CN107722138A - A kind of chitin prepares the new method of water-soluble carboxymethyl chitosan - Google Patents
A kind of chitin prepares the new method of water-soluble carboxymethyl chitosan Download PDFInfo
- Publication number
- CN107722138A CN107722138A CN201710658165.1A CN201710658165A CN107722138A CN 107722138 A CN107722138 A CN 107722138A CN 201710658165 A CN201710658165 A CN 201710658165A CN 107722138 A CN107722138 A CN 107722138A
- Authority
- CN
- China
- Prior art keywords
- chitin
- concentration
- water
- carboxymethyl chitosan
- chitosan
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
- C08B37/0027—2-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
- C08B37/003—Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Molecular Biology (AREA)
- Engineering & Computer Science (AREA)
- General Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Cosmetics (AREA)
Abstract
The present invention relates to one kind using chitin as raw material, use sodium chloroacetate to prepare the production technology of water-soluble carboxymethyl chitosan for reactant and improve new method, it is characterised in that:Chitosan powder is substituted as raw material using chitin powder, the strong and stimulating and corrosive monoxone for replacing using in conventional production using sodium chloroacetate are reacted, and reaction dissolvent is certain density ethanol solution.Prepared carboxymethyl chitosan dissolves in the range of being 6.0~8.0 in pH, substitution value > 80%, deacetylation > 70%, purity >=85%, such chitosan derivatives have preferable bacteria resistance and moisture absorbability and moisture retentivity, and further purification can be widely applied to the fields such as medicine, food or cosmetics.Chitin prepares water-soluble carboxymethyl chitosan process schematic and refers to Figure of abstract.
Description
Technical field
The present invention relates to field of fine chemical, belongs to marine chemical industry engineering technology, is a kind of new N, O- substituted carboxymethyls
Preparing Technology for Chinosan technology, it is a kind of new method that water-soluble carboxymethyl chitosan is prepared using chitin as raw material.By crust
Plain powder reacts with sodium chloroacetate in ethanol solution obtains water miscible N, O-CMC.Compared with prior art,
High with the preparation method raw material availability of the present invention, working environment improves notable, product purity height, high income, such chitosan
Derivative C6Position -0H and C2Substitution value on the-NH2 of position is up to 80~110%, and water solubility preferably, and has preferable antibacterial bacteriostatic
Property and moisture absorbability and moisture retentivity, further purification can be widely applied to the fields such as medicine, food or cosmetics.
Background technology:
Chitin, also known as chitin, chitin, β-(1-4) -2- acetylaminohydroxyphenylarsonic acid 2-deoxy-D-glucoses, is nature
The most abundant resource of second.Be prevalent in shrimp crab shell, arthropod, fungal cell wall and certain plants cell membrane it
In, the chitin of synthesis reaches 10,000,000,000 tons of jin in annual nature biotechnology body.But chitin is not soluble in water and usual vehicle, limits
It is applied.
Chitosan is the product after the chemically treated deacetylation of chitin, is a kind of natural cationic polymerization
Thing, its nontoxic, harmless, safe and reliable, easily biological-degradable, there is good biocompatibility.But chitosan is dissolved only in acid or acid
In property solution, its application strongly limit.Therefore, chemical modification is carried out to chitosan to improve its dissolubility in water
Research, just it is significant.In numerous chitosan derivatives, the research of carboxymethyl chitosan is more early, not only has
Good water solubility, the advantageous property of chitosan is also equipped with, had in fields such as medicine, food, environmental protection, printing and dyeing and biological health-care products
Prospect is widely applied, there is huge economic benefit and social benefit.
At present, it is using chitosan powder as raw material, after basification, in isopropanol reaction that industrialized production, which uses more,
Monoxone is added dropwise in solvent and carries out graft reaction, production process has problems.
1st, need sodium hydroxide high alkali liquid and high-temperature process during preparing chitosan from chitin, the alkali number of preparation process consumption and
It is more to post-process neutral hourly water consumption.
2nd, chitosan prepares carboxymethyl chitosan reaction monoxone early stage and sodium hydroxide neutralizes, very exothermic, monoxone
A large amount of hydrolysis, cause the accessory substances such as diglycolic acid more, and carboxylation degree is easily influenceed by temperature fluctuation, and reaction speed is slow, the time compared with
It is about more than 20 hours, complex procedures when post processing purifies, cost is higher.
3rd, chloroacetic harmfulness:It is hypertoxic, flammable, there is excitant and corrosivity, human body can be caused to burn.Industrial production is used
Chloroacetic acid solution add ethanol to prepare for solid monoxone, accelerate its volatility, suck the high concentration product steam or skin connects
After touching its solution, it can largely absorb rapidly, cause acute poisoning.Patient can have twitch, stupor, shock, blood urine and renal function to decline
Exhaust.Acid mist can cause irritated eyes and ambustio corneae.Skin burn may occur in which blister.Often in contact with the low concentration product acid mist,
Can there are headache, dizzy phenomenon.Poisonous corrosive fume is produced by high thermal decomposition.So monoxone is in transport, storage and uses
Etc. risk be present in each link, cause to have a strong impact on to industrialized production.
4th, the harmfulness of isopropanol:It is a kind of volatile liquid, high concentration steam has obvious anesthetic effect, to eye, exhales
The mucous membrane for inhaling road has stimulation, can damage retina and optic nerve.It can be absorbed by the body by skin.It is inflammable, can under normal temperature
Ignite burning, its steam mixes with air easily forms explosive mixture.Contact high concentration steam appearance headache, drowsiness and eye,
Nose, larynx irritation, operating personnel should wear a gas mask.
Due to these problems present on existing production Technology, extreme influence is caused to industrial production.This patent
Using chitin powder as initiation material, it is reaction system to select ethanol, and reagent is inexpensive and environmentally friendly sodium chloroacetate, is urged without other
Agent, course of reaction mild condition, product purity are high.
Brief description of the drawings
Accompanying drawing is that chitin prepares water-soluble carboxymethyl chitosan process schematic, refers to Figure of description.
The content of the invention
It is an object of the invention to:Change it is traditional using chitosan powder as initiation material, this patent use chitin powder for
Raw material, handled with concentrated base, chitin is deacetylated to turn into chitosan, without isolation, using ethanol solution as reaction system, is directly added into
Sodium chloroacetate is that reactant carries out carboxymethylation reaction, crude product ethyl alcohol purification, and the product substitution value after purification processes exists
More than 80%, deacetylation is up to more than 70%.This technology reduces the dosage of alkali, reduces the cost of raw material, greatly changes
Production operation environment has been apt to it, has simplified production procedure corollary equipment, shorten the reaction time, has significantly reduced being manufactured into for product
This, product is water-soluble preferably can be completely dissolved in the range of extensive pH, and this invention prepares industry for carboxymethyl chitosan
Bring huge effect.The technical solution of the present invention is as follows:
Method after improvement:A certain amount of chitin powder is weighed to put into agitator tank, 5~10 times of chitin weight of addition
The NaOH solution of 40~50% concentration, after 1.5~3h of normal temperature basification, add the 80~95% of 5~10 times of chitin weight
Concentration ethanol solution, then the sodium chloroacetate of 1.5~2.5 times of chitin weight is added in system, in 50~70 DEG C of heat preservation strips
3.0~6.0h is reacted under part.The dissolving of reacting rear material purified water is refiltered, and after ethyl alcohol purification separates out, pH is adjusted extremely with diluted acid
Neutrality, then washed twice with the ethanol solution of 70~80% concentration, 90~99% concentration ethanols are dehydrated once, are vacuumized dry
Product.
The remarkable effect of the present invention:The preparation method of the present invention is simple and easy to operate, and chitosan is replaced using chitin
Production link is shortened for initiation material, reduces production cost, the chloroethene used in conventional production is substituted using sodium chloroacetate
Acid and isopropanol is replaced to prepare carboxymethyl chitosan using ethanol, compared with prior art, the present invention is with beneficial below
Effect (illustrates) by taking sodium chloroacetate as an example.
1st, the raw material chitin used in the present invention, valency is low to be easy to get, and eliminates the process by concentrated base processing deacetylation, letter
Change production process, be directly successfully prepared water miscible carboxymethyl chitosan by raw material of chitin.
2nd, the ethanol and sodium chloroacetate used in the present invention, is readily transported, stores, and nonirritant and corrosivity is easy to operate,
Production environment is significantly improved, while reduces transport to raw material, keeping and operates with, production equipment etc.
It is required that production cost is low.
3rd, existing technology is that monoxone is added dropwise in aqueous isopropanol, and working environment penetrating odor is larger, reacts early stage
With being difficult to control in sodium hydroxide with very exothermic, temperature of reaction system, to consersion unit reaction early stage cooling and late phase reaction
The requirement of heating is higher, but uses sodium chloroacetate to substitute monoxone and produced, and easy to operate, reaction condition is gentle, reaction
Process environmental protection.
