CN116162199A - Fluororubber raw rubber and preparation method thereof - Google Patents
Fluororubber raw rubber and preparation method thereof Download PDFInfo
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- CN116162199A CN116162199A CN202111415316.3A CN202111415316A CN116162199A CN 116162199 A CN116162199 A CN 116162199A CN 202111415316 A CN202111415316 A CN 202111415316A CN 116162199 A CN116162199 A CN 116162199A
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- 229920001973 fluoroelastomer Polymers 0.000 title claims abstract description 73
- 229920001971 elastomer Polymers 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000003999 initiator Substances 0.000 claims abstract description 89
- 239000000178 monomer Substances 0.000 claims abstract description 45
- 238000004073 vulcanization Methods 0.000 claims abstract description 38
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 33
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims abstract description 29
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims abstract description 25
- 239000012429 reaction media Substances 0.000 claims abstract description 22
- 230000000977 initiatory effect Effects 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000012986 chain transfer agent Substances 0.000 claims abstract description 13
- 238000007720 emulsion polymerization reaction Methods 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 51
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims description 40
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 claims description 40
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 40
- 239000007789 gas Substances 0.000 claims description 24
- 239000000839 emulsion Substances 0.000 claims description 20
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 239000003995 emulsifying agent Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- NZZFYRREKKOMAT-UHFFFAOYSA-N diiodomethane Chemical compound ICI NZZFYRREKKOMAT-UHFFFAOYSA-N 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- ROUYUBHVBIKMQO-UHFFFAOYSA-N 1,4-diiodobutane Chemical compound ICCCCI ROUYUBHVBIKMQO-UHFFFAOYSA-N 0.000 claims description 4
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 4
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 4
- -1 trifluorobromoethylene, 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 3
- AYCANDRGVPTASA-UHFFFAOYSA-N 1-bromo-1,2,2-trifluoroethene Chemical group FC(F)=C(F)Br AYCANDRGVPTASA-UHFFFAOYSA-N 0.000 claims description 3
- SNGREZUHAYWORS-UHFFFAOYSA-M 2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctanoate Chemical group [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 SNGREZUHAYWORS-UHFFFAOYSA-M 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000009826 distribution Methods 0.000 abstract description 16
- 238000012545 processing Methods 0.000 abstract description 13
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 21
- 150000003254 radicals Chemical class 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- 238000007906 compression Methods 0.000 description 10
- 230000006835 compression Effects 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 230000015271 coagulation Effects 0.000 description 6
- 238000005345 coagulation Methods 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 6
- LWHQXUODFPPQTL-UHFFFAOYSA-M sodium;2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctanoate Chemical compound [Na+].[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 LWHQXUODFPPQTL-UHFFFAOYSA-M 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-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
- 230000008859 change Effects 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- PZVZTKFRZJMHEM-UHFFFAOYSA-N iodotrifluoroethylene Chemical group FC(F)=C(F)I PZVZTKFRZJMHEM-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 241001441571 Hiodontidae Species 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 238000009472 formulation Methods 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
- 125000005843 halogen group Chemical group 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000010060 peroxide vulcanization Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- WPDDXKNWUVLZMQ-UHFFFAOYSA-M potassium;2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctanoate Chemical compound [K+].[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 WPDDXKNWUVLZMQ-UHFFFAOYSA-M 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F214/18—Monomers containing fluorine
- C08F214/28—Hexyfluoropropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F214/18—Monomers containing fluorine
- C08F214/22—Vinylidene fluoride
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
- Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The invention provides fluororubber raw rubber and a preparation method thereof. The preparation method comprises the following steps: taking a main monomer and a vulcanization point monomer as raw materials, taking water as a reaction medium, and performing emulsion polymerization reaction in the presence of an initiator and a chain transfer agent to generate fluororubber raw rubber; the initiator comprises a first initiator and a second initiator, wherein the first initiator is added during chain initiation, and the second initiator is added after the polymerization reaction reaches a chain growth period; the first initiator comprises ammonium persulfate and potassium persulfate with the mass ratio of (1-4) being 1, and the second initiator comprises ammonium persulfate and potassium persulfate with the mass ratio of (2-5); the mass ratio of the first initiator to the second initiator is 1 (0.5-3). Compared with fluororubber raw rubber prepared by using a single initiator, the fluororubber raw rubber prepared by the method provided by the invention has higher molecular weight, narrower molecular weight distribution, good vulcanization performance and processing fluidity.
Description
Technical Field
The invention belongs to the technical field of fluororubber materials, and particularly relates to fluororubber raw rubber and a preparation method thereof.
