CN112920579B - Degradable composite material for manufacturing uterine curettage spoon - Google Patents
Degradable composite material for manufacturing uterine curettage spoon Download PDFInfo
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- CN112920579B CN112920579B CN202110309750.7A CN202110309750A CN112920579B CN 112920579 B CN112920579 B CN 112920579B CN 202110309750 A CN202110309750 A CN 202110309750A CN 112920579 B CN112920579 B CN 112920579B
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- polylactic acid
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- 239000002131 composite material Substances 0.000 title claims abstract description 84
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 39
- 239000000463 material Substances 0.000 claims abstract description 61
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 54
- 229920000747 poly(lactic acid) Polymers 0.000 claims abstract description 50
- 239000004626 polylactic acid Substances 0.000 claims abstract description 50
- 239000011256 inorganic filler Substances 0.000 claims abstract description 45
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 45
- RQFQJYYMBWVMQG-IXDPLRRUSA-N chitotriose Chemical compound O[C@@H]1[C@@H](N)[C@H](O)O[C@H](CO)[C@H]1O[C@H]1[C@H](N)[C@@H](O)[C@H](O[C@H]2[C@@H]([C@@H](O)[C@H](O)[C@@H](CO)O2)N)[C@@H](CO)O1 RQFQJYYMBWVMQG-IXDPLRRUSA-N 0.000 claims abstract description 35
- 229920001577 copolymer Polymers 0.000 claims abstract description 33
- ULKFLOVGORAZDI-UHFFFAOYSA-N 3,3-dimethyloxetan-2-one Chemical compound CC1(C)COC1=O ULKFLOVGORAZDI-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000012745 toughening agent Substances 0.000 claims abstract description 29
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 16
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 16
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 14
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 14
- 239000002245 particle Substances 0.000 claims abstract description 12
- 239000000835 fiber Substances 0.000 claims description 78
- ZFOZVQLOBQUTQQ-UHFFFAOYSA-N Tributyl citrate Chemical compound CCCCOC(=O)CC(O)(C(=O)OCCCC)CC(=O)OCCCC ZFOZVQLOBQUTQQ-UHFFFAOYSA-N 0.000 claims description 46
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 29
- 229920000433 Lyocell Polymers 0.000 claims description 29
- 239000004917 carbon fiber Substances 0.000 claims description 29
- 239000002202 Polyethylene glycol Substances 0.000 claims description 23
- 229920001223 polyethylene glycol Polymers 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 19
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 18
- OIPILFWXSMYKGL-UHFFFAOYSA-N acetylcholine Chemical compound CC(=O)OCC[N+](C)(C)C OIPILFWXSMYKGL-UHFFFAOYSA-N 0.000 claims description 17
- 239000002608 ionic liquid Substances 0.000 claims description 17
- RWXQMVKCJBXSLO-UHFFFAOYSA-N B(O)(O)O.B(O)(O)O.B(O)(O)O.B(O)(O)O.C(CCC)N1CN(C=C1)C Chemical compound B(O)(O)O.B(O)(O)O.B(O)(O)O.B(O)(O)O.C(CCC)N1CN(C=C1)C RWXQMVKCJBXSLO-UHFFFAOYSA-N 0.000 claims description 16
- 239000000741 silica gel Substances 0.000 claims description 7
- 229910002027 silica gel Inorganic materials 0.000 claims description 7
- 108010025899 gelatin film Proteins 0.000 claims description 2
- CRSOQBOWXPBRES-UHFFFAOYSA-N neopentylidene Natural products CC(C)(C)C CRSOQBOWXPBRES-UHFFFAOYSA-N 0.000 claims 1
- -1 poly (neopentane lactone Chemical class 0.000 claims 1
- 230000002787 reinforcement Effects 0.000 claims 1
- 230000015556 catabolic process Effects 0.000 abstract description 20
- 238000006731 degradation reaction Methods 0.000 abstract description 20
- 230000000694 effects Effects 0.000 abstract description 5
- 239000011248 coating agent Substances 0.000 description 13
- 238000000576 coating method Methods 0.000 description 13
- 229930182843 D-Lactic acid Natural products 0.000 description 8
- JVTAAEKCZFNVCJ-UWTATZPHSA-N D-lactic acid Chemical compound C[C@@H](O)C(O)=O JVTAAEKCZFNVCJ-UWTATZPHSA-N 0.000 description 8
- 238000005452 bending Methods 0.000 description 8
- 229940022769 d- lactic acid Drugs 0.000 description 8
- 239000000377 silicon dioxide Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 5
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000003014 reinforcing effect Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000007792 addition Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- HRRABTJSQPBHCJ-UHFFFAOYSA-N 1-butyl-3-methylimidazol-3-ium tetraborate Chemical compound [O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].CCCC[N+]=1C=CN(C)C=1.CCCC[N+]=1C=CN(C)C=1.CCCC[N+]=1C=CN(C)C=1.CCCC[N+]=1C=CN(C)C=1.CCCC[N+]=1C=CN(C)C=1.CCCC[N+]=1C=CN(C)C=1.CCCC[N+]=1C=CN(C)C=1.CCCC[N+]=1C=CN(C)C=1.CCCC[N+]=1C=CN(C)C=1.CCCC[N+]=1C=CN(C)C=1.CCCC[N+]=1C=CN(C)C=1.CCCC[N+]=1C=CN(C)C=1 HRRABTJSQPBHCJ-UHFFFAOYSA-N 0.000 description 1
- 206010011409 Cross infection Diseases 0.000 description 1
- 206010029803 Nosocomial infection Diseases 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000003759 clinical diagnosis Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920006238 degradable plastic Polymers 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 210000004696 endometrium Anatomy 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
