Note: Descriptions are shown in the official language in which they were submitted.
CA 02548200 2006-05-25
FLUID AND HEAT RESISTANT CHLORINATED POLYETHYLENES (CPE)
FIELD OF THE INVENTION
[00011 The present application relates to chlorinated polyethylene rubber
compositions which have good fluid resistance, e.g. automatic transmission
fluids,
or have good high heat resistance.
BACKGROUND OF THE INVENTION
[0002] Heretofore, numerous rubber compounds were utilized as sheets, tubings,
liners, and the like. However, generally no chlorinated polyethylene rubber
compositions have existed which had good resistance to transmission fluids,
especially the recent new types of "E-fluids".
[0003] Similarly, while numerous types of high temperature-resistant rubbers
were available, generally no blend of a chlorinated polyethylene elastomer, an
ethylene-octene copolymer, and an ethylene-acrylic and/or a polyacrylic
elstomer
was known which had good heat resistance as at approximately 150 C.
SUMMARY OF THE INVENTION
[0004] Fluid resistant rubbers generally comprise 70 parts by weight of
chlorinated polyethylene, and about 5 to about 49 parts by weight of an
ethylene-
acrylic elastomer having a Mooney viscosity (ML 1+4/100 C) of about 10 to
about 25 and/or a polyacrylic elastomer having a Mooney viscosity of from
about
to about 70.
[0005] Rubber compositions having good high heat resistance generally comprise
70 parts by weight of a chlorinated polyethylene rubber containing from about
25% to about 45% chlorine by weight, from about 5 to about 49 parts by weight
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CA 02548200 2006-05-25
of an ethylene-octene copolymer having an octene content of from about 25% to
about 55% by weight, from about 5 to about 49 parts by weight of an ethylene-
acrylic elastomer having a Mooney viscosity of from about 10 to about 25
and/or
an polyacrylic rubber having a Mooney viscosity of from about 10 to about 70,
and
optionally from about 10 to about 50 parts by weight of an EPDM rubber
containing from about 30% to about 70% by weight of ethylene repeat units and
from about 0.1 % to about 8% of diene repeat units.
DETAILED DESCRIPTION OF THE INVENTION
Fluid Resistant Rubber Compositions
[0006] The various components of the chlorinated rubber composition are based
upon 70 parts by weight of at least one chlorinated polyethylene elastomer.
The
chlorinated elastomer generally contains from about 25% to about 50% by
weight,
desirably from about 30% to about 45% by weight, and preferably from about
36% to about 42% by weight of chlorine therein. Examples of suitable
chlorinated
polyethylene elastomers are known to the literature and to the art and
specific
commercial examples of such compounds include Tyrin CM 0836 which contains
approximately 36% by weight of chlorine and has a Mooney viscosity (ML
1+4/100 C) of about 100, Tyrin CM 0136 which contains approximately 36% by
weight of chlorine and has a Mooney viscosity of about 80, and Tyrin CM 4211 P
which contains approximately 42% by weight of chlorine and has a Mooney
viscosity of about 80. All of the Tyrin chlorinated polyethylene elastomers
are
available from DuPont Dow.
[0007] Whenever reference is made to a Mooney viscosity in the present
invention it is an (ML 1+4/100 C) Mooney viscosity.
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[0008] An important aspect of the chlorinated polyethylene elastomers of the
present invention is that they are desirably curable by peroxides such as
those set
forth herein below, as well as by various thio compounds such as thiadiazole
derivatives, and also by irradiation. If two or more chlorinated polyethylene
elastomers are utilized, the range of any one elastomer can generally be from
about
1% to about 99% by weight and desirably from about 25% to about 75% by
weight based upon the total weight of all of the chlorinated polyethylene
elastomers.
[0009] Another important component of the chlorinated rubber composition is at
least one ethylene-acrylic elastomer wherein the acrylic can be an alkyl
acrylate
wherein the alkyl portion desirably has from about 1 to about 8 carbon atoms
and
preferably is methyl acrylate. The ethylene-acrylic elastomer generally has a
Mooney viscosity of from about 10 to about 25 and desirably from about 13 to
about 19. The total amount of the one or more ethylene-acrylic elastomers is
generally from about 5 to about 49 parts, desirably from about 5 to about-40
parts,
and preferably from about 25 to about 35 parts by weight per 70 parts by
weight
of said one or more chlorinated polyethylene elastomers. Examples of suitable
ethylene-acrylic elastomers include the various Vamac elastomers available
from
DuPont Industrial Polymers such as Vamac D, Vamac DLS, Vamac G, Vamac GLS,
and Vamac HG with Vamac DP being highly preferred.
