Polyether grafted macromolecular dye as well as preparation method and application thereof

Abstract

The invention discloses a polyether grafted macromolecular dye as well as a preparation method and application thereof. The structural general formula of the polyether grafted macromolecular dye is shown in the specification, x / Y is the same or different selected from NH and O atoms, R1 is alkyl, R2 and R3 are different and are respectively selected from H and methyl, Dye is a dye chromophoric group, 0 < = n < = 20 and n is an integer, 0 < = m < = 20 and m is an integer. The polyether grafted macromolecular dye has the advantages of controllable molecular weight, mild preparation conditions, no generation of toxic by-products and good color development performance, and can be used as water-based writing ink, marking ink, water-based printing ink, water-based paint and raw material color paste of daily chemical washing and nursing materials.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of water-based paint, ink colorant application, and specifically relates to a polyether grafted macromolecular dye, a preparation method and application thereof. BACKGROUND

[0002] The polyether macromolecular dye has good safety, stability, compatibility, low staining and the like, and is more and more widely applied in water-based paint, ink and washing care products.

[0003] At present, the preparation methods of the polyether macromolecule include an epoxy ring-opening method, a polyether amine active dye modification method and a sulfonated polyether amine modification method. The epoxy ring-opening method is to open the ring of the dye or dye intermediate containing an amino group or a hydroxyl group under high temperature and high pressure. However, the epoxy ring-opening activity of the dye is low, the polymerization is difficult, a higher temperature, a special catalyst and a preparation process are needed, the danger degree and the cost are higher than those of the common epoxy ring-opening method, and small molecular weight products are easily generated, which affects washability and safety. The polyether amine active dye modification method has good washability and safety, but the color development of the active dye is weak, resulting in a high addition amount and a high cost. The sulfonated polyether amine modification method is only reported in the literature because of high pollution and high danger in the dye sulfonation process.

[0004] Therefore, it is urgent to improve the prior art. SUMMARY

[0005] The present application solves the technical problems of the prior art, and provides a polyether grafted macromolecular dye, a preparation method and application thereof. The present application provides a novel polyether dye, specifically a macromolecular dye formed by a single isocyanate group polyether grafted dye. The macromolecular dye is prepared by single-end reaction of a hydrophilic single amino group polyether or an alkoxy polyether and diisocyanate (a feed ratio is less than or equal to 1.0) to obtain an isocyanate group polyether, and then the isocyanate group polyether is reacted with a hydroxyl / amino dye to obtain the polyether grafted macromolecular dye. The novel polyether dye has a controllable molecular weight, mild preparation conditions, no toxic by-products, good color development performance, and can be used as a raw material color paste of water-based writing ink, marking ink, water-based printing ink, water-based paint and daily washing care products.

[0006] The technical scheme adopted by the present application to solve the above technical problems is as follows. A polyether grafted macromolecular dye has the following general structure: ;

[0007] In the formula, X / Y is the same or different and is selected from NH and O atoms, R1 is a hydrocarbon group, R2 and R3 are different and are selected from H and methyl, Dye is a dye color development group, 0≤n≤20 and n is an integer, and 0≤m≤20 and m is an integer.

[0008] Preferably, the macromolecular dye is an aqueous polyether dye having a molecular weight of 300-10000 and a ratio of the total number of polyoxypropylene additions to the total number of polyoxyethylene additions being 0-1.

[0009] Preferably, the macromolecular dye is an oily polyether dye having a molecular weight of 300-10000 and a ratio of the total number of polyoxypropylene additions to the total number of polyoxyethylene additions being greater than 1.

[0010] The method for preparing the polyether grafted macromolecular dye as described above comprises the following steps: (1) preparing an isocyanate-terminated polyether: Main reaction:

[0011] Side reaction:

