MXPA98000098A - Processing and tenacity of ethical copolymer materials - Google Patents
Processing and tenacity of ethical copolymer materialsInfo
- Publication number
- MXPA98000098A MXPA98000098A MXPA/A/1998/000098A MX9800098A MXPA98000098A MX PA98000098 A MXPA98000098 A MX PA98000098A MX 9800098 A MX9800098 A MX 9800098A MX PA98000098 A MXPA98000098 A MX PA98000098A
- Authority
- MX
- Mexico
- Prior art keywords
- composition
- polymer
- copolymer
- ethylene
- alpha
- Prior art date
Links
- 229920001577 copolymer Polymers 0.000 title claims abstract description 18
- 239000000463 material Substances 0.000 title description 6
- 239000000203 mixture Substances 0.000 claims abstract description 17
- 229920000642 polymer Polymers 0.000 claims abstract description 16
- 239000004711 α-olefin Substances 0.000 claims abstract description 11
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000005977 Ethylene Substances 0.000 claims abstract description 6
- 239000003054 catalyst Substances 0.000 claims description 12
- 229920000098 polyolefin Polymers 0.000 claims description 10
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- 150000007942 carboxylates Chemical class 0.000 claims description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 2
- 125000003010 ionic group Chemical group 0.000 claims 3
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 claims 1
- 229920000554 ionomer Polymers 0.000 abstract description 5
- 159000000000 sodium salts Chemical class 0.000 description 6
- 150000003751 zinc Chemical class 0.000 description 6
- 229920001038 ethylene copolymer Polymers 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- JDCCCHBBXRQRGU-UHFFFAOYSA-N 5-phenylpenta-2,4-dienenitrile Chemical class N#CC=CC=CC1=CC=CC=C1 JDCCCHBBXRQRGU-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical class C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000010128 melt processing Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- -1 zinc salts Chemical class 0.000 description 1
Abstract
The present invention relates to: In one embodiment of the present invention, there is provided a composition comprising a predominant amount of a copolymer of ethylene and alpha-olefin and a small amount of a low molecular weight ionomer polymer.
Description
"PROCESSING AND TENACITY OF ETHYLENE COPOLYMER MATERIALS"
FIELD OF THE INVENTION
The present invention relates to polyolefin and polyolefin copolymer compositions. More particularly, the invention relates to improving the toughness and processability of polyolefin polymers and copolymers that have been prepared using single site catalysts.
BACKGROUND OF THE INVENTION
In recent years, a new class of polyolefin and polyolefin copolymers has been developed based on the use of so-called single-site catalysts. These catalysts, which are organometallic coordination compounds of cyclopentadienyl derivatives of metals of Group IVB of the Periodic Table of Elements (Edition 56 of the Manual of Chemistry and Physics, CRC Press (1975)), produce polyolefins that have a molecular weight distribution. more limited to that achieved with conventional Ziegler-Natta type catalysts. This limited molecular weight distribution results in polymeric materials that have better properties than those achieved with typical Ziegler-Natta type catalysts. Despite these improved physical properties, however, there remains a need to lend greater tenacity to the prepared polymers of single-site catalysts. In addition, because the limited molecular weight distribution of these materials, they tend to be more difficult to process. Accordingly, there is also a need to provide a method for improving the processability of polyolefins and olefin copolymers prepared with catalysts from a site.
COMPENDIUM OF THE INVENTION
The present invention is based on the discovery that the ethylene-alpha-olefin polymers that are prepared in the presence of a single site catalyst have their improved toughness and processability by including in the copolymer an effective amount of a molecular weight ionomeric copolymer low. Therefore, in one embodiment of the present invention, there is provided a composition comprising a predominant amount of an ethylene-alpha-olefin copolymer and a small amount of a low molecular weight ionomer polymer. These and other embodiments of the present invention will become apparent upon reading the detailed description of the invention which will be given below.
DETAILED DESCRIPTION OF THE INVENTION
Polymers useful in the present invention include ethylene-alpha-olefin copolymers that have been prepared using single-site catalysts, especially those catalysts described in U.S. Patent No. 5,391,629, which is incorporated herein by reference. Typically, the copolymers useful in the present invention will have weight average molecular weights of between about 10,000, and about 2 million, and preferably between about 50,000 and about 300,000. Also, these ethylene-alpha-olefin polymers generally contain from 30 percent to 90 percent ethenyne, the remainder being an alpha-olefin of about 3 to 12 carbon atoms. Preferably, the alpha-olefin has 3 or 4 carbon atoms. The compositions of the present invention also include a small amount of a low molecular weight ionomeric polymer or copolymer, ie, one having a weight average molecular weight of between about 1,000 and 20,000 and more preferably, between 2,000 and 10, 000. Generally, the ionomeric polymer will have from about 0.1 to about 200 milliequivalents of the ionomeric groups suspended per 100 grams of the polymer and preferably from about 1.0 to 100 milliequivalents of the suspended ionomeric groups. Examples of the useful ionomeric groups are carboxylate, phosphate and sulfonate. Preferably, the ionomeric groups will also be neutralized by approximately 50 percent with Group IA metal, IIA, IB or IIB (see Table of Elements cited above), an amine or ammonia. The amount of the ionomeric polymer or copolymer will be used in amounts ranging from less than about 20 weight percent, based on the total weight of the composition and typically within the range of from about 0.5 percent to about 10.0 percent by weight. The ionomeric polymers and copolymers especially suitable in the practice of the present invention include sulfonated polystyrene copolymers. sulfonated tertiary butyl sulfoth polystyrene, sulfonated ethylene, sulfonated propylene copolymers, sulfonated styrene-acrylonitrile copolymers, sulfonated styrene-methyl methacrylate copolymers, sulfonated polystyrene, sulfonated ethylene-propylene terpolymers, sulfonated polyisoprene and sulfonated elastomers and their copolymers. A preferred ionomeric carboxylate is the copolymer of ethylene and acrylic acid. The compositions of the present invention can be prepared by any convenient method. For example, the compositions can be prepared by mixing in an appropriate mixer such as a Brabender mixer. The following examples illustrate the invention.Examples 1 to 5
A copolymer of ethylene and butene prepared using a single-site catalyst and having a melt index of 4.5, a density of 0.873 gram per cubic centimeter and a polydispersity of about 2.2 was melt blended with varying amounts of an ethylene copolymer. and acrylic acid having a weight average molecular weight of 2,000 grams per mole which were neutralized with sodium and zinc, respectively. The melt processing was carried out in a Brabender mixer heated to 193 ° C. The materials were mixed for 5 minutes at 100 revolutions per minute. The material was cooled to room temperature, cut into pieces and subsequently compression molded (193 ° C) into tension specimens. The mixtures were formed into the final form through compression molding into pads of approximately 5.08 centimeters by 5.08 centimeters by 508 mm, using the following conditions: 2 minutes of preheating at 193 ° C, followed by three minutes of cycle in the press to 29 tons (193 ° C) and finally, 4 minutes of cooling to room temperature (again under pressure of 29 tons). The sample size appropriate for stress test measurements are cut from these pads. The mechanical properties were obtained from a
Instron® Voltage Tester with a clamp speed of 0.2 centimeter per minute. Table 1 below lists the typical mechanical property values for the copolymer where different amounts of the low molecular weight ionomers (sodium and zinc salts) were melted by melting. The mechanical properties of the unmixed polymer are also included in the table for comparison purposes.
TABLE 1 MEASURES OF MECHANICAL PROPERTIES AND REDUCTION OF TORQUE
TORSION
Module Additive Energy to ionomer (%) (kg / cm-) breakage (kirk)
For comparison 1 Sodium salt 0.0 21.16 .146
Example 2 Sodium salt 1.0 47.80 .155
Example 3 Sodium salt 5.0 76.70 .132
Example 4 Zinc salt 1.0 49.28 .207
Example 5 Zinc salt 3.0 64.54.206
Example 6 Zinc salt 5.0 75.78 .182
TABLE 1 (CONTINUED)
Reduction Lengthening Resistance of torque at break to tension torsion (%) (%) (kg / cm2)
For comparison 1 Sodium salt 0.0 1059.0 133.92
Example 2 Sodium Salt 20.0 1074.0 116.49
Example 3 Sodium salt 18.0 1018.0 98.14
Example 4 Zinc salt 14.0 1099.0 124.85 Example 5 Zinc salt 17.0 1099.0 121.48
Example 6 Zinc salt 16.0 1069.0 117.89
The data confirm that the addition of the low molecular weight ionomer to the ethylene copolymer product markedly reduces the torque and therefore, improved processability is observed. In addition, the solid state properties show an improvement in the mechanical properties, that is, in the tenacity.
Claims (7)
1. An improved toughness polymer composition comprising a predominant amount of an ethylene-alpha-olefin copolymer prepared using a single-site catalyst of a cyclopentadienyl derivative of a Group IVB metal; and a small amount of a second polymer or copolymer having a weight-average molecular weight within the range of 11,000 to about 20,000, and of from about 0.1 to about 200 milliequivalents of suspended ionic groups which are selected from carboxylate, phosphate and phosphate groups. sulfonate which are about 50 percent neutralized metal, amine or ammonia, the composition having improved tenacity relative to the ethylene and alpha-olefin copolymer.
The composition of claim 1, wherein the second polymer has a weight average molecular weight within the range of about 11,000 to about 20,000.
The composition of claim 1, wherein the second polymer or copolymer is present in an amount ranging from 0.5 percent to 20 percent by weight, based on the total weight of the composition.
4. The composition of claim 3, wherein the ionic group is a carboxylate group.
The composition of claim 4, wherein the ionic group is neutralized metal.
6. The composition of claim 5, wherein the alpha-olefin of the ethylene and alpha-olefin polymer has from 3 to 12 carbon atoms. The composition of claim 6, wherein the second polymer is a copolymer of ethylene and acrylic acid.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US49926495A | 1995-07-07 | 1995-07-07 | |
| US499264 | 1995-07-07 | ||
| PCT/US1996/011309 WO1997003126A1 (en) | 1995-07-07 | 1996-07-05 | Processing and toughening of ethylene copolymer materials |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| MX9800098A MX9800098A (en) | 1998-03-29 |
| MXPA98000098A true MXPA98000098A (en) | 1998-10-15 |
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