CN105061773B - A kind of chitin modified epoxy resin-matrix macromolecule dyestuff and preparation method thereof - Google Patents
A kind of chitin modified epoxy resin-matrix macromolecule dyestuff and preparation method thereof Download PDFInfo
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- CN105061773B CN105061773B CN201510566350.9A CN201510566350A CN105061773B CN 105061773 B CN105061773 B CN 105061773B CN 201510566350 A CN201510566350 A CN 201510566350A CN 105061773 B CN105061773 B CN 105061773B
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Abstract
The present invention provides a kind of chitin modified epoxy resin-matrix macromolecule dyestuff and preparation method thereof, and specific preparation method is：(1) after epoxy resin is stirred evenly with aniline, heating reaction, is cooled to room temperature, epoxy resin precursor is obtained after purified；(2) chitosan is added in sodium hydroxide solution, be stirred at room temperature, add bischloroethylamines hydrochloride, heating is reacted, and is acidified product after question response, dialyses 3 days, water-solubility chitosan derivative is obtained after freeze-drying；(3) by weight, epoxy resin precursor is added into N, N dimethylformamides, are stirred at room temperature to it and are completely dissolved, add water-solubility chitosan derivative and auxiliary agent, obtain chitin modified epoxy resin precursor；(4) in chitin modified epoxy resin precursor and azo chromophore mixed with polymers, through diazo coupling in ice-water bath, chitin modified epoxy resin-matrix macromolecule dyestuff is then obtained after precipitating filtering drying.
Description
Technical field：
The invention belongs to textile material technical field, and in particular to a kind of chitin modified epoxy resin-matrix macromolecule dye
Material and preparation method thereof.
Background technology：
High molecular dye is a kind of colored polymeric, due to being colored dyes and colourless polymer chemical bond, height
The light absorbs of the existing dye matrix of molecular dye, light Master, photoconductive, the function such as selection absorption of acid-base discoloration and enzyme, also have
There are the features such as stability, compatibility, hygiene and the easy film forming of polymer, there is relatively broad pass in dope dyeing field
Note.Due to high molecular dye and traditional part azo dyes, carcinogenic arylamine synthetic dyestuffs, the activity heavily fortified point with covalent bond effect
Tough, low molecular weight disperse dyes are compared, not only with molecule macromolecule easy processing, heat-resisting, solvent resistant, it is resistance to migration, to biology
The good performance of the harmless grade of body, and dosage is greatly reduced, and bright-colored, color fastness, dye utilization rate height etc. can be shown
Advantage.
The methods of high molecular dye can be modified method, metal complex by monomer polymerization method, polymer chemistry is made, wherein
Polymer modification method is to use a kind of more method, i.e., the grafting dyestuff with high reaction activity point on macromolecular scaffold
Son.The high molecular dye of common polymer modification has the multiple types such as polyurethanes, polyesters, polyethers, chitin modified class
Type.
Epoxy resin refers generally to the organic compound containing two and above epoxide group in molecule, in epoxy resin due to
Containing active epoxide group, reaction can be crosslinked with multiple compounds and forms net structure high polymer, and asphalt mixtures modified by epoxy resin
The product size stability of fat is good, and hardness is good, and pliability is good, to alkali and most of solvent-stable, therefore epoxy resin is used for
Preparing high molecular dye has good application prospect.
Polymer diazotization and coupling synthetic epoxy resin family macromolecule disclosed in Chinese patent CN 1112412C (publication date)
The method of dyestuff, prepares epoxy resin primary polymer first, and aromatic amino compound is prepared into diazol, most laggard
The diazonium coupled reaction of row polymer, obtains the product of the present invention, and the reaction yield and conversion ratio of this method are both greater than 90%, production
Thing can be used for preparing various cations, anion and dispersed polymeric azo dyestuff and pigment, have adhesion, water-wash resistance
With stability it is good the advantages that.A kind of diazotization and coupling prepares water-soluble disclosed in Chinese patent CN 101787222B (publication date)
The method of vinyl sulfone epoxy resin-matrix macromolecule reactive dye, its epoxy resin precursor is high polymer main chain, through ethoxy
The aromatic amino compound of sulfone sulfate class is prepared into diazol, most carries out diazonium through diazol and epoxy resin precursor afterwards
Coupling reaction, obtains finished product, the finished product good water solubility, in alkaline conditions, can be reacted with hydroxyl or the material of amino groups
To complete fixation, the Fastness Problems of dyeing are solved.From the above-mentioned prior art, the kind of epoxy resin-matrix macromolecule dyestuff
It is more, it is soluble good, covalent bond can be formed with multiple fiber storeroom, obtain the dyestuff of good color fastness, however the color and luster that dyes and
Brightness is not very good.
Chitosan is cationic polymer, has similar structure to cellulose, has unique biocompatibility, biology
Degradability, antibiotic property, nontoxicity, bioactivity and physicochemical properties, can increase the affinity to dyestuff, and increase dyestuff
Color depth, contaminates effect in raising, therefore has application prospect at the hyperchromic aspect of textile printing and dyeing.
The content of the invention：
The technical problem to be solved in the present invention is to provide a kind of chitin modified epoxy resin-matrix macromolecule dyestuff and its
Preparation method, chitin modified asphalt mixtures modified by epoxy resin is combined to form by the epoxy resin precursor of purifying and water-solubility chitosan derivative
Fat, then changing the surface grafting azo chromophore polymer of epoxy resin, obtain chitin modified epoxy resin-matrix macromolecule
Dyestuff.Chitin modified epoxy resin-matrix macromolecule dyestuff prepared by the present invention possesses the dual spy of chitosan and epoxy resin
Property, the good film-forming property of dyestuff, washable and weathering color fastness is high, and upper dye is beautiful in colour, and colourity is deep, can more reduce dye
The dosage of material, improves the economic value of textile.
In order to solve the above technical problems, the technical scheme is that：
A kind of chitin modified epoxy resin-matrix macromolecule dyestuff, it is characterised in that chitin modified epoxy resin
Based high molecular dyestuff is the product combined through chitin modified epoxy resin with azo chromophore polymer.
Preferably, the chitosan is water-soluble modified chitosan derivatives.
The present invention also provides a kind of preparation method of chitin modified epoxy resin-matrix macromolecule dyestuff, its feature exists
In：Comprise the following steps：
(1) by weight, after 10 parts of epoxy resin and 3-5 parts of aniline being stirred evenly, it is heated to 120-150 DEG C
When reaction 48-60 is small, it is cooled to room temperature, epoxy resin precursor is obtained after purified；
(2) by weight, 1 part of chitosan is added in 80-100 parts of sodium hydroxide solution, 40- is stirred at room temperature
50min, adds 0.3-0.5 parts of bischloroethylamines hydrochloride, and heating is reacted, and is acidified product after question response, dialysis 3
My god, water-solubility chitosan derivative is obtained after freeze-drying；
(3) by weight, the epoxy resin precursor prepared by (1) the step of 1 part adds 50-100 parts of N, N- bis-
Methylformamide, is stirred at room temperature to it and is completely dissolved, and water soluble chitosan prepared by the step of adding 15-35 parts (2) derives
Thing and 0-20 parts of auxiliary agent, obtain chitin modified epoxy resin precursor；
(4) count by volume, by the step of 50-80 parts (3) prepare chitin modified epoxy resin precursor with
0.1-10 parts of azo chromophore mixed with polymers, through diazo coupling in ice-water bath, then after precipitating filtering drying
Obtain chitin modified epoxy resin-matrix macromolecule dyestuff.
As the preferred of above-mentioned technical proposal, in the step (1), epoxy resin is bisphenol A epoxide resin.
As the preferred of above-mentioned technical proposal, in the step (1), the molecular weight of epoxy resin precursor is 50000-
60000。
As the preferred of above-mentioned technical proposal, in the step (2), the temperature for heating reaction is 70-80 DEG C, heating reaction
Time be 10-15h.
As the preferred of above-mentioned technical proposal, in the step (2), the molecular weight of water-solubility chitosan derivative is
90000-100000。
As the preferred of above-mentioned technical proposal, in the step (3), auxiliary agent is in water, ethanol, acetone or isopropanol
It is one or more of.
As the preferred of above-mentioned technical proposal, in the step (4), azo chromophore polymer is that at least one azo is given birth to
Color reunion compound.
As the preferred of above-mentioned technical proposal, in the step (4), mixed method is dripping method.
Compared with prior art, the invention has the advantages that：
(1) the chitin modified epoxy resin-matrix macromolecule dyestuff for preparing of the present invention possesses chitosan and epoxy resin
Double grading, the good film-forming property of dyestuff, performance are stablized, and washable and weathering color fastness is high, and upper dye beautiful in colour, colourity
It is deep, the dosage of dyestuff can be more reduced, improves the economic value of textile.
(2) chitin modified epoxy resin-matrix macromolecule dyestuff prepared by the present invention belongs to modified azo dyes, closes
It is simple into technique, it is easy to control, the high molecular dye of different colours can be prepared according to the azo chromophoric polymer of different colours, can be with
Irregular colour caused by avoiding dye particles dispersion is even.
(3) chitosan is contained in chitin modified epoxy resin-matrix macromolecule dyestuff prepared by the present invention, thus it is also simultaneous
Has the effect of certain antibacterial bacteriostatic, moreover it is possible to improve the biodegradable properties of the high molecular dye.
Embodiment：
Below in conjunction with specific embodiment, the present invention will be described in detail, herein illustrative examples and explanation of the invention
For explaining the present invention, but it is not as a limitation of the invention.
Embodiment 1：
(1) by weight, after 10 parts of bisphenol A epoxide resin and 3 parts of aniline being stirred evenly, 120 DEG C are heated to
React 48 it is small when, be cooled to room temperature, it is 50000 epoxy resin precursors that molecular weight is obtained after purified.
(2) by weight, 1 part of chitosan is added in 80 parts of sodium hydroxide solution, 40min is stirred at room temperature, then
0.3 part of bischloroethylamines hydrochloride is added, reaction 10h is heated at 70 DEG C, product is acidified after question response, dialyses 3 days,
The water-solubility chitosan derivative that molecular weight is 90000 is obtained after freeze-drying.
(3) by weight, the epoxy resin precursor prepared by (1) the step of 1 part adds 50 parts of N, N- dimethyl
Formamide, is stirred at room temperature to it and is completely dissolved, and water-solubility chitosan derivative prepared by the step of adding 15 parts (2), obtains
Chitin modified epoxy resin precursor.
(4) count by volume, by chitin modified epoxy resin precursor prepared by (3) the step of 50 parts and 0.1 part
A kind of azo chromophore polymer mixing is added dropwise with the speed of 5 drops/min, through diazo coupling, Ran Houjing in ice-water bath
Chitin modified epoxy resin-matrix macromolecule dyestuff is obtained after precipitation filtering drying.
Embodiment 2：
(1) by weight, after 10 parts of bisphenol A epoxide resin and 5 parts of aniline being stirred evenly, 150 DEG C are heated to
React 60 it is small when, be cooled to room temperature, obtained after purified molecular weight be 60000 epoxy resin precursor.
(2) by weight, 1 part of chitosan is added in 100 parts of sodium hydroxide solution, 50min is stirred at room temperature, then
0.5 part of bischloroethylamines hydrochloride is added, reaction 15h is heated at 80 DEG C, product is acidified after question response, dialyses 3 days,
The water-solubility chitosan derivative that molecular weight is 100000 is obtained after freeze-drying.
