CN106633049B - A kind of reducing dye ozone fastness elevator and its preparation method and application - Google Patents
A kind of reducing dye ozone fastness elevator and its preparation method and application Download PDFInfo
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- CN106633049B CN106633049B CN201611109173.2A CN201611109173A CN106633049B CN 106633049 B CN106633049 B CN 106633049B CN 201611109173 A CN201611109173 A CN 201611109173A CN 106633049 B CN106633049 B CN 106633049B
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- pamam
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- reducing dye
- polyethylene polyamine
- ozone
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- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 230000001603 reducing effect Effects 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229920000768 polyamine Polymers 0.000 claims abstract description 29
- 239000004698 Polyethylene Substances 0.000 claims abstract description 28
- -1 polyethylene Polymers 0.000 claims abstract description 28
- 239000004744 fabric Substances 0.000 claims abstract description 26
- 229920000573 polyethylene Polymers 0.000 claims abstract description 24
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims abstract description 22
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000004753 textile Substances 0.000 claims abstract description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 141
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 69
- 238000013019 agitation Methods 0.000 claims description 48
- 238000005292 vacuum distillation Methods 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 239000005457 ice water Substances 0.000 claims description 24
- 238000010992 reflux Methods 0.000 claims description 24
- 239000002904 solvent Substances 0.000 claims description 23
- 238000009833 condensation Methods 0.000 claims description 22
- 230000005494 condensation Effects 0.000 claims description 22
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 19
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 16
- 235000019441 ethanol Nutrition 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- 238000001291 vacuum drying Methods 0.000 claims description 16
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 14
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 9
- 150000001412 amines Chemical group 0.000 claims description 9
- 238000009835 boiling Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 238000002386 leaching Methods 0.000 claims description 9
- 239000000344 soap Substances 0.000 claims description 9
- 229960001124 trientine Drugs 0.000 claims description 9
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 8
- 230000009435 amidation Effects 0.000 claims description 8
- 238000007112 amidation reaction Methods 0.000 claims description 8
- 150000002148 esters Chemical class 0.000 claims description 8
- 239000000376 reactant Substances 0.000 claims description 8
- 239000011780 sodium chloride Substances 0.000 claims description 8
- 229920000742 Cotton Polymers 0.000 claims description 7
- 238000007598 dipping method Methods 0.000 claims description 4
- 229920000297 Rayon Polymers 0.000 claims description 3
- 239000000835 fiber Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229920000962 poly(amidoamine) Polymers 0.000 claims 12
- 238000006482 condensation reaction Methods 0.000 claims 1
- 235000000177 Indigofera tinctoria Nutrition 0.000 abstract description 11
- 229940097275 indigo Drugs 0.000 abstract description 11
- COHYTHOBJLSHDF-UHFFFAOYSA-N indigo powder Natural products N1C2=CC=CC=C2C(=O)C1=C1C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-UHFFFAOYSA-N 0.000 abstract description 11
- 238000005562 fading Methods 0.000 abstract description 8
- 238000006845 Michael addition reaction Methods 0.000 abstract description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 2
- 239000000975 dye Substances 0.000 description 18
- 238000004043 dyeing Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 3
- 240000008564 Boehmeria nivea Species 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 description 2
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/028—Polyamidoamines
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/22—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using vat dyestuffs including indigo
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/52—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing synthetic macromolecular substances
- D06P1/5264—Macromolecular compounds obtained otherwise than by reactions involving only unsaturated carbon-to-carbon bonds
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Coloring (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The present invention with the indigo reducing dye for representative by ozone influenced and cause its dyed fabric fade aiming at the problem that, a kind of reducing dye ozone fastness elevator is provided, be epoxy-terminated ultrabranching polyamide-amine.The preparation method of above-mentioned reducing dye ozone fastness elevator is, 3.5 polyamide-amine (PAMAM) dendritic macromole is prepared first with the Michael addition reaction between ethylenediamine and methyl acrylate, the modified PAMAM of polyethylene polyamine is prepared with polyethylene polyamine reaction again, then it is reacted with epoxychloropropane with the modified PAMAM of polyethylene polyamine, prepares epoxy-terminated ultrabranching polyamide-amine.Above-mentioned reducing dye ozone fastness elevator can be applied in textile.The resulting reducing dye ozone fastness elevator of the present invention significantly improves the resistance to ozone fading fastness of adsorption volume.
Description
Technical field
The invention belongs to technical field of textile chemistry, and in particular to a kind of reducing dye ozone fastness elevator and its system
Preparation Method and application.
Background technique
With the quickening of process of industrialization and the sharp increase of city automobile quantity, ozone concentration is gradually risen in air.As
A kind of electrophilic reagent, ozone understand the electronics pair in the unsaturated structures such as attack carbon-carbon double bond, lead to unsaturated organic molecular structure
Variation.To contain a large amount of unsaturated bond in the indigo reducing dye molecular structure for representative, ozone concentration is quick in air
Increase, the colour fading of reducing dye dyed fabric certainly will be will lead to.Resistance to ozone jail of the external many companies for inlet and outlet textile
Degree proposes corresponding requirement, and therefore, it is tight to solve certain reducing dyes chance ozone that urgent need develops a kind of ozone fastness elevator
It fades again this defect, there is no people to study in the field both at home and abroad at present.
