CN101736619B - Cation type reactive polyurethane coloring stabilizer and preparation method thereof - Google Patents
Cation type reactive polyurethane coloring stabilizer and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a cation type reactive polyurethane coloring stabilizer seen in a molecular formula (I) and a preparation method of the coloring stabilizer. The method comprises the following steps of: weighing 34-804 parts of polyalcohol, 12-596 parts of diisocyanate, 0.2-7 parts of catalyst, 2-100 parts of polyhydroxy tertiary amines compound, 6-236 parts of alkylation reagent, 2-40 parts of sealant, 20-120 parts of organic solvent a, 20-120 parts of organic solvent b, 30-120 parts of organic solvent c, 2.5-40 parts of acidification reagent and 60-900 parts of deionized water according to proportion by weight; sequentially preparing polyurethane prepolymer; carrying out chain extending reaction, sealing reaction and alkylation reaction, removing the solvent and emulsifying to obtain the coloring stabilizer. The coloring stabilizer and the preparation method are used for dyeing and treating, can improve the dyed washing fastness and the dry and wet friction color fastness of anion type dyes and maintain the soft hand feel of fabrics. In the formula, X is a sealed group, Y is a diisocyanate main group, Z is a polyurethane soft segment, and R and R' are alkyl or alkylhydroxyl.
Description
Technical field
The invention belongs to the textile dyeing and finishing technical field, be specifically related to a kind of cation type reactive polyurethane coloring stabilizer, the invention still further relates to the preparation method of this color-fixing agent.
Background technology
Textiles is after dyeing such as anionic dyestuff such as direct dyes, ACID DYES; Its wet process COLOR FASTNESS is relatively poor; Promptly use the fabric of reactive dyeing; Its fastness to wet rubbing also is not enough to satisfy quality requirement, so generally also must pass through fixation treatment, each item COLOR FASTNESS standard that just can reach dress and use.Color-fixing agent such as color fixing agent Y, color fixing agent M and crosslinking agent DE are disabled because of containing free formaldehyde.Using more aldehyde-free colour stabilizer at present is polyamines family macromolecule compound mostly; Like the color-fixing agent DM-2518 of Guangzhou dolantin chemical industry Co., Ltd, the aldehyde-free colour stabilizer TF-233 of Zhejiang development of evil in febrile disease chemistry Group Co.,Ltd etc.; Direct dyes, reactive dyeing that these color-fixing agent are applied to cotton textiles, polyester-cotton blend and wash binding textiles have colour fixation preferably, but to very general than the colour fixation of fabrics such as deep-colour fabric and silk, wool.
Summary of the invention
The purpose of this invention is to provide a kind of cation type reactive polyurethane coloring stabilizer, solved existing color-fixing agent the bad problem of colour fixation than fabrics such as deep-colour fabric and silk, wools.
Another object of the present invention provides the preparation method of above-mentioned cation type reactive polyurethane coloring stabilizer.
The technical scheme that the present invention adopted is, a kind of cation type reactive polyurethane coloring stabilizer, and its molecular formula is:
In the formula, X-blocking groups; Y-vulcabond main body group; Z-flexible polyurethane section;
R, R '-alkyl or alkane hydroxyl.
Another technical scheme that the present invention adopted is, a kind of method for preparing above-mentioned color-fixing agent is specifically implemented according to following steps:
Step 1:, take by weighing 34-804 part polyvalent alcohol, 12-596 part vulcabond, 0.2-7 part catalyst, 2-100 part polyhydroxy tertiary amine compounds, 6-236 part alkylating reagent, 2-40 part sealer, 20-120 part organic solvent a, 20-120 part organic solvent b, 30-120 part organic solvent c, 2.5-40 part acidizing reagent and 60-900 part deionized water according to weight ratio;
Step 2: the preparation of base polyurethane prepolymer for use as
The polyvalent alcohol that step 1 takes by weighing is inserted in the reactor, and the vacuum purifying is 1-2 hour under 100-110 ℃ condition, cools to add the organic solvent a that step 1 takes by weighing after 30-60 ℃; Obtain the polyvalent alcohol behind the purifying, in the reactor of drying, add the vulcabond that step 1 takes by weighing, the polyvalent alcohol under nitrogen protection behind the dropping purifying; And add the catalyst that step 1 takes by weighing; The control temperature insulation reaction 1-2.5 hour, obtains base polyurethane prepolymer for use as at 40-90 ℃;
Step 3: chain extending reaction
The base polyurethane prepolymer for use as that step 2 is made cools to 35-60 ℃, under nitrogen protection, drips the polyhydroxy tertiary amine compounds that step 1 takes by weighing, and reacts 1-2.5 hour, makes the polymer that end group is an isocyanate groups;
Step 4: capping
The polymer of step 3 preparation is cooled to 2-10 ℃, under the high speed shear of 600-5000r/m, add the organic solvent b that step 1 takes by weighing, add the sealer that step 1 takes by weighing again, capping 0.5-2 hour, obtain end-blocked polyether polyols with reduced unsaturation;
Step 5: alkylated reaction
In the end-blocked polyether polyols with reduced unsaturation that step 4 makes, add the organic solvent c that step 1 takes by weighing, be warmed up to 50-120 ℃, drip the alkylating reagent that step 1 takes by weighing, back flow reaction 2-5 hour, obtain the polyurethane/cationic ester polymer;
Step 6: remove solvent and emulsification
Polyurethane/cationic ester polymer decompression distillation under vacuum condition that step 5 is made removes organic solvent; Be cooled to room temperature; Acidizing reagent with step 1 takes by weighing is regulated the pH value to 5.5-6.5; Add the deionized water that step 1 takes by weighing then, under the high speed shear of 1000-5000r/m emulsification 0.5-1 hour, obtain the cation type reactive polyurethane coloring stabilizer of emulsion form.
