CN115703861B - Trifluoro chloroethylene modified peroxide vulcanized fluororubber and preparation method thereof - Google Patents
Trifluoro chloroethylene modified peroxide vulcanized fluororubber and preparation method thereof Download PDFInfo
- Publication number
- CN115703861B CN115703861B CN202110897653.4A CN202110897653A CN115703861B CN 115703861 B CN115703861 B CN 115703861B CN 202110897653 A CN202110897653 A CN 202110897653A CN 115703861 B CN115703861 B CN 115703861B
- Authority
- CN
- China
- Prior art keywords
- chlorotrifluoroethylene
- fluororubber
- monomer
- modified
- reactor
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229920001973 fluoroelastomer Polymers 0.000 title claims abstract description 41
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 150000002978 peroxides Chemical class 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000000178 monomer Substances 0.000 claims abstract description 45
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 34
- 238000004073 vulcanization Methods 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000003999 initiator Substances 0.000 claims abstract description 13
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 8
- 239000012986 chain transfer agent Substances 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 230000001502 supplementing effect Effects 0.000 claims abstract description 7
- 239000012429 reaction media Substances 0.000 claims abstract description 6
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims description 14
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 claims description 14
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 14
- 239000000839 emulsion Substances 0.000 claims description 8
- 239000012071 phase Substances 0.000 claims description 8
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 6
- 239000008346 aqueous phase Substances 0.000 claims description 5
- AYCANDRGVPTASA-UHFFFAOYSA-N 1-bromo-1,2,2-trifluoroethene Chemical group FC(F)=C(F)Br AYCANDRGVPTASA-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- -1 trifluoroethylene, trifluoroiodoethylene Chemical group 0.000 claims description 4
- JILAKKYYZPDQBE-UHFFFAOYSA-N 1,1,2,2,3,3,4,4-octafluoro-1,4-diiodobutane Chemical compound FC(F)(I)C(F)(F)C(F)(F)C(F)(F)I JILAKKYYZPDQBE-UHFFFAOYSA-N 0.000 claims description 2
- ROUYUBHVBIKMQO-UHFFFAOYSA-N 1,4-diiodobutane Chemical compound ICCCCI ROUYUBHVBIKMQO-UHFFFAOYSA-N 0.000 claims description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 2
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 claims description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000003431 cross linking reagent Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- NZZFYRREKKOMAT-OUBTZVSYSA-N diiodomethane Chemical group I[13CH2]I NZZFYRREKKOMAT-OUBTZVSYSA-N 0.000 claims 1
- SNGREZUHAYWORS-UHFFFAOYSA-N perfluorooctanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F SNGREZUHAYWORS-UHFFFAOYSA-N 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 230000001070 adhesive effect Effects 0.000 abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000007789 gas Substances 0.000 description 9
- 238000007906 compression Methods 0.000 description 8
- 230000006835 compression Effects 0.000 description 7
- 229910052731 fluorine Inorganic materials 0.000 description 6
- 239000011737 fluorine Substances 0.000 description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 239000004636 vulcanized rubber Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- NZZFYRREKKOMAT-UHFFFAOYSA-N diiodomethane Chemical compound ICI NZZFYRREKKOMAT-UHFFFAOYSA-N 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 239000004677 Nylon Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- YOALFLHFSFEMLP-UHFFFAOYSA-N azane;2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctanoic acid Chemical compound [NH4+].[O-]C(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YOALFLHFSFEMLP-UHFFFAOYSA-N 0.000 description 2
- 230000015271 coagulation Effects 0.000 description 2
- 238000005345 coagulation Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 241001441571 Hiodontidae Species 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 239000012431 aqueous reaction media Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Abstract
The invention provides a trifluoro chloroethylene modified peroxide vulcanized fluororubber and a preparation method thereof. The method comprises the following steps: adding initial mixed monomer into a reactor which is pre-added with a water phase reaction medium, an emulsifying agent and a vulcanization point monomer to enable the pressure of the reactor to reach 1.6-3.5 MPa, and adding an initiator and a chain transfer agent to start polymerization reaction; and adding additional mixed monomer containing the chlorotrifluoroethylene in the polymerization process in a supplementing way, controlling the pressure in the reaction kettle to be 1.6-3.5 MPa, and controlling the mole fraction of the chlorotrifluoroethylene in a gas phase part in the reactor to be 5-15% after the feeding amount of the polymerized monomer reaches 30% of the total feeding amount. The high-fluorine-content peroxide vulcanized fluororubber obtained by the invention has good processability, and the modified monomer chlorotrifluoroethylene is uniformly distributed in the fluororubber molecular chain segment, so that the adhesive property of the high-fluorine-content peroxide vulcanized fluororubber is improved.
