U.S. patent application number 12/702446 was filed with the patent office on 2010-08-12 for two-part liquid shim compositions.
This patent application is currently assigned to 3M Innovative Properties Company. Invention is credited to Sohaib ELGIMIABI.
Application Number | 20100203249 12/702446 |
Document ID | / |
Family ID | 42184430 |
Filed Date | 2010-08-12 |
United States Patent
Application |
20100203249 |
Kind Code |
A1 |
ELGIMIABI; Sohaib |
August 12, 2010 |
TWO-PART LIQUID SHIM COMPOSITIONS
Abstract
Epoxy curatives and two-part compositions comprising epoxy
curative and epoxy resin parts are provided as well as methods of
their use in liquid shim applications. Epoxy curatives comprise at
least one cycloaliphatic polyamine curative and at least one second
curative selected from a) an aliphatic polyamidoamine and b) an
adduct of an excess of an unbranched polyetherdiamine with an epoxy
resin.
Inventors: |
ELGIMIABI; Sohaib; (Neuss,
DE) |
Correspondence
Address: |
3M INNOVATIVE PROPERTIES COMPANY
PO BOX 33427
ST. PAUL
MN
55133-3427
US
|
Assignee: |
3M Innovative Properties
Company
|
Family ID: |
42184430 |
Appl. No.: |
12/702446 |
Filed: |
February 9, 2010 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
61151076 |
Feb 9, 2009 |
|
|
|
Current U.S.
Class: |
427/386 |
Current CPC
Class: |
C08G 2650/50 20130101;
C09D 163/00 20130101; C08G 59/54 20130101; C08G 59/56 20130101;
B29K 2063/00 20130101; B29C 70/845 20130101; B29K 2105/20 20130101;
C08G 59/504 20130101; C08G 59/184 20130101; C08G 59/60
20130101 |
Class at
Publication: |
427/386 |
International
Class: |
B05D 3/02 20060101
B05D003/02 |
Claims
1. An epoxy curative comprising at least one cycloaliphatic
polyamine curative and at least one second curative selected from
a) an aliphatic polyamidoamine and b) an adduct of an excess of an
unbranched polyetherdiamine with an epoxy resin.
2. The epoxy curative according to claim 1 wherein the at least one
second curative is a) an aliphatic polyamidoamine.
3. The epoxy curative according to claim 1 wherein the at least one
second curative is b) an adduct of an excess of an unbranched
polyetherdiamine with an epoxy resin.
4. The epoxy curative according to claim 3 wherein the unbranched
polyetherdiamine is a compound according to Formula I:
H.sub.2N--[(CH.sub.2).sub.xO].sub.y--(CH.sub.2).sub.x--NH.sub.2 [I]
where y is 1, 2, 3 or 4, and where each x is independently selected
from 2, 3, or 4.
5. The epoxy curative according to claim 3 wherein the adduct of an
excess of an unbranched polyetherdiamine with an epoxy resin is an
adduct of between 2 and 8 parts unbranched polyetherdiamine per
part of epoxy resin.
6. The epoxy curative according to claim 4 wherein the adduct of an
excess of an unbranched polyetherdiamine with an epoxy resin is an
adduct of between 2 and 8 parts unbranched polyetherdiamine per
part of epoxy resin.
7. The epoxy curative according to claim 1 wherein the epoxy
curative additionally comprises at least one calcium nitrate
accelerator.
8. The epoxy curative according to claim 1 wherein the epoxy
curative comprises no particulate metal.
9. A method of filling a gap comprising the steps of: a) mixing an
epoxy component comprising an epoxy resin with an epoxy curative
according to claim 1 to make a mixture; b) filling the gap with the
mixture; and c) allowing the mixture to cure.
10. A method of filling a gap comprising the steps of: a) mixing an
epoxy component comprising tetraglycidyl meta-xylenediamine with an
epoxy curative according to claim 2 to make a mixture; b) filling
the gap with the mixture; and c) allowing the mixture to cure.
11. A method of filling a gap comprising the steps of: a) mixing an
epoxy component comprising an epoxy novolac resin with an epoxy
curative according to claim 3 to make a mixture; b) filling the gap
with the mixture; and c) allowing the mixture to cure.
