CN101186667B - Method for preparing high-strength ternary fluororubber - Google Patents
Method for preparing high-strength ternary fluororubber Download PDFInfo
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Abstract
The invention provides a preparation method of high-strength ternary fluorine elastomer, which uses emulsion polymerization, uses 50-70mol% 1, 1-difluoroethylene, 10-30mol% fluoropropene and 10-20mol% perfluoroethylene as coplymeric units, uses 0.001-3 weight account of emulsifier in each 100 weight account of water medium, uses 0.1-7wt% persulfate water solution as initiator, to obtain high-strength elastomer via free radical emulsion polymerization, while the strength of the product can reach at least 20MPa and extensibility can reach at least 200%, with better sulfuration property, better liquid resistance, ability for producing die product,and better abrasion resistance.
Description
Technical field
The present invention relates to a kind of preparation method of high-strength ternary fluororubber, specifically, relate to preparation and comprise 1 of specific molar ratio, the copolymerization units of 1-difluoroethylene, tetrafluoroethylene, perfluoro propylene, its intensity reaches more than the 20MPa, elongation has the good energy of anti-the fluidity concurrently more than 200%, has the method for the fluoroelastomer of better curability simultaneously.
Background technology
Viton is with its good heat-resisting, anti-liquid and oil-proofness and good physical and mechanical properties, electrical insulating property and radiation resistance.Can be 250 ℃ of following long term operations, 300 ℃ of following short-term jobs.
Viton can be widely used in aerospace, automobile and Der Gelaendewagen, oil production and petrochemical complex, industrial pollution control and aspects such as hydraulic pressure and pneumatics.Particularly in recent years along with the viton Application Expansion, the requirement of viton is increased day by day, existing viton grade more and more can not satisfy market, and this has also stimulated the application market of extraordinary viton.Under situation about being becoming tight energy day, the appearance of the novel environment friendly energy, fuel requires viton to have the excellent solvent-resistance energy.But in some field of national defense industry, automotive industry, the intensity of conventional ternary fluororubber can only reach 1.6MPa, can't bear the requirement of its severe rugged environment.Therefore it is imperative to satisfy its needs greater than the high-strength ternary fluororubber of 2.0MPa to develop a kind of intensity.
Technology with letex polymerization production fluoroelastomer has been that the present technique field is known both at home and abroad, such as U.S. Pat 4214060.Usually, the fluoroelastomer product comprises the vinylidene fluoride of following copolymerization units: 65mol%; The tetrafluoroethylene of 20mol%; The perfluoro propylene of 15mol%.Generally about 68%, its intensity is generally about 1.6MPa for the fluorine content of this type of fluoroelastomer.And the intensity of general ternary fluororubber is after reaching 20Mpa, and curability obviously descends, and processing characteristics is relatively poor.
Therefore,, need to adjust monomer structure and form, when improving intensity, ensure its stretching and curability for obtaining high-strength ternary fluororubber, and good processing properties.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of high-strength ternary fluororubber, this method adds persulfate initiator by the adjustment monomer structure, comes effective Quality Initiative end structure, obtains high strength, better the fluoroelastomer of curability and anti-fluidity energy.
In order to realize the object of the invention, the preparation method of a kind of high-strength ternary fluororubber of the present invention, adopt emulsion polymerisation process, copolymerization units is: 1 of 50~70mol%, the perfluoro propylene of 1-difluoroethylene, 10~30mol% and the tetrafluoroethylene of 10~20mol%, contain 0.001~3 weight part emulsifying agent in per 100 weight parts water media, the amount of initiator is to add in per 100 weight parts water media to contain 0.001~5 weight part, and described initiator is 0.1~7 weight % persulphate aqueous solution.
Wherein, the copolymerization units that contains 30~60 weight parts in per 100 weight parts water media.
Described emulsifying agent is a fluorine carbon solubilising emulsifying agent, i.e. perfluoro-carbon (PFC), and consumption is to contain 0.001~3 weight part emulsifying agent in the 100 weight parts water media.
Described persulphate is Potassium Persulphate or ammonium persulfate.
In order to control the molecular weight of fluoro-resin, also can in polyreaction, add described chain-transfer agent and be selected from two or more mixing in tetracol phenixin, formic acid, acetate, diethyl malonate, succinate or the ethyl acetate etc.Its consumption is to add in per 100 weight parts water media to contain 0.01~0.1 weight part.
Adopting pH regulator agent control pH in the polymerization process is 3~5, and described pH regulator agent is the agent of borax pH regulator.
Polymerization pressure of the present invention is 0.7~5.0MPa, preferred 1.0~3.5MPa.
Polymeric reaction temperature is 20~100 ℃, is preferably 60~100 ℃.
The preparation method of high-strength ternary fluororubber of the present invention, it comprises the steps:
1) water medium of adding persulphate emulsifying agent in reactor, the concentration of described emulsifying agent in water medium is to contain 0.001~3 weight part in per 100 weight parts water media, and the add-on of water medium leaves the vapour space that is enough to accept gaseous monomer and is advisable making in the reactor;
2) vapour space at reactor adds 1 of 50~70mo1%, the mix monomer of the perfluoro propylene of 1-difluoroethylene, 10~30mol% and the tetrafluoroethylene of 10~20mol%, add in per 100 weight parts water media and contain 30~60 weight parts, constantly mix described water medium and monomer mixture, to form emulsion;
3) by in emulsion, adding persulfate initiator, chain-transfer agent, PH conditioning agent, at 20~100 ℃, 0.7~5Mpa, pH is 3~5 times polyreactions, the amount of initiator is to add the initiator that contains 0.001~5 weight part in per 100 weight parts water media, and this initiator adds in the reactor in the mode of 0.1~7 weight % aqueous solution;
4) in polymerization process, keep constant voltage in the reactor, reach till 40~800,000 up to the number-average molecular weight of fluoroelastomer product;
5) emulsion after the polymerization is through cohesion, washing and dry.
High-strength ternary fluororubber of the present invention comprises the vinylidene fluoride of following copolymerization units: 50~70mol%, the perfluoro propylene of 10~30mol% and the tetrafluoroethylene of 10~20mol%.If the content of vinylidene fluoride is less than 30mol%, then rate of polymerization is very slow, the curability variation, and elongation reduces, and can not obtain good resistance to low temperature.Can cause the fluorine content of elastomeric fluoroelastomer on the low side if vinylidene fluoride weight is higher than 70mol%, solvent resistance reduces.
Perfluoro propylene content of the present invention is 10~30mol%, is preferably 12~28mol%; Ensure that elastomerics has good snappiness, the content of perfluoro propylene can suitably be increased to 25mol%, because the reactivity ratio of perfluoro propylene is lower, and speed of response is very slow, increases production cost when still surpassing 40mol%.
The copolymerization units amount of tetrafluoroethylene of the present invention can reach 10~20mol%.The existence of the copolymerization units of TFE is feasible, and this can increase fluorine content, can excessively not damage low-temperature flexibility simultaneously.High strength fluorine measurer has good resistance to liquid.If but the tetrafluoroethylene too high levels causes the elastomerics rigidity to strengthen, processibility reduces, and the amount of TFE is higher than 20mol% can cause some polymer crystallizations, to influence its low temperature compression set.Therefore such viton tetrafluoroethylene content is preferably 15~20mol%.
In addition, owing to during the preparation fluoroelastomer, also selected compound chain-transfer agent for use.The present invention has carried out the test that multiple chain-transfer agent is regulated the molecular weight size and distributed, and after instruments such as employing gel chromatography, nucleus magnetic resonance are analyzed and researched to sample, has determined the optimum range of molecular weight distribution.By adopting compound chain-transfer agent, can control molecular weight distribution and end structure exactly, make molecular weight rubber be controlled at 40~800,000, be good more than 500,000.
