CN103657725A - Method for preparing catalyst for preparing 1,1,5-trihydroperfluoropentyl methacrylate - Google Patents
Method for preparing catalyst for preparing 1,1,5-trihydroperfluoropentyl methacrylate Download PDFInfo
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- exchange resin
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- perfluorinated sulfonic
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- sulfonic acid
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- 239000003054 catalyst Substances 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 13
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 title abstract 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000003456 ion exchange resin Substances 0.000 claims abstract description 43
- 229920003303 ion-exchange polymer Polymers 0.000 claims abstract description 43
- 239000008139 complexing agent Substances 0.000 claims abstract description 11
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid group Chemical group C(CC(O)(C(=O)O)CC(=O)O)(=O)O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 40
- 150000003460 sulfonic acids Chemical class 0.000 claims description 38
- 229910052739 hydrogen Inorganic materials 0.000 claims description 21
- 239000001257 hydrogen Substances 0.000 claims description 21
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 15
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 10
- 125000005395 methacrylic acid group Chemical group 0.000 claims description 8
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 4
- 235000014655 lactic acid Nutrition 0.000 claims description 2
- 239000004310 lactic acid Substances 0.000 claims description 2
- 239000011347 resin Substances 0.000 abstract description 11
- 229920005989 resin Polymers 0.000 abstract description 11
- 239000000126 substance Substances 0.000 abstract description 7
- -1 neodymium ions Chemical class 0.000 abstract description 6
- 239000011159 matrix material Substances 0.000 abstract description 3
- 230000004048 modification Effects 0.000 abstract description 3
- 238000012986 modification Methods 0.000 abstract description 3
- 238000005809 transesterification reaction Methods 0.000 abstract description 3
- 239000007791 liquid phase Substances 0.000 abstract description 2
- 238000004062 sedimentation Methods 0.000 abstract description 2
- WYRSPTDNOIZOGA-UHFFFAOYSA-K neodymium(3+);trifluoromethanesulfonate Chemical compound [Nd+3].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F WYRSPTDNOIZOGA-UHFFFAOYSA-K 0.000 abstract 3
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 abstract 2
- 230000002378 acidificating effect Effects 0.000 abstract 1
- 238000010668 complexation reaction Methods 0.000 abstract 1
- 230000002035 prolonged effect Effects 0.000 abstract 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 21
- 235000015165 citric acid Nutrition 0.000 description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 7
- 230000032050 esterification Effects 0.000 description 7
- 238000005886 esterification reaction Methods 0.000 description 7
- 239000011737 fluorine Substances 0.000 description 6
- 229910052731 fluorine Inorganic materials 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 229910052681 coesite Inorganic materials 0.000 description 4
- 229910052906 cristobalite Inorganic materials 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- 229910052682 stishovite Inorganic materials 0.000 description 4
- 238000010189 synthetic method Methods 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical group ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- 229910052905 tridymite Inorganic materials 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910006069 SO3H Inorganic materials 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 239000011973 solid acid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- KUGBQWBWWNPMIT-UHFFFAOYSA-N 1,1,2,2,3,3,4,4-octafluoropentan-1-ol Chemical compound CC(F)(F)C(F)(F)C(F)(F)C(O)(F)F KUGBQWBWWNPMIT-UHFFFAOYSA-N 0.000 description 1
- JUGSKHLZINSXPQ-UHFFFAOYSA-N 2,2,3,3,4,4,5,5-octafluoropentan-1-ol Chemical compound OCC(F)(F)C(F)(F)C(F)(F)C(F)F JUGSKHLZINSXPQ-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical class CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 150000001263 acyl chlorides Chemical class 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- 239000005548 dental material Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- 239000000382 optic material Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000012781 shape memory material Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a method for preparing a catalyst for preparing 1,1,5-trihydroperfluoropentyl methacrylate. According to the method, perfluorosulfonate ion-exchange resin is used as a carrier and then loaded with neodymium trifluoromethanesulfonate with a liquid-phase sedimentation method, meanwhile, a complexing agent is used for modification, and a product of the catalyst is produced. The perfluorosulfonate ion-exchange resin in the catalyst is a new kind of ion-exchange resin and has the advantages of high acidity, high thermal stability, high chemical stability and the like. The catalyst loaded with the neodymium trifluoromethanesulfonate has the good transesterification catalyzing performance. The complexation of the complexing agent and the neodymium trifluoromethanesulfonate can be realized under the acidic condition, so that neodymium ions are adsorbed on a resin matrix firmer and not prone to loss, and the service life of the catalyst is prolonged.
Description
Technical field
The present invention relates to a kind of method of Kaolinite Preparation of Catalyst, particularly a kind of methacrylic acid-1 of preparing, the method for preparing catalyst of 1,5-, tri-hydrogen perfluor pentyl esters.
Background technology
Methacrylic acid 1,1,5-tri-hydrogen perfluor pentyl esters (referred to as OF-PMA) are the same with common floride-free acrylate monomer has good homopolymerization and copolymerizable.Its homopolymers and copolymer have the advantages such as surface free energy is low, index of refraction is low, radiation hardness, resistant to chemical media, nearest multiplex wearability, weatherability, chemicals-resistant, waterproof, the grease proofing coating done, and surface treatment coating of plastic lens, heat-resisting shape-memory material, antireflection film, silicones medicine equipment, fibre finish, fiber optic materials, dental material etc.
At present, the synthetic method of fluorinated acrylate mainly contains carboxylic acid anhydrides-fluorine alcohol synthetic method, acyl chlorides-fluorine alcohol synthetic method, carboxylic acid-fluorine alcohol synthetic method. but carboxylic acid anhydrides and acyl chlorides need to synthesize on the spot, and due to multistep reaction, total yield is low; And methacrylic acid and 1,1, the esterification of 5-tri-hydrogen perfluor amylalcohols is synthetic, generally adopts a large amount of sulfuric acid as catalyst, and oxidation and polymerization can occur long-time pyroreaction under a large amount of effect of sulfuric acid, and fluorine-containing alcohol can produce decomposition, is beneficial to side reaction and occurs.And production equipment seriously corroded, three wastes difficult treatment.
DE4342448 adds fluorine-containing ether in the process of (methyl) acrylic acid and N1 alcohol, the direct esterification of N2 alcohol, utilize fluorine-containing ether can dissolve esterification products and with the characteristic of water lower than 5% compatibility, by backflow, shift out the water producing from esterification, driving a reaction carries out to positive direction, thereby can improve the yield of esterification products.
Lin Yi etc., in document " methacrylic acid 1,1,5 one three hydrogen perfluor pentyl esters synthetic ", under fen thiophene crop and sulfuric acid exist, adopt the method for methacrylic acid and octafluoropentanol direct esterification to study methacrylic acid 1,1,5 one three hydrogen perfluor pentyl esters synthetic.The impact of consumption, reactant ratio, reaction temperature and the reaction time that sulfuric acid has been discussed on product yield.And discussed and take anhydrous sodium sulfate during as dehydrating agent, the impact on product yield.The liquid catalysts such as this process using sulfuric acid, have the shortcomings such as corrosivity is strong, the three wastes are many, product purification complexity.
Song Shi is at document " methacrylic acid 1H, 1H, 5H-octafluoropentanol ester study on the synthesis " in methacrylic acid and 1H, 1H, 5H-octafluoropentanol esterification system is that research object has designed the compound perfluorinated sulfonic resin solid acid catalyst of a series of silica nanometers by investigating the catalysis rule of liquid acid, studied the correlation of its structure and performance, the industrial production catalyst of this class special acrylic monomers is selected to have done technical research with design, between the preparation structure of discovery catalyst and catalytic activity, having certain concentration that is related to medium NaOH is 0.08-1mol/L, the catalyst activity that FR6.2 load capacity obtains while being 20wt% is the strongest, FR6.2/SiO2 has extraordinary reusing simultaneously.Compare with other catalyst, but the catalytic activity of FR6.2/SiO2 is higher than gel resin FR6.2 and macropore sulfuric acid resin lower than liquid acid PTS.The compound perfluorinated sulfonic resin solid acid catalyst of this process using silica nanometer, catalytic activity is lower, and service life is short, can not use for a long time.
Prior art has certain disadvantages as known from the above.In order to promote domestic production, reduce production costs, be necessary further to study, find suitable methacrylic acid-1, the preparation method of 1,5-, tri-hydrogen perfluor pentyl ester catalyst.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of methacrylic acid-1 of preparing, the method for preparing catalyst of 1,5-, tri-hydrogen perfluor pentyl esters.
The present invention be take and had perfluorinated sulfonic acid ion exchange resin as carrier, then, by liquid phase sedimentation load TFMS neodymium, uses complexing agent to carry out modification simultaneously, makes this catalyst prod.
The invention provides a kind of methacrylic acid-1 of preparing, the preparation method of the catalyst of 1,5-, tri-hydrogen perfluor pentyl esters, comprises the following steps:
Perfluorinated sulfonic acid ion exchange resin is soaked to 2～5h in the TFMS that accounts for perfluorinated sulfonic acid ion exchange resin mass percent 50～200%, add that to account for perfluorinated sulfonic acid ion exchange resin mass percent be 5～10%, neodymium oxide, add the complexing agent that perfluorinated sulfonic acid ion exchange resin mass percent is 0.1～0.5%, in reaction temperature, be to react 10～20h at 30～80 ℃, with ethanol, clean, dry, obtain the perfluorinated sulfonic acid ion-exchange resin catalyst product of load TFMS neodymium.
Wherein:
The mass percent that TFMS accounts for perfluorinated sulfonic acid ion exchange resin is preferably 150%; The mass percent that TFMS accounts for perfluorinated sulfonic acid ion exchange resin is preferably 8%; The mass percent that neodymium oxide accounts for perfluorinated sulfonic acid ion exchange resin is preferably 0.2%; The time of soaking is preferably 4h; Reaction temperature is preferably 60 ℃; The time of reaction is preferably 15h.
Perfluorinated sulfonic acid ion exchange resin is commercially available prod, and as Shandong Huaxia Shenzhou New Material Co., Ltd. produces product, Shandong Dongyue Chemical Industry Co., Ltd. produces product etc., group pattern Rf-SO3H.
Complexing agent is citric acid, lactic acid, tartaric one or more.Optimization citric acid, chemical name: 2-hydroxy propane-1,2,3-tricarboxylic acids, molecular formula is C6H8O7.
This catalyst prod has following beneficial effect:
1. the advantages such as the perfluorinated sulfonic acid ion exchange resin of this catalyst is the novel ion exchange resin of a class, has acidity strong, and heat endurance is strong, and chemical stability is strong.
2. the catalyst of load TFMS neodymium has the performance of good catalyzed transesterification.Complexing agent can be under acid condition and the complexing of TFMS neodymium, and what make that neodymium ion adsorbs on resin matrix is more firm, be difficult for running off, thus the service life of having improved catalyst, and keep for a long time high activity.
The specific embodiment
Following instance is only to further illustrate the present invention, is not restriction the scope of protection of the invention.Embodiment 1:
Perfluorinated sulfonic acid ion exchange resin is commercially available prod, for Shandong Huaxia Shenzhou New Material Co., Ltd. produces CHF115 type product, group pattern Rf-SO3H.
Perfluorinated sulfonic acid ion exchange resin is soaked to 4h in the TFMS that accounts for perfluorinated sulfonic acid ion exchange resin mass percent 150%, add and account for the neodymium oxide that perfluorinated sulfonic acid ion exchange resin mass percent is 8%, add the citric acid that perfluorinated sulfonic acid ion exchange resin mass percent is 0.2%, 60 ℃ of reaction 10h, with ethanol, clean, dry, obtain the perfluorinated sulfonic acid ion-exchange resin catalyst product of load TFMS neodymium.Be numbered M-1.
Embodiment 2
Add and account for the neodymium oxide that perfluorinated sulfonic acid ion exchange resin mass percent is 5%, the other the same as in Example 1.Products obtained therefrom is numbered M-2.
Embodiment 3
Add and account for the neodymium oxide that perfluorinated sulfonic acid ion exchange resin mass percent is 10%, the other the same as in Example 1.Products obtained therefrom is numbered M-3.
Embodiment 4
Add and account for the citric acid that perfluorinated sulfonic acid ion exchange resin mass percent is 0.1%, the other the same as in Example 1.Products obtained therefrom is numbered M-4.
Embodiment 5
Add and account for the citric acid that perfluorinated sulfonic acid ion exchange resin mass percent is 0.1%, the other the same as in Example 2.Products obtained therefrom is numbered M-5.
Embodiment 6
Add and account for the citric acid that perfluorinated sulfonic acid ion exchange resin mass percent is 0.1%, the other the same as in Example 3.Products obtained therefrom is numbered M-6.
Embodiment 7
Add and account for the citric acid that perfluorinated sulfonic acid ion exchange resin mass percent is 0.5%, the other the same as in Example 1.Products obtained therefrom is numbered M-7.
Embodiment 8
Add and account for the citric acid that perfluorinated sulfonic acid ion exchange resin mass percent is 0.5%, the other the same as in Example 2.Products obtained therefrom is numbered M-8.
Embodiment 9
Add and account for the citric acid that perfluorinated sulfonic acid ion exchange resin mass percent is 0.5%, the other the same as in Example 3.Products obtained therefrom is numbered M-9.
Comparative example 1
Add and account for the citric acid that perfluorinated sulfonic acid ion exchange resin mass percent is 0%, the other the same as in Example 3.Products obtained therefrom is numbered M-10.
Comparative example 2
Use perfluorinated sulfonic acid ion exchange resin as a comparison, production code member is M-11.
Comparative example 3
Press document " methacrylic acid 1H, 1H, 5H-octafluoropentanol ester study on the synthesis " P34 page and make FR6.2/SiO2 catalyst as a comparison, production code member is M-12.
Embodiment 10
Catalyst is used for methacrylic acid 1,1, the evaluation of 5-tri-hydrogen perfluor pentyl esters reactions
The resin catalyst product obtaining in embodiment 1-9 and comparative example 1-3 is put into there-necked flask build-in test, raw material methacrylic acid and 1H, 1H, the mol ratio of 5H-octafluoropentanol is 2:1, solvent is carbon tetrachloride, and consumption is 50ml, and resin catalyst consumption is methacrylic acid 2%, reaction temperature is 120 ℃, reaction 8h finishes, and generates methacrylic acid 1,1,5-tri-hydrogen perfluor pentyl esters, timing sampling.With its content of gas chromatographic analysis.Calculate methacrylic acid 1,1, the yield of 5-tri-hydrogen perfluor pentyl esters.
Table 1: methacrylic acid 1,1 while using different catalysts, the yield of 5-tri-hydrogen perfluor pentyl esters
Embodiment 11
Catalyst is used for methacrylic acid 1,1, the evaluation of 5-tri-hydrogen perfluor pentyl esters reactions
The resin catalyst product obtaining in embodiment 1-9 and comparative example 1-2 is put into there-necked flask build-in test, raw material methacrylic acid and 1H, 1H, the mol ratio of 5H-octafluoropentanol is 2.3:1, solvent is carbon tetrachloride, and consumption is 55ml, and resin catalyst consumption is methacrylic acid 4%, reaction temperature is 130 ℃, reaction 8h finishes, and generates methacrylic acid 1,1,5-tri-hydrogen perfluor pentyl esters, timing sampling.With its content of gas chromatographic analysis.Calculate methacrylic acid 1,1, the yield of 5-tri-hydrogen perfluor pentyl esters.
Table 2: methacrylic acid 1,1 while using different catalysts, the yield of 5-tri-hydrogen perfluor pentyl esters
By table 1, table 2 is known: use this catalyst prod to compare with the simple FR6.2/SiO2 that uses perfluorinated sulfonic acid ion exchange resin (comparative example 2), prepares without catalyst (comparative example 1) and the employing prior art of complexing agent modification, yield is all significantly improved, and the activity of visible catalyst of the present invention is higher; And using after 6 times, methacrylic acid 1,1, the yield of 5-tri-hydrogen perfluor pentyl esters can also reach 80%, so the good stability of catalyst of the present invention, can use for a long time.The advantages such as perfluorinated sulfonic acid ion exchange resin is the novel ion exchange resin of a class, has acidity strong, and heat endurance is strong, and chemical stability is strong.The catalyst of load TFMS neodymium has the performance of good catalyzed transesterification.Citric acid can be under acid condition and the complexing of TFMS neodymium, and what make that neodymium ion adsorbs on resin matrix is more firm, is difficult for running off.Make the active ingredient of catalyst also can keep higher activity through long-term use, long-time stability are good, thereby have good market prospects.
Claims (10)
1. prepare methacrylic acid-1 for one kind, the method for preparing catalyst of 1,5-, tri-hydrogen perfluor pentyl esters, is characterized in that, described preparation method comprises the following steps:
Perfluorinated sulfonic acid ion exchange resin is soaked to 2～5h in the TFMS that accounts for perfluorinated sulfonic acid ion exchange resin mass percent 50～200%, then add and account for the neodymium oxide that perfluorinated sulfonic acid ion exchange resin mass percent is 5～10%, add again the complexing agent that perfluorinated sulfonic acid ion exchange resin mass percent is 0.1～0.5%, in reaction temperature, be to react 10～20h at 30～80 ℃, with ethanol, clean, dry, obtain the perfluorinated sulfonic acid ion-exchange resin catalyst product of load TFMS neodymium.
2. preparation method claimed in claim 1, wherein perfluorinated sulfonic acid ion exchange resin is as catalyst carrier.
3. preparation method claimed in claim 1, adds and accounts for the TFMS that perfluorinated sulfonic acid ion exchange resin mass percent is 150%.
4. preparation method claimed in claim 1, adds and accounts for the complexing agent that perfluorinated sulfonic acid ion exchange resin mass percent is 0.2%.
5. preparation method claimed in claim 1, adds and accounts for the neodymium oxide that perfluorinated sulfonic acid ion exchange resin mass percent is 8%.
6. the preparation method of one of claim 1-5, wherein complexing agent is citric acid, lactic acid, tartaric one or more.
7. the preparation method of one of claim 1-5, wherein complexing agent is citric acid.
8. preparation method claimed in claim 1, wherein reaction temperature is 60 ℃; The time of reaction is 15h.
9. what according to the described preparation method of one of claim 1-5, obtain prepares methacrylic acid-1, the catalyst of 1,5-, tri-hydrogen perfluor pentyl esters.
10. the catalyst of claim 9 is being produced methacrylic acid-1, the application in 1,5-, tri-hydrogen perfluor pentyl esters.
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| CN201310697834.8A CN103657725B (en) | 2013-12-17 | 2013-12-17 | Method for preparing catalyst for preparing 1,1,5-trihydroperfluoropentyl methacrylate |
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| CN103657725B CN103657725B (en) | 2015-04-08 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104803849A (en) * | 2015-04-28 | 2015-07-29 | 上海大学 | Synthesizing method of acrylic fluorine-containing ester and derivatives thereof through catalyzed synthesis of solid acid |
| CN107737611A (en) * | 2017-10-24 | 2018-02-27 | 万华化学集团股份有限公司 | A kind of composite catalyst and the method that 5 hexenoic acids are prepared using the composite catalyst |
| CN114292191A (en) * | 2021-12-17 | 2022-04-08 | 重庆新氟科技有限公司 | Preparation method of fluorine-containing methacrylic acid monomer |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1302848C (en) * | 2004-05-27 | 2007-03-07 | 华东理工大学 | Rare earth contained perfluorocarboxylic Lewis acid catalyst and its preparation |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104803849A (en) * | 2015-04-28 | 2015-07-29 | 上海大学 | Synthesizing method of acrylic fluorine-containing ester and derivatives thereof through catalyzed synthesis of solid acid |
| CN107737611A (en) * | 2017-10-24 | 2018-02-27 | 万华化学集团股份有限公司 | A kind of composite catalyst and the method that 5 hexenoic acids are prepared using the composite catalyst |
| CN114292191A (en) * | 2021-12-17 | 2022-04-08 | 重庆新氟科技有限公司 | Preparation method of fluorine-containing methacrylic acid monomer |
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