申请人:Haas Thomas
公开号:US20110118504A1
公开(公告)日:2011-05-19
The present invention relates to a process for preparing hydroxycarboxylic acids, preferably α- and β-hydroxycarboxylic acids, from ammonium carboxylates of the general formula
in which R
1
, R
2
and R
3
are each independently H, OH, (C
1
-C
6
)-alkyl optionally substituted by a hydroxyl group, (C
1
-C
6
)-alkenyl optionally substituted by a hydroxyl group, (C
1
-C
6
)-alkoxy optionally substituted by a hydroxyl group, (C
1
-C
6
) -alkylthio-(C
1
-C
6
)-alkyl optionally substituted by a hydroxyl group, (C
6
-C
10
)-aryl optionally substituted by a hydroxyl group, (C
7
-C
12
)-aralkyl optionally substituted by a hydroxyl group, (C
3
-C
5
)-heteroaryl optionally substituted by a hydroxyl group, with the proviso that at least one hydroxyl group is present in at least one R
1
, R
2
and R
3
radical,
preferably R
1
═H, CH
3
, CH
2
CH
3
, C
6
H
5
, (CH
2
)
2
SCH
3
and R
2
═H, CH
3
and R
3
═OH,
equally preferably R
1
═CH
2
OH, CHOHCH
3
and R
2
═R
3
═H, CH
3
,
more preferably R
1
═R
2
═CH
3
and R
3
═OH,
equally more preferably R
1
═CH
2
OH, R
2
═CH
3
and R
3
═H, comprising the following step:
heating an aqueous starting solution comprising the ammonium carboxylate to form, by thermal decomposition of the ammonium carboxylate, the hydroxycarboxylic acid and ammonia, and simultaneously to remove at least a portion of the free water and of the ammonia formed from the solution and thus to obtain a product fraction comprising the hydroxycarboxylic acid,
characterized in that
the content of the ammonium salt in the starting solution is less than 60% by weight, the thermal decomposition of the ammonium salt and the removal of the free water and of the ammonia formed are effected in one process step, the conversion of the ammonium salt being more than 20 mol %, preferably more than 30 mol %, more preferably more than 50 mol %, especially preferably more than 75 mol %, very especially preferably more than 90 mol % and especially more than 95 mol %, and no ether, alcohol or hydrocarbon is used as an entraining agent.
本发明涉及一种从一般式的铵羧酸盐制备羟基羧酸,优选为α-和β-羟基羧酸的过程,其中该一般式中,R1、R2和R3各自独立地为H、OH、(C1-C6)烷基,该烷基可选地被羟基取代,(C1-C6)烯基,该烯基可选地被羟基取代,(C1-C6)烷氧基,该烷氧基可选地被羟基取代,(C1-C6)烷硫基-(C1-C6)烷基,该烷基可选地被羟基取代,(C6-C10)芳基,该芳基可选地被羟基取代,(C7-C12)芳基烷基,该芳基烷基可选地被羟基取代,(C3-C5)杂环芳基,该杂环芳基可选地被羟基取代,但至少在R1、R2和R3中的一个基团中存在一个羟基,优选为R1═H、CH3、CH2CH3、C6H5、(CH2)2SCH3和R2═H、CH3以及R3═OH,同样优选为R1═CH2OH、CHOHCH3且R2═R3═H、CH3,更优选为R1═R2═CH3且R3═OH,同样更优选为R1═CH2OH、R2═CH3且R3═H。该过程包括以下步骤:加热含铵羧酸盐的水溶液,通过铵羧酸盐的热分解形成羟基羧酸和氨,并同时从溶液中去除至少一部分游离水和形成的氨,从而得到包含羟基羧酸的产品组分。其特点在于,起始溶液中铵盐的含量小于60%重量,铵盐的热分解和游离水和形成的氨的去除在一个过程步骤中完成,铵盐的转化率大于20摩尔%,优选大于30摩尔%,更优选大于50摩尔%,特别优选大于75摩尔%,非常特别优选大于90摩尔%,尤其是大于95摩尔%,且不使用醚、醇或烃作为夹带剂。