U.S. patent application number 10/118066 was filed with the patent office on 2002-11-28 for fluoroelastomer compositions.
This patent application is currently assigned to Ausimont SpA. Invention is credited to Albano, Margherita, Apostolo, Marco, Arcella, Vincenzo, Marchese, Enrico.
Application Number | 20020177664 10/118066 |
Document ID | / |
Family ID | 11381994 |
Filed Date | 2002-11-28 |
United States Patent
Application |
20020177664 |
Kind Code |
A1 |
Albano, Margherita ; et
al. |
November 28, 2002 |
Fluoroelastomer compositions
Abstract
Fluoropolymers comprising a fluoroelastomer matrix incorporating
therein particles of a semicrystalline fluoropolymer formed of
tetrafluoroethylene (TFE) homopolymers or copolymers, wherein the
average particle sizes of the semicrystalline fluoropolymer latex
range from 10 to 100 nm.
Inventors: |
Albano, Margherita; (Milano,
IT) ; Apostolo, Marco; (Novara, IT) ; Arcella,
Vincenzo; (Milano, IT) ; Marchese, Enrico;
(Asti, IT) |
Correspondence
Address: |
ARENT FOX KINTNER PLOTKIN & KAHN
1050 CONNECTICUT AVENUE, N.W.
SUITE 400
WASHINGTON
DC
20036
US
|
Assignee: |
Ausimont SpA
|
Family ID: |
11381994 |
Appl. No.: |
10/118066 |
Filed: |
April 9, 2002 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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10118066 |
Apr 9, 2002 |
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09511949 |
Feb 23, 2000 |
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6395834 |
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Current U.S.
Class: |
525/199 |
Current CPC
Class: |
C08L 2666/04 20130101;
C08L 2666/04 20130101; C08L 29/10 20130101; C08L 27/12 20130101;
C08L 29/10 20130101; C08L 27/12 20130101; C08L 2205/02 20130101;
C08L 27/18 20130101 |
Class at
Publication: |
525/199 |
International
Class: |
C08L 027/12 |
Foreign Application Data
Date |
Code |
Application Number |
Feb 23, 1999 |
IT |
MI99 A 000357 |
Claims
1. Fluoropolymers comprising a fluoroelastomer matrix incorporating
therein particles of a semicrystalline fluoropolymer latex formed
by tetrafluoroethylene (TFE) homopolymers, or TFE copolymers with
one or more monomers containing at least one unsaturation of
ethylene type in amounts ranging from 0.01% to 10% by moles,
preferably from 0.05% to 5% by moles, wherein the average particle
sizes of the semicrystalline fluoropolymer latex range from 10 to
100 nm for at least 60% by weight of the semicrystalline
fluoropolymer.
2. Fluoropolymers according to claim 1 wherein the latex particle
sizes of the semicrystalline fluoropolymer range from 10 to 60
nm.
3. Fluoropolymers according to claims 1-2 obtainable by mixing the
semicrystalline fluoropolymer latex with the fluoroelastomer latex
and subsequent coagulation.
4. Fluoropolymers according to claimns 1-2 obtainable by
polymerizing in a first step the semicrystalline fluoropolymer and
in a second step the fluoroelastomer.
5. Fluoropolymers according to claims 1-4 wherein the
semicrystalline fluoropolymer amount inside the fluoroelastomer
matrix is in the range 2%-40% by weight on the total of the
polymeric mixture.
6. Fluoropolymers according to claim 5 wherein the semicrystalline
fluoropolymer amount inside the fluoroelastomer matrix is in the
range 5-30% by weight on the total of the polymeric mixture.
7. Fluoropolymers according to claims 1-6 wherein the
semicrystalline polymer is based on PTFE modified with comonomers
with ethylene unsaturation both of hydrogenated and fluorinated
type.
8. Fluoropolymers according to claim 7 wherein the hydrogenated
comonomers are selected from ethylene, propylene,
methylmethacrylate, methacrylic acid, butylacrylate,
hydroxyethylhexylacrylate, styrene.
9. Fluoropolymers according to claim 7 wherein the fluorinated
comonomers are selected from: perfluoroolefins C.sub.3-C.sub.8,
such as hexafluoropropene (HFP), hexafluoroisobutene; hydrogenated
fluorolefins C.sub.2-C.sub.8, such as vinyl fluoride (VF),
vinylidene fluoride (VDF), trifluoroethylene,
perfluoroalkylethylene CH.sub.2.dbd.CH--R.sub.f, wherein R.sub.f is
a perfluoroalkyl C.sub.1-C.sub.6; chloro- and/or bromo- and/or
iodo-fluoroolefins C.sub.2-C.sub.8, such as chlorotrifluoroethylene
(CTFE); (per)fluoroalkylvinylethers (PAVE) CF.sub.2.dbd.CFOR.sub.f,
wherein R.sub.f is a (per)fluoroalkyl C.sub.1-C.sub.6, for example
CF.sub.3, C.sub.2F.sub.5, C.sub.3F.sub.7;
(per)fluoro-oxyalkyvinylethers CF.sub.2.dbd.CFOX, wherein X is: an
alkyl C.sub.1-C.sub.12, or an oxyalkyl C.sub.1-C.sub.12, or a
(per)fluoro-oxyalkyl C.sub.1-C.sub.12 having one or more ether
groups, for example perfluoro-2-propoxy-propyl; fluorodioxoles.
10. Fluoropolymers according to claims 7-9 wherein the preferred
comonomers are perfluoromethyl-, ethyl-, propylvinylether and
perfluorodioxoles.
11. Fluoropolymers according to claims 1-10 wherein the
fluoroelastomer is selected from the following classes: (1)
vinylidene fluoride (VDF)-based copolymers, wherein VDF is
copolymerized with at least one comonomer selected from the
following ones: perfluoroolefins C.sub.2-C.sub.8, such as
tetrafluoroethylene (TFE), hexafluoropropene (HFP); chloro- and/or
bromo- and/or iodo-fluoroolefins C.sub.2-C.sub.8, such as
chlorotrifluoroethylene (CTFE) and bromotrifluoroethylene;
(per)fluoroalkylvinylethers (PAVE) CF.sub.2.dbd.CFOR.sub.f, wherein
R.sub.f is a (per)-fluoroalkyl C.sub.1-C.sub.6, for example
trifluoromethyl, bromodifluoromethyl, pentafluoropropyl;
perfluoro-oxyalkylvinylethers CF.sub.2.dbd.CFOX, wherein X is a
perfluoro-oxyalkyl C.sub.1-C.sub.12 having one or more ether
groups, for example perfluoro-2-propoxy-propyl; non fluorinated
olefins (Ol) C.sub.2-C.sub.8, for example ethylene and propylene;
(2) tetrafluoroethylene (TFE)-based copolymers, wherein TFE is
copolymerized with at least one comonomer selected from the
following: (per)fluoroalkylvinylethers (PAVE)
CF.sub.2.dbd.CFOR.sub.f, wherein R.sub.f is as above defined;
perfluoro-oxyalkylvinylethers CF.sub.2.dbd.CFOX, wherein X is as
above defined; fluoroolefins C.sub.2-C.sub.8 containing hydrogen
and/or chlorine and/or bromine and/or iodine atoms; non fluorinated
olefins (Ol) C.sub.2-C.sub.8; perfluorovinylethers containing
hydrocyanic groups.
12. Fluoropolymers according to claim 11 wherein the preferred
fluoroelastomer is selected from the following compositions
expressed by moles: (a) vinylidene fluoride (VDF) 45-85%,
hexafluoropropene (HFP) 15-45%, tetrafluoroethylene (TFE) 0-30%;
(b) vinylidene fluoride (VDF) 50-80%, perfluoroalkylvinylether
(PAVE) 5-50%, tetrafluoroethylene (TFE) 0-20%; (c) vinylidene
fluoride (VDF) 20-30%, non fluorinated olefins (Ol) C.sub.2-C.sub.8
10-30%, hexafluoropropene (HFP) and/or perfluoroalkylvinylether
(PAVE) 18-27%, tetrafluoroethylene (TFE) 10-30%; (d)
tetrafluoroethylene (TFE) 50-80%, perfluoroalkylvinylether (PAVE)
20-50%; (e) tetrafluoroethylene (TFE) 45-65%, non fluorinated
olefins (Ol) C.sub.2-C.sub.8 20-55%, vinylidene fluoride 0-30%; (f)
tetrafluoroethylene (TFE) 32-60% by moles, non fluorinated olefins
(Ol) C.sub.2-C.sub.8 10-40%, perfluoroalkylvinylether (PAVE)
20-40%; (g) tetrafluoroethylene (TFE) 33-75%,
perfluoroalkylvinylether (PAVE) 15-45%, vinylidene fluoride (VDF)
5-30%.
13. Fluoropolymers according to claims 1-12 wherein the
fluoroelastomer comprises also monomer units deriving from a
bis-olefin having general formula: 2wherein: R.sub.1, R.sub.2,
R.sub.3, R.sub.4 , R.sub.5, R.sub.6, equal to or different from
each other, are H or alkyls C.sub.1-C.sub.5; Z is a linear or
branched, alkylene or cycloalkylene C.sub.1-C.sub.18 radical,
optionally containing oxygen atoms, preferably at least partially
fluorinated, or a (per)fluoropolyoxyalkylene radical.
14. Fluoropolymers according to claim 13 wherein the unit amount in
the chain deriving from the bis-olefin is in the range 0.01-1.0% by
moles of the other monomer units forming the fluoroelastomer base
structure.
15. Fluoropolymers according to claims 1-14 wherein the
fluoroelastomers are cured by peroxidic route.
16. Fluoropolymers according to claims 1-14 wherein the
fluoroelastomers when they contain cyano groups are cured by tin
organic compounds and/or di-aromatic aminic compounds.
17. Fluoropolymers according to claim 16 wherein the
fluoroelastomers are cured by tin organic compounds and/or
di-aromatic aminic compounds and optionally by peroxidic route if
in the polymeric chair iodine and/or bromine atoms are present.
18. Use of fluoropolymers according to claims 1-17 for the
preparation of sealing manufactured articles.
Description
[0001] The present invention relates to fluoropolymers essentially
formed by a mixture of a fluoroelastomer and a semicrystalline
fluoropolymer usable for sealing manufactured articles in the
electronic, optical and pharmaceutical industry.
[0002] More specifically the present invention relates to
fluoropolymers formed by a mixture of a fluoroelastomer and a
semicrystalline fluoropolymer, characterized by improved mechanical
properties combined with good properties of elastic retention
(lower compression set) and very good surface appearance without
roughness. It is well known that one of the fluoroelastomer uses is
the preparation of O-rings for seals: for this application it is
essential that the O-ring surface is smooth.
[0003] The use of fluoroelastomers containing
polytetrafluoroethylene (PTFE) particles to improve the properties
of abrasion-resistance and of hot tearing the obtained manufactured
articles is known in the prior art. As described in Japanese patent
57-107,336, the fluoroelastomer abrasion-resistance is improved by
physically mixing solid curable fluoroelastomers with PTFE powders
having a low molecular weight, in the range 500-200,000 as average
molecular weight by number (M.sub.n). Said PTFE is prepared by
thermal decomposition at a temperature between 450.degree. C. and
600.degree. C. for prolonged times or by irradiation with ionic
radiation of high molecular weight PTFE. An alternative method for
obtaining PTFE having a low molecular weight is that to polymerize
TFE in the presence of chain transfer agents. The fluoroelastomer
and the PTFE powders are mixed in Banbury or in calender.
[0004] In U.S. Pat. No. 4,879,362 and U.S. Pat. No. 4,904,726
mixtures of fluoroelastomers with resins of PTFE modified with the
addition of comonomers such as hexafluoropropene (HFP),
perfluoropropylvinylether (PPVE), etc., are used, in order to avoid
PTFE fibrillation problems without losing the reinforcement
properties that the PTFE gives to the obtained fluoroelastomers.
The comonomer results much more present on the polymeric particle
surface, so as to allow an uniform distribution in the
fluoroelastomer without the formation of visible agglomerates. The
latter should be the cause of fibrillation phenomena.
[0005] In EP 708,797 fluoroelastomer compositions formed by a
fluoroelastomer and by a semicrystalline fluorinated filler in the
form of micropowder which are obtained in curing compounds not
containing metal species, are described. Said compositions give a
low release of metal species under conditions where an high purity
is required, but they show poor mechanical properties. Tests
carried out by the Applicant (see the comparative Examples), have
shown that the surface of the manufactured articles obtained from
said fluoroelastomer compositions shows roughness. It is well known
that in the O-ring preparation, typical fluoroelastomer
application, surfaces having a low roughness in order to obtain
good sealing properties, are required. The semicrystalline
fluorinated filler is based on PTFE or PTFE modified with a
comonomer and obtained by emulsion or suspension polymerization.
The high molecular weight PTFE is subjected to irradiation, as
above said, in order to reduce the molecular weight. This makes
easier the PTFE milling produced by a suspension process; it
eliminates the fibrillation and reduces the PTFE agglomeration
obtained by an emulsion process.
[0006] The need was felt to have available fluoroelastomer
compositions comprising a semicrystalline fluorinated filler having
improved properties compared with those of the prior art and
specifically with the following property combination:
[0007] improved mechanical properties
[0008] good elastic retention properties (lower compression
set--very good seal)
[0009] very good surface appearance roughness free.
[0010] The Applicant has unexpectedly and surprisingly found that
it is possible to obtain the combination of the above mentioned
properties, by incorporating in the fluoroelastomer matrix PTFE
particles or its copolymers having well defined sizes as specified
hereinafter.
[0011] It is therefore an object of the present invention
fluoropolymers comprising a fluoroelastomer matrix incorporating
therein particles of a semicrystalline fluoropolymer latex formed
by tetrafluoroethylene (TFE) homopolymers, or TFE copolymers with
one or more monomers containing at least one ethylene unsaturation
in amounts ranging from 0.01% to 10% by moles, preferably from
0.05% to 5% by moles, wherein the average particle sizes of the
semicrystalline fluoropolymer latex range from 10 to 100 nm,
preferably from 10 to 60 nm. Also semycrystalline fluoropolymers
wherein the latex particle sizes have the above mentioned value for
at least 60% by weight, preferably 70% by weight of the
semicrystalline fluoropolymer, can be used.
[0012] The invention compositions are obtainable by mixing the
semicrystalline fluoropolymer latex with the fluoroelastomer latex
and subsequent coagulation. Alternatively the invention
compositions can be polymerized in the same reactor in two
subsequent steps: in a first step the semicrystalline fluoropolymer
with the mentioned nanometric sizes is polymerized and in a second
step the fluoroelastomer is polymerized. By operating in this way
the fluoroelastomer should cover the semicrystalline fluoropolymer
latex particles, allowing to obtain a very good dispersion of the
latter in the fluoroelastomer.
[0013] The semicrystalline fluoropolymer amount inside the
fluoroelastomer matrix is in the range 2%-40% by weight, preferably
5-30% by weight, more preferably 10-20% by weight on the total of
the polymeric mixture.
[0014] The semicrystalline fluoropolymer particles having the above
mentioned sizes are obtainable for example by a polymerization
process in an aqueous microemulsion of perfluoropolyoxyalkylenes as
described for example in the European patent application EP
99112083.3 in the name of the Applicant, herein incorporated by
reference. Microemulsion polymerization methods can also be used,
wherein the oil phase is formed by polymerizable unsaturated
monomers, as described in U.S. Pat. No. 5,523,346 and in U.S. Pat.
No. 5,616,648.
[0015] The fluoroelastomers can be prepared by copolymerization of
the monomers in aqueous emulsion, according to well known methods
in the prior art, in the presence of radical initiators (for
example alkaline or ammonium persulphates, perphosphates,
perborates, percarbonates), optionally in combination with ferrous,
cuprous or silver salts, or of other easily oxidizable metals. In
the reaction medium also surfactants of various kind, among which
the fluorinated surfactants are particularly preferrred, are
usually present.
[0016] Alternatively the fluoroelastomers can be prepared in bulk
or in suspension, in an organic liquid in which a suitable radical
initiator is present, according to well known techniques.
[0017] The polymerization reaction is generally carried out at
temperatures in the range 25.degree.-150.degree. C., under a
pressure up to 10 MPa.
[0018] The fluoroelastomers are preferably prepared in
microemulsion of perfluoropolyoxyalkylens, according to U.S. Pat.
No. 4,789,717 and U.S. Pat. No. 4,864,006.
[0019] The Applicant has found that in order to obtain the results
of the present invention it is essential that the semi-crystalline
fluoropolymer filler latex has the mentioned nanometric sizes,
while the size of the latex of the fluoroelastomer is not
critical.
[0020] When the semi-crystalline fluorinated filler is based on
modified PTFE, for its preparation comonomers having an ethylene
unsaturation both of hydrogenated and fluorinated type, can be
used. Among those hydrogenated, ethylene, propylene, acrylic
monomers, for example methylmethacrylate, (meth)acrylic acid,
butylacrylate, hydroxyethylhexyl-acrylate, styrene monomers can be
mentioned.
[0021] Among the fluorinated comonomers we can mention:
[0022] perfluoroolefins C.sub.3-C.sub.8, such as hexafluoropropene
(HFP), hexafluoroisobutene;
[0023] hydrogenated fluorolefins C.sub.2-C.sub.8, such as vinyl
fluoride (VF), vinylidene fluoride (VDF), trifluoroethylene,
perfluoroalkylethylene CH.sub.2.dbd.CH--R.sub.f, wherein R.sub.f is
a perfluoroalkyl C.sub.1-C.sub.6;
[0024] chloro- and/or bromo- and/or iodo-fluoroolefins
C.sub.2-C.sub.8, such as chlorotrifluoroethylene (CTFE);
[0025] (per)fluoroalkylvinylethers (PAVE) CF.sub.2.dbd.CFOR.sub.f,
wherein R.sub.f is a (per)fluoroalkyl C.sub.1-C.sub.6, for example
CF.sub.3, C.sub.2F.sub.5, C.sub.3F.sub.7;
[0026] (per)fluoro-oxyalkylvinylethers CF.sub.2.dbd.CFOX, wherein X
is:
[0027] an alkyl C.sub.1-C.sub.12, or an oxyalkyl C.sub.1-C.sub.12,
or a (per)fluoro-oxyalkyl C.sub.1-C.sub.12 having one or more ether
groups, for example perfluoro-2-propoxy-propyl; fluorodioxoles,
preferably perfluorodioxoles.
[0028] PAVEs are preferred comonomers, specifically
perfluoromethyl-, ethyl-, propylvinylether and fluorodioxoles,
preferably perfluorodioxoles.
[0029] The fluoroelastomers used in the present invention belong to
the following classes:
[0030] (1) VDF-based copolymers, wherein VDF is copolymerized with
at least one comonomer selected from the following:
[0031] perfluoroolefins C.sub.2-C.sub.8, such as
tetrafluoroethylene (TFE), hexafluoropropene (HFP); chloro- and/or
bromo- and/or iodo-fluoroolefins C.sub.2-C.sub.8, such as
chlorotrifluoroethylene (CTFE) and bromotrifluoroethylene;
(per)fluoroalkylvinylethers (PAVE) CF.sub.2.dbd.CFOR.sub.f, wherein
R.sub.f is a (per)-fluoroalkyl C.sub.1-C.sub.6, for example
trifluoromethyl, bromodifluoromethyl, pentafluoropropyl;
perfluorooxyalkylvinylethers CF.sub.2.dbd.CFOX, wherein X is a
perfluorooxyalkyl C.sub.1-C.sub.12 having one or more ether groups,
for example perfluoro-2-propoxy-propyl; non fluorinated olefins
(Ol) C.sub.2-C.sub.8, for example ethylene and propylene;
[0032] (2) TFE-based copolymers, wherein TFE is copolymerized with
at least one comonomer selected from the following:
[0033] (per)fluoroalkylvinylethers (PAVE) CF.sub.2.dbd.CFOR.sub.f,
wherein R.sub.f is as above defined; perfluoro-oxyalkylvinylethers
CF.sub.2.dbd.CFOX, wherein X is as above defined; fluoroolefins
C.sub.2-C.sub.8 containing hydrogen and/or chloro and/or bromo
and/or iodo atoms; non fluorinated olefins (Ol) C.sub.2-C.sub.8;
perfluorovinylethers containing hydrocyanic groups as described in
U.S. Pat. No. 4,281,092, U.S. Pat. No. 5,447,993, U.S. Pat.
No.5,789,489.
[0034] Preferably the invention fluoroelastomers contain
perfluorinated monomers, and preferably the base structure of these
fluoroelastomers is selected from the copolymers of class (2),
wherein TFE is polymerized with one or more perfluorinated
comonomers as above mentioned.
[0035] Within the above defined classes, preferred compositions by
moles of the monomers forming the base structure of the
fluoroelastomer are the following:
[0036] (a) vinylidene fluoride (VDF) 45-85%, hexa-fluoropropene
(HFP) 15-45%, tetrafluoroethylene (TFE) 0-30%;
[0037] (b) vinylidene fluoride (VDF) 50-80%,
perfluoroalkylvinylether (PAVE) 5-50%, tetrafluoroethylene (TFE)
0-20%;
[0038] (c) vinylidene fluoride (VDF) 20-30%, non fluorinated
olefins (Ol) C.sub.2-C.sub.8 10-30%, hexafluoropropene (HFP) and/or
perfluoroalkylvinylether (PAVE) 18-27%, tetrafluoroethylene (TFE)
10-30%;
[0039] (d) tetrafluoroethylene (TFE) 50-80%,
perfluoroalkylvinylether (PAVE) 20-50%;
[0040] (e) tetrafluoroethylene (TFE) 45-65%, non fluorinated
olefins (Ol) C.sub.2-C.sub.8 20-55%, vinylidene fluoride 0-30%;
[0041] (f) tetrafluoroethylene (TFE) 32-60% by moles, non
fluorinated olefins (Ol) C.sub.2-C.sub.8 10-40%,
perfluoroalkylvinylether (PAVE) 20-40%;
[0042] (g) tetrafluoroethylene (TFE) 33-75%,
perfluoroalkylvinylether (PAVE) 15-45%, vinylidene fluoride (VDF)
5-30%.
[0043] Specific particularly preferred compositions are:
[0044] (d) TFE 50-80%, PAVE 20-50%;
[0045] (g) TFE 33-75%, PAVE 15-45%, VDF 5-30%.
[0046] Optionally the fluoroelastomers comprise also monomer units
deriving from a bis-olefin having general formula: 1
[0047] wherein:
[0048] R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6, equal
to or different from each other, are H or alkyls
C.sub.1-C.sub.5;
[0049] Z is a linear or branched, alkylene or cycloalkylene
C.sub.1-C.sub.18 radical, optionally containing oxygen atoms,
preferably at least partially fluorinated, or a
(per)fluoropolyoxyalkylene radical, as described in EP 661,304 in
the name of the Applicant.
[0050] The unit amount in the chain deriving from said bis-olefins
is generally in the range 0.01-1.0 by moles, preferably 0.03-0.5 by
moles, still more preferably 0.05-0.2% by moles for 100 moles of
the other above mentioned monomer units forming the fluoroelastomer
base structure.
[0051] The fluoropolymers of the present invention can be cured by
peroxidic route, wherefore they preferably contain along the chain
and/or in terminal position of the macromolecules iodine and/or
bromine atoms. The introduction of such iodine and/or bromine atoms
can be achieved by addition, in the reaction mixture, of brominated
and/or iodinated cure-site comonomers, such as bromo and/or iodo
olefins having from 2 to 10 carbon atoms (as described for example
in U.S. Pat. No. 4,035,565 and U.S. Pat. No. 4,694,045), or iodo
and/or bromo fluoroalkylvinylethers (as described in U.S. Pat. No.
4,745,165, U.S. Pat. No. 4,564,662 and EP 199,138), in such amounts
so that the content of cure-site comonomers in the final product is
generally in the range 0.05-2 moles for 100 moles of the other base
monomer units.
[0052] Other usable iodinated compounds are the triodinated
deriving from triazines as described in European patent application
EP 860,436 and in the European patent application EP
99114823.0.
[0053] Alternatively or also in association with the cure-site
comonomers it is possible to introduce iodine and/or bromine end
atoms by addition to the reaction mixture of iodinated and/or
brominated chain transfer agents, such as for example the compounds
of formula R.sub.f(I).sub.x(Br).sub.y, wherein R.sub.f is a
(per)fluoroalkyl or a (per)fluorochloroalkyl having from 1 to 8
carbon atoms, while x and y are integers between 0 and 2, with
1.gtoreq.x+y.gtoreq.2 (see for example U.S. Pat. No. 4,243,770 and
U.S. Pat. No. 4,943,622). It is also possible to use, as chain
transfer agents, alkaline or earth-alkaline metal iodides and/or
bromides, according to U.S. Pat. No. 5,173,553.
[0054] In association with the chain transfer agents containing
iodine and/or bromine, other chain transfer agents known in the
prior art, such as ethyl acetate, diethylmalonate, etc., can be
used.
[0055] Curing by peroxidic route is carried out, according to known
techniques, by addition of a suitable peroxide capable to generate
radicals by thermal decomposition. Among the most commonly used we
mention: dialkylperoxides, such as for example di-terbutyl-peroxide
and 2,5-dimethyl-2,5-di-(terbutylperoxy)hexane; dicumyl peroxide;
dibenzoyl peroxide; diterbutyl perbenzoate;
di[1,3-dimethyl-3-(terbutylperoxy)-buty- l]carbonate. Other
peroxidic systems are described, for example, in European patent
applications EP 136,596 and EP 410,351.
[0056] To the compound (curable blend) other products are then
added, such as:
[0057] (a) curing coagents, in an amount generally in the range
0.5-10%, preferably 1-7% by weight with respect to the poly-ymer;
among them, triallyl-cyanurate; triallyl-isocyanurate (TAIC);
tris(diallylamine)-s-tr- iazine; triallylphosphite;
N,N-diallyl-acrylamide; N,N,N',N'-tetraallylmal- onamide;
trivinyl-isoyanurate; 2,4,6-trivinyl-methyl-trisiloxane, etc., are
commonly used; TAIC is particularly preferred; other preferred
crosslinking agents are bis-olefins described in the European
patent application
[0058] EP 769,520. Other crosslinking agents which can be used are
the triazines described in the European patent applications EP
860,436 and WO97/05122.
[0059] (b) optionally a metal compound, in an amount in the range
1-15%, preferably 2-10%, by weight with respect to the polymer,
selected from oxides or hydroxides of divalent metals, such as for
example, Mg, Zn, Ca or Pb, optionally associated to a weak acid
salt, such as for example stearates, benzoates, carbonates,
oxalates or phosphites of Ba, Na, K, Pb, Ca;
[0060] (c) optionally acid acceptors of the non metal oxide type,
such as 1,8 bis dimethyl amino naphthalene, octadecyl-amine etc. as
described in EP 708,797.
[0061] (d) other conventional additives, such as thickening
fillers, pigments, antioxidants, stabilizers and the like.
[0062] When the fluoroelastomer matrix contains cyano groups, the
fluoropolymer curing of the present invention is carried out by
using as crosslinking agents tin organic compounds or di-aromatic
aminic compounds, as described in U.S. Pat. No. 4,394,489, U.S.
Pat. No. 5,767,204, U.S. Pat. No. 5,789,509. This type of curing
can be associated to a curing of peroxidic type, when the
fluoroelastomer matrix contains iodine or bromine atoms, preferably
end atoms, as described in U.S. Pat. No. 5,447,993.
[0063] The present invention will be better illustrated by the
following Examples, which have a merely indicative but not
limitative purpose of the scope of the invention itself.
EXAMPLE 1
[0064] a) Preparation of the Semicrystalline Fluoropolymer
[0065] In a 10 l autoclave, equipped with a stirrer working at 545
rpm, after evacuation, 6.5 l of demineralized water and 272 ml of a
perfluoropolyoxyalkylene microemulsion were introduced: the latter
was previously obtained by mixing:
[0066] 59 ml of a perfluoropolyoxyalkylene, having an acid end
group, of formula:
CF.sub.2ClO(CF.sub.2--CF(CF.sub.3)O).sub.n(CF.sub.2O).sub.mCF.sub.2COOH
[0067] wherein n/m=10, having average molecular weight of 600;
[0068] 59 ml of a 30% by volume NH.sub.4OH aqueous solution;
[0069] 118 ml of demineralized water;
[0070] 36 ml of Galden.sup.(R) D02 of formula:
CF.sub.3O(CF.sub.2--CF(CF.sub.3)O).sub.n(CF.sub.2O).sub.mCF.sub.3
[0071] wherein n/m=20, having average molecular weight of 450.
[0072] The autoclave was then heated up to 80.degree. C. and
maintained at said temperature for the whole reaction duration.
0.48 bar of C.sub.2H.sub.6 were fed into the autoclave and the
pressure was increased and maintained constant at 11 bar during the
whole polymerization with TFE.
[0073] 6.5 g of ammonium persulphate (APS) as initiator agent were
then introduced into the autoclave. After 37 minutes of reaction,
the autoclave was cooled and the latex discharged. The latex
characteristics are reported in Table 1.
[0074] b) Preparation of the Fluoroelastomer
[0075] In a 10 l autoclave, equipped with a stirrer working at 545
rpm, after evacuation, 6.5 l of demineralized water and 67 ml of a
perfluoropolyoxyalkylene microemulsion were introduced: the latter
was previously obtained by mixing:
[0076] 14.5 ml of a perfluoropolyoxyalkylene, having an acid end
group, of formula:
CF.sub.2ClO(CF.sub.2--CF(CF.sub.3)O).sub.n(CF.sub.2O).sub.mCF.sub.2COOH
[0077] wherein n/m=10, having average molecular weight of 600;
[0078] 14.5 ml of a 30% by volume NH.sub.4OH aqueous solution;
[0079] 29 ml of demineralized water;
[0080] 9 ml of Galden.sup.(R) D02 of formula:
CF.sub.3O(CF.sub.2--CF(CF.sub.3)O).sub.n(CF.sub.2O).sub.mCF.sub.3
[0081] wherein n/m=20, having average molecular weight of 450.
[0082] The autoclave was then heated up to 80.degree. C. and
maintained at said temperature for the whole reaction duration. The
following mixture of monomers was then fed:
[0083] perfluoromethylvinylether (PMVE) 60% by moles
[0084] tetrafluoroethylene (TFE) 40% by moles so as to increase the
pressure to 25 bar.
[0085] 0.32 g of ammonium persulphate (APS) as initiator agent;
[0086] 26 g of 1,6-diiodoperfluorohexane (C.sub.6F.sub.12I.sub.2)
as chain transfer agent;
[0087] 5 g of bis-olefin of formula
CH.sub.2.dbd.CH--(CF.sub.2).sub.6--CH.- dbd.CH.sub.2; the addition
was carried out in 20 portions, each of 0.25 g, starting from the
polymerization beginning and for every 5% increase in the monomer
conversion, were then introduced in the autclave.
[0088] The 25 bar pressure was maintained constant for the whole
duration of the polymerization by feeding a mixture formed by:
[0089] perfluoromethylvinylether (PMVE) 40% by moles
[0090] tetrafluoroethylene (TFE) 60% by moles
[0091] After 137 minutes of reaction, the autoclave was cooled and
the latex discharged. The latex properties are reported in Table
1.
[0092] c) Mixing of the Latexes--Preparation of the Final
Polymer
[0093] 635.6 ml of the latex obtained in Example 1a are mixed with
1517 ml of the Example 1b latex. After mixing, the latex is
coagulated with an aluminum sulphate solution (6 g of
Al.sub.2(SO.sub.4).sub.3 for every liter of latex) and dried at
80.degree. C. in an air-circulating oven for 10 hours. 500 g of
polymer, characterized as shown in Table 2, were obtained.
EXAMPLE 2 COMPARATIVE
[0094] a) Preparation of the Semicrystalline Fluoropolymer
[0095] In a 50 l autoclave, equipped with a stirrer working at 245
rpm, 32 l of demineralized water, 12 g of ammonium
prfluorooctanoate and 140 g of paraffin with melting point
52-56.degree. C. were introduced, after evacuation.
[0096] The autoclave was then heated to 89.degree. C. and
progressively increased up to 102.1.degree. C. with a rate of
1.degree. C. per minute for the whole reaction duration. 350 mbar
of ethane were fed into the autoclave and the pressure was
increased and maintained at 20 bar by continuously feeding TFE
during the polymerization.
[0097] 3.5 g of ammonium prsulphate (APS) as initiator agent and
subsequently further 2 g of an APS aqueous solution at a flow-rate
of 50 cc/min were introduced in the autoclave.
[0098] After 73 minutes of reaction, the autoclave was cooled and
the latex discharged. The latex characteristics are reported in
Table 1.
[0099] b) Preparation of the Fluoroelastomer
[0100] The fluoroelastomer latex was obtained as described in
Example 1b.
[0101] c) Mixing of the Latexes--Preparation of the Final
Polymer
[0102] 428.5 ml of the latex obtained in Example 2a are mixed with
1517 ml of the Example 2b latex. After mixing, the latex is
coagulated with an aluminum sulphate solution (6 g of
Al.sub.2(SO.sub.4).sub.3 for every liter of latex) and dried at
80.degree. C. in an air-circulating oven for 10 hours. 500 g of
polymer, characterized as shown in Table 2, were obtained.
EXAMPLE 3 COMPARATIVE
[0103] a) Preparation of the Semicrystalline Fluoropolymer
[0104] The PTFE latex was obtained in the presence of a
microemulsion as in Example 1a. The latex was subsequently
coagulated with an aluminum sulphate solution (6 g of
Al.sub.2(SO.sub.4).sub.3 for each liter of latex) and dried at
150.degree. C. in an air-circulation oven for 24 hours.
[0105] b) Preparation of the Fluoroelastomer
[0106] The perfluoroelastomer latex was obtained as described in
Example 1b. The latex was subsequently coagulated with an aluminum
sulphate solution (6 g of Al.sub.2(SO.sub.4).sub.3 for each liter
of latex) and dried at 100.degree. C. in an air-circulation oven
for 12 hours.
[0107] c) Mechanical Mixing--Preparation of the Final Polymer
[0108] 425 g of fluoroelastomer of Example 3b were mixed with 75 g
of PTFE powder obtained from Example 3a in an open mixer with
rollers heated at 60.degree. C. In the mixing process the
perfluoroelastomer is introduced first with the rollers completely
near the one to the other and mixed until a continuous polymer film
is obtained. The PTFE powder was then added until obtaining an
uniform mixing. The obtained mixture was characterized as reported
in Table 2.
EXAMPLE 4 COMPARATIVE
[0109] 425 g of fluoroelastomer obtained in Example 3b were mixed
in an open mixer with 75 g of PTFE MP 1600 by Du Pont by using the
procedure described in Example 3c. The mixture properties are
reported in Table 2.
EXAMPLE 5
[0110] a) Preparation of the Semicrystalline Fluoropolymer
[0111] In a 50 l autoclave, equipped with a stirrer working at 245
rpm, after evacuation, 32 l of demineralized water, 140 g of a
paraffin with melting point 52.degree.-56.degree. C. and 300 ml of
a perfluoropolyoxyalkylene microemulsion were introduced: the
latter was previously obtained by mixing:
[0112] 65 ml of a perfluoropolyoxyalkylene, having an acid end
group, of formula:
CF.sub.2ClO(CF.sub.2--CF(CF.sub.3)O).sub.n(CF.sub.2O).sub.mCF.sub.2COOH
[0113] wherein n/m=10, having average molecular weight of 600;
[0114] 65 ml of a 30% by volume NH.sub.4OH aqueous solution;
[0115] 130 ml of demineralized water;
[0116] 40 ml of Galden.sup.(R) D02 of formula:
CF.sub.3O(CF.sub.2--CF(CF.sub.3)O).sub.n(CF.sub.2O).sub.mCF.sub.3
[0117] wherein n/m=20, having average molecular weight of 450.
[0118] The autoclave was then heated up to 80.degree. C. and the
temperature was progressively increased up to 96.degree. C. with a
rate of 0.6.degree. C./min for the whole reaction duration. 370
mbar of C.sub.2H.sub.6 were fed into the autoclave and the pressure
was increased and maintained constant at 20 bar during the whole
polymerization by feeding TFE.
[0119] 2.5 g of ammonium persulphate (APS) as initiator agent were
then introduced into the autoclave and subsequently by feeding,
starting from 10% of conversion, 0.54 g of APS every 10% of monomer
conversion. After 64 minutes of reaction, the autoclave was cooled
and the latex discharged. The latex characteristics are reported in
Table 3.
[0120] b) Preparation of the Fluoroelastomer
[0121] The fluoroelastomer latex was obtained as described in
Example 1b, except that the amount of 1,6-diiodoperfluorohexane was
of 30 g instead of 26 g.
[0122] c) Mixing of the Latexes--Preparation of the Final
Polymer
[0123] 347 ml of the latex obtained in Example 5a are mixed with
1197 ml of the Example 5b latex. After mixing, the latex is
coagulated with an aluminum sulphate solution (6 g of
Al.sub.2(SO.sub.4).sub.3 for each liter of latex) and dried at
80.degree. C. in an air-circulating oven for 10 hours. 500 g of
polymer, characterized as shown in Table 4, were obtained.
EXAMPLE 6
[0124] In a 10 l autoclave, equipped with a stirrer working at 545
rpm, after evacuation, 6.5 l of demineralized water and 260 ml of a
perfluoropolyoxyalkylene microemulsion were introduced: the latter
was previously obtained by mixing:
[0125] 56.3 ml of a perfluoropolyoxyalkylene having an acid end
group of formula:
CF.sub.2ClO(CF.sub.2--CF(CF.sub.3)O).sub.n(CF.sub.2O).sub.mCF.sub.2COOH
[0126] wherein n/m=10, having average molecular weight of 600;
[0127] 56.3 ml of a 30% by volume NH.sub.4OH aqueous solution;
[0128] 112.7 ml of demineralized water;
[0129] 34.7 ml of Galden.sup.(R) D02 of formula:
CF.sub.3O(CF.sub.2--CF(CF.sub.3)O).sub.n(CF.sub.2O).sub.mCF.sub.3
[0130] wherein n/m=20, having average molecular weight of 450.
[0131] The autoclave was then heated up to 80.degree. C. and
maintained at said temperature for the whole reaction duration.
0.48 bar of ethane were fed into the autoclave and the pressure was
increased and maintained constant at 11 bar by continuously feeding
TFE during the polymerization.
[0132] 6.5 g of ammonium persulphate (APS) were then introduced
into the autoclave as initiator. After 15 minutes of reaction, the
autoclave was cooled, degassed and discharged. The latex
characteristics are reported in Table 3. Subsequently 2368 ml
(corresponding to 449.9 g of polymer) of the latex are introduced
again in the 10 liter reactor to which 4132 liters of demineralized
water are added. The autoclave is then brought to 90.degree. C. and
maintained for one hour at said temperature in order to decompose
all the residual initiator agent. Subsequently the temperature is
increased to 80.degree. C. and maintained constant for the whole
duration of the polymerization. The following mixture of monomers
was then fed:
[0133] perfluoromethylvinylether (PMVE) 60% by moles
[0134] tetrafluoroethylene (TFE) 40% by moles so as to increase the
pressure to 25 bar.
[0135] 0.32 g of ammonium persulphate (ADS) as initiator agent;
[0136] 22.3 g of 1,6-diiodoperfluorohexane (C.sub.6F.sub.12I.sub.2)
as chain transfer agent;
[0137] 4.28 g of bis-olefin of formula
CH.sub.2.dbd.CH--(CF.sub.2).sub.6--- CH.dbd.CH.sub.2; the addition
was carried out in 20 portions, each of 0.214 g, starting from the
polymerization beginning and for every 5% increase in the monomer
conversion, were then introduced in the autoclave.
[0138] The 25 bar pressure was maintained constant for the whole
duration of the polymerization by feeding a mixture formed by:
[0139] perfluoromethylvinylether (PMVE) 40% by moles
[0140] tetrafluoroethylene (TFE) 60% by moles
[0141] After 45 minutes of reaction corresponding to 2550 g of
elastomer, the autaoclave was cooled and the latex discharged. The
latex is coagulated with an aluminum sulphate solution (6 g of
Al.sub.2(SO.sub.4).sub.3 for each liter of latex) and dried at
80.degree. C. in an air-circulating oven for 10 hours. The obtained
polymer was characterized as shown in Table 4.
EXAMPLE 7
[0142] a) Preparation of the Semicrystalline Fluoropolymer
[0143] The PTFE latex was obtained as described in Example 5a. The
latex characteristics are reported in Table 3.
[0144] b) Preparation of the Fluoroelastomer
[0145] The fluoroelastomer latex was obtained as described in
Example 5b. The characteristics are reported in Table 3.
[0146] c) Mixing of the Latexes--Preparation of the Final
Polymer
[0147] 463 ml of the latex obtained in Example 7a are mixed with
1127 ml of the Example 7b latex. After mixing, the latex is
coagulated with an aluminum sulphate solution (6 g of
Al.sub.2(SO.sub.4).sub.3 for each liter of latex) and dried at
80.degree. C. in an air-circulating oven for 10 hours. The obtained
polymer was characterized as shown in Table 4.
EXAMPLE 8
[0148] The polymer obtained in Example 7c was crosslinked with
bis-olefin of formula
CH.sub.2.dbd.CH--(CF.sub.2).sub.6--CH.dbd.CH.sub.2, instead of
TAIC. The compound characteristics are reported in Table 4.
EXAMPLE 9
[0149] a) Preparation of the Semicrystalline Fluoropolymer
[0150] The PTFE latex was obtained as reported in Example 1a. The
latex characteristics are reported in Table 5.
[0151] b) Preparation of the Fluoroelastomer
[0152] In a 10 l autoclave, equipped with a stirrer working at 545
rpm, 6.5 l of demineralized water and 26 g of ammonium
perfluorooctanoate were introduced, after evacuation.
[0153] The autoclave was then heated up to 80.degree. C. and
maintained at said temperature for the whole reaction duration. The
following mixture of monomers was then fed:
[0154] perfluoromethylvinylether (PMVE) 60% by moles
[0155] tetrafluoroethylene (TFE) 40% by moles so as to increase the
pressure to 25 bar.
[0156] 6.5 g of ammonium persulphate (APS) as initiator agent;
[0157] 25 g of 1,6-diiodoperfluorohexane (C.sub.6F.sub.12I.sub.2)
as chain transfer agent;
[0158] 5 g of bis-olefin of formula
CH.sub.2.dbd.CH--(CF.sub.2).sub.6--CH.- dbd.CH.sub.2; the addition
was carried out in 20 portions, each of 0.25 g, starting from the
polymerization beginning and for every 5% increase in the monomer
conversion, were then introduced in the autoclave.
[0159] The 25 bar pressure was maintained constant for the whole
duration of the polymerization by feeding a mixture formed by:
[0160] perfluoromethylvinylether (PMVE) 40% by moles
[0161] tetrafluoroethylene (TFE) 60% by moles
[0162] After 500 minutes of reaction, the autoclave was cooled and
the latex discharged. The latex properties are reported in Table
5.
[0163] c) Mixing of the Latexes--Preparation of the Final
Polymer
[0164] 551.5 ml of the latex obtained in Example 9a are mixed with
1393.5 ml of the Example 9b latex. After mixing, the latex is
coagulated with an aluminum sulphate solution (6 g of
Al.sub.2(SO.sub.4).sub.3 for each liter of latex) and dried at
80.degree. C. in an air-circulating oven for 10 hours. 500 g of
polymer, characterized as shown in Table 6, were obtained.
EXAMPLE 10
[0165] a) Preparation of the Semicrystalline Fluoropolymer
[0166] In a 10 l autoclave, equipped with a stirrer working at 545
rpm, after evacuation, 6.5 l of demineralized water and 65.1 ml of
a perfluoropolyoxyalkylene microemulsion were introduced: the
latter was previously obtained by mixing:
[0167] 14.1 ml of a perfluoropolyoxyalkylene, having an acid end
group, of formula:
CF.sub.2ClO(CF.sub.2--CF(CF.sub.3)O).sub.n(CF.sub.2O).sub.mCF.sub.2COOH
[0168] wherein n/m=10, having average molecular weight of 600;
[0169] 14.1 ml of a 30% by volume NH.sub.4OH aqueous solution;
[0170] 28.2 ml of demineralized water;
[0171] 8.7 ml of Galden.sup.(R) D02 of formula:
CF.sub.3O(CF.sub.2--CF(CF.sub.3)O).sub.n(CF.sub.2O).sub.mCF.sub.3
[0172] wherein n/m=20, having average molecular weight of 450.
[0173] The autoclave was then heated up to 80.degree. C. and
maintained at said temperature for the whole reaction duration. The
autoclave was pressurized to the pressure of 0.56 bar with ethane
and then to the pressure of 25 bar with a monomer mixture
constituted by 10% by moles of perfluoromethylvinylether (PMVE) and
90% by moles of tetrafluoroethylene (TFE).
[0174] 1.3 g of ammonium persulphate (APS) as initiator agent were
then introduced in the autoclave. During the reaction the pressure
is maintained at 25 bar by continuously feeding the following
monomer mixture: 3.5% by moles of PMVE and 96.5% of TFE.
[0175] After 60 minutes of reaction, the autoclave was cooled and
the latex discharged. The latex characteristics are reported in
Table 7.
[0176] b) Preparation of the Fluoroelastomer
[0177] In a 22 l autoclave, equipped with a stirrer working at 460
rpm, after evacuation, 15 l of demineralized water and 154.5 ml of
a perfluoropolyoxyalkylene microemulsion were introduced: the
latter was previously obtained by mixing:
[0178] 33.46 ml of a perfluoropolyoxyalkylene, having an acid end
group, of formula:
CF.sub.2ClO(CF.sub.2--CF(CF.sub.3)O).sub.n(CF.sub.2O).sub.mCF.sub.2COOH
[0179] wherein n/m=10, having average molecular weight of 600;
[0180] 33.46 ml of a 30% by volume NH.sub.4OH aqueous solution;
[0181] 66.93 ml of demineralized water;
[0182] 20.65 ml of Galden.sup.(R) D02 of formula:
CF.sub.3O(CF.sub.2--CF(CF.sub.3)O).sub.n(CF.sub.2O).sub.mCF.sub.3
[0183] wherein n/m=20, having average molecular weight of 450.
[0184] The autoclave was then heated up to 80.degree. C. and
maintained at said temperature for the whole reaction duration. The
following mixture of monomers was then fed:
[0185] perfluoromethylvinylether (PMVE) 60% by moles
[0186] tetrafluoroethylene (TFE) 40% by moles so as to increase the
pressure to 25 bar.
[0187] 0.75 g of ammonium persulphate (APS) as initiator agent;
[0188] 69.24 g of 1,6-diiodoperfluorohexane
(C.sub.6F.sub.12I.sub.2) as chain transfer agent;
[0189] 11.09 g of bis-olefin of formula
CH.sub.2.dbd.CH--(CF.sub.2).sub.6-- -CH.dbd.CH.sub.2; the addition
was made in 20 portions, each of 0.554 g, starting from the
polymerization beginning and for every 5% increase in the monomer
conversion, were then introduced in the autoclave.
[0190] The 25 bar pressure was maintained constant for the whole
duration of the polymerization by feeding a mixture formed by:
[0191] perfluoromethylvinylether (PMVE) 40% by moles
[0192] tetrafluoroethylene (TFE) 60% by moles
[0193] After 110 minutes of reaction, the autoclave was cooled and
the latex discharged. The latex properties are reported in Table
7.
[0194] c) Mixing of the Latexes--Preparation of the Final
Polymer
[0195] 238 ml of the latex obtained in Example 10a are mixed with
1187 ml of the Example 10b latex. After mixing, the latex is
coagulated with an aluminum sulphate solution (6 g of
Al.sub.2(SO.sub.4).sub.3 for each liter of latex) and dried at
80.degree. C. in an air-circulating oven for 10 hours. 500 g of
polymer, characterized as shown in Table 8, were obtained.
EXAMPLE 11
[0196] In a 5 l autoclave, equipped with stirrer working at 630
rpm, after evacuation, 3.5 l of demineralized water and 35 ml of a
perfluoropolyoxyalkylene microemulsion were introduced: the latter
was previously obtained by mixing:
[0197] 7.58 ml of a perfluoropolyoxyalkylene, having an acid end
group, of formula:
CF.sub.2ClO(CF.sub.2--CF(CF.sub.3)O).sub.n(CF.sub.2O).sub.mCF.sub.2COOH
[0198] wherein n/m=10, having average molecular weight of 600;
[0199] 7.58 ml of a 30% by volume NH.sub.4OH aqueous solution;
[0200] 15.16 ml of demineralized water;
[0201] 4.68 ml of Galden.sup.(R) D02 of formula:
CF.sub.3O(CF.sub.2--CF(CF.sub.3)O).sub.n(CF.sub.2O).sub.mCF.sub.3
[0202] wherein n/m=20, having average molecular weight of 450.
[0203] The autoclave was then heated up to 80.degree. C. and
maintained at said temperature for the whole reaction duration. The
autoclave was pressurized to the pressure of 0.56 bar with ethane
and then to the pressure of 25 bar with a monomer mixture formed by
10% by moles of perfluoromethylvinylether (PMVE) and 90% by moles
of tetrafluoroethylene (TFE).
[0204] In the autoclave 0.7 g of ammonium persulphate (APS) as
initiator agent were then introduced. During the reaction the
pressure is maintained at 25 bar by continuously feeding the
following monomer mixture: 3.5% by moles of PMVE and 96.5% of
TFE.
[0205] After 10 minutes of reaction, the autoclave was cooled,
degassed and discharged. The latex characteristics are reported in
Table 7. Subsequently 747 ml (corresponding to 225 g of polymer) of
the latex are introduced again in the 5 liters reactor to which
2.703 liters of demineralized water are added. The autoclave is
then heated up to 90.degree. C. and maintained for one hour at said
temperature in order to decompose all the residual initiator agent.
Subsequently the temperature is brought to 80.degree. C. and
maintained constant for the whole duration of the polymerization.
The following mixture of monomers was then fed:
[0206] perfluoromethylvinylether (PMVE) 60% by moles
[0207] tetrafluoroethylene (TFE) 40% by moles so as to increase the
pressure to 25 bar.
[0208] 0.175 g of ammonium persulphate (APS) as initiator
agent;
[0209] 11.14 g of 1,6-diiodoperfluorohexane
(C.sub.6F.sub.12I.sub.2) as chain transfer agent;
[0210] 2.14 g of bis-olefin of formula
CH.sub.2.dbd.CH--(CF.sub.2).sub.6--- CH.dbd.CH.sub.2; the addition
was carried out in 20 portions, each of 0.107 g, starting from the
polymerization beginning and for every 5% increase in the monomer
conversion, were then introduced in the autoclave.
[0211] The 25 bar pressure was maintained constant for the whole
duration of the polymerization by feeding a mixture formed by:
[0212] perfluoromethylvinylether (PMVE) 40% by moles
[0213] tetrafluoroethylene (TFE) 60% by moles
[0214] After 95 minutes of reaction corresponding to 1275 g of
produced elastomer, the autoclave was cooled and the latex
discharged.
[0215] The latex is coagulated with an aluminum sulphate solution
(6 g of Al.sub.2(SO.sub.4).sub.3 for each liter of latex) and dried
at 80.degree. C. in an air-circulating oven for 10 hours. The
obtained polymer was characterized as shown in Table 8.
EXAMPLE 12 COMPARATIVE
[0216] a) Preparation of the Semicrystalline Fluoropolymer
[0217] In a 10 l autoclave, equipped with a stirrer working at 545
rpm, after evacuation, 6.5 l of demineralized water and 16.25 ml of
a perfluoropolyoxyalkylene microemulsion were introduced: the
latter was previously obtained by mixing:
[0218] 3.52 ml of a perfluoropolyoxyalkylene, having an acid end
group, of formula:
CF.sub.2ClO(CF.sub.2--CF(CF.sub.3)O).sub.n(CF.sub.2O).sub.mCF.sub.2COOH
[0219] wherein n/m=10, having average molecular weight of 600;
[0220] 3.52 ml of a 30% by volume NH.sub.4OH aqueous solution;
[0221] 7.04 ml of demineralized water;
[0222] 2.17 ml of Galden.sup.(R) D02 of formula:
CF.sub.3O(CF.sub.2--CF(CF.sub.3)O).sub.n(CF.sub.2O).sub.mCF.sub.3
[0223] wherein n/m=20, having average molecular weight of 450.
[0224] The autoclave was then heated up to 80.degree. C. and
maintained at said temperature for the whole reaction duration. The
autoclave was pressurized to the pressure of 0.56 bar with ethane
and then to the pressure or 25 bar with a monomer mixture formed by
10% by moles of perfluoromethylvinylether (PMVE) and 90% by moles
of tetrafluoroethylene (TFE).
[0225] In the autoclave 1.3 g of ammonium persulphate (APS) as
initiator agent were then introduced.
[0226] During the reaction the pressure is maintained at 25 bar by
continuously feeding the following monomer mixture: 3.5% by moles
of PMVE and 96.5% of TFE.
[0227] After 65 minutes of reaction, the autoclave was cooled and
the latex discharged. The latex characteristics are reported in
Table 7.
[0228] b) Preparation of the Fluoroelastomer
[0229] The perfluoroelastomer latex was obtained as reported in
Example 10b. The latex characteristics are reported in Table 7.
[0230] c) Mixing of the Latexes--Preparation of the Final
Polymer
[0231] 233.7 ml of the latex obtained in Example 12a are mixed with
1187 ml of the Example 12b latex. After mixing, the latex is
coagulated with an aluminum sulphate solution (6 g of
Al.sub.2(SO.sub.4).sub.3 for each liter of latex) and dried at
80.degree. C. in an air-circulating oven for 10 hours. 500 g of
polymer, characterized as shown in Table 8, were obtained.
EXAMPLE 13
[0232] a) Preparation of the Semicrystalline Fluoropolymer
[0233] The PTFE latex is obtained as reported in Example 9a. The
latex properties are reported in Table 9.
[0234] b) Preparation of the Fluoroelastomer
[0235] In a 10 l autoclave, equipped with stirrer working at 545
rpm, after evacuation, 6.5 l of demineralized water and 65.1 ml of
a perfluoropolyoxyalkylene microemulsion were introduced: the
latter was previously obtained by mixing:
[0236] 14.1 ml of a perfluoropolyoxyalkylene, having an acid end
group of formula:
CF.sub.2ClO(CF.sub.2--CF(CF.sub.3)O).sub.n(CF.sub.2O).sub.mCF.sub.2COOH
[0237] wherein n/m=10, having average molecular weight of 600;
[0238] 14.1 ml of a 30% by volume NH.sub.4OH aqueous solution;
[0239] 28.2 ml of demineralized water;
[0240] 8.7 ml of Galden.sup.(R) D02 of formula:
CF.sub.3O(CF.sub.2--CF(CF.sub.3)O).sub.n(CF.sub.2O).sub.mCF.sub.3
[0241] wherein n/m=20, having average molecular weight of 450.
[0242] The autoclave was then heated up to 80.degree. C. and
maintained at said temperature for the whole reaction duration. The
following mixture of monomers was then fed:
[0243] vinylidene fluoride (VDF) 28% by moles
[0244] tetrafluoroethylene (TFE) 15% by moles
[0245] hexafluoropropene (HFP) 57% by moles so as to increase the
pressure to 30 bar.
[0246] 1.3 g of ammonium persulphate (APS) as initiator agent;
[0247] 16.17 g of diiodomethane (CH.sub.2I.sub.2) as chain transfer
agent fed with the following procedure: 20% at the reaction
beginning, 40% when the conversion is equal to 20% and 40% when the
conversion is equal to 80%;
[0248] 9 g of bis-olefin of formula
CH.sub.2.dbd.CH--(CF.sub.2).sub.6--CH.- dbd.CH.sub.2; the addition
was made in 20 portions, each of 0.45 g, starting from the
polymerization beginning and for every 5% increase in the monomer
conversion, were then introduced in the autclave.
[0249] The 30 bar pressure was maintained constant for the whole
duration of the polymerization by feeding a mixture formed by:
[0250] vinylidene fluoride (VDF) 50% by moles
[0251] tetrafluoroethylene (TFE) 25% by moles
[0252] hexafluoropropene (HFP) 25% by moles
[0253] After 270 minutes of reaction, the autoclave was cooled and
the latex discharged. The latex properties are reported in Table
9.
[0254] c) Mixing of the Latexes--Preparation of the Final
Polymer
[0255] 552 ml of the latex obtained in Example 14a are mixed with
1412 ml of the Example 14b latex. After mixing, the latex is
coagulated with an aluminum sulphate solution (6 g of
Al.sub.2(SO.sub.4).sub.3 for each liter of latex) and dried at
80.degree. C. in an air-circulating oven for 10 hours. 500 g of
polymer, characterized as shown in Table 10, were obtained.
EXAMPLE 14
[0256] a) Preparation of the Semicrystalline Fluoropolymer
[0257] In a 10 l autoclave, equipped with a stirrer working at 545
rpm, after evacuation, 6.5 l of demineralized water and 130 ml of a
perfluoropolyoxyalkylene microemulsion were introduced: the latter
was previously obtained by mixing:
[0258] 28.15 ml of a perfluoropolyoxyalkylene, having an acid end
group, of formula:
CF.sub.2ClO(CF.sub.2--CF(CF.sub.3)O).sub.n(CF.sub.2O).sub.mCF.sub.2COOH
[0259] wherein n/m=10, having average molecular weight of 600;
[0260] 28.15 ml of a 30% by volume NH.sub.4OH aqueous solution;
[0261] 56.3 ml of demineralized water;
[0262] 17.4 ml of Galden.sup.(R) D02 of formula:
CF.sub.3O(CF.sub.2--CF(CF.sub.3)O).sub.n(CF.sub.2O).sub.mCF.sub.3
[0263] wherein n/m=20, having average molecular weight of 450.
[0264] The autoclave was then heated up to 80.degree. C. and
maintained at said temperature for the whole reaction duration. The
autoclave was pressurized to the pressure of 0.56 bar with ethane
and then to the pressure of 20 bar by feeding a monomer mixture
formed by 1,8% by moles of perfluoropropylvinylether (PPVE) and
98,2% by moles of tetrafluoroethylene (TFE).
[0265] In the autoclave 1.3 g of ammonium persulphate (APS) were
then introduced as initiator. During the reaction the pressure is
maintained at 20 bar by continuously feeding the following monomer
mixture: 1.8% of PPVE and 98.2% of TFE.
[0266] After 18 minutes of reaction, the autoclave was cooled and
the latex discharged. The latex characteristics are reported in
Table 9.
[0267] b) Preparation of the Fluoroelastomer
[0268] In a 10 l autoclave, equipped with a stirrer working at 545
rpm, after evacuation, 6.5 l of demineralized water and 65.1 ml of
a perfluoropolyoxyalkylene microemulsion were introduced: the
latter was previously obtained by mixing:
[0269] 14.1 ml of a perfluoropolyoxyalkylene, having an acid end
group, of formula:
CF.sub.2ClO(CF.sub.2--CF(CF.sub.3)O).sub.n(CF.sub.2O).sub.mCF.sub.2COOH
[0270] wherein n/m=10, having average molecular weight of 600;
[0271] 14.1 ml of a 30% by volume NH.sub.4OH aqueous solution;
[0272] 28.2 ml of demineralized water;
[0273] 8.7 ml of Galden.sup.(R) D02 of formula:
CF.sub.3O(CF.sub.2--CF(CF.sub.3)O).sub.n(CF.sub.2O).sub.mCF.sub.3
[0274] wherein n/m=20, having average molecular weight of 450.
[0275] The autoclave was then heated up to 80.degree. C. and
maintained at said temperature for the whole reaction duration. The
following mixture of monomers was then fed:
[0276] perfluoromethylvinylether (PMVE) 60% by moles
[0277] tetrafluoroethylene (TFE) 40% by moles so as to increase the
pressure to 25 bar.
[0278] 0.32 g of ammonium persulphate (APS) as initiator agent;
[0279] 17 g of 1,6-diiodoperfluorohexane (C.sub.6F.sub.12I.sub.2)
as chain transfer agent;
[0280] 5 g of bis-olefin of formula
CH.sub.2.dbd.CH--(CF.sub.2).sub.6--CH.- dbd.CH.sub.2; the addition
was effected in 20 portions, each of 0.25 g, starting from the
polymerization beginning and for every 5% increase in the monomer
conversion, were then introduced in the autoclave.
[0281] The 25 bar pressure was maintained constant for the whole
duration of the polymerization by feeding a mixture formed by:
[0282] perfluoromethylvinylether (PMVE) 40% by moles
[0283] tetrafluoroethylene (TFE) 60% by moles
[0284] After 80 minutes of reaction, the autoclave was cooled and
the latex discharged. The latex properties are reported in Table
9.
[0285] c) Mixing of the Latexes--Preparation of the Final
Polymer
[0286] 528 ml of the latex obtained in Example 15a are mixed with
1218 ml of the Example 15b latex. After mixing, the latex is
coagulated with an aluminum sulphate solution (6 g of
Al.sub.2(SO.sub.4).sub.3 for each liter of latex) and dried at
80.degree. C. in an air-circulating oven for 10 hours. 500 g of
polymer, characterized as shown in Table 10, were obtained.
1 TABLE 1 Latex con- Particle MFI.sup.(1) Mooney centration
diameter ASTM (1 + 10).sup.121.degree. C. (g/l) (nm) D 1238 ASTM D
1646 Example 1a 118 12 82.7 -- Example 1b 280 54 -- 27 Example 2a
175 197 0.2 -- (comp.) Example 2b 280 54 -- 27 (comp.) .sup.(1)MFI
has been determined at 380.degree. C. with 3 Kg
[0287]
2 TABLE 2 EXAMPLE Ex. 2c Ex. 3c Ex. 4 Ex. 1c comp. comp. comp. % by
weight of plastomer 15 15 15 15 ML (1 + 10).sup.121.degree. C.
(ASTM D 1646) 58 nd 27 -- Formulation: Elastomer (phr) 100 100 100
100 TAIC (phr) 1.5 1.5 1.5 1.5 Luperco (phr) 2 2 2 2 ZnO (phr) 5 5
5 5 ODR (177.degree. C., 12' arc 3.degree.) (ASTM D 2084-81): ML
Lbf. in. 11 nd 17 13 MH Lbf. in. 118 nd 115 140 Ts2 sec 45 nd 45 51
T' 90 sec 99 nd 90 109 Molding in press at 180.degree. C. for 10
min: Sheet surface smooth nd rough rough Mechanical properties
after post cure at 200.degree. C. for 1 hour (ASTM D 412-83): M100
Mpa 4.9 nd 10.1 6.3 C.R. Mpa 19.3 nd 18.5 18.7 A.R. % 174 nd 145
174 ShA Hardness points 69 nd 85 76 Compression set on O-ring (ASTM
D 395): 200.degree. C. for 70 hours (%) 29 nd 40 broken 230.degree.
C. for 70 hours (%) 47 nd broken --
[0288]
3 TABLE 3 Latex con- Particle MFI.sup.(1) Mooney centration
diameter ASTM (1 + 10).sup.121.degree. C. (g/l) (nm) D 1238 ASTM D
1646 Example 5a 216 90 2 -- Example 5b 355 60 -- 20 Example 6 190
50 54.1 -- Example 7a 216 90 2 -- Example 7b 355 60 -- 18
.sup.(1)MFI has been determined at 380.degree. C. with 3 Kg
[0289]
4 TABLE 4 EXAMPLE Ex. 5c Ex. 6 Ex. 7c Ex. 8 % by weight of
plastomer 15 15 20 20 ML (1 + 10).sup.121.degree. C. (ASTM D 1646)
35 39 41 35 Formulation: Elastomer (phr) 100 100 100 100 TAIC (phr)
1.5 1.5 1.5 -- BO.sup.(2) -- -- -- 4 Luperco (phr) 2 2 2 4 ZnO
(phr) 5 5 5 5 ODR (177.degree. C., 12' arc 3.degree.) (ASTM D
2084-81): ML Lbf. in. 8 6 12 4 MH Lbf. in. 131 108 133 77 Ts2 sec
45 52 60 78 T' 90 sec 285 138 123 330 Molding in press at
180.degree. C. for 10 min: Sheet surface smooth smooth smooth
smooth Mechanical properties after post cure at 200.degree. C. for
1 h (ASTM D 412-83): M100 Mpa 5.6 4.5 7.9 10.1 C.R. Mpa 16.4 16.9
18.4 18.5 A.R. % 164 190 154 145 ShA Hardness points 73 72 78 85
Compression set on O-ring (ASTM D 395): 200.degree. C. for 70 hours
(%) 28 49 33 43 .sup.(2)Bisolefin of formula
CH.sub.2.dbd.CH--(CF.sub.2).sub.6--CH.dbd.CH.sub.2
[0290]
5 TABLE 5 Latex con- Particle MFI Mooney centration diameter ASTM
(1 + 10).sup.121.degree. C. (g/l) (nm) D 1238 ASTM D 1646 Example
9a 136 12 82.7.sup.(1) -- Example 9b 305 163 -- 38 .sup.(1)MFI has
been determined at 380.degree. C. with 3 Kg
[0291]
6 TABLE 6 EXAMPLE Ex. 9c % by weight of plastomer 15 ML (1 +
10).sup.121.degree. C. (ASTM D 1646) 48 Formulation: Elastomer
(phr) 100 TAIC (phr) 1.5 Luperco (phr) 2 ZnO (phr) 5 ODR
(177.degree. C., 12' arc 3.degree.) (ASTM D 2084-81): ML Lbf. in.
11 MH Lbf. in. 95 Ts2 sec 48 T' 90 sec 103 Molding in press at
180.degree. C. for 10 min: Sheet surface smooth Mechanical
properties after post cure at 200.degree. C. for 1 hour (ASTM D
412-83): M100 Mpa 6.3 C.R. Mpa 22.2 A.R. % 184 ShA hardness points
73 Compession set on O-ring (ASTM D 395): 200.degree. C. for 70
hours (%) 47
[0292]
7 TABLE 7 Latex con- Particle MFI Mooney centration diameter ASTM
(1 + 10).sup.121.degree. C. (g/l) (nm) D 1238 ASTM D 1646 Example
10a 315 60 295.sup.(1) -- Example 10b 358 54 -- 15 Example 11 301
26 216.sup.(2) -- Ex. 12a comp. 321 103 245.sup.(1) -- Ex. 12b
comp. 358 54 -- 15 .sup.(1)MFI has been measured at 372.degree. C.
with 5 Kg .sup.(2)MFI has been measured at 372.degree. C. with 10
Kg
[0293]
8 TABLE 8 EXAMPLE Ex. 12c Ex. 10c Ex. 11 comp. % by weight of
plastomer 15 15 15 ML (1 + 10).sup.121.degree. C. (ASTM D 1646) 27
55 28 Formulation: Elastomer (phr) 100 100 100 TAIC (phr) 1.5 1.5
1.5 Luperco (phr) 2 2 2 ZnO (phr) 5 5 5 ODR (177.degree. C., 12'
arc 3.degree.) (ASTM D 2084-81): ML Lbf. in. 5 20 5 MH Lbf. in. 129
134 83 Ts2 sec 54 46 54 T' 90 sec 114 97 99 Molding in press at
180.degree. C. for 10 min: Sheet surface smooth smooth rough
Mechanical properties after post cure at 200.degree. C. for 1 hour
(ASTM D 412-83): M100 Mpa 5.7 7.1 6.6 C.R. Mpa 16.4 19.0 18.4 A.R.
% 175 183 177 ShA hardness points 70 79 73 Compression set on
O-ring (ASTM D 395): 200.degree. C. for 70 hours (%) 29 47 --
[0294]
9 TABLE 9 Latex con- Particle MFI Mooney centration diameter ASTM
(1 + 10).sup.121.degree. C. (g/l) (nm) D 1238 ASTM D 1646 Example
13a 136 12 29.1.sup.(1) -- Example 13b 301 72 -- 51 Example 14a 142
60 80.sup.(2) -- Example 14b 349 54 -- 68 .sup.(1)MFI has been
measured at 380.degree. C. with 3 Kg .sup.(2)MFI has been measured
at 372.degree. C. with 5 Kg
[0295]
10 TABLE 10 EXAMPLE Ex. 13c Ex. 14c % by weight of plastomer 15 15
ML (1 + 10).sup.121.degree. C. (ASTM D 1646) 73 73 Formulation:
Elastomer (phr) 100 100 TAIC (phr) 3 1.5 Luperco (phr) 4 2 ZnO
(phr) 5 5 ODR (177.degree. C., 12' arc 3.degree.) (ASTM D 2084-81):
ML Lbf. in. 12 30 MH Lbf. in. 96 130 Ts2 sec 55 55 T' 90 sec 115
118 Molding in press at 180.degree. C. for 10 min: Sheete surface
smooth smooth Mechanical properties after post cure at 200.degree.
C. for 1 hour (ASTM D 412-83): M100 Mpa 4 6.2 C.R. Mpa 16.5 15.0
A.R. % 344 164 ShA hardness points 65 73 Compression set on O-ring
(ASTM D 395): 200.degree. C. for 70 hours (%) -- 32
* * * * *