In the emulsion polymerisation process of the present invention, (1) introduces the vapour space above the water medium in the reactor with the gaseous monomer mixture (initial monomers is reinforced) of required composition.Water medium comprises fluorine carbon solubilising emulsifying agent, and its content is 0.001~3 weight part/100 weight parts water media.Normally monomer mixture is scattered in the water medium then, when stirred reaction mixture, also can adds auxiliary agents such as persulfate initiator, chain-transfer agent, PH conditioning agent with mechanical stirring.In initial gas is reinforced, every kind of monomeric relative quantity is determined that by reaction kinetics its set amount will cause comonomer unit that required (promptly selected) mol ratio (i.e. the very slow monomer of reaction must have higher molar weight than required gaseous monomer in the fluoroelastomer that is produced is formed) is arranged; (2) temperature of reaction remains on 20~100 ℃, is preferably 60~100 ℃; (3) this polyreaction adds the persulphate initiation, and the amount of persulphate is the persulphate/100 weight parts water media of 0.001~5 weight part.This persulphate adds with the form of the aqueous solution.According to the character of the fluoroelastomer that will produce and total polymerization time, in polymerization process, also may need add persulfate initiator in reactor, with the content of keeping persulphate in above-mentioned scope; (4) in whole polymerization process, add the gaseous state mix monomer (stage increment reinforced) of required amount of filling with controlled rate, to remain on the constant reaction pressure under the controllable temperature.Because rate of polymerization is constant increase in reaction process, thus the flow of gaseous state mix monomer also must in reaction process, increase, to keep the constant pressure in the reactor.The relative quantity (be mol ratio) of gaseous state mix monomer in the stage incremental feed is close with the selected mol ratio of copolymerization units in the fluoroelastomer that will prepare.The weight of the polymkeric substance that forms is similar to the weight of stage incremental feed.
The present invention comes controlled polymerization speed by the controlled polymerization temperature and by the amount that adds initiator.Polymerization time under the normal circumstances is 2~20 hours.
Polymerization temperature of the present invention is preferably 60~100 ℃.If temperature is lower than 60 ℃, the too slow plant-scale effecting reaction of incompatibility of copolymerization speed, if but temperature is higher than 100 ℃, and then formed fluoroelastomer copolymer emulsion is with retrogradation, be easy in polymerization reactor, cause obstruction, make the stability that is difficult to keep emulsion during the polyreaction.
Polymerization pressure of the present invention is 0.7~5.0MPa, preferred 1.0~3.5MPa.Required polymerization pressure is to reach by the amount that is adjusted in the gaseous monomer in initial the feeding in raw material when beginning, and after the reaction beginning, pressure is fed in raw material by the stage increment of controlling gaseous monomer and regulates.Polymerization pressure is set in the above-mentioned scope, because if pressure is lower than 0.7MPa, then the monomer concentration of polymerization reaction system is too low, can not reach satisfied speed of reaction.Molecular weight can not effectively increase in addition.If pressure is higher than 3.5MPa, the amount of monomer that then liquefies in reactor increases, and has not only increased the amount of monomer that is consumed thus, and has made production efficiency poor.In addition, if pressure is higher than 3.5MPa,, increased production cost to having relatively high expectations of equipment and system, pipeline.
It is easier that the flow that the present invention adds mix monomer by control keeps the constant pressure of reactor during whole polyreaction.At the commitment of polyreaction, when rate of polymerization was low, polymerization reactor pressure descended very slow, and the stage charging increment of gaseous state mix monomer is very little, to keep the constant pressure of reactor.When rate of polymerization increased, polymerization reactor pressure descended very fast, and the flow that can increase the gaseous state mix monomer that enters reactor is to keep the constant pressure of reactor.Between reactor and mix monomer source, need under meter measuring device and pressurestat,, and keep the constant voltage of reactor thus with accurate dominant discharge.
The feeding quantity of adding mix monomer that the amount of the fluoroelastomer that forms equals to add approx, its scope is 50~150 weight part multipolymers/100 weight fraction water mediums, is preferably 50~100 weight part multipolymers/100 weight parts water media.Because if it is less than 50 weight parts, then its productivity is too low, and is nonconforming, and if surpass 150 weight parts, then solid content can become too high, emulsion is very sticking, the stirring that can not be satisfied with.And emulsion is easy to cause heat transfer efficiency poor attached to the polymeric kettle inwall.The initial reinforced monomer that monomer is formed and the stage increment is reinforced is made up of gas chromatograph for determination.
