HK1063777B - Amine modified catalysts for bisphenol production - Google Patents

Description

Amine modified catalysts for bisphenol production

Technical Field

The present invention relates to amine modified acidic resin catalysts and their use in reactions of hydroxyaromatic compounds with aldehydes and ketones in the presence of thiol promoters to provide bisphenols such as bisphenol a (bpa).

Background

Bisphenols, exemplified by BPA, are widely used in the manufacture of polymeric materials and are typically prepared by the condensation of hydroxyaromatic compounds with aldehydes or ketones in the presence of an acidic catalyst. Bisphenol A is the principal monomer used in the production of bisphenol A polycarbonate, which is a commercial engineering thermoplastic material. The manufacture of bisphenol a from acetone and phenol is carried out worldwide on a scale producing hundreds of million pounds per year. Typically, phenol is reacted with acetone in the presence of an acidic catalyst and a thiol promoter. The role of the thiol promoter is to improve the rate and selectivity of BPA formation in the acid-catalyzed condensation reaction of phenol and acetone. Many different combinations of acidic catalysts and thiol promoters have been investigated, and some thiol promoters, such as 3-mercaptopropionic acid, have been used in commercial scale production of BPA. Despite the earlier research efforts and the impressive improvements they bring in the manufacture of bisphenolic compounds such as bisphenol a, there is still a need for further improvements in both the rate and selectivity of bisphenol formation in the acid catalyzed condensation of hydroxyaromatic compounds with aldehydes or ketones.

Summary of The Invention

One aspect of the present invention relates to a process for the manufacture of bisphenols, said process comprising contacting a mixture comprising a hydroxyaromatic compound and a ketone or aldehyde with an amine-modified acidic resin catalyst in the presence of a thiol promoter at a temperature in the range of about 25 ℃ to about 95 ℃. In another aspect, the present invention also relates to amine modified acidic resin catalysts.

Detailed Description

The present invention may be understood more readily by reference to the following preferred embodiments of the invention and the examples included therein. In this specification and in the claims which follow, reference will be made to a number of terms which shall be defined to have the following meanings.

As used herein, "amine-modified acidic resin catalyst" refers to an acidic resin, a portion of the acidic functionality of which has been neutralized by treatment with an amine. For example, a sulfonated polystyrene resin has about 5 to 50 percent-SO therein after treatment with a corresponding amount of an amine, such as pyridine₃The H group is converted to the corresponding pyridinium salt, thus constituting an amine modified acidic resin catalyst. The amine used is distinguished from any thiol promoter which itself contains an amino group. In the case where the thiol promoter comprises an amino group, such as hemin amine, such an amine modified acidic resin catalyst is understood to contain at least one additional amine which is not both amines contained in the thiol promoter.

"BPA" is defined herein as bisphenol A and is also known as 2, 2-bis (4-hydroxyphenyl) propane, 4' -isopropylidenediphenol and P, P-BPA.

"O, P-BPA" is defined herein as ortho, para bisphenol A and is also known as 2- (2-hydroxyphenyl) -2- (4-hydroxyphenyl) propane and 2, 4' isopropylidenediphenol.

As used herein, the term "fragranceThe group "means a group having a valence of at least one, and containing at least one aromatic group. Examples of aromatic groups include phenyl, pyridyl, furyl, thienyl, imidazolyl, naphthyl, phenylene, and biphenyl. The term also includes groups containing both aromatic and aliphatic components, such as benzyl. Further, C₃-C₄₀The aryl group means an aryl group containing carbon atoms of 3 to 40. The following 2-imidazolyl (i) illustrates one C₃An aromatic group:

as used herein, the term "aliphatic radical" refers to a radical having a valence of at least one, and comprising a linear or branched array of atoms which is not cyclic. Heteroatoms such as nitrogen, sulfur and oxygen may be included in the array or may be composed exclusively of carbon and hydrogen. Examples of aliphatic groups include methyl, methylene, ethyl, ethylene, hexyl, and hexamethylene.

As used herein, the term "alicyclic" refers to a radical having a valence of at least one and comprising a cyclic array of atoms which is not aromatic. Heteroatoms such as nitrogen, sulfur and oxygen may be included in the array or may be composed exclusively of carbon and hydrogen atoms. Examples of alicyclic groups include cyclopropyl, cyclopentyl, cyclohexyl, and tetrahydrofuranyl.

The term "carbamoyl" as used herein refers to a functional group containing an array of OCONH atoms. For example, carbamoyl groups may be present in the reaction product of an alcohol and an isocyanate, exemplified by the compound 1-naphthylmethylcarbamate, which has a CAS No. of 63-25-2.

As used herein, the term "Boc group" refers to a protecting group for an amino group which contains a t-butyloxycarbonyl moiety. The bound nitrogen atom bearing a hydrogen atom and a Boc group is an example of a carbamoyl group.

The term "thiol promoter" as used herein refers to a molecule that incorporates a thiol group (-SH). The thiol promoter functions to improve the rate and selectivity of bisphenol formation when a hydroxyaromatic compound is condensed with an aldehyde or ketone in the presence of an acidic catalyst over that of the same reaction conducted in the absence of a thiol promoter.

The term "silylmethanethiol" refers to a thiol compound in which one silicon atom and one sulfur atom are each attached to the same carbon atom.

The present invention provides a process for the preparation of bisphenols, such as bisphenol a, by the acid catalyzed condensation of a hydroxyaromatic compound, such as phenol, with an aldehyde, such as butyraldehyde, or a ketone, such as acetone, in the presence of a thiol promoter and a modified acidic resin catalyst.

The present invention further provides such amine modified acidic resin catalysts which, when used to prepare bisphenolic compounds such as bisphenol a, provide selectivity over known acidic catalyst systems. The amine modified acidic resin catalyst is prepared by treating a polymeric material containing acidic functional groups, such as sulfonic acid groups, with an amount of amine such that about 0.1 to about 50 percent of the acidic functional groups are neutralized. The amine-modified acidic resins of the present invention are more selective catalysts, i.e., when phenol and acetone are reacted in the presence of said amine-modified acidic resin and a thiol promoter, a greater measure of selectivity to form P, P-BPA is observed relative to when a thiol promoter is combined with a known acidic resin catalyst, such as sulfonated styrene.

Typically, the acidic resin catalyst that is converted to the amine-modified acidic resin catalyst is a sulfonated styrene derivative containing the structural unit I:

the polymeric acidic resin comprising structural units (I) can be used as Amberlyst^®131、Amberlyst^®15 and Amberlyst^®36, which are all strong acid ion exchange resins commercially available from Rohm and hass Company.

Other suitable polymeric acidic resin catalysts that may be converted to the amine-modified acidic resin catalysts of the present invention also include Nafion, commercially available from DuPont^®A perfluorinated acidic resin.

Typically, such acidic resin catalysts contain from about 0.1 to about 6, preferably from about 2 to about 5 milliequivalents of acidic functional groups per gram. Typically, such acidic functional groups are sulfonic acid groups. In the practice of the present invention, it has been found to be beneficial to neutralize from about 0.1 to about 50 percent of the acidic functional groups present in the acidic resin, preferably from about 5 to about 40 percent, more preferably from about 20 to about 35 percent of the acidic functional groups, with a sufficient amount of amine. Thus, 1 g of the sulfonated polyethylene resin containing the structural unit (I) was treated SO as to contain about 5 milliequivalents of sulfonic acid groups (-SO) per gram of the resin₃H) Then, when treated with 1 milliequivalent of an amine such as pyridine, 20% of the sulfonic acid groups in the provided amine-modified acidic resin catalyst have been converted to the corresponding pyridinium sulfonate, assuming that the reaction between pyridine and the sulfonic acid groups of the resin can proceed to completion. The amine-modified acidic resin catalyst of the present invention exhibits product selectivity advantages over the unmodified acidic resin catalyst. Product selectivity can be expressed as the ratio of the weight percent of the P, P-bisphenol isomer relative to the weight percent of the 0, P-bisphenol isomer in the product mixture. In addition, product selectivity can also be expressed as the weight percent of the desired P, P-bisphenol product relative to all other products formed.

Amines suitable for use in preparing the amine modified acidic resin catalyst include aliphatic, alicyclic, and aromatic amines which are sufficiently basic to permit the attachment of the amine to the resin based on an ionic chain formed between the acidic group and the amine, such as may be found in pyridinium sulfonates.

As the aliphatic amines, triethylamine, trimethylamine, tributylamine and N, N-dimethylbutylamine can be exemplified. Illustrative alicyclic amines are piperidine, morpholine, 1, 8-diazabicyclo [5.4.0 ]]Undec-7-ene (DBU) and diazabicyclo [2.2.2]Octane (Dabco). Aromatic amines are illustrated by pyridine, imidazole, quinoline and piperazine. Generally, simple C₁-C₁₀Fatty amine, C₄-C₁₀Alicyclic amines and C₅-C₉Aromatic amines are preferred.

Thiol cocatalysts which may be employed include aliphatic, alicyclic and aromatic thiols which may be substituted with a basic group such as an amine or an acidic group such as a carboxylic acid. The thiol promoter may be used as a "bulk" promoter, meaning that such thiol promoters are not suitable for attachment to the amine-modified acidic resin, or "attached" promoters. Where the thiol promoter contains a basic functional group such as an amine, the thiol promoter may be attached to the amine-modified acidic resin catalyst and is referred to as an "attached" promoter. The functional groups present in the thiol promoter include amide, imine, and carbamoyl groups in addition to amino groups, which facilitate the attachment of the thiol promoter to the amine-modified acidic resin catalyst, such as those found in amides, imides, and carbamates, respectively.

Bulk mercaptan promoters include cycloaliphatic mercaptans such as cyclohexyl mercaptan and cyclopentyl mercaptan, aromatic mercaptans such as thiophenol and benzyl mercaptan, aliphatic mercaptans such as butyl mercaptan, hexyl mercaptan, octadecyl mercaptan, and 3-mercaptopropionic acid.

The attached thiol promoters include 2-mercaptomethylpyridine, cysteamine, and 4-aminobutylthiol immobilized on an amine-modified acidic resin catalyst, such as a sulfonated polystyrene, in which about 20% of the sulfonic acid groups have been neutralized with pyridine.

Among the aliphatic thiols suitable for use in the present invention, silylmercaptols having the following formula (II) have been found to be particularly effective as thiol promoters:

wherein R is¹And R²Each independently is hydrogen, C₁-C₄₀Fatty radical, C₃-C₄₀Aryl radical, C₃-C₄₀An alicyclic group; or R¹And R²Together form a C₁-C₄₀Alicyclic group of or C₄-C₄₀An aromatic group;

R³-R⁵each independently is C₁-C₄₀Fatty radical, C₃-C₄₀Aryl or C₃-C₄₀An alicyclic group; or R³-R⁵Any two of which together form a C₅-C₄₀Alicyclic group of or C₅-C₄₀An aromatic group; or R³-R⁵The genes together forming a C₉-C₄₀Alicyclic group of or C₁₀-C₄₀An aromatic group.

R in Structure II¹-R⁵Where any of the groups contains a basic functional group such as an amino group, such a silylmethanethiol promoter can be attached to the amine-modified acidic resin catalyst. The functional groups present in the silylmethanethiol may be, in addition to the amino groups which enable the co-catalyst to be readily attached to the amine-modified acidic resin catalyst, amide groups, imide groups and carbamoyl groups, which may be found in amides, imides and carbamates, respectively.

Silyl methanethiols of formula II are known in the chemical literature and methods for their preparation have also been described, for example, in j. org. chem, 53(5)844 (1987); chem, 51(18), 3428(1986) and Tetrahedron Letters 26(11), 14251985, etc. In some instances, the silyl methanethiol of formula (II) is commercially available, for example, as trimethylsilyl electrothiol, from TCI chemical company of Portland, Oregon. Other members of this class of compounds can be prepared by reacting chloromethylsilane of formula (III) with a sulfur-containing nucleophile such as sodium sulfide, sodium thioacetate, or thiourea. The silylmethanethiol (II) can be obtained directly in the case of sodium sulfide. In the case where a thioacetate is used as the nucleophile, the acetate derivative (IV) is obtained. The acetate derivative (IV) is readily converted to the corresponding thiol (II) upon solvation, for example by heating the acetate derivative (IV) with methanol in the presence of a basic catalyst such as triethylamine.

Chloromethyl silicon compounds corresponding to formula (III) can be prepared by a number of methods in which the hydrosilylation reaction of the olefin of formula (V) with chloromethylsilane VI incorporates a silicon hydride functional group. Thus, an olefin V in which the radical R is⁶Corresponding to the radical R⁵The homologues of at least two carbon atoms can be reacted with chloromethylsilane (VI) in the presence of a noble metal catalyst to provide chloromethylsilicon derivative (III).

The chloromethylsilane compound (III) can be converted into the silylmethanethiol compound (II) and the acetate derivative of silylmethanethiol (IV) under various reaction conditions. Typically, chloromethylsilane (III) is combined with a slight excess of sodium sulfide or sodium thioacetate in a polar solvent such as methanol or dimethylformamide, and the reaction mixture is stirred at a temperature between about 0 deg.C and about 100 deg.C until the starting chloromethylsilane (III) has been consumed, as determined by analytical techniques such as gas chromatography, thin layer chromatography, and the like. The reaction mixture is then partitioned between water and a solvent such as dichloromethane, toluene or ethyl acetate. The separated organic layer is then washed with water to complete removal of the inorganic salts and then dried with a suitable drying agent such as magnesium sulfate. Filtration and evaporation of the solvent yields a crude product which can be used as a thiol promoter in BPA production or can be purified, for example by column chromatography or recrystallization, before use.

Examples of silylmethanethiol compounds that can be used as a co-catalyst in the production of bisphenols include, but are not limited to, trimethylsilylmethanethiol, triethylsilylmercaptan, tripropylsilylmethanethiol, tributylsilylmethanethiol, 1-trimethylsilyl-1-ethylmethanethiol, and 1-trimethylsilyl-1-benzylmethanethiol.

Where a silylmethanethiol promoter is used as the bulk promoter, the preferred silylmethanethiol promoter is trimethylsilylmethanethiol, since it is readily available, easily prepared, and easily recovered or removed from the reaction product.

In certain cases, it may be beneficial to employ derivatives of silylmethanethiol, such as trimethylsilylmethanethiol acetate, in the process of the invention. In such cases, it is believed that the silylmethanethiol acetate is converted to the active silylmethanethiol promoter under the reaction conditions. Silyl mercaptan acetate and other silyl mercaptan derivatives, which provide silyl mercaptan under the reaction conditions, may be advantageously used in the same concentrations as when the silyl mercaptan itself is used.

In some cases, the silylmethanethiol promoter may function as an adhesion promoter, as in the case of silylmethanethiols that incorporate an amine functional group that can be used to form an adhesion to the amine modified acidic resin catalyst. The attachment of the silylmethanethiol to the amine modified acidic resin catalyst may be based on strong hydrogen bonding interactions or the formation of covalent bonds. Examples of silylmethanethiols that can be used as attached co-catalysts in the production of bisphenols include 3-aminopropyldimethylsilylmethanethiol, 3-N-methylaminopropyldimethylsilylmethanethiol, 3-N, N-dimethylaminopropyldimethylsilanethiol, 3- (1-piperidinyl) propyldimethylsilylmethanethiol and 2- (4-pyridinyl) ethyldimethylsilylmethanethiol.

Derivatives of such materials incorporating an acylated thiol group and a protected amino group, in addition to the silylmethanethiol group incorporating the free amino group, may also be employed. For example, N-Boc-3-aminopropyldimethylsilylmethanethiol acetate derivative VII, which has also been found to be useful as an attachment promoter in the production of bisphenols, thioacetate VII, is believed to be converted to 3-aminopropyldimethyl-silylthiol VIII:

as already stated, the present invention provides a process for the preparation of bisphenols, such as bisphenol A, wherein an amine-modified acidic resin catalyst is employed which, together with a thiol promoter, effects the condensation of a hydroxyaromatic compound with an aldehyde or ketone. Examples of hydroxyaromatic compounds include phenol, o-cresol, m-cresol, 2-tert-butyl phenol, 2-propyl phenol and 1-naphthol. Examples of aldehydes include formaldehyde, acetaldehyde, propionaldehyde, and butyraldehyde. Examples of ketones include acetone, cyclohexanone; 3, 3, 5-trimethylcyclohexanone, 2-butanone and fluorenone.

There are many bisphenol compounds such as 2, 2-bis (4-hydroxyphenyl) propane, 2-bis (4-hydroxy-3-methylphenyl) propane, 1-bis (4-hydroxyphenyl) cyclohexane, 1-bis (4-hydroxy-3-methylphenyl) cyclohexane and 1, 1-bis (4-hydroxyphenyl) -3, 3, 5-trimethylcyclohexane, etc., which can be prepared by the process of the present invention. The invention is best illustrated by its application in the preparation of bisphenol A, namely via the condensation of phenol, a hydroxy aromatic compound, with acetone, a ketone compound. The mixture containing phenol and acetone may be contacted with the amine-modified acidic resin catalyst and the thiol promoter at a temperature of between about 20 ℃ and about 100 ℃, more preferably between about 40 ℃ and about 90 ℃, and most preferably between about 50 ℃ and about 80 ℃.

The process of the present invention may be used as a batch process or a continuous process. When the process of the present invention is applied as a continuous process, the amine-modified acidic resin catalyst may be disposed in a fixed bed or stirred tank reactor such that the reactants phenol, acetone and mercaptan promoter may be continuously supplied to and removed from the catalyst in a continuous manner. Alternatively, the amine-modified acidic resin catalyst may be pretreated with a thiol promoter containing a group such as an amine or carbamate capable of attaching to the amine-modified acidic resin catalyst. With the attached thiol promoter, it may be possible to eliminate the need to include a thiol promoter in the feed stream containing phenol and acetone. Where a thiol promoter is used that contains a basic functional group, it may be attached to the amine-modified acidic resin itself or may be included in the preparation of the amine-modified acidic resin from the unmodified acidic resin.

When the process of the present invention is applied as a continuous process, the various reactants are combined to give a feed mixture that is introduced at a space velocity of from about 0.1 to about 0.6, preferably from about 1 to about 4, more preferably from about 2 to about 3.5 pounds of feed mixture per pound of catalyst per hour by weight per hour. The feed mixture comprises about 0.1 to about 10 weight percent acetone and about 70 to about 99 weight percent phenol; preferably about 3 to about 8 weight percent acetone and about 85 to about 96 weight percent phenol; most preferably about 3 to about 6 weight percent acetone and about 90 to about 96 weight percent phenol. When used as a co-catalyst as a whole, the thiol co-catalyst is present in an amount in the range of from about 5 to about 100 millimoles (in millimoles per liter of feed solution) per liter of feed solution, preferably from about 10 to about 75 millimoles per liter of feed solution, and even more preferably from about 20 to about 40 millimoles per liter of feed solution. When used as an attached promoter, the mercaptan is present in an amount in the range of between about 0.1 and about 3 milliequivalents per gram of amine-modified acidic resin catalyst, preferably in the range of between about 0.5 and about 2 milliequivalents per gram of amine-modified acidic resin catalyst.

Examples

The following examples are put forth so as to provide those skilled in the art with a complete disclosure and description of how the methods claimed herein can be evaluated. Unless otherwise stated. Parts are by weight, temperature is in degrees celsius. The materials and test procedures used to achieve the results are described herein below:

the starting material and product compositions were determined by gas chromatography on a Hewlett Packard model 5890 gas chromatograph. Chromatograph-mass spectrometry data were obtained using a Hewlett Packard model 5971 GC-MS instrument. The laboratory robot used was 8 probes G: of the type lsom 215, modified to enable transfer of molten phenol solution. The reaction zone is heated by means of a heating zone and the reaction temperature is brought to 70 ℃. + -. 1 ℃.

The surprising effect of the amine modified acidic resin catalyst was demonstrated on a laboratory scale by conducting the test in a reaction vessel designed for use as a stirred tank reactor operating in a continuous production mode. Sampling was performed under steady state conditions. The modification of the acidic resin catalyst is carried out as follows: a solid acidic resin catalyst (47-49 mg), such as Amberlyst131, is added to each well of a 96-well polypropylene reaction zone equipped with magnetic stirring sealed with a septum and, with the aid of a laboratory robot, a mixture containing an amine, such as pyridine, and optionally a thiol promoter, such as cysteamine, which can attach to the resin. The amounts of amine and cocatalyst are selected such that 5 to 50 percent of the total number of acid sites on the resin are neutralized. In the case where the thiol promoter does not contain a basic functional group such as an amine, the amine is not included in the catalyst modification step because it is attached to the acidic resin catalyst by the amine, but rather is added as part of the phenol-acetone feed mixture. A mixture of the solid acidic resin catalyst and the amine-containing phenol and optionally the thiol promoter is heated with agitation to 70 ℃ for one hour to provide the amine-modified acidic resin catalyst. The reactants phenol, acetone and optionally thiol promoter are then added and the mixture is heated with stirring at 70 ℃ for 7 minutes. At this point a portion of the reaction mixture was withdrawn, taking care to ensure that a supernatant, rather than a solid catalyst, was withdrawn. After a further 7 minutes, an amount of reactant solution equal to the volume removed in the previous step was added. The reaction volume was "compensated" with fresh reactants and one cycle was completed. The residence time of the liquid was about one hour and the production rate of the stock solution was about 3 grams of stock solution per gram of resin catalyst per hour. After 40 cycles, the reaction mixture is considered to have reached a steady state, at which point the reaction mixture may be sampled and analyzed by gas chromatography. Each reaction was performed twice.

Examples 1 to 35 and comparative examples 1 to 6

The reactor was charged with 4% cross-linked sulfonated styrene beads and treated with the amines shown in Table 1 as described in the general experimental section. The stock solution of the reactants contained about 4.5 weight percent acetone, about 95 weight percent phenol. This stock solution further contains a thiol promoter (3-mercaptopropionic acid, benzylthiol, or trimethylsilylmethanethiol) at a concentration ranging between about 20.5 and about 41 millimoles per liter. The data are provided in tables 1-3. Examples 1-35 demonstrate the improved selectivity of amine modified acidic resin catalysts. Comparative examples 1-6 illustrate the lower selectivity associated with the use of unmodified acidic resin catalysts.

TABLE 1 thiol promoter is 3-mercaptopropionic acid

Example numbering	Mercaptan co-catalyst	Amines as pesticidesc	Amine loading	pp+/op	pp-BPA
							(mmole/l)b)		(milliequivalents/g)d)	Mean value ofe	SelectingAverage value of sexf
1	20.5	Pyridine compound	0.5	15.42	92.64
						2	20.5	Pyridine compound	1	16.77	93.20
3	20.5	Pyridine compound	1.5	18.37	93.79
						4	20.5	Triethylamine	0.5	15.35	92.45
5	20.5	Triethylamine	1	16.70	93.18
						6	20.5	Triethylamine	1.5	18.56	93.80
CE-1a	20.5		0	14.35	91.98
						7	41	Pyridine compound	0.5	17.69	93.36
8	41	Pyridine compound	1	19.58	94.01
						9	41	Pyridine compound	1.5	22.05	94.67
10	41	Triethylamine	0.5	17.33	93.33
						11	41	Triethylamine	1	20.09	94.13
12	41	Triethylamine	1.5	23.06	94.68
						CE-2a	41		0	15.95	92.70

Notes in the table:

^acomparative example (c);^bconcentration in millimoles per liter;^camines used to modify acidic resin catalysts;

^dmilliequivalents of amine per gram of acidic resin catalyst;^eselectivity expressed as the weight percent of P, P-BPA present in the reaction mixture divided by the weight percent of O, P-BPA present in the reaction mixture;

^fselectivity expressed as% by weight of P, P-BPA present in the product mixture relative to all other phenol/acetone condensation products present in the reaction mixture.

TABLE 2 mercaptan promoter is benzylmercaptan

Example numbering	Mercaptan co-catalyst	Amines as pesticidesc	Amine loading	pp/op	pp-BPA
							(mmole/l)b)		(milliequivalents/g)d)	Mean value ofe	Mean value of selectivityf
13	20.5	Pyridine compound	0.5	15.57	92.62
						14	20.5	Pyridine compound	1	17.70	93.48
15	20.5	Pyridine compound	1.5	20.66	94.31
						16	20.5	Triethylamine	1	17.68	93.38
17	20.5	Triethylamine	1.5	20.77	94.31
						CE-3a	20.5		0	14.38	91.97
						18	41	Pyridine compound	0.5	17.98	93.45
19	41	Pyridine compound	1	20.79	94.23
						20	41	Pyridine compound	1.5	24.15	95.03
21	41	Triethylamine	0.5	17.96	93.41
						22	41	Triethylamine	1	21.34	94.43
23	41	Triethylamine	1.5	25.42	95.12
						CE-4a	41		0	15.59	92.42

Notes in the table:

^acomparative example (c);^bconcentration in millimoles per liter;^camines used to modify acidic resin catalysts;

^dmilliequivalents of amine per gram of acidic resin catalyst;^eas P, P-BPA present in the reaction mixture

Selectivity expressed as the weight percent of O, P-BPA present in the reaction mixture divided by the weight percent of O, P-BPA present in the reaction mixture;

^fselectivity expressed as% by weight of P, P-BPA present in the product mixture relative to all other phenol/acetone condensation products present in the reaction mixture.

TABLE 3 mercaptan promoter is trimethylsilylmethanethiol

Example numbering	Mercaptan co-catalyst	Amines as pesticidesc	Amine loading	pp/op	pp-BPA
							(mmole/l)b)		(milliequivalents/g)d)	Mean value ofe	Mean value of selectivityT
24	20.5	Pyridine compound	0.5	18.80	93.67
						25	20.5	Pyridine compound	1	21.60	94.49
26	20.5	Pyridine compound	1.5	24.78	95.11
						27	20.5	Triethylamine	0.5	18.58	93.63
28	20.5	Triethylamine	1	22.34	94.64
						29	20.5	Triethylamine	1.5	26.40	95.24
CE-5a	20.5		0	16.38	92.80
						30	41	Pyridine compound	0.5	20.43	94.14
31	41	Pyridine compound	1	24.10	94.95
						32	41	Pyridine compound	1.5	27.73	95.44
33	41	Triethylamine	0.5	20.52	94.10
						34	41	Triethylamine	1	25.39	95.11
35	41	Triethylamine	1.5	29.31	95.62
						CE-6a	41		0	17.44	93.19

Notes in the table:

^acomparative example (c);^bconcentration in millimoles per liter;^camines used to modify acidic resin catalysts;

^dthe number of milliamines per gram of acidic resin catalyst;^eselectivity expressed as the weight percent of P, P-BPA present in the reaction mixture divided by the weight percent of O, P-BPA present in the reaction mixture;

^fselectivity expressed as% by weight of P, P-BPA present in the product mixture relative to all other phenol/acetone condensation products present in the reaction mixture.

Examples 36 to 55 and comparative examples 7 to 10

The reactor was charged with 4% cross-linked sulfonated polystyrene beads and treated with amine and thiol co-catalyst cysteamine as described in the general experimental section. The total amine amount and the amount of the thiol promoter cysteamine attached should be between about 0.5 and about 2 milliequivalents per gram of resin catalyst. The stock solution of the reactants contained about 4.5 weight percent acetone and about 95.5 weight percent phenol. The data are provided in table 4. Examples 36-55 demonstrate that the amine-modified acidic resin catalyst with attached co-catalyst cysteamine has excellent selectivity. For example, examples 36-40 and comparative example 7 demonstrate that at 2 milliequivalents of cysteamine per gram of acidic resin catalyst, the observed selectivity is maintained at the level of pyridine-containing amine-modified acidic resin catalyst, the total amine content of which is kept constant. The data demonstrates that lower cysteamine concentrations can be used without sacrificing selectivity to form bisphenol a. Examples 41 to 45 and comparative example 8 announce the same effect in different concentration ranges as was done for examples 45 to 60 and comparative example 9. Examples 51-55 and comparative example 10 demonstrate that at relatively low amine concentrations, i.e., 0.5 milliequivalents per gram of acidic resin catalyst, the system will provide lower selectivity for P, P-BPA formation when cysteamine is replaced with pyridine.

TABLE 4 attached Co-catalyst on amine modified acidic resin catalyst

Example numbering	Total amines b	Pyridine c	Cysteamine d	BPA Selectivity e
						(milliequivalent/gram)	(milliequivalent/gram)	(milliequivalent/gram)	Mean value of
CE-7a	2	0	2	94.95
					36	2	0.4	1.6	95.01
37	2	0.8	1.2	95.19
					38	2	1.2	0.8	95.40
39	2	1.6	0.4	95.17
					40	2	1.8	0.2	95.14
CE-8	1.5	0	1.5	94.89
					41	1.5	0.3	1.2	94.87
42	1.5	0.6	0.9	94.85
					43	1.5	0.9	0.6	94.97
44	1.5	1.2	0.3	94.72
					45	1.5	1.35	0.15	94.36
CE-9	1	0	1	94.29
					46	1	0.2	0.8	94.27
47	1	0.4	0.6	94.25
					48	1	0.6	0.4	94.15
49	1	0.8	0.2	93.74
					50	1	0.9	0.1	93.43
CE-10a	0.5	0	0.5	93.60
					51	0.5	0.1	0.4	93.48
52	0.5	0.2	0.3	93.24
					53	0.5	0.3	0.2	93.05
54	0.5	0.4	0.1	92.25
					55	0.5	0.45	0.05	91.75

Notes in the table:

^acomparative example^bThe total amount of cysteamine and pyridine expressed as milliequivalents per gram of acidic resin;

^cthe number of milliequivalents of pyridine per gram of acidic resin catalyst;

^dmilliequivalents of cysteamine per gram of acidic resin catalyst;

^eselectivity expressed as the weight% of P, P-BPA in the product mixture relative to all other phenol/acetone condensation products present in the reaction mixture.

Preparation of silylmethanethiol derivatives VII

To a 250 ml three-neck round bottom flask equipped with a reflux condenser tube, nitrogen inlet, heating mantle with thermometer, isobaric dropping funnel and magnetic stirrer were added 14.36 g (91.3 mmol) of tert-butyl N-allylcarbamate and 150 ml of toluene. The olefin and solvent were stirred and heated to about 70 deg.C, then 10 microliters of Karstedt's catalyst (5% Pt solution, about 30ppm Pt based on olefin) was added. A solution containing 12 g (110.5 mmol) chloromethyldimethylsilane in 20 ml toluene was carefully added over about 30 minutes at a rate to maintain the temperature of the reaction between about 80 ℃ and about 100 ℃. After the addition was complete, the reaction was stirred and heated at about 85 ℃ for about 1 hour. GC-MS analysis indicated that the olefin had reacted completely to form the silylated compound, N-Boc-3-aminopropylchloromethyl dimethylsilane. The solution was transferred to a 500 ml single neck round bottom flask and stripped of solvent and excess silane via a rotary evaporator to yield 25 grams of crude product (quantitative yield based on olefin).

Solid potassium thioacetate (1.37 g, 0.012 mol) was added to a 125 ml reaction flask equipped with a magnetic stirrer in a dry box filled with nitrogen. And taking out the reaction bottle from the drying box after a diaphragm is arranged on the reaction bottle cap. Methanol (30 ml) was added and the mixture was stirred to dissolve the potassium thioacetate. Crude N-Boc-3-aminopropylchloromethyldimethylsilane (2.65 g, 0.01 mol) was then added via syringe and the mixture was warmed at about 50 ℃ for about 4.5 hours. The mixture was then allowed to stand at room temperature for about 48 hours. Water (50 ml) and dichloromethane (50 ml) were added and the phases separated. The organic layer was taken out, washed twice with water, dried over sodium sulfate, filtered through a silica gel column and concentrated under reduced pressure to give N-Boc-3-aminopropyldimethylsilylmethanethiol acetate derivative VII (2.84 g) as a nearly colorless oil. It¹HNMR、¹³CNMR and GC-MS are in full agreement with Structure VII.

The invention has been described in detail with particular reference to preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention.

Claims (10)

1. A process for the manufacture of bisphenols, said process comprising contacting a mixture comprising a hydroxyaromatic compound and a ketone or aldehyde with an amine-modified acidic resin catalyst prepared from an acidic resin comprising acidic functional groups by neutralizing a portion of said acidic functional groups with an amine other than any thiol promoter which itself comprises an amine group, in the presence of a thiol promoter at a temperature in the range of between 25 ℃ and 95 ℃.

2. The process of claim 1 wherein said amine modified acidic resin catalyst is prepared from sulfonated polystyrene having the following repeating unit I:

3. the process of claim 2 wherein said amine modified acidic resin catalyst contains from about 0.1 to about 6 milliequivalents of sulfonic acid groups per gram of resin.

4. The process of claim 1 wherein the amine used in the preparation of the amine-modified acidic resin is an aliphatic, aromatic or cycloaliphatic amine.

5. The process of claim 1 wherein said thiol promoter is selected from the group consisting of aliphatic thiols, alicyclic thiols, and aromatic thiols.

6. The method of claim 1 wherein the bisphenol is selected from the group consisting of 2, 2-bis (4-hydroxyphenyl) propane; 2, 2-bis (4-hydroxy-3-methylphenyl) propane; 1, 1-bis (4-hydroxyphenyl) cyclohexane; 1, 1-bis (4-hydroxy-3-methylphenyl) cyclohexane; 1, 1-bis (4-hydroxyphenyl) -3, 3, 5-trimethylcyclohexane and 9, 9-bis (4-hydroxyphenyl) fluorene.

7. The process of claim 1 wherein said mixture comprising a hydroxyaromatic compound and a ketone or aldehyde comprises about 0.1 to about 10 weight percent acetone and about 70 to about 99 weight percent phenol.

8. A process for the manufacture of bisphenol a, said process comprising contacting a mixture of phenol and acetone, said phenol being present in an amount ranging between about 90 to about 95 percent by weight, and said acetone being present in an amount ranging between about 4 to about 6 percent by weight, with a thiol promoter at a temperature ranging between about 50 ℃ to about 80 ℃ in the presence of an amine-modified acidic resin catalyst, said thiol promoter being present in an amount ranging between about 10 to about 100 millimoles per liter of reactants, said amine-modified acidic resin catalyst being prepared from an acidic resin containing acidic functional groups by neutralizing a portion of said acidic functional groups with an amine that is different from any thiol promoter that itself contains an amine group.

9. A process for the manufacture of bisphenol A, said process comprising reacting bisphenol A at a temperature in the range of between about 50 ℃ and about 80 ℃, contacting a mixture of phenol and acetone in the presence of an amine-modified acidic resin catalyst, said phenol being present in an amount ranging between about 90 to about 95 percent by weight of said mixture and said acetone being present in an amount ranging between about 4 to about 6 percent by weight of said mixture, the amine-modified acidic resin catalyst is prepared from an acidic resin containing acidic functional groups by neutralizing a portion of the acidic functional groups with an amine, the amine being different from any thiol promoter that itself contains an amine group, the amine-modified acidic resin catalyst also contains a thiol promoter, the thiol promoter contains a functional group selected from the group consisting of an amino group, an amide group, an imine group, and a carbamoyl group; the thiol promoter is present in an amount of between about 0.5 and about 2 millimoles per gram of resin.

10. An amine-modified acidic resin catalyst prepared from an acidic resin containing acidic functional groups by neutralizing a portion of the acidic functional groups with an amine that is different from any thiol promoter that itself contains an amine group, which contains; sulfonated polystyrene unit (I):

residues derived from aromatic, aliphatic and cycloaliphatic amines; the catalyst also contains a thiol promoter that contains amino, amido, imido, or carbamoyl groups.