CN106317264B - A kind of support type MgCl2/TiCl4 catalyst and its preparation method and application with salicylic alidehyde imine type modifier modification - Google Patents
A kind of support type MgCl2/TiCl4 catalyst and its preparation method and application with salicylic alidehyde imine type modifier modification Download PDFInfo
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Abstract
The present invention provides a kind of support type MgCl with salicylic alidehyde imine type modifier modification2/TiCl4Catalyst and preparation method thereof and the application being used to prepare in ethylene/alpha-olefin copolymer.By using the salicylic alidehyde imine type modifying agent containing different substituents to existing support type MgCl2/TiCl4Catalyst does modification, and is catalyzed ethylene and alpha-olefin copolymer conjunction.The salicylic alidehyde imine type modifying agent synthetic method that the present invention uses is simple, the catalytic activity of modified catalyst prepared therefrom is slightly below or slightly above before modified, the ethylene/alpha-olefin copolymer polymerizeing at the same time has the characteristics that form distribution narrow, molecular weight increase.
Description
Technical field
The invention belongs to chemical field, in particular to a kind of support type with salicylic alidehyde imine type modifier modification
MgCl2/TiCl4Catalyst and preparation method thereof and preparing the application in ethylene/alpha-olefin copolymer.
Background technique
Linear low density polyethylene (LLDPE) (LLDPE) be the 1970s exploitation polyethylene kind, mainly by ethylene with
Alpha-olefin is copolymerized to obtain by coordination polymerization, and the alpha-olefin for being commonly used in synthesis LLDPE mainly has 1- butylene, 1- hexene, 1-
Octene etc..Compared with traditional low density polyethylene (LDPE), since it can controllably adjust the length and the degree of branching of branch,
Tensile strength, tearing toughness, environmental stress crack resistance etc. are obviously improved.
The catalyst for being industrially usually used in synthesizing LLDPE mainly has metallocene catalyst and Ziegler-Natta catalysis
Agent.Metallocene catalyst is a kind of catalyst of single active center, therefore has relatively narrow molecular weight point by the copolymer that it is produced
Cloth and composition are distributed, in this way but also the LLDPE that it is produced has excellent mechanical property and environmental stress cracking resistance.In
State's patent of invention 200780023588.0 reports a kind of preparation side of ethylene/alpha-olefin copolymer based on metallocene catalyst
Method, and there is excellent environmental stress crack resistance by the copolymer that experiment measures its preparation.In addition, Chinese invention patent
201010598250.1, it 200980125348.0,200880015294.8,201010120116.0 etc. also reports respectively not
Congener metallocene catalyst is used for the preparation of ethylene and alpha olefin copolymer.But metallocene catalyst also has disadvantage, by
Higher aluminium titanium molar ratio is needed when its polymerization, and (usually 2000 or so, highest can be more than 5000), so to produce
Cheng Zhonghui consumes a large amount of co-catalyst MAO, not only will increase cost in this way, but also remaining aluminium oxide needs in final polymer
It is handled and is removed by deliming.
Different from metallocene catalyst, Ziegler-Natta catalyst is a kind of dynamics model catalyst, production
Molecular weight distribution and the composition distribution of copolymer are all wider.On the one hand this wide molecular weight distribution and composition distribution can make to produce
Object has preferable processing performance, but on the other hand also results in his mechanical property and the copolymerization of metallocene catalyst preparation
Object is compared to less better.Composition is uniformly in order to obtain, cost is relatively low while the simple LLDPE of preparation method, industry and science
A large amount of exploration is all done in boundary.Chinese patent 200510028284.6, which reports, a kind of prepares the new of ethylene/alpha-olefin copolymer
Method, used catalyst are the Nonmetallocene organic catalysts of beta-diimine class.It is total to by this method catalysis ethylene/alpha-olefin
Not only 1- ahexene content is very high in active very high but also copolymer when poly- and is uniformly distributed in the copolymer.And in polymerization process
The MAO of consumption is significantly reduced compared with metallocene catalysis system.But existing industrial production equipment is all with heterogeneous
It is designed based on Ziegler-Natta catalyst, this homogeneous catalyst is applied to industrial production and is needed to existing life
Device is produced to do biggish transformation or even need to redesign.
The problem of based on appearing above, we again focus on sight on Ziegler-Natta catalyst, it is desirable to be able to
By selecting suitable organic ligand to do simple modification to Ziegler-Natta catalyst, can obtain forming more
Add uniform copolymer.Dupuy etc., which is reported, a kind of to be modified Ziegler-Natta catalyst with the ligand containing cyclopentadienyl
Method (Journal of Applied Polymer Science, 1997,65,2281-2288).By changing for this method preparation
Property catalyst activity significantly improves, while the molecular weight distribution sharp of copolymerization product.Model will is strong etc. to report a kind of use
The fortified phenol method modified to Ziegler-Natta (Chinese Journal of Polymer Science, 2013,
31,110-121).Become narrower by the finally obtained ethylene of this method and the composition distribution of 1- hexene copolymer, at the same time
The relative molecular mass of polymer also increases.
By analyzing above, it is believed that be a kind of effective method to Ziegler-Natta catalyst modification.It
It has the following advantages that：(1) LLDPE prepared forms more uniform, performance boost；It (2) can be hardly to existing LLDPE work
Industry process units, which makes any adjustments, can directly apply to industrial production, improve efficiency, and reduce cost.
Summary of the invention
The object of the present invention is to provide a kind of support type MgCl with salicylic alidehyde imine type modifier modification2/TiCl4Catalysis
Agent.
The second object of the present invention is to provide the preparation method of such catalyst.
The third object of the present invention is to provide the application that such catalyst is used to prepare in ethylene/alpha-olefin copolymer.
To achieve the goals above, the present invention uses following technical scheme：It is a kind of to use salicylic alidehyde imine type modifier modification
Support type MgCl2/TiCl4The molecular formula of catalyst, used modifying agent is：
R1And R2Respectively：
A kind of support type MgCl with salicylic alidehyde imine type modifier modification2/TiCl4The preparation method of catalyst, including with
Lower step：In support type MgCl2/TiCl4Normal heptane is added in catalyst, it is molten that reaction is added after modifying agent is dissolved in normal heptane
In liquid, continue to be stirred to react 4 hours at 30 DEG C, stratification, export supernatant liquor, then cleaned 2 times with normal heptane, exports upper layer
Clear liquid, finally vacuum drying obtains the support type MgCl with salicylic alidehyde imine type modifier modification at 60 DEG C2/TiCl4Catalysis
Agent.
The modifying agent and support type MgCl2/TiCl4The molar ratio of Ti element is 0.1~2.0 in catalyst.
The support type TiCl4/MgCl2The preparation of catalyst is by by MgCl2It is dissolved in organic epoxy compound object, has
In machine phosphorus compound and inert diluent, Large ratio surface porous inert carrier is added in the presence of alkane precipitation additive, and be added
TiCl4It is eutectoid out and is prepared.
A kind of support type MgCl with salicylic alidehyde imine type modifier modification2/TiCl4Catalyst is used to prepare ethylene/alpha-
Application in olefin copolymer, includes the following steps：Using the catalyst as major catalyst, TEA, MAO, MMAO or TIBA
As co-catalyst, aluminium titanium molar ratio is 50~200, and polymerization temperature is 40~90 DEG C, and polymerization pressure is 0.1~1.5MPa, α-
Alkene is 1- hexene, 1- octene or 1- decene, and co-monomer concentration is 0.1~1.0mol/L when polymerization, is catalyzed ethylene and alpha-olefin
Combined polymerization 30~60 minutes.
The salicylic alidehyde imine type modifying agent synthetic method used is simple, the catalytic activity of modified catalyst prepared therefrom compared with
Before modified without significantly sacrificing, some are even slightly improved, and the ethylene/alpha-olefin being polymerize using this modified catalyst is total
Polymers has the characteristics that composition is distributed more uniform, molecular weight and increases.
Compared with prior art, the present invention beneficial effect is：Do not changing original process units and production technology
Under the conditions of, the insertion of alpha-olefin in ethylene/alpha-olefin copolymer is significantly improved, keeps Composition distribution of copolymer more uniform, altogether
The molecular weight of polymers improves.
Specific embodiment
The present invention will be described in detail With reference to embodiment.The scope of the present invention is not with specific embodiment party
Formula is limited, but is limited by the scope of the claims.
A kind of support type MgCl with salicylic alidehyde imine type modifier modification2/TiCl4Catalyst, used modifying agent
Molecular formula is：
R1And R2Respectively：
Comparative example 1
Use 17mg support type TiCl4/MgCl2Catalyst is as major catalyst, under nitrogen protection, in 100mL round bottom
In flask, ethylene and 1- hexene slurry polymerization are catalyzed under 60 DEG C, normal pressure.It is wherein that 100 addition TEA make according to aluminium titanium molar ratio
For co-catalyst, 1- hexene is added as co-monomer according to the concentration of 0.2mol/L, 50mL normal heptane divides as solvent, polyase 13 0
Clock obtains 2.7g polymer.Catalytic activity is 318g polymer/g catalyst h, and the weight average molecular weight of polymer is 97.9kg/
Mol, molecular weight distributing index 8.0,1- hexene structural unit content is 7.9mol% in polymer.
Copolymerization product extracts 12 hours through boiling n-heptane using Soxhlet extractor, is divided into two fractions：It boils positive heptan
The solvable fraction of alkane (C7-Sol) and the insoluble fraction of boiling n-heptane (C7-Insol).It is measured respectively by the method for infrared analysis
The content of alpha-olefin structural unit in two fractions of C7-Sol and C7-Insol, is denoted as [H] s and [H] i respectively.They ratio
Value ([H] s/ [H] i) can reflect out the composition homogeneity of ethylene/alpha-olefin copolymer.Ratio is smaller, shows the group of copolymer
At more uniform.[H] s/ [H] i=11.5 of polymerizate in comparative examples 1.
Embodiment 1
Take the industrial support type TiCl of 1g or so4/MgCl220mL normal heptane is added in catalyst.According to modifying agent and Ti
Molar ratio be 0.5 modifer L 1 for taking corresponding amount, be dissolved in 30mL normal heptane, it is disposable to be all added in reaction systems, 30 DEG C
Under continue to be stirred to react 4 hours.Stratification exports supernatant liquor, then is cleaned 2 times with 20mL normal heptane, exports supernatant liquor,
Finally vacuum drying obtains modified catalyst Cat-1 at 60 DEG C.
Using 17mg Cat-1 as major catalyst, under nitrogen protection, in 100mL round-bottomed flask, urged under 60 DEG C, normal pressure
Change ethylene and 1- hexene slurry polymerization.It is wherein 100 addition TEA as co-catalyst according to aluminium titanium molar ratio, according to 0.2mol/
1- hexene is added as co-monomer in the concentration of L, and 50mL normal heptane polyase 13 0 minute, obtains 4.1g polymer as solvent.Catalysis is lived
Property be 483g polymer/g catalyst h.The weight average molecular weight of polymer is 122.8kg/mol, and molecular weight distributing index is
7.2,1- hexene structural unit content is 6.4mol%, [H] s/ [H] i=9.8 in polymer.
Embodiment 2
Co-catalyst TEA is only changed to MAO with embodiment 1 by the preparation method and polymerizing condition of modified catalyst.?
4.7g polymer.Catalytic activity is 554g polymer/g catalyst h.The weight average molecular weight of polymer is 143.9kg/mol, point
Son amount profile exponent is 6.7, and 1- hexene structural unit content is 7.6mol%, [H] s/ [H] i=5.2 in polymer.
Embodiment 3
Co-catalyst TEA is only changed to MMAO with embodiment 1 by the preparation method and polymerizing condition of modified catalyst.?
4.9g polymer.Catalytic activity is 578g polymer/g catalyst h.The weight average molecular weight of polymer is 152.3kg/mol, point
Son amount profile exponent is 5.8, and 1- hexene structural unit content is 7.8mol%, [H] s/ [H] i=3.8 in polymer.
Embodiment 4
The molar ratio of modified catalyst preparation method reference embodiment 1, modified ligand L2, ligand and titanium is 0.5, is obtained
To modified catalyst Cat-2.
Using 20mg Cat-2 as major catalyst, under nitrogen protection, in 200mL polymeric kettle, under 80 DEG C, 0.3MPa
It is catalyzed ethylene and 1- hexene slurry polymerization.It is wherein 100 TEA to be added as co-catalyst according to aluminium titanium molar ratio, according to
1- hexene is added as co-monomer in the concentration of 0.4mol/L, and 100mL normal heptane polyase 13 0 minute, obtains 11.3g polymerization as solvent
Object.Catalytic activity is 1130g polymer/g catalyst h.The weight average molecular weight of polymer is 113.2kg/mol, molecular weight point
Cloth index is 7.2, and 1- hexene structural unit content is 7.1mol%, [H] s/ [H] i=7.6 in polymer.
Embodiment 5
The molar ratio of modified catalyst preparation method reference embodiment 1, modified ligand L3, ligand and titanium is 1, is changed
Property catalyst Cat-3.
Using 17mg Cat-3 as major catalyst, under nitrogen protection, in 100mL round-bottomed flask, urged under 60 DEG C, normal pressure
Change ethylene and 1- hexene slurry polymerization.TIBA wherein are added as co-catalyst according to 0.2mol/ for 200 according to aluminium titanium molar ratio
1- hexene is added as co-monomer in the concentration of L, and 50mL normal heptane is as solvent, and polyase 13 0 minute.Products weight 4.5g, obtains
11.3g polymer.Catalytic activity is 530g polymer/g catalyst h.The weight average molecular weight of polymer is 280.1kg/mol,
Molecular weight distributing index is 6.1, and 1- hexene structural unit content is 4.3mol%, [H] s/ [H] i=9.1 in polymer.
Embodiment 6
The molar ratio of modified catalyst preparation method reference embodiment 1, modified ligand L4, ligand and titanium is 1.5, is obtained
To modified catalyst Cat-4.
Using 45mg Cat-4 as major catalyst, under nitrogen protection, in 10L polymeric kettle, urged under 90 DEG C, 1.5MPa
Change ethylene and 1- hexene slurry polymerization.It is wherein 100 addition TEA as co-catalyst according to aluminium titanium molar ratio, according to 0.8mol/
1- hexene is added as co-monomer in the concentration of L, and 3L n-hexane polymerize 60 minutes as solvent, obtains 496g polymer.Catalytic activity
For 11022g polymer/g catalyst h.The weight average molecular weight of polymer is 473.7kg/mol, and molecular weight distributing index is
5.0,1- hexene structural unit content is 10.3mol%, [H] s/ [H] i=8.2 in polymer.
Embodiment 7
The molar ratio of modified catalyst preparation method reference embodiment 1, modified ligand L5, ligand and titanium is 1.5, is obtained
Modified catalyst Cat-5.
Using 45mg Cat-5 as major catalyst, under nitrogen protection, in 10L polymeric kettle, urged under 80 DEG C, 1.5MPa
Change ethylene and 1- hexene slurry polymerization.It is wherein 200 TIBA to be added as co-catalyst according to aluminium titanium molar ratio, according to
1- hexene is added as co-monomer in the concentration of 0.8mol/L, and 3L n-hexane polymerize 60 minutes as solvent.Obtain 531g polymer.
Catalytic activity is 11800g polymer/g catalyst h.The weight average molecular weight of polymer is 483.1kg/mol, molecular weight distribution
Index is 6.2, and 1- hexene structural unit content is 11.1mol%, [H] s/ [H] i=8.9 in polymer.
Embodiment 8
The molar ratio of modified catalyst preparation method reference embodiment 1, modified ligand L6, ligand and titanium is 1.5, is obtained
To modified catalyst Cat-6.
Using 17mg Cat-6 as major catalyst, under nitrogen protection, in 100mL round-bottomed flask, urged under 60 DEG C, normal pressure
Change ethylene and 1- hexene slurry polymerization.It is wherein 100 addition TEA as co-catalyst according to aluminium titanium molar ratio, according to 0.2mol/
1- hexene is added as co-monomer in the concentration of L, and 50mL normal heptane polyase 13 0 minute, obtains 3.5g polymer as solvent.Catalysis is lived
Property be 412g polymer/g catalyst h.The weight average molecular weight of polymer be 13.6kg/mol, molecular weight distributing index 6.8,
1- hexene structural unit content is 6.1mol%, [H] s/ [H] i=5.6 in polymer.
Embodiment 9
The molar ratio of modified catalyst preparation method reference embodiment 1, modified ligand L7, ligand and titanium is 0.1, is obtained
To modified catalyst Cat-7.
Using 17mg Cat-7 as major catalyst, under nitrogen protection, in 100mL round-bottomed flask, urged under 60 DEG C, normal pressure
Change ethylene and 1- octene slurry polymerization.It is wherein 100 addition TEA as co-catalyst according to aluminium titanium molar ratio, according to 0.2mol/
1- octene is added as co-monomer in the concentration of L, and 50mL normal heptane polyase 13 0 minute, obtains 3.5g polymer as solvent.Catalysis is lived
Property be 412g polymer/g catalyst h.The weight average molecular weight of polymer be 12.3kg/mol, molecular weight distributing index 8.1,
1- octene structural unit content is 7.5mol%, [H] s/ [H] i=9.8 in polymer.
Embodiment 10
The molar ratio of modified catalyst preparation method reference embodiment 1, modified ligand L8, ligand and titanium is 1, is changed
Property catalyst Cat-8.
Using 20mg Cat-8 as major catalyst, under nitrogen protection, in 200mL polymeric kettle, urged under 50 DEG C, 0.4MPa
Change ethylene and 1- octene slurry polymerization.It is wherein 200 TIBA to be added as co-catalyst according to aluminium titanium molar ratio, according to
1- octene is added as co-monomer in the concentration of 0.4mol/L, and 100mL normal heptane is as solvent, and polyase 13 0 minute.Obtain 5.6g polymerization
Object.Catalytic activity is 560g polymer/g catalyst h.The weight average molecular weight of polymer is 24.7kg/mol, molecular weight distribution
Index is 7.9, and 1- octene structural unit content is 6.9mol%, [H] s/ [H] i=8.8 in polymer.
Embodiment 11
The molar ratio of modified catalyst preparation method reference embodiment 1, modified ligand L9, ligand and titanium is 1, is changed
Property catalyst Cat-9.
Using 20mg Cat-9 as major catalyst, under nitrogen protection, in 200mL polymeric kettle, under 70 DEG C, 0.4MPa
It is catalyzed ethylene and 1- decene slurry polymerization.It is wherein 200 TIBA to be added as co-catalyst according to aluminium titanium molar ratio, according to
1- decene is added as co-monomer in the concentration of 1.0mol/L, and 100mL normal heptane is as solvent, and polyase 13 0 minute.Obtain 6.7g polymerization
Object.Catalytic activity is 670g polymer/g catalyst h.The weight average molecular weight of polymer is 123.6kg/mol, molecular weight distribution
Index is 10.8, and 1- decene structural unit content is 8.7mol%, [H] s/ [H] i=8.3 in polymer.
Embodiment 12
The molar ratio of modified catalyst preparation method reference embodiment 1, modified ligand L10, ligand and titanium is 2.0, is obtained
To modified catalyst Cat-10.
Using 17mg Cat-10 as major catalyst, under nitrogen protection, in 100mL round-bottomed flask, under 40 DEG C, normal pressure
It is catalyzed ethylene and 1- decene slurry polymerization.It is wherein 50 TEA to be added as co-catalyst according to aluminium titanium molar ratio, according to
1- decene is added as co-monomer in the concentration of 0.1mol/L, and 50mL normal heptane is as solvent, and polyase 13 0 minute.Obtain 2.3g polymerization
Object.Catalytic activity is 271g polymer/g catalyst h.The weight average molecular weight of polymer is 112.6kg/mol, molecular weight distribution
Index is 6.5, and 1- decene structural unit content is 4.1mol%, [H] s/ [H] i=9.2 in polymer.
Claims (5)
1. a kind of support type MgCl with salicylic alidehyde imine type modifier modification2/TiCl4Catalyst, it is characterised in that：
The molecular formula of used modifying agent is：
R1And R2Respectively：
2. the preparation method of catalyst according to claim 1, it is characterised in that include the following steps：In support type MgCl2/
TiCl4Normal heptane is added in catalyst, is added in reaction solution after modifying agent is dissolved in normal heptane, it is anti-to continue stirring at 30 DEG C
It answers 4 hours, stratification, exports supernatant liquor, then cleaned 2 times with normal heptane, export supernatant liquor, finally taken out at 60 DEG C true
Sky is dried to obtain the support type MgCl with salicylic alidehyde imine type modifier modification2/TiCl4Catalyst.
3. the preparation method of catalyst according to claim 2, it is characterised in that：The modifying agent and support type MgCl2/
TiCl4The molar ratio of Ti element is 0.1~2.0 in catalyst.
4. the preparation method of catalyst according to claim 2, it is characterised in that：The support type TiCl4/MgCl2Catalyst
Preparation be by by MgCl2It is dissolved in organic epoxy compound object, organic phosphorus compound and inert diluent, helps analysis in alkane
Large ratio surface porous inert carrier is added in the presence of agent out, and TiCl is added4It is eutectoid out and is prepared.
5. catalyst is used to prepare the application in ethylene/alpha-olefin copolymer according to claim 1, it is characterised in that including
Following steps：Using the catalyst as major catalyst, TEA, MAO, MMAO or TIBA are as co-catalyst, aluminium titanium molar ratio
50~200, polymerization temperature is 40~90 DEG C, and polymerization pressure is 0.1~1.5MPa, and alpha-olefin is 1- hexene, 1- octene or the 1- last of the ten Heavenly stems
Alkene, co-monomer concentration is 0.1~1.0mol/L when polymerization, and catalysis ethylene and alpha-olefin copolymer close 30~60 minutes.
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| US5637739A (en) * | 1990-03-21 | 1997-06-10 | Research Corporation Technologies, Inc. | Chiral catalysts and catalytic epoxidation catalyzed thereby |
| CN1884311A (en) * | 2006-05-22 | 2006-12-27 | 中国科学院上海有机化学研究所 | Mono-active center Ziegler-Natta catalyst for olefinic polymerization |
| CN101412766A (en) * | 2007-10-16 | 2009-04-22 | 中国石化扬子石油化工有限公司 | Magnesium compound load type non-metallocene catalyst and preparation thereof |
| CN101798361A (en) * | 2010-02-10 | 2010-08-11 | 中国科学院上海有机化学研究所 | Olefin polymerization catalysts |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6521561B1 (en) * | 1998-05-01 | 2003-02-18 | President And Fellows Of Harvard College | Main-group metal based asymmetric catalysts and applications thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5637739A (en) * | 1990-03-21 | 1997-06-10 | Research Corporation Technologies, Inc. | Chiral catalysts and catalytic epoxidation catalyzed thereby |
| CN1884311A (en) * | 2006-05-22 | 2006-12-27 | 中国科学院上海有机化学研究所 | Mono-active center Ziegler-Natta catalyst for olefinic polymerization |
| CN101412766A (en) * | 2007-10-16 | 2009-04-22 | 中国石化扬子石油化工有限公司 | Magnesium compound load type non-metallocene catalyst and preparation thereof |
| CN101798361A (en) * | 2010-02-10 | 2010-08-11 | 中国科学院上海有机化学研究所 | Olefin polymerization catalysts |
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