CN105949425B - A kind of polyurethane black high molecular dye, preparation method and application - Google Patents
A kind of polyurethane black high molecular dye, preparation method and application Download PDFInfo
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- CN105949425B CN105949425B CN201610418079.9A CN201610418079A CN105949425B CN 105949425 B CN105949425 B CN 105949425B CN 201610418079 A CN201610418079 A CN 201610418079A CN 105949425 B CN105949425 B CN 105949425B
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- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B69/00—Dyes not provided for by a single group of this subclass
- C09B69/10—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds
- C09B69/106—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds containing an azo dye
Abstract
The invention discloses a kind of polyurethane black high molecular dye, preparation method and application, polymer polyatomic alcohol is warming up to 90~110 DEG C, under the conditions of vacuum degree≤0.1MPa, 1~2h of dehydration is passed through nitrogen protection；60~80 DEG C are cooled to, is added at isocyanates and 60~90 DEG C of catalyst and reacts 1~3 hour；Then small molecule black dyes, solvent and catalyst is added, is reacted 3~8 hours at 60~90 DEG C, is made and has black dyes base polyurethane prepolymer for use as；Chain extender is added, is reacted 1~3 hour at 50~90 DEG C；Last vacuum desolvation agent.Polyurethane black high molecular dye prepared by the present invention is to access small molecule black dyes in polyurethane chain, can be adjusted according to the needs content of the small molecule black dyes in polyurethane chain, realize the controllable of amount of dye.Adapt to different dyeing requirements.It can match colors with other dyestuff blendings, a variety of colors dyeing very wide suitable for chromatography.
Description
Technical field
The present invention relates to a kind of high molecular dye more particularly to a kind of polyurethane black high molecular dyes, preparation
Method and application.
Background technique
Small molecule black dyes has very important status in printing and dyeing, leather, coating, medicine and other fields.Due to small point
Sub- dyestuff binding force is not strong, dye utilization rate is low and the shortcoming of the aspect of performance such as resistance to migration, heat-resisting and solvent resistant, and
Pollution on the environment is serious in use process, limits the application in various fields.
The small molecule black dyes of early stage is mainly that azo benzidine is derivative, has good pitch black degree, dye-uptake and fixation
The high advantage of rate can generate carcinogenic benzidine intermediate in production and use process.Last century the seventies, are spread out by benzidine
Raw all black dyes are in succession disabled.Although developing country still uses this dyestuff, developed country has stopped
Produce benzidine dye.
It is poly- that Chinese patent CN201410472297.1 discloses a kind of black water based on black chromophore in dihydric alcohol
The preparation method of urethane dyestuff, dyestuff persistence is good, and color fastness is high, and safety is good.But reaction process is more complicated, separation mentions
Pure difficulty, and can only be used in aqueous environments.
Chinese " functional material " (the 2nd 351-354 pages of phases of volume 42 in 2011), which report, is utilizing Mordant Black T (EBT)
It is introduced into polyurethane molecular chain as chain extender, black water polyurethane dyestuff (EBT-PU) is prepared, due to acid mordant black
Low in acetic acid -2-ethoxy-ethyl ester solubility, access amount is limited.Again due to water soluble dyestuffs, only limit the use of in aqueous medium.
Summary of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of polyurethane black high molecular dye,
Preparation method and application, realization are added in polyurethane small molecule black dyes.
The present invention is achieved by the following technical solutions: the present invention the following steps are included:
(1) polymer polyatomic alcohol is warming up to 90~110 DEG C, under the conditions of vacuum degree≤0.1MPa, 1~2h of dehydration,
It is passed through nitrogen protection；
(2) 60~80 DEG C are cooled to, is added at isocyanates and 60~90 DEG C of catalyst and reacts 1~3 hour；
(3) small molecule black dyes, solvent and catalyst is then added, is reacted 3~8 hours at 60~90 DEG C, band is made
There is black dyes base polyurethane prepolymer for use as；
(4) chain extender is added, is reacted 1~3 hour at 50~90 DEG C；
(5) last vacuum desolvation agent.
