JPS59115316A - Water-soluble copolymer, manufacture and use - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel water-soluble copolymers. Tore is the residue 1-86 of general formula (1) with statistical 4 distribution.
9-80% by weight of residues of the general formula (II), 5-90% by weight of residues of the general formula (Ill) 2 IJH2, and optionally 5-90% by weight of residues of the general formula (IV).
) and (or) (V) and (or) (Xu Co-R' residues totaling 0 to 30% by weight.

In general formula (1) to M), R1 represents O, -0, preferably C4 or C2 alkyl group, R2 and R5
represents a hydrogen atom or a methyl group independently of each other, R3 and R' independently represent a hydrogen atom, a methyl group, or an ethyl group, or together represent a trimethylene group or a pentamethylene group, Y is a direct bond, Phenylene residue or formula -Co-IJH-0 (0H3).

-CH2- represents a residue, X (l is a proton (H+)
Or indicates a cation.

The invention also relates to the production of this copolymer and its use as an auxiliary agent in textile dyeing plants and as a post-tanning substance.

The cations X1 can in principle be derived from known water-soluble bases, the strength of which is sufficient to neutralize the sulfo- and phosphonic acid groups of the copolymers which can be used according to the invention, but Xo is advantageously meant an alkaline earth or preferably alkaline cation, in particular a cation derived from a sodium or potassium cation, ammonium or a lower aliphatic amine. Cation X
Lower aliphatic amines from which may be derived are primary, secondary or tertiary amines, optionally having an -OH- group 1 [thus substituted a, -C, alkyl group]. with at least one β-hydroxyethyl residue, such as β-
amine ethanol, β-dimethylamino-ethanol,
Bis-(β-hydroxyethyl)-methylamine, tris-(β-hydroxyethyl)-amine, diethyl-β
-hydroxyethylamine, bis-(β-hydroxyethyl)-ethylamine are preferred.

Preferred copolymers according to the invention have a statistical distribution of 1-
10 weight consists of residues represented by general formula (1), 10-7
0 weight consists of a residue of general formula (II), 29-8
0 weight is the general formula (consisting of residues and 0-.20
The weight π consists of residues of the general formulas (IV), (V) and/or (■).

Particularly preferably used vine copolymers have the general formula (II) where Yba-00-NH-C(01'(,)t-(1!
Indicates a residue H,-. ) has the following residues.

Copolymers according to the invention may also have the general formula (1) or ■
) and (■) can naturally contain many different individuals in which the meanings of the symbols Y or R1-R5 are different.

Therefore, for example, A'[BS
- and vinyl sulfonic acid-substrates or ring-closed vinylamide-substrates of the general formula (IV) may contain ring-opened ones or vinylphosphonic acid esters having various alkyl groups R1 of different chain lengths. . It generally contains various substrates of the general formula (11 to IVj and hyuh-).

The production of water-soluble polymers containing sulfonic acid groups introduced into macromolecules has already been described in detail in numerous patents as well as in the specialized literature. For example, the synthesis of copolymers of vinyl sulfonic acid with acrylamide and vinylpyrrolidone is described in J. POI-ymer Sci., 58147 (1957).
) is disclosed in

DE 1.101.760 describes a process for preparing water-soluble copolymers of vinylsulfonic acid and acrylonitrile or methacrylonitrile, optionally in mixtures with other ethylenically unsaturated compounds. There is. Copolymers of vinyl or alkyl sulfonates with acrylamide and vinylamide are described, for example, in German Patent Application No. 2,444,108.

A water-soluble copolymer containing 2-acrylamido-2-methyl-propanesulfonic acid-(s)-, 11, hereinafter abbreviated as ATBS, as a comonomer is described in US Pat.
No. 953.342, No. 5,768,565, No. 3.9
07.927 and 3.926.718 and German Patent Applications Nos. 2,502,012 and 2
．． No. 547.773.

The copolymers according to the invention, insofar as they contain copolymerized comonomers of the general formula (IV) in which R3 and R4 together represent a trimethylene group or a pentamethylene group, can be prepared in a manner known from the prior art, e.g. about 10 as described in U.S. Pat. No. 3,929,741.
It can be prepared in the presence of a suitable polymerization catalyst at a temperature of ~120'O1, preferably from 40 to 80'0. In this case there is no need to neutralize the acidic groups before polymerization, and copolymers according to the invention in which Xo is a proton are immediately obtained.