Summary of the invention
Technical problem to be solved by the present invention lies in overcome to be influenced and lead by ozone with the indigo reducing dye for representative
The problem of causing its dyed fabric to fade provides a kind of reducing dye ozone fastness elevator and its preparation method and application.
To solve above-mentioned technical problem the technical solution adopted by the present invention is that: first with ethylenediamine and methyl acrylate it
Between Michael addition reaction prepare 3.5 polyamide-amine (PAMAM) dendritic macromole, then with polyethylene polyamine reaction system
Then the standby modified PAMAM of polyethylene polyamine is reacted with the modified PAMAM of polyethylene polyamine with epoxychloropropane, is prepared epoxy-terminated
Ultrabranching polyamide-amine improves the binding strength of PAMAM and textile, utilizes a large amount of reproducibility in PAMAM molecular structure
Amino to achieve the purpose that prevent dyed textiles from fading with ozone reaction, protection reducing dye.
The preparation method of above-mentioned reducing dye ozone fastness elevator, the specific steps are as follows:
(1) it weighs 0.15mol ethylenediamine and 2.0-5.0mol methanol is successively added to magnetic agitation, reflux condensation mode
It manages, in the three-necked flask of thermometer, is put into the methyl acrylate that 0.9-1.5mol is added dropwise in ice-water bath dropwise under agitation；
24-48h is reacted after dripping at 25-30 DEG C, then under 30 DEG C, 125P pressure, is evaporated under reduced pressure with Rotary Evaporators
It removes solvent methanol and excessive methacrylate and obtains 0.5 generation ester terminal PAMAM in 60-80 DEG C of vacuum drying 12-24h；
(2) above-mentioned 0.5 generation PAMAM and the 2.0-5.0mol methanol of 50mmol is successively added to magnetic agitation, reflux
Condenser pipe, thermometer three-necked flask in, be put into ice-water bath under agitation dropwise be added dropwise ethylenediamine (n0.5 generation PAMAM:nEthylenediamine
=1:8-1:24)；24-48h is reacted after being added dropwise to complete at 25-30 DEG C, then under 30 DEG C, 125P pressure, uses rotary evaporation
Instrument carries out vacuum distillation removing solvent methanol and excessive ethylenediamine and obtains 1.0 generation amine in 60-80 DEG C of vacuum drying 12-24h
End group PAMAM；
(3) it respectively according to the feed ratio and operating condition of (1) and (2), repeats Michael's addition and amidation condensation is anti-
It answers, then respectively obtains 1.5 generations, 2.0 generations, 2.5 generations, 3.0 generations, 3.5 generation PAMAM；
(4) above-mentioned 3.5 generation PAMAM and the 2.0-5.0mol methanol of 50mmol is successively added to magnetic agitation, reflux
Condenser pipe, thermometer three-necked flask in, be put into ice-water bath and polyethylene polyamine be added dropwise dropwise under agitation；It is added dropwise to complete
24-48h is reacted at 25-30 DEG C afterwards, then under 30 DEG C, 125P pressure, it is molten to carry out vacuum distillation removing with Rotary Evaporators
Agent methanol and excessive polyethylene polyamine obtain the modified PAMAM of polyethylene polyamine in 60-80 DEG C of vacuum drying 12-24h；
(5) 250mL ethyl alcohol is added in 1000mL three-necked flask, the modified PAMAM of 0.2mol polyethylene polyamine is then added,
After stirring 10-20min, warming-in-water is added dropwise epoxychloropropane under stirring condition, adds in 1.0-2.0h, then to 28-30 DEG C
5-8h is reacted at this temperature, is kept temperature in reaction flask to be no more than 30 DEG C in reaction process, is then heated to 40-45 DEG C, 2h
The NaOH solution of mass fraction 50% is inside at the uniform velocity added dropwise, after dripping off, maintains 40-45 DEG C of reaction 1-2h, after reaction, crosses and filters out
NaCl is removed, then vacuum distillation removes remaining reactant, second alcohol and water.
Polyethylene polyamine described in step (4) be one of diethylenetriamine, triethylene tetramine, tetraethylenepentamine,
3.5 generation PAMAM and polyethylene polyamine molar ratio are n3.5 generation PAMAM:nPolyethylene polyamine=1:8-1:24.
The modified PAMAM of polyethylene polyamine described in step (5) and epoxychloropropane molar ratio are nPolyethylene polyamine is modified PAMAM:
nEpoxychloropropane=1:3-1:6, NaOH and epoxychloropropane molar ratio are nNaOH:nEpoxychloropropane=1:1.1-1:1.3.
As shown from the above technical solution: the present invention first will there is the polyethylene polyamine compared with strong reducing property to be introduced into PAMAM
In molecular structure, reducing dye is protected with ozone reaction using amino a large amount of in molecular structure, while it is more to solve more ethylene
Effumability present in the direct use process of amine has certain irritating problem；Using epoxychloropropane to polyethylene polyamine
Modified PAMAM carries out functionalization, using the reactivity worth between hydroxyl in epoxy group and cellulose fibre, to improve more second
The binding strength of alkene modified polyamine PAMAM and textile.
Above-mentioned reducing dye ozone fastness elevator can be applied in textile.
Its application carries out as follows:
Reducing dye ozone fastness elevator 2-4g is weighed, 100mL is diluted with water to, wherein by textile dipping, 2-
It is taken out after 5min, roll roll compacting fabric, two leachings two are rolled, and then pick-up 70%-90% is dried at 80 DEG C, then through 100-150 DEG C
3-5min is baked, is then washed 3-5 times, soap boiling, drying.
Textile described in above-mentioned applying step is one or both of cotton, fiber crops, viscose fabric blending product.
The beneficial effects of the present invention are:
(1) reducing dye is protected using the reproducibility of amino a large amount of in polyethylene polyamine and PAMAM molecular structure.
(2) binding strength of PAMAM molecule and textile is improved using the reactivity of epoxychloropropane.
Specific embodiment
Below with reference to specific embodiment, description is of the invention in further detail.It should be understood that these embodiments are intended merely to
It illustrates the present invention, rather than limits the scope of the invention in any way.
Embodiment 1
(1) it weighs 0.15mol ethylenediamine and 2.0mol methanol is successively added to magnetic agitation, reflux condensing tube, temperature
It spends in the three-necked flask of meter, is put into the methyl acrylate that 0.9mol is added dropwise in ice-water bath dropwise under agitation；After dripping
48h is reacted at 25 DEG C, then under 30 DEG C, 125P pressure, with Rotary Evaporators carry out vacuum distillation remove solvent methanol and
Excessive methacrylate is dried in vacuo for 24 hours at 60 DEG C, obtains 0.5 generation ester terminal PAMAM；
(2) above-mentioned 0.5 generation PAMAM and the 2.0mol methanol of 50mmol is successively added to magnetic agitation, reflux condensation mode
It manages, in the three-necked flask of thermometer, is put into ice-water bath and ethylenediamine (n is added dropwise dropwise under agitation0.5 generation PAMAM:nEthylenediamine=1:
8)；48h is reacted after being added dropwise to complete at 25 DEG C, then under 30 DEG C, 125P pressure, vacuum distillation is carried out with Rotary Evaporators and removes
Solvent methanol and excessive ethylenediamine are removed, is dried in vacuo for 24 hours at 60 DEG C, obtains 1.0 generation amine end groups PAMAM；
(3) it respectively according to the feed ratio and operating condition of (1) and (2), repeats Michael's addition and amidation condensation is anti-
It answers, then respectively obtains 1.5 generations, 2.0 generations, 2.5 generations, 3.0 generations, 3.5 generation PAMAM；
(4) above-mentioned 3.5 generation PAMAM and the 2.0mol methanol of 50mmol is successively added to magnetic agitation, reflux condensation mode
Pipe, thermometer three-necked flask in, be put into ice-water bath and diethylenetriamine be added dropwise dropwise under agitation, 3.5 generation PAMAM with
Diethylenetriamine molar ratio is n3.5 generation PAMAM:nDiethylenetriamine=1:8；48h is reacted after being added dropwise to complete at 25 DEG C, then 30 DEG C,
Under 125P pressure, vacuum distillation is carried out with Rotary Evaporators and removes solvent methanol and excessive diethylenetriamine, in 60 DEG C of vacuum
Drying for 24 hours, obtains the modified PAMAM of diethylenetriamine；
(5) 250mL ethyl alcohol is added in 1000mL three-necked flask, the modified PAMAM of 0.2mol diethylenetriamine is then added,
After stirring 10min, warming-in-water is added dropwise 0.6mol epoxychloropropane, adds in 1.0h, then herein to 28 DEG C under stirring condition
At a temperature of react 5h, keep temperature in reaction flask to be no more than 30 DEG C in reaction process, then heat to 40 DEG C, be at the uniform velocity added dropwise in 2h
(NaOH is n with epoxychloropropane molar ratio to the NaOH solution of mass fraction 50%NaOH:nEpoxychloropropane=1:1.1), after dripping off, dimension
It holds 40 DEG C of reaction 2h and is filtered to remove NaCl after reaction, then vacuum distillation removes remaining reactant, second alcohol and water, i.e.,
It can；
(6) above-mentioned reducing dye ozone fastness elevator 2g is weighed, 100mL is diluted with water to, it will be through indigo dyeing cotton
Fabric impregnates wherein, takes out after 2min, roll roll compacting fabric, and two leachings two are rolled, then pick-up 70% is dried at 80 DEG C, then passed through
100 DEG C bake 5min, then wash 3 times, soap boiling, drying.
Comparative example 1
(1) it weighs 0.15mol ethylenediamine and 2.0mol methanol is successively added to magnetic agitation, reflux condensing tube, temperature
It spends in the three-necked flask of meter, is put into the methyl acrylate that 0.9mol is added dropwise in ice-water bath dropwise under agitation；After dripping
48h is reacted at 25 DEG C, then under 30 DEG C, 125P pressure, with Rotary Evaporators carry out vacuum distillation remove solvent methanol and
Excessive methacrylate is dried in vacuo for 24 hours at 60 DEG C, obtains 0.5 generation ester terminal PAMAM；
(2) above-mentioned 0.5 generation PAMAM and the 2.0mol methanol of 50mmol is successively added to magnetic agitation, reflux condensation mode
It manages, in the three-necked flask of thermometer, is put into ice-water bath and ethylenediamine (n is added dropwise dropwise under agitation0.5 generation PAMAM:nEthylenediamine=1:
8)；48h is reacted after being added dropwise to complete at 25 DEG C, then under 30 DEG C, 125P pressure, vacuum distillation is carried out with Rotary Evaporators and removes
Solvent methanol and excessive ethylenediamine are removed, is dried in vacuo for 24 hours at 60 DEG C, obtains 1.0 generation amine end groups PAMAM；
(3) it respectively according to the feed ratio and operating condition of (1) and (2), repeats Michael's addition and amidation condensation is anti-
It answers, then respectively obtains 1.5 generations, 2.0 generations, 2.5 generations, 3.0 generations, 3.5 generation PAMAM；
(4) above-mentioned 3.5 generation PAMAM and the 2.0mol methanol of 50mmol is successively added to magnetic agitation, reflux condensation mode
Pipe, thermometer three-necked flask in, be put into ice-water bath and diethylenetriamine be added dropwise dropwise under agitation, 3.5 generation PAMAM with
Diethylenetriamine molar ratio is n3.5 generation PAMAM:nDiethylenetriamine=1:8；48h is reacted after being added dropwise to complete at 25 DEG C, then 30 DEG C,
Under 125P pressure, vacuum distillation is carried out with Rotary Evaporators and removes solvent methanol and excessive diethylenetriamine, in 60 DEG C of vacuum
Drying for 24 hours, obtains the modified PAMAM of diethylenetriamine；
(5) the modified PAMAM 2g of above-mentioned diethylenetriamine is weighed, 100mL is diluted with water to, the cotton through indigo dyeing is knitted
Object impregnates wherein, takes out after 2min, roll roll compacting fabric, and two leachings two are rolled, and then pick-up 70% is dried at 80 DEG C, then through 100
DEG C 5min is baked, then washed 3 times, soap boiling, drying.
Embodiment 2
(1) it weighs 0.15mol ethylenediamine and 5.0mol methanol is successively added to magnetic agitation, reflux condensing tube, temperature
It spends in the three-necked flask of meter, is put into the methyl acrylate that 1.5mol is added dropwise in ice-water bath dropwise under agitation；After dripping
Reacted at 30 DEG C for 24 hours, then under 30 DEG C, 125P pressure, with Rotary Evaporators carry out vacuum distillation remove solvent methanol and
Excessive methacrylate obtains 0.5 generation ester terminal PAMAM in 80 DEG C of vacuum drying 12h；
(2) above-mentioned 0.5 generation PAMAM and the 5.0mol methanol of 50mmol is successively added to magnetic agitation, reflux condensation mode
It manages, in the three-necked flask of thermometer, is put into ice-water bath and ethylenediamine (n is added dropwise dropwise under agitation0.5 generation PAMAM:nEthylenediamine=1:
24)；It reacts for 24 hours at 30 DEG C after being added dropwise to complete, then under 30 DEG C, 125P pressure, is evaporated under reduced pressure with Rotary Evaporators
It removes solvent methanol and excessive ethylenediamine and obtains 1.0 generation amine end groups PAMAM in 80 DEG C of vacuum drying 12h；
(3) it respectively according to the feed ratio and operating condition of (1) and (2), repeats Michael's addition and amidation condensation is anti-
It answers, then respectively obtains 1.5 generations, 2.0 generations, 2.5 generations, 3.0 generations, 3.5 generation PAMAM；
(4) above-mentioned 3.5 generation PAMAM and the 5.0mol methanol of 50mmol is successively added to magnetic agitation, reflux condensation mode
Pipe, thermometer three-necked flask in, be put into ice-water bath and triethylene tetramine be added dropwise dropwise under agitation, 3.5 generation PAMAM with
Triethylene tetramine molar ratio is n3.5 generation PAMAM:nTriethylene tetramine=1:24；Reacted for 24 hours at 30 DEG C after being added dropwise to complete, then 30 DEG C,
Under 125P pressure, vacuum distillation is carried out with Rotary Evaporators and removes solvent methanol and excessive triethylene tetramine, in 80 DEG C of vacuum
Dry 12h obtains the modified PAMAM of triethylene tetramine；
(5) 250mL ethyl alcohol is added in 1000mL three-necked flask, the modified PAMAM of 0.2mol triethylene tetramine is then added,
After stirring 20min, warming-in-water is added dropwise 1.2mol epoxychloropropane, adds in 2.0h, then herein to 30 DEG C under stirring condition
At a temperature of react 8h, keep temperature in reaction flask to be no more than 30 DEG C in reaction process, then heat to 45 DEG C, be at the uniform velocity added dropwise in 2h
(NaOH is n with epoxychloropropane molar ratio to the NaOH solution of mass fraction 50%NaOH:nEpoxychloropropane=1:1.3), after dripping off, dimension
It holds 45 DEG C of reaction 1h and is filtered to remove NaCl after reaction, then vacuum distillation removes remaining reactant, second alcohol and water, i.e.,
It can；
(6) above-mentioned reducing dye ozone fastness elevator 4g is weighed, 100mL is diluted with water to, it will be through indigo dyeing
Linen impregnates wherein, takes out after 5min, roll roll compacting fabric, and two leachings two are rolled, then pick-up 90% is dried at 80 DEG C, then
3min is baked through 120 DEG C, is then washed 5 times, soap boiling, drying.
Comparative example 2
(1) 250mL ethyl alcohol is added in 1000mL three-necked flask, 0.2mol triethylene tetramine is then added, stir 20min
Afterwards, warming-in-water is added dropwise 1.2mol epoxychloropropane, adds in 2.0h to 30 DEG C under stirring condition, then anti-at this temperature
8h is answered, keeps temperature in reaction flask to be no more than 30 DEG C in reaction process, then heats to 45 DEG C, mass fraction is at the uniform velocity added dropwise in 2h
(NaOH is n with epoxychloropropane molar ratio to 50% NaOH solutionNaOH:nEpoxychloropropane=1:1.3), after dripping off, 45 DEG C of maintenance are anti-
1h is answered, after reaction, is filtered to remove NaCl, then vacuum distillation removes remaining reactant, second alcohol and water；
(2) above-mentioned product 4g is weighed, 100mL is diluted with water to, wherein by the linen dipping through indigo dyeing, after 5min
It takes out, roll roll compacting fabric, two leachings two are rolled, pick-up 90%, are then dried at 80 DEG C, then bake 3min through 120 DEG C, then water
It washes 5 times, soap boiling, drying.
Embodiment 3
(1) it weighs 0.15mol ethylenediamine and 3.0mol methanol is successively added to magnetic agitation, reflux condensing tube, temperature
It spends in the three-necked flask of meter, is put into the methyl acrylate that 1.2mol is added dropwise in ice-water bath dropwise under agitation；After dripping
36h is reacted at 28 DEG C, then under 30 DEG C, 125P pressure, with Rotary Evaporators carry out vacuum distillation remove solvent methanol and
Excessive methacrylate obtains 0.5 generation ester terminal PAMAM in 70 DEG C of vacuum drying 18h；
(2) above-mentioned 0.5 generation PAMAM and the 3.0mol methanol of 50mmol is successively added to magnetic agitation, reflux condensation mode
It manages, in the three-necked flask of thermometer, is put into ice-water bath and ethylenediamine (n is added dropwise dropwise under agitation0.5 generation PAMAM:nEthylenediamine=1:
16)；36h is reacted after being added dropwise to complete at 28 DEG C, then under 30 DEG C, 125P pressure, is evaporated under reduced pressure with Rotary Evaporators
It removes solvent methanol and excessive ethylenediamine and obtains 1.0 generation amine end groups PAMAM in 70 DEG C of vacuum drying 18h；
(3) it respectively according to the feed ratio and operating condition of (1) and (2), repeats Michael's addition and amidation condensation is anti-
It answers, then respectively obtains 1.5 generations, 2.0 generations, 2.5 generations, 3.0 generations, 3.5 generation PAMAM；
(4) above-mentioned 3.5 generation PAMAM and the 3.0mol methanol of 50mmol is successively added to magnetic agitation, reflux condensation mode
Pipe, thermometer three-necked flask in, be put into ice-water bath and tetraethylenepentamine be added dropwise dropwise under agitation, 3.5 generation PAMAM with
Tetraethylenepentamine molar ratio is n3.5 generation PAMAM:nTetraethylenepentamine=1:16；36h is reacted after being added dropwise to complete at 28 DEG C, then 30 DEG C,
Under 125P pressure, vacuum distillation is carried out with Rotary Evaporators and removes solvent methanol and excessive tetraethylenepentamine, in 70 DEG C of vacuum
Dry 18h obtains the modified PAMAM of tetraethylenepentamine；
(5) 250mL ethyl alcohol is added in 1000mL three-necked flask, the modified PAMAM of 0.2mol tetraethylenepentamine is then added,
After stirring 15min, warming-in-water is added dropwise 0.8mol epoxychloropropane, adds in 1.5h, then herein to 29 DEG C under stirring condition
At a temperature of react 6h, keep temperature in reaction flask to be no more than 30 DEG C in reaction process, then heat to 42 DEG C, be at the uniform velocity added dropwise in 2h
(NaOH is n with epoxychloropropane molar ratio to the NaOH solution of mass fraction 50%NaOH:nEpoxychloropropane=1:1.2), after dripping off, dimension
It holds 42 DEG C of reaction 1.5h and is filtered to remove NaCl after reaction, then vacuum distillation removes remaining reactant, second alcohol and water,
?；
(6) above-mentioned reducing dye ozone fastness elevator 3g is weighed, 100mL is diluted with water to, it will be through indigo dyeing
Cotton ramie blended spinning fabric impregnates wherein, takes out after 3min, roll roll compacting fabric, and two leachings two are rolled, then pick-up 80% is dried at 80 DEG C
It is dry, then 4min is baked through 130 DEG C, it then washes 4 times, soap boiling, drying.
