Colored crayon and preparation method thereof

Abstract

The invention discloses a colored crayon and a preparation method thereof.The colored crayon comprises, by mass, 20%-60% of solid paraffin, 5%-10% of liquid paraffin, 20%-50% of filler, 5%-20% of macromolecular dye, 5%-10% of calcium stearate and 5%-10% of zinc stearate, and the sum of the mass percentages of all the components is 100%. The dye is modified, PO chain segments are connected into the dye, the molecular weight of the dye is increased, the dye is difficult to absorb by skin and has good safety, the intermiscibility of the dye and wax oil is improved, and the manufactured crayon is uniform in color, smooth and bright.

Description

Technical Field

[0001] The invention relates to the technical field of colored crayon preparation, in particular to a colored crayon and a preparation method thereof. Background Art

[0002] The dyes used in children's colored crayons currently on the market are mainly some solvent-based small molecule dyes on the market. Once these dyes stick to the skin, they are difficult to remove and may cause symptoms such as skin allergies. Long-term contact is very harmful to the human body. In addition, traditional powder dyes and crayons have poor solubility, resulting in uneven colors, rough and dull surfaces in the crayons produced. There are also some natural dye colored crayons that are single in color and expensive. Summary of the Invention

[0003] The present invention aims to overcome the technical deficiencies of the prior art and provide colored crayons and a method for preparing the same. The present invention modifies the dye by inserting PO chains into the dye to increase its molecular weight, making it difficult for the dye to be absorbed by the skin and providing excellent safety. Furthermore, the compatibility between the dye and wax oil is increased, resulting in a crayon with uniform color, smoothness, and a bright appearance. Furthermore, the macromolecular dye prepared by the present invention has a rich color palette and is made from readily available and inexpensive raw materials.

[0004] The technical solutions adopted by the present invention to solve the above technical problems are as follows:

[0005] A macromolecular dye precursor, which is an aniline polyether with PO segment substituted or unsubstituted (abbreviated as PAN-PPO), has the following general structural formula:

[0006]

[0007] Wherein R1, R2, R3, and R4 are any one of -H, -CH3, -Cl, and -Br; 8≤n≤30 and n is an integer.

[0008] Preferably, in the formula, R1, R2, R3, and R4 are all -H; and n=9.

[0009] Preferably, in the formula, R1 is -CH3, R2, R3, and R4 are all -H; and n=9.

[0010] The method for preparing the macromolecular dye precursor as described above comprises the following steps:

[0011] (1) Add 1 molar equivalent of substituted or unsubstituted aniline and 2.1 molar equivalents of hydrochloric acid to a reaction kettle, replace the air in the reaction kettle with N2 several times, raise the temperature to 90-120°C, control the pressure, and slowly introduce 2 molar equivalents of propylene oxide to react. After the addition is completed, continue to keep the temperature to react, thereby synthesizing substituted or unsubstituted N,N-dihydroxyisopropylaminoaniline;

[0012] (2) The above-mentioned substituted or unsubstituted N,N-dihydroxyisopropylaminoaniline is added with 0.04 molar equivalent of a base catalyst, and 16 to 60 molar equivalents of propylene oxide are blown into the mixture to carry out a heat-insulating reaction at 100 to 120° C. to synthesize an aniline polyether substituted or unsubstituted with a PO segment, i.e., a macromolecular dye precursor.

[0013] Preferably, in step (1), the substituted or unsubstituted aniline is aniline or m-toluidine.

[0014] Preferably, in step (1), the concentration of the hydrochloric acid is 36 wt %.

[0015] Preferably, in step (1), the pressure is 0.3 MPa.

[0016] Preferably, in step (1), the insulation reaction time is 1 hour.

[0017] Preferably, in step (1), the substituted or unsubstituted N,N-dihydroxyisopropylaminoaniline is cooled to 30° C., chloroform and water are added, extracted and purified, and the organic layer is evaporated to dryness to obtain pure N,N-dihydroxyisopropylaminoaniline.

[0018] Preferably, in step (2), the base catalyst is KOH.

[0019] Preferably, in step (2), the insulation reaction time is 2 hours.

[0020] A macromolecular dye, wherein the structure of the macromolecular dye is any one of the following structural formulas:

[0021]

[0022]

[0023] Wherein R1, R2, R3, and R4 are any one of -H, -CH3, -Cl, and -Br; R5, R6, and R7 are any one of -H, -CH3, -COH3, -CN, -Br, -NO2, -Cl, and -NHCOCH3; R8 and R9 are any one of -C1 and -Br; R 10 is any one of -NO2, -Br, and -Cl; R 11 is any one of -H, -SO3H, and -OH; R 12 It is any one of -H, -SO3H, and -Cl; 5≤n≤30 and n is an integer.

[0024] The structures and colors corresponding to the different structures of the macromolecular dye are as follows:

[0025] When R1, R2, R3, and R4 in formula (1) are -H, or R2, R3, and R4 are -H, R1 is -CH3, 5≤n≤30 and n is an integer, R5 is -NO2, and R6 and R7 are both -Br, a macromolecular brown polymer liquid dye can be prepared;

[0026] When R1, R2, R3, and R4 in formula (1) are all -H, or R2, R3, and R4 are all -H, R1 is -CH3, 5≤n≤30 and n is an integer, R5 is -NO2, R6 is -Cl, -Br or -CN, and R7 is -H, a macromolecular purple polymer liquid dye can be prepared;

[0027] When R1, R2, R3, and R4 in formula (1) are all -H, 5≤n≤30 and n is an integer, R5 is -NO2, and R6 and R7 are all -H, a macromolecular yellow-red polymer liquid dye can be prepared;

[0028] When R2, R3, and R4 in formula (1) are -H, R1 is -CH3, 5≤n≤30 and n is an integer, R5 is -NO2, and R6 and R7 are both -H, a macromolecular red polymer liquid dye can be prepared;

[0029] When R2, R3, and R4 in formula (1) are -H, R1 is -NHCOCH3, 5≤n≤30 and n is an integer, R5 is -NO2, and R6 and R7 are both -H, a macromolecular burgundy polymer liquid dye can be prepared;

[0030] When R1, R2, R3, and R4 in formula (1) are -H, 5≤n≤30 and n is an integer, R5 is -COH3, and R6 and R7 are both -H, a macromolecular brilliant yellow polymer liquid dye can be prepared;

[0031] When R1, R2, R3, and R4 in formula (1) are -H, 5≤n≤30 and n is an integer, R5 is -H, and R6 and R7 are both -Cl, a macromolecular brilliant orange polymer liquid dye can be prepared;

[0032] When R1, R2, R3, and R4 in formula (2) are -H, or R2, R3, and R4 are -H, R1 is -CH3 or -NHCOCH3, 5≤n≤30 and n is an integer, and R8 and R9 are both -Br or -Cl, a brilliant red macromolecular polymer liquid dye can be prepared;

[0033] When R1, R2, R3, and R4 in formula (3) are -H, or R2, R3, and R4 are -H, R1 is -CH3 or -NHCOCH3, 5≤n≤30 and n is an integer, R 10 -NO2, can be used to prepare macromolecular royal blue polymer liquid dye;

[0034] When R1, R2, R3, and R4 in formula (4) are -H, or R2, R3, and R4 are -H, R1 is -CH3 or -NHCOCH3, 5≤n≤30 and n is an integer, R 11 -H, R 12 -SO3Na or R 11 、R 12 Both are -SO3Na, which can be used to prepare macromolecular bright blue polymer liquid dyes; R 11 、R 12 Both are -H, which can be used to prepare bright green macromolecular polymer liquid dyes; R 11 -OH, R 12 For -H, a brilliant purple macromolecular polymer liquid dye can be prepared.

[0035] The method for preparing the macromolecular dye as described above comprises the following steps:

[0036] When the macromolecular dye is of formula (1), formula (2), or formula (3), the preparation method thereof comprises the following steps:

[0037] (1) Preparation of aniline diazo liquid derivatives;

[0038] (2) coupling the aniline diazo liquid derivative with the macromolecular dye precursor PAN-PPO in ice water;

[0039] (3) adding alkali to adjust the pH of the coupling solution to neutral, then adding chloroform for extraction and purification, and evaporating the solvent to obtain the macromolecular dye;

[0040] When the macromolecular dye is of formula (4), the preparation method thereof comprises the following steps:

[0041] (1) Mixing benzaldehyde derivatives with macromolecular dye precursor PAN-PPO, using sulfuric acid solution as solvent and urea as catalyst, and carrying out condensation reaction at 90-110°C;

[0042] (2) diluting with water, using manganese dioxide as an oxidant and sulfuric acid as a pH regulator, carrying out oxidation reaction at 10-35°C, and then using calcium hydroxide as an acid-binding agent to adjust the pH to 5.5-6.0;

[0043] (3) Filter and distill the filtrate to remove water to obtain a macromolecular dye.

[0044] A colored crayon comprises the following components, calculated by mass percentage: 20% to 60% of solid paraffin, 5% to 10% of liquid paraffin, 20% to 50% of filler, 5% to 20% of macromolecular dye, 5% to 10% of calcium stearate, and 5% to 10% of zinc stearate, the total mass percentage of each component being 100%.

[0045] Preferably, the filler is any one or both of calcium carbonate and talc.

[0046] The preparation method of the above-mentioned colored crayon comprises the following steps:

[0047] (1) putting solid paraffin, liquid paraffin, calcium stearate and zinc stearate into a stirring kettle, heating and melting, stirring evenly, adding filler and macromolecular dye under stirring and keeping warm;

[0048] (2) Molding and cooling to obtain colored crayons.

[0049] The main features of the above process are: eliminating the pigment three-roller grinding step, reducing workshop dust pollution, and obtaining a product with stable performance.

