CN100500699C - Method for preparing polythene derivative in supercritical fluid - Google Patents

Method for preparing polythene derivative in supercritical fluid Download PDF

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CN100500699C
CN100500699C CNB2007100183892A CN200710018389A CN100500699C CN 100500699 C CN100500699 C CN 100500699C CN B2007100183892 A CNB2007100183892 A CN B2007100183892A CN 200710018389 A CN200710018389 A CN 200710018389A CN 100500699 C CN100500699 C CN 100500699C
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fluid
monomer
methacrylate
syringe pump
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CN101121760A (en
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刘昭铁
陈建刚
刘忠文
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Shaanxi Normal University
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Shaanxi Normal University
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Abstract

The utility model relates to a preparation method of polyethylene derivatives in supercritical fluid. The utility model consists of a polymerization reaction step and a purification step by means of a reaction axe 8, and a vacuum pump 1 used for vacuumizing. Compared with the existing preparation method of polyethylene derivatives in supercritical fluid, the utility model takes use of the vacuum pump 1 to vacuumize the reaction axe 8. And then monomer is added into the reaction axe 8. When the reaction axe 8 is heated to the reaction temperature, initiator is added into the reaction axe 8 for polymerization reaction. Through a large number of laboratory research, the experiment results indicate that the processing steps of the utility model reduces the loss of raw materials in the reaction process, the environmental pollution, as well as the polymer molecule distribution, enhances the yield rate of the polymerization reaction products and improves the performance of the products. The utility model also reduces the production cost. The utility model can be used for the preparation of polyethylene derivatives after the medium enlarging experiment.

Description

The method that in supercutical fluid, prepares polythene derivative
Technical field
The invention belongs to technical field of polymer materials, be specifically related in supercutical fluid, prepare the method for polythene derivative.
Background technology
Polythene derivative is meant the family macromolecule compound that the derivative by vinyl monomer obtains by polyreaction, the ethylenic monomer derived thing mainly is meant vinyl monomer containing oxygen derivative, nitrogen containing derivative and fluorine-containing derivant at this, can be used as general purpose material by these monomers through the macromolecular material that polymerization obtains, as plastics, coating etc. also can be used as functional materials and are applied to medical science, aerospace, machinery and microelectronics industry field.
Supercutical fluid is meant that temperature and pressure is in critical temperature and the above fluid of emergent pressure, and supercritical co is its typical case's representative.Come the method for synthetic macromolecule can be divided into interrupter method and continuous processing with supercritical co as medium, existing document and patent report at home and abroad.CN1242021 discloses a kind of continuation method of a kind of fluorine monomer polymeric in carbonic acid gas, and this method required equipment and technology are very complicated, and product property is subjected to the inside reactor condition influence very big.More be reported as interrupter method.DeSimone, and J.M. (Science1992,257,945-947) disclosed method is: monomer and radical initiator are added autoclave, and with about 10 minutes excluding airs of purgings such as argon gas, pressurization heats up, and carries out polyreaction; Cooper, (Macromolecules 1999,32 (7), and 2156-2166) reported method is that monomer and radical initiator are added autoclave, uses CO for A.I. 2Purge 20～30 minutes excluding airs, Okahata, Y. (Macromolecules2006,39 (2), 604-608) reported method is that initiator is added reactor, reactor freezing and vacuumize with vacuum pump after, add monomer, pressurization heats up and carries out polyreaction.The main drawback of these methods is: one is because most of monomers have volatility, and some monomer is taken away by sweeping gas in purging emptying gas process, has wasted raw material, has reduced productive rate, has polluted environment, has changed the basis of quantitative Analysis.Radical initiator did not add before temperature reaches set(ting)value in addition, in temperature-rise period, unavoidably decompose gradually, initiated polymerization in bigger temperature range causes the molecular weight distribution of reaction product to broaden, and also makes the controllability and the circulation ratio variation of reaction process.
Summary of the invention
Technical problem to be solved by this invention is to overcome above-mentioned polythene derivative preparation method's shortcoming, provide a kind of reasonable in design, method is simple, environmental pollution is little, the method for preparing polythene derivative in supercutical fluid of narrow molecular weight distribution.
Solving the problems of the technologies described above the technical scheme that adopts is that it comprises the steps:
1, reactor vacuumizes
Room temperature charges into CO with syringe pump in reactor 2Or N 2Or Ar gas to the pressure in the reactor is 0.3～1MPa, emits the gas that charges into, and vacuumizes with vacuum pump and makes that vacuum tightness is 0.09MPa in the reactor, repeats above-mentioned steps 2 times.
2, polyreaction
Monomer is joined reactor with volume pump, charging into fluid to the pressure in the reactor in reactor is 3.5～7MPa, monomer and fluidic volume are 20%～30% of reactor volume, be warmed up to 47.5～115 ℃ with well heater, radical initiator joins reactor by sample hose with syringe pump, the mol ratio of monomer and radical initiator is 1:0.001～0.02, stir with stirrer, with syringe pump fluid replacement to reacting kettle inner pressure is 10～40MPa, carry out chemical reaction, chemical equation is as follows:
(1) R in the formula 1, R 2Be H or F, R 1, R 2Identical; R 3Be H or CH 3Or F, R 4Be C 6H 5Or F or Cl or OCOR or COOR, R is C mH 2mn+1Or C nH 2F 2n-1, m is 1～4, and n is 2～4, and p is the polymerization degree.Reacted 6～48 hours, and stopped to stir, ice-water bath is cooled to 0～5 ℃, opens micrometering valve, and the fluid in the reactor is discharged and gasification, and the snubber assembly of flowing through is collected and carried component, and tail gas is discharged or recycled after purification, exits to normal pressure, collects thick product.
Above-mentioned monomer comprises vinyl-acetic ester or acrylate or N-N-isopropylacrylamide or methacrylic ester or methacrylate based propyl trimethoxy silicane or vinyl pyrrolidone or trifluoroethyl methacrylate or trifluorochloroethylene or tetrafluoroethylene or vinyl fluoride or vinylidene fluoride; Described acrylate comprises methyl acrylate, ethyl propenoate, butyl acrylate, Octyl acrylate, and described methacrylic ester comprises methyl methacrylate, Jia Jibingxisuanyizhi, butyl methacrylate, dimethylaminoethyl methacrylate; If monomer can homopolymerization, monomer polymerization separately forms homopolymer, also can form multipolymer with one or more other monomers.If the formation multipolymer, selected monomer must be can copolymerization.Above-mentioned radical initiator is Diisopropyl azodicarboxylate or benzoyl peroxide or di-t-butyl peroxide.Above-mentioned fluid is carbonic acid gas or 1,1,1,2-Tetrafluoroethane or trifluoromethane.
3, separate purification
Thick product is joined apparatus,Soxhlet's with the ethanol of 20～30 times of weight or water extraction 3～10 times, and separating residual monomer, the product after the separation 50 ℃ of dryings 24 hours in vacuum drying oven are prepared into polythene derivative.
In polymerization procedure 2 of the present invention, monomer is joined reactor, fluid charges into reactor, preferably be warmed up to 55～62.5 ℃ with well heater, radical initiator joins reactor by sample hose with syringe pump, and the mol ratio of monomer and radical initiator is preferably 1:0.005～0.015, stirs with stirrer, be preferably 15～40MPa with syringe pump 5 fluid replacement to reacting kettle inner pressure, carry out chemical reaction.
In polymerization procedure 2 of the present invention, monomer is joined reactor, fluid charges into reactor, with well heater optimum temperature rise to 55 ℃, radical initiator joins reactor by sample hose with syringe pump, and mol ratio the best of monomer and radical initiator is 1:0.01, stirs with stirrer, with syringe pump fluid replacement to reacting kettle inner pressure the best is 32.5MPa, carries out chemical reaction.
In chemical equation of the present invention (1), R 3Be preferably CH 3Or F, R 1Be preferably F or COOR.
The present invention compares with the preparation method of existing polythene derivative in supercutical fluid, and the present invention adopts and earlier reactor vacuumized with vacuum pump, to wherein adding monomer, when reactor is heated to desired reaction temperature, adds initiator again, carries out polyreaction.The present invention is through a large amount of laboratory study experiments, experimental result shows, processing step of the present invention, reduced raw-material in reaction process loss, reduced environmental pollution, reduced the molecular weight distribution of polymkeric substance, the yield that has improved polymeric reaction product and performance, reduced production cost.The present invention can be used for preparing polythene derivative behind middle amplification test.
Description of drawings
Fig. 1 is a process flow sheet of the present invention.
Fig. 2 is the infrared spectrogram of polymethyl acrylic acid trifluoro ethyl ester.
Fig. 3 is the hydrogen nuclear magnetic resonance spectrogram of polymethyl acrylic acid trifluoro ethyl ester.
Fig. 4 is the carbon-13 nmr spectra figure of polymethyl acrylic acid trifluoro ethyl ester.
Fig. 5 is the infrared spectrogram of the polymethyl acrylic acid trifluoro ethyl ester of differential responses time preparation.