Background
Fluororubbers are synthetic high-molecular polymers containing fluorine atoms in the main chain or side chain carbon atoms, and are usually vulcanized in practical use. Peroxide (or radical) cured fluororubbers were originally developed and commercialized by dupont in the united states in the early 70 s of the 20 th century, and then developed by japan large gold company and the asu-wei company. The rubber has excellent performances of high temperature resistance, corrosion resistance and the like peculiar to fluororubber, also has outstanding performances of hot tearing property, superheated steam resistance, organic medium resistance and the like, and has wide application in the fields of electronic and electric industry, chemical industry, mechanical industry, national defense industry and the like.
The industrial unvulcanized fluororubber is prepared by emulsion polymerization of fluoromonomers (such as vinylidene fluoride (VDF), hexafluoropropylene (HFP), tetrafluoroethylene (TFE) and the like) and vulcanization point monomers (such as CSM) in a certain proportion by taking water as a reaction medium. For example, CN 104098730A discloses a fluororubber with low Mooney and high fluorine content and a preparation method thereof, and the fluorine content of the fluororubber prepared by introducing special modified monomers and adjusting the proportion of other monomers is up to more than 72%, and the Mooney viscosity is less than or equal to 30.CN 105111353a discloses a preparation method of special low temperature resistant fluororubber, which makes the prepared fluororubber resistant to low temperature of minus 40 ℃ by adopting photochemical reaction and special fluoromonomer.
However, the fluororubber prepared by the method has the advantages of low molecular weight, wide molecular weight distribution, and poor processing fluidity and vulcanization performance in the processing process. In recent years, with the expansion of applications of fluororubbers, the requirements on the performances of fluororubbers are increasing, and the existing fluororubbers cannot meet the market demands. Therefore, a fluororubber material with higher molecular weight, narrower molecular weight distribution and better vulcanization performance and processing fluidity is to be researched to meet the requirements of practical application.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide fluororubber raw rubber and a preparation method thereof. Compared with fluororubber raw rubber prepared by using a single initiator, the fluororubber raw rubber has higher molecular weight and narrower molecular weight distribution, and good vulcanization performance and processing flowability.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing a raw fluororubber, comprising the steps of:
taking a main monomer and a vulcanization point monomer as raw materials, taking water as a reaction medium, and performing emulsion polymerization reaction in the presence of an initiator and a chain transfer agent to generate fluororubber raw rubber;
wherein the initiator comprises a first initiator and a second initiator, the first initiator is added when the chain is initiated, and the second initiator is added after the polymerization reaction reaches the chain growth period;
the first initiator comprises ammonium persulfate and potassium persulfate in a mass ratio of (1-4) 1 (e.g., may be 1:1, 1.2:1, 1.5:1, 1.8:1, 2:1, 2.2:1, 2.5:1, 2.8:1, 3:1, 3.2:1, 3.5:1, 3.8:1, or 4:1, etc.);
the second initiator comprises ammonium persulfate and potassium persulfate in a mass ratio of 1 (2-5) (e.g., may be 1:2, 1:2.2, 1:2.5, 1:2.8, 1:3, 1:3.2, 1:3.5, 1:3.8, 1:4, 1:4.2, 1:4.5, 1:4.8, or 1:5, etc.);
the mass ratio of the first initiator to the second initiator is 1 (0.5-3), for example, 1:0.5, 1:0.8, 1:1, 1:1.2, 1:1.5, 1:1.8, 1:2, 1:2.2, 1:2.5, 1:2.8 or 1:3, etc.
The main monomer in the present invention refers to a main monomer used for synthesizing the fluororubber raw rubber by polymerization, that is, a monomer except for a vulcanization point monomer among all monomers used for preparing the fluororubber raw rubber. The vulcanization point monomer refers to a monomer providing vulcanization points for the raw fluororubber. The time to reach the chain extension period can be determined according to methods conventional in the art, typically 30-50 minutes after chain initiation in the present invention.
Compared with fluororubber raw rubber prepared by using a single initiator, the fluororubber raw rubber prepared by using the method has the advantages that the first initiator and the second initiator with specific components and proportions are respectively adopted in a chain initiation period and a chain growth period, the decomposition rate of the initiator is effectively controlled and complemented by utilizing the synergistic effect of the first initiator and the second initiator, the chain initiation rate can be controlled, the chain growth rate is improved, the number of free radicals generated in different reaction periods is balanced, and other materials, process conditions and steps are combined, so that the fluororubber raw rubber with higher molecular weight, narrower molecular weight distribution and better vulcanization performance and processing fluidity is obtained. If the molecular weight distribution of the obtained polymer is wider, the low molecular weight polymer is increased, and the low molecular weight polymer chain is shorter, so that the content of the crosslinking point monomer in the low molecular weight polymer is relatively smaller in the peroxide vulcanization process, and the low molecular weight polymer cannot form a compact crosslinked network after vulcanization. And the presence of low molecular weight polymers can also cause rubber sticking phenomena and the like due to the relatively high temperature (160-200 ℃) during the vulcanization process.
