• 专利附录
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    • 专利摘要:
    Disclosed are novel polymeric quaternary ammonium salts containing specific di-tertiary amino substituted cationic recurring units. Said salts are useful as dyeing and finishing agents, especially for dyeing textile materials, such as polyacrylonitrile fiber materials, as dispersing agents and emulsifiers, as antistatic, antimicrobial and flocculating agents and as precipitants.
    公开号:SU890980A3
    申请号:SU782629400
    申请日:1978-06-07
    公开日:1981-12-15
    发明作者:Хаазе Ярослав；Хорн Ульрих；Берендт Ханс-Ульрих
    申请人:Циба-Гейги Аг (Фирма)；
    IPC主号:
    专利说明:

    where R, R / 2, Rn and R are the same or different radicals selected from the group including alkyl cycloalkyl or alkynyl with not more than 20 carbon atoms, aryl, aralkyl, and RQ, and / or R and R with the nitrogen atom to which they are attached, form a substituted heterocyclic ring with 5 or b members in the ring; A, and A are the same or different and equal to -CpHijo-, where n is an integer from 1 to 12, for n equal to 1 the bond is not through a nitrogen atom or an oxygen atom, or is phenylene and phenylene substituted by halogen, hydroxyl , alkyl, haloalkyl, alkoxy. All equals - ,,, where n is an integer 2 - 12, X - means the bivalent residue of the formulas -NHCONH-) -NHCOX CONH-; -CONH-, -OCONH -; - COO-COXi CO-; NH-Xif-TIH-CiO where X is a single bond, alkylene, alkenylene, arylene, diaminoalkene flax, diaminoarylene, dioxyalkylene, polyoxyalkylene or dioxyarylene; Chl-diaminoalkylene, dioxyalkylene, ylioxyalkylene or dithioalkylene} X is arylene and X 4 is alkylene or arylene, and compounds containing the formula 5-g-G are used as dihalide compounds, where A is a bivalent residue selected from the group including -CHf O -Rs-ochi -; K: Hi (ORb) pOCHQ -; -CHiiCOCHQ-; -CHQ CHOHCHQ; -; -eng - ciHaeng-, -eng exgde where RC means linear or branched, unsubstituted or substituted alkylene with 2-12 carbon atoms of the genus; R is equal to, (CH) where m is an integer from 2 to 12 and p is an integer from 2 to 15, and Xj is a halogen. Compared with the known ammonium polymeric salts, to obtain the proposed polymeric fourth ammonium salts, in which turning cationic structural diagrams are shown in the following forums 1 and 11, other diains and (or dihalides or other combinations of diamines and dihalides are used). The use of new raw materials has improved the properties of the products obtained. The proposed method allows to obtain polymeric quaternary ammonium salts containing cationic structural units of the formula 1 Y А -1 AI-X-AZ-1 AZ The ingredients of the ingredients listed above are, if necessary, combined with cationic structural units according to the formula, g TR4 in which A means, where n is 2 - 12, AZ is -C, "Na", -; -CH O-Rj-OCHo -; -CH, j (OR6) pOCHn-; -CHQ COCHj -; -CH / CHONSN -; ciH, -, dHz-; -CHN, C1H | - where Rg means a linear or branched halogen-substituted alkyl with 2 to 12 carbon atoms , RJ, equals -CH -CH / j, -cjHz-dH - CJH,) or - (CH | 2) -. The residues R, RI., Rj and R4 in the composition of cationic structural units of polymer quaternary ammonium salts according to formulas 1 and 11 can be straight chain or branched alkyl residues with 1 to 20 carbon atoms, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, hexyl, octyl, isooctyl, tert-octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, or eicosyl. Hbi is preferred alkyl residues with 1-10, especially 1-4, carbon atoms, for example methyl and ethyl.
    Substituted alkyl residues are, for example, oxyalkyl, cyanoalkyl, alkoxyalkyl, alkylthioalkyl, alkylcarbonylalkyl, alkylsulfonylalkyl, arylcarbonylalkyl and arylsulfonylalkyl, where aryl is an aromatic hydrocarbon with one, two or three, or phenylmethyl, or phenylmethyl, or arylcarbonylalkyl, aryl is an aromatic hydrocarbon with one, two or three, or phenylmethyl, or arylcarbonylalkyl, and arylcarboxylic. alkylcarboxylic acids of carbschkoxy- and dicarbgcoxyalkyl-J amidalkylcarboxylic acids, N- or N, N-substituted by lower alkyl (or aryl, for example, phenyl, in the case of a cycloalkyl residue, cyclopentyl and cyclohexyl, which may be substituted, are preferably used.
