U.S. patent application number 09/960053 was filed with the patent office on 2002-03-21 for amide polymer/silicone polymer blends.
This patent application is currently assigned to Eastman Chemical Company. Invention is credited to Darnell, William R., Hale, Wesley R., Jones, Allan Scott, Murray, David Logan.
Application Number | 20020035200 09/960053 |
Document ID | / |
Family ID | 22489129 |
Filed Date | 2002-03-21 |
United States Patent
Application |
20020035200 |
Kind Code |
A1 |
Jones, Allan Scott ; et
al. |
March 21, 2002 |
Amide polymer/silicone polymer blends
Abstract
The invention provides a method of making an amide-type
polymer/silicone polymer blend comprising the steps of preparing a
silicone polymer emulsion comprising a silicone polymer dispersed
in a liquid continuous phase; introducing the silicone polymer
emulsion into an amide-type polymerization reaction medium prior to
or during the reaction, wherein the reaction medium comprises 1) a
diacid component and a diamine component, an oligomer of a diacid
and a diamine component, or a mixture thereof, and polymerizing the
components of b)1, thereby providing an amide-type polymer/silicone
polymer blend. A amide-type polymer/silicone polymer blends are
also provided.
Inventors: |
Jones, Allan Scott;
(Limestone, TN) ; Darnell, William R.; (Weber
City, VA) ; Murray, David Logan; (Fall Branch,
TN) ; Hale, Wesley R.; (Kingsport, TN) |
Correspondence
Address: |
Jacqueline M. Hutter
NEEDLE & ROSENBERG, P.C.
The Candler Building, Suite 1200
127 Peachtree Street, N.E.
Atlanta
GA
30303-1811
US
|
Assignee: |
Eastman Chemical Company
|
Family ID: |
22489129 |
Appl. No.: |
09/960053 |
Filed: |
September 20, 2001 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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09960053 |
Sep 20, 2001 |
|
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09517254 |
Mar 2, 2000 |
|
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60139966 |
Jun 18, 1999 |
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Current U.S.
Class: |
524/731 |
Current CPC
Class: |
C08L 77/06 20130101;
C08L 83/04 20130101; C08L 77/00 20130101; C08L 77/12 20130101; C08G
69/32 20130101; C08G 77/14 20130101; C08G 77/26 20130101; C08L
83/04 20130101; C08G 77/06 20130101; C08G 69/265 20130101; C08G
77/20 20130101; C08L 77/10 20130101; C08G 69/44 20130101; C08G
77/28 20130101; C08L 83/00 20130101; C08G 77/70 20130101; C08G
69/04 20130101; C08L 77/00 20130101; C08G 77/16 20130101; C08L
77/06 20130101; C08L 77/12 20130101; C08L 83/00 20130101; C08L
77/10 20130101; C08L 83/00 20130101; C08L 83/00 20130101; C08L
2666/14 20130101; C08L 83/00 20130101 |
Class at
Publication: |
524/731 |
International
Class: |
C08L 001/00 |
Claims
What is claimed is:
1. A method of making an amide-type polymer/silicone polymer blend
comprising the steps of: (a) preparing a silicone polymer emulsion
comprising a silicone polymer dispersed in a liquid continuous
phase; (b) introducing the silicone polymer emulsion into an
amide-type polymerization reaction medium prior to or during the
reaction, wherein the reaction medium comprises 1) a diacid
component and a diamine component, an oligomer of a diacid and a
diamine component, or a mixture thereof; and (c) polymerizing the
components of b)l, thereby providing an amide-type polymer/silicone
polymer blend.
2. The method of claim 1, wherein the continuous phase comprises
water substantially in the absence of diol, thereby providing a
polyamide polymer.
3. The method of claim 1, wherein the continuous phase comprises
from about 10% to about 100% water.
4. The method of claim 1, wherein the continuous phase comprises
from about 10% to about 100% diol.
5. The method of claim 4, wherein the diol comprises ethylene diol;
1,3-trimethylene diol; 1,3-propylene diol; tripropylene diol;
1,4-butanediol; 1,5-pentanediol; 1,6 hexanediol; 1,7-heptanediol;
1,8-octanediol; 1,9-nonanediol; neopentyl diol; cis- or trans
cyclohexanedimethanol; cis or trans 2,2,4,4-tetramethyl-1,3
cyclobutanediol; diethylene diol, or a mixture thereof.
6. The method of claim 1, wherein the silicone polymer comprises
homo or copolymers of polydimethylsiloxane, wherein the homo or
copolymers comprise aminopropyl; vinyl; mercaptopropyl;
phenylmethyl; epoxy or amino-ethylaminopropyl functionalities.
7. The method of claim 1, wherein the silicone polymer emulsion
comprises a surfactant and wherein the surfactant comprises an
anionic surfactant, a cationic surfactant, a nonionic surfactant,
or a mixture thereof.
8. The method of claim 1, wherein the diacid comprises isophthalic
acid, terephthalic acid; cyclohexanedicarboxylic acid; a 6 to 12
carbon aliphatic diacid; or a mixture thereof.
9. The method of claim 1, wherein the diamine comprises
meta-xylylene diamine; para-xylylene diamine;
1,3-cyclohexane(bis)methylamine; 1,4-cyclohexane(bis)methylamine; a
6 to 12 carbon aliphatic diamine or lactam; a 4 to 12 carbon
aliphatic diamine; or a mixture thereof.
10. The method of claim 1, wherein the amide-type polymer comprises
a partially aromatic polyamide and wherein the partially aromatic
polyamide comprises poly(m-xylylene adipamide); poly(hexamethylene
isophthalamide); poly(hexamethylene adipamide-co-isophthalamide);
poly(hexamethylene adipamide-co-terephthalamide);
poly(hexamethylene isophthalamide-co-terep- hthalamide); or a
mixture thereof.