4th, without using any other catalyst, directly reacted, hydrolyzed without monoxone secondary using sodium chloroacetate
The presence of reaction, reaction is gentle, and grafting rate is high, improves the utilization rate of reaction reagent, and raw material is cheap and easy to get, that is, reduces carboxylic
The manufacturing cost of methyl chitosan.
5th, the pH 6.0-8.0, substitution value > 80%, deacetylation > 70% of detection product carboxymethyl chitosan, purity >=
85%.
The improved method that this patent proposes greatly improves working environment, simplifies production procedure, considerably reduces
Production cost and the requirement to equipment, remarkable effect is brought for the industrialized production of water-soluble carboxymethyl chitosan industry.
Embodiment
Embodiment 1:
20g chitin powder is added into the beaker for be provided with electric mixer, prepares the NaOH solution of 200g45% concentration,
Pour into chitin powder, stirring alkalization 1.5h, separation of solid and liquid, add 120ml 95% ethanol, be stirring evenly and then adding into 40g chlorine
Sodium acetate, 3.0h is reacted under 60 DEG C of heat-retaining conditions, reaction terminates rear separation of solid and liquid, and diluted acid adjusts pH to neutrality, then with 75% concentration
Ethanol solution 200ml wash twice, 95% concentration ethanol 100ml is dehydrated once, vacuumizes dry product, according to
《YY0953-2015 medical carboxymethyl chitosans》In method detection pH 7.0, substitution value 96.1%, deacetylation
81.7%, purity 86.3%.
Embodiment 2:
20g chitin powder is added into the beaker for be provided with electric mixer, prepares the NaOH solution of 200g45% concentration,
Pour into chitin powder, stir 1.5h basifications, separation of solid and liquid, add 150ml 95% ethanol, be stirring evenly and then adding into
50g sodium chloroacetates, 3.5h is reacted under 65 DEG C of heat-retaining conditions, reaction terminates rear separation of solid and liquid, and diluted acid adjusts pH to neutrality, then with 75%
The ethanol solution 200ml of concentration is washed twice, and 95% concentration ethanol 100ml is dehydrated once, vacuumizes dry product, according to
《YY0953-2015 medical carboxymethyl chitosans》In method detection pH 7.2, substitution value 92.3%, deacetylation
78.9%, purity 90.8%.
Embodiment 3:
Weigh 10kg chitin raw materials to put into agitator tank, prepare the NaOH solution 100kg of 45% concentration, stirred under normal temperature
After mixing basification 2h, separation of solid and liquid, the concentration ethanol solution of 60kg 95% is added, then 20kg sodium chloroacetates are added to system
In, react 5.0h under 60 DEG C of heat-retaining conditions.React and dissolve crude product with purified water after terminating, filter, adopt through 3 μm of accurate filters
With 95% ethanol solution Precipitation, separation of solid and liquid, pH is adjusted to wash two to neutrality, then with the ethanol solution of 75% concentration with diluted acid
Secondary, 95% concentration ethanol is dehydrated once, is vacuumized and be dry, pulverize and obtained after 80 eye mesh screens product.After testing, product pH
7.3, substitution value 111.2%, deacetylation 87.9%, purity 94.7%.
Above content is to combine specific preferred embodiment further description made for the present invention, it is impossible to is assert
The embodiment of the present invention is only limitted to this, for general technical staff of the technical field of the invention, is not taking off
On the premise of from present inventive concept, some simple deduction or replace can also be made, should all be considered as belonging to the present invention by institute
Claims of submission determine scope of patent protection.
Claims (6)
1. a kind of chitin prepares the new method of water-soluble carboxymethyl chitosan, it is characterised in that:Its product is C2- N, C6- O- carboxylics
Methyl chitosan, C2- N- carboxymethyl chitosans, C6- O-CMC, C6- O- carboxymethyl chitins are one or more.
2. a kind of chitin prepares the new method of water-soluble carboxymethyl chitosan, it is characterised in that:Shell is substituted with chitin powder to gather
Icing Sugar is raw material, and the monoxone for replacing using in conventional production using sodium chloroacetate is reacted, and reaction dissolvent is finite concentration
Ethanol solution.
3. a kind of chitin prepares the new method of water-soluble carboxymethyl chitosan, its characterization method is:Weigh a certain amount of crust
Plain powder is put into agitator tank, adds the NaOH solution of 40~50% concentration of 5~10 times of chitin weight, normal temperature basification
After 1.5~3h, 80~95% concentration ethanol solution of 5~10 times of chitin weight are added, then by 1.5~2.5 times of chitin weights
The sodium chloroacetate of amount is added in system, and 3.0~6.0h is reacted under 50~70 DEG C of heat-retaining conditions.
