CN101070364A - Pallution-free preparing method for molecular-weight-distribution controllable ethylene-styrene series copolymer - Google Patents
Pallution-free preparing method for molecular-weight-distribution controllable ethylene-styrene series copolymer Download PDFInfo
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- CN101070364A CN101070364A CN 200710041570 CN200710041570A CN101070364A CN 101070364 A CN101070364 A CN 101070364A CN 200710041570 CN200710041570 CN 200710041570 CN 200710041570 A CN200710041570 A CN 200710041570A CN 101070364 A CN101070364 A CN 101070364A
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Abstract
This invention relates to green preparation method of ethylene/ styrene department copolymer that has controllable molecular weight distribution. The ethylene and styrene department monomer is generated by latices catalytic polymerization at water phase system, the emulsifying agent for emulsion polymerization is anionic emulsifier and unionic emulsifier matching, at 15 to 65 deg C, ethylene keep presure at 0.5 to 6MPa, internal polymerization for 0.5 to 4hours. Ethylene / styrene department copolymer construction and molecular weight distribution is regulated and controlled by stereoscopic effect and electronic effect of group on catalyst benzene ring.
Description
Technical field
The invention belongs to the olefin coordination polymerization field, relate to a kind of Pallution-free preparation method of ethylene of controllable molecular weight distribution.Specifically, the present invention relates to and use the organic transition metal catalyzer to prepare the method that ethylene/styrene is the monomer copolymer emulsion, comprise that mainly the selection of catalyst system, emulsification system and styrenic monomers and ethylene/styrene are that monomeric water catalyzed copolymerization is closed at aqueous phase.
Background technology
For many years, Functionalization of Polyolefins research is the focus (J.Polym.Sci.A:Polym.Chem.2002,40,2842) that people study always, and expectation improves polyolefinic consistency, wettability, dyeability, ventilation property and clinging power, widens its range of application.Because vinylbenzene (S) does not have toxicity to coordination polymerization catalysts, and by number of chemical reaction on the phenyl ring, can introduce functional group easily, vinylbenzene becomes the reactive group that ideal is used for the polyethylene functionalization.Yet the polymerization between ethene (E) and vinylbenzene differs bigger, consistency is relatively poor, all be difficult to synthesize the E/S multipolymer that styrene content surpasses 5% excellent property by free radical polymerization process or traditional Ziegler-Natta catalyst, the product that obtains is ethene and cinnamic homopolymer (Polym.Bull.1988 often, 20,237; Macromolecules, 1994,27,3136).
Afterwards, the development of metallocene and single site catalysts had reignited interest (Macromolecules, 1995,28,2588 of people to ethene, styrene copolymerized research; 1997,30,685; J.Adv.Mater.2000,12,1759; J.Polym.Sci.B:Polym.Phys.2000,38,2976).Up to the present, the report of relevant ethene, styrene copolymerisation is a lot, according to catalyst system feature and reaction conditions, can synthesize random, block, alternately and false random copolymers.In early days, Lin Shangan (polymer journal, 1994,3,282) etc. adopted once that to contain the rare earth titanium be that catalyst system has synthesized ethene-styrene random multipolymer.Pellecchia (Macromolecules, 1996,29,1158) etc. adopted Cp afterwards
*TiBz
3/ B (C
6F
5)
3Catalyst system prepares alternating copolymer; Nineteen ninety-five, the Oliva luxuriant zirconium compounds homogeneous catalysis systems of usefulness such as (Macromolecules, 1995,28,4665) obtains ethene-styrene random multipolymer; Lin Shangan etc. (polymer journal, 1998,6,720) adopt CpTi (OBz)
3/ MAO is that catalyst system synthesizes ethene-styrene block copolymer; (the J.Appl.Polym.Sci.1998 of Dow chemical company, 70,109) adopt the insite technology to synthesize ethene-cinnamic false random copolymers that microstructure can change to amorphous from crystallization, the vinylbenzene massfraction changes (J.Polym.Sci. between 15%-77%, B:Polym.Phy.2002,38,2976).
