CN116554619B - Fluororubber elastomer and preparation method thereof - Google Patents
Fluororubber elastomer and preparation method thereof Download PDFInfo
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- CN116554619B CN116554619B CN202310754878.3A CN202310754878A CN116554619B CN 116554619 B CN116554619 B CN 116554619B CN 202310754878 A CN202310754878 A CN 202310754878A CN 116554619 B CN116554619 B CN 116554619B
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- rubber
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 82
- 229920001973 fluoroelastomer Polymers 0.000 title claims abstract description 60
- 239000000806 elastomer Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 37
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 22
- 150000001875 compounds Chemical class 0.000 claims abstract description 11
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000004519 manufacturing process Methods 0.000 claims description 13
- 238000004073 vulcanization Methods 0.000 claims description 12
- 239000000945 filler Substances 0.000 claims description 10
- 239000012752 auxiliary agent Substances 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 238000007599 discharging Methods 0.000 claims description 8
- 229920006169 Perfluoroelastomer Polymers 0.000 claims description 5
- CKQHAYFOPRIUOM-UHFFFAOYSA-N 3'-Aminoacetophenone Chemical compound CC(=O)C1=CC=CC(N)=C1 CKQHAYFOPRIUOM-UHFFFAOYSA-N 0.000 claims description 4
- NIQIPYGXPZUDDP-UHFFFAOYSA-N 3-aminocyclohexan-1-ol Chemical compound NC1CCCC(O)C1 NIQIPYGXPZUDDP-UHFFFAOYSA-N 0.000 claims description 4
- CGLVZFOCZLHKOH-UHFFFAOYSA-N 8,18-dichloro-5,15-diethyl-5,15-dihydrodiindolo(3,2-b:3',2'-m)triphenodioxazine Chemical compound CCN1C2=CC=CC=C2C2=C1C=C1OC3=C(Cl)C4=NC(C=C5C6=CC=CC=C6N(C5=C5)CC)=C5OC4=C(Cl)C3=NC1=C2 CGLVZFOCZLHKOH-UHFFFAOYSA-N 0.000 claims description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 4
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 4
- 239000006229 carbon black Substances 0.000 claims description 4
- 238000004898 kneading Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- GTDQGKWDWVUKTI-UHFFFAOYSA-N o-aminoacetophenone Chemical compound CC(=O)C1=CC=CC=C1N GTDQGKWDWVUKTI-UHFFFAOYSA-N 0.000 claims description 4
- 229940099800 pigment red 48 Drugs 0.000 claims description 3
- 239000004014 plasticizer Substances 0.000 claims description 3
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- 229920006172 Tetrafluoroethylene propylene Polymers 0.000 claims description 2
- 239000006096 absorbing agent Substances 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 2
- 229910001634 calcium fluoride Inorganic materials 0.000 claims description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000292 calcium oxide Substances 0.000 claims description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 2
- 238000003490 calendering Methods 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- 239000002270 dispersing agent Substances 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 239000000080 wetting agent Substances 0.000 claims description 2
- 230000006835 compression Effects 0.000 abstract description 9
- 238000007906 compression Methods 0.000 abstract description 9
- 125000000524 functional group Chemical group 0.000 abstract description 8
- -1 amino, imino, azo Chemical group 0.000 abstract description 7
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052736 halogen Inorganic materials 0.000 abstract description 6
- 150000002367 halogens Chemical class 0.000 abstract description 6
- 150000001409 amidines Chemical class 0.000 abstract description 3
- 238000004132 cross linking Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 8
- 125000003118 aryl group Chemical group 0.000 description 6
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- MSTZGVRUOMBULC-UHFFFAOYSA-N 2-amino-4-[2-(3-amino-4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropan-2-yl]phenol Chemical group C1=C(O)C(N)=CC(C(C=2C=C(N)C(O)=CC=2)(C(F)(F)F)C(F)(F)F)=C1 MSTZGVRUOMBULC-UHFFFAOYSA-N 0.000 description 3
- VQQVWGVXDIPORV-UHFFFAOYSA-N Tryptanthrine Chemical group C1=CC=C2C(=O)N3C4=CC=CC=C4C(=O)C3=NC2=C1 VQQVWGVXDIPORV-UHFFFAOYSA-N 0.000 description 3
- 229910021485 fumed silica Inorganic materials 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 125000000041 C6-C10 aryl group Chemical group 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229920002313 fluoropolymer Polymers 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- 229910002018 Aerosil® 300 Inorganic materials 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920001774 Perfluoroether Polymers 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical group C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000002971 oxazolyl group Chemical group 0.000 description 1
- UJMWVICAENGCRF-UHFFFAOYSA-N oxygen difluoride Chemical compound FOF UJMWVICAENGCRF-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or 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; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or 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; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions of homopolymers or 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; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
-
- 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
Abstract
The invention belongs to the technical field of fluororubber, and particularly relates to a fluororubber elastomer and a preparation method thereof. The invention selects aminophenol vulcanizing agent and adds compound containing amino, imino, azo, amidine, ether, hydroxyl, carbonyl, halogen and other reactive functional groups as auxiliary crosslinking agent, the prepared fluororubber elastomer has improved hardness, tensile strength and compression set, the system of the invention can be compatible with auxiliary crosslinking agents with various structures, excellent performance improvement effect can be realized, the compression set rate of the fluororubber elastomer is obviously reduced, the auxiliary crosslinking agent is cheap and easy to obtain, and can achieve better performance improvement effect only by less addition amount, thus having extremely high industrialization value.
