MXPA98000099A - Compositions of copolymer of ethylene-ionomer monofuncio - Google Patents
Compositions of copolymer of ethylene-ionomer monofuncioInfo
- Publication number
- MXPA98000099A MXPA98000099A MXPA/A/1998/000099A MX9800099A MXPA98000099A MX PA98000099 A MXPA98000099 A MX PA98000099A MX 9800099 A MX9800099 A MX 9800099A MX PA98000099 A MXPA98000099 A MX PA98000099A
- Authority
- MX
- Mexico
- Prior art keywords
- copolymer
- ethylene
- alpha
- olefin
- composition
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 22
- 229920001577 copolymer Polymers 0.000 title claims description 24
- 229920000554 ionomer Polymers 0.000 title description 3
- 239000004711 α-olefin Substances 0.000 claims abstract description 25
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims description 13
- 229920000642 polymer Polymers 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 3
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 125000004429 atoms Chemical group 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 229920001038 ethylene copolymer Polymers 0.000 abstract 1
- -1 ethylene-ethylene Chemical group 0.000 abstract 1
- 238000000034 method Methods 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 229920000098 polyolefin Polymers 0.000 description 4
- 239000012467 final product Substances 0.000 description 3
- KEAYESYHFKHZAL-UHFFFAOYSA-N sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- VSGNNIFQASZAOI-UHFFFAOYSA-L Calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 2
- DJWUNCQRNNEAKC-UHFFFAOYSA-L Zinc acetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O DJWUNCQRNNEAKC-UHFFFAOYSA-L 0.000 description 2
- WFDIJRYMOXRFFG-UHFFFAOYSA-N acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000001639 calcium acetate Substances 0.000 description 2
- 229960005147 calcium acetate Drugs 0.000 description 2
- 235000011092 calcium acetate Nutrition 0.000 description 2
- 125000004432 carbon atoms Chemical group C* 0.000 description 2
- 230000005591 charge neutralization Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000001264 neutralization Effects 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 238000006277 sulfonation reaction Methods 0.000 description 2
- 239000004246 zinc acetate Substances 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000000875 corresponding Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 230000000737 periodic Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
Abstract
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 lower molecular weight ethylene-alpha-olefin copolymer or an ethylene-ethylene copolymer. sulfonated alpha-olefin neutralizes
Description
"COMPOSITIONS OF COPOLYMER OF ETHYLENE-IONOMER MONOFUNCTIONAL"
FIELD OF THE INVENTION
The present invention relates to ethylene-alpha-olefin copolymer compositions. More particularly, the present invention relates to improving the processability of ethylene-alpha-olefin and the copolymers 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 organo-metallic coordination compounds of the cyclopentadienyl derivatives of the Group IVB metals of the Periodic Table of the Elements (Edition 56 of the Manual of Chemistry and Physics, CRC Press (1975)), produce polyolefins that possess a more limited molecular weight distribution than can be achieved with conventional Ziegler-Natta type catalysts. This limited molecular weight distribution results in polymeric materials having better physical properties than those achieved of typical Ziegler-Natta type. However, due to the limited molecular weight distribution of these materials, they tend to be more difficult to process. Accordingly, there is a need to provide a method for improving the processability of the ethylene-alpha-olefin copolymers prepared with single-site catalysts.