[0050] Compared with the prior art, the present invention has the following beneficial effects:

[0051] The present invention modifies the dye by inserting PO chains into the dye to increase its molecular weight, making it difficult to be absorbed by the skin and having good safety. It also increases the compatibility of the dye and wax oil, so that the prepared crayons have uniform color, smoothness and brightness. In addition, the macromolecular dye prepared by the present invention has rich colors and the raw materials are easily available and inexpensive. DETAILED DESCRIPTION

[0052] In order to better understand the content of the present invention, the following is further described in conjunction with specific examples. It should be understood that these examples are only used to further illustrate the present invention and are not intended to limit the scope of the present invention. In addition, it should be understood that after reading the content described in the present invention, those skilled in the art may make some non-essential changes or adjustments to the present invention, which still fall within the scope of protection of the present invention.

[0053] Example 1

[0054] A. Preparation of polymer dye precursor aniline 10PO polyether

[0055] In a reactor equipped with a stirrer, a thermometer, a gas inlet and outlet, a reflux condenser, and a bubbler, 93.1 g (1 mol) of aniline and 213 g of 36 wt% hydrochloric acid were added. The air in the reactor was replaced with N2 three times. The temperature was slowly raised to 100°C. Under a certain pressure (0.3 MPa), 2 mol of propylene oxide was introduced and the reaction was kept warm for 1 hour to synthesize N,N-dihydroxyisopropylaminoaniline. The temperature was then lowered to 30°C, 200 g of chloroform and 200 g of water were added, and the product was extracted and purified. The organic layer was evaporated to dryness to obtain pure N,N-dihydroxyisopropylaminoaniline.

[0056] Take 1 mol of N,N-dihydroxyisopropylaminoaniline, add 2.24 g of KOH, raise the temperature to 120°C, introduce 8 mol of propylene oxide to react, and keep the temperature to react for 2 hours to obtain aniline 10PO polyether with 10PO chain segments.

[0057] B. Preparation of polymer dye precursor m-toluidine 10PO polyether

[0058] In a reactor equipped with a stirrer, a thermometer, a gas inlet and outlet, a reflux condenser and a bubbler, 107.2 g (1 mol) of m-toluidine and 213 g of 36 wt% hydrochloric acid were added, the air in the reactor was replaced with N2 three times, the temperature was slowly raised to 100 ° C., and a certain pressure (0.3 MPa) was controlled. 2 mol of propylene oxide was introduced to synthesize N, N-dihydroxyisopropylaminoaniline; the temperature was lowered to 30 ° C., 200 g of chloroform and 200 g of water were added, and the product was extracted and purified. The organic layer was evaporated to dryness to obtain pure N, N-dihydroxyisopropylamino-m-toluidine.

[0059] Take 1 mol of N,N-dihydroxyisopropylamino-m-toluidine, add 2.24 g of KOH, raise the temperature to 120°C, introduce 8 mol of propylene oxide to react, and keep the temperature for 2 hours to obtain m-toluidine 10PO polyether with 10PO segments.

[0060] Example 2

[0061] A. Preparation of macromolecular yellow-red polymer liquid dye

[0062] Add 15 g (0.21 mol) of sodium nitrite to a 50 ml beaker, add 30 g of water, stir until dissolved, and set aside.

[0063] 50 g of ice water, 80 g (0.79 mol) of 36 wt% hydrochloric acid, and 27.9 g (0.2 mol) of p-nitroaniline were added to a 250 ml flask, and the mixture was stirred and cooled to 0-5°C in an ice-water bath; 50 g of ice was added, and after the ice was added, the prepared sodium nitrite aqueous solution was slowly added dropwise over a period of about 20 minutes. After the addition was complete, the mixture was kept warm at 0-5°C and reacted for 1-1.5 hours; after the end point was reached, the mixture was filtered with suction using a Buchner funnel, the filtrate was collected, poured into a 250 ml flask, stirred, and 0.1 g of aminosulfonic acid was added to eliminate excess sodium nitrite to obtain a p-nitroaniline diazo solution.

[0064] To a 2000 ml flask, 137.3 g (0.204 mol) of the aniline 10PO polyether prepared in Example 1 (A) above was added, followed by 550 g of ice water. Stirring was started, an ice-water bath was placed, and the temperature was controlled at 5-8°C. The diazo solution was slowly added dropwise over a period of about 1 hour. After completion of the addition, the temperature was maintained at 10-15°C and the reaction was carried out for 4-6 hours to complete the coupling reaction. Sodium carbonate was added to the reacted coupling solution to adjust the pH to 6.5-7.0. After the adjustment, 250 g of chloroform was added, and stirring was continued for 30 minutes. After the stirring was turned off, the lower organic layer was collected and evaporated to dryness on a rotary evaporator to obtain a macromolecular yellow-red polymer liquid dye.

[0065] B. Preparation of macromolecular red polymer liquid dye

[0066] According to the preparation method of the yellow-red polymer liquid dye in Example 2, p-nitroaniline diazo liquid was synthesized.

[0067] A 2000 ml flask was charged with 140 g (0.204 mol) of the m-toluidine 10PO polyether prepared in Example 1 (B) above, and 550 g of ice water. The mixture was stirred and placed in an ice-water bath at a temperature of 5-8°C. The diazo solution was slowly added dropwise over a period of about 1 hour. After completion of the addition, the temperature was maintained at 10-15°C and the reaction was carried out for 4-6 hours to complete the coupling reaction. Sodium carbonate was added to the reacted coupling solution to adjust the pH to 6.5-7.0. After the adjustment, 250 g of chloroform was added, and the mixture was stirred for 30 minutes. The stirring was then turned off and the mixture was allowed to stand for 30 minutes. The lower organic layer was collected and evaporated to dryness on a rotary evaporator to obtain a macromolecular, bright red polymer liquid dye.

[0068] Example 3

[0069] Preparation of macromolecular brilliant yellow polymer liquid dye:

[0070] Add 14.5 g (0.204 mol) of sodium nitrite to a 50 ml beaker, add 29 g of water, stir until dissolved, and set aside.

[0071] First, add 80g of ice water to a 250ml flask, add 60.8g (0.60mol) of 36wt% hydrochloric acid, start stirring, then add 25.4g (0.2mol) of p-methoxyaniline, cool in an ice bath, slurry and disperse for 2 to 2.5 hours, cool to about 5°C in an ice bath, and then add 100g of ice; slowly add the prepared sodium nitrite solution dropwise, controlling the temperature below 5°C, and after the addition is completed, keep warm for 1 hour, add 0.1g of aminosulfonic acid to eliminate excess sodium nitrite to obtain p-methoxyaniline diazo solution.

[0072] 200 g of ice water was added to a 2000 ml flask, and 137.3 g (0.204 mol) of the aniline 10PO polyether in Example 1 (A) was added. Stirring was started, and diazo solution was added dropwise. The temperature was controlled at 5-15° C. during the process, and the addition was completed over about 15 minutes. After the diazo solution was added, sodium bicarbonate was added to slowly adjust the pH to 3.5-4.0, and then sodium carbonate powder was added to slowly adjust the pH to 7.5-8.5. After the adjustment, the pH was continued to be maintained and the reaction was allowed to proceed naturally for 6-8 hours to complete the coupling reaction. 250 g of chloroform was added, and stirring was continued for 30 minutes. Then, stirring was turned off, and the lower organic layer was collected and evaporated to dryness on a rotary evaporator to obtain a macromolecular bright yellow polymer liquid dye.

[0073] Example 4

[0074] Preparation of macromolecular brilliant orange polymer liquid dye:

[0075] Add 14.5 g (0.204 mol) of sodium nitrite to a 50 ml beaker, add 29 g of water, stir until dissolved, and set aside.

[0076] First, add 80g of ice water to a 250ml flask, add 60.8g (0.60mol) of 36wt% hydrochloric acid, start stirring, then add 33g (0.2mol) of 2,6-dichloroaniline, put in an ice bath, beat for 1 to 1.5 hours to make it evenly dispersed, and cool to below 10°C; add 40g of ice, slowly add sodium nitrite aqueous solution dropwise, control the temperature at 0 to 5°C after the dropwise addition, keep warm for 1.5 to 2h, add 0.1g of aminosulfonic acid to eliminate excess sodium nitrite, and react to obtain 2,6-dichloroaniline diazo solution.

[0077] Place 200 g of ice water in a 2000 ml beaker, start stirring and add 137.3 g (0.204 mol) of aniline 10PO polyether in Example 1 (A), stir for 5 minutes and stir evenly, add 34 g of baking soda, stir for 10 minutes, stir evenly, and control the temperature at 5-10°C; slowly add the diazo solution dropwise to the coupling component, maintaining the pH at 6.5-7.5. If the pH is lower than 6.5, add baking soda in time, and maintain the temperature at 10-15°C; after the addition is completed, the pH is 6.5-7.5, and react naturally for 6-8 hours to complete the coupling reaction; add 250 g of chloroform, continue stirring for 30 minutes, turn off the stirring, let stand for 30 minutes, collect the lower organic layer, and evaporate to dryness on a rotary evaporator to obtain a macromolecular bright orange polymer liquid dye.

[0078] Example 5

[0079] Preparation of macromolecular royal blue polymer liquid dye:

[0080] 120 g (1.2 mol) of 98 wt% sulfuric acid was added to a 250 ml flask, and the mixture was cooled to below 20°C in an ice-water bath. Stirring was started, and 64 g (0.206 mol) of 41 wt% nitrosylsulfuric acid was added; the mixture was cooled to below 0-5°C in an ice bath, and 39.8 g (0.2 mol) of 2-amino-5-nitrobenzisothiazole was slowly added. The temperature was controlled at 5-8°C, and the reaction was kept warm for 3-4 hours. The reaction was completed to obtain 2-amino-5-nitrobenzisothiazole diazo solution.

[0081] 1500 g of ice water was added to a 3000 ml beaker, and 140 g (0.204 mol) of the m-toluidine 10PO polyether in Example 1 (B) was added, followed by 0.5 g of urea. An ice-water bath was placed, stirring was started, and the diazo solution was added dropwise. The temperature during the addition was controlled at 0-5° C. and the addition was completed in about 2 hours. After the addition was completed, the mixture was kept at 0-5° C. for 2-3 hours, and then naturally reacted for 4-5 hours to complete the coupling reaction. Sodium carbonate was added to the reacted coupling solution to adjust the pH to 6.5-7.0. After the adjustment was completed, 250 g of chloroform was added, and stirring was continued for 30 minutes. The stirring was turned off, and the lower organic layer was collected and evaporated to dryness on a rotary evaporator to obtain a macromolecular royal blue polymer liquid dye.

[0082] Example 6

[0083] Preparation of macromolecular bright blue polymer liquid dye:

[0084] In a 1000ml flask, 137.3g (0.204mol) of aniline 10PO polyether in Example 1 (A) was added, 2g of urea was added, 2g of water was added, and 21.9g (0.1mol) of sodium o-sulfonate benzaldehyde was added with stirring. After stirring for 10 minutes, 8.6g (0.086mol) of 98%wt sulfuric acid was slowly added dropwise. After the addition, the temperature was slowly raised to 105-110°C and kept warm for 24 hours to terminate the condensation reaction.

[0085] The condensation reaction mixture was cooled to 60°C, 400 g of ice water was added and cooled to 15-20°C, 98% wt sulfuric acid was added to adjust the pH to 1.0-1.5, stirred for 10 minutes after addition, and the temperature was controlled at 25-30°C. 16 g (0.16 mol) of manganese dioxide was slowly added over 40-60 minutes. After addition, the mixture was kept at 25-30°C and reacted for 5 hours. Calcium hydroxide (0.01 mol) was added to adjust the pH to 5.5-6.0, and the filtrate was collected by filtration. The filtrate was evaporated to dryness on a rotary evaporator to obtain a macromolecular bright blue polymer liquid dye.

[0086] Example 7

[0087] Preparation of macromolecular deep purple polymer liquid dye:

[0088] To a 250ml flask, add 120g (1.2mol) of 98wt% sulfuric acid, cool to below 20°C in an ice-water bath, start stirring, and add 64g (0.206mol) of 41wt% nitrosylsulfuric acid; then cool to below 0-5°C in an ice-water bath, slowly add 33.25g (0.2mol) of 2-cyano-4-nitroaniline, control the temperature at 8-15°C, and keep the reaction warm for 3-4 hours. The reaction is completed to obtain a 2-cyano-4-nitroaniline diazo solution.

[0089] 1500 g of ice water was added to a 3000 ml beaker, 140 g (0.204 mol) of the m-toluidine 10PO polyether in Example 1 (B) above was added, 0.5 g of urea was added, an ice-water bath was placed, stirring was turned on, and the diazo solution was added dropwise. The temperature during the addition was controlled at 0-5° C. and the addition was completed in about 2 hours. After the addition was completed, the mixture was kept at 0-5° C. for 2-3 hours, and then naturally reacted for 4-5 hours to complete the coupling reaction. Sodium carbonate was added to the reacted coupling solution to adjust the pH to 6.5-7.0. After the adjustment was completed, 250 g of chloroform was added, and stirring was continued for 30 minutes. After the stirring was turned off, the lower organic layer was collected and evaporated to dryness on a rotary evaporator to obtain a macromolecular deep purple-red polymer liquid dye.

[0090] Example 8

[0091] Preparation of macromolecular brilliant red polymer liquid dye:

[0092] 84 g (0.1 mol) of 22% wt 5.6-dichlorobenzothiazole was added to a 250 ml flask, and 32 g (0.103 mol) of 41 wt % liquid was slowly added with stirring, and stirred for 10 minutes.

[0093] First, add 55g of water to a 250ml flask, start stirring and slowly add 50g (0.5mol) of 98wt% sulfuric acid. Cool to below 0°C in an ice bath, add 0.5g of emulsifier AEO-09, and then slowly add the prepared diazo component after the temperature reaches 5°C. Control the temperature to ≤5°C and add the mixture over about 2 to 3 hours. After the addition, continue the reaction for 2 to 3 hours. The reaction is completed to obtain 5.6-dichlorobenzothiazole diazo solution.

[0094] 250 g of ice water was added to a 2000 ml beaker, and 25 g (0.25 mol) of sulfuric acid was slowly added with stirring. 70 g (0.103 mol) of the m-toluidine 10PO polyether in Example 1 (B) was added, and the temperature was cooled to about 5°C in an ice bath. 250 g of ice was added before coupling, and the temperature was kept below 0°C after the addition. The diazo solution was slowly added, and the temperature was controlled below 5°C during the addition process. After the addition was completed, the reaction was kept warm for 2 hours and then naturally reacted for 6 hours to complete the coupling reaction. Sodium carbonate was added to the reacted coupling solution to adjust the pH to 6.5-7.0. After the adjustment, 125 g of chloroform was added, and stirring was continued for 30 minutes. The stirring was turned off, and the lower organic layer was collected and evaporated to dryness on a rotary evaporator to obtain a macromolecular brilliant red polymer liquid dye.

[0095] Comparative Example 1

[0096] Preparation of polymer dye precursor aniline 10EO polyether:

[0097] In a reaction kettle equipped with a stirrer, a thermometer, a gas inlet and outlet, a reflux condenser and a bubbler, 93.1 g (1 mol) of aniline and 213 g of 36 wt% hydrochloric acid were added. The air in the reaction kettle was replaced with N2 three times. The temperature was slowly raised to 90-120°C. Under a certain pressure (0.3 MPa), 2 mol of ethylene oxide was introduced to synthesize N,N-dihydroxyethylaniline. The temperature was then lowered to 30°C, 200 g of chloroform and 200 g of water were added, and the product was extracted and purified. The organic layer was evaporated to dryness to obtain pure N,N-dihydroxyethylaniline.

[0098] Take 1 mol of N,N-dihydroxyethylaniline, add 2.24 g of KOH, raise the temperature to 150-170°C, introduce 8 mol of ethylene oxide for reaction, and keep the temperature for 2 hours to obtain aniline 10EO polyether with 10EO chain segments.

[0099] A. Preparation of Aniline-Containing 10EO Polyether Macromolecule Yellow-Red Polymer Liquid Dye

[0100] The preparation method is basically the same as that of Example 2 (A), except that the aniline 10PO polyether is replaced with the aniline 10EO polyether prepared in Comparative Example 1, and the feed amount is 108.7 g (0.204 mol).

[0101] B. Preparation of aniline 10EO polyether macromolecular brilliant yellow polymer liquid dye

[0102] The preparation method is basically the same as that of Example 3, except that the aniline 10PO polyether is replaced by the aniline 10EO polyether prepared in Comparative Example 1, and the feed amount is 108.7 g (0.204 mol).

[0103] C. Preparation of bright blue polymer liquid dye containing aniline 10EO polyether macromolecule

[0104] The preparation method is basically the same as that of Example 6, except that the aniline 10PO polyether is replaced by the aniline 10EO polyether prepared in Comparative Example 1, and the feed amount is 108.7 g (0.204 mol).

[0105] Comparative Example 2

[0106] Preparation of polymer dye precursor aniline 5EO-5PO polyether:

[0107] In a reaction kettle equipped with a stirrer, a thermometer, a gas inlet and outlet, a reflux condenser and a bubbler, 93.1 g (1 mol) of aniline and 213 g of 36 wt% hydrochloric acid were added. The air in the reaction kettle was replaced with N2 three times. The temperature was slowly raised to 90-120°C. Under a certain pressure (0.3 MPa), 2 mol of ethylene oxide was introduced to synthesize N,N-dihydroxyethylaniline. The temperature was then lowered to 30°C, 200 g of chloroform and 200 g of water were added, and the product was extracted and purified. The organic layer was evaporated to dryness to obtain pure N,N-dihydroxyethylaniline.

[0108] To 1 mol of N,N-dihydroxyethylaniline, add 2.24 g of KOH, raise the temperature to 120°C, introduce 5 mol of propylene oxide, and keep the reaction at this temperature for 2 hours. Then, introduce 4 mol of ethylene oxide and keep the reaction at this temperature for 2 hours to obtain aniline 5EO-5PO polyether with 5EO-5PO chain segments.

[0109] A. Preparation of 5EO-5PO Polyether Macromolecule Royal Blue Polymer Liquid Dye Containing Aniline

[0110] The preparation method is basically the same as that of Example 5, except that the m-toluidine 10PO polyether is replaced by the m-toluidine 5EO-5PO polyether prepared in Comparative Example 2, and the feed amount is 123.0 g (0.204 mol).

[0111] B. Preparation of aniline-containing 5EO-5PO polyether macromolecular brilliant red polymer liquid dye

[0112] The preparation method is basically the same as that of Example 8, except that the m-toluidine 10PO polyether is replaced by the m-toluidine 5EO-5PO polyether prepared in Comparative Example 2, and the feed amount is 123.0 g (0.204 mol).

[0113] C. Preparation of deep purple-red polymer liquid dye containing aniline 5EO-5PO polyether macromolecule

[0114] The preparation method is the same as that of Example 7, except that the m-toluidine 10PO polyether is replaced with the m-toluidine 5EO-5PO polyether prepared in Comparative Example 2, and the feed amount is 123.0 g (0.204 mol).

