CA2031329A1 - Basic polysaccharides - Google Patents
Basic polysaccharidesInfo
- Publication number
- CA2031329A1 CA2031329A1 CA002031329A CA2031329A CA2031329A1 CA 2031329 A1 CA2031329 A1 CA 2031329A1 CA 002031329 A CA002031329 A CA 002031329A CA 2031329 A CA2031329 A CA 2031329A CA 2031329 A1 CA2031329 A1 CA 2031329A1
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- Canada
- Prior art keywords
- denotes
- group
- polysaccharides
- cellulose
- denote
- 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.)
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-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5263—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using natural chemical compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B11/00—Preparation of cellulose ethers
- C08B11/02—Alkyl or cycloalkyl ethers
- C08B11/04—Alkyl or cycloalkyl ethers with substituted hydrocarbon radicals
- C08B11/14—Alkyl or cycloalkyl ethers with substituted hydrocarbon radicals with nitrogen-containing groups
- C08B11/15—Alkyl or cycloalkyl ethers with substituted hydrocarbon radicals with nitrogen-containing groups with carbamoyl groups, i.e. -CO-NH2
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B11/00—Preparation of cellulose ethers
- C08B11/193—Mixed ethers, i.e. ethers with two or more different etherifying groups
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Materials Engineering (AREA)
- Biochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
Basic Polysaccharides A B S T R A c T
Polysaccharides with recurrent units of the formula wherein S denotes a monosaccharide unit, A denotes a group of the formula and B denotes a group of the formula
Polysaccharides with recurrent units of the formula wherein S denotes a monosaccharide unit, A denotes a group of the formula and B denotes a group of the formula
Description
2~3~2~
Basic Polvsa-ccharides The present invention relates to new polysaccharides, to a process for their preparation and to their use.
Basic and cationic polysaccharides are much in demand as auxiliary agents for the manufacture of paper, as starting materials for the p;^oduction of highly active filter materials used for medical purposes and in the food industry, and as additives for hygienic and cosmetic cleansing and skin care products. As a general rule, they are the more effective the larger the number of basic and/or cationic groups they contain.
Basic polysaccharides are used inter alia as ion exchangers (US-A 4 199 485), for the preparation of acid soluble poly-saccharides (VS-A 2 623 041) and as starting materials for the synthesis of cationic polysaccharides (see US-A 2 768 162).
It is therefore desirable to be able to substitute poly-saccharides to a greater or less degree according to the individual requirements. Cellulose sulphonates have long ago been reacted with amines for producing celluloses containing nitrogen, but the degrees of substitution obtained were insufficient (e.g. 0.8~ by weight N; see Angew. Chem. 39, 1509-36 (1926)) and the yields were low (see J. Amer. Chem. Soc. 63, 1688-1691).
Cationisation of cotton for improving the dye absorption capacity for basic dyes is described in GB-PS 1 082 880 and US-A 4 178 438. The agents used for this purpose are N-methylol-chloroacetamide (GB-PS) or N-methylol-~-amino-propionamides (US-PS), which are made to react with the fibre and are then cationised with tertiary amines (GB-PS) or with alkylating agents (VS-PS). The degrees of substitution are low and the maximum amount of basic and hence quaternisable nitrogen is in both cases about 1.3% by s ~ ~ .
~:.
, :
weisht. 2~3~32~
According to US-A 3 472 840, cationic cellulose ethers are obt~ined by the alkylation of cellulose hydroxyethyl ether with 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride or with 2,3-epoxypropyl-trimethyl ammonium chloride obtained therefrom in the presence of an alkali metal hydroxide. Although the alkylating agent is in many cases used in large excess, the degree of substitution does not exceed 0.4. Much the same applies to the process according to EP-A-233 336 in which the same alkylating agent is proposed for the cationisation of starch under particularly advantageous process conditions. The degree of substitution remains bel;ow 0.2.
Another variation of the process according to US-A-3 472 840 is proposed in EP-A-189 935, which leads to the formation of hydrophobic cationic cellulose ethers. Epoxy quaternary salts are again used as alkylating agents. The results are similar to those of US-A 3 472 840. Higher degrees of substitution are obtained in the cellulose ethers disclosed in US-A 2 768 162. In the examples given there, it is stated that a DS of 0.7 is obtained because a preliminary product already containing this DS is used as starting material. The process appears to be simple and practicable but the starting materials are difficult to obtain. They may be obtained by the processes according to US-A 26 23 041 and US-A 26 23 042 of alkylating celluloses and cellulose ethers with dialkylaminoethyl chloride hydrochloride. In the process according to VS-A 26 23 041, which is carried out in solution, only small proportions by weight of cellulose, based on the total quantity, can be dissolved in a highly concentrated a~ueous solution of trimethylben2yl ammonium hydroxide. This quaternary ammonium base is not only very expensive but also very difficult to regenerate from the salt formed in the process. In the process according to US-A 26 23 042, alkylation is alleged to be carried out in suspension.
1~ 5289 3 - , .
.
- ~
, ~ ~3~ 32~
This is difficult to understand since again only small quantities of cellulose are used per quantity of reaction mixture and large quantities of the quaternary ammonium base are used as in ~S-A 23 26 041. The use of similar conditions would suggest that here again at least partial solution of the cellulose takes place, as may be recognised from the small quantities of cellulose which can undergo reaction. ~he dialkylaminoethyl chloride hydrochloride used as reactant is ambivalent in its reaction under the conditions of alkylation. It is capable of reacting not only with cellulose but also with itself.
.
In all these cases there are obtained dimeric to oligomeric quaternary ammonium compounds which link pointwise with the cellulose and are capable of simulating a high degree of substitution or are only aggregated with the cellulose and can be removed with difficulty by cleaning operations.
The doubts raised here are supported by DE-A-25 09 937, which describes a process for the cationisation of ethyl cellulose by alkylation with diethylaminoethyl chloride.
In this process, cellulose may be alkylated in the heterogeneous ph2se in the presence of ~aOH as base and only low degrees of substitution, amounting to 0.1 - 0.22, are obtained on the tertiary amino group in spite of the excess alkylating agent used. This preliminary product is then reacted with ethyl chloride to form amino substituted ethyl cellulose. Alternatively, the process may be carried out in solution with previously prepared ethyl cellulose which is then alkylated with diethylaminoethyl chloride.
Even under these more favourable conditions, the degrees of substitution are about equal under comparable conditions.
Even if attempts are made to increase the ~egree of substitution by the use of massive quantities of alkylating agent, as in Examples 4 to 6, the increase achieved is very limited, from 0.30 to 0.38. At the same time, the yield, based on the ~uantity of alkylating agent used, falls disproportionately from 38~ to 20~. Ihe results obviously 52~9 4 , . . .
.: :
,: :: . :
., - .
2 ~ ~ ~ 3 r l ~
approach a limiting value which cannot be exceeded even with a great increase in alkylating agent.
All the other processes discussed here are also carried out with cationising agents which are capable of reacting with themselves, with the result that the substitution on the polysaccharide is reduced and byproducts and polymers are formed which contaminate the basic or cationic poly-saccharide and may be impossible to remove. From the formulae given in US-A 34 72 840 it may be seen that poly-ether groups containing quaternary groups are grafted on cellulose and as this grafting may begin on a cell-0~
group, it may with equal probability and possibly even greater probability start with an OH~ ion since both the ion and the alkylating agent are in solution but the cellulose is in the heterogeneous phase.
Furthermore, rapid saponification to the guaternary diol may take place (see Das Papier 35, (12), 555 (1981)).
AlXylation must therefore always be followed by an elaborate process of purification and precipitation to separate the cationised cellulose from the cationic poly-ethers (see Examples 1 to 3 of US-A 34 72 840).
Added to these difficulties are the high cost and well known high toxicity of the above mentioned epoxy quaternary salts. ~he homopolymerisation and autocondensation described above with reference to the example of cationisation with dialkylaminoethyl chloride and epoxy guaternary salts also apply to all of the other alkylating agents mentioned. It is well known that the N-methylol amides of G~ 10 82 880 and US-A 41 78 438 readily react with one another to form unusable byproducts and polymers.
It has been recognised on the basis of the literature available that cationisation of polysaccharides by way of .: -: ::
~ 2~3 ~ 3~
dialkylaminoalkyl derivatives is not practicable in the technical field and alkylation has in practice therefore been carried out almost exclusively with 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride mentioned in VS-A
Basic Polvsa-ccharides The present invention relates to new polysaccharides, to a process for their preparation and to their use.
Basic and cationic polysaccharides are much in demand as auxiliary agents for the manufacture of paper, as starting materials for the p;^oduction of highly active filter materials used for medical purposes and in the food industry, and as additives for hygienic and cosmetic cleansing and skin care products. As a general rule, they are the more effective the larger the number of basic and/or cationic groups they contain.
Basic polysaccharides are used inter alia as ion exchangers (US-A 4 199 485), for the preparation of acid soluble poly-saccharides (VS-A 2 623 041) and as starting materials for the synthesis of cationic polysaccharides (see US-A 2 768 162).
It is therefore desirable to be able to substitute poly-saccharides to a greater or less degree according to the individual requirements. Cellulose sulphonates have long ago been reacted with amines for producing celluloses containing nitrogen, but the degrees of substitution obtained were insufficient (e.g. 0.8~ by weight N; see Angew. Chem. 39, 1509-36 (1926)) and the yields were low (see J. Amer. Chem. Soc. 63, 1688-1691).
Cationisation of cotton for improving the dye absorption capacity for basic dyes is described in GB-PS 1 082 880 and US-A 4 178 438. The agents used for this purpose are N-methylol-chloroacetamide (GB-PS) or N-methylol-~-amino-propionamides (US-PS), which are made to react with the fibre and are then cationised with tertiary amines (GB-PS) or with alkylating agents (VS-PS). The degrees of substitution are low and the maximum amount of basic and hence quaternisable nitrogen is in both cases about 1.3% by s ~ ~ .
~:.
, :
weisht. 2~3~32~
According to US-A 3 472 840, cationic cellulose ethers are obt~ined by the alkylation of cellulose hydroxyethyl ether with 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride or with 2,3-epoxypropyl-trimethyl ammonium chloride obtained therefrom in the presence of an alkali metal hydroxide. Although the alkylating agent is in many cases used in large excess, the degree of substitution does not exceed 0.4. Much the same applies to the process according to EP-A-233 336 in which the same alkylating agent is proposed for the cationisation of starch under particularly advantageous process conditions. The degree of substitution remains bel;ow 0.2.
Another variation of the process according to US-A-3 472 840 is proposed in EP-A-189 935, which leads to the formation of hydrophobic cationic cellulose ethers. Epoxy quaternary salts are again used as alkylating agents. The results are similar to those of US-A 3 472 840. Higher degrees of substitution are obtained in the cellulose ethers disclosed in US-A 2 768 162. In the examples given there, it is stated that a DS of 0.7 is obtained because a preliminary product already containing this DS is used as starting material. The process appears to be simple and practicable but the starting materials are difficult to obtain. They may be obtained by the processes according to US-A 26 23 041 and US-A 26 23 042 of alkylating celluloses and cellulose ethers with dialkylaminoethyl chloride hydrochloride. In the process according to VS-A 26 23 041, which is carried out in solution, only small proportions by weight of cellulose, based on the total quantity, can be dissolved in a highly concentrated a~ueous solution of trimethylben2yl ammonium hydroxide. This quaternary ammonium base is not only very expensive but also very difficult to regenerate from the salt formed in the process. In the process according to US-A 26 23 042, alkylation is alleged to be carried out in suspension.
1~ 5289 3 - , .
.
- ~
, ~ ~3~ 32~
This is difficult to understand since again only small quantities of cellulose are used per quantity of reaction mixture and large quantities of the quaternary ammonium base are used as in ~S-A 23 26 041. The use of similar conditions would suggest that here again at least partial solution of the cellulose takes place, as may be recognised from the small quantities of cellulose which can undergo reaction. ~he dialkylaminoethyl chloride hydrochloride used as reactant is ambivalent in its reaction under the conditions of alkylation. It is capable of reacting not only with cellulose but also with itself.
.
In all these cases there are obtained dimeric to oligomeric quaternary ammonium compounds which link pointwise with the cellulose and are capable of simulating a high degree of substitution or are only aggregated with the cellulose and can be removed with difficulty by cleaning operations.
