CN1609132A - Prepn process of polyepoxy succinic acid with calcium sulfate as catalyst - Google Patents
Prepn process of polyepoxy succinic acid with calcium sulfate as catalyst Download PDFInfo
- Publication number
- CN1609132A CN1609132A CN 200310101836 CN200310101836A CN1609132A CN 1609132 A CN1609132 A CN 1609132A CN 200310101836 CN200310101836 CN 200310101836 CN 200310101836 A CN200310101836 A CN 200310101836A CN 1609132 A CN1609132 A CN 1609132A
- Authority
- CN
- China
- Prior art keywords
- succinic acid
- acid
- lime carbonate
- epoxysuccinic acid
- epoxysuccinic
- 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
Landscapes
- Epoxy Compounds (AREA)
Abstract
The process of preparing polyepoxy succinic acid with calcium carbonate as catalyst includes the following steps: dissolving epoxy succinic acid in deionized water of 1-3 times; adding sodium hydroxide in the amount of 0.1-0.2 time epoxy succinic acid to alkalify at temperature below 80 deg.c and to produce sodium epoxy succinate; adding catalyst calcium carbonate in the amount of 0.02-0.2 time epoxy succinic acid to polymerize at 90-105 deg.c for 3-6 hr to prepare coarse polyepoxy succinic acid; and filtering and refining to obtain polyepoxy succinic acid product. Calcium carbonate as catalyst has the advantages of no corrosion, no water absorption, water insolubility and less degradation, and the polyepoxy succinic acid preparing process has smooth reaction, short process, high product yield, easy product separation and relatively high molecular weight.
Description
Technical field
The present invention relates to a kind of method by the synthetic poly-epoxy succinic acid of Epoxysuccinic acid, this method is to be catalyzer with lime carbonate.
Background technology
Poly-epoxy succinic acid is a kind of water-soluble polymers with powerful chelating and scale inhibition performance, and not phosphorous in its molecular structure, nitrogen element can not cause body eutrophication, and biological degradability is good, is a kind of green polymer.It is strong to calcium, magnesium, the isoionic chelating ability of iron, and has threshold effect, and scale inhibition performance is good, is applicable to high-alkali high solid water system, and high concentration multiple and zero blowdown are handled, and are the renewal products of existing Scale inhibitors.
The structural formula of the poly-epoxy succinic acid that United States Patent (USP) " polymers detergent builders " (US, 776,850) proposes is:
Wherein R is H or other appointment group, and n is preferably 2-6 from 2-40.When n is 3 or 4, compound scale removal better performances.Its preparation method is to be that catalyzer is from the Epoxysuccinic acid monomer polymerization with the boron trifluoride.This method can be prepared the poly-epoxy succinic acid mixture of very low n=3 of content and n=4, but is difficult to realize industrialization.
The structural formula of the poly-epoxy succinic acid that United States Patent (USP) " Ether hydroxypolycarboxylate detergency builders " (US 4,654,159) proposes is:
In the formula, M is H, NH
4Or alkali metal cation, R is H or C
1-4Alkyl, n are more preferably 2~10 from 2~15, and preferably 2~4.Its preparation method is in liquid phase medium, the calcium hydroxide reaction that the epoxy succinic hydrochlorate of solubility is suitable with molar weight, and the reactant esterification separates ester from reaction mixture, the ester saponification is generated an alkali metal salt of poly-epoxy succinic acid again.The reaction conditions of epoxy succinic hydrochlorate and calcium hydroxide: will be equivalent to output at least 5%, preferably 1/2 of 10%~80% mole calcium hydroxide amount adds in the epoxy succinic acid salt solution of pH value 5~7, be heated to 100 ℃ and constant temperature 2h, the calcium hydroxide that adds all the other 1/2 amounts then is heated to 100 ℃ and constant temperature 2h.This method productive rate is higher, and synthetic product is effective to polyvalent cations such as chelating calcium, magnesium, and can be used as washing auxiliary detergent, to substitute phosphorus be auxiliary agent.But this method is strong as the calcium hydroxide corrodibility of catalyzer, easily moisture absorption and apt to deteriorate, and reaction product need pass through ion-exchange, esterification and processing such as carboxylate separation and saponification, and it is low etc. that the target product relative molecular mass is crossed.