Fig. 6 is the hydrogen nuclear magnetic resonance spectrogram of the polymethyl acrylic acid trifluoro ethyl ester of differential responses time preparation.
Fig. 7 is the hydrogen nuclear magnetic resonance spectrogram of the polymethyl acrylic acid trifluoro ethyl ester of differing temps, pressure, the preparation of radical initiator consumption.
Fig. 8 is the infrared spectrogram of trifluoroethyl methacrylate and vinylpyrrolidone copolymer.
Fig. 9 is the hydrogen nuclear magnetic resonance spectrogram of trifluoroethyl methacrylate and vinylpyrrolidone copolymer.
Embodiment
The present invention is described in more detail below in conjunction with drawings and Examples, but the invention is not restricted to these embodiment.
Embodiment 1
Used raw material trifluoroethyl methacrylate 10.214g (0.0608 mole) is that example used other raw material and step of preparation process are as follows with preparation polymethyl acrylic acid trifluoro ethyl ester:
1, reactor vacuumizes
Room temperature charges into CO with syringe pump 5 in reactor 8 2Gas to the pressure in the reactor 8 are 0.5MPa, emit the gas that charges into, and vacuumize with vacuum pump 1 and make that vacuum tightnesss are 0.09MPa in the reactor 8, repetition above-mentioned steps 2 times.Also can in reactor, charge into N 2Gas can also charge into Ar gas, charges into N in the reactor 2Or the pressure of Ar gas and the reactor vacuum tightness after vacuumizing with charge into CO 2Identical during gas.
2, polyreaction
The present embodiment monomer is selected trifluoroethyl methacrylate for use, and radical initiator is selected Diisopropyl azodicarboxylate for use, and fluid is selected CO for use 2Trifluoroethyl methacrylate 10.214g is joined reactor 8 with volume pump 6, in reactor 8, charge into CO with syringe pump 5 2Pressure to reactor 8 is 7MPa, trifluoroethyl methacrylate and CO in the reactor 8 2Volume be reactor 8 volumetrical 20%～30%, reactor 8 usefulness well heaters 7 are warmed up to 55 ℃, get Diisopropyl azodicarboxylate 0.101g and join reactor 8 by sample hose 4 usefulness syringe pumps 5, the mol ratio of trifluoroethyl methacrylate and Diisopropyl azodicarboxylate is 1:0.01, stir with stirrer 9, replenish CO with syringe pump 5 2To reactor 8 internal pressures be 32.6MPa, carry out chemical reaction, chemical equation is as follows:
Figure C200710018389D00071
Reacted 24 hours, and stopped to stir, ice-water bath is cooled to 0～5 ℃, open micrometering valve 2, the fluid in the reactor 8 is discharged and gasification, and the snubber assembly of flowing through is collected and carried component, discharge tail gas or after purification, recycle, exit, collect the thick product of polymethyl acrylic acid trifluoro ethyl ester to normal pressure.
3, separate purification
The thick product of polymethyl acrylic acid trifluoro ethyl ester is joined apparatus,Soxhlet's with the alcohol extraction of 25 times of weight 3～10 times, the 50 ℃ of vacuum-drying 24 hours in vacuum drying oven of separating monomer, also used water extracting and separating monomer, the product after the separation.The spectral data of prepared product is as follows:
IR (pressing potassium bromide troche) υ: 3000,2972,1753,1490,1457,1421,1282,1185,1031,972,893,844,746,659cm -1
1H?NMR(300MHz，CDCl 3)δ：4.35(2H)，2.0～1.9(2H)，1.1～0.9(3H)ppm。
13C?NMR(75MHz，CDCl 3)δ：176，123，62.5，54.2，45.6，19.5，17.8ppm。Spectral data shows that product is the polymethyl acrylic acid trifluoro ethyl ester, and productive rate is 88.3%, and molecular weight is 57916, and molecular weight distribution is 1.2055.Its structural formula is as follows:
Embodiment 2
Used raw material trifluoroethyl methacrylate 10.214g (0.0608 mole) is that example used other raw material and step of preparation process are as follows with preparation polymethyl acrylic acid trifluoro ethyl ester:
In polymerization procedure 2, the present embodiment monomer is selected trifluoroethyl methacrylate for use, and radical initiator is selected Diisopropyl azodicarboxylate for use, and fluid is selected CO for use 2Trifluoroethyl methacrylate 10.214g is joined reactor 8 with volume pump 6, in reactor 8, charge into CO with syringe pump 5 2Pressure to reactor 8 is 6.9MPa, trifluoroethyl methacrylate and CO in the reactor 8 2The fluidic volume is reactor 8 volumetrical 20%～30%, reactor 8 usefulness well heaters 7 are warmed up to 47.5 ℃, get Diisopropyl azodicarboxylate 0.0099g and join reactor 8 by sample hose 4 usefulness syringe pumps 5, the mol ratio of trifluoroethyl methacrylate and Diisopropyl azodicarboxylate is 1:0.001, stir with stirrer 9, replenish CO with syringe pump 5 2To reactor 8 internal pressures be 18.8MPa, carry out chemical reaction, reacted 24 hours, stop to stir, ice-water bath is cooled to 0～5 ℃, opens micrometering valve 2, fluid in the reactor 8 is discharged and gasification, the snubber assembly of flowing through is collected and is carried component, discharges tail gas or recycle collection polymethyl acrylic acid trifluoro ethyl ester crude product after purification.
In process for separating and purifying step 3, thick product joins apparatus,Soxhlet's with the alcohol extraction of 20 times of weight 3～10 times, separating residual monomer, the product after the separation 50 ℃ of dryings 24 hours in vacuum drying oven.
Other processing step is identical with embodiment 1.The spectral data of prepared product is as follows:
IR (pressing potassium bromide troche) υ: 3000,2972,1753,1490,1457,1421,1282,1185,1031,972,893,844,746,659cm -1
1H?NMR(300MHz，CDCl 3)δ：4.35(2H)，2.0～1.9(2H)，1.1～0.9(3H)ppm。Spectral data shows that product is the polymethyl acrylic acid trifluoro ethyl ester, and productive rate is 16.7.
Embodiment 3
Used raw material trifluoroethyl methacrylate 10.214g (0.0608 mole) is that example used other raw material and step of preparation process are as follows with preparation polymethyl acrylic acid trifluoro ethyl ester:
In polymerization procedure 2, the present embodiment monomer is selected trifluoroethyl methacrylate for use, and radical initiator is selected Diisopropyl azodicarboxylate for use, and fluid is selected CO for use 2Trifluoroethyl methacrylate 10.214g is joined reactor 8 with volume pump 6, and charging into CO2 with syringe pump 5 in reactor 8 is 6.7MPa to the pressure in the reactor 8, trifluoroethyl methacrylate and CO in the reactor 8 2The fluidic volume is reactor 8 volumetrical 20%～30%, reactor 8 usefulness well heaters 7 are warmed up to 70 ℃, get Diisopropyl azodicarboxylate 0.223g and join reactor 8 by sample hose 4 usefulness syringe pumps 5, the mol ratio of trifluoroethyl methacrylate and Diisopropyl azodicarboxylate is 1:0.02, stir with stirrer 9, replenish CO with syringe pump 5 2To reactor 8 internal pressures be 37.5MPa, carry out chemical reaction, reacted 24 hours, stop to stir, ice-water bath is cooled to 0～5 ℃, opens micrometering valve 2, fluid in the reactor 8 is discharged and gasification, the snubber assembly of flowing through is collected and is carried component, discharges tail gas or recycle the thick product of collection polymethyl acrylic acid trifluoro ethyl ester after purification.
In process for separating and purifying step 3, thick product joins apparatus,Soxhlet's with the alcohol extraction of 30 times of weight 3～10 times, separating residual monomer, the product after the separation 50 ℃ of dryings 24 hours in vacuum drying oven.
Other processing step is identical with embodiment 1.The spectral data of prepared product is as follows:
IR (pressing potassium bromide troche) υ: 3000,2972,1753,1490,1457,1421,1282,1185,
1031，972，893，844，746，659cm -1。
1HNMR(300MHz，CDCl 3)δ：4.35(2H)，2.0～1.9(2H)，1.1～0.9(3H)ppm。Spectral data shows that product is the polymethyl acrylic acid trifluoro ethyl ester, and productive rate is 95.1%, and molecular weight is 12506, and molecular weight distribution is 1.2350.
