CN104558296A - Low isotatic polypropylene catalyst and application thereof - Google Patents
Low isotatic polypropylene catalyst and application thereof Download PDFInfo
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- CN104558296A CN104558296A CN201310486025.2A CN201310486025A CN104558296A CN 104558296 A CN104558296 A CN 104558296A CN 201310486025 A CN201310486025 A CN 201310486025A CN 104558296 A CN104558296 A CN 104558296A
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Abstract
The invention discloses a low isotatic polypropylene catalyst which comprises an active component, a catalyst promoter and an external donor compound represented as the formula I, wherein R1 is selected from hydrogen or C1-C4 linear chain or branching aliphatic groups; R2-R11 are independently selected from hydrogen, linear chain aliphatic groups, and branching or annular aliphatic groups. The invention further provides a preparation method of low isotatic polypropylene and low isotatic polypropylene prepared with the method.
Description
Technical field
The present invention relates to polyalcohol catalyst field, be specifically related to a kind of LIPP catalyzer, more specifically to a kind of high polymerization activity, low vertical structure directional property external electron donor and application thereof.
Background technology
Lower than the homo-polypropylene of 90% isotactic index, body, slurry or solution polymerization time, polymer particles is easily clamminess, caking, be unfavorable for discharging.Said high isotatic polypropylene (i-PP) refers generally to the polypropylene product of isotactic index >=90%.And for LIPP (Li-PP), refer generally to polypropylene series product between Jie's Atactic Polypropelene (a-PP) and high isotatic polypropylene (i-PP), comprise the polypropylene-base product containing a small amount of comonomer, its isotactic index is for being greater than 0 and being less than 90%.Compared with high isotatic polypropylene, it is little that LIPP has density, the features such as good toughness, low temperature are soft, heat-sealing temperature is low, handling ease; Compared with traditional random polypropylene, LIPP has suitable degree of isotacticity and certain degree of crystallinity, higher relative molecular mass, lower surface viscosity, good resistance toheat.Wide market outlook are had in modifying asphalt, water-proof material, rubber and plastic processing and hotmelt field.
The conventional preparation method of LIPP mainly contains three kinds.1. the by product be separated when producing high isotatic polypropylene; 2. by metallocene catalyst synthesis preparation LIPP; 3. select low stereoregular Ziegler-Natta catalyst system to adopt suitable technique directly to synthesize LIPP product.
The method of by product LIPP when patent documentation CN1205236C reports a kind of separation of produced high isotatic polypropylene, the method LIPP is a by product, and therefore productivity ratio is lower; Patent documentation CN1137158C and US4710563 reports the treatment process of LIPP, can obtain evengranular product, but does not relate to the preparation method of LIPP; Patent CN1067693C, CN1122048C, CN1315885C, US4777216, apply for a patent CN200410017170.7 and apply for a patent the preparation method that CN02160046.5 reports LIPP Ziegler-Natta catalyst, the method mainly realizes the preparation of LIPP catalyzer by the activated form of adding the low internal electron donor of isotactic index or change carrier, it is low to there is polymerization activity in catalyzer prepared by the method, the shortcoming that the polymkeric substance ash content of synthesis is high.
Patent documentation EP1023339B1, US4754004, US5391789, US4542199, EP283739, US4931417, EP399347, US6028140, US6121377 and US6683150B1 report the method adopting different metallocene catalyst to prepare LIPP, the LIPP of preparation has the advantages such as degree of isotacticity is low, comonomer distribution is even, molecular size range is adjustable, transparency is good, but metallocene catalyst and promotor (MAO) is expensive, production cost is high.At present less about selecting low stereoregular Ziegler-Natta catalyst system to adopt suitable technique directly to synthesize the report of LIPP product.
Summary of the invention
For deficiency of the prior art, the present inventor, through further investigation, proposes a kind of catalyzer containing special external electron donor, and use in LIPP preparation and the LIPP that obtains thus.
More specifically, it is a kind of special that the present invention invents, as external donor compound, it can be used as the external electron donor component in polypropylene catalyst, achieve the preparation of LIPP, there is very high polymerization activity, and molecular chain size can be adjusted, control lower tacticity with hydrogen, also can close with ethene or other alpha-olefin copolymer the degree of crystallinity adjusting material further, and then realize obtaining desirable different isotactic index and the preparation of molecular size range LIPP.
First, the invention provides a kind of LIPP catalyzer, comprise active ingredient, promotor and structure such as formula the external donor compound shown in I;
Wherein, R
1be selected from the aliphatic group of hydrogen or C1 ~ C4 straight chain or branching; R
2-R
11be selected from the aliphatic group of hydrogen, straight chain aliphatic, branching or ring-type independently of one another.
In a preferred embodiment of the present invention, described external electron donor is selected from least one in following compound: 2, and 2,6,6-tetramethyl piperidine, 2,2,6,6-tetraethyl-piperidines, 2,2,6,6-tetra-n-propyl piperidines, 2,2,6,6-tetra isopropyl piperidines, 2,2,6,6-tetra-isobutyl-piperidines, 2,2,4,4-tetramethyl piperidine, 2,2,4,4-tetraethyl-piperidines, 2,2,5,5-tetramethyl piperidine, 2,2,5,5-tetraethyl-piperidines, 2-methyl-2-cyclohexyl-6-methyl-6-ethyl piperidine and 2,2-bicyclopentyl-6,6-lupetidine.
In a preferred implementation of catalyzer of the present invention, described active ingredient is magnesium chloride and/or silica supported titanium solid active agent and internal electron donor.Concrete, described solids containing titanium active ingredient can be selected from TiCl
4/ MgCl
2/ internal electron donor, TiCl
4/ SiO
2/ internal electron donor or TiCl
4/ MgCl
2/ SiO
2/ internal electron donor.
In a preferred implementation of catalyzer of the present invention, described promotor is organo-aluminium compound.
In further preferred implementation, described organo-aluminium compound is alkylaluminium cpd and/or methylaluminoxane, preferred described alkylaluminium cpd is trialkylaluminium, is more preferably at least one in triethyl aluminum, triisobutyl aluminium, three n-butylaluminum, three hexyl aluminium.
In a preferred implementation of catalyzer of the present invention, described internal electron donor is selected from least one in diester class, ethers, succinate compound, 1,3-alkoxide and sulfamide compound.
In a preferred implementation of catalyzer of the present invention, the active ingredient in described catalyst composition and the mol ratio of promotor count 1:10 ~ 500 with titanium and al mole ratio, preferred 1:25 ~ 100.
Present invention also offers a kind of polyacrylic preparation method, comprising:
Under the existence of described catalyzer and hydrogen, pass into propylene and carry out propylene polymerization and prepare described polypropylene.
In a preferred implementation of using method of the present invention, in described polyreaction, add alpha-olefin and propylene carries out copolymerization; The polymerization temperature of preferred described polyreaction is 40 ~ 120 DEG C, more preferably 60 ~ 85 DEG C; Hydrogen partial pressure is 0.5-3.0MPa.
Concrete, preparation method of polypropylene of the present invention carries out according to the following steps:
Add propylene, described catalyst composition to polymeric kettle and optionally add other alpha-olefins a small amount of, under 40 ~ 120 DEG C of polymerization temperatures, preferably 60 ~ 85 DEG C, carry out the polyreaction of propylene or propylene and other alpha-olefins, by the LIPP regulating the concentration of the hydrogen passed into obtain target molten index.
In another embodiment of the present invention, the organic solvents such as propylene, described catalyst composition, the alkane of 5 ~ 10 carbon atoms and/or the aromatic hydrocarbon of 5 ~ 10 carbon atoms can be added to polymeric kettle and optionally add other alpha-olefins a small amount of, under 40 ~ 120 DEG C of polymerization temperatures, preferably 60 ~ 85 DEG C, under regulating density of hydrogen, carry out the polyreaction of propylene or propylene and other alpha-olefins, obtain the LIPP of target molten index.The melting index scope of gained LIPP is 0.5 ~ 2000g/10min, is preferably 2 ~ 240g/10min, and dimethylbenzene insolubles content is more than 10 weight and lower than 90 % by weight, preferably 25 ~ 85 % by weight.
In aforesaid method, described polyreaction carries out propylene polymerization in the reactor of single or multiple serial operation, and polymerization can be the continuous prepolymerization of liquid-phase bulk, can also be batch pre-polymerization in the presence of an inert solvent.
In aforesaid method, the described catalyzer comprising external electron donor can directly join in reactor, after the pre-contact also can known altogether through industry and/or prepolymerization, then joins in reactor.Described prepolymerization refers to that catalyzer carries out the prepolymerization of certain multiplying power at a lower temperature, to obtain desirable particle shape and dynamic behavior control.Described prepolymerization can be the continuous prepolymerization of liquid-phase bulk, can also be batch pre-polymerization in the presence of an inert solvent.Prepolymerization temperature is generally-10 ~ 50 DEG C, is preferably 5 ~ 30 DEG C.Before prepolymerization technology, optionally pre-contacting steps is set.Described pre-contacting steps refers to that promotor in catalyst system, external electron donor and Primary Catalysts (solid active components) carry out the complex reaction of catalyst system, its objective is and catalyst components is mixed, to obtain the catalyst system with polymerization activity.The temperature of pre-contacting steps controls as-10 ~ 50 DEG C usually, is preferably 5 ~ 30 DEG C.
Present invention also offers a kind of above-mentioned polypropylene prepared according to method, described polyacrylic melting index scope is 0.5 ~ 2000g/10min, be preferably 2 ~ 240g/10min, dimethylbenzene insolubles content is more than 10 % by weight and lower than 90 % by weight, preferably 25 ~ 85 % by weight.Wherein dimethylbenzene insolubles content is isotactic index.That is the invention provides a kind of degree of isotacticity lower than 90% LIPP and preparation method thereof.
Beneficial effect of the present invention:
Do not need the Primary Catalysts of change polymerization system, reactor design, polymerization technique and operational condition, under high polymerization activity, can significantly reduce polyacrylic tacticity by means of only adding low stereoregular external electron donor in polymerization catalyst system, there is the advantage such as simple and effective, easy enforcement, grade transition convenience.
Catalyst activity of the present invention is high, transformation efficiency is high.And the melting index scope using catalyzer of the present invention to carry out polypropylene reaction gained LIPP is 0.5 ~ 2000g/10min, is preferably 2 ~ 240g/10min, dimethylbenzene insolubles content (isotactic index) is more than 10 % by weight and lower than 90 % by weight.
Embodiment
Below in conjunction with embodiment, the present invention is described in detail, but scope of the present invention is not limited to following examples.
Polymkeric substance relevant data obtains by following testing method in an embodiment of the present invention:
1. polymkeric substance cold xylene solubles content (isotactic index mensuration): measure according to method described in ASTM D5492;
2. melt mass flow rate (MFR): according to method described in ASTM D1238, with CEAST company 7026 type fusion index instrument, at 230 DEG C, measures under 2.16kg load;
3. co-monomer content: utilize nucleus magnetic resonance (13C-NMR) method to measure;
4. the mensuration of bulk density: measure by the method described in GB/T1636-2008.
Embodiment 1
The polyreaction of propylene is carried out in the polymeric kettle reactor of the 5L with magnetic agitation, first displacement is carried out three times to reactor nitrogen, get 1.5mmol promotor triethyl aluminum, 0.3mmol external electron donor 2,2,6,6-tetramethyl piperidine (TMPIP) and 12-14mg DQT active ingredient (MgCl
2/ TiCl
4/ phenylformic acid diisobutyl ester compounds) (China Petrochemical Industry's catalyst Co. Beijing Ao Da branch office provides), the pre-complex reaction of room temperature two minutes is carried out in catalyst addition tube, then catalyst mixed liquid is joined in reactor, add 0.05MPa hydrogen (in polymeric kettle reactor dividing potential drop), stirring is started add 2.2L propylene monomer in 5L polymeric kettle after, be heated to 70 ± 2 DEG C, after reaction 1hr, terminate reaction.Emptying for residue propylene monomer, from lower bottom valve discharging.Polymkeric substance is carried out drying treatment, weighing, analysis and characterization.The physicals of gained LIPP analytical results and described LIPP is as shown in table 1.