Description
Technical Field
The invention relates to the field of fluororubber synthesis, in particular to trifluoro chloroethylene modified peroxide vulcanized fluororubber and a preparation method thereof.
Background
The fluorine mass fraction of the fluoropolymer obtained by copolymerizing vinylidene fluoride (VDF), hexafluoropropylene (HFP), tetrafluoroethylene (TFE) and a vulcanization point monomer (CSM) in a certain proportion is 64-71%, and the rubber has excellent performances of high temperature resistance, corrosion resistance and the like peculiar to the fluororubber, and also has outstanding performances of hot tearing resistance, superheated steam resistance, organic medium resistance and the like. Peroxide cured fluororubbers were originally developed and commercialized by dupont in the united states in the early 70 s of the last century, and then japanese gold and italy suwei developed a series of brands of products, currently in a production facility on a kiloton scale.
Disclosure of Invention
The invention aims to provide a trifluoro chloroethylene modified peroxide vulcanized fluororubber and a preparation method thereof, which effectively solve the problem of poor adhesiveness of the peroxide vulcanized fluororubber with high fluorine content and improve the application field of materials.
Specifically, the invention provides the following technical scheme:
a preparation method of trifluorochloroethylene modified peroxide vulcanized fluororubber comprises the following steps:
(1) Adding initial mixed monomer containing vinylidene fluoride, tetrafluoroethylene and hexafluoropropylene into a reactor which is pre-added with aqueous phase reaction medium, emulsifying agent and vulcanization point monomer to enable the pressure of the reactor to reach 1.6-3.5 MPa, adding initiator and chain transfer agent, and starting polymerization reaction;
(2) Adding additional mixed monomers containing chlorotrifluoroethylene, vinylidene fluoride, tetrafluoroethylene and hexafluoropropylene in the polymerization process, controlling the pressure in the reaction kettle to be 1.6-3.5 MPa, and controlling the mole fraction of the chlorotrifluoroethylene in a gas phase part in the reactor to be 5-15% after the feeding amount of the polymerized monomers reaches 30% of the total feeding amount;
(3) Ending the reaction when the mass percentage of solids in the emulsion obtained by the polymerization reaction reaches 25-35%, and condensing, washing and drying the obtained polymerization emulsion;
(4) Vulcanizing the fluororubber obtained in the step (3) to obtain vulcanized fluororubber, wherein a cross-linking agent used for vulcanization is a peroxide vulcanizing agent.
The peroxide vulcanized fluororubber with high fluorine content obtained by the method has good processability, and the modified monomer trifluorochloroethylene is uniformly distributed in the fluororubber molecular chain segment, so that the adhesive property of the high-fluorine peroxide is improved.
It is further preferable that in the step (2), after the amount of the fed polymerized monomer reaches 30% of the total amount of the fed polymerized monomer, the mole fraction of chlorotrifluoroethylene in the gas phase part in the reactor is controlled to be 10 to 15%.
In order to further improve the comprehensive performance of the modified peroxide-cured fluororubber, the invention further preferably comprises the following steps of: (15-30): (40-55).
In order to further improve the comprehensive performance of the modified peroxide vulcanized fluororubber, the invention further preferably comprises the following additional mixed monomers of chlorotrifluoroethylene, vinylidene fluoride, tetrafluoroethylene and hexafluoropropylene in a molar ratio of (5-20): (35-54): (18-25): (18-35).
The invention can heat to the reaction temperature before introducing the initial mixed monomer, or can heat and introduce the initial mixed monomer at the same time. In order to ensure sufficient reaction of the above mixed monomers, the polymerization reaction temperature in the present invention is preferably 50 to 100 ℃, more preferably 70 to 100 ℃.
The emulsifier is preferably perfluoro octoate ammonium salt, sodium salt or potassium salt; the addition amount is 0.01-5 parts by weight of emulsifier per 100 parts by weight of the aqueous phase reaction medium.
The vulcanization point monomer is preferably one or more of trifluorobromoethylene, trifluoroiodoethylene, perfluoro-iodo-alkyl vinyl ether, perfluoro-bromo-alkyl vinyl ether and 3, 4-tetrafluoro-4-bromobut-1-ene, and is further preferably trifluorobromoethylene or 3, 4-tetrafluoro-4-bromobut-1-ene; the addition amount is 0.5-3 wt% of the total feeding amount of the polymerized monomers.
The initiator is preferably ammonium persulfate or potassium persulfate; it is further preferred that in step (1) 0.01 to 5 parts by weight of initiator is added per 100 parts by weight of the aqueous reaction medium.
In order to shorten the polymerization time, the invention preferably continuously supplements an initiator solution in the polymerization reaction process, wherein the initiator solution is an aqueous solution with the mass fraction of 5% of the initiator; more preferably, the rate of adding the initiator solution is 10 to 100g/10min, still more preferably 30 to 60g/10min.
The chain transfer agent of the present invention is preferably an α, ω -diiodoalkane or an α, ω -diiodoperfluoroalkane, further preferably diiodomethane, 1, 4-diiodobutane or 1, 4-diiodoperfluorobutane; the addition amount of the catalyst is 0.01-5 wt% of the total addition amount of the polymerization monomer.
The invention also protects the trifluoro chloroethylene modified peroxide vulcanized fluororubber prepared by the preparation method.
The method of the invention has the following beneficial effects:
according to the method for preparing the peroxide vulcanized fluororubber, provided by the invention, a certain amount of chlorotrifluoroethylene monomer is added in the polymerization process, and the gas phase composition of the polymerization kettle is continuously detected, so that the mole fraction of chlorotrifluoroethylene in the kettle in the polymerization process is controlled to be 5-15%, the obtained high-fluorine-content peroxide vulcanized fluororubber has good processability, and the modified monomer chlorotrifluoroethylene is uniformly distributed in a fluororubber molecular chain segment, so that the adhesive property of the high-fluorine-content peroxide vulcanized fluororubber is improved.
Detailed Description
The present invention will be described in detail below with reference to specific examples for the purpose of understanding. It is to be particularly pointed out that the specific examples are for illustrative purposes only and that various modifications and variations can be made by a person skilled in the art in light of the description herein, without departing from the spirit of the invention, and are intended to be within the scope of the invention.
In the following examples, the equipment and the like used were conventional products available for purchase by a regular channel manufacturer, without specifying the manufacturer. The methods are conventional methods unless otherwise specified, and the starting materials are commercially available from the public sources unless otherwise specified.
The performance test method comprises the following steps:
raw rubber mooney: ML (1+10), measured at 121℃using an L (large) rotor according to ASTM D1646, wherein the preheating time is one minute and the rotor operating time is 10 minutes, unless otherwise indicated.
Tensile strength and elongation test method: the standard compound was press-vulcanized 1 time and oven-vulcanized 2 times under standard vulcanization conditions to produce a sheet having a thickness of 2mm, which was measured in accordance with JIS-K6251.
Permanent compression set test method: a circular ring (P-24) was produced by press-vulcanizing the following standard compound 1 times and oven-vulcanizing 2 times under standard vulcanizing conditions 1 or 2, and the compression set after press-vulcanizing 1 time and the compression set after oven-vulcanizing 2 times were measured in accordance with JIS-K6301 (the sample was held at 200℃for 72 hours under 25% press-compression, and then left in a constant temperature chamber at 25℃for 30 minutes, to make the measurement).
