CN107805375A - Medical lactic acid composite material and the disposable syringe of preparation - Google Patents

Medical lactic acid composite material and the disposable syringe of preparation Download PDF

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Publication number
CN107805375A
CN107805375A CN201711075741.6A CN201711075741A CN107805375A CN 107805375 A CN107805375 A CN 107805375A CN 201711075741 A CN201711075741 A CN 201711075741A CN 107805375 A CN107805375 A CN 107805375A
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China
Prior art keywords
titanium
pla
parts
nucleator
composite
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Withdrawn
Application number
CN201711075741.6A
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Chinese (zh)
Inventor
应剑军
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Liandu Lishui Jun Zheng Die Factory
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Liandu Lishui Jun Zheng Die Factory
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Priority to CN201711075741.6A priority Critical patent/CN107805375A/en
Publication of CN107805375A publication Critical patent/CN107805375A/en
Withdrawn legal-status Critical Current

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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/04Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20Oxides; Hydroxides
    • C08K3/22Oxides; Hydroxides of metals
    • C08K2003/2237Oxides; Hydroxides of metals of titanium
    • C08K2003/2241Titanium dioxide
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/30Sulfur-, selenium- or tellurium-containing compounds
    • C08K2003/3009Sulfides
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/06Biodegradable
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00Applications
    • C08L2203/02Applications for biomedical use
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/24Crystallisation aids
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00Properties characterising the ingredient of the composition
    • C08L2207/04Thermoplastic elastomer

Abstract

The present invention relates to medical lactic acid composite material and the disposable syringe of preparation.It is specifically a kind of medical degradable composite material, it contains PLA(PLA), toughener and nucleator, wherein every 100 parts by weight PLA(PLA) containing 10 50 parts of toughener, 15 parts of nucleator.The whole blend components of the present invention are medical grade non-toxic product, its synthon and corresponding polymer are to human body totally nontoxic, water and carbon dioxide can be degraded to automatically in 46 months under composting conditionses, small molecule plasticizer is free of in blending resin, such compound will not occur and separate out, pollute decoction and enter the danger of human body.It can be as the PP Pipe Compound of disposable degradable syringe, for preparing disposable degradable syringe.Material property in terms of antibacterial, degraded is substantially better than pure polylactic acid raw material.Inventive formulation rationally, it is stable performance, free from environmental pollution, can produce in enormous quantities in cleaning shop.

