CN101514250A - Polyolefin thermoplastic elastomer blood storage material and preparation method thereof - Google Patents

Polyolefin thermoplastic elastomer blood storage material and preparation method thereof Download PDF

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Publication number
CN101514250A
CN101514250A CNA2009100200435A CN200910020043A CN101514250A CN 101514250 A CN101514250 A CN 101514250A CN A2009100200435 A CNA2009100200435 A CN A2009100200435A CN 200910020043 A CN200910020043 A CN 200910020043A CN 101514250 A CN101514250 A CN 101514250A
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component
blood
thermoplastic elastomer
storage material
polyolefin thermoplastic
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栾世方
殷敬华
王建卫
杜兰平
朱连超
李忠志
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Changchun Institute of Applied Chemistry of CAS
Shandong Weigao Group Medical Polymer Co Ltd
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Changchun Institute of Applied Chemistry of CAS
Shandong Weigao Group Medical Polymer Co Ltd
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Abstract

The invention relates to a polyolefin thermoplastic elastomer blood storage material which comprises component A, component B and component C; wherein the middle part of component A is a random copolymer segmer of ethene and 1-butylene or a random copolymer segmer of ethene and propylene, two ends are provided with a block polymer with styrene block for end capping, and the component A takes 60-76 percent of the gross weight of the material; component B is ethene-vinyl acetate (EVA) resin and takes 10-28 percent of the gross weight of the material; component C is polyethylene (PE) resin and takes 10-20 percent of the gross weight of the material. A preparation method is combining the pre-irradiation treatment of one component with a melt-blending and micro-crosslinking method to prepare the polyolefin thermoplastic elastomer blood storage material. The invention can be used for manufacturing a blood bag, a conduit, a component and the like for storing human blood and blood component. During the processing, promoters such as plasticizer, antioxidant and the like are not added, micromolecular organic substance separation and pollution of liquid medicine and blood do not occur, and the polyolefin thermoplastic elastomer blood storage material is harmless to human body and the environment.

Description

Polyolefin thermoplastic elastomer blood storage material and preparation method thereof
Technical field
The invention belongs to the technical field of polyolefin blend resin, is polyolefin thermoplastic elastomer blood storage material and preparation method thereof specifically, and this resin can be used for making blood and blood ingredient storage vessel.
Background technology
We know, polyvinyl chloride (PVC) low price, and comprehensive physical and mechanical properties is good, generally is used as the material of infusion sets for single use, blood transfusion utensil at home and abroad.Along with clinical application extensively and profoundly with the relevant medical science and technology development, it is found that itself there is potential safety hazard in the PVC material, processing and use properties on also have many defectives.Polyvinyl chloride resin can produce a spot of vinyl chloride monomer in producing or processing, this compound has been proved to be carcinogenic substance.In order to obtain the flexible PVC goods, must use softening agent (up to the organic esters of 40%~60% parts by weight, as DEHP softening agent etc.) in the processing, this class softening agent can enter soup and blood, and enters human body thereupon, and HUMAN HEALTH is formed hidden danger.For preventing that PVC from adding the thermolysis in man-hour, add thermo-stabilizer (metal ion is based on calcium ion and zine ion) usually, excessive suction also can have a negative impact to human body.The waste treatment difficulty of PVC medical disposable material is buried for a long time and is not degraded, and burns then to produce hydrogenchloride with toxic gases such as dioxin, contaminate environment.In addition, PVC adds can decompose the generation hydrogen chloride gas man-hour, not only corrosion processing equipment, and threat operator ' s health.
In addition, blood that the PVC material is made and blood ingredient storage vessel also exist: the quality guaranteed period lacks (containing Precerving liquid), after empty bag is placed half a year, and phenomenon such as easily exceed standard such as pure leachable, reducing substance, zine ion and pH value.An important indicator of blood and blood ingredient storage vessel performance requriements is a ventilation property.PVC blood and blood ingredient storage vessel need the softening agent of big consumption to improve its flexibility and toughness, and plasticizer consumption is big, and general ventilation property will be lower.Lower ventilation property is disadvantageous to some blood ingredient as hematoblastic storage.
In view of the problem of PVC material and blood and the existence of blood ingredient storage vessel, the novel material that all on the research and development price, can contend with both at home and abroad, performance satisfies service requirements with PVC.So far.Developed the multiple non-PVC material that is suitable for stored blood and blood ingredient,,, also had problems, be further improved though these material physical properties, chemical property can both satisfy service requirements mainly based on polyolefine material.
Shen Qing non-PVC blood bag material patent has in recent years: United States Patent (USP) 5,026, and 347 disclose the SIS/SEBS/butyryl citric acid tri-n-hexyl ester/non-PVC blood of polyacrylic blend bag material; Chinese patent CN 95191306.9 discloses the non-PVC blood of the blend bag material of ethylene-vinyl acetate copolymer/SIS/SEBS/ultra-low density polyethylene; United States Patent (USP) 5,952,423 disclose the non-PVC blood of the blend bag material of polypropylene/SIS/SEBS/nylon/citrate/vitamin E; United States Patent (USP) 5,683,768 disclose the non-PVC blood of the blend bag material of polypropylene/SIS/SEBS/nylon; United States Patent (USP) 6,579,583 disclose the non-PVC blood of the blend bag material of ethylene-vinyl acetate copolymer/SIS/SEBS/ultra-low density polyethylene; United States Patent (USP) 4,479,989 disclose the non-PVC blood of the blend bag material of linear low density polyethylene/SIS/SEBS; United States Patent (USP) 4,561, the non-PVC blood of the blend of 110 disclosed polyolefine/ethylene-vinyl acetate copolymers bag material etc.The U.S. hundred special companies 40% thrombocyte bag has adopted polyolefine material to make.
Many can not the reducing completely that is used to make blood and the existence of blood ingredient storage vessel material that above-mentioned patent is related: (1) material thermal resistance is bad, and this can make blood or blood ingredient storage bag bag deformation occur when high-temperature steam is sterilized.And oxyethane steam dissolves in the Precerving liquid, and make blood or the blood ingredient storage vessel goods that contain Precerving liquid can not be used ethylene oxide sterilizing, and this limits the application of these materials greatly.(2) material mechanical performance is relatively poor.Though the blood of these material preparations or blood ingredient storage bag bag intensity can satisfy the GB requirement, bag intensity is still not high, is prone to phenomenons such as breakage, leakage in the practical application.(3) for improving the small molecular ester compound that material anti-hemolysis performance is added, as: butyryl citric acid tri-n-hexyl ester, citrate, can infiltrate in blood or the soup, human body is caused potential hazard.
Summary of the invention
Technical problem to be solved by this invention is to overcome above-mentioned the deficiencies in the prior art, provide a kind of prescription reasonable, preparation is simple, material flexibility, elasticity, good toughness, the resistance toheat height, free from environmental pollution during destruction, can replace polyolefin thermoplastic elastomer blood storage material of PVC use and preparation method thereof.
The technical scheme that the present invention solves the problems of the technologies described above employing is: a kind of polyolefin thermoplastic elastomer blood storage material, form by three kinds of components:
