID=84126744
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211116160.3A Pending CN115385879A (en) | 2022-09-14 | 2022-09-14 | Furyl diamine and synthesis method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115385879A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115960061A (en) * | 2022-12-13 | 2023-04-14 | 慧迈材料科技(广东)有限公司 | Synthesis method and application of biomass-based diamine |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111100012A (en) * | 2019-12-16 | 2020-05-05 | 上海交通大学 | Method for preparing m-phenylenediamine |
| CN112812019A (en) * | 2021-01-28 | 2021-05-18 | 上海呼龙科技开发有限公司 | Preparation method of o-phenylenediamine |
| CN112978709A (en) * | 2019-12-12 | 2021-06-18 | 中国科学院大连化学物理研究所 | Carbon quantum dot precursor composition, carbon quantum dot and preparation method thereof |
-
2022
- 2022-09-14 CN CN202211116160.3A patent/CN115385879A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112978709A (en) * | 2019-12-12 | 2021-06-18 | 中国科学院大连化学物理研究所 | Carbon quantum dot precursor composition, carbon quantum dot and preparation method thereof |
| CN111100012A (en) * | 2019-12-16 | 2020-05-05 | 上海交通大学 | Method for preparing m-phenylenediamine |
| CN112812019A (en) * | 2021-01-28 | 2021-05-18 | 上海呼龙科技开发有限公司 | Preparation method of o-phenylenediamine |
Non-Patent Citations (1)
| Title |
|---|
| 胡炳成 等: "一种合成3,5-二氨基吡啶及3,5-二甲氧羰基氨基吡啶的新路线", 《应用化学》, vol. 29, no. 1, pages 504 - 506 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115960061A (en) * | 2022-12-13 | 2023-04-14 | 慧迈材料科技(广东)有限公司 | Synthesis method and application of biomass-based diamine |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104817691B (en) | Polyene ether compounds and preparation method thereof | |
| CN115385879A (en) | Furyl diamine and synthesis method thereof | |
| CN109384775A (en) | A kind of biological base epoxy presoma and its preparation method and application containing cyclic amide structure | |
| CN107857746B (en) | Furanodioic acid monomer, soluble aromatic polyamide and cross-linked polyamide capable of being repeatedly processed, and preparation method and application thereof | |
| CN103980486A (en) | Preparation method of nylon | |
| CN107868243A (en) | The preparation method of the phosphorous acid water reducer of one derived from amino acid | |
| US10745515B2 (en) | Biomass-based epoxy resin and preparation method thereof | |
| CN109180492B (en) | Rosin benzocyclobutene monomer capable of free radical polymerization, preparation method and application thereof | |
| CN104072471A (en) | Green catalysis preparation method for 14-aryl group-14 H-dibenzo [a, j] xanthene type derivative | |
| CN103030803B (en) | Biologic polyamide quadripolymer and synthesis method thereof | |
| CN102250318A (en) | Full-rosinyl epoxy resin composite and condensate thereof | |
| CN111944143B (en) | Bio-based polyarylether resin containing furan ring structure and preparation method thereof | |
| CN105837812A (en) | Aliphatic-aromatic-copolymerization-type carborane polyester and preparing method thereof | |
| CN109384748A (en) | Biological base epoxy based on natural amino acid and its preparation method and application | |
| CN113214482A (en) | Preparation method of lipoic acid compound polymer | |
| CN109651955B (en) | Preparation method of acetoacetate-based modified castor oil cured coating | |
| CN102086181A (en) | Synthesis method of 2,2'-diaryl-4,4',5,5'-biphenyl tetraacid dianhydride monomer | |
| CN106046363B (en) | One kind is containing fluorene structured high dissolubility Nomex of tetramethoxy and preparation method thereof | |
| CN103554489B (en) | Azobenzene polymer, preparation method and the usage | |
| CN103819308A (en) | Solidifiable poly-meta-phenylene as well as preparation method and application thereof | |
| CN109776518B (en) | Novel AB type benzoxazine monomer and preparation method thereof | |
| CN110563943A (en) | Bio-based polymer and preparation method thereof | |
| CN109867784B (en) | Method for catalytically synthesizing polyaspartic acid by grafting sulfomontmorillonite on surface | |
| CN105153407A (en) | Thermosetting rosinyl resin composition and preparation method thereof | |
| CN102977300A (en) | Preparation method of maleated rosin glycerin ester phenol formaldehyde resin |
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 |