CN1673227A - Process for preparing alkylaluminoxane - Google Patents
Process for preparing alkylaluminoxane Download PDFInfo
- Publication number
- CN1673227A CN1673227A CN 200410029717 CN200410029717A CN1673227A CN 1673227 A CN1673227 A CN 1673227A CN 200410029717 CN200410029717 CN 200410029717 CN 200410029717 A CN200410029717 A CN 200410029717A CN 1673227 A CN1673227 A CN 1673227A
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- CN
- China
- Prior art keywords
- preparation
- suspension
- crystalline hydrate
- reactor
- organic solvent
- Prior art date
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Links
- 238000004519 manufacturing process Methods 0.000 title description 4
- 238000002360 preparation method Methods 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 239000000725 suspension Substances 0.000 claims abstract description 16
- 125000005234 alkyl aluminium group Chemical group 0.000 claims abstract description 9
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 7
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 7
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 7
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 12
- -1 isobutyl- Chemical group 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 4
- 238000006073 displacement reaction Methods 0.000 claims description 3
- 238000005259 measurement Methods 0.000 claims description 3
- 238000011160 research Methods 0.000 claims description 3
- 238000012360 testing method Methods 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 239000002002 slurry Substances 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims 1
- 238000010792 warming Methods 0.000 claims 1
- 125000000217 alkyl group Chemical group 0.000 abstract description 4
- 229910052723 transition metal Inorganic materials 0.000 abstract description 3
- 150000003624 transition metals Chemical class 0.000 abstract description 3
- 239000013078 crystal Substances 0.000 abstract 1
- 229910007926 ZrCl Inorganic materials 0.000 description 17
- 239000004411 aluminium Substances 0.000 description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 12
- 238000006116 polymerization reaction Methods 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000002904 solvent Substances 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 5
- 229920002554 vinyl polymer Polymers 0.000 description 5
- 230000008030 elimination Effects 0.000 description 3
- 238000003379 elimination reaction Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 239000011343 solid material Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000012968 metallocene catalyst Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
Abstract
The present invention provides a preparation method of alkyl aluminoxane as metallocene and late transition metal cocatalyst, and is characterized by that it adopts the suspension formed from crystal hydrate and hydrocarbon organic solvent and alkyl aluminium to make continuous reaction so as to prepare the alkyl aluminoxane.
Description
Technical field
The present invention relates to for olefines polymerization metallocene, rear transition metal promotor---the preparation method of alkylaluminoxane.
Background technology
The preparation method of alkylaluminoxane is a lot, but can be summarized as following two big classes: directly water conservancy project skill and water conservancy project skill indirectly.Directly the yield of water conservancy project skill target product is higher, but production process danger is bigger, simultaneously, in order to solve the danger of production process, often need to design various specific installations, this makes the investment cost of plant construction increase (US4924018 greatly, US4772736, US4937363, US4908463, US5087713, US5041585).General crystalline hydrate and the aluminum alkyls of adopting of water conservancy project skill reacts indirectly.The preparation technology of existing bibliographical information is mixed with suspension with crystalline hydrate and solvent in reactor, the preparation technology who under constantly stirring alkyl aluminum solutions is reacted while adding.Its main drawback is: owing to be that alkyl aluminum solutions is added in the suspension of crystalline hydrate gradually, the initial aluminum alkyls overwhelming majority that adds is Al (OH) by water transform excessive relatively in the system
3, have only when the free-water concentration in the system is reduced to a certain degree, generate Al (OH)
3Side reaction just be reduced to accessory degree.Therefore, the yield of this synthesis technique target product is lower, causes the cost of the finished product higher; Adopt this technology, the yield of target product generally is no more than 40% (US5099050, US5041583, EP393358A
2, EP383255A
2, EP208561A
2, US5248801).
The inventor provides a kind of method of synthesis of alkyl aikyiaiurnirsoxan beta in Chinese patent application 03104815.3.The key points for operation that comprised are as follows: reaction unit through the displacement of sufficient inertia after, in the disposable adding reactor of alkyl aluminum solutions that the First Astronautic Research Institute for Measurement and Test is needed, under constantly stirring, powdery crystalline hydrate solid is added in the reactor continuously.This technology is compared with the technology that adds aluminum alkyls in crystalline hydrate suspension has following advantage: (1) is owing to be to add crystalline hydrate in the alkyl aluminum solutions continuously, aluminum alkyls in the reaction system is in superfluous state all the time, thereby can avoid generating Al (OH) effectively
3Side reaction take place; What (2) add in the reaction system is the crystalline hydrate solid, can reduce the solvent load of required input in the reaction process effectively, thereby improves the throughput of device, reduces the quantity of solvent of required processing in the last handling process.
But the problem that this preparation technology exists is: because aluminum alkyls and alkylaluminoxane are to the high susceptibility of moisture and air, to feeder for solid materials sealing requirements height; Because the crystalline hydrate flowability of salt is relatively poor, therefore in operating process, there is crane span structure to a certain degree, reinforced even inadequately, and need often cleaning.
Summary of the invention
The present invention provides a kind of improved indirect water conservancy project skill preparation method on the basis of above-mentioned prior art.
Technical scheme provided by the invention is: in the disposable adding reactor of alkyl aluminum solutions; Crystalline hydrate and hydrocarbon organic solvent are mixed with suspension; Under the agitation condition suspension is added in the reactor continuously.
Concrete process comprises: after reaction unit passes through sufficient inertia displacement, in the disposable adding reactor of alkyl aluminum solutions with First Astronautic Research Institute for Measurement and Test's need; Crystalline hydrate and hydrocarbon organic solvent are mixed with suspension in a preparation still; Under constantly stirring, the suspension that will contain crystalline hydrate by a slurry feed device adds in the reactor continuously, behind reinforced the finishing, heat up and continue to stir 10-30 hour, after reaction finishes after filtration, drying obtains product.
The input speed of suspension is not done special qualification among the present invention, but for obtaining well behaved product, the choosing of suggestion speed preferably keep reactor temperature steadily, temperature fluctuation is controlled at ± 5 ℃.
Temperature in of the present invention during the charging preferably is controlled at-30-25 ℃, and temperature is controlled at 25-60 ℃ during reaction.
Crystalline hydrate of the present invention can be general obtainable various crystalline hydrates, as: MgCl
26H
2O, CuSO
45H
2O, Al
2(SO
4)
318H
2O, LiOHH
2O, Na
2CO
310H
2O etc. wherein, are preferably Al
2(SO
4)
318H
2O.
The used aluminum alkyls raw material of technological process of the present invention is the trialkylaluminium that meets following formula:
AlR
3
Wherein, R is C
1~C
20Alkyl, be preferably methyl and isobutyl-.
By this law synthetic alkylaluminoxane product is the various alkylaluminoxanes corresponding with above-mentioned alkyl, is preferably methylaluminoxane (MAO) and isobutyl aluminium alkoxide.
The preferred toluene of hydrocarbon organic solvent of the present invention.
Preparation method of the present invention has the following advantages: the advantage that 1) has kept technology described in the Chinese patent application 03104815.3; 2) can adopt the trialkylaluminium solution of higher concentration is raw material, improves the throughput of device; 3) solved the crane span structure problem that exists in the reinforced process of direct adding pressed powder effectively; 4) adopt liquid phase reinforced, compare cost of equipment with feeder for solid materials and reduce.The alkylaluminoxane that is obtained by the present invention is good luxuriant, rear transition metal promotor.
Embodiment
The yield of alkylaluminoxane calculates by following formula:
Embodiment 1
Reaction flask adds 500ml4molL through behind sufficient vacuum-nitrogen replacement
-1The TMA toluene solution starts stirring, under the room temperature by shurry pump with 92gAl
2(SO
4)
318H
2The suspension that O and 500ml toluene are mixed with adds in the reaction flask gradually.Reinforced finishing progressively is warmed up to 40 ℃, stirs stopped reaction 13 hours.The elimination solids, removal of solvent under reduced pressure gets white methylaluminoxane solid 59.4g.The yield of purpose product methylaluminoxane is 51.2%.
Get this methylaluminoxane 1.7 gram and 0.05gCp
2ZrCl
2, at 60 ℃, under the 0.8Mpa, made vinyl polymerization 1 hour, get 732 gram polyethylene;
Get this methylaluminoxane 1.7 grams and 0.08g (2,4-diMePh)
2PBIMe
2FeCl
2, at 60 ℃, under the 0.8Mpa, made vinyl polymerization 1 hour, get 608 gram polyethylene.
