CN106633049A - Vat dye ozone-proof fastness improver as well as preparation method and application thereof - Google Patents

Abstract

Aiming at the problem that vat dyes represented by indigo are affected by ozone and cause the dyed fabrics to fade, the invention provides a vat dye ozone fastness improving agent, which is an epoxy-terminated hyperbranched polyamide-amine. The preparation method of the above-mentioned vat dye fastness to ozone fastness enhancer is as follows: firstly, the Michael addition reaction between ethylenediamine and methyl acrylate is used to prepare 3.5 generation polyamide-amine (PAMAM) dendritic macromolecules; Polyethylene polyamine-modified PAMAM is prepared by polyamine reaction, and then epoxy chlorohydrin is used to react with polyethylene polyamine-modified PAMAM to prepare epoxy-terminated hyperbranched polyamide-amine. The above mentioned agent for improving the ozone fastness of vat dyes can be applied in textiles. The ozone fastness improving agent of the vat dye obtained in the invention obviously improves the ozone fading fastness of indigo dyed fabrics.

Description

A kind of vat dye ozone fastness improving agent and its preparation method and application

technical field

The invention belongs to the technical field of textile chemistry, and in particular relates to an agent for improving the ozone fastness of vat dyes, a preparation method and application thereof.

Background technique

With the acceleration of industrialization and the sharp increase in the number of urban vehicles, the concentration of ozone in the air is gradually increasing. As an electrophile, ozone will attack electron pairs in unsaturated structures such as carbon-carbon double bonds, resulting in structural changes in unsaturated organic molecules. The molecular structure of vat dyes represented by indigo contains a large number of unsaturated bonds. The rapid increase of ozone concentration in the air will inevitably lead to the fading of vat dye dyed fabrics. Many foreign companies have put forward corresponding requirements for the ozone fastness of imported and exported textiles. Therefore, it is urgent to develop an ozone fastness enhancer to solve the defect that some vat dyes are severely faded when exposed to ozone. No research.

Contents of the invention

The technical problem to be solved by the present invention is to overcome the problem that the vat dyes represented by indigo are affected by ozone and cause the dyed fabrics to fade, and to provide a vat dye ozone fastness improving agent and its preparation method and application.

In order to solve the above-mentioned technical problems, the technical scheme adopted in the present invention is: at first utilize the Michael addition reaction between ethylenediamine and methyl acrylate to prepare 3.5 generation polyamide-amine (PAMAM) dendritic macromolecule, then with polyethylenepolyamine The reaction prepares polyethylene polyamine modified PAMAM, and then reacts with epichlorohydrin and polyethylene polyamine modified PAMAM to prepare epoxy-terminated hyperbranched polyamide-amine, which improves the binding fastness of PAMAM and textiles, and uses PAMAM molecules A large number of reducing amino groups in the structure react with ozone to protect vat dyes and prevent fading of dyed textiles.

The preparation method of the above-mentioned vat dye ozone fastness improving agent, the specific steps are as follows:

(1) Weigh 0.15 mol of ethylenediamine and 2.0-5.0 mol of methanol and add them to a three-necked flask with magnetic stirring, reflux condenser and thermometer, put them in an ice-water bath and add 0.9-1.5 mol dropwise under stirring conditions. mol of methyl acrylate; after the dropwise addition, react at 25-30°C for 24-48h, then at 30°C and 125P pressure, use a rotary evaporator to distill off the solvent methanol and excess methyl acrylate under reduced pressure. Vacuum drying at -80°C for 12-24 hours to obtain 0.5-generation ester end group PAMAM;

(2) 50mmol of the above-mentioned 0.5 generation PAMAM and 2.0-5.0mol methanol were successively added to a three-necked flask with magnetic stirring, a reflux condenser, and a thermometer, and they were put into an ice-water bath, and ethylenediamine was added dropwise under stirring conditions ( n _{0.5 generation PAMAM} : n _{ethylenediamine} = 1:8-1:24); after the dropwise addition, react at 25-30°C for 24-48h, then depressurize with a rotary evaporator at 30°C and 125P pressure The solvent methanol and excess ethylenediamine were distilled off, and vacuum-dried at 60-80°C for 12-24 hours to obtain 1.0-generation amine-terminated PAMAM;

(3) Repeat the Michael addition and amidation condensation reactions according to the feeding ratio and operating conditions of (1) and (2), respectively, to obtain 1.5 generation, 2.0 generation, 2.5 generation, 3.0 generation, and 3.5 generation PAMAM;

