Method of catalysis for the production of bisphenol A

Abstract

Provided is a process for producing 2,2-bis(4-hydroxyphenyl)propane, comprising condensing phenol with acetone in the presence of an acid catalyst; wherein the acid catalyst comprises a collection of sulfonated polymeric beads, wherein the sulfonated polymeric beads comprise (i) 75 to 99% by weight, based on the weight of the bead, polymerized units of monofunctional vinyl monomer, and (ii) 1 to 25% by weight, based on the weight of the bead, polymerized units of multifunctional vinyl monomer; wherein 90% or more of the beads by volume are uniform beads.

Claims

1. A process for producing 2,2-bis(4-hydroxyphenyl)propane, comprising condensing phenol with acetone in the presence of an acid catalyst to produce dihydric phenol 2,2-bis(4-hydroxyphenyl) propane; wherein the acid catalyst comprises a collection of sulfonated polymeric beads, wherein the sulfonated polymeric beads comprise (i) 75 to 99% by weight, based on the weight of the bead, polymerized units of monofunctional vinyl monomer, and (ii) 1 to 25% by weight, based on the weight of the bead, polymerized units of multifunctional vinyl monomer; wherein, within each bead, the average concentration of moles of polymerized units of multifunctional vinyl monomer per cubic micrometer is MVAV; and wherein, within each bead, T1000 is a sequence of 1,000 unique connected polymerized monomer units; wherein, within each T1000, MVSEQ is the weight percent polymerized units of multifunctional vinyl monomer, based on the weight of T1000; wherein MVRATIO=MVSEQ/MVAV; and wherein 90% or more of the beads by volume are uniform beads, wherein a uniform bead is a bead in which 90% or more of all T1000 sequences has MVRATIO of 1.5 or less.

2. The process of claim 1, wherein the acid catalyst additionally comprises a thiol compound.

3. The process of claim 1, wherein the condensation is conducted at 55 C. or above.

4. The process of claim 1, wherein 35% or less of the T1000 sequences have MVRATIO of 0.5 or less.

Description

COMPARATIVE EXAMPLE A1-COMP (NO ADDITION OF MONOMER AFTER INITIATION OF POLYMERIZATION), USING PROTOCOL A

(1) Aqueous suspension polymerization was conducted on the reaction mixture as follows. A combination of reaction temperature and BPO concentration was chosen to result in an extent of conversion of 80-85% within 330-390 minutes. Once conversion to polymer was in the 80-85% range, pH was adjusted by Tris addition to the reactorsuch that the final pH was in the 8-9 range. The reaction system was heated to 97 C. After 1 hour at 97 C., the system was cooled to ambient temperature and the beads were dewatered, washed with water, and dried at ambient temperature. Two identical polymerizations were conducted.

EXAMPLE A-2A AND A-2B, ALSO USING PROTOCOL A

(2) Aqueous suspension polymerization was conducted on the reaction mixture as follows. A combination of reaction temperature and BPO concentration was chosen to result in an extent of conversion of 80-85% within 390-550 minutes. Once reaction temperature was reached, DVB was fed to the reactor, over the extent range shown in the table in Example R1 below, with the DVB feed rate varying with time. Two duplicate polymerizations of A-2a were performed, labeled A-2a(1) and A-2a(2).

(3) Once conversion to polymer was in the 60-75% range, Tris was added to the reactor, such that the final pH was in the range of 8-9. The reaction system was heated to 97 C. within 60 minutes of Tris addition. After 1 hour, the system was cooled to ambient temperature and the beads were dewatered, washed with water and dried at ambient temperature.

EXAMPLE A-2C, ALSO USING PROTOCOL A

(4) Aqueous suspension polymerization was conducted on the reaction mixture as follows. A combination of reaction temperature and BPO concentration was chosen to result in an extent of conversion of 80-85% within 390-550 minutes Once reaction temperature was reached, DVB was fed to the reactor, over the extent range shown in the table in Example R1 below, with the DVB feed rate varying with time.

(5) Once conversion to polymer was in the 60-75% range, Tris was added to the reactor, such that the final pH was in the 8-9 range. The reaction system was heated to 97 C. within 60 minutes of the Tris addition. After 1 hour, the system was cooled to ambient temperature and the beads were dewatered, washed with water and dried at ambient temperature.

COMPARATIVE EXAMPLE B1-COMP (NO ADDITION OF MONOMER AFTER INITIATION OF POLYMERIZATION), USING PROTOCOL B

(6) Aqueous suspension polymerization was conducted on the reaction mixture as follows. A combination of reaction temperature and BPO concentration was chosen to result in an extent of conversion of 80-85% within 480-560 minutes. Once at reaction temperature, a feed of 0.1% tBC in water to the reactor was started. The tBC feed rate varied with time, to simulate the tBC feed that would normally accompany a DVB feed.

(7) tBC was gradually added from Extent 0% to 57%. Prior to initiation of polymerization, tBC concentration in the monomer droplets was 0.0055% by weight. At the end of the tBC feed, the tBC concentration in the monomer droplets (partially or fully converted to polymer) was 0.0101% by weight.

(8) Once conversion to polymer was in the 80-85% range, pH was adjusted by Tris addition to the reactor, such that the final pH was in the range of 8-9. The reaction system was heated to 97 C. After 1 hour, the system was cooled to ambient temperature and the beads were dewatered, washed with water, and dried at ambient temperature.

EXAMPLES B-2A, B-2B, B-2C, B-2D, B-2E, AND B-2F, ALSO USING PROTOCOL B

(9) Duplicate samples of B-2b were made, labeled B-2b(1) and B-2b(2).

(10) Aqueous suspension polymerization was conducted on the reaction mixture as follows. A combination of reaction temperature and BPO concentration is chosen to result in an extent of conversion of 80-85% within 420-600 minutes. Once reaction temperature was reached, DVB was fed to the reactor, over the extent range shown in the table in Example R1 below, with the DVB feed rate varying with time.

(11) Once conversion to polymer was in the 60-85% range, Tris was added to the reactor, such that the final pH was in the 8-9 range. The reaction system was heated to 97 C. within 60 minutes of the Tris addition. After 1 hour, the system was cooled to ambient temperature and the beads were dewatered, washed with water and dried at ambient temperature.

COMPARATIVE EXAMPLE C1-COMP (NO ADDITION OF MONOMER AFTER INITIATION OF POLYMERIZATION), USING PROTOCOL C

(12) Aqueous suspension polymerization was conducted on the reaction mixture as follows. A combination of reaction temperature and BPO concentration is chosen to result in an extent of conversion of 80-85% within 330-390 minutes. Once reaction temperature was reached, Tris was added to the reactor such that the final aqueous pH was in the 8-9 range. Once conversion was in the 80-85% range, the system was heated to 97 C. After 1 hour at 97 C., the system was cooled to ambient temperature and the beads were dewatered, washed with water, and dried at ambient temperature.

EXAMPLE C-2, USING PROTOCOL C

(13) Aqueous suspension polymerization was conducted on the reaction mixture as follows. A combination of reaction temperature and BPO concentration is chosen to result in an extent of conversion of 80-85% within 420-600 minutes. Once reaction temperature was reached, DVB was fed to the reactor, over the extent range shown in the table in Example R1 below, with the DVB feed rate varying with time.

(14) Once conversion was in the 60-85% range, Tris was added to the reactor such that the final pH was in the 8-9 range. The reaction system was heated to 97 C. within 60 minutes of the Tris addition. After 1 hour, the system was cooled to ambient temperature and the beads were dewatered, washed with water and dried at ambient temperature.

COMPARATIVE EXAMPLE D1-COMP (NO ADDITION OF MONOMER AFTER INITIATION OF POLYMERIZATION), USING PROTOCOL D

(15) Aqueous suspension polymerization was conducted on the reaction mixture as follows. A combination of reaction temperature and BPO concentration is chosen to result in an extent of conversion of 80-85% within 420-600 minutes. Once conversion to polymer was in the 80-85% range, pH was adjusted by Tris addition to the reactorsuch that the final pH is in the 8-9 range. The reaction system was heated to 97 C. After 1 hour, the system was cooled to ambient temperature and the beads were dewatered, washed with water, and dried at ambient temperature. Two identical polymerizations were conducted.

EXAMPLE D-2A, USING PROTOCOL D

(16) Aqueous suspension polymerization was conducted on the reaction mixture as follows. A combination of reaction temperature and BPO concentration is chosen to result in an extent of conversion of 80-85% within 390-550 minutes. Once reaction temperature was reached, DVB was fed to the reactor, over the extent range shown in the table in Example R1 below, with the DVB feed rate varying with time. Two duplicate polymerizations, labeled D-2a(1) and D-2a(2), were performed.

(17) Once conversion to polymer was in the 20-30% range, Tris buffer was added to the reactor, such that the final pH was in the 8-9 range. Additional Tris buffer was added when conversion reached 80-85% such that the final pH was in the range of 8-9. The reaction system was then heated to 97 C. within 60 minutes of the Tris addition. After 1 hour, the system was cooled to ambient temperature and the beads were dewatered, washed with water and dried at ambient temperature.

EXAMPLE D-2B, USING PROTOCOL D

(18) The same protocol as in D-2a was used, except that DVB was gradually added over the extent range shown in the table in Example R1 below. Two duplicate polymerizations, labeled D 2b(1) and D-2b(2), were performed.

COMPARATIVE EXAMPLE E-1COMP (NO ADDITION OF MONOMER AFTER INITIATION OF POLYMERIZATION), USING PROTOCOL E

(19) Aqueous suspension polymerization was conducted on the reaction mixture as follows. A combination of reaction temperature and BPO concentration is chosen to result in an extent of conversion of 80-85% within 210-270 minutes. Once conversion to polymer was in the 80-85% range, the reaction system was heated to 92 C. After 1 hour, the system was cooled to ambient temperature and the beads were dewatered, washed with water, and dried at ambient temperature.

EXAMPLE E-2, USING PROTOCOL E

(20) Aqueous suspension polymerization was conducted on the reaction mixture as follows. A combination of reaction temperature and BPO concentration is chosen to result in an extent of conversion of 80-85% within 300-360 minutes. Once reaction temperature was reached, DVB was fed to the reactor, over the extent range shown in the table in Example R1 below, with the DVB feed rate varying with time.

(21) Once conversion to polymer was in the 80-85% range, the reaction system was heated to 92 C. After 1 hour, the system was cooled to ambient temperature and the beads were dewatered, washed with water and dried at ambient temperature.

COMPARATIVE EXAMPLE F1-COMP (NO ADDITION OF MONOMER AFTER INITIATION OF POLYMERIZATION), USING PROTOCOL F

(22) Aqueous suspension polymerization was conducted on the reaction mixture as follows. A combination of reaction temperature and BPO concentration is chosen to result in an extent of conversion of 80-85% within 300-360 minutes. Once conversion to polymer was in the 80-85% range, pH was adjusted by Tris addition to the reactorsuch that the final pH is in the 8-9 range. The reaction system was heated to 97 C. After 1 hour, the system was cooled to ambient temperature and the beads were dewatered, washed with water, and dried at ambient temperature.

EXAMPLE F-2, USING PROTOCOL F

(23) Aqueous suspension polymerization was conducted on the reaction mixture as follows. A combination of reaction temperature and BPO concentration is chosen to result in an extent of conversion of 80-85% within 330-390 minutes. Once reaction temperature was reached, tBC-free DVB was fed to the reactor, over the extent range shown in the table in Example R1 below, with the DVB feed rate varying with time.

(24) Once conversion to polymer was in the 80-85% range, Tris was added to the reactor, such that the final pH was in the 8-9 range. The reaction system was heated to 97 C. within 60 minutes of the Tris addition. After 1 hour, the system was cooled to ambient temperature and the beads were dewatered, washed with water and dried at ambient temperature.

COMPARATIVE EXAMPLE G1-COMP (NO ADDITION OF MONOMER AFTER INITIATION OF POLYMERIZATION), USING PROTOCOL G

(25) Aqueous suspension polymerization was conducted on the reaction mixture as follows. A combination of reaction temperature and BPO concentration is chosen to result in an extent of conversion of 80-85% within 300-360 minutes. Once conversion to polymer was in the 80-85% range, the reaction system was heated to 90 C. After 3 hours, the system was cooled to ambient temperature and the beads were dewatered, washed with water and dried at ambient temperature.

EXAMPLE G-2, USING PROTOCOL G

(26) Aqueous suspension polymerization was conducted on the reaction mixture as follows. A combination of reaction temperature and BPO concentration was chosen to result in an extent of conversion of 80-85% within 420-600 minutes. Once reaction temperature was reached, DVB was fed to the reactor, over the extent range shown in the table in Example R1 below, with the DVB feed rate varying with time.

(27) Once conversion to polymer was in the 80-85% range, the reaction system was heated to 90 C. After 3 hours, the system was cooled to ambient temperature and the beads were dewatered, washed with water and dried at ambient temperature.

EXAMPLE R1: RESULTS OF PHYSICAL STABILITY TESTING SAC RESINS

(28) Copolymers made with the above protocols were converted to SAC resins and tested as described above. Results were as follows. Where duplicate samples were tested, the average results are shown. method=refers to whether the polymerization method had the gradual addition (GA) step of the present invention or not. init DVB=the amount of DVB in the monomer droplets prior to initiation of polymerization, (by weight based on the weight of the monomer droplets) final DVB=the amount of polymerized units of DVB in the finished polymer, by weight based on the total weight of all monomer used in the entire process, including the initial droplets and the DVB fed during polymerization EXTSTART=extent of reaction at which DVB feed was begun EXTSTOP=extent of reaction at which DVB feed was ended DIAM=harmonic mean diameter of polymeric beads

(29) TABLE-US-00004 init final EXT- EXT- Exam- meth- DVB DVB START STOP DIAM Crush OS ple od (%) (%) (%) (%) (m) (g/bd) (%) A-1 no 4.65 4.65 none none 450 806 12.4 Comp GA A-2a GA 2 4.65 0 60 450 3242 1.8 A-2b GA 2 4.65 0 85 450 2882 2.7 A-2c GA 0.8 4.65 0 58 450 2458 1.1 B-1 no 5.2 5.2 none none 450 1375 1.7 Comp GA B-2a GA 2.25 5.2 0 78 450 3271 1.6 B-2b GA 2.25 5.2 0 59 450 3649 1.2 B-2c GA 2.25 5.2 0 24 450 3736 0.6 B-2d GA 2.25 5.2 0 5 450 4215 0.4 B-2e GA 2.25 5.2 15 43 450 2700 0.4 B-2f GA 2.25 5.2 27 33 450 2673 0.7 C-1 no 4.65 4.65 none none 450 838 13.8 Comp GA C-2 GA 2.25 5.2 0 62 450 2646 2.7 D-1 no 2.0 2.0 none none 450 916 11.1 Comp GA D-2a GA 0.8 2.0 0 74 or 75 450 1470 2.3 D-2b GA 1.1 2.8 0 80 or 85 450 1773 2.0 E-1 no 4.65 4.65 none none 460 830 17.2 Comp GA E-2 GA 2.0 4.65 0 80 460 1044 3.9 F-1 no 9.2 9.2 none none 450 2125 0.4 Comp GA F-2 GA 4.65 11.0 0 67% 450 3412 0.1 G-1 no 7.6 7.6 none none 450 560 8.6 Comp GA G-2 GA 450 2420 1.4

EXAMPLE R2: RESULTS OF TESTING OF SAMPLES OF PROTOCOL E

(30) From the copolymers of protocol E, Strong Base Anion (SBA) exchange resins were made by a standard process of chloromethylation using chloromethyl ether followed by amination using trimethyl amine, such that at least 95 mole % of aromatic rings on polymerized units of monofunctional vinyl monomer, based on the total polymerized units of monofunctional vinyl monomer, had an amine-containing group attached.

(31) The SBA resins were tested as in Example A-R. Results were as follows:

(32) TABLE-US-00005 init final EXT- EXT- DVB DVB START STOP DIAM Crush OS Example method (%) (%) (%) (%) (m) (g/bd) (%) H-1Comp no GA 4.65 4.65 none none 450 160 53.8 H2 GA 2.0 4.65 0 80% 450 324 37.0

EXAMPLE R3: RESULTS OF CATALYSIS

(33) Various functionalized resin samples were tested for activity in catalyzing the reaction between phenol and acetone to make bisphenol-A (BPA). The catalytic activity is characterized by the time to 60% conversion (T60%). Shorter times reflect higher level of catalytic activity.

(34) The catalysis reactions were carried out as follows: Resin was rinsed with phenol to remove moisture from the beads. Phenol was added to a glass reactor and heated at 50 C. to melt the phenol. Dry resin, loaded with promoter, was added to the reactor and allowed to swell in the phenol. Reactor temperature was regulated at a temperature between 45 C. and 80 C. Acetone was added to the reactor. At time intervals, a small sample of the liquid in the reactor was removed by pipette, placed in a vial, and mixed with excess N-Methyl-N-(trimethylsilyl) trifluoroacetamide. Vials were stored for 30 minutes at 60 C., then cooled to ambient temperature, then tested by Gas Chromatography for BPA content.

(35) The catalysis results were as follows. All of the samples shown had total amount of polymerized units of DVB of 4.65%.

(36) TABLE-US-00006 Example A-2a A-2b A-2c C-1Comp T60% (min) 52 52 47 71

(37) Samples A-2a, A-2b, and A-2c, which were made using gradual addition according to the present invention, had much shorter times to 60% conversion than the comparative sample.

EXAMPLE R4: RESULTS OF STORAGE FOR 30 DAYS AT AMBIENT TEMPERATURE

(38) Storage results were as follows:

(39) TABLE-US-00007 Example: A-1Comp A-2a A-2b C-1Comp C-2 Conductivity 169 127 160 189 126 (S) Absorbance 0.225 0.165 0.171 0.235 0.137

(40) Each Example resin showed lower conductivity and absorbance than its corresponding comparative example. That is, samples A-2a and A-2b showed lower conductivity and absorbance than comparative A-1Comp. Similarly, sample C-2 showed lower conductivity and absorbance than comparative C-1Comp. This result shows that the Example resins have greater stability during storage.