U.S. patent application number 10/494408 was filed with the patent office on 2004-12-23 for prestabilization of halogen-containing polymers.
Invention is credited to Friedrich, Hans-Helmut, Kuhn, Karl-Josef.
Application Number | 20040259988 10/494408 |
Document ID | / |
Family ID | 7707879 |
Filed Date | 2004-12-23 |
United States Patent
Application |
20040259988 |
Kind Code |
A1 |
Kuhn, Karl-Josef ; et
al. |
December 23, 2004 |
Prestabilization of halogen-containing polymers
Abstract
The invention relates to a process for preparing a stabilized
suspen-sion/emulsion polymer of halogen-containing monomers with
addition of a polymer stabilizer mixture compatible with the
polymerization medium prior to, during or directly after the
polymerization process, and to the polymers pre-pared by this
process.
Inventors: |
Kuhn, Karl-Josef;
(Lautertal-Gadernheim, DE) ; Friedrich, Hans-Helmut;
(Lautertal-Gadernheim, DE) |
Correspondence
Address: |
Michael P Dilworth
Crompton Corporation
Benson Road
Middlebury
CT
06749
US
|
Family ID: |
7707879 |
Appl. No.: |
10/494408 |
Filed: |
May 3, 2004 |
PCT Filed: |
December 2, 2002 |
PCT NO: |
PCT/EP02/13628 |
Current U.S.
Class: |
524/186 ;
524/402; 524/700; 524/714 |
Current CPC
Class: |
C08K 5/17 20130101; C08K
5/17 20130101; C08L 57/08 20130101; C08K 3/24 20130101 |
Class at
Publication: |
524/186 ;
524/402; 524/700; 524/714 |
International
Class: |
C08L 11/00 |
Foreign Application Data
Date |
Code |
Application Number |
Dec 4, 2001 |
DE |
101 59 344.9 |
Claims
1. A process for preparing a stabilized suspension/emulsion polymer
of halogen-containing monomers comprising adding a polymer thermal
stabilizer mixture compatible with the polymerization medium prior
to, during or directly after the polymerization process prior to
isolation of the polymer.
2. The process of claim 1,--wherein the polymer thermal stabilizer
mixture comprises perchlorate compounds and/or alkanolamines and/or
salts of these.
3. The process of claim 1 wherein the polymer thermal stabilizer
mixture comprises at least a) a perchlorate and/or b) an
alkanolamine of the formula (I) 3where x=1, 2 or 3; y=1, 2, 3, 4, 5
or 6; n=from 1 to 10; R.sup.1 and R.sup.2=independently of one
another H, C.sub.1-C.sub.22-alkyl,
-[--(CHR.sup.3.sub.a).sub.y-CHR.sup.3.sub.b-O--].- sub.n-H,
-[--(CHR.sup.3.sub.a).sub.y-CHR.sup.3.sub.b-O--].sub.n-CO--R.sup.-
4, C.sub.2-C.sub.20-alkenyl, C.sub.2-C.sub.18-acyl,
C.sub.4-C.sub.8-cycloalkyl, where this may have OH substitution in
the .beta.-position, C.sub.6-C.sub.10-aryl,
C.sub.7-C.sub.10-alkaryl or C.sub.7-C.sub.10-aralkyl, or, if x=1,
R.sup.1 and R.sup.2 may also, together with the N, form a closed
ring having from 4 to 10 members, composed of carbon atoms and,
where appropriate, of up to 2 heteroatoms, or if x=2, R.sup.1 may
also be C.sub.2-C.sub.18-alkylene which, at both .beta.-carbon
atoms, may have OH substitution and/or have interruption by one or
more O atoms and/or one or more NR.sup.2 groups, or be
dihydroxy-substituted tetrahydrodicyclopentadienylene,
dihydroxy-substituted ethylcyclohexanylene, dihydroxy-substituted
4,4'-(bisphenol A dipropyl ether)ylene, isophoronylene,
dimethylcyclohexanylene, dicyclohexylmethanylene or
3,3'-dimethyldicyclohexylmethanylene, and if x=3, R.sup.1 may also
be trihydroxy-substituted (tri-N-propyl isocyanurate)triyl;
R.sup.3.sub.a and R.sup.3.sub.b=independently of one another
C.sub.1-C.sub.22-alkyl, C.sub.2-C.sub.6-alkenyl,
C.sub.6-C.sub.10-aryl, H or CH.sub.2--X--R.sup.5, where X.dbd.O, S,
--O--CO-- or --CO--O--; R.sup.4.dbd.C.sub.1-C.sub.18-alkyl/alkenyl
or phenyl; and R.sup.5.dbd.H, C.sub.1-C.sub.22-alkyl,
C.sub.2-C.sub.22-alkenyl or C.sub.6-C.sub.10-aryl, and/or c) the
salts of a) and b).
4. The process of claim 1 wherein the polymer thermal stabilizer
mixture comprises at least a) a perchlorate salt and/or b) a
reaction product of a mono- or polyfunctional epoxide and ammonia
or, respectively, a mono- or polyfunctional dialkyl(aryl)- or
monoalkyl(aryl)amine and/or c) salts of a) and b).
5. The process of claim 4, wherein the polyfunctional epoxide is
dicyclopentadiene dioxide, vinylcyclohexene diepoxide, bishpenol A
diglycidyl ether or trisglycidyl isocyanurate and the dialkylamine
is diethanolamine or diisopropanolamine and the monoalkylamine is
monoethanolamine or monoisopropanolamine.
6. The process of claim 3 wherein the perchlorate salt is a
compound of the formula M(ClO.sub.4).sub.n, where M is H, Li, Na,
K, Mg, Ca, Sr, Ba, Zn, Al, La, Ce or NH.sub.4 and n is either 1, 2
or 3 as required by the valency of M.
7. The process of claim 3 wherein, in the compound having the
general formula (I), R.sup.3.sub.a and R.sup.3.sub.b, independently
of one another, are H or CH.sub.3 and y=1.
8. The process of claim 3 wherein, in the compound having the
general formula (I),
R.sup.1.dbd.R.sup.2.dbd.CH.sub.2--CHR.sub.3--OH.
9. The process of claim 6 wherein, in the perchlorate salt, M=Na or
K and n=1.
10. The process of claim 3 wherein the compounds of the general
formula (I) are selected from the group consisting of
tris(2-hydroxy-1-propyl)ami- ne, tris(2-hydroxy-ethyl)amine,
bis(2-hydroxyethyl)-2-hydroxy-1-propylamin- e,
alkyl/alkenylbis(2-hydroxyethyl)amine,
alkyl/alkenyl(2-hydroxy-1-propyl- )-amine,
N-(2-hydroxyhexadecyl)diethanolamine,-2-hydroxy-3-octyloxypropyl)-
diethanolamine, N-(2-hydroxy-3-decyloxypropyl)diethanolamine, and
mixtures of these.
11. The process of claim 3 wherein the polymer thermal stabilizer
mixture is comprised of from 0.01 to 3.00 parts by weight of sodium
perchlorate and/or from 0 to 8.00 parts by weight of alkanolamines
of the general formula (I) and/or from 0.01 to 5.00 parts by weight
of the salts of a) and b), per hundred parts of polymer.
12. The process of claim 1 further comprising the step of
subsequently stabilizing the polymer using conventional stabilizers
and/or additives.
13. A composition comprising a polymer that has been prepared by
the process of claim 1.
14. A process for manufacturing useful articles comprising
employing halogen-containing polymers prepared according to claim
1.
15. An article of manufacture comprising a thermally stabilized
halogen-containing polymer prepared by the process of claim 1.
Description
[0001] The invention relates to a process for preparing a
stabilized suspension/emulsion polymer of halogen-containing
monomers with addition of a polymer stabilizer mixture compatible
with the polymerization medium prior to, during or directly after
the polymerization process, and to the polymers prepared by this
process.
[0002] Suspension or emulsion homopolymers and copolymers of
halogen-containing monomers have limited thermal stability which
has to be optimized by adding various stabilizer systems or
combinations of these so that the materials can be processed to
give industrially useful final products.
[0003] PVC polymerization may be taken here as an example of the
polymerization of halogen-containing polymers. In PVC
polymerization, the polymer is mostly prepared in aqueous systems
in the form of suspension, microsuspension or emulsion PVC. In this
process, the monomer(s) is/are added to the aqueous polymerization
medium composed of a mixture of polymerization catalyst
(initiator), dispersion systems, agents to prevent adhesion,
(protective) colloids or dispersants, and the polymerization is
carried out. Once the reaction has ended, the polymer formed is
processed by spray drying to give polymer powder or is isolated by
filtration, centrifuging, or similar separation steps, and where
appropriate washed and finally dried at elevated temperatures.
[0004] The drying generally leads to the first thermal stress
placed on the polymer and should therefore in principle be carried
out very gently in order to prevent thermal degradation and
associated discoloration of the vinyl polymer.
[0005] The drying gives a white or near-white fine powder which can
then be treated with other additives, processing aids, and also
heat or light stabilizers and can be processed with heat in the
melt or on rolls or in kneaders, extruders, or other equipment, to
give the desired final products (mouldings, etc.).
[0006] The optimized polymer mixture for the particular application
can only be made available by adding additives, modifiers and/or
other stabilizers of varying type.
[0007] Until now the polymer has always been stabilized only after
its isolation from the aqueous reaction medium of the
polymerization reactor, since there have been no available
stabilizers which are compatible with the polymerization medium or
soluble therein. A polymerization medium based on water is usually
used. The stabilizer systems used hitherto are not only
incompatible or insoluble in the polymerization medium but are also
incompatible or insufficiently compatible with the polymerization
process. This means that they can lead to coagulation (breaking of
the polymer dispersion) or even inhibit the polymerization and thus
lead to yield losses or worse. Attempts to stabilize the polymer
dispersion have therefore hitherto been unsuccessful.
[0008] JP 61-009451 indicates a stabilizer system specifically for
PVC, composed of a combination of ethanolamine and perchloric acid.
This involves perchlorate salts with ammonium salt structure, and
these can be obtained by adding primary, secondary or tertiary
ethanolamines to a perchloric acid solution.
[0009] Ammonium perchlorate salts are generally compounds which are
sensitive to heat and shock and therefore are accompanied by a
certain risk of explosion, making them unsuitable for large-scale
industrial applications in plastics processing. This combination is
used only after polymerization has ended, since the components have
an adverse effect on the polymerization procedure. The molar ratios
in which the components have to be used also severely restrict the
ideal range of use of the stabilizer combination.
[0010] EP 0 281 210 describes a stabilizer system composed of a
homogenized suspension of an antioxidant which is insoluble in the
polymerization mixture and has to be added to the modified
polymerization mixture towards the end of the polymerization of
vinyl chloride, but is not effective against the known ionic
thermal degradation of PVC.
[0011] U.S. Pat. No. 4,252,705 discloses stabilizer systems for
PVC, but these are based on insoluble N,N'-diphenylurea and
severely restrict the scope of application of the resultant
PVC.
[0012] Other additives usually used for post-stabilization of
finished PVC powders cannot be used because of incompatibility or
hydrolytic decomposition.
[0013] For example, the halogen-containing polymer PVC can be
stabilized by a number of additives. Compounds of the heavy metals
lead, barium and cadmium are particularly well suited to this
purpose, but are nowadays subject to criticism on environmental
grounds or due to their heavy metal content; other stabilization
systems based on Ca/Zn or tin or based on organic materials are
also known, but for the reasons mentioned cannot be used for
prestabilization (cf. "Kunststoffadditive" [Plastics additives], R.
Gchter/H. Muller, Carl Hanser Verlag, 3rd edn. 1989, pages 303-311
(see also 4th edition of 2001) and "Kunststoff Handbuch PVC"
[Plastics Handbook PVC], volume 2/1, W. Becker/D. Braun, Carl
Hanser Verlag, 2nd edn., 1985, pages 531-538; and also Kirk-Othmer:
"Encyclopedia of Chemical Technology", 4th ed. 1994, Vol. 12, Heat
Stabilizers, pp. 1071-1091).
[0014] It has now been found that the stabilization of the
halogen-containing polymer can take place while the polymerization
medium is still present, prior to isolation of the polymer from its
mother liquor or prior to breakdown (breaking) of the polymer
dispersion. For the purposes of this invention, the general term
polymerization medium encompasses dispersion systems, colloid
systems, emulsion systems or suspension systems, i.e. various
systems which can arise during polymerization of halogen-containing
monomers. The term polymerization of halogen-containing monomers
also encompasses copolymerization of halogen-containing monomers
with one or more non-halogen-containing monomers or a mixture of
these.
[0015] This means that, even though the reaction medium is mostly
aqueous, stabilization can take place prior to, during and after
the polymerization.
[0016] Surprisingly, this addition of substances foreign to the
polymerization has no adverse effect on the polymerization medium.
Nor is there any adverse effect on polymerization activity and
polymer yield, and indeed in some cases the yields found are
higher.
[0017] The invention therefore provides a process for preparing a
stabilized suspension/emulsion polymer of halogen-containing
monomers with addition of a polymer stabilizer mixture compatible
with the polymerization medium prior to, during or directly after
the polymerization process.
[0018] To this end, the stabilizer system is added to or dissolved
in the polymerization medium by the usual laboratory methods,
directly in the form of a solid or mixture of solids, or in the
form of a solution or dispersion in a suspension medium or,
respectively, solvent compatible with the polymerization medium.
The addition may take place prior to, during, or after the
polymerization. The dispersion medium is then, where appropriate,
separated off and the polymeric product is dried. Commonly used
industrial methods such as filtration, centrifuging, or else
preferably spray drying are used to remove the dispersion medium.
This gives a very intimate mixture of the stabilizer system with
the polymer, and even during the required first drying of the
polymer powder the stabilizer can begin to exert its stabilizing
action and thus prevent thermal degradation during the drying
procedure. In addition, its incorporation into the polymer is more
thorough than in the processes which have been carried out hitherto
and do not bring the stabilizer system into contact with the
polymer until drying is complete. The result of this intimate
contact of the stabilizer system with the polymer is substantially
less initial thermal stress on the polymer for incorporation of the
stabilizer into the polymer network; indeed, this stress can be
avoided completely, since thermal shaping can take place directly
without any further stabilization. Nevertheless, it is also
possible for the identical additional stabilizing materials to be
added subsequently to the resultant polymer powders in the usual
way--if necessary.
[0019] It has been found that stabilizer mixtures which are
compatible with the polymerization medium, i.e. which are
compatible with the dispersion/emulsion systems of the
polymerization and with the polymerization process, can be used in
the process of the invention. In particular, these stabilizer
systems may be systems which are water-soluble and
dispersion-compatible.
[0020] The present invention therefore provides a process for
preparing a stabilized suspension/emulsion polymer of
halogen-containing monomers with addition of a polymer stabilizer
mixture compatible with the polymerization medium prior to, during
or directly after the polymerization process, characterized in that
the polymer stabilizer mixture encompasses at least
[0021] a) a perchlorate and/or
[0022] b) an alkanolamine of the formula (I) 1
[0023] where
[0024] x=1, 2 or 3;
[0025] y=1, 2, 3, 4, 5 or 6;
[0026] n=from 1 to 10;
[0027] R.sup.1,R.sup.2=independently of one another H,
C.sub.1-C.sub.22-alkyl,
-[--(CHR.sup.3.sub.a).sub.y-CHR.sup.3.sub.b-O--].- sub.n-H,
-[--(CHR.sup.3.sub.a).sub.y-CHR.sup.3.sub.b---O--].sub.n-CO--R.su-
p.4, C.sub.2-C.sub.20-alkenyl, C.sub.2-C.sub.18-acyl,
C.sub.4-C.sub.8-cycloalkyl, where this may have OH substitution in
the .beta.-position, C.sub.6-C.sub.10-aryl,
C.sub.7-C.sub.10-alkaryl or C.sub.7-C.sub.10-aralkyl, or, if x=1,
R.sup.1 and R.sup.2 may also, together with the N, form a closed
ring having from 4 to 10 members, composed of carbon atoms and,
where appropriate, of up to 2 heteroatoms, or if x=2, R.sup.1 may
also be C.sub.2-C.sub.18-alkylene which, at both .beta.-carbon
atoms, may have OH substitution and/or have interruption by one or
more O atoms and/or one or more NR.sup.2 groups, or be
dihydroxy-substituted tetrahydrodicyclopentadienylene,
dihydroxy-substituted ethylcyclohexanylene, dihydroxy-substituted
4,4'-(bisphenol A dipropyl ether)ylene, isophoronylene,
dimethylcyclohexanylene, dicyclohexylmethanylene or
3,3'-dimethyldicyclohexylmethanylene, and if x=3, R.sup.1 may also
be trihydroxy-substituted (tri-N-propyl isocyanurate)triyl;
[0028] R.sup.3.sub.a and R.sup.3.sub.b=independently of one another
C.sub.1-C.sub.22-alkyl, C.sub.2-C.sub.6-alkenyl,
C.sub.6-C.sub.10-aryl, H or CH.sub.2--X--R.sup.5, where X.dbd.O, S,
--O--CO--or --CO--O--;
[0029] R.sup.4.dbd.C.sub.1-C.sub.18-alkyl/alkenyl or phenyl;
and
[0030] R.sup.5.dbd.H, C.sub.1-C.sub.22-alkyl,
C.sub.2-C.sub.22-alkenyl or C.sub.6-C.sub.10-aryl, and/or
[0031] c) the salts of a) and b).
[0032] The invention also provides a process which uses stabilizer
mixtures compatible with and/or soluble in the polymerization
medium, encompassing at least
[0033] a) a perchlorate salt and/or
[0034] b) a reaction product of a mono- or polyfunctional epoxide
and ammonia or, respectively, a mono- or polyfunctional
dialkyl(aryl)- or mono-alkyl(aryl)amine and/or
[0035] c) the salts of a) and b).
[0036] Examples of the alkanolamines of the general formula (I) are
compounds where R.sup.1 and R.sup.2=methyl, ethyl, propyl, butyl,
cyclohexyl, octyl, lauryl, tetradecyl, hexadecyl, stearyl, oleyl,
allyl, phenyl or benzyl or hydroxyalkyl and R.sup.3.dbd.H, methyl,
ethyl, propyl or butyl. Preference is given to alkanolamines where
R.sup.1=lauryl, tetradecyl, hexadecyl, stearyl, or oleyl, where
R.sup.2=hydroxyalkyl. It is also possible to use ethoxylates and
propoxylates of triethanol- and triisopropanolamine, and also of
fatty amines of vegetable or animal origin. Preference is given to
trialkanolamines and monoalkyl/alkenyldialkanolamines where
R.sup.3.dbd.H or methyl and y=1, in particular fatty amines which
have been reacted twice with ethylene oxide or with propylene
oxide.
[0037] Other compounds with very good suitability can be found in
the following list.
[0038] Methyl- or dimethylamine reacted once or twice with ethylene
oxide or with propylene oxide.
[0039] Propyl- or dipropylamine reacted once or twice with ethylene
oxide or with propylene oxide.
[0040] Isopropyl- or diisopropylamine reacted once or twice with
ethylene oxide or with propylene oxide.
[0041] Butyl- or dibutylamine reacted once or twice with ethylene
oxide or with propylene oxide.
[0042] Isobutyl- or diisobutylamine reacted once or twice with
ethylene oxide or with propylene oxide.
[0043] Pentyl- or dipentylamine reacted once or twice with ethylene
oxide or with propylene oxide.
[0044] Isopentyl- or diisopentylamine reacted once or twice with
ethylene oxide or with propylene oxide.
[0045] Hexyl- or dihexylamine reacted once or twice with ethylene
oxide or with propylene oxide.
[0046] Isohexyl- or diisohexylamine reacted once or twice with
ethylene oxide or with propylene oxide.
[0047] Heptyl- or diheptylamine reacted once or twice with ethylene
oxide or with propylene oxide.
[0048] Isoheptyl- or diisoheptylamine reacted once or twice with
ethylene oxide or with propylene oxide.
[0049] Octyl- or dioctylamine reacted once or twice with ethylene
oxide or with propylene oxide.
[0050] Isooctyl- or diisooctylamine reacted once or twice with
ethylene oxide or with propylene oxide.
[0051] Nonyl- or dinonylamine reacted once or twice with ethylene
oxide or with propylene oxide.
[0052] Isononyl- or diisononylamine reacted once or twice with
ethylene oxide or with propylene oxide.
[0053] Decyl- or didecylamine reacted once or twice with ethylene
oxide or with propylene oxide.
[0054] Isodecyl- or diisodecylamine reacted once or twice with
ethylene oxide or with propylene oxide.
[0055] Undecyl- or diundecylamine reacted once or twice with
ethylene oxide or with propylene oxide.
[0056] Isoundecyl- or diisoundecylamine reacted once or twice with
ethylene oxide or with propylene oxide.
[0057] Dodecyl- or didodecylamine reacted once or twice with
ethylene oxide or with propylene oxide.
[0058] Isododecyl- or diisododecylamine reacted once or twice with
ethylene oxide or with propylene oxide.
[0059] Tridecyl- or ditridecylamine reacted once or twice with
ethylene oxide or with propylene oxide.
[0060] Isotridecyl- or diisotridecylamine reacted once or twice
with ethylene oxide or with propylene oxide.
[0061] Tetradecyl- or ditetradecylamine reacted once or twice with
ethylene oxide or with propylene oxide.
[0062] Hexadecyl- or dihexadecylamine reacted once or twice with
ethylene oxide or with propylene oxide.
[0063] Octadecyl- or dioctadecylamine reacted once or twice with
ethylene oxide or with propylene oxide.
[0064] Eicosyl- or dieicosylamine reacted once or twice with
ethylene oxide or with propylene oxide.
[0065] Docosyl- or didocosylamine reacted once or twice with
ethylene oxide or with propylene oxide.
[0066] N-Methylbutylamine reacted with ethylene oxide or with
propylene oxide.
[0067] N-Ethylbutylamine reacted with ethylene oxide or with
propylene oxide.
[0068] Allyl- or diallylamine reacted once or twice with ethylene
oxide or with propylene oxide.
[0069] Crotyl- or dicrotylamine reacted once or twice with ethylene
oxide or with propylene oxide.
[0070] Octadecenyl- or dioctadecenylamine reacted once or twice
with ethylene oxide or with propylene oxide.
[0071] Benzyl- or dibenzylamine reacted once or twice with ethylene
oxide or with propylene oxide.
[0072] Cyclohexyl- or dicyclohexylamine reacted once or twice with
ethylene oxide or with propylene oxide.
[0073] N-Methylcyclohexylamine reacted with ethylene oxide or with
propylene oxide.
[0074] N-Ethylcyclohexylamine reacted with ethylene oxide or with
propylene oxide.
[0075] 4-Vinyl-1-cyclohexene diepoxide reacted twice with
diethanol- or diisopropanolamine.
[0076] Dicyclopentadiene diepoxide reacted twice with diethanol- or
diisopropanolamine.
[0077] Bisphenol A diglycidyl ether reacted twice with diethanol-
or diisopropanolamine.
[0078] Trisglycidyl isocyanurate reacted three times with
diethanol- or diisopropanolamine.
[0079] Preference is given to trialkanolamines and
monoalkyl/alkenyldialka- nolamines and alkanolamines where
R.sup.3.sub.a and R.sup.3.sub.b=independently of one another H or
methyl and y=1.
[0080] According to the invention it is also possible to use
compounds of the general formula (I) where x=2, i.e. compounds
which have two hydroxyalkylamino groups per molecule. Examples of
these are N,N,N',N'-tetrakis(2-hydroxyethyl)ethylenediamine,
N,N,N',N'-tetrakis(2-hydroxy-1-propyl)ethylenediamine,
N,N,N',N'-tetrakis(2-hydroxyethyl)propylenediamine and
N,N,N',N'-tetrakis(2-hydroxy-1-propyl)propylenediamine and
N,N,N',N'-tetrakis(2-hydroxyethyl)hexamethylenediamine, preference
being given to four-fold reactions of 1,6-hexamethylene- or
1,8-octamethylenediamine or neopentanediamine with ethylene oxide
or with propylene oxide, or analogous reactions of
bisaminomethylcyclohexane or isophoronediamine or
4,4'-diaminodicyclohexylmethane or
3,3'-dimethyl-4,4'-diaminodicyclohexylmethane.
[0081] According to the invention, it is also possible to use
compounds of the general formula (I) where x=3, i.e. those which
have three hydroxyalkylamino groups per molecule. An example of
these is a reaction product of trisglycidyl isocyanurate with mono-
or diethanolamine or mono- or dipropanolamine.
[0082] The alkanolamines of the general formula (I) are chemicals
which can be purchased or can be prepared by known methods via
N-alkylation of an appropriate amine or ammonia (cf. Kirk-Othmer,
Vol. 2, Alkanolamines).
[0083] Examples of the preferred alkanolamines of the general
formula (I) are tris(2-hydroxyethyl)amine,
tris(2-hydroxy-1-propyl)amine,
bis(2-hydroxyethyl)-2-hydroxy-1-propylamine,
N-n-butyl-N,N-bis(2-hydroxye- thyl)amine,
N,N-bis(n-butyl)-N-(2-hydroxyethyl)amine,
N-(3-n-butyloxy-2-hydroxy-1-propyl)-N,N-bis(2-hydroxy-ethyl)amine,
N-(1,3-dihydroxy-2-hydroxymethyl-2-propyl)-N,N-bis(2-hydroxyethyl)amine,
N,N-bis(2-hydroxyethyl)-N-palmitylamine,
N,N-bis(2-hydroxy-ethyl)-N-oleyl- amine,
N,N-bis(2-hydroxyethyl)-N-stearylamine,
N,N-bis(2-hydroxyethyl)-N-s- tearylamine,
N-(2-hydroxyethyl)morpholine and N-(2,3-dihydroxy-1-propyl)mo-
rpholine, bishydroxyethylpiperazine and
bishydroxyisopropylpiperazine and reaction products of glycidyl
ethers with mono- or dialkylamine or ammonia, and also the
alkanolamines derived therefrom, for example ethanolamine,
diethanolamine, mono- and di-n-propanolamine, and mono- and
diisopropanolamine.
[0084] Particular preference is also given to addition products of
olefins oxides, such as butene oxide, butadiene oxide, hexene
oxide, hexadiene oxide, octene oxide, octadiene oxide, decene
oxide, dodecene oxide, tetradecene oxide, hexadecene oxide,
octadecene oxide, eicosene oxide and docosene oxide, and also to
epoxystearyl alcohol with diethanol- or diisopropanolamine, and
also to other compounds with OH function in the .beta.-position,
for example N-(2-hydroxyhexadecyl)diethanolamine,
N-(2-hydroxy-3-octyl(oxypropyl)diethanolamine,
N-(2-hydroxy-3-decyloxypro- pyl)diethanolamine,
N-(2-hydroxy-3-octyloxypropyl)diethanolamine and
bis-N-(2-hydroxy-3-phenyloxypropyl)ethanolamine.
[0085] This list is given merely by way of example.
[0086] The perchlorates are known to the skilled worker. Examples
are those of the formula M(ClO.sub.4)n, where M is H, Li, Na, K,
Mg, Ca, Sr, Ba, Zn, Al, La, Ce or NH.sub.4; n is 1, 2 or 3 as
required by the valency of M. Aqueous ammonium perchlorate
solutions or aqueous perchloric acid solutions may also be used in
the use of the invention in an aqueous polymerization medium.
[0087] Various commonly used supply forms (formulations) of the
perchlorates may be used here; for example as salt or solution in
water or in an organic solvent. Other examples of these perchlorate
formulations are perchlorates dissolved or complexed using alcohols
(polyols, cyclodextrins) or using ether alcohols or ester alcohols
or crown ethers. Other embodiments are described in EP 0 394 547,
EP 0 457 471 and WO 94/24200.
[0088] It is preferable to use the salts sodium/potassium
perchlorate.
[0089] The prestabilized polymer compositions prepared by these
processes are likewise provided by the invention and feature
intimate mixing, not previously achieved, of the halogen-containing
polymer with the stabilizer system before they have undergone any
thermal stress. The first step hitherto needed of incorporation of
the stabilizer mixture is thus omitted, while the polymer prepared
is directly ready for use. The distribution of the stabilizer
mixture in the polymer here is almost homogeneous. The polymer
compositions of the invention include dispersions of the
prestabilized polymers and the prestabilized polymers in dry
form.
[0090] It is advantageous to use from 0 to 8 parts by weight,
preferably from 0.05 to 5 parts by weight, in particular from 0.1
to 2 parts by weight, of the compounds of the general formula (I)
listed under (b), based on 100 parts by weight of PVC, to achieve
stabilization in the chlorine-containing polymer in these
compositions. The amount used of the perchlorates listed under (a)
may be from 0.01 to 3 parts by weight, particularly preferably from
0.01 to 2 parts by weight, based on 100 parts by weight of PVC.
Finally, use may be made of amounts of from 0.01 to 5 parts by
weight, preferably from 0.1 to 2 parts by weight, of the salts of
a) and b) listed under c).
[0091] The invention also provides a process for preparing
ready-to-use polymer mixtures (compounded materials) in which,
after the prestabilization of the invention, subsequent additional
stabilization of the polymer takes place using conventional
stabilizers and/or additives. The result is ready-to-use polymer
mixtures in which further stabilizers and/or additives were added
to a previously heat-stabilized, prestabilized polymer. These
polymer mixtures, which are also included within the invention,
feature optimized thermal and optical properties, an example being
that the prestabilization has a favourable effect on the starting
colour when the initial thermal stress occurs.
[0092] Examples of stabilizers and/or additives which can be used
in the post-stabilization process are phosphites, polyols and
disaccharide alcohols, glycidyl compounds, hydrotalcites, zeolites
(aluminosilicates of alkali metals or of alkaline earth metals),
fillers, metal soaps, other compounds of alkali metals or of
alkaline earth metals, fillers/pigments, lubricants, plasticizers,
pigments, epoxidized fatty esters, and other epoxy compounds,
antioxidants, UV absorbers, light stabilizers, optical brighteners,
wetting agents, antisettling agents and blowing agents. Examples of
these additional components are listed and illustrated below (cf.
"Handbook of PVC-Formulating" by E. J. Wickson, John Wiley &
Sons, New York 1993).
[0093] Polyols and Disaccharide Alcohols
[0094] Examples of possible compounds of this type are:
[0095] pentaerythritol, dipentaerythritol, tripentaerythritol,
trimethylolethane, bis(trimethylolpropane), polyvinyl alcohol,
bis(trimethylolethane), trimethylolpropane, sugars, sugar alcohols.
Of these, preference is given to the disaccharide alcohols. It is
also possible to use polyol syrups, such as sorbitol syrup,
mannitol syrup and maltitol syrup.
[0096] Examples of the amounts of the polyols used are from 0.01 to
20 parts by weight, advantageously from 0.1 to 20 parts by weight
and in particular from 0.1 to 10 parts by weight, based on 100
parts by weight of PVC.
[0097] Glycidyl Compounds
[0098] These contain the glycidyl group 2
[0099] bonded directly to carbon, oxygen, nitrogen or sulphur
atoms, either where both of R.sub.1 and R.sub.3 are hydrogen,
R.sub.2 is hydrogen or methyl and n=0 or where R.sub.1 and R.sub.3
together are --CH.sub.2--CH.sub.2-- or
--CH.sub.2--CH.sub.2--CH.sub.2--, R.sub.2 then being hydrogen and n
being 0 or 1.
[0100] It is preferable to use glycidyl compounds having two
functional groups. However, it is also possible in principle to use
glycidyl compounds having one, three or more functional groups.
[0101] Use is predominantly made of diglycidyl compounds having
aromatic groups.
[0102] The amounts used of the terminal epoxy compounds are
preferably at least 0.1 part, preferably from 0.1 to 50 parts by
weight, advantageously from 1 to 30 parts by weight and in
particular from 1 to 25 parts by weight, based on 100 parts by
weight of PVC.
[0103] Hydrotalcites
[0104] The chemical composition of these compounds is known to the
skilled worker, e.g. from the patents DE 3 843 581, U.S. Pat. No.
4,000,100, EP 0 062 813 and WO 93/20135. Compounds from the
hydrotalcite series may be described by the following general
formula
[0105] M.sup.2+.sub.1-xM.sup.3+.sub.x(OH).sub.2
(A.sup.b-).sub.x/b.d H.sub.2O,
[0106] where
[0107] M.sup.2+=one or more of the metals selected from the group
consisting of Mg, Ca, Sr, Zn and Sn,
[0108] M.sup.3+=Al or B,
[0109] A.sup.n an anion of valency n,
[0110] b is a number from 1 to 2,
[0111] 0<x<0.5,
[0112] d is a number from 0 to 20.
[0113] Preference is given to compounds with
[0114] A.sup.n=OH.sup.---, ClO.sub.4.sup.-, HCO.sub.3.sup.-,
CH.sub.3COO.sup.-, C.sub.6H.sub.5COO.sup.-, CO.sub.3.sup.2-,
[0115] (CHOHCOO).sub.2.sup.2-, (CH.sub.2COO).sub.2.sup.2-,
CH.sub.3CHOHCOO.sup.-, HPO.sub.3.sup.- or HPO.sub.4.sup.2-.
[0116] Examples of hydrotalcites are
[0117] Al.sub.2O.sub.3.6MgO.CO.sub.2.12H.sub.2O (i),
Mg.sub.4.5Al.sub.2(OH).sub.13.CO.sub.3.3.5H.sub.2O (ii),
[0118] 4MgO.Al.sub.2O.sub.3.CO.sub.2.9H.sub.2O (iii),
4MgO.Al.sub.2O.sub.3.CO.sub.2.6H.sub.2O,
[0119] ZnO.3MgO.Al.sub.2O.sub.3.CO.sub.2.8-9H.sub.2O and
ZnO.3MgO.Al.sub.2O.sub.3.CO.sub.2.5-6H.sub.2O.
[0120] Very particular preference is given to the types Alkamizer
2, Alkamizer P 93-2 (ex Kyowa) and L-CAM (lithium-modified
hydrotalcite ex Fuji). It is preferable to use dehydrated
hydrotalcites.
[0121] Zeolites (Aluminosilicates of Alkali Metals and/or of
Alkaline Earth Metals)
[0122] These may be described by the following general formula
M.sub.x/n[(AlO.sub.2).sub.x(SiO.sub.2).sub.y].wH.sub.2O,
[0123] where n is the charge on the cation M;
[0124] M is an element of the first or second main group, such as
Li, Na, K, Mg, Ca, Sr or Ba;
[0125] y: x is a number from 0.8 to 15, preferably from 0.8 to 1.2;
and
[0126] w is a number from 0 to 300, preferably from 0.5 to 30.
[0127] Examples of zeolites are sodium aluminosilicates of the
formulae
[0128] Na.sub.12Al.sub.12Si.sub.12O.sub.48.27 H.sub.2O [zeolite A],
Na.sub.6Al.sub.6Si.sub.6O.sub.24.2 NaX.7.5 H.sub.2O, X.dbd.OH,
halogen,
[0129] ClO.sub.4 [sodalite]; Na.sub.6Al.sub.6Si.sub.30O.sub.72.24
H.sub.2O; Na.sub.8Al.sub.8Si.sub.40O.sub.96.24 H.sub.2O;
Na.sub.16Al.sub.16Si.sub.24O.sub.80.16 H.sub.2O;
Na.sub.16Al.sub.16Si.sub- .32O.sub.96.16 H.sub.2O;
Na.sub.56Al.sub.56Si.sub.136O.sub.384.250 H.sub.2O [zeolite Y],
[0130] Na.sub.86Al.sub.86Si.sub.106O.sub.384.264 H.sub.2O [zeolite
X];
[0131] or the zeolites which can be prepared by partial or complete
exchange of the Na atoms by Li atoms, K atoms, Mg atoms, Ca atoms,
Sr atoms or Zn atoms, for example
[0132] (Na,K).sub.10Al.sub.10Si.sub.22O.sub.64.20 H.sub.2O;
Ca.sub.4.5Na.sub.3[(AlO.sub.2).sub.12(SiO.sub.2).sub.12].30
H.sub.2O;
[0133] KgNa.sub.3[(AlO.sub.2).sub.12(SiO.sub.2).sub.12].27
H.sub.2O.
[0134] Very particular preference is given to Na zeolite A and Na
zeolite P.
[0135] The hydrotalcites and/or zeolites may be used in amounts of,
for example, 0.1 to 20 parts by weight, expediently 0.1 to 10 parts
by weight and in particular 0.1 to 5 parts by weight, based on 100
parts by weight of halogen-containing polymers.
[0136] Fillers
[0137] Fillers such as calcium carbonate, dolomite, wollastonite,
magnesium oxide, magnesium hydroxide, silicates, china clay, talc,
glass fibres, glass beads, wood flour, mica, metal oxides or metal
hydroxides, carbon black, graphite, rock flour, heavy spar, glass
fibres, talc, kaolin and chalk are used. Preference is given to
chalk (HANDBOOK OF PVC FORMULATING E. J. Wickson, John Wiley &
Sons, Inc., 1993, pp. 393-449) and reinforcing agents (TASCHENBUCH
der Kunststoffadditive [Plastics Additives Handbook], R. Gchter
& H. Muller, Carl Hanser, 1990, pp. 549-615).
[0138] The fillers may be used in amounts of preferably at least
one part by weight, for example 5 to 200 parts by weight,
expediently 5 to 150 parts by weight and in particular from 5 to
100 parts by weight, based on 100 parts by weight of PVC.
Metal Soaps
[0139] Metal soaps are primarily metal carboxylates, preferably of
relatively long-chain carboxylic acids. Well-known examples of
these are stearates and laurates, and also oleates and salts of
relatively short-chain aliphatic or aromatic carboxylic acids, such
as acetic acid, propionic acid, butyric acid, valeric acid,
hexanoic acid, sorbic acid; oxalic acid, malonic acid, succinic
acid, glutaric acid, adipic acid, fumaric acid, citric acid,
benzoic acid, salicylic acid, phthalic acids, hemimellitic acid,
trimellitic acid, pyromellitic acid.
[0140] Metals which should be mentioned are: Li, Na, K, Mg, Ca, Sr,
Ba, Zn, Al, La, Ce and rare earth metals. Use is frequently made of
so-called synergistic mixtures, such as barium/zinc stabilizers,
magnesium/zinc stabilizers, calcium/zinc stabilizers or
calcium/magnesium/zinc stabilizers. The metal soaps may be used
either alone or in mixtures. An overview of common metal soaps is
found in Ullmann's Encyclopedia of Industrial Chemistry, 5th Ed.,
Vol. A16 (1985), pp. 361 et seq.
[0141] The metal soaps or mixtures of these may be used in amounts
of, for example, 0.001 to 10 parts by weight, expediently 0.01 to 8
parts by weight, particularly preferably 0.05 to 5 parts by weight,
based on 100 parts by weight of PVC.
[0142] Alkali Metal and Alkaline Earth Metal Compounds
[0143] For the purposes of the present invention, these are mainly
the carboxylates of the acids described above, but also
corresponding oxides or, respectively, hydroxides or carbonates.
Mixtures of these with organic acids are also possible. Examples
are LiOH, NaOH, KOH, CaO, Ca(OH).sub.2, MgO, Mg(OH).sub.2,
Sr(OH).sub.2, Al(OH).sub.3, CaCO.sub.3 and MgCO.sub.3 (and also
basic carbonates, such as magnesia alba and huntite), and also
fatty-acid salts of Na and of K. In the case of alkaline earth
carboxylates and Zn carboxylates it is also possible to use adducts
of these with MO or M(OH).sub.2 (M=Ca, Mg, Sr or Zn), so-called
"overbased" compounds. In addition to the stabilizers according to
the invention it is preferable to use alkali metal carboxylates,
alkaline earth metal carboxylates and/or aluminium
carboxylates.
[0144] Lubricants
[0145] Examples of possible lubricants are: montan wax, fatty
esters, PE waxes, amide waxes, chloroparaffins, glycerol esters and
alkaline earth metal soaps, and fatty ketones, and also the
lubricants, or combinations of the lubricants, listed in EP 0 259
783. Calcium stearate is preferred.
[0146] Plasticizers
[0147] Examples of organic plasticizers are those from the
following groups:
[0148] A) Phthalates: such as preferably di-2-ethylhexyl,
diisononyl and diisodecyl phthalate, also known by the common
abbreviations DOP (dioctyl phthalate, di-2-ethylhexylphthalate),
DINP (diisononyl phthalate), DIDP (diisodecyl phthalate).
[0149] B) Esters of aliphatic dicarboxylic acids, in particular
esters of adipic, azelaic, and sebacic acid: preferably
di-2-ethylhexyl adipate and diisooctyl adipate.
[0150] C) Trimellitic esters, such as tri-2-ethylhexyl
trimellitate, triisodecyl trimellitate (mixture), triisotridecyl
trimellitate, triisooctyl trimellitate (mixture), and also
tri-C.sub.6-C.sub.8-alkyl, tri-C.sub.6-C.sub.10-alkyl,
tri-C.sub.7-C.sub.9-alkyl and tri-C.sub.9-C.sub.11-alkyl
trimellitate. Common abbreviations are TOTM (trioctyl trimellitate,
tri-2-ethylhexyl trimellitate), TIDTM (triisodecyl trimellitate)
and TTTDTM (triisotridecyl trimellitate).
[0151] D) Epoxy plasticizers: these are primarily epoxidized
unsaturated fatty acids, e.g. epoxidized soybean oil.
[0152] E) Polymeric plasticizers: the commonest starting materials
for preparing polyester plasticizers are: dicarboxylic acids, such
as adipic, phthalic, azelaic or sebacic acid; diols, such as
1,2-propanediol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol,
neopentyl glycol and diethylene glycol.
[0153] F) Phosphoric esters: a definition of these esters is given
in the abovementioned "Taschenbuch der Kunststoffadditive"
["Plastics Additives Handbook"], Chapter 5.9.5, pp. 408-412.
Examples of these phosphoric esters are tributyl phosphate,
tri-2-ethylbutyl phosphate, tri-2-ethylhexyl phosphate,
trichloroethyl phosphate, 2-ethylhexyl diphenyl phosphate, cresyl
diphenyl phosphate, triphenyl phosphate, tricresyl phosphate and
trixylenyl phosphate. Preference is given to tris(2-ethylhexyl)
phosphate and Reofos.RTM. 50 and 95 (Ciba Spezialittenchemie).
[0154] G) Chlorinated hydrocarbons (paraffins)
[0155] H) Hydrocarbons
[0156] I) Monoesters, e.g. butyl oleate, phenoxyethyl oleate,
tetrahydrofurfuryl oleate and alkylsulphonates.
[0157] J) Glycol esters, e.g. diglycol benzoates.
[0158] A definition of these plasticizers and examples for the same
are given in "Kunststoffadditive" ["Plastics Additives"], R.
Gchter/H. Muller, Carl Hanser Verlag, 3rd Ed., 1989, Chapter 5.9.6,
pp. 412-415, and in "PVC Technology", W. V. Titow, 4th Ed.,
Elsevier Publ., 1984, pp. 165-170. It is also possible to use
mixtures of different plasticizers.
[0159] The plasticizers may be used in amounts of, for example, 5
to 20 parts by weight, expediently 10 to 20 parts by weight, based
on 100 parts by weight of PVC. Rigid or semirigid PVC preferably
comprises up to 10%, particularly preferably up to 5%, of
plasticizer, or no plasticizer.
[0160] Pigments
[0161] Suitable substances are known to the skilled worker.
Examples of inorganic pigments are TiO.sub.2, pigments based on
zirconium oxide, BaSO.sub.4, zinc oxide (zinc white) and lithopones
(zinc sulphide/barium sulphate), carbon black, carbon
black-titanium dioxide mixtures, iron oxide pigments,
Sb.sub.2O.sub.3, (Ti,Ba,Sb)O.sub.2, Cr.sub.2O.sub.3, spinels, such
as cobalt blue and cobalt green, Cd(S,Se), ultramarine blue.
Examples of organic pigments are azo pigments, phthalocyanine
pigments, quinacridone pigments, perylene pigments,
diketopyrrolopyrrole pigments and anthraquinone pigments. TiO.sub.2
in micronized form is also preferred. A definition and further
descriptions are found in the "Handbook of PVC Formulating", E. J.
Wickson, John Wiley & Sons, New York, 1993.
[0162] Phosphites
[0163] Organic phosphites are known costabilizers for
chlorine-containing polymers. Examples of these are trioctyl,
tridecyl, tridodecyl, tritridecyl, tripentadecyl, trioleyl,
tristearyl, triphenyl, trilauryl, tricresyl, tris(nonylphenyl),
tris(2,4-tert-butylphenyl) and tricyclohexyl phosphite.
[0164] Other suitable phosphites are various mixed aryl dialkyl or
alkyl diarylphosphites, such as phenyl dioctyl, phenyl didecyl,
phenyl didodecyl, phenyl ditridecyl, phenyl ditetradecyl, phenyl
dipentadecyl, octyl diphenyl, decyl diphenyl, undecyl diphenyl,
dodecyl diphenyl, tridecyl diphenyl, tetradecyl diphenyl,
pentadecyl diphenyl, oleyl diphenyl, stearyl diphenyl and dodecyl
bis(2,4-di-tert-butylphenyl) phosphite. Advantageous use may also
be made of phosphites of various di- or polyols: e.g.
tetraphenyldipropylene glycol diphosphite, poly(dipropylene glycol)
phenyl phosphite, tetraisodecyl dipropylene glycol diphosphite,
tris(dipropylene glycol) phosphite, tetramethylolcyclohexanol decyl
diphosphite, tetramethylolcyclohexanol butoxyethoxyethyl
diphosphite, tetramethylolcyclohexanol nonylphenyl diphosphite,
bis(nonylphenyl) di(trimethylolpropane) diphosphite,
bis(2-butoxyethyl) di(trimethylolpropane) diphosphite,
tris(hydroxyethyl) isocyanurate hexadecyl triphosphite, didecyl
pentaerythrityl diphosphite, distearyl pentaerythrityl diphosphite,
bis(2,4-di-tert-butylphenyl) pentaerythrityl diphosphite, and also
mixtures of these phosphites and aryl/alkyl phosphite mixtures of
empirical composition
(H.sub.19C.sub.9--C.sub.6H.sub.4O).sub.1.5P(OC.sub.12,13H.sub.25,27).sub.-
1.5 or
[C.sub.8H.sub.17--C.sub.6H.sub.4--O--].sub.2P[i-C.sub.8H.sub.17O],
(H.sub.19C.sub.9--C.sub.6H.sub.4O).sub.1.5P(OC.sub.9,11H.sub.19,23).sub.1-
.5.
[0165] Examples of the amounts of the organic phosphites used are
from 0.01 to 10 parts by weight, advantageously from 0.05 to 5
parts by weight and in particular from 0.1 to 3 parts by weight,
based on 100 parts by weight of PVC.
[0166] Epoxidized Fatty Acid Esters and Other Epoxy Compounds
[0167] The stabilizer combination of the invention may additionally
and preferably comprise at least one epoxidized fatty acid ester.
Possible compounds here are especially esters of fatty acids from
natural sources (fatty acid glycerides), such as soya oil or
rapeseed oil. However, it is also possible to use synthetic
products, such as epoxidized butyl oleate. Use may also be made of
epoxidized polybutadiene and polyisoprene, if desired also in a
partially hydroxylated form, or of glycidyl acrylate and glycidyl
methacrylate as homo- or copolymer. These epoxy compounds may also
have been applied to an alumino salt compound; in this connection
see also DE-A-4 031 818.
[0168] Antioxidants
[0169] Alkylated monophenols, e.g.
2,6-di-tert-butyl-4-methylphenol, alkylthiomethylphenols, e.g.
2,4-dioctylthiomethyl-6-tert-butylphenol, alkylated hydroquinones,
e.g. 2,6-di-tert-butyl-4-methoxyphenol, hydroxylated thiodiphenyl
ethers, e.g. 2,2'-thiobis(6-tert-butyl-4-methyl- phenol),
alkylidenebisphenols, e.g. 2,2'-methylenebis(6-tert-butyl-4-methy-
lphenol), benzyl compounds, e.g.
3,5,3',5'-tetratert-butyl-4,4'-di-hydroxy- dibenzyl ether,
hydroxybenzylated malonates, e.g. dioctadecyl
2,2-bis(3,5-di-tert-butyl-2-hydroxybenzyl) malonate, hydroxybenzyl
aromatics, e.g.
1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trime-
thylbenzene, triazine compounds, e.g.
2,4-bis-octylmercapto-6-(3,5-di-tert-
-butyl-4-hydroxyanilino)-1,3,5-triazine, phosphonates and
phosphonites, e.g. dimethyl
2,5-di-tert-butyl-4-hydroxybenzylphosphonate, acylaminophenols,
e.g. 4-hydroxylauranilide, esters of
beta-(3,5-ditert-butyl-4-hydroxyphenyl)propionic acid,
beta-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid,
beta-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid, esters of
3,5-ditert-butyl-4-hydroxyphenylacetic acid with mono- or
polyhydric alcohols, amides of
beta-(3,5-ditert-butyl-4-hydroxyphenyl)propionic acid, for example,
N,N'-bis(3,5-ditert-butyl-4-hydroxyphenylpropionyl)hex-
amethylenediamine, vitamin E (tocopherol) and derivatives.
[0170] Examples of the amounts of the antioxidants used are from
0.01 to 10 parts by weight, advantageously from 0.1 to 10 parts by
weight and in particular from 0.1 to 5 parts by weight, based on
100 parts by weight of PVC.
[0171] UV Absorbers and Light Stabilizers
[0172] Examples of these are: 2-(2'-hydroxyphenyl)benzotriazoles,
such as 2-(2'-hydroxy-5'-methylphenyl)benzotriazole,
2-hydroxybenzophenones, esters of unsubstituted or substituted
benzoic acids, such as 4-tert-butylphenyl salicylate, phenyl
salicylate, acrylates, nickel compounds, oxalamides, such as
4,4'-dioctyloxyoxanilide,
2,2'-dioctyloxy-5,5'-ditert-butyloxanilide,
2-(2-hydroxyphenyl)-1,3,5-tri- azines, such as
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-
, sterically hindered amines, such as
bis(2,2,6,6-tetramethylpiperidin-4-y- l) sebacate,
bis(2,2,6,6-tetra-methylpiperidin-4-yl) succinate.
[0173] Blowing Agents
[0174] Examples of blowing agents are organic azo compounds and
organic hydrazo compounds, tetrazoles, oxazines, isatoic anhydride,
and also soda and sodium bicarbonate. Preference is given to
azodicarbonamide and sodium bicarbonate and also mixtures of
these.
[0175] Definitions for and examples of impact modifiers and
processing aids, gelling agents, antistats, biocides, metal
deactivators, optical brighteners, flame retardants, antifogging
agents and compatibilizers are given in "Kunststoffadditive"
["Plastics Additives"], R. Gchter/H. Muller, Carl Hanser Verlag,
3rd Ed., 1989, and 4th Ed. 2001, and in "Handbook of Polyvinyl
Chloride Formulating" E. J. Wilson, J. Wiley & Sons, 1993, and
also in "Plastics Additives" G. Pritchard, Chapman & Hall,
London, 1st edition, 1998.
[0176] Impact modifiers are also described in detail in "Impact
Modifiers for PVC", J. T. Lutz/D. L. Dunkelberger, John Wiley &
Sons, 1992.
[0177] Examples of the prestabilized chlorine-containing polymers
to be prepared are: polymers of vinyl chloride, of vinylidene
chloride, vinyl resins whose structure contains vinyl chloride
units, for example copolymers of vinyl chloride and vinyl esters of
aliphatic acids, in particular vinyl acetate, copolymers of vinyl
chloride with esters of (meth)acrylic acid and with acrylonitrile,
copolymers of vinyl chloride with diene compounds and with
unsaturated dicarboxylic acids or anhydrides of these, for example
copolymers of vinyl chloride with diethyl maleate, diethyl
fumarate, or maleic anhydride, post-chlorinated polymers and
copolymers of vinyl chloride, copolymers of vinyl chloride and of
vinylidene chloride with unsaturated aldehydes, ketones and other
compounds, for example acrolein, crotonaldehyde, vinyl methyl
ketone, vinyl methyl ether, vinyl isobutyl ether, and the like;
polymers of vinylidene chloride and copolymers of the same with
vinyl chloride and with other polymerizable compounds; polymers of
vinyl chloroacetate and of dichlorodivinyl ether; chlorinated
polymers of vinyl acetate, chlorinated polymeric esters of acrylic
acid and of alpha-substituted acrylic acid; polymers of chlorinated
styrenes, such as dichlorostyrene; chlorinated rubbers; chlorinated
polymers of ethylene; polymers and post-chlorinated polymers of
chlorobutadiene and copolymers of these with vinyl chloride,
chlorinated natural and synthetic rubbers, and mixtures of the
polymers mentioned with each other or with other polymerizable
compounds. For the purposes of this invention, PVC includes
copolymers with polymerizable compounds, such as acrylonitrile,
vinyl acetate, or ABS, and the materials may involve suspension,
bulk or emulsion polymers.
[0178] Preference is given to a PVC homopolymer or a PVC
homopolymer combined with polyacrylates.
[0179] Use may also be made of graft polymers of PVC with EVA, ABS
and MBS. Other preferred substrates are mixtures of the
abovementioned homo- and copolymers, in particular vinyl chloride
homopolymers, with other thermoplastic and/or elastomeric polymers,
in particular blends with ABS, MBS, NBR, SAN, EVA, CPE, MBAS, PMA,
PMMA, EPDM and with polylactones, in particular those from the
group ABS, NBR, NAR, SAN and EVA. The abbreviations used for the
copolymers are familiar to the skilled worker and have the
following meaning: ABS: acrylonitrile-butadienestyrene; SAN:
styrene-acrylonitrile; NBR: acrylonitrile-butadiene; NAR:
acrylonitrile-acrylate; EVA: ethylene-vinyl acetate. Other
particular materials which may be used are acrylate-based
styrene-acrylonitrile copolymers (ASA).
[0180] Polymer compositions which comprise a mixture of from 25 to
75% by weight of PVC and 75 to 25% by weight of the copolymers
mentioned as components (i) and (ii) are preferred here.
Compositions composed of (i) 100 parts by weight of PVC and (ii)
from 0 to 300 parts by weight of ABS and/or SAN-modified ABS and
from 0 to 80 parts by weight of the copolymers NBR, NAR and/or EVA,
PMA, PMMA, but in particular EVA, PMA and PMMA, are a particularly
important component.
[0181] The compounds which may be used concomitantly according to
the invention, and also the chlorine-containing polymers, are well
known to the skilled worker and are described in detail in
"Kunstoffadditive" [Plastics additives], R. Gchter/H. Muller, Carl
Hanser Verlag, 3rd and 4th edn., 1989 and 2001; and in DE 197 41
778 and EP-A 99 105 418.0 of 17.03.1999, expressly incorporated
herein by way of reference.
[0182] The monomers are polymerized by traditional emulsion or
suspension polymerization. More details on the polymerization
process can be found in DE 1 269 350 or EP 0 281 210. The commonly
used polymerization initiators are mostly peroxidic or azo
compounds used as free-radical initiators. Examples of these are:
persulphates, organic and inorganic peroxide salts, hydrogen
peroxide, percarbonates and peresters, benzoyl peroxide, ketone
peroxides, polyester peroxides, polyether peroxides, cyclohexanone
peroxide, methyl ethyl ketone peroxide, cumyl hydroperoxide, diacyl
peroxides, and tert-butyl hydroperoxides. The prestabilization of
the Invention can be used with any of the industrially relevant
processes for polymerization of halogen-containing monomers.
[0183] The stabilizer system is added to or dissolved In the
polymerization medium by the usual laboratory methods, directly in
the form of a solid or mixture of solids, or in the form of a
solution or dispersion in a suspension medium or, respectively,
solvent compatible with the polymerization medium. The addition may
take place prior to, during, or after the polymerization.
[0184] The following methods may be used to incorporate the
stabilizers and/or additives into the prestabilized polymers: an
emulsion or dispersion method (one example being the use of a
mixture which is a paste); a dry mixture method during the mixing
of additional components; a method with direct addition to the
process apparatus (e.g. calender, mixer, kneader, extruder or the
like) or a method involving a solution or melt or what are known as
flakes or pellets in dust-free or one-pack form.
[0185] The ready-to-use polymer mixtures comprising all of the
additives, known as compounded polymer materials, may be prepared
in a manner known per se, and to this end use is made of apparatus
known per se, such as the abovementioned process apparatus, to mix
further stabilizers and/or additives with the prestabilized PVC.
These stabilizers or additives may be added individually or in a
mixture, or else in the form of what are known as
masterbatches.
[0186] The ready-to-use PVC prepared by the present invention may
be brought to the desired form by known methods. Examples of these
processes are milling, calendering, extruding, injection moulding
and spinning, and extrusion with blowing. The stabilized PVC may
also be processed to give foams.
[0187] Examples of uses for which a ready-to-use PVC prepared by
the present invention is particularly suitable are hollow articles
(bottles), packaging films (thermoforming films), blown films,
pipes, foams, heavy profiles (window frames), thin-wall profiles,
construction profiles, films (including Luvitherm), PVC pipes,
profiles, sidings, fittings, office sheeting and apparatus housings
(computers, household devices). The PVC of the invention is
particularly suitable for semirigid and flexible formulations, in
particular in the form of flexible formulations for cable
sheathing, cable insulation, floorcoverings, wallpapers, motor
vehicle components, flexible films, injection mouldings, and hoses,
these being particularly preferred. In the form of semirigid
formulations the PVC of the invention is particularly suitable for
decorative films, foams, agricultural sheeting, hoses, sealing
profiles and office sheeting.
[0188] Examples of the application of the PVC of the invention as a
plastisol are synthetic leather, floorcoverings, textile coatings,
wallpapers, coil coatings and underbody protection for motor
vehicles.
[0189] Examples of sintered PVC applications of the stabilized
ready-to-use PVC of the invention are slush, slush-mould and coil
coatings for plastisol formulations, semirigid formulations and
flexible formulations.
[0190] For more details in this connection see "Kunststoffhandbuch
PVC" [Plastics Handbook PVC], volume 2/2, W. Becker/H. Braun, 2nd
edn., 1985, Carl Hanser Verlag, pages 1236-1277.
[0191] The examples below illustrate the invention but do not limit
the same. As in the remainder of the Description, parts and
percentage data are based on weight.
EXAMPLES
[0192]
1TABLE 1 Stabilizers used Stabilizer Name 1 Triethanolamine + 13%
sodium perchlorate monohydrate 2 Triethanolamine 3 Sodium
perchlorate monohydrate 4 Oleyldiethanolamine + 13% sodium
perchlorate monohydrate 5 Oleyldiethanolamine 6 Triisopropanolamine
+ 13% sodium perchlorate monohydrate 7 Triisopropanolamine 8
Tri-n-octylamine 9 Sodium carbonate 10 Diphenylurea
Example 1
[0193] Preparation of Prestabilized PVC Powder
[0194] A suspension PVC (SPVC) was prepared in a 500 ml stainless
steel autoclave from monomeric vinyl chloride (VCM) by free-radical
polymerization. The process parameters were retained for all of the
experiments:
[0195] temperature: 57.2.degree. C.
[0196] stirring rate: 1 800 rpm
[0197] suspension medium: 2% Methocel F-50
(hydroxypropylmethylcellulose in water, NOXOL (polyvinyl alcohol)
as anticaking agent)
[0198] reaction time: about 210 min
[0199] conversion rate: about 80%.
[0200] Two different initiator systems were used for the
free-radical polymerization.
[0201] Experimental series 1: Esperox 939 M (75% strength solution
of cumyl peroxyneodecanoate)
[0202] Experimental series 2: Espercarb S 840 M (75% strength
solution of di-2-ethylhexyl peroxydicarbonate)
[0203] (both being commercially available initiators from Crompton
for free-radical polymerization processes).
[0204] As shown in Table 2 the initiators were used at 0.1 or 0.12%
by weight, based on VCM.
[0205] The stabilizers listed in Table 1--in each case 0.5% by
weight, based on VCM--were added at various times, either at the
start of the polymerization or once conversion had reached about
80% (at the "end of the reaction").
[0206] Once the polymerization process had ended, the solid polymer
was filtered off, washed and dried to give a fine white powder,
which was tested for thermal stability (DHC, statistical heat test)
and processability (pasting+film production).
[0207] Thermal Stabilization Test/Dehydrochlorination Test
[0208] The PVC powder prepared in this way was subjected to a
dehydrochlorination test (DHC) to DIN 53381 at 180.degree. C. (see
Table 2.0).
[0209] Statistical Heat Test
[0210] 45 g of the "PVC powder"were roll-milled with 15 g of
diisononyl phthalate (DINP), 0.1 g of calcium stearate and 0.15 g
of Loxiol G 71 S (pentaerythrityl adipate=complex ester lubricant)
for 3 minutes at 180.degree. C. Test strips of thickness 0.5 mm
were taken from the resultant PVC sheet and the colour was then
determined via Yellowness Index (YI) to ASTM D1925-70 (see Tab. 2.0
and Tab. 2.1).
2TABLE 2.0 DHC of powder Colour PVC 10 200 (YI value)* powder
Initiator Stab. [.mu.S/cm] [.mu.S/cm] of sheet 1) Esperox 939 M --
14 35 27.39 0.10% by weight 5) Espercarb S 840 M -- 8 27 21.87
0.12% by weight 9) Esperox 939 M 1.sup. 17 42 15.44 0.10% by weight
11) Espercarb S 840 M 1.sup. 30 51 18.32 0.12% by weight 15)
Esperox 939 M 4.sup. 21 53 14.64 0.10% by weight *high values mean
poor starting colour .sup. Addition at start of polymerization
.sup. Addition at end of polymerization
[0211] Experiments 9, 11 and 15 (according to the invention) show
the marked superiority in terms of thermal stability (longer
induction times at 10 and 200 .mu.S/cm) and the better starting
colour of the sheets produced (YI values).
3 TABLE 2.1 Discoloration Discoloration without post- with post-
stabilization stabilization** PVC (YI value)* (YI value)* powder
Description Stab. 5 min 30 min 5 min 30 min Ref. Evipol SH 7020
Without 16 47 7 15 from EVC*** prestab. 15) Esperox 939 4.sup. 6 28
5 7 initiator 0.1% by weight 13) Esperox 939 1.sup. 8 40 5 7
initiator 0.1% by weight *high values mean poor starting colour
**Mark BZ 561 Ba/Zn stabilizer from Crompton Vinyl Additives GmbH
***conventional SPVC from EVC (without prestabilization) .sup.
Addition at start of polymerization .sup. Addition at end of
polymerization
[0212] It is clear that prestabilized PVC grades show marked
advantages when use is made of conventional post-stabilization
systems, and have markedly improved thermal stability even without
post-stabilization.
Example 2
[0213] Preparation of PVC powder 3
[0214] A mixture made from 50 g of an aqueous dispersion composed
of about 50% of solid PVC and 50% of water with additives such as
4-alkylbenzenesulphonic acid derivative/antiblocking
agent/polymerization auxiliary and 0.125 g of a stabilizer as
described in Table 1 was stirred at 80.degree. C. for 60 minutes.
This mixture was then dried in a crystallization dish at about
20.degree. C. (powder 3).
[0215] Dehydrochlorination Test
[0216] The PVC powder thus prepared were then subjected to a
dehydrochlorination test (DHC) to DIN 53381 at 180.degree. C. The
results are seen in Table 3.
4 TABLE 3 DHC 10 [.mu.S/cm] Stabilizer min Without stabilizer 14 1
50 2 44 3 10 4 35 5 25 6 38 7 28 8 16 10 15
[0217] Each of the stabilizer mixtures which may be used according
to the invention shows a marked advantage over the individual
components or absence of stabilizers, this being apparent from the
longer induction times (10 [.mu.S/cm]min).
Example 3
[0218] 20 g of "powder (3)" PVC powder were processed with 20 g of
dioctyl phthalate (DOP) in a dissolver to give a PVC paste and
gelled in a Mathis oven at 190.degree. C. to give a sheet of
thickness 0.5 mm.
[0219] Statistical Heat Test
[0220] The Yellowness Index (YI) of this sheet was then determined
to ASTM D1925-70 (Table 4). Low YI values mean good stabilization
and starting colour.
5 TABLE 4 Stabilizer YI value of sheet Without stabilizer 11.65 1
6.05 2 6.98 3 8.77 4 6.56 5 8.30 6 6.02 7 8.26 8 9.07 9 8.43 10
17.22
[0221] Each of the mixtures 1, 4 and 6 of the invention shows an
improved starting colour (lower YI value) when compared with the
reference 10 known from the literature or with the unstabilized
sheet.
Example 4
[0222] Preparation of PVC powder 4
[0223] A mixture made from 50 g of an aqueous PVC dispersion
composed of about 40% of solid PVC and 60% of water with additions
of sorbitan ester, polymerization auxiliaries, emulsifiers and
0.125 g of a stabilizer as described in Table 1 was stirred at
80.degree. C. for 60 minutes. This mixture was then dried in a
crystallization dish at about 20.degree. C. (PVC powder 4).
[0224] Dehydrochlorination Test
[0225] The PVC powder thus prepared was then subjected to a
dehydrochlorination test (DHC) to DIN 53381 at 180.degree. C.
(Table 5).
6 TABLE 5 DHC 10 [.mu.S/cm] 200 [.mu.S/cm] Stabilizer min min
Without stabilizer 40 51 1 62 78 2 32 38 3 35 47 8 19 26 9 43 49 10
55 69
[0226] It is clearly apparent that, as previously described in
Examples 1 and 3, the stabilizer mixture 1 of the invention is more
effective than the individual components and the stabilizers 9+10
described in the literature, this being apparent from the longer
induction times (10 and 200 [.mu.S/cm]min).
Example 5
[0227] 20 g of "powder (4)" PVC powder prepared as in Example 4
were processed with 20 g of dioctyl phthalate in a dissolver to
give a PVC paste and gelled in a Mathis oven at 190.degree. C. to
give a sheet of thickness 0.5 mm. Test strips of thickness 0.5 mm
were taken from this sheet and heated at 180.degree. C. in the
Mathis oven, and the Yellowness Index (YI) to ASTM D1925-70 was
determined at intervals of 2 minutes.
7TABLE 6 Statistical heat test YI value after Stabilizer 2 min 10
min 24 min Without stabilizer 8.02 16.30 Terminated 1 6.69 10.76
23.57 2* 7.87 28.56 Terminated *pure amine has a "degrading"
action, as described in the literature
[0228] As in Examples 2 and 3, it is again clear that PVC
compositions which have been prepared by the process of the
invention have high stability.
* * * * *