Embodiment 4
With the used raw material trifluoroethyl methacrylate 11.0888 (0.066 mole) of preparation polymethyl acrylic acid trifluoro ethyl ester is that example used other raw material and step of preparation process are as follows:
In polymerization procedure 2, the present embodiment monomer is selected trifluoroethyl methacrylate for use, and radical initiator is selected Diisopropyl azodicarboxylate for use, and fluid selects 1,1,1 for use, the 2-Tetrafluoroethane.Trifluoroethyl methacrylate 11.0888g is joined reactor 8 with volume pump 6, in reactor 8, charge into 1,1,1, the 2-Tetrafluoroethane is 3.5MPa to the pressure in the reactor 8, trifluoroethyl methacrylate and 1 in the reactor 8,1,1, the volume of 2-Tetrafluoroethane is reactor 8 volumetrical 30%, and reactor 8 usefulness well heaters 7 are warmed up to 70 ℃, get Diisopropyl azodicarboxylate 0.1163 3g and join reactor 8 by sample hose 4 usefulness syringe pumps 5, the mol ratio of trifluoroethyl methacrylate and Diisopropyl azodicarboxylate is 1:0.011, stirs with stirrer 9, replenishes 1 with syringe pump 5,1,1,2-Tetrafluoroethane to reactor 8 internal pressures are 25MPa, carry out chemical reaction, reacted 24 hours, stop to stir, ice-water bath is cooled to 0～5 ℃, opens micrometering valve 2, fluid in the reactor 8 is discharged and gasification, the snubber assembly of flowing through is collected and is carried component, discharges tail gas or recycle the thick product of collection polymethyl acrylic acid trifluoro ethyl ester after purification.
Other processing step is identical with embodiment 2.The spectral data of prepared product is as follows:
IR (pressing potassium bromide troche) υ: 3000,2972,1753,1490,1457,1421,1282,1185,1031,972,893,844,746,659cm -1
1H?NMR(300MHz，CDCl 3)δ：4.35(2H)，2.0～1.9(2H)，1.1～0.9(3H)ppm。Spectral data shows that product is the polymethyl acrylic acid trifluoro ethyl ester, and productive rate is 82.1%, and molecular weight is 18893, and molecular weight distribution is 1.1.336.
The monomer trifluoroethyl methacrylate of present embodiment can be replaced with methacrylic acid five fluorine propyl ester (n is 3 in structural formula) or methacrylic acid seven fluorine butyl esters (n is 4 in structural formula), and the mol ratio of methacrylic acid five fluorine propyl ester or methacrylic acid seven fluorine butyl esters and Diisopropyl azodicarboxylate is 1:0.011.Be prepared into polymethyl acrylic acid five fluorine propyl ester or polymethyl acrylic acid seven fluorine butyl esters.
Embodiment 5
Used raw material methyl methacrylate 10.01g (0.1 mole) is that example used other raw material and step of preparation process are as follows with the preparation polymethylmethacrylate:
In polymerization procedure 2, the present embodiment monomer is selected methyl methacrylate for use, and radical initiator is selected benzoyl peroxide for use, and fluid is selected CO for use 2Methyl methacrylate 10.01g is joined reactor 8 with volume pump 6, and charging into CO2 with syringe pump 5 in reactor 8 is 7MPa to the pressure in the reactor 8, methyl methacrylate and CO in the reactor 8 2Volume be reactor 8 volumetrical 20%～30%, reactor 8 usefulness well heaters 7 are warmed up to 57.5 ℃, get benzoyl peroxide 0.242g and join reactor 8 by sample hose 4 usefulness syringe pumps 5, the mol ratio of trifluoroethyl methacrylate and benzoyl peroxide is 1:0.01, stir with stirrer 9, replenish CO with syringe pump 5 2To reactor 8 internal pressures be 15MPa, carry out chemical reaction, reacted 6 hours, stop to stir, ice-water bath is cooled to 0～5 ℃, opens micrometering valve 2, fluid in the reactor 8 is discharged and gasification, the snubber assembly of flowing through is collected and is carried component, discharges tail gas or recycle the thick product of collection polymethylmethacrylate after purification.
Other processing step is identical with embodiment 1.The spectral data of prepared product is as follows:
IR (pressing potassium bromide troche) υ: 3000,2954,2847,1728,1454,1597,1451,1385,1275,1197,1147,1062,990,844,752cm -1
1H?NMR(300MHz，CDCl 3)δ：3.61(3H)，1.64～1.5(2H)，1.29～1.24(3H)ppm。Spectral data shows that product is a polymethylmethacrylate, and productive rate is 86.3%, and molecular weight is 29791, and molecular weight distribution is 1.355.Its structural formula is as follows:
Figure C200710018389D00111
Monomers methyl methacrylate in the present embodiment can be replaced with Jia Jibingxisuanyizhi or butyl methacrylate or dimethylaminoethyl methacrylate, and the mol ratio of Jia Jibingxisuanyizhi or butyl methacrylate or dimethylaminoethyl methacrylate and benzoyl peroxide is 1:0.01.Be prepared into polyethyl methacrylate or poly-n-butyl methacrylate or polymethyl acrylic acid dimethylaminoethyl.
Embodiment 6
Used raw material methyl methacrylate 10.01g (0.1 mole) is that example used other raw material and step of preparation process are as follows with the preparation polymethylmethacrylate:
In polymerization procedure 2, the present embodiment monomer is selected methyl methacrylate for use, and radical initiator is selected benzoyl peroxide for use, and fluid is selected CO for use 2The methyl methacrylate consumption is 10.01g, in reactor 8 with syringe pump 5 charge into CO2 to the pressure in the reactor 8 be 6MPa, reactor 8 usefulness well heaters 7 are warmed up to 65 ℃, the benzoyl peroxide consumption is 0.0242g, the mol ratio of trifluoroethyl methacrylate and benzoyl peroxide is 1:0.001, replenishes CO with syringe pump 5 2To reactor 8 internal pressures be 25MPa, carry out chemical reaction, reacted 48 hours.Other technological process of this processing step is identical with embodiment 4.
Other processing step is identical with embodiment 1.Be prepared into polymethylmethacrylate.
Embodiment 7
As follows with other raw material and step of preparation process that used raw material methyl methacrylate 10.01g (0.1 mole) the side example of preparation polymethylmethacrylate is used:
In polymerization procedure 2, the present embodiment monomer is selected methyl methacrylate for use, and radical initiator is selected benzoyl peroxide for use, and fluid selects 1,1,1 for use, the 2-Tetrafluoroethane.The methyl methacrylate consumption is 10.01g, and the benzoyl peroxide consumption is 0.484g, and the mol ratio of trifluoroethyl methacrylate and benzoyl peroxide is 1:0.02.Other technological process of this processing step is identical with embodiment 4.
Other processing step is identical with embodiment 1.The spectral data of prepared product is as follows:
IR (pressing potassium bromide troche) υ: 3000,2954,2847,1728,1454,1597,1451,1385,1275,1197,1147,1062,990,844,752cm -1
1H?NMR(300MHz，CDCl 3)δ：3.61(3H)，1.64～1.5(2H)，1.29～1.24(3H)ppm。Spectral data shows that product is a polymethylmethacrylate, and productive rate is 91.4%.
Embodiment 8
Used raw material vinyl pyrrolidone 6.006g (0.541 mole) is that example used other raw material and step of preparation process are as follows with the preparation Polyvinylpyrolidone (PVP):
In polymerization procedure 2, the present embodiment monomer is selected vinyl pyrrolidone for use, and radical initiator is selected Diisopropyl azodicarboxylate for use, and fluid is selected CO for use 2The vinyl pyrrolidone consumption is 6.006g, and the consumption of Diisopropyl azodicarboxylate is 0.0444g, and the mol ratio of vinyl pyrrolidone and Diisopropyl azodicarboxylate is 1:0.005, and reactor 8 usefulness well heaters 7 are warmed up to 62.5 ℃, replenishes CO with syringe pump 5 2To reactor 8 internal pressures be 25MPa, reacted 24 hours.Other technological process of this processing step is identical with embodiment 1.
Other processing step is identical with embodiment 2.The spectral data of prepared product is as follows:
IR (pressing potassium bromide troche) υ: 3441,2929,1638,1431,1287cm -1
1HNMR(300MHz，CDCl 3)δ：3.76(1H)，3.40(2H)，2.23(2H)，2.00(2H)，1.55(2H)ppm。Spectral data shows that product is a Polyvinylpyrolidone (PVP), and productive rate is 84.9%, and number-average molecular weight is 29284, and molecular weight distribution is 1.3836.Its structural formula is as follows:
Figure C200710018389D00121
Embodiment 9
The used methacrylate based propyl trimethoxy silicane 12.4175g of raw material (0.5 mole) is that example used other raw material and step of preparation process are as follows with preparation polymethacrylate base propyl trimethoxy silicane:
In polymerization procedure 2, the present embodiment monomer is selected methacrylate based propyl trimethoxy silicane for use, and radical initiator is selected Diisopropyl azodicarboxylate for use, and fluid is selected CO for use 2The consumption of methacrylate based propyl trimethoxy silicane is 12.4175g, and the consumption of Diisopropyl azodicarboxylate is 0.0821g, and the mol ratio of methacrylate based propyl trimethoxy silicane and Diisopropyl azodicarboxylate is 1:0.01.Reactor 8 usefulness well heaters 7 are warmed up to 70 ℃, replenish CO with syringe pump 5 2To reactor 8 internal pressures be 25MPa, reacted 24 hours.Other technological process of this processing step is identical with embodiment 1.
