CN101724202A - Preparation method of polypropylene resin suitable for manufacturing medical infusion bottle by using injection stretch blow moulding process - Google Patents
Preparation method of polypropylene resin suitable for manufacturing medical infusion bottle by using injection stretch blow moulding process Download PDFInfo
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- CN101724202A CN101724202A CN200810202110A CN200810202110A CN101724202A CN 101724202 A CN101724202 A CN 101724202A CN 200810202110 A CN200810202110 A CN 200810202110A CN 200810202110 A CN200810202110 A CN 200810202110A CN 101724202 A CN101724202 A CN 101724202A
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- oxidation inhibitor
- polypropylene resin
- antioxidant
- acrylic resin
- resin base
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Abstract
The invention relates to a preparation method of polypropylene resin suitable for manufacturing a medical infusion bottle by using an injection stretch blow moulding process, comprising the following steps of: evenly mixing polypropylene resin base material and additive and then melting, mixing and pelleting to obtain a polypropylene resin product, wherein the melting heating temperature is 190 to 250 DEG; the resin base material is propylene and ethylene random copolymer with the ethylene content of 0.5 to 4 percent by weight and the melting flow rate of 5.0 to 10.0g/10min; the additive comprises an acid neutralizer, an antioxidant A and an antioxidant B, wherein the antioxidant A is 1,1,3-tri(2-methyl-4-hydroxyl-5-tertiary butyl phenyl) butane; the antioxidant B is diphosphorous acid bi(2,4-teritiary dibutyl phenyl) pentaerythritol ester; the ratio of the antioxidant A to the antioxidant B is 1: 0.3-10; the ratio of the polypropylene resin base material to the acid neutralizer is 100: 0.01-0.05; and the ratio of the polypropylene resin base material to (the antioxidant A and the antioxidant B) is 100: 0.02-0.28.
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 the propylene-ethylene random copolymers of a kind of ethylene content less than 10wt%.With regard to performances such as thermotolerance, intensity, toughness and transparency, it is compared with the superpolymer materials such as polyvinyl chloride of early stage use has remarkable advantages, typical in U.S. Pat 5,286, and 540, Chinese patent application 200410017402.9 introduced.On the other hand, the system bottle process of medical infusion bottle then mostly changes injection stretch blow moulding into by direct extrusion blow technology, promptly earlier raw material is made bottle base by injection moulding, blow molding under the tensile state then.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 process 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 take place, and this can influence 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 neutralizing agent, and oxidation inhibitor is major ingredients, and acid neutralizing agent then is used to stop 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 technology 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 that is used to make 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 method for preparing polypropylene resin that is applicable to 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 method for preparing polypropylene resin that is applicable to manufacturing medical infusion bottle by using injection stretch blow moulding process, this method comprises and will carry out the melting mixing granulation behind acrylic resin base-material and the additive uniform mixing, obtain the acrylic resin product, the fusion 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 neutralizing agent, 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 is 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 neutralizing agent=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 neutralizing agent 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 fusion Heating temperature is preferably 200～230 ℃, and fusion was generally 2～4 minutes heat-up time.
The contriver is through a large amount of screening experiments, selected a kind of compound oxidant of forming by Hinered phenols antioxidant and phosphite ester kind antioxidant, they are 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 antioxygen property especially.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 fusion, the ascendant trend of the melt flow rate (MFR) of resin is obviously slowed down, and therefore is more suitable for being used to annotate the stretch blow bottle producing process.
Below will the invention will be further described by specific embodiment, because key of the present invention is the adjustment or the improvement of oxidation inhibitor, other parts and prior art do not have 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 carrying out the melting mixing granulation behind acrylic resin base-material and the additive uniform mixing, obtain the acrylic resin product.The fusion Heating temperature is 200～230 ℃, and fusion 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 neutralizing agent, 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 is two (2, the 4-di-tert-butyl-phenyl) pentaerythritol esters of diphosphorous acid;
Acid neutralizing agent is the calcium stearate and the hydrogenation talcum powder of identical weight part.
The proportioning of each each material of embodiment sees Table 1.
[comparative example 1～2]
Hinered phenols antioxidant A adopt prior art commonly used 1,3,5-trimethylammonium-2,4,6-three (3,5-di-t-butyl-4 hydroxybenzyl) benzene, phosphite ester kind antioxidant B adopts prior art three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester commonly used, and all the other are with embodiment 1～6.
The acrylic resin of each embodiment and comparative example is heated to fusion, and cooling granulation, reheat be to fusion, cooling granulation, 5 times so repeatedly.Measure the melt flow rate (MFR) MFR (3) and the MFR (5) of acrylic resin after the 3rd time, the 5th fusion and granulation respectively, the results are shown in Table 2.
Table 1.
| Oxidation inhibitor A/ oxidation inhibitor B (weight ratio) | Resin binder/acid neutralizing agent total amount (weight ratio) | Resin binder/oxidation inhibitor total amount (weight ratio) | |
| Embodiment 1 | ????1/0.3 | ????100/0.01 | ????100/0.25 |
| Embodiment 2 | ????1/10 | ????100/0.05 | ????100/0.15 |
| Embodiment 3 | ????1/2 | ????100/0.04 | ????100/0.28 |
| Embodiment 4 | ????1/3 | ????100/0.05 | ????100/0.10 |
| Embodiment 5 | ????1/0.8 | ????100/0.02 | ????100/0.09 |
| Embodiment 6 | ????1/7 | ????100/0.03 | ????100/0.02 |
| Comparative example 1 | ????1/2 | ????100/0.04 | ????100/0.28 |
| Comparative example 2 | ????1/3 | ????100/0.05 | ????100/0.10 |
Table 2.
| ????MFR(3)????(g/10min) | ????MFR(5)????(g/10min) | |
| Embodiment 1 | ????7.5 | ????8.1 |
| Embodiment 2 | ????7.3 | ????7.5 |
| Embodiment 3 | ????7.2 | ????7.5 |
| Embodiment 4 | ????7.4 | ????7.9 |
| Embodiment 5 | ????7.6 | ????8.2 |
| Embodiment 6 | ????8.0 | ????8.6 |
| Comparative example 1 | ????8.5 | ????9.5 |
| Comparative example 2 | ????8.6 | ????9.9 |
Annotate: the initial melt flow rate (MFR) of the resin that each embodiment and comparative example obtain is 7.0g/10min.
Claims (6)
1. method for preparing polypropylene resin that is applicable to manufacturing medical infusion bottle by using injection stretch blow moulding process, this method comprises and will carry out the melting mixing granulation behind acrylic resin base-material and the additive uniform mixing, obtain the acrylic resin product, the fusion 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 neutralizing agent, 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 is 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 neutralizing agent=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 is characterized in that described acid neutralizing agent is calcium stearate and the talcous mixture of hydrogenation, in weight ratio, and calcium stearate: hydrogenation talcum powder=1: 0.8～1.3.
5. method for preparing polypropylene resin according to claim 1, when it is characterized in that carrying out the melting mixing granulation, the fusion Heating temperature is 200～230 ℃.
6. method for preparing polypropylene resin according to claim 1, when it is characterized in that carrying out the melting mixing granulation, fusion heat-up time is 2～4 minutes.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810202110A CN101724202A (en) | 2008-10-31 | 2008-10-31 | Preparation method of polypropylene resin suitable for manufacturing medical infusion bottle by using injection stretch blow moulding process |
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| CN200810202110A CN101724202A (en) | 2008-10-31 | 2008-10-31 | Preparation method of polypropylene resin suitable for manufacturing medical infusion bottle by using injection stretch blow moulding process |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101724199B (en) * | 2008-10-31 | 2013-04-10 | 中国石化上海石油化工股份有限公司 | Preparation method of polypropylene resin used for manufacturing medical infusion bottle by injection stretch blow moulding |
| CN111100381A (en) * | 2018-10-25 | 2020-05-05 | 中国石油化工股份有限公司 | Polypropylene resin for low-precipitation injection-stretch blow molding |
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2008
- 2008-10-31 CN CN200810202110A patent/CN101724202A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101724199B (en) * | 2008-10-31 | 2013-04-10 | 中国石化上海石油化工股份有限公司 | Preparation method of polypropylene resin used for manufacturing medical infusion bottle by injection stretch blow moulding |
| CN111100381A (en) * | 2018-10-25 | 2020-05-05 | 中国石油化工股份有限公司 | Polypropylene resin for low-precipitation injection-stretch blow molding |
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Application publication date: 20100609 |