The A component, a kind of by ethene and 1-butylene the random copolymers segment or the random copolymers segment of ethene and propylene as middle portion, and the segmented copolymer that constitutes by vinylbenzene segment end-blocking, melt flow rate (MFR) (230 ℃ 5kg) are 0.5~10.0g/10min.A component shared weight ratio in blood storage material is 60~76%.The A component mainly rises increases the goods transparency, improve the film flexibility, and elastic effect is provided.
The B component, a kind of ethylene-vinyl acetate (EVA) resin, melt flow rate (MFR) (230 ℃ 2.16kg) are 5.0~20.0g/10min.B component shared weight ratio in blood storage material is 10~28%.The B component has good anti-hemolysis performance, can give proprietary material good blood compatibility, avoids using the small molecular ester material.
C component, a kind of polyvinyl resin, its comonomer are 1-butylene, 1-hexene or 1-octene, melt flow rate (MFR) (190 ℃ 2.16kg) are 0.5~10.0g/10min.C component shared weight ratio in blood storage material is 10~20%.The C component has rigidity, intensity and adhesive property preferably, can improve the physical and mechanical properties of proprietary material, gives its good heat sealability.
The preparation method of said polyolefins thermoplastic elastomer blood storage material of the present invention comprises the steps:
(1) adopt electron beam or gamma-rays that any component in A component, B component, the C component is carried out pre-irradiation earlier and handle, irradiation dose is 2~12K6y, obtains containing the constituent materials of macromolecular radical.
(2) constituent materials of in proportion pre-irradiation being handled and not the constituent materials of irradiation join in Henschel mixing tank or drum tumbler or the V-type mixing tank mechanically mixing after 2~8 minutes, in the response type twin screw extruder in fusion and little crosslinked, setting forcing machine is 140~260 ℃ along charging opening to a mouthful mould direction temperature, die temperature is 180~240 ℃, and the residence time of blend material in forcing machine is 1.0~3.0 minutes.
(3) blend per os mould extrude, pelletizing, drying, prepare polyolefin thermoplastic elastomer blood storage material.
Polyolefin thermoplastic elastomer blood storage material of the present invention, except physicals, chemical property and biological property satisfied the GB requirement fully, a lot of performances were better than blood and blood ingredient storage vessel pvc material greatly.The major advantage that this material has is: all constituent materials is the nontoxic product of medical grade through authentication, and its synthon and corresponding polymer have been avoided the toxicity problem of PVC material itself to the human body totally nontoxic; In the proprietary material preparation process, do not add any auxiliary agent that comprises softening agent, thermo-stabilizer, the danger that does not exist micromolecular compound to separate out, pollute soup and then enter human body.
Preparation method of the present invention prepares blood storage material by a kind of constituent materials being carried out the pre-irradiation processing in conjunction with melt blending and little cross-linking method, thereby under the prerequisite of not using the small molecules initiator, obviously improve the thermotolerance of blood storage material, improve the mechanical property of material, make the proprietary material that obtains really have practical value.
Polyolefin thermoplastic elastomer blood storage material of the present invention can be used for the preparation of disposable transfusion set tool, blood bag etc.Can adopt methods such as blowing, extrusion molding, calendering to prepare film forming, also can be extruded into linking conduit, and can adopt modes such as laser welding, sweating soldering that film material and tubing are assembled into the blood bag product.The blood of this material preparation and blood ingredient storage vessel can not discharge any small-molecule substance, human body are not caused potential hazard.The excellent heat resistance of this material, blood bag bag deformation do not occur under moist heat sterilization.The physical and mechanical properties of this proprietary material is good, and flexibility, elasticity, good toughness phenomenons such as breakage, leakage can not occur in high speed centrifugation and the practical application.
Embodiment
The invention will be further described below in conjunction with embodiment, but scope of the present invention is not limited to these embodiment.
The physical index of resin raw material that each embodiment uses sees table 1 for details.
Employed constituent materials and performance perameter among table 1 embodiment
Figure A20091002004300061
* MFR, melt flow rate (MFR), the g/10min of unit.The test condition of A1 is 200 ℃, 5.0Kg;
The test condition of B1, B2, C1 and C2 is 190 ℃, 2.16Kg.
Embodiment 1
Weight ratio by 70/20/10 takes by weighing A1, B1 and C1 constituent materials, and with B1 component electron beam pre-irradiation, irradiation dose 5KGy mixed three kinds of constituent materialss 5 minutes in high speed agitator, obtain Preblend.Preblend is added in the response type twin screw extruder, and the screw diameter of forcing machine is 40mm, and length-to-diameter ratio is 36, and setting forcing machine is 150~230 ℃ along charging opening to a mouthful mould direction temperature, and die temperature is 220 ℃.Blend per os mould is extruded, cooling, pelletizing, obtains blood storage material.The test results such as melt flow rate (MFR), transmittance, mist degree, surface hardness and mechanical property of liquid and blood ingredient storage vessel proprietary material are listed in the table 2.
Embodiment 2
Weight ratio by 65/15/20 takes by weighing A2, B2 and C2 constituent materials, with C2 component electron beam pre-irradiation, irradiation dose 10KGy, three kinds of constituent materialss were mixed in high speed agitator 5 minutes, obtaining Preblend is set at 230 ℃ except that forcing machine is set at 150~240 ℃ and die temperature along charging opening to a mouthful mould direction temperature, employed equipment, processing conditions and step etc. are all identical with embodiment 1, adopt the method identical to carry out sample preparation with embodiment 1, and test respective performances index, the results are shown in Table 2.
Embodiment 3
Weight ratio by 60/25/15 takes by weighing A1, B2 and C1 constituent materials, with A1 component gamma-rays pre-irradiation, irradiation dose 3KGy, other employed equipment, processing conditions and step etc. are all identical with embodiment 1, adopt the method identical to carry out sample preparation with embodiment 1, and test respective performances index, the results are shown in Table 2.
Embodiment 4
Weight ratio by 68/16/16 takes by weighing A1, B2 and C2 constituent materials, and with B1 component gamma-rays pre-irradiation, irradiation dose 12KGy mixed three kinds of constituent materialss 5 minutes in high speed agitator, obtain Preblend.Preblend is added in the response type twin screw extruder, and the screw diameter of forcing machine is 70mm, and length-to-diameter ratio is 48, and setting forcing machine is 140~230 ℃ along charging opening to a mouthful mould direction temperature, and die temperature is 220 ℃.Reactant per os mould is extruded, cooling, pelletizing, obtains blood storage material.Adopt the method identical with embodiment 1 to carry out sample preparation, and test the respective performances index, the results are shown in Table 2.
Embodiment 5
Weight ratio by 76/10/14 takes by weighing A1, B1 and C2 constituent materials, with C1 component gamma-rays pre-irradiation, irradiation dose 8KGy, except that being set at 150~240 ℃ and die temperature along charging opening to a mouthful mould direction temperature, forcing machine is set at 230 ℃, employed equipment, processing conditions and step etc. are all identical with embodiment 4, adopt the method identical with embodiment 1 to carry out sample preparation, and test the respective performances index, the results are shown in Table 2.
Embodiment 6
Weight ratio by 62/28/10 takes by weighing A2, B1 and C1 constituent materials, with B1 component electron beam pre-irradiation, irradiation dose 6KGy uses equipment, processing conditions and step etc. all identical with embodiment 5, adopt the method identical to carry out sample preparation with embodiment 1, and test respective performances index, the results are shown in Table 2.
Embodiment 7
Weight ratio by 74/14/12 takes by weighing A2, B1 and C2 constituent materials, with C2 component electron beam pre-irradiation, irradiation dose 6KGy, use equipment, processing conditions and step etc. are all identical with embodiment 1, adopt the method identical to carry out sample preparation with embodiment 1, and test respective performances index, the results are shown in Table 2.
Embodiment 8
Weight ratio by 75/15/10 takes by weighing A2, B2 and C1 constituent materials, with A2 component electron beam pre-irradiation, irradiation dose 2KGy, use equipment, processing conditions and step etc. are all identical with embodiment 1, adopt the method identical to carry out sample preparation with embodiment 1, and test respective performances index, the results are shown in Table 2.
The present invention presses the method for GB/T 19789-2005 (China) and measures oxygen gas permeability.Gained the results are shown in the following table 3.The testing method principle is as follows: will permeate the chamber with sample to be tested and be separated into two independently air flow systems, at first clean with the carrier gas of anaerobic, deviate from remnant oxygen in the scavenge system and oxygen that sample is absorbed, after reaching balanced null point, begin test, one side of sample is mobile test gas (can be purity oxygen or oxygenous mixed gas), and opposite side is the mobile drying nitrogen.The pressure on sample both sides equates, but the oxygen partial pressure difference.Under the effect of difference in oxygen concentration between, oxygen sees through film and is delivered in the transmitter (coulomb electric charge method transmitter) by nitrogen gas stream, accurately measures the amount of oxygen that carries in the nitrogen gas stream by transmitter, thereby calculates the OTR oxygen transmission rate of material.
Used test equipment is the MOCON OX-TRAN2/21MH of U.S. Mocon Inc. gas-permeable instrument.Laboratory sample is of a size of 10.8 * 10.8cm 2, useful area is 50cm 2, full test thickness 2mm, thickness of sample be at 0.40~0.5mm, test duration 48h, oxygen concentration 10%.
Each component blend proportioning and blend performance among table 2 embodiment
Figure A20091002004300091
* PVC1 is the red corpuscle blood bag PVC material that Medical High Molecular Product Co., Ltd., Shandong Weigao Group produces in the comparative example; PVC2 is the thrombocyte bag PVC material that the U.S. hundred special companies produce.
The material of table 3. embodiment preparation and the oxygen transit dose of PVC material
Material number Oxygen transit dose (cc/m 2/d)
Comparative example 1 57
Comparative example 2 84
Embodiment 1 78
Embodiment 2 87
Embodiment 3 100
Embodiment 4 112
Embodiment 5 91
Embodiment 6 102
Embodiment 7 96
Embodiment 8 84
* PVC1 is the red corpuscle blood bag PVC material that Medical High Molecular Product Co., Ltd., Shandong Weigao Group produces in the comparative example; PVC2 is the thrombocyte bag PVC material that the U.S. hundred special companies produce.
Contrast as seen, the OTR oxygen transmission rate of the blending resin material that embodiment 1 prepares is between two kinds of PVC blood bag materials, is slightly less than thrombocyte blood bag material, and greater than red corpuscle blood bag material, promptly this material is suitable for storage of red blood cells fully.The OTR oxygen transmission rate of the specialized material of embodiment 2~embodiment 9 preparation is all greater than two kinds of PVC blood bag film materials, and promptly the blending resin that provides of this patent has better ventilation property, is suitable for red corpuscle and hematoblastic storage.

Claims (6)

1. polyolefin thermoplastic elastomer blood storage material is characterized in that its composition comprises:
The A component accounts for the segmented copolymer of material gross weight 60~76%, and the middle portion of this segmented copolymer is made up of the random copolymers segment of ethene and 1-butylene or the random copolymers segment of ethene and propylene, and two ends are by vinylbenzene segment end-blocking;
The B component accounts for ethylene-vinyl acetate (EVA) resin of material gross weight 10~28%;
The C component accounts for polyethylene (PF) resin of material gross weight 10~20%.
2. polyolefin thermoplastic elastomer blood storage material according to claim 1 is characterized in that melt flow rate (MFR) (230 ℃ 5kg) are 0.5~10.0g/10min of segmented copolymer in the described A component.
3. polyolefin thermoplastic elastomer blood storage material according to claim 1 is characterized in that melt flow rate (MFR) (230 ℃ 2.16kg) are 5.0~20.0g/10min of described B component ethylene-vinyl acetate (EVA) resin.
4. polyolefin thermoplastic elastomer blood storage material according to claim 1, it is characterized in that comonomer is 1-butylene, 1-hexene or 1-octene in the described C component polyvinyl resin, melt flow rate (MFR) (190 ℃ 2.16kg) are 0.5~10.0g/10min.
5. the preparation method of the described polyolefin thermoplastic elastomer blood storage material of claim 1 is characterized in that it comprises the steps:
(1) adopts electron beam or gamma-rays that any component in described A component, B component, the C component is carried out pre-irradiation earlier and handle, obtain containing the constituent materials of macromolecular radical;
(2) constituent materials of in proportion pre-irradiation being handled and not the constituent materials of irradiation join in Henschel mixing tank or drum tumbler or the V-type mixing tank mechanically mixing after 2~8 minutes, melt blending and little crosslinked in the response type twin screw extruder, setting forcing machine is 140~260 ℃ along charging opening to a mouthful mould direction temperature, die temperature is 180~240 ℃, and the residence time of blend material in forcing machine is 1.0~3.0 minutes;
(3) blend per os mould extrude, pelletizing, drying, make polyolefin thermoplastic elastomer blood storage material.
6. the preparation method of polyolefin thermoplastic elastomer blood storage material according to claim 5 is characterized in that described electron beam or gamma-ray irradiation dose are 2~12KGy.
CNA2009100200435A 2009-03-27 2009-03-27 Polyolefin thermoplastic elastomer blood storage material and preparation method thereof Pending CN101514250A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102108146A (en) * 2010-03-29 2011-06-29 宁波先锋新材料股份有限公司 Polyolefin thermoplastic elastomer (TPE) composition and preparation method thereof
CN103566431A (en) * 2013-11-15 2014-02-12 北京伏尔特技术有限公司 Composite layer medical tube, co-extrusion machine head and method for manufacturing medical tubes
CN104403122A (en) * 2014-11-12 2015-03-11 无锡中科光远生物材料有限公司 Blood stabilizer, blood bag and preparation method thereof
CN104725720A (en) * 2015-03-10 2015-06-24 中国科学院长春应用化学研究所 Anti-hemolytic polypropylene blend and preparation method thereof

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102108146A (en) * 2010-03-29 2011-06-29 宁波先锋新材料股份有限公司 Polyolefin thermoplastic elastomer (TPE) composition and preparation method thereof
CN102108146B (en) * 2010-03-29 2012-11-21 宁波先锋新材料股份有限公司 Polyolefin thermoplastic elastomer (TPE) composition and preparation method thereof
CN103566431A (en) * 2013-11-15 2014-02-12 北京伏尔特技术有限公司 Composite layer medical tube, co-extrusion machine head and method for manufacturing medical tubes
CN104403122A (en) * 2014-11-12 2015-03-11 无锡中科光远生物材料有限公司 Blood stabilizer, blood bag and preparation method thereof
CN104403122B (en) * 2014-11-12 2018-05-08 无锡中科光远生物材料有限公司 A kind of blood stabilizer, blood bag and preparation method thereof
CN104725720A (en) * 2015-03-10 2015-06-24 中国科学院长春应用化学研究所 Anti-hemolytic polypropylene blend and preparation method thereof

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