Ethene and styrene copolymerized used catalyzer nearly all are the early transition metal catalyzer, make it be difficult to use in the aqueous phase emulsion polymerization to the susceptibility of water.In water, carry out the olefin catalytic polymerization, except the distinct advantages of water, also can provide different polymer micro-structurals, prepare some novel materials that known free radical technology can't obtain as reaction medium.Thereby it is very attractive to carry out catalyzed polymerization in water.Compare with early transition metal, late transition metal complex has low oxytropism, basically polarizable medium is had less susceptibility.The research of aqueous phase rear transition metal catalysis in olefine polymerization have remarkable progress (Latetransition metal polymerization catalysis.Wiley-VCH, Weinheim, 2003, chapter7).Recently, (Macromolecules 2002 for Claverie, 35,1513) adopt micro-emulsion technology, use P, complex-catalyzed ethene of O-chelating nickel (II) and styrene emulsion copolymerization can get solid content and be 12.6% copolymer emulsion, cinnamic insertion rate is 73% in the multipolymer, but the molecular weight of the resulting polymkeric substance of this catalyst system lower (Mw=987).
Water as reaction medium have high polarity, do not dissolve each other with most of organic compound, high characteristics such as thermal capacitance, water also is environment amenable security medium simultaneously.Solvent-free reaction is selected in the reaction that relates in the Green Chemistry, or carry out in as reaction medium at water, supercritical co, ionic liquid or perfluoroparaffin, this collaborates at Paul T.Anastas and John C.Warner, there be relevant the summary to introduce in " Green Chemistry, Theory and Practice " by Cambridge University Press's publication in 2000.Waterborne polymeric mainly gets by solution, emulsion and three kinds of water based polymerization reactions of suspension, and industrial various polymer latexs are all got by emulsion polymerization technique.The advantage of letex polymerization comprises that favourable reaction kinetics, safety, environmental protection, composition are controlled, high solids content and high conversion.Letex polymerization generally realizes by heterogeneous free radical reaction, but this polymerization mechanism can't be controlled effectively to the structure of polymkeric substance.The water miscible liquid catalyzed polymerization then can be controlled the composition and the structure of waterborne polymeric, the preparation novel material
Summary of the invention
The invention describes the Pallution-free preparation method of the controlled ethylene of molecular weight.With the nickel metal complexes that contains the bigcatkin willow aldimine is catalyzer, can realize that ethene and styrenic monomers carry out the water copolymerization under 15～65 ℃, 0.5～6MPa ethylene pressure.The structure of the salicylic alidehyde imine neutral nickel catalyst that the present invention is used is as follows:
X＝I(I)，Br(II)，Cl(III)a：R
1＝CH(CH
3)
2；R
2＝CH(CH
3)
2b：R
1＝CH
2CH
3； R
2＝CH
2CH
3c：R
1＝CH
3； R
2＝CH
3d：R
1＝CH
3； R
2＝CH
2CH
3e：R
1＝H； R
2＝H
Promotor is a kind of phosphine thing of taking by force, and this phosphine trapping agent has: Ni (COD)
2, B (C
6F
5)
3The perhaps complex compound of metal rhodium, the structure of rhodium complex is as follows:
IV：R
1＝R
2＝CH
3；V：R
1＝R
2＝Ph；VI：R
1＝CH
3，R
2＝Ph
Ethylene/styrene is that used catalyst system is by a kind of and promotor IV, V among Ia～Ie, IIa～IIe or the IIIa～IIIe or a kind of composition the among the VI in the water catalyzed polymerization, and Ia/IV is the ideal catalyst system.
But synthetic reference [Neutral nickel (II)-based catalys for ethylenepolymerization.Organometallics, 1998, the 17:3149-3151 of catalyzer and promotor; Olefin coordination compounds ofrhodium:the barrier to rotation of coordinated ethylene and the mechanism of olefin exchange.J.Am.Chem.Soc., 1964,86:217-222; Organometallic Chemistry is synthesized handbook. Chemical Industry Press, 1986,30] synthetic, can with the toluene wiring solution-forming, also can with the styrenic monomers wiring solution-forming, or with organic solvent and monomer miscible fluid wiring solution-forming, wherein the mass percent of catalyzer is 10～80%, catalyst levels is that every milliliter of aqueous phase adds 0.1～3 μ mol.
Emulsifying agent in the aqueous phase emulsion catalyzed polymerization is the used emulsifying agent of letex polymerization, and nonionic emulsifier has polyethylene oxide alkyl ethers, polyoxyethylenealkylphenol ether, polyoxyethylene alkyl ester and polyoxyethylene sorbose alkyl oxide; Anionic emulsifier has lipid acid (tetradecanoic acid, palmitinic acid, oleic acid and linolenic acid) salt, alkylbenzene sulfonate such as Sodium dodecylbenzene sulfonate, higher alcohol sulfate salt and alkyl sulfo succinate; Cationic emulsifier has alkyl trimethyl ammonium chloride, dialkylammonium chloride, benzyl ammonium chloride; The sulphonate of copolymerization emulsifying agent such as unsaturated carboxylic acid, α, beta-unsaturated carboxylic acid sulfuric ester and sulfonic group alkyl aryl ether.Mainly be the composite use of negatively charged ion and nonionic emulsifying agent, both ratios are 1: 1～1: 10, the emulsifying agent consumption be in the system water weight 1～10%.
Can be vinylbenzene, alpha-methyl styrene, 4-vinyl toluene, 3-vinyl toluene, 2-methyl styrene and with the styrenic monomers of ethylene copolymerization among the present invention to a 1-chloro-4-methyl-benzene, optimization styrene.
The composition of the ethylene of water miscible liquid catalyzed polymerization and molecular weight distribution can be regulated by substituent volume effect and electronic effect on the phenyl ring in the catalyzer salicylic alidehyde imine nickel complex among the present invention.Cinnamic molar content can be regulated by the sterically hindered selection of aniline substitution in ring base in the catalyzer in the multipolymer, and molar content is 30～100%.The molecular weight of ethylene/styrene multipolymer is 100,000～3,000,000, selects to control the bimodal distribution of molecular weight of copolymer by the power of electron-withdrawing group on the sterically hindered and phenol oxygen ring of aniline substitution in ring base in the catalyzer.The requirement that the high molecular weight ethylene/styrene based copolymer that obtains like this can satisfy actual processing and use.
The temperature of water miscible liquid catalyzed polymerization of the present invention is 15～65 ℃, and the dwell pressure of ethene is 0.5～6MPa in the polyreaction, and polymerization time is 0.5～4 hour.The ethylene/styrene of polymerization gained is that the pH of copolymerization water miscible liquid is 7～9, and the mass percent of solid content is 0.5～30%.
The content of styrenic monomers can be calculated by nmr spectrum in the ethylene that gets by the water miscible liquid catalyzed polymerization, the molecular weight of multipolymer and distribution thereof can be tested and be got by gel permeation chromatograph (GPC), and second-order transition temperature of multipolymer (Tg) and crystallization phases melt temperature (Tm) can be recorded by differential scanning calorimeter (DSC).
The present invention compared with prior art has following obvious advantage: the resulting emulsion system of the present invention has good stability, and deposits several months stable existence still; Obtained the segmented copolymer of ethylene/styrene, and can regulate cinnamic percentage composition in the multipolymer by different catalyst system, the molecular weight distribution of control ethylene/styrene multipolymer is unimodal or bimodal distribution.
Further specify the present invention below by embodiment.
Ethylene/styrene is that the primary process that the water miscible liquid catalyzed copolymerization is closed is: the autoclave that 150mL is equipped with glass-lined is being heated under the situation about vacuumizing more than 50 ℃, keeps 30min, to remove the air and the aqueous vapor that may exist in the autoclave.Under the situation of finding time, be cooled to temperature of reaction again, close vacuum system, charge into ethene or argon gas.In the Schlenk bottle, add a certain amount of nonionic emulsifier polyoxyethylene nonyl phenyl Vinyl Ether OP-10, anionic emulsifier sodium lauryl sulphate SDS and deionized water, applying argon gas bubbling 30min, to remove the air in the solution, and then stirring adding catalyst solution down fast, this mixture is after stirring 5min under 25 ℃ of conditions.It is transferred to take out in the roasting good autoclave, close the autoclave opening for feed, ethene or argon pressure are adjusted to desirable value, under certain temperature, carry out polyreaction.After reaction finishes, close intake valve, the gas in the blowdown system obtains the ethylene/styrene polymkeric substance of controllable molecular weight distribution.
Embodiment
Embodiment 1
Catalyst solution is title complex (Ia) 50 μ mol, take the mixture of the thing of seeing (IV) 25 μ mol and styrene monomer 6mL by force.Polyreaction is carried out 2h under 0.4MPa argon gas state, 50 ℃ of conditions, get milky milk sap.The emulsion that takes a morsel is dry 2h under 120 ℃, and recording solid content is 7.8%.
GPC records Mw:25 * 10 of polystyrene
5, Mw/Mn:4.5; DSC records Tg:108.62 ℃ of polystyrene.
Embodiment 2
Catalyst solution is title complex (Ia) 50 μ mol, take the mixture of the thing of seeing (IV) 25 μ mol and toluene 2mL by force.Polyreaction is carried out 2h, milk sap that must be stable under 5.0MPa ethylene pressure, 50 ℃ of conditions.The emulsion that takes a morsel is dry 2h under 120 ℃, and recording solid content is 0.7%.
DSC records poly Tm:96.65 ℃.
Embodiment 3
Catalyst solution is title complex (Ia) 50 μ mol, take the mixture of the thing of seeing (IV) 25 μ mol, toluene 2mL and vinylbenzene 2mL by force.Polyreaction is carried out 2h, milk sap that must be stable in 5.0MPa ethylene pressure, 50 ℃ of conditions.The emulsion that takes a morsel is dry 2h under 120 ℃, and recording solid content is 3.31%.
1HNMR records that cinnamic percentage composition is 84.70mol% in the multipolymer; GPC records Mw:9.9 * 10 of multipolymer
5, Mw/Mn:11.1; DSC records Tm:96.45 ℃ of multipolymer, and molecular weight of copolymer is distributed with an acromion.
Embodiment 4
Catalyst solution is title complex (Ib) 50 μ mol, take the mixture of the thing of seeing (IV) 25 μ mol, toluene 2mL and vinylbenzene 2mL by force.Polyreaction is carried out 2h, milk sap that must be stable under 5.0MPa ethylene pressure, 50 ℃ of conditions.The emulsion that takes a morsel is dry 2h under 120 ℃, and recording solid content is 2.20%.
1HNMR records that cinnamic percentage composition is 94.63mol% in the multipolymer; GPC records Mw:17 * 10 of multipolymer
5, Mw/Mn:3.8; DSC records Tg:108.03 ℃ of multipolymer, and molecular weight of copolymer is distributed as unimodal distribution.
Embodiment 5
Catalyst solution is title complex (Ic) 50 μ mol, take the mixture of the thing of seeing (IV) 25 μ mol, toluene 2mL and vinylbenzene 2mL by force.Polyreaction is carried out 2h, milk sap that must be stable in 5.0MPa ethylene pressure, 50 ℃ of conditions.The emulsion that takes a morsel is dry 2h under 120 ℃, and recording solid content is 2.33%.
1HNMR records that cinnamic percentage composition is 95.11mol% in the multipolymer; GPC records Mw:8.0 * 10 of multipolymer
5, Mw/Mn:4.2; DSC records Tg:108.27 ℃ of multipolymer, and molecular weight of copolymer is distributed as unimodal.
Embodiment 6
Catalyst solution is title complex (Id) 50 μ mol, take the mixture of the thing of seeing (IV) 25 μ mol, toluene 2mL and vinylbenzene 2mL by force.Polyreaction is carried out 2h, milk sap that must be stable in 5.0MPa ethylene pressure, 50 ℃ of conditions.The emulsion that takes a morsel is dry 2h under 120 ℃, and recording solid content is 2.05%.
1HNMR records that cinnamic percentage composition is 93.74mol% in the multipolymer; GPC records Mw:11 * 10 of multipolymer
5, Mw/Mn:5.3; DSC records Tg:107.28 ℃ of multipolymer, and molecular weight of copolymer is distributed as unimodal.
Embodiment 7
Catalyst solution is title complex (Ie) 50 μ mol, take the mixture of the thing of seeing (IV) 25 μ mol, toluene 2mL and vinylbenzene 2mL by force.Polyreaction is carried out 2h, milk sap that must be stable in 5.0MPa ethylene pressure, 50 ℃ of conditions.The emulsion that takes a morsel is dry 2h under 120 ℃, and recording solid content is 2.43%.
1H NMR records that cinnamic percentage composition is 100mol% in the multipolymer; GPC records Mw:3.1 * 10 of multipolymer
5, Mw/Mn:2.8; DSC records Tg:108.10 ℃ of multipolymer, and molecular weight of copolymer is distributed as unimodal.
Embodiment 8
Catalyst solution is title complex (IIa) 50 μ mol, take the mixture of the thing of seeing (IV) 25 μ mol, toluene 2mL and vinylbenzene 2mL by force.Polyreaction is carried out 2h, milk sap that must be stable in 5.0MPa ethylene pressure, 50 ℃ of conditions.The emulsion that takes a morsel is dry 2h under 120 ℃, and recording solid content is 1.86%.
1H NMR records that cinnamic percentage composition is 52.83mol% in the multipolymer; The molecular weight distribution of multipolymer is shown as bimodal; DSC records Tm:87.28 ℃ of multipolymer.
Embodiment 9
Catalyst solution is title complex (IIIa) 50 μ mol, take the mixture of the thing of seeing (IV) 25 μ mol, toluene 2mL and vinylbenzene 2mL by force.Polyreaction is carried out 2h, milk sap that must be stable in 5.0MPa ethylene pressure, 50 ℃ of conditions.The emulsion that takes a morsel is dry 2h under 120 ℃, and recording solid content is 1.43%.
1H NMR records that cinnamic percentage composition is 47.92mol% in the multipolymer; The molecular weight distribution of multipolymer is shown as bimodal; Mw:9.9 * 10
5, Mw/Mn:11.1; DSC records Tm:89.20 ℃ of multipolymer.
Embodiment 10
Catalyst solution is title complex (Ia) 50 μ mol, promotor Ni (COD)
2The mixture of 100 μ mol, toluene 2mL and vinylbenzene 2mL.Polyreaction is carried out 2h, milk sap that must be stable in 5.0MPa ethylene pressure, 50 ℃ of conditions.The emulsion that takes a morsel is dry 2h under 120 ℃, and recording solid content is 2.03%.
1H NMR records that cinnamic percentage composition is 81.97mol% in the multipolymer; GPC records Mw:4.6 * 10 of multipolymer
5, Mw/Mn:3.4; DSC records Tg:107.12 ℃ of multipolymer.
Embodiment 11
Catalyst solution is title complex (Ia) 50 μ mol, cocatalyst B (C
6F
5)
3The mixture of 100 μ mol, toluene 2mL and vinylbenzene 2mL.Polyreaction is carried out 2h, milk sap that must be stable in 5.0MPa ethylene pressure, 50 ℃ of conditions.The emulsion that takes a morsel is dry 2h under 120 ℃, and recording solid content is 1.87%.
Embodiment 12
Catalyst solution is title complex (Ia) 50 μ mol, take the mixture of the thing of seeing (V) 25 μ mol, toluene 2mL and vinylbenzene 2mL by force.Polyreaction is carried out 2h, milk sap that must be stable in 5.0MPa ethylene pressure, 50 ℃ of conditions.The emulsion that takes a morsel is dry 2h under 120 ℃, and recording solid content is 3.35%.
Embodiment 13
Catalyst solution is title complex (Ia) 50 μ mol, take the mixture of the thing of seeing (VI) 25 μ mol, toluene 2mL and vinylbenzene 2mL by force.Polyreaction is carried out 2h, milk sap that must be stable in 5.0MPa ethylene pressure, 50 ℃ of conditions.The emulsion that takes a morsel is dry 2h under 120 ℃, and recording solid content is 3.28%.
Embodiment 14
Catalyst solution is title complex (Ia) 50 μ mol, take the mixture of the thing of seeing (IV) 25 μ mol, toluene 2mL and alpha-methyl styrene 2mL by force.Polyreaction is carried out 2h, milk sap that must be stable in 5.0MPa ethylene pressure, 50 ℃ of conditions.The emulsion that takes a morsel is dry 2h under 120 ℃, and recording solid content is 3.12%.
Embodiment 15
Catalyst solution is title complex (Ia) 50 μ mol, take the mixture of the thing of seeing (IV) 25 μ mol, toluene 2mL and right-1-chloro-4-methyl-benzene 2mL by force.Polyreaction is carried out 2h, milk sap that must be stable in 5.0MPa ethylene pressure, 50 ℃ of conditions.The emulsion that takes a morsel is dry 2h under 120 ℃, and recording solid content is 2.94%.
Embodiment 16
Catalyst solution is title complex (Ia) 50 μ mol, take the mixture of the thing of seeing (IV) 25 μ mol, toluene 2mL and 4-vinyl toluene 2mL by force.Polyreaction is carried out 2h, milk sap that must be stable in 5.0MPa ethylene pressure, 50 ℃ of conditions.The emulsion that takes a morsel is dry 2h under 120 ℃, and recording solid content is 3.24%.
