CN103724511B - The preparation method of a kind of fluororubber for oil seal - Google Patents
The preparation method of a kind of fluororubber for oil seal Download PDFInfo
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Abstract
The present invention relates to the preparation method of a kind of fluororubber for oil seal. This preparation method is by copolymerized units: vinylidene, R 1216 or vinylidene, R 1216, tetrafluoroethylene, and employing water is medium, and inorganic salt are initiator, through cohesion, washing, dries, shaping obtained finally by plasticating. Synthetic method provided by the invention passes through molecular weight control, prepare that molecular weight is higher, mobility is better, there is the viton of better molecular weight distribution, solve the technical barrier improving its flowing property while improving viton physical strength, can be applicable in multiple industry field, particularly automotive industry.
Description
Technical field
The present invention relates to the preparation method of a kind of fluororubber for oil seal, particularly relate to the preparation method of fluororubber for oil seal, belong to technical field of fluorine chemical industry.
Background technology
Viton refers to a kind of macromolecular elastomer with property being connected with fluorine atom on the carbon atom of main chain or side chain. Heat-resisting, the resistance to liquid excellent because of it and oil-proofness and good physical and mechanical properties, electrical insulating property and radiation resistance, be widely used in the aspects such as aviation, space flight, automobile and petrochemical complex. Such as the sealing of engine crankshaft and camshaft, the sealing of Hydraulic Elements (pump, motor), the sealing of automobile industry transmission system (such as wheel casing, wheel hub, bridge axle, differential mechanism), the sealing of the agricultural machine such as forklift, excavator and engineering machinery transmission. In recent years, when energy day is becoming tight, at chemical engineering industry and automotive field, along with the appearance of the novel environment friendly energy, fuel, such as methanol fuel oil, ethanol fuel oil, it is desired to viton has excellent solvent resistance.
Also there is certain gap in current domestic fluororubber for oil seal, mainly show as compared with abroad: the phenomenons such as molecular weight is not high, and processing fluidity is poor, and surface irregularity is rough.
The domestic and international technology with letex polymerization production fluorine-containing rubber has been known by the art, such as Chinese patent literature CN101186667A(application number 200710166448.0) adopt emulsion polymerisation process, copolymerization units is: the 1 of 50～70mol%, 1-bis-vinyl fluoride, the perfluoro propylene of 10～30mol% and the tetrafluoroethylene of 10～20mol%, prepare high-strength ternary fluororubber. But in prior art while focusing on product tensile property, often sacrifice processibility and mobility.
Chinese patent literature CN101429264A(application number 200810238475.9) provide a kind of width distribution fluoroelastomer preparation method, Mw is 10000-9000000, Mw/Mn is 2.5～20, and the method take organo-peroxide as initiator, generate organic groups. But the polymkeric substance of 100% organic groups degree of adhesion in last handling process is big, it is difficult to processing and process. This patent molecular weight Mw is 500000～1500000, Mn is 10000～100000, Mw/Mn is 5～30, under the prerequisite ensureing high molecular, by control lower molecular weight, namely number-average molecular weight Mn controls 10000～100000, and molecular weight distribution coefficient is improved greatly, Mw/Mn brings up to 30 by 20, and processing characteristics improves greatly.
In addition, Chinese patent literature CN101033319A discloses the oil sealing fluoroelastomer of methanol gasoline resistant, it is using with by different mooney viscosity fluoroelastomer, improve the processing characteristics of sizing material, but use the problems such as uneven, time-consuming, effort with rubber in the fluoroelastomer course of processing prepared by this method with.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, it is provided that the preparation method of a kind of fluororubber for oil seal.
The technical scheme of the present invention is as follows:
A preparation method for fluororubber for oil seal, comprises the steps:
(1) Xiang Shuizhong adds emulsifying agent and pH adjusting agent, and emulsifying agent accounts for the 0.01～0.2% of water weight, and pH adjusting agent accounts for the 0.01～0.5% of water weight, obtained solution A;
(2) adding monomer in the obtained solution A of step (1), water and the mass ratio of monomer in step (1) are 1:(0.01～1), stir even, obtained solution B;
(3) add, in the obtained solution B of step (2), the inorganic initiator solution initiated polymerization that concentration is 1～10wt%, polymerization pressure 1.0～4.0Mpa, temperature of reaction are 50～150 DEG C, and the add-on of inorganic initiator is the 0.005～1% of the weight of water in step (1);
(4) when 10～20% of the total charging capacity of monomer in monomer reaction weight to step (2), add molecular weight telogen, described molecular weight telogen add-on is 0.1～1wt% of the water weight in step (1), simultaneously by adding monomer in reaction vessel continuously, gas phase composition in reaction vessel is made to keep constant;
When 40～65% of the total charging capacity of monomer in monomer reaction weight to step (2), add molecular weight telogen again, described molecular weight telogen add-on is 0.05～1wt% of the water weight in step (1), and add inorganic initiator, the add-on of inorganic initiator is 0.005～1wt% of the weight of water in step (1), when 90～100% of the total charging capacity of monomer in monomer reaction weight to step (2), stopped reaction, obtained polymerized emulsion;
(5) undertaken the polymerized emulsion that step (4) is obtained condensing, wash, dry, plasticate through rubber mixing machine shaping, to obtain final product. This aftertreatment of step system and formed package, can refer to Chinese patent literature CN101186667A(application number 200710166448.0) adopt this area usual way to carry out.
The monomer of described step (2) is selected from one of following a～g:
A, 45～65% vinylidenes, 35～55% the mixture of R 1216, or the mixture of 10～50% vinylidenes, the R 1216 of 25～65% and the tetrafluoroethylene of 5～35%, is mass percent;
Preferably, the mixture of 50～60% vinylidenes and 40～50% R 1216s, or the mixture of 25～50% vinylidenes, 30～50% R 1216s and 15～30% tetrafluoroethylene; Prepared by this monomer copolymerization is binary or ternary fluororubber;
B, fluorochemical monomer mix with hydrocarbon monomer arbitrary proportion, the mixing of one or both any ratios that fluorochemical monomer is selected from trifluorochloroethylene, tetrafluoroethylene, vinylidene, R 1216, perfluoroalkyl (alkoxyl group) vinyl ether; Hydrocarbon monomer is selected from ethene and/or propylene; Prepared by this monomer copolymerization is binary or ternary fluororubber;
The mixing of c, trifluorochloroethylene and vinylidene arbitrary proportion; Gained viton is the multipolymer of trifluorochloroethylene and vinylidene;
The mixing of d, vinylidene and perfluoroalkyl (alkoxyl group) vinyl ether arbitrary proportion; Gained viton is vinylidene and the multipolymer of perfluoroalkyl (alkoxyl group) vinyl ether;
The mixing of e, ethene and R 1216 arbitrary proportion;Gained viton is the multipolymer of ethene and R 1216;
The mixing of f, tetrafluoroethylene and propylene arbitrary proportion; Gained viton is the multipolymer of tetrafluoroethylene and propylene;
The mixing of g, tetrafluoroethylene and perfluoroalkyl (alkoxyl group) vinyl ether arbitrary proportion; Gained viton is tetrafluoroethylene and the multipolymer of perfluoroalkyl (alkoxyl group) vinyl ether.
Emulsifying agent in described step (1) is selected from nonionic emulsifier or ionic emulsifying agent; Preferably, emulsifying agent is selected from ionic emulsifying agent perfluorooctanoic acid salt; Preferred further, emulsifying agent is selected from Sodium perfluorooctanoate or ammonium perfluorocaprylate.
PH adjusting agent in described step (1) is weak base salt, it is preferable that dipotassium hydrogen phosphate or sodium tetraborate.
Inorganic initiator in described step (3) and step (4) is persulphate; Preferably, inorganic initiator is Potassium Persulphate or ammonium persulphate.
Molecular weight telogen in described step (4) is selected from one of iso-pentane, diethyl malonate, succinate, ethyl acetate or the combination of two kinds of any ratios; Preferably, the molecular weight telogen in described step (4) is iso-pentane.
Useful effect
1, the present invention adopts water as medium, take emulsifying agent as dispersion agent, adopts inorganic initiator, and the height by molecular weight telogen Molecular regulator amount, utilizes chemical coagulation method to carry out condensing and wash, dewater. The fluororubber for oil seal molecular weight distribution coefficient thus obtained is between 5～20, high molecular weight peak is 500000～1500000, lower molecular weight peak is 10000～100000, for bimodal distribution, there is good mechanical property and the viton of processing flowability, tensile strength 15.0～20.0Mpa, tensile yield 180～300%, meets the needs of oil seal articles.
2, the present invention is divided into three sections to carry out in polymerization process, the first stage, adds initiator initiation reaction and generates high molecular system; When monomer reaction weight to the total charging capacity of monomer 10～20% time, enter subordinate phase, add molecular weight telogen, the molecular weight of polymer that control generates, make sizing material molecular weight both high, processing fluidity is better again; When monomer reaction weight to the total charging capacity of monomer 40～65% time, enter the phase III, add quantitative molecular amount telogen, the method improve sizing material processing characteristics, make oil sealing surface light.
Embodiment
Below by embodiment, the technical scheme of the present invention is described further, but institute of the present invention protection domain is not limited to this.
Mobility in viton processing characteristics detects by the following method:
1. viton is made rubber unvulcanizate according to same formula of rubber hose of extruding, it is pressed into certain thickness thin slice with mill, then become rule circular by die-cut, put into the first layer of the mould of detection mobility. Simulate the temperature of oil sealing preparation process and pressure with thermocompressor, by put into the first layer sizing material slowly by the aperture on mould, be pressed into the second layer with scale, characterize sizing material in the mobility necessarily extruding sizing material under condition by the scale number of degrees;
2. viton is made rubber unvulcanizate according to same oil sealing formula, extruded by the forcing machine of certain temperature and pressure. By checking smoothness of the surface, characterize the processing flowability of sizing material.
Viton molecular weight distribution coefficient detects by the following method:
Viton is dissolved in THF, measures its weight-average molecular weight (Mw), number-average molecular weight (Mn) by gel chromatography (GPC), mark peak-peak, and according to formula: distribution coefficient=Mw/Mn calculates molecular weight distribution coefficient.
Embodiment 1, for the polymeric kettle of 10L, preparation binary viton
6.5kg deionized water and 65ml concentration 10wt% Perfluorocaprylic Acid sodium solution, 10g dipotassium hydrogen phosphate is added in clean polymeric kettle; Find time, deoxygenation, be qualified to oxygen level≤30ppm; Then 40%(mass percent is used) R 1216 and 60%(mass percent) vinylidene, it is mixed with mixture as monomer, polymeric kettle is boosted to 1.6MPa, when the still temperature rise of still to be polymerized is to 80 DEG C, the potassium persulfate solution reaction that 20g concentration is 10wt% is squeezed into volume pump, monomer reaction weight to the total charging capacity of initial monomer 10% time, add 5ml molecular weight telogen iso-pentane, and add the potassium persulfate solution that 3g concentration is 10wt%, simultaneously by adding monomer in reaction vessel continuously, gas phase composition in reaction vessel is made to keep constant. Monomer reaction weight to the total charging capacity of initial monomer 50% time, add 45ml molecular weight telogen iso-pentane, and to add initiator 5g concentration be the potassium persulfate solution of 10wt%, until initial monomer complete reaction, stopped reaction. Through condensing, wash, dry, open the type of being smelt, to obtain final product.
After testing, the molecular weight distribution of this viton is bimodal distribution, and weight-average molecular weight Mw is 1305120. Mobility-detected is 283mm, oil sealing glue smooth surface.
Embodiment 2, for the polymeric kettle of 10L, preparation binary viton
The dipotassium hydrogen phosphate of 6.5kg deionized water and 65ml concentration 10wt% Perfluorocaprylic Acid sodium solution, 10g is added in clean polymeric kettle, find time, deoxygenation, be qualified to oxygen level≤30ppm, then 40%(mass percent is used) R 1216 and 60%(mass percent) vinylidene, it is mixed with mixture as monomer, polymeric kettle is boosted to 1.5MPa, when the still temperature rise of still to be polymerized is to 110 DEG C, squeeze into, with volume pump, the potassium persulfate solution 20g that concentration is 10wt% to react, monomer reaction weight to the total charging capacity of initial monomer 10% time, add 3ml molecular weight telogen diethyl malonate, and add the potassium persulfate solution that 5g concentration is 10wt%, simultaneously by adding monomer in reaction vessel continuously, gas phase composition in reaction vessel is made to keep constant. monomer reaction weight to the total charging capacity of initial monomer 50% time, add 50ml molecular weight telogen diethyl malonate, and add the potassium persulfate solution that 10g concentration is 10wt%, until initial monomer complete reaction, stopped reaction. through condensing, wash, dry, open the type of being smelt, to obtain final product.
After testing, the molecular weight distribution of this viton is bimodal distribution, and weight-average molecular weight Mw is 1012056. Mobility-detected is 267mm, oil sealing glue smooth surface.
Comparative example 1, for the polymeric kettle of 10L, preparation binary viton
The dipotassium hydrogen phosphate of 6.5kg deionized water and 65ml concentration 10wt% Perfluorocaprylic Acid sodium solution, 10g is added in clean polymeric kettle; Find time, deoxygenation, be qualified to oxygen level≤30ppm. Then 25%(mass percent is used) R 1216 and 75%(mass percent) vinylidene, it is mixed with mixture as monomer, polymeric kettle is boosted to 1.5Mpa, when the still temperature rise of still to be polymerized is to 110 DEG C, squeeze into, with volume pump, the potassium persulfate solution 10g that concentration is 10wt% to react, simultaneously by adding monomer in reaction vessel continuously, gas phase composition in reaction vessel is made to keep constant. Monomer reaction weight to the total charging capacity of initial monomer 60% time, add 50ml molecular weight telogen diethyl malonate, and add the potassium persulfate solution that 7g concentration is 10wt%, until initial monomer complete reaction, stopped reaction.Through condensing, wash, dry, open the type of being smelt, to obtain final product.
After testing, the molecular weight distribution of this viton is wide distribution, and weight-average molecular weight Mw is 505203. Mobility-detected is 192mm, oil sealing glue smooth surface.
Embodiment 3～4
According to the polymerization process of embodiment 1, adjust emulsifying agent and consumption respectively, pH adjusting agent and consumption, initiator and consumption, molecular weight telogen, add fashionable reaction pressure drop and consumption, obtaining the viton of different molecular weight distribution, molecular weight distribution and the mobility-detected of its polymerisate are as shown in table 1.
Table 1
Note: 1, in molecular weight telogen and consumption (ml), 5/10, represent that first time adds 5ml, first time adds 10ml, Yu Tong;
2, molecular weight telogen adds fashionable weight, 10%/50%, represent when monomer reaction weight to the total charging capacity of monomer 10% time first time add telogen, when monomer reaction weight to the total charging capacity of monomer 50% time for the second time add telogen.
3, in comparative example 1, molecular weight telogen and consumption (ml) diethyl malonate 50 be when monomer reaction weight to the total charging capacity of monomer 60% time disposable add.
Embodiment 5, for the polymeric kettle of 10L, prepare ternary fluororubber
The dipotassium hydrogen phosphate of 6.5kg deionized water and 65ml concentration 10wt% perfluoro ammonium caprylate solution, 10g is added in clean polymeric kettle, find time, deoxygenation, be qualified to oxygen level≤30ppm. then 60%(mass percent is used) R 1216, 20%(mass percent) tetrafluoroethylene and 40%(mass percent) vinylidene, it is mixed with mixture as monomer, polymeric kettle is boosted to 1.6Mpa, when the still temperature rise of still to be polymerized is to 100 DEG C, squeezing into concentration with volume pump is 10% potassium persulfate solution 20g initiation reaction, monomer reaction weight to the total charging capacity of initial monomer 20% time, add 5ml molecular weight telogen iso-pentane, and add the potassium persulfate solution that 2g concentration is 10wt%, simultaneously by adding monomer in reaction vessel continuously, gas phase composition in reaction vessel is made to keep constant. monomer reaction weight to the total charging capacity of initial monomer 50% time, add 45ml molecular weight telogen iso-pentane, and add the potassium persulfate solution that 6g concentration is 10wt%, until initial monomer complete reaction, stopped reaction. through condensing, wash, dry, open the type of being smelt, to obtain final product.
After testing, the molecular weight distribution of this viton is bimodal distribution, and weight-average molecular weight Mw is 1052301. Mobility-detected is 265mm, oil sealing glue smooth surface.
