Impact modification of thermoplastics with ethylene/alpha-olefin interpolymers
Compositions having good impact performance can be made from a thermoplastic (e.g., a polyolefin such as polypropylene or HDPE) and an ethylene multi-block copolymer. The compositions are easily molded and often have particular utility in making, for example, automotive facia, parts and other household articles.
1. A composition comprising:
A) a thermoplastic polymer composition, and
B) an impact modifying amount of an ethylene/α-olefin multi-block interpolymer polymerized in the presence of a catalyst composition comprising a first olefin polymerization catalyst having a first comonomer incorporation index, a second olefin polymerization catalyst having a second comonomer incorporation index different than the first comonomer incorporation index, and a chain shuttling agent, wherein the ethylene/α-olefin interpolymer comprises at least 50 mole percent ethylene and:
(a) has a Mw/Mn from about 1.7 to about 3.5, at least one melting point, Tm, in degrees Celsius, and a density, d, in grams/cubic centimeter, wherein the numerical values of Tm and d correspond to the relationship:
Tm>− 2002.9+4538.5( d )−2422.2( d ) 2 ; and either:
(b) has a Mw/Mn from about 1.7 to about 3.5, and is characterized by a heat of fusion, ΔH in J/g, and a delta quantity, ΔT, in degrees Celsius defined as the temperature difference between the tallest DSC peak and the tallest CRYSTAF peak, wherein the numerical values of ΔT and ΔH have the following relationships:
Δ T>− 0.1299(Δ H )+62.81 for Δ H greater than zero and up to 130 J/g,
Δ≧48° C. for Δ H greater than 130 J/g,
wherein the CRYSTAF peak is determined using at least 5 percent of the cumulative polymer, and if less than 5 percent of the polymer has an identifiable CRYSTAF peak, then the CRYSTAF temperature is 30° C.; or
(c) is characterized by an elastic recovery, Re, in percent at 300 percent strain and 1 cycle measured with a compression-molded film of the ethylene/α-olefin interpolymer, and has a density, d, in grams/cubic centimeter, wherein the numerical values of Re and d satisfy the following relationship when the ethylene/α-olefin interpolymer is substantially free of a cross-linked phase:
Re> 1481−1629( d ); or
(d) has a molecular fraction which elutes between 40° C. and 130° C. when fractionated using TREF, characterized in that the fraction has a molar comonomer content of at least 5 percent higher than that of a comparable random ethylene interpolymer fraction eluting between the same temperatures, wherein said comparable random ethylene interpolymer has the same comonomer(s) and has a melt index, density, and molar comonomer content (based on the whole polymer) within 10 percent of that of the ethylene/α-olefin interpolymer.
2. The composition of claim 1 wherein the thermoplastic polymer composition comprises one or more polymers selected from the group consisting of polyurethanes, polyvinyl chlorides, styrenics, polyolefins, polycarbonates, thermoplastic polyester, polyamides, polyactals, and polysulfones.
3. The composition of claim 1 wherein the thermoplastic polymer composition comprises polypropylene.
4. The composition of claim 1 wherein the thermoplastic polymer composition comprises high density polyethylene.
5. The composition of claim 1 wherein the ethylene/α-olefin interpolymer has a Mw/Mn from about 1.7 to about 3.5, and is characterized by a heat of fusion, ΔH in J/g, and a delta quantity, ΔT, in degrees Celsius defined as the temperature difference between the tallest DSC peak and the tallest CRYSTAF peak, wherein the numerical values of ΔT and ΔH have the following relationships:
Δ T>− 0.1299(Δ H )+62.81 for Δ H greater than zero and up to 130 J/g,
Δ T≧ 48° C. for Δ H greater than 130 J/g,
wherein the CRYSTAF peak is determined using at least 5 percent of the cumulative polymer, and if less than 5 percent of the polymer has an identifiable CRYSTAF peak, then the CRYSTAF temperature is 30° C.
6. The composition of claim 1 wherein the ethylene/α-olefin interpolymer is characterized by an elastic recovery, Re, in percent at 300 percent strain and 1 cycle measured with a composition-molded film of the ethylene/α-olefin interpolymer, and has a density, d, in grams/cubic centimeter, wherein the numerical values of Re and d satisfy the following relationship when ethylene/α-olefin interpolymer is substantially free of a cross-linker phase:
Re> 1481−1629( d ).
