CN104358119A - Reaction type anionic modifier and preparation method thereof - Google Patents
Reaction type anionic modifier and preparation method thereof Download PDFInfo
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- CN104358119A CN104358119A CN201410571707.8A CN201410571707A CN104358119A CN 104358119 A CN104358119 A CN 104358119A CN 201410571707 A CN201410571707 A CN 201410571707A CN 104358119 A CN104358119 A CN 104358119A
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Abstract
The invention provides a reaction type anionic modifier and a preparation method thereof. The reaction type anionic modifier comprises a compound represented by the formula I and/or one or a combination of several of compounds represented by the formula II shown in the description, wherein R1 is selected from -H, -CH3 and -CH2CH3; R2 is selected from aromatic radical with one or multiple water-soluble groups; R3 is selected from materials a, b and c of whish formulas shown in the description; R4 comprises materials c and d. The reaction type anionic modifier provided by the invention can realize modification by being reacted with cellulosic fibers in an aqueous solution, and yellowing of a textile can be avoided; the reaction type anionic modifier is suitable for industrial production at present.
Description
Technical field
The present invention relates to anion-modified dose of a kind of response type and preparation method thereof, particularly relate to anion-modified dose of a kind of lint cellulose fiber staining and preparation method thereof, belong to technical field of textile printing.
Background technology
In the processing and washing process of fabric, the staining of cellulose base fiber fabric intersection is very important problem for source mill and consumer.This problem of current solution is mainly by adopting anti-staining washing agent, but anti-staining washing agent is not fully effective for preventing staining.The main cause that staining occurs when washing cellulose base fiber fabric is the anionic species dyestuff that cellulose fibre attracts hydrolysis.
Application number is 99812552.0 application discloses and a kind ofly improve comfortableness and the anion-modified cotton of arbitrarily washing, and it adopts Amcide Ammate to carry out modification to cellulose fibre.But this process need high temperature bakes, cause the xanthochromia of fabric or yarn more serious.In addition, the method is not suitable for production procedure main at present, as: knitting stripe, tatting yarn-dyed fabric, knitting stripe, tatting yarn-dyed fabric two kinds of fabrics need cheese in process of production, and cheese is not suitable for the production method that the above-mentioned high temperature of employing bakes.
Therefore, development one can modification in aqueous, can avoid xanthochromia again, and anion-modified dose that is applicable to current suitability for industrialized production is the problem of needs solution at present.
Summary of the invention
In order to solve the problem, the object of the present invention is to provide anion-modified dose of a kind of response type, anion-modified dose of this response type can react with cellulose fibre in aqueous, carries out modification, and fabric can be avoided again to turn yellow and be applicable to current suitability for industrialized production.
In order to achieve the above object, the invention provides anion-modified dose of a kind of response type, it comprises the combination of one or more in the compound shown in formula I and/or the compound shown in formula II:
Wherein, R
1be selected from-H ,-CH
3,-CH
2cH
3;
R
2be selected from the aryl radical with one or more water soluble groups;
R
3be selected from
R
4be selected from
In anion-modified dose of response type provided by the invention, preferably, the R of employing
2be selected from:
According to specific embodiment of the invention scheme, preferably, anion-modified dose of this response type comprises the combination of one or more in following compounds:
Present invention also offers the preparation method of anion-modified dose of above-mentioned response type, comprise the following steps:
By compound N HR
1r
2be added to containing R
3compound solution in, wherein, compound N HR
1r
2with containing R
3the mol ratio of compound be 1:0.95-1.05, at 0 DEG C-100 DEG C, react 0.2h-8h, adjustment pH is 3-5, obtains the thick product solution of the compound shown in formula I, after purifying, drying, namely obtain the compound N R shown in formula I
1r
2r
3, i.e. anion-modified dose of described response type.
In the preparation method that response type provided by the invention is anion-modified dose, preferably, the purification of the thick product solution of the compound shown in formula I is comprised thick product solution neutralized and saltouts; Or
Thick product solution is carried out decompression distillation or solvent extraction, and be then 20 DEG C-40 DEG C (more preferably, temperature is 30 DEG C) in temperature, pressure is under the condition of 1kPa-4kPa, collects volatile materials, until solution is condensed into thick pulpous state or Powdered; Main component in the thick pulpous state of gained or powdered substance is the compound shown in formula I, can directly as the use of anion-modified dose of response type, also can through decompression distillation or solvent extraction, obtain after the compound shown in the higher formula of purity I as the use of anion-modified dose of response type.
