U.S. patent application number 11/804529 was filed with the patent office on 2007-12-06 for concentrated fluoropolymer dispersions stabilized with anionic polyelectrolyte dispersing agents.
Invention is credited to Robert John Cavanaugh, Clay Woodward Jones.
Application Number | 20070282044 11/804529 |
Document ID | / |
Family ID | 38537831 |
Filed Date | 2007-12-06 |
United States Patent
Application |
20070282044 |
Kind Code |
A1 |
Cavanaugh; Robert John ; et
al. |
December 6, 2007 |
Concentrated fluoropolymer dispersions stabilized with anionic
polyelectrolyte dispersing agents
Abstract
An aqueous fluoropolymer dispersion comprising fluoropolymer
particles having an average particle size of about 10 to about 400
nm. The dispersion has a solids content of at least about 35 to
about 70 wt % and comprises about 0.03 wt % to about 10 wt %
anionic polyelectrolyte dispersing agent based on the weight of
fluoropolymer solids. The dispersion has a Gel Time of at least
about 100 seconds.
Inventors: |
Cavanaugh; Robert John;
(Cincinnati, OH) ; Jones; Clay Woodward;
(Washington, WV) |
Correspondence
Address: |
E I DU PONT DE NEMOURS AND COMPANY;LEGAL PATENT RECORDS CENTER
BARLEY MILL PLAZA 25/1128, 4417 LANCASTER PIKE
WILMINGTON
DE
19805
US
|
Family ID: |
38537831 |
Appl. No.: |
11/804529 |
Filed: |
May 18, 2007 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
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60809714 |
May 31, 2006 |
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Current U.S.
Class: |
524/244 ;
524/502; 524/544 |
Current CPC
Class: |
C08K 3/24 20130101; C08L
27/18 20130101; C08L 33/02 20130101; C08L 27/18 20130101; C09D
127/18 20130101; C08L 27/18 20130101; C08L 79/08 20130101; C09D
127/18 20130101; C08L 27/18 20130101; C09D 127/18 20130101; C08L
1/08 20130101; C09D 127/18 20130101; C08L 33/14 20130101; C08L
2666/04 20130101; C08L 2666/26 20130101; C08L 2666/26 20130101;
C08L 2666/20 20130101; C08L 2666/20 20130101; C08L 2666/04
20130101 |
Class at
Publication: |
524/244 ;
524/544; 524/502 |
International
Class: |
D06P 1/52 20060101
D06P001/52; C09B 67/00 20060101 C09B067/00 |
Claims
1. An aqueous fluoropolymer dispersion comprising fluoropolymer
particles having an average particle size of about 10 to about 400
nm, said dispersion having a solids content of about 35 to about 70
wt % and comprising about 0.03 wt % to about 10 wt % anionic
polyelectrolyte dispersing agent based on the weight of
fluoropolymer solids, said dispersion being substantially free of
nonionic surfactant and having a Gel Time of at least about 100
seconds.
2. The dispersion of claim 1 further comprising acrylic polymer of
acid content of 20% or more by weight.
3. The dispersion of claim 1 wherein said fluoropolymer particles
have an average particle size of about 100 to about 350 nm.
4. The dispersion of claim 1 wherein the solids content of the
dispersion is about 50 to about 70 wt %.
5. The dispersion of claim 1 wherein said anionic polyelectrolyte
dispersing agent is present in an amount of about 0.1 wt % to about
10 wt % based on the weight of fluoropolymer solids.
6. The dispersion of claim 2 wherein said acrylic polymer of acid
content of 20% or more is present in an amount of about 0.01 to
about 0.5 wt % based the weight of the aqueous portion of the
dispersion.
7. The dispersion of claim 2 wherein said acrylic polymer of acid
content of 20% or more is present in an amount of about 0.02 to
about 0.4 wt % based the weight of the aqueous portion of the
dispersion.
8. The dispersion of claim 1 wherein said dispersion contains less
than about 300 ppm fluorosurfactant based on the weight of said
dispersion
9. The dispersion of claim 1 wherein said dispersion contains less
than about 100 ppm fluorosurfactant based on the weight of said
dispersion.
10. The dispersion of claim 1 wherein said dispersion contains less
than about 50 ppm fluorosurfactant based on the weight of said
dispersion.
11. The dispersion of claim 1 wherein said dispersion has a Gel
Time of at least 300 seconds.
12. The dispersion of claim 1 wherein said dispersion has a Gel
Time of at least 500 seconds.
13. The dispersion of claim 1 further comprising anionic
surfactant.
14. The dispersion of claim 13 wherein said anionic surfactant is
present in an amount of about 0.05 to about 10 wt % based on the
weight of fluoropolymer solids.
15. The dispersion of claim 1 having a pH of at least about
9.0.
16. The dispersion of claim 1 having a pH of at least about
9.5.
17. The dispersion of claim 1 having a surface tension of greater
than about 35 mS/cm.
18. The dispersion of claim 1 wherein the anionic polyelectrolyte
dispersing agent is an anionic polymer, having a linear or branched
structure, with anionic groups distributed along the polymeric
chain.
19. The dispersion of claim 1 wherein the anionic polyelectrolyte
dispersing agent has an equivalent weight greater than about
150.
20. The dispersion of claim 1 wherein the equivalent weight of the
anionic polyelectrolyte dispersing agent is less than about
50,000.
21. The dispersion of claim 1 wherein the number average molecular
weight of the anionic polyelectrolyte dispersing agent is at least
about 500.
22. The dispersion of claim 1 wherein the anionic polyelectrolyte
dispersing agent contains at least 2 anionic functional groups per
molecule.
23. The dispersion of claim 1 wherein the anionic polyelectrolyte
dispersing agent contains anionic functional groups selected from
carboxylates, sulphates, sulphonates, phosphates, and
phosphonates.
24. The dispersion of claims 1 wherein the anionic polyelectrolyte
dispersing agent does not contain fluorine atoms.
25. The dispersion of claims 1 wherein the anionic polyelectrolyte
dispersing agents are selected from anionic homopolymers or
copolymers of monomers selected from acrylic or vinyl monomers.
26. The dispersion of claim 25 wherein the acrylic monomers are
selected from (meth)acrylamide, (meth)acrylic acid in the form of
the corresponding salts, (meth)acrylonitrile, linear or branched
C.sub.1-C.sub.4 hydroxyesters of the (meth)acrylic acid,
C.sub.1-C.sub.12 alkyl(meth)acrylates, wherein the alkyl can be
linear or branched, compounds of the following general formula:
##STR00004## wherein: R.sub.1 is H or CH.sub.3; R.sub.2 and
R.sub.3, equal or different, are H or C.sub.1-C.sub.8 alkyl,
optionally branched; M is an alkaline or alkaline-earth metal or
ammonium and A is NH, O or NCH.sub.3.
27. The dispersion of claim 25 wherein said anionic polyelectrolyte
dispersing agent is an acrylic copolymer.
28. The dispersion of claim 27 wherein said anionic polyelectrolye
dispersing agent is present in an amount of about 0.5 wt % to about
5.5 wt % based on the weight of fluoropolymer solids.
29. The dispersion of claim 27 wherein said acrylic copolymer
dispersing agent has a molecular weight of about 2,000 to about
100,000.
30. The dispersion of claim 27 wherein said acrylic copolymer
dispersing agent is hydrophobic.
31. The dispersion of claim 27 wherein said acrylic copolymer
dispersing agent comprises methacrylic acid/butyl methacrylate
copolymer.
32. The dispersion of claim 31 wherein said methacrylic acid/butyl
methacrylate copolymer comprises about 30 to about 50 mol %
methacrylic acid units and about 50 to about 70 mol % butyl
methacrylate units.
33. The dispersion of claim 25 wherein the vinyl monomers are
selected from vinylaromatic monomers, C.sub.1-C.sub.12 alkyl
vinylethers, and vinyl esters of C.sub.1-C.sub.18 aliphatic
monocarboxylic acids.
34. The dispersion of claim 33 wherein said vinylaromatic monomers
are selected from styrene and its derivatives obtained by
substituting one or more hydrogen atoms of the aromatic ring with a
hydroxyl or a methyl and/or of vinyl with a methyl.
35. The dispersion of claim 1 wherein the anionic polyelectrolyte
dispersing agent comprise polyamic acids.
36. The dispersion of claim 35 wherein the anionic polyelectrolyte
dispersing agent comprise polyamic acids selected from aromatic
polyamic acids or polyamidoamic acids.
37. The dispersion of claim 35 wherein the polyamic acids contain
the following units: ##STR00005## wherein R.sup.II is a divalent
arylene radical.
38. The dispersion of claims 1 wherein the anionic polyelectrolyte
dispersing agent comprise carboxyalkyl celluloses, wherein alkyl
comprises from 1 to 5 carbon atoms.
39. A process for reducing the fluorosurfactant content of and
concentrating an aqueous fluorosurfactant-containing fluoropolymer
dispersion comprising: stabilizing fluoropolymer dispersion
comprising fluoropolymer particles having an average size of about
10 to about 400 nm and a solids content of about 15 to about 55 wt
% with anionic polyelectrolyte dispersing agent; contacting said
stabilized fluorosurfactant-containing aqueous fluoropolymer
dispersion with an anion exchange resin to reduce fluorosurfactant
content to a predetermined level; separating said anion exchange
resin from said dispersion after the fluorosurfactant content has
been reduced to produce a reduced-fluorosurfactant dispersion; and
concentrating said dispersion to at least about 35% by weight using
a method which produces dispersion substantially free of nonionic
surfactants.
40. The process of claim 39 wherein said concentrating is performed
by adding acrylic polymer of acid content of 20% or more by weight
to said reduced-fluorosurfactant dispersion in an amount of about
0.01 to about 1 wt % based on aqueous content of said dispersion
and subjecting said dispersion to conditions causing said
dispersion to separate into a lower phase high in fluoropolymer
solids and an upper phase low in fluoropolymer solids and
recovering said lower phase as concentrated reduced
fluorosurfactant dispersion.
41. The process of claim 40 wherein the pH of said stabilized
fluoropolymer dispersion is at least about 6 when said adding of
acrylic polymer of acid content of 20% or more is performed.
42. The process of claim 40 wherein the pH of said stabilized
fluoropolymer dispersion is at least about 9 when said adding of
acrylic polymer of acid content of 20% or more is performed.
43. The process of claim 40 wherein the pH of said stabilized
fluoropolymer dispersion is at least about 9.5 when said adding of
acrylic polymer of acid content of 20% or more is performed.
44. The process of claim 39 wherein said concentrating is performed
by electrodecantation.
45. The process of claim 39 wherein said concentrated reduced
fluorosurfactant dispersion recovered has a solids content of about
35 to about 70 wt %.
46. The process of claim 39 wherein said concentrated reduced
fluorosurfactant dispersion recovered comprises less than about 300
ppm fluorosurfactant.
47. A process for applying fluoropolymer to a substrate comprising:
providing a concentrated aqueous fluoropolymer dispersion
comprising fluoropolymer particles and having a solids content of
about 35 to about 70 wt %, said dispersion comprising about 0.03 wt
% to about 10 wt % anionic polyelectrolyte dispersing agent based
on the weight of fluoropolymer solids and containing less than
about 300 ppm fluorosurfactant based on the weight of said
dispersion, said dispersion being substantially free of nonionic
dispersion; applying said dispersion to said substrate; and heating
said substrate coated with dispersion to coalesce said
fluoropolymer particles on said substrate.
48. The process of claim 47 wherein said substrate is metal.
49. The process of claim 47 wherein said aqueous dispersion further
comprises chromic acid.
50. The process of claim 47 wherein said substrate is catheter
guide wire.
51. A coating composition comprising the dispersion of claim 1
further comprising chromic acid.
Description
FIELD OF INVENTION
[0001] The present invention relates to concentrated fluoropolymer
dispersions and more particularly to concentrated stabilized
dispersions with reduced fluorosurfactant content.
BACKGROUND OF THE INVENTION
[0002] Fluoropolymers are applied to a wide number of substrates in
order to confer release, chemical and heat resistance, corrosion
protection, cleanability, low flammability, and weatherability.
Coatings of polytetrafluoroethylene (PTFE) homopolymers and
modified PTFE provide the highest heat stability among the
fluoropolymers, but unlike tetrafluoroethylene (TFE) copolymers,
cannot be melt processed to form films and coatings. Therefore,
other processes have been developed for applying coatings of PTFE
homopolymers and modified PTFE. One such process is dispersion
coating which applies the fluoropolymer in dispersion form.
Dispersions used in coating processes are usually in a concentrated
form and contain a significant quantity of nonionic surfactant,
e.g. 6-8 weight percent, as taught in Marks et al., U.S. Pat. No.
3,037,953. Similar dispersions and coating processes are also used
for making coatings of melt-processible fluoropolymers.
[0003] For some specialized fluoropolymer coating dispersions,
common nonionic surfactants such as alkyl phenol ethoxylates or
aliphatic alcohols ethoxylates for stabilization are unsuitable.
One such dispersion is a formulation in which chromic acid is used
as a component of a primer coating to increase adherence to metal
substrates. Chromic acid has been shown to attack nonionic
surfactants such as TRITON.RTM. X-100, an alkyl phenol ethoxylate.
Historically, an anionic surfactant such as sodium lauryl sulfate
has been used in this primer formulation because it is stable in
the presence of chromic acid.
[0004] Fluorosurfactants are typically used as an ingredient in the
dispersion polymerization of fluoropolymers, the fluorosurfactants
functioning as a non-telogenic dispersing agent. For example, an
early description of this use of fluorosurfactants is found in U.S.
Pat. No. 2,559,752 to Berry. However because of environmental
concerns and because fluorosurfactants are expensive, processes
have been developed for reducing and recovering fluorosurfactant
from aqueous fluoropolymer dispersions.
[0005] One common method is to remove fluorosurfactant by
adsorption onto an ion exchange resin as taught in U.S. Pat. No.
3,882,153 (Seki et al) and U.S. Pat. No. 4,282,162 (Kuhls) and U.S.
Pat. No. 6,833,403 (Bladel et al.) For effective removal, such
dispersions are stabilized with a nonionic surfactant, such as
alkyl phenol ethoxylates or aliphatic alcohol ethoxylates as
disclosed in U.S. Pat. No. 3,037,953 to Marks et al.; U.S. Pat. No.
6,153,688 to Miura et al.; and U.S. Pat. No. 6,956,078 to Cavanaugh
et al. Dispersions stabilized with nonionic surfactant are used
since removal of the fluorosurfactant without nonionic surfactant
being present generally results in coagulation of the
dispersion.
[0006] If it is attempted to use an anion exchange process for the
fluoropolymer dispersions discussed above that are stabilized with
an anionic hydrocarbon surfactant such as sodium lauryl sulfate
instead of nonionic surfactant, the anionic hydrocarbon surfactant
will be removed from the dispersion together with the
fluorosurfactant causing coagulation of the dispersion.
[0007] Improved stabilized concentrated fluoropolymer dispersions
with reduced fluorosurfactant content are desired.
BRIEF SUMMARY OF THE INVENTION
[0008] The present invention provides an aqueous fluoropolymer
dispersion comprising fluoropolymer particles having an average
particle size of about 10 to about 400 nm. The dispersion has a
solids content of at least about 35 to about 70 wt % and comprises
about 0.03 wt % to about 10 wt % anionic polyelectrolyte dispersing
agent based on the weight of fluoropolymer solids. The dispersion
has a Gel Time of at least about 100 seconds.
[0009] In a preferred embodiment of the dispersion of the
invention, the anionic polyelectrolyte dispersing agent has an
equivalent weight greater than about 150. Preferably, the
equivalent weight of the anionic polyelectrolyte dispersing agent
is less than about 50,000. The anionic polyelectrolyte dispersing
agent preferably has a number average molecular weight of at least
about 500. One preferred embodiment employs an acrylic copolymer
dispersing agent having a molecular weight of about 2000 to about
100,000. Preferably, the dispersion comprises less than about 300
ppm fluorosurfactant based on the weight of the dispersion.
[0010] The invention further provides a process for reducing the
fluorosurfactant content of and concentrating an aqueous
fluorosurfactant-containing fluoropolymer dispersion comprising
stabilizing fluoropolymer dispersion comprising fluoropolymer
particles having an average size of about 10 to about 400 nm and a
solids content of about 15 to about 55 wt % with anionic
polyelectrolyte dispersing agent, contacting the stabilized
fluorosurfactant-containing aqueous fluoropolymer dispersion with
an anion exchange resin to reduce fluorosurfactant content to a
predetermined level, separating the anion exchange resin from the
dispersion after the fluorosurfactant content has been reduced to
produce a reduced-fluorosurfactant dispersion, and concentrating
the dispersion to at least about 35% by weight using a method which
produces dispersion substantially free of nonionic surfactants.
[0011] The invention further relates to a process for applying
fluoropolymer to a substrate comprising providing a concentrated
aqueous fluoropolymer dispersion comprising fluoropolymer particles
and having a solids content of about 35 to about 70 wt %, the
dispersion comprising about 0.03 wt % to about 10 wt % anionic
polyelectrolyte dispersing agent based on the weight of
fluoropolymer solids and containing less than about 300 ppm
fluorosurfactant based on the weight of the dispersion, the
dispersion being substantially free of nonionic dispersion;
applying the dispersion to the substrate; and heating the substrate
coated with dispersion to coalesce the fluoropolymer particles on
the substrate.
DETAILED DESCRIPTION OF THE INVENTION
Fluoropolymers
[0012] The aqueous fluoropolymer dispersion in accordance with the
present invention is made by dispersion polymerization (also known
as emulsion polymerization). Fluoropolymer dispersions are
comprised of particles of polymers made from monomers wherein at
least one of the monomers contains fluorine. The fluoropolymer of
the particles of the aqueous dispersions of this invention is
independently selected from the group of polymers and copolymers of
trifluoroethylene, hexafluoropropylene,
monochlorotrifluoroethylene, dichlorodifluoroethylene,
tetrafluoroethylene, perfluoroalkyl ethylene monomers,
perfluoro(alkyl vinyl ether) monomers, vinylidene fluoride, and
vinyl fluoride.
[0013] Preferred fluoropolymer particles used in the dispersion
employed in this invention are non-melt-processible particles of
polytetrafluoroethylene (PTFE) including modified PTFE which is not
melt-processible. Polytetrafluoroethylene (PTFE) refers to the
polymerized tetrafluoroethylene by itself without any significant
comonomer present. Modified PTFE refers to copolymers of TFE with
such small concentrations of comonomer that the melting point of
the resultant polymer is not substantially reduced below that of
PTFE. The concentration of such comonomer is preferably less than 1
wt %, more preferably less than 0.5 wt %. A minimum amount of at
least about 0.05 wt % is preferably used to have significant
effect. The modified PTFE preferably contains a comonomer modifier
which improves film forming capability during baking (fusing), such
as perfluoroolefin, notably hexafluoropropylene (HFP) or
perfluoro(alkyl vinyl)ether (PAVE), where the alkyl group contains
1 to 5 carbon atoms, with perfluoro(ethyl vinyl)ether (PEVE) and
perfluoro(propyl vinyl)ether (PPVE) being preferred.
Chlorotrifluoroethylene (CTFE), perfluorobutyl ethylene (PFBE), or
other monomer that introduces bulky side groups into the molecule
are also included. In this preferred form of the invention, the
PTFE typically has a melt creep viscosity of at least
1.times.10.sup.9 Pas. The resins in the dispersion used in this
form of the invention when isolated and dried are thus
non-melt-processible.
[0014] By non-melt-processible, it is meant that no melt flow is
detected when tested by the standard melt viscosity determining
procedure for melt-processible polymers. This test is according to
ASTM D-1238-00 modified as follows: The cylinder, orifice and
piston tip are made of corrosion resistant alloy, Haynes Stellite
19, made by Haynes Stellite Co. The 5.0 g sample is charged to the
9.53 mm (0.375 inch) inside diameter cylinder which is maintained
at 372.degree. C. Five minutes after the sample is charged to the
cylinder, it is extruded through a 2.10 mm (0.0825 inch diameter),
8.00 mm (0.315 inch) long square-edge orifice under a load (piston
plus weight) of 5000 grams. This corresponds to a shear stress of
44.8 KPa (6.5 pounds per square inch). No melt extrudate is
observed.
[0015] In one preferred embodiment, the fluoropolymer particles in
the dispersion used in this invention comprise a core of high
molecular weight polytetrafluoroethylene (PTFE) and a shell of
lower molecular weight polytetrafluoroethylene or modified
polytetrafluoroethylene.
[0016] The preferred non-melt-processible PTFE or modified PTFE
have a standard specific gravity (SSG) of about 2.13 to about 2.50.
Preferably, the SSG is less than about 2.40, more preferably less
than about 2.30, and most preferably less than about 2.25. The SSG
is generally inversely proportional to the molecular weight of PTFE
or modified PTFE.
[0017] The fluoropolymer particles in the dispersion used in this
invention have a number average particle size of about 10 nm to
about 400 nm, preferably, about 100 nm to about 350 nm.
[0018] A typical process for the aqueous dispersion polymerization
of preferred PTFE polymer is a process wherein TFE vapor is fed to
a heated reactor containing fluorosurfactants, paraffin wax and
deionized water. A chain transfer agent may also be added if it is
desired to reduce the molecular weight of the PTFE. A free-radical
initiator solution is added and, as the polymerization proceeds,
additional TFE is added to maintain the pressure. The exothermic
heat of reaction is removed by circulating cooling water through
the reactor jacket. After several hours, the feeds are stopped, the
reactor is vented and purged with nitrogen, and the raw dispersion
in the vessel is transferred to a cooling vessel. Paraffin wax is
removed and the dispersion is isolated and stabilized with
dispersing agent.
[0019] The fluorosurfactant used in the manufacture of the
dispersion is a non-telogenic, anionic dispersing agent, soluble in
water and comprising an anionic hydrophilic group and a hydrophobic
portion. Preferably, the hydrophobic portion is an aliphatic
fluoroalkyl group containing at least four carbon atoms and bearing
fluorine atoms and having no more than two carbon atoms not bearing
fluorine atoms adjacent to the hydrophilic group. These
fluorosurfactants are used as a polymerization aid for dispersing
and, because they do not chain transfer, they do not cause
formation of polymer with undesirable short chain length. An
extensive list of suitable fluorosurfactants is disclosed in U.S.
Pat. No. 2,559,752 to Berry. Preferably, the fluorosurfactant is a
perfluorinated carboxylic or sulfonic acid having 6-10 carbon atoms
and is typically used in salt form. Suitable fluorosurfactants are
ammonium perfluorocarboxylates, e.g., ammonium perfluorocaprylate
or ammonium perfluorooctanoate. The fluorosurfactants are usually
present in the amount of 0.02 to 1 wt % with respect to the amount
of polymer formed. The fluorinated surfactant is used to aid the
polymerization process but the amount remaining in the dispersion
is significantly reduced as will be explained below.
[0020] The initiators, preferably used to make dispersion of this
invention are free radical initiators. They may be those having a
relatively long half-life, preferably persulfates, e.g., ammonium
persulfate or potassium persulfate. To shorten the half-life of
persulfate initiators, reducing agents such as ammonium bisulfite
or sodium metabisulfite, with or without metal catalysis salts such
as Fe (III), can be used. Alternatively, short half-life initiators
such as potassium permanganate/oxalic acid can be used.
[0021] In addition to the long half-life persulfate initiators,
small amounts of short chain dicarboxylic acids such as succinic
acid or initiators that produce succinic acid such as disuccinic
acid peroxide (DSP) may be also be added in order to reduce
coagulum
[0022] To produce dispersion with low fluorosurfactant content as
described below, sufficient anionic polyelectrolyte dispersing
agent as is described in more detail hereinafter is added to
prevent coagulation of the dispersion when the fluorosurfactant
content is reduced. Typically, dispersing agent is added for
stabilization prior to fluorosurfactant reduction
[0023] The dispersion is concentrated as will be described below.
The concentrated aqueous dispersion has a fluoropolymer solids
content of at least about 35 wt %, preferably at least about 40 wt
%, and more preferably at least about 45 wt %. The concentrated
aqueous dispersion can range in fluoropolymer solids content from
at least about 35 wt % to about 70 wt %, preferably at least about
40 wt % to about 70 wt %, more preferably at least about 45 wt % to
about 70 wt % and especially at least about 50 wt % to about 70 wt
%.
[0024] The aqueous dispersion in accordance with the invention is
substantially free of nonionic surfactants. "Substantially free"
means that the dispersion contains either no nonionic surfactant or
so little nonionic surfactant that such nonionic surfactant will
not interfere with end-use applications. Preferably, the dispersion
contains less than about 2 wt % of nonionic surfactant based on
dispersion weight, preferably less than about 1 wt %, more
preferably less than about 0.5 wt % and especially less than 0.1 wt
%.
Dispersing Agents
[0025] Fluoropolymer dispersions are typically stabilized with
surfactants. A surfactant has a hydrophilic portion and a
hydrophobic portion on the same molecule. These can be either
cationic, nonionic or anionic. A typical cationic surfactant has a
positively charged hydrophilic portion such as an alkylated
ammonium halide and a hydrophobic portion such as a long chain
fatty acid. An anionic surfactant has a negatively charged
hydrophilic portion such as a carboxylate or sulfate salt and a
long chain hydrocarbon portion as the hydrophobic portion. A
nonionic surfactant does not contain a charged group but has a
hydrophobic portion that is typically a long chain hydrocarbon
similar to the other two types of surfactants. The hydrophilic
portion of the nonionic surfactant typically contains water soluble
functionality such as a chain of ethylene ether derived from
polymerization with ethylene oxide. Water solubility is due to
hydrogen bonding of the ether oxygen atoms with protons from the
water. Surfactants stabilize polymer particles by coating the
particles with the hydrophobic portion of the surfactant oriented
towards the particle and the hydrophilic portion of the surfactant
in the water phase. In the case of charged surfactants, some
stability is also due to repulsion of the electrical charges
between particles. Surfactants typically reduce surface tension
significantly and allow better wetting of surfaces with the
dispersion. In contrast, anionic polyelectrolyte dispersing agents
are employed in dispersions in accordance with the invention for
stabilization. These dispersing agents are different from
surfactants in that they do not contain distinct hydrophilic and
hydrophobic portions. It is believed that stabilization of
fluoropolymer dispersions occurs when the anionic polyelectrolyte
dispersing agents coat the fluoropolymer particles. The anionic
groups carried on the dispersing agents increase the surface charge
on the particle and confer stability by repulsion of the electrical
charges between particles. Unlike surfactants, these dispersing
agents typically have little if any significant effect on surface
tension of the dispersion. The surface tension of the dispersion
containing anionic polyelectrolyte dispersing agents remains high
unless surfactants are added to alter wetting properties, for
viscosity control, improve stability, etc. Nonionic surfactants,
substantially reduce the surface tension of the aqueous solutions.
In contrast the polyelectrolytes are often used as flocculating
agents of colloidal dispersions whereas surfactants are normally
used to stabilize colloidal dispersions. Surface tension of a
preferred dispersion in accordance with the present invention is
greater than about 35 dyne/cm at 25.degree. C., preferably greater
than about 40 dyne/cm, still more preferably greater than about 45
dyne/cm.
[0026] The anionic polyelectrolyte dispersing agents employed in
accordance with dispersions and processes of the present invention
are preferably anionic polymers, having a linear or branched
structure, with anionic groups distributed along the polymeric
chain, optionally present also in the chain end groups. The
polyelectrolytes preferably have an equivalent weight, defined as
molecular weight/number of anionic groups present in the
polyelectrolyte, greater than about 150, preferably greater than
about 200, still more preferably greater than about 250. Generally
the equivalent weight of the anionic polyelectrolyte dispersing
agents usable in the process of the present invention is less than
about 50,000, preferably less than about 10,000, more preferably
less than about 3,000, still more preferably less than about
1,500.
[0027] The number average molecular weight of the anionic
polyelectrolyte dispersing agent is preferably at least about 500,
more preferably in the range of about 500 to about 100,000. More
preferably, the molecular weight is at least about 1,000.
Especially preferred embodiments have a molecular weight of about
2,000 to about 100,000 and preferably 5,000 to about 20,000.
[0028] The anionic polyelectrolyte dispersing agents usable in the
process according to the present invention preferably contain in
the molecule a number of anionic functional groups higher than or
equal to 2, more preferably greater than or equal to 5. The anionic
groups present in the molecule of the anionic polyelectrolyte
agents are preferably selected from carboxylates, sulphates,
sulphonates, phosphates, phosphonates, are more preferably
carboxylates, sulphates, sulphonates, and still more preferably are
carboxylates. Generally, the anionic polyelectrolyte dispersing
agents do not contain fluorine atoms.
[0029] Preferably, the anionic polyelectrolyte dispersing agents
used according to the present invention are selected from anionic
homopolymers or copolymers of monomers selected from acrylic or
vinyl monomers which preferably provide a number of anionic groups
as mentioned above give the equivalent weight as defined above.
Preferably, acrylic monomers are selected from (meth)acrylamide,
(meth)acrylic acid in the form of the corresponding salts,
(meth)acrylonitrile, linear or branched C.sub.1-C.sub.4
hydroxyesters of the (meth)acrylic acid, C.sub.1-C.sub.12
alkyl(meth)acrylates, wherein the alkyl can be linear or branched,
compounds of the following general formula:
##STR00001##
wherein: R.sub.1 is H or CH.sub.3; R.sub.2 and R.sub.3, equal or
different, are H or C.sub.1-C.sub.8 alkyl, optionally branched; M
is an alkaline or alkaline-earth metal or ammonium and A is NH, O
or NCH.sub.3.
[0030] Among the vinyl monomers which can provide anionic
polyelectrolytes for use in accordance with the present invention,
vinylaromatic monomers can be used, preferably styrene and its
derivatives obtained by substituting one or more hydrogen atoms of
the aromatic ring with a hydroxyl or a methyl and/or of vinyl with
a methyl, for example, alpha-methylstyrene; C.sub.1-C.sub.12 alkyl
vinylethers, such as methyl-, ethyl-, n-propyl-, isopropyl-,
n-butyl-, isobutyl- and 2-ethylhexyl-vinyl ether; and vinyl esters
of C.sub.1-C.sub.18 aliphatic monocarboxylic acids, such as vinyl
acetate, vinyl propionate, vinyl butyrate, vinyl-2-ethyl-hexanoate,
and vinyl stearate.
[0031] Homopolymers or copolymers of one or more monomers selected
from acrylic or vinyl monomers are obtainable by aqueous suspension
polymerization by radical or ionic addition, according to well
known methods of the prior art. See for example Kirk Othmer
"Encyclopedia of Chemical Technology", III Ed., vol. 18, pages
720-744. In case of radical polymerization in aqueous suspension,
as radical initiators, those soluble in monomers are preferably
used and furthermore suspending agents, surfactants are used.
[0032] As radical initiators, aliphatic and aromatic peroxides are
for example used, as for example t-butylperoxy-2-ethylhexanoate,
dibenzoylperoxide, benzoylperoxide, laurylperoxide,
t-butylperoxydiethylacetate or unstable azocompounds as for example
azodiisobutyronitrile. In the monomeric mixture also a chain
transfer agent can optionally be used. Mercaptan compounds, as
mercaptoethanol, mercaptopropanol, mercaptobutanol, mercaptoacetic
acid, mercaptopropionic acid, butylmercaptan, n-dodecylmercaptan,
can for example be mentioned. The polymerization temperatures are
those at which there is the initiator decomposition, and are
generally from about 50.degree. C. to about 120.degree. C. For the
suspending agents see for example EP 457,356.
[0033] Other usable anionic polyelectrolyte dispersing agents are
polyamic acids, preferably aromatic polyamic acids or polyamidoamic
acids. Examples of repeating units of these polymers are:
amido-amic acid:
##STR00002##
amidoimidic unit:
##STR00003##
wherein R.sup.II is a divalent arylene radical. See, for example,
U.S. Pat. No. 6,479,581 which describes preparation of such
polymers.
[0034] Other usable anionic polyelectrolyte dispersing agents are
carboxyalkyl celluloses, wherein the alkyl comprises from 1 to 5
carbon atoms, preferably from 1 to 3, for example
carboxymethylcellulose.
[0035] The polyelectrolyte dispersing agents usable in accordance
with the invention are, for example, those sold under the
trademarks Craymul.RTM. 8212 (Cray Valley), Torlon.RTM. AI30
(Solvay Advanced Polymers), Torlon.RTM. AI50 (Solvay Advanced
Polymers), Elvacite.RTM. 2669 and Elvacite.RTM. 2776 (Lucite
International), and Joncryl.RTM. DFC 3025 (Johnson Polymer).
[0036] Anionic polyelectrolytes for used in accordance with the
present invention are generally soluble in water. Co-solvents
miscible with water such as alcohols, e.g., isopropyl alcohol,
ketones, e.g., N-methylpyrrolidone, can optionally be added.
[0037] The anionic polyelectrolyte dispersing agent is added in an
amount of about 0.03 to about 10 wt %, preferably about 0.1 wt % to
about 10 wt %, more preferably from about 0.2 wt % to about 5 wt %,
still more preferably from about 0.5 wt % to about 3 wt % in
percent by weight based on the weight of the fluoropolymer solids.
The polyelectrolyte amount generally depends on the type of
polyelectrolyte used. One skilled in the art is easily able
determine an appropriate amount sufficient to confer the stability
desired.
[0038] One class of preferred anionic dispersing agents are acrylic
copolymers, more preferably acrylic copolymer dispersing agents
described as being hydrophobic acrylic copolymers. Examples of
polymer of this type are sold under the trademarks TAMOL.RTM. 681,
TAMOL.RTM. 2001, TAMOL.RTM. 165A and TAMOL.RTM. 731A sold by Rohm
and Haas. Such dispersing agents are known for use in acrylic-based
paints to prevent agglomeration of pigments but they are not known
for use in fluoropolymer dispersions. A preferred acrylic copolymer
dispersing agent for use in this invention comprises methacrylic
acid/butyl methacrylate copolymer. More preferably the methacrylic
acid/butyl methacrylate copolymer comprises about 30 to about 50
mol % methacrylic acid units and about 50 to about 70 mol % butyl
methacrylate units. In embodiments of the invention employing this
type of acrylic copolymer anionic polyelectrolyte, amounts acrylic
copolymer of about 0.5 wt % to about 5.5 wt % based on the weight
of fluoropolymer solids have been found to be especially useful.
Percentages of the acrylic copolymer dispersing agent are based on
active ingredients.
[0039] A preferred acrylic copolymer dispersing agent for this
invention has a molecular weight of about 2,000 to about 100,000
and more preferably has a molecular weight of about 5,000 to about
20,000.
[0040] Although the acrylic copolymer dispersing agent may be
supplied in acid form, it is employed in salt form in the
fluoropolymer dispersions of the invention for effective
stabilization. Although various salt forms can be used, a preferred
form of the acrylic copolymer dispersing agent is in the form of an
ammonium salt so that it does not introduce extraneous cations into
the dispersion. For the acrylic copolymer dispersing agent to be
predominantly in salt form and soluble in water, the pH of the
fluoropolymer dispersion is preferably at least about 9, more
preferably at least about 9.5.
Dispersion Shear Stability--Gel Time
[0041] In accordance with the invention, the dispersion has a Gel
Time of at least about 100 seconds as determined by the Gel Time
test described in the Test Methods of this application. Gel Time is
a measurement of resistance of the dispersion to coagulation under
high shear conditions and thus is an indicator of the stability of
the dispersion during processing which subjects the dispersion to
shear. Although affected by a variety of factors including solids
content, pH, molecular weight of the polymer, polymer particle
morphology, other materials in the dispersion, etc., a Gel Time of
at least 100 indicates that the anionic polyelectrolyte dispersing
agent is functioning to stabilize the polymer sufficiently for
normal handling and processing, e.g., is sufficiently stabilized
for fluorosurfactant removal in an anion exchange column. More
preferably, the Gel Time is at least about 300 seconds, even more
preferably at least about 500 seconds, even more preferably at
least about 1000 seconds, and most preferably at least about 1500
seconds. A preferred range of Gel Time provided by the present
invention is about 100 seconds to about 2000 seconds. In accordance
with a preferred form of the invention, the dispersion contains
less than about 300 ppm fluorosurfactant based on the weight of the
dispersion and has the Gel Times as indicated above. Preferably,
the Gel Times described above are observed when the
fluorosurfactant content is less than about 100 ppm, most
preferably less than about 50 ppm.
[0042] Hydrophobic acrylic copolymer anionic polyelectrolytes
described above are especially useful in accordance with the
invention for providing desirable gel times.
Fluorosurfactant Reduction
[0043] In accordance with the process of the invention for reducing
the fluorosurfactant content of and concentrating a
fluorosurfactant-containing aqueous fluoropolymer dispersion, the
fluorosurfactant content of the dispersion stabilized with anionic
polyelectrolyte dispersing agent is reduced to a predetermined
level. The resulting dispersion has reduced fluorosurfactant
content than as polymerized dispersion and preferably has a
fluorosurfactant content of less than about 300 ppm based on the
total dispersion weight. Preferably, the fluorosurfactant content
is less than about 100 ppm, more preferably less than about 50
ppm.
[0044] The fluorosurfactant content can be reduced by any of a
variety of procedures as known in the art. In the preferred
embodiment of the present invention, the fluorosurfactant is
removed by adsorption onto an anion exchange resin. Contacting of
the dispersion with anion exchange resin is preferably performed
before concentration especially when a preferred concentration
method is employed using the addition of an acrylic polymer with
high acid content described in U.S. Pat. No. 5,272,186 to Jones
because the acrylic polymer with high acid content may be adsorbed
onto the anion exchange resin.
[0045] Any of a variety of techniques which bring the dispersion in
contact with the anion exchange resin can be used to carry out ion
exchange of the process. For example, the process can be carried
out by addition of ion exchange resin bead to the dispersion in a
stirred tank, in which a slurry of the dispersion and resin is
formed, followed by separation of dispersion from the anion
exchange resin beads by filtration. Another suitable method is to
pass the dispersion through a fixed bed of anion exchange resin
instead of using a stirred tank. Flow can be upward or downward
through the bed and no separate separation step is needed since the
resin remains in the fixed bed.
[0046] The contacting of the dispersion is performed at a
temperature which is sufficiently high to facilitate the rate of
ion exchange and to reduce the viscosity of the dispersion but
being below a temperature at which the resin degrades at a
detrimentally high rate or a viscosity increase in observed. Upper
treatment temperature will vary with the type of polymer and
nonionic surfactant employed. Typically, temperatures will be
between 20.degree. C. and 80.degree. C.
[0047] The fluorosurfactant can be recovered from the anion
exchange resin if desired or the resin with the fluorosurfactant
can be disposed of in an environmentally acceptable method, e.g.,
by incineration. If it is desired to recover the fluorosurfactant,
the fluorosurfactant may be removed from resin by elution. Elution
of fluorosurfactant adsorbed on the anion exchange resin is readily
achieved by use of ammonia solution as demonstrated by Seki in U.S.
Pat. No. 3,882,153, by a mixture of dilute mineral acid with
organic solvent (e.g., HCl/ethanol) as demonstrated by Kuhls in
U.S. Pat. No. 4,282,162, or by strong mineral acids such as
sulfuric acid and nitric, transferring the adsorbed fluorinated
carboxylic acid to the eluent. The fluorosurfactant in the eluent
in high concentration can easily be recovered in the form of a pure
acid or in the form of salts by common methods such as
acid-deposition, salting out, and other methods of concentration,
etc.
Ion Exchange Resins
[0048] The ion exchange resins for use in reducing the
fluorosurfactant content of the aqueous dispersion include anionic
resins but can also include other resin types such as cationic
resins, e.g., in a mixed bed. The anionic resins employed can be
either strongly basic or weakly basic. Suitable weakly basic anion
exchange resins contain primary, secondary amine, or tertiary amine
groups. Suitable strongly basic anion exchange resin contain
quaternary ammonium groups. Although weakly basic resins are useful
because they can be regenerated more easily, strongly basis resins
are preferred when it is desired to reduce fluorosurfactant to very
low levels and for high utilization of the resin. Strongly basic
ion exchange resins also have the advantage of less sensitivity to
the pH of the media. Strong base anion exchange resins have an
associated counter ion and are typically available in, chloride or
hydroxide form but are readily converted to other forms if desired.
Anion exchange resins with hydroxide, chloride, sulfate, and
nitrate can be used for the removal of the fluorosurfactant but
anion exchange resins in the form of hydroxide are preferred to
prevent the introduction of additional anions and to increase pH
during anion exchange because a high pH, i.e., greater than 9, is
desirable in the product prior to shipping to inhibit bacterial
growth. Examples of suitable commercially-available strong base
anion exchange resins with quaternary ammonium groups with a
trimethylamine moiety include DOWEX.RTM. 550A, US Filter A464-OH,
SYBRON M-500-OH, SYBRON ASB1-OH, PUROLITE A-500-OH, Itochu TSA
1200, AMBERLITE.RTM. IR 402. Examples of suitable
commercially-available strong base anion exchange resins with
quaternary ammonium groups with a dimethyl ethanol amine moiety
include US Filter A244-OH, AMBERLITE.RTM. 410, DOWEX.RTM. MARATHON
A2, and DOWEX.RTM. UPCORE Mono A2.
[0049] Ion exchange resin used to reduce fluorosurfactant for use
in the process is preferably monodisperse. Preferably, the ion
exchange resin beads have a number average size distribution in
which 95% of the beads have a diameter within plus or minus 100
.mu.m of the number average bead diameter.
Concentration
[0050] Concentration is carried out in accordance with the
invention using a method which provides a concentrated dispersion
substantially free of nonionic surfactants. Nonionic surfactants,
such as alkyl phenol ethoxylates or aliphatic alcohols ethoxylates,
typically used for stabilization of fluoropolymer dispersions have
a cloud point between about 30.degree. C. and about 90.degree. C.
which enable concentration by a phase separation process such as
that disclosed in U.S. Pat. No. 3,037,953 to Marks et al. Anionic
polyelectrolyte dispersing agents, on the other hand, typically
have no significant cloud point between about 30.degree. C. and
about 90.degree. C. Therefore, other methods are used in accordance
with the invention to provide the desired concentration which
leaves the concentrated dispersion free of nonionic
surfactants.
[0051] One preferred method for concentration employs acrylic
polymers of high acid content as described in U.S. Pat. No.
5,272,186 to Jones. The concentrating is performed by adding
acrylic polymer of acid content of 20% or more by weight to the
reduced-fluorosurfactant dispersion in an amount of about 0.01 to
about 1 wt % based on aqueous content of the dispersion and
subjecting the dispersion to conditions causing the dispersion to
separate into a lower phase high in fluoropolymer solids and an
upper phase low in fluoropolymer solids and recovering the lower
phase as concentrated reduced fluorosurfactant dispersion.
[0052] To carry out the preferred concentration process, U.S. Pat.
No. 5,272,186 states that the pH of the dispersion should be
adjusted to at least about 6. As discussed above, it is preferable
for the pH of the dispersion to be at least about 9, more
preferably at least 9.5 for effective stabilization by the
preferred anionic polyelectrolyte dispersing agent so that
adjustment usually will not be necessary. If pH adjustment is
necessary, typically a base such as ammonium hydroxide is used. The
acrylic polymer concentrating agent preferably used in
concentration has an acid content of 20% or more by weight.
Preferably, the acrylic polymer of high acid content has a
weight-average molecular weight of about 50,000 to about 1,000,000,
and is employed in an amount of about 0.01 wt % to about 0.5 wt %
based on the weight of the aqueous portion of the dispersion, more
preferably about 0.02 to about 0.4 wt %. In a preferred embodiment,
the acrylic polymers have a molecular weight of about 200,000 to
1,000,000. In another preferred embodiment the acrylic polymer is
added in amount of about 0.03 to about 0.2 wt % based on the weight
of the aqueous portion of the dispersion. An especially preferred
acrylic polymer of high acid content is polyacrylic acid.
[0053] After addition of the acrylic polymer having an acid content
of 20% or more by weight, the dispersion is subjected to conditions
which cause a phase separation to occur. Typically, this involves
letting the dispersion stand at ambient condition, preferably
without agitation. The phase separation forms a concentrated
dispersion of typical solids content of about 35 wt % to about 70
wt %, preferably about 40 wt % to about 70 wt % and more preferably
about 50 wt % to about 70 wt %, as a lower phase. The upper phase
will have substantially lower solids, preferably less than about 1
wt %.
[0054] Another preferred method for concentration is
electrodecantation. Concentration of solids by electrodecantation
is achieved by electrophoretic migration of PTFE particles
employing direct current potential which is applied from electrodes
at either end of a container containing the dispersion. Negatively
charged PTFE particles surrounded by anionic dispersing agent move
in the applied field toward the anode. Semi-permeable membrane
barriers are suspended vertically in the container between the
electrodes and form concentrating cells and prevent the particles
from contacting the anode. Concentrated dispersion moves downward
along one face of the membrane and depleted dispersion moves upward
on the other face. The concentrated dispersion being denser settles
to the bottom of the container and can be drawn of at intervals.
The supernatant liquid remains overhead.
Coating Applications
[0055] The invention further relates to a process for applying
fluoropolymer to a substrate comprising providing a concentrated
aqueous fluoropolymer dispersion comprising fluoropolymer particles
and having a solids content of about 35 to about 70 wt %, the
dispersion comprising about 0.03 wt % to about 10 wt % anionic
polyelectrolyte dispersing agent based on the weight of
fluoropolymer solids and containing less than about 300 ppm
fluorosurfactant based on the weight of the dispersion, the
dispersion being substantially free of nonionic dispersion;
applying the dispersion to the substrate; and heating the substrate
coated with dispersion to coalesce the fluoropolymer particles on
the substrate.
[0056] The process of the invention is especially suitable for
metal substrates, preferably for coating compositions which contain
chromic acid as a component of a primer coating to increase
adherence to the metal. One such application is the coating of
catheter guide wire. Other applications include the coating of any
of a variety of metal process equipment components such as rollers,
tanks, trays, etc. Known techniques and equipment for coating
application can be adapted for use in accordance with the process
of the present invention.
[0057] For some applications, anionic surfactant such as ammonium
or alkali metal lauryl sulfate, e.g., sodium lauryl sulfate is
added to the fluoropolymer dispersion of this invention. Addition
of anionic surfactant can lower the viscosity and enhance the
stability of the dispersion. For coating uses, anionic surfactant
can improve wetting characteristics. The anionic surfactant can be
added can be added to the dispersion at any time after
fluorosurfactant reduction. However, it is generally preferable to
add the anionic surfactant after concentration to prevent loss of
the anionic surfactant with the water phase removed during
concentration. Preferably, the anionic surfactant is present in the
stabilized dispersion of this invention in an amount of about 0.05
to about 5 wt % based on the weight of the fluoropolymer
solids.
Test Methods
[0058] Solids content of raw (as polymerized) fluoropolymer
dispersion are determined gravimetrically by evaporating a weighed
aliquot of dispersion to dryness, and weighing the dried solids.
Solids content is stated in weight % based on combined weights of
PTFE and water. Alternately solids content can be determined by
using a hydrometer to determine the specific gravity of the
dispersion and then by reference to a table relating specific
gravity to solids content. (The table is constructed from an
algebraic expression derived from the density of water and density
of as polymerized PTFE.)
[0059] Number average dispersion particle size on raw dispersion is
measured by photon correlation spectroscopy.
[0060] Standard specific gravity (SSG) of PTFE resin is measured by
the method of ASTM D-4895. If a surfactant is present, it can be
removed by the extraction procedure in ASTM-D-4441 prior to
determining SSG by ASTM D-4895.
[0061] Surfactant and solids content of stabilized dispersion are
determined gravimetrically by evaporating a small weighed aliquot
of dispersion to dryness following in general ASTM D-4441 but using
a time and temperature such that water but not the surfactant is
evaporated. This sample is then heated at 380.degree. C. to remove
the surfactant and reweighed. Surfactant content is stated in wt %
based on fluoropolymer solids.
[0062] Gel time is measured by the time it takes a dispersion to
completely gel in a blender. 200 ml of dispersion is placed in a
Waring commercial explosion resistant blender (Model 707SB, one
quart size, run at high speed, air requirements--10 scfm @ 10 psi,
available from Waring of New Hartford, Conn.). This blender has a
capacity of 1 liter and has an air purge for the motor. The
dispersion is stirred at the highest speed until the dispersion
gels. The gel point is quite sharp and easy to determine. The Gel
Time is recorded is seconds. If the dispersion does not gel in 1/2
hour (1800 seconds), the test is terminated to avoid damage to the
blender. The blender is then completely disassembled and cleaned
after each determination.
[0063] Fluorosurfactant Content is measured by a GC technique in
which the fluorosurfactant is esterified with acidic methanol.
Perfluoroheptanoic acid is used as an internal standard. Upon
addition of electrolyte and hexane the ester is extracted into the
upper hexane layer. The hexane layer is analyzed by injection onto
a glass GC column of 20 ft..times.2 mm I.D. packed with 10% OV-210
on 70/80 mesh Chromosorb W.AW.DMCS. held at 120 C. The detector is
ECD and the carrier gas of 95% argon/5% methane has a flow rate of
20 to 30 ml/min.
EXAMPLES
Fluoropolymers
[0064] TFE is polymerized to produce a raw PTFE homopolymer
dispersion containing PTFE particles having an SSG of about 2.20
and a number average particle size of approximately 220 nm. The raw
as-polymerized dispersion contains approximately 45% fluoropolymer
solids and has an APFO content of about 1800 ppm. In order to
determine Gel Times, raw as-polymerized dispersion is used as
described in the examples below.
Dispersing Agents
[0065] TAMOL.RTM. 681 supplied by Rohm and Haas is the ammonium
salt of a copolymer containing about 39% methacrylic acid and about
61% butyl methacrylate with a molecular weight of approximately
10,000. The dispersing agent is received as a very viscous liquid
in water having a viscosity of 9700 cps and contains 35% active
ingredients. The copolymer is described as being hydrophobic.
[0066] TAMOL.RTM. 2001 supplied by Rohm and Haas is the sodium salt
of a same as TAMOL.RTM. 681. The dispersing agent is received as
milky white liquid in propylene glycol having a viscosity of 20 cps
with a pH of 3.4 and contains 42% active ingredients. For effective
use, ammonium hydroxide is added to form an ionized salt. Adding
ammonium hydroxide to Tamol 2001 results in a very high viscosity,
approximately 38,000 cps. If the Tamol is diluted to 20% or lower,
the viscosity is less than 40 cps when ammonium hydroxide is added.
Alternatively the Tamol can be mixed into the dispersion and then
ammonium hydroxide can be added.
[0067] TAMOL.RTM. 165A--Hydrophobic acrylic copolymer. TAMOL.RTM.
165A has a viscosity of 660 cps. This grades contains 21% active
ingredients.
[0068] TAMOL.RTM. 731A--Hydrophobic acrylic copolymer. The
TAMOL.RTM. 731A has a viscosity of 56 cps and contains 25% active
ingredients.
[0069] TAMOL.RTM. 1124--Hydrophillic acrylic copolymer containing
50% active ingredients.
[0070] TAMOL.RTM. 963--A poly-acid dispersant containing 35% active
ingredients.
Ion Exchange Resin
[0071] A244-OH by US Filter is commercially-available strong base
anion exchange resin with quaternary ammonium groups with a
dimethyl ethanol amine moiety in hydroxide form.
Example 1
[0072] Several samples of 200 grams of as-polymerized (raw) PTFE
dispersion at 41 wt % solids are placed in 8-ounce glass jars. The
jars are approximately 3/4 full. [0073] Sample 1 contains only
as-polymerized PTFE dispersion. [0074] Sample 2 contains
as-polymerized PTFE dispersion stabilized with 1.22 wt % TAMOL.RTM.
681 (active ingredient basis) based on the dry weight of PTFE.
[0075] Sample 3 contains as-polymerized PTFE dispersion with 6 wt %
of wet US Filter A-244-OH ion exchange resin [0076] Sample 4
contains as-polymerized PTFE dispersion stabilized with 1.22 wt %
TAMOL.RTM. 681 based on the dry weight of PTFE and 6 wt % of wet US
Filter A-244-OH ion exchange resin.
[0077] The jars are placed on a Brunnell Wrist Action Shaker and
shaken on a speed setting of 1 at room temperature, a suitable
setting to get good mixing of the ion exchange resin and PTFE
dispersion in Samples 3 and 4. [0078] Sample 1 containing only PTFE
dispersion is 2/3 coagulated after shaking for about 1.5 hours.
[0079] Sample 2 containing 1.22 wt % TAMOL.RTM. 681 based on the
dry weight of PTFE is unchanged visually after 2 hours of shaking
indicating that the TAMOL.RTM. 681 provided a degree of shear
stability. [0080] Sample 3 containing ion exchange resin shows
immediate clumping as soon as ion exchange resin is added. After
shaking one hour, the pH rose from 3.5 to 4.1 and the conductivity
fell from 1685 microsiemens per cm to 183 indicating that APFO
removal is taking place. After two hours the PTFE is completely
coagulated and the ion exchange resin is encapsulated by the PTFE
gel. [0081] Sample 4 containing 3.5% TAMOL.RTM. 681 and 6 wt %
A-244-OH ion exchange resin is visually unchanged after two hours
of shaking, i.e. no coagulation is present and the ion exchange
resin still floated on the surface of the dispersion. The pH rose
and the conductivity fell indicating that some APFO removal had
occurred.
Example 2
Shear Stability as Measured by Gel Time
[0082] To establish an effective level of TAMOL.RTM. 681, samples
of as-polymerized PTFE dispersion and TAMOL.RTM. 681 are sheared in
a Waring blender at high speed until the dispersion gelled. The
resulting Gel Times are shown below in Table 1. The shear stability
is found to be highly dependent on concentration of TAMOL.RTM.. The
wt % Tamol 681 is expressed on the basis of active ingredients
relative to PTFE solids.
TABLE-US-00001 TABLE 1 wt % TAMOL .RTM. 681 Gel Time, seconds 0.35
2 0.70 4 1.05 3 1.49 43 1.75 727
Example 3
Fluorosurfactant Removal
[0083] A dispersion containing 1.75 wt % TAMOL.RTM. 681 (active
ingredients basis) in as-polymerized PTFE with 41 wt % solids is
prepared. Additional ammonium hydroxide is added to insure the pH
remains above 9.5. Varying level of A-244-OH ion exchange resin are
added and the samples are shaken on the Brunnell Wrist Action
Shaker at a speed setting of 1 for 3 hours. The samples are then
analyzed for APFO levels based on the total dispersion weight. The
results are shown below.
TABLE-US-00002 TABLE 2 wt % A-244-OH Resin APFO, ppm 1.2 879 3.5
434 5.8 232 8.1 149 10.5 99.8 12.8 64
[0084] The results indicate that the TAMOL.RTM. 681 provides
sufficient stability to allow ion exchange to reduce the level of
APFO in fluoropolymer dispersions. It is also a good indication
that the ion exchange resin is not removing the TAMOL.RTM. as well
as the APFO.
[0085] The rate of ion exchange can be further improved by using
additional ion exchange resin or by increasing the temperature at
which the ion exchange is conducted.
