Thermoplastic resin composition

Patent metadata

Field	Value
Publication number	US-12441877-B2
Application number	US-202118018340-A
Country	US
Kind code	B2
Filing date	Aug 6, 2021
Priority date	Aug 7, 2020
Publication date	Oct 14, 2025
Grant date	Oct 14, 2025

Abstract

The present invention relates to a thermoplastic resin composition including a polyolefin-polystyrene-based multi-block copolymer having a structure in which a polystyrene chain is attached to both ends of a polypropylene and polyolefin chain, and the thermoplastic resin composition according to the present invention exhibits high fluidity properties as well as soft feel and high restoring force.

First claim

The invention claimed is:

1. A thermoplastic resin composition comprising:
(1) polypropylene; and
(2) a polyolefin-polystyrene-based multi-block copolymer satisfying the following conditions (a) and (b) in the temperature range of −80 to 40° C. in a graph showing an amount of change in loss tangent (tan δ) (y axis) according to temperature (x-axis) obtained by dynamic mechanical analysis (DMA):
(a) the height of a tan δ peak is 0.45 to 0.60; and
(b) the half-width of a tan δ peak is 22.5 to 30.0° C.

2. The thermoplastic resin composition of claim 1 , wherein under the condition (a), the tan δ peak appears as one peak in the range of −50 to −30° C.

3. The thermoplastic resin composition of claim 1 , wherein under the condition (b), the half-width of a tan δ peak is 23.0 to 29.0° C.

4. The thermoplastic resin composition of claim 1 , wherein the polyolefin-polystyrene-based multi-block copolymer further satisfies the following (c) and (d) conditions:
(c) the tan δ value at −10 to −30° C. is 0.10 to 0.30; and
(d) the tan δ value at 15 to 30° C. is 0.05 to 0.50.

5. The thermoplastic resin composition of claim 4 , wherein the polyolefin-polystyrene-based multi-block copolymer has a storage modulus value E′ of 1 to 200 MPa and a loss modulus value E″ of 1 to 100 MPa at −10 to −30° C.

6. The thermoplastic resin composition of claim 4 , wherein the polyolefin-polystyrene-based multi-block copolymer has a storage modulus value E′ of 0.1 to 50 MPa and a loss modulus value E″ of 0.01 to 5 MPa at 15 to 30° C.

7. The thermoplastic resin composition of claim 1 , wherein the polyolefin-polystyrene-based multi-block copolymer has a weight average molecular weight of 40,000 g/mol to 300,000 g/mol.

8. The thermoplastic resin composition of claim 1 , wherein the polyolefin-polystyrene-based multi-block copolymer has a molecular weight distribution of 1.0 to 3.0.

9. The thermoplastic resin composition of claim 1 , wherein the polyolefin-polystyrene-based multi-block copolymer is one or more selected from the group consisting of a polystyrene-poly(ethylene-co-propylene)-polystyrene block copolymer, a polystyrene-poly(ethylene-co-1-butene)-polystyrene block copolymer, a polystyrene-poly(ethylene-co-1-pentene)-polystyrene block copolymer, a polystyrene-poly(ethylene-co-1-hexene)-polystyrene block copolymer, a polystyrene-poly(ethylene-co-1-heptene)-polystyrene block copolymer, and a polystyrene-poly(ethylene-co-1-octene)-polystyrene block copolymer.

10. The thermoplastic resin composition of claim 1 , wherein the polyolefin-polystyrene-based multi-block copolymer comprises a polystyrene-based block in an amount of 10 wt % to 30 wt %.

11. The thermoplastic resin composition of claim 1 , wherein the polyolefin-polystyrene-based multi-block copolymer is prepared without a hydrogenation reaction for a double bond in a copolymer main chain.

12. The thermoplastic resin composition of claim 1 , wherein the (1) polypropylene and the (2) polyolefin-polystyrene-based multi-block copolymer have a weight ratio of 10:90 to 90:10.