[0010] In lieu of the ethylene-acrylic elastomer or in any portion therewith,
one
or more polyacrylate elastomers can be utilized which are known to the art and
to
the literature. Generally, polyacrylate elastomers contain repeat units of
alkyl
acrylates wherein the alkyl portion desirably has from 1 to about 8 carbon
atoms,
and preferably is methyl acrylate or ethyl acrylata, Generally lesser amounts
of
alkoxy acrylates are also utilized wherein the alkoxy portion generally has
from 1 to
CA 02548200 2006-05-25
carbon atoms with methoxy or ethoxy being preferred. The Mooney viscosity of
the one or more acrylate elastomers is generally from about 10 to about 70 and
preferably from about 25 to about 40 or 55. The amount of the polyacrylic
elastomers is generally from about 5 to about 49 parts, desirably from about 5
to
about 40 parts, and preferably from about 25 to about 35 parts by weight per
70
parts by weight of said chlorinated polyethylene elastomers. The polyacrylic
elastomer can be utilized either in lieu of the one or more ethylene-acrylic
elastomers or partially substituted therefore. In other words, any combination
of
the ethylene-acrylic elastomers or the polyacrylic elastomers can be utilized
with
the total amount of both being from about 5 to about 49 parts by weight,
desirably
from about 5 to about 40 parts by weight and preferably from about 25 to about
35 parts by weight per 70 parts by weight of said polychlorinated polyethylene
elastomers. Inasmuch as the present invention generally relates to peroxide
cure,
polyacrylates are utilized which are curable by a peroxide. Since the
polyacrylates
have a saturated backbone, crosslinking is accomplished via incorporation of a
co-
polymerized reactive cure site such as through the use of suitable peroxide
reactive
compounds such as a carboxylic acid, and the like. A suitable polyacrylic
elastomer is HyTemp PV-04 made by Zeon Chemicals.
[0011] An optional but desired component of the chlorinated rubber composition
is a chlorosulfonated polyethylene which generally contains from about 25% to
about 45%, desirably from about 30% to about 40% and preferably from about
33% to about 38% by weight of chlorine therein. The amount of sulfur is
generally very low as from about 0.25% to about 2%, desirably from about 0.5%
to about 1.5%, and preferably from about 0.75% to about 1.25% by weight based
upon the total weight of the chlorosulfonated polyethylene. One or more
chlorosulfonatod poly thylones whon utilized io penerally from about 5 to ab
ut 48
parts by weight, desirably from about 10 to about 40, and preferably from
about
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25 to about 35 parts by weight per 70 parts by weight of said one or more
chlorinated polyethylene elastomers. Examples of such suitable compounds
include
the various Hypalon compounds from DuPont Dow such as Hypalon 20, Hypalon
30, with Hypalon 40 being preferred which contains approximately 35% chlorine
by weight and approximately 1 % sulfur by weight.
[0012] The chlorinated rubber composition of the present invention is
compounded utilizing generally conventional additives known to the art and to
the
literature such as activators and/or acid scavengers, processing aids, various
fillers
which can also serve as reinforcing aids, plasticizers, vulcanizing compounds
such
as various peroxides, co-agents such as curing activators, lubricants,
stabilizers,
and the like.
[0013] Activators and/or acid scavengers include various metal hydroxyls
and/or
carbonates such as magnesium aluminum hydroxy carbonate, metal oxides such as
magnesium dioxide, lead oxide, organic lead bases, and the like. A preferred
activator/acid scavenger is Maglite D or DE produced by the C.P. Hall Company.
The total amount of such activator and/or acid scavenger(s) is generally low
such
as from about 3 to about 20 and desirably from about 5 to about 15 parts by
weight per 70 parts by weight of said one or more chlorinated polyethylene
elastomers.
[0014] Processing aids include various waxes such as low molecular weight
polyethylene waxes, polystyrene waxes, paraffin wax, fatty acids, and the like
with
the polyethylene waxes being preferred. Suitable amounts of processing aid(s)
generaily range from about 0.1 to about 10 and desirably from about 1 to about
5
parta by weight p r 70 parta by weight of said ona or more ahlorinated
polyethylene elastomers.
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[0015] Suitable fillers include Kaolin clay, mica, calcium, carbonate, and the
like.
The amount of said filler(s) is generally from about 5 to about 80 parts by
weight
per 70 parts by weight of said one or more chlorinated polyethylene
elastomers.
Reinforcing fillers such as carbon black preferably have high surface area and
iodine
numbers of from about 25 to about 32. Specific examples include an N762, N774,
N550, and N990 produced by Cancarb. The amount of the reinforcing agent(s) is
generally high as from about 50 to about 300 parts by weight, desirably from
about 100 to about 250 parts by weight, and preferably from about 125 to about
200 parts by weight per 70 parts by weight of said one or more chlorinated
polyethylene elastomers.
[0016] Numerous types of plasticizers can be utilized to impart heat and light
stability such as one or more epoxidized soybean oils, various diphthalates
such as
diallyl phthalate, di-2-ethylhexyl phthalate, diisopropyl phthalate, linear CB-
C,o
phthalates, and linear C7-Cõ phthalates; various trimellitates such as tri-2-
ethylhexyl trimellitate, triisooctyl trimellitate, and triisononyl
trimellitates; various
adipates such as diisooctyl adipate, di-2-ethylhexyl adipate, diisononyl
adipate, and
diisodecyl adipate; various azelates such as di-2-ethylhexyl azelate; various
glutarates such as diisodecyl glutarate; and various sebacates such as di-2-
ethyihexyl sebacate. The total amount of the one or more different types of
plasticizer(s) is generally from about 1 to about 60 parts by weight and
desirably
from about 7 to about 50 parts by weight per 70 parts by weight of said one or
more chlorinated polyethylene elastomers.
