CA2196336A1 - Process for preparing aspartic acid polycondensates with improved biological degradability and their use - Google Patents
Process for preparing aspartic acid polycondensates with improved biological degradability and their useInfo
- Publication number
- CA2196336A1 CA2196336A1 CA 2196336 CA2196336A CA2196336A1 CA 2196336 A1 CA2196336 A1 CA 2196336A1 CA 2196336 CA2196336 CA 2196336 CA 2196336 A CA2196336 A CA 2196336A CA 2196336 A1 CA2196336 A1 CA 2196336A1
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- Canada
- Prior art keywords
- aspartic acid
- water
- acid
- polycondensation
- mol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
- C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
- C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
- C02F5/12—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1092—Polysuccinimides
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3719—Polyamides or polyimides
Abstract
A process is disclosed for preparing aspartic acid polycondensates with improved biological degradability by thermal polycondensation of finely powdered aspartic acid in solid phase, at temperatures from 180 to 250 ~C, until maximum 70 % by weight of the theoretically possible amount of water produced during polycondensation are removed from the reaction mixture. Also disclosed is the use of the thus produced polycondensates as additives for washing and cleaning agents and as scale inhibitors.
Description
BASF Aktiengesell5chaft 940339 0~2. 0050/4507~
Pr-paration of aspartic acid poly~o~ Ate~ w~th improved ~iode-_ gra~h~ 1; ty and uce thereo~
5 The pre~ent invention relates to a proce~ ~or prepar~ng aspartic acid polyconden~ate~ with i~rvved biodegra~h;l~ty by the ther-mal polyCondensation of a~partic acid and to the use of the poly-conden~ate~ as additive in detergents and cleaner~.
10 Numerous ~.Gces~es are known for preparing aspartic acid polycon-densates. one po~ibility i~ the ther~al polycondensation of a~partic acid in the absence of cataly~t~. Such a process i5 known for ~mrl e from US_A -5 057 597. In t~is proce~ inely divided aspartic acid i6 polycondensed ln an agitated powder bed 15 at t~mperature~ from about 180 to 250 C with distillati~e re~oYal of water, the particle size being not more than 150 ~m. The polymerization takes place ~n solid phase withou~ melting of the aspartic acid crystals. ~or thi~ reason no sticky phase~ occur in the course of the polycondensatlon. ~he reaction product~ can be 20 carried off for further use without further ~-OL~up or purifi-cation 6tep~.
US-A-5 221 733 likewi~ disclose~ a proce~8 for the thermal poly-condensation of aspartic acid whercin pulverulent L-aspartic acid 2~ is initially heated to a temperature of about 18a C to start off the conden~ation and then the reaction mixture is heated and con-densed at a temperature o~ at least 216 C until at lea~t 80~ of the a~partic acid has been condensed to form poly~ucclnimide. ~he polysuccinimide is subseguently hydrolyz~d with a ba~e, the prod -30 uct being a polya~partic a~id salt.
The abo~e-de~cribed processes ~eek to ~-xi i~e the con~ercion of the aspa~tic acid used in the poly~on~n~ation~ ~owever, they have the disadvantage that the polyconden8ation ~s acco~panied by 35 the format~on of by-products which are not readily biodegradable.
EP-A-0 454 126 di~close~ u~ing polyaspartic acid in amounts ~rom 5 to 50~ by weight as b~ r in detergent formulations contain-ing from 10 to 40% by weig~t of at leant one sur~ace-ac~ive agent 40 and from 5 to 50~ by w~ight of at lea3t one ~odium aluminum ~ilicate .
EP--~--O 511 037 disclo3es detergent for~lAt~on9 cv~u~t~Lising for example poly~ucc;nimide a~ at least par~ially biodegrada~le 45 builder.
sASF Aktiengesellschaft 940339 O.Z. 0050/45075 It is an o~ject of the present invention to provide a pro~e~ for preparing polycondensate~ of aspartic acid with better biodegrad-_ ability than those obtained by existing proce~e~.
5 We have found that th~s o~ct $~ achieved by a pro~e~ for pre-paring aspartic acid polycondensates with il,.~,G~ed biodegradabil-ity, which c~Lises polycondensing ~inely di~ided aspartic acid by thermal polyeonden~ation in Rolid phase at t~r~rature~ from 180 to 250 C until not more than 70~ by weight of the theoreti-10 cally possibl~ amount of water which is formed in the course ofthe polycondensation ha~ been ~ ~ed from the reaction mixture.
The aspartic acid polyconden~ate~ thus obt~ h~ are used as additive in detergent~ and cleaner8.
15 ~he process of the present invention in~ol~es subjecting a finely divided a~par~ic acid to thermal polyconden~ation in ~olid phase.
The aFpartic acid can be uaed in the polyconden~ation in the form of ~ry_tals or a~ '.er. ~he aspartic ac~d cry~tal~ range in ~ize for example fro~ 0.001 to 5 mm. Aspartic acid powders have 20 for ~mrle a~erage particle ~ er~ from 0.0~ to 3~ preferably from 0.1 to 2, ~m. The polycondensation is carried out in custom-ary apparatus, for exa~ple in a tumble dryer or in a stirred bed of solids. In the laboratory, the polycondenQation i~ usually carried out in a rotary evaporator. Apparatu~ suitable for carry-2s ing ou~ the polycondensation on an industriaI scale includes forexample paddle dryers, di~k dryers, plough share ~ixers, paddle mixer~, extruders, fluidized bed_ with or wi~hout stirring, double cone mixers, rotary tubes, bed~ of ~olid~ with or wtthou~
stirring, cone mixerR, silos, tubular reactor~, ~tirred tanks 30 (especially with cro~sbeam ~tirrers), conveyor belts, drum mixers and ball mill~.
The polycondensation of the aspartic acid according to ~he pres-ent inventlon is effected thermally, ie. by 5imply heating ~inely 35 divided polyaspartic acid to tG~Le~a~ures f~om 180 to 250 C, pre~erably 200-240 C. A th~ -l polycondensation is carried out without the use of catalyQt_, ~uch as pho~phoric acid or hydro-chloric acid. Since ~he a~partic acid c~ystals do not melt in the cour~e of the ~herma~ polyco~ensation, no ~ticky phases occur, 40 so that finely divided poly~on~n~ates are o~tained. The a~erage diameter and the particle size distribu~ion of ~he polyconden-sate~ obtained sub~ta~tially correspond to the average dia~eter and the particle ~ize di~tribution of the finely divided a~partic acid used as ~tarttng material.
sASF Akt~eng~ellsch~ft 940339 o.z. 0050t45075 ~ccording to the present invention, the polycondensation i~ car-ried on only until 70~ by weight of the theore~ically possible _ amount of water formed ln the course of the polycondensation has been .l v~d from the reaction m~xture. The course of the poly-5 condensation i9 therefore very easy to monitor by determin~ng the amount o~ water removed from the reaction mixture. For example, the amount of wat~r di~tilled out of the reaction mixture can be determined volumetrically or gra~imetrically. As ~oon as 10~ by weight, proferably not more than 60~ by weight, of ~he theoreti-10 cally possible a~ount of water formed in the course o~ the poly-condensation has been remo~ed from the reaction mixture, the polycondensation i8 di~continued by cool; ng the reaction mixture.