Other processing step is identical with embodiment 2.The spectral data of prepared product is as follows:
IR (pressing potassium bromide troche) υ: 2951,2838,1729,1473,1407,1321,1297,1192,1088,975,820cm -1
1H?NMR(300MHz，CDCl 3)δ：3.81(2H)，3.51(9H)，1.67(4H)，0.94～0.70(3H)，0.59(2H)ppm。Spectral data shows that product is a polymethacrylate base propyl trimethoxy silicane, and productive rate is 72.1%.Its structural formula is as follows:
Figure C200710018389D00131
Embodiment 10
Used raw material trifluorochloroethylene 10.0g (0.86 mole) is that example used other raw material and step of preparation process are as follows with the preparation voltalef:
In polymerization procedure 2, the present embodiment monomer is selected trifluorochloroethylene for use, and radical initiator is selected di-t-butyl peroxide for use, fluid selects 1,1 for use, and 1,2-Tetrafluoroethane, the consumption of trifluorochloroethylene are 10g, and the consumption of di-t-butyl peroxide is 0.1256g, the mol ratio of trifluorochloroethylene and di-t-butyl peroxide is 1:0.01, and reactor 8 usefulness well heaters 7 are warmed up to 115 ℃, replenishes 1 with syringe pump 5,1,1,2-Tetrafluoroethane to reactor 8 internal pressures are 10MPa, react 12 hours.Other technological process of this processing step is identical with embodiment 1.
Other processing step is identical with embodiment 2.Be prepared into voltalef.
Monomer trifluorochloroethylene in the present embodiment can be replaced with vinyl fluoride or vinylidene fluoride, and the mol ratio of vinyl fluoride or vinylidene fluoride and di-t-butyl peroxide is 1:0.01.Be prepared into fluorinated ethylene propylene or poly(vinylidene fluoride).
Embodiment 11
Used raw acetic acid vinyl acetate 8.6g (0.1 mole) is that example used other raw material and step of preparation process are as follows with the preparation polyvinyl acetate:
In polymerization procedure 2, the present embodiment monomer is selected vinyl-acetic ester for use, and radical initiator is selected Diisopropyl azodicarboxylate for use, and fluid is selected trifluoromethane for use.The vinyl-acetic ester consumption is 8.6g, and the consumption of Diisopropyl azodicarboxylate is 0.164g, and the mol ratio of vinyl-acetic ester and Diisopropyl azodicarboxylate is 1:0.01, and replenishing trifluoromethane to reactor 8 internal pressures with syringe pump 5 is 25MPa.Other technological process of this processing step is identical with embodiment 4.
Other processing step is identical with embodiment 2.Be prepared into polyvinyl acetate.
Embodiment 12
Used raw material tetrafluoroethylene 10.0g (0.1 mole) is that example used other raw material and step of preparation process are as follows with the preparation tetrafluoroethylene:
In polymerization procedure 2, the present embodiment monomer is selected tetrafluoroethylene for use, and radical initiator is selected benzoyl peroxide for use, and fluid is selected trifluoromethane for use.The tetrafluoroethylene consumption is 10g, and the benzoyl peroxide consumption is 0.0484g, and the mol ratio of tetrafluoroethylene and benzoyl peroxide is 1:0.005, and replenishing trifluoromethane to reactor 8 internal pressures with syringe pump 5 is 15MPa.Other technological process of this processing step is identical with embodiment 4.
Other processing step is identical with embodiment 2.Be prepared into tetrafluoroethylene.
Embodiment 13
The raw material propylene acid methyl esters 8.6g (0.1 mole) used with the preparation polymethyl acrylate is that example used other raw material and step of preparation process are as follows:
In polymerization procedure 2, the present embodiment monomer is selected methyl acrylate for use, and radical initiator is selected Diisopropyl azodicarboxylate for use, and fluid is selected CO for use 2, the methyl acrylate consumption is 8.6g, and the Diisopropyl azodicarboxylate consumption is 0.164g, and the mol ratio of methyl acrylate and Diisopropyl azodicarboxylate is 1:0.01.Other technological process of this processing step is identical with embodiment 8.
Other processing step is identical with embodiment 2.Be prepared into polymethyl acrylate.
Also available ethyl propenoate of methyl acrylate in the present embodiment or butyl acrylate or Octyl acrylate are replaced, and the mol ratio of ethyl propenoate or butyl acrylate or Octyl acrylate and Diisopropyl azodicarboxylate is 1:0.01.Be prepared into polyethyl acrylate or butyl polyacrylate or polyacrylic acid monooctyl ester.
Embodiment 14
Used raw material N-N-isopropylacrylamide 8.475g (0.075 mole) is that example used other raw material and step of preparation process are as follows with the preparation poly N-isopropyl acrylamide:
In polymerization procedure 2, the present embodiment monomer is selected the N-N-isopropylacrylamide for use, and radical initiator is selected Diisopropyl azodicarboxylate for use, and fluid is selected CO for use 2, the consumption of N-N-isopropylacrylamide is 8.475g, and the consumption of Diisopropyl azodicarboxylate is 0.1231g, and the mol ratio of N-N-isopropylacrylamide and Diisopropyl azodicarboxylate is 1:0.01.Replenish CO with syringe pump 5 2To reactor 8 internal pressures be 40MPa, other technological process of this processing step is identical with embodiment 8.
Other processing step is identical with embodiment 2.Be prepared into poly N-isopropyl acrylamide.
Embodiment 15
To prepare methyl methacrylate and trifluoroethyl methacrylate multipolymer used raw material methyl methacrylate 7.5g (0.075 mole), trifluoroethyl methacrylate 12.6g (0.075 mole) is that example used other raw material and step of preparation process are as follows:
In polymerization procedure 2, the present embodiment monomer is selected methyl methacrylate and trifluoroethyl methacrylate for use, and radical initiator is selected Diisopropyl azodicarboxylate for use, and fluid is selected CO for use 2The consumption of methyl methacrylate is 7.5g, the consumption of trifluoroethyl methacrylate is 12.6g, the consumption of Diisopropyl azodicarboxylate is 0.246g, the mol ratio of methyl methacrylate and trifluoroethyl methacrylate and Diisopropyl azodicarboxylate is 1:0.01, reactor 8 usefulness well heaters 7 are warmed up to 62.5 ℃, replenish CO with syringe pump 5 2To reactor 8 internal pressures be 27MPa, reacted 6 hours.Other technological process of this processing step is identical with embodiment 4.
Other processing step is identical with embodiment 1.The spectral data of prepared product is as follows:
IR (pressing potassium bromide troche) υ: 3002,2959,1752,1461,1418,1288,1178,1031,969,892,842,753,659cm -1
1H?NMR(300MHz，CDCl 3)δ：4.36，3.62，1.92，1.48，1.24～0.86ppm。Spectral data shows that product is trifluoroethyl methacrylate and methylmethacrylate copolymer, and productive rate is 88.7%, and number-average molecular weight is 27108, and molecular weight distribution is 1.404.
Embodiment 16
To prepare trifluoroethyl methacrylate and vinylpyrrolidone copolymer used raw material trifluoroethyl methacrylate 6.624g (0.039 mole), vinyl pyrrolidone 4.0010g (0.036 mole) is that example used other raw material and step of preparation process are as follows:
In polymerization procedure 2, the present embodiment monomer is selected trifluoroethyl methacrylate and vinyl pyrrolidone for use, and radical initiator is selected Diisopropyl azodicarboxylate for use, and fluid is selected CO for use 2The consumption of trifluoroethyl methacrylate is 6.624g, the consumption of vinyl pyrrolidone is 4.0010g, the consumption of Diisopropyl azodicarboxylate is 0.0616g, the mol ratio of trifluoroethyl methacrylate and vinyl pyrrolidone and Diisopropyl azodicarboxylate is 1:0.005, reactor 8 usefulness well heaters 7 are warmed up to 62.5 ℃, replenish CO with syringe pump 5 2To reactor 8 internal pressures be 30MPa, reacted 24 hours.Other technological process of this processing step is identical with embodiment 4.
Other processing step is identical with embodiment 1.The spectral data of prepared product is as follows:
IR (pressing potassium bromide troche) υ: 2986,2929,1752,1684,1466,1425,1287,1166,1031,975,840,655cm -1
1H?NMR(300MHz，CDCl 3)δ：4.41，3.20，2.18～1.94，1.55，1.10ppm。Spectral data shows that product is trifluoroethyl methacrylate and vinylpyrrolidone copolymer, and productive rate is 87.1%, and number-average molecular weight is 206802, and molecular weight distribution is 1.255.
Embodiment 17
To prepare trifluoroethyl methacrylate and methacrylate based propyl trimethoxy silicane multipolymer used raw material trifluoroethyl methacrylate 9.4g (0.056 mole), methacrylate based propyl trimethoxy silicane 2.0g (0.008 mole) is that example used other raw material and step of preparation process are as follows:
In polymerization procedure 2, the present embodiment monomer is selected trifluoroethyl methacrylate and methacrylate based propyl trimethoxy silicane for use, radical initiator is selected Diisopropyl azodicarboxylate for use, fluid selects 1 for use, 1,1, the 2-Tetrafluoroethane, the consumption of trifluoroethyl methacrylate is 9.4g, the consumption of methacrylate based propyl trimethoxy silicane is 2.0g, charges into 1,1 in reactor 8,1, the 2-Tetrafluoroethane is 4MPa to the pressure in the reactor 8, and reactor 8 usefulness well heaters 7 are warmed up to 70 ℃, and the consumption of Diisopropyl azodicarboxylate is 0.105g, trifluoroethyl methacrylate and methacrylate based propyl trimethoxy silicane and Diisopropyl azodicarboxylate mol ratio be 1:0.01, replenish 1,1,1 with syringe pump 5,2-Tetrafluoroethane to reactor 8 internal pressures are 20MPa, react 24 hours.Other technological process of this processing step is identical with embodiment 1.
Other processing step is identical with embodiment 2.Productive rate is 91.1%, and number-average molecular weight is 16609, and molecular weight distribution is 1.388.The spectral data of prepared product is as follows:
IR (pressing potassium bromide troche) υ: 3459,2970,2847,1753,1456,1419,1287,1173,970,825,658cm -1
1H?NMR(300MHz，CDCl 3)δ：4.61，4.10，3.55，1.91，1.61，1.30，0.58ppm。Spectral data shows that product is the polymethyl acrylic acid trifluoro ethyl ester, and productive rate is 91.1%, and number-average molecular weight is 16609, and molecular weight distribution is 1.388.
Embodiment 18
To prepare trifluoroethyl methacrylate and styrol copolymer used raw material trifluoroethyl methacrylate 16.8g (0.1 mole), vinylbenzene 10.4g is that example used other raw material and step of preparation process are as follows:
In polymerization procedure 2, the present embodiment monomer is selected trifluoroethyl methacrylate and vinylbenzene for use, and radical initiator is selected Diisopropyl azodicarboxylate for use, and fluid is selected CO for use 2The consumption of trifluoroethyl methacrylate is 16.8g, cinnamic consumption is 10.4g, in reactor 8 with syringe pump 5 charge into CO2 to the pressure in the reactor 8 be 7MPa, reactor 8 usefulness well heaters 7 are warmed up to 62.5 ℃, the consumption of Diisopropyl azodicarboxylate is 0.2884g, the mol ratio of trifluoroethyl methacrylate and vinylbenzene and Diisopropyl azodicarboxylate is 1:0.009, replenishes CO with syringe pump 5 2To reactor 8 internal pressures be 28MPa, reacted 24 hours.Other technological process of this processing step is identical with embodiment 1.
Other processing step is identical with embodiment 1.The spectral data of prepared product is as follows:
IR (pressing potassium bromide troche) υ: 3459,3065,3031,2980,2947,1751,1605,1510,1455,1416,1285,1169,1118,1035,965,910,842,703,658cm -1
1H?NMR(300MHz，CDCl 3)δ：7.10～6.88，4.14，2.43，1.99～0.54ppm。Spectral data shows that product is trifluoroethyl methacrylate and cinnamic multipolymer, and productive rate is 84.3%, and number-average molecular weight is that 37126 molecular weight distribution are 1.486.
In order to determine the processing step of the best of the present invention, the contriver has carried out a large amount of laboratory study tests, and various test situation are as follows:
Laboratory apparatus: Fourier transformation infrared spectrometer, model are EQUINX55, and German Brucher company produces; Superconduction digital nuclear magnetic resonance instrument, model are AVANCF300MHZ, and Switzerland Bruker company produces; Gel permeation chromatograph, model are Waters-Breeze, and U.S. waters company produces.
1, the equal polymerization of trifluoroethyl methacrylate
Room temperature charges into CO with syringe pump 5 in reactor 8 2Gas to the pressure in the reactor 8 are 0.5MPa, emit the gas that charges into, and vacuumize with vacuum pump 1 and make that vacuum tightnesss are 0.09MPa in the reactor 8, repetition above-mentioned steps 2 times.
Trifluoroethyl methacrylate 10.2138g is joined reactor 8 with volume pump 6, in reactor 8, charge into CO with syringe pump 5 2Fluid to the pressure in the reactor 8 is 7MPa, trifluoroethyl methacrylate and CO in the reactor 8 2The fluidic volume is reactor 8 volumetrical 30%, reactor 8 usefulness well heaters 7 are warmed up to 55 ℃, get Diisopropyl azodicarboxylate 0.101g and join reactor 8 by sample hose 4 usefulness syringe pumps 5, the mol ratio of trifluoroethyl methacrylate and Diisopropyl azodicarboxylate is 1:0.01, stir with stirrer 9, replenish CO with syringe pump 5 2Fluid to reactor 8 internal pressures are 32.6MPa, carry out chemical reaction, and chemical equation is as follows:
Figure C200710018389D00171
Reacted 24 hours, and stopped to stir, ice-water bath is cooled to 0～5 ℃, open micrometering valve 2, the fluid in the reactor 8 is discharged and gasification, and the snubber assembly of flowing through is collected and carried component, discharge tail gas or after purification, recycle, exit, collect the thick product of polymethyl acrylic acid trifluoro ethyl ester to normal pressure.
The thick product of polymethyl acrylic acid trifluoro ethyl ester is joined apparatus,Soxhlet's with the alcohol extraction of 25 times of weight 3～10 times, separating monomer, also used water extracting and separating monomer, solid after the extraction was prepared into the polymethyl acrylic acid trifluoro ethyl ester in 24 hours 50 ℃ of following vacuum-dryings, productive rate is 88.3%, molecular weight is 57916, and molecular weight distribution is 1.2055, and number-average molecular weight and molecular weight distribution are measured according to standard GB 6599-66 with gel permeation chromatography.
The infrared spectra of prepared product is seen Fig. 2, and proton nmr spectra is seen Fig. 3, and carbon-13 nmr spectra is seen Fig. 4, and spectral data is as follows:
IR (pressing potassium bromide troche) υ: 3000,2972,1753,1490,1457,1421,1282,1185,1031,972,893,844,746,659cm -1
1HNMR(300MHz，CDCl 3)δ：4.35(2H)，2.0～1.9(2H)，1.1～0.9(3H)ppm。
13C?NMR(75MHz，CDCl 3)δ：176，123，62.5，54.2，45.6，19.5，17.8ppm。Spectral data shows that product is the polymethyl acrylic acid trifluoro ethyl ester, and its structural formula is as follows:
Figure C200710018389D00181
2, the equal polymerization reaction times of trifluoroethyl methacrylate determines
Room temperature charges into CO with syringe pump 5 with syringe pump 55 in reactor 8 2Gas to the pressure in the reactor 8 is 0.5MPa, emits the CO that charges into 2Gas vacuumizes with vacuum pump 1 and to make that vacuum tightnesss are 0.09MPa in the reactor 8, repeats above-mentioned with vacuum pump 1 vacuum 2 times; The 16.8g trifluoroethyl methacrylate is joined reactor 8 with volume pump 6, in reactor 8, charge into CO with syringe pump 5 2Fluid to the pressure in the reactor 8 is 6.8MPa, trifluoroethyl methacrylate and CO in the reactor 8 2The fluidic volume is reactor 8 volumetrical 30%, reactor 8 usefulness well heaters 7 are warmed up to 70 ℃, get Diisopropyl azodicarboxylate 0.164g and join reactor 8 by sample hose 4 usefulness syringe pumps 5, the mol ratio of trifluoroethyl methacrylate and Diisopropyl azodicarboxylate is 1:0.010, stir with stirrer 9, replenish CO with syringe pump 5 2Fluid to reactor 8 internal pressures are that 25MPa implements polymerization; Reacting 6,12,24,36,48 hours from reactor 8 samplings respectively with stopple coupon 3, recover pressure after each sampling with syringe pump 5 fluid replacement along thief hole, 3 to 0～5 ℃ of each stopple coupons after the ice-water bath cooling sampling, open micrometering valve 2, fluid in the stopple coupon 3 is discharged and gasification, exits to normal pressure, opens stopple coupon 3 and collects sample, analysis list transformation rate, polymericular weight and distribution thereof.Fig. 5 is seen in the contrast of various kinds product infrared spectra, and Fig. 6 (mark expression reaction times among the figure) is seen in the nucleus magnetic resonance contrast, and spectral data shows that product is the polymethyl acrylic acid trifluoro ethyl ester.Monomeric transformation efficiency is calculated as follows:
Con . % = A 4.35 / 2 A 4.35 / 2 + A 6 . 26 × 100 - - - ( 2 )
A in the formula 6..26, A 4.35Represent that respectively sample exists 16.26ppm, 4.35ppm place integral area in the H NMR collection of illustrative plates, Con.% represents the transformation efficiency of monomer methacrylic acid trifluoro.
Differential responses time trifluoroethyl methacrylate sample number average molecular weight, molecular weight distribution and monomer conversion analytical results see Table 1.