4. the dissolving of reacting rear material purified water refilters, after ethanol precipitation, pH is adjusted to neutrality with diluted acid, then with 70~80%
The ethanol solution of concentration is washed twice, and 90~99% concentration ethanols are dehydrated once, vacuumizes dry product.
5. chitin as claimed in claim 3 prepares the new method of water-soluble carboxymethyl chitosan, it is characterised in that:The water
Dissolubility carboxymethyl chitosan according to《YY0953-2015 medical carboxymethyl chitosans》In method detect its pH6.0-8.0, substitute
Spend > 80%, deacetylation > 70%, purity >=85%.
6. chitin as claimed in claim 3 prepares the new method of water-soluble carboxymethyl chitosan, it is characterised in that:Using one
The ethanol solution for determining concentration is reaction system, and the determination of concentration of alcohol is by the sodium hydroxide solution compound concentration that alkalizes, alkalization
Material moisture, the addition of ethanol and concentration are realized afterwards.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710658165.1A CN107722138A (en) | 2017-07-31 | 2017-07-31 | A kind of chitin prepares the new method of water-soluble carboxymethyl chitosan |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710658165.1A CN107722138A (en) | 2017-07-31 | 2017-07-31 | A kind of chitin prepares the new method of water-soluble carboxymethyl chitosan |
Publications (1)
Publication Number | Publication Date |
---|---|
CN107722138A true CN107722138A (en) | 2018-02-23 |
Family
ID=61204639
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201710658165.1A Pending CN107722138A (en) | 2017-07-31 | 2017-07-31 | A kind of chitin prepares the new method of water-soluble carboxymethyl chitosan |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN107722138A (en) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109734519A (en) * | 2019-03-15 | 2019-05-10 | 招远市金虹精细化工有限公司 | A kind of nutrient solution and its application method for administering grassland desertification |
CN110317280A (en) * | 2019-04-10 | 2019-10-11 | 青岛童医生海洋生物科技股份有限公司 | A kind of different degree of substitution Preparation Technology of Carboxymethyl-chitosan |
CN110484578A (en) * | 2019-08-02 | 2019-11-22 | 威海迪素制药有限公司 | A kind of method of enzyme process preparation low molecular weight carboxymethylchitosan |
CN110734505A (en) * | 2019-11-15 | 2020-01-31 | 华熙生物科技股份有限公司 | Preparation method of carboxymethyl chitin |
CN111320710A (en) * | 2020-04-28 | 2020-06-23 | 东华大学 | Method for preparing high-substitution-degree high-molecular-weight carboxymethyl chitosan from chitin |
CN112125984A (en) * | 2020-11-03 | 2020-12-25 | 江苏金壳生物医药科技有限公司 | Preparation method of carboxymethyl chitosan |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1629196A (en) * | 2004-10-20 | 2005-06-22 | 中国海洋大学 | Process for preparing carboxymethyl chitosan and its application |
CN104045842A (en) * | 2014-06-30 | 2014-09-17 | 中国药科大学 | Preparation method of O-carboxymethyl chitosan resin |
CN104725530A (en) * | 2014-09-11 | 2015-06-24 | 迪沙药业集团有限公司 | Preparation method of O-carboxylated chitin |
CN104788584A (en) * | 2014-01-17 | 2015-07-22 | 厦门大学 | New technology for clean production of chitosan and carboxymethyl chitosan by using crustacean shell raw materials |
CN105153325A (en) * | 2015-09-16 | 2015-12-16 | 中华全国供销合作总社南京野生植物综合利用研究所 | Improved production process of carboxymethyl chitosan |
-
2017
- 2017-07-31 CN CN201710658165.1A patent/CN107722138A/en active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1629196A (en) * | 2004-10-20 | 2005-06-22 | 中国海洋大学 | Process for preparing carboxymethyl chitosan and its application |
CN104788584A (en) * | 2014-01-17 | 2015-07-22 | 厦门大学 | New technology for clean production of chitosan and carboxymethyl chitosan by using crustacean shell raw materials |
CN104045842A (en) * | 2014-06-30 | 2014-09-17 | 中国药科大学 | Preparation method of O-carboxymethyl chitosan resin |
CN104725530A (en) * | 2014-09-11 | 2015-06-24 | 迪沙药业集团有限公司 | Preparation method of O-carboxylated chitin |
CN105153325A (en) * | 2015-09-16 | 2015-12-16 | 中华全国供销合作总社南京野生植物综合利用研究所 | Improved production process of carboxymethyl chitosan |
