CN112143184B - Biodegradable color master batch and preparation method thereof - Google Patents
Biodegradable color master batch and preparation method thereof Download PDFInfo
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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); 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. 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
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 the 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 190-220 ℃, 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 prepare 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 is required to be added to achieve the purpose of coloring, however, at present, most color masters use traditional polymers (such as polyethylene) as carriers, but the compatibility of the color master and the degradable plastics is poor, the dispersibility of the color master 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. 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 consists of microcrystalline cellulose, ethyl cellulose, tributyl citrate and castor oil in a weight ratio of (3-5).
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 a proportion, taking polycaprolactone and a plasticizer, uniformly mixing at the temperature of 50-60 ℃, adding polybutylene terephthalate-adipate, heating to 130-150 ℃, and carrying out melting, extrusion and granulation to obtain a PBAT premix;
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 5-10min.
By adopting the technical scheme, all the raw materials are mixed at the speed of 800-1200r/min, which is beneficial to improving the uniformity of the raw material mixing.
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:
(1) 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 part, and uniformly stirring to obtain titanium dioxide slurry;
(2) 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;
(3) dropwise adding 30-40 parts of 5wt% aluminum sulfate solution into the titanium dioxide-silicate slurry within 1h, adjusting the pH to 7.0-7.5 after dropwise adding, and standing at normal temperature for 4-6h to obtain an alumina-coated titanium dioxide suspension;
(4) and 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 300-500 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 1000-2000r/min for 6-10h to obtain pretreated lignin;
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 of the carbon black is generally between 10 and 100nm, the smaller the carbon black is, the higher the carbon black content is, the larger the surface area of the carbon black is, the higher the tinting strength is, but the intermolecular force for quality inspection of carbon black aggregates is also enhanced, the dispersion of the carbon black is influenced, and as the carbon black is a nano material, the surface structure degree is very high, in the process of melt blending, the molecular chain of carrier resin can be wound on the surface of the carbon black to form physical crosslinking, so that the fluidity of the resin is reduced, the viscosity of the whole system is improved, and the processability is poor; 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 example of modified titanium dioxide the lithium silicate in the following preparation examples is selected from 4.85 modulus lithium silicate provided by jonan huifeng chemical limited; 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: (1) grinding and sieving calcium silicate to obtain calcium silicate powder with particle size of 1-5 μm; 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;
(2) 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;
(3) adding 1-3kg of silicate mixture into the titanium dioxide slurry, stirring at 2000r/min for 30min, and standing at 70-80 ℃ for 4-6h to obtain titanium dioxide-silicate slurry;
(4) dropwise adding 30kg of 5wt% aluminum sulfate solution into the titanium dioxide-silicate slurry within 1h, adjusting the pH to 7.0 after the dropwise adding is finished, and standing at normal temperature for 4h to obtain an alumina-coated titanium dioxide suspension;
(5) and standing the alumina-coated titanium dioxide suspension for 24h to obtain a precipitate, filtering to remove water, washing the precipitate with deionized water, and drying at 80 ℃ for 4h to obtain the modified titanium dioxide.
Preparation example 2 of modified titanium dioxide: (1) grinding and sieving calcium silicate to obtain calcium silicate powder with particle size of 1-5 μm; 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;
(2) 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 0.75kg 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;
(3) adding 2kg of silicate mixture into the titanium dioxide slurry, stirring at 2000r/min for 30min, and standing at 75 ℃ for 5h to obtain titanium dioxide-silicate slurry;
(4) 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;
(5) and standing the alumina-coated titanium dioxide suspension for 24h to obtain a precipitate, filtering to remove water, washing the precipitate with deionized water, and drying at 85 ℃ for 5h to obtain the modified titanium dioxide.
Preparation example 3 of modified titanium dioxide: (1) grinding and sieving calcium silicate to obtain calcium silicate powder with particle size of 1-5 μm; 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 4000r/min for 2h to obtain a silicate mixture;
(2) 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 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;
(3) adding 3kg of silicate mixture into the titanium dioxide slurry, stirring at 2000r/min for 30min, and standing at 80 ℃ for 6h to obtain titanium dioxide-silicate slurry;
(4) dropwise adding 40kg of 5wt% aluminum sulfate solution into the titanium dioxide-silicate slurry within 1h, adjusting the pH to 7.5 after the dropwise adding is finished, and standing at normal temperature for 6h to obtain an alumina-coated titanium dioxide suspension;
(5) and standing the alumina-coated titanium dioxide suspension for 24h to obtain a precipitate, filtering to remove water, washing the precipitate with deionized water, and drying at 90 ℃ for 6h to obtain the modified titanium dioxide.
Preparation example 4 of modified titanium dioxide: (1) 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;
(2) dropwise adding 30kg of 5wt% aluminum sulfate solution into the titanium dioxide slurry within 1h, adjusting the pH to 7.0 after the dropwise adding is finished, and standing at normal temperature for 4h to obtain an alumina-coated titanium dioxide suspension;
(3) and (3) standing the alumina-coated titanium dioxide suspension for 24 hours to obtain a precipitate, filtering to remove water, washing the precipitate with deionized water, and drying 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 90m 2 (ii)/g, oil absorption of 450mL/100g, tinting strength of 115%, pH 4; the lignin is selected from lignin available from Strand corporation; the polyvinylpyrrolidone is polyvinylpyrrolidone provided by Basff and is kollidon 30; the titanate coupling agent is selected from mono-alkoxy fatty acid titanate coupling agents provided by Shandong Moore chemical Co., ltd, and the model number of the coupling agent is TC-130.
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 supplied by blue mountain tun of xinjiang under the designation TH 801; 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 number of G1203, provided by Zuogao Gao plastification 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, the temperature of a sixth zone, the temperature of a machine of the double-screw extruder of 145 ℃, the temperature of a fifth zone and the temperature of a sixth zone, and the rotating speed of a screw of a PBAT premix;
s2, mixing PBAT premix, 55kg pigment and 1kg dispersant at the speed of 800r/min for 5min, then placing the mixed materials into a double-screw extruder, wherein the temperature of each zone of the double-screw extruder is 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; the dispersing agent is polyethylene wax.
Example 2: the biodegradable color master batch is prepared by the following method:
s1, uniformly mixing 4kg of polycaprolactone and 6kg of plasticizer at 55 ℃, placing the mixed polycaprolactone and plasticizer in 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 of the double-screw extruder being 130 ℃, 135 ℃, 150 ℃ and 135 ℃ respectively, and the temperature of a fifth zone, 135 ℃ and 135 ℃ respectively to obtain PBAT premix;
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 temperature of each zone of the double-screw extruder is 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; 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 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 to obtain a PBAT premix, wherein the temperature of each zone of the double-screw extruder is 130 ℃ in the first zone, 135 ℃ in the second zone, 145 ℃ in the third zone, 150 ℃ in the fourth zone, 145 ℃ in the fifth zone, 135 ℃ in the sixth zone, 135 ℃ in the head and 135 ℃ in the rotating speed of a screw;
s2, mixing PBAT premix, 65kg pigment and 3kg dispersing agent at the speed of 1200r/min for 5-10min, and then placing the mixed material in a double-screw extruder, wherein the temperatures of all zones of the double-screw extruder are respectively 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 rotating speed of a screw, 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; 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 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 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 pigment carbon black supplied by degussa 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 limited.
Example 14: this example differs from example 1 in that the pigment is E60 gardenia yellow supplied by Biochemical engineering, 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.
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.
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 is different from example 1 in that 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 embodiments 1-14 and the comparative examples 1-5, uniformly mixing, placing in a film blowing machine, setting the parameters of the film blowing machine as 140 ℃ in a first area of a material cylinder, 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 ℃ of a machine head, and 60r/min of screw speed, and carrying out film blowing on the PBAT resin 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/cm 3 Melt and meltThe melt index (190 ℃,2.16 kg) 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 resin is verified by observing whether the surface of the film has irregular color dot numbers; 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 performance: 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 10min; 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, test methods for 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 magnitude of the covering power can be represented by the optical density value, and the dispersion condition of the pigment can also be reflected, wherein the more uniform the pigment is dispersed, the finer the particles are, the higher the optical density value is, the stronger the covering power is, 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 I 0 When 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 I 1 Transmittance O =1/T = I 0 /I 1 Optical density D = lgO = lgI 0 /I 1 。
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
According to the data in table 1, the number of color dots of the films 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 application has good dispersibility in degradable plastics and has 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.
Combining with the examples, 6, 7 and 8, it can be seen that the number of color dots, the dispersion degree and the highest torque in examples 6-8 are significantly lower than those in example 1, and the tensile strength, the elongation at break, the hiding power and the tinting strength in examples 4 and 5 are significantly higher than those in example 1, which indicates that the aggregation phenomenon of the modified titanium dioxide prepared by the preparation example of the modified titanium dioxide of the present application in the polymer is significantly reduced, the dispersion of the modified titanium dioxide in the carrier resin can be significantly improved, the processing flowability of the white color masterbatch can be improved, and the dispersion of the color masterbatch in the plastic product and the tinting strength of the masterbatch on the plastic resin can be improved.
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.
It can be known by combining example 1, comparative example 1 and comparative example 2 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 dispersion 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, the dispersion degree, and the highest torque of comparative example 4 are significantly higher than those of example 6, and the tensile strength, the elongation at break, the hiding power, and the tinting strength of comparative example 4 are significantly lower than those of example 6, which indicates that when the titanium dioxide is modified, the surface of the titanium dioxide is treated in advance by adding the silicate mixture to improve the subsequent coating of alumina, so that the dispersion degree of the 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 specific embodiments are only for explaining the present application and are not limiting to the present application, and those skilled in the art can make modifications to the embodiments without inventive contribution as required after reading the present specification, but all the embodiments are protected by patent law within the scope of the claims of the present application.
Claims (3)
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 consists of microcrystalline cellulose, ethyl cellulose, tributyl citrate and castor oil in a weight ratio of (3-5);
the compatilizer is one of maleic anhydride grafted polyethylene and maleic anhydride grafted polypropylene;
the pigment is carbon black;
the carbon black is modified by the following method before use:
a. taking 100 parts of carbon black and 300-500 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 1000-2000r/min for 6-10h to obtain pretreated lignin;
c. adding the pretreated lignin into the oxidized carbon black, and grinding for 20-24h at the speed of 1000-2000r/min to obtain modified carbon black;
the preparation method of the biodegradable color master batch comprises the following steps:
s1, according to a proportion, taking polycaprolactone and a plasticizer, uniformly mixing at the temperature of 50-60 ℃, adding polybutylene terephthalate-adipate, heating to 130-150 ℃, and carrying out melting, extrusion and granulation to obtain a PBAT premix;
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.
2. The biodegradable color masterbatch according to claim 1, wherein the dispersant is one of polyethylene wax, distearamide, erucamide or a combination thereof.
3. Biodegradable color masterbatch according to claim 1, characterized in that the mixing speed of the PBAT premix, the pigment and the compatibilizer is 800-1200r/min and the mixing time is 5-10min.
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| 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 |
| CN115678214B (en) * | 2022-10-10 | 2023-12-19 | 万华化学（宁波）有限公司 | High-stiffness degradable transparent functional master batch as well as preparation method and application thereof |
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