[0115] The structures of the compounds corresponding to the above examples are shown in the table below:

[0116]

[0117]

[0118]

[0119] The specific application implementation is as follows:

[0120] Example A: A method for preparing a black crayon

[0121] A black crayon, the specific components by mass percentage are shown in the table below.

[0122] The preparation method is as follows: solid paraffin, white oil, calcium stearate and zinc stearate are put into a stirring kettle, heated and melted, stirred evenly, fillers and macromolecular dyes are added in the stirring state, kept warm, molded, and cooled to obtain crayons.

[0123] The macromolecular dye is composed of the macromolecular bright blue polymer liquid dye in Example 6, the macromolecular brilliant orange polymer liquid dye in Example 4, and the macromolecular brilliant yellow polymer liquid dye in Example 3 in a mass ratio of 10:2:3.

[0124] Examples B to I are based on Example A with changes in material ratios, dye types, and filler types. The specific component compositions are shown in the table below.

[0125] Wherein embodiment B is a lake blue crayon, embodiment C is an orange crayon, embodiment D is a red crayon, embodiment E is a bright yellow crayon, embodiment F is a bright orange crayon, embodiment G is a royal blue crayon, embodiment H is a bright blue crayon, and embodiment I is a dark purple crayon.

[0126] Comparative Example a is based on Example A, except that the macromolecular dye is replaced with pigment carbon black. The specific component composition is shown in the table below.

[0127] Comparative Example b is based on Example D, except that the macromolecular dye is replaced with an aqueous bright red slurry. The specific component composition is shown in the table below.

[0128]

[0129]

[0130] The application test results are shown in the table below:

[0131]

[0132] The application test methods in the above table are as follows:

[0133] (1) Writing fluency: Use the prepared crayon to draw a line on paper to test its smoothness, uniformity of line thickness, and continuity;

[0134] (2) Migration resistance: Draw a line on paper with the prepared crayon to test the migration of the dye on the paper;

[0135] (3) Washability: draw the prepared crayon on a six-fiber cloth, then wash it in a 5% soapy water machine and observe the residue on the cloth;

[0136] (4) Vibrance: Draw a line on paper with the prepared crayon and observe its brightness;

[0137] (5) Powder shedding: Draw a line on paper with the prepared crayon, shake the paper, or touch it with your hands to observe the powder shedding state;

[0138] (6) Compatibility: During the preparation of crayons, observe their solubility and whether they will form granules.

[0139] Comparative Examples 1a, 1b, 1c, 2a, 2b, and 2c correspond to the three application schemes A, B, and C in Comparative Example 1 and Comparative Example 2, respectively. The above six comparative examples only change the color scheme based on the solution in Example A. The test results are as follows:

[0140]

[0141] Note: The above rating standard is 5 is the best and 0 is the worst.

[0142] The above description is not intended to limit the present invention, and the present invention is not limited to the above examples. Any changes, modifications, additions or substitutions made by persons of ordinary skill in the art within the spirit and scope of the present invention shall also fall within the scope of protection of the present invention.

Claims

1. A colored crayon, characterized in that: The composition comprises the following components by mass percentage: 20% to 60% of solid paraffin, 5% to 10% of liquid paraffin, 20% to 50% of filler, 5% to 20% of macromolecular dye, 5% to 10% of calcium stearate, and 5% to 10% of zinc stearate, and the sum of the mass percentages of the components is 100%; The structure of the macromolecular dye is any one of the following structural formulas: Wherein R1, R2, R3, and R4 are any one of -H, -CH3, -Cl, and -Br; R5, R6, and R7 are any one of -H, -CH3, -COH3, -CN, -Br, -NO2, -Cl, and -NHCOCH3; R8 and R9 are any one of -Cl and -Br; R 10 is any one of -NO2, -Br, and -Cl; R 11 is any one of -H, -SO3H, and -OH; R 12 It is any one of -H, -SO3H, and -Cl; 5≤n<30 and n is an integer.

2. A colored crayon as claimed in claim 1, characterized in that: The structures and colors corresponding to the different structures of the macromolecular dye are as follows: When R1, R2, R3, and R4 in formula (1) are -H, or R2, R3, and R4 are -H, R1 is -CH3, 5≤n<30 and n is an integer, R5 is -NO2, and R6 and R7 are both -Br, a macromolecular brown polymer liquid dye can be prepared; When R1, R2, R3, and R4 in formula (1) are all -H, or R2, R3, and R4 are all -H, R1 is -CH3, 5≤n<30 and n is an integer, R5 is -NO2, R6 is -Cl, -Br or -CN, and R7 is -H, a macromolecular purple polymer liquid dye can be prepared; When R1, R2, R3, and R4 in formula (1) are all -H, 5≤n<30 and n is an integer, R5 is -NO2, and R6 and R7 are all -H, a macromolecular yellow-red polymer liquid dye can be prepared; When R2, R3, and R4 in formula (1) are -H, R1 is -CH3, 5≤n<30 and n is an integer, R5 is -NO2, and R6 and R7 are both -H, a macromolecular red polymer liquid dye can be prepared; When R2, R3, and R4 in formula (1) are -H, R1 is -NHCOCH3, 5≤n<30 and n is an integer, R5 is -NO2, and R6 and R7 are both -H, a macromolecular burgundy polymer liquid dye can be prepared; When R1, R2, R3, and R4 in formula (1) are -H, 5≤n<30 and n is an integer, R5 is -COH3, and R6 and R7 are both -H, a macromolecular brilliant yellow polymer liquid dye can be prepared; When R1, R2, R3, and R4 in formula (1) are -H, 5≤n<30 and n is an integer, R5 is -H, and R6 and R7 are both -Cl, a macromolecular brilliant orange polymer liquid dye can be prepared; When R1, R2, R3, and R4 in formula (2) are -H, or R2, R3, and R4 are -H, R1 is -CH3 or -NHCOCH3, 5≤n<30 and n is an integer, and R8 and R9 are both -Br or -Cl, a brilliant red macromolecular polymer liquid dye can be prepared; When R1, R2, R3, and R4 in formula (3) are -H, or R2, R3, and R4 are -H, R1 is -CH3 or -NHCOCH3, 5≤n<30 and n is an integer, R 10 -NO2, can be used to prepare macromolecular royal blue polymer liquid dye; When R1, R2, R3, and R4 in formula (4) are -H, or R2, R3, and R4 are -H, R1 is -CH3 or -NHCOCH3, 5≤n<30 and n is an integer, R 11 -H, R 12 -SO3Na or R 11 、R 12 Both are -SO3Na, which can be used to prepare macromolecular bright blue polymer liquid dyes; R 11 、R 12 Both are -H, which can be used to prepare bright green macromolecular polymer liquid dyes; R 11 -OH, R 12 For -H, a brilliant purple macromolecular polymer liquid dye can be prepared.

3. A colored crayon as claimed in claim 1, characterized in that: The preparation method of the macromolecular dye comprises the following steps: When the macromolecular dye is of formula (1), formula (2), or formula (3), the preparation method thereof comprises the following steps: (1) Preparation of aniline diazo liquid derivatives; (2) carrying out a coupling reaction between the aniline diazo liquid derivative and a macromolecular dye precursor in ice water; (3) adding alkali to adjust the pH of the coupling solution to neutral, then adding chloroform for extraction and purification, and evaporating the solvent to obtain the macromolecular dye; When the macromolecular dye is of formula (4), the preparation method thereof comprises the following steps: (1) mixing a benzaldehyde derivative material with a macromolecular dye precursor, using sulfuric acid solution as the solvent and urea as the catalyst to carry out a condensation reaction; (2) diluting with water, using manganese dioxide as an oxidant and sulfuric acid as a pH regulator to carry out an oxidation reaction, and then using calcium hydroxide as an acid binding agent to adjust the pH; (3) Filter and distill the filtrate to remove water to obtain a macromolecular dye. The macromolecular dye precursor is an aniline polyether with a PO segment substituted or unsubstituted, and its general structural formula is as follows: Wherein R1, R2, R3, and R4 are any one of -H, -CH3, -Cl, and -Br; 8≤n≤30 and n is an integer.

4. A colored crayon as claimed in claim 3, characterized in that: When the macromolecular dye is of formula (4), in step (1), the temperature of the condensation reaction is 90 to 110°C.

5. A colored crayon as claimed in claim 3, characterized in that: When the macromolecular dye is of formula (4), in step (2), the temperature of the oxidation reaction is 10 to 35°C.

6. A colored crayon as claimed in claim 3, characterized in that: wherein R1, R2, R3, and R4 are all -H; and n=9.

7. A colored crayon as claimed in claim 3, characterized in that: In the formula, R1 is -CH3, R2, R3, and R4 are all -H; and n=9.

8. A colored crayon as claimed in claim 3, characterized in that: The method for preparing the macromolecular dye precursor comprises the following steps: (1) adding substituted or unsubstituted aniline and hydrochloric acid to a reaction kettle, replacing the air in the reaction kettle with nitrogen several times, raising the temperature, controlling the pressure, slowly introducing propylene oxide to react, and continuing to keep the temperature after the addition is completed to synthesize substituted or unsubstituted N,N-dihydroxyisopropylaminoaniline; (2) Adding a base catalyst to the substituted or unsubstituted N,N-dihydroxyisopropylaminoaniline, and blowing propylene oxide into it to carry out heat-insulating reaction to synthesize a macromolecular dye precursor.

9. A colored crayon as claimed in claim 1, characterized in that: The filler is any one or both of calcium carbonate and talc.

10. The method for preparing a colored crayon according to claim 1, wherein: The steps include: (1) putting solid paraffin, liquid paraffin, calcium stearate and zinc stearate into a stirring kettle, heating and melting, stirring evenly, adding filler and macromolecular dye under stirring and keeping warm; (2) Molding and cooling to obtain colored crayons.

Images