CN105801401A - Preparation and separation method of high-purity p-acrylic pimaric acid - Google Patents
Preparation and separation method of high-purity p-acrylic pimaric acid Download PDFInfo
- Publication number
- CN105801401A CN105801401A CN201610221929.6A CN201610221929A CN105801401A CN 105801401 A CN105801401 A CN 105801401A CN 201610221929 A CN201610221929 A CN 201610221929A CN 105801401 A CN105801401 A CN 105801401A
- Authority
- CN
- China
- Prior art keywords
- acrylic acid
- rosin
- preparation
- modified
- product
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/47—Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/353—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by isomerisation; by change of size of the carbon skeleton
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Developing Agents For Electrophotography (AREA)
Abstract
The invention relates to a preparation and separation method of high-purity p-acrylic pimaric acid and discloses a preparation and separation method of p-acrylic pimaric acid. The preparation and separation method comprises steps as follows: 1) rosin and acrylic acid are taken as raw materials and subjected to a Diels-Alder reaction under the microwave-assisted condition, and acrylic acid modified rosin is obtained; 2) acrylic pimaric acid is obtained through purification; 3) a p-acrylic pimaric acid product is prepared from the acrylic acid modified rosin or acrylic pimaric acid serving as a raw material through cyclodextrin modified silica gel column chromatography with benzene and ethyl acetate in different volume ratios as developing solvents and has the purity higher than 95%. The method is simple, convenient, efficient and high in repeatability, the obtained p-acrylic pimaric acid has high purity and can be used as a high-purity chemical material or an intermediate, and additional utilization values of rosin can be effectively increased.
Description
Technical field
The present invention relates to the preparation method of a kind of rosin derivative rosin acrylic acid, particularly to a kind of p-propylene sea
Pine acid (para-position rosin acrylic acid) purity product more than 95% and preparation method thereof.
Background technology
Colophonium is that the Renewable resource that China is important, yield and export volume are sure to occupy the first in the world always, but profound adds
Chemical product is fewer, therefore develops the high value added product of Colophonium, significant to China's Gum Rosin Industry.
The main component of Colophonium is resinic acid, and resinic acid usually contains a carboxyl functional group.By chemical modification, tree
The carboxyl of fat acid can occur various structures to change, and forms multiple abietyl and derives chemicals.Rosin acrylic acid is
The modified product of Colophonium, containing two carboxyl functional groups, can prepare various new colophony based functional by modification
Property derivant (COATES G W, HILLMYER M A.A virtual tissue of macromolecules:
“Polymers from renewable resources”.Macromolecules,2009,42(21):7987-7989；
STANKIEWICZ-DROGON A, PALCHYKOVSKA L G, KOSTINA V G, et a1.New
acridone-4-carboxylic acid derivatives as potential inhibitors of hepatitis C virus
Infection.Bioorganic&Medicinal Chemistry, 2008,16 (19): 8846-8852), at coating, gather
The aspects such as urethane resin, adhesive have good application prospect (LIU Xiao-qing, XIN Wen-bo,
ZHANG Jin-wen.Rosin-derived imide-diacids as epoxy curing agents for enhanced
performance.Bioresource Technology,2010,101(7):2520–2524；LIU X Q,HUANG
W,JIANG Y H,et al.Preparation of a bio-based epoxy with comparable properties to
those of petroleum-based counterparts.Express Polymer Letters,2012,6(4):
293–298)。
Although rosin acrylic acid (APA) the most at home and abroad has certain report, but all there is reaction condition
Harsh, conversion efficiency is low, the shortcoming of poor product quality, as far back as 1961, (Noah J H, the John A such as Noah
W,Ray V L.A preparation and some of the reactions of the Diels-Alder adducts of
levopimaric acid and acrylonitrile.Journal of Organic Chemistry,1961,26(8):
2641-2643) just it is prepared for acrylic acid modified rosin by Diels-Alder reaction, and rosin acrylic acid is carried out
Isolated and purified, obtain rosin acrylic acid.(the Aldrich P H.Process for separation of such as Aldrich
Rosin adducts from mixtures with rosin:US, 3562243.1971) acrylic acid prepared is changed
Property Colophonium, obtain rosin acrylic acid with methanol, normal heptane and water by the method for extraction is isolated and purified.Ioan(Ioan
B.Polymers from a levopimaric acid-acrylic acid Diels-Alder adduct:Synthesis and
characterization[J].Journal of Polymer Science Part A:Polymer Chemistry,2007,45
(24): 5979-5990) on the basis of petroleum ether prepares acrylic acid modified rosin, third has been separated with acetone recrystallization
Alkene dextropimaric acid.Xie Hui (Xie Hui. the research of acrylic acid modified rosin synthesis of polyurethane coating. Nanjing: Nanjing forestry
University's master thesis, 1997) the optimal synthesis technique bar of acrylic acid modified rosin is obtained by orthogonal test
Part, in the product obtained, the gas chromatogram content of rosin acrylic acid is the highest, and only 69%；(the business such as Wang Hongxiao
Scholar is refined, Wang Hongxiao, Song Zhanqian, etc. preparation method .CN 101591238 B of rosin acrylic acid) apply for special
Profit is to use chemical method to prepare rosin acrylic acid, owing to rosin acrylic acid has two kinds of isomerss and several skeleton
The rosin acrylic acid of structure, therefore products therefrom is still the mixture of rosin acrylic acid.(the Cao Qi such as Cao Qifeng
Wind, Zhu Changchun, Song Wensheng, etc. the study on the synthesis of acrylic acid modified rosin. China's adhesive, 2007,16 (12):
26-28) synthesize acrylic acid modified rosin, but only discuss acid number and the softening point of acrylic acid modified rosin, and
Not providing the G/C content of APA under optimal conditions, the most the concrete structure to product does not carries out separating and characterizes；Woods
Bright great waves etc. (Lin Mingtao, Wang Jifu, Liu Yupeng, etc. the study on the synthesis of rosin acrylic acid. application chemical industry, 2012,
41 (5): 802-806) rosin acid and each resinic acid in acrylic acid Diels-Alder course of reaction are had studied in detail
Participating in the situation of reaction, even if acrylic acid excess during addition, abietic type acid can not join completely
Account for 2% and 7% respectively with reaction, unreacted resinic acid and abietic acid content, and passed through theoretical implications
The ratio of the amount going out the material of para-position product and metacompaund is 4:1, but does not have two kinds of isomerss
The separation of body resolves.The rosin acrylic acid result obtained by said method is not ideal, or the making of solvent
Consumption is big, cost is high, or to separate through repeatedly recrystallization, operates comparatively laborious, and separating effect is bad.
Summary of the invention
It is an object of the invention to provide product of a kind of p-rosin acrylic acid and preparation method thereof, product purity is more than
95%, simple to operate, effective.
The technical scheme is that preparation and the separation method of a kind of p-rosin acrylic acid product, with purification third
Alkene dextropimaric acid or acrylic acid modified rosin are raw material, and using benzene and ethyl acetate is developing solvent, by particle diameter is
The cyclo-dextrin-modified silica gel column chromatography of 0.044～0.075mm, extraction purification obtains p-rosin acrylic acid product；
Described acrylic acid modified rosin is with Colophonium and acrylic acid as raw material, passes through under conditions of microwave-assisted
Diels-Alder reaction prepares；Described purification rosin acrylic acid is to be purified by acrylic acid modified rosin
Gained.
Described purification rosin acrylic acid is by after the dissolving of acrylic acid modified rosin excess base, titrates with dilute hydrochloric acid
To pH 6.0, filtration under diminished pressure removes unreacted resinic acid filter cake, continues to be titrated to acid by gained filtrate
Acid, filtration under diminished pressure obtains the rosin acrylic acid with several isomers product, and wherein isomers is main
Including m-rosin acrylic acid and p-rosin acrylic acid.
Used fixing in described silica gel column chromatography be the silica gel of cyclo-dextrin-modified mutually, and eluent is benzene and acetic acid second
Ester admixture, benzene and ethyl acetate volume ratio are 5～20: 1, and the flow rate of eluent is 0.5～4
mL/min。
The silicagel column of described cyclo-dextrin-modified, by cyclodextrin structure is bonded to silica gel particle surface, specifically walks
Suddenly it is: step one, by the hydroxyl of Silica Surface by thionyl chloride chlorination；Step 2, by hydroxy propyl-Beta-ring
Dextrin and metallic sodium react formation negative oxygen ion；Step 3, by step one, the product reaction of two, obtains ring and sticks with paste
The silica gel that essence is modified.
Described Colophonium includes any one in gum rosin, wood rosin, Starex, and wherein gum rosin includes wetland
Loosely any one in perfume, Pinus massoniana Lamb Colophonium, pinus yunnanensis faranch Colophonium, Pinus kesiya Royle ex Gord. Var. Langbianensis (A. Chev.) Gaussen, pinus caribaea's Colophonium or appoint
Several compositionss.
The p-rosin acrylic acid product that the preparation of described p-rosin acrylic acid product and separation method obtain, p-
Rosin acrylic acid G/C content is more than 95%, and a small amount of composition contained is its isomer m-rosin acrylic acid.
Beneficial effect
1. using microwave assisting method synthesizing propylene dextropimaric acid, compared with document report, content improves 5%, and
Reproducible；
2. use back titration method to purify rosin acrylic acid, it is to avoid the usage amount of solvent is big, will through repeatedly weighing
The operating procedure that Crystallization Separation etc. are loaded down with trivial details；
The silica gel using cyclo-dextrin-modified first carries out the separation of p-rosin acrylic acid, it is thus achieved that content > 95%
High purity product.
Accompanying drawing explanation
Fig. 1 is the gas chromatogram of the embodiment of the present invention 4 gained p-rosin acrylic acid, and in figure, 1# peak is m-
Rosin acrylic acid, 2# peak is p-rosin acrylic acid, and G/C content is 95.7%.
Fig. 2 is the rosin acrylic acid after purification prepared by the present invention, and 1# peak is m-rosin acrylic acid, 2# peak
For p-rosin acrylic acid, G/C content is respectively 16.0% and 72.3%, additionally contains 10.3% other types
Rosin acrylic acid (skeleton D-A addition compound product).
Detailed description of the invention
Further illustrate the present invention below in conjunction with detailed description of the invention, but the scope of protection of present invention is not
It is confined to following embodiments.
The method for separating and preparing of a kind of p-rosin acrylic acid, with Colophonium and acrylic acid as raw material, at microwave-assisted
Under the conditions of through Diels-Alder reaction prepare acrylic acid modified rosin.With acrylic acid modified rosin or its
Purified product rosin acrylic acid is raw material, and using benzene and ethyl acetate is developing solvent, is 0.044～0.075 at particle diameter
The cyclo-dextrin-modified silica gel column chromatography of mm is continuously added developing solvent, obtains from collecting the stepwise elution liquid obtained
Obtain p-rosin acrylic acid.It is as follows that concrete column chromatography processes step:
Cyclo-dextrin-modified silica gel: 1) weigh 7g tlc silica gel and put in 250mL flask, add 35mL
Benzene, 40mL thionyl chloride, stirring under conditions of reflux 10h, reaction terminate after filter, by product in
Put in vacuum drying oven for 90 DEG C and be dried, dried white powder.2) weigh 9g hydroxy propyl-Beta-ring to stick with paste
Essence, adds dry DMF 80mL, 0.4g Na, stirring reaction 2-3h at 90 DEG C.3) treat that Na is complete
After full response, add the silica gel after chlorination, and react 12h in 70-100 DEG C, product is used triangular funnel mistake
Filter, stood the elimination supernatant, will be deposited at 70 DEG C vacuum drying 12h, and obtain cyclo-dextrin-modified silica gel.
Purification rosin acrylic acid is that acrylic acid modified rosin passes through the product being further purified, and is by acrylic acid modified
After Colophonium dissolves with excess base, remove filter cake with filtration under diminished pressure after 5% HCI to pH 6.0 (unreacted
Resinic acid), gained filtrate is continued to be titrated to peracid with acid, filtration under diminished pressure obtains having several isomers
The rosin acrylic acid of product, wherein isomers mainly includes m-rosin acrylic acid and p-rosin acrylic acid.
Fixing used by column chromatography for separation is column chromatography silica gel mutually, and eluent is benzene and ethyl acetate mixture, two
Person's volume ratio is 5: 1～20: 1, and the flow rate of eluent is 0.5～4mL/min.
Colophonium can use any one in gum rosin, wood rosin, Starex, and wherein gum rosin has wetland loosely
Any one in perfume, Pinus massoniana Lamb Colophonium, pinus yunnanensis faranch Colophonium, Pinus kesiya Royle ex Gord. Var. Langbianensis (A. Chev.) Gaussen, pinus caribaea's Colophonium or its two kinds
And two or more compositionss.
P-rosin acrylic acid product, it is characterised in that gained p-rosin acrylic acid product purity more than 95%, this
Outer possibly together with a small amount of m-rosin acrylic acid.
Embodiment 1
In flask, add 10g Colophonium and 2.4g acrylic acid, be placed in microwave reaction work station, at microwave power
Under the conditions of 300W, reaction temperature 230 DEG C, response time 90min, prepare acrylic acid modified rosin.
With this acrylic acid modified rosin as raw material, using benzene and ethyl acetate volume ratio 5:1 is developing solvent, mistake
0.044～0.075mm cyclo-dextrin-modified column chromatography silica gel post, extracting solution is concentrated to dryness, and obtains p-propylene Korean pine
Acid.The yield of isolated p-rosin acrylic acid is 35.4%, obtains p-rosin acrylic acid by column chromatography
G/C content is 85.6%.
Embodiment 2
In flask, add 10g Colophonium and 4.8g acrylic acid, be placed in microwave reaction work station, at microwave power
Under the conditions of 400W, reaction temperature 200 DEG C, response time 110min, prepare acrylic acid modified rosin.
With this acrylic acid modified rosin as raw material, using benzene and ethyl acetate volume ratio 8:1 is developing solvent, mistake
0.044～0.075mm cyclo-dextrin-modified column chromatography silica gel post, extracting solution is concentrated to dryness, and obtains p-propylene Korean pine
Acid.The yield 29.7% of isolated p-rosin acrylic acid, obtains the GC of p-rosin acrylic acid by column chromatography
Content is 85.6%.
Embodiment 3
In flask, add 10g Colophonium and 2.4g acrylic acid, be placed in microwave reaction work station, at microwave power
Under the conditions of 500W, reaction temperature 210 DEG C, response time 100min, prepare acrylic acid modified rosin.
With this acrylic acid modified rosin as raw material, using benzene and ethyl acetate volume ratio 20:1 is developing solvent, mistake
0.044～0.075mm cyclo-dextrin-modified column chromatography silica gel post, extracting solution is concentrated to dryness, and obtains p-propylene Korean pine
Acid.The yield of isolated p-rosin acrylic acid is 17.2%, obtains p-rosin acrylic acid by column chromatography
G/C content is 84.3%.
Embodiment 4
In flask, add 10g Colophonium and 2.4g acrylic acid, be placed in microwave reaction work station, at microwave power
Under the conditions of 300W, reaction temperature 230 DEG C, response time 90min, prepare acrylic acid modified rosin,
After it being dissolved with excess base, remove filter cake with filtration under diminished pressure after 5%wt HCI to pH 6.0, by institute
Obtaining filtrate and continue to be titrated to peracid with acid, filtration under diminished pressure obtains isomers product propylene dextropimaric acid.With this third
Alkene dextropimaric acid is raw material, and using benzene and ethyl acetate volume ratio 9:1 is developing solvent, crosses 0.044～0.075mm
Cyclo-dextrin-modified column chromatography silica gel post, extracting solution is concentrated to dryness, and obtains p-rosin acrylic acid.Isolated p-
The yield of rosin acrylic acid is 19.4%, and the G/C content being obtained p-rosin acrylic acid by column chromatography is 95.7%.
Claims (6)
1. the preparation of a p-rosin acrylic acid product and separation method, it is characterised in that: with purification rosin acrylic acid
Or acrylic acid modified rosin is raw material, using benzene and ethyl acetate is developing solvent, is 0.044～0.075 by particle diameter
The cyclo-dextrin-modified silica gel column chromatography of mm, extraction purification obtains p-rosin acrylic acid product；Described acrylic acid
Modified rosin is with Colophonium and acrylic acid as raw material, reacts through Diels-Alder under conditions of microwave-assisted
Prepare；Described purification rosin acrylic acid is that acrylic acid modified rosin is purified gained.
2. the preparation of p-rosin acrylic acid product as claimed in claim 1 and separation method, it is characterised in that institute
The purification rosin acrylic acid stated is by after the dissolving of acrylic acid modified rosin excess base, is titrated to pH with dilute hydrochloric acid
After 6.0, filtration under diminished pressure removes unreacted resinic acid filter cake, continues to be titrated to peracid with acid by gained filtrate, subtracts
Press filtration obtains the rosin acrylic acid with several isomers product, and wherein isomers mainly includes
M-rosin acrylic acid and p-rosin acrylic acid.
3. the preparation of p-rosin acrylic acid product as claimed in claim 1 and separation method, it is characterised in that institute
Fixing the silica gel mutually for cyclo-dextrin-modified used by the silica gel column chromatography stated, eluent is that benzene mixes with ethyl acetate
Thing, benzene and ethyl acetate volume ratio are 5～20: 1, and the flow rate of eluent is 0.5～4mL/min.
4. the preparation of p-rosin acrylic acid product as claimed in claim 3 and separation method, it is characterised in that institute
The silicagel column of the cyclo-dextrin-modified stated, by cyclodextrin structure is bonded to silica gel particle surface, concretely comprises the following steps:
Step one, by the hydroxyl of Silica Surface by thionyl chloride chlorination；Step 2, by HP-β-CD with
Metallic sodium reaction forms negative oxygen ion；Step 3, by step one, the product reaction of two, obtains cyclo-dextrin-modified
Silica gel.
5. the preparation of p-rosin acrylic acid product as claimed in claim 1 and separation method, it is characterised in that institute
State Colophonium and include any one in gum rosin, wood rosin, Starex, wherein gum rosin include slash pine rosin,
Any one in Pinus massoniana Lamb Colophonium, pinus yunnanensis faranch Colophonium, Pinus kesiya Royle ex Gord. Var. Langbianensis (A. Chev.) Gaussen, pinus caribaea's Colophonium or several group
Compound.
6. the p-propylene that the preparation of the arbitrary described p-rosin acrylic acid product of Claims 1 to 4 obtains with separation method
Dextropimaric acid product, it is characterised in that p-rosin acrylic acid G/C content is more than 95%, a small amount of composition contained
For its isomer m-rosin acrylic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610221929.6A CN105801401B (en) | 2016-04-11 | 2016-04-11 | A kind of preparation of high-purity p rosin acrylic acids and separation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610221929.6A CN105801401B (en) | 2016-04-11 | 2016-04-11 | A kind of preparation of high-purity p rosin acrylic acids and separation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105801401A true CN105801401A (en) | 2016-07-27 |
| CN105801401B CN105801401B (en) | 2018-02-09 |
Family
ID=56460884
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610221929.6A Active CN105801401B (en) | 2016-04-11 | 2016-04-11 | A kind of preparation of high-purity p rosin acrylic acids and separation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105801401B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101591238A (en) * | 2009-06-19 | 2009-12-02 | 中国林业科学研究院林产化学工业研究所 | The preparation method of rosin acrylic acid |
| CN102336657A (en) * | 2011-09-15 | 2012-02-01 | 中国林业科学研究院林产化学工业研究所 | Purification method for acrylpimaric acid |
-
2016
- 2016-04-11 CN CN201610221929.6A patent/CN105801401B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101591238A (en) * | 2009-06-19 | 2009-12-02 | 中国林业科学研究院林产化学工业研究所 | The preparation method of rosin acrylic acid |
| CN102336657A (en) * | 2011-09-15 | 2012-02-01 | 中国林业科学研究院林产化学工业研究所 | Purification method for acrylpimaric acid |
Non-Patent Citations (2)
| Title |
|---|
| JIAN LI, ET AL.: "Synthesis and antibacterial activity of amide derivatives from acrylopimaric acid", 《BIORESOURCES》 * |
| 李健 等: "丙烯海松双酰基硫脲衍生物的合成", 《化学试剂》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105801401B (en) | 2018-02-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Li et al. | Efficient and reusable amine-functionalized polyacrylonitrile fiber catalysts for Knoevenagel condensation in water | |
| JP5256679B2 (en) | Lignin derivatives and their secondary derivatives | |
| WO2014142289A1 (en) | Method for manufacturing lignin degradation product | |
| Verma et al. | An efficient biomaterial supported bifunctional organocatalyst (ES-SO3− C5H5NH+) for the synthesis of β-amino carbonyls | |
| Auclair et al. | Acrylated betulin as a comonomer for bio-based coatings. Part I: Characterization, photo-polymerization behavior and thermal stability | |
| CN106146307A (en) | Polyunsaturated vegetable oil alkylates based on UV light-catalyzed reaction and preparation method | |
| CN105646800B (en) | A kind of preparation method of abietyl hydroxylated polymer microballoon | |
| CN106519186A (en) | Refuse lac chain-extended modification powder and preparation method thereof | |
| JP5338793B2 (en) | Method for producing lignin derivative and method for producing lignin secondary derivative | |
| CN105801401A (en) | Preparation and separation method of high-purity p-acrylic pimaric acid | |
| CN101362924B (en) | Method for decolorization preparation of pale rosin by rosin containing non-decoloring agent | |
| CN106861645A (en) | A kind of preparation method of the thio strong oil absorption material of aminated lignin base | |
| CN102603564B (en) | Synthesis technique of alpha-cyanoacrylate monomer | |
| CN107233921A (en) | The methods and applications that SalenMX prepares catalyst are loaded with modified cellulose | |
| CN102659573B (en) | Preparation method for 7-carbonyl group-8, 15-isopimaric acid | |
| CN100453569C (en) | High-specific-surface acrylates adsorption resin and synthesizing method | |
| Lu et al. | Synthesis of allyl acrylpimarate by microwave irradiation and phase-transfer catalytic reaction and its UV-curing reactions as a new monomer | |
| CN102698813A (en) | Method for preparing multifunctional solid superacid catalyst and method using waste cooking oil as raw material to synthesize biodiesel | |
| JP5338792B2 (en) | Method for producing lignin derivative and method for producing lignin secondary derivative | |
| CN105503789B (en) | Montmorillonite load metal ion solid acid catalysis xylose is the method for furfural | |
| CN104710285A (en) | Method for recycling ethylene glycol monomethyl ether | |
| CN103265675B (en) | Preparation method of phenolic resin with cross-linked amino structure and application thereof | |
| CN103880855B (en) | The method of Epoxidation of Dicyclopentadiene preparative separation bicyclopentadiene dioxide | |
| CN111330641A (en) | Preparation method and application of carbon-based solid acid catalyst | |
| CN106497225B (en) | A kind of high adhesion force printing ink adhesive and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20230301 Address after: No. 229, Wuhua Road, Changyue Foreign Investment Industrial Zone, Xinjian District, Nanchang, Jiangxi 330000 Patentee after: NANCHANG CITY LONGRAN INDUSTRY CO.,LTD. Address before: Five suojin village of Nanjing city in Jiangsu province 210042 No. 16 Patentee before: INSTITUTE OF CHEMICAL INDUSTRY OF FOREST PRODUCTS, CAF |
|
| TR01 | Transfer of patent right |