13. The thermoplastic resin composition of claim 1 , wherein the thermoplastic resin composition is a thermoplastic resin composition satisfying the physical properties of the following (A) to (D):
(A) Shore A hardness of 1 to 90,
(B) Permanent compression set of 0 to 80%,
(C) Melt flow rate (MFR, 230° C. and 2.16 kg) of 0.1 to 300 g/10 min, and
(D) Melt flow rate (MFR, 230° C. and 5 kg) of 0.1 to 500 g/10 min.

14. The thermoplastic resin composition of claim 1 , wherein a polystyrene chain is attached to both ends of polypropylene and polyolefin chains.

15. The thermoplastic resin composition of claim 1 , wherein the polypropylene is a polypropylene homopolymer, or a copolymer of propylene and an alpha-olefin monomer.

16. The thermoplastic resin composition of claim 1 , wherein the polyolefin-polystyrene-based multi-block copolymer is prepared by a process comprising:
(S1) forming a polyolefin block by polymerizing an olefin-based monomer using an organozinc compound as a chain transfer agent in the presence of a catalyst composition including a transition metal compound represented by Formula 1 below, and
(S2) forming a polystyrene block by anionic polymerization of the polyolefin block and a styrene-based monomer in the presence of an alkyl lithium compound including silicon atom and a triamine compound,

in Formula 1 above,
R 1 to R 11 are each independently hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkoxy group having 7 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, an alkylsilyl group having 1 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms,
two or more of R 1 to R 11 which are adjacent to each other are optionally connected to each other to form an aliphatic ring having 3 to 20 carbon atoms or an aromatic ring having 6 to 20 carbon atoms, and
X 1 and X 2 are each independently hydrogen, halogen, a hydroxyl group, an amino group, a thio group, a silyl group, a cyano group, a nitro group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, a heteroaryl group having 5 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an alkylamino group having 1 to 20 carbon atoms, an arylamino group having 6 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, an arylthio group having 6 to 20 carbon atoms, an alkylsilyl group having 1 to 20 carbon atoms, or an arylsilyl group having 6 to 20 carbon atoms.

17. The thermoplastic resin composition of claim 16 , wherein the hafnium compound is represented by any one among Formula 1-1 to Formula 1-5:

18. The thermoplastic resin composition of claim 16 , wherein the organozinc compound is a compound represented by Formula 4 below:

in Formula 4 above,
A is alkylene having 1 to 20 carbon atoms, arylene having 6 to 20 carbon atoms, or arylene having 6 to 20 carbon atoms substituted with halogen, alkyl having 1 to 12 carbon atoms, cycloalkyl having 3 to 12 carbon atoms, alkoxy having 1 to 8 carbon atoms, or aryl having 6 to 12 carbon atoms, and
B is arylene having 6 to 12 carbon atoms substituted with alkenyl having 2 to 12 carbon atoms.

19. The thermoplastic resin composition of claim 16 , wherein the olefin monomer used in Step (S1) is ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, and 1-eicosene, or a mixture thereof.

20. The thermoplastic resin composition of claim 16 , wherein the styrene-based monomer used in Step (S2) comprises ethylene substituted with an aryl group having 6 to 2

Assignees

• Lg Chemical Ltd

Inventors

• Kim Tae Hee
• Lee Ki Soo
• Shin Eun Ji
• Sa Seok Pil
• Im Seul Ki
• Lee Hyun Mo
• Park Ji Hyun
• Kim Yun Kon
• Yu Seung Jung

Classifications

• C08L23/14

  Copolymers of propene (C08L23/16 takes precedence) · CPC title

• C08F297/06 Primary

  using a catalyst of the coordination type · CPC title

• C08F210/16

  Copolymers of ethene with alpha-alkenes, e.g. EP rubbers · CPC title

• C08F2/38

  Polymerisation using regulators, e.g. chain terminating agents {, e.g. telomerisation} · CPC title

• C08F2410/01

  Additive used together with the catalyst, excluding compounds containing Al or B · CPC title