Comparative example 3
(1) it weighs 0.15mol ethylenediamine and 3.0mol methanol is successively added to magnetic agitation, reflux condensing tube, temperature
It spends in the three-necked flask of meter, is put into the methyl acrylate that 1.2mol is added dropwise in ice-water bath dropwise under agitation；After dripping
36h is reacted at 28 DEG C, then under 30 DEG C, 125P pressure, with Rotary Evaporators carry out vacuum distillation remove solvent methanol and
Excessive methacrylate obtains 0.5 generation ester terminal PAMAM in 70 DEG C of vacuum drying 18h；
(2) above-mentioned 0.5 generation PAMAM and the 3.0mol methanol of 50mmol is successively added to magnetic agitation, reflux condensation mode
It manages, in the three-necked flask of thermometer, is put into ice-water bath and ethylenediamine (n is added dropwise dropwise under agitation0.5 generation PAMAM:nEthylenediamine=1:
16)；36h is reacted after being added dropwise to complete at 28 DEG C, then under 30 DEG C, 125P pressure, is evaporated under reduced pressure with Rotary Evaporators
It removes solvent methanol and excessive ethylenediamine and obtains 1.0 generation amine end groups PAMAM in 70 DEG C of vacuum drying 18h；
(3) it respectively according to the feed ratio and operating condition of (1) and (2), repeats Michael's addition and amidation condensation is anti-
It answers, then respectively obtains 1.5 generation PAMAM；
(4) above-mentioned 1.5 generation PAMAM and the 3.0mol methanol of 50mmol is successively added to magnetic agitation, reflux condensation mode
Pipe, thermometer three-necked flask in, be put into ice-water bath and tetraethylenepentamine be added dropwise dropwise under agitation, 1.5 generation PAMAM with
Tetraethylenepentamine molar ratio is n1.5 generation PAMAM:nTetraethylenepentamine=1:16；36h is reacted after being added dropwise to complete at 28 DEG C, then 30 DEG C,
Under 125P pressure, vacuum distillation is carried out with Rotary Evaporators and removes solvent methanol and excessive tetraethylenepentamine, in 70 DEG C of vacuum
Dry 18h obtains the modified PAMAM of tetraethylenepentamine；
(5) 250mL ethyl alcohol is added in 1000mL three-necked flask, the modified PAMAM of 0.2mol tetraethylenepentamine is then added,
After stirring 15min, warming-in-water is added dropwise 0.8mol epoxychloropropane, adds in 1.5h, then herein to 29 DEG C under stirring condition
At a temperature of react 6h, keep temperature in reaction flask to be no more than 30 DEG C in reaction process, then heat to 42 DEG C, be at the uniform velocity added dropwise in 2h
(NaOH is n with epoxychloropropane molar ratio to the NaOH solution of mass fraction 50%NaOH:nEpoxychloropropane=1:1.2), after dripping off, dimension
It holds 42 DEG C of reaction 1.5h and is filtered to remove NaCl after reaction, then vacuum distillation removes remaining reactant, second alcohol and water,
?；
(6) above-mentioned reducing dye ozone fastness elevator 3g is weighed, 100mL is diluted with water to, it will be through indigo dyeing
Cotton ramie blended spinning fabric impregnates wherein, takes out after 3min, roll roll compacting fabric, and two leachings two are rolled, then pick-up 80% is dried at 80 DEG C
It is dry, then 4min is baked through 130 DEG C, it then washes 4 times, soap boiling, drying.
Embodiment 4
(1) it weighs 0.15mol ethylenediamine and 4.0mol methanol is successively added to magnetic agitation, reflux condensing tube, temperature
It spends in the three-necked flask of meter, is put into the methyl acrylate that 1.1mol is added dropwise in ice-water bath dropwise under agitation；After dripping
28h is reacted at 27 DEG C, then under 30 DEG C, 125P pressure, with Rotary Evaporators carry out vacuum distillation remove solvent methanol and
Excessive methacrylate obtains 0.5 generation ester terminal PAMAM in 65 DEG C of vacuum drying 16h；
(2) above-mentioned 0.5 generation PAMAM and the 4.0mol methanol of 50mmol is successively added to magnetic agitation, reflux condensation mode
It manages, in the three-necked flask of thermometer, is put into ice-water bath and ethylenediamine (n is added dropwise dropwise under agitation0.5 generation PAMAM:nEthylenediamine=1:
12)；28h is reacted after being added dropwise to complete at 27 DEG C, then under 30 DEG C, 125P pressure, is evaporated under reduced pressure with Rotary Evaporators
It removes solvent methanol and excessive ethylenediamine and obtains 1.0 generation amine end groups PAMAM in 65 DEG C of vacuum drying 16h；
(3) it respectively according to the feed ratio and operating condition of (1) and (2), repeats Michael's addition and amidation condensation is anti-
It answers, then respectively obtains 1.5 generations, 2.0 generations, 2.5 generations, 3.0 generations, 3.5 generation PAMAM；
(4) above-mentioned 3.5 generation PAMAM and the 4.0mol methanol of 50mmol is successively added to magnetic agitation, reflux condensation mode
Pipe, thermometer three-necked flask in, be put into ice-water bath under agitation dropwise be added dropwise 3.5 generation of tetraethylenepentamine PAMAM with
Tetraethylenepentamine molar ratio is n3.5 generation PAMAM:nTetraethylenepentamine=1:12；28h is reacted after being added dropwise to complete at 27 DEG C, then 30 DEG C,
Under 125P pressure, vacuum distillation is carried out with Rotary Evaporators and removes solvent methanol and excessive tetraethylenepentamine, in 65 DEG C of vacuum
Dry 16h obtains the modified PAMAM of tetraethylenepentamine；
(5) 250mL ethyl alcohol is added in 1000mL three-necked flask, the modified PAMAM of 0.2mol polyethylene polyamine is then added,
After stirring 12min, warming-in-water is added dropwise 1.0mol epoxychloropropane, adds in 1.2h, then herein to 30 DEG C under stirring condition
At a temperature of react 7h, keep temperature in reaction flask to be no more than 30 DEG C in reaction process, then heat to 43 DEG C, be at the uniform velocity added dropwise in 2h
(NaOH is n with epoxychloropropane molar ratio to the NaOH solution of mass fraction 50%NaOH:nEpoxychloropropane=1:1.15), after dripping off, dimension
It holds 43 DEG C of reaction 1.2h and is filtered to remove NaCl after reaction, then vacuum distillation removes remaining reactant, second alcohol and water,
?；
(6) above-mentioned reducing dye ozone fastness elevator 3.5g is weighed, 100mL is diluted with water to, it will be through indigo dyeing
Viscose fabric dipping wherein, taken out after 4min, roll roll compacting fabric, two leachings two are rolled, then pick-up 75% is dried at 80 DEG C
It is dry, then 3.5min is baked through 150 DEG C, it then washes 5 times, soap boiling, drying.
Embodiment 5
Fabric obtained by indigo dyeing pure cotton fabric, embodiment 1-4, comparative example 1-3 is placed in self-control ozone fading test dress
In setting, with reference to GB/T l1039.3-2005, " textile color stability tests the color fastness of resistance to atmosphere pollution third portion to experimental rig: big
Gas ozone ", test its color fastness to ozone.Specimen size is 7.5cm × 4cm, test temperature (30 ± 5) DEG C, relative humidity (85
± 5) %, ozone concentration 0.9787mg/L, testing time 180s.Matched using U.S.'s Datacolor company SF600 type Computer color testing
Color instrument (D65 light source, 10 ° of visual angles, the aperture 9.9mm) measures the discoloration rank of tinctorial pattern before and after the processing, as a result such as table 1.
1 finish fabric ozone fastness test result of table
Can be seen that from the experimental data of embodiment 1-4, adsorption volume through color fastness to ozone elevator arrangement after,
Resistance to ozone fading performance significantly improves, and 1-2 grade when by not arranging originally is increased to 3 grades or so.Comparative example 1 directlys adopt diethyl
The modified PAMAM of alkene triamine arranges dyed fabric, due to not containing active group in finishing agent, so that finishing agent and weaving
The binding strength of product is poor, and finish fabric is intolerant to washing, and after washed, the ozone fading fastness of fabric, which has no, to be significantly improved.It is right
Ratio 2 directlys adopt triethylene tetramine and epichlorohydrin reaction to prepare ozone fastness elevator, compared with PAMAM, three
The amino amount contained in ethylene tetramine is less, and through its finish fabric, ozone fading fastness is slightly improved.In comparative example 3,
The algebra of PAMAM is less, and the amino amount contained in finishing agent is also less, and through its finish fabric, ozone fading fastness is improved
It is less obvious.
