CN1955167A - Fluorine-containing chain hydrocarbon melamine derivate with ester-base alkyl ether and carboxylic end group and its preparation method - Google Patents
Fluorine-containing chain hydrocarbon melamine derivate with ester-base alkyl ether and carboxylic end group and its preparation method Download PDFInfo
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Abstract
This invention discloses a category of fluorinated hydrocarbons chain melamine derivate which has end group of esterfunction/alkyl ether and its preparation. Fluorinated hydrocarbons chain melamine derivate has end group of esterfunction/ alkyl ether, of which structural formula is formula I, x,p,z=0,1,2;And x+y=2,p+q=2,e+z=2 but x,p,z does not equal 2 at the same time, among them Rf is formula II, Y=CF2OCH3 or COOCH3n=0-4. in condition of hydrolization/ oxidation, the composite fluorinated hydrocarbons chain melamine derivate that has end group of esterfunction/alkyl ether can be transformed into fluorinated hydrocarbons chain melamine derivate that has end group of reactive carboxy group, among them the end group of carboxylic acid can also participate reaction, form fluorinated hydrocarbons chain melamine derivate that has end group of Carboxylic salt.
Description
Technical field
The present invention relates to a class and contain fluorinated organic compound of trimeric cyanamide structure and preparation method thereof.Specifically a class has ester group, alkyl oxide or the fluorine-containing chain hydrocarbon melamine derivate of carboxylic end group and preparation method thereof.
Background technology
Trimeric cyanamide is a kind of broad-spectrum organic chemical industry's intermediates with uniform texture, and topmost purposes is as the raw material of producing melamine formaldehyde resin; Other purposes mainly contains the following aspects: 1, decoration veneer: can be made into fire prevention, antidetonation, heat-stable veneer sheet; 2, coating: trimeric cyanamide is to can be used as linking agent in the coating at acrylic acid series, alkyd system, epoxy; 3, molding powder: can be made into pure white, anti-daily utensil of beating, sanitary ware and imitative porcelain tableware, the high-grade insulating materials of electrical equipment etc.; 4, paper treating agent; 5, fire retardant.On the other hand, we know that the perfluor chain hydrocarbon polymkeric substance has good thermotolerance, oxidation-resistance, oilness and uninflammability, this class material has performances such as excellent high-low temperature resistant, anti-severe rugged environment, plays irreplaceable vital role in industry such as nuclear power, aerospace.
Summary of the invention
Technical problem to be solved by this invention provide a class new have a perfluoro organic compound that contains the trimeric cyanamide structure of temperature tolerance, weathering resistance and oilness preferably, the present invention provides the preparation method of this compound simultaneously.
The perfluoro organic compound that contains the trimeric cyanamide structure provided by the present invention is that a class has ester group/fluorine-containing chain hydrocarbon melamine derivate of alkyl oxide end group, and its general molecular formula is:
X, p, z=0,1,2; And x+y=2, p+q=2, e+z=2
But x, p, z do not equal 2 simultaneously
R wherein
fFor:
Y=CF
2OCH
3Or COOCH
3
n＝0～4
The present invention provides a class to have the fluorine-containing chain hydrocarbon melamine derivate of carboxylic end group simultaneously, and its general structure is expressed as:
X, p, z=0,1,2; And x+y=2, p+q=2, e+z=2
But x, p, z do not equal 2 simultaneously
R wherein
fFor:
n＝0～4
This fluorine-containing chain hydrocarbon melamine derivate that has carboxylic end group is to have ester group/fluorine-containing chain hydrocarbon melamine derivate of alkyl oxide end group by hydrolysis/oxydrolysis reaction, change the fluorine-containing chain hydrocarbon melamine derivate that has carboxylic end group into, and the carboxylic end group that has in the fluorine-containing chain hydrocarbon melamine derivate structure of carboxylic end group can further participate in reaction, forms the fluorine-containing chain hydrocarbon melamine derivate that has the carboxylate salt end group.