12. The method according to claim 9 wherein the epoxy component
additionally comprises a core-shell impact modifier.
13. The composition obtained by mixing and allowing to cure: a) an
epoxy component comprising an epoxy resin and b) an epoxy curative
according to claim 1.
14. The composition obtained by mixing and allowing to cure: a) an
epoxy component comprising an epoxy resin and b) an epoxy curative
according to claim 2.
15. The composition according to claim 14 wherein the epoxy
component comprises tetraglycidyl meta-xylenediamine.
16. The composition obtained by mixing and allowing to cure: a) an
epoxy component comprising an epoxy resin and b) an epoxy curative
according to claim 3.
17. The composition according to claim 16 wherein the epoxy
component comprises an epoxy novolac resin.
18. The composition obtained by mixing and allowing to cure: a) an
epoxy component comprising an epoxy resin and b) an epoxy curative
according to claim 4.
19. The composition obtained by mixing and allowing to cure: a) an
epoxy component comprising an epoxy resin and b) an epoxy curative
according to claim 5.
20. The composition according to claim 13 wherein the epoxy
component additionally comprises a core-shell impact modifier.
Description
CROSS REFERENCE TO RELATED APPLICATION
[0001] This application claims the benefit of U.S. Provisional
Patent Application No. 61/151,076, filed Feb. 9, 2009, the
disclosure of which is incorporated by reference herein in its
entirety.
FIELD OF THE DISCLOSURE
[0002] This disclosure relates to curative compositions and
two-part compositions comprising curative and epoxy resin parts,
which may be useful in liquid shim applications, as well as methods
of their use.
BACKGROUND OF THE DISCLOSURE
[0003] Shims are used in many facets of assembly operations to
position and fill gaps between assembled parts. The need for
shimming is particularly acute in aerospace assembly operations due
to the tight tolerance requirements and need to eliminate gaps at
interfaces. Shims used for assembly operations generally fall
within three categories. Solid shims are, in some cases, made of
the same material as the interfacing parts. Laminated peelable
shims may be made of foil layers that can be removed one-by-one
until a good fit is achieved. Liquid shim materials may be useful
in filling irregular or tapered interfaces. Liquid shim materials
are typically used to fill gaps no bigger than 0.7 mm in width.
SUMMARY OF THE DISCLOSURE
[0004] The present disclosure provides epoxy compositions, curative
compositions, and two-part compositions comprising the present
epoxy and curative compositions, which may be useful as liquid shim
applications and methods of their use.
[0005] Briefly, the present disclosure provides an epoxy curative
comprising at least one cycloaliphatic polyamine curative and at
least one second curative selected from a) an aliphatic
polyamidoamine and b) an adduct of an excess of an unbranched
polyetherdiamine with an epoxy resin. In some embodiments, the at
least one second curative is an aliphatic polyamidoamine. In some
embodiments, the at least one second curative is an adduct of an
excess of an unbranched polyetherdiamine with an epoxy resin. In
some such embodiments, the unbranched polyetherdiamine is a
compound according to Formula I:
H.sub.2N--[(CH.sub.2).sub.xO].sub.y--(CH.sub.2).sub.x--NH.sub.2
[I]
where y is 1, 2, 3 or 4, and where each x is independently selected
from 2, 3, or 4. In some such embodiments, the adduct of an excess
of an unbranched polyetherdiamine with an epoxy resin is an adduct
of between 2 and 8 parts unbranched polyetherdiamine per part of
epoxy resin. In some embodiments, the epoxy curative additionally
comprises at least one calcium nitrate accelerator. In some
embodiments, the epoxy curative comprises no particulate metal.
[0006] In another aspect, the present disclosure provides a method
of filling a gap comprising the steps of: a) mixing an epoxy
component comprising an epoxy resin with an epoxy curative
according to the present disclosure to make a mixture; b) filling
the gap with the mixture; and c) allowing the mixture to cure. In
some embodiments, the epoxy component additionally comprises a
core-shell impact modifier. In some embodiments, the epoxy
component comprises tetraglycidyl meta-xylenediamine, particularly
where the epoxy curative is an aliphatic polyamidoamine. In some
embodiments, the epoxy component comprises an epoxy novolac resin,
particularly where the epoxy curative is an adduct of an excess of
an unbranched polyetherdiamine with an epoxy resin.
