CN104558334A - A preparing method of an anti-shock polypropylene special-purpose material with a high melt index - Google Patents
A preparing method of an anti-shock polypropylene special-purpose material with a high melt index Download PDFInfo
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- CN104558334A CN104558334A CN201310471494.7A CN201310471494A CN104558334A CN 104558334 A CN104558334 A CN 104558334A CN 201310471494 A CN201310471494 A CN 201310471494A CN 104558334 A CN104558334 A CN 104558334A
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Abstract
A preparing method of an anti-shock polypropylene special-purpose material with a high melt index is disclosed. A multi-section loop process is adopted. A new external electron donor is added during polymerization. The polymerization molecular weight is controlled by adjusting the ethylene adding amount. The mass ratio of a catalyst to propylene is 1:170000-190000. The mass ratio of a cocatalyst to the propylene is 1:5700-6700. The mass ratio of the cocatalyst to the external electron donor is 1.5-3:1. Compared with present products, a product of the polypropylene special-purpose material is long in stabilization period, almost free of odor, more in high molecular weight part, wide in molecular weight distribution, long in oxidation induction time and good in antishock performance.
Description
Technical field
The present invention relates to a kind of method preparing high melting means impact polypropylene PP Pipe Compound, particularly adopt novel external electron donor technology, directly obtain high melting means impact polypropylene resin in the course of the polymerization process.
Background technology
High flowing impact polypropylene has high flow rate and good physicals, and the production of the large thin-wall injected articles of complex structural designs can be made to become feasible.Can shorten the process-cycle in process of production, reduce processing temperature, injection pressure and energy consumption, have processibility good, mold filling character is excellent and can reduce the advantages such as product buckling deformation.Its goods are mainly used in packaging, transport, household electrical appliances, automobile, office, current consumption articles for use, medical article etc.
In prior art, in order to obtain the good high flow polypropylene of over-all properties, generally take following two kinds of methods: one is adopt suitable controllable rheology technology, in extruding pelletization process, in acrylic resin, namely adds organo-peroxide make melt mass flow rate (MFR) corresponding raising; Two is the polymerization techniques adopting new catalyzer and improvement, the impact polypropylene rosin products of the directly high flowing of synthesis in the reactor.The product stability obtained by peroxide degradation method is poor, the polypropylene of preparation easily turns to be yellow, yellowness index is higher in other words, and volatile organic compounds (VOC) content is high, smell is larger, limits its application in household supplies, automotive upholstery, food product pack etc.And by the height flowing impact polypropylene that hydrogen adjusts method to produce, its yellowness index is low, low, the basic odorlessness of volatile organic compounds (VOC) content, has become a kind of trend of development.
Summary of the invention
The invention provides a kind of preparation method of high melting means impact polypropylene PP Pipe Compound, by loop po lymerisation technique, propylene, under the acting in conjunction of Primary Catalysts, promotor and external electron donor, generates polyacrylic method through loop po lymerisation.The polypropylene dedicated material of the present invention's synthesis has the characteristic of high melting means anti-impact, and yellowness index is low, pollutes the features such as little.
