Polyether grafted macromolecular dye, its preparation method and application

Abstract

The application discloses a polyether grafted macromolecular dye, a preparation method and application thereof, and a structural general formula of the polyether grafted macromolecular dye is as follows: wherein 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 chromophore, 0<=n<=20 and n is an integer, 0<=m<=20 and m is an integer. The polyether grafted macromolecular dye has controllable molecular weight, mild preparation conditions, no toxic by-products, good chromogenic 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 chemical washing and care products.

Description

Technical Field

[0001] This invention relates to the field of water-based coatings and ink colorant application technology, specifically to a polyether-grafted macromolecular dye, its preparation method and application. Background Technology

[0002] Polyether macromolecular dyes are increasingly widely used in water-based coatings, inks, and detergents due to their excellent safety, stability, compatibility, and low staining properties.

[0003] Currently, methods for preparing polyether macromolecules include epoxy ring-opening, polyetheramine reactive dye modification, and sulfonated polyetheramine modification. Epoxy ring-opening involves ring-opening an amino or hydroxyl-containing dye or dye intermediate under high temperature and pressure. However, the epoxy ring-opening activity of dye molecules is relatively low, making polymerization difficult and requiring higher temperatures, special catalysts, and advanced preparation processes. This method is more hazardous and costly than conventional epoxy ring-opening and is prone to producing low-molecular-weight products, affecting washability and safety. While polyetheramine reactive dye modification offers better washability and safety, the weak color development of reactive dyes leads to higher addition amounts and higher costs. Sulfonated polyetheramine modification is currently only reported in the literature due to the high pollution and risk associated with the dye sulfonation process.

[0004] Therefore, there is an urgent need to improve the existing technology. Summary of the Invention

[0005] The technical problem to be solved by this invention is to overcome the technical defects of the prior art and provide a polyether-grafted macromolecular dye, its preparation method, and its application. This invention provides a novel polyether dye, specifically a macromolecular dye formed by grafting a monoisocyanate-based polyether dye. It is prepared by reacting a hydrophilic monofunctional amino polyether or alkoxy polyether with a diisocyanate (feed ratio ≤ 1.0) at one end to obtain a terminal isocyanate-based polyether, which is then reacted with a hydroxyl / amino dye to obtain the polyether-grafted macromolecular dye. The resulting novel polyether dye has a controllable molecular weight, is prepared under mild conditions, produces no toxic byproducts, and has good color development performance. It can be used as a raw material pigment for water-based writing inks, marking inks, water-based printing inks, water-based coatings, and daily chemical washing and care products.

[0006] The technical solution adopted by the present invention to solve the above-mentioned technical problems is as follows:

[0007] A polyether-grafted macromolecular dye has the following general structural formula:

[0008] ;

[0009] 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.

[0010] Preferably, the macromolecular dye is an aqueous polyether dye with a molecular weight of 300 to 10,000, and the ratio of the total number of additions of polyoxypropylene to the total number of additions of polyoxyethylene is 0 to 1.

[0011] Preferably, the macromolecular dye is an oil-based polyether dye with a molecular weight of 300-10000, and the ratio of the total number of additions of polyoxypropylene to the total number of additions of polyoxyethylene is greater than 1.

[0012] The preparation method of the polyether-grafted macromolecular dye as described above includes the following steps:

[0013] (1) Preparation of isocyanate-terminated polyethers:

[0014] Main reaction:

[0015]

[0016] Side reactions:

[0017]

[0018] A. Dehydrate the monoamino polyether or alkoxy polyether;

[0019] 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;

[0020] 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;

[0021] 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 light until the isocyanate signal peak is significantly lower than that of the initial reaction solution and no longer changes after half an hour. The terminal isocyanate polyether is then ready for the next step.

[0022] (2) Grafting reaction of terminal isocyanate polyethers with dyes containing hydroxyl or amino groups:

[0023] Main reaction:

[0024]

[0025] Side reactions:

[0026]

[0027] In step (1), 1 part of a hydroxyl or amino-containing dye and 10-300 parts of solvent are added to the reactor, stirred and dissolved, and mixed evenly. Then, the temperature is raised to an appropriate temperature to carry out the addition reaction of isocyanate with hydroxyl or amino groups. The reaction process is monitored by TLC until the hydroxyl or amino-containing dye is completely grafted onto the isocyanate-based polyether. The solvent is removed under reduced pressure to obtain a novel polyether-grafted macromolecular dye pure material. It can be dissolved in water to prepare water-based ink for writing ink, or for water-based coatings and water-based printing inks, and can be used in conjunction with curable resins for coloring. It can also be used as a colorant for daily chemical washing and care.

