JPH0223574B2 - - Google Patents
Info
- Publication number
- JPH0223574B2 JPH0223574B2 JP13542188A JP13542188A JPH0223574B2 JP H0223574 B2 JPH0223574 B2 JP H0223574B2 JP 13542188 A JP13542188 A JP 13542188A JP 13542188 A JP13542188 A JP 13542188A JP H0223574 B2 JPH0223574 B2 JP H0223574B2
- Authority
- JP
- Japan
- Prior art keywords
- fluororubber
- weight
- dbn
- parts
- diazabicyclo
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- -1 tetrafluoroborate group Chemical group 0.000 claims description 42
- 229920001973 fluoroelastomer Polymers 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 17
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 9
- 150000001491 aromatic compounds Chemical class 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 2
- 238000004073 vulcanization Methods 0.000 description 19
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 238000004898 kneading Methods 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 5
- 150000004820 halides Chemical class 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000007906 compression Methods 0.000 description 4
- 230000006835 compression Effects 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 3
- AGEZXYOZHKGVCM-UHFFFAOYSA-N benzyl bromide Chemical compound BrCC1=CC=CC=C1 AGEZXYOZHKGVCM-UHFFFAOYSA-N 0.000 description 3
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 3
- 229940073608 benzyl chloride Drugs 0.000 description 3
- ZFVMWEVVKGLCIJ-UHFFFAOYSA-N bisphenol AF Chemical compound C1=CC(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C=C1 ZFVMWEVVKGLCIJ-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- SGUVLZREKBPKCE-UHFFFAOYSA-N 1,5-diazabicyclo[4.3.0]-non-5-ene Chemical compound C1CCN=C2CCCN21 SGUVLZREKBPKCE-UHFFFAOYSA-N 0.000 description 2
- 239000000370 acceptor Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 238000005349 anion exchange Methods 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 2
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical compound FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910001495 sodium tetrafluoroborate Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- NDMMKOCNFSTXRU-UHFFFAOYSA-N 1,1,2,3,3-pentafluoroprop-1-ene Chemical compound FC(F)C(F)=C(F)F NDMMKOCNFSTXRU-UHFFFAOYSA-N 0.000 description 1
- OQMIRQSWHKCKNJ-UHFFFAOYSA-N 1,1-difluoroethene;1,1,2,3,3,3-hexafluoroprop-1-ene Chemical compound FC(F)=C.FC(F)=C(F)C(F)(F)F OQMIRQSWHKCKNJ-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
- DVMSVWIURPPRBC-UHFFFAOYSA-N 2,3,3-trifluoroprop-2-enoic acid Chemical compound OC(=O)C(F)=C(F)F DVMSVWIURPPRBC-UHFFFAOYSA-N 0.000 description 1
- XSQHUYDRSDBCHN-UHFFFAOYSA-N 2,3-dimethyl-2-propan-2-ylbutanenitrile Chemical compound CC(C)C(C)(C#N)C(C)C XSQHUYDRSDBCHN-UHFFFAOYSA-N 0.000 description 1
- AGPJEGDSGBAREQ-UHFFFAOYSA-N 2-chloro-1,3,3,4,4,5,6,6,7,8,8,8-dodecafluorooct-1-ene Chemical compound FC(C(F)(F)F)C(C(C(C(C(=CF)Cl)(F)F)(F)F)F)(F)F AGPJEGDSGBAREQ-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- HTVITOHKHWFJKO-UHFFFAOYSA-N Bisphenol B Chemical compound C=1C=C(O)C=CC=1C(C)(CC)C1=CC=C(O)C=C1 HTVITOHKHWFJKO-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910020808 NaBF Inorganic materials 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001198 elastomeric copolymer Polymers 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920006027 ternary co-polymer Polymers 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/136—Phenols containing halogens
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
- C08K5/3462—Six-membered rings
- C08K5/3465—Six-membered rings condensed with carbocyclic rings
Description
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[Industrial Application Field] The present invention relates to a fluororubber composition. More specifically, the present invention relates to a fluororubber composition containing a quaternary ammonium salt compound as a vulcanization accelerator component. [Prior art] Fluororubber vulcanizates have useful properties in terms of heat resistance, chemical resistance, oil resistance, weather resistance, etc. at high temperatures, so they are used as sealing materials for gaskets, O-rings, packings, etc. Demand for hoses, sheets, etc. is rapidly increasing in fields such as the automobile industry, hydraulic industry, general machinery industry, and aircraft industry. In other words, in addition to the demand for more efficient molding processes, various demands regarding fluororubber vulcanizates are becoming more diverse and stricter. Vulcanization of fluorocarbon rubber was initially carried out using polyamine derivatives such as hexamethylene diamine carbamate and methylene bis(cyclohexyl) amine carbamate, but these vulcanization systems had poor scorch resistance (processing safety, However, it had disadvantages in terms of storage stability) and compression set of the vulcanizate. Subsequently, as a vulcanization system capable of improving these drawbacks, a method of crosslinking with a polyhydroxy aromatic compound in the presence of a vulcanization accelerator and an acid acceptor was proposed, and has been put into practical use to this day. As a vulcanization accelerator in this vulcanization system, quaternary
Phosphonium salt compound (JP-A-47-191),
Quaternary ammonium salt compound (Japanese Patent Publication No. 52-38072, Japanese Patent Publication No. 47-3831), 8-alkyl (or aralkyl)-1,8-diazabicyclo[5,4,0]-undec-7-ene quaternary ammonium salt compound (Japanese Patent Publication No. 52-8863, JP-A-48-55231, JP-A-63-51441) or 1, in an amount that does not substantially vulcanize the fluororubber. Combination with 8-diazabicyclo[5,4,0]-undec-7-ene (Japanese Patent Publication No. 57-20333), 5-alkyl (or aralkyl)-1,
Quaternary ammonium salt compound of 5-diazabicyclo[4,3,0]-5-nonene (JP-A-59-206451
Publication No. 59-232137, Publication No. 63-51441), etc. are used. However, these quaternary ammonium salt compounds used as vulcanization accelerators, especially 5-alkyl (or aralkyl)-1,5-diazabicyclo[4,3,0]-5-nonene quaternary ammonium salt compounds, Generally, it has the following drawbacks. (1) It is highly hygroscopic and hygroscopic, making it difficult to handle during storage, kneading, etc. (2) It is difficult to prepare masterbatch dispersions with fluoro rubber due to poor kneading processability and dispersibility. Even if it can be adjusted, care must be taken when storing it.(3) Poor moldability due to insufficient mold releasability.(4) Vulcanized physical properties such as elongation and tensile strength, compression set, etc. [Problem to be solved by the invention] The object of the present invention is to use 5-alkyl (or aralkyl)-1,5-diazabicyclo[4] as a vulcanization accelerator. The object of the present invention is to provide a vulcanizable fluororubber composition that does not exhibit these drawbacks when a quaternary ammonium salt compound of ,3,0]-5-nonene is used. [Means for Solving the Problems] The object of the present invention is to provide (a) fluororubber, (b) divalent metal oxide and/or hydroxide, (c) polyhydroxy aromatic compound, and ( d) General formula (wherein, R is an alkyl group having 1 to 24 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, and X - is a tetrafluoroborate group or hexafluorophosphate group) This is achieved by a fluororubber composition containing. The fluororubber to be vulcanized is a highly fluorinated elastomeric copolymer; for example, a copolymer of vinylidene fluoride and another fluorine-containing olefin can be used. Specifically, for example, vinylidene fluoride, hexafluoropropene, pentafluoropropene, trifluoroethylene, trifluorochloroethylene, tetrafluoroethylene, vinyl fluoride, perfluoroacrylate, perfluoroalkyl acrylate, perfluoromethyl Examples include one or more copolymers such as vinyl ether and perfluoropropyl vinyl ether, preferably vinylidene fluoride-hexafluoropropene binary copolymers and vinylidene fluoride-tetrafluoroethylene-hexafluoropropene ternary copolymers. Examples include copolymers. Divalent metal oxides used as acid acceptors,
Hydroxides include magnesium, calcium,
One or more types of oxides and hydroxides of divalent metals such as barium, lead, and zinc are
It is generally used in a proportion of about 1 to 40 parts by weight, preferably about 3 to 15 parts by weight. Examples of the polyhydroxy aromatic compound as a crosslinking agent include 2,2-bis(4-hydroxyphenyl)propane [bisphenol A], 2,2-
Bis(4-hydroxyphenyl) perfluoropropane [bisphenol AF], hydroquinone, catechol, resorcinol, 4,4'-dihydroxydiphenyl, 4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenyl sulfone,
Examples include 2,2-bis(4-hydroxyphenyl)butane, preferably bisphenol A,
Bisphenol AF, hydroquinone, etc. are used. They may also be in the form of alkali metal or alkaline earth metal salts. These crosslinking agents are used in amounts of about 0.5 to 100 parts by weight of fluorocarbon rubber.
It is used in a proportion of 10 parts by weight, preferably about 0.5 to 6 parts by weight. If the usage ratio is less than this, the crosslinking density will be insufficient, while if it is more than this, the crosslinking density will become too high and there will be a tendency to lose rubber-like elasticity. As the quaternary ammonium salt compound represented by the above general formula, preferably a compound in which R is a benzyl group is used. Such 5-benzyl-1,
5-Diazabicyclo[4,3,0]-5-nonenium tetrafluoroborate (abbreviation: DBN-
F) or hexafluorophosphate (abbreviation:
DBN-P) is an aqueous solution of 5-benzyl-1,5-diazabicyclo[4,3,0]-5-nonenium halide with a tetrafluoroborate salt compound or hexafluorophosphate salt compound, generally the sodium salt thereof. When the compound is added, it quickly precipitates out, and can be easily separated from the solvent and by-product salts by simply filtering it. A typical 5-benzyl-1,5-diazabicyclo[4,3,0]-5-nonenium salt conventionally used is chloride (abbreviation: DBN-C).
or halide such as bromide (abbreviation: DBN-B), which is synthesized by combining 1,5-diazabicyclo[4,3,0]-5-nonene with benzyl chloride or benzyl bromide in a solvent such as toluene. The crystals formed are deliquescent, so there is a restriction that removal and filtration must be carried out in substantially moisture-free air (dry air) or under a nitrogen atmosphere. Of course, similar considerations are required during storage and formulation. In the synthesis of tetrafluoroborate or hexafluorophosphate used in the present invention, such deliquescence of the halide can be utilized in the form of an aqueous solution, and the product can be easily obtained as a crystal. By the way, other anions,
For example, NO 3 - , SO 4 -- , PO 4 --- , RCOO - ,
CO 3 -- , BO 2 - , SCN - , SiF 6 -- , RSO 3 - ,
With anions such as TiF 6 --, crystals do not precipitate through an anion exchange reaction with halides, and the target product can only be separated by applying means such as concentration and separation of by-product salts, whereas with BF 4 -- In the case of , PF 6 - , it is extremely easy to separate the crystals produced by the anion exchange reaction by simply filtering them. Moreover, the obtained 5-benzyl-1,5-diazabicyclo[4,3,0]-5-nonenium tetrafluoroborate or hexafluorophosphate has extremely low hygroscopicity, and therefore it is difficult to absorb dry air during filtration separation. A nitrogen gas atmosphere is not required, and the same applies during storage and compounding. Incidentally, these quaternary ammonium salt compounds were placed in a shear dish and left in a constant temperature and humidity chamber at 25°C and 100% humidity for 2 days, and then the moisture content (increased weight/initial weight x 100) was measured. 5-benzyl-1,
When compared with 5-diazabicyclo[4,3,0]-5-nonenium salt or 8-benzyl-1,8-diazabicyclo[5,4,0]-undec-7-enium chloride (abbreviation: DBU-C) , the following results were obtained. Moisture content of salt compound at 100â (%) DBN-F Liquid 6.5 DBN-P ã 4.8 DBN-C Solid 42.5 DBN-B ã 46.3 DBU-C ã 27.4 Furthermore, these tetrafluoroborates and hexafluorophosphates , have melting points of approximately 80°C and 100°C, respectively, and are easily melted during heat kneading (100°C) using rolls, kneaders, banburys, etc., so that a significant improvement in dispersibility can be achieved. One or two of these quaternary ammonium salt compounds are used in a proportion of about 0.1 to 5 parts by weight, preferably about 0.1 to 2 parts by weight, per 100 parts by weight of fluororubber. If the proportion used is less than this, the crosslinking properties will be poor, and if the proportion is greater than this, the properties of the vulcanizate will be significantly adversely affected. At this time, the quaternary ammonium salt compound can be used as a masterbatch with the fluororubber. Generally, the vulcanization accelerator component of fluororubber tends to cause poor dispersion due to its small blending ratio, and therefore it is often used as a masterbatch as a means to prevent this. The concentration of the vulcanization accelerator in the masterbatch is generally about 20 to 50%, and if it is less than this, the amount to be blended becomes too large, which is not preferable. The quaternary ammonium salt compound used in the present invention, unlike the corresponding halide, can be easily made into master batches. Specifically, when the kneading properties of 500 g of master batches with various vulcanization accelerator concentrations were evaluated, the following results were obtained. The results were obtained.
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æ°Žæ§åªäœäžã§ãé£é移åå€ãšããŠã¢ã»ãã³ã䜿
çšããéåéå§å€ãšããŠéç¡«é
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åšäžã«ããåãããªãã³ãšãããµãã«ãªãããã
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ã¢ã«æ¯78ïŒ22ã溶液ç²åºŠÎ·spïŒc0.98ïŒ35âãã¢ã»
ãã³äžãïœïŒ1.0ïŒãéåäœã ãŒããŒç²åºŠ
ML1+1053ïŒ121âïŒïŒããçŽ ãŽã ã«ã€ããŠã次
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åç©ãïŒã€ã³ãã
ãã·ã³ã°ããŒã«ã§æ··ç·ŽããããçŽ ãŽã çµæç©ã調
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The fluororubber composition according to the present invention is similar to the conventional
Ammonium salt compounds, especially the known 5-benzyl-1,5-diazabicyclo[4,3,0]-5-
The hygroscopicity, which is a drawback of nonenium salts, has been improved, and as a result, the ease of handling and stability have also been significantly improved. In addition, kneading operability, dispersibility, and processability have been improved by lowering the melting point and creating a masterbatch, and furthermore, excellent improvements have been achieved in terms of vulcanization physical properties, shaping properties, and mold contamination. . [Example] Next, the present invention will be explained with reference to an example. Reference examples 1-2 Capacity with stirring device and Dimroth cooler
26.05g of 1,5-diazabicyclo[4,3,0]-5-nonene in a 300ml separable flask
(0.21 mol), 100 g of toluene and benzyl chloride
27.8g (0.22 mole) or 37.6g benzyl bromide
(0.22 mol) was added one by one, and while stirring, 100~
After reacting at 110°C for about 1.5 hours, white crystals of 5-benzyl-1,5-diazabicyclo[4,3,0]-
5-nonenium chloride (DBN-C) or bromide (DBN-B) was formed. After the reaction is complete, add approximately 50 ml of water to the reaction mixture in the separable flask, and add DBN-C or DBN-B.
The mixture was separated into an aqueous solution layer and a toluene layer containing unreacted benzyl chloride or benzyl bromide dissolved therein. When 23 g (0.21 mol) of sodium tetrafluoroborate NaBF 4 is added to each of these aqueous solutions with stirring, water-insoluble white crystals will gradually precipitate, and after about 5 minutes, they should be filtered, washed with water, and dried. 5-benzyl-1,5-diazabicyclo[4,3,0]-5-nonenium tetrafluoroborate (DBN-F) is converted into DBN-C
57.3g (90% yield) or from DBN-B
56.7g (yield 89%) was obtained. Reference Example 3 In Reference Examples 1 and 2, when 35.3 g (0.21 mol) of sodium hexafluorophosphate NaPF 6 is used instead of sodium tetrafluoroborate, 5-benzyl-1,5-diazabicyclo[4,3 ,0]-5-nonenium hexafluorophosphate (DBN-P) (68.4 g (yield 90
%) obtained. DBN-F obtained in each of the above reference examples or
DBN-P is 35% by weight and 65% by weight of fluoro rubber.
They were each used as a masterbatch (the blending amounts in Tables 1 and 3 below are the masterbatch amounts). Examples 1-2, Comparative Examples 1-3 Copolymerization of vinylidene fluoride and hexafluoropropene in an aqueous medium using acetone as a chain transfer agent and in the presence of ammonium persulfate as a polymerization initiator Copolymer [comonomer component molar ratio 78:22, solution viscosity ηsp/c 0.98 (35°C, in acetone, c = 1.0), polymer Mooney viscosity
ML 1+10 53 (121°C); Fluororubber A], a fluororubber composition was prepared by kneading the formulation shown in Table 1 below using an 8-inch mixing roll. Note that all amounts below are in parts by weight.
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å®ãšãªãïŒã121âã®æž¬å®æž©åºŠã§æž¬å®ããã
æŽã«ãçµæç©ã180âã§ïŒåéãã¬ã¹å ç¡«ãã
次ãã§230âã®ãªãŒãã³äžã§22æéã®äºæ¬¡å ç¡«ã
è¡ãªããåå ç¡«ç©ã®è«žç©æ§å€ãJIS â6301ã«åŸ
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âãªã³ã°ãåãæ¡ä»¶ã§å ç¡«ããŠè£œäœããããã25
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è¡šïŒã«ç€ºãããã[Table] Mooney viscosity and scorch time (the time required for the Mooney viscosity to reach the minimum value + 5, which is a guideline for the storage stability and processing safety of the dough) for the various fluororubber compositions obtained. ) was measured at a measurement temperature of 121°C. Furthermore, the composition was press-vulcanized at 180°C for 5 minutes,
Next, secondary vulcanization was performed in an oven at 230°C for 22 hours, and various physical properties of each vulcanized product were measured according to JIS K-6301. Measurement of compression set is performed using O of P-24.
- Manufactured by vulcanizing the ring under the same conditions, and 25
% compression and measurement. The results of these measurements are shown in Table 2 below.
ãè¡šããtableã
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次ã®è¡šïŒã«ç€ºãããé
ååŠæ¹ã®é
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ã³ãããã·ã³ã°ããŒã«ã§æ··ç·ŽããããçŽ ãŽã çµæ
ç©ã調補ããã[Table] Examples 3 to 4, Comparative Example 4 The formulations shown in Table 3 below were kneaded using an 8-inch mixing roll to prepare a fluororubber composition.
ãè¡šã
åŸãããããçŽ ãŽã çµæç©ã«ã€ããŠãå®æœäŸïŒ
ãïŒãšåæ§ã«ãè«žç©æ§ãªãã³ã«è«žç¹æ§ã®æž¬å®ãè¡
ãªã€ãããã ããå ç¡«ã¯ã170âã§ïŒåéãã¬ã¹
å ç¡«åŸ200âã§22æéãªãŒãã³äžã§äºæ¬¡å ç¡«ãã
ããšã«ããè¡ããããæŽã«ãå®å
¬æ53â33206å·
å
¬å ±ã«èšèŒããããããªåœ¢ç¶ã®ãã«ãã¹ãã ã·ãŒ
ã«ãããã®çµæç©ããé¢åå€ã䜿çšããã«é£ç¶ç
ã«æ圢ããå ç¡«æ圢æïŒ170âãïŒåéãã¬ã¹å
ç¡«ïŒã®è³Šåœ¢æ§ããã³éåã®æ±æç¶æ³ïŒæåã¯éå
è¡šé¢ã®ããããšããŠèŠ³å¯ãããæŽã«ç¶ããŠæ圢ã
ããšéåã«ã«ã¹ä»ããçºçããïŒãããããè©äŸ¡
ããã以äžã®çµæã¯ã次ã®è¡šïŒã«ç€ºãããã[Table] Regarding the obtained fluororubber composition, Example 1
- In the same manner as in 2, various physical properties and characteristics were measured. However, vulcanization was performed by press vulcanization at 170°C for 8 minutes, followed by secondary vulcanization in an oven at 200°C for 22 hours. Furthermore, a valve stem seal having a shape as described in Japanese Utility Model Publication No. 53-33206 was continuously molded from this composition without using a mold release agent, and during vulcanization molding (170°C, 8 minutes). The formability of press vulcanization) and the contamination of the mold (which was initially observed as cloudiness on the mold surface, and when molding continued, scum formed on the mold) were evaluated. The above results are shown in Table 4 below.
ãè¡šããtableã
Claims (1)
åç©ããã³ïŒãŸãã¯æ°Žé žåç©çŽïŒã40éééšã(c)
ããªããããã·è³éŠæååç©çŽ0.5ã10éééšã
ãã³(d)äžè¬åŒ ïŒããã§ãã¯ççŽ æ°ïŒã24ã®ã¢ã«ãã«åºãŸã
ã¯ççŽ æ°ïŒã20ã®ã¢ã©ã«ãã«åºã§ãããX-ã¯ã
ãã©ãã«ãªããã¬ãŒãåºãŸãã¯ãããµãã«ãªãã
ã¹ããšãŒãåºã§ããïŒã§è¡šãããã第ïŒã¢ã³ã¢ã
ãŠã å¡©ååç©çŽ0.1ãïŒéééšãå«æããŠãªãã
ãçŽ ãŽã çµæç©ã ïŒ (d)æå第ïŒã¢ã³ã¢ããŠã å¡©ååç©ã(a)æåã
ãçŽ ãŽã ãšã®ãã¹ã¿ãŒããããšããŠçšããè«æ±é
ïŒèšèŒã®ããçŽ ãŽã çµæç©ã ïŒ è«æ±é ïŒèšèŒã®(d)æå第ïŒã¢ã³ã¢ããŠã å¡©å
åç©ãš(a)æåããçŽ ãŽã ãšã®ãã¹ã¿ãŒãããã[Claims] 1 (a) 100 parts by weight of fluororubber, (b) about 1 to 40 parts by weight of divalent metal oxide and/or hydroxide, (c)
About 0.5 to 10 parts by weight of a polyhydroxy aromatic compound and (d) general formula (wherein, R is an alkyl group having 1 to 24 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, and X - is a tetrafluoroborate group or hexafluorophosphate group) A fluororubber composition containing about 0.1 to 5 parts by weight. 2. The fluororubber composition according to claim 1, wherein the quaternary ammonium salt compound (d) is used as a masterbatch with the fluororubber (a). 3. A masterbatch of the quaternary ammonium salt compound (d) according to claim 1 and the fluororubber (a).
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP13542188A JPH01306454A (en) | 1988-06-03 | 1988-06-03 | Fluoro rubber composition |
DE19893915318 DE3915318A1 (en) | 1988-06-03 | 1989-05-10 | Fluororubber composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP13542188A JPH01306454A (en) | 1988-06-03 | 1988-06-03 | Fluoro rubber composition |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH01306454A JPH01306454A (en) | 1989-12-11 |
JPH0223574B2 true JPH0223574B2 (en) | 1990-05-24 |
Family
ID=15151341
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP13542188A Granted JPH01306454A (en) | 1988-06-03 | 1988-06-03 | Fluoro rubber composition |
Country Status (2)
Country | Link |
---|---|
JP (1) | JPH01306454A (en) |
DE (1) | DE3915318A1 (en) |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
IT1255853B (en) * | 1992-10-12 | 1995-11-17 | Ausimont Spa | COMPOSITIONS OF VULCANIZABLE ELASTOMERIC POLYMERS BY IONIC WAY |
CN100354358C (en) * | 2003-04-21 | 2007-12-12 | Nokæ ªåŒäŒç€Ÿ | Method for producing low-friction fluorine rubber crosslinked body |
US7977433B2 (en) | 2005-11-16 | 2011-07-12 | Nok Corporation | Fluororubber composition and production method of cross-linked fluororubber product |
WO2009157361A1 (en) * | 2008-06-26 | 2009-12-30 | ãŠããããã¯æ ªåŒäŒç€Ÿ | Rubber laminate |
JP5422940B2 (en) * | 2008-08-26 | 2014-02-19 | ïœïœæ ªåŒäŒç€Ÿ | Fluororubber composition and method for producing crosslinked fluororubber |
US20110245423A1 (en) * | 2008-09-04 | 2011-10-06 | Kashihara Takayuki | Fluororubber composition and process for producing crosslinked fluororubber |
CN109627647A (en) * | 2019-01-08 | 2019-04-16 | æ°ä¹æ³°ç§ïŒåŠéšïŒæ°æææéå ¬åž | A kind of high adhesiveness fluororubber compounded rubber and preparation method thereof |
-
1988
- 1988-06-03 JP JP13542188A patent/JPH01306454A/en active Granted
-
1989
- 1989-05-10 DE DE19893915318 patent/DE3915318A1/en active Granted
Also Published As
Publication number | Publication date |
---|---|
DE3915318A1 (en) | 1989-12-07 |
JPH01306454A (en) | 1989-12-11 |
DE3915318C2 (en) | 1993-04-15 |
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