CN114671968A - Preparation method of gamma radiation resistant polypropylene special material for medical injector - Google Patents

Preparation method of gamma radiation resistant polypropylene special material for medical injector Download PDF

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CN114671968A
CN114671968A CN202210166724.8A CN202210166724A CN114671968A CN 114671968 A CN114671968 A CN 114671968A CN 202210166724 A CN202210166724 A CN 202210166724A CN 114671968 A CN114671968 A CN 114671968A
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special material
medical injector
gamma radiation
polypropylene
radiation resistant
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王楠
孙洪伟
孙钰淇
武振东
刘刚
刘忠全
付莹
李春晖
修忠海
姜翠
张帆
肖大君
韩丽君
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North Huajin Chemical Industries Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/04—Monomers containing three or four carbon atoms
    • C08F210/06—Propene
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • 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
    • C08K5/134—Phenols containing ester groups
    • C08K5/1345—Carboxylic esters of phenolcarboxylic 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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/32—Compounds containing nitrogen bound to oxygen
    • 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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3432—Six-membered rings
    • C08K5/3435—Piperidines
    • 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
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • 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
    • 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

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The invention belongs to the field of medical high-end polypropylene special materials, and particularly discloses a preparation method of a gamma radiation resistant polypropylene special material for a medical injector. The method effectively ensures that the product has better consistent performance before and after radiation, each index meets the use requirement of the medical injector, and the physical and chemical properties and the color of the special material for the medical injector are not changed or are changed very little after the special material for the medical injector is sterilized by gamma rays (30KGy), thereby meeting the use requirement of customers.

Description

Preparation method of gamma radiation resistant polypropylene special material for medical injector
Technical Field
The invention belongs to the field of polyolefin materials, and particularly relates to a preparation method of a gamma radiation resistant polypropylene special material for a medical injector.
Background
China is the biggest world producing country of medical injectors, 170 hundred million injectors are produced in about one year, the production accounts for seven percent of the total world production, the proportion of the injectors exported in one year is about 40 percent, and the annual growth rate of the domestic market is about 8 percent. The amount of atactic transparent polypropylene consumed in this application is about 20 million tons per year in our country.
With the gamma radiation resistant sterilization becoming the main mode of medical supplies sterilization, the medical radiation resistant PP material has become a hot spot of competitive development in various countries. However, the radiation stability of the ordinary medical PP injection device is poor, the physical and mechanical properties of the PP injection device after radiation sterilization are deteriorated, the color is yellowed, and the aging phenomenon is aggravated along with the increase of the storage time, so that the use performance is lost.
Patent CN 101967247A introduces a medical low temperature resistant toughened anti-gamma ray impact-resistant transparent polypropylene material and a preparation method thereof, but the method uses homopolymerized polypropylene, and because more additives are used, the processing cost is increased and the processing control in the modification process is complicated.
Patent CN 110283388A describes a preparation method of a gamma irradiation resistant polypropylene transparent medical material, but the performances before and after irradiation are not compared, and particularly the yellow index performance is not excellent enough. The material requires that the physical, chemical and color of the material are not changed or changed slightly after the Co source or the electron accelerator (25KGy) is radiated for sterilization, which is very critical for preparing the injector.
Disclosure of Invention
The technical problem to be solved by the invention is mainly to overcome the defects, and the invention provides a preparation method of a gamma radiation resistant polypropylene special material for a medical injector.
In order to achieve the purpose, the invention adopts the technical scheme that:
a preparation method of a gamma radiation resistant polypropylene special material for a medical injector comprises the following steps:
s1 is made from propylene, main catalyst and cocatalyst are added into a prepolymerization reactor, ethylene is respectively introduced into a loop reactor R201 and a loop reactor R202, antistatic agent is added at the blanking part of a second loop reactor R202, and the hydrogen concentration of the two loop reactors is controlled to be 3500 ppm-; the density of the slurry in the loop reactors R201 and R202 is 510-560kg/m3。
S2 the slurry from the loop reactor enters a high-pressure flash tank D301 for gas-solid separation, and the polypropylene powder is discharged from the high-pressure flash tank D301 and enters a bag filter F301. Feeding the polypropylene powder from the bag filter F301 into a steamer D501 by gravity, decomposing a catalyst and an external electron Donor Donor by a steaming method, removing residual hydrocarbon, feeding the steamed polypropylene powder from the steamer D501 into a fluidized bed dryer D502, reversely contacting the polypropylene powder reaching the dryer D502 with high-temperature nitrogen, removing water in the polymer, and obtaining the random copolymerization polypropylene powder with the melt mass flow rate of 25 +/-5 g/10 min;
And S3, the polypropylene powder enters a granulation section, and is melted, homogenized, filtered and granulated with a nucleating agent, an antioxidant, an absorbent, a light stabilizer and a toughened thermoplastic elastomer in an extruder to produce a gamma radiation resistant polypropylene resin product.
Furthermore, the main catalyst is a CS-2 catalyst.
Furthermore, the ethylene addition in both loop reactors is 2-5 wt%.
Further, the hydrogen concentration of the loop reactor R201 is 3000-3500ppm, and the hydrogen concentration of the loop reactor R202 is 1500-2000 ppm.
Further, the nucleating agent is Asahi audio-visual NA-21.
Further, the slurry density in the loop reactor R201 is 510-560kg/m3The slurry density in the loop reactor R202 is 510-560kg/m3。
Further, the mass ratios of the random copolymerization polypropylene to the antioxidant, the nucleating agent, the absorbent and the light stabilizer are respectively as follows:
0.05 to 0.2 percent of antioxidant
Acid absorbent 0.02-0.06%
0.3 to 0.4 percent of nucleating agent
Light stabilizer 0.05-0.2%
The antioxidant is a multi-element hindered phenol antioxidant 1076: n-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, organic phosphite antioxidant AT168: tris (2, 4-di-tert-butylphenyl) phosphite and the phenol-free antioxidant FS042 (dioctadecylhydroxylamine). Preferably, 1076: AT168: FS 042: 1:2: 1.
The acid absorbent is a mixture of calcium stearate and hydrotalcite, preferably, the acid absorbent is calcium stearate: hydrotalcite 1: 1.
The light stabilizer is 770: in particular to sebacic acid bis-2, 2,6, 6-tetramethyl piperidinol ester (CAS NO: 52829-07-9).
The preparation method of the gamma radiation resistant polypropylene special material for the medical injector has the following advantages:
1. the production device and the process adopt a hydrogen adjusting process to control the melt index, so that the environment is not polluted, the requirement of environmental protection is met, the product has low smell, and the sanitary safety is greatly improved.
2. The process solves the problems of high cost, complex process and the like caused by excessive additives, and ethylene is added into the two reactors, so that the catalyst has higher activity, good product toughness and higher transparency. The produced product has good melt fluidity, high crystallization temperature, high crystallization speed, easy demoulding and short injection molding period.