    Apenyl residues may contain 2-20 carbon atoms. Preferred alkenyl residues with 2 to 10, or, especially, with 2 to 4 carbon atoms. Ashkenyl residues corresponding to the alkyl radicals mentioned are suitable. Substituents named for alkyl residues can usually also be used for alkenyl residues.
    Aryl and aralkyl residues are preferably phenyl and benzyl, which under certain conditions are replaced by hydroxyl, cyano, halogen (fluorine, chlorine, bromine, iodine), carboxyl, alkyl, oxyalkyl, cyanoalkyl, alkoxy and alkylthio, and the lower alkyl or the same alkoxyalkyl radicals are preferred by alkoxyalkyl, carbalkoxy and dicarbalkoxyalkyl, and in the alkyl or alkoxy parts are present in each individual case, look at the circumstances, preferably 1-4 carbon atoms: alkylcarboxylic acid, where alkyl l contains 1-4 carbon atoms amidalkyl carboxylic acid, N or N, N-substituted lower alkyl
    Further, both substituents at each nitrogen can form together with the nitrogen atom to which they are attached a substituted heterocyclic ring with 5 or 6 members in the ring. Examples of such heterocyclic rings are the piperidimorpholine, timorpholine, pyrrolidine or imidazolium ring.
    A and A, which can have the same value or differ from each other, are, for example, the alkyl-alkali groups of FORMULA -Cf, where n is an integer of 1 - 12, preferably 1-6. For a value of 1, i.e. for grouping, communication with member X, forming a bridge, must be via a different atom than nitrogen and oxygen, especially a carbon atom is suitable for communication. The sum of the values of n for both groups A- and A0 should be at least 3. As already
    indicated for the formula —C „H1 -, alkylene residues may be branched and linear, with the latter being preferred. A and A may be an aromatic bridging member, especially under certain conditions, in the form of substituted phenyl. As a possible substituent for this aromatic bridging member, we mean, as a rule, lower Gshil, lower Q, hydroxy or gals-alkyl, with 1-4 carbon atoms, hydroxyl or halogen, especially chlorine or bromine.
    A may be branched, however, linear alkylene with 2 to 12
    s carbon atoms, for example - (SNP) ,, - (CHa) 5-; - (CH) - or - (CH), 2.
    Residue A is holed and can be represented by the formula (j, where m is 2 to 12,
    0 in particular,,, Ct ,,, C (jHjQ-,
    ia.24
    These groups can be motorized or branched. In addition, AZ is a grouping
    5 -CH, O-R -OCHi -, where RJ means linear or branched agitates with 2-12 carbon atoms. In particular, these groups are meant here, which can be substituted with halogen, preferably chlorine or bromine. Further, Hell can be -CHij (ORf,) рОСНО -, where R means -CH-CHi- or - (SI5) 4- and
    CH-i
    five
    has a value of 2 - 15, or groups-CHA-COCH (1-, CH 2 SNONSN 2-,
    40
    (besides p, p-isomers, other isomers may also be used) or
    50
    The bridge member X corresponds to the divalent residue of the formula -NHCONH-; -NHCOX CONH-; -CONH-; -OCONH-; -Cox |
    000r
    -OCl-Xj-J-O-j -Od-NH-Xif-TflH-C where X / is a direct bond, alkylene of 1 to 12 carbon atoms. Along with methylene (-CHij -), the groups already mentioned for Ai are used.
    which can be linear or branched. If X., means alkenylene, it can be expressed by the formulas, -CH CH-CH CH-, then YNZ CH, s, C-CH (. Aromatic,
     the bridge member (X - Allen) can be represented by the formulas
    ,, f; j, i; 5, - {,
    n
    Dioxy arylene residue may
    -O ,, - ,, 0sootvetstvat formula
    5 and especially the formula 0
    About and the phenyl core can be substituted by halogen, especially chlorine or bromine, alkyl, especially with 1-4 carbon atoms, one or more substituents may be present in the phenyl core. Also apply the residue of the formula
    ipch
    moreover, the aromatic rings may be substituted with halogen, especially chlorine or bromine, C1 L
    and / or alkoxy. Alkyl and alkoxy residues generally have 1 to 15 carbon atoms and are, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl amyl or isoamyl, methoxy, ethoxy, propoxy, butoxy or pentoxy and the corresponding branched isomers . Aromatic rings may contain one or more substituents. X is a diaminoalkyl, for example, of the formula -HH-CH gtHH-, or especially -NH (CHr) NH-, where ha is an integer of 2-12. Alkylene groups already mentioned in the definition of A are preferred. A diaminoarylenic residue may be a residue having an NH 4.f-V formula of T especially.
