CN103483758B - A kind of production method of long acting antibiotic polypropylene dedicated material - Google Patents
A kind of production method of long acting antibiotic polypropylene dedicated material Download PDFInfo
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- CN103483758B CN103483758B CN201310436761.7A CN201310436761A CN103483758B CN 103483758 B CN103483758 B CN 103483758B CN 201310436761 A CN201310436761 A CN 201310436761A CN 103483758 B CN103483758 B CN 103483758B
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Abstract
The invention discloses a kind of production method of long acting antibiotic polypropylene dedicated material, carry out in the Amoco Horizontal stirring reactor of two series connection, adopt the method for general commercial Z-N polymerizing catalyst and direct polymerization, by the adjustment hydrogen response of catalyzer between Amoco gas phase polymerization apparatus different reactor and the copolymerization performance of propylene and ethene, double-reactor series polymerizations mode is utilized to obtain polypropene composition base-material, special composite antibacterial adjuvant system is added at pelletization stage, antiseptic-germicide is uniformly dispersed in polypropylene, there is long acting antibiotic performance, be directly applied for the household electrical appliances higher to antibacterial requirement, automobile, the fields such as daily necessities.
Description
Technical field
The present invention relates to field of new, particularly relate to a kind of method of producing long acting antibiotic polypropylene dedicated material.
Background technology
Along with the develop rapidly of national economy, the material of people, culture, standard of living progressively improve, and plastics occupy more and more consequence in daily life.Polypropylene is a kind of non-toxic plastic, has higher thermotolerance and good intensity, is widely used in a lot of field.But polypropylene is the same with other plastics easy in various unwanted bacteria and mould contamination, when humiture is applicable to, easier bacterial growth.For this reason, domestic a lot of modifying plastics enterprise by adding the method for antibacterial raw material to solve the easy contaminated problem of polypropylene product in polypropylene product, but this easily makes the yellowish of polypropylene articles, and antiseptic-germicide can not be made to be uniformly dispersed in polypropylene, antibacterial effect can not keep lasting.
Plastic antimicrobial agent conventional is at present divided into organic antibacterial agent and inorganic antiseptic two class.Organic antibacterial agent mainly contains ethers, phenol, biphenyl ethers, quaternary ammonium salt, thiazole compound etc., and be characterized in that sterilization speed is fast, has a broad antifungal spectrum, but resistance toheat is poor, antibacterial validity period is short.Inorganic antiseptic is mainly silver, zinc plasma and compound thereof or complex compound, and be characterized in good heat resistance, has a broad antifungal spectrum, security is high, and antibacterial validity period is long.But silver-series antibacterial agent colour stability is poor, meeting variable color in use procedure, and the antimicrobial component in polypropylene can not be made to be uniformly dispersed, antibacterial effect can not be lasting.
Summary of the invention
The object of this invention is to provide a kind of balance, Material Physics mechanical property and long acting antibiotic performance with good rigidity and toughness higher, the production method of the long acting antibiotic polypropylene dedicated material in the fields such as household electrical appliances, automobile, daily necessities can be directly applied for.
To achieve these goals, the present invention by the following technical solutions: a kind of production method of long acting antibiotic polypropylene dedicated material, two series connection Amoco Horizontal stirring reactors in carry out, comprise the following steps:
(1) in the first reactor, continue to pass into propylene monomer, catalyzer, promotor, hydrogen and external electron donor, control polymerization temperature 60 ~ 80 DEG C, polymerization pressure is at 2 ~ 3MPa, H
2/ C
3mass ratio controls to carry out vapour phase polymerization under the condition of 0.1 ‰ ~ 0.2 ‰, and in the first reactor, product out enters the second reactor;
(2) in the second reactor, add comonomer ethylene, add-on at 1.5 ~ 2.5Kg/hr, polymerization temperature 70 ~ 80 DEG C, polymerization pressure 2 ~ 3MPa, in polymkeric substance, ethylene content controls 7.0% ~ 8.0%;
Reactant in (3) second reactors carries out extruding pelletization in granulating equipment, and add nano-rubber compound auxiliary system, namely discharging obtains long acting antibiotic polypropylene dedicated material.
Described catalyzer is Z-N catalyzer, is the compound system of a kind of in TK, ND, NA, CDI, NG or any two kinds; Described catalyzer can directly add in the first reactor, or and promotor through pre-complexing or and the prepolymerization of part propylene monomer after add in the first reactor.
Described promotor is organo-aluminium compound, can directly add in the first reactor, or adds in the first reactor after pre-complexing with catalyzer.Described promotor is triethyl aluminum, triisobutyl aluminium or three n-butylaluminum.The ratio of described catalyst component and organo-aluminium compound with Ti/Al molar ratio computing for 1:25 ~ 1:100.
Described external electron donor is one or both compound systems of silicoorganic compound, the general formula of silicoorganic compound is RnSi (OR ') 4-n, 0<n≤3 in formula, in general formula, R and R ' is identical or different alkyl, cycloalkyl, aryl, haloalkyl, and R also can be halogen or hydrogen atom.Described external electron donor is dimethyldimethoxysil,ne, trimethylmethoxysilane or tetraethoxysilane.
Described nano-rubber compound auxiliary system is by inorganic antiseptic or organic antibacterial agent load on ultra-fine fully vulcanized powder rubber, forms nano level composite antibacterial adjuvant system.Described inorganic antiseptic is silver, zn cpds or complex compound; Described organic antibacterial agent is ethers, phenol, biphenyl ethers, quaternary ammonium salt or thiazole compound.
AMOCO horizontal gas phase agitated bed production equipment, with the design of its uniqueness, in propylene polymerization, there is a lot of advantage: the piston flow that (1) unique reactor design can form material runs, and polymerization process shortens dramatically, the switching of the trade mark is easier, and transiting product is less; (2) its service efficiency is high, and energy consumption is low, does not rely on vapor phase stream to move and fluidized-bed, material just can be made fully to mix; (3) there is not liquid hydrocarbon in reaction process, also do not have the discharge of fluent meterial, various gaseous component can be discharged into torch, therefore good operation safety.
Present method adopts the method for general commercial Z-N polymerizing catalyst and direct polymerization, by the adjustment hydrogen response of catalyzer between Amoco gas phase polymerization apparatus different reactor and the copolymerization performance of propylene and ethene, double-reactor series polymerizations mode is utilized to obtain polypropene composition base-material, special composite antibacterial adjuvant system is added at pelletization stage, antiseptic-germicide is uniformly dispersed in polypropylene, there is long acting antibiotic performance, be directly applied for the field such as household electrical appliances, automobile, daily necessities higher to antibacterial requirement.
The long acting antibiotic polypropylene dedicated material that the present invention produces has good rigidity and the balance of toughness under the prerequisite keeping higher mobility (melt flow rate (MFR) 10 ~ 30g/10min).By the design to auxiliary formula system, add the nano-rubber compound auxiliary system that appropriate specific loads has antiseptic-germicide, realize the comprehensive raising of Material Physics mechanical property and long acting antibiotic performance, be directly applied for the field such as household electrical appliances, automobile, daily necessities higher to long acting antibiotic requirement.
Embodiment
Below the specific embodiment of the present invention is described in detail, but it is pointed out that protection scope of the present invention not by the restriction of these embodiments, but determined by claims.
Embodiment 1
After catalyzer TK and polypropylene segment monomer are carried out prepolymerization, add the first reactor with promotor triethyl aluminum and external electron donor dimethyldimethoxysil,ne, propylene monomer, hydrogen, temperature of reaction 65 DEG C, reaction pressure 2 ~ 3MPa, H
2/ C
3mass ratio controls, 0.15 ‰, to carry out vapour phase polymerization.Reaction product enters the second reactor, adds comonomer ethylene, and add-on controls at 1.8Kg/hr, and temperature of reaction 75 DEG C, reaction pressure 2 ~ 3MPa, in polymkeric substance, ethylene content controls 7.5%.Reaction product adds in granulating working procedure the nano-rubber compound auxiliary system 0.3% that load has antiseptic-germicide, and discharging obtains long acting antibiotic polypropylene dedicated material.
Embodiment 2
After catalyst n D and promotor triethyl aluminum are carried out pre-complexing, the first reactor is added with external electron donor (dimethyldimethoxysil,ne and tetraethoxysilane composite), propylene monomer, hydrogen, temperature of reaction 70 DEG C, reaction pressure 2 ~ 3MPa, H
2/ C
3mass ratio controls 0.1 ‰, carries out vapour phase polymerization.Reaction product enters the second reactor, adds comonomer ethylene, and add-on controls at 1.5Kg/hr, and temperature of reaction 80 DEG C, reaction pressure 2 ~ 3MPa, in polymkeric substance, ethylene content controls 7.0%.Reaction product adds in granulating working procedure the nano-rubber compound auxiliary system 0.4% that load has antiseptic-germicide, and discharging obtains long acting antibiotic polypropylene dedicated material.
Embodiment 3
Catalyzer CDI and NG is first composite, after carrying out prepolymerization with polypropylene segment monomer again, the first reactor is added with promotor triethyl aluminum and external electron donor (dimethyldimethoxysil,ne and tetraethoxysilane composite), propylene monomer, hydrogen, temperature of reaction 60 DEG C, reaction pressure 2 ~ 3MPa, H
2/ C
3mass ratio controls 0.2 ‰, carries out vapour phase polymerization.Reaction product enters the second reactor subsequently, adds comonomer ethylene, and add-on controls at 2.0Kg/hr, and temperature of reaction 75 DEG C, reaction pressure 2 ~ 3MPa, in polymkeric substance, ethylene content controls 7.5%.Reaction product adds in granulating working procedure the nano-rubber compound auxiliary system 0.5% that load has antiseptic-germicide, and discharging obtains long acting antibiotic polypropylene dedicated material.
Embodiment 4
Catalyzer CDI and NG is first composite, after carrying out prepolymerization with polypropylene segment monomer again, the first reactor is added with promotor triethyl aluminum and external electron donor (dimethyldimethoxysil,ne and tetraethoxysilane composite), propylene monomer, hydrogen, temperature of reaction 80 DEG C, reaction pressure 2 ~ 3MPa, H
2/ C
3mass ratio controls, 0.18 ‰, to carry out vapour phase polymerization.Reaction product enters the second reactor subsequently, adds comonomer ethylene, and add-on controls at 2.5Kg/hr, and temperature of reaction 72 DEG C, reaction pressure 2 ~ 3MPa, in polymkeric substance, ethylene content controls 8.0%.Reaction product adds in granulating working procedure the nano-rubber compound auxiliary system 0.5% that load has antiseptic-germicide, and discharging obtains long acting antibiotic polypropylene dedicated material.
Embodiment 5
Catalyzer CDI and NG is first composite, after carrying out prepolymerization with polypropylene segment monomer again, the first reactor is added with promotor triethyl aluminum and external electron donor (dimethyldimethoxysil,ne and tetraethoxysilane composite), propylene monomer, hydrogen, temperature of reaction 75 DEG C, reaction pressure 2 ~ 3MPa, H
2/ C
3mass ratio controls 0.1 ‰, carries out vapour phase polymerization.Reaction product enters the second reactor subsequently, adds comonomer ethylene, and add-on controls at 1.8Kg/hr, and temperature of reaction 74 DEG C, reaction pressure 2 ~ 3MPa, in polymkeric substance, ethylene content controls 7.3%.Reaction product adds in granulating working procedure the nano-rubber compound auxiliary system 0.6% that load has antiseptic-germicide, and discharging obtains long acting antibiotic polypropylene dedicated material.
The performance test methods of antibacterial polypropylene and index are in table 1, and specific embodiment performance is in table 2.
The performance test methods of table 1 antibacterial polypropylene and index
The performance of resin prepared by table 2 embodiment
Although be described in detail the specific embodiment of the present invention above in conjunction with the embodiments, it is pointed out that protection scope of the present invention not by the restriction of these embodiments, but determined by claims.Those skilled in the art can carry out suitable change to these embodiments in the scope not departing from technological thought of the present invention and purport, and the embodiment after these changes is obviously also included within protection scope of the present invention.