(3) by weight, the epoxy resin precursor prepared by (1) the step of 1 part adds 100 parts of N, N- dimethyl
Formamide, is stirred at room temperature to it and is completely dissolved, water-solubility chitosan derivative prepared by the step of adding 35 parts (2) and 20 parts
Isopropanol auxiliary agent, obtain chitin modified epoxy resin precursor.
(4) count by volume, by chitin modified epoxy resin precursor prepared by (3) the step of 80 parts and 10 parts
Mixing is added dropwise with the speed of 10 drops/min in a kind of azo chromophore polymer, through diazo coupling, Ran Houjing in ice-water bath
Chitin modified epoxy resin-matrix macromolecule dyestuff is obtained after precipitation filtering drying.
Embodiment 3：
(1) by weight, after 10 parts of bisphenol A epoxide resin and 4 parts of aniline being stirred evenly, 135 DEG C are heated to
React 55 it is small when, be cooled to room temperature, obtained after purified molecular weight be 55000 epoxy resin precursor.
(2) by weight, 1 part of chitosan is added in 90 parts of sodium hydroxide solution, 45min is stirred at room temperature, then
0.4 part of bischloroethylamines hydrochloride is added, reaction 13h is heated at 75 DEG C, product is acidified after question response, dialyses 3 days,
The water-solubility chitosan derivative that molecular weight is 95000 is obtained after freeze-drying.
(3) by weight, the epoxy resin precursor prepared by (1) the step of 1 part adds 80 parts of N, N- dimethyl
Formamide, is stirred at room temperature to it and is completely dissolved, water-solubility chitosan derivative prepared by the step of adding 25 parts (2) and 10 parts
Ethanol water auxiliary agent, obtain chitin modified epoxy resin precursor.
(4) count by volume, by chitin modified epoxy resin precursor prepared by (3) the step of 70 parts and 1 part
Mixing is added dropwise with the speed of 8 drops/min in two kinds of azo chromophore polymer, through diazo coupling in ice-water bath, then through heavy
Chitin modified epoxy resin-matrix macromolecule dyestuff is obtained after the filtering drying of shallow lake.
Embodiment 4：
(1) by weight, after 10 parts of bisphenol A epoxide resin and 3.5 parts of aniline being stirred evenly, 140 are heated to
DEG C reaction 54 it is small when, be cooled to room temperature, obtained after purified molecular weight be 59000 epoxy resin precursor.
(2) by weight, 1 part of chitosan is added in 85 parts of sodium hydroxide solution, 40min is stirred at room temperature, then
0.3 part of bischloroethylamines hydrochloride is added, reaction 15h is heated at 70 DEG C, product is acidified after question response, dialyses 3 days,
The water-solubility chitosan derivative that molecular weight is 93000 is obtained after freeze-drying.
(3) by weight, the epoxy resin precursor prepared by (1) the step of 1 part adds 70 parts of N, N- dimethyl
Formamide, is stirred at room temperature to it and is completely dissolved, water-solubility chitosan derivative prepared by the step of adding 25 parts (2) and 5 parts
Acetone auxiliary agent, obtain chitin modified epoxy resin precursor.
(4) count by volume, by chitin modified epoxy resin precursor prepared by (3) the step of 60 parts and 5 parts
Mixing is added dropwise with the speed of 5 drops/min in a kind of azo chromophore polymer, through diazo coupling in ice-water bath, then through heavy
Chitin modified epoxy resin-matrix macromolecule dyestuff is obtained after the filtering drying of shallow lake.
Embodiment 5：
(1) by weight, after 10 parts of bisphenol A epoxide resin and 3 parts of aniline being stirred evenly, 135 DEG C are heated to
React 60 it is small when, be cooled to room temperature, obtained after purified molecular weight be 58000 epoxy resin precursor.
