U.S. patent application number 12/902224 was filed with the patent office on 2011-02-03 for dispersing agents in nanocomposites.
Invention is credited to Katherine Maree Dean, Guoxin Li, Roshan Tyrrel Anton Mayadunne, Graeme Moad, Rudolf Pfaendner, George Philip Simon, Hendrik Wermter.
Application Number | 20110028633 12/902224 |
Document ID | / |
Family ID | 32946975 |
Filed Date | 2011-02-03 |
United States Patent
Application |
20110028633 |
Kind Code |
A1 |
Moad; Graeme ; et
al. |
February 3, 2011 |
Dispersing Agents in Nanocomposites
Abstract
The instant invention discloses a composition, preferably a
nanocomposite material, comprising (a) a synthetic polymer, (b) a
filler such as for example a natural or synthetic phyllosilicate or
a mixture of such phyllosilicates, preferably in nanoparticles, and
(c) a dispersing agent prepared by controlled free radical
polymerization (CFRP).
Inventors: |
Moad; Graeme; (Sassafras,
AU) ; Simon; George Philip; (Glenhuntly, AU) ;
Dean; Katherine Maree; (Collingwood, AU) ; Li;
Guoxin; (Mulgrave, AU) ; Mayadunne; Roshan Tyrrel
Anton; (Wheelers Hill, AU) ; Wermter; Hendrik;
(Bensheim, DE) ; Pfaendner; Rudolf; (Rimbach,
DE) |
Correspondence
Address: |
BASF Corporation;Patent Department
500 White Plains Road, P.O. Box 2005
Tarrytown
NY
10591
US
|
Family ID: |
32946975 |
Appl. No.: |
12/902224 |
Filed: |
October 12, 2010 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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10547264 |
Aug 29, 2005 |
7837899 |
|
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PCT/EP04/50183 |
Feb 23, 2004 |
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12902224 |
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Current U.S.
Class: |
524/447 ;
524/445; 524/449; 524/570; 977/773 |
Current CPC
Class: |
C08L 23/10 20130101;
C08L 23/12 20130101; C08L 33/08 20130101; C08L 23/10 20130101; C08L
23/10 20130101; C08L 23/12 20130101; C08L 2666/24 20130101; C08L
2666/24 20130101; C08L 2666/04 20130101 |
Class at
Publication: |
524/447 ;
524/570; 524/445; 524/449; 977/773 |
International
Class: |
C08K 3/34 20060101
C08K003/34 |
Foreign Application Data
Date |
Code |
Application Number |
Mar 3, 2003 |
EP |
03405141.7 |
Claims
1. A composition comprising a) a synthetic polymer, b) a filler,
and c) a dispersing agent prepared by controlled free radical
polymerization (CFRP).
2. A composition according to claim 1, wherein component (a) is a
polyolefin.
3. A composition according to claim 1, wherein component (b) is a
filler in nanoparticles.
4. A composition according to claim 1, wherein component (b) is a
natural or synthetic phyllosilicate or a mixture of such
phyllosilicates.
5. A composition according to claim 1, wherein component (b) is a
layered silicate clay.
6. A composition according to claim 1, wherein component (b) is a
montmorillonite, bentonite, beidelite, mica, hectorite, saponite,
nontronite, sauconite, vermiculite, ledikite, magadite, kenyaite,
stevensite, volkonskoite, hydrotalcite or a mixture thereof.
7. A composition according to claim 1, wherein component (c) is a
random, block, star or comb copolymer prepared by controlled free
radical polymerization.
8. A composition according to claim 1, wherein component (c) is a
block or comb acrylic co-polymer prepared by controlled free
radical polymerization.
9. A composition according to claim 1, wherein component (b) is
present in an amount of from 0.1 to 40%, based on the weight of
component (a).
10. A composition according to claim 1, wherein component (c) is
present in an amount of from 0.1 to 20%, based on the weight of
component (a)
11. A composition according to claim 1, comprising in addition,
besides components (a), (b) and (c), further additives.
12. A composition according to claim 11, comprising as further
additives phenolic antioxidants, light-stabilizers, processing
stabilizers, solvents, pigments, dyes, plasticizers,
compatibilizers, toughening agents and/or thixotropic agents.
13. A composition according to claim 1 in the form of a masterbatch
or concentrate comprising component (a) in an amount of from 5 to
90%, component (b) in an amount of from 5 to 80%, and component (c)
in an amount of from 0.5 to 50% by weight.
14. A process for the preparation of a synthetic polymer
nanocomposite material which comprises melt mixing a mixture of a)
a synthetic polymer, b) a filler, and c) a dispersing agent
prepared by controlled free radical polymerization (CFRP).
15. A process according to claim 14, wherein the melt mixing occurs
between 120 and 290.degree. C.
16. A synthetic polymer nanocomposite obtained by a process
according to claim 14.
17. A method to exfoliate a filler and disperse the filler in a
synthetic polymer matrix to form a nanocomposite material, which
comprises melt mixing a mixture of a) a synthetic polymer, b) a
filler, and c) an effective dispersing amount of a dispersing agent
prepared by controlled free radical polymerization and then forming
the nanocomposite material.
Description
[0001] This application is a continuation of co-pending application
Ser. No. 10/547,264, filed on Aug. 29, 2005 which is the National
Stage of International Application PCT/EP04/050183, filed Feb. 23,
2004, the contents of which are herein incorporated by
reference.
[0002] The present invention relates to a composition, preferably a
nanocomposite material, comprising (a) a synthetic polymer,
especially a polyolefin, (b) a filler, especially a natural or
synthetic phyllosilicate or a mixture of such phyllosilicates,
preferably in nanoparticles, and (c) a dispersing agent prepared by
controlled free radical polymerization (CFRP). The present
invention relates also to a process for the preparation of a
synthetic polymer nanocomposite material which comprises melt
mixing a mixture of a) a synthetic polymer, b) a filler, and c) a
dispersing agent prepared by controlled free radical polymerization
and to the use of the latter to intercalate and exfoliate a filler
and disperse the filler in a synthetic polymer matrix to form a
nanocomposite material.
[0003] The addition of fillers to organic materials, especially
polymers, is known and is described for example in Hans Zweifel
(editor), Plastics Additives Handbook, 5th Edition, pages 901-948,
Hanser Publishers, Munich 2001. The use of fillers in polymers has
the advantage that it is possible to bring about improvement in,
for example, the mechanical properties, especially the density,
hardness, rigidity (modulus) or reduced shrinkage of the
polymer.
[0004] Using extremely small filler particles (with one dimension
<200 nm), so-called nano-scale fillers, mechanical properties,
heat distortion temperature stability or flame retardant property
of the polymers can be improved with a much lower concentration,
typically 2 to 10% by weight compared to 20 to 50% by weight with
the normal micro-scale filler particles. Polymers containing
nano-scale fillers combine favourable mechanical properties like
strength, modulus and impact, and show improved surface qualities
like gloss, lower tool wear during processing and better conditions
for recycling. Coatings and films comprising nano-scale fillers
show improved stability, flame retardance, gas barrier properties
and scratch resistance.
[0005] Nano-scale fillers possess an extremely large surface area
with high surface energy. The deactivation of the surface energy
and the compatibilization of the nano-scale fillers with a
polymeric substrate is, therefore, even more important than with a
common micro-scale filler in order to avoid aggregation during
processing or conversion of the filled polymer and to reach an
excellent dispersion of the nano-scaled filler in the final
article.
[0006] There is a substantial recent literature on
organic-inorganic nanocomposites based on clays or layered
silicates such as montmorillonite and synthetic polymers.
Polyolefin nanocomposites have been prepared from organic modified
clays. The clays used are generally modified with alkyl or dialkyl
ammonium ions or amines or in a few cases other onium ions, like
for example phosphonium ions. The ammonium ion/amine additives are
usually incorporated into the clay structure by a separate solution
intercalation step.
[0007] These conventional organic modified clays have a number of
disadvantages when used for the preparation of polyolefin
nanocomposites. Ammonium salts are thermally unstable at
temperatures used in polyolefin processing or may be otherwise
reactive under processing conditions. These instabilities result in
poor processing stability, inferior mechanical properties,
discoloration, odor formation and reduced long-term stability in
addition to the formation of volatile by-products.
[0008] In order to improve the polyolefin nanocomposite formation
by melt processing the use of an additional compatibilizer has been
proposed, most often a maleic anhydride grafted polypropylene,
which in working examples is present as a major component of the
final product.
[0009] M. Kawasumi et al., Macromolecules 1997, 30, 6333-6338 or
U.S. Pat. No. 5,973,053 disclose that a polypropylene nanocomposite
is obtained when a clay, premodified with octadecylammonium salts,
is compounded with polypropylene in the presence of polyolefin
oligomers containing polar functionality, for example maleic
anhydride grafted polypropylene.
[0010] Although compatibilizers can improve the stability of
nanocomposites mainly with regard to avoiding agglomeration of the
filler, the other weaknesses of the nanocomposites are not
improved.
[0011] It has now been found that improved synthetic polymer
materials with better long term thermostability and with reduced
odor and reduced undesired discoloration which occurs as a result
of the decomposition of the modification agents, can be prepared by
the use of a dispersing agent prepared by controlled free radical
polymerization.
[0012] The present invention therefore provides a composition
comprising [0013] a) a synthetic polymer, [0014] b) a filler, and
[0015] c) a dispersing agent prepared by controlled free radical
polymerization (CFRP).
[0016] Preferably, component (b) is a filler in nanoparticles.
[0017] Of interest are also compositions comprising as component
(b) a filler in nanoparticles or a material which produces a filler
in nanoparticles under processing conditions.
[0018] Component (c) is suitable for intercalating and exfoliating
a filler and dispersing the filler in a synthetic polymer matrix,
especially a thermoplastic polymer, to form a nanocomposite
material.
[0019] Examples of such synthetic polymers are:
[0020] 1. Polymers of monoolefins and diolefins, for example
polypropylene, polyisobutylene, poly(but-1-ene),
poly(4-methylpent-1-ene), poly(vinylcyclohexane), polyisoprene or
polybutadiene, as well as polymers of cycloolefins, for instance of
cyclopentene or norbornene, polyethylene (which optionally can be
crosslinked), for example high density polyethylene (HDPE), high
density and high molecular weight polyethylene (HDPE-HMW), high
density and ultrahigh molecular weight polyethylene (HDPE-UHMW),
medium density polyethylene (MDPE), low density polyethylene
(LDPE), linear low density polyethylene (LLDPE), (VLDPE) and
(ULDPE).
[0021] Polyolefins, i.e. the polymers of monoolefins exemplified in
the preceding paragraph, preferably polyethylene and polypropylene,
can be prepared by different, and especially by the following,
methods: [0022] a) radical polymerisation (normally under high
pressure and at elevated temperature). [0023] b) catalytic
polymerisation using a catalyst that normally contains one or more
than one metal of groups IVb, Vb, VIb or VIII of the Periodic
Table. These metals usually have one or more than one ligand,
typically oxides, halides, alcoholates, esters, ethers, amines,
alkyls, alkenyls and/or aryls that may be either .pi.- or
.sigma.-coordinated. These metal complexes may be in the free form
or fixed on substrates, typically on activated magnesium chloride,
titanium(III) chloride, alumina or silicon oxide. These catalysts
may be soluble or insoluble in the polymerisation medium. The
catalysts can be used by themselves in the polymerisation or
further activators may be used, typically metal alkyls, metal
hydrides, metal alkyl halides, metal alkyl oxides or metal
alkyloxanes, said metals being elements of groups Ia, IIa and/or
IIIa of the Periodic Table. The activators may be modified
conveniently with further ester, ether, amine or silyl ether
groups. These catalyst systems are usually termed Phillips,
Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont), metallocene
or single site catalysts (SSC).
[0024] 2. Mixtures of the polymers mentioned under 1), for example
mixtures of polypropylene with polyisobutylene, polypropylene with
polyethylene (for example PP/HDPE, PP/LDPE) and mixtures of
different types of polyethylene (for example LDPE/HDPE).
[0025] 3. Copolymers of monoolefins and diolefins with each other
or with other vinyl monomers, for example ethylene/propylene
copolymers, linear low density polyethylene (LLDPE) and mixtures
thereof with low density polyethylene (LDPE), propylene/but-1-ene
copolymers, propylene/isobutylene copolymers, ethylene/but-1-ene
copolymers, ethylene/hexene copolymers, ethylene/methylpentene
copolymers, ethylene/heptene copolymers, ethylene/octene
copolymers, ethylene/vinylcyclohexane copolymers,
ethylene/cycloolefin copolymers (e.g. ethylene/norbornene like
COC), ethylene/1-olefins copolymers, where the 1-olefin is
generated in-situ; propylene/butadiene copolymers,
isobutylene/isoprene copolymers, ethylene/vinylcyclohexene
copolymers, ethylene/alkyl acrylate copolymers, ethylene/alkyl
methacrylate copolymers, ethylene/vinyl acetate copolymers or
ethylene/acrylic acid copolymers and their salts (ionomers) as well
as terpolymers of ethylene with propylene and a diene such as
hexadiene, dicyclopentadiene or ethylidene-norbornene; and mixtures
of such copolymers with one another and with polymers mentioned in
1) above, for example polypropylene/ethylene-propylene copolymers,
LDPE/ethylene-vinyl acetate copolymers (EVA), LDPE/ethylene-acrylic
acid copolymers (EAA), LLDPE/EVA, LLDPE/EAA and alternating or
random polyalkylene/carbon monoxide copolymers and mixtures thereof
with other polymers, for example polyamides.