The doubts raised here are supported by DE-A-25 09 937, which describes a process for the cationisation of ethyl cellulose by alkylation with diethylaminoethyl chloride.
In this process, cellulose may be alkylated in the heterogeneous ph2se in the presence of ~aOH as base and only low degrees of substitution, amounting to 0.1 - 0.22, are obtained on the tertiary amino group in spite of the excess alkylating agent used. This preliminary product is then reacted with ethyl chloride to form amino substituted ethyl cellulose. Alternatively, the process may be carried out in solution with previously prepared ethyl cellulose which is then alkylated with diethylaminoethyl chloride.
Even under these more favourable conditions, the degrees of substitution are about equal under comparable conditions.
Even if attempts are made to increase the ~egree of substitution by the use of massive quantities of alkylating agent, as in Examples 4 to 6, the increase achieved is very limited, from 0.30 to 0.38. At the same time, the yield, based on the ~uantity of alkylating agent used, falls disproportionately from 38~ to 20~. Ihe results obviously 52~9 4 , . . .
.: :
,: :: . :
., - .
2 ~ ~ ~ 3 r l ~
approach a limiting value which cannot be exceeded even with a great increase in alkylating agent.
All the other processes discussed here are also carried out with cationising agents which are capable of reacting with themselves, with the result that the substitution on the polysaccharide is reduced and byproducts and polymers are formed which contaminate the basic or cationic poly-saccharide and may be impossible to remove. From the formulae given in US-A 34 72 840 it may be seen that poly-ether groups containing quaternary groups are grafted on cellulose and as this grafting may begin on a cell-0~
group, it may with equal probability and possibly even greater probability start with an OH~ ion since both the ion and the alkylating agent are in solution but the cellulose is in the heterogeneous phase.
Furthermore, rapid saponification to the guaternary diol may take place (see Das Papier 35, (12), 555 (1981)).
AlXylation must therefore always be followed by an elaborate process of purification and precipitation to separate the cationised cellulose from the cationic poly-ethers (see Examples 1 to 3 of US-A 34 72 840).
Added to these difficulties are the high cost and well known high toxicity of the above mentioned epoxy quaternary salts. ~he homopolymerisation and autocondensation described above with reference to the example of cationisation with dialkylaminoethyl chloride and epoxy guaternary salts also apply to all of the other alkylating agents mentioned. It is well known that the N-methylol amides of G~ 10 82 880 and US-A 41 78 438 readily react with one another to form unusable byproducts and polymers.
It has been recognised on the basis of the literature available that cationisation of polysaccharides by way of .: -: ::
~ 2~3 ~ 3~
dialkylaminoalkyl derivatives is not practicable in the technical field and alkylation has in practice therefore been carried out almost exclusively with 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride mentioned in VS-A
3~ 72 840 and EP-A 233 336 or the 2,3-epoxypropyl-trimethyl ammonium chloride obtained therefrom tsee Das Papier 34 ~1980) pages 575 to 579 (1980); 35 (lOA), pages V 33 - V 38 (1981); and 35 (12), pages 555 - 562 (1981)).
Whichever of the last three classes of compounds mentioned may be used, it is always necessary to observe strict safety measures on account of the high toxicity and cationic polysaccharides obtained with these compounds must be carefully separated from byproducts and all aqueous waste liguors must be worked up and disposed of on account of their content in toxic guaternary byproducts, which can only be done at great expense.
Since the excess alkylating reagent added in the quaternising reactions is used up in side reactions and cannot be recovered, high degrees of substitution could hardly be realised economically.
It was an object of the present invention to prepare basic and cationic polysaccharides having a clearly predetermined and flexibly adjustable substitution and as high a degree of substitution as possible by clearly defined reactions using as far as possible inexpensive reagents.
The present invention relates to polysaccharides containing recurrent units I or a salt II thereof S I S / II
j\Bm l\B- Xe - .
: ' : ';, ' :
3 ~ ~
, wherein S denotes a monosaccharide unit, A denotes a group of the formula Ic attached to the monosaccharide units S by an oxygen atom O
-(CH2)n-C-OR Ic xe denotes an anionic group B denotes a group of the formula Ib attached to the monosaccharide unit S by an oxygen atom o i: -(CH2)n-C-NRl-R2-NR3R5 Ib p stands for a number from 0 to 2.9, m stands for a number from 0.05 to 2.9, m + p denotes a number frcm 0.05 to 3.0, R denotes Cl_l2 alkyl, Cs_6 cycloalkyl, C6-12 aryl~ C7-12 aralkyl, ~-hydroxyalXyl and/or l/Z Me wherein Me is a cation and Z is the valency of the cation, Rl denotes H or Cl_4 alkyl, R2 denotes an alkylene group which may be interrupted by at least one O or N atom or by an olefinic double bond, R3 denotes H, an alkyl group which is optionally substituted by an OH group or by an olefinic group and may be interrupted by at least one heteroatom, or it denotes an aralkyl group or the group of a polysaccharide corresponding to formula la Ap S ~(CH2)n-CO-NRl-R~
¦ m wherein the indices and substituents have the meanings indicated above W~ 5?89 7 .
: .. :.,: , .
:.- , ~ ,;:~ : ' -~ 2~ ~ 3~
R4 is equivalent or different of R3 and is linked with the same nitrogen atom as R3 and cannot have at the same time with R3 the meaning C2 - C8-alkylen or Ia, and R5 denotes H or an al~yl, aralkyl or aryl group and/or R3 and R5 together with their common N atom denote a ring optionally containing another heteroatom and/or Rl and R5 together with R2 form a ring and 10 n stands for ~ integer with a value from l to 6(i.e. 1,2,3,4,5 or 6).
In a preferred embodiment, in particular when the two N
atoms connected by R2 do not together stand in a ring, R2 preferably denotes a group corresponding to the general structure III
~[R6-Y~]qR7 wherein R6 and R7 may be identical or different and denote an :~ alkylene group with 2 to 6 C atoms optionally interrupted by an O atom, 20 Y stands for O or a group corresponding to one of the following formulae:
R3 ~N-, -N / 4 R4 ~ N-: ' , - '' ~ ,, ' ; ', :, ' . ' .
.' ` , ' , , : : ' - ' :
':. , : ~, ' , :
:, ' '' ~;' ' : ' ` ' --~`` 2~3~2~
wherein R3 has the meaning indicated above, X~ is an anion and R4 has the same meaning as R3 except that only R3 may correspond to the formula Ia, and q denotes an integer with a value from 1 to 5.
The substituents preferably have the following meanings:
R = H, Na, K, CH3, CH2CH20H- C2H5~ CH2, 3 OH
Rl: H, CH3 R3 and R4: H, CH3, C2Hs, C3H~, C4Hg, cycloalXyl, CH2-CH2-0H, CH2-CH2-OCH3, / CH3 ~
CH2-CH~ ~ CH2~=~
OH
fH3 CH2-CH=CH2, CH2-C=CH21 2 CH2 , CH2-cH2-cH2-~ -(CH2)6~~ -cH2-cH2-o-cH2-cH2 -CH2-CH=CH-CH2 .
-CH2-CH-CH2, Z OH
j R3 may also correspond to the formula Ia, ~ .
lS R5: H, CH3, C2H5, C3H7, C4Hg, phenyl, CH2-CH \
OH
CH2-CH2-H, CH2-CH2-OCH3, and R2 -CH2CH2-~ -(CH2-)3-~ -(CH2-)4-1 -(CH2-)6-1 CH2-CH-~ -~CH2-)3-O-~cH2-)2-. -cH2-cH=cH
R4 X~
-~CH2-)2-O-(CH2-)2-, -~CH2-)2-2~-~cH2-)2-, -(CH2-)2-21Z-(cH2-)2-~ -~CH2-)2-N ~ N-(CH2-)2-~
~W 5289 9 . v , ~ . , . .. . : , : . .. .
. ~ . : : .. . - . , -: : ~. : .
.- . . .
.: . ~ .. . ~ . : ~ .
~3~ 3~.~
-(CH2-)2-N-(CH2-)2-N-(CH2-)2--(CH2-)2-lN-(cH2-)2-~N-(cH2-)2-N-(cH2-) R13 X~ R3 X~
-~CH2-)2-N~-(CH2-)2-N~-~CH2-)2-R4 ~ /R4 -(CH2-)2-N N-(CH2-)2-X~ \ ~/ X~ , R \ ~
-(CH2-)2-N~ N-(CX2-)2-X~ \--J , R3 and R5 together with the N atom may for~ a group corresponding to one of the following formulae ,: j.
-R ~ ~ ~ X~, -N ~ O X~
-N N-R4 X~, -N ~ \ R4 X~
or the corresponding basic heterocyclic compounds prior to salt formation or quaternisation -N ~ , -N ~ , -N ~ O , -N N-R4 Rl, R2 and R5 together with the N atom may form a group corresponding to one of the following formulae .
.
,.. . . , . ... . ~ : - ...
.. . . . . , ., . ~,.
.. . . .
2~3~32~
-N~ r -N. N~ or -N N-R3, \ R4 --/ R5 X~3 x'3 -N~ N-R5 X~ denotes chloride, bro~ide, iodide, R3504~, benzene sulphonate, toluene sulphonate, methane sulphonate, phosphate, :
O O
- R9-P , R9-P
I ~o~
,i ORl wherein R9 = OH, ORl or Rl, in particular OH, CH30, C2H50, CH3 or C2H5, m = O.l - 2. 5 10 i P = 0.1 - 2. 5 and n = 1 - 4.
The following meanings are particularly preferred:
R H, ~a, CH3, C2Hs, C2H4H, CH2-~CH-CH3 ,~ OH
: H
15 R3 and R4: H, CH3, C2H5, CH2CH20H, -CH
~:: CIH3 ; CH2=CH-CH2, CH2=C-CH2 '~ .
1~ .
Si~89 li :
'~
Y . . , . , ~ . ~ . ~
S,"i'': ~. ~ . ;.` ' , ' , ':: ' :' ,: ' ., ' '. . ~: ` : , . , r-~ 2 0 3 1 3 ~, ~
.
R3 or R4 additionally -CH2-CH2-, -(CH2)4-~ -(CH2)6 ~ CH2 CH 2 ' OH
-cH2-cH=cH-cH2- .
R3 may in addition correspond to formula Ia, R5 CH3, C2Hs, CH2CH2H~
R2 - ~CH2-) 2-, - (CH2-) 3-' - (CH2) 6--(CH2-)2-N-[(cH2-)2-N-]l 3(CH2-)2-R R
/----\N
-(CH2-)2-N-(CH2-)2-~ -(CH2)2-N~, -(CH2-)2 -(CH2-)3-1-(CH2-)3 or the corresponding salt type or quaternised groups R3 and R5 together with the N atom may denote a group corresponding to one of the following formulae:
- ~ 0 , -N ~ N-CH3 or the corresponding quaternised groups, X~ denotes chloride, bromide, iodide, R1504~, toluene sulphonate or methane sulphonate, m = 0.2 - 2.5 n = l or 2 and j.
p - O.l - 2.2.
The ~ollowing meanings are particularly preferred:
20 R: H, Na or CH3, Rl H .
R3, R4 and R5: H, CH3, CH2CH20H, C2Hs, . , :- .; . -- - ~ - , . .
., 2Q~2~
R4 or R3 also -CH2-CH-CH2-, -(CH2)6-OH
R3 may also denote a group of the formula Ia, R2 _(C~2-)3-X~: chloride, CH3S04~ or bromide, 5 n = l, m = 0.2 - 2.0 and p = 0.1 - 1.9.
The invention further relates to a process for the prep-aration of a polysaccharide by the reaction of esters having the structure IV:
O
I / ~(CH2)n-C-O l/Z Me~r s . tIV,~
[ (C3~2~n~~C~O-R8~s o with an amine having the structure V:
HN- R2 _ ~ (V) Rl R5 wherein 15 r stands for a number from O to 2.5, s stands for a number from 2.9 to O.05 and r + s stands for a number from 0.05 to 3.0, and RB denotes Cl-l2 alkyl, Cs-6 cycloalkyl, C6-l2 aryl, C7-l2 aralkyl or ~-hydroxyalkyl and wherein the other substituents have the meanings indicated in Claim l.
j.
Formation of the polysaccharide derivatives according to the invention taXes place with removal of the group R80H
optionally in t~ie presence of H~ and/or OH~ ions.