[0017] The vulcanizing compound is desirably a peroxide and numerous types
thereof are known to the art and to the litaratura, Exampl s of suitablQ
paroxidos
include 4,4-bis(tert-butyl peroxy) butyl valerate, t-butyl perbenzoate, 2,5-
dimethyl-
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2, 5-di(t-butylperoxy)-3-hexyne, n-butyl-4,4-bis(t-butylperoxy)valerate, 1, 1 -
bis(t-
butylperoxy)3,3,5-trimethyl cyclohexane, di-(2-tert -
butylperoxyisopropyl)benzene,
dibenzoyl peroxide, 2,5-dimethyl-2,5-di(t-buylperoxy)hexane, dicumyl peroxide,
and
combinations thereof. Preferred peroxides include 2,2'-bis(tert-
butylperoxydiisopropylbenzene) and 1-1-di(tert-butylperoxy)-3,3,5-
trimethytcyclhexane available respectfully as Vulcup 40KE and Trigonox 20-40B-
PD
both of which are available from Harwick Standard. A total amount of the one
or
more vulcanizing compounds is generally from about 0. 1 to about 10 and
desirably
from about 3 to about 6 parts by weight per 70 parts by weight of said one or
more chlorinated polyethylene elastomers.
[00181 Co-agents generally include two types with Type I serving to improve
state of cure and also rate of reaction whereas Type II generally only affects
state
of cure. Examples of suitable Type I co-agents include methacrylate products
such as, trimethylolpropane trimethacrylate (TMPTMA), and various Bis-
maleimides
such as N,N'-m-phenylene dimaleimide (I-+VA-2), and various acrylates such as
trimethylolpropane triacrylate (TMPTA). Suitable Type I) co-agents include
triallyl
cyanurate (TAC), triallyl isocyanurate (TAIC), diallyl terephthalate, and 1,2-
Vinyl
polybutadienes (Ricons), and the like. Numerous other co-agent exist and the
same
are known to the art and to the literature. The total amount of the one or
more co-
agents is generally from about 0. 1 to about 15 parts by weight and desirably
from
about 3 to about 12 parts by weight per 70 parts by weight of said one or more
chlorinated polyethylene elastomers.
[00191 The above various compounds and components are compounded and
subsequently formed into desired end use shapes such as a tube. More
specifically, a desired compounding process involves mixing all of the non-
curing
compounds (other than vulcanizing agents and co-agents) in any order in a
7
CA 02548200 2006-05-25
continuous high shear mixer with the one or more polymers being added last.
Thus, in any order, the one or more activators and/or acid scavengers, the one
or
more processing aids, the one or more fillers such as a reinforcing filler,
and the
one or more plasticizers are added singly in any order with continuous mixing
until
all of them have been added and blended in a high shear mixer. Generally any
high
shear mixer is suitable and a Thyssen Krupp GK 250 E was utilized in the
following
examples. After all the various additives have been added and mixed, the
polymers, that is the one or more chlorinated polyethylene elastomers, the one
or
more optional chlorosulfinated polyethylenes, and the one or more ethylene-
acrylic
elastomers are added generally in any order and mixed until generally a
homogenius
blend is obtained. The compounded rubber can then be cooled in any manner and
deposited as a slab which desirably has an anti-crack agent on the surface
thereof.
When desired, the compounded chlorinated rubber composition of the present
invention in then added to a high shear mixing device which can be the same or
different as utilized in the formation of the compounded rubber and is mixed
with
the one or more vulcanizing agents and one or more co-agents at a low
temperature so that the composition is not cured. The compounded rubber
containing the curing additives can be formed into any desired shape such as a
tube utilizing an extruder. The chlorinated rubber compositions of the present
invention generally have a good shelf life as from about 35 to about 45 days
whereby they can be transferred to an end fabricator and cured at suitable
temperatures.
[0020] Suitable end forms include sheets, tubes, hoses, and seals. A desired
end use of the chlorinated rubber compositions of the present invention are as
a
hose or a tube for use in conveying vehicle transmission fluids and especially
E-
typs trensmission fluids inssmuoh =s ths oompounded rubbsrs hevw Qood
resistance thereto. An automatic transmission "E" fluid specification is WSA-
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CA 02548200 2006-05-25
M96D26-A of the Ford Motor Company. Such specification is hereby substantially
reproduced as follows:
HOSE, REINFORCED RUBBER, AUTOMATIC WSA-M96D26-A
TRANSMISSION FLUID RESISTANT
[0021] 1. SCOPE
[0022] This specification defines a straight or formed synthetic rubber hose
reinforced with a single ply of braided textile, with good resistance to
automatic
transmission fluid.
[0023] 2. APPLICATION
[0024] This specification was released originally for an automatic
transmission oil
cooler hose. The hose is resistant to long term exposure to automatic
transmission
fluid up to 150 C and air temperatures up to 125 C. For applications requiring
air
temperatures above 125 C, consider WSD-M96D13-A.
[0025] 3. REQUIREMENTS
[0026] 3.1 QUALITY SYSTEM REQUIREMENTS
Material suppliers and part producers must conform to Quality System
Requirements, QS-9000. Material specification requirements are to be used for
initial qualification of materials. A Control Plan for ongoing production
verification is
required. This plan must be reviewed and approved by the relevant Ford
Materials
activity and/or Ford Supplier Technical Assistance (STA) prior to production
parts
submission. Appropriate statistical tools must be used to analyze
process/product
data and assure consistent processing of the materials.