(4) Add 50 mmol of the above-mentioned 3.5-generation PAMAM and 2.0-5.0 mol of methanol successively into a three-necked flask with magnetic stirring, reflux condenser, and thermometer, put it in an ice-water bath, and add polyethylene polyamine drop by drop under stirring conditions ;After the dropwise addition, react at 25-30°C for 24-48h, then at 30°C and 125P pressure, use a rotary evaporator to carry out vacuum distillation to remove solvent methanol and excess polyethylene polyamine, vacuum at 60-80°C Dry for 12-24 hours to obtain polyethylene polyamine modified PAMAM;

(5) Add 250mL ethanol to a 1000mL three-necked flask, then add 0.2mol polyethylene polyamine modified PAMAM, stir for 10-20min, then heat up the water bath to 28-30°C, add epichlorohydrin dropwise under stirring, 1.0 Add within -2.0h, then react at this temperature for 5-8h, keep the temperature in the reaction bottle not exceeding 30°C during the reaction, then raise the temperature to 40-45°C, add NaOH solution with a mass fraction of 50% at a constant speed within 2h , after the drop, maintain 40-45 ° C for 1-2h, after the reaction, filter to remove NaCl, and then distill under reduced pressure to remove the remaining reactants, ethanol and water.

The polyethylene polyamine described in step (4) is a kind of in diethylene triamine, triethylene tetramine, tetraethylene pentamine, and 3.5 generations of PAMAM and polyethylene polyamine mol ratio are n _{3.5 generations of PAMAM} : n _{more Ethylene polyamine} =1:8-1:24.

Polyethylene polyamine modified PAMAM and epichlorohydrin mol ratio described in step (5) are n _{polyethylene polyamine modified PAMAM} :n _{epichlorohydrin} =1:3-1:6, NaOH and epoxy chloride The propane molar ratio is n _NaOH :n _{epichlorohydrin} =1:1.1-1:1.3.

It can be seen from the above technical scheme that the present invention firstly introduces polyethylene polyamines with strong reducibility into the molecular structure of PAMAM, utilizes a large number of amino groups in the molecular structure to react with ozone to protect vat dyes, and simultaneously solves the problem of direct use of polyethylene polyamines. Volatile and irritating problems in the process; use epichlorohydrin to functionalize polyethylene polyamine modified PAMAM, and use the reaction performance between epoxy groups and hydroxyl groups on cellulose fibers to Improve the binding fastness of polyethylene polyamine modified PAMAM and textiles.

The above-mentioned vat dye ozone fastness improving agent can be applied in textiles.

Its application proceeds as follows:

Weigh 2-4g of the vat dye ozone fastness improving agent, add water to dilute to 100mL, soak the textile in it, take it out after 2-5min, roll and press the fabric, two dipping and two rolling, the excess rate is 70%-90%, and then Dry at 80°C, then bake at 100-150°C for 3-5 minutes, then wash with water 3-5 times, soap boil and dry.

The textiles described in the above application steps are one of cotton, linen and viscose fabrics or a blended product of the two.

The beneficial effects of the present invention are:

(1) Utilize the reducibility of a large number of amino groups in polyethylene polyamine and PAMAM molecular structure to protect vat dyes.

(2) Use the reactivity of epichlorohydrin to improve the binding fastness between PAMAM molecules and textiles.

detailed description

The present invention will be described in further detail below in conjunction with specific embodiments. It should be understood that these examples are only for illustration of the present invention, but not to limit the scope of the present invention in any way.

Example 1

(1) Weigh 0.15mol ethylenediamine and 2.0mol methanol and add them to a three-necked flask with magnetic stirring, reflux condenser, and thermometer, put them in an ice-water bath, and add 0.9mol of methyl acrylate dropwise under stirring conditions Esters; react at 25°C for 48h after the dropwise addition, then use a rotary evaporator to distill off the solvent methanol and excess methyl acrylate under reduced pressure at 30°C and 125P pressure, and dry under vacuum at 60°C for 24h to obtain 0.5 generation Ester-terminated PAMAM;

(2) Add 50mmol of the above-mentioned 0.5 generation PAMAM and 2.0mol methanol successively into a three-necked flask with magnetic stirring, reflux condenser, and thermometer, put it into an ice-water bath, and add ethylenediamine dropwise under stirring conditions (n _{0.5 Replacing PAMAM} : n _{ethylenediamine} =1:8); After the dropwise addition, react at 25°C for 48h, then at 30°C and 125P pressure, use a rotary evaporator to carry out vacuum distillation to remove solvent methanol and excess ethylenediamine , dried under vacuum at 60°C for 24 hours to obtain 1.0-generation amine-terminated PAMAM;

(3) Repeat the Michael addition and amidation condensation reactions according to the feeding ratio and operating conditions of (1) and (2), respectively, to obtain 1.5 generation, 2.0 generation, 2.5 generation, 3.0 generation, and 3.5 generation PAMAM;

(4) 50mmol of the above-mentioned 3.5 generation PAMAM and 2.0mol methanol were successively added to a three-necked flask with magnetic stirring, reflux condenser, and thermometer, put into an ice-water bath and added diethylenetriamine dropwise under stirring conditions, 3.5 The molar ratio of substituted PAMAM and diethylenetriamine is n _{3.5 substituted PAMAM} :n _{diethylenetriamine} =1:8; after the dropwise addition is completed, react at 25°C for 48h, then use a rotary evaporator at 30°C and 125P pressure The solvent methanol and excess diethylenetriamine were distilled off under reduced pressure, and vacuum-dried at 60°C for 24 hours to obtain diethylenetriamine-modified PAMAM;

(5) Add 250mL of ethanol to a 1000mL three-necked flask, then add 0.2mol of diethylenetriamine modified PAMAM, stir for 10min, then raise the temperature of the water bath to 28°C, add 0.6mol of epichlorohydrin dropwise under stirring, within 1.0h After adding, react at this temperature for 5 hours, keep the temperature in the reaction bottle no more than 30 DEG C during the reaction, then raise the temperature to 40 DEG C, and dropwise add NaOH solution with a mass fraction of 50% (NaOH and epichlorohydrin mole The ratio is n _NaOH :n _{epichlorohydrin} = 1:1.1), after dropping, maintain 40°C for 2h, after the reaction, remove NaCl by filtration, then distill under reduced pressure to remove the remaining reactants, ethanol and water. ;

(6) Weigh 2 g of the above-mentioned vat dye ozone fastness improving agent, add water to dilute to 100 mL, soak the indigo-dyed cotton fabric in it, take it out after 2 min, and roll the fabric, dipping and rolling twice, the excess rate is 70%, Then dry it at 80°C, then bake it at 100°C for 5 minutes, wash it with water three times, boil it with soap and dry it.

Comparative example 1

(1) Weigh 0.15mol ethylenediamine and 2.0mol methanol and add them to a three-necked flask with magnetic stirring, reflux condenser, and thermometer, put them in an ice-water bath, and add 0.9mol of methyl acrylate dropwise under stirring conditions Esters; react at 25°C for 48h after the dropwise addition, then use a rotary evaporator to distill off the solvent methanol and excess methyl acrylate under reduced pressure at 30°C and 125P pressure, and dry under vacuum at 60°C for 24h to obtain 0.5 generation Ester-terminated PAMAM;

(2) Add 50mmol of the above-mentioned 0.5 generation PAMAM and 2.0mol methanol successively into a three-necked flask with magnetic stirring, reflux condenser, and thermometer, put it into an ice-water bath, and add ethylenediamine dropwise under stirring conditions (n _{0.5 Replacing PAMAM} : n _{ethylenediamine} =1:8); After the dropwise addition, react at 25°C for 48h, then at 30°C and 125P pressure, use a rotary evaporator to carry out vacuum distillation to remove solvent methanol and excess ethylenediamine , dried under vacuum at 60°C for 24 hours to obtain 1.0-generation amine-terminated PAMAM;

(3) Repeat the Michael addition and amidation condensation reactions according to the feeding ratio and operating conditions of (1) and (2), respectively, to obtain 1.5 generation, 2.0 generation, 2.5 generation, 3.0 generation, and 3.5 generation PAMAM;

(4) 50mmol of the above-mentioned 3.5 generation PAMAM and 2.0mol methanol were successively added to a three-necked flask with magnetic stirring, reflux condenser, and thermometer, put into an ice-water bath and added diethylenetriamine dropwise under stirring conditions, 3.5 The molar ratio of substituted PAMAM and diethylenetriamine is n _{3.5 substituted PAMAM} :n _{diethylenetriamine} =1:8; after the dropwise addition is completed, react at 25°C for 48h, then use a rotary evaporator at 30°C and 125P pressure The solvent methanol and excess diethylenetriamine were distilled off under reduced pressure, and vacuum-dried at 60°C for 24 hours to obtain diethylenetriamine-modified PAMAM;

