CN108409896A - Ziegler-Natta catalyst composition and its application - Google Patents
Ziegler-Natta catalyst composition and its application Download PDFInfo
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- CN108409896A CN108409896A CN201810296059.8A CN201810296059A CN108409896A CN 108409896 A CN108409896 A CN 108409896A CN 201810296059 A CN201810296059 A CN 201810296059A CN 108409896 A CN108409896 A CN 108409896A
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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
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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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
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/04—Monomers containing three or four carbon atoms
- C08F110/06—Propene
Abstract
A kind of ziegler natta catalyst composition of present invention offer and its application.Ziegler natta catalyst composition provided by the invention includes main catalyst component, cocatalyst component and external electron donor component, the major catalyst includes titanium-containing compound, esters or ethers internal electron donor compound and magnesium chloride support, the cocatalyst component includes alkyl aluminum, the external electron donor component is made of first kind external electron donor and the second class external electron donor, the first kind external electron donor is that alkoxyl silicone alkanes founds structure selection control agent, and the second class external electron donor is undersaturated aliphatic ester high temperature active inhibitor.The application in the homopolymerization polymerisation of propylene that the present invention also provides the ziegler natta catalyst compositions and the application in propylene is reacted at least one copolymerisable monomer co-polymeric.The carbon monoxide-olefin polymeric of the present invention can effectively reduce the activity of high temperature polymerization process, it is ensured that reacting balance carries out.
Description
Technical field
The present invention relates to field of olefin polymerisation, more particularly to one kind, and there is high temperature active to inhibit to make in olefin polymerization process
Polyolefin catalyst composition and the olefin Polymerization catalyst compositions.
Background technology
Polyolefin industry used catalyst is mainly the MgCl2 containing two esters or two ethers internal electron donors negative at present
Load type ziegler-nata (Ziegler-Natta) catalyst (abbreviation Z-N catalyst), the use of such catalyst will coordinate alkane
Base aluminum cocatalyst and vertical structure selection control agent external electron donor component.Especially in the α-with 3 carbon or more carbon atom
Higher yields and the polymer compared with high isotactic can be obtained in olefinic polymerization, wherein interior external donor compound is catalyst
One of essential ingredient in component, and as polyolefin catalyst is continuously updated the replacement, the group of interior external electron donor
Close is also to have developed different balanced constants.Currently, a variety of electron donor compounds have largely been disclosed, such as interior electron
Body often uses monocarboxylic esters or multi-carboxylate, ketone, monoether or polyether, amine etc. and its derivative, external electron donor often to use alcoxyl
Radical siloxane compound.Individual alkoxy silane external electron donor coordinates with existing solid catalyst, is applied to catalysis propylene
Polymerization can have higher activity and capacity of orientation, and in gas phase reaction process, the stationarity of polymerisation is mainly by poly-
Highly exothermic influence during conjunction, removing reaction thermal energy in time or reducing pyroreaction exothermic process effectively to reduce
The risk of reaction kettle caking.The patent CN1856514B of Dow Global Technologies Inc. discloses a kind of comprising as work
Property limitation agent myristic acid esters compound Z-N catalyst systems, have control polymeric kettle in pyroreaction exothermic process,
But its dosage is larger and to the low temperature of polymerization (typical polymerization temperature：67-70 DEG C) activity influence is larger.The present invention develops one kind
The Z-N carbon monoxide-olefin polymerics that pyroreaction activity suppression efficiency is stronger and low temperature active is better.
Invention content
It is an object of the present invention to provide a kind of Z-N carbon monoxide-olefin polymerics with stronger high temperature active inhibiting effect
And its application in propylene polymerization.
In order to achieve the above object, on the one hand the following technical solutions are proposed by the present invention：
A kind of Ziegler-Natta catalyst composition, it includes main catalyst component, cocatalyst component and outer electrons
Body component, the major catalyst includes titanium-containing compound, esters or ethers internal electron donor compound and magnesium chloride support, described
Cocatalyst component includes alkyl aluminum, and the external electron donor component is by first kind external electron donor and the second class external electron donor
Composition, the first kind external electron donor are that alkoxyl silicone alkanes founds structure selection control agent, and the second class external electron donor is
Undersaturated aliphatic ester high temperature active inhibitor.
Preferably, wherein the first kind external electron donor includes selected from Cyclohexylmethyldimethoxysilane, two isobutyls
Base dimethoxysilane, dicyclopentyl dimethoxyl silane, n-propyl trimethoxy silane, diisopropyl dimethoxy silane and
It is one or more in tetraethoxysilane；Molar content of the first kind in the external electron donor component be
1%~99%.
Including being selected from structureUnsaturated ester compound, R1, R2, R3, R4
It is respectively selected from the alkyl of C1-C16 or the aryl of C6-C12；
Optionally, wherein the second class external electron donor component include acrylic acid acrylic ester, 3-butenoic acid acrylic ester,
3- penetenoic acids acrylic ester, 5- hexenoic acid -3- butene esters, 6- heptenoic acid -3- butene esters, -4 amylene ester of 7- octenoic acids, 8- nonenoic acids -
5- hexene esters, 9- decylenic acid -9- ubidecarenones, 10 hendecenoic acid-acrylic ester, 11- lauroleic acid -2- butene esters, 11- laurylenes
Acid -3- butene esters, -4 octene ester of 5- tridecylenic acids, -4 hexene ester of 13- tetradecenoic acids, 15 enesters of 14- pentadecylenic acids -14-,
15- gaidic acid -15- hexadecylenes ester, 17 enesters of 16- heptadecenoic acids -16-, benzoic acid-acrylic ester, 6- phenyl hexenoic acid -
Acrylic ester, -6 phenyl hexene ester of 12- phenyl lauroleic acid, 6- naphthalenes hexenoic acid-acrylic ester, the own ester of acrylic acid benzene and 5- heptenoic acids
It is one or more in phenethyl ester
Preferably, wherein the titanium-containing compound is TiCl4.
Preferably, wherein the co-catalyst co-catalyst is triethyl aluminum.
Optionally, wherein the carbon monoxide-olefin polymeric, the titanium elements in aluminium element and major catalyst in co-catalyst
Molar ratio be 10:1~500:1, it preferably is selected from 10:1~200:1.
Preferably, wherein in the internal electron donor compound, ester type compound is selected from ethyl benzoate, O-phthalic
In sour diisobutyl ester, n-butyl phthalate, 2,3- diisopropyls succinic acid diisobutyl ester and 2,4-PD ester
It is one or more；Ethers internal electron donor compound is bis- (hydroxymethyl, methyl) fluorenes of 9,9-.
Preferably, wherein the carbon monoxide-olefin polymeric, internal electron donor compound account for the weight hundred of the major catalyst
Divide than being 6wt%~15wt%.
Optionally, wherein the carbon monoxide-olefin polymeric, wherein the first kind external electron donor in major catalyst
The molar ratio of titanium elements is 1:1~1000:1.
Preferably, wherein the carbon monoxide-olefin polymeric, wherein the first kind external electron donor in major catalyst
The molar ratio of titanium elements is 10:1-100:1.
In the external electron donor component of the carbon monoxide-olefin polymeric of the present invention, first kind external electron donor is mainly and main catalytic
The cooperation of agent component has the function of adjusting control polypropylene isotacticity and hydrogen response, and the second class external electron donor is in propylene
Pyroreaction can be inhibited in gas-phase polymerization processes, to reduce the generation that high temperature is cruelly poly- in polymeric kettle.
On the other hand, the present invention provides a kind of olefine polymerizing process comprising：In polymer reactor, in polymerizing condition
Under, so that alkene is contacted with the Z-N carbon monoxide-olefin polymerics of the present invention with high temperature active inhibiting effect.
In another aspect, the following technical solutions are proposed by the present invention：
Preferably, the homopolymerization of the alkene or copolymerization are the homopolymerization reaction of propylene or propylene and other alkene
The copolymerization of monomer.
It is highly preferred that the homopolymerization or copolymerization are gas phase, ontology or slurry polymerization.
In order to better illustrate the present invention the effect of, calculates " normalization activity ", at temperature T using concentration changed factor
Normalization activity definition be that activity under temperature T is multiplied by concentration correction factor, wherein P (67) is the density of propylene at 67 DEG C,
The concentration of propylene when P (T) is temperature T.Normalizing active equation is：
The concentration correction factor of propylene is：67 DEG C (correction factor=1), 90 DEG C (correction factor=1.67), 100 DEG C of (schools
Positive divisor=1.93), 110 DEG C (correction factor=2.16), 120 DEG C (correction factor=2.57).
Normalization activity is calculated than AT/A67 by calculating the normalization activity AT under temperature T, which can conduct
Activity with temperature change instruction, it has been found that, in liquid phase propylene polymerization, when temperature reaches 100 DEG C, normalization activity
When ratio A100/A67 is less than or equal to 0.35, illustrate that the catalyst system and catalyzing has self-extinguishment, also means that the external electron donor has
There is high temperature active inhibiting effect.
The present inventor is during the experiment it was unexpectedly observed that contain undersaturated aliphatic ester compounds as outside to electricity
The normalization activity ratio A100/A67 of the carbon monoxide-olefin polymeric of daughter is in the range of 0.15~0.26, hence it is evident that is less than using other
Normalization activity ratio A100/A67 of the monoesters as the carbon monoxide-olefin polymeric of external electron donor, and use undersaturated aliphatic
It can ensure that polymerisation low temperature active is higher when ester.This shows that the carbon monoxide-olefin polymeric of the present invention has stronger high temperature active
Inhibiting effect and do not influence low-temperature reactivity.It is further demonstrated in experimentation and using other monoesters as outer electron
The carbon monoxide-olefin polymeric of body is compared, and of the invention contains carbon monoxide-olefin polymeric of the undersaturated aliphatic ester as external electron donor
Pyroreaction exothermic process in polymeric kettle can be effectively controlled, it is ensured that reacting balance carries out.
Conventional method known in the art may be used to prepare in the major catalyst of the present invention.Preferably, the main catalytic
The carrier of agent is porous magnesium chloride support, and major catalyst can pass through magnesium ethylate carrier or ethyl alcohol-magnesium chloride support and tetrachloro
Change titanium reaction to prepare, it is possible to use the alcohol adduct of magnesium dichloride-alcohol is prepared in titanium tetrachloride by recrystallization method.Main catalytic
The preparation method of agent is not limited to both the above method.For example, application for a patent for invention can be used in the major catalyst of the present invention
The method for preparing catalyst that CN1320644A or application for a patent for invention CN1453298A are provided obtains.
Specific implementation mode
The technical solution further illustrated the present invention below by specific implementation mode.
Examples set forth below is in order to better illustrate the present invention, to be not intended to be limiting of the invention.
Test method：
1, polyacrylic isotacticity is measured using heptane extraction process, and 3-5g polypropylene is placed in Soxhlet extractor, with boiling
It rises heptane to extract 6 hours, residual polymer is dried to constant weight, weigh and calculate polyacrylic weight and extracting after extracting
Preceding polyacrylic weight ratio is the isotacticity of acrylic resin.
2, the melt flow index (MFR) of product is measured according to testing standard ASTM D1238, and experiment condition is
2.16Kg, 230 DEG C.
Embodiment 1-16
The heating of 5L autoclaves is vacuumized, is replaced 3 times with nitrogen, it is phthalic acid that internal electron donor, which is then added,
The TiCl4 main catalyst components of the MgCl2 loads of diisobutyl ester, the content of Ti elements is with the weight of major catalyst in major catalyst
It is calculated as 2.5wt%, the content of internal electron donor diisobutyl phthalate is calculated as 8.6wt% with the weight of major catalyst.It helps
Catalyst and external electron donor component sequentially add, and are added a small amount of hydrogen and 1200g propylene, and the molar ratio of hydrogen and propylene is
0.004/1.Kettle temperature is rapidly heated to 67 DEG C, starts to polymerize, after reacting 1h, unreacted propylene is discharged, product is taken out and carries out
Test is weighed, specific experiment condition is shown in Table 1, and polymerization result is shown in Table 2.
Comparative example 1-10
Polymerization process is same as Example 1, only changes the external electron donor of addition and the type of interior electron, first
Molar ratio, internal electron donor between class external electron donor and the second class external electron donor account for major catalyst weight percent,
In the molar ratio of the titanium elements in aluminium element and major catalyst in co-catalyst, the second class external electron donor and major catalyst
The molar ratio and polymerization temperature of titanium elements, specific experiment condition are shown in Table 1, and polymerization result is shown in Table 2.
The type of external electron donor, internal electron donor used by table 1 embodiment 1-16 and comparative example 1-10 and polymerization temperature
Degree
The polymerization result of table 2 embodiment 1-16 and comparative example 1-10
In actual production, when low temperature (67 DEG C) activity value is less than 30KgPP/g, polymerization activity is relatively low, and reaction is slow, meeting
Production yield is influenced, while when normalization activity is less than 0.35 than A100/A67, the reaction of polymerization process high temperature will be by
Inhibit, and normalize activity it is lower than A100/A67 illustrate that the activity suppression of first kind external electron donor is better, to avoid
The fluctuation of reaction ensure that the stability of production.
The type and addition of the second class external electron donor are to polymerisation it can be seen from the experimental result in table 1-2
Activity has larger impact,
By embodiment 1-16 (contain the second class external electron donor) and comparative example 9-10 (being free of the second class external electron donor),
It can be found that the addition of the second class external electron donor component slightly influences the low temperature polymerization activity of catalyst, but it is to height
Warm polymerization activity has apparent inhibiting effect.
By embodiment 1-2 and comparative example 1-2, embodiment 3-4 with comparative example 3-4, embodiment 5-16 with comparative example 7-8's
From the point of view of polymerization experiment result, the addition of olefin(e) acid enester class external electron donor both can guarantee that (67 DEG C) polymerizations of low temperature of catalyst were lived
Property, and better high temperature active can be obtained, function, the ratio of A100/A67 is inhibited to be significantly lower than isopropyl myristate, explanation
The activity suppression function of olefin(e) acid enol ester compounds.
The technical principle of the present invention is described above in association with specific embodiment.These descriptions are intended merely to explain the present invention's
Principle, and it cannot be construed to limiting the scope of the invention in any way.Based on the explanation herein, the technology of this field
Personnel would not require any inventive effort the other specific implementation modes that can associate the present invention, these modes are fallen within
Within protection scope of the present invention.
Claims (10)
1. a kind of Ziegler-Natta catalyst composition, it includes main catalyst component, cocatalyst component and external electron donors
Component, the major catalyst includes titanium-containing compound, esters or ethers internal electron donor compound and magnesium chloride support, described to help
Catalytic component includes alkyl aluminum, and the external electron donor component is by first kind external electron donor and the second class external electron donor group
At the first kind external electron donor is that alkoxyl silicone alkanes founds structure selection control agent, and the second class external electron donor is not
The aliphatic ester high temperature active inhibitor of saturation.
2. Ziegler-Natta catalyst composition according to claim 1, wherein the first kind external electron donor includes
Selected from Cyclohexylmethyldimethoxysilane, second, isobutyl dimethoxy silane, dicyclopentyl dimethoxyl silane, n-propyl three
It is one or more in methoxy silane, diisopropyl dimethoxy silane and tetraethoxysilane；The first kind is described
Molar content in external electron donor component is 1%~99%.
3. Ziegler-Natta catalyst composition according to claim 1, wherein the second class external electron donor includes
It is selected from structureUnsaturated ester compound, R1, R2, R3, R4 are respectively selected from C1-C16
Alkyl or C6-C12 aryl；It is further preferred that being respectively selected from acrylic acid acrylic ester, 3-butenoic acid acrylic ester, 3- amylenes
Acid propylene ester, 5- hexenoic acid -3- butene esters, 6- heptenoic acid -3- butene esters, -4 amylene ester of 7- octenoic acids, 8- nonenoic acid -5- hexenes
Ester, 9- decylenic acid -9- ubidecarenones, 10 hendecenoic acid-acrylic ester, 11- lauroleic acid -2- butene esters, 11- lauroleic acid -3- fourths
Enester, -4 octene ester of 5- tridecylenic acids, -4 hexene ester of 13- tetradecenoic acids, 15 enesters of 14- pentadecylenic acids -14-, 15- hexadecylenes
Acid -15- hexadecylenes ester, 17 enesters of 16- heptadecenoic acids -16-, benzoic acid-acrylic ester, 6- phenyl hexenoic acid-acrylic ester, 12-
In -6 phenyl hexene ester of phenyl lauroleic acid, 6- naphthalenes hexenoic acid-acrylic ester, the own ester of acrylic acid benzene and 5- heptenoic acid phenethyl esters
It is one or more.
4. Ziegler-Natta catalyst composition according to claim 1, wherein the titanium-containing compound is TiCl4.
5. Ziegler-Natta catalyst composition according to any one of claim 1 to 4, the co-catalyst is three
The molar ratio of aluminium ethide, the titanium elements in aluminium element and major catalyst in the co-catalyst is 10:1~500:1, it preferably is selected from
10:1~200:1.
6. Ziegler-Natta catalyst composition according to any one of claim 1 to 4, wherein being given in the esters
Electron compound is selected from ethyl benzoate, diisobutyl phthalate, n-butyl phthalate, 2,3- diisopropyls
It is one or more in succinic acid diisobutyl ester and 2,4-PD ester；Ethers internal electron donor compound is the bis- (hydroxyls of 9,9-
Methyl) fluorenes.
7. Ziegler-Natta catalyst composition according to any one of claim 1 to 4, wherein the interior electron
The weight percent that body compound accounts for the major catalyst is 6wt%~15wt%.
8. Ziegler-Natta catalyst composition according to any one of claim 1 to 4, wherein outside the first kind
The molar ratio of electron donor and the titanium elements in the major catalyst is 1:1~1000:1.
9. Ziegler-Natta catalyst composition the answering in the homopolymerization polymerisation of propylene according to claim 1-8
Application in being reacted at least one copolymerisable monomer co-polymeric with or propylene.
10. purposes according to claim 9, wherein the homopolymerization polymerization or co-polymeric reaction be gas phase, ontology or
Slurry polymerization.
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| CN100339399C (en) * | 2003-01-23 | 2007-09-26 | 三星阿托菲纳株式会社 | Method of polymerization and copolymerization of ethylene |
| CN101848946A (en) * | 2007-08-24 | 2010-09-29 | 陶氏环球技术公司 | Gas phase polymerization process |
| CN104371046A (en) * | 2013-08-16 | 2015-02-25 | 中国石油化工股份有限公司 | Catalyst system used for olefin polymerization and propylene copolymer |
| CN105524192A (en) * | 2015-12-09 | 2016-04-27 | 大唐国际化工技术研究院有限公司 | Polypropylene catalyst composition with high-temperature activity inhibitory effect and application thereof |
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2018
- 2018-04-04 CN CN201810296059.8A patent/CN108409896B/en active Active
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3429901B2 (en) * | 1995-05-12 | 2003-07-28 | 昭和電工株式会社 | Modified polypropylene |
| CN1180712A (en) * | 1997-11-18 | 1998-05-06 | 化学工业部北京化工研究院 | Catalyzer for ethylene polymerization and copolymerization and preparaing method thereof |
| CN100339399C (en) * | 2003-01-23 | 2007-09-26 | 三星阿托菲纳株式会社 | Method of polymerization and copolymerization of ethylene |
| CN101848946A (en) * | 2007-08-24 | 2010-09-29 | 陶氏环球技术公司 | Gas phase polymerization process |
| CN104371046A (en) * | 2013-08-16 | 2015-02-25 | 中国石油化工股份有限公司 | Catalyst system used for olefin polymerization and propylene copolymer |
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Effective date of registration: 20230118 Address after: 200233 room 405G, floor 4, building 33, No. 680, Guiping Road, Xuhui District, Shanghai Patentee after: PULAN POLYOLEFIN TECHNOLOGY DEVELOPMENT (SHANGHAI) Co.,Ltd. Patentee after: Puenejing New Energy Materials (Shanghai) Co.,Ltd. Address before: 200233 Room 401, block B, 410 Guiping Road, Xuhui District, Shanghai Patentee before: PULAN POLYOLEFIN TECHNOLOGY DEVELOPMENT (SHANGHAI) Co.,Ltd. |
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Effective date of registration: 20230608 Address after: Room 702, Building 56, No. 248, Guanghua Road, Minhang District, Shanghai, 201108 Patentee after: Puenejing New Energy Materials (Shanghai) Co.,Ltd. Address before: 200233 room 405G, floor 4, building 33, No. 680, Guiping Road, Xuhui District, Shanghai Patentee before: PULAN POLYOLEFIN TECHNOLOGY DEVELOPMENT (SHANGHAI) Co.,Ltd. Patentee before: Puenejing New Energy Materials (Shanghai) Co.,Ltd. |