Table 1 differential responses time trifluoroethyl methacrylate sample number average molecular weight, molecular weight distribution and monomer conversion analytical results
Reaction times (hour) Number-average molecular weight Molecular weight distribution Monomer conversion (%)
6 15211 1.203 55.7
12 16475 1.315 66.6
24 16553 1.331 85.4
36 16294 1.422 89.9
48 16193 1.447 90.5
By table 1 as seen, polymerization reaction time is got and was advisable in 24 hours, at this moment, monomer conversion reaches more than 85%, molecular weight is maximum and distribution relative narrower in 5 samples, though time expand can be improved transformation efficiency, may molecular weight be reduced because of superpolymer decomposes, distributing broadens.For trifluoroethyl methacrylate all polymerizations in supercritical co, the selective reaction time of the present invention is 6～48 hours, and optimum reacting time is 24 hours.
3, the equal polymerization temperature of trifluoroethyl methacrylate, pressure, radical initiator amount are optimized
Adopt orthogonal experimental design method, the level of factor table sees Table 2.
Table 2 level of factor table
Level of factor Temperature T (℃) A Pressure P (MPa) B The radical initiator amount compares C
1 70.0 25.0 1:0.010
2 62.5 32.5 1:0.005
3 55.0 17.5 1:0.020
Experiment 1: room temperature charges into CO with syringe pump 5 in reactor 8 2Gas to the pressure in the reactor 8 is 0.6MPa, emits the CO that charges into 2Gas vacuumizes with vacuum pump 1 and to make that vacuum tightnesss are 0.09MPa in the reactor 8, repeats above-mentioned with vacuum pump 1 vacuum 2 times; The 10.0011g trifluoroethyl methacrylate is joined reactor 8 with volume pump 6, and charging into the CO2 fluid with syringe pump 5 in reactor 8 is 6.8MPa to the pressure in the reactor 8, trifluoroethyl methacrylate and CO in the reactor 8 2The fluidic volume is reactor 8 volumetrical 30%, reactor 8 usefulness well heaters 7 are warmed up to 70 ℃, get Diisopropyl azodicarboxylate 0.0920g and join reactor 8 by sample hose 4 usefulness syringe pumps 5, the mol ratio of trifluoroethyl methacrylate and Diisopropyl azodicarboxylate is 1:0.0094, stir with stirrer 9, replenish CO with syringe pump 5 2Fluid to reactor 8 internal pressures are 25MPa, reacted 24 hours, stop to stir, ice-water bath is cooled to 0～5 ℃, opens micrometering valve 2, and fluid is discharged and gasification, the snubber assembly of flowing through is collected and is carried component, discharge tail gas or after purification, recycle, exit, collect the thick product of polymethyl acrylic acid trifluoro ethyl ester to normal pressure.Analyze monomeric transformation efficiency, transformation efficiency calculates by (2) formula.The thick product of polymethyl acrylic acid trifluoro ethyl ester is joined the alcohol extraction of apparatus,Soxhlet's with 25 times of weight, solid after the extraction was prepared into the polymethyl acrylic acid trifluoro ethyl ester in 24 hours 50 ℃ of following vacuum-dryings, productive rate is 88.3%, and number-average molecular weight is 57916, and molecular weight distribution is 1.2055.Molecular weight and distribution thereof are measured according to standard GB 6599-66 with gel permeation chromatography.
Experiment 2～9 operating procedures are identical with experiment 1, and the experimental implementation parameter sees Table 3, polymeric articles 1H NMR collection of illustrative plates is seen Fig. 7 (mark digitized representation experiment numbers among the figure).
Experimental result sees Table 3.
The equal polymerization parameters Optimization of table 3 trifluoroethyl methacrylate
Figure C200710018389D00201
As shown in Table 3, monomer/radical initiator in 1:0.0050～0.0203, temperature at 55～70 ℃, pressure in 17.5～32.6MPa scope, the polymethyl acrylic acid trifluoro ethyl ester molecular weight distribution of preparation is 1.1734～1.3943, avoid monomer to run off with the working method that the present invention sets, reaction yield is improved, avoided temperature not reach the set(ting)value decomposition initiated polymerization of radical initiator in temperature-rise period before, made the molecular weight of product distribution narrow.
The transformation efficiency analysis of Influential Factors sees Table 4.
Table 4 experiment parameter is to the variance analysis of transformation efficiency
Figure C200710018389D00211
K in the table represents the level effect value of factor, and Q represents each sum of squares of deviations, and X is that monomer conversion (%) p is a number of levels at this, and r is the experiment number of each level.
V i = Σ K i 2 / r , R = Σ p Σ r X 2 ij = 56420.52 , W = ( Σ p Σ r Xij ) 2 / pr = 54003.56
Q A＝V A-W＝545.54，Q B＝V B-W＝897.85，Q C＝V C-W＝544.54，Q T＝R-W＝2416.96
Q e＝Q I-Q A-Q B-Q C＝429.03
By above-mentioned analytical results as can be known, pressure has the greatest impact and presents positive correlation monomer conversion, and temperature and radical initiator amount are more less and experimental error is approaching than relative influence, consider that from improving transformation efficiency pressure, temperature, radical initiator amount best of breed are A 2B 2C 3, promptly pressure selects the mol ratio of 32.5MPa, 62.5 ℃ of temperature selections, monomer and radical initiator to select 1:0.020, and with this understanding, transformation efficiency can reach 90.3%, and augmenting response pressure helps transformation efficiency to improve most.
The molecular weight analysis of Influential Factors sees Table 5.
Table 5 experiment parameter is to the variance analysis of molecular weight
K in the table represents the level effect value of factor, and Q represents each sum of squares of deviations, and X is a number-average molecular weight at this, and p is a number of levels, and r is the experiment number of each level.
V i = Σ K i 2 / r , R = Σ p Σ r X 2 ij = 8603728325 , W = ( Σ p Σ r Xij ) 2 / pr = 5569686653
According to last table can be regarded as the value of each sum of squares of deviations Q.
Q A＝V A-W＝1775713129，Q B＝V B-W＝172383991，Q C＝V C-W＝522635001，Q T＝R-W＝3034041672，Q e＝Q T-Q A-Q B-Q C＝563309551
By above-mentioned analytical results as can be known, temperature has the greatest impact and is negative correlation polymericular weight, and pressure is more less than relative influence with the radical initiator amount, reduces the raising that temperature of reaction helps molecular weight of product, consider that from improving molecular weight its best of breed is A 3B 3C 2, promptly optimum temps be 55 ℃, optimum response pressure to be that the mol ratio of 17.5MPa, monomer and radical initiator is best be 1:0.0050, with this understanding, number-average molecular weight can reach 58614.
Above Orthogonal experiment results shows, reaction pressure having the greatest impact and being proportionate monomer conversion, the relative influence with the radical initiator amount of temperature is less, the distribution that reaction pressure improves molecular weight reduces, aspects such as transformation efficiency, product performance are all increased, but pressurize, energy consumption increases, the corresponding raising of cost; Temperature has the greatest impact and is negative correlation polymericular weight, reduces the raising that temperature of reaction helps molecular weight of product, and the relative influence with the radical initiator amount of reaction pressure is less, but temperature is low, and chain starting reaction is suppressed, and rate of polymerization is slow, transformation efficiency is low, and molecular weight distribution broadens; Big radical initiator amount helps to accelerate speed of reaction, shortens polymerization time, but is unfavorable for the raising of molecular weight of product, and the radical initiator amount is very few, and rate of polymerization is slow, and transformation efficiency is low, and molecular weight distribution broadens.Take all factors into consideration transformation efficiency, molecular weight and distribution thereof, energy consumption and cost, polymerization time is 24 hours in supercritical co, and the equal polymerization temperature of trifluoroethyl methacrylate, pressure, radical initiator amount best of breed are A 3B 2C 1, promptly temperature is preferably selected 55～62.5 ℃, reaction pressure best monomer conversion is 88.3% for the optimum mole ratio of 32.5MPa, monomer and radical initiator is 1:0.01, and number-average molecular weight is 57916, and molecular weight distribution is 1.2055.
4, the equal polymerization of trifluoroethyl methacrylate
Trifluoroethyl methacrylate 11.0888g is joined reactor 8 with volume pump 6, in reactor 8, charge into 1,1,1,2-Tetrafluoroethane fluid is 3.5MPa to the pressure in the reactor 8, trifluoroethyl methacrylate and 1 in the reactor 8,1,1,2-Tetrafluoroethane fluidic volume is reactor 8 volumetrical 30%, and reactor 8 usefulness well heaters 7 are warmed up to 70 ℃, get Diisopropyl azodicarboxylate 0.11633g and join reactor 8 by sample hose 4 usefulness syringe pumps 5, the mol ratio of trifluoroethyl methacrylate and Diisopropyl azodicarboxylate is 1:0.011, stirs with stirrer 9, replenishes 1 with syringe pump 5,1,1,2-Tetrafluoroethane fluid to reactor 8 internal pressures are 25MPa, carry out chemical reaction, reacted 24 hours, stop to stir, ice-water bath is cooled to 0～5 ℃, opens micrometering valve 2, fluid in the reactor 8 is discharged and gasification, the snubber assembly of flowing through is collected and is carried component, discharges tail gas or recycle the thick product of collection polymethyl acrylic acid trifluoro ethyl ester after purification.