3. The special material for the gamma radiation resistant polypropylene produced by the process has stronger client pertinence, more excellent performance than the existing special material for the gamma radiation resistant polypropylene, small changes of physical and chemical properties and color before and after radiation, and particularly the yellow index (30kGy) can reach-6.
The preparation method of the special gamma radiation resistant polypropylene material for the medical injector has the following technical difficulties:
1. In the polymerization process, the ethylene is added too much, the powder viscosity is increased, the feeding of a high-pressure flash tank D301 and a steaming tank D501 is not smooth, the feeding of propylene in a loop is influenced, the power of an axial flow pump is unstable or climbs, and therefore the control of the concentration of the slurry in a reactor is very important.
2. After the ethylene is added, the reaction is violent, the isotacticity is reduced, and the addition of the ethylene needs to be slowed down according to the actual reaction condition.
3. The selection and the proportion of the catalyst and the auxiliary agent are optimal, the normal operation of the device is not influenced, and the final performance of the product is ensured.
Drawings
FIG. 1 is a schematic flow chart of the preparation method of the present invention;
Detailed Description
In order to better meet various requirements of the market of gamma radiation resistant polypropylene for medical injectors, the invention provides a preparation method of a special gamma radiation resistant polypropylene material for medical injectors, the preparation method has more perfect indexes, and the problems of obvious changes of product color, yellow index, impact strength, bending modulus and the like before and after radiation are solved.
The following examples are provided to further illustrate the technical solutions of the present invention, but it should be noted that the following examples are only illustrative of the invention and should not be construed as limiting the scope of the present invention.
Example 1
The invention provides a preparation method of a gamma radiation resistant polypropylene special material for a medical injector.
The method comprises the following steps:
taking propylene as a raw material, adding a main catalyst and a cocatalyst into a prepolymerization reactor, respectively introducing ethylene into a loop reactor R201 and a loop reactor R202, adding an antistatic agent into the blanking part of the loop reactor R202, and controlling the hydrogen concentration of the two loop reactors to be 1500-3500 ppm; the slurry density in the loop reactors R201 and R202 is 510-560kg/m3。
And (3) feeding the slurry from the loop reactor into a high-pressure flash tank D301 for gas-solid separation, and discharging the polypropylene powder into a bag filter F301 through the high-pressure flash tank D301. Feeding the polypropylene powder from the bag filter F301 into a steamer D501 by gravity, decomposing a catalyst and an external electron Donor Donor by a steaming method, removing residual hydrocarbon, feeding the steamed polypropylene powder into a fluidized bed dryer D502 from the steamer D501, reversely contacting the steamed polypropylene powder with high-temperature nitrogen to remove water in a polymer to obtain the random copolymerization polypropylene powder; the specific production process is shown in attached appendix 1.
Table 1: main polymerization process parameters
Main process parameters R201 R202
Hydrogen gas concentration (ppm) 3000 1500
Density of slurry (kg/m)3) 520 520
The powder index obtained was 22.4g/10 min.
And (3) the polymer powder enters a granulation section and is mixed with 0.3% of nucleating agent, 1076% of antioxidant, AT168: FS042, 1:2:1, calcium stearate serving as an absorbent: mixing hydrotalcite 1:1 and light stabilizer 0.05%, and pelletizing to produce polypropylene resin product.
Table 2: test result of special material performance
Figure BDA0003516481760000051
Example 2
Table 1: main polymerization process parameters
Main process parameters R201 R202
Hydrogen concentration (ppm) 3500 2000
Density of slurry (kg/m)3) 520 520
The powder index obtained was 27.2g/10 min.
Table 2: test result of special material performance
Figure BDA0003516481760000061
Example 3
Table 1: main polymerization process parameters
Main process parameters R201 R202
Hydrogen concentration (ppm) 3500 2000
Density of slurry (kg/m)3) 550 550
The powder index obtained was 25.8g/10 min.
Table 2: test result of special material performance
Figure BDA0003516481760000062
Example 4
Table 1: main polymerization process parameters
Main process parameters R201 R202
Hydrogen concentration (ppm) 3500 2000
Density of slurry (kg/m)3) 550 550
The powder index obtained was 25.5g/10 min.
And 0.4% of nucleating agent, 1076: AT168: FS 042: 1:2:1, absorbent calcium stearate: mixing hydrotalcite 1:1 and light stabilizer 0.05%, and pelletizing to produce polypropylene resin product.
Table 2: test result of special material performance
Figure BDA0003516481760000071
From examples 1 to 3, when the hydrogen concentration in loop reactor R201 was 3500ppm and the hydrogen concentration in loop reactor R202 was 2000 ppm; the slurry density in the loop reactor R201/R202 was 550/550kg/m 3The index value of the powder is ideal.
The materials obtained in examples 3 and 4 have the advantages that when the addition amount of the nucleating agent is 0.4%, the special material for the gamma radiation-resistant polypropylene produced in the granulation section has more excellent performance, and the physical properties and the color change before and after radiation are small. And selecting a product to carry out chemical performance test, wherein the key indexes meet the requirements of customers, and the specific data are as follows:
color appearance: without change
Physical properties: index 25 + -5 g/10min
The impact strength of the gap of the cantilever beam is more than or equal to 3.0KJ/m2
Tensile yield stress is more than or equal to 24.0Mpa
Flexural modulus is more than or equal to 800Mpa
The haze is less than or equal to 12 percent
Yellow index (after 25KGy radiation) is less than or equal to 0
Chemical properties: pH value is less than or equal to 1.0
The heavy metal content is less than or equal to 1.0ug/ml
Chromium content is less than or equal to 1.0ug/ml
The ultraviolet absorbance is less than or equal to 0.8.

