CN103483758A - Method for production of long-acting antibacterial PP special material - Google Patents
Method for production of long-acting antibacterial PP special material Download PDFInfo
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- CN103483758A CN103483758A CN201310436761.7A CN201310436761A CN103483758A CN 103483758 A CN103483758 A CN 103483758A CN 201310436761 A CN201310436761 A CN 201310436761A CN 103483758 A CN103483758 A CN 103483758A
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Abstract
The invention discloses a method for production of long-acting antibacterial PP special material. The production process is performed in two horizontal Amoco stirred reactors which are connected in series, an ordinary commercial Z-N polymerization catalyst and a direct polymerization method are adopted, and through adjusting the hydrogen regulation sensitivities of the catalyst in different stirred reactors in an Amoco gas-phase polymerization device and the performance of copolymerization of propylene and ethylene, a double-reactor series-connection polymerization mode is utilized to obtain polypropylene composition base material, and a special composite antibacterial auxiliary system is added in the granulation stage, and an antibacterial agent is uniformly dispersed in the PP. The long-acting antibacterial PP special material has a long-acting antibacterial property, and can be directly suitable for fields such as household appliances, automobiles and daily necessaries which have higher antibacterial requirements.
Description
Technical field
The present invention relates to field of new, relate in particular to a kind of method of producing the long acting antibiotic polypropylene dedicated material.
Background technology
Along with the develop rapidly of national economy, people's material, 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 fields.But polypropylene is the same with other plastics easy in various unwanted bacterias and mould contamination, in the situation that humiture is applicable, more easily breeds bacterium.For this reason, the method of domestic a lot of modifying plastics enterprise by adding antibiotic raw material in polypropylene product is to solve the easy contaminated problem of polypropylene product, but this easily makes the color jaundice of polypropylene articles, and can not make antiseptic-germicide be uniformly dispersed in polypropylene, it is lasting that antibacterial effect can not keep.
Plastic antimicrobial agent commonly used is divided into organic antibacterial agent and inorganic antiseptic two classes at present.Organic antibacterial agent mainly contains ethers, phenol, biphenyl ethers, quaternary ammonium salt, thiazole compound etc., be characterized in that sterilization speed is fast, has a broad antifungal spectrum, but resistance toheat is poor, and antibiotic validity period is short.Inorganic antiseptic is mainly silver, zinc plasma and compound or complex compound, is characterized in good heat resistance, and has a broad antifungal spectrum is safe, and antibiotic validity period is long etc.But the silver-series antibacterial agent colour stability is poor, meeting variable color in use procedure, and can not make the antimicrobial component in polypropylene be uniformly dispersed, antibacterial effect can not be lasting.
Summary of the invention
The purpose 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, can be directly applied for the production method of the long acting antibiotic polypropylene dedicated material in the fields such as household electrical appliances, automobile, daily necessities.
To achieve these goals, the present invention by the following technical solutions: a kind of production method of long acting antibiotic polypropylene dedicated material, in the Amoco of two series connection Horizontal stirring reactor, 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 at 60～80 ℃, polymerization pressure at 2～3MPa, H
2/ C
3mass ratio is controlled under 0.1 ‰～0.2 ‰ condition and carries out vapour phase polymerization, and in the first reactor, product out enters the second reactor;
(2) in the second reactor, add comonomer ethene, add-on is at 1.5～2.5Kg/hr, 70～80 ℃ of polymerization temperatures, polymerization pressure 2～3MPa, in polymkeric substance, ethylene content is controlled at 7.0%～8.0%;
Reactant in (3) second reactors carries out extruding pelletization in granulating equipment, adds nano-rubber compound auxiliary system, and discharging obtains the long acting antibiotic polypropylene dedicated material.
Described catalyzer is the 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 add in the first reactor after pre-complexing with catalyzer.Described promotor is triethyl aluminum, triisobutyl aluminium or three n-butylaluminum.Described catalyst component be take the Ti/Al molar ratio computing as 1:25～1:100 with the ratio of organo-aluminium compound.
One or both compound systems that described external electron donor is silicoorganic compound, the general formula of silicoorganic compound is RnSi (OR ') 4-n, 0<n in formula≤3, in general formula, R and R ' they are identical or different alkyl, cycloalkyl, aryl, haloalkyl, R can be also halogen or hydrogen atom.Described external electron donor is dimethyldimethoxysil,ne, trimethylammonium methoxy silane or tetraethoxysilane.
Described nano-rubber compound auxiliary system is that inorganic antiseptic or organic antibacterial agent are loaded on ultra-fine fully vulcanized powder rubber, forms nano level composite antibiosis 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.
The horizontal gas phase agitated bed of AMOCO production equipment, with the design of its uniqueness, a lot of advantages are arranged in propylene polymerization: (1) unique reactor design can form the piston flow operation of material, 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, just can make material fully mix; (3) do not have liquid hydrocarbon in reaction process, also there is no the discharge of fluent meterial, various gaseous components can be discharged into torch, so good operation safety.
Present method adopts the method for general commercial Z-N polymerizing catalyst and direct polymerization, by adjusting the hydrogen response of catalyzer between Amoco gas phase polymerization apparatus different reactor and the copolymerization performance of propylene and ethene, utilize double-reactor series connection polymerization methods to obtain the polypropene composition base-material, add special composite antibiosis adjuvant system in the granulation stage, antiseptic-germicide is uniformly dispersed in polypropylene, there is the long acting antibiotic performance, be directly applied for fields such as antibiotic household electrical appliances of having relatively high expectations, automobile, daily necessities.
There is good rigidity and the balance of toughness under the prerequisite of the long acting antibiotic polypropylene dedicated material that the present invention produces higher mobility (melt flow rate (MFR) 10～30g/10min) in maintenance.By the design to the auxiliary formula system, add appropriate specific loads the nano-rubber compound auxiliary system of antiseptic-germicide is arranged, realize the comprehensive raising of Material Physics mechanical property and long acting antibiotic performance, be directly applied for the fields such as household electrical appliances that long acting antibiotic is had relatively high expectations, automobile, daily necessities.
Embodiment
Below the specific embodiment of the present invention is elaborated, but it is pointed out that protection scope of the present invention is not subject to the restriction of these embodiments, but determined by claims.
Embodiment 1
After catalyzer TK and polypropylene segment monomer are carried out to prepolymerization, add the first reactor with promotor triethyl aluminum and external electron donor dimethyldimethoxysil,ne, propylene monomer, hydrogen, 65 ℃ of temperature of reaction, reaction pressure 2～3MPa, H
2/ C
3mass ratio is controlled at 0.15 ‰, carries out vapour phase polymerization.Reaction product enters the second reactor, adds comonomer ethene, and add-on is controlled at 1.8Kg/hr, 75 ℃ of temperature of reaction, and reaction pressure 2～3MPa, in polymkeric substance, ethylene content is controlled at 7.5%.Reaction product adds load that the nano-rubber compound auxiliary system 0.3% of antiseptic-germicide is arranged in granulating working procedure, and discharging obtains the long acting antibiotic polypropylene dedicated material.
Embodiment 2
After catalyst n D and promotor triethyl aluminum are carried out to pre-complexing, and external electron donor (dimethyldimethoxysil,ne and tetraethoxysilane are composite), propylene monomer, hydrogen add the first reactor, 70 ℃ of temperature of reaction, reaction pressure 2～3MPa, H
2/ C
3mass ratio is controlled at 0.1 ‰, carries out vapour phase polymerization.Reaction product enters the second reactor, adds comonomer ethene, and add-on is controlled at 1.5Kg/hr, 80 ℃ of temperature of reaction, and reaction pressure 2～3MPa, in polymkeric substance, ethylene content is controlled at 7.0%.Reaction product adds load that the nano-rubber compound auxiliary system 0.4% of antiseptic-germicide is arranged in granulating working procedure, and discharging obtains the long acting antibiotic polypropylene dedicated material.
Embodiment 3
Catalyzer CDI and NG is first composite, after carrying out prepolymerization with the polypropylene segment monomer again, add the first reactor with promotor triethyl aluminum and external electron donor (dimethyldimethoxysil,ne and tetraethoxysilane are composite), propylene monomer, hydrogen, 60 ℃ of temperature of reaction, reaction pressure 2～3MPa, H
2/ C
3mass ratio is controlled at 0.2 ‰, carries out vapour phase polymerization.Reaction product enters the second reactor subsequently, adds comonomer ethene, and add-on is controlled at 2.0Kg/hr, 75 ℃ of temperature of reaction, and reaction pressure 2～3MPa, in polymkeric substance, ethylene content is controlled at 7.5%.Reaction product adds load that the nano-rubber compound auxiliary system 0.5% of antiseptic-germicide is arranged in granulating working procedure, and discharging obtains the long acting antibiotic polypropylene dedicated material.
Embodiment 4
Catalyzer CDI and NG is first composite, after carrying out prepolymerization with the polypropylene segment monomer again, add the first reactor with promotor triethyl aluminum and external electron donor (dimethyldimethoxysil,ne and tetraethoxysilane are composite), propylene monomer, hydrogen, 80 ℃ of temperature of reaction, reaction pressure 2～3MPa, H
2/ C
3mass ratio is controlled at 0.18 ‰, carries out vapour phase polymerization.Reaction product enters the second reactor subsequently, adds comonomer ethene, and add-on is controlled at 2.5Kg/hr, 72 ℃ of temperature of reaction, and reaction pressure 2～3MPa, in polymkeric substance, ethylene content is controlled at 8.0%.Reaction product adds load that the nano-rubber compound auxiliary system 0.5% of antiseptic-germicide is arranged in granulating working procedure, and discharging obtains the long acting antibiotic polypropylene dedicated material.
Embodiment 5
Catalyzer CDI and NG is first composite, after carrying out prepolymerization with the polypropylene segment monomer again, add the first reactor with promotor triethyl aluminum and external electron donor (dimethyldimethoxysil,ne and tetraethoxysilane are composite), propylene monomer, hydrogen, 75 ℃ of temperature of reaction, reaction pressure 2～3MPa, H
2/ C
3mass ratio is controlled at 0.1 ‰, carries out vapour phase polymerization.Reaction product enters the second reactor subsequently, adds comonomer ethene, and add-on is controlled at 1.8Kg/hr, 74 ℃ of temperature of reaction, and reaction pressure 2～3MPa, in polymkeric substance, ethylene content is controlled at 7.3%.Reaction product adds load that the nano-rubber compound auxiliary system 0.6% of antiseptic-germicide is arranged in granulating working procedure, and discharging obtains the long acting antibiotic polypropylene dedicated material.
The performance test methods of antibacterial polypropylene and index are in Table 1, and the 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
The specific embodiment of the present invention is had been described in detail although above in conjunction with the embodiments, it is pointed out that protection scope of the present invention is not subject to 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 that does not break away from technological thought of the present invention and purport, and within these embodiments after changing obviously are also included within protection scope of the present invention.
Claims (9)
1. the production method of a long acting antibiotic polypropylene dedicated material is characterized in that: carry out in the Amoco of two series connection gas phase Horizontal stirring reactor, comprise the following steps:
In the first reactor, continue to pass into propylene monomer, catalyzer, promotor, hydrogen and external electron donor, control polymerization temperature at 60～80 ℃, polymerization pressure at 2～3MPa, H
2/ C
3mass ratio is controlled under 0.1 ‰～0.2 ‰ condition and carries out vapour phase polymerization, and in the first reactor, product out enters the second reactor;
In the second reactor, add comonomer ethene, add-on is at 1.5～2.5Kg/hr, 70～80 ℃ of polymerization temperatures, polymerization pressure 2～3MPa, in polymkeric substance, ethylene content is controlled at 7.0%～8.0%;
Reactant in the second reactor carries out extruding pelletization in granulating equipment, adds the nano-rubber compound auxiliary system of reactant weight 0.3%～0.6%, and discharging obtains the long acting antibiotic polypropylene dedicated material.
2. the production method of long acting antibiotic polypropylene dedicated material according to claim 1, it is characterized in that: described catalyzer is the 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.
3. the production method of long acting antibiotic polypropylene dedicated material according to claim 1, it is characterized in that: described promotor is organo-aluminium compound, can directly add in the first reactor, or and catalyzer after pre-complexing, add in the first reactor.
4. the production method of long acting antibiotic polypropylene dedicated material according to claim 3, it is characterized in that: described promotor is triethyl aluminum, triisobutyl aluminium or three n-butylaluminum.
5. according to the described arbitrary production method of claim 3 or 4, it is characterized in that: described catalyst component be take the Ti/Al molar ratio computing as 1:25～1:100 with the ratio of organo-aluminium compound.
6. the production method of long acting antibiotic polypropylene dedicated material according to claim 1 is characterized in that: one or both compound systems that described external electron donor is silicoorganic compound, the general formula of silicoorganic compound is RnSi (OR ')
4-n, 0<n in formula≤3, in general formula, R and R ' they are identical or different alkyl, cycloalkyl, aryl, haloalkyl, R can be also halogen or hydrogen atom.
7. the production method of long acting antibiotic polypropylene dedicated material according to claim 6, it is characterized in that: described external electron donor is dimethyldimethoxysil,ne, trimethylammonium methoxy silane or tetraethoxysilane.
8. the production method of long acting antibiotic polypropylene dedicated material according to claim 1, it is characterized in that: described nano-rubber compound auxiliary system is that inorganic antiseptic or organic antibacterial agent are loaded on ultra-fine fully vulcanized powder rubber, forms nano level composite antibiosis adjuvant system.
9. the production method of long acting antibiotic polypropylene dedicated material according to claim 8, it is characterized in that: 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.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
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| CN1081683A (en) * | 1992-05-29 | 1994-02-09 | 阿莫科公司 | The polymerization of alpha-olefin |
| CN101735351A (en) * | 2008-11-07 | 2010-06-16 | 中国石油天然气股份有限公司 | Method for preparing high-fluidity wide-distribution polypropylene and product thereof |
| CN102060951A (en) * | 2009-11-12 | 2011-05-18 | 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 |
| CN103073784A (en) * | 2011-10-26 | 2013-05-01 | 中国石油化工股份有限公司 | Antibacterial polypropylene composition and preparation method thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1081683A (en) * | 1992-05-29 | 1994-02-09 | 阿莫科公司 | The polymerization of alpha-olefin |
| CN101735351A (en) * | 2008-11-07 | 2010-06-16 | 中国石油天然气股份有限公司 | Method for preparing high-fluidity wide-distribution polypropylene and product thereof |
| CN102060951A (en) * | 2009-11-12 | 2011-05-18 | 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 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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