Thick product joins the alcohol extraction of apparatus,Soxhlet's with 20 times of weight, and separating residual monomer, the product after the separation 50 ℃ of dryings 24 hours in vacuum drying oven are prepared into the polymethyl acrylic acid trifluoro ethyl ester.The spectral data of prepared product is as follows:
IR (pressing potassium bromide troche) υ: 3000,2972,1753,1490,1457,1421,1282,1185,1031,972,893,844,746,659cm -1
1H?NMR(300MHz，CDCl 3)δ：4.35(2H)，2.0～1.9(2H)，1.1～0.9(3H)ppm。Spectral data shows that product is the polymethyl acrylic acid trifluoro ethyl ester.
5, the equal polymerization of methyl methacrylate
Methyl methacrylate 10.00g is joined reactor 8 with volume pump 6, in reactor 8, charge into CO with syringe pump 5 2Fluid to the pressure in the reactor 8 is 7MPa, methyl methacrylate and CO2 fluidic volume are reactor 8 volumetrical 20%～30% in the reactor 8, reactor 8 usefulness well heaters 7 are warmed up to 57.5 ℃, get benzoyl peroxide 0.242g and join reactor 8 by sample hose 4 usefulness syringe pumps 5, the mol ratio of methyl methacrylate and benzoyl peroxide is 1:0.01, stir with stirrer 9, replenish CO with syringe pump 5 2Fluid to reactor 8 internal pressures are 15MPa, carry out chemical reaction, reacted 6 hours, stop to stir, ice-water bath is cooled to 0～5 ℃, opens micrometering valve 2, fluid in the reactor 8 is discharged and gasification, the snubber assembly of flowing through is collected and is carried component, exits to normal pressure, collects the thick product of polymethylmethacrylate.The thick product of polymethylmethacrylate is joined the alcohol extraction of apparatus,Soxhlet's with 20 times of weight, and the solid after the extraction was prepared into polymethylmethacrylate in 24 hours 50 ℃ of following vacuum-dryings.The spectral data of prepared product is as follows:
IR (pressing potassium bromide troche) υ: 3000,2954,2847,1728,1454,1385,1275,1197,1147,1062,990,844,752cm -1
1H?NMR(300MHz，CDCl 3)δ：3.61(3H)，1.64～1.5(2H)，1.29～1.24(3H)ppm。Spectral data shows that product is a polymethylmethacrylate, and productive rate is 82.1%, and number-average molecular weight is 27844, and molecular weight distribution is 1.3185.Its structural formula is as follows:
Figure C200710018389D00241
6, the equal polymerization of vinyl pyrrolidone
Vinyl pyrrolidone 6.006g is joined reactor 8 with volume pump 6, in reactor 8, charge into CO with syringe pump 5 2Fluid to the pressure in the reactor 8 is 6.4MPa, vinyl pyrrolidone and CO in the reactor 8 2The fluidic volume is reactor 8 volumetrical 25%, reactor 8 usefulness well heaters 7 are warmed up to 62.5 ℃, get Diisopropyl azodicarboxylate 0.0444g and join reactor 8 by sample hose 4 usefulness syringe pumps 5, the mol ratio of vinyl pyrrolidone and Diisopropyl azodicarboxylate is 1:0.005, stir with stirrer 9, replenish CO with syringe pump 5 2Fluid to reactor 8 internal pressures are 25MPa, react 24 hours.Stop to stir, ice-water bath is cooled to 0～5 ℃, open micrometering valve 2, fluid in the reactor 8 is discharged and gasification, the snubber assembly of flowing through is collected and is carried component, exits to normal pressure, collects the thick product of Polyvinylpyrolidone (PVP), thick product is joined the alcohol extraction of apparatus,Soxhlet's with 20 times of weight, and the solid after the extraction was prepared into Polyvinylpyrolidone (PVP) in 24 hours 50 ℃ of following vacuum-dryings.The spectral data of prepared product is as follows:
IR (pressing potassium bromide troche) υ: 3441,2929,1638,1431,1287cm -1
1H?NMR(300MHz，CDCl 3)δ：3.76(1H)，3.40(2H)，2.23(2H)，2.00(2H)，1.55(2H)ppm。Spectral data shows that product is a Polyvinylpyrolidone (PVP), and productive rate is 84.9%, and number-average molecular weight is 29284, and molecular weight distribution is 1.3836.
Its structural formula is as follows:
Figure C200710018389D00251
7, the equal polymerization of N-N-isopropylacrylamide
8.475g joins reactor 8 with volume pump 6 with the N-N-isopropylacrylamide, charges into CO with syringe pump 5 in reactor 8 2Fluid to the pressure in the reactor 8 is 6.4MPa, N-N-isopropylacrylamide and CO in the reactor 8 2The fluidic volume is reactor 8 volumetrical 20%～30%, reactor 8 usefulness well heaters 7 are warmed up to 55 ℃, get Diisopropyl azodicarboxylate 0.1231g and join reactor 8 by sample hose 4 usefulness syringe pumps 5, the mol ratio of N-N-isopropylacrylamide and Diisopropyl azodicarboxylate is 1:0.01, reactor 8 usefulness well heaters 7 are warmed up to 62.5 ℃, stir with stirrer 9, replenish CO with syringe pump 5 2Fluid to reactor 8 internal pressures are 25MPa, carry out chemical reaction, reacted 24 hours, stop to stir, ice-water bath is cooled to 0～5 ℃, opens micrometering valve 2, fluid in the reactor 8 is discharged and gasification, the snubber assembly of flowing through is collected and is carried component, discharges tail gas or recycle collection poly N-isopropyl acrylamide crude product after purification.Thick product joins the alcohol extraction of apparatus,Soxhlet's with 20 times of weight, and product 50 ℃ of dryings 24 hours in vacuum drying oven are prepared into poly N-isopropyl acrylamide, and it is 1 identical that other experimental procedure and the equal polymerization of trifluoroethyl methacrylate are tested.The spectral data of prepared product is as follows:
IR (pressing potassium bromide troche) υ: 3463,3299,2976,1663,1545,1443,1279,1175,688cm -1
1H?NMR(300MHz，CDCl 3)δ：8.1(1H)，3.8(1H)，2.6(1H)，1.6(2H)，1.3(2H)ppm。Spectral data shows that product is a poly N-isopropyl acrylamide, and productive rate is 80.4%, and number-average molecular weight is 31342, and molecular weight distribution is 1.376, and its structural formula is as follows:
Figure C200710018389D00252
8, the equal polymerization of trifluorochloroethylene
The consumption of trifluorochloroethylene is 10g, the consumption of di-t-butyl peroxide is 0.1256g, the mol ratio of trifluorochloroethylene and di-t-butyl peroxide is 1:0.01, and reactor 8 usefulness well heaters 7 are warmed up to 115 ℃, replenishes 1 with syringe pump 5,1,1,2-Tetrafluoroethane fluid to reactor 8 internal pressures are 25MPa, react 12 hours, other step is identical with equal polymerization 5 experiments of methyl methacrylate, and productive rate is 76.8%.
9, the equal polymerization of methacrylate based propyl trimethoxy silicane
The consumption of methacrylate based propyl trimethoxy silicane is 12.4175g, and the consumption of Diisopropyl azodicarboxylate is 0.0821g, and the mol ratio of methacrylate based propyl trimethoxy silicane and Diisopropyl azodicarboxylate is 1:0.01.Reactor 8 usefulness well heaters 7 are warmed up to 70 ℃, replenish CO with syringe pump 5 2Fluid to reactor 8 internal pressures are 25MPa, react 24 hours, and it is 6 identical that other step and the equal polymerization of vinyl pyrrolidone are tested.Prepared product spectral data is as follows:
IR (pressing potassium bromide troche) υ: 2951,2838,1729,1473,1407,1321,1297,1192,1088,975,820cm -1
1H?NMR(300MHz，CDCl 3)δ：3.81(2H)，3.51(9H)，1.67(4H)，0.94～0.70(3H)，0.59(2H)ppm。Spectral data shows that product is a polymethacrylate base propyl trimethoxy silicane, and productive rate is 72.1%, and structural formula is as follows:
Figure C200710018389D00261
10, methyl methacrylate and trifluoroethyl methacrylate copolymerization
The consumption of methyl methacrylate is 7.5g, the consumption of trifluoroethyl methacrylate is 12.6g, the mol ratio of methyl methacrylate and trifluoroethyl methacrylate is 1:1, the consumption of Diisopropyl azodicarboxylate is 0.246g, the mol ratio of methyl methacrylate and trifluoroethyl methacrylate and Diisopropyl azodicarboxylate is 1:0.01, reactor 8 usefulness well heaters 7 are warmed up to 62.5 ℃, replenish CO with syringe pump 5 2Fluid to reactor 8 internal pressures are 27MPa, react 6 hours.It is 4 identical that other technological process of this experimental procedure and the equal polymerization of trifluoroethyl methacrylate are tested.It is 6 identical that other experimental procedure and the equal polymerization of vinyl pyrrolidone are tested.The spectral data of prepared product is as follows:
IR (pressing potassium bromide troche) υ: 3002,2959,1752,1461,1418,1288,1178,1031,969,892,842,753,659cm -1
1H?NMR(300MHz，CDCl 3)δ：4.36，3.62，1.92，1.48，1.24～0.86ppm。Spectral data shows that product is trifluoroethyl methacrylate and methylmethacrylate copolymer, and productive rate is 86.1%, and number-average molecular weight is 37108, and molecular weight distribution is 1.248.
11, trifluoroethyl methacrylate and methacrylate based propyl trimethoxy silicane copolymerization
In polymerization procedure 2, this experiment monomer is selected trifluoroethyl methacrylate and methacrylate based propyl trimethoxy silicane for use, radical initiator is selected Diisopropyl azodicarboxylate for use, fluid selects 1 for use, 1,1, the 2-Tetrafluoroethane, the consumption of trifluoroethyl methacrylate is 9.4g, the consumption of methacrylate based propyl trimethoxy silicane is 2.0g, charges into 1,1 in reactor 8,1,2-Tetrafluoroethane fluid is 4MPa to the pressure in the reactor 8, and reactor 8 usefulness well heaters 7 are warmed up to 70 ℃, and the consumption of Diisopropyl azodicarboxylate is 0.105g, base vinylformic acid trifluoro ethyl ester and methacrylate based propyl trimethoxy silicane and Diisopropyl azodicarboxylate mol ratio be 1:0.01, replenish 1,1,1 with syringe pump 5,2-Tetrafluoroethane fluid to reactor 8 internal pressures are 20MPa, react 24 hours.It is 6 identical that other process of this step and the equal polymerization of vinyl pyrrolidone are tested, and it is 6 identical that other experimental procedure and the equal polymerization of vinyl pyrrolidone are tested.The spectral data of prepared product is as follows:
IR (pressing potassium bromide troche) υ: 3459,2970,2847,1753,1456,1419,1287,1173,970,825,658cm -1
1H?NMR(300MHz，CDCl 3)δ：4.61，4.10，3.55，1.91，1.61，1.30，0.58ppm。Spectral data shows that product is the polymethyl acrylic acid trifluoro ethyl ester, and productive rate is 91.1%, and number-average molecular weight is 16609, and molecular weight distribution is 1.388.
12, trifluoroethyl methacrylate and styrene copolymerisation
In polymerization procedure 2, this experiment monomer is selected trifluoroethyl methacrylate and vinylbenzene for use, and radical initiator is selected Diisopropyl azodicarboxylate for use, and fluid is selected CO for use 2The consumption of trifluoroethyl methacrylate is 16.8g, and cinnamic consumption is 10.4g, charges into CO with syringe pump 5 in reactor 8 2Fluid is 7MPa to the pressure in the reactor 8, and reactor 8 usefulness well heaters 7 are warmed up to 62.5 ℃, and the consumption of Diisopropyl azodicarboxylate is 0.2884g, and the mol ratio of trifluoroethyl methacrylate and vinylbenzene and Diisopropyl azodicarboxylate is 1:0.009, replenishes CO with syringe pump 5 2Fluid to reactor 8 internal pressures are 28MPa, react 24 hours, and it is 1 identical that other process of this step and the equal polymerization of trifluoroethyl methacrylate are tested, and it is 1 identical that other experimental procedure and the equal polymerization of trifluoroethyl methacrylate are tested.The spectral data of prepared product is as follows:
IR (pressing potassium bromide troche) υ: 3459,3065,3031,2980,2947,1751,1605,1510,1455,1416,1285,1169,1118,1035,965,910,842,703,658cm -1
1H?NMR(300MHz，CDCl 3)δ：7.10～6.88，4.14，2.43，1.99～0.54ppm。Spectral data shows that product is trifluoroethyl methacrylate and cinnamic multipolymer, and productive rate is 84.3%, and number-average molecular weight is that 37126 molecular weight distribution are 1.486.
13, trifluoroethyl methacrylate and vinyl pyrrolidone copolymerization
The consumption of trifluoroethyl methacrylate is 6.624g, the consumption of vinyl pyrrolidone is 4.0010g, the consumption of Diisopropyl azodicarboxylate is 0.0616g, the mol ratio of trifluoroethyl methacrylate and vinyl pyrrolidone and Diisopropyl azodicarboxylate is 1:0.005, reactor 8 usefulness well heaters 7 are warmed up to 62.5 ℃, replenish CO with syringe pump 5 2Fluid to reactor 8 internal pressures are 30MPa, react 24 hours, and other process of this step is identical with experiment 6, and other experimental procedure is identical with experiment 6.The infrared spectra of prepared product is seen Fig. 8, and proton nmr spectra is seen Fig. 9, and spectral data is as follows:
IR (pressing potassium bromide troche) υ: 2986,2929,1752,1684,1466,1425,1287,1166,1031,975,840,655cm -1
1H?NMR(300MHz，CDCl 3)δ：4.41，3.20，2.18～1.94，1.55，1.10ppm。Spectral data shows that product is trifluoroethyl methacrylate and vinylpyrrolidone copolymer, and productive rate is 87.1%, and number-average molecular weight is 206802, and molecular weight distribution is 1.255.

Claims (4)

1, a kind of method for preparing polythene derivative in supercutical fluid is characterized in that it comprises the steps:
(1) reactor vacuumizes
Room temperature charges into CO with syringe pump (5) in reactor (8) 2Or N 2Or the pressure of Ar gas to the reactor (8) is 0.3～1MPa, emits the gas that charges into, and vacuumizes with vacuum pump (1) that to make the interior vacuum tightness of reactor (8) be 0.09MPa, repetition above-mentioned steps 2 times;
(2) polyreaction
Monomer is joined reactor (8) with volume pump (6), charging into fluid to the pressure in the reactor (8) in reactor (8) is 3.5～7MPa, monomer and fluidic volume are reactor (8) volumetrical 20%～30%, be warmed up to 47～115 ℃ with well heater (7), radical initiator joins reactor (8) by sample hose (4) with syringe pump (5), the mol ratio of monomer and radical initiator is 1:0.001～0.02, stir with stirrer (9), with syringe pump (5) fluid replacement to reactor (8) internal pressure is 10～40MPa, carry out chemical reaction, chemical equation is as follows:
Figure C200710018389C00021
(1) R in the formula 1, R 2Be H or F, R 1, R 2Identical; R 3Be H or CH 3Or F, R 4Be C 6H 5Or F or Cl or OCOR or COOR, R is C mH 2mn+1Or C nH 2F 2n-1, m is 1～4, and n is 2～4, and p is the polymerization degree; Reacted 6～48 hours, and stopped to stir, ice-water bath is cooled to 0～5 ℃, open micrometering valve (2), the fluid in the reactor (8) is discharged and gasification, and the snubber assembly of flowing through is collected and carried component, tail gas is discharged or is recycled after purification, exits to normal pressure, collects thick product;
Above-mentioned monomer comprises vinyl-acetic ester or acrylate or N-N-isopropylacrylamide or methacrylic ester or methacrylate based propyl trimethoxy silicane or vinyl pyrrolidone or trifluoroethyl methacrylate or trifluorochloroethylene or tetrafluoroethylene or vinyl fluoride or vinylidene fluoride, described acrylate comprises methyl acrylate, ethyl propenoate, butyl acrylate, Octyl acrylate, and described methacrylic ester comprises methyl methacrylate, Jia Jibingxisuanyizhi, butyl methacrylate, dimethylaminoethyl methacrylate; Above-mentioned radical initiator is Diisopropyl azodicarboxylate or benzoyl peroxide or di-t-butyl peroxide; Above-mentioned fluid is carbonic acid gas or 1,1,1,2-Tetrafluoroethane or trifluoromethane;
(3) separate purification
Thick product is joined apparatus,Soxhlet's with the ethanol of 20～30 times of weight or water extraction 3～10 times, and separating residual monomer, the product after the separation 50 ℃ of dryings 24 hours in vacuum drying oven are prepared into polythene derivative.
2, according to the described method that in supercutical fluid, prepares polythene derivative of claim 1, it is characterized in that: in polymerization procedure (2), monomer is joined reactor (8), fluid charges into reactor (8), wherein be warmed up to 55～62.5 ℃ with well heater (7), radical initiator joins reactor (8) by sample hose (4) with syringe pump (5), the mol ratio of monomer and radical initiator wherein is 1:0.005～0.015, stir with stirrer (9), with syringe pump (5) fluid replacement to reactor (8) internal pressure wherein is 15～40MPa, carries out chemical reaction.
3, according to the described method that in supercutical fluid, prepares polythene derivative of claim 1, it is characterized in that: in polymerization procedure (2), monomer is joined reactor (8), fluid charges into reactor (8), wherein be warmed up to 55 ℃ with well heater (7), radical initiator joins reactor (8) by sample hose (4) with syringe pump (5), the mol ratio of monomer and radical initiator wherein is 1:0.01, stir with stirrer (9), with syringe pump (5) fluid replacement to reactor (8) internal pressure wherein is 32.5MPa, carries out chemical reaction.
4, according to the described method that in supercutical fluid, prepares polythene derivative of claim 1, it is characterized in that: in chemical equation (1), R 3Wherein be CH 3Or F, R 4Wherein be F or COOR.
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