Description
Technical Field
The invention belongs to the technical field of fluororubber, and particularly relates to the field of IPC (industrial personal computer) classification No. C08K5/00, in particular to a fluororubber elastomer and a preparation method thereof.
Background
Fluororubber is a rubber material with excellent physical and mechanical properties, chemical corrosion resistance and ageing resistance, and has wide application in the fields of sealing products, aerospace, semiconductors, petrochemical industry and the like. The vulcanizing agents commonly used in industry are mainly peroxides, organic amines and bisphenols, wherein a crosslinking system formed by the vulcanizing agents with amino groups and bisphenol groups has higher high temperature resistance, can resist the high temperature of 320 ℃, and is more concerned in the special field. The vulcanization mechanism is mainly ion type, and in the vulcanization process, phenolic hydroxyl and amino at the ortho position on a benzene ring and a carbon-nitrogen triple bond in nitrile groups at vulcanization points of fluororubber carry out crosslinking reaction:
。
the prior art CN 106317598B discloses a crosslinked fluoroplastic heat-shrinkable sleeve, wherein an alkenyl-containing cyanate compound is added as a crosslinking aid, and the prepared crosslinked fluoroplastic heat-shrinkable sleeve has better high-temperature resistance and electrical property, but has no obvious improvement on mechanical properties such as compression set and the like.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a fluororubber elastomer with high hardness, high tensile strength and low compression set.
Another object of the present invention is to provide a method for producing the above-mentioned fluororubber elastomer.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
a fluororubber elastomer is prepared from the following raw materials: fluororubber raw rubber, filler, vulcanizing agent, auxiliary crosslinking agent and auxiliary agent;
the auxiliary crosslinking agent is a compound with a reactive functional group connected through a connecting group;
the linking group is selected from a substituted or unsubstituted aliphatic carbon chain, an aliphatic carbon ring, an aromatic ring, or a combination thereof;
the reactive functional group comprises two or more of substituted or unsubstituted amino, imino, azo, amidino, ether, hydroxyl, carbonyl and halogen.
Preferably, the two or more reactive functional groups are attached at ortho or meta positions of the aliphatic carbocyclic ring or aromatic ring.
Preferably, the fatty carbon chain is a C1-20 carbon chain; the aliphatic carbocycle is C3-8 carbocycle; the aromatic ring is a C6-10 aromatic ring; the aliphatic carbon chain, the aliphatic carbon ring and the aromatic ring can be substituted by one or more groups of C1-6 alkyl, C6-10 aryl, hydroxyl, carbonyl, cyano, sulfonyl, nitro and halogen.
Preferably, the reactive functional group can be substituted by one or more groups of C1-6 alkyl, C6-10 aryl, hydroxyl, carbonyl, cyano, sulfonyl, nitro and halogen.
Preferably, the co-crosslinking agent is selected from pigment Red 48:2 (CAS number: 7023-61-2), permanent violet RL (CAS number: 6358-30-1), o-aminoacetophenone (CAS number: 551-93-9), m-aminoacetophenone (CAS number: 99-03-6), ethanolamine (CAS number: 141-43-5), or 3-aminocyclohexanol (CAS number: 6850-39-1).
