CN115418092A - Polyglycolic acid material and preparation method and application thereof - Google Patents
Polyglycolic acid material and preparation method and application thereof Download PDFInfo
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Abstract
The application relates to the field of high polymer materials, and particularly discloses a polyglycolic acid material, and a preparation method and application thereof. The paint comprises the following components in parts by weight: 10-40 parts of polyglycolic acid, 2.5-10 parts of toughened 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 fibers comprise seaweed carbon fibers and polyester fibers in a mass ratio of 0.3-0.7; 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 hydrolytic reaction activity at room temperature and good durability.
Description
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 global emphasis on plastic pollution, degradable plastics have become a focus as a substitute for some plastic products which are not easy or easy to recycle. The polymers which are applied in large scale in the biodegradable plastic at present are mainly polylactic acid and PBAT, the main raw material of the polylactic acid is lactic acid from starch, the PBAT is mainly from fossil base, the PBAT and the polylactic acid have higher cost and poorer barrier property at present, and the polylactic acid has slower degradation rate in soil and seawater environment.
Polyglycolic acid (PGA), also called polyglycolic acid, is an aliphatic polyester polymer material with the least carbon number of units, a completely decomposable ester structure and the fastest degradation speed, and the application and development of the material become research hotspots. Different from traditional polymer materials with stable performance, such as plastics, rubber and the like, polyglycolic acid as a material is 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 environment, is one of the polymer materials with the best degradation performance at present, is also a few of polymer materials which are rapidly degraded in marine environment, and has great significance for solving the problem of severe white pollution at present.
Polyglycolic acid is mainly applied to the fields of medical sutures, drug controlled release carriers, fracture fixation materials, tissue engineering scaffolds, reinforcing materials, oil fields and the like, but is also a rigid high-crystalline thermoplastic polymer, and has large brittleness caused by short molecular chain structural units and poor chain flexibility, so that the processing application of the polyglycolic acid in many fields is severely restricted.
Disclosure of Invention
The application provides a polyglycolic acid material, a preparation method and application thereof, in order to improve the toughness of the polyglycolic acid material, reduce the brittleness and reduce the brittle fracture.
In a first aspect, the present application provides a polyglycolic acid material, which adopts the following technical scheme:
a polyglycolic acid material comprises the following components in parts by weight: 10-40 parts of polyglycolic acid, 2.5-10 parts of toughened 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 in a mass ratio of 0.3-0.7.
By adopting the technical scheme, the seaweed carbon fiber is prepared by crushing seaweed carbon into ultrafine particles and spinning the ultrafine particles and a polyester solution, has the effects of releasing negative ions and resisting bacteria, has higher impact strength and elongation at break, is a fiber material with obdurability, and is not melted again when the polyglycolic acid material is melted because the seaweed carbon fiber and the polyester fiber are prepared from thermosetting polyester, so the seaweed carbon fiber and the polyester fiber can be uniformly dispersed in the polyglycolic acid material under the action of the compatilizer and are mutually lapped 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: 0.3-0.5 part of polyvinyl alcohol aqueous solution with the concentration of 0.5-1wt% and 0.1-0.3 part of modified carbon nano tube are mixed and ultrasonically treated, dried, melted and extruded to prepare solid master batch, and then the solid master batch is mixed with 1-2 parts of PET slices and spun to prepare 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 because the carbon nano tube is extremely easy to agglomerate and is difficult to disperse in PET, the carbon nano tube and the polyvinyl alcohol are blended and extruded, the polyvinyl alcohol is an amphoteric high 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, the hydrophobic group of the polyvinyl alcohol is combined with the carbon nano tube by van der Waals force, and the hydrophilic group extends into the solution, so that the carbon nano tube has electronegativity, thereby preventing the carbon nano tube from agglomerating, and then the solid master batch formed by the carbon nano tube and the polyvinyl alcohol is blended and spun with the PET to prepare the polyester fiber with high mechanical property.
Optionally, the preparation method of the modified carbon nanotube includes the following steps:
adding cellulose nanofiber and glutaraldehyde into deionized water, and performing ultrasonic dispersion to prepare a suspension;
adding the carbon nano tube and the polyamic acid solution into the suspension, and performing ultrasonic dispersion for 20-30min to obtain a mixed dispersion liquid;
freezing the mixed dispersion liquid at the temperature of between 18 and 20 ℃ below zero for 20 to 24 hours, and then freezing and drying the mixed dispersion liquid for 40 to 48 hours to prepare mixed aerogel;
and carbonizing the mixed aerogel in a nitrogen atmosphere to obtain the modified carbon nano tube.
By adopting the technical scheme, the cellulose nano-fibers are uniformly dispersed in the 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 the high toughness of the mixed aerogel are realized, oxygen-containing functional groups in the polyamide acid solution can form strong hydrogen bonds with hydroxyl on the surfaces 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 cross-linking at high temperature under the action of glutaraldehyde, so that the mechanical property and the thermal stability of a three-dimensional framework are enhanced; the periphery of a main chain ester bond of polyglycolic acid has no hydrophobic group, and the glass transition temperature is low, so that a polyglycolic acid molecular chain has strong activity capability in a room temperature environment, hydrolysis degradation reaction is easy to occur, the performance of a product is reduced, the hydrolysis degradation reaction of polyvinyl alcohol is aggravated because the aerogel has hydrophilicity, a polyamide acid solution can coat cellulose nanofibers, and a second continuous network structure is formed, so that 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 nanotubes is improved, the hydrolysis resistance of the polyglycolic acid is improved, the crosslinking among the cellulose nanofibers is firmer, and the toughness and the elasticity of the modified carbon nanotubes are improved.
Optionally, the modified carbon nanotube is prepared from the following raw materials in parts by weight: 1-1.5 parts of cellulose nano-fiber, 0.1-0.5 part of glutaraldehyde, 10-15 parts of deionized water, 1.5-2 parts of carbon nano-tube and 2-4 parts of polyamic 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% and a mass ratio of 1.
By adopting the technical scheme, the polyamide acid solution is prepared from the triethylamine-terminated polyamide acid with the solid content of 15wt%, triethylamine and the like, and the polyamide acid solution is dehydrated at high temperature in a nitrogen atmosphere and is converted into the polyimide with high heat resistance.
Optionally, the polyglycolic acid is pretreated by:
mixing the nano-cellulose whiskers with deionized water to prepare a nano-cellulose whisker suspension with the concentration of 2-2.5wt%, and carbonizing for 2-3 hours at 600-700 ℃ 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 in parts by weight, heating to 90-95 ℃ in a water bath for 4-5h, 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 performing melt extrusion and granulation.
By adopting the technical scheme, because the glass transition temperature of the polyglycolic acid is low, and no hydrophobic group is contained in a molecular chain, the polyglycolic acid is very easy to generate hydrolytic degradation reaction at room temperature, and the service life of a product is influenced; firstly, the nano-cellulose whisker is carbonized at high temperature after being frozen and dried, a large number of hydroxyl groups exist in the cellulose nano-whisker, during freezing and drying, the adjacent hydroxyl groups finish self-assembly through the action of hydrogen bonds, and after high-temperature carbonization, the hydroxyl groups are removed and the molecules are rearranged, so that aromatic ring skeleton C = C and aromatic ketone C = O structures are 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, and the nano-cellulose whisker becomes oleophilic and hydrophobic; and then mixing the carbide with polyethylene glycol and stannous octoate, wherein the interface adhesion between the carbide and polyglycolic acid is strong, the impact strength and the elongation at break of the polyglycolic acid can be improved, the elongation at break is increased due to the plasticizing effect of the polyethylene glycol, the toughness is increased, the polysiloxane has more epoxy groups and amino groups, and can react with carboxyl and hydroxyl at the chain end of the polyglycolic acid to realize the bonding on polyglycolic acid molecules, and the PGA filled with the polysiloxane can increase the micro-nano structure of the PGA, improve the contact angle of the PGA and water and further improve the hydrolysis stability of the polyglycolic acid.
Optionally, the seaweed carbon fiber is prepared by mixing and electrospinning seaweed carbon, polyester chips and an organic solvent according to a mass ratio of 0.5-1:1-1.5.
Through adopting above-mentioned technical scheme, the seaweed carbon is the ash that natural seaweed made through the high temperature calcination, the sodium content is few in the seaweed carbon, contain abundant mineral substance, good far infrared radiation efficiency has, can soak the subcutaneous sufficient amazing blood vessel of human skin, make blood circulation good, make histiocyte activation, promote metabolism in vivo, when being used for the operation stylolite, can be better promote wound healing, and the seaweed carbon has the hydrophobicity, the seaweed carbon fiber who makes with polyester section spinning is under the effect of polyester section, the moisture absorption is weak, hydrolysis resistance is strong, the difficult hydrolytic degradation of goods at room temperature, the durability is good.
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 and adopting the process for spinning, the prepared polyester fiber has high impact strength, large 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 due to the dispersion problem of ultrafine lead sulfide particles in a polymer melt, the dispersibility of the ultrafine lead sulfide particles in the polyglycolic acid melt is improved by a surface modification method, the KH560 can effectively solve the agglomeration problem, the powder is changed from high surface energy to low surface energy, the powder is better combined with the polymer, the melting temperature of the 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 during molding, and the application of the PGA is limited.
Optionally, the compatilizer is selected from one or more of maleic anhydride grafted POE and maleic anhydride grafted styrene copolymer;
optionally, the antioxidant is selected from one or more of antioxidant 1010, antioxidant 168 and 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 preparation method of a polyglycolic acid material comprises the following steps: 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 is improved by using materials such as toughening 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:
an application of polyglycolic acid material in the fields of packaging, textile, medical material, disposable plastic products 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 material, reduce the brittleness of various plastic products and prevent cracking.
In summary, the present application has the following beneficial effects:
1. according to the application, the seaweed carbon fiber and the polyester fiber are doped into the polyglycolic acid and are matched with materials such as a compatilizer and an antioxidant to prepare the polyglycolic acid material, the seaweed carbon fiber is prepared from the seaweed carbon and the polyester solution, so that the seaweed carbon fiber 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, an anti-cracking effect is generated, the brittleness of the polyglycolic acid is reduced, and the impact strength and the elongation at break of the polyglycolic acid are improved.
2. In the application, the modified carbon nano tube, polyvinyl alcohol and PET are preferably selected to prepare the polyester fiber through blending spinning, the modified carbon nano tube is prepared by blending, freeze drying and carbonizing cellulose nano fiber, the carbon nano tube and polyamide acid solution, and the like, the cellulose nano fiber and the carbon nano tube can form a continuous three-dimensional network, oxygen-containing functional groups in the polyamide acid solution and the cellulose nano fiber form strong hydrogen bonds to improve the compatibility of the cellulose nano fiber and the carbon nano tube, polyimide is formed after carbonization, a second continuous network structure is formed, the tensile resistance and the 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. According to the application, the cellulose nanowhiskers are carbonized to form oleophilic and hydrophobic carbides, and then the oleophilic and hydrophobic carbides are 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 ultrasonically dispersing for 20min at the power of 500W to prepare a suspension;
(2) Adding 2kg of carbon nanotubes and 4kg of a polyamic acid solution into the suspension, and ultrasonically dispersing for 20min at a power of 600W to prepare a mixed dispersion solution, wherein the carbon nanotubes are multi-walled carbon nanotubes, the diameter of the carbon nanotubes is 10-20nm, the purity of the carbon nanotubes is 95%, the polyamic acid solution is prepared by mixing triethylamine-terminated polyamic acid with a solid content of 15wt% and triethylamine and deionized water in a mass ratio of 1: 4.31g of 4,4' -diaminodiphenyl ether and 51g of dimethylacetamide are mixed and dissolved, 4.69g of pyromellitic anhydride is added in 3 times, the mixture is stirred for 5 hours in an ice-water bath at the temperature of 0 ℃, 2.18g of triethylamine is added, the mixture is stirred for 5 hours, the mixture is poured into deionized water at the temperature of 0 ℃ for deposition, and after the mixture is washed for three times, the mixture is frozen and then freeze-dried;
(3) Freezing the mixed dispersion liquid at-18 ℃ for 24 hours, and then carrying out vacuum freeze drying for 40 hours to prepare a mixed aerogel;
(4) The mixed aerogel is carbonized in a nitrogen atmosphere, and the carbonization method comprises the following steps: heating to 100 deg.C at a speed of 2 deg.C/min, maintaining the temperature for 30min, heating to 200 deg.C at a speed of 2 deg.C/min, maintaining the temperature for 30min, heating to 300 deg.C at a speed of 2 deg.C/min, and maintaining the temperature for 60min.
Preparation example 2: (1) Adding 1kg of cellulose nanofiber and 0.1kg of glutaraldehyde into 10kg of deionized water, and ultrasonically dispersing for 20min at the power of 500W to prepare a suspension;
(2) Adding 1.5kg of carbon nanotubes and 2kg of polyamic acid solution into the suspension, and ultrasonically dispersing for 30min at 600W to prepare a mixed dispersion solution, wherein the carbon nanotubes are multi-walled carbon nanotubes, the diameter of the carbon nanotubes is 10-20nm, the purity of the carbon nanotubes is 95%, the carbon nanotubes are selected from Shenzhen nanotechnology harbors, the polyamic acid solution is prepared by mixing 15wt% of triethylamine-terminated polyamic acid, triethylamine and deionized water, and the mass ratio of the triethylamine-terminated polyamic acid to the polyamic acid solution is 1: 4.31g of 4,4' -diaminodiphenyl ether and 51g of dimethylacetamide are mixed and dissolved, 4.69g of pyromellitic anhydride is added in 3 times, the mixture is stirred for 5 hours in an ice-water bath at the temperature of 0 ℃, 2.18g of triethylamine is added, the mixture is stirred for 5 hours, the mixture is poured into deionized water at the temperature of 0 ℃ for deposition, and after the mixture is washed for three times, the mixture is frozen and then freeze-dried;
(3) Freezing the mixed dispersion liquid at-20 ℃ for 20h, and then carrying out vacuum freeze drying for 48h to obtain mixed aerogel;
(4) The mixed aerogel is carbonized in a nitrogen atmosphere, and the carbonization method comprises the following steps: heating to 100 deg.C at a speed of 2 deg.C/min, maintaining the temperature for 30min, heating to 200 deg.C at a speed of 2 deg.C/min, maintaining the temperature for 30min, heating to 300 deg.C at a speed of 2 deg.C/min, and maintaining 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 example 1 is that the mixed aerogel was not carbonized.
Preparation example 5: the difference from preparation example 1 is that equal amount of nanocellulose whiskers was used instead of cellulose nanofibers.
Examples
Example 1: a polyglycolic acid material comprises the following raw materials in parts by weight: 40kg of polyglycolic acid, 10kg of toughened fibers, 0.8kg of compatilizer, 2kg of nucleating agent, 2.5kg of antioxidant and 0.8kg of lubricant, wherein the polyglycolic acid is selected from Wuhan Haishan science and technology, the intrinsic viscosity is 1.39dL/g, the toughened fibers comprise seaweed carbon fibers and polyester fibers with the mass ratio of 0.7.
The preparation method of the polyglycolic acid material comprises the following steps:
mixing polyglycolic acid, compatilizer, antioxidant, nucleating agent, lubricant and toughening fiber, melting at 230 ℃, extruding and granulating.
Example 2: a polyglycolic acid material comprises the following raw materials in percentage by weight: 10kg of polyglycolic acid, 2.5kg of toughening fibers, 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 Wuhan Haishan technology, the intrinsic viscosity is 1.39dL/g, the toughening fibers comprise seaweed carbon fibers and polyester fibers in a mass ratio of 0.3.
Example 3: a polyglycolic acid material, which is different from example 1 in that a polyester fiber is prepared by mixing 0.3kg of a polyvinyl alcohol aqueous solution having a concentration of 0.5wt% with 0.1kg of modified carbon nanotubes, subjecting the mixture to ultrasonic treatment for 2min, drying the mixture, melt-extruding the mixture at 170 ℃ to prepare a solid master batch, blending the solid master batch with 1kg of PET chips, and melt-spinning the mixture to prepare a polyester fiber, wherein the spinning temperature is 270 ℃, the take-up distance is 10cm, the diameter of a spinneret hole is 0.65mm, the spinning voltage is 16kv, the modified carbon nanotubes are prepared according to preparation example 1, and the degree of alcoholysis of polyvinyl alcohol is 99%.
Example 4: a polyglycolic acid material different from example 1 in that a polyester fiber was prepared by mixing 0.5kg of a polyvinyl alcohol aqueous solution having a concentration of 1wt% and 0.3kg of modified carbon nanotubes, ultrasonic treating for 2min, drying, melt-extruding at 180 ℃ to prepare a solid master batch, blending with 2kg of PET chips, and spinning at 270 ℃ with a receiving distance of 10cm, a spinneret hole diameter of 0.65mm and a spinning voltage of 16kv to prepare a polyester fiber, wherein the modified carbon nanotubes were prepared according to preparation example 2 and a degree of alcoholysis of polyvinyl alcohol was 99%.
Example 5: a polyglycolic acid material, which is different from example 4 in that a modified carbon nanotube was produced by preparative example 3.
Example 6: a polyglycolic acid material, which is different from example 4 in that a modified carbon nanotube was produced according to preparation example 4.
Example 7: a polyglycolic acid material different from example 4 in that modified carbon nanotubes were prepared as in preparation example 5.
Example 8: a polyglycolic acid material different from that of example 4 in that polyvinyl alcohol was not added at the time of preparing the polyester fiber.
Example 9: a polyglycolic acid material is different from that in example 4 in that modified carbon nanotubes are not added at the time of preparing polyester fibers.
Example 10: a polyglycolic acid material, differing from example 3 in that polyglycolic acid was pretreated by: mixing the nano-cellulose whiskers with deionized water to prepare a nano-cellulose whisker suspension with the concentration of 2wt%, and carbonizing at 600 ℃ for 3 hours after freeze drying to prepare carbide;
mixing 0.05kg of the carbide with 2kg of polyethylene glycol with molecular weight of 6000 and 0.01kg of stannous octoate, heating to 90 ℃ in a water bath for 5h, adding ethanol for termination, centrifuging, dialyzing in water, and freeze-drying to prepare mixed powder;
the mixed powder, 0.5kg of polysiloxane and 5kg of polyglycolic acid were mixed, melt-extruded at 230 ℃ and granulated.
Example 11: a polyglycolic acid material, differing from example 3 in that polyglycolic acid was pretreated by: mixing the nano-cellulose whiskers with deionized water to prepare a nano-cellulose whisker suspension with the concentration of 2.5wt%, and carbonizing for 2 hours at 700 ℃ after freeze drying to prepare carbide;
mixing 0.1kg of the carbide with 4kg of polyethylene glycol with molecular weight of 6000 and 0.02kg of stannous octoate, heating to 95 ℃ in a water bath for 4h, adding ethanol for termination, centrifuging, dialyzing in water, and freeze-drying to prepare mixed powder;
the mixed powder, 1kg of polysiloxane and 8kg of polyglycolic acid were mixed, melt-extruded at 230 ℃ and granulated.
Example 12: a polyglycolic acid material, which is different from that of example 11 in that no polysiloxane was added.
Example 13: a polyglycolic acid material, which is different from that of example 11 in that polyethylene glycol is not added.
Example 14: a polyglycolic acid material, differing from example 11 in that the nanocellulose whisker suspension was not freeze-dried and carbonized.
Comparative example
Comparative example 1: a polyglycolic acid material which differs from example 1 in that no toughening fibers are added.
Comparative example 2: a polyglycolic acid material which is different from that of example 1 in that no algal charcoal fiber is added.
Comparative example 3: a polyglycolic acid material, which is different from that of example 1 in that no polyester fiber is added.
Comparative example 4: a modified PGA material with high processing performance comprises the following raw materials in percentage by weight: 10 parts of a plasticizer, 80 parts of polyglycolic acid (PGA) having a molecular weight of 30 ten thousand g/mol, and 10 parts of a compatibilizer (epoxy equivalent of 300 and molecular weight of 8000 g/mol); the plasticizer is a blending material which is obtained by mixing polyvinyl alcohol with alcoholysis degree of 88% and 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 then mixing for 30 minutes by a high-speed mixer;
the materials are extruded by a double screw extruder, the raw materials are mixed for 15min by a high-speed mixer, the obtained mixed material is dried for 14h at the relative humidity of 25% and the temperature of 25-30 ℃, and the obtained mixed material is put into the double screw extruder for granulation after the weight-loss water content is 1.5-2%; the length-diameter ratio of the double-screw extruder at least reaches 1 to 55, the temperature of a feeding section is kept at about 170 ℃, the temperature of a mixing section is 230 ℃, and the temperature of an extrusion section is kept at about 190 ℃; granulating by adopting an underwater granulating mode.
Comparative example 5: polyglycolic acid, purchased from Shanghai Pu Jing, having a specific gravity of 1.24g/m3, a melt 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 with reference to the following methods, and the measurement results are reported in table 1.
1. Impact strength: the detection is carried out according to GB/T1843-2008 'determination of plastic cantilever beam impact strength', the sample size is 80mm multiplied by 10mm multiplied by 4mm, and the notch depth is 2mm;
2. elongation at break: testing according to GB/T1040-2006 'determination of plastic tensile property', wherein the tensile rate is set to be 10mm/min;
3. contact angle: detecting by using an SL15 type optical contact angle tester;
4. hydrolysis rate: the polyglycolic acid material was subjected to hydrolysis test at 65 ℃ using a CA water bath constant temperature oscillator, and dried at a hydrolysis time of 20 hours, weighed, and the hydrolysis rate was calculated: w = (1-m) 2 /m 1 ) 100%, wherein: w is the hydrolysis ratio, m 2 M is mass after hydrolysis 1 Mass before hydrolysis; and (3) continuously placing 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%, wherein L is the retention of impact strength, L 1 As initial impact strength, L 2 To test the post impact strength.
TABLE 1 Performance test results for polyglycolic acid materials
As can be seen from the data in Table 1, in examples 1 and 2, the seaweed carbon fiber and the polyester fiber are used as the toughening fiber, the seaweed carbon fiber is made of seaweed carbon and polyester chips, the impact strength of the polyglycolic acid material reaches more than 8J/m, the elongation at break is more than 50%, and the polyglycolic acid material has good toughness and elongation at break.
In examples 3 and 4, the modified carbon nanotubes prepared in production examples 1 and 2 were used as compared with example 1, and table 1 shows that the polyglycolic acid materials prepared in examples 3 and 4 have improved impact strength and elongation at break, improved hydrophobicity, and improved hydrolysis resistance.
Example 5 using the modified carbon nanotubes prepared in preparation example 3, the polyglycolic acid material prepared in example 5 had a smaller contact angle, a higher hydrolysis ratio, and a lower hydrolysis resistance than those of example 1.
Example 6 the modified carbon nanotubes prepared in preparation example 4 were used, the mixed aerogel in preparation example 4 was not carbonized, and the polyglycolic acid material prepared in example 6 was reduced in impact strength and elongation at break, contact angle and hydrolysis resistance.
In example 7, the modified carbon nanotubes prepared in preparation example 5 were used, and in preparation example 5, the nanocellulose whiskers were used instead of the cellulose nanofibers, and the polyglycolic acid material prepared in example 7 was lower in impact strength and elongation at break and lower in toughness than in example 1, but the hydrolysis resistance was not much different from that in example 3.
Example 8 is different from example 3 in that polyvinyl alcohol was not added to the polyester fiber, and table 1 shows that the contact angle of the polyglycolic acid material with water did not change much, but the impact strength and elongation at break were decreased.
In example 9, since the modified carbon nanotubes were not added to the polyester fibers, the polyglycolic acid material had lower hydrophobicity and lower hydrolysis resistance than in example 3.
The difference between examples 10 and 11 and example 3 is that polyglycolic acid was also pretreated with a carbide of nanocellulose whisker, polyethylene glycol, stannous octoate, etc., and table 1 shows that polyglycolic acid materials prepared in examples 10 and 11 have increased impact strength and elongation at break, increased contact angle with water, and increased hydrolysis resistance.
In example 12, compared with example 11, in table 1, without adding polysiloxane, it is shown that the polyglycolic acid material prepared in example 10 has a significantly increased contact angle with water, an increased hydrolysis ratio, a high strength retention after hydrolysis, and an enhanced hydrolysis resistance.
In example 13, compared to example 11, without addition of polyethylene glycol, it is shown in table 1 that the polyglycolic acid material prepared in example 11 has decreased impact strength and elongation at break, and decreased toughness.
In example 14, compared with example 11, the toughness of the polyglycolic acid material prepared without freeze-drying and carbonization of the nanocellulose whisker suspension was not much different from that of example 9, but the contact angle with water was decreased, the hydrolysis rate was increased, the retention rate of impact strength after hydrolysis was decreased, and the hydrolysis resistance was decreased.
Comparative example 1 compared to example 1, the polyglycolic acid material had decreased toughness without the addition of toughening fibers, comparative example 2 and comparative example 3 did not include alginate fibers and polyester fibers, respectively, and the polyglycolic acid materials made in comparative example 2 and comparative example 3 had greater impact strength and elongation at break than comparative example 1, improved toughness, but still inferior to example 1.
In comparative example 4, when PGA, a plasticizer, a compatibilizer, etc. were used to balance the modified PGA material, the impact strength and elongation at break were inferior to those of example 1, and the hydrolysis resistance was slightly lowered.
Comparative example 5 is a commercially available polyglycolic acid having a small contact angle with water, poor mechanical strength, and poor toughness and hydrolysis resistance.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (10)
1. A 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 toughened 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 fibers comprise seaweed carbon fibers and polyester fibers in a mass ratio of 0.3-0.7.
2. A polyglycolic acid material according to claim 1, characterized in that: the preparation method of the polyester fiber comprises the following steps: 0.3 to 0.5 portion of polyvinyl alcohol aqueous solution with the concentration of 0.5 to 1 weight percent and 0.1 to 0.3 portion of modified carbon nano tube are mixed, ultrasonically treated, dried, melted and extruded to prepare solid master batch, and then the solid master batch is mixed with 1 to 2 portions of PET slices and spun to prepare the polyester fiber.
3. The polyglycolic acid material according to claim 2, wherein the method for preparing the modified carbon nanotubes comprises the steps of:
adding cellulose nanofiber and glutaraldehyde into deionized water, and performing ultrasonic dispersion to prepare a suspension;
adding the carbon nano tube and the polyamic acid solution into the suspension, and performing ultrasonic dispersion for 20-30min to obtain a mixed dispersion liquid;
freezing the mixed dispersion liquid at the temperature of between 18 and 20 ℃ below zero for 20 to 24 hours, and then freezing and drying the mixed dispersion liquid for 40 to 48 hours to prepare mixed aerogel;
and carbonizing the mixed aerogel in a nitrogen atmosphere to obtain the modified carbon nano tube.
4. The polyglycolic acid material according to claim 3, wherein the modified carbon nanotubes are prepared from the following raw materials in parts by weight:
1-1.5 parts of cellulose nano-fiber, 0.1-0.5 part of glutaraldehyde, 10-15 parts of deionized water, 1.5-2 parts of carbon nano-tube and 2-4 parts of polyamic acid solution.
5. The polyglycolic acid material according to claim 3, wherein the polyamic acid solution is prepared by mixing triethylamine-terminated polyamic acid with a solid content of 15wt% and triethylamine, and deionized water in a mass ratio of 1.
6. The polyglycolic acid material according to claim 1, which is pre-treated with:
mixing the nano-cellulose whiskers with deionized water to prepare a nano-cellulose whisker suspension with the concentration of 2-2.5wt%, and carbonizing for 2-3 hours at 600-700 ℃ 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 in parts by weight, heating to 90-95 ℃ in a water bath for 4-5h, 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 performing melt extrusion and granulation.
7. The polyglycolic acid material according to claim 1, wherein the seaweed carbon fiber is prepared by mixing and electrospinning seaweed carbon, polyester chips and an organic solvent in a mass ratio of 0.5-1:1-1.5.
8. The polyglycolic acid material according to claim 1, wherein the nucleating agent is ultrafine lead sulfide particles treated with a silane coupling agent.
9. A method of preparing a polyglycolic acid material according to any one of claims 1 to 8, comprising the steps of:
mixing polyglycolic acid, compatilizer, antioxidant, nucleating agent, lubricant and toughening fiber, melting, extruding and granulating.
10. Use of a polyglycolic acid material according to any one of claims 1 to 8 for packaging, textile, medical materials, disposable plastic articles, agricultural films.
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