[0028] Preferably, 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.

[0029] Preferably, in step (1), in step A, 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.

[0030] Preferably, in step (1), in step A, the monoamino polyether or alkoxy polyether is dehydrated for 2-3 hours at 100-110°C and a vacuum degree ≤0.1MPa.

[0031] 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, etc.

[0032] Preferably, in step (1), in step B, the isocyanate is an aliphatic diisocyanate, more preferably any one or a combination of the following: isophorone diisocyanate, hexamethylene diisocyanate, 4,4-dicyclohexylmethane diisocyanate and methylcyclohexyl diisocyanate.

[0033] Preferably, in step (1), in step B, the ratio of monoamino polyether or alkoxy polyether to isocyanate in the reactants is ≤1.0.

[0034] Preferably, in step (1), in step B, the reaction temperature of the monoamino polyether is controlled between 0 and 35°C.

[0035] Preferably, in step (1), in step B, the reaction temperature of the alkoxy polyether is controlled between 50 and 85°C.

[0036] Preferably, in step (2), the hydroxyl or amino-containing dye can be selected from any dye molecule with two hydroxyl functional groups, containing one or more of the following chromophores: azo, azo metal complex, phthalocyanine, anthraquinone, aza

[18] arbutin, formazane-copper-complex, triphenyl dioxazine, nitroso, nitro, diarylmethane, triarylmethane, xanthracene, acridine, methine, thiazole, indamine, acridine, oxazine, thiazine, quinoline, indigo, indophenol, lactone, amino ketone, hydroxy ketone, and stilbene.

[0037] More preferably, the hydroxyl or amino-containing dye is selected from the color index (Society of Dyers and Colourists, Bradford, UK). UK Dispersed Red (CI) numbers: CI Dispersed Red 4, CI Dispersed Red 5, CI Dispersed Red 7, CI Dispersed Red 11, CI Dispersed Red 15, CI Dispersed Red 17, CI Dispersed Red 19, CI Dispersed Red 30, CI Dispersed Red 58, CI Dispersed Red 60, CI Dispersed Red 64, CI Dispersed Red 107, CI Dispersed Red 118, CI Dispersed Yellow 4, CI Dispersed Yellow 6, CI Dispersed Yellow 104, CI Dispersed Yellow 123, CI Dispersed Yellow 68, CI Dispersed Blue 1, CI Dispersed Blue 7, CI Dispersed Blue 23, CI Dispersed Blue 60, CI Dispersed Blue 96, CI Dispersed Blue 99, CI Dispersed Blue 128, CI Dispersed Blue 143, CI Dispersed Blue 176, CI Dispersed Green 5, CI Dispersed Brown 1, CI Dispersed Brown 4, CI Dispersed Black 1, CI Dispersed Black 2, CI Dispersed Black 6, CI Dispersed Black 27, CI Dispersed Violet 1, CI Dispersed Violet 8, CI Dispersed Violet 26, CI Dispersed Violet 28, CI Dispersed Violet 35, CI Dispersed Violet 38, CI Dispersed Violet 43, CI Dispersed Violet 46, CI Disperse Violet 62, Alizarin, Curcumin, Indigo, Shikonin, CI Basic Yellow 5, CI Basic Red 2, and 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... One or more of the following: 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, and Basic Blue 159.

[0038] Preferably, in step (2), the solvent can be selected from anhydrous aprotic solvents such as acetone, butanone, cyclohexanone, acetonitrile, tetrahydrofuran, dioxane, dichloroethane, toluene, ethyl acetate, etc.

[0039] Preferably, in step (2), for amino-containing dyes, the reaction temperature is controlled between 25 and 60°C.

[0040] Preferably, in step (2), for dyes containing hydroxyl groups, the reaction temperature is controlled between 60 and 110°C.

