# US 7,612,148 B2 · Hydrogenation catalyst composition and method for hydrogenation of conjugated diene polymer

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- Number: US 7,612,148 B2
- Document ID: US7612148B2
- Status: Granted
- Kind: B2
- Application number: 12/002,812
- Filed: 2007-12-19
- Published: 2008-06-19
- Granted: 2009-11-03
- Earliest claimed: 2006-12-19
- Assignees: TSRC Corporation
- Inventors: Chin-Kuang Tsai; Chien-Cheng Chen; Jung-Sheng Pan
- Web page: https://patentgrep.com/patent/US7612148B2

## CPC

- B01J 31/2295: {Cyclic compounds, e.g. cyclopentadienyls}
- B01J 31/0259: {comprising phosphorous acid (-ester) groups ((RO)P(OR')2) or the isomeric phosphonic acid (-ester) groups (R(R'O)2P=O), i.e. R= C, R'= C, H}
- B01J 31/0261: {comprising phosphonous acid (-ester) groups (RP(OR')2) or the isomeric phosphinic acid (-ester) groups (R2(R'O)P=O), i.e. R= C, R'= C, H}
- B01J 31/143: {of aluminium}
- C08C 19/02: Hydrogenation
- C08F 8/04: Reduction, e.g. hydrogenation
- B01J 2231/645: of C=C or C-C triple bonds
- B01J 2531/46: Titanium
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- C08C: TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS

## Abstract

A method for hydrogenation of a conjugated diene polymer is provided. The conjugated diene polymer in an inert organic solvent is brought into contact with hydrogen in the presence of a hydrogenation catalyst composition to selectively hydrogenate the unsaturated double bonds in the conjugated diene units of the conjugated diene polymer. The hydrogenation catalyst composition includes: (a) a titanium compound; (b) a compound represented by formula (II) or formula (III): wherein R is C1-C12 alkyl, C3-C12 cycloalkyl, aryl or alkyl aryl, M is C1-C12 alkyl, C1-C12 alkoxy, aryl, alkyl aryl, phenoxy or hydroxyl, and n=1˜3; and (c) a alkylaluminum compound.

## Claims

### Claim 1

A catalyst composition for hydrogenating a polymer having a conjugated diene, comprising:
(a) a first composition having one of a titanium compound of a formula (I):
wherein:
R1 and R2 are ones selected from the group consisting of hydrogen, halogen, C1˜C8 alkyl, C1˜C8 alkoxy, C6˜C12 cycloalkyl, phenyl, phenoxy, C7˜C10 arylalkoxy, C7˜C10 arylalkyl, carboxy, —CH2P(phenyl)2, —CH2Si(C1˜C5 alkyl)3 and —P(phenyl)2; and
Cp* is one selected from the group consisting of cyclopendienyl, fluorenyl, indenyl and derivatives thereof,
(b) a second composition having one of a first compound of a formula (II) and a second compound of a formula (III):
wherein R is one selected from the group consisting of C1˜C12 alkyl, C3˜C12 cycloalkyl, aryl, and alkyl aryl, M is one selected from the group consisting of C1˜C12 alkyl, C1˜C12 alkoxy, aryl, alkyl aryl, phenoxy and hydroxyl and n=1 to 3; and
(c) a third composition having an alkylaluminum compound of a formula (IV):
wherein the R4, R5 and R6 are ones selected from the group consisting of C1˜C12 alkyl, C6˜C12 aryl, hydrogen and halogen.

### Claim 2 (depends on 1)

The catalyst composition as claimed in claim 1, wherein the first composition is one selected from the group consisting of a bis(cyclopentadienyl)titanium halide, bis(cyclopentadienyl)titanium, bifluorenyl titanium halide, biindenyl titanium halide, bifluorenyl titanium, biindenyl titanium and a derivative thereof.

### Claim 3 (depends on 1)

The catalyst composition as claimed in claim 1, wherein the second composition is a compound of the formula (II) and R is one selected from the group of C1˜C12 alkyl, C1˜C12 cycloalkyl, aryl and alkyl aryl, where n=3.

### Claim 4 (depends on 1)

The catalyst composition as claimed in claim 1, wherein the second composition is a compound of the formula (II), R is one selected from the group consisting of C1˜C12 alkyl, and M is one selected from the group consisting of C1˜C12 alkyl, alkoxy, aryl, alkyl aryl, phenoxy and hydroxyl, where n=2.

### Claim 5 (depends on 1)

The catalyst composition as claimed in claim 1, wherein the second composition is a compound of the formula (II), R is one of aryl and alkyl aryl, and M is one selected from the group consisting of C1˜C12 alkyl, alkoxy, aryl, alkyl aryl, phenoxy and hydroxyl.

### Claim 6 (depends on 1)

The catalyst composition as claimed in claim 1, wherein the second composition is a compound of the formula (III) and R is one selected from the group consisting of C1˜C12 alkyl, C3˜C12 cycloalkyl, aryl and alkyl aryl, where n=3.

### Claim 7 (depends on 1)

The catalyst composition as claimed in claim 1, wherein the second composition is a compound of the formula (III), R is one selected from the group consisting of C1˜C12 alkyl, and M is one selected from the group consisting of C1˜C12 alkyl, alkoxy, aryl, alkyl aryl and phenoxy.

### Claim 8 (depends on 1)

The catalyst composition as claimed in claim 1, wherein the third composition is one selected from the group consisting of trimethyl aluminum, triethyl aluminum, tri-n-propyl aluminum, triisopropyl aluminum, tributyl aluminum, tri(sec-butyl) aluminum, tri(isobutyl)aluminum, tri(n-pentyl)aluminum, tri(isopentyl)aluminum, tri(n-hexyl) aluminum, tri(isohexyl)aluminum, tri(1-methylpentyl)aluminum, tri(2,5-dimethyloctyl) aluminum, tri(2,6-dimethyloctyl)aluminum, triphenyl aluminum, diethyl aluminum chloride, ethyl aluminum dichloride, tripropyl aluminum chloride, dibutyl aluminum chloride, diisobutyl aluminum chloride, butyl aluminum dichloride and compositions thereof.

### Claim 9 (depends on 1)

The catalyst composition as claimed in claim 1, wherein polymer is obtained through one of an anionic polymerization, a free radical polymerization, a coordination polymerization and a cationic polymerization.

### Claim 10 (depends on 1)

The catalyst composition as claimed in claim 1, wherein the first composition, the second composition and the third composition are respectively added into a solution of the polymer at the same time.

### Claim 11 (depends on 1)

The catalyst composition as claimed in claim 1, wherein the first composition, the second composition and the third composition are respectively added into a solution of the polymer at random.

### Claim 12 (depends on 1)

The catalyst composition as claimed in claim 1, wherein the content of the first composition is ranged from 0.001 to 50 millimoles per 100 g of the polymer.

### Claim 13 (depends on 1)

The catalyst composition as claimed in claim 1, wherein a molar ratio of the second composition to the first composition is from 0.1 to 50.

### Claim 14 (depends on 1)

The catalyst composition as claimed in claim 1, wherein a molar ratio of the third composition to the first composition is from 0.1 to 50.

### Claim 15 (depends on 1)

The catalyst composition as claimed in claim 1, wherein one unit of the polymer has a molecular weight of 1,000 to 1,000,000.

### Claim 16 (depends on 1)

The catalyst composition as claimed in claim 1, wherein the hydrogenation catalyst composition is applied to one of a conjugated diene homopolymer and a copolymer of a vinyl aromatic hydrocarbon and the conjugated diene.

### Claim 17 (depends on 16)

The catalyst composition as claimed in claim 16, wherein the copolymer is one selected from the group consisting of styrene-butadiene copolymer, styrene-isoprene copolymer and styrene-(butadiene/isoprene) copolymer.

### Claim 18 (depends on 17)

The catalyst composition as claimed in claim 17, an arrangement of the copolymer is one selected from the group consisting of a block arrangement, a random arrangement and a taper arrangement.

### Claim 19 (depends on 17)

The catalyst composition as claimed in claim 17, the styrene-butadiene copolymer is hydrogenated into a styrene-ethylene-butylene-styrene (SEBS) copolymer.

### Claim 20 (depends on 17)

The catalyst composition as claimed in claim 17, the styrene-isoprene copolymer is hydrogenated into a styrene-ethylene-propylene-styrene (SEPS) copolymer.

### Claim 21 (depends on 17)

The catalyst composition as claimed in claim 17, the styrene-(butadiene/isoprene) copolymer is hydrogenated into a styrene-ethylene-ethylene-propylene-styrene (SEEPS) copolymer.

### Claim 22 (depends on 1)

A method for hydrogenating a polymer having a conjugated diene, wherein the polymer is one of a conjugated diene homopolymer and a conjugated diene copolymer, comprising steps of:
dissolving the polymer into an inert organic solvent; and
hydrogenating the dissolved polymer in a presence of a catalyst composition comprising the first, second and third composition as claimed in claim 1, so as to selectively hydrogenate an unsaturated double bond in the polymer.

### Claim 23 (depends on 22)

The method as claimed in claim 22, wherein the step of hydrogenating is performed at a temperature ranged from 0° C. to 200° C. and at a hydrogen pressure ranged from 1 to 90 kg/cm2.

### Claim 24 (depends on 22)

The method as claimed in claim 22, wherein at least 50% of the unsaturated double bond in the polymer are hydrogenated.

### Claim 25 (depends on 22)

The method as claimed in claim 22, wherein a percentage of an aromatic ring double bond in the vinyl aromatic hydrocarbon being hydrogenated is under 10%.