Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Mixing of two or more solid polymers; mixing of solid...
Reexamination Certificate
1998-08-26
2001-05-15
Lipman, Bernard (Department: 1713)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Mixing of two or more solid polymers; mixing of solid...
C525S331700, C525S332800, C525S332900
Reexamination Certificate
active
06232410
ABSTRACT:
BACKGROUND OF THE INVENTION:
1. Field of the Invention
This invention relates to processes for modifying elastomers, the modified elastomers made thereby, and processes for making products from the modified elastomers.
2. Background Information
The term “elastomer” was first defined in 1940 to mean synthetic thermosetting high polymers having properties similar to those of vulcanized natural rubber, e.g. having the ability to be stretched to at least twice their original length and to retract very rapidly to approximately their original length when released. Representative of these “high polymers” were styrene-butadiene copolymer, polychloroprene, nitrite butyl rubber and ethylene-propylene polymers (aka EP and EPDM elastomers). The term “elastomer” was later extended to include uncrosslinked thermoplastic polyolefins, i.e. TPOs.
ASTM D 1566 defines various physical properties of elastomers, and the test methods for measuring these properties. U.S. Pat. No. 5,001,205 provides an overview of known elastomers comprising ethylene copolymerized with an &agr;-olefin. As described therein, commercially viable elastomers have various minimum properties, e.g. a Mooney viscosity no less than 10, a weight average molecular weight (M
w
) no less than 110,000, a glass transition temperature below −20° C., and a degree of crystallinity no greater than 25%.
A dilemma faced in the production of commercially viable cured elastomers is that a high weight average molecular weight is generally desired to improve physical properties such as tensile strength, toughness, compression set, etc., in the cured product, but the uncured high molecular weight elastomers are more difficult to process than their lower molecular weight counterparts. In particular, the uncured higher molecular weight uncured elastomers are typically more difficult it is to isolate from solvents and residual monomer following polymerization of the elastomer. The uncured higher molecular weight elastomers are also typically more difficult to extrude at high rates, since they are generally prone to shear fracture at lower extrusion rates and require more power consumption by polymer processing equipment such as batch mixers, continuous mixers, extruders, etc., and cause increased wear on the parts of such equipment exposed to high shear stresses, such as expensive extruder components. These disadvantages reduce production rates and/or increase the cost of production.
A conventional approach for resolving this dilemma is to make a relatively low molecular weight elastomer and then fully crosslink the final product to obtain the desired tensile strength, toughness, compression set, etc. A disadvantage of that approach is that the low molecular weight of the elastomer also generally corresponds to a low “green strength” (i.e., strength prior to crosslinking). That disadvantage is particularly noticeable in applications such as coating wire and cable, continuous extrusion of gaskets, etc., where low green strength results in sags or uneven polymer thickness. The present invention addresses these and other disadvantages.
SUMMARY OF THE INVENTION
This invention provides a process for improving the green strength of ethylene/&agr;-olefin/diene polymers comprising:
(A) selecting an ethylene/&agr;-olefin/diene polymer having a Mooney ML1+4 viscosity, measured according to ASTM D 1646 at 125 C, up to about 80 and a percent gel (% gel), measured according to ASTM D2765, Procedure A, up to about 30 percent and
(B) partially crosslinking the ethylene/&agr;-olefin/diene polymer selected in step (A) to make a modified ethylene/&agr;-olefin/diene polymer satisfying the following equations:
W
≤
(
MS
2
-
MS
1
MS
1
)
wherein MV is the Mooney viscosity of the modified polymer measured as defined above, MS
1
is the melt strength in centiNewtons of the polymer selected in step (A) at 110 C, when formulated according to ASTM D3568#2, MS
2
is the melt strength in centiNewtons of the modified polymer produced by step (B) measured under the same conditions, and W is 0.3.
Another aspect of this invention is the modified ethylene/&agr;-olefin/diene polymers obtainable according to the above process, preferably when they satisfy the equation:
MS
2
≥
(
MV
X
+
%
gel
Y
)
Z
in which MS
2
, MV and % gel of the modified polymer are measured as defined above, X is 50, Y is 20, and Z is 40.
This invention also provides a process for making an article comprising an ethylene/&agr;-olefin/diene polymer comprising:
(A1) melt processing the modified polymer described above;
(B1) forming the product of step (A1) into a shape; and
(C1) curing the product of step (B1) to form an article comprising a crosslinked ethylene/&agr;-olefin/diene polymer.
This invention also provides intermediates for making modified ethylene/&agr;-olefin/diene polymers according to the above process comprising a polymer selected according to step (A) in combination with unreacted peroxide crosslinking agent in an amount appropriate to modify the selected polymer according to that process under melt processing conditions.
This invention also provides another process for making an article comprising an ethylene/&agr;-olefin/diene polymer comprising:
(A1) melt processing the above intermediate;
(B1) forming the product of step (A1) into a shape; and
(C1) curing the product of step (B1) to form an article comprising a crosslinked ethylene/&agr;-olefin/diene polymer.
DETAILED DESCRIPTION OF THE INVENTION
Unless indicated to the contrary, all parts, percentages and ratios are by weight. The expression “up to” when used to specify a numerical range includes any value less than or equal to the numerical value which follows this expression. The expression “wt %” means “weight percent”.
The term “crosslinking” as used herein refers to both tetrafunctional (H-type) long chain branching resulting from a covalent linkage between two polymer molecule backbones and trifunctional (T-type) long chain branching produced when a terminal group of a polymer molecule forms a covalent linkage with the backbone of another polymer molecule.
The term “gel” refers to a three-dimensional polymer network which is formed from covalently linked polymer chains. The amount of gel is expressed in terms of weight-percent based on the total weight of the polymer as determined by ASTM D2765, Procedure A.
The term “melt strength” refers to the strength of the elastomer measured in centiNewtons at 110 C when it is formulated according to ASTM D3568#2 according to a procedure described in more detail in the examples below.
Unless specified otherwise, the term “Mooney viscosity” as used herein means viscosity which is measured according to ASTM D1646, incorporated herein by reference, using a sheer rheometer at 125 C and measured according to ML 1+4.
The ethylene/&agr;-olefin/diene polymers used to make rheology-modified polymers according to this invention are polymers of ethylene (CH
2
═CH
2
) with at least one aliphatic C
3
-C
20
&agr;-olefin and at least one C
4
-C
20
diene. The diene ay be conjugated or nonconjugated.
Examples of the aliphatic C
3
-C
20
&agr;-olefins include propene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicosene. The &agr;-olefin can also contain a cyclic structure such as cyclohexane or cyclopentane, resulting in an &agr;-olefin such as 3-cyclohexyl-1-propene (allylcyclohexane) and vinyl-cyclohexane.
Examples of nonconjugated dienes include aliphatic dienes such as 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 2-methyl-1,5-hexadiene, 1,6-heptadiene, 6-methyl-1,5-heptadiene, 1,6-octadiene, 1,7-octadiene, 7-methyl-1,6-octadiene, 1,13-tetradecadiene, 1,19-eicosadiene, and the like; cyclic dienes such as 1,4-cyclohexadiene, bicyclo[2.2.1]hept-2,5-diene, 5-ethylidene-2-norbornene (ENB), 5-methylene-2-norbornene, 5-vinyl-2-norbornene, bicyclo[2.2.2]oct-2,5-diene, 4-vinylcyclohex-I-ene, bicyclo[2.2.2]oct2,6-diene, 1,7,7-trimethylbicycl
Kao Che I.
Rowland Michael E.
Lipman Bernard
The Dow Chemical Company
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