Comparative Examples 1-a
Reaction flask is through behind sufficient vacuum-nitrogen replacement, with 4.6gAl
2(SO
4)
318H
2O adds in the reaction flask and adds 25ml toluene, starts stirring, adds 50ml2molL by dropping funnel under the room temperature
-1The TMA toluene solution.Reinforced finishing progressively is warmed up to 40 ℃, stirs stopped reaction 13 hours.The elimination solids, removal of solvent under reduced pressure gets white methylaluminoxane solid 1.97g.The yield of methylaluminoxane is 34%.
Get this methylaluminoxane 1.7 gram and 0.05gCp
2ZrCl
2, at 60 ℃, under the 0.8Mpa, made vinyl polymerization 1 hour, get 728 gram polyethylene.
Comparative Examples 1-b
Reaction flask adds 50ml2molL through behind sufficient vacuum-nitrogen replacement
-1The TMA toluene solution starts stirring, under the room temperature by feeder for solid materials with 4.6gAl
2(SO
4)
318H
2The O powder adds in the reaction flask gradually.Reinforced finishing progressively is warmed up to 40 ℃, stirs stopped reaction 13 hours.The elimination solids, removal of solvent under reduced pressure gets white methylaluminoxane solid 3.0g.The yield of purpose product methylaluminoxane is 51.7%.
Get this methylaluminoxane 1.7 gram and 0.05gCp
2ZrCl
2, at 60 ℃, under the 0.8Mpa, made vinyl polymerization 1 hour, get 721 gram polyethylene.
The preparation process of other embodiment and corresponding Comparative Examples thereof is with reference to embodiment 1, Comparative Examples 1-a, Comparative Examples 1-b among the present invention, and it the results are shown in Table 1.
Table 1 embodiment of the invention and reaction result
Embodiment | Aluminum alkyls | Crystalline hydrate | Charge temperature, ℃ | Temperature of reaction, ℃ | The reinforced time, h | The alkylaluminoxane yield, % |
???1 | ??500ml4mol·L -1Trimethyl aluminium | 92gAl 2(SO 4) 3·18H 2O | Room temperature | ??40 | ?2 | ??51.2 |
Contrast 1-a | ??50ml2mol·L -1Trimethyl aluminium | 4.6gAl 2(SO 4) 3·18H 2O | Room temperature | ??40 | ?0.5 | ??34 |
Contrast 1-b | ??50ml2mol·L -1Trimethyl aluminium | 4.6gAl 2(SO 4) 3·18H 2O | Room temperature | ??40 | ?0.5 | ??51.7 |
???2 | ??500ml3.5mol·L -1Triisobutyl aluminium | 80gAl 2(SO 4) 3·18H 2O | Room temperature | ??40 | ?1.8 | ??52.4 |
Contrast 2-a | ??50ml2mol·L -1Triisobutyl aluminium | 4.6gAl 2(SO 4) 3·18H 2O | Room temperature | ??40 | ?0.5 | ??37.8 |
Contrast 2-b | ??50ml2mol·L -1Triisobutyl aluminium | 4.6gAl 2(SO 4) 3·18H 2O | Room temperature | ??40 | ?0.5 | ??52 |
???3 | ??500ml2.5mol·L -1Trimethyl aluminium | 68gMgCl 2·6H 2O | Room temperature | ??40 | ?1.5 | ??49 |
Contrast 3-a | ??50ml2.5mol·L -1Trimethyl aluminium | 6.8gMgCl 2·6H 2O | Room temperature | ??40 | ?0.5 | ??31.7 |
Contrast 3-b | ??50ml2.5mol·L -1Trimethyl aluminium | 6.8gMgCl 2·6H 2O | Room temperature | ??40 | ?0.5 | ??46.9 |
???4 | ??500ml2mol·L -1Triisobutyl aluminium | 46gNa 2CO 3·10H 2O | Room temperature | ??40 | ?1.2 | ??51 |
Contrast 4-a | ??50ml2mol·L -1Triisobutyl aluminium | 4.6gNa 2CO 3·10H 2O | Room temperature | ??40 | ?0.5 | ??34.8 |
Contrast 4-b | ??50ml2mol·L -1Triisobutyl aluminium | 4.6gNa 2CO 3·10H 2O | Room temperature | ??40 | ?0.5 | ??50.3 |
???5 | ??500ml4mol·L -1Trimethyl aluminium | 92gAl 2(SO 4) 3·18H 2O | ??-20 | ??40 | ?1.5 | ??52.2 |
???6 | ??500ml4mol·L -1Trimethyl aluminium | 92gAl 2(SO 4) 3·18H 2O | ??-10 | ??40 | ?1.8 | ??52.6 |
The alkylaluminoxane that the foregoing description obtains helps catalyzed ethylene polymerization, its reaction conditions and the results are shown in Table 2.
The alkylaluminoxane that table 2 the present invention obtains is used for the vinyl polymerization result
Alkylaluminoxane | Metallocene catalyst | Polymerization temperature, ℃ | Polymerization pressure, MPa | Polymerization time, h | Polyethylene production, g |
Embodiment 1 | ???Cp 2ZrCl 2 | ??60 | ????0.8 | ?1 | ???732 |
???(2,4-diMePh) 2PBIMe 2FeCl 2 | ??60 | ????0.8 | ?1 | ???608 | |
Comparative Examples 1-a | ???Cp 2ZrCl 2 | ??60 | ????0.8 | ?1 | ???728 |
Comparative Examples 1-b | ???Cp 2ZrCl 2 | ??60 | ????0.8 | ?1 | ???721 |
Embodiment 2 | ???Cp 2ZrCl 2 | ??60 | ????0.8 | ?1 | ???653 |
???(2,6-diMePh) 2PBIMe 2FeCl 2 | ??60 | ????0.8 | ?1 | ???597 | |
Comparative Examples 2-a | ???Cp 2ZrCl 2 | ??60 | ????0.8 | ?1 | ???644 |
Comparative Examples 2-b | ???Cp 2ZrCl 2 | ??60 | ????0.8 | ?1 | ???665 |
Embodiment 3 | ???Cp 2ZrCl 2 | ??60 | ????0.8 | ?1 | ???703 |
???(2,6-diMePh) 2PBIMe 2FeCl 2 | ??60 | ????0.8 | ?1 | ???680 | |
Comparative Examples 3-a | ???Cp 2ZrCl 2 | ??60 | ????0.8 | ?1 | ???709 |
Comparative Examples 3-b | ???Cp 2ZrCl 2 | ??60 | ????0.8 | ?1 | ???715 |
Embodiment 4 | ???Cp 2ZrCl 2 | ??60 | ????0.8 | ?1 | ???684 |
???(2,6-diMePh) 2PBIMe 2FeCl 2 | ??60 | ????0.8 | ?1 | ???625 | |
Comparative Examples 4-a | ???Cp 2ZrCl 2 | ??60 | ????0.8 | ?1 | ???681 |
Comparative Examples 4-b | ???Cp 2ZrCl 2 | ??60 | ????0.8 | ?1 | ???670 |
Embodiment 5 | ???Cp 2ZrCl 2 | ??60 | ????0.8 | ?1 | ???725 |
???(2,4-diMePh) 2PBIMe 2FeCl 2 | ??60 | ????0.8 | ?1 | ???613 | |
Embodiment 6 | ???Cp 2ZrCl 2 | ??60 | ????0.8 | ?1 | ???738 |
Claims (10)
1, the preparation method of alkylaluminoxane is a raw material with crystalline hydrate and aluminum alkyls, it is characterized in that in the disposable adding reactor of alkyl aluminum solutions; Crystalline hydrate and hydrocarbon organic solvent are mixed with suspension; Under the agitation condition suspension is added in the reactor continuously.
2, preparation method according to claim 1 is characterized in that the adding of suspension realizes by the slurry feed device.
3, preparation method according to claim 2 is characterized in that the adjusting of the input speed of suspension should guarantee that the reactor temperature fluctuation is at ± 5 ℃.
4, preparation method according to claim 3 is characterized in that preparation process is: after reaction unit passes through sufficient inertia displacement, in the disposable adding reactor of alkyl aluminum solutions with First Astronautic Research Institute for Measurement and Test's need; Crystalline hydrate and hydrocarbon organic solvent are mixed with suspension in a preparation still; constantly stir and-30-25 ℃ temperature under, the suspension that will contain crystalline hydrate by a shurry pump adds in the reactor continuously, behind reinforced the finishing, be warming up to 25-60 ℃ and continue to stir 10-30 hour, after reaction finishes after filtration, drying obtains product.
5, according to one of the described preparation method of claim 1 to 4, it is characterized in that crystalline hydrate is MgCl
26H
2O, CuSO
45H
2O, Al
2(SO
4)
318H
2O, LiOHH
2O, Na
2CO
310H
2Wherein a kind of of O.
6,, it is characterized in that crystalline hydrate is Al according to the described preparation method of claim 5
2(SO
4)
318H
2O.
7, the preparation method one of described according to claim 1 to 4 is characterized in that the aluminum alkyls raw material is the trialkylaluminium that meets following formula:
AlR
3
Wherein, R is C
1~C
20Alkyl.
8, preparation method according to claim 7 is characterized in that R is a methyl.
9, preparation method according to claim 7 is characterized in that R is an isobutyl-.
10, the preparation method one of described according to claim 1 to 4 is characterized in that hydrocarbon organic solvent is a toluene.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CNB2004100297175A CN1309724C (en) | 2004-03-24 | 2004-03-24 | Process for preparing alkylaluminoxane |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CNB2004100297175A CN1309724C (en) | 2004-03-24 | 2004-03-24 | Process for preparing alkylaluminoxane |
Publications (2)
Publication Number | Publication Date |
---|---|
CN1673227A true CN1673227A (en) | 2005-09-28 |
CN1309724C CN1309724C (en) | 2007-04-11 |
Family
ID=35046029
Family Applications (1)
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---|---|---|---|
CNB2004100297175A Expired - Fee Related CN1309724C (en) | 2004-03-24 | 2004-03-24 | Process for preparing alkylaluminoxane |
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CN (1) | CN1309724C (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102190677A (en) * | 2010-03-03 | 2011-09-21 | 中国石油天然气股份有限公司 | Atomization synthesis device and application thereof in synthesis of alkylaluminoxane |
CN102286012A (en) * | 2010-06-21 | 2011-12-21 | 中国石油天然气股份有限公司 | Preparation method of alkylaluminoxane solution |
CN101993452B (en) * | 2009-08-12 | 2012-10-17 | 中国石油天然气股份有限公司 | Preparation method of anti-gel methylaluminoxane solution |
CN114456610A (en) * | 2021-12-14 | 2022-05-10 | 长安大学 | Epoxy-terminated low-molecular-weight polyethylene asphalt modifier and preparation method thereof |
CN114716468A (en) * | 2022-03-18 | 2022-07-08 | 浙江石油化工有限公司 | Synthetic method of modified MAO |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5099050A (en) * | 1991-04-15 | 1992-03-24 | Ethyl Corporation | Preparation of aluminoxanes |
US5248801A (en) * | 1992-08-27 | 1993-09-28 | Ethyl Corporation | Preparation of methylaluminoxanes |
CN1058267C (en) * | 1997-04-30 | 2000-11-08 | 中国石油化工总公司 | Method for preparing aluminium alkyl oxide |
PT1115727E (en) * | 1998-09-24 | 2003-04-30 | Akzo Nobel Nv | ALIMINOXAN SYNTHESIS USING A REDUCED QUANTITY OF TRIALQUILALUMINIO COMPOUND |
-
2004
- 2004-03-24 CN CNB2004100297175A patent/CN1309724C/en not_active Expired - Fee Related
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101993452B (en) * | 2009-08-12 | 2012-10-17 | 中国石油天然气股份有限公司 | Preparation method of anti-gel methylaluminoxane solution |
CN102190677A (en) * | 2010-03-03 | 2011-09-21 | 中国石油天然气股份有限公司 | Atomization synthesis device and application thereof in synthesis of alkylaluminoxane |
CN102190677B (en) * | 2010-03-03 | 2013-07-31 | 中国石油天然气股份有限公司 | Atomization synthesis device and application thereof in synthesis of alkylaluminoxane |
CN102286012A (en) * | 2010-06-21 | 2011-12-21 | 中国石油天然气股份有限公司 | Preparation method of alkylaluminoxane solution |
CN102286012B (en) * | 2010-06-21 | 2013-10-16 | 中国石油天然气股份有限公司 | Preparation method of alkylaluminoxane solution |
CN114456610A (en) * | 2021-12-14 | 2022-05-10 | 长安大学 | Epoxy-terminated low-molecular-weight polyethylene asphalt modifier and preparation method thereof |
CN114456610B (en) * | 2021-12-14 | 2022-11-29 | 长安大学 | Epoxy-terminated low-molecular-weight polyethylene asphalt modifier and preparation method thereof |
CN114716468A (en) * | 2022-03-18 | 2022-07-08 | 浙江石油化工有限公司 | Synthetic method of modified MAO |
Also Published As
Publication number | Publication date |
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