Characteristics of the present invention also are,
Polyvalent alcohol wherein adopts polyoxyethylene enediol, polyoxypropyleneglycol, polytetrahydrofuran diol, polyethylene glycol adipate glycol, gathers adipic acid diglycol esterdiol, gathers adipic acid-1; 4-butanediol ester glycol, gather adipate glycol-propylene glycol ester glycol or gather carbonic acid-1; A kind of in the 6-hexylene glycol esterdiol, or wherein two or more mixtures.
Vulcabond wherein adopts IPDI, Methylcyclohexyl diisocyanate, dicyclohexyl methyl hydride diisocyanate, the stupid dimethylene diisocyanate of tetramethyl, 1; Hexamethylene-diisocyanate, toluene di-isocyanate(TDI), stupid dimethylene diisocyanate, naphthalene-1; 5-vulcabond or diphenyl methane-4,4 '-a kind of in the vulcabond.
Wherein catalyst adopts a kind of in dibutyl tin laurate, stannous octoate, lead octoate, cobalt octoate, iron octoate, zinc naphthenate or metatitanic acid four isobutyl esters.
Wherein organic solvent adopts acetone, butanone, N, a kind of in dinethylformamide, N-Methyl pyrrolidone, ethyl acetate, butyl acetate, toluene, pyridine or the oxolane.
Wherein polyhydroxy tertiary amine compounds adopts triethanolamine, N-alkyl diethanol amine, N-isopropyl diethanol amine, N-ethyldiethanolamine, N butyl diethanol amine or 3-dimethylamino-1, a kind of in the 2-propylene glycol, or wherein two or more mixtures.
Wherein sealer adopts a kind of in sodium hydrogensulfite, methyl ethyl ketoxime, phenol or the caprolactam.
Wherein alkylating reagent adopts a kind of in dimethyl suflfate, dithyl sulfate, dimethyl carbonate, diethyl carbonate, ethylene dimethyl, dimethyl malenate, dimethyl succinate, dimethyl glutarate, benzyl chloride, cylite, bromoalkane or the idoalkane.
Wherein acidizing reagent adopts a kind of in oxalic acid, glacial acetic acid, propionic acid, hydrochloric acid, sulfuric acid or the nitric acid.
The invention has the beneficial effects as follows that this color-fixing agent is used for the textile dyeing post processing, can improve the washing fastness and dried, wet friction COLOR FASTNESS of various anionic dyeings, and keep fabrics feel soft.
The specific embodiment
Below in conjunction with the specific embodiment the present invention is elaborated.
Cation type reactive polyurethane coloring stabilizer of the present invention, its structural formula is:
In the formula, the X blocking groups; Y-vulcabond main body group; Z-flexible polyurethane section;
R, R '-alkyl, alkane hydroxyl etc.
The preparation method of cation type reactive polyurethane coloring stabilizer of the present invention, specifically implement according to following steps:
Step 1:, take by weighing 34-804 part polyvalent alcohol, 12-596 part vulcabond, 0.2-7 part catalyst, 2-100 part polyhydroxy tertiary amine compounds, 6-236 part alkylating reagent, 2-40 part sealer, 20-120 part organic solvent a, 20-120 part organic solvent b, 30-120 part organic solvent c, 2.5-40 part acidizing reagent and 60-900 part deionized water according to weight ratio;
Polyvalent alcohol wherein adopts polyoxyethylene enediol (polyethylene glycol; PEG), polyoxypropyleneglycol (polypropylene glycol; PPG), polytetrahydrofuran diol (PTMG), polyethylene glycol adipate glycol (PEA), gather adipic acid diglycol esterdiol (PDA), gather adipic acid-1; 4-butanediol ester glycol (PBA), gather adipate glycol-propylene glycol ester glycol or gather carbonic acid-1, the mixture of one or more in the 6-hexylene glycol esterdiol (PHC);
Vulcabond wherein adopts IPDI (IPDI), Methylcyclohexyl diisocyanate (HTDI), dicyclohexyl methyl hydride diisocyanate (HMDI), the stupid dimethylene diisocyanate of tetramethyl (TMXDI), 1; Hexamethylene-diisocyanate (HDI), toluene di-isocyanate(TDI) (TDI), stupid dimethylene diisocyanate (XDI), naphthalene-1; 5-vulcabond (NDI) or diphenyl methane-4,4 '-a kind of in the vulcabond (MDI);
Wherein catalyst adopts a kind of in dibutyl tin laurate (DBTDL), stannous octoate, lead octoate (24%Pb), cobalt octoate (6%Co), iron octoate (6%Fe), zinc naphthenate (14.5%Zn) or metatitanic acid four isobutyl esters;
Organic solvent a wherein, organic solvent b, organic solvent c adopt acetone, butanone, N, a kind of in dinethylformamide (DMF), N-Methyl pyrrolidone, ethyl acetate, butyl acetate, toluene, pyridine or the oxolane;
Polyhydroxy tertiary amine compounds wherein adopts triethanolamine (TEA), N-alkyl diethanol amine (MDEA), N-isopropyl diethanol amine, N-ethyldiethanolamine (EDEA), N butyl diethanol amine (BDEA) or 3-dimethylamino-1, the mixture of one or more in the 2-propylene glycol;
Wherein sealer adopts a kind of in sodium hydrogensulfite, methyl ethyl ketoxime, phenol or the caprolactam;
Wherein alkylating reagent adopts a kind of in dimethyl suflfate, dithyl sulfate, dimethyl carbonate, diethyl carbonate, ethylene dimethyl, dimethyl malenate, dimethyl succinate, dimethyl glutarate, benzyl chloride, cylite, bromoalkane or the idoalkane;
Wherein acidizing reagent adopts a kind of in oxalic acid, glacial acetic acid, propionic acid, hydrochloric acid, sulfuric acid or the nitric acid.
