Coloring agent and intermediate thereof, and preparation method and application thereof

Abstract

The invention discloses a coloring agent and an intermediate thereof, and a preparation method and application thereof, and belongs to the technical field of polymer coloring agents. The preparation method of the intermediate comprises the following steps: carrying out reduced pressure distillation on the polymer polyol and the modified color at 100-105 DEG C until the water content is less than or equal to 0.1%; cooling to 40-60 DEG C, adding part of the solvent, then adding diisocyanate and a catalyst, and reacting for 1.5-3 hours when the internal temperature reaches 80-90 DEG C; cooling to 40-60 DEG C, adding part of the solvent, then adding micromolecular dihydric alcohol to carry out chain extension reaction, and reacting for 2-3 hours when the internal temperature reaches 70-85 DEG C; and adding a terminating agent, adding the residual solvent, and reacting for 0.5-1.5 hours when the internal temperature is 70-80 DEG C. According to the method, the colorant intermediate capable of improving the light resistance and migration resistance of the colorant can be obtained; the colorant prepared from the intermediate and an acrylic monomer is especially suitable for automobile leather.

Description

Technical Field

[0001] The present invention relates to the technical field of colorants, and in particular to a colorant and an intermediate thereof, and a preparation method and application thereof. Background Art

[0002] Traditionally, leather materials for automotive interiors are mainly genuine leather, PVC leather and textiles. As the requirements for automotive interior materials for durability, flame retardancy, anti-fouling, and environmental protection continue to increase, polyurethane (PU) synthetic leather and its composite materials have been expanded in the field of automotive interiors, forming a good alternative to natural leather, PVC artificial leather and fabrics, with a broad market space. As a new type of organic polymer material, PU synthetic leather has superior properties such as high durability, good hand feel, high softness, and long service life compared to PVC artificial leather, but it also has the disadvantages of greater environmental pollution during the production process, poor comfort, and strong odor. Genuine leather pollutes the environment more seriously during its own production process, and the heavy metal content is easily exceeded. The yield rate is low during the processing of interior parts, and its cost is high.

[0003] PU synthetic leather will be colored during the manufacturing process, and the colorants used are generally pigments and dyes. When using pigments for coloring, the luster of leather products is relatively dull, and it is impossible to create a three-dimensional effect with a sense of hierarchy; when using dyes for coloring, although it has the characteristics of high brilliance, good transparency, and strong coloring power, dyes are small molecules and have poor migration resistance, which leads to mutual contact and contamination of the leather surface, and the release paper is also easily contaminated during the dry-paste process of leather making; in addition, another major disadvantage of dyes is that they have poor light resistance. After a certain period of light exposure, the color of the synthetic leather produced becomes lighter or faded, making its products unable to be used in the fields of luggage, shoes, clothing, etc., let alone in the field of automotive leather.

[0004] With the upgrading of market consumption and the emergence of new energy vehicles, automobile manufacturers are also constantly introducing new technologies to improve the comfort of car rides. As an important part of automobiles, automobile leather has gradually replaced leather due to its outstanding performance and has become a new favorite of automobile consumers. As a high-quality, high-performance, and high-tech synthetic leather, automobile leather achieves the perfect unity of composite aesthetic requirements in appearance and excellent internal quality. It has the properties of water resistance, wear resistance, flame retardancy, solvent resistance, yellowing resistance, sun resistance, and harmlessness to the human body. Therefore, the product grade of automobile leather in industrial products is relatively high, and the performance grade requirements are also relatively high. The color used must meet the sun resistance grade ≥6 and the migration resistance grade ≥4~5 before it can be used in the field of automobile leather. On the market, there are very few conventional dyes that can meet the above performance at the same time.

[0005] In view of this, the present invention is proposed. Summary of the invention

[0006] The object of the present invention is to provide a colorant and its intermediates and a preparation method and application thereof, so as to solve or improve the above technical problems.

[0007] The present invention can be implemented like this:

[0008] In a first aspect, the present invention provides a method for preparing a colorant intermediate, comprising the following steps:

[0009] After the polymer polyol and the modified color are mixed in a reaction container, vacuum distillation is performed at 100°C to 105°C until the water content of the mixture is ≤0.1%;

[0010] Cool down to 40-60°C, add 30%-40% of the total weight of the solvent, then add diisocyanate and catalyst, and react for 1.5-3 hours when the internal temperature reaches 80-90°C;

[0011] Cool down to 40-60°C, add 20%-30% of the total weight of the solvent, and then add a small molecule diol to carry out a chain extension reaction. When the internal temperature reaches 70-85°C, react for 2-3 hours;

[0012] Add a terminator and the remaining solvent, and react for 0.5 h to 1.5 h at an internal temperature of 70° C. to 80° C. to obtain a colorant intermediate;

[0013] The molar ratio of diisocyanate to polymer polyol is 1:0.03 to 1:0.06;

[0014] The molar ratio of diisocyanate to modified color is 1:0.2 to 1:0.3;

[0015] The molar ratio of diisocyanate to small molecule diol is 1:0.6 to 1:0.7;

[0016] The molar ratio of diisocyanate to terminator is 1:0.02 to 1:0.07;

[0017] The weight of the catalyst is 0.02% to 0.04% of the total weight of the material;

[0018] The total weight of the solvent is 60% to 70% of the total weight of the material;

[0019] The total weight of the materials is the total weight of the polymer polyol, modified color, solvent, diisocyanate, catalyst, small molecule diol and terminator.

[0020] In an optional embodiment, the polymer polyol includes at least one of a polyether polyol, a polyester polyol, a polycarbonate polyol, and a polytetramethylene glycol polyol;

[0021] And / or, the modified color includes at least one of TPF-3178 crimson, TPF-3273 bright yellow, and TPF-3342 blue.

[0022] In an optional embodiment, the diisocyanate includes at least one of diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, xylylene diisocyanate and toluene diisocyanate;

[0023] And / or, the catalyst includes at least one of organotin and organobismuth.

[0024] In an optional embodiment, the small molecule diol includes at least one of ethylene glycol, propylene glycol, butanediol, 1,5-pentanediol, neopentyl glycol, hexanediol, diethylene glycol and 3-methyl-1,5-pentanediol;

[0025] and / or, the terminator comprises at least one of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate and hydroxypropyl methacrylate;

[0026] And / or, the solvent includes at least one of acetone, butanone, N-methylpyrrolidone, N-ethylpyrrolidone, dioxane, N,N-dimethylformamide, N,N-diethylformamide, toluene, xylene, ethyl acetate, butyl acetate, propylene glycol methyl ether acetate and isopropanol.

[0027] In a second aspect, the present invention provides a colorant intermediate, which is prepared by the preparation method of any one of the aforementioned embodiments.

[0028] In a third aspect, the present invention provides a method for preparing a colorant, the method for preparing the colorant comprising:

[0029] Under a protective atmosphere, a mixed solution of acrylic acid monomer and initiator is added dropwise to the heated colorant intermediate; the addition time is 2h to 4h, and the addition temperature is 75°C to 90°C;

[0030] After the dropwise addition is completed, the reaction is maintained at 80°C to 95°C for 4h to 6h to obtain a colorant.

[0031] In an optional embodiment, the mass ratio of the acrylic monomer to the colorant intermediate is 40:60 to 50:50;

[0032] The mass of the initiator is 0.1% to 5% of the total mass of the acrylic monomer and the colorant intermediate.

[0033] In an optional embodiment, the acrylic monomer includes at least one of methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate and styrene;

[0034] And / or, the initiator includes at least one of AIBN, BPO, LPO, TBPO and TAPO.

[0035] In a fourth aspect, the present invention provides a colorant, which is prepared by the preparation method of any one of the aforementioned embodiments.

[0036] In a fifth aspect, the present invention provides a leather, wherein the colorant of the aforementioned embodiment is used in the preparation process of the leather.

[0037] In an alternative embodiment, the leather comprises automotive leather.

[0038] The beneficial effects of the present invention include:

[0039] The light-resistant chromophore group introduced into the colorant intermediate provided by the present invention can meet the light resistance requirement of polymer colorant ≥ level 6; through the step-by-step addition reaction, on the one hand, the color can be locked in the molecular structure, and on the other hand, by forming a polymer product, the thermal motion rate of the molecule can be slowed down, so that the product meets the requirement of migration resistance ≥ level 4 to 5, which is conducive to further preparing a colorant with better light resistance and migration resistance. The above-mentioned colorant intermediate is reacted with an acrylic monomer, and the CC main chain in the acrylic resin structure does not contain easily oxidized and hydrolyzed groups, which has good antioxidant, medium resistance, light resistance and aging resistance, and further improves the light fastness of the colorant product.

[0040] The colorant provided by the invention has high light fastness (≥6 levels), excellent migration resistance (≥4-5 levels), and good color fastness to rubbing (≥4-5 levels), and can meet the performance requirements and market demands of automobile leather. DETAILED DESCRIPTION

[0041] In order to make the purpose, technical scheme and advantages of the embodiments of the present invention clearer, the technical scheme in the embodiments of the present invention will be described clearly and completely below. If the specific conditions are not specified in the embodiments, they are carried out according to conventional conditions or conditions recommended by the manufacturer. If the manufacturer of the reagents or instruments used is not specified, they are all conventional products that can be purchased commercially.

[0042] The colorant and its intermediates provided by the present invention and their preparation methods and applications are described in detail below.

[0043] The present invention provides a method for preparing a colorant intermediate, comprising the following steps:

[0044] S1: After mixing the polymer polyol and the modified color in a reaction container, distill under reduced pressure at 100°C to 105°C until the water content of the mixture is ≤0.1%;

[0045] S2: Cooling to 40°C to 60°C, adding a portion of solvent accounting for 30% to 40% of the total weight of the solvent, and then adding diisocyanate and catalyst, and reacting for 1.5h to 3h when the internal temperature reaches 80°C to 90°C;

[0046] S3: Cooling to 40°C to 60°C, adding 20% ​​to 30% of the total weight of the solvent, and then adding a small molecule diol to carry out a chain extension reaction. When the internal temperature reaches 70°C to 85°C, react for 2h to 3h;

[0047] S4: Add a terminator and the remaining solvent, and react for 0.5 h to 1.5 h at an internal temperature of 70° C. to 80° C. to obtain a colorant intermediate.

[0048] In some optional embodiments, in the above S1, the reaction temperature can be 100°C, 101°C, 102°C, 103°C, 104°C or 105°C, etc., or other values ​​within the range of 100°C to 105°C.

[0049] In the above S1, after the reduced pressure distillation, the water content of the mixture can be, for example, 0.1 wt%, 0.08 wt%, 0.05 wt% or 0.01 wt%.

[0050] In some optional embodiments, the molar ratio of diisocyanate to polymer polyol can be 1:0.03 to 1:0.06, such as 1:0.03, 1:0.04, 1:0.05 or 1:0.06, or other values ​​within the range of 1:0.03 to 1:0.06.

[0051] As an example, the diisocyanate may include, by way of example but not limitation, diphenylmethane diisocyanate (MDI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), dicyclohexylmethane diisocyanate (HDI), 12 At least one of MDI, xylylene diisocyanate (XDI) and toluene diisocyanate (TDI).

[0052] The polymer polyol may illustratively but not limitatively include at least one of polyether polyol, polyester polyol, polycarbonate polyol, and polytetramethylene glycol polyol.

[0053] In some optional embodiments, the molar ratio of diisocyanate to modified color can be 1:0.2 to 1:0.3, such as 1:0.2, 1:0.25 or 1:0.3, or other values ​​within the range of 1:0.2 to 1:0.3. If the amount of modified color is too high, it is easy to cause incomplete color reaction, which is not conducive to the migration resistance and wet and dry rubbing resistance of the product.

[0054] As an example, the modified color may include, by way of example but not limitation, at least one of TPF-3178 red, TPF-3273 bright yellow, and TPF-3342 blue. The above modified colors can all be purchased from Caihua Technology Company.

[0055] In some optional embodiments, in the above S2, the temperature after cooling can be 40°C, 45°C, 50°C, 55°C or 60°C, etc., or other values ​​within the range of 40°C to 60°C.

[0056] The weight of the partial solvent added in S2 is 30%, 32%, 35%, 38% or 40% of the total solvent, etc., and may also be other values ​​within the range of 30% to 40%.

[0057] The internal temperature in S2 may be 80°C, 82°C, 85°C, 88°C or 90°C, etc., or may be other values ​​within the range of 80°C to 90°C.

[0058] The reaction time in S2 can be 1.5 h, 2 h, 2.5 h or 3 h, etc., or other values ​​within the range of 1.5 h to 3 h.

[0059] In some optional embodiments, the total weight of the solvent is 60% to 70% of the total weight of the material, such as 60%, 62%, 65%, 68% or 70%, etc., or other values ​​within the range of 60% to 70%.

[0060] It should be noted that, in this article, the total weight of materials is the total weight of polymer polyols, modified colors, solvents, diisocyanates, catalysts, small molecule diols and terminators.

[0061] By way of example, the solvent may illustratively but not limitatively include at least one of acetone, butanone, N-methylpyrrolidone (NMP), N-ethylpyrrolidone (NEP), dioxane, N,N-dimethylformamide (DMF), N,N-diethylformamide (DEF), toluene, xylene, ethyl acetate, butyl acetate, propylene glycol methyl ether acetate (PMA) and isopropyl alcohol.

[0062] In some optional embodiments, the weight of the catalyst can be 0.02% to 0.04% of the total weight of the material, such as 0.02%, 0.025%, 0.03%, 0.035% or 0.04%, etc., or other values ​​within the range of 0.02% to 0.04%.

[0063] By way of example, the catalyst may illustratively but not limitingly include at least one of an organotin and an organobismuth.

[0064] In some optional embodiments, in the above S3, the temperature after cooling can be 40°C, 45°C, 50°C, 55°C or 60°C, etc., or other values ​​within the range of 40°C to 60°C.

[0065] The weight of the partial solvent added in S3 is 20%, 22%, 25%, 28% or 30% of the total solvent, etc., and may also be other values ​​within the range of 20% to 30%.

[0066] In some optional embodiments, the molar ratio of diisocyanate to small molecule diol can be 1:0.6 to 1:0.7, such as 1:0.6, 1:0.65 or 1:0.7, or other values ​​within the range of 1:0.6 to 1:0.7.

[0067] As an example, the small molecule diol may illustratively but not limitatively include at least one of ethylene glycol, propylene glycol, butanediol, 1,5-pentanediol, neopentyl glycol, hexanediol, diethylene glycol, and 3-methyl-1,5-pentanediol.

[0068] The internal temperature in S3 may be 70°C, 72°C, 75°C, 78°C, 80°C, 82°C or 85°C, etc., or may be other values ​​within the range of 70°C to 85°C.

[0069] The reaction time in S3 can be 2 h, 2.5 h or 3 h, etc., or other values ​​within the range of 2 h to 3 h.

[0070] In some optional embodiments, in the above S4, the molar ratio of diisocyanate to terminator can be 1:0.02 to 1:0.07, such as 1:0.02, 1:0.03, 1:0.04, 1:0.05, 1:0.06 or 1:0.07, or other values ​​within the range of 1:0.02 to 1:0.07.

[0071] By way of example, the terminator may illustratively but not limitingly include at least one of hydroxyethyl acrylate (HEA), hydroxypropyl acrylate (HPA), hydroxyethyl methacrylate (HEMA), and hydroxypropyl methacrylate (HPMA).

[0072] Correspondingly, the present invention also provides a colorant intermediate, which is prepared by the above preparation method.

[0073] The introduction of light-resistant chromophore groups into the above-mentioned colorant intermediates can meet the light resistance requirements of polymer colorants ≥ level 6; through gradual addition reactions, on the one hand, the color can be locked in the molecular structure, and on the other hand, by forming a polymer product, the thermal motion rate of the molecules can be slowed down, so that the product meets the requirements of migration resistance ≥ level 4 to 5.

[0074] In addition, the present invention also provides a method for preparing a colorant, which comprises:

[0075] Under a protective atmosphere, a mixed solution of acrylic acid monomer and initiator is added dropwise to the heated colorant intermediate; the addition time is 2h to 4h, and the addition temperature is 75°C to 90°C;

[0076] After the dropwise addition is completed, the reaction is maintained at 80°C to 95°C for 4h to 6h to obtain a colorant.

[0077] In some optional embodiments, the protective atmosphere may include a nitrogen atmosphere or an argon atmosphere, etc.

[0078] The temperature of the heated colorant intermediate may be 75°C, 78°C, 80°C, 82°C, 85°C, 88°C or 90°C, or may be other values ​​within the range of 75°C to 90°C.

[0079] In some optional embodiments, the mass ratio of the acrylic monomer to the colorant intermediate may be 40:60 to 50:50, such as 40:60, 42:58, 45:55, 48:52 or 50:50, or other values ​​within the range of 40:60 to 50:50.

[0080] If the amount of acrylic acid monomer used is too small, the content of small molecule monomers will be reduced, which is not conducive to free radical reaction and the conversion rate will be reduced; if the amount of acrylic acid monomer used is too large, the content of colored intermediates will be low and the overall color value will be reduced, which is not conducive to the market application of the product.

[0081] By way of example, the acrylic monomer may illustratively but not limitatively include at least one of methyl acrylate (MA), ethyl acrylate (EA), butyl acrylate (BA), 2-ethylhexyl acrylate (2-EHA), methyl methacrylate (MMA), butyl methacrylate (BMA), 2-ethylhexyl methacrylate (2-EHMA) and styrene.

[0082] In some optional embodiments, the mass of the initiator can be 0.1% to 5% of the total mass of the acrylic monomer and the colorant intermediate, such as 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5% or 5%, etc., or other values ​​within the range of 0.1% to 5%.

[0083] By way of example, the initiator may illustratively but not limitingly include at least one of AIBN, BPO, LPO, TBPO, and TAPO.

[0084] By reacting the colorant intermediate with the acrylic monomer, the CC main chain in the acrylic resin structure does not contain easily oxidized and hydrolyzed groups, and has good antioxidant, medium resistance, light resistance and aging resistance, which further improves the light fastness of the product.

[0085] In some optional embodiments, the dropping temperature can be 75°C, 78°C, 80°C, 82°C, 85°C, 88°C or 90°C, etc., or other values ​​within the range of 75°C to 90°C.

[0086] If the dropping temperature is too low, the reaction speed is too slow, which is not conducive to the improvement of molecular weight and monomer conversion rate; if the dropping temperature is too high, too many free radicals are generated per unit time, which will make it difficult to control the reaction temperature and cause explosion and gelation.

[0087] The dropping time may be 2 h, 2.5 h, 3 h, 3.5 h or 4 h, etc., or may be other values ​​within the range of 2 h to 4 h.

[0088] In some optional embodiments, the insulation temperature may be 80°C, 82°C, 85°C, 88°C, 90°C, 92°C or 95°C, etc., or other values ​​within the range of 80°C to 95°C.

[0089] The insulation time can be 4h, 4.5h, 5h, 5.5h or 6h, etc., or other values ​​within the range of 4h to 6h.

[0090] If the insulation time is too short, the free radical reaction will not be complete, the conversion rate will be low, and the migration resistance and dry and wet rubbing resistance will be reduced; if the insulation time is too long, the monomer conversion rate will increase, but the energy consumption will be high, which is not conducive to industrial production.

[0091] Correspondingly, the present invention also provides a colorant, which is prepared by the above preparation method.

[0092] The colorant has high light fastness (≥grade 6), excellent migration resistance (≥grade 4-5), and good color fastness to rubbing (≥grade 4-5).

[0093] In addition, the present invention also provides a leather, wherein the colorant is used in the preparation process of the leather.

[0094] In some embodiments, the leather may include bag leather, shoe leather, clothing leather or automobile leather, etc. In some typical embodiments, the leather using the colorant is automobile leather.

[0095] The features and performance of the present invention are further described in detail below in conjunction with the embodiments.

[0096] Example 1

[0097] This embodiment provides a colorant, and the preparation method thereof includes:

[0098] S1: 6.0 kg of polyether diol with a number average molecular weight of 2000, 6.0 kg of polyester diol with a number average molecular weight of 2000 and 11.5 kg of TPF-3178 red were added to a reactor, the temperature was raised to 100° C., and water was evaporated under reduced pressure for 2 hours to make the moisture content of the mixture ≤0.1%.

[0099] S2: Cool the contents of the reactor to 50°C, add 29.8 kg of DMF, then add 32.0 kg of IPDI and 43.0 g of dibutyltin dilaurate, and react for 2 h when the internal temperature reaches 85°C.

[0100] S3: Cool the contents of the reactor to 50°C, add 29.8 kg of DMF, then add 9.05 kg of butanediol, and react for 2 h when the internal temperature reaches 85°C.

[0101] S4: Add 1.6 kg of HEA and 39.7 kg of butyl acetate, and react for 1 hour at an internal temperature of 75° C. to obtain a colorant intermediate.

[0102] S5: Add 55 kg of the colorant intermediate into the reactor, introduce nitrogen and start heating until the temperature rises to 82±2°C.

[0103] S6: Mix 5 kg of MMA, 40 kg of BMA and 0.3 kg of AIBN evenly and add them into the dropping tank. The dropping time is 4 hours and the dropping temperature is 82±2°C.

[0104] S7: After the dropwise addition is completed, the temperature is maintained at 82±2° C. and the reaction is carried out for 4 hours to obtain a coloring agent.

[0105] The molar ratio of the above-mentioned diisocyanate to polymer polyol is 1:0.042, the molar ratio of diisocyanate to modified color is 1:0.21; the molar ratio of diisocyanate to small molecule diol is 1:0.7; the molar ratio of diisocyanate to terminator is 1:0.048; the weight of the catalyst is 0.026% of the total weight of S1, S2, S3, and S4 materials; the total weight of the solvent is 60% of the total weight of S1, S2, S3, and S4 materials; the weight of the solvent used in S2 is 18% of the total weight of S1, S2, S3, and S4 materials, the weight of the solvent used in S3 is 18% of the total weight of S1, S2, S3, and S4 materials, and the weight of the solvent used in S4 is 24% of the total weight of S1, S2, S3, and S4 materials.

[0106] Example 2

[0107] This embodiment provides a colorant, and the preparation method thereof includes:

[0108] S1: 8.0 kg of polytetrahydrofuran diol with a number average molecular weight of 1000 and 17.0 kg of TPF-3273 bright yellow are added to a reaction kettle, the temperature is raised to 100° C., and water is evaporated under reduced pressure for 1 hour to make the moisture content of the mixture ≤0.1%.

[0109] S2: Cool the contents of the reactor to 50°C, add 68.3 kg of DMF, then add 40.0 kg of IPDI, 10.4 kg of H 12 MDI and 87.4 g of organic bismuth were added and reacted for 1.5 h when the internal temperature reached 90°C.

[0110] S3: Cool the contents of the reactor to 100°C, add 47.8 kg of DMF, and then add 16.7 kg of hexanediol. When the internal temperature reaches 80°C, react for 2 hours.

[0111] S4: Add 4.0 kg of HEMA and 78.0 kg of PMA, and react for 1.5 hours at an internal temperature of 70° C. to obtain a colorant intermediate.

[0112] S5: Add 60 kg of the colorant intermediate into the reactor, introduce nitrogen and start heating until the temperature rises to 85±2°C.

[0113] S6: Mix 10 kg of MA, 25 kg of BA, 5 kg of styrene, 1.0 kg of TAPO and 1.0 kg of TBPO evenly and add them into the dropping tank. The dropping time is 2 h and the dropping temperature is 85±2°C.

[0114] S7: After the dropwise addition is completed, the temperature is maintained at 91±2° C. for 5 hours to obtain a colorant.

[0115] The molar ratio of the above-mentioned diisocyanate to polymer polyol is 1:0.036, the molar ratio of diisocyanate to modified color is 1:0.25; the molar ratio of diisocyanate to small molecule diol is 1:0.64; the molar ratio of diisocyanate to terminator is 1:0.07; the weight of the catalyst is 0.03% of the total weight of S1, S2, S3, and S4 materials; the total weight of the solvent is 67% of the total weight of S1, S2, S3, and S4 materials; the weight of the solvent used in S2 is 23.5% of the total weight of S1, S2, S3, and S4 materials, the weight of the solvent used in S3 is 16.5% of the total weight of S1, S2, S3, and S4 materials, and the weight of the solvent used in S4 is 27% of the total weight of S1, S2, S3, and S4 materials.

[0116] Example 3

[0117] This embodiment provides a colorant, and the preparation method thereof includes:

[0118] S1: 10.0 kg of polycarbonate diol with a number average molecular weight of 1000 and 16.0 kg of TPF-3342 blue were added to a reaction kettle, the temperature was raised to 100° C., and water was evaporated under reduced pressure for 2 h to make the moisture content of the mixture ≤ 0.1%.

[0119] S2: Cool the contents of the reactor to 50°C, add 50.0 kg of DMF, then add 14 kg of IPDI, 19 kg of HDI and 38.5 g of organic bismuth, and react for 3 h when the internal temperature reaches 80°C.

[0120] S3: Cool the contents of the reactor to 50°C, add 25.0 kg of butanone, then add 7.3 kg of ethylene glycol, and react for 3 hours when the internal temperature reaches 75°C.

[0121] S4: Add 1.05 kg of HPMA and 50 kg of DMF, and react for 0.5 h at an internal temperature of 80° C. to obtain a colorant intermediate.

[0122] S5: Add 50 kg of the colorant intermediate into the reactor, introduce nitrogen and start heating until the temperature rises to 78±2°C.

[0123] S6: 7 kg of MMA, 25 kg of 2-EHMA, 18 kg of BA, 2.0 kg of BPO and 1.0 kg of LPO were mixed evenly and added to the dropping tank. The dropping time was 3 h and the dropping temperature was 78±2°C.

[0124] S7: After the dropwise addition is completed, the temperature is maintained at 91±2° C. for 6 hours to obtain a colorant.

[0125] The molar ratio of the above-mentioned diisocyanate to polymer polyol is 1:0.057, the molar ratio of diisocyanate to modified color is 1:0.25; the molar ratio of diisocyanate to small molecule diol is 1:0.67; the molar ratio of diisocyanate to terminator is 1:0.02; the weight of the catalyst is 0.02% of the total weight of S1, S2, S3, and S4 materials; the total weight of the solvent is 65% of the total weight of S1, S2, S3, and S4 materials; the weight of the solvent used in S2 is 26% of the total weight of S1, S2, S3, and S4 materials, the weight of the solvent used in S3 is 13% of the total weight of S1, S2, S3, and S4 materials, and the weight of the solvent used in S4 is 26% of the total weight of S1, S2, S3, and S4 materials.

[0126] Comparative Example 1

[0127] The performance of the conventional small molecule dye Disperse Red 2 and the modified polymer colorant of Example 1 were compared.

[0128] Comparative Example 2

[0129] The performance of the conventional small molecule dye Solvent Yellow 58 and the modified polymer colorant of Example 2 were compared.

[0130] Comparative Example 3

[0131] The performance of the conventional small molecule dye Reactive Brilliant Blue X-BR and the modified polymer colorant of Example 3 were compared.

[0132] Comparative Example 4

[0133] This comparative example provides a colorant, and its preparation method comprises:

[0134] S1: 6.0 kg of polyether diol with a number average molecular weight of 2000, 6.0 kg of polyester diol with a number average molecular weight of 2000 and 27.4 kg of TPF-3178 red were added to a reactor, the temperature was raised to 100° C., and water was evaporated under reduced pressure for 2 hours to make the moisture content of the mixture ≤0.1%.

[0135] S2: Cool the contents of the reactor to 50°C, add 36.95 kg of DMF, then add 32.0 kg of IPDI and 43.0 g of dibutyltin dilaurate, and react for 2 h when the internal temperature reaches 85°C.

[0136] S3: Cool the contents of the reactor to 50°C, add 36.95 kg of DMF, then add 9.05 kg of butanediol, and react for 2 h when the internal temperature reaches 85°C.

[0137] S4: Add 1.6 kg of HEA and 49.3 kg of butyl acetate, and react for 1 hour at an internal temperature of 75° C. to obtain a colorant intermediate.

[0138] S5: Add 55 kg of the colorant intermediate into the reactor, introduce nitrogen and start heating until the temperature rises to 82±2°C.

[0139] S6: Mix 5 kg of MMA, 40 kg of BMA and 0.3 kg of AIBN evenly and add them into the dropping tank. The dropping time is 4 hours and the dropping temperature is 82±2°C.

[0140] S7: After the dropwise addition is completed, the temperature is maintained at 82±2° C. and the reaction is carried out for 4 hours to obtain a coloring agent.

[0141] Comparative Example 5

[0142] This comparative example provides a colorant, and its preparation method comprises:

[0143] S1: 6.0 kg of polyether diol with a number average molecular weight of 2000, 6.0 kg of polyester diol with a number average molecular weight of 2000 and 11.5 kg of TPF-3178 red were added to a reactor, the temperature was raised to 100° C., and water was evaporated under reduced pressure for 2 hours to make the moisture content of the mixture ≤0.1%.

[0144] S2: Cool the contents of the reactor to 50°C, add 29.8 kg of DMF, then add 32.0 kg of IPDI and 43.0 g of dibutyltin dilaurate, and react for 2 h when the internal temperature reaches 85°C.

[0145] S3: Cool the contents of the reactor to 50°C, add 29.8 kg of DMF, then add 9.05 kg of butanediol, and react for 2 h when the internal temperature reaches 85°C.

[0146] S4: Add 1.6 kg of HEA and 39.7 kg of butyl acetate, and react for 1 hour at an internal temperature of 75° C. to obtain a colorant intermediate.

[0147] S5: Add 70 kg of the colorant intermediate into the reactor, introduce nitrogen and start heating until the temperature rises to 82±2°C.

[0148] S6: Mix 5 kg of MMA, 25 kg of BMA and 0.3 kg of AIBN and add them into the dropping tank. The dropping time is 4 hours and the dropping temperature is 82±2°C.

[0149] S7: After the dropwise addition is completed, the temperature is maintained at 82±2° C. and the reaction is carried out for 4 hours to obtain a coloring agent.

[0150] Comparative Example 6

[0151] This comparative example provides a colorant, and its preparation method comprises:

[0152] S1: 6.0 kg of polyether diol with a number average molecular weight of 2000, 6.0 kg of polyester diol with a number average molecular weight of 2000 and 11.5 kg of TPF-3178 red were added to a reactor, the temperature was raised to 100° C., and water was evaporated under reduced pressure for 2 hours to make the moisture content of the mixture ≤0.1%.

[0153] S2: Cool the contents of the reactor to 50°C, add 29.8 kg of DMF, then add 32.0 kg of IPDI and 43.0 g of dibutyltin dilaurate, and react for 2 h when the internal temperature reaches 85°C.

[0154] S3: Cool the contents of the reactor to 50°C, add 29.8 kg of DMF, then add 9.05 kg of butanediol, and react for 2 h when the internal temperature reaches 85°C.

[0155] S4: Add 1.6 kg of HEA and 39.7 kg of butyl acetate, and react for 1 hour at an internal temperature of 75° C. to obtain a colorant intermediate.

[0156] S5: Add 40 kg of the colorant intermediate into the reactor, introduce nitrogen and start heating until the temperature rises to 82±2°C.

[0157] S6: Mix 6.7 kg of MMA, 53.3 kg of BMA and 0.3 kg of AIBN and add them into the dropping tank. The dropping time is 4 hours and the dropping temperature is 82±2°C.

[0158] S7: After the dropwise addition is completed, the temperature is maintained at 82±2° C. and the reaction is carried out for 4 hours to obtain a coloring agent.

[0159] Comparative Example 7

[0160] This comparative example provides a colorant, and its preparation method comprises:

[0161] S1: 6.0 kg of polyether diol with a number average molecular weight of 2000, 6.0 kg of polyester diol with a number average molecular weight of 2000 and 11.5 kg of TPF-3178 red were added to a reactor, the temperature was raised to 100° C., and water was evaporated under reduced pressure for 2 hours to make the moisture content of the mixture ≤0.1%.

[0162] S2: Cool the contents of the reactor to 50°C, add 29.8 kg of DMF, then add 32.0 kg of IPDI and 43.0 g of dibutyltin dilaurate, and react for 2 h when the internal temperature reaches 85°C.

[0163] S3: Cool the contents of the reactor to 50°C, add 29.8 kg of DMF, then add 9.05 kg of butanediol, and react for 2 h when the internal temperature reaches 85°C.

[0164] S4: Add 1.6 kg of HEA and 39.7 kg of butyl acetate, and react for 1 hour at an internal temperature of 75° C. to obtain a colorant intermediate.

[0165] S5: Add 55 kg of the colorant intermediate into the reactor, introduce nitrogen and start heating until the temperature rises to 82±2°C.

[0166] S6: Mix 5 kg of MMA, 40 kg of BMA and 0.3 kg of AIBN evenly and add them into the dropping tank. The dropping time is 4 hours and the dropping temperature is 82±2°C.

[0167] S7: After the dropwise addition is completed, the temperature is maintained at 82±2°C for 2 hours to obtain a coloring agent.

[0168] Comparative Example 8

[0169] This comparative example provides a colorant, and its preparation method comprises:

[0170] S1: 6.0 kg of polyether diol with a number average molecular weight of 2000, 6.0 kg of polyester diol with a number average molecular weight of 2000 and 11.5 kg of TPF-3178 red were added to a reactor, the temperature was raised to 100° C., and water was evaporated under reduced pressure for 2 hours to make the moisture content of the mixture ≤0.1%.

[0171] S2: Cool the contents of the reactor to 50°C, add 29.8 kg of DMF, then add 32.0 kg of IPDI and 43.0 g of dibutyltin dilaurate, and react for 2 h when the internal temperature reaches 85°C.

[0172] S3: Cool the contents of the reactor to 50°C, add 29.8 kg of DMF, then add 9.05 kg of butanediol, and react for 2 h when the internal temperature reaches 85°C.

[0173] S4: Add 1.6 kg of HEA and 39.7 kg of butyl acetate, and react for 1 hour at an internal temperature of 75° C. to obtain a colorant intermediate.

[0174] S5: Add 55 kg of the colorant intermediate into the reactor, introduce nitrogen and start heating until the temperature rises to 82±2°C.

[0175] S6: Mix 5 kg of MMA, 40 kg of BMA and 0.3 kg of AIBN evenly and add them into the dropping tank. The dropping time is 4 hours and the dropping temperature is 82±2°C.

[0176] S7: After the dropwise addition is completed, the temperature is maintained at 82±2° C. and the reaction is carried out for 8 hours to obtain a coloring agent.

[0177] Test example

[0178] The colorants prepared in Examples 1 to 3 and Comparative Examples 4 to 8 and the conventional small molecule dyes provided in Comparative Examples 1 to 3 were applied to the surface treatment process of automotive synthetic leather under the same conditions to obtain automotive synthetic leather products. The light fastness, migration resistance, and color fastness to rubbing of each automotive synthetic leather product were tested. The test results are shown in Table 1.

[0179] Among them, the light fastness is tested according to the following method: after the leather is placed under a xenon lamp for 72 hours, the light fastness of the leather is tested according to the test method specified in QB / T 2727-2017 "Color fastness of leather to artificial light: xenon arc".

[0180] Migration resistance is tested according to GB / T 3903.42-2019 method.

[0181] The color fastness to rubbing is tested according to the following method: after the leather sample is rubbed back and forth 100 times under a pressure of 9N, the color fastness to rubbing of the leather is tested according to the test method specified in GB / T 2537 "Color fastness to rubbing of leather".

[0182] Table 1 Performance index test results

[0183]

[0184]

[0185] It can be seen from Table 1 that comparative examples 1, 2, 3, 4, 5, and 7 have obvious defects in performance; although comparative example 6 has acceptable performance, the content of colored intermediates is low, resulting in low color value, which is not conducive to market application; comparative example 8 has a long reaction time and high energy consumption. The colorant prepared in the embodiment of the present invention exhibits more excellent performance, specifically: high light fastness (≥6 levels), excellent migration resistance (≥4-5 levels), and good rubbing fastness (≥4-5 levels), which can meet the performance requirements and market demand of automotive leather.

[0186] In summary, the colorant provided by the present invention can meet the light resistance requirements of polymer colorants ≥ level 6 by introducing light-resistant chromophoric groups; through step-by-step addition reactions, on the one hand, the color can be locked in the molecular structure, and on the other hand, by forming a polymer product, the thermal motion rate of the molecules can be slowed down, so that the product meets the requirements of migration resistance ≥ level 4 to 5; by reacting the colorant intermediate with the acrylic monomer, the CC main chain in the acrylic resin structure does not contain easily oxidized and hydrolyzed groups, and has good antioxidant properties, medium resistance, light resistance and aging resistance, thereby further improving the light fastness of the product.

[0187] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A method for preparing a colorant intermediate, characterized in that: The following steps are involved: After the polymer polyol and the modified color are mixed in a reaction container, vacuum distillation is performed at 100°C to 105°C until the water content of the mixture is ≤0.1%; Cool down to 40-60°C, add 30%-40% of the total weight of the solvent, then add diisocyanate and catalyst, and react for 1.5-3 hours when the internal temperature reaches 80-90°C; Cool down to 40-60°C, add 20%-30% of the total weight of the solvent, and then add a small molecule diol to carry out a chain extension reaction. When the internal temperature reaches 70-85°C, react for 2h-3h; Add a terminator and the remaining solvent, and react for 0.5 h to 1.5 h at an internal temperature of 70° C. to 80° C. to obtain the colorant intermediate; The molar ratio of the diisocyanate to the polymer polyol is 1:0.03 to 1:0.06; The molar ratio of the diisocyanate to the modified color is 1:0.2 to 1:0.3; The molar ratio of the diisocyanate to the small molecule diol is 1:0.6 to 1:0.7; The molar ratio of the diisocyanate to the terminator is 1:0.02 to 1:0.07; The weight of the catalyst is 0.02% to 0.04% of the total weight of the material; The total weight of the solvent is 60% to 70% of the total weight of the material; The total weight of the materials is the total weight of the polymer polyol, modified color, solvent, diisocyanate, catalyst, small molecule diol and terminator.

2. The preparation method according to claim 1, characterized in that: The polymer polyol comprises at least one of polyether polyol, polyester polyol, polycarbonate polyol and polytetramethylene glycol; And / or, the modified color includes at least one of TPF-3178 crimson, TPF-3273 bright yellow and TPF-3342 blue.

3. The preparation method according to claim 1, characterized in that: The diisocyanate includes at least one of diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, xylylene diisocyanate and toluene diisocyanate; And / or, the catalyst includes at least one of organic tin and organic bismuth.

4. The preparation method according to claim 1, characterized in that: The small molecule diol includes at least one of ethylene glycol, propylene glycol, butanediol, 1,5-pentanediol, neopentyl glycol, hexanediol, diethylene glycol and 3-methyl-1,5-pentanediol; and / or, the terminator comprises at least one of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate and hydroxypropyl methacrylate; And / or, the solvent includes at least one of acetone, butanone, N-methylpyrrolidone, N-ethylpyrrolidone, dioxane, N,N-dimethylformamide, N,N-diethylformamide, toluene, xylene, ethyl acetate, butyl acetate, propylene glycol methyl ether acetate and isopropanol.

5. A colorant intermediate, characterized in that: The invention is prepared by the preparation method according to any one of claims 1 to 4.

6. A method for preparing a colorant, characterized in that: The preparation method of the colorant comprises: Under a protective atmosphere, a mixed solution of acrylic acid monomer and initiator is added dropwise to the heated colorant intermediate as claimed in claim 5; the addition time is 2h to 4h, and the addition temperature is 75°C to 90°C; After the dropwise addition is completed, the reaction is carried out at 80° C. to 95° C. for 4 h to 6 h to obtain the colorant.

7. The preparation method according to claim 6, characterized in that: The mass ratio of the acrylic acid monomer to the colorant intermediate is 40:60 to 50:50; The mass of the initiator is 0.1% to 5% of the total mass of the acrylic monomer and the colorant intermediate.

8. The preparation method according to claim 6 or 7, characterized in that: The acrylic monomer includes at least one of methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate and styrene; And / or, the initiator includes at least one of AIBN, BPO, LPO, TBPO and TAPO.

9. A colorant, characterized in that The colorant is prepared by the preparation method according to any one of claims 1 to 8.

10. A leather, characterized in that: The leather preparation process uses the colorant according to claim 9; Preferably, the leather comprises automotive leather.

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