A process method for carrier-free colored oil

Abstract

The present invention provides a process method for carrier-free color oil, which has the functions of antistatic and anti-precipitation, has a longer storage time, and no precipitation occurs after 18 months of storage at room temperature. The method adopted by the present invention is to carboxylate nano-SiO2, add lauryl alcohol polyoxyethylene ether to react with carboxylated nano-SiO2, and graft lauryl alcohol polyoxyethylene ether onto the surface of carboxylated nano-SiO2 to prepare a storage agent; utilize the porous property of nano-SiO2 to adsorb and store color powder. At the same time, due to the grafting of lauryl alcohol polyoxyethylene ether onto the surface of carboxylated nano-SiO2, the dispersion performance is more stable, and no precipitation occurs even after long-term storage, without affecting the overall uniformity and stability of the color oil system. When preparing carrier-free color oil, a certain amount of additives are added to improve the compatibility between the carrier-free color oil and plastics, and avoid the occurrence of phenomena such as uneven coloring and colored dot stripes of the product.

Description

Technical Field

[0001] The present invention belongs to the technical field of plastic colorants, and particularly relates to a process method for carrier-free color oil. Background Art

[0002] Plastic colorants can be divided into four types according to their physical forms, among which color powder is in powder form, masterbatch is in solid form, color paste is in paste form, and color oil is in liquid form. In the coloring of the plastic industry, color powder and masterbatch are relatively widely used. Directly adding an appropriate amount of powdery additives to plastic particles with color powder has good dispersibility of the color powder, but it will cause certain dust pollution; mixing the masterbatch with a carrier and then using it for plastic coloring improves the environmental pollution problem caused by the flying of color powder. However, due to the poor compatibility and dispersibility of the added carrier, the cost is relatively high, and the preparation process is complex, which limits its wide application; the color paste is convenient to use and can be directly put into the processing process for molding and plate coloring, but the color paste has a higher cost and is not easy to store.

[0003] Color oil has good dispersibility, a low addition ratio, a long storage time, and more stable properties, and is gradually being promoted and applied. However, antistatic agents cannot be added to color oil, resulting in the product being unable to prevent dust. Color oil requires special adding equipment, including screw-type color oil metering pumps, peristaltic color oil metering pumps, and screw oil pumping metering pumps. At present, peristaltic color oil metering pumps are mainly used in China to add color oil.

[0004] Color oil is a liquid pigment concentrate without a resin carrier, usually prepared by mixing color powder and diffusion oil. The color powder includes organic pigments and inorganic pigments. Compared with organic pigments, inorganic pigments have poor dispersibility and weak coloring power, but they have strong high-temperature resistance and lower prices. However, whether it is organic pigments or inorganic pigments, color oil will produce certain precipitation after long-term storage, and due to the small addition ratio of color oil, uneven color mixing, poor compatibility, and colored dot stripes are likely to occur after addition, affecting the uniformity of product coloring. Summary of the Invention

[0005] To solve the problems existing in the prior art, the present invention provides a process method for carrier-free color oil to achieve the invention purposes of antistatic and anti-precipitation.

[0006] To solve the above technical problems, the present invention adopts the following technical solutions:

[0007] A process method for carrier-free color oil, comprising the following steps:

[0008] S1. Preparation of carboxylated nano-SiO₂

[0009] Put the porous nano-SiO2 into dimethylformamide, ultrasonically disperse it for 10 - 20 min at room temperature, with an ultrasonic frequency of 100 - 120 kHz. Then add aminopropyltriethoxysilane and maleic anhydride, heat up to 50 - 60 °C and stir for 30 - 50 min, with a stirring rate of 500 - 800 r / min. Then carry out ultrasonic reaction for 3 - 4 h, with an ultrasonic frequency of 150 - 180 kHz, centrifuge for 15 - 20 min, wash the precipitate with absolute ethanol, and dry it at 80 - 100 °C for 2 - 3 h to obtain carboxylated nano-SiO2.

[0010] Preferably, the mass ratio of the porous nano-SiO2, aminopropyltriethoxysilane and maleic anhydride is 10 - 14:1 - 2:2 - 4.

[0011] Preferably, the particle size of the porous nano-SiO2 is 20 - 50 nm.

[0012] S2. Preparation of storage agent

[0013] Add the carboxylated nano-SiO2 and lauryl alcohol polyoxyethylene ether to an appropriate amount of dichloromethane, then add dicyclohexylcarbodiimide and 4-dimethylaminopyridine, stir and react at room temperature for 3 - 5 h, with a stirring rate of 100 - 150 r / min. After the reaction, centrifuge, filter and wash with absolute ethanol, and obtain the storage agent after vacuum drying.

[0014] Preferably, the mass ratio of the carboxylated nano-SiO2, lauryl alcohol polyoxyethylene ether, dicyclohexylcarbodiimide and 4-dimethylaminopyridine is 14 - 18:5 - 7:1 - 2:0.7 - 1.2.

[0015] Carboxylate the nano-SiO2, and then modify the carboxylated nano-SiO2 with lauryl alcohol polyoxyethylene ether, so that the lauryl alcohol polyoxyethylene ether is grafted onto the surface of the carboxylated nano-SiO2, making the stability of the non-carrier color oil in the dispersion better and enabling long-term storage.

[0016] S3. Preparation of non-carrier color oil

[0017] Put the diffusion oil, storage agent and color powder into a stirrer, stir at 30 - 40 °C for 30 - 40 min, then add the auxiliary agent and continue to stir for 40 - 60 min, with a stirring rate of 500 - 600 r / min. After stirring, obtain the non-carrier color oil.

[0018] Preferably, the mass ratio of the diffusion oil, storage agent and color powder is 50 - 60:6 - 8:17 - 20.

[0019] Preferably, the auxiliary agent includes polyisobutene, polyacrylate, antioxidant 1010 and dioctyl adipate.

[0020] Further, the addition amount of the auxiliary agent is 2-5 wt% of the toner powder.

[0021] Further, the mass ratio of the polyisobutylene, polyacrylate, antioxidant 1010, and dioctyl adipate added is 10-12:6-9:1-2:2-4.

[0022] Due to the adoption of the above technical solution, the technical effects achieved by the present invention are as follows:

[0023] 1. The carrier-free color oil prepared by the present invention has the functions of antistatic and anti-precipitation, has a longer storage time, and no precipitation occurs after 18 months of storage at room temperature.

[0024] 2. The nano-SiO₂ is carboxylated, and lauryl alcohol polyoxyethylene ether is added to react with the carboxylated nano-SiO₂. The lauryl alcohol polyoxyethylene ether is used to modify the carboxylated nano-SiO₂, so that the lauryl alcohol polyoxyethylene ether is grafted onto the surface of the carboxylated nano-SiO₂ to form a storage agent; by utilizing the porous property of the nano-SiO₂, the toner powder is adsorbed and stored. At the same time, since the lauryl alcohol polyoxyethylene ether is grafted onto the surface of the carboxylated nano-SiO₂, the dispersion performance is more stable. Even after long-term storage, no precipitation occurs, and the overall uniformity and stability of the color oil system are not affected.

[0025] 3. When preparing the carrier-free color oil, a certain amount of auxiliary agent is added, which improves the compatibility between the carrier-free color oil and the plastic, and avoids the occurrence of phenomena such as uneven coloring and colored dot stripes of the product. Specific Embodiments

[0026] The following combines specific embodiments to further illustrate the present invention.

[0027] Example 1 A process method for carrier-free color oil

[0028] S1. Preparation of carboxylated nano-SiO₂

[0029] The porous nano-SiO₂ is placed in dimethylformamide, ultrasonically dispersed at room temperature for 15 min, the ultrasonic frequency is 120 kHz, then aminopropyltriethoxysilane and maleic anhydride are added, the temperature is raised to 55 °C and stirred for 40 min, the stirring rate is 600 r / min, then ultrasonically reacted for 4 h, the ultrasonic frequency is 160 kHz, centrifuged for 20 min, and the precipitate is washed with absolute ethanol and dried at 90 °C for 3 h to obtain carboxylated nano-SiO₂.

[0030] The mass ratio of the porous nano-SiO₂, aminopropyltriethoxysilane, and maleic anhydride is 12:2:3.

[0031] The particle size of the porous nano-SiO₂ is 20 nm.

[0032] S2. Preparation of the storage agent

[0033] Carboxylated nano-SiO₂ and polyoxyethylene lauryl ether were added to an appropriate amount of dichloromethane, and then dicyclohexylcarbodiimide and 4-dimethylaminopyridine were added. The mixture was stirred at room temperature for 4 h at a stirring rate of 120 r / min. After the reaction, it was centrifuged, filtered and washed with absolute ethanol, and then dried in vacuo to obtain the storage agent.