Embodiment 2
The catalyzer that embodiment 2 uses, polymerizing condition are identical with embodiment 1.Difference from Example 1 is: in polymerization reactor, also add 15g ethylene comonomer (mass flowmeter calculated flow rate), the physicals of gained LIPP analytical results and described LIPP is as shown in table 1.
Embodiment 3
The catalyzer that embodiment 3 uses is identical with embodiment 1 with polymerizing condition.Difference from Example 1 is: in polymerization reactor, add 50g1-butene comonomer (mass flowmeter calculated flow rate), the physicals of gained LIPP analytical results and described LIPP is as shown in table 1.
Embodiment 4
The catalyzer that embodiment 4 uses is identical with embodiment 1 with polymerizing condition.Difference from Example 1 is: in polymerization reactor, add 90g1-hexene co-monomer (mass flowmeter calculated flow rate), the physicals of gained LIPP analytical results and described LIPP is as shown in table 1.
Embodiment 5
The catalyzer that embodiment 5 uses is identical with embodiment 1 with polymerizing condition.Difference from Example 1 is: in polymerization reactor, add 250g1-hexene co-monomer (mass flowmeter calculated flow rate), the physicals of gained LIPP analytical results and described LIPP is as shown in table 1.
Embodiment 6
The catalyzer that embodiment 6 uses is identical with embodiment 1 with polymerizing condition.Difference from Example 1 is: hydrogen partial pressure changes 0.1MPa into respectively.The physicals of gained LIPP analytical results and described LIPP is as shown in table 1.
Embodiment 7
The catalyzer that embodiment 7 uses is identical with embodiment 1 with polymerizing condition.Difference from Example 1 is: hydrogen partial pressure changes 0.5MPa into respectively.The physicals of gained LIPP analytical results and described LIPP is as shown in table 1.
Embodiment 8
The catalyzer that embodiment 8 uses is identical with embodiment 1 with polymerizing condition.Difference from Example 1 is: hydrogen partial pressure changes 3MPa into respectively.The physicals of gained LIPP analytical results and described LIPP is as shown in table 1.
Comparative example 1
The polymerizing condition that comparative example 1 uses is identical with embodiment 1.Difference from Example 1 is: external electron donor use Cyclohexylmethyldimethoxysilane (DONOR-C) in described catalyzer replaces the TMPIP in embodiment 1.The physicals of gained LIPP analytical results and described LIPP is as shown in table 1.
Comparative example 2
The polymerizing condition that comparative example 2 uses is identical with embodiment 1.Difference from Example 1 is: external electron donor use dicyclopentyl dimethoxyl silane (DONOR-D) in described catalyzer replaces the TMPIP in embodiment 1.The physicals of gained LIPP analytical results and described LIPP is as shown in table 1.
Comparative example 3
The polymerizing condition that comparative example 3 uses is identical with embodiment 3.Difference from Example 3 is: external electron donor use Cyclohexyl Methyl Dimethoxysilane (DONOR-C) in described catalyzer replaces the TMPIP in embodiment 3.The physicals of gained LIPP analytical results and described LIPP is as shown in table 1.
According to the result shown in table 1, as compared to wherein using the comparative example 1 ~ 3 of conventional external electron DONOR-C with DONOR-D, TMPIP has higher polymerization activity, stronger copolymerized ability and lower isotactic index.Wherein the cold xylene insolubles content (isotactic index) of embodiment 1-8 is all lower than 90 % by weight.