11. The method of claim 1, wherein the amide-type polymer comprises
an aliphatic polyamide and wherein the aliphatic polyamide
comprises polyethylene-adipamide (nylon 2,6);
polytetramethylene-adipamide (nylon 4,6);
polyhexamethylene-adipamide (nylon 6,6);
polyhexamethylene-sebacami- de (nylon 6,10);
polyhexamethylene-dodecamide (nylon 6,12);
polyoctamethylene-adipamide (nylon 8,6);
polydecamethylene-adipamide (nylon 10,6);
polydodecamethylene-adipamide (nylon 12,6);
polydodecamethylene-sebacamide (nylon 12,8); or a mixture
thereof.
12. The method of claim 1, wherein glass fibers are added to the
amide-type polymerization reaction medium prior to or during the
polymerization reaction.
13. The product made by the process of claim 1.
14. An amide-type polymer/silicone polymer blend comprising: (a) a
silicone polymer emulsion comprising a silicone polymer; and (b)
amide-type polymer, wherein the amide-type polymer is formed by
introducing the silicone polymer emulsion into an amide-type
polymerization reaction medium prior to or during the reaction,
wherein the reaction medium comprises 1) a diacid component and a
diamine component, an oligomer of a diacid and a diamine component,
or a mixture thereof.
15. The polymer blend of claim 14, wherein the silicone polymer
emulsion comprises: (a) a silicone polymer; (b) a surfactant; and
(c) a liquid continuous phase.
16. The polymer blend of claim 15, wherein the continuous phase
comprises water substantially in the absence of a diol, thereby
providing a polyamide polymer.
17. The polymer blend of claim 15, wherein the continuous phase
comprises from about 10% to about 100% water.
18. The polymer blend of claim 15, wherein the continuous phase
comprises water and diol, thereby providing a polyesteramide.
19. The polymer blend of claim 15, wherein the continuous phase
comprises from about 10% to about 100% diol.
20. The polymer blend of claim 19, wherein the diol comprises
ethylene diol; 1,3-trimethylene diol; 1,3-propylene diol;
tripropylene diol; 1,4-butanediol; 1,5-pentanediol; 1,6 hexanediol;
1,7-heptanediol; 1,8-octanediol; 1,9-nonanediol; neopentyl diol;
cis- or trans cyclohexanedimethanol; cis or trans
2,2,4,4-tetramethyl-1,3 cyclobutanediol; diethylene diol, or a
mixture thereof.
21. The polymer blend of claim 15, wherein the silicone polymer
comprises homo or copolymers of polydimethylsiloxane, wherein the
homo or copolymers comprise aminopropyl; vinyl; mercaptopropyl;
phenyhnethyl; epoxy or amino-ethylaminopropyl functionalities.
22. The polymer blend of claim 15, wherein the surfactant comprises
an anionic surfactant, a cationic surfactant, a nonionic
surfactant, or a mixture thereof.
23. The polymer blend of claim 15, wherein the diacid comprises
isophthalic acid; terephthalic acid; cyclohexanedicarboxylic acid;
a 6 to 12 carbon aliphatic diacid; or a mixture thereof.
24. The polymer blend of claim 15, comprising a diamine, wherein
the diamine comprises meta-xylylene diamine; para-xylylene diamine;
1,3-cyclohexane(bis)methylamine; 1,4-cyclohexane(bis)methylamine; a
6 to 12 carbon aliphatic diamine or lactam; a 4 to 12 carbon
aliphatic diamine; or a mixture thereof.
25. The polymer blend of claim 15, comprising a partially aromatic
polyamide, wherein the partially aromatic polyamide comprises
poly(m-xylylene adipamide); poly(hexamethylene isophthalamide;
poly(hexamethylene adipamide-co-isophthalamide); poly(hexamethylene
adipamide-co-terephthalamide); poly(hexamethylene
isophthalamide-co-terep- hthalamide); or a mixture thereof.
26. The polymer blend of claim 15, comprising an aliphatic
polyamide, wherein the aliphatic polyamide comprises
polyethylene-adipamide (nylon 2,6); polytetramethylene-adipamide
(nylon 4,6); polyhexamethylene-adipami- de (nylon 6,6);
polyhexamethylene-sebacamide (nylon 6,10);
polyhexamethylene-dodecamide (nylon 6,12);
polyoctamethylene-adipamide (nylon 8,6);
polydecamethylene-adipamide (nylon 10,6);
olydodecamethylene-adipamide (nylon 12,6);
polydodecamethylene-sebacamide (nylon 12,8); or a mixture
thereof.
27. The polymer blend of claim 15, wherein glass fibers are added
to the amide-type polymerization reaction medium prior to or during
the polymerization reaction.
28. A method of making an amide-type polymer/silicone polymer blend
comprising the steps of: (a) preparing a silicone polymer emulsion
comprising a liquid continuous phase; (b) introducing the silicone
polymer emulsion into an amide-type polymer; and (c) extruding the
silicone polymer emulsion and the amide-type polymer, thereby
providing an amide-type polymer/silicone polymer blend.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims priority to U.S. Provisional
Application Ser. No. 60/139,966, filed Jun. 18, 1999, the
disclosure of which is incorporated herein in its entirety.
FIELD OF THE INVENTION
[0002] The present invention relates to processes for making
amide-type polymers that are modified with a silicone polymer
emulsion comprising a silicone polymer. The silicone polymer
emulsion may comprise water, diol, or a mixture thereof. The
silicone polymer emulsion may also optionally comprise cosolvents.
The invention further relates to amide-type polymer/silicone
polymer blends.
BACKGROUND OF THE INVENTION
[0003] It is known to modify polyamide polymers by blending the
polyamide polymer with another polymer in an extruder. To improve
the impact properties of a polyamide, a low Tg elastomer is
typically added to the polymer in a twin-screw extruder. For
example, Polymer Engineering and Science, Vol. 23, 7, Page 380
(1983) discloses the use of maleated LDPE blended into nylon 6,6 in
a torque rheometer. The effects of polyamide blend component
properties and final blend morphology on properties are shown in
Adv. Chem. Ser. (1993), 233 (Toughened Plastics 1), 70-104. The use
of epoxy, carboxylic acid, and imide functionality in
polyamide/core-shell rubber blends is disclosed in Japanese Patent
No. 04175370. Using anhydride and epoxy functionality in polyamide
blends with rubbery ethylene copolymers is disclosed in WO 9522570.
The size of the dispersed phase is critical in attaining good
properties as taught in J. Appl. Polym. Sci. (1994), 54(3), pg
339-54. However, these previously disclosed methods of modifying
polyamide polymers each require a separate blending step. Such
blending processes are energy intensive, sometimes resulting in the
reduction of the physical properties of the polymer, in particular
the molecular weight, and the blending step is required, which
utilizes more resources and more time.
[0004] There exists a need for a process for producing a polymer
blend by more economical methods. Such a need has been solved by
the present invention, which can achieve such a blend in a
polymerization reactor, wherein the physical properties of the
condensation polymer are maintained or improved.
SUMMARY OF THE INVENTION
[0005] In one aspect, the invention provides a method of making an
amide-type polymer/silicone polymer blend comprising the steps
of:
[0006] a. preparing a silicone polymer emulsion comprising a
silicone polymer dispersed in a liquid continuous phase;
[0007] b. introducing the silicone polymer emulsion into an
amide-type polymerization reaction medium prior to or during the
reaction, wherein the reaction medium comprises 1) a diacid
component and a diamine component, an oligomer of a diacid and a
diamine component, or a mixture thereof; and
[0008] c. polymerizing the components of b)1, thereby providing an
amide-type polymer/silicone polymer blend.
[0009] Still further, the invention provides, an amide-type
polymer/silicone polymer blend comprising:
[0010] a. a silicone polymer emulsion comprising a silicone
polymer; and
[0011] b. amide-type polymer
[0012] wherein the amide-type polymer is formed by introducing the
silicone polymer emulsion into an amide-type polymerization
reaction medium prior to or during the reaction and wherein the
reaction medium comprises 1) a diacid component and a diamine
component, an oligomer of a diacid and a diamine component, or a
mixture thereof.
[0013] Still further, the invention provides a method of making an
amide-type polymer/silicone polymer blend comprising the steps
of:
[0014] a. preparing a silicone polymer emulsion comprising a liquid
continuous phase;
[0015] b. introducing the silicone polymer emulsion into an
amide-type polymer; and
[0016] c. extruding the silicone polymer emulsion and the
amide-type polymer, thereby providing an amide-type
polymer/silicone polymer blend.
[0017] Additional advantages of the invention will be set forth in
part in the description which follows, and in part will be apparent
from the description, or may be learned by practice of the
invention. The advantages of the invention will be realized and
attained by means of the elements and combinations particularly
pointed out in the appended claims. It is to be understood that
both the foregoing general description and the following detailed
description are exemplary and explanatory only and are not
restrictive of the invention, as claimed.
DETAILED DESCRIPTION OF THE INVENTION
[0018] The present invention may be understood more readily by
reference to the following detailed description of preferred
embodiments of the invention and the Examples included therein.
[0019] Before the present compositions of matter and methods are
disclosed and described, it is to be understood that this invention
is not limited to specific synthetic methods or to particular
formulations, as such may, of course, vary. It is also to be
understood that the terminology used herein is for the purpose of
describing particular embodiments only and is not intended to be
limiting.
[0020] In this specification and in the claims which follow,
reference will be made to a number of terms which shall be defined
to have the following meanings:
[0021] The singular forms "a," "an" and "the" include plural
referents unless the context clearly dictates otherwise.
[0022] "Optional" or "optionally" means that the subsequently
described event or circumstances may or may not occur, and that the
description included instances where said event or circumstance
occurs and instances where it does not.
[0023] "Silicone polymer emulsion" is herein defined as a
dispersion of polymeric particles in a continuous phase, the
polymeric particles preferably having a size range of from about
0.20 to about 1000 microns. Further preferably, the polymeric
polymers have a particle size of from about 0.1 to about 10
microns. The silicone polymers of the present invention preferably
have a molecular weight of about 5,000 to about 1,000,000 Daltons.
The polymeric particles are preferably produced through emulsion
polymerization processes. Alternatively, such emulsions may be
prepared through direct emulsification e.g., mechanical
emulsification processes.
[0024] "Diol" is a synonym for glycol or dihydric alcohol. "Polyol"
is a polyhydric alcohol containing three or more hydroxyl
groups.
[0025] The abbreviation "nm" means nanometers. "Tg" means glass
transition temperature.
[0026] Throughout this application, where publications are
referenced, the disclosures of these publications in their
entireties are hereby incorporated by reference into this
application to more fully describe the state of the art to which
this invention pertains.
[0027] Ranges are often expressed herein as from about one
particular value, and/or to about another particular value. When
such a range is expressed, it is to be understood that another
embodiment is from the one particular value and/or to the other
particular value. Similarly, when values are expressed as
approximations, by use of the antecedent "about," it will be
understood that the particular value is another embodiment.
[0028] In one aspect, the invention provides a method of making an
amide-type polymer/silicone polymer blend comprising the steps
of:
[0029] a. preparing a silicone polymer emulsion comprising a
silicone polymer dispersed in a liquid continuous phase;
[0030] b. introducing the silicone polymer emulsion into an
amide-type polymerization reaction medium prior to or during the
reaction, wherein the reaction medium comprises 1) a diacid
component and a diamine component, an oligomer of a diacid and a
diamine component, or a mixture thereof, and
[0031] c. polymerizing the components of b) 1, thereby providing an
amide-type polymer/silicone polymer blend.
[0032] Still further, the invention provides, an amide-type
polymer/silicone polymer blend comprising:
[0033] (a) a silicone polymer emulsion comprising a silicone
polymer; and
[0034] (b) amide-type polymer
[0035] wherein the amide-type polymer is formed by introducing the
silicone polymer emulsion into an amide-type polymerization
reaction medium prior to or during the reaction and wherein the
reaction medium comprises 1) a diacid component and a diamine
component, an oligomer of a diacid and a diamine component, or a
mixture thereof.