    NH and NH phenyl formula
    The nucleus can be substituted with halogen, especially chlorine or bromine, alkyl, especially with 1–5 carbon atoms, or alkoxy, especially with 1–4 carbon atoms, or one or more substituents may be present in the phenyl core. A dioxyl or polyoxyshylene residue which is used as a bridge member X can be expressed by the formulas -ORrO or (OR (5) pO-, where RJ, R and p have the indicated meanings. Examples of the dioxyalkylene residue are -0 (CH ( ) O- or -O (CHij) 4O- and for the polyoxyalkylene residue -OCHaCHiiOCHfi .CHQ.0- - () 150-,
    -SNSNGOSNSNGOSN,
    Sn.
    or - Soya (CH / i) HCH i 5
    where R-, Kg are hydrogen or methyl. The bridging member Xij within the -COX.jCO group is a diaminoskyl, dioxyalkyl or polyoxyalkylene and may have the same values as those previously defined for the same groupings for X. If Xj is dithioalkylene, this residue may be represented predominantly by -SRjS-, where RJ has the given value. Xj means Allen and can be phenylene, and the phenyl ring may contain as a substituent ggshogen or lower alkyl, for example with 1 to 4 carbon atoms.
    Hf means hyskylene, especially straight chain alkylene with 1-12, preferably with 2-6 carbon atoms. If X is Allen, it has, in particular, the meanings given for Xj.
    The quaternary ammonium salts according to the invention contain cationic structural units according to formula 1, in a particular case combined with cationic structural units of formula 11, for example
    R, i Ai-X-AjА, t: kc
    to.
     -A.-N-AZI 1 I
    R
    R4
    These units may be located in a molecule, for example, in alternating order and / or forming blocks. Preferred are polymeric quaternary ammonium salts, which only contain repeating structural units of formula 1, where
    tionic structural units correspond to the formula
    I / PM / T
    -K A1-X7-Ar-1G (VI /;
    A., L
    ten
    where X is -CONH-; -OCONH- or -COO-, and A, Arj, -) 0 R-f- and. Have the cited values. Particularly suitable representatives with repeating structural units according to formula VII are those in which the cationic structural units correspond to the formula
    CCHH-A -H - (iHj
    iH,
    SNgtvjj)
    where Ay is alkylene of 1-4 carbon atoms or phenylene, and A is alkylene of 2 - b carbon atoms or phenylene. ,
    Another group of successfully applicable polymer quaternary ammonium salts with repeating structural units according to formula 1 contains cationic structural units of the formula
    OO
    - od-MK- (c1ng) -ln-sil
    where m is 2-12,
    a a
    one
      have given
    Rgf og value.