The isocyanates is selected from least one of aromatic isocyanate and aliphatic isocyanates, in mass ratio example
Additional amount is 10~35 parts.
The polymer polyatomic alcohol is selected from least one of pure and mild polyester polyol of polyether polyols, and example in mass ratio is added
Amount is 20~60 parts.
The chain extender is selected from ethylene glycol, 1,4-butanediol, diglycol, glycerol, hydroxymethyl-cyclohexane, three hydroxyls
At least one of methylpropane, methyl propane diamine, isophorone diamine, diethylenetriamine, in mass ratio example additional amount be 0~
10 parts.
The solvent is selected from acetone, butanone, dioxane, N, and N- dimethylformamide, N-Methyl pyrrolidone, dimethyl are sub-
Sulfone, ethyl acetate, acetic acid -2-ethoxy-ethyl ester, 1,2- dimethoxy-ethane, ethylene glycol monomethyl ether, 2-Butoxyethyl acetate, second
At least one of the tertiary butyl ether of glycol list, ethylene glycol monobutyl ether, in mass ratio example additional amount are 30~50 parts.
The catalyst be organic tin catalyst, at least one in stannous octoate and dibutyl tin dilaurate
Kind, example additional amount is 0.1~0.3 part in mass ratio.
The small organic molecule black dyes is black selected from the dispersion black GNN of diazonium (CAS No.:6054-48-4), dispersion diazonium
3BF (CAS No.:6232-57-1), Direct fast light black G (CAS No.:6428-31-5), eriochrome black T (CAS No.:1787-61-
7), Mordant Black 2B (CAS No.:25747-08-4), directly black FF (CAS:8003-62-1), direct fast black L-3BG (CAS
At least one of No.:6428-31-5), example additional amount is 10~30 parts in mass ratio.
Dyestuff made from a kind of preparation method of polyurethane black high molecular dye.
The dyestuff is on the basis of the quality of total reactant, in polyurethane chain, the quality containing small molecule black dyes
Content is 10~30%；In polyurethane backbone, the mass content containing polyethers and/or polyester segment is 20~60%.
A kind of application of dyestuff in dyeing.
Macromolecule black dyes be by certain chemical reaction by small molecule black dyes introduce high molecular main chain or
It is formed on side chain.Black dyes high molecular dye has the function of dual: i.e. high molecular high-intensitive, easy film forming, resistance to
Solvent borne, resistance to migration, heat resistance and machinability, but organic dyestuff shows good color fastness, dyestuff to the strong absorbent of light
The features such as utilization rate is high, nontoxic and easy to use.
Polyurethane black dyes be by way of chemical bonding by small molecule dyes be introduced into polyurethane main chain or
Side chain forms polyurethane dyestuff, has dyestuff and polyurethane respectively advantage concurrently.It is steady not only to solve small organic molecule black dyes
The disadvantages of qualitative poor, dye utilization rate is low and substrate intermiscibility is bad, and have polyurethane easily form a film, easy processing and health
The advantages that property is good.Polyurethane dyestuff is related to many multi-disciplinary cross disciplines such as electronics, chemistry, physics, in laser, liquid crystal
Show, solar battery, the fields such as pharmacy all have huge research and development application value.
Polymer polyatomic alcohol is reacted to form polyurethane by the present invention first by the method for poly- addition with excess isocyanate
Performed polymer, then small organic molecule black dyes is accessed into base polyurethane prepolymer for use as chain, molecular weight then is adjusted by introducing chain extender,
Solvent is finally sloughed, polyurethane black high molecular dye is made.
The present invention have the advantage that compared with prior art the present invention obtain material be suitable for coating, textile, plastics,
The multiple fields such as rubber, laser recording, nonlinear optical material, food, medicine.It is pitch-black with high dye-uptake, high colour-fast rate, height
The features such as degree, high lifting force, light resistance, heat resistance, washable, wear-resisting, resistance to migration, resistance to wet process, easy film forming, machinability.This
The material of invention has easy to use, at low cost, nontoxic, advantages of environment protection.Polyurethane black high score prepared by the present invention
Sub- dyestuff is to access small molecule black dyes in polyurethane chain, can be adjusted according to the needs small molecule black dyes in poly- ammonia
Content in ester chain realizes the controllable of amount of dye.Adapt to different dyeing requirements.It can match colors, be applicable in other dyestuff blendings
In the very wide a variety of colors dyeing of chromatography.
Specific embodiment
It elaborates below to the embodiment of the present invention, the present embodiment carries out under the premise of the technical scheme of the present invention
Implement, the detailed implementation method and specific operation process are given, but protection scope of the present invention is not limited to following implementation
Example.
Embodiment 1
In N2Under protection, 100g, the poly- tetrahydro of 0.1mol will be added in the four-hole bottle that blender, condenser pipe, thermometer are housed
Furans glycol, 110 DEG C, under the conditions of 0.1MPa, dehydration 2h.
Be cooled to 70 DEG C, be added dropwise 44.5g, 0.2mol isophorone diisocyanate, 40mlN- methyl pyrrolidone and
0.02g dibutyl tin dilaurate reacts 3 hours at 90 DEG C.
Then plus 11.3g, 0.043mol disperse the black GNN of diazonium, rise temperature 60 C and react 2h.
Add 0.53g, 0.005mol diglycol reacts 1 hour at 60 DEG C.
Finally vacuum distillation abjection N-Methyl pyrrolidone, obtains that polyurethane black high molecular dye is made.
Products therefrom ultraviolet most strong absworption peak 510nm, 250~360 DEG C of first stage thermal decomposition temperature, second stage
360~550 DEG C of thermal decomposition temperature, 59 DEG C of glass transition temperature.
Embodiment 2
In N2Under protection, 100g will be added in the four-hole bottle that blender, condenser pipe, thermometer are housed, 0.1mol gathers in oneself
Esterdiol, 110 DEG C, under the conditions of 0.1MPa, dehydration 2h.
Be cooled to 70 DEG C, 50g, 0.2mol 4,4- methyl diphenylene diisocyanate (MDI), 20ml dioxane and
0.02g stannous octoate reacts 3 hours at 90 DEG C.
18.5g, 0.022mol Direct fast light black G is then added, cooling temperature 50 C reacts 2h.
Add 0.45g, the 1,4-butanediol () of 0.005mol is reacted 1 hour at 50 DEG C.
Finally vacuum distillation abjection N-Methyl pyrrolidone, obtains that polyurethane black high molecular dye is made.
Products therefrom ultraviolet most strong absworption peak 520nm, 265~380 DEG C of first stage thermal decomposition temperature, second stage
380~550 DEG C of thermal decomposition temperature, 66 DEG C of glass transition temperature.
Embodiment 3
To equipped in thermometer, blender, reflux condenser and dropping funel flask, 100g, 0.1mol polyoxy is added
Change propylene glycol, 110 DEG C, under the conditions of 0.1MPa, dehydration 1.5h.
It is cooled to 80 DEG C, is added dropwise 34.8g, 0.2mol toluene di-isocyanate(TDI), 20ml butanone and 0.02g stannous octoate, 90
It is reacted 3 hours at DEG C.
11g is then added, 0.043mol disperses the black 3BF of diazonium, rises temperature 60 C and reacts 2h.
Add 0.32g, 0.005mol ethylene glycol reacts 1 hour at 60 DEG C.
Finally vacuum distillation abjection N-Methyl pyrrolidone, obtains that polyurethane black high molecular dye is made.
Products therefrom ultraviolet most strong absworption peak 530nm, 255~350 DEG C of first stage thermal decomposition temperature, second stage
350~550 DEG C of thermal decomposition temperature, 61 DEG C of glass transition temperature.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (9)
1. a kind of preparation method of polyurethane black high molecular dye, which comprises the following steps:
(1) polymer polyatomic alcohol is warming up to 90~110 DEG C, under the conditions of vacuum degree≤0.1MPa, 1~2h of dehydration is passed through
Nitrogen protection；
(2) 60~80 DEG C are cooled to, is reacted 1~3 hour at addition isocyanates, solvent and 60~90 DEG C of catalyst；
(3) small molecule black dyes is then added, is reacted 3~8 hours at 60~90 DEG C, is made pre- with black dyes polyurethane
Aggressiveness；
(4) chain extender is added, is reacted 1~3 hour at 50~90 DEG C；
(5) last vacuum desolvation agent；
The dyestuff is on the basis of the quality of total reactant, in polyurethane chain, the mass content containing small molecule black dyes
It is 10~30%；In polyurethane backbone, the mass content containing polyethers and/or polyester segment is 20~60%.
2. a kind of preparation method of polyurethane black high molecular dye according to claim 1, which is characterized in that described
Isocyanates be selected from least one of aromatic isocyanate and aliphatic isocyanates, in mass ratio example additional amount be 10~
35 parts.
3. a kind of preparation method of polyurethane black high molecular dye according to claim 1, which is characterized in that described
Polymer polyatomic alcohol is selected from least one of pure and mild polyester polyol of polyether polyols, and example additional amount in mass ratio is 20~60
Part.
4. a kind of preparation method of polyurethane black high molecular dye according to claim 1, which is characterized in that described
Chain extender is selected from ethylene glycol, Isosorbide-5-Nitrae-butanediol, diglycol, glycerol, hydroxymethyl-cyclohexane, trimethylolpropane, first
At least one of base propane diamine, isophorone diamine, diethylenetriamine, in mass ratio example additional amount are 0~10 part.
5. a kind of preparation method of polyurethane black high molecular dye according to claim 1, which is characterized in that described
Solvent be selected from acetone, butanone, dioxane, N, N- dimethylformamide, N-Methyl pyrrolidone, dimethyl sulfoxide, ethyl acetate,
Acetic acid -2-ethoxy-ethyl ester, 1,2- dimethoxy-ethane, ethylene glycol monomethyl ether, 2-Butoxyethyl acetate, the tertiary fourth of ethylene glycol list
At least one of ether, ethylene glycol monobutyl ether, in mass ratio example additional amount are 30~50 parts.
6. a kind of preparation method of polyurethane black high molecular dye according to claim 1, which is characterized in that described
Catalyst is organic tin catalyst, is selected from least one of stannous octoate and dibutyl tin dilaurate, in mass ratio example
Additional amount is 0.1~0.3 part.
7. a kind of preparation method of polyurethane black high molecular dye according to claim 1, which is characterized in that described
Small molecule black dyes is selected from the black GNN of dispersion diazonium, the black 3BF of dispersion diazonium, Direct fast light black G, eriochrome black T, Mordant Black 2B, straight
At least one of black FF, direct fast black L-3BG are met, example additional amount in mass ratio is 10~30 parts.
8. dyestuff made from a kind of preparation method of the polyurethane black high molecular dye as described in any one of claim 1~7.
9. application of the dyestuff as claimed in claim 8 in dyeing.
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107501511B (en) * | 2017-09-14 | 2019-12-27 | 安徽建筑大学 | Anionic compound waterborne polyurethane-based black dye and preparation method thereof |
| CN107541094A (en) * | 2017-09-14 | 2018-01-05 | 安徽建筑大学 | One kind compounding polyurethane-base macromolecule black dyes and preparation method thereof |
| CN107573477B (en) * | 2017-09-14 | 2019-12-27 | 安徽建筑大学 | Cationic compound aqueous polyurethane-based black dye and preparation method thereof |
| CN109517406A (en) * | 2018-11-12 | 2019-03-26 | 安徽富瑞雪化工科技股份有限公司 | A kind of preparation method of color-changing polyurethane acrylate dyestuff |
| CN110616572A (en) * | 2019-09-29 | 2019-12-27 | 中国皮革制鞋研究院有限公司 | Heat-resistant, sun-resistant and high-color-fastness high-molecular dye for leather |
| CN113451414B (en) * | 2020-06-18 | 2022-07-29 | 重庆康佳光电技术研究院有限公司 | Thin film transistor device and preparation method thereof |
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