# US 10,766,985 B2 · Olefin polymer and preparation method thereof

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- Number: US 10,766,985 B2
- Document ID: US10766985B2
- Status: Granted
- Kind: B2
- Application number: 15/760,986
- Filed: 2017-02-22
- Published: 2018-09-06
- Granted: 2020-09-08
- Earliest claimed: 2016-02-24
- Assignees: LG Chem, Ltd.
- Applicants: LG Chem, Ltd.
- Inventors: Sol Cho; Sung Hyun Park; Oh Joo Kwon; Ki Soo Lee; Heon Yong Kwon; Dae Sik Hong; Myung Han Lee; Hyun Jee Kwon
- Web page: https://patentgrep.com/patent/US10766985B2

## CPC

- C08F 210/02: Ethene
- C08F 210/16: Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
- C08L 23/0815: {with aliphatic 1-olefins containing one carbon-to-carbon double bond}
- C08F 4/65916: {supported on a carrier, e.g. silica, MgCl2, polymer}
- C08F 4/65925: {two cyclopentadienyl rings being mutually non-bridged}
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)

## Abstract

The present invention relates to an olefin polymer and a preparation method thereof. The olefin polymer exhibits excellent mechanical strength and high processability, and thus is expected to be utilized as a material for various products. Particularly, the olefin polymer can be stably produced into films by a melt-blowing process and thus is expected to be usefully used as a material for products prepared by a melt-blowing process.

## Claims

### Claim 1

An olefin polymer,
wherein the olefin polymer has SF of 65 or more which is calculated by the following Equation 1:
SF=Mw/104+5/(Mw/105)*exp(ratio of increase in elongational viscosity) [Equation 1]
in the above equation 1, Mw means a weight average molecular weight,
the ratio of increase in elongational viscosity is a value in which the highest elongational viscosity value measured for the olefin polymer at Hencky strain rate of 1 s−1 at 170° C. using an elongational viscosity fixture attached to the ARES rheometer is divided by the elongational viscosity value of the extrapolated straight line at the time when the highest elongational viscosity value is obtained, wherein the extrapolated straight line is a straight line in which a straight line having the average slope of the section where the elongational viscosity increases steadily with time is extended to a section where the elongational viscosity increases sharply while maintaining the above average slope,
wherein a ratio of increase in elongational viscosity is 2.5 or more and 5.0 or less,
wherein a weight average molecular weight of the olefin polymer is 100,000 to 160,000 g/mol, and
wherein the olefin polymer is prepared by a method comprising: a step of polymerizing an olefin monomer in the presence of a hybrid supported catalyst comprising a carrier, a crosslinking type transition metal compound represented by the following Chemical Formula 1 that is supported on the carrier, and a non-crosslinking type transition metal compound represented by the following Chemical Formula 2 that is supported on the carrier:
wherein in the above Chemical Formulae 1 and 2, M1 and M2 are the same as or different from each other, and each independently represent Ti, Zr or Hf,
X1, X2, X3 and X4 are the same as or different from each other, and each independently represent any one of halogen, a nitro group, an amido group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkoxyalkyl group having 2 to 20 carbon atoms, a silyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a sulfonate group having 1 to 20 carbon atoms, and a sulfone group having 1 to 20 carbon atoms,
T is C, Si, Ge, Sn or Pb,
Q1 and Q2 are the same as or different from each other, and each independently represent any one of hydrogen, halogen, an alkyl group having 1 to 20 carbon atoms, a heterocycloalkyl group having 2 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkoxyalkyl group having 2 to 20 carbon atoms, a carboxylate having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a heteroaryl group having 5 to 20 carbon atoms,
R1 to R6 are the same as or different from each other, and each independently represent any one of hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkoxyalkyl group having 2 to 20 carbon atoms, a silyl group having 1 to 20 carbon atoms, a silylalkyl group having 1 to 20 carbon atoms, a silyloxyalkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms,
R7 to R14 are the same as or different from each other, and each independently represent any one of hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkoxyalkyl group having 2 to 20 carbon atoms, a silyl group having 1 to 20 carbon atoms, a silylalkyl group having 1 to 20 carbon atoms, a silyloxyalkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms, or one or more pairs of adjacent substituents of R7 to R14 are connected with each other to form a substituted or unsubstituted aliphatic or aromatic ring, and
R15 to R24 are the same as or different from each other, and each independently represent any one of hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkoxyalkyl group having 2 to 20 carbon atoms, a silyl group having 1 to 20 carbon atoms, a silylalkyl group having 1 to 20 carbon atoms, a silyloxyalkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms, or one or more pairs of adjacent substituents of R15 to R24 are connected with each other to form a substituted or unsubstituted aliphatic or aromatic ring.

### Claim 2 (depends on 1)

The olefin polymer of claim 1, wherein a density of the olefin polymer is 0.910 g/cm3 to 0.940 g/cm3.

### Claim 3 (depends on 1)

The olefin polymer of claim 1, wherein a number average molecular weight of the olefin polymer is 20,000 to 50,000 g/mol.

### Claim 4 (depends on 1)

The olefin polymer of claim 1, wherein a melt index of the olefin polymer is 0.5 g/10 min or more and less than 3 g/10 min, which is measured at a temperature of 190° C. under a load of 2.16 kg according to standard ASTM D1238.

### Claim 5 (depends on 1)

The olefin polymer of claim 1, wherein MFRR (21.6/2.16) of the olefin polymer is 20 or more and less than 40 in which a melt flow rate (MFR21.6) measured at a temperature of 230° C. under a load of 21.6 kg according to ISO 1133 is divided by a melt flow rate (MFR2.16) measured at a temperature of 230° C. under a load of 2.16 kg according to ISO 1133.

### Claim 6 (depends on 1)

The olefin polymer of claim 1, wherein the olefin polymer is a copolymer of ethylene and alpha olefin.

### Claim 7 (depends on 6)

The olefin polymer of claim 6, wherein the alpha olefin includes 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 mixtures thereof.

### Claim 8 (depends on 1)

A method for preparing the olefin polymer according to claim 1, which comprises a step of polymerizing an olefin monomer in the presence of a hybrid supported catalyst comprising a carrier, a crosslinking type transition metal compound represented by the following Chemical Formula 1 that is supported on the carrier, and a non-crosslinking type transition metal compound represented by the following Chemical Formula 2 that is supported on the carrier:
in the above formulae 1 and 2, M1 and M2 are the same as or different from each other, and each independently represent Ti, Zr or Hf,
X1, X2, X3 and X4 are the same as or different from each other, and each independently represent any one of halogen, a nitro group, an amido group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkoxyalkyl group having 2 to 20 carbon atoms, a silyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a sulfonate group having 1 to 20 carbon atoms, and a sulfone group having 1 to 20 carbon atoms,
T is C, Si, Ge, Sn or Pb,
Q1 and Q2 are the same as or different from each other, and each independently represent any one of hydrogen, halogen, an alkyl group having 1 to 20 carbon atoms, a heterocycloalkyl group having 2 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkoxyalkyl group having 2 to 20 carbon atoms, a carboxylate having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a heteroaryl group having 5 to 20 carbon atoms,
R1 to R6 are the same as or different from each other, and each independently represent any one of hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkoxyalkyl group having 2 to 20 carbon atoms, a silyl group having 1 to 20 carbon atoms, a silylalkyl group having 1 to 20 carbon atoms, a silyloxyalkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms,
R7 to R14 are the same as or different from each other, and each independently represent any one of hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkoxyalkyl group having 2 to 20 carbon atoms, a silyl group having 1 to 20 carbon atoms, a silylalkyl group having 1 to 20 carbon atoms, a silyloxyalkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms, or one or more pairs of adjacent substituents of R7 to R14 are connected with each other to form a substituted or unsubstituted aliphatic or aromatic ring, and
R15 to R24 are the same as or different from each other, and each independently represent any one of hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkoxyalkyl group having 2 to 20 carbon atoms, a silyl group having 1 to 20 carbon atoms, a silylalkyl group having 1 to 20 carbon atoms, a silyloxyalkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms, or one or more pairs of adjacent substituents of R15 to R24 are connected with each other to form a substituted or unsubstituted aliphatic or aromatic ring.

### Claim 9 (depends on 8)

The method for preparing the olefin polymer of claim 8, wherein R1 to R4 are each independently any one of hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an alkenyl group having 2 to 20 carbon atoms;
R5 and R6 are each independently any one of hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an alkenyl group having 2 to 20 carbon atoms;
R7 to R14 are each independently any one of hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an alkenyl group having 2 to 20 carbon atoms, or one or more pairs of adjacent substituents of R7 to R14 are connected with each other to form a substituted or unsubstituted aliphatic ring; and
Q1 to Q2 are each independently any one of an alkyl group having 1 to 20 carbon atoms and an aryl group having 6 to 20 carbon atoms.

### Claim 10 (depends on 8)

The method for preparing the olefin polymer of claim 8, wherein X1 to X4 are each independently any one of halogen, an alkyl group having 1 to 20 carbon atoms, and an alkoxy group having 1 to 20 carbon atoms.

### Claim 11 (depends on 8)

The method for preparing the olefin polymer of claim 8, wherein R15 to R24 are each independently any one of hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an alkenyl group having 2 to 20 carbon atoms, or one or more pairs of adjacent substituents of R15 to R24 are connected with each other to form a substituted or unsubstituted aliphatic ring.

### Claim 12 (depends on 8)

The method for preparing the olefin polymer of claim 8, wherein the crosslinking type transition metal compound represented by Chemical Formula 1 is any one of compounds represented by Chemical Formulas 3 and 4 below:
in the above formulae 3 and 4, R25 and R26 are the same as or different from each other, and each independently represent any one of hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkoxyalkyl group having 2 to 20 carbon atoms, an alkylsilyl group having 1 to 20 carbon atoms, a silylalkyl group having 1 to 20 carbon atoms, an alkoxysilyl group having 1 to 20 carbon atoms, a silyloxyalkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, and an arylalkyl group having 7 to 20 carbon atoms, and
l is an integer between 0 and 5.

### Claim 13 (depends on 8)

The method for preparing the olefin polymer of claim 8, wherein the non-crosslinking type transition metal compound represented by Formula 2 is any one of compounds represented by Chemical Formulas 5 and 6 below:
in the above formulae 5 and 6, R27 to R30 are the same as or different from each other, and each independently represent any one of hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkoxyalkyl group having 2 to 20 carbon atoms, an alkylsilyl group having 1 to 20 carbon atoms, a silylalkyl group having 1 to 20 carbon atoms, an alkoxysilyl group having 1 to 20 carbon atoms, a silyloxyalkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, and an arylalkyl group having 7 to 20 carbon atoms.

### Claim 14 (depends on 8)

The method for preparing the olefin polymer of claim 8, wherein it further includes at least one cocatalyst selected from the group consisting of compounds represented by Chemical Formulas 7 to 9 below:
R31—[Al(R32)—O]n—R33 [Chemical Formula 7]
in the above formula 7,
R31, R32 and R33 are each independently any one of hydrogen, halogen, a hydrocarbyl group having 1 to 20 carbon atoms and a hydrocarbyl group having 1 to 20 carbon atoms substituted with halogen, and
n is an integer of 2 or more,
D(R34)3 [Chemical Formula 8]
in the above formula 8,
D is aluminum or boron,
each R34 is independently any one of halogen, a hydrocarbyl group having 1 to 20 carbon atoms, and a hydrocarbyl group having 1 to 20 carbon atoms substituted with halogen,
[L-H]+[Z(A)4]−or [L]+[Z(A)4]− [Chemical Formula 9]
in the above formula 9,
L is a neutral or cationic Lewis base, H is a hydrogen atom,
Z is a Group 13 element, and A is each independently any of a hydrocarbyl group having 1 to 20 carbon atoms; a hydrocarbyloxy group having 1 to 20 carbon atoms; and substituents in which at least one hydrogen atom of the above substituents is substituted with at least one substituent of halogen, a hydrocarbyloxy group having 1 to 20 carbon atoms and a hydrocarbylsilyl group having 1 to 20 carbon atoms.

### Claim 15 (depends on 8)

The method for preparing the olefin polymer of claim 8, wherein the carrier is silica, alumina, magnesia, or a mixture thereof.

### Claim 16 (depends on 8)

The method for preparing the olefin polymer of claim 8, wherein the crosslinking type transition metal compound represented by Chemical Formula 1 and the non-crosslinking type transition metal compound represented by Chemical Formula 2 is contained in a weight ratio of 50:1 to 1:1.

### Claim 17 (depends on 8)

The method for preparing the olefin polymer of claim 8, wherein ethylene and an alpha olefin are used as the olefin monomer.

### Claim 18 (depends on 17)

The method for preparing the olefin polymer of claim 17, wherein 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 mixtures thereof are used as the alpha olefin.