The preparation method that response type provided by the invention is anion-modified dose is further comprising the steps of:
By the compound N R shown in formula I
1r
2r
3thick product solution or the compound shown in formula I with containing R
4the solution mixing of compound, wherein, the compound shown in formula I and containing R
4the mol ratio of compound be 1:0.95-1.05,0.2h-8h is reacted under 0 DEG C-100 DEG C (being more preferably 0 DEG C-50 DEG C), adjustment pH is 4-6, obtains the thick product solution of the compound shown in formula II, after purifying, drying, namely obtain the compound shown in formula II.
In the preparation method that response type provided by the invention is anion-modified dose, preferably, the purification of the thick product solution of the compound shown in formula II is comprised thick product solution neutralized and saltouts; Or
The thick product solution of the compound shown in formula II is carried out decompression distillation or solvent extraction, then be 20 DEG C-40 DEG C (more preferably, temperature is 30 DEG C) in temperature, pressure is under the condition of 1kPa-4kPa, collect volatile materials, until solution is condensed into thick pulpous state or Powdered; Main component in the thick pulpous state of gained or powdered substance is the compound shown in formula II, can directly as the use of anion-modified dose of response type, also can through decompression distillation, obtain after the compound shown in the higher formula of purity II as the use of anion-modified dose of response type.
According to specific embodiment of the invention scheme, when comprising several combination in the compound shown in the compound shown in formula I and formula II when anion-modified dose of described response type, according to the above-mentioned preparation method compound shown in obtained formula I and the compound shown in formula II respectively, then carry out in a conventional manner mixing.
According to specific embodiment of the invention scheme, decompression distillation or solvent extraction conveniently operate to be carried out.
According to specific embodiment of the invention scheme, preferably, when purifying, thick product solution is carried out neutralizing and saltouing, to remove residual unreacted compound and accessory substance, then dry, pulverizing, finally obtains pulverulent solids and is anion-modified dose of response type.
According to specific embodiment of the invention scheme, preferably, when purifying, thick product solution is carried out decompression distillation or solvent extraction, object removes residual unreacted compound and accessory substance, then it is 20 DEG C-40 DEG C in temperature, pressure is under the condition of 1kPa-4kPa, volatile materials is collected by dry ice collector, until solution is condensed into thick pulpous state or Powdered, the thick pulpous state of gained or pulverous material can directly as the uses of anion-modified dose of response type, also can through decompression distillation or solvent extraction, obtain after the higher compound of purity as the use of anion-modified dose of response type.
In anion-modified dose of response type provided by the invention, compound N HR
1r
2be added drop-wise to gradually containing R
3compound solution in react, obtain the compound N R shown in formula I
1r
2r
3reaction equation as follows:
By the compound N R shown in formula I
1r
2r
3thick product solution or purification afterproduct solution with containing R
4the solution of compound react further, the reaction equation obtaining the compound shown in formula II is as follows:
When anion-modified dose of response type provided by the invention is specifically for modification, containing in the solution of inorganic salts, adding anion-modified dose of described response type wherein with caustic soda or soda ash (is generally the caustic soda when containing epoxy radicals in anion-modified dose of response type, with soda ash in other situations), mix, to pure cotton fabric modification 0.1-1 hour at 0-100 DEG C, then through 2 road washing and pickling, namely complete response type of the present invention anion-modified dose of modification to COTTON FABRIC.
Anion-modified dose of response type provided by the invention tool compared with existing ion modification agent has the following advantages:
Response type provided by the invention anion-modified dose of energy reacts, to cellulose CSP at the aqueous solution and cellulose fibre;
Anion-modified dose of response type provided by the invention can avoid the xanthochromia of fabric, is applicable to current suitability for industrialized production.
detailed description of the invention
In order to there be understanding clearly to technical characteristic of the present invention, object and beneficial effect, existing following detailed description is carried out to technical scheme of the present invention, but can not be interpreted as to of the present invention can the restriction of practical range.
Embodiment 1
Present embodiments provide anion-modified dose of a kind of response type, it is prepared by following steps:
Cyanuric Chloride is carried out in ice-water bath pull an oar and join in reactor, start agitator, in reactor, slowly drip the prior dissolving of Cyanuric Chloride 1.05 times of molar weights and cool to the aniline-2 of 0-5 DEG C, 4-sodium disulfonate solution, dropwise in 30 minutes, temperature controls, at about 5 DEG C, to use NaHCO
3regulate pH, pH is remained on 3-3.5, obtains thick product solution;
In above-mentioned thick product solution, add the para-ester of its 0.95 times of molar weight, control pH is 4-4.5, is slowly warming up to lower than 60 DEG C, detects with amino agents, and boundary line nondiscolouring then reaches reaction end;
Then carried out neutralizing, saltout and precipitating by the product of gained, the solid matter through low temperature drying gained is anion-modified dose of response type, shown in I-1:
The product of above-mentioned gained is used for cellulose CSP and evaluates:
By the mixed solution of anion-modified for the response type of gained dose and soda ash, (in mixed solution, the concentration of anion-modified dose of response type is 15g/L, Na
2sO
4concentration be 70g/L, pure paper mill wastewater is 20g/L), pure cotton fabric is carried out to the modification of 1 hour at 70 DEG C, then be the acetic acid pickling of 1g/L through 2 road washings and concentration, do Crockmeter Test by the blue hydrolysed reactive dye of 10g/L, contrast with the common pure cotton fabric not carrying out modification.
Final result shows, after response type anion-modified dose of modification of the present embodiment, pure cotton fabric does not have staining, and the common pure cotton fabric staining not carrying out modification is serious.
Embodiment 2
The present embodiment provides anion-modified dose of a kind of response type, and it is prepared by following steps:
Cyanuric fluoride is carried out in ice-water bath pull an oar and join in reactor, start agitator, in reactor, slowly drip the prior dissolving of cyanuric fluoride 1 times of molar weight and cool to the aniline-2 of 0-5 DEG C, 4-sodium disulfonate solution, dropwise in 30 minutes, temperature controls, at about 1 DEG C, to use NaHCO
3regulate pH, pH is remained on 3-3.5, obtains thick product solution;
In above-mentioned thick product solution, add the para-ester of its 1 times of molar weight, control pH is 4-4.5, is slowly warming up to lower than 60 DEG C, detects with amino agents, and boundary line nondiscolouring then reaches reaction end;
Then carried out neutralizing, saltout and precipitating by the product of gained, the solid matter through low temperature drying gained is anion-modified dose of response type, shown in I-2:
The product of above-mentioned gained is used for cellulose CSP and evaluates:
By the mixed solution of anion-modified for the response type of gained dose and soda ash, (in mixed solution, the concentration of anion-modified dose of response type is 15g/L, Na
2sO
4concentration be 70g/L, pure paper mill wastewater is 20g/L), pure cotton fabric is carried out to the modification of 1 hour under the condition of 60 DEG C, then be the acetic acid pickling of 1g/L through 2 road washings and concentration, do Crockmeter Test by the blue hydrolysed reactive dye of 10g/L, contrast with the common pure cotton fabric not carrying out modification.
Final result shows, after response type anion-modified dose of modification of the present embodiment, pure cotton fabric does not have staining, and the common pure cotton fabric staining not carrying out modification is serious.
