CN102154052A - Preparation method of fluorine resin - Google Patents
Preparation method of fluorine resin Download PDFInfo
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- CN102154052A CN102154052A CN2011100315243A CN201110031524A CN102154052A CN 102154052 A CN102154052 A CN 102154052A CN 2011100315243 A CN2011100315243 A CN 2011100315243A CN 201110031524 A CN201110031524 A CN 201110031524A CN 102154052 A CN102154052 A CN 102154052A
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- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 37
- 239000011737 fluorine Substances 0.000 title claims abstract description 35
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000011347 resin Substances 0.000 title abstract 3
- 229920005989 resin Polymers 0.000 title abstract 3
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 239000003999 initiator Substances 0.000 claims abstract description 13
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical group CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 9
- -1 perfluoroalkyl iodide Chemical compound 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 9
- 239000004342 Benzoyl peroxide Substances 0.000 claims abstract description 8
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical group C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims abstract description 8
- 235000019400 benzoyl peroxide Nutrition 0.000 claims abstract description 8
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 claims abstract description 8
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical group CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims abstract description 7
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 150000001336 alkenes Chemical class 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 229940087305 limonene Drugs 0.000 claims abstract description 4
- 235000001510 limonene Nutrition 0.000 claims abstract description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 9
- 230000018044 dehydration Effects 0.000 claims description 8
- 238000006297 dehydration reaction Methods 0.000 claims description 8
- 238000010792 warming Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 4
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 claims description 2
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 abstract description 8
- 238000005516 engineering process Methods 0.000 abstract description 4
- 238000005553 drilling Methods 0.000 abstract description 3
- 238000005461 lubrication Methods 0.000 abstract description 3
- 238000001914 filtration Methods 0.000 abstract description 2
- 230000008014 freezing Effects 0.000 abstract description 2
- 238000007710 freezing Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 abstract 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 abstract 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 abstract 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract 2
- 239000006227 byproduct Substances 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 239000008096 xylene Substances 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 12
- 150000002221 fluorine Chemical class 0.000 description 7
- 238000010992 reflux Methods 0.000 description 6
- OGSJMFCWOUHXHN-UHFFFAOYSA-N 1-iodononane Chemical compound CCCCCCCCCI OGSJMFCWOUHXHN-UHFFFAOYSA-N 0.000 description 2
- OMOUYWRNCDFZAM-UHFFFAOYSA-N 2-iodoundecane Chemical compound CC(CCCCCCCCC)I OMOUYWRNCDFZAM-UHFFFAOYSA-N 0.000 description 2
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 2
- KWXGJTSJUKTDQU-UHFFFAOYSA-N 1,1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8-heptadecafluoro-8-iodooctane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)I KWXGJTSJUKTDQU-UHFFFAOYSA-N 0.000 description 1
- BULLJMKUVKYZDJ-UHFFFAOYSA-N 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluoro-6-iodohexane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)I BULLJMKUVKYZDJ-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 244000248349 Citrus limon Species 0.000 description 1
- 235000005979 Citrus limon Nutrition 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Landscapes
- Lubricants (AREA)
Abstract
The invention discloses a preparation method of fluorine resin, comprising the following steps of: mixing 33-62 parts by weight of perfluoroalkyl iodide and 0.3-0.8 parts by weight of initiator, and then heating to 60-100 DEG C, wherein the initiator is benzoyl peroxide or azobisisobutyronitrile; dropping 7-14 parts by weight of olefin, wherein the olefin is one or two of styrene, octylene, pinene and limonene; reacting at 60-100 DEG C for 3-5 hours; then adding 75-100 parts by weight of solvent, 28-33 parts by weight of acetic acid and 65-70 parts by weight of zinc powder, wherein the solvent is isopropanol or xylene; reacting at 60-100 DEG C for 3-5 hours to obtain a product; and filtering, water-washing, dehydrating and separating the product to obtain a target product. A continuous adding manner is adopted in the method, the reaction is easy to control, no byproduct is generated, the obtained product is easy to separate, and has high selectivity, low frictional factor (0.05-0.1), a water repellence angle of over 110 DEG and high oil repellency up to the first grade, does not freeze at 35 DEG C below zero, and does not decompose at 350 DEG C; and the fluorine resin can be used in the fields such as deep-sea drilling, ignitable ice exploiting, astronautical technology, equipment lubrication under the working condition of permanent freezing layers, and the like.
Description
Technical field
The present invention relates to a kind of preparation method of fluorocarbon, particularly a kind of preparation method of fluorine fat.
Background technology
Existing fluorine fat is applied to deep-sea drilling more, the exploitation of combustible ice, fields such as aeronautical and space technology, causes its duration of service short because little, the molecular weight of its hydrocarbon key bond energy is low, high and low temperature resistance is poor, causes and can't use freezing below-30 ℃, anti-contamination is poor, big (〉 0.1 of frictional coefficient).Along with development of science and technology in recent years, the equipment lubrication that forever freezes under layer working condition need have lubricity at-35 ℃ to 350 ℃, frictional coefficient low (0.05-0.1), and the lubricating grease of existing fluorine fat preparation can't meet the demands.
Summary of the invention
A kind of-35 ℃ to 350 ℃ preparation methods that the technical problem to be solved in the present invention provides with lubricity, frictional coefficient is low, Application Areas is wide fluorine fat.
Technical solution of the present invention is:
A kind of preparation method of fluorine fat, its step is as follows:
According to the parts by weight meter with 33-62 part perfluoroalkyl iodides be warming up to 60-100 ℃ after 0.3-0.8 part initiator mixes; described initiator is benzoyl peroxide or Diisopropyl azodicarboxylate; drip 7-14 part alkene; described alkene is vinylbenzene; octene; firpene; in the limonene one or both; reacted 3-5 hour down at 60-100 ℃; add 75-100 part solvent then; 28-33 part acetate; 6.5-7.0 part zinc powder; described solvent is Virahol or dimethylbenzene; obtained product in 3-5 hour 60-100 ℃ of reaction, this product is filtered; washing; dehydration separates the acquisition target product.
Above-mentioned perfluoroalkyl iodides molecular formula is F (CF
2)
nI or F (CF
2)
nCH
2CH
2I, wherein n is 6-20 even number.
Above-mentioned perfluoroalkyl iodides is n=2,14,16,18 and 20 mixture.
Compared with prior art, present method adopts the mode that adds continuously, is major ingredient with the perfluoroalkyl iodides and the alkene of high fluorocarbon chain, initiator, acetate and zinc powder are the method for feedstock production fluorine fat, easy control of reaction system, the product of acquisition is easily separated, no coupling product, the selectivity height, frictional coefficient low (0.05-0.1) ,-35 ℃ are not freezed, and 350 ℃ are not decomposed, refuse the water angle and can reach more than 110 °, refuse oil and can reach one-level; Can be applicable to the exploitation, spationautics of deep-sea drilling, combustible ice, forever freeze fields such as equipment lubrication under layer working condition.
Embodiment
Embodiment 1
The mixture that adds perfluoroalkyl iodides in the 500ml flask that stirring, electrically heated cover, thermometer, reflux exchanger, dropping funnel, inflating catheter are housed is F (CF wherein
2) 12I 315g, F (CF
2) 14I 90g, F (CF
2) 16I 31.5g, F (CF
2) 18I 9g, F (CF
2) 20I 4.5g, add initiator benzoyl peroxide 3g, be heated to 70 ℃, keep temperature of reaction 70-85 ℃ in the beginning drip styrene dropping process, vinylbenzene drops to 70g to be stopped to drip, and continues reaction 4h, and the product that obtains is moved in the 2000ml flask, add the 800g Virahol, 300g acetate, the 65g zinc powder, be warming up to 90 ℃ of reaction 3h after stirring, the product of acquisition after filtration, washing, dehydration separates acquisition fluorine fat, and this product has aromatic odour, the ski frictional coefficient of handling with this fluorine fat is 0.06,-36 ℃ are not freezed, and 390 ℃ are not decomposed, and refusing the water angle is 113 °, refusing oil and can reach one-level, is a kind of fluorine fat of excellent performance.
Embodiment 2
Stirring is being housed, the electrically heated cover, thermometer, reflux exchanger, dropping funnel, add perfluoro octyl iodide F (CF2) 8I 330g in the 500ml flask of inflating catheter, add initiator benzoyl peroxide 5g, be heated to 80 ℃, add the 5g limonene, keep temperature of reaction 80-95 ℃ in the beginning drip styrene dropping process, vinylbenzene is added drop-wise to 65g to be stopped to drip, continue reaction 4h, the product that obtains is moved in the 2000ml flask, add the 900g Virahol, 300g acetate, the 68g zinc powder, be warming up to 90 ℃ of reaction 5h after stirring, the product that obtains filters, washing, dehydration separates acquisition product fluorine fat, have good low temperature properties, wear resistance through this fluorine fat of wipe test.This product has the fluorine fat of lemon smell, and the ski frictional coefficient of handling with this hydrogen fluorine fat is 0.08 ,-40 ℃ and does not freeze that 360 ℃ are not decomposed, and refusing the water angle is 111 °, refuses oil and can reach one-level, is a kind of fluorine fat of excellent performance.
Embodiment 3
Stirring is being housed, the electrically heated cover, thermometer, reflux exchanger, dropping funnel, add perfluoro-hexyl iodide F (CF2) 6I 404g in the 500ml flask of inflating catheter, add initiator benzoyl peroxide 8g, be heated to 60 ℃, begin to drip and keep temperature of reaction 60-75 ℃ in the octene dropping process, octene is added drop-wise to 110g to be stopped to drip, continue reaction 3h, the product that obtains is moved in the 2000ml flask, add the 1000g Virahol, 300g acetate, the 70g zinc powder, be warming up to 60 ℃ of reaction 4h after stirring, the product that obtains filters, washing, dehydration separate to obtain product fluorine fat, is 0.1 ,-35 ℃ with the ski frictional coefficient of this fluorine fat processing and does not freeze, 380 ℃ are not decomposed, refusing the water angle is 110 °, refuses oil and can reach one-level, is a kind of fluorine fat of excellent performance.
Embodiment 4
Stirring is being housed, the electrically heated cover, thermometer, reflux exchanger, dropping funnel, add perfluor nonyl iodine F (CF2) 10I 450g in the 500ml flask of inflating catheter, add initiator benzoyl peroxide 4g, be heated to 90 ℃, begin to drip and keep temperature of reaction 85-100 ℃ in the octene dropping process, octene is added drop-wise to 85g to be stopped to drip, continue reaction 4h, the product that obtains is moved in the 2000ml flask, add the 850g Virahol, 280g acetate, the 67g zinc powder, be warming up to 80 ℃ of reaction 3.5h after stirring, the product that obtains filters, washing, dehydration separate to obtain fluorine fat, is 0.05 ,-38 ℃ with the ski frictional coefficient of this fluorine fat processing and does not freeze, 370 ℃ are not decomposed, refusing the water angle is 120 °, refuses oil and can reach one-level, is a kind of fluorine fat of excellent performance.
Embodiment 5
Stirring is being housed, the electrically heated cover, thermometer, reflux exchanger, dropping funnel, add perfluor nonyl iodine F (CF2) 10I 620g in the 500ml flask of inflating catheter, add initiator benzoyl peroxide 6g, be heated to 100 ℃, begin to drip and keep temperature of reaction 85-100 ℃ in the firpene dropping process, firpene is added drop-wise to 138g to be stopped to drip, continue reaction 5h, the product that obtains is moved in the 2000ml flask, add the 750g Virahol, 310g acetate, the 70g zinc powder, be warming up to 90 ℃ of reaction 3h after stirring, the product that obtains filters, washing, dehydration separate to obtain fluorine fat, is 0.10 ,-37 ℃ with the ski frictional coefficient of this fluorine fat processing and does not freeze, 350 ℃ are not decomposed, refusing the water angle is 118 °, refuses oil and can reach one-level, is a kind of fluorine fat of excellent performance.
Embodiment 6
Stirring is being housed, the electrically heated cover, thermometer, reflux exchanger, dropping funnel, add perfluor nonyl iodoethane F (CF2) 10CH2CH2I 560g in the 500ml flask of inflating catheter, add initiator azo-bis-isobutyl cyanide 8g, be heated to 90 ℃, begin to drip and keep temperature of reaction 80-95 ℃ in the firpene dropping process, firpene is added drop-wise to 120g to be stopped to drip, continue reaction 4.5h, the product that obtains is moved in the 2000ml flask, add 1000g dimethylbenzene, 328g acetate, the 68g zinc powder, be warming up to 90 ℃ of reaction 4.5h after stirring, the product that obtains filters, washing, dehydration separate to obtain fluorine fat, is 0.05 ,-35 ℃ with the ski frictional coefficient of this fluorine fat processing and does not freeze, 360 ℃ are not decomposed, refusing the water angle is 110 °, refuses oil and can reach one-level, is a kind of fluorine fat of excellent performance.
Perfluor nonyl iodoethane F (CF2) 10CH2CH2I among the embodiment 6 can also use the mixture of F (CF2) 6CH2CH2I, F (CF2) 8CH2CH2I or F (CF2) 12CH2CH2I, F (CF2) 14CH2CH2I, F (CF2) 16CH2CH2I, F (CF2) 18CH2CH2I and F (CF2) 20CH2CH2I to replace, and molecular formula is F (CF among the embodiment 1-embodiment 5
2)
nThe material of I also can replace with above-mentioned substance.
By embodiment 1-6, can obtain to have lubricity at-35 ℃-350 ℃, low temperature-35 ℃ does not freeze, 350 ℃ are not decomposed, and frictional coefficient low (0.05-0.10) is refused the water angle and can be reached more than 110 °, refuse the fluorine fat that oil can reach one-level, this fluorine fat can have special smell simultaneously.
Claims (3)
1. the preparation method of a fluorine fat; it is characterized in that: according to the parts by weight meter with 33-62 part perfluoroalkyl iodides be warming up to 60-100 ℃ after 0.3-0.8 part initiator mixes; described initiator is benzoyl peroxide or Diisopropyl azodicarboxylate; drip 7-14 part alkene; described alkene is vinylbenzene; octene; firpene; in the limonene one or both; reacted 3-5 hour down at 60-100 ℃; add 75-100 part solvent then; 28-33 part acetate; 6.5-7.0 part zinc powder; described solvent is Virahol or dimethylbenzene, obtains product in 3-5 hour 60-100 ℃ of reaction, and this product is filtered; washing; dehydration separates the acquisition target product.
2. the preparation method of fluorine fat according to claim 1 is characterized in that: the molecular formula of perfluoroalkyl iodides is F (CF
2)
nI or F (CF
2)
nCH
2CH
2I, wherein n is 6-20 even number.
3. the preparation method of fluorine fat according to claim 2 is characterized in that: perfluoroalkyl iodides is n=12,14,16,18 and 20 mixture.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110031524 CN102154052B (en) | 2011-01-29 | 2011-01-29 | Preparation method of fluorine resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110031524 CN102154052B (en) | 2011-01-29 | 2011-01-29 | Preparation method of fluorine resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102154052A true CN102154052A (en) | 2011-08-17 |
| CN102154052B CN102154052B (en) | 2013-07-17 |
Family
ID=44435729
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|---|---|---|---|
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102659507A (en) * | 2012-04-13 | 2012-09-12 | 阜新恒通氟化学有限公司 | Perfluoro alkyl alkane preparation method |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3226449A (en) * | 1962-06-06 | 1965-12-28 | Du Pont | Process for preparing perfluoroalkyl iodides |
| CN1196347A (en) * | 1998-03-27 | 1998-10-21 | 中国科学院上海有机化学研究所 | Long carbonchain poly fluoro iodo alkane and preparation method |
| CN1809621A (en) * | 2003-04-15 | 2006-07-26 | 科莱恩有限公司 | Partially fluorinated lubricants for solid surfaces |
| CN101434511A (en) * | 2008-12-17 | 2009-05-20 | 上海三爱富新材料股份有限公司 | Method for synthesizing middle chain length polyfluoroalkyl ethyl iodide |
-
2011
- 2011-01-29 CN CN 201110031524 patent/CN102154052B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3226449A (en) * | 1962-06-06 | 1965-12-28 | Du Pont | Process for preparing perfluoroalkyl iodides |
| CN1196347A (en) * | 1998-03-27 | 1998-10-21 | 中国科学院上海有机化学研究所 | Long carbonchain poly fluoro iodo alkane and preparation method |
| CN1809621A (en) * | 2003-04-15 | 2006-07-26 | 科莱恩有限公司 | Partially fluorinated lubricants for solid surfaces |
| CN101434511A (en) * | 2008-12-17 | 2009-05-20 | 上海三爱富新材料股份有限公司 | Method for synthesizing middle chain length polyfluoroalkyl ethyl iodide |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102659507A (en) * | 2012-04-13 | 2012-09-12 | 阜新恒通氟化学有限公司 | Perfluoro alkyl alkane preparation method |
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