CN107880404A - A kind of high-flowability polypropylene resin for the manufacture of disposable medical syringe and preparation method thereof - Google Patents
A kind of high-flowability polypropylene resin for the manufacture of disposable medical syringe and preparation method thereof Download PDFInfo
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- CN107880404A CN107880404A CN201610866648.6A CN201610866648A CN107880404A CN 107880404 A CN107880404 A CN 107880404A CN 201610866648 A CN201610866648 A CN 201610866648A CN 107880404 A CN107880404 A CN 107880404A
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- Prior art keywords
- nucleator
- propylene
- polypropylene resin
- antioxidant
- ethylene random
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/05—Alcohols; Metal alcoholates
- C08K5/053—Polyhydroxylic alcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
- C08K5/523—Esters of phosphoric acids, e.g. of H3PO4 with hydroxyaryl compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
- C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/02—Applications for biomedical use
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/24—Crystallisation aids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/10—Peculiar tacticity
- C08L2207/14—Amorphous or atactic polypropylene
Abstract
The invention discloses a kind of high-flowability polypropylene resin for the manufacture of disposable medical syringe and preparation method thereof.Then the high-flowability polypropylene resin of the present invention carries out extruding pelletization and is prepared by the way that propylene is mixed 2~5 minutes at normal temperatures and pressures with ethylene random acrylic resin copolymer and additive.It is made up of 98~99.7% propylene with ethylene random acrylic resin copolymer and 0.03~2% additive.The beneficial effects of the present invention are：The acrylic resin of the present invention has suitable fluidity of molten and rigidity, can meet the processing request and mechanical property requirements of disposable medical syringe.
Description
Technical field
The present invention relates to a kind of high-flowability polypropylene resin for the manufacture of disposable medical syringe, the present invention also relates to
And the preparation method of the high flow polypropylene resin for being used for the manufacture of disposable medical syringe.
Background technology
Existing polypropylene for medical article syringe PP Pipe Compound uses the technique productions of controlled degradation, the more difficult control of yellow colour index, deposits
In smell, and melt flow rate (MFR) is relatively low (230 DEG C, 2.16kg/10min, less than 25), now produces high flowing nothing by hydrogen-regulating method
Advise COPP, its yellow colour index is low, VOC (VOC) content is low, basic odorlessness and meltflow ability compared with
High (230 DEG C, 2.16kg/10min, more than 25).
The content of the invention
An object of the present invention is to provide a kind of high-flowability polypropylene tree for the manufacture of disposable medical syringe
Fat, the resin are prepared using propylene and ethylene random acrylic resin copolymer, its have good processing characteristics, optical property,
Mechanical property, and have excellent additive system, yellow colour index is low, VOC (VOC) content is low, substantially without
Smell, its performance meet YYT0242-2007《Medical infusion, blood transfusion, instrument used for injection polypropylene dedicated material》Professional standard, and
Melt flow rate (MFR) is higher, can meet production and the requirement of disposable medical syringe.
The second object of the present invention is to provide using the above-mentioned high fluidity poly- third manufactured for disposable medical syringe
The preparation method of olefine resin.
The purpose of the present invention is achieved through the following technical solutions, and is described in detail below.
The present invention provides a kind of high-flowability polypropylene resin for the manufacture of disposable medical syringe, the high fluidity
Acrylic resin is made up of 98~99.7% propylene with ethylene random acrylic resin copolymer and 0.03~2% additive；
Wherein：In the propylene and ethylene random co-polypropylene resin, the content of ethene is between 0.5~4.5wt%, its melt flows
Speed is 25~50g/10min under conditions of 230 DEG C, 2.16kg/10min, and isotactic index is 95~99%, number-average molecular weight
Between 7~100,000, molecular weight distributing index is between 4~6；The additive includes antioxidant, plumper and nucleator.
In the present invention, the ethylene random acrylic resin copolymer is made by the following method：With propylene, ethene and hydrogen
For raw material, and catalyst, co-catalyst, electron donor and antistatic additive are added in annular-pipe reactor, in 65~72 DEG C of temperature
Degree, 3.3~4.0MPa pressure, density of hydrogen react under conditions of being 1000~6000ppm, so as to obtain propylene and ethene without
Advise acrylic resin copolymer.Preferably, catalyst uses DQ- III, and co-catalyst uses triethyl aluminum TEAL, described electron
Body uses CDONOR, and described antistatic additive uses Atmer 163.
In the present invention, the antioxidant is antioxidant A and antioxidant B combination, wherein：Antioxidant A is 1,1,3- tri- (2-
Methyl -4- hydroxyl -5- tert-butyl-phenyls) butane；Antioxidant B is three (2,4- di-tert-butyl-phenyl) phosphite esters；Antioxidant A and
Antioxidant B mass ratio 1: 0.3~1：10.
In the present invention, the nucleator is nucleator A, nucleator B and nucleator C combination, wherein, nucleator A is sub-
Double (2, the 4- di-tert-butyl-phenyl) aluminum phosphates of methyl, nucleator B is two-(3,4- dimethyl benzal) sorbierites, and nucleator C is two
(to methyl benzylidene) xylitol；Nucleator A, nucleator B and nucleator C mass ratioes are (0.01~1)：(0.01~1)：
(0.01~1).
In the present invention, described plumper is calcium stearate and the combination for hydrogenating talcum powder；Wherein calcium stearate and hydrogenation
The mass ratio of talcum powder is 1：0.8~1：1.3.
In the present invention, propylene is 100: 0.01~100 with the mass ratio of ethylene random acrylic resin copolymer and plumper：
0.2。
In the present invention, propylene is 100: 0.01~100 with the mass ratio of ethylene random acrylic resin copolymer and antioxidant：
1。
In the present invention, propylene is 100: 0.01~100 with the mass ratio of ethylene random acrylic resin copolymer and nucleator：
0.8.
The present invention also provides a kind of system of the above-mentioned high-flowability polypropylene resin for the manufacture of disposable medical syringe
Preparation Method, its by the way that propylene is mixed 2~5 minutes at normal temperatures and pressures with ethylene random acrylic resin copolymer and additive,
Then extruding pelletization is carried out, obtains being exclusively used in the acrylic resin of disposable medical syringe manufacture.
The present invention has advantages below compared with prior art：
The physicochemical property of the high-flowability polypropylene resin of gained of the invention is as shown in table 1, and it has suitable melt flow
Dynamic property and rigidity, can meet the processing request and mechanical property requirements of disposable medical syringe, meet YYT0242-
2007《Medical infusion, blood transfusion, instrument used for injection polypropylene dedicated material》The requirement of professional standard.
The acrylic resin typical performance of table 1
| Test event | Detection method | Unit | Desired value |
| Melt mass flow rate | GB/T3682-2000 | g/10min | 25~50 |
| Bending modulus | GB/T 9341-2000 | MPa | ＞ 800 |
| Simply supported beam notch impact strength (23 DEG C) | GB/T 1843-1996 | kJ/m2 | ＞ 4.5 |
| Light transmittance, % | GB/T2410-2008 | % | ≥75 |
| Yellow colour index | HG/T3862-2006 | ≤-1 |
The acrylic resin of the present invention is propylene (0.5~4.5wt% of ethylene contents), meets the light of disposable syringe
Learn performance requirement and toughness reguirements.As adjust density of hydrogen come adjustment control obtained by ethylene random COPP have compared with
High melt flow rate (MFR), with the processing characteristics of reinforced resin, it can further improve processing temperature and production efficiency.
Embodiment
The preparation of the propylene-ethylene atactic copolymerized polypropene of embodiment 1
Using the propylene, ethene, hydrogen of polymer grade as raw material, add in annular-pipe reactor, and add catalyst DQ- III, help
Catalyst triethyl aluminum (TEAL), electron donor DONOR and antistatic additive Atmer 163 stir.Wherein：Catalyst DQ-
III adds according to yield 40kg/ tons, TEAL/ propylene=0.21；TEAL/DONOR=3, antistatic additive Atmer 163 be 2~
3kg/h.65~72 DEG C of reaction temperature in annular-pipe reactor is controlled, reaction pressure is 3.3~4.0MPa, density of hydrogen 4500~
5500ppm, so as to obtain propylene and ethylene random acrylic resin copolymer.Its performance is shown in Table 2.
The acrylic resin physical property of table 2
| Project | Testing standard | Test result |
| Melt flow rate (MFR), g/10min | GB/T 3682 | 30±2.0 |
| Isotactic index, % | MA 15763 | 97.0±1.0 |
Propylene-ethylene atactic copolymerized polypropene, antioxidant and the plumper prepared as the proportioning shown in table 3, Example 1
100L super mixers are added, are mixed at normal temperatures and pressures, incorporation time 2~5 minutes, then using double screw extruder
It is granulated to obtain, temperature control carries out physical property at 170~240 DEG C, to the acrylic resin of disposable medical syringe
Test analysis, it the results are shown in Table 4.
The embodiment of table 3 matches
| Embodiment 1 | Embodiment 2 | Embodiment 3 | |
| Atactic copolymerized polypropene | |||
| 1,1,3- tri- (2- methyl -4- hydroxyl -5- tert-butyl-phenyls) butane | 0.035% | 0.05% | 0.065% |
| Three (2,4- di-tert-butyl-phenyl) phosphite esters | 0.035% | 0.050% | 0.100% |
| Di-2-ethylhexylphosphine oxide (2,4- di-tert-butyl-phenyls) aluminum phosphate | 0.01% | 0.1% | 0.2% |
| Two-(3,4- dimethyl benzal) sorbierites | 0.2% | 0.1% | 0.4% |
| Two (to methyl benzylidene) xylitols | 0.01% | 0.1% | 0.4% |
| Calcium stearate | 0.050% | 0.050% | 0.050% |
| Hydrogenate talcum powder | 0.030% | 0.030% | 0.030% |
Table 4 is used for the physicochemical property of the acrylic resin of disposable medical syringe manufacture
The present invention can be summarized with others without prejudice to the concrete form of spirit or essential characteristics of the present invention.The present invention's is upper
The description of the invention rather than limitation can only be all considered by stating embodiment, and every substantial technological according to the present invention is to real above
The subtle modifications, equivalent variations and modifications that example is made are applied, are belonged in the range of technical solution of the present invention.
Claims (10)
- A kind of 1. high-flowability polypropylene resin for the manufacture of disposable medical syringe, it is characterised in that the high fluidity Acrylic resin is made up of 98~99.7% propylene with ethylene random acrylic resin copolymer and 0.03~2% additive； Wherein：In the propylene and ethylene random co-polypropylene resin, the content of ethene is between 0.5~4.5wt%, its melt flows Speed is 25~50g/10min under conditions of 230 DEG C, 2.16kg/10min, and isotactic index is 95~99%, number-average molecular weight Between 7~100,000, molecular weight distributing index is between 4~6；The additive includes antioxidant, plumper and nucleator.
- 2. high-flowability polypropylene resin according to claim 1, it is characterised in that the ethylene random COPP Resin is made by the following method：Using propylene, ethene and hydrogen as raw material, and add catalyst, co-catalyst, electron donor and Antistatic additive is in annular-pipe reactor, in 65~72 DEG C of temperature, 3.3~4.0MPa pressure, and density of hydrogen is 1000~ Reacted under conditions of 6000ppm, so as to obtain propylene and ethylene random acrylic resin copolymer.
- 3. high-flowability polypropylene resin according to claim 2, it is characterised in that catalyst uses DQ- III, co-catalysis Agent uses triethyl aluminum TEAL, and described electron donor uses CDONOR, and described antistatic additive uses Atmer 163.
- 4. high-flowability polypropylene resin according to claim 1, it is characterised in that：The antioxidant be antioxidant A and Antioxidant B combination, wherein：Antioxidant A is 1,1,3- tri- (2- methyl -4- hydroxyl -5- tert-butyl-phenyls) butane；Antioxidant B For three (2,4- di-tert-butyl-phenyl) phosphite esters；Antioxidant A and antioxidant B mass ratio 1: 0.3~1：10.
- 5. high-flowability polypropylene resin according to claim 1, it is characterised in that the nucleator be nucleator A, into Core agent B and nucleator C combination, wherein, nucleator A is di-2-ethylhexylphosphine oxide (2,4- di-tert-butyl-phenyl) aluminum phosphate, and nucleator B is Two-(3,4- dimethyl benzal) sorbierites, nucleator C are two (to methyl benzylidene) xylitols；Nucleator A, nucleator B and Nucleator C mass ratioes are (0.01~1)：(0.01~1)：(0.01~1).
- 6. high-flowability polypropylene resin according to claim 1, it is characterised in that described plumper is calcium stearate With the combination of hydrogenation talcum powder；Wherein the mass ratio of calcium stearate and hydrogenation talcum powder is 1：0.8~1：1.3.
- 7. high-flowability polypropylene resin according to claim 1, it is characterised in that propylene and ethylene random copolymerization poly- third The mass ratio of olefine resin and plumper is 100: 0.01~100：0.2.
- 8. high-flowability polypropylene resin according to claim 1, it is characterised in that propylene and ethylene random copolymerization poly- third The mass ratio of olefine resin and antioxidant is 100: 0.01~100：1.
- 9. high-flowability polypropylene resin according to claim 1, it is characterised in that propylene and ethylene random copolymerization poly- third The mass ratio of olefine resin and nucleator is 100: 0.01~100：0.8.
- A kind of 10. high-flowability polypropylene for being used for the manufacture of disposable medical syringe according to one of claim 1~9 The preparation method of resin, it is characterised in that by propylene and ethylene random acrylic resin copolymer and additive at normal temperatures and pressures Mixing 2~5 minutes, then carries out extruding pelletization, obtains being exclusively used in the acrylic resin of disposable medical syringe manufacture.
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| CN201610866648.6A CN107880404A (en) | 2016-09-29 | 2016-09-29 | A kind of high-flowability polypropylene resin for the manufacture of disposable medical syringe and preparation method thereof |
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| CN201610866648.6A CN107880404A (en) | 2016-09-29 | 2016-09-29 | A kind of high-flowability polypropylene resin for the manufacture of disposable medical syringe and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109320842A (en) * | 2018-09-30 | 2019-02-12 | 杨战军 | A kind of polypropylene for medical article thermoplastic elastomer (TPE) and its preparation method and application |
| CN110283388A (en) * | 2019-05-30 | 2019-09-27 | 中韩(武汉)石油化工有限公司 | A kind of preparation method of the medical material of resistance to gamma-irradiation polypropylene transparent |
| CN114163720A (en) * | 2021-11-05 | 2022-03-11 | 北方华锦化学工业股份有限公司 | Special polypropylene material for two-piece type injector piston assembly and preparation method thereof |
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| CN101338056A (en) * | 2007-07-03 | 2009-01-07 | 中国石化上海石油化工股份有限公司 | Acrylic resin for manufacturing syringes for medical use |
| CN101583663A (en) * | 2007-01-12 | 2009-11-18 | 陶氏环球技术公司 | Composition suitable for thin-wall injection molded articles |
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| CN105585778A (en) * | 2014-10-20 | 2016-05-18 | 中国石油化工股份有限公司 | Polypropylene resin special for manufacturing of medical ampoule bottles |
| CN105980457A (en) * | 2013-12-18 | 2016-09-28 | 博里利斯股份公司 | Bopp film with improved stiffness/toughness balance |
-
2016
- 2016-09-29 CN CN201610866648.6A patent/CN107880404A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101583663A (en) * | 2007-01-12 | 2009-11-18 | 陶氏环球技术公司 | Composition suitable for thin-wall injection molded articles |
| CN101338056A (en) * | 2007-07-03 | 2009-01-07 | 中国石化上海石油化工股份有限公司 | Acrylic resin for manufacturing syringes for medical use |
| CN102399395A (en) * | 2010-09-07 | 2012-04-04 | 中国石油天然气股份有限公司 | Preparation method of high-flowing high ethylene content polypropylene randon transparent copolymer resin |
| CN105980457A (en) * | 2013-12-18 | 2016-09-28 | 博里利斯股份公司 | Bopp film with improved stiffness/toughness balance |
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| CN104629178A (en) * | 2015-01-30 | 2015-05-20 | 上海日之升新技术发展有限公司 | Low-smell glass-fiber-reinforced halogen-free flame-retardant polypropylene composition and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109320842A (en) * | 2018-09-30 | 2019-02-12 | 杨战军 | A kind of polypropylene for medical article thermoplastic elastomer (TPE) and its preparation method and application |
| CN110283388A (en) * | 2019-05-30 | 2019-09-27 | 中韩(武汉)石油化工有限公司 | A kind of preparation method of the medical material of resistance to gamma-irradiation polypropylene transparent |
| CN114163720A (en) * | 2021-11-05 | 2022-03-11 | 北方华锦化学工业股份有限公司 | Special polypropylene material for two-piece type injector piston assembly and preparation method thereof |
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Application publication date: 20180406 |