CA2150343A1 - Curable fluoroelastomeric compositions - Google Patents
Curable fluoroelastomeric compositionsInfo
- Publication number
- CA2150343A1 CA2150343A1 CA002150343A CA2150343A CA2150343A1 CA 2150343 A1 CA2150343 A1 CA 2150343A1 CA 002150343 A CA002150343 A CA 002150343A CA 2150343 A CA2150343 A CA 2150343A CA 2150343 A1 CA2150343 A1 CA 2150343A1
- Authority
- CA
- Canada
- Prior art keywords
- adduct
- weight
- curing agent
- vdf
- compositions according
- 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.)
- Abandoned
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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
- C08K5/49—Phosphorus-containing compounds
- C08K5/50—Phosphorus bound to carbon only
-
- 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
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0025—Crosslinking or vulcanising agents; including accelerators
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
- C08K5/19—Quaternary ammonium compounds
-
- 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
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/37—Thiols
-
- 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
- C08K5/49—Phosphorus-containing compounds
- C08K5/5399—Phosphorus bound to nitrogen
Abstract
Curable flurooelastomeric compositions employable for prepa-ring fuel hoses or O-rings for injectors comprising:
A) 100 phr (parts) copolymers or terpolymers based on VDF
with a content in fluorine of at least 67% by weig-ht, the VDF being comprised from 30 to 50% by weig-ht, from 20 to 60% by weight of HFP optionally other monomeric units deriving from a monomer having ethylene unsaturation; the sum of the comonomers being 100;
B) 1 to 5 phr of an adduct between an accelerator and a curing agent in molar ratio from 1:2 to 1:5, the acce-lerator being an onio-organic compound having a positi-ve charge, the curing agent being a di- or polyhydroxy or di- or polythiol compound; the adduct being obtained by melting of the reaction product between accelerator and curing agent in the indicated molar ratios, or by melting of the adduct mixture 1:1 added with the curing agent in the indicated amounts.
A) 100 phr (parts) copolymers or terpolymers based on VDF
with a content in fluorine of at least 67% by weig-ht, the VDF being comprised from 30 to 50% by weig-ht, from 20 to 60% by weight of HFP optionally other monomeric units deriving from a monomer having ethylene unsaturation; the sum of the comonomers being 100;
B) 1 to 5 phr of an adduct between an accelerator and a curing agent in molar ratio from 1:2 to 1:5, the acce-lerator being an onio-organic compound having a positi-ve charge, the curing agent being a di- or polyhydroxy or di- or polythiol compound; the adduct being obtained by melting of the reaction product between accelerator and curing agent in the indicated molar ratios, or by melting of the adduct mixture 1:1 added with the curing agent in the indicated amounts.
Description
215~3~3 C ~'R~ FLUOROELASTOMERIC COMPOSITIONS
*****
The present invention relates to curable vinylidene-fluoride copolymers having a high content in fluorine, the other comonomers deriving from fluorinated monomers with ethylene unsaturation.
More in detail the present invention relates in parti-cular to fluoroelastomeric copolymers based on vinylidene-fluoride (VDF), hexafluoropropene (HFP), optionally in the presence of one or more comonomers ethylenically unsatura-ted, the F amount being higher than 67~ by weight.
More particularly the invention relates to fluoroela-stomeric copolymers based on VDF suitable to the preparation of fuel hoses and shaft seals.
It is known that for the preparation of these arti-cles, fluoroelastomeric polymers are required having good resistance to motor oils and/or to petrols containing polar substances, in particular alcohols.
This property must be combined with good elastomeric properties such as compression set and good mechanical pro-perties and good processability in molding both by compres-ta~370 ---t) 2 21S034~
sion, by injection and by extrusion.
The same copolymers can be also used for preparing 0-rings used in the injectors coming into contact with petrols and/or oils containing polar substances.
It is known making articles based on VDF, HFP and te-trafluoroethylene (TFE), optionally in the presence of per-fluoroalkylvinylethers (PAVE), using the peroxidic curing.
The disadvantage is that the compression set obtained are poor and the removal from molds is unsatisfactory.
It is also known from the previous patent application of the Applicant, EP 525687, to carry out the ionic curing with known accelerators and curing agents. The drawback is that these products show mechanical properties lower than the products cured with peroxides.
To obviate these inconveniences in the art it is known to use also processing aids such as sulphones or sulphoxi-des. The drawback is that the addition of these products, even though they lead to an improved rubber processing, wor-sen the mechanical properties and depending on the accelera-ting system worsen also the compression set.
It is known, moreover, that the elastomeric polymers having high content of fluorine show a bad processability due to the high viscosi~y of the compound.
(~F93 7 0 - ~9~: ) 21~03a~
All the disadvantages of the copolymes based on VDF
with low content in fluorine (less than 67~ by weight), are even more stressed in case of VDF copolymers having high content in fluorine, as indicated above.
~ n case of copolymers or terpolymers, indeed, having high content in fluorine, the crosslinking is even more dif-ficult and wherefore the mechanical and elastic properties and the processability of the artic~e result poor.
It has surprisingly and unexpectedly been found that it is possible to prepare fluoroelastomeric polymers based on VDF having a very good combination of - high mechanical properties, - low compression set, - low viscosity of the compound such as to allow an easy processing both by compression, by injection and by extrusion, - high resistance to oils and to petrols containing polar sub tances, such as alcohols or ethers.
This has been made possible by using ionic curing with a particular accelerating/curing system as herein defined.
Ac~ordingly, in one ot it& ~SQects~ th~ pr~s~lnt in~ntion r~l~t~S to cYr~bl~ ~luor~l~sto.~ric co~po~ltion& co~priSing A) 100 phr (parts) copolymers of terpolymers based on VDF
(AP9370 ---t) 21503~
having a content in fluorine of at least 67~ by weight, the VDF being comprised from 30 to 50~ by weight, from 20 to 60~ by weight of HFP, optionally other mono-meric units deriving from a monomer having ethyelene unsaturation; the sum of the comonomers being 100. In case of copolymers, the VDF ranges from 40 to 50 and HFP ranges from 50 to 60~ by weight. The other comono-mers are preferably from 0 to 30~ of TFE and from 0 to 40~ of perfuoroalkylvinylethers, preferably 0-20~;
B) 1 to 5 phr, preferably 2 to 4.5, of an adduct between an accelerator and a curing agent in molar ratio from 1:2 to 1:5, preferably 1:2 to 1:3, the accelerator being an onio-organic compound having a positive char-ge, the curing agent being a di- or polyhydroxy or di-or polythiol compound; the adduct being obtained by melting of the reaction product between accelerator and curing agent in the indicated molar ratios, or by mel-ting of the adduct 1:1 added with the curing agent in the amounts to reach the 1:2 to 1:5 adduct;
optionally C) the accelerator indicated in B) in amounts from 0.05 to 0.5 phr.
The onium compound used as accelerator in B) and C) and (AF9370 -e~t) _ 5 forming the adduct cation is generally selected from the following classes:
I) aminophosphonium [P(NR'R") n (R1 R2 R3) 4-n] +
wherein n is an integer from 1 to 3;
R', R" and Rl R2 R3, equal or different from each other, are alkylic, cycloalkylic, arylic, arylalkylic, oxy-alkylic or polyoxyalkylic groups having a free or este-rified terminal -OH function;
R' and R" contain from 1 to 7 carbon atoms and can be linked each other so as to form an heterocyclic ring with the nitrogen atom while R1, R2, R3 equal or diffe-rent from each other contain from 1 to 18 carbon atoms;
II) compounds having the formula Q+(RaRbRcRd) wherein Q is selected from nitrogen, phosphorus, arse-nlc, ant1monlum;
(III) compounds having formula:
S+(Ra Rb Rc)3 wherein in II) and III) Ra, Rb, RC, Rd are selected from alkyls, aryls, alkylaryls or their combinations, two of said free radicals can be linked each other and the Q or S atom can form an heterocyclic ring.
Preferred compounds are quaternary phosphonium com-~AP9370 --~e) 21~0~3 _ 6 pounds containing at least a phosphorus atom linked by four covalent simple bonds to four organic radicals, the organic radicals generally containing from 1 to 30 carbon atoms, preferably from 2 to 8. The organic ra-dical, being linear or branched, can contain hetero-atoms. Preferred compounds are triphenylbenzylphospho-nium, tetrabutylphosphonium.
The accelerator can be also a blend of the compounds of the single classes I) to III), or of more compounds of the same class.
The anion forming the adduct must be a curing agent and is generally selected from the polyhydroxy or polythiol com-pounds comprising the following classes:
X1) A(BH)m wherein A is an arylene radical optionally substituted with alkylic groups, such radical including optionally alkyl groups has from 6 to 14 carbon atoms, B is oxygen or sulphur and m is equal to 2 or 3;
X2 ) HB-R"'-BH
wherein R4a is an alkylene or cycloalkylene radical optionally substituted with alkylic groups, such radi-cal including optionally alkyl groups has from 6 to 18 carbon atoms and B is oxygen or sulphur;
(AP9370-eot) ~i~0~4~
X3) HO
~ ~ R2a _ <~
OH
wherein R2a is -SO-, -SO2-, -CO- or a linear or bran-ched alkylene radical containing from 1 to 9 carbon atoms and wherein the H atoms can be partially or wholly substituted with F atoms;
X4) HoCH2-R3a-CH2oH
wherein R3a is a perfluoropolyether or polyfluoroether chain, the average molecular weight by number Mn being from 360 to 2,000.
The accelerators forming the cation are described in the art for instance in USP 4259463 for aminophosphonium compounds, in USP 3712877 for quaternary phosphonium salts, USP 3655727 for quaternary ammonium salts, in EP 337705 for class III).
The preferred cations are those deriving from aminopho-sphonium wherein the phosphorus atom is linked to a nitrogen atom and the other three covalent bonds are formed by orga-nic radicals wherein the carbon is linked to phosphorus.
The following compounds can be cited:
(A~9370 -e~t) 2l~o3~l3 IC6Hs [C6Hs-cH2-pl-N-(cH2cH3) 2 ]
C6Hs IC6Hs [ C6Hs ~ CH2 ~ P ~ N ~ ( CH2 CH3 ) 2 ]
[((cH3)2N)3p-cH2-cH3]
[((CH3)2N)3P-CH3]
[P(N(CH3) 2) 2 (C6Hs) 2]
[P (N(C2Hs) 2) 2- (C6Hs) 2]
[P(N(CH3)z) 2 (C6Hs) (C6HscH2) ]
[P(N(C2Hs) 2) 2 (C6Hs) (C6HscH2) ]
[P(N(CH3) 2) 2 (C6Hs)(CH3)]
[P (N(C2Hs) 2) 3(C6HsCH2)]
The compound 1,1-diphenyl-1-benzyl-N-diethytl-phospho-ramine is particularly preferred.
Among the quaternary phosphonium compounds it can be cited (CH3) 2 (C2Hs) 2P
(C2Hs)3(claH37)p (CycloC6Hll) 2 (C6H13) 2P
(AF9370 -e~t) - 215~3 l~ _ 9 (C4Hg)3CH2=CH-CH2P
(C4Hg)4P
(C6Hs)3(c6HscH2)p (C6Hs)3(CH30C2Hs)P+
(C8Hl,)3[(cH3)2NcH2cH2cH2]P
(C,3H~,)3(HOc2H4)P
+P(C2Hs)3cH2cH2cH2cH2(c2Hs)3p Tetrabutyl phosphonium is particularly preferred.
Among anions the bisphenol compounds (class X3), whe-rein the R2a radical is the perfluoroalkyl group from 3 to 7 carbon atoms, and the OH are in para position, are prefer-red. The most preferred compound is R2a = -C(CF3) 2- .
The adduct can be prepared as follows.
The polyhydroxy or polythiol compound is reacted, in aqueous solution or in a suitable solvent, for instance me-thanol, wherein the accelerator is soluble, in a first step, with a basic substance, for instance NaOH, KOH, Ca(OH) 2 and tBuO-K+, generally by using one equivalent gram of basic sub-stance for mole of accelerator. The reaction product is then reacted in a second step with an accelerator salt, for instance a chloride. The desired salt precipitates. After filtering and drying, the product is melted which through cooling, solidifies in flakes or pellets giving the adduct (AF9370~ t) 21503~
utilized in the present invention. This solid form is parti-cularly suitable for its handling and its compounding in the blends.
The polyhydroxy or polythiol compounds are used in mo-lar ratios from 2:1 to 5:1 with respect to the accelerator.
Without being bound to any theory, it seems by IR
spectra that the excess of polyhydroxy compound results linked to the cation also when this results in excess with respect to the stoichiometric, as it must be according to the present invention.
Tests carried out by the Applicant have shown that the adducts with excess of bisphenol with respect to the accele-rator show superior properties if the amount of curing agent is added in excess during the adduct preparation or after the adduct achievement in molar ratios 1:1 between accelera-tor and curing agent, before bringing to melting the re-action mixture containing the excess of curing agent.
As a matter of fact, if the adduct in molar ratio 1:1 is prepared and the reaction product is melted and only afterwards the desired amount of curing agent is added, the improved results according to the present invention are not obtained.
The curing blend comprises moreover, in order to obtain (AE793 70 - ge ) 2150~43 the cured products through heating, a) one or more acceptors of inorganlc acids selected among the ones known in ionic vulcanisation of vinylidene fluoride copolymers, in amounts 1-40 parts for 100 parts fluoroelastomeric copolymer;
b) one or more basic compounds selected from those known in ionic vulcanisation of vinylidene fluoride copoly-mers, in amounts from 0.5 to 10 parts for 100 parts of fluoroelastomeric copolymer.
As also known, the basic compounds of point b) are usually selected from the group consisting of Ca(OH) 2' Sr(OH)z, Ba(OH)2, metal salts of weak acids, such as for in-stance carbonates, benzoates, oxalates and phosphites of Ca, Sr, Ba, Na and K and mixtures of the aforesaid hydroxides with the abovesaid metal salts.
The composition according to the present invention com-~nly ~a~ ~ls~ o~er ~n con~ nts, 6u~ as ~ r5, ~or instance, carbon black, silica and dyes, generally from 5 to30 phr; and processing adjuvants, for instance plastici-zers, generally from 0.1 to 5 phr.
However an advantage according to the present invention consists in that optimum results are obtained without using processing adjuvants, such as sulphones, which generally (A~9370---e) 21~03ll~
1~
lead to a worsening of the final properties depending on the used accelerating system.
rhe fluoroelastomeric copolymers, as said above, are vinylidenefluoride copolymers with one or more fluorinated monomers having ethylene unsaturation. In particular the copolymers of the present invention are VDF copolymers with hexafluoropropene.
Other comonomers having ethylene unsaturation which can be used are vinylethers (PAVE) in amounts from 0 to 40~ by weight, preferably 0-20~. The preferred vinylethers are per-fluoroalkylperfluorovinylethers, in particular perfluoro-methylperfluorovinylether (MVE) and perfluoropropylperfluo-rovinylether. Utilizable perfluorovinylethers and perfluo-roalkoxyvinylethers are described in USP 3291843.
Other comonomers which can be utilized in amounts from 0 to 30~ are for instance tetrafluoroethylene and/or chloro-trifluoroethylene.
The olefinic monomers having up to 4C are for instance selected from ethylene and propene, the preferred being ethylene (Et), and are used in amounts from 0 to 25~ by weight, preferably from 0 to 10~.
The preferred copolymers forming of the pre-ent invention are characterized by the following preferable (AP9370~ t) 2 ~ ~ 0 3 d~ r~
composition by weight of monomeric units:
% by weight VDF 40-50%
HFP 50-60%;
or by the composition:
% by weight VDF 30-50%
HFP 20-60%
TFE 10-30%;
or by the composition:
% by weight VDF 30-47%
HFP (hexafluoropropene) 20-40%
PAVE 3-20%
TFE 10-30%.
The copolymers of the invention combine a good chemical resistance with a high curing rate, essential requirement in transformation techniques such as injection molding.
Such copolymers are capable of meeting more and more severe marketing specifications, which require good resi-stance to alcohols and to petrols containing alcohols espe-cially methanol.
The VDF copolymers containing olefins particularly sui-(AP9370-e~t) 215 0 ~ 3 table due to their high resistance to alcohols and to bases, in particular oils containing amines, contain preferably the following monomer units:
~ by weight ethylene 2-15 TFE 0-30~
The fluoroelastomeric copolymers according to the pre-sent inve~ntion ~y b~ pr~p~r~d by ~ul~ion poly~rization ~c-cording to well known techniques, preferably in the presence of radicalic initiators such as for instance persulphates, perphosphates, alkaline or ammonium perborates or percarbo-nates, optionally in combination with reducing agents such as sulphites, bisulphites, hyposulphites, phosphites, hypo-phosphites of alkaline or ammonium metals, or in combination with ferrous, cupreous or silver salts, or of other easily oxidable metals. Such methods are described in Kirk Othmer, Encyclopaedia of Chemical Technology, vol. 8, pag. 500 and on, 1979. As polymerization methods can be used, in parti-cular, the mass polymerization, that in solution of organic solvents and the one in emulsion or suspension in water.
*****
The present invention relates to curable vinylidene-fluoride copolymers having a high content in fluorine, the other comonomers deriving from fluorinated monomers with ethylene unsaturation.
More in detail the present invention relates in parti-cular to fluoroelastomeric copolymers based on vinylidene-fluoride (VDF), hexafluoropropene (HFP), optionally in the presence of one or more comonomers ethylenically unsatura-ted, the F amount being higher than 67~ by weight.
More particularly the invention relates to fluoroela-stomeric copolymers based on VDF suitable to the preparation of fuel hoses and shaft seals.
It is known that for the preparation of these arti-cles, fluoroelastomeric polymers are required having good resistance to motor oils and/or to petrols containing polar substances, in particular alcohols.
This property must be combined with good elastomeric properties such as compression set and good mechanical pro-perties and good processability in molding both by compres-ta~370 ---t) 2 21S034~
sion, by injection and by extrusion.
The same copolymers can be also used for preparing 0-rings used in the injectors coming into contact with petrols and/or oils containing polar substances.
It is known making articles based on VDF, HFP and te-trafluoroethylene (TFE), optionally in the presence of per-fluoroalkylvinylethers (PAVE), using the peroxidic curing.
The disadvantage is that the compression set obtained are poor and the removal from molds is unsatisfactory.
It is also known from the previous patent application of the Applicant, EP 525687, to carry out the ionic curing with known accelerators and curing agents. The drawback is that these products show mechanical properties lower than the products cured with peroxides.
To obviate these inconveniences in the art it is known to use also processing aids such as sulphones or sulphoxi-des. The drawback is that the addition of these products, even though they lead to an improved rubber processing, wor-sen the mechanical properties and depending on the accelera-ting system worsen also the compression set.
It is known, moreover, that the elastomeric polymers having high content of fluorine show a bad processability due to the high viscosi~y of the compound.
(~F93 7 0 - ~9~: ) 21~03a~
All the disadvantages of the copolymes based on VDF
with low content in fluorine (less than 67~ by weight), are even more stressed in case of VDF copolymers having high content in fluorine, as indicated above.
~ n case of copolymers or terpolymers, indeed, having high content in fluorine, the crosslinking is even more dif-ficult and wherefore the mechanical and elastic properties and the processability of the artic~e result poor.
It has surprisingly and unexpectedly been found that it is possible to prepare fluoroelastomeric polymers based on VDF having a very good combination of - high mechanical properties, - low compression set, - low viscosity of the compound such as to allow an easy processing both by compression, by injection and by extrusion, - high resistance to oils and to petrols containing polar sub tances, such as alcohols or ethers.
This has been made possible by using ionic curing with a particular accelerating/curing system as herein defined.
Ac~ordingly, in one ot it& ~SQects~ th~ pr~s~lnt in~ntion r~l~t~S to cYr~bl~ ~luor~l~sto.~ric co~po~ltion& co~priSing A) 100 phr (parts) copolymers of terpolymers based on VDF
(AP9370 ---t) 21503~
having a content in fluorine of at least 67~ by weight, the VDF being comprised from 30 to 50~ by weight, from 20 to 60~ by weight of HFP, optionally other mono-meric units deriving from a monomer having ethyelene unsaturation; the sum of the comonomers being 100. In case of copolymers, the VDF ranges from 40 to 50 and HFP ranges from 50 to 60~ by weight. The other comono-mers are preferably from 0 to 30~ of TFE and from 0 to 40~ of perfuoroalkylvinylethers, preferably 0-20~;
B) 1 to 5 phr, preferably 2 to 4.5, of an adduct between an accelerator and a curing agent in molar ratio from 1:2 to 1:5, preferably 1:2 to 1:3, the accelerator being an onio-organic compound having a positive char-ge, the curing agent being a di- or polyhydroxy or di-or polythiol compound; the adduct being obtained by melting of the reaction product between accelerator and curing agent in the indicated molar ratios, or by mel-ting of the adduct 1:1 added with the curing agent in the amounts to reach the 1:2 to 1:5 adduct;
optionally C) the accelerator indicated in B) in amounts from 0.05 to 0.5 phr.
The onium compound used as accelerator in B) and C) and (AF9370 -e~t) _ 5 forming the adduct cation is generally selected from the following classes:
I) aminophosphonium [P(NR'R") n (R1 R2 R3) 4-n] +
wherein n is an integer from 1 to 3;
R', R" and Rl R2 R3, equal or different from each other, are alkylic, cycloalkylic, arylic, arylalkylic, oxy-alkylic or polyoxyalkylic groups having a free or este-rified terminal -OH function;
R' and R" contain from 1 to 7 carbon atoms and can be linked each other so as to form an heterocyclic ring with the nitrogen atom while R1, R2, R3 equal or diffe-rent from each other contain from 1 to 18 carbon atoms;
II) compounds having the formula Q+(RaRbRcRd) wherein Q is selected from nitrogen, phosphorus, arse-nlc, ant1monlum;
(III) compounds having formula:
S+(Ra Rb Rc)3 wherein in II) and III) Ra, Rb, RC, Rd are selected from alkyls, aryls, alkylaryls or their combinations, two of said free radicals can be linked each other and the Q or S atom can form an heterocyclic ring.
Preferred compounds are quaternary phosphonium com-~AP9370 --~e) 21~0~3 _ 6 pounds containing at least a phosphorus atom linked by four covalent simple bonds to four organic radicals, the organic radicals generally containing from 1 to 30 carbon atoms, preferably from 2 to 8. The organic ra-dical, being linear or branched, can contain hetero-atoms. Preferred compounds are triphenylbenzylphospho-nium, tetrabutylphosphonium.
The accelerator can be also a blend of the compounds of the single classes I) to III), or of more compounds of the same class.
The anion forming the adduct must be a curing agent and is generally selected from the polyhydroxy or polythiol com-pounds comprising the following classes:
X1) A(BH)m wherein A is an arylene radical optionally substituted with alkylic groups, such radical including optionally alkyl groups has from 6 to 14 carbon atoms, B is oxygen or sulphur and m is equal to 2 or 3;
X2 ) HB-R"'-BH
wherein R4a is an alkylene or cycloalkylene radical optionally substituted with alkylic groups, such radi-cal including optionally alkyl groups has from 6 to 18 carbon atoms and B is oxygen or sulphur;
(AP9370-eot) ~i~0~4~
X3) HO
~ ~ R2a _ <~
OH
wherein R2a is -SO-, -SO2-, -CO- or a linear or bran-ched alkylene radical containing from 1 to 9 carbon atoms and wherein the H atoms can be partially or wholly substituted with F atoms;
X4) HoCH2-R3a-CH2oH
wherein R3a is a perfluoropolyether or polyfluoroether chain, the average molecular weight by number Mn being from 360 to 2,000.
The accelerators forming the cation are described in the art for instance in USP 4259463 for aminophosphonium compounds, in USP 3712877 for quaternary phosphonium salts, USP 3655727 for quaternary ammonium salts, in EP 337705 for class III).
The preferred cations are those deriving from aminopho-sphonium wherein the phosphorus atom is linked to a nitrogen atom and the other three covalent bonds are formed by orga-nic radicals wherein the carbon is linked to phosphorus.
The following compounds can be cited:
(A~9370 -e~t) 2l~o3~l3 IC6Hs [C6Hs-cH2-pl-N-(cH2cH3) 2 ]
C6Hs IC6Hs [ C6Hs ~ CH2 ~ P ~ N ~ ( CH2 CH3 ) 2 ]
[((cH3)2N)3p-cH2-cH3]
[((CH3)2N)3P-CH3]
[P(N(CH3) 2) 2 (C6Hs) 2]
[P (N(C2Hs) 2) 2- (C6Hs) 2]
[P(N(CH3)z) 2 (C6Hs) (C6HscH2) ]
[P(N(C2Hs) 2) 2 (C6Hs) (C6HscH2) ]
[P(N(CH3) 2) 2 (C6Hs)(CH3)]
[P (N(C2Hs) 2) 3(C6HsCH2)]
The compound 1,1-diphenyl-1-benzyl-N-diethytl-phospho-ramine is particularly preferred.
Among the quaternary phosphonium compounds it can be cited (CH3) 2 (C2Hs) 2P
(C2Hs)3(claH37)p (CycloC6Hll) 2 (C6H13) 2P
(AF9370 -e~t) - 215~3 l~ _ 9 (C4Hg)3CH2=CH-CH2P
(C4Hg)4P
(C6Hs)3(c6HscH2)p (C6Hs)3(CH30C2Hs)P+
(C8Hl,)3[(cH3)2NcH2cH2cH2]P
(C,3H~,)3(HOc2H4)P
+P(C2Hs)3cH2cH2cH2cH2(c2Hs)3p Tetrabutyl phosphonium is particularly preferred.
Among anions the bisphenol compounds (class X3), whe-rein the R2a radical is the perfluoroalkyl group from 3 to 7 carbon atoms, and the OH are in para position, are prefer-red. The most preferred compound is R2a = -C(CF3) 2- .
The adduct can be prepared as follows.
The polyhydroxy or polythiol compound is reacted, in aqueous solution or in a suitable solvent, for instance me-thanol, wherein the accelerator is soluble, in a first step, with a basic substance, for instance NaOH, KOH, Ca(OH) 2 and tBuO-K+, generally by using one equivalent gram of basic sub-stance for mole of accelerator. The reaction product is then reacted in a second step with an accelerator salt, for instance a chloride. The desired salt precipitates. After filtering and drying, the product is melted which through cooling, solidifies in flakes or pellets giving the adduct (AF9370~ t) 21503~
utilized in the present invention. This solid form is parti-cularly suitable for its handling and its compounding in the blends.
The polyhydroxy or polythiol compounds are used in mo-lar ratios from 2:1 to 5:1 with respect to the accelerator.
Without being bound to any theory, it seems by IR
spectra that the excess of polyhydroxy compound results linked to the cation also when this results in excess with respect to the stoichiometric, as it must be according to the present invention.
Tests carried out by the Applicant have shown that the adducts with excess of bisphenol with respect to the accele-rator show superior properties if the amount of curing agent is added in excess during the adduct preparation or after the adduct achievement in molar ratios 1:1 between accelera-tor and curing agent, before bringing to melting the re-action mixture containing the excess of curing agent.
As a matter of fact, if the adduct in molar ratio 1:1 is prepared and the reaction product is melted and only afterwards the desired amount of curing agent is added, the improved results according to the present invention are not obtained.
The curing blend comprises moreover, in order to obtain (AE793 70 - ge ) 2150~43 the cured products through heating, a) one or more acceptors of inorganlc acids selected among the ones known in ionic vulcanisation of vinylidene fluoride copolymers, in amounts 1-40 parts for 100 parts fluoroelastomeric copolymer;
b) one or more basic compounds selected from those known in ionic vulcanisation of vinylidene fluoride copoly-mers, in amounts from 0.5 to 10 parts for 100 parts of fluoroelastomeric copolymer.
As also known, the basic compounds of point b) are usually selected from the group consisting of Ca(OH) 2' Sr(OH)z, Ba(OH)2, metal salts of weak acids, such as for in-stance carbonates, benzoates, oxalates and phosphites of Ca, Sr, Ba, Na and K and mixtures of the aforesaid hydroxides with the abovesaid metal salts.
The composition according to the present invention com-~nly ~a~ ~ls~ o~er ~n con~ nts, 6u~ as ~ r5, ~or instance, carbon black, silica and dyes, generally from 5 to30 phr; and processing adjuvants, for instance plastici-zers, generally from 0.1 to 5 phr.
However an advantage according to the present invention consists in that optimum results are obtained without using processing adjuvants, such as sulphones, which generally (A~9370---e) 21~03ll~
1~
lead to a worsening of the final properties depending on the used accelerating system.
rhe fluoroelastomeric copolymers, as said above, are vinylidenefluoride copolymers with one or more fluorinated monomers having ethylene unsaturation. In particular the copolymers of the present invention are VDF copolymers with hexafluoropropene.
Other comonomers having ethylene unsaturation which can be used are vinylethers (PAVE) in amounts from 0 to 40~ by weight, preferably 0-20~. The preferred vinylethers are per-fluoroalkylperfluorovinylethers, in particular perfluoro-methylperfluorovinylether (MVE) and perfluoropropylperfluo-rovinylether. Utilizable perfluorovinylethers and perfluo-roalkoxyvinylethers are described in USP 3291843.
Other comonomers which can be utilized in amounts from 0 to 30~ are for instance tetrafluoroethylene and/or chloro-trifluoroethylene.
The olefinic monomers having up to 4C are for instance selected from ethylene and propene, the preferred being ethylene (Et), and are used in amounts from 0 to 25~ by weight, preferably from 0 to 10~.
The preferred copolymers forming of the pre-ent invention are characterized by the following preferable (AP9370~ t) 2 ~ ~ 0 3 d~ r~
composition by weight of monomeric units:
% by weight VDF 40-50%
HFP 50-60%;
or by the composition:
% by weight VDF 30-50%
HFP 20-60%
TFE 10-30%;
or by the composition:
% by weight VDF 30-47%
HFP (hexafluoropropene) 20-40%
PAVE 3-20%
TFE 10-30%.
The copolymers of the invention combine a good chemical resistance with a high curing rate, essential requirement in transformation techniques such as injection molding.
Such copolymers are capable of meeting more and more severe marketing specifications, which require good resi-stance to alcohols and to petrols containing alcohols espe-cially methanol.
The VDF copolymers containing olefins particularly sui-(AP9370-e~t) 215 0 ~ 3 table due to their high resistance to alcohols and to bases, in particular oils containing amines, contain preferably the following monomer units:
~ by weight ethylene 2-15 TFE 0-30~
The fluoroelastomeric copolymers according to the pre-sent inve~ntion ~y b~ pr~p~r~d by ~ul~ion poly~rization ~c-cording to well known techniques, preferably in the presence of radicalic initiators such as for instance persulphates, perphosphates, alkaline or ammonium perborates or percarbo-nates, optionally in combination with reducing agents such as sulphites, bisulphites, hyposulphites, phosphites, hypo-phosphites of alkaline or ammonium metals, or in combination with ferrous, cupreous or silver salts, or of other easily oxidable metals. Such methods are described in Kirk Othmer, Encyclopaedia of Chemical Technology, vol. 8, pag. 500 and on, 1979. As polymerization methods can be used, in parti-cular, the mass polymerization, that in solution of organic solvents and the one in emulsion or suspension in water.
3 7 0 ~
2 1 ~ 4 ~
~5 . Surfactants, such as for instance ammonium perfluoro-octanoate or others known to be suitable in preparing fluo-roelastomers can be present in the polymerization medium, for example ammonium perfluoro-octanoate.
Chain transfer agents can generally be used as molecu-lar weight regulators. Among them ethyl acetate, ethyl malo-nate, iodided and/or brominated chain transfer agents, such as for instance the compounds having the general formula Rf(I)x(Br)y wherein Rf = perfluorinated hydrocarbon radical containing from 1 to 8 carbon atoms, x, y being integers comprised between 0 and 2, with at least x or y = 1 and x +
y is at most 2. It can also be used compounds having also some I or Br in the place of F of the perfluorinated hydro-carbon. These are known as polyiodided or polybrominated compounds. Moreover iodides and/or bromides of alkaline or alkaline-earth metals as described in European patent appli-cation No. 407937 can be used.
When the polymerization is over, the fluoroelastomer is isolated from the polymeric latex by known methods, such as coagulation by addition of electrolytes or by cooling.
The polymerization reaction is generally carried out at temperatures from 25C to 150C, under pressure up to 10 MPa.
(AF9370 -e~e) 2i3U~1~
-The preparation of the elastomeric copolymers according to the invention can be carried out also by polymerization in the presence of a microemulsion formed by one or more perfluoropolyoxyalkylenes and water, according to the method described in European patent application No. 250767.
The polymerization can be carried out also by using, instead of a microemulsion, an emulsion or a dispersion of perfluoropolyoxyalkylenes and water according to the method described in USA patent No. 4789717.
Also the emulsions and dispersions of perfluorooxy-alkylenes and water described for instance in European pa-tent applications Nos. 196904, 280312 and 360292, can be used for this purpose.
For the curing of the polymers of the invention the elastomeric composition must be heated under pressure, at a temperature from 130C to 230C, preferably from 160C to 200C, for a period of time comprised from 0.5 to 60 minutes and, preferably, from 1 to 15 minutes. The obtained arti-cles can then be post-cured in stove or in oven, at atmo-spheric pressure, at a temperature from 130 to 300C, pre-ferably from 200C to 275C, for a period of time from 5 to 48 hours, and, preferably, from 10 to 24 hours.
The following examples are given for illustrative pur-(AF9370 -~9t) - 21S034~
-pose but do not limit the scope of the present invention.
EXAMPLES
Preparation of the adduct 2 adducts according to the present invention are prepared by starting from the accelerator indicated below and from the bisphenol AF (BAF):
HO - ~ C ~ ~ OH
The accelerator has the following formula:
IC6Hs [C6Hs-cH2-pl-N- (CH2CH3) 2] + Cl-C6Hs The preparation of the adduct produced starting from one accelerator mole and 5 (or 2 moles in case of 1:2 ratio, 3 moles for 1:3, and 4 moles for 1:4), moles of bisphenol AF
gives the adduct in the molar ratio specified above.
In a 10 1 glass reactor, equipped with a dropping fun-nel and a stirrer, 352.8 g (1.05 moles) of bisphenol AF are dispersed under stirring into 5 1 of water. A solution of 8.4 g (0.21 moles) of NaOH in 500 cc of water is then qui-ckly dropped in the reactor. The reactor is kept under stir-ring at room temperature for 30 minutes. Then a solution of (AF9370 -e~t) 21 SQ3'13 80.5 g (0.21 moles) of amino-phosphonium dissolved in 800 cc of water is dropped under stirring in the reactor. A very thick suspension is obtained; it is kept under stirring at room temperature for 2 hours; then it is let to stay for about 4 hours. It is filtered on cloth and washed twice with overall 2 l of water. It is dried in a vacuum stove to 50-60C for 20 hours and then the reaction mixture is brought to melt by heating at 100-120C and it is allowed to cool, thus obtaining the adduct 1:5 according to the present invention.
In Table 1 the formulation of 3 compounds is reported, the first of which (compound No. 1) is a composition wherein an adduct according to the present invention was not used, but, separately, the accelerator and the bisphenol AF.
In the compounds 2 and 3 the adduct prepared according to the present invention was utilized.
The fluoroelastomer is TECNOFLON(R) TH 340 of Ausimont, vin-ylidene fluoride, hexafluoropropene and tetrafluoroethylene terpolymer having a Mooney viscosity ML (1+10) at 121C
equal to 58, whose composition is:
VDF 37% by weight HFP 37% "
(AE'9370-e~t) 21~03'1~
~ lS
TFE 26% "
(Fluorine: 70% by weight) TABLE 1: FORMnLATION OF THE COMPOUND
Ex. 1 Ex. 2 Ex. 3 (cfr) (phr) (phr) (phr) Fluoroelastomer TH 340 100 100 100 Bisphenol AF 2.7 - -Accelerator (I) 1.35 Adduct (II) - 4.5 Adduct (III) - - 3.5 MgO 3 3 3 Ca(OH) 2 6 6 6 MT Black . 30 30 30 Accelerators (I): [Ph2~-N-(CH2CH~)2]+Cl-CH2Ph Adduct (II): molar ratio accelerator/bisphenol 1:3 obtai-ned by melting the reaction mixture.
AddUCt (III): 1: 5 obtained by melting of the reaction mix-ture.
(A~9370 -~3t) 21~034~
_ ~C
Characterization of the compound of Table lA
These blends were cured at 170C in press and then to a post-curing in air stove between 200C and 250C for 24 hours.
The curing evaluation was carried out by oscillating disc rheometer (ODR) of Monsanto type according to ASTM D
2084/81.
The data relating to the blends viscosity, the curing chara-cteristics and the mechanical properties are reported in Table lA.
(AP9370-e8t) 21aO~43 . 21 TABLE lA: characteristics of the compound of Table 1.
Ex 1 Ex. 2 Ex. 3 (cfr) Rheometric properties Mooney Viscosity (ASTM D1646-82) ML(1+10) at 121C (Mooney)106 82 103 Mooney Scorch at 135C
Minimum Viscosity (in Mooney) 44 32 45 Time for increasing of 15 points the viscosity (min) 11'45" 33~20ll 30 ODR 12' at 177C, Arc +/- 3 (ASTM D2084-81) ML (lbf in) 16 13 16 MH (lbf-in) 72 108 96 ts2 (sec) 123 141 168 t90 (sec) 249 270 333 V~ax (lbf-in/sec) 0.8 1.8 1.2 Mechanical properties (ASTM D412-83) Post cure @ 250C x 8+16 hours Modulus 100~ (MPa) 6.6 7.9 6.9 Tensile stress (MPa) 13.5 16 15.5 Elongation at break (~) 228 181 219 Hardness Shore A 82 82 85 Compression Set 70 h at 200C
(ASTM D 395 Method B) O-rings 214 (~) 66 31 32 (AP9370 -egt) 2; ~) O ~J ~1 ~
-~ 22 From the above results it is noticed that the viscosity de-creases by indicating an improved processability; the scorch increases therefore indicating a greater compound safety;
the curing (ODR) shows a greater crosslinking yield (MH) and higher curing rate (v~ax). The balance of the mechanical properties is surprisingly very satisfactory: a higher ten-sile stress/elongation ratio is obtained. The compression set is unexpectedly improved to a great extent.
Examples 1-3 were repeated using a fluoroelastomer TECNOFLO-N(R) T428E of Ausimont: terpolymer of vinylidenefluoride, he-xafluoropropene and tetrafluoroethylene, having a Mooney ML
(1+10) viscosity at 121C equal to 20, whose composition is:
VDF 45% by weight HFP 33% "
TFE 22% I~
(Fluorine: 68.5% by weight); [~]MEK30C = 55 (intrinsic visco-sity).
The formulations are reported in Table 2 and the chara-cteristics are reported in Table 2A.
~AP9370-e~t) 215~3~3 ~3 TABLE 2: COMPOUNDS FORMULATION
EX. 4 EX. 5 (cfr) (phr) (phr) Fluoroelastomer NMA2 100 100 Bisphenol AF 1.5 Accelerant (I) 0.6 Adduct (II) - 2 MgO 3 3 Ca(OH) 2 6 6 MT Black 30 30 (AP9370 -es~) 215 03 !l~
._ TABLE 2A: characteristics of the compound of Table 1.
Ex. 4Ex. 5 (cfr) Rheometric properties Mooney Viscosity (ASTM D 1646-82) ML(1+10) at 121C (in Mooney) 39 39 Mooney Scorch at 135C
Minimum Viscosity (in Mooney) 14 13 Time for increasing of 15 points the viscosity (min) 37~30~ 40l30 ODR 12' at 177C Arc+/-3 (ASTM D2084-81) ML (lbf in) 4 4 MH (lbf-in) 44 52 ts2 (sec) 195 168 t90 (sec) 285 237 vmax (lbf-in/sec) 0.8 1.4 Mechanical properties (ASDTM D412-83) Post curing @ 250C x 8+16 hours Modulus 100~ (MPa) 2.5 4.0 Tensile strength (MPa) 12 14 Elongation at break (~) 329 286 Hardness Shore A 63 62 Compression Set 70h at 200C (ASTM
D 395 Method B) O-rings 214 (~) 54 34 Compression Set 70h at 23C
O-rings 214 (~) 44 30 (AP9370 -e9e) 21~1~343 -The results show the same previous trends, in particular as regards the curing rate (vmax), compression set and the im-proved balance of the mechanical properties.
Examples 1-3 were repeated with the fluoroelastomer indica-ted below; the formulations are reported in Table 3 and the characteristics in Table 3A.
High fluorine tetrapolymer TECNOFLON(R) LX 5291 having compo-sition:
VDF 32~ by weight HFP 30~ ~I
MVE 7~ " (perfluoromethylvinylether) TFE 31% "
(Fluorine 70~ ML(1+10) at 121C = 31.
TABLE 3: COMPOUND FORMULATION
EX. 6 EX. 7 (cfr) (phr) (phr) Fluoroelastomer 100 100 Bisphenol AF 2.7 Accelerant (I) 1.35 0.3 Adduct III - 3.5 MgO 3 3 Ca(OH)2 6 6 MT Black 30 30 (AP9370-e~t) - 2~.~aO3li3 _ 2&
TABLE 3A: characteristics of the compound of Table 3.
Ex. 6 Ex. 7 (cfr) Rheometric properties Mooney Viscosity (ASTM D 1646-82) ML(1+10) at 121C (in Mooney) 78 74 ODR 12' at 177C Arc+/-3 (ASTM D2084-81) ML (lbf-in) 10 9 MH (lbf-in) 54 77 ts2 (sec) 225 246 t90 (sec) 350 390 vmax (lbf-in/sec) 0.5 1.1 Mechanical properties (ASDTM D412-83) Post curing @ 250C x 8+16 hours Modulus 100~ (MPa) 5.3 6.0 Tensile strength (MPa) 11 13 Elongation at break (~) 220 203 Hardness Shore A 79 81 Compression Set 70h at 200C
(ASTM D 395 Method B) O-rings 214 (~) 63 30 (AEr9370 -el~t) 21~0~t~
By comparing the results it is noted the same trend of the previous examples: an improved processability (lower Mooney of the compound); improved crosslinking yield (MH) and crosslinking rate (v~ax); the balance of the mechanical and elastomeric properties shows a clear improvement.
~AE'9370 -e9t)
2 1 ~ 4 ~
~5 . Surfactants, such as for instance ammonium perfluoro-octanoate or others known to be suitable in preparing fluo-roelastomers can be present in the polymerization medium, for example ammonium perfluoro-octanoate.
Chain transfer agents can generally be used as molecu-lar weight regulators. Among them ethyl acetate, ethyl malo-nate, iodided and/or brominated chain transfer agents, such as for instance the compounds having the general formula Rf(I)x(Br)y wherein Rf = perfluorinated hydrocarbon radical containing from 1 to 8 carbon atoms, x, y being integers comprised between 0 and 2, with at least x or y = 1 and x +
y is at most 2. It can also be used compounds having also some I or Br in the place of F of the perfluorinated hydro-carbon. These are known as polyiodided or polybrominated compounds. Moreover iodides and/or bromides of alkaline or alkaline-earth metals as described in European patent appli-cation No. 407937 can be used.
When the polymerization is over, the fluoroelastomer is isolated from the polymeric latex by known methods, such as coagulation by addition of electrolytes or by cooling.
The polymerization reaction is generally carried out at temperatures from 25C to 150C, under pressure up to 10 MPa.
(AF9370 -e~e) 2i3U~1~
-The preparation of the elastomeric copolymers according to the invention can be carried out also by polymerization in the presence of a microemulsion formed by one or more perfluoropolyoxyalkylenes and water, according to the method described in European patent application No. 250767.
The polymerization can be carried out also by using, instead of a microemulsion, an emulsion or a dispersion of perfluoropolyoxyalkylenes and water according to the method described in USA patent No. 4789717.
Also the emulsions and dispersions of perfluorooxy-alkylenes and water described for instance in European pa-tent applications Nos. 196904, 280312 and 360292, can be used for this purpose.
For the curing of the polymers of the invention the elastomeric composition must be heated under pressure, at a temperature from 130C to 230C, preferably from 160C to 200C, for a period of time comprised from 0.5 to 60 minutes and, preferably, from 1 to 15 minutes. The obtained arti-cles can then be post-cured in stove or in oven, at atmo-spheric pressure, at a temperature from 130 to 300C, pre-ferably from 200C to 275C, for a period of time from 5 to 48 hours, and, preferably, from 10 to 24 hours.
The following examples are given for illustrative pur-(AF9370 -~9t) - 21S034~
-pose but do not limit the scope of the present invention.
EXAMPLES
Preparation of the adduct 2 adducts according to the present invention are prepared by starting from the accelerator indicated below and from the bisphenol AF (BAF):
HO - ~ C ~ ~ OH
The accelerator has the following formula:
IC6Hs [C6Hs-cH2-pl-N- (CH2CH3) 2] + Cl-C6Hs The preparation of the adduct produced starting from one accelerator mole and 5 (or 2 moles in case of 1:2 ratio, 3 moles for 1:3, and 4 moles for 1:4), moles of bisphenol AF
gives the adduct in the molar ratio specified above.
In a 10 1 glass reactor, equipped with a dropping fun-nel and a stirrer, 352.8 g (1.05 moles) of bisphenol AF are dispersed under stirring into 5 1 of water. A solution of 8.4 g (0.21 moles) of NaOH in 500 cc of water is then qui-ckly dropped in the reactor. The reactor is kept under stir-ring at room temperature for 30 minutes. Then a solution of (AF9370 -e~t) 21 SQ3'13 80.5 g (0.21 moles) of amino-phosphonium dissolved in 800 cc of water is dropped under stirring in the reactor. A very thick suspension is obtained; it is kept under stirring at room temperature for 2 hours; then it is let to stay for about 4 hours. It is filtered on cloth and washed twice with overall 2 l of water. It is dried in a vacuum stove to 50-60C for 20 hours and then the reaction mixture is brought to melt by heating at 100-120C and it is allowed to cool, thus obtaining the adduct 1:5 according to the present invention.
In Table 1 the formulation of 3 compounds is reported, the first of which (compound No. 1) is a composition wherein an adduct according to the present invention was not used, but, separately, the accelerator and the bisphenol AF.
In the compounds 2 and 3 the adduct prepared according to the present invention was utilized.
The fluoroelastomer is TECNOFLON(R) TH 340 of Ausimont, vin-ylidene fluoride, hexafluoropropene and tetrafluoroethylene terpolymer having a Mooney viscosity ML (1+10) at 121C
equal to 58, whose composition is:
VDF 37% by weight HFP 37% "
(AE'9370-e~t) 21~03'1~
~ lS
TFE 26% "
(Fluorine: 70% by weight) TABLE 1: FORMnLATION OF THE COMPOUND
Ex. 1 Ex. 2 Ex. 3 (cfr) (phr) (phr) (phr) Fluoroelastomer TH 340 100 100 100 Bisphenol AF 2.7 - -Accelerator (I) 1.35 Adduct (II) - 4.5 Adduct (III) - - 3.5 MgO 3 3 3 Ca(OH) 2 6 6 6 MT Black . 30 30 30 Accelerators (I): [Ph2~-N-(CH2CH~)2]+Cl-CH2Ph Adduct (II): molar ratio accelerator/bisphenol 1:3 obtai-ned by melting the reaction mixture.
AddUCt (III): 1: 5 obtained by melting of the reaction mix-ture.
(A~9370 -~3t) 21~034~
_ ~C
Characterization of the compound of Table lA
These blends were cured at 170C in press and then to a post-curing in air stove between 200C and 250C for 24 hours.
The curing evaluation was carried out by oscillating disc rheometer (ODR) of Monsanto type according to ASTM D
2084/81.
The data relating to the blends viscosity, the curing chara-cteristics and the mechanical properties are reported in Table lA.
(AP9370-e8t) 21aO~43 . 21 TABLE lA: characteristics of the compound of Table 1.
Ex 1 Ex. 2 Ex. 3 (cfr) Rheometric properties Mooney Viscosity (ASTM D1646-82) ML(1+10) at 121C (Mooney)106 82 103 Mooney Scorch at 135C
Minimum Viscosity (in Mooney) 44 32 45 Time for increasing of 15 points the viscosity (min) 11'45" 33~20ll 30 ODR 12' at 177C, Arc +/- 3 (ASTM D2084-81) ML (lbf in) 16 13 16 MH (lbf-in) 72 108 96 ts2 (sec) 123 141 168 t90 (sec) 249 270 333 V~ax (lbf-in/sec) 0.8 1.8 1.2 Mechanical properties (ASTM D412-83) Post cure @ 250C x 8+16 hours Modulus 100~ (MPa) 6.6 7.9 6.9 Tensile stress (MPa) 13.5 16 15.5 Elongation at break (~) 228 181 219 Hardness Shore A 82 82 85 Compression Set 70 h at 200C
(ASTM D 395 Method B) O-rings 214 (~) 66 31 32 (AP9370 -egt) 2; ~) O ~J ~1 ~
-~ 22 From the above results it is noticed that the viscosity de-creases by indicating an improved processability; the scorch increases therefore indicating a greater compound safety;
the curing (ODR) shows a greater crosslinking yield (MH) and higher curing rate (v~ax). The balance of the mechanical properties is surprisingly very satisfactory: a higher ten-sile stress/elongation ratio is obtained. The compression set is unexpectedly improved to a great extent.
Examples 1-3 were repeated using a fluoroelastomer TECNOFLO-N(R) T428E of Ausimont: terpolymer of vinylidenefluoride, he-xafluoropropene and tetrafluoroethylene, having a Mooney ML
(1+10) viscosity at 121C equal to 20, whose composition is:
VDF 45% by weight HFP 33% "
TFE 22% I~
(Fluorine: 68.5% by weight); [~]MEK30C = 55 (intrinsic visco-sity).
The formulations are reported in Table 2 and the chara-cteristics are reported in Table 2A.
~AP9370-e~t) 215~3~3 ~3 TABLE 2: COMPOUNDS FORMULATION
EX. 4 EX. 5 (cfr) (phr) (phr) Fluoroelastomer NMA2 100 100 Bisphenol AF 1.5 Accelerant (I) 0.6 Adduct (II) - 2 MgO 3 3 Ca(OH) 2 6 6 MT Black 30 30 (AP9370 -es~) 215 03 !l~
._ TABLE 2A: characteristics of the compound of Table 1.
Ex. 4Ex. 5 (cfr) Rheometric properties Mooney Viscosity (ASTM D 1646-82) ML(1+10) at 121C (in Mooney) 39 39 Mooney Scorch at 135C
Minimum Viscosity (in Mooney) 14 13 Time for increasing of 15 points the viscosity (min) 37~30~ 40l30 ODR 12' at 177C Arc+/-3 (ASTM D2084-81) ML (lbf in) 4 4 MH (lbf-in) 44 52 ts2 (sec) 195 168 t90 (sec) 285 237 vmax (lbf-in/sec) 0.8 1.4 Mechanical properties (ASDTM D412-83) Post curing @ 250C x 8+16 hours Modulus 100~ (MPa) 2.5 4.0 Tensile strength (MPa) 12 14 Elongation at break (~) 329 286 Hardness Shore A 63 62 Compression Set 70h at 200C (ASTM
D 395 Method B) O-rings 214 (~) 54 34 Compression Set 70h at 23C
O-rings 214 (~) 44 30 (AP9370 -e9e) 21~1~343 -The results show the same previous trends, in particular as regards the curing rate (vmax), compression set and the im-proved balance of the mechanical properties.
Examples 1-3 were repeated with the fluoroelastomer indica-ted below; the formulations are reported in Table 3 and the characteristics in Table 3A.
High fluorine tetrapolymer TECNOFLON(R) LX 5291 having compo-sition:
VDF 32~ by weight HFP 30~ ~I
MVE 7~ " (perfluoromethylvinylether) TFE 31% "
(Fluorine 70~ ML(1+10) at 121C = 31.
TABLE 3: COMPOUND FORMULATION
EX. 6 EX. 7 (cfr) (phr) (phr) Fluoroelastomer 100 100 Bisphenol AF 2.7 Accelerant (I) 1.35 0.3 Adduct III - 3.5 MgO 3 3 Ca(OH)2 6 6 MT Black 30 30 (AP9370-e~t) - 2~.~aO3li3 _ 2&
TABLE 3A: characteristics of the compound of Table 3.
Ex. 6 Ex. 7 (cfr) Rheometric properties Mooney Viscosity (ASTM D 1646-82) ML(1+10) at 121C (in Mooney) 78 74 ODR 12' at 177C Arc+/-3 (ASTM D2084-81) ML (lbf-in) 10 9 MH (lbf-in) 54 77 ts2 (sec) 225 246 t90 (sec) 350 390 vmax (lbf-in/sec) 0.5 1.1 Mechanical properties (ASDTM D412-83) Post curing @ 250C x 8+16 hours Modulus 100~ (MPa) 5.3 6.0 Tensile strength (MPa) 11 13 Elongation at break (~) 220 203 Hardness Shore A 79 81 Compression Set 70h at 200C
(ASTM D 395 Method B) O-rings 214 (~) 63 30 (AEr9370 -el~t) 21~0~t~
By comparing the results it is noted the same trend of the previous examples: an improved processability (lower Mooney of the compound); improved crosslinking yield (MH) and crosslinking rate (v~ax); the balance of the mechanical and elastomeric properties shows a clear improvement.
~AE'9370 -e9t)
Claims (17)
1. Curable fluoroelastomeric compositions comprising:
A) 100 phr copolymers or terpolymers based on VDF
having a content in fluorine of at least 67% by weight, the VDF being comprised from 30 to 50% by weight, from 20 to 60% by weight of HFP, optio-nally other monomeric units deriving from a mono-mer having ethylene unsaturation; the sum of the comonomers being 100;
B) from 1 to 5 phr of an adduct between an accelera-tor and a curing agent in molar ratio from 1:2 to 1:5, the accelerator being an onio-organic com-pound having a positive charge, the curing agent being a di- or polyhydroxy or di- or polythiol compound; the adduct being obtained by melting of the reaction product between accelerator and cu-ring agent in the indicated molar ratios, or by melting of the adduct mixture 1:1 added with the curing agent in the indicated amounts; optionally C) the accelerator indicated in B) in amounts from 0.05 to 0.5 phr.
A) 100 phr copolymers or terpolymers based on VDF
having a content in fluorine of at least 67% by weight, the VDF being comprised from 30 to 50% by weight, from 20 to 60% by weight of HFP, optio-nally other monomeric units deriving from a mono-mer having ethylene unsaturation; the sum of the comonomers being 100;
B) from 1 to 5 phr of an adduct between an accelera-tor and a curing agent in molar ratio from 1:2 to 1:5, the accelerator being an onio-organic com-pound having a positive charge, the curing agent being a di- or polyhydroxy or di- or polythiol compound; the adduct being obtained by melting of the reaction product between accelerator and cu-ring agent in the indicated molar ratios, or by melting of the adduct mixture 1:1 added with the curing agent in the indicated amounts; optionally C) the accelerator indicated in B) in amounts from 0.05 to 0.5 phr.
2. Compositions according to claim 1 wherein the other monomeric units are from 0 to 30% by weight of TFE and from 0 to 40 by weight of perfluoroalkylvinylethers.
3. Compositions according to claims 1 and 2 wherein B) ranges from 2 to 4.5 phr and the adduct is 1:2 or 1:3.
4. Compositions according to claims 1-3 wherein the acce-lerator forming the adduct cation is selected from the following classes:
I) aminophosphonium [P(NR'R") n (R1 R2 R3) +-n] +
wherein n is an integer from 1 to 3;
R', R" and R1 R2 R3, equal or different from each other, are alkylic, cycloalkylic, arylic, arylalkylic, oxy-alkylic or polyoxyalkylic groups having a free or este-rified terminal -OH function;
R' and R" contain from 1 to 7 carbon atoms and can be linked each other so as to form an heterocyclic ring with the nitrogen atom while R1, R2, R3 equal or diffe-rent from each other contain from 1 to 18 carbon atoms;
II) compounds having the formula Q+(RaRbRcRd)4 wherein Q is selected from nitrogen, phosphorus, arse-nic, antimonium;
III) compounds having formula:
S+ (Ra Rb RC) 3 wherein in II) and III) Ra, Rb, RC, Rd are selected from alkyls, aryls, alkylaryls or their combinations, two of said free radicals can be linked each other and the Q or S atom can form an heterocyclic ring.
I) aminophosphonium [P(NR'R") n (R1 R2 R3) +-n] +
wherein n is an integer from 1 to 3;
R', R" and R1 R2 R3, equal or different from each other, are alkylic, cycloalkylic, arylic, arylalkylic, oxy-alkylic or polyoxyalkylic groups having a free or este-rified terminal -OH function;
R' and R" contain from 1 to 7 carbon atoms and can be linked each other so as to form an heterocyclic ring with the nitrogen atom while R1, R2, R3 equal or diffe-rent from each other contain from 1 to 18 carbon atoms;
II) compounds having the formula Q+(RaRbRcRd)4 wherein Q is selected from nitrogen, phosphorus, arse-nic, antimonium;
III) compounds having formula:
S+ (Ra Rb RC) 3 wherein in II) and III) Ra, Rb, RC, Rd are selected from alkyls, aryls, alkylaryls or their combinations, two of said free radicals can be linked each other and the Q or S atom can form an heterocyclic ring.
5. Compositions according to claim 4 wherein the accele-rator is selected from the quaternary phosphonium com-pounds containing at least a phosphorus atom linked with four simple covalent bonds to four organic radi-cals, the organic radicals generally containing from 2 to 8 carbon atoms, the organic radical, being linear or branched, optionally containing heteroatoms; or from aminophosphonium derivatives wherein the phosphorus atom is linked to a nitrogen atom and the other three covalent bonds are organic radicals wherein the carbon is linked to the phosphorus.
6. Compositions according to claims from 1 to 5 wherein the anion obtained from the curing agent is selected from the polyhydroxy or polythiol compounds from the following classes:
X1) A(BH)m wherein A is an arylene radical optionally substituted with alkylic groups, such radical including optionally alkyl groups has from 6 to 14 carbon atoms, B is oxygen or sulphur and m is equal to 2 or 3;
X2) HB-R4a-BH
wherein R4a is an alkylene or cycloalkylene radical optionally substituted with alkylic groups, such radi-cal including optionally alkyl groups has from 6 to 18 carbon atoms and B is oxygen or sulphur;
X3) wherein R2a is -SO-, -SO2-, -CO- or a linear or bran-ched alkylene radical containing from 1 to 9 carbon atoms and wherein the H atoms can be partially or wholly substituted with F atoms X4) HOCH2-R3a-CH2OH
wherein R3a is a perfluoropolyether or polyfluoroether chain, the averge molecular weight by number Mn being from 360 to 2,000.
X1) A(BH)m wherein A is an arylene radical optionally substituted with alkylic groups, such radical including optionally alkyl groups has from 6 to 14 carbon atoms, B is oxygen or sulphur and m is equal to 2 or 3;
X2) HB-R4a-BH
wherein R4a is an alkylene or cycloalkylene radical optionally substituted with alkylic groups, such radi-cal including optionally alkyl groups has from 6 to 18 carbon atoms and B is oxygen or sulphur;
X3) wherein R2a is -SO-, -SO2-, -CO- or a linear or bran-ched alkylene radical containing from 1 to 9 carbon atoms and wherein the H atoms can be partially or wholly substituted with F atoms X4) HOCH2-R3a-CH2OH
wherein R3a is a perfluoropolyether or polyfluoroether chain, the averge molecular weight by number Mn being from 360 to 2,000.
7. Curable compositions according to claims from 1 to 6 wherein to obtain the cured product it comprises:
a) one or more acceptors of inorganic acids selected from those known in ionic vulcanisation of vinyli-dene fluoride copolymers, in amounts 1-40 parts for 100 parts fluoroelastomeric copolymer;
b) one or more basic compounds selected from those known in ionic curing of vinylidenefluoride co-polymers, in amounts from 0.5 to 10 parts for 100 parts of fluoroelastomeric copolymer.
a) one or more acceptors of inorganic acids selected from those known in ionic vulcanisation of vinyli-dene fluoride copolymers, in amounts 1-40 parts for 100 parts fluoroelastomeric copolymer;
b) one or more basic compounds selected from those known in ionic curing of vinylidenefluoride co-polymers, in amounts from 0.5 to 10 parts for 100 parts of fluoroelastomeric copolymer.
8. Curable compositions according to claims 1 and 2 whe-rein is present also an olefin in amounts from 0 to 25 by weight as ethylenically unsaturated monomer.
9. Curable cmpositions according to claims from 1 to 7 wherein the monomeric composition by weight is:
VDF 40-50%
HFP 50-60%.
VDF 40-50%
HFP 50-60%.
10. Curable compositions according to claims 1-7 wherein the monomeric composition by weight is:
VDF 30-50%
HFP 20-60%.
TFE 10-30%.
VDF 30-50%
HFP 20-60%.
TFE 10-30%.
11. Curable composition according to claims 1-7, wherein the monomeric composition by weight is:
VDF 30-47%
HFP (hexafluoropropene) 20-40%
PAVE 3-20%
TFE 10-30%.
VDF 30-47%
HFP (hexafluoropropene) 20-40%
PAVE 3-20%
TFE 10-30%.
12. Curable compositions according to claim 8, wherein the monomeric composition by weight is:
VDF 30-50%
HFP 20-58%
PAVE 0-40%
ethylene 2-15%
TFE 0-30%.
VDF 30-50%
HFP 20-58%
PAVE 0-40%
ethylene 2-15%
TFE 0-30%.
13. Use of the compositions according to claims 1-12 for preparing fuel hoses and shaft seals.
14. Use of the compositions according to claims 1-12 for preparing O-rings for injectors.
15. Use according to claims 13 and 14 wherein the fluoro-elastomeric compositions are those of claim 10.
16. Adduct between an accelerator and a curing agent in molar ratio from 1:2 to 1:5, the accelerator being an onio-organic compound having a positive charge, the curing agent being a di- or polyhydroxy or di- or poly-thiol compound; the adduct being obtained by melting of the reaction product between accelerator and curing agent in the indicated molar ratios, or by melting of the adduct mixture 1:1 added with the curing agent in the indicated amounts.
17. Adduct according to claim 16, wherein the cation is selected from the classes of claim 4 and the anion from the compounds of claim 6.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| ITMI941080A IT1269845B (en) | 1994-05-27 | 1994-05-27 | VULCANIZABLE FLUOROELASTOMERIC COMPOSITIONS |
| ITMI94A001080 | 1994-05-27 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2150343A1 true CA2150343A1 (en) | 1995-11-28 |
Family
ID=11368990
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002150343A Abandoned CA2150343A1 (en) | 1994-05-27 | 1995-05-26 | Curable fluoroelastomeric compositions |
Country Status (9)
| Country | Link |
|---|---|
| US (2) | US5648430A (en) |
| EP (1) | EP0684277B1 (en) |
| JP (1) | JP3979681B2 (en) |
| CN (2) | CN1100821C (en) |
| AT (1) | ATE324404T1 (en) |
| CA (1) | CA2150343A1 (en) |
| DE (1) | DE69534957T2 (en) |
| IT (1) | IT1269845B (en) |
| RU (1) | RU2152962C1 (en) |
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| JP3629828B2 (en) * | 1996-07-24 | 2005-03-16 | ユニマテック株式会社 | Fluorine-containing elastomer composition |
| IT1286042B1 (en) * | 1996-10-25 | 1998-07-07 | Ausimont Spa | O-RINGS FROM VULCANIZABLE FLUOROELASTOMERS BY IONIC WAY |
| IT1292361B1 (en) * | 1997-05-20 | 1999-01-29 | Ausimont Spa | VOLCANIZABLE FLUOROELASTOMERIC COMPOSITIONS |
| WO2001000696A1 (en) * | 1999-06-29 | 2001-01-04 | Daikin Industries, Ltd. | Fluoroelastomer and vulcanized molding |
| IT1318487B1 (en) * | 2000-04-21 | 2003-08-25 | Ausimont Spa | FLUORO-ELASTOMERS. |
| IT1318488B1 (en) * | 2000-04-21 | 2003-08-25 | Ausimont Spa | FLUOROVINYLETERS AND POLYMERS THAT CAN BE OBTAINED. |
| US7534845B2 (en) | 2000-04-21 | 2009-05-19 | Solvay Solexis S.P.A. | Fluorovinyl ethers and polymers obtainable therefrom |
| US6730760B2 (en) * | 2001-01-31 | 2004-05-04 | 3M Innovative Properties Company | Perfluoroelastomers having a low glass transition temperature and method of making them |
| ITMI20011062A1 (en) | 2001-05-22 | 2002-11-22 | Ausimont Spa | FLUOROELASTOMERIC COMPOSITIONS |
| ITMI20011059A1 (en) | 2001-05-22 | 2002-11-22 | Ausimont Spa | FLUOROELASTOMERIC COMPOSITIONS |
| ITMI20011060A1 (en) | 2001-05-22 | 2002-11-22 | Ausimont Spa | FLUOROELASTOMERIC COMPOSITIONS |
| ITMI20012164A1 (en) * | 2001-10-18 | 2003-04-18 | Ausimont Spa | FLUORO-ELASTOMERS |
| ITMI20020598A1 (en) * | 2002-03-22 | 2003-09-22 | Ausimont Spa | VULCANIZABLE FLUOROELASTOMERS |
| US6833418B2 (en) * | 2002-04-05 | 2004-12-21 | 3M Innovative Properties Company | Dispersions containing perfluorovinyl ether homopolymers and use thereof |
| US6822059B2 (en) * | 2002-04-05 | 2004-11-23 | 3M Innovative Properties Company | Dispersions containing bicomponent fluoropolymer particles and use thereof |
| CA2441641C (en) * | 2003-09-23 | 2006-01-31 | Westport Research Inc. | A high pressure gaseous fuel supply system for an internal combustion engine and a method of sealing connections between components to prevent leakage of a high pressure gaseous fuel |
| US20050268782A1 (en) * | 2004-03-26 | 2005-12-08 | Kulkarni Sudhir S | Novel polyimide based mixed matrix membranes |
| US7527673B2 (en) * | 2004-03-26 | 2009-05-05 | L'air Liquide, Societe Anonyme A Directoire Et Conseil De Surveillance Pour L'etude Et L'exploitation Des Procedes Georges Claude | Polyimide based mixed matrix composite membranes |
| ITMI20040830A1 (en) | 2004-04-27 | 2004-07-27 | Solvay Solexis Spa | VULCANIZABLE FLUOROELASTOMERS |
| ITMI20041253A1 (en) | 2004-06-22 | 2004-09-22 | Solvay Solexis Spa | FLUOROELASTOMER GEL |
| ITMI20041573A1 (en) | 2004-07-30 | 2006-01-31 | Solvay Solexis Spa | FLUORO-ELASTOMERS |
| US8354472B2 (en) | 2007-01-03 | 2013-01-15 | Solvay Solexis, Inc. | Fluoroelastomer composition |
| JP5465175B2 (en) | 2007-08-29 | 2014-04-09 | ソルヴェイ・スペシャルティ・ポリマーズ・イタリー・エッセ・ピ・ア | (Per) fluoroelastomer composition |
| ATE541894T1 (en) * | 2007-11-22 | 2012-02-15 | Solvay Solexis Spa | VULCANIZABLE FLUORELASTOMER COMPOSITIONS |
| EP2065441A1 (en) | 2007-11-30 | 2009-06-03 | Solvay Solexis S.p.A. | Fluoroelastomer composition |
| US8263708B2 (en) | 2008-12-05 | 2012-09-11 | Solvay Solexis S.P.A. | Vulcanized (per) fluoroelastomer sealing articles |
| EP2194094A1 (en) | 2008-12-08 | 2010-06-09 | Solvay Solexis S.p.A. | (Per)fluoroelastomer composition |
| US9260543B2 (en) | 2009-12-18 | 2016-02-16 | Solvay Specialty Polymers Italy S.P.A. | Method for manufacturing fluoroelastomers |
| KR101853987B1 (en) | 2010-07-14 | 2018-05-02 | 솔베이 스페셜티 폴리머스 이태리 에스.피.에이. | Fluoroelastomer composition |
| TWI523900B (en) | 2010-07-20 | 2016-03-01 | 首威索勒希斯股份有限公司 | Fluoroelastomer composition |
| CN103282392B (en) | 2010-10-15 | 2016-03-30 | 索尔维特殊聚合物意大利有限公司 | Fluoroelastomer |
| WO2012084587A1 (en) | 2010-12-20 | 2012-06-28 | Solvay Specialty Polymers Italy S.P.A. | Low viscosity fluoroelastomers |
| WO2012150256A1 (en) | 2011-05-03 | 2012-11-08 | Solvay Specialty Polymers Italy S.P.A. | Method for manufacturing fluoroelastomers |
| WO2012168351A1 (en) | 2011-06-09 | 2012-12-13 | Solvay Specialty Polymers Italy S.P.A. | Hyperbranched fluoroelastomer additive |
| US9518178B2 (en) | 2011-08-17 | 2016-12-13 | Solvay Specialty Polymers Italy S.P.A. | Milling process |
| JP5994352B2 (en) * | 2012-04-19 | 2016-09-21 | セントラル硝子株式会社 | Method for producing 2,2-bis (4-hydroxyphenyl) hexafluoropropane-quaternary phosphonium salt |
| EP3013873A1 (en) | 2013-06-28 | 2016-05-04 | Solvay Specialty Polymers Italy S.p.A. | Fluoroelastomers |
| CN104356563B (en) * | 2014-11-17 | 2016-05-25 | 中昊晨光化工研究院有限公司 | The fluororubber compounded rubber of high temperature high voltage resistant and water vapour |
| EP3350237B1 (en) | 2015-09-18 | 2020-07-08 | Solvay Specialty Polymers Italy S.p.A. | Fluoroelastomer composition |
| JP7005495B2 (en) | 2015-12-14 | 2022-01-21 | ソルベイ スペシャルティ ポリマーズ イタリー エス．ピー．エー． | Fluoroelastomer composition |
| JP7321168B2 (en) | 2018-02-12 | 2023-08-04 | ソルベイ スペシャルティ ポリマーズ イタリー エス．ピー．エー． | Fluoroelastomer curable composition |
| JP7210900B2 (en) * | 2018-05-14 | 2023-01-24 | 日立金属株式会社 | Thermoplastic fluororesin composition, wire and cable |
| CN113544205A (en) | 2019-03-20 | 2021-10-22 | 索尔维特殊聚合物意大利有限公司 | Fluoroelastomer composition |
| CN114126862A (en) | 2019-07-17 | 2022-03-01 | 索尔维特殊聚合物意大利有限公司 | Composite material comprising polyamide and fluoroelastomer |
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| US262490A (en) * | 1882-08-08 | Door-alarm | ||
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| US3655727A (en) * | 1970-01-16 | 1972-04-11 | Minnesota Mining & Mfg | Curing systems for vinylidine fluoride elastomers |
| US3712877A (en) * | 1971-07-06 | 1973-01-23 | Minnesota Mining & Mfg | Curable vinylidene fluoride elastomers containing phosphonium curing agents |
| DK553478A (en) | 1977-12-14 | 1979-06-15 | Montedison Spa | VULCANIZED MIXTURES BASED ON VINYLIDENE FLUORIDE LASTOMERS AND PROCEDURES FOR VULCANIZING SUCH MIXTURES |
| JPS5923577B2 (en) * | 1979-02-10 | 1984-06-02 | エヌオーケー株式会社 | Fluoroelastomer-vulcanized formulations containing novel molecular compounds |
| JPS6050380B2 (en) * | 1981-06-03 | 1985-11-08 | 日本メクトロン株式会社 | Fluorine-containing elastomer composition |
| IT1183530B (en) * | 1985-03-29 | 1987-10-22 | Monteluos S P A | COMPOSITIONS FOR COSMETICS INCLUDING PERFLUOROPOLYETERS |
| IT1189092B (en) * | 1986-04-29 | 1988-01-28 | Ausimont Spa | POLYMERIZATION PROCESS IN WATER DISPERSION OF FLUORINATED MONOMERS |
| IT1204903B (en) * | 1986-06-26 | 1989-03-10 | Ausimont Spa | POLYMERIZATION PROCESS IN WATER DISPERSION OF FLORATED MONOMERS |
| IT1203514B (en) | 1987-02-26 | 1989-02-15 | Ausimont Spa | MICROEMULSIONS BASED ON THREE IMMISCIBLE LIQUIDS, INCLUDING A PERFLUOROPOLETERE |
| US4868234A (en) * | 1987-04-28 | 1989-09-19 | E. I. Du Pont De Nemours And Company | Fluoroelastomer compositions containing a tetraalkylammonium halide and vulcanization accelerator |
| US4957975A (en) * | 1988-03-14 | 1990-09-18 | E. I. Du Pont De Nemours And Company | Fluoroelastomer composition with low tendency to foul molds |
| CA1328533C (en) * | 1988-04-01 | 1994-04-12 | Werner Marie Aschille Grootaert | Fluoroelastomer composition |
| GB2217338B (en) | 1988-04-11 | 1991-12-18 | Sericol Group Ltd | Printing inks |
| JP2725023B2 (en) * | 1988-06-15 | 1998-03-09 | 日本メクトロン株式会社 | Fluoro rubber composition |
| IT1227206B (en) * | 1988-09-23 | 1991-03-27 | Ausimont Spa | PROCEDURE FOR THE PREPARATION OF DETERGENT EMULSIONS FOR COSMETICS COSMETIC PRODUCTS OBTAINED. |
| CA2017628C (en) * | 1989-06-22 | 2002-10-01 | Werner M. A. Grootaert | Fluoroelastomer composition with improved bonding properties |
| IT1235545B (en) | 1989-07-10 | 1992-09-09 | Ausimont Srl | FLUOROELASTOMERS EQUIPPED WITH BETTER PROCESSABILITY AND PREPARATION PROCEDURE |
| IT1250699B (en) * | 1991-07-24 | 1995-04-21 | Ausimont Spa | VINYLIDENFLUORIDE-BASED FLUOROELASTOMERIC COPOLYMERS MODIFIED WITH PERFLUOROALKYLVINYLETE |
| US5260392A (en) * | 1991-07-24 | 1993-11-09 | Ausimont S.P.A. | Ionically vulcanizable fluoroelastomeric copolymers |
| IT1250700B (en) | 1991-07-24 | 1995-04-21 | Ausimont Spa | VULCANIZABLE FLUOROELASTOMERIC COPOLYMERS WITH IONIC SYSTEMS |
| US5262490A (en) * | 1992-08-24 | 1993-11-16 | Minnesota Mining And Manufacturing Company | Fluoroelastomer composition with organo-onium compounds |
-
1994
- 1994-05-27 IT ITMI941080A patent/IT1269845B/en active IP Right Grant
-
1995
- 1995-05-24 RU RU95108224/04A patent/RU2152962C1/en not_active IP Right Cessation
- 1995-05-26 AT AT95108042T patent/ATE324404T1/en not_active IP Right Cessation
- 1995-05-26 US US08/451,160 patent/US5648430A/en not_active Expired - Lifetime
- 1995-05-26 CA CA002150343A patent/CA2150343A1/en not_active Abandoned
- 1995-05-26 EP EP95108042A patent/EP0684277B1/en not_active Expired - Lifetime
- 1995-05-26 DE DE69534957T patent/DE69534957T2/en not_active Expired - Lifetime
- 1995-05-27 CN CN95108540A patent/CN1100821C/en not_active Expired - Fee Related
- 1995-05-29 JP JP13047895A patent/JP3979681B2/en not_active Expired - Fee Related
-
1997
- 1997-04-07 US US08/833,534 patent/US5830381A/en not_active Expired - Lifetime
-
2001
- 2001-06-08 CN CNB011208937A patent/CN100369965C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0812840A (en) | 1996-01-16 |
| ITMI941080A0 (en) | 1994-05-27 |
| CN100369965C (en) | 2008-02-20 |
| DE69534957T2 (en) | 2007-01-25 |
| EP0684277B1 (en) | 2006-04-26 |
| CN1126222A (en) | 1996-07-10 |
| US5648430A (en) | 1997-07-15 |
| CN1328078A (en) | 2001-12-26 |
| EP0684277A1 (en) | 1995-11-29 |
| ATE324404T1 (en) | 2006-05-15 |
| DE69534957D1 (en) | 2006-06-01 |
| CN1100821C (en) | 2003-02-05 |
| US5830381A (en) | 1998-11-03 |
| RU2152962C1 (en) | 2000-07-20 |
| ITMI941080A1 (en) | 1995-11-27 |
| IT1269845B (en) | 1997-04-15 |
| RU95108224A (en) | 1997-03-20 |
| JP3979681B2 (en) | 2007-09-19 |
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