- ~ ',', : `
`' ` ~ ` `
~ ~3~.3 -~articularly preferred polysaccharides are characterised in that R denotes H, Na or CH3, Rl denotes hydrogen, R2 denoteS (CH2)3~
R3, R4 and R5 denote CH3, CH2CH20H, C2Hs or H, : X~ denotes chloride, CH3S04~ or bromide, n = 1, r = 0.1 - 1.9, 10 s = 0.2 - 2.0 and S stands for a glucose or pentose unit.
In a particularly preferred embodiment, the monosaccharide unit S is linked to a substituted cellulose unit.
Another particularly preferred embodiment is characterised 15 in that the polysaccharide is present as a salt II and in that B corresponds to the following formula:
-(CH2)n-Co-NRl-R2-N9-R X~
wherein n, Rl, R2, R3, R4, R5 and Xe have the meanings indicated in Claim 1.
20 Salts II are preferably prepared by the reaction of poly-saccharide derivatives corresponding to ~ormula (I) with compounds corresponding to formula (VI) (R10)UX VI
wherein 25 R10 = R4 with the exception of the rest Ia or .~ . . , .... . : , .
~ 2~3~32~
X denotes a substituent forming an anion Xa commonly found in polysaccharide chemistry u = l or 2.
Esters of carboxymethyl cellulose have already been reacted with amines accordinq to VS-PS 3 904 600. Both the esterification of carboxymethyl cellulose and aminolysis of the ester, however, were carried out by ~ery expensive and complicated methods in solution. A product having the following structural element Cell-C~2CO-N~ ~ COO-C~2CH2-NEt2-~Cl was obtained from aminolysis with 2-diethylamino-p-amino benzoate. This group is unsuitable for the use of basic and cationic polysaccharide derivatives mentioned in the present invention since it is very bulky and contains a readily saponifiable ester group so that splitting off of the group HO-CH2CX2-Net2.HCl may already take place during synthesis of the compound in competition with aminolysis of the cellulose ether; further, during storage and in use in aqueous solution, the basic amino group may be split off, the activity of the polysaccharide derivative may fall and undesirable physiological effects may be produced.
Suitable polysaccharide esters for the preparation of the polysaccharides according to the invention include those ha~inq the structure II as described, for example, in DPS
957 938, EP 104 567 and J. App. Polym. Sci. 32 (6~ 5657-9 (1986) and especially those prepared according to DE P 38 42 947Ø Starting materials for such esters are: Polysaccharides~
including polyglycosanes such as cellulose, various '~ ' ' ' ~ ` .
2 ~ 3 ~ derivatives of cellulose such as methyl cellulose and mixed cellulose ethers such as methyl-hydroxyethyl celluloses, carboxymethyl cellulose and their various salts with sodium, potassium, calcium or ammonium ions, especially ~uaternary ammonium ions: cellulose sulphate with various counterions, e.g. of sodium, potassium, calcium, ammonium or quaternary ammonium groups; starches, dextrins, and glycogen; polyfructosanes such as inulin and graminine; polymannosanes and polygalactosanes; and mixed polysaccharides such as hemicelluloses as well as poly-xylosanes and polyarabinosanes.
Cellulose and its derivatives and starch and dextrins are preferred starting materials, the following being partic-ularly preferred: cellulose, methyl cellulose, ethylcellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose and salts and starches thereof.
Suitable amines for the preparation of the polysaccharide derivatives according to the invention are those having the general structure V. When R3 2nd/or R5 stand for H, the products obtained a~ter the reaction with IV may be insoluble in water and cap2ble of swelling in water as in the case of the structure I in which R = Ia, which indicates cross-linking. When R3 and R5 in formula V are not H, the products obtained are generally soluble in water and in some c2ses also soluble in alcohols.
The solubility of the amino- or zmmonium-polysaccharides according to the invention in alcohols or water depends both on the starting material, on the amine (see above), on the degree of substitution, on the alkylating agent and on the degree of ~uaternisation and may be adjusted according to re~uirement. Thus, for example, bis-primary diamines give rise to cross-linked, insoluble products, primary~
tertiary diamines give rise to soluble products and bifunctional alkylating agents give rise to insoluble polysaccharide derivatives.
~ 5289 16 . .. : -~3~
In some cases, ~uaternised derivatives also containing carboxyl end groups may form insoluble products, especially after prolonged drying, presu~ably due to a form of "inner"
salt formation. They may, however, readily be brought into by means of small quantities of bases.
The following are examples of suitable amines corresponding to formula V:
H2N-(CH2)2-N H2N-(CH2)3-N \ H2N-(CH2)6-N \
HN-(CH2)2-N(C~3)2l HN-(CH2)31.N(CH3)2 . 15 CH3 CH3 H2N-(CH2)2-N ~ N-CH3/ H2N-(CH2)3-/--\ CH2CH2oH
H2N-(CH2)3-N O , H2N(CH2)2-N-CH3 H2l~-(cH2)2-[NH-(cH2)2~l-s-NH2~ H2N-(cH2)3N(cH2cH2oH)2 i HN-(CH3)31~(C2H5)2~ H2N-(CH2)2-0-(CH2)2-N(CH3)2, 1 25C2~s ~ ~
H2N-(cH2)3-N~NH~ H2N-(CH2)2-1~ ~N-(CH2)2-N(CH3)2l H2 N - ( CH2 ) 3 -N ~ N- ( CH 2 ~ 2 -N ~0 , H2 N- ( CH 2 ~ 2 N~3 ICH3 CIH3 ~CH3 H2N-CH2-CH-N(CH3)2~ H2N-CH2-CH-O-CH-CH2-N(CH3)2, H2N-(cH2)3-N~ I H2N-(CH2)3-N~cH2cH20cH3)2 OH ~ N
HN-(CH2)3-N(CH2-cH-cH3)2l H2N-(CH2)6-C2H5 \.=.
1~ 5289 17 ,:
....
~3 ~ ~2~
~=~N N - N
HN ~ ~ H2N ~
/=~N N
H2N-(CH2)3-N ¦ I H2N-(CH2)3 N
\ ~ N
The following, for example, are preferred:
H2N-(CH2)2N(C~3)2 , H2N-(CH2)3-N(CH3)2 H2N(C~2)6-J~(CH3)2 , H2N-(cH2)3N(cx2c~2oH)2 ~
H2N(CH2)3~N(C2Hs)2 , H2N-(CH2~3-N N-CH3 , 15 N2N-(C1~2)2-N ~O, H~N-(C}~2~21N~N}~ , H2N-(CX2)2-N\ ' H2N-(CH2)3-N \
X2N-(CH2)2-NH-(C~2)2-~H2 The following are examples of suitable compounds (R10~ux of formula VI: HCl, HBr, CH3S03H, H3P03, H3P04 . CH3PO(OH)2, ~ .
CH3 ~ S03H, ~-S03H
as well 2S methyl chloride, ethyl chloride, propyl chloride, butyl chloride, chloroethanol, chloropropanol, epichlorohydrin, l-chloropropane diol-(2,3), chlorobutanol, 1-chloro-2-methoxy ethane, 1-chloropropanol-2, benzyl chloride, (meth)allyl chloride, methyl bromide, methyl iodide, methyl methane sulphonate, methyl benzene sulphonate, methyl toluene sulphonate, trimethyl phosphate, methyl-o,o-dimethyl phosophonate, benzylmethane sulphonate, allyl tosylate and benzyl mesylate; further, 1,2-dichloroethane, 1,4-dibromobutane, 1,6-dibromohexane, epichlorohydrin, 1,4'-dichlorobutene-2 and 1,6-ditosyl-hexane, l,6-dimesyl-hexane, ~,~'-dibromodiethyl ether and 3 2 ~
, B,~'-dichlorodiethyl ether.
The following, for example, are preerred: methyl chloride, chloroethanol, dimethyl sulphate, methyl mesylate, methyl tosylate, (meth)allyl chloride, benzyl chloride, 1,6-dibromohexane, epichlorohydrin and 1,4-dichlorobutene-2.
The reaction may be carried out in an excess of the amine used as reactant or in a dispersing agent. Examples of suitable dispersing agents include hydrocarbons, halogenated hydrocarbons, ethers, alcohols and carboxylic acid amides.
The following are specific examples: cyclohexane, heptane, isooctane, benzene, toluene, xylene, chlorobenzene, di-chlorobenzene, methylene chloride, chloroform, diethyl ether, diisopropyl ether, dibutyl ether, dioxane, benzo-dioxane, anisol, dimethoxybenzene, ethylene glycol dimethyl ether, isopropanol, isobutanol, methanol, tert.-butanol, isoamyl alcohol, dimethyl formamide, dimethyl acetamide, ~-methyl pyrrolidone, N-methylcaprolactam. ~hese solvents may be used both for the amination reaction and for the alkylating reaction.
The reactions of the carbalkoxy esters of polysaccharides with amines to form amino amides and their alkylation to form cationic polysaccharides should not be carried out on completely dry polysaccharide derivatives as this frequently results in a very slow and insufficient and therefore not accurately reproducible reaction and substitution. The polysaccharides generally contain a few percentages of water so that the addition of water is not necessary in all cases but if the water content is low or unknown it is advisable to add water to the reaction mixture. Ihe amount added may be from 1 to 200% by weight, preferably from 2 to 170~ by weight, more preferably from 3 to 150% by weight, most preferably from 4 to 120% by weight, based on the quantity of polysaccharide put into ~ 5289 19 .
:, . , . :
.
. ' .
2 ~
the process. The amount of water added is not very critical but should not be sufficient to cause unduly strong swelling or even solution of the polysaccharide as this would render control of the reaction and working up more 5 difficult.
The reaction is carried out at temperatures from 0 to 160~C, preferably at 10 to 140~C, more preferably at 15 to 125'C and most preferably at 20 to llO-C. Acids or alkalis may be added 25 catalysts in quantities of from 0.01 to 5%
by weight, based on the cellulose derivative. The following are examples of suitable catalysts: HCl, H2SO4, H3P03, NaOH, XOH, LioH~ Ca(OH)2 and Ng(OH)2.
The molar ratio of the polysaccharide esters to the amines V or to the compounds VI is from 1:0.1 to l:loa~ preferably from 1:0.2 to 1:50, most preferably from 1:0-5 to 1:10 although molar ratios outside the range of 1:10 may safely be used.
~i The reaction time is generally from one hour to ~0 hours, preferably from 2 to 24 hours, most preferably from 3 to 20 hours.
I
The products are worked up by known methods of separation and washing with solvents to remove the hydroxyl compound R8OH which has been split off and excess amine or excess (R10)UX. With suitable choice of solvents, hydroxyl compounds R8OH, amine and alkylating agent, these compounds may be recovered from the reaction solutions by distillation and reused.
The new functional polysaccharides are also zwitter ionic compounds in which, when r > 0 and/or R8 , H or Me, the ionic qroup VII
O
-(CH2)n-c-o~ (VII) t.~ 5289 20 ,~
: .
,, , ~ .. .. . .
- . :
. . ~, .
~ 2~3~ 3~
and the cationic group VIII
-(CH2)n-C-N-R2-~ -R4 (VIII) R R
are present side by side in the s2me molecule. The anionic or cationic character predominates according to which of the two gr~ups has a greater DS.
The water-soluble cationic po]ysaccharides according to the invention are suitab]e for use as additives in hygienic and cosmetic cleansing and skin care products, as auxiliary agents for the manufacture of paper and for the treatment of textile fibres 15 to impro~e the handle thereof.
The water-so]uble cationic polysaccharides can also be used as aggregating agents.
Aggregation is understood to refer to flocculation, coagu]ation and precipitation.
Flocculating agents are processing auxiliaries which allow solid/liquid separation processes to be carried out in an economically efficient manner. With their aid it is 20 possible to improve considerably the rate of sedimentation of solids which are suspended in water and are frequently in colloidal form. Effective flocculating agents bring about almost complete flocculation of the suspended particles, thusresulting in substantial minimisation of the residual solids contents of the liquid phase. The use of flocculating agents also increases the solids content of the solid 25 phase, thus allowing mechanical dewatering of the sedimented slurries to be carried out in a technically and economically advanlageous manner.
Among flocculating agents a distinction must be made between primary flocculating agents and flocculation auxiliaries. Primary flocculating agents are chemical compounds which form precipitates which are poorly soluble in water. These 30 include the Fe, Al and Ca salts widely used in practice. When such compounds are added the charge of the particles in the suspension, which ha~e for the most part been stabilised by negali~le surface charges, is subsequently neutralised, as a result of wllich the electric double layer of the particles is destroyed and rapid coagulation occurs. As the h~drol~sis of Ihe inorganic compounds progresses water-satura~ed ~. - , . . . . . .
,:
., . ~ . , - . .. ,: .
2~3~
voluminous flocs a~e forrned ~ hich entrap the substances contained in Ihe water and cause them to precipita~e. Factors which have a disadvantageous effect on nocculalion using inexpensi~e inorganic metal salts are the dependence on temperalure of the fJocculation process, the requirement of a narrow pH range, the relatively low rate of sedimentation of the flocs and the formation of large volumes of slurry.
Floccu]ation auxi]iaries are cationic, anionic or neutral water-soluble polymers of high molecular weight, which do not display these disadvantages. Here as well, as a result of ionic and dipolar interactions between the polymers and the suspended particles, coagulation of the colloidal particles initially occurs. Where the molecular weights are sufficiently high the macromolecules are capable of linking several deslabilised particles to fomm rapidly sedimenting shear-resistant macroflocs.
Flocculation auxiliaAes are widely used industrially for water-conditioning and waste water treatment in the petroleum, paper, coal and ore industries as well as in some branches of the chemical industry.
The cationic polysaccharides produced according to the in~ention can advantageously be used in quantities of 0.01 - O.S~o by weight. They can be tailored for use in all fields of application according to their degree of cationisation and their molecular ~eight.
In many fields concemed with the production and storage of liquid and semi-solidproducts microorganisms present a problem as a result of their ability to multiply and their metabolism. Thus no methods are at present available for the removal of already fommed mycotoxins whule at the same time preser~ing the quality of the food concerned (H. K. Frank, SchAftenreihe des Bundes fur Lebensmit~elrecht und Lebensmittelkunde, Edition 76, 1974). The water-insoluble cationic polysaccharides produced according to the in~ention are used for the production of highly acti~e filter mateAals. For the abo~ementioned reasons these are in greatdemand in the pharmaceutical industry and the be~erage industry.
The mode of operation of filter beds is based mainly on - the mechanical screening effect, - the penetratioll effect and - the adsorplion effect.
:..
- ~ i 2Q3~3~
As a result of the mechanical screening effect coarse particles of sediment are retained on the surface of the bed. They do not penetrate into the pores. Finer particles of sediment penetrate more deeply into the bed, become entrapped in the net of material and gradually block the pores (penetration effect). Main]y as a result of the e]ectrical charges prevailing between the particles of sediment and the raw materials those sedimented substances which have penetrated into the bed areadsorbed onto the surfaces of the pores (adsorption effect). These effects are dependent on the material properties of the raw materials (kieselguhr, cellulose, cotton). The capacity of a filter bed is defined by its clarification efficiency. This is determined by the inleraction of screening, penetration and adsorption effects.
In bacterial filtration conventional filter beds disp]ay inadequate clarification efficiency due to a lack of adsorbing power.
Test filters in which a portion of the raw material cellulose was replaced by the cationic polysaccharides according to the invention were more highly effective against pyrogenic and endotoxic bacteria in bacterial filtration than fibre filters or filter beds filled with aluminium oxide.
- , ~ . . .
.
;
-~ Example 1 120 g (0.5 mol) of a sodium carboxymethyl cellulose having a DS of 1 was reacted with 76 g (0.6 mol) of dimethyl sulphate in 300 ml of a mixture of 10% water and 90~ iso-propanol at 25'C for two hours and at 70'C for two hours.
The reaction product was then suction filtered, washed with isopropanol and dried in a vacuum at 50 C. 141 g of a water insoluble cellulose ether showing a strong ester band at 1755 cm~l and a weak carboxylate band at 1610 cm~l in the IR spectrum were obtained. Fsterification thus proceeded to an extent of 78~.
ExamPle 2 30 g of the product from Example 1 and 21 g of 3-N,N-dimethylamino--propylamine are stirred in 100 ml of toluene at lOO C for 5 hours. After the solution has been decanted, repeatedly washed out with isopropanol and dried under vacuum at 50'C, 22 g of a water soluble amino cellulose having a nitrogen content of 6.7 are obtained. This corresponds to about 90% conversion of the ester into aminoamide and a DS of 0.7 on the amino function and 0.2 to 0.3 on the carboxylate function. The IR spectrum has a broad, strong carbonamide band at 1670 cm~l.
Fxam~le 3 ; 120 g (0.5 mol) of a carboxymethyl cellulose have a DS of 1.0 and a moisture content of 8.3% are suspended in chloroform and boiled under reflux with 76 g (0.6 mol) of dimethyl sulphate for two hours. After suction filtration, 1 repeated washing with chloroform and drying in air, 142 g of a cellulose derivative which has carboxylate bands and carboxylic ester bands (1757 and 1610 cm~l) in the IR
spectrum and is insoluble in water are obtained. The degree of esterification is 50% (IR analysis).
:.
f~5289 24 i L
:1 ' ' " : ..
Example 4 62~3 ~ 3~
71 g of the cellulose derivative from Example 3 and 51 g (0.5 mol) of 1-amino-3-(dimethylamino)-propane are stirred s up in toluene at 95'C for 8 hours. After suction filtration, washing with toluene and repeated washing with isopropanol followed by drying in a vacuum at 105'C, 53 g of pulverulent aminoamide cellulose are obtained. The product has a nitrogen content of 3.7~, corresponding to a DS of about 0.4 on the aminoamide group, and it shows amide and carboxylate band in the IR spectrum.
Example 5 . I' 278 g ~about 1 mol) of a freshly prepared sodium carboxy-methyl cellulose (DS 1, moisture about 15%) are reacted with an approximately 12 to 13 molar excess of methyl chloride at 90'C and 25 bar for 15 hours. The reaction mixture obtained is cooled, depressurised, washed with 70 methanol and dried in a vacuum at 50-C.
233 g of water insoluble esterified carboxymethyl cellulose having a strong ester band at 1755 cm~l and a weak carboxylate ~and at 1610 cm~l in the IR spectrum are obtained. Conversion of the sodium carboxylate to the ester amounts to 82~.
Exam~le 6 80 g of esterified carboxymethyl cellulose from Example 5 are sucpended in 200 ml of toluene and 106 g of 3-N,N-dimethylamino propylamine and stirred at 60 C for 9 hours.
Ester aminolysis has proceeded by about 90~ at the end of that time and is completed after a further 6 hours at ~5'C~
After suction filtration, repeated washing with toluene and drying at 50'C in a vacuum, 86 g of pulverulent, water soluble amino cellulose having a nitroqen content of 8.1%
and a DS of about 0.8 on the amino function are obtained.
l~ ~289 25 .. . . . :
.. . . : ..
. .
:~
Exam~le 7 100 g of the product from ~xample 6 are suspended in 300 ml or toluene and 100 g of dimethyl sulphate and stirred at 50'C for 12 hours. After suction filtration, washing with toluene and drying at 50'C in a vacuum, 110 g of a water soluble cationic cellulose derivative having a nitrogen content of 5.5% and a sulphur content of 6.2% are obtained. The DS with respect to the ammonium group is about 0.8.
Exam~les 8 to 17 i' General method of procedure:
Carboxymethyl celluloses having a total DS expressed as DSg and an ester DS expressed as DSest in which the unesterified part is present as sodium salt are suspended in isopropanol or toluene. The amine selected for the reaction is added and the reaction mixture is stirred at 90 to 95'C for 10 hours, suction filtered, freed from excess amine by washing with toluene or isopropanol and dried in a vacuum at 50~C. The nitrogen content of the amino-amido celluloses obtained is determined by elementary analysis. IR analysis in each case shows amide, ester and carboxylate bands, the strengths of which vary according to the DS.
The individual data and results are shown in Table 1 below.
~ 52~9 26 .
~ $ ~ _ 2 ~
~1 ~ I ~ + I +
~ ~ _ _ t, ~o + + + , + + + , I +
U~, c JJ ~n 0 ~ D 0 0 0 Z ~ 0 ~ ~ ,/ o ~ 0 Q~ ~ 0 0 o~ o ~q _I ~ ~ ~ o H ~ ~D 0 ~D H N 0 ~
, i' .;
,, &
O
~-~1 ~1 _I O _I O _I O _1 0 _I O _~ O ~1 0 0 0 0 0 :~ O O O O O O O O O O O O O 11~ 0 U~ ~,q o ~Q O
( 7 ~ ~ ~ ~ ~ ~ P~- O 1~1 0 ~ O
~3 1': 0 ~ O ~ O ~1 10'1 It~ W O 'q N ~ N Et Ll~ ~S N
~:1 ~ N a N a ~ a ~ a t: a) o o o o o o~ o o o o N O O 11~ ) O ~ N 11~ N
01 N ~
.
U~ N O Ul ~ ~ r-l o ~ 0 11~
~ ~ U7 0 0 U~ 1~ 0 0 U) U~
a o o ,~ o o ,~ o o o i~ O O N O O ~O O O N
U~
a o o ,~ o o ~1 . o o o _~
Q) _, Q O 0 1~ 0 -1 N 1`7 ~ U`) U~
E-~ a:
WW ~289 27 :' ~' ` `-. - ~, ` , .
` Leaend to Table 1 2 0 3 ~
CMC = carboxymethyl cellulose derivative DAPA - 3-N,N-dimethylaminopropylamine PEXA - pentaethylenehexamine DETA = diethylenetria~ine AEP = aminoethylpiperazine ATA ~ 3-aminot;-iazole + = soluble (+) = partly dissolved or strongly swelled - 5 insoluble Examples 18 ~o 24 General method of procedure:
Aminocarbonamide celluloses from Examples 9, 10, 11, 12, 13 and 16 are suspended. An equal quantity of chloroethanol is added in each case and the reaction mixture iæ stirred at 70-C for 15 hours, thoroughly washed several times with toluene Dnd drled in D V2CUU= at SO'C ~see TDble 2).
: ' ~!W 5 2 8 9 28 r . -J~ 2~3~ 3~
o d~ N ~ ~1 Il --I O ~
t,) N ~ tl~ ~ I~ O
rl C~
u~
C
:Z
~1 ~ ~ ~ 1` ~ O
-~ ~ ~ o u~
j. ~
O U~ O ~ O OO ~D O ~ O O O O
O ~1 0~ rtO ~I N ~ I O ~ O _I
t~ ~ ~ N
a) C) Q~ U a) c) Q) ~ C~ O ~ O a~ o ~ o C) o ~ o G) O
Q C ~ N ~ N :~ N :~ N :~ N ~ t~
~( O O O O O O O
u~ E~+ E~+ E~+ E-l+ E-~+ E~+ E~+
,~ ~
C ~ U~ O O O O O O
o5~3 1` t`
:
' U~ ~ O U~
C~ O O ~1 0 0 O O N O O ~ N
V~
a o O ~1 0 0 ,. ..
:
o Z
_I o O ~ 0~ C~ ~ O O _/ --I N N ~ (~ O
1;~ ~ ~; ~ ~ ~ N ~I N
E~ _ 528q . ` , ~. `
. ` . ` . ~ : .
. . ...
` .
2~3~ 3?~
The results of Experiments 17 to 23 are listed in Table 2.
The high degrees of substitution calculated from the N- and Cl-contents are due to the starting materials, the esterified carboxymethyl celluloses.
Exam~les 25 to 31 General method of procedure:
Aminocarbonamide celluloses from Examples 9, 10, 13 and 14 are suspended and reacted with various alkylating agents at 50-C for 10 hours with stirring. After the reaction mixture has been washed with the dispersing agent used to remove excess alkylating agent, the quaternised celluloses are dried in a vacuum at 50'C.
:.
Further in~ormation and results are given in Table 3.
.
1~ 5289 30 - , , : :
- .. ~ . - ..
: ~ . ,.. . - .. .
.. , ,.... .: :
,. .. ~; - ,- . :
. , , .,;, . ~ . - ~ .:
::
2 ~ 9 ,, ~ ~
.~ ~ + + + + ~ , , , ~ _ _ ~o U~
I~
~n o~P ~ r c~
P:
~ ,I r o o~o r ~D
~) Z _l ~ ~ ~ ~D In ~n _ 0~ ~u~
o . ,~ r~ I
~ U~
_IS :~~: XO ~o ~)o Xo :~:o mu~
.~-~ a ~~ ~ a n ~ u~ m u~ a ~3 ~0 ~0 Q, ~ O
o o o o ~: o P. R. oP' ~ o~ ~
t;~ r J o O O U~ 0 ~: a)a) 5'1 ~ ~ H + H + a) u~
Q) S
~ _I O ~ O O O O O O O O ,1 0 _I ~ O
0-~1 O O O O U~ O ~ O U~ O ~D O CD O O r~
:1 3 E~ ~ H ~ H ~ H ~ H ~ E-~
:~
~J
O O O O O O O L~
~q . ~ ~
J~ ~ ~ ~ ~,~ X
Q~ ~ S
U~ ~ h O O
~,~ O O O ~ a . O O O ~ ~ ~D ~ ~ ~ ~S
~ G~ D ~S
a o o o ,~ N I
,~
.,~
~ ~ ll ll ll ll Q ~ O ô~ c r~ ô cr ô o~ r~ o ~ mr E~ h ~ ~ m a l~W 5289 31 ' '- ., - : .
2~3:~3~
ExamPle of Practical application 1 Method of flocculating test 0.2% solutions of the flocculating agents to be tested are prepared.
7.5 g or SPS China Clay used as filler are weighed in each case into a 500 ml graduated cylinder. The volume in the cylinder is then made up to 500 ml by the addition of pure water or water which has been adjusted to a particular concentration of flocculating agent by the addition of the appropriate quantity of one of the above mentioned solutions of flocculating agents. The contents of the cylinder are then vigorously shaken and flocculation is observed. After the cylinder has been left to stand for 5 minutes, the height of flocculation ~ml) is determined and the cloudiness of the zone of water above the filler is assessed visually.
A hydroxyethyl cellulose quaternised with l-chloro-2-hydroxy-3-trimethyl discloced in DOS 1 593 657, having a DS
of 0.4, is used as comparison product.
(see Table 4) l~ 5289 32 .
.
3 "~ ~3~2~
U~
a o +
~ U~ o U~ ~ ~ ~D
a o o o U~
. I o ~ In o ~1 o ~ El . o u~ ~ In i O ~
'. :i o U~ . o o o U~
-~ O O~ I~ i~ I`
0~O e ~ ~ ~
-~1 . U~ O
S O O~
o~ ~ o o ,~ . o I o I o O ~ ~ ~
U~
. ~
JJ C
o a O G~
' ~ Q~
U C
o ~ u~ 8 ~ ~ ~ 3 ~ ~ o ~ ,~ o o ~ o ~ o ~ ~
C ~ J~ o o 1 C-~
_~ Ll ~ r~
:~ O) ~
Q) t~ ~ S ~ S ~ ~
~ o ~ 8 ~ ~ ~ ~
~ ,, o ~ o~ o ~, ~ ., ~ ., ~ ,, E~ ~ P~ O ~: O ~: O :~
W\~l ~28q 33 ,- - ` - . .. . .. . . .... . . ... .
: . :,.,. , . - . , ~, , : . - ~ . : . . .
- - ~ ` . :; , : .: - : i - :~ :
~ ~ 3 ~ t~
Table 4 shows that the derivatised cellulose derivatives according to the invention produce significantly more rapid sedimentation of china clay than the commercial product, Polymer IR 125. The superiority of the new cellulose derivatives prevails even when the amount of active substance contained therein (Example 19, DS 0.25) is less than in the comparison substance. When the DS rises to 0.6, the improved effect is very mar~ed. It is surprisingly found that the basic product from Example 9 which is not quaternised also serves as excellent flocculating agent.
.
Whichever of the last three classes of compounds mentioned may be used, it is always necessary to observe strict safety measures on account of the high toxicity and cationic polysaccharides obtained with these compounds must be carefully separated from byproducts and all aqueous waste liguors must be worked up and disposed of on account of their content in toxic guaternary byproducts, which can only be done at great expense.
Since the excess alkylating reagent added in the quaternising reactions is used up in side reactions and cannot be recovered, high degrees of substitution could hardly be realised economically.
It was an object of the present invention to prepare basic and cationic polysaccharides having a clearly predetermined and flexibly adjustable substitution and as high a degree of substitution as possible by clearly defined reactions using as far as possible inexpensive reagents.
The present invention relates to polysaccharides containing recurrent units I or a salt II thereof S I S / II
j\Bm l\B- Xe - .
: ' : ';, ' :
3 ~ ~
, wherein S denotes a monosaccharide unit, A denotes a group of the formula Ic attached to the monosaccharide units S by an oxygen atom O
-(CH2)n-C-OR Ic xe denotes an anionic group B denotes a group of the formula Ib attached to the monosaccharide unit S by an oxygen atom o i: -(CH2)n-C-NRl-R2-NR3R5 Ib p stands for a number from 0 to 2.9, m stands for a number from 0.05 to 2.9, m + p denotes a number frcm 0.05 to 3.0, R denotes Cl_l2 alkyl, Cs_6 cycloalkyl, C6-12 aryl~ C7-12 aralkyl, ~-hydroxyalXyl and/or l/Z Me wherein Me is a cation and Z is the valency of the cation, Rl denotes H or Cl_4 alkyl, R2 denotes an alkylene group which may be interrupted by at least one O or N atom or by an olefinic double bond, R3 denotes H, an alkyl group which is optionally substituted by an OH group or by an olefinic group and may be interrupted by at least one heteroatom, or it denotes an aralkyl group or the group of a polysaccharide corresponding to formula la Ap S ~(CH2)n-CO-NRl-R~
¦ m wherein the indices and substituents have the meanings indicated above W~ 5?89 7 .
: .. :.,: , .
:.- , ~ ,;:~ : ' -~ 2~ ~ 3~
R4 is equivalent or different of R3 and is linked with the same nitrogen atom as R3 and cannot have at the same time with R3 the meaning C2 - C8-alkylen or Ia, and R5 denotes H or an al~yl, aralkyl or aryl group and/or R3 and R5 together with their common N atom denote a ring optionally containing another heteroatom and/or Rl and R5 together with R2 form a ring and 10 n stands for ~ integer with a value from l to 6(i.e. 1,2,3,4,5 or 6).
In a preferred embodiment, in particular when the two N
atoms connected by R2 do not together stand in a ring, R2 preferably denotes a group corresponding to the general structure III
~[R6-Y~]qR7 wherein R6 and R7 may be identical or different and denote an :~ alkylene group with 2 to 6 C atoms optionally interrupted by an O atom, 20 Y stands for O or a group corresponding to one of the following formulae:
R3 ~N-, -N / 4 R4 ~ N-: ' , - '' ~ ,, ' ; ', :, ' . ' .
.' ` , ' , , : : ' - ' :
':. , : ~, ' , :
:, ' '' ~;' ' : ' ` ' --~`` 2~3~2~
wherein R3 has the meaning indicated above, X~ is an anion and R4 has the same meaning as R3 except that only R3 may correspond to the formula Ia, and q denotes an integer with a value from 1 to 5.
The substituents preferably have the following meanings:
R = H, Na, K, CH3, CH2CH20H- C2H5~ CH2, 3 OH
Rl: H, CH3 R3 and R4: H, CH3, C2Hs, C3H~, C4Hg, cycloalXyl, CH2-CH2-0H, CH2-CH2-OCH3, / CH3 ~
CH2-CH~ ~ CH2~=~
OH
fH3 CH2-CH=CH2, CH2-C=CH21 2 CH2 , CH2-cH2-cH2-~ -(CH2)6~~ -cH2-cH2-o-cH2-cH2 -CH2-CH=CH-CH2 .
-CH2-CH-CH2, Z OH
j R3 may also correspond to the formula Ia, ~ .
lS R5: H, CH3, C2H5, C3H7, C4Hg, phenyl, CH2-CH \
OH
CH2-CH2-H, CH2-CH2-OCH3, and R2 -CH2CH2-~ -(CH2-)3-~ -(CH2-)4-1 -(CH2-)6-1 CH2-CH-~ -~CH2-)3-O-~cH2-)2-. -cH2-cH=cH
R4 X~
-~CH2-)2-O-(CH2-)2-, -~CH2-)2-2~-~cH2-)2-, -(CH2-)2-21Z-(cH2-)2-~ -~CH2-)2-N ~ N-(CH2-)2-~
~W 5289 9 . v , ~ . , . .. . : , : . .. .
. ~ . : : .. . - . , -: : ~. : .
.- . . .
.: . ~ .. . ~ . : ~ .
~3~ 3~.~
-(CH2-)2-N-(CH2-)2-N-(CH2-)2--(CH2-)2-lN-(cH2-)2-~N-(cH2-)2-N-(cH2-) R13 X~ R3 X~
-~CH2-)2-N~-(CH2-)2-N~-~CH2-)2-R4 ~ /R4 -(CH2-)2-N N-(CH2-)2-X~ \ ~/ X~ , R \ ~
-(CH2-)2-N~ N-(CX2-)2-X~ \--J , R3 and R5 together with the N atom may for~ a group corresponding to one of the following formulae ,: j.
-R ~ ~ ~ X~, -N ~ O X~
-N N-R4 X~, -N ~ \ R4 X~
or the corresponding basic heterocyclic compounds prior to salt formation or quaternisation -N ~ , -N ~ , -N ~ O , -N N-R4 Rl, R2 and R5 together with the N atom may form a group corresponding to one of the following formulae .
.
,.. . . , . ... . ~ : - ...
.. . . . . , ., . ~,.
.. . . .
2~3~32~
-N~ r -N. N~ or -N N-R3, \ R4 --/ R5 X~3 x'3 -N~ N-R5 X~ denotes chloride, bro~ide, iodide, R3504~, benzene sulphonate, toluene sulphonate, methane sulphonate, phosphate, :
O O
- R9-P , R9-P
I ~o~
,i ORl wherein R9 = OH, ORl or Rl, in particular OH, CH30, C2H50, CH3 or C2H5, m = O.l - 2. 5 10 i P = 0.1 - 2. 5 and n = 1 - 4.
The following meanings are particularly preferred:
R H, ~a, CH3, C2Hs, C2H4H, CH2-~CH-CH3 ,~ OH
: H
15 R3 and R4: H, CH3, C2H5, CH2CH20H, -CH
~:: CIH3 ; CH2=CH-CH2, CH2=C-CH2 '~ .
1~ .
Si~89 li :
'~
Y . . , . , ~ . ~ . ~
S,"i'': ~. ~ . ;.` ' , ' , ':: ' :' ,: ' ., ' '. . ~: ` : , . , r-~ 2 0 3 1 3 ~, ~
.
R3 or R4 additionally -CH2-CH2-, -(CH2)4-~ -(CH2)6 ~ CH2 CH 2 ' OH
-cH2-cH=cH-cH2- .
R3 may in addition correspond to formula Ia, R5 CH3, C2Hs, CH2CH2H~
R2 - ~CH2-) 2-, - (CH2-) 3-' - (CH2) 6--(CH2-)2-N-[(cH2-)2-N-]l 3(CH2-)2-R R
/----\N
-(CH2-)2-N-(CH2-)2-~ -(CH2)2-N~, -(CH2-)2 -(CH2-)3-1-(CH2-)3 or the corresponding salt type or quaternised groups R3 and R5 together with the N atom may denote a group corresponding to one of the following formulae:
- ~ 0 , -N ~ N-CH3 or the corresponding quaternised groups, X~ denotes chloride, bromide, iodide, R1504~, toluene sulphonate or methane sulphonate, m = 0.2 - 2.5 n = l or 2 and j.
p - O.l - 2.2.
The ~ollowing meanings are particularly preferred:
20 R: H, Na or CH3, Rl H .
R3, R4 and R5: H, CH3, CH2CH20H, C2Hs, . , :- .; . -- - ~ - , . .
., 2Q~2~
R4 or R3 also -CH2-CH-CH2-, -(CH2)6-OH
R3 may also denote a group of the formula Ia, R2 _(C~2-)3-X~: chloride, CH3S04~ or bromide, 5 n = l, m = 0.2 - 2.0 and p = 0.1 - 1.9.
The invention further relates to a process for the prep-aration of a polysaccharide by the reaction of esters having the structure IV:
O
I / ~(CH2)n-C-O l/Z Me~r s . tIV,~
[ (C3~2~n~~C~O-R8~s o with an amine having the structure V:
HN- R2 _ ~ (V) Rl R5 wherein 15 r stands for a number from O to 2.5, s stands for a number from 2.9 to O.05 and r + s stands for a number from 0.05 to 3.0, and RB denotes Cl-l2 alkyl, Cs-6 cycloalkyl, C6-l2 aryl, C7-l2 aralkyl or ~-hydroxyalkyl and wherein the other substituents have the meanings indicated in Claim l.
j.
Formation of the polysaccharide derivatives according to the invention taXes place with removal of the group R80H
optionally in t~ie presence of H~ and/or OH~ ions.
- ~ ',', : `
`' ` ~ ` `
~ ~3~.3 -~articularly preferred polysaccharides are characterised in that R denotes H, Na or CH3, Rl denotes hydrogen, R2 denoteS (CH2)3~
R3, R4 and R5 denote CH3, CH2CH20H, C2Hs or H, : X~ denotes chloride, CH3S04~ or bromide, n = 1, r = 0.1 - 1.9, 10 s = 0.2 - 2.0 and S stands for a glucose or pentose unit.
In a particularly preferred embodiment, the monosaccharide unit S is linked to a substituted cellulose unit.
Another particularly preferred embodiment is characterised 15 in that the polysaccharide is present as a salt II and in that B corresponds to the following formula:
-(CH2)n-Co-NRl-R2-N9-R X~
wherein n, Rl, R2, R3, R4, R5 and Xe have the meanings indicated in Claim 1.
20 Salts II are preferably prepared by the reaction of poly-saccharide derivatives corresponding to ~ormula (I) with compounds corresponding to formula (VI) (R10)UX VI
wherein 25 R10 = R4 with the exception of the rest Ia or .~ . . , .... . : , .
~ 2~3~32~
X denotes a substituent forming an anion Xa commonly found in polysaccharide chemistry u = l or 2.
Esters of carboxymethyl cellulose have already been reacted with amines accordinq to VS-PS 3 904 600. Both the esterification of carboxymethyl cellulose and aminolysis of the ester, however, were carried out by ~ery expensive and complicated methods in solution. A product having the following structural element Cell-C~2CO-N~ ~ COO-C~2CH2-NEt2-~Cl was obtained from aminolysis with 2-diethylamino-p-amino benzoate. This group is unsuitable for the use of basic and cationic polysaccharide derivatives mentioned in the present invention since it is very bulky and contains a readily saponifiable ester group so that splitting off of the group HO-CH2CX2-Net2.HCl may already take place during synthesis of the compound in competition with aminolysis of the cellulose ether; further, during storage and in use in aqueous solution, the basic amino group may be split off, the activity of the polysaccharide derivative may fall and undesirable physiological effects may be produced.
Suitable polysaccharide esters for the preparation of the polysaccharides according to the invention include those ha~inq the structure II as described, for example, in DPS
957 938, EP 104 567 and J. App. Polym. Sci. 32 (6~ 5657-9 (1986) and especially those prepared according to DE P 38 42 947Ø Starting materials for such esters are: Polysaccharides~
including polyglycosanes such as cellulose, various '~ ' ' ' ~ ` .
2 ~ 3 ~ derivatives of cellulose such as methyl cellulose and mixed cellulose ethers such as methyl-hydroxyethyl celluloses, carboxymethyl cellulose and their various salts with sodium, potassium, calcium or ammonium ions, especially ~uaternary ammonium ions: cellulose sulphate with various counterions, e.g. of sodium, potassium, calcium, ammonium or quaternary ammonium groups; starches, dextrins, and glycogen; polyfructosanes such as inulin and graminine; polymannosanes and polygalactosanes; and mixed polysaccharides such as hemicelluloses as well as poly-xylosanes and polyarabinosanes.
Cellulose and its derivatives and starch and dextrins are preferred starting materials, the following being partic-ularly preferred: cellulose, methyl cellulose, ethylcellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose and salts and starches thereof.
Suitable amines for the preparation of the polysaccharide derivatives according to the invention are those having the general structure V. When R3 2nd/or R5 stand for H, the products obtained a~ter the reaction with IV may be insoluble in water and cap2ble of swelling in water as in the case of the structure I in which R = Ia, which indicates cross-linking. When R3 and R5 in formula V are not H, the products obtained are generally soluble in water and in some c2ses also soluble in alcohols.
The solubility of the amino- or zmmonium-polysaccharides according to the invention in alcohols or water depends both on the starting material, on the amine (see above), on the degree of substitution, on the alkylating agent and on the degree of ~uaternisation and may be adjusted according to re~uirement. Thus, for example, bis-primary diamines give rise to cross-linked, insoluble products, primary~
tertiary diamines give rise to soluble products and bifunctional alkylating agents give rise to insoluble polysaccharide derivatives.
~ 5289 16 . .. : -~3~
In some cases, ~uaternised derivatives also containing carboxyl end groups may form insoluble products, especially after prolonged drying, presu~ably due to a form of "inner"
salt formation. They may, however, readily be brought into by means of small quantities of bases.
The following are examples of suitable amines corresponding to formula V:
H2N-(CH2)2-N H2N-(CH2)3-N \ H2N-(CH2)6-N \
HN-(CH2)2-N(C~3)2l HN-(CH2)31.N(CH3)2 . 15 CH3 CH3 H2N-(CH2)2-N ~ N-CH3/ H2N-(CH2)3-/--\ CH2CH2oH
H2N-(CH2)3-N O , H2N(CH2)2-N-CH3 H2l~-(cH2)2-[NH-(cH2)2~l-s-NH2~ H2N-(cH2)3N(cH2cH2oH)2 i HN-(CH3)31~(C2H5)2~ H2N-(CH2)2-0-(CH2)2-N(CH3)2, 1 25C2~s ~ ~
H2N-(cH2)3-N~NH~ H2N-(CH2)2-1~ ~N-(CH2)2-N(CH3)2l H2 N - ( CH2 ) 3 -N ~ N- ( CH 2 ~ 2 -N ~0 , H2 N- ( CH 2 ~ 2 N~3 ICH3 CIH3 ~CH3 H2N-CH2-CH-N(CH3)2~ H2N-CH2-CH-O-CH-CH2-N(CH3)2, H2N-(cH2)3-N~ I H2N-(CH2)3-N~cH2cH20cH3)2 OH ~ N
HN-(CH2)3-N(CH2-cH-cH3)2l H2N-(CH2)6-C2H5 \.=.
1~ 5289 17 ,:
....
~3 ~ ~2~
~=~N N - N
HN ~ ~ H2N ~
/=~N N
H2N-(CH2)3-N ¦ I H2N-(CH2)3 N
\ ~ N
The following, for example, are preferred:
H2N-(CH2)2N(C~3)2 , H2N-(CH2)3-N(CH3)2 H2N(C~2)6-J~(CH3)2 , H2N-(cH2)3N(cx2c~2oH)2 ~
H2N(CH2)3~N(C2Hs)2 , H2N-(CH2~3-N N-CH3 , 15 N2N-(C1~2)2-N ~O, H~N-(C}~2~21N~N}~ , H2N-(CX2)2-N\ ' H2N-(CH2)3-N \
X2N-(CH2)2-NH-(C~2)2-~H2 The following are examples of suitable compounds (R10~ux of formula VI: HCl, HBr, CH3S03H, H3P03, H3P04 . CH3PO(OH)2, ~ .
CH3 ~ S03H, ~-S03H
as well 2S methyl chloride, ethyl chloride, propyl chloride, butyl chloride, chloroethanol, chloropropanol, epichlorohydrin, l-chloropropane diol-(2,3), chlorobutanol, 1-chloro-2-methoxy ethane, 1-chloropropanol-2, benzyl chloride, (meth)allyl chloride, methyl bromide, methyl iodide, methyl methane sulphonate, methyl benzene sulphonate, methyl toluene sulphonate, trimethyl phosphate, methyl-o,o-dimethyl phosophonate, benzylmethane sulphonate, allyl tosylate and benzyl mesylate; further, 1,2-dichloroethane, 1,4-dibromobutane, 1,6-dibromohexane, epichlorohydrin, 1,4'-dichlorobutene-2 and 1,6-ditosyl-hexane, l,6-dimesyl-hexane, ~,~'-dibromodiethyl ether and 3 2 ~
, B,~'-dichlorodiethyl ether.
The following, for example, are preerred: methyl chloride, chloroethanol, dimethyl sulphate, methyl mesylate, methyl tosylate, (meth)allyl chloride, benzyl chloride, 1,6-dibromohexane, epichlorohydrin and 1,4-dichlorobutene-2.
The reaction may be carried out in an excess of the amine used as reactant or in a dispersing agent. Examples of suitable dispersing agents include hydrocarbons, halogenated hydrocarbons, ethers, alcohols and carboxylic acid amides.
The following are specific examples: cyclohexane, heptane, isooctane, benzene, toluene, xylene, chlorobenzene, di-chlorobenzene, methylene chloride, chloroform, diethyl ether, diisopropyl ether, dibutyl ether, dioxane, benzo-dioxane, anisol, dimethoxybenzene, ethylene glycol dimethyl ether, isopropanol, isobutanol, methanol, tert.-butanol, isoamyl alcohol, dimethyl formamide, dimethyl acetamide, ~-methyl pyrrolidone, N-methylcaprolactam. ~hese solvents may be used both for the amination reaction and for the alkylating reaction.
The reactions of the carbalkoxy esters of polysaccharides with amines to form amino amides and their alkylation to form cationic polysaccharides should not be carried out on completely dry polysaccharide derivatives as this frequently results in a very slow and insufficient and therefore not accurately reproducible reaction and substitution. The polysaccharides generally contain a few percentages of water so that the addition of water is not necessary in all cases but if the water content is low or unknown it is advisable to add water to the reaction mixture. Ihe amount added may be from 1 to 200% by weight, preferably from 2 to 170~ by weight, more preferably from 3 to 150% by weight, most preferably from 4 to 120% by weight, based on the quantity of polysaccharide put into ~ 5289 19 .
:, . , . :
.
. ' .
2 ~
the process. The amount of water added is not very critical but should not be sufficient to cause unduly strong swelling or even solution of the polysaccharide as this would render control of the reaction and working up more 5 difficult.
The reaction is carried out at temperatures from 0 to 160~C, preferably at 10 to 140~C, more preferably at 15 to 125'C and most preferably at 20 to llO-C. Acids or alkalis may be added 25 catalysts in quantities of from 0.01 to 5%
by weight, based on the cellulose derivative. The following are examples of suitable catalysts: HCl, H2SO4, H3P03, NaOH, XOH, LioH~ Ca(OH)2 and Ng(OH)2.
The molar ratio of the polysaccharide esters to the amines V or to the compounds VI is from 1:0.1 to l:loa~ preferably from 1:0.2 to 1:50, most preferably from 1:0-5 to 1:10 although molar ratios outside the range of 1:10 may safely be used.
~i The reaction time is generally from one hour to ~0 hours, preferably from 2 to 24 hours, most preferably from 3 to 20 hours.
I
The products are worked up by known methods of separation and washing with solvents to remove the hydroxyl compound R8OH which has been split off and excess amine or excess (R10)UX. With suitable choice of solvents, hydroxyl compounds R8OH, amine and alkylating agent, these compounds may be recovered from the reaction solutions by distillation and reused.
The new functional polysaccharides are also zwitter ionic compounds in which, when r > 0 and/or R8 , H or Me, the ionic qroup VII
O
-(CH2)n-c-o~ (VII) t.~ 5289 20 ,~
: .
,, , ~ .. .. . .
- . :
. . ~, .
~ 2~3~ 3~
and the cationic group VIII
-(CH2)n-C-N-R2-~ -R4 (VIII) R R
are present side by side in the s2me molecule. The anionic or cationic character predominates according to which of the two gr~ups has a greater DS.
The water-soluble cationic po]ysaccharides according to the invention are suitab]e for use as additives in hygienic and cosmetic cleansing and skin care products, as auxiliary agents for the manufacture of paper and for the treatment of textile fibres 15 to impro~e the handle thereof.
The water-so]uble cationic polysaccharides can also be used as aggregating agents.
Aggregation is understood to refer to flocculation, coagu]ation and precipitation.