    In addition, polymeric quaternary ammonium salts, in which the structural repeating units correspond to the formula
    -K-dmjHgmjl HCJONRCimiHimi-N --L -, - 1BT 17
    where R-j, R.j and the same or different and mean alkyl, oxyalkyl, alkoxyalkyl, alkylthioalkyl and cyanoalkyl with 1 to 4 carbon atoms, cyclopentyl, cyclohexyl,
    CHjCOOCHj -, A -NHCiOCJJlz or phenyl, or benzyl, substituted by hydroxyl, cyano, fluorine, chlorine, bromine, alkyl, oxyalkyl, cyanoalkyl, alkoxy and alkylthio with 1 to 2 carbon atoms, alkoxyalkyl, carbalkoxyalkyl, and alkoxyalkyl alkyl groups, alkoxyalkyl, alkoxyalkyl, alkoxyalkyl, alkoxyalkyl, alkoxyalkyl, alkoxy, and alkyloxy. 2 carbon atoms in the alkyl part and the alkoxy part,, - (CHrj), amidalkyl carboxylic acid with 1 or 2 carbon atoms in the hypochond part and N-substituted by lower terminal, or R c, and and / or R -, (j VI together with the nitrogen atom to which they are attached form a heterocyclic ring by the formulas
    -ABOUT . -Oh rd
    U
    AT means -CLH ,, -; -CHnCOCHo-; 4Q -CH, iCHOHCH ,,
    -dHe
    dHa-,
    ,
    SigciHz
    where m is 2 to 12 and m-) is 2-6. Such compounds with repeated
    structural units according to formula X, in which R ;,, R-tfe and R-, 7 are the same or different, and alkyl contains 1-4 carbon atoms, or R, Rfe Ri7 together with the carbon atom to which they are attached , form a piperidine ring, and AT, m, ni have the given values, and their cationic structural units are represented by the formula
    CHj
    I-
    - St Ngt YakoyynSgtsNgt
    Uhj
    where A-, and m have the indicated meanings; or formula
    dH,
    -A, CH,
    2 enz
    Y (eNg)., BNS01№ (Y1g)
     HH,
    UTO
    CH,
    Especially preferred are polymeric quaternary ammonium salts with repeating structural units of formula 1, in which R, R, Rg
    and R,
    same or different
    between each other, they mean methyl or ethyl, or R and RQ and / or RJ and R together with the nitrogen atom to which they are bound form a piperidine ring, A and A, mean - (СНз) n where n means the number 1 - 3, and the sum of the numbers p for A and Ad is at least 3, or is phenylene, Aj means -CmHi -, -CH / iO (CHQ) f, jOCHi, -CHqCOCn, -,
    -CHfj -CHOHCH CjHt
    - SNG dH-t-
    O-SNG-L-O - {
    en
    g
    where, n 2-6iH means bivalent, forming a bridge member, expressed by the formulas -NHCONH-, -NHCOX-, -CONH-, -CONH-, -COXg CO-,
    ABOUT II N
    odxjcio
    or
    where X, is saturated bond, alkylene with 1-6 carbon atoms, phenylene, diamino-nitkylene with 1-6 carbon atoms or diaminophenylene, the phenylene ring, under certain conditions, containing methyl as a substituent; X | j means -NH (CHQ) n. NH-, Xj - phenylene and X alkylene with 2 to 6 carbon atoms or phenylene.
    As an anion for the polymeric quaternary ammonium salts of this invention, all conventional inorganic or organic anions that do not form with cations of sparingly soluble complexes are applicable, since ammonium salts should preferably be soluble in water, for example, anions of mineral acids or low molecular weight organic acids. Suitable, for example, halogen anions, such as, Br® and especially CS®, methyl sulfate (CHjSO®), ethyl sulfate () f toluene sulfonate, nitrate
    0 and sulfate
    The polymeric quaternary ammonium salts of this invention may have a molecular weight of 1000-100,000, preferably
    5,000 to 50,000, and especially 40,000 to 20,000. They are soluble in water.
    To obtain the ammonium salts, the diamine (a mixture of diamines) is subjected to an exchange reaction with the corresponding
    0 by a dihalogen compound (binding mixture) in a molar ratio of from about 1: 2 to 2: 1, preferably in an equimolar ratio.
    So, connect with khzimis repeat
    5 structural units according to the formula 1 and according to the formula 11 are obtained by an exchange reaction carried out between the diamine according to the formula
    Biv 5
    N-AI-X-AZ-N
    (mj
    if necessary mixed with diamine
    45
    R, and.
    K - N I
    R4 h
    AO, A and X
    L -1
    where R, R 5y R-x ,,
    have the meanings
    and dihalide, or with a mixture of dihalides of the formula
    five
    Kg-Xj, XV where X5 is halogen, especially chlorine or bromine, and AO has the indicated value.