7. The composition of claim 1 wherein the ethylene/α-olefin interpolymer has a molecular fraction which elutes between 40° C. and 130° C. when fractionated using TREF, characterized in that the fraction has a molar comonomer content of at least 5 percent higher than that of a comparable random ethylene interpolymer fraction eluting between the same temperatures, wherein said comparable random ethylene interpolymer has the same comonomer(s) and has a melt index, density, and molar comonomer content (based on the whole polymer) within 10 percent of that of the ethylene/α-olefin interpolymer.
8. A fabricated article made from the composition of claim 1 .
9. A composition of claim 1 , further comprising at least one additive selected from the group consisting of antioxidants, phosphites, cling additives, antiblock additives, pigments, and fillers.
10. A composition comprising:
A) at least one propylene polymer; and
B) from about 1 to about 25 weight percent based on the total composition of an ethylene/α-olefin multi-block interpolymer polymerized in the presence of a catalyst composition comprising a first olefin polymerization catalyst having a first comonomer incorporation index, a second olefin polymerization catalyst having a second comonomer incorporation index different than the first comonomer incorporation index, and a chain shuttling agent, wherein the ethylene/α-olefin interpolymer comprises at least 50 mole percent ethylene and:
(a) has a Mw/Mn from about 1.7 to about 3.5, at least one melting point, Tm, in degrees Celsius, and a density, d, in grams/cubic centimeter, wherein the numerical values of Tm and d correspond to the relationship:
Tm>− 2002.9+4538.5( d )−2422.2( d ) 2 ; and either:
(b) has a Mw/Mn from about 1.7 to about 3.5, and is characterized by a heat of fusion, ΔH in J/g, and a delta quantity, ΔT, in degrees Celsius defined as the temperature difference between the tallest DSC peak and the tallest CRYSTAF peak, wherein the numerical values of ΔT and ΔH have the following relationships:
Δ T>− 0.1299(Δ H )+62.81 for Δ H greater than zero and up to 130 J/g,
Δ T≧ 48° C. for Δ H greater than 130 J/g,
wherein the CRYSTAF peak is determined using at least 5 percent of the cumulative polymer, and if less than 5 percent of the polymer has an identifiable CRYSTAF peak, then the CRYSTAF temperature is 30° C.; or
(c) is characterized by an elastic recovery, Re, in percent at 300 percent strain and 1 cycle measured with a compression-molded film of the ethylene/α-olefin interpolymer, and has a density, d, in grams/cubic centimeter, wherein the numerical values of Re and d satisfy the following relationship when the ethylene/α-olefin interpolymer is substantially free of a cross linked phase:
Re> 1481−1629( d ); or
(d) has a molecular fraction which elutes between 40° C. and 130° C. when fractionated using TREF, characterized in that the fraction has a molar comonomer content of at least 5 percent higher than that of a comparable random ethylene interpolymer fraction eluting between the same temperatures, wherein said comparable random ethylene interpolymer has the same comonomer(s) and has a melt index, density, and molar comonomer Content (based on the whole polymer) within 10 percent of that of the ethylene/α-olefin interpolymer.
11. The composition of claim 10 wherein the notched Izod impact strength at 20° C. is at least 10% higher as compared to the same propylene polymer composition without the ethylene/α-olefin interpolymer.
12. The composition of claim 10 wherein the notched Izod impact strength at 20° C. is at least 10% higher as compared to the same propylene polymer composition without the ethylene/α-olefin interpolymer.
13. The composition of claim 10 wherein the notched Izod impact strength at 20° C. is at least 15% higher as compared to the same propylene polymer composition without the ethylene/α-olefin interpolymer.
14. The composition of claim 10 wherein the ethylene/α-olefin interpolymer was prepared by using from about 50 ppm to about 300 ppm chain shuttling agent.
15. The composition of claim 14 wherein the chain shuttling agent is diethyl zinc.
16. The composition of claim 10 wherein the ethylene/α-olefin interpolymer has a density of from about 0.85 to about 0.93 g/cm 3 .
17. A fabricated article made from the composition of claim 10 .
18. A composition comprising:
A) high density polyethylene having a density of at least about 0.94 g/cm 3 ; and
B) from about 1 to about 25 weight percent based on the total composition of an ethylene/α-olefin multi-block interpolymer polymerized in the presence of a catalyst composition comprising a first olefin polymerization catalyst having a first comonomer incorporation index, a second olefin polymerization catalyst having a second comonomer incorporation index different than the first comonomer incorporation index, and a chain shuttling agent, wherein the ethylene/α-olefin interpolymer comprises at least 50 mole percent ethylene and:
(a) has a Mw/Mn from about 1.7 to about 3.5, at least one melting point, Tm, in degrees Celsius, and a density, d, in grams/cubic centimeter, wherein the numerical values of Tm and d correspond to the relationship:
Tm>− 2002.9+4538.5( d )−2422.2( d ) 2 ; and either:
(b) has a Mw/Mn from about 1.7 to about 3.5, and is characterized by a heat of fusion, ΔH in J/g, and a delta quantity, ΔT, in degrees Celsius defined as the temperature difference between the tallest DSC peak and the tallest CRYSTAF peak, wherein the numerical values of ΔT and ΔH have the following relationships:
Δ T>− 0.299(Δ H )+62.81 for Δ H greater than zero and up to 130 J/g,
Δ T≧ 48° C. for Δ H greater than 130 J/g,
wherein the CRYSTAF peak is determined using at least 5 percent of the cumulative polymer, and if less than 5 percent of the polymer has an identifiable CRYSTAF peak, then the CRYSTAF temperature is 30° C.; or
(c) is characterized by an elastic recovery, Re, in percent at 300 percent strain and 1 cycle measured with a compression-molded film of the ethylene/α-olefin interpolymer, and has a density, d, in grams/cubic centimeter, wherein the numerical values of Re and d satisfy the following relationship when the ethylene/α-olefin interpolymer is substantially free of a cross-linked phase:
Re> 1481−1629( d ); or
(d) has a molecular fraction which elutes between 40° C. and 130° C. when fractionated using TREF, characterized in that the fraction has a molar comonomer content of at least 5 percent higher than that of a comparable random ethylene interpolymer fraction eluting between the same temperatures, wherein said comparable random ethylene interpolymer has the same comonomer(s) and has a melt index, density, molar comonomer content (based on the whole polymer) within 10 percent of that of the ethylene/α-olefin interpolymer.
19. The composition of claim 18 wherein the notched Izod impact strength at 20° C. is at least 5% higher as compared to the same high density polyethylene composition without the ethylene/α-olefin interpolymer.
20. The composition of claim 18 wherein the notched Izod impact strength at 20° C. is at least 10% higher as compared to the same high density polyethylene composition without the ethylene/α-olefin interpolymer.
21. The composition of claim 18 wherein the notched Izod impact strength at 20° C. is at least 15% higher as compared to the same high density polyethylene composition without the ethylene/α-olefin interpolymer.
22. The composition of claim 18 wherein the ethylene/α-olefin interpolymer was prepared by using from about 50 ppm to about 300 ppm chain shuttling agent.
23. The composition of claim 22 wherein the chain shuttling agent is diethyl zinc.
24. The composition of claim 18 wherein the ethylene/α-olefin interpolymer has a density of form about 0.85 to about 0.93 g/cm 3 .
25. A fabricated article made from the composition of claim 18 .
26. A composition comprising:
A) a thermoplastic polymer composition; and
B) an impact modifying amount of an ethylene/α-olefin multi-block interpolymer polymerized in the presence of a catalyst composition comprising a first olefin polymerization catalyst having a first comonomer incorporation index a second olefin polymerization catalyst having a second comonomer incorporation index different than the first comonomer incorporation index, and a chain shuttling agent, wherein the ethylene/α-olefin interpolymer comprises at least 50 mole percent ethylene and:
(a) has at least one molecular fraction which elutes between 40° C. and 130° C. when fractionated using TREF, characterized in that the fraction has a block index of at least 0.5 and up to about 1; and
(b) has an average block index greater than zero and up to about 1.0 and a molecular weight distribution, Mw/Mn, greater than about 1.3; and
(c) has a storage modulus at 25° C., G′ (25° C.) and a storage modulus at 100° C., G′ (100° C.), wherein the ratio of G′ (25° C.) to G′ (100° C.) is in the range of about to about 9:1.
27. The composition of claim 26 wherein the notched Izod impact strength at 20° C. is at least 5% higher as compared to the same propylene polymer composition without the ethylene/α-olefin interpolymer.
28. The composition of claim 26 wherein the notched Izod impact strength at 20° C. is at least 10% higher as compared to the same propylene polymer composition without the ethylene/α-olefin interpolymer.
29. The composition of claim 26 wherein the notched Izod impact strength at 20° C. is at least 15% higher as compared to the same propylene polymer composition without the ethylene/α-olefin interpolymer.
30. A fabricated article made from the composition of claim 26 .