In some embodiments of the invention, the primary monomers are vinylidene fluoride, tetrafluoroethylene, and hexafluoropropylene.
In some embodiments of the invention, the preparation method comprises the steps of:
(1) Adding water into a reactor as a reaction medium, removing air in the reactor, dissolving an emulsifying agent into the water, and introducing a first mixed gas of vinylidene fluoride, tetrafluoroethylene and hexafluoropropylene;
(2) Adding the first initiator, the chain transfer agent and the vulcanization point monomer to start initiating polymerization reaction;
(3) And in the reaction process, continuously adding a second mixed gas of vinylidene fluoride, tetrafluoroethylene and hexafluoropropylene to maintain the reaction pressure, adding a second initiator when the reaction reaches a chain growth period, and ending the reaction when the vinylidene fluoride, the tetrafluoroethylene and the hexafluoropropylene which participate in the reaction reach a preset feeding amount to generate the fluororubber raw rubber.
In some embodiments of the present invention, the molar ratio of vinylidene fluoride, tetrafluoroethylene, and hexafluoropropylene in the first mixed gas introduced in step (1) is (15-45): 15-30): 40-55.
In some embodiments of the present invention, the molar ratio of vinylidene fluoride, tetrafluoroethylene, and hexafluoropropylene in the second mixed gas fed in step (3) is (40-54): 18-25): 28-42.
In some embodiments of the invention, the volume of the reaction medium is 60-70% of the reactor volume; for example, 60%, 62%, 63%, 65%, 66%, 68% or 70% may be used.
In some embodiments of the invention, the emulsifier is a perfluorooctanoate, such as ammonium perfluorooctanoate, sodium perfluorooctanoate, potassium perfluorooctanoate.
In some embodiments of the invention, the emulsifier is used in an amount of 0.01 to 5% by mass of the reaction medium; for example, 0.01%, 0.05%, 0.1%, 0.3%, 0.5%, 0.8%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5% or 5% may be used.
In some embodiments of the invention, the first initiator is used in an amount of 0.1 to 1% by mass of the reaction medium; for example, 0.1%, 0.3%, 0.5%, 0.8%, 1% or the like may be used.
In some embodiments of the invention, the cure site monomer is a halogenated fluoroolefin, preferably selected from one or a combination of at least two of trifluorobromoethylene, trifluoroiodoethylene, perfluoroiodoalkyl vinyl ether, perfluorobromoalkyl vinyl ether, and 3, 4-tetrafluoro-4-bromo-1-butene, more preferably trifluorobromoethylene and/or 3, 4-tetrafluoro-4-bromo-1-butene.
The halogenated fluoroolefins in the present invention are fluoroolefins substituted with halogen atoms other than fluorine.
In some embodiments of the invention, the amount of the cure site monomer is 0.5-3% of the total charge mass of the main monomer; for example, 0.5%, 0.8%, 1%, 1.2%, 1.5%, 1.8%, 2%, 2.2%, 2.5%, 2.8%, 3%, or the like may be used.
It should be noted that, the total feeding mass of the main monomers in the present invention refers to the total mass of the main monomers actually participating in the reaction. When the main monomers are vinylidene fluoride, tetrafluoroethylene and hexafluoropropylene, the total mass of the vinylidene fluoride, tetrafluoroethylene and hexafluoropropylene actually participating in the reaction is meant.
In some embodiments of the invention, the chain transfer agent is an iodoalkane, preferably an α, ω -diiodoalkane and/or an α, ω -diiodoperfluoroalkane, further preferably one or a combination of at least two selected from diiodomethane, 1, 4-diiodobutane and 1, 4-diiodoperfluorobutane.
In some embodiments of the invention, the chain transfer agent is used in an amount of 0.01 to 5% of the total charge mass of the main monomer; for example, 0.01%, 0.03%, 0.05%, 0.08%, 0.1%, 0.2%, 0.3%, 0.5%, 0.8%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5% or 5% may be used.
In some embodiments of the invention, the temperature of the reaction is 50-100deg.C, such as 50deg.C, 55deg.C, 60deg.C, 65deg.C, 70deg.C, 75deg.C, 80deg.C, 85deg.C, 90deg.C, 95deg.C, 100deg.C, etc.; preferably 70-100 ℃.
In some embodiments of the invention, the pressure of the reaction is 1.6-3.5MPa, which may be, for example, 1.6MPa, 1.8MPa, 2.0MPa, 2.2MPa, 2.3MPa, 2.5MPa, 2.8MPa, 3MPa, 3.2MPa, or 3.5MPa, etc.; preferably 2.0-3.5MPa.