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- 239000002657 fibrous material Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002906 medical waste Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000001225 therapeutic effect Effects 0.000 description 1
- 210000004291 uterus Anatomy 0.000 description 1
Classifications
-
- 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
-
- 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
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
-
- 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
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- 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
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
-
- 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
Abstract
The invention relates to a degradable composite material for manufacturing a uterine curettage spoon, and belongs to the technical field of medical instrument materials. In order to solve the problem that the existing non-disposable uterine curettage spoon is easy to infect, a degradable composite material for manufacturing the uterine curettage spoon is provided, and the degradable composite material comprises the following components in parts by weight: polylactic acid-glycolic acid copolymer: 60-70 parts of; chitosan oligosaccharide: 10-15; poly (pivalolactone): 5.0 to 6.2; antioxidant: 1.0 to 8.0; a composite toughening agent: 8.0 to 9.0; biodegradable fiber-reinforced material: 10-13; modified inorganic filler: 2.0-5.0, wherein the modified inorganic filler is prepared by polylactic acid coated nano silicon dioxide particles. The invention can ensure that the whole material has basically complete degradation capability and has the effect of high strength performance.
Description
Technical Field
The invention relates to a degradable composite material for manufacturing a uterine curettage spoon, and belongs to the technical field of medical instrument materials.
Background
Uterine curettage is a common method for clinical diagnosis and treatment of gynecological diseases, and is an operation for curettage endometrium or uterine cavity contents, which is divided into diagnostic uterine curettage and therapeutic uterine curettage. At present, the main appliance in clinical uterine curettage for patients is a uterine curettage spoon, and usually, when clinical uterine curettage is carried out on patients, a probe is firstly used for probing the depth of a uterus, and then the uterine curettage spoon is used for cleaning and curettage. The current uterine curettes are usually made of stainless steel materials and are used for a plurality of times, however, the uterine curettes usually need to be disinfected before being used, and the risk of inadequate disinfection or cross infection in the transferring process exists in the using process, and the workload of medical staff is increased by the disinfection process. Although the prior uterine curettage spoon made of plastic is also available, the uterine curettage spoon is poor in degradation performance or is made of non-degradable plastic directly, the degradation performance is mostly not considered, a large amount of plastic pollution is easily caused after the uterine curettage spoon is used, and the uterine curettage spoon serving as medical waste can cause serious environmental pollution.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a degradable composite material for manufacturing a uterine curettage spoon, and solves the problem of how to realize the degradable material for the disposable uterine curettage spoon, and the degradable material has good strength performance.
The purpose of the invention is realized by the following technical scheme, and the degradable composite material for manufacturing the uterine curettage spoon comprises the following components in parts by weight:
polylactic acid-glycolic acid copolymer: 60-70 parts of; chitosan oligosaccharide: 10-15; poly (pivalolactone): 5.0 to 6.2; antioxidant: 1.0 to 8.0; a composite toughening agent: 8.0-9.0; biodegradable fiber-reinforced material: 10-13; modified inorganic filler: 2.0-5.0, wherein the modified inorganic filler is prepared by polylactic acid coated nano silicon dioxide particles.
The polylactic acid-glycolic acid copolymer is adopted as a main material, so that the degradable uterine curettage spoon has high degradation performance, and the uterine curettage spoon needs to have certain hardness requirement when being used as a uterine curettage spoon material; meanwhile, the adopted chitosan oligosaccharide and the adopted poly-pivalolactone have good degradation performance, so that the whole material can be ensured to have basically complete degradation capability, and the plastic pollution problem caused by incapability of degradation can be effectively avoided even if the material is used as a disposable uterine curettage spoon material; in addition, the compatibility between materials can be effectively improved by coating the nano silicon dioxide with polylactic acid, and the polylactic acid-glycolic acid copolymer in the matrix material have the same raw materials, so that the inorganic filler has better compatibility, and the performance of the material is improved.