Table 1 polymkeric substance test data
Embodiment 9
The polymerizing condition that embodiment 9 uses is identical with embodiment 3.Difference from Example 3 is: external electron donor use 2,2,6,6-tetraethyl-piperidines (TEPIP) in described catalyzer replaces the TMPIP in embodiment 3.The physicals of gained LIPP analytical results and described LIPP is as shown in table 2.
Embodiment 10
The polymerizing condition that embodiment 10 uses is identical with embodiment 3.Difference from Example 3 is: it is the TMPIP that 2,2,6,6-tetra-n-propyl piperidines (TNPPIP) replaces in embodiment 3 that the external electron donor in described catalyzer uses.The physicals of gained LIPP analytical results and described LIPP is as shown in table 2.
Embodiment 11
The polymerizing condition that embodiment 11 uses is identical with embodiment 3.Difference from Example 3 is: external electron donor use 2,2,6,6-tetra isopropyl piperidines (TIPPIP) in described catalyzer replaces the TMPIP in embodiment 3.The physicals of gained LIPP analytical results and described LIPP is as shown in table 2.
Embodiment 12
The polymerizing condition that embodiment 12 uses is identical with embodiment 3.Difference from Example 3 is: external electron donor use 2,2,6,6-tetra-isobutyl-piperidines (TIBPIP) in described catalyzer replaces the TMPIP in embodiment 3.The physicals of gained LIPP analytical results and described LIPP is as shown in table 2.
Embodiment 13
The polymerizing condition that embodiment 13 uses is identical with embodiment 3.Difference from Example 3 is: external electron donor use 2,2,4,4-tetramethyl piperidine (TMMPIP) in described catalyzer replaces the TMPIP in embodiment 3.The physicals of gained LIPP analytical results and described LIPP is as shown in table 2.
Embodiment 14
The polymerizing condition that embodiment 14 uses is identical with embodiment 3.Difference from Example 3 is: external electron donor use 2,2,4,4-tetraethyl-piperidines (TEMPIP) in described catalyzer replaces the TMPIP in embodiment 3.The physicals of gained LIPP analytical results and described LIPP is as shown in table 2.
Embodiment 15
The polymerizing condition that embodiment 15 uses is identical with embodiment 3.Difference from Example 3 is: external electron donor use 2,2,5,5-tetramethyl piperidine (TMPPIP) in described catalyzer replaces the TMPIP in embodiment 3.The physicals of gained LIPP analytical results and described LIPP is as shown in table 2.
Embodiment 16
The polymerizing condition that embodiment 16 uses is identical with embodiment 3.Difference from Example 3 is: external electron donor use 2,2,5,5-tetraethyl-piperidines (TEPPIP) in described catalyzer replaces the TMPIP in embodiment 3.The physicals of gained LIPP analytical results and described LIPP is as shown in table 2.
Embodiment 17
The polymerizing condition that embodiment 17 uses is identical with embodiment 3.Difference from Example 3 is: external electron donor use 2-methyl-2-cyclohexyl-6-methyl-6-ethyl piperidine (MCHMEPIP) in described catalyzer replaces the TMPIP in embodiment 3.The physicals of gained LIPP analytical results and described LIPP is as shown in table 2.
Embodiment 18
The polymerizing condition that embodiment 18 uses is identical with embodiment 3.Difference from Example 3 is: external electron donor use 2,2-bicyclopentyl-6,6-lupetidine (BCPBMPIP) in described catalyzer replaces the TMPIP in embodiment 3.The physicals of gained LIPP analytical results and described LIPP is as shown in table 2.The physicals of gained LIPP analytical results and described LIPP is as shown in table 2.
Table 2 polymkeric substance test data
Claims (10)
1. a LIPP catalyzer, comprises active ingredient, promotor and structure such as formula the external donor compound shown in I;
Wherein, R
1be selected from the aliphatic group of hydrogen or C1 ~ C4 straight chain or branching; R
2-R
11be selected from the aliphatic group of hydrogen, straight chain aliphatic, branching or ring-type independently of one another.
