CS216081B3 - Method of preparation of the bisphenols - Google Patents

Description

The present invention relates to a process for the preparation of bisphenols by condensation of suitable phenolic and ketone compounds under cation exchange with a special polymeric material structure which ensures a high condensation rate.

The author's certificate is dependent on the author's certificate No. 200 351.

The synthesis of bisphenols is very sensitive to the polymer structure of the ion exchange catalyst. At high speed, it only takes place in a very permeable, low crosslinked polymer mass. However, the polymer mass of the ion exchange catalyst of such properties is very soft and easily deformable, so that conventional low crosslinked ion exchangers cannot be used in an industrial reactor. According to MS. AO 200 351 is advantageous to carry out the preparation of bisphenols in the presence of a special ion exchange catalyst which, due to the higher crosslinking, has good mechanical properties but, despite the relatively high content of crosslinking agent, has a high catalytic activity, similar to low crosslinked ion exchangers. In the polymeric backbone of this special ion exchange catalyst, the crosslinking component is particularly unevenly distributed, so that, in addition to a substantial proportion of the low crosslinked polymer mass, it also contains a higher crosslinking reinforcing component. This is accomplished by adding solvents to the polymerization mixture to prepare their polymer backbone.

These solvents may be of two types. On the one hand, those in which the polymer formed does not swell, and on the other hand those in which the resulting polymer does not swell, the so-called precipitants. It is advantageous to use mixtures of both types of solvents. A certain disadvantage of the precipitants, specifically designed for the preparation of the ion exchange catalyst and the polymer structure particularly suitable for catalysis in AO 200 351, i.e. aliphatic hydrocarbons having 5 to 13 C or fatty acids at 15 to 20 C, is their difficulty in removing from the finished copolymers. The present invention provides a process for preparing bisphenols using a similar ion exchange catalyst as proposed for this purpose in AO 200 351, but prepared using alcohols having 1 to 10 ° C as modifying solvents. The addition of alcohols, in particular lower C 1 to 4 C, can be used as an erupting agent in the sense of the desired effects according to AO 200 351 and optionally supplemented with an admixture of botnels as 6 to 9 C aromatic hydrocarbons, 1 to 4 C aliphatic halogenated hydrocarbons or halogenated benzene derivatives. . In contrast to the precipitates recommended in the AO 200 351 certificate, the removal of alcohols from the finished copolymers is much easier. In addition, for alcohols, by changing the length of the polymer chain, the lipophilic character of the molecule can be controlled and the desired modification of the polymer structure can be achieved with a one-component additive without the particular addition of botnels, which may be technologically advantageous.

Example 1

A mixture of 21.75 g of styrene and 2.33 g of technical divinyl benzene (61.5% DVB), 0.15 g of dibenzoyl peroxide (81% active ingredient) and 15.5 g of n-butanol is dispersed in 100 ml of a 0.12% solution. polyvinyl alcohol in which 0.35 g of potato starch was dissolved. It is polymerized with stirring for 4 h at 80 ° C and 2 h at 90 ° C, then the inerts and unreacted components are removed by steam distillation. The copolymer is washed with water and dried at 80 ° C for 10 h.

A fraction of 0.25 to 1 mm is separated from the dry copolymers. The sorted copolymer was sulfonated by an eight-fold excess of 98 wt% after pre-swelling in 1,2-dichloroethane. of sulfuric acid at 80 to 125 ° C for 6 h. A strongly acid cation exchanger was obtained and had a exchange capacity of 5.23 meq / g.

Example 2

A mixture of 209 g of styrene, 30.7 g of divinyl benzene (62.5% DVB), 196.2 g of 2-ethylhexanol and

1.5 g of dibenzoyl peroxide (80% active ingredient) are dispersed in 1200 g of a 0.15% polyvinyl alcohol solution in which 4.5 g of potato starch was dissolved. The polymer is polymerized for 5 hours at 76 ° C and 5 hours at 90 ° 0, then the inerts and unreacted components are distilled off with steam. The copolymer is dried for 6 hours at 40 ° C and for 6 hours at 80 ° C. The separated 0.25-1.2 mm fraction was sulfonated as described in Example 1. A strongly acidic cation exchanger was obtained with a exchange capacity of 5.12 meq / g. Example 3

A homogeneous mixture of 180.5 g styrene, 19.5 g divinylbensaau (61.5% DVB), 100 g n-butaaol, 100 g toluene and 1.2 g dibenzoyl peroxide (80% active ingredient) is dispersed in 800 g 0.2 % polyvinyl alcohol solution. It is polymerized for 4 hours at 80 ° C and 6 hours at 90 ° C. The inerts and unreacted components are distilled off with steam, the copolymer is washed with water and dried at 80 ° C for 10 h. A grain fraction of 0.25 to 1 mm in size was sulfonated according to Example 1 to give a strongly acidic cation exchanger having a exchange capacity of 5.20 meq / g.

Examples of use

All of the catalysts in Preparation Examples 1-3 were tested for the reaction of the synthesis of 4,4- (1-methylidene) bisphenol (commercial names bisphenol A, dian) in a flow tube microreactor at 70 ° C with a phenol / acetone reaction mixture in a molar ratio 8 «1,

Commercial cation exchangers A and B, which are declared by the manufacturer as special ion exchangers for catalysis, were also included in the test. All ion exchangers tested were pre-modified by neutralizing 15 L of the acidic active groups with mercaptoethylamine. The results are shown in the table below:

Test results of ion exchange catalyst activity. Synthesis of bisphenols A, 70 ° C, phenol / acetone reaction mixture 8: 1.

Catalyst Catalyst load (g cat.h / mol acetone) Acetone conversion (%) Example 1 65 45 90 49 130 55 Example 2 65 43 90 51 130 55 Example 3 60 50 90 53 130 61 AND 250 26 500 50 (B) 130 39 260 44 350 58

SUBJECT OF THE INVENTION

Claims (1)

A process for the preparation of bisphenols according to A.O. No. 200 351, characterized in that the reaction is carried out in the presence of a strongly acidic ion exchange catalyst in which the heterogeneous distribution of the crosslinking component is achieved by solvents of the C 1 -C 10 alcohol type. 0 to 60 wt. aromatic hydrocarbons having from 6 to 9 carbon atoms, aliphatic halogenated hydrocarbons having from 1 to 4 carbon atoms, or halogenated derivatives of benzene, added to the polymerization mixture in the preparation of the polymer backbone.