Claims (11)
1. the preparation method of a fluororubber for oil seal, it is characterised in that, comprise the steps:
(1) Xiang Shuizhong adds emulsifying agent and pH adjusting agent, and emulsifying agent accounts for the 0.01～0.2% of water weight, and pH adjusting agent accounts for the 0.01～0.5% of water weight, obtained solution A;
(2) adding monomer in the obtained solution A of step (1), water and the mass ratio of monomer in step (1) are 1:(0.01～1), stir even, obtained solution B;
Described monomer is selected from one of following a～g:
A, 45～65% vinylidenes, 35～55% the mixture of R 1216, or the mixture of 10～50% vinylidenes, the R 1216 of 25～65% and the tetrafluoroethylene of 5～35%, is mass percent;
The mixing of c, trifluorochloroethylene and vinylidene arbitrary proportion;
The mixing of d, vinylidene and perfluoroalkyl vinyl ether arbitrary proportion, or the mixing of vinylidene and perfluorinated alkoxy vinyl ether arbitrary proportion;
The mixing of e, ethene and R 1216 arbitrary proportion;
The mixing of f, tetrafluoroethylene and propylene arbitrary proportion;
The mixing of g, tetrafluoroethylene and perfluoroalkyl vinyl ether arbitrary proportion, or the mixing of tetrafluoroethylene and perfluorinated alkoxy vinyl ether arbitrary proportion;
(3) add, in the obtained solution B of step (2), the inorganic initiator solution initiated polymerization that concentration is 1～10wt%, polymerization pressure 1.0～4.0Mpa, temperature of reaction are 50～150 DEG C, and the add-on of inorganic initiator is the 0.005～1% of the weight of water in step (1);
(4) when 10～20% of the total charging capacity of monomer in monomer reaction weight to step (2), add molecular weight telogen, described molecular weight telogen add-on is 0.1～1wt% of the water weight in step (1), simultaneously by adding monomer in reaction vessel continuously, gas phase composition in reaction vessel is made to keep constant;
When 40～65% of the total charging capacity of monomer in monomer reaction weight to step (2), add molecular weight telogen again, described molecular weight telogen add-on is 0.05～1wt% of the water weight in step (1), and add inorganic initiator, the add-on of inorganic initiator is 0.005～1wt% of the weight of water in step (1), when 90～100% of the total charging capacity of monomer in monomer reaction weight to step (2), stopped reaction, obtained polymerized emulsion;
(5) undertaken the polymerized emulsion that step (4) is obtained condensing, wash, dry, plasticate through rubber mixing machine shaping, to obtain final product.
2. preparation method as claimed in claim 1, it is characterised in that, the pH adjusting agent in described step (1) is weak base salt.
3. preparation method as claimed in claim 2, it is characterised in that, the pH adjusting agent in described step (1) is dipotassium hydrogen phosphate or sodium tetraborate.
4. preparation method as claimed in claim 1, it is characterised in that, the emulsifying agent in described step (1) is selected from nonionic emulsifier or ionic emulsifying agent.
5. preparation method as claimed in claim 4, it is characterised in that, the emulsifying agent in described step (1) is selected from ionic emulsifying agent perfluorooctanoic acid salt.
6. preparation method as claimed in claim 5, it is characterised in that, emulsifying agent is selected from Sodium perfluorooctanoate or ammonium perfluorocaprylate.
7. preparation method as claimed in claim 1, it is characterized in that, the monomer a of described step (2) is: the mixture of 50～60% vinylidenes and 40～50% R 1216s, or the mixture of 25～50% vinylidenes, 30～50% R 1216s and 15～30% tetrafluoroethylene.
8. preparation method as claimed in claim 1, it is characterised in that, the inorganic initiator in described step (3) and step (4) is persulphate.
9. preparation method as claimed in claim 8, it is characterised in that, the inorganic initiator in described step (3) and step (4) is Potassium Persulphate or ammonium persulphate.
10. preparation method as claimed in claim 1, it is characterised in that, the molecular weight telogen in described step (4) is selected from one of iso-pentane, diethyl malonate, succinate, ethyl acetate or the combination of two kinds of any ratios.
11. preparation methods as claimed in claim 10, it is characterised in that, the molecular weight telogen in described step (4) is iso-pentane.
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| DE69022008T2 (en) * | 1989-12-20 | 1996-05-02 | Du Pont | Fluorine-containing elastomer composition. |
| JPH07118349A (en) * | 1993-10-15 | 1995-05-09 | E I Du Pont De Nemours & Co | Fluoroelastomer |
| EP1432744B2 (en) * | 2001-05-02 | 2014-10-01 | 3M Innovative Properties Company | Aqueous emulsion polymerization in the presence of ethers as chain transfer agents to produce fluoropolymers |
| WO2002088206A2 (en) * | 2001-05-02 | 2002-11-07 | 3M Innovative Properties Company | Emulsifier free aqueous emulsion polymerization process for making fluoropolymers |
| JP2007056215A (en) * | 2005-08-26 | 2007-03-08 | Daikin Ind Ltd | Peroxide-crosslinkable fluororubber |
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