[0026] 4. Hydrocarbon resins (for example C.sub.5-C.sub.9)
including hydrogenated modifications thereof (e.g. tackifiers) and
mixtures of polyalkylenes and starch.
[0027] Homopolymers and copolymers from 1.)-4.) may have any
stereostructure including syndio-tactic, isotactic, heterotactic or
atactic. Stereoblock polymers are also included.
[0028] 5. Polystyrene, poly(p-methylstyrene),
poly(.alpha.-methylstyrene).
[0029] 6. Aromatic homopolymers and copolymers derived from vinyl
aromatic monomers including styrene, .alpha.-methylstyrene, all
isomers of vinyl toluene, especially p-vinyltoluene, all isomers of
ethylstyrene, propyistyrene, vinylbiphenyl, vinylnaphthalene, and
vinylanthracene, and mixtures thereof. Homopolymers and copolymers
may have any stereostructure including syndiotactic, isotactic,
heterotactic or atactic; where atactic polymers are preferred.
Stereoblock polymers are also included.
[0030] 6a. Copolymers including aforementioned vinyl aromatic
monomers and comonomers selected from ethylene, propylene, dienes,
nitriles, acids, maleic anhydrides, maleimides, vinyl acetate and
vinyl chloride or acrylic derivatives and mixtures thereof, for
example styrene/butadiene, styrene/acrylonitrile, styrene/ethylene
(interpolymers), styrene/alkyl methacrylate,
styrene/butadiene/alkyl acrylate, styrene/butadiene/alkyl
methacrylate, styrene/maleic anhydride,
styrene/acrylonitrile/methyl acrylate; mixtures of high impact
strength of styrene copolymers and another polymer, for example a
polyacrylate, a diene polymer or an ethylene/propylene/diene
terpolymer; and block copolymers of styrene such as
styrene/butadiene/styrene, styrene/isoprene/styrene,
styrene/ethylene/butylene/styrene or
styrene/ethylene/propylene/styrene.
[0031] 6b. Hydrogenated aromatic polymers derived from
hydrogenation of polymers mentioned under 6.), especially including
polycyclohexylethylene (PCHE) prepared by hydrogenating atactic
polystyrene, often referred to as polyvinylcyclohexane (PVCH).
[0032] 6c. Hydrogenated aromatic polymers derived from
hydrogenation of polymers mentioned under 6a.).
[0033] Homopolymers and copolymers may have any stereostructure
including syndiotactic, isotactic, hemi-isotactic or atactic; where
atactic polymers are preferred. Stereoblock polymers are also
included.
[0034] 7. Graft copolymers of vinyl aromatic monomers such as
styrene or .alpha.-methylstyrene, for example styrene on
polybutadiene, styrene on polybutadiene-styrene or
polybutadiene-acrylonitrile copolymers; styrene and acrylonitrile
(or methacrylonitrile) on polybutadiene; styrene, acrylonitrile and
methyl methacrylate on polybutadiene; styrene and maleic anhydride
on polybutadiene; styrene, acrylonitrile and maleic anhydride or
maleimide on polybutadiene; styrene and maleimide on polybutadiene;
styrene and alkyl acrylates or methacrylates on polybutadiene;
styrene and acrylonitrile on ethylene/propylene/diene terpolymers;
styrene and acrylonitrile on poly(alkyl acrylates) or poly(alkyl
methacrylates), styrene and acrylonitrile on acrylate/butadiene
copolymers, as well as mixtures thereof with the copolymers listed
under 6), for example the copolymer mixtures known as ABS, MBS, ASA
or AES polymers.
[0035] 8. Halogen-containing polymers such as polychloroprene,
chlorinated rubbers, chlorinated and brominated copolymer of
isobutylene-isoprene (halobutyl rubber), chlorinated or
sulfo-chlorinated polyethylene, copolymers of ethylene and
chlorinated ethylene, epichlorohydrin homo- and copolymers,
especially polymers of halogen-containing vinyl compounds, for
example poly(vinyl chloride), poly(vinylidene chloride), poly(vinyl
fluoride), poly(vinylidene fluoride), as well as copolymers thereof
such as vinyl chloride/vinylidene chloride, vinyl chloride/vinyl
acetate or vinylidene chloride/vinyl acetate copolymers.
[0036] 9. Polymers derived from .alpha.,.beta.-unsaturated acids
and derivatives thereof such as polyacrylates and
polymethacrylates; polymethyl methacrylates, polyacrylamides and
polyacrylonitriles, which can be impact-modified with butyl
acrylate.
[0037] 10. Copolymers of the monomers mentioned under 9) with each
other or with other unsaturated monomers, for example
acrylonitrile/butadiene copolymers, acrylonitrile/alkyl acrylate
copolymers, acrylonitrile/alkoxyalkyl acrylate or
acrylonitrile/vinyl halide copolymers or acrylonitrile/alkyl
methacrylate/butadiene terpolymers.
[0038] 11. Polymers derived from unsaturated alcohols and amines or
the acyl derivatives or acetals and their hydrolysis products, for
example poly(vinyl alcohol), poly(vinyl acetate), poly(vinyl
stearate), poly(vinyl benzoate), poly(vinyl maleate), poly(vinyl
butyral), poly(allyl phthalate) or poly(allyl melamine); as well as
their copolymers with olefins mentioned in 1) above.
[0039] 12. Homopolymers and copolymers of cyclic ethers such as
poly(alkylene glycols), poly(ethylene oxide), poly(propylene oxide)
or copolymers thereof with bisglycidyl ethers.
[0040] 13. Polyacetals such as polyoxymethylene and those
polyoxymethylenes which contain ethylene oxide as a comonomer;
polyacetals modified with thermoplastic polyurethanes, acrylates or
MBS.
[0041] 14. Polyphenylene oxides and sulfides, and mixtures of
polyphenylene oxides with styrene polymers or polyamides.
[0042] 15. Polyurethanes derived from hydroxyl-terminated
polyethers, polyesters or polybutadienes on the one hand and
aliphatic or aromatic polyisocyanates on the other, as well as
precursors thereof.
[0043] 16. Polyamides and copolyamides derived from diamines and
dicarboxylic acids and/or from aminocarboxylic acids or the
corresponding lactams, for example polyamide 4, polyamide 6,
polyamide 6/6, 6/10, 6/9, 6/12, 4/6, 12/12, polyamide 11, polyamide
12, aromatic polyamides starting from m-xylene diamine and adipic
acid; polyamides prepared from hexamethylenediamine and isophthalic
or/and terephthalic acid and with or without an elastomer as
modifier, for example poly-2,4,4,-trimethylhexamethylene
terephthalamide or poly-m-phenylene iso-phthalamide; and also block
copolymers of the aforementioned polyamides with polyolefins,
olefin copolymers, ionomers or chemically bonded or grafted
elastomers; or with polyethers, e.g. with polyethylene glycol,
polypropylene glycol or polytetramethylene glycol; as well as
polyamides or copolyamides modified with EPDM or ABS; and
polyamides condensed during processing (RIM polyamide systems).
[0044] 17. Polyureas, polyimides, polyamide-imides, polyetherimids,
polyesterimids, polyhydantoins and polybenzimidazoles.
[0045] 18. Polyesters derived from dicarboxylic acids and diols
and/or from hydroxycarboxylic acids or the corresponding lactones,
for example polyethylene terephthalate, polybutylene terephthalate,
poly-1,4-dimethylolcyclohexane terephthalate, polyalkylene
naphthalate (PAN) and polyhydroxybenzoates, as well as block
copolyether esters derived from hydroxyl-terminated polyethers; and
also polyesters modified with polycarbonates or MBS.
[0046] 19. Polycarbonates and polyester carbonates.
[0047] 20. Polyketones.
[0048] 21. Polysulfones, polyether sulfones and polyether
ketones.
[0049] 22. Crosslinked polymers derived from aldehydes on the one
hand and phenols, ureas and melamines on the other hand, such as
phenol/formaldehyde resins, urea/formaldehyde resins and
melamine/formaldehyde resins.
[0050] 23. Drying and non-drying alkyd resins.
[0051] 24. Unsaturated polyester resins derived from copolyesters
of saturated and unsaturated dicarboxylic acids with polyhydric
alcohols and vinyl compounds as crosslinking agents, and also
halogen-containing modifications thereof of low flammability.
[0052] 25. Crosslinkable acrylic resins derived from substituted
acrylates, for example epoxy acrylates, urethane acrylates or
polyester acrylates.
[0053] 26. Alkyd resins, polyester resins and acrylate resins
crosslinked with melamine resins, urea resins, isocyanates,
isocyanurates, polyisocyanates or epoxy resins.
[0054] 27. Crosslinked epoxy resins derived from aliphatic,
cycloaliphatic, heterocyclic or aromatic glycidyl compounds, e.g.
products of diglycidyl ethers of bisphenol A and bisphenol F, which
are crosslinked with customary hardeners such as anhydrides or
amines, with or without accelerators.
[0055] 28. Blends of the aforementioned polymers (polyblends), for
example PP/EPDM, Poly-amide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS,
PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates,
POM/thermoplastic PUR, PC/thermoplastic PUR, POM/acrylate, POM/MBS,
PPO/HIPS, PPO/PA 6.6 and copolymers, PA/HDPE, PA/PP, PA/PPO,
PBT/PC/ABS or PBT/PET/PC.
[0056] The synthetic polymers to be protected are preferably
thermoplastic polymers, especially polyolefins, polystyrenes,
polyamides, polyesters, polyacrylates, most preferably polyolefins,
in particular polyethylene and polypropylene or copolymers thereof
with mono- and diolefins.
[0057] Preferred fillers are for example natural or synthetic
phyllosilicates or a mixture of such phyllosilicates.
[0058] Of interest are compositions wherein component (b) is a
natural or synthetic phyllosilicate or a mixture of such
phyllosilicates wherein component (b) can be modified or unmodified
by a modification agent such as, for example, an ammoium, an amine
or a phosphonium compound.
[0059] Fillers of special interest are for example layered silicate
clays. Of very special interest are compositions comprising as
component (b) a montmorillonite, bentonite, beidelite, mica,
hectorite, saponite, nontronite, sauconite, vermiculite, ledikite,
magadite, kenyaite, stevensite, volkonskoite, hydrotalcite or a
mixture thereof.
[0060] Component (b) can be unmodified or modified by a
modification agent such as, for example, an ammonium, an amine or a
phosphonium compound.
[0061] Examples of modification agents for nano-clays are for
example:
[0062] 1. Amine and ammonium compounds, for example,
distearyldimethylammonium chloride, stearylbenzyldimethylammonium
chloride, stearylamine, stearyldiethoxyamine or aminododecanoic
acid [commercially available as Nanofil.RTM. from Sudchemie,
Germany]; dimethyl ditallow ammonium, trioctylmethyl ammonium,
dipolyoxyethylenealkylmethyl ammonium or
polyoxypropylenemethyldiethyl ammonium [commercially available as
modified Somasif.RTM. from CO-OP Chemical]; octadecylamine,
triethoxysilanyl-propylamine [commercially available as
Nanomer.RTM. from Nanocor], polyalkoxylated ammonium compounds such
as for example octadecyl bis(polyoxyethylene[15]amine
[Ethomeen.RTM. from Eastman] or octadecyl methyl
bis(polyoxyethylene[15]ammonium chloride [Etoquad.RTM. from
Eastman] or just the corresponding free amines.
[0063] 2. Phosphonium compounds, for example tetrabutylphosphonium
or octadecyl triphenyl phosphonium [commercially available from
Eastman].
[0064] 3. Others, for example, triethoxy octyl silane [commercially
available as Nanomer.RTM. from Nanocor], ammonium, sulfonium or
pyridium compounds as disclosed for example in WO-A-01/04050 or
WO-A-99/67790 ; block graft copolymers such as for example PEO-b-PS
or poly-4-vinylpyridine-b-PS; or solvents for swelling such as for
example .gamma.-butyrolactone, 2-pyrrolidone, dimethylsulfoxide,
diglyme, tetrahydrofuran or furfuryl alcohol.
[0065] Compositions which are of interest include those comprising
as component (c) a random, block, star or comb copolymer prepared
by controlled free radical polymerization.
[0066] Such dispersing agents prepared by controlled free radical
polymerization are known. Their preparation is disclosed for
example in C. Auschra et al., Progress in Organic Coatings 45,
83-93 (2002).
[0067] The preparation of the dispersing agents by controlled free
radical polymerization (CFRP) can preferally occur by four suitable
routes: [0068] a1) Polymerization in the presence of alkoxyamine
initiator/regulator compounds; [0069] a2) Polymerization in the
presence of a stable nitroxyl free radical and a radical initiator
(source of free radicals); [0070] a3) Polymerization under atom
transfer radical polymerization (ATRP); or [0071] a4) RAFT
polymerization which refers to a method of polymer synthesis by
radical polymerization using chain transfer agents which react by
reversible addition--fragmentation chain transfer.
[0072] For example U.S. Pat. No. 4,581,429 or EP-A-0 621 878
discloses the preparation of block copolymers by method a1).