Summary of the invention
The purpose of this invention is to provide a kind of method that with lime carbonate is catalyzer from the synthetic poly-epoxy succinic acid of Epoxysuccinic acid.Calcium carbonate catalyst has non-hygroscopic, the non-advantage such as water-soluble and not perishable of no burn into.This method is synthesized the poly-epoxy succinic acid reacting balance, and technical process is short, the product yield height, and product separation is easy, and relative molecular mass is higher.
The present invention is a kind of method that is catalyzer from the synthetic poly-epoxy succinic acid of Epoxysuccinic acid with lime carbonate.Comprise following operation steps:
(1) Epoxysuccinic acid is dissolved in the deionized water, the mass ratio of Epoxysuccinic acid and deionized water is 1: 1~1: 3;
(2) add sodium hydroxide, the mass ratio of Epoxysuccinic acid and sodium hydroxide is 1: 0.1~1: 0.2; Temperature is controlled at below 80 ℃ and generates epoxy sodium succinate through alkalization;
(3) add catalyzer carbonic acid calcium, the mass ratio of Epoxysuccinic acid and lime carbonate is 1: 0.02~1: 0.2; Polymeric reaction temperature is 90~105 ℃, and polymerization reaction time is 3~6h, promptly makes the poly-epoxy succinic acid crude product, the refining after filtration then poly-epoxy succinic acid that obtains.
The mass ratio of Epoxysuccinic acid of the present invention and deionized water is preferably 1: 2~and 1: 2.2.
The mass ratio of Epoxysuccinic acid of the present invention and sodium hydroxide is preferably 1: 0.15~and 1: 0.17.
The mass ratio of Epoxysuccinic acid of the present invention and lime carbonate is preferably 1: 0.05~and 1: 0.1.
The best temperature of polyreaction of the present invention is 90~100 ℃, and polymerization reaction time is 4h.
The mass ratio of Epoxysuccinic acid of the present invention and deionized water is 1: 1~1: 3, and the product solid content reduces during hypervolia, and operation was stable inadequately when the water yield was very few.The mass ratio of Epoxysuccinic acid and sodium hydroxide is 1: 0.1~1: 0.2, and amount of sodium hydroxide too much reduces with the very few product relative molecular mass that all can make.The temperature of reaction of Epoxysuccinic acid and sodium hydroxide is no more than 80 ℃, can cause the epoxy succinic acid hydrolysis when temperature is too high.The mass ratio of Epoxysuccinic acid and lime carbonate is 1: 0.02~1: 0.2, suitably reduces calcium carbonate quantity the product relative molecular mass is improved, but product yield is reduced when very few, and the product relative molecular mass is reduced.The adding temperature of lime carbonate without limits, preferably 70~100 ℃.The polymeric reaction temperature of Epoxysuccinic acid is 90~105 ℃ behind the adding catalyzer carbonic acid calcium, and preferably 90~100 ℃, polymerization reaction time is 4h.The poly-epoxy succinic acid of preparation adopts the gel chromatography relative molecular mass.The method that provides with invention can obtain product yield up to 100%, relative molecular mass is 300~1500 poly-epoxy succinic acid.The structural formula of the poly-epoxy succinic acid A that makes is:
Raw material Epoxysuccinic acid, lime carbonate and sodium hydroxide that the present invention uses can adopt commercially available technical grade product, calcium carbonate catalyst is compared with the calcium hydroxide catalyzer, lime carbonate has non-hygroscopic, the non-advantage such as water-soluble and not perishable of no burn into, lime carbonate adds alkali can not generate calcium hydroxide, is a kind of safer, stable catalyst more.With lime carbonate is that catalyzer synthesizes poly-epoxy succinic acid from Epoxysuccinic acid, reacting balance, and technical process is simple, the product yield height, the product relative molecular mass is higher.The poly-epoxy succinic acid of the inventive method preparation has threshold effect, is a kind of Scale inhibitors of excellent performance, and calcium ion is had very high tolerance, is applicable to that high-alkali high solid water is.