In some embodiments of the invention, the preparation method comprises the steps of:
(1) Adding 100 parts by weight of water as a reaction medium into a reactor, wherein the volume of the reaction medium is 60-70% of the volume of the reactor, evacuating the reactor until the oxygen content is less than or equal to 30ppm, adding 0.01-5 parts of emulsifier, heating to 50-100 ℃, and introducing a first mixed gas with the mol ratio of vinylidene fluoride, tetrafluoroethylene and hexafluoropropylene of (15-45) to (15-30) to (40-55) until the pressure in the reactor is 1.6-3.5MPa;
(2) Adding 0.1-1 part of a first initiator, wherein the first initiator consists of ammonium sulfate and potassium persulfate according to the mass ratio of (1-4): 1, and comprises 0.01-5% of chain transfer agent and 0.5-3% of vulcanization point monomer, wherein the chain transfer agent and the vulcanization point monomer respectively account for the total feeding mass of vinylidene fluoride, tetrafluoroethylene and hexafluoropropylene;
(3) Continuously adding a second mixed gas with the mole ratio of (40-54), of (18-25) and of (28-42) into the reaction process, maintaining the reaction pressure constant, adding a second initiator after the reaction reaches a chain growth period, wherein the second initiator consists of ammonium sulfate and potassium persulfate according to the mass ratio of 1 (2-5), the mass ratio of the first initiator to the second initiator is 1 (0.5-3), and ending the reaction when the vinylidene fluoride, the tetrafluoroethylene and the hexafluoropropylene which participate in the reaction reach a preset feeding amount;
(4) And (3) condensing, washing and drying the polymerization emulsion obtained in the step (3) to obtain the fluororubber raw rubber.
In a second aspect, the present invention provides a fluororubber raw rubber prepared by the preparation method of the first aspect.
Compared with the prior art, the invention has the following beneficial effects:
compared with fluororubber raw rubber prepared by using a single initiator, the fluororubber raw rubber prepared by using the method has the advantages that the first initiator and the second initiator with specific components and proportions are respectively adopted in a chain initiation period and a chain growth period, the decomposition rate of the initiator is effectively controlled and complemented by utilizing the synergistic effect of the first initiator and the second initiator, the chain initiation rate can be controlled, the chain growth rate is improved, the number of free radicals generated in different reaction periods is balanced, and other materials, process conditions and steps are combined, so that the fluororubber raw rubber with higher molecular weight, narrower molecular weight distribution and better vulcanization performance and processing fluidity is obtained.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It should be apparent to those skilled in the art that the detailed description is merely provided to aid in understanding the invention and should not be taken as limiting the invention in any way.
Example 1
The embodiment provides a fluororubber raw rubber, which is prepared by the following steps:
(1) Adding 30L of deionized water as a reaction medium into a 50L reactor, evacuating the reactor until the oxygen content is less than or equal to 30ppm, adding 35g of sodium perfluorooctanoate, heating to 85 ℃, and introducing a first mixed gas with the molar ratio of vinylidene fluoride, tetrafluoroethylene and hexafluoropropylene being 34:22:44 until the pressure in the reactor is 3.0MPa;
(2) 45g of a first initiator (composed of ammonium persulfate and potassium persulfate in a mass ratio of 1:1), 25g of diiodomethane and 70g of trifluoroiodoethylene are added to start the polymerization reaction;
(3) Continuously adding a second mixed gas with the mole ratio of vinylidene fluoride, tetrafluoroethylene and hexafluoropropylene of 42:20:38 in the reaction process, keeping the absolute pressure in a reactor at 3.0+/-0.02 MPa, adding 25g of a second initiator (consisting of ammonium persulfate and potassium persulfate in a mass ratio of 1:4) after the reaction reaches a chain extension period (after chain initiation for 32 min), ending the reaction when the solid content of the polymerization emulsion reaches 30% (the reaction time is 2.5h, and the mole ratio of the vinylidene fluoride, the tetrafluoroethylene and the hexafluoropropylene which participate in the reaction is 42:23:35), recovering unreacted monomers, and putting the polymerization emulsion into a coagulation barrel;
(4) Adding MgCl into the polymerization emulsion obtained in the step (3) 2 Condensing, washing, and vacuum drying at 100 ℃ to obtain the fluororubber raw rubber.
Example 2
The embodiment provides a fluororubber raw rubber, which is prepared by the following steps:
(1) Adding 32L of deionized water as a reaction medium into a 50L reactor, evacuating the reactor until the oxygen content is less than or equal to 30ppm, adding 40g of ammonium perfluorooctanoate, heating to 92 ℃, and introducing a first mixed gas with the molar ratio of vinylidene fluoride, tetrafluoroethylene and hexafluoropropylene being 31:23:46 until the pressure in the reactor is 2.3MPa;
(2) 38g of a first initiator (composed of ammonium persulfate and potassium persulfate in a mass ratio of 4:1), 35g of 1, 4-diiodobutane and 80g of trifluorobromoethylene are added to start the polymerization reaction;
(3) Continuously adding a second mixed gas with the mole ratio of vinylidene fluoride, tetrafluoroethylene and hexafluoropropylene of 48:22:30 in the reaction process, keeping the absolute pressure in a reactor at 2.3+/-0.02 MPa, adding 45g of a second initiator (consisting of ammonium persulfate and potassium persulfate in a mass ratio of 1:2) after the reaction reaches a chain extension period (after 38min of chain initiation), ending the reaction when the solid content of the polymerization emulsion reaches 28% (the reaction time is 3.5h, and the mole ratio of vinylidene fluoride, tetrafluoroethylene and hexafluoropropylene which participate in the reaction is 45:24:31), recovering unreacted monomers, and putting the polymerization emulsion into a coagulation barrel;
(4) Adding MgCl into the polymerization emulsion obtained in the step (3) 2 Condensing, washing, and vacuum drying at 100 ℃ to obtain the fluororubber raw rubber.
Example 3
The embodiment provides a fluororubber raw rubber, which is prepared by the following steps:
(1) Adding 30L of deionized water as a reaction medium into a 50L reactor, evacuating the reactor until the oxygen content is less than or equal to 30ppm, adding 1500g of sodium perfluorooctanoate, heating to 50 ℃, and introducing a first mixed gas with the molar ratio of vinylidene fluoride, tetrafluoroethylene and hexafluoropropylene being 45:15:40 until the pressure in the reactor is 1.6MPa;
(2) Adding 100g of a first initiator (composed of ammonium persulfate and potassium persulfate in a mass ratio of 2:1), 48g of 1, 4-diiodoperfluorobutane and 105g of perfluoro 2-bromotetrafluoroethyl trifluorovinyl ether, and starting to initiate polymerization;
(3) Continuously adding a second mixed gas with the mole ratio of vinylidene fluoride, tetrafluoroethylene and hexafluoropropylene of 54:18:28 in the reaction process, keeping the absolute pressure in a reactor at 1.6+/-0.02 MPa, adding 150g of a second initiator (consisting of ammonium persulfate and potassium persulfate in a mass ratio of 1:5) after the reaction reaches a chain extension period (after chain initiation for 35 min), ending the reaction when the solid content of the polymerization emulsion reaches 31% (the reaction time is 2.8h, and the mole ratio of vinylidene fluoride, tetrafluoroethylene and hexafluoropropylene which participate in the reaction is 39:26:35), recovering unreacted monomers, and putting the polymerization emulsion into a coagulation barrel;
(4) Adding MgCl into the polymerization emulsion obtained in the step (3) 2 Condensing, washing, and vacuum drying at 100 ℃ to obtain the fluororubber raw rubber.
Example 4
The embodiment provides a fluororubber raw rubber, which is prepared by the following steps:
(1) Adding 30L of deionized water as a reaction medium into a 50L reactor, evacuating the reactor until the oxygen content is less than or equal to 30ppm, adding 500g of sodium perfluorooctanoate, heating to 70 ℃, and introducing a first mixed gas with the molar ratio of vinylidene fluoride, tetrafluoroethylene and hexafluoropropylene being 25:25:50 until the pressure in the reactor is 2.0MPa;
(2) 200g of a first initiator (consisting of ammonium persulfate and potassium persulfate in a mass ratio of 3:1), 60g of diiodomethane and 120g of 3, 4-tetrafluoro-4-bromo-1-butene were added to initiate polymerization;
(3) Continuously adding a second mixed gas with the mol ratio of vinylidene fluoride, tetrafluoroethylene and hexafluoropropylene of 45:20:35 in the reaction process, keeping the absolute pressure in a reactor at 2.0+/-0.02 MPa, adding 315g of a second initiator (consisting of ammonium persulfate and potassium persulfate in a mass ratio of 1:3) after the reaction reaches a chain growth period (after 48min of chain initiation), ending the reaction when the solid content of the polymerization emulsion reaches 28% (the reaction time is 4.2h, and the mol ratio of vinylidene fluoride, tetrafluoroethylene and hexafluoropropylene which participate in the reaction is 41:25:34), recovering unreacted monomers, and putting the polymerization emulsion into a coagulation barrel;
(4) Adding MgCl into the polymerization emulsion obtained in the step (3) 2 Condensing, washing, and vacuum drying at 100 ℃ to obtain the fluororubber raw rubber.