[0027] Part producers using this material in their products, must use Ford
approved materials and must conform to a process control plan which has been
approved by STA and/or the relevant Materials Activity.
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[0028] 3.2 INFRARED SPECTROPHOTOMETRY AND/OR THERMAL ANALYSIS
[0029] Ford Motor Company, at its option, may conduct infrared and/or thermal
analysis of material/parts supplied to this specification. The IR spectra and
thermograms established for initial approval shall constitute the reference
standard
and shall be kept on file at the designated material laboratory. All samples
shall
produce IR spectra and thermograms that correspond to the reference standard
when tested under the same conditions.
[0030] 3.3 CONDITIONING AND TEST CONDITIONS
[00311 All test values indicated herein are based on material conditioned in a
controlled atmosphere of 23 +/- 2 C and 50 +/- 5% relative humidity for not
less
than 24 hours prior to testing and tested under the same conditions unless
otherwise specified.
[0032] 3.4 HOSE CONSTRUCTION
[0033] The hose shall consist of a smooth bore synthetic rubber tube and high
temperature and oil resistant synthetic rubber cover (see paragraph 5.2). The
tube
shall be covered with a single ply of suitable braided reinforced textile. The
hose
may be coupled with a crimped metal end-fittings.
[0034] 3.5 MATERIAL TESTING
[0035] The following tests shall be performed on finished hoses and/or test
specimens cut from them. The test specimens shall be die-cut from the finished
parts and buffed or slit to the required thickness where necessary. When not
feasible, specimens cut from moulded test slabs manufactured from the same
material with an equivalent state of cure shall be used. The test slabs shall
have
the following dimensions: 1 50 x 1 50 mm, min x 2.0 +/- 0.2 mm
CA 02548200 2006-05-25
[0036] 3.6 ORIGINAL PROPERTIES
Tube Cover
3.6.1 Hardness, International(ISO 1183, Method 65 - 80 65 - 80
A/ASTM D 1415)
3.6.2 Hardness, Durometer A 65 - 80 65 - 80
(ISO 868/ASTM D 2240, instantaneous,
plied-up specimen)
3.6.3 Tensile Strength, MPa, min 9 9
(ISO 37/ASTM D 4123, Die C)
3.6.4 Elongation, %, min 110 200
(ASTM D 412, Die C)
3.6.5 Ozone Resistance, Rating, max 0 0
(FLTM BP 101-01 m Procedure A or B)
3.6.6 Compression Set, %, max 60 65
(ISO 815/ASTM D 395, Method B, 70 h
at 125 +/- 2 C)
[0037] 3.7 AGED PROPERTIES
3.7.1 Heat Aged, Cover Only
(ISO 188/ASTM D 573, 168 h at 150 +/- 2 C)
Hardness Change 0 to + 10 IRHD
Tensile Strength Change, max - 10%
Elongation at Break Change, max - 40%
Visual Evaluation
No surface tackiness or cracks when folded flat
against itself.
3.7.2 Heat Aged, Cover Only
(ISO 188/ASTM D 573, 1000 h at 120 +/- 2 C)
Hardness Change 0 to 25 IRHD
Tensile Strength Change, max - 20%
Elongation at Break Change, max - 65%
Visual Evaluation
No surface tackiness or cracks when folded flat
against itself.
11
CA 02548200 2006-05-25
3.7.3 Immersion in Currently Released Production
Automatic Transmission Fluid, Tube Only
(ISO 1817/ASTM D 471, 168 h at 150 +/- 2 C, see
paragraph 5.1)
Hardness Change 15 IRHD
Tensile Strength Change, max - 50%
Elongation at Break Change, max - 65%
Volume Change 0 to + 35%
Visual Evaluation
No surface tackiness or cracks when folded flat
against itself.
3.7.4 Immersion in Currently Released Production
Automatic Transmission Fluid, Tube Only
(ISO 1817/ASTM D 471, 1000 h at 135 +/-
2 C, see paragraph 5.1)
Hardness Change 15 IRHD
Tensile Strength Change, max - 60%
Elongation at Break Change, max - 85%
Volume Change 0 to 35%
Visual Evaluation
No surface tackiness or cracks when folded flat
against itself.
3.7.5 Immersion in Oil IRM 903
(ISO 1817/ASTM D 471, 168 h at 150 +/- 2 C)
Hardness Change - 25 IRHD
Tensile Strength Change, max - 40%
Elongation at Break Change, max - 55%
Volume Change, max 0 to + 65%
Visual Evaluation
No surface tackiness or cracks when folded flat
against itself.
12
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[0038] 3.8 FINISHED PART
3.8.1 Burst Pressure, min 6.9 MPa
(ASTM D 380)
3.8.2 Adhesion, min 1.4 N/mm
(ASTM D 413, Strip Method, Type A)
3.8.3 Tensile Strength
(ASTM D 380, 25 mm/minute)
[0039] This requirement applies only when couplings are used with the hose.
Assemblies must withstand a minimum pull of 1.1 kN without the couplings
separating from the hose, leakage at coupling connection or rupture of the
hose.
3.8.4 Low Temperature Flexibility No breaks or cracks
Oil Aging/Cold Soak
[0040] Test Method: Hose assembly shall be filled with current production
approved automatic transmission fluid (see Paragraph 5.1), closed at both ends
and
heat aged at 150 +/- 2 C for 24 h. The aged assemblies, after cooling to 23 +/-
2
C, shall be conditioned at - 40 +/- 1 C for 24 h. After conditioning and while
in the
cold box, the hose assembly shall be bent around a temperature conditioned
mandrel, having a radius equal to the minimum bend radius of 10 times the I.D.
Flexing shall be accomplished within 4 s.
3.8.5 Accelerated Impulse Test
[00411 Test Method: Hose assemblies and/or uncouple d hose, where applicable
shall be preconditioned by filling with current production approved automatic
transmission fluid (see paragraph 5.1), closed at both ends and heat aged at
150
+/- 2 C for 70 h prior to impulse testing. For initial qualification the aged
hose
assemblies must withstand 250,000 impulse cycles at maximum working pressure
of 1.1 MPa without bursting or show any signs of failure. Hose assemblies
removed from test stand and burst pressure tested shall not average more than
13
CA 02548200 2006-05-25
20% below the average of original results per paragraph 3.8.1. Periodic
certification testing thereafter shall require aged assemblies to withstand
100,000
impulse cycles at maximum working pressure of 1.1 MPa without failure while
maintaining temperatures of transmission fluid at 150 C and the ambient air
chamber at 125 C. Burst strength values from hose assemblies after completion
of
100,000 impulse cycles shall not average more than 15 % below the average of
original results (paragraphs 3.8.1 and 3.8.3).
Impulse Test Conditions:
Oil Temperature 150 +/- 3 C
Ambient Temperature 125 +/- 5 C
Cycle Rate 30 - 40/minute
Cycle Data:
Pressure Rise Time 0.20 +/- 0.02 s
High Pressure Hold Time 0.65 +/- 0.02 s
Pressure Drop 0.20 +/- 0.10 s
Pressure Variation 0 - 1.10 MPa
Hydraulic Fluid Currently Released Automatic
Transmission Fluid (see para 5.1)
3.8.5.1 Oil and Heat Resistance
[00421 After successful completion of 100,000 impulse cycles according to
paragraph 3.8.5, standardized ASTM specimens taken from the hose shall not
exceed the following values:
Tube Cover
Hardness, Change, max - 15 + 15
Tensile Strength Change, % max - 50 + 35
Elongation at Break Change, % max - 60 - 65
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3.8.6 Resistance to Kinking
[0043] Test Method: Insert required length of hose on test fixture securing
each
end with metal clamps. When installing hose, it shall be bent within 5 s in
the same
plane and direction as its free state curvature. Place fixture in an oven at
120 +/-
2 C for 1 h. Remove fixture from oven and within 5 minutes pass a steel ball
of
specified diameter through hose installed on fixture. Ball must pass freely.
I.D. Test Sample Length, Ball Diameter
Typical Range min +/- 3.0 mm mm
mm mm
7.1 - 8.7 300 3.20 +/- 0.05
8.8 - 10.1 350 3.95 +/- 0.05
12.1 - 13.3 450 5. 5+/- 0.05
US O. J. eCL:31. '3
~.:..._T.L.S .. 'A~ :1
.Ø"'Ei.. 05!? 3-6
.S@C.,.~? __35~ - D.
1 / 1
t T
/ / ~
t
E % ' E 7
.1M
[0044] Sample Selection: Production hose selected for the kink test should
represent, as nearly as possible, minimum wall thickness. When recording
results
include wall thickness, ovality, and dimension "A" (see above). This dimension
is
measured while sample is on the test fixture.
[0045] The invention will be better understood by reference to the following
examples which serve to illustrate the invention but not to limit the same.
CA 02548200 2006-05-25
TABLE 1
EXAMPLE
INGREDIENTS CHEMICAL NAME FUNCTION OF INGREDIENT A
Tyrin CM 0836 Chlorinated Polyethylene Polymer-36% Cl, Polymer
Mooney 100 70
Vamac DP Ethylene/Acrylic Elastomer-High levels of Polymer
methyacrylate in polymers, composition
proprietary 30
Maglite DE Magnesium Dioxide Activator / Acid Scavenger 3.5
DHT-4A-2 Magnesium Aluminum Hydroxy Carbonate Activator/Acid Scavenger 7.5
AC Poly 617A Pol eth lene Wax Process Aid 2
N990 Carbon Black Filler 135
Hubercarb Q325 Calcium Carbonate Filler 10
Paraplex G62 Epoxidized Soybean Oil Plasticizer 15
Plasthall P-670 Pol ester Adipate Plasticizer 27
Vulcup 40KE 2,2-bis tert-but Iperox isop ropy Ibenzene Vulkanizing Agent 5
Trigonox 29-40B-PD 1-1-di(tert-butylperoxy)-3,3,5- Vulkanizing Agent
trim ethIc clhexane 0.15
TAC DLC-A Triallyl Cyanurate Co-Agent 7.5
Vanax MBM N-N'-m hen lenedimaleimide Co-Agent 0.5
Total 313.15
EXAMPLES
[00461 The various ingredients of Table 1 were compounded in a manner as set
forth above. That is all the non-curing components were added one by one to a
high shear mixer such as those made by Farrel or Krupp and blended with the
polymers being added last. Total mixing time was generally from about 3 to
about
minutes with about 4 minutes being preferred, and the mixing temperature of
the mixer was 250 F to about 320 F with approximately 300 F being preferred.
After cooling and forming into slabs, the chlorinated polyethylene composition
was
then mixed with the indicated curing agents at a low temperature of at about
200 F to 250 F and then extruded into a shape of a tube. Subsequently, the
tube
was cured at about 345 O F for approximately 13 minutes and tested. Examples
1,
3 and 4 were rubber compositions tested after various production runs whereas
Example 2 was a rubber composition made in the form of a hose and removed
there from and teeted. The following propertlea were obteined.
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TABLE 2
Example 1 Example 2 Example 3 Example 4
(production) Off Hose (Production) Production
WSA-M96D26-A
Tensile, psi (1305 min) 1470 -- 1680 1620
Elon ation, % 110% min 212 175 190 193
Durometer, 65- 80 73 65 73 73
50% Modulus -- -- 420 404
Compression Set, Plied - -- - -
70 hrs. at 125 C, 60% max 61 54.1 60.7 61.6
ATF-D, 168 hours at 150 C
Tensile Change, %-50% max.) -3 3 0 5
Elongation Change, %-65% max.) -37 -23 -22 -25
Hardness Change, (-15 pts. Max.) -2 -11 -1 -1
%Volume Change, 0 / +35 % 8.3 7 9.4 8.2
ATF-E, 168 hours at 150 C 8 14 5 32
Tensile Change, % (-50% max.) -60 -62 -51 -52
Elongation Change, %-65% max.) 9 -2 9 12
Hardness Change, -15 pts. Max.) 9.9 6.1 10.7 9.2
% Volume Change, 0/+35 % - - 1082 1218
50% Modulus 8 14 5 32
IRM 903 Oil, 168 hours at 150 C
Tensile Change, %-40% max.) 8 14 5 32
Elongation Change, % (-55% max.) -60 -62 -51 -52
Hardness Change, -25 pts. Max.) 9 -2 9 12
% Volume Change, 0/+65 % 9.9 6.1 10.7 9.2
[0047] Examples 1 through 4 gave excellent results with respect to low change
in various properties such as tensile strength, elongation, hardness, and
percent
volume at high temperatures. Moreover, such tubing passed the "E" type
transmission fluids tests.
High Heat Resistant Rubber Compositions
[00481 The formulations of the high heat resistant rubber compositions are
based
upon 70 parts by weight of one or more chlorinated polyethylene elastomers.
The
amount of chlorine in the elastomer is generally from about 20% to about 45%
by
weight, and preferably from about 25% to about 30% by weight. If two or more
different chlorinated polyethylene elastomers are utilized, the amount of one
of the
17
CA 02548200 2006-05-25
elastomers is generally from about 1 % to about 99% and desirably from about
25% to about 75% by weight based upon the total weight of the chlorinated
polyethylene elastomers. Such elastomers are known to the art and to the
literature. Examples of such suitable chlorinated polyethylene elastomers
include
Tyrin CM 0730 which contains about 30% by weight of chlorine and has a
Mooney viscosity (ML 1+4/1001C) of about 65, Tyrin CM 0836 which contains
about 36% by weight of chlorine and has a Mooney viscosity of about 100, and
Tyrin CM 0136 which contains about 36% by weight of chlorine and has a
Mooney viscosity of about 80. The Tyrin chlorinated polyethylene elastomers
are
produced by DuPont Dow.
[0049] An important aspect of the present invention is to utilize an ethylene-
octene copolymer in an amount of from about 5 to about 49 parts by weight,
desirably from about 12 to about 30 and preferably from about 10 to about 20
parts by weight per 70 parts by weight of the one or more chlorinated
polyethylene
elastomers. Such copolymers generally contain from about 25% to about 55% by
weight and desirably from about 35% to about 45% by weight of the octene unit.
Desirably the copolymers have a low specific gravity of from about 08.5 to
about
08.7 and have a melt index of from about 0.25 to about 5.0 dg/min. Such
copolymers are available as the Engaged polymers produced by DuPont Dow such
as Engaged CL 8001, Engaged CL 8002, Engaged EG 8200, and preferably
Engaged EG 8150.
[0050] An important component utilized to form the high heat resistance rubber
composition generally comprise one or more ethylene-acrylic elastomers wherein
the acrylic portion can be an alkyl acrylate wherein the alkyl desirably has
from
about 1 to about 8 carbon atoms and preferably is methyl acrylate. The
ethylene-
acrylic elastomers generally have a Mooney viscosity of from about 10 to about
25
18
CA 02548200 2006-05-25
and preferably from about 13 to about 19. The total amount of the one or more
ethylene-acrylic elastomers is generally from about 5 to about 49 parts,
desirably
from about 5 to about 35 parts, and preferably from about 10 to about 30 parts
by
weight per 70 parts by weight of said one or more chlorinated poiyethylene
elastomers. Examples of suitable elastomers include Vamac D, Vamac DLS, Vamac
G, Vamac GLS, and Vamac HG with Vamac DP being highly preferred.
[00511 In lieu of the ethylene-acrylic elastomer or in any portion therewith,
one
or more polyacrylate elastomers can be utilized which are known to the art and
to
the literature. Generally, polyacrylate elastomers contain repeat units of
alkyl
acrylates wherein the alkyl portion desirably has from 1 to about 8 carbon
atoms,
and preferably is methyl acrylate or ethyl acrylate. Generally lesser amounts
of
alkoxy acrylates are also utilized wherein the alkoxy portion generally has
from 1 to
carbon atoms with methoxy or ethoxy being preferred. The Mooney viscosity of
the one or more acrylate elastomers is generally from about 10 to about 70 and
preferably from about 25 to about 40 or 55. The amount of the polyacrylic
elastomers is generally from about 5 to about 49 parts, desirably from about 5
to
about 35 parts, and preferably from about 10 to about 30 parts by weight per
70
parts by weight of said chlorinated polyethylene elastomers. The polyacrylic
elastomer can be utilized either in lieu of the one or more ethylene-acrylic
elastomers or partially substituted therefore. In other words, any combination
of
the ethylene-acrylic elastomers or the polyacrylic elastomers can be utilized
with
the total amount of both being from about 5 to about 49 parts by weight,
desirably
from about 5 to about 35 parts by weight and preferably from about 10 to about
30 parts by weight per 70 parts by weight of said polychlorinated polyethylene
elastomers. Inasmuch as the present invention generally relates to peroxide
cure,
pQlyaveylwtw= are utili:ed whioh are oursbl* by w peroxidQ, SinoQ the
polymarylist.=
have a saturated backbone, crosslinking is accomplished via incorporation of a
co-
19
CA 02548200 2006-05-25
polymerized reactive cure site such as through the use of suitable peroxide
reactive
compounds such as a carboxylic acid, and the like. A suitable polyacrylic
elastomer is HyTemp PV-04 made by Zeon Chemicals.
[00521 An optional component of the high heat resistant rubber composition are
various EPDM polymers wherein the amount of ethylene repeat groups is
generally
from about 30% to about 70% and preferably from about 35% to about 60% by
weight, and wherein the amount of diene is generally from about 0.1 to about
8%
and desirably from about 0.2% to about 2% by weight based upon the total
weight
of the copolymer. The amount of the EPDM rubber is generally from about 10 to
about 50 parts by weight, desirably from about 12 to about 35 parts by weight
and preferably from about 15 to about 25 parts by weight per 70 parts by
weight
of the one or more chlorinated polyethylene elastomers. A preferred commercial
example of such as compound is Nordel IP NDR-125 produced by R. T. Vanderbilt.
[00531 An optional component of the chlorinated rubber composition is a
chlorosulfonated polyethylene which generally contains from about 25% to about
45%, desirably from about 30% to about 40% and preferably from about 33% to
about 38% by weight of chlorine therein. The amount of sulfur is generally
very
low as from about 0.25% to about 2%, desirably from about 0.5% to about 1.5%,
and preferably from about 0.75% to about 1.25% by weight based upon the total
weight of the chlorosulfonated polyethylene. One or more chlorosulfonated
polyethylenes when utilized is generally from about 5 to about 49 parts by
weight,
desirably from about 10 to about 40, and preferably from about 25 to about 35
parts by weight per 70 parts by weight of said one or more chlorinated
polyethylene elastomers. Examples of such suitable compounds include the
various
Hypalon oompounde from DuPont Dow such as Hypalon 20, Hypalon 30, with
CA 02548200 2006-05-25
Hypalon 40 being preferred which contains approximately 35% chlorine by weight
and approximately 1 % sulfur by weight.
[0054] One or more antioxidants are utilized to help impart high heat
resistance
to the composition. Numerous antioxidants exist and the same are known to the
art and to the literature. Specific preferred examples of such compounds
include
Tetrakis [methylene (3,5-di-t-butyl-4-hydroxylhydrocinnamate)] methane mixed
with
Pentaerythritol tris ester and 3-(3,5-di-(tert)-butyl-4-hydroxyphenyl)proionic
acid;
Thiodiethylene Bis(3,5-Di(tert)-Butyl-4-hydroxyhydrocinnamate; and the like.
The
total amount of such one or more compounds is generally from about 0.1 to
about
4, and preferably from about 0.5 to about 2 parts by weight per 70 total parts
by
weight of the one or more chlorinated polyethylene elastomers. Commercial
examples of such antioxidants include Irganox 1010 and Irganox 1035 produced
by
Ciba Speciality Chemicals.
[0055] The high heat resistant rubber compositions can generally contain
conventional additives known to the art and to the literature. Such additives
can
be the same as set forth above, that is various activators and/or acid
scavengers,
processing aids, various fillers which also serve as reinforcing aids,
plasticizers,
vulcanizing compounds and co-agents such as activators, lubricants,
stabilizers,
and the like. Since the description of such additives is set forth hereinabove
with
respect to the chlorinated rubber fluid resistant compositions, they are
hereby fully
incorporated by reference. Generally the same types of additives can be
utilized
and the amounts of the various additives are generally the same. However, with
respect to carbon black, generally a smaller amount is utilized as from about
40 to
about 200 parts by weight, and desirably from about 70 to about 150 parts by
woiaht per 70 partc by woiqht of th= ono or more chlorinatod polyethylene
elastomers, Moreover, the amount of the calcium carbonate fillers is generally
from
21
CA 02548200 2006-05-25
about 5 to about 50 parts by weight and desirably from about 10 to about 40
parts
by weight per 70 parts by weight of the one or more chlorinated polyethylene
eiastomers.
[0056] Various vulcanizing agents as well as co-agents (accelerators) can be
utilized. Numerous such compounds exist and are known to the art and to the
literature. With respect to specific chemical examples and specific commercial
examples, generally the same compounds can be utilized as set forth above with
regard to the chlorinated rubber compositions and generally the same amounts
of
the vulcanizing agents and co-agents can be utilized. Accordingly, they are
hereby
fully incorporated by reference.
[0057] A preferred end use of the present invention is to co-extrude the high
heat resistant rubber composition about the chlorinated polyethylene rubber
fluid
resistant composition in the form of a tube to form a laminated tube, hose, or
the
like. In order to impart strength to the hose, reinforcing fibers, either non-
woven or
preferably woven, can be used.
[0058] A preferred end use is a formation of a hose for use with a vehicle
automatic transmission fluid such as the above noted E-type fluid.
[0059] The invention will be better understood by reference to the following
example which serves to illustrate but not to limit the present invention.
[0060] In formation of the high heat resistant rubber composition of Table 3,
the
various additives are added in any order, one by one to a high shear mixer
followed
by the addition of the various polymers, as for example one at a time, and
mixed at
a suitable temperature and time to achieve a blend of a high heat resistant
rubber
22
CA 02548200 2006-05-25
composition. The compounding procedure is essentially the same as set forth
above with regard to the chlorinated polyethylene rubber fluid resistant
composition. Thus, the high shear mixer utilized can be the same. The mixing
temperature of the high shear mixer with respect to the high heat resistant
rubber
composition is generally from about 250 F to about 230 F with about 300
F
being preferred and the mixing time can vary from about 3 to about 10 minutes
with about 4 minutes being preferred. As before, once the composition is
blended,
it can be cooled and stored. At some subsequent time, the one or more
vulcanizing
agents and co-agents are added and mixed at a low temperature such as at about
200 F to about 250 F so as not to cure the rubber.
[0061] Once it is desired to form an end product, the high heat resistant
rubber
compositions containing the curing compounds therein can be mixed at a higher
temperature and formed or shaped into a suitable end product and cured as at a
temperature of from about 330 F to about 360 F for about 10 to about 18
minutes. Suitable end products include sheets, jackets on existing tubing or
hoses,
seals, and the like.
23
CA 02548200 2006-05-25
TABLE 3
Function of Example
INGREDIENTS Chemical Name Ingredient A
Tyrin CM 0730 Chlorinated Pol eth lene Polymer-30% Cl, Mooney 65 Polymer 70
Engage 8150 Ethylene-Octene Polymer - 39% Comonomer, .868 sp.
Gravity, Melt Index 0.5 dg/min Polymer 15
Varnac DP Ethylene/Acrylic Dipolymer-High levels of methyacrylate
in polymers, composition proprietary Polymer 15
Maglite DE Magnesium Dioxide Activator /
Acid
Scavenger 3.5
AC Poly 617A Polyethylene Wax Processing
Aid 2
lrganox 1010 Tetrakis [methylene (3,5-di-t-butyl-4-
hydroxyhydrocinnamate)] methane mixed with
Pentaerythritol tris ester and 3-(3,5-di-(tert)-butyl-4-
h drox phen I proionic acid Antioxidant 1
Activator /
Acid
DHT-4A-2 Magnesium Aluminum Hydroxy Carbonate Scavenger 7.5
N990 Carbon Black Filler 90
Hubercarb Q325 Calcium Carbonate Filler 20
Paraplex G62 Epoxidized Soybean Oil Plasticizer 11
TOTM Trioctyl Trimellitate Plasticizer 11
Nordel IP NDR-125 Ethylene-Propylene-Diene Terpolymer - 42.5% Polymer /
Ethylene, 0.5% Diene Plasticizer 20
Vulcup 40KE Vulkanizing
2,2'-bis tert-but I erox diiso pro Ibenzene Agent . 4.5
Trigonox 29-40B-PD Vulkanizing
1 -1-di(tert-butylperox)-3,3,5-trimethylcyclhexane Agent 0.15
Ricon 152 DLC 70% 1,2-Pol butadiene dispersed on Calcium Silicate Co-Agent 8
TAC DLC-A Triallyl Cyanurate Co-Agent 4.5
Vanax MBM N-N'-m-phen lenedimaleimide Co-Agent 0.75
Total 283.90
[0062] When the high heat resistant rubber composition was prepared, and
tested, the following data was obtained:
24
CA 02548200 2006-05-25
TABLE 4
Function of Example
INGREDIENTS Chemical Name Ingredient A
'NSA-1;t96D26-A
Tensile, psi (1305 min 1790
Elongation, %
110% min 230
Durometer, 65- 80 78
70 hrs. at 125 C, 65%
max 42.8
Tensile Change, %
-10% max. 10
Elongation Change, %
(-40% max.) -21
Hardness Change, pts.
+10 pts.) 7
Ozone, D518-99, Conditioned for 24 hrs. pass
[0063] As apparent from the above data, the high heat chlorinated polyethylene
rubber composition had small changes in various properties such as tensile
strength, elongation and hardness when tested 168 hours at 150 C.
[0064] While in accordance with the patent statutes the best mode and
preferred
embodiment have been set forth, the scope of the invention is not intended to
be
limited thereto, but only by the scope of the attached claims.