[0041] Preferably, in step (2), for hydroxyl-containing dyes with weaker reactions, 0.0001 to 0.003 parts of organotin or organobismuth catalyst are added appropriately.

[0042] More preferably, the organotin can be a catalyst used in the synthesis of conventional polyurethanes, such as stannous octoate, dibutyltin diacetate, or dibutyltin dilaurate.

[0043] The application of polyether-grafted macromolecular dyes as described above in ink pastes, daily chemical pastes, and wood coating pastes.

[0044] Compared with the prior art, the beneficial effects of the present invention are:

[0045] The waterborne isocyanate-modified polyether macromolecular dye of the present invention has the same properties as conventional polyether dyes, is mild and safe, and has good compatibility, but has better coloring performance, a milder and more controllable preparation process, no toxic by-products, and the raw material dye is readily available. The product has high color intensity and reasonable cost, and can meet the requirements of colorant raw materials for writing inks and marking inks. It can also be used in combination with curable resins for waterborne color pastes in printing inks and waterborne coatings. Due to the safe and mild properties of polyether dyes, it can also meet the requirements of various detergents or care products that come into contact with the human body, including laundry detergent, laundry pods, hand soap, shampoo, and shower gel. Detailed Implementation

[0046] To better understand the content of this invention, further description is provided below with reference to specific embodiments. It should be understood that these embodiments are only for further illustration of the invention and are not intended to limit the scope of the invention. Furthermore, it should be understood that after reading the description of this invention, those skilled in the art may make some non-essential modifications or adjustments to the invention, which still fall within the protection scope of this invention.

[0047] Example 1

[0048] CI Disperse Violet 43 Mw:434.53

[0049] A method for preparing a polyether-grafted macromolecular dye, comprising the following steps:

[0050] (1) Take 230g (2.3 parts) of dehydrated (100~110℃, vacuum degree ≤0.1MPa, 2~3 hours) terminal amino polyether JEFFAMINE® M-1000 and dissolve it in 400g acetone (69 parts). Slowly drop it into a mixture containing 51.19g (2.3 parts) isophorone diisocyanate and 90g (15.5 parts) acetone and stirred at 25℃. Control the drop to be completed in 30min. Then continue the reaction for 2h until the isocyanate signal peak of infrared test no longer changes. Then proceed to the next step for use.

[0051] (2) In the reaction vessel of step (1), add 43.453g (1 part) CI Disperse Violet 43 and 290g (50 parts) acetone and 0.061g (0.0015 parts) stannous octoate. After mixing evenly, heat to 80℃ and reflux for 3h. TLC chromatographic test, the developing solvent is dichloromethane:methanol=5:1. Monitor until the dye raw materials are consumed, then remove acetone under reduced pressure to obtain a new type of polyether purple macromolecular dye.

[0052] Example 2

[0053] CI Disperse Red 12 Mw411.9

[0054] A method for preparing a polyether-grafted macromolecular dye, comprising the following steps:

[0055] (1) Take 500g (2.5 parts) of dehydrated (100~110℃, vacuum degree ≤0.1MPa, 2~3 hours) amino-terminated polyether JEFFAMINE® M-2070 and dissolve it in 500g of dichloroethane (50.5 parts). Slowly drop it into a mixture containing 42.05g (2.5 parts) hexamethylene diisocyanate and 100g (10 parts) dichloroethane, stirred at 25℃. Control the drop to be completed in 30min. Then continue the reaction for 2h until the isocyanate signal peak of infrared test no longer changes. Then proceed to the next step for use.

[0056] (2) In the reaction vessel of step (1), add 41.19g (1 part) CI Disperse Red 12 and 300g (30 parts) dichloroethane and 0.081g (0.002 parts) stannous octoate. After mixing evenly, heat to 85℃ and reflux for 3h. TLC chromatographic test, the developing solvent is dichloromethane:methanol = 2:1. Monitor until the dye raw materials are consumed, then remove dichloroethane under reduced pressure to obtain a new type of polyether red macromolecular dye.