Cohesion of the present invention, washing and dry this area common process that adopts carry out.
The present invention prepares the method for high-strength ternary fluororubber, by adjusting monomer structure, add persulfate initiator, compound chain-transfer agent, the optimization of the reaction conditions of polyreaction (as increasing reaction pressure etc.), effectively control molecular weight and molecular weight distribution thereof (viton molecular weight 〉=400,000) and end structure, the intensity of the fluoroelastomer of acquisition reaches more than the 20MPa, and elongation is also more than 200%, have the good energy of anti-the fluidity concurrently, have curability preferably simultaneously.
The high-strength ternary fluororubber that the present invention produces passes through through molding and sulfuration during making product such as sealing member, metal wire coating, flexible pipe etc.General vulcanization process uses many alcohol, polyamine or adds the vulcanizing agent organo-peroxide.Preferred cross-linking agents is a peroxide vulcanizing system.
The high-strength ternary fluororubber of the present invention's preparation is applicable to many industry, during particularly automotive industry is used, comprises product, goods such as sealing member, wire coating, laminate, automobile oil seal.
Embodiment
Following examples are used to illustrate the present invention, but are not used for limiting the scope of the invention.
Embodiment 1
In the reactor of 50L, carry out letex polymerization of the present invention, with the preparation fluoroelastomer.Add the deionized water that 30L contains 10g fluorine carbon solubilising emulsifying agent (composition is a perfluoro-carbon) in the reactor.Reactor should carry out evacuation processes, when treating its oxygen level≤30ppm, adds borax 30g, diethyl malonate 10ml, CCL
45ml.Content in the reactor is heated to 70 ℃, and with containing 44.02% vinylidene, 15.78% tetrafluoroethylene (TFE), the monomer mixture of 40.2% perfluoro propylene (HFP) (mol ratio) rises to 2.76MPa with its pressure.Beginning is stirred with 88r/min speed, is set in the automatic operational stage under the 2.76MPa pressure at the reactor pressure controller.
Remain on 70 ℃ of following times at temperature of reactor, make pressurestat pressure increase to 3.0MPa with adding mix monomer, this mixture contains the TFE of the VDF of 58.4 moles of %, 16.2 moles of % and the HFP of 25.4 moles of %, in case when pressurestat reaches 3.0MPa, be enabled in automatic working pressure controller between the 3.0-2.95MPa.When 3.0MPa, the monomer feed valve cuts out, and the monomer feed valve is opened when 2.95MPa.
Add Potassium Persulphate 3g this moment and begin reaction.After polyreaction is carried out, make by replenishing mix monomer that absolute pressure maintains between the 3.0-2.95MPa in the reactor, additional time is about 4h, emulsion solid content reaches about 30% (mass percent), finish polyreaction, reclaim unreacted monomer, milk ejection liquid is to the cohesion bucket, stir speed machinery cohesion under 45HZ, 120 ℃ of left and right sides vacuum-dryings.The polymkeric substance that produces surpasses 15Kg, and its characteristic is listed in table 1.
The The performance test results of table 1 fluoroelastomer
Annotate: the curability checking adopts the evaluation prescription of 3# vulcanization system to measure.
By similar above-mentioned polymerization process, post-treating method keeps auxiliary agent content unanimity, adjusts its reaction pressure respectively and sees Table 2 (being respectively embodiment 2-embodiment 4); Detected result
See Table 4.
The reaction pressure of table 2 embodiment 1-4
Project | Reaction pressure, MPa |
Embodiment 1 | 3.0 |
Embodiment 2 | 2.6 |
Embodiment 3 | 2.2 |
Embodiment 4 | 1.8 |
Embodiment 5
In the reactor of 50L, carry out letex polymerization of the present invention, with the preparation fluoroelastomer.Add the deionized water that 30L contains 10g fluorine carbon solubilising emulsifying agent in the reactor.Reactor should carry out evacuation processes, when treating its oxygen level≤30ppm, adds borax 30g.Content in the reactor is heated to 70 ℃, with the vinylidene (VF that contains 44.02%
2), 15.78% tetrafluoroethylene (TFE), the monomer mixture of 40.2% perfluoro propylene (HFP) (mol ratio) rises to 2.36MPa with its pressure.Beginning is stirred with 88r/min speed, is set in the automatic operational stage under the 2.36MPa pressure at the reactor pressure controller.
Remain on 70 ℃ of following times at temperature of reactor, make pressurestat pressure increase to 2.6MPa with adding mix monomer, this mixture contains the TFE of the VDF of 58.4 moles of %, 16.2 moles of % and the HFP of 25.4 moles of %, in case when pressurestat reaches 3.0MPa, be enabled in automatic working pressure controller between the 2.6-2.55Mpa.When 2.6MPa, the monomer feed valve cuts out, and the monomer feed valve is opened when 2.55MPa.
Add Potassium Persulphate 3g this moment and begin reaction.After polyreaction is carried out, make by replenishing mix monomer that absolute pressure maintains between the 2.6-2.55Mpa in the reactor, proceeding to monomer conversion in polyreaction is 25%, adds chain-transfer agent diethyl malonate 50ml, acetate 15ml, and additional time is about 4h, emulsion solid content reaches about 30% (mass percent), finish polyreaction, reclaim unreacted monomer, milk ejection liquid is to the cohesion bucket, stir speed machinery cohesion under 45HZ, 120 ℃ of left and right sides vacuum-dryings.The polymkeric substance that produces surpasses 15Kg.
On the basis of embodiment 5, adopt similar above-mentioned polymerization process, post-treating method, adjusting chain-transfer agent consumption and joining day see Table 3 (embodiment 5-7).Obtain the viton of different physicochemical characteristics, its detected result sees Table 4.
The different joining days and the add-on of table 3 chain-transfer agent
Project | Joining day | Add-on, ml |
Embodiment 1 | Reaction conversion ratio is 0% o'clock | 15 |
Embodiment 5 | Reaction conversion ratio is 25% o'clock | 50 |
Project | Joining day | Add-on, ml |
Embodiment 6 | Reaction conversion ratio is 50% o'clock | 100 |
Embodiment 7 | Reaction conversion ratio is 75% o'clock | 200 |
The performance test results of the fluoroelastomer of each embodiment of table 4
Annotate: 1, the mooney viscosity test condition is: ML
1+10 121℃;
2, the evaluation prescription of curability checking 3# vulcanization system is measured.
Conclusion: high-strength ternary fluororubber of the present invention has high tensile strength, better curability and the energy of anti-the fluidity.
Though above the present invention is described in detail with a general description of the specific embodiments, on basis of the present invention, can make some modifications or improvements it, this will be apparent to those skilled in the art.Therefore, these modifications or improvements all belong to the scope of protection of present invention without departing from theon the basis of the spirit of the present invention.
Claims (10)
1. the preparation method of a high-strength ternary fluororubber, adopt emulsion polymerisation process, it is characterized in that, copolymerization units is: 1 of 50~70mol%, the perfluoro propylene of 1-difluoroethylene, 10~30mol% and the tetrafluoroethylene of 10~20mol%, contain 0.001~3 weight part emulsifying agent in per 100 weight parts water media, the amount of initiator is to add in per 100 weight parts water media to contain 0.001~5 weight part, and described initiator is 0.1~7 weight % persulphate aqueous solution; During polymerization, also add described compound chain-transfer agent, described compound chain-transfer agent is selected from two or more the mixing in tetracol phenixin, formic acid, acetate, diethyl malonate, succinate or the ethyl acetate etc., the consumption of described compound chain-transfer agent is to add in per 100 weight parts water media to contain 0.01~0.1 weight part, and polymerization pressure is 0.7~5.0MPa.
2. the preparation method of high-strength ternary fluororubber according to claim 1 is characterized in that, contains the multipolymer of 30~60 weight parts in per 100 weight parts water media.
3. the preparation method of high-strength ternary fluororubber according to claim 1 and 2 is characterized in that, described emulsifying agent is a fluorine carbon solubilising emulsifying agent.
4. the preparation method of high-strength ternary fluororubber according to claim 3 is characterized in that, polymerization pressure is 1.0~3.5MPa.
5. the preparation method of high-strength ternary fluororubber according to claim 1 and 2 is characterized in that, polymerization pressure is 1.0~3.5MPa.
6. according to the preparation method of claim 1 or 2 described high-strength ternary fluororubbers, it is characterized in that polymeric reaction temperature is 20~100 ℃.
7. the preparation method of high-strength ternary fluororubber according to claim 6 is characterized in that, polymeric reaction temperature is 60~100 ℃.
8. the preparation method of high-strength ternary fluororubber according to claim 1 and 2 is characterized in that, described perfluoro propylene content is 12~28mol%.
9. the preparation method of high-strength ternary fluororubber according to claim 1 and 2 is characterized in that, described tetrafluoroethylene content is 15~20mol%.
10. the preparation method of high-strength ternary fluororubber according to claim 1 is characterized in that, it comprises the steps:
1) water medium of adding fluorine carbon solubilising emulsifying agent in reactor, the concentration of described emulsifying agent in water medium is to contain 0.001~3 weight part in per 100 weight parts water media, and the add-on of water medium leaves the vapour space that is enough to accept gaseous monomer and is advisable making in the reactor;
2) add the mix monomer of the tetrafluoroethylene of the perfluoro propylene of vinylidene fluoride, 10~30mol% of 50~70mol% and 10~20mol% in the vapour space of reactor, constantly mix described water medium and monomer mixture, to form emulsion;
3) by in emulsion, adding persulfate initiator, chain-transfer agent, pH regulator agent, at 20~100 ℃, 0.7~5Mpa, pH is 3~5 times polyreactions, the amount of initiator is to add the initiator that contains 0.001~5 weight part in per 100 weight parts water media, and this initiator adds in the reactor in the mode of 0.1~7 weight % persulphate aqueous solution;
4) in polymerization process, keep constant voltage in the reactor, reach till 40~800,000 up to the number-average molecular weight of fluoroelastomer product;
5) emulsion after the polymerization is through cohesion, washing and dry.
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CN111363076A (en) * | 2020-04-24 | 2020-07-03 | 四川道弘科技有限公司 | Ternary peroxide fluororubber and preparation method thereof, and intelligent wearing material and preparation method thereof |
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CN102464730B (en) * | 2010-11-02 | 2013-12-25 | 中昊晨光化工研究院 | Preparation method of fluorine-containing microemulsion and application thereof |
CN102329402B (en) * | 2011-06-30 | 2013-07-10 | 浙江孚诺林化工新材料有限公司 | Preparation method of low-temperature-resistant binary fluorine rubber |
CN102516438B (en) * | 2011-11-30 | 2013-09-25 | 中昊晨光化工研究院 | Method for preparing fluorine-containing rubber for automobile rubber pipe |
CN103694396B (en) * | 2013-12-27 | 2016-03-02 | 中昊晨光化工研究院有限公司 | A kind of polymer fluorine-containing rubber and its preparation method and application |
CN103739767B (en) * | 2013-12-30 | 2016-03-02 | 山东华夏神舟新材料有限公司 | A kind of preparation method of fluoroelastomer |
CN104497189A (en) * | 2014-10-28 | 2015-04-08 | 浙江巨圣氟化学有限公司 | Preparation method of thermally-stable raw fluorubber |
CN106543370A (en) * | 2015-09-16 | 2017-03-29 | 中国石油天然气股份有限公司 | The preparation method of fluoropolymer modifier microgranule |
CN110038503B (en) * | 2018-01-17 | 2020-07-14 | 中昊晨光化工研究院有限公司 | Synthesis process system and method of fluororubber |
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Address after: 643201 Zigong County, Sichuan Province, Chenguang Road, No. 135, Fushun Patentee after: Zhonghao Chenguang Chemical Institute Co., Ltd. Address before: 643201, Chenguang Road, Fu town, Fushun County, Zigong, Sichuan, 135 Patentee before: Zhonghao Chenguang Chemical Research Inst. |