Embodiment 3
The present embodiment provides anion-modified dose of a kind of response type, and it is prepared by following steps:
Cyanuric Chloride is carried out in ice-water bath pull an oar and join in reactor, start agitator, in reactor, slowly drip the prior dissolving of Cyanuric Chloride 1.05 times of molar weights and cool to the aniline-2 of 0-5 DEG C, 4-sodium disulfonate solution, dropwise in 30 minutes, temperature controls, at about 5 DEG C, to use NaHCO
3regulate pH, pH is remained on 3-3.5, obtains thick product solution;
In above-mentioned thick product solution, add position ester between its 1.05 times of molar weights, control pH is 4-4.5, is slowly warming up to lower than 60 DEG C, detects with amino agents, and boundary line nondiscolouring then reaches reaction end;
Then carried out neutralizing, saltout and precipitating by the product of gained, the solid matter through low temperature drying gained is anion-modified dose of response type, shown in I-3:
The product of above-mentioned gained is used for cellulose CSP and evaluates:
By the mixed solution of anion-modified for the response type of gained dose and soda ash, (in mixed solution, the concentration of anion-modified dose of response type is 15g/L, Na
2sO
4concentration be 70g/L, pure paper mill wastewater is 20g/L), pure cotton fabric is carried out to the modification of 1 hour under the condition of 70 DEG C, then be the acetic acid pickling of 1g/L through 2 road washings and concentration, do Crockmeter Test by the blue hydrolysed reactive dye of 10g/L, contrast with the common pure cotton fabric not carrying out modification.
Final result shows, after response type anion-modified dose of modification of the present embodiment, pure cotton fabric does not have staining, and the common pure cotton fabric staining not carrying out modification is serious.
Embodiment 4
The present embodiment provides anion-modified dose of a kind of response type, and it is prepared by following steps:
Cyanuric Chloride is carried out in ice-water bath pull an oar and join in reactor, start agitator, in reactor, slowly drip the prior dissolving of Cyanuric Chloride 1.05 times of molar weights and cool to the aniline-2 of 0-5 DEG C, 4-sodium disulfonate solution, dropwise in 30 minutes, temperature controls, at about 5 DEG C, to use NaHCO
3regulate pH, pH is remained on 3-3.5, obtains thick product solution;
In above-mentioned thick product solution, add the sulfonation para-ester of its 1 times of molar weight, control pH is 4-4.5, is slowly warming up to lower than 60 DEG C, detects with amino agents, and boundary line nondiscolouring then reaches reaction end;
Then carried out neutralizing, saltout and precipitating by the product of gained, the solid matter through low temperature drying gained is anion-modified dose of response type, shown in I-4:
The product of above-mentioned gained is used for cellulose CSP and evaluates:
By the mixed solution of anion-modified for the response type of gained dose and soda ash, (in mixed solution, the concentration of anion-modified dose of response type is 15g/L, Na
2sO
4concentration be 70g/L, pure paper mill wastewater is 20g/L), pure cotton fabric is carried out to the modification of 1 hour under the condition of 70 DEG C, then be the acetic acid pickling of 1g/L through 2 road washings and concentration, do Crockmeter Test by the blue hydrolysed reactive dye of 10g/L, contrast with the common pure cotton fabric not carrying out modification.
Final result shows, after response type anion-modified dose of modification of the present embodiment, pure cotton fabric does not have staining, and the common pure cotton fabric staining not carrying out modification is serious.
Embodiment 5
The present embodiment provides anion-modified dose of a kind of response type, and it is prepared by following steps:
Cyanuric Chloride is carried out in ice-water bath pull an oar and join in reactor, start agitator, in reactor, slowly drip the prior dissolving of Cyanuric Chloride 0.95 times of molar weight and cool to the benzene methanamine-2 of 0-5 DEG C, 4-sodium disulfonate solution, dropwise in 30 minutes, temperature controls, at about 10 DEG C, to use NaHCO
3regulate pH, pH is remained on 3-3.5, obtains thick product solution;
In above-mentioned thick product solution, add the sulfonation para-ester of its 1 times of molar weight, control pH is 4-4.5, is slowly warming up to lower than 60 DEG C, detects with amino agents, and boundary line nondiscolouring then reaches reaction end;
Then carried out neutralizing, saltout and precipitating by the product of gained, the solid matter through low temperature drying gained is anion-modified dose of response type, shown in I-5:
The product of above-mentioned gained is used for cellulose CSP and evaluates:
By the mixed solution of anion-modified for the response type of gained dose and soda ash, (in mixed solution, the concentration of anion-modified dose of response type is 15g/L, Na
2sO
4concentration be 70g/L, pure paper mill wastewater is 20g/L), pure cotton fabric is carried out to the modification of 1 hour under the condition of 70 DEG C, then be the acetic acid pickling of 1g/L through 2 road washings and concentration, do Crockmeter Test by the blue hydrolysed reactive dye of 10g/L, contrast with the common pure cotton fabric not carrying out modification.
