CN116751428A - Preparation method of high-temperature low-compression permanent deformation perfluoroether elastomer composition - Google Patents
Preparation method of high-temperature low-compression permanent deformation perfluoroether elastomer composition Download PDFInfo
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- CN116751428A CN116751428A CN202311065720.1A CN202311065720A CN116751428A CN 116751428 A CN116751428 A CN 116751428A CN 202311065720 A CN202311065720 A CN 202311065720A CN 116751428 A CN116751428 A CN 116751428A
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- emulsion
- vulcanization
- perfluoroether
- elastomer composition
- fluorine
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- 229920001774 Perfluoroether Polymers 0.000 title claims abstract description 117
- 229920001971 elastomer Polymers 0.000 title claims abstract description 117
- UJMWVICAENGCRF-UHFFFAOYSA-N oxygen difluoride Chemical compound FOF UJMWVICAENGCRF-UHFFFAOYSA-N 0.000 title claims abstract description 114
- 239000000806 elastomer Substances 0.000 title claims abstract description 111
- 239000000203 mixture Substances 0.000 title claims abstract description 68
- 238000007906 compression Methods 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 238000004073 vulcanization Methods 0.000 claims abstract description 125
- 239000000178 monomer Substances 0.000 claims abstract description 104
- 239000000839 emulsion Substances 0.000 claims abstract description 90
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 45
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 42
- 230000006835 compression Effects 0.000 claims abstract description 42
- 239000011737 fluorine Substances 0.000 claims abstract description 42
- 125000002560 nitrile group Chemical group 0.000 claims abstract description 40
- 238000002156 mixing Methods 0.000 claims abstract description 30
- 239000003999 initiator Substances 0.000 claims abstract description 27
- 229920000642 polymer Polymers 0.000 claims abstract description 27
- 239000012986 chain transfer agent Substances 0.000 claims abstract description 24
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 22
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 22
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 20
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- 239000008367 deionised water Substances 0.000 claims abstract description 13
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000000748 compression moulding Methods 0.000 claims abstract description 10
- 238000009777 vacuum freeze-drying Methods 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 10
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 7
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 4
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 25
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 20
- 229910052740 iodine Inorganic materials 0.000 claims description 15
- 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 13
- 238000000465 moulding Methods 0.000 claims description 13
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 12
- 239000011630 iodine Substances 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- 239000001301 oxygen Substances 0.000 claims description 11
- 230000009471 action Effects 0.000 claims description 10
- 238000006116 polymerization reaction Methods 0.000 claims description 10
- -1 polyoxyethylene Polymers 0.000 claims description 10
- 239000003792 electrolyte Substances 0.000 claims description 9
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 9
- 238000005063 solubilization Methods 0.000 claims description 9
- 230000007928 solubilization Effects 0.000 claims description 9
- CRHIAMBJMSSNNM-UHFFFAOYSA-N tetraphenylstannane Chemical compound C1=CC=CC=C1[Sn](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 CRHIAMBJMSSNNM-UHFFFAOYSA-N 0.000 claims description 8
- WIEYKFZUVTYEIY-UHFFFAOYSA-N 1,1,2,2,3,3-hexafluoro-1,3-diiodopropane Chemical compound FC(F)(I)C(F)(F)C(F)(F)I WIEYKFZUVTYEIY-UHFFFAOYSA-N 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000009833 condensation Methods 0.000 claims description 4
- 230000005494 condensation Effects 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- SRDQTCUHAMDAMG-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8-hexadecafluoro-1,8-diiodooctane Chemical compound FC(F)(I)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)I SRDQTCUHAMDAMG-UHFFFAOYSA-N 0.000 claims description 3
- JOQDDLBOAIKFQX-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,5,6,6-dodecafluoro-1,6-diiodohexane Chemical compound FC(F)(I)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)I JOQDDLBOAIKFQX-UHFFFAOYSA-N 0.000 claims description 3
- AAAXMNYUNVCMCJ-UHFFFAOYSA-N 1,3-diiodopropane Chemical compound ICCCI AAAXMNYUNVCMCJ-UHFFFAOYSA-N 0.000 claims description 3
- ROUYUBHVBIKMQO-UHFFFAOYSA-N 1,4-diiodobutane Chemical compound ICCCCI ROUYUBHVBIKMQO-UHFFFAOYSA-N 0.000 claims description 3
- QLIMAARBRDAYGQ-UHFFFAOYSA-N 1,6-diiodohexane Chemical compound ICCCCCCI QLIMAARBRDAYGQ-UHFFFAOYSA-N 0.000 claims description 3
- KZDTZHQLABJVLE-UHFFFAOYSA-N 1,8-diiodooctane Chemical compound ICCCCCCCCI KZDTZHQLABJVLE-UHFFFAOYSA-N 0.000 claims description 3
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 3
- 229920006197 POE laurate Polymers 0.000 claims description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 3
- 150000001735 carboxylic acids Chemical class 0.000 claims description 3
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 3
- 239000012025 fluorinating agent Substances 0.000 claims description 3
- 229940049964 oleate Drugs 0.000 claims description 3
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 3
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 3
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 3
- RZJRJXONCZWCBN-UHFFFAOYSA-N octadecane Chemical compound CCCCCCCCCCCCCCCCCC RZJRJXONCZWCBN-UHFFFAOYSA-N 0.000 claims 2
- 229940038384 octadecane Drugs 0.000 claims 1
- 238000005345 coagulation Methods 0.000 abstract description 6
- 230000015271 coagulation Effects 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 2
- 238000004132 cross linking Methods 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000009396 hybridization Methods 0.000 description 8
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 7
- 238000002161 passivation Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 4
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 description 4
- 238000004334 fluoridation Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000013638 trimer Substances 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 229920002313 fluoropolymer Polymers 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 238000007363 ring formation reaction Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000003682 fluorination reaction Methods 0.000 description 2
- 229920001973 fluoroelastomer Polymers 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- GWTYBAOENKSFAY-UHFFFAOYSA-N 1,1,1,2,2-pentafluoro-2-(1,2,2-trifluoroethenoxy)ethane Chemical compound FC(F)=C(F)OC(F)(F)C(F)(F)F GWTYBAOENKSFAY-UHFFFAOYSA-N 0.000 description 1
- BLTXWCKMNMYXEA-UHFFFAOYSA-N 1,1,2-trifluoro-2-(trifluoromethoxy)ethene Chemical compound FC(F)=C(F)OC(F)(F)F BLTXWCKMNMYXEA-UHFFFAOYSA-N 0.000 description 1
- WUMVZXWBOFOYAW-UHFFFAOYSA-N 1,2,3,3,4,4,4-heptafluoro-1-(1,2,3,3,4,4,4-heptafluorobut-1-enoxy)but-1-ene Chemical compound FC(F)(F)C(F)(F)C(F)=C(F)OC(F)=C(F)C(F)(F)C(F)(F)F WUMVZXWBOFOYAW-UHFFFAOYSA-N 0.000 description 1
- BZPCMSSQHRAJCC-UHFFFAOYSA-N 1,2,3,3,4,4,5,5,5-nonafluoro-1-(1,2,3,3,4,4,5,5,5-nonafluoropent-1-enoxy)pent-1-ene Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)=C(F)OC(F)=C(F)C(F)(F)C(F)(F)C(F)(F)F BZPCMSSQHRAJCC-UHFFFAOYSA-N 0.000 description 1
- KURZCZMGELAPSV-UHFFFAOYSA-N [Br].[I] Chemical compound [Br].[I] KURZCZMGELAPSV-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 238000010060 peroxide vulcanization Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
- 230000036962 time dependent Effects 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
- C08L27/18—Homopolymers or copolymers or tetrafluoroethene
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
-
- 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
- C08F214/26—Tetrafluoroethene
- C08F214/262—Tetrafluoroethene with fluorinated vinyl ethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- 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 application provides a preparation method of a high-temperature low-compression permanent deformation perfluoroether elastomer composition, which comprises the following steps: adding deoxidized deionized water, an emulsifier, a vulcanization point monomer containing bromine or iodine, a chain transfer agent, an initiator and a copolymerization fluorine-containing monomer into a reactor to obtain polymer emulsion; taking polymer emulsion as seed, adding nitrile group-containing vulcanization point monomer, chain transfer agent and copolymerized fluorine-containing monomer in gradient or quantitative manner to obtain perfluoroether elastomer emulsion containing two vulcanization point monomers, and synthesizing PFA emulsion at the same time; mixing the perfluoroether elastomer emulsion and the PFA emulsion, washing after coagulation, vacuum freeze-drying, passivating the fluorinated end groups, and mixing to obtain the perfluoroether elastomer; and blending the perfluoroether elastomer with a vulcanization crosslinking agent and a catalyst, performing compression molding, and performing secondary vulcanization to obtain the high-temperature low-compression permanent deformation perfluoroether elastomer composition. The perfluoro ether elastomer composition prepared by the application has the characteristics of stable chemical property, excellent mechanical property and low compression set at high temperature.
Description
Technical Field
The application relates to the field of preparation of perfluoroether elastomers, in particular to a preparation method of a perfluoroether elastomer composition with high temperature and low compression set.
Background
The perfluoro ether elastomer is a copolymer polymerized by Tetrafluoroethylene (TFE), perfluoro alkyl vinyl ether (PAVE, including perfluoro methyl vinyl ether PMVE, perfluoro ethyl vinyl ether PEVE, perfluoro propyl vinyl ether PPVE), a third monomer (vulcanization point monomer CSM) and other monomers, and the perfluoro ether elastomer composition has the same excellent high temperature resistance and chemical medium resistance as PTFE, and can be applied to the field of elastic sealing. The performance of perfluoroether elastomer compositions is closely related to the cross-linked structure of the perfluoroether elastomer composition in addition to its molecular structure. The general peroxide-cured perfluoroether elastomer is mainly applied to a strong medium environment, and the maximum use temperature is about 230 ℃. In the early 21 st century, italy Solvay developed peroxide-initiated crosslinking high temperature-resistant perfluoroether vulcanization aid, which was used in PFR 95HT perfluoroether rubber, and which was excellent in dielectric properties and high temperature resistance, and the maximum use temperature was 300 ℃. The perfluoro ether rubber with higher use temperature is vulcanized by nitrile groups, an amine vulcanizing agent or triazine structures are generated among macromolecules, and the maximum working temperature can reach 327 ℃, such as Kalrez series products of DuPont company in U.S.
However, a high compression set as compared to other fluororubbers is one of the few disadvantages of perfluoroether elastomer compositions. How to reduce the compression set at high temperature under the condition of keeping the other properties of the perfluoroether elastomer composition unchanged is an insurmountable problem in the application in the semiconductor industry (high temperature low compression set means that the compression set is less than 20% when the temperature is 200 ℃ and less than 50% when the temperature is 300 ℃).
Patent CN115413289B provides a fluorocopolymer composition capable of forming a crosslinked rubber article which is small in compression set at high temperature and which does not break after compression, and a crosslinked rubber article. The application employs two fluorocopolymer compositions: a fluorine-containing copolymer A comprising a unit having a nitrile group and a tetrafluoroethylene-based unit; a fluorocopolymer B which is contained in the composition in the form of particles and has units of at least 1 functional group selected from the group consisting of a group having a carbonyl group, a hydroxyl group, an epoxy group and an isocyanate group, and units based on tetrafluoroethylene; and a crosslinking agent.
In the conventional vulcanization method of the nitrile group of the perfluoro ether elastomer, tetraphenyltin is used as a catalyst, and the nitrile group forms a triazine ring of a trimer in the vulcanization process, but the cyclized crosslinking vulcanization speed is slow, and the molding is difficult. The vulcanization method using bromine or iodine as the vulcanization site is a radical crosslinking reaction, and has better curability than the nitrile vulcanization method, but on the other hand, the problem of entering the sulfide structure due to the hydrocarbon groups in the vulcanizing agent organic peroxide and the vulcanization aid is also considered. The application adopts two vulcanization point monomers, but shares one vulcanization system. The hybrid crosslinking is realized by adopting a seed solubilization emulsion polymerization technology, and the respective advantages of the nitrile group vulcanization point monomer and the peroxide vulcanization point monomer containing bromine or iodine are fully exerted.
The nano filler is beneficial to increasing the interaction between the nano filler and the fluorine-containing polymer, obviously enhancing the mechanical property of the material and is an effective means for improving the permanent deformation of high-temperature compression. But at the same time, the nano particles are easy to agglomerate, the viscosity of the fluorine-containing polymer is also larger, so that the fluorine-containing polymer is difficult to achieve uniform dispersion of nano size, and the performance of the rubber material is influenced by the effect of filler dispersion. Thus, achieving good dispersion of the nanoparticles in the rubber matrix is an important prerequisite for the manufacture of the ideal nanocomposite.
Based on this, a new solution is needed to achieve a low compression set at high temperatures while maintaining the other properties of the perfluoroether elastomer composition.
Disclosure of Invention
In view of this, the present application provides in a first aspect a process for preparing a high temperature low compression set perfluoroether elastomer composition comprising the steps of:
s1: adding deoxidized deionized water accounting for 60-70% of the volume of the deoxidized deionized water, an emulsifier, a vulcanization point monomer containing bromine or iodine, a chain transfer agent, an initiator and a copolymerization fluorine-containing monomer into a reactor with the oxygen concentration lower than 20ppm, and performing emulsion polymerization reaction under the action of the initiator to form polymer emulsion;
s2: taking the polymer emulsion prepared in the step S1 as seeds, adding nitrile group-containing vulcanization point monomers, chain transfer agents and copolymerized fluorine-containing monomers in a gradient or quantitative manner to carry out seed solubilization emulsion polymerization, obtaining perfluoroether elastomer emulsion containing the two vulcanization point monomers after polymerization reaction is stopped, and synthesizing PFA emulsion in another reactor;
s3: mixing the perfluoroether elastomer emulsion prepared in the step S2 with the PFA emulsion, performing electrolyte coagulation, washing, vacuum freeze-drying, fluorination, end group passivation and thin-pass mixing to obtain the perfluoroether elastomer;
s4: hybridization crosslinking of the perfluoro ether elastomer prepared in S3, a vulcanization crosslinking agent and a catalyst, thin blending, compression molding and secondary vulcanization to obtain the perfluoro ether elastomer composition with high temperature and low compression set,
wherein the mass ratio of the fluorine-containing monomers in the S1 and the S2 is 1:1-3:1, and the total addition amount of the fluorine-containing monomers is 15wt% to 25wt% of the total mass of the polymer emulsion in the S1; the PFA emulsion in the S2 consists of 91-98 wt% of TFE, 1-8 wt% of PPVE and 0.5-1.5 wt% of nitrile group-containing vulcanization point monomer.
Preferably, the emulsifier in S1 includes any one of fluoroether carboxylic acid, polyoxyethylene oleate and polyoxyethylene laurate; the addition amount of the emulsifier is 0.5-2 wt% of the total amount of the fluorine-containing monomers in the S1 and the S2.
Preferably, the vulcanization point monomer containing bromine or iodine in the S1 comprises R 1 CH=CR 2 CR 3 、R f -I and I-R f -any of I, wherein R 1 、R 2 、R 3 Selected from H, br, F, R f Or R is f Br, and R 1 、R 2 、R 3 At least one of which is Br or R f Br，R f Is perfluoroalkyl; the addition amount of the vulcanization point monomer containing bromine and/or iodine is 0.4-0.6 wt% of the total amount of the co-polymerized fluorine-containing monomers in the S1 and the S2.
Preferably, the S1 and S2 medium chain transferThe transfer agent is I- (CF) 2 ) n -I, comprising 1, 3-diiodopropane, 1, 4-diiodobutane, 1, 6-diiodohexane, 1, 8-diiodooctane, 1, 3-diiodoperfluoropropane, 1, 4-diiodoperfluorobutane, 1, 6-diiodoperfluorohexane or 1, 8-diiodoperfluorooctane; the addition amount of the chain transfer agent in the S1 and the S2 is 0.05-2 wt% of the total amount of the fluorine-containing monomers in the S1 and the S2.
Preferably, the initiator in S1 includes any one of sodium persulfate, potassium persulfate and ammonium persulfate; the addition amount of the initiator is 0.05 to 0.5 weight percent of the total amount of the fluorine-containing monomers in the S1 and the S2.
Preferably, the comonomer in S1 and S2 comprises tetrafluoroethylene and perfluoroalkyl vinyl ether.
Preferably, the nitrile group-containing cure site monomer in S2 and the nitrile group-containing cure site monomer in PFA are each independently selected from CF 2 =CF-O-R f X, wherein X is O- (CF) 2 ) n CN or CN; the addition amount of the nitrile group-containing vulcanization point monomer in the S2 is 1.5-3 wt% of the total amount of the co-polymerized fluorine-containing monomers in the S1 and the S2.
Preferably, the vulcanization crosslinking agent in the step S4 is tetraphenyltin, and the catalyst is hexaoxy-cyclo-octadecane; the addition amounts of the vulcanization crosslinking agent and the catalyst are respectively 1.5-3 wt% and 2.5-5 wt% of the total mass of the perfluoroether elastomer emulsion and the PFA emulsion, wherein the mass ratio of the perfluoroether elastomer emulsion to the PFA emulsion is 10:1-5:1.
Preferably, the fluorinating agent used in the step S3 is 10wt% of fluorine gas, and the balance gas is nitrogen gas.
Preferably, the molding condition in the step S4 is that the pressure is 8-10MPa, the temperature is 160-175 ℃ and the time is 5-16min; the secondary vulcanization condition is that the temperature is 200-220 ℃ and the time is 10-24 hours.
In a second aspect, the present application provides a high temperature low compression set perfluoroether elastomer composition made by the above-described method of preparation.
Compared with the prior art, the beneficial effects that above-mentioned at least one technical scheme that this description embodiment adopted can reach include at least:
(1) In the application, two vulcanization point monomers are added simultaneously in the process of preparing the perfluoroether elastomer composition, a vulcanization method with nitrile groups as vulcanization positions is a cyclization crosslinking reaction, although the vulcanization point monomers containing nitrile groups are added to form a triazine ring of a trimer in the vulcanization process, the cyclization crosslinking vulcanization speed is slow, the molding is difficult, the vulcanization method with bromine or iodine as the vulcanization positions is a free radical crosslinking reaction, compared with the nitrile group vulcanization method, the vulcanization performance is better, and the vulcanization reaction speed can be accelerated by adding the vulcanization point monomers containing nitrile groups and bromine or iodine, and the triazine ring of the trimer can well realize the effect of high-temperature low-compression permanent deformation of the perfluoroether elastomer composition;
(2) The PFA emulsion synthesized by the application is composed of TFE, PPVE and nitrile-group-containing vulcanization point monomers, on one hand, the nitrile-group-containing vulcanization point monomers can crosslink TFE chain segments and PPVE chain segments in the PFA to form a partial grid structure, and on the other hand, in the subsequent secondary vulcanization stage, the PFA emulsion and the perfluoroether elastomer emulsion containing the two vulcanization point monomers can be better crosslinked, meanwhile, the application adopts a seed emulsion polymerization mode to synthesize the perfluoroether elastomer emulsion, adopts a triazine curing system, takes polymer emulsion obtained by bromine-or iodine-containing vulcanization point monomers as seeds, takes emulsion formed by nitrile-group-containing vulcanization point monomers as a shell, and forms the perfluoroether elastomer emulsion with a core-shell structure, and the prepared PFA emulsion and the perfluoroether elastomer emulsion can be better crosslinked further, so that the prepared perfluoroether elastomer composition has high-temperature low-compression permanent deformation and excellent mechanical properties.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and that other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic representation of the time-dependent parameters of the seed-solubilizing emulsion polymerization process of the present application, wherein the parameters are plotted on the ordinateThe numbers include pressure (MPa), temperature (. Degree.C.), concentration (mol/m) 3 ) Or feed rate (mol/hr), with time (hr) on the abscissa; s1, S2 and S3 represent synthetic steps; a, B and C represent the end points of the corresponding synthesis steps; k (k) 1 ，k 2 And k 3 Represents gradient, k 1 、k 2 、k 3 And 0. Gtoreq.and a larger value indicates a larger rate of change per unit time.
Detailed Description
Embodiments of the present application will be described in detail below with reference to the accompanying drawings.
Other advantages and effects of the present application will become apparent to those skilled in the art from the following disclosure, which describes the embodiments of the present application with reference to specific examples. It will be apparent that the described embodiments are only some, but not all, embodiments of the application. The application may be practiced or carried out in other embodiments that depart from the specific details, and the details of the present description may be modified or varied from the spirit and scope of the present application. It should be noted that the following embodiments and features in the embodiments may be combined with each other without conflict. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
It should be apparent that the aspects described herein may be embodied in a wide variety of forms and that any specific structure and/or function described herein is merely illustrative. Based on the present disclosure, one skilled in the art will appreciate that one aspect described herein may be implemented independently of any other aspect, and that two or more of these aspects may be combined in various ways. For example, apparatus may be implemented and/or methods practiced using any number and aspects set forth herein. In addition, such apparatus may be implemented and/or such methods practiced using other structure and/or functionality in addition to one or more of the aspects set forth herein.
It should also be noted that the illustrations provided in the following embodiments merely illustrate the basic concept of the present application by way of illustration, and only the components related to the present application are shown in the drawings and are not drawn according to the number, shape and size of the components in actual implementation, and the form, number and proportion of the components in actual implementation may be arbitrarily changed, and the layout of the components may be more complicated.
In addition, in the following description, specific details are provided in order to provide a thorough understanding of the examples. However, it will be understood by those skilled in the art that the present application may be practiced without these specific details.
The high compression set as compared to other fluororubbers is one of the few disadvantages of perfluoroether elastomer compositions. How to reduce the compression set at high temperature under the condition of keeping the other properties of the perfluoroether elastomer composition unchanged is an insurmountable problem in the application in the semiconductor industry (high temperature low compression set means that the compression set is less than 20% when the temperature is 200 ℃ and less than 50% when the temperature is 300 ℃). Generally, nitrile groups form triazine rings of a trimer in the vulcanization process of the perfluoroether elastomer, but the vulcanization speed of cyclization crosslinking is slow, the molding is difficult, and the vulcanization method which takes bromine and iodine as vulcanization positions is used as a free radical crosslinking reaction, so that the vulcanization performance is better than that of the nitrile group vulcanization method. The application provides a preparation method of a perfluoroether elastomer composition with high temperature and low compression set, which realizes the high temperature and low compression set while not changing other properties of the perfluoroether elastomer composition.
Based on the method, the application provides a preparation method of the perfluoroether elastomer composition with high temperature and low compression set, wherein two vulcanization point monomers are added in the preparation process of the perfluoroether elastomer composition, and the vulcanization reaction speed is accelerated under the combined action of the two vulcanization point monomers, and the formed trimeric triazine ring can well realize the effect of the perfluoroether elastomer composition with high temperature and low compression set.
The following describes the technical scheme provided by each embodiment of the present application with reference to the accompanying drawings.
The present application provides in a first aspect a process for preparing a high temperature low compression set perfluoroether elastomer composition comprising the steps of:
s1: as shown in FIG. 1, deoxidized deionized water, an emulsifier, a vulcanization point monomer containing bromine or iodine, a chain transfer agent, an initiator and a copolymerization fluorine-containing monomer, which are 60 to 70% by volume of the deoxidized deionized water, are added into a reactor with an oxygen content of less than 20ppm, and the reactor pressure is maintained to fluctuate within a small range (k) 1 >0, i.e. the reaction is continued), the addition is stopped until the reaction is terminated (k 1 =0), emulsion polymerization is carried out under the action of an initiator to form polymer emulsion;
s2: the polymer emulsion prepared in S1 is used as seed, and the nitrile group-containing vulcanization point monomer (k) is added in a gradient or quantitative way 2 >0, i.e., continuous reaction), chain transfer agent and copolymerized fluoromonomer, stopping feeding until the polymerization reaction is stopped (k) 2 =0) obtaining a perfluoroether elastomer emulsion containing two vulcanization point monomers while synthesizing a PFA emulsion in another reactor;
s3: mixing the perfluoroether elastomer emulsion prepared in the step S2 with the PFA emulsion, performing electrolyte coagulation, washing, vacuum freeze-drying, fluorination, end group passivation and thin-pass mixing to obtain the perfluoroether elastomer;
s4: hybridization crosslinking of the perfluoro ether elastomer prepared in S3, a vulcanization crosslinking agent and a catalyst, thin blending, compression molding and secondary vulcanization to obtain the perfluoro ether elastomer composition with high temperature and low compression set,
wherein the mass ratio of the fluorine-containing monomers in the S1 and the S2 is 1:1-3:1, and the total addition amount of the fluorine-containing monomers is 15wt% to 25wt% of the total mass of the polymer emulsion in the S1; the PFA emulsion in the S2 consists of 91-98 wt% of TFE, 1-8 wt% of PPVE and 0.5-1.5 wt% of nitrile group-containing vulcanization point monomer.
In a second aspect, the present application provides a high temperature low compression set perfluoroether elastomer composition prepared by the method described above.
In order not to increase the amount of the initiator, it is necessary to prevent a trace amount of polymerization inhibiting impurities (such as oxygen) from entering the reaction system, and therefore, a preferred embodiment is as follows: by inert gas N 2 Purging andthe oxygen content in the reactor was monitored to be not higher than 20ppm.
Preferably, the emulsifier in S1 includes any one of fluoroether carboxylic acid, polyoxyethylene oleate and polyoxyethylene laurate; the addition amount of the emulsifier is 0.5-2 wt% of the total amount of the fluorine-containing monomers in the S1 and the S2.
Preferably, the vulcanization point monomer containing bromine or iodine in the S1 comprises R 1 CH=CR 2 CR 3 、R f -I and I-R f -any of I, wherein R 1 、R 2 、R 3 Selected from H, br, F, R f Or R is f Br, and R 1 、R 2 、R 3 At least one of which is Br or R f Br，R f Is perfluoroalkyl; the addition amount of the vulcanization point monomer containing bromine and/or iodine is 0.4-0.6 wt% of the total amount of the co-polymerized fluorine-containing monomers in the S1 and the S2.
Preferably, the chain transfer agent in S1 and S2 is I- (CF) 2 ) n -I, comprising 1, 3-diiodopropane, 1, 4-diiodobutane, 1, 6-diiodohexane, 1, 8-diiodooctane, 1, 3-diiodoperfluoropropane, 1, 4-diiodoperfluorobutane, 1, 6-diiodoperfluorohexane or 1, 8-diiodoperfluorooctane; the addition amount of the chain transfer agent in the S1 and the S2 is 0.05-2 wt% of the total amount of the fluorine-containing monomers in the S1 and the S2.
Preferably, the initiator in S1 includes any one of sodium persulfate, potassium persulfate and ammonium persulfate; the addition amount of the initiator is 0.05 to 0.5 weight percent of the total amount of the fluorine-containing monomers in the S1 and the S2.
Preferably, the comonomer in S1 and S2 comprises tetrafluoroethylene and perfluoroalkyl vinyl ether.
Preferably, the nitrile group-containing cure site monomer in S2 and the nitrile group-containing cure site monomer in PFA are each independently selected from CF 2 =CF-O-R f X, wherein X is O- (CF) 2 ) n CN or CN; the addition amount of the nitrile group-containing vulcanization point monomer in the S2 is 1.5-3 wt% of the total amount of the co-polymerized fluorine-containing monomers in the S1 and the S2.
Preferably, the vulcanization crosslinking agent in the step S4 is tetraphenyltin, and the catalyst is hexaoxy-cyclo-octadecane; the addition amounts of the vulcanization crosslinking agent and the catalyst are respectively 1.5-3 wt% and 2.5-5 wt% of the total mass of the perfluoroether elastomer emulsion and the PFA emulsion, wherein the mass ratio of the perfluoroether elastomer emulsion to the PFA emulsion is 10:1-5:1.
Preferably, the fluorinating agent used in the step S3 is 10wt% of fluorine gas, and the balance gas is nitrogen gas.
Preferably, the molding condition in the step S4 is that the pressure is 8-10MPa, the temperature is 160-175 ℃ and the time is 5-16min; the secondary vulcanization condition is that the temperature is 200-220 ℃ and the time is 10-24 hours.
It should be understood that the following limitations on the types and contents of the emulsifier, the bromine-or iodine-containing vulcanization point monomer, the chain transfer agent, the initiator, the nitrile group-containing vulcanization point monomer, the vulcanization crosslinking agent, the catalyst content, the molding conditions and the secondary vulcanization conditions in the present application are all preferred examples, and should not be construed as limiting the scope of protection.
Specific examples are listed below:
example 1
S1: into a 5L reactor having an oxygen concentration of not more than 20ppm, 3L of deoxidized deionized water and 3g of emulsifier CF were charged 3 -CF 2 -CF 2 -O-(CF 2 -CF 2 -O) 2 -CF 2 -COOH, 2.4g of bromine-containing cure site monomer BTFB, 0.3g of chain transfer agent 1, 4-diiodoperfluorobutane, 0.3g of initiator potassium persulfate, and 300g of a mixture of copolymerized fluoromonomers TFE and PMVE, emulsion polymerization under the action of initiator to form a polymer emulsion;
s2: taking the polymer emulsion prepared in the step S1 as seeds, adding 9g of nitrile group-containing vulcanization point monomer 8-CNVE, 0.3g of chain transfer agent 1, 4-diiodoperfluorobutane and 300g of mixture of copolymerized fluoromonomers TFE and PMVE for seed solubilization emulsion polymerization, obtaining perfluoroether elastomer emulsion containing two vulcanization point monomers after polymerization reaction is stopped, and simultaneously synthesizing PFA (weight percent is TFE: PPVE: nitrile group-containing vulcanization point monomer 8-CNVE=93:6:1) emulsion in another reactor;
s3: mixing 300g of perfluoroether elastomer emulsion and 30g of PFA emulsion, performing electrolyte coagulation, washing, vacuum freeze-drying, fluoridation of 10wt% of fluorine gas, end group passivation and thin-pass mixing to obtain the perfluoroether elastomer;
s4: and (3) carrying out hybridization crosslinking on the perfluoroether elastomer prepared in the step (S3) with 9.9g of a vulcanization crosslinking agent tetraphenyltin and 16.5g of a catalyst hexaoxacyclooctadecane, carrying out thin-pass blending, carrying out compression molding at 8MPa and 160 ℃ for 5min for molding, and keeping at 200 ℃ for 10h for secondary vulcanization to obtain the high-temperature low-compression permanent deformation perfluoroether elastomer composition.
Example 2
S1: into a 5L reactor having an oxygen concentration of not more than 20ppm, 3.5L of deoxidized deionized water and 5g of emulsifier CF were charged 3 -CF 2 -CF 2 -O-(CF 2 -CF 2 -O) 2 -CF 2 -COOH, 4.5g of bromine-containing cure site monomer BTFB, 15g of chain transfer agent 1, 3-diiodoperfluoropropane, 3.75g of initiator potassium persulfate, and 525g of a mixture of copolymerized fluoromonomers TFE and PMVE, emulsion polymerization under the action of initiator to form a polymer emulsion;
s2: taking the polymer emulsion prepared in the step S1 as seeds, adding 22.5g of nitrile group-containing vulcanization point monomer 8-CNVE, 15g of chain transfer agent 1, 3-diiodoperfluoropropane and 175g of mixture of copolymerized fluoromonomers TFE and PMVE for seed solubilization emulsion polymerization, obtaining perfluoroether elastomer emulsion containing two vulcanization point monomers after polymerization reaction is stopped, and simultaneously synthesizing PFA (weight percent is TFE: PPVE: nitrile group-containing vulcanization point monomer 8-CNVE=93:6:1) emulsion in another reactor;
s3: mixing 250g of perfluoroether elastomer emulsion and 50g of PFA emulsion, performing electrolyte coagulation, washing, vacuum freeze-drying, fluoridation of 10wt% of fluorine gas, end group passivation and thin-pass mixing to obtain the perfluoroether elastomer;
s4: and (3) carrying out hybridization crosslinking on the perfluoro ether elastomer prepared in the step (S3) with 4.5g of a vulcanization crosslinking agent tetraphenyltin and 7.5g of a catalyst hexaoxacyclooctadecane, carrying out thin-pass blending, carrying out compression molding at 10MPa and 175 ℃ for 16min for molding, and keeping at 220 ℃ for 24h for secondary vulcanization to obtain the high-temperature low-compression permanent deformation perfluoro ether elastomer composition.
Since the bromine-and iodine-containing vulcanization point monomers are peroxy-based vulcanization point monomers, it is necessary to use biwurtzite as a vulcanization crosslinking agent and TAIC (triallyl isocyanurate) as a vulcanization crosslinking assistant in the secondary vulcanization stage when the above-mentioned vulcanization point monomers are added alone.
Comparative example 1
S1: into a 5L reactor having an oxygen concentration of not more than 20ppm, 3L of deoxidized deionized water and 3g of emulsifier CF were charged 3 -CF 2 -CF 2 -O-(CF 2 -CF 2 -O) 2 -CF 2 -COOH, 11.4g of bromine-containing cure site monomer BTFB, 0.3g of chain transfer agent 1, 4-diiodoperfluorobutane, 0.3g of initiator potassium persulfate, and 300g of a mixture of copolymerized fluoromonomers TFE and PMVE, emulsion polymerization under the action of initiator to form a polymer emulsion;
s2: taking the polymer emulsion prepared in the step S1 as seeds, adding 0.3g of chain transfer agent 1, 4-diiodoperfluorobutane and 300g of mixture of copolymerized fluoromonomer TFE and PMVE for seed solubilization emulsion polymerization, and obtaining perfluoroether elastomer emulsion of monomer containing bromine vulcanization point after polymerization reaction is stopped;
s3: mixing 300g of perfluoroether elastomer emulsion and 30g of PFA (3M ™ Dyeon ™ Fluoroplastic PFA 6900GZ, solid content 40% and particle size 200 nm) emulsion, performing electrolyte condensation, washing, vacuum freeze drying, fluoridizing 10wt% of fluorine gas, passivating end groups, and thin-pass mixing to obtain the perfluoroether elastomer;
s4: and (3) carrying out hybridization crosslinking on the perfluoro ether elastomer prepared in the step (S3) and 9.9g of a vulcanization crosslinking agent Bispenta-penta and 16.5g of a vulcanization crosslinking auxiliary agent TAIC, carrying out thin-pass blending, carrying out compression molding at 8MPa and 160 ℃ for 5min for molding, and keeping at 200 ℃ for 10h for secondary vulcanization to obtain the high-temperature low-compression permanent deformation perfluoro ether elastomer composition.
Comparative example 2
S1: into a 5L reactor having an oxygen concentration of not more than 20ppm, 3L of deoxidized deionized water and 3g of emulsifier CF were charged 3 -CF 2 -CF 2 -O-(CF 2 -CF 2 -O) 2 -CF 2 -COOH, 0.3g of chain transfer agent 1, 4-diiodoperfluorobutane, 0.3g of initiator potassium persulfate, and 300g of a mixture of copolymerized fluoromonomers TFE and PMVE, emulsion polymerization under the action of initiator to form a polymer emulsion;
s2: taking the polymer emulsion prepared in the step S1 as seeds, adding 11.4g of nitrile-group-containing vulcanization point monomer 8-CNVE, 0.3g of chain transfer agent 1, 4-diiodoperfluorobutane and 300g of mixture of copolymerized fluoromonomers TFE and PMVE for seed solubilization emulsion polymerization, and obtaining the perfluoroether elastomer emulsion containing nitrile-group-containing vulcanization point monomer after polymerization reaction is stopped;
s3: mixing 300g of perfluoroether elastomer emulsion and 30g of PFA (3M ™ Dyeon ™ Fluoroplastic PFA 6900GZ, solid content 40% and particle size 200 nm) emulsion, performing electrolyte condensation, washing, vacuum freeze-drying, fluoridation of 10wt% of fluorine gas, end group passivation and thin-pass mixing to obtain the perfluoroether elastomer;
s4: and (3) carrying out hybridization crosslinking on the perfluoroether elastomer prepared in the step (S3) with 9.9g of a vulcanization crosslinking agent tetraphenyltin and 16.5g of a catalyst hexaoxacyclooctadecane, carrying out thin-pass blending, carrying out compression molding at 8MPa and 160 ℃ for 5min for molding, and keeping at 200 ℃ for 10h for secondary vulcanization to obtain the high-temperature low-compression permanent deformation perfluoroether elastomer composition.
Comparative example 3
S1: into a 5L reactor having an oxygen concentration of not more than 20ppm, 3L of deoxidized deionized water and 3g of emulsifier CF were charged 3 -CF 2 -CF 2 -O-(CF 2 -CF 2 -O) 2 -CF 2 -COOH, 11.4g of bromine-containing cure site monomer BTFB, 0.3g of chain transfer agent 1, 4-diiodoperfluorobutane, 0.3g of initiator potassium persulfate, and 300g of a mixture of copolymerized fluoromonomers TFE and PMVE, emulsion polymerization under the action of initiator to form a polymer emulsion;
s2: taking the polymer emulsion prepared in the step S1 as seeds, adding 0.3g of chain transfer agent 1, 4-diiodoperfluorobutane and 300g of mixture of copolymerized fluorine-containing monomers TFE and PMVE for seed solubilization emulsion polymerization, obtaining perfluoroether elastomer emulsion of bromine-containing vulcanization point monomers after polymerization reaction is stopped, and simultaneously synthesizing PFA (weight percent is TFE: PPVE: nitrile-based vulcanization point monomers 8-CNVE=93:6:1) emulsion in another reactor;
s3: mixing 300g of perfluoroether elastomer emulsion and 30g of PFA emulsion, performing electrolyte coagulation, washing, vacuum freeze-drying, fluoridation of 10wt% of fluorine gas, end group passivation and thin-pass mixing to obtain the perfluoroether elastomer;
s4: and (3) carrying out hybridization crosslinking on the perfluoro ether elastomer prepared in the step (S3) and 9.9g of a vulcanization crosslinking agent Bispenta-penta and 16.5g of a vulcanization crosslinking auxiliary agent TAIC, carrying out thin-pass blending, carrying out compression molding at 8MPa and 160 ℃ for 5min for molding, and keeping at 200 ℃ for 10h for secondary vulcanization to obtain the high-temperature low-compression permanent deformation perfluoro ether elastomer composition.
Comparative example 4
S1: into a 5L reactor having an oxygen concentration of not more than 20ppm, 3L of deoxidized deionized water and 3g of emulsifier CF were charged 3 -CF 2 -CF 2 -O-(CF 2 -CF 2 -O) 2 -CF 2 -COOH, 2.4g of bromine-containing cure site monomer BTFB, 0.3g of chain transfer agent 1, 4-diiodoperfluorobutane, 0.3g of initiator potassium persulfate, and 300g of a mixture of copolymerized fluoromonomers TFE and PMVE, emulsion polymerization under the action of initiator to form a polymer emulsion;
s2: taking the polymer emulsion prepared in the step S1 as seeds, adding 9g of nitrile group-containing vulcanization point monomer 8-CNVE, 0.3g of chain transfer agent 1, 4-diiodoperfluorobutane and 300g of mixture of copolymerized fluoromonomers TFE and PMVE for seed solubilization emulsion polymerization, and obtaining perfluoroether elastomer emulsion containing two vulcanization point monomers after polymerization reaction is stopped;
s3: mixing 300g of perfluoroether elastomer emulsion and 30g of PFA (3M ™ Dyeon ™ Fluoroplastic PFA 6900GZ, solid content 40% and particle size 200 nm) emulsion, performing electrolyte condensation, washing, vacuum freeze drying, fluoridizing 10wt% of fluorine gas, passivating end groups, and thin-pass mixing to obtain the perfluoroether elastomer;
s4: and (3) carrying out hybridization crosslinking on the perfluoroether elastomer prepared in the step (S3) with 9.9g of a vulcanization crosslinking agent tetraphenyltin and 16.5g of a catalyst hexaoxacyclooctadecane, carrying out thin-pass blending, carrying out compression molding at 8MPa and 160 ℃ for 5min for molding, and keeping at 200 ℃ for 10h for secondary vulcanization to obtain the high-temperature low-compression permanent deformation perfluoroether elastomer composition.
The high temperature low compression set perfluoroether elastomer compositions prepared in examples 1-2 and comparative examples 1-4 were tested for various performance criteria, including Shore hardness, tensile strength, tensile elongation at break, compression set and compression set, using test methods ASTM D2240-2004, ASTM D412-06a, GB/T1683-2018 and GB/T1683-2018, respectively, and the relevant criteria test results are shown in Table 1.
TABLE 1 Performance index of perfluoroether elastomer compositions prepared in examples and comparative examples
Note that: a is 250 ℃, i.e., the perfluoroether elastomer composition prepared in comparative example 3 loses its low compression set properties at 250 ℃, so the perfluoroether elastomer composition prepared in comparative example 3 also loses its properties at 300 ℃; whereas comparative example 1, comparative example 2 and comparative example 4 had low compression set properties at 250 ℃, but lost this property at 300 ℃.
As can be seen from the test results of the table above, the perfluoroether elastomer composition prepared by reacting the perfluoroether elastomer emulsion containing two vulcanization point monomers with the PFA emulsion containing nitrile group-containing vulcanization point monomers has higher hardness and strength, examples 1-2 all have lower permanent compression set, and after 72 hours of compression at 200 ℃, examples 1-2 have a permanent compression set of 18-20%, which is significantly lower than that of the comparative example; after 72 hours of compression at 300 ℃, the permanent compression set of examples 1-2 is 43-49%; meanwhile, as can be seen from the comparative examples, the prepared perfluoroether elastomer composition has good properties and permanent compression set only when the perfluoroether elastomer emulsion containing two kinds of vulcanization point monomers and the vulcanization point monomer PFA emulsion containing nitrile groups are used together, which means that the vulcanization point monomers containing nitrile groups in the PFA emulsion can crosslink not only TFE segments and PPVE segments in PFA but also better with the perfluoroether elastomer emulsion containing two kinds of vulcanization point monomers. From these results, the perfluoroether elastomer composition prepared by the present application has an effect of low compression set at high temperature while maintaining other excellent properties.
The foregoing is merely illustrative of the present application, and the present application is not limited thereto, and any changes or substitutions easily contemplated by those skilled in the art within the scope of the present application should be included in the present application.
Claims (11)
1. A process for preparing a high temperature low compression set perfluoroether elastomer composition comprising the steps of:
s1: adding deoxidized deionized water accounting for 60-70% of the volume of the deoxidized deionized water, an emulsifier, a vulcanization point monomer containing bromine or iodine, a chain transfer agent, an initiator and a copolymerization fluorine-containing monomer into a reactor with the oxygen concentration lower than 20ppm, and performing emulsion polymerization reaction under the action of the initiator to form polymer emulsion;
s2: taking the polymer emulsion prepared in the step S1 as seeds, adding nitrile group-containing vulcanization point monomers, chain transfer agents and copolymerized fluorine-containing monomers in a gradient or quantitative manner to carry out seed solubilization emulsion polymerization, obtaining perfluoroether elastomer emulsion containing the two vulcanization point monomers after polymerization reaction is stopped, and synthesizing PFA emulsion in another reactor;
s3: mixing the perfluoroether elastomer emulsion prepared in the step S2 with the PFA emulsion, performing electrolyte condensation, washing, vacuum freeze-drying, passivating fluorinated end groups and thin-pass mixing to obtain the perfluoroether elastomer;
s4: blending the perfluoro ether elastomer prepared in the step S3 with a vulcanization crosslinking agent and a catalyst hybridized crosslinking agent in a thin way, performing compression molding, performing secondary vulcanization to obtain a perfluoro ether elastomer composition with high temperature and low compression set,
wherein the mass ratio of the fluorine-containing monomers in the S1 and the S2 is 1:1-3:1, and the total addition amount of the fluorine-containing monomers is 15wt% to 25wt% of the total mass of the polymer emulsion in the S1; the PFA emulsion in the S2 consists of 91-98 wt% of TFE, 1-8 wt% of PPVE and 0.5-1.5 wt% of nitrile group-containing vulcanization point monomer.
2. The method for preparing a high-temperature low-compression set perfluoroether elastomer composition according to claim 1, wherein the emulsifier in S1 comprises any one of fluoroether carboxylic acid, polyoxyethylene oleate and polyoxyethylene laurate; the addition amount of the emulsifier is 0.5-2 wt% of the total amount of the fluorine-containing monomers in the S1 and the S2.
3. The process for producing a high-temperature low-compression set perfluoroether elastomer composition according to claim 1,characterized in that the vulcanization point monomer containing bromine or iodine in S1 comprises R 1 CH=CR 2 CR 3 、R f -I and I-R f -any of I, wherein R 1 、R 2 、R 3 Selected from H, br, F, R f Or R is f Br, and R 1 、R 2 、R 3 At least one of which is Br or R f Br，R f Is perfluoroalkyl; the addition amount of the vulcanization point monomer containing bromine and/or iodine is 0.4-0.6 wt% of the total amount of the co-polymerized fluorine-containing monomers in the S1 and the S2.
4. The method for preparing a high temperature low compression set perfluoroether elastomer composition according to claim 1, wherein the chain transfer agent in S1 and S2 is I- (CF) 2 ) n -I, comprising 1, 3-diiodopropane, 1, 4-diiodobutane, 1, 6-diiodohexane, 1, 8-diiodooctane, 1, 3-diiodoperfluoropropane, 1, 4-diiodoperfluorobutane, 1, 6-diiodoperfluorohexane or 1, 8-diiodoperfluorooctane; the addition amount of the chain transfer agent in the S1 and the S2 is 0.05-2 wt% of the total amount of the fluorine-containing monomers in the S1 and the S2.
5. The method for preparing a high temperature low compression set perfluoroether elastomer composition according to claim 1, wherein the initiator in S1 comprises any one of sodium persulfate, potassium persulfate and ammonium persulfate; the addition amount of the initiator is 0.05 to 0.5 weight percent of the total amount of the fluorine-containing monomers in the S1 and the S2.
6. The method of preparing a high temperature low compression set perfluoroether elastomer composition according to claim 1, wherein the S1 and S2 co-polymerized fluoromonomers comprise tetrafluoroethylene and a perfluoroalkyl vinyl ether.
7. The method for preparing a high-temperature low-compression permanent set perfluoroether elastomer composition according to claim 1, wherein said S2 nitrile group-containing vulcanization point monomer and said PFA nitrile group-containing vulcanization point monomer are eachFrom independently selected from CF 2 =CF-O-R f X, wherein X is O- (CF) 2 ) n CN or CN; the addition amount of the nitrile group-containing vulcanization point monomer in the S2 is 1.5-3 wt% of the total amount of the co-polymerized fluorine-containing monomers in the S1 and the S2.
8. The method for preparing a high-temperature low-compression permanent deformation perfluoroether elastomer composition according to claim 1, wherein the vulcanization crosslinking agent in S4 is tetraphenyltin, and the catalyst is hexaoxolane octadecane; the addition amounts of the vulcanization crosslinking agent and the catalyst are respectively 1.5-3 wt% and 2.5-5 wt% of the total mass of the perfluoroether elastomer emulsion and the PFA emulsion, wherein the mass ratio of the perfluoroether elastomer emulsion to the PFA emulsion is 10:1-5:1.
9. The method for preparing a high-temperature low-compression permanent deformation perfluoroether elastomer composition according to claim 1, wherein the fluorinating agent used in the step S3 is 10wt% fluorine gas and nitrogen gas is an equilibrium gas.
10. The method for preparing a high-temperature low-compression permanent deformation perfluoroether elastomer composition according to claim 1, wherein the molding condition in S4 is that the pressure is 8-10MPa, the temperature is 160-175 ℃ and the time is 5-16min; the secondary vulcanization condition is that the temperature is 200-220 ℃ and the time is 10-24 hours.
11. A high temperature low compression set perfluoroether elastomer composition prepared by the process of any one of claims 1-10.
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