In the degradable composite material for making the uterine curettage spoon, preferably, the weight average molecular weight of the polylactic acid-glycolic acid copolymer is 5000-10000 Da, and the weight average molecular weight of the polylactic acid-glycolic acid copolymer is: chitosan oligosaccharide: the weight ratio of the poly (pivalolactone) is 65: 11-12: 5.1 to 5.3. The material can be wholly provided with high degradation performance, and meanwhile, the formed uterine curettage spoon can be provided with better toughness and strength performance through the dosage proportion. More preferably, the weight average molecular weight of the poly (pivalolactone) is 6000 to 8000 Da. Through the improvement and control of the molecular weight, the degradation capability of the whole material can be ensured, and the material has better structural strength characteristics and ensures the strength performance through the control of the molecular weight. Further, it is preferable that the weight average molecular weight of the chitosan oligosaccharide is less than or equal to 3200 Da.
In the degradable composite material for manufacturing the uterine curettage spoon, preferably, the biodegradable fiber reinforced material is one or a mixture of several selected from tencel fibers, polylactic acid fibers and carbon fibers. The fiber reinforced materials not only ensure the strength performance of the composite material and play a role in enhancing the mechanical strength through fibers, but also adopt biodegradable materials and have high degradation performance.
In the above degradable composite material for making the uterine curettage spoon, preferably, the biodegradable fiber reinforced material is selected from a mixture of tencel fibers, polylactic acid fibers and carbon fibers, and the aspect ratio of the carbon fibers is larger than that of the tencel fibers and the polylactic acid fibers. The length of the biodegradable fiber reinforced material can be 2-4 mm. The carbon fiber has a large length-diameter ratio, so that the material has better strength performance as a whole, and the tencel fiber and the polylactic acid fiber which have relatively small length-diameter ratio are matched to enable the material to adopt a mixing mode which is equivalent to different grading of the length-diameter ratio to add the fiber material, so that the fiber distribution between the fibers is better ensured, the defect of uneven fiber distribution in the material can be reduced, and better reinforcing performance is realized. More preferably, the aspect ratio of the carbon fiber is 5 to 6: 1, the length-diameter ratio of the tencel fiber and the polylactic acid fiber is respectively and independently selected from 2-3: 1. it is preferable that the aspect ratio of the carbon fiber is 5.5: 1, the length-diameter ratio of the tencel fiber is 2: 1, the length-diameter ratio of the polylactic acid fiber is 3: 1. a better fiber grading combination mode is formed, and the overall reinforcing performance of the material is improved. More preferably, the using amount ratio of the carbon fiber, the tencel fiber and the polylactic acid fiber is 1: 0.2-0.5: 0.6-0.8, the reinforced fiber composite material formed by the grading mixing mode and different length-diameter ratios can better improve the strength performance of the material, so that the material has better toughness and strength performance, and the use amount ratio of carbon fibers, tencel fibers and polylactic acid fibers is preferably 1: 0.4: 0.6.
in the degradable composite material for manufacturing the uterine curettage spoon, preferably, after the degradable composite material is used for manufacturing the uterine curettage spoon, a silica gel film layer is coated on the surface of the uterine curettage spoon. Through the coating at the surface have the silica gel rete, can have better travelling comfort, through the setting of surperficial silica gel rete, the safety in utilization of improvement curettage spoon that can be better makes the thickness control of silica gel rete at 3 ~ 6mm best.
In the degradable composite material for manufacturing the uterine curettage spoon, preferably, the composite toughening agent is a mixture of tributyl citrate and polyethylene glycol. The toughness of the material can be better improved, and the material has better strength performance.
In the degradable composite material for manufacturing the curettage spoon, preferably, the degradable composite material further contains choline acetate ionic liquid and/or 1-butyl-3-methylimidazole tetraborate, and the weight part of the choline acetate ionic liquid and/or the 1-butyl-3-methylimidazole tetraborate is 0.5-1.0. In the research process, the inventor finds that the material can better promote the degradation effect of the fiber in the environment, better degrade the fiber and have better degradation rate performance by adding a small amount of the choline acetate ionic liquid and/or the 1-butyl-3-methylimidazole tetraborate, and more importantly, the existence of the choline acetate ionic liquid and/or the 1-butyl-3-methylimidazole tetraborate also has better improvement on the strength performance of the material, so that the material has better impact strength and bending strength performance, and further preferably, the mixture of the choline acetate ionic liquid and the 1-butyl-3-methylimidazole tetraborate is preferably used, and the ratio of the dosage of the choline acetate ionic liquid to the dosage of the 1-butyl-3-methylimidazole tetraborate is 1: 0.2 to 0.4.
