CN101724199B - Preparation method of polypropylene resin used for manufacturing medical infusion bottle by injection stretch blow moulding - Google Patents
Preparation method of polypropylene resin used for manufacturing medical infusion bottle by injection stretch blow moulding Download PDFInfo
- Publication number
- CN101724199B CN101724199B CN 200810202098 CN200810202098A CN101724199B CN 101724199 B CN101724199 B CN 101724199B CN 200810202098 CN200810202098 CN 200810202098 CN 200810202098 A CN200810202098 A CN 200810202098A CN 101724199 B CN101724199 B CN 101724199B
- Authority
- CN
- China
- Prior art keywords
- oxidation inhibitor
- polypropylene resin
- acrylic resin
- melting
- tert
- 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.)
- Active
Links
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Medical Preparation Storing Or Oral Administration Devices (AREA)
Abstract
The invention relates to a preparation method of polypropylene resin used for manufacturing medical infusion bottle by injection stretch blow moulding, including that polypropylene resin matrix and additive are mixed and then melting, mixing and pelleting are carried out to obtain the polypropylene resin product. The resin matrix is propene ethane random copolymer, content of ethane is 0.5-4wt%, and melt flowing speed is 5.0-10.0g/10min. The additive comprises acid acceptor, antioxidant A and antioxidant B; wherein the antioxidant A is 1, 1, 3-tri(2-methyl-4-hydroxy-5-tert-butyl phenyl) butane; and the antioxidant B is tri(2, 4-ditertiary butyl phenyl) phosphite ester or bis(2, 4-di-tert-butyl phenyl) pentaerythritol phosphite ester. The invention has the advantages that thermal degradation resistance of the manufactured resin is greatly improved, the rising trend of melt flowing speed of the resin is obviously retarded through a plurality of times of heating and melting, thus being more applicable to the injection stretch blow moulding bottle-making process.
Description
Technical field
The present invention relates to a kind of method for preparing polypropylene resin, particularly be exclusively used in the preparation method of the acrylic resin of making medical infusion bottle.
Background technology
At present, the manufacturing raw material of plastics medical infusion bottle substantially all adopts special-purpose acrylic resin, and it is that a kind of ethylene content is less than the propylene-ethylene random copolymers of 10wt%.With regard to the performances such as thermotolerance, intensity, toughness and transparency, it is compared with the superpolymer materials such as polyvinyl chloride of early application has obvious advantage, typical in US Patent No. 5,286, and 540, Chinese patent application 200410017402.9 introduces.On the other hand, the bottle process processed of medical infusion bottle then mostly changes injection stretch blow moulding into by direct extrusion blow technique, namely first raw material is made bottle base by injection moulding, then blow molding under the state that stretches.Because orientation degree improves behind the moulding process superpolymer macromole drawn, bottle intensity obviously increases, and bottle is minimized at the impregnable prerequisite lower wall thickness of mechanical property.This has not only improved the transparency of bottle, and has reduced the raw material consumption of system bottle.
In the whole manufacturing processed of medical infusion bottle, system bottle raw material acrylic resin need experience the heating and melting under the aerobic environment, and therefore polymer macromolecule can thermal destruction occur, and this can affect the mechanical property of bottle at last.In order to improve the antioxygen property of acrylic resin, it is necessary adding antioxidant additive in the resin.The component of antioxidant additive generally comprises oxidation inhibitor and acid-acceptor, and oxidation inhibitor is main composition, and acid-acceptor then is used for stoping the resistates of polymerizing catalyst to cause the inner formation of polymkeric substance sour environment, because sour environment will promote the generation of degraded.The direct extrusion blow technique of comparing, injection stretch blow moulding has had more the manufacturing of bottle base in earlier stage, and the heating and melting number of times of raw material under aerobic environment increases the easier generation thermal destruction of polymer macromolecule.In the prior art, the general acrylic resin raw material for the manufacture of medical infusion bottle is not adjusted antioxidant additive because of the change of manufacturing process usually targetedly, therefore when being used for injection stretch blow moulding, just manifested the dissatisfactory defective of antioxygen property.
Summary of the invention
The invention provides a kind of for the method for preparing polypropylene resin with manufacturing medical infusion bottle by using injection stretch blow moulding process, its technical problem to be solved is by the antioxygen additive formulations is adjusted targetedly, improve the antioxidant property of resin, thereby overcome the defective that prior art exists.