Embodiment
Embodiment 1: under constantly stirring, 100g Epoxysuccinic acid, 16g sodium hydroxide are added in the 217g deionized water, keep temperature of reaction to be no more than 65 ℃, get the Epoxysuccinic acid sodium solution, in the time of 80 ℃, add lime carbonate 7.6g, react 4h down at 98 ℃, remove by filter lime carbonate, promptly make poly-epoxy succinic acid, yield 100%, solid content 30%, relative molecular mass 400~1000 (being equivalent to n=4 in the poly-epoxy succinic acid structural formula~9).
Embodiment 2: under constantly stirring, 100g Epoxysuccinic acid, 15g sodium hydroxide are added in the 217g deionized water, keep temperature of reaction to be no more than 65 ℃, get the Epoxysuccinic acid sodium solution, in the time of 80 ℃, add lime carbonate 7.6g, react 4h down at 98 ℃, remove by filter lime carbonate, promptly make poly-epoxy succinic acid, yield 100%, solid content 30%, relative molecular mass 400~1000 (being equivalent to n=4~9).
Embodiment 3: under constantly stirring, 100g Epoxysuccinic acid, 17g sodium hydroxide are added in the 217g deionized water, keep temperature of reaction to be no more than 65 ℃, get the Epoxysuccinic acid sodium solution, in the time of 80 ℃, add lime carbonate 7.6g, react 4h down at 98 ℃, remove by filter lime carbonate, promptly make poly-epoxy succinic acid, yield 100%, solid content 30%, relative molecular mass 400~1000 (being equivalent to n=4~9).
Embodiment 4: under constantly stirring, 100g Epoxysuccinic acid, 16g sodium hydroxide are added in the 200g deionized water, keep temperature of reaction to be no more than 65 ℃, get the Epoxysuccinic acid sodium solution, in the time of 80 ℃, add lime carbonate 7.6g, react 4h down at 98 ℃, remove by filter lime carbonate, promptly make poly-epoxy succinic acid, yield 100%, solid content 30%, relative molecular mass 400~1000 (being equivalent to n=4~9).
Embodiment 5: under constantly stirring, 100g Epoxysuccinic acid, 16g sodium hydroxide are added in the 220g deionized water, keep temperature of reaction to be no more than 65 ℃, get the Epoxysuccinic acid sodium solution, in the time of 80 ℃, add lime carbonate 7.6g, react 4h down at 98 ℃, remove by filter lime carbonate, promptly make poly-epoxy succinic acid, yield 100%, solid content 30%, relative molecular mass 400~1000 (being equivalent to n=4~9).
Embodiment 6: under constantly stirring, 100g Epoxysuccinic acid, 16g sodium hydroxide are added in the 217g deionized water, keep temperature of reaction to be no more than 60 ℃, get the Epoxysuccinic acid sodium solution, in the time of 80 ℃, add lime carbonate 7.6g, react 4h down at 98 ℃, remove by filter lime carbonate, promptly make poly-epoxy succinic acid, yield 100%, solid content 30%, relative molecular mass 400~1000 (being equivalent to n=4~9).
Embodiment 7: under constantly stirring, 100g Epoxysuccinic acid, 16g sodium hydroxide are added in the 217g deionized water, keep temperature of reaction to be no more than 80 ℃, get the Epoxysuccinic acid sodium solution, in the time of 80 ℃, add lime carbonate 7.6g, react 4h down at 98 ℃, remove by filter lime carbonate, promptly make poly-epoxy succinic acid, yield 100%, solid content 30%, relative molecular mass 400~1000 (being equivalent to n=4~9).
Embodiment 8: under constantly stirring, 100g Epoxysuccinic acid, 16g sodium hydroxide are added in the 217g deionized water, keep temperature of reaction to be no more than 65 ℃, get the Epoxysuccinic acid sodium solution, in the time of 70 ℃, add lime carbonate 7.6g, react 4h down at 98 ℃, remove by filter lime carbonate, promptly make poly-epoxy succinic acid, yield 100%, solid content 30%, relative molecular mass 400~1000 (being equivalent to n=4~9).
Embodiment 9: under constantly stirring, 100g Epoxysuccinic acid, 16g sodium hydroxide are added in the 217g deionized water, keep temperature of reaction to be no more than 65 ℃, get the Epoxysuccinic acid sodium solution, in the time of 100 ℃, add lime carbonate 7.6g, react 4h down at 98 ℃, remove by filter lime carbonate, promptly make poly-epoxy succinic acid, yield 100%, solid content 30%, relative molecular mass 400~1000 (being equivalent to n=4~9).
Embodiment 10: under constantly stirring, 100g Epoxysuccinic acid, 16g sodium hydroxide are added in the 217g deionized water, keep temperature of reaction to be no more than 65 ℃, get the Epoxysuccinic acid sodium solution, in the time of 80 ℃, add lime carbonate 5g, react 4h down at 98 ℃, remove by filter lime carbonate, promptly make poly-epoxy succinic acid, yield 100%, solid content 30%, relative molecular mass 600~1500 (being equivalent to n=5~12).
Embodiment 11: under constantly stirring, 100g Epoxysuccinic acid, 16g sodium hydroxide are added in the 217g deionized water, keep temperature of reaction to be no more than 65 ℃, get the Epoxysuccinic acid sodium solution, in the time of 80 ℃, add lime carbonate 10g, react 4h down at 98 ℃, remove by filter lime carbonate, promptly make poly-epoxy succinic acid, yield 100%, solid content 30%, relative molecular mass 300~800 (being equivalent to n=2~7).
Embodiment 12: under constantly stirring, 100g Epoxysuccinic acid, 16g sodium hydroxide are added in the 217g deionized water, keep temperature of reaction to be no more than 65 ℃, get the Epoxysuccinic acid sodium solution, in the time of 80 ℃, add lime carbonate 7.6g, react 4h down at 95 ℃, remove by filter lime carbonate, promptly make poly-epoxy succinic acid, yield 100%, solid content 30%, relative molecular mass 400~1000 (being equivalent to n=4~9).
Embodiment 13: under constantly stirring, 100g Epoxysuccinic acid, 16g sodium hydroxide are added in the 217g deionized water, keep temperature of reaction to be no more than 65 ℃, get the Epoxysuccinic acid sodium solution, in the time of 80 ℃, add lime carbonate 7.6g, react 4h down at 100 ℃, remove by filter lime carbonate, promptly make poly-epoxy succinic acid, yield 100%, solid content 30%, relative molecular mass 400~1000 (being equivalent to n=4~9).
Embodiment 14: under constantly stirring, 100g Epoxysuccinic acid, 16g sodium hydroxide are added in the 217g deionized water, keep temperature of reaction to be no more than 65 ℃, get the Epoxysuccinic acid sodium solution, in the time of 80 ℃, add lime carbonate 7.6g, react 3.5h down at 98 ℃, remove by filter lime carbonate, promptly make poly-epoxy succinic acid, yield 100%, solid content 30%, relative molecular mass 400~1000 (being equivalent to n=4~9).
Embodiment 15: under constantly stirring, 100g Epoxysuccinic acid, 16g sodium hydroxide are added in the 217g deionized water, keep temperature of reaction to be no more than 65 ℃, get the Epoxysuccinic acid sodium solution, in the time of 80 ℃, add lime carbonate 7.6g, react 5h down at 98 ℃, remove by filter lime carbonate, promptly make poly-epoxy succinic acid, yield 100%, solid content 30%, relative molecular mass 400~1500 (being equivalent to n=4~12).
Embodiment 16: under constantly stirring, 100g Epoxysuccinic acid, 10g sodium hydroxide are added in the 217g deionized water, keep temperature of reaction to be no more than 65 ℃, get the Epoxysuccinic acid sodium solution, in the time of 80 ℃, add lime carbonate 7.6g, react 4h down at 98 ℃, remove by filter lime carbonate, promptly make poly-epoxy succinic acid, yield 100%, solid content 30%, relative molecular mass 300~900 (being equivalent to n=2~8).
Embodiment 17: under constantly stirring, 100g Epoxysuccinic acid, 20g sodium hydroxide are added in the 217g deionized water, keep temperature of reaction to be no more than 65 ℃, get the Epoxysuccinic acid sodium solution, in the time of 80 ℃, add lime carbonate 7.6g, react 4h down at 98 ℃, remove by filter lime carbonate, promptly make poly-epoxy succinic acid, yield 100%, solid content 30%, relative molecular mass 300~900 (being equivalent to n=2~8).
Embodiment 18: under constantly stirring, 100g Epoxysuccinic acid, 16g sodium hydroxide are added in the 100g deionized water, keep temperature of reaction to be no more than 65 ℃, get the Epoxysuccinic acid sodium solution, in the time of 80 ℃, add lime carbonate 7.6g, react 4h down at 98 ℃, remove by filter lime carbonate, promptly make poly-epoxy succinic acid, yield 100%, solid content 40%, relative molecular mass 400~1000 (being equivalent to n=4~9).
Embodiment 19: under constantly stirring, 100g Epoxysuccinic acid, 16g sodium hydroxide are added in the 300g deionized water, keep temperature of reaction to be no more than 65 ℃, get the Epoxysuccinic acid sodium solution, in the time of 80 ℃, add lime carbonate 7.6g, react 4h down at 98 ℃, remove by filter lime carbonate, promptly make poly-epoxy succinic acid, yield 100%, solid content 20%, relative molecular mass 400~1000 (being equivalent to n=4~9).
Embodiment 20: under constantly stirring, 100g Epoxysuccinic acid, 16g sodium hydroxide are added in the 217g deionized water, keep temperature of reaction to be no more than 65 ℃, get the Epoxysuccinic acid sodium solution, in the time of 80 ℃, add lime carbonate 2g, react 4h down at 98 ℃, remove by filter lime carbonate, promptly make poly-epoxy succinic acid, yield 93%, solid content 30%, relative molecular mass 600~1500 (being equivalent to n=5~12).
Embodiment 21: under constantly stirring, 100g Epoxysuccinic acid, 16g sodium hydroxide are added in the 217g deionized water, keep temperature of reaction to be no more than 65 ℃, get the Epoxysuccinic acid sodium solution, in the time of 80 ℃, add lime carbonate 20g, react 4h down at 98 ℃, remove by filter lime carbonate, promptly make poly-epoxy succinic acid, yield 100%, solid content 30%, relative molecular mass 300~800 (being equivalent to n=2~7).
Embodiment 22: under constantly stirring, 100g Epoxysuccinic acid, 16g sodium hydroxide are added in the 217g deionized water, keep temperature of reaction to be no more than 65 ℃, get the Epoxysuccinic acid sodium solution, in the time of 80 ℃, add lime carbonate 7.6g, react 4h down at 90 ℃, remove by filter lime carbonate, promptly make poly-epoxy succinic acid, yield 100%, solid content 30%, relative molecular mass 400~1000 (being equivalent to n=4~9).
Embodiment 23: under constantly stirring, 100g Epoxysuccinic acid, 16g sodium hydroxide are added in the 217g deionized water, keep temperature of reaction to be no more than 65 ℃, get the Epoxysuccinic acid sodium solution, in the time of 80 ℃, add lime carbonate 7.6g, react 4h down at 105 ℃, remove by filter lime carbonate, promptly make poly-epoxy succinic acid, yield 100%, solid content 30%, relative molecular mass 400~1000 (being equivalent to n=4~9).
Claims (5)
1, a kind of is the preparing polyepoxy succinic acid of catalyzer with lime carbonate, comprises following operation steps:
(1) Epoxysuccinic acid is dissolved in the deionized water, the mass ratio of Epoxysuccinic acid and deionized water is 1: 1~1: 3;
(2) add sodium hydroxide, the mass ratio of Epoxysuccinic acid and sodium hydroxide is 1: 0.1~1: 0.2; Temperature is controlled at below 80 ℃ and generates epoxy sodium succinate through alkalization;
(3) add catalyzer carbonic acid calcium, the mass ratio of Epoxysuccinic acid and lime carbonate is 1: 0.02~1: 0.2; Polymeric reaction temperature is 90~105 ℃, and polymerization reaction time is 3~6h, promptly makes the poly-epoxy succinic acid crude product, the refining after filtration then poly-epoxy succinic acid that obtains.
2, method according to claim 1 is characterized in that: the mass ratio of Epoxysuccinic acid and deionized water is 1: 2~1: 2.2.
3, method according to claim 1 is characterized in that: the mass ratio of Epoxysuccinic acid and sodium hydroxide is 1: 0.15~1: 0.17.
4, method according to claim 1 is characterized in that: the mass ratio of Epoxysuccinic acid and lime carbonate is 1: 0.05~1: 0.1.
5, method according to claim 1 is characterized in that: polymeric reaction temperature is 90~100 ℃, and polymerization reaction time is 4h.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN 200310101836 CN1240746C (en) | 2003-10-20 | 2003-10-20 | Prepn process of polyepoxy succinic acid with calcium sulfate as catalyst |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN 200310101836 CN1240746C (en) | 2003-10-20 | 2003-10-20 | Prepn process of polyepoxy succinic acid with calcium sulfate as catalyst |
Publications (2)
Publication Number | Publication Date |
---|---|
CN1609132A true CN1609132A (en) | 2005-04-27 |
CN1240746C CN1240746C (en) | 2006-02-08 |
Family
ID=34756261
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN 200310101836 Expired - Fee Related CN1240746C (en) | 2003-10-20 | 2003-10-20 | Prepn process of polyepoxy succinic acid with calcium sulfate as catalyst |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN1240746C (en) |
-
2003
- 2003-10-20 CN CN 200310101836 patent/CN1240746C/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
CN1240746C (en) | 2006-02-08 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN1096436C (en) | Cement additives | |
EP2180004B1 (en) | Olefinically unsaturated phosphonate compounds, polymers made therefrom and their use | |
US5312967A (en) | Process for making activated aldarate esters, ester/lactones and lactones | |
US4435556A (en) | Method of making and using novel scale inhibiting terpolymer | |
KR20140088877A (en) | Small particle size hypophosphite telomers of unsaturated carboxylic acids | |
CN1724447A (en) | Water reducing agent of poly carboxylic acid series concrete and its preparation process | |
CN1699338A (en) | Thiosulfuric acid derivant preparation | |
CA2634745C (en) | Improved biodegradability of antiscalant formulations | |
FR2892420A1 (en) | New polymer having a principal hydrocarbon chain and phosphonated and polyoxyalkylated lateral groups useful e.g. to liquefy mineral particle suspension, particularly cement composition | |
CN1240745C (en) | Prepn process of polyepoxy succinic acid with calcium sulfate as catalyst | |
CN1240746C (en) | Prepn process of polyepoxy succinic acid with calcium sulfate as catalyst | |
CN1636921A (en) | Concrete water reducing agent of polyacrylic acid and its synthesis process | |
CN1014979B (en) | Making method used in oil field for flocculated-etching-retarding agent | |
CN1675259A (en) | Method for producing polyvinylacetals | |
CN1214703A (en) | Process for suspension polymerization of vinyl chloride | |
US5519102A (en) | Aqueous polymerization method for poly(isopropenylphosphonic acid) | |
FI57118B (en) | SAMPOLYMER AV AKRYLSYRA VILKA AER ANVAENDBARA SAOSOM KOMPLEXBILDARE OCH / ELLER SEQUENTING SEED FOR OVER FLERVAERDA METAL IONER OCH FOERFARANDE FOER DERAS FRAMSTAELLNING | |
CN1830986A (en) | Method for preparing ammonium salts of cyclohexanpentol phosphate ester | |
AU2012332645A1 (en) | Vinyl monomers having chelating functionality | |
RU2618220C2 (en) | Method for polyester convertion to polymeric acid | |
CN110845664A (en) | Calcium carbonate scale inhibitor and preparation method thereof | |
CN109264875B (en) | PER-PAMAM and PESA phosphorus-free composite scale inhibitor | |
CN1319876C (en) | Method for preparing biodegradable water treatment agent PECS | |
US4201858A (en) | Method of preparing polyacetal carboxylates | |
US4492788A (en) | Partially deacylated ultra-high molecular weight poly(N-propionylethylenimines) |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
C19 | Lapse of patent right due to non-payment of the annual fee | ||
CF01 | Termination of patent right due to non-payment of annual fee |