Embodiment 17
Catalyst solution is title complex (Ia) 50 μ mol, take the mixture of the thing of seeing (IV) 25 μ mol, toluene 2mL and 3-vinyl toluene 2mL by force.Polyreaction is carried out 2h, milk sap that must be stable in 5.0MPa ethylene pressure, 50 ℃ of conditions.The emulsion that takes a morsel is dry 2h under 120 ℃, and recording solid content is 3.20%.
Embodiment 18
Catalyst solution is title complex (Ia) 50 μ mol, take the mixture of the thing of seeing (IV) 25 μ mol, toluene 2mL and 2-methyl styrene 2mL by force.Polyreaction is carried out 2h, milk sap that must be stable in 5.0MPa ethylene pressure, 50 ℃ of conditions.The emulsion that takes a morsel is dry 2h under 120 ℃, and recording solid content is 3.15%.
Claims (12)
1. the Pallution-free preparation method of the ethene-styrene based copolymer of a controllable molecular weight distribution, be in the Schlenk bottle, to add emulsifying agent and deionized water, stir fast and add catalyst solution down, this water miscible liquid is transferred in the anhydrous and oxygen-free autoclave pressure that is connected with ethene or argon gas again, ethene is adjusted to required pressure, under certain temperature, carries out polyreaction and obtain the water multipolymer.
2. the Pallution-free preparation method of the ethene-styrene based copolymer of controllable molecular weight distribution according to claim 1, it is characterized in that adopting the water catalyzed polymerization to prepare the ethene-styrene based copolymer of controllable molecular weight distribution, can be aqueous suspension polymerization, also can aqueous emulsion polymerization.
3. the Pallution-free preparation method of the ethene-styrene based copolymer of controllable molecular weight distribution according to claim 1 is characterized in that water catalyzed polymerization catalyst system therefor is a salicylic alidehyde imine neutral nickel title complex, and its molecular structure is:
X=I wherein, Br or Cl; R
1, R
2=CH (CH
3)
2, CH
2CH
3, CH
3Or H.
4. the Pallution-free preparation method of the ethene-styrene based copolymer of controllable molecular weight distribution according to claim 1 is characterized in that the used promotor of water catalyzed polymerization is Ni (COD)
2, B (C
6F
5)
3The perhaps complex compound of following metal rhodium
R wherein
1, R
2=CH
3Or Ph.
5. the Pallution-free preparation method of the ethene-styrene based copolymer of controllable molecular weight distribution according to claim 1, it is characterized in that the used emulsifying agent of water catalyzed polymerization is an anionic emulsifier and nonionic emulsifier is composite forms, both ratios are 1: 1～1: 10, the emulsifying agent consumption be in the system water weight 1～10%.
6. the Pallution-free preparation method of the ethene-styrene based copolymer of controllable molecular weight distribution according to claim 1 is characterized in that styrenic monomers has vinylbenzene, alpha-methyl styrene, 4-vinyl toluene, 3-vinyl toluene and 2-methyl styrene and right-1-chloro-4-methyl-benzene in the multipolymer.
7. the Pallution-free preparation method of the ethene-styrene based copolymer of controllable molecular weight distribution according to claim 1, it is characterized in that cinnamic molar content can be regulated by the sterically hindered selection of aniline substitution in ring base in the catalyzer in the multipolymer, molar content is 30～100%.
8. the Pallution-free preparation method of the ethene-styrene based copolymer of controllable molecular weight distribution according to claim 1 is characterized in that by aniline substitution in ring base in the catalyzer power of electron-withdrawing group on the sterically hindered and phenol oxygen ring selects to control the bimodal distribution of molecular weight of copolymer.
9. the Pallution-free preparation method of the ethene-styrene based copolymer of controllable molecular weight distribution according to claim 1, the molecular weight that it is characterized in that the ethylene/styrene multipolymer is 100,000～3,000,000.
10. the Pallution-free preparation method of the ethene-styrene based copolymer of controllable molecular weight distribution according to claim 1, the temperature that it is characterized in that the water catalyzed polymerization is 15～65 ℃.
11. the Pallution-free preparation method of the ethene-styrene based copolymer of controllable molecular weight distribution according to claim 1, the time that it is characterized in that the water catalyzed polymerization is 0.5～4 hour.
12. the Pallution-free preparation method of the ethene-styrene based copolymer of controllable molecular weight distribution according to claim 1, the dwell pressure that it is characterized in that ethene in the water catalyzed polymerization is 0.5～6MPa.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102181005A (en) * | 2011-03-28 | 2011-09-14 | 浙江大学宁波理工学院 | Method for preparