CN114940836A - Preparation method of self-dispersed nano biomass charcoal and high-concentration polyester master batch - Google Patents

Preparation method of self-dispersed nano biomass charcoal and high-concentration polyester master batch Download PDF

Info

Publication number
CN114940836A
CN114940836A CN202210590412.XA CN202210590412A CN114940836A CN 114940836 A CN114940836 A CN 114940836A CN 202210590412 A CN202210590412 A CN 202210590412A CN 114940836 A CN114940836 A CN 114940836A
Authority
CN
China
Prior art keywords
biomass charcoal
self
nano
temperature
polyester
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202210590412.XA
Other languages
Chinese (zh)
Other versions
CN114940836B (en
Inventor
陈向玲
王华平
吉鹏
王朝生
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Donghua University
Original Assignee
Donghua University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Donghua University filed Critical Donghua University
Priority to CN202210590412.XA priority Critical patent/CN114940836B/en
Publication of CN114940836A publication Critical patent/CN114940836A/en
Application granted granted Critical
Publication of CN114940836B publication Critical patent/CN114940836B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/44—Carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • 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
    • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/006—Combinations of treatments provided for in groups C09C3/04 - C09C3/12
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/04—Physical treatment, e.g. grinding, treatment with ultrasonic vibrations
    • C09C3/041—Grinding
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Nanotechnology (AREA)
  • Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Composite Materials (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biophysics (AREA)
  • Optics & Photonics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Manufacturing & Machinery (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

The invention relates to a preparation method of self-dispersing nano biomass charcoal and high-concentration polyester master batch, which comprises the steps of mixing a nano biomass charcoal material with an aqueous solution of bis (dioctyloxy pyrophosphate) ethylene titanate or an aqueous solution of a chelate of bis (dioctyloxy pyrophosphate) ethylene titanate and triethanolamine, and then carrying out hydrothermal activation (the temperature of the hydrothermal activation is 150-250 ℃) to prepare the nano biomass charcoal with self-dispersing effect; and injecting the nano biomass charcoal with the self-dispersion effect, polyester chips and an antioxidant into a double-screw extruder for blending granulation to prepare the high-concentration polyester master batch with the biomass charcoal content of 20-35 wt%. The biomass charcoal material with developed pore structure, specific surface area and excellent dispersibility is prepared by integrating carbonization, steam activation and dispersion; the prepared high-concentration biomass charcoal polyester master batch has the advantages of uniform dispersion of biomass charcoal, good master batch fluidity, good compatibility with polyester, good application prospect and good market value.

Description

Preparation method of self-dispersed nano biomass charcoal and high-concentration polyester master batch
Technical Field
The invention belongs to the technical field of biochar preparation and polyester preparation, and relates to a preparation method of self-dispersed nano biomass charcoal and high-concentration polyester master batch.
Background
China is a big agricultural country, the yield of wastes from agriculture and forestry is high, only the agricultural straw production amount in China is about 8-10 hundred million tons, and most of China adopts incineration treatment, so that not only is the environmental pollution caused, but also the resources are greatly wasted, and the resource utilization of agricultural wastes is urgent. The pyrolysis is to convert the biomass raw material into other products for utilization in a heating decomposition mode, is simple to implement, is beneficial to large-scale treatment of the biomass raw material, and is one of effective methods for solving the problems of the agriculture and forestry waste biomass raw material. The biomass charcoal material has wide raw material sources, diversified biomass materials including bamboo, corn straw, rice hull, coconut shell, hickory nut, Chinese torreya shell and the like are used for preparing microporous carbon, and the variety of the charcoal materials is very wide. The domestic patents include a preparation method of carbon-rich magnetic biochar (CN113634232), a preparation method of high-yield biochar (CN104371748), a preparation method of magnetic torreya grandis husk activated carbon (CN 10669822), a removal method of coffee residue biochar and urea in water (CN113526648) and the like all describe preparation methods of biomass carbon materials, but most of the patents adopt an activation method, and the prepared biomass is mainly applied to the fields of adsorption and environment and is relatively limited in application field. In recent years, with the rise of the biochar industry, researchers are gradually applying biochar to the field of polyester chemical fiber textile. The application of biomass charcoal in textile has basically three ways: (1) direct addition suitable for solution spinning systems: in the spinning process, the nano-scale biomass carbon powder is directly added into a spinning solution, and the functional fiber is prepared by wet spinning. The method is generally used for preparing functional viscose fiber and cellulose fiber. (2) A subsequent finishing coating method: after being mixed with functional additives, the biomass carbon powder is directly coated on the surface of the fabric, and the textile prepared by the method has poor function durability, and the function is continuously attenuated along with the increase of washing times. (3) Master batch addition suitable for melt spinning systems: grinding biomass charcoal into nano-scale powder, adding a dispersing agent, melt blending with polyester, polyamide and the like to prepare bamboo charcoal master batches, and then melt blending spinning or composite spinning with polyester and polyamide chips to prepare functional polyester and polyamide fibers. For example, in patent application CN103014907A, bamboo charcoal particles are surface-treated with silicon, then mixed with manganese phenate under stirring, and then mixed with polyester chips to prepare polyester masterbatch, and blended and spun to prepare functional polyester fiber. The application published patent CN101857977A discloses a preparation method of tea carbon fiber, which is to simply blend nano-scale tea carbon powder, resin, auxiliary agent, colorant and adhesive directly to prepare master batch, and then blend and spin the master batch and slices to prepare anion fiber. Patent CN103820879 describes a hydrophilic polyester fiber containing coffee carbon and a preparation method thereof, wherein nano-scale silicon dioxide powder is attached to the surface pores of the nano-scale coffee carbon powder to prepare composite powder, and then the composite powder is prepared into master batch and slices to carry out blended spinning and alkali washing to prepare the functional polyester fiber. In patent CN102828274 and patent CN10382087, etc., biomass charcoal is used as a functional powder, and is directly added into a resin matrix to be blended to prepare master batch, and then is blended and spun with resin slices. The prior art is comprehensively analyzed, and basically, the biomass carbon powder is directly or simply subjected to surface treatment by adopting a silane coupling agent and then is blended with a resin matrix. The direct blending method has high surface energy of the biomass charcoal, is easy to agglomerate, and seriously influences the spinnability and the function and effect performance of the resin. After the silane coupling agent is adopted for treatment, the coupling agent is coated on the surface of the biomass charcoal, so that the dispersibility of the biomass charcoal can be improved preliminarily, but the silane coupling agent is poor in hydrolysis resistance, is generally effective to a filler containing a silicon element and is more suitable for thermosetting resin, and the rigidity of the resin can be increased after the silane coupling agent is added, so that in the actual production process, the improvement of the dispersion effect of the silane coupling agent on the biomass charcoal material is limited, the rigidity of resin fibers is increased, the hand feeling of the resin fibers is poor, and the application is limited.
With the diversified demand of polyester fiber products, the development of novel functional polyester fiber materials is more and more urgent. At present, the main technical means for developing new products of polyester and fiber are copolymerization modification, blending modification and surface coating finishing. The copolymerization modification has low degree of flexibility and poor processing adaptability (the same production line can only produce the same variety), and the popularization degree is low. The surface coating finishing has the problem of functional durability, the functionality of the product is continuously reduced along with the increase of the washing times, and the method is limited in application. The master batch addition modification has low requirements on equipment, flexible variety slicing and lasting functional effect, and is widely popular with polyester processing enterprises. The quality (fluidity, thermal stability, and dispersibility of functional components) of the masterbatch used as a functional carrier is a key factor affecting the variety of fibers. The existing preparation method of master batches only adopts a direct blending method, and polyester matrix and functional materials are blended and granulated to obtain the functional master batches. In patent CN108129808 (a polyester master batch for spinning and a production process thereof), a functional master batch is prepared by using primary and regenerated polyester chips as a matrix and adding a compatibilizer, a nano inorganic filler sol, a coupling agent and the like, wherein the content of nano inorganic powder is 1-3%. Patents CN110079059 (hydrophilic easy-to-clean polyester master batch and its preparation method), CN107880500 (a silver-series antibacterial polyester master batch and its preparation method) and the like all adopt a direct blending method, and the functional material and the polyester matrix are blended and dispersed under the action of a dispersant, an antioxidant and a stabilizer. In patent CN112724607 (high content pigment carbon black-thermoplastic polyester master batch and preparation method thereof), polyester is used as a matrix, high pigment carbon black is modified by oxidation with ozone or nitric acid to improve the surface hydrophilicity, then silane coupling agent is used for modification, and a self-made special structure dispersing agent is used to improve the dispersibility of the pigment carbon black in thermoplastic polyester carrier resin, and a banbury mixer and a twin-screw extrusion granulation process are combined to realize the high pigment carbon black-thermoplastic polyester master batch with high blackness and high gloss. However, the preparation process of the dispersing agent is complex, the addition amount and the dispersibility of the carbon black are increased mainly by physically blending a polyester matrix, the carbon black, the dispersing agent, a coupling agent and the like and performing high shear and the like, and the problems of compatibility and further dispersion of the carbon black exist when the master batch and the polyester are spun. In patent CN109180923 (a high-fluidity stain-resistant and easily-dyeable polyester master batch and its preparation), acid or acid anhydride with a branched structure and dihydric alcohol are used for polymerization modification to prepare a high-fluidity polyester master batch with a low melt index, and the master batch is mainly used for cation-dyeable modification to improve the fluidity and stain resistance of the master batch. Patents CN106634060 (a preparation method of oily self-dispersible nano carbon black) and CN106634059 (a preparation method of aqueous self-dispersible nano carbon black) mainly graft a silane coupling agent on the surface of carbon black, and then copolymerize the group on the silane coupling agent with other oily/aqueous monomers, and coat a layer of polymer with dispersing and stabilizing effects on the surface of carbon black, thereby realizing self-dispersion in an oily/aqueous solvent. The self-dispersing carbon black prepared by the patent is mainly applicable to a low-temperature and low-concentration solution system by utilizing the principle of similarity and intermiscibility, and is not applicable to a high-temperature and high-viscosity polymer melt system.
Therefore, the development of the biomass charcoal and the high-concentration polyester master batch with the self-dispersion effect has important practical significance and application value.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a preparation method of self-dispersed nano biomass charcoal and high-concentration polyester master batch.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of nano biomass charcoal with self-dispersion effect comprises the steps of mixing a nano biomass charcoal material with a modifier solution, and then carrying out hydrothermal activation to prepare the nano biomass charcoal with self-dispersion effect; in the hydrothermal activation process, carbon elements in the biomass carbon react with water vapor to generate carbon monoxide and hydrogen, and the surface of the biomass carbon is further etched to generate a microporous structure; in the hydrothermal activation process, bis (dioctyloxy pyrophosphate) ethylene titanate or a chelate of bis (dioctyloxy pyrophosphate) ethylene titanate and triethanolamine reacts with hydroxyl or carboxyl in cellulose and lignin which are not completely decomposed in the biomass charcoal, and is anchored on the surface of the biomass charcoal;
the modifier solution is an aqueous solution of bis (dioctyloxy pyrophosphate) ethylene titanate or an aqueous solution of a chelate of bis (dioctyloxy pyrophosphate) ethylene titanate and triethanolamine;
the temperature of the hydrothermal activation is 150-250 ℃. When the temperature of the hydrothermal activation is lower than 150 ℃, the pressure of water vapor is small, and the generated activation energy can not effectively etch the surface of the biomass carbon; the temperature is higher than 250 ℃, the stability of the chelate of the (dioctyloxy pyrophosphate) ethylene titanate or the bis (dioctyloxy pyrophosphate) ethylene titanate and the triethanolamine is easily influenced, so the temperature range is set to be 150-250 ℃, the biomass charcoal can be fully activated and effectively etched, and the stability of the chelate of the (dioctyloxy pyrophosphate) ethylene titanate or the bis (dioctyloxy pyrophosphate) ethylene titanate and the triethanolamine can be ensured.
As a preferred technical scheme:
the preparation method of the nano biomass charcoal with the self-dispersion effect comprises the following specific preparation steps:
(1) heating the biomass raw material to 400-600 ℃ at a speed of 5-15 ℃/min in a nitrogen atmosphere, and preserving heat for 1-2 hours to obtain a biomass charcoal material;
(2) crushing and grinding the biomass charcoal material in a crusher to obtain a nano biomass charcoal material;
(3) dissolving bis (dioctyloxypyrophosphate) ethylene titanate or a chelate of bis (dioctyloxypyrophosphate) ethylene titanate and triethanolamine in water according to the addition of 0.5-2.5 wt% to obtain a modifier solution;
(4) adding the nano biomass charcoal material into a modifier solution according to the addition of 10-50 wt%, and performing ultrasonic dispersion to obtain a nano biomass charcoal mixed solution; the hydrothermal activation is carried out after the step is finished, and when the addition proportion of the nano biomass charcoal is too low and is lower than 10%, the efficiency is low, and energy is wasted; the addition amount is more than 50 percent, which can cause the infiltration and activation of the carbon material in the mixed solution and the contact with the bis (dioctyloxy pyrophosphate) ethylene titanate or the chelate of the bis (dioctyloxy pyrophosphate) ethylene titanate and triethanolamine, and the reaction is uneven and insufficient.
(5) And (3) putting the nano biomass charcoal mixed solution into a closed container, heating to 150-250 ℃ at the speed of 5-10 ℃/min, preserving the heat for 1-2 hours, carrying out hydrothermal activation, and then drying the hydrothermal activation product to obtain the nano biomass charcoal with the self-dispersion effect.
According to the preparation method of the nano biomass charcoal with the self-dispersion effect, in the step (1), the biomass raw material is phyllostachys pubescens, rice hulls, corncobs, Chinese torreya shells or coconut shells; the yield of the biomass charcoal material is 30-45%.
According to the preparation method of the nano biomass charcoal with the self-dispersion effect, in the step (2), the average particle size of the nano biomass charcoal material is 10-30 nm.
According to the preparation method of the nano biomass charcoal with the self-dispersion effect, in the step (4), the ultrasonic frequency is 50-100 kHz, and the ultrasonic time is 15-45 minutes.
The preparation method of the nano biomass charcoal with the self-dispersion effect comprises the step (5), wherein the drying temperature is 100-110 ℃ and the drying time is 6 hours.
The preparation method of the nano biomass charcoal with the self-dispersion effect has the self-dispersion effect, and the surface of the nano biomass charcoal contains the groups
Figure BDA0003664912440000041
Or alternatively
Figure BDA0003664912440000042
And with
Figure BDA0003664912440000043
In the nano biomass charcoal with the self-dispersion effect, the content of bis (dioctyloxy pyrophosphate) ethylene titanate or a chelate of bis (dioctyloxy pyrophosphate) ethylene titanate and triethanolamine is 1-5 wt%;
the specific surface area of the nano biomass carbon with the self-dispersion effect is 100-500 m 2 (ii) a specific volume of pores per gram, an average pore diameter of 3 to 10nm, and a total pore volume of 0.1 to 1.5cm 3 /g；
After the nano biomass charcoal with the self-dispersion effect is kept stand in water for 15 days, the Zeta potential is-45 to-55 mV; zeta potential is used for representing the dispersion stability of the nano material, and the higher the absolute value of the Zeta potential is, the more stable the system is, namely the dissolution or dispersion can resist aggregation.
The invention also provides a preparation method of the high-concentration polyester master batch, which comprises the steps of injecting the nano biomass charcoal with the self-dispersion effect, polyester slices and the antioxidant into a double-screw extruder for blending granulation to prepare the high-concentration polyester master batch;
the content of the biomass charcoal in the high-concentration polyester master batch is 20-35 wt%. In the common master batch, the addition amount of the functional powder can reach about 20 percent at most, and the concentration of the biochar in the master batch prepared by the method can reach 35 percent.
The unsaturated bond in the chelate of dioctyloxy pyrophosphate) ethylene titanate or bis (dioctyloxy pyrophosphate) ethylene titanate and triethanolamine reacts with the carboxyl end group and diethylene glycol in the polyester in the high-temperature melting process, and the molecular chain contains
Figure BDA0003664912440000044
And (3) chain segments.
As a preferred technical scheme:
according to the preparation method of the high-concentration polyester master batch, the polyester chips are dried, and the drying process comprises the following steps: firstly, carrying out air blast drying on a polyester chip at 120-150 ℃ for 1-3 h, and then transferring the polyester chip to a dehumidification drying oven to be dried at 140-170 ℃ for 4-6 h;
the intrinsic viscosity of the polyester chip is 0.60-0.8 dl/g, and the melt index is 16-25 g/min (250 ℃, 2.16 Kg); the polyester chip has a carboxyl end group content of 20 to 36mol/t and a diethylene glycol content of 1.0 to 3.0 wt%.
According to the preparation method of the high-concentration polyester master batch, the screw processing temperature of the double-screw extruder is 200-270 ℃.
According to the preparation method of the high-concentration polyester master batch, the double-screw extruder is divided into eleven temperature control areas, the temperature of the first area is 200-210 ℃, the temperature of the second area, the third area and the fourth area is 265-275 ℃, the temperature of the fifth area and the sixth area is 245-255 ℃, the temperature of the seventh area and the eighth area is 235-245 ℃, the temperature of the ninth area is 225-235 ℃, the temperature of the tenth area is 220-230 ℃, and the temperature of the eleventh area is 245-255 ℃;
the temperature of a machine head of the double-screw extruder is 265-275 ℃;
the screw rotating speed of the screw extruder is 200-300 rpm.
According to the preparation method of the high-concentration polyester master batch, the antioxidant is antioxidant 1010, antioxidant 168, antioxidant 1076 or antioxidant 1098; the addition amount of the antioxidant is 0.1-1.0 wt% of the polyester chip.
The preparation method of the high-concentration polyester master batch has the advantages that the intrinsic viscosity of the high-concentration polyester master batch is 0.6-0.8 dl/g, and the melt index is 18-30 g/min (250 ℃ and 2.16 Kg).
Mechanism of the invention
The invention relates to a preparation method of nano biomass charcoal and high-concentration master batch with self-dispersion effect, which comprises the steps of firstly preparing a nano biomass charcoal material with self-dispersion effect by adopting a carbonization-dispersion one-step method, and then blending and granulating the nano biomass charcoal and a polyester matrix to prepare the high-concentration polyester master batch. The biomass charcoal and the nano biochar have small particle size and high specific surface energy, the prior art generally needs to adopt a coupling agent for dispersion treatment, and the coupling agent is generally used in a small amount (0.5-2%), so that the coupling agent must be uniformly dispersed in the biochar to exert the optimal effect, otherwise, the dispersion effect cannot be achieved. But the traditional direct blending method is difficult to ensure that the coupling agent is uniformly distributed in the nano biochar material. In order to improve the self-dispersion effect of the nano biomass charcoal, bis (dioctyloxy pyrophosphate) ethylene titanate or a chelate of bis (dioctyloxy pyrophosphate) ethylene titanate and triethanolamine is dissolved in water, and is mixed with the nano biomass charcoal material for hydrothermal activation. In the activation process, under the action of water vapor, water molecules can further etch pores of the biomass charcoal material, so that surface groups of the biomass charcoal material are enriched; meanwhile, as dioctyloxy pyrophosphate) ethylene titanate or a chelate of bis (dioctyloxy pyrophosphate) ethylene titanate and triethanolamine is dissolved in water to form a homogeneous system with water, the water is continuously boiled to generate steam in the hydrothermal activation process of 150-250 ℃, the steam can be fully and uniformly mixed with the biochar, and as the biomass carbon material has abundant surface groups, the chelate of the dioctyloxy pyrophosphate) ethylene titanate or the bis (dioctyloxy pyrophosphate) ethylene titanate and triethanolamine reacts with the groups in the biomass carbon under the action of heat, and is anchored on the surface of the biomass carbon to play a role in stable dispersion.
In the process of polyester blending granulation, unsaturated bonds in (dioctyloxy pyrophosphate) ethylene titanate or a chelate of bis (dioctyloxy pyrophosphate) ethylene titanate and triethanolamine can react with polyester in a high-temperature melting process, so that the requirement on the content of terminal carboxyl and diethylene glycol of a polyester chip is low during the preparation of master batches, the adaptability is wide, and even the terminal carboxyl and the diethylene glycol in the polyester chip can be utilized to react with the chelate of (dioctyloxy pyrophosphate) ethylene titanate or bis (dioctyloxy pyrophosphate) ethylene titanate and triethanolamine to play a role in bridging, so that the biomass charcoal is uniformly and stably dispersed in the polyester. In addition, because a large number of long-chain carbon atom groups are grafted in the biomass charcoal material, the compatibility with a polyester system is improved, the surface energy of the interface between the nano biomass charcoal material and the polyester is changed, the nano biomass charcoal material has the functions of flexibility and stress transfer, a self-lubricating effect is generated, the viscosity of a blending system is reduced, and the flowing property and the processing technology of the polyester are improved, so that the method is very suitable for preparing high-concentration polyester master batches, and the concentration of the prepared polyester master batches can reach 35 wt%.
Has the advantages that:
(1) according to the preparation method of the self-dispersed nano biomass charcoal, the biomass charcoal material with developed pore structure, specific surface area and excellent dispersibility is prepared by integrating carbonization, steam activation and dispersion, the cost is low, the equipment and the process are simple, and the application value is high;
(2) the high-concentration biomass charcoal polyester master batch prepared by the invention has the advantages of uniform dispersion of biomass charcoal, good master batch fluidity, good compatibility with polyester, good application prospect and market value.
Drawings
FIG. 1 is an electron micrograph (SEM) of the unpulverized bamboo charcoal of example 1;
FIG. 2 is an electron micrograph (SEM) of unpulverized rice husk carbon of example 2;
FIG. 3 is an electron micrograph (SEM photograph) of the crushed torreya grandis carbon in example 3.
FIG. 4 is an electron micrograph (i.e., SEM photograph) of unpulverized coconut shell carbon of example 4.
FIG. 5 is an electron micrograph (i.e., SEM photograph) of unpulverized corncob carbon of example 5.
Detailed Description
The invention will be further illustrated with reference to specific embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention can be made by those skilled in the art after reading the teaching of the present invention, and these equivalents also fall within the scope of the claims appended to the present application.
Example 1
A preparation method of high-concentration polyester master batch comprises the following specific steps:
(1) heating a biomass raw material (phyllostachys pubescens) to 600 ℃ at a speed of 5 ℃/min in a nitrogen atmosphere, and preserving heat for 1 hour to obtain a biomass charcoal material shown in figure 1, wherein the yield of the biomass charcoal material is 30.46%;
(2) crushing and grinding the biomass charcoal material in a crusher to obtain a nano biomass charcoal material with the average particle size of 10 nm;
(3) dissolving bis (dioctyloxypyrophosphate) ethylene titanate in water according to the addition of 1 wt% to obtain a modifier solution;
(4) adding the nano biomass charcoal material into a modifier solution according to the addition of 25 wt%, and performing ultrasonic dispersion (the ultrasonic frequency is 80kHz, and the ultrasonic time is 25 minutes) to obtain a nano biomass charcoal mixed solution;
(5) putting the nano biomass charcoal mixed solution into a closed container, heating to 250 ℃ at the speed of 5 ℃/min, preserving heat for 1 hour, carrying out hydrothermal activation, and drying a hydrothermal activation product at 100 ℃ for 6 hours to obtain the nano biomass charcoal with the self-dispersion effect;
the specific surface area of the prepared nano biomass charcoal with self-dispersion effect is 494m 2 G, average pore diameter of 3nm, total pore volume of 1.44cm 3 Per g, the surface of which contains the groups:
Figure BDA0003664912440000071
in the prepared nano biomass charcoal with self-dispersion effect, the content of bis (dioctyloxy pyrophosphate) ethylene titanate is 4 wt%;
standing the prepared nano biomass charcoal with the self-dispersion effect in water for 15 days, wherein the Zeta potential is-54 mV;
(6) firstly, carrying out forced air drying on polyester chips at 120 ℃ for 2 hours, and then transferring the polyester chips to a dehumidifying and drying box to dry the polyester chips at 150 ℃ for 6 hours; the intrinsic viscosity of the polyester chip is 0.6dl/g, and the melt index is 16g/min (250 ℃, 2.16 Kg); the carboxyl end group content of the polyester chip is 25mol/t, and the diethylene glycol content is 2 wt%;
(7) injecting the nano biomass charcoal with the self-dispersion effect prepared in the step (5), the polyester slices dried in the step (6) and the antioxidant 1010 into a double-screw extruder for blending granulation to prepare high-concentration polyester master batches;
wherein the addition amount of the polyester chip is 10kg, the addition amount of the nano biomass charcoal with self-dispersion effect is 3.5kg, and the addition amount of the antioxidant 1010 is 0.1 kg;
the double-screw extruder is divided into eleven temperature control areas, wherein the temperature of the first area is 200 ℃, the temperature of the second area is 265 ℃, the temperature of the third area is 265 ℃, the temperature of the fourth area is 265 ℃, the temperature of the fifth area is 245 ℃, the temperature of the sixth area is 245 ℃, the temperature of the seventh area is 235 ℃, the temperature of the eighth area is 235 ℃, the temperature of the ninth area is 225 ℃, the temperature of the tenth area is 220 ℃, and the temperature of the eleventh area is 245 ℃; the head temperature of the double-screw extruder is 265 ℃; the screw speed of the screw extruder was 200 rpm.
The biomass charcoal content in the finally prepared high-concentration polyester master batch is 35 wt%; the obtained high-concentration polyester master batch has the intrinsic viscosity of 0.6dl/g and the melt index of 18g/min (250 ℃ and 2.16 Kg).
Example 2
A preparation method of high-concentration polyester master batch comprises the following specific steps:
(1) heating a biomass raw material (rice hull) to 400 ℃ at a speed of 15 ℃/min in a nitrogen atmosphere, and preserving heat for 1.5 hours to obtain a biomass charcoal material shown in figure 2, wherein the yield of the biomass charcoal material is 43.23%;
(2) crushing and grinding the biomass charcoal material in a crusher to obtain a nano biomass charcoal material with the average particle size of 30 nm;
(3) dissolving a chelate of bis (dioctyloxypyrophosphate) ethylene titanate and triethanolamine in water according to the addition of 0.9 wt% to obtain a modifier solution;
(4) adding the nano biomass charcoal material into a modifier solution according to the addition of 30 wt%, and performing ultrasonic dispersion (the ultrasonic frequency is 80kHz, and the ultrasonic time is 40 minutes) to obtain a nano biomass charcoal mixed solution;
(5) putting the nano biomass charcoal mixed solution into a closed container, heating to 150 ℃ at the speed of 10 ℃/min, preserving heat for 2 hours, carrying out hydrothermal activation, and drying a hydrothermal activation product at 100 ℃ for 6 hours to obtain the nano biomass charcoal with the self-dispersion effect;
the specific surface area of the prepared nano biomass charcoal with self-dispersion effect is 113m 2 G, average pore diameter of 8nm and total pore volume of 0.17cm 3 Per g, the surface of which contains the groups:
Figure BDA0003664912440000081
in the prepared nano biomass charcoal with self-dispersion effect, the content of the chelate of bis (dioctyloxy pyrophosphate) ethylene titanate and triethanolamine is 3 wt%;
standing the prepared nano biomass charcoal with the self-dispersion effect in water for 15 days, wherein the Zeta potential is-46 mV;
(6) firstly, blowing and drying the polyester slices at 130 ℃ for 2.5h, and then transferring the polyester slices to a dehumidifying and drying box to dry at 160 ℃ for 5 h; the intrinsic viscosity of the polyester chip is 0.65dl/g, and the melt index is 18g/min (250 ℃, 2.16 Kg); the carboxyl end group content of the polyester chip is 36mol/t, and the diethylene glycol content is 1.5 wt%;
(7) injecting the nano biomass charcoal with the self-dispersion effect prepared in the step (5), the polyester slices dried in the step (6) and the antioxidant 168 into a double-screw extruder for blending granulation to prepare high-concentration polyester master batches;
wherein the addition amount of the polyester chip is 10kg, the addition amount of the nano biomass charcoal with self-dispersion effect is 2.5kg, and the addition amount of the antioxidant 168 is 0.1 kg;
the double-screw extruder is divided into eleven temperature control areas, wherein the temperature of the first area is 203 ℃, the temperature of the second area is 268 ℃, the temperature of the third area is 268 ℃, the temperature of the fourth area is 268 ℃, the temperature of the fifth area is 247 ℃, the temperature of the sixth area is 247 ℃, the temperature of the seventh area is 240 ℃, the temperature of the eighth area is 239 ℃, the temperature of the ninth area is 228 ℃, the temperature of the tenth area is 223 ℃, and the temperature of the eleven area is 247 ℃; the head temperature of the double-screw extruder is 267 ℃; the screw speed of the screw extruder was 225 rpm.
The biomass charcoal content in the finally prepared high-concentration polyester master batch is 25 wt%; the obtained high-concentration polyester master batch has the intrinsic viscosity of 0.63dl/g and the melt index of 19g/min (250 ℃ and 2.16 Kg).
Example 3
A preparation method of high-concentration polyester master batch comprises the following specific steps:
(1) heating a biomass raw material (Chinese torreya shells) to 500 ℃ at a speed of 10 ℃/min in a nitrogen atmosphere, and preserving heat for 2 hours to obtain a biomass charcoal material shown in figure 3, wherein the yield of the biomass charcoal material is 34.29%;
(2) crushing and grinding the biomass charcoal material in a crusher to obtain a nano biomass charcoal material with the average particle size of 16 nm;
(3) dissolving bis (dioctyloxy pyrophosphate) ethylene titanate in water according to the addition of 2.5 wt% to obtain a modifier solution;
(4) adding the nano biomass charcoal material into a modifier solution according to the addition of 50 wt%, and performing ultrasonic dispersion (the ultrasonic frequency is 100kHz, and the ultrasonic time is 30 minutes) to obtain a nano biomass charcoal mixed solution;
(5) putting the nano biomass charcoal mixed solution into a closed container, heating to 150 ℃ at the speed of 6 ℃/min, preserving heat for 1.5 hours, carrying out hydrothermal activation, and drying a hydrothermal activation product at 100 ℃ for 6 hours to obtain the nano biomass charcoal with the self-dispersion effect;
the specific surface area of the prepared nano biomass charcoal with self-dispersion effect is 319m 2 G, average pore diameter of 7nm and total pore volume of 0.76cm 3 Per g, its surface contains the groups:
Figure BDA0003664912440000091
in the prepared nano biomass charcoal with self-dispersion effect, the content of bis (dioctyloxy pyrophosphate) ethylene titanate is 5 wt%;
standing the prepared nano biomass charcoal with the self-dispersion effect in water for 15 days, wherein the Zeta potential is-51 mV;
(6) firstly, carrying out forced air drying on the polyester chips at 140 ℃ for 3h, and then transferring the polyester chips to a dehumidifying drying oven to dry the polyester chips at 140 ℃ for 5.5 h; the intrinsic viscosity of the polyester chip is 0.7dl/g, and the melt index is 20g/min (250 ℃, 2.16 Kg); the carboxyl end group content of the polyester chip is 20mol/t, and the diethylene glycol content is 1 wt%;
(7) injecting the nano biomass charcoal with the self-dispersion effect prepared in the step (5), the polyester slices dried in the step (6) and the antioxidant 1076 into a double-screw extruder for blending granulation to prepare high-concentration polyester master batches;
wherein the addition amount of the polyester chip is 15kg, the addition amount of the nano biomass charcoal with self-dispersion effect is 4.5kg, and the addition amount of the antioxidant 1076 is 75 g;
the double-screw extruder is divided into eleven temperature control areas, wherein the temperature of the first area is 205 ℃, the temperature of the second area is 270 ℃, the temperature of the third area is 270 ℃, the temperature of the fourth area is 270 ℃, the temperature of the fifth area is 251 ℃, the temperature of the sixth area is 249 ℃, the temperature of the seventh area is 241 ℃, the temperature of the eighth area is 241 ℃, the temperature of the ninth area is 231 ℃, the temperature of the tenth area is 225 ℃, and the temperature of the eleventh area is 250 ℃; the head temperature of the double-screw extruder is 270 ℃; the screw speed of the screw extruder was 250 rpm.
The biomass charcoal content in the finally prepared high-concentration polyester master batch is 30 wt%; the obtained high-concentration polyester master batch has the intrinsic viscosity of 0.7dl/g and the melt index of 24g/min (250 ℃ and 2.16 Kg).
Example 4
A preparation method of high-concentration polyester master batch comprises the following specific steps:
(1) heating a biomass raw material (coconut shell) to 450 ℃ at a speed of 10 ℃/min in a nitrogen atmosphere, and preserving heat for 2 hours to obtain a biomass charcoal material shown in figure 4, wherein the yield of the biomass charcoal material is 41.6%;
(2) crushing and grinding the biomass charcoal material in a crusher to obtain a nano biomass charcoal material with the average particle size of 28 nm;
(3) dissolving a chelate of bis (dioctyloxypyrophosphate) ethylene titanate and triethanolamine in water according to the addition of 0.5 wt% to obtain a modifier solution;
(4) adding the nano biomass charcoal material into a modifier solution according to the addition of 50 wt%, and performing ultrasonic dispersion (the ultrasonic frequency is 100kHz, and the ultrasonic time is 45 minutes) to obtain a nano biomass charcoal mixed solution;
(5) putting the nano biomass charcoal mixed solution into a closed container, heating to 180 ℃ at the speed of 7 ℃/min, preserving heat for 2 hours, carrying out hydrothermal activation, and drying a hydrothermal activation product at 105 ℃ for 6 hours to obtain the nano biomass charcoal with the self-dispersion effect;
the specific surface area of the prepared nano biomass charcoal with self-dispersion effect is 261m 2 G, average pore diameter of 6nm and total pore volume of 0.59cm 3 Per g, the surface of which contains the groups:
Figure BDA0003664912440000101
in the prepared nano biomass charcoal with self-dispersion effect, the content of the chelate of bis (dioctyloxy pyrophosphate) ethylene titanate and triethanolamine is 1 wt%;
standing the prepared nano biomass charcoal with the self-dispersion effect in water for 15 days, wherein the Zeta potential is-45 mV;
(6) firstly, blowing and drying the polyester chips for 1.5h at 150 ℃, and then transferring the polyester chips to a dehumidifying and drying box for drying for 4.5h at 170 ℃; the intrinsic viscosity of the polyester chip is 0.75dl/g, and the melt index is 22g/min (250 ℃, 2.16 Kg); the carboxyl end group content of the polyester chip is 32mol/t, and the diethylene glycol content is 3 wt%;
(7) injecting the nano biomass charcoal with the self-dispersion effect prepared in the step (5), the polyester slices dried in the step (6) and an antioxidant 1098 into a double-screw extruder for blending granulation to prepare high-concentration polyester master batches;
wherein the addition amount of the polyester chip is 5kg, the addition amount of the nano biomass charcoal with self-dispersion effect is 1kg, and the addition amount of the antioxidant 1098 is 300 g;
the double-screw extruder is divided into eleven temperature control regions, wherein the temperature of the first region is 207 ℃, the temperature of the second region is 273 ℃, the temperature of the third region is 273 ℃, the temperature of the fourth region is 273 ℃, the temperature of the fifth region is 253 ℃, the temperature of the sixth region is 251 ℃, the temperature of the seventh region is 243 ℃, the temperature of the eighth region is 243 ℃, the temperature of the ninth region is 233 ℃, the temperature of the tenth region is 227 ℃, and the temperature of the eleventh region is 252 ℃; the head temperature of the double-screw extruder is 272 ℃; the screw speed of the screw extruder was 280 rpm.
The biomass charcoal content in the finally prepared high-concentration polyester master batch is 20 wt%; the prepared high-concentration polyester master batch has the intrinsic viscosity of 0.73dl/g and the melt index of 24g/min (250 ℃ and 2.16 Kg).
Example 5
A preparation method of high-concentration polyester master batch comprises the following specific steps:
(1) heating a biomass raw material (corncob) to 550 ℃ at a speed of 15 ℃/min in a nitrogen atmosphere, and preserving heat for 1 hour to obtain a biomass charcoal material shown in figure 5, wherein the yield of the biomass charcoal material is 35.2%;
(2) crushing and grinding the biomass charcoal material in a crusher to obtain a nano biomass charcoal material with the average particle size of 15 nm;
(3) dissolving bis (dioctyloxy pyrophosphate) ethylene titanate in water according to the addition of 1.6 wt% to obtain a modifier solution;
(4) adding the nano biomass charcoal material into a modifier solution according to the addition of 40 wt%, and performing ultrasonic dispersion (the ultrasonic frequency is 80kHz, and the ultrasonic time is 40 minutes) to obtain a nano biomass charcoal mixed solution;
(5) putting the nano biomass charcoal mixed solution into a closed container, heating to 200 ℃ at the speed of 8 ℃/min, preserving heat for 1.5 hours, carrying out hydrothermal activation, and then drying a hydrothermal activation product at 105 ℃ for 6 hours to obtain the nano biomass charcoal with the self-dispersion effect;
the specific surface area of the prepared nano biomass charcoal with self-dispersion effect is 407m 2 G, average pore diameter of 6nm and total pore volume of 1.02cm 3 Per g, the surface of which contains the groups:
Figure BDA0003664912440000111
in the prepared nano biomass charcoal with self-dispersion effect, the content of bis (dioctyloxy pyrophosphate) ethylene titanate is 4 wt%;
standing the prepared nano biomass charcoal with the self-dispersion effect in water for 15 days, wherein the Zeta potential is-52 mV;
(6) firstly, carrying out forced air drying on the polyester chips at 130 ℃ for 1h, and then transferring the polyester chips to a dehumidification drying oven to dry the polyester chips at 160 ℃ for 4 h; the intrinsic viscosity of the polyester chip is 0.8dl/g, and the melt index is 25g/min (250 ℃, 2.16 Kg); the polyester chip has the carboxyl end group content of 32mol/t and the diethylene glycol content of 2.5 wt%;
(7) injecting the nano biomass charcoal with the self-dispersion effect prepared in the step (5), the polyester chips dried in the step (6) and an antioxidant 1010 into a double-screw extruder for blending granulation to prepare high-concentration polyester master batches;
wherein the addition amount of the polyester chip is 15kg, the addition amount of the nano biomass charcoal with self-dispersion effect is 4.8kg, and the addition amount of the antioxidant 1010 is 120 g;
the double-screw extruder is divided into eleven temperature control areas, wherein the temperature of the first area is 210 ℃, the temperature of the second area is 275 ℃, the temperature of the third area is 275 ℃, the temperature of the fourth area is 275 ℃, the temperature of the fifth area is 255 ℃, the temperature of the sixth area is 255 ℃, the temperature of the seventh area is 245 ℃, the temperature of the eighth area is 245 ℃, the temperature of the ninth area is 235 ℃, the temperature of the tenth area is 230 ℃, and the temperature of the eleventh area is 255 ℃; the head temperature of the double-screw extruder is 275 ℃; the screw speed of the screw extruder was 300 rpm.
The biomass charcoal content in the finally prepared high-concentration polyester master batch is 32 wt%; the obtained high-concentration polyester master batch has the intrinsic viscosity of 0.8dl/g and the melt index of 30g/min (250 ℃ and 2.16 Kg).
Example 6
A preparation method of high-concentration polyester master batch comprises the following specific steps:
(1) heating a biomass raw material (coconut shell) to 500 ℃ at a speed of 10 ℃/min in a nitrogen atmosphere, and preserving heat for 1.5 hours to obtain a biomass charcoal material, wherein the yield of the biomass charcoal material is 43.42%;
(2) crushing and grinding the biomass charcoal material in a crusher to obtain a nano biomass charcoal material with the average particle size of 20 nm;
(3) dissolving a chelate of bis (dioctyloxypyrophosphate) ethylene titanate and triethanolamine in water according to the addition of 0.5 wt% to obtain a modifier solution;
(4) adding the nano biomass charcoal material into a modifier solution according to the addition of 10 wt%, and performing ultrasonic dispersion (the ultrasonic frequency is 50kHz, and the ultrasonic time is 15 minutes) to obtain a nano biomass charcoal mixed solution;
(5) putting the nano biomass charcoal mixed solution into a closed container, heating to 220 ℃ at the speed of 9 ℃/min, preserving heat for 1 hour, carrying out hydrothermal activation, and drying a hydrothermal activation product at 105 ℃ for 6 hours to obtain the nano biomass charcoal with the self-dispersion effect;
the specific surface area of the prepared nano biomass charcoal with self-dispersion effect is 416m 2 G, average pore diameter of 5nm and total pore volume of 1.23cm 3 Per g, the surface of which contains the groups:
Figure BDA0003664912440000121
in the prepared nano biomass charcoal with self-dispersion effect, the content of the chelate of bis (dioctyloxy pyrophosphate) ethylene titanate and triethanolamine is 5 wt%;
standing the prepared nano biomass charcoal with the self-dispersion effect in water for 15 days, wherein the Zeta potential is-50 mV;
(6) firstly, blowing and drying the polyester chips at 130 ℃ for 2 hours, and then transferring the polyester chips to a dehumidifying and drying box to dry for 5.5 hours at 150 ℃; the intrinsic viscosity of the polyester chip is 0.7dl/g, and the melt index is 20g/min (250 ℃, 2.16 Kg); the carboxyl end group content of the polyester chip is 30mol/t, and the diethylene glycol content is 2 wt%;
(7) injecting the nano biomass charcoal with the self-dispersion effect prepared in the step (5), the polyester slices dried in the step (6) and the antioxidant 168 into a double-screw extruder for blending granulation to prepare high-concentration polyester master batches;
wherein the addition amount of the polyester chip is 5kg, the addition amount of the nano biomass charcoal with self-dispersion effect is 1.5kg, and the addition amount of the antioxidant 168 is 15 g;
the double-screw extruder is divided into eleven temperature control zones, wherein the temperature of the first zone is 204 ℃, the temperature of the second zone is 269 ℃, the temperature of the third zone is 269 ℃, the temperature of the fourth zone is 269 ℃, the temperature of the fifth zone is 250 ℃, the temperature of the sixth zone is 248 ℃, the temperature of the seventh zone is 240 ℃, the temperature of the eighth zone is 240 ℃, the temperature of the ninth zone is 230 ℃, the temperature of the tenth zone is 224 ℃, and the temperature of the eleven zone is 249 ℃; the head temperature of the double-screw extruder is 269 ℃; the screw speed of the screw extruder was 225 rpm.
The biomass charcoal content in the finally prepared high-concentration polyester master batch is 30 wt%; the obtained high-concentration polyester master batch has the intrinsic viscosity of 0.7dl/g and the melt index of 21g/min (250 ℃ and 2.16 Kg).
Example 7
A preparation method of high-concentration polyester master batch comprises the following specific steps:
(1) heating a biomass raw material (phyllostachys pubescens) to 450 ℃ at a speed of 5 ℃/min in a nitrogen atmosphere, and preserving heat for 1.5 hours to obtain a biomass charcoal material, wherein the yield of the biomass charcoal material is 39.88%;
(2) crushing and grinding the biomass charcoal material in a crusher to obtain a nano biomass charcoal material with the average particle size of 25 nm;
(3) dissolving bis (dioctyloxy pyrophosphate) ethylene titanate in water according to the addition of 0.6 wt% to obtain a modifier solution;
(4) adding the nano biomass charcoal material into a modifier solution according to the addition of 20 wt%, and performing ultrasonic dispersion (the ultrasonic frequency is 50kHz, and the ultrasonic time is 30 minutes) to obtain a nano biomass charcoal mixed solution;
(5) putting the nano biomass charcoal mixed solution into a closed container, heating to 240 ℃ at the speed of 7 ℃/min, preserving heat for 2 hours, carrying out hydrothermal activation, and then drying a hydrothermal activation product at 110 ℃ for 6 hours to obtain the nano biomass charcoal with the self-dispersion effect;
the specific surface area of the prepared nano biomass charcoal with self-dispersion effect is 392m 2 (ii)/g, average pore diameter of 4nm and total pore volume of 0.94cm 3 Per g, the surface of which contains the groups:
Figure BDA0003664912440000131
in the prepared nano biomass charcoal with self-dispersion effect, the content of bis (dioctyloxy pyrophosphate) ethylene titanate is 3 wt%;
standing the prepared nano biomass charcoal with the self-dispersion effect in water for 15 days, wherein the Zeta potential is-48 mV;
(6) firstly, carrying out forced air drying on the polyester chips at 140 ℃ for 2.5h, and then transferring the polyester chips to a dehumidifying drying oven to dry the polyester chips at 170 ℃ for 4.5 h; the intrinsic viscosity of the polyester chip is 0.65dl/g, and the melt index is 18g/min (250 ℃, 2.16 Kg); the carboxyl end group content of the polyester chip is 30mol/t, and the diethylene glycol content is 2 wt%;
(7) injecting the nano biomass charcoal with the self-dispersion effect prepared in the step (5), the polyester slices dried in the step (6) and the antioxidant 1076 into a double-screw extruder for blending granulation to prepare high-concentration polyester master batches;
wherein the addition amount of the polyester chip is 10kg, the addition amount of the nano biomass charcoal with self-dispersion effect is 2.5kg, and the addition amount of the antioxidant 1076 is 70 g;
the double-screw extruder is divided into eleven temperature control areas, wherein the temperature of the first area is 203.5 ℃, the temperature of the second area is 268 ℃, the temperature of the third area is 268 ℃, the temperature of the fourth area is 268 ℃, the temperature of the fifth area is 246 ℃, the temperature of the sixth area is 247.5 ℃, the temperature of the seventh area is 240.5 ℃, the temperature of the eighth area is 240 ℃, the temperature of the ninth area is 228.5 ℃, the temperature of the tenth area is 223.5 ℃, and the temperature of the eleven area is 247.5 ℃; the head temperature of the double-screw extruder is 267.5 ℃; the screw speed of the screw extruder was 230 rpm.
The biomass charcoal content in the finally prepared high-concentration polyester master batch is 25 wt%; the obtained high-concentration polyester master batch has the intrinsic viscosity of 0.66dl/g and the melt index of 23g/min (250 ℃ and 2.16 Kg).
Example 8
A preparation method of high-concentration polyester master batch comprises the following specific steps:
(1) heating a biomass raw material (Chinese torreya shells) to 600 ℃ at a speed of 10 ℃/min in a nitrogen atmosphere, and preserving heat for 2 hours to obtain a biomass charcoal material, wherein the yield of the biomass charcoal material is 32.17%;
(2) crushing and grinding the biomass charcoal material in a crusher to obtain a nano biomass charcoal material with the average particle size of 12 nm;
(3) dissolving a chelate of bis (dioctyloxypyrophosphate) ethylene titanate and triethanolamine in water according to the addition of 0.8 wt% to obtain a modifier solution;
(4) adding the nano biomass charcoal material into a modifier solution according to the addition of 40 wt%, and performing ultrasonic dispersion to obtain a nano biomass charcoal mixed solution;
wherein the ultrasonic frequency is 90kHz, and the ultrasonic time is 40 minutes;
(5) putting the nano biomass charcoal mixed solution into a closed container, heating to 160 ℃ at the speed of 8 ℃/min, preserving heat for 1.5 hours, carrying out hydrothermal activation, and drying a hydrothermal activation product at 110 ℃ for 6 hours to obtain the nano biomass charcoal with the self-dispersion effect;
the specific surface area of the prepared nano biomass charcoal with self-dispersion effect is 336m 2 (ii)/g, average pore diameter of 10nm and total pore volume of 0.88cm 3 Per g, the surface of which contains the groups:
Figure BDA0003664912440000141
in the prepared nano biomass charcoal with self-dispersion effect, the content of the chelate of bis (dioctyloxy pyrophosphate) ethylene titanate and triethanolamine is 2 wt%;
standing the prepared nano biomass charcoal with the self-dispersion effect in water for 15 days, wherein the Zeta potential is-49 mV;
(6) firstly, carrying out forced air drying on the polyester chips at 140 ℃ for 2h, and then transferring the polyester chips to a dehumidifying drying oven to dry the polyester chips at 160 ℃ for 4 h; the intrinsic viscosity of the polyester chip is 0.75dl/g, and the melt index is 22g/min (250 ℃, 2.16 Kg); the carboxyl end group content of the polyester chip is 28mol/t, and the diethylene glycol content is 2.5 wt%;
(7) injecting the nano biomass charcoal with the self-dispersion effect prepared in the step (5), the polyester slices dried in the step (6) and an antioxidant 1098 into a double-screw extruder for blending granulation to prepare high-concentration polyester master batches;
wherein the addition amount of the polyester chip is 10kg, the addition amount of the nano biomass charcoal with self-dispersion effect is 2.7kg, and the addition amount of the antioxidant 1098 is 90 g;
the double-screw extruder is divided into eleven temperature control areas, wherein the temperature of the first area is 208 ℃, the temperature of the second area is 273.5 ℃, the temperature of the third area is 273.5 ℃, the temperature of the fourth area is 273.5 ℃, the temperature of the fifth area is 252 ℃, the temperature of the sixth area is 252 ℃, the temperature of the seventh area is 244 ℃, the temperature of the eighth area is 244 ℃, the temperature of the ninth area is 234 ℃, the temperature of the tenth area is 228 ℃, and the temperature of the eleventh area is 253 ℃; the head temperature of the double-screw extruder is 273 ℃; the screw speed of the screw extruder was 280 rpm.
The biomass charcoal content in the finally prepared high-concentration polyester master batch is 27 wt%; the obtained high-concentration polyester master batch has the intrinsic viscosity of 0.74dl/g and the melt index of 25g/min (250 ℃ and 2.16 Kg).

Claims (13)

1. A preparation method of nano biomass charcoal with self-dispersion effect is characterized by comprising the following steps: mixing the nano biomass charcoal material with a modifier solution, and then carrying out hydrothermal activation to prepare nano biomass charcoal with a self-dispersion effect;
the modifier solution is an aqueous solution of bis (dioctyloxy pyrophosphate) ethylene titanate or an aqueous solution of a chelate of bis (dioctyloxy pyrophosphate) ethylene titanate and triethanolamine;
the temperature of the hydrothermal activation is 150-250 ℃.
2. The preparation method of the nano biomass charcoal with the self-dispersion effect according to claim 1 is characterized by comprising the following specific preparation steps:
(1) heating the biomass raw material to 400-600 ℃ at a speed of 5-15 ℃/min in a nitrogen atmosphere, and preserving heat for 1-2 hours to obtain a biomass charcoal material;
(2) crushing and grinding the biomass charcoal material in a crusher to obtain a nano biomass charcoal material;
(3) dissolving bis (dioctyloxypyrophosphate) ethylene titanate or a chelate of bis (dioctyloxypyrophosphate) ethylene titanate and triethanolamine in water according to the addition of 0.5-2.5 wt% to obtain a modifier solution;
(4) adding the nano biomass charcoal material into a modifier solution according to the addition of 10-50 wt%, and performing ultrasonic dispersion to obtain a nano biomass charcoal mixed solution;
(5) and (3) putting the nano biomass charcoal mixed solution into a closed container, heating to 150-250 ℃ at the speed of 5-10 ℃/min, preserving the heat for 1-2 hours, carrying out hydrothermal activation, and then drying the hydrothermal activation product to obtain the nano biomass charcoal with the self-dispersion effect.
3. The method for preparing nano biomass charcoal with self-dispersion effect according to claim 2, wherein the biomass raw material in the step (1) is phyllostachys pubescens, rice hulls, corncobs, torreya grandis shells or coconut shells; the yield of the biomass charcoal material is 30-45%.
4. The method for preparing nano biomass charcoal with self-dispersion effect according to claim 2, wherein the average particle size of the nano biomass charcoal material in the step (2) is 10-30 nm.
5. The preparation method of the nano biomass charcoal with the self-dispersion effect according to claim 2, wherein the ultrasonic frequency in the step (4) is 50-100 kHz, and the ultrasonic time is 15-45 minutes.
6. The method for preparing nano biomass charcoal with self-dispersion effect according to claim 2, wherein the drying treatment in the step (5) is performed at 100-110 ℃ for 6 hours.
7. The method for preparing nano biomass charcoal with self-dispersion effect according to claim 1 or 2, wherein the nano biomass charcoal with self-dispersion effect has groups on the surface
Figure FDA0003664912430000011
Or
Figure FDA0003664912430000021
And
Figure FDA0003664912430000022
in the nano biomass charcoal with the self-dispersion effect, the content of a chelate of bis (dioctyloxy pyrophosphate) ethylene titanate or bis (dioctyloxy pyrophosphate) ethylene titanate and triethanolamine is 1-5 wt%;
the specific surface area of the nano biomass carbon with the self-dispersion effect is 100-500 m 2 (ii) a specific volume of pores per gram, an average pore diameter of 3 to 10nm, and a total pore volume of 0.1 to 1.5cm 3 /g；
After the nano biomass charcoal with the self-dispersion effect is kept still in water for 15 days, the Zeta potential is-45 to-55 mV.
8. A preparation method of high-concentration polyester master batch is characterized by comprising the following steps: injecting the nano biomass charcoal with self-dispersion effect, polyester chips and an antioxidant into a double-screw extruder for blending granulation to prepare high-concentration polyester master batch, wherein the nano biomass charcoal and the polyester chips have the self-dispersion effect;
the content of the biomass charcoal in the high-concentration polyester master batch is 20-35 wt%.
9. The method for preparing the high-concentration polyester masterbatch according to claim 8, wherein the polyester chips are dried, and the drying process comprises the following steps: firstly, carrying out air blast drying on a polyester chip at 120-150 ℃ for 1-3 h, and then transferring the polyester chip to a dehumidification drying oven to be dried at 140-170 ℃ for 4-6 h;
the intrinsic viscosity of the polyester chip is 0.60-0.8 dl/g, and the melt index is 16-25 g/min; the polyester chip has a carboxyl end group content of 20 to 36mol/t and a diethylene glycol content of 1.0 to 3.0 wt%.
10. The method for preparing the high-concentration polyester master batch according to claim 8, wherein the screw processing temperature of the twin-screw extruder is 200-270 ℃.
11. The preparation method of the high-concentration polyester master batch according to claim 10, wherein the double-screw extruder is divided into eleven temperature control zones, the temperature of the first zone is 200-210 ℃, the temperature of the second zone, the temperature of the third zone and the temperature of the fourth zone are 265-275 ℃, the temperature of the fifth zone and the temperature of the sixth zone are 245-255 ℃, the temperature of the seventh zone and the temperature of the eighth zone are 235-245 ℃, the temperature of the ninth zone is 225-235 ℃, the temperature of the tenth zone is 220-230 ℃, and the temperature of the eleventh zone is 245-255 ℃;
the head temperature of the double-screw extruder is 265-275 ℃;
the screw rotating speed of the screw extruder is 200-300 rpm.
12. The method for preparing the high-concentration polyester masterbatch according to claim 8, wherein the antioxidant is 1010, 168, 1076 or 1098; the addition amount of the antioxidant is 0.1-1.0 wt% of the polyester chip.
13. The method of claim 8, wherein the high concentration polyester masterbatch has an intrinsic viscosity of 0.6 to 0.8dl/g and a melt index of 18 to 30 g/min.
CN202210590412.XA 2022-05-26 2022-05-26 Preparation method of self-dispersed nano biomass charcoal and high-concentration polyester master batch Active CN114940836B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210590412.XA CN114940836B (en) 2022-05-26 2022-05-26 Preparation method of self-dispersed nano biomass charcoal and high-concentration polyester master batch

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210590412.XA CN114940836B (en) 2022-05-26 2022-05-26 Preparation method of self-dispersed nano biomass charcoal and high-concentration polyester master batch

Publications (2)

Publication Number Publication Date
CN114940836A true CN114940836A (en) 2022-08-26
CN114940836B CN114940836B (en) 2023-03-10

Family

ID=82909797

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210590412.XA Active CN114940836B (en) 2022-05-26 2022-05-26 Preparation method of self-dispersed nano biomass charcoal and high-concentration polyester master batch

Country Status (1)

Country Link
CN (1) CN114940836B (en)

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105420835A (en) * 2015-12-21 2016-03-23 上海德福伦化纤有限公司 Manufacturing method of antibacterial and far infrared health polyester fibers
CN107778531A (en) * 2017-11-17 2018-03-09 青岛黑猫炭黑科技有限责任公司 A kind of method that carbon black dry process prepares slurries
CN107955209A (en) * 2017-11-17 2018-04-24 青岛黑猫炭黑科技有限责任公司 A kind of method that carbon black wet-treating prepares slurries
CN108084744A (en) * 2017-12-22 2018-05-29 江南大学 A kind of method that self-dispersing nano carbon black is prepared based on sulfydryl-alkene click-reaction
KR20180062026A (en) * 2016-11-30 2018-06-08 주식회사 휴비스 Non-Woven Sheet Containing Charcoal
CN111604029A (en) * 2020-05-15 2020-09-01 吴丹妮 Modified activated carbon composite material and preparation method thereof
CN112374941A (en) * 2020-11-19 2021-02-19 中国农业科学院草原研究所 Soil remediation agent prepared from crop straws and biochar

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105420835A (en) * 2015-12-21 2016-03-23 上海德福伦化纤有限公司 Manufacturing method of antibacterial and far infrared health polyester fibers
KR20180062026A (en) * 2016-11-30 2018-06-08 주식회사 휴비스 Non-Woven Sheet Containing Charcoal
CN107778531A (en) * 2017-11-17 2018-03-09 青岛黑猫炭黑科技有限责任公司 A kind of method that carbon black dry process prepares slurries
CN107955209A (en) * 2017-11-17 2018-04-24 青岛黑猫炭黑科技有限责任公司 A kind of method that carbon black wet-treating prepares slurries
CN108084744A (en) * 2017-12-22 2018-05-29 江南大学 A kind of method that self-dispersing nano carbon black is prepared based on sulfydryl-alkene click-reaction
CN111604029A (en) * 2020-05-15 2020-09-01 吴丹妮 Modified activated carbon composite material and preparation method thereof
CN112374941A (en) * 2020-11-19 2021-02-19 中国农业科学院草原研究所 Soil remediation agent prepared from crop straws and biochar

Also Published As

Publication number Publication date
CN114940836B (en) 2023-03-10

Similar Documents

Publication Publication Date Title
CN104672495B (en) A kind of organo-mineral complexing heat filling and preparation method thereof and its application
CN104845301B (en) A kind of ultraviolet light screener and preparation method thereof and polylactic acid film comprising the ultraviolet light screener and preparation method thereof
CN101289183A (en) Method for preparing starch based active carbon microballoons with high specific surface area
CN102181140B (en) Carbon fiber silk waste reinforced polycarbonate composite material and preparation method of the carbon fiber silk waste reinforced polycarbonate composite material
CN103059596A (en) Nano-reinforced wood-plastic composite and preparation method thereof
CN102675804A (en) Thermoplastic konjac glucomannan/graphene oxide compound material and preparation method thereof
CN109852044A (en) Thermally conductive nylon of a kind of boron nitride orientation and preparation method thereof
CN111944065B (en) Biomass board and preparation method thereof
CN109233230B (en) Organic/inorganic hybrid modified polylactic acid membrane material and preparation method thereof
CN106497149B (en) A method of utilizing lignin prepare with scale nanometer carbon black
CN104177696A (en) Filling material master batch used for non-woven fabrics and preparing process thereof
CN109369898A (en) A kind of high fluidity conductive polyester master batch and preparation method thereof
Tsou et al. Reinforced distiller’s grains as bio-fillers in environment-friendly poly (ethylene terephthalate) composites
CN101168616B (en) Method for preparing polysaccharide nano particle grafting polyester modified polylactic acid material
CN101225218B (en) Polyester and polyamide blending modified plastic and preparation method therof
CN107964221B (en) Poly (ethylene 2, 5-furandicarboxylate)/poly (butylene adipate-terephthalate) composite material and preparation method thereof
CN114940836B (en) Preparation method of self-dispersed nano biomass charcoal and high-concentration polyester master batch
CN110540741A (en) Degradable composite material and preparation method and application thereof
CN104497609B (en) A kind of preparation method of Whole fiber degradable composite material
CN108822511A (en) A kind of preparation method of the full biomass 3D printing nano combined wire rod of PLA
CN114921868B (en) Preparation method of nano biochar modified melt direct-spun superfine denier polyester fiber
CN115850851B (en) Modified polypropylene composite material and preparation method thereof
CN114085539B (en) Super-hydrophobic low-precipitation degradable material and preparation method thereof
CN110643102A (en) Bamboo fiber reinforced thermoplastic resin composite material and preparation method thereof
CN104974423A (en) Diatomite/polypropylene composite material and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant