CATALYST RESIN

Abstract

A method of making a plurality of resin beads comprising (a) providing a reaction mixture comprising monovinyl aromatic monomer, multivinyl aromatic monomer, and porogen, (b) performing aqueous suspension polymerization on said reaction mixture to form resin beads, and (c) sulfonating said resin beads. Also provided is a plurality of resin beads, wherein said resin beads comprise polymerized units of monovinyl aromatic monomer and polymerized units of multivinyl aromatic monomer, wherein said resin beads have BET surface area of 15 to 38 m.sup.2/g and volume capacity of 0.7 or higher. Also provided is a method of making a product of the chemical reaction of one or more reactants, said method comprising reacting said one or more reactants with each other in the presence of the plurality of such resin beads.

Claims

1. A plurality of resin beads, wherein said resin beads comprise (i) 93.5% to 96% polymerized units of monovinyl aromatic monomer, by weight based on the weight of said resin beads, (ii) 4% to 6.5% polymerized units of multivinyl aromatic monomer, by weight based on the weight of said resin beads, wherein said resin beads have BET surface area of 15 to 38 m.sup.2/g and volume capacity of 0.7 or higher.

2. The plurality of resin beads of claim 1, wherein said resin beads have pore volume of 0.1 to 0.29 cm.sup.3/g.

Description

EXAMPLE 1: METHODS OF AQUEOUS SUSPENSION POLYMERIZATION AND SULFONATION TO FORM RESIN BEADS

[0060] Aqueous suspension polymerization was conducted using standard techniques, using 300 g of aqueous phase (water and suspending agents), 270 g of organic phase (monomers (styrene (STY) and Divinyl Benzene (DVB), initiators and porogen). The porogen used was methyl isobutyl carbinol (MIBC) in 34-40% based on total organic phase. Typical mixing, time and temperatures were used for the synthesis steps. After polymerization, the resulting polymer beads were washed with excess water and oven dried. Sulfonation of this resin was performed by standard sulfonation methods. The result is a crosslinked poly(STY-co-DVB) sulfonated resin.

EXAMPLE 2: CONVERSION TO ACID FORM

[0061] Some commercial resins were obtained in the sodium form. Prior to use as catalyst, these resins were converted to acid form as follows. 70 mL of resin was charged to a column along with deionized water. 1 liter solution of HCl 4% (by weight) was downflowed at 250 mL/h, followed by 2 liter of deionized water at 250 mL/h. Final pH of effluent was confirmed to be within 2-3.

EXAMPLE 3: REACTION OF METHANOL WITH METHACRYLIC ACID

[0062] 60 mL of catalyst in acid form were washed with 600 mL deionized water in a column with downflow process at 120 mL/hour. The catalyst was dried in a Buchner funnel to remove excess water and charged again into the column with MeOH. 2000 mL of methanol were flowed through the column in downflow process at 120 mL/hour. At the end of the process the catalyst was transferred as slurry in methanol to a graduated cylinder and the volume registered. The catalyst was then dried in a Buchner funnel to remove excess methanol. 150.0 g of Methanol were weighed and used to charge the catalyst and methanol to the 500 mL reactor. 40 mg of inhibitor, MEHQ, was weighed and charged to the reactor and stirred at 300 rpm for all the runs. The reactor was heated to 60 C. within 30 minutes. 40 g of Methacrylic Acid (GMAA) was charged to the reactor and the reaction held at 60 C. for 6 hours. 1 mL samples for gas chromatography were taken at the following reaction times: 10 seconds, 1 hour, 2 hour, 3 hour and 4 hour. In situ infrared measurements were started before the GMAA was charged and samples measured every 30 seconds during the 4 hour run. In situ Infrared measurements were used to follow kinetics for the runs and estimate the reaction rate observed constants.

EXAMPLE 4: POROSITY MEASUREMENTS BY BET METHOD

[0063] Resin Example 11 was made as in Example 1. Resin Example 11 is a styrene/divinyl benzene copolymer with 6% DVB, made with 35% MIBC. Comparative Example C12 was made with 7% DVB and 35% MIBC as in Example 1. Also tested were Diaion PK-208 resin and Diaion PK-212 resin, from Mitsubishi Chemical; and Dowex CM-4 resin from Dow Chemical Company.

[0064] Samples were prepared as follows. 60 ml of resin that was wet with water was prepared in a vertical column 500 ml of methanol was flowed down through the column at 2 BV/hr, followed by 500 ml of toluene at 2 BV/hr, followed by 500 ml of isooctane at 2 BV/hr. The resin was then dried at 45 C. under vacuum for 24 hours.

[0065] Porosity included surface area (SA), total pore volume (PV), and mean diameter (diam) of the pores. The results were as follows:

TABLE-US-00002 Pore % % SA PV diam Sample DVB.sup.(1) MIBC.sup.(2) VC.sup.(3) (m.sup.2/g) (cm.sup.3/g) (nm) Diaion PK-208 4 1.32 13.28 0.0866 26.1 Diaion PK-212 6 1.75 6.38 0.0304 19.0 Dowex CM-4 4 note.sup.(4) 0.65 26.27 0.2980 45.4 Example Resin 11 6 35 1.23 32.68 0.2037 25.0 Comparative Resin C12 7 35 1.24 40.02 0.3056 30.5 Note .sup.1polymerized units of divinylbenzene, by weight based on the dry weight of polymer Note .sup.(2)methylisobutyl carbinol, used as porogen while making the resin, by weight based on the dry weight of the polymer. Note .sup.3Volume Capacity (meq/L) Note .sup.4The amount of porogen used in making Dowex CM-4 is greater than 39% by weight based on the weight of monovinyl aromatic monomer plus the weight of multivinyl aromatic monomer.

EXAMPLE 5: PHYSICAL TOUGHNESS

[0066] Physical toughness of the resin was assessed by osmotic shock attrition (OSA), which is performed by osmotic shock attrition (OSA), which is performed by volume expansion effect of the catalysts making a column of a packed bed of the resin and then flowing the following solutions through the column: deonized water, then diluted acid (4% by weight aqueous HCl), then deionized water, then 4% by weight aqueous NaOH, and finishing with deionized water wash. 40 cycles were done, and resin breakage measured at the end of the process. The resin breakage was measured by microscope observation where 100 total beads were counted and the broken one recorded as a percent. The less physical toughness the resin had, the higher the % Breakdown.

[0067] The following styrene/divinyl benzene copolymer resins were made as in Example 1: Comparative Resins C1-C2 and Example Resins 3-5. Also tested was Diaion PK-212 resin, from Mitsubishi Chemical. Comparative Resins C1 and C2 are comparative because the level of MIBC is too low. Diaion PK-212 resin is comparative because it has BET surface area lower than 15 m.sup.2/g.

[0068] These resins were tested, and the OSA results were as follows:

TABLE-US-00003 Sample % DVB.sup.(1) % MIBC.sup.(2) % Breakdown Comparative Resin C1 6 0 47 Comparative Resin C2 6 34 15 Example Resin 3.sup.(3) 6 35 2 Example Resin 4 6 36 1 Comparative Resin 5 7 35 1 PK-212 6% unknown 5 Note .sup.(1)polymerized units of divinylbenzene, by weight based on the dry weight of polymer Note .sup.(2)methylisobutyl carbinol, used as porogen while making the resin, by weight based on the dry weight of the polymer. Note .sup.(3)Example Resin 3 is a duplicate preparation of Example Resin 11

[0069] Comparative Resin C1 had 0% MIBC; because there was no porogen, it had very low porosity and had very high % breakdown. Comparative Resin C2 had only 34% MIBC; its porosity was still not high enough, and it had unacceptably high % breakdown. PK-212 had porosity of 6.38 m2/g (surface area), 0.0304 cm3/g (Pore volume), microporosity 0.0010 cm3/g, and 19.01 nm (Pore Diameter 4V/A) and had unacceptably high % breakdown.

EXAMPLE 6: CONVERSION OF METHACRYLIC ACID TO METHYL METHACRYLATE

[0070] The infrared measurement described above yielded the % conversion, which is the moles of methyl methacrylate produced divided by the moles of methacrylic acid present at the beginning of the reaction. The % conversion (% Conv) is considered to be a measure of the effectiveness of the catalyst.

[0071] Samples were made as in Example 1 and tested as described in Example 3. Results were as follows (nt means not tested). Comparative C21 had too little DVB. Comparative C26 had too much MIBC.

TABLE-US-00004 % % % Conv % Conv % Conv Sample DVB.sup.(1) MIBC.sup.(2) at 2 hours at 3 hours at 4 hours Comparative C21 3 36 60 nt 77 Resin 22 4 36 60 nt 78 Resin 23 5 36 61 nt 76 Resin 24 6 36 57 67 76 Comparative 25 7 36 49 nt 71 Comparative C26 6 40 40 50 57 Note .sup.(1)polymerized units of divinylbenzene, by weight based on the dry weight of polymer Note .sup.(2)methylisobutyl carbinol, used as porogen while making the resin, by weight based on the dry weight of the polymer.
The Example resins 22-24 show catalytic effectiveness superior to Comparatives C25 and C26. Example resins 22-24 show a trend that, at equal MIBC, increasing DVB leads to decreasing % conversion; from this trend, it is concluded that samples with higher levels of DVB would have even lower % conversion. Therefore it is concluded that samples with DVB of 7% or above would have unacceptably low % conversion. Comparative C21 shows acceptable catalytic effectiveness, but it also is expected to show unacceptably low physical toughness. A sample that was nearly identical to C21 was made and tested as follows:

TABLE-US-00005 Sample % DVB.sup.(1) % MIBC.sup.(2) % Breakdown Comparative C27 3 35 33.09 Notes .sup.(1) and .sup.(2) as above

EXAMPLE 7: CHARACTERISTICS

[0072] Various resins were made with the following characteristics. unk means unknown; nt means not tested.

TABLE-US-00006 Wt. Vol. MeOH Example % DVB % MIBC % MHC Cap. Cap. HMPS Density shrink 31 5.0 34.8 70.6 5.18 1.11 0.661 1.12 0.854 32 4.0 34.8 73.6 5.20 0.99 0.668 1.10 0.771 C33.sup.(1) 3.0 34.8 77.8 5.24 0.83 0.779 1.08 0.735 C34.sup.(1) 7.0 34.8 67.6 5.13 1.20 0.809 1.13 0.900 C35.sup.(1) 7.0 34.8 68.2 5.19 1.24 0.584 1.13 0.871 PK-208.sup.(1) 4.0 unk 69.0 5.14 1.19 0.650 nt 0.841 PK-212.sup.(1) 6.0 unk 60.4 5.12 1.57 0.734 nt 0.860 PK-216.sup.(1) 8.0 unk 55.0 5.16 1.85 0.683 nt 0.916 PK-218.sup.(1) 9.0 unk 53.5 5.04 1.88 0.679 nt 0.909 Note .sup.(1)Comparative

EXAMPLE 8: PARTITIONING TEST

[0073] Various samples were measured using the Partitioning Test. The cutoff size above which the pore volume drops below 0.1 ml/g is shown below:

TABLE-US-00007 Example % DVB % MIBC cutoff size 31 5.0 34.8 greater than 10 nm 32 4.0 34.8 greater than 10 nm PK-208.sup.(1) 4.0 unk less than 2 nm PK-212.sup.(1) 6.0 unk less than 2 nm PK-216.sup.(1) 8.0 unk less than 2 nm PK-218.sup.(1) 9.0 unk less than 2 nm Note .sup.(1)Comparative