Below technical scheme of the present invention:
Prepare a method for high melting means impact polypropylene PP Pipe Compound, mainly comprise the following steps:
1) propylene is under the acting in conjunction of Primary Catalysts, promotor and external electron donor, through pre-polymerization reactor, propylene polymerization is generated polypropylene, the mass ratio of catalyzer and all charging propylene is 1:170000 ~ 190000, the mass ratio of promotor and all charging propylene is 1:5700 ~ 6700, promotor and external electron donor mass ratio are 1.5 ~ 3:1, hydrogen is 1:4500 ~ 5500 with entering pre-polymerization reactor fresh propylene mass ratio, temperature of reaction is 14 ~ 20 DEG C, reaction pressure is 3.4 ~ 3.8MPa, and the reaction times is 8 ~ 12 minutes;
2) the prepolymerization product obtained by step 1) and fresh propylene and hydrogen enter first ring pipe reactor and proceed polyreaction, hydrogen is 1:4500 ~ 5500 with entering first ring pipe reactor fresh propylene mass ratio, temperature of reaction is 68 ~ 72 DEG C, reaction pressure is 3.4 ~ 3.8MPa, and the reaction times is 50 ~ 65 minutes;
3) by step 2) polymeric reaction product and fresh propylene and the hydrogen that obtain enters the second annular-pipe reactor and proceeds to be polymerized, hydrogen is 1:4500 ~ 5500 with entering the second annular-pipe reactor fresh propylene mass ratio, temperature of reaction is 68 ~ 72 DEG C, reaction pressure is 3.4 ~ 3.8MPa, and the reaction times is 25 ~ 40 minutes;
4) polymeric reaction product obtained by step 3) and fresh propylene, ethene, hydrogen and anti-scaling enter Gas-phase reactor and proceed polyreaction, the mass ratio of hydrogen, ethene and fresh propylene is 1:350 ~ 450:1050 ~ 1350, the mass ratio of anti-scaling and promotor is 1:2.5 ~ 3.5, temperature of reaction is 72 ~ 78 DEG C, reaction pressure is 1.2 ~ 1.4MPa, and the reaction times is 30 ~ 45 minutes;
Above-mentioned steps 1) described external electron donor is the mixture of Bicvclopentyl methyl dimethoxysilane and second, isobutyl dimethoxy silane;
Above-mentioned steps 1) described Primary Catalysts is six type spherical catalysts (Ao Da), promotor is triethyl aluminum;
Above-mentioned steps 1) mass ratio of described catalyzer and all charging propylene is preferably 1:175000 ~ 185000, the mass ratio of promotor and propylene is preferably 1:6000 ~ 6300, promotor and external electron donor mass ratio are preferably 1.8 ~ 2.2:1, hydrogen and fresh propylene mass ratio are preferably 1:4800 ~ 5200 temperature of reaction and are preferably 16 ~ 18 DEG C, reaction pressure is preferably 3.5 ~ 3.6MPa, and the reaction times is preferably 10 ~ 11 minutes;
Above-mentioned steps 2) described hydrogen with enter first ring pipe reactor fresh propylene mass ratio and be preferably 1:4800 ~ 5200, temperature of reaction is preferably 69 ~ 71 DEG C, and reaction pressure is preferably 3.5 ~ 3.6MPa, and the reaction times is preferably 55 ~ 58 minutes;
Above-mentioned steps 3) described hydrogen with enter the second annular-pipe reactor fresh propylene mass ratio and be preferably 1:4800 ~ 5200, temperature of reaction is preferably 69 ~ 71 DEG C, and reaction pressure is preferably 3.5 ~ 3.6MPa, and the reaction times is preferably 30 ~ 35 minutes;
Above-mentioned steps 4) mass ratio of described hydrogen, ethene and fresh propylene is preferably 1:380 ~ 420:1140 ~ 1260, the mass ratio of anti-scaling and promotor is preferably 1:2.8 ~ 3.2, temperature of reaction is preferably 74 ~ 76 DEG C, reaction pressure is preferably 1.25 ~ 1.35MPa, and the reaction times is preferably 35 ~ 40 minutes;
The defect that the present invention be directed to the existence of existing technique synthesis impact polypropylene product is improved, contriver finds by adding new external electron donor in propylene polymerization processes after deliberation, obtained product high melting means impact polypropylene compared with currently available products is long for stationary phase, basic odorlessness, high molecular weight moieties is more, molecular weight distribution is wider, and oxidation induction time is longer, and shock resistance is better; And in prior art, the poor stability of the product adopting controllable rheology technology to obtain, the polypropylene of preparation easily turns to be yellow, and smell is larger, and its oxidation inhibitor used is also many than the high melting means impact polypropylene adjusting method to prepare with hydrogen.
Below by concrete embodiment, the invention will be further described, and in an embodiment, the testing standard of each physical index is respectively:
Melt index determination: GB/T3682-2000
Ethylene content measures: Q/SPC1032
Degree of isotacticity measures: Q/SPC4045
Simple beam impact strength measures: GB/T1043.1-2008
Accompanying drawing explanation
Fig. 1 is process flow diagram of the present invention
Embodiment
[embodiment 1 ~ 8]
Propylene 2 is under the acting in conjunction of Primary Catalysts, promotor and external electron donor 1, through prepolymerization R1(4L), first ring pipe reactor R2(235L), the second annular-pipe reactor R3(235L) and Gas-phase reactor R4(950L) synthesize polypropylene, in synthesis process, reaction raw materials proportioning, catalyst levels are with each reactor process operational condition in table 1, table 2 and table 3, and acrylic resin product indices is in table 4
Table 1
| Promotor: propylene | Promotor: external electron donor | Catalyzer: propylene | |
| Embodiment 1 | 1：6250 | 3 | 1:190000 |
| Embodiment 2 | 1：6250 | 1.5 | 1:170000 |
| Embodiment 3 | 1：6250 | 2.2 | 1:180000 |
| Embodiment 4 | 1：6250 | 1.8 | 1:180000 |
| Embodiment 5 | 1：5700 | 2 | 1:180000 |
| Embodiment 6 | 1：5700 | 2 | 1:190000 |
| Embodiment 7 | 1：6700 | 2 | 1:170000 |
| Embodiment 8 | 1：6000 | 2 | 1:185000 |
| Embodiment 9 | 1：6300 | 2 | 1:175000 |
| Embodiment 10 | 1：6250 | 2 | 1:180000 |
Table 2
Table 3
Table 4
Claims (7)
1. prepare a method for high melting means impact polypropylene PP Pipe Compound, it is characterized in that mainly comprising following steps:
1) propylene is under the acting in conjunction of Primary Catalysts, promotor and external electron donor, through pre-polymerization reactor, propylene polymerization is generated polypropylene, the mass ratio of catalyzer and all charging propylene is 1:170000 ~ 190000, the mass ratio of promotor and all charging propylene is 1:5700 ~ 6700, promotor and external electron donor mass ratio are 1.5 ~ 3:1, hydrogen is 1:4500 ~ 5500 with entering pre-polymerization reactor fresh propylene mass ratio, temperature of reaction is 14 ~ 20 DEG C, reaction pressure is 3.4 ~ 3.8MPa, and the reaction times is 8 ~ 12 minutes;
2) the prepolymerization product obtained by step 1) and fresh propylene and hydrogen enter first ring pipe reactor and proceed polyreaction, hydrogen is 1:4500 ~ 5500 with entering first ring pipe reactor fresh propylene mass ratio, temperature of reaction is 68 ~ 72 DEG C, reaction pressure is 3.4 ~ 3.8MPa, and the reaction times is 50 ~ 65 minutes;
3) by step 2) polymeric reaction product and fresh propylene and the hydrogen that obtain enters the second annular-pipe reactor and proceeds to be polymerized, hydrogen is 1:4500 ~ 5500 with entering the second annular-pipe reactor fresh propylene mass ratio, temperature of reaction is 68 ~ 72 DEG C, reaction pressure is 3.4 ~ 3.8MPa, and the reaction times is 25 ~ 40 minutes;
4) polymeric reaction product obtained by step 3) and fresh propylene, ethene, hydrogen and anti-scaling enter Gas-phase reactor and proceed polyreaction, the mass ratio of hydrogen, ethene and fresh propylene is 1:350 ~ 450:1050 ~ 1350, the mass ratio of anti-scaling and promotor is 1:2.5 ~ 3.5, temperature of reaction is 72 ~ 78 DEG C, reaction pressure is 1.2 ~ 1.4MPa, and the reaction times is 30 ~ 45 minutes.
2. a kind of method preparing high melting means impact polypropylene according to claim 1, is characterized in that external electron donor described in step 1) is the mixture of Bicvclopentyl methyl dimethoxysilane and second, isobutyl dimethoxy silane.
3. a kind of method preparing high melting means impact polypropylene according to claim 1, it is characterized in that Primary Catalysts described in step 1) is six type spherical catalysts (Ao Da), promotor is triethyl aluminum.
4. a kind of method preparing high melting means impact polypropylene according to claim 1, it is characterized in that the mass ratio of catalyzer described in step 1) and all charging propylene is preferably 1:175000 ~ 185000, the mass ratio of promotor and propylene is preferably 1:6000 ~ 6300, promotor and external electron donor mass ratio are preferably 1.8 ~ 2.2:1, hydrogen and fresh propylene mass ratio are preferably 1:4800 ~ 5200 temperature of reaction and are preferably 16 ~ 18 DEG C, reaction pressure is preferably 3.5 ~ 3.6MPa, and the reaction times is preferably 10 ~ 11 minutes.