Step 2: the preparation of base polyurethane prepolymer for use as
The polyvalent alcohol that step 1 is taken by weighing drops in the reactor, and the vacuum purifying is 1-2 hour under 100-110 ℃ condition, cools to add 20-120 part organic solvent a that step 1 takes by weighing after 30-60 ℃, seals subsequent use.In the reactor of drying, add the vulcabond that step 1 takes by weighing, the polyvalent alcohol under nitrogen protection behind the above-mentioned purifying of dropping, and add the catalyst that step 1 takes by weighing, the control temperature insulation reaction 1-2.5 hour, obtains base polyurethane prepolymer for use as at 40-90 ℃;
Step 3: chain extending reaction
The base polyurethane prepolymer for use as that step 2 is made cools to 35-60 ℃, under nitrogen protection, drips the polyhydroxy tertiary amine compounds that step 1 takes by weighing, and reacts 1-2.5 hour, makes the polymer that end group is an isocyanate groups;
Step 4: capping
The polymer of step 3 preparation is cooled to 2-10 ℃, under the high speed shear of 600-5000r/min, add the organic solvent b that step 1 takes by weighing, add the sealer that step 1 takes by weighing again fast, capping 0.5-2 hour, obtain end-blocked polyether polyols with reduced unsaturation;
Step 5: alkylated reaction
In the end-blocked polyether polyols with reduced unsaturation that step 4 makes, add the organic solvent c that step 1 takes by weighing, be warmed up to 50-120 ℃, drip the alkylating reagent that step 1 takes by weighing, back flow reaction 2-5 hour, obtain the polyurethane/cationic ester polymer.
Step 6: remove solvent and emulsification
Polyurethane/cationic ester polymer decompression distillation under vacuum condition that step 5 is made removes organic solvent; Be cooled to room temperature; Acidizing reagent with step 1 takes by weighing is regulated the pH value to 5.5-6.5; Add the deionized water that step 1 takes by weighing then,, obtain the cation type reactive polyurethane coloring stabilizer of emulsion form with high-speed emulsifying machine under 1000-5000r/min emulsification 0.5-1 hour.
Cation type reactive polyurethane coloring stabilizer of the present invention has been introduced the quaternary ammonium group cation group on the polyurethane macromolecular chain, can combine with ionic bond with the dyestuff anionic group on the fiber, reduces the water-soluble of dyestuff; Simultaneously; Owing to adopted the lower sealer of deblocking temperature, when high temperature baked, the sealing base on the color-fixing agent molecule was separated and is honored as a queen; Discharge the reactive group of capacity; Can also form covalent bonds with hydroxyl on fiber and the dye molecule, amino, carboxylic hydroxyl etc., thereby improve COLOR FASTNESS, especially the wet process COLOR FASTNESS of dyestuff.Because the polyurethane high polymer has characteristics such as excellent elasticity and pliability, the color-fixing agent of this color-fixing agent and other types is compared, and handles the soft of back fabric.
Embodiment 1
Step 1: polyurethane prepolymerization reaction
34 parts of PPG1000 are dropped in the reactors,, add 20 parts of acetone after cooling to 50 ℃, seal subsequent use 100-110 ℃ of following vacuum purifying 1-2 hour.In the reactor of drying, add 12 parts of HDI, under nitrogen protection, drip above-mentioned 33.5 parts PPG1000 with dropping funel, and add 0.2 part of catalyst dibutyl tin laurate, the control temperature is at 60 ℃, and insulation reaction 1 hour makes base polyurethane prepolymer for use as.
Step 2: chain extending reaction
The base polyurethane prepolymer for use as that makes in the above-mentioned steps 1 is cooled to 50 ℃, under nitrogen protection, drip 2 parts of MDEA, carry out chain extending reaction, the reaction time is 1 hour, makes the polymer that end group is an isocyanate groups.
Step 3: capping
The polymer of preparation in the above-mentioned steps 2 is cooled to 4 ℃, under the high speed shear of 1000r/min, add 20 parts of isopropyl alcohols, add 2 parts sealer sodium hydrogensulfite more fast, capping 1.5 hours obtains end-blocked polyether polyols with reduced unsaturation.
Step 4: alkylated reaction
In the end-blocked polyether polyols with reduced unsaturation that in above-mentioned steps 3, makes, add 30 parts of isopropyl alcohols, be warmed up to 50 ℃, drip 6 parts of alkylating reagent bromohexadecanes, back flow reaction 2 hours obtains the polyurethane/cationic ester polymer.
Step 5: remove solvent and emulsification
Polyurethane/cationic ester polymer decompression distillation under vacuum condition that above-mentioned steps 4 is made removes organic solvent; Be cooled to room temperature; Regulate pH value to 5.5 with 2.5 parts of glacial acetic acid; Add 60 parts of deionized waters then,, obtain the cation type reactive polyurethane coloring stabilizer emulsion with high-speed emulsifying machine emulsification 0.8 hour under 2000r/min.
Embodiment 2
Step 1: polyurethane prepolymerization reaction
With 600 parts of PTMG600,204 parts of PEG600 drop in the reactors, 100-110 ℃ of following vacuum purifying 1-2 hour, add 120 parts of acetone after cooling to 30 ℃, seal subsequent use.In the reactor of drying, add 596 parts of IPDI, under nitrogen protection, drip the mixture of above-mentioned polyvalent alcohol with dropping funel, and add 7 parts of catalyst dibutyl tin laurates, the control temperature is at 65 ℃, and insulation reaction 2.5 hours makes base polyurethane prepolymer for use as.
Step 2: chain extending reaction
The base polyurethane prepolymer for use as that makes in the above-mentioned steps 1 is cooled to 55 ℃, under nitrogen protection, drip 100 parts of TEA, carry out chain extending reaction, the reaction time is 2.5 hours, makes the polymer that end group is an isocyanate groups.
Step 3: capping
The polymer of preparation in the above-mentioned steps 2 is cooled to 4 ℃, add 120 parts of absolute ethyl alcohols under the high speed shear of 3000r/min, add 40 parts sealer sodium hydrogensulfite fast, capping 1.5 hours obtains end-blocked polyether polyols with reduced unsaturation.
Step 4: alkylated reaction
In the end-blocked polyether polyols with reduced unsaturation that in above-mentioned steps 3, makes, add 120 parts of isopropyl alcohols, be warmed up to 120 ℃, drip 236 parts of alkylating reagent iodohexadecanes, back flow reaction 2 hours obtains the polyurethane/cationic ester polymer.
Step 5: remove solvent and emulsification
Polyurethane/cationic ester polymer decompression distillation under vacuum condition that above-mentioned steps 4 is made removes organic solvent; Be cooled to room temperature; Regulate pH value to 6.5 with 40 parts of glacial acetic acid; Add 900 parts of deionized waters then,, obtain the cation type reactive polyurethane coloring stabilizer emulsion with high-speed emulsifying machine emulsification 0.5 hour under 1500r/min.
Embodiment 3
Step 1: polyurethane prepolymerization reaction
With 60 parts of PEA1000,30 parts of PEG1000 drop in the reactors, 100-110 ℃ of following vacuum purifying 1-2 hour, add 40 parts of ethyl acetate after cooling to 60 ℃, seal subsequent use.In the reactor of drying, add 31.4 parts of TDI, under nitrogen protection, drip the mixture of above-mentioned polyvalent alcohol with dropping funel, and add the inferior tin of 0.6 part of octoate catalyst, the control temperature is at 55 ℃, and insulation reaction 2.5 hours makes base polyurethane prepolymer for use as.
Step 2: chain extending reaction
The base polyurethane prepolymer for use as that makes in the above-mentioned steps 1 is cooled to 35 ℃; Under nitrogen protection, drip the mixture of 4.5 parts of N-isopropyl diethanol amine and 2.4 parts of BDEA, carry out chain extending reaction; Reaction time is 1.5 hours, makes the polymer that end group is an isocyanate groups.
Step 3: capping
The polymer of preparation in the above-mentioned steps 2 is cooled to 2 ℃, add 60 parts of isopropyl alcohols under the high speed shear of 600r/min, add 4.2 parts sealer phenol fast, capping 2 hours obtains end-blocked polyether polyols with reduced unsaturation.
Step 4: alkylated reaction
In the end-blocked polyether polyols with reduced unsaturation that in above-mentioned steps 3, makes, add 60 parts of normal propyl alcohols, be warmed up to 65 ℃, drip 14.5 parts of alkylating reagent dithyl sulfates, back flow reaction 2.5 hours obtains the polyurethane/cationic ester polymer.
Step 5: remove solvent and emulsification
Polyurethane/cationic ester polymer decompression distillation under vacuum condition that above-mentioned steps 4 is made removes organic solvent; Be cooled to room temperature; With 4.5 parts of salt acid for adjusting pH value to 5.0; Add 230 parts of deionized waters then,, obtain the cation type reactive polyurethane coloring stabilizer emulsion with high-speed emulsifying machine emulsification 1 hour under 1000r/min.
Embodiment 4
Step 1: polyurethane prepolymerization reaction
With 60 parts of PHC1500,30 parts of PEA1000,30 parts of PEG1000 drop in the reactors, 100-110 ℃ of following vacuum purifying 1-2 hour, add 60 parts of ethyl acetate after cooling to 50 ℃, seal subsequent use.In the reactor of drying, add 60 parts of MDI, under nitrogen protection, drip the mixture of above-mentioned polyvalent alcohol with dropping funel, and add the inferior tin of 0.9 part of octoate catalyst, the control temperature is at 40 ℃, and insulation reaction 1.5 hours makes base polyurethane prepolymer for use as.
Step 2: chain extending reaction
The base polyurethane prepolymer for use as that makes in the above-mentioned steps 1 is cooled to 45 ℃; Under nitrogen protection; Drip 4.5 parts of N-isopropyl diethanol amine, 2.4 parts of BDEA and 1.8 parts of 3-dimethylamino-1, the mixture of 2-propylene glycol carries out chain extending reaction; Reaction time is 1.5 hours, makes the polymer that end group is an isocyanate groups.
Step 3: capping
The polymer of preparation in the above-mentioned steps 2 is cooled to 10 ℃, add 80 parts of isopropyl alcohols under the high speed shear of 1000r/min, add 5.6 parts sealer sodium hydrogensulfite fast, capping 0.5 hour obtains end-blocked polyether polyols with reduced unsaturation.
Step 4: alkylated reaction
In the end-blocked polyether polyols with reduced unsaturation that in above-mentioned steps 3, makes, add 80 parts of isopropyl alcohols, be warmed up to 60 ℃, drip 9.35 parts of alkylating reagent dithyl sulfates, back flow reaction 5 hours obtains the polyurethane/cationic ester polymer.
Step 5: remove solvent and emulsification
Polyurethane/cationic ester polymer decompression distillation under vacuum condition that above-mentioned steps 4 is made removes organic solvent; Be cooled to room temperature; With 6.0 parts of sulphur acid for adjusting pH value to 6.0; Add 300 parts of deionized waters then,, obtain the cation type reactive polyurethane coloring stabilizer emulsion with high-speed emulsifying machine emulsification 1 hour under 1500r/min.
Embodiment 5
Step 1: polyurethane prepolymerization reaction
With 60 parts of PHC1500,30 parts of PEA1000,40 parts of PPG800 drop in the reactors, 100-110 ℃ of following vacuum purifying 1-2 hour, add 70 parts of ethyl acetate after cooling to 50 ℃, seal subsequent use.In the reactor of drying, add 63 parts of HMDI, under nitrogen protection, drip the mixture of above-mentioned polyvalent alcohol with dropping funel, and add 0.4 part of octoate catalyst lead (24%Pb), the control temperature is at 90 ℃, and insulation reaction 2 hours makes base polyurethane prepolymer for use as.
Step 2: chain extending reaction
The base polyurethane prepolymer for use as that makes in the above-mentioned steps 1 is cooled to 60 ℃; Under nitrogen protection; Drip 4.5 parts of N-isopropyl diethanol amine, 2.4 parts of BDEA and 1.8 parts of 3-dimethylamino-1, the mixture of 2-propylene glycol carries out chain extending reaction; Reaction time is 2 hours, makes the polymer that end group is an isocyanate groups.
Step 3: capping
The polymer of preparation in the above-mentioned steps 2 is cooled to 5 ℃, add 75 parts of isopropyl alcohols under the high speed shear of 1000r/min, add 6.7 parts sealer caprolactam fast, capping 1.5 hours obtains end-blocked polyether polyols with reduced unsaturation.
Step 4: alkylated reaction
In the end-blocked polyether polyols with reduced unsaturation that in above-mentioned steps 3, makes, add 75 parts of isopropyl alcohols, be warmed up to 70 ℃, drip 7.1 parts of alkylating reagent ethylene dimethyls, back flow reaction 2 hours obtains the polyurethane/cationic ester polymer.
Step 5: remove solvent and emulsification
Polyurethane/cationic ester polymer decompression distillation under vacuum condition that above-mentioned steps 4 is made removes organic solvent; Be cooled to room temperature; Regulate pH value to 6.0 with 6.5 parts of glacial acetic acid; Add 320 parts of deionized waters then,, obtain the cation type reactive polyurethane coloring stabilizer emulsion with high-speed emulsifying machine emulsification 1 hour under 1500r/min.
The comparing result of table 1 the present invention and other color-fixing agent
| The color-fixing agent kind | Do/fastness to wet rubbing (level) | WASHING COLOR FASTNESS (level) | Feel | Formaldehyde |
| Color-fixing agent DM-2518 | 3-4/2-3 | 3-4 | Harder | Do not have |
| Color-fixing agent TF-233 | 3-4/2-3 | 3-4 | Harder | Do not have |
| The embodiment of the invention 1 | 4/3 | 4 | Soft | Do not have |
| The embodiment of the invention 2 | 4/3-4 | 4 | Soft | Do not have |
| The embodiment of the invention 3 | 4/3-4 | 4 | Soft | Do not have |
| The embodiment of the invention 4 | 4/3-4 | 4 | Soft | Do not have |
| The embodiment of the invention 5 | 4/3-4 | 4 | Soft | Do not have |
| The embodiment of the invention 6 | 4/3 | 4 | Soft | Do not have |
Annotate: 1. dried, fastness to wet rubbing: GB/T3920-1997
2. soaping fastness: GB/T3921.1-1997
3. formaldehyde: GB/T2912.1-1998. first aqueous extraction method
Can find out that from table 1 color-fixing agent of the present invention has cationic and the double grading response type color-fixing agent concurrently, and because the flexibility and the resilient characteristic of polyurethane, arrangement back fabrics feel soft, the doing of DYED FABRICS, fastness to wet rubbing and washing fastness are all splendid.
Claims (2)
1. a cation type reactive polyurethane coloring stabilizer is characterized in that, its molecular formula is:
In the formula, the X-blocking groups; Y-vulcabond main body group; Z-flexible polyurethane section; R, R '-alkyl or alkane hydroxyl.
2. a method for preparing the said color-fixing agent of claim 1 is characterized in that, specifically implements according to following steps:
Step 1: polyurethane prepolymerization reaction
34 parts of polyoxypropyleneglycols 1000 are dropped in the reactors,, add 20 parts of acetone after cooling to 50 ℃ 100-110 ℃ of following vacuum purifying 1-2 hour; Seal subsequent usely, in the reactor of drying, add 12 parts of hexamethylene diisocyanates; Under nitrogen protection, drip above-mentioned polyoxypropyleneglycol 1000 with dropping funel, and add 0.2 part of catalyst dibutyl tin laurate, the control temperature is at 60 ℃; Insulation reaction 1 hour makes base polyurethane prepolymer for use as;
Step 2: chain extending reaction
The base polyurethane prepolymer for use as that makes in the above-mentioned steps 1 is cooled to 50 ℃, under nitrogen protection, drip 2 parts of N-alkyl diethanol amine, carry out chain extending reaction, the reaction time is 1 hour, makes the polymer that end group is an isocyanate groups;
Step 3: capping
The polymer of preparation in the above-mentioned steps 2 is cooled to 4 ℃, under the high speed shear of 1000r/min, add 20 parts of isopropyl alcohols, add 2 parts sealer sodium hydrogensulfite more fast, capping 1.5 hours obtains end-blocked polyether polyols with reduced unsaturation;
Step 4: alkylated reaction
In the end-blocked polyether polyols with reduced unsaturation that in above-mentioned steps 3, makes, add 30 parts of isopropyl alcohols, be warmed up to 50 ℃, drip 6 parts of alkylating reagent bromohexadecanes, back flow reaction 2 hours obtains the polyurethane/cationic ester polymer;
Step 5: remove solvent and emulsification
Polyurethane/cationic ester polymer decompression distillation under vacuum condition that above-mentioned steps 4 is made removes organic solvent; Be cooled to room temperature; Regulate pH value to 5.5 with 2.5 parts of glacial acetic acid; Add 60 parts of deionized waters then,, obtain the cation type reactive polyurethane coloring stabilizer emulsion with high-speed emulsifying machine emulsification 0.8 hour under 2000r/min;
Perhaps,
Step 1: polyurethane prepolymerization reaction
600,204 parts of polyoxyethylene enediols of 600 parts of polytetrahydrofuran diols 600 are dropped in the reactors, 100-110 ℃ of following vacuum purifying 1-2 hour; Add 120 parts of acetone after cooling to 30 ℃, seal subsequent use, 596 parts of IPDIs of adding in the reactor of drying; Under nitrogen protection, drip the mixture of above-mentioned polyvalent alcohol with dropping funel, and add 7 parts of catalyst dibutyl tin laurates, the control temperature is at 65 ℃; Insulation reaction 2.5 hours makes base polyurethane prepolymer for use as;
Step 2: chain extending reaction
The base polyurethane prepolymer for use as that makes in the above-mentioned steps 1 is cooled to 55 ℃, under nitrogen protection, drip 100 parts of triethanolamines, carry out chain extending reaction, the reaction time is 2.5 hours, makes the polymer that end group is an isocyanate groups;
Step 3: capping
The polymer of preparation in the above-mentioned steps 2 is cooled to 4 ℃, add 120 parts of absolute ethyl alcohols under the high speed shear of 3000r/min, add 40 parts sealer sodium hydrogensulfite fast, capping 1.5 hours obtains end-blocked polyether polyols with reduced unsaturation;
Step 4: alkylated reaction
In the end-blocked polyether polyols with reduced unsaturation that in above-mentioned steps 3, makes, add 120 parts of isopropyl alcohols, be warmed up to 120 ℃, drip 236 parts of alkylating reagent iodohexadecanes, back flow reaction 2 hours obtains the polyurethane/cationic ester polymer;
Step 5: remove solvent and emulsification
Polyurethane/cationic ester polymer decompression distillation under vacuum condition that above-mentioned steps 4 is made removes organic solvent; Be cooled to room temperature; Regulate pH value to 6.5 with 40 parts of glacial acetic acid; Add 900 parts of deionized waters then,, obtain the cation type reactive polyurethane coloring stabilizer emulsion with high-speed emulsifying machine emulsification 0.5 hour under 1500r/min;
Perhaps,
Step 1: polyurethane prepolymerization reaction
1000,30 parts of polyoxyethylene enediols of 60 parts of polyethylene glycol adipate glycol 1000 are dropped in the reactors, 100-110 ℃ of following vacuum purifying 1-2 hour; Add 40 parts of ethyl acetate after cooling to 60 ℃, seal subsequent use, 31.4 parts of toluene di-isocyanate(TDI)s of adding in the reactor of drying; Under nitrogen protection, drip the mixture of above-mentioned polyvalent alcohol with dropping funel, and add the inferior tin of 0.6 part of octoate catalyst, the control temperature is at 55 ℃; Insulation reaction 2.5 hours makes base polyurethane prepolymer for use as;
Step 2: chain extending reaction
The base polyurethane prepolymer for use as that makes in the above-mentioned steps 1 is cooled to 35 ℃; Under nitrogen protection, drip the mixture of 4.5 parts of N-isopropyl diethanol amine and 2.4 parts of N butyl diethanol amines, carry out chain extending reaction; Reaction time is 1.5 hours, makes the polymer that end group is an isocyanate groups;
Step 3: capping
The polymer of preparation in the above-mentioned steps 2 is cooled to 2 ℃, add 60 parts of isopropyl alcohols under the high speed shear of 600r/min, add 4.2 parts sealer phenol fast, capping 2 hours obtains end-blocked polyether polyols with reduced unsaturation;
Step 4: alkylated reaction
In the end-blocked polyether polyols with reduced unsaturation that in above-mentioned steps 3, makes, add 60 parts of normal propyl alcohols, be warmed up to 65 ℃, drip 14.5 parts of alkylating reagent dithyl sulfates, back flow reaction 2.5 hours obtains the polyurethane/cationic ester polymer;
Step 5: remove solvent and emulsification
Polyurethane/cationic ester polymer decompression distillation under vacuum condition that above-mentioned steps 4 is made removes organic solvent; Be cooled to room temperature; With 4.5 parts of salt acid for adjusting pH value to 5.0; Add 230 parts of deionized waters then,, obtain the cation type reactive polyurethane coloring stabilizer emulsion with high-speed emulsifying machine emulsification 1 hour under 1000r/min;
Perhaps,
Step 1: polyurethane prepolymerization reaction
Gather carbonic acid-1,1500,30 parts of polyethylene glycol adipate glycol 1000 of 6-hexylene glycol esterdiol with 60 parts; 30 parts of polyoxyethylene enediols 1000 drop in the reactors, 100-110 ℃ of following vacuum purifying 1-2 hour, add 60 parts of ethyl acetate after cooling to 50 ℃; Seal subsequent use, in the reactor of drying, add 60 parts of diphenyl methanes-4,4 '-vulcabond; Under nitrogen protection, drip the mixture of above-mentioned polyvalent alcohol with dropping funel, and add the inferior tin of 0.9 part of octoate catalyst, the control temperature is at 40 ℃; Insulation reaction 1.5 hours makes base polyurethane prepolymer for use as;
Step 2: chain extending reaction
The base polyurethane prepolymer for use as that makes in the above-mentioned steps 1 is cooled to 45 ℃; Under nitrogen protection; Drip 4.5 parts of N-isopropyl diethanol amine, 2.4 parts of N butyl diethanol amines and 1.8 parts of 3-dimethylamino-1, the mixture of 2-propylene glycol carries out chain extending reaction; Reaction time is 1.5 hours, makes the polymer that end group is an isocyanate groups;
Step 3: capping
The polymer of preparation in the above-mentioned steps 2 is cooled to 10 ℃, add 80 parts of isopropyl alcohols under the high speed shear of 1000r/min, add 5.6 parts sealer sodium hydrogensulfite fast, capping 0.5 hour obtains end-blocked polyether polyols with reduced unsaturation;
Step 4: alkylated reaction
In the end-blocked polyether polyols with reduced unsaturation that in above-mentioned steps 3, makes, add 80 parts of isopropyl alcohols, be warmed up to 60 ℃, drip 9.35 parts of alkylating reagent dithyl sulfates, back flow reaction 5 hours obtains the polyurethane/cationic ester polymer;
Step 5: remove solvent and emulsification