[0073] For example EP-A-0 621 878 discloses the preparation of
block copolymers by method a2).
[0074] For example WO-A-01/51534 discloses the preparation of comb
copolymers by the ATRP method a3).
[0075] For example WO-A-99/31144 discloses the preparation of block
copolymers by method a4).
[0076] Preferred chain transfer agents include thiocarbonylthio
chain transfer agents of formulae I, II and III, and macromonomers
of formula IV and a combination thereof,
##STR00001##
[0077] wherein R, R.sup.1 and P are free radical leaving groups;
and wherein,
[0078] R is selected from the group consisting of unsubstituted or
substituted C.sub.1-C.sub.18alkyl, unsubstituted or substituted
C.sub.2-C.sub.18alkenyl, unsubstituted or substituted
C.sub.2-C.sub.18alkynyl, unsubstituted or substituted saturated
carbocyclic ring, unsubstituted or substituted unsaturated
carbocyclic ring, unsubstituted or substituted aromatic carbocyclic
ring, unsubstituted or substituted saturated heterocyclic ring,
unsubstituted or substituted unsaturated heterocyclic ring,
unsubstituted or substituted aromatic heterocyclic ring,
unsubstituted or substituted alkylthio group, and a first polymer
chain having a number average degree of polymerization in the range
of 5 to 1000;
[0079] Z is selected from the group consisting of hydrogen,
chlorine, unsubstituted or substituted C.sub.1-C.sub.18alkyl,
unsubstituted or substituted aryl, unsubstituted or substituted
C.sub.3-C.sub.18 heterocyclic ring, unsubstituted or substituted
C.sub.1-C.sub.18alkylthio, SR, unsubstituted or substituted
arylthio, unsubstituted or substituted C.sub.1-C.sub.18alkoxy,
unsubstituted or substituted aryloxy, unsubstituted or substituted
amino, unsubstituted or substituted C.sub.1-C.sub.18alkoxycarbonyl,
unsubstituted or substituted aryloxycarbonyl, carboxy,
unsubstituted or substituted C.sub.1-C.sub.18acyloxy, unsubstituted
or substituted aroyloxy, unsubstituted or substituted carbamoyl,
cyano, C.sub.2-C.sub.18-dialkyl-phosphonato, diaryl-phosphonato,
C.sub.1-C.sub.18dialkyl-phosphinato, diaryl-phosphinato and a
second polymer chain having a number average degree of
polymerization in the range of 5 to 1000;
[0080] R.sup.1 is an n-valent moiety derived from R;
[0081] Z.sup.1 is an m-valent moiety derived from a species
selected from the group consisting of unsubstituted or substituted
C.sub.1-C.sub.18 alkyl, unsubstituted or substituted aryl and a
third polymer chain having a number average degree of
polymerization in the range of 5 to 1000 wherein the connecting
moieties in said polymer chain are selected from the group
consisting of C.sub.1-C.sub.18-aliphatic carbon, aromatic carbon,
oxygen, sulfur and a combination thereof;
[0082] P is an oligomer or polymer having a number average degree
of polymerization in the range of 2 to 1000 or said first polymer
chain;
[0083] X is selected from the group consisting of unsubstituted or
substituted aryl, C.sub.1-C.sub.18-alkoxycarbonyl, unsubstituted or
substituted aryloxycarboyl, carboxy, unsubstituted or substituted
aryl-oxycarbonyl, C.sub.1 to C.sub.18 carboxy, and cyano;
[0084] n and m are integers in the range of 1 to 6; and
[0085] wherein the substituents for the substituted groups for R,
R.sup.1, Z, Z.sup.1 and X are independently selected from the group
consisting of hydroxy, tertiary amino, halogen, cyano, epoxy,
carboxylic acid, alkoxy, alkyl having 1 to 32 carbon atoms, aryl,
alkenyl having 2 to 32 carbon atoms, alkynyl having from 2 to 32
carbon atoms, saturated carbocyclic rings having 3 to 14 carbon
atoms, unsaturated carbocyclic rings having 4 to 14 carbon atoms,
aromatic carbocyclic rings having 6 to 14 carbon atoms, saturated
heterocyclic rings having 3 to 14 carbon atoms, unsaturated
heterocyclic rings having 3 to 14 carbon atoms and aromatic
carbocyclic rings having 6 to 14 carbon atoms.
[0086] By a "polymer chain" referred to above for R, R.sup.1, Z,
Z.sup.1 and P is meant conventional condensation polymers, such as
polyesters [for example, polycaprolactone, poly(ethylene
terephthalate), poly(lactic acid)], polycarbonates, poly(alkylene
oxide)s [for example, poly(ethylene oxide), poly(tetramethylene
oxide)], nylons, polyurethanes or chain polymers such as those
formed by coordination polymerization (for example polyethylene,
polypropylene), radical polymerization (for example,
poly(meth)acrylates and polystyrenics, anionic polymerization (for
example, polystyrene, polybutadiene), cationic polymerization (for
example, polyisobutylene) and group transfer polymerization (for
example, poly(meth)acrylates).
[0087] The groups R, R.sup.1, Z and Z.sup.1 are preferably chosen
so as to be appropriate for use with the desired monomers or
monomer combination and the polymerization method as disclosed in
WO-A-98/01478, WO-A-99/05099 and WO-A-99/31144, all of which are
incorporated herein by reference.
[0088] The synthesis of block copolymers by RAFT polymerization can
be carried out in emulsion, solution or suspension in either a
batch, semi-batch, continuous, or feed mode. For lowest
polydispersity block copolymers, the RAFT agent is typically added
before polymerization is commenced. For example, when carried out
in a batch mode in solution, the reactor is typically charged with
a RAFT agent and a monomer, or a polymerization medium plus the
monomer. Block copolymers with broader, yet controlled,
polydispersity or with multimodal molecular weight distribution can
be produced by controlled addition of the RAFT agent over the
course of the polymerization process.
[0089] In the case of emulsion or suspension polymerization, the
polymerization medium will often be predominantly water and the
conventional stabilizers, dispersants and other additives can be
present.
[0090] For solution polymerization, the polymerization medium can
be chosen from a wide range of media to suit the monomer(s) being
used. For example, aromatic hydrocarbons, such as, petroleum
naphtha or xylenes; ketones, such as, methyl amyl ketone, methyl
isobutyl ketone, methyl ethyl ketone or acetone; esters, such as,
butyl acetate or hexyl acetate; and glycol ether esters, such as,
propylene glycol monomethyl ether acetate.
[0091] The use of feed polymerization conditions allows the use of
RAFT agents with lower chain transfer constants and allows the
synthesis of block copolymers that are not readily achieved using
batch polymerization processes. If the RAFT polymerization is
carried out as a feed system, the reaction can be carried out as
follows:
[0092] The reactor is charged with the chosen polymerization
medium, the RAFT agent and optionally a portion of the monomer
mixture. Into a separate vessel is placed the remaining monomer
mixture. The free radical initiator is dissolved or suspended in
polymerization medium in another separate vessel. The medium in the
reactor is heated and stirred while the monomer mixture plus the
medium and the initiator plus the medium, is introduced, for
example by a syringe pump or other pumping device. The rate and
duration of feed is largely determined by the quantity of the
solution, the desired monomer/RAFT agent/initiator ratio and the
rate of the polymerization. When the feed is complete, heating may
be continued for an additional period.
[0093] Following completion of the polymerization, the block
copolymer can be isolated by stripping off the medium and unreacted
monomer(s) or by precipitation with a non-solvent. Alternatively,
the polymer solution/emulsion can be used as such, if appropriate
to its application.
[0094] Block and multi-block and gradient copolymers may be
prepared by varying the rate of monomer(s) addition and/or by
varying the sequence in which the monomer(s) may be added to the
polymerization medium. Gradient block may also be prepared in a
one-step process by making use of the inherent difference in
reactivity of the monomer(s). For gradient block copolymers, it is
often desirable to pick comonomers with disparate reactivity
ratios. For example, maleic anhydride and styrene or
(meth)acrylates.
[0095] By appropriate selection of the groups R, R.sup.1, Z,
Z.sup.1, P and X of the RAFT chain transfer agent of formulae I-IV
above, block copolymers with specific end functionalities can be
readily produced. Block copolymer may be prepared by starting with
an existent polymer chain prepared by means other than RAFT
polymerization and then modifying the end or other functionality
such that the polymer chain is incorporated in a compound of
formulae I-IV so as to create a macromolecular RAFT agent that can
be chain extended by RAFT polymerization.
[0096] The "source of free radicals" or "initiator" suitable for
use in the present invention includes those compounds that provide
initiating radicals that add to monomers to produce propagating
radicals.
[0097] The amount of initiator used depends upon the desired
polydispersity, molecular weight and polymer structure of the
resulting polymer. However, generally less than 10 weight percent
based on the total amount of monomer mixture is used. Preferably
the amount of initiator used is in the range of 0.001 to 5.0 weight
percent.
[0098] The source of initiating radicals includes such sources as
the thermally induced homolytic scission of a suitable initiator,
such as peroxides, peroxyesters, or azo compounds; the spontaneous
generation from monomer, such as styrene; redox initiating systems;
photochemical initiating systems or high energy radiation source,
such as electron beam, X- or .gamma.-radiation or a combination of
these methods. The initiating system is chosen such that under the
reaction conditions there is substantially no adverse interaction
of the initiator or the initiating radicals with the RAFT agent
under the reaction conditions. The initiator should also have the
requisite solubility in the reaction medium or the monomer
mixture.
[0099] Examples of suitable sources of free radicals for the
process include azo compounds and peroxides such as for example
2,2'-azobis(isobutyronitrile), 2,2'-azobis(2-cyano-2-butane),
dimethyl 2,2'-azobis(methyl isobutyrate),
4,4'-azobis(4-cyanopentanoic acid),
4,4'-azobis(4-cyanopentan-1-ol),
1,1'-azobis(cyclohexanecarbonitrile),
2-(t-butylazo)-2-cyanopropane,
2,2'-azobis[2-methyl-N-(1,1)-bis(hydoxymethyl)-2-hydroxyethyl]propionamid-
e, 2,2'-azobis[2-methyl-N-hydroxyethyl)]-propionamide,
2,2'-azobis(N,N'-dimethyleneisobutyramidine) di-hydrochloride,
2,2'-azobis(2-amidinopropane)dihydrochloride,
2,2'-azobis(N,N'-dimethylene-isobutyramine),
2,2'-azobis(2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propionamid-
e),
2,2'-azobis(2-methyl-N-[1,1-bis(hydroxymethyl)ethyl]propionamide),
2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide],
2,2'-azobis(isobutyramide)dihydrate,
2,2'-azobis-(2,2,4-trimethylpentane), 2,2'-azobis(2-methylpropane),
tert-butyl peroxyacetate, tert-butyl peroxybenzoate, t-butyl
peroxyoctoate, tert-butyl peroxyneodecanoate, tert-butylperoxy
isobutyrate, tert-amyl peroxypivalate, tert-butyl peroxypivalate,
di-isopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate,
dicumyl peroxide, dibenzoyl peroxide, dilauroyl peroxide, potassium
peroxydisulfate, ammonium peroxydisulfate, di-t-butyl hyponitrite,
or dicumyl hyponitrite.
[0100] Photochemical initiator systems are chosen to have the
requisite solubility in the reaction medium or monomer mixture and
have an appropriate quantum yield for radical production under the
conditions of the polymerization. Examples include benzoin
derivatives, benzophenone, acyl phosphine oxides, and photo-redox
systems. Free radicals may also be derived by direct photolysis of
the compound of formula I-III.
[0101] Redox initiator systems are chosen to have the requisite
solubility in the reaction medium or monomer mixture and have an
appropriate rate of radical production under the conditions of the
polymerization; these initiating systems can include combinations
of the following oxidants and reductants: Oxidants: potassium
peroxydisulfate, hydrogen peroxide, and tert-butyl hydroperoxide.
Reductants: iron (II), titanium (III), potassium thiosulfite, and
potassium bisulfite.
[0102] Other suitable initiating systems are described in recent
texts. See, for example, Moad and Solomon "The Chemistry of Free
Radical Polymerization", Pergamon, London, 1995, pp 53-95.
[0103] Compositions which are of interest include those comprising
as component (c) a block or comb copolymer having at least one clay
compatible block and at least one matrix polymer compatible block
prepared by controlled free radical polymerization.
[0104] Preferably, a clay compatible block is based on hydrophilic
or "clayophilic" monomers which contain polar groups such as for
example ether [--O--], amide
##STR00002##
thioamide
##STR00003##
nitrile, anhydride, hydroxy, amine, pyridine, ammonium and
phosphonium in appropriate proximity.
[0105] Preferred hydrophilic or "clayophilic" monomers are for
example PEO acrylate, 1-vinyl-2-pyrrolidinone, N,N-dimethyl
acrylamide, acrylonitrile, maleic anhydride, hydroxyethyl acrylate,
hydroxypropyl acrylate, tert-butyl .alpha.-hydroxymethacrylate,
N,N'-dimethylaminoethyl acrylate, 4-vinylbenzyldihydroxyethylamine,
4-vinylpyridine or 4-vinylbenzyltributylphosphonium chloride.
[0106] The molecular weight of the acrylic copolymer is preferably
between 1000 and 100000 and the polydispersity between 1.05 and
3.0. More preferably the molecular weight is between 2000 and 20000
and the polydispersity is between 1.05 and 2.0.
[0107] Copolymers of the above polymers with other monomers may
also be used.
[0108] The polar (hydrophilic) or "clayophilic" segments may also
be derived from a polar condensation or other polymers such as for
example poly(ethylene oxide).
[0109] Preference is given therefore to compositions comprising as
component (c) a block or comb acrylic copolymer prepared by
controlled free radical polymerization.
[0110] The block or comb copolymers prepared by controlled free
radical polymerisation can also be described as polymeric
dispersing or solvating agents having amphiphilic properties. They
have polar and nonpolar groups in the same molecule and they are,
for example, dispersing or solvating agents based on polyethylene
glycols (PEG), polyacrylates, polysiloxanes, poly-vinyl acetate or
on block copolymers containing at least one block copolymer based
on acrylate, acrylic acid or methacrylate.
[0111] Block copolymers are, for example, diblock copolymers (A-B
type) or triblock copolymers (A-B-A or A-B-C type) and so-called
tapered structures.
[0112] Diblock copolymers (A-B type) are, for example,
poly(styrene-b-methylmethacrylate),
poly-(styrene-b-tert-butylmethacrylate),
poly(styrene-b-methylacrylate), poly(styrene-b-n-butyl-acrylate),
poly(styrene-b-tert-butylacrylate), poly(styrene-b-butadiene),
poly(styrene-b-iso-prene[1,4-addition]), tapered block copolymer
poly(styrene-b-butadiene), tapered block copolymer
poly(styrene-b-ethylene), poly(styrene-b-2-vinylpyridine),
poly(styrene-b-4-vinyl-pyridine),
poly(styrene-bis-tert-butylstyrene),
poly(styrene-b-dimethylsiloxane),
poly(butadiene-b-dimethylsiloxane),
poly(butadiene[1,4-addition]b-methylmethacrylate),
poly(isoprene[1-4-addition]-b-methylmethacrylate),
poly(butadiene-b-tert-butylmethacrylate),
poly(butadiene-b-tert-butylacrylate),
poly(isoprene-b-2-vinylpyridine),
poly(butadiene-b-4-vinylpyridine), poly-(styrene-b-methyl
methacrylate), poly(methyl methacrylate-b-tert-butyl methacrylate),
poly-(methyl methacrylate-b-tert-butyl acrylate), poly(tert-butyl
acrylate-b-methyl methacrylate),
poly(n-butylacrylate-b-methylmethacrylate),
poly(2-vinylpyridine-b-methyl methacrylate), poly(tert-butyl
methacrylate-b-tert-butyl acrylate), poly(tert-butyl
methacrylate-b-2-vinylpyridine), poly(tert-butyl
methacrylate-b-4-vinylpyridine), poly(tert-butyl
acrylate-b-2-vinylpyridine),
poly(2-vinylpyridine-b-4-vinylpyridine), poly(ethylene-b-methyl
methacrylate), poly-(ethylene-b-2-vinylpyridine) or
poly(ethylene-b-4-vinylpyridine).
[0113] Triblock copolymers of the A-B-A type are, for example,
poly(methyl methacrylate-b-styrene-b-methyl methacrylate),
poly(tert-butyl methacrylate-b-styrene-b-tert-butyl methacrylate),
poly(tert-butylacrylate-b-styrene-b-tert-butylacrylate),
poly(2-vinylpyridine-b-styrene-b-tert-butyl acrylate),
poly(4-vinylpyridine-b-styrene-b-4-vinylpyridine),
poly(butadiene[1,2-addition]-b-styrene-b-butadiene[1,2-addition]),
poly(butadiene[1,4-addition]-b-styrene-b-butadiene[1,4-addition]),
poly(styrene-b-butadiene[1,4- and 1,2-addition]-b-styrene),
poly(methyl methacrylate-b-butadiene[1,4- or 1,2-addition]-b-methyl
methacrylate), poly(tert-butyl methacrylate-b-methyl
methacrylate-b-tert-butyl methacrylate), poly(tert-butyl
acrylate-b-methyl methacrylate-b-tert-butyl acrylate), poly(methyl
methacrylate-b-2-vinylpyridine-b-methyl methacrylate),
poly(4-vinylpyridine-b-methyl methacrylate-b-4-vinylpyridine),
poly(methyl methacrylate-b-tert-butyl acrylate-b-methyl
methacrylate), poly(methyl methacrylate-b-n-butyl acrylate-b-methyl
methacrylate), poly(tert-butyl methacrylate-b-tert-butyl
acrylate-b-tert-butyl methacrylate),
poly(2-vinylpyridine-b-tert-butyl acrylate-b-2-vinylpyridine),
poly(4-vinylpyridine-b-tert-butyl acrylate-b-4-vinylpyridine),
poly(styrene-b-n-butyl acrylate-b-styrene), poly(styrene-b-ethyl
acrylate-b-styrene), poly(styrene-b-ethylene-b-styrene),
poly(styrene-b-butylene-b-styrene), poly(ethylene
oxide-b-styrene-b-ethylene oxide), poly(styrene-b-ethylene
oxide-b-styrene) or poly(styrene-b-acrylic acid-b-styrene).
[0114] Triblock copolymers of the A-B-C type are, for example,
poly(styrene-b-butadiene-b-2-vinyl-pyridine),
poly(styrene-b-butadiene-b-4-vinylpyridine),
poly(styrene-b-tert-butyl methacrylate-b-2-vinylpyridine),
poly(styrene-b-tert-butylmethacrylate-b-4-vinylpyridine),
poly(styrene-b-2-vinylpyridine-b-4-vinylpyridine),
poly(butadiene-b-styrene-b-methyl methacrylate),
poly(styrene-b-butadiene-b-methyl methacrylate),
poly(styrene-b-2-vinylpyridine-b-ethyl oxide),
poly-(styrene-b-tert-butyl acrylate-b-methyl methacrylate),
poly(styrene-b-acrylic acid-b-methyl methacrylate),
poly(styrene-b-a-methylstyrene-b-methyl methacrylate) or
poly(styrene-b-a-methylstyrene-b-tert-butyl acrylate).
[0115] Particularly suitable dispersing or solvating agents having
amphiphilic properties are, for example, poly(butadiene-b-methyl
methacrylate), poly(isoprene-b-methylmethacrylate),
poly-(ethylene-b-methyl methacrylate),
poly(styrene-b-4-vinylpyridine), poly(styrene-2-b-vinylpyridine),
poly(styrene-b-n-butyl acrylate), poly(styrene-b-tert-butyl
acrylate), poly(styrene-b-sodium acrylate), poly(styrene-b-acrylic
acid), poly(methyl methacrylate-b-sodium acrylate), poly(methyl
methacrylate-b-sodium methacrylate), poly(ethylene
oxide-b-c-caprolactone), poly(2-vinylpyridine-b-ethylene oxide),
poly(butadiene-b-ethylene oxide), poly(butadiene-b-sodium
acrylate), poly(ethylene-b-ethylene oxide),
poly(ethylene-b-propylene oxide),
poly-(styrene-b-ethylacrylate-b-styrene), poly(ethylene
oxide-b-styrene-b-ethylene oxide), poly-(styrene-b-acrylic
acid-styrene), poly(styrene-b-butadiene-b-methyl methacrylate),
poly(styrene-b-vinylpyridine-b-ethylene oxide),
poly(styrene-b-4-vinylbenzoic acid),
poly(styrene-b-polyglycidyl-methacrylate), poly(ethylene-b-glycidyl
methacrylate), poly(propylene-b-acrylic acid),
poly(ethylene-b-acrylic acid), poly(propylene-b-maleic anhydride),
poly(ethylene-b-maleic anhydride), poly(styrene-b-maleic
anhydride), poly(methacrylic acid)-poly(alkylene oxide) block
copolymers, for example according to EP-A-0 859 028,
polysiloxane-polyoxy-alkylene, copolymers of maleates and styrene
or styrene derivatives, for example according to EP-A-0 791 024,
polystyrene-polysiloxane block copolymers,
polyacrylate-polysiloxane block copolymers and
cyclosiloxane-radiale copolymers, prepared e.g. using ATRP
technology according to EP-A-0 870 774, methylacrylate-styrene
copolymer, methylmethacrylate-styrene,
polybutadiene-methylacrylates, prepared by nitroxyl-initiated
radical polymerisation according to EP-A-0 135 280.
[0116] The polyalkylene oxides are preferably polyethylene oxide,
polypropylene oxide and polybutylene oxide.
[0117] Suitable block copolymers are, for example,
polyacrylate/polystyrene, polymethacrylate/poly-ethylene oxide,
polyacrylate/polyethylene oxide, polyacrylate/polyethylene,
polyvinyl acetate/polyethylene, polystyrene/polybutadiene,
polyacrylate/polybutadiene, polyacrylate/polyisoprene,
polyisoprene/polymethylmethacrylate,
polyethylene/polymethylmethacrylate, polyethylene/polyethylene
oxide or polyethylene/polypropylene oxide.
[0118] Particularly suitable dispersing or solvating agents having
amphiphilic properties are, for example, poly(styrene-bis-sodium
acrylate), polystyrene-bis-acrylic acid), poly(styrene-bis-sodium
methacrylate), poly(styrene-bis-N-methyl-4-vinylpyridinium iodide),
poly(isoprene-bis-N-methyl-2-vinylpyridinium iodide),
poly(styrene-bis-ethylene oxide),
poly(methylmethacrylate-bis-sodium acrylate),
poly(methylmethacrylate-bis-sodium methacrylate),
poly(methyl-methacrylate-bis-ethylene oxide),
poly(tert-butylmethacrylate-bis-ethylene oxide),
poly-(methylmethacrylate-bis-N-methyl-4-vinylpyridinium iodide),
poly(ethylene oxide-bis-lactate), poly(2-vinylpyridine-bis-ethylene
oxide), poly(butadiene-bis-sodium acrylate),
poly(butadiene-bis-sodium methacrylate),
poly(butadiene-bis-N-methyl-4-vinylpyridinium iodide),
poly(buta-diene-bis-ethylene oxide), poly(ethylene-bis-ethylene
oxide) or poly(ethylene-bis-propylene oxide).
[0119] Other likewise preferred dispersing or solvating agents
based on polyacrylates are described, inter alia, in U.S. Pat. No.
5,133,898.
[0120] Preferably, component (b) is present in the composition in
an amount of from 0.1 to 40%, more preferably 0.5 to 20%, most
preferably from 1 to 10%, based on the weight of the synthetic
polymer [component (a)].
[0121] Preferably, component (c) is present in the composition in
an amount of from 0.1 to 20%, more preferably 0.1 to 15%, most
preferably from 0.1 to 10%, based on the weight of the synthetic
polymer [component (a)].
[0122] In addition to components (a), (b) and (c) the novel
compositions may comprise further additives, such as, for example,
the following:
[0123] 1. Antioxidants
[0124] 1.1. Alkylated monophenols, for example
2,6-di-tert-butyl-4-methylphenol, 2-butyl-4,6-di-methylphenol,
2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol,
2,6-di-tert-butyl-4-isobutylphenol,
2,6-dicyclopentyl-4-methylphenol,
2-(a-methylcyclohexyl)-4,6-di-methylphenol,
2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol,
2,6-di-tert-butyl-4-methoxymethylphenol, linear nonylphenols or
nonylphenols branched in the side-chain, e.g.
2,6-dinonyl-4-methylphenol,
2,4-dimethyl-6-(1'-methylundec-1'-yl)-phenol,
2,4-dimethyl-6-(1'-methylheptadec-1'-yl)-phenol,
2,4-dimethyl-6-(1'-nnethyltridec-1'-yl)-phenol and mixtures
thereof.
[0125] 1.2. Alkylthiomethylphenols, for example
2,4-dioctylthiomethyl-6-tert-butylphenol,
2,4-dioctyl-thiomethyl-6-methylphenol,
2,4-dioctylthiomethyl-6-ethylphenol,
2,6-didodecylthiomethyl-4-nonylphenol.
[0126] 1.3. Hydroquinones and alkylated hydroquinones, for example
2,6-di-tert-butyl-4-methoxy-phenol, 2,5-di-tert-butylhydroquinone,
2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octa-decyloxyphenol,
2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole,
3,5-di-tert-butyl-4-hydroxyanisole,
3,5-di-tert-butyl-4-hydroxyphenyl stearate,
bis(3,5-di-tert-butyl-4-hydroxyphenyl)adipate.
[0127] 1.4. Tocopherols, for example .alpha.-tocopherol,
.beta.-tocopherol, .gamma.-tocopherol, .delta.-tocopherol and
mixtures thereof (Vitamin E).
[0128] 1.5. Hydroxylated thiodiphenyl ethers, for example
2,2'-thiobis(6-tert-butyl-4-methylphenol),
2,2'-thiobis(4-octylphenol),
4,4'-thiobis(6-tert-butyl-3-methylphenol),
4,4'-thiobis(6-tert-butyl-2-methylphenol),
4,4'-thiobis(3,6-di-sec-amylphenol),
4,4'-bis(2,6-dimethyl-4-hydroxyphenyl)disulfide.
[0129] 1.6. Alkylidene bisphenols, for example
2,2'-methylenebis(6-tert-butyl-4-methylphenol),
2,2'-methylenebis(6-tert-butyl-4-ethylphenol),
2,2'-methylenebis[4-methyl-6-(.alpha.-methylcyclohexyl)-phenol],
2,2'-methylenebis(4-methyl-6-cyclohexylphenol),
2,2'-methylenebis(6-nonyl-4-methylphenol),
2,2'-methylenebis(4,6-di-tert-butylphenol),
2,2'-ethylidenebis(4,6-di-tert-butyl-phenol),
2,2'-ethylidenebis(6-tert-butyl-4-isobutylphenol),
2,2'-methylenebis[6-(.alpha.-methylbenzyl)-4-nonylphenol],
2,2'-methylenebis[6-(.alpha.,.alpha.-dimethylbenzyl)-4-nonylphenol],
4,4'-methylenebis(2,6-di-tert-butylphenol),
4,4'-methylenebis(6-tert-butyl-2-methylphenol),
1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,
2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol,
1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,
1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutane,
ethylene glycol
bis[3,3-bis(3'-tert-butyl-4'-hydroxyphenyl)butyrate],
bis(3-tert-butyl-4-hydroxy-5-methylphenyl)dicyclopentadiene,
bis[2-(3'-tert-butyl-2'-hydroxy-5'-methylbenzyl)-6-tert-butyl-4-methylphe-
nyl]terephthalate, 1,1-bis(3,5-dimethyl-2-hydroxyphenyl)butane,
2,2-bis(3,5-di-tert-butyl-4-hydroxyphenyl)propane,
2,2-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-4-n-dodecylmercaptobutane,
1,1,5,5-tetra(5-tert-butyl-4-hydroxy-2-methylphenyl)pentane.
[0130] 1.7. O--, N-- and S-benzyl compounds, for example
3,5,3',5'-tetra-tert-butyl-4,4'-dihydroxy-dibenzyl ether,
octadecyl-4-hydroxy-3,5-dimethylbenzyl mercaptoacetate,
tridecyl-4-hydroxy-3,5-di-tert-butylbenzyl mercaptoacetate,
tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine,
bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate,
bis(3,5-di-tert-butyl-4-hydroxy-benzyl)sulfide,
isooctyl-3,5-di-tert-butyl-4-hydroxybenzyl mercaptoacetate.
[0131] 1.8. Hydroxybenzylated malonates, for example dioctadecyl
2,2-bis(3,5-di-tert-butyl-2-hydroxybenzyl)malonate, dioctadecyl
2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)malonate,
didodecylmercaptoethyl
2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate,
di-[4-(1,1,3,3-tetramethylbutyl)phenyl]2,2-bis(3,5-di-tert-butyl-4-hydrox-
ybenzyl)malonate.
[0132] 1.9. Hydroxybenzyl aromatic compounds, for example
1,3,5-tris(3,5-di-tert-butyl-4-hydroxy-benzyl)-2,4,6-trimethylbenzene,
1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetra-methylbenzene,
2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.
[0133] 1.10. Triazine compounds, for example
2,4-bisoctylmercapto-6-(3,5-di-tert-butyl-4-hydroxy-anilino)-1,3,5-triazi-
ne,
2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-tria-
zine,
2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-tr-
iazine,
2,4,6-tris-(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine,
1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate,
1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate,
2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazine,
1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexahydro-1,3,5-tri-
azine,
1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate.
[0134] 1.11. Benzylphosphonates, for example dimethyl
2,5-di-tert-butyl-4-hydroxybenzyl-phosphonate, diethyl
3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl
3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl
5-tert-butyl-4-hydroxy-3-methylbenzyl-phosphonate, calcium salt of
3,5-di-tert-butyl-4-hydroxybenzyl-phosphonic acid monoethyl
ester.
[0135] 1.12. Acylaminophenols, for example 4-hydroxylauric acid
anilide, 4-hydroxystearic acid anilide,
N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamic acid octyl ester.
[0136] 1.13. Esters of
.beta.-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid with mono-
or poly-hydric alcohols, for example with methanol, ethanol,
n-octanol, isooctanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol,
ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene
glycol, diethylene glycol, triethylene glycol, pentaerythritol,
tris(hydroxyethyl) isocyanurate, N,N'-bis(hydroxyethyl)oxalic acid
diamide, 3-thiaundecanol, 3-thiapentadecanol, trimethyl-hexanediol,
trimethylolpropane,
4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
[0137] 1.14. Esters of
.beta.-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with
mono- or polyhydric alcohols, for example with methanol, ethanol,
n-octanol, isooctanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol,
ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene
glycol, diethylene glycol, triethylene glycol, pentaerythritol,
tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxalic acid
diamide, 3-thiaundecanol, 3-thiapentadecanol, trimethyl-hexanediol,
trimethylolpropane,
4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane;
3,9-bis[2-{3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dim-
ethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane.
[0138] 1.15. Esters of
.beta.-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid with mono-
or poly-hydric alcohols, for example with methanol, ethanol,
octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene
glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol,
diethylene glycol, triethylene glycol, pentaerythritol,
tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxalic acid
diamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,
trimethylolpropane,
4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
[0139] 1.16. Esters of 3,5-di-tert-butyl-4-hydroxyphenylacetic acid
with mono- or poly-hydric alcohols, for example with methanol,
ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol,
ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene
glycol, diethylene glycol, triethylene glycol, pentaerythritol,
tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxalic acid
diamide, 3-thiaundecanol, 3-thiapentadecanol, trimethyl-hexanediol,
trimethylolpropane,
4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
[0140] 1.17. Amides of
.beta.-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid, for
example
N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamide,
N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)trimethylenediamide,
N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenyl-propionyl)hydrazide),
N,N'-bis[2-(3-[3,5-di-tert-butyl-4-hydroxyphenyl]-propionyloxy)ethyl]-oxa-
mide (Naugard.RTM.XL-1 from Uniroyal).
[0141] 1.18. Ascorbic acid (Vitamin C).
[0142] 1.19. Amine-type antioxidants, for example
N,N'-di-isopropyl-p-phenylenediamine,
N,N'-di-sec-butyl-p-phenylenediamine,
N,N'-bis(1,4-dimethylpentyl)-p-phenylenediamine,
N,N'-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine,
N,N'-bis(1-methylheptyl)-p-phenylenediamine,
N,N'-dicyclohexyl-p-phenylenediamine,
N,N'-diphenyl-p-phenylenediamine,
N,N'-di(2-naphthyl)-p-phenylenediamine,
N-isopropyl-N'-phenyl-p-phenylenediamine,
N-(1,3-dimethyl-butyl)-N'-phenyl-p-phenylenediamine,
N-(1-methylheptyl)-N'-phenyl-p-phenylenediamine,
N-cyclohexyl-N'-phenyl-p-phenylenediamine,
4-(p-toluenesulfonamido)-diphenylamine,
N,N'-dimethyl-N,N'-di-sec-butyl-p-phenylenediamine, diphenylamine,
N-allyldiphenylamine, 4-isopropoxydiphenylamine,
N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine,
N-phenyl-2-naphthylamine, octylated diphenylamine, for example
p,p'-di-tert-octyl-diphenylamine, 4-n-butylaminophenol,
4-butyrylaminophenol, 4-nonanoylaminophenol,
4-dodecanoylaminophenol, 4-octadecanoylaminophenol,
di(4-methoxyphenyl)amine,
2,6-di-tert-butyl-4-dimethylaminomethylphenol,
2,4'-diaminodiphenylmethane, 4,4'-diamino-diphenylmethane,
N,N,N',N'-tetramethyl-4,4'-diaminodiphenylmethane,
1,2-di[(2-methyl-phenyl)amino]ethane, 1,2-di(phenylamino)propane,
(o-tolyl)-biguanide, di[4-(1',3'-dimethyl-butyl)phenyl]amine,
tert-octylated N-phenyl-1-naphthylamine, mixture of mono- and
di-alkylated tert-butyl-/tert-octyl-diphenylamines, mixture of
mono- and di-alkylated nonyl-diphenylamines, mixture of mono- and
di-alkylated dodecyldiphenylamines, mixture of mono- and
di-alkylated isopropyl-/isohexyl-diphenylamines, mixtures of mono-
and di-alkylated tert-butyldiphenylamines,
2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine,
mixture of mono- and di-alkylated
tert-butyl-/tert-octyl-phenothiazines, mixture of mono- and
di-alkylated tert-octylphenothiazines, N-allylphenothiazine or
N,N,N',N'-tetraphenyl-1,4-diaminobut-2-ene.
[0143] 2. UV absorbers and light stabilizers 2.1.
2-(2'-Hydroxyphenyl)-benzotriazoles, for example
2-(2'-hydroxy-5'-methylphenyl)-benzotriazole,
2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-benzotriazole,
2-(5'-tert-butyl-2'-hydroxyphenyl)-benzotriazole,
2-(2'-hydroxy-5'-(1,1,3,3-tetramethylbutyl)-phenyl)-benzotriazole,
2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-chlorobenzotriazole,
2-(3'-tert-butyl-2'-hydroxy-5'-methylphenyl)-5-chlorobenzotriazole,
2-(3'-sec-butyl-5'-tert-butyl-2'-hydroxyphenyl)-benzotriazole,
2-(2'-hydroxy-4'-octyloxyphenyl)-benzotriazole,
2-(3',5'-di-tert-amyl-2'-hydroxyphenyl)-benzotriazole,
2-(3',5'-bis(.alpha.,.alpha.-dimethylbenzyl)-2'-hydroxyphenyl)-benzotriaz-
ole,
2-(3'-tert-butyl-2'-hydroxy-5'-(2-octyloxycarbonylethyl)phenyl)-5-chl-
orobenzotriazole,
2-(3'-tert-butyl-5'-[2-(2-ethylhexyloxy)carbonylethyl]-2'-hydroxyphenyl)--
5-chlorobenzotriazole,
2-(3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl)-5-chlorobe-
nzotriazole,
2-(3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl)-benzotriaz-
ole,
2-(3'-tert-butyl-2'-hydroxy-5'-(2-octyloxy-carbonylethyl)phenyl)-benz-
otriazole,
2-(3'-tert-butyl-5'-[2-(2-ethylhexyloxy)carbonylethyl]-2'-hydro-
xyphenyl)-benzotriazole,
2-(3'-dodecyl-2'-hydroxy-5'-methylphenyl)-benzotriazole,
2-(3'-tert-butyl-2'-hydroxy-5'-(2-isooctyloxycarbonylethyl)-phenyl-benzot-
riazole,
2,2'-methylenebis-[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazol-2--
yl-phenol]; transesterification product of
2-[3'-tert-butyl-5'-(2-methoxycarbonylethyl)-2'-hydroxyphenyl]-benzotriaz-
ole with polyethylene glycol 300;
[R--CH.sub.2CH.sub.2--COO--CH.sub.2CH.sub.2 .sub.2 wherein
R=3'-tert-butyl-4'-hydroxy-5'-2H-benzotriazol-2-yl-phenyl;
2-[2'-hydroxy-3'-(.alpha.,.alpha.-dimethylbenzyl)-5'-(1,1,3,3-tetramethyl-
butyl)-phenyl]-benzotriazole;
2-[2'-hydroxy-3'-(1,1,3,3-tetramethylbutyl)-5'-(.alpha.,.alpha.-dimethylb-
enzyl)-phenyl]-benzotriazole.
[0144] 2.2. 2-Hydroxybenzophenones, for example the 4-hydroxy,
4-methoxy, 4-octyloxy, 4-decyl-oxy, 4-dodecyloxy, 4-benzyloxy,
4,2',4'-trihydroxy or 2'-hydroxy-4,4'-dimethoxy derivative.
[0145] 2.3. Esters of unsubstituted or substituted benzoic acids,
for example 4-tert-butyl-phenyl salicylate, phenyl salicylate,
octyiphenyl salicylate, dibenzoylresorcinol,
bis(4-tert-butylbenzoyl)resorcinol, benzoylresorcinol,
3,5-di-tert-butyl-4-hydroxybenzoic acid 2,4-di-tert-butylphenyl
ester, 3,5-di-tert-butyl-4-hydroxybenzoic acid hexadecyl ester,
3,5-di-tert-butyl-4-hydroxybenzoic acid octadecyl ester,
3,5-di-tert-butyl-4-hydroxybenzoic acid
2-methyl-4,6-di-tert-butylphenyl ester.
[0146] 2.4. Acrylates, for example
.alpha.-cyano-.beta.,.beta.-diphenylacrylic acid ethyl ester or
isooctyl ester, .alpha.-methoxycarbonylcinnamic acid methyl ester,
.alpha.-cyano-.beta.-methyl-p-methoxycinnamic acid methyl ester or
butyl ester, .alpha.-methoxycarbonyl-p-methoxycinnamic acid methyl
ester,
N-(.beta.-methoxycarbonyl-.beta.-cyanovinyl)-2-methyl-indoline.
[0147] 2.5. Nickel compounds, for example nickel complexes of
2,2'-thio-bis[4-(1,1,3,3-tetra-methylbutyl)phenol], such as the 1:1
or 1:2 complex, optionally with additional ligands, such as
n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel
dibutyl dithiocarbamate, nickel salts of
4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid monoalkyl esters,
such as of the methyl or ethyl ester, nickel complexes of
ketoximes, such as of 2-hydroxy-4-methylphenylundecyl ketoxime,
nickel complexes of 1-phenyl-4-lauroyl-5-hydroxypyrazole,
optionally with additional ligands.
[0148] 2.6. Sterically hindered amines, for example
bis(2,2,6,6-tetramethylpiperid-4-yl)sebacate,
bis(2,2,6,6-tetramethylpiperid-4-yl)succinate,
bis(1,2,2,6,6-pentamethylpiperid-4-yl)sebacate,
bis(1-octyloxy-2,2,6,6-tetramethylpiperid-4-yl)sebacate,
n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonic acid
bis(1,2,2,6,6-pentamethylpiperidyl)ester, condensation product of
1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic
acid, linear or cyclic condensation products of
N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and
4-tert-octylamino-2,6-dichloro-1,3,5-s-triazine,
tris(2,2,6,6-tetramethyl-4-piperidyl) nitrilo-triacetate,
tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetetraoate,
1,1'-(1,2-ethane-diyl)bis(3,3,5,5-tetramethylpiperazinone),
4-benzoyl-2,2,6,6-tetramethylpiperidine,
4-stearyl-oxy-2,2,6,6-tetramethylpiperidine,
bis(1,2,2,6,6-pentamethylpiperidyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tert-bu-
tylbenzyl) malonate,
3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione,
bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)sebacate,
bis(1-octyloxy-2,2,6,6-tetra-methylpiperidyl)succinate, linear or
cyclic condensation products of
N,N'-bis(2,2,6,6-tetra-methyl-4-piperidyl)hexamethylenediamine and
4-morpholino-2,6-dichloro-1,3,5-triazine, condensation product of
2-chloro-4,6-di(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-1,3,5-triazi-
ne and 1,2-bis(3-aminopropylamino)ethane, condensation product of
2-chloro-4,6-di(4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5-tria-
zine and 1,2-bis(3-aminopropylamino)-ethane,
8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-d-
ione,
3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidyl)pyrrolidine-2,5-dione,
3-dodecyl-1-(1,2,2,6,6-pentamethyl-4-piperidyl)pyrrolidine-2,5-dione,
mixture of 4-hexadecyloxy- and
4-stearyloxy-2,2,6,6-tetramethylpiperidine, condensation product of
N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and
4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, condensation product
of 1,2-bis(3-aminopropylamino)ethane and
2,4,6-trichloro-1,3,5-triazine and
4-butyl-amino-2,2,6,6-tetramethylpiperidine (CAS Reg. No.
[136504-96-6]); condensation product of 1,6-diaminohexane and
2,4,6-trichloro-1,3,5-triazine and also N,N-dibutylamine and
4-butyl-amino-2,2,6,6-tetramethylpiperidine (CAS Reg. No.
[192268-64-7]);
N-(2,2,6,6-tetramethyl-4-piperidyl)-n-dodecylsuccinimide,
N-(1,2,2,6,6-pentamethyl-4-piperidyl)-n-dodecylsuccinimide,
2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxo-spiro[4.5]decane,
reaction product of
7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro[4.5]decane
and epichlorohydrin,
1,1-bis(1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl)-2-(4-methoxyphenyl)-
ethene,
N,N'-bis-formyl-N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethy-
lenediamine, diester of 4-methoxymethylenemalonic acid with
1,2,2,6,6-pentamethyl-4-hydroxypiperidine,
poly[methyl-propyl-3-oxy-4-(2,2,6,6-tetramethyl-4-piperidyl)]siloxane,
reaction product of maleic anhydride .alpha.-olefin copolymer and
2,2,6,6-tetramethyl-4-aminopiperidine or
1,2,2,6,6-pentamethyl-4-aminopiperidine.
[0149] 2.7. Oxalic acid diamides, for example 4,4'-dioctyloxy
oxanilide, 2,2'-diethoxy oxanilide,
2,2'-dioctyloxy-5,5'-di-tert-butyl oxanilide,
2,2'-didodecyloxy-5,5'-di-tert-butyl oxanilide, 2-ethoxy-2'-ethyl
oxanilide, N,N'-bis(3-dimethylaminopropyl)oxalamide,
2-ethoxy-5-tert-butyl-2'-ethyl oxanilide and a mixture thereof with
2-ethoxy-2'-ethyl-5,4'-di-tert-butyl oxanilide, mixtures of o- and
p-methoxy- and also of o- and p-ethoxy-di-substituted
oxanilides.
[0150] 2.8. 2-(2-Hydroxyphenyl)-1,3,5-triazines, for example
2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine,
2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine-
,
2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,
2,4-bis(2-hydroxy-4-propyl-oxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazi-
ne,
2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine,
2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazi-
ne,
2-(2-hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-tr-
iazine,
2-[2-hydroxy-4-(2-hydroxy-3-butyloxypropyloxy)phenyl]-4,6-bis(2,4--
dimethylphenyl)-1,3,5-triazine,
2-[2-hydroxy-4-(2-hydroxy-3-octyloxypropyloxy)phenyl]-4,6-bis(2,4-dimethy-
lphenyl)-1,3,5-triazine,
2-[4-(dodecyloxy/tridecyloxy-2-hydroxypropoxy)-2-hydroxyphenyl]-4,6-bis(2-
,4-dimethylphenyl)-1,3,5-triazine,
2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxypropoxy)phenyl]-4,6-bis(2,4-dimethy-
lphenyl)-1,3,5-triazine,
2-(2-hydroxy-4-hexyloxy)phenyl-4,6-diphenyl-1,3,5-triazine,
2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine,
2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-1,3,5-triazine,
2-(2-hydroxyphenyl)-4-(4-methoxyphenyl)-6-phenyl-1,3,5-triazine,
2-{2-hydroxy-4-[3-(2-ethylhexyl-1-oxy)-2-hydroxypropyloxy]phenyl}-4,6-bis-
(2,4-dimethylphenyl)-1,3,5-triazine.
[0151] 3. Metal deactivators, for example N,N'-diphenyloxalic acid
diamide, N-salicylal-N'-salicyloyl-hydrazine,
N,N'-bis(salicyloyl)hydrazine,
N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hydrazine,
3-salicyloylamino-1,2,4-triazole, bis(benzylidene)oxalic acid
dihydrazide, oxanilide, isophthalic acid dihydrazide, sebacic acid
bis-phenylhydrazide, N,N'-diacetyladipic acid dihydrazide,
N,N'-bis-salicyloyloxalic acid dihydrazide,
N,N'-bis-salicyloylthiopropionic acid dihydrazide.
[0152] 4. Phosphites and phosphonites, e.g. triphenyl phosphite,
diphenylalkyl phosphites, phenyl-dialkyl phosphites,
tris(nonylphenyl)phosphite, trilauryl phosphite, trioctadecyl
phosphite, distearyl-pentaerythritol diphosphite,
tris(2,4-di-tert-butylphenyl)phosphite, diisodecylpentaerythritol
diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol
diphosphite, bis(2,4-di-cumylphenyl)-pentaerythritol diphosphite,
bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite,
bis-isodecyloxy-pentaerythritol diphosphite,
bis(2,4-di-tert-butyl-6-methylphenyl)pentaerythritol diphosphite,
bis(2,4,6-tri-tert-butylphenyl)pentaerythritol diphosphite,
tristearyl sorbitol triphosphite,
tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylene diphosphonite,
6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenzo[d,g]-1,3,2-dioxaphosp-
hocine, bis(2,4-di-tert-butyl-6-methylphenyl)methylphosphite,
bis(2,4-di-tert-butyl-6-methyl-phenyl)ethylphosphite,
6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenzo[d,g]-1,3,2-dioxa-pho-
sphocine,
2,2',2''-nitrilo[triethyl-tris(3,3',5,5'-tetra-tert-butyl-1,1'-b-
iphenyl-2,2'-diyl)-phosphite],
2-ethylhexyl-(3,3',5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl)phosphit-
e,
5-butyl-5-ethyl-2-(2,4,6-tri-tert-butylphenoxy)-1,3,2-dioxaphosphirane.
[0153] 5. Hydroxylamines, for example N,N-dibenzylhydroxylamine,
N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine,
N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine,
N,N-dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine,
N-hexadecyl-N-octadecyl-hydroxylamine,
N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine
from hydrogenated tallow fatty amines.
[0154] 6. Nitrones, for example N-benzyl-alpha-phenylnitrone,
N-ethyl-alpha-methylnitrone, N-octyl-alpha-heptylnitrone,
N-lauryl-alpha-undecylnitrone, N-tetradecyl-alpha-tridecylnitrone,
N-hexadecyl-alpha-pentadecylnitrone,
N-octadecyl-alpha-heptadecylnitrone,
N-hexadecyl-alpha-heptadecylnitrone,
N-octadecyl-alpha-pentadecylnitrone,
N-heptadecyl-alpha-hepta-decylnitrone,
N-octadecyl-alpha-hexadecylnitrone, nitrones derived from
N,N-dialkyl-hydroxylamines prepared from hydrogenated tallow fatty
amines.
[0155] 7. Thiosynergistic compounds, for example thiodipropionic
acid dilauryl ester or thio-dipropionic acid distearyl ester.
[0156] 8. Peroxide-destroying compounds, for example esters of
.beta.-thio-dipropionic acid, for example the lauryl, stearyl,
myristyl or tridecyl ester, mercaptobenzimidazole, the zinc salt of
2-mercaptobenzimidazole, zinc dibutyldithiocarbamate,
dioctadecyldisulfide, pentaerythritol
tetrakis(.beta.-dodecylmercapto)propionate.
[0157] 9. Polyamide stabilisers, for example copper salts in
combination with iodides and/or phosphorus compounds and salts of
divalent manganese.
[0158] 10. Basic co-stabilisers, for example melamine,
polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea
derivatives, hydrazine derivatives, amines, polyamides,
polyurethanes, alkali metal and alkaline earth metal salts of
higher fatty acids, for example calcium stearate, zinc stearate,
magnesium behenate, magnesium stearate, sodium ricinoleate,
potassium palmitate, antimony pyrocatecholate or zinc
pyrocatecholate.
[0159] 11. Nucleating agents, for example inorganic substances,
e.g. talc, metal oxides, such as titanium dioxide or magnesium
oxide, phosphates, carbonates or sulfates of preferably alkaline
earth metals; organic compounds, such as mono- or poly-carboxylic
acids and their salts, e.g. 4-tert-butylbenzoic acid, adipic acid,
diphenylacetic acid, sodium succinate or sodium benzoate; polymeric
compounds, for example ionic copolymerisates ("ionomers"). Special
preference is given to
1,3:2,4-bis(3',4'-dimethylbenzylidene)sorbitol,
1,3:2,4-di(paramethyldibenzylidene)sorbitol and
1,3:2,4-di(benzylidene)sorbitol.
[0160] 12. Fillers and reinforcing agents, for example calcium
carbonate, silicates, glass fibres, glass beads, talc, kaolin,
mica, barium sulfate, metal oxides and hydroxides, carbon black,
graphite, wood powders, and powders and fibres of other natural
products, synthetic fibres.
[0161] 13. Other additives, for example plasticisers, lubricants,
emulsifiers, pigments, rheology additives, catalysts, flow
improvers, optical brighteners, flame retardants, antistatics,
blowing agents.
[0162] 14. Benzofuranones and indolinones, for example as described
in U.S. Pat. No. 4,325,863; U.S. Pat. No. 4,338,244; U.S. Pat. No.
5,175,312, U.S. Pat. No. 5,216,052; U.S. Pat. No. 5,252,643; DE-A-4
316 611; DE-A-4 316 622; DE-A-4 316 876; EP-A-0 589 839 or EP-A-0
591 102, or
344-(2-acetoxyethoxy)phenyl]-5,7-di-tert-butyl-benzofuran-2-one,
5,7-di-tert-butyl-344-(2-stearoyl-oxyethoxy)phenyl]benzofuran-2-one,
3,3'-bis[5,7-di-tert-butyl-3-(4-[2-hydroxyethoxy]phenyl)-benzofuran-2-one-
], 5,7-di-tert-butyl-3-(4-ethoxyphenyl)benzofuran-2-one,
3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one,
3-(3,5-dimethyl-4-pivaloyloxy-phenyl)-5,7-di-tert-butyl-benzofuran-2-one,
3-(3,4-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one,
3-(2,3-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one.
[0163] The costabilizers are added, for example, in concentrations
of 0.01 to 10%, relative to the total weight of the synthetic
polymer to be stabilized.
[0164] Preferred further additives are phenolic antioxidants,
light-stabilizers, processing stabilizers, solvents, pigments,
dyes, plasticizers, compatibilizers, toughening agents and/or
thixotropic agents.
[0165] In addition to the nano fillers other fillers may be used as
reinforcing agents (item 12 in the list), for example talc, calcium
carbonate, hydrotalcite, mica, kaolin, metal hydroxides, especially
aluminium hydroxide or magnesium hydroxide. These are added to the
synthetic polymers in concentrations, for example, of from 0.01 to
40%, based on the overall weight of the synthetic polymers to be
stabilized.
[0166] Carbon black as filler is added to the synthetic polymers in
concentrations, judiciously, of from 0.01 to 5%, based on the
overall weight of the synthetic polymers to be stabilized.
[0167] Glass fibers as reinforcing agents are added to the
synthetic polymers in concentrations, judiciously, of from 0.01 to
20%, based on the overall weight of the synthetic polymers to be
stabilized.