COMPENDIUM OF THE INVENTION
The present invention is based on the discovery that ethylene-alpha-olefin polymers having weight average molecular weights greater than about 30,000 which are prepared in the presence of a single-site catalyst, have their properties and processability improved including in the copolymer, an effective amount of an ethylene-alpha-olefin of lower molecular weight or a sulfonated ethylene-alpha-olefin neutralized. 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 an ethylene-alpha-olefin of lower molecular weight or an ethylene- sulfonated alpha-olefin neutralized. 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
The polymers that constitute the predominant portion of the compositions of the present invention include ethylene-alpha-olefin copolymers having from about 3 to 12 carbon atoms in the alpha-olefin that have been prepared using single site catalysts, especially those catalysts described in U.S. Patent No. 5,391,629, U.S. Patent Number 4,668,834, and U.S. Patent Publications Number 128,046 and Number 129,368 all of which are incorporated herein by reference. Typically, the copolymers useful in the present invention will have weight average molecular weights of between about 30,000 and about 1 million, and preferably between about 30,000 and about 300,000. The compositions of the present invention will also include a small amount of the lower molecular weight ethylene-alpha-olefin or a neutralized sulfonated ethylene-alpha-olefin copolymer, that is, one having a weight average molecular weight of between about 600 and 50,000, and more preferably, between 800 and 20,000 and from 3 to 12 carbon atoms in the alpha-olefin. The ethylene-alpha-olefin copolymers are prepared using the single site catalysts, as described in the North American Patents and European Patent Publications mentioned above. The preparation of the neutralized sulfonated polymers is disclosed in U.S. Patent No. 5,389,271, which is incorporated herein by reference. Because these lower molecular weight, neutralized, sulfonated, ethylene-alpha olefin copolymers are also prepared from polymers having considerable terminal unsaturation., the functionality added is essentially at the end of the polymer chain. In general, the ionomeric polymer will have from about 0.5 to about 200 milliequivalents of the neutralized sulphonate groups suspended per 100 grams of the polymer and preferably from about 1.0 to 100 milliequivalents of the neutralized sulphonate groups. Preferably, the sulfonate groups will be neutralized by about 50 percent with a Group IA, IIA, IB or IIB metal (see the above-mentioned Table of Elements), an amine or ammonia. In the compositions of the present invention, the alpha-olefin of the lower molecular weight copolymer is preferred to be the same alpha-olefin as that of the high molecular weight copolymer. 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 mixer
Brabender. The following examples will demonstrate the improved toughness and improved processability of the polyolefin compositions of the present invention. In all the examples that will be given below, the compositions were melt processed in a heated Brabender mixer to
193 ° C. The materials were mixed for 5 minutes at 100 revolutions per minute. After mixing the material was cooled to room temperature, cut into pieces and compression molded at 193 ° C into tension specimens.
The specimens were compression molded into pads of approximately 5.08 centimeters by 5.08 centimeters by .508 millimeters at 29 tons of pressure. The sample size appropriate for the stress test measurements are cut from these pads.
The mechanical properties were obtained from an Instron® Voltage Tester at 25 ° C with a clamp speed of 0.2 centimeter per minute.
Example 1
An ethylene-1-butene copolymer prepared using a single site catalyst containing 82.3 weight percent ethylene content and having a weight average molecular weight of 7,400 grams per mole was used to form the neutralized sulfonated copolymer. The sulfonation process is described as follows: in a four-liter capacity flask equipped with a nitrogen gas feed, a thermometer, an air-driven stirrer, a condenser, a heating mantle, were added 300 milliliters of ethane. Subsequently, 30 grams of the ethylene-butene copolymer (EB) was dissolved. The temperature of the solution was raised to about 90 ° C (i.e., 89 ° C to 95 ° C) in order to ensure complete dissolution of the semicrystalline EB. During the thermal equilibrium, 2.3 milliliters of acetic anhydride were dissolved followed by the slow addition of 0.9 milliliter of sulfuric acid. The time period for the addition of the sulfuric acid was about 15 to 20 minutes, after 30 minutes of continuous stirring, the functionalized EB copolymer was neutralized with 2.58 grams of sodium acetate dissolved in 6 milliliters of water and 3 milliliters of methanol The temperature during this procedure was allowed to cool to room temperature. The neutralized copolymer was isolated through steam purification. The material was recovered, dried in the air and then dried more completely in a vacuum oven at 60 ° C for about 24 hours. The bitertiary sulfur analysis was carried out and the sulfur content was used to calculate the sulfonation level. In this specific procedure, the sulfur analysis is 0.43 by weight, which corresponds to 13.5 milliequivalents / 100 grams of the polymer. The final product is a neutralized (monofunctional) sulfonated EB copolymer.
Example 2
The procedure detailed in Example 1 was repeated with the exception that the neutralization procedure involved using zinc acetate, i.e.
. 78 grams of zinc acetate dissolved in 8 milliliters of water and 3 milliliters of methanol. The sulfur content was 0.58 percent by weight corresponding to 18.2 milliequivalents per 100 grams of the polymer. The final product is a neutralized (monofunctional) sulfonized EB copolymer.
Example 3
The procedure detailed in the
Example 1, with the exception that the neutralization procedure involved using calcium acetate, ie, 4.99 grams of calcium acetate dissolved in 16 milliliters of water / 3 milliliters of methanol. The sulfur content was 0.64 weight percent which corresponds to 20.0 milliequivalents per 100 grams of the polymer. The final product is a sulfonated carbon neutralized (monofunctional) EB copolymer.
Example 4 to 11
The semicrystalline monofunctional ionomers of sulphonated EBs mentioned above were melt mixed in various amounts with an ethylene-butene copolymer which was made with a single-site catalyst and having a melt index of 4.5 and a density of 0.873 gram per cubic centimeter.
The tensile properties of the different mixtures and the reduction in torque were obtained and are listed in the Table given below.
Examples 12 to 14
Mixtures were made using the non-functionalized lower copolymer, the EB copolymer of molecular weight (7400 grams per mole) and an EB copolymer having a melt index of 4.5 and a density of 0.8739 per cubic centimeter. The tensile properties and torque reduction that were observed for these mixtures are also provided in the accompanying Table.
Comparison Example 1
Tension properties of the unmixed EB copolymers were obtained and are included in the accompanying Table.
TABLE 1 MEASURES TO REDUCE MECHANICAL PROPERTIES AND PAR
TORSION
Counterion Additive Module Metal reduction (%) (kg / cmr) of torque (%)
Comparison None 0.0 21.16 0.0
Example 4 Sodium 1.0 46.89 10.0
Example 5 Sodium 3.0 49.77 30.0
Example 6 Sodium 5.0 48.86 27.0
Comparison None 0.0 21.16 0.0
Example 7 Zinc 1.0 51.88 10.0
Example 8 Zinc 3.0 72.27 22.0
Example 9 Zinc 5.0 73.18 18.0 Comparison None 0.0 21.16 0.0
Example 10 Calcium 1.0 42.88 15.0
Example 11 Calcium 5.0 60.74 22.0
Comparison None 0.0 21.16 0.0 Example 12 None 1.0 52.23 28.0
Example 13 None 3.0 63.55 27.0
Example 14 None 5.0 83.94 27.0
TABLE 1 (CONTINUED)
Energy at Elongation Resistance at break to stress (kilogrammeters) [%) (kg / cm2)
For comparison .146 1059.0 133.92
Example 4 156 1055.0 123.04
Example 5 146 1013.0 121.13
Example 6 137 1037 126.68
Comparison .146 1059.0 133.92
Example 7 .150 1043.0 120.28
Example 8 118 966.0 106.86
Example 9 140 995.0 112.62
For comparison .146 1059.0 133.92
Example 10 .147 1041.0 119.16 Example 11. 129 970. 0 119. 02
Comparison 146 1059.0 133.92
Example 12 .184 1097.0 122.25
Example 13 145 1018.0 121.34 Example 14 .130 935.0 110.51
Claims (7)
1. A composition comprising: (a) a predominant amount of a first ethylene-alpha-olefin copolymer prepared using a single-site catalyst of a cyclopentadienyl derivative of a Group IVB metal; and having a weight average molecular weight greater than about 30,000; and (b) a small amount of an ethylene-alpha-olefin copolymer prepared using a single site catalyst of a cyclopentadienyl derivative of a Group IVB metal and having a lower molecular weight than the first copolymer and within the scale from about 600 to about 50,000 or a sulphonated derivative thereof, about 50 percent of which is a metal, amine or neutralized ammonia.
The composition of claim 1, wherein the lower molecular weight copolymer has a weight average molecular weight within the range of about 600 to about 50,000.
3. The composition of claim 2, wherein the alpha-olefin of each copolymer has from about 3 to about 12 atoms of carbon.
4. The composition of claim 3, wherein the alpha-olefin is the same for each copolymer.
The composition of claim 4, wherein the ionomeric polymer has from about 10 to about 200 milliequivalents of the ionomeric groups per one hundred grams of the polymer, about 50 percent of which is metal, amine or neutralized ammonia.
6. The composition of claim 5, wherein the ionomeric groups are sulfonate groups. The composition of claim 6, wherein the ionomeric groups are neutralized with metal.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/499,262 US5677381A (en) | 1995-07-07 | 1995-07-07 | Ethylene copolymer-monofunctional ionomer compositions |
| US08499262 | 1995-07-07 | ||
| PCT/US1996/011308 WO1997003125A1 (en) | 1995-07-07 | 1996-07-05 | Ethylene copolymer-monofunctional ionomer compositions |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| MX9800099A MX9800099A (en) | 1998-03-31 |
| MXPA98000099A true MXPA98000099A (en) | 1998-10-15 |
Family
ID=
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA2301644C (en) | Rheology modification of low density polyethylene | |
| JP5252763B2 (en) | Rheologically modified thermoplastic elastomer composition using peroxide and free radical coagent | |
| EP0472956B1 (en) | Dynamically partially crosslinked thermoplastic elastomer containing polybutene-1 | |
| JP4478106B2 (en) | Rheologically modified thermoplastic elastomer composition for extruded profiles | |
| KR19990023813A (en) | Manufacturing method of polypropylene graft copolymer containing anhydride group | |
| Kim et al. | Processabilities and mechanical properties of surlyn‐treated starch/LDPE blends | |
| US4587304A (en) | Sulfomaleation of polyolefins | |
| EP0837906A1 (en) | Processing and toughening of ethylene copolymer materials | |
| EP0837904B1 (en) | Enhanced toughening and improved processability of polyolefins and polyolefin copolymers with low molecular weight additives | |
| MXPA98000099A (en) | Compositions of copolymer of ethylene-ionomer monofuncio | |
| US5677381A (en) | Ethylene copolymer-monofunctional ionomer compositions | |
| Kweon | Preparation and characteristics of chitosan-g-PDMS copolymer | |
| Robeson et al. | Novel ionomers based on blends of ethylene‐acrylic acid copolymers with poly (vinyl amine) | |
| Bagrodia et al. | Sulphonated polyisobutylene telechelic ionomers: 12. Solid-state mechanical properties | |
| US3842147A (en) | Crystalline poly-alpha-olefine composition having improved dyeability | |
| MXPA98000098A (en) | Processing and tenacity of ethical copolymer materials | |
| MXPA98000094A (en) | Increased tenacity and improved processability depoliolephines and copolymers of low-weight syndrives molecule | |
| JP2001520705A (en) | Foamed crystalline ionomer polyolefin | |
| Robeson et al. | Reactive Extrusion Compatibilization of Poly (Vinyl Alcohol)—Polyolefin Blends | |
| CA1252588A (en) | Alloys of vinylidene chloride interpolymers and olefin polymers | |
| Greco et al. | Acid and base functionalization of ethylene‐propylene rubbers, 2. Influence of type and content of functional groups on the mechanical and thermal behaviour of elastomeric network | |
| JPS58129006A (en) | Preparation of thermoplastic elastomer | |
| JPS6383150A (en) | Water-absorbing resin composition and production thereof | |
| JPS62101615A (en) | Production of modified ethylene/alpha-olefin copolymer composition | |
| JPH02269109A (en) | Production of modified polypropylene |