CN106866848A - Vinyl polymerization major catalyst and preparation method thereof, the ethylene rolymerization catalyst containing the major catalyst - Google Patents
Vinyl polymerization major catalyst and preparation method thereof, the ethylene rolymerization catalyst containing the major catalyst Download PDFInfo
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- CN106866848A CN106866848A CN201510917544.9A CN201510917544A CN106866848A CN 106866848 A CN106866848 A CN 106866848A CN 201510917544 A CN201510917544 A CN 201510917544A CN 106866848 A CN106866848 A CN 106866848A
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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
- C08F10/02—Ethene
Abstract
The present invention relates to a kind of vinyl polymerization major catalyst and preparation method thereof, the ethylene rolymerization catalyst containing the major catalyst.The major catalyst includes magnesium compound, double solvents, silane compound and titanium compound；Its preparation method comprises the following steps：Magnesium compound and double solvents are mixed, clear solution is formed；The clear solution is mixed complete to precipitation with silane compound and titanium compound respectively, major catalyst suspension is obtained；The major catalyst suspension is carried out into slaking reaction；Major catalyst suspension after the curing is washed, is dried, obtained major catalyst.Catalyst of the present invention includes above-mentioned major catalyst and organo-aluminum compound.Major catalyst of the invention has activity very high, good particle shape and very narrow size distribution, can be the polyethylene for preparing broad peak molecular weight distribution the characteristics of the most prominent.
Description
Technical field
The present invention relates to a kind of major catalyst for olefinic polymerization particularly ethylene homo conjunction or combined polymerization
And preparation method thereof, and the catalyst containing the major catalyst and application thereof, belong to olefinic polymerization and urge
Agent field.
Background technology
From the seventies after efficient Zigler-Natta ethylene rolymerization catalysts are succeeded in developing, world's polyethylene
Industry there occurs great change.Over nearly more than 20 years, with the development of ethene polymerization process, with polymerization technique phase
Supporting catalyst also achieves significant progress, and wherein Ziegler-Natta catalyst is excellent by its
Polymerization and maturation application technology still occupy important ground in polyethylene catalysts field
Position, still has substantial amounts of patent application to occur in recent years.In these patent applications, research core is not outer
It is the hydrogen tune of the polymerization activity of catalyst, the particle shape of catalyst and particle diameter distribution, catalyst
Sensitiveness etc..
In terms of polyethylene product, the polyethylene (letter below that molecular weight distribution is distributed in bimodal or broad peak
Claiming bimodal polyethylene) product is always one of focus of industry research.Bimodal polyethylene mainly passes through two
The approach of kind realizes that a kind of approach is two polymer reactors using series connection, poly- in two reactors
Conjunction condition is different, and the molecular weight of polyethylene prepared is of different sizes, so as to realize the double of molecular weight distribution
Peaking or broad peak；Another approach is used containing two kinds of composite catalysts in activated centre, in list
In one reactor, the polyethylene of different molecular weight is prepared using the performance difference in activated centre.
In patent CN1140722, CN1229092 and CN102040688, preparation is disclosed respectively
The method of ethylene rolymerization catalyst, the catalyst prepared using respective method is connected work in slurry stirred tank
Bimodal polyethylene can be produced in skill.But in the catalyst preparation technology of these patent disclosures, although
The activity of catalyst, particle shape and hydrogen regulation performance meet series reactor process and produce bimodal poly- second
The requirement of alkene, but in terms of copolymerization performance, the insertion rate of comonomer is low, it is necessary to add in the reaction
Larger amount of comonomer, the long period that have impact on technological process is steadily operated, and increased technological operation
Difficulty.And in terms of composite catalyst, the method for generally using is to use different metallic compounds,
Bimodal polyethylene is realized in such as titanium and zirconium metal active.Although such catalyst can be single anti-
Realization prepares bimodal polyethylene in answering device, can be in catalyst preparation, it is necessary to by different activated centres
It is supported in same catalyst carrier, load process is inevitable complicated, and most metals compound is needed
It is often also very high using the high metallocene compound of price, the preparation cost of such catalyst.
Patent " a kind of distribution polyolefin catalyst wide and its preparation and the application of the present inventor
CN103113499 " is introduced as long as disclosing in traditional Ziegler-Natta catalyst preparation method
A kind of silane compound of special construction, in the presence of only titanium activated centre, it is possible to single
Broad peak polyethylene is prepared in reactor.But catalyst prepared by the patent of invention is in particle shape and altogether
Poly- aspect of performance Shortcomings.
The content of the invention
It is an object of the invention to provide a kind of vinyl polymerization major catalyst and preparation method thereof, the catalysis
Agent has that catalysis activity is high, particle shape is good, particle diameter distribution is narrow, copolymerization performance good, can produce broad peak
The advantages of polyethylene.
Gather another object of the present invention is to provide a kind of ethene containing above-mentioned vinyl polymerization major catalyst
Close catalyst.
It is that, up to above-mentioned purpose, the present invention provides a kind of vinyl polymerization major catalyst, by magnesium compound, again
Bonding solvent, silane compound and titanium compound are made, the magnesium compound, double solvents, silanization
The mol ratio of compound and titanium compound is：1:1.1-10:0.05-2:0.5-50；
The magnesium compound is magnesium chloride or diethoxy magnesium；
The double solvents includes tributyl phosphate, epoxychloropropane and ethanol, the double solvents
In terms of every mole of magnesium compound, tributyl phosphate is 0.3-3.5 moles to consumption, and epoxychloropropane is 0.3-3.5
Mole, ethanol is 0.5-3.0 moles；
Shown in the structural formula of the silane compound such as formula (I)：
Wherein, R2、R3、R4And R5It is C1-C15Alkyl, C3-C20Cycloalkyl or C6-C30
Aryl, and substituent R2、R3、R4And R5In at least two differ；
Shown in the formula of the titanium compound such as formula (III)：Ti(OR6)mCl4-m(Ⅲ)；Wherein,
R6It is C2~C20Alkyl.
Vinyl polymerization major catalyst of the present invention, wherein, the silane compound is preferably by three
Ethyoxyl isopropoxy silane, diethoxy isopropoxy tert-butoxy silane, the tertiary fourth of three isopropoxies
TMOS, the tert-butoxy silane of diisopropoxy two, diethoxy cyclohexyloxy tert-butoxy silane,
Diethoxy phenoxy group tert-butoxy silane, an ethyoxyl diisopropoxy tert-butoxy silane and ethoxy
Base isopropoxy tert-butoxy cyclohexyloxy silane constitutes at least one in group.
Vinyl polymerization major catalyst of the present invention, wherein, the titanium compound be preferably selected from by
TiCl4、Ti(OCH3)Cl3、Ti(OCH3)2Cl2、Ti(OC2H5)Cl3、Ti(OC2H5)2Cl2、
Ti(OC2H5)3Cl、Ti(OC4H9)Cl3、Ti(OC4H9)2Cl2With Ti (OC4H9)3Cl is constituted in group
At least one.
Vinyl polymerization major catalyst of the present invention, wherein, the double solvents preferably also includes lazy
Property dispersant, the inertia dispersant is preferably hydro carbons and/or halogenated hydrocarbon.
Vinyl polymerization major catalyst of the present invention, wherein, the inertia dispersant be preferably selected from by
Hexane, heptane, octane, toluene, dimethylbenzene, 1,2- dichloroethanes, chlorocyclohexane and chlorobenzene institute group
Into at least one in group.
The present invention also provides a kind of preparation method of vinyl polymerization major catalyst, the vinyl polymerization main catalytic
Agent is above-mentioned vinyl polymerization major catalyst, is comprised the following steps：
S1：At 25-100 DEG C, magnesium compound and double solvents are mixed, sustained response 10 minutes is extremely
20 hours so that formed clear solution；
S2：At -10 DEG C to 50 DEG C, the clear solution is mixed with silane compound and titanium compound respectively
Close, titanium compound added clear solution in 30 minutes to 5 hours several times, and sustained response is led
Catalyst suspension；
S3：At 25 DEG C to 150 DEG C, the major catalyst suspension is carried out into slaking reaction 0.5 to 15
Hour；
S4：Major catalyst suspension after the curing is washed, is dried, obtained major catalyst.
The preparation method of vinyl polymerization major catalyst of the present invention, in step S3, it is preferred that
Slaking reaction 1 to 5 hour.
The preparation method of vinyl polymerization major catalyst of the present invention, in step S4, the inertia is molten
Agent is preferably selected from least be made up of iso-butane, pentane, hexane, heptane and hexamethylene in group
Kind.
The present invention also provides a kind of ethylene rolymerization catalyst, including following components：
Above-mentioned vinyl polymerization major catalyst or vinyl polymerization major catalyst obtained in above-mentioned preparation method；
Organo-aluminum compound, it is formula AlRgX3-gAt least one in shown compound, in formula,
R is C1-C20Alkyl, X is halogen, and g is integer and 1<g≤3.
Ethylene rolymerization catalyst of the present invention, wherein, the organo-aluminum compound be preferably by
AlEt3、Al(iso-Bu)3、Al(n-C6H13)3、Al(n-C8H17)3And AlEt2Cl is constituted in group
It is at least one.
Beneficial effects of the present invention are：Using the dissolution system of catalyst component of the invention, with reference to institute
The use of silane compound is stated, not only makes catalyst that there is good particle shape and very narrow granularity
Distribution, and the polyvinyl resin of molecular weight distribution wide can be produced in single-reactor；Additionally,
Caltalyst of the invention is tied up in the copolymerization of catalysis ethene and other alpha-olefins, comonomer
Insertion rate it is significantly higher, better than existing catalyst.
Brief description of the drawings：
Fig. 1 is the Laser particle-size distribution curve of catalyst prepared by embodiment 1.
Specific embodiment
The present invention is further illustrated by the following examples, but the present invention is not limited to these embodiments.
The test of the average grain diameter and its size distribution of catalyst
By catalyst sample dispersion in hexane, using Malvern Instruments Ltd. companies of Britain
The size distribution curve of Mastersizer laser particle size analyzer test samples, wherein,
The average grain diameter of catalyst is given with D (50)；
Size distribution Span=(D (90)-D (10))/D (50) of catalyst；
D (50) is complete in the size distribution curve of Mastersizer laser particle size analyzers test in formula
Diameter value of the diameter of the 50% of portion's particle less than the value；D (10) is that the diameter of the 10% of whole particles is low
In the diameter value of the value；D (90) is the diameter value of the diameter less than the value of the 90% of whole particles.
Ethylene homo is closed
The major catalyst of 1L hexanes, 1mmol triethyl aluminums (co-catalyst) and 10mg is added to
In 2L stainless steel stirred tanks, temperature is then risen to 80 DEG C, the hydrogen of disposable addition 0.2MPa,
Then the gross pressure of system is maintained into 1.0MPa with ethene carries out polymerisation, after reacting 2 hours,
Stop adding ethene, cooling, pressure release, polyethylene powder to weigh.With the weight of polyethylene powder divided by
The consumption of major catalyst calculates the activity of catalyst.
Ethene and butene-1 combined polymerization
By the master of 1L hexanes, 1mmol triethyl aluminums (co-catalyst), 20ml butene-1s and 10mg
Catalyst is added in 2L stainless steel stirred tanks, and temperature then is risen into 80 DEG C, disposable to add
The hydrogen of 0.2MPa, the gross pressure of system then is maintained into 1.0MPa with ethene carries out polymerisation,
After reaction 2 hours, stop adding ethene, cooling, pressure release, polyethylene powder to weigh.With polyethylene
The weight of powder calculates the activity of catalyst divided by the consumption of major catalyst.
The mean molecule quantity of polyethylene, the measurement of molecular weight distribution width (PDI)
Using the GPC V2000 gel permeation chrommatographs of Waters companies, with 1,2,4- trichloro-benzenes are solvent,
140 DEG C, under 1mL/min constant flow rates, by Composition distribution, use with polystyrene as standard specimen
Universal calibration method, determines the number-average molecular weight Mn and weight average molecular weight Mw of polyethylene, and calculates accordingly
Molecular weight distribution width PD1=Mw/Mn.
Embodiment 1
In the reactor being sufficiently displaced from by nitrogen, magnesium dichloride 4.0g, toluene 60 are sequentially added
Ml, ethanol 6.0ml, tributyl phosphate 3.0ml, epoxychloropropane 2.0ml, are warming up to 65 DEG C,
It is stirred continuously until that solid is completely dissolved to form homogeneous solution.- 5 DEG C are then cooled to, 5.5g is added
Diethoxy isopropoxy tert-butoxy silane, then it is slowly added dropwise 30ml TiCl4, after being added dropwise to complete, rise
Temperature is to 85 DEG C of stirring reaction 2h.After the completion of reaction, stop stirring, staticly settle, filter, then with oneself
After alkane washs 4 times, solid main catalyst particle is dried to obtain.
Major catalyst and co-catalyst triethyl aluminum collectively constitute catalyst, the size distribution of catalyst,
The characterization result of activity and polymer resin is as shown in table 1.
Embodiment 2
5.5g diethoxy isopropoxies tert-butoxy silane in prepared by the major catalyst of embodiment 1 is adjusted
Whole is 2.3g triethoxy isopropoxy silane, and other conditions are same as Example 1.
Embodiment 3
5.5g diethoxy isopropoxies tert-butoxy silane in prepared by the major catalyst of embodiment 1 is adjusted
Whole is the tertiary fourth oxosilane of 4.8g triethoxies, and other conditions are same as Example 1.
Embodiment 4
5.5g diethoxy isopropoxies tert-butoxy silane in prepared by the major catalyst of embodiment 1 is adjusted
It is whole for 2.5g other conditions are same as Example 1.
Embodiment 5
5.5g diethoxy isopropoxies tert-butoxy silane in prepared by the major catalyst of embodiment 1 is adjusted
Whole is the 5.1g tertiary fourth oxosilanes of diethoxy hexamethylene oxygen, and other conditions are same as Example 1.
Embodiment 6
5.5g diethoxy isopropoxies tert-butoxy silane in prepared by the major catalyst of embodiment 1 is adjusted
Whole is 8.2g diethoxy isopropoxy benzene TMOSs, and other conditions are same as Example 1.
Embodiment 7
5.5g diethoxy isopropoxies tert-butoxy silane in prepared by the major catalyst of embodiment 1 is adjusted
Whole is 4.0g diethoxy isopropoxy benzene TMOSs, and other conditions are same as Example 1.
Comparative example 1
In the preparation of the major catalyst of embodiment 1, diethoxy isopropoxy tert-butoxy silane is not used,
Other conditions are same as Example 1.
Comparative example 2
5.5g diethoxy isopropoxies tert-butoxy silane in prepared by the major catalyst of embodiment 1 is adjusted
Whole is 3.2g tetraethoxysilanes, and other conditions are same as Example 1.
Comparative example 3
The method of the embodiment 1 announced with reference to Chinese patent CN103113499 prepares catalyst, specifically
Step is as follows.
In the reactor being sufficiently displaced from by nitrogen, magnesium dichloride 1g, ethanol 9ml are sequentially added,
100 DEG C are warming up under toluene 70ml, stirring, solid is completely dissolved after forming homogeneous solution, it is permanent
Warm 1h；100 DEG C are then cooled to, 1.7ml Ti (OBu) is added dropwise4, after reaction 1h, it is cooled to 70 DEG C
Constant temperature, adds 3.5ml diethoxy isopropoxy tert-butoxy silanes, is slowly added dropwise 11.0ml SiCl4,
Reaction 2h, stops stirring, staticly settles, and filters, and washing is dried, and obtains solid particle.Will
To solid particle dispersions in 30ml toluene, 0 DEG C is added dropwise 20ml TiCl4, rear 0-10 DEG C of maintenance
1h, 60 DEG C of reaction 3h.Stop stirring, stand suspension, layering extracts supernatant liquor, and toluene is washed
Wash twice, hexane is washed twice, nitrogen drying obtains solid main catalyst.
Major catalyst and co-catalyst triethyl aluminum collectively constitute catalyst, the size distribution of catalyst,
The characterization result of activity and polymer resin is as shown in table 1.
Table 1
Knowable to the data of table 1, using silane compound of the present invention, poly- second can be widened
The molecular weight distribution width (comparative example 1 and 2) of alkene, with Chinese patent CN103113499 preparations
Catalyst (comparative example 3) is compared, and the breadth of particle size distribution Span values of catalyst of the invention are respectively less than
1.1, less than Span values in comparative example 3, and when in catalysis ethene with butene-1 combined polymerization, fourth
The insertion rate of alkene -1 illustrates that the size distribution of catalyst of the invention is narrower apparently higher than comparative example 3,
Copolymerization performance is more preferable.It is to sum up shown, the granularity of catalyst can be not only made using catalyst of the invention
Distribution narrow, and the polyvinyl resin of molecular weight distribution wide can be prepared.
Certainly, the present invention can also have other various embodiments, without departing substantially from spirit of the invention and its essence
In the case of, those of ordinary skill in the art can make various corresponding changes and change according to the present invention
Shape, but these corresponding changes and deformation should all belong to protection scope of the present invention.
Claims (10)
1. a kind of vinyl polymerization major catalyst, it is characterised in that by magnesium compound, double solvents, silicon
Hydride compounds and titanium compound are made, the magnesium compound, double solvents, silane compound and titanizing
The mol ratio of compound is：1:1.1-10:0.05-2:0.5-50；
The magnesium compound is magnesium chloride or diethoxy magnesium；
The double solvents includes tributyl phosphate, epoxychloropropane and ethanol, the double solvents
In terms of every mole of magnesium compound, tributyl phosphate is 0.3-3.5 moles to consumption, and epoxychloropropane is 0.3-3.5
Mole, ethanol is 0.5-3.0 moles；
Shown in the structural formula of the silane compound such as formula (I)：
Wherein, R2、R3、R4And R5It is C1-C15Alkyl, C3-C20Cycloalkyl or C6-C30
Aryl, and substituent R2、R3、R4And R5In at least two differ；
Shown in the formula of the titanium compound such as formula (III)：Ti(OR6)mCl4-m(Ⅲ)；Wherein,
R6It is C2~C20Alkyl.
2. vinyl polymerization major catalyst according to claim 1, it is characterised in that the silane
Compound is by triethoxy isopropoxy silane, diethoxy isopropoxy tert-butoxy silane, three
Isopropoxy tert-butoxy silane, the tert-butoxy silane of diisopropoxy two, diethoxy cyclohexyloxy
Tert-butoxy silane, diethoxy phenoxy group tert-butoxy silane, a tertiary fourth of ethyoxyl diisopropoxy
TMOS and ethyoxyl isopropoxy tert-butoxy cyclohexyloxy silane constitute at least in group
Kind.
3. vinyl polymerization major catalyst according to claim 1, it is characterised in that the titanizing
Compound is selected from by TiCl4、Ti(OCH3)Cl3、Ti(OCH3)2Cl2、Ti(OC2H5)Cl3、Ti(OC2H5)2Cl2、
Ti(OC2H5)3Cl、Ti(OC4H9)Cl3、Ti(OC4H9)2Cl2With Ti (OC4H9)3Cl is constituted in group
At least one.
4. vinyl polymerization major catalyst according to claim 1, it is characterised in that described compound
Solvent also includes inertia dispersant, and the inertia dispersant is hydro carbons and/or halogenated hydrocarbon.
5. vinyl polymerization major catalyst according to claim 4, it is characterised in that the inertia
Dispersant is selected from by hexane, heptane, octane, toluene, dimethylbenzene, 1,2- dichloroethanes, chloro hexamethylene
Alkane and chlorobenzene constitute at least one in group.
6. a kind of preparation method of vinyl polymerization major catalyst, the vinyl polymerization major catalyst will for right
Seek the vinyl polymerization major catalyst described in any one of 1-3, it is characterised in that comprise the following steps：
S1：At 25-100 DEG C, magnesium compound and double solvents are mixed, sustained response 10 minutes is extremely
20 hours so that formed clear solution；
S2：At -10 DEG C to 50 DEG C, the clear solution is mixed with silane compound and titanium compound respectively
Close, titanium compound added clear solution in 30 minutes to 5 hours several times, and sustained response is led
Catalyst suspension；
S3：At 25 DEG C to 150 DEG C, the major catalyst suspension is carried out into slaking reaction 0.5 to 15
Hour；
S4：Major catalyst suspension after the curing is washed, is dried, obtained major catalyst.
7. the preparation method of vinyl polymerization major catalyst according to claim 6, it is characterised in that
In step S3, slaking reaction 1 to 5 hour.
8. the preparation method of vinyl polymerization major catalyst according to claim 6, it is characterised in that
In step S4, the atent solvent is selected from by iso-butane, pentane, hexane, heptane and hexamethylene institute group
Into at least one in group.
9. a kind of ethylene rolymerization catalyst, it is characterised in that including following components：
Vinyl polymerization major catalyst described in claim any one of 1-3 or as being made described in claim 4
Vinyl polymerization major catalyst obtained in Preparation Method；
Organo-aluminum compound, it is formula AlRgX3-gAt least one in shown compound, in formula, R
It is C1-C20Alkyl, X is halogen, and g is integer and 1<g≤3.
10. ethylene rolymerization catalyst according to claim 9, it is characterised in that described organic
Aluminium compound is by AlEt3、Al(iso-Bu)3、Al(n-C6H13)3、Al(n-C8H17)3And AlEt2Cl institutes
At least one in composition group.
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| JP2021502471A (en) * | 2017-11-13 | 2021-01-28 | ダブリュー・アール・グレース・アンド・カンパニー−コーンＷ Ｒ Ｇｒａｃｅ ＆ Ｃｏ−Ｃｏｎｎ | Catalyst components for propylene polymerization |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101885791A (en) * | 2010-07-22 | 2010-11-17 | 中国石油天然气股份有限公司 | Broad/multimodal distributed polyolefin catalyst, preparation and application thereof |
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- 2015-12-10 CN CN201510917544.9A patent/CN106866848A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101885791A (en) * | 2010-07-22 | 2010-11-17 | 中国石油天然气股份有限公司 | Broad/multimodal distributed polyolefin catalyst, preparation and application thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2021502471A (en) * | 2017-11-13 | 2021-01-28 | ダブリュー・アール・グレース・アンド・カンパニー−コーンＷ Ｒ Ｇｒａｃｅ ＆ Ｃｏ−Ｃｏｎｎ | Catalyst components for propylene polymerization |
| JP7366912B2 (en) | 2017-11-13 | 2023-10-23 | ダブリュー・アール・グレース・アンド・カンパニー－コーン | Catalyst components for propylene polymerization |
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Application publication date: 20170620 |