Description

Medical lactic acid composite material and the disposable syringe of preparation
Technical field
The present invention relates to a kind of high polymer material, the medical degradable syringe of specifically a kind of blending and modifying, which is used, to be gathered Lactic acid composite, and the syringe prepared.
Background technology
China medical macromolecular materials product development starts late, just develop the 1970s disposable transfusion device, The product such as syringe and plastic blood bag, at present disposable syringe base material generally given up using material, this kind of syringe such as polypropylene It can not voluntarily be degraded after abandoning, pollute environment, endanger the health of people.Common centralized burning destroys method, not only can not be real Existing resources circulation recycles, and can aggravate environmental pollution.Driven by interests, discarded syringe is illegal sharp again by criminal With the medical hidden danger such as cross-infection can be produced.So the disposable medical infusion apparatus of exploitation fully biodegradable is carved and not allowed It is slow.
The fusing point of PLA is higher(175 °C), its physical property is between PET (poly terephthalic acid class plastics)And PA-6 (nylon plastic(s))Between, crystallinity is big, excellent transparency, has good solvent resistance, protection against the tide, grease resistance, gas permeability, also has Certain fungus resistance, anti-flammability and ultraviolet-resistent property.PLA(PLA) there is excellent biocompatibility, biodegradability, gather Lactic acid also has preferable processing characteristics, can be suitably used for the processing methods such as traditional extrusion, injection, blowing, poly-lactic acid material Can and processing characteristics Shortcomings, it is mainly more crisp, and existing poly-lactic acid material is significantly improved sky in terms of sterilization Between.
The content of the invention
The technical problems to be solved by the invention are to overcome above-mentioned the deficiencies in the prior art, there is provided one kind formula is reasonable, property Can be stable, bactericidal property is good, and degradation speed is fast, the disposable syringe that can produce in enormous quantities in cleaning shop with it is medical can Degrading composite, and the syringe prepared.
The present invention solves the technical scheme that above-mentioned technical problem uses:A kind of medical degradable composite material, its feature It is:Contain PLA(PLA), toughener and nucleator, wherein every 100 parts by weight PLA(PLA toughener 10-50) is contained Part, nucleator 1-5 parts.
Toughener of the present invention is thermoplastic elastomer (TPE), can be thermoplastic polyurethane() or phenylethylene thermoplastic TPU Property elastomer (SEBS or SBS).
Described nucleator is inorganic nucleator or organic nucleating agent.
Further, described nucleator includes montmorillonite.
Further, titanium elements are contained in described degradable composite material, on the basis of the weight of composite, titanium member Cellulose content is 50ppm-10000ppm.Preferably, titanium elements content is 100-5000ppm, is more highly preferred to, and titanium elements content is 300-2000ppm.In one of embodiment, titanium elements content is 100ppm, and in one embodiment in addition, titanium elements contain Measure as 200ppm, in one embodiment in addition, titanium elements content is 300ppm.Secondly, titanium elements content can also be 500ppm、800ppm、1000ppm、1500ppm。
Described titanium elements are provided by the compound of titaniferous, optionally there is titanium oxide, titanium hydroxide, titanium sulfide, four chlorinations Titanium, titanium trichloride, titanium fluoride, titanium bromide, titanium boride, titanium silicide, titanate, titanate esters etc..
Titanium elements have excellent catalytic effect, and have good antibiotic property and corrosion resistance.The addition of titanium elements can To cause the composite to have excellent antibacterial effect, titanium elements bactericide can prevent and treat fungal disease, and and can preventing and treating is thin Fungal disease.But moreover, we have surprisingly found that, the addition of titanium elements can also improve the degradation property of material, can be with Reduce about 1/4 degradation time, this for reduce discarded object accumulation be highly beneficial.
In addition, the present invention also provides a kind of disposable medical syringe, it is prepared by above-mentioned degradable material.
The method that syringe is prepared for degradable material is not limited, and method generally in the art may be selected, such as note Shaping, extrusion molding etc. are penetrated, is preferably injection moulded.
Beneficial effects of the present invention:
The present invention selects the PLA of proper ratio(PLA), toughener, and the titanium elements for adding appropriate level are prepared and can dropped Solve composite.Toughener thermoplasticity elastomer(TPU or SEBS or SBS), using its titanium line-shear band toughening mechanism, carry The toughness of high material.The addition of nucleator can further improve the intensity of material.The addition of titanium elements can improve composite wood The antibiotic property of material, and be found surprisingly that and can improve degradation property.The composite processing process is simple, practical, can answer For manufacturing disposable degradable syringe.
The present invention is with PLA(PLA) be material of main part medical degradable composite material, the composite it is main Feature is:Whole blend components are medical grade non-toxic product, its synthon and corresponding polymer to human body totally nontoxic, Water and carbon dioxide can be degraded to automatically in 4-6 under composting conditionses months, small molecule plasticizer is free of in blending resin, will not Such compound occurs and separates out, pollute decoction and enter the danger of human body.It can be as disposable degradable syringe PP Pipe Compound, for preparing disposable degradable syringe.It is fast that disposable syringe voluntarily destroys speed, solves useless modeling The pollution problem of material, disposable syringe is set to be really achieved disposable purpose.The material is in terms of antibacterial, degraded Property is substantially better than pure polylactic acid raw material.Inventive formulation rationally, it is stable performance, free from environmental pollution, being can be large quantities of in cleaning shop Amount production, the PP Pipe Compound suitable for making a one-time use only degradable syringe.
Embodiment
With reference to embodiment, the invention will be further described:
A kind of medical degradable composite material of the present invention, a kind of medical degradable composite material, it is characterized in that:Contain PLA (PLA), toughener, wherein every 100 parts by weight PLA(PLA) containing toughener 10-50 parts, nucleator 1-5 parts.
Toughener of the present invention is thermoplastic elastomer (TPE), can be thermoplastic polyurethane() or phenylethylene thermoplastic TPU Property elastomer (SEBS or SBS).
Described nucleator is inorganic nucleator or organic nucleating agent.
Further, described nucleator includes montmorillonite.
Further, titanium elements are contained in described degradable composite material, on the basis of the weight of composite, titanium member Cellulose content is 50ppm-10000ppm.Preferably, titanium elements content is 100-5000ppm, is more highly preferred to, and titanium elements content is 300-2000ppm.In one of embodiment, titanium elements content is 100ppm, and in one embodiment in addition, titanium elements contain Measure as 200ppm, in one embodiment in addition, titanium elements content is 300ppm.Secondly, titanium elements content can also be 500ppm、800ppm、1000ppm、1500ppm。
Described titanium elements are provided by the compound of titaniferous, optionally there is titanium oxide, titanium hydroxide, titanium sulfide, four chlorinations Titanium, titanium trichloride, titanium fluoride, titanium bromide, titanium boride, titanium silicide, titanate, titanate esters etc..
Various embodiments of the present invention are formulated various raw materials and are well mixed, and are then granulated in double-screw extruding pelletizing machine, will be upper State premix to be transported in double screw extruder, obtain composite, and test respective performances index.Then in 100,000 grades of purifications Injection molding is carried out on injection machine in workshop, obtains product.Resulting product uniform color, outward appearance are good.
Embodiment 1:
Weigh 100 parts of PLA, 10 parts of SEBS, 2 parts of montmorillonite in proportion, add titanium oxide so that titanium elements content is 300ppm, 5min is blended using high speed agitator, mixed material is added in double-screw extruding pelletizing machine and is granulated, cools down, pelletizing, Obtained material is carried out testing its mechanical property, anti-microbial property and degradation property.
Embodiment 2:
Weigh 100 parts of PLA, 20 parts of SEBS, 2 parts of montmorillonite in proportion, add titanium sulfide so that titanium elements content is 500ppm, 5min is blended using high speed agitator, mixed material is added in double-screw extruding pelletizing machine and is granulated, cools down, pelletizing, Obtained material is carried out testing its mechanical property, anti-microbial property and degradation property.
Embodiment 3:
Weigh 100 parts of PLA, 30 parts of SEBS, 2 parts of montmorillonite in proportion, add titanium tetrachloride so that titanium elements content is 800ppm, 5min is blended using high speed agitator, mixed material is added in double-screw extruding pelletizing machine and is granulated, cools down, pelletizing, Obtained material is carried out testing its mechanical property, anti-microbial property and degradation property.
Embodiment 4:
Weigh 100 parts of PLA, 40 parts of SEBS, 2 parts of montmorillonite in proportion, add titanate so that titanium elements content is 1000ppm, 5min is blended using high speed agitator, mixed material is added in double-screw extruding pelletizing machine and is granulated, cools down, cuts Grain, carries out testing its mechanical property, anti-microbial property and degradation property to obtained material.
Embodiment 5:
Weigh 100 parts of PLA, 50 parts of SEBS, 2 parts of montmorillonite in proportion, add titanate esters so that titanium elements content is 1500ppm, 5min is blended using high speed agitator, mixed material is added in double-screw extruding pelletizing machine and is granulated, cools down, cuts Grain, carries out testing its mechanical property, anti-microbial property and degradation property to obtained material.
Comparative example 1:
100 parts of PLA, 20 parts of SEBS, 2 parts of montmorillonite are weighed in proportion, 5min are blended using high speed agitator, by mixture Material is added in double-screw extruding pelletizing machine and is granulated, and is cooled down, pelletizing, obtained material is carried out testing its mechanical property, antibiotic property Energy and degradation property.
Test the results are shown in Table 1
Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5 Comparative example 1
Elongation at break/% 109 168 199 226 272 168
Tensile strength/MPa 42 37 31 26 23 37
Anti-microbial property 82% 85% 87% 88% 90% 40%
Degradation property*/ day 74 68 65 62 59 87
* the time therein is the time of degraded half weight.
It can be seen that the addition of titanium elements effectively improves the anti-microbial property of lactic acid composite material.Moreover, titanium elements Add improves the degradation property of material simultaneously, and degradation time about shortens 1/4 or so.
The explanation of above example is only intended to help the core concept for understanding the present invention.It should be pointed out that for this area Those of ordinary skill for, under the premise without departing from the principles of the invention, can also to the present invention carry out it is some improvement and repair Decorations, but these are improved and modification is also fallen into the range of the claims in the present invention are claimed.

Claims (10)

1. a kind of medical degradable composite material, it is characterized in that:Contain PLA(PLA), toughener and nucleator, wherein often 100 parts by weight PLAs(PLA) containing toughener 10-50 parts, nucleator 1-5 parts.
2. composite according to claim 1, described toughener is thermoplastic elastomer (TPE).
3. composite according to claim 1, described toughener can be thermoplastic polyurethane() or styrene TPU Analog thermoplastic elastomer (SEBS or SBS).
4. composite according to claim 1, described nucleator is inorganic nucleator or organic nucleating agent.
5. composite according to claim 1, described nucleator includes montmorillonite.
6. composite according to claim 1, contain titanium elements in described degradable composite material.
7. composite according to claim 1, on the basis of the weight of composite, described titanium elements content is 50ppm-10000ppm, preferably 100-5000ppm, more preferably 300-2000ppm.
8. according to the composite described in claim any one of 5-7, described titanium elements are provided by the compound of titaniferous.
9. composite according to claim 8, described titanium-containing compound optionally has titanium oxide, titanium hydroxide, sulphur Change titanium, titanium tetrachloride, titanium trichloride, titanium fluoride, titanium bromide, titanium boride, titanium silicide, titanate, titanate esters etc..
10. a kind of disposable medical syringe, it is prepared as the composite described in claim any one of 1-9.
CN201711075741.6A 2017-11-06 2017-11-06 Medical lactic acid composite material and the disposable syringe of preparation Withdrawn CN107805375A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108384210A (en) * 2018-04-04 2018-08-10 中国科学院长春应用化学研究所 A kind of application of pyruvates and polydactyl acid
CN114085483A (en) * 2021-11-26 2022-02-25 安徽江南医疗器械股份有限公司 Preparation method of completely biodegradable disposable infusion hose

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101519527A (en) * 2009-03-24 2009-09-02 山东威高集团医用高分子制品股份有限公司 Medical degradable composite material
CN105623217A (en) * 2016-02-27 2016-06-01 江苏金扬子包装科技有限公司 Polylactic acid bio-based special material for disposable syringe

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101519527A (en) * 2009-03-24 2009-09-02 山东威高集团医用高分子制品股份有限公司 Medical degradable composite material
CN105623217A (en) * 2016-02-27 2016-06-01 江苏金扬子包装科技有限公司 Polylactic acid bio-based special material for disposable syringe

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108384210A (en) * 2018-04-04 2018-08-10 中国科学院长春应用化学研究所 A kind of application of pyruvates and polydactyl acid
CN114085483A (en) * 2021-11-26 2022-02-25 安徽江南医疗器械股份有限公司 Preparation method of completely biodegradable disposable infusion hose
CN114085483B (en) * 2021-11-26 2022-09-02 安徽江南医疗器械股份有限公司 Preparation method of completely biodegradable disposable infusion hose

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