Polyurethane/cationic ester polymer decompression distillation under vacuum condition that above-mentioned steps 4 is made removes organic solvent; Be cooled to room temperature; With 6.0 parts of sulphur acid for adjusting pH value to 6.0; Add 300 parts of deionized waters then,, obtain the cation type reactive polyurethane coloring stabilizer emulsion with high-speed emulsifying machine emulsification 1 hour under 1500r/min;
Perhaps,
Step 1: polyurethane prepolymerization reaction
Gather carbonic acid-1,1500,30 parts of polyethylene glycol adipate glycol 1000 of 6-hexylene glycol esterdiol with 60 parts; 40 parts of polyoxypropyleneglycols 800 drop in the reactors, 100-110 ℃ of following vacuum purifying 1-2 hour, add 70 parts of ethyl acetate after cooling to 50 ℃; Seal subsequent usely, in the reactor of drying, add 63 parts of dicyclohexyl methyl hydride diisocyanates, under nitrogen protection, drip the mixture of above-mentioned polyvalent alcohol with dropping funel; And add 0.4 part of octoate catalyst lead; The control temperature is at 90 ℃, and insulation reaction 2 hours makes base polyurethane prepolymer for use as;
Step 2: chain extending reaction
The base polyurethane prepolymer for use as that makes in the above-mentioned steps 1 is cooled to 60 ℃; Under nitrogen protection; Drip 4.5 parts of N-isopropyl diethanol amine, 2.4 parts of N butyl diethanol amines and 1.8 parts of 3-dimethylamino-1, the mixture of 2-propylene glycol carries out chain extending reaction; Reaction time is 2 hours, makes the polymer that end group is an isocyanate groups;
Step 3: capping
The polymer of preparation in the above-mentioned steps 2 is cooled to 5 ℃, add 75 parts of isopropyl alcohols under the high speed shear of 1000r/min, add 6.7 parts sealer caprolactam fast, capping 1.5 hours obtains end-blocked polyether polyols with reduced unsaturation;
Step 4: alkylated reaction
In the end-blocked polyether polyols with reduced unsaturation that in above-mentioned steps 3, makes, add 75 parts of isopropyl alcohols, be warmed up to 70 ℃, drip 7.1 parts of alkylating reagent ethylene dimethyls, back flow reaction 2 hours obtains the polyurethane/cationic ester polymer;
Step 5: remove solvent and emulsification
Polyurethane/cationic ester polymer decompression distillation under vacuum condition that above-mentioned steps 4 is made removes organic solvent; Be cooled to room temperature; Regulate pH value to 6.0 with 6.5 parts of glacial acetic acid; Add 320 parts of deionized waters then,, obtain the cation type reactive polyurethane coloring stabilizer emulsion with high-speed emulsifying machine emulsification 1 hour under 1500r/min.
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| CN101914857B (en) * | 2010-08-04 | 2012-04-11 | 辽宁恒星精细化工有限公司 | Method for preparing reactive polyurethane film-forming color fixing agent |
| CN102251416B (en) * | 2011-04-15 | 2013-06-26 | 西安工程大学 | Waterborne polyurethane graft-modified polyamine color fixing agent and preparation method thereof |
| CN103421158B (en) * | 2013-08-06 | 2015-07-29 | 陕西科技大学 | A kind of preparation method and application's method of the fixing and hyperchromicity agent for superfine fiber chemical leather dyeing |
| CN103614935A (en) * | 2013-11-21 | 2014-03-05 | 湖州厉华妤婕联合纺织有限公司 | Improved color fixative for textiles |
| CN105175672A (en) * | 2015-10-22 | 2015-12-23 | 上海上萃精细化工有限公司 | Anionic polyurethane color fixative and synthesis method thereof |
| CN105625062B (en) * | 2016-01-25 | 2018-05-15 | 东莞市佳乾新材料科技有限公司 | A kind of preparation method for the titanium modified aqueous polyurethane color fixing agent for being used to weave |
| CN106758413B (en) * | 2016-12-12 | 2018-11-02 | 江西德盛精细化学品有限公司 | A kind of preparation method of activity chlorine-resistant aldehyde-free colour stabilizer and color fixing agent obtained |
| CN106996046A (en) * | 2017-03-07 | 2017-08-01 | 吉安迅达科技有限公司 | The factory formula and production technology of a kind of long effective environmental protection type color fixing agent |
| CN106917308B (en) * | 2017-04-10 | 2019-01-15 | 南通大学 | A kind of dedicated color fixing agent of cotton-polyester blended fabric co-bathing dyeing |
| CN107964116B (en) * | 2017-08-02 | 2019-09-13 | 合肥思敬齐化工材料有限责任公司 | A kind of water-soluble additives and preparation method thereof of cationic ultraviolet radiation preventing |
| CN110156953B (en) * | 2019-05-29 | 2021-02-05 | 苏州大学 | Color fixing agent for reactive dye and preparation method thereof |
| CN110804146B (en) * | 2019-12-06 | 2021-09-07 | 万华化学集团股份有限公司 | Storage-stable closed isocyanate composition and preparation method and application thereof |
| CN112250833A (en) * | 2020-10-23 | 2021-01-22 | 万桦（常州）新材料科技有限公司 | Synthetase and fabric color fixing method |
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