CN114058161B - Black master batch capable of completely biodegrading plastic - Google Patents
Black master batch capable of completely biodegrading plastic Download PDFInfo
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- CN114058161B CN114058161B CN202111530629.3A CN202111530629A CN114058161B CN 114058161 B CN114058161 B CN 114058161B CN 202111530629 A CN202111530629 A CN 202111530629A CN 114058161 B CN114058161 B CN 114058161B
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- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
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Abstract
The invention provides a completely biodegradable black master batch, which takes poly (butylene terephthalate-adipate-co-terephthalate) (PBAT) resin as a main component, adds polyglycolic acid (PGA) for blending modification, and simultaneously adds epoxidized lignin as a dispersant and a compatilizer for improving the dispersibility of carbon black in a PBAT/PGA blending system, thereby realizing the uniform dispersion of all components and having good coloring performance and biodegradability. The organic solvent is added in the preparation process of the master batch to promote the dispersion of the carbon black, and the solvent is removed again before banburying and mixing, so that the dispersion effect of the carbon black is further improved, the process is simple, the cost is low, the method is suitable for large-scale industrial production, and the method has good economic benefit and wide market prospect.
Description
Technical Field
The invention relates to the technical field of plastic color master batches, in particular to a black color master batch capable of completely biodegrading plastic.
Background
The appearance of polymer plastics brings convenience for production and life and causes serious white pollution, and meanwhile, due to the continuous reduction of petroleum resources and the increase of the cost of the traditional plastic industry which takes petroleum as a raw material, the replacement of traditional plastics by biodegradable materials becomes a research and development hotspot.
At present, the biodegradable materials mainly comprise polylactic acid, polybutylene succinate, adipic acid-terephthalic acid-butylene succinate copolymer, polycaprolactone, polyhydroxyalkanoate), polyvinyl alcohol, poly-beta-hydroxybutyrate and the like. In order to endow the biodegradable material with new physical and chemical properties and expand the application range of the biodegradable material, the pigment or the filling powder material needs to be dispersed in the biodegradable material through a double-screw extruder and adding various dispersing aids, so that the process is complicated and the dispersing effect is general. The master batch is also called as color master batch and plastic master batch, is a plastic colorant prepared by well dispersing pigment or additive and thermoplastic resin with high proportion, and when the master batch and the biodegradable material are used for filling modification, the master batch and the biodegradable material are simply blended, so that the process is simple and convenient.
The poly (butylene terephthalate-adipate-co-terephthalate) (PBAT) is a novel biodegradable copolyester, takes terephthalic acid, adipic acid and butanediol as raw materials, is a biodegradable material polymerized by a direct esterification or ester exchange method, has the performances of PBA and PET, contains flexible fat chain segments, and ensures that a molecular chain has good flexibility; the molecular chain contains benzene ring, thus improving the thermal stability of the molecule and having wider application. However, PBAT has problems of poor crystallinity, low melt strength, easy occurrence of adhesion, high price, etc., which limits its application, and requires a certain modification of PBAT to achieve the effects of reducing cost and improving comprehensive properties.
Meanwhile, with the trend of individuation and differentiation of the PBAT product, the PBAT product is developed towards color diversification, and the requirement for coloring is increasingly increased. At present, when the PBAT is colored by using the color master batch, the common color master batch has poor fluidity, so that the dispersion uniformity of the color master batch in the PBAT is easily poor, the prepared product has unstable color, is easy to fade, and the color difference is difficult to control. In addition, the degradation performance of common color master batches is not good enough, and the degradation performance of PBAT products can be influenced by coloring the common color master batches. Therefore, it is necessary to develop a black master batch for completely biodegradable plastics.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a completely biodegradable black master batch, which takes polybutylene terephthalate-adipate (PBAT) resin as a main material, polyglycolic acid (PGA) is added for blending modification, and meanwhile, in order to improve the dispersibility of carbon black in a PBAT/PGA blending system, epoxidized lignin is added as a dispersing agent and a compatilizer, so that the uniform dispersion of all components is realized, and the completely biodegradable black master batch is prepared and has good coloring performance and biodegradability.
In order to achieve the purpose, the invention adopts the following technical scheme that the completely biodegradable black master batch comprises the following raw materials in parts by weight:
70-90 parts of polybutylene terephthalate-adipate (PBAT), 30-50 parts of polyglycolic acid (PGA), 60-80 parts of carbon black, 10-20 parts of epoxidized lignin, 3-5 parts of cellulose nanocrystals, 1-3 parts of a plasticizer, 3-5 parts of a coupling agent and 0.5-2 parts of an antioxidant;
the epoxidized lignin is prepared by the following preparation method, which comprises the following steps:
(1) adding 20 wt% sodium hydroxide solution into lignin, dissolving, filtering to remove insoluble substances, adjusting pH of the filtrate to 2-3 with hydrochloric acid solution, and filtering; fully washing the filter cake to be neutral by using distilled water, and drying for later use;
(2) weighing 100 parts of lignin treated in the step (1), adding N, N-dimethylformamide with the weight 1-3 times of that of the lignin, heating to 70-80 ℃, fully dissolving, adding stannous isooctanoate with the weight 0.5-1% of that of the lignin, and continuously introducing nitrogen;
(3) weighing a mixed monomer according to the molar ratio of caprolactone to lactide of 3-5:1, wherein the use amount of the mixed monomer is 8-10 times of that of lignin, adding the mixed monomer into the reaction system obtained in the step (2), heating to 150 ℃ and 170 ℃, and reacting for 20-24 h; after the reaction is finished, drying to obtain modified lignin;
(4) uniformly mixing the modified lignin prepared in the step (3) with epichlorohydrin according to a weight ratio of 1:6-8, heating to 60-70 ℃, adding 20 Wt% of sodium hydroxide solution, wherein the ratio of the amount of the sodium hydroxide solution to the modified lignin is 5-8ml:1g, reacting for 5-6h, and removing unreacted epichlorohydrin through reduced pressure distillation to obtain epoxidized lignin.
Preferably, the weight average molecular weight of the polybutylene terephthalate-adipate (PBAT) is 80000-150000g/mol, and the melt index is 10-15g/10min (190 ℃, 2.16 kg);
the weight-average molecular weight of the polyglycolic acid (PGA) is 50000-80000g/mol, and the melt index is 5-10g/10min (230 ℃, 2.16 kg);
the particle size of the carbon black is 100-200nm, and the carbon black is preferably modified by the following method, which comprises the following steps:
(1) weighing 100 parts of carbon black according to parts by weight, adding concentrated nitric acid which is 3-5 times of the weight of the carbon black, heating to 60 +/-5 ℃, reacting for 6-8h, filtering, washing filter residues to be neutral by water, and drying for later use;
(2) adding 100 parts by weight of the carbon black obtained in the step (1) into dimethylbenzene of which the weight is 3-5 times that of the carbon black, ultrasonically dispersing for 10-20min, adding 50-70 parts by weight of hexamethylene diisocyanate, reacting for 20-40min under an ice bath condition, heating to 120 +/-10 ℃, continuing to react for 40-60min, and distilling under reduced pressure to remove unreacted hexamethylene diisocyanate and dimethylbenzene to obtain isocyanate modified carbon black;
(3) and (3) adding 100 parts of isocyanate modified carbon black obtained in the step (2) into xylene of which the weight is 3-5 times that of the isocyanate modified carbon black, performing ultrasonic dispersion for 10-20min, adding 50-70 parts of polyether glycol, adding 0.03-0.05 part of dibutyl tin dilaurate, reacting for 20-40min under an ice bath condition, heating to 120 +/-10 ℃, continuing to react for 40-60min, filtering after the reaction is finished, and cleaning and drying filter residues with water to obtain the modified carbon black.
Preferably, the number average molecular weight of the polyether glycol is 200-300 g/mol.
The diameter of the fiber nanocrystal is 20-30nm, and the length of the fiber nanocrystal is 500-700 nm;
the plasticizer is selected from at least one of polyethylene glycol, polypropylene glycol and tributyl citrate;
the coupling agent is silane coupling agent and is selected from at least one of gamma-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane and epoxy butyl trimethoxysilane;
the antioxidant is selected from at least one of phenol antioxidant, phosphite antioxidant and sulfur-containing ester antioxidant; preferably, at least one selected from the group consisting of 2, 6-di-t-butylphenol, 2, 6-di-t-butyl-4-ethylphenol, 4-hydroxymethyl-2, 6-di-t-butylphenol, 2, 6-di-t-butyl-4-n-butylphenol, triphenyl phosphite, tris (nonylphenyl) phosphite, triisooctyl phosphite, triisodecyl phosphite, diisodecyl phosphite, dilauryl thiodipropionate, and distearyl thiodipropionate.
The invention also aims to provide a preparation method of the completely biodegradable black master batch, which comprises the following steps:
(1) uniformly mixing carbon black, cellulose nanocrystal and a coupling agent, and then carrying out ball milling for 10-20min at 0-5 ℃; then adding N, N-dimethylformamide and epoxidized lignin which are 5-10 times of the weight of the carbon black, and then carrying out ultrasonic dispersion for 20-40 min; then adding polybutylene terephthalate-adipate (PBAT), polyglycolic acid (PGA), a plasticizer and an antioxidant, uniformly stirring, heating to 160 +/-5 ℃, continuously stirring to remove N, N-dimethylformamide, then transferring to an internal mixer for mixing for 40-60min, and controlling the internal mixing temperature at 230-;
(2) and (2) transferring the banburying product obtained in the step (1) to a double-screw extruder for extrusion granulation to obtain the completely biodegradable black master batch.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention provides a completely biodegradable black master batch, which takes PBAT resin as a main component, is added with polyglycolic acid (PGA) for blending modification, and is added with epoxidized lignin as a dispersant and a compatilizer for improving the dispersibility of carbon black in a PBAT/PGA blending system, thereby realizing the uniform dispersion of all components, and the completely biodegradable black master batch prepared has good coloring performance and biodegradability.
(2) The modified lignin is used as a dispersing agent and a compatilizer, the polyester chain segment with a structure similar to that of PBAT and PGA and the epoxy group capable of reacting with the PBAT and the PGA are grafted on the lignin, so that the compatibility of the PBAT and the PGA is provided, and the dispersibility of the carbon black in a PBAT/PGA blending system is improved.
(3) According to the invention, the organic solvent is added in the preparation process of the master batch to promote the dispersion of the carbon black, and the solvent is removed again before banburying and mixing, so that the dispersion effect of the carbon black is further improved, the black master batch with high blackness and gloss is prepared, the process is simple, the cost is low, the method is suitable for large-scale industrial production, and the method has good economic benefits and wide market prospects.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the present invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the present invention and is not intended to limit the scope of the claims which follow. All starting materials for the present invention, without particular limitation as to their source, may be purchased commercially or prepared according to conventional methods well known to those skilled in the art.
1. Preparation example
1.1 preparation of epoxidized Lignin I
The epoxidized lignin I is prepared by the following preparation method, which comprises the following steps:
(1) adding 20 wt% of sodium hydroxide solution into lignin, dissolving, filtering to remove insoluble substances, adjusting the pH value of the filtrate to 2 by using hydrochloric acid solution, and filtering; fully washing the filter cake to be neutral by using distilled water, and drying for later use;
(2) weighing 100 parts of lignin treated in the step (1), adding N, N-dimethylformamide 2 times the weight of the lignin, heating to 80 ℃ for full dissolution, adding stannous isooctanoate 0.5% of the weight of the lignin, and continuously introducing nitrogen;
(3) weighing a mixed monomer according to the molar ratio of caprolactone to lactide of 5:1, wherein the use amount of the mixed monomer is 10 times of the weight of lignin, adding the mixed monomer into the reaction system obtained in the step (2), heating to 170 ℃, and reacting for 20 hours; after the reaction is finished, drying to obtain modified lignin;
(4) and (3) uniformly mixing the modified lignin prepared in the step (3) with epichlorohydrin according to a weight ratio of 1:6, heating to 70 ℃, adding 20 Wt% of sodium hydroxide solution, wherein the ratio of the amount of the sodium hydroxide solution to the modified lignin is 8ml:1g, reacting for 6 hours, and then carrying out reduced pressure distillation to remove unreacted epichlorohydrin to obtain epoxidized lignin I.
1.2 preparation of epoxidized Lignin II
The epoxidized lignin II is prepared by the following preparation method, which comprises the following steps:
(1) adding 20 wt% sodium hydroxide solution into lignin, dissolving, filtering to remove insoluble substances, adjusting pH of the filtrate to 3 with hydrochloric acid solution, and filtering; fully washing the filter cake to be neutral by using distilled water, and drying for later use;
(2) weighing 100 parts of lignin treated in the step (1), adding N, N-dimethylformamide with the weight 3 times that of the lignin, heating to 80 ℃ for fully dissolving, adding stannous isooctanoate with the weight 0.8% of that of the lignin, and continuously introducing nitrogen;
(3) weighing a mixed monomer according to the mole ratio of caprolactone to lactide of 4:1, wherein the using amount of the mixed monomer is 9 times of that of lignin, adding the mixed monomer into the reaction system obtained in the step (2), heating to 160 ℃, and reacting for 22 hours; after the reaction is finished, drying to obtain modified lignin;
(4) and (4) uniformly mixing the modified lignin prepared in the step (3) with epichlorohydrin according to a weight ratio of 1:7, heating to 65 ℃, adding 20 Wt% of sodium hydroxide solution, reacting for 6 hours, and distilling under reduced pressure to remove unreacted epichlorohydrin to obtain epoxidized lignin II, wherein the ratio of the sodium hydroxide solution to the modified lignin is 6ml:1 g.
1.3 preparation of epoxidized Lignin III
The epoxidized lignin III is prepared by the following preparation method, which comprises the following steps:
(1) adding 20 wt% of sodium hydroxide solution into lignin, dissolving, filtering to remove insoluble substances, adjusting the pH value of the filtrate to 2 by using hydrochloric acid solution, and filtering; fully washing the filter cake to be neutral by using distilled water, and drying for later use;
(2) weighing 100 parts of lignin treated in the step (1), adding N, N-dimethylformamide with the weight 3 times that of the lignin, heating to 70 ℃ for full dissolution, adding stannous isooctanoate with the weight 1% of that of the lignin, and continuously introducing nitrogen;
(3) weighing a mixed monomer according to the molar ratio of caprolactone to lactide of 3:1, wherein the use amount of the mixed monomer is 8 times of the weight of lignin, adding the mixed monomer into the reaction system obtained in the step (2), heating to 170 ℃, and reacting for 24 hours; after the reaction is finished, drying to obtain modified lignin;
(4) and (4) uniformly mixing the modified lignin prepared in the step (3) with epichlorohydrin according to a weight ratio of 1:8, heating to 70 ℃, adding 20 Wt% of sodium hydroxide solution, wherein the ratio of the amount of the sodium hydroxide solution to the modified lignin is 8ml:1g, reacting for 5h, and removing unreacted epichlorohydrin by reduced pressure distillation to obtain epoxidized lignin III.
1.4 modification treatment of carbon Black
The particle size of the carbon black is 100-200nm, and the carbon black is modified by the following method, which comprises the following steps:
(1) weighing 100 parts of carbon black according to parts by weight, adding concentrated nitric acid which is 5 times of the weight of the carbon black, heating to 60 +/-5 ℃, reacting for 8 hours, filtering, washing filter residues to be neutral by water, and drying for later use;
(2) adding 100 parts by weight of the carbon black obtained in the step (1) into dimethylbenzene of which the weight is 5 times that of the carbon black, ultrasonically dispersing for 20min, adding 70 parts of hexamethylene diisocyanate, reacting for 40min under an ice bath condition, heating to 120 +/-10 ℃, continuing to react for 60min, and distilling under reduced pressure to remove unreacted hexamethylene diisocyanate and dimethylbenzene to obtain isocyanate modified carbon black;
(3) and (3) adding 100 parts of isocyanate modified carbon black obtained in the step (2) into dimethylbenzene with the weight being 4 times that of the isocyanate modified carbon black, performing ultrasonic dispersion for 20min, adding 70 parts of polyether glycol, adding 0.03 part of dibutyl tin dilaurate, reacting for 40min under an ice bath condition, heating to 120 +/-10 ℃, continuing to react for 60min, filtering after the reaction is finished, and cleaning and drying filter residues with water to obtain modified carbon black I, wherein the number average molecular weight of the polyether glycol is 210 g/mol.
2. Examples of the embodiments
2.1 example 1
A completely biodegradable black master batch comprises the following raw materials in parts by weight: 90 parts of polybutylene terephthalate-adipate (PBAT), 40 parts of polyglycolic acid (PGA), 70 parts of carbon black, 15 parts of epoxidized lignin I, 4 parts of cellulose nanocrystals, 2 parts of plasticizer, 5 parts of coupling agent and 0.5 part of antioxidant;
the weight average molecular weight of the polybutylene terephthalate-adipate (PBAT) is 90000g/mol, and the melt index is 15g/10min (190 ℃, 2.16 kg); the polyglycolic acid (PGA) has a weight-average molecular weight of 50000g/mol and a melt index of 10g/10min (230 ℃ C., 2.16 kg); the particle size of the carbon black is 200nm, the diameter of the fiber nanocrystal is 30nm, and the length of the fiber nanocrystal is 700 nm; the plasticizer is polyethylene glycol; the coupling agent is gamma-aminopropyl triethoxysilane; the antioxidant is 2, 6-di-tert-butylphenol.
The preparation method of the completely biodegradable black master batch comprises the following steps:
(1) uniformly mixing carbon black, cellulose nanocrystal and a coupling agent, and then carrying out ball milling for 20min at 0 ℃; then adding N, N-dimethylformamide and epoxidized lignin I which are 10 times of the weight of the carbon black, and performing ultrasonic dispersion for 30 min; then adding polybutylene terephthalate-adipate (PBAT), polyglycolic acid (PGA), a plasticizer and an antioxidant, uniformly stirring, heating to 160 +/-5 ℃, continuously stirring to remove N, N-dimethylformamide, then transferring to an internal mixer for mixing for 60min, and controlling the mixing temperature at 250 ℃;
(2) and (2) transferring the banburying product obtained in the step (1) to a double-screw extruder for extrusion granulation to obtain the completely biodegradable black master batch.
2.2 example 2
A completely biodegradable black master batch comprises the following raw materials in parts by weight: 75 parts of polybutylene terephthalate-adipate (PBAT), 35 parts of polyglycolic acid (PGA), 60 parts of carbon black, 10 parts of epoxidized lignin II, 3 parts of cellulose nanocrystals, 1 part of plasticizer, 4 parts of coupling agent and 1 part of antioxidant;
the weight average molecular weight of the polybutylene terephthalate-adipate (PBAT) is 120000g/mol, and the melt index is 13g/10min (190 ℃, 2.16 kg); the weight-average molecular weight of the polyglycolic acid (PGA) is 70000g/mol, and the melt index is 8g/10min (230 ℃, 2.16 kg); the particle size of the carbon black is 150 nm; the diameter of the fiber nanocrystal is 25nm, and the length of the fiber nanocrystal is 600 nm; the plasticizer is tributyl citrate; the coupling agent is gamma-glycidoxypropyltrimethoxysilane; the antioxidant is dilauryl thiodipropionate.
The preparation method of the completely biodegradable black master batch comprises the following steps:
(1) uniformly mixing carbon black, cellulose nanocrystal and a coupling agent, and then carrying out ball milling for 15min at 5 ℃; then adding N, N-dimethylformamide and epoxidized lignin II which are 6 times of the weight of the carbon black, and performing ultrasonic dispersion for 40 min; then adding polybutylene terephthalate-adipate (PBAT), polyglycolic acid (PGA), a plasticizer and an antioxidant, uniformly stirring, heating to 160 +/-5 ℃, continuously stirring to remove N, N-dimethylformamide, then transferring to an internal mixer for mixing for 50min, and controlling the internal mixing temperature at 240 ℃;
(2) and (2) transferring the banburying product obtained in the step (1) to a double-screw extruder for extrusion granulation to obtain the completely biodegradable black master batch.
2.3 example 3
A completely biodegradable black master batch comprises the following raw materials in parts by weight: 80 parts of polybutylene terephthalate-adipate (PBAT), 30 parts of polyglycolic acid (PGA), 80 parts of carbon black, 20 parts of epoxidized lignin III, 5 parts of cellulose nanocrystals, 3 parts of a plasticizer, 3 parts of a coupling agent and 2 parts of an antioxidant;
the weight average molecular weight of the polybutylene terephthalate-adipate (PBAT) is 140000g/mol, and the melt index is 13g/10min (190 ℃, 2.16 kg); the polyglycolic acid (PGA) has a weight average molecular weight of 80000g/mol and a melt index of 7g/10min (230 ℃, 2.16 kg); the particle size of the carbon black is 180 nm; the diameter of the fiber nanocrystal is 30nm, and the length of the fiber nanocrystal is 700 nm; the plasticizer is polypropylene glycol; the coupling agent is epoxy butyl trimethoxy silane; the antioxidant is 4-hydroxymethyl-2, 6-di-tert-butylphenol.
The preparation method of the completely biodegradable black master batch comprises the following steps:
(1) uniformly mixing carbon black, cellulose nanocrystal and a coupling agent, and then carrying out ball milling for 20min at 0 ℃; then adding N, N-dimethylformamide and epoxidized lignin III which are 8 times of the weight of the carbon black, and performing ultrasonic dispersion for 40 min; then adding polybutylene terephthalate-adipate (PBAT), polyglycolic acid (PGA), a plasticizer and an antioxidant, uniformly stirring, heating to 160 +/-5 ℃, continuously stirring to remove N, N-dimethylformamide, then transferring to an internal mixer for mixing for 50min, and controlling the internal mixing temperature at 250 ℃;
(2) and (2) transferring the banburying product obtained in the step (1) to a double-screw extruder for extrusion granulation to obtain the completely biodegradable black master batch.
2.4 example 4
A completely biodegradable black master batch comprises the following raw materials in parts by weight: 70 parts of polybutylene terephthalate-adipate (PBAT), 50 parts of polyglycolic acid (PGA), 70 parts of carbon black, 10-20 parts of epoxidized lignin II, 4 parts of cellulose nanocrystals, 2 parts of a plasticizer, 4 parts of a coupling agent and 0.5 part of an antioxidant;
the weight average molecular weight of the polybutylene terephthalate-adipate (PBAT) is 100000g/mol, and the melt index is 14g/10min (190 ℃, 2.16 kg); the polyglycolic acid (PGA) has a weight average molecular weight of 60000g/mol and a melt index of 8g/10min (230 ℃ C., 2.16 kg); the particle size of the carbon black is 200 nm; the diameter of the fiber nanocrystal is 25nm, and the length of the fiber nanocrystal is 650 nm; the plasticizer is polyethylene glycol; the coupling agent is gamma-aminopropyltriethoxysilane; the antioxidant is 2, 6-di-tert-butyl-4-ethylphenol.
The preparation method of the completely biodegradable black master batch comprises the following steps:
(1) uniformly mixing carbon black, cellulose nanocrystal and a coupling agent, and then carrying out ball milling for 15min at 3 ℃; then adding N, N-dimethylformamide and epoxidized lignin which are 7 times of the weight of the carbon black, and performing ultrasonic dispersion for 30 min; then adding polybutylene terephthalate-adipate (PBAT), polyglycolic acid (PGA), a plasticizer and an antioxidant, uniformly stirring, heating to 160 +/-5 ℃, continuously stirring to remove N, N-dimethylformamide, then transferring to an internal mixer for mixing for 40min, and controlling the internal mixing temperature at 230 ℃;
(2) and (2) transferring the banburying product obtained in the step (1) to a double-screw extruder for extrusion granulation to obtain the completely biodegradable black master batch.
2.5 example 5
The modified carbon black I was selected to replace carbon black, and the remaining composition and process were completely the same as in example 4.
3. Comparative example
3.1 comparative example 1
The epoxidized lignin II is replaced by the modified lignin, and the rest components and the process are completely consistent with the example 4, wherein the preparation method of the modified lignin comprises the following steps:
(1) adding 20 wt% sodium hydroxide solution into lignin, dissolving, filtering to remove insoluble substances, adjusting pH of the filtrate to 3 with hydrochloric acid solution, and filtering; fully washing the filter cake to be neutral by using distilled water, and drying for later use;
(2) weighing 100 parts of lignin treated in the step (1), adding N, N-dimethylformamide with the weight 3 times that of the lignin, heating to 80 ℃ for fully dissolving, adding stannous isooctanoate with the weight 0.8% of that of the lignin, and continuously introducing nitrogen;
(3) weighing a mixed monomer according to the molar ratio of caprolactone to lactide of 4:1, wherein the using amount of the mixed monomer is 9 times of that of lignin, adding the mixed monomer into the reaction system obtained in the step (2), heating to 160 ℃, and reacting for 22 hours; and after the reaction is finished, drying to obtain the modified lignin.
3.2 comparative example 2
The epoxidized lignin II was replaced by lignin, the remaining composition and process being completely in accordance with example 4, wherein the lignin was treated by the following method comprising the steps of: adding 20 wt% of sodium hydroxide solution into lignin, dissolving, filtering to remove insoluble substances, adjusting the pH value of the filtrate to 3 by using hydrochloric acid solution, and filtering; and fully washing the filter cake to be neutral by using distilled water, and drying for later use.
3.3 comparative example 3
The cellulose nanocrystals were not contained, and the remaining composition and process were completely identical to those of example 4.
4. Performance testing
4.1 surface gloss measurement
The completely biodegradable black master batches prepared in examples 1 to 5 and comparative examples 1 to 3 were weighed, added to a PBAT resin (weight average molecular weight of 150000, melt index (190 ℃, 2.16Kg) of 15g/10min) in an amount of 1%, and molded at 250 ℃ to prepare a square plate having a length, width and thickness of 100mm by 2mm, the square plate having a bright surface, and the composition was measured for surface gloss by a surface gloss meter to read a value of 60 °.
4.2 Dispersion test
The completely biodegradable black master batches prepared in examples 1 to 5 and comparative examples 1 to 3 were weighed, added to a PBAT resin (weight average molecular weight 150000, melt index (190 ℃, 2.16Kg) 15g/10min) in an amount of 1%, blown at 250 ℃ to a film thickness of 80 μm, and tested for the number of color points (particle size > 10 μm).
4.3 Torque rheology
Taking 50g of completely biodegradable black master batch, heating to 250 ℃, controlling the rotating speed to be 30r/min and the time to be 10min, and testing the highest torque (N.m) by adopting a torque rheometer.
4.4 Water vapor Barrier test
The completely biodegradable black master batches prepared in examples 1 to 5 and comparative examples 1 to 3 were weighed, added to a PBAT resin (weight average molecular weight 150000, melt index (190 ℃, 2.16Kg) 15g/10min) in an amount of 1%, and a film having a thickness of 80 μm was blown at 250 ℃ to test the water vapor transmission coefficient (g.cm/cm 2.s.Pa).
Through tests, the test results of the completely biodegradable black master batches prepared in examples 1-5 and comparative examples 1-3 are shown in table 1.
TABLE 1
| Number of | Gloss/60 ° | Number of color dots/m 2 | Maximum torque/N.m | Water vapor transmission coefficient/g.cm/cm 2.s.Pa |
| Example 1 | 82 | 8 | 18.5 | 0.85×10 -12 |
| Example 2 | 83 | 7 | 17.8 | 0.92×10 -12 |
| Example 3 | 80 | 8 | 19.2 | 0.89×10 -12 |
| Example 4 | 81 | 9 | 19.3 | 0.95×10 -12 |
| Example 5 | 85 | 5 | 18.2 | 0.82×10 -12 |
| Comparative example 1 | 75 | 15 | 22.3 | 1.5×10 -12 |
| Comparative example 2 | 70 | 24 | 25.1 | 1.8×10 -12 |
| Comparative example 3 | 79 | 12 | 20.5 | 1.05×10 -12 |
From the test data in table 1, it can be found that the invention provides a completely biodegradable black master batch, which has good surface quality, better compatibility of each component, more uniform dispersion of carbon black, and higher processability and water vapor barrier property.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (11)
1. A black master batch capable of being completely biodegraded is characterized in that: the feed comprises the following raw materials in parts by weight:
70-90 parts of polybutylene terephthalate-adipate (PBAT), 30-50 parts of polyglycolic acid (PGA), 60-80 parts of carbon black, 10-20 parts of epoxidized lignin, 3-5 parts of cellulose nanocrystals, 1-3 parts of a plasticizer, 3-5 parts of a coupling agent and 0.5-2 parts of an antioxidant;
the epoxidized lignin is prepared by the following preparation method, and comprises the following steps:
(1) adding 20 wt% of sodium hydroxide solution into lignin, dissolving, filtering to remove insoluble substances, adjusting pH of the filtrate to 2-3 with hydrochloric acid solution, and filtering; fully washing the filter cake to be neutral by using distilled water, and drying for later use;
(2) weighing 100 parts of lignin treated in the step (1), adding N, N-dimethylformamide with the weight 1-3 times that of the lignin, heating to 70-80 ℃ for fully dissolving, adding stannous isooctanoate with the weight 0.5-1% of the lignin, and continuously introducing nitrogen;
(3) weighing a mixed monomer according to the molar ratio of caprolactone to lactide of 3-5:1, wherein the use amount of the mixed monomer is 8-10 times of that of lignin, adding the mixed monomer into the reaction system obtained in the step (2), heating to 150 ℃ and 170 ℃, and reacting for 20-24 h; after the reaction is finished, drying to obtain modified lignin;
(4) and (3) uniformly mixing the modified lignin prepared in the step (3) with epichlorohydrin according to a weight ratio of 1:6-8, heating to 60-70 ℃, adding 20w t% sodium hydroxide solution, reacting for 5-6h, and distilling under reduced pressure to remove unreacted epichlorohydrin to obtain the epoxidized lignin, wherein the ratio of the sodium hydroxide solution to the modified lignin is 5-8ml:1 g.
2. A fully biodegradable black masterbatch according to claim 1, wherein: the weight-average molecular weight of the polybutylene terephthalate-adipate (PBAT) is 80000-150000g/mol, the melt index is 10-15g/10min, and the test conditions are 190 ℃ and 2.16 kg.
3. A fully biodegradable black masterbatch according to claim 1, wherein: the weight-average molecular weight of the polyglycolic acid (PGA) is 50000-80000g/mol, the melt index is 5-10g/10min, and the test conditions are 230 ℃ and 2.16 kg.
4. A fully biodegradable black masterbatch according to claim 1, wherein: the particle size of the carbon black is 100-200 nm.
5. A fully biodegradable black masterbatch according to claim 4, wherein: the carbon black is modified by the following method, comprising the following steps:
(1) weighing 100 parts of carbon black according to parts by weight, adding concentrated nitric acid which is 3-5 times of the weight of the carbon black, heating to 60 +/-5 ℃, reacting for 6-8h, filtering, washing filter residues to be neutral by water, and drying for later use;
(2) adding 100 parts by weight of the carbon black obtained in the step (1) into dimethylbenzene of which the weight is 3-5 times that of the carbon black, ultrasonically dispersing for 10-20min, adding 50-70 parts by weight of hexamethylene diisocyanate, reacting for 20-40min under an ice bath condition, heating to 120 +/-10 ℃, continuing to react for 40-60min, and distilling under reduced pressure to remove unreacted hexamethylene diisocyanate and dimethylbenzene to obtain isocyanate modified carbon black;
(3) and (3) adding 100 parts of isocyanate modified carbon black obtained in the step (2) into xylene with the weight 3-5 times of that of the isocyanate modified carbon black, performing ultrasonic dispersion for 10-20min, adding 50-70 parts of polyether glycol, adding 0.03-0.05 part of dibutyl tin dilaurate, reacting for 20-40min under an ice bath condition, heating to 120 +/-10 ℃, continuing to react for 40-60min, filtering after the reaction is finished, and washing and drying filter residues with water to obtain the modified carbon black.
6. A fully biodegradable black masterbatch according to claim 5, wherein: the number average molecular weight of the polyether diol is 200-300 g/mol.
7. A fully biodegradable black masterbatch according to claim 1, wherein: the diameter of the fiber nanocrystal is 20-30nm, and the length of the fiber nanocrystal is 500-700 nm.
8. A fully biodegradable black masterbatch according to claim 1, wherein: the plasticizer is selected from at least one of polyethylene glycol, polypropylene glycol and tributyl citrate; the coupling agent is silane coupling agent and is selected from at least one of gamma-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane and epoxy butyl trimethoxysilane.
9. A fully biodegradable black masterbatch according to claim 1, characterized in that: the antioxidant is at least one selected from phenolic antioxidants, phosphite antioxidants and sulfur-containing ester antioxidants.
10. A fully biodegradable black masterbatch according to claim 9, wherein: the antioxidant is selected from at least one of 2, 6-di-tert-butylphenol, 2, 6-di-tert-butyl-4-ethylphenol, 4-hydroxymethyl-2, 6-di-tert-butylphenol, 2, 6-di-tert-butyl-4-n-butylphenol, triphenyl phosphite, tris (nonylphenyl) phosphite, triisooctyl phosphite, triisodecyl phosphite, diisodecyl phosphite, dilauryl thiodipropionate and distearyl thiodipropionate.
11. A process for the preparation of a fully biodegradable black masterbatch according to any of claims 1-10, wherein: the method comprises the following steps:
(1) uniformly mixing carbon black, cellulose nanocrystal and a coupling agent, and then carrying out ball milling for 10-20min at 0-5 ℃; then adding N, N-dimethylformamide and epoxidized lignin which are 5-10 times of the weight of the carbon black, and then carrying out ultrasonic dispersion for 20-40 min; then adding polybutylene terephthalate-adipate (PBAT), polyglycolic acid (PGA), plasticizer and antioxidant, stirring uniformly, heating to 160 +/-5 ℃, continuously stirring to remove N, N-dimethylformamide, then transferring to an internal mixer for mixing for 40-60min, and controlling the mixing temperature at 230-;
(2) and (2) transferring the banburying product obtained in the step (1) to a double-screw extruder for extrusion granulation to obtain the completely biodegradable black master batch.
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