[0057] Example 3

[0058] CI Disperse Yellow 4 Mw265.27

[0059] A method for preparing a polyether-grafted macromolecular dye, comprising the following steps:

[0060] (1) Take 240g (4.0 parts) of dehydrated (100~110℃, vacuum degree ≤0.1MPa, 2~3 hours) terminal amino polyether JEFFAMINE® M-600 and dissolve it in 500g acetone (86 parts). Slowly drop it into a mixture containing 67.28g (4 parts) hexamethylene diisocyanate and 116g (20 parts) acetone and stirred at 25℃. Control the drop to be completed in 30min. Then continue the reaction for 2h until the isocyanate signal peak of infrared test no longer changes. Then proceed to the next step for use.

[0061] (2) In the reaction vessel of step (1), add 26.53g (1 part) CI Disperse Yellow 4 and 250g (43 parts) acetone and 0.0189g (0.0003 parts) dibutyltin dilaurate. After mixing evenly, heat to 80℃ and reflux for 5h. TLC chromatographic test, the developing solvent is dichloromethane:methanol=1:2. Monitor until the dye raw materials are consumed, then remove acetone under reduced pressure to obtain a new type of polyether purple macromolecular dye.

[0062] Example 4

[0063] CI Disperse Blue 60 Mw:379.37

[0064] A method for preparing a polyether-grafted macromolecular dye, comprising the following steps:

[0065] (1) Take 630g (2.1 parts) of dehydrated (100~110℃, vacuum degree ≤0.1MPa, 2~3 hours) amino-terminated polyether JEFFAMINE® M-3085 and dissolve it in 900g of dichloroethane (91.8 parts). Slowly drop it into a mixture containing 46.68g (2.1 parts) of isophorone diisocyanate and 100g (10 parts) of dichloroethane, stirred at 25℃. Control the drop to be completed in 30min. Then continue the reaction for 2h until the isocyanate signal peak of infrared test no longer changes. Then proceed to the next step for use.

[0066] (2) In the reaction vessel of step (1), add 37.94g (1 part) CI Disperse Blue 60 and 200g (34.5 parts) dichloroethane, mix evenly and heat to 50℃ for 3h. TLC chromatographic test, the developing solvent is dichloromethane:methanol = 2:1. Monitor until the dye raw material is consumed, then remove dichloroethane under reduced pressure to obtain a new type of polyether blue macromolecular dye.

[0067] Example 5

[0068] Diethanolamine-modified CI Acid Blue 15 Mw:807.26

[0069] A method for preparing a polyether-grafted macromolecular dye, comprising the following steps:

[0070] (1) Take 300g (3.0 parts) of dehydrated (100~110℃, vacuum degree ≤0.1MPa, 2~3 hours) polyethylene glycol monomethyl ether MPEG1000 and dissolve it in 500g acetone (86 parts). Slowly drop it into a mixture containing 50.46g (3.0 parts) hexamethylene diisocyanate and 116g (20 parts) acetone and stirred at 60℃. Control the drop to be completed in 30min. Then continue the reaction for 2h until the isocyanate signal peak of infrared test no longer changes. Then proceed to the next step for use.

[0071] (2) In the reaction vessel of step (1), add 80.72g (1 part) of diethanolamine modified CI Acid Blue 15 and 360g (62 parts) of acetone and 0.081g (0.002 parts) of stannous octoate. After mixing evenly, heat to 80℃ and reflux for 3h. TLC chromatographic test, the developing solvent ethanol:water = 10:1. Monitor until the dye raw materials are consumed, then remove acetone under reduced pressure to obtain a new type of polyether blue macromolecular dye.

[0072] Example 6

[0073] Ethanolamine-modified CI Reactive Blue 15 Mw:1355.7

[0074] A method for preparing a polyether-grafted macromolecular dye, comprising the following steps:

[0075] (1) Take 500g (2.5 parts) of dehydrated (100~110℃, vacuum degree ≤0.1MPa, 2~3 hours) polyethylene glycol monomethyl ether MPEG2000 and dissolve it in 600g acetone (103 parts). Slowly drop it into a mixture containing 55.57g (2.5 parts) isophorone diisocyanate and 116g (20 parts) acetone, stirred at 60℃. Control the drop to be completed in 30min. Then continue the reaction for 2h until the infrared test shows that the isocyanate signal peak no longer changes. Then proceed to the next step for use.

[0076] (2) In the reaction vessel of step (1), add 135.57g (1 part) of ethanolamine modified CI reactive blue 15 and 580g (100 parts) of acetone and 0.0631g (0.001 parts) of dibutyltin dilaurate. After mixing evenly, keep the mixture at 45°C for 1 hour, then heat it to 80°C and reflux for 3 hours. TLC chromatography test, the developing solvent ethanol:water = 5:1. Monitor that the dye raw materials are consumed, then remove the acetone under reduced pressure to obtain a new type of polyether type cyan macromolecular dye.

[0077] Example 7

[0078] CI Disperse Red 12 Mw411.9

[0079] A method for preparing a polyether-grafted macromolecular dye, comprising the following steps:

[0080] (1) Take 100g (2.5 parts) of methoxy polyether MPEG400 after dehydration (100~110℃, vacuum degree ≤0.1MPa, 2~3 hours) and dissolve it in 200g of dichloroethane (20.2 parts). Slowly drop it into a mixture containing 42.05g (2.5 parts) of hexamethylene diisocyanate and 100g (10 parts) of dichloroethane, stirred at 55℃. Control the drop to be completed in 30min. Then continue the reaction for 2h until the isocyanate signal peak of infrared test no longer changes. Then proceed to the next step for use.

[0081] (2) In the reaction vessel of step (1), add 41.19g (1 part) CI Disperse Red 12 and 300g (30 parts) dichloroethane and 0.081g (0.002 parts) stannous octoate. After mixing evenly, heat to 85℃ and reflux for 3h. TLC chromatographic test, the developing solvent is dichloromethane:methanol = 2:1. Monitor until the dye raw materials are consumed, then remove dichloroethane under reduced pressure to obtain a new type of polyether red macromolecular dye.

[0082] Example 8

[0083] CI Disperse Blue 60 Mw:379.37

[0084] A method for preparing a polyether-grafted macromolecular dye, comprising the following steps:

[0085] (1) Take 107.9g (2.1 parts) of butanol polyoxyethylene ether 10EO (hydroxyl value 109) after dehydration (100~110℃, vacuum degree ≤0.1MPa, 2~3 hours) and dissolve it in 200g of dichloroethane (20.2 parts). Slowly drop it into a mixture containing 46.68g (2.1 parts) of isophorone diisocyanate and 100g (10 parts) of dichloroethane, stirred at 55℃. Control the drop to be completed in 30min. Then continue the reaction for 2h until the isocyanate signal peak of infrared test no longer changes. Then proceed to the next step for use.

[0086] (2) In the reaction vessel of step (1), add 37.94g (1 part) CI Disperse Blue 60 and 200g (34.5 parts) dichloroethane, mix evenly, and keep the reaction at 50℃ for 3h. TLC chromatography test, the developing solvent is dichloromethane:methanol = 2:1. Monitor until the dye raw material is consumed, then remove dichloroethane under reduced pressure to obtain a new type of polyether blue macromolecular dye.

[0087] Comparative Example 1

[0088] Compared to Example 1, the amount of terminal amino polyether added was reduced to 150g (1.5 parts), while the proportions of other components remained the same as in subsequent steps.

[0089] Comparative Example 2

[0090] Compared to Example 1, the amount of isophorone diisocyanate added was reduced to 33.35g (1.5 parts), while the proportions of other components remained the same as in subsequent steps.

[0091] Comparative Example 3

[0092] Compared to Example 1, the modified amino-terminated polyether was added by direct pouring, while the proportions of other components remained the same as in subsequent steps.

[0093] Comparative Example 4

[0094] Compared to Example 7, the molecular weight of the methoxy polyether was changed to 100 (MPEG100), and the corresponding amount added was changed to 25g (2.5 parts). The proportions of other components were the same as in the subsequent steps.

[0095] The synthesis results of Examples 1-8 and Comparative Examples 1-4 are shown in Table 1.