In the above degradable composite material for making a uterine curettage spoon, preferably, the modified inorganic filler comprises polylactic acid: the mass ratio of the nano silicon dioxide particles is 1: 0.1 to 0.3.
In summary, compared with the prior art, the invention has the following advantages:
1. the polylactic acid-glycolic acid copolymer is mixed with a certain amount of chitosan oligosaccharide and poly-pivalolactone for synergistic action, and a small amount of modified inorganic filler and fiber reinforced material are added, so that the strength performance requirement is better, and the hardness requirement is better when the uterine curettage spoon is acted; meanwhile, the adopted chitosan oligosaccharide and the adopted poly-pivalolactone also have good degradation performance, so that the whole material can be ensured to have basically complete degradation capability, and the material can be used as a disposable uterine curettage spoon material and has good performance in tensile strength and impact strength performance.
2. By adding a small amount of choline acetate ionic liquid and/or 1-butyl-3-methylimidazole tetraborate, the degradation effect of the fiber in the environment can be better promoted, the complete degradation performance is better played, and meanwhile, the existence of the choline acetate ionic liquid and/or the 1-butyl-3-methylimidazole tetraborate is more importantly found to better promote the strength performance of the material, and particularly the bending strength performance is better.
Detailed Description
The technical solution of the present invention is further specifically described below by way of specific examples, but the present invention is not limited to these examples.
The degradable composite material for manufacturing the uterine curettage spoon comprises the following components in parts by weight:
polylactic acid-glycolic acid copolymer: 60-70 parts of; chitosan oligosaccharide: 10-15; poly (pivalolactone): 5.0 to 6.2; antioxidant: 1.0 to 8.0; a composite toughening agent: 8.0-9.0; biodegradable fiber-reinforced material: 10-13; modified inorganic filler: 2.0-5.0, wherein the modified inorganic filler is prepared by polylactic acid coated nano silicon dioxide particles. The composite material can be processed and granulated by a conventional method and then processed into a corresponding product, the polylactic acid-glycolic acid copolymer preferably has the weight-average molecular weight of 5000-10000 Da, so that the composite material has better strength performance, the weight-average molecular weight of the poly (neopentanolactone) can be 6000-8000 Da, the weight-average molecular weight of the chitosan oligosaccharide is less than or equal to 3200Da, and the polylactic acid-glycolic acid copolymer is preferably prepared by the following steps: chitosan oligosaccharide: the weight ratio of the poly (pivalolactone) is 65: 11-12: 5.1-5.3, the material has better toughness and strength performance and high bending strength performance by adjusting the proportion, and the optimal scheme is that the polylactic acid-glycolic acid copolymer: chitosan oligosaccharide: the weight ratio of the poly (pivalolactone) is 65: 11: 5.2; furthermore, the biodegradable fiber reinforced material is preferably made of one or a mixture of tencel fiber, polylactic acid fiber and carbon fiber, the length of the biodegradable fiber reinforced material is 2-4 mm, preferably 3mm, and the length-diameter ratio of the carbon fiber is preferably 5-6: 1, the length-diameter ratio of the tencel fiber and the polylactic acid fiber is respectively and independently selected from 2-3: 1. optimally, the length-diameter ratio of the carbon fiber is 5.5: 1, the length-diameter ratio of the tencel fiber is 2: 1, the length-diameter ratio of the polylactic acid fiber is 3: 1; in order to better exert the reinforcing performance of a fiber mixed system, the dosage ratio of the carbon fiber, the tencel fiber and the polylactic acid fiber is 1: 0.2-0.5: 0.6-0.8, preferably 1: 0.4: 0.6.
in a further scheme, the adopted composite toughening agent adopts a mixture of tributyl citrate and polyethylene glycol, preferably the dosage ratio of the tributyl citrate to the polyethylene glycol is 1: 0.4 to 0.6. The material has better toughening performance and further ensures the strength effect.
In a further preferred scheme, choline acetate ionic liquid and/or 1-butyl-3-methylimidazole tetraborate are/is added into the composite material, and the weight part of the choline acetate ionic liquid and/or 1-butyl-3-methylimidazole tetraborate is 0.5-1.0, so that the composite material has better degradation performance, high impact strength and bending strength performance, the bending strength performance reaches over 160MPa, the notch impact strength reaches over 90MPa, and the degradation rate reaches over 96% by adding a small amount of the choline acetate ionic liquid and/or 1-butyl-3-methylimidazole tetraborate in the research process; preferably, a mixture of the choline acetate ionic liquid and 1-butyl-3-methylimidazole tetraborate is adopted, and the dosage ratio of the choline acetate ionic liquid to the 1-butyl-3-methylimidazole tetraborate is 1: 0.2 to 0.4.
The modified inorganic filler may further contain, as the components: the mass ratio of the nano silicon dioxide particles is 1: 0.1 to 0.3. The particle size of the nano silica particles is preferably 50nm to 150 nm. The antioxidant is preferably 1010, 168 or 245, so that the composite material has better oxidation resistance.
Example 1
The degradable composite material for manufacturing the uterine curettage spoon comprises the following components in parts by weight:
polylactic acid-glycolic acid copolymer: 70; chitosan oligosaccharide: 15, and the weight average molecular weight of the chitosan oligosaccharide is 3000 Da; poly (pivalolactone): 6.2; antioxidant: 8.0, adopting an antioxidant 1010; a composite toughening agent: 9.0, adopting a composite toughening agent of tributyl citrate and polyethylene glycol; biodegradable fiber reinforced material polylactic acid fiber: 13, length 2 mm; modified inorganic filler: 5.0, the modified inorganic filler is prepared by coating polylactic acid on nano silicon dioxide particles, and the mass ratio of the polylactic acid to the nano silicon dioxide in the modified inorganic filler is 1: 0.3.
the method for manufacturing the uterine curettage spoon by using the composite material adopts a conventional processing mode in the field, and the uterine curettage spoon can be specifically processed by the following steps:
selecting corresponding raw materials according to the weight ratio of the components of the composite material, adding the raw materials into a granulator for granulation and molding, and then putting the granulated and molded composite material particles into an injection molding machine for injection molding to obtain the corresponding uterine curettage spoon.
Example 2
The degradable composite material for manufacturing the uterine curettage spoon comprises the following components in parts by weight:
polylactic acid-glycolic acid copolymer: 60, adding a solvent to the mixture; chitosan oligosaccharide: 10, and the weight average molecular weight of the chitosan oligosaccharide is 3000 Da; poly (pivalolactone): 5.0; antioxidant: 8.0, adopting an antioxidant 1010; a composite toughening agent: 8.0, adopting a composite toughening agent of tributyl citrate and polyethylene glycol; biodegradable fiber reinforced material polylactic acid fiber: 12, the length is 3 mm; modified inorganic filler: 4.0, the modified inorganic filler is prepared by coating polylactic acid on nano silicon dioxide particles, and the mass ratio of the polylactic acid to the nano silicon dioxide in the modified inorganic filler is 1: 0.25.
the manufacturing method of this embodiment is the same as that of embodiment 1, and is not described herein again.
Example 3
The degradable composite material for manufacturing the uterine curettage spoon comprises the following components in parts by weight:
polylactic acid-glycolic acid copolymer: 65; chitosan oligosaccharide: 13, and the weight average molecular weight of the chitosan oligosaccharide is 2500 Da; poly (pivalolactone): 5.5; antioxidant: 6.0, adopting an antioxidant 1010; a composite toughening agent: 8.5, adopting a composite toughening agent of tributyl citrate and polyethylene glycol; biodegradable fiber reinforced material polylactic acid fiber: 10, length 4 mm; modified inorganic filler: 2.0, the modified inorganic filler is prepared by coating polylactic acid on nano silicon dioxide particles, and the mass ratio of the polylactic acid to the nano silicon dioxide in the modified inorganic filler is 1: 0.2.
the manufacturing method of this embodiment is the same as that of embodiment 1, and is not described herein again.
Example 4
The degradable composite material for manufacturing the uterine curettage spoon comprises the following components in parts by weight:
polylactic acid-glycolic acid copolymer: 65; chitosan oligosaccharide: 11, and the weight average molecular weight of the chitosan oligosaccharide is 2500 Da; poly (pivalolactone): 5.1; antioxidant: 1.0; a composite toughening agent: 8.7, adopting a composite toughening agent of tributyl citrate and polyethylene glycol, wherein the mass ratio of the tributyl citrate to the polyethylene glycol is 1: 0.5; biodegradable fiber-reinforced material: 10, adopting tencel fiber with the length of 2 mm; modified inorganic filler: 2.0, the modified inorganic filler is prepared by coating poly D-lactic acid on nano silica particles, and the mass ratio of the polylactic acid to the nano silica in the modified inorganic filler is 1: 0.2; the weight average molecular weights of the polylactic acid-glycolic acid copolymer and the poly-pivalolactone are both 8000 Da;
the manufacturing method of this embodiment is the same as that of embodiment 1, and is not described herein again.
Example 5
The degradable composite material for manufacturing the uterine curettage spoon comprises the following components in parts by weight:
polylactic acid-glycolic acid copolymer: 65; chitosan oligosaccharide: 12, and the weight average molecular weight of the chitosan oligosaccharide is 2500 Da; poly (pivalolactone): 5.3; antioxidant: 3.0; a composite toughening agent: 8.0, adopting a composite toughening agent of tributyl citrate and polyethylene glycol, wherein the mass ratio of the tributyl citrate to the polyethylene glycol is 1: 0.4; biodegradable fiber-reinforced material: 11, adopting carbon fiber, wherein the length is 2 mm; modified inorganic filler: 3.0, the modified inorganic filler is prepared by coating poly D-lactic acid on nano silica particles, and the mass ratio of the polylactic acid to the nano silica in the modified inorganic filler is 1: 0.2; the weight average molecular weight of the polylactic acid-glycolic acid copolymer is 10000Da, and the weight average molecular weight of the poly-pivalolactone is 6000 Da;
the manufacturing method of this embodiment is the same as that of embodiment 1, and is not described herein again.
Example 6
The degradable composite material for manufacturing the uterine curettage spoon comprises the following components in parts by weight:
polylactic acid-glycolic acid copolymer: 65; chitosan oligosaccharide: 11.5, and the weight average molecular weight of the chitosan oligosaccharide is 2500 Da; poly (pivalolactone): 5.2; antioxidant: 4.0; a composite toughening agent: 8.5, adopting a composite toughening agent of tributyl citrate and polyethylene glycol, wherein the mass ratio of the tributyl citrate to the polyethylene glycol is 1: 0.4 of the total weight of the mixture; biodegradable fiber-reinforced material: 12, adopting a mixture of tencel fibers and carbon fibers, wherein the lengths of the tencel fibers and the carbon fibers are both 3 mm; modified inorganic filler: 4.0, the modified inorganic filler is prepared by coating poly D-lactic acid on nano silica particles, and the mass ratio of the polylactic acid to the nano silica in the modified inorganic filler is 1: 0.1; the weight average molecular weight of the polylactic acid-glycolic acid copolymer is 5000Da, and the weight average molecular weight of the poly-pivalolactone is 7000 Da;
the manufacturing method of this embodiment is the same as that of embodiment 1, and is not described herein again.
Example 7
The degradable composite material for manufacturing the uterine curettage spoon comprises the following components in parts by weight:
polylactic acid-glycolic acid copolymer: 65; chitosan oligosaccharide: 11.5, and the weight average molecular weight of the chitosan oligosaccharide is 2500 Da; poly (pivalolactone): 5.2; antioxidant: 4.0; a composite toughening agent: 8.5, adopting a composite toughening agent of tributyl citrate and polyethylene glycol, wherein the mass ratio of the tributyl citrate to the polyethylene glycol is 1: 0.4; biodegradable fiber-reinforced material: 12, adopting a mixture of polylactic acid fiber, tencel fiber and carbon fiber; modified inorganic filler: 4.0, the modified inorganic filler is prepared by coating poly D-lactic acid on nano silica particles, and the mass ratio of the polylactic acid to the nano silica in the modified inorganic filler is 1: 0.1; the weight average molecular weight of the polylactic acid-glycolic acid copolymer is 5000Da, the weight average molecular weight of the poly-pivalolactone is 7000Da, and the length-diameter ratio of the polylactic acid fiber is 2: 1, the length-diameter ratio of the tencel fiber is 3: 1, the length-diameter ratio of the carbon fiber is 6: 1;
the manufacturing method of this embodiment is the same as that of embodiment 1, and is not described herein again.
Example 8
The degradable composite material for manufacturing the uterine curettage spoon comprises the following components in parts by weight:
polylactic acid-glycolic acid copolymer: 65; chitosan oligosaccharide: 11.5, and the weight average molecular weight of the chitosan oligosaccharide is 2500 Da; poly (pivalolactone): 5.2; antioxidant: 4.0; a composite toughening agent: 8.5, adopting a composite toughening agent of tributyl citrate and polyethylene glycol, wherein the mass ratio of the tributyl citrate to the polyethylene glycol is 1: 0.4; biodegradable fiber-reinforced material: 12, adopting a mixture of polylactic acid fiber, tencel fiber and carbon fiber; modified inorganic filler: 4.0, the modified inorganic filler is prepared by coating poly D-lactic acid on nano-silica particles, and the mass ratio of the polylactic acid to the nano-silica in the modified inorganic filler is 1: 0.1; the weight average molecular weight of the polylactic acid-glycolic acid copolymer is 5000Da, the weight average molecular weight of the poly-pivalolactone is 7000Da, and the length-diameter ratio of the polylactic acid fiber is 2: 1, the length-diameter ratio of the tencel fiber is 3: 1, the length-diameter ratio of the carbon fiber is 5: 1;
the manufacturing method of this embodiment is the same as that of embodiment 1, and is not described herein again.
Example 9
The degradable composite material for manufacturing the uterine curettage spoon comprises the following components in parts by weight:
polylactic acid-glycolic acid copolymer: 60, adding a solvent to the mixture; chitosan oligosaccharide: 12, and the weight average molecular weight of the chitosan oligosaccharide is 3000 Da; poly (pivalolactone): 5.6; antioxidant: 5.0; a composite toughening agent: 8.5, adopting a composite toughening agent of tributyl citrate and polyethylene glycol, wherein the mass ratio of the tributyl citrate to the polyethylene glycol is 1: 0.5; biodegradable fiber-reinforced material: 12, adopting a mixture of polylactic acid fiber, tencel fiber and carbon fiber; modified inorganic filler: 5.0, the modified inorganic filler is prepared by coating poly D-lactic acid on nano-silica particles, and the mass ratio of the polylactic acid to the nano-silica in the modified inorganic filler is 1: 0.2; choline acetate ionic liquid: 1.0. the weight average molecular weight of the polylactic acid-glycolic acid copolymer is 7000Da, the weight average molecular weight of the poly-pivalolactone is 8000Da, and the length-diameter ratio of the polylactic acid fiber is 2: 1, the length-diameter ratio of the tencel fiber is 3: 1, the length-diameter ratio of the carbon fiber is 5: 1;
the manufacturing method of this embodiment is the same as that of embodiment 1, and is not described herein again.
Example 10
The degradable composite material for manufacturing the uterine curettage spoon comprises the following components in parts by weight:
polylactic acid-glycolic acid copolymer: 60, adding a solvent to the mixture; chitosan oligosaccharide: 12, and the weight average molecular weight of the chitosan oligosaccharide is 3000 Da; poly (pivalolactone): 5.6; antioxidant: 5.0; a composite toughening agent: 8.5, adopting a composite toughening agent of tributyl citrate and polyethylene glycol, wherein the mass ratio of the tributyl citrate to the polyethylene glycol is 1: 0.5; biodegradable fiber-reinforced material: 12, adopting a mixture of polylactic acid fibers, tencel fibers and carbon fibers; modified inorganic filler: 5.0, the modified inorganic filler is prepared by coating poly D-lactic acid on nano-silica particles, and the mass ratio of the polylactic acid to the nano-silica in the modified inorganic filler is 1: 0.2; 1-butyl-3-methylimidazole tetraborate: 0.5. the weight average molecular weight of the polylactic acid-glycolic acid copolymer is 7000Da, the weight average molecular weight of the poly-pivalolactone is 8000Da, and the length-diameter ratio of the polylactic acid fiber is 2: 1, the length-diameter ratio of the tencel fiber is 3: 1, the length-diameter ratio of the carbon fiber is 5: 1;
the manufacturing method of this embodiment is the same as that of embodiment 1, and is not described herein again.
Example 11
The degradable composite material for manufacturing the uterine curettage spoon comprises the following components in parts by weight:
polylactic acid-glycolic acid copolymer: 65; chitosan oligosaccharide: 13, and the weight average molecular weight of the chitosan oligosaccharide is 3000 Da; poly (pivalolactone): 5.5; antioxidant: 4.0; a composite toughening agent: 8.0, adopting a composite toughening agent of tributyl citrate and polyethylene glycol, wherein the mass ratio of the tributyl citrate to the polyethylene glycol is 1: 0.5; biodegradable fiber-reinforced material: 12, adopting a mixture of polylactic acid fibers, tencel fibers and carbon fibers; modified inorganic filler: 3.0, the modified inorganic filler is prepared by coating poly D-lactic acid on nano silica particles, and the mass ratio of the polylactic acid to the nano silica in the modified inorganic filler is 1: 0.2; choline acetate ionic liquid and 1-butyl-3-methylimidazolium tetraborate: 1.0. the weight average molecular weight of the polylactic acid-glycolic acid copolymer is 7000Da, the weight average molecular weight of the poly-pivalolactone is 8000Da, and the length-diameter ratio of the polylactic acid fiber is 2: 1, the length-diameter ratio of the tencel fiber is 3: 1, the length-diameter ratio of the carbon fiber is 5: 1;
the manufacturing method of this embodiment is the same as that of embodiment 1, and is not described herein again.
Example 12
After the degradable composite material for manufacturing the uterine curettage spoon is manufactured into the corresponding uterine curettage spoon, the surface of the uterine curettage spoon is coated with a silica gel layer, and the thickness of the silica gel layer is 2 mm. The degradable composite material herein used the corresponding degradable composite material of example 6.
The corresponding composite materials obtained in the above embodiments are randomly selected to be made into bars with a diameter of 3mm for corresponding performance tests, and the specific test results are shown in table 1 below:
the various strengths (tensile strength and bending strength) can be tested according to the standard, the bending strength is tested according to GB/T9341-2008, and the testing speed is 2 mm/min; the tensile strength is carried out according to GB/T1040-; the notched impact strength was tested in accordance with ASTM D256.
The test results show that the composite material has the effects of high strength performance and degradation rate, can be more effectively used as a material of a disposable uterine curettage spoon, and particularly can realize more excellent degradation performance and bending strength performance by adding a small amount of choline acetate ionic liquid and/or 1-butyl-3-methylimidazole tetraborate, and can also well improve the strength performance of the material by carrying out a mixed addition mode of grading the added fiber reinforced material.
The specific embodiments described herein are merely illustrative of the spirit of the invention. Various modifications or additions may be made to the described embodiments or alternatives may be employed by those skilled in the art without departing from the spirit or ambit of the invention as defined in the appended claims.
While the invention has been described in detail and with reference to specific examples thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.
Claims (9)
1. A degradable composite material for manufacturing a uterine curettage spoon is characterized by comprising the following components in parts by weight:
polylactic acid-glycolic acid copolymer: 60-70 parts of; chitosan oligosaccharide: 10-15; poly (pivalolactone): 5.0 to 6.2; antioxidant: 1.0 to 8.0; a composite toughening agent: 8.0-9.0; biodegradable fiber-reinforced material: 10-13; modified inorganic filler: 2.0-5.0, wherein the modified inorganic filler is prepared by polylactic acid coated nano silicon dioxide particles;
the degradable composite material also contains 0.5-1.0 part by weight of choline acetate ionic liquid and/or 1-butyl-3-methylimidazole tetraborate.
2. The degradable composite material for making the uterine curettage spoon according to claim 1, wherein the molecular weight of the polylactic acid-glycolic acid copolymer is 5000-10000 Da, and the weight ratio of the polylactic acid-glycolic acid copolymer: chitosan oligosaccharide: the weight ratio of the poly (neopentane lactone) is as follows: 65: 11-12: 5.1 to 5.3.
3. The degradable composite material for uterine curettage spoon production according to claim 2, characterized in that the molecular weight of the polypivalolactone is: 6000Da to 8000 Da.
4. The degradable composite material for making the curettage spoon according to claim 1, 2 or 3, wherein the biodegradable fiber reinforced material is one or more selected from tencel fiber, polylactic acid fiber and carbon fiber.
5. The degradable composite material for uterine curettage spoon production according to claim 4, characterized in that the biodegradable fiber reinforcement material is selected from the group consisting of lyocell fibers, polylactic acid fibers and a mixture of carbon fibers, and the aspect ratio of the carbon fibers is larger than the aspect ratio of lyocell fibers and polylactic acid fibers.
6. The degradable composite material for the curettage spoon as claimed in claim 5, wherein the aspect ratio of the carbon fibers is 5-6: 1, the length-diameter ratio of the tencel fiber and the polylactic acid fiber is respectively and independently selected from 2-3: 1.
7. the degradable composite material for making the curettage spoon according to claim 1, 2 or 3, wherein the curettage spoon made of the degradable composite material is coated with a silica gel film layer on the surface.
8. The degradable composite material for making the curettage spoon according to claim 1, 2 or 3, wherein the composite toughening agent is a mixture of tributyl citrate and polyethylene glycol.
9. The degradable composite material for making a uterine curettage spoon according to claim 1, 2 or 3, wherein the ratio of polylactic acid: the mass ratio of the nano silicon dioxide particles is 1: 0.1 to 0.3.
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| KR100840394B1 (en) * | 2007-02-12 | 2008-06-23 | 최명 | Injectable polymer biodegradable granules for tissue regeneration and how to produce method there of |
| CN102727940B (en) * | 2011-04-12 | 2015-09-02 | 上海林静医疗器械有限公司 | Degradation type disposable uterine probe and preparation method |
| CN106147164B (en) * | 2015-04-23 | 2018-05-01 | 上海微创医疗器械（集团）有限公司 | A kind of medical composite material and preparation method thereof |
| CN108752887B (en) * | 2018-06-20 | 2021-03-26 | 台州市中心医院（台州学院附属医院） | Environment-friendly degradable composite material for disposable vaginal dilator |
| CN108939172B (en) * | 2018-08-13 | 2020-12-25 | 台州市中心医院（台州学院附属医院） | Degradable material for disposable uterine probe |
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