Preferably, the preparation raw materials comprise, by weight, 80-150 parts of fluororubber raw rubber, 15-30 parts of filler, 1-5 parts of vulcanizing agent, 0.1-2 parts of auxiliary crosslinking agent and 0.1-5 parts of auxiliary agent.
Further preferably, the preparation raw materials comprise, by weight, 100 parts of fluororubber raw rubber, 25 parts of filler, 1 part of vulcanizing agent, 0.5-2 parts of auxiliary crosslinking agent and 0.5 part of auxiliary agent.
Preferably, the vulcanizing agent is an aminophenol vulcanizing agent.
Preferably, the vulcanizing agent is 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (CAS number 83558-87-6).
The invention can improve the hardness, strength, pressure change and other performances of the fluororubber elastomer by adding the compound containing the reactive functional groups such as amino, imino, azo, amidine, ether, hydroxyl, carbonyl or halogen and the like as the auxiliary crosslinking agent. The invention specifically selects the compound with the similar reaction group with the vulcanizing agent to enable the compound to participate in the crosslinking reaction in the system, so as to improve the crosslinking degree of the system, form a more compact structure and further improve the mechanical property of the fluororubber. The inventor discovers in the research that when the molecule of the auxiliary cross-linking agent contains nitrogen-containing groups and hydrogen is arranged on nitrogen, the cross-linking degree is higher, the mechanical property of the fluororubber is better, and amino or imino can react with cyano in the raw fluororubber to form an amidine bond, so that the auxiliary cross-linking effect is achieved. The inventor also discovers that when the ortho-position or meta-position of the nitrogen-containing group of the auxiliary cross-linking agent has an oxygen-containing group such as hydroxyl or carbonyl, the auxiliary cross-linking agent can simultaneously react with cyano groups of the vulcanized point of the fluororubber to generate an oxazole ring structure with a stable rigid structure, so that the cross-linking degree is remarkably improved, and the hardness, the strength, the pressure change and other performances of the fluororubber elastomer are further improved. In addition, the auxiliary cross-linking agent selected by the invention has a similar structure with the aminophenol vulcanizing agent, so that the compatibility of the system is good.
Preferably, the fluororubber raw rubber is FKM (vinylidene fluoride) raw rubber, FFKM (perfluoroether) raw rubber or FEPM (tetrapropylfluoride) raw rubber.
Fluororubber raw rubber is commercially available, and its purchase source may not be particularly limited.
The FFKM raw rubber is FFKM raw rubber produced by Solvay.
Preferably, the filler comprises one or more of white carbon black, calcium sulfate, barium sulfate, calcium carbonate, calcium oxide, calcium fluoride and carbon fiber.
Further preferably, the white carbon black is vapor phase white carbon black.
Fumed silica is commercially available, and the source of purchase thereof is not particularly limited.
As an example, the fumed silica is AEROSIL300 produced by Yingsheng, germany.
Preferably, the auxiliary agent comprises one or more of a plasticizer, an acid absorber, a scorch retarder, a wetting agent and a dispersing agent.
Preferably, the plasticizer is a fluorowax.
The fluorowax is commercially available, and the source of purchase thereof may not be particularly limited.
Preferably, the fluorowax is purchased from Shanghai Yiba chemical industry raw materials Co.
In another aspect, the present invention provides a method for preparing the above fluororubber elastomer, comprising the steps of:
s1: kneading fluororubber raw rubber at 100-120 ℃ for 1-3 min, adding filler, continuously banburying for 1-5 min, discharging rubber, calendaring to obtain sheets, and cooling the sheets for later use;
s2: putting the rubber sheet into a roll of an open mill, sequentially adding an auxiliary agent, an auxiliary cross-linking agent and a vulcanizing agent, uniformly mixing, carrying out thin pass for 2-5 times, discharging the rubber sheet to obtain a rubber compound, and cooling for later use;
s3: vulcanizing the mixed rubber at 120-200 ℃ for the first time to obtain a primary vulcanized product; and (3) placing the primary vulcanization product at 200-300 ℃ for secondary vulcanization to obtain the fluororubber elastomer.
Preferably, the temperature of the adhesive discharge in the step S1 is 150-170 ℃;
preferably, the pressure of primary vulcanization in the step S3 is 10-20 mpa, and the vulcanization time is 5-15 min.
Preferably, the secondary vulcanization time in the step S3 is 12-24 hours.
Further preferably, the specific steps of the preparation method include:
s1: placing fluororubber raw rubber into a banburying chamber for kneading for 2min after the temperature of the banburying machine is stable at 100-120 ℃, opening an upper top bolt to add filler into the banburying chamber, putting down the upper top bolt for continuous banburying for 2min, discharging rubber, rolling out sheets on an open mill at 150-170 ℃, and standing for more than 12h for cooling for later use;
s2: regulating the roll gap to 0.5mm in an open mill, putting the cooled rubber sheet into the open mill and wrapping the rubber sheet with the rubber sheet, sequentially adding an auxiliary agent, an auxiliary crosslinking agent and a vulcanizing agent, uniformly mixing, regulating the roll gap to 0.2mm, carrying out thin ventilation for 3-5 times, regulating the roll gap of the open mill to 1.0mm, discharging the rubber sheet to obtain rubber compound, and standing for more than 12 hours for cooling;
s3: placing the rubber compound into a flat vulcanizing machine, and vulcanizing once at the temperature of 150-200 ℃ and the pressure of 10-20 MPa for 5-15 min to obtain a once vulcanized product; and (3) putting the primary vulcanized product into a blast drying oven at 200-300 ℃ for secondary vulcanization, wherein the time is controlled to be 12-24 hours, and obtaining the fluororubber elastomer.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention selects a plurality of auxiliary crosslinking agents with different structures, has excellent auxiliary crosslinking effect, obviously reduces the compression set of the fluororubber elastomer, and has wider application range and longer service life;
2. the addition of the auxiliary crosslinking agent can also improve the hardness and tensile strength of the fluororubber elastomer, and effectively improve the mechanical properties of the fluororubber elastomer;
3. the invention selects the vulcanizing agent containing amino and phenol groups, and the prepared fluororubber elastomer has higher high temperature resistance and can resist the high temperature of 320 ℃;
4. the auxiliary crosslinking agent selected by the invention is low in cost and easy to obtain, and can achieve better performance improvement effect only by less addition amount, thereby having extremely high industrialization value;
5. based on the findings of the present invention, a skilled person can select different auxiliary crosslinking agents according to the needs of the actual application scenario, so as to obtain the required performance.
Detailed Description
Example 1
The embodiment provides a fluororubber elastomer, which is prepared from the following raw materials in parts by weight: 100 parts of FFKM raw rubber, 25 parts of fumed silica, 1 part of vulcanizing agent, 0.5 part of auxiliary crosslinking agent and 0.5 part of fluorine wax; the vulcanizing agent is 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, and the auxiliary crosslinking agent is pigment red 48:2.
The embodiment also provides a preparation method of the fluororubber elastomer, which comprises the following specific steps:
s1: placing fluororubber raw rubber into a banburying chamber for kneading for 2min after the temperature of the banburying machine is stable, opening an upper top bolt to add filler into the banburying chamber, putting down the upper top bolt for continuous banburying for 2min, discharging rubber, rolling out sheets on an open mill at 150 ℃, and standing for 12h for cooling for standby;
s2: adjusting the roll gap to 0.5mm in an open mill, putting the cooled rubber sheet into the open mill and wrapping the rubber sheet with the rubber sheet, sequentially adding fluorine wax, auxiliary crosslinking agent and vulcanizing agent, uniformly mixing, adjusting the roll gap to 0.2mm, thinning the rubber sheet for 3 times, adjusting the roll gap of the open mill to 1.0mm, discharging the rubber sheet to obtain rubber compound, and standing for 12 hours for cooling;
s3: placing the rubber compound into a flat vulcanizing machine, and vulcanizing for 10min at 180 ℃ under 15MPa to obtain a primary vulcanized product; and (3) putting the primary vulcanized product into a blast drying oven at 250 ℃ for secondary vulcanization, and controlling the time to be 24 hours to obtain the fluororubber elastomer.
Example 2
This example provides a fluororubber elastomer and a method for producing the same, and the embodiment is the same as example 1, except that: the auxiliary cross-linking agent is permanent violet RL.
Example 3
This example provides a fluororubber elastomer and a method for producing the same, and the embodiment is the same as example 1, except that: the auxiliary cross-linking agent is o-amino acetophenone.
Example 4
This example provides a fluororubber elastomer and a method for producing the same, and the embodiment is the same as example 1, except that: the auxiliary cross-linking agent is m-amino acetophenone.
Example 5
This example provides a fluororubber elastomer and a method for producing the same, and the embodiment is the same as example 1, except that: the auxiliary cross-linking agent is ethanolamine.
