Note: Descriptions are shown in the official language in which they were submitted.
CA 02834380 2013-10-25
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Extruded plastics profiles comprising continuously introduced insulation
elements
Description
The present invention relates to a continuous process for producing a profile
comprising at least
one core made of a polyurethane foam or a mixture comprising a polyurethane
foam, at least
one jacket made of at least one thermoplastic material, and optionally at
least one foil between
core and jacket, to a profile produced via said process, to the use of this
profile for producing
windowframes, doorframes, or in the fitting-out of interiors, or in
apparatuses in which, during
operation, temperature differences arise between interior space and exterior
space, and also to
an apparatus for carrying out the process of the invention.
The process of the invention can produce profiles from which windowframes or
doorframes can
be produced for house construction.
Within the prior art there are known processes for producing similar profiles
and, respectively,
windowframes or doorframes.
DE 28 44 006 Al discloses a process for extruding plastics profiles which have
a core made of
foamed plastic enclosed on all sides by a jacket made of a plastic, where, in
a single operation,
the material for the jacket is introduced into the extruder die system, and at
the same time the
core material is introduced into the cavity of the shaped 'jacket, where gases
introduced into the
cavity of the jacket during the foaming of the core material are dissipated by
way of the extruder
die system. A problem with this process is that, although the gases generated
are dissipated,
the foam obtained in the profile is not particularly uniform. Another
disadvantage of this process
is that the reactive system for the foamed plastic has to be passed through
the hot extruder die
system, with disadvantages in terms of energy and of process technology.
WO 99/16996 Al discloses a process for producing frame profiles for windows or
doors, where
the outer profile is first produced from a thermoplastic and then a foamable
mixture based on a
polyurethane is introduced into the profile, and when the mixture is foamed to
fill the available
space a strong adhesive bond is generated between exterior profile and foam.
This document
CA 02834380 2013-10-25
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also discloses a process where a prefabricated, fully foamed core is inserted
into the pre-
shaped exterior profile.
DE 199 61 306 Al likewise discloses a process for producing a profile via
extrusion. This profile
comprises an exterior shell and a foamed interior core. In this process, the
exterior shell of the
profile is first extruded, and then a foamable material is foamed to fill the
available space.
DE 1 959 464 likewise discloses a process for continuously extruding
continuous profiles with a
jacket made of thermoplastic and with a foam core, where the jacket made of
thermoplastic is
first produced via extrusion and a foamable material is then used to fill the
available space
therein.
The process of DE 1 779 271 produces a flexible plastics profile strip by
using extrusion to pro-
duce the flexible exterior sheath and the foamed core simultaneously.
US 2006/0255488 Al likewise discloses a process for producing plastics
profiles which have a
foamed core, via simultaneous extrusion of the two materials, respectively in
the molten state.
EP 2 072 743 A2 discloses a process for foaming to fill the available space in
a hollow win-
dowframe or hollow doorframe. For this, plastics profiles produced via
extrusion are assembled
to give finished windowframes or finished doorframes, and a foamable material
is then intro-
duced to fill the available space.
The prior art also discloses processes for producing these profiles having a
foamed core where
fully foamed inserts are inserted into the extruded profiles, see by way of
example DE
202009003392 U1 or WO 02/090703A2.
An example of a disadvantage of the processes mentioned from the prior art is
that plastics pro-
files are produced via melt extrusion and then after a short time a foamable
material has to be
inserted into these profiles. The profiles are therefore still hot or at least
warm, and this has an
adverse effect on the filling of the available space by foamable material
introduced. Further-
more, when foaming fills the available space of one chamber of the plastics
profile in a continu-
ous process it is possible to produce only profiles with one, and no more than
one, chamber
CA 02834380 2013-10-25
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comprising foam, since the lance through which the reactive system is
introduced has to be in-
troduced into the profile. Another disadvantage is that the reactive
polyurethane system has to
be passed through the hot extruder die system.
In the light of the prior art, it is an object of the present invention to
provide a continuous pro-
cess which can produce profiles comprising at least one core made of a foamed
material and
one jacket made of a thermoplastic material, where a feature of the process is
that it provides
access to appropriate profiles which feature particularly uniform and
homogeneous distribution
of the foam within the profile chamber intended for that purpose. The foaming
in the process is
moreover intended to take place under conditions which permit ideal
development of the foam.
The process is moreover intended to permit avoidance of complicated process
technology for
the individual precursor compounds for jacket or core.
The invention achieves these objects via a continuous process for producing a
profile compris-
ing at least one core made of a polyurethane foam or a mixture comprising a
polyurethane
foam, one jacket made of at least one thermoplastic material, and optionally
at least one foil
between core and jacket, comprising at least the steps of:
(A) optionally introducing a foil into a gripper-belt system which has the
shape of the profile,
(B) introducing at least one liquid, foamable reactive system of the core
comprising a polyiso-
cyanate a) and at least one higher molecular compound having groups reactive
towards
isocyanate groups into the gripper-belt system in such a way that any foil
present at least
to some extent encloses the reactive mixture,
(C) shaping of the core in the gripper-belt system,
(D) optionally cooling the core from step (C),
(E) introducing the core from step (C) or (D) into an extruder with attached
extrusion die for
producing hollow profiles, in order to sheath the core with a jacket made of
at least one
thermoplastic material and thus obtain the profile,
CA 02834380 2013-10-25
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(F) optionally cooling the profile from step (E), and
(G) optional cutting of the profile from step (E) or (F).
The process of the invention serves for producing a profile comprising at
least one core made of
a polyurethane foam or a mixture comprising a polyurethane foam, at least one
jacket made of
at least one thermoplastic material, and optionally at least one foil between
core and jacket.
The profile produced in the invention comprises at least one core made of a
polyurethane foam
or a mixture comprising a polyurethane foam.
In one particularly preferred embodiment, the at least one foamed material
located in the core is
a polyurethane foam.
Polyurethanes, in particular in foamed form, are known per se to the person
skilled in the art,
and are described by way of example in DE 10 124 333.
In the invention, it is particularly preferable to use rigid polyurethane
foams in the core of the
profile of the invention. -
The polyurethane foam or the mixture comprising a polyurethane foam according
to the present
invention is obtained according to the present invention from a liquid
reactive system comprising
at least one polyisocyanate a) and at least one higher molecular compound
having groups reac-
tive towards isocyanate groups b).
In contrast to the processes known from the prior art in the process according
to the present
invention, not a readily polymerized material is introduced into the gripper-
belt or the foil and
foamed but a liquid reactive system, comprising the starting compounds for the
preparation of
polyurethane foams, i. e. at least one polyisocyanate a) and at least one
higher molecular corm
pound having groups being reactive towards isocyanate groups b), is introduced
and the
polymerization reaction for forming the polymeric polyurethanes and the
foaming for preparation
of the foam take place, preferably at the same time.
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Polyurethane foams, in particular rigid polyurethane foams, have been known
for a long time
and are widely described in the literature. They are usually produced via
reaction of organic
polyisocyanates a) with compounds b1) having at least two groups reactive
toward isocyanate
groups, mostly polyols and/or polyamines. The at least one higher molecular
compound having
5 groups reactive towards isocyanate groups b) is according to the present
invention preferably a
compound having at least two groups reactive towards isocyanate groups b1).
Organic polyisocyanates a) that can be used are preferably aromatic
polyfunctional isocyanates.
Individual examples that may be mentioned are tolylene 2,4- and 2,6-
diisocyanate (TDI) and the
corresponding isomer mixtures, diphenylmethane 4,4'-, 2,4'-, and 2,2'-
diisocyanate (MDI) and
the corresponding isomer mixtures, mixtures made of diphenylmethane 4,4' and
2,4'.
diisocyanates, polyphenyl polymethylene polyisocyanates, mixtures made of
diphenylmethane
4,4'-, 2,4'-, and 2,2'-diisocyanates, and of polyphenyl polymethylene
polyisocyanates (crude
MDI), and mixtures made of crude MDI and of tolylene diisocyanates. The
organic di- and polyi-
socyanates can be used individually or in the form of mixtures.
Other materials often used are those known as modified polyfunctional
isocyanates, i.e. prod-
ucts which are obtained via chemical reaction of organic di- and/or
polyisocyanates. Examples
that may be mentioned are di- and/or polyisocyanates comprising isocyanurate
groups and/or
comprising urethane groups. The modified polyisocyanates can optionally be
mixed with one
another or with unmodified organic polyisocyanates, e.g. diphenylmethane 2,4'-
and/or 4,4'-
diisocyanate, crude MDI, and/or tolylene 2,4- and/or 2,6-diisocyanate.
Materials that can also be used alongside these are reaction products of
polyfunctional isocya-
nates with polyfunctional polyols so called polyisocyanate prepolymers, and
also mixtures of
these with other di- and polyisocyanates.
The polyisocyanate component a) is preferably introduced in the form of
polyisocyanate prepol-
ymers. These polyisocyanate prepolymers are obtainable by reaction of the
above-mentioned
polyisocyanates with polyols to obtain the prepolymer, for example at a
temperature of 30 to
100 C, preferably at about 80 C. In a preferred embodiment, 4,4'-MDI is used
with uretone
imine modified MDI and commercially available polyols based on polyesters, for
example on
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adipic acid, polyethers, for example based on ethylene oxide and/or propylene
oxide or polytet-
rahydrofurane (PTHF) or polycarbonatols, for example as mentioned in European
patent appli-
cation EP 3007101407.0, are used for the preparation of prepolymers according
to the present
invention.
Polyols are known to the skilled artisan and are described for example in
"Kunststoffhandbuch,
Band 7, Polyurethane" Carl Hanser Verlag, 3. Auflage 1993, Kapitel 3.1.
Prepolymers on ether
basis are preferably obtained by reaction of polyisocyanates, particularly
preferably 4,4'-MDI,
with bi- to three-functional polyoxipropylene- and/or polyoxipropylene-
polyoxyethylene polyols.
Their preparation is usually conducted by the known basically catalyzed
addition of propylene
oxide alone, in mixture with ethylene oxide or blockwise to H-functional,
preferably OH-
functional starting compounds. Starting compounds are for example water,
ethylene glycols or
propylene glycols or glycerine or trimethylol propane. Further, as catalysts
multimetal cyanide
compounds, so called DMC-catalysts, can be used. Furthermore, catalysts of
Lewis-acids, like
bortrifluoride, can be used. Preferably polyethers are used as polyol, as
mentioned under b) in
the following.
When ethylene oxide-/propylene oxide mixtures are used, ethylene oxide is used
in an amount
of 10 to 50 % by weight, in respect of the total amount of alkylene oxide. The
integration of al-
kylene oxides can take place blockwise or as a statistical mixture.
Particularly preferred is addi-
tion of an ethylene oxide- and endcap ('EO-cap") in order to increase the
amount of more reac-
tive primary OH-end groups. The number average molecular weight of the polyols
is preferably
between 400 and 4500 g/mol.