(5) Weigh 2g of the above-mentioned diethylenetriamine modified PAMAM, add water to dilute to 100mL, soak the indigo-dyed cotton fabric in it, take it out after 2min, and roll the fabric, dipping and rolling twice, the excess rate is 70%, Then dry it at 80°C, then bake it at 100°C for 5 minutes, wash it with water three times, boil it with soap and dry it.

Example 2

(1) Weigh 0.15mol of ethylenediamine and 5.0mol of methanol into a three-necked flask with magnetic stirring, reflux condenser, and thermometer, put it into an ice-water bath, and add 1.5mol of methyl acrylate dropwise under stirring conditions Esters; after the dropwise addition, react at 30°C for 24h, then use a rotary evaporator to distill off methanol and excess methyl acrylate under reduced pressure at 30°C and 125P pressure, and dry under vacuum at 80°C for 12h to obtain 0.5 generation Ester-terminated PAMAM;

(2) Add 50mmol of the above-mentioned 0.5 generation PAMAM and 5.0mol methanol successively into a three-necked flask with magnetic stirring, reflux condenser, and thermometer, put it into an ice-water bath, and add ethylenediamine dropwise under stirring conditions (n _{0.5 Replacing PAMAM} : n _{ethylenediamine} =1:24); After the dropwise addition, react at 30°C for 24h, then at 30°C and 125P pressure, use a rotary evaporator to carry out vacuum distillation to remove solvent methanol and excess ethylenediamine , dried under vacuum at 80°C for 12 hours to obtain 1.0-generation amine-terminated PAMAM;

(3) Repeat the Michael addition and amidation condensation reactions according to the feeding ratio and operating conditions of (1) and (2), respectively, to obtain 1.5 generation, 2.0 generation, 2.5 generation, 3.0 generation, and 3.5 generation PAMAM;

(4) 50mmol of the above-mentioned 3.5 generation PAMAM and 5.0mol methanol were successively added into a three-necked flask with magnetic stirring, a reflux condenser, and a thermometer, and they were put into an ice-water bath and triethylenetetramine was added dropwise under stirring conditions, 3.5 The molar ratio of PAMAM and triethylenetetramine is n _{3.5 generation PAMAM} :n _{triethylenetetramine} = 1:24; after the dropwise addition, react at 30°C for 24h, then use a rotary evaporator at 30°C and 125P pressure The solvent methanol and excess triethylenetetramine were distilled off under reduced pressure, and vacuum-dried at 80°C for 12 hours to obtain triethylenetetramine-modified PAMAM;

(5) Add 250mL ethanol to a 1000mL three-necked flask, then add 0.2mol triethylenetetramine modified PAMAM, stir for 20min, then heat up the water bath to 30°C, add 1.2mol epichlorohydrin dropwise under stirring condition, within 2.0h After adding, react at this temperature for 8 hours, keep the temperature in the reaction bottle no more than 30°C during the reaction, then raise the temperature to 45°C, and add NaOH solution with a mass fraction of 50% (NaOH and epichlorohydrin mole The ratio is n _NaOH :n _{epichlorohydrin} =1:1.3), after dropping, maintain 45°C for 1h reaction, after the reaction, remove NaCl by filtration, then distill under reduced pressure to remove the remaining reactant, ethanol and water. ;

(6) Weigh 4g of the above-mentioned vat dye ozone fastness improving agent, add water to dilute to 100mL, dip the hemp fabric dyed with indigo into it, take it out after 5min, roll and press the fabric, two dips and two rolls, the excess rate is 90% , then dried at 80°C, then baked at 120°C for 3 minutes, washed 5 times with water, soaped and dried.

