U.S. patent application number 14/477043 was filed with the patent office on 2015-03-05 for tube connectors based on a polyamide composition.
This patent application is currently assigned to ARKEMA FRANCE. The applicant listed for this patent is ARKEMA FRANCE. Invention is credited to Sylvain BENET, Yves DEYRAIL, Zhenzhong LI, Thibaut MONTANARI.
Application Number | 20150065641 14/477043 |
Document ID | / |
Family ID | 49578458 |
Filed Date | 2015-03-05 |
United States Patent
Application |
20150065641 |
Kind Code |
A1 |
DEYRAIL; Yves ; et
al. |
March 5, 2015 |
TUBE CONNECTORS BASED ON A POLYAMIDE COMPOSITION
Abstract
A tube connector made from a polyamide composition, the
polyamide composition including at least one first polyamide A
having an average number of carbon atoms per nitrogen atom C.sub.A
and at least one second polyamide B having an average number of
carbon atoms per nitrogen atom C.sub.B, wherein C.sub.A.ltoreq.8.5
and C.sub.B.gtoreq.7.5, and wherein C.sub.A<C.sub.B. The
composition may include a third polyamide C having an average
number of carbon atoms per nitrogen atom C.sub.C, wherein
C.sub.B.ltoreq.C.sub.C.
Inventors: |
DEYRAIL; Yves; (Evreux,
FR) ; MONTANARI; Thibaut; (Menneval, FR) ; LI;
Zhenzhong; (Jiangsu, CN) ; BENET; Sylvain;
(Bernay, FR) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
ARKEMA FRANCE |
Colombes |
|
FR |
|
|
Assignee: |
ARKEMA FRANCE
Colombes
FR
|
Family ID: |
49578458 |
Appl. No.: |
14/477043 |
Filed: |
September 4, 2014 |
Current U.S.
Class: |
524/538 ;
264/328.1; 525/432 |
Current CPC
Class: |
B29D 23/003 20130101;
F16L 47/02 20130101; C08L 77/06 20130101; B29C 45/0001 20130101;
C08L 77/02 20130101; C08L 77/06 20130101; B29K 2077/00 20130101;
C08L 77/02 20130101; C08K 7/14 20130101; C08L 2205/02 20130101;
C08L 2205/025 20130101; C08L 77/02 20130101; C08K 7/14 20130101;
C08K 7/14 20130101; C08L 77/06 20130101 |
Class at
Publication: |
524/538 ;
525/432; 264/328.1 |
International
Class: |
C08L 77/06 20060101
C08L077/06; B29D 23/00 20060101 B29D023/00; B29C 45/00 20060101
B29C045/00 |
Foreign Application Data
Date |
Code |
Application Number |
Sep 5, 2013 |
FR |
13.58494 |
Claims
1. A tube connector part made from a polyamide composition, the
polyamide composition comprising at least one first polyamide A
having an average number of carbon atoms per nitrogen atom C.sub.A
and at least one second polyamide B having an average number of
carbon atoms per nitrogen atom C.sub.B, wherein C.sub.A.ltoreq.8.5
and C.sub.B.gtoreq.7.5, and wherein C.sub.A<C.sub.B.
2. The tube connector part of claim 1, wherein the difference
C.sub.B-C.sub.A is from 1 to 6.
3. The tube connector part of claim 1, wherein
C.sub.A.ltoreq.7.5.
4. The tube connector part of claim 1, wherein the at least one
first polyamide A is selected from PA 6, PA 4.6, PA 6.6, PA 6/6.6,
PA 6/6.T, PA 6.6/6.T, PA 6.6/6.1, PA 6.1/6.T, PA 6.6/6.1/6.T, PA
6.10 and mixtures thereof.
5. The tube connector part of claim 1, wherein the composition
comprises from 1 to 70 wt. % of the at least one first polyamide
A.
6. The tube connector part of claim 1, wherein the second polyamide
B is selected from PA 6.10, PA 6.12, PA 6.14, PA 10.10, PA 11, PA
12, PA 10.12, PA 6.18, PA 12.T, PA 12/10.T, PA 10.10/10.T, PA B.12,
PA B.10/10.10, PA IPD.10, PA B.I/12 and mixtures thereof.
7. The tube connector part of claim 1, wherein the composition
comprises from 1 to 70 wt. % of the at least second polyamide
B.
8. The tube connector part of claim 1, wherein the composition
consists of one first polyamide A, one second polyamide B and,
optionally, non-polyamide additives.
9. The tube connector part of claim 1, wherein the composition
comprises, in addition to the first polyamide A and the second
polyamide B, at least one third polyamide C having an average
number of carbon atoms per nitrogen atom C.sub.C, wherein
C.sub.C.gtoreq.7.5 and C.sub.C.gtoreq.C.sub.B.
10. The tube connector part of claim 9, wherein C.sub.C.gtoreq.7.5
and C.sub.C>C.sub.B.
11. The tube connector part of claim 9, wherein the difference
C.sub.C-C.sub.B is from 1 to 4.
12. The tube connector part of claim 9, wherein the second
polyamide B is selected from PA 6.10, PA 6.12 and a mixture
thereof; and the third polyamide C is selected from PA 6.14, PA
10.10, PA 11, PA 12, PA 10.12, PA 6.18, PA 12.T, PA 12/10.T, PA
10.10/10.T, PA B.12, PA B.10/10.10, PA IPD.10, PA B.I/12 and
mixtures thereof.
13. The tube connector part of claim 9, wherein the composition
comprises from 1 to 80 wt. % of the at least one second polyamide
B; and the composition comprises from 1 to 70 wt. % of the at least
one third polyamide C.
14. The tube connector part of claim 9, wherein the composition
consists of one first polyamide A, one second polyamide B, one
third polyamide C and, optionally, non-polyamide additives.
15. The tube connector part of claim 1, wherein the amount of
polyamides in the composition is from 30 to 100 wt. %.
16. The tube connector part of claim 1, wherein the composition
further comprises additives selected from impact modifiers,
processing aids, fillers, stabilizers, nucleating agents, dyes,
pigments, fireproofing agents and mixtures thereof.
17. The tube connector part of claim 1, which is configured for
being welded to one or more tubes.
18. The tube connector part of claim 1, which is part of a circuit
for conveying liquids or gases in motor vehicles.
19. A process of making the tube connector part of claim 1,
comprising melting and shaping the polyamide composition.
20. The process of claim 19, which is an injection molding process.
Description
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] The present application claims the benefit of French
Application No. FR 13.58494, filed on Sep. 5, 2013. The entire
contents of French Application No. FR 13.58494 are hereby
incorporated herein by reference in their entirety.
TECHNICAL FIELD
[0002] Embodiments of the disclosure relates to tube connectors or
tube connector parts based on a polyamide composition as well as to
a process for making same.
TECHNICAL BACKGROUND
[0003] Tubes are needed to store and convey different types of
fluids. For instance, in motor vehicles, tubes are used for feeding
fuel from the tank to the engine, for the cooling circuit, for the
hydraulic system, for the air-conditioning system, etc.
[0004] Polyamides are widely used for making such tubes. In view of
all the technical requirements at stake, it is often necessary to
resort to multilayer structures. For instance, use is commonly made
of at least one outer layer based on polyamide having a relatively
high average number of carbon atoms per nitrogen atom (such as PA
11 or PA 12), providing the desired flexibility and mechanical
resistance to the tubes; and of at least one inner layer called a
barrier layer, providing the required impermeability to the
conveyed fluids. Polyamides having a relatively low average number
of carbon atoms per nitrogen atom (such as PA 6 or PA 6.6 for
instance), as well as non-polyamide materials such as
ethylene-vinyl alcohol copolymer, may be included in the barrier
layer.
[0005] The above tubes are either linked together or linked to
functional parts (such as filters), using connectors.
[0006] Conventional connectors are usually manufactured by
injection molding, using a polyamide material, such as PA 11 or PA
12, generally reinforced with glass fibers.
[0007] A conventional method to link the connectors to the tubes
and/or functional parts is based on mechanical anchoring achieved
owing to a relief on the connectors.
[0008] A safer and more effective fixation method involves the
partial melting of the polymers in the connectors and tubes and/or
functional parts. Such partial melting may be achieved for example
by spin welding, ultrasound welding or the like. However, the
adhesion of one substrate made from a polyamide to another
substrate made from another polyamide is variable: for instance the
adhesion of PA 12 with PA 12 or PA 11 is good, but the adhesion of
PA 12 with PA 6 is not.
[0009] There is therefore still a need for connectors exhibiting a
better adhesion with respect to various kinds of tubular
substrates, and in particular with respect to various types of
polyamide-based tubular substrates, especially in the context of a
welding assembly process such as spin welding.
[0010] Another constraint is that shrinkage should remain as low as
possible at the end of the manufacturing process (just like with
conventional connectors made from PA 12 for instance).
SUMMARY
[0011] It is a first object of an embodiment of the disclosure to
provide a tube connector part made from a polyamide composition,
the polyamide composition comprising at least one first polyamide A
having an average number of carbon atoms per nitrogen atom C.sub.A
and at least one second polyamide B having an average number of
carbon atoms per nitrogen atom C.sub.B, wherein C.sub.A.ltoreq.8.5
and C.sub.B.gtoreq.7.5, and wherein C.sub.A<C.sub.B.