[0168] Further preferred compositions comprise in addition to
components (a), (b) and (c) further additives as well, especially
alkaline earth metal salts of higher fatty acids, for example
calcium stearate.
[0169] As a conventional stabilizer combination for processing
synthetic polymers, for example polyolefins, to form corresponding
mouldings, the combination of a phenolic antioxidant with a
secondary antioxidant based on an organic phosphite or phosphonite
is recommended.
[0170] Incorporation of components (b) and (c) and, if desired,
further additives into the synthetic polymers is carried out by
known methods, for example before or during moulding or else by
applying the dissolved or dispersed compounds to the synthetic
polymer, if appropriate with subsequent slow evaporation of the
solvent.
[0171] The present invention also relates to a nanocomposite
material in the form of a masterbatch or concentrate comprising
component (a) in an amount of from 5 to 90%, component (b) in an
amount of from 5 to 80%, and component (c) in an amount of from 0.5
to 50% by weight.
[0172] Components (b) and (c) and, if desired, further additives,
can also be added before or during polymerisation or before
crosslinking.
[0173] Components (b) and (c), with or without further additives,
can be incorporated in pure form or encapsulated in waxes, oils or
polymers into the synthetic polymer.
[0174] Components (b) and (c), with or without further additives,
can also be sprayed onto the synthetic polymer. It is able to
dilute other additives (for example the conventional additives
indicated above) or their melts so that they too can be sprayed
together with these additives onto the polymer. Addition by
spraying on during the deactivation of the polymerization catalysts
is particularly advantageous, it being possible to carry out
spraying using, for example, the steam used for deactivation.
[0175] In the case of spherically polymerized polyolefins it may,
for example, be advantageous to apply components (b) and (c), with
or without other additives, by spraying.
[0176] The synthetic polymers prepared in this way can be employed
in a wide variety of forms, for example as foams, films, fibres,
tapes, moulding compositions, as profiles or as binders for coating
materials, especially powder coatings, adhesives, putties or
especially as thick-layer polyolefin mouldings which are in
long-term contact with extractive media, such as, for example,
pipes for liquids or gases, films, fibres, geomembranes, tapes,
profiles or tanks.
[0177] The preferred thick-layer polyolefin mouldings have a layer
thickness of from 1 to 50 mm, in particular from 1 to 30 mm, for
example from 2 to 10 mm.
[0178] The compositions according to the invention can be
advantageously used for the preparation of various shaped articles.
Examples are:
[0179] I-1) Floating devices, marine applications, pontoons, buoys,
plastic lumber for decks, piers, boats, kayaks, oars, and beach
reinforcements.
[0180] I-2) Automotive applications, in particular bumpers,
dashboards, battery, rear and front linings, moldings parts under
the hood, hat shelf, trunk linings, interior linings, air bag
covers, electronic moldings for fittings (lights), panes for
dashboards, headlamp glass, instrument panel, exterior linings,
upholstery, automotive lights, head lights, parking lights, rear
lights, stop lights, interior and exterior trims; door panels; gas
tank; glazing front side; rear windows; seat backing, exterior
panels, wire insulation, profile extrusion for sealing, cladding,
pillar covers, chassis parts, exhaust systems, fuel filter/filler,
fuel pumps, fuel tank, body side mouldings, convertible tops,
exterior mirrors, exterior trim, fasteners/fixings, front end
module, glass, hinges, lock systems, luggage/roof racks,
pressed/stamped parts, seals, side impact protection, sound
deadener/insulator and sunroof.
[0181] I-3) Road traffic devices, in particular sign postings,
posts for road marking, car accessories, warning triangles, medical
cases, helmets, tires.
[0182] I-4) Devices for plane, railway, motor car (car, motorbike)
including furnishings.
[0183] I-5) Devices for space applications, in particular rockets
and satellites, e.g. reentry shields.
[0184] I-6) Devices for architecture and design, mining
applications, acoustic quietized systems, street refuges, and
shelters.
[0185] II-1) Appliances, cases and coverings in general and
electric/electronic devices (personal computer, telephone, portable
phone, printer, television-sets, audio and video devices), flower
pots, satellite TV bowl, and panel devices.
[0186] II-2) Jacketing for other materials such as steel or
textiles.
[0187] II-3) Devices for the electronic industry, in particular
insulation for plugs, especially computer plugs, cases for electric
and electronic parts, printed boards, and materials for electronic
data storage such as chips, check cards or credit cards.
[0188] II-4) Electric appliances, in particular washing machines,
tumblers, ovens (microwave oven), dish-washers, mixers, and
irons.
[0189] II-5) Covers for lights (e.g. street-lights,
lamp-shades).
[0190] II-6) Applications in wire and cable (semi-conductor,
insulation and cable-jacketing).
[0191] II-7) Foils for condensers, refrigerators, heating devices,
air conditioners, encapsulating of electronics, semi-conductors,
coffee machines, and vacuum cleaners.
[0192] III-1) Technical articles such as cogwheel (gear), slide
fittings, spacers, screws, bolts, handles, and knobs.
[0193] III-2) Rotor blades, ventilators and windmill vanes, solar
devices, swimming pools, swimming pool covers, pool liners, pond
liners, closets, wardrobes, dividing walls, slat walls, folding
walls, roofs, shutters (e.g. roller shutters), fittings,
connections between pipes, sleeves, and conveyor belts.
[0194] III-3) Sanitary articles, in particular shower cubicles,
lavatory seats, covers, and sinks.
[0195] III-4) Hygienic articles, in particular diapers (babies,
adult incontinence), feminine hygiene articles, shower curtains,
brushes, mats, tubs, mobile toilets, tooth brushes, and bed
pans.
[0196] III-5) Pipes (cross-linked or not) for water, waste water
and chemicals, pipes for wire and cable protection, pipes for gas,
oil and sewage, guttering, down pipes, and drainage systems.
[0197] III-6) Profiles of any geometry (window panes) and
siding.
[0198] III-7) Glass substitutes, in particular extruded plates,
glazing for buildings (monolithic, twin or multiwall), aircraft,
schools, extruded sheets, window film for architectural glazing,
train, transportation, sanitary articles, and greenhouse.
[0199] III-8) Plates (walls, cutting board), extrusion-coating
(photographic paper, tetrapack and pipe coating), silos, wood
substitute, plastic lumber, wood composites, walls, surfaces,
furniture, decorative foil, floor coverings (interior and exterior
applications), flooring, duck boards, and tiles.
[0200] III-9) Intake and outlet manifolds.
[0201] III-10) Cement-, concrete-, composite-applications and
covers, siding and cladding, hand rails, banisters, kitchen work
tops, roofing, roofing sheets, tiles, and tarpaulins.
[0202] IV-1) Plates (walls and cutting board), trays, artificial
grass, astroturf, artificial covering for stadium rings
(athletics), artificial floor for stadium rings (athletics), and
tapes.
[0203] IV-2) Woven fabrics continuous and staple, fibers
(carpets/hygienic articles/geotextiles/monofilaments; filters;
wipes/curtains (shades)/medical applications), bulk fibers
(applications such as gown/protection clothes), nets, ropes,
cables, strings, cords, threads, safety seat-belts, clothes,
underwear, gloves; boots; rubber boots, intimate apparel, garments,
swimwear, sportswear, umbrellas (parasol, sunshade), parachutes,
paraglides, sails, "balloon-silk", camping articles, tents,
airbeds, sun beds, bulk bags, and bags.
[0204] IV-3) Membranes, insulation, covers and seals for roofs,
tunnels, dumps, ponds, dumps, walls roofing membranes,
geomembranes, swimming pools, curtains (shades)/sun-shields,
awnings, canopies, wallpaper, food packing and wrapping (flexible
and solid), medical packaging (flexible & solid),
airbags/safety belts, arm- and head rests, carpets, centre console,
dashboard, cockpits, door, overhead console module, door trim,
headliners, interior lighting, interior mirrors, parcel shelf, rear
luggage cover, seats, steering column, steering wheel, textiles,
and trunk trim.
[0205] V) Films (packaging, dump, laminating, agriculture and
horticulture, greenhouse, mulch, tunnel, silage), bale wrap,
swimming pools, waste bags, wallpaper, stretch film, raffia,
desalination film, batteries, and connectors.
[0206] VI-1) Food packing and wrapping (flexible and solid),
bottles.
[0207] VI-2) Storage systems such as boxes (crates), luggage,
chest, household boxes, pallets, shelves, tracks, screw boxes,
packs, and cans.
[0208] VI-3) Cartridges, syringes, medical applications, containers
for any transportation, waste baskets and waste bins, waste bags,
bins, dust bins, bin liners, wheely bins, container in general,
tanks for water/used water/chemistry/gas/oil/gasoline/diesel; tank
liners, boxes, crates, battery cases, troughs, medical devices such
as piston, ophthalmic applications, diagnostic devices, and packing
for pharmaceuticals blister.
[0209] VII-1) Extrusion coating (photo paper, tetrapack, pipe
coating), household articles of any kind (e.g. appliances, thermos
bottle/clothes hanger), fastening systems such as plugs, wire and
cable clamps, zippers, closures, locks, and snap-closures.
[0210] VII-2) Support devices, articles for the leisure time such
as sports and fitness devices, gymnastics mats, ski-boots,
inline-skates, skis, big foot, athletic surfaces (e.g. tennis
grounds); screw tops, tops and stoppers for bottles, and cans.
[0211] VII-3) Furniture in general, foamed articles (cushions,
impact absorbers), foams, sponges, dish clothes, mats, garden
chairs, stadium seats, tables, couches, toys, building kits
(boards/figures/balls), playhouses, slides, and play vehicles.
[0212] VII-4) Materials for optical and magnetic data storage.
[0213] VII-5) Kitchen ware (eating, drinking, cooking,
storing).
[0214] VII-6) Boxes for CD's, cassettes and video tapes; DVD
electronic articles, office supplies of any kind (ball-point pens,
stamps and ink-pads, mouse, shelves, tracks), bottles of any volume
and content (drinks, detergents, cosmetics including perfumes), and
adhesive tapes.
[0215] VII-7) Footwear (shoes/shoe-soles), insoles, spats,
adhesives, structural adhesives, food boxes (fruit, vegetables,
meat, fish), synthetic paper, labels for bottles, couches,
artificial joints (human), printing plates (flexographic), printed
circuit boards, and display technologies.
[0216] VII-8) Devices of filled polymers (talc, chalk, china clay
(kaolin), wollastonite, pigments, carbon black, TiO.sub.2, mica,
nanocomposites, dolomite, silicates, glass, asbestos).
[0217] Thus, a further embodiment of the present invention relates
to a shaped article, in particular a film, pipe, profile, bottle,
tank or container, fiber containing a composition as described
above.
[0218] A further embodiment of the present invention relates to a
molded article containing a composition as described above. The
molding is in particular effected by injection, blow, compression,
roto-molding or slush-molding or extrusion.
[0219] The present invention also relates to a process for the
preparation of a synthetic polymer nanocomposite material which
comprises melt mixing a mixture of a) a synthetic polymer, b) a
filler, and c) a dispersing agent prepared by controlled free
radical polymerization (CFRP).
[0220] The melt mixing can be carried out in any heatable container
equipped with a stirrer, for example in a closed apparatus such as
a kneader, mixer or stirred vessel. The incorporation is preferably
carried out in an extruder or in a kneader. It is immaterial
whether processing takes place in an inert atmosphere or in the
presence of oxygen.
[0221] The addition of components (a), (b) and (c) can be carried
out in all customary mixing machines in which the polymer is melted
and mixed with the additives. Suitable machines are known to those
skilled in the art. They are predominantly mixers, kneaders and
extruders. The process is preferably carried out in an extruder by
introducing the additive during processing. Particularly preferred
processing machines are single-screw extruders, contrarotating and
corotating twin-screw extruders, planetary-gear extruders, ring
extruders or cokneaders. It is also possible to use processing
machines provided with at least one gas removal compartment to
which a vacuum can be applied. Suitable extruders and kneaders are
described, for example, in Handbuch der Kunststoffextrusion, Vol.
1, Grundlagen, Editors F. Hensen, W. Knappe, H. Potente, 1989, pp.
3-7, ISBN:3-446-14339-4; and Vol. 2 Extrusions-anlagen 1986, ISBN
3-446-14329-7. For example, the screw length is 1-60 screw
diameters, preferably 35-48 screw diameters. The rotational speed
of the screw is preferably 10 to 600 rotations per minute (rpm),
for example 25-300 rpm. The maximum throughput is dependent on the
screw diameter, the rotational speed and the driving force. The
process of the present invention can also be carried out at a level
lower than maximum throughput by varying the parameters mentioned
or employing weighing machines delivering dosage amounts. If a
plurality of components are added, these can be premixed or added
individually.
[0222] Also of interest is a process for the preparation of a
synthetic polymer nanocomposite material, wherein the melt mixing
of the components (synthetic polymer, filler and dispersing agent
prepared by controlled free radical polymerization) occurs between
120 and 290.degree. C., preferably between 140 and 250.degree. C.,
for example between 170 and 230.degree. C.
[0223] The present invention also relates to synthetic polymer
nanocomposites obtained by the above mentioned process.
[0224] The preferred components (b) and (c), and optionally further
additives, in the process for the preparation of a synthetic
polymer nanocomposite material are the same as those described for
the composition.
[0225] A preferred embodiment of the present invention is also the
use of a dispersing agent prepared by controlled free radical
polymerization to intercalate and exfoliate a filler and disperse
the filler in a synthetic polymer matrix to form a nanocomposite
material.
[0226] The preferred dispersing agent, filler and synthetic
polymer, and optionally further additives, for this use are the
same as those described for the composition.
[0227] The following examples illustrate the invention further.
Parts or percentages relate to weight.
EXAMPLE 1
Preparation of Dispersing Agents by Controlled Free Radical
Polymerization
[0228] The preparation and characterization of block or comb
copolymers by controlled free radical polymerization is disclosed
for example in C. Auschra et al., Progress in Organic Coatings 45,
83-93 (2002). Based on these procedures the following block
copolymers are prepared with the properties disclosed in Table
1.
TABLE-US-00001 TABLE 1 Dispersing agent Block 1 Block 2 (Example)
Block 1 length.sup.1) Block 2 length.sup.2) M.sub.n.sup.3)
M.sub.w/M.sub.n.sup.4) 1a PBA.sup.5) 58 PDMAEA.sup.6) 16 7400 1.44
1b PBA.sup.5) 100 PDMAEA.sup.6) 30 11200 1.55 1c PBMA.sup.7) 66
PDMAEA.sup.6) 25 n.d..sup.8) n.d..sup.8) .sup.1)Average number of
monomer units of the first block. .sup.2)Average number of monomer
units of the second block. .sup.3)Molecular weight obtained from
.sup.1HNMR integration. .sup.4)Polydispersity of polymer obtained
from GPC with THF as solvent. .sup.5)PBA is poly(butyl acrylate).
.sup.6)PDMAEA is poly(dimethylaminoethyl acrylate). .sup.7)PBMA is
poly(butyl methacrylate). .sup.8)n.d. means "not determined".
EXAMPLE 2
Preparation of Polypropylene Nanocomposites in a Batch Mixer Based
on Unmodified Sodium Montmorillonite
[0229] 50 g of polypropylene [Basell KY 6100.RTM.], is blended with
0.25% of Irganox 1010.RTM. (pentaerythritol
tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]) and
0.25% of Irgafos 168.RTM. (tris(2,4-di-tert-butylphenyl)phosphite),
5% of a montmorillonite clay [Cloisite (Na.sup.+).RTM. obtained
from Southern Clay Industries] and 2.5% of a dispersing agent
prepared by controlled free radical polymerisation (CFRP) according
to Table 1 in a plastic cup and then added to a batch mixer
operating at 25 rpm and 180.degree. C., the mixture is then taken
to 50 rpm for 10 minutes. Small scale injection moulding is
performed with a CS-183 MMX Minimax moulder. The mixing chamber is
preheated to 230.degree. C. and the mould is oven heated to
120.degree. C. for one hour prior to injection moulding.
Approximately 5 g of the material is placed in the mixing chamber
and heated for 4 to 5 minutes. A small shot is taken form the
CS-183 MMX Minimax moulder prior to placing the mould in position.
Six tensile bars with the dimensions 18 mm by 5 mm by 0.85 mm are
produced for each of the 5 g material.
[0230] Tensile testing is performed according to ASTM D 638 with a
Rheometrics mini material tensile tester [Minimat 2000.RTM.]
equipped with a 1000 N load cell (40 mm/min). The results are
summarized in Table 2.
TABLE-US-00002 TABLE 2 Normalized d-001 in Modulus of Elongation
Example Dispersing agent .ANG..sup.c) Elasticity.sup.d) at break
(%).sup.e) 2a.sup.a) none (and no filler) -- 1.00 1.00 2b.sup.a)
None 10 1.12 0.97 2c.sup.b) Example 1a 13 1.32 1.30 2d.sup.b)
Example 1b 13 1.04 1.26 2e.sup.b) Example 1c n.d..sup.f)
n.d..sup.f) n.d..sup.f) .sup.a)Comparative Example. .sup.b)Example
according to the invention. .sup.c)Interlayer distance determined
by X-ray diffraction. .sup.d)Normalized modulus of elasticity
relative to polypropylene processed under similar conditions
(=1.0). .sup.e)Normalized elongation at break relative to
polypropylene processed under similar conditions (=1.0).
.sup.f)n.d. means "not determined".
[0231] The X-ray diffraction (XRD) spectra show that all copolymers
synthesized via CFRP according to Table 2 intercalate the used clay
in the direct melt blending experiments in the batch mixer. This is
demonstrated by an increase in d-spacing of from 10.ANG.
(comparative Example 2b) to 13.ANG. (Examples 2c and 2d according
to the invention). The elasticity modulus of samples is enhanced by
4-32% with respect to polypropylene without dispersing agent and/or
filler. Surprisingly, the elongation at break is also enhanced by
26-30%.
EXAMPLE 3
Preparation of Acrylic Block or Gradient Copolymers by RAFT
Polymerization
[0232] a) Preparation of poly(butyl acrylate) (PBA).
[0233] A solution 200 g (1.56 mol) of butyl acrylate, 21.3 g (0.056
mol) of S-dodecyl S'-phenylethyl trithiocarbonate) and 915 mg
(0.0056 mol) of AlBN in 200 ml of dry toluene is degassed by
purging with argon for 3 hours. Polymerization is carried out at
70.degree. C. with stirring under argon for 20 hours (.sup.1H NMR:
conversion 95%; GPC: Mn 3700, Mw/Mn 1.16).
[0234] b) Preparation of poly(butyl acrylate)-block-poly(PEGMEA)
(PBA-b-PPEGMEA).
[0235] A solution of 78.7 g (0.173 mol) of methyl (polyethylene
glycol) monoacrylate (average DP=3.1) and 915 mg (0.0056 mol) of
AlBN in 100 ml of dry toluene is degassed by purging with argon for
3 hours. This solution is added to the above solution [Example 3a]
by syringe. The mixture is stirred at 60.degree. C. under argon for
22 hours. The solvent is removed by evaporation under vacuum.
(viscous yellow oil; .sup.1H NMR: total conversion .about.100%;
GPC: Mn 4400, Mw/Mn 1.15).
[0236] c) Preparation of poly(butyl acrylate)-block-poly(DEGEEA)
(PBA-b-PDEGEEA).
[0237] A solution of 39.2 g (0.208 mol) of di(ethylene glycol)ethyl
ether acrylate and 916 mg (0.0056 mol) of AlBN in 100 ml of dry
toluene is degassed by purging with argon for 3 hours. This
solution was added to the above solution [Example 3a] by syringe.
The mixture is stirred at 60.degree. C. under argon for 48 hours.
The solvent is removed by evaporation under vacuum. (viscous yellow
oil; .sup.1H NMR: total conversion .about.100%; GPC: not available
due to incomplete solubility in THF).
[0238] d) Preparation of poly(MMA-grad-PEGMEA).
[0239] A solution of 240.0 g (2.392 mol) of methyl methacrylate,
60.0 g (0.132 mol) poly(ethylene glycol) methyl ether acrylate,
22.9 g (0.060 mol) of S-dodecyl S'-phenylethyl trithiocarbonate)
and 1.47 g (0.0090 mol) of AlBN in 300 ml of dry toluene is
degassed by purging with argon for 3 hours. The mixture is stirred
at 70.degree. C. under argon for 48 hours. The polymer is collected
by precipitation into methanol. (yellow solid; .sup.1H NMR: total
conversion .about.100%; GPC: Mn 7100, Mw/Mn 1.47).
[0240] e) Preparation of poly(MMA-grad-DEGEEA).
[0241] A solution of 240.0 g (2.392 mol) of methyl methacrylate,
60.0 g (0.319 mol) di(ethylene glycol) ethyl ether acrylate, 22.9 g
(0.060 mol) of S-dodecyl S'-phenylethyl trithiocarbonate) and 985
mg (0.0060 mol) of AlBN in 300 ml of dry toluene is degassed by
purging with argon for 3 hours. The mixture is stirred at
70.degree. C. under argon for 48 hours. The polymer is collected by
precipitation into methanol. (viscous yellow oil; .sup.1H NMR:
total conversion .about.99%; GPC: Mn 5100, Mw/Mn 1.50).
TABLE-US-00003 TABLE 3 Dispersing agent Block 1 Block 2 (Example)
Block 1 length.sup.1) Block 2 length.sup.2) M.sub.n.sup.3)
M.sub.w/M.sub.n.sup.4) 3b PBA.sup.5) 25.2 PPEGMEA.sup.6) 2.8 4400
1.15 3c PBA.sup.5) 28 PDEGEEA.sup.7) 3.1 4600 -- 3d
PMMA-grad-PEGMEA.sup.9) 56.6 -- 7100 1.47 3e
PMMA-grad-DEGEEA.sup.8) 42.5 -- 5100 1.50 .sup.1)Average number of
monomer units of the first block. .sup.2)Average number of monomer
units of the second block. .sup.3)Molecular weight obtained from
.sup.1HNMR integration. .sup.4)Polydispersity of polymer obtained
from GPC with THF as solvent. .sup.5)PBA is poly(butyl acrylate).
.sup.6)PPEGMEA is poly(poly(ethylene glycol) methyl acrylate).
.sup.7)PDEGEEA is poly(diethylene glycol ethyl acrylate).
.sup.8)PMMA-grad-DEGEEA is poly(methyl methacrylate-grad-diethylene
glycol ethyl acrylate) gradient copolymer (weight ratio MMA:DEGEEA
4:1) .sup.9)PMMA-grad-PEGMEA is poly(methyl
methacrylate-grad-[poly(ethylene glycol) methyl acrylate)])
gradient copolymer (weight ratio MMA:PEGMEA 4:1)
EXAMPLE 4
Preparation of Polypropylene Nanocomposites in a Twin Screw
Extruder
[0242] Processing is carried out with a Japan Steel Works 30 mm
diameter twin screw extruder of L/D ratio 42 (JSW TEX 30) that
comprises ten temperature controlled barrel sections each with L/D
of 3.5, three unheated sampling zones with L/D 1.167, and a cooled
feed block with L/D 3.5. The screw configuration consists of a
combination of mixing, kneading and conveying elements familiar to
those skilled in the art. Materials are fed into the extruder via a
JSW TTF20 gravimetric feeder (Feed 1) and a K-Tron KQX gravimetric
feeder (Feed 2). The JSW TEX 30 is operated in a co rotating
(intermeshing self wiping) mode with throughput of 10 kg/hr and a
screw speed of 200 rpm. Vacuum venting is applied to the final
barrel section. The extrudate is cooled in a water filled strand
bath and pelletized.
[0243] In a first step a 10 wt % clay masterbatch is prepared. Feed
1 comprises a dry blend of polypropylene [Basell HP400N.RTM.] and a
stabilizer which is composed of 0.25 wt % of lrganox 1010.RTM.
(pentaerythritol
tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]) and 0.25
wt % of Irgafos 168.RTM. (tris(2,4-di-tert-butylphenyl)phosphite).
Feed 2 comprises a blend of the clay [Cloisite (Na.sup.+).RTM.
obtained from Southern Clay Industries] and the non-ionic
surfactant in the ratio defined in Table 4. All barrel sections are
heated to 170.degree. C.
[0244] In the second step the masterbatch is let down to the
required clay level (see Table 4) by blending the masterbatch (Feed
2) with further polypropylene plus stabilizer (Feed 1). The first
barrel section is heated at 180.degree. C. the remaining barrel
sections are heated at 200.degree. C.
[0245] Injection moulding of the extruded samples are preformed
with a Cincinnati Milacron VS55 28 mm diameter injection moulding
machine comprising four temperature controlled sections of L/D23/1.
The machine is operated at a clamp force of 50 tons and at a
maximum injection pressure of 2005 bar.
[0246] Tensile testing is performed according to ISO 521 using an
Instron 5500R material tensile tester. Tensile properties (vs
polypropylene) for nanocomposite prepared with a ratio of
copolymer:clay of 1:5 are summarized in Tables 4 and 5.
TABLE-US-00004 TABLE 4 Amount Tensile Modulus of Elongation Exam-
of Strength Elasticity at Break ple Cloisite Copolymer (MPa))
(MPa).sup.d) (%) 4a.sup.a) none none 26.3 1470 >800 4b.sup.b) 5%
1% Example 3b 26.9 1560 106 4c.sup.b) 5% 1% Example 3c 26.8 1540
141 4d.sup.b) 5% 1% Example 3d 26.3 1530 34 4e.sup.b) 5% 1% Example
3e 26.5 1590 31 4f.sup.b) 5% 1% Example 1a 26.8 1520 180 4g.sup.b)
5% 1% Example 1c 26.6 1510 140
TABLE-US-00005 TABLE 5 Amount Tensile Modulus of Elongation Exam-
of Strength Elasticity at Break ple Cloisite Copolymer (MPa))
(MPa).sup.d) (%) 5a.sup.a) none none 25.5 1470 >800 5b.sup.b) 1%
1% Example 1a 25.5 1826 49 .sup.a)Comparative Example.
.sup.b)Example according to the invention.
[0247] All examples of Table 4 demonstrate that the mechanical
properties can be improved compared to polypropylene by using
copolymers prepared by controlled radical polymerization according
to the present invention.
* * * * *