Claims (6)
1. a kind of preparation method of reducing dye ozone fastness elevator, it is characterised in that: specific step is as follows:
(1) it weighs 0.15mol ethylenediamine and 2.0-5.0mol methanol is successively added to magnetic agitation, reflux condensing tube, temperature
It spends in the three-necked flask of meter, is put into the methyl acrylate that 0.9-1.5mol is added dropwise in ice-water bath dropwise under agitation；It is added dropwise
24-48h is reacted after complete at 25-30 DEG C, then under 30 DEG C, 125P pressure, carries out vacuum distillation removing with Rotary Evaporators
Solvent methanol and excessive methacrylate obtain 0.5 generation ester terminal PAMAM in 60-80 DEG C of vacuum drying 12-24h；
(2) above-mentioned 0.5 generation PAMAM and the 2.0-5.0mol methanol of 50mmol is successively added to magnetic agitation, reflux condensation mode
It manages, in the three-necked flask of thermometer, is put into ice-water bath and ethylenediamine is added dropwise dropwise under agitation, wherein n0.5 generation PAMAM:nEthylenediamine=1:8-1:24；24-48h is reacted after being added dropwise to complete at 25-30 DEG C, then under 30 DEG C, 125P pressure, is steamed with rotation
Hair instrument carries out vacuum distillation removing solvent methanol and excessive ethylenediamine and obtained for 1.0 generations in 60-80 DEG C of vacuum drying 12-24h
Amine end groups PAMAM；
(3) Michael's addition and amidation condensation reaction are repeated, then according to the feed ratio and operating condition of (1) and (2) respectively
Respectively obtain 1.5 generations, 2.0 generations, 2.5 generations, 3.0 generations, 3.5 generation PAMAM；
(4) above-mentioned 3.5 generation PAMAM and the 2.0-5.0mol methanol of 50mmol is successively added to magnetic agitation, reflux condensation mode
It manages, in the three-necked flask of thermometer, is put into ice-water bath and polyethylene polyamine is added dropwise dropwise under agitation；After being added dropwise to complete
24-48h is reacted at 25-30 DEG C, then under 30 DEG C, 125P pressure, is carried out vacuum distillation with Rotary Evaporators and is removed solvent first
Pure and mild excessive polyethylene polyamine obtains the modified PAMAM of polyethylene polyamine in 60-80 DEG C of vacuum drying 12-24h；
(5) 250mL ethyl alcohol is added in 1000mL three-necked flask, the modified PAMAM of 0.2mol polyethylene polyamine, stirring is then added
After 10-20min, warming-in-water is added dropwise epoxychloropropane under stirring condition, adds in 1.0-2.0h, then herein to 28-30 DEG C
At a temperature of react 5-8h, keep temperature in reaction flask to be no more than 30 DEG C in reaction process, then heat to 40-45 DEG C, it is even in 2h
The NaOH solution of mass fraction 50% is added dropwise in speed, after dripping off, 40-45 DEG C of reaction 1-2h is maintained to be filtered to remove after reaction
NaCl, then vacuum distillation removes remaining reactant, second alcohol and water.
2. a kind of preparation method of reducing dye ozone fastness elevator according to claim 1, it is characterised in that: step
Suddenly polyethylene polyamine described in (4) is one of diethylenetriamine, triethylene tetramine, tetraethylenepentamine, 3.5 generation PAMAM
It is n with polyethylene polyamine molar ratio3.5 generation PAMAM:nPolyethylene polyamine=1:8-1:24.
3. a kind of preparation method of reducing dye ozone fastness elevator according to claim 1, it is characterised in that: step
Suddenly the modified PAMAM of polyethylene polyamine described in (5) and epoxychloropropane molar ratio are nPolyethylene polyamine is modified PAMAM:nEpoxychloropropane=1:3-1:
6, NaOH with epoxychloropropane molar ratio be nNaOH:nEpoxychloropropane=1:1.1-1:1.3.
4. resistance to ozone jail prepared by a kind of preparation method of reducing dye ozone fastness elevator according to claim 1
Spend application of the elevator in textile.
5. resistance to ozone jail prepared by a kind of preparation method of reducing dye ozone fastness elevator according to claim 4
Spend application of the elevator in textile, it is characterised in that: carry out as follows:
Reducing dye ozone fastness elevator 2-4g is weighed, 100mL is diluted with water to, wherein by textile dipping, 2-5min
After take out, roll roll compacting fabric, two leachings two are rolled, pick-up 70%-90%, are then dried at 80 DEG C, then bake through 100-150 DEG C
Then 3-5min is washed 3-5 times, soap boiling, drying.
6. resistance to ozone jail prepared by a kind of preparation method of reducing dye ozone fastness elevator according to claim 5
Spend application of the elevator in textile, it is characterised in that: the textile is one of cotton, fiber crops, viscose fabric or two
Person's blending product.
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| CN110628019B (en) * | 2019-10-14 | 2021-12-07 | 四川瑞冬科技有限公司 | Purification method of dendrimer PAMAM |
| CN113603885B (en) * | 2021-07-23 | 2024-01-26 | 上海工程技术大学 | Modified dendritic polyamide-amine, preparation method thereof and application thereof in damping chlorinated butyl rubber |
| CN115678271B (en) * | 2022-11-02 | 2023-08-22 | 常州大学 | Preparation method of bio-based polyamide plant dye masterbatch |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101684621A (en) * | 2009-06-09 | 2010-03-31 | 陕西科技大学 | Dendriform cationic leather fixing agent and preparation method thereof |
| CN104313926A (en) * | 2014-11-17 | 2015-01-28 | 上海雅运纺织助剂有限公司 | Preparation method for hydrophilic dye-fixing agent for reactive dyeing |
-
2016
- 2016-12-06 CN CN201611109173.2A patent/CN106633049B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101684621A (en) * | 2009-06-09 | 2010-03-31 | 陕西科技大学 | Dendriform cationic leather fixing agent and preparation method thereof |
| CN104313926A (en) * | 2014-11-17 | 2015-01-28 | 上海雅运纺织助剂有限公司 | Preparation method for hydrophilic dye-fixing agent for reactive dyeing |
Non-Patent Citations (1)
| Title |
|---|
| 环氧氯丙烷改性PAMAM的制备及其在染整中的应用;李颖;《中国优秀硕士学位论文全文数据库工程科技I辑》;20160315;B024-45 * |
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