(2) by weight, 1 part of chitosan is added in 90 parts of sodium hydroxide solution, 40min is stirred at room temperature, then
0.5 part of bischloroethylamines hydrochloride is added, reaction 10h is heated at 80 DEG C, product is acidified after question response, dialyses 3 days,
The water-solubility chitosan derivative that molecular weight is 92000 is obtained after freeze-drying.
(3) by weight, the epoxy resin precursor prepared by (1) the step of 1 part adds 100 parts of N, N- dimethyl
Formamide, is stirred at room temperature to it and is completely dissolved, water-solubility chitosan derivative prepared by the step of adding 15 parts (2) and 15 parts
Ethanol auxiliary agent, obtain chitin modified epoxy resin precursor.
(4) count by volume, by chitin modified epoxy resin precursor prepared by (3) the step of 80 parts and 1 part
Mixing is added dropwise with the speed of 10 drops/min in a kind of azo chromophore polymer, through diazo coupling, Ran Houjing in ice-water bath
Chitin modified epoxy resin-matrix macromolecule dyestuff is obtained after precipitation filtering drying.
Embodiment 6：
(1) by weight, after 10 parts of bisphenol A epoxide resin and 4 parts of aniline being stirred evenly, 150 DEG C are heated to
React 50 it is small when, be cooled to room temperature, obtained after purified molecular weight be 54000 epoxy resin precursor.
(2) by weight, 1 part of chitosan is added in 95 parts of sodium hydroxide solution, 40min is stirred at room temperature, then
0.3 part of bischloroethylamines hydrochloride is added, reaction 15h is heated at 70 DEG C, product is acidified after question response, dialyses 3 days,
The water-solubility chitosan derivative that molecular weight is 950000 is obtained after freeze-drying.
(3) by weight, the epoxy resin precursor prepared by (1) the step of 1 part adds 80 parts of N, N- dimethyl
Formamide, is stirred at room temperature to it and is completely dissolved, water-solubility chitosan derivative prepared by the step of adding 20 parts (2) and 5 parts
Acetone auxiliary agent, obtain chitin modified epoxy resin precursor.
(4) count by volume, by chitin modified epoxy resin precursor prepared by (3) the step of 60 parts and 2 parts
Mixing is added dropwise with the speed of 7 drops/min in two kinds of azo chromophore polymer, through diazo coupling in ice-water bath, then through heavy
Chitin modified epoxy resin-matrix macromolecule dyestuff is obtained after the filtering drying of shallow lake.
After testing, the chitin modified epoxy resin-matrix macromolecule dyestuff and the prior art that prepared by embodiment 1-6
K/S values, color fastness, the result of biodegradable of epoxy resin-matrix macromolecule dyestuff are as follows：
As seen from the above table, the color depth of chitin modified epoxy resin-matrix macromolecule dyestuff prepared by the present invention is obvious
Improve, and water-fastness, rub resistance, colour fasteness to sunlight are all fine, meet the standard of textile printing and dyeing dyestuff.
The above-described embodiments merely illustrate the principles and effects of the present invention, not for the limitation present invention.It is any ripe
Know the personage of this technology all can carry out modifications and changes under the spirit and scope without prejudice to the present invention to above-described embodiment.Cause
This, those of ordinary skill in the art is complete without departing from disclosed spirit and institute under technological thought such as
Into all equivalent modifications or change, should by the present invention claim be covered.
Claims (10)
- A kind of 1. chitin modified epoxy resin-matrix macromolecule dyestuff, it is characterised in that chitin modified epoxy resin-matrix High molecular dye is the product combined through chitin modified epoxy resin with azo chromophore polymer.
- 2. a kind of chitin modified epoxy resin-matrix macromolecule dyestuff according to claim 1, it is characterised in that described Chitosan is water-soluble modified chitosan derivatives.
- A kind of 3. preparation method of chitin modified epoxy resin-matrix macromolecule dyestuff, it is characterised in that：Comprise the following steps：(1) by weight, after 10 parts of epoxy resin and 3-5 parts of aniline being stirred evenly, it is heated to 120-150 DEG C of reaction When 48-60 is small, it is cooled to room temperature, epoxy resin precursor is obtained after purified；(2) by weight, 1 part of chitosan is added in 80-100 parts of sodium hydroxide solution, 40-50min is stirred at room temperature, 0.3-0.5 parts of bischloroethylamines hydrochloride is added, heating is reacted, and is acidified product after question response, is dialysed 3 days, freezing Water-solubility chitosan derivative is obtained after drying；(3) by weight, the epoxy resin precursor prepared by (1) the step of 1 part adds 50-100 parts of N, N- dimethyl Formamide, is stirred at room temperature to it and is completely dissolved, water-solubility chitosan derivative prepared by the step of adding 15-35 parts (2) and 0-20 parts of auxiliary agent, obtains chitin modified epoxy resin precursor；(4) count by volume, chitin modified epoxy resin precursor and 0.1-10 prepared by (3) the step of 50-80 parts The azo chromophore mixed with polymers of part, through diazo coupling in ice-water bath, then obtains shell after precipitating filtering drying The epoxy resin-matrix macromolecule dyestuff that glycan is modified.
- 4. a kind of preparation method of chitin modified epoxy resin-matrix macromolecule dyestuff according to claim 3, it is special Sign is：In the step (1), epoxy resin is bisphenol A epoxide resin.
- 5. a kind of preparation method of chitin modified epoxy resin-matrix macromolecule dyestuff according to claim 3, it is special Sign is：In the step (1), the molecular weight of epoxy resin precursor is 50000-60000.
- 6. a kind of preparation method of chitin modified epoxy resin-matrix macromolecule dyestuff according to claim 3, it is special Sign is：In the step (2), the temperature for heating reaction is 70-80 DEG C, and the time for heating reaction is 10-15h.
- 7. a kind of preparation method of chitin modified epoxy resin-matrix macromolecule dyestuff according to claim 3, it is special Sign is：In the step (2), the molecular weight of water-solubility chitosan derivative is 90000-100000.
- 8. a kind of preparation method of chitin modified epoxy resin-matrix macromolecule dyestuff according to claim 3, it is special Sign is：In the step (3), auxiliary agent is the one or more in water, ethanol, acetone or isopropanol.
- 9. a kind of preparation method of chitin modified epoxy resin-matrix macromolecule dyestuff according to claim 3, it is special Sign is：In the step (4), azo chromophore polymer is at least one azo chromophore polymer.
- 10. a kind of preparation method of chitin modified epoxy resin-matrix macromolecule dyestuff according to claim 3, it is special Sign is：In the step (4), mixed method is dripping method.
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| CN106009776B (en) * | 2016-02-04 | 2018-01-02 | 南通纺织丝绸产业技术研究院 | Flower cyanines cationic fluorescent dyestuff of a kind of macromolecular half and preparation method thereof |
| CN107011698A (en) * | 2017-04-06 | 2017-08-04 | 霍邱县淮美奇工艺品有限公司 | A kind of extracting method of the willow leaf colouring substance of high stability |
| CN108219070A (en) * | 2017-12-29 | 2018-06-29 | 中国科学院海洋研究所 | A kind of novel salt tolerant super absorbent resin and preparation method thereof |
| CN114953075B (en) * | 2022-05-09 | 2023-08-08 | 浙江升华云峰新材股份有限公司 | Preparation method of high-color-fastness recombined decorative veneer |
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| CN1284524A (en) * | 2000-09-01 | 2001-02-21 | 清华大学 | Diazo coupling process of polymer to synthesize high molecular epoxy resin dye |
| CN101787222B (en) * | 2010-01-08 | 2015-06-03 | 武汉科技学院 | Method for preparing water-soluble vinyl sulfone epoxy resin-matrix macromolecule reactive dye by diazo coupling |
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