5. a kind of method preparing high melting means impact polypropylene according to claim 1, it is characterized in that step 2) described hydrogen with enter first ring pipe reactor fresh propylene mass ratio and be preferably 1:4800 ~ 5200, temperature of reaction is preferably 69 ~ 71 DEG C, reaction pressure is preferably 3.5 ~ 3.6MPa, and the reaction times is preferably 55 ~ 58 minutes.
6. a kind of method preparing high melting means impact polypropylene according to claim 1, it is characterized in that hydrogen described in step 3) and enter the second annular-pipe reactor fresh propylene mass ratio being preferably 1:4800 ~ 5200, temperature of reaction is preferably 69 ~ 71 DEG C, reaction pressure is preferably 3.5 ~ 3.6MPa, and the reaction times is preferably 30 ~ 35 minutes.
7. a kind of method preparing high melting means impact polypropylene according to claim 1, it is characterized in that the mass ratio of hydrogen described in step 4), ethene and fresh propylene is preferably 1:380 ~ 420:1140 ~ 1260, the mass ratio of anti-scaling and promotor is preferably 1:2.8 ~ 3.2, temperature of reaction is preferably 74 ~ 76 DEG C, reaction pressure is preferably 1.25 ~ 1.35MPa, and the reaction times is preferably 35 ~ 40 minutes.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109111643A (en) * | 2018-06-15 | 2019-01-01 | 中国石油化工股份有限公司 | A kind of high flowing High-impact Polypropylene and preparation method thereof |
| CN109776955A (en) * | 2018-12-18 | 2019-05-21 | 东华能源(宁波)新材料有限公司 | A method of polypropylene material is prepared using hydrogen-regulating method |
| CN110577612A (en) * | 2019-09-05 | 2019-12-17 | 北方华锦化学工业股份有限公司 | production method of high-melt-index, high-impact-resistance and high-rigidity polypropylene resin |
| CN111100226A (en) * | 2018-10-25 | 2020-05-05 | 中国石油化工股份有限公司 | Production method capable of adjusting rigidity-toughness balance of impact-resistant polypropylene |
| CN111499978A (en) * | 2020-05-28 | 2020-08-07 | 徐州海天石化有限公司 | High-melt-index PP powder material capable of being used for producing melt-blown material and preparation method of polypropylene melt-blown material |
| CN112759692A (en) * | 2019-10-21 | 2021-05-07 | 中国石油化工股份有限公司 | Production method of haze-adjustable impact-resistant polypropylene cast film |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109111643A (en) * | 2018-06-15 | 2019-01-01 | 中国石油化工股份有限公司 | A kind of high flowing High-impact Polypropylene and preparation method thereof |
| CN111100226A (en) * | 2018-10-25 | 2020-05-05 | 中国石油化工股份有限公司 | Production method capable of adjusting rigidity-toughness balance of impact-resistant polypropylene |
| CN111100226B (en) * | 2018-10-25 | 2023-03-28 | 中国石油化工股份有限公司 | Production method capable of adjusting rigidity-toughness balance of impact-resistant polypropylene |
| CN109776955A (en) * | 2018-12-18 | 2019-05-21 | 东华能源(宁波)新材料有限公司 | A method of polypropylene material is prepared using hydrogen-regulating method |
| CN110577612A (en) * | 2019-09-05 | 2019-12-17 | 北方华锦化学工业股份有限公司 | production method of high-melt-index, high-impact-resistance and high-rigidity polypropylene resin |
| CN112759692A (en) * | 2019-10-21 | 2021-05-07 | 中国石油化工股份有限公司 | Production method of haze-adjustable impact-resistant polypropylene cast film |
| CN111499978A (en) * | 2020-05-28 | 2020-08-07 | 徐州海天石化有限公司 | High-melt-index PP powder material capable of being used for producing melt-blown material and preparation method of polypropylene melt-blown material |
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Application publication date: 20150429 |