[0096] Table 1. Results of synthesis experiments in Examples 1-8 and Comparative Examples 1-4

[0097] Serial Number color Average molecular weight Color content Example 1 Rose Red 2824 13.8% Example 2 Big Red 4815 7.1% Example 3 Bright yellow 1887 8.6% Example 4 sapphire 6836 5.30% Example 5 Bright Blue 3211 19.2% Example 6 Turquoise 5752 20.1% Example 7 Rose Red 1604 22.7% Example 8 sapphire 1798 20.6% Comparative Example 1 Rose Red 2359 18.1% Comparative Example 2 Rose Red 2167 14.3% Comparative Example 3 Rose Red 2703 13.8% Comparative Example 4 Rose Red 811 36.6%

[0098] Application Examples:

[0099] I. Application Examples in the Field of Writing Ink

[0100] The polyether dyes prepared in Examples 1-6 and Comparative Examples 1-3 were dissolved in water to prepare a 10% color paste, which was used as a raw material to prepare colorant ink for marker pens. The formulation composition was as follows, by mass percentage: 8% polyether dye, 25% 1,2-propanediol, 10% glycerol, 1% surfactant, 55.9% water, and 0.1% preservative. The performance of the colorant ink was tested on the pens (the writing performance was judged by drawing circles on the paper continuously, and the writing performance was judged by drawing 2-3 lines, from best to worst: 1. Smooth writing feel; 2. Average writing feel; 3. Occasional ink breaks, poor writing feel; 4. Poor writing feel, many ink breaks; 5. Rough writing feel, severe ink breaks). The test results are shown in Table 2.

[0101] Table 2 Marker application performance test results

[0102] Test object Viscosity / mPa·s pH Surface tension mN / m Writing effect Example 1 6.7 7.0 28.3 The lines draw normally, and the writing feel is smooth. Example 2 9.4 7.0 28.3 The lines draw normally, and the writing feel is smooth. Example 3 6.3 7.0 28.3 The lines draw normally, and the writing feel is smooth. Example 4 11.7 7.0 28.3 The lines draw normally, and the writing feel is smooth. Example 5 7.8 7.0 28.4 The lines draw normally, and the writing feel is smooth. Example 6 10.1 7.0 28.6 The lines draw normally, and the writing feel is smooth. Comparative Example 1 16.1 7.0 28.3 The ink occasionally breaks when drawing lines, resulting in a poor writing feel. Comparative Example 2 10.7 7.0 28.3 Frequent ink breaks when drawing lines, resulting in poor writing feel. Comparative Example 3 7.9 7.0 28.3 The lines are fine, but the writing feel is a bit thick.

[0103] As shown in Table 2, the polyether dyes prepared in Examples 1 to 6 all exhibit good performance in marker pens.

[0104] In Comparative Example 1, reducing the amount of polyether reaction raw materials resulted in a slight decrease in average molecular weight, but it may have led to a decrease in water solubility, resulting in a significant increase in viscosity and causing ink breakage.

[0105] In Comparative Example 2, reducing the amount of isocyanate resulted in a more significant decrease in molecular weight. Although the viscosity did not increase much in the test, some particles were observed to precipitate out, and the ink frequently failed to run after being formulated. This was likely due to blockage caused by insoluble particles.

[0106] In Comparative Example 3, changing the feeding method to direct mixing led to an increase in double end capping and a decrease in the actual grafting rate of monoisocyanate polyether, resulting in a slight decrease in molecular weight. Although the water solubility was still good and the writing ink flow was normal, there was still some ink flow resistance, and it was not particularly smooth.

[0107] II. Examples of Application of Colorant in Daily Chemicals

[0108] The polyether dyes prepared in Examples 1-6 and Comparative Examples 1-3 were adjusted to have consistent color values ​​according to their color systems. Then, 0.02% dye was added to the base material of a certain brand of laundry detergent to make the finished laundry detergent. The staining test of the finished laundry detergent was performed as follows.

[0109] Staining test:

[0110] Six-fiber cloth: Soak an 8cm long x 1cm wide six-fiber cloth in the base material for 4 hours. After taking it out, rub it repeatedly under tap water for 1 minute. After drying for 2 hours, observe whether there is any color staining on the six-fiber cloth.

[0111] The results of the staining test are shown in Table 3.

[0112] Table 3 Results of staining test

[0113] 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

[0114] As shown in Table 3, the polyether dyes prepared in Examples 1-6 all showed good washability when added to laundry detergent. However, the polyether dyes prepared in Comparative Examples 1-3 showed poor washability when added to laundry detergent due to poor polyether grafting effect and poor water dispersibility, resulting in staining.

