U.S. patent application number 13/059546 was filed with the patent office on 2011-06-16 for silanol condensation catalysts for the cross-linking of filled and unfilled polymer compounds.
This patent application is currently assigned to Evonik Degussa GmbH. Invention is credited to Bastian Bielawski, Aristidis Ioannidis, Kerstin Weissenbach.
Application Number | 20110144278 13/059546 |
Document ID | / |
Family ID | 41056825 |
Filed Date | 2011-06-16 |
United States Patent
Application |
20110144278 |
Kind Code |
A1 |
Weissenbach; Kerstin ; et
al. |
June 16, 2011 |
SILANOL CONDENSATION CATALYSTS FOR THE CROSS-LINKING OF FILLED AND
UNFILLED POLYMER COMPOUNDS
Abstract
The invention relates to a composition of an organofunctional
silane compound, particularly of a mono-unsaturated silane
compound, and of an organic acid or a precursor compound which
releases said organic acid, and to a method for the production of
polymer compounds such as granulates and/or finished products from
thermoplastic base polymers and/or monomers and/or prepolymers of
the thermoplastic base polymer utilizing the composition, the
organic acid, or the precursor compound which releases said organic
acid. The invention also relates to the produced polymers, filled
plastics such as, for example, granulates, finished products,
molded bodies and/or articles such as pipes or cables. In addition,
the invention relates to a kit containing the composition.
Inventors: |
Weissenbach; Kerstin;
(Hillsborough, NJ) ; Ioannidis; Aristidis;
(Rheinfelden, DE) ; Bielawski; Bastian;
(Rheinfelden, GB) |
Assignee: |
Evonik Degussa GmbH
Essen
DE
|
Family ID: |
41056825 |
Appl. No.: |
13/059546 |
Filed: |
July 9, 2009 |
PCT Filed: |
July 9, 2009 |
PCT NO: |
PCT/EP2009/058721 |
371 Date: |
February 17, 2011 |
Current U.S.
Class: |
525/288 ;
502/158 |
Current CPC
Class: |
C08F 230/08 20130101;
C08F 110/02 20130101; C08K 5/5419 20130101; C07F 7/1896
20130101 |
Class at
Publication: |
525/288 ;
502/158 |
International
Class: |
C08F 10/02 20060101
C08F010/02; B01J 31/02 20060101 B01J031/02 |
Foreign Application Data
Date |
Code |
Application Number |
Sep 9, 2008 |
DE |
102008041918.4 |
Claims
1. A composition, comprising: a) at least one silicon-comprising
precursor compound of an organic acid, and/or one organofunctional
silane compound; and, optionally, b) one organic acid, and/or one
silicon-free precursor compound comprising an organic acid.
2. The composition of claim 1, wherein in a), i) the at least one
silicon-comprising precursor compound of an organic acid
corresponds to formula I and/or II
(A).sub.zSiR.sup.2.sub.x(OR.sup.1).sub.4-z-x (I)
(R.sup.1O).sub.3-y-u(R.sup.2).sub.u(A).sub.ySi-A-Si(A).sub.y(R.sup.2).sub-
.u(OR.sup.1).sub.3-y-u (II), wherein mutually independently, z is
0, 1, 2, or 3, x is 0, 1, 2, or 3, y is 0, 1, 2, or 3, and u is 0,
1, 2, or 3, with the proviso that in formula L z+x is smaller than
or equal to (.ltoreq.)3, and, in formula II, y+u is independently
smaller than or equal to (.ltoreq.)2, A is mutually independently
in formula I and/or II a monovalent olefin group, and A in the form
of a divalent moiety in formula II is a divalent olefin group,
R.sup.1 is, mutually independently, a carbonyl-R.sup.3 group, where
R.sup.3 corresponds to a hydrocarbon moiety, having from 1 to 45
carbon atoms, and R.sup.2 corresponds, mutually independently, to a
hydrocarbon group, and/or ii) the organofunctional silane compound
corresponds to an unsaturated alkoxysilane of formula III
(B).sub.bSiR.sup.4.sub.a(OR.sup.5).sub.3-b-a (III), wherein
mutually independently, b is 0, 1, 2, or 3, and a is 0, 1, 2, or 3,
with the proviso that in formula III, b+a is smaller than or equal
to 3, B, mutually independently, is a monovalent
(R.sup.7).sub.2C.dbd.C(R.sup.7)-E.sub.q- group in formula III, in
which R.sup.7 are identical or different, and R.sup.7 is a hydrogen
atom or a methyl group or a phenyl group, E is --CH.sub.2--,
--(CH.sub.2).sub.2--, --(CH.sub.2).sub.3--,
--O(O)C(CH.sub.2).sub.3--, or --C(O)O--(CH.sub.2).sub.3--, q is 0
or 1, or isoprenyl, hexenyl, cyclohexenyl, terpenyl, squalanyl,
squalenyl, polyterpenyl, betulaprenoxy, cis/trans-polyisoprenyl, or
an
R.sup.6-D.sub.p-[C(R.sup.6).dbd.C(R.sup.6)--C(R.sup.6).dbd.C(R.sup.6)].su-
b.t-D.sub.p- group, in which R.sup.6 are identical or different,
and R.sup.6 is a hydrogen atom or an alkyl group having from 1 to 3
carbon atoms, or an aryl group, or an aralkyl group, groups D are
identical or different, and D is --CH.sub.2--,
--(CH.sub.2).sub.2--, --(CH.sub.2).sub.3--,
--O(O)C(CH.sub.2).sub.3--, or --C(O)O--(CH.sub.2).sub.3--, p is 0
or 1, and t is 1 or 2, R.sup.5 is, mutually independently, methyl,
ethyl, n-propyl, or isopropyl, R.sup.4 is, mutually independently,
a substituted or unsubstituted hydrocarbon group.
3. The composition of claim 1, wherein b) is present and, in b),
the at least one organic acid is present and comprises at least one
selected from the group consisting of iii.a) a saturated fatty
acid, and unsaturated fatty acid, a natural amino acid, a synthetic
amino acid, iii.b) an acid-comprising silicon-free precursor
compound, an anhydride, and an ester.
4. The composition of claim 1, further comprising c), at least one
free-radical generator.
5. The composition of claim 4, wherein the at least one
free-radical generator is selected from the group consisting of an
organic peroxide and an organic perester.
6. The composition of claim 1, further comprising d), at least one
selected from the group consisting of a stabilizer and a further
added substance.
7. The composition of claim 1, further comprising e), a
thermoplastic parent polymer, a silane-grafted parent polymer, or a
silane-copolymerized parent polymer, and/or a monomer and/or
prepolymer of said parent polymers, and/or a mixture of these.
8. The composition of claim 1, wherein the silicon-comprising
precursor compound of an organic acid is present and is in a form
that is liquid, waxy, solid, or bound on a carrier material, and/or
the organofunctional silane compound is present and is in a form
that is liquid, highly viscous, waxy, solid, or bound on a carrier
material.
9. A masterkit, comprising the composition of claim 1, comprising:
as component A, 0.1 to 10% by weight, in component A, of the at
least one silicon-comprising precursor compound of an organic acid,
or the at least one organic acid, or the one silicon-free precursor
compound comprising an organic acid, is present, and, making up
100% by weight of component A, one carrier material, one
stabilizer, one added substance, or a mixture of these, and
optionally, as component B, from 60 to 99.9% by weight, in
component B, of the organofunctional silane compound of the formula
III (B).sub.bSiR.sup.4.sub.a(OR.sup.5).sub.3-b-a (III), wherein
mutually independently, b is 0, 1, 2, or 3, and a is 0, 1, 2, or 3,
with the proviso that, in formula III, b+a is smaller than or equal
to (.ltoreq.)3, B, mutually independently, is a monovalent
(R.sup.7).sub.2C.dbd.C(R.sup.7)-E.sub.q- group in formula III, in
which R.sup.7 are identical or different, and R.sup.7 is a hydrogen
atom or a methyl group or a phenyl group, E is --CH.sub.2--,
--(CH.sub.2).sub.2--, --(CH.sub.2).sub.2--, --O(O)C(CH).sub.3--, or
--C(O)O--(CH.sub.2).sub.2--, q is 0 or 1, or isoprenyl, hexenyl,
cyclohexenyl, terpenyl, squalanyl, squalenyl, polyterpenyl,
betulaprenoxy, cis/trans-polyisoprenyl, or an
R.sup.6-D.sub.p-[C(R.sup.6).dbd.C(R.sup.6)--C(R.sup.6).dbd.C(R.sup.6)].su-
b.t-D.sub.p- group, in which R.sup.6 are identical or different,
and R.sup.6 is a hydrogen atom or an alkyl group having from 1 to 3
carbon atoms, or an aryl group, or an aralkyl group, groups D are
identical or different, and D is --CH.sub.2--,
--(CH.sub.2).sub.2--, --(CH.sub.2).sub.3--,
--O(O)C(CH.sub.2).sub.3--, or --C(O)O--(CH.sub.2).sub.3--, p is 0
or 1, and t is 1 or 2, R.sup.5 is, mutually independently, methyl,
ethyl, n-propyl, or isopropyl, R.sup.4 is, mutually independently,
a substituted or unsubstituted hydrocarbon group, and optionally,
from 0.05 to 10% by weight of a free-radical generator and,
optionally, from 0.05 to 10% by weight of at least one stabilizer,
and/or from 0.05 to 99.99% by weight of at least one carrier
material, stabilizer, added substance, or a mixture of these,
summing to a total of 100% by weight in component B.
10. A process for producing a compounded polymer material, the
process comprising: 1) reacting a mixture comprising at least one
thermoplastic parent polymer with a) at least one
silicon-comprising precursor compound of an organic acid and/or one
organofunctional silane compound and, optionally, b) an organic
acid, a silicon-free precursor compound comprising an organic acid,
and a free-radical generator, in a compounding apparatus, or 2)
reacting the mixture, first, with a) the organofunctional silane
compound, and the free-radical generator, to give a material, and
shaping the material subsequently, with addition of the at least
one silicon-comprising precursor compound of an organic acid, the
one silicon-free precursor compound comprising an organic acid,
and/or the one organic acid, to give a second material, and
crosslinking the second material by exposure to moisture, or 3)
reacting the mixture first with a) at least one olefinic
silicon-comprising precursor compound of an organic acid, and the
free-radical generator, to give a material and shaping the material
in a subsequent step, with addition of the at least one
silicon-comprising precursor of an organic acid, the one
silicon-free precursor compound comprising an organic acid, and/or
the one organic acid, to give a second material, and crosslinking
the second material by exposure to moisture, or 4) reacting a
different mixture comprising at least one monomer and/or prepolymer
of the at least one thermoplastic parent polymer with a) the
organofunctional silane compound, and the free-radical generator,
to give a material, and shaping the material, subsequently, with
addition of the at least one silicon-comprising precursor compound
of an organic acid, the one organic acid, and/or the one
silicon-free precursor compound comprising an organic acid, to give
a second material, and then crosslinking the second material with
exposure to moisture.
11. A process for producing a compounded polymer material, the
process comprising 1) reacting a mixture comprising at least one
thermoplastic parent polymer with component B of the masterkit and
component A of the masterkit of claim 9, in a compounding
apparatus, or 2) reacting the mixture first component B of the
masterkit of claim 9, to give a material, and shaping the material
subsequently, with addition of component A of the masterkit of
claim 9, and crosslinking the second material by exposure to
moisture, or 3) reacting a different mixture comprising at least
one monomer and/or prepolymer of the at least one thermoplastic
parent polymer with component B of the masterkit of claim 9, to
give a material, and shaping the material subsequently, with
addition of component A of the masterkit of claim 9, to give a
second material, and then crosslinking the second material by
exposure to moisture, or 4) reacting the mixture with a composition
comprising: a) at least one silicon-comprising precursor compound
of an organic acid, and/or one organofunctional silane compound;
and, optionally, b) one organic acid, and/or one silicon-free
precursor compound comprising an organic acid, or the masterkit of
claim 9, in a monosil process, or 5) reacting the mixture with a
composition comprising: a) at least one silicon-comprising
precursor compound of an organic acid, and/or one organofunctional
silane compound; and, optionally, b) one organic acid, and/or one
silicon-free precursor compound comprising an organic acid, or the
masterkit of claim 9, in a sioplas process, or 6) reacting the
different mixture with a composition comprising: a) at least one
silicon-comprising precursor compound of an organic acid, and/or
one organofunctional silane compound; and, optionally, b) one
organic acid, and/or one silicon-free precursor compound comprising
an organic acid, or the masterkit of claim 9, in a copolymerization
process.
12. The process of claim 1, wherein at least one silane-grafted or
silane-copolymerized, and/or filled or unfilled compounded polymer
material, and/or crosslinked, filled, or crosslinked, unfilled
polymer is produced.
13. A polymer, a compounded polymer material, or an unfilled or
filled plastic, obtained by the process of claim 10.
14. A molding, obtained by the process of claim 10.
15. A polymer kit, comprising: a composition comprising: a) at
least one silicon-comprising precursor compound of an organic acid,
and/or one organofunctional silane compound; and, optionally, b)
one organic acid, and/or one silicon-free precursor compound
comprising an organic acid, and/or the masterkit of claim 9, and
separately therefrom, at least one selected from the group
consisting of a thermoplastic parent polymer, a silane-grafted
parent polymer, a silane-copolymerized parent polymer, a monomer of
the parent polymer, and prepolymer of the parent polymer.
16. (canceled)
17. The composition of claim 3, wherein the ester is present and is
selected from the group consisting of a natural triglyceride, a
synthetic triglyceride, and a phosphoglyceride.
18. The composition of claim 4, wherein the free-radical generator
is at least one selected from the group consisting of tert-butyl
peroxypivalate, tert-butyl 2-ethylperoxyhexanoate, dicumyl
peroxide, di-tert-butyl peroxide, tert-butyl cumyl peroxide,
1,3-di(2-tert-butylperoxyisopropyl)benzene,
2,5-dimethyl-2,5-bis(tert-butylperoxy)hex-3-yne, di-tert-amyl
peroxide, 1,3,5-tris(2-tert-butylperoxyisopropyl)benzene,
1-phenyl-1-tert-butylperoxyphthalide,
alpha,alpha'-bis(tert-butylperoxy)diisopropylbenzene,
2,5-dimethyl-2,5-di-tert-butylperoxyhexane,
1,1-di(tert-butylperoxy)-3,3,5-trimethylcyclohexane, n-butyl
4,4-di(tert-butylperoxy)valerate, ethyl
(3,3-di(tert-butylperoxy)butyrate, and
3,3,6,9,9-hexamethyl-1,2,4,5-tetraoxacyclononane.
19. The masterkit of claim 10, wherein as component A, the at least
one silicon-comprising precursor compound has formula I and/or II
(A).sub.zSiR.sup.2.sub.x(OR.sup.1).sub.4-z-x (I)
(R.sup.1O).sub.3-y-u(R.sup.2).sub.u(A).sub.ySi-A-Si(A).sub.y(R.sup.2).sub-
.u(OR.sup.1).sub.3-y-u (II), wherein mutually independently, z is
0, 1, 2, or 3, x is 0, 1, 2, or 3, y is 0, 1, 2, or 3, and u is 0,
1, 2, or 3, with the proviso that, in formula I, z+x is smaller
than or equal to (.ltoreq.)3, and, in formula II, y+u is
independently smaller than or equal to (.ltoreq.)2, A is mutually
independently in formula I and/or II a monovalent olefin group, and
A in the form of a divalent moiety in formula II is a divalent
olefin group, R.sup.1 is, mutually independently, a
carbonyl-R.sup.3 group, where R.sup.3 corresponds to a hydrocarbon
moiety, having from 1 to 45 carbon atoms, and R.sup.2 corresponds,
mutually independently, to a hydrocarbon group.
20. The composition of claim 3, further comprising: c), at least
one free-radical generator.
21. The composition of claim 3, further comprising: d), at least
one selected from the group consisting of a stabilizer and a
further added substance.
Description
[0001] The invention relates to a composition of an
organofunctional silane compound, in particular of a
monounsaturated silane compound, and of an organic acid, or of a
precursor compound that liberates an acid, and in particular
relates to an olefinic silicon-containing precursor compound of an
organic acid, and also to processes for producing compounded
polymer materials, such as granules and/or finished products, made
of thermoplastic parent polymers, and/or monomers, and/or
prepolymer of the thermoplastic parent polymers, with use of the
composition, of the organic acid, or of the precursor compound that
liberates said acid. The invention further relates to the polymers
produced, to filled plastics, for example in the form of granules,
finished product, moldings, and/or items such as pipes or cables. A
kit comprising the composition is also disclosed.
[0002] It is known that filled and unfilled compounded polymer
materials, in particular polyethylene (PE) and copolymers thereof,
can be produced by using organotin compounds or aromatic sulfonic
acids (Borealis) Ambicat.RTM. as silanol condensation catalysts for
the crosslinking of silane-grafted or silane-copolymerized
polyethylenes. A disadvantage of the organotin compounds is their
significant toxicity, while the sulfonic acids are notable for
their pungent odor, which continues through all stages of the
process into the final product. The compounded polymer materials
crosslinked by sulfonic acids are generally not suitable for use in
the food-and-drinks sector or in the drinking-water-supply sector,
for example for production of drinking-water pipes, because of
reaction byproducts. Dibutyltin dilaurate (DBTDL) and dioctyltin
dilaurate (DOTL) are conventional tin-based silanol condensation
catalysts, and act as catalyst by way of their coordination
sphere.
[0003] It is known that moisture-crosslinkable polymers can be
produced by grafting silanes onto polymer chains in the presence of
free-radical generators, where moisture-crosslinking is carried out
in the presence of the abovementioned silane hydrolysis catalysts
and/or silanol condensation catalysts, after the shaping process.
Moisture-crosslinking of polymers using hydrolyzable unsaturated
silanes is practiced worldwide for the production of cables, pipes,
foams, etc. Processes of this type are known as the sioplas process
(DE 19 63 571 C3, DE 21 51 270 C3, U.S. Pat. No. 3,646,155) and the
monosil process (DE 25 54 525 C3, U.S. Pat. No. 4,117,195). Whereas
the monosil process adds the crosslinking catalyst before the first
step of processing is complete, the sioplas process delays addition
of the crosslinking catalyst to the subsequent step. Another
possibility is to copolymerize vinyl-functional silanes together
with the monomers and/or prepolymers directly to give the parent
polymer, or to couple these subsequently by way of grafting onto
the polymer chains.
[0004] EP 207 627 discloses further tin-containing catalyst systems
and, with these, modified copolymers based on the reaction of
dibutyltin oxide with ethylene-acrylic acid copolymers. JP 58013613
uses Sn(acetyl).sub.2 as catalyst, and JP 05162237 teaches the use
of carboxylates of tin, of zinc, or of cobalt together with
hydrocarbon groups as silanol condensation catalysts, e.g.
dioctyltin maleate, monobutyltin oxide, dimethyloxybutyltin, or
dibutyltin diacetate. JP 3656545 uses zinc and aluminum soaps for
crosslinking, examples being zinc octylate and aluminum laurate. JP
1042509 likewise discloses the use of organic tin compounds for the
crosslinking of silanes, but also discloses alkyl titanic esters
based on titanium chelate compounds. JP09-040713 discloses the
production of silane-modified polyolefins by reacting a polyolefin
and two modified silane compounds with use of an organic acid as
silanol condensation catalyst.
[0005] It is an object of the present invention to develop novel
silane hydrolysis catalysts and/or silanol condensation catalysts
which do not have the above-mentioned disadvantages of the known
catalysts from the prior art, and which can preferably undergo a
homogenization process or dispersion process with silane-grafted,
and/or silane-copolymerized polymers, and/or monomers, or
prepolymers. It is preferable that the silane hydrolysis catalysts
and/or silanol condensation catalysts are waxy to solid, and/or
have been applied to a carrier material.
[0006] The object is achieved via the composition of the invention,
corresponding to the features of claim 1, the masterkit as claimed
in claim 9, and the processes of the invention with the features of
claims 10 and 11, and also by using the products of the invention,
e.g. polymers, compounded polymer materials, products, and the
polymer kit corresponding to the features of claims 13, 14, and 15,
and also by the use as claimed in claim 16. Preferred embodiments
can be found in the dependent claims and in the description.
[0007] Surprisingly, it has been found that the composition which
comprises at least one hydrolyzable precursor compound of an
organic acid, and also, if appropriate, an organofunctional silane
compound, can be reacted in a simple and cost-effective manner with
thermoplastic parent polymers, monomers, and/or prepolymers of the
parent polymers, to give compounded polymer materials, and does not
have the abovementioned disadvantages, such as toxicity and odor
impairment. Another factor, dependent on the composition, is that
there is then overall no liberation of alcohols in the process for
producing compounded polymer materials.
[0008] By way of example, when at least one silicon-containing
precursor compound of an organic acid, for example of the general
formula I, where z=1, 2, or 3, and/or II, where y=0, 1, 2, or 3,
and/or where z=0, and OR.sup.1 corresponds to an unsaturated
carboxylate moiety, is grafted onto a parent polymer, or is
copolymerized with a monomer and/or prepolymer of the parent
polymer, if appropriate in the presence of a free-radical
generator, or is mixed with a corresponding carboxy-substituted
silane-grafted parent polymer and, if appropriate, after the
shaping process a crosslinking process takes place in the presence
of moisture. The grafting process or copolymerization process can
also take place in the presence of an organofunctional silane
compound, an example being an unsaturated alkoxysilane of the
general formula III.
[0009] The invention therefore provides a composition which
comprises, as components of group a), at least one
silicon-containing precursor compound of an organic acid, and/or
one organofunctional silane compound and, if appropriate, as
components of group b), one organic acid, and one silicon-free
precursor compound containing an organic acid, an example being an
alkali-metal or, respectively, alkaline-earth-metal salt of an
organic acid, sodium myristate, magnesium dimyristate, sodium
laurate, magnesium laurate, sodium stearate, magnesium distearate;
or an anhydride or ester, examples being the triglycerides that
occur in fats and in oils.
[0010] Particularly preferred compositions comprise, as components,
at least one organofunctional silane compound and, selected from
the group of the acids or precursor compounds of the acids, at
least one silicon-containing precursor compound of an organic acid,
and/or one organic acid, and/or one silicon-free precursor compound
containing organic acid. By way of example, said preferred
composition can comprise an unsaturated alkoxysilane of the general
formula III, an example being vinylalkoxysilane, and a compound of
the general formula I and/or II, and/or one of the fatty acids
mentioned hereinafter.
[0011] Alternative preferred compositions comprise, from the group
of the acids or precursor compounds of the acids, at least one
silicon-containing precursor compound of an organic acid, and/or
one organic acid, and/or one silicon-free precursor compound at
least two of the compounds mentioned, i.e. of the precursor
compounds or acid and, if appropriate, at least one
organofunctional silane compound.
[0012] One example of these types of compositions is a
silicon-containing precursor compound of an organic acid, an
example being a carboxy-substituted silane, e.g.
vinyltristearylsilane and, as second compound, an organic acid,
such as myristic acid or oleic acid. Another example is a
composition comprising a tetracarboxy-substituted silane, such as
tetramyristylsilane, tetralaurylsilane, tetracaprinylsilane, or
corresponding mixed silanes, or a mixture of the silanes with
myristic acid, capric acid, lauric acid, and/or else behenic
acid.
[0013] Compositions of the invention are suitable for use in a
monosil process or sioplas process with thermoplastic parent
polymers, or in a copolymerization process with monomers and/or
prepolymers of thermoplastic parent polymers.
[0014] Thermoplastic parent polymers for the purposes of the
invention are in particular acrylonitrile-butadiene-styrene (ABS),
polyamides (PA), polymethyl methacrylate (PMMA), polycarbonate
(PC), polyethylene (PE), polypropylene (PP), polystyrene (PS),
polyvinyl chloride (PVC), and also ethylene-vinyl acetate
copolymers (EVA), EPDM, or EPM, which are polymers based on
ethylene units, and/or celluloid, or silane-copolymerized polymers,
and monomers and/or prepolymers are precursor compounds of said
parent polymers, examples being ethylene and propylene. Other
thermoplastic parent polymers are mentioned below.
[0015] In particular, the composition is in essence anhydrous, in
order to suppress any undesired hydrolysis and/or condensation
prior to the actual use in the monosil process or sioplas process,
or cocondensation process.
[0016] The composition comprises, as component of group a), at
least one
[0017] i) silicon-containing precursor compound of an organic acid
of the general formula I and/or II, and/or
[0018] ii) an organofunctional silane compound which corresponds to
an unsaturated alkoxysilane,
[0019] where i) corresponds to the general formula I and/or II
(A).sub.zSiR.sup.2.sub.x(OR.sup.1).sub.4-z-x (I)
(R.sup.1O).sub.3-y-u(R.sup.2).sub.u(A).sub.ySi-A-Si(A).sub.y(R.sup.2).su-
b.u(OR.sup.1).sub.3-y-u (II) [0020] where, mutually independently,
z is 0, 1, 2, or 3, x is 0, 1, 2, or 3, y is 0, 1, 2, or 3, and u
is 0, 1, 2, or 3, with the proviso that in formula I z+x is smaller
than or equal to 3, and in formula II y+u is independently smaller
than or equal to 2, and preference is given to the
tricarboxysilanes of the formula I where z=1, x=0 or, z=0 and x=1,
and/or tetracarboxysilanes where z=0 and x=0, are suitable, as also
are the dicarboxysilanes, where z=1 and x=1, [0021] where A is
mutually independently in formula I and/or II a monovalent olefin
group, particular examples being [0022]
(R.sup.9).sub.2C.dbd.C(R.sup.9)-M.sub.k-, in which R.sup.9 are
identical or different, and R.sup.9 is a hydrogen atom or a methyl
group or a phenyl group, the group M is a group from --CH.sub.2--,
--(CH.sub.2).sub.2--, --(CH.sub.2).sub.3--,
--O(O)C(CH.sub.2).sub.3--, or --C(O)O--(CH.sub.2).sub.3--, k is 0
or 1, examples being vinyl, allyl, 3-methacryloxypropyl, and/or
acryloxypropyl, n-3-pentenyl, n-4-butenyl, or [0023] isoprenyl,
3-pentenyl, hexenyl, cyclohexenyl, terpenyl, squalanyl, squalenyl,
polyterpenyl, betulaprenoxy, cis/trans-polyisoprenyl, or [0024]
R.sup.8--F.sub.g--[C(R.sup.8).dbd.C(R.sup.8)--C(R.sup.8).dbd.C(R.sup.8)].-
sub.r--F.sub.g--, in which R.sup.8 are identical or different, and
R.sup.6 is a hydrogen atom or an alkyl group having from 1 to 3
carbon atoms, or an aryl group, or an aralkyl group, preferably a
methyl group or a phenyl group, groups F are identical or
different, and F is a group from --CH.sub.2--,
--(CH.sub.2).sub.2--, --(CH.sub.2).sub.3--,
--O(O)C(CH.sub.2).sub.3--, or --C(O)O--(CH.sub.2).sub.3--, r is
from 1 to 100, in particular 1 or 2, and g is 0 or 1, [0025] and
where A takes the form of a divalent olefin moiety in formula II,
examples being the corresponding alkenylenes, such as
2-pentenylene, 1,3-butadienylene, iso-3-butenylene, pentenylene,
hexenylene, hexenedienylene, cyclohexenylene, terpenylene,
squalanylene, squalenylene, polyterpenylene,
cis/trans-polyisoprenylene, [0026] R.sup.1 in formula I and/or II
corresponds mutually independently to a carbonyl-R.sup.3 group,
i.e. a --(CO)R.sup.3 group (--(C.dbd.O)--R.sup.3), so that
--OR.sup.1 is --O(CO)R.sup.3, where R.sup.3 corresponds to a
hydrocarbon moiety having from 1 to 45 carbon atoms, in particular
to an unsubstituted or substituted hydrocarbon moiety (HC moiety)
having from 4 to 45 carbon atoms, in particular having from 6 to 45
carbon atoms, preferably having from 6 to 22 carbon atoms,
particularly preferably having from 6 to 14 carbon atoms, with
preference having from 8 to 13 carbon atoms, and in particular to a
linear, branched, and/or cyclic unsubstituted and/or substituted
hydrocarbon moiety, and particularly preferably to a hydrocarbon
moiety of a natural or synthetic fatty acid, and in particular
R.sup.3 in R.sup.1 is, mutually independently, a saturated HC
moiety using --C.sub.nH.sub.2n+1, where n=4 to 45, examples being
--C.sub.4H.sub.9, --C.sub.5H.sub.11, --C.sub.6H.sub.13,
--C.sub.7H.sub.15, --C.sub.8H.sub.17, --C.sub.9H.sub.19,
--C.sub.10H.sub.21, --C.sub.11H.sub.23, --C.sub.12H.sub.25,
--C.sub.13H.sub.27, --C.sub.14H.sub.29, --C.sub.15H.sub.31,
--C.sub.16H.sub.33, --C.sub.17H.sub.35, --C.sub.18H.sub.37,
--C.sub.19H.sub.39, --C.sub.20H.sub.41, --C.sub.21H.sub.43,
--C.sub.22H.sub.45, --C.sub.23H.sub.47, --C.sub.24H.sub.49,
--C.sub.25H.sub.51, --C.sub.26H.sub.53, --C.sub.27H.sub.55,
--C.sub.28H.sub.57, --C.sub.29H.sub.59, or else preferably an
unsaturated HC moiety, examples being --C.sub.10H.sub.19,
--C.sub.15H.sub.29, --C.sub.17H.sub.33, --C.sub.17H.sub.32,
--C.sub.19H.sub.37, --C.sub.21H.sub.41, --C.sub.21H.sub.41,
--C.sub.21H.sub.41, --C.sub.23H.sub.45, --C.sub.17H.sub.31,
--C.sub.17H.sub.29, --C.sub.17H.sub.29, --C.sub.19H.sub.31,
--C.sub.19H.sub.29, --C.sub.21H.sub.33 and/or --C.sub.21H.sub.31.
The composition can likewise use the relatively short-chain HC
moieties R.sup.3, examples being --C.sub.4H.sub.9,
--C.sub.3H.sub.7, --C.sub.2H.sub.5, --CH.sub.3 (acetyl) and/or
R.sup.3.dbd.H (formyl). However, because of the low hydrophobicity
of the HC moieties, the composition is generally based on compounds
of the formula I and/or II in which R.sup.1 is a carbonyl-R.sup.3
group selected from the group of R.sup.3 having an unsubstituted or
substituted hydrocarbon moiety having from 4 to 45 carbon atoms, in
particular having from 6 to 22 carbon atoms, preferably having from
8 to 22 carbon atoms, particularly preferably having from 6 to 14
carbon atoms, or with preference having from 8 to 13 carbon
atoms.
[0027] R.sup.2 is mutually independently a hydrocarbon group, in
particular a substituted or unsubstituted linear, branched, and/or
cyclic alkyl, alkenyl, alkylaryl, alkenylaryl, and/or aryl group
having from 1 to 24 carbon atoms, preferably having from 1 to 18
carbon atoms, and in particular having from 1 to 3 carbon atoms in
the case of alkyl groups. Particularly suitable alkyl groups are
ethyl groups, n-propyl groups, and/or isopropyl groups. Suitable
substituted hydrocarbons are in particular halogenated
hydrocarbons, examples being 3-halopropyl, such as 3-chloropropyl
or 3-bromopropyl groups, where these are, if appropriate,
accessible to nucleophilic substitution or else improve
processability.
[0028] It is therefore preferably also possible to use
silicon-containing precursor compounds of an organic acid of the
general formula I and/or II which correspond to alkyl-substituted
di- or tricarboxysilanes where z=0 and x=1 or 2. Examples here are
methyl-, dimethyl-, ethyl-, or methylethyl-substituted
carboxysilanes based on capric acid, myristic acid, oleic acid, or
lauric acid.
[0029] Carbonyl-R.sup.3 groups are the acid moieties of the organic
carboxylic acids, an example being R.sup.3--(CO)--, where these in
the form of carboxy groups in accordance with the formulae have
bonding to the silicon Si--OR.sup.1, as set out above. The acid
moieties of the formula I and/or II can generally be obtained from
naturally occurring or synthetic fatty acids, examples being the
saturated fatty acids valeric acid (pentanoic acid,
R.sup.3.dbd.C.sub.4H.sub.9), caproic acid (hexanoic acid,
R.sup.3.dbd.C.sub.5H.sub.11), enanthic acid (heptanoic acid,
R.sup.3.dbd.C.sub.6H.sub.13), caprylic acid (octanoic acid,
R.sup.3.dbd.C.sub.7H.sub.15), pelargonic acid (nonanoic acid,
R.sup.3.dbd.C.sub.8H.sub.17), capric acid (decanoic acid,
R.sup.3=C.sub.9H.sub.19), lauric acid (dodecanoic acid,
R.sup.3.dbd.C.sub.9H.sub.19), undecanoic acid
(R.sup.3.dbd.C.sub.10H.sub.23), tridecanoic acid
(R.sup.3.dbd.C.sub.12H.sub.25), myristic acid (tetradecanoic acid,
R.sup.3.dbd.C.sub.13H.sub.27), pentadecanoic acid
(R.sup.3.dbd.C.sub.14H.sub.29), palmitic acid (hexadecanoic acid,
R.sup.3.dbd.C.sub.15H.sub.31), margaric acid (heptadecanoic acid,
R.sup.3.dbd.C.sub.16H.sub.33), stearic acid (octadecanoic acid,
R.sup.3.dbd.C.sub.17H.sub.35) nonadecanoic acid
(R.sup.3.dbd.C.sub.18H.sub.37), arachic acid (eicosanoic/icosanoic
acid, R.sup.3.dbd.C.sub.19H.sub.39), behenic acid (docosanoic acid,
R.sup.3.dbd.C.sub.21H.sub.43) lignoceric acid (tetracosanoic acid,
R.sup.3.dbd.C.sub.23H.sub.47), cerotinic acid (hexacosanoic acid,
R.sup.3.dbd.C.sub.25H.sub.51), montanic acid (octacosanoic acid,
R.sup.3.dbd.C.sub.27H.sub.55), and/or melissic acid (triacontanoic
acid, R.sup.3.dbd.C.sub.29H.sub.59), and also the short-chain
unsaturated fatty acids, such as valeric acid (pentanoic acid,
R.sup.3.dbd.C.sub.4H.sub.9), butyric acid (butanoic acid,
R.sup.3.dbd.C.sub.3H.sub.7), propionic acid (propanoic acid,
R.sup.3.dbd.C.sub.2H.sub.5), acetic acid (R.sup.3.dbd.CH.sub.3),
and/or formic acid (R.sup.3.dbd.H), and can be used as
silicon-containing precursor compound of the formula I and/or II of
the otherwise purely organic silanol condensation catalysts.
[0030] It is however preferable, in the formula I and/or II, to use
fatty acids having a hydrophobic HC moiety, where these are
sufficiently hydrophobic, do not exhibit any unpleasant odor after
liberation, and do not exude from the polymers produced. By way of
example, said exudation restricts the possible use of relatively
high concentrations of stearic acid and palmitic acid. By way of
example, at a concentration above a value as low as about 0.01% by
weight of the liberated stearic acid or palmitic acid, based on the
overall constitution of the polymer, a waxy exudation is observed
on the polymers produced. Preferred acids in the formulae I and/or
II are therefore capric acid, lauric acid, and myristic acid, but
behenic acid can also be used with advantage.
[0031] The naturally occurring or synthetic unsaturated fatty acids
can similarly preferably be converted to the precursor compounds of
the formula I and/or II. They can simultaneously perform two
functions, firstly serving as silanol condensation catalyst, and,
by virtue of their unsaturated hydrocarbon moieties, participating
directly in the free-radical polymerization reaction. Preferred
unsaturated fatty acids are sorbic acid
(R.sup.3.dbd.C.sub.5H.sub.7), undecylenic acid
(R.sup.3.dbd.C.sub.10H.sub.19), palmitoleic acid
(R.sup.3.dbd.C.sub.15H.sub.29), oleic acid
(R.sup.3.dbd.C.sub.17H.sub.33), elaidic acid
(R.sup.3.dbd.C.sub.17H.sub.33), vaccenic acid
(R.sup.3.dbd.C.sub.19H.sub.37), icosenoic acid
(R.sup.3.dbd.C.sub.21H.sub.41), cetoleic acid
(R.sup.3.dbd.C.sub.21H.sub.41), erucic acid
(R.sup.3.dbd.C.sub.21H.sub.41), nervonic acid
(R.sup.3.dbd.C.sub.23H.sub.45), linoleic acid
(R.sup.3.dbd.C.sub.17H.sub.31), alpha-linolenic acid
(R.sup.3.dbd.C.sub.17H.sub.29), gamma-linolenic acid
(R.sup.3.dbd.C.sub.17H.sub.29), arachidonic acid
(R.sup.3.dbd.C.sub.19H.sub.31), timnodonic acid
(R.sup.3.dbd.C.sub.19H.sub.29), clupanodonic acid
(R.sup.3.dbd.C.sub.21H.sub.33), ricinoleic acid
(12-hydroxy-9-octadecenoic acid (R.sup.3.dbd.C.sub.17H.sub.33),
and/or cervonic acid (R.sup.3.dbd.C.sub.21H.sub.31).
[0032] Other advantageous acids from which the precursor compounds
of the formula I and/or II having R.sup.3--COO or R.sup.1O can be
produced are glutaric acid, lactic acid (R.sup.1 being
(CH.sub.3)(HO)CH--), citric acid (R.sup.1 being
HOOCCH.sub.2C(COOH)(OH)CH.sub.2--), vulpinic acid, terephthalic
acid, gluconic acid, and adipic acid, where it is also possible
that all of the carboxy groups have been Si-functionalized, benzoic
acid (R.sup.1 being phenyl), nicotinic acid (vitamin B3, B5).
However, it is also possible to use the natural or synthetic amino
acids, in such a way that R.sup.1 corresponds to appropriate
moieties such as those deriving from tryptophan, L-arginine,
L-histidine, L-phenylalanine, or L-leucine, where L-leucine can be
used with preference. It is also correspondingly possible to use
the corresponding D-amino acids or a mixture of L- and D-amino
acids, or an acid such as D[(CH.sub.2).sub.d)COOH].sub.3, where
D=N, P, and d is from 1 to 12, preferably 1, 2, 3, 4, 5, or 6,
where the hydroxy group of each carboxylic acid function can
independently have been Si-functionalized.
[0033] The composition can therefore also comprise corresponding
compounds of the formula I and/or II based on moieties of said
acids.
[0034] The silicon-containing precursor compound of an organic acid
is in particular active in hydrolyzed form as silane hydrolysis
catalyst and/or silane condensation catalyst, and is also itself
suitable in hydrolyzed or nonhydrolyzed form for grafting on a
polymer and/or copolymerization with a parent polymer,
polymer/monomer, or prepolymer. In hydrolyzed form, the silanol
compound formed contributes to crosslinking by means of resultant
Si--O--Si siloxane bridges during the condensation reaction. Said
crosslinking can use other silanols, siloxanes, or can generally
use functional groups which are present on substrates, on fillers,
and/or on carrier materials and which are suitable for the
crosslinking reaction. Preferred fillers and/or carrier materials
are therefore aluminum hydroxides, magnesium hydroxides, fumed
silica, precipitated silica, silicates, and also other fillers and
carrier materials mentioned below.
[0035] Very particularly preferably the inventive composition
comprises, as component (i) in group a), vinylsilane trimyristate,
vinylsilane trilaurate, vinylsilane tricaprate, or else
corresponding allylsilane compounds of the abovementioned acids,
and/or silane tetracarboxylates Si(OR.sup.1).sub.4, examples being
silane tetramyristate, silane tetralaurate, and silane
tetra-caprate, and it can also be advantageous to add a certain
amount of vinylsilane tristearate, vinylsilane tripalmitate,
allylsilane tristearate, and/or allylsilane tripalmitate. The
amounts used of silane stearates and/or silane palmitates should
preferably be such that no more than 1.0% by weight, preferably
from 0.001% by weight to 0.8% by weight, in particular from 0.01%
to 0.6% by weight, of liberated acid, such as stearic acid or
palmitic acid, is present in the overall constitution in % by
weight of the resultant compounded polymer material or polymer. A
corresponding limit also applies when adding free stearic and/or
palmitic acid.
[0036] Particular preference is always given to those compounds of
group a) and/or b) in which the organic acid has at least one
hydrophobic group which permits solvation or dispersibility in
respect of the plastic. These are in particular long-chain,
branched or cyclic, nonpolar, in particular unsubstituted
hydrocarbon moieties, in particular having from 6 to 22 carbon
atoms, preferably having from 8 to 14 carbon atoms, particularly
preferably having from 8 to 13 carbon atoms, having at least one
carboxylic acid group. Preferred substituted hydrocarbon moieties
that can be used are halogen-substituted HC moieties.
[0037] As indicated above, the composition comprises, as component
of group a), at least one i) silicon-containing precursor compound
of an organic acid of the general formula I and/or II, and/or
[0038] ii) one organofunctional silane compound which corresponds
to an unsaturated or olefinic alkoxysilane, where the silane
compound ii) particularly preferably corresponds to a
monounsaturated alkoxysilane.
[0039] For the purposes of the present invention, the
organofunctional silane compound is particularly suitable for
grafting on a polymer and/or for copolymerization with a monomer,
prepolymer, or parent polymer, and subsequent
moisture-crosslinking. For the purposes of the present invention,
it is preferable that the silicon-containing precursor compound I
and/or II is also suitable for grafting on a polymer and/or
copolymerization with a monomer, prepolymer, or parent polymer, and
subsequent moisture-crosslinking.
[0040] The production of the carboxysilanes has long been known to
the person skilled in the art. By way of example, U.S. Pat. No.
4,028,391 discloses processes for their production in which
chlorosilanes are reacted with fatty acids in pentane. U.S. Pat.
No. 2,537,073 discloses another process. The acid can, for example,
be heated directly in a nonpolar solvent, such as pentane, with
trichlorosilane or with a functionalized trichlorosilane, at
reflux, to give the carboxysilane. In an example for production of
tetracarboxysilanes, tetrachlorosilane is reacted with the
corresponding acid in a suitable solvent (Zeitschrift fur Chemie
(1963), 3(12), 475-6). Other processes relate to the reaction of
the salts or anhydrates of the acids with tetrachlorosilane or with
functionalized trichlorosilanes.
[0041] As organofunctional silane compound ii) of group a) it is in
particular possible to use a compound corresponding to the general
formula III,
(B).sub.bSiR.sup.4.sub.a(OR.sup.5).sub.3-b-a (III) [0042] where,
mutually independently, b is 0, 1, 2, or 3, and a is 0, 1, 2, or 3,
with the proviso that in formula III a +b is smaller than or equal
to 3, [0043] where B, mutually independently, is a monovalent
(R.sup.7).sub.2C.dbd.C(R.sup.7)-E.sub.q- group in formula III, in
which R.sup.7 are identical or different, and R.sup.7 is a hydrogen
atom or a methyl group or a phenyl group, the group E is a group
from --CH.sub.2--, --(CH.sub.2).sub.2--, --(CH.sub.2).sub.3--,
--O(O)C(CH.sub.2).sub.3--, or --C(O)O--(CH.sub.2).sub.3--, q is 0
or 1, examples being vinyl, allyl, n-3-pentyl, n-4-butenyl,
3-methacryloxypropyl, and/or acryloxypropyl, or isoprenyl, hexenyl,
cyclohexenyl, terpenyl, squalanyl, squalenyl, polyterpenyl,
betulaprenoxy, cis/trans-polyisoprenyl, or B comprises an olefin
group, for example
R.sup.6-D.sub.p-[C(R.sup.6).dbd.C(R.sup.6)--C(R.sup.6).dbd.C(R.sup.6)].su-
b.t-D.sub.p-, in which R.sup.6 are identical or different, and
R.sup.6 is a hydrogen atom or an alkyl group having from 1 to 3
carbon atoms, or an aryl group, or an aralkyl group, preferably a
methyl group or a phenyl group, the groups D are identical or
different, and D is a group from --CH.sub.2--,
--(CH.sub.2).sub.2--, --(CH.sub.2).sub.3--,
--O(O)C(CH.sub.2).sub.3--, or --C(O)O--(CH.sub.2).sub.3--, and p is
0 or 1, and t is 1 or 2. [0044] R.sup.5 is, mutually independently,
methyl, ethyl, n-propyl, or isopropyl, [0045] R.sup.4 is, mutually
independently, a substituted or unsubstituted hydrocarbon group, in
particular a substituted or unsubstituted linear, branched, and/or
cyclic alkyl, alkenyl, alkylaryl, alkenylaryl, and/or aryl group
having from 1 to 24 carbon atoms, in particular having from 1 to 16
carbon atoms, preferably having from 1 to 8 carbon atoms. In
particular, the substituted groups are hydrophobic. [0046] A
particularly suitable alkyl group is an ethyl, n-propyl, isopropyl,
n-butyl, isobutyl, cyclohexyl, n-octyl, isooctyl, or hexadecyl
group, and a particularly suitable substituted alkyl group is a
haloalkyl group having chlorine substituents or bromine
substituents, preference being given to haloalkyl groups suitable
for nucleophilic substitution, examples being 3-chloropropyl groups
or 3-bromopropyl groups.
[0047] In particular if the composition has no components of group
b), it is particularly preferable that B comprises at least one
olefin group, an example being polyethylene, polypropylene,
propylene copolymer, or ethylene copolymer, if appropriate together
with a free-radical generator and with other stabilizers and/or
additives.
[0048] It is very particularly preferable that the inventive
composition comprises, as component (ii), vinyltrimethoxysilane,
vinyltriethoxysilane, vinylmethyldialkoxysilane,
vinyltriethoxymethoxysilane (VTMOEO), vinyltriisopropoxysilane,
vinyltri-n-butoxysilane, 3-methacryloxypropyltriethoxysilane,
3-methacryloxypropyltrimethoxysilane (MEMO), and/or
vinylethoxydimethoxysilane, and/or allylalkoxysilanes, such as
allyltriethoxysilane, or unsaturated siloxanes, preferred examples
being oligomeric vinylsiloxanes, or a mixture of the abovementioned
compounds. Preferred organofunctional silane compounds contain
either a vinyl group or methacrylic group, since these compounds
are reactive toward free radicals and are suitable for grafting
onto a polymer chain or for copolymerization with monomers or with
prepolymers.
[0049] The form taken by the composition is usually liquid.
However, it is preferable, for greater ease of metering, that the
composition is provided in the form of solid, flowable formulation,
for example on a carrier material and/or filler. The carrier can be
porous, particulate, swellable or, if appropriate, take the form of
a foam. Suitable carrier materials are in particular polyolefins,
such as PE, PP, EVA, or polymer blends, and suitable fillers are in
particular inorganic or mineral fillers which can advantageously
have reinforcing, extending, or else flame-retardant effect. The
carrier materials and fillers are specified in more detail
below.
[0050] In one preferred embodiment, the composition is composed of
a selection i) of a precursor compound of the formula I and/or II,
and/or ii) of a monounsaturated alkoxysilane, and/or of an organic
acid, and/or of a free-radical generator and also, if appropriate,
of at least one stabilizer and/or additional substance, and/or a
mixture of these.
[0051] In another preferred embodiment, the composition is composed
of a selection i) of a precursor compound of the formula I and/or
II, where R.sup.1 corresponds to a carbonyl-R.sup.3 group where
R.sup.3 is from 4 to 45 carbon atoms, preferably having from 6 to
45 carbon atoms, in particular having from 6 to 22 carbon atoms,
preferably having from 8 to 22 carbon atoms, particularly
preferably having from 6 to 14 carbon atoms, with particular
preference where R.sup.3 is from 8 to 13 carbon atoms, in
particular where R.sup.3 is from 11 to 13 carbon atoms, and/or ii)
of an olefinic alkoxysilane, and/or of a free-radical generator,
and also, if appropriate, of at least one stabilizer and/or
additional substance, and/or a mixture of these.
[0052] In alternative preferred embodiments, the composition is
composed of a selection i) of a precursor compound of the formula I
and/or II, in particular where R.sup.1 corresponds to a
carbonyl-R.sup.3 group where R.sup.3 is from 4 to 45 carbon atoms,
preferably having from 6 to 45 carbon atoms, in particular having
from 6 to 22 carbon atoms, preferably having from 8 to 22 carbon
atoms, particularly preferably having from 6 to 14 carbon atoms,
with particular preference where R.sup.3 is from 11 to carbon
atoms, and/or ii) of an olefinic alkoxysilane, and also, if
appropriate, of at least one stabilizer and/or additional
substance, and/or a mixture of these.
[0053] As at least one organic acid can comprise as components in
group b): [0054] iii.a) a saturated and/or unsaturated fatty acid
(naturally occurring or synthetic) [0055] an example being valeric
acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid,
capric acid, lauric acid, undecanoic acid, tridecanoic acid,
myristic acid, pentadecanoic acid, palmitic acid, margaric acid,
stearic acid, nonadecanoic acid, arachic acid, behenic acid,
lignoceric acid, cerotinic acid, montanic acid, melissic acid,
valeric acid, butyric acid, propionic acid, acetic acid, formic
acid, undecylenic acid, palmitoleic acid, oleic acid, elaidic acid,
vaccenic acid, icosenoic acid, cetoleic acid, erucic acid, nervonic
acid, linoleic acid, alpha-linolenic acid, gamma-linolenic acid,
arachidonic acid, timnodonic acid, clupanodonic acid, cervonic
acid, lignoceric acid (H.sub.3C--(CH.sub.2).sub.22--COOH),
cerotinic acid, lactic acid, citric acid, benzoic acid, nicotinic
acid, arachidonic acid (5,8,11,14-eicosatetraenoic acid,
C.sub.20H.sub.32O.sub.2), erucic acid (cis-13-docosenoic acid,
H.sub.3C--(CH.sub.2).sub.7--CH.dbd.CH--(CH.sub.2).sub.11--COOH),
gluconic acid, icosenoic acid
(H.sub.3C--(CH.sub.2).sub.7--CH.dbd.CH--(CH.sub.2).sub.9--COOH),
ricinoleic acid (12-hydroxy-9-octadecenoic acid), sorbic acid
(C.sub.6H.sub.8O.sub.2), and/or naturally occurring or else
synthetic amino acids, such as tryptophan, L-arginine, L-histidine,
L-phenylalanine, or L-leucine, where L-leucine is preferred, a
dicarboxylic acid, such as adipic acid, glutaric acid, terephthalic
acid (benzene-1,4-dicarboxylic acid), where lauric acid and
myristic acid are preferred, or an acid such as
D[(CH.sub.2).sub.d)COOH].sub.3, where D=N, P, and n=1 to 12,
preferably 1, 2, 3, 4, 5, or 6,
[0056] and/or as [0057] iii.b) an acid-containing silicon-free
precursor compound, an example being an organic anhydride or an
ester, in particular of the abovementioned acids, or else natural
or synthetic triglycerides and/or phosphoglycerides.
[0058] In general terms, the acids having relatively long
hydrophobic hydrocarbon moieties, beginning with valeric acid, and
preferably capric acid, lauric acid, and/or myristic acid, have
good suitability as silanol condensation catalyst. The less
hydrophobic acids are regarded merely as useful for the reaction
with thermoplastic hydrophobic polymers, examples being propionic
acid, acetic acid, and formic acid. Correspondingly, the fatty
acids that have strong odors, for example butyric acid and caprylic
acid are also only useful or have low to zero suitability for use
in a composition, masterkit, polymer kit, or a process of the
invention, because of the pungent odor. This is particularly
applicable when the resultant polymers or compounded polymer
materials are intended for further use in the production of
drinking-water pipes.
[0059] Organic acids are carboxylic acids which have no sulfate
groups or sulfonic acid groups, and in particular they are organic
acids corresponding to R.sup.3--COOH; the anhydrides, esters, or
salts of these organic acids can also be regarded as silicon-free
precursor compound, and they particularly preferably have a
long-chain, nonpolar, in particular substituted or unsubstituted
hydrocarbon moiety, where the hydrocarbon moiety can be saturated
or unsaturated, for example where R.sup.3 is from 1 to 45 carbon
atoms, in particular having from 4 to 45 carbon atoms, preferably
having from 8 to 45 carbon atoms, in particular having from 6 to 22
carbon atoms, preferably having from 8 to 22 carbon atoms,
particularly preferably having from 6 to 14 carbon atoms, with
particular preference where R.sup.3 is from 8 to 13 carbon atoms,
where particular preference is given to R.sup.3 being from 11 to 13
carbon atoms; an example of these materials is lauric acid or
myristic acid; or hydrogen (R.sup.3) and at least one carboxylic
acid group (COOH). Materials explicitly excluded from the
definition of the organic acids are organic arylsulfonic acids,
such as sulfophthalic acid, and also naphthalenedisulfonic
acids.
[0060] Marked preference is therefore given to those acids having
long-chain, hydrophobic hydrocarbon moieties. These acids can also
function as dispersing agents and/or processing aids. In general
terms, the acids that can be used in the form of organic acids as
silanol condensation catalyst comprise the naturally occurring or
synthetic fatty acids, examples being the following saturated fatty
acids: valeric acid (pentanoic acid, R.sup.3.dbd.C.sub.4H.sub.9),
caproic acid (hexanoic acid, R.sup.3.dbd.C.sub.5H.sub.11), enanthic
acid (heptanoic acid, R.sup.3.dbd.C.sub.6H.sub.13), caprylic acid
(octanoic acid, R.sup.3.dbd.C.sub.7H.sub.15), pelargonic acid
(nonanoic acid, R.sup.3.dbd.C.sub.8H.sub.17), capric acid (decanoic
acid, R.sup.3.dbd.C.sub.9H.sub.19), undecanoic acid
(R.sup.3.dbd.C.sub.10H.sub.23), tridecanoic acid
(R.sup.3.dbd.C.sub.12H.sub.25), lauric acid (dodecanoic acid,
R.sup.3.dbd.C.sub.9H.sub.19), myristic acid (tetradecanoic acid,
R.sup.3.dbd.C.sub.13H.sub.27), pentadecanoic acid
(R.sup.3.dbd.C.sub.14H.sub.29), palmitic acid (hexadecanoic acid,
R.sup.3.dbd.C.sub.15H.sub.31), margaric acid (heptadecanoic acid,
R.sup.3.dbd.C.sub.1614.sub.33), stearic acid (octadecanoic acid,
R.sup.3.dbd.C.sub.17H.sub.35), nonadecanoic acid
(R.sup.3.dbd.C.sub.18H.sub.37), arachic acid (eicosanoic/icosanoic
acid, R.sup.3.dbd.C.sub.19H.sub.39), behenic acid (docosanoic acid,
R.sup.3.dbd.C.sub.2114.sub.43), lignoceric acid (tetra-cosanoic
acid, R.sup.3.dbd.C.sub.23H.sub.47), cerotinic acid (hexacosanoic
acid, R.sup.3.dbd.C.sub.25H.sub.51), montanic acid (octacosanoic
acid, R.sup.3.dbd.C.sub.27H.sub.55), and/or melissic acid
(triacontanoic acid, R.sup.3.dbd.C.sub.29H.sub.59), and also the
short-chain unsaturated fatty acids, such as valeric acid
(pentanoic acid, R.sup.3.dbd.C.sub.4H.sub.9), butyric acid
(butanoic acid, R.sup.3.dbd.C.sub.3H.sub.7), propionic acid
(propanoic acid, R.sup.3.dbd.C.sub.2H.sub.5), acetic acid
(R.sup.3.dbd.CH.sub.3), and/or formic acid (R.sup.3.dbd.H), where
the short-chain fatty acids mentioned are not suitable as
dispersing agents and/or processing aids and can therefore be
omitted in preferred compositions. Lauric acid and/or myristic acid
are particularly preferred.
[0061] Similarly preferred is the use of naturally occurring or
synthetic unsaturated fatty acids which can perform two functions,
firstly serving as silanol condensation catalyst, and, by virtue of
their unsaturated hydrocarbon moieties, being capable of
participating directly in the free-radical polymerization reaction.
Preferred unsaturated fatty acids are sorbic acid
(R.sup.3.dbd.C.sub.5H.sub.7), undecylenic acid
(R.sup.3.dbd.C.sub.10H.sub.19), palmitoleic acid
(R.sup.3.dbd.C.sub.15H.sub.29), oleic acid
(R.sup.3.dbd.C.sub.17H.sub.33), elaidic acid
(R.sup.3.dbd.C.sub.17H.sub.33), vaccenic acid
(R.sup.3.dbd.C.sub.19H.sub.37), icosenoic acid
(R.sup.3.dbd.C.sub.21H.sub.41;
(H.sub.3C--(CH.sub.2).sub.7--CH.dbd.CH--(CH.sub.2).sub.9--COOH)),
cetoleic acid (R.sup.3.dbd.C.sub.21H.sub.41), erucic acid
(R.sup.3.dbd.C.sub.21H.sub.41; cis-13-docosenoic acid,
H.sub.3C--(CH.sub.2).sub.7--CH.dbd.CH--(CH.sub.2).sub.11--COOH),
nervonic acid (R.sup.3.dbd.C.sub.23H.sub.45), linoleic acid
(R.sup.3.dbd.C.sub.17H.sub.31), alpha-linolenic acid
(R.sup.3.dbd.C.sub.17H.sub.29), gamma-linolenic acid
(R.sup.3.dbd.C.sub.17H.sub.29), arachidonic acid
(R.sup.3.dbd.C.sub.19H.sub.31, 5,8,11,14-eicosatetraenoic acid,
C.sub.20H.sub.32O.sub.2), timnodonic acid
(R.sup.3.dbd.C.sub.19H.sub.29), clupanodonic acid
(R.sup.3.dbd.C.sub.21H.sub.33), ricinoleic acid
(12-hydroxy-9-octadecenoic acid (R.sup.3.dbd.C.sub.17H.sub.33O),
and/or cervonic acid (R.sup.3.dbd.C.sub.21H.sub.31).
[0062] Other advantageous acids are lignoceric acid
(H.sub.3C--(CH.sub.2).sub.22--COOH), cerotic acid, lactic acid,
citric acid, benzoic acid, nicotinic acid (vitamin B3, B5),
gluconic acid or a mixture of the acids. However, it is also
possible to use the natural or synthetic amino acids, such as
tryptophan, L-arginine, L-histidine, L-phenylalanine, or L-leucine,
where L-leucine is preferred, and it is correspondingly also
possible to use the corresponding D-amino acids, or a mixture of
the amino acids, or a dicarboxylic acid, such as adipic acid,
glutaric acid, terephthalic acid (benzene-1,4-dicarboxylic acid),
or else an acid such as D[(CH.sub.2).sub.d)COOH].sub.3, where D=N,
and P and n=from 1 to 12, preferably 1, 2, 3, 4, 5, or 6. The
corresponding anhydrides, esters or salts, for example alkali-metal
salts, alkaline-earth-metal salts, or ammonium salts, of these
acids can likewise be used.
[0063] In general terms it is also possible that the
acid-containing silicon-free precursor compound used comprises
esters and/or lactones, in particular of the abovementioned acids
or, for example, the triglycerides that occur in fats or in oils,
particular examples being neutral fats, or else phosphoglycerides,
such as lecithin, phosphatidylethanolamine, phosphatidylinositol,
phosphatidylserine, and/or diphosphatidylglycerol. It is also
possible to use synthetic triglycerides, alongside naturally
occurring triglycerides of vegetable origin and of animal
origin.
[0064] A general requirement placed upon the precursor compound
(silicon-containing and/or silicon-free) is that it is hydrolyzable
under the conditions of the monosil and/or sioplas process, and
thus liberates the free organic acid. It is preferable that the
onset of the hydrolysis does not precede the crosslinking step of
the processes, and that in particular it occurs after the shaping
process, for example with introduction into the waterbath, or after
the shaping process in the presence of moisture. Compounds excluded
from the silicon-free precursor compounds are advantageously those
which when hydrolyzed give an inorganic and an organic acid. An
inorganic acid here does not include a silanol. By way of example,
the term silicon-free precursor compounds does not cover acyl
chlorides or in general terms corresponding acyl halides of the
abovementioned organic acids. Nor are organic acid peroxides to be
understood as silicon-free precursor compound.
[0065] One preferred composition which is particularly suitable for
producing compounded polymer materials comprises, as component c),
at least one free-radical generator. Preferred free-radical
generators are organic peroxides and/or organic peresters, or a
mixture of these, preferred examples being tert-butyl
peroxypivalate, tert-butyl 2-ethylperoxyhexanoate, dicumyl
peroxide, di-tert-butyl peroxide, tert-butyl cumyl peroxide,
1,3-di(2-tert-butylperoxyisopropyl)benzene,
2,5-dimethyl-2,5-bis(tert-butylperoxy)hex-3-yne, di-tert-amyl
peroxide, 1,3,5-tris(2-tert-butylperoxyisopropyl)benzene,
1-phenyl-1-tert-butylperoxyphthalide,
alpha,alpha'-bis(tert-butylperoxy)diisopropylbenzene,
2,5-dimethyl-2,5-di-tert-butylperoxyhexane,
1,1-di(tert-butylperoxy)-3,3,5-trimethylcyclohexane (TMCH). It can
also be advantageous to use n-butyl
4,4-di(tert-butylperoxy)valerate, ethyl
3,3-di(tert-butylperoxy)butyrate, and/or
3,3,6,9,9-hexamethyl-1,2,4,5-tetraoxacyclononane.
[0066] The composition can moreover comprise, as component d), at
least one stabilizer and/or other additional substance, and/or a
mixture of these. The stabilizer and/or other additional substances
used can, if appropriate, comprise metal deactivators, processing
aids, inorganic or organic pigments, fillers, carrier materials,
and adhesion promoters. Examples of these are titanium dioxide
(TiO.sub.2), talc, clay, quartz, kaolin, aluminum hydroxide,
magnesium hydroxide, bentonite, montmorillonite, mica (muscovite
mica), calcium carbonate (chalk, dolomite), dyes, pigments, talc,
carbon black, SiO.sub.2, precipitated silica, fumed silica,
aluminum oxides, such as alpha- and/or gamma-aluminum oxide,
aluminum oxide hydroxides, boehmite, baryte, barium sulfate, lime,
silicates, aluminates, aluminum silicates, and/or ZnO, or a mixture
of these. It is preferable that the carrier materials or additional
substances, such as pigments or fillers, are pulverulent,
particulate, porous, or swellable or, if appropriate, take the form
of a foam.
[0067] Examples of preferred metal deactivators are
N,N'-bis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propion-yl)hydrazine,
and also
tris(2-tert-butyl-4-thio(2'-methyl-4-hydroxy-5'-tert-butyl)phenyl-5--
methyl)phenyl phosphite.
[0068] The composition can moreover comprise, as additional
component, at least one heat stabilizer, an example being
pentaerythritol
tetrakis[3-(3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl)propionate],
octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, or else
4,4'-bis(1,1-dimethylbenzyl)diphenylamine.
[0069] The fillers are generally inorganic or mineral fillers and
can advantageously have reinforcing, extending, or else
flame-retardant effect. At least at their surfaces, they bear
groups which can react with the alkoxy groups of the unsaturated
organosilane/mixtures. The result of this can be that the silicon
atom, with the functional group bonded thereto, becomes chemically
fixed on the surface. Particular examples of groups of this type on
the surface of the filler are hydroxy groups.
[0070] Preferred fillers are accordingly metal hydroxides having a
stoichiometric proportion of hydroxy groups or, in the various
dehydrated forms thereof, having a substoichiometric proportion of
hydroxy groups, extending as far as oxides having comparatively few
residual hydroxy groups, where these are however detectable by
DRIFT-IR spectroscopy.
[0071] Examples of suitable fillers are aluminum trihydroxide
(ATH), aluminum oxide hydroxide (AlOOH.aq), magnesium dihydroxide
(MDH), brucite, huntite, hydromagnesite, mica, and montmorillonite.
Other fillers that can be used are calcium carbonate, talc, and
also glass fibers. It is also possible to use the materials known
as "char formers", examples being ammonium polyphosphate,
stannates, borates, talc, or materials of these types in
combination with other fillers.
[0072] The composition may comprise, as further component e), a
thermoplastic parent polymer, a silane-grafted parent polymer, a
silane-copolymerized parent polymer, and/or monomers and/or
prepolymers of said parent polymers, or else silane block
coprepolymers or block coprepolymers, and/or a mixture of these. It
is preferable that the thermoplastic parent polymer is a nonpolar
polyolefin, an example being polyethylene or polypropylene, or a
polyvinyl chloride, or a silane-grafted polyolefin and/or
silane-copolymerized polyolefin, and/or a copolymer of one or more
olefins and of one or more comonomers which contain polar
groups.
[0073] The thermoplastic parent polymer can also function to some
extent or completely as carrier material, for example in a
masterbatch, comprising, as carrier material, a thermoplastic
parent polymer or a polymer and the silicon-containing precursor
compound of an organic acid and an organofunctional silane compound
or, in an alternative, a thermoplastic parent polymer, or a polymer
and an organofunctional silane compound, in particular of the
formula III, and an organic acid.
[0074] Other examples of silane-copolymerized thermoplastic parent
polymers are ethylene-silane copolymers, for example
ethylene-vinyltrimethoxysilane copolymer,
ethylene-vinyltriethoxysilane copolymer,
ethylene-dimethoxyethoxysilane copolymer,
ethylene-gamma-trimethoxysilane copolymer,
ethylene-gamma-(meth)acryloxypropyltriethoxysilane copolymer,
ethylene-gamma-acryloxypropyltriethoxysilane copolymer,
ethylene-gamma-(meth)acryloxypropyltrimethoxysilane copolymer,
ethylene-gamma-acryloxypropyltrimethoxysilane copolymer, and/or
ethylene-triacetoxysilane copolymer.
[0075] The nonpolar thermoplastic parent polymers used can comprise
thermoplastics such as in particular an unmodified PE grade, an
example being LDPE, LLDPE, HDPE, or mPE. Parent polymers bearing
polar groups give by way of example improved fire performance, i.e.
lower flammability and smoke density, and increase capability to
accept filler. Examples of polar groups are hydroxy, nitrile,
carbonyl, carboxy, acyl, acyloxy, and carboalkoxy groups, and amino
groups, and also halogen atoms, in particular chlorine atoms.
Olefinic double bonds and carbon-carbon triple bonds are nonpolar.
Suitable polymers are not only polyvinyl chloride but also
copolymers of one or more olefins and of one or more comonomers
which contain polar groups, e.g. vinyl acetate, vinyl propionate,
(meth)acrylic acid, methyl(meth)acrylate, ethyl(meth)acrylate,
butyl(meth)acrylate, or acrylonitrile. Examples of the amounts of
the polar groups in the copolymers are from 0.1 to 50 mol %,
preferably from 5 to 30 mol %, based on the polyolefin units.
Particularly suitable parent polymers are ethylene-vinyl acetate
copolymers (EVA). By way of example, a suitable commercially
available copolymer contains 19 mol % of vinyl acetate units and 81
mol % of ethylene units.
[0076] Particularly suitable parent polymers are polyethylene,
polypropylene, and also corresponding silane-modified polymers. In
particular, therefore, the use of inventive compositions or
masterbatches (masterkit or polymer kit) can give silane-grafted,
silane-copolymerized, and/or silane-crosslinked PE, PP, polyolefin
copolymer, EVA, EPDM, or EPM in an advantageous manner. The
silane-grafted polymers can be in a form filled with fillers or in
an unfilled form and, if appropriate, can be moisture-crosslinked
subsequently, after a shaping process. A corresponding situation
applies to the silane-copolymerized polymers in a form filled with
fillers or in unfilled form, and these polymers can, if
appropriate, be moisture-crosslinked subsequently, after a shaping
process.
[0077] The composition of the invention is suitable as additive in
a monosil process, in a sioplas process, and/or in a
copolymerization process. It is particularly appropriate that the
silane hydrolysis catalyst and/or silanol condensation catalyst
does not become active until additional moisture is added. The
final crosslinking of the unfilled or filled polymer therefore
generally takes place in a known manner in a waterbath, in a steam
bath, or else via atmospheric moisture, at ambient temperatures
(the process known as "ambient curing").
[0078] The form taken by the components of the composition, a
particular example being the silicon-containing precursor compound
of an organic acid, is advantageously liquid and preferably waxy or
solid, or bound on a carrier material, and/or the form taken by the
organofunctional silane compound can be liquid, highly viscous,
waxy, or solid, or bound on a carrier material. In particular, the
silicon-containing precursor compound of an organic acid is in
essence waxy or solid, i.e. is in essence in solid phase, which can
have amorphous or crystalline regions. This measure can make it
easy to store the precursor compound in anhydrous form, and to
meter the precursor compound. Undesired hydrolysis and/or
condensation prior to use, in particular in a monosil process,
sioplas process, or copolymerization process, can be
suppressed.
[0079] In order to permit better regulation of metering capability
and, if appropriate, susceptibility to hydrolysis, the
silicon-containing precursor compound of an organic acid of the
general formula I and/or II, the organofunctional silane compound
and, if appropriate, the free-radical generator can have been
applied to a carrier material, for example as described in EP 0 426
073.
[0080] To the extent that the silicon-containing precursor compound
I and/or II is itself solid, it can itself be used as carrier
material, in particular for an organofunctional silane, for example
as a carrier material for a silane of the general formula III, for
example of vinyltriethoxysilane, vinyltrimethoxysilane,
vinyltris(methoxyethoxy)silane (VTMOEO), vinyl (co)oligomers, or
other liquid silanes of the formula III.
[0081] Preferable suitable carrier material is a porous polymer
selected from polypropylene, polyolefins, ethylene copolymer using
low-carbon alkenes, ethylene-vinyl acetate copolymer, high-density
polyethylene, low-density polyethylene, or linear low-density
polyethylene, where the porous polymer can have a pore volume of
from 30 to 90% and in particular can be used in the form of
granules or pellets.
[0082] As an alternative, the carrier material can also be a filler
or additional substance, in particular a nanoscale filler.
Preferred carrier materials, fillers, or additional substances are
aluminum hydroxide, magnesium hydroxide, fumed silica, precipitated
silica, wollastonite, calcined variants, chemically and/or
physically modified materials, such as kaolin, modified kaolin, and
in particular ground, exfoliating materials, such as
phyllosilicates, preferably specific kaolins, a calcium silicate, a
wax, such as a polyolefin wax based on LDPE (low-density
polyethylene), or a carbon black.
[0083] The carrier material can encapsulate the silicon-containing
precursor compound and/or the silane compound of group a), and/or
the free-radical generator, or can retain these in physically or
chemically bound form. It is advantageous here if the loaded or
unloaded carrier material is swellable, in particular in a solvent.
The amount of the silane components of group a) is usually in the
range from 0.01% by weight to 99.9% by weight, preferably from 0.1%
by weight to 70% by weight, preferably from 0.1% by weight to 50%
by weight, with particular preference from 0.1% by weight to 30% by
weight, based on the total weight of the composition comprising the
carrier material, particularly preferably in the form of
masterbatch. The amount present of the carrier material is
therefore generally from 99.99 to 0.01% by weight, based on the
total weight of the composition (giving 100% by weight).
[0084] In order to facilitate metering of the composition and
protect it from premature hydrolysis, it is particularly preferable
that the silicon-containing precursor compound of an organic acid,
the organofunctional silane compound, or a mixture of the two
compounds is in a form that is waxy or solid or bound to a carrier
material.
[0085] Individual preferred carrier materials that may be mentioned
are: ATH (aluminum trihydroxide, Al(OH).sub.3), magnesium hydroxide
(Mg(OH).sub.2), or fumed silica, which is produced on an industrial
scale via continuous hydrolysis of silicon tetrachloride in a
hydrogen/oxygen flame. This process vaporizes the silicon
tetrachloride which then reacts spontaneously and quantitatively
within the flame with the water derived from the hydrogen/oxygen
reaction. Fumed silica is an amorphous form of silicon dioxide and
is a free-flowing, bluish powder. Particle size is usually in the
region of a few nanometers, and specific surface area is therefore
large, generally being from 50 to 600 m.sup.2/g. The process by
which the vinylalkoxysilanes and/or the silicon-containing
precursor compound, or a mixture of these, becomes attached to the
material here is therefore in essence adsorption. Precipitated
silicas are generally produced from sodium waterglass solutions,
via neutralization with inorganic acids under controlled
conditions. After isolation from the liquid phase, washing, and
drying, the crude product is finely ground, e.g. in steam-jet
mills. Again, precipitated silica is a substantially amorphous
silicon dioxide, the specific surface area of which is generally
from 50 to 150 m.sup.2/g. Unlike fumed silica, precipitated silica
has a certain porosity, for example about 10% by volume. The
process by which the vinylalkoxysilanes and/or the
silicon-containing precursor compound, or a mixture of these,
becomes attached to the material can therefore be either adsorption
on the surface or absorption within the pores. Calcium silicate is
generally produced industrially by fusing quartz or kieselguhr with
calcium carbonate or calcium oxide, or via precipitation of aqueous
sodium metasilicate solutions with water-soluble calcium compounds.
The carefully dried product is generally porous and can absorb up
to five times the amount by weight of water or oils.
[0086] Porous polyolefins, such as polyethylene (PE) or
polypropylene (PP), and also copolymers, such as ethylene
copolymers with low-carbon alkenes, such as propene, butene,
hexene, or octene, or ethylene-vinyl acetate (EVA) are produced via
specific polymerization techniques and polymerization processes.
Particle sizes are generally from 3 to <1 mm, and porosity can
be above 50% by volume, and the products can therefore absorb
suitably large amounts of unsaturated organosilane/mixtures, for
example of the general formula III, and/or of the
silicon-containing precursor compound, or a mixture of these,
without losing their free-flow properties.
[0087] Particularly suitable waxes are polyolefin waxes based on
low-density polyethylene (LDPE), preferably branched, with long
side chains. The melting and freezing point is generally from 90 to
120.degree. C. The waxes generally give good results in mixing with
the unsaturated organosilanes, such as vinylalkoxysilane, and/or
with the silicon-containing precursor compound, or a mixture of
these, in a low-viscosity melt. The solidified mixture is generally
sufficiently hard to be capable of granulation.
[0088] The various commercially available forms of carbon black are
suitable by way of example for producing black cable sheathing.
[0089] The following methods inter alia are available for producing
the compositions (dry liquids) on carriers, examples being
compositions made of olefinic silane carboxylates, such as
vinylsilane carboxylate of myristic acid or lauric acid, and
carrier material, or else of vinylsilane stearate and carrier
material, or of a tetracarboxysilane and vinylalkoxysilane with
carrier material:
[0090] Among the best-known methods is spray drying. Alternative
methods are explained in more detail below: mineral carriers or
porous polymers are generally preheated, e.g. to 60.degree. C. in
an oven, and charged to a cylindrical container which has been
flushed with, and filled with, dry nitrogen. A vinylalkoxysilane
and/or vinylcarboxysilane is generally then added, and the
container is placed in a roller apparatus which rotates it for
about 30 minutes. After this time, the carrier substance and the
liquid, high-viscosity or waxy alkoxysilane and/or carboxysilane
have usually formed flowable, dry-surface granules which are
advantageously stored under nitrogen in containers impermeable to
light. As an alternative, the heated carrier substance can be
charged to a mixer flushed and filled with dry nitrogen, e.g. a
plowshare mixer of LODIGE type or a propeller mixer of HENSCHEL
type. The mixer element can then be operated and the olefinic
alkoxysilane and/or carboxysilane, in particular of the formula I,
or a mixture of these, can be sprayed in by way of a nozzle once
the maximum mixing rate has been reached. When addition has been
completed, homogenization generally continues for a further
approximately 30 minutes, and the product is then discharged into
nitrogen-filled containers impermeable to light, for example by
means of a pneumatic conveying system operated with dry
nitrogen.
[0091] Polyethylene wax or any other wax in pelletized form with a
melting point of from 90 to 120.degree. C. or above can be melted
in portions in a heatable vessel with stirrer, reflux condenser,
and liquid-addition apparatus, and maintained in the molten state.
Dry nitrogen is suitably passed through the apparatus during the
entire production process. By way of the liquid-addition apparatus
it is possible by way of example to add the liquid
vinylcarboxysilane/mixtures progressively to the melt and mix these
with the wax by vigorous stirring. The melt is then generally
discharged into molds to solidify, and the solidified product is
granulated. As an alternative, the melt can be allowed to drip onto
a cooled molding belt on which it solidifies in the form of
user-friendly pastilles.
[0092] The invention also provides a masterkit, in particular
comprising a composition described above, where the masterkit
comprises, as component A [0093] from 0.1 to 20% by weight, in
particular from 0.1 to 10% by weight, preferably from 0.1 to 5% by
weight, particularly preferably from 0.1 to 3% by weight,
preferably from 0.5 to 5% by weight, in component A, of at least
one silicon-containing precursor compound of an organic acid, in
particular of the general formula I and/or II as defined above, or
at least one organic acid, or one silicon-free precursor compound
comprising an organic acid, in particular as defined above, and a
carrier material making up 100% by weight of component A, or [0094]
in alternatives, also a stabilizer, an added substance, or a
mixture of these, making up 100% by weight of component A, and
[0095] if appropriate, as component B, from 60 to 99.9% by weight,
in component B, of an organofunctional silane compound of the
formula III, where the definitions of b, a, B, R.sup.4, and R.sup.5
are as above, and also [0096] if appropriate from 0.05 to 10% by
weight of a free-radical generator, and [0097] if appropriate from
0.05 to 10% by weight of at least one stabilizer, and/or [0098]
from 0.05 to 99.99% by weight of at least one carrier material,
stabilizer, added substance, or a mixture of these, where added
substances that can be used comprise fillers and additives or a
mixture of these, where the quantitative data give a total of 100%
by weight in component B. Suitable added substances have been
described above.
[0099] Particular carrier materials that can be used are those
mentioned above, examples being PE, PP, and also others mentioned
above. Similar considerations apply to the free-radical generator
and to the stabilizer. Components A and B are preferably present
separately from one another within the masterkit where the
intention is to use them in two steps of the process. In the case
of simultaneous use, the two components A and B can be present
together in a physical mixture, for example in the form of powder,
granules, or pellets, or else can be present in a single
formulation, for example in pellet form or tablet form. A
masterbatch of the invention comprises a vinyltriethoxysilane, for
example vinyltrimethoxysilane, a peroxide, and also a processing
aid, and also a silicon-containing precursor compound of an organic
acid, if appropriate with a carrier material.
[0100] One preferred masterkit comprises by way of example 2% by
weight of an organic acid, such as a fatty acid, in particular
myristic acid, or lauric acid, on a polymeric carrier material,
such as HDPE, where the amount of HDPE present is 98% by weight of
the masterkit (component A), making up the balance of 100% by
weight. Other masterkits comprise as organic acid preferably
behenic acid, L-leucine, capric acid, oleic acid, lauric acid,
and/or myristic acid, if appropriate in a mixture on a carrier
material, for example HDPE.
[0101] The component B present can preferably comprise an
unsaturated alkoxysilane, in particular of the formula III, or
oligomeric siloxanes produced therefrom, preferably
vinyltrimethoxysilane or vinyltriethoxysilane, together with a
free-radical generator and with a stabilizer, if appropriate with
further additives. Preferably on a carrier material, for example in
the form of granules.
[0102] The invention also provides a process for producing
compounded polymer materials, examples being granules, finished
products, and moldings, in particular of unfilled or filled
polymers, by [0103] 1) reacting a mixture made of thermoplastic
parent polymer, in particular with a component of group a) at least
one silicon-containing precursor compound of an organic acid and/or
one organofunctional silane compound and, if appropriate, in
particular with a component of group b) an organic acid, a
silicon-free precursor compound containing an organic acid, and
also a free-radical generator, in a compounding apparatus, in
particular in the presence of moisture, or [0104] 2) reacting a
mixture made of thermoplastic parent polymer, in a first step, with
a) an organofunctional silane compound, and also a free-radical
generator, in particular for producing silane-grafted polymer, and
shaping the material, in a subsequent, in particular immediately
subsequent, step, with addition of at least one silicon-containing
precursor compound of an organic acid, one organic acid, and/or one
silicon-free precursor compound containing an organic acid, and
crosslinking the material with exposure to moisture, or [0105] 3)
reacting a mixture made of thermoplastic parent polymer, in a first
step, with a) at least one olefinic silicon-containing precursor
compound of an organic acid, in particular of the general formulae
I and/or II, where z=1, 2, or 3, and also with a free-radical
generator, and shaping the material, in a subsequent step, with
addition of at least one silicon-containing precursor compound of
an organic acid, one silicon-free precursor compound containing an
organic acid, and/or one organic acid, and crosslinking the
material with exposure to moisture, or [0106] 4) reacting a mixture
made of monomer and/or prepolymer of the thermoplastic parent
polymers with a) an organofunctional silane compound, and also a
free-radical generator, in particular for producing
silane-copolymerized parent polymer, and shaping the material, in a
subsequent, in particular immediately subsequent or nearly
subsequent, step, with addition of at least one silicon-containing
precursor compound of an organic acid, one organic acid, and/or one
silicon-free precursor compound containing an organic acid, and
then crosslinking the material with exposure to moisture.
[0107] In an alternative process of the invention for producing
compounded polymer materials, such as granules, finished products,
moldings, and in particular unfilled or filled polymers, [0108] 1)
a mixture made of thermoplastic parent polymer is reacted with
component B of the masterkit and component A of the masterkit
described above in a compounding apparatus, and if appropriate is
shaped at a given juncture, and crosslinked by moisture, or [0109]
2) a mixture made of thermoplastic parent polymer is reacted, in a
first step, with component B of the masterkit described above and,
in a subsequent step, is shaped, with addition of component A of a
masterkit described above, and is crosslinked with exposure to
moisture, or [0110] 3) a mixture made of monomer and/or prepolymer
of the thermoplastic parent polymers is reacted with component B of
the masterkit, as described in the introduction, and is shaped, in
a subsequent step, with addition of component A of the masterkit,
and is then crosslinked with exposure to moisture, and in
particular a thermoplastic parent polymer is mixed with component B
of the masterkit and reacted, and then granulated and, if
appropriate, drawn off or packed by way of example in the form of
PEg (PE granules) in an aluminum-coated sack. In a subsequent step,
component A is added to the granules (PEg), and mixed, and if
appropriate shaped, and during this process or subsequently
crosslinked in the presence of moisture; or [0111] 4) a mixture
made of thermoplastic parent polymer is reacted with the
composition described above or with a masterkit described above in
a monosil process, in particular one of the abovementioned
preferred compositions, or [0112] 5) a mixture made of
thermoplastic parent polymer is reacted with the composition
described above, or with a masterkit described above, in a sioplas
process, or [0113] 6) a mixture made of monomer and/or prepolymer
of the thermoplastic parent polymers is reacted with a composition
described above or with a masterkit described above, in a
copolymerization process.
[0114] The invention also provides the reaction of a polymer kit,
in particular as claimed in claim 15, in a monosil process or
sioplas process, or in a copolymerization process.
[0115] One embodiment of the invention uses the composition
described above, in particular as claimed in claims 1 to 8, and/or
the masterkit, or the polymer kit, in the production of
silane-grafted, silane-copolymerized, and/or crosslinked, in
particular siloxane-crosslinked, filled or unfilled polymers.
[0116] The invention also provides the use of the composition or of
the masterkit, or of the polymer kit, in particular in a monosil,
sioplas, or copolymerization process, for producing filled and/or
unfilled compounded polymer materials, which can take crosslinked
or uncrosslinked form, and/or of crosslinked filled and/or unfilled
polymers based on thermoplastic parent polymers. For the purposes
of the invention, crosslinking in particular means the formation of
an Si--O-substrate bond or Si--O-filler or Si--O-carrier material,
or Si--O'Si bridging, i.e. the condensation of an Si--OH group with
a condensable other group of a substrate.
[0117] Preference is given to the use for the production of
silane-grafted, silane-copolymerized, and/or crosslinked, in
particular siloxane-crosslinked, filled or unfilled polymers. The
abovementioned polymers can also comprise block copolymers. It is
preferable that the fillers are likewise crosslinked with the
silicon-containing compounds, in particular by way of an
Si--O-filler/carrier material bond. Particular fillers that can be
used are the abovementioned fillers or carrier materials. In some
of the abovementioned processes, it is preferable to use the
unsaturated fatty acids. There are therefore sometimes no
conventional organic acids used, examples being acetic acid, formic
acid, maleic acid, maleic anhydride, or stearic acid.
[0118] The process as claimed in claim 10 paragraph 1) is
preferably conducted with at least one monounsaturated alkoxysilane
corresponding to the formula III or one silicon-containing
precursor compound of an organic acid, in particular of the
formulae I and/or III, or with a mixture of the abovementioned
compounds.
[0119] Preferred silicon-containing precursor compounds of the
general formulae I and/or II are compounds where R.sup.1 is a
carbonyl-R.sup.3 group selected from the group of the natural
saturated and unsaturated fatty acids, in particular having
hydrophobic hydrocarbon moieties having from 4 to 45 carbon atoms,
in particular having from 6 to 45 carbon atoms, in particular
having from 6 to 22 carbon atoms, preferably having from 8 to 22
carbon atoms, particularly preferably having from 6 to 14 carbon
atoms, with particular preference where R.sup.3 is from 11 to 13
carbon atoms, particularly preferably where z is 0 or 1. It can be
preferable to use, in compositions, a monounsaturated alkoxysilane
together with a compound of the formula I and/or II, where z is 0,
1, 2, or 3.
[0120] Preferred organic acids used for the thermoplastic parent
polymers, or the silane-grafted and/or silane-copolymerized parent
polymers, but in particular not for polyvinyl chlorides, are fatty
acids selected from the group of the natural saturated and mono- or
polyunsaturated fatty acids, in particular having hydrophobic
hydrocarbon moieties having from 4 to 45 carbon atoms, in
particular having from 6 to 45 carbon atoms in R.sup.3, in
particular having from 6 to 22 carbon atoms, preferably having from
8 to 22 carbon atoms, particularly preferably having from 6 to 14
carbon atoms,
[0121] with particular preference where R.sup.3 is from 11 to 13
carbon atoms, particularly preferably myristic acid and/or lauric
acid. It can be preferable, in particular in a single-step process,
to use, either alone or in compositions, a mono- or polyunsaturated
alkoxysilane where a is 0, with no other alkylsilane.
[0122] The moisture-crosslinked unfilled or filled compounded
polymer materials of the invention are generally produced via
appropriate mixing of the respective starting-material components
in the melt, as explained above for the processes, advantageously
with exclusion of moisture. The usual heatable homogenization
apparatuses are generally suitable for this purpose, examples being
kneaders or advantageously for continuous operation Buss cokneaders
or twin-screw extruders. As an alternative to these, it is also
possible to use a single-screw extruder. A possible method here
introduces the components continuously, in each case individually
or in partial mixtures, in the prescribed quantitative proportion,
to the extruder, which has been heated to a temperature above the
melting point of the thermoplastic parent polymer. It is
advantageous that the temperature rises in the direction toward the
end of the screw, in order to establish a low viscosity and thus
permit intensive mixing. In an advantageous method, the extrudates
are still liquid when they are introduced to an apparatus for the
molding of granules or of moldings, such as pipes. The final
crosslinking of the unfilled or filled polymer generally takes
place in a known manner in a waterbath, in a steam bath, or else
via atmospheric moisture at ambient temperatures (the process known
as "ambient curing").
[0123] At least one stabilizer and/or at least one further added
substance, corresponding to the statements above, can be added in
the process of the invention, prior to and/or during the process,
and/or during one step of the process.
[0124] The invention also provides a polymer, for example a
crosslinked filled or crosslinked unfilled polymer; a compounded
polymer material, such as a compounded cable material, or a
flame-retardant cable, for example filled with Mg(OH).sub.2 or
Al(OH).sub.3, or with exfoliating materials, such as
phyllosilicates; a filled plastic, an unfilled plastic and/or a
molding and/or article obtainable by the process of the invention,
in particular as claimed in any of claims 10 to 12. Appropriate
moldings and/or items are cables, pipes, such as drinking-water
lines, or products which can be used in the food-and-drinks sector
or in the sector of hygiene products, or in the sector of medical
technology, for example as medical instrument or part of a medical
instrument, Braunule, trocar, stent, clot retriever, vascular
prosthesis, or component of a catheter, to mention just a few
possibilities.
[0125] The invention further provides a polymer kit comprising the
composition described above, in particular the components of group
a), b), c), and/or d), and also, in particular separately from
these, in the form of further component, component e) a
thermoplastic parent polymer, an example being a silane-grafted
parent polymer or silane-copolymerized parent polymer, or a monomer
or prepolymer of the parent polymer, and/or a mixture of these.
Components of group a), b), c), and/or d) can respectively be
separated or, supported on a carrier in the polymer kit, can take
the form of a mixture on fillers or on mineral carrier materials,
for example on the abovementioned carrier materials, or else on
carbon, an example being activated charcoal or carbon black.
[0126] An alternative polymer kit comprises the masterkit described
above and also, as further component, a thermoplastic parent
polymer, an example being a silane-grafted parent polymer or
silane-copolymerized parent polymer, or a monomer or prepolymer of
the parent polymer, and/or a mixture of these.
[0127] An example of a polymer kit is: 63.5% by weight of HDPE,
1.5% by weight of myristic acid, 5% by weight of Irganox 1010
(methyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate), and 30%
by weight of Printex alpha pigment.
[0128] In the case of single-stage processes, for example in the
case of the monosil process, the polymer and the composition that
initiates crosslinking, the masterkit, or, in an alternative, the
polymer kit only, are charged to the extruder, and the resultant
melt is processed in one step to give the final product. The
inventive composition used is appropriately a composition which
comprises an organofunctional silane compound, in particular of the
formula III, and which comprises a free-radical generator, and
which also comprises a silicon-containing precursor compound of an
organic acid or comprises an organic acid, and also, if
appropriate, comprises a stabilizer.
[0129] For the production of filled plastics, the inorganic filler
is mostly introduced directly to the compounding assembly and
processed with the polymer to give the final product. The filler
can also optionally be introduced at a later juncture into the
assembly, for example in the case of a twin-screw extruder or
cokneader. The graft polymer produced using the inventive
composition or the inventive masterkit can give markedly better
compatibility of nonpolar polymer and polar filler, for example
aluminum hydroxide or magnesium hydroxide.
[0130] It is also possible to produce a graft polymer, in
particular sioplas material, separately and, if appropriate, to
granulate and package the material, in particular with protection
from moisture, and to store the same and then to supply the same as
feedstock to a processor, for example a cable producer or pipe
producer, who in turn incorporates fillers to produce final filled
plastics products.
[0131] The following examples provide further illustration of the
inventive compositions, the masterkit, the polymer kit, and the
inventive processes, but the invention is not restricted to these
examples.
A) Production of alkyl- or alkenyltricarboxysilane, or
tetracarboxysilane
GENERAL EXAMPLES
[0132] a) For the production of alkenyltricarboxysilane, 1 mol of
an alkenyltrichlorosilane, or in general terms an
alkenyltrihalosilane, is reacted directly with 3 mol, or with an
excess, of the organic monocarboxylic acid, or reacted in an inert
solvent, in particular at elevated temperature. [0133] b) For the
production of an alkyltricarboxysilane, 1 mol of an
alkyltrichlorosilane is correspondingly reacted directly with 3
mol, or with an excess, of an organic monocarboxylic acid, or is
reacted in an inert solvent. It is preferable that the reaction
takes place at elevated temperature, for example at up to the
boiling point of the solvent, or at around the melting point of the
organic fatty acid or of the organic acid. [0134] c) For the
production of tetracarboxysilanes, 1 mol of tetrahalosilane, in
particular tetrachlorosilane or tetrabromosilane, is reacted with 4
mol, or with an excess, of at least one monocarboxylic acid, for
example one fatty acid or fatty acid mixture. The reaction can take
place directly via melting or in an inert solvent, preferably at
elevated temperature.
Example 1
Production of vinyltristearylsilane
[0135] Reaction of 1 mol of vinyltrichlorosilane with 3 mol of
stearic acid in toluene as solvent: 50 g of stearic acid (50.1 g)
were used as initial charge with 150.0 g of toluene in a flask. The
solid dissolves after gentle heating. Cooling gives a cloudy,
highly viscous mass, which when reheated again forms a clear
liquid. The oil bath was set to 95.degree. C. at the start of the
experiment, and about 20 minutes of mixing time gave a clear
liquid. 9.01 g of vinyltrichlorosilane were then rapidly added
dropwise with a pipette. After about 10 min the mixture was a clear
liquid, and the oil temperature was adjusted to 150.degree. C.
After about a further 3 h after the start of the experiment, the
mixture was cooled under inert gas. It was worked up by
distillative removal of the toluene. This gave a white solid which
when melted had an oily and yellowish appearance. For further
purification, the solid can be subjected to further rotary
evaporator treatment, for example for a prolonged period (3-5 h) at
an oil bath temperature of about 90.degree. C. and at a vacuum<1
mbar. The solid was characterized as vinyltrichlorosilane by way of
NMR (.sup.1H, .sup.13C, .sup.29Si).
Example 2
Production of vinyltridecanoic acid
[0136] Reaction of 1 mol of vinyltrichlorosilane with 3 mol of
capric acid in toluene as solvent: 60.0 g of capric acid (decanoic
acid) were used as initial charge with 143.6 g of toluene in a
flask. The oil bath was set to 80.degree. C. at the start of the
experiment, and the vinyltrichlorosilane was slowly added dropwise
(about 0.5 h for 19.1 g) while the temperature of the mixture was
about 55.degree. C. After about 45 min, the temperature of the oil
was increased to 150.degree. C. After a reaction time of about a
further 2 h, the oil bath was switched off, but the stirring, the
water-cooling, and the nitrogen blanketing were continued until
cooling was complete. The clear liquid was transferred to a
single-necked flask, and the toluene was drawn off in a rotary
evaporator. The oil bath temperature was set to about 80.degree. C.
The vacuum was adjusted stepwise to <1 mbar. The product was a
clear liquid. The liquid was characterized as vinyltricaprylsilane
by way of NMR (1H, .sup.13C, .sup.29Si).
Example 3
Production of hexadecyltricaprylsilane
[0137] Reaction of 1 mol of Dynasylan.RTM. 9016
(hexadecyltrichlorosilane) with 3 mol of capric acid in toluene as
solvent: 73.1 g of capric acid (decanoic acid) were used as initial
charge with 156.2 g of toluene in a flask. The oil bath was set to
95.degree. C. at the start of the experiment, and 50.8 g of
Dynasylan.RTM. 9016 were added dropwise over a period of about 25
minutes. After about min, the temperature of the oil was increased
to 150.degree. C. The experiment was terminated after reflux for
about 1.5 h. The toluene was drawn off from the clear liquid in a
rotary evaporator. The oil bath temperature was set to about
80.degree. C. The vacuum was adjusted stepwise to <1 mbar. The
product was a yellow oily liquid with a slightly pungent odor. The
liquid was characterized in essence as hexadecyltricaprylsilane by
way of NMR (.sup.1H, .sup.13C, .sup.29Si).
Example 4
Production of vinyltripalmitylsilane
[0138] Reaction of 1 mol of vinyltrichlorosilane with 3 mol of
palmitic acid in toluene as solvent: 102.5 g of palmitic acid were
used as initial charge with 157.0 g of toluene in a flask. The oil
bath was set to 92.degree. C. at the start of the experiment, and
the 22.0 g of vinyltrichlorosilane were slowly added dropwise over
a period of about 15 minutes. After about 70 min, the temperature
of the oil was increased to 150.degree. C. The mixture was heated
at reflux for about 4 h, and then the toluene was removed by
distillation. The oil bath temperature was adjusted to about
80.degree. C., and the vacuum was adjusted stepwise to 2 mbar.
Cooling of the product gave a white, remeltable solid. The solid
was characterized as vinyltripalmitylsilane by way of NMR (.sup.1H,
.sup.13C, .sup.29Si).
Example 5
Production of chloropropyltripalmitylsilane
[0139] Reaction of 1 mol of CPTCS (chloropropyltrichlorosilane)
with 3 mol of palmitic acid in toluene as solvent: 40.01 g of
palmitic acid were used as initial charge in a three-necked flask,
and the oil bath was heated. Once all of the palmitic acid had
dissolved, 11.03 g of the CPTCS (99.89% purity (GC/TCD)) were added
dropwise within a period of about 10 min. The temperature was
finally increased to 130.degree. C. After about 3.5 h no further
gas activity was observed in an attached gas-washer bottle, and the
synthesis was terminated. The toluene was removed in a rotary
evaporator. At a subsequent juncture, the solid was remelted and
stirred at an oil bath temperature of about 90.degree. C. under a
vacuum of <1 mbar. After about 4.5 h, no further gas bubbles
were observed. The solid was characterized as
chloropropyltripalmitylsilane by way of NMR (.sup.1H, .sup.13C,
.sup.29Si).
Example 6
Production of propyltrimyristylsilane
[0140] Reaction of 1 mol of PTCS (propyltrichlorosilane, 98.8%
purity) with 3 mol of myristic acid in toluene as solvent. The
reaction was analogous to that in the above examples. The reaction
product was characterized as propyltrimyristylsilane.
Example 7
Production of vinyltrimyristylsilane
[0141] Reaction of Dynasylan.RTM. VTC with myristic acid: 40.5 g of
myristic acid and 130 g of toluene are used as initial charge in
the reaction flask, and mixed and heated to about 60.degree. C. 9.5
g of Dynasylan.RTM. VTC are added dropwise within a period of 15
min by means of a dropping funnel. The temperature in the flask
increases by about 10.degree. C. during addition. After addition,
stirring is continued for 15 minutes, and then the temperature of
the oil bath is increased to 150.degree. C. During the continued
stirring, gas evolution (HCL gas) can be observed. Stirring was
continued until no further gas evolution was observed (gas
discharge valve), and stirring was continued for 3 h. After cooling
of the mixture, unreacted Dynasylan.RTM. VTC and toluene were
removed by distillation at about 80.degree. C. at reduced pressure
(0.5 mbar). The product remaining in the reaction flask is stored
overnight in the flask with N.sub.2 blanketing and then discharged
without further work-up. The product subsequently solidifies. About
44.27 g of crude product were obtained.
Example 8
Production of propyltrimyristylsilane
[0142] Reaction of Dynasylan.RTM. PTCS with myristic acid: 40.5 g
of myristic acid and 150 g of toluene are used as initial charge in
the reaction flask, and mixed and heated to about 60.degree. C.
Dynasylan.RTM. PTCS is added dropwise within a period of 15 minutes
by means of a dropping funnel. The temperature in the flask
increases by about 10.degree. C. during addition. After addition
the temperature of the oil bath is increased to 150.degree. C. and
stirring is continued for 3 h. During the continued stirring, gas
evolution, HCL gas, can be observed. Stirring was continued until
no further gas evolution was observed at the gas discharge valve.
After cooling of the mixture, unreacted Dynasylan.RTM. PTCS and
toluene were removed by distillation at about 80.degree. C. at
reduced pressure (0.5 mbar). The product was stored under inert gas
and solidified. About 44.0 g of crude product were obtained.
B) Crosslinking Examples
[0143] Dynasylan.RTM. SILFIN 24 (vinyltrimethoxy (VTMO), peroxide,
and processing aid)
Example 9
[0144] Grafting of Dynasylan.RTM. SILFIN 24 HDPE with
Masterbatch
[0145] Grafting of 95% by weight of Dynasylan.RTM. SILFIN 24 HDPE
with 5% by weight of masterbatch, and crosslinking at 80.degree. C.
in a waterbath. The masterbatch comprised 2% by weight of
catalyst.
TABLE-US-00001 TABLE 1 Overview of starting materials and gel
contents Gel [%] Gel [%] Gel [%] 4 h at 80.degree. C. 22 h at
80.degree. C. Catalyst 0 h Waterbath Waterbath Behenic acid 17 36
53 Tryptophan 9 18 34 L-phenylalanine 16 26 39 L-leucine 1 30 46
Blind value 13 16 34 Caprylic acid 25 37 49 Oleic acid 22 42 52
Capric acid 23 36 44 Stearic acid 24 44 56 Palmitic acid 25 39 53
Myristic acid 23 37 49 Lauric acid 31 37 48
[0146] All of the fatty acids and amino acids tested accelerate a
crosslinking reaction within the silane-modified polymer.
Example 10
[0147] Grafting of Dynasylan.RTM. SILFIN 24 HDPE with
Masterbatch
[0148] As Example 9, only with 0.2% by weight catalyst content
within the masterbatch.
TABLE-US-00002 TABLE 2 Overview of starting materials and gel
contents Gel [%] Gel [%] Gel [%] 4 h at 80.degree. C. 22 h at
80.degree. C. Catalyst 0 h Waterbath Waterbath Blind value 1.00 11
25.37 Stearic acid 34 54.08 62.35 Palmitic acid 29 48.60 62.43
Example 11
[0149] Grafting of Dynasilan.RTM. SILFIN 24 HDPE with
Masterbatch
[0150] As Example 9, only with 0.5% by weight catalyst content
within the masterbatch.
TABLE-US-00003 TABLE 3 Overview of starting materials and gel
contents Gel [%] Gel [%] Gel [%] 4 h at 80.degree. C. 22 h at
80.degree. C. Catalyst 0 h Waterbath Waterbath Blind value 1 11 25
Capric acid 39 60 60 Caprylic acid 39 60 61 Myristic acid 38 59 64
Behenic acid 37 58 64 Stearic acid 37 61 66 Oleic acid 49 62 65
Palmitic acid 48 63 66 Tegokat 216 67 70 69 (DOTL)
Example 12
[0151] Grafting of Dynasylan.RTM. SILFIN 24 HDPE with
Masterbatch
[0152] As Example 9, only with 1.0% by weight catalyst content
within the masterbatch.
TABLE-US-00004 TABLE 4 Overview of starting materials and gel
contents Gel [%] Gel [%] Gel [%] 4 h at 80.degree. C. 22 h at
80.degree. C. Catalyst 0 h Waterbath Waterbath Blind value 12.51
16.43 33.60 Behenic acid 16.64 35.71 52.97 Stearic acid 24.17 43.86
55.72 Oleic acid 22.38 41.78 52.37 Palmitic acid 24.78 38.82 53.19
Myristic acid 23.08 37.40 48.97 Capric acid 22.91 35.79 44.18
Tegokat 216 44.12 61.37 65.79 (DOTL) Caprylic acid 24.87 37.40
49.26
Example 13
[0153] Grafting of Dynasylan.RTM. SILFIN 24 HPDE with
Masterbatch
[0154] Silane-grafted HDPE is reacted with various amounts of added
myristic acid.
TABLE-US-00005 TABLE 5 Overview of starting materials and gel
contents, 1.2 phr of Dynasylan .RTM. SILFIN 24 Gel [%] Gel [%] Gel
[%] 4 h at 80.degree. C. 22 h at 80.degree. C. Catalyst 0 h
Waterbath Waterbath Blind value 0 0 26 0.2% by weight 29 60 70 of
myristic acid 0.075% by weight 40 70 73 of DOTL 0.5% by weight 33
68 75 of myristic acid 1.0% by weight 47 72 76 of myristic acid
Example 14
[0155] Grafting of Dynasylan.RTM. SILFIN 24 HPDE with
Masterbatch
[0156] Silane-grafted HDPE is reacted with various amounts of added
myristic acid.
TABLE-US-00006 TABLE 6 Overview of starting materials and gel
contents, 1.4 phr of Dynasylan .RTM. SILFIN 24 Gel [%] Gel [%] Gel
[%] 4 h at 80.degree. C. 22 h at 80.degree. C. Catalyst 0 h
Waterbath Waterbath Blind value -0.37 0.73 29.72 0.2% by weight
21.46 58.79 70.39 of myristic acid 0.075% by weight 38.97 70.97
75.19 of DOTL 0.5% by weight 21.46 58.79 70.39 of myristic acid
1.0% by weight 37.69 70.16 76.02 of myristic acid
Example 15
[0157] Grafting of Dynasylan.RTM. SILFIN 24 HDPE with
Masterbatch
[0158] Silane-grafted HDPE is reacted with various amounts of added
myristic acid.
TABLE-US-00007 TABLE 7 Overview of starting materials and gel
contents, 1.6 phr of Dynasylan .RTM. SILFIN 24 Gel [%] Gel [%] Gel
[%] 4 h at 80.degree. C. 22 h at 80.degree. C. Catalyst 0 h
Waterbath Waterbath Blind value 0 2 35 0.2% by weight 27 65 73 of
myristic acid 0.075% by weight 44 73 78 of DOTL 0.5% by weight 36
71 76 of myristic acid 1.0% by weight 56 77 78 of myristic acid
[0159] The above experiments provide evidence that myristic acid
achieves gel contents comparable to those achieved with DOTL. When
myristic acid is used, the amount of exudation observed on the
crosslinked products is zero to small, even at high
concentrations.
[0160] The following catalyst was used for the above Examples to
15: 0.2, 0.5, and 1.0% by weight of catalyst content (myristic
acid) and 0.075% by weight of DOTL (standard masterbatch), compared
with a blind value. Grafted HDPE was produced here with 1.2; 1.4,
and 1.6 phr of Dynasylan.RTM. SILFIN 24. In each case, the
silane-grafted PE was mixed with 5% by weight of the catalyst
masterbatch, and processed in the kneader. A HAAKE laboratory
kneader was used for processing, and plaques were then
compression-molded at 200.degree. C. and crosslinked at 80.degree.
C. in the waterbath.
[0161] Processing Parameters:
[0162] Kneader, feed hopper, belt mold, belt take-off; filled feed
zone,
[0163] Rotation rate: 30 rpm,
[0164] temperature profile: 140.degree. C./3 min; 2 min at
210.degree. C.; 210.degree. C./5 min
[0165] Crosslinking time: 0 h, 4 h and 22 h
Example 16
[0166] Step A--Grafting of MG9641S HDPE from Borealis with
Dynasylan.RTM. SILFIN 24 Mixtures
[0167] The grafting took place in a (ZE 25) twin-screw extruder
from Berstorff. The experiments produced strands. The crosslinking
agent preparation was in each case applied for 1 h to the PE in a
mixing drum, after predrying at 70.degree. C. for about 1 h. The
grafted strands were granulated after extrusion. The granules were
packaged directly after the granulation process in bags coated with
an aluminum layer and these were closed by welding. Prior to the
welding process, the granules were blanketed with nitrogen.
[0168] Processing parameters for the grafting reaction in the ZE
25
[0169] Temperature profile: -/150/160/200/200/210/210/210.degree.
C.
[0170] Rotation rate: about 100 rpm, addition: 1.5 phr of
Dynasylan.RTM. SILFIN 24
[0171] Step B--Processing for the Crosslinking Study
[0172] The silane-grafted polyethylene was kneaded in a laboratory
kneader (Thermo HAAKE, 70 cm.sup.3) with the respective catalyst
(temperature profile: 140.degree. C./3 min; 2 min up to 210.degree.
C.; 210.degree. C./5 min, kneader rotation rate: 30 rpm). The
mixture was then pressed at 200.degree. C. to give sheets.
Crosslinking took place in a waterbath at 80.degree. C. (4 h). The
gel contents of the crosslinked sheets were determined (8 h,
p-xylene, Soxhlet extraction).
[0173] 1) Screening with Various Fatty Acids as Catalyst at 0.5% by
Weight Concentration in Comparison with Tin Catalyst
TABLE-US-00008 TABLE 8 Gel contents for the study with various
fatty acids as catalyst in comparison with tin catalyst Gel [%], 4
h at 80.degree. C. Catalyst Waterbath Comments No catalyst 11
Caprylic acid 60 strong, pungent odor Myristic acid 59 Stearic acid
61 waxy exudation on surface of specimen Palmitic acid 63 waxy
exudation on surface of specimen Dioctyltin 70 dilaurate
[0174] 2) Screening with Fatty Acids, Precursor Compounds of the
Fatty Acids, and Amino Acids
[0175] In each case 95% by weight of silane-grafted PE with 5% by
weight of catalyst masterbatch, where the catalyst masterbatch
comprised 98% by weight of HDPE and 2% by weight of catalyst
(organic acid). The results can be found in table 9.
TABLE-US-00009 TABLE 1 Gel contents for the study with various
catalysts Gel [%] 22 h at 80.degree. C. Catalyst Waterbath Catalyst
type No catalyst 34 -- Magnesium stearate 37 Organic-acid-
containing, silicon-free precursor compound of the fatty acid
L-leucine 46 Amino acid Hexadecyltripalmitic 49 Silicon-containing
acid silane precursor compound of a fatty acid Behenic acid 53
Fatty acid Tegokat 216 (DOTL) 66 Tin catalyst
Example 17
[0176] a) Grafting of MG9641S HDPE from Borealis with
Dynasylan.RTM. SILFIN 24
[0177] The grafting took place in a ZE 25 extruder from Berstorff.
The crosslinking agent preparation was in each case applied for 1 h
to the PE in a mixing drum, after predrying at 70.degree. C. for
about 1 h. The grafted strands were granulated after extrusion. The
granules were packaged directly after the granulation process in
polyethylene-aluminum-polyethylene packaging and these were closed
by welding. Prior to the welding process, the granules were
blanketed with nitrogen.
[0178] Processing Parameters for the Grafting Reaction in the ZE
25
[0179] Temperature profile: -/150/160/200/200/210/210/210.degree.
C.
[0180] Rotation rate: about 100 rpm,
[0181] Addition: 1.5 phr of Dynasylan.RTM. SILFIN 24
(CS/V039/08)
[0182] b) Kneading Processes
[0183] For the production of the masterbatch, 49.0 g of PE were
kneaded in a HAAKE laboratory kneader with 1.0 g of catalyst,
organic acid, or silicon-containing precursor compound.
[0184] Processing Parameters:
[0185] Kneader, feed hopper, tape die, tape take-off; filled feed
zone,
[0186] Rotation rate: 30 rpm,
[0187] Temperature profile: 200.degree. C./5 min
[0188] c) Production of Mixture Made of 95% By Weight of Silfin 24
HDPE with 5% By Weight of Masterbatch
[0189] A mixture made of 95% by weight of Silfin 24 HDPE with 5% by
weight of the masterbatch comprising the catalyst is produced.
Processing took place in a HAAKE laboratory kneader. A mixture made
of 95% by weight of Silfin 24 HDPE mixture with 5% by weight of
masterbatch is kneaded, then pressed at 200.degree. C. to give
sheets, and finally crosslinked in a waterbath at 80.degree. C.
[0190] Processing Parameters:
[0191] Kneader, feed hopper, tape die, tape take-off; filled feed
zone,
[0192] Rotation rate: 30 rpm,
[0193] Temperature profile: 140.degree. C./3 min; 2 min up to
210.degree. C.; 210.degree. C./5 min
[0194] Crosslinking time: 0 h, 4 h, and 22 h
Example 18
[0195] Crosslinking of Silane-Grafted HDPE
[0196] Polyethylene was modified chemically (grafted, rotation
rate: 30 rpm, temperature profile: 3 min at 140.degree. C., 2 min
from 140.degree. C. to 200.degree. C., 10 min 200.degree. C.) with
various vinylsilanes with addition of peroxide in a HAAKE
data-gathering kneader. Once the graft reaction had been concluded,
aluminum trihydroxide (ATH) was added to the kneader as water
donor. The presence of postcrosslinking detectable by way of a
marked increase in torque was checked. The following mixtures were
used:
TABLE-US-00010 TABLE 10 Experimental mixtures Dynasylan .RTM.
Vinyltripalmitic Vinyltricapric VTMO acid silane acid silane BCUP
(tert-butyl ~0.1 g ~0.14 g ~0.1 cumyl peroxide) Silane-containing
~0.55 g ~1.1 g ~1.3 compound HDPE 50 g ATH 2 g
[0197] Both experiments using vinyltricarboxysilanes revealed a
marked increase in torque after addition of the ATH. The increase
was considerably more marked than with vinyltrimethoxysilane. The
conclusion from this is that the extent of crosslinking reaction is
greater.
Example 19
[0198] Crosslinking of HDPE--Comparison of Vinyltripalmitic acid
silane with Dynasylan.RTM. SILFIN 06
[0199] For this study, the individual crosslinking preparations
were admixed with the HDPE power and processed in the kneader
(rotation rate: 35 rpm, temperature profile: 2 min at 150.degree.
C., in 3 min from 150 to 210.degree. C., 5 min at 210.degree. C.).
Table 11 lists the formulations:
TABLE-US-00011 TABLE 11 Formulation Vinyltripalmitic acid silane
DCUP (dicumyl peroxide) 0.025 g Silane-containing compound 1.5 g
HDPE 50 g
[0200] The kneaded specimen was pressed to give a sheet and then
crosslinked at 80.degree. C. in the waterbath. The gel content of
the crosslinked specimens was measured after various storage
times.
TABLE-US-00012 TABLE 12 Gel contents of crosslinked specimens
Crosslinking time Gel content for Waterbath, 80.degree. C.
vinyltripalmitic acid silane [%] 0.5 h 32 1 h 32 2 h 31 4 h 33 24 h
31
Example 20
[0201] Masterkit (Masterbatch)
[0202] The carboxysilanes produced were used as catalysts in the
sioplas process. For this, 95% by weight of a polyethylene grafted
with Dynasylan.RTM. SILFIN 24 were kneaded with 5% by weight of the
catalyst concentrate (catMB) of the invention. First, a masterbatch
was produced with 1 g of the respective catalyst and 49 g of HDPE
in the kneader (temperature profile: 5 min at 200.degree. C.). 2.5
g of this were then kneaded together with 47.5 g of the extruded
Dynasylan.RTM. SILFIN 24 HDPE (temperature profile: 3 min at
140.degree. C., from 140.degree. C. to 210.degree. C. in 2 min, 5
min at 210.degree. C.), and then pressed at 200.degree. C. to give
sheets, and finally crosslinked at 80.degree. C. in the waterbath.
The catMB included respectively 2% by weight of the respective
catalyst, in particular of the vinyltricarboxysilanes or fatty
acids. The results were compared with a mixture without catalyst.
The sheets were crosslinked at 80.degree. C. in the waterbath.
Table 13 shows the results of this crosslinking study.
TABLE-US-00013 TABLE 13 Overview of catalyst study in the sioplas
process Catalyst/ Gel content [%] Gel content [%] experiment Gel
content [%] 4 h at 80.degree. C. 22 h at 80.degree. C. number
Uncrosslinked Waterbath Waterbath Blind value - 13 16 34 no cat.
Vinyltri- 17 33 46 palmitic acid silane Hexadecyltri- 18 40 49
palmitic acid silane Vinyltricapric 23 36 46 acid silane
Hexadecyltri- 23 39 45 capric acid silane Capric acid 23 36 44
Palmitic acid 25 39 53
* * * * *