Comparative example 2

(1) Add 250mL of ethanol to a 1000mL three-necked flask, then add 0.2mol of triethylenetetramine, stir for 20 minutes, then raise the temperature of the water bath to 30°C, add 1.2mol of epichlorohydrin dropwise under stirring, and finish adding within 2.0h. Then react at this temperature for 8h, keep the temperature in the reaction bottle no more than 30°C during the reaction, then raise the temperature to 45°C, and add dropwise a NaOH solution with a mass fraction of 50% in 2h (the molar ratio of NaOH to epichlorohydrin is n _NaOH :n _{epichlorohydrin} =1:1.3), after dropping, maintain 45 DEG C to react for 1h, after the reaction finishes, filter to remove NaCl, then remove residual reactant, ethanol and water by vacuum distillation, and get final product;

(2) Weigh 4g of the above product, add water to dilute to 100mL, dip the hemp fabric dyed with indigo into it, take it out after 5min, roll and press the fabric, two dips and two rolls, the excess rate is 90%, and then dry at 80°C , and then baked at 120°C for 3 minutes, then washed 5 times with water, soaped and dried.

Example 3

(1) Weigh 0.15mol of ethylenediamine and 3.0mol of methanol and add them successively into a three-necked flask with magnetic stirring, reflux condenser and thermometer, put them in an ice-water bath and add 1.2mol of methyl acrylate dropwise under stirring conditions Esters; react at 28°C for 36h after the dropwise addition, then use a rotary evaporator to distill off the solvent methanol and excess methyl acrylate under reduced pressure at 30°C and 125P pressure, and dry under vacuum at 70°C for 18h to obtain 0.5 generation Ester-terminated PAMAM;

(2) Add 50mmol of the above-mentioned 0.5 generation PAMAM and 3.0mol methanol successively into a three-necked flask with magnetic stirring, reflux condenser, and thermometer, put it into an ice-water bath, and add ethylenediamine dropwise under stirring conditions (n _{0.5 Replacing PAMAM} : n _{ethylenediamine} =1:16); After the dropwise addition, react at 28°C for 36h, then at 30°C and 125P pressure, carry out vacuum distillation with a rotary evaporator to remove solvent methanol and excess ethylenediamine , dried under vacuum at 70°C for 18 hours to obtain 1.0-generation amine-terminated PAMAM;

(3) Repeat the Michael addition and amidation condensation reactions according to the feeding ratio and operating conditions of (1) and (2), respectively, to obtain 1.5 generation, 2.0 generation, 2.5 generation, 3.0 generation, and 3.5 generation PAMAM;

(4) 50mmol of the above-mentioned 3.5 generation PAMAM and 3.0mol methanol were successively added into a three-necked flask with magnetic stirring, reflux condenser, and thermometer, put into an ice-water bath and added tetraethylenepentamine dropwise under stirring conditions, 3.5 The molar ratio of PAMAM and tetraethylenepentamine is n _{3.5 generation PAMAM} : n _{tetraethylenepentamine} = 1:16; after the dropwise addition is completed, react at 28°C for 36h, then use a rotary evaporator at 30°C and 125P pressure The solvent methanol and excess tetraethylenepentamine were distilled off under reduced pressure, and vacuum-dried at 70°C for 18 hours to obtain tetraethylenepentamine-modified PAMAM;

(5) Add 250mL ethanol to a 1000mL three-necked flask, then add 0.2mol tetraethylenepentamine-modified PAMAM, stir for 15 minutes, raise the temperature of the water bath to 29°C, add 0.8mol epichlorohydrin dropwise under stirring conditions, within 1.5h After adding, react at this temperature for 6 hours, keep the temperature in the reaction bottle no more than 30 DEG C during the reaction, then raise the temperature to 42 DEG C, and dropwise add NaOH solution with a mass fraction of 50% (NaOH and epichlorohydrin mole The ratio is n _NaOH :n _{epichlorohydrin} =1:1.2), after dropping, maintain 42 DEG C to react for 1.5h, after the reaction finishes, remove NaCl by filtration, then remove residual reactants, ethanol and water by distillation under reduced pressure, namely Can;

(6) Weigh 3g of the above-mentioned vat dye ozone fastness improving agent, add water to dilute to 100mL, dip the cotton and linen blended fabric dyed with indigo into it, take it out after 3min, roll and press the fabric, two dips and two rolls, the excess rate 80%, then dried at 80°C, then baked at 130°C for 4 minutes, then washed 4 times with water, soaped and dried.

Comparative example 3

(1) Weigh 0.15mol of ethylenediamine and 3.0mol of methanol and add them successively into a three-necked flask with magnetic stirring, reflux condenser and thermometer, put them in an ice-water bath and add 1.2mol of methyl acrylate dropwise under stirring conditions Esters; react at 28°C for 36h after the dropwise addition, then use a rotary evaporator to distill off the solvent methanol and excess methyl acrylate under reduced pressure at 30°C and 125P pressure, and dry under vacuum at 70°C for 18h to obtain 0.5 generation Ester-terminated PAMAM;

(2) Add 50mmol of the above-mentioned 0.5 generation PAMAM and 3.0mol methanol successively into a three-necked flask with magnetic stirring, reflux condenser, and thermometer, put it into an ice-water bath, and add ethylenediamine dropwise under stirring conditions (n _{0.5 Replacing PAMAM} : n _{ethylenediamine} =1:16); After the dropwise addition, react at 28°C for 36h, then at 30°C and 125P pressure, carry out vacuum distillation with a rotary evaporator to remove solvent methanol and excess ethylenediamine , dried under vacuum at 70°C for 18 hours to obtain 1.0-generation amine-terminated PAMAM;

(3) Repeat the Michael addition and amidation condensation reactions according to the feeding ratio and operating conditions of (1) and (2) respectively, and then obtain 1.5 generations of PAMAM respectively;

(4) 50mmol of the above-mentioned 1.5 generation PAMAM and 3.0mol methanol were successively added to a three-necked flask with magnetic stirring, reflux condenser, and thermometer, put into an ice-water bath and added tetraethylenepentamine dropwise under stirring conditions, 1.5 The molar ratio of substituted PAMAM and tetraethylenepentamine is n _{1.5 substituted PAMAM} :n _{tetraethylenepentamine} =1:16; after the dropwise addition, react at 28°C for 36h, then use a rotary evaporator at 30°C and 125P pressure The solvent methanol and excess tetraethylenepentamine were distilled off under reduced pressure, and vacuum-dried at 70°C for 18 hours to obtain tetraethylenepentamine-modified PAMAM;

(5) Add 250mL ethanol to a 1000mL three-necked flask, then add 0.2mol tetraethylenepentamine-modified PAMAM, stir for 15 minutes, raise the temperature of the water bath to 29°C, add 0.8mol epichlorohydrin dropwise under stirring conditions, within 1.5h After adding, react at this temperature for 6 hours, keep the temperature in the reaction bottle no more than 30 DEG C during the reaction, then raise the temperature to 42 DEG C, and dropwise add NaOH solution with a mass fraction of 50% (NaOH and epichlorohydrin mole The ratio is n _NaOH :n _{epichlorohydrin} =1:1.2), after dropping, maintain 42 DEG C to react for 1.5h, after the reaction finishes, remove NaCl by filtration, then remove residual reactants, ethanol and water by distillation under reduced pressure, namely Can;

(6) Weigh 3g of the above-mentioned vat dye ozone fastness improving agent, add water to dilute to 100mL, dip the cotton and linen blended fabric dyed with indigo into it, take it out after 3min, roll and press the fabric, two dips and two rolls, the excess rate 80%, then dried at 80°C, then baked at 130°C for 4 minutes, then washed 4 times with water, soaped and dried.

Example 4

(1) Weigh 0.15 mol of ethylenediamine and 4.0 mol of methanol into a three-necked flask with magnetic stirring, reflux condenser, and thermometer, put it into an ice-water bath, and add 1.1 mol of methyl acrylate dropwise under stirring conditions Esters; react at 27°C for 28h after the dropwise addition, then use a rotary evaporator to distill off the solvent methanol and excess methyl acrylate under reduced pressure at 30°C and 125P pressure, and dry under vacuum at 65°C for 16h to obtain 0.5 generation Ester-terminated PAMAM;

(2) Add 50mmol of the above-mentioned 0.5 generation PAMAM and 4.0mol methanol successively into a three-necked flask with magnetic stirring, reflux condenser, and thermometer, put it into an ice-water bath, and add ethylenediamine dropwise under stirring conditions (n _{0.5 Replacing PAMAM} : n _{ethylenediamine} =1:12); After the dropwise addition, react at 27°C for 28h, then at 30°C and 125P pressure, use a rotary evaporator to carry out vacuum distillation to remove solvent methanol and excess ethylenediamine , dried under vacuum at 65°C for 16 hours to obtain 1.0-generation amine-terminated PAMAM;

(3) Repeat the Michael addition and amidation condensation reactions according to the feeding ratio and operating conditions of (1) and (2), respectively, to obtain 1.5 generation, 2.0 generation, 2.5 generation, 3.0 generation, and 3.5 generation PAMAM;

(4) Add 50 mmol of the above-mentioned 3.5-generation PAMAM and 4.0 mol of methanol successively into a three-necked flask with magnetic stirring, reflux condenser, and thermometer, put it in an ice-water bath, and add tetraethylenepentamine 3.5-generation dropwise under stirring conditions. The molar ratio of PAMAM and tetraethylenepentamine is n _{3.5 generation PAMAM} : n _{tetraethylenepentamine} =1:12; after the dropwise addition, react at 27°C for 28h, then at 30°C and 125P pressure, use a rotary evaporator to reduce The solvent methanol and excess tetraethylenepentamine were removed by pressure distillation, and vacuum-dried at 65°C for 16 hours to obtain tetraethylenepentamine-modified PAMAM;

(5) Add 250mL ethanol to a 1000mL three-necked flask, then add 0.2mol polyethylene polyamine modified PAMAM, stir for 12 minutes, then heat up the water bath to 30°C, add 1.0mol epichlorohydrin dropwise under stirring conditions, within 1.2h After adding, react at this temperature for 7 hours, keep the temperature in the reaction bottle no more than 30°C during the reaction, then raise the temperature to 43°C, add 50% NaOH solution (NaOH and epichlorohydrin mole Ratio is n _NaOH :n _{epichlorohydrin} =1:1.15), after dropping, maintain 43 ℃ of reaction 1.2h, after reaction finishes, filter and remove NaCl, then depressurizing distillation removes residual reactant, ethanol and water, namely Can;

(6) Weigh 3.5g of the above-mentioned vat dye ozone fastness improving agent, add water to dilute to 100mL, dip the viscose fabric dyed with indigo into it, take it out after 4min, roll and press the fabric, two dips and two rolls, the excess rate 75%, then dried at 80°C, then baked at 150°C for 3.5 minutes, washed 5 times with water, soaped and dried.

Example 5

Place the indigo-dyed pure cotton fabric, embodiment 1-4, and the fabric obtained in comparative example 1-3 in the self-made ozone fading test device, and the test device refers to GB/T l1039.3-2005 "Textile Color Fastness Test Air Pollution Resistance Color Fastness Part 3: Atmospheric Ozone", test its color fastness to ozone. The sample size is 7.5cm×4cm, the test temperature is (30±5)°C, the relative humidity is (85±5)%, the ozone concentration is 0.9787mg/L, and the test time is 180s. The SF600 computer color measuring and matching instrument (D65 light source, 10° viewing angle, 9.9 mm aperture) of American Datacolor Company was used to measure the discoloration level of the color samples before and after treatment, and the results are shown in Table 1.

Table 1 Finished Fabric Ozone Fastness Test Results

From the experimental data of Examples 1-4, it can be seen that after the indigo-dyed fabric is finished with the ozone-resistant color fastness improving agent, its ozone fading resistance is significantly improved, from the original unfinished level 1-2 to about 3 levels . Comparative Example 1 directly uses diethylenetriamine modified PAMAM to finish the dyed fabric. Since the finishing agent does not contain active groups, the combination fastness between the finishing agent and the textile is poor, and the finishing fabric is not washable. After washing, The ozone fading fastness of the fabric has not been significantly improved. Comparative example 2 directly adopts the reaction of triethylenetetramine and epichlorohydrin to prepare the ozone fastness improving agent, compared with PAMAM, the amount of amino groups contained in triethylenetetramine is less, through its finishing fabric, the ozone fading fastness slightly improved. In comparative example 3, PAMAM has less algebra, and the number of amino groups contained in the finishing agent is also less, and the improvement of the ozone fading fastness is not obvious after finishing the fabric.

Claims (8)

1. A vat dye ozone fastness improving agent, characterized in that: the epoxy-terminated hyperbranched polyamide-amine synthesized by polyethylene polyamine modified PAMAM and epichlorohydrin as main raw materials. 2. a kind of vat dye ozone fastness improving agent according to claim 1, is characterized in that: first utilize the Michael addition reaction between ethylenediamine and methyl acrylate to prepare 3.5 generation polyamide-amine (PAMAM) The dendritic macromolecule is reacted with polyethylene polyamine to prepare polyethylene polyamine modified PAMAM, and then reacted with epichlorohydrin and polyethylene polyamine modified PAMAM to prepare epoxy-terminated hyperbranched polyamide-amine. 3. a kind of vat dye ozone fastness improving agent according to claim 2, is characterized in that: concrete steps are as follows: (1) Weigh 0.15 mol of ethylenediamine and 2.0-5.0 mol of methanol and add them to a three-necked flask with magnetic stirring, reflux condenser and thermometer, put them in an ice-water bath and add 0.9-1.5 mol dropwise under stirring conditions. mol of methyl acrylate; after the dropwise addition, react at 25-30°C for 24-48h, then at 30°C and 125P pressure, use a rotary evaporator to distill off the solvent methanol and excess methyl acrylate under reduced pressure. Vacuum drying at -80°C for 12-24 hours to obtain 0.5-generation ester end group PAMAM; (2) 50mmol of the above-mentioned 0.5 generation PAMAM and 2.0-5.0mol methanol were successively added to a three-necked flask with magnetic stirring, a reflux condenser, and a thermometer, and they were put into an ice-water bath, and ethylenediamine was added dropwise under stirring conditions ( n _{0.5 generation PAMAM} : n _{ethylenediamine} = 1:8-1:24); after the dropwise addition, react at 25-30°C for 24-48h, then depressurize with a rotary evaporator at 30°C and 125P pressure The solvent methanol and excess ethylenediamine were distilled off, and vacuum-dried at 60-80°C for 12-24 hours to obtain 1.0-generation amine-terminated PAMAM; (3) Repeat the Michael addition and amidation condensation reactions according to the feeding ratio and operating conditions of (1) and (2), respectively, to obtain 1.5 generation, 2.0 generation, 2.5 generation, 3.0 generation, and 3.5 generation PAMAM; (4) Add 50 mmol of the above-mentioned 3.5-generation PAMAM and 2.0-5.0 mol of methanol successively into a three-necked flask with magnetic stirring, reflux condenser, and thermometer, put it in an ice-water bath, and add polyethylene polyamine drop by drop under stirring conditions ;After the dropwise addition, react at 25-30°C for 24-48h, then at 30°C and 125P pressure, use a rotary evaporator to carry out vacuum distillation to remove solvent methanol and excess polyethylene polyamine, vacuum at 60-80°C Dry for 12-24 hours to obtain polyethylene polyamine modified PAMAM; (5) Add 250mL ethanol to a 1000mL three-necked flask, then add 0.2mol polyethylene polyamine modified PAMAM, stir for 10-20min, then heat up the water bath to 28-30°C, add epichlorohydrin dropwise under stirring, 1.0 Add within -2.0h, then react at this temperature for 5-8h, keep the temperature in the reaction bottle not exceeding 30°C during the reaction, then raise the temperature to 40-45°C, add NaOH solution with a mass fraction of 50% at a constant speed within 2h , after the drop, maintain 40-45 ° C for 1-2h, after the reaction, filter to remove NaCl, and then distill under reduced pressure to remove the remaining reactants, ethanol and water. 4. a kind of vat dye ozone fastness improving agent according to claim 3, is characterized in that: the polyethylene polyamine described in step (4) is diethylenetriamine, triethylenetetramine, tetraethylenepenta One of the amines, the molar ratio of 3.5-generation PAMAM to polyethylene polyamine is n _{3.5-generation PAMAM} :n _{polyethylene polyamine} =1:8-1:24. 5. described a kind of vat dye ozone fastness improving agent according to claim 3, it is characterized in that: polyethylene polyamine modified PAMAM described in step (5) and epichlorohydrin mol ratio are n _{Polyethylene polyamine modified PAMAM} :n _{epichlorohydrin} =1:3-1:6, the molar ratio of NaOH to epichlorohydrin is n _NaOH :n _{epichlorohydrin} =1:1.1-1:1.3. 6. the application of a kind of vat dye ozone fastness improving agent according to claim 1 in textiles. 7. the application of a kind of vat dye ozone fastness improving agent according to claim 6 in textiles, is characterized in that: carry out as follows: Weigh 2-4g of the vat dye ozone fastness improving agent, add water to dilute to 100mL, soak the textile in it, take it out after 2-5min, roll and press the fabric, two dipping and two rolling, the excess rate is 70%-90%, and then Dry at 80°C, then bake at 100-150°C for 3-5 minutes, then wash with water 3-5 times, soap boil and dry. 8. The application of a vat dye ozone fastness improving agent according to claim 7 in textiles, characterized in that: said textiles are one or both blended products of cotton, linen and viscose fabrics .