Final result shows, after response type anion-modified dose of modification of the present embodiment, pure cotton fabric does not have staining, and the common pure cotton fabric staining not carrying out modification is serious.
Embodiment 6
The present embodiment provides anion-modified dose of a kind of response type, and it is prepared by following steps:
Cyanuric fluoride is carried out in ice-water bath pull an oar and join in reactor, start agitator, in reactor, slowly drip the prior dissolving of cyanuric fluoride 1.05 times of molar weights and cool to the aniline-2 of 0-5 DEG C, 4-sodium disulfonate solution, dropwise in 30 minutes, temperature controls, at about 1 DEG C, to use NaHCO
3regulate pH, pH is remained on 3-3.5, obtains thick product solution;
In above-mentioned thick product solution, add the sulfonation para-ester of its 0.95 times of molar weight, control pH is 4-4.5, is slowly warming up to lower than 60 DEG C, detects with amino agents, and boundary line nondiscolouring then reaches reaction end;
Then carried out neutralizing, saltout and precipitating by the product of gained, the solid matter through low temperature drying gained is anion-modified dose of response type, shown in I-6:
The product of above-mentioned gained is used for cellulose CSP and evaluates:
By the mixed solution of anion-modified for the response type of gained dose and soda ash, (in mixed solution, the concentration of anion-modified dose of response type is 15g/L, Na
2sO
4concentration be 70g/L, pure paper mill wastewater is 20g/L), pure cotton fabric is carried out to the modification of 1 hour under the condition of 60 DEG C, then be the acetic acid pickling of 1g/L through 2 road washings and concentration, do Crockmeter Test by the blue hydrolysed reactive dye of 10g/L, contrast with the common pure cotton fabric not carrying out modification.
Final result shows, after response type anion-modified dose of modification of the present embodiment, pure cotton fabric does not have staining, and the common pure cotton fabric staining not carrying out modification is serious.
Embodiment 7
The present embodiment provides anion-modified dose of a kind of response type, and it is prepared by following steps:
Cyanuric fluoride is carried out in ice-water bath pull an oar and join in reactor, start agitator, in reactor, slowly drip the prior dissolving of cyanuric fluoride 1.05 times of molar weights and cool to the benzene methanamine-2 of 0-5 DEG C, 4-sodium disulfonate solution, dropwise in 30 minutes, temperature controls, at about 15 DEG C, to use NaHCO
3regulate pH, pH is remained on 3-3.5, obtains thick product solution;
In above-mentioned thick product solution, add position ester between its 1 times of molar weight, control pH is 4-4.5, and slowly heat up lower than 60 DEG C, detect with amino agents, boundary line nondiscolouring then reaches reaction end;
Then carried out neutralizing, saltout and precipitating by the product of gained, the solid matter through low temperature drying gained is anion-modified dose of response type, shown in I-7:
The product of above-mentioned gained is used for cellulose CSP and evaluates:
By the mixed solution of anion-modified for the response type of gained dose and soda ash, (in mixed solution, the concentration of anion-modified dose of response type is 15g/L, Na
2sO
4concentration be 70g/L, pure paper mill wastewater is 20g/L), pure cotton fabric is carried out to the modification of 1 hour under the condition of 60 DEG C, then be the acetic acid pickling of 1g/L through 2 road washings and concentration, do Crockmeter Test by the blue hydrolysed reactive dye of 10g/L, contrast with the common pure cotton fabric not carrying out modification.
Final result shows, after response type anion-modified dose of modification of the present embodiment, pure cotton fabric does not have staining, and the common pure cotton fabric staining not carrying out modification is serious.