    You can also use if necessary dihalide formula
    0
    XVI
    X5-X in a mixture with a dihalide of the formula XU11
    Xg- 5 where Ah ,, Aj, A, X and Hu have the indicated meanings. For ammonium salts containing repeating structural units of the formula IV, for example, a diamine of the formula 1 can be used; G-Ai-NH (ociX5) o COBH-Ar - N ЕIL 10KIZ where Rg,, R ,, R ,,, A , A, Xj and q are given values. For ammonium salts, the repeating units of the formula Y contain suitable amines of the formula. B ".- R: N - d O Ci ONHd of ggNgti - N R14B XX and dihalogens of the formula Xj-A4-Xj, XX where A, X5 and t have the given values. For the ammonium salt with repeating structural units in the Y1 and Y11 formulas, diamines of the formulas N-Ai-ciO-Xg-CiO-AE Y can be used (x AI-X.7 -AZ - N where RU, R, jj, R , R ,, A, Ajj, X and X have the given meanings. Ammonium salts with repeating structural units can be obtained by the formula, for example, by the exchange reaction of the diamine of the formula XXXY U (fH3 K - AS - CJO - JJH-Ab - N ix where A5 and A have the indicated values, with 4,4-bis- (chloromethyl) -diphenyl. To obtain ammonium salts with repeating structural units of the formula IX, it is possible to obtain by the exchange of diamine the form where N, A, A, Rg, ,, R and X are given values, perform exchange reactions with a dihaloide of the formula Xg - AZ 5 de Xg and A. have the indicated values. Get ammonium salts on the board X can be achieved by reacting a benzene diamine of the formula .am. ° .5. With a dihalide of the formula Xj-- X5XXU11 where% R-fb 5 and have the given meanings. Especially if R,, R, R are the same or different, and alkyl contains 1-4 carbon atoms, preferably methyl, or 15 and / or (, to form together with the nitrogen to which they are attached, a piperidine ring, while to A has a predetermined value, and m is 2-6, preferably 3. The starting compounds (diamines dihalides) to obtain the invention lists a polymeric quaternary ammonium salts are generally known compounds readily available by chemical synthesis. The dihalides according to the formula XXU11 represent, for example, the following compounds: Br (CHP) Br; Br (CHfl) oBr; Br (CHii) (, CfCH2 COCH2Ce; dHgcii Aromatic halides can be easily obtained, for example, by chloromethylation. Diamines with a bridge-forming carbs1-amide member (HNCONH-) and a bridge-forming alkylene member belonging to tertiary nitrogen atoms can be obtained by exchange reaction between carbamide and alkylenediamine, which contains a tertiary nitrogen atom. This reaction takes place at an elevated temperature and is accompanied by the elimination of ammonia. Another possibility of obtaining a diamine is to conduct an exchange reaction between the corresponding el, OK dihalide compound and secondary amine. Diamine with a bridge member, a derivative
    from dicarboxylic acid, can be obtained, for example, from dichloride or dialkylamino acid and alkylenediamine. Ammonium salts can be prepared in inert solvents with respect to the reactants. An example of such solvents is acetone or cyclic ethers, such as dioxa or tetrahydrofuran. Lower alcohols are preferable, especially methanol. The reaction temperature is usually determined by the boiling point of the solvent used and can be selected from about 20 to 150 ° C, preferably 50%. Under certain conditions, it is possible to work with water or a water-alcohol mixture as a solvent, and in certain cases, without solvent at all.
    Chlorine ion is preferred as the anion. The introduction of other anions can be carried out by exposing the ammonium salt containing chlorine ions (reaction product) to an ion exchange resin having other, necessary anions.
    The polymeric quaternary ammonium salts prepared according to the invention are usually soluble in water and upon receipt fall out, as a rule, in quantitative yield, as a mixture of compounds that do not differ in purity. For this reason, the reducible molecular weights can be considered only as their average values.
    The quaternary ammonium polymers of the invention can be used for a wide variety of applications. Liquid media containing such salts (baths) may be neutral, acidic or alkaline. Preferably, they are used in a dyeing method or applying a printed pattern to textile materials from natural fibers or from synthetic fibers. In these cases, the C1MMONIUM polymer quaternary salts are used as an aid in dyeing, especially as a means of leveling the color shades. Among textile materials based on fibers of natural origin, cellulose-containing materials, especially cotton, then wool and natural silk are primarily meant. Synthetic fiber textiles include, for example, high molecular weight polyesters, for example polyethylene terephthalate or polycyclohexanedimethylene terephthalate; polyamides obtained, in particular, from polyhexamethylene diamine adipate, polycaprolactam, or polyamine undecanoic acid; polyolefins or polyacrylonitriles, in addition, from polyurethanes, polyvinyl chloride, polyvinyl acetate, as well as from 2,5-diacetate and cellulose triacetate. Said synthetic fibers can also be used in blends with each other or in blends with fibers of natural origin, such as fibers.
    0 cellulose and / or wool. Said fibrous materials may be in any suitable for processing by continuous method, textile forms, such as, for example, cable
    5 (cable), combed batt (combed tape), threads, yarn, fabrics, knitted goods, knitwear, knitted fabric, non-woven products.