[0034] The mass ratio of the carboxylated nano-SiO₂, polyoxyethylene lauryl ether, dicyclohexylcarbodiimide and 4-dimethylaminopyridine is 16:6:1.8:0.9.

[0035] S3. Preparation of carrier-free color oil

[0036] Diffusion oil, storage agent and color powder were placed in a stirrer and stirred at 35 °C for 40 min, and then additives were added and stirring was continued for 50 min at a stirring rate of 500 r / min. After stirring, carrier-free color oil was obtained.

[0037] The mass ratio of the diffusion oil, storage agent and color powder is 55:7:18.

[0038] The additives include polyisobutene, polyacrylate, antioxidant 1010 and dioctyl adipate.

[0039] The addition amount of the additives is 4 wt% of the color powder.

[0040] The mass ratio of the added polyisobutene, polyacrylate, antioxidant 1010 and dioctyl adipate is 11:7:2:3.

[0041] Example 2 A process method for carrier-free color oil

[0042] S1. Preparation of carboxylated nano-SiO₂

[0043] Porous nano-SiO₂ was placed in dimethylformamide and ultrasonically dispersed at room temperature for 10 min with an ultrasonic frequency of 100 kHz. Then aminopropyltriethoxysilane and maleic anhydride were added, and the temperature was raised to 50 °C and stirred for 30 min at a stirring rate of 500 r / min. Then ultrasonic reaction was carried out for 3 h with an ultrasonic frequency of 150 kHz, centrifuged for 15 min, and the precipitate was washed with absolute ethanol and dried at 80 °C for 3 h to obtain carboxylated nano-SiO₂.

[0044] The mass ratio of the porous nano-SiO₂, aminopropyltriethoxysilane and maleic anhydride is 10:1:2.

[0045] The particle size of the porous nano-SiO₂ is 50 nm.

[0046] S2. Preparation of storage agent

[0047] Carboxylated nano-SiO₂ and lauryl alcohol polyoxyethylene ether were added to an appropriate amount of dichloromethane, and then dicyclohexylcarbodiimide and 4-dimethylaminopyridine were added. The mixture was stirred at room temperature for 3 h at a stirring rate of 100 r / min. After the reaction, it was centrifuged, filtered and washed with absolute ethanol, and then dried in vacuum to obtain the storage agent.

[0048] The mass ratio of the carboxylated nano-SiO₂, lauryl alcohol polyoxyethylene ether, dicyclohexylcarbodiimide and 4-dimethylaminopyridine is 14:5:1:0.7.

[0049] S3. Preparation of carrier-free color oil

[0050] Diffusion oil, storage agent and color powder were placed in a stirrer and stirred at 30 °C for 30 min, then additives were added and stirring continued for 40 min at a stirring rate of 500 r / min. After stirring, carrier-free color oil was obtained.

[0051] The mass ratio of the diffusion oil, storage agent and color powder is 50:6:17.

[0052] The additives include polyisobutene, polyacrylate, antioxidant 1010 and dioctyl adipate.

[0053] The addition amount of the additives is 2 wt% of the color powder.

[0054] The mass ratio of the added polyisobutene, polyacrylate, antioxidant 1010 and dioctyl adipate is 10:6:1:2.

[0055] Example 3. A process for preparing carrier-free color oil

[0056] S1. Preparation of carboxylated nano-SiO₂

[0057] Porous nano-SiO₂ was placed in dimethylformamide and ultrasonically dispersed at room temperature for 20 min at an ultrasonic frequency of 120 kHz. Then aminopropyltriethoxysilane and maleic anhydride were added, and the temperature was raised to 60 °C and stirred for 50 min at a stirring rate of 800 r / min. Then ultrasonic reaction was carried out for 4 h at an ultrasonic frequency of 180 kHz, centrifuged for 20 min, and the precipitate was washed with absolute ethanol and dried at 100 °C for 2 h to obtain carboxylated nano-SiO₂.

[0058] The mass ratio of the porous nano-SiO₂, aminopropyltriethoxysilane and maleic anhydride is 14:2:4.

[0059] The particle size of the porous nano-SiO₂ is 50 nm.

[0060] S2. Preparation of storage agent

[0061] Carboxylated nano-SiO2 and polyoxyethylene lauryl ether were added to an appropriate amount of dichloromethane, and then dicyclohexylcarbodiimide and 4-dimethylaminopyridine were added. The mixture was stirred at room temperature for 5 h at a stirring rate of 150 r / min. After the reaction, it was centrifuged, filtered and washed with absolute ethanol, and then dried in vacuum to obtain the storage agent.

[0062] The mass ratio of the carboxylated nano-SiO2, polyoxyethylene lauryl ether, dicyclohexylcarbodiimide and 4-dimethylaminopyridine is 18:7:2:1.2.

[0063] S3. Preparation of carrier-free color oil

[0064] Diffusion oil, storage agent and color powder were placed in a stirrer and stirred at 40 °C for 35 min, then an auxiliary agent was added and stirring was continued for 60 min at a stirring rate of 600 r / min. After stirring, carrier-free color oil was obtained.

[0065] The mass ratio of the diffusion oil, storage agent and color powder is 60:8:20.

[0066] The auxiliary agent includes polyisobutene, polyacrylate, antioxidant 1010 and dioctyl adipate.

[0067] The addition amount of the auxiliary agent is 5 wt% of the color powder.

[0068] The mass ratio of the added polyisobutene, polyacrylate, antioxidant 1010 and dioctyl adipate is 12:9:2:4.

[0069] Comparative Example 1

[0070] The storage agent was replaced with polyoxyethylene lauryl ether, and the others were the same as in Example 1, specifically as follows:

[0071] Diffusion oil, polyoxyethylene lauryl ether and color powder were placed in a stirrer and stirred at 35 °C for 40 min, then an auxiliary agent was added and stirring was continued for 50 min at a stirring rate of 500 r / min. After stirring, carrier-free color oil was obtained.

[0072] The mass ratio of the diffusion oil, polyoxyethylene lauryl ether and color powder is 55:2:18.

[0073] The auxiliary agent includes polyisobutene, polyacrylate, antioxidant 1010 and dioctyl adipate.

[0074] The addition amount of the auxiliary agent is 4 wt% of the color powder.

[0075] The mass ratio of the added polyisobutene, polyacrylate, antioxidant 1010 and dioctyl adipate is 11:7:2:3.

[0076] Comparative Example 2

[0077] Replace the storage agent with polyoxyethylene lauryl ether and porous nano-SiO₂, and the rest is the same as in Example 1, specifically as follows:

[0078] Put the diffusion oil, polyoxyethylene lauryl ether, porous nano-SiO₂, and toner powder into a stirrer and stir at 35 °C for 40 min, then add the additives and continue to stir for 50 min. The stirring rate is 500 r / min. After stirring, carrier-free color oil is obtained.

[0079] The mass ratio of the diffusion oil, polyoxyethylene lauryl ether, porous nano-SiO₂, and toner powder is 55:2:5:18.

[0080] The additives include polyisobutene, polyacrylate, antioxidant 1010, and dioctyl adipate.

[0081] The addition amount of the additives is 4 wt% of the toner powder.

[0082] The mass ratio of the added polyisobutene, polyacrylate, antioxidant 1010, and dioctyl adipate is 11:7:2:3.

[0083] Comparative Example 3

[0084] Remove the additives in step S3, and the rest is the same as in Example 1. The specific steps are as follows:

[0085] S1. Preparation of carboxylated nano-SiO₂

[0086] Put the porous nano-SiO₂ into dimethylformamide, ultrasonically disperse it at room temperature for 15 min, with an ultrasonic frequency of 120 kHz. Then add 3-aminopropyltriethoxysilane and maleic anhydride, heat up to 55 °C and stir for 40 min, with a stirring rate of 600 r / min. Then carry out ultrasonic reaction for 4 h, with an ultrasonic frequency of 160 kHz, centrifuge for 20 min, wash the precipitate with absolute ethanol, and dry it at 90 °C for 3 h to obtain carboxylated nano-SiO₂.

[0087] The mass ratio of the porous nano-SiO₂, 3-aminopropyltriethoxysilane, and maleic anhydride is 12:2:3.

[0088] The particle size of the porous nano-SiO₂ is 20 nm.

[0089] S2. Preparation of the storage agent

[0090] Add the carboxylated nano-SiO₂ and polyoxyethylene lauryl ether to an appropriate amount of dichloromethane, then add dicyclohexylcarbodiimide and 4-dimethylaminopyridine, and stir and react at room temperature for 4 h, with a stirring rate of 120 r / min. After the reaction, centrifuge, filter, wash with absolute ethanol, and dry in vacuum to obtain the storage agent.

[0091] The mass ratio of the carboxylated nano-SiO2, lauryl alcohol polyoxyethylene ether, dicyclohexylcarbodiimide and 4-dimethylaminopyridine is 16:6:1.8:0.9.

[0092] S3. Preparation of carrier-free color oil

[0093] Put the diffusion oil, storage agent and color powder into a stirrer and stir at 35 °C for 90 min at a stirring rate of 500 r / min. After stirring, carrier-free color oil is obtained.

[0094] The mass ratio of the diffusion oil, storage agent and color powder is 55:7:18.

[0095] The carrier-free color oils prepared in Examples 1-3 and Comparative Examples 1-3 were added to ABS by a peristaltic color oil metering pump at an addition amount of 0.2%, and injection molded, and their coloring effects and anti-precipitation performance effects were compared. The comparison results are shown in Table 1.

[0096] Table 1

[0097]

[0098]

[0099] It can be seen from Table 1 that grafting lauryl alcohol polyoxyethylene ether onto the surface of carboxylated nano-SiO2 to prepare a storage agent has more stable dispersion performance. Even after long-term storage, no precipitation occurs, and it does not affect the overall uniformity and stability of the color oil system; adding a certain amount of auxiliary agent improves the compatibility between the carrier-free color oil and the plastic, and avoids the occurrence of phenomena such as uneven coloring and colored dot stripes of the product.

[0100] Unless otherwise specified, the ratios described in the present invention are all mass ratios, and the percentages are all mass percentages; the raw materials are all commercially available.

[0101] Finally, it should be noted that the above are only the preferred embodiments of the present invention and are not used to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments, or perform equivalent replacements for some of the technical features. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims

1. A process method for carrier-free colored oil, characterized in that The process method includes the preparation of carboxylated nano-SiO2, the preparation of a storage agent, and the preparation of carrier-free color oil; The preparation of the carboxylated nano-SiO2 includes placing porous nano-SiO2 in dimethylformamide, ultrasonically dispersing it at room temperature for 10 - 20 min with an ultrasonic frequency of 100 - 120 kHz, then adding aminopropyltriethoxysilane and maleic anhydride, heating to 50 - 60 °C and stirring for 30 - 50 min at a stirring rate of 500 - 800 r / min, then ultrasonically reacting for 3 - 4 h with an ultrasonic frequency of 150 - 180 kHz, centrifuging for 15 - 20 min, washing the precipitate with absolute ethanol, and drying at 80 - 100 °C for 2 - 3 h to obtain carboxylated nano-SiO2; The preparation of the storage agent includes adding carboxylated nano-SiO2 and polyoxyethylene lauryl ether to an appropriate amount of dichloromethane, then adding dicyclohexylcarbodiimide and 4-dimethylaminopyridine, stirring and reacting at room temperature for 3 - 5 h at a stirring rate of 100 - 150 r / min. After the reaction, centrifuge, filter, and wash with absolute ethanol, and obtain the storage agent after vacuum drying; The preparation of the carrier-free color oil includes placing diffusion oil, the storage agent, and color powder in a stirrer and stirring at 30 - 40 °C for 30 - 40 min, then adding an auxiliary agent and continuing to stir for 40 - 60 min at a stirring rate of 500 - 600 r / min. After stirring is completed, carrier-free color oil is obtained.

2. The process method of a carrier-free color oil according to claim 1, characterized in that, The mass ratio of the porous nano-SiO2, aminopropyltriethoxysilane, and maleic anhydride is 10 - 14:1 - 2:2 - 4.

3. The process method of a carrier-free color oil according to claim 1, characterized in that, The mass ratio of the carboxylated nano-SiO2, polyoxyethylene lauryl ether, dicyclohexylcarbodiimide, and 4-dimethylaminopyridine is 14 - 18:5 - 7:1 - 2:0.7 - 1.

2.

4. The process method of a carrier-free color oil according to claim 1, characterized in that The mass ratio of the diffusion oil, the storage agent, and the color powder is 50 - 60:6 - 8:17 - 20.

5. A process method of carrier-free color oil according to claim 1, characterized in that The auxiliary agent includes polyisobutene, polyacrylate, antioxidant 1010, and dioctyl adipate.

6. The process method of a carrier-free color oil according to claim 1, characterized in that, The addition amount of the auxiliary agent is 2 - 5 wt% of the color powder.

7. A process method for carrier-free color oil according to claim 5, characterized in that, The mass ratio of the added polyisobutene, polyacrylate, antioxidant 1010, and dioctyl adipate is 10 - 12:6 - 9:1 - 2:2 - 4.

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