Method of producing fluoroelastomers

专利摘要:
1496084 Fluoroelastomers E I DU PONT DE NEMOURS & CO 30 Jan 1975 [31 Jan 1974] 4145/75 Heading C3P Fluoroelastomers are copolymers of (by weight) 4-15% tetrafluoroethylene, 48-65% vinylidene fluoride, 8-23% hexafluoropropene and 17-30% of perfluoro (C 1 -C 5 ) alkyl perfluorovinyl ether. They are prepared in examples by emulsion polymerization.
公开号:SU822755A3
申请号:SU752106666
申请日:1975-01-30
公开日:1981-04-15
发明作者:Лерой Бэйрд Ричард；Даниэль Маклачлан Джеймс
申请人:Е.И.Дюпон Де Немур Энд Компани (Фирма)；
IPC主号:

专利说明:

The invention relates to a process for the preparation of fluoroelastomers and can be used in the chemical industry. A known method for the preparation of fluoroelastomers by a water emulsion copolymerization of tetrafluoroethylene, vinyl, idfluoride and perfluoro (C-Su-alkyl) perfluoro ethyl ether in the presence of emulsifiers and radical initiators l. The disadvantage of this method is the relatively low elasticity of the fluoroelastomers at low temperatures. The purpose of the invention is to reduce the elasticity of fluoroelastomers at low temperatures while maintaining their high heat resistance and resistance to solvents. This goal is achieved by the fact that according to the method of producing fluoroelastomers by water emulsion copolymerization of tetrafluoroethylene, vinylidene fluoride and perfluoro (C-CJ. ether in the presence of emulsifiers and radical initiators, the process is carried out in the presence of hexafluoropropylene as an additional monomer in the following ratio of components to monomer mixture, wt.% Tetrafluoroethylene 5-11 Vinylidene fluoride 50-58 Hexafluoropropylene 10-18 Perfluoro (C C alkyl) perfluorovinyl ether 20-30 Ammonium, sodium, potassium persulfates or their mixture, as well as other water-soluble inorganic peroxide can be used as initiators compounds, e.g., persulphates, perborates and percarbonates of sodium, potassium and ammonium. The initiator may be used in a mixture with a reducing agent such as sulfite, bisulfite, metabisulfite, hyposulfite, thiosulfate, phosphite or sodium, potassium and ammonium hypophosphite in combination with an iron, copper or silver salt or easily oxidizable metal compounds. Organic initiators can also be used, preferably in combination with a suitable surfactant such as sodium lauryl sulfate and ammonium perfluorooctane, sodium.
During polymerization, a suitable known chain transfer agent can be obtained.
After polymerization is complete, the copolymer can be separated from the final polymer latex by known methods, for example, by coagulation by adding electrolyte or freezing, followed by centrifuging or filtering and then drying the copolymer.
Example 1. A fluoroelastomer is manufactured in a continuous process consisting of the following operations.
. 1, Continuous supply of four monomers to a one-liter stainless steel reactor under pressure (polymerization reaction zone), which is flushed with nitrogen, at. this reactor agitator makes 700 rev .. / min, pass. through the mixture of the contents of the reactor, heated before and under a pressure of 63.3 kg / cm so that the reaction mixture formed in stage 2 undergoes an emulsion polymerization reaction as it passes through the reactor, the residence time in the reactor is about 15 minutes and depends on the ratio of one liter of reactor to the emulsion formation rate of approximately 4 liters per hour, the monomers and the feed rate of each should be the same as shown in table 1.
2.During operation 1, a solution containing 2.73 g of ammonium persulfate dissolved in 3409 ml of water is continuously fed into the reactor through the first metering pump every hour, and simultaneously the solution containing 0.81 g containing it is hourly fed into the reactor via the second metering pump. sodium hydroxide and O, 5 g sodium lauryl sulfate, dissolved in 598 ml of water, the pH of the reaction mixture is maintained at 4.1.
3. Continuously removing the copolymer latex from the reactor, forming during the first and second operations, the latex passes first through a regulating check valve installed to maintain the desired pressure in the reactor at 63.3 kg / cm and then through a closed container from which the waste gas (unreacted monomers) are fed to a gas chromatograph and where its composition is determined and is recorded in Table 1.
4. After discarding the latex obtained during the first four time periods, collect the desired amount of latex and mix it for homogeneity; the latex has a pH of about 4.1 and contains a solid copolymer in a concentration of 24.73%.
5. Separating the final copolymer from the latex by slowly adding 4% aqueous aluminum sulphate solution until the copolymer is coagulated, the copolymer particles are washed with distilled water, the water is separated using filtering equipment and then the copolymer is dried in a circulating thermostat until moisture less than 0.2%.
Table 1
At the preliminary stage of the process, it is possible to initiate the polymer formation reaction by feeding the solutions described in step 2 at a rate that is 3 times higher than specified until the polymerization reaction is established, which is detected by the presence of the polymer emulsion in the effluent stream.
The resulting copolymer is an elastomer that can be cured
0 in the manner described in Example 5. As can be seen from the last column of Table 1 for each. 1QO g of polymerized parts accounted for 9.6 g of polymerized tetrafluoroethylene, 53.5 g of polymerized vinylidene fluoride, 16.9 g
polymerized hexafluoropropylene and 20 g of polymerized perfluoromethylperfluorovinyl ether. The internal viscosity of the copolymer is 1.99%. It is determined at 30 ° C with a polymer concentration of 0.1% by weight in a solution consisting of 87% by volume of tetrahydrofuran and 13% by volume K, M-dimethylformamide. The copolymer is insoluble in aliphatic and aromatic hydrocarbons. The copolymer has a Mooney viscosity of 142 at. This is a measurement of volume. The viscosity is carried out in a Mooney viscometer using a large rotor and a 10-minute time shift. The copolymer is used in the production of rings and other products and: h the cured elastomer.
Example 2. Copolymer 1k .-) are similarly similar to the example .1 m-t I: kpyuche5 nik:
a) residence time in the reactor 14.2 min; I
b) in stage 2, the solution / feed (per hour) through the first metering pump, contains 4.91 g of ammonium persulfate dissolved in 3636 ml of water and the solution supplied through the second metering pump, contains a solution of 0.81 centners of sodium hydroxide, 0 55 g of sodium sulfite and 0. 72 g of sodium lauryl sulfate in 600 ml of water
c) in stage 3, the composition of the exhaust gases is determined, shown in Table 2;
d) in stage 4, a latex is obtained having a pH of about 4 and a solid polymer content of 22.8%,
table 2
Tabli ca
Tetraftor63, 5 0.25 63.2 4.7 ethylene
Vinyl or 799, 3 9.53 780 57.9 denfluoride
Hexafluorod244,913.2 232 17.2 propylene
Perfluoromethylperfluorovinyl
281.2 8.6 273 20.2 ether
Tetrafluoroethylene Vinylidene fluoride Hexafluoropropylene Perfluoromethyl perfluorine 281 33.1 248 19, lovy ether Copolyme.rnual product has the composition shown in the last column of Table 1; it has an internal viscosity of 1.38 and a Muni viscosity 87.5. T (. Of this example is. This value is determined using a differential DSC scanning calorimeter. Example 3. A fluto-4 elastomer is obtained by repeating example 1 with the following: a) in stage 1, the feed rate of the monomer as shown in Table. 3; b) at stage 2, the solution supplied (per hour) through the second dosing pump contains 0.72 g of sodium lauryl sulfate; . c) at stage 3, Gas waste is determined to have a composition, shown in Table. 3; d) in stage 4, a latex is obtained having a pH of about 4.4 and a solid polymer content of 2G, 19%. The copolymer has the composition shown in the last column of Table 3, its internal viscosity is 2.04, and Mooney viscosity is 150. 1.JJ is 30 ° C when measured by TC using the DSC method. Example 4. A fluoroelastomer is prepared analogously to example 1, except for: a) a two-liter reactor and a residence time in the reactor of 30 MIN are used; b) in stage 1, the feed rate of the monomers, as shown in table 4; c). in stage 2, the solution supplied (per hour) through the first metering pump consists of 3.33 g of ammonium persulfate in 3409 ml of water and the solution supplied through the second metering pump consists of 8.6 g of BUT in 598 ml of water ; d) in stage 3, the determination of the composition of the waste gases is lowered due to a high conversion degree, in the order of 97%; e) in stage 4, the pH and solid content of the polymer are not determined. The composition of the polymer of example 4 is shown in table 4. Table 4 Tetraftor102 102 ethylene Vinylidene fluoride 464 464

权利要求:
Claims (1)
[1]
Claim
A method of producing fluoroelastomers by water-emulsion copolymerization of tetrafluoroethylene, vinylidene fluoride and perfluoro (C ^ -Salkyl) perfluorovinyl ether in the presence of emulsifiers and radical initiators, characterized in that, in order to increase the elasticity of fluoroelastomers at low temperatures while maintaining their high thermal and solvent resistance , the process is carried out in the presence of hexafluoropropylene as an additional monomer in the following ratio of components in the monomer mixture, wt.%:
Tetraftor ethylene 5-11 Vinylidene fluoride 50-58 Hexafluoropropylene Perfluoro (C | -Su-alkyl) perfluorovinyl 10-18 ether 20-30

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同族专利:

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法律状态:

优先权:

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申请号 | 申请日 | 专利标题

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US43842674A| true| 1974-01-31|1974-01-31|

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