Non-Patent Citations (1)
Title |
---|
刘音等: ""甲壳素的改性及其对 Cr(Ⅵ )吸附性能的研究"", 《水利渔业》 * |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109734519A (en) * | 2019-03-15 | 2019-05-10 | 招远市金虹精细化工有限公司 | A kind of nutrient solution and its application method for administering grassland desertification |
CN110317280A (en) * | 2019-04-10 | 2019-10-11 | 青岛童医生海洋生物科技股份有限公司 | A kind of different degree of substitution Preparation Technology of Carboxymethyl-chitosan |
CN110484578A (en) * | 2019-08-02 | 2019-11-22 | 威海迪素制药有限公司 | A kind of method of enzyme process preparation low molecular weight carboxymethylchitosan |
CN110734505A (en) * | 2019-11-15 | 2020-01-31 | 华熙生物科技股份有限公司 | Preparation method of carboxymethyl chitin |
CN111320710A (en) * | 2020-04-28 | 2020-06-23 | 东华大学 | Method for preparing high-substitution-degree high-molecular-weight carboxymethyl chitosan from chitin |
CN111320710B (en) * | 2020-04-28 | 2021-11-19 | 东华大学 | Method for preparing high-substitution-degree high-molecular-weight carboxymethyl chitosan from chitin |
CN112125984A (en) * | 2020-11-03 | 2020-12-25 | 江苏金壳生物医药科技有限公司 | Preparation method of carboxymethyl chitosan |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN107722138A (en) | A kind of chitin prepares the new method of water-soluble carboxymethyl chitosan | |
CN106106522B (en) | A kind of nano zine oxide-load silver chitosan compound anti-bacteria agent and preparation method thereof | |
CN107474161B (en) | A kind of selective oxidation chitosan and its heterogeneous preparation method | |
US4016354A (en) | Preparation of pharmacologically active hydroxyalkyl starch | |
CN103570844B (en) | A kind of preparation method of carboxyethyl welan gum | |
CN102153672B (en) | Method for extracting chondroitin sulfate | |
CN106167581A (en) | A kind of preparation method of antibacterial polypropylene | |
CN103539868A (en) | Method for preparing carboxymethyl chitosan | |
CN112940148A (en) | Hyaluronic acid purification method | |
CN107163159B (en) | A kind of halogen-containing chitosan quaternary ammonium salt and its preparation method and application | |
CN106435055A (en) | Antibacterial retanning agent and preparation method thereof | |
CN101570555A (en) | Preparation method of calcium supplement carboxymethyl chitosan oligosaccharide calcium | |
CN107903338A (en) | A kind of chitosan oligosaccharide derivative and its preparation method and application | |
CN107602726B (en) | Low molecular weight C6-carboxyl chitin and preparation method thereof | |
CN106519060A (en) | Preparation of carboxymethyl curdlan | |
CN105153325A (en) | Improved production process of carboxymethyl chitosan | |
CN101570554B (en) | Method for preparing zinc supplementing agent carboxymethyl chitosan oligosaccharide zinc | |
CN106749712B (en) | A kind of method of semidry method preparation carboxymethyl starch | |
CN103509129A (en) | Carbonyl starch oxidized by Fenton similar system, and preparation method of carbonyl starch | |
CN110452316A (en) | A method of extracting β-chitin from squid cartilage | |
CN106432537B (en) | A kind of cationic chitosan and its preparation method and application | |
CN107362747A (en) | A kind of polymeric anion shell polysaccharide surfactant and preparation method | |
CN110317280A (en) | A kind of different degree of substitution Preparation Technology of Carboxymethyl-chitosan | |
CN113603812A (en) | Preparation method of selenium chromium-loaded double-element chelate and product thereof | |
CN104193836A (en) | Production process for medicinal hydroxypropyl starch |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
TA01 | Transfer of patent application right |
Effective date of registration: 20190729 Address after: 266000 Qianjiashan Road 359, Huangdao District, Qingdao City, Shandong Province Applicant after: Qingdao Tong Doctor Marine Biotechnology Co., Ltd. Address before: 272100 Guhuai Road West, Mechatronics Road North, Jining City, Shandong Province (Humanities Jiayuan Street Commerce) Applicant before: Shandong humanities Co., Ltd. |
|
TA01 | Transfer of patent application right | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20180223 |
|
WD01 | Invention patent application deemed withdrawn after publication |