# Patent

## Title
Heterogeneous catalyst and method for selectively hydrogenating copolymer utilizing the same

## Abstract

Disclosed is a method for selectively hydrogenating a copolymer, including contacting a heterogeneous catalyst with a copolymer to process hydrogenation. The copolymer includes aromatic rings and double bonds, and the double bonds are hydrogenated, and the aromatic rings are substantially not hydrogenated. The heterogeneous catalyst includes a metal catalyst such as platinum, palladium, platinum-iridium alloy, or platinum-rhenium alloy formed on a porous support. The hydrogenation is processed at a temperature of 40° C. to 150° C. under a hydrogen pressure of 10 kg/cm2 to 50 kg/cm2.

## Background
CROSS REFERENCE TO RELATED APPLICATIONS
The application is based on, and claims priority from, Taiwan Application Serial Number 10216217, filed on Jul. 23, 2013, the disclosure of which is hereby incorporated by reference herein in its entirety
TECHNICAL FIELD
The technical field relates to a heterogeneous catalyst, and in particular, relates to selective hydrogenate copolymers utilizing the same.
BACKGROUND
SBS and SIS belong to a styrene-based thermoplastic elastomer (also named styrenic block copolymers, SBCs) with properties of thermoplastic plastics and rubbers. For example, the SBCs are similar to rubber at room temperature due to their softness, toughness, and flexibility. Furthermore, the SBCs at high temperature are flowable and moldable. As with natural rubber and the synthetic rubber, the SBCs are classified as a third generation rubber. In the thermoplastic elastomer field, the SBCs' properties are mostly similar to that of rubber. In addition, the SBCs are the greatest yield thermoplastic elastomers in global. In recent years, SBCs include four types: styrene-butadiene-styrene block copolymer (SBS), styrene-isopentadiene-styrene block copolymer (SIS), styrene-ethylene-butylene-styrene block copolymer (SEBS), and styrene-ethylene-propylene-styrene block copolymer (SEPS). The SEBS and the SEPS are a hydrogenated SBS and SIS, respectively. The SEBS and the SEPS with excellent properties have a higher price (2 to 4 times) than that of the SBS and the SIS. The SBS is the most commonly SBC that is mass produced (over 70%), has the lowest-cost of the SBCs, and the more widely used product among the SBCs. The SBS is a triblock copolymer polymerized of styrene and butadiene. The SBS sir simultaneously has plastic and rubber properties, and is the greatest yield thermoplastic elastomer due to its excellent chemical resistance, excellent tensile strength, high surface friction coefficient, excellent low temperature properties, excellent electrical properties, and excellent processibility.
The polybutadiene segment of the SBS and the polyisopentadiene diene segment of the SIS include carbon-carbon double bonds. As such, the SBS and SIS have disadvantages such as low thermal resistance and low climate resistance (e.g. ozone resistance, UV resistance, and oxygen resistance). The disadvantages can be overcome by hydrogenating the carbon-carbon double bonds of the polybutadiene segment and the polyisopentadiene segment, thereby forming the SEBS (see Formula 1) and the SEPS (see Formula 2), respectively. The hydrogenated products SEBS and SEPS can be applied as engineering and medical materials due to better climate resistance and properties.




Accordingly, a novel method and corresponding catalyst for forming the SEBS and the SEPS is called for, e.g. selectively hydrogenating the carbon-carbon double bonding of the SBS and the SIS without hydrogenating the aromatic ring of the SBS and the SIS.
SUMMARY
One embodiment of the disclosure provides a method for selectively hydrogenating a copolymer, comprising: contacting a heterogeneous catalyst with a copolymer including aromatic rings and double bonds to process a hydrogenation at a temperature of 40° C. to 150° C. under a hydrogen pressure of 10 kg/cm2 to 50 kg/cm2 for hydrogenating the double bonds and substantially not hydrogenating the aromatic rings, wherein the heterogeneous catalyst comprises a metal catalyst formed on a porous support, and the metal catalyst comprises platinum, palladium, platinum-rhenium alloy, or platinum-iridium alloy.
One embodiment of the disclosure provides a heterogeneous catalyst, including a metal catalyst formed on a porous support, wherein the metal catalyst comprises platinum, palladium, platinum-rhenium alloy, or platinum-iridium alloy, and the porous support comprises titanium oxide, aluminum oxide, zirconium oxide, or silicon oxide.
A detailed description is given in the following embodiments.


DETAILED DESCRIPTION
In the following detailed description, for purposes of explanation, numerous specific details are set forth in order to provide a thorough understanding of the disclosed embodiments. It will be apparent, however, that one or more embodiments may be practiced without these specific details. In other instances, well-known structures and devices are schematically shown in order to simplify the drawing.
One embodiment of the disclosure provides a method for selectively hydrogenating a copolymer. First, the copolymer and a heterogeneous catalyst are contacted to process hydrogenation. The heterogeneous catalyst is a metal catalyst such as platinum, palladium, platinum-rhenium alloy, or platinum-iridium alloy formed on a porous support such as titanium oxide, aluminum oxide, zirconium oxide, or silicon oxide. In one embodiment, the platinum and the iridium (or rhenium) had a weight ratio of 5:0.1 to 1:5. A catalyst with an overly low amount of platinum has low activity, thereby reducing the hydrogenation yield. The porous support has a specific surface area of greater than or equal to 40 m2/g. On the basis of the total weight (100 wt %) of the porous support and the metal catalyst of the heterogeneous catalyst, the heterogeneous catalyst contains 0.2 wt % to 10 wt % of the metal catalyst. Alternatively, the heterogeneous catalyst contains 1 wt % to 5 wt % of the metal catalyst. A catalyst with an overly low amount of the metal catalyst has low activity, thereby reducing the hydrogenation yield. A catalyst with an overly high amount of the metal catalyst has a high cost, thereby lacking economic benefits.
The heterogeneous palladium catalyst can be formed by an incipient wetness method. For example, palladium acetate is dissolved in water, and the water volume is equal to the pore volume of the porous support. A dried porous support is soaked in the aqueous solution, and the water thereof is then removed, and the palladium salt adsorbed on the porous support is then heated to 120° C. to directly form palladium on the porous support, e.g. Pd/TiO2, Pd/SiO2, PdZrO2, or Pd/Al2O3.
The heterogeneous platinum catalyst can be formed by an incipient wetness method. For example, platinum salt such as H2PtCl6 is dissolved in water, and the water volume is equal to the pore volume of the porous support. A dried porous support is soaked in the aqueous solution, and the water thereof is then removed, and the platinum salt adsorbed on the porous support is then heated to 120° C. to directly form platinum on the porous support, e.g. Pt/TiO2, Pt/SiO2, Pt/ZrO2, or Pt/Al2O3.
The heterogeneous platinum-iridium catalyst can be formed by an incipient wetness method. For example, an appropriate ratio of platinum salt (such as H2PtCl6) and iridium salt (such as IrCl3) are dissolved in water, and the water volume is equal to the pore volume of the porous support. A dried porous support s soaked in the aqueous solution, and the water thereof is then removed, and the metal salt adsorbed on the porous support is then heated and hydrogenated, and the chemically reduced metal salt is passivated by air to form a platinum-iridium alloy on the porous support, e.g. Pt—Ir/TiO2, Pt—Ir/SiO2, Pt—Ir/ZrO2, or Pt—Ir/Al2O3.
The heterogeneous platinum-rhenium catalyst can be formed by an incipient wetness method. For example, platinum salt such as (H2PtCl6) and rhenium salt (such as HReCl4 or HReO4) are dissolved in water, and the water volume is equal to the pore volume of the porous support. A dried porous support is soaked in the aqueous solution, and the water thereof is then removed, and the metal salt adsorbed on the porous support is then heated and hydrogenated, and the chemically reduced metal salt is passivated by air to form a platinum-rhenium alloy on the porous support, e.g. Pt—Re/TiO2, Pt—Re/SiO2, Pt—Re/ZrO2, or Pt—Re/Al2O3.
In one embodiment, the copolymer can be polymerized of polyenic monomer and vinyl aromatic monomer. The polyenic monomer can be butadiene, isopentadiene, other monomers having at least two carbon-carbon double bonds, or combinations thereof. The vinyl aromatic monomer can be styrene, α-methylstyrene, other vinyl aromatic monomers, or combinations thereof. The copolymer includes an aromatic ring and carbon-carbon double bond, such as the SBS (copolymerized of styrene and butadiene) or the SIS (polymerized of styrene and isopentadiene).
In one embodiment, hydrogenation is performed at a temperature of 40° C. to 150° C. under a hydrogen pressure of 10 kg/cm2 50 kg/cm2. In another embodiment, hydrogenation is performed at a temperature of 70° C. to 120° C. under a hydrogen pressure of 30 kg/cm2 to 40 kg/cm2. Hydrogenation cannot be performed at an overly low temperature and/or under an overly low hydrogen pressure. Hydrogenation not only hydrogenates the carbon-carbon double bonds of the copolymer, but also hydrogenates the aromatic rings of the copolymer at an overly high temperature and/or under an overly high hydrogen pressure.
Accordingly, the disclosed heterogeneous catalyst may selectively hydrogenate the carbon-carbon double bonds of the copolymer, and substantially not hydrogenate the aromatic rings of the copolymer. For example, only less than 5% of the aromatic rings in the copolymer are hydrogenated, but more than 97% of the carbon-carbon double bonds in the copolymer are hydrogenated.
Below exemplary embodiments will be described in detail with reference to the accompanying drawings so as to be easily realized by a person having ordinary knowledge in the art. The inventive concept may be embodied in various forms without being limited to the exemplary embodiments set forth herein. Descriptions of well-known parts are omitted for clarity, and like reference numerals refer to like elements throughout.
EXAMPLES
Preparation Example 1
9.55 g of SiO2 (Q50, commercially available from Fuji silysia) serving as a porous support was put into an oven at 110° C. to be dried overnight, and then put into a round bottom bottle. 7.35 g of H2PtCl6 and 1.55 g of IrCl3 were dissolved in water. The aqueous solution was added to the round bottom bottle and stood for 2 hours, whereby the metal salts were adsorbed on the porous support. The mixture in the round bottom bottle was heated to 110° C. and vacuumed to remove water thereof to obtain a dried powder. The dried powder was put into a glass tube, 2 vol % of hydrogen was then conducted through the glass tube, and the dried powder was heated to 200° C. and left at 200° C. for 4 hours. As a result the metal salts adsorbed on the porous support were chemically reduced. The heated powder was cooled to room temperature, and air was then conducted through the glass tube to passivate the catalyst surface. Therefore, a 3.5 wt % Pt-1 wt % Ir/95.5 wt % SiO2 catalyst was completed.
Preparation Example 2
9.8 g of SiO2 (Q50, commercially available from Fuji silysia) serving as a porous support was put into an oven at 110° C. to be dried overnight, and then put into a round bottom bottle, 4.22 g of palladium acetate was dissolved in water. The aqueous solution was added to the round bottom bottle and stood for 2 hours, whereby the metal salt was adsorbed on the porous support. The mixture in the round bottom bottle was heated to 110° C. and vacuumed to remove water thereof to obtain a dried powder, 2 wt % Pd/98 wt % SiO2 catalyst.
Preparation Example 3
9.8 g of ZrO2 (XZ16075, commercially available from Norpro) serving as a porous support was put into an oven at 110° C. to be dried overnight, and then put into a round bottom bottle. 4.22 g of palladium acetate was dissolved in water. The aqueous solution was added to the round bottom bottle and stood for 2 hours, whereby the metal salt was adsorbed on the porous support. The mixture in the round bottom bottle was heated to 110° C. and vacuumed to remove water thereof to obtain a dried powder, 2 wt % Pd/198 wt % ZrO2 catalyst.
Preparation Example 4
9.8 g of Al2O3 (IS0600, commercially available from UOP) serving as a porous support was put into an oven at 110° C. to be dried overnight, and then put into a round bottom bottle. 4.22 g of palladium acetate was dissolved in water. The aqueous solution was added to the round bottom bottle and stood for 2 hours, whereby the metal salt was adsorbed on the porous support. The mixture in the round bottom bottle was heated to 110° C. and vacuumed to remove water thereof to obtain a dried powder, 2 wt % Pd/98 wt % Al2O3 catalyst.
Preparation Example 5
9.55 g of TiO2 (ST31119 commercially available from Norpro) serving as a porous support was put into an oven at 110° C. to be dried overnight, and then put into a round bottom bottle. 7.35 g of H2PtCl6 and 1.35 g of HReO4 were dissolved in water. The aqueous solution was added to the round bottom bottle and stood for 2 hours, whereby the metal salts were adsorbed on the porous support. The mixture in the round bottom bottle was heated to 110° C. and vacuumed to remove water thereof to obtain a dried powder. The dried powder was put into a glass tube, 2 vol % of hydrogen was then conducted through the glass tube, and the dried powder was heated to 200° C. and left at 200° C. for 4 hours. As a result, the metal salts adsorbed on the porous support were chemically reduced. The heated powder was cooled to room temperature, and air was then conducted through the glass tube to passivate the catalyst surface. Therefore, a 3.5 wt % Pt-1 wt % Re/95.5 wt % TiO2 catalyst was completed.
Preparation Example 6
9.65 g of SiO2 (Q50, commercially available from Fuji silysia) serving as a porous support was put into an oven at 110° C. to be dried overnight, and then put into a round bottoms bottle. 7.35 g of H2PtCl6 was dissolved in water. The aqueous solution was added to the round bottom bottle and stood for 2 hours, whereby the metal salt was adsorbed on the porous support, The mixture in the round bottom bottle was heated to 110° C. and vacuumed to remove water thereof to obtain a dried powder. The dried powder was put into a glass tube, 2 vol % of hydrogen was then conducted through the glass tube, and the dried powder was heated to 200° C. and left at 200° C. for 4 hours. As a result, the metal salt adsorbed on the porous support was chemically reduced. The heated powder was cooled to room temperature, and air was then conducted through the glass tube to passivate the catalyst surface. Therefore, a 3.5 wt % Pt/96.5 wt % SiO2 catalyst was completed.
Preparation Example 7
9.55 g of SiO2 (Q50, commercially available from Fuji silysia) serving as a porous support was put into an oven at 110° C. to be dried overnight, and then put into a round bottom bottle. 7.35 g of H2PtCl6 and 1.35 g of HReO4 were dissolved in water. The aqueous solution was added to the round bottom bottle and stood for 2 hours, whereby the metal salts were adsorbed on the porous support. The mixture in the round bottom bottle was heated to 110° C. and vacuumed to remove water thereof to obtain a dried powder. The dried powder was put into a glass tube, 2 vol % of hydrogen was then conducted through the glass tube, and the dried powder was heated to 200° C. and left at 200° C. for 4 hours. As a result the metal salts adsorbed on the porous support were chemically reduced. The heated powder was cooled to room temperature, and air was then conducted through the glass tube to passivate the catalyst surface. Therefore, a 3.5 wt % Pt-1 wt % Re/95.5 wt % SiO2 catalyst was completed.
Example 1
9 g of the styrene-isopentadiene-styrene block copolymer (SIS, Kraton D1161) was dissolved in 111 g of cyclohexane to forma SIS solution (7.5 wt %). The SIS solution was put into a reaction vessel. 1.8 g of the Pt—Ir/SiO2 catalyst prepared in Preparation Example 1 was added to the reaction vessel. The reaction vessel was sealed, and hydrogen of 40 kg/cm2 was conducted to the reaction vessel. The reaction vessel was heated to 120° C. to process the hydrogenation for 2.6 hours, and the heating process was then stopped. The conversion ratio of the hydrogenation was measured by FT-IR and UV-VIS spectrometers, as tabulated in Table 1.
Example 2
9 g of the SIS (Kraton D1161) was dissolved in 111 g of cyclohexane to form a SIS solution (7.5 wt %). The SIS solution was put into a reaction vessel. 1.8 g of the Pd/SiO2 catalyst prepared in Preparation Example 2 was added to the reaction vessel. The reaction vessel was sealed, and hydrogen of 40 kg/cm2 was conducted to the reaction vessel. The reaction vessel was heated to 110° C. to process the hydrogenation for 4.2 hours, and the heating process was then stopped. The conversion ratio of the hydrogenation was measured by FT-IR and UV-VIS spectrometers, as tabulated in Table 1.
Example 3
9 g of the SIS (Kraton D1161) was dissolved 111 g of cyclohexane to form a SIS solution (7.5 wt %). The SIS solution was put into a reaction vessel. 1.8 g of the Pd/ZrO2 catalyst prepared in Preparation Example 3 was added to the reaction vessel. The reaction vessel was sealed, and hydrogen of 40 kg/cm2 was conducted to the reaction vessel. The reaction vessel was heated to 120° C. to process the hydrogenation for 3.5 hours, and the heating process was then stopped. The conversion ratio of the hydrogenation was measured by FT-IR and UV-VIS spectrometers, as tabulated in Table 1.
Example 4
9 g of the SIS (Kraton D1161.) was dissolved in 111 g of cyclohexane to form a SIS solution (7.5 wt %). The SIS solution was put into a reaction vessel. 1.8 g of the Pd/Al2O3 catalyst prepared in Preparation Example 4 was added to the reaction vessel. The reaction vessel was sealed, and hydrogen of 40 kg/cm2 was conducted to the reaction vessel. The reaction vessel was heated to 120° C. to process the hydrogenation for 3.8 hours, and the heating process was then stopped. The conversion ratio of the hydrogenation was measured by FT-IR and UV-VIS spectrometers, as tabulated in Table 1.
Example 5
18 g of the styrene-butadiene-styrene block copolymer (SBS, Aldrich 182877) was dissolved in 102 g of cyclohexane to form an SBS solution (15 wt %). The SBS solution was put into a reaction vessel, 1.2 g of the Pt—Re/TiO2 catalyst prepared in Preparation Example 5 was added to the reaction vessel. The reaction vessel was sealed, and hydrogen of 40 kg/cm2 was conducted to the reaction vessel. The reaction vessel was heated to 100° C. to process the hydrogenation for 0.41 hours, and the heating process was then stopped. The conversion ratio of the hydrogenation was measured by FT-IR and UV-VIS spectrometers, as tabulated in Table 1.
Example 6
18 g of the SBS (Aldrich 182877) was dissolved in 102 g of cyclohexane to form an SBS solution (15 wt %). The SBS solution was put into a reaction vessel. 1.2 g of the Pt—Re/TiO2 catalyst prepared in Preparation Example 5 was added to the reaction vessel. The reaction vessel was sealed, and hydrogen of 40 kg/cm2 was conducted to the reaction vessel. The reaction vessel was heated to 90° C. to process the hydrogenation for 0.49 hours, and the heating process was then stopped. The conversion ratio of the hydrogenation was measured by FT-IR and UV-VIS spectrometers, as tabulated in Table 1. Compared to Example 5, the product still had a high carbon-carbon double bond conversion ratio even with a lower hydrogenation temperature and a longer hydrogenation period.
Example 7
18 g of the SBS (Aldrich 182877) was dissolved in 102 g of cyclohexane to form an SBS solution (15 wt %). The SBS solution was put into a reaction vessel. 1.2 g of the Pt/SiO2 catalyst prepared in Preparation Example 6 vas added to the reaction vessel. The reaction vessel was sealed, and hydrogen of 40 kg/cm2 was conducted to the reaction vessel. The reaction vessel was heated to 100° C. to start the hydrogenation, and then slowly heated to 130° C. for total 6.4 hours, and the heating process was then stopped. The conversion ratio of the hydrogenation was measured by FT-IR and UV-VIS spectrometers, as tabulated in Table 1. Compared to Examples 5 and 6, the catalyst having platinum without other metals needed a longer hydrogenation period, and the hydrogenation product had a lower carbon-carbon double bond conversion ratio.
Example 8
18 g of the SBS (Aldrich 182877) was dissolved in 102 g of cyclohexane to form an SBS solution (15 wt %). The SBS solution was put into a reaction vessel. 1.2 g of the Pt—Re/SiO2 catalyst prepared in Preparation Example 7 was added to the reaction vessel. The reaction vessel was sealed, and hydrogen of 40 kg/cm2 as conducted to the reaction vessel. The reaction vessel was heated to 100° C., to process the hydrogenation for 0.95 hours, and the heating process was then stopped. The conversion ratio of the hydrogenation was measured by FT-IR and UV-VIS spectrometers as tabulated in Table 1. Compared to Examples 5 and 6, the catalyst with silicon oxide serving as the porous support ceded a longer hydrogenation period, and the hydrogenation product had a lower carbon-carbon double bond conversion ratio.











TABLE 1











Conversion ratio



Hydrogenation

(%)
















temperature
Hydrogenation
Double
Benzene



Catalyst
Copolymer
(° C.)
period (hour)
bond
ring

















Example 1
Pt—Ir/SiO2
SIS
120
2.6
98
<2


Example 2
Pd/SiO2
SIS
110
4.2
97
<5


Example 3
Pd/ZrO2
SIS
120
3.5
99
<1


Example 4
Pd/Al2O3
SIS
120
3.8
92
<5


Example 5
Pt—Re/TiO2
SBS
100
0.41
99
<1


Example 6
Pt—Re/TiO2
SBS
90
0.49
99
<1


Example 7
Pt/SiO2
SBS
130
6.4
92
<1


Example 8
Pt—Re/SiO2
SBS
100
0.95
98
<1









It will be apparent to those skilled in the art that various modifications and variations can be made to the disclosed methods and materials. It is intended that the specification and examples be considered as exemplary only, with a true scope of the disclosure being indicated by the following claims and their equivalents.

## Claims

1. A method for selectively hydrogenating a copolymer, comprising:
contacting a heterogeneous catalyst with a copolymer including aromatic rings and double bonds to process a hydrogenation at a temperature of 40° C. to 150° C. under a hydrogen pressure of 10 kg/cm2 to 50 kg/cm2 for hydrogenating the double bonds, wherein less than 5% of the aromatic rings are hydrogenated, wherein the heterogeneous catalyst consists of a metal catalyst formed on a porous support, and the metal catalyst is platinum-rhenium alloy.

2. The method as claimed in claim 1, wherein the porous support comprises titanium oxide, aluminum oxide, zirconium oxide, or silicon oxide.

3. The method as claimed in claim 1, wherein the copolymer is copolymerized of a polyenic monomer and a vinyl aromatic monomer.

4. The method as claimed in claim 3, wherein the polyenic monomer comprises butadiene, isopentadiene, or combinations thereof.

5. The method as claimed in claim 3, wherein the vinyl aromatic monomer comprises styrene, α-methylstyrene, or combinations thereof.

6. The method as claimed in claim 1, wherein the hydrogenation is processed at a temperature of 70° C. to 120° C. under a hydrogen pressure of 30 kg/cm2 to 40 kg/cm2.

7. The method as claimed in claim 1, wherein the metal catalyst has a platinum-rhenium weight ratio of 5:0.1 to 1:5.

8. The method as claimed in claim 1, wherein the heterogeneous catalyst comprises 0.2 wt % to 10 wt % of the metal catalyst.

9. The method as claimed in claim 1, wherein the heterogeneous catalyst comprises 1 wt % to 5 wt % of the metal catalyst.