Under similar conditions, ATBS, sterol- or vinyl sulfonic acid and non-ring-closed N-vinylamide, i.e. with the general formula % (where RA and R4 together represent a trimethylene group or a pentamethylene group) When carrying out the copolymerization of , it is necessary to convert the acidic component into a salt with the cation x0 by addition of a base before the polymerization.

The bases preferably used in this case are the hydroxide of the cation X'' or its salts with weak acids, such as carbonic acid or phosphoric acid, or, in the case of amine bases, the NH1 parent is the free amine.

However, neutralization of acidic components before polymerization is possible and even generally advantageous during copolymerization of ring-closing compounds.

Preferably, therefore, 1 to 86 parts by weight of an ester of the general formula (Ia), Cl1a) :O
9-80 parts by weight of olefinically unsaturated sulfonic acid H2,=C"d-Y-80,H, optionally methacrylic-
and/or 0-50 parts by weight of acrylic acid and/or vinylphosphonic acid in water/alkanol mixture - in which the resulting copolymer is still soluble or miscible with water. Dissolve in organic solvent.

If R3 and R4 together do not represent a tri- or pentamethylene group, and if R31 and R4 together represent a tri- or pentamethylene group, the acidic group is optionally neutralized by addition of a base, and then the general formula (IVa) 3 (In the formula, R3 and I are the same or different and independently represent a hydrogen atom, a methyl group or an ethyl group, or a trimethylene group or a pentamethylene group.) 0 to 50 weight by weight and 5 to 90 parts by weight of acrylamide and/or methacrylamide, the copolymerization is started in a known manner, and 10-20'O
It will be carried out. If the copolymerization is carried out after neutralization, the copolymer according to the invention (wherein X0 represents a proton) can be prepared by adding an equivalent of a sufficiently strong acid, preferably an inorganic acid, to the acidic groups of the copolymer according to known methods. It can be obtained liberated by

Preferred copolymers according to the invention are obtained when: In other words, the general formula (
Ia) 1-10 parts by weight of vinylphosphonic acid ester,
10-70 parts by weight of unsaturated sulfonic acid of general formula (Ila), 29-80 parts of acrylamide and (Sl) methacrylamide and vinylacrylamine and/or vinylphosphonic acid of general formula U/a) and/or ) 20 parts by weight of acrylic and/or methacrylic acid are used.

The polymerization can be carried out as a solution polymerization, as a precipitation polymerization or in reverse emulsion form.

If water or a water/alkanol mixture is used as solvent - a, -a which is miscible with the water removal.

If an alkanol is used and the finished copolymer is soluble in the water/alkanol mixture, the polymerization proceeds under conditions of solution polymerization, resulting in a viscous aqueous or aqueous/alkanolic solution of the copolyi according to the invention, The product can be isolated from this by precipitation by evaporation of the solvent or by mixing this solution with a water-miscible organic solvent, such as methanol, ethanol, acetone, etc.

However, it is preferred to apply the resulting aqueous or aqueous/alkanolic solution immediately, optionally after preparation to the desired γψ solution, to the intended use.

When copolymerization is carried out in an organic solvent that is miscible with water,
Carry out under precipitation polymerization conditions. In this case, the polymer immediately forms as a solid and can be isolated by distilling off the solvent or by taking it off with suction and drying.

Water-miscible organic solvents suitable for carrying out the process according to the invention include, in particular, water-soluble alkanols, namely C,-
a, alkanols, such as methanol, ethanol, propatool, inglobanol, n-18- and iso-butanol, preferably t-butanol.

The water content of the lower alkanol used as a solvent must not exceed 6% by weight.

This is because agglomeration can also occur during polymerization. Preference is given to operating with a water content of 0-6 weight tons.

The amount of solvent that may be used depends to some extent on the type of comonomer used.

Generally, the total monomer is 100 I, and the solvent is 200 to iooo
Use g.

If the polymerization is carried out in the form of an inverse emulsion, the aqueous monomer solution is prepared in a known manner in a water-immiscible organic solvent, such as cyclohexane, doluol, quidyrole, heptane or the h 4+ m point Henzing fraction. 5-8% by weight, preferably 1-4% by weight of known emulsifiers (W2O
emulsification under the addition of (type) and polymerization using conventional radical-forming initiators.