Example 4
[0086] Alternate grades of TAMOL.RTM. are tested for shear
stability in as-polymerized PTFE dispersion with APFO present. As
will be seen below, hydrophobic acrylic copolymers exhibit good
shear stability where hydrophilic acrylic copolymers do not. Tests
are conducted to determine the minimum amount of the different
grades to give adequate shear stability as shown in the Table
below. As shown below, hydrophobic copolymer dispersing agents
exhibit desirable shear stability whereas the hydrophilic copolymer
dispersing agents and poly-acid grade do not.
TABLE-US-00003 TABLE 3 Gel Times with Different Grades of TAMOL
.RTM. TAMOL .RTM. wt % TAMOL .RTM. Type Active Ingred.* Gel Time,
sec Description T-2001 1.79 385 Hydrophobic T-2001 3.19 1042
Hydrophobic T-165A 2.43 >1800 Hydrophobic T-165A 1.77 >1800
Hydrophobic T-165A 1.46 430 Hydrophobic T-731A 2.43 >1800
Hydrophobic T-731A 1.76 509 Hydrophobic T-1124 3.19 2 Hydrophilic
T-1124 6.38 2 Hydrophilic T-963 3.19 0 poly acid, PTFE gelled when
added *Based on PTFE
Example 5
[0087] This example illustrates reduction of
fluorosurfactant-containing fluoropolymer dispersion containing
acrylic copolymer dispersing agents in an anion exchange column and
subsequent concentration using acrylic polymer of high acid
content.
[0088] 100 parts of as-polymerized PTFE (43.5 wt % solids) is mixed
with 1.74 parts TAMOL.RTM. 2001 (active ingredients basis). The
dispersion is gently stirred and ammonium hydroxide is added to
bring the pH up to 9.8. The dispersion is passed through a column
containing US Filter A-244 OH ion exchange resin. The column is 14
inches in diameter and has a length to diameter ratio of 8:1. The
temperature of the dispersion is maintained at 52-54.degree. C. The
flow rate through the column is approximately 10 pounds per minute.
This results in a reduction of the APFO level from 1600 ppm to 8.1
ppm.
[0089] After ion exchange, the solids level is measured at 41.2 wt
%. A solution of polyacrylic acid (PAA) is prepared to concentrate
the dispersion. 42.7 grams of Aquatreat AR-7H (available from Alco
Chemicals as a 15% solution) are added to 157.3 grams water.
Ammonium hydroxide is added to raise the pH to 9.5 to convert the
PAA to the ammonium salt (raising the viscosity of the stock
solution from 13 cps to 238 cps) causing the PAA the be added to
the dispersion in salt form. If added in the acidic form, the PAA
will lower the pH of the dispersion and the TAMOL.RTM. will become
insoluble resulting in localized coagulation of the PTFE
dispersion.
[0090] 37.2 grams of the PAA stock solution is added to 2058 grams
of the TAMOL.RTM. stabilized dispersion that has been subjected to
the ion exchange process. The mixture is heated to 75.degree. C.
with stirring and the stirrer is then turned off to allow
concentration to occur. After one hour, the upper layer is removed.
The concentrated lower layer contains 66.0% PTFE solids. The
viscosity of the dispersion is 318 cps.
[0091] The concentrated dispersion is diluted to 60.0% solids with
demineralized water. This reduces the viscosity to 84 cps. 2.4%
sodium lauryl sulfate is added based on PTFE solids to improve
wetting characteristics, reducing the viscosity further to 33
cps.
Example 6
[0092] This example illustrates reduction of
fluorosurfactant-containing fluoropolymer dispersion containing
acrylic copolymer dispersing agents in an anion exchange column and
subsequent concentration using electrodecantation.
[0093] Similar to Example 5, 100 parts of as-polymerized PTFE (43.5
wt % solids) is mixed with 1.74 parts TAMOL.RTM. 2001 (active
ingredients basis). The dispersion is gently stirred and ammonium
hydroxide is added to bring the pH up to 9.8. The dispersion is
passed through a column containing US Filter A-244 OH ion exchange
resin. The column is 14 inches in diameter and has a length to
diameter ratio of 8:1. The temperature of the dispersion is
maintained at 52-54.degree. C. The flow rate through the column is
approximately 10 pounds per minute. This results in a reduction of
the APFO level from 1600 ppm to 8.1 ppm.
[0094] After ion exchange, the solids level is measured at 41.2 wt
%. Concentration of solids is performed by electrodecantation. The
dispersion is fed to a container and a direct current potential is
applied from electrodes at either end of the container (240 V
d.c.). Negatively charged PTFE particles surrounded by anionic
dispersing agent move in the applied field toward the anode. A
plurality of semi permeable membrane barriers suspended vertically
in the container between the electrodes form concentrating cells
and prevent the particles from contacting the anode. Concentrated
dispersion moves downward along one face of a membrane and depleted
dispersion moves upward on the other face. Periodic current
reversal prevents compaction and coagulation of the resin
particles. The concentrated dispersion being denser settles to the
sloping bottom of the container which is not separated into
concentrating cells. The concentrated dispersion is withdrawn form
the bottom of the decanter in 30 minute intervals. The supernatant
liquid remains overhead. The applied current is alternated every 90
seconds to reverse the flow of the PTFE particles thus preventing
coagulation of PTFE powder on the membranes and electrodes. The
concentrated lower layer contains 54.0% PTFE solids. The viscosity
of the dispersion is approximately 30 cps.
Example 7
[0095] This example illustrates the coating process in accordance
with the invention for the application of fluoropolymer to catheter
guide wire. Catheter guide wire, typically stainless steel, is
coated with fluoropolymer to facilitate access into the arterial
system.
[0096] The dispersion as prepared in Example 6 is used. Such
dispersion is formulated into a coating composition as explained in
U.S. Pat. No. 2,562,118 to Osdal. The coating composition is formed
from 100 parts of PTFE dispersion containing about 1 wt % sodium
lauryl sulfate blended with 35 parts of an acid accelerator system
containing chromic acid and phosphoric acid. The coating
composition is sprayed wet onto a stainless steel wire (outer
diameter of 0.15 to 0.40 inches, 3.8 to 10 mm) which has been
thoroughly cleaned and dried to remove all milling oils, dirt,
etc., to a dry film thickness of 10-15 micrometers. The coating is
cured by baking at a temperature of 750.degree. F. (399.degree. C.)
for 3-5 minutes
Example 8
[0097] This example illustrates the coating process in accordance
with the invention for the application of fluoropolymer as an
industrial finish such as would be applied, for example, to the
inside of a chemical processing tank.
[0098] The dispersion as prepared in Example 6 is further used to
coat a substrate of carbon steel. A substrate of carbon steel is
roughened by grit blasting with aluminum oxide to achieve a surface
roughness Ra of about 75 to about 125 micrometers using a coarse
grit (10-20 mesh) and 90-100 psi (0.62-0.69 MPa) air pressure. The
dispersion of Example 6 is formulated into a coating composition as
explained in U.S. Pat. No. 2,562,118 to Osdal and applied as a
primer to the prepared substrate. The coating composition is formed
from 100 parts of PTFE dispersion containing about 1 wt % sodium
lauryl sulfate, blended with 35 parts of an acid accelerator system
containing chromic acid and phosphoric acid. The primer is applied
wet by conventional methods to a film thickness of about 12 to 25
micrometers.
[0099] A first layer of PFA powder (Type 350, product code 532-5450
manufactured by the DuPont Company) is applied electrostatically to
the wet primer using a powder spray gun supplied by ITW GEMA
Company. Gun settings are 15 kV, 3.0 conveying air, 10 dosing air
and 6 bar pressure. The first coating layer is applied onto the wet
primer and a thermocouple is attached to the coated substrate. The
coated substrate is heated, and while heating, the temperature of
the substrate is measured with the thermocouple and the coated
substrate is baked for 10 minutes at 725-750.degree. F.
(385-399.degree. C.) The substrate is removed the oven and the
second and subsequent layers are applied. Each layer is applied at
about 80 to about 120 microns DFT per coat and the recoated
substrate is then baked for 10 minutes at 700-725.degree. F.
(371-385.degree. C.) The baking time can be extended if desired to
insure complete melting and coalescence of the coating. The
substrate is coated repeatedly with PFA powder composition until a
DFT in the range of 625 micrometers is reached.
* * * * *