The adhesive force test method comprises the following steps: GB9286-98 standard.
Example 1
The embodiment relates to a preparation method of trifluorochloroethylene modified peroxide vulcanized fluororubber, which comprises the following steps:
(1) Into a 50L reactor was charged 30L deionized water. The reactor should be evacuated, when the oxygen content is less than or equal to 30ppm, 35g of ammonium perfluorooctanoate is added, 60g of trifluorobromoethylene is added, the temperature of the reactor is heated to 95 ℃, and the stirring speed is 220 r/min;
(2) Introducing vinylidene fluoride, tetrafluoroethylene and hexafluoropropylene according to a molar ratio of 30:28:42, raising the pressure of the reactor to 2.0MPa, and then adding 15g of potassium persulfate and 30g of diiodomethane to start polymerization reaction;
(3) Continuously supplementing an aqueous solution containing 5% of potassium persulfate after the polymerization reaction is carried out, wherein the supplementing rate is 50g/10min; simultaneously, continuously adding the components of chlorotrifluoroethylene, vinylidene fluoride, tetrafluoroethylene and hexafluoropropylene according to the molar ratio of 18:35:20:27, when the feeding amount of the polymerized monomer reaches 20%, 30%, 40%, 50%, 60%, 70%, 80% and 90% of the total feeding amount, taking gas sample composition analysis in the reactor, and controlling the mole fraction of the chlorotrifluoroethylene in the gas phase part of the reactor after the total feeding amount of the polymerized monomer reaches 30% to be 12+/-0.5% by adjusting the feeding rate of the additional mixed monomer (namely controlling the polymerization pressure to be 1.7-2.3MPa, if the chlorotrifluoroethylene content in the polymerization reactor is lower, increasing the feeding rate of the additional mixed monomer, increasing the pressure, and if the chlorotrifluoroethylene content in the polymerization reactor is higher, reducing the feeding rate of the additional mixed monomer, and reducing the pressure, thereby realizing the control of the mole fraction of the chlorotrifluoroethylene in the gas phase part of the polymerization reactor;
(4) When the solid content of the emulsion reaches about 30 percent (mass percent), ending the polymerization reaction, wherein the reaction time in the polymerization process is about 3 hours, recycling unreacted monomers, and placing the emulsion into a coagulation barrel; adding a certain amount of MgCl 2 Condensing; vacuum drying at about 100deg.C; the resulting peroxide cured fluororubber was about 9Kg.
The raw rubber product had a nylon viscosity of 65 (ML1+10min 121 ℃ C.), and a fluorine content: 70.3% of modified peroxide vulcanized fluororubber prepared by the method is vulcanized by the following vulcanization formula:
the first stage of vulcanization is carried out at 168 ℃ for 10min, and the second stage of vulcanization is carried out at 232 ℃ for 4h.
The tensile strength of the vulcanized rubber was 22.5MPa, the elongation was 220%, the compression set (200 ℃ C.. Times.70 h) was 17%, the methanol resistance (. DELTA.V) was 0.56, and the adhesion to the substrate was IV-grade.
Example 2
(1) Into a 50L reactor was charged 30L deionized water. The reactor should be evacuated, when the oxygen content is less than or equal to 30ppm, 30g of ammonium perfluorooctanoate is added, 65g of trifluorobromoethylene is added, the temperature of the reactor is heated to 90 ℃, and the stirring speed is 220 r/min;
(2) Introducing vinylidene fluoride, tetrafluoroethylene and hexafluoropropylene according to a molar ratio of 40:20:40, raising the pressure of the reactor to 2.8MPa, and then adding 22g of potassium persulfate and 35g of diiodomethane to start polymerization reaction;
(3) Continuously supplementing an aqueous solution containing 5% of potassium persulfate after the polymerization reaction is carried out, wherein the supplementing rate is 40g/10min; simultaneously, the molar ratio of chlorotrifluoroethylene, vinylidene fluoride, tetrafluoroethylene and hexafluoropropylene is continuously added to 15:45:22:18, maintaining the absolute pressure in the reactor between 2.8+/-0.3 MPa, taking gas sample composition analysis in the reactor when the feeding amount of the polymerized monomer reaches 20%, 30%, 40%, 50%, 60%, 70%, 80% and 90% of the total feeding amount, and controlling the mole fraction of the chlorotrifluoroethylene in a gas phase part in the reactor after the total feeding amount of the polymerized monomer reaches 30% to be 14+/-0.5% by adjusting the feeding rate of the additional monomer;
(4) The solid content of the emulsion reaches about 32 percent (mass percent), the polymerization reaction is finished, the reaction time in the polymerization process is about 3.2 hours, the unreacted monomers are recovered, and the emulsion is put into a coagulation barrel; adding a certain amount of MgCl 2 Condensing; vacuum drying at about 100deg.C; the resulting peroxide cured fluororubber was about 9.5Kg.