A material that has proven particularly successful as organic polyisocyanate
is crude MDI hav-
ing from 29 to 33% by weight NCO content and having a viscosity at 25 C in the
range from 150
to 1000 mPa.s.
As higher molecular compounds with groups reactive towards isocyanate groups
b), preferably
as compounds b1) which have at least two groups reactive towards isocyanate
are in particular
polyether alcohols and/or polyester alcohols, and/or polycarbonate alcohols
having OH numbers
in the range from 100 to 1200 mg KOH/g.
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In a preferred embodiment according to the present invention mixtures
comprising polyetherols
and polyesterols are used as higher molecular compounds b).
Higher molecular compounds b) with groups reactive towards isocyanate groups
have prefera-
bly a molecular weight of more than 400 g/mol according to the present
invention, preferably,
the molecular weight is higher than 550 g/mol. The average functionality of
the higher molecular
compounds with groups reactive towards isocyanate groups is preferably less
than 2.5.
The polyester alcohols are mostly produced via condensation of polyhydric
alcohols, preferably
diols, having from 2 to 12 carbon atoms, preferably from 2 to 6 carbon atoms,
with polybasic
carboxylic acids having from 2 to 12 carbon atoms, e.g. succinic acid,
glutaric acid, adipic acid,
suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, maleic
acid, fumaric acid, and
preferably phthalic acid, isophthalic acid, terephthalic acid, and the
isomeric naphthalenedicar-
boxylic acids.
The dicarboxylic acids can be used separately or as a mixture among one
another. Instead of
the free dicarboxylic acids, the corresponding dicarboxylic acid derivatives,
for example dicar-
boxylic esters of alcohols with one to four carbon atoms or dicarboxylic acid
anhydrides can be
used. Preferably, dicarboxylic acid mixtures of succinic-, glutaric- and
adipic acid in proportions
of for example 20 to 35: 35 to 50: 20 to 32: 35 to 50: 20 to 32 parts by
weight, and preferably
adipic acid. Examples of 2 and more valent alcohols, preferably diols are:
ethane diol, diethy-
lene glycol, 1,2- or 1,3-propane diol, dipropylene glycol, 1,4-butane diol,
1,5-pentane diol, 1,6-
hexane diol, 1,10-decane diol, glycerine and trimethylol propane. Preferably,
ethan diol, diethy-
lene glycole, 1,4-butane diole, 1,5-pentane diol and 1,6-hexane diole are
used. Moreover, poly-
ester polyols of lactones, for example epsilon-caprolactone or
hydroxycarboxylic acids, for ex-
ample omega-hydroxycaproic acids, can be used.
For the preparation of polyester polyols, organic, for example aromatic and
preferably aliphatic
polycarboxylic acids and/or derivatives and polyvalent alcohols can be
polycondensed without a
catalyst or preferably in the presence of esterification catalyst,
advantageously in an atmos-
phere of inert gas, for example nitrogen, carbon monoxide, helium, argon and
others, in melt at
temperatures of 150 to 250 C, preferably 180 to 220 C, optionally under
decreased pressure,
up to a desired acid number, which is preferably lower than 10, particularly
preferably lower than
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2. According to a preferred embodiment, the esterification mixture is
polycondensed at above-
mentioned temperatures up to an acid number of 80 to 30, preferably 40 to 30,
under normal
pressure and subsequently under a pressure of less than 500 mbar, preferably
50 to 150 mbar.
Iron-, cadmium-, cobalt-, lead-, zinc-, antimony-, magnesium-, titanium- and
tin-catalysts in the
form of metals, metal oxides or metal salts can be used as esterification
catalysts. The polycon-
densation can also be conducted in liquid phase in the presence of dillution-
and/or entrainers,
for example benzene, toluene, xylene or chlorobenzene for aciotropic
distillation of the conden-
sation water. For the preparation of polyester polyols, organic polycarboxylic
acids and/or deriv-
atives and polyvalent alcohols are advantageously polycondensated in a molar
ratio of 1 : 1 to
1.8, preferably 1 : 1.05 to 1.2.
The polyester polyols obtained advantageously have a functionality of 1.8 to
4, particularly pref-
erably of 1.9 to 3 and particularly of 2.0 to 2.5 and a molecular weight of
480 to 5000, preferably
1000 to 4500 g/mol and preferably 1600 to 4500.
The functionality of the preferred polyether used in the invention is
preferably from 2 to 8, in
particular from 3 to 8.
In particular, it is possible to use polyether polyols b1H) which are produced
by known process-
es, for example via anionic polymerization of alkylene oxides in the presence
of catalysts, pref-
erably alkali metal hydroxides, amines, or what are known as DMC catalysts.
Alkylene oxides mostly used are ethylene oxide and/or propylene oxide,
preferably pure propyl-
ene 1,2-oxide.
Particular starter molecules that are used are compounds having at least 3,
preferably from 4 to
8, hydroxy groups, or having at least two primary amino groups in the
molecule.
Starter molecules which are used having at least 3, preferably from 4 to 8,
hydroxy groups in the
molecule are preferably trimethylolpropane, glycerol, toluenediamine,
pentaerythritol, sugar
compounds, such as glucose, sorbitol, mannitol, and sucrose, polyhydric
phenols, resols, e.g.
oligomeric condensates derived from phenol and formaldehyde, and Mannich
condensates de-
rived from phenols, formaldehyde, and from dialkanolamines, and also melamine.
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Starter molecules used having at least two primary amino groups in the
molecule are preferably
aromatic di- and/or polyamines, e.g. phenylenediamines, tolylene-2,3-, 2,4-,
3,4-, and 2,6-
diamine, and 4,4'-, 2,4'-, and 2,2'-diaminodiphenylmethane, and also aliphatic
di- and polyam-
ines, such as ethylenediamine.
The functionality of the polyether polyols is preferably from 3 to 8, and
their hydroxy numbers
are preferably from 100 mg KOH/g to 1200 mg KOH/g, and in particular from 240
mg KOH/g to
570 mg KOH/g.
Among the compounds b1) having at least two hydrogen atoms reactive toward
isocyanate are
also the optionally concomitantly used chain extenders and crosslinking
agents. It can prove
advantageous for modification of mechanical properties to add difunctional
chain extenders,
crosslinking agents of functionality 3 or higher, or else optionally mixtures
thereof. Chain ex-
tenders and/or crosslinking agents used are preferably alkanolamines and in
particular diols
and/or triols having molecular weights smaller than 400, preferably from 60 to
300.
The amount advantageously used of chain extenders, crosslinking agents, or
mixtures thereof is
from 1 to 20% by weight, preferably from 2 to 5% by weight, based on polyol
component b1).
Further information concerning the polyether alcohols and polyester alcohols
used, and also
production of these, is found by way of example in Kunststoffhandbuch
[Plastics handbook],
volume 7 "Polyurethane" [Polyurethanes], edited by Gunter Oertel, Carl-Hanser-
Verlag, Munich,
3rd edition, 1993, pages 57 to 74.
In an embodiment to which preference is further given, within the
polyurethanes that are present
in the invention within the core of the profile of the invention, there are
further additives present,
for example selected from the group consisting of flame retardants, surfactant
substances, foam
stabilizers, cell regulators, fillers, pigments, dyes, flame retardants,
hydrolysis stabilizers, anti-
static agents, agents having fungistatic and bacteriostatic effect, and
mixtures thereof.
Flame retardants that can be used are organic phosphoric and or phosphonic
esters. It is pref-
erable to use compounds that are not reactive toward isocyanate groups. Among
the preferred
CA 02834380 2013-10-25
compounds are also phosphoric esters comprising chlorine. Typical
representatives of this
group of flame retardants are triethyl phosphate, diphenyl cresyl phosphate,
tris(chloropropyl)
phosphate, and also diethyl ethanephosphonate.
5 Alongside these, flame retardants comprising bromine can also be used.
Flame retardants used
comprising bromine are preferably compounds having groups reactive toward the
isocyanate
group. Compounds of this type are esters of tetrabromophthalic acid with
aliphatic diols and
alkoxylation products of dibromobutenediol. It is also possible to use
compounds which derive
from the group of the brominated neopentyl compounds comprising OH groups.
For production of the polyurethanes preferably used in the invention in the
core of the profile of
the invention it is usual to use blowing agents, catalysts, and cell
stabilizers, and also, if neces-
sary, further auxiliaries and/or additives.
Water can be used as blowing agent, and reacts with isocyanate groups with
elimination of car-
bon dioxide. It is also possible to use what are known as physical blowing
agents in combination
with, or instead of, water. These are compounds which are inert toward the
starting components
and which are mostly liquid at room temperature, and which evaporate under the
conditions of
the urethane reaction. The boiling point of said compounds is preferably below
50 C. Among the
physical blowing agents are also compounds which are gaseous at room
temperature and
which are introduced under pressure into the starting components or are
dissolved therein, ex-
amples being carbon dioxide, low-boiling-point alkanes, and fluoroalkanes.
The compounds are mostly selected from the group consisting of alkanes and/or
cycloalkanes
having at least 4 carbon atoms, dialkyl ethers, esters, ketones, acetals,
fluoroalkanes having
from 1 to 8 carbon atoms, and tetraalkylsilanes having from 1 to 3 carbon
atoms in the alkyl
chain, in particular tetramethylsilane.
Examples that may be mentioned are propane, n-butane, iso- and cyclobutane, n-
, iso-, and
cyclopentane, cyclohexane, dimethyl ether, methyl ethyl ether, methyl butyl
ether, methyl for-
mate, acetone, and also fluoroalkanes which can be degraded in the troposphere
and are not
therefore hazardous to the ozone layer, e.g. trifluoromethane,
difluoromethane, 1,1,1,3,3-
pentafluorobutane, 1,1,1,3,3-pentafluoropropane, 1,1,1,2-tetrafluoroethane,
difluoroethane, and
CA 02834380 2013-10-25
11
heptafluoropropane; fluoroalkenes can also be used. The physical blowing
agents mentioned
can be used alone or in any desired combinations with one another.
Catalysts used are in particular compounds which greatly accelerate the
reaction of the isocya-
nate groups with the groups reactive toward isocyanate groups. Examples of
these catalysts are
strongly basic amines, e.g. secondary aliphatic amines, imidazoles, amidines,
and also alka-
nolamines.
If the intention is to incorporate isocyanurate groups into the polyurethane
foam, specific cata-
lysts are required. Usual isocyanurate catalysts used are metal carboxylates,
in particular po-
tassium acetate and solutions thereof.
As a function of requirement, the catalysts can be used alone or in any
desired mixtures with
one another.
Further additives used are the substances known per se for this purpose, for
example surfactant
substances, foam stabilizers, cell regulators, fillers, pigments, dyes, flame
retardants, hydrolysis
stabilizers, antistatic agents, agents having fungistatic and bacteriostatic
effect.
More detailed information concerning a process for producing the polyurethanes
preferably
used in the invention, and also concerning the starting materials, blowing
agents, and catalysts
used, and also auxiliaries and/or additives is found by way of example in
Kunststoffhandbuch
[Plastics handbook], volume 7 "Polyurethane" [Polyurethanes], Carl-Hanser-
Verlag, Munich, 1st
edition, 1966, 2nd edition, 1983 and 3rd edition, 1993, pages 104 to 192.
To produce the rigid polyurethane foams, the polyisocyanates a) and polyol
component b) are
reacted in amounts such that the isocyanate index is from 90 to 220,
preferably from 100 to 200,
in particular from 110 to 190.
The density of the rigid polyurethane foams preferably used in the invention
is preferably from
10 to 400 kg/m3, particularly preferably from 20 to 200 kg/m3, very
particularly preferably from
30 to 100 kg/m3.
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Details of the production of the polyurethane foams according to the invention
are specified in
steps (B) and (C).
The core of the profile of the invention can generally have any desired shape
which appears to
the person skilled in the art to be suitable for the desired application. The
cross-sectional shape
of the core can be round and/or angular. The core can moreover be of uniform
or nonuniform
shape and by way of example can have cavities, grooves, ridges, etc., where
these profiling
effects can run either parallel to or perpendicularly to the direction of
production. In one pre-
ferred embodiment, the core shaped in step (C) of the process of the invention
provides the
shape of the profile to be produced or, respectively, provides the region
enclosed by the insulat-
ing element. In another embodiment of the profile produced in the invention,
for example in the
case of a window profile, the core produced in the invention is sheathed by a
jacket to which
fillets have been bonded, onto which further fillets are then optionally
bonded. The entirety
made of core, jacket, and fillets forms the resultant profile of the
invention.
The shape of the core is in turn prescribed via the shape of the gripper-belt
system used in the
invention. The dimensions of the core are generally from 5 to 250 mm,
preferably from 10 to
150 mm, particularly preferably from 20 to 100 mm, in particular from 25 to 80
mm, and in the
case of nonuniformly shaped cores these dimensions describe the greatest
available distances
in one direction.
The profile produced in the invention comprises at least one core made of a
polyurethane foam
or a mixture comprising a polyurethane foam. In one preferred embodiment, the
profile pro-
duced in the invention comprises precisely one core made of a polyurethane
foam or a mixture
comprising a polyurethane foam. It is also possible in the invention that the
profile has two,
three or fore cores made of a polyurethane foam or a mixture comprising a
polyurethane foam.
If there are two, three, or four cores present in the profile produced in the
invention, these can
have identical or different shapes.
The profile produced in the invention comprises, alongside the at least one
core, at least one
jacket made of at least one thermoplastic material. The term "jacket" in the
invention means a
coating of the core of the profile of the invention. The jacket here encloses
the core to some
CA 02834380 2013-10-25
13
extent or entirely, preferably entirely. In one preferred embodiment, the
jacket moreover has
fillets bonded thereto.
The thickness of the jacket per se or of the jacket and of the optionally
present fillets of the jack-
et is generally from 1 to 20 mm, preferably from 2 to 15 mm, particularly
preferably from 3 to
mm, and the thicknesses of the jacket and of the fillets here can be different
or identical. In
one preferred embodiment, the jacket or the fillets has/have various
thicknesses at various sites
on the profile, where the thicknesses are identical in a longitudinal
direction but can be different
in a transverse direction. This is a function by way of example of the shape
of the profile, which
10 in turn is a function of the subsequent application.
The jacket of the profile to be produced in the invention generally comprises
at least one ther-
moplastic material. Suitable thermoplastic materials are known per se to the
person skilled in
the art and by way of example are those selected from the group consisting of
polyolefins, by
way of example acrylonitrile-butadiene-styrene (ABS), polymethyl methacrylate
(PMMA), poly-
ethylene (PE), polypropylene (PP), polystyrene (PS), or polyvinyl chloride
(PVC), polyconden-
sates, such as polyamides (PA), e.g. PA 6 or PA 6,6, polylactate (PLA),
polycarbonates (PC),
polyesters, such as polyethylene terephthalate (PET), polyether ether ketone
(PEEK), polyad-
ducts, such as thermoplastic polyurethane, wood-plastics composites, and
mixtures thereof. In a
particularly preferred embodiment, the jcket of the profile to be produced in
the invention com-
prises polyvinyl chloride (PVC). Polyvinyl chloride (PVC) and its preparation
by polymerization
of vinyl chloride is known per se to the person skilled in the art.
In one preferred embodiment, the jacket comprises a thermoplastic material
which has a melting
point below 220 C.
In the profile produced in the invention, there is optionally at least one
foil between core and
jacket. The term "foil" in the invention means a layer or coating optionally
present between core
and jacket in the profile produced in the invention. Said foil can generally
be composed of any
material which appears to the person skilled in the art to be suitable for the
profile of the inven-
tion.
CA 02834380 2013-10-25
14
In one preferred embodiment, the foil optionally present between core and
jacket comprises a
material selected from the group consisting of thermoplastic polyurethane,
polyolefins, such as
polyethylene, polypropylene, polystyrene, polyvinyl chloride, and/or paper,
paperboard, textiles,
nonwovens, Teflon, metal, metal-plastics composite materials, and mixtures
thereof. The mate-
rials mentioned, and processes for producing same, are known per se to the
person skilled in
the art. The invention can also use a foil which is composed of more than one
material, the term
used being composite materials.
In one particularly preferred embodiment, the foil comprises Teflon between
core and jacket of
the profile produced in the invention, and it is very particularly preferable
that the foil is com-
posed of Teflon. In this embodiment, the foil present prevents permanent
adhesion of the core
to the jacket, in such a way that articles produced from the profile produced
in the invention, for
example windowframes or doorframes, can easily be recycled after use, because
the different
plastics, for example polyurethane foam of the core and polyvinyl chloride of
the jacket, can
easily be separated from one another.
In another preferred embodiment, the foil comprises a thermoplastic
polyurethane. The result is
particularly strong adhesion of the foil to the core. Another result is
particularly good adhesion of
the foil to the jacket, the overall result therefore being particularly good
and strong adhesion of
the three components to one another, and a particularly stable profile.
Thermoplastic polyure-
thanes preferably used are by way of example composed mainly of MDI and PTHF
polyols, for
example as described in DE 10234007.
In another preferred embodiment, the foil comprises a metal or a metal-
plastics composite ma-
terial, by way of example described in DE 10211274. In said embodiment, there
is a gastight
sheath around the core, which preferably comprises a polyurethane foam. It is
thus possible in
the invention that blowing agent, in particular pentane, present in the foam
cannot escape by
evaporation from the core. The core therefore also retains its low lambda
value over a very long
period, and the insulating effect of the core or of the entire profile
therefore remains in essence
constant over a long period.
CA 02834380 2013-10-25
The thickness of the foil which is optionally present between core and jacket
is by way of exam-
ple from 10 to 3000 pm, preferably from 25 to 1000 pm, particularly preferably
from 50 to
750 pm, in particular from 100 to 500 pm.
5 A detailed explanation is provided below of the individual steps of the
continuous process of the
invention:
Step (A):
10 The optional step (A) of the process of the invention comprises
introducing a foil into a gripper-
belt system which has the shape of the profile.
Step (A) of the process of the invention is carried out if a foil is to be
present between the core
and the jacket of the profile to be produced. The invention preferably
provides said foil in the
15 form of a roll and introduces it by means of an unwind apparatus or,
respectively, conveying
apparatus known to the person skilled in the art into the actual apparatus for
producing the pro-
file.
In step (A), the foil is introduced into a gripper-belt system known to the
person skilled in the art.
It is essential to the invention here that said gripper-belt system has the
shape of the profile to
be produced. Figures 2, 3 and 4 depict possible embodiments of said gripper-
belt system in the
invention.
A gripper-belt system with an appropriate number of elements is provided in
step (A), designed
appropriately for the number of cores to be comprised in the profile to be
produced. If there is
one core present in the profile to be produced, a gripper-belt system with two
elements is pref-
erably suitable. If there are two cores present in the profile to be produced,
a gripper-belt sys-
tem with three elements is used. If there are three cores present in the
profile to be produced, it
is preferable to use a gripper-belt system with four elements. If there are
four cores present in
the profile to be produced, it is preferable to use a gripper-belt system with
five elements. If
more than one core is present in the profile to be produced in the invention,
these can have
been arranged within the profile so as to be alongside one another and/or
mutually superposed.
The known continuous processes cannot produce a profile of this type with two
or four cores.
CA 02834380 2013-10-25
16
The gripper-belt system used in the invention is known per se to the person
skilled in the art and
is described by way of example in DE 102004023881.
In step (A) of the process of the invention, the foil is introduced into the
gripper-belt system in
such a way that it preferably lies on the floor of the gripper-belt system
and, on the sides of the
gripper-belt system, is conducted as far as the upper edge. In one preferred
embodiment, the
dimensions of the foil are such that it overlaps the upper edge of the gripper-
belt system and, by
virtue of the temperature prevailing in the gripper-belt system, to the extent
that the temperature
of the gripper-belt system or the temperature of the reacting PU foam is above
the Tg or the Tm
of the foil used, fuses to itself in such a way that the foil introduced forms
a tube, where the
shape of the tube is preferably exactly that prescribed by the gripper-belt
system for the profile
to be produced.
In another preferred embodiment, step (A) is carried out in such a way that
when the foil is in-
troduced into the gripper-belt system the jaws have not yet been closed
completely. This em-
bodiment makes it easier to introduce the foil and permits crease-free
introduction.
It is preferable to introduce the foil into the gripper-belt system by way of
a shaping apparatus,
preferably a forming shoulder.
Step (A) of the process of the invention is preferably carried out at a
temperature from room
temperature to 40 C, particularly preferably from room temperature to 30 C.
Step (B):
Step (B) of the process of the invention comprises introducing at least one
liquid foamable reac-
tive system of the core comprising at least one polyisocyanate a) and at least
one higher mo-
lecular compound with groups reactive against isocyanate groups b) into the
gripper-belt sys-
tem, so that any optionally present foil at least to some extent encloses the
precursor material.
In the invention, a reactive system means a mixture of precursor compounds for
the foamed
material present in the core.
CA 02834380 2013-10-25
17
Step (B) of the process of the invention uses apparatuses known to the person
skilled in the art
to introduce the material. According to the present invention the components
needed for produc-
ing the polyurethane foam, in particular a polyisocyanate component and a
polyol component,
and also the other components mentioned at an earlier stage above are
introduced. In one par-
ticularly preferred embodiment, the method for step (B) introduces a mixture
comprising the
diisocyanate component and the polyol component. The mixture is produced from
the individual
substances in mixing equipment known to the person skilled in the art. By way
of example, the
catalysts and the blowing agents are metered into the polyol component by way
of further me-
tering pumps.
In one particularly preferred embodiment, in which step (A) of the process of
the invention has
been carried out, at least one liquid foamable reactive system of the core is
charged in step (B)
into the foil introduced in step (A), and it is preferable here that the foil
has formed a tube in step
(A) or forms a tube in step (B). The amount of the precursor material to be
charged here is
judged by the person skilled in the art in such a way that, after foaming, the
entire space availa-
ble for the core has been filled with polyurethane foam.
If step (A) of the process of the invention is not carried out, it is
preferable that the gripper-belt
system is provided with a release agent before charging of the precursor
material in step (B) of
the process of the invention.
Any of the blowing agents known to the person skilled in the art is generally
suitable, and sili-
cones or waxes are particularly suitable.
Step (B) of the process of the invention is preferably carried out at room
temperature, and the
temperatures of the starting components for polyurethane production here are
those known to
the person skilled in the art.
Step (C):
Step (C) of the process of the invention comprises the shaping of the core in
the gripper-belt
system.
CA 02834380 2013-10-25
18
The invention preferably carries out step (C) in such a way that the foamable
precursor material
introduced in step (B) is foamed in the gripper-belt system. The precursor
material here, or the
core being formed here, is preferably transported via the movement of the
gripper-belt system.
In a further preferred embodiment, a train unit, for example two motor-powered
wheel systems,
are present after the gripper-belt system, that pull the foil, preferably at
start, through the grip-
per-belt system. In a further preferred embodiment, preferably after start, i.
e. when the process
is running in a stable way, the cured hart foam profile which is surrounded
with foil, is transport-
ed by a train unit, for example two motor-powered wheel systems.
By virtue of the pressure conditions and temperature conditions prevailing in
the gripper-belt
system, the precursor materials present, in particular the polyisocyanate
component and polyol
component, react to give the desired foam. The shaping of the gripper-belt
system, or of the foil
present in the gripper-belt system, causes the foam to assume the shape of the
desired profile
during the foaming process. "Overfill", which is a function of the amount
introduced and of the
free-foamed density, is used to obtain compaction, thus giving the foam high
homogeneity and
stability.
Step (C) of the process of the invention is preferably carried out at a
temperature from room
temperature to 55 C, particularly preferably from room temperature to 45 C.
Any gases produced in step (C) during the shaping of the core are preferably
not dissipated in
the invention, but instead remain within the material of the core. To this
end, the amount of pre-
cursor material can preferably be judged by the person skilled in the art in
such a way that, after
the foaming process, the foam charged to the gripper-belt system or to a foil
present therein, or
to a tube shaped therefrom, has a desired density and quality.
The pressure at which step (C) of the process of the invention is generally
carried out is from
0.8 to 1.2 bar (a), preferably from 0.9 to 1.1 bar (a), particularly
preferably atmospheric pres-
sure.
Step (D):
CA 02834380 2013-10-25
19
The optional step (D) of the process of the invention comprises the cooling of
the core from step
(C).
Step (D) of the process of the invention is carried out if the temperature of
the core made of a
polyurethane foam or a mixture comprising a polyurethane foam optionally at
least to some ex-
tent sheathed by at least one foil is too high for the next step (E) of the
process of the invention.
Cooling can be carried out by the processes known to the person skilled in the
art. By way of
example, the core just formed can be passed through an appropriate coolant,
such as water or
air. In one preferred embodiment, the optional step (D) of the process of the
invention is carried
out.
The temperature to which the core is preferably cooled in step (D) of the
process of the inven-
tion is from room temperature to 70 C, preferably from room temperature to 50
C.
Step (E):
Step (E) of the process of the invention comprises introducing the core from
step (C) or (D) into
an extruder with attached extrusion die for producing annular profiles, in
order to sheath the
core with a jacket made of at least one thermoplastic material, thus obtaining
the profile.
In step (E), the core obtained in step (B) and optionally sheathed by a foil
is introduced into an
extruder which comprises a die which replicates the shape of the profile. In
the extruder of step
(E), the thermoplastic material which is to form the jacket is now applied in
molten form to the
core. Embodiments of this extruder used in the invention are in general terms
known to the per-
son skilled in the art and are described by way of example in WO 2009/098068.
Step (E) gives the profile of the invention comprising at least one core made
of at least one
foamed material, at least one jacket made of at least one thermoplastic
material, and optionally
at least one foil between core and jacket.
Step (E) of the process of the invention is preferably carried out at a
temperature at which the
thermoplastic material of the jacket is molten, for example from 100 to 220 C,
particularly pref-
erably from 130 to 190 C.
CA 02834380 2013-10-25
The prevailing temperature at which the thermoplastic material solidifies
after leaving the ex-
truder is preferably by way of example from 25 to 180 C, preferably from 50 to
150 C.
5 Extrusion of thermoplastic materials is known per se to the person
skilled in the art and is de-
scribed by way of example in "EinfOhrung in die Kunststoffverarbeitung"
[Introduction to plastics
processing], 5th edition, September 2006; pp. 87 - 180; Walter Michaeli;
Hanser Fachbuchver-
lag.
10 The present invention also provides the process of the invention where,
in step (E), reinforce-
ment is introduced into the gripper-belt system or, respectively, into the
extrusion die, i.e. into
the profile-shaped die, of the extruder in such a way that said reinforcement
system is present in
the profile between core and jacket or in essence entirely within the jacket.
The presence of
reinforcement in this type of profile is known per se to the person skilled in
the art. The rein-
15 forcement can be composed of any material which appears to the person
skilled in the art to be
suitable. By way of example, the reinforcement introduced comprises at least
one material se-
lected from the group consisting of metals, such as aluminum or iron,
plastics, such as polyes-
ters, e.g. polyethylene terephthalate or polybutylene terephthalate,
glassfiber-reinforced plas-
tics, and mixtures thereof. Preference is given here to reinforcement made of
plastic or of glass-
20 fiber-reinforced plastic.
If reinforcement is introduced into the profile in the invention, this
reinforcement can have its
final shape when it is introduced into the extruder, an example being the
shape of a strip. In a
second embodiment, the reinforcement is extruded in the extruder
simultaneously with the jack-
et of the profile. To this end, the material of the reinforcement is
introduced, preferably in the
molten state, along the extruder.
In one preferred embodiment of the invention, the dimensions of the
reinforcement are depend-
ent on the dimensions of the profile and can maximize the stability of the
reinforced profile. The
design of this reinforcement gives reduced heat transmission within the
profile, for example in
windowframes or doorframes.
Step (F):
CA 02834380 2013-10-25
21
The optional step (F) of the process of the invention comprises the cooling of
the profile from
step (E). This cooling can be carried out by processes known to the person
skilled in the art, for
example by passing the resultant profile through an appropriate coolant, such
as air or water.
The temperature to which the profile is preferably cooled in step (F) of the
process of the inven-
tion is from room temperature to 60 C, preferably from room temperature to 40
C, achieved by
processes known to the person skilled in the art.
Step (G):
The optional step (G) of the process of the invention comprises the cutting of
the profile from
step (E) or (F) of the process of the invention. Apparatuses for cutting the
profile of step (G) are
known in general terms to the person skilled in the art, an example being
sawing. The continu-
ous process of the invention can in principle produce a continuous profile,
and this can therefore
be cut in step (G) of the process of the invention into lengths suitable for
the application, for ex-
ample pieces of from 1 to 12 m, preferably from 2 to 8 m.
The invention can provide the resultant profiles with a coating. By way of
example, this is nec-
essary or useful when the plastic used for the jacket is not per se resistant
to light and/or to
weathering. The invention can use a coating based on acrylate or based on
aliphatic polyure-
thane in order to obtain profiles that are resistant to light and/or to
weathering. The coating can
be applied after production of the jacket, for example after step (E), (F),
and/or (G). Processes
and apparatuses for coating the jacket are known per se to the person skilled
in the art.
The present invention also provides the profile that can be produced via the
process of the in-
vention. In relation to the details and to the preferred embodiments, see the
statements relating
to the process.
The present invention also provides a profile comprising a core made of a
polyurethane foam or
a mixture comprising a polyurethane foam, a jacket made of at least one
thermoplastic material,
and optionally a foil between core and jacket. In relation to the details and
to the preferred em-
bodiments, see the statements relating to the process.
CA 02834380 2013-10-25
22
In one particularly preferred embodiment, the profile of the invention
comprises a core made of
a polyurethane foam, a jacket made of polyvinyl chloride (PVC), and a foil
between core and
jacket made of thermoplastic polyurethanes, Teflon, metal, or a composite
material comprising
metal, textile, and combinations thereof. It is further preferable that the
profile of the invention
comprises reinforcement, preferably made of the abovementioned materials,
particularly prefer-
ably made of plastic or of glassfiber-reinforced plastic.
In one preferred embodiment of the profile of the invention, the foil encloses
the core at least to
some extent, preferably entirely.
In another preferred embodiment, the present invention therefore provides the
profile of the in-
vention where the at least one foil comprises at least one material selected
from the group con-
sisting of thermoplastic polyurethanes, Teflon, metal, composite material
comprising metal, tex-
tile, and combinations thereof.
The present invention also provides the use of the profile of the invention
for producing win-
dowframes, doorframes, or in the fitting-out of interiors, or in apparatuses
in which, during oper-
ation, temperature differences arise between interior space and exterior
space, examples being
cold rooms, air-conditioning equipment, ventilation systems, refrigerators,
(deep) freezer chests,
or pool covers. The profiles of the invention are preferably used here for
edging, or as profile for
a space surrounded by a structure.
The present invention also provides an apparatus for carrying out the process
of the invention,
comprising a unit for introducing the liquid precursor material of the foamed
core, optionally a
unit for introducing a foil, a gripper-belt system, an extruder with attached
extrusion die for pro-
ducing hollow profiles, and optionally units for cooling and cutting.
It is known that the individual elements of the apparatus of the invention are
known to the per-
son skilled in the art.
CA 02834380 2013-10-25
23
Figures
Figure 1 shows an apparatus of the invention, where this is preferably used
for carrying out the
process of the invention. The meanings of the reference signs here are as
follows:
1 Profile produced
2 Cooling unit
3 Extruder with profile-shaped die
5 Cooling zone
6 Feed vessel for polyol and optionally additives
7 Feed vessel for diisocyanate
8 Pump 1
9 Pump 2
10 Mixing unit
11 Foil
12 Unwind unit
13 Forming shoulder
14 Gripper-belt system
15 Saw
Figure 2 shows a gripper-belt system which can be used in the invention in
order to produce a
profile with a foam core. 16 and 17 here indicate the two jaws.
Figure 3 shows a gripper-belt system which can be used in the invention for
producing a profile
of the invention with two foam-element cores. Reference signs 18, 19 and 20
here indicate the
three jaws of this gripper-belt system. A indicates the separation between the
foam elements.
Figure 4 shows two gripper-belt systems that are arranged one upon the other,
where reference
signs 21, 22, 23 and 24 describe the single jaws. B describes the distance
between the jaws of
the gripper-belt.