[0036] Still further, the invention provides a method of making an
amide-type polymer/silicone polymer blend comprising the steps
of:
[0037] a. preparing a silicone polymer emulsion comprising a liquid
continuous phase;
[0038] b. introducing the silicone polymer emulsion into an
amide-type polymer; and
[0039] c. extruding the silicone polymer emulsion and the
amide-type polymer, thereby providing an amide-type
polymer/silicone polymer blend.
[0040] I. Silicone Polymer Emulsion
[0041] In one embodiment, the invention provides silicone polymer
emulsions comprising a plurality of particles of a silicone polymer
dispersed in a continuous phase. The silicone polymers of the
present invention may preferably have functional groups. Such
functional groups may comprise amino, epoxy, vinyl, mercapto,
carbonate, isocyanate or silicone hydride. In a particularly
preferred embodiment, the silicone polymer is silanol terminated
polydiorganosiloxane ("PDOS"). Other preferred silicone polymers
include alkylmethylsiloxanes or aminopropylsiloxanes.
[0042] The silicone polymer emulsion preferably contains at least
one surfactant that stabilizes the dispersed silicone polymer
particles in the continuous phase of the emulsion. The emulsion
should preferably have an average particle size from about 0.1 to
about 10 microns. Such emulsions may be prepared, for example, by
methods wherein a cyclic or linear oligomeric silicone polymer,
such as PDOS, are dispersed in an aqueous continuous phase with the
aid of a surfactant and are thereafter emulsion polymerized by the
introduction of an acid or base catalyst. Such emulsions can be
illustrated by the disclosures of, among others, U.S. Pat. Nos.
4,954,565, 4,618,642, 3,294,725, and 2,891,920, the disclosures of
which are each hereby incorporated herein in their entireties by
this reference.
[0043] In a further embodiment, the silicone polymer emulsions are
prepared by a direct (mechanical) emulsification process. In this
process, a mixture of the continuous phase liquid i.e., water
and/or diol, silicone polymer and one or more surfactants are
processed under high shear conditions using either conventional
mixing equipment or high shear devices such as a Microfuidizer.TM..
Methods for preparing these polymer emulsions are given in U.S.
Pat. Nos. 4,177,177 and 4,788,001, the disclosures of which are
each herein incorporated in their entireties by this reference. For
example, PDOS can be added to a surfactant and water and/or diol
slowly added with constant shear. The resulting PDOS emulsions can
then be crosslinked using common methods known to crosslink the
PDOS.
[0044] In still a further embodiment, the continuous phase
comprises a water component, wherein the water component is present
in an amount of from about 1 to about 100% by weight, based upon
the total weight of the continuous phase, and further preferably,
from about 10 to about 100% by weight, based upon the total weight
of the continuous phase, and still preferably, from about 20 to
about 100% by weight, based upon the total weight of the continuous
phase. Further preferably, the water component is present at from
about 30 to about 100%, based upon the total weight of the
continuous phase, still preferably from about 40 to about 100% by
weight of the continuous phase, still further preferably , from
about 50 to about 100% by weight of the continuous phase. In yet
further preferred embodiments, the water component is present at
from about 60 to about 100% by weight of the continuous phase,
further preferably, from about 70 to about 100% by weight of the
continuous phase, still preferably, from about 80 to about 100% by
weight of the continuous phase, and still further preferably from
about 90 to about 100% by weight of the continuous phase .
[0045] In a further, still preferred embodiment, the continuous
phase of the silicone polymer emulsions of the present invention
comprise a diol component. Diol components useful for the
continuous phase of the silicone polymer emulsion compositions
include, but are not limited to, any aliphatic or cycloaliphatic
diol having from about 2 to about 10 carbon atoms, or a mixture
thereof. Preferred diols include ethylene diol, 1,3-trimethylene
diol, propylene diol, tripropylene diol, 1,4-butanediol,
1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol,
1,9-nonanediol, neopentyl diol, cis- or trans-
cyclohexanedimethanol, cis- or trans-
2,2,4,4-tetramethyl-1,3-cyclobutane- diol, diethylene diol,
2,2,4-trimethyl-1,3-pentanediol, 2-methyl-1,3-propanediol,
2-methyl-1,3-pentanediol, or a mixture thereof. More preferred
diols include ethylene diol, propylene diol, tripropylene diol,
1,4-butanediol, diethylene diol, neopentyl diol, cis and trans-
cyclohexanedimethanol, or a mixture thereof; even more preferred
diols include neopentyl diol, ethylene diol, cis or trans
cyclohexanedimethanol, 1,4 butanediol, or a mixture thereof.
Preferably, the diol comprises an aliphatic or cycloaliphatic diol
having from about 2 to about 10 carbon atoms, or a mixture
thereof.
[0046] In an embodiment of the invention herein, the diol component
is present in the continuous phase of the silicone polymer emulsion
in an amount of from about 1 to about 100% by weight, based on the
total weight of the continuous phase, still preferably, from about
10 to about 100% of the continuous phase, still further,
preferably, from about 20 to about 100% by weight of the continuous
phase. In yet further embodiments, the diol component is present in
an amount of from about 30 to about 100% by weight, based on the
total weight of the continuous phase, more preferably, from about
40 to about 100% by weight, based on the total weight of the
continuous phase, more preferably, from about 50 to about 100% by
weight, based on the total weight of the continuous phase, and even
more preferably, from about 60 to about 100% by weight, based on
the total weight of the continuous phase. In a further embodiment,
the diol component is present at from about 70 to about 100% by
weight of the continuous phase, in a further embodiment, from about
80 to about 100% by weight of the continuous phase, and, in still a
further embodiment, from about 90 to about 100% by weight of the
continuous phase. In a further embodiment, the continuous phase of
the silicone polymer emulsion consists essentially of diol.
[0047] In a preferred embodiment, the diol component consists
essentially of tripropylene glycol, 1,4-butanediol, neopentyl
glycol, cyclohexanedimethanol, or a mixture thereof.
[0048] The total weight of the continuous phase includes the weight
of the water component and/or diol component and any co-solvent.
The weight of any surfactant or additional components is not
included in the total weight of the continuous phase.
[0049] In a preferred embodiment, a surfactant is present in the
silicone polymer emulsions. One of skill in the art would recognize
that the type and amount of surfactant used in the mechanical
emulsification depends on the particular monomer combinations and
polymerization conditions. Surfactants used in the mechanical
emulsification may be anionic, cationic, or nonionic surfactants.
Anionic surfactants that may be used in the invention include
surfactants such as alkali metal or ammonium salts of alkyl, aryl
or alkylaryl sulfonates, sulfates, phosphates, or a mixture
thereof. Further, suitable nonionic surfactants include, but are
not limited to, alkyl and alkylaryl polydiol ethers, such as
ethoxylation products of lauryl, oleyl and stearyl alcohol, alkyl
phenol glycol ethers, including but not limited to, ethoxylation
products of octyl or nonylphenol. Suitable surfactants may be found
in McCutcheon's Volume I: Emulsifiers and Detergents 1996 North
American Edition, MC Publishing Co., Glen Rock, N.J., 1996.
[0050] In addition to the water component and/or diol component,
the continuous phase may contain one or more polyol components.
Representative polyol components that may be used in the continuous
phase include, but are not limited to, glycerol,
trimethylolpropane, pentaerythritol, 1,2,6-hexanetriol, sorbitol,
1,1,4,4-tetrakis(hydroxymet- hyl)cyclohexane,
tris-(2,hydroxyethyl)isocyanurate, dipentaerythritol, or a mixture
thereof. In addition to low molecular weight polyols, higher
molecular weight polyols (MW about 400 to about 3000), preferably
triols derived by condensing alkylene oxides having from about 2 to
about 3 carbons, e.g., ethylene oxide or propylene oxide, with
polyol initiators, having from about 3 to about 6 carbons, e.g.,
glycerol, can also be used.
[0051] The continuous phase of the silicone polymer emulsion may
also comprise a cosolvent. These cosolvents include, but are not
limited to water, methanol, ethanol, propanol, n-butanol, or a
mixture thereof. The cosolvent may be present in the amount of less
than about 60% by weight, more preferably less than about 40% by
weight, based on the total weight of the continuous phase of the
silicone polymer emulsion.
[0052] Preferably, the silicone polymers utilized to form the
emulsions of the present invention may be crosslinked prior to
addition of the emulsion to an amide-type polymerization reaction.
Many methods are present in the literature to crosslink silicone
polymer emulsions. For example, U.S. Pat. No. 4,370,160 discloses
microparticles, such as microspheres and microcapsules, comprising
a solid PDOS prepared by irradiation of a dispersion of discrete
particles with ultraviolet light. The discrete particles are
dispersed in a U.V. transparent fluid continuous phase and are
sphere-like particles of a U.V. curable, liquid PDOS component
containing a material to be encapsulated.
[0053] In another example, U.S. Pat. No. 4,618,642 also discloses
how to crosslink aqueous emulsions of silicone particles. The
crosslinking is carried out by mixing an anionic emulsion
containing dispersed particles of hydroxyl functional PDOS, a
dialkyltindicarboxylate and a trifunctional organosilane. U.S. Pat.
No. 5,674,937, also discloses methods of curing phase inverted
silicone polymer emulsions.
[0054] The silicone polymer emulsions of this present invention may
also be prepared by emulsion polymerization techniques. Such
emulsions may be prepared, for example, by methods wherein a cyclic
or linear oligomer siloxane polymer, such as PDOS, are dispersed in
a glycol continuous phase with the aid of a surfactant and are
thereafter emulsion polymerized by the introduction of an acid or
base catalyst. Examples of suitable acid and base catalysts are
illustrated in the disclosures of, for example, U.S. Pat. Nos.
4,954,595, 4,618,642, 3,294,725 and 2,891,920.
[0055] II. INCORPORATION OF A SILICONE POLYMER INTO A
POLYAMIDE-TYPE POLYMER BLEND
[0056] In a major embodiment, the invention relates to the
introduction of a silicone polymer emulsion into a reaction that
forms an amide-type polymer, resulting in a product having polymer
particles incorporated into an amide-type polymer blend. The
silicone polymer emulsion that is introduced into the
polymerization reaction is herein defined as silicone polymer
particles dispersed in a continuous phase, as further described in
Section I above.
[0057] In the silicone polymer emulsion, the solvent or continuous
phase may comprise water, a diol, a polyol, or a mixture thereof.
Further, the continuous phase of the silicone polymer emulsion may
consist essentially of or consist of water, a diol or polyol, or
may comprise any proportion of either component.
[0058] In the silicone polymer emulsions comprising diol in the
continuous phase, the diols in the continuous phase co-react with
ester, acid or amide functionality, or a mixture thereof that
comprise the reaction medium which forms the amide-type polymer. In
such a co-reaction, a polyesteramide is preferably formed.
[0059] The total weight of the continuous phase includes the weight
of the water component, diol component, and polyol component and/or
co-solvent, if any. The weight of any surfactant is not included in
the total weight of the continuous phase.
[0060] Alternatively, the silicone polymer emulsion may be blended
into the fully or partially formed condensation polymer directly in
an extruder at temperatures from about 200 to about 320.degree. C.
In this process, since the silicone polymer emulsion is added
directly to the amide-type polymer, there is no need to harvest the
silicone polymer from the silicone polymer emulsion. This provides
a more economical process over those in the prior art.
[0061] As noted, the silicone polymer emulsion can be added at any
stage of the reaction. The final blend can be affected by the time
the silicone polymer emulsion is added. While not wishing to be
bound by any mechanism, it is believed that the properties of the
amide-type polymer/silicone polymer blend can be affected by the
time of the addition of the silicone polymer emulsion. Also,
particular chemical interaction between the silicone polymer of the
silicone polymer emulsion and amide-type polymers is affected by
time of addition, which, in consequence, affects final blend
properties.
[0062] The amount of silicone polymer in the amide-type
polymer/silicone polymer blend may comprise a wide range of values.
However, it is particularly preferred that the amount of silicone
polymer in the blend is greater than about 5% by weight of the
blend. Still further, it is preferred that the amount of silicone
polymer in the amide-type polymer/silicone polymer blend be from
greater than about 5 to about 50% by weight of the blend, and,
still further preferably, from greater than about 5 to about 25% by
weight of the blend.
[0063] The term "polyamide," as used herein, refers to any
unit-type of polyamide falling within the scope of the polyamide
portion of the blend, including, but not limited to,
homopolyamides, and copolyamides (two or more types of acid and/or
diamine residues of monomeric units). The polyamides of the present
invention preferably comprise an acid residue and a diamine
residue. The acid residues of the polyamides of the present
invention total about 100 mol % and the diamine residues of the
polyamides of the present invention total about 100 mol %. It
should be understood that use of the corresponding derivatives,
specifically acid anhydrides, esters and acid chlorides of these
acids is included throughout the application in the term "acid
residue." In addition to the acid residue and the diamine residue,
the polyamide may comprise other modifying residues. These
modifying residues include, but are not limited to, a diol, which
would result in a polyesteramide.
[0064] When the amide-type polymer utilized in the present
invention is a polyamide, the polymer may be aliphatic, partially
aromatic or entirely aromatic. Combinations of such polyamides are
also included within the scope of the invention. By "partially
aromatic polyamide" it is meant that the amide linkage of the
partially aromatic polyamide contains at least one aromatic ring
and a nonaromatic species.
[0065] The polyamides are prepared from a diacid and a diamine.
Polyamides are formed from isophthalic acid, terephthalic acid,
cyclohexanedicarboxylic acid and meta- or para-xylylene diamine,
1,3- or 1 ,4-cyclohexane(bis)methylamine, aliphatic diacids with
about 6 to about 12 carbon atoms, aliphatic amino acids or lactams
with 6 to 12 carbon atoms, aliphatic diamines with about 4 to about
12 carbon atoms, or a mixture thereof. Other generally known
polyamide forming diacids and diamines can also be used. The
polyamides may also contain small amounts of trifunctional or
tetrafunctional comonomers such as trimellitic anhydride,
pyromellitic dianhydride, or other polyamide forming polyacids and
polyamines known in the art.
[0066] Preferred partially aromatic polyamides include:
poly(m-xylylene adipamide), poly(hexamethylene isophthalamide),
poly(hexamethylene adipamide-co-isophthalamide), poly(hexamethylene
adipamide-co-terephthala- mide), and poly(hexamethylene
isophthalamide-co-terephthalamide), or a mixture thereof.
[0067] Preferred aliphatic polyamides include
polyethylene-adipamide (nylon 2,6), polytetramethylene-adipamide
(nylon 4,6), polyhexamethylene-adipamide (nylon 6,6),
polyhexamethylene-sebacamide (nylon 6,10),
polyhexamethylene-dodecamide (nylon 6,12),
polyoctamethylene-adipamide (nylon 8,6),
polydecamethylene-adipamide (nylon 10,6),
polydodecamethylene-adipamide (nylon 12,6),
polydodecamethylene-sebacamide (nylon 12,8), or a mixture
thereof.
[0068] The amide-type polymers are generally prepared by melt phase
polymerization from a diacid-diamine complex which may be prepared
either in situ or in a separate 25 step. In either method, the
diacid and diamine are used as starting materials. Alternatively,
an ester form of the diacid may be used, preferably the dimethyl
ester. If the ester is used, the reaction must be carried out at a
relatively low temperature, generally from about 80.degree. C. to
about 120.degree. C., until the ester is converted to an amide. The
mixture is then heated to the preferred polymerization
temperature.
[0069] The molecular weight of the resulting amide-type polymer is
controlled by the diacid-diamine ratio. An excess of diamine
produces a higher concentration of terminal amino groups. If the
diacid-diamine complex is prepared in a separate step, excess
diamine is added prior to the polymerization. The polymerization
can be carried out either at atmospheric pressure or at elevated
pressures.
[0070] In a preferred embodiment, the amide-type polymers of the
invention herein may be formed from oligomers of a diamine and a
diacid. Such oligomers are preferably further reacted in the
presence of suitable reactants to provide the amide-type polymers
of the present invention.
[0071] When a diol is present in the amide-type polymerization
reaction, a polyesteramide will preferably result. The diol may be
present in the silicone polymer emulsion or may be added to the
amide-type reaction medium. In a preferred embodiment, ethylene
diol and/or butanediol is added to an amide-type reaction medium to
provide a polyesteramide. Suitable diol components for the
continuous phase of the silicone polymer emulsion include, but are
not limited to, the diol components described in Section I.
[0072] It is preferred that the amide-type polymers of the
invention are essentially linear. The amide-type polymers may be
modified with low levels of one or more branching agents. A
branching agent is herein defined as a molecule that has at least
three functional groups that can participate an amide-type polymer
forming reaction, such as amino, carboxylic acid, or carboxylic
ester.
[0073] Branching agents useful in preparing the amide-type polymers
of the invention include, but are not limited to glycerol,
pentaerythritol, trimellitic anhydride, pyromellitic dianhydride,
tartaric acid, or a mixture thereof. If branching agents are used
in the amide-type polymer reaction, a preferred range for the
branching agent is from about 0.1 to about 2.0 weight %, more
preferably from about 0.2 to about 1.0 weight %, based on the total
weight of the amide-type polymer.
[0074] Addition of branching agents at low levels does not have a
significant detrimental effect on the physical properties of the
amide-type polymers and provides additional melt strength which can
be very useful in film extruding operations. High levels of
branching agents incorporated in the co-amide-type polymers results
in co-amide-type polymers with poor physical properties, for
example low elongation.
[0075] In one embodiment of the invention herein, an amide-type
polymer/silicone polymer blend is provided. In a preferred
embodiment, a method of making such a material is provided
according to the following steps: a) preparing a silicone polymer
emulsion comprising a silicone polymer dispersed in a liquid
continuous phase; b) introducing the silicone polymer emulsion into
an amide-type polymerization reaction medium comprising 1) a
diamine component and a diacid component, an oligomer of a diamine
and diacid, or a mixture thereof; and c) polymerizing the
components of b)1 thereby providing an amide-type polymer/silicone
polymer blend.
[0076] In a particularly preferred embodiment relating to the
amide-type polymers of the present invention, the liquid continuous
phase of the silicone polymer emulsion comprises a water component
substantially in the absence of a diol and/or a polyol to provide
an amide-type polymer. In one aspect of this invention, the
silicone polymer of the silicone polymer emulsion is incorporated
into the amide-type polymer to provide an amide-type
polymer/silicone polymer blend.
[0077] In a further particularly preferred embodiment relating to
the amide-type polymer of the present invention, the liquid
continuous phase comprises a diol component to provide a
polyesteramide polymer. In one aspect of this embodiment, the
silicone polymer of the silicone polymer emulsion is incorporated
into the amide-type polymer to provide a polyesteramide-type
polymer/silicone polymer blend.
[0078] In a further particularly preferred embodiment relating to
the amide-type polymer of the present invention, the liquid
continuous phase comprises a mixture of water and diol. In one
aspect of this embodiment, the silicone polymer of the silicone
polymer emulsion will be incorporated into the amide-type polymer
to provide an amide-type polymer/silicone polymer blend. One of
skill in the art will recognize that by varying the amount of
glycol in the silicone polymer emulsion, the number of ester
moieties in the polyesteramide can be varied. Accordingly, in
various preferred embodiments of the present invention, the
diol/water ratio in the liquid continuous phase is varied to
provide polyesteramide polymers with differing amounts of ester
moieties.
[0079] The silicone polymer that is introduced into the amide-type
reaction medium in one embodiment of the invention herein is
defined as polymer particles dispersed in a continuous phase, the
polymer particles preferably having a particle size in the range of
from about 0.020 microns to about 1000 microns, further preferably,
the polymer particles have a particle size in the range of about
0.1 to about 10 microns.
[0080] The process of the invention does not require the isolation
of the silicone polymer in the silicone polymer emulsion from the
continuous phase, for example, by spray drying. Thus, the present
invention overcomes the necessity of preparing a core- shell
polymer or the necessity of harvesting the polymer from the
emulsion. Further, since blending takes place during the
preparation of the amide-type polymer in the polymerization
reactor, there is no need for a polymer/polymer post blending step
that is energy intensive, expensive and often leads to the
reduction of the molecular weight of the amide-type polymer.
[0081] The silicone polymer emulsion may be introduced into the
amide-type polymerization reaction at various stages. For example,
in an amide-type polymerization reaction, the silicone polymer
emulsion can be added 1) "up-front" with the starting materials; 2)
after initiation of the polymerization; 3) during the
polymerization; or 4) near the completion of the polymerization.
The final blend can be affected by the time at which the silicone
polymer emulsion is added. While not wishing to be bound by any
mechanism, it is believed that the size and shape of the silicone
polymer in the amide-type polymer blend can be affected by the time
of the addition of the silicone polymer emulsion. Also, particular
chemical interaction between the silicone polymer and amide-type
polymers is affected by time of addition, and they, in consequence,
affect final blend properties.
[0082] The polymer compositions of this invention may be buffered.
Buffers can be utilized to control the formation of diethylene
glycol, among other uses, in a polyesteramide ester. Preferred
buffers include sodium acetate, potassium acetate, lithium acetate,
sodium phosphate monobasic, potassium phosphate dibasic, sodium
carbonate, or a mixture thereof. Buffering agents are useful to
limit the amount of acidic species which, in turn, causes
dehydration of the diols to give ether diol. Accordingly, it can be
desirable to limit such acid species through the use of buffering
agents.
[0083] The final stage of the reaction is generally conducted under
high vacuum (<about 10 mm of Hg) in order to produce a high
molecular weight amide-type polymer.
[0084] Other ingredients may optionally be added to the
compositions of the present invention to enhance the performance
properties of the amide-type polymer/silicone polymer blend. For
example, reinforcing agents, surface lubricants, denesting agents,
stabilizers, antioxidants, ultraviolet light absorbing agents, mold
release agents, metal deactivators, colorants such as black iron
oxide and carbon black, nucleating agents, phosphate stabilizers,
zeolites, fillers, mixtures thereof, and the like, can be included
herein. All of these additives and the use thereof are well known
in the art. Any of these compounds can be used so long as they do
not hinder the present invention from accomplishing its
objects.
[0085] In a particularly preferred embodiment relating to the
addition of reinforcing agents to the compositions of the present
invention, glass fibers may be added to the amide-type polymer
compositions to provide particular advantages to the resulting
compositions. Glass fibers that are preferred in the present
invention conventionally have an average standard diameter of
greater than about 5 microns, with a range of from about 1 to about
20 microns. The length of the glass filaments whether or not they
are bundled into fibers, and whether the fibers are further bundled
into yarns, ropes or rovings, and the like, are not critical to
this invention. However, for the purpose of preparing the present
compositions, it is preferable to use filamentous glass in the form
of chopped strands of from about 1.5 mm to about 10 mm long, and
preferably less than about 6 mm long. In the pellets and molded
articles of the compositions, even shorter lengths will be
encountered, because during compounding, considerable fragmentation
occurs. This is, however, desirable because the best properties are
exhibited for injection molded articles where the filament lengths
are between about 0.03 mm and about 1 mm. Especially preferred are
glass fibers having an average standard diameter in the range of
greater than about 5 microns, preferably about 5 to about 14
microns, and the average filament length dispersed in the molded
articles being between about 0.15 and about 0.4 mm. Consequently,
glass filaments are dispersed uniformly and the molded articles
exhibit uniform and balanced mechanical properties, especially
surface smoothness.
[0086] The amount of the glass fibers can vary broadly from about
10 to about 50% by weight, and most preferably about 10 to about
40% by weight, based on the total polymer composition. These glass
fibers are typically conventionally sized with coupling agents,
such as aminosilanes and epoxysilanes and titanates, and adhesion
promoters such as epoxies, urethanes, cellulosics, starch,
cyanurates, and the like.
[0087] In one embodiment, when the glass fiber is present in the
polymer molding composition, the polymer is preferably from about
70 to about 85% by weight of the total composition based on the
total weight percentages of the amide-type polymer/silicone polymer
blend equaling 100%. Preferably, the polymer in the polymer molding
composition comprises an amide-type polymer.
[0088] Examples of other reinforcing agents that are useful in
addition to glass fibers, include, but are not limited to, carbon
fibers, mica, clay, talc, wollastonite, calcium carbonate or a
combination thereof. The polymer compositions of the invention may
be reinforced with a mixture of glass and other reinforcing agents
as described above, such as mica or talc, or with other
additives.
[0089] In accordance with the invention herein, the silicone
polymer emulsion and glass fibers, as well as other reinforcing
agents, may be introduced into the amide-type polymerization
reaction at various stages of the process. In a particularly
preferred embodiment of the invention herein, the glass fibers are
added directly to the amide-type polymerization reaction. Since the
glass fibers can be sufficiently blended during this stage, there
is no need for a post-blending step, such as extrusion, to
incorporate the glass fibers into the compositions. This is
particularly advantageous to the present invention because a
post-blending step is energy intensive, expensive and may often
cause a reduction in the molecular weight of the amide-type
polymer.
[0090] End-use applications for the compositions of the amide-type
polymers produced according to the instant invention include
impact-modified polymers, elastomers, high barrier films and
coatings, improved barrier polymers, and polymers having improved
mechanical properties, such as improved tensile strength, improved
elongation at break, better weathering properties, and improved
flexural strength. Other end-use applications include engineering
resins, coatings, containers for barrier applications and molding
plastics. The polymers produced by this invention are useful for
thermoplastic engineering resins, elastomers, films, sheets and
container plastics.
[0091] In a preferred embodiment, an impact modified amide-type
polymer is prepared comprising a silicone polymer derived from a
silicone polymer emulsion. In another preferred embodiment, a
hydroxyl functionalized amide-type polymer coating is prepared
comprising a silicone polymer derived from a silicone polymer
emulsion.
[0092] In one embodiment of the invention, a modified amide-type
polymer, including, but not limited to, an impact modified plastic,
is produced from a silicone polymer emulsion comprising silicone
polymers which are either cross-linked or uncross-linked polymers,
and an amide-type polymer.
[0093] End-use applications for the compositions of the modified
amide-type polymer/silicone polymer blends produced according to
the instant invention include impact-modified polymers, elastomers,
high barrier films and coatings, improved barrier polymers, and
polymers having improved mechanical properties, such as improved
tensile strength, improved elongation at break, better weathering
properties, and improved flexural strength. Other end-use
applications include engineering resins, coatings, containers for
barrier applications and molding plastics. The polymer blends
produced by this invention are useful for thermoplastic engineering
resins, elastomers, films, sheets and container plastics.
[0094] In a further preferred embodiment, an impact modified
amide-type polymer is prepared comprising a silicone polymer
emulsion to provide a modified amide-type/silicone polymer blend.
In one particularly preferred embodiment of the invention, a
modified amide-type polymer, including, but not limited to, an
impact modified plastic, is produced from silicone polymer
emulsions and a modified amide-type polymer.
[0095] In a major embodiment, the invention concerns the
introduction of a silicone polymer emulsion into a reaction that
forms a modified amide-type polymer, resulting in a polymer blend
having a silicone polymer dispersed within a modified
amide-type/silicone polymer blend.
[0096] In a further preferred embodiment, modified amide-type
polymer/silicone polymer blends are provided.
EXAMPLES
[0097] The following examples are put forth so as to provide those
of ordinary skill in the art with a complete disclosure and
description of how the compositions of matter and methods claimed
herein are made and evaluated, and are not intended to limit the
scope of what the inventors regard as their invention. Efforts have
been made to insure accuracy with respect to numbers (e.g.,
amounts, temperature, etc.) but some errors and deviations should
be accounted for. Unless indicated otherwise, parts are by weight,
temperature is in .degree. C. or is at room temperature and
pressure is at or near atmospheric.
Example 1
[0098] Into a 34/45, single-necked, heavy-walled, 1-L, round-bottom
flask was weighed 146.14 g (1.00 moles) adipic acid (D), 167.66 g
(1.01 moles) 1,6 hexamediamine (MW=116.2 w/70% H.sub.2O (NA)),
46.99 g of a silicone latex composition, and 180.10 g (10.00 moles)
distilled water (H.sub.2O). The NA was calculated at a 1% excess
and the H.sub.2O was calculated at 10.times. the moles of NA. No
catalysts were needed for this reaction, neither was pulling vacuum
required, but during the preparation of these polyamides, a vacuum
of 400 torr was applied. The slight vacuum allowed the polyamide to
increase in molecular weight, but was not strong enough to pull off
any essential components.
[0099] A sequence for preparing the Polyamide/Silicone composite is
in Table 1.
1TABLE 1 Sequence for Preparation of D(NA)/Rubber Murloy. Time Temp
Vac Stir Power Flags Estimated Stage Min .degree. C. Torr RPM % S T
C End Time 1 1 115 730 415 0 0 0 0 12:08:32 2 45 115 730 415 0 0 0
0 12:53:32 3 3 120 730 415 0 0 0 0 12:56:32 4 15 120 730 415 0 0 0
0 13:11:32 5 4 135 730 415 0 0 0 0 13:15:32 6 30 135 730 15 0 0 0 0
13:45:32 7 60 275 730 175 0 0 0 0 14:45:32 8 60 285 730 415 0 0 0 0
15:45:32 9 6 285 400 250 0 0 0 0 15:51:32 10 75 285 400 250 0 0 0 0
17:06:32 Flags: S = Stirrer Slaved, T = Service Traps, C = Add
Catalyst *The stirrer was mostly controlled manually during these
two stages.
[0100] The invention has been described in detail with particular
reference to preferred embodiments thereof, but it will be
understood that variations and modifications can be effected
without departing from the scope and spirit of the invention.
* * * * *