[0007] In another aspect, the present disclosure provides a
composition obtained by mixing and allowing to cure: a) an epoxy
component comprising an epoxy resin and b) an epoxy curative
according to the present disclosure. In some embodiments, the epoxy
component additionally comprises a core-shell impact modifier. In
some embodiments, the epoxy component comprises tetraglycidyl
meta-xylenediamine, particularly where the epoxy curative is an
aliphatic polyamidoamine. In some embodiments, the epoxy component
comprises an epoxy novolac resin, particularly where the epoxy
curative is an adduct of an excess of an unbranched
polyetherdiamine with an epoxy resin.
DETAILED DESCRIPTION
[0008] The present disclosure provides epoxy compositions, curative
compositions, and two-part compositions comprising the present
epoxy and curative compositions, which may be useful as liquid shim
applications. The present disclosure additionally provides
compositions obtained by mixing the two parts of the disclosed
two-part compositions.
[0009] Any suitable epoxy compositions may be used in the two-part
compositions of the present disclosure. Typically a polyfunctional
resin having three or more epoxy groups per molecule is used. In
some embodiments an epoxy novolac resin may be used. In some
embodiments an epoxy resin based on meta-xylenediamine such as
ERISYS GA 240, may be used. The epoxy composition may additionally
comprise additives which may include impact modifiers, fillers,
rheology modifiers and/or pigments.
[0010] Any suitable curative composition may be used in the
two-part compositions of the present disclosure. The curative
composition typically comprises two or more curative species, which
are typically polyamines. In some embodiments the curative
composition comprises at least one cycloaliphatic polyamine. In
some embodiments the curative composition comprises at least one
adduct of an excess of an unbranched polyetherdiamine with an epoxy
resin, typically an excess of more than 200%, more typically more
than 250%, more typically more than 280%, more typically more than
300%, in some embodiments more than 350%, and in some embodiments
more than 400%. In some embodiments the curative composition
comprises at least one adduct of an excess of an unbranched
polyetherdiamine with an epoxy resin, where the excess is typically
less than 800%, more typically less than 700%, more typically less
than 600%, more typically less than 500% and more typically less
than 450%. The unbranched polyetherdiamine typically has a
molecular weight of less than 500, more typically less than 400,
more typically less than 300, more typically less than 280, more
typically less than 260, and more typically less than 240. The
unbranched polyetherdiamine typically has a molecular weight of at
least 130, more typically at least 150, more typically at least 180
and more typically at least 200. The unbranched polyetherdiamine
typically has between one and four ether oxygens and more typically
two or three ether oxygens. In some embodiments the unbranched
polyetherdiamine may be a compound according to Formula I:
H.sub.2N--[(CH.sub.2).sub.xO].sub.y--(CH.sub.2).sub.x--NH.sub.2
[I]
[0011] where y is 1, 2, 3 or 4, more typically 2 or 3, and where
each x is independently selected from 2, 3, or 4, more typically 2
or 3. In some embodiments y is 2. In some embodiments y is 2 and
each x is independently selected from 2 or 3. In some embodiments y
is 3. In some embodiments y is 3 and each x is independently
selected from 2 or 3. In some embodiments the unbranched
polyetherdiamine may be 4,7,10-trioxa tridecane 1,13-diamine (TTD).
In some embodiments the unbranched polyetherdiamine may be
4,7-dioxa decane 1,10-diamine, commercially available as
Jeffamine.RTM. EDR 176.
[0012] In some embodiments the curative composition comprises both
the unbranched polyetherdiamine/epoxy adduct and at least one
cycloaliphatic polyamine. The curative composition may additionally
comprise calcium nitrates as accelerators, as disclosed in PCT
Published App. No. WO2008/089410 [Atty. Docket No. 62522WO005], the
disclosure of which is incorporated herein by reference. The
curative composition may additionally comprise additives which may
include impact modifiers, fillers, rheology modifiers and/or
pigments. However the curative composition according to the present
disclosure typically comprises no particulate metal filler or
additive. The curative composition according to the present
disclosure typically comprises no particulate aluminum or aluminum
alloy filler or additive. The curative composition according to the
present disclosure typically comprises no particulate iron, steel,
or iron alloy filler or additive. The curative composition
according to the present disclosure typically comprises no
particulate copper or copper alloy filler or additive.
[0013] In many embodiments liquid shim compositions will cure fully
at room temperature in twenty-four to forty-eight hours and can be
sanded or drilled four hours after application. In many embodiments
liquid shim compositions will have about 3hours pot life (time for
positioning and adjusting) and may be cured at an accelerated rate
with application of mild heat, typically curing in less than 30
minutes at 70.degree. C.
[0014] In many embodiments liquid shim compositions will
demonstrate characteristics prior to cure including a combination
of low viscosity such as may be suitable for injection or
application by syringe together with a low degree of sag or creep
upon application.
[0015] In many embodiments liquid shim compositions will
demonstrate characteristics after cure including: good compression
strength without brittleness, reasonable strength properties at low
and high temperatures (-55 to 120.degree. C.), and resistance to
most solvents, oils, hydraulic fluids, and the like. In many
embodiments the present compositions will demonstrate Tg after cure
of greater than 120.degree. C., more typically greater than
140.degree. C., more typically greater than 160.degree. C., and
more typically greater than 180.degree. C. In many embodiments
liquid shim compositions must meet the requirements of Airbus AIMS
qualification 10-07-001.
[0016] Objects and advantages of this invention are further
illustrated by the following examples, but the particular materials
and amounts thereof recited in these examples, as well as other
conditions and details, should not be construed to unduly limit
this invention.
Examples
[0017] Unless otherwise noted, all reagents were obtained or are
available from Aldrich Chemical Co., Milwaukee, Wis., or may be
synthesized by known methods.
Epoxy Resin Compositions
[0018] The epoxy resin compositions presented in Table I were made
by mixing in a small lab mixer. Manufacturing of formulation B4 was
done in 21 doppel Z lab mogul. The Novolac resin was introduced
into the mogul and blended with the Kane Ace 156. After about 30
minutes mixing Aerosil was added followed by addition of Titanium
dioxide powder. The whole was then mixed for at least 40 min under
vacuum. The result was a homogeneous white paste.
TABLE-US-00001 TABLE I Formulation Chemical Nominal (wt % of
Components) Component Description Role B1 B2 B3 B4 ERISYS
tetra-functional Base 38 0 0 0 GA 240 epoxy resin based resin on
meta- Xylenediamine Epon 828 Epoxy Base 0 38 0 0 Bisphenol A resin
E-8250 Epoxy novolac Base 0 0 38 0 resin resin D.E.N. 431 Epoxy
novolac Base 0 0 0 30 resin resin Kane Ace p-Butadiene Core Impact
20 20 20 38 156 shell into modifier DGEBA resin Paraloid Core shell
based impact 5 5 5 0 on butadiene modifier rubber Kronos Titanium
dioxide Filler 32 32 32 30 Aerosil Treated fumed Rheology 5 5 5 2
silica Modifier TOTAL 100 100 100 100
Curative Compositions
[0019] The curative compositions presented in Table II were made by
mixing in a small lab mixer. Manufacture of formulations A1 and A2
was done in the same mogul described for part B4. The first step
was introduction of the Ancamine 2167 and calcium nitrate. These
were heated to 80.degree. C. and mixed for 1 hour. After cooling
down to room temperature (RT) Aerosil was added and mixed until
homogeneity. After that the TTD and Epikote 828 adduct was
introduced and mixed at RT for about 30 min. After that Minsil and
Carbon Black were incorporated and mixed under vacuum for 1 hour.
The TTD and Epikote 828 adduct was made by reacting 180 parts of
TTD with 60 parts of Epikote 828. The two components were mixed at
RT for 1 h and then heated up to 80 C. The temperature was
maintained for one hour to complete the pre-polymerization
reaction.
TABLE-US-00002 TABLE II Formulation (wt % of Chemical Nominal
Components) Component Description Role A0 A1 A2 Ancamine Cyclo
aliphatic Curative 1 40 40 35 2167 polyamine MC 273 Aliphatic
Curative 2 15 15 0 polyamidoamine TTD & 4,7,10- Curative 2 0 0
20 Epikote trioxatridecane 828 adduct 1,13-diamine & epoxy
resin Calcium Calcium Nitrate Accelerator 0 2 2 Nitrate Aerosil
Treated Fumed Rheology 5 5 5 Silica Minsil SF Silica particles
Filler 40 37.9 37.9 20 (Amorphous) Carbon Pigment 0 0.1 0.1 Black
Total 100 100 100
Resin/Curative Combinations
[0020] The present disclosure contemplates any combination of B and
A parts, including B1/A0, B1/A1, B1/A2, B2/A0, B2/A1, B2/A2, B3/A0,
B3/A1, B3/A2, B4/A0, B4/A1 and B4/A2. The following combinations of
B and A parts were made at a ratio of two parts by volume B to one
part by volume A: B1/A0, B2/A0, B3/A0, B4/A1 and B4/A2. The mixed
viscosity of formulations B4/A1 and B4/A2 were measured to be below
600 Pascals (Pa), measured on Haake RheoWin instrument.
Results--Cure Time
[0021] The pot life of the B1/A0, B2/A0 and B3/A0 formulations were
determined by DSC measurement (Degree of cure). Table III reports
curing potential as function of time after mixing for these three
combinations.
TABLE-US-00003 TABLE III B1/A0 B2/A0 B3/A0 Curing potential (total)
100% 100% 100% 3 h after mixing 90% 70% 73% 3 h after mixing + 35%
28% 33% 30 min @70.degree. C.
[0022] The pot life of B4/A1 was observed to be approximately 120
min. The pot life of B4/A2 was observed to be approximately 90
min.
Results--Mechanical Testing
[0023] Mechanical testing was performed according to Airbus AIMS
qualification 10-07-001. Results are disclosed in Tables IV, V and
VI.
TABLE-US-00004 TABLE IV Overlap Shear (MPa) on Aluminum substrates
Minimum B1/A0 B2/A0 B3/A0 B4/A1 B4/A2 RT 21 23 24 21 18 24
-55.degree. C. 18 18.5 21 19 12 27 80.degree. C. 19 22 18 16.5 11
21 120.degree. C. 8.5 14 5 7.7 8 16
TABLE-US-00005 TABLE V Peel Load Minimum B1/A0 B2/A0 B3/A0 B4/A1
B4/A2 23.degree. C. 50 80 100 95 60 100 -55.degree. C. 20 45 119 54
15 120 120.degree. C. 10 33 15 8 23 35
TABLE-US-00006 TABLE VI Compression Strength Minimum B1/A0 B2/A0
B3/A0 B4/A1 B4/A2 RT 55 100 65 70 100 95 -55.degree. C. 150 170 94
132 175 160 80.degree. C. 37 75 32 40.5 24 52 120.degree. C. 28 35
12 17 17 34
[0024] The B1/A0 and B4/A2 formulations showed the best mechanical
characteristics. Additional characterization was performed for the
B4/A2 formulation, including fluid resistance and aging tests,
reported in Tables VII, VIII and IX.
TABLE-US-00007 TABLE VII B4/A2 Overlap shear strength (MPa) Test
Temp Condition Duration .degree. C. Min. Results Methyl ethyl
ketone (MEK) 1 h 120 8 10 Dry heat 120.degree. C. 7 days 120 8.5 18
Water at 70.degree. C. 7 days 120 7 10 Skydrol/H2O mixture 1000 h
120 7.5 9 Skydrol 1000 h 1000 h 120 8 13
TABLE-US-00008 TABLE VIII B4/A2 Peel Load (N) Test Temp Condition
Duration .degree. C. Min. Results Dry heat 120.degree. C. 7 days 23
50 107
TABLE-US-00009 TABLE IX B4/A2 Compression strength (MPa) Test Temp
Condition Duration .degree. C. Min. Results 85% R.H. &
70.degree. C. 1000 h 23 55 93 85% R.H. & 70.degree. C. 1000 h
-55 150 160 85% R.H. & 70.degree. C. 1000 h 120 18 24
[0025] Various modifications and alterations of this invention will
become apparent to those skilled in the art without departing from
the scope and principles of this invention, and it should be
understood that this invention is not to be unduly limited to the
illustrative embodiments set forth hereinabove.
* * * * *