Claims (10)

1. A preparation method of a gamma radiation resistant polypropylene special material for a medical injector is characterized by comprising the following steps:
s1 is prepared by adding a main catalyst and a cocatalyst into a prepolymerization reactor to perform prepolymerization reaction by using propylene as a raw material, respectively introducing ethylene into two loop reactors R201 and R202 connected in series after the reaction, adding an antistatic agent at the blanking part of the second loop reactor R202, and controlling the hydrogen concentration of the two loop reactors to be 1500-3500 ppm; the slurry density of the two loop reactors is 510-560kg/m 3；
S2, feeding the slurry from the loop reactor into a high-pressure flash tank D301 for gas-solid separation to obtain polypropylene powder, and feeding the polypropylene powder discharged from the high-pressure flash tank D301 into a bag filter F301; feeding the polypropylene powder from the bag filter F301 into a steamer D501 by gravity, decomposing a catalyst and an external electron Donor Donor by a steaming method, removing residual hydrocarbon, feeding the steamed polypropylene powder into a fluidized bed dryer D502 from the steamer D501, reversely contacting the polypropylene powder reaching the fluidized bed dryer D502 with high-temperature nitrogen, removing moisture in the polymer, and obtaining the random copolymerization polypropylene powder with the melt mass flow rate of 25 +/-5 g/10 min;
s3, the obtained polypropylene random copolymer powder enters a granulation section, and is melted, homogenized, filtered and granulated with a nucleating agent, an antioxidant, an acid-absorbing agent and a light stabilizer in an extruder, and finally a gamma radiation resistant polypropylene resin product is produced.
2. The preparation method of the gamma radiation resistant polypropylene special material for the medical injector as claimed in claim 1, wherein the main catalyst is a CS-2 type catalyst, and the cocatalyst is triethylaluminum and an electron donor.
3. The method for preparing the gamma radiation resistant polypropylene special material for the medical injector according to claim 1, wherein the temperature of the loop reactor R201/R202 is 67.5-70 ℃.
4. The preparation method of the gamma radiation resistant polypropylene special material for the medical injector as claimed in claim 1, wherein the hydrogen concentration of the loop reactor R201 is 3000-3500ppm, and the hydrogen concentration of the loop reactor R202 is 1500-2000 ppm.
5. The method for preparing the gamma radiation resistant polypropylene special material for the medical injector according to claim 1, wherein the addition amount of the ethylene in the two loop reactors is 2-5% of the consumption amount of the propylene raw material.
6. The preparation method of the gamma radiation resistant polypropylene special material for the medical injector according to any one of claims 1 to 5, wherein the mass ratio of the random copolymer polypropylene to the antioxidant, the nucleating agent, the acid acceptor and the light stabilizer is respectively as follows:
100 percent of random copolymerization polypropylene
Antioxidant 0.05-0.2%
0.3 to 0.4 percent of nucleating agent
Acid absorbent 0.02-0.06%
0.05 to 0.2 percent of light stabilizer.
7. The method for preparing the gamma radiation resistant polypropylene special material for the medical injector according to claim 6, wherein the antioxidant is a multi-component hindered phenol antioxidant 1076: n-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, organic phosphite antioxidant AT 168: any one of tris (2, 4-di-tert-butylphenyl) phosphite, phenol-free antioxidant FS042 (dioctadecylhydroxylamine), or a mixture thereof.
8. The method for preparing the gamma-radiation-resistant polypropylene special material for the medical injector according to claim 6, wherein the acid-absorbing agent is any one of calcium stearate and hydrotalcite.
9. The method for preparing the gamma radiation resistant polypropylene special material for the medical injector according to claim 6, wherein the nucleating agent is Asahi electro-chemical NA-21.
10. The preparation method of the gamma radiation resistant polypropylene special material for the medical injector according to claim 6, wherein the light stabilizer is 770: in particular to sebacic acid bis-2, 2,6, 6-tetramethyl piperidinol ester (CAS NO: 52829-07-9).
CN202210166724.8A 2022-02-23 2022-02-23 Preparation method of gamma radiation resistant polypropylene special material for medical injector Pending CN114671968A (en)

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