CN112143184A - Biodegradable color master batch and preparation method thereof - Google Patents

Biodegradable color master batch and preparation method thereof Download PDF

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CN112143184A
CN112143184A CN202011050158.1A CN202011050158A CN112143184A CN 112143184 A CN112143184 A CN 112143184A CN 202011050158 A CN202011050158 A CN 202011050158A CN 112143184 A CN112143184 A CN 112143184A
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titanium dioxide
parts
carbon black
master batch
pigment
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CN112143184B (en
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李双利
周锐
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Qingdao Zhoushi Plastic Packing Co ltd
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Qingdao Zhoushi Plastic Packing Co ltd
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    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
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Abstract

The application relates to the field of plastic additives, and particularly discloses a biodegradable color master batch and a preparation method thereof. A biodegradable color master batch is prepared from the following raw materials: polybutylene terephthalate-adipate, polycaprolactone, pigment, plasticizer, dispersant and compatilizer; the plasticizer consists of microcrystalline cellulose, ethyl cellulose, tributyl citrate and castor oil in a weight ratio of 3-5:2-4:1-2: 1-2; the preparation method comprises the following steps: premixing polycaprolactone and a plasticizer, adding polybutylene terephthalate-adipate, and carrying out melting, extrusion and granulation to obtain a PBAT premix; mixing the PBAT premix, the pigment, the dispersing agent and the compatilizer, and then melting, extruding and granulating the mixture to obtain the PBAT pigment. The biodegradable color master batch can be used for dyeing degradable plastic products, and has the advantages of degradability and high dispersibility in the plastic products.

Description

Biodegradable color master batch and preparation method thereof
Technical Field
The application relates to the field of plastic additives, in particular to a biodegradable color master batch and a preparation method thereof.
Background
The master batch is also called as color master batch and plastic master batch, and is a plastic colorant prepared by well dispersing pigment or dye and thermoplastic resin with high proportion; for the special color master batch, the resin which is the same as the plastic product is selected as the carrier, so the special color master batch has good compatibility with the plastic resin, is more easily dispersed in the plastic product after being heated and melted, and is beneficial to improving the color stability of the plastic product.
In general, color masterbatch is composed of pigment, carrier, dispersant and additive; in the prior art, a patent application document with an application number of 200810122122.2 discloses a general white master batch and a preparation method thereof, wherein the general white master batch comprises the following components in percentage by weight: 15-20% of carrier resin, 40-80% of pigment, 5-10% of dispersing agent, 0-5% of processing aid, 0-2% of heat stabilizer and 0-40% of filler. The components are proportioned according to a proportion, premixed at a low speed for 0-10min in a mixer, then mixed at a high speed for 5-25min, melted and blended by a double-screw extruder, the temperature is controlled at 220 ℃ plus one sugar, the screw rotating speed is 80-400r/min, the pigment is uniformly dispersed in carrier resin by shearing and mixing of the screw, and then granulation, drying and packaging are carried out to obtain the color master batch.
In recent years, because the problem of environmental pollution caused by disposable plastic packaging products is becoming more and more serious, the research and application of degradable plastics are more and more paid more attention by people; the biodegradable plastic mainly uses polylactic acid (PLA), polybutylene terephthalate-adipate (PBAT), polybutylene succinate (PBS) and the like as materials of matrix resin, and the plastic materials can be degraded under specific conditions (such as composting conditions) under the action of microorganisms existing in nature and finally completely degraded into substances such as carbon dioxide, water and the like. For some degradable plastics with requirements on appearance color, a certain amount of color master batch needs to be added to achieve the purpose of coloring, however, at present, most of color master batches take traditional polymers (such as polyethylene) as carriers, but the compatibility of the color master batch and the degradable plastics is poor, the dispersibility of the color master batch in the degradable plastics is influenced, the color distribution of products is uneven, and the biodegradability of the degradable plastics is influenced by the addition of the traditional color master batch. Therefore, a degradable color masterbatch with good dispersibility is needed.
Disclosure of Invention
In order to improve the dispersibility of the color master batch in the processing of plastic products, the application provides a biodegradable color master batch.
In a first aspect, the application provides a biodegradable color master batch, which adopts the following technical scheme:
a biodegradable color master batch is prepared from the following raw materials in parts by weight: 30-40 parts of polybutylene terephthalate-adipate, 3-5 parts of polycaprolactone, 55-65 parts of pigment, 4-8 parts of plasticizer, 1-3 parts of dispersant and 0-2 parts of compatilizer; the plasticizer is composed of microcrystalline cellulose, ethyl cellulose, tributyl citrate and castor oil in a weight ratio of 3-5:2-4:1-2: 1-2.
By adopting the technical scheme, the poly (butylene terephthalate-adipate-co-terephthalate) (PBAT) is an aliphatic and aromatic copolymer, and integrates excellent degradability of aliphatic polyester and good mechanical property of aromatic polyester; polycaprolactone not only has good compatibility with high polymer but also has good biodegradability; the color master batch adopting PBAT as a carrier material has good biodegradability, and the compatibility of the PBAT color master batch and biodegradable plastics can be increased by adding a certain amount of polycaprolactone, so that the dispersibility of the color master batch in the material is improved. Because PBAT is a semi-crystalline polymer and Polycaprolactone (PCL) is a high-crystalline polymer, the crystallinity of resin molecules can be reduced and the plasticity of the resin molecules can be increased by adding a plasticizer compounded by microcrystalline cellulose, ethyl cellulose, tributyl citrate and castor oil, so that the melt flowability of the resin is improved and the dispersion uniformity of the pigment in the resin molecules is improved.
Preferably, the pigment is one of titanium dioxide, carbon black and vegetable dye.
By adopting the technical scheme, the titanium dioxide and the carbon black are used as dyes with high color shading capability and good coloring capability; the plant dye is prepared by extracting pigments from flowers, grasses, trees, roots, stems, leaves and the like in the nature, has good compatibility with the environment and good biodegradability; the color master batch adopting titanium dioxide and carbon black as pigments has good coloring capacity and certain biodegradability, and the color master batch adopting vegetable dye as pigments has excellent biodegradability; the addition amount of the color master in the plastic product is generally 4-5%, and the degradation rate of the common plastic product reaches 90%, so that the requirement of the degradable plastic can be met when the color master is used for processing the plastic product.
Preferably, the dispersant is one of polyethylene wax, distearamide and erucamide or a composite of the polyethylene wax, the distearamide and the erucamide.
By adopting the technical scheme, the polyethylene wax, the distearic acid amide and the erucamide can play good dispersing and lubricating properties during color master batch processing, can improve the dispersibility of the pigment in resin and improve the processing performance.
Preferably, the compatilizer is one of maleic anhydride grafted polyethylene and maleic anhydride grafted polypropylene.
By adopting the technical scheme, the compatilizer adopts maleic anhydride graft, and the compatibility of the inorganic pigment and PBAT can be improved by adding the compatilizer, so that the dispersibility of the pigment in the compatilizer is improved, the processing flowability of the color master is improved, and the dispersion performance and the coloring effect of the color master during the processing of plastic products are improved.
In a second aspect, the application provides a preparation method of a biodegradable color master batch, which adopts the following technical scheme:
a preparation method of biodegradable color master batch comprises the following steps:
s1, according to the proportion, taking polycaprolactone and a plasticizer, uniformly mixing at the temperature of 50-60 ℃, adding poly (butylene terephthalate) -adipate, heating to 130-150 ℃, and obtaining PBAT premix after melting, extruding and granulating;
s2, uniformly mixing the PBAT premix, the pigment, the dispersing agent and the compatilizer, and then melting, extruding and granulating at the temperature of 130-150 ℃ to obtain the biodegradable color master batch.
By adopting the technical scheme, the preparation method is simple and easy to operate, and the biodegradable color master batch is obtained by mixing the PBAT premix, the pigment, the dispersing agent and the compatilizer, melting, extruding and granulating.
Preferably, the mixing speed of the PBAT premix, the pigment and the compatilizer is 800-1200r/min, and the mixing time is 5-10 min.
By adopting the technical scheme, all the raw materials are mixed at the speed of 800-.
Preferably, the pigment in S2 is one of titanium dioxide, carbon black and vegetable dye.
Preferably, the titanium dioxide is modified by the following method before use:
firstly, taking a titanium dioxide raw material, grinding and sieving the titanium dioxide raw material to obtain titanium dioxide micro powder with the particle size of 1-5 mu m; adding 0.5-1 part of polycarboxylic acid sodium salt dispersing agent and 200-300 parts of water into 10 parts of titanium dioxide micro powder by weight parts, and uniformly stirring to obtain titanium dioxide slurry;
adding 1-3 parts of silicate mixture into the titanium dioxide slurry, uniformly stirring, and standing for 4-6 hours at the temperature of 70-80 ℃ to obtain titanium dioxide-silicate slurry;
thirdly, 30-40 parts of 5wt% aluminum sulfate solution is dripped into the titanium dioxide-silicate slurry within 1 hour, after the dripping is finished, the pH is adjusted to 7.0-7.5, and the mixture is kept stand at normal temperature for 4-6 hours to obtain alumina coated titanium dioxide suspension;
and fourthly, precipitating, filtering, washing and drying the alumina coated titanium dioxide suspension to obtain the modified titanium dioxide.
By adopting the technical scheme, the titanium dioxide raw material is ground to refine and crush the titanium dioxide, so that the particle size of the titanium dioxide is reduced, the surface area of the titanium dioxide is increased, and the covering power of the titanium dioxide is improved, but when the particle size of the titanium dioxide is reduced, the surface free energy of the titanium dioxide is also increased, so that the titanium dioxide is more likely to agglomerate, and the dispersibility of the titanium dioxide in carrier resin is influenced; by adding the silicate mixture into the refined titanium dioxide slurry, the silicate mixture carries out primary treatment on the surface of the nano powder, so that the surface energy of the titanium dioxide is reduced, the particle size of the aggregate is reduced, the covering power of the aggregate is improved, the compactness and the structural stability of a subsequent coating film can be improved, and an alumina coating film is formed on the surface of the titanium dioxide through the deposition of alumina; after the titanium dioxide is modified, the dispersibility of the titanium dioxide in the carrier resin can be greatly improved, and the covering power of the titanium dioxide is improved, so that the titanium dioxide has a good coloring effect.
Preferably, the silicate mixture is prepared from the following raw materials in parts by weight: grinding and sieving calcium silicate to obtain calcium silicate powder with particle size of 1-5 μm; 0.1 to 0.2 part of a silane coupling agent and 3 to 5 parts of lithium silicate are added to 10 parts of calcium silicate powder, and the mixture is ground to obtain a silicate mixture.
By adopting the technical scheme, when the titanium dioxide is treated by the silicate mixture compounded by calcium silicate, silane coupling agent and lithium silicate, the surface energy of the titanium dioxide is reduced, the particle size of the aggregate is reduced, the covering power of the aggregate is improved, and the compactness and the structural stability of a subsequent coating film can be improved.
Preferably, the carbon black is modified before use by the following method:
a. taking 100 parts of carbon black and 500 parts of concentrated nitric acid solution by weight, and carrying out stirring reaction for 6-8h at the temperature of 60-70 ℃ and the stirring speed of 200-600r/min to obtain pretreated carbon black; washing the pretreated carbon black with water to neutrality, and drying to obtain oxidized carbon black;
b. grinding 10 parts of lignin, 3-5 parts of polyvinylpyrrolidone and 0.1-0.2 part of titanate coupling agent at the speed of 1000-;
c. adding the pretreated lignin into the oxidized carbon black, and grinding for 20-24h at the speed of 1000-2000r/min to obtain the modified carbon black.
By adopting the technical scheme, the carbon black is a nano material, the primary particle size is generally between 10 and 100nm, the smaller the carbon black, the higher the carbon black content, the larger the surface area, the higher the tinting strength but also the strengthening of intermolecular force for quality inspection of carbon black aggregates, and the dispersion of the carbon black is influenced; the surface area and the porosity of the carbon black can be changed by oxidizing the carbon black; the lignin molecular structure contains reactive active points such as phenolic hydroxyl, carbonyl, active hydrogen and the like, and the pretreated lignin obtained after pretreatment is used for treating the oxidized carbon black, so that the dispersion stability of the carbon black in the resin can be remarkably improved, and the dispersion of the color master batch in a plastic product is improved, and meanwhile, a certain reinforcing effect on the plastic product can be achieved.
In summary, the present application has the following beneficial effects:
1. according to the preparation method, the PBAT and the PCL are compounded, and the plasticizer compounded by microcrystalline cellulose, ethyl cellulose, tributyl citrate and castor oil is added, so that the crystallinity of resin molecules can be reduced, the plasticity of the resin molecules can be increased, the melt flowability of the resin can be improved, and the dispersion uniformity of the pigment in the resin molecules can be improved.
2. According to the method, before the titanium dioxide is mixed with other raw materials, the titanium dioxide is subjected to modification treatment, so that the dispersibility of the titanium dioxide in carrier resin can be greatly improved, the covering power of the titanium dioxide is improved, and the titanium dioxide has a good coloring effect.
3. The surface area and the porosity of the carbon black can be changed by oxidizing the carbon black; the lignin molecular structure contains reactive active points such as phenolic hydroxyl, carbonyl, active hydrogen and the like, and the pretreated lignin obtained after pretreatment is used for treating the oxidized carbon black, so that the dispersion stability of the carbon black in the resin can be remarkably improved, and the dispersion of the color master batch in a plastic product is improved, and meanwhile, a certain reinforcing effect on the plastic product can be achieved.
Detailed Description
The present application will be described in further detail with reference to examples.
Preparation of modified titanium dioxide the lithium silicate in the following preparation is selected from 4.85 modulus lithium silicate provided by chemical ltd of juanzai fengda; the titanium dioxide is selected from rutile titanium dioxide with the model of R838 provided by Jinan Yuxing chemical Limited liability company; the sodium polycarboxylate dispersant is selected from YL-5040 sodium polycarboxylate dispersants provided by Nantong Yongle chemical Co.
Preparation example 1 of modified titanium dioxide: firstly, taking calcium silicate, grinding and sieving the calcium silicate to obtain calcium silicate powder with the particle size of 1-5 mu m; adding 0.1kg of silane coupling agent KH570 and 3kg of lithium silicate into 10kg of calcium silicate powder, and grinding at the speed of 2000r/min for 4h to obtain a silicate mixture;
secondly, taking rutile type titanium dioxide, grinding and sieving the rutile type titanium dioxide to obtain titanium dioxide micro powder with the particle size of 1-5 mu m; adding 0.5kg of polycarboxylic acid sodium salt dispersing agent and 200kg of water into 10kg of titanium dioxide micro powder, and stirring at the speed of 2000r/min for 30min to obtain titanium dioxide slurry;
thirdly, adding 1-3kg of silicate mixture into the titanium dioxide slurry, stirring for 30min at the speed of 2000r/min, and standing for 4-6h at the temperature of 70-80 ℃ to obtain titanium dioxide-silicate slurry;
dripping 30kg of 5wt% aluminum sulfate solution into the titanium dioxide-silicate slurry within 1h, adjusting the pH to 7.0 after finishing dripping, and standing at normal temperature for 4h to obtain an alumina-coated titanium dioxide suspension;
fifthly, standing the alumina-coated titanium dioxide suspension for 24 hours to obtain a precipitate, then filtering the precipitate to remove water, washing the precipitate with deionized water, and drying the precipitate at the speed of 80 ℃ for 4 hours to obtain the modified titanium dioxide.
Preparation example 2 of modified titanium dioxide: firstly, taking calcium silicate, grinding and sieving the calcium silicate to obtain calcium silicate powder with the particle size of 1-5 mu m; adding 0.15kg KH570 and 4kg lithium silicate into 10kg calcium silicate powder, and grinding at 3000r/min for 3 hr to obtain silicate mixture;
secondly, taking rutile type titanium dioxide, grinding and sieving the rutile type titanium dioxide to obtain titanium dioxide micro powder with the particle size of 1-5 mu m; adding 0.75kg of polycarboxylic acid sodium salt dispersing agent and 250kg of water into 10kg of titanium dioxide micro powder, and stirring at the speed of 2000r/min for 30min to obtain titanium dioxide slurry;
thirdly, adding 2kg of silicate mixture into the titanium dioxide slurry, stirring for 30min at the speed of 2000r/min, and standing for 5h at the temperature of 75 ℃ to obtain titanium dioxide-silicate slurry;
dripping 35kg of 5wt% aluminum sulfate solution into the titanium dioxide-silicate slurry within 1h, adjusting the pH to 7.2 after finishing dripping, and standing at normal temperature for 5h to obtain an alumina-coated titanium dioxide suspension;
fifthly, standing the alumina-coated titanium dioxide suspension for 24 hours to obtain a precipitate, then filtering the precipitate to remove water, washing the precipitate with deionized water, and drying the precipitate at the speed of 85 ℃ for 5 hours to obtain the modified titanium dioxide.
Preparation example 3 of modified titanium dioxide: firstly, taking calcium silicate, grinding and sieving the calcium silicate to obtain calcium silicate powder with the particle size of 1-5 mu m; adding 0.1kg of silane coupling agent KH570, 0.1kg of silane coupling agent KH791 and 5kg of lithium silicate into 10kg of calcium silicate powder, and grinding at the speed of 4000r/min for 2 hours to obtain a silicate mixture;
secondly, taking rutile type titanium dioxide, grinding and sieving the rutile type titanium dioxide to obtain titanium dioxide micro powder with the particle size of 1-5 mu m; adding 1kg of polycarboxylic acid sodium salt dispersing agent and 300kg of water into 10kg of titanium dioxide micro powder, and stirring at the speed of 2000r/min for 30min to obtain titanium dioxide slurry;
thirdly, adding 3kg of silicate mixture into the titanium dioxide slurry, stirring for 30min at the speed of 2000r/min, and standing for 6h at the temperature of 80 ℃ to obtain titanium dioxide-silicate slurry;
dripping 40kg of 5wt% aluminum sulfate solution into the titanium dioxide-silicate slurry within 1h, adjusting the pH to 7.5 after finishing dripping, and standing at normal temperature for 6h to obtain an alumina-coated titanium dioxide suspension;
fifthly, standing the alumina-coated titanium dioxide suspension for 24 hours to obtain a precipitate, then filtering the precipitate to remove water, washing the precipitate with deionized water, and drying the precipitate at the speed of 90 ℃ for 6 hours to obtain the modified titanium dioxide.
Preparation example 4 of modified titanium dioxide: firstly, taking rutile type titanium dioxide, grinding and sieving the rutile type titanium dioxide to obtain titanium dioxide micropowder with the particle size of 1-5 mu m; adding 0.5kg of polycarboxylic acid sodium salt dispersing agent and 200kg of water into 10kg of titanium dioxide micro powder, and stirring at the speed of 2000r/min for 30min to obtain titanium dioxide slurry;
dropping 30kg of 5wt% aluminum sulfate solution into the titanium dioxide slurry within 1h, adjusting the pH to 7.0 after the dropping, and standing at normal temperature for 4h to obtain an alumina-coated titanium dioxide suspension;
standing the alumina-coated titanium dioxide suspension for 24 hours to obtain a precipitate, filtering the precipitate to remove water, washing the precipitate with deionized water, and drying the precipitate at the speed of 80 ℃ for 4 hours to obtain the modified titanium dioxide.
Preparation example of modified carbon Black
The carbon black in the following preparation examples is selected from the pigment carbon blacks available from Degussa under the model number PRINTEX140V, with a particle size of 29nm and a specific surface area of 90m2Oil absorption of 450mL/100g and tinting strength of 115% and the pH value is 4; the lignin is selected from lignin available from Strand corporation; the polyvinylpyrrolidone is polyvinylpyrrolidone provided by BASF and is kollidon 30; the titanate coupling agent is selected from mono-alkoxy fatty acid titanate coupling agent with the model number TC-130 provided by Shandong Moore chemical industry Co.
Preparation example 1 of modified carbon black:
a. taking 100kg of carbon black and 300kg of concentrated nitric acid solution with the mass fraction of 68%, and stirring and reacting for 6 hours at the temperature of 60 ℃ and the stirring speed of 200r/min to obtain pretreated carbon black; washing the pretreated carbon black with water to neutrality, and drying at 70 ℃ for 6h to obtain oxidized carbon black;
b. grinding 10kg of lignin, 3kg of polyvinylpyrrolidone and 0.1kg of titanate coupling agent at the speed of 1000r/min for 6h to obtain pretreated lignin;
c. adding the pretreated lignin into the oxidized carbon black, and grinding for 20 hours at the speed of 1000r/min to obtain the modified carbon black.
Preparation example 2 of modified carbon black:
a. taking 100kg of carbon black and 400kg of concentrated nitric acid solution with the mass fraction of 68%, and stirring and reacting for 7 hours at the temperature of 65 ℃ and the stirring speed of 400r/min to obtain pretreated carbon black; washing the pretreated carbon black with water to neutrality, and drying at 70 ℃ for 6h to obtain oxidized carbon black;
b. grinding 10kg of lignin, 4kg of polyvinylpyrrolidone and 0.15kg of titanate coupling agent at the speed of 1500r/min for 8 hours to obtain pretreated lignin;
c. adding the pretreated lignin into the oxidized carbon black, and grinding for 22h at the speed of 1500r/min to obtain the modified carbon black.
Preparation example 3 of modified carbon black:
a. taking 100kg of carbon black and 500kg of concentrated nitric acid solution with the mass fraction of 68%, and stirring and reacting for 8 hours at the temperature of 70 ℃ and the stirring speed of 600r/min to obtain pretreated carbon black; washing the pretreated carbon black with water to neutrality, and drying at 70 ℃ for 6h to obtain oxidized carbon black;
b. grinding 10kg of lignin, 5kg of polyvinylpyrrolidone and 0.2kg of titanate coupling agent at the speed of 2000r/min for 10 hours to obtain pretreated lignin;
c. adding the pretreated lignin into the oxidized carbon black, and grinding for 24 hours at the speed of 2000r/min to obtain the modified carbon black.
Preparation example 4 of modified carbon black: this preparation example differs from preparation example 1 of modified carbon black in that step b is not included, and the oxidized carbon black obtained in step a is ground at a speed of 1000r/min for 20 hours to obtain a modified carbon black.
Examples
The polybutylene terephthalate-adipate in the following examples was selected from PBAT resin having a designation TH801 supplied by tun river, blue, xinjiang; selecting polycaprolactone with model number ESUN-600C provided by Shenzhen Guanghua Webber Limited; the maleic anhydride grafted polyethylene is selected from maleic anhydride grafted polyethylene with the model G1203, which is provided by Kagaozhi high plasticizing Co., Ltd, in Fushan city; the maleic anhydride grafted polypropylene is selected from maleic anhydride grafted polypropylene with the model number of KHPP-1020 provided by Ningbo Ersanke plastic technology company Limited; the plant dye is extracted from plant capable of extracting pigment, and the plant containing the extracted pigment is beet, fructus Gardeniae, radix Rubiae, herba Rhododendri Dahurici, flos Buddlejae, fructus Gardeniae, indigo, Carthami flos, herba Spinaciae, sweet potato leaf, fructus Cucurbitae Moschatae, ilex chinensis, Curcuma rhizome, herba Hyperici Japonici, Perillae herba, etc.
Example 1: the biodegradable color master batch is prepared by the following method:
s1, taking 3kg of polycaprolactone and 4kg of plasticizer, uniformly mixing at 50 ℃, putting the mixed polycaprolactone and plasticizer into a double-screw extruder, adding 30kg of polybutylene terephthalate-adipate, and melting, extruding and granulating at the speed of 30r/min at the temperature of a first zone, the temperature of a second zone, the temperature of a third zone, the temperature of a fourth zone, the temperature of a fifth zone, the temperature of a sixth zone, the temperature of a nose of a machine of the double-screw extruder of 130 ℃, the temperature of a third zone, the temperature of a fourth zone, the temperature of a fifth zone and the temperature of a sixth zone of 145 ℃, the temperature of the machine of a fourth zone and the temperature of a fifth zone of 145 ℃, the temperature of a sixth;
s2, mixing PBAT premix, 55kg pigment and 1kg dispersant at the speed of 800r/min for 5min, and then placing the mixed materials into a double-screw extruder, wherein the temperatures of the two zones of the double-screw extruder are 130 ℃ in the first zone, 140 ℃ in the second zone, 145 ℃ in the third zone, 150 ℃ in the fourth zone, 150 ℃ in the fifth zone, 140 ℃ in the sixth zone, 140 ℃ in the head, and 30r/min in the screw speed, and then carrying out melting, extrusion and granulation to obtain the biodegradable color master;
wherein the pigment is common rutile type titanium dioxide with the particle size of 1-5 mu m; the plasticizer consists of microcrystalline cellulose, ethyl cellulose, tributyl citrate and castor oil in a weight ratio of 3:2:1: 1; the dispersing agent is polyethylene wax.
Example 2: the biodegradable color master batch is prepared by the following method:
s1, taking 4kg of polycaprolactone and 6kg of plasticizer, uniformly mixing at 55 ℃, putting the mixed polycaprolactone and plasticizer into a double-screw extruder, adding 35kg of polybutylene terephthalate-adipate, and melting, extruding and granulating at the speed of 30r/min at the temperature of a first zone, the temperature of a second zone, the temperature of a third zone, the temperature of a fourth zone, the temperature of a fifth zone, the temperature of a sixth zone, the temperature of a nose of a machine head of the double-screw extruder of 130 ℃, the temperature of a third zone, the temperature of a fourth zone, the temperature of a fifth zone and the temperature of a sixth zone of 145 ℃, the temperature of the fourth zone and the temperature of a fifth zone of 145 ℃;
s2, mixing PBAT premix, 60kg pigment and 2kg dispersant at the speed of 1000r/min for 8min, and then placing the mixed materials into a double-screw extruder, wherein the temperatures of the two zones of the double-screw extruder are 130 ℃ in the first zone, 140 ℃ in the second zone, 145 ℃ in the third zone, 150 ℃ in the fourth zone, 150 ℃ in the fifth zone, 140 ℃ in the sixth zone, 140 ℃ in the head, and 30r/min in the screw speed, and then carrying out melting, extrusion and granulation to obtain the biodegradable color master;
wherein the pigment is common rutile type titanium dioxide with the particle size of 1-5 mu m; the plasticizer consists of microcrystalline cellulose, ethyl cellulose, tributyl citrate and castor oil in a weight ratio of 4:3:1.5: 1.5; the dispersant is bis stearamide.
Example 3: the biodegradable color master batch is prepared by the following method:
s1, taking 5kg of polycaprolactone and 8kg of plasticizer, uniformly mixing at the temperature of 60 ℃, putting the mixed polycaprolactone and plasticizer into a double-screw extruder, adding 40kg of polybutylene terephthalate-adipate, and melting, extruding and granulating at the speed of 30r/min at the temperature of a first zone, the temperature of a second zone, the temperature of a third zone, the temperature of a fourth zone, the temperature of a fifth zone, the temperature of a sixth zone, the temperature of a nose of a machine head of the double-screw extruder of 130 ℃, the temperature of a third zone, the temperature of a fourth zone, the temperature of a fifth zone and the temperature of a sixth zone of 135 ℃, so as to obtain PBAT premix;
s2, mixing PBAT premix, 65kg pigment and 3kg dispersant at the speed of 1200r/min for 5-10min, then placing the mixed materials in a double-screw extruder, wherein the temperatures of the two zones of the double-screw extruder are 130 ℃ in the first zone, 140 ℃ in the second zone, 145 ℃ in the third zone, 150 ℃ in the fourth zone, 150 ℃ in the fifth zone, 140 ℃ in the sixth zone, 140 ℃ in the head and 30r/min in the screw speed, and then carrying out melting, extrusion and granulation to obtain the biodegradable color master;
wherein the pigment is common rutile type titanium dioxide with the particle size of 1-5 mu m; the plasticizer consists of microcrystalline cellulose, ethyl cellulose, tributyl citrate and castor oil in a weight ratio of 5:4:2: 2; the dispersant is erucamide.
Example 4: the difference between this example and example 1 is that 2kg of a compatibilizer, which is maleic anhydride-grafted polyethylene, was further added to the raw material of S2.
Example 5: the difference between this example and example 1 is that 2kg of a compatibilizer, which is maleic anhydride-grafted polypropylene, was further added to the raw material of S2.
Example 6: the difference between this example and example 1 is that the pigment is titanium dioxide prepared from preparation example 1 of modified titanium dioxide.
Example 7: the difference between this example and example 1 is that the pigment is titanium dioxide prepared from preparation example 2 of modified titanium dioxide.
Example 8: the difference between this example and example 1 is that the pigment is titanium dioxide prepared from preparation example 3 of modified titanium dioxide.
Example 9: this example differs from example 1 in that the pigment is a pigmented carbon black supplied by Texaco under the model number PRINTEX 140V.
Example 10: this example differs from example 1 in that the pigment was the carbon black prepared in preparation example 1 of modified carbon black.
Example 11: this example differs from example 1 in that the pigment was the carbon black prepared in preparation example 2 of modified carbon black.
Example 12: this example differs from example 1 in that the pigment was the carbon black prepared in preparation example 3 of modified carbon black.
Example 13: the difference between this example and example 1 is that the pigment is E2 beet red pigment provided by Wuhan Lin Baolai Biotech, Inc.
Example 14: this example differs from example 1 in that the pigment was E60 gardenia yellow supplied by Biotechnology, Inc., of Western Haoyao.
Comparative example
Comparative example 1: this comparative example differs from example 1 in that the plasticizer consists only of microcrystalline cellulose, ethyl cellulose in a weight ratio of 3: 2.
Comparative example 2: this comparative example differs from example 1 in that the plasticizer consists only of tributyl citrate and castor oil in a weight ratio of 1: 1.
Comparative example 3: this comparative example differs from example 1 in that the polycaprolactone in the starting material was replaced by an equal amount of polybutylene terephthalate-adipate.
Comparative example 4: the difference between the comparative example and the example 1 is that the titanium dioxide in the raw material is prepared by the preparation example 4 of the modified titanium dioxide.
Comparative example 5: this comparative example differs from example 1 in that the carbon black in the raw material was prepared using modified carbon black of preparation example 4.
Performance test
The application method comprises the following steps: weighing 100g of PBAT, respectively adding 5g of the color master batches prepared in the examples 1-14 and the comparative examples 1-5, uniformly mixing, placing in a film blowing machine, setting various parameters of the film blowing machine as 140 ℃ in a first area of a charging barrel, 145 ℃ in a second area, 150 ℃ in a third area, 155 ℃ in a fourth area, 150 ℃ in a fifth area, 145 ℃ in a sixth area, 145 ℃ in a head, and 60r/min of screw rotation, and carrying out blow molding on the PBAT resin to form a film, so as to obtain a PBAT film with the thickness of 80 mu m; the performance of the color master batch is tested by testing the performance of the film according to the following method, and the test result is shown in table 1; wherein the raw material PBAT of the film is selected from PBAT resin with the brand number TH801 provided by Xinjiang blue mountain Tunghe, and the density of the PBAT resin is 1.21g/cm3The melt index (190 ℃, 2.16kg) is 4.0g/10min, the tensile strength is more than or equal to 25MPa, and the elongation at break is more than or equal to 400 percent.
With reference to the method in QB/T1648-1992 polyethylene coloring masterbatch, the appearance of the product is observed, and the dispersion uniformity of the color masterbatch in the resin is verified by observing whether the surface of the film has irregular color dots; for first-class products, the color points with the diameter more than 1.0mm and more than 0.6-1.0mm are not allowed to appear, and the number of the color points with the diameter of 0.3-0.6mm is less than or equal to 5; the dispersity is less than or equal to 3.
Torque rheology: by testing the highest torque of the color master batch, the processing fluidity of the standard color master batch can be measured, so that the compatibility of the pigment in the color master batch and the carrier resin is reflected, a Brabender PLV-151 type torque rheometer is adopted, 50g of the color master batch is taken, the test temperature is 130 ℃, the rotating speed is 30r/min, and the time is 10 min; the lower the maximum torque value, the lower the viscosity of the system, and the better the processing fluidity of the product.
Tensile strength: the test was carried out according to the method of GB/T13022-1991 "method for testing tensile Properties of Plastic films".
Covering power: the transmittance of the film was measured by a Datacolor model 650 colorimeter and converted into an optical density value of a standard film thickness (0.02 mm). The optical density value can be used for representing the covering power and reflecting the dispersion condition of the pigmentThe more uniform the dispersion, the finer the particles, the higher the optical density value, the stronger the hiding power and vice versa. In color measurement, light transmission is measured by the spectral transmittance T, which is defined when the intensity of a beam is I0When the light irradiates on the film, part of the light is scattered and absorbed by pigment particles in the film except for reflection, and the rest part of the light is transmitted, and the transmitted light intensity is I1Transmittance O1/T I0/I1Optical density D-lgO-lgI0/I1。
Tinting strength (whiteness value): the film sample passes through a Datacolor 650 type color measuring instrument to test the whiteness value of the film sample, and the larger the whiteness value is, the better the tinting strength of the white master batch is.
TABLE 1 film Performance test tables for examples 1-14 and comparative examples 1-5
Figure BDA0002709303730000111
According to the data in table 1, the number of color dots of the film in examples 1-3 is less than or equal to 3, the number of dispersion degrees is less than or equal to 2, the highest torque is less than 16.5, the tensile strength is greater than 27Mpa, the elongation at break is greater than 420%, and the color shading degree and the tinting strength are good, which indicates that the color master batch prepared by using the raw materials of the present application has good dispersibility in degradable plastics and good tinting effect on the degradable plastics.
Combining examples 1, 4 and 5, it is known that the number of color dots, the dispersion degree, and the maximum torque of examples 4 and 5 are significantly lower than those of example 1, and the tensile strength, the elongation at break, the hiding power, and the tinting strength of examples 4 and 5 are significantly higher than those of example 1, which indicates that when maleic anhydride grafted polyethylene or maleic anhydride grafted polypropylene is added to the raw material of the color masterbatch, the compatibility between the pigment and the carrier resin can be improved, so that the dispersion degree and the tinting strength of the color masterbatch in the plastic product can be improved, and the mechanical strength of the product can be improved to some extent.
It can be known from the combination of the examples 6, 7 and 8 that the number, dispersion degree and maximum torque of the color dots in examples 6 to 8 are significantly lower than those in example 1, and the tensile strength, elongation at break, covering power and tinting strength of examples 4 and 5 are significantly higher than those in example 1, which indicates that the modified titanium dioxide prepared by using the preparation example of the modified titanium dioxide of the present application has significantly reduced agglomeration phenomenon in the polymer, can significantly improve the dispersibility in the carrier resin, is beneficial to improving the processing fluidity of the white color masterbatch, and improves the dispersibility of the color masterbatch in plastic products and the tinting strength of the color masterbatch on plastic resins, compared with the common titanium dioxide.
By combining examples 9 and 10-12, it can be seen that when the black color masterbatch is used in the processing of plastic products, the number, dispersion degree, and maximum torque of the color dots of examples 10-12 are significantly lower than those of example 9, and the tensile strength, elongation at break, hiding power, and tinting strength of examples 10-12 are significantly higher than those of example 9, which indicates that the modified carbon black prepared by the preparation example of the modified carbon black of the present application has significantly reduced agglomeration phenomenon in the polymer and improved dispersibility in the carrier resin, compared with the common pigment carbon black, which is not only beneficial to improving the processing flowability of the black color masterbatch, improving the dispersibility of the color masterbatch in the plastic products and tinting strength of the color masterbatch on the plastic resins, but also has a certain reinforcing effect on the plastic products.
The red color master batch is used in the embodiment 14, the yellow color master batch is used in the embodiment 15, the number of color points of the embodiment 14 and the embodiment 15 is less than or equal to 5, the dispersity is less than or equal to 3, and the product has better mechanical property and hiding power, which shows that the red color master batch and the yellow color master batch have better dispersity and hiding power in plastic products.
Combining example 1, comparative example 1 and comparative example 2, it can be seen that the number of color points, dispersion degree and maximum torque of comparative example 1 and comparative example 2 are significantly higher than those of example 1, and the tensile strength, elongation at break, hiding power and tinting strength of comparative example 1 and comparative example 2 are significantly lower than those of example 1, which shows that the plasticizers microcrystalline cellulose, ethyl cellulose, tributyl citrate and castor oil adopted in the present application have a good compounding synergistic effect, can improve the plasticity of the carrier resin, improve the fluidity thereof, and thus are beneficial to improving the dispersibility of the pigment in the carrier resin, so as to improve the dispersion effect of the color master in the plastic product.
Combining example 1 and comparative example 3, it can be seen that the number of color dots, dispersion degree, and maximum torque of comparative example 3 are significantly higher than those of example 1, and the tensile strength, elongation at break, hiding power, and tinting strength of comparative example 3 are significantly lower than those of example 1, which indicates that adding a certain amount of polycaprolactone to the carrier resin of the color masterbatch is beneficial to improving the processing flowability of the system, thereby being beneficial to improving the dispersion of the pigment in the carrier resin and improving the dispersion effect of the color masterbatch in the plastic product.
Combining example 6 and comparative example 4, it can be seen that the number of color dots, dispersion degree, and maximum torque of comparative example 4 are significantly higher than those of example 6, and the tensile strength, elongation at break, hiding power, and tinting strength of comparative example 4 are significantly lower than those of example 6, which indicates that when titanium dioxide is modified, the surface of titanium dioxide is treated in advance by adding the silicate mixture to improve the subsequent coating of alumina, so that the dispersion degree of titanium dioxide and the performance of the modified color master batch can be further improved.
Combining example 10 and comparative example 5, it can be seen that the number of color dots, dispersion degree, and maximum torque of comparative example 5 are significantly higher than those of example 1, and the tensile strength, elongation at break, hiding power, and tinting strength of comparative example 5 are significantly lower than those of example 10, which shows that when the carbon black is modified, the dispersion of the carbon black in the carrier resin can be improved, and the reinforcing effect of the color master batch on the plastic product can also be improved after the pretreatment lignin obtained by treating the carbon black with lignin, polyvinylpyrrolidone, and titanate coupling agent is added.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.

Claims (10)

1. The biodegradable color master batch is characterized by being prepared from the following raw materials in parts by weight: 30-40 parts of polybutylene terephthalate-adipate, 3-5 parts of polycaprolactone, 55-65 parts of pigment, 4-8 parts of plasticizer, 1-3 parts of dispersant and 0-2 parts of compatilizer;
the plasticizer is composed of microcrystalline cellulose, ethyl cellulose, tributyl citrate and castor oil in a weight ratio of 3-5:2-4:1-2: 1-2.
2. The biodegradable color masterbatch of claim 1, wherein the pigment is one of titanium dioxide, carbon black and vegetable dye.
3. The biodegradable color masterbatch according to claim 1, wherein the dispersant is one of polyethylene wax, distearamide, erucamide or a combination thereof.
4. The biodegradable color masterbatch of claim 1, wherein the compatibilizer is one of maleic anhydride grafted polyethylene and maleic anhydride grafted polypropylene.
5. A method for preparing biodegradable color masterbatch according to claim 1, comprising the following steps:
s1, according to the proportion, taking polycaprolactone and a plasticizer, uniformly mixing at the temperature of 50-60 ℃, adding poly (butylene terephthalate) -adipate, heating to 130-150 ℃, and obtaining PBAT premix after melting, extruding and granulating;
s2, uniformly mixing the PBAT premix, the pigment, the dispersing agent and the compatilizer, and then melting, extruding and granulating at the temperature of 130-150 ℃ to obtain the biodegradable color master batch.
6. The preparation method of biodegradable color masterbatch according to claim 5, wherein the mixing speed of PBAT premix, pigment and compatibilizer is 800-1200r/min, and the mixing time is 5-10 min.
7. The preparation method of biodegradable color masterbatch according to claim 5, wherein the pigment in S2 is one of titanium dioxide, carbon black and vegetable dye.
8. The preparation method of the biodegradable color master batch according to claim 7, wherein the titanium dioxide is modified by the following method before use:
firstly, taking a titanium dioxide raw material, grinding and sieving the titanium dioxide raw material to obtain titanium dioxide micro powder with the particle size of 1-5 mu m; adding 0.5-1 part of polycarboxylic acid sodium salt dispersing agent and 200-300 parts of water into 10 parts of titanium dioxide micro powder by weight parts, and uniformly stirring to obtain titanium dioxide slurry;
adding 1-3 parts of silicate mixture into the titanium dioxide slurry, uniformly stirring, and standing for 4-6 hours at the temperature of 70-80 ℃ to obtain titanium dioxide-silicate slurry;
thirdly, 30-40 parts of 5wt% aluminum sulfate solution is dripped into the titanium dioxide-silicate slurry within 1 hour, after the dripping is finished, the pH is adjusted to 7.0-7.5, and the mixture is kept stand at normal temperature for 4-6 hours to obtain alumina coated titanium dioxide suspension;
and fourthly, precipitating, filtering, washing and drying the alumina coated titanium dioxide suspension to obtain the modified titanium dioxide.
9. The preparation method of the biodegradable color masterbatch according to claim 8, wherein the silicate mixture is prepared from the following raw materials in parts by weight: grinding and sieving calcium silicate to obtain calcium silicate powder with particle size of 1-5 μm; 0.1 to 0.2 part of a silane coupling agent and 3 to 5 parts of lithium silicate are added to 10 parts of calcium silicate powder, and the mixture is ground to obtain a silicate mixture.
10. The preparation method of the biodegradable color master batch as claimed in claim 7, wherein the carbon black is modified before use by adopting the following method:
a. taking 100 parts of carbon black and 500 parts of concentrated nitric acid solution by weight, and carrying out stirring reaction for 6-8h at the temperature of 60-70 ℃ and the stirring speed of 200-600r/min to obtain pretreated carbon black; washing the pretreated carbon black with water to neutrality, and drying to obtain oxidized carbon black;
b. grinding 10 parts of lignin, 3-5 parts of polyvinylpyrrolidone and 0.1-0.2 part of titanate coupling agent at the speed of 1000-;
c. adding the pretreated lignin into the oxidized carbon black, and grinding for 20-24h at the speed of 1000-2000r/min to obtain the modified carbon black.
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CN111235923A (en) * 2020-03-11 2020-06-05 华维新材料科技(杭州)有限公司 Preparation and dyeing process of nano liquid black

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CN114058085A (en) * 2021-12-31 2022-02-18 广东宏开新材料科技有限公司 CAB solid color master batch and preparation method thereof
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CN115160681A (en) * 2022-07-13 2022-10-11 广东九彩新材料有限公司 Low-odor high-carbon-black-content polyethylene color master batch and preparation method thereof
CN115160681B (en) * 2022-07-13 2023-02-03 广东九彩新材料有限公司 Low-odor high-carbon-black-content polyethylene color master batch and preparation method thereof
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