[0012] According to one embodiment, the mass-weighted mean of the
heats of fusion of these polyamides A and B in the said composition
is greater than 25 J/g (DSC, ISO 11357-3 (2013)).
[0013] According to one embodiment, each of the polyamides A and B
has a heat of fusion of greater than 25 J/g (DSC, ISO 11357-3
(2013)).
[0014] The tube connector part may be a complete connector or may
represent only part of a tube connector, such as an end part
intended to provide the connection with at least one tube or
functional part, e.g. by welding.
[0015] According to one embodiment, the difference C.sub.B-C.sub.A
is from 1 to 6, more preferably from 2 to 4, or from 2 to 3.
[0016] According to one embodiment, C.sub.A.ltoreq.7.5, preferably
C.sub.A.ltoreq.6.5 and most preferably C.sub.A=6.
[0017] According to one embodiment, B is different from a PA 6/12
copolyamide provided that the composition comprises or consists of
two polyamides A and B.
[0018] According to one embodiment, A and B are different from a PA
6/12 copolyamide provided that the composition comprises only or
consists in two polyamides A and B.
[0019] According to one embodiment, the at least one first
polyamide A is selected from PA 6, PA 4.6, PA 6.6, PA 6/6.6, PA
6/6.T, PA 6.6/6.T, PA 6.6/6.1, PA 6.1/6.T, PA 6.6/6.1/6.T, PA 6.10
and mixtures thereof, and preferably is PA 6.
[0020] According to one embodiment, the composition comprises from
1 to 70 wt. %, preferably from 2 to 60 wt. % and more preferably
from 3 to 50 wt. %, in particular from 3 to 35% wt. % of the at
least one first polyamide A.
[0021] According to one embodiment, the second polyamide B is
selected from PA 6.10, PA 6.12, PA 6.14, PA 10.10, PA 11, PA 12, PA
10.12, PA 6.18, PA 12.T, PA 12/10.T, PA 10.10/10.T, PA B.12, PA
B.10/10.10, PA IPD.10, PA B.1/12 and mixtures thereof, preferably
from PA 6.10, PA 6.12, PA 10.10, PA 10.12, PA 12 and mixtures
thereof, and more preferably is PA 6.12, optionally in admixture
with another polyamide.
[0022] According to one embodiment, the composition comprises from
1 to 70 wt. %, preferably from 10 to 60 wt. % and more preferably
from 20 to 50 wt. % of the at least second polyamide B.
[0023] According to one embodiment, the composition consists of one
first polyamide A, one second polyamide B and optionally
non-polyamide additives; and, preferably, the first polyamide A is
PA 6 and the second polyamide B is PA 6.12.
[0024] According to one embodiment, at least one of A and B in the
composition comprising only or consisting in two polyamides is a
homopolyamide.
[0025] According to one embodiment, A and B in the composition
comprising only or consisting in two polyamides are
homopolyamides.
[0026] According to one embodiment, the composition comprises, in
addition to the first polyamide A and the second polyamide B, at
least one third polyamide C having an average number of carbon
atoms per nitrogen atom C.sub.C, wherein C.sub.C.gtoreq.7.5 and
C.sub.C.gtoreq.C.sub.B.
[0027] According to one embodiment, C.sub.C.gtoreq.7.5 and
C.sub.C>C.sub.B.
[0028] According to one embodiment, the mass-weighted mean of the
heats of fusion of these polyamides A, B and C in the said
composition is greater than 25 J/g (DSC, ISO 11357-3 (2013)).
[0029] According to one embodiment, each of the polyamides A, B and
C has a heat of fusion of greater than 25 J/g (DSC, ISO 11357-3
(2013)).
[0030] In the above defined composition comprising at least a third
polyamide C, A and/or B and/or C can be a copolyamide, in
particular PA 6/12.
[0031] According to one embodiment, the difference C.sub.C-C.sub.B
is from 1 to 4, preferably from 2 to 3.
[0032] According to one embodiment, the difference C.sub.B-C.sub.A
is from 1 to 6, and the difference C.sub.C-C.sub.B is from 1 to
4.
[0033] According to one embodiment, the difference C.sub.B-C.sub.A
is from 1 to 6, and the difference C.sub.C-C.sub.B is from 2 to
3.
[0034] According to one embodiment, the difference C.sub.B-C.sub.A
is from 2 to 4, and the difference C.sub.C-C.sub.B is from 1 to
4.
[0035] According to one embodiment, the difference C.sub.B-C.sub.A
is from 2 to 4, and the difference C.sub.C-C.sub.B is from 2 to
3.
[0036] According to one embodiment, the difference C.sub.B-C.sub.A
is from 2 to 3, and the difference C.sub.C-C.sub.B is from 1 to
4.
[0037] According to one embodiment, the difference C.sub.B-C.sub.A
is from 2 to 3, and the difference C.sub.C-C.sub.B is from 2 to
3.
[0038] According to one embodiment, C.sub.A.ltoreq.8.5,
C.sub.B.gtoreq.7.5, and C.sub.C.gtoreq.7.5, wherein
C.sub.A<C.sub.B and C.sub.C>C.sub.B and most preferably
C.sub.A=8.
[0039] According to one embodiment, C.sub.A.ltoreq.7.5, preferably
C.sub.A.ltoreq.6.5 and most preferably C.sub.A=6.
[0040] According to one embodiment, the second polyamide B is
selected from PA 6.10, PA 6.12 and a mixture thereof; and/or the
third polyamide C is selected from PA 6.14, PA 10.10, PA 11, PA 12,
PA 10.12, PA 6.18, PA 12.T, PA 12/10.T, PA 10.10/10.T, PA B.12, PA
B.10/10.10, PA IPD.10, PA B.I/12 and mixtures thereof, preferably
from PA 10.10, PA 10.12 and PA 12 and a mixture thereof; and more
preferably is PA 12.
[0041] According to one embodiment, the second polyamide B is PA
6.10; and the third polyamide C is selected from PA 6.14, PA 10.10,
PA 11, PA 12, PA 10.12, PA 6.18, PA 12.T, PA 12/10.T, PA
10.10/10.T, PA B.12, PA B.10/10.10, PA IPD.10, PA B.I/12 and
mixtures thereof, preferably from PA 10.10, PA 10.12 and PA 12 and
a mixture thereof; and more preferably is PA 12.
[0042] According to one embodiment, the second polyamide B is PA
6.12; and the third polyamide C is selected from PA 6.14, PA 10.10,
PA 11, PA 12, PA 10.12, PA 6.18, PA 12.T, PA 12/10.T, PA
10.10/10.T, PA B.12, PA B.10/10.10, PA IPD.10, PA B.I/12 and
mixtures thereof, preferably from PA 10.10, PA 10.12 and PA 12 and
a mixture thereof; and more preferably is PA 12.
[0043] According to one embodiment, the composition comprises from
1 to 80 wt. %, preferably from 5 to 70 wt. % and more preferably
from 10 to 65 wt. % of the at least one second polyamide B; and/or
the composition comprises from 1 to 70 wt. %, preferably from 2 to
60 wt. % and more preferably from 3 to 50 wt. % of the at least one
third polyamide C.
[0044] According to one embodiment, the composition consists of one
first polyamide A, one second polyamide B, one third polyamide C
and optionally non-polyamide additives; and preferably, the first
polyamide A is PA 6, the second polyamide B is PA 6.10 or PA 6.12,
and the third polyamide C is PA 10.10, PA 10.12 or PA 12.
[0045] According to one embodiment, the composition consists of one
first polyamide A, one second polyamide B, one third polyamide C
and optionally non-polyamide additives; and preferably, the first
polyamide A is PA 6, the second polyamide B is PA 6.10 and the
third polyamide C is PA 10.10, PA 10.12 or PA 12.
[0046] According to one embodiment, the composition consists of one
first polyamide A, one second polyamide B, one third polyamide C
and optionally non-polyamide additives; and preferably, the first
polyamide A is PA 6, the second polyamide B is PA 6.12, and the
third polyamide C is PA 10.10, PA 10.12 or PA 12.
[0047] According to one embodiment, the amount of polyamides in the
composition is from 30 to 100 wt. %, preferably from 50 to 99 wt.
%, more preferably from 60 to 95 wt. %, and most preferably from 65
to 85 wt. %.
[0048] According to one embodiment, the composition further
comprises additives selected from impact modifiers, processing
aids, fillers, stabilizers, nucleating agents, dyes, pigments,
fireproofing agents and mixtures thereof; and the composition
preferably comprises additives selected from fillers, impact
modifiers, stabilizers and combinations thereof; and the
composition more preferably comprises: [0049] from 10 to 40 wt. %
of fillers, in particular glass fibers; and/or [0050] from 0.1 to 2
wt. % of at least one stabilizer; and/or [0051] from 5 to 20 wt. %
of at least one functionalized impact modifier, in particular a
copolymer of ethylene, preferably ethylene propylene elastomer
copolymer.
[0052] According to one embodiment, the tube connector part is
configured for being welded to one or more tubes, preferably by
spin welding, said tubes being preferably polyamide tubes.
[0053] According to one embodiment, the tube connector part is part
of a circuit for conveying liquids or gases in motor vehicles.
[0054] An embodiment of the disclosure also relates to a process of
making the above-described tube connector part, comprising melting
and shaping the polyamide composition.
[0055] According to one embodiment, the process is an injection
molding process.
[0056] An embodiment of the disclosure makes it possible to
overcome the drawbacks of the known art. In particular, certain
embodiments of the disclosure provide connectors adhering well to
various kinds of materials, in particular to various types of
polyamide materials, such as PA 6 (or PA 6.T-based copolymers), PA
12 (or PA10.10), PA 6.10 (or PA 6.12) and PA 10.12; besides, these
connectors may be manufactured with a satisfactorily low level of
shrinkage.
[0057] An embodiment of the disclosure is particularly useful in
the context of a connection to multilayer tubes containing
different polyamide components in the inner and outer layers, such
as multilayer tubes having a PA 12-based outer layer and a PA
6-based inner layer. The connectors of an embodiment of the
disclosure can advantageously be welded to both types of surfaces
and the resistance of the connection can therefore be
maximized.
[0058] This may be achieved by using a composition comprising at
least two (and, according to some preferred embodiments, at least
three) polyamide components having different average numbers of
carbon atoms by nitrogen atom.
DESCRIPTION OF EMBODIMENTS
[0059] An embodiment of the disclosure will now be described in
more detail without limitation in the following description.
[0060] An embodiment of the disclosure relies on a composition
comprising at least two polyamide components, one within a lower
range of average number of carbon atoms per nitrogen atom, and the
other one within a higher range of average number of carbon atoms
per nitrogen atom. Optionally, a third polyamide component may be
present in the composition. In this case the first polyamide
component is within a low range of average number of carbon atoms
per nitrogen atom, the second polyamide component within an
intermediate range of average number of carbon atoms per nitrogen
atom, and the third polyamide component is within a high range of
average number of carbon atoms per nitrogen atom.
[0061] Polyamides encompass homopolyamides and copolyamides.
[0062] According to the present application, the term "polyamide",
also noted PA, is directed towards: [0063] homopolymers or
homopolyamides, [0064] copolymers or copolyamides, based on
different amide units, for instance polyamide 6/12 with amide units
derived from lactam-6 and from lactam-12, [0065] polyamide alloys,
provided that the polyamide is the major constituent.
[0066] There also exists a category of copolyamides in the broad
sense, which, although not preferred, falls within the context of
an embodiment of the disclosure. These are copolyamides comprising
not only amide units (which will be predominant, hence the fact
that they should be considered as copolyamides in the broad sense),
but also units of non-amide nature, for example ether units. The
best-known examples are the PEBAs or polyether-block-amides and
variants thereof copolyamide-ester-ether, copolyamide-ether and
copolyamide-ester. Among these, mention will be made of PEBA-12 in
which the polyamide units are the same as those of PAI2, and
PEBA-6.12 in which the polyamides units are the same as those of
PA6.12.
[0067] The nomenclature used to define polyamides is described in
the standard ISO 1874-1:1992 "Plastics--polyamide (PA) materials
for moulding and extrusion--Part 1: Designation", especially on
page 3 (Tables 1 and 2) and is well known to those skilled in the
art.
[0068] Homopolyamides are generally designated as PA X, wherein X
represents the residues of an amino-acid; or PA X.Y, wherein X
represents the residues of a diamine and Y represents the residues
of a diacid.
[0069] For a polyamide PA X, the average number of carbon atoms per
nitrogen atoms corresponds to the number of carbon atoms in the
amino-acid residue. For instance this average number is 6 for PA 6
(polycaprolactame), 11 for PA 11 (polyundecanamide) and 12 for PA
12 (polydodecanamide).
[0070] For a polyamide PA X.Y, the average number of carbon atoms
per nitrogen atoms corresponds to the mean of the number of carbon
atoms in the diamine X residues and in the diacid Y residues. For
instance, this average number is 8 for PA 6.10 (polyhexamethylene
sebacate), 9 for PA 6.12 (polyhexamethylene dodecanediamide), 10
for PA 10.10 (polydecamethylene sebacate), 10 for PA 12.T
(polydodecamethylene terephthalate--T representing residues from
terephthalic acid, comprising 8 carbon atoms), etc.
[0071] Copolyamides are generally designated as PA X/Y, or PA X/Y/Z
in the case of terpolymers, wherein X, Y and Z represent
homopolyamide units as described above.
[0072] For such polyamides, the average number of carbon atoms per
nitrogen atom corresponds to the molar pro rata of the various
amide units.
[0073] By way of example, in a PA 6.T/6.6 copolymer containing 60
mol. % of 6.T units and 40 mol. % of 6.6 units, the average number
is 6.6 (namely 60%.times.(6+8)/2+40%.times.(6+6)/2=6.6).
[0074] In case of a copolyamide containing non-amide units, the
calculation is performed solely on the amide units. Thus, for
example, PEBA 12, which is a block copolymer of amide units of the
PA 12 type and of ether units, the mean number of carbon atoms per
nitrogen atom is 12, like for PA 12; for PEBA 6.12, it is 9, like
for PA 6.12.
[0075] The polyamides used in an embodiment of the disclosure may
be homopolyamides or copolyamides. Preferably, they are
homopolyamides.
[0076] Preferably, the copolyamides used in an embodiment of the
disclosure contain only amide units.
[0077] The composition of an embodiment of the disclosure comprises
at least one first polyamide A having an average number of carbon
atoms per nitrogen atom C.sub.A and one second polyamide B having
an average number of carbon atoms per nitrogen atom C.sub.B, with
C.sub.A.ltoreq.8.5 and C.sub.B.gtoreq.7.5 and
C.sub.A<C.sub.B.
[0078] According to some embodiments, C.sub.A.ltoreq.7.5; or
C.sub.A<7.5.
[0079] According to some embodiments, C.sub.A is from 4 to 4.5; or
from 4.5 to 5; or from 5 to 5.5; or from 5.5 to 6; or from 6 to
6.5; or from 6.5 to 7; or from 7 to 7.5; or from 7.5 to 8; or from
8 to 8.5. An advantageous range for C.sub.A may be from 5.8 to
6.2.
[0080] The first polyamide A is preferably PA 6. Alternatively,
other polyamide components may be used such as PA 4.6
(polytetramethylene adipamate), PA 6.6 (polyhexamethylene
adipamate), or such as various copolyamides, including PA 6/6.T, PA
6/6.6, PA 6.T/6.6, PA 6.1/6.6 and PA 6.T/6.1/6.6 (I representing
residues from isophthalic acid).
[0081] PA 6.10 may also be used as the first polyamide A, in which
case C.sub.B must be greater than 8. For instance, the second
polyamide B may be PA 12 in this case.
[0082] Preferably, only one polyamide A is used. Alternatively, it
is possible to use a mixture of two or more such polyamides.
Combinations of PA 6+PA 4.6 and of PA 6+PA 6.6 are examples of such
a mixture.
[0083] Turning to the second polyamide B, according to various
embodiments, C.sub.B is from 7.5 to 8; or from 8 to 8.5; or from
8.5 to 9; or from 9 to 9.5; or from 9.5 to 10; or from 10 to 10.5;
or from 10.5 to 11; or from 11 to 11.5; or from 11.5 to 12; or from
12 to 12.5; or from 12.5 to 13; or from 13 to 13.5; or from 13.5 to
14; or above 14. An advantageous range for C.sub.B may be from 8 to
12.
[0084] According to some embodiments, the difference
C.sub.B-C.sub.A is from 0.5 to 1; or from 1 to 1.5; or from 1.5 to
2; or from 2 to 2.5; or from 2.5 to 3; or from 3 to 3.5; or from
3.5 to 4; or from 4 to 4.5; or from 4.5 to 5; or from 5 to 5.5; or
from 5.5 to 6; or from 6 to 6.5; or from 6.5 to 7.
[0085] The second polyamide B may notably be selected from PA 6.10,
PA 6.12, PA 6.14, PA 10.10, PA 11, PA 12, PA 10.12
(polydecamethylene sebacamate), PA 6.18, PA 12.T. Copolyamides such
as PA 12/10.T and PA 10.10/10.T may also be used, as well as PA
B.12, PA B.10/10.10, PA IPD.10 and PA B.1/12, wherein B represents
the residue obtained from the condensation of
bis-(3-methyl-4-aminocyclohexyl)-methane (BMACM) and IPD represents
the residue obtained from the condensation of isophorone
diamine.
[0086] According to one embodiment, only one polyamide B with an
average number of carbon atoms per nitrogen atom C.sub.B.gtoreq.7.5
is used. In this case, C.sub.B is preferably greater than 8, more
preferably greater than 8.5; and/or the difference C.sub.B-C.sub.A
is preferably greater than 1; or greater than 1.5; or greater than
2; or greater than 2.5; or greater than 3.
[0087] Alternatively, it is possible to use at least two polyamides
having an average number of carbon atoms per nitrogen atom greater
than or equal to 7.5. In this case, it is convenient to designate
these at least two polyamides as a second polyamide B with an
average number of carbon atoms per nitrogen atom
C.sub.B.gtoreq.7.5, and a third polyamide C with an average number
of carbon atoms per nitrogen atom C.sub.C.gtoreq.7.5.
[0088] Preferably, the second polyamide B has an intermediate
average number of carbon atoms per nitrogen atom, namely
7.5.ltoreq.C.sub.B<10, and the third polyamide C has a high
average number of carbon atoms per nitrogen atom, namely
C.sub.C.gtoreq.10--although alternatively both polyamides may have
average numbers of carbon atoms per nitrogen atom within the same
range, i.e. either 7.5.ltoreq.C.sub.B<10 and
7.5.ltoreq.C.sub.C<10; or C.sub.B.gtoreq.10 and
C.sub.C.gtoreq.10.
[0089] According to some embodiments the difference C.sub.C-C.sub.B
is from 0.5 to 1; or from 1 to 1.5; or from 1.5 to 2; or from 2 to
2.5; or from 2.5 to 3; or from 3 to 3.5; or from 3.5 to 4; or from
4 to 4.5; or from 4.5 to 5.
[0090] In the above case of three polyamides A, B and C, the second
polyamide B may notably be selected from PA 6.10 and PA 6.12 and
the third polyamide C may notably be selected from PA 6.14, PA
10.10, PA 11, PA 12, PA 10.12, PA 6.18, PA 12.T, PA 12/10.T, PA
10.10/10.T PA B.12, PA B.10/10.10, PA IPD.10, PA B.I/12. PA 12, PA
10.12 and PA 10.10 are preferred.
[0091] In the above case of three polyamides A, B and C, the second
polyamide B is PA 6.10 and the third polyamide C may notably be
selected from PA 6.14, PA 10.10, PA 11, PA 12, PA 10.12, PA 6.18,
PA 12.T, PA 12/10.T, PA 10.10/10.T PA B.12, PA B.10/10.10, PA
IPD.10, PA B.I/12. PA 12, PA 10.12 and PA 10.10 are preferred.
[0092] In the above case of three polyamides A, B and C, the second
polyamide B is PA 6.12 and the third polyamide C may notably be
selected from PA 6.14, PA 10.10, PA 11, PA 12, PA 10.12, PA 6.18,
PA 12.T, PA 12/10.T, PA 10.10/10.T PA B.12, PA B.10/10.10, PA
IPD.10, PA B.I/12. PA 12, PA 10.12 and PA 10.10 are preferred.
[0093] Preferably, only one polyamide B with an average number of
carbon atoms per nitrogen atom 7.5.ltoreq.C.sub.B<10 is used.
Alternatively, it is possible to use mixtures of two or more such
polyamides. A combination of PA 6.10+PA 6.12 is then preferred.
[0094] Preferably, only one polyamide C with an average number of
carbon atoms per nitrogen atom C.sub.C.gtoreq.10 is used.
Alternatively, it is possible to use mixtures of two or more such
polyamides. A combination of PA 12+PA 10.10 is then preferred.
[0095] The weight proportion of each polyamide A, B and optionally
C within the total composition may vary significantly.
[0096] Some embodiments of binary formulations based on one
polyamide A and one polyamide B (plus the optional additives
described below), with C.sub.A.ltoreq.8.5 and 7.5.ltoreq.C.sub.B,
are summarized in the following table, the weight proportions being
relative to the total composition:
TABLE-US-00001 Formulation No. A (wt. %) B (wt. %) 1 1 to 5% 1 to
5% 2 1 to 5% 5 to 10% 3 1 to 5% 10 to 15% 4 1 to 5% 15 to 20% 5 1
to 5% 20 to 25% 6 1 to 5% 25 to 30% 7 1 to 5% 30 to 35% 8 1 to 5%
35 to 40% 9 1 to 5% 40 to 45% 10 1 to 5% 45 to 50% 11 1 to 5% 50 to
55% 12 1 to 5% 55 to 60% 13 1 to 5% 60 to 65% 14 1 to 5% 65 to 70%
15 1 to 5% 70 to 75% 16 1 to 5% 75 to 80% 17 1 to 5% 80 to 85% 18 1
to 5% 85 to 90% 19 1 to 5% 90 to 95% 20 5 to 10% 1 to 5% 21 5 to
10% 5 to 10% 22 5 to 10% 10 to 15% 23 5 to 10% 15 to 20% 24 5 to
10% 20 to 25% 25 5 to 10% 25 to 30% 26 5 to 10% 30 to 35% 27 5 to
10% 35 to 40% 28 5 to 10% 40 to 45% 29 5 to 10% 45 to 50% 30 5 to
10% 50 to 55% 31 5 to 10% 55 to 60% 32 5 to 10% 60 to 65% 33 5 to
10% 65 to 70% 34 5 to 10% 70 to 75% 35 5 to 10% 75 to 80% 36 5 to
10% 80 to 85% 37 5 to 10% 85 to 90% 38 5 to 10% 90 to 95% 39 10 to
15% 1 to 5% 40 10 to 15% 5 to 10% 41 10 to 15% 10 to 15% 42 10 to
15% 15 to 20% 43 10 to 15% 20 to 25% 44 10 to 15% 25 to 30% 45 10
to 15% 30 to 35% 46 10 to 15% 35 to 40% 47 10 to 15% 40 to 45% 48
10 to 15% 45 to 50% 49 10 to 15% 50 to 55% 50 10 to 15% 55 to 60%
51 10 to 15% 60 to 65% 52 10 to 15% 65 to 70% 53 10 to 15% 70 to
75% 54 10 to 15% 75 to 80% 55 10 to 15% 80 to 85% 56 10 to 15% 85
to 90% 57 15 to 20% 1 to 5% 58 15 to 20% 5 to 10% 59 15 to 20% 10
to 15% 60 15 to 20% 15 to 20% 61 15 to 20% 20 to 25% 62 15 to 20%
25 to 30% 63 15 to 20% 30 to 35% 64 15 to 20% 35 to 40% 65 15 to
20% 40 to 45% 66 15 to 20% 45 to 50% 67 15 to 20% 50 to 55% 68 15
to 20% 55 to 60% 69 15 to 20% 60 to 65% 70 15 to 20% 65 to 70% 71
15 to 20% 70 to 75% 72 15 to 20% 75 to 80% 73 15 to 20% 80 to 85%
74 20 to 25% 1 to 5% 75 20 to 25% 5 to 10% 76 20 to 25% 10 to 15%
77 20 to 25% 15 to 20% 78 20 to 25% 20 to 25% 79 20 to 25% 25 to
30% 80 20 to 25% 30 to 35% 81 20 to 25% 35 to 40% 82 20 to 25% 40
to 45% 83 20 to 25% 45 to 50% 84 20 to 25% 50 to 55% 85 20 to 25%
55 to 60% 86 20 to 25% 60 to 65% 87 20 to 25% 65 to 70% 88 20 to
25% 70 to 75% 89 20 to 25% 75 to 80% 90 25 to 30% 1 to 5% 91 25 to
30% 5 to 10% 92 25 to 30% 10 to 15% 93 25 to 30% 15 to 20% 94 25 to
30% 20 to 25% 95 25 to 30% 25 to 30% 96 25 to 30% 30 to 35% 97 25
to 30% 35 to 40% 98 25 to 30% 40 to 45% 99 25 to 30% 45 to 50% 100
25 to 30% 50 to 55% 101 25 to 30% 55 to 60% 102 25 to 30% 60 to 65%
103 25 to 30% 65 to 70% 104 25 to 30% 70 to 75% 105 30 to 35% 1 to
5% 106 30 to 35% 5 to 10% 107 30 to 35% 10 to 15% 108 30 to 35% 15
to 20% 109 30 to 35% 20 to 25% 110 30 to 35% 25 to 30% 111 30 to
35% 30 to 35% 112 30 to 35% 35 to 40% 113 30 to 35% 40 to 45% 114
30 to 35% 45 to 50% 115 30 to 35% 50 to 55% 116 30 to 35% 55 to 60%
117 30 to 35% 60 to 65% 118 30 to 35% 65 to 70% 119 35 to 40% 1 to
5% 120 35 to 40% 5 to 10% 121 35 to 40% 10 to 15% 122 35 to 40% 15
to 20% 123 35 to 40% 20 to 25% 124 35 to 40% 25 to 30% 125 35 to
40% 30 to 35% 126 35 to 40% 35 to 40% 127 35 to 40% 40 to 45% 128
35 to 40% 45 to 50% 129 35 to 40% 50 to 55% 130 35 to 40% 55 to 60%
131 35 to 40% 60 to 65% 132 40 to 45% 1 to 5% 133 40 to 45% 5 to
10% 134 40 to 45% 10 to 15% 135 40 to 45% 15 to 20% 136 40 to 45%
20 to 25% 137 40 to 45% 25 to 30% 138 40 to 45% 30 to 35% 139 40 to
45% 35 to 40% 140 40 to 45% 40 to 45% 141 40 to 45% 45 to 50% 142
40 to 45% 50 to 55% 143 40 to 45% 55 to 60% 144 45 to 50% 1 to 5%
145 45 to 50% 5 to 10% 146 45 to 50% 10 to 15% 147 45 to 50% 15 to
20% 148 45 to 50% 20 to 25% 149 45 to 50% 25 to 30% 150 45 to 50%
30 to 35% 151 45 to 50% 35 to 40% 152 45 to 50% 40 to 45% 153 45 to
50% 45 to 50% 154 45 to 50% 50 to 55% 155 50 to 55% 1 to 5% 156 50
to 55% 5 to 10% 157 50 to 55% 10 to 15% 158 50 to 55% 15 to 20% 159
50 to 55% 20 to 25% 160 50 to 55% 25 to 30% 161 50 to 55% 30 to 35%
162 50 to 55% 35 to 40% 163 50 to 55% 40 to 45% 164 50 to 55% 45 to
50% 165 55 to 60% 1 to 5% 166 55 to 60% 5 to 10% 167 55 to 60% 10
to 15% 168 55 to 60% 15 to 20% 169 55 to 60% 20 to 25% 170 55 to
60% 25 to 30% 171 55 to 60% 30 to 35% 172 55 to 60% 35 to 40% 173
55 to 60% 40 to 45% 174 60 to 65% 1 to 5% 175 60 to 65% 5 to 10%
176 60 to 65% 10 to 15% 177 60 to 65% 15 to 20% 178 60 to 65% 20 to
25% 179 60 to 65% 25 to 30% 180 60 to 65% 30 to 35% 181 60 to 65%
35 to 40% 182 65 to 70% 1 to 5% 183 65 to 70% 5 to 10% 184 65 to
70% 10 to 15% 185 65 to 70% 15 to 20% 186 65 to 70% 20 to 25% 187
65 to 70% 25 to 30% 188 65 to 70% 30 to 35% 189 70 to 75% 1 to 5%
190 70 to 75% 5 to 10% 191 70 to 75% 10 to 15% 192 70 to 75% 15 to
20% 193 70 to 75% 20 to 25% 194 70 to 75% 25 to 30% 195 75 to 80% 1
to 5% 196 75 to 80% 5 to 10% 197 75 to 80% 10 to 15% 198 75 to 80%
15 to 20% 199 75 to 80% 20 to 25% 200 80 to 85% 1 to 5% 201 80 to
85% 5 to 10% 202 80 to 85% 10 to 15% 203 80 to 85% 15 to 20% 204 85
to 90% 1 to 5% 205 85 to 90% 5 to 10% 206 85 to 90% 10 to 15% 207
90 to 95% 1 to 5% 208 90 to 95% 5 to 10% 209 95 to 99% 1 to 5%
[0097] It should be understood that similar formulations to those
mentioned in the above table can also be prepared based on two (or
more than two) polyamides A and/or two (or more than two)
polyamides B, in which case the weight proportions indicated in the
table relate to the total of the polyamide(s) A on the one hand and
the total of the polyamide(s) B on the other hand.
[0098] Some embodiments of ternary formulations based on one
polyamide A, one polyamide B and one polyamide C (plus the optional
additives described below), with C.sub.A<C.sub.B<C.sub.C (and
with for example C.sub.A.ltoreq.7.5, 7.5.ltoreq.C.sub.B<10 and
10.ltoreq.C.sub.C) are summarized in the following table, the
weight proportions being relative to the total composition:
TABLE-US-00002 Formulation No. A (wt. %) B (wt. %) C (wt. %) 210 1
to 10% 1 to 10% 1 to 10% 211 1 to 10% 1 to 10% 10 to 20% 212 1 to
10% 1 to 10% 20 to 30% 213 1 to 10% 1 to 10% 30 to 40% 214 1 to 10%
1 to 10% 40 to 50% 215 1 to 10% 1 to 10% 50 to 60% 216 1 to 10% 1
to 10% 60 to 70% 217 1 to 10% 1 to 10% 70 to 80% 218 1 to 10% 1 to
10% 80 to 90% 219 1 to 9% 1 to 9% 90 to 98% 220 1 to 10% 10 to 20%
1 to 10% 221 1 to 10% 10 to 20% 10 to 20% 222 1 to 10% 10 to 20% 20
to 30% 223 1 to 10% 10 to 20% 30 to 40% 224 1 to 10% 10 to 20% 40
to 50% 225 1 to 10% 10 to 20% 50 to 60% 226 1 to 10% 10 to 20% 60
to 70% 227 1 to 10% 10 to 20% 70 to 80% 228 1 to 10% 10 to 19% 80
to 89% 229 1 to 10% 20 to 30% 1 to 10% 230 1 to 10% 20 to 30% 10 to
20% 231 1 to 10% 20 to 30% 20 to 30% 232 1 to 10% 20 to 30% 30 to
40% 233 1 to 10% 20 to 30% 40 to 50% 234 1 to 10% 20 to 30% 50 to
60% 235 1 to 10% 20 to 30% 60 to 70% 236 1 to 10% 20 to 29% 70 to
79% 237 1 to 10% 30 to 40% 1 to 10% 238 1 to 10% 30 to 40% 10 to
20% 239 1 to 10% 30 to 40% 20 to 30% 240 1 to 10% 30 to 40% 30 to
40% 241 1 to 10% 30 to 40% 40 to 50% 242 1 to 10% 30 to 40% 50 to
60% 243 1 to 10% 30 to 39% 60 to 69% 244 1 to 10% 40 to 50% 1 to
10% 245 1 to 10% 40 to 50% 10 to 20% 246 1 to 10% 40 to 50% 20 to
30% 247 1 to 10% 40 to 50% 30 to 40% 248 1 to 10% 40 to 50% 40 to
50% 249 1 to 10% 40 to 49% 50 to 59% 250 1 to 10% 50 to 60% 1 to
10% 251 1 to 10% 50 to 60% 10 to 20% 252 1 to 10% 50 to 60% 20 to
30% 253 1 to 10% 50 to 60% 30 to 40% 254 1 to 10% 50 to 59% 40 to
49% 255 1 to 10% 60 to 70% 1 to 10% 256 1 to 10% 60 to 70% 10 to
20% 257 1 to 10% 60 to 70% 20 to 30% 258 1 to 10% 60 to 69% 30 to
39% 259 1 to 10% 70 to 80% 1 to 10% 260 1 to 10% 70 to 80% 10 to
20% 261 1 to 10% 70 to 79% 20 to 29% 262 1 to 10% 80 to 90% 1 to
10% 263 1 to 10% 80 to 89% 10 to 19% 264 1 to 9% 90 to 98% 1 to 9%
265 10 to 20% 1 to 10% 1 to 10% 266 10 to 20% 1 to 10% 10 to 20%
267 10 to 20% 1 to 10% 20 to 30% 268 10 to 20% 1 to 10% 30 to 40%
269 10 to 20% 1 to 10% 40 to 50% 270 10 to 20% 1 to 10% 50 to 60%
271 10 to 20% 1 to 10% 60 to 70% 272 10 to 20% 1 to 10% 70 to 80%
273 10 to 19% 1 to 10% 80 to 89% 274 10 to 20% 10 to 20% 1 to 10%
275 10 to 20% 10 to 20% 10 to 20% 276 10 to 20% 10 to 20% 20 to 30%
277 10 to 20% 10 to 20% 30 to 40% 278 10 to 20% 10 to 20% 40 to 50%
279 10 to 20% 10 to 20% 50 to 60% 280 10 to 20% 10 to 20% 60 to 70%
281 10 to 20% 10 to 20% 70 to 80% 282 10 to 20% 20 to 30% 1 to 10%
283 10 to 20% 20 to 30% 10 to 20% 284 10 to 20% 20 to 30% 20 to 30%
285 10 to 20% 20 to 30% 30 to 40% 286 10 to 20% 20 to 30% 40 to 50%
287 10 to 20% 20 to 30% 50 to 60% 288 10 to 20% 20 to 30% 60 to 70%
289 10 to 20% 30 to 40% 1 to 10% 290 10 to 20% 30 to 40% 10 to 20%
291 10 to 20% 30 to 40% 20 to 30% 292 10 to 20% 30 to 40% 30 to 40%
293 10 to 20% 30 to 40% 40 to 50% 294 10 to 20% 30 to 40% 50 to 60%
295 10 to 20% 40 to 50% 1 to 10% 296 10 to 20% 40 to 50% 10 to 20%
297 10 to 20% 40 to 50% 20 to 30% 298 10 to 20% 40 to 50% 30 to 40%
299 10 to 20% 40 to 50% 40 to 50% 300 10 to 20% 50 to 60% 1 to 10%
301 10 to 20% 50 to 60% 10 to 20% 302 10 to 20% 50 to 60% 20 to 30%
303 10 to 20% 50 to 60% 30 to 40% 304 10 to 20% 60 to 70% 1 to 10%
305 10 to 20% 60 to 70% 10 to 20% 306 10 to 20% 60 to 70% 20 to 30%
307 10 to 20% 70 to 80% 1 to 10% 308 10 to 20% 70 to 80% 10 to 20%
309 10 to 19% 80 to 89% 1 to 10% 310 20 to 30% 1 to 10% 1 to 10%
311 20 to 30% 1 to 10% 10 to 20% 312 20 to 30% 1 to 10% 20 to 30%
313 20 to 30% 1 to 10% 30 to 40% 314 20 to 30% 1 to 10% 40 to 50%
315 20 to 30% 1 to 10% 50 to 60% 316 20 to 30% 1 to 10% 60 to 70%
317 20 to 29% 1 to 10% 70 to 79% 318 20 to 30% 10 to 20% 1 to 10%
319 20 to 30% 10 to 20% 10 to 20% 320 20 to 30% 10 to 20% 20 to 30%
321 20 to 30% 10 to 20% 30 to 40% 322 20 to 30% 10 to 20% 40 to 50%
323 20 to 30% 10 to 20% 50 to 60% 324 20 to 30% 10 to 20% 60 to 70%
325 20 to 30% 20 to 30% 1 to 10% 326 20 to 30% 20 to 30% 10 to 20%
327 20 to 30% 20 to 30% 20 to 30% 328 20 to 30% 20 to 30% 30 to 40%
329 20 to 30% 20 to 30% 40 to 50% 330 20 to 30% 20 to 30% 50 to 60%
331 20 to 30% 30 to 40% 1 to 10% 332 20 to 30% 30 to 40% 10 to 20%
333 20 to 30% 30 to 40% 20 to 30% 334 20 to 30% 30 to 40% 30 to 40%
335 20 to 30% 30 to 40% 40 to 50% 336 20 to 30% 40 to 50% 1 to 10%
337 20 to 30% 40 to 50% 10 to 20% 338 20 to 30% 40 to 50% 20 to 30%
339 20 to 30% 40 to 50% 30 to 40% 340 20 to 30% 50 to 60% 1 to 10%
341 20 to 30% 50 to 60% 10 to 20% 342 20 to 30% 50 to 60% 20 to 30%
343 20 to 30% 60 to 70% 1 to 10% 343 20 to 30% 60 to 70% 10 to 20%
344 20 to 29% 70 to 79% 1 to 10% 345 30 to 40% 1 to 10% 1 to 10%
346 30 to 40% 1 to 10% 10 to 20% 347 30 to 40% 1 to 10% 20 to 30%
348 30 to 40% 1 to 10% 30 to 40% 349 30 to 40% 1 to 10% 40 to 50%
350 30 to 40% 1 to 10% 50 to 60% 351 30 to 39% 1 to 10% 60 to 69%
352 30 to 40% 10 to 20% 1 to 10% 353 30 to 40% 10 to 20% 10 to 20%
354 30 to 40% 10 to 20% 20 to 30% 355 30 to 40% 10 to 20% 30 to 40%
356 30 to 40% 10 to 20% 40 to 50% 357 30 to 40% 10 to 20% 50 to 60%
358 30 to 40% 20 to 30% 1 to 10% 359 30 to 40% 20 to 30% 10 to 20%
360 30 to 40% 20 to 30% 20 to 30% 361 30 to 40% 20 to 30% 30 to 40%
362 30 to 40% 20 to 30% 40 to 50% 363 30 to 40% 30 to 40% 1 to 10%
364 30 to 40% 30 to 40% 10 to 20% 365 30 to 40% 30 to 40% 20 to 30%
366 30 to 40% 30 to 40% 30 to 40% 367 30 to 40% 40 to 50% 1 to 10%
368 30 to 40% 40 to 50% 10 to 20% 369 30 to 40% 40 to 50% 20 to 30%
370 30 to 40% 50 to 60% 1 to 10% 371 30 to 40% 50 to 60% 10 to 20%
372 30 to 39% 60 to 69% 1 to 10% 373 40 to 50% 1 to 10% 1 to 10%
374 40 to 50% 1 to 10% 10 to 20% 375 40 to 50% 1 to 10% 20 to 30%
376 40 to 50% 1 to 10% 30 to 40% 377 40 to 50% 1 to 10% 40 to 50%
378 40 to 49% 1 to 10% 50 to 59% 379 40 to 50% 10 to 20% 1 to 10%
380 40 to 50% 10 to 20% 10 to 20% 381 40 to 50% 10 to 20% 20 to 30%
382 40 to 50% 10 to 20% 30 to 40% 383 40 to 50% 10 to 20% 40 to 50%
384 40 to 50% 20 to 30% 1 to 10% 385 40 to 50% 20 to 30% 10 to 20%
386 40 to 50% 20 to 30% 20 to 30% 387 40 to 50% 20 to 30% 30 to 40%
388 40 to 50% 30 to 40% 1 to 10% 389 40 to 50% 30 to 40% 10 to 20%
390 40 to 50% 30 to 40% 20 to 30% 391 40 to 50% 40 to 50% 1 to 10%
392 40 to 50% 40 to 50% 10 to 20% 393 40 to 49% 50 to 59% 1 to 10%
394 50 to 60% 1 to 10% 1 to 10% 395 50 to 60% 1 to 10% 10 to 20%
396 50 to 60% 1 to 10% 20 to 30% 397 50 to 60% 1 to 10% 30 to 40%
398 50 to 59% 1 to 10% 40 to 49% 399 50 to 60% 10 to 20% 1 to 10%
400 50 to 60% 10 to 20% 10 to 20% 401 50 to 60% 10 to 20% 20 to 30%
402 50 to 60% 10 to 20% 30 to 40% 403 50 to 60% 20 to 30% 1 to 10%
404 50 to 60% 20 to 30% 10 to 20% 405 50 to 60% 20 to 30% 20 to 30%
406 50 to 60% 30 to 40% 1 to 10% 407 50 to 60% 30 to 40% 10 to 20%
408 50 to 59% 40 to 49% 1 to 10% 409 60 to 70% 1 to 10% 1 to 10%
410 60 to 70% 1 to 10% 10 to 20% 411 60 to 70% 1 to 10% 20 to 30%
412 60 to 69% 1 to 10% 30 to 39% 413 60 to 70% 10 to 20% 1 to 10%
414 60 to 70% 10 to 20% 10 to 20% 415 60 to 70% 10 to 20% 20 to 30%
416 60 to 70% 20 to 30% 1 to 10% 417 60 to 70% 20 to 30% 10 to 20%
418 60 to 69% 30 to 39% 1 to 10% 419 70 to 80% 1 to 10% 1 to 10%
420 70 to 80% 1 to 10% 10 to 20% 421 70 to 79% 1 to 10% 20 to 29%
422 70 to 80% 10 to 20% 1 to 10% 423 70 to 80% 10 to 20% 10 to 20%
424 70 to 79% 20 to 29% 1 to 10% 425 80 to 90% 1 to 10% 1 to 10%
426 80 to 89% 1 to 10% 10 to 19% 427 80 to 89% 10 to 19% 1 to 10%
428 90 to 98% 1 to 9% 1 to 9%
[0099] It should be understood that similar formulations to those
mentioned in the above table can also be prepared based on two (or
more than two) polyamides A and/or two (or more than two)
polyamides B and/or two (or more than two) polyamides C, in which
case the weight proportions indicated in the table relate to the
total of the polyamide(s) A, B and C respectively.
[0100] The total weight proportion of polyamides in the composition
may be from 30 to 35%; or from 35 to 40%; or from 40 to 45%; or
from 45 to 50%; or from 50 to 55%; or from 55 to 60%; or from 60 to
65%; or from 65 to 70%; or from 70 to 75%; or from 75 to 80%; or
from 80 to 85%; or from 85 to 90%; or from 90 to 95%; or from 95 to
100%.
[0101] The composition may comprise various additives in addition
to the above-described polyamides.
[0102] The additives may comprise an impact modifier, a processing
aid, a filler, a stabilizer, a nucleating agent, a dye, a pigment
and/or a fireproofing agent.
[0103] The impact modifier may be a non-rigid polymer having a
flexural modulus of less than 100 MPa measured according to the ISO
178:2010 standard.
[0104] This polymer preferably has a low glass transition
temperature, i.e. of less than 0.degree. C.
[0105] The impact modifier is, very preferentially, chemically
functionalized so as to be able to react with the above polyamides
and to form an alloy with them.
[0106] The impact modifier is preferentially one or more
polyolefins, some or all of them bearing a function selected from
carboxylic acid, carboxylic anhydride and epoxide functions and any
other function capable of chemically reacting with polyamides,
typically via the amine chain ends (in the case of carboxylic acid
or carboxylic anhydride) or via the acid chain ends (in the case of
epoxide, in particular glycidyl methacrylate).
[0107] The polyolefin may more particularly be selected from:
[0108] a copolymer of ethylene and propylene of elastomeric nature
(EPR), [0109] an ethylene-propylene-diene copolymer of elastomeric
nature (EPDM) and [0110] an ethylene/alkyl (meth)acrylate
copolymer.
[0111] Another possibility is to use a polyether block amide (PEBA)
as an non-functionalized impact modifier, said PEBA having a
flexural modulus of less than 100 MPa measured according to the ISO
178:2010 standard.
[0112] The weight proportion of impact modifier in the composition,
when present, is advantageously from 1 to 40%, preferably from 3 to
30%, more preferably from 5 to 20%.
[0113] A stabilizer may also be used, and in particular a thermal
stabilizer. The weight proportion of thermal stabilizer in the
composition may be from 0 to 4%, notably from 0.01 to 2% or from
0.1 to 1.5%.
[0114] A copper-based thermal stabilizer may be used, in particular
a copper salt or a copper salt derivative, such as copper iodide,
copper bromide, copper halides, derivatives of mixtures thereof.
Copper salts I are preferred. Examples are copper iodide, copper
bromide, copper chloride, copper fluoride, copper thiocyanate,
copper nitrate, copper acetate, copper naphthenate, copper caprate,
copper laurate, copper stearate, copper acetylacetonate, copper
oxide.
[0115] Another possible thermal stabilizer is a metallic halide
salt such as LiI, NaI, KI, MgI.sub.2, KBr or CaI.sub.2. KI and KBr
are preferred.
[0116] Preferably, the copper-based thermal stabilizer is a mixture
of potassium iodide and copper iodide (KI/CuI), more preferably
with a weight ratio of 90:10 to 70:30. Such a stabilizer is
marketed under the designation Polyadd P201 by Ciba.
[0117] Copper-based stabilizers are further described in document
U.S. Pat. No. 2,705,227.
[0118] Complexed copper may also be used, as marketed by
Brueggemann under the designations Bruggolen H3336, H3337,
H3373.
[0119] Other possible thermal stabilizers are sterically-hindered
phenolic antioxidants.
[0120] These compounds are described in document US 2012/0279605,
at paragraphs [0025] et [0026], incorporated herein by
reference.
[0121] UV stabilizers may also be present, in particular phosphites
or sterically hindered amine-based stabilizers (HALS), which are
2,2,6,6-tetramethylpiperidine derivatives. They can be used e.g.
within a range of 0 to 1 wt. %, or 0.01 a 0.5 wt. %.
[0122] Processing aids may include lubricants and/or release
agents.
[0123] Among the processing aids, mention may be made of stearates,
such as calcium or zinc stearate, natural waxes, and
tetrafluoroethylene-based polymers. The weight proportion of
processing aids in the composition, if present, may typically be
from 0.01 to 0.3%, notably from 0.02 to 0.1%.
[0124] Among the dyes and pigments, mention may be made notably of
carbon black and of optical brighteners. The weight proportion of
dyes and/or pigments in the composition, if present, may typically
be from 0.1 to 0.2%.
[0125] Among the fillers, mention may be made of silica, graphite,
expanded graphite, carbon black, glass beads, kaolin, magnesia,
slag, talc, carbon nanocharges (such as carbon nanotubes), metallic
oxides (titanium oxide), metals, and more preferably fibers
(aramides, glass fibers, carbon fibers).
[0126] The weight proportion of fillers in the composition may be
from 1 to 65%, preferably from 1 to 50%, more preferably from 5 to
40%, most preferably be from 10 to 35%. In particular, glass fibers
may be present in a weight proportion of from 10 to 65%, preferably
from 20 to 40%. Alternatively or complementarily, carbon fibers may
be present in a weight proportion from 5 to 40%, preferably of 5 to
25%, preferably from 10 to 20%. A mixture of carbon fibers and
glass fibers may also be used.
[0127] The use of fibers is particularly useful for reinforcing the
connectors made from the composition. Said fibers may for instance
have an average length of 0.05 to 1 mm, notably of 0.1 to 0.5 mm.
Their average diameter can be from 5 to 20 .mu.m, preferably from 6
to 14 .mu.m.
[0128] Some of the fillers may be antistatic compounds and may also
have a coloring effect on the composition.
[0129] The composition of an embodiment of the disclosure may
comprise one or more additional polymers, in addition to the above
polyamides (and optionally the above polyolefins).
[0130] Such additional polymers may be for instance phenylene
polysulfide (PPS), polyphenylene oxide (PPO), a fluorinated
polymer, and mixtures thereof.
[0131] The composition may contain up to 20 wt. % of such
additional polymers.
[0132] Alternatively and preferably, the composition does not
contain any such additional polymer.
[0133] According to one embodiment, the composition of an
embodiment of the disclosure comprises, or essentially consists of,
or consists of: [0134] 1 to 50 wt. %, preferably 2 to 45 wt. % of
the abovementioned first polyamide A (notably PA 6); [0135] 10 to
80 wt. %, preferably 20 to 70 wt. % of the abovementioned second
polyamide B (and optionally third polyamide C); [0136] 0 to 15 wt.
% of impact modifier(s), such as EPR; [0137] 10 to 40 wt. % of
filler(s), such as glass fibers or carbon fibers; [0138] 0 to 2% of
stabilizer(s).
[0139] The composition used in an embodiment of the disclosure may
be prepared by compounding all components together. The composition
is usually recovered in the form of pellets or granules.
[0140] The connectors or connector parts can be manufactured by
injection molding. Injection molding consists of high pressure
injection of the raw material (polyamide composition) into a mold
which shapes it into the desired shape.
[0141] The polyamide composition is preferably provided in a
pelletized form. It is fed through a hopper into a heated barrel
with a reciprocating screw. The screw delivers the raw material
forward, up through a check valve. The melted material is collected
at the front of the screw. It is then forced at high pressure and
velocity into the mold. The molded part is cooled. The polyamide
recrystallizes during the cooling time.
[0142] It should be noted that as an alternative to feeding the
complete composition to the heated barrel in the form of granules
or pellets, it is also possible to add part (or all) of the
components separately to the barrel, in which case the complete
composition is made in situ during the injection molding
process.
[0143] The connectors or connector parts of an embodiment of the
disclosure are preferably made of one piece and are preferably made
of a single layer. They preferably have a uniform composition.
[0144] The connectors or connector parts of an embodiment of the
disclosure may be welded to one or more tubes and/or to other
functional objects (such as a filter).
[0145] Welding may notably be achieved by hot gas welding, speed
tip welding, extrusion welding, contact welding, overmolding, hot
plate welding, high frequency welding, injection welding,
ultrasound welding, friction welding, spin welding and solvent
welding.
[0146] The connectors or connector parts may in particular be
welded to articles or layers made of polyamide compositions, such
as polyamide compositions based on PA 6, or on
[0147] PA 6.T, or on PA 12, or on PA 6.10, or on PA 6.12 or on PA
10.12.
[0148] The connectors or connector parts of an embodiment of the
disclosure may thus be incorporated into fluidic circuits such as
circuits for storing and conveying liquid or gases, in particular
fuel or refrigerant, and more particularly in a motor vehicle.
EXAMPLES
[0149] The following examples illustrate an embodiment of the
disclosure without limiting it.
[0150] Eleven polyamide compositions I-1 to I-11 according to an
embodiment of the disclosure, as well as four comparative polyamide
compositions C-1 to C-4 were prepared as follows:
[0151] The compositions were prepared using a usual compounding
process. Use was made of a Werner 40 twin-screw extruder, running
at 300 rpm, 60 kg/h, with the temperature set at 280.degree. C. on
all the barrels in order to melt the polymers. The polymers
(polyamides and impact modifier) were introduced at the beginning
of the screw, the reinforcing agent (glass fiber, carbon fiber) was
introduced using a side feeder, in the middle of the screw.
[0152] The respective formulations are summarized in the table
below, the proportions being expressed in weight percentage:
TABLE-US-00003 Ex. PA PA PA Stab. Stab. No. 6.10 6.12 10.10 PA 6 PA
12 EPR CF GF #1 #2 1-1 44 -- -- 10 15 -- -- 30 1 -- 1-2 -- 44 -- 10
15 -- -- 30 1 -- 1-3 10 -- -- 44 15 -- -- 30 1 -- 1-4 10 -- -- 15
44 -- -- 30 1 -- 1-5 10 -- 44 15 -- -- -- 30 1 -- 1-6 63 -- -- 3 3
-- -- 30 1 -- 1-7 -- 44 -- 5 10 10 -- 30 1 -- 1-8 44.5 -- -- 10 15
-- -- 30 -- 0.5 1-9 59 -- -- 10 15 -- 15 -- 1 -- 1-10 -- 44 -- 15
-- 10 -- 30 1 -- 1-11 15 -- -- -- 44 10 -- 30 1 -- C-1 -- -- -- --
69 -- -- 30 1 -- C-2 -- 69 -- -- -- -- -- 30 1 -- C-3 -- -- 69 --
-- -- -- 30 1 -- C-4 -- 59 -- -- -- 10 -- 30 1 --
[0153] In the above table, EPR means "ethylene propylene rubber"
(Exxellor VA1801 from Exxon), CF means "carbon fibers" (Tenax A 243
from Toho Tenax), GF means "glass fibers" (type 3540, from PPG),
Stab.#1 designates a mixture of organic stabilizers composed of
0.8% phenol (Lowinox 44B25 from Great Lakes) and 0.2% phosphite
(Irgafos 168 from Ciba) and Stab.#2 designates a mixture of mineral
stabilizers based on copper iodide and potassium iodide (Polyadd
P201 from Ciba).
[0154] The PA 6.10 polyamide has a number-average molecular mass Mn
of 19,000 and a melting point of 223.degree. C.
[0155] The PA 6.12 polyamide has a number-average molecular mass Mn
of 19,000 and a melting point of 218.degree. C.
[0156] The PA 10.10 polyamide has a number-average molecular mass
Mn of 20,000 and a melting point of 198.degree. C.
[0157] The PA 6 polyamide has a number-average molecular mass Mn of
18,000 and a melting point of 220.degree. C.
[0158] The PA 12 polyamide has a number-average molecular mass Mn
of 23,000 and a melting point of 178.degree. C.
[0159] Melting points have been determined according to ISO 11357-3
(2013).
[0160] These various compositions were tested in terms of shrinkage
and adhesion to several polyamide-based substrates, according to
the following protocols.
[0161] Shrinkage evaluation: the various compositions were shaped
by injection molding into 100.times.100.times.2 mm plates. The
plate dimensions were accurately measured after a conditioning time
of 24 hours at room temperature and then compared to the initial
dimensions of the mold at the same temperature used for plate
molding. All compositions were molded with a conventional injection
molding machine with the barrel heated at 290.degree. C., the mold
cavity being temperature controlled at 60.degree. C. The thickness
of the plates was in the same range of thickness than that of usual
connectors, and the plates were produced using the same processing
technique so as to be representative of the actual shrinkage of the
connectors.
[0162] Adhesion evaluation: adhesion was assessed using an
overmolding process, i.e. a two-step process. First, an insert part
was molded out of one reference polyamide A, B or C. Second, the
insert molded in the first part was placed in a mold with the same
part geometry but with a higher thickness, and was overmolded by
one of the tested compositions. This procedure was then repeated
for all the compositions described in the examples, the insert part
being alternatively polyamide A, B or C. The overmolded geometry
was chosen so as to be able to perform a peeling test where the
adhesion between the tested composition and the reference polyamide
A, B or C was characterized.
[0163] During an overmolding process, when the overmolding material
(here, the composition described in the examples) flows onto the
insert material, due to the high temperature of the molten polymer
(typically 290.degree. C.), a small interface region between the
two materials is molten (about 100 .mu.m). Therefore, the
overmolding process is found to be representative of welding
techniques such as spin welding, plate welding, ultrasonic welding
or high frequency welding,-where a partial melting of the material
to be welded is used to generate adhesion.
[0164] The results are summarized in the table below, with the
following nomenclature: 1=fully satisfactory; 2=acceptable;
3=unsatisfactory; 4=extremely unsatisfactory.
TABLE-US-00004 Ex. Adhesion to PA 6 Adhesion to Adhesion to No. or
PA 6.T PA 12 PA 6.10 or PA 6.12 Shrinkage 1-1 1 1 1 1 1-2 1 1 1 1
1-3 1 1 1 1 1-4 1 1 1 1 1-5 1 1 1 1 1-6 1 1 1 1 1-7 1 1 1 1 1-8 1 1
1 1 1-9 1 1 1 1 1-10 1 2 1 1 1-11 2 1 1 1 C-1 4 1 3 1 C-2 3 3 1 4
C-3 1 4 3 4 C-4 3 3 1 4
[0165] Embodiments of the disclosure may include:
1. A tube connector part made from a polyamide composition, the
polyamide composition comprising at least one first polyamide A
having an average number of carbon atoms per nitrogen atom C.sub.A
and at least one second polyamide B having an average number of
carbon atoms per nitrogen atom C.sub.B, wherein C.sub.A.ltoreq.8.5
and C.sub.B.gtoreq.7.5, and wherein C.sub.A<C.sub.B. 2. The tube
connector part of embodiment 1, wherein the difference
C.sub.B-C.sub.A is from 1 to 6, more preferably from 2 to 4, or
from 2 to 3. 3. The tube connector part of embodiments 1 or 2,
wherein C.sub.A 7.5, preferably C.sub.A.ltoreq.6.5 and most
preferably C.sub.A=6. 4. The tube connector part of one of
embodiments 1 to 3, wherein the at least one first polyamide A is
selected from PA 6, PA 4.6, PA 6.6, PA 6/6.6, PA 6/6.T, PA 6.6/6.T,
PA 6.6/6.1, PA 6.1/6.T, PA 6.6/6.1/6.T, PA 6.10 and mixtures
thereof, and preferably is PA 6. 5. The tube connector part of one
of embodiments 1 to 4, wherein the composition comprises from 1 to
70 wt. %, preferably from 2 to 60 wt. % and more preferably from 3
to 50 wt. %, in particular from 3 to 35 wt. % of the at least one
first polyamide A. 6. The tube connector part of one of embodiments
1 to 5, wherein the second polyamide B is selected from PA 6.10, PA
6.12, PA 6.14, PA 10.10, PA 11, PA 12, PA 10.12, PA 6.18, PA 12.T,
PA 12/10.T, PA 10.10/10.T, PA B.12, PA B.10/10.10, PA IPD.10, PA
B.I/12 and mixtures thereof, preferably from PA 6.10, PA 6.12, PA
10.10, PA 10.12, PA 12 and mixtures thereof, and more preferably is
PA 6.12, optionally in admixture with another polyamide. 7. The
tube connector part of one of embodiments 1 to 6, wherein the
composition comprises from 1 to 70 wt. %, preferably from 10 to 60
wt. % and more preferably from 20 to 50 wt. % of the at least
second polyamide B. 8. The tube connector part of one of
embodiments 1 to 7, wherein the composition consists of one first
polyamide A, one second polyamide B and optionally non-polyamide
additives; and wherein, preferably, the first polyamide A is PA 6
and the second polyamide B is PA 6.12. 9. The tube connector part
of one of embodiments 1 to 7, wherein the composition comprises, in
addition to the first polyamide A and the second polyamide B, at
least one third polyamide C having an average number of carbon
atoms per nitrogen atom C.sub.C, wherein C.sub.C.gtoreq.7.5 and
C.sub.C.gtoreq.CB. 10. The tube connector part of embodiment 9,
wherein C.sub.C.gtoreq.7.5 and C.sub.C>C.sub.B. 11. The tube
connector part of embodiments 9 or 10, wherein the difference
C.sub.C-C.sub.B is from 1 to 4, preferably from 2 to 3. 12. The
tube connector part of one of embodiments 9 to 11, wherein the
second polyamide B is selected from PA 6.10, PA 6.12 and a mixture
thereof; and/or the third polyamide C is selected from PA 6.14, PA
10.10, PA 11, PA 12, PA 10.12, PA 6.18, PA 12.T, PA 12/10.T, PA
10.10/10.T, PA B.12, PA B.10/10.10, PA IPD.10, PA B.I/12 and
mixtures thereof, preferably from PA 10.10, PA 10.12, PA 12 and a
mixture thereof; and more preferably is PA 12. 13. The tube
connector part of one of embodiments 9 to 12, wherein the
composition comprises from 1 to 80 wt. %, preferably from 5 to 70
wt. % and more preferably from 10 to 65 wt. % of the at least one
second polyamide B; and/or the composition comprises from 1 to 70
wt. %, preferably from 2 to 60 wt. % and more preferably from 3 to
50 wt. % of the at least one third polyamide C. 14. The tube
connector part of one of embodiments 9 to 13, wherein the
composition consists of one first polyamide A, one second polyamide
B, one third polyamide C and optionally non-polyamide additives;
and wherein, preferably, the first polyamide A is PA 6, the second
polyamide B is PA 6.10 or PA 6.12, and the third polyamide C is PA
10.10, PA 10.12 or PA 12. 15. The tube connector part of one of
embodiments 1 to 14, wherein the amount of polyamides in the
composition is from 30 to 100 wt. %, preferably from 50 to 99 wt.
%, more preferably from 60 to 95 wt. %, and most preferably from 65
to 85 wt. %. 16. The tube connector part of one of embodiments 1 to
15, wherein the composition further comprises additives selected
from impact modifiers, processing aids, fillers, stabilizers,
nucleating agents, dyes, pigments, fireproofing agents and mixtures
thereof; and wherein the composition preferably comprises additives
selected from fillers, impact modifiers, stabilizers and
combinations thereof; and the composition more preferably
comprises: [0166] from 10 to 40 wt. % of fillers, in particular
glass fibers; and/or [0167] from 0.1 to 2 wt. % of at least one
stabilizer; and/or [0168] from 5 to 20 wt. % of at least one
functionalized impact modifier, in particular a copolymer of
ethylene, preferably ethylene propylene elastomer copolymer. 17.
The tube connector part of one of embodiments 1 to 16, which is
configured for being welded to one or more tubes, preferably by
spin welding, said tubes being preferably polyamide tubes. 18. The
tube connector part of one of embodiments 1 to 17, which is part of
a circuit for conveying liquids or gases in motor vehicles. 19. A
process of making the tube connector part of one of embodiments 1
to 18, comprising melting and shaping the polyamide composition.
20. The process of embodiment 19, which is an injection molding
process.
* * * * *