The principles of convertible emulsion polymerization are described in U.S. Pat. No. 3,284,593.
It is known from the specification no. In this process, water-soluble monomers or mixtures thereof are polymerized into a hot strip polymeric copolymer. In this case, firstly, the water-in-oil type water-in-oil type
Addition of emulsifier emulsifies in an organic solvent forming a relevant layer that is immiscible with sewage water and this emulsion is
f [Presence of initiator] Heat. The resulting comonomer is part one! 1 They can be emulsified in water-immiscible organic solvents or used in the form of aqueous solutions containing from 100 to 5 parts by weight of comonomers and from 0 to 95 parts by weight of water. In this case, the composition of the aqueous solution is determined by the solubility of the comonomer in water and the expected polymerization temperature. The ratio of water to monomer layer varies over a wide range and is generally 70:30,50 near zero.

To emulsify the monomer layer into a water-in-oil emulsion in a water-immiscible organic solvent, a water-in-oil emulsifier is added to the mixture in an amount of 1 to 10 parts by weight based on the oil layer. It is preferred to use emulsifiers with relatively low HT.p-%'G-nee,'. As oil phase it is possible in principle to use all inert water-insoluble liquids, ie in principle all hydrophobic organic solvents. Generally, within the scope of the present invention, hydrocarbons with boiling points in the range 120-5500' are used. The hydrocarbons can be saturated, linear or branched paraffinic hydrocarbons, such as those predominantly present in petroleum distillates. In this case, the dough can additionally contain the customary proportions of naphthenic hydrocarbons. However, it is also possible to use aromatic hydrocarbons, such as doluol or pheasant, as well as mixtures of the above-mentioned hydrocarbons, as the oil layer. Preference is given to using a mixture of saturated normal and iso-rough-in hydrocarbons containing up to 20% naphthene by weight.

A detailed description of the process can be found in German Patent No. 1.089.175 and in US Pat. No. 3.284.393 and US Pat. No. 3.624. (It is in the specification of No. 119.

If the polymerization is carried out in the form of an aqueous solution according to the method of so-called gel polymerization, copolymers with a particularly moderate degree of polymerization are obtained. In this case, an aqueous solution of 15 to 60% of the copolymer is thoroughly mixed mechanically using a known suitable catalyst system using the Tromsdorff Norritschew effect (Bto
sFinal Rap, 563.22: Mak
romo'l, 0heno, i, 169 (1947))
Polymerize. Based on the usual model concepts relating to the viscosity and average molecular weight of the polymeric substances from the viscosity of the aqueous solutions of the water-soluble copolymers according to the invention and which can be used according to the invention produced in this way, as well as regarding the products according to the invention. The average molecular weight can be estimated to be 10', considering the comparative value of 1A for polymers produced by conventional methods.

The polymerization reaction is carried out at -20' to +50' O1, preferably from 5 to
It is carried out within a temperature range of 90'0. In this case, it is possible to work under normal pressure and under elevated pressure.

Polymerization is generally carried out in a protective gas atmosphere, preferably under nitrogen.

To induce the polymerization, energetic electromagnetic radiation or conventional chemical polymerization initiators can be applied. For example, organic peroxides, such as benzoyl peroxide,
tert-butyl hydroperoxide, methylethyl-ketone-peroxide, spider-hydroperoxide, azo compounds such as azo-diiso-butyro-nitrile or 2-azo-bis-(2-amidinepropane)-dihydrochloride HN= O(CH,), -N, -N-C(OH,)2-
0-NH12HC1■ Ryo NH2 ParahiK Inorganic peroxide compound, for example (NH,)
2B, 08 2S208 or H20
II) or in combination with redox systems containing as reducing components aliphatic and aromatic sulfinic acids such as penzole sulfinic acid and doluol sulfinic acid or derivatives of these acids - 1 such as sulfinic acids, aldehydes and Mannich adducts from amino-compounds, such as those described in German Patent No. 1.301.56.
It is described in the specification of No. 6. Generally from 0.03 to 2 g of polymerization initiator are used per 100 g of total monomer.

The polymer gel obtained after gel polymerization treatment is heated at 50 to 130°.
The quality properties of the polymer can still be improved by heating for several hours within the temperature range of 0, preferably 70-100'O.

The copolymers according to the invention produced in this way in the form of aqueous gelatin can be dissolved in water and used immediately after mechanical grinding in suitable equipment. However, it can also be obtained in solid form after removal of the water by known drying processes and can be dissolved in water again before its use.

The new copolymers according to the invention can be used as dye factory auxiliaries.
It is particularly advantageously suitable for dyeing cellulose-containing fibrous materials according to the Pazinder cold-dwelling method. By adding the copolymers according to the invention, the dye liquor absorption of the cellulose-containing fiber materials to be dyed is significantly increased. This leads to improved dyeing of even bulky textile flat structures, such as tricot. This results in dyeings with high levelness and excellent product formation.

When using the novel copolymers according to the invention in pigment dyeing plants, highly level and intense dyeings are obtained.

The new copolymers according to the invention, when added to a padding liquid containing disperse dyes, which are used for example for dyeing polyester materials, thereby exhibit outstanding dyeing advantages, independent of their value. Produces even dyeing and gloss.

Furthermore, the copolymers according to the invention with a molecular opening of less than 50,000 are preferably suitable as so-called post-tanning materials, in particular for chlorine leather.

The copolymers according to the invention are also suitable as auxiliaries in secondary and tertiary oil and gas transport in petroleum reserves.

The following example illustrates the preparation of a polymer according to the invention.

All "πli'Ft" is "weight".

The abbreviations used in the examples and anomalies have the following meanings: AM Niacrylamide VTMA: N-vinyl-N-methyl-acetamide VTPY: N-vinylpyrrolidone ATBS: 2-acrylamino-2-methyl-propanesulfonic acid ■A: Pinylacetamide VTFA, Vinylformamide VSS-Na: Sodium vinylsulfonate styrene SS Nistyrene sulfonic acid vps: Vinylphosphonic acid VPE, Vinylphosphonic acid-methyl ester A
S; Acrylic acid MAS: Methacrylic acid I+1JL (emulsion polymerization) ■Arkopal N 100 (oxyethylated n
, nonionic emulsifier based on phenol derivatives)
7.2g and ■5pan80 (≠1 sugar 7/l/-
19.4 g of Tsopar M (about 200-2
4 ' A technical mixture of isoparaffins with a boiling point of 0 ° 0) and the resulting solution is poured into the 11 - reaction vessel.

This vessel is equipped with a stirrer, a thermometer and a nitrogen inlet tube. The monomer solution was then mixed with 97.2 g of acrylamide, AT
It is prepared by dissolving 7 g of BS q and 1.1 g of vinylphosphonic acid monomethyl ester (VPFi) in 105 ml of water. Adjust the monomer value to 8.5 using ammonia (to 25). Add the aqueous monomer solution to the organic layer with a rapid stirrer.

The reaction vessel is evacuated and then filled with nitrogen. A solution of 0.0275 g of ammonium versulfate in 6 ml of water is added to this mixture, thereby starting the polymerization. The reaction lasts 14 hours.

Keep the reaction temperature between 50-400℃. Using commercially available surfactants, a stable emulsion is obtained which can be converted to water in a manner known per se.

The resulting polymer solution has a pH value of 148.9.

T) The acidic groups of the resulting copolymer can be liberated by acidifying the aqueous solution with H2.

Example 2. (Solution Polymerization) 200 ml of water in an 11-capacity polymerization flask equipped with a flat polished, polished container, stirrer, thermometer and gas inlet tube. !
Dissolve 70 g of AIB S in and dilute with ammonia (25 min.). Then 10g of acrylamide and vp
Add z + Og. Adjust the pH-value to 8.5 and N
- Add 10 g of vinyl-N-methyl-acetamide.

The reaction mixture is heated to 60'O while stirring and introducing nitrogen. In addition, 1 g of dibutylamine-HCl solution and 1 jift of ammonium persulfate were added to the aqueous solution.
Join. The reaction lasts approximately 50 minutes. At this time, the temperature was 70
It rises to ゛C. The reaction mixture becomes viscous.

Heat at 80'C for a further 2 hours with stirring. A clear, highly viscous solution is obtained. The K-value is 166.7.

When prepared, the pH value of the viscous polymer solution was adjusted to 7 by adding hydrochloric acid, and then adjusted to 60 and 4.5 with acetic acid, and then immediately used as a padding aid for disperse dye padding composition. A solution is obtained.