Claims (3)
1. a production method for long acting antibiotic polypropylene dedicated material, is characterized in that: carry out in the Amoco gas phase Horizontal stirring reactor of two series connection, comprise the following steps:
In the first reactor, continue to pass into propylene monomer, catalyzer, promotor, hydrogen and external electron donor, control polymerization temperature 60 ~ 80 DEG C, polymerization pressure is at 2 ~ 3MPa, H
2/ C
3mass ratio controls to carry out vapour phase polymerization under the condition of 0.1 ‰ ~ 0.2 ‰, and in the first reactor, product out enters the second reactor;
In the second reactor, add comonomer ethylene, add-on at 1.5 ~ 2.5Kg/hr, polymerization temperature 70 ~ 80 DEG C, polymerization pressure 2 ~ 3MPa, in polymkeric substance, ethylene content controls 7.0% ~ 8.0%;
Reactant in second reactor carries out extruding pelletization in granulating equipment, and add the nano-rubber compound auxiliary system of reactant weight 0.3% ~ 0.6%, namely discharging obtains long acting antibiotic polypropylene dedicated material;
Described catalyzer is Z-N catalyzer, is the compound system of any two kinds in TK, ND, NA, CDI, NG; Described catalyzer can directly add in the first reactor, or and promotor through pre-complexing or and the prepolymerization of part propylene monomer after add in the first reactor;
Described promotor is organo-aluminium compound, can directly add in the first reactor, or adds after pre-complexing in the first reactor with catalyzer;
Described promotor is triethyl aluminum, triisobutyl aluminium or three n-butylaluminum;
The ratio of described catalyst component and organo-aluminium compound with Ti/Al molar ratio computing for 1:25 ~ 1:100;
Described nano-rubber compound auxiliary system is by inorganic antiseptic or organic antibacterial agent load on ultra-fine fully vulcanized powder rubber, forms nano level composite antibacterial adjuvant system;
Described inorganic antiseptic is silver, zn cpds or silver, zinc complex; Described organic antibacterial agent is ethers, phenol, quaternary ammonium salt or thiazole compound.
2. the production method of long acting antibiotic polypropylene dedicated material according to claim 1, it is characterized in that: described external electron donor is one or both compound systems of silicoorganic compound, the general formula of silicoorganic compound is R
nsi (OR ')
4-n, 0<n≤3 in formula, in general formula, R and R ' is identical or different alkyl, cycloalkyl, aryl, haloalkyl, and R also can be halogen or hydrogen atom.
3. the production method of long acting antibiotic polypropylene dedicated material according to claim 2, is characterized in that: described external electron donor is dimethyldimethoxysil,ne, trimethylmethoxysilane or tetraethoxysilane.
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| CN109401071A (en) * | 2017-08-18 | 2019-03-01 | 中国石化扬子石油化工有限公司 | A kind of antibacterial PPR hot water tube material and preparation method thereof |
| CN109294149A (en) * | 2018-09-16 | 2019-02-01 | 郑州成济堂生物科技有限公司 | A kind of preparation method of durable antibiotic polypropylene plastic cup |
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| DE69308209T2 (en) * | 1992-05-29 | 1997-06-12 | Amoco Corp | POLYMERIZATION OF ALPHA OLEFINS |
| CN101735351B (en) * | 2008-11-07 | 2011-10-05 | 中国石油天然气股份有限公司 | Method for preparing high-fluidity wide-distribution polypropylene and product thereof |
| CN102060951B (en) * | 2009-11-12 | 2012-12-19 | 中国石油化工股份有限公司 | Process for continuously producing co-polypropylene with high ethylene content by using propylene gas-phase polymerization device |
| CN102382375A (en) * | 2010-09-03 | 2012-03-21 | 中国石油化工股份有限公司 | Special polypropylene material for automobile bumpers or upholsteries |
| CN103073784B (en) * | 2011-10-26 | 2015-09-16 | 中国石油化工股份有限公司 | A kind of Antibacterial polypropylene composition and preparation method thereof |
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