2. catalyzer according to claim 1, is characterized in that, described external electron donor is selected from least one in following compound: 2,2,6,6-tetramethyl piperidine, 2,2,6,6-tetraethyl-piperidines, 2,2,6,6-tetra-n-propyl piperidines, 2,2,6,6-tetra isopropyl piperidines, 2,2,6,6-tetra-isobutyl-piperidines, 2,2,4,4-tetramethyl piperidine, 2,2,4,4-tetraethyl-piperidines, 2,2,5,5-tetramethyl piperidine, 2,2,5,5-tetraethyl-piperidines, 2-methyl-2-cyclohexyl-6-methyl-6-ethyl piperidine and 2,2-bicyclopentyl-6,6-lupetidine.
3. catalyzer according to claim 1 and 2, is characterized in that, described active ingredient is magnesium chloride and/or silica supported titanium solid active agent and internal electron donor.
4. the catalyzer according to any one of claim 1-3, is characterized in that, described promotor is organo-aluminium compound.
5. catalyzer according to claim 4, it is characterized in that, described organo-aluminium compound is alkylaluminium cpd and/or methylaluminoxane, preferred described alkylaluminium cpd is trialkylaluminium, is more preferably at least one in triethyl aluminum, triisobutyl aluminium, three n-butylaluminum, three hexyl aluminium.
6. the catalyzer according to any one of claim 3-5, is characterized in that, described internal electron donor is selected from least one in diester class, ethers, succinate compound, 1,3-alkoxide and sulfamide compound.
7. the catalyzer according to any one of claim 4-6, is characterized in that, the active ingredient in described catalyzer and the mol ratio of promotor count 1:10 ~ 500 with titanium and al mole ratio, preferred 1:25 ~ 100.
8. a polyacrylic preparation method, comprising:
Under the existence of the catalyzer according to any one of claim 1-7 and hydrogen, pass into propylene and carry out propylene polymerization and prepare described LIPP.
9. method according to claim 8, is characterized in that, adds alpha-olefin and propylene carries out copolymerization in described polyreaction; The polymerization temperature of preferred described polyreaction is 40 ~ 120 DEG C, more preferably 60 ~ 85 DEG C; Hydrogen partial pressure is 0.5-3.0MPa.
10. the LIPP for preparing of the method for a kind according to Claim 8 or 9, the melting index scope of described LIPP is 0.5 ~ 2000g/10min, be preferably 2 ~ 240g/10min, dimethylbenzene insolubles content more than 10 % by weight lower than 90 % by weight, preferably 25 ~ 85 % by weight.
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Citations (3)
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|---|---|---|---|---|
| EP0156512A1 (en) * | 1984-02-28 | 1985-10-02 | Toa Nenryo Kogyo Kabushiki Kaisha | Process for preparing catalyst component for polymerization of olefins |
| WO2009029447A1 (en) * | 2007-08-24 | 2009-03-05 | Dow Global Technologies Inc. | Self-limiting catalyst composition with no silane |
| CN101747455A (en) * | 2008-12-08 | 2010-06-23 | 中国石油天然气股份有限公司 | Load type olefin polymerization main catalyst and preparation method thereof |
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2013
- 2013-10-16 CN CN201310486025.2A patent/CN104558296B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0156512A1 (en) * | 1984-02-28 | 1985-10-02 | Toa Nenryo Kogyo Kabushiki Kaisha | Process for preparing catalyst component for polymerization of olefins |
| WO2009029447A1 (en) * | 2007-08-24 | 2009-03-05 | Dow Global Technologies Inc. | Self-limiting catalyst composition with no silane |
| CN101747455A (en) * | 2008-12-08 | 2010-06-23 | 中国石油天然气股份有限公司 | Load type olefin polymerization main catalyst and preparation method thereof |
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| Title |
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| 上海市第三十一棉纺织厂: "《丙纶生产基本知识》", 31 August 1980 * |
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