Flocculating agents are processing auxiliaries which allow solid/liquid separation processes to be carried out in an economically efficient manner. With their aid it is 20 possible to improve considerably the rate of sedimentation of solids which are suspended in water and are frequently in colloidal form. Effective flocculating agents bring about almost complete flocculation of the suspended particles, thusresulting in substantial minimisation of the residual solids contents of the liquid phase. The use of flocculating agents also increases the solids content of the solid 25 phase, thus allowing mechanical dewatering of the sedimented slurries to be carried out in a technically and economically advanlageous manner.
Among flocculating agents a distinction must be made between primary flocculating agents and flocculation auxiliaries. Primary flocculating agents are chemical compounds which form precipitates which are poorly soluble in water. These 30 include the Fe, Al and Ca salts widely used in practice. When such compounds are added the charge of the particles in the suspension, which ha~e for the most part been stabilised by negali~le surface charges, is subsequently neutralised, as a result of wllich the electric double layer of the particles is destroyed and rapid coagulation occurs. As the h~drol~sis of Ihe inorganic compounds progresses water-satura~ed ~. - , . . . . . .
,:
., . ~ . , - . .. ,: .
2~3~
voluminous flocs a~e forrned ~ hich entrap the substances contained in Ihe water and cause them to precipita~e. Factors which have a disadvantageous effect on nocculalion using inexpensi~e inorganic metal salts are the dependence on temperalure of the fJocculation process, the requirement of a narrow pH range, the relatively low rate of sedimentation of the flocs and the formation of large volumes of slurry.
Floccu]ation auxi]iaries are cationic, anionic or neutral water-soluble polymers of high molecular weight, which do not display these disadvantages. Here as well, as a result of ionic and dipolar interactions between the polymers and the suspended particles, coagulation of the colloidal particles initially occurs. Where the molecular weights are sufficiently high the macromolecules are capable of linking several deslabilised particles to fomm rapidly sedimenting shear-resistant macroflocs.
Flocculation auxiliaAes are widely used industrially for water-conditioning and waste water treatment in the petroleum, paper, coal and ore industries as well as in some branches of the chemical industry.
The cationic polysaccharides produced according to the in~ention can advantageously be used in quantities of 0.01 - O.S~o by weight. They can be tailored for use in all fields of application according to their degree of cationisation and their molecular ~eight.
In many fields concemed with the production and storage of liquid and semi-solidproducts microorganisms present a problem as a result of their ability to multiply and their metabolism. Thus no methods are at present available for the removal of already fommed mycotoxins whule at the same time preser~ing the quality of the food concerned (H. K. Frank, SchAftenreihe des Bundes fur Lebensmit~elrecht und Lebensmittelkunde, Edition 76, 1974). The water-insoluble cationic polysaccharides produced according to the in~ention are used for the production of highly acti~e filter mateAals. For the abo~ementioned reasons these are in greatdemand in the pharmaceutical industry and the be~erage industry.
The mode of operation of filter beds is based mainly on - the mechanical screening effect, - the penetratioll effect and - the adsorplion effect.
:..
- ~ i 2Q3~3~
As a result of the mechanical screening effect coarse particles of sediment are retained on the surface of the bed. They do not penetrate into the pores. Finer particles of sediment penetrate more deeply into the bed, become entrapped in the net of material and gradually block the pores (penetration effect). Main]y as a result of the e]ectrical charges prevailing between the particles of sediment and the raw materials those sedimented substances which have penetrated into the bed areadsorbed onto the surfaces of the pores (adsorption effect). These effects are dependent on the material properties of the raw materials (kieselguhr, cellulose, cotton). The capacity of a filter bed is defined by its clarification efficiency. This is determined by the inleraction of screening, penetration and adsorption effects.
In bacterial filtration conventional filter beds disp]ay inadequate clarification efficiency due to a lack of adsorbing power.
Test filters in which a portion of the raw material cellulose was replaced by the cationic polysaccharides according to the invention were more highly effective against pyrogenic and endotoxic bacteria in bacterial filtration than fibre filters or filter beds filled with aluminium oxide.
- , ~ . . .
.
;
-~ Example 1 120 g (0.5 mol) of a sodium carboxymethyl cellulose having a DS of 1 was reacted with 76 g (0.6 mol) of dimethyl sulphate in 300 ml of a mixture of 10% water and 90~ iso-propanol at 25'C for two hours and at 70'C for two hours.
The reaction product was then suction filtered, washed with isopropanol and dried in a vacuum at 50 C. 141 g of a water insoluble cellulose ether showing a strong ester band at 1755 cm~l and a weak carboxylate band at 1610 cm~l in the IR spectrum were obtained. Fsterification thus proceeded to an extent of 78~.
ExamPle 2 30 g of the product from Example 1 and 21 g of 3-N,N-dimethylamino--propylamine are stirred in 100 ml of toluene at lOO C for 5 hours. After the solution has been decanted, repeatedly washed out with isopropanol and dried under vacuum at 50'C, 22 g of a water soluble amino cellulose having a nitrogen content of 6.7 are obtained. This corresponds to about 90% conversion of the ester into aminoamide and a DS of 0.7 on the amino function and 0.2 to 0.3 on the carboxylate function. The IR spectrum has a broad, strong carbonamide band at 1670 cm~l.
Fxam~le 3 ; 120 g (0.5 mol) of a carboxymethyl cellulose have a DS of 1.0 and a moisture content of 8.3% are suspended in chloroform and boiled under reflux with 76 g (0.6 mol) of dimethyl sulphate for two hours. After suction filtration, 1 repeated washing with chloroform and drying in air, 142 g of a cellulose derivative which has carboxylate bands and carboxylic ester bands (1757 and 1610 cm~l) in the IR
spectrum and is insoluble in water are obtained. The degree of esterification is 50% (IR analysis).
:.
f~5289 24 i L
:1 ' ' " : ..
Example 4 62~3 ~ 3~
71 g of the cellulose derivative from Example 3 and 51 g (0.5 mol) of 1-amino-3-(dimethylamino)-propane are stirred s up in toluene at 95'C for 8 hours. After suction filtration, washing with toluene and repeated washing with isopropanol followed by drying in a vacuum at 105'C, 53 g of pulverulent aminoamide cellulose are obtained. The product has a nitrogen content of 3.7~, corresponding to a DS of about 0.4 on the aminoamide group, and it shows amide and carboxylate band in the IR spectrum.
Example 5 . I' 278 g ~about 1 mol) of a freshly prepared sodium carboxy-methyl cellulose (DS 1, moisture about 15%) are reacted with an approximately 12 to 13 molar excess of methyl chloride at 90'C and 25 bar for 15 hours. The reaction mixture obtained is cooled, depressurised, washed with 70 methanol and dried in a vacuum at 50-C.
233 g of water insoluble esterified carboxymethyl cellulose having a strong ester band at 1755 cm~l and a weak carboxylate ~and at 1610 cm~l in the IR spectrum are obtained. Conversion of the sodium carboxylate to the ester amounts to 82~.
Exam~le 6 80 g of esterified carboxymethyl cellulose from Example 5 are sucpended in 200 ml of toluene and 106 g of 3-N,N-dimethylamino propylamine and stirred at 60 C for 9 hours.
Ester aminolysis has proceeded by about 90~ at the end of that time and is completed after a further 6 hours at ~5'C~
After suction filtration, repeated washing with toluene and drying at 50'C in a vacuum, 86 g of pulverulent, water soluble amino cellulose having a nitroqen content of 8.1%
and a DS of about 0.8 on the amino function are obtained.
l~ ~289 25 .. . . . :
.. . . : ..
. .
:~
Exam~le 7 100 g of the product from ~xample 6 are suspended in 300 ml or toluene and 100 g of dimethyl sulphate and stirred at 50'C for 12 hours. After suction filtration, washing with toluene and drying at 50'C in a vacuum, 110 g of a water soluble cationic cellulose derivative having a nitrogen content of 5.5% and a sulphur content of 6.2% are obtained. The DS with respect to the ammonium group is about 0.8.
Exam~les 8 to 17 i' General method of procedure:
Carboxymethyl celluloses having a total DS expressed as DSg and an ester DS expressed as DSest in which the unesterified part is present as sodium salt are suspended in isopropanol or toluene. The amine selected for the reaction is added and the reaction mixture is stirred at 90 to 95'C for 10 hours, suction filtered, freed from excess amine by washing with toluene or isopropanol and dried in a vacuum at 50~C. The nitrogen content of the amino-amido celluloses obtained is determined by elementary analysis. IR analysis in each case shows amide, ester and carboxylate bands, the strengths of which vary according to the DS.
The individual data and results are shown in Table 1 below.
~ 52~9 26 .
~ $ ~ _ 2 ~
~1 ~ I ~ + I +
~ ~ _ _ t, ~o + + + , + + + , I +
U~, c JJ ~n 0 ~ D 0 0 0 Z ~ 0 ~ ~ ,/ o ~ 0 Q~ ~ 0 0 o~ o ~q _I ~ ~ ~ o H ~ ~D 0 ~D H N 0 ~
, i' .;
,, &
O
~-~1 ~1 _I O _I O _I O _1 0 _I O _~ O ~1 0 0 0 0 0 :~ O O O O O O O O O O O O O 11~ 0 U~ ~,q o ~Q O
( 7 ~ ~ ~ ~ ~ ~ P~- O 1~1 0 ~ O
~3 1': 0 ~ O ~ O ~1 10'1 It~ W O 'q N ~ N Et Ll~ ~S N
~:1 ~ N a N a ~ a ~ a t: a) o o o o o o~ o o o o N O O 11~ ) O ~ N 11~ N
01 N ~
.
U~ N O Ul ~ ~ r-l o ~ 0 11~
~ ~ U7 0 0 U~ 1~ 0 0 U) U~
a o o ,~ o o ,~ o o o i~ O O N O O ~O O O N
U~
a o o ,~ o o ~1 . o o o _~
Q) _, Q O 0 1~ 0 -1 N 1`7 ~ U`) U~
E-~ a:
WW ~289 27 :' ~' ` `-. - ~, ` , .
` Leaend to Table 1 2 0 3 ~
CMC = carboxymethyl cellulose derivative DAPA - 3-N,N-dimethylaminopropylamine PEXA - pentaethylenehexamine DETA = diethylenetria~ine AEP = aminoethylpiperazine ATA ~ 3-aminot;-iazole + = soluble (+) = partly dissolved or strongly swelled - 5 insoluble Examples 18 ~o 24 General method of procedure:
Aminocarbonamide celluloses from Examples 9, 10, 11, 12, 13 and 16 are suspended. An equal quantity of chloroethanol is added in each case and the reaction mixture iæ stirred at 70-C for 15 hours, thoroughly washed several times with toluene Dnd drled in D V2CUU= at SO'C ~see TDble 2).
: ' ~!W 5 2 8 9 28 r . -J~ 2~3~ 3~
o d~ N ~ ~1 Il --I O ~
t,) N ~ tl~ ~ I~ O
rl C~
u~
C
:Z
~1 ~ ~ ~ 1` ~ O
-~ ~ ~ o u~
j. ~
O U~ O ~ O OO ~D O ~ O O O O
O ~1 0~ rtO ~I N ~ I O ~ O _I
t~ ~ ~ N
a) C) Q~ U a) c) Q) ~ C~ O ~ O a~ o ~ o C) o ~ o G) O
Q C ~ N ~ N :~ N :~ N :~ N ~ t~
~( O O O O O O O
u~ E~+ E~+ E~+ E-l+ E-~+ E~+ E~+
,~ ~
C ~ U~ O O O O O O
o5~3 1` t`
:
' U~ ~ O U~
C~ O O ~1 0 0 O O N O O ~ N
V~
a o O ~1 0 0 ,. ..
:
o Z
_I o O ~ 0~ C~ ~ O O _/ --I N N ~ (~ O
1;~ ~ ~; ~ ~ ~ N ~I N
E~ _ 528q . ` , ~. `
. ` . ` . ~ : .
. . ...
` .
2~3~ 3?~
The results of Experiments 17 to 23 are listed in Table 2.
The high degrees of substitution calculated from the N- and Cl-contents are due to the starting materials, the esterified carboxymethyl celluloses.
Exam~les 25 to 31 General method of procedure:
Aminocarbonamide celluloses from Examples 9, 10, 13 and 14 are suspended and reacted with various alkylating agents at 50-C for 10 hours with stirring. After the reaction mixture has been washed with the dispersing agent used to remove excess alkylating agent, the quaternised celluloses are dried in a vacuum at 50'C.
:.
Further in~ormation and results are given in Table 3.
.
1~ 5289 30 - , , : :
- .. ~ . - ..
: ~ . ,.. . - .. .
.. , ,.... .: :
,. .. ~; - ,- . :
. , , .,;, . ~ . - ~ .:
::
2 ~ 9 ,, ~ ~
.~ ~ + + + + ~ , , , ~ _ _ ~o U~
I~
~n o~P ~ r c~
P:
~ ,I r o o~o r ~D
~) Z _l ~ ~ ~ ~D In ~n _ 0~ ~u~
o . ,~ r~ I
~ U~
_IS :~~: XO ~o ~)o Xo :~:o mu~
.~-~ a ~~ ~ a n ~ u~ m u~ a ~3 ~0 ~0 Q, ~ O
o o o o ~: o P. R. oP' ~ o~ ~
t;~ r J o O O U~ 0 ~: a)a) 5'1 ~ ~ H + H + a) u~
Q) S
~ _I O ~ O O O O O O O O ,1 0 _I ~ O
0-~1 O O O O U~ O ~ O U~ O ~D O CD O O r~
:1 3 E~ ~ H ~ H ~ H ~ H ~ E-~
:~
~J
O O O O O O O L~
~q . ~ ~
J~ ~ ~ ~ ~,~ X
Q~ ~ S
U~ ~ h O O
~,~ O O O ~ a . O O O ~ ~ ~D ~ ~ ~ ~S
~ G~ D ~S
a o o o ,~ N I
,~
.,~
~ ~ ll ll ll ll Q ~ O ô~ c r~ ô cr ô o~ r~ o ~ mr E~ h ~ ~ m a l~W 5289 31 ' '- ., - : .
2~3:~3~
ExamPle of Practical application 1 Method of flocculating test 0.2% solutions of the flocculating agents to be tested are prepared.
7.5 g or SPS China Clay used as filler are weighed in each case into a 500 ml graduated cylinder. The volume in the cylinder is then made up to 500 ml by the addition of pure water or water which has been adjusted to a particular concentration of flocculating agent by the addition of the appropriate quantity of one of the above mentioned solutions of flocculating agents. The contents of the cylinder are then vigorously shaken and flocculation is observed. After the cylinder has been left to stand for 5 minutes, the height of flocculation ~ml) is determined and the cloudiness of the zone of water above the filler is assessed visually.
A hydroxyethyl cellulose quaternised with l-chloro-2-hydroxy-3-trimethyl discloced in DOS 1 593 657, having a DS
of 0.4, is used as comparison product.
(see Table 4) l~ 5289 32 .
.
3 "~ ~3~2~
U~
a o +
~ U~ o U~ ~ ~ ~D
a o o o U~
. I o ~ In o ~1 o ~ El . o u~ ~ In i O ~
'. :i o U~ . o o o U~
-~ O O~ I~ i~ I`
0~O e ~ ~ ~
-~1 . U~ O
S O O~
o~ ~ o o ,~ . o I o I o O ~ ~ ~
U~
. ~
JJ C
o a O G~
' ~ Q~
U C
o ~ u~ 8 ~ ~ ~ 3 ~ ~ o ~ ,~ o o ~ o ~ o ~ ~
C ~ J~ o o 1 C-~
_~ Ll ~ r~
:~ O) ~
Q) t~ ~ S ~ S ~ ~
~ o ~ 8 ~ ~ ~ ~
~ ,, o ~ o~ o ~, ~ ., ~ ., ~ ,, E~ ~ P~ O ~: O ~: O :~
W\~l ~28q 33 ,- - ` - . .. . .. . . .... . . ... .
: . :,.,. , . - . , ~, , : . - ~ . : . . .
- - ~ ` . :; , : .: - : i - :~ :
~ ~ 3 ~ t~
Table 4 shows that the derivatised cellulose derivatives according to the invention produce significantly more rapid sedimentation of china clay than the commercial product, Polymer IR 125. The superiority of the new cellulose derivatives prevails even when the amount of active substance contained therein (Example 19, DS 0.25) is less than in the comparison substance. When the DS rises to 0.6, the improved effect is very mar~ed. It is surprisingly found that the basic product from Example 9 which is not quaternised also serves as excellent flocculating agent.
.
Claims (7)
1. Polysaccharides containing recurrent units I or a salt II thereof I II
wherein S denotes a monosaccharide unit, A denotes a group of the formula Ic attached to the monosaccharide unit S by an oxygen atom Ic B denotes a group of the formula Ib attached to the monosaccharide group S by an oxygen atom Ib p denotes a number from 0 to 2.9, m denotes a number from 0.05 to 2.9, m + p denotes a number from 0.05 to 3.0, R denotes C1-12 alkyl, C5-6 cycloalkyl, C6-12 aryl, C7-12 aralkyl, .beta.-hydroxyalkyl and/or 1/Z Me wherein Me is a cation and Z is the valency of the cation, R1 denotes H or C1-4 alkyl, R2 denotes an alkylene group which may be interrupted by at least one O or N atom or by an olefinic double bond, R3 denotes H, an alkyl group which is optionally substituted by an OH or by an olefinic group and may be interrupted by at least one heteroatom, an aralkyl group or the group of a polysaccharide of the formula Ia wherein the indices and substituents have the meanings indicated above, (Ia) R4 is equivalent or different of R3 and is linked with the same nitrogen atom as R3 and cannot have at the same time with R3 the meaning C2-C8-alkylene or Ia R5 denotes H or an alkyl, aralkyl or aryl group and/or R3 and R5 together with their common nitrogen atom denote a ring optionally containing another heteroatom, R1 and R5 together with R2 denote a ring and n denotes an integer with a value from 1 to 6.
wherein S denotes a monosaccharide unit, A denotes a group of the formula Ic attached to the monosaccharide unit S by an oxygen atom Ic B denotes a group of the formula Ib attached to the monosaccharide group S by an oxygen atom Ib p denotes a number from 0 to 2.9, m denotes a number from 0.05 to 2.9, m + p denotes a number from 0.05 to 3.0, R denotes C1-12 alkyl, C5-6 cycloalkyl, C6-12 aryl, C7-12 aralkyl, .beta.-hydroxyalkyl and/or 1/Z Me wherein Me is a cation and Z is the valency of the cation, R1 denotes H or C1-4 alkyl, R2 denotes an alkylene group which may be interrupted by at least one O or N atom or by an olefinic double bond, R3 denotes H, an alkyl group which is optionally substituted by an OH or by an olefinic group and may be interrupted by at least one heteroatom, an aralkyl group or the group of a polysaccharide of the formula Ia wherein the indices and substituents have the meanings indicated above, (Ia) R4 is equivalent or different of R3 and is linked with the same nitrogen atom as R3 and cannot have at the same time with R3 the meaning C2-C8-alkylene or Ia R5 denotes H or an alkyl, aralkyl or aryl group and/or R3 and R5 together with their common nitrogen atom denote a ring optionally containing another heteroatom, R1 and R5 together with R2 denote a ring and n denotes an integer with a value from 1 to 6.
2. Polysaccharides according to Claim 1, characterised in that R2 stands for a group III
-[R6-y-]qR7- III
wherein R6 and R7, which may be identical or different, denote an alkylene group with 2 to 6 C atoms optionally interrupted by an O atom, Y denotes O or a group of one of the following formulae:
, , , or wherein R3 has the meaning indicated above and R4 has the meaning of R3 except that R4 is not Ia, q denotes an integer with a value from 1 to 5 and Xe denotes an anion.
-[R6-y-]qR7- III
wherein R6 and R7, which may be identical or different, denote an alkylene group with 2 to 6 C atoms optionally interrupted by an O atom, Y denotes O or a group of one of the following formulae:
, , , or wherein R3 has the meaning indicated above and R4 has the meaning of R3 except that R4 is not Ia, q denotes an integer with a value from 1 to 5 and Xe denotes an anion.
3. Polysaccharides according to at least one of the preceding Claims, characterised in that R denotes H, Na or CH3, R1 denotes hydrogen, R2 denotes -(CH2-)3-, R3, R4 and R5 denote CH3, CH2CH2OH or H, R3 may in addition denote Ia, Xe denotes chloride, CH3SO4? or bromide, n = 1, p = 0.1 to 1.9, m = 0.2 to 2.0 and S denotes a glucose or pentose unit.
4. Polysaccharides according to at least one of the preceding Claims, characterised in that the monosaccharide units S are linked to a cellulose unit.
5. Polysaccharides according to Claim 1, characterised in that they are present in a form of a salt II and in that corresponds to the following formula X.THETA.
X.THETA.
wherein n, R1, R2, R3, R4, R5 and X.THETA., p and m have the meanings given in Claim 1 and wherein L has one of the meanings indicated for R2.
X.THETA.
wherein n, R1, R2, R3, R4, R5 and X.THETA., p and m have the meanings given in Claim 1 and wherein L has one of the meanings indicated for R2.
6. Process for the preparation of polysaccharides by the reaction of esters having the following structure IV
(IV) with an amine of the structure V
(V) wherein r denotes a number from 0 to 2.5, s denotes a number from 2.9 to 0.05 and r + s denotes a number from 0.05 to 3.0, R8 denotes C1-12 alkyl, C5-6 cycloalkyl, C6-12 aryl, C7-12 aralkyl or .beta.-hydroxyalkyl and the other substituents have the meanings indicated in Claim 1.
(IV) with an amine of the structure V
(V) wherein r denotes a number from 0 to 2.5, s denotes a number from 2.9 to 0.05 and r + s denotes a number from 0.05 to 3.0, R8 denotes C1-12 alkyl, C5-6 cycloalkyl, C6-12 aryl, C7-12 aralkyl or .beta.-hydroxyalkyl and the other substituents have the meanings indicated in Claim 1.
7. Use of the polysaccharide derivatives according to at least one of the preceding Claims as flocculation auxiliaries.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3939951A DE3939951A1 (en) | 1989-12-02 | 1989-12-02 | BASIC POLYSACCHARID |
| DEP3939951.6 | 1989-12-02 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2031329A1 true CA2031329A1 (en) | 1991-06-03 |
Family
ID=6394710
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002031329A Abandoned CA2031329A1 (en) | 1989-12-02 | 1990-12-03 | Basic polysaccharides |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0431387B1 (en) |
| CA (1) | CA2031329A1 (en) |
| DE (2) | DE3939951A1 (en) |
| FI (1) | FI905889A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11566167B2 (en) | 2019-12-18 | 2023-01-31 | King Fahd University Of Petroleum And Minerals | Gemini surfactants containing an unsaturated linker for clay swelling inhibition |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1150351A (en) * | 1955-08-18 | 1958-01-10 | Henkel & Cie Gmbh | Process for the preparation of amides of carboxylic acids of cellulose ethers |
| FR1493421A (en) * | 1965-08-03 | 1967-09-01 | Scholten Chemische Fab | Quaternary ammonium derivatives of polysaccharides, and their use |
| DE3302456A1 (en) * | 1983-01-26 | 1984-07-26 | Henkel KGaA, 4000 Düsseldorf | Cationic cellulose derivatives, their preparation and use in cosmetic compositions |
| DE3820031A1 (en) * | 1988-06-13 | 1989-12-14 | Goldschmidt Ag Th | DERIVATIVES CONTAINING NITROGEN OF CARBOXYMETHYLCELLULOSE, THEIR PRODUCTION AND THEIR USE IN COSMETIC PREPARATIONS |
-
1989
- 1989-12-02 DE DE3939951A patent/DE3939951A1/en not_active Withdrawn
-
1990
- 1990-11-20 DE DE59009626T patent/DE59009626D1/en not_active Expired - Fee Related
- 1990-11-20 EP EP90122136A patent/EP0431387B1/en not_active Expired - Lifetime
- 1990-11-29 FI FI905889A patent/FI905889A/en not_active Application Discontinuation
- 1990-12-03 CA CA002031329A patent/CA2031329A1/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| FI905889A (en) | 1991-06-03 |
| FI905889A0 (en) | 1990-11-29 |
| DE3939951A1 (en) | 1991-06-06 |
| EP0431387B1 (en) | 1995-09-06 |
| DE59009626D1 (en) | 1995-10-12 |
| EP0431387A1 (en) | 1991-06-12 |
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