To calculate the o~;mll~ theoretically possible amount of water whieh can be el;~in~ted in the course of the polycon~en~ation, ~t 15 i assumed that the polyconden~atlon of 1 mol (133 g) aspartic acid to polyaspartic acid w~ll on complete convers~on release 2 ~ol (36 g~ of water. The weight loss due to the ~limln~ion o~
water during the r~action is thus 27~ by weight, based on the aspartic acid u3ed. 70~ of the t~eoretically possible amount of 20 water mean~ that the polyconden~ation is di~continued when 1. 4 mol ( 25 . 2 g) of water have ~een distilled out of the reaction mixture. Thi~ corre~ponds to a weight 108~ of 18.9S, based on the weight of the a~partic a~id u~ed.
25 The polyconden~ation of aspartic acid can be schematically repre-sented as follow~:
aspartic acid H 0~ polyaspart~c acid ~ 0~ polys~ccln;~;d~
~able 1 reveals the nature of ~e calculation of the amount of water fo~med in the course of the reaction.
BASF Akti~ngesellschaft 940339 0.2. 0050~45075 Table 1 Amount of water di6tllled out of the polyconden6ation mixture -[mol~ ~ of ~qYi , po~sible [g] Based on aspartic acid amount used t a by weigh~J
2.0 100 36.027.0 1.4 70 25.218.9 1.2 60 21.6~6.2 10 1.0 50 18.013.5 The product~ obtAi~ are a6p~ tic acid polyconden~ate~ which contain 15 a) alpha- and beta-l;n~ed aspartic acid units of the ~tructures - ~NH C~ - CO)n- and ~N~ CH2 - CH CO)n (I) (II), b) polyasparti~;de uni~s of the structure ~ ~ f N (IIl) and --n C ) a8par~ic acid.
~he co~po~ition of the polycondensation product8 depend~ on the t~mr~rature during the polyc~ n~ation and on the re i~r~e time in the polycon~ tion zone. The polycon~len~ation can be carried o~t for eY~rl e in ~uch a way that no aspart~c ac~d n ~or ~ur-vive~ lnto the end product. If, for e~mrle, 1 mol of aspartic acid i~ u~ed and initially 1 mol of water i~ di~ ~ out of the polyconden~at~on mix~ure, thi3 will initially re~ult in the formation of 1 mol of polya~partic acid unit~, from which 0.4 mol 4S of water i8 then ~l;~i n~tQd to leave 0.4 mol of polysuccin; mi de units. Thi8 mean~ that a polyconden~ation 0~ 1 mol of a8par~ic acid where 1.4 mol of water are remo~ed by dist~llation will giYe ~ASF Akti~ng~soll~chaft 940339 O.Z. OOSO/g5075 rise to a product cont~i n; ng 60 mol ~ o~ polya~p -tic acid units in the alpha- and beta-form and 40 mol ~ of polysucri~ e _ units.
5 However, the polyco~e~ation can a7 90 be carried out in 3~ch a way that, of l mol of a~partic acid used, 0.1 ~ol r~-in~
unchanged in the reaction mix~ure. On the assumption that 1.4 mol o~ water have been ~ ~d from the polycondensation o~ 1 mol of aspartic acid, the reaction mixture may contain up to 0.4 ~ol of ~o polya~partic acid units and up to 0.5 mol of polysl~cc;n;mide units. The polyco~en~ation can also be carried out in such a way that the u~e of 1 mol of aspartic ac~d leave~ 0.2 mol of unchanged acpart$c acid behi~d in the reaction m xture, wherea~
the el; ;n ~tion of 1.4 mol o~ water can lead to the formation o~
15 up to 0.2 mol of polyaspartic acid units and up to 0.6 mol of poly~ucc; n i~;d~ unit~.
Table 2 indicates ~he c ,-3i~ions of polyconden3ate3 on removing from the react~on mlxture 70~ - the maxlmum allowed by the 20 pr~nt invent~on - of the water formed in ~he course of the Qolycondensation.
Table 2 Composition of polyconden~ates after ti~tillati~e ~ val of 70 25 by weight of the theoretically possible amount of water A~partic acid tmol S] 0 10 20 30 Polya~partic acid ~mol ~3 60 40 20 0 30 Polysuccin~m~d~ tmol ~] 40 50 60 70 ~he ~ 09ition of polyco~s~QateQ after the distillative remo~al ~rom the aspartic acid polycondenoation mix~ure of 60 and 50~ of the theoret~cally po~ le amount of water is i~dicated tn 35 Tables 3 and 4, re~pectiYely.
Table ~
Aspartic acid [mol %] o 10 20 30 40 Polyaspartic acid lmol %3 80 60 40 20 PolyQt~c~;n;~;de [mol ~l 20 30 40 50 Table 4 45 Aspartic acid tmol ~ 0 10 20 30 ~olya~partic acid ~mol %~ 100 80 60 40 Polys~ccinim~de tmol ~] 0 10 20 30 . BASF Aktiengesello-~f~ 940339 0 Z OOS0/45075 The polycond~n~tion i~ preferably c~rried out ~ such a way that in any event the poly~n~raat- contalns le~s than 20 mol ~ of _ unchanged aspartic acid. ~he aspartic acid content of the poly-condensate can range for eY~mrle from 0 to 19% by weight.
The a~part~c acid condensation products can be analyzed for example using spectroscopic or chromatographic ~ethods. The analytically preparative ~eparat~on of the reaction mixture into its individual ~v~ ents can be carried out for example by means 10 of an extraction uti~ i7ing the differences in the water solu-bility of the ind~v~dual ~ ~nent~.
~or in~tance, the reaction mixture can be extracted first for example with water, in which case the fract~on ~eparated off 15 con3ists e~entlally o~ polya~partic acid or a cocondensatQ which contain~ aspar~ic acid unit~ and succin; m; de units, the aspartic acid units being presen~ in the cocon~nsate in an amount o f more than 50~. The water-soluble portion i~olated f rom the reaction mixture u~ually ~V~y~ae~ from 20 to 80, preferably from 30 to 20 70, % by wei~ht, based on the a~partic acid u~ed. ~he water-in-~oluble re~i~u~ is a~partic acid and poly~ccini~ide. It i9 treated ~or ~urther sxtraction with lN hydrochloric acid, cau~ing aspartic acid to di~sol~e by formation of a~partic acid hydro-chloride. The proportion of a~partic acid i8 usually below 20, 25 preferably below 15, ~ by weight, based on t~e amount of aspartic acid u~d. The resldue wh~ch ~ insoluble in water and hydrochlo-ric ac~d cons~ts pr~ ntly of polysuccinimide and i8 pregent in the condensation ~LG~t in an amount from 5 to 80, preferably from 15 to 70, ~ by weight. The quantitatiYe determina~Ton of the 30 individual ~ractions is by drying and weighing. The amount of aspartic acid used can ~e used to calculate the percentage ~hares of polyaspar~lc acid and poly~T~-rini~ide.
The polycon~-nsation i8 carried out within the temperature range 35 from 180 to 250 C, preferably within the t~p~rature range from l90 to 250 c. ~he hi~her the c~ a~ion t~re~ature which i~
chosen, the shorter i9 the reaction time. At a polycondensation t~p~ra~ure ~f 225-C, for ~ ls, 50% of the theoretical amount o~ water for~ed in the course of the polycondensatio~ can be dis-40 tilled out of the reaction m xture in the ~our~e of a conden~a-tion time of about 2.5 h. The reaction mixture then contains 50~
of water-~oluble polycondensAte and 50~ of water-insoluble poly-condensate. The K ~alue~ of the polycondenYate3 of aspartic acid range from ~ to 30, preferably from lO to 25, determined by the 4S method of H. Fikent~cher on lS Qtrength agueous codiu~ salt 501u-~ion~ of the polyco~n~ate at pH ? a~d 2S C. The molec~lar BASF Aktiengesellschaft 940339 O.Z. 0050~5075 weights M~ of the polycondensate range from 500 to 7 000, prefer-ably from 800 ~o S 000.
In ~he ~Y~rles which follow, parts are by weight. The R values 5 of the polycondensates were dete~ by the method of H. Pikent~cher, Cellulo~e-Chemie 13 ~1932)~ 58-64, 71-74, in aqueous solution on the sodium salts of the polycondensates at a concentration of lt ~y weight, a p~ of 7 and a temperature o~
25-C.
~Y~mrle 1 A 2~0 1 c~r~ity tumble dryer is charged with 50 kg of L-a~partic acid ~average particle diameter 0.1-2 mm) and heated by mean~ of 15 an external oil cycle to a tQmperature of 240 C. During the poly-condensation the reactor is flushed with 100 1 of nitrogen/h. As ~oon as the t~mro~ature of the finely divided a~partic acid has reached 200 C, the polyco~den~ation starts, as i9 discernible from the accumulation of water ~n the conden~er. once the polycon-~0 den~ation has ~tarted at 200 C ~t ls continued untll, after3 hours, 7.5 1 of water have been 8eparated off. This amount of water of conden~ation correqponds to a 55~ conversion. The poly-condensate is analyzed extractlvely and spectro~opically. It is found to eontain 5~ of a~partic acid, 50% of water-3cluble aspar-2~ tlc ac~d polyco~e~ate and 45% of water-insoluble polysuccini-mide. The course of the polycondensation i9 9~own in Table 5.
The react~on product iB not completely 901uble in dime~hylforma-~;de. It can be converted with sodium hydroxide solu~ion into the 30 sodium salt of polyaspartic acid. The ~odium 3alt of the con-den~ation product, as a 1~ strength ~olution, has a R value of 18.8 at pH 7 and 25 C.
~able 5 Time ~h~ at~l~ ~ternalA~ount of ~ of theoretic-of oll cycle t~, ~tu~ wa~~ dio--ally po~ibl~3 t~C] t~C] tilled offamount~ of tl] wa~er of condensation 0 20 20 0 ~
2 232 203 dripping 0 3 240 21g 3.5 25.9 4 240 229 5.0 37.0 ~ BASF Aktienge~ellscha~t 940339 O.Z. 0050/4S075 ~8 21 96336 5 1 240 1 2~8 1 7.5 1 55.5 Co~l; n g -5 Comparative ~rle 1 The tumble dryer de~cribed in ~Y~p~ charged with 50 kg o~
L - aspartic acid having an average particle diameter of 0.1- 2 mm and heated by means of an external oil cycle to a temperature of 10 240 C. The reactor i3 flushed with 100 1 of nitrogen~h. A~ soon as the t~mr~ature o~ the reaction material has reached 200 C, the polycondensation ~tarts, as i~ di~cernible from the fact that water collects in the conden~er. The amount ~f wa~er i~ deter-mined Yolumetrically. The polyc~nden~ation i~ continued under the 1~ conditions indicated in Table 6 for 6 h, in the cour~e of which 12.2 1 oS water separate off. The amount of water distilled out of thQ reaction mlxture and the theoretically po~ible amount of water (100~ = 13.3 ~g of water) are u6ed to calculate the ~onver-sion. It i~ found to be g2.5~. Af~er the polycondensation ha~
20 ended, ~h~ reactor i~ found to contain 37.5 kg of water-insoluble aspartic acid polyco~n~ate ~determ~ned ~y mean~ of the extrac-tion method). The reaction produ~t i~ soluble in dlmethylforma-mide. It can be con~e~ted with sodium h~ide ~olution into the ~od~um salt of polya~partic acid. ~h~ sodium ~alt of the con-25 den.~ation product, a~ a lS qtrength aqueous solution, has aR value of 26.6 at pH 7 and 25 C.
Table 6 ~i~e [h] Te~p~ Internal A~ount of * of theoretic-of oil cycle t~ ~ ~ture water di~- ally possible t~Cl ~~C] tilled offamount~ o~
tl3 water of conden~ation 2 235 203 dripping 0 3 238 217 2.0 14.8 4 240 227 5.5 40.7 240 227 7.0 51.9 6 240 227 9.0 66.7 240 228 10.3 76.3 ~ 240 230 12.5 92.6 45 Coo~
;F Aktieng~s~ h~ft 940339 o. z . 0050/45075 Example~ 2 to 14 A rotary e~aporator i~ charged in each case with 133 g ~1 mol) of aspar~ic acid (particle diameter 0.1-2 mm) and heated in an oil 5 bath which ha~ the t~srature indicated in Table 7 for the time indicated ~n ~able 7.
Table 7 Ex. T~mp. TLme [h] ~ of th~oretic- ~ value of poly-tocl ~lly p~ibl~ ~r~ te hydro -a~oun~ of wat~ lyzed with NaO~
of cY~ tion 2 240 1 74 1~.0 3 240 0.5 49 12.0 4 240 0.25 40 10.0 190 5 9 8.0 6 190 7 14 ~.7 7 190 16 31 12.4 8 200 3 11 8.5 9 200 6 27 10.8 200 16 39 14.1 11 210 2 17 9.7 12 210 7 34 12.8 13 220 2 22 10.4 14 220 6 35 13.7 30 Correlation betweon ~ value and M~
R value Mw Ecological te~t~
Ecological te~t~ were carried out in accordance with the modified Zahn-Wellen~ test as laid down in the OECD G~ 1; nes for Testing of Chemicals ( 1981 ), 302 B. The DOC ~tarting concentration (DOC =
di~solved organic carbon) was 200 mg/l.
' ~ASF Aktlengesellschaft 940339 O.Z. 0050~qSO75 ~ 21 96336 The cour~e of the DOC dqcreasa is listed in TablQ 8 ~or ~he polycon~n~ate~ prepared in ~le 1 and ~r~rative Example 1.
It is clsarly apparent from the DO~ decrease that early di~con-5 tinuation of the polycondenaation at 55.~ cor,~ sion can b~ u~ed to improve the ecolog~cal p~o~ ies of the polyaspartic acid.
For instance, 48% of the polycondensate are rapidly biodegraded within one day without adaptio~, whereas it take~ 20 day~ ~o achieve 40% degrada~on in the ca~e Of the comparative e~mrle.
Pr-paration of aspartic acid poly~o~ Ate~ w~th improved ~iode-_ gra~h~ 1; ty and uce thereo~
5 The pre~ent invention relates to a proce~ ~or prepar~ng aspartic acid polyconden~ate~ with i~rvved biodegra~h;l~ty by the ther-mal polyCondensation of a~partic acid and to the use of the poly-conden~ate~ as additive in detergents and cleaner~.
10 Numerous ~.Gces~es are known for preparing aspartic acid polycon-densates. one po~ibility i~ the ther~al polycondensation of a~partic acid in the absence of cataly~t~. Such a process i5 known for ~mrl e from US_A -5 057 597. In t~is proce~ inely divided aspartic acid i6 polycondensed ln an agitated powder bed 15 at t~mperature~ from about 180 to 250 C with distillati~e re~oYal of water, the particle size being not more than 150 ~m. The polymerization takes place ~n solid phase withou~ melting of the aspartic acid crystals. ~or thi~ reason no sticky phase~ occur in the course of the polycondensatlon. ~he reaction product~ can be 20 carried off for further use without further ~-OL~up or purifi-cation 6tep~.
US-A-5 221 733 likewi~ disclose~ a proce~8 for the thermal poly-condensation of aspartic acid whercin pulverulent L-aspartic acid 2~ is initially heated to a temperature of about 18a C to start off the conden~ation and then the reaction mixture is heated and con-densed at a temperature o~ at least 216 C until at lea~t 80~ of the a~partic acid has been condensed to form poly~ucclnimide. ~he polysuccinimide is subseguently hydrolyz~d with a ba~e, the prod -30 uct being a polya~partic a~id salt.
The abo~e-de~cribed processes ~eek to ~-xi i~e the con~ercion of the aspa~tic acid used in the poly~on~n~ation~ ~owever, they have the disadvantage that the polyconden8ation ~s acco~panied by 35 the format~on of by-products which are not readily biodegradable.
EP-A-0 454 126 di~close~ u~ing polyaspartic acid in amounts ~rom 5 to 50~ by weight as b~ r in detergent formulations contain-ing from 10 to 40% by weig~t of at leant one sur~ace-ac~ive agent 40 and from 5 to 50~ by w~ight of at lea3t one ~odium aluminum ~ilicate .
EP--~--O 511 037 disclo3es detergent for~lAt~on9 cv~u~t~Lising for example poly~ucc;nimide a~ at least par~ially biodegrada~le 45 builder.
sASF Aktiengesellschaft 940339 O.Z. 0050/45075 It is an o~ject of the present invention to provide a pro~e~ for preparing polycondensate~ of aspartic acid with better biodegrad-_ ability than those obtained by existing proce~e~.
5 We have found that th~s o~ct $~ achieved by a pro~e~ for pre-paring aspartic acid polycondensates with il,.~,G~ed biodegradabil-ity, which c~Lises polycondensing ~inely di~ided aspartic acid by thermal polyeonden~ation in Rolid phase at t~r~rature~ from 180 to 250 C until not more than 70~ by weight of the theoreti-10 cally possibl~ amount of water which is formed in the course ofthe polycondensation ha~ been ~ ~ed from the reaction mixture.
The aspartic acid polyconden~ate~ thus obt~ h~ are used as additive in detergent~ and cleaner8.
15 ~he process of the present invention in~ol~es subjecting a finely divided a~par~ic acid to thermal polyconden~ation in ~olid phase.
The aFpartic acid can be uaed in the polyconden~ation in the form of ~ry_tals or a~ '.er. ~he aspartic ac~d cry~tal~ range in ~ize for example fro~ 0.001 to 5 mm. Aspartic acid powders have 20 for ~mrle a~erage particle ~ er~ from 0.0~ to 3~ preferably from 0.1 to 2, ~m. The polycondensation is carried out in custom-ary apparatus, for exa~ple in a tumble dryer or in a stirred bed of solids. In the laboratory, the polycondenQation i~ usually carried out in a rotary evaporator. Apparatu~ suitable for carry-2s ing ou~ the polycondensation on an industriaI scale includes forexample paddle dryers, di~k dryers, plough share ~ixers, paddle mixer~, extruders, fluidized bed_ with or wi~hout stirring, double cone mixers, rotary tubes, bed~ of ~olid~ with or wtthou~
stirring, cone mixerR, silos, tubular reactor~, ~tirred tanks 30 (especially with cro~sbeam ~tirrers), conveyor belts, drum mixers and ball mill~.
The polycondensation of the aspartic acid according to ~he pres-ent inventlon is effected thermally, ie. by 5imply heating ~inely 35 divided polyaspartic acid to tG~Le~a~ures f~om 180 to 250 C, pre~erably 200-240 C. A th~ -l polycondensation is carried out without the use of catalyQt_, ~uch as pho~phoric acid or hydro-chloric acid. Since ~he a~partic acid c~ystals do not melt in the cour~e of the ~herma~ polyco~ensation, no ~ticky phases occur, 40 so that finely divided poly~on~n~ates are o~tained. The a~erage diameter and the particle size distribu~ion of ~he polyconden-sate~ obtained sub~ta~tially correspond to the average dia~eter and the particle ~ize di~tribution of the finely divided a~partic acid used as ~tarttng material.
sASF Akt~eng~ellsch~ft 940339 o.z. 0050t45075 ~ccording to the present invention, the polycondensation i~ car-ried on only until 70~ by weight of the theore~ically possible _ amount of water formed ln the course of the polycondensation has been .l v~d from the reaction m~xture. The course of the poly-5 condensation i9 therefore very easy to monitor by determin~ng the amount o~ water removed from the reaction mixture. For example, the amount of wat~r di~tilled out of the reaction mixture can be determined volumetrically or gra~imetrically. As ~oon as 10~ by weight, proferably not more than 60~ by weight, of ~he theoreti-10 cally possible a~ount of water formed in the course o~ the poly-condensation has been remo~ed from the reaction mixture, the polycondensation i8 di~continued by cool; ng the reaction mixture.
To calculate the o~;mll~ theoretically possible amount of water whieh can be el;~in~ted in the course of the polycon~en~ation, ~t 15 i assumed that the polyconden~atlon of 1 mol (133 g) aspartic acid to polyaspartic acid w~ll on complete convers~on release 2 ~ol (36 g~ of water. The weight loss due to the ~limln~ion o~
water during the r~action is thus 27~ by weight, based on the aspartic acid u3ed. 70~ of the t~eoretically possible amount of 20 water mean~ that the polyconden~ation is di~continued when 1. 4 mol ( 25 . 2 g) of water have ~een distilled out of the reaction mixture. Thi~ corre~ponds to a weight 108~ of 18.9S, based on the weight of the a~partic a~id u~ed.
25 The polyconden~ation of aspartic acid can be schematically repre-sented as follow~:
aspartic acid H 0~ polyaspart~c acid ~ 0~ polys~ccln;~;d~
~able 1 reveals the nature of ~e calculation of the amount of water fo~med in the course of the reaction.
BASF Akti~ngesellschaft 940339 0.2. 0050~45075 Table 1 Amount of water di6tllled out of the polyconden6ation mixture -[mol~ ~ of ~qYi , po~sible [g] Based on aspartic acid amount used t a by weigh~J
2.0 100 36.027.0 1.4 70 25.218.9 1.2 60 21.6~6.2 10 1.0 50 18.013.5 The product~ obtAi~ are a6p~ tic acid polyconden~ate~ which contain 15 a) alpha- and beta-l;n~ed aspartic acid units of the ~tructures - ~NH C~ - CO)n- and ~N~ CH2 - CH CO)n (I) (II), b) polyasparti~;de uni~s of the structure ~ ~ f N (IIl) and --n C ) a8par~ic acid.
