阅读说明：本技术 3,3,5-三甲基环己叉基双酚的制备方法 (Preparation method of 3,3,5-trimethylcyclohexylidene bisphenol ) 是由 J·范登艾恩德 E·施卢伊茨 K·海伦 M·特拉温 V·米歇尔 于 2019-08-15 设计创作，主要内容包括：本发明涉及3,3,5-三甲基环己叉基双酚(BP-TMC)的制备。特别地,本发明涉及在气态酸性催化剂存在下由3,3,5-三甲基环己酮(TMC-酮)和苯酚制备3,3,5-三甲基环己叉基双酚(BP-TMC)。优选连续进行制备。本发明的目的是当将气态酸性酸计量加入反应容器中的包含TMC-酮和苯酚的反应混合物中时,防止固体,特别是结晶的BP-TMC,更特别是结晶的BP-TMC-苯酚-加合物堵塞气态酸性酸的计量阀的出口。(The invention relates to the preparation of 3,3,5-trimethylcyclohexylidene bisphenol (BP-TMC). In particular, the present invention relates to the preparation of 3,3, 5-trimethylcyclohexylidenebisphenol (BP-TMC) from 3,3, 5-trimethylcyclohexanone (TMC-ketone) and phenol in the presence of a gaseous acidic catalyst. The preparation is preferably carried out continuously. The object of the present invention is to prevent solids, in particular crystalline BP-TMC, more in particular crystalline BP-TMC-phenol-adduct, from clogging the outlet of the metering valve for gaseous acidic acid when metering gaseous acidic acid into a reaction mixture comprising TMC-ketone and phenol in a reaction vessel.)

1. A continuously conducted process for the preparation of 3,3, 5-trimethylcyclohexylidenebisphenol (BP-TMC) in the presence of a gaseous acidic catalyst, said process comprising at least the steps of:

or

(a1) Providing a separate first stream comprising:

    (i) 3,3, 5-trimethylcyclohexanone (TMC-ketone), said TMC-ketone having a purity of at least 90 wt. -%, preferably of at least 95 wt. -%, more preferably of at least 98 wt. -%, and said TMC-ketone comprising less than 1 wt. -%, preferably less than 0.5 wt. -%, more preferably less than 0.2 wt. -%, most preferably less than 0.1 wt. -% phenol,

    (ii) a gaseous acid catalyst;

(b1) providing a separate second stream comprising:

    (iii) a phenol,

    (iv) additional components;

or

(a2) Providing a separate first stream comprising:

    (v) phenol having a purity of at least 90 wt.%, preferably at least 95 wt.%, more preferably at least 99 wt.%, most preferably at least 99.9 wt.% and comprising less than 0.5 wt.%, preferably less than 0.2 wt.%, more preferably less than 0.1 wt.%, most preferably less than 0.05 wt.% of TMC-ketone,

    (vi) a gaseous acid catalyst;

(b2) providing a separate second stream comprising:

    (vii) phenol,

    (viii) TMC-ketone,

    (ix) a further component;

and then subsequently

(c) Combining the first stream and the second stream together in a reaction vessel to form a reaction mixture.

2. The method of claim 1, wherein in step (a1), in the first separate stream

TMC-ketone is present in an amount of 40 to 80 wt. -%, preferably in an amount of 50 to 70 wt. -%, more preferably in an amount of 55 to 65 wt. -%, and

the gaseous acid catalyst is present in an amount of from 20 to 60 wt. -%, preferably in an amount of from 30 to 50 wt. -%, more preferably in an amount of from 35 to 45 wt. -%,

wherein the sum of the amounts of TMC-ketone and gaseous acidic catalyst is 100 wt.%.

3. The method of claim 1, wherein in step (b1), in the second separate stream

Phenol is present in an amount of at least 75 wt.%, preferably in an amount of at least 80 wt.%, more preferably in an amount of at least 85 wt.%,

the further component is present in an amount of less than 25 wt. -%, preferably in an amount of less than 20 wt. -%, more preferably in an amount of less than 15 wt. -%,

wherein the sum of the amounts of phenol and further components is 100 wt.%.

4. The process according to claim 1, wherein in step (b1), the separate second stream further comprises TMC-ketone, BP-TMC and by-products as further components.

5. The method of claim 5, wherein in step (b1), in the second separate stream

Phenol is present in an amount of at least 75 wt.%, preferably in an amount of at least 80 wt.%, more preferably in an amount of at least 85 wt.%,

TMC-ketone is present in an amount of less than 6 wt. -%, preferably in an amount of less than 2 wt. -%, more preferably in an amount of less than 1 wt. -%,

BP-TMC is present in an amount of less than 5 wt. -%, preferably in an amount of less than 3 wt. -%, more preferably in an amount of less than 1 wt. -%,

the by-products are present in an amount of less than 23 wt. -%, preferably in an amount of less than 15 wt. -%, more preferably in an amount of less than 4 wt. -%,

wherein the sum of the amounts of phenol, TMC-ketone, BP-TMC and by-products is 100% by weight.

6. The method of claim 1, wherein in step (a2), in the first separate stream

Phenol is present in an amount of 40 to 80 wt.%, preferably in an amount of 50 to 70 wt.%, more preferably in an amount of 55 to 65 wt.%, and

the gaseous acid catalyst is present in an amount of from 20 to 60 wt. -%, preferably in an amount of from 30 to 50 wt. -%, more preferably in an amount of from 35 to 45 wt. -%,

wherein the sum of the amounts of phenol and gaseous acidic catalyst is 100 wt.%.

7. The method of claim 1, wherein in step (b2), in the second separate stream

Phenol is present in an amount of at least 65 wt.%, preferably in an amount of at least 70 wt.%, more preferably in an amount of at least 75 wt.%,

TMC-ketone is present in an amount of 15 to 25 wt%,

the further component is present in an amount of less than 20 wt. -%, preferably in an amount of less than 15 wt. -%, more preferably in an amount of less than 10 wt. -%,

wherein the sum of the amounts of phenol, TMC-ketone and further components is 100 wt.%.

8. The process of claim 1, wherein in step (b2), the separate second stream further comprises BP-TMC and by-products as additional components.

9. The method of claim 9, wherein in step (b2), in the second separate stream

Phenol is present in an amount of at least 65 wt.%, preferably in an amount of at least 70 wt.%, more preferably in an amount of at least 75 wt.%,

TMC-ketone is present in an amount of 15 to 25 wt%,

BP-TMC is present in an amount of less than 5 wt. -%, preferably in an amount of less than 3 wt. -%, more preferably in an amount of less than 1 wt. -%,

the by-products are present in an amount of less than 19 wt%, preferably in an amount of less than 12 wt%, more preferably in an amount of less than 9 wt%,

wherein the sum of the amounts of phenol, TMC-ketone, BP-TMC and by-products is 100% by weight.

10. The process of claim 1 wherein the gaseous acid catalyst comprises hydrogen sulfide and hydrogen chloride.

11. The process according to claim 7, wherein the molar ratio between hydrogen chloride and hydrogen sulfide is from 4:1 to 20:1, preferably from 6:1 to 15:1, in particular 10: 1.

12. The process of claim 1, wherein the total molar amount of phenol in the first separate stream and the second separate stream is in excess, relative to the total molar amount of TMC-ketone in the first separate stream and the second separate stream, with respect to the stoichiometric amount.

13. The process according to claim 1, wherein the ratio between the mass flow rates of the first individual stream and the second individual stream is from 2:25 to 15:25, preferably from 2:10 to 1: 10.

14. The method of claim 1, wherein in step (d) the method further comprises

A product stream is removed from the reaction vessel comprising 55 to 70 wt% unreacted phenol, less than 5 wt% unreacted TMC-ketone, 15 to 22 wt% BP-TMC and 3.5 to 5.5 wt% dissolved acidic catalyst, 0.5 to 2 wt%, preferably about 1 wt% water, and 5 to 20 wt%, preferably 10 to 15 wt% by-product, or 1 to 4 wt%, preferably 2 to 3 wt% by-product, wherein the sum of the amounts of unreacted phenol, unreacted TMC-ketone, BP-TMC, water and by-product is 100 wt%.

embodiment (A)

(a1) Providing a separate first stream comprising:

(i) 3,3, 5-trimethylcyclohexanone (TMC-ketone), said TMC-ketone having a purity of at least 90 wt. -%, preferably of at least 95 wt. -%, more preferably of at least 98 wt. -%, and said TMC-ketone comprising less than 1 wt. -%, preferably less than 0.5 wt. -%, more preferably less than 0.2 wt. -%, most preferably less than 0.1 wt. -% phenol,

(ii) a gaseous acid catalyst;

(b1) providing a separate second stream comprising:

(iii) the reaction mixture of phenol and water is reacted with phenol,

(iv) an additional component;

and then subsequently

(c) Combining the first stream and the second stream together in a reaction vessel to form a reaction mixture.