The green rubber product had a nylon viscosity of 47 (ML1+10min 121 ℃ C.), and a fluorine content: 69.5%, vulcanizing the modified peroxide vulcanized fluororubber prepared by the method by using the following vulcanization formula:
the first stage of vulcanization is carried out at 168 ℃ for 10min, and the second stage of vulcanization is carried out at 232 ℃ for 4h.
The tensile strength of the vulcanized rubber was 21.6MPa, the elongation was 240%, the compression set (200 ℃ C.. Times.70 h) was 15%, the methanol resistance (. DELTA.V) was 0.7, and the adhesion to the substrate was IV-grade.
Comparative example 1
In comparison with example 1, the difference is that in the polymerization reaction, a mixture of vinylidene fluoride, tetrafluoroethylene and hexafluoropropylene was fed in a molar ratio of 44:22:34, and the pressure in the reactor is maintained between 2.0+/-0.3 MPa.
The vulcanized rubber obtained in comparative example 1 had a tensile strength of 22.5MPa, an elongation of 210%, a compression set (200 ℃ C.. Times.70 h) of 20%, a methanol resistance (. DELTA.V) of 0.45 and an adhesion to a substrate of class II.
Comparative example 2
In comparison with example 1, the difference is that in the polymerization reaction, a molar ratio of 25:32:18:25, the pressure in the reactor is maintained between 2.0 plus or minus 0.3MPa, and the mole fraction of the chlorotrifluoroethylene in the gas phase part in the reactor is controlled to be 21 plus or minus 0.5 percent after the total feeding amount of the polymerized monomers reaches 30 percent by adjusting the feeding rate of the additional mixed monomers.
The vulcanized rubber obtained in comparative example 2 had a tensile strength of 24.8MPa, an elongation of 160%, a compression set (200 ℃ C.. Times.70 h) of 23%, a methanol resistance (. DELTA.V) of 2.1% and an adhesion to a substrate of grade IV.
While the invention has been described in detail in the foregoing general description, embodiments and experiments, it will be apparent to those skilled in the art that modifications and improvements can be made thereto. Accordingly, such modifications or improvements may be made without departing from the spirit of the invention and are intended to be within the scope of the invention as claimed.
Claims (10)
1. The preparation method of the trifluorochloroethylene modified peroxide vulcanized fluororubber is characterized by comprising the following steps of:
(1) Adding initial mixed monomer containing vinylidene fluoride, tetrafluoroethylene and hexafluoropropylene into a reactor which is pre-added with aqueous phase reaction medium, emulsifying agent and vulcanization point monomer to enable the pressure of the reactor to reach 1.6-3.5 MPa, adding initiator and chain transfer agent, and starting polymerization reaction; the initial mixed monomer is prepared from vinylidene fluoride, tetrafluoroethylene and hexafluoropropylene in a molar ratio of (15-45): (15-30): (40-55);
(2) Adding additional mixed monomers containing chlorotrifluoroethylene, vinylidene fluoride, tetrafluoroethylene and hexafluoropropylene in the polymerization process, controlling the pressure in the reaction kettle to be 1.6-3.5 MPa, and controlling the mole fraction of the chlorotrifluoroethylene in a gas phase part in the reactor to be 10-15% after the feeding amount of the polymerized monomers reaches 30% of the total feeding amount; the additional mixed monomer is prepared from chlorotrifluoroethylene, vinylidene fluoride, tetrafluoroethylene and hexafluoropropylene in a molar ratio of (5-20): (35-54): (18-25): (18-35);
(3) Ending the reaction when the mass percentage of solids in the emulsion obtained by the polymerization reaction reaches 25-35%, and condensing, washing and drying the obtained polymerization emulsion;
(4) Vulcanizing the fluororubber obtained in the step (3) to obtain vulcanized fluororubber, wherein a cross-linking agent used for vulcanization is a peroxide vulcanizing agent.
2. The method for producing a chlorotrifluoroethylene modified peroxide curable fluororubber according to claim 1, wherein the polymerization reaction temperature is 50 to 100 ℃.
3. The method for producing a chlorotrifluoroethylene modified peroxide curable fluororubber according to claim 2, wherein the polymerization reaction temperature is 70 to 100 ℃.
4. A process for the preparation of a chlorotrifluoroethylene modified peroxide curable fluororubber according to any one of claims 1 to 3, wherein the emulsifier is an ammonium, sodium or potassium salt of perfluorooctanoic acid;
and/or the addition amount of the emulsifier is 0.01-5 parts by weight of the emulsifier per 100 parts by weight of the aqueous phase reaction medium.
5. A process for the preparation of a chlorotrifluoroethylene modified peroxide curable fluororubber according to any one of claims 1 to 3, wherein said cure site monomer is selected from one or more of trifluoroethylene, trifluoroiodoethylene, perfluoroalkyl vinyl ether, 3, 4-tetrafluoro-4-bromobut-1-ene;
and/or the addition amount of the vulcanization point monomer is 0.5-3% of the total feeding amount of the polymerized monomer.
6. The method for preparing a trifluorochloroethylene modified peroxide vulcanized fluororubber as defined in claim 5, wherein the vulcanization point monomer is trifluorobromoethylene or 3, 4-tetrafluoro-4-bromobut-1-ene.
7. A process for the preparation of a chlorotrifluoroethylene modified peroxide cured fluororubber according to any one of claims 1 to 3, wherein the initiator is ammonium persulfate or potassium persulfate;
and/or, in the step (1), adding 0.01 to 5 parts by weight of an initiator per 100 parts by weight of the aqueous phase reaction medium;
and/or, continuously supplementing an initiator solution with the mass fraction of 5% in the polymerization reaction process in the step (2), wherein the rate of supplementing the initiator solution is 10-100 g/10min.
8. A process for the preparation of a chlorotrifluoroethylene modified peroxide curable fluororubber according to any one of claims 1 to 3 wherein the chain transfer agent is an α, ω -diiodoalkane or an α, ω -diiodoperfluoroalkane;
and/or the addition amount of the chain transfer agent is 0.01-5% of the total feeding amount of the polymerized monomers.
9. The method for producing a chlorotrifluoroethylene modified peroxide curable fluororubber according to claim 8, wherein the chain transfer agent is diiodomethane, 1, 4-diiodobutane or 1, 4-diiodoperfluorobutane.
10. The chlorotrifluoroethylene modified peroxide vulcanized fluororubber prepared by the preparation method according to any one of claims 1 to 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110897653.4A CN115703861B (en) | 2021-08-05 | 2021-08-05 | Trifluoro chloroethylene modified peroxide vulcanized fluororubber and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110897653.4A CN115703861B (en) | 2021-08-05 | 2021-08-05 | Trifluoro chloroethylene modified peroxide vulcanized fluororubber and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115703861A CN115703861A (en) | 2023-02-17 |
| CN115703861B true CN115703861B (en) | 2024-04-02 |
Family
ID=85178846
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110897653.4A Active CN115703861B (en) | 2021-08-05 | 2021-08-05 | Trifluoro chloroethylene modified peroxide vulcanized fluororubber and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115703861B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104530291A (en) * | 2014-12-17 | 2015-04-22 | 中昊晨光化工研究院有限公司 | Chlorotrifluoroethylene modified fluorinated ethylene propylene resin and preparation method thereof |
| CN106832072A (en) * | 2015-12-04 | 2017-06-13 | 中昊晨光化工研究院有限公司 | A kind of daiflon and preparation method thereof |
| WO2018065306A1 (en) * | 2016-10-05 | 2018-04-12 | Solvay Specialty Polymers Italy S.P.A. | Vinylidene fluoride and trifluoroethylene containing polymers latexes |
| CN110684141A (en) * | 2018-07-06 | 2020-01-14 | 中昊晨光化工研究院有限公司 | Peroxide vulcanized fluororubber with low Mooney viscosity and high fluorine content |
-
2021
- 2021-08-05 CN CN202110897653.4A patent/CN115703861B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104530291A (en) * | 2014-12-17 | 2015-04-22 | 中昊晨光化工研究院有限公司 | Chlorotrifluoroethylene modified fluorinated ethylene propylene resin and preparation method thereof |
| CN106832072A (en) * | 2015-12-04 | 2017-06-13 | 中昊晨光化工研究院有限公司 | A kind of daiflon and preparation method thereof |
| WO2018065306A1 (en) * | 2016-10-05 | 2018-04-12 | Solvay Specialty Polymers Italy S.P.A. | Vinylidene fluoride and trifluoroethylene containing polymers latexes |
| CN110684141A (en) * | 2018-07-06 | 2020-01-14 | 中昊晨光化工研究院有限公司 | Peroxide vulcanized fluororubber with low Mooney viscosity and high fluorine content |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115703861A (en) | 2023-02-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US9745398B2 (en) | Method of preparing fluoroelastomer capable of being vulcanized by using peroxide | |
| EP1432744B2 (en) | Aqueous emulsion polymerization in the presence of ethers as chain transfer agents to produce fluoropolymers | |
| JPH0320405B2 (en) | ||
| RU2349608C2 (en) | Fluoroelastomers with low temperature characteristics and resistance to solvents | |
| RU2412951C2 (en) | Method of producing elastic fluorocopolymer and cross linked fluoro-rubber | |
| JPS6236407A (en) | Production of curable fluoroelastomer and thus obtained product | |
| JPH0352907A (en) | New fluoroelastomer having improved processability and preparation thereof | |
| JPH03221510A (en) | Peroxide-curing fluoroelastomer and chlorofluoroelastomer which have bromine and iodine curing sites, and manufacture thereof | |
| CN104558364B (en) | Fluoroelastomer and preparation method thereof | |
| CN110684141A (en) | Peroxide vulcanized fluororubber with low Mooney viscosity and high fluorine content | |
| CN110713564A (en) | Wide-temperature-range perfluoroether rubber and synthesis method thereof | |
| CN110078857A (en) | A kind of preparation method of crude fluororubber | |
| CN106854254A (en) | Short vulcanization fluoroelastomer and preparation method thereof | |
| CN113461852A (en) | Peroxide vulcanized fluororubber and preparation method thereof | |
| CN115703860B (en) | Tetrafluoroethylene modified peroxide vulcanized binary fluororubber and preparation method thereof | |
| CN115703861B (en) | Trifluoro chloroethylene modified peroxide vulcanized fluororubber and preparation method thereof | |
| CN110818825A (en) | Peroxide-curable fluorine-containing elastomer and preparation method thereof | |
| CN114621383B (en) | Perfluoroether elastomer emulsion, preparation method and perfluoroether elastomer | |
| JP3657614B2 (en) | Fluorine-containing polymers and their preparation | |
| JPH07224201A (en) | Fluorocopolymer composition | |
| JPS63308008A (en) | Production of fluorine-containing elastomer vulcanizable with peroxide | |
| CN101508753A (en) | Preparation of ethylene and tetrafluoroethylene copolymer | |
| CN116162199A (en) | Fluororubber raw rubber and preparation method thereof | |
| JPH10130341A (en) | Production of fluorine-containing graft copolymer | |
| CN112300314B (en) | Tetrafluoroethylene modified fluororubber and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |