U.S. patent application number 17/606789 was filed with the patent office on 2022-07-07 for blends that consist of tpu and polyamide.
This patent application is currently assigned to BASF SE. The applicant listed for this patent is BASF SE. Invention is credited to Oliver Steffen Henze, Tanja Lange, Birte Nitz.
Application Number | 20220213266 17/606789 |
Document ID | / |
Family ID | |
Filed Date | 2022-07-07 |
United States Patent
Application |
20220213266 |
Kind Code |
A1 |
Henze; Oliver Steffen ; et
al. |
July 7, 2022 |
Blends that consist of TPU and polyamide
Abstract
A composition contains at least a thermoplastic polyurethane
(TPU-1) and a copolyamide (PA-1), prepared by polymerization of at
least one lactam and of a monomer mixture (M). The monomer mixture
(M) contains at least a C.sub.32-C.sub.40 dimer acid as a component
(B1), and at least a C.sub.4-C.sub.12 diamine as a component (B2).
A process can be used for preparing such compositions, and the
composition can be used for producing shaped articles.
Inventors: |
Henze; Oliver Steffen;
(Lemfoerde, DE) ; Nitz; Birte; (Lemfoerde, DE)
; Lange; Tanja; (Lemfoerde, DE) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
BASF SE |
Ludwigshafen am Rhein |
|
DE |
|
|
Assignee: |
BASF SE
Ludwigshafen am Rhein
DE
|
Appl. No.: |
17/606789 |
Filed: |
April 29, 2020 |
PCT Filed: |
April 29, 2020 |
PCT NO: |
PCT/EP2020/061844 |
371 Date: |
October 27, 2021 |
International
Class: |
C08G 69/36 20060101
C08G069/36; C08K 3/016 20060101 C08K003/016; C08K 3/32 20060101
C08K003/32; C08G 18/76 20060101 C08G018/76; C08L 77/08 20060101
C08L077/08; C08L 75/08 20060101 C08L075/08 |
Foreign Application Data
Date |
Code |
Application Number |
Apr 30, 2019 |
EP |
19171847.7 |
Claims
1-14. (canceled)
15: A composition, comprising at least: (I) a thermoplastic
polyurethane (TPU-1), and (II) a copolyamide (PA-1), prepared by
polymerization of (A) at least one lactam, and (B) a monomer
mixture (M) comprising the following components: (B1) at least one
C32-C40 dimer acid, and (B2) at least one C4-C12 diamine.
16: The composition according to claim 15, wherein the
thermoplastic polyurethane (TPU-1) is based on an aromatic
diisocyanate.
17: The composition according to claim 16, wherein the
thermoplastic polyurethane (TPU-1) has a Shore hardness in the
range from 70 A to 85 D, determined in accordance with DIN
53505.
18: The composition according to claim 15, wherein the
thermoplastic polyurethane (TPU-1) is based on an aliphatic
diisocyanate.
19: The composition according to claim 15, wherein a proportion of
the thermoplastic polyurethane (TPU-1) in the composition is in a
range from 5% to 95% by weight, based on a sum total of components
(I) and (II).
20: The composition according to claim 15, wherein a proportion of
the copolyamide (PA-1) in the composition is in a range from 5% to
95% by weight, based on a sum total of components (I) and (II).
21: The composition according to claim 15, wherein the composition
comprises at least one flame retardant selected from the group
consisting of melamine cyanurate, magnesium hydroxide, and a
phosphorus-containing flame retardant.
22: The composition according to claim 15, wherein the composition
comprises at least one first phosphorus-containing flame retardant
(F1) selected from the group consisting of a derivative of
phosphoric acid and a derivative of phosphonic acid, and wherein
the composition comprises at least one further
phosphorus-containing flame retardant (F2) selected from the group
consisting of a derivative of phosphinic acid.
23: The composition according to claim 22, wherein the at least one
first phosphorus-containing flame retardant (F1) is a
phosphinate.
24: The composition according to claim 23, wherein the phosphinate
is selected from the group consisting of an aluminum phosphinate
and a zinc phosphinate.
25: The composition according to claim 22, wherein the at least one
further phosphorus-containing flame retardant (F2) is a phosphoric
ester.
26: The composition according to claim 22, wherein the at least one
first flame retardant (F1) is selected from the group consisting of
resorcinol bis(diphenyl phosphate) (RDP), bisphenol A bis(diphenyl
phosphate) (BDP), and diphenyl cresyl phosphate (DPK).
27: A process for producing a composition (Z-1), comprising: (a)
providing the following components (I) a thermoplastic polyurethane
(TPU-1), and (II) a copolyamide (PA-1), prepared by polymerizing at
least one lactam and a monomer mixture (M) comprising (B1) at least
one C32-C40 dimer acid, and (B2) at least one C4-C12 diamine; and
(b) mixing components (I) and (II).
28: A method, comprising: producing a shaped article with the
composition according to claim 15.
29: A shaped article, comprising the composition according to claim
15.
Description
[0001] The present invention relates to a composition comprising at
least one thermoplastic polyurethane (TPU-1) and a copolyamide
(PA-1), prepared by polymerizing at least one lactam, and a monomer
mixture (M) comprising at least one C32-C40 dimer acid as component
(B1) and at least one C4-C12 diamine as component (B2). The present
invention further relates to a process for producing such
compositions and to the use of a composition of the invention for
production of shaped articles.
[0002] Thermoplastic polyurethanes are widely known and are used as
materials in many sectors. The properties can be adjusted within
wide ranges. Typically, thermoplastic polyurethanes can be
processed within a particular temperature range. A problem in the
processing is the redissociation of the urethane bond, which, in
the course of processing, can lead to degradation of the
thermoplastic polyurethanes and to very low melt strengths, and
hence to problems in extrusion.
[0003] Particularly hard TPUs over and above about 40 D are
difficult to process. For processing, the semicrystalline materials
firstly have to be melted at high temperatures; secondly, the
materials break down at these high temperatures. As a result,
materials can be processed only within a very small temperature
range. This is a problem especially when different temperatures
occur at the nozzle in processes for extrusion of large shaped
articles. In that case, there may be instances where the material
in the colder zones of the nozzle has not yet completely melted,
but is already breaking down in the hotter zones of the nozzle.
[0004] Polyamides generally have, in contrast, high melt strength
and very wide processing ranges. Polyamides are of particular
significance in industry since they feature very good mechanical
properties and especially have high strength and toughness, good
chemical stability and high abrasion resistance. They are used, for
example, for production of fishing line, climbing rope and carpet
backing. Furthermore, polyamides find use for production of packing
films and packing sheaths.
[0005] For packing films and packing sheaths, copolyamides that
combine positive properties of different polyamides are frequently
also used. The prior art describes various copolyamides.
[0006] EP 0 352 562 describes films composed of copolyamides,
wherein the copolyamides have been prepared from
.epsilon.-caprolactam and preferably 1 to 10 parts by weight of a
dimer acid and a diamine. DE 28 46 596 describes shaped articles
composed of a copolyamide of caprolactam, fatty acid dimers and
hexamethylenediamine. Of particular industrial interest are nylon-6
and nylon-6,6, owing to their excellent properties can be used in
many sectors. However, nylon-6 and nylon-6,6 have very high melting
temperatures.
[0007] WO 2018/050487 A1 describes copolyamides, wherein the
copolyamide has been prepared by polymerizing at least one lactam
(A) and a monomer mixture (M). Additionally described is the
production of a polymer film (P) comprising such copolyamides.
[0008] Proceeding from the prior art, it was an object of the
present invention to provide materials that have improved melt
strength and hence a broad processing range, particularly within
the hardness range from 40 to 90 D. It was a further object of the
present invention to provide materials that have improved melt
strength and hence a broad processing range, and are additionally
transparent.
[0009] This object is achieved in accordance with the invention by
a composition (Z-1) comprising at least [0010] (I) a thermoplastic
polyurethane (TPU-1) and [0011] (II) a copolyamide (PA-1), prepared
by polymerization of [0012] (A) at least one lactam, and [0013] (B)
a monomer mixture (M) comprising the following components: [0014]
(B1) at least one C32-C40 dimer acid and [0015] (B2) at least one
C4-C12 diamine.
[0016] It has been found that, surprisingly, copolyamide (PA-1) can
be blended with various thermoplastic polyurethanes. The blends
have excellent mechanical properties, high toughness and high melt
strength. It has also been found that many flame retardants,
including flame retardants having relatively low breakdown
temperature, can be incorporated directly into a corresponding
blend or else into the copolyamide (PA-1). The materials obtained
have excellent mechanical properties, high toughness and good
flammability performance.
[0017] The composition (Z-1) of the invention comprises at least
one thermoplastic polyurethane (TPU-1) and a copolyamide
(PA-1).
[0018] Thermoplastic polyurethanes are known in principle. They are
typically produced by reaction of isocyanates and
isocyanate-reactive compounds and chain extenders optionally in the
presence of at least one catalyst and/or customary auxiliaries
and/or additives. Isocyanates, isocyanate-reactive compounds and
chain extenders are also referred to, individually or collectively,
as formation components.
[0019] In the context of the present invention, the customarily
used isocyanates and isocyanate-reactive compounds are suitable in
principle.
[0020] Isocyanate-reactive compounds that may be used in principle
include all suitable compounds known to those skilled in the art.
According to the invention, at least one diol is preferably used as
isocyanate-reactive compound. It is possible here in the context of
the present invention to use any suitable diols, for example
polyether diols or polyester diols or mixtures of two or more of
these.
[0021] According to the invention, the thermoplastic polyurethane
(TPU-1) is prepared preferably by using a polyol composition
typically comprising at least one polyol (P1) as
isocyanate-reactive compound. In the context of the present
invention, it is possible in principle to use any polyols suitable
per se, for example polyesterols, polyetherols and/or polycarbonate
diols. For example, the polyol used may have a molecular weight
(Mn) in the range from 500 g/mol to 8000 g/mol, and preferably an
average functionality with respect to isocyanates of 1.8 to 2.3,
preferably 1.9 to 2.2, especially 2. The number-average molecular
weight is determined to DIN 55672-1 unless stated otherwise.
[0022] The polyol (P1) used preferably has a molecular weight in
the range from 600 to 2000 daltons, further preferably a molecular
weight in the range from 750 to 5000 daltons, especially a
molecular weight of about 1000 daltons.
[0023] Polyesters used may be polyesters based on diacids and
diols. Diols used are preferably diols having 2 to 10 carbon atoms,
for example ethanediol, butanediol or hexanediol, especially
butane-1,4-diol or mixtures thereof. Diacids used may be any known
diacids, for example linear or branched-chain diacids having four
to 12 carbon atoms or mixtures thereof.
[0024] It is further possible in the context of the present
invention to use polyether polyols, for example those based on
commonly known starter substances and customary alkylene oxides,
preferably ethylene oxide, propylene oxide and/or butylene oxide,
further preferably polyetherols based on 1,2-propylene oxide and
ethylene oxide, and especially polyoxytetramethylene glycols. One
advantage of the polyether polyols is that they have relatively
high hydrolysis stability.
[0025] Also suitable are polyetherols having a low level of
unsaturation. Polyols having a low level of unsaturation in the
context of this invention are especially understood to mean
polyether alcohols having a content of unsaturated compounds of
less than 0.02 meq/g, preferably less than 0.01 meq/g. Such
polyether alcohols are usually prepared by addition of alkylene
oxide, especially ethylene oxide, propylene oxide and mixtures
thereof, onto the above-described diols or triols in the presence
of highly active catalysts.
[0026] Such highly active catalysts are preferably cesium hydroxide
and multi metal cyanide catalysts, also referred to as DMC
catalysts. A frequently and preferentially used DMC catalyst is
zinc hexacyanocobaltate. The DMC catalyst can be left in the
polyether alcohol after the reaction; it is typically removed, for
example by sedimentation or filtration.
[0027] In addition, in the context of the present invention, it is
possible to use polytetrahydrofurans, for example having an average
molecular weight Mn in the range from 400 to 1800 g/mol, preferably
from polytetrahydrofurans having an average molecular weight Mn in
the range from 600 to 1500 g/mol, more preferably from
polytetrahydrofurans having an average molecular weight Mn in the
range from 750 to 1250 g/mol, for example in the range from 900 to
1100 g/mol.
[0028] It has been found that compositions having a particularly
advantageous profile of properties are obtained especially in the
case of use of polyols having an average molecular weight in the
range from 900 to 1100 g/mol. For instance, the compositions of the
invention firstly have a low melting point, and secondly good
low-temperature properties.
[0029] Examples of suitable polycarbonate diols include
polycarbonate diols based on alkanediols. Suitable polycarbonate
diols are strictly difunctional OH-functional polycarbonate diols,
preferably strictly difunctional OH-functional aliphatic
polycarbonate diols. Suitable polycarbonate diols are based, for
example, on butane-1,4-diol, pentane-1,5-diol or hexane-1,6-diol,
especially butane-1,4-diol, pentane-1,5-diol, hexane-1,6-diol,
3-methylpentane-1,5-diol or mixtures thereof, more preferably
butane-1,4-diol, pentane-1,5-diol, hexane-1,6-diol or mixtures
thereof. In the context of the present invention, preference is
given to using polycarbonate diols based on butane-1,4-diol and
hexane-1,6-diol, polycarbonate diols based on pentane-1,5-diol and
hexane-1,6-diol, polycarbonate diols based on hexane-1,6-diol and
mixtures of two or more of these polycarbonate diols. Suitable
polycarbonate diols have, for example, an average molecular weight
Mn in the range from 800 to 1200 g/mol.
[0030] It has been found that the use of polycarbonate diols
affords compositions suitable for those applications having good
hydrolysis stability and good aging resistance. For instance, the
compositions of the invention, when polycarbonate diols are used as
polyols, as well as good low-temperature properties, also have high
hydrolysis resistance and good aging resistance.
[0031] However, the polymer composition, in the context of the
present invention, as well as the polyol (P1), may also comprise
one or more chain extenders (KV1) and optionally (KV2) and further
isocyanate-reactive compounds. For example, the polyol composition
may comprise further polyols having an average molecular weight Mn
in the range from 800 to 1200 g/mol.
[0032] According to the invention, it is also possible to use
mixtures of different chain extenders. Chain extenders (KV1) and
(KV2) used may be commonly known aliphatic, araliphatic, aromatic
and/or cycloaliphatic compounds having a molecular weight,
preferably average molecular weight, of 50 g/mol to 499 g/mol,
preferably difunctional compounds. Preference is given, for
example, to alkanediols having 2 to 10 carbon atoms in the alkylene
radical, preferably butane-1,4-diol, hexane-1,6-diol and/or di-,
tri-, tetra-, penta-, hexa-, hepta-, octa-, nona- and/or
decaalkylene glycols having 3 to 8 carbon atoms, further preferably
unbranched alkanediols, especially propane-1,3-diol,
butane-1,4-diol and hexane-1,6-diol.
[0033] In a further embodiment, the present invention accordingly
also relates to a composition as described above, wherein the chain
extender (KV1) and/or the chain extender (KV2) is selected from the
group consisting of ethane-1,2-diol, propane-1,3-diol,
butane-1,4-diol and hexane-1,6-diol, diethylene glycol, triethylene
glycol, hydroquinone bis(2-hydroxyethyl) ether and
bis(2-hydroxyethyl) terephthalate.
[0034] The chain extender (KV1) in the context of the present
invention is further preferably selected from the group consisting
of ethane-1,2-diol, propane-1,3-diol, butane-1,4-diol and
hexane-1,6-diol. In a further embodiment, the present invention
accordingly also relates to a composition as described above,
wherein the chain extender (KV1) is butane-1,4-diol.
[0035] According to the invention, it is also possible to use
further chain extenders in the polyol composition.
[0036] It is also possible in accordance with the invention to use
a polyhydric alcohol, for example propanediol and/or a further
diol, that has been obtained at least partly from renewable raw
materials. It is possible here that the polyhydric alcohol has been
obtained partly or entirely from renewable raw materials. According
to the invention, at least one of the polyhydric alcohols used may
be obtained at least partly from renewable raw materials.
[0037] What is called bio-propane-1,3-diol is obtainable, for
example, from corn and/or sugar. A further option is the conversion
of glycerol wastes from biodiesel production. In a further
preferred embodiment of the invention, the polyhydric alcohol is
propane-1,3-diol that has been at least partly obtained from
renewable raw materials.
[0038] In a further embodiment, the present invention accordingly
relates to a composition as described above, wherein the
thermoplastic polyurethane is based to an extent of at least 30% on
renewable raw materials. One suitable method of determination is
the C14 method, for example.
[0039] In the context of the present invention, the organic
isocyanates customarily used are suitable in principle. Organic
isocyanates used may be aliphatic, cycloaliphatic, araliphatic
and/or aromatic isocyanates, more preferably tri-, tetra-, penta-,
hexa-, hepta- and/or octamethylene diisocyanate,
2-methylpentamethylene 1,5-diisocyanate, 2-ethylbutylene
1,4-diisocyanate, pentamethylene 1,5-diisocyanate, butylene
1,4-diisocyanate,
1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane
(isophorone diisocyanate, IPDI), 1,4- and/or
1,3-bis(isocyanatomethyl)cyclohexane (HXDI), cyclohexane
1,4-diisocyanate, 1-methylcyclohexane 2,4- and/or 2,6-diisocyanate
and/or dicyclohexylmethane 4,4'-, 2,4'- and 2,2'-diisocyanate,
diphenylmethane 2,2'-, 2,4'- and/or 4,4'-diisocyanate (MDI),
naphthylene 1,5-diisocyanate (NDI), tolylene 2,4- and/or
2,6-diisocyanate (TDI), dimethyl diphenyl 3,3'-diisocyanate,
1,2-diphenylethane diisocyanate and/or phenylene diisocyanate.
Particular preference is given to using 4,4'-MDI only.
[0040] Accordingly, the present invention, in a further embodiment,
also relates to a composition as described above, wherein the
thermoplastic polyurethane (TPU-1) is based on an aromatic
diisocyanate.
[0041] In an alternative embodiment, the present invention, in a
further embodiment, also relates to a composition as described
above, wherein the thermoplastic polyurethane (TPU-1) is based on
an aliphatic diisocyanate.
[0042] In a further embodiment, the present invention accordingly
relates to a composition as described above, wherein the
thermoplastic polyurethane is based on diphenylmethane
4.4'-diisocyanate.
[0043] Further suitable aliphatic isocyanates are, for example,
hexamethylene diisocyanate (HDI), or
1-isocyanato-4-[(4-isocyanatocyclohexyl) methyl]cyclohexane
(H12MDI).
[0044] According to the invention, particularly preferred
isocyanates are hexamethylene diisocyanate (HDI), diphenylmethane
2,2'-, 2,4'- and/or 4,4'-diisocyanate (MDI) and tolylene 2,4-
and/or 2,6-diisocyanate (TDI), or
1-isocyanato-4-[(4-isocyanatocyclohexyl)methyl]cyclohexane
(H12MDI), particular preference being given to diphenylmethane
2,2'-, 2,4'- and/or 4,4'-diisocyanate (MDI), especially
diphenylmethane 4,4'-diisocyanate.
[0045] As well as the isocyanate composition and the polyol
composition, the thermoplastic polyurethane (TPU1) may be prepared
using further components, for example suitable catalysts or
auxiliaries.
[0046] In a preferred embodiment, catalysts that accelerate
especially the reaction between the NCO groups of the diisocyanates
and the hydroxyl groups of the isocyanate-reactive compound and the
chain extender are tertiary amines, especially triethylamine,
dimethylcyclohexylamine, N-methylmorpholine,
N,N'-dimethylpiperazine, 2-(dimethylaminoethoxy)ethanol,
diazabicyclo[2.2.2]octane; in another preferred embodiment, these
are organic metal compounds such as titanate esters, iron
compounds, preferably iron(III) acetylacetonate, tin compounds,
preferably tin diacetate, tin dioctoate, tin dilaurate or the
dialkyltin salts of aliphatic carboxylic acids, preferably
dibutyltin diacetate, dibutyltin dilaurate, or bismuth salts in
which bismuth is preferably in oxidation states 2 or 3, especially
3. Salts of carboxylic acids are preferred. Carboxylic acids used
are preferably carboxylic acids having 6 to 14 carbon atoms, more
preferably having 8 to 12 carbon atoms. Examples of suitable
bismuth salts are bismuth(III) neodecanoate, bismuth
2-ethylhexanoate and bismuth octanoate.
[0047] The catalysts are preferably used in amounts of 0.0001 to
0.1 parts by weight per 100 parts by weight of the
isocyanate-reactive compound. Preference is given to using tin
catalysts, especially tin dioctoate.
[0048] In addition to catalysts it is also possible to add
customary auxiliaries. Examples include surface-active substances,
fillers, further flame retardants, nucleation agents, oxidation
stabilizers, lubrication and demolding aids, dyes and pigments,
optionally stabilizers, for example against hydrolysis, light, heat
or discoloration, inorganic and/or organic fillers, reinforcers and
plasticizers. Suitable auxiliary and additive substances may be
found for example in Kunststoffhandbuch, volume VII, edited by
Vieweg and Hochtlen, Carl Hanser Verlag, Munich 1966 (p.
103-113).
[0049] Production processes suitable for thermoplastic
polyurethanes are disclosed for example in EP 0 922 552 A1. DE 101
03 424 A1 or WO 2006/072461 A1. Production is typically effected on
a belt apparatus or in a reactive extruder, but can also be
effected on the laboratory scale, for example in a manual casting
method. Depending on the physical properties of the components
these are all mixed with one another directly or individual
components are premixed and/or prereacted, for example to give
prepolymers, and only then subjected to polyaddition. In a further
embodiment a thermoplastic polyurethane is first produced from the
building block components, optionally together with catalyst, into
which auxiliaries may optionally also be incorporated. In that
case, at least one filler is introduced into this material and
distributed homogeneously. Homogeneous distribution is preferably
effected in an extruder, preferably in a twin-screw extruder.
According to the invention, it is preferable to add the filler in
portions, for example a portion of the extruder intake and a
further portion of a second dosage site, for example a side feeder.
The hardness of the TPUs can be set within relatively broad molar
ratios by varying the amounts of the formation components used,
typically with rising hardness as the content of chain extender
increases.
[0050] According to the invention, the mixing ratio of the
components used for preparation of the thermoplastic polyurethane
may vary within wide ranges. For example, the chain extenders and
the polyol used may be used in a molar mixing ratio in the range
from 20:1 to 1:1, preferably in the range from 18:1 to 2:1, further
preferably in the range from 17:1 to 3:1, more preferably in the
range from 15:1 to 4:1.
[0051] If the mixtures of different chain extenders are used, the
mixing ratio of the chain extenders used may vary within wide
ranges. For example, the chain extenders may be used in a molar
mixing ratio KV1:KV2 in the range from 20:1 to 3:1, preferably in
the range from 15:1 to 4:1, further preferably in the range from
17:1 to 3:1, more preferably in the range from 15:1 to 4:1.
[0052] The thermoplastic polyurethane used in accordance with the
invention preferably has a hardness in the range from 70 A to 90 D
determined according to DIN ISO 7619-1 (Shore A hardness test
(3s)), preferably in the range from 80 A to 95 A determined
according to DIN ISO 7619-1, more preferably in the range from 80 A
to 90 A determined according to DIN ISO 7619-1, especially
preferably in the range from 85 A to 90 A determined according to
DIN ISO 7619-1.
[0053] In a further embodiment, the present invention accordingly
also relates to a composition as described above, wherein the
thermoplastic polyurethane (TPU-1) has a Shore hardness in the
range from 70 A to 90 D determined according to DIN 53505.
[0054] For preparation of the thermoplastic polyurethanes of the
invention, the formation components are preferably reacted in the
presence of catalysts and optionally auxiliaries and/or additives
in such amounts that the ratio of equivalence of NCO groups in the
diisocyanates to the sum total of the hydroxyl groups in the
further formation components is 0.9 to 1.1:1, preferably 0.95 to
1.05:1 and especially about 0.95 to 1.00:1.
[0055] Preference is given in accordance with the invention to
using thermoplastic polyurethanes where the thermoplastic
polyurethane has an average molecular weight (Mw) in the range from
50 000 to 500 000 Da. The upper limit for the average molecular
weight (Mw) of the thermoplastic polyurethanes is generally
determined by processibility and by the spectrum of properties
desired. Further preferably, the thermoplastic polyurethane has an
average molecular weight (Mw) in the range from 50 000 to 250 000
Da, especially preferably in the range from 50 000 to 150 000
Da.
[0056] It is also possible in accordance with the invention for the
composition to comprise two or more thermoplastic polyurethanes
differing for example in their average molecular weight or in their
chemical composition. For example, the composition of the invention
may comprise a first thermoplastic polyurethane TPU-1 and a second
thermoplastic polyurethane TPU-2, for example a thermoplastic
polyurethane TPU-1 based on an aliphatic diisocyanate and a further
TPU-2 based on an aromatic diisocyanate.
[0057] TPU-1 is prepared here using an aliphatic isocyanate, and
TPU-2 using an aromatic isocyanate.
[0058] Organic isocyanates used to prepare the TPU-1 are preferably
aliphatic or cycloaliphatic isocyanates, more preferably tri-,
tetra-, penta-, hexa-, hepta- and/or octamethylene diisocyanate,
2-methylpentamethylene 1,5-diisocyanate, 2-ethylbutylene
1,4-diisocyanate, pentamethylene 1,5-diisocyanate, butylene
1,4-diisocyanate,
1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane
(isophorone diisocyanate, IPDI), 1,4- and/or
1,3-bis(isocyanatomethyl)cyclohexane (HXDI), cyclohexane
1,4-diisocyanate, 1-methylcyclohexane 2.4- and/or 2,6-diisocyanate
and/or dicyclohexylmethane 4,4'-, 2,4'- and 2,2'-diisocyanate.
[0059] In a further embodiment, the present invention therefore
relates to a composition as described above, wherein the
thermoplastic polyurethane TPU-1 is based on at least one aliphatic
diisocyanate selected from the group consisting of hexamethylene
diisocyanate and di(isocyanatocyclohexyl)methane.
[0060] Organic isocyanates (a) used for the preparation of TPU-2
are preferably araliphatic and/or aromatic isocyanates, more
preferably diphenylmethane 2,2'-, 2,4'- and/or 4,4'-diisocyanate
(MDI), naphthylene 1,5-diisocyanate (NDI), tolylene 2.4- and/or
2,6-diisocyanate (TDI), dimethyl diphenyl 3,3'-diisocyanate,
1,2-diphenylethane diisocyanate and/or phenylene diisocyanate.
Particular preference is given to using 4,4'-MDI.
[0061] In a further embodiment, the present invention therefore
relates to a composition as described above, wherein the
thermoplastic polyurethane TPU-2 is based on diphenylmethane
diisocyanate (MDI).
[0062] Isocyanate-reactive compounds used with preference for TPU-1
and TPU-2 are a polycarbonate diol or a polytetrahydrofuran polyol.
Suitable polytetrahydrofuran polyols have, for example, a molecular
weight in the range from 500 to 5000, preferably 500 to 2000, more
preferably 800 to 1200.
[0063] According to the invention, TPU-1 and TPU-2 are prepared
preferably by using at least one polycarbonate diol, preferably an
aliphatic polycarbonate diol. Examples of suitable polycarbonate
diols include polycarbonate diols based on alkanediols. Suitable
polycarbonate diols are strictly difunctional OH-functional
polycarbonate diols, preferably strictly difunctional OH-functional
aliphatic polycarbonate diols. Suitable polycarbonate diols are
based, for example, on butanediol, pentanediol or hexanediol,
especially butane-1,4-diol, pentane-1,5-diol, hexane-1,6-diol,
3-methylpentane-1,5-diol or mixtures thereof, more preferably
butane-1,4-diol, pentane-1,5-diol, hexane-1,6-diol or mixtures
thereof. Preference is given in the context of the present
invention to using polycarbonate diols based on butanediol and
hexanediol, polycarbonate diols based on pentanediol and
hexanediol, polycarbonate diols based on hexanediol and mixtures of
two or more of these polycarbonate diols.
[0064] It is preferable when the polycarbonate diols used for
preparation of TPU-1 and TPU-2 have a number-average molecular
weight Mn in the range from 500 to 4000 determined by GPC,
preferably in the range from 650 to 3500 determined by GPC, more
preferably in the range from 800 to 3000 determined by GPC.
[0065] Chain extenders which may be used for preparation of TPU-1
and TPU-2 preferably include aliphatic, araliphatic, aromatic
and/or cycloaliphatic compounds having a molecular weight of 0.05
kg/mol to 0.499 kg/mol, preferably difunctional compounds, for
example diamines and/or alkanediols having 2 to 10 carbon atoms in
the alkylene radical, di-, tri-, tetra-, penta-, hexa-, hepta-,
octa-, nona- and/or decaalkylene glycols having 3 to 8 carbon
atoms, especially 1,2-ethylene glycol, propane-1,3-diol,
butane-1,4-diol, hexane-1,6-diol, preferably corresponding oligo-
and/or polypropylene glycols, and it is also possible to use
mixtures of the chain extenders. The compounds (c) preferably have
primary hydroxyl groups only, and very particularly preference is
given to using mixtures of butane-1,4-diol with a further chain
extender selected from the compounds recited above, for example
mixtures comprising butane-1,4-diol and a second chain extender in
a molar ratio in the range from 100:1 to 1:1, preferably in a range
from 95:1 to 5:1, more preferably in a range from 90:1 to 10:1.
[0066] In a further embodiment, the present invention therefore
relates to a composition as described above, wherein the
thermoplastic polyurethane is prepared using, as chain extender, a
mixture of butane-1,4-diol and a further chain extender.
[0067] According to the invention, TPU-1 preferably has a hardness
in the range from 85 A to 70 D determined according to DIN ISO
7619-1, preferably in the range from 95 A to 70 D determined
according to DIN ISO 7619-1, more preferably in the range from 55 D
to 65 D determined according to DIN ISO 7619-1.
[0068] According to the invention, TPU-2 preferably has a hardness
in the range from 70 A to 70 D determined according to DIN ISO
7619-1, more preferably in the range from 80 A to 60 D determined
according to DIN ISO 7619-1, more preferably in the range from 80 A
to 90 A determined according to DIN ISO 7619-1.
[0069] In a further embodiment, the present invention therefore
relates to a composition as described above, wherein the
thermoplastic polyurethane TPU-1 has a Shore hardness in the range
from 85 A to 65 D determined according to DIN ISO 7619-1. In a
further embodiment, the present invention therefore relates to a
composition as described above, wherein the thermoplastic
polyurethane TPU-2 has a Shore hardness in the range from 70 A to
65 D determined according to DIN ISO 7619-1.
[0070] TPU-1 preferably has a molecular weight of more than 100 000
Da; TPU-2 preferably has a molecular weight in the range from 150
000 to 300 000 Da. The upper limit for the number-average molecular
weight of the thermoplastic polyurethanes is generally determined
by processibility and also the desired spectrum of properties.
[0071] In a further embodiment, the present invention therefore
relates to a composition as described above, wherein the
thermoplastic polyurethane TPU-1 has a molecular weight in the
range from 100 000 Da to 400 000 Da. In a further embodiment, the
present invention therefore relates to a composition as described
above, wherein the thermoplastic polyurethane TPU-2 has a molecular
weight in the range from 150 000 Da to 300 000 Da.
[0072] The composition of the invention comprises, for example, the
at least one thermoplastic polyurethane TPU-1 and the at least one
thermoplastic polyurethane TPU-2 in a sum total amount in the range
from 5% by weight to 95% by weight based on the overall
composition, especially in the range from 20% by weight to 80% by
weight based on the overall composition, preferably in the range
from 25% by weight to 75% by weight, more preferably in the range
from 30% by weight to 70% by weight, based in each case on the sum
total of components (I) and (II).
[0073] The thermoplastic polyurethanes may be prepared batchwise or
continuously by the known processes, for example using reactive
extruders or the belt process, by the "one-shot" process or the
prepolymer process, preferably by the "one-shot" process. In these
processes, the components to be reacted may be mixed with one
another successively or simultaneously, with immediate onset of the
reaction. In the extruder process, the formation components are
introduced into the extruder individually or as a mixture, for
example reacted preferably at temperatures of 100.degree. C. to
280.degree. C., more preferably 140.degree. C. to 250.degree. C.,
and the polyurethane obtained is then extruded, cooled, and
pelletized.
[0074] The composition of the invention comprises the at least one
thermoplastic polyurethane (TPU1) in an amount in the range from 5%
by weight to 95% by weight based on the overall composition,
especially in the range from 20% by weight to 80% by weight based
on the overall composition, preferably in the range from 25% by
weight to 75% by weight, based in each case on the sum total of
components (I) and (II).
[0075] Accordingly, the present invention also relates, in a
further embodiment, to a composition as described above, wherein
the proportion of the thermoplastic polyurethane (TPU-1) in the
composition is in the range from 5% to 95% by weight, based on the
sum total of components (I) and (II).
[0076] The sum of components (I) and (II) here adds up to 100% by
weight in each case.
[0077] In addition, the composition (Z-1) of the invention
comprises at least one copolyamide (PA-1). The proportion of the
copolyamide (PA-1) in the composition may vary within wide ranges
and is, for example, in the range from 5% by weight to 95% by
weight based on the overall composition, especially in the range
from 20% by weight to 80% by weight based on the overall
composition, preferably in the range from 25% by weight to 75% by
weight, based in each case on the sum total of components (I) and
(II).
[0078] Accordingly, the present invention also relates, in a
further embodiment, to a composition as described above, wherein
the proportion of the copolyamide (PA-1) in the composition is in
the range from 5% to 95% by weight, based on the sum total of
components (I) and (II).
[0079] In the context of the present invention, "at least one
copolyamide" is understood to mean either exactly one copolyamide
or a mixture of two or more copolyamides.
[0080] According to the invention, the copolyamide (PA-1) is
obtainable by polymerizing the components (A) at least one lactam,
and (B) a monomer mixture (M) comprising components (B1) at least
one C32-C40 dimer acid and (B2) at least one C4-C12 diamine.
[0081] According to the invention, the ratio of components (A) and
(B) used may vary within wide ranges. Suitable copolyamides are
described, for example, in WO 2018/050487 A1. The copolyamide
(PA-1) is preferably obtainable by polymerizing the following
components:
(A) 15% to 84% by weight of at least one lactam, (B) 16% to 85% by
weight of a monomer mixture (M) comprising the following
components: (B1) at least one C32-C40 dimer acid and (B2) at least
one C4-C12 diamine,
[0082] where the percentages by weight of components (A) and (B)
are each based on the sum total of the percentages by weight of
components (A) and (B).
[0083] In the context of the present invention, the terms
"component (A)" and "at least one lactam" are used synonymously and
therefore have the same meaning.
[0084] The same applies to the terms "component (B)" and "a monomer
mixture (M)". These terms are likewise used synonymously in the
context of the present invention and therefore have the same
meaning.
[0085] In the context of the present invention, "at least one
lactam" means either exactly one lactam or a mixture of two or more
lactams. Preference is given to exactly one lactam.
[0086] According to the invention, the at least one copolyamide is
preferably prepared by polymerizing 15% to 84% by weight of
component (A) and 16% to 85% by weight of component (B), preference
being given to preparing the copolyamide by polymerizing 40% to 83%
by weight of component (A) and 17% to 60% by weight of component
(B), and the at least one copolyamide especially preferably being
prepared by polymerizing 60% to 80% by weight of component (A) and
20% to 40% by weight of component (B), where the percentages by
weight of components (A) and (B) are each based on the sum total of
the percentages by weight of components (A) and (B).
[0087] Preferably, the sum total of the percentages by weight of
components (A) and (B) is 100% by weight.
[0088] In the context of the present invention, the percentages by
weight of components (A) and (B) are based on the percentages by
weight of components (A) and (B) prior to the polymerization, i.e.
when components (A) and (B) have not yet reacted with one another.
During the polymerization, the weight ratio of components (A) and
(B) may change if appropriate.
[0089] According to the invention, the copolyamide is prepared by
polymerizing components (A) and (B). The polymerization of
components (A) and (B) is known per se to those skilled in the art.
Typically, the polymerization of components (A) and (B) is a
condensation reaction. During the condensation reaction, component
(A) reacts with components (B1) and (B2) present in component (B)
and if appropriate with component (B3) which is described further
down and may likewise be present in component (B). This forms amide
bonds between the individual components. Typically, component (A)
is at least partly in open-chain form, i.e. as the amino acid,
during the polymerization.
[0090] The polymerization of components (A) and (B) can take place
in the presence of a catalyst. Suitable catalysts are all catalysts
known to those skilled in the art that catalyze the polymerization
of components (A) and (B). Such catalysts are known to those
skilled in the art. Preferred catalysts are phosphorus compounds,
for example sodium hypophosphite, phosphorous acid,
triphenylphosphine or triphenyl phosphite.
[0091] The polymerization of components (A) and (B) forms the
copolyamide, which therefore gains structural units derived from
component (A) and structural units derived from component (B).
Structural units derived from component (B) comprise structural
units derived from components (B1) and (B2) and, optionally, from
component (B3).
[0092] The polymerization of components (A) and (B) forms the
copolyamide as a copolymer. The copolymer may be a random copolymer
but it may likewise be a block copolymer.
[0093] In a block copolymer there is formation of blocks of units
derived from component (B), and blocks of units derived from
component (A). These alternate. In a random copolymer, there is
alternation of structural units derived from component (A) with
structural units derived from component (B). This alternation takes
place randomly; for example, two structural units derived from
component (B) may be followed by one structural unit derived from
component (A), which is followed in turn by one structural unit
derived from component (B), which is then followed by a structural
unit comprising three structural units derived from component
(A).
[0094] The at least one copolyamide (PA-1) is preferably a random
copolymer.
[0095] The present invention therefore also provides a polymer film
in which the at least one copolyamide is a random copolymer.
[0096] The preparation of the at least one copolyamide preferably
comprises the following steps: [0097] a) polymerizing components
(A) and (B) to obtain at least one first copolyamide, [0098] b)
pelletizing the at least one first copolyamide obtained in step a)
to obtain at least one pelletized copolyamide, [0099] c) extracting
the at least one pelletized copolyamide obtained in step b) with
water to obtain at least one extracted copolyamide, [0100] d)
drying the at least one extracted copolyamide obtained in step c)
at a temperature (Tr) to obtain the at least one copolyamide.
[0101] Suitable reaction conditions are described, for example, in
WO 2018/050487 A1.
[0102] The polymerization in step a) may take place in any reactor
known to those skilled in the art. Preference is given to stirred
tank reactors. It is also possible to use auxiliaries for improving
reaction management that are known to those skilled in the art, for
example defoamers such as polydimethylsiloxane (PDMS).
[0103] In step b), the at least one first copolyamide obtained in
step a) may be pelletized by any methods known to those skilled in
the art, for example by strand pelletization or underwater
pelletization.
[0104] The extraction in step c) may be effected by any methods
known to those skilled in the art.
[0105] During the extraction in step c), by-products formed in step
a) during the polymerization of components (A) and (B) are
typically extracted from the at least one pelletized
copolyamide.
[0106] In step d), the at least one extracted copolyamide obtained
in step c) is dried. Processes for drying are known to those
skilled in the art. According to the invention, the at least one
extracted copolyamide is dried at a temperature (Tr). The
temperature (Tr) is preferably above the glass transition
temperature (TG.sub.C) of the at least one copolyamide and below
the melting temperature (TM.sub.C) of the at least one
copolyamide.
[0107] The drying in step d) is typically effected for a period in
the range from 1 to 100 hours, preferably in the range from 2 to 50
hours and especially preferably in the range from 3 to 40
hours.
[0108] The at least one copolyamide typically has a glass
transition temperature (TG.sub.C). The glass transition temperature
(TG.sub.C) is for example in the range from 20 to 50.degree. C.,
preferably in the range from 23 to 47.degree. C. and especially
preferably in the range from 25 to 45.degree. C., determined
according to ISO 1 1357-2: 2014.
[0109] Component (A) in the context of the present invention is at
least one lactam. Lactams are known per se to those skilled in the
art. Preference is given in accordance with the invention to
lactams having 4 to 12 carbon atoms.
[0110] In the context of the present invention, "lactams" are
understood to mean cyclic amides having preferably 4 to 12 carbon
atoms, more preferably 5 to 8 carbon atoms, in the ring. Suitable
lactams are selected for example from the group consisting of
3-aminopropanolactam (propio-3-lactam; .beta.-lactam;
.beta.-propiolactam), 4-aminobutanolactam (butyro-4-lactam;
.gamma.-lactam; .gamma.-butyrolactam), 5-aminopentanolactam
(2-piperidinone; .delta.-lactam; .delta.-valerolactam),
6-aminohexanolactam (hexano-6-lactam; .epsilon.-lactam;
.epsilon.-caprolactam), 7-aminoheptanolactam (heptano-7-lactam;
.zeta.-lactam; .zeta.-heptanolactam), 8-aminooctanolactam
(octano-8-lactam; .eta.-lactam; .eta.-octanolactam),
9-aminononanolactam (nonano-9-lactam; .theta.-lactam;
.theta.-nonanolactam), 10-aminodecanolactam (decano-10-lactam;
.omega.-decanolactam), 11-aminoundecanolactam (undecano-11-lactam;
.omega.-undecanolactam) and 12-aminododecanolactam
(dodecano-12-lactam; .omega.-dodecanolactam).
[0111] According to the invention, the lactams may be unsubstituted
or at least monosubstituted. If at least monosubstituted lactams
are used, the nitrogen atom and/or the ring carbon atoms thereof
may bear one, two or more substituents selected independently from
the group consisting of C5- to C10-alkyl. C5- to C6-cycloalkyl, and
C5- to C10-aryl.
[0112] Suitable C5- to C10-alkyl substituents are, for example,
methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, and
tert-butyl. A suitable C5- to C6-cycloalkyl substituent is, for
example, cyclohexyl. Preferred C5- to C10-aryl substituents are
phenyl and anthranyl.
[0113] Preference is given to using unsubstituted lactams,
preference being given to .gamma.-lactam (.gamma.-butyrolactam),
.delta.-lactam (.delta.-valerolactam) and .epsilon.-lactam
(.epsilon.-caprolactam). Particular preference is given to
.delta.-lactam (.delta.-valerolactam) and .epsilon.-lactam
(.epsilon.-caprolactam), and .epsilon.-caprolactam is especially
preferred.
[0114] According to the invention, component (B) is a monomer
mixture (M). The monomer mixture (M) comprises components (B1), at
least one C32-C40 dimer acid, and (B2), at least one C4-C12
diamine.
[0115] In the context of the present invention, a monomer mixture
(M) is understood to mean a mixture of two or more monomers, where
at least components (B1) and (B2) are present in the monomer
mixture (M).
[0116] In the context of the present invention, the terms
"component (B1)" and "at least one C32-C40 dimer acid" are used
synonymously and therefore have the same meaning. The same applies
to the terms "component (B2)" and "at least one C4-C12
diamine".
[0117] These terms are likewise used synonymously in the context of
the present invention and therefore have the same meaning.
[0118] The monomer mixture (M) comprises, for example, in the range
from 45 to 55 mol % of component (B1) and in the range from 45 to
55 mol % of component (B2), based in each case on the sum total of
the molar percentages of components (B1) and (B2), preferably based
on the total molar amount of component (B).
[0119] Preferably, component (B) comprises in the range from 47 to
53 mol % of component (B1) and in the range from 47 to 53 mol % of
component (B2), based in each case on the sum total of the molar
percentages of components (B1) and (B2), preferably based on the
total molar amount of component (B).
[0120] More preferably, component (B) comprises in the range from
49 to 51 mol % of component (B1) and in the range from 49 to 51 mol
% of component (B2), based in each case on the sum total of the
molar percentages of components (B1) and (B2), preferably based on
the total molar amount of component (B).
[0121] The sum total of the molar percentages of components (B1)
and (B2) present in component (B) typically adds up to 100 mol
%.
[0122] Component (B) may also additionally comprise a component
(B3), at least one C4-C20 diacid. In the context of the present
invention, the terms "component (B3)" and "at least one C4-C20
diacid" are used synonymously and therefore have the same
meaning.
[0123] When component (B) additionally comprises component (B3), it
is preferable that component (B) comprises in the range from 25 to
54.9 mol % of component (B1), in the range from 45 to 55 mol % of
component (B2) and in the range from 0.1 to 25 mol % of component
(B3), based in each case on the total molar amount of component
(B).
[0124] More preferably, component (B) in that case comprises in the
range from 13 to 52.9 mol % of component (B1), in the range from 47
to 53 mol % of component (B2) and in the range from 0.1 to 13 mol %
of component (B3), based in each case on the total molar amount of
component (B).
[0125] Further preferably, component (B) in that case comprises in
the range from 7 to 50.9 mol % of component (B1), in the range from
49 to 51 mol % of component (B2) and in the range from 0.1 to 7 mol
% of component (B3), based in each case on the total molar amount
of component (B).
[0126] When component (B) additionally comprises component (B3),
the molar percentages of components (B1), (B2) and (B3) typically
add up to 100 mole percent.
[0127] The monomer mixture (M) may further comprise water.
[0128] Components (B1) and (B2) and optionally (B3) of component
(B) can react with one another to obtain amides. This reaction is
known per se to those skilled in the art. Therefore, component (B)
may comprise components (B1) and (B2) and optionally (B3) in fully
reacted form, in partly reacted form or in unreacted form.
Preferably, component (B) comprises components (B1), (B2) and
optionally (B3) in unreacted form.
[0129] In the context of the present invention, "in unreacted form"
thus means that component (B1) is present as the at least one
C32-C40 dimer acid and component (B2) as the at least one C4-C12
diamine, and component (B3), if present, as the at least one C4-C20
diacid.
[0130] If components (B1) and (B2) and any (B3) present have at
least partly reacted with one another, components (B1) and (B2) and
any (B3) present are at least partly in amide form.
[0131] According to the invention, component (B1) is at least one
C32-C40 dimer acid. In the context of the present invention. "at
least one C32-C40 dimer acid" means either exactly one C32-C40
dimer acid or a mixture of two or more C32-C40 dimer acids.
[0132] Dimer acids are also referred to as dimer fatty acids.
C32-C40 dimer acids are known per se to those skilled in the art
and are typically prepared by dimerizing unsaturated fatty acids.
This dimerization may be catalyzed by aluminas, for example.
Suitable unsaturated fatty acids for preparing the at least one
C32-C40 dimer acid are known to those skilled in the art and are,
for example, unsaturated C16 fatty acids, unsaturated C16 fatty
acids and unsaturated C20 fatty acids.
[0133] Component (B1) is therefore preferably prepared proceeding
from unsaturated fatty acids selected from the group consisting of
unsaturated C16 fatty acids, unsaturated C18 fatty acids and
unsaturated C20 fatty acids, particular preference being given to
the unsaturated C18 fatty acids. An example of a suitable
unsaturated C16-fatty acid is palmitoleic acid
((9Z)-hexadeca-9-enoic acid).
[0134] Suitable unsaturated C18 fatty acids are, for example,
selected from the group consisting of petroselinic acid
((6Z)-octadeca-6-enoic acid), oleic acid ((9Z)-octadeca-9-enoic
acid), elaidic acid ((9E)-octadeca-9-enoic acid), vaccenic acid
((11E)-octadeca-11-enoic acid), linoleic acid
((9Z,12Z)-octadeca-9,12-dienoic acid), alpha-linolenic acid
((9Z,12Z,15Z)-octadeca-9,12,15-trienoic acid), gamma-linolenic acid
((6Z,9Z,12Z)-octadeca-6,9,12-trienoic acid), calendulic acid
((8E,10E,12Z)-octadeca-8,10,12-trienoic acid), punicic acid
((9Z,11E,13Z)-octadeca-9,11,13-trienoic acid),
[0135] alpha-eleostearic acid
((9Z,11E,13E)-octadeca-9,11,13-trienoic acid) and beta-eleostearic
acid ((9E,11E,13E)-octadeca-9,11,13-trienoic acid). Particular
preference is given to unsaturated cis fatty acids selected from
the group consisting of petroselinic acid ((6Z)-octadeca-6-enoic
acid), oleic acid ((9Z)-octadeca-9-enoic acid), elaidic acid
((9E)-octadeca-9-enoic acid), vaccenic acid
((11E)-octadeca-11-enoic acid), linoleic acid
((9Z,12Z)-octadeca-9,12-dienoic acid).
[0136] Suitable unsaturated C20 fatty acids are for example
selected from the group consisting of gadoleic acid
((9Z)-eicosa-9-enoic acid), icosenoic acid ((11Z)-eicosa-11-enoic
acid), arachidonic acid
((5Z,8Z,11Z,14Z)-eicosa-5,8,11,14-tetraenoic acid) and timnodonic
acid ((5Z,8Z,11Z,14Z,17Z)-eicosa-5,8,11,14,17-pentaenoic acid).
[0137] Component (B1) is especially preferably at least one C36
dimer acid.
[0138] The at least one C36-dimer acid is preferably prepared from
unsaturated cis fatty acids. The C36 dimer acid is more preferably
prepared proceeding from cis fatty acids selected from the group
consisting of petroselinic acid ((6Z)-octadeca-6-enoic acid), oleic
acid ((9Z)-octadeca-9-enoic acid), elaidic acid
((9E)-octadeca-9-enoic acid),
[0139] vaccenic acid ((11E)-octadeca-11-enoic acid) and linoleic
acid ((9Z,12Z)-octadeca-9,12-dienoic acid).
[0140] The preparation of component (B1) from unsaturated fatty
acids can additionally form trimer acids; residues of unreacted
unsaturated fatty acid may also remain.
[0141] The formation of trimer acids is known to those skilled in
the art.
[0142] Preferably in accordance with the invention, component (B1)
comprises at most 0.5% by weight of unreacted unsaturated fatty
acid and at most 0.5% by weight of trimer acid, more preferably at
most 0.2% by weight of unreacted unsaturated fatty acid and at most
0.2% by weight of trimer acid, based in each case on the total
weight of component (B1).
[0143] Dimer acids (also known as dimerized fatty acids or dimer
fatty acids) thus refer generally, and especially in the context of
the present invention, to mixtures that are prepared by
oligomerization of unsaturated fatty acids. They are preparable,
for example, by catalytic dimerization of plant-derived unsaturated
fatty acids, using unsaturated C16- to C20-fatty acids in
particular as starting materials. The bond formation proceeds
primarily by the Diels-Alder mechanism, and results, depending on
the number and position of the double bonds in the fatty acids used
to prepare the dimer acids, in mixtures of primarily dimeric
products having cycloaliphatic, linear aliphatic, branched
aliphatic, and also C6 aromatic hydrocarbon groups between the
carboxyl groups. Depending on the mechanism and/or any subsequent
hydrogenation, the aliphatic radicals may be saturated or
unsaturated and the proportion of aromatic groups may also vary.
The radicals between the carboxylic acid groups then comprise 32 to
40 carbon atoms for example. They are preferably prepared using
fatty acids having 18 carbon atoms, so that the dimeric product
thus has 36 carbon atoms. The radicals which join the carboxyl
groups of the dimer fatty acids preferably comprise no unsaturated
bonds and no aromatic hydrocarbon radicals.
[0144] In the context of the present invention, preference is thus
given to using Cie fatty acids in the preparation. It is
particularly preferable to use linolenic acid, linoleic acid and/or
oleic acid.
[0145] Depending on reaction management the above-described
oligomerization affords mixtures which comprise primarily dimeric,
but also trimeric, molecules and also monomeric molecules and other
by-products. Purification by distillation is customary. Commercial
dimer acids generally comprise at least 80% by weight of dimeric
molecules, up to 19% by weight of trimeric molecules, and not more
than 1% by weight of monomeric molecules and of other
by-products.
[0146] It is preferable to use dimer acids that consist to an
extent of at least 90% by weight, preferably to an extent of at
least 95% by weight, most preferably to an extent of at least 98%
by weight, of dimeric fatty acid molecules.
[0147] The proportions of monomeric, dimeric, and trimeric
molecules and of other by-products in the dimer acids may be
determined by gas chromatography (GC), for example. The dimer acids
are converted to the corresponding methyl esters by the boron
trifluoride method (cf. DIN EN ISO 5509) before GC analysis and
then analyzed by GC.
[0148] In the context of the present invention it is thus a
fundamental feature of "dimer acids" that production thereof
comprises oligomerization of unsaturated fatty acids. This
oligomerization gives rise principally, in other words to an extent
preferably of at least 80% by weight, more preferably to an extent
of at least 90% by weight, even more preferably to an extent of at
least 95% by weight and more particularly to an extent of at least
98% by weight, to dimeric products. The fact that the
oligomerization thus forms predominantly dimeric products
comprising exactly two fatty acid molecules justifies this
designation, which is in any case commonplace. An alternative
expression for the relevant term "dimer acids" is thus "mixture
comprising dimerized fatty acids".
[0149] The dimer acids to be used are obtainable as commercial
products. Examples include Radiacid 0970, Radiacid 0971, Radiacid
0972, Radiacid 0975, Radiacid 0976, and Radiacid 0977 from Oleon,
Pripol 1006, Pripol 1009, Pripol 1012, and Pripol 1013 from Croda,
Empol 1008. Empol 1012. Empol 1061, and Empol 1062 from BASF SE,
and Unidyme 10 and Unidyme TI from Arizona Chemical.
[0150] Component (B1) has, for example, an acid number in the range
from 190 to 200 mg KOH/g.
[0151] According to the invention, component (B2) is at least one
C4-C12 diamine. In the context of the present invention, "at least
one C4-C12 diamine" means either exactly one C4-C12 diamine or a
mixture of two or more C4-C12 diamines. In the context of the
present compound. "C4-C12 diamine" is understood to mean aliphatic
and/or aromatic compounds having four to twelve carbon atoms and
two amino groups (--NH2 groups). The aliphatic and/or aromatic
compounds may be unsubstituted or additionally at least
monosubstituted. If the aliphatic and/or aromatic compounds are
additionally at least monosubstituted, they may bear one, two or
more substituents that do not take part in the polymerization of
components (A) and (B). Such substituents are for example alkyl or
cycloalkyl substituents.
[0152] These are known per se to those skilled in the art. The at
least one C4-C12 diamine is preferably unsubstituted.
[0153] Examples of suitable components (B2) are selected from the
group consisting of 1,4-diaminobutane (butane-1,4-diamine;
tetramethylenediamine; putrescine), 1,5-diaminopentane
(pentamethylenediamine; pentane-1,5-diamine; cadaverine),
1,6-diaminohexane (hexamethylenediamine; hexane-1,6-diamine),
1-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane,
1,10-diaminodecane (decamethylenediamine), 1,11-diaminoundecane
(undecamethylenediamine) and 1,12-diaminododecane
(dodecamethylenediamine).
[0154] Preferably, component (B2) is selected from the group
consisting of tetramethylenediamine, pentamethylenediamine,
hexamethylenediamine, decamethylenediamine and
dodecamethylenediamine.
[0155] According to the invention, any component (B3) present in
component (B) is at least one C4-C20 diacid. In the context of the
present invention, "at least one C4-C20 diacid" means either
exactly one C4-C20 diacid or a mixture of two or more C4-C20
diacids.
[0156] In the context of the present invention, "C4-C20 diacid" is
understood to mean aliphatic and/or aromatic compounds having two
to eighteen carbon atoms and two carboxyl groups (--COOH groups).
The aliphatic and/or aromatic compounds may be unsubstituted or
additionally at least monosubstituted. If the aliphatic and/or
aromatic compounds are additionally at least monosubstituted, they
may bear one, two or more substituents that do not take part in the
polymerization of components (A) and (B). Such substituents are for
example alkyl or cycloalkyl substituents. These are known to those
skilled in the art. The at least one C4-C20 diacid is preferably
unsubstituted.
[0157] Suitable components (B3) are for example selected from the
group consisting of butanedioic acid (succinic acid), pentanedioic
acid (glutaric acid), hexanedioic acid (adipic acid), heptanedioic
acid (pimelic acid), octanedioic acid (suberic acid), nonanedioic
acid (azelaic acid), decanedioic acid (sebacic acid), undecanedioic
acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic
acid and hexadecanedioic acid.
[0158] Preferably, component (B3) is selected from the group
consisting of pentanedioic acid (glutaric acid), hexanedioic acid
(adipic acid), decanedioic acid (sebacic acid) and dodecanedioic
acid.
[0159] According to the invention, the composition (Z1) can be
produced, for example, by mixing the individual components, for
example the thermoplastic polyurethane (TPU1) and the polyamide
(PA1), for example in a suitable apparatus such as an extruder or a
kneader. The composition (Z1) can be produced here under conditions
known per se.
[0160] According to the invention, it is also possible to use
further additives, for example flame retardants or fillers.
Suitable fillers, plasticizers or flame retardants are known per se
to the person skilled in the art.
[0161] In a further embodiment, the present invention accordingly
relates to a composition (Z1) as described above, wherein the
composition comprises at least one flame retardant.
[0162] In a further embodiment, the present invention also relates
to a composition (Z1) as described above, wherein the composition
comprises at least one filler.
[0163] In the context of the present invention, preference can be
given to using flame retardants selected from the group consisting
of metal hydroxides, nitrogen-containing flame retardants and
phosphorus-containing flame retardants. Preference is given in
accordance with the invention to flame retardants selected from the
group consisting of melamine cyanurate, magnesium hydroxide and
phosphorus-containing flame retardants.
[0164] In a further embodiment, the present invention also relates
to a composition (Z1) as described above, wherein the flame
retardant is selected from the group consisting of metal
hydroxides, nitrogen-containing flame retardants and
phosphorus-containing flame retardants.
[0165] In a further embodiment, the present invention also further
relates to a composition as described above, wherein the
composition comprises at least one flame retardant selected from
the group consisting of melamin cyanurate, magnesium hydroxide and
phosphorus-containing flame retardants.
[0166] Also suitable in the context of the present invention, for
example, are mixtures of different flame retardants, for example
mixtures comprising one or more phosphorus-containing flame
retardants.
[0167] Accordingly, the present invention, in a further embodiment,
also relates to a composition as described above, wherein the
composition comprises at least one first phosphorus-containing
flame retardant (F1) selected from the group consisting of
derivatives of phosphoric acid and derivatives of phosphonic acid,
and at least one further phosphorus-containing flame retardant (F2)
selected from the group consisting of derivatives of phosphinic
acid.
[0168] Suitable flame retardants are, for example, also metal
hydroxides. In the event of fire, metal hydroxides released
exclusively water and therefore do not form any toxic or corrosive
smoke gas products. Furthermore, these hydroxides are capable of
reducing smoke gas density in the event of fire. However, a
disadvantage of these substances is that, in some cases, they
promote the hydrolysis of thermoplastic polyurethanes and also
affect the oxidative aging of the polyurethanes.
[0169] Suitable hydroxides in the context of the present invention
are preferably those of magnesium, calcium, zinc and/or aluminum or
mixtures thereof. More preferably, the metal hydroxide is selected
from the group consisting of aluminum hydroxides, aluminum oxide
hydroxides, magnesium hydroxide and a mixture of two or more of
these hydroxides.
[0170] The compositions of the invention may also comprise a
phosphorus-containing flame retardant. According to the invention,
it is possible in principle to use any known phosphorus-containing
flame retardants for thermoplastic polyurethanes.
[0171] Preference is given, in the context of the present
invention, to using derivatives of phosphoric acid, derivatives of
phosphonic acid or derivatives of phosphinic acid or mixtures of
two or more of these derivatives. In a further preferred
embodiment, the phosphorus-containing flame retardant is liquid at
21.degree. C.
[0172] Preferably, the derivatives of phosphoric acid, phosphonic
acid or phosphinic acid are salts with an organic or inorganic
cation or organic esters. Organic esters are derivatives of the
phosphorus-containing acids in which at least one oxygen atom
bonded directly to the phosphorus has been esterified with an
organic radical. In a preferred embodiment the organic ester is an
alkyl ester, and in another preferred embodiment an aryl ester.
More preferably, all hydroxyl groups of the corresponding
phosphorus-containing acid have been esterified.
[0173] Suitable organic phosphate esters are, for example, the
triesters of phosphoric acid, such as trialkyl phosphates and
especially triaryl phosphates, for example resorcinol bis(diphenyl
phosphate).
[0174] Especially suitable in accordance with the invention are
salts of the respective derivatives of phosphoric acid, phosphonic
acid or phosphinic acid, more preferably phosphinate salts.
Suitable examples in the context of the present invention are
melamine polyphosphate or diethylaluminum phosphinate.
[0175] In addition, it is also possible in the context of the
present invention to use nitrogen-containing flame retardants.
According to the invention, it is possible in principle to use any
known nitrogen-containing flame retardants for thermoplastic
polyurethanes.
[0176] Suitable flame retardants in the context of the present
invention are, for example, also melamine derivatives such as, in
particular, melamine polyphosphate or melamine cyanurate.
[0177] In the context of the present invention, it is also possible
that the composition, as well as the thermoplastic polyurethane,
comprises mixtures of various flame retardants, for example a
melamine derivative and a derivative of phosphoric acid, or a
melamine derivative and a derivative of phosphinic acid, or a
melamine derivative, a derivative of phosphoric acid and a
derivative of phosphinic acid.
[0178] The melamine derivative may preferably be a melamine
cyanurate. Accordingly, the present invention, in a further
embodiment, may also relate to a composition comprising, as well as
the thermoplastic polyurethane, for example, a melamine cyanurate
and a derivative of phosphoric acid, or a melamine cyanurate and a
derivative of phosphinic acid, or a melamine cyanurate, a
derivative of phosphoric acid and a derivative of phosphinic acid.
For example, the composition of the invention comprises at least
one thermoplastic polyurethane, at least melamine cyanurate, at
least one first phosphorus-containing flame retardant (F1) selected
from the group consisting of derivatives of phosphoric acid and
derivatives of phosphonic acid and at least one further
phosphorus-containing flame retardant (F2) selected from the group
consisting of derivatives of phosphinic acid.
[0179] Preferably, the composition, aside from the melamine
cyanurate, the at least one phosphorus-containing flame retardant
(F1) and the at least one phosphorus-containing flame retardant
(F2), does not comprise any further flame retardants. Further
preferably, the composition of the invention comprises melamine
cyanurate, exactly one phosphorus-containing flame retardant (F1)
selected from the group consisting of derivatives of phosphoric
acid and derivatives of phosphonic acid and exactly one
phosphorus-containing flame retardant (F2) selected from the group
consisting of derivatives of phosphinic acid.
[0180] Accordingly, the present invention, in a further embodiment,
also relates to a composition as described above, wherein the
phosphorus-containing flame retardant (F1) is a phosphinate.
[0181] In a further embodiment, the present invention also further
relates to a composition as described above, wherein the
phosphinate is selected from the group consisting of aluminum
phosphinates or zinc phosphinates.
[0182] In addition, the present invention, in a further embodiment,
also relates to a composition as described above, wherein the
phosphorus-containing flame retardant (F2) is a phosphoric
ester.
[0183] In a further embodiment, the present invention also relates
to a composition as described above, wherein the flame retardant
(F1) is selected from the group consisting of resorcinol
bis(diphenyl phosphate) (RDP), bisphenol A bis(diphenyl phosphate)
(BDP) and diphenyl cresyl phosphate (DPK).
[0184] The proportion of the flame retardant (F) in the composition
is, for example, in the range from 2.5% to 40% by weight, based on
the overall composition, preferably in the range from 5% to 30% by
weight, based on the overall composition, more preferably in the
range from 10% to 20% by weight, based on the overall
composition.
[0185] In a further embodiment, the present invention accordingly
also relates to a composition as described above, wherein the flame
retardant (F) is present in an amount in the range from 2.5% to 40%
by weight, based on the overall composition.
[0186] In one embodiment, for preparation of the compositions of
the invention, thermoplastic polyurethane and flame retardant are
processed in one step. In other preferred embodiments, for
production of the compositions of the invention, a reaction
extruder, a belt system or other suitable apparatus is firstly used
to produce a thermoplastic polyurethane, preferably in pellet form,
into which at least one further flame retardant is then introduced
in at least one further step, or else two or more steps.
[0187] The mixing of the thermoplastic polyurethane with the at
least one flame retardant is effected, for example, in a mixing
unit which is preferably an internal kneader or an extruder,
preferably a twin-screw extruder. In another preferred embodiment
using an extruder, the flame retardant introduced is liquid at the
temperature that exists downstream of the addition thereof to the
extruder in flow direction.
[0188] The composition of the invention may further comprise a
filler (FS1). According to the invention, the chemical nature and
form of the filler (FS1) may vary within wide ranges, provided that
compatibility with the composition (Z1) is sufficient. The filler
(FS1) should be chosen here such that the form and particle size of
the filler enable sufficient miscibility and homogeneous
distribution in the composition.
[0189] Suitable fillers are for example glass fibers, glass beads,
carbon fibers, aramid fibers, potassium titanate fibers, fibers of
liquid-crystal polymers, organic fibrous fillers or inorganic
reinforcing materials. Organic fibrous fillers are for example
cellulose fibers, hemp fibers, sisal or kenaf. Inorganic
reinforcing materials are, for example, ceramic fillers, such as
aluminum nitride and boron nitride, or mineral fillers, such as
asbestos, talc, wollastonite, microvit, silicates, chalk, calcined
kaolins, mica and quartz flour. Preferably in accordance with the
invention, the filler (FS1) is selected from the group consisting
of glass fibers, carbon fibers, aramid fibers, potassium titanates
fibers, fibers of liquid-crystalline polymers, metal fibers,
polyester fibers, polyamide fibers, organic fibrous fillers and
inorganic fibrous fillers.
[0190] In a further embodiment, the present invention accordingly
also relates to a composition as described above, wherein the
filler (FS1) is selected from the group consisting of glass fibers,
carbon fibers, aramid fibers, potassium titanates fibers, fibers of
liquid-crystalline polymers, metal fibers, polyester fibers,
polyamide fibers, organic fibrous fillers and inorganic fibrous
fillers.
[0191] Fibrous fillers are preferred in the context of the present
invention. In a further embodiment, the present invention
accordingly also relates to a composition as described above,
wherein the filler (FS1) is fibrous.
[0192] The dimensions of the fillers used may vary within customary
ranges. The filler used preferably has a length in the range from 3
mm to 4 mm and a diameter in the range from 1 .mu.m to 20 .mu.m,
each determined in accordance with ASTM D578-98. In a further
embodiment, the present invention accordingly also relates to a
composition as described above, wherein the filler (FS1) has a
length in the range from 3 mm to 4 mm and a diameter in the range
from 1 .mu.m to 20 .mu.m, each determined in accordance with ASTM
D578-98.
[0193] The fillers, for example the fibrous fillers, may have been
pretreated for better compatibility with the thermoplastic, for
example with a silane compound.
[0194] Preference is given to using inorganic fibrous fillers. When
using inorganic fibrous fillers, a greater reinforcing effect and a
higher heat resistance are observed.
[0195] According to the invention, the composition may also
comprise two or more fillers.
[0196] The proportion of the filler (FS1) in the composition is,
for example, in the range from 40% to 60% by weight, based on the
overall composition, preferably in the range from 45% to 55% by
weight, based on the overall composition, more preferably in the
range from 48% to 52% by weight, based on the overall
composition.
[0197] In a further embodiment, the present invention accordingly
also relates to a composition as described above, wherein the
filler (FS1) is present in an amount in the range from 40% to 60%
by weight, based on the overall composition.
[0198] According to the invention, the composition may comprise
further components, for example demolding aids, UV protection,
antioxidant or color pigments.
[0199] In a further aspect, the present invention also relates to a
process for producing a composition (Z-1). The present invention
relates to a process for producing a composition (Z-1), comprising
the following steps: [0200] (a) providing [0201] (I) a
thermoplastic polyurethane (TPU-1) and [0202] (II) a copolyamide
(PA-1), prepared by polymerizing at least one lactam, and a monomer
mixture (M) comprising components (B1) at least one C32-C40 dimer
acid and (B2) at least one C4-C12 diamine, and [0203] (b) mixing
components (I) and (II).
[0204] This process of the invention comprises at least steps (a)
and (b). The process may comprise further steps, for example drying
steps or temperature adjustments. According to the invention, it is
also possible to add further components, for example the
aforementioned auxiliaries and additives.
[0205] In a further aspect, the present invention accordingly
relates to a process as described above, wherein the components
used are dried, for example at a temperature in the range from 80
to 100.degree. C. For example, the drying can be effected at a
temperature in the range from 80 to 100.degree. C. for a period of
2 to 4 hours.
[0206] According to the invention, in step (b), the copolyamide
(PA-1) and the thermoplastic polyurethane (TPU-1) are mixed. This
can be effected in apparatuses known per se to the person skilled
in the art, for example in an extruder. Suitable extruders and
process conditions are known per se to the person skilled in the
art. For example, the mixing in an extruder can be effected at a
temperature in the range from 180 to 240.degree. C., preferably at
a temperature in the range from 190.degree. C. to 230.degree. C.,
more preferably at a temperature in the range from 200.degree. C.
to 225.degree. C.
[0207] Suitable dwell times in the extruder are, for example, in
the range from 5 to 20 minutes, preferably 10 to 15 minutes.
[0208] With regard to the preferred embodiments, reference is made
to the above details of the components used with preference.
[0209] Suitable processes for producing the composition are known
per se to the person skilled in the art. In the context of the
present invention, processes known per se are typically used for
compounding.
[0210] For example, the composition can be produced in an extruder
in a manner known per se, for example in a twin-screw extruder.
According to the invention, it is preferable to add the filler in
portions, for example a portion of the extruder intake and a
further portion of a second dosage site, for example a side feeder.
The temperature here is preferably in the range from 160 to
230.degree. C. In the context of the present invention, the
extruder can be operated, for example, at a speed in the range from
150 to 300 revolutions per minute.
[0211] The present invention further relates to a composition
obtained or obtainable by a process of the invention.
[0212] The present invention also relates to the use of the
composition (Z1) of the invention or of a composition obtained or
obtainable by a process of the invention for production of a shaped
article.
[0213] In a further aspect, the present invention also further
relates to shaped articles comprising a composition of the
invention according to or a composition obtained or obtainable by a
process of the invention.
[0214] The present invention also relates to the use of the
composition of the invention comprising at least one
flame-retardant thermoplastic polyurethane as described above for
production of coatings, damping elements, bellows, films or fibers,
molded articles, floors for buildings and transport, random-laid
webs, preferably seals, rollers, shoe soles, hoses, cables, cable
connectors, cable sheathings, cushions, laminates, profiles, belts,
saddles, foams, plug connectors, trailing cables, solar modules,
automotive trim. Use for the production of cable sheathings is
preferred. Production is preferably effected from pellet materials
by injection molding, calendering, powder sintering or extrusion
and/or by additional foaming of the composition of the
invention.
[0215] On account of their good mechanical properties and good
thermal characteristics, the thermoplastic polyurethanes of the
invention and the compositions of the invention are especially
suitable for production of films, moldings, wheels/rollers, fibers,
automotive trim, hoses, cable plugs, bellows, trailing cables,
cable sheathings, seals, belts or damping elements.
[0216] The present invention thus also provides films, moldings,
wheels/rollers, fibers, automotive trim, hoses, cable plugs,
bellows, trailing cables, cable sheathings, seals, belts or damping
elements comprising a thermoplastic polyurethane as described above
or a composition as described above.
[0217] Further embodiments of the present invention can be found in
the claims and the examples. It will be appreciated that the
features of the subject matter/process of the invention or of the
uses of the invention recited hereinabove and elucidated
hereinbelow may be used not only in the combination specified in
each case but also in other combinations without departing from the
scope of the invention. Thus, for example, the combination of a
preferred feature with a particularly preferred feature, or of a
feature not characterized further with a particularly preferred
feature etc., is also encompassed implicitly even if this
combination is not mentioned explicitly.
[0218] Illustrative embodiments of the present invention are
detailed hereinbelow, but are not intended to limit the present
invention. In particular, the present invention also encompasses
those embodiments that result from the dependency references and
hence combinations specified hereinbelow. [0219] 1. A composition
comprising at least [0220] (1) a thermoplastic polyurethane (TPU-1)
and [0221] (II) a copolyamide (PA-1), prepared by polymerization of
[0222] (A) at least one lactam, and [0223] (B) a monomer mixture
(M) comprising the following components: [0224] (B1) at least one
C32-C40 dimer acid and [0225] (B2) at least one C4-C12 diamine.
[0226] 2. The composition according to embodiment 1, wherein the
thermoplastic polyurethane (TPU-1) is based on an aromatic
diisocyanate. [0227] 3. The composition according to embodiment 2,
wherein the thermoplastic polyurethane (TPU-1) has a Shore hardness
in the range from 70 A to 85 D, determined in accordance with DIN
53505. [0228] 4. The composition according to embodiment 1, wherein
the thermoplastic polyurethane (TPU-1) is based on an aliphatic
diisocyanate. [0229] 5. The composition according to any of
embodiments 1 to 4, wherein the proportion of the thermoplastic
polyurethane (TPU-1) in the composition is in the range from 5% to
95% by weight, based on the sum total of components (I) and (II).
[0230] 6. The composition according to any of embodiments 1 to 5,
wherein the proportion of the copolyamide (PA-1) in the composition
is in the range from 5% to 95% by weight, based on the sum total of
components (I) and (II). [0231] 7. The composition according to any
of embodiments 1 to 6, wherein the composition comprises at least
one flame retardant selected from the group consisting of melamine
cyanurate, magnesium hydroxide and phosphorus-containing flame
retardants. [0232] 8. The composition according to any of
embodiments 1 to 7, wherein the composition comprises at least one
first phosphorus-containing flame retardant (F1) selected from the
group consisting of derivatives of phosphoric acid and derivatives
of phosphonic acid and at least one further phosphorus-containing
flame retardant (F2) selected from the group consisting of
derivatives of phosphinic acid. [0233] 9. The composition according
to embodiment 8, wherein the phosphorus-containing flame retardant
(F1) is a phosphinate. [0234] 10. The composition according to
embodiment 9, wherein the phosphinate is selected from the group
consisting of aluminum phosphinates or zinc phosphinates. [0235]
11. The composition according to any of embodiments 8 to 10,
wherein the phosphorus-containing flame retardant (F2) is a
phosphoric ester. [0236] 12. The composition according to any of
embodiments 8 to 11, wherein the flame retardant (F1) is selected
from the group consisting of resorcinol bis(diphenyl phosphate)
(RDP), bisphenol A bis(diphenyl phosphate) (BDP) and diphenyl
cresyl phosphate (DPK). [0237] 13. A process for producing a
composition (Z-1), comprising the steps of [0238] (a) providing
[0239] (I) a thermoplastic polyurethane (TPU-1) and [0240] (II) a
copolyamide (PA-1), prepared by polymerizing at least one lactam,
and a monomer mixture (M) comprising components (B1) at least one
C32-C40 dimer acid and (B2) at least one C4-C12 diamine, and [0241]
(b) mixing components (I) and (II). [0242] 14. The use of a
composition according to any of embodiments 1 to 12 for production
of shaped articles. [0243] 15. A shaped article comprising a
composition according to any of embodiments 1 to 12. [0244] 16. A
shaped article comprising a composition according to any of
embodiments 14 to 20. [0245] 17. A shaped article comprising a
composition according to any of embodiments 22 to 23.
[0246] The examples that follow serve to illustrate the invention,
but are in no way limiting in respect of the subject matter of the
present invention.
EXAMPLES
1. Starting Materials
[0247] Ultramid RX2298.RTM.: copolymer of nylon-6 and nylon-6,36
(PA 6/6.36) from BASF SE.RTM., sold under the Ultramid RX2298.RTM.
brand name, having a viscosity number to DIN 53727 (0.005 g/ml
H.sub.2SO.sub.4) of 28 ml/g, an MVR (230.degree. C./10 kg) of 115
cm.sup.3/10 min, a melting temperature of 201.degree. C. and a
density of 1.054 g/cm.sup.3.
[0248] Elastollan 1180 A10: TPU of Shore hardness 80 A from BASF
Polyurethanes GmbH, Elastogranstrasse 60, 49448 Lemforde, based on
polytetrahydrofuran polyol (PTHF) having a molecular weight of 1000
g/mol, butane-1,4-diol, diphenylmethane 4,4'-diisocyanate.
[0249] Elastollan 1160 D12: TPU of Shore hardness 60 D from BASF
Polyurethanes GmbH, Elastogranstrasse 60, 49448 Lemforde, based on
polytetrahydrofuran polyol (PTHF) having a molecular weight of
1000, butane-1,4-diol, MDI.
[0250] Elastollan 1278 D11U: TPU of Shore hardness 78 D from BASF
Polyurethanes GmbH, Elastogranstrasse 60, 49448 Lemforde, based on
polytetrahydrofuran polyol (PTHF) having a molecular weight of
1000, butane-1,4-diol, MDI.
[0251] Elastollan 1283 D11U: TPU of Shore hardness 83 D from BASF
Polyurethanes GmbH, Elastogranstrasse 60, 49448 Lemforde, based on
polytetrahydrofuran polyol (PTHF) having a molecular weight of
1000, butane-1,4-diol. MDI.
[0252] Elastollan 685 A10: TPU of Shore hardness 85 A from BASF
Polyurethanes GmbH, Elastogranstrasse 60, 49448 Lemforde, based on
butanediol adipate ester, butane-1,4-diol, MDI.
[0253] Elastollan B60 D11: TPU of Shore hardness 85 A from BASF
Polyurethanes GmbH, Elastogranstrasse 60, 49448 Lemforde, based on
butanediol adipate ester, butane-1,4-diol, MDI.
[0254] Elastollan AC85 A12: TPU of Shore hardness 60 A from BASF
Polyurethanes GmbH, Elastogranstrasse 60, 49448 Lemforde, based on
polyester polyol (adipic acid, butane-1,4-diol and hexane-1,6-diol)
having a molecular weight of 2000, butane-1,4-diol, hexamethylene
diisocyanate.
[0255] Elastollan L1160 D10N: TPU of Shore hardness 60 D from BASF
Polyurethanes GmbH, Elastogranstrasse 60, 49448 Lemforde, based on
polytetrahydrofuran polyol (PTHF) having a molecular weight of 1000
g/mol, 1,4-butanediol, 4,4'-diisocyanatodicyclohexylmethane.
[0256] Exolit OP 1230: Aluminum diethylphosphinate, CAS #:
225789-38-8, Clariant Produkte (Deutschland) GmbH, Chemiepark
Knapsack, 50351 HOrth, water content % (w/w) <0.2, average
particle size (D50) 20-40 .mu.m.
[0257] Fyrolflex RDP: Resorcinol bis(diphenyl phosphate), CAS #:
125997-21-9, Supresta Netherlands B.V., Office Park De Hoef,
Hoefseweg 1, 3821 AE Amersfoort, the Netherlands, viscosity at
25.degree. C.=700 mPas, acid number <0.1 mg KOH/g, water content
% (w/w)<0.1.
[0258] Melapur MC 15 ED: Melamine cyanurate
(1,3,5-triazine-2,4,6(1H,3H,5H)-trione, compound with
1,3,5-triazine-2,4,6-triamine (1:1)), CAS #: 37640-57-6, BASF SE,
67056 Ludwigshafen, GERMANY, particle size D99% </=50 .mu.m,
D50%<=4.5 .mu.m, water content % (w/w)<0.2.
[0259] Melapur MC 200/70: Melamine polyphosphate (nitrogen content
42-44% by wt., phosphorous content 12-14% by wt.)), CAS #:
218768-84-4. BASF SE, 67056 Ludwigshafen, GERMANY, particle size
D99% </=70 .mu.m, average particle diameter D50%<=10 .mu.m,
water content % (w/w)<0.3.
[0260] Chopvantage HP3550 EC10-3,8: Glass fibers from PPG
Industries Fiber Glass, Energieweg 3, 9608 PC Westerbroek, The
Netherlands. E glass, filament diameter 10 .mu.m, length 3.8
mm.
2. Production Examples
[0261] The tables that follow list compositions in which the
individual constituents are stated in parts by weight (PW). The
mixtures were each produced with a Berstorff ZE 40 A twin-screw
extruder with screw length 35 D divided into 10 barrel sections.
Pelletization was effected using standard underwater pelletization
apparatus from Gala (UWG).
[0262] Density, Shore hardness, tensile strength, tear propagation
resistance, abrasion and elongation at break were determined on
films having a thickness of 1.6 mm. The films were extruded with an
Arenz single-screw extruder having a three-zone screw with a mixing
section (screw ratio 1:3). The films were assessed in accordance
with their appearance.
[0263] UL 94V and HB flame tests were conducted either on 1.6 mm
films or on 2 mm injection-molded plaques.
[0264] Moduli of elasticity, impact resistances and notched impact
resistances were determined on injection-molded test specimens. For
this purpose, test specimens were produced on an Arburg 520S having
a screw diameter of 30 mm.
[0265] Burst pressures were determined on hoses having an external
diameter of 8.0 mm and an internal diameter of 5.5 mm. The hoses
were extruded with a Kuhne single-screw extruder having a
three-zone screw with a mixing section (screw ratio 1:3).
[0266] The results are summarized in the tables that follow.
2.1 Example 1
[0267] Blends produced from Elastollan 1180 A10 and Ultramid
RX2298.
TABLE-US-00001 Example No. 1.1 1.2 1.3 Elastollan 1180A10 80 60 20
Ultramid RX 2298 20 40 80 Density Density DIN EN ISO 1183-1, 1.094
1.088 1.070 [g/cm.sup.3] A: Shore A A DIN 53505 86 95 98 Shore D D
DIN ISO 7619-1: 33 43 63 Tensile strength [MPa] DIN EN ISO 527 25
14 38 Elongation at break [%] DIN EN ISO 527 560 230 250 Tear
propagation kN/m DIN ISO 34-1, B: 23 39 129 resistance Abrasion
mm.sup.3 DIN 53516 99 141 142 Modulus of elasticity [MPa] DIN EN
ISO 527 18 122 1155 Appearance transparent transparent translucent
UL 94V (1.6 mm) V2 HB HB
2.2 Example 2
[0268] Blends produced from Elastollan 1160 D10 and Ultramid
RX2298.
TABLE-US-00002 Example No. 2.1 2.2 2.3 2.4 Elastollan 1160D10 80 60
40 20 Ultramid RX 2298 20 40 60 80 Density Density DIN EN ISO 1183-
1.148 1.124 1.103 1.078 [g/cm.sup.3] 1, A: Shore D D DIN ISO
7619-1: 60 65 71 71 Tensile strength [MPa] DIN EN ISO 527 38 31 35
40 Elongation at break [%] DIN EN ISO 527 370 150 70 30 Tear
propagation kN/m DIN ISO 34-1, B: 145 164 184 185 resistance
Abrasion mm.sup.3 DIN 53516 53 83 108 120 Modulus of elasticity
[MPa] DIN EN ISO 527 306 620 988 1277 Charpy impact 23.degree. C.
[kJ/m.sup.2] DIN EN ISO 179- unbroken unbroken unbroken unbroken
1/1eU Charpy impact -30.degree. C. [kJ/m.sup.2] DIN EN ISO 179-
unbroken unbroken unbroken 87.5 1: Charpy notched impact
[kJ/m.sup.2] DIN EN ISO 179 108.47 119.53 10.5 18.1 resistance
23.degree. C. 1 (1eA) Charpy notched impact [kJ/m.sup.2] DIN EN ISO
179 18.94 14.91 9.47 6.47 resistance -30.degree. C. 1 (1eA)
Appearance translucent translucent translucent translucent UL 94V
(1.6 mm) V2 HB HB HB Burst pressure at [bar] 64 not not not
23.degree. C. determined determined determined Burst pressure at
[bar] 20 not not not 70.degree. C. determined determined determined
Burst pressure at [bar] 20 not not not 100.degree. C. determined
determined determined
2.3 Example 3
[0269] Blends produced from Elastollan 1178 D11U and Ultramid
RX2298.
TABLE-US-00003 Example No. 3.1 3.2 3.3 3.4 Elastollan 1178D11U 80
60 40 20 Ultramid RX 2298 20 40 60 80 Density Density DIN EN ISO
1183- 1.167 1.140 1.107 1.085 [g/cm.sup.3] 1, A: Shore A A DIN
53505 -- -- -- -- Shore D D DIN ISO 7619-1: 73 74 73 76 Tensile
strength [MPa] DIN EN ISO 527 33 32 37 48 Elongation at break [%]
DIN EN ISO 527 320 150 145 130 Tear propagation kN/m DIN ISO 34-1,
B: 180 181 145 285 resistance Abrasion mm.sup.3 DIN 53516 62 86 131
94 Modulus of elasticity [MPa] DIN EN ISO 527 762 1148 1565 1448
Charpy impact 23.degree. C. [kJ/m.sup.2] DIN EN ISO 179- unbroken
unbroken unbroken unbroken 1: Charpy impact -30.degree. C.
[kJ/m.sup.2] DIN EN ISO 179- 88.28 78.08 84.98 unbroken 1: Charpy
notched impact [kJ/m.sup.2] DIN EN ISO 179 20.25 14.53 7.91 9.85
resistance 23.degree. C. 1 (1eA) Charpy notched impact [kJ/m.sup.2]
DIN EN ISO 179 6.37 7.31 7.22 5.91 resistance -30.degree. C. 1
(1eA) Appearance translucent translucent translucent translucent UL
94V (1.6 mm) V2 V2 HB HB
2.4 Example 4
[0270] Blends produced from Elastollan 1183 D11U and Ultramid
RX2298.
[0271] It was possible to obtain a film only for one mixture. Shore
hardness was determined on injection moldings in this case.
TABLE-US-00004 Example No. 4.1 4.2 4.3 4.4 Elastollan 1183D11U 80
60 40 20 Ultramid RX 2298 20 40 60 80 Density Density DIN EN ISO
1183- 1.191 1.153 1.122 Blend not [g/cm.sup.3] 1, A: producible
Shore A A DIN 53505 Shore D D DIN ISO 7619-1: 79 72 77 Tensile
strength [MPa] DIN EN ISO 527 60 not not determined determined
Elongation at break [%] DIN EN ISO 527 20 not not determined
determined Tear propagation kN/m DIN ISO 34-1, B: 261 not not
resistance determined determined Abrasion mm.sup.3 DIN 53516 85 93
103 Modulus of elasticity [MPa] DIN EN ISO 527 2008 2017 2015
Charpy impact 23.degree. C. [kJ/m.sup.2] DIN EN ISO 179- unbroken
unbroken unbroken 1: Charpy impact -30.degree. C. [kJ/m.sup.2] DIN
EN ISO 179- 66.83 174.68 32.75 1: Charpy notched impact
[kJ/m.sup.2] DIN EN ISO 179 5.63 6.75 7.5 resistance 23.degree. C.
1 (1eA) Charpy notched impact [kJ/m.sup.2] DIN EN ISO 179 4.78 5.53
6.94 resistance -30.degree. C. 1 (1eA) Appearance translucent
translucent translucent UL 94 V (1.6 mm) V2 HB HB
2.5 Example 5
[0272] Blends produced from Elastollan 685 A10 and Ultramid
RX2298.
TABLE-US-00005 Example No. 5.1 5.2 Elastollan 685A10 80 20 Ultramid
RX 2298 20 80 Density Density [g/cm.sup.3] DIN EN ISO 1183-1, A:
1.174 1.086 Shore A A DIN 53505 90 -- Shore D D DIN ISO 7619-1: 42
70 Tensile strength [MPa] DIN EN ISO 527 46 21 Elongation at break
[%] DIN EN ISO 527 490 110 Tear propagation resistance kN/m DIN ISO
34-1, B: 58 161 Abrasion mm.sup.3 DIN 53516 71 116 Modulus of
elasticity [MPa] DIN EN ISO 527 36 1209 Appearance transparent
transparent UL 94V (1.6 mm) V2 HB
2.6 Example 6
[0273] Blends produced from Elastollan B60 D11 and Ultramid
RX2298.
TABLE-US-00006 Example No. 6.1 6.2 Elastollan B60D11 80 20 Ultramid
RX 2298 20 80 Density Density [g/cm.sup.3] DIN EN ISO 1183-1, A:
1.191 1.089 Shore A A DIN 53505 -- -- Shore D D DIN ISO 7619-1: 57
74 Tensile strength [MPa] DIN EN ISO 527 42 51 Elongation at break
[%] DIN EN ISO 527 430 340 Tear propagation resistance kN/m DIN ISO
34-1, B: 115 197 Abrasion mm.sup.3 DIN 53516 65 102 Modulus of
elasticity [MPa] DIN EN ISO 527 587 1700 Appearance translucent
transparent UL 94V (1.6 mm) V2 HB
2.7 Example 7
[0274] Blends produced from Elastollan AC85 A12 and Ultramid
RX2298.
TABLE-US-00007 Example No. 7.1 7.2 7.3 7.4 Elastollan AC 85A12 80
60 40 20 Ultramid RX 2298 20 40 60 80 Density Density DIN EN ISO
1183- 1.124 1.108 1.080 1.079 [g/cm.sup.3] 1, A; Shore A A DIN
53505 -- -- -- -- Shore D D DIN ISO 7619-1: 43 44 57 71 Tensile
strength [MPa] DIN EN ISO 527 14 16 26 38 Elongation at break [%]
DIN EN ISO 527 490 160 110 230 Tear propagation kN/m DIN ISO 34-1,
B: 44 57 125 251 resistance Abrasion mm.sup.3 DIN 53516 51 62 110
101 Modulus of elasticity [MPa] DIN EN ISO 527 29 67 370 1131
Charpy impact 23.degree. C. [kJ/m.sup.2] DIN EN ISO 179- unbroken
unbroken unbroken unbroken 1: Charpy impact -30.degree. C.
[kJ/m.sup.2] DIN EN ISO 179- unbroken unbroken unbroken unbroken 1:
Charpy notched impact unbroken unbroken unbroken 39.19 resistance
23.degree. C. Charpy notched impact 110.35 67.88 8.07 6.38
resistance -30.degree. C. Appearance opaque opaque opaque opaque UL
94V (1.6 mm) HB HB HB HB Burst pressure at [bar] 89 not not not
23.degree. C. determined determined determined Burst pressure at
[bar] 49 not not not 70.degree. C. determined determined determined
Burst pressure at [bar] 40 not not not 100.degree. C. determined
determined determined
2.8 Example 8
[0275] Blends produced from Elastollan L1160 D12 and Ultramid
RX2298.
TABLE-US-00008 Example No. 8.1 8.2 8.3 8.4 Elastollan AC 85A12 80%
60% 40% 20% Ultramid RX 2298 20% 40% 60% 80% Density Density DIN EN
ISO 1183- 1.089 1.080 1.076 1.069 [g/cm.sup.3] 1, A: Shore A A DIN
53505 99 99 99 99 Shore D D DIN ISO 7619-1: 57 62 66 72 Tensile
strength [MPa] DIN EN ISO 527 41 44 38 53 Elongation at break [%]
DIN EN ISO 527 390 400 330 410 Tear propagation kN/m DIN ISO 34-1,
B: 133 144 179 218 resistance Abrasion mm.sup.3 DIN 53516 95 104 96
60 Modulus of elasticity [MPa] DIN EN ISO 527 201 359 640 885
Appearance translucent translucent translucent translucent UL 94V
(1.6 mm) HB HB HB HB
2.9 Example 9
[0276] Mixtures produced from Ultramid RX2298, Exolit OP 1230 and
melamine cyanurate 15ED.
TABLE-US-00009 Example No. 9.1 9.2 Ultramid RX 2298 80 70 Melamine
cyanurate MC 15ED 10 20 Exolit OP 1230 10 10 Density Density
[g/cm.sup.3] DIN EN ISO 1183-1, 1.123 1.147 A: Shore A A DIN 53505
-- -- Shore D D DIN ISO 7619-1: 77 79 Tensile strength [MPa] DIN EN
ISO 527 41 36 Elongation at break [%] DIN EN ISO 527 30 90 Tear
propagation resistance kN/m DIN ISO 34-1, B: 177 192 Abrasion
mm.sup.3 DIN 53516 83 134 Modulus of elasticity [MPa] DIN EN ISO
527 1374 2032 Charpy notched impact [kJ/m.sup.2] DIN EN ISO 179
4.03 not resistance 23.degree. C. 1 (1eA) determined Charpy notched
impact [kJ/m.sup.2] DIN EN ISO 179 3.29 not resistance -30.degree.
C. 1 (1eA) determined Visual assessment opaque opaque UL 94 V (1.6
mm) V2 V0
2.10 Example 10
[0277] Various illustrative mixtures produced from Ultramid RX2298,
AC85 A12, 1160 D0, Exolit OP 1230, Fyrolflex RDP, melamine
polyphosphate MC 200/70 and melamine cyanurate MC 15ED.
TABLE-US-00010 Example No. 10.1 10.2 10.3 10.4 Ultramid RX 2298 20
20 70 20 AC 85A12 50 10 60 1160D10 50 Melamine cyanurate 10 MC 15ED
Exolit OP 1230 20 20 10 10 Melamine 10 10 polyphosphate MC 200/70
Fyrolflex RDP 10 Density Density DIN EN ISO 1183- 1.142 1.125 1.124
1.107 [g/cm.sup.3] 1, A: Shore A A DIN 53505 -- 97 -- 99 Shore D D
DIN ISO 7619-1: 69 62 75 62 Tensile strength [MPa] DIN EN ISO 527
26 7 35 25 Elongation at break [%] DIN EN ISO 527 300 70 50 330
Tear propagation kN/m DIN ISO 34-1, B: 143 90 152 133 resistance
Abrasion mm.sup.3 DIN 53516 129 125 109 110 Modulus of elasticity
[MPa] DIN EN ISO 527 not not 1955 not determined determined
determined Visual assessment opaque opaque opaque opaque UL 94 V
(1.6 mm) V0 V2 V0 V2
2.11 Example 11
[0278] Various illustrative mixtures produced from Ultramid RX2298,
AC85 A12, 1160 D10, Exolit OP 1230, Fyrolflex RDP, melamine
polyphosphate MC 200/70 and melamine cyanurate MC 15ED.
TABLE-US-00011 Example No. 11.1 11.2 11.3 11.4 11.5 11.6 Ultramid
RX 2298 55 60 54 60 55 55 AC 85A12 5 5 5 5 5 5 Melamine cyanurate
10 10 10 20 MC 15ED Exolit OP 1230 10 20 20 20 20 10 Melamine 10 10
polyphosphate MC 200/70 Fyrolflex RDP Chopvantage 20 5 10 5 10 10
HP3550 EC10-3,8 Density Density DIN EN ISO 1.282 1.174 1.197 1.186
1.236 1.197 [g/cm.sup.3] 1183-1, A: Tensile strength [MPa] DIN EN
ISO 527 57 37 56 41 57 62 Elongation at break [%] DIN EN ISO 527 5
12 8 12 8 8 Modulus of elasticity [MPa] DIN EN ISO 527 16726 2640
3695 2736 3818 4075 Visual assessment opaque opaque opaque opaque
opaque opaque UL 94 V (2.0 mm) V0 V0 V0 V0 V0 V0
CITED LITERATURE
[0279] EP 0 352 562 A1 [0280] DE2846596 A1 [0281] WO 2018/050487 A1
[0282] EP 0 922 552 A1 [0283] DE 101 03 424 A1 [0284] WO
2006/072461 A1
* * * * *