[0115] III. Examples of Wood Coating Application

[0116] The polyether dyes prepared in Examples 3, 7, and 8, as well as Comparative Example 4, were mixed with water to form a 30% color paste, which was used as a colorant paste for wood coatings. The dye in Comparative Example 4 had low solubility in water, so ethylene glycol was used instead of water to prepare the color paste.

[0117] Preparation of wood coating: 8% color paste, 43% acrylic emulsion, and 35% waterborne polyurethane dispersion are added to a paint mixing tank. 0.3% pH adjuster AMP95 and 2% nano-silica dispersion are added. After rapid and uniform stirring, 0.5% defoamer BYK024 is diluted with 8% deionized water and slowly added to the system. The mixture is dispersed at 1500 r / min until no pinholes are observed on a fineness tester. Then, 0.5% wetting agent WetKL270, 0.6% leveling agent Glide450, and 0.8% matting agent TSW 100W are added sequentially. The viscosity is then adjusted to the appropriate level using 0.8% thickener AR8959. 0.5% antibacterial agent is added and stirred thoroughly until uniform. Finally, the mixture is filtered to obtain the waterborne wood coating.

[0118] The water-based wood coatings obtained in Examples 3, 7, and 8 and Comparative Example 4 were sprayed onto the surface of wooden specimens. After spraying, the coatings were heated and cured, and the following coating performance tests were conducted:

[0119] Coating adhesion test: The adhesion was determined according to GB / T9286 1998 "Cross-cut test for paint and varnish film".

[0120] Coating hardness test: The hardness of the coating film was determined according to GB / T6739-2006 "Paints and Varnishes - Pencil Method for Determination of Hardness of Coating Film".

[0121] Water immersion resistance test of coating: Use paraffin to seal the edges of the wooden specimen to prevent water from entering from the edges of the wooden specimen. Immerse half of the wooden specimen in water and leave the other half for comparison. After a certain period of time, take it out and observe the tested paint film with the naked eye to see if wrinkling or peeling occurs.

[0122] The results are shown in Table 4.

[0123] Table 4 Results of Wood Coating Application Tests

[0124] Test object Adhesion hardness 50h water soaking Example 3 0 2H No abnormalities Example 7 0 2H No abnormalities Example 8 0 2H No abnormalities Comparative Example 4 0 2H No abnormalities

[0125] 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 coating formulations; however, 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.

[0126] This invention discloses a novel waterborne polyether-type macromolecular dye, which is prepared by reacting hydrophilic monofunctional amino polyether or alkoxy polyether with diisocyanate (feed ratio ≤1.0) at one end to obtain terminal isocyanate-based polyether, which is then reacted with hydroxy / amino dye to obtain polyether-grafted macromolecular dye. The resulting novel polyether dye has a controllable molecular weight, is prepared under mild conditions, produces no toxic byproducts, and has good color development performance. It can be used as a raw material pigment for waterborne writing ink, marking ink, waterborne printing ink, waterborne coatings, and daily chemical washing and care products.

[0127] The foregoing description is not intended to limit the invention, nor is the invention limited to the examples given. Any changes, modifications, additions, or substitutions made by those skilled in the art within the scope of the invention should also be considered within the protection scope of the invention.

Claims

1. A polyether-grafted macromolecular dye, characterized in that, The preparation method 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; and 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 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; and 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; B. Mix 2-8 parts of dehydrated monoamino polyether or alkoxy polyether with 20-200 parts of solvent, and slowly dropwise add the mixture to a temperature-controlled and stirred reaction solution containing 2-8 parts of isocyanate and 10-100 parts of solvent. Monitor the reaction with infrared light until the isocyanate signal peak shows a significant decrease compared to the initial reaction solution and remains unchanged for a period of time to obtain terminal isocyanate-based polyether. The isocyanate is an aliphatic diisocyanate, and the feed ratio of monoamino polyether or alkoxy polyether to isocyanate in the reaction materials is ≤1.

0. (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.

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

3. The 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.

4. The 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℃.

5. The 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.

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

Images