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CN-122011402-A - PGA resin edge grafting modified graphene, composition, preparation method and application thereof, biodegradable polyester material, application thereof and temporary plugging ball

CN122011402ACN 122011402 ACN122011402 ACN 122011402ACN-122011402-A

Abstract

The invention belongs to the technical field of high polymer materials, and discloses PGA resin edge grafting modified graphene, a composition, a preparation method and application thereof, a biodegradable polyester material and an application and temporary plugging ball thereof, wherein the PGA resin edge grafting modified graphene comprises graphene and a polyglycolic acid resin grafted on the edge of the PGA resin edge grafting modified graphene, and the mass percentage of the polyglycolic acid resin grafted in the PGA resin edge grafting modified graphene is 1-20%, preferably 3-15% based on the total mass of the PGA resin edge grafting modified graphene. The PGA resin edge grafting modified graphene has good thermal conductivity and large aspect ratio.

Inventors

  • GUO PENG
  • LV MINGFU
  • WU CHANGJIANG
  • ZHANG ZONGYIN
  • XU YAOHUI
  • ZHANG SHIJUN
  • GAO DALI
  • ZHANG HAO
  • WANG XINGGUO

Assignees

  • 中国石油化工股份有限公司
  • 中石化(北京)化工研究院有限公司

Dates

Publication Date
20260512
Application Date
20241112

Claims (20)

  1. 1. The PGA resin edge grafting modified graphene is characterized by comprising graphene and a polyglycolic acid resin grafted on the edge of the graphene, wherein the mass percentage of the polyglycolic acid resin grafted in the PGA resin edge grafting modified graphene is 1-20%, preferably 3-15%, based on the total mass of the PGA resin edge grafting modified graphene.
  2. 2. The PGA-based resin edge-grafted modified graphene according to claim 1, wherein the PGA-based resin edge-grafted modified graphene has an average sheet diameter of 2-6 μm; And/or the aspect ratio of the PGA resin edge grafting modified graphene is (180-1850): 1, preferably (200-1750): 1, and more preferably (560-1650): 1.
  3. 3. The PGA-based resin edge-grafted modified graphene according to claim 1, wherein the thermal conductivity of the PGA-based resin edge-grafted modified graphene is 200-400W/m-K, preferably 220-320W/m-K.
  4. 4. A method for preparing the PGA-based resin edge-grafted modified graphene according to any one of claims 1 to 3, comprising the steps of: And in the presence of non-inflammable mixed gas, grinding and mixing the polyglycolic acid resin and graphite to obtain the PGA resin edge grafting modified graphene.
  5. 5. The process according to claim 4, wherein the graphite is natural graphite and/or artificial graphite, the natural graphite is selected from crystalline graphite and/or aphanitic graphite, and the artificial graphite is selected from thermally cracked graphite and/or highly oriented thermally cracked graphite; The graphite is preferably crystalline graphite, and the crystalline graphite is preferably crystalline flake graphite, more preferably, the fixed carbon mass content of the crystalline flake graphite is more than or equal to 99.9% or the fixed carbon mass content is 94% -99.9%, and even more preferably, the fixed carbon mass content of the crystalline flake graphite is more than or equal to 99.9%; the aphanitic graphite is preferably a graphite in the form of a soil; The particle size of the graphite is 100 to 5000 mesh, preferably 200 to 4000 mesh, further preferably 200 to 2000 mesh, and more preferably 200 to 400 mesh.
  6. 6. The process according to claim 4, wherein the melt flow rate of the polyglycolic acid-based resin at 230 ℃ under a load of 2.16kg is 5-60g/10min, preferably 10-50g/10min, more preferably 15-45g/10min; And/or the weight average molecular weight of the polyglycolic acid-based resin is 1 ten thousand to 80 ten thousand, preferably 2 ten thousand to 30 ten thousand, more preferably 5 ten thousand to 20 ten thousand; and/or the molecular weight distribution width Mw/Mn of the polyglycolic acid-based resin is 1 to 5, preferably 1.5 to 3.5; And/or, the polyglycolic acid resin is homo-polyglycolic acid and/or co-polyglycolic acid, preferably homo-polyglycolic acid.
  7. 7. The preparation method of claim 4, wherein the non-flammable mixed gas comprises 30-50wt% of carbon dioxide, 45-65wt% of nitrogen and 0-5wt% of argon, based on the total weight of the non-flammable mixed gas; the conditions of the milling and mixing include a milling rotation speed of 5-250 rpm, preferably 10-200 rpm, a cyclic milling time of 10-300 hours, preferably 15-200 hours, more preferably 24-120 hours, a pressure of 15-25MPa in the milling and mixing device, and a milling and mixing temperature of 40-50 ℃; the grinding and mixing are preferably carried out in a closed system with a circulation function, and more preferably in a high-pressure millstone kettle with a supercritical fluid circulation function.
  8. 8. A PGA composition containing PGA resin edge grafting modified graphene is characterized by comprising a polyglycolic acid resin, the PGA resin edge grafting modified graphene according to any one of claims 1-3, a bio-based elastomer, an antioxidant, a nucleating agent, a chain extender and a hydrolysis inhibitor.
  9. 9. PGA composition according to claim 8, wherein the antioxidant is contained in an amount of 0.15 to 0.25 parts by weight, the nucleating agent is contained in an amount of 0.13 to 0.46 parts by weight, the chain extender is contained in an amount of 0.1 to 2 parts by weight, preferably 0.2 to 1 part by weight, and the hydrolysis inhibitor is contained in an amount of 0.1 to 2 parts by weight, preferably 0.5 to 1.2 parts by weight, relative to 100 parts by weight of the resin composition; The resin composition consists of polyglycolic acid, the PGA resin edge grafting modified graphene in any one of claims 1-3 and a bio-based elastomer, wherein the mass ratio of the polyglycolic acid resin to the PGA resin edge grafting modified graphene in any one of claims 1-3 to the bio-based elastomer is (80-95): 4-18): 1-6; Preferably, the antioxidant comprises a primary antioxidant and a secondary antioxidant, and the mass ratio of the primary antioxidant to the secondary antioxidant is (0.5-1): 1.
  10. 10. The PGA composition of claim 8 or 9, wherein the bio-based elastomer is selected from at least one of a poly (sebacate-glycerol) ester elastomer, an acrylated poly (sebacate-glycerol) ester elastomer, a poly (citrate-1, 8-octanediol) ester elastomer, a copolymer of lactide-caprolactone, a glycolide-lactide copolymer, a glycolide-lactide-caprolactone terpolymer, a poly (ester-carbonate) elastomer, a poly (citrate-octanediol-sebacate) ester elastomer, a poly (sebacate-glycerol-citrate) ester elastomer, a poly (sebacate-1, 2-propanediol-citrate) ester elastomer, a poly (itaconate-isoprene-glycidyl methacrylate) elastomer, a soybean oil-based elastomer, a tri-epoxy structure-containing itaconate elastomer, and a myrcene bio-based elastomer; preferably, the bio-based elastomer has a weight average molecular weight of 5 to 10 ten thousand and a molecular weight distribution width Mw/Mn of 1 to 3.
  11. 11. The PGA composition of claim 9, wherein the primary antioxidant is at least one selected from the group consisting of antioxidant 1010 (pentaerythritol tetrakis [ β - (3, 5-di-t-butyl-4-hydroxyphenyl) propionate; CAS No. 6683-19-8), antioxidant 3114 (1, 3, 5-tris (3, 5-di-t-butyl-4-hydroxybenzyl) isocyanuric acid; CAS: 27676-62-6), antioxidant 245 (triethylene glycol bis [ β - (3-t-butyl-4-hydroxy-5-methylphenyl) propionate ]) and antioxidant 330 (1, 3, 5-trimethyl-2, 4, 6-tris (3, 5-t-butyl-4-hydroxybenzyl) benzene; CAS: 1709-70-2); The secondary antioxidant is at least one selected from antioxidant 168 (tris [2, 4-di-tert-butylphenyl ] phosphite; CAS: 31570-04-4), antioxidant 618 (distearyl pentaerythritol diphosphite; CAS: 3806-34-6), bis (2, 4-dicumylphenyl) pentaerythritol-diphosphite, distearyl pentaerythritol diphosphite and antioxidant 2,2' -ethylenebis (4, 6-di-tert-butylphenyl) fluorophosphite (CAS: 118337-09-0).
  12. 12. PGA composition according to claim 8 or 9, wherein the chain extender is selected from at least one of styrene-glycidyl methacrylate copolymer, styrene-butyl acrylate-glycidyl methacrylate terpolymer, methyl styrene-methacrylate-glycidyl acrylate terpolymer, styrene-methyl methacrylate-glycidyl methacrylate terpolymer and ethylene-butyl acrylate-glycidyl methacrylate terpolymer.
  13. 13. PGA composition according to claim 8 or 9, wherein the hydrolysis inhibitor is selected from polycarbodiimide, monomeric carbodimethylamine, dicyclohexylcarbodiimide, N ' -diisopropylcarbodiimide, 2',6,6' -tetraisopropyl carbodiimide, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, 1- (3-dimethylaminopropyl) -3-ethyl-carbodiimide hydrochloride, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, 1-ethyl-3- (3-dimethylaminopropyl) ammonium carbonate, 1- (3-dimethylaminopropyl) -3-ethyl-carbodiimide hydrochloride, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, 1-ethyl- (3-dimethylaminopropyl) 3-ethylcarbodiimide hydrochloride, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, and the like, at least one of N- (3-dimethylaminopropyl) -N' -ethyl-carbodiimide hydrochloride and (3-dimethylaminopropyl) -3-ethylcarbodiamine.
  14. 14. PGA composition according to claim 8 or 9, wherein the nucleating agent is selected from at least one of hyperbranched polyamides, ethylene-methacrylic acid ionomers, sebacic acid diphenyl dihydrazide, adipic acid diphenyl dihydrazide and phenyl zinc phosphate.
  15. 15. PGA composition according to claim 8 or 9, wherein the polyglycolic acid-based resin has a melt flow rate of 5-60g/10min, preferably 10-50g/10min, more preferably 15-45g/10min at 230 ℃ under a load of 2.16 kg; And/or the weight average molecular weight of the polyglycolic acid-based resin is 1 ten thousand to 80 ten thousand, preferably 2 ten thousand to 30 ten thousand, more preferably 5 ten thousand to 20 ten thousand; and/or the molecular weight distribution width Mw/Mn of the polyglycolic acid-based resin is 1 to 5, preferably 1.5 to 3.5; and/or the polyglycolic acid-based resin is homo-polyglycolic acid and/or co-polyglycolic acid, preferably homo-polyglycolic acid.
  16. 16. The method for preparing the PGA composition according to any one of claims 8 to 15, which comprises uniformly mixing the polyglycolic acid-based resin, the PGA resin edge grafting modified graphene according to any one of claims 1 to 3, the bio-based elastomer, the antioxidant, the nucleating agent, the chain extender and the hydrolysis inhibitor to obtain the PGA composition.
  17. 17. Biodegradable polyester material, characterized in that it is obtained by a process comprising the step of melt-mixing the PGA composition according to any one of claims 8 to 15, to obtain said biodegradable polyester material.
  18. 18. Use of a PGA composition according to any one of claims 8 to 15 and a biodegradable polyester material according to claim 17 as a starting material for the preparation of temporary plug balls of PGA.
  19. 19. The temporary blocking ball of the PGA is characterized by being prepared by a method comprising the following steps: performing injection molding and annealing on the biodegradable polyester material according to claim 17 to obtain the PGA temporary plugging ball.
  20. 20. The temporary plugging ball of PGA according to claim 19, wherein the technological parameters of the injection molding process include an injection pressure of 70-100bar, a holding pressure of 70-120bar, a mold temperature of 60-110 ℃, and an injection speed of 10-20cm 3 /s; the annealing temperature is 80-110 ℃ and the annealing time is 1-5h.

Description

PGA resin edge grafting modified graphene, composition, preparation method and application thereof, biodegradable polyester material, application thereof and temporary plugging ball Technical Field The invention relates to the technical field of high polymer materials, in particular to a PGA resin edge grafting modified graphene and a preparation method thereof, a PGA composition and a preparation method and application thereof, a biodegradable polyester material and an application thereof, and a PGA temporary plugging ball. Background With the continuous exploitation of the existing ascertained oil and gas field, the oil and gas abundance of the reservoir gradually decreases. Reservoir fracturing engineering is therefore commonly used to adjust the permeability of subsurface reservoirs to achieve sustainable recovery of hydrocarbon resources in increasingly depleted subsurface reservoirs. As a most widely used layered fracturing technology at present, the ball-throwing layered fracturing method utilizes the characteristic of large liquid absorption of a pressed oil and gas layer, after the completion of a target layered fracturing construction, a certain amount of temporary plugging balls are brought into holes of the pressed layer by fracturing liquid to plug the holes of the layer, the fracturing liquid is forced to enter other uncrushed layers, and the fracturing pressure is increased, so that another target reservoir with higher required fracturing pressure is pressed. And repeating the steps until all the target layers in the fracturing layer section are pressed open, so that the purpose of pressing open a plurality of production layers by one-time construction is achieved. In the above operations, the temporary plugging ball is the most commonly used downhole production tool. However, the existing temporary plugging ball material is generally non-degradable plastic, rubber, metal alloy and the like. When the method is applied to underground exploitation, temporary blocking balls are required to be unblocked after a section of exploitation. The conventional temporary plugging balls are often difficult to dissolve by using common medicaments. Either the dissolution is difficult and insoluble for a long time, or even the dissolution is easy to be blocked in the borehole, and it is difficult to flow back out of the borehole after the temporary plugging diverting fracturing construction is finished. Aiming at the problems, the temporary plugging ball needs to be additionally provided with measures to drill, grind or salvage, so that the operation cost is greatly increased, the production efficiency is reduced, more liquid is generally used in the drilling and grinding process, and secondary pollution is easily caused to an underground reservoir. In addition, the temporary plugging ball made of the metal alloy material has high rigidity and strength, a large amount of electrolyte salts are required to be added into the produced liquid, and after dissolution, the alloy tends to form residues, so that further pollution is caused to an underground reservoir. When the shape of the blasthole is irregular, the deformation suitable for the blasthole with the irregular shape cannot be generated due to the high rigidity and low plasticity of the alloy material, so that the tightness of the blasthole is poor, stable bearing strength is difficult to form, and the temporary plugging steering fracturing effect is greatly influenced. The Chinese patent application 202011020847.8 discloses a temporary plugging ball with a three-layer composite structure, which has good temporary plugging effect, but has complex formula, contains non-degradable component polyvinyl alcohol, is not easy to be reflected out along with fracturing fluid after plugging removal, and can cause secondary pollution after being left in stratum. Chinese patent application 202110861989.5 discloses a degradable temporary plugging ball. However, the temporary plugging balls contain 15-30 parts by weight of functional filler (functional zeolite powder) and 4-8 parts of EVA grafted MAH, and the components cannot be completely degraded in the stratum. Graphene has been attracting attention due to its high light transmittance, high electrical conductivity, high thermal conductivity, high specific surface area, and excellent mechanical properties. In order to expand the application field and fully exert the performance characteristics, the development of a preparation technology of high-quality low-cost functionalized graphene is a key and precondition for large-scale commercial application. Redox, mechanical exfoliation, chemical vapor deposition, arc discharge, electrochemical, etc. are common graphene preparation methods. Among them, the chemical vapor deposition method, the arc discharge method and the electrochemical method have high cost and complex preparation process. The mechanical stripping method and the oxidation-reduction method both take natura