Example 6
This example provides a fluororubber elastomer and a method for producing the same, and the embodiment is the same as example 1, except that: the auxiliary cross-linking agent is 3-aminocyclohexanol.
Example 7
This example provides a fluororubber elastomer and a method for producing the same, and the embodiment is the same as example 1, except that: the addition amount of the auxiliary crosslinking agent is 1.0 weight parts.
Example 8
This example provides a fluororubber elastomer and a method for producing the same, and the embodiment is the same as example 1, except that: the addition amount of the auxiliary crosslinking agent is 1.5 parts by weight.
Example 9
This example provides a fluororubber elastomer and a method for producing the same, and the embodiment is the same as example 1, except that: the addition amount of the auxiliary crosslinking agent is 2.0 parts by weight.
Comparative example 1
This comparative example provides a fluororubber elastomer and a method for producing the same, the embodiment being the same as example 1, except that: no auxiliary cross-linking agent is added.
Comparative example 2
This comparative example provides a fluororubber elastomer and a method for producing the same, the embodiment being the same as example 1, except that: the auxiliary cross-linking agent is tryptanthrin (CAS number: 13220-57-0).
Comparative example 3
This comparative example provides a fluororubber elastomer and a method for producing the same, the embodiment being different from comparative example 1 in that: the addition amount of the vulcanizing agent was 1.5 parts by weight.
Performance testing
Hardness, tensile strength, compression set test: examples 1 to 9 and comparative examples 1 to 3 were tested for hardness, tensile strength, compression set, according to GB/T531.1-2008 (hardness), GB/T528-2009 (tensile strength), GB T7759.1-2015 (compression set), respectively, and the results are shown in Table 1.
TABLE 1
According to test data, in the system of the invention, the auxiliary crosslinking agents containing amino, imino, azo, amidine, ether, hydroxyl, carbonyl, halogen and other reactive groups can play roles in promoting crosslinking to different degrees so as to improve the performance of the fluororubber elastomer; moreover, the test results also prove that the auxiliary crosslinking agent required by the system has higher compatibility to the connecting groups, can realize the effect of auxiliary crosslinking no matter carbon chain connection, aliphatic ring connection or aromatic ring connection, has different structures of the connecting groups and different relative positions of the reactive functional groups, has different effects of improving the performance of the fluororubber elastomer, and has the most obvious improvement of the hardness, tensile strength and compression set of the fluororubber elastomer when the reactive functional groups are nitrogen-containing groups, especially amino groups and ortho-oxygen-containing groups.
Claims (5)
1. The fluororubber elastomer is characterized by comprising, by weight, 80-150 parts of fluororubber raw rubber, 15-30 parts of filler, 1-5 parts of vulcanizing agent, 0.1-2 parts of auxiliary crosslinking agent and 0.1-5 parts of auxiliary agent;
the auxiliary cross-linking agent is selected from pigment red 48:2, permanent violet RL, o-aminoacetophenone, m-aminoacetophenone or 3-aminocyclohexanol;
the vulcanizing agent is an aminophenol vulcanizing agent.
2. The fluoroelastomer of claim 1 wherein said fluororubber green is FKM green, FFKM green or FEPM green.
3. The fluororubber elastomer according to claim 1, wherein the filler comprises one or more of white carbon black, calcium sulfate, barium sulfate, calcium carbonate, calcium oxide, calcium fluoride, carbon fiber.
4. The fluororubber elastomer according to claim 1, wherein the auxiliary agent comprises one or more of a plasticizer, an acid absorber, a scorch retarder, a wetting agent, and a dispersing agent.
5. A method for producing the fluororubber elastomer according to any one of claims 1 to 4, comprising the steps of:
s1: kneading fluororubber raw rubber at 100-120 ℃ for 1-3 min, adding filler, continuously banburying for 1-5 min, discharging rubber, calendaring to obtain sheets, and cooling the sheets for later use;
s2: putting the rubber sheet into a roll of an open mill, sequentially adding an auxiliary agent, an auxiliary cross-linking agent and a vulcanizing agent, uniformly mixing, carrying out thin pass for 2-5 times, discharging the rubber sheet to obtain a rubber compound, and cooling for later use;
s3: vulcanizing the mixed rubber at 120-200 ℃ for the first time to obtain a primary vulcanized product; and (3) placing the primary vulcanization product at 200-300 ℃ for secondary vulcanization to obtain the fluororubber elastomer.
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