~he co~po~ition of the polycondensation product8 depend~ on the t~mr~rature during the polyc~ n~ation and on the re i~r~e time in the polycon~ tion zone. The polycon~len~ation can be carried o~t for eY~rl e in ~uch a way that no aspart~c ac~d n ~or ~ur-vive~ lnto the end product. If, for e~mrle, 1 mol of aspartic acid i~ u~ed and initially 1 mol of water i~ di~ ~ out of the polyconden~at~on mix~ure, thi3 will initially re~ult in the formation of 1 mol of polya~partic acid unit~, from which 0.4 mol 4S of water i8 then ~l;~i n~tQd to leave 0.4 mol of polysuccin; mi de units. Thi8 mean~ that a polyconden~ation 0~ 1 mol of a8par~ic acid where 1.4 mol of water are remo~ed by dist~llation will giYe ~ASF Akti~ng~soll~chaft 940339 O.Z. OOSO/g5075 rise to a product cont~i n; ng 60 mol ~ o~ polya~p -tic acid units in the alpha- and beta-form and 40 mol ~ of polysucri~ e _ units.
5 However, the polyco~e~ation can a7 90 be carried out in 3~ch a way that, of l mol of a~partic acid used, 0.1 ~ol r~-in~
unchanged in the reaction mix~ure. On the assumption that 1.4 mol o~ water have been ~ ~d from the polycondensation o~ 1 mol of aspartic acid, the reaction mixture may contain up to 0.4 ~ol of ~o polya~partic acid units and up to 0.5 mol of polysl~cc;n;mide units. The polyco~en~ation can also be carried out in such a way that the u~e of 1 mol of aspartic ac~d leave~ 0.2 mol of unchanged acpart$c acid behi~d in the reaction m xture, wherea~
the el; ;n ~tion of 1.4 mol o~ water can lead to the formation o~
15 up to 0.2 mol of polyaspartic acid units and up to 0.6 mol of poly~ucc; n i~;d~ unit~.
Table 2 indicates ~he c ,-3i~ions of polyconden3ate3 on removing from the react~on mlxture 70~ - the maxlmum allowed by the 20 pr~nt invent~on - of the water formed in ~he course of the Qolycondensation.
Table 2 Composition of polyconden~ates after ti~tillati~e ~ val of 70 25 by weight of the theoretically possible amount of water A~partic acid tmol S] 0 10 20 30 Polya~partic acid ~mol ~3 60 40 20 0 30 Polysuccin~m~d~ tmol ~] 40 50 60 70 ~he ~ 09ition of polyco~s~QateQ after the distillative remo~al ~rom the aspartic acid polycondenoation mix~ure of 60 and 50~ of the theoret~cally po~ le amount of water is i~dicated tn 35 Tables 3 and 4, re~pectiYely.
Table ~
Aspartic acid [mol %] o 10 20 30 40 Polyaspartic acid lmol %3 80 60 40 20 PolyQt~c~;n;~;de [mol ~l 20 30 40 50 Table 4 45 Aspartic acid tmol ~ 0 10 20 30 ~olya~partic acid ~mol %~ 100 80 60 40 Polys~ccinim~de tmol ~] 0 10 20 30 . BASF Aktiengesello-~f~ 940339 0 Z OOS0/45075 The polycond~n~tion i~ preferably c~rried out ~ such a way that in any event the poly~n~raat- contalns le~s than 20 mol ~ of _ unchanged aspartic acid. ~he aspartic acid content of the poly-condensate can range for eY~mrle from 0 to 19% by weight.
The a~part~c acid condensation products can be analyzed for example using spectroscopic or chromatographic ~ethods. The analytically preparative ~eparat~on of the reaction mixture into its individual ~v~ ents can be carried out for example by means 10 of an extraction uti~ i7ing the differences in the water solu-bility of the ind~v~dual ~ ~nent~.
~or in~tance, the reaction mixture can be extracted first for example with water, in which case the fract~on ~eparated off 15 con3ists e~entlally o~ polya~partic acid or a cocondensatQ which contain~ aspar~ic acid unit~ and succin; m; de units, the aspartic acid units being presen~ in the cocon~nsate in an amount o f more than 50~. The water-soluble portion i~olated f rom the reaction mixture u~ually ~V~y~ae~ from 20 to 80, preferably from 30 to 20 70, % by wei~ht, based on the a~partic acid u~ed. ~he water-in-~oluble re~i~u~ is a~partic acid and poly~ccini~ide. It i9 treated ~or ~urther sxtraction with lN hydrochloric acid, cau~ing aspartic acid to di~sol~e by formation of a~partic acid hydro-chloride. The proportion of a~partic acid i8 usually below 20, 25 preferably below 15, ~ by weight, based on t~e amount of aspartic acid u~d. The resldue wh~ch ~ insoluble in water and hydrochlo-ric ac~d cons~ts pr~ ntly of polysuccinimide and i8 pregent in the condensation ~LG~t in an amount from 5 to 80, preferably from 15 to 70, ~ by weight. The quantitatiYe determina~Ton of the 30 individual ~ractions is by drying and weighing. The amount of aspartic acid used can ~e used to calculate the percentage ~hares of polyaspar~lc acid and poly~T~-rini~ide.
The polycon~-nsation i8 carried out within the temperature range 35 from 180 to 250 C, preferably within the t~p~rature range from l90 to 250 c. ~he hi~her the c~ a~ion t~re~ature which i~
chosen, the shorter i9 the reaction time. At a polycondensation t~p~ra~ure ~f 225-C, for ~ ls, 50% of the theoretical amount o~ water for~ed in the course of the polycondensatio~ can be dis-40 tilled out of the reaction m xture in the ~our~e of a conden~a-tion time of about 2.5 h. The reaction mixture then contains 50~
of water-~oluble polycondensAte and 50~ of water-insoluble poly-condensate. The K ~alue~ of the polycondenYate3 of aspartic acid range from ~ to 30, preferably from lO to 25, determined by the 4S method of H. Fikent~cher on lS Qtrength agueous codiu~ salt 501u-~ion~ of the polyco~n~ate at pH ? a~d 2S C. The molec~lar BASF Aktiengesellschaft 940339 O.Z. 0050~5075 weights M~ of the polycondensate range from 500 to 7 000, prefer-ably from 800 ~o S 000.
In ~he ~Y~rles which follow, parts are by weight. The R values 5 of the polycondensates were dete~ by the method of H. Pikent~cher, Cellulo~e-Chemie 13 ~1932)~ 58-64, 71-74, in aqueous solution on the sodium salts of the polycondensates at a concentration of lt ~y weight, a p~ of 7 and a temperature o~
25-C.
~Y~mrle 1 A 2~0 1 c~r~ity tumble dryer is charged with 50 kg of L-a~partic acid ~average particle diameter 0.1-2 mm) and heated by mean~ of 15 an external oil cycle to a tQmperature of 240 C. During the poly-condensation the reactor is flushed with 100 1 of nitrogen/h. As ~oon as the t~mro~ature of the finely divided a~partic acid has reached 200 C, the polyco~den~ation starts, as i9 discernible from the accumulation of water ~n the conden~er. once the polycon-~0 den~ation has ~tarted at 200 C ~t ls continued untll, after3 hours, 7.5 1 of water have been 8eparated off. This amount of water of conden~ation correqponds to a 55~ conversion. The poly-condensate is analyzed extractlvely and spectro~opically. It is found to eontain 5~ of a~partic acid, 50% of water-3cluble aspar-2~ tlc ac~d polyco~e~ate and 45% of water-insoluble polysuccini-mide. The course of the polycondensation i9 9~own in Table 5.
The react~on product iB not completely 901uble in dime~hylforma-~;de. It can be converted with sodium hydroxide solu~ion into the 30 sodium salt of polyaspartic acid. The ~odium 3alt of the con-den~ation product, as a 1~ strength ~olution, has a R value of 18.8 at pH 7 and 25 C.
~able 5 Time ~h~ at~l~ ~ternalA~ount of ~ of theoretic-of oll cycle t~, ~tu~ wa~~ dio--ally po~ibl~3 t~C] t~C] tilled offamount~ of tl] wa~er of condensation 0 20 20 0 ~
2 232 203 dripping 0 3 240 21g 3.5 25.9 4 240 229 5.0 37.0 ~ BASF Aktienge~ellscha~t 940339 O.Z. 0050/4S075 ~8 21 96336 5 1 240 1 2~8 1 7.5 1 55.5 Co~l; n g -5 Comparative ~rle 1 The tumble dryer de~cribed in ~Y~p~ charged with 50 kg o~
L - aspartic acid having an average particle diameter of 0.1- 2 mm and heated by means of an external oil cycle to a temperature of 10 240 C. The reactor i3 flushed with 100 1 of nitrogen~h. A~ soon as the t~mr~ature o~ the reaction material has reached 200 C, the polycondensation ~tarts, as i~ di~cernible from the fact that water collects in the conden~er. The amount ~f wa~er i~ deter-mined Yolumetrically. The polyc~nden~ation i~ continued under the 1~ conditions indicated in Table 6 for 6 h, in the cour~e of which 12.2 1 oS water separate off. The amount of water distilled out of thQ reaction mlxture and the theoretically po~ible amount of water (100~ = 13.3 ~g of water) are u6ed to calculate the ~onver-sion. It i~ found to be g2.5~. Af~er the polycondensation ha~
20 ended, ~h~ reactor i~ found to contain 37.5 kg of water-insoluble aspartic acid polyco~n~ate ~determ~ned ~y mean~ of the extrac-tion method). The reaction produ~t i~ soluble in dlmethylforma-mide. It can be con~e~ted with sodium h~ide ~olution into the ~od~um salt of polya~partic acid. ~h~ sodium ~alt of the con-25 den.~ation product, a~ a lS qtrength aqueous solution, has aR value of 26.6 at pH 7 and 25 C.
Table 6 ~i~e [h] Te~p~ Internal A~ount of * of theoretic-of oil cycle t~ ~ ~ture water di~- ally possible t~Cl ~~C] tilled offamount~ o~
tl3 water of conden~ation 2 235 203 dripping 0 3 238 217 2.0 14.8 4 240 227 5.5 40.7 240 227 7.0 51.9 6 240 227 9.0 66.7 240 228 10.3 76.3 ~ 240 230 12.5 92.6 45 Coo~
;F Aktieng~s~ h~ft 940339 o. z . 0050/45075 Example~ 2 to 14 A rotary e~aporator i~ charged in each case with 133 g ~1 mol) of aspar~ic acid (particle diameter 0.1-2 mm) and heated in an oil 5 bath which ha~ the t~srature indicated in Table 7 for the time indicated ~n ~able 7.
Table 7 Ex. T~mp. TLme [h] ~ of th~oretic- ~ value of poly-tocl ~lly p~ibl~ ~r~ te hydro -a~oun~ of wat~ lyzed with NaO~
of cY~ tion 2 240 1 74 1~.0 3 240 0.5 49 12.0 4 240 0.25 40 10.0 190 5 9 8.0 6 190 7 14 ~.7 7 190 16 31 12.4 8 200 3 11 8.5 9 200 6 27 10.8 200 16 39 14.1 11 210 2 17 9.7 12 210 7 34 12.8 13 220 2 22 10.4 14 220 6 35 13.7 30 Correlation betweon ~ value and M~
R value Mw Ecological te~t~
Ecological te~t~ were carried out in accordance with the modified Zahn-Wellen~ test as laid down in the OECD G~ 1; nes for Testing of Chemicals ( 1981 ), 302 B. The DOC ~tarting concentration (DOC =
di~solved organic carbon) was 200 mg/l.
' ~ASF Aktlengesellschaft 940339 O.Z. 0050~qSO75 ~ 21 96336 The cour~e of the DOC dqcreasa is listed in TablQ 8 ~or ~he polycon~n~ate~ prepared in ~le 1 and ~r~rative Example 1.
It is clsarly apparent from the DO~ decrease that early di~con-5 tinuation of the polycondenaation at 55.~ cor,~ sion can b~ u~ed to improve the ecolog~cal p~o~ ies of the polyaspartic acid.
For instance, 48% of the polycondensate are rapidly biodegraded within one day without adaptio~, whereas it take~ 20 day~ ~o achieve 40% degrada~on in the ca~e Of the comparative e~mrle.
10 A~ter an adaption pha~e of 20 days, Example 1 give3 further degradation up to 90~. In the ca~e of the comparat~ve example, the degradation values only rise to 80%.
~able 8 Time [d] Decrease ~n dis~olved organic carbon ~Y~rl~ 1 Compara~ive ~Y~mrle l O O
1 48 ~1 5~ 40 30 Result:
Measures according to the pre~ent invention make it possible to achieve a distinct ~mp~v~ ?nt in the degree of degradation of the aspartic acid polycon~ncates over the first 8 days. ~n addition, higher final degradation valueq are achieved at the 35 e~d.
The polycondensates of Example~ 2, 3 and 4 were subjectRd to a Zahn-Wellen~ test. ~y day 20 the di~solved organic carbon had decreased to the value~ indicated in Tab1Q 9.
BASF Aktienge~ell~chaft 940339 O.Z. 0050~4S075 Table 9 ~ ~Y~ e Decrease in di~olved organic carbon by day 20 [%]
10Comr~rati~e ~Y~mrle 1 40 Application test6 The polyco~den~ates of a~partlc acid prepared by ~he process of the pre~ent invention are ~uitable for u~e as water treatment 15 agents. The polyconden~ates of FY~P~ e 1 and C~r~rative Example 1 were tested for calcium ion compatibil~ ty by preparing in each ca~e aqueous solutions cont~ n~g 4S ppm of poly~o~en-~a~e a~d 1000 ppm of calcium ions and detc~i n; r~g the transmi~-sivity of the solution~. Eoth aqueous solution~ we~e found to 20 have a transmissivity of 99.8~, i.c. ~either sample combines with calcium ion~ to form ~paringly water-soluble calc~um salts.
The polycondensates of PY~rl~ 1 and ~ , rative FYA~rle 1 were al~o tested for dyn ~; c calcium ~arbonate ;n~; h; tion at a con-2s centration of 2 ppm of polyco~d~n~ates Calcium carbonate inhibition (2 ppm of polycocol.den~ateco~centrat~on~
30 Two test solutionQ are prepared. ~e~t solution 1 is water having a hardne~ of 20- (Ger~an) and a m~gne~ium hardnes~ of 10 ~German3. Test Qolution 2 is an aqueou~ solution ha~ing a ~odium carbonate hardne~ of 4.7- (~ ) and a sodi~ bicarbonate hard-ne~s of 12.3- (German).
A 500 ml capacity round-bottom flask equipped with ntirrer, reflux condenser and gag ~nlet tube i8 charged with 150 ml of test solution 1 and 150 ml of teYt ~olution 2 and al80 2 ppm oS
the in-test polymer and heated at 70-C for 1 hour or 2 hours while ~0 air is being pas~ed in at a rate of 3 1th. The flagk content~ are cooled down and ~iltered through a fluted ~ilter. The filtrate is titra~ed compl~Y~ ~~,ically to determine the calcium conten~ in a conventional manner.
g5 The ~ollowing calc~um carbonate inhibition values were determined:
BA5F Aktienge~ellscbaft 940339 O.Z. 0050~45075 ' 2196336 1~
CaC03 ; nh; h; tion after 1 hour 2 hours ~Y~rle 1 45 ~ 37 %
5 Ct ,-~ative ~-~rle 15~ ~ 47 %
As the result~ show, both polyconden~ates inhibit the formation of calcium carbonate. When u~ed as water treatment agents, for 10 example for scale ; nhi h; tion, the poly~ond~n~at~ are u~ually used in amount~ from 1 to 500, preferably from 2 to 100, ppm.
The polyconA~n~ates o~t~in~le by the proce~s of the present invention are al~o suitable for u~e ag detergent additive.
The polyco~Aen~ation product~ obt~;nah~e by the proce~s of the pre~ent invention can be ~ncluded in detergents and cleaners either directly or in the form of th~ alkali m~tal, alkaline earth metal or am~onium ~alt~. Preference is gi~en to using the 20 sodium salt~ of the polyco~en~ates. They are ob~in~ble by treating the polycon~en~te~ with aqueou~ baYe~. Instead of the ~odium calts it i~ also po~sible to uRe ammonium sal~s, for ex~mrle the salts for~ed by treating polycon~ensate~ prepared accordlng to the present lnvention with ethano~ ~m1 n~, 25 diethanolamine or triethan~l~;"e. The polycondensate~ are included in phosphate-free or reduced-pho3p~atQ detRrgents (ie.
detergents having a pho~phate co~tent of les~ than 25~ by weigh~, calculated a~ trisodium polyphoQphate) to enhance the detergency and as ~ncrus~ation inhibitor. The amount~ of polycondensate 30 ra~ge ~rom 0.1 t~ 50, preferably from 1 to 30, % by weight, ba~ed on the detergent or cleaner.
Some of thQ polycondensates prepared by the proces~ of the pres~nt invention were ~ubjected to the CD test and al~o to a 35 determination of the ~lay-de~ch; ng power in the pre~ence of nonionic surfactants (the test methods are ind~cated for example in W0-A-g4/11486).
The re~ult~ ob~;ne~ in the CD test and the effectiveness test 40 werQ a~ follow~:
e F~fectivene~s ~]
t~n~
~5 1 340.2 89.2 2 291.8 81.3 ~ BASF Aktiengesellschaft 940339 O.Z. OOSO/45075 21 ~6336 3 367.2 75.4 4 383.8 76.4 C ~rative Example 1 328.~ 87.7 As the results sho~, the effectivenes~ values and the di8persing conctant~ of the polyconden6ate~ prepared according to the present invention correspond to tho~e of comple~ely polycon~n~ed aspart~c ac~ds.
The te~t of the clay-det~chi ng pow~r in the pre~ence of nonionic surfac~ants indicate~ an effectivenes~ of 93% for polyconden6ates a~ per Example 1 and of ~9% for the polyoon~nsates of Comparative ~ _- e 1.
~able 8 Time [d] Decrease ~n dis~olved organic carbon ~Y~rl~ 1 Compara~ive ~Y~mrle l O O
1 48 ~1 5~ 40 30 Result:
Measures according to the pre~ent invention make it possible to achieve a distinct ~mp~v~ ?nt in the degree of degradation of the aspartic acid polycon~ncates over the first 8 days. ~n addition, higher final degradation valueq are achieved at the 35 e~d.
The polycondensates of Example~ 2, 3 and 4 were subjectRd to a Zahn-Wellen~ test. ~y day 20 the di~solved organic carbon had decreased to the value~ indicated in Tab1Q 9.
BASF Aktienge~ell~chaft 940339 O.Z. 0050~4S075 Table 9 ~ ~Y~ e Decrease in di~olved organic carbon by day 20 [%]
10Comr~rati~e ~Y~mrle 1 40 Application test6 The polyco~den~ates of a~partlc acid prepared by ~he process of the pre~ent invention are ~uitable for u~e as water treatment 15 agents. The polyconden~ates of FY~P~ e 1 and C~r~rative Example 1 were tested for calcium ion compatibil~ ty by preparing in each ca~e aqueous solutions cont~ n~g 4S ppm of poly~o~en-~a~e a~d 1000 ppm of calcium ions and detc~i n; r~g the transmi~-sivity of the solution~. Eoth aqueous solution~ we~e found to 20 have a transmissivity of 99.8~, i.c. ~either sample combines with calcium ion~ to form ~paringly water-soluble calc~um salts.
The polycondensates of PY~rl~ 1 and ~ , rative FYA~rle 1 were al~o tested for dyn ~; c calcium ~arbonate ;n~; h; tion at a con-2s centration of 2 ppm of polyco~d~n~ates Calcium carbonate inhibition (2 ppm of polycocol.den~ateco~centrat~on~
30 Two test solutionQ are prepared. ~e~t solution 1 is water having a hardne~ of 20- (Ger~an) and a m~gne~ium hardnes~ of 10 ~German3. Test Qolution 2 is an aqueou~ solution ha~ing a ~odium carbonate hardne~ of 4.7- (~ ) and a sodi~ bicarbonate hard-ne~s of 12.3- (German).
A 500 ml capacity round-bottom flask equipped with ntirrer, reflux condenser and gag ~nlet tube i8 charged with 150 ml of test solution 1 and 150 ml of teYt ~olution 2 and al80 2 ppm oS
the in-test polymer and heated at 70-C for 1 hour or 2 hours while ~0 air is being pas~ed in at a rate of 3 1th. The flagk content~ are cooled down and ~iltered through a fluted ~ilter. The filtrate is titra~ed compl~Y~ ~~,ically to determine the calcium conten~ in a conventional manner.
g5 The ~ollowing calc~um carbonate inhibition values were determined:
BA5F Aktienge~ellscbaft 940339 O.Z. 0050~45075 ' 2196336 1~
CaC03 ; nh; h; tion after 1 hour 2 hours ~Y~rle 1 45 ~ 37 %
5 Ct ,-~ative ~-~rle 15~ ~ 47 %
As the result~ show, both polyconden~ates inhibit the formation of calcium carbonate. When u~ed as water treatment agents, for 10 example for scale ; nhi h; tion, the poly~ond~n~at~ are u~ually used in amount~ from 1 to 500, preferably from 2 to 100, ppm.
The polyconA~n~ates o~t~in~le by the proce~s of the present invention are al~o suitable for u~e ag detergent additive.
The polyco~Aen~ation product~ obt~;nah~e by the proce~s of the pre~ent invention can be ~ncluded in detergents and cleaners either directly or in the form of th~ alkali m~tal, alkaline earth metal or am~onium ~alt~. Preference is gi~en to using the 20 sodium salt~ of the polyco~en~ates. They are ob~in~ble by treating the polycon~en~te~ with aqueou~ baYe~. Instead of the ~odium calts it i~ also po~sible to uRe ammonium sal~s, for ex~mrle the salts for~ed by treating polycon~ensate~ prepared accordlng to the present lnvention with ethano~ ~m1 n~, 25 diethanolamine or triethan~l~;"e. The polycondensate~ are included in phosphate-free or reduced-pho3p~atQ detRrgents (ie.
detergents having a pho~phate co~tent of les~ than 25~ by weigh~, calculated a~ trisodium polyphoQphate) to enhance the detergency and as ~ncrus~ation inhibitor. The amount~ of polycondensate 30 ra~ge ~rom 0.1 t~ 50, preferably from 1 to 30, % by weight, ba~ed on the detergent or cleaner.
Some of thQ polycondensates prepared by the proces~ of the pres~nt invention were ~ubjected to the CD test and al~o to a 35 determination of the ~lay-de~ch; ng power in the pre~ence of nonionic surfactants (the test methods are ind~cated for example in W0-A-g4/11486).
The re~ult~ ob~;ne~ in the CD test and the effectiveness test 40 werQ a~ follow~:
e F~fectivene~s ~]
t~n~
~5 1 340.2 89.2 2 291.8 81.3 ~ BASF Aktiengesellschaft 940339 O.Z. OOSO/45075 21 ~6336 3 367.2 75.4 4 383.8 76.4 C ~rative Example 1 328.~ 87.7 As the results sho~, the effectivenes~ values and the di8persing conctant~ of the polyconden6ate~ prepared according to the present invention correspond to tho~e of comple~ely polycon~n~ed aspart~c ac~ds.
The te~t of the clay-det~chi ng pow~r in the pre~ence of nonionic surfac~ants indicate~ an effectivenes~ of 93% for polyconden6ates a~ per Example 1 and of ~9% for the polyoon~nsates of Comparative ~ _- e 1.
Claims (4)
1. A process for preparing aspartic acid polycondensates with improved biodegradability, which comprises polycondensing finely divided aspartic acid by thermal polycondensation in solid phase at temperatures from 180 to 250°C until not more than 70% by weight of the theoretica1ly possible amount of water which is formed in the course of the polycondensation has been removed from the reaction mixture.
2. A process as claimed in claim 1 wherein the proportion of the theoretically possible amount of water formed in the course of the polycondensation which is removed from the reaction mixture is not more than 60% by weight.
3. The use of the aspartic acid polycondensates obtainable as claimed in claim 1 or 2 as additive in detergents and cleaners and as scale inhibitor.
4. A use as claimed in claim 3 wherefor the aspartic acid polycondensates are used in the form of the alkali metal, alkaline earth metal or ammonium salts.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19944427287 DE4427287A1 (en) | 1994-08-02 | 1994-08-02 | Process for the preparation of polycondensates of aspartic acid with improved biodegradability and their use |
| DEP4427287.1 | 1994-08-02 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2196336A1 true CA2196336A1 (en) | 1996-02-15 |
Family
ID=6524698
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2196336 Abandoned CA2196336A1 (en) | 1994-08-02 | 1995-07-21 | Process for preparing aspartic acid polycondensates with improved biological degradability and their use |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0773970A1 (en) |
| JP (1) | JPH10504335A (en) |
| CA (1) | CA2196336A1 (en) |
| DE (1) | DE4427287A1 (en) |
| WO (1) | WO1996004330A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7132390B2 (en) | 2003-07-25 | 2006-11-07 | Clariant Gmbh | Phyllosilicate adsorbate and its use |
| US7256169B2 (en) | 1996-12-21 | 2007-08-14 | Clariant Produkte (Deutschland) Gmbh | Pulverulent laundry and cleaning detergent ingredient consisting of polycarbosylate and silicate |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19819187A1 (en) | 1998-04-30 | 1999-11-11 | Henkel Kgaa | Solid dishwasher detergent with phosphate and crystalline layered silicates |
| JP2002102886A (en) * | 2000-10-02 | 2002-04-09 | Sakai Chem Ind Co Ltd | Scale inhibitor and scale preventing method |
| US20160222163A1 (en) * | 2013-09-16 | 2016-08-04 | Basf Se | Modified polyaspartic acids, the production thereof and their use as dispersants and encrustation inhibitors in laundry detergents, dishwashing detergents and cleaning product compositions, and in water treatmentcleaning product compositions, and in water treatment |
| BR112017012488B1 (en) | 2014-12-12 | 2021-10-19 | Basf Se | METHOD TO PRODUCE POLYASPARTIC ACID THROUGH A PRE-CONDENSATE |
| WO2023100260A1 (en) * | 2021-11-30 | 2023-06-08 | 日清紡ホールディングス株式会社 | Marine biodegradable polymer compound, marine biodegradation promoter, and marine biodegradable resin composition |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT1240684B (en) * | 1990-04-26 | 1993-12-17 | Tecnopart Srl | POLYAMINO ACIDS SUCH AS BUILDERS FOR DETERGENT FORMULATIONS |
| US5057597A (en) * | 1990-07-03 | 1991-10-15 | Koskan Larry P | Process for the manufacture of anhydro polyamino acids and polyamino acids |
| US5221733A (en) * | 1991-02-22 | 1993-06-22 | Donlar Corporation | Manufacture of polyaspartic acids |
| US5152902A (en) * | 1991-03-19 | 1992-10-06 | Donlar Corporation | Polyaspartic acid as a calcium carbonate and a calcium phosphate inhibitor |
| US5116513A (en) * | 1991-03-19 | 1992-05-26 | Donlar Corporation | Polyaspartic acid as a calcium sulfate and a barium sulfate inhibitor |
| FR2675153B1 (en) * | 1991-04-15 | 1994-07-22 | Rhone Poulenc Chimie | DETERGENT COMPOSITION CONTAINING A POLYIMIDE BIOPOLYMER HYDROLYSABLE IN A WASHING MEDIUM. |
| US5329020A (en) * | 1993-10-05 | 1994-07-12 | Monsanto Company | Preparation of polysuccinimide |
-
1994
- 1994-08-02 DE DE19944427287 patent/DE4427287A1/en not_active Withdrawn
-
1995
- 1995-07-21 EP EP95926969A patent/EP0773970A1/en not_active Withdrawn
- 1995-07-21 WO PCT/EP1995/002892 patent/WO1996004330A1/en not_active Application Discontinuation
- 1995-07-21 CA CA 2196336 patent/CA2196336A1/en not_active Abandoned
- 1995-07-21 JP JP8506145A patent/JPH10504335A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7256169B2 (en) | 1996-12-21 | 2007-08-14 | Clariant Produkte (Deutschland) Gmbh | Pulverulent laundry and cleaning detergent ingredient consisting of polycarbosylate and silicate |
| US7132390B2 (en) | 2003-07-25 | 2006-11-07 | Clariant Gmbh | Phyllosilicate adsorbate and its use |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH10504335A (en) | 1998-04-28 |
| EP0773970A1 (en) | 1997-05-21 |
| WO1996004330A1 (en) | 1996-02-15 |
| DE4427287A1 (en) | 1996-02-08 |
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