Embodiment 8
The present embodiment provides anion-modified dose of a kind of response type, and it is prepared by following steps:
Cyanuric fluoride is carried out in ice-water bath pull an oar and join in reactor, start agitator, in reactor, slowly drip the prior dissolving of cyanuric fluoride 1.05 times of molar weights and cool to the aniline-2 of 0-5 DEG C, 4-sodium disulfonate solution, dropwise in 30 minutes, temperature controls, at about 1 DEG C, to use NaHCO
3regulate pH, pH is remained on 3-3.5, obtains product;
Then carried out neutralizing, saltout and precipitating by the product of gained, the solid matter through low temperature drying gained is anion-modified dose of response type, shown in I-8:
The product of above-mentioned gained is used for cellulose CSP and evaluates:
By the mixed solution of anion-modified for the response type of gained dose and soda ash, (in mixed solution, the concentration of anion-modified dose of response type is 15g/L, Na
2sO
4concentration be 70g/L, pure paper mill wastewater is 20g/L), pure cotton fabric is carried out to the modification of 1 hour under the condition of 30 DEG C, then be the acetic acid pickling of 1g/L through 2 road washings and concentration, do Crockmeter Test by the blue hydrolysed reactive dye of 10g/L, contrast with the common pure cotton fabric not carrying out modification.
Final result shows, after response type anion-modified dose of modification of the present embodiment, pure cotton fabric does not have staining, and the common pure cotton fabric staining not carrying out modification is serious.
Embodiment 9
The present embodiment provides anion-modified dose of a kind of response type, and it is prepared by following steps:
Cyanuric Chloride is carried out in ice-water bath pull an oar and join in reactor, start agitator, in reactor, slowly drip the prior dissolving of Cyanuric Chloride 1.05 times of molar weights and cool to the aniline-2 of 0-5 DEG C, 4-sodium disulfonate solution, dropwise in 30 minutes, temperature controls, at about 5 DEG C, to use NaHCO
3regulate pH, pH is remained on 3-3.5, obtains product;
Then carried out neutralizing, saltout and precipitating by the product of gained, the solid matter through low temperature drying gained is anion-modified dose of response type, shown in I-9:
The product of above-mentioned gained is used for cellulose CSP and evaluates:
By the mixed solution of anion-modified for the response type of gained dose and soda ash, (in mixed solution, the concentration of anion-modified dose of response type is 15g/L, Na
2sO
4concentration be 70g/L, pure paper mill wastewater is 20g/L), pure cotton fabric is carried out to the modification of 1 hour under the condition of 40 DEG C, then be the acetic acid pickling of 1g/L through 2 road washings and concentration, do Crockmeter Test by the blue hydrolysed reactive dye of 10g/L, contrast with the common pure cotton fabric not carrying out modification.
Final result shows, after response type anion-modified dose of modification of the present embodiment, pure cotton fabric does not have staining, and the common pure cotton fabric staining not carrying out modification is serious.
Embodiment 10
The present embodiment provides anion-modified dose of a kind of response type, and it is prepared by following steps:
Cyanuric Chloride is carried out in ice-water bath pull an oar and join in reactor, start agitator, in reactor, slowly drip the prior dissolving of Cyanuric Chloride 1.05 times of molar weights and cool to the p-sulfonic acid sodium aniline solution of 0-5 DEG C, dropwising in 30 minutes, temperature controls, at about 5 DEG C, to use NaHCO
3regulate pH, pH is remained on 3-3.5, obtains product;
Then carried out neutralizing, saltout and precipitating by the product of gained, the solid matter through low temperature drying gained is anion-modified dose of response type, shown in I-10:
The product of above-mentioned gained is used for cellulose CSP and evaluates:
By the mixed solution of anion-modified for the response type of gained dose and soda ash, (in mixed solution, the concentration of anion-modified dose of response type is 15g/L, Na
2sO
4concentration be 70g/L, pure paper mill wastewater is 20g/L), pure cotton fabric is carried out to the modification of 1 hour under the condition of 40 DEG C, then be the acetic acid pickling of 1g/L through 2 road washings and concentration, do Crockmeter Test by the blue hydrolysed reactive dye of 10g/L, contrast with the common pure cotton fabric not carrying out modification.
Final result shows, after response type anion-modified dose of modification of the present embodiment, cotton textiles do not have staining, and the common pure cotton fabric staining not carrying out modification is serious.
Embodiment 11
The present embodiment provides anion-modified dose of a kind of response type, and it is prepared by following steps:
In the reactor that reflux condenser is housed, add aniline-2,4-sodium disulfonate solution, start agitator, by in the epoxychloropropane of aniline-2,4-sodium disulfonate 1.05 times of molar weights at ambient temperature slow dropwise reaction still, after dripping off, continue reaction 6h, stop reaction, obtain product;
Then the product of gained is carried out decompression distillation purification, the unreacted compound that removing is residual as far as possible and accessory substance, hierarchy of control temperature is at about 30 DEG C, pressure is at 1-4kPa, collect volatile materials by dry ice collector, until product solution is condensed into thick pulpous state (quality is substantially constant is reaction end), the thick slurry matter of gained is through decompression distillation, obtain anion-modified dose of the higher response type of purity, shown in I-11:
The product of above-mentioned gained is used for cellulose CSP and evaluates:
By the mixed solution of anion-modified for the response type of gained dose and caustic soda (in mixed solution, the concentration of anion-modified dose of response type is 15g/L, burning paper mill wastewater is 5g/L), pure cotton fabric is carried out to the modification of 1 hour under the condition of 70 DEG C, then be the acetic acid pickling of 1g/L through 2 road washings and concentration, do Crockmeter Test by the blue hydrolysed reactive dye of 10g/L, contrast with the common pure cotton fabric not carrying out modification.
Final result shows, after response type anion-modified dose of modification of the present embodiment, pure cotton fabric does not have staining, and the common pure cotton fabric staining not carrying out modification is serious.
In sum, anion-modified dose of response type provided by the invention is that one can carry out modification to cellulose fibre in aqueous, makes cellulose base fiber fabric that the modifier of intersection staining not occur.
Claims (9)
1. anion-modified dose an of response type, it comprises the combination of one or more in the compound shown in formula I and/or the compound shown in formula II,
Wherein, R
1be selected from-H ,-CH
3,-CH
2cH
3;
R
2be selected from the aryl radical with one or more water soluble groups;
R
3be selected from
R
4be selected from
2. anion-modified dose of response type according to claim 1, wherein, described R
2be selected from
3. anion-modified dose of response type according to claim 1, wherein, anion-modified dose of this response type comprises the combination of one or more in following compounds:
4. the preparation method that the response type described in any one of claim 1-3 is anion-modified dose, comprises the following steps:
By compound N HR
1r
2be added to containing R
3compound solution in, wherein, compound N HR
1r
2with containing R
3the mol ratio of compound be 1:0.95-1.05, at 0-100 DEG C, react 0.2h-8h, adjustment pH is 3-5, obtains the thick product solution of the compound shown in formula I, namely the compound shown in formula I is obtained, i.e. anion-modified dose of described response type after purifying, drying.
5. preparation method according to claim 4, wherein, comprises the purification of the thick product solution of the compound shown in formula I and to be neutralized by thick product solution and saltout; Or
Thick product solution is carried out decompression distillation or solvent extraction, and be then 20 DEG C-40 DEG C in temperature, pressure is under the condition of 1kPa-4kPa, collects volatile materials, until solution is condensed into thick pulpous state or Powdered.
6. preparation method according to claim 5, wherein, the temperature of described collection volatile materials is 30 DEG C.
7. preparation method according to claim 4, wherein, the method is further comprising the steps of:
By the compound shown in the thick product solution of the compound shown in formula I or formula I and containing R
4the solution mixing of compound, wherein, the compound shown in formula I with containing R
4the mol ratio of compound be 1:0.95-1.05, at 0-100 DEG C, react 0.2h-8h, adjustment pH is 4-6, obtains the thick product solution of the compound shown in formula II, after purifying, drying, namely obtain the compound shown in formula II.
8. preparation method according to claim 7, wherein, comprises the purification of the thick product solution of the compound shown in formula II and the thick product solution of the compound shown in formula II is neutralized and saltoutd; Or
The thick product solution of the compound shown in formula II is carried out decompression distillation or solvent extraction, and be then 20 DEG C-40 DEG C in temperature, pressure is under the condition of 1kPa-4kPa, collects volatile materials, until solution is condensed into thick pulpous state or Powdered.
9. preparation method according to claim 8, wherein, the temperature of described collection volatile materials is 30 DEG C.
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