CN115418092B - Polyglycolic acid material and preparation method and application thereof - Google Patents

Polyglycolic acid material and preparation method and application thereof Download PDF

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CN115418092B
CN115418092B CN202211242253.0A CN202211242253A CN115418092B CN 115418092 B CN115418092 B CN 115418092B CN 202211242253 A CN202211242253 A CN 202211242253A CN 115418092 B CN115418092 B CN 115418092B
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polyglycolic acid
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fiber
mixing
acid material
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CN115418092A (en
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李双利
周锐
郝艳平
陈军
杨索成
赵宁
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Dawn Zhoushi Qingdao Composite Packaging Materials Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D01F1/103—Agents inhibiting growth of microorganisms
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • C08K2003/3009—Sulfides
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/16—Applications used for films
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
    • C08L2205/16—Fibres; Fibrils
    • 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
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
    • Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics

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  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
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Abstract

The application relates to the field of high polymer materials, and particularly discloses a polyglycolic acid material, a preparation method and application thereof. Comprises the following components in parts by weight: 10-40 parts of polyglycolic acid, 2.5-10 parts of toughening fiber, 0.01-0.8 part of compatilizer, 0.2-2 parts of nucleating agent, 0.1-2.5 parts of antioxidant and 0.2-0.8 part of lubricant; the toughening fiber comprises seaweed carbon fiber and polyester fiber with the mass ratio of 0.3-0.7:1; the preparation method comprises the following steps: mixing polyglycolic acid, compatilizer, antioxidant, nucleating agent, lubricant and toughening fiber, melting, extruding and granulating. The polyglycolic acid material can be used for preparing packaging, textile and medical materials, disposable plastic products and agricultural films, and has the advantages of high toughness, low brittleness, high impact strength, difficult cracking, low hydrolysis reaction activity at room temperature and good durability.

Description

Polyglycolic acid material and preparation method and application thereof
Technical Field
The application relates to the technical field of high polymer materials, in particular to a polyglycolic acid material and a preparation method and application thereof.
Background
With the growing global importance of plastic contamination problems, degradable plastics have become a focus of attention as a substitute for some plastic products that are not easily or easily recycled. The polymers which are applied to the large-scale at present in the biodegradable plastic are mainly polylactic acid and PBAT, the main raw materials of the polylactic acid are lactic acid from starch at present, the PBAT is mainly derived from fossil base, the current cost of the PBAT and the polylactic acid is high, the barrier performance is relatively poor, and the degradation rate of the polylactic acid in soil and seawater environment is slow.
Polyglycolic acid (PGA), also known as polyglycolic acid, is an aliphatic polyester-based polymer material having a minimum number of carbon atoms, a completely decomposable ester structure, and a highest decomposition rate, and has been developed as a research hot spot. Unlike traditional polymer materials with stable performance, such as plastics, rubber and the like, polyglycolic acid is used as a material to be gradually degraded after being used for a certain time, and finally becomes carbon dioxide and water which are harmless to human bodies, animals, plants and natural environments, is one of the polymer materials with the best degradation performance known at present, is also a few polymer materials which are rapidly degraded in marine environments, and has great significance for solving the problem of severe white pollution at present.
Polyglycolic acid is mainly applied to the fields of medical suture lines, drug controlled release carriers, fracture fixing materials, tissue engineering scaffolds, reinforcing materials, oil fields and the like, but is also a rigid high-crystalline thermoplastic polymer, has short molecular chain structural units and poor chain flexibility, so that the polyglycolic acid has high brittleness, severely restricts the processing application of the polyglycolic acid in a plurality of fields, and aiming at the related technologies, the inventor discovers that the polyglycolic acid has poor toughness and is easy to crack in practical application.
Disclosure of Invention
In order to improve the toughness of a polyglycolic acid material, reduce brittleness and reduce brittle fracture, the application provides a polyglycolic acid material, a preparation method and application thereof.
In a first aspect, the present application provides a polyglycolic acid material, which adopts the following technical scheme:
the polyglycolic acid material comprises the following components in parts by weight: 10-40 parts of polyglycolic acid, 2.5-10 parts of toughening fiber, 0.01-0.8 part of compatilizer, 0.2-2 parts of nucleating agent, 0.1-2.5 parts of antioxidant and 0.2-0.8 part of lubricant;
the toughening fiber comprises seaweed carbon fiber and polyester fiber with the mass ratio of 0.3-0.7:1.
By adopting the technical scheme, the seaweed carbon fiber is fiber which is prepared by crushing seaweed carbon into ultrafine particles and spinning with polyester solution, has the effects of releasing anions and resisting bacteria, has higher impact strength and elongation at break, is a fiber material with strong toughness, and can not be melted again when the polyglycolic acid material is melted by using thermosetting polyester because the seaweed carbon fiber and the polyester fiber are prepared by using thermosetting polyester, so that the seaweed carbon fiber and the polyester fiber can be uniformly dispersed in the polyglycolic acid material under the action of a compatilizer and are mutually overlapped to form a network structure, thereby improving the toughness of the polyglycolic acid material and improving the impact strength and the elongation at break of the polyglycolic acid material.
Optionally, the preparation method of the polyester fiber comprises the following steps: mixing 0.3-0.5 part of polyvinyl alcohol aqueous solution with concentration of 0.5-1wt% and 0.1-0.3 part of modified carbon nano tube by weight, carrying out ultrasonic treatment, drying, melt extrusion to obtain a solid master batch, and then blending with 1-2 parts of PET slices, and spinning to obtain the polyester fiber.
By adopting the technical scheme, the carbon nano tube has extremely large specific surface area, light weight, high strength and good thermal stability, but is extremely easy to agglomerate and difficult to disperse in PET, so that the carbon nano tube is blended and extruded with polyvinyl alcohol, the polyvinyl alcohol is an amphoteric high molecular polymer, can be strongly adsorbed on the solid surface of the carbon nano tube in aqueous solution and forms a uniform coating on the surface of the carbon nano tube, hydrophobic groups of the polyvinyl alcohol are combined with the carbon nano tube in van der Waals force, hydrophilic groups extend into the solution, so that the carbon nano tube has electronegativity, the carbon nano tube is prevented from agglomerating, and then the carbon nano tube and solid master batch formed by the polyvinyl alcohol are blended and spun with PET to prepare the polyester fiber with high mechanical property.
Optionally, the preparation method of the modified carbon nanotube comprises the following steps:
adding cellulose nanofiber and glutaraldehyde into deionized water, and performing ultrasonic dispersion to prepare a suspension;
adding carbon nano tubes and a polyamide acid solution into the suspension, and performing ultrasonic dispersion for 20-30min to obtain a mixed dispersion;
the mixed dispersion liquid is placed at the temperature of between 18 and 20 ℃ for freezing for 20 to 24 hours, and then is frozen and dried for 40 to 48 hours, so as to prepare the mixed aerogel;
and (3) carbonizing the mixed aerogel in a nitrogen atmosphere to obtain the modified carbon nanotube.
By adopting the technical scheme, the cellulose nano-fibers are uniformly dispersed in deionized water, the dispersibility of the carbon nano-tubes in the deionized water can be improved, the cellulose nano-fibers and the deionized water are tightly wound to form a double-network structure, a large number of pore structures are formed by interweaving the fibers, the porosity of the network structure is improved, moisture is removed by freezing, a honeycomb-like network structure is obtained after vacuum drying, the high elasticity and high toughness of the mixed aerogel are realized, the oxygen-containing functional groups in the polyamide acid solution can form strong hydrogen bonds with the hydroxyl groups on the surface of the cellulose nano-fibers, the compatibility of the two components is enhanced, the polyamide solution is uniformly dispersed in the mixed dispersion liquid to form a second continuous network structure, and the cellulose nano-fibers form crosslinking at high temperature under the action of glutaraldehyde so as to enhance the mechanical property and the thermal stability of the three-dimensional framework; the main chain ester bond of the polyglycolic acid is free of hydrophobic groups, the glass transition temperature is low, the polyglycolic acid molecular chain has stronger activity capability in the room temperature environment, hydrolysis degradation reaction is easy to occur, the product performance is reduced, the hydrolysis degradation reaction of the polyvinyl alcohol is aggravated because the aerogel has hydrophilicity, the polyamide acid solution can coat the cellulose nanofiber to form a second continuous network structure, therefore, the mixed aerogel is carbonized at high temperature to form polyimide, a plurality of polar groups of the polyimide are embedded into an internal network, the hydrophilicity of the aerogel is reduced, the hydrophobic effect of the carbon nanotube is improved, the hydrolysis resistance of the polyglycolic acid is improved, the crosslinking between the cellulose nanofiber is firmer, and the toughness and the elasticity of the modified carbon nanotube are improved.
Optionally, the modified carbon nanotube is prepared from the following raw materials in parts by weight: 1 to 1.5 parts of cellulose nanofiber, 0.1 to 0.5 part of glutaraldehyde, 10 to 15 parts of deionized water, 1.5 to 2 parts of carbon nanotubes and 2 to 4 parts of polyamide acid solution.
By adopting the technical scheme, the modified carbon nano tube with good hydrophobicity, elasticity and toughness can be prepared by using the raw materials with the above dosage.
Optionally, the polyamic acid solution is prepared by mixing triethylamine terminated polyamic acid with a solid content of 15wt% with triethylamine and deionized water according to a mass ratio of 1:1:100-120.
By adopting the technical scheme, the polyamide acid solution is prepared from triethylamine-terminated polyamide acid with the solid content of 15wt%, triethylamine and the like, and is dehydrated at high temperature under the nitrogen atmosphere to be converted into polyimide with high heat resistance.
Optionally, the polyglycolic acid is pretreated by:
mixing the nanocellulose whisker with deionized water to prepare nanocellulose whisker suspension with the concentration of 2-2.5wt%, and carbonizing at 600-700 ℃ for 2-3 hours after freeze drying to prepare carbide;
mixing 0.05-0.1 part of carbide, 2-4 parts of polyethylene glycol and 0.01-0.02 part of stannous octoate by weight, heating to 90-95 ℃ in a water bath for 4-5 hours, adding ethanol for termination, centrifuging, dialyzing in water, and freeze-drying to prepare mixed powder; mixing the mixed powder, 0.5-1 part of polysiloxane and 5-8 parts of polyglycolic acid, and carrying out melt extrusion and granulation.
By adopting the technical scheme, as the glass transition temperature of the polyglycolic acid is low and the molecular chain does not contain hydrophobic groups, hydrolysis degradation reaction is easy to occur at room temperature, and the service life of the product is influenced; firstly, freezing and drying the nano cellulose whisker, carbonizing the nano cellulose whisker at a high temperature, wherein a large number of hydroxyl groups exist in the cellulose nano whisker, when the cellulose nano whisker is frozen and dried, the adjacent hydroxyl groups are subjected to hydrogen bonding to complete self-assembly, after the nano cellulose whisker is carbonized at a high temperature, the hydroxyl groups are removed, molecules are rearranged, an aromatic ring skeleton C=C and an aromatic ketone C=O structure is generated in the carbonized nano cellulose whisker, the possibility of self aggregation is reduced, the dispersion uniformity is improved, the heat-resistant stability is improved, and hydrophilic groups disappear after carbonization, so that the nano cellulose nano whisker becomes oleophylic and hydrophobic; and then mixing carbide with polyethylene glycol and stannous octoate, wherein the interface adhesion between the carbide and polyglycolic acid is strong, so that the impact strength and elongation at break of the polyglycolic acid can be improved, the elongation at break is increased, the toughness is increased due to the plasticizing effect of the polyethylene glycol, polysiloxane has more epoxy groups and amino groups and can react with carboxyl groups and hydroxyl groups of the chain ends of the polyglycolic acid, bonding on polyglycolic acid molecules is realized, the PGA filled with polysiloxane can increase the micro-nano structure of the PGA, the contact angle between the PGA and water is improved, and the hydrolysis stability of the polyglycolic acid is further improved.
Optionally, the seaweed carbon fiber is prepared by mixing and electrostatic spinning of seaweed carbon, polyester chips and an organic solvent in a mass ratio of 0.5-1:1-1.5:10.
By adopting the technical scheme, the seaweed carbon is ash prepared by roasting natural seaweed at high temperature, contains little sodium, contains abundant mineral substances, has good far infrared radiation efficiency, can permeate the subcutaneous foot of human skin to stimulate blood vessels, has good blood circulation, activates tissue cells, promotes metabolism in vivo, can better promote wound healing when being used for surgical suture lines, has hydrophobicity, has weak moisture absorption effect and strong hydrolysis resistance under the action of polyester slices with seaweed carbon fiber prepared by spinning polyester slices, and is difficult to hydrolyze and degrade at room temperature and has good durability.
Preferably, the electrostatic spinning speed is 0.1-0.2ml/min, the spinning voltage is 16-18kv, the rotating speed of the receiving roller is 80-90r/min, and the receiving distance is 15-18cm.
By adopting the technical scheme, the polyester fiber prepared by adopting the process for spinning has high impact strength, high elongation at break and strong mechanical property.
Optionally, the nucleating agent is ultrafine lead sulfide particles treated by a silane coupling agent.
By adopting the technical scheme, the development of polyglycolic acid materials is limited to a great extent by the dispersion problem of ultrafine lead sulfide particles in the polymer melt, the dispersibility of ultrafine lead sulfide particles in the polyglycolic acid melt is improved by a surface modification method, the problem of agglomeration can be effectively solved by KH560, the powder is changed from high surface energy to low surface energy, the powder is better combined with the polymer, the melting temperature of PGA is reduced, the PGA is prevented from being degraded due to the fact that the melting temperature is close to the thermal degradation temperature, and the application of the PGA is limited.
Optionally, the compatilizer is one or more selected from maleic anhydride grafted POE and maleic anhydride grafted styrene copolymer;
optionally, the antioxidant is selected from one or more of antioxidant 1010, antioxidant 168, antioxidant 626;
optionally, the lubricant is selected from one or more of polyethylene wax and polyethylene wax grafted glycidyl methacrylate.
In a second aspect, the present application provides a method for preparing a polyglycolic acid material, which adopts the following technical scheme: a method for preparing a polyglycolic acid material, comprising the steps of: mixing polyglycolic acid, compatilizer, antioxidant, nucleating agent, lubricant and toughening fiber, melting, extruding and granulating.
By adopting the technical scheme, the toughness of the polyglycolic acid material is improved by using materials such as toughened fibers, so that the toughness of the polyglycolic acid material is improved, and the polyglycolic acid material is not easy to break or crack due to high brittleness.
In a third aspect, the present application provides an application of a polyglycolic acid material, which adopts the following technical scheme:
the polyglycolic acid material is used in packing, spinning, medical material, disposable plastic product and agriculture.
By adopting the technical scheme, the polyglycolic acid material is used in the fields of packaging materials, textile materials and the like, and can improve the toughness of the materials, so that the brittleness of each plastic product is reduced, and the plastic product is not easy to crack.
In summary, the present application has the following beneficial effects:
1. because the seaweed carbon fiber and the polyester fiber are doped into the polyglycolic acid and are matched with materials such as compatilizer and antioxidant to prepare the polyglycolic acid material, the seaweed carbon fiber is made of seaweed carbon and polyester solution and is not easy to melt at high temperature, and the polyester fiber and the seaweed carbon fiber can form a mutually lapped network structure in the polyglycolic acid, so that when the polyglycolic acid is subjected to external stress, the anti-cracking effect is generated, the brittleness of the polyglycolic acid is reduced, and the impact strength and the breaking elongation of the polyglycolic acid are improved.
2. In the application, the modified carbon nano-tube, the polyvinyl alcohol and the PET are preferably blended to prepare the polyester fiber, the modified carbon nano-tube is prepared by blending cellulose nano-fiber, carbon nano-tube, polyamide acid solution and the like, freeze drying and carbonization, the cellulose nano-fiber and the carbon nano-tube can form a continuous three-dimensional network, an oxygen-containing functional group in the polyamide acid solution and the cellulose nano-fiber form a strong hydrogen bond, the compatibility of the cellulose nano-fiber and the cellulose nano-tube is improved, polyimide is formed after carbonization, a second continuous network structure is formed, the stretching resistance and elasticity of the modified carbon nano-tube are improved, the hydrophobicity of the modified carbon nano-tube is enhanced, and the room temperature hydrolysis resistance of polyglycolic acid is enhanced.
3. In the application, the cellulose nano whisker is carbonized to form oleophylic and hydrophobic carbide, and then is mixed with polysiloxane and polyglycolic acid for modification, so that the hydrophobicity of the polyglycolic acid is improved, and the hydrolysis resistance of the polyglycolic acid is improved.
Detailed Description
Preparation examples 1 to 5 of modified carbon nanotubes
Preparation example 1: (1) Adding 1.5kg of cellulose nanofiber and 0.5kg of glutaraldehyde into 15kg of deionized water, and performing ultrasonic dispersion for 20min at a power of 500W to prepare a suspension;
(2) Adding 2kg of carbon nano tubes and 4kg of polyamic acid solution into the suspension, performing ultrasonic dispersion for 20min at the power of 600W to obtain mixed dispersion, wherein the carbon nano tubes are multi-wall carbon nano tubes, have the diameter of 10-20nm and the purity of 95%, are selected from Shenzhen nanotechnology harbors, the polyamic acid solution is prepared by mixing triethylamine-terminated polyamic acid with the solid content of 15wt% and triethylamine and deionized water in the mass ratio of 1:1:100, and the triethylamine-terminated polyamic acid with the solid content of 15wt% is prepared by the following steps: 4.31g of 4,4' -diaminodiphenyl ether and 51g of dimethylacetamide are mixed and dissolved, 4.69g of pyromellitic anhydride is added for 3 times, stirred for 5 hours in an ice water bath at 0 ℃, 2.18g of triethylamine is added, stirred for 5 hours, poured into deionized water at 0 ℃ for deposition, washed for three times, frozen and freeze-dried;
(3) Freezing the mixed dispersion liquid at the temperature of minus 18 ℃ for 24 hours, and then carrying out vacuum freeze drying for 40 hours to obtain mixed aerogel;
(4) Carbonizing the mixed aerogel in a nitrogen atmosphere, wherein the carbonization method comprises the following steps: heating to 100 ℃ at the speed of 2 ℃/min, keeping the temperature for 30min, then heating to 200 ℃ at the speed of 2 ℃/min, keeping the temperature for 30min, heating to 300 ℃ at the speed of 2 ℃/min, and keeping the temperature for 60min.
Preparation example 2: (1) Adding 1kg of cellulose nanofiber and 0.1kg of glutaraldehyde into 10kg of deionized water, and performing ultrasonic dispersion for 20min at a power of 500W to prepare a suspension;
(2) Adding 1.5kg of carbon nano tube and 2kg of polyamic acid solution into the suspension, performing ultrasonic dispersion for 30min at the power of 600W to obtain mixed dispersion, wherein the carbon nano tube is multi-wall carbon nano tube, the diameter is 10-20nm, the purity is 95%, the mixed dispersion is selected from Shenzhen nanotechnology port, the polyamic acid solution is prepared by mixing triethylamine-terminated polyamic acid with the solid content of 15wt% and triethylamine and deionized water in the mass ratio of 1:1:120, and the triethylamine-terminated polyamic acid with the solid content of 15wt% is prepared by the following steps: 4.31g of 4,4' -diaminodiphenyl ether and 51g of dimethylacetamide are mixed and dissolved, 4.69g of pyromellitic anhydride is added for 3 times, stirred for 5 hours in an ice water bath at 0 ℃, 2.18g of triethylamine is added, stirred for 5 hours, poured into deionized water at 0 ℃ for deposition, washed for three times, frozen and freeze-dried;
(3) Freezing the mixed dispersion liquid at the temperature of minus 20 ℃ for 20 hours, and then performing vacuum freeze drying for 48 hours to prepare mixed aerogel;
(4) Carbonizing the mixed aerogel in a nitrogen atmosphere, wherein the carbonization method comprises the following steps: heating to 100 ℃ at the speed of 2 ℃/min, keeping the temperature for 30min, then heating to 200 ℃ at the speed of 2 ℃/min, keeping the temperature for 30min, heating to 300 ℃ at the speed of 2 ℃/min, and keeping the temperature for 60min.
Preparation example 3: the difference from preparation example 1 is that no polyamic acid solution was added.
Preparation example 4: the difference from preparation 1 is that the mixed aerogel was not carbonized.
Preparation example 5: the difference from preparation 1 is that an equal amount of nanocellulose whiskers was used instead of cellulose nanofibers.
Examples
Example 1: the polyglycolic acid material comprises the following raw materials in parts by weight: 40kg of polyglycolic acid, 10kg of toughening fiber, 0.8kg of compatilizer, 2kg of nucleating agent, 2.5kg of antioxidant and 0.8kg of lubricant, wherein the polyglycolic acid is selected from the technology of Wuhan mountain, the intrinsic viscosity is 1.39dL/g, the toughening fiber comprises seaweed carbon fiber and polyester fiber with the mass ratio of 0.7:1, the compatilizer is maleic anhydride grafted POE, the nucleating agent is ultrafine lead sulfide particles pretreated by silane coupling agent KH560, the antioxidant is antioxidant 1010, the lubricant is polyethylene wax, the seaweed carbon fiber is prepared by mixing seaweed carbon, polyester chips and organic solvent with the mass ratio of 0.5:1:10, the electrostatic spinning speed is 0.1mm/min, the spinning voltage is 16kv, the receiving drum rotating speed is 80r/min, the receiving distance is 15cm, and the organic solvent is trifluoroacetic acid and methylene dichloride with the mass ratio of 9:1.
The preparation method of the polyglycolic acid material comprises the following steps:
polyglycolic acid, compatilizer, antioxidant, nucleating agent, lubricant and toughening fiber are mixed, melted at 230 ℃, extruded and granulated.
Example 2: the polyglycolic acid material comprises the following raw materials in parts by weight: 10kg of polyglycolic acid, 2.5kg of toughening fiber, 0.01kg of compatilizer, 0.2kg of nucleating agent, 0.1kg of antioxidant and 0.2kg of lubricant, wherein the polyglycolic acid is selected from the technology of Wuhan mountain, the intrinsic viscosity is 1.39dL/g, the toughening fiber comprises seaweed carbon fiber and polyester fiber with the mass ratio of 0.3:1, the compatilizer is maleic anhydride grafted POE, the nucleating agent is ultrafine lead sulfide particles pretreated by a silane coupling agent KH560, the antioxidant is antioxidant 1010, the lubricant is polyethylene wax, the seaweed carbon fiber is prepared by mixing and electrostatic spinning seaweed carbon, polyester chips and an organic solvent with the mass ratio of 1:1.5:10, the electrostatic spinning speed is 0.1mm/min, the spinning voltage is 16kv, the rotating speed of a receiving roller is 80r/min, the receiving distance is 15cm, and the organic solvent is trifluoroacetic acid and methylene dichloride with the mass ratio of 9:1.
Example 3: a polyglycolic acid material, differing from example 1 in that a polyester fiber was produced by mixing 0.3kg of a 0.5wt% aqueous polyvinyl alcohol solution with 0.1kg of modified carbon nanotubes, sonicating for 2min, drying, melt-extruding at 170℃to produce a solid master batch, then blending with 1kg of PET chips, melt-spinning to produce a polyester fiber at 270℃with a receiving distance of 10cm, a spinneret diameter of 0.65mm, a spinning voltage of 16kv, and a modified carbon nanotube produced from production example 1 with a polyvinyl alcohol alcoholysis degree of 99%.
Example 4: a polyglycolic acid material, differing from example 1 in that a polyester fiber was produced by mixing 0.5kg of a polyvinyl alcohol aqueous solution having a concentration of 1wt% with 0.3kg of a modified carbon nanotube, sonicating for 2min, drying, melt-extruding at 180℃to obtain a solid master batch, then blending with 2kg of PET chips, spinning to obtain a polyester fiber at 270℃with a receiving distance of 10cm, a spinneret diameter of 0.65mm, a spinning voltage of 16kv, and a modified carbon nanotube produced from production example 2 with a polyvinyl alcohol alcoholysis degree of 99%.
Example 5: a polyglycolic acid material was different from example 4 in that modified carbon nanotubes were produced from production example 3.
Example 6: a polyglycolic acid material was different from example 4 in that modified carbon nanotubes were produced in production example 4.
Example 7: a polyglycolic acid material was different from example 4 in that modified carbon nanotubes were produced in production example 5.
Example 8: a polyglycolic acid material was different from example 4 in that no polyvinyl alcohol was added in the preparation of the polyester fiber.
Example 9: a polyglycolic acid material was different from example 4 in that modified carbon nanotubes were not added when the polyester fiber was prepared.
Example 10: a polyglycolic acid material differing from example 3 in that the polyglycolic acid was pretreated by: mixing the nanocellulose whisker with deionized water to prepare a nanocellulose whisker suspension with the concentration of 2wt%, and carbonizing at 600 ℃ for 3 hours after freeze drying to prepare carbide;
mixing 0.05kg of carbide with 2kg of polyethylene glycol with molecular weight of 6000 and 0.01kg of stannous octoate, heating in water bath at 90 ℃ for 5 hours, adding ethanol for termination, centrifuging, dialyzing in water, and freeze-drying to obtain mixed powder;
the mixed powder, 0.5kg of polysiloxane and 5kg of polyglycolic acid were mixed, melt extruded at 230℃and pelletized.
Example 11: a polyglycolic acid material differing from example 3 in that the polyglycolic acid was pretreated by: mixing the nanocellulose whisker with deionized water to prepare nanocellulose whisker suspension with the concentration of 2.5wt%, and carbonizing at 700 ℃ for 2 hours after freeze drying to prepare carbide;
mixing 0.1kg of carbide, 4kg of polyethylene glycol with molecular weight of 6000 and 0.02kg of stannous octoate, heating to 95 ℃ in a water bath for 4 hours, adding ethanol for termination, centrifuging, dialyzing in water, and freeze-drying to obtain mixed powder;
the mixed powder, 1kg of polysiloxane and 8kg of polyglycolic acid were mixed, melt extruded at 230℃and pelletized.
Example 12: a polyglycolic acid material differs from example 11 in that no polysiloxane was added.
Example 13: a polyglycolic acid material was different from example 11 in that polyethylene glycol was not added.
Example 14: a polyglycolic acid material differs from example 11 in that the nanocellulose whisker suspension is not freeze-dried and carbonized.
Comparative example
Comparative example 1: a polyglycolic acid material differs from example 1 in that no toughening fibers are added.
Comparative example 2: a polyglycolic acid material was different from example 1 in that seaweed carbon fibers were not added.
Comparative example 3: a polyglycolic acid material was different from example 1 in that no polyester fiber was added.
Comparative example 4: the modified PGA material with higher processability comprises the following raw materials in parts by weight: 10 parts of plasticizer, 80 parts of polyglycolic acid (PGA) with a molecular weight of 30 ten thousand g/mol, 10 parts of compatilizer (with an epoxy equivalent of 300 and a molecular weight of 8000 g/mol); the plasticizer is a blending material obtained by mixing polyvinyl alcohol with the alcoholysis degree of 88% and the molecular weight of 800g/mol and industrial grade ethylene glycol according to the mass ratio of 1:1, drying for 6 hours at 65 ℃, and mixing for 30 minutes by a high-speed mixer;
mixing the materials by a double-screw extrusion process for 15min by a high-speed mixer, drying the obtained mixed materials for 14h at the temperature of 25-30 ℃ and the relative humidity of 25%, and granulating by putting the mixed materials into double screws after the weight loss water content is 1.5-2%; the length-diameter ratio of the double-screw extruder is at least 1:55, meanwhile, the temperature of a feeding section is kept at about 170 ℃, the temperature of a mixing section is 230 ℃, and the temperature of an extruding section is kept at about 190 ℃; granulating by adopting an underwater granulating mode.
Comparative example 5: polyglycolic acid, purchased from Shanghai Pu Jing company, having a specific gravity of 1.24g/m3, a melt flow rate at 210℃of 2.16kg/10min and a number average molecular weight of 100000.
Performance test
Polyglycolic acid materials were prepared according to the above examples and comparative examples, and the properties of polyglycolic acid were measured by referring to the following methods, and the measurement results are recorded in table 1.
1. Impact strength: the detection is carried out according to GB/T1843-2008 'determination of impact strength of Plastic cantilever beam', the sample size is 80mm multiplied by 10mm multiplied by 4mm, and the notch depth is 2mm;
2. elongation at break: the test is carried out according to GB/T1040-2006 "measurement of Plastic tensile Property", and the tensile rate is set to 10mm/min;
3. contact angle: detection was performed using a SL15 optical contact angle tester;
4. hydrolysis rate: hydrolysis test was performed on polyglycolic acid material using a CA water bath thermostatted shaker at 65 ℃ and dried at hydrolysis time of 20h, weighed and the hydrolysis rate calculated: w= (1-m) 2 /m 1 ) V×100%, where: w is the hydrolysis rate, m 2 For the quality after hydrolysis, m 1 Is the mass before hydrolysis; and (5) continuing to stand for 30 days, taking out, measuring the impact strength, and calculating the retention rate of the impact strength: l=l 2 /L 1 X 100%, where L is impactRetention of strength, L 1 For initial impact strength, L 2 To test the post impact strength.
TABLE 1 results of Performance test of polyglycolic acid materials
Figure BDA0003885210810000091
As can be seen from the data in Table 1, in examples 1 and 2, seaweed carbon fibers and polyester fibers were used as toughening fibers, the seaweed carbon fibers were made of seaweed carbon and polyester chips, and the impact strength of the polyglycolic acid material reached 8J/m or more, and the elongation at break was more than 50%, with good toughness and elongation at break.
The modified carbon nanotubes prepared in preparation examples 1 and 2 were used in examples 3 and 4, and it is shown in table 1 that the polyglycolic acid materials prepared in examples 3 and 4 were improved in both impact strength and elongation at break, and improved in hydrophobicity and hydrolysis resistance, as compared with example 1.
Example 5 using the modified carbon nanotube produced in production example 3, the contact angle of the polyglycolic acid material produced in example 5 was decreased, the hydrolysis rate was increased, and the hydrolysis resistance was decreased as compared with example 1.
Example 6 Using the modified carbon nanotube produced in production example 4, the mixed aerogel was not carbonized in production example 4, and the polyglycolic acid material produced in example 6 was reduced in impact strength and elongation at break, reduced in contact angle, and reduced in hydrolysis resistance.
In example 7, modified carbon nanotubes prepared in preparation example 5 were used, and in preparation example 5, nanocellulose whiskers were used instead of cellulose nanofibers, and the polyglycolic acid material prepared in example 7 was inferior in impact strength and elongation at break, and was inferior in toughness, but was not much different in hydrolysis resistance from example 3, as compared with example 1.
Example 8 differs from example 3 in that no polyvinyl alcohol was added to the polyester fiber, and it is shown in table 1 that the contact angle of the polyglycolic acid material with water does not change much, but the impact strength and elongation at break decrease.
In example 9, since the modified carbon nanotubes were not added to the polyester fiber, the hydrophobicity of the polyglycolic acid material was decreased and the hydrolysis resistance was decreased as compared with example 3.
Examples 10 and 11 differ from example 3 in that polyglycolic acid was also pretreated with nanocellulose whisker carbide, polyethylene glycol, stannous octoate, and the like, and the impact strength and elongation at break of the polyglycolic acid materials prepared in examples 10 and 11 are shown in table 1 to be increased, and the contact angle with water is increased, and the hydrolysis resistance is enhanced.
In example 12, as compared with example 11, the contact angle with water was significantly increased, the hydrolysis rate was increased, the strength retention rate after hydrolysis was large, and the hydrolysis resistance was enhanced, as shown in table 1, for the polyglycolic acid material prepared in example 10.
In example 13, the impact strength and elongation at break of the polyglycolic acid material prepared in example 11 were reduced and the toughness was reduced, as compared with example 11, without polyethylene glycol.
Example 14 compared with example 11, without freeze-drying and carbonization of the nanocellulose whisker suspension, the toughness of the prepared polyglycolic acid material is not much different from that of example 9, but the contact angle with water is reduced, the hydrolysis rate is increased, the retention rate of impact strength after hydrolysis is reduced, and the hydrolysis resistance is reduced.
Comparative example 1 has no toughening fiber added and the toughness of the polyglycolic acid material is lowered compared with example 1, and in comparative examples 2 and 3, no alginate fiber and polyester fiber are added, respectively, and the impact strength and elongation at break of the polyglycolic acid materials prepared in comparative examples 2 and 3 are greater than those of comparative example 1, and toughness is improved but still worse than that of example 1.
In comparative example 4, the modified PGA material prepared by using PGA, plasticizer, compatibilizer, etc. was inferior in impact strength and elongation at break to example 1, and the hydrolysis resistance was slightly lowered.
Comparative example 5 is a commercially available polyglycolic acid, which has a small contact angle with water, poor mechanical strength, and poor toughness and hydrolysis resistance.
The present embodiment is merely illustrative of the present application and is not intended to be limiting, and those skilled in the art, after having read the present specification, may make modifications to the present embodiment without creative contribution as required, but is protected by patent laws within the scope of the claims of the present application.

Claims (5)

1. The polyglycolic acid material is characterized by comprising the following components in parts by weight: 10-40 parts of polyglycolic acid, 2.5-10 parts of toughening fiber, 0.01-0.8 part of compatilizer, 0.2-2 parts of nucleating agent, 0.1-2.5 parts of antioxidant and 0.2-0.8 part of lubricant;
the toughening fiber comprises seaweed carbon fiber and polyester fiber with the mass ratio of 0.3-0.7:1;
the preparation method of the polyester fiber comprises the following steps: mixing 0.3-0.5 part of polyvinyl alcohol aqueous solution with concentration of 0.5-1wt% with 0.1-0.3 part of modified carbon nano tube by weight, carrying out ultrasonic treatment, drying, melt extrusion to obtain a solid master batch, and then blending with 1-2 parts of PET slices, and spinning to obtain polyester fiber;
the seaweed carbon fiber is prepared by mixing and electrostatic spinning of seaweed carbon, polyester chips and an organic solvent in a mass ratio of 0.5-1:1-1.5:10;
the preparation method of the modified carbon nano tube comprises the following steps:
adding cellulose nanofiber and glutaraldehyde into deionized water, and performing ultrasonic dispersion to prepare a suspension;
adding carbon nano tubes and a polyamide acid solution into the suspension, and performing ultrasonic dispersion for 20-30min to obtain a mixed dispersion;
the mixed dispersion liquid is placed at the temperature of between 18 and 20 ℃ for freezing for 20 to 24 hours, and then is frozen and dried for 40 to 48 hours, so as to prepare the mixed aerogel;
carbonizing the mixed aerogel in a nitrogen atmosphere to obtain a modified carbon nanotube;
the modified carbon nanotube is prepared from the following raw materials in parts by weight:
1-1.5 parts of cellulose nanofiber, 0.1-0.5 part of glutaraldehyde, 10-15 parts of deionized water, 1.5-2 parts of carbon nanotubes and 2-4 parts of polyamic acid solution, wherein the polyamic acid solution is prepared by mixing triethylamine-terminated polyamic acid, triethylamine and deionized water, and the solid content of which is 15wt% in a mass ratio of 1:1:100-120.
2. The polyglycolic acid material of claim 1, wherein the polyglycolic acid is pretreated by:
mixing the nanocellulose whisker with deionized water to prepare nanocellulose whisker suspension with the concentration of 2-2.5wt%, and carbonizing at 600-700 ℃ for 2-3 hours after freeze drying to prepare carbide;
mixing 0.05-0.1 part of carbide, 2-4 parts of polyethylene glycol and 0.01-0.02 part of stannous octoate by weight, heating to 90-95 ℃ in a water bath for 4-5 hours, adding ethanol for termination, centrifuging, dialyzing in water, and freeze-drying to prepare mixed powder;
mixing the mixed powder, 0.5-1 part of polysiloxane and 5-8 parts of polyglycolic acid, and carrying out melt extrusion and granulation.
3. The polyglycolic acid material of claim 1, wherein the nucleating agent is ultra-fine lead sulfide particles treated with a silane coupling agent.
4. A process for the preparation of a polyglycolic acid material according to any one of claims 1 to 3, comprising the steps of:
mixing polyglycolic acid, compatilizer, antioxidant, nucleating agent, lubricant and toughening fiber, melting, extruding and granulating.
5. Use of the polyglycolic acid material of any one of claims 1-3 in packaging, textile, medical materials, disposable plastic articles, agricultural films.
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