Preferred x, p, z are respectively 0 or 1 corresponding derivative that obtains simultaneously in the said structure formula.
Having ester group/fluorine-containing chain hydrocarbon melamine derivate of alkyl oxide end group, is to obtain by fluorine-containing acyl fluorides monomer and the trimeric cyanamide condensation reaction with ester group/alkyl oxide end group, and reaction formula is as follows:
Y=CF
2OCH
3Or COOCH
3
X, p, z=0,1,2; And x+y=2, p+q=2, e+z=2
But x, p, z do not equal 2 simultaneously
R wherein
fFor:
Y=CF
2OCH
3Or COOCH
3
n＝0～4
Six ripple hydrogen alive in the melamine molecule on three amidos can be generated melamine derivative by some or all of condensation reaction: be displaced to six hydrogen from a hydrogen and all be substituted general molecular formula C
3H
(6-d)N
6(R
f)
d, d=1～6 wherein.
Condensation reaction between the monomer both can be that body carries out condensation reaction, also can be that body carries out condensation reaction in solution, and concrete preparation method is as follows:
1, under 40～180 ℃, carries out the body condensation reaction by containing ester group/alkyl oxide end group fluorine-containing chain hydrocarbon acyl fluorides monomer and trimeric cyanamide.Reaction times 8h～24h.
2, contain ester group/alkyl oxide end group fluorine-containing chain hydrocarbon acyl fluorides monomer by organic solvent dissolution and trimeric cyanamide is that 40～180 ℃ of following polycondensations prepare in temperature of reaction, the reaction times is 5h～16h.The solvent that is adopted in the reaction can be: acetonitrile, pyridine, dimethyl formamide, N-Methyl pyrrolidone etc., and the add-on of solvent should satisfy the reactant solid content 20%～30% in the system; The gas HF that produces in the reaction process can utilize alkali lye to absorb and remove.
The preparation method who has the fluorine-containing chain hydrocarbon melamine derivate of carboxylic end group is to be obtained by hydrolysis/oxydrolysis reaction by the above-mentioned ester group/fluorine-containing chain hydrocarbon melamine derivate of preparing earlier of alkyl oxide end group that has.Concrete preparation method is as follows:
Have in the fluorine-containing chain hydrocarbon melamine derivate of ester group end group and pass through aqueous sodium hydroxide solution earlier, regulate pH value between 7～8, the stirring at room reaction, then regulate pH value and equal 7 with dilute hydrochloric acid, extract with ethyl acetate, distilled water wash obtains having the fluorine-containing chain hydrocarbon melamine derivate of carboxylic end group.The preparation method drips 21% aqueous sodium hydroxide solution in having the fluorine-containing chain hydrocarbon melamine derivate of ester group end group more specifically, until pH value between 7～8, stirring at room reaction 3h, then handle to pH value and equal 7 with 10% dilute hydrochloric acid, distilled water wash is used in the ethyl acetate extraction, takes off a layer oily liquids, vacuum-drying is the fluorine-containing chain hydrocarbon melamine derivate that has carboxylic end group.
Have in the fluorine-containing chain hydrocarbon melamine derivate of alkyl oxide end group and to add 98% vitriol oil and carry out stirring reaction for 120 ℃, the dropping sodium aqueous solution in reaction system then, until pH value between 7～8, the stirring at room reaction, then regulate pH value and equal 7 with dilute hydrochloric acid, distilled water wash is used in the ethyl acetate extraction, obtains having the fluorine-containing chain hydrocarbon melamine derivate of carboxylic end group.The preparation method adds 98% vitriol oil to stir 4h for 120 ℃ in having the fluorine-containing chain hydrocarbon melamine derivate of alkyl oxide end group more specifically, stirring at room 16h, then drip 21% aqueous sodium hydroxide solution in reaction system, between 7～8, stirring at room is reacted 3h until pH value, then handle to pH value and equal 7 with 10% dilute hydrochloric acid, distilled water wash is used in the ethyl acetate extraction, takes off a layer oily liquids, vacuum-drying can obtain having the fluorine-containing chain hydrocarbon melamine derivate of carboxylic end group.
In the reaction process that carboxyl end groups changes, can isolate a class at the fluorine-containing melamine derivative of ester group/alkyl oxide end group and have the fluorine-containing melamine derivative of carboxylate salt end group, also can obtain by the alkaline solution prepared in reaction of carboxyl end groups perfluor melamine derivative and basic metal or alkaline-earth metal, its structural formula is:
X, p, z=0,1,2; And x+y=2, p+q=2, e+z=2
But x, p, z do not equal 2 simultaneously
R wherein
fFor:
The preferred Na of M=, K, Mg, Ca, Li n=0～4
The present invention is that parent carries out functionalization with the trimeric cyanamide, synthetic a series of ester group/fluorine-containing chain hydrocarbon melamine derivates of alkyl oxide end group that have, be to utilize simple raw material monomer to prepare the clear and definite fluorine-containing chain hydrocarbon compound that contains functional end group of a class formation by condensation polymerization, because PFPE has good thermotolerance, oxidation-resistance, oilness and uninflammability, therefore this class material has excellent high-low temperature resistant, oilness, performances such as anti-severe rugged environment, at nuclear power, play irreplaceable vital role in the industry such as aerospace, have very high using value.This compounds of while is functionalization further, have ester group/fluorine-containing chain hydrocarbon melamine derivate of alkyl oxide end group by institute's synthetic and under the situation of hydrolysis/oxydrolysis, can change the fluorine-containing chain hydrocarbon melamine derivate that has reactive carboxyl end groups smoothly into, can prepare miscellaneous block polymer by the reaction of carboxyl with high molecular backbone, being a kind of fluorine material intermediate of excellence, is all to occupy a tiny space in daily use or in the special material field; On the other hand, the carboxyl end groups in the derivative can be converted into carboxylate salt, in the biological activity field potential application prospect is arranged.This series has ester group/fluorine-containing chain hydrocarbon melamine derivate of alkyl oxide end group and can be used as the efficient oxidation stablizer of fluorine-containing linking agent, fire retardant, fluorine material intermediate, lubricating oil, vacuum pump wet goods, have good thermotolerance.
Embodiment
The present invention is described by the following examples, but does not limit the present invention.
Embodiment 1:
6.3g (0.05mol) trimeric cyanamide placed be furnished with heating, three mouthfuls of round-bottomed flasks of 500ml of mechanical stirring, nitrogen protection device; add 250ml anhydrous acetonitrile dissolution with solvents; elevated temperature to 60 ℃ remains on and adds 3-methoxycarbonyl-perfluoro-propionyl fluoride (n=0) 46.8g (0.3mol) under this temperature, and reaction keeps 8～12h; after reaction finishes; with the product cooling, repeatedly wash 100 ℃ of dryings of vacuum with deionized water; get colourless thickness oily product liquid, productive rate 91%.Product is tested through ultimate analysis:
| C | H | F | O | N | |
| Theoretical value (%) | 34.41 | 1.93 | 24.19 | 30.56 | 8.92 |
| Measured value (%) | 34.39 | 1.95 | 24.23 | 30.53 | 8.96 |
The structure of this material is:
Embodiment 2:
Be equipped with heating, mechanical stirring, steaming in three mouthfuls of round-bottomed flasks of 100ml of reflux condensate device, add embodiment 1 product 18.49g (0.02mol), stirring at room drips 20% aqueous sodium hydroxide solution 24g, after dropwising, stirring reaction 3h, heat up, steam the methyl alcohol and the redundant moisture that generate in the system.Cooling equals 6 with the PH ester of dilute hydrochloric acid regulator solution, with the ethyl acetate extraction, takes off a layer liquid with the separating funnel separatory, and drying removes by filter siccative, distills and removes ethyl acetate, vacuum drying oven drying, productive rate 97%.Product is tested through ultimate analysis:
| C | H | F | O | N | |
| Theoretical value (%) | 29.39 | 0.70 | 26.56 | 33.55 | 9.79 |
| Measured value (%) | 29.37 | 0.74 | 26.51 | 33.51 | 9.79 |
The structure of this material is:
Embodiment 3:
Product 1.433g (0.00167mol) among the embodiment 2 is dissolved in the 20ml water, splash into two phenolphthalein indicators, color is a pink, adopt 8.33% standard hydrogen sodium oxide titration, when the amount of the sodium hydroxide that splashes into is 4.812g, indicator is colourless, adds into a sodium hydroxide solution, and color becomes blueness.Know from reacting phenomenon the acid-base neutralisation reaction taken place that generated carboxylate salt end group perfluor melamine derivative, its structural formula is:
Embodiment 4:
6.3g (0.05mol) trimeric cyanamide placed be furnished with heating, three mouthfuls of round-bottomed flasks of 250ml of mechanical stirring, nitrogen protection device; add 100ml anhydrous acetonitrile dissolution with solvents; elevated temperature to 60 ℃ remains on and adds 3-methoxycarbonyl-perfluoro-propionyl fluoride (n=0) 23.4g (0.15mol) under this temperature, and reaction keeps 5～13h; after reaction finishes; with the product cooling, repeatedly wash 100 ℃ of dryings of vacuum with deionized water; get colourless thickness oily product liquid, productive rate 94%.Product is tested through ultimate analysis:
| C | H | F | O | N | |
| Theoretical value (%) | 33.73 | 2.26 | 21.34 | 26.95 | 15.73 |
| Measured value (%) | 33.69 | 2.31 | 21.33 | 26.93 | 15.76 |
The structure of this material is:
Embodiment 5:
Be equipped with heating, mechanical stirring, steaming in three mouthfuls of round-bottomed flasks of 100ml of reflux condensate device, add embodiment 4 product 10.68g (0.02mol), stirring at room drips 20% aqueous sodium hydroxide solution 12g, after dropwising, stirring reaction 3h, heat up, steam the methyl alcohol and the redundant moisture that generate in the system.Cooling equals 6 with the PH ester of dilute hydrochloric acid regulator solution, with the ethyl acetate extraction, takes off a layer liquid with the separating funnel separatory, and drying removes by filter siccative, distills and removes ethyl acetate, vacuum drying oven drying, productive rate 95%.Product is tested through ultimate analysis:
| C | H | F | O | N | |
| Theoretical value (%) | 29.28 | 1.23 | 23.16 | 29.26 | 17.07 |
| Measured value (%) | 29.27 | 1.24 | 23.11 | 29.21 | 17.09 |
The structure of this material is:
Embodiment 6:
6.3g (0.05mol) trimeric cyanamide placed be furnished with heating, three mouthfuls of round-bottomed flasks of 500ml of mechanical stirring, nitrogen protection device; add 250ml anhydrous pyridine dissolution with solvents; elevated temperature to 110 ℃; remain under this temperature and add 2; 5-dimethyl-3; 6-two oxa-s-9-methoxycarbonyl-perfluor nonanoyl fluorine (n=2) 146.4g (0.3mol); reaction keeps 8～12h; after reaction finishes; with the product cooling, repeatedly wash 100 ℃ of dryings of vacuum with deionized water; get colourless thickness oily product liquid, productive rate 85%.Product is tested through ultimate analysis:
| C | H | F | O | N | |
| Theoretical value (%) | 25.78 | 0.62 | 54.38 | 16.36 | 2.86 |
| Measured value (%) | 25.76 | 0.65 | 54.33 | 16.33 | 2.82 |
The structure of this material is:
Embodiment 7:
6.3g (0.05mol) trimeric cyanamide placed be furnished with heating, three mouthfuls of round-bottomed flasks of 250ml of mechanical stirring, nitrogen protection device; add the anhydrous N-Methyl pyrrolidone dissolution with solvents of 150ml; elevated temperature to 140 ℃; remain under this temperature and add 2; 5; 8-trimethylammonium-3; 6,9-trioxa-12-methoxycarbonyl-perfluor dodecane acyl fluorides (n=3) 98.1g (0.15mol), reaction keeps 8～12h; after reaction finishes; with the product cooling, repeatedly wash 100 ℃ of dryings of vacuum with deionized water; get colourless thickness oily product liquid, productive rate 75%.Product is tested through ultimate analysis:
| C | H | F | O | N | |
| Theoretical value (%) | 24.87 | 0.60 | 56.20 | 14.20 | 4.14 |
| Measured value (%) | 24.83 | 0.65 | 56.23 | 14.23 | 4.12 |
The structure of this material is:
Embodiment 8:
6.3g (0.05mol) trimeric cyanamide placed be furnished with heating, three mouthfuls of round-bottomed flasks of 250ml of mechanical stirring, nitrogen protection device; add the anhydrous N-Methyl pyrrolidone dissolution with solvents of 150ml; elevated temperature to 140 ℃; remain under this temperature and add 2; 5; 8-trimethylammonium-3; 6,9-trioxa-12-methoxycarbonyl-perfluor dodecane acyl fluorides (n=3) 196.2g (0.3mol), reaction keeps 10～14h; after reaction finishes; with the product cooling, repeatedly wash 100 ℃ of dryings of vacuum with deionized water; get colourless thickness oily product liquid, productive rate 65%.Product is tested through ultimate analysis:
| C | H | F | O | N | |
| Theoretical value (%) | 24.75 | 0.46 | 58.00 | 14.65 | 2.14 |
| Measured value (%) | 24.73 | 0.48 | 57.93 | 14.63 | 2.12 |
The structure of this material is:
Embodiment 9:
Be equipped with heating, mechanical stirring, steaming in three mouthfuls of round-bottomed flasks of 100ml of reflux condensate device, adding embodiment 8 product 3.93g (0.001mol), stirring at room drips 20% aqueous sodium hydroxide solution 0.6g, after dropwising, stirring reaction 3h equals 6 with the PH ester of dilute hydrochloric acid regulator solution, extracts with ethyl acetate, take off a layer liquid with the separating funnel separatory, drying removes by filter siccative, and ethyl acetate is removed in distillation, the vacuum drying oven drying, productive rate 78%.Product is tested through ultimate analysis:
| C | H | F | O | N | |
| Theoretical value (%) | 23.42 | 0.16 | 59.27 | 14.97 | 2.18 |
| Measured value (%) | 23.47 | 10.14 | 59.19 | 14.91 | 2.19 |
The structure of this material is:
Embodiment 10:
6.3g (0.05mol) trimeric cyanamide placed be furnished with heating, three mouthfuls of round-bottomed flasks of 1000ml of mechanical stirring, nitrogen protection device; add the anhydrous N-Methyl pyrrolidone dissolution with solvents of 560ml; elevated temperature to 160 ℃; remain under this temperature and add 2; 5,8,11-tetramethyl--3; 6; 9,12-four oxa-s-15-methoxycarbonyl-perfluor pentadecane acyl fluorides (n=4) 246g (0.3mol), reaction keeps 8～12h; after reaction finishes; with the product cooling, repeatedly wash 100 ℃ of dryings of vacuum with deionized water; get colourless thickness oily product liquid, productive rate 45%.Product is tested through ultimate analysis:
| C | H | F | O | N | |
| Theoretical value (%) | 24.13 | 0.37 | 60.15 | 13.64 | 1.71 |
| Measured value (%) | 24.11 | 0.39 | 60.13 | 13.63 | 1.72 |
The structure of this material is:
Embodiment 11:
6.3g (0.05mol) trimeric cyanamide placed be furnished with heating, three mouthfuls of round-bottomed flasks of 500ml of mechanical stirring, nitrogen protection device; add 250ml anhydrous acetonitrile dissolution with solvents; elevated temperature to 80 ℃; remain on adding 3 methyl ethers-propionyl fluoride 53.4g (0.3mol) under this temperature, reaction keeps 8～12h, after reaction finishes; product is cooled off; repeatedly wash 100 ℃ of dryings of vacuum, productive rate 96% with deionized water.Product is tested through ultimate analysis:
| C | H | F | O | N | |
| Theoretical value (%) | 30.18 | 1.69 | 42.44 | 17.87 | 7.82 |
| Measured value (%) | 30.16 | 1.65 | 42.43 | 17.83 | 7.86 |
The structure of this material is:
Embodiment 12:
Be equipped with heating, mechanical stirring, steaming in three mouthfuls of round-bottomed flasks of 250ml of reflux condensate device, add embodiment 11 product 10.74g (0.01mol), then add 98% vitriol oil 15g, stirring is warming up to 120 ℃ and keeps 4h, after being cooled to room temperature reaction 12～16h, in reaction flask, add 21% aqueous sodium hydroxide solution adjusting pH value and equal 6, extract with ethyl acetate, separatory, anhydrous magnesium sulfate drying spends the night, and removes by filter siccative, and ethyl acetate is removed in underpressure distillation, vacuum-drying, productive rate 85%.
Product is tested through ultimate analysis:
| C | H | F | O | N | |
| Theoretical value (%) | 28.00 | 0.52 | 39.36 | 24.86 | 7.26 |
| Measured value (%) | 27.96 | 0.55 | 39.33 | 24.83 | 7.26 |
The structure of this material is:
Embodiment 13:
In having the 150ml single necked round bottom flask of whipping appts, adding embodiment 11 product 11.58g (0.01mol) is dissolved in the 50ml water, splash into two phenolphthalein indicators, color is a pink, adopt 8.33% standard hydrogen sodium oxide titration, when the amount of the sodium hydroxide that splashes into was 4.812g, indicator was colourless, add into a sodium hydroxide solution, color becomes blueness.Know from reacting phenomenon the acid-base neutralisation reaction taken place that generated the fluorine-containing melamine derivative of carboxylate salt end group, its structural formula is:
Embodiment 14:
6.3g (0.05mol) trimeric cyanamide placed be furnished with heating, three mouthfuls of round-bottomed flasks of 500ml of mechanical stirring, nitrogen protection device; add 250ml anhydrous pyridine dissolution with solvents, elevated temperature to 110 ℃ remains under this temperature and adds 2; 5-dimethyl 3; 6-two oxa-s-9-methyl ether-nonanoyl fluorine (n=2) 76.5g (0.15mol), reaction keeps 8～12h, after reaction finishes; product is cooled off; repeatedly wash 100 ℃ of dryings of vacuum, productive rate 86% with deionized water.
Product is tested through ultimate analysis:
| C | H | F | O | N | |
| Theoretical value (%) | 24.83 | 0.76 | 57.12 | 12.03 | 5.26 |
| Measured value (%) | 24.76 | 0.65 | 57.13 | 12.19 | 5.26 |
The structure of this material is:
Embodiment 15:
6.3g (0.05mol) trimeric cyanamide placed be furnished with heating, three mouthfuls of round-bottomed flasks of 500ml of mechanical stirring, nitrogen protection device; add the anhydrous N-Methyl pyrrolidone dissolution with solvents of 350ml; elevated temperature to 160 ℃; remain under this temperature and add 2; 5; 8,11-tetramethyl-3,6; 9; 12-four oxa-s-15-methyl ether-pentadecane acyl fluorides (n=4) 126.3g (0.15mol), reaction keeps 8～12h, after reaction finishes; product is cooled off; repeatedly wash 100 ℃ of dryings of vacuum, productive rate 46% with deionized water.Product is tested through ultimate analysis:
| C | H | F | O | N | |
| Theoretical value (%) | 23.63 | 0.47 | 61.56 | 11.11 | 3.24 |
| Measured value (%) | 23.56 | 0.45 | 61.53 | 11.19 | 3.26 |
The structure of this material is:
Embodiment 16:
6.3g (0.05mol) trimeric cyanamide placed be furnished with heating, three mouthfuls of round-bottomed flasks of 1000ml of mechanical stirring, nitrogen protection device; add the anhydrous N-Methyl pyrrolidone dissolution with solvents of 450ml; elevated temperature to 160 ℃; remain under this temperature and add 2; 5; 8,11-tetramethyl-3,6; 9; 12-four oxa-s-15-methyl ether-pentadecane acyl fluorides (n=4) 252.6g (0.3mol), reaction keeps 10～14h, after reaction finishes; product is cooled off; repeatedly wash 100 ℃ of dryings of vacuum, productive rate 46% with deionized water.Product is tested through ultimate analysis:
| C | H | F | O | N | |
| Theoretical value (%) | 23.50 | 0.36 | 63.09 | 11.39 | 1.66 |
| Measured value (%) | 23.46 | 0.41 | 63.03 | 11.39 | 1.66 |
The structure of this material is:
Embodiment 17:
Be equipped with heating, mechanical stirring, steaming in three mouthfuls of round-bottomed flasks of 100ml of reflux condensate device, add embodiment 16 product 5.06g (0.001mol), then add 98% vitriol oil 12g, stirring is warming up to 120 ℃ and keeps 4h, after being cooled to room temperature reaction 12～16h, in reaction flask, add 21% aqueous sodium hydroxide solution adjusting pH value and equal 6, extract with ethyl acetate, separatory, anhydrous magnesium sulfate drying spends the night, and removes by filter siccative, and ethyl acetate is removed in underpressure distillation, vacuum-drying, productive rate 85%.
Product is tested through ultimate analysis:
| C | H | F | O | N | |
| Theoretical value (%) | 23.12 | 0.12 | 62.06 | 13.07 | 1.63 |
| Measured value (%) | 23.09 | 0.15 | 62.03 | 13.03 | 1.58 |
The structure of this material is:
Embodiment 18:
Embodiment 17 product 5.14g (0.001mol) are dissolved in the 20ml water, place the 50ml Erlenmeyer flask, add two phenolphthalein indicators, the solution pinkiness, adopt 8.33% standard hydrogen sodium oxide titration, when the amount of the sodium hydroxide that splashes into was 2.881g, indicator was colourless, add into a sodium hydroxide solution, color becomes blueness.Know from reacting phenomenon the acid-base neutralisation reaction taken place that generated carboxylate salt end group perfluor melamine derivative, its structural formula is:
Claims (10)
1, band ester group or the fluorine-containing chain hydrocarbon melamine derivate of alkyl oxide end group, its general structure is expressed as:
In the formula: x, p, z=0,1,2, and x+y=2, p+q=2, e+z=2, but x, p, z do not equal 2 simultaneously, wherein R
fFor:
2, have the carboxylic end group fluorine-containing chain hydrocarbon melamine derivate, its general structure is expressed as:
In the formula: x, p, z=0,1,2, and x+y=2, p+q=2, e+z=2, but x, p, z do not equal 2 simultaneously, wherein R
fFor:
3, derivative according to claim 1 and 2 is characterized in that x, p, z preferably are respectively 0 or 1 simultaneously in the described general structure.
4, the preparation method of described band ester group of a kind of claim 1 or the fluorine-containing chain hydrocarbon melamine derivate of alkyl oxide end group is characterized in that carrying out the body condensation reaction under 40～180 ℃ or having to carry out the solution condensation reaction in the presence of the solvent by containing ester group/alkyl oxide end group fluorine-containing chain hydrocarbon acyl fluorides monomer and trimeric cyanamide.
5, preparation method according to claim 4 is characterized in that described solvent is acetonitrile, pyridine, dimethyl formamide or N-Methyl pyrrolidone.
6, preparation method according to claim 4 is characterized in that the reactant solid content is 20%～30% in the reaction system solution in the presence of solvent is arranged.
7, the described preparation method who has the carboxylic end group fluorine-containing chain hydrocarbon melamine derivate of a kind of claim 1, it is characterized in that it being to make and have the carboxylic end group fluorine-containing chain hydrocarbon melamine derivate by hydrolysis/oxydrolysis reaction by having ester group/fluorine-containing chain hydrocarbon melamine derivate of alkyl oxide end group, have the carboxylic end group fluorine-containing chain hydrocarbon melamine derivate by with alkali reaction, formation has the fluorine-containing chain hydrocarbon melamine derivate of basic metal or alkaline earth metal carboxylation's end group, and having ester group/fluorine-containing chain hydrocarbon melamine derivate of alkyl oxide end group is to carry out body under 40～180 ℃ or having the solution condensation in the presence of the solvent to react by containing ester group/alkyl oxide end group fluorine-containing chain hydrocarbon acyl fluorides monomer and trimeric cyanamide.
8, preparation method according to claim 7, it is characterized in that preparation has ester group/fluorine-containing chain hydrocarbon melamine derivate of alkyl oxide end group, described solvent is acetonitrile, pyridine, dimethyl formamide or N-Methyl pyrrolidone, and the reactant solid content is 20%～30%.
9, preparation method according to claim 7, it is characterized in that having in the fluorine-containing chain hydrocarbon melamine derivate of ester group end group and pass through aqueous sodium hydroxide solution earlier, regulate pH value between 7～8, the stirring at room reaction, then regulate pH value and equal 7 with dilute hydrochloric acid, with ethyl acetate extraction, distilled water wash, obtain having the fluorine-containing chain hydrocarbon melamine derivate of carboxylic end group.
10, preparation method according to claim 7, it is characterized in that having in the fluorine-containing chain hydrocarbon melamine derivate of alkyl oxide end group and to add 98% vitriol oil and carry out stirring reaction for 120 ℃, the dropping sodium aqueous solution in reaction system then, until pH value between 7～8, the stirring at room reaction is then regulated pH value with dilute hydrochloric acid and is equaled 7, the ethyl acetate extraction, use distilled water wash, obtain having the fluorine-containing chain hydrocarbon melamine derivate of carboxylic end group.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102414251A (en) * | 2009-04-21 | 2012-04-11 | 优迈特株式会社 | Method for producing fluorine-containing polyether carboxylic acid amide |
| EP2486923A1 (en) * | 2011-02-11 | 2012-08-15 | Dr. Felix Jäger und Dr. Stefan Drinkuth Laborgemeinschaft OHG | Histone deacetylase (HDAC) inhibiting compounds and method of making same |
| CN106316972A (en) * | 2016-07-20 | 2017-01-11 | 天津科技大学 | Method for preparing methylated fluorine-containing amino resin |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5034525A (en) * | 1988-09-19 | 1991-07-23 | Takateru Dekura | Synthetic lubricant |
| US5225549A (en) * | 1988-10-08 | 1993-07-06 | Takateru Dekura | Perfluoropolyether lubricants for electromagnetic recording media |
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2005
- 2005-10-24 CN CNB2005100449806A patent/CN100448851C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102414251A (en) * | 2009-04-21 | 2012-04-11 | 优迈特株式会社 | Method for producing fluorine-containing polyether carboxylic acid amide |
| CN102414251B (en) * | 2009-04-21 | 2013-07-17 | 优迈特株式会社 | Method for producing fluorine-containing polyether carboxylic acid amide |
| EP2486923A1 (en) * | 2011-02-11 | 2012-08-15 | Dr. Felix Jäger und Dr. Stefan Drinkuth Laborgemeinschaft OHG | Histone deacetylase (HDAC) inhibiting compounds and method of making same |
| CN106316972A (en) * | 2016-07-20 | 2017-01-11 | 天津科技大学 | Method for preparing methylated fluorine-containing amino resin |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100448851C (en) | 2009-01-07 |
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