[0012] A. subjecting a monoamino polyether or an alkoxy polyether to dehydration treatment; The monoamino polyether has the structure of NH2(CH(CH3)CH2O) x (CH2CH2O) y R1, wherein 0≤x<100 and x is an integer, 6≤y<300 and y is an integer, and R1 is an alkyl group; The alkoxy polyether has the structure of HO(CH(CH3)CH2O) m (CH2CH2O) n R2, wherein 0≤m<100 and m is an integer, 6≤n≤300 and n is an integer, and R2 is an alkyl group; B. mixing 2-8 parts of the dehydrated monoamino polyether or alkoxy polyether with 20-200 parts of a solvent, slowly dropping the mixture into a reaction solution containing 2-8 parts of isocyanate and 10-100 parts of a solvent under temperature control and stirring, monitoring the reaction by infrared spectroscopy until the isocyanate signal peak is greatly reduced compared with the initial reaction solution and does not change for half an hour, obtaining an isocyanate-terminated polyether, which is ready for the next step; (2) grafting reaction of the isocyanate-terminated polyether with a dye containing a hydroxyl group or an amino group: Main reaction:

[0013] Side reaction:

[0014] In the reactor of step (1), 1 part of the dye containing hydroxyl or amino group and 10-300 parts of solvent are put in, stirred and dissolved, mixed uniformly, then heated to appropriate temperature to carry out addition reaction of isocyanate and hydroxyl or amino group; the reaction progress is monitored by TLC until the dye containing hydroxyl or amino group is completely grafted with terminal isocyanate group of polyether; the solvent is removed under reduced pressure to obtain novel macromolecular dye grafted with polyether; it is dissolved in water to prepare water-based ink for writing ink, or used in water-based paint and water-based printing ink, and coloring with curable resin; it can also be used as colorant for daily washing and care.

[0015] Preferably, in step (1), in step A, the molecular weight of the monoamino polyether is 300-10000, and the ratio of the total addition number of polyoxypropylene to the total addition number of polyoxyethylene is 0-1.

[0016] Preferably, in step (1), in step A, the molecular weight of the monoamino polyether is 300-10000, and the ratio of the total addition number of polyoxypropylene to the total addition number of polyoxyethylene is 0-1.

[0017] Preferably, in step (1), in step A, the monoamino polyether or alkoxyl polyether is dehydrated at 100-110°C under vacuum condition of ≤0.1 MPa for 2-3 hours.

[0018] Preferably, in step (1), in step B, the solvent can be selected from anhydrous aprotic solvents such as acetone, butanone, cyclohexanone, acetonitrile, tetrahydrofuran, dioxane, dichloroethane, toluene, ethyl acetate and other boiling point solvents.

[0019] Preferably, in step (1), in step B, the isocyanate is aliphatic diisocyanate, more preferably any one or combination of isophorone diisocyanate, hexamethylene diisocyanate, 4,4-dicyclohexylmethane diisocyanate and methylcyclohexyl diisocyanate.

[0020] Preferably, in step (1), in step B, the feeding ratio of monoamino polyether or alkoxyl polyether to isocyanate in the reaction material is ≤1.0.

[0021] Preferably, in step (1), in step B, the reaction temperature of the monoamino polyether is controlled between 0-35°C.

[0022] Preferably, in step (1), in step B, the reaction temperature of the alkoxyl polyether is controlled between 50-85°C.

[0023] Preferably, in step (2), the hydroxyl or amino group containing dye can be selected from any one of the dye molecules with two hydroxyl functional groups, comprising one or more of the following chromophores: azo, azo metal complex, phthalocyanine, anthraquinone, nitro, nitroso, nitroso metal complex, formazane-copper complex, triphenodioxazine, diazene, diarylmethane, triarylmethane, xanthene, acridine, methine, thiazole, indamine, azine, oxazine, thiazine, quinoline, indigoid, indophenol, lactone, aminoketone, hydroxyketone and stilbene.

[0024] More preferably, the hydroxyl or amino group containing dye is selected from one or more of the following: C.I. Disperse Red 4, C.I. Disperse Red 5, C.I. Disperse Red 7, C.I. Disperse Red 11, C.I. Disperse Red 15, C.I. Disperse Red 17, C.I. Disperse Red 19, C.I. Disperse Red 30, C.I. Disperse Red 58, C.I. Disperse Red 60, C.I. Disperse Red 64, C.I. Disperse Red 107, C.I. Disperse Red 118, C.I. Disperse Yellow 4, C.I. Disperse Yellow 6, C.I. Disperse Yellow 104, C.I. Disperse Yellow 123, C.I. Disperse Yellow 68, C.I. Disperse Blue 1, C.I. Disperse Blue 7, C.I. Disperse Blue 23, C.I. Disperse Blue 60, C.I. Disperse Blue 96, C.I. Disperse Blue 99, C.I. Disperse Blue 128, C.I. Disperse Blue 143, C.I. Disperse Blue 176, C.I. Disperse Green 5, C.I. Disperse Brown 1, C.I. Disperse Brown 4, C.I. Disperse Black 1, C.I. Disperse Black 2, C.I. Disperse Black 6, C.I. Disperse Black 27, C.I. Disperse Violet 1, C.I. Disperse Violet 8, C.I. Disperse Violet 26, C.I. Disperse Violet 28, C.I. Disperse Violet 35, C.I. Disperse Violet 38, C.I. Disperse Violet 43, C.I. Disperse Violet 46, C.I. Disperse Violet 62, alizarin, curcumin, indigo, shikonin, C.I. Basic Yellow 5, C.I. Basic Red 2, and the like, as well as one or more of the following: Direct Violet 9, Direct Violet 35, Direct Violet 48, Direct Violet 51, Direct Violet 66, Direct Violet 99, Direct Blue 1, Direct Blue 71, Direct Blue 80, Direct Blue 279, Acid Red 17, Acid Red 52, Acid Red 73, Acid Red 88, Acid Red 150, Acid Violet 15, Acid Violet 17, Acid Violet 24, Acid Violet 43, Acid Red 52, Acid Violet 49, Acid Violet 50, Acid Blue 15, Acid Blue 17, Acid Blue 25, Acid Blue 29, Acid Blue 40, Acid Blue 45, Acid Blue 75, Acid Blue 80, Acid Blue 83, Acid Blue 90, Acid Blue 113, Acid Black 1, Basic Violet 1, Basic Violet 3, Basic Violet 4, Basic Violet 10, Basic Violet 35, Basic Blue 3, Basic Blue 16, Basic Blue 22, Basic Blue 47, Basic Blue 66, Basic Blue 75, Basic Blue 159.

[0025] Preferably, in step (2), the solvent can be selected from anhydrous aprotic solvents such as boiling point solvents like acetone, butanone, cyclohexanone, acetonitrile, tetrahydrofuran, dioxane, dichloroethane, toluene, ethyl acetate and the like.

[0026] Preferably, in step (2), the reaction temperature is controlled between 25 to 60 °C for amino group containing dyes.

[0027] Preferably, in step (2), the reaction temperature is controlled between 60-110℃ for the hydroxyl-containing dyes.

[0028] Preferably, in step (2), 0.0001-0.003 parts of an organic tin or bismuth catalyst is added for the weakly reactive hydroxyl-containing dyes.

[0029] More preferably, the organic tin catalysts can be the conventional catalysts for polyurethane synthesis, such as stannous octoate, dibutyltin diacetate, dibutyltin dilaurate.

[0030] The polyether-grafted macromolecular dye as described above is applied in ink color paste, daily-use color paste, and wood paint color paste.

[0031] Compared with the prior art, the present application has the following advantages: The waterborne isocyanate-modified polyether macromolecular dye of the present application has the same properties as conventional polyether dyes, is mild and safe, has good compatibility, has better coloring performance, has a more mild and controllable preparation process, has no toxic byproducts, and the raw dye is easy to obtain, the product has high color strength, and the cost is suitable, so that the present application can meet the requirements of coloring agent raw materials for writing ink and marking ink, and can be used in waterborne color paste in printing ink and waterborne paint together with curable resin; because of the safe and mild properties of the polyether dye, the present application can also meet the requirements of various detergents or care agents that come into contact with the human body, including laundry liquid, laundry beads, hand sanitizer, shampoo, and shower gel. DETAILED DESCRIPTION

[0032] In order to better understand the content of the present application, the following further describes the present application with specific examples. It should be understood that these examples are only used to further illustrate the present application, and are not used to limit the scope of the present application. In addition, it should be understood that after reading the content described in the present application, those skilled in the art can make some non-essential modifications or adjustments to the present application, and still fall within the protection scope of the present application.

[0033] Example 1

[0034] C.I. Disperse Violet 43 Mw: 434.53 A method for preparing a polyether-grafted macromolecular dye, the steps are as follows: (1) 230 g (2.3 parts) of amino-terminated polyether JEFFAMINE® M-1000 after dehydration (100-110℃, vacuum degree ≤0.1 MPa, 2-3 hours) is dissolved in 400 g of acetone (69 parts), and slowly dropped into a 25℃ stirred mixture liquid containing 51.19 g (2.3 parts) of isophorone diisocyanate and 90 g (15.5 parts) of acetone, the dropping is completed in 30 min, and then the reaction is continued for 2 h, until the infrared test isocyanate signal peak does not change, and then the next step is used; (2) In the reactor of step (1), put in 41.19 g (1 part) of C.I. Disperse Red 12 and 300 g (30 parts) of dichloroethane, and 0.081 g (0.002 parts) of stannous octoate, mix well, then heat to 85°C and reflux for 3h, TLC test, developing agent dichloromethane:methanol=2:1, monitor the consumption of dye raw materials, i.e. remove dichloroethane under reduced pressure, to obtain a new polyether type red macromolecular dye.

[0035] Example 2

[0036] C.I. Disperse Red 12 Mw 411.9 A method for preparing a polyether grafted macromolecular dye, the steps are as follows: (1) Take 500 g (2.5 parts) of dehydrated (100-110°C, vacuum degree ≤0.1 MPa, 2-3 hours) amino-terminated polyether JEFFAMINE® M-2070 dissolved in 500 g of dichloroethane (50.5 parts), slowly drop into the mixed solution containing 42.05 g (2.5 parts) of hexamethylene diisocyanate and 100 g (10 parts) of dichloroethane stirred at 25°C, control 30 min drop, then continue to react for 2h, until the infrared test isocyanate signal peak does not change, for next step; (2) In the reactor of step (1), put in 41.19 g (1 part) of C.I. Disperse Red 12 and 300 g (30 parts) of dichloroethane, and 0.081 g (0.002 parts) of stannous octoate, mix well, then heat to 85°C and reflux for 3h, TLC test, developing agent dichloromethane:methanol=2:1, monitor the consumption of dye raw materials, i.e. remove dichloroethane under reduced pressure, to obtain a new polyether type red macromolecular dye.

[0037] Example 3

[0038] C.I. Disperse Yellow 4 Mw 265.27 A method for preparing a polyether grafted macromolecular dye, the steps are as follows: (1) Take 240 g (4.0 parts) of dehydrated (100-110°C, vacuum degree ≤0.1 MPa, 2-3 hours) amino-terminated polyether JEFFAMINE® M-600 dissolved in 500 g of acetone (86 parts), slowly drop into the mixed solution containing 67.28 g (4 parts) of hexamethylene diisocyanate and 116 g (20 parts) of acetone stirred at 25°C, control 30 min drop, then continue to react for 2h, until the infrared test isocyanate signal peak does not change, for next step; (2) In the reactor of step (1), put in 26.53 g (1 part) C.I. Disperse Yellow 4 and 250 g (43 parts) acetone, and 0.0189 g (0.0003 part) dibutyltin dilaurate, mix well, then heat to 80°C and reflux for 5 h. TLC test with developing agent dichloromethane:methanol = 1:2. When the dye raw material is consumed, remove the acetone under reduced pressure to obtain a novel polyether-type purple macromolecular dye.

[0039] Example 4

[0040] C.I. Disperse Blue 60 Mw: 379.37 A method for preparing a polyether grafted macromolecular dye, comprising the following steps: (1) Put 630 g (2.1 parts) of amino-terminated polyether JEFFAMINE® M-3085 after dehydration (100-110°C, vacuum degree ≤0.1 MPa, 2-3 hours) into 900 g of dichloroethane (91.8 parts), slowly drop into a mixture containing 46.68 g (2.1 parts) of isophorone diisocyanate and 100 g (10 parts) of dichloroethane stirred at 25°C, control the drop for 30 min, then continue to react for 2 h until the infrared test isocyanate signal peak does not change, and then proceed to the next step; (2) In the reactor of step (1), put in 37.94 g (1 part) C.I. Disperse Blue 60 and 200 g (34.5 parts) dichloroethane, mix well, then heat to 50°C and react for 3 h. TLC test with developing agent dichloromethane:methanol = 2:1. When the dye raw material is consumed, remove the dichloroethane under reduced pressure to obtain a novel polyether-type blue macromolecular dye.

[0041] Example 5

[0042] Diethanolamine modified C.I. Acid Blue 15 Mw: 807.26 A method for preparing a polyether grafted macromolecular dye, comprising the following steps: (1) Put 300 g (3.0 parts) of polyethylene glycol monomethyl ether MPEG1000 after dehydration (100-110°C, vacuum degree ≤0.1 MPa, 2-3 hours) into 500 g of acetone (86 parts), slowly drop into a mixture containing 50.46 g (3.0 parts) of hexamethylene diisocyanate and 116 g (20 parts) of acetone stirred at 60°C, control the drop for 30 min, then continue to react for 2 h until the infrared test isocyanate signal peak does not change, and then proceed to the next step; (2) In the reactor of step (1), put in 80.72 g (1 part) diethanolamine modified C.I. Acid Blue 15 and 360 g (62 parts) acetone, and 0.081 g (0.002 parts) stannous octoate, mix well, then heat to 80°C and reflux for 3 h. TLC test, developing agent: ethanol: water = 10:1. When the dye raw material is consumed, remove the acetone under reduced pressure to obtain a novel polyether type blue macromolecular dye.

[0043] Example 6

[0044] Diethanolamine modified C.I. Reactive Blue 15 Mw: 1355.7 A method for preparing a polyether grafted macromolecular dye, the steps are as follows: (1) Take 500 g (2.5 parts) of polyethylene glycol monomethyl ether MPEG2000 after dehydration (100-110°C, vacuum degree ≤0.1 MPa, 2-3 hours) and dissolve in 600 g of acetone (103 parts), slowly drop into the mixed solution containing 55.57 g (2.5 parts) of isophorone diisocyanate and 116 g (20 parts) of acetone stirred at 60°C, control 30 min drop, then continue to react for 2 h, until the infrared test isocyanate signal peak does not change, for next step; (2) In the reactor of step (1), put in 135.57 g (1 part) diethanolamine modified C.I. Reactive Blue 15 and 580 g (100 parts) acetone, and 0.0631 g (0.001 parts) dibutyltin dilaurate, mix well, then first at 45°C for 1 h, then heat to 80°C and reflux for 3 h. TLC test, developing agent: ethanol: water = 5:1. When the dye raw material is consumed, remove the acetone under reduced pressure to obtain a novel polyether type blue macromolecular dye.

[0045] Example 7

[0046] C.I. Disperse Red 12 Mw 411.9 A method for preparing a polyether grafted macromolecular dye, the steps are as follows: (1) Take 100 g (2.5 parts) of methoxy polyether MPEG400 after dehydration (100-110°C, vacuum degree ≤0.1 MPa, 2-3 hours) and dissolve in 200 g of dichloroethane (20.2 parts), slowly drop into the mixed solution containing 42.05 g (2.5 parts) of hexamethylene diisocyanate and 100 g (10 parts) of dichloroethane stirred at 55°C, control 30 min drop, then continue to react for 2 h, until the infrared test isocyanate signal peak does not change, for next step; (2) In the reactor of step (1), 41.19 g (1 part) of C.I. Disperse Red 12 and 300 g (30 parts) of dichloroethane, and 0.081 g (0.002 parts) of stannous octoate were added and mixed uniformly, and then heated to 85°C to reflux for 3 h. TLC chromatography test was performed with dichloromethane:methanol = 2:1 as the developing agent. When the dye raw material was consumed, the dichloroethane was removed under reduced pressure to obtain a novel polyether type red macromolecular dye.

[0047] Example 8

[0048] C.I. Disperse Blue 60 Mw: 379.37 A method for preparing a polyether grafted macromolecular dye, the steps are as follows: (1) 107.9 g (2.1 parts) of dehydrated (100-110°C, vacuum degree ≤0.1 MPa, 2-3 hours) butanol polyoxyethylene ether 10EO (hydroxyl value 109) was dissolved in 200 g of dichloroethane (20.2 parts), and slowly dropped into a mixed solution containing 46.68 g (2.1 parts) of isophorone diisocyanate and 100 g (10 parts) of dichloroethane stirred at 55°C. The dropping was completed in 30 min, and then the reaction was continued for 2 h until the infrared test isocyanate signal peak no longer changed, and then the next step was used; (2) In the reactor of step (1), 37.94 g (1 part) of C.I. Disperse Blue 60 and 200 g (34.5 parts) of dichloroethane were added and mixed uniformly, and then reacted at 50°C for 3 h. TLC chromatography test was performed with dichloromethane:methanol = 2:1 as the developing agent. When the dye raw material was consumed, the dichloroethane was removed under reduced pressure to obtain a novel polyether type blue macromolecular dye.

[0049] Comparative Example 1 Compared with Example 1, the amount of terminal amino polyether was reduced to 150 g (1.5 parts), and the proportions of other components and subsequent steps were consistent.

[0050] Comparative Example 2 Compared with Example 1, the amount of isophorone diisocyanate was reduced to 33.35 g (1.5 parts), and the proportions of other components and subsequent steps were consistent.

[0051] Comparative Example 3 Compared with Example 1, the terminal amino polyether was added directly, and the proportions of other components and subsequent steps were consistent.

[0052] Comparative Example 4 Compared with Example 7, the methoxy polyether molecular weight was changed to 100 (MPEG100), and the corresponding addition amount was changed to 25 g (2.5 parts), and the proportions of other components and subsequent steps were consistent.

[0053] The results of the synthesis experiments of Examples 1-8 and Comparative Examples 1-4 are shown in Table 1.

[0054] Table 1 Results of the synthesis experiments of Examples 1-8 and Comparative Examples 1-4 No. Color Average molecular weight Color content Example 1 Magenta 2824 13.8% Example 2 Red 4815 7.1% Example 3 Bright yellow 1887 8.6% Example 4 Turquoise blue 6836 5.30% Example 5 Bright blue 3211 19.2% Example 6 Turquoise blue 5752 20.1% Example 7 Magenta 1604 22.7% Example 8 Turquoise blue 1798 20.6% Comparative Example 1 Magenta 2359 18.1% Comparative Example 2 Magenta 2167 14.3% Comparative Example 3 Magenta 2703 13.8% Comparative Example 4 Magenta 811 36.6% Application Examples: I. Application Examples in the Field of Writing Inks The polyether dyes prepared in Examples 1-6 and Comparative Examples 1-3 above were dissolved in water to form 10% color paste, which was used as raw material to prepare colorant ink for markers. The formulation consisted of, by mass percentage, 8% polyether dye, 25% 1,2-propanediol, 10% glycerol, 1% surfactant, 55.9% water, and 0.1% preservative. The colorant ink was tested for performance by continuously drawing circles on paper, and the writing performance was judged by the number of lines drawn, from good to bad: 1, smooth hand feeling; 2, general hand feeling; 3, occasional ink breakage, poor writing hand feeling; 4, poor hand feeling, more ink breakage; 5, rough hand feeling, severe ink breakage. The test results are shown in Table 2.

[0055] Table 2 Test results of the application performance of markers Test object Viscosity / mPa·s pH Surface tension mN / m Writing effect Example 1 6.7 7.0 28.3 Line drawing normal, writing smooth Example 2 9.4 7.0 28.3 Line drawing normal, writing smooth Example 3 6.3 7.0 28.3 Line drawing normal, writing smooth Example 4 11.7 7.0 28.3 Line drawing normal, writing smooth Example 5 7.8 7.0 28.4 Line drawing normal, writing smooth Example 6 10.1 7.0 28.6 Line drawing normal, writing smooth Comparative Example 1 16.1 7.0 28.3 Line drawing occasionally ink break, writing poor Comparative Example 2 10.7 7.0 28.3 Line drawing frequently ink break, writing poor Comparative Example 3 7.9 7.0 28.3 Line drawing normal, writing a little rough As shown in Table 2, the polyether dyes prepared in Examples 1-6 all had good application performance in markers.

[0056] In Comparative Example 1, the average molecular weight of the polyether reaction raw material was reduced, but the water solubility was poorer, resulting in a large increase in viscosity and causing ink breakage.

[0057] In Comparative Example 2, the amount of isocyanate was reduced, and the molecular weight decreased more obviously. Although the viscosity did not increase much, some particles were observed to precipitate, and the ink frequently broke when the ink was prepared, which was believed to be caused by blockage of insoluble particles.

[0058] In Comparative Example 3, the feeding method was changed to direct mixing, which resulted in an increase in double-end capping and a decrease in the grafting rate of the actual monoisocyanate-based polyether, resulting in a slight decrease in molecular weight. Although the water solubility was still good and the ink was normally written, there was some resistance to ink flow, and it was not particularly smooth.

[0059] II. Application Examples in the Field of Daily Chemical Color Pastes The polyether dyes prepared in Examples 1-6 and Comparative Examples 1-3 above were adjusted to the same color value according to the color system, and then two parts per million of the dyes were added to a certain brand of laundry detergent base to prepare a finished laundry detergent product. The finished laundry detergent was tested for color picking as follows.

[0060] Color picking test: Six-fiber cloth: the six-fiber cloth with a length of 8 cm and a width of 1 cm was soaked in the base material for 4 hours, and then repeatedly washed under running water for 1 minute. After drying for 2 hours, whether the six-fiber cloth was stained was observed.

[0061] The results of the staining test are shown in Table 3.

[0062] Table 3: Staining test results Test object Six-fiber cloth Example 1 1 Example 2 0 Example 3 0 Example 4 0 Example 5 1 Example 6 0 Comparative Example 1 3 Comparative Example 2 4 Comparative Example 3 2 As shown by the results in Table 3, the polyether dyes prepared in Examples 1-6 have good washability when added to laundry detergent, while the polyether dyes prepared in Comparative Examples 1-3 have poor washability due to poor polyether grafting and poor water dispersibility, resulting in staining.

[0063] III. Wood paint application examples The polyether dyes prepared in Examples 3, 7 and 8, and Comparative Example 4 were diluted with water to form a 30% color paste, which was used as a colorant paste for wood paint. The dye in Comparative Example 4 has low solubility in water, and a color paste was prepared by replacing water with ethylene glycol.

[0064] Wood paint preparation: 8% color paste, 43% acrylic emulsion and 35% waterborne polyurethane dispersion were added to the paint mixing tank, 0.3% pH regulator AMP95 and 2% nano-silica dispersion were added, and the mixture was stirred quickly until uniform. Then, 0.5% defoamer BYK024 was diluted with 8% deionized water, and the mixture was slowly added to the system. The mixture was dispersed at 1500 r / min until no shrinkage was observed on the fineness plate. Then, 0.5% wetting agent Wet KL270, 0.6% leveling agent Glide450 and 0.8% matting agent TSW 100W were added in sequence. The viscosity was adjusted to the required value by adding 0.8% thickening agent AR8959, and then 0.5% antibacterial agent was added. The mixture was stirred thoroughly until uniform, and then filtered to obtain the waterborne wood paint.

[0065] The waterborne wood paints obtained from Examples 3, 7 and 8, and Comparative Example 4 were sprayed on the surface of wooden test pieces by spraying. After spraying, the paints were cured by heating, and the following paint film performance tests were conducted: Paint film adhesion test: determined according to GB / T9286 1998 "Paints and varnishes - Cross-hatch adhesion test"; Paint film hardness test: determined according to GB / T6739 2006 "Paints and varnishes - Determination of film hardness by pencil test"; Paint film water immersion resistance test: the edges of the wooden test pieces were sealed with paraffin to prevent water from entering from the edges. Half of the wooden test pieces were immersed in water, and the other half were used as a control. After a certain period of time, the test pieces were taken out and observed visually to see if the paint film had wrinkles or peeled off.

[0066] The results are shown in Table 4.

[0067] Table 4 Wood paint application test results Test object Adhesion Hardness 50h water immersion Example 3 0 2H No abnormality Example 7 0 2H No abnormality Example 8 0 2H No abnormality Comparative Example 4 0 2H No abnormality As can be seen from Table 4, the polyether dyes prepared in Examples 3, 7 and 8 do not affect the adhesion and hardness when used in wood paint formulations; while the polyether dye prepared in Comparative Example 4 has a small molecular weight and poor water solubility, and needs to be formulated into a pseudo-water formulation for application.

[0068] The application discloses a novel water-based polyether macromolecular dye, which is prepared by single-end reaction of hydrophilic single-group amino polyether or alkoxy polyether and diisocyanate (the feeding ratio is less than or equal to 1.0) to obtain an isocyanate-terminated polyether, and then by reaction of the isocyanate-terminated polyether and a hydroxyl / amino dye to obtain a polyether grafted macromolecular dye. The novel polyether dye has controllable molecular weight, mild preparation conditions, no toxic by-products, good color performance, and can be used as a raw material color paste for water-based writing ink, marking ink, water-based printing ink, water-based paint and daily chemical washing and care products.

[0069] The above description is not a limitation of the application, and the application is not limited to the above examples. Changes, modifications, additions or substitutions made by those skilled in the art within the scope of the application should also be within the protection scope of the application.

Claims

1. A polyether-grafted macromolecular dye, characterized in that, Its general structural formula is as follows: ； In the formula, X / Y, whether the same or different, are selected from NH and O atoms, R1 is a hydrocarbon group, R2 and R3 are different and are selected from H and methyl respectively, Dye is the dye chromophore, 0≤n≤20 and n is an integer, 0≤m≤20 and m is an integer.

2. The method for preparing a polyether-grafted macromolecular dye as described in claim 1, characterized in that, Includes the following steps: (1) Preparation of isocyanate-terminated polyethers: A. Dehydrate the monoamino polyether or alkoxy polyether; The structure of the monoamino polyether is: NH2(CH(CH3)CH2O) x (CH2CH2O) y R1, where 0 ≤ x < 100 and x is an integer, 6 ≤ y < 300 and y is an integer, and R1 is an alkyl group; The structure of the alkoxy polyether is: HO(CH(CH3)CH2O) m (CH2CH2O) n R2, where 0≤m<100 and m is an integer, 6≤n≤300 and n is an integer, and R2 is an alkyl group; B. Mix 2-8 parts of the dehydrated monoamino polyether or alkoxy polyether with 20-200 parts of solvent, and slowly drop it into a temperature-controlled and stirred reaction solution containing 2-8 parts of isocyanate and 10-100 parts of solvent. Monitor the reaction with infrared until the isocyanate signal peak is significantly lower than that of the initial reaction solution and does not change for a period of time, to obtain terminal isocyanate polyether. (2) Grafting reaction of terminal isocyanate polyethers with dyes containing hydroxyl or amino groups: In step (1), 1 part of a hydroxyl or amino dye and 10 to 300 parts of solvent are added to the reactor, stirred and dissolved, mixed evenly, and then heated to an appropriate temperature to carry out the addition reaction of isocyanate and hydroxyl or amino. The reaction process is monitored until the hydroxyl or amino dye is completely grafted onto the isocyanate polyether. The solvent is removed under reduced pressure to obtain the polyether-grafted macromolecular dye.

3. The method for preparing a polyether-grafted macromolecular dye as described in claim 1, characterized in that, In step (1), in step A, the molecular weight of the monoamino polyether is 300~10000, and the ratio of the total number of additions of polyoxypropylene to the total number of additions of polyoxyethylene is 0~1; the molecular weight of the alkoxy polyether is 300~10000, and the ratio of the total number of additions of polyoxypropylene to the total number of additions of polyoxyethylene is 0~1.

4. The method for preparing a polyether-grafted macromolecular dye as described in claim 1, characterized in that, In steps (1) and (2), the solvent is an anhydrous aprotic solvent.

5. The method for preparing a polyether-grafted macromolecular dye as described in claim 1, characterized in that, In step (1), in step B, the isocyanate is an aliphatic diisocyanate.

6. The method for preparing a polyether-grafted macromolecular dye as described in claim 1, characterized in that, In step (1), in step B, the ratio of monoamino polyether or alkoxy polyether to isocyanate in the reaction materials is ≤1.

0.

7. The method for preparing a polyether-grafted macromolecular dye as described in claim 1, characterized in that, In step (1), in step B, the reaction temperature of the monoamino polyether is controlled between 0 and 35°C; the reaction temperature of the alkoxy polyether is controlled between 50 and 85°C.

8. The method for preparing a polyether-grafted macromolecular dye as described in claim 1, characterized in that, In step (2), for dyes containing amino groups, the reaction temperature is 25~60℃; for dyes containing hydroxyl groups, the reaction temperature is 60~110℃.

9. The method for preparing a polyether-grafted macromolecular dye as described in claim 1, characterized in that, In step (2), for dyes containing hydroxyl groups, add 0.0001 to 0.003 parts of organotin or organobismuth catalyst as appropriate.

10. The application of the polyether-grafted macromolecular dye as described in claim 1 in ink pastes, daily chemical pastes, and wood varnish pastes.

Images