Example 5
The embodiment provides a fluororubber raw rubber, which is prepared by the following steps:
(1) Adding 30L of deionized water as a reaction medium into a 50L reactor, evacuating the reactor until the oxygen content is less than or equal to 30ppm, adding 50g of sodium perfluorooctanoate, heating to 90 ℃, and introducing a first mixed gas with the molar ratio of vinylidene fluoride, tetrafluoroethylene and hexafluoropropylene being 30:30:40 until the pressure in the reactor is 2.5MPa;
(2) 80g of a first initiator (consisting of ammonium persulfate and potassium persulfate in a mass ratio of 2.5:1), 70g of 1, 4-diiodobutane and 150g of 3, 4-tetrafluoro-4-bromo-1-butene were added to initiate polymerization;
(3) Continuously adding a second mixed gas with the mole ratio of vinylidene fluoride, tetrafluoroethylene and hexafluoropropylene of 50:25:25 in the reaction process, keeping the absolute pressure in a reactor at 2.5+/-0.02 MPa, adding 150g of a second initiator (consisting of ammonium persulfate and potassium persulfate in a mass ratio of 1:3.5) after the reaction reaches a chain extension period (after chain initiation for 47 min), ending the reaction when the solid content of the polymerization emulsion reaches 26% (the reaction time is 5h, and the mole ratio of vinylidene fluoride, tetrafluoroethylene and hexafluoropropylene which participate in the reaction is 33:25:43), recovering unreacted monomers, and putting the polymerization emulsion into a coagulation barrel;
(4) Adding MgCl into the polymerization emulsion obtained in the step (3) 2 Condensing, washing, and vacuum drying at 100 ℃ to obtain the fluororubber raw rubber.
Comparative example 1
Provided is a fluororubber raw rubber, the preparation method of which is as follows:
(1) Adding 30L of deionized water as a reaction medium into a 50L reactor, evacuating the reactor until the oxygen content is less than or equal to 30ppm, adding 35g of sodium perfluorooctanoate, heating to 85 ℃, and introducing mixed gas of vinylidene fluoride, tetrafluoroethylene and hexafluoropropylene in a molar ratio of 34:22:44 until the pressure in the reactor is 3.0MPa;
(2) The polymerization was initiated by adding 25.5g of ammonium persulfate and 34.5g of potassium persulfate, 25g of diiodomethane and 70g of trifluoroiodoethylene;
(3) Continuously adding mixed gas with the mole ratio of vinylidene fluoride, tetrafluoroethylene and hexafluoropropylene being 42:20:38 in the reaction process, keeping the absolute pressure in a reactor at 3.0+/-0.02 MPa, ending the reaction when the solid content of the polymerized emulsion reaches 30% (the mole ratio of vinylidene fluoride, tetrafluoroethylene and hexafluoropropylene participating in the reaction is 33:25:43), recovering unreacted monomers, and placing the polymerized emulsion into a coagulation barrel;
(4) Adding MgCl into the polymerization emulsion obtained in the step (3) 2 Condensing, washing, and vacuum drying at 100 ℃ to obtain the fluororubber raw rubber.
Comparative example 2
There is provided a fluororubber raw rubber, the preparation method of which differs from example 1 in that: the first initiator consists of ammonium persulfate and potassium persulfate in a mass ratio of 5:1, and the second initiator consists of ammonium persulfate and potassium persulfate in a mass ratio of 1:6.
Comparative example 3
There is provided a fluororubber raw rubber, the preparation method of which differs from example 1 in that: the first initiator consists of ammonium persulfate and potassium persulfate in a mass ratio of 0.6:1, and the second initiator consists of ammonium persulfate and potassium persulfate in a mass ratio of 1:1.5.
Comparative example 4
There is provided a fluororubber raw rubber, the preparation method of which differs from example 1 in that: the first initiator was added in an amount of 5g and the second initiator was added in an amount of 55g.
Comparative example 5
There is provided a fluororubber raw rubber, the preparation method of which differs from example 1 in that: the first initiator was added in an amount of 58g and the second initiator was added in an amount of 2g.
Performance test:
the number average molecular weight and molecular weight distribution of the fluororubber raw rubber obtained in the above examples and comparative examples were tested by Gel Permeation Chromatography (GPC), and the test results are shown in table 1 below.
The fluororubber raw rubber obtained in the above examples and comparative examples was vulcanized with the following vulcanization formulation:
the vulcanization method comprises the following steps:
pressing the 3.5mm sheet into a 160mm×110mm×2mm test piece with a press and a steel film; cutting a cylindrical bar with the diameter of 28mm into a section of cylindrical blank with the diameter of 15g, and then molding into a cylindrical sample with the diameter of 29mm multiplied by 12.5 mm;
firstly, carrying out one-stage vulcanization on the test piece and the cylindrical sample, wherein the one-stage vulcanization condition is that the pressure is 6MPa, the temperature is 177 ℃, and the pressure of the vulcanized rubber sheet is maintained for 10min, and then the pressure is maintained for 20min under 30% of compression;
then carrying out secondary vulcanization on the test piece after primary vulcanization and the cylindrical test piece;
wherein, the test piece after the first-stage vulcanization is hung in a blast oven for the second-stage vulcanization, and the second-stage vulcanization conditions are as follows: sequentially preserving heat for 2h at room temperature, preserving heat for 2h at 150 ℃, preserving heat for 2h at 180 ℃, preserving heat for 2h at 200 ℃ and preserving heat for 4h at 230 ℃, and naturally cooling to room temperature without opening an oven door;
the cylindrical sample after the first section of vulcanization is firstly placed in a stainless steel plate and then placed in an oven, and is subjected to heat preservation for 4 hours at 230 ℃ to carry out the second section of vulcanization, and then the oven door is not opened to naturally cool to the room temperature.
The properties of the obtained vulcanized fluororubber were tested as follows:
tensile strength and elongation at break:
compression set: compression is carried out for 70h at 200 ℃ with 30% compression;
methanol resistance (Δv): soaking the sample in methanol at 23 ℃ for 70 hours, and measuring the volume change rate of the soaked sample;
rheological properties: testing maximum torque MH and minimum torque ML
The results of the above performance tests are shown in table 1 below:
TABLE 1
As can be seen from Table 1, the fluororubber raw rubber provided by the invention has a number average molecular weight of 7-10 ten thousand and a molecular weight distribution coefficient of 1.6-1.8, and has higher molecular weight and narrower molecular weight distribution. The vulcanized fluororubber obtained after vulcanization has the tensile strength of 22.0-23.5, the elongation at break of 240-280%, the compression set (200 ℃ multiplied by 70 h) of 18-20%, the volume change rate after methanol soaking for 70h of 2-3%, the maximum torque MH of 2.30-2.35 N.m and the minimum torque ML of 0.45-0.56 N.m, and has good vulcanization performance and processing fluidity after observing that a vulcanized test piece has no sulfur mark and no flower spot.
Compared with example 1, in comparative example 1, the initiator is added at one time in the initial stage, so that the concentration of free radicals in the initial stage of the polymerization reaction is too high, the obtained fluororubber raw rubber has uneven distribution of comonomer chain segments, more oligomers are generated, the molecular weight distribution is wider, the tensile strength and the maximum torque MH (crosslinking density) of vulcanized fluororubber are relatively lower, the compression resistance and the methanol resistance are poorer, and the phenomenon of sticking to rollers is caused during processing.
Compared with the example 1, the mass ratio of ammonium persulfate to potassium persulfate in the first initiator in the comparative example 2 is too large, the mass ratio of ammonium persulfate to potassium persulfate in the second initiator is too small, so that the concentration of free radicals in the chain initiation period is too high, the concentration of free radicals in the chain growth period is too low, the number of free radicals in the chain initiation period and the number of free radicals in the chain growth period are unbalanced, the obtained fluororubber raw rubber has wider molecular weight distribution, the vulcanized fluororubber has lower tensile strength, the uneven grafting of a monomer at a vulcanization point in a polymer chain segment causes poor compression resistance, and the phenomenon of sticking to rollers is caused during processing.
Compared with example 1, in comparative example 3, if the mass ratio of ammonium persulfate to potassium persulfate in the first initiator is too small, the mass ratio of ammonium persulfate to potassium persulfate in the second initiator is too large, resulting in too low concentration of free radicals in the chain initiation period, too high concentration of free radicals in the chain growth period, unbalanced number of free radicals in the chain initiation period and the chain growth period, the obtained fluororubber raw rubber has wider molecular weight distribution, lower tensile strength, poorer compression resistance and roll sticking phenomenon during processing.
Compared with the example 1, the mass ratio of the first initiator to the second initiator in the comparative example 4 is too small, so that the concentration of free radicals in the chain initiation period and the chain growth period is too low, the polymerization reaction time is longer, the raw fluororubber obtained by the method has lower molecular weight, wider molecular weight distribution, lower tensile strength of vulcanized fluororubber, fewer monomer access chain segments at vulcanization points, lower maximum torque MH, poorer compression resistance and roll sticking phenomenon during processing.
Compared with the example 1, the mass ratio of the first initiator to the second initiator in the comparative example 5 is too large, so that the free radical concentration in the chain initiation period and the chain growth period is too high, the polymerization rate is higher, the obtained fluororubber raw rubber has wider molecular weight distribution, the vulcanized fluororubber has lower tensile strength, the monomer at the vulcanization point is not uniformly connected with the rubber chain segment, the maximum torque MH is lower, the compression resistance is poorer, and the phenomenon of sticking to rollers is generated during processing.
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. A method for preparing fluororubber raw rubber, which is characterized by comprising the following steps:
taking a main monomer and a vulcanization point monomer as raw materials, taking water as a reaction medium, and performing emulsion polymerization reaction in the presence of an initiator and a chain transfer agent to generate fluororubber raw rubber;
wherein the initiator comprises a first initiator and a second initiator, the first initiator is added when the chain is initiated, and the second initiator is added after the polymerization reaction reaches the chain growth period;
the first initiator comprises ammonium persulfate and potassium persulfate with the mass ratio of (1-4) being 1;
the second initiator comprises ammonium persulfate and potassium persulfate with the mass ratio of (2-5) being 1;
the mass ratio of the first initiator to the second initiator is 1 (0.5-3).
2. The method according to claim 1, wherein the main monomers are vinylidene fluoride, tetrafluoroethylene, and hexafluoropropylene;
preferably, the preparation method comprises the following steps:
(1) Adding water into a reactor as a reaction medium, removing air in the reactor, dissolving an emulsifying agent into the water, and introducing a first mixed gas of vinylidene fluoride, tetrafluoroethylene and hexafluoropropylene;
(2) Adding the first initiator, the chain transfer agent and the vulcanization point monomer to start initiating polymerization reaction;
(3) And in the reaction process, continuously adding a second mixed gas of vinylidene fluoride, tetrafluoroethylene and hexafluoropropylene to maintain the reaction pressure, adding a second initiator when the reaction reaches a chain growth period, and ending the reaction when the vinylidene fluoride, the tetrafluoroethylene and the hexafluoropropylene which participate in the reaction reach a preset feeding amount to generate the fluororubber raw rubber.
3. The preparation method according to claim 2, wherein the molar ratio of vinylidene fluoride, tetrafluoroethylene and hexafluoropropylene in the first mixed gas introduced in the step (1) is (15-45): 15-30): 40-55;
preferably, the mole ratio of vinylidene fluoride, tetrafluoroethylene and hexafluoropropylene in the second mixed gas added in the step (3) is (40-54): (18-25): (28-42);
preferably, the volume of the reaction medium is 60-70% of the reactor volume.
4. A method of preparation according to any one of claims 1 to 3 wherein the emulsifier is perfluorooctanoate;
preferably, the emulsifier is used in an amount of 0.01-5% by mass of the reaction medium.
5. The process of any one of claims 1 to 4, wherein the first initiator is used in an amount of 0.1 to 1% by mass of the reaction medium.
6. The method of any one of claims 1 to 5, wherein the cure site monomer is a halogenated fluoroolefin, preferably selected from one or a combination of at least two of trifluorobromoethylene, trifluoroiodoethylene, perfluoroalkyl vinyl ether, and 3, 4-tetrafluoro-4-bromo-1-butene, further preferably trifluorobromoethylene and/or 3, 4-tetrafluoro-4-bromo-1-butene;
preferably, the dosage of the vulcanization point monomer is 0.5-3% of the total feeding mass of the main monomer.
7. The preparation process according to any one of claims 1 to 6, characterized in that the chain transfer agent is an iodoalkane, preferably an α, ω -diiodoalkane and/or an α, ω -diiodoperfluoroalkane, further preferably one or a combination of at least two selected from diiodomethane, 1, 4-diiodobutane and 1, 4-diiodoperfluorobutane;
preferably, the chain transfer agent is used in an amount of 0.01 to 5% of the total charged mass of the main monomer.
8. The preparation method according to any one of claims 2 to 7, wherein the temperature of the reaction is 50 to 100 ℃, preferably 70 to 100 ℃;
preferably, the pressure of the reaction is 1.6-3.5MPa, preferably 2.0-3.5MPa.
9. The preparation method according to any one of claims 1 to 8, characterized in that the preparation method comprises the steps of:
(1) Adding 100 parts by weight of water as a reaction medium into a reactor, wherein the volume of the reaction medium is 60-70% of the volume of the reactor, evacuating the reactor until the oxygen content is less than or equal to 30ppm, adding 0.01-5 parts of emulsifier, heating to 50-100 ℃, and introducing a first mixed gas with the mol ratio of vinylidene fluoride, tetrafluoroethylene and hexafluoropropylene of (15-45) to (15-30) to (40-55) until the pressure in the reactor is 1.6-3.5MPa;
(2) Adding 0.1-1 part of a first initiator, wherein the first initiator consists of ammonium sulfate and potassium persulfate according to the mass ratio of (1-4): 1, and comprises 0.01-5% of chain transfer agent and 0.5-3% of vulcanization point monomer, wherein the chain transfer agent and the vulcanization point monomer respectively account for the total feeding mass of vinylidene fluoride, tetrafluoroethylene and hexafluoropropylene;
(3) Continuously adding a second mixed gas with the mole ratio of (40-54), of (18-25) and of (28-42) into the reaction process, maintaining the reaction pressure constant, adding a second initiator after the reaction reaches a chain growth period, wherein the second initiator consists of ammonium sulfate and potassium persulfate according to the mass ratio of 1 (2-5), the mass ratio of the first initiator to the second initiator is 1 (0.5-3), and ending the reaction when the vinylidene fluoride, the tetrafluoroethylene and the hexafluoropropylene which participate in the reaction reach a preset feeding amount;
(4) And (3) condensing, washing and drying the polymerization emulsion obtained in the step (3) to obtain the fluororubber raw rubber.
10. A fluororubber raw rubber prepared by the preparation method according to any one of claims 1 to 9.
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