    Solutions for dyeing can be aqueous solutions, as such or with the addition of organic substances, or dispersions, as well as thickeners, inks in a concentrated form. Such agents, along with dye and
    5 of the polymeric quaternary ammonium salt of the invention may also contain other additives, for example acids, salts, urea, and other auxiliary substances such as oxyalkylation products of fatty amines, fatty alcohols, alkylphenols, fatty acids and fatty acid amides.
    Polsh "black Quaternary salts
    Ammonium 5 is particularly suitable as a moderator when dyeing polyacrylonitrile fiber materials with cationic dyes, as well as crushing anion-modified polyester fiber materials. Said salts exhibit significant efficacy in retarding and leveling floral shades for uniform coloring. Suitable for dyeing
    5, cationic dyes can fall into the most diverse categories of m. Suitable dyes are, for example, diphenylmethane, triphenylmethane, rhodamine, and
    0 azo- or anthraquinone containing onium groups. Further, it should be noted thiazine, oxazine, methine and azomethine dyes.
    Dyeing polyacrylonitrile
    5 textile materials can be produced in the usual manner, according to which the textile material or fabrics to be dyed is placed in an aqueous dye bath heated to about 50 ° C containing a cationic dye, a polymeric quaternary ammonium salt, salt additions such as sodium acetate or sodium sulfate, also acids - acetic or formic.
    five
    Then the temperature of the dyebath is boiled to about a temperature of about 30 minutes and then the dyebath is held at this temperature until exhaustion. A basic dye can also be added to the dye bath, but only additionally, for example, after the bath temperature reaches about 60 ° C. The textile material or fabric to be dyed is pretreated at 40-100 ° C in a bath containing common salts and acids, including the ammonium polymer salt, but E is also lack of dye. A dye is then added and dyed at 100 ° C. By polyacrylonitrile fibrous materials are meant to be taje such, in the manufacture of which other vinyl compounds are used in addition to acrylonitrile, for example vinyl chloride, vinyl acetate, vinylidene chloride, vinyl esanide and acrylic acid alkyl ester. However, the proportion of these vinyl compounds should not exceed 20% based on the weight of the material. Amounts of the polymeric quaternary ammonium salt suitable for use in these dyeing methods are usually 0.01-5% by weight, especially 0.05-2 or 0.1-1% by weight, based on the weight of fibrous material.
    Dyed polyacrylonitrile fiber textiles obtained with an auxiliary agent in the form of a polymeric quaternary ammonium salt are characterized by very good color uniformity along with a good yield of dye per fiber.
    Other uses for polymeric quaternary ammonium salts are: an aid in dyeing polyacrylonitrile fibers; dispersants, for example for pigments; emulsifiers; a cationic fixative to improve the authenticity of color when wetted on textiles made from cellulose fiber or paper, colored with direct and dispersive dyes; antistatic agents, especially for textiles containing synthetic organic fibers; antimicrobial agents; coagulating agents, for example, for wastewater treatment or precipitating agents that form flocculent sediments, for example for coagulating colloidal, aqueous dispersions, for example a dye.
    The compounds are preferably used as a moderator in dyeing polyacrylonitrile fiber textile materials.
    as well as when fixing dyes, except for SARS, KciK, antistatic and anti-mycotic drugs, coagulants and flocculants.
    Example 1. Equimolecular 5 quantities (each 0.2 mol) given in Table. 1 dihalides and 1, 3-BIS- (3-dimethylamino-propyl) -carbamide (obtained from 1-dimethylamino-3-aminopropane and urea
    during the removal of ammonia), heated in 200 ml of methanol for 24 hours under reflux. As the reaction progresses, the viscosity of the reaction mixture gradually increases. Upon completion of the reaction, the reaction mixture is cooled and
    5, the solvent is removed in vacuo. Obtained with a quantitative yield (100% of theory) the products of the exchange reaction; are given in table. 1, with repeating structural units. The products of the exchange reaction are soluble in water. Stable aqueous solutions contain, for example, 20% by weight of an exchange reaction product. Intrinsic viscosity (dl / g) is measured
    5 in methanol at a concentration of 0.5% (g / volume) at.
    Example 2. Example 1 is repeated. At the same time receive the results given in table. 2
    l The resulting water-soluble polymers contain repeating units of the formula XXXU111,
    Example 3. An exchange reaction is carried out between equimolecular amounts (each 0.2 mol) listed in Table. 3. diamines with 4,4-bis- (chloromethyl) -diphenyl in accordance with example 1. Obtain with a quantitative yield (100% of theory) the products of an exchange reaction with repeating structural units, given in Table. 3. Example 4. Equimolecular amounts (each 0.2 mol) are given in Table. 4 dihalides
    5-and 1,2-bis- (dimethylaminopropyloxyamide) (obtained from oxalic acid diethyl ester and 1-dimethylamino-3-aminopropane) are subjected to an exchange reaction, as indicated in Example 1. It is obtained with a quantitative OUTPUT (100% of theory) exchange products with repeating structural units are given in Table. four.
    Example 5. Equimolecular amounts (each of 0.2 mol) listed in Table. 5 dihalogenides and 1,6-Bis- (3-dimethylaminopropyl) -adipamide (obtained from adipic acid diethyl ester and 1-dimethylamino-3-aminopropane) are subjected to an exchange reaction as indicated in Example I. The preparation is obtained in a quantitative yield (100%
    5 from theory) exchange reaction products
    with repeated structural units listed in Table. five.
    Example 6. An exchange reaction between equimolecular amounts (0.2 mol each) of 1,6-dibromhexane and diamine is carried out according to the formula
    NHUONH
    - gwg
    The intrinsic viscosity (H) was 0.18 dl / g. The content of ionogenic bound bromine was 97% of theory.
    Example 7 An exchange reaction between equimolecular amounts (each 0.2 mol) listed in Table 2 is carried out. b diamines and 4,4-Bis- (chloromethyl) -diphenyl, as indicated in Example 1. An exchange reaction product with repeating structural units shown in Table 1 is obtained in quantitative yield (100% of theory). 6
    Example 8. An exchange reaction between a mixture of dihalide and diamine (equivalent amounts of dihalide and diamine) is carried out as indicated in Example 1a. With a quantitative yield (100% of theory), decomposition products having the composition shown in Table 2 are obtained. 7
    Used dihalogenides or diamines:
    And sesn / 1 .- (11с1Нг- / У- СНгС11
    Al BrCHiiCHlCHiCHiiCHQ CHiBr
    In (CHj) .iNCH, CHiiN (CH4) i
    HF (CHo,) lNCH (iCH2.CHl, N (CHb) l
    5 BR (CH3) aNCHaCH.2CH, iCH2CHriCH, 2N (CH3) 2 V. (CH), j NC3H NHCONHCaH N (CH5) 2
    Bj (CH3), LNCjH NHCOCONfiCaH6N (CH3), j.
    Example 9. 5 g of polyacrylonitrile tissue (Orlon 42, a foreign company, DuPont) is treated in a dyeing machine in 200 ml of dye-containing solution containing 0.01 g of exchange product with repetitive structural units according to the formula XXX111 as an auxiliary substance, the reaction which was brought to pH 4 by the addition of 80% acetic acid. The treatment is carried out for 20 minutes at 98 s with a constant movement of the fabric.
    Then the dye solution is added in the form of a mixture of the following composition: 0.007 g of the dye according to the formula
    to to
    n
    0,007 dye formula
    -NH
    SNSPNN ..J-N
    Tn
    moreover, the temperature is maintained at 98 ° C.
    Continue dyeing at this temperature for 60 minutes to gradually cool the dyebath until, then the fabric is rinsed and dried.
    as a result of the addition of the auxiliary agent (retarder), slowed down, accompanied by the alignment of color shades, the formation of the color tone of the fiber is achieved. Routine cooling after pre-plating was not necessary. The resulting gray color is characterized by excellent evenness and good wet strength.
    Equally good results are obtained when using as an adjuvant 0.1 g of any of the remaining reaction products of examples 1-8,
    Example 10. Polyester fiber fabric is impregnated into baths containing 15 g / l of polymeric quaternary ammonium salt with repeating structural units according to formula (101), then squeezed to 110% gain and dried for 30 minutes at. The fabric is then subjected to a 30-second heat-setting at 170 °. The surface resistance of the fabric is measured. With this, the following results are obtained, Ohm: Polyester non-fine-molded 4-10 Polyester treated. 3 ny 1-10 Example 11. In the precipitation tank of the lighting installation, industrial fluxes containing about 100 h, per million mixtures of reactive dyes and acid dyes are mixed with a stream of solution of the excipient of Example 1a so that the concentration of the excipient in the solution is brought to 100 ppm. Spontaneous sedimentation of the dyes occurs, after 30 minutes the separated dye can be separated by filtration, and the remaining wastewater is completely colorless and can be directed to the sewage system. As a rule, there is no need to resort to filtering, since the outgoing waste is collected as a sediment. The precipitated dye settles at the bottom of the tank in about 5-6 hours, after which sedimentary, completely discolored water can be pumped out into the sewer system.
    Thus, the use of the invention will make it possible to obtain broad-spectrum polymeric quaternary ammonium salts with improved performance characteristics.
    1: 0.97 1: 0.94 1: 0.90
    Table,. 2
    1.42 0.83 0.22
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    权利要求:
    Claims (1)
    [1]
    Claim
    A method for producing Polymeric quaternary ammonium salts by polycondensation of di-tertiary diamine with a dihaloid compound / characterized in that, in order to expand the functionality and improve the operational characteristics of polymeric quaternary ammonium salts, a diamine of the formula or a mixture thereof with a diamine of the formula are used as a two-tertiary diamine
    K— A.- N
    The r Bn where, Rfp Rg, and R 4 are identical or different radicals selected from the group consisting of alkyl, cycloalkyl or alkenyl group with a carbon number less than 20, aryl, aralkyl, and Rt and R and / or R 2, and R 4 together with the nitrogen atom to which they are attached form a substituted heterocyclic ring with 5 or 6 members in the ring, 'A 4 and Aodinakova are different or equal to -C P H (] _ And , where η is an integer from 1 to 12 , for η equal to 1, the bond is not through a nitrogen atom or an oxygen atom, or are phenylene and phenylene substituted by halogen, hydroxyl m, alkyl, haloalkyl or alkoxy group, and / is equal to C n ^^ - ,. Hz where an integer of 2 - 12, X - represents a divalent
    Order 11041/89
    VNIIIPI ______
    Branch of PPP Patent,
    the remainder of the formulas rNHCONH-j — NHCOX ^ CONH-k ’, -CONH-; —OCONH 'about Oh
    -oA-X 5
    where X 1. means flax, alkenylene,. f 1Ί11 w h-z νΙΊΓ1 f,} -COO-; ' -COX e CO- /
    -OC-KH-X ^ -KH-CO-, single bond, alkyl 4 arylene, diaminoalkylene, diaminoarylene, dioxyalkylene, polyoxyalkylene or dioxyarylene; ' Xq_ is diaminoalkylene, dioxyalkylene, polyoxyalkylene or dithioalkylene; Xj is arylene and X4 is alkylene or arylene, and as a dihaloid compound, a compound of the formula X 5 - - X F is used , where A 5 is a divalent residue selected from the group consisting of -C ^ Nodt, -, -CHqO-Rj-OCHq -,
    - CH q_ (OR b ) p OCH Q-, -CHjCOCH ^ -, -CHqCHOHCHq-,
    -CHj
    SI
    -in-Oh-oh Oh ‘’ Ό-soi-O->
    where R <; means a linear or branched unsubstituted or substituted by halogen alkylene with 2 to 12 carbon atoms; Rfc is -CHq-CHq-, - - - (CH - 12 and
    15, and X
    -sn ^ - ^ where w is equal to the integer 2 p is equal to the integer 2 is halogen.
    类似技术:
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    SU890980A3|1981-12-15|Method of preparing polymeric quaternary ammonium salts
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    同族专利:
    公开号 | 公开日
    CH638362A|1983-09-30|
    CA1090363A|1980-11-25|
    CH638362B|
    ES471150A1|1979-09-01|
    ZA783331B|1979-06-27|
    FR2399451A1|1979-03-02|
    JPS544999A|1979-01-16|
    US4247476A|1981-01-27|
    PL113058B1|1980-11-29|
    BR7803709A|1979-02-20|
    FR2399451B1|1982-12-10|
    AU3697778A|1979-12-13|
    NL7806242A|1978-12-12|
    DE2824743A1|1978-12-21|
    DK258378A|1978-12-11|
    BE868001A|1978-12-11|
    DD137350A5|1979-08-29|
    GB2000164A|1979-01-04|
    GB2000164B|1982-02-17|
    SE7806722L|1978-12-11|
    PL207517A1|1979-03-12|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    CH717877A|CH638362A|1977-06-10|1977-06-10|
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