Example 3 (Gel Polymerization) Acrylamide 6 was prepared in an 11 volume polymerization flask equipped with a flat polished lid, a stirrer, a thermometer and a gas inlet tube.
0 g, ATBEt 50. ! A monomer solution is prepared by dissolving i' and VPElog in 250 g of water. Dibutylamine-1' (
1 g of Cl-solution and 0.0 g of ammonium persulfate.
Add 1g. Stir at high speed for 3 minutes before introducing nitrogen. The nitrogen introduction is completed and the inlet tube and stirrer are lifted up. Polymerization takes place after 50 minutes of induction. At this time 2
The temperature at 0'O is increased to 7°0°0, converting the solution into a stable gel. The K-value is 218.8.

Example 4 (precipitation polymerization) 4.9.7 g of acrylamide in t-butanol 440, AT in an 11-capacity polymerization flask equipped with a PT stirrer, reflux condenser, thermometer dropping funnel and gas introduction tube.
Dissolve 7.1 g of BS, 7 g of VPE and 3,6/i of MAS.

Heat the solution to 50' with stirring and introduction of nitrogen and add azoisobutyronide I dissolved in DMFSd.
Drop 1 g of Jru. After 50 minutes of rusting, polymerization takes place.

The reaction temperature increases to 68°0 and the polymer precipitates. Heat at 80°0 for a further 2 hours. The copolymer is isolated by suction and drying. However, solvents can also be immediately reduced to seedlings.

The polymer is obtained in the form of a white, light powder, which is well soluble in water and has a value of 115.0.

The following copolymers can also be prepared according to these four processing methods.

Example 5゜(a) A mixed fabric consisting of polyester and rayon stable in a mixing ratio of 70:50 is padded with the following dye liquor with a liquor absorption of 60 per dry weight:
Disperse dye in commercial form 0.0% in 11% water. T, 1350 g of dispersed orange and front side 7 prepared according to example 2
Copolymer 4 of the composition containing solution 15 and 2
Adjust to a value of 5.5 by adding 0% acetic acid.

The padded fabric is dried at a temperature of 130°0 and then thermosolized for 60 seconds at a temperature of 210'O.

The dyeing is then worked up by boiling. An orange dyeing is obtained in the polyester part of the fabric, which has extremely high gloss and flat dyeing properties.

(b) The copolymers according to the invention used in column (a) are prepared as follows: in an 11-volume polymerization flask equipped with a flat polished lid, a stirrer, a thermometer and a gas introduction tube. Al in 200g of water
B510.9' and VPS 20g'r are dissolved and neutralized with ammonia (25 to 25%). Then acrylamide 85
g and VPE 5y. The pH was adjusted to 8.5 and the reaction mixture was then heated to 60°C under stirring and nitrogen introduction.
Heat to. Furthermore, dibutylamine-Hcl was added to the aqueous 10.
-ma 1g and ammonium bursulfuni) 0.
Add 4 g. The reaction lasts approximately 30 minutes. The temperature rises to 70°C.

The reaction mixture becomes viscous. Heat at 80°C for 2 hours with stirring. A clear, highly viscous solution is obtained. K-value is 166
．． It is 7.

The produced viscous polymer solution was diluted to 7 by adding hydrochloric acid.
When adjusted to 30 and then adjusted to 4.5 with acetic acid,
A solution is obtained which is used as a padding aid for dispersion dye-padding removal.

Example: 6゜cotton towel fabric per 11 dye Remazol 410
- padding with a dye liquor containing 4 g of the commercial form of Ichishibu 61, 50 g of sodium sulfate, 20 g of caustic soda solution (in 52,5 tons) and 20 ml of a 4% by weight solution of the L-da copolymer prepared according to Example 5(b). do.

The padded material is pressed to a liquor absorption of 90 and rolled up. The product is retained for 20 hours by gradual rotation of the roll. The dyed material is then soaped, hot-bladed and cold-washed and dried in the usual manner. A very bright yellow dyeing is obtained which has a smooth levelness and a complete dyeing.

In a similar manner to Examples 5 and 6, other copolymers mentioned in Examples 1 to 4 and in the table can also be used for improving the levelness and dyeing integrity of textile dyeing.

Example Z (a) 100 parts of conventionally neutralized and chrome-tanned horsetail leather in 200 parts of water and dry, 5 parts of polymer calculated per substance (front side 8) - this is as per Example 4. After-treatment at 30° C. for 11 hours.

After a short wash #, post-processing? The leather is added in a conventional manner using 4 to 6 parts of a light-fast fatliquoring agent based on sulfonated whale oil, and then dried.

A light-toned leather of excellent light resistance is obtained with a perfectly soft hand and fine scarring.

(b) The copolymer used in column (a) was obtained as follows: (in an 11-volume polymerization flask equipped with a stirrer, reflux condenser, thermometer, dropping funnel and gas introduction tube) Aku IJ/l/amide 52.8 g in t-butanol 440 d
, ATBS 8.59, vpg 7.1 g and styrene sulfonic acid (styrene-8s) 2.1 g. The monomer solution under stirring and introduction of nitrogen is heated to 50 °C and 1 g of azoisobutyronitrile dissolved in DMF5T (il) is added dropwise. After an induction period of 30 minutes, polymerization occurs and the reaction temperature is 68 °C. 0 and the polymer precipitates.Heat for a further 2 hours at 80'O.The copolymer can be isolated by suction and drying.However, the solvent can be immediately distilled off under reduced pressure. It is obtained in the form of a white, light powder, which dissolves well in water and has a value of 45.

Example 8 (a) 4° for 100 chrome-tanned sheepskin leather
Add 200 parts of water. Thereafter, 10 parts (calculated on the dry substance) of the polymer from face 2 prepared according to Example 1 are added to the solution and left to act on the leather at 40 DEG C. for 2 hours. After washing, the treated leather is fatliquored with about 5 parts of a conventional fatliquor and then dried. A fully supple leather with tight, firmly adhering forging marks is obtained.

■ (b) Arkopal N 100 (non-ionic emulsifier based on oxyethylated phenol derivative) 7.2 g and ■5pan13Q (non-ionic emulsifier based on ≠ 4 mer alcohol-stearard) 19.49 ■l5Opar M (approx. 200-2
technical mixture of isoparaffins with a boiling point of 40°0)
and pour the resulting solution into the il-reaction vessel.

This vessel is equipped with a stirrer, a thermometer and a nitrogen inlet tube. The monomer solution was then mixed with 5.4 g of acrylamide and ATBS.
+6.2.9. It is prepared by dissolving 5.4 g of VPS and 81 E of vinylphosphonic acid monomethyl ester (VPE) in water. The pH value of the monomers is adjusted to 8.5 using ammonia (25%).

Add Zimmer's solution to the aqueous organic layer over rapid stirring. The reaction vessel is evacuated and then filled with nitrogen. A solution of 0.0275.9 ammonium persulfur in water is added to this mixture, and the polymerization is initiated. The reaction lasts 11 parts and 2 hours. Reaction temperature 60-40'0
Keep it. Using commercially available surfactants, a stable emulsion is obtained which can be converted to water in a manner known per se. The resulting polymer solution has a pH value of 14.4.

Agent: Hikaru Esaki Preferred Agent: Hikaru Esaki Continuing from page 1 of History Claim of priority @December 24, 1982 ■West Germany (D
E)■P3248031.8 M Author: Juliane Baltzel Frankfurt, Federal Republic of Germany 61 Steinauerstrasse 4 @ Inventor Walter Dursch Konigstein, Federal Republic of Germany 4 In der Praubach 4 0 Inventor: Hanseuerg. Kleinerdois, Romberg 2, Altke 12, Zuchstrasse 11,

Claims (11)

[Claims] (1) Statistical distribution shows 1-86% by weight of residues of general formula (1) 1 and 9-86% of residues of general formula (II).
80% by weight, general formula (Ill) 2, Q=0 NH. 5-90% by weight of residues of the general formula (IV
) and (or) (V) and (or) (vOhayashi0-R4, R2 and R5 independently represent a hydrogen atom or a methyl group, R3 and R4 independently represent a hydrogen atom,
Represents a methyl group or an ethyl group, or together represents a trimethylene group or a pentamethylene group, Y is a direct bond, a phenylene residue or the formula -〇〇-NH-0(CH,) 2-
A water-soluble copolymer consisting of a 0H2- residue, Xo is a proton (H+), and the father is a cation. (2) Based on a statistical distribution, 1-10% by weight of the residue of the general formula (1) is divided into 10-70% by weight of the residue of the general formula (I[
), 29-80% by weight of the residue of general formula (III)
and 0-20 parts by weight of the residue of general formula (IV),
A water-soluble copolymer according to claim 1, comprising (V) and/or (■). (3) Y in the residue of the above general formula (I[) is of the formula -C
o-NE-[E(OH,)2-C! 2. A water-soluble copolymer according to claim 1, comprising a crosslinking member tearyl H. (4) The water-soluble copolymer according to claim 1, wherein Xo is a cation derived from an alkaline earth or alkali cation, ammonium or a lower aliphatic amine. (5) The general formula (
) % formula % ) Ester 1-86 heavy part, general formula (I[a) :O
H,=OH-Y-8o3H, 9-parts by weight of olefinically unsaturated sulfonic acid, in which case methacrylic acid and/or acrylic acid and/or vinylphosphonic acid 0-
50 parts by weight are dissolved in water or in a water/alkanol mixture, in which the resulting copolymer is still soluble, or in an organic solvent that is miscible with water, so that R3 and R4 together are If it does not represent a pentamethylene group, if R3 and R' together represent a tri- or pentamethylene group, the acidic group is optionally neutralized by addition of a base, and then the general formula (IVa) 3 OR2=OHN -COR' (■a) (in the formula, R3 and R' are the same or different and independently represent a hydrogen atom, a methyl group or an ethyl group, or together represent a trimethylene group or a pentamethylene group) 0 to 30 parts by weight and 5 to 90 parts by weight of acrylamide and/or methacrylamide are added, and the copolymerization is started in a known manner, starting from 10 to +20 parts by weight.
% residues of the general formula (1)% by weight, 9-86% by weight of the residues of the general formula flI)
80% by weight, 5-90% by weight of residues of general formula (III) 2 NH7 and optionally general formula (W)
and (or) (V) and (or) (■) -〇4-OH- N-R” (IV) and (or) CuO-R
4 and R5 independently represent a hydrogen atom or a methyl group, R3 and R4 independently represent a hydrogen atom, a methyl group, or an ethyl group, or together represent a trimethylene group or a pentamethylene group, and Y directly a bond, a phenylene residue or a residue of the formula -Co-NH-C(CH3)2-0H2-, and Xo represents a proton (H+) or a cation. (6) The general formula (
Ia) 1-10 parts by weight of vinylphosphonic acid ester,
10-70 parts by weight of unsaturated sulfonic acid represented by general formula (Ila), 2 parts by weight of acrylamide and (or) methacrylamide
9-80 M parts and 0-20 parts by weight of vinyl acrylamine and/or vinyl phosphonic acid and/or acrylic and/or methacrylic acid of general formula (R/a) The manufacturing method according to scope item 5. (7) The method according to claim 5 or 6, which comprises emulsifying the aqueous monomer solution in an organic solvent that is immiscible with water before polymerization. (8) As an auxiliary agent in textile dyeing factories, the statistical distribution is 1-86% by weight of residues of general formula (1), 9-86% by weight of residues of general formula (II)
80% by weight, 5-90% by weight of residues of general formula (I[I)2 糺2 and optionally general formula fft
+) and (or) (V) and (or) (■-CH2-C
H-Akebono and R5 each independently represent a hydrogen atom or a methyl group; R3 and R4 independently represent a hydrogen atom, a methyl group, or an ethyl group, or together represent a trimethylene group or a pentamethylene group; yH Direct bond, a phenylene residue or a residue with the formula -00-NH-0(OH3), -CFI2-, and X'Il represents a proton (1') or a cation. Method. (9) A method according to claim 8, comprising using the water-soluble copolymer as described above as a badging aid. (10) The method according to claim 8, which comprises using the above-mentioned water-soluble copolymer as a leveling agent. (11) As a post-tanning material, residues 1-86 of the general formula (I) 1 and 9-86 weight of the residues of the general formula (CIt) have an average molecular weight (50,000 and have a statistical distribution)
80 weight, 5-90 weight residues of general formula Cm')2 high2 and optionally general formula
T (- and P independently represent a hydrogen atom or a methyl group,
R3 and R4 independently represent a hydrogen atom, a methyl group, or an ethyl group, or together represent a merimethylene group or a pentamethylene group, and Y is a direct bond, a phenylene residue, or a compound of the formula -〇〇-NH-C(OH3 ) A method using a water-soluble copolymer which represents a residue of 2-DH,-, and X(, 41 represents a proton (H+) or a cation).