CN101451011A - Polyolefin thermoplastic elastomer blending resin and preparation method thereof - Google Patents
Polyolefin thermoplastic elastomer blending resin and preparation method thereof Download PDFInfo
- Publication number
- CN101451011A CN101451011A CNA2007101148966A CN200710114896A CN101451011A CN 101451011 A CN101451011 A CN 101451011A CN A2007101148966 A CNA2007101148966 A CN A2007101148966A CN 200710114896 A CN200710114896 A CN 200710114896A CN 101451011 A CN101451011 A CN 101451011A
- Authority
- CN
- China
- Prior art keywords
- resin
- thermoplastic elastomer
- polyolefin thermoplastic
- weight
- blending resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Medical Preparation Storing Or Oral Administration Devices (AREA)
Abstract
The invention provides a polyolefin thermoplastic elastomer blended resin and a method for preparation the same. The resin is prepared through a melting and blending method and comprises the following compositions: (A) a segmented copolymer accounting for 60 to 80 percent of gross weight of which the middle part is an irregular copolymer chain segment of ethene and 1-butylene, and two ends are capped through styrene chain segments; (B) polypropylene resin accounting for 10 to 30 percent of gross weight; and (C) polyethylene resin accounting for 5 to 20 percent of gross weight. The blended resin has innocuity, does not need to add a plasticizer in processing, does not have dangers that a compound is precipitated out, pollutes medical liquid and enters human body, and can be used for manufacturing a vessel for storing human blood and blood compositions.
Description
Technical field
The invention belongs to the technical field of polyolefin blend resin, specifically, the present invention relates to medical polyolefin thermoplastic elastomer blending resin and preparation method thereof, this resin can be used for making the container of store human body blood and blood ingredient.
Background technology
We know, because polyvinyl chloride (PVC) low price, comprehensive physical and mechanical properties is good, generally are used as the raw materials for production 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, all deficiencies are also arranged on the use properties.As the residual vinyl chloride monomer that minute quantity is arranged in the polyvinyl chloride resin, this compound has been proved to be carcinogenic substance.In order to obtain the flexible PVC goods, must use softening agent (up to the various organic esterses of 40%～60% parts by weight, as DEHP etc.) man-hour adding, make finished product post-plasticization agent meeting to be extracted gradually, and enter human body thereupon by soup and blood.Announce at U.S. FDA apparatus and radiation health research center: DEHP is poisonous, can discharge female hormone, and contact DEHP can cause the reproductive system dysplasia, and precocious and boy's physiological development is unsound etc. as girl.For preventing that PVC from adding the thermolysis in man-hour, add the compound used as stabilizers of metal ion (calcium ion and zine ion are main) usually, when these metallic compounds contact with human body health there is harm.The waste treatment difficulty of PVC medical disposable material, underground burying do not degraded decades, burns and then produces the toxic gas dioxin, and the two all causes severe contamination to environment.In addition, PVC adds can decompose the hydrogenchloride that produces trace man-hour, and processing units is caused corrosion, and operator's health is brought threat.
Container (blood bag) with store human body blood and blood ingredient is an example: the quality guaranteed period of PVC blood bag (containing Precerving liquid) is shorter, and after empty bag was placed half a year, pure leachable, reducing substance, zine ion and pH value etc. can surpass the relevant national standard set quota.PVC blood bag product can not adopt γ-ray or electron beam irradiation method to carry out sterilising treatment, can cause the aging and variable color of PVC material.The blood bag product that contains Precerving liquid can not be used ethylene oxide sterilizing, because oxyethane steam dissolves in the Precerving liquid.Do not contain the thrombocyte blood bag epoxy available ethane sterilization of Precerving liquid, but sterilization is not thorough, may have the dead angle.Another key character of blood bag is a ventilation property.For PVC blood bag material, along with the minimizing of plasticizer consumption, ventilation property generally reduces.The reduction of ventilation property is disadvantageous to some blood ingredient such as hematoblastic storage.
In view of this, both at home and abroad all can contend with PVC on the research and development price, suitable with it novel material on the performance.Rise the eighties in 20th century two during the decade, the U.S. hundred special companies have applied for the patent of a series of relevant non-PVC blood bag material aspects, they mainly are the blends of polyolefine and thermoplastic elastomer: United States Patent (USP) 5,026,347 disclosed SIS/SEBS/butyryl citric acid three is ester/polyacrylic blend just; The blend of Chinese patent CN 95191306.9 disclosed ethylene-vinyl acetate copolymer/SIS/SEBS/ultra-low density polyethylenes; United States Patent (USP) 5,952, the blend of 423 disclosed polypropylene/SIS/SEBS/nylon/citrate/vitamin Es; United States Patent (USP) 5,683, the blend of 768 disclosed polypropylene/SIS/SEBS/nylon; United States Patent (USP) 6,579, the multipolymer of 583 disclosed ethylene-vinyl acetate copolymer/styrene-ethylene-butadiene-styrenes/ultra-low density polyethylene blend etc.Patent had also once been reported other non-PVC materials that can be used for producing the blood bag, as United States Patent (USP) 4,479, and 989 disclosed linear low density polyethylene/SIS/SEBS blends; United States Patent (USP) 4,561, the blend of 110 disclosed polyolefine/ethylene-vinyl acetate copolymers; United States Patent (USP) 5,529,821 disclosed multilayer complex films etc.
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, stable performance, flexibility, elasticity, good toughness, free from environmental pollution during destruction, can replace the method that PVC is used as the polyolefin thermoplastic elastomer blending resin of disposable transfusion set tool and prepares this resin.
The technical scheme that the present invention solves the problems of the technologies described above employing is: a kind of polyolefin thermoplastic elastomer blending resin, and its component comprises:
Component A, a kind of random copolymers segment by ethene and 1-butylene is as middle portion, and by the segmented copolymer that vinylbenzene segment end-blocking constitutes, wherein comprises the mid-block multipolymer of 60%～80% (weight), its melt flow rate (MFR) (230 ℃ 5kg) are 0.5～10.0g/10min.Preferred mid-block multipolymer content is 65%～75%, and melt flow rate (MFR) is the segmented copolymer of 0.5～5.0g/10min.Component A shared weight ratio in co-mixing system is 60%～80%, preferred 70%～78%.Component A mainly plays in co-mixing system and increases transparency and elastic effect is provided.
B component, a kind of acrylic resin, its comonomer are ethene, content is 4%～18% (weight), its melt flow rate (MFR) (230 ℃ 2.16kg) are 0.5～20.0g/10Cmin.Optimal ethylene content is 5%～8%, and melt flow rate (MFR) is the acrylic resin of 1.0～10.0g/10min.B component shared weight ratio in co-mixing system is 10%～30%, preferred 12%～20%.B component has certain rigid and intensity, can guarantee the physical and mechanical properties of blending resin.
Component C, a kind of polyvinyl resin, its comonomer are 1-butylene, 1-alkene or 1-octene, and content is 1%～8% (weight), its melt flow rate (MFR) (190 ℃ 2.16kg) are 0.5～10.0g/10min.Preferred comonomers is the 1-octene, and monomer content is 3%～6%, and melt flow rate (MFR) is the polyvinyl resin of 0.5～5.0g/10min.Component C shared weight ratio in co-mixing system is 5%～20%, preferred 8%～12%.Component C can guarantee that blending resin has good heat sealability.
Get above-mentioned three kinds of components by 100 parts of gross weights and carry out proportioning, the raw material that proportioning is good joins that mechanically mixing obtained pre-mixed resin in 2～10 minutes in Henschel mixing tank, drum tumbler or the V-type mixing tank; Again pre-mixed resin is joined twin screw extruder, setting forcing machine is 130～250 ℃ along charging opening to a mouthful mould direction temperature, and die temperature is 190～230 ℃; The residence time of blend material in forcing machine is 1.5～3.0 minutes, and each component obtains thorough mixing in molten state in this process; At last, blend per os mould is extruded, pelletizing, is drying to obtain product.
The major advantage of this resin is: all blend components is the nontoxic product of medical grade, and its synthon and corresponding polymer have been avoided the toxicity problem of PVC material itself to the human body totally nontoxic; The danger that this compounds was separated out, polluted soup and enters human body can not take place in plasticizer-containing not in the blending resin.
Blending resin of the present invention is having a wide range of applications aspect the disposable transfusion set tool, can adopt methods such as blowing, extrusion molding, calendering to prepare film forming; Also can be extruded into linking conduit; And use modes such as sweating soldering, laser welding that film material and tubing are assembled into the blood bag product.This non-PVC blood bag has the optical transparence that can be used for clarity test; Soft collapsible, and possess good low-temperature pliability, can be at-80 ℃ of following freezing preservation blood ingredients; Possess effective thermotolerance, can bear the high-temperature steam sterilization process and indeformable or self-adhesive, particularly available gamma-radiation of thrombocyte bag or electron beam irradiation sterilization; Possess enough ventilation properties, so that the cellular constituent of living or the vitality of other cellular material to be provided wherein; Depleted blood bag is handled relatively easy, can not produce the problem of environmental pollution when handling PVC blood bag.
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 embodiment uses sees table 1 for details.
Embodiment 1 is made into blending resin by 42/28/20/10 weight ratio with component A1, A2, B2 and C1, mixes 5 minutes in high speed agitator, obtains Preblend.Above-mentioned Preblend is transported 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 140～230 ℃ along charging opening to a mouthful mould direction temperature, and die temperature is 220 ℃.Blend per os mould is extruded, cooling, pelletizing, obtains blending resin, and the test melt flow rate (MFR).The standard model that blending resin is molded into 0.5mm is tested its transmittance, mist degree; Blending resin is injection molded into the standard batten, test surfaces hardness and mechanical property.Test result gathers lists in the table 2.
Embodiment 2 is made into blending resin by 45/30/15/10 weight ratio with component A1, A3, B1 and C2, 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 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 is made into blending resin by 55/25/12/8 weight ratio with component A2, A3, B2 and C2, employed equipment, processing conditions and step etc. are all identical with embodiment 2, 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 4 is made into blending resin by 25/35/20/20 weight ratio with component A1, A2, B3 and C1, mixes 5 minutes in high speed agitator, obtains Preblend.Above-mentioned Preblend is transported 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 blending resin, and the test melt flow rate (MFR).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 is made into blending resin by 48/26/14/12 weight ratio with component A1, A3, B1 and C1, 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 to carry out sample preparation with embodiment 1, and test respective performances index, the results are shown in Table 2.
Embodiment 6 is made into blending resin by 36/42/10/12 weight ratio with component A2, A3, B2 and C2, use equipment, processing conditions and step etc. are all identical with embodiment 5, 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 7 is made into blending resin by 70/20/10 weight ratio with component A2, B2 and C1, use equipment, processing conditions and step etc. are all identical with embodiment 1, 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 8 is made into blending resin by 35/40/15/10 weight ratio with component A1, A2, B1 and C2, use equipment, processing conditions and step etc. are all identical with embodiment 1, 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 9 is made into blending resin by 60/10/20/10 weight ratio with component A3, B1, B3 and C1, use 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.
Employed thermoplastic elastomer and polyolefin resin among table 1 embodiment
*MFR, melt flow rate (MFR), the g/10min of unit.The test condition of A1, A2 and A3 is 230 ℃, 5.0Kg; The test condition of B1, B2 and B3 is 230 ℃, 2.16Kg, and the test condition of C1 and C2 is 190 ℃, 2.16Kg.
Each component blend proportioning and blend performance among table 2 embodiment
*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 blood bag PVC material that Dutch higher bit company produces.
The air permeability test result of the various embodiments described above polyolefin thermoplastic elastomer blending resin film of the present invention is as follows:
Press the method for GB/T 19789-2005 and measure oxygen gas permeability.The testing method principle is as follows: utilize sample to be tested will permeate the chamber and be separated into two independently air flow systems, at first clean with the carrier gas of anaerobic, with the remnant oxygen in the scavenge system and the oxygen that absorbs on the sample is deviate from, 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, thickness of sample is at 0.40～0.5mm, test duration 48h, oxygen concentration 10%.Gained the results are shown in the following table 3.
Table 3. embodiment make blend the oxygen transit dose and with the comparison of PVC material
| Material number | Oxygen transit dose (cc/m 2/d) |
| Comparative example 1 | 46.94 |
| Comparative example 2 | 86.67 |
| Embodiment 1 | 79.71 |
| Embodiment 2 | 88.43 |
| Embodiment 3 | 98.60 |
| Embodiment 4 | 123.12 |
| Embodiment 5 | 90.04 |
| Embodiment 6 | 104.32 |
| Embodiment 7 | 86.70 |
| Embodiment 8 | 96.31 |
| Embodiment 9 | 118.94 |
*The red corpuscle blood bag PVC material that comparative example 1 is produced for Medical High Molecular Product Co., Ltd., Shandong Weigao Group;
Comparative example 2 is the thrombocyte blood bag PVC material that Dutch higher bit company produces.
Contrast finds that the OTR oxygen transmission rate of the blending resin material of embodiment 1 preparation 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 blending resin 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 (9)
1. polyolefin thermoplastic elastomer blending resin, it is characterized in that: its component comprises:
(A) account for the segmented copolymer of gross weight 60%～80%, the middle portion of this segmented copolymer is made of the random copolymers segment of ethene and 1-butylene, and two ends are by vinylbenzene segment end-blocking;
(B) account for the acrylic resin of gross weight 10%～30%;
(C) account for the polyvinyl resin of gross weight 5%～20%.
2. polyolefin thermoplastic elastomer blending resin according to claim 1 is characterized in that comprising in the said segmented copolymer mid-block multipolymer of 60%～80% (weight), melt flow rate (MFR) (230 ℃ 5kg) are 0.5～10.0g/10min.
3. polyolefin thermoplastic elastomer blending resin according to claim 2 is characterized in that comprising in the said segmented copolymer mid-block multipolymer of 65%～75% (weight), melt flow rate (MFR) (230 ℃ 5kg) are 0.5～5.0g/10min.
4. polyolefin thermoplastic elastomer blending resin according to claim 1, it is characterized in that the comonomer in the said acrylic resin is an ethene, content is 4%～18% (weight), melt flow rate (MFR) (230 ℃ 2.16kg) are 0.5～20.0g/10min.
5. polyolefin thermoplastic elastomer blending resin according to claim 4 is characterized in that the comonomer in the acrylic resin is an ethene, and content is 5%～8% (weight), melt flow rate (MFR) (230 ℃ 2.16kg) are 1.0～10.0g/10min.
6. polyolefin thermoplastic elastomer blending resin according to claim 1, it is characterized in that comonomer is 1-butylene, 1-alkene or 1-octene in the said polyvinyl resin, content is 1%～8% (weight), melt flow rate (MFR) (190 ℃ 2.16kg) are 0.5～10.0g/10min.
7. polyolefin thermoplastic elastomer blending resin according to claim 6 is characterized in that comonomer is the 1-octene in the polyvinyl resin, and content is 3%～6% (weight), its melt flow rate (MFR) (190 ℃ 2.16kg) are 0.5～5.0g/10min.
8. polyolefin thermoplastic elastomer blending resin according to claim 1 is characterized in that this resin is made up of following component:
(a) account for the segmented copolymer of gross weight 70%～78%, the middle portion of this segmented copolymer is made of the random copolymers of ethene and 1-butylene, and two ends are by vinylbenzene segment end-blocking;
(b) account for the acrylic resin of gross weight 12%～20%;
(c) account for the polyvinyl resin of gross weight 8%～12%.
9. preparation method according to each described polyolefin thermoplastic elastomer blending resin of claim 1～8 is characterized in that by weight ratio above-mentioned raw materials was joined in Hensche1 mixing tank, drum tumbler or the V-type mixing tank mechanically mixing 2～10 minutes; To obtain pre-mixed resin and join twin screw extruder, setting forcing machine is 130～250 ℃ along charging opening to a mouthful mould direction temperature, and die temperature is 190～230 ℃, and the residence time of blend material in forcing machine is 1.5～3.0 minutes; At last, blend per os mould is extruded, pelletizing, is drying to obtain product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007101148966A CN101451011A (en) | 2007-11-29 | 2007-11-29 | Polyolefin thermoplastic elastomer blending resin and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007101148966A CN101451011A (en) | 2007-11-29 | 2007-11-29 | Polyolefin thermoplastic elastomer blending resin and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101451011A true CN101451011A (en) | 2009-06-10 |
Family
ID=40733507
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2007101148966A Pending CN101451011A (en) | 2007-11-29 | 2007-11-29 | Polyolefin thermoplastic elastomer blending resin and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101451011A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101845173A (en) * | 2010-05-19 | 2010-09-29 | 安徽双鹤药业有限责任公司 | Manufacturing process and production equipment for medical infusion bags |
| CN101851370A (en) * | 2010-05-19 | 2010-10-06 | 安徽双鹤药业有限责任公司 | Material special for medicinal transfusion bag |
| CN102501374A (en) * | 2011-11-10 | 2012-06-20 | 中国科学院长春应用化学研究所 | Cryogenic storage vessel and preparation method thereof |
| CN103013023A (en) * | 2012-12-07 | 2013-04-03 | 安徽荣盛橡塑科技有限公司 | Medicinal thermoplastic elastomer bottle stopper and preparation method thereof |
| CN105175939A (en) * | 2015-09-09 | 2015-12-23 | 深圳恒方大高分子材料科技有限公司 | High-oxygen-permeability medical PVC (polyvinyl chloride) material and preparation method of high-oxygen-permeability medical PVC material |
-
2007
- 2007-11-29 CN CNA2007101148966A patent/CN101451011A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101845173A (en) * | 2010-05-19 | 2010-09-29 | 安徽双鹤药业有限责任公司 | Manufacturing process and production equipment for medical infusion bags |
| CN101851370A (en) * | 2010-05-19 | 2010-10-06 | 安徽双鹤药业有限责任公司 | Material special for medicinal transfusion bag |
| CN102501374A (en) * | 2011-11-10 | 2012-06-20 | 中国科学院长春应用化学研究所 | Cryogenic storage vessel and preparation method thereof |
| CN103013023A (en) * | 2012-12-07 | 2013-04-03 | 安徽荣盛橡塑科技有限公司 | Medicinal thermoplastic elastomer bottle stopper and preparation method thereof |
| CN103013023B (en) * | 2012-12-07 | 2016-02-10 | 安徽荣盛橡塑科技有限公司 | Medicinal thermoplastic elastomer bottle stopper and preparation method thereof |
| CN105175939A (en) * | 2015-09-09 | 2015-12-23 | 深圳恒方大高分子材料科技有限公司 | High-oxygen-permeability medical PVC (polyvinyl chloride) material and preparation method of high-oxygen-permeability medical PVC material |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101550257B (en) | Thermoplastic elastomer composite material | |
| CA2104968A1 (en) | Material for medical grade products and products made therefrom | |
| CN101376730A (en) | Thermoplastic elastomer material, preparation thereof and method for manufacturing medicinal bottle stopper by using the same | |
| CN108299711B (en) | Antibacterial packaging film and processing method | |
| EP1373377A2 (en) | Flexible monolayer elastromer films containing seps and bags for medical use | |
| CN101451011A (en) | Polyolefin thermoplastic elastomer blending resin and preparation method thereof | |
| CN101519517B (en) | Medical rubber-plastic composite material | |
| CN104558854B (en) | A kind of ampoule bottle polypropene composition | |
| CN102911475A (en) | Medical artificial rubber material and preparation method thereof | |
| CN101921451B (en) | Thermoplastic elastomer composite material | |
| CN102304257A (en) | Medical PVC material adopted for steam sterilization, and preparation method thereof | |
| CN110511489A (en) | A kind of high-performance radiation resistance polypropylene dedicated material and preparation method thereof | |
| CN104387678B (en) | Medical thermoplastic elastomer composition and preparation method of medical tube thereof | |
| CN101508808B (en) | Biological medical large transfusion soft bag connector material and preparation thereof | |
| CN101514250A (en) | Polyolefin thermoplastic elastomer blood storage material and preparation method thereof | |
| US20110288236A1 (en) | Resin composition | |
| EP3042927B1 (en) | Method for producing sterilized medical molded body | |
| CN110157135B (en) | Medical membrane material, preparation method thereof and disposable intravenous nutrition infusion bag | |
| KR20160141725A (en) | Injection fluid bag and injection preparation | |
| CN104130542A (en) | Medical polyolefin elastomer pellet and preparation method thereof | |
| CN101462389A (en) | Polyolefin multi-layer co-extrusion infusion film and technique of preparing the same | |
| CN101423633A (en) | Thermoplastic elastomer composite material | |
| CN109320842A (en) | A kind of polypropylene for medical article thermoplastic elastomer (TPE) and its preparation method and application | |
| CN110128774A (en) | A kind of thermoplastic elastomer composite material, preparation method and application | |
| CN104497415B (en) | Infusion bag thermoplastic elastomer (TPE) and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Open date: 20090610 |