Below be the concrete technical scheme of the present invention:
A kind of for the method for preparing polypropylene resin with manufacturing medical infusion bottle by using injection stretch blow moulding process, the method comprise with the acrylic resin base-material with carry out the melting mixing granulation after additive evenly mixes, obtain the acrylic resin product, the melting Heating temperature is 190～250 ℃.
Above-mentioned acrylic resin base-material is propylene and ethylene atactic copolymer, and its ethylene content is 0.5～4wt%; Melt temperature is 140～165 ℃; Melt flow rate (MFR) is 5.0～10.0g/10min.
Above-mentioned additive comprises acid-acceptor, oxidation inhibitor A and oxidation inhibitor B, wherein:
Oxidation inhibitor A is 1,1,3-three (2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane;
Oxidation inhibitor B takes from three (2,4-di-tert-butyl-phenyl) phosphorous acid esters or two (2, the 4-di-tert-butyl-phenyl) pentaerythritol esters of diphosphorous acid.
In weight ratio, the proportioning of each material is:
Oxidation inhibitor A: oxidation inhibitor B=1: 0.3～10;
Acrylic resin base-material: acid-acceptor=100: 0.01～0.05;
Acrylic resin base-material: (oxidation inhibitor A+ oxidation inhibitor B)=100: 0.02～0.28.
The melt flow rate (MFR) of above-mentioned acrylic resin base-material is preferably 6.5～8.5g/10min;
Above-mentioned oxidation inhibitor A: oxidation inhibitor B=1: 0.8～7 for better;
Above-mentioned acid-acceptor is preferably calcium stearate and the talcous mixture of hydrogenation, in weight ratio, and calcium stearate: hydrogenation talcum powder=1: 0.8～1.3.
When carrying out the melting mixing granulation, the melting Heating temperature is preferably 200～230 ℃, and melting is generally 2～4 minutes heat-up time.
The contriver is through a large amount of screening experiments, selected a kind of compound oxidant that is formed by Hinered phenols antioxidant and phosphite ester kind antioxidant, Hinered phenols antioxidant wherein (oxidation inhibitor A) is not adopted by prior art usually, and obtained unexpected result of use with the oxidation inhibitor that this makes up, it is more continual and steady to be embodied in especially antioxygen property.Compared with prior art, advantage of the present invention is that the heat-resisting degradation property of resin that makes improves a lot, and through the heating for multiple times melting, the ascendant trend of the melt flow rate (MFR) of resin is obviously slowed down, and therefore is more suitable for for annotating the stretch blow bottle producing process.
The below will the invention will be further described by specific embodiment, because key of the present invention is adjustment or the improvement of oxidation inhibitor, other parts and prior art be without the difference of essence, so embodiment will pay attention to enumerating of oxidation inhibitor in the antioxidant additive and proportioning thereof.
Embodiment
[embodiment 1～6]
With the acrylic resin base-material with carry out the melting mixing granulation after additive evenly mixes, obtain the acrylic resin product.The melting Heating temperature is 200～230 ℃, and melting heat-up time is 2～4 minutes.
Above-mentioned acrylic resin base-material is propylene and ethylene atactic copolymer, and its ethylene content is 0.5～4wt%; Melt temperature is 140～165 ℃, and melt flow rate (MFR) is 7.0g/10min;
Above-mentioned additive comprises acid-acceptor, oxidation inhibitor A and oxidation inhibitor B, wherein:
Oxidation inhibitor A is 1,1,3-three (2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane; Acid-acceptor is calcium stearate and the hydrogenation talcum powder of identical weight part.
The concrete oxidation inhibitor B of each embodiment sees Table 1, the proportioning of each material sees Table 1 and table 2.
[comparative example 1～2]
Except Hinered phenols antioxidant A adopt prior art commonly used 1,3,5-trimethylammonium-2,4, outside 6-three (3, the 5-di-t-butyl-4 hydroxybenzyl) benzene, all the other are with embodiment 1～6.
The acrylic resin that each embodiment and comparative example are obtained is heated to melting, and cooling granulation reheats to melting, cooling granulation, 5 times so repeatedly.Measure respectively melt flow rate (MFR) MFR (3) and the MFR (5) of acrylic resin after the 3rd time, the 5th melting and granulation, the results are shown in Table 3.
Table 1.
Table 2.
Table 3.
Annotate: the initial melt flow rate (MFR) of the resin that each embodiment and comparative example obtain is 7.0g/10min.
Claims (5)
1. method for preparing polypropylene resin that is used for manufacturing medical infusion bottle by using injection stretch blow moulding process, the method comprise with the acrylic resin base-material with carry out the melting mixing granulation after additive evenly mixes, obtain the acrylic resin product, the melting Heating temperature is 190～250 ℃;
Above-mentioned acrylic resin base-material is propylene and ethylene atactic copolymer, and its ethylene content is 0.5～4wt%, and melt temperature is 140～165 ℃, and melt flow rate (MFR) is 5.0～10.0g/10min;
Above-mentioned additive comprises acid-acceptor, oxidation inhibitor A and oxidation inhibitor B, wherein:
Oxidation inhibitor A is 1,1,3-three (2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane;
Oxidation inhibitor B takes from three (2,4-di-tert-butyl-phenyl) phosphorous acid esters or two (2, the 4-di-tert-butyl-phenyl) pentaerythritol esters of diphosphorous acid;
Acid-acceptor is calcium stearate and the talcous mixture of hydrogenation;
In weight ratio, the proportioning of each material is:
Oxidation inhibitor A: oxidation inhibitor B=1: 0.3～10;
Calcium stearate: hydrogenation talcum powder=1: 0.8～1.3;
Acrylic resin base-material: acid-acceptor=100: 0.01～0.05;
Acrylic resin base-material: (oxidation inhibitor A+ oxidation inhibitor B)=100: 0.02～0.28.
2. method for preparing polypropylene resin according to claim 1, the melt flow rate (MFR) that it is characterized in that described acrylic resin base-material is 6.5～8.5g/10min.
3. method for preparing polypropylene resin according to claim 1 is characterized in that described oxidation inhibitor A: oxidation inhibitor B=1: 0.8～7.
4. method for preparing polypropylene resin according to claim 1, when it is characterized in that carrying out the melting mixing granulation, the melting Heating temperature is 200～230 ℃.
5. method for preparing polypropylene resin according to claim 1, when it is characterized in that carrying out the melting mixing granulation, melting heat-up time is 2～4 minutes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200810202098 CN101724199B (en) | 2008-10-31 | 2008-10-31 | Preparation method of polypropylene resin used for manufacturing medical infusion bottle by injection stretch blow moulding |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200810202098 CN101724199B (en) | 2008-10-31 | 2008-10-31 | Preparation method of polypropylene resin used for manufacturing medical infusion bottle by injection stretch blow moulding |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101724199A CN101724199A (en) | 2010-06-09 |
| CN101724199B true CN101724199B (en) | 2013-04-10 |
Family
ID=42445794
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200810202098 Active CN101724199B (en) | 2008-10-31 | 2008-10-31 | Preparation method of polypropylene resin used for manufacturing medical infusion bottle by injection stretch blow moulding |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101724199B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102952330B (en) * | 2011-08-30 | 2015-03-25 | 中国石油化工股份有限公司 | Low-odor polypropylene resin and preparation method thereof |
| CN103319782B (en) * | 2013-04-03 | 2016-08-31 | 吉林恒辉新材料有限公司 | A kind of PP composite material of low smell and preparation method thereof |
| CN105585777A (en) * | 2014-10-20 | 2016-05-18 | 中国石油化工股份有限公司 | Preparation method of polypropylene resin for manufacturing medical ampoule bottles by extrusion blow molding technology |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1656162A (en) * | 2002-05-27 | 2005-08-17 | 大湖化学公司欧洲分公司 | Stabilised polypropylene |
| CN1676544A (en) * | 2004-04-02 | 2005-10-05 | 中国石化上海石油化工股份有限公司 | Polypropylene resin for manufacturing medical transfusion container |
| CN1685001A (en) * | 2002-10-08 | 2005-10-19 | 玻利阿黎斯技术有限公司 | Stabilized polymer composition |
| US20070203269A1 (en) * | 2005-10-17 | 2007-08-30 | Dieter Freitag | Compositions comprising polyphosphonates and additives that exhibit an advantageous combination of properties, and methods related thereto |
| CN101724202A (en) * | 2008-10-31 | 2010-06-09 | 中国石化上海石油化工股份有限公司 | Preparation method of polypropylene resin suitable for manufacturing medical infusion bottle by using injection stretch blow moulding process |
-
2008
- 2008-10-31 CN CN 200810202098 patent/CN101724199B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1656162A (en) * | 2002-05-27 | 2005-08-17 | 大湖化学公司欧洲分公司 | Stabilised polypropylene |
| CN1685001A (en) * | 2002-10-08 | 2005-10-19 | 玻利阿黎斯技术有限公司 | Stabilized polymer composition |
| CN1676544A (en) * | 2004-04-02 | 2005-10-05 | 中国石化上海石油化工股份有限公司 | Polypropylene resin for manufacturing medical transfusion container |
| US20070203269A1 (en) * | 2005-10-17 | 2007-08-30 | Dieter Freitag | Compositions comprising polyphosphonates and additives that exhibit an advantageous combination of properties, and methods related thereto |
| CN101724202A (en) * | 2008-10-31 | 2010-06-09 | 中国石化上海石油化工股份有限公司 | Preparation method of polypropylene resin suitable for manufacturing medical infusion bottle by using injection stretch blow moulding process |
Non-Patent Citations (1)
| Title |
|---|
| JP特开2006-182988A 2006.07.13 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101724199A (en) | 2010-06-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103571039B (en) | High melting means polypropene composition and preparation method thereof | |
| CN106147033B (en) | A kind of no tiger fur line PP composite material and the preparation method and application thereof | |
| CN103360656B (en) | A kind of regenerated polythene composition and method of making the same | |
| CN102643468B (en) | Regeneration polyethylene resin combination for sheath production and preparation method thereof | |
| CN102492225B (en) | Transparent cold resistance high melt-strength polypropylene material used for automobile expansion water tank and its preparation method | |
| CN103382274B (en) | A kind of block copolymerization polypropylene composite additive | |
| CN101724203A (en) | Polypropylene resin suitable for manufacturing medical infusion bottle by using injection stretch blow moulding process | |
| CN101724199B (en) | Preparation method of polypropylene resin used for manufacturing medical infusion bottle by injection stretch blow moulding | |
| CN104327369A (en) | Polypropylene composition and polypropylene pellet | |
| CN104356579A (en) | High-impact polypropylene bottle cap material and preparation method thereof | |
| CN101724200B (en) | Polypropylene resin used for manufacturing medical infusion bottle by injection stretch blow moulding | |
| CN107974025B (en) | Non-filling low-shrinkage polypropylene composite material and preparation method thereof | |
| CN102120846B (en) | Ethylene-propylene block copolymer-based polypropylene resin composition having high impact strength, surface properties and flowability | |
| CN107383255A (en) | A kind of transparent wide molecular weight distribution atactic copolymerized polypropene plastics sucking moulding is resin dedicated and preparation method | |
| CN101724201A (en) | Polypropylene resin suitable for manufacturing medical infusion bottle by using injection stretch blow moulding process | |
| CN105733023B (en) | High density polyethylene (HDPE) pressure resistant pipe material composite assistant and preparation method thereof and the resin raw material containing the composite assistant | |
| CN112280167A (en) | Preparation method of heat-resistant high-rigidity transparent low-shrinkage homo-polypropylene resin with wide molecular weight distribution | |
| CN103360681B (en) | Halogen-free flame retardant highlight polypropylene and preparation method thereof | |
| CN101724202A (en) | Preparation method of polypropylene resin suitable for manufacturing medical infusion bottle by using injection stretch blow moulding process | |
| CN103224668B (en) | A kind of polypropylene-base bamboo moulds the preparation method of foam composite material | |
| CN104558808B (en) | Prolylene polymer composition and product prepared therefrom | |
| CN101967241B (en) | Carbon black composition mixed material and preparation method thereof | |
| CN105585777A (en) | Preparation method of polypropylene resin for manufacturing medical ampoule bottles by extrusion blow molding technology | |
| CN114456474B (en) | Thin-wall multilayer hollow blow molding material and preparation method thereof | |
| CN101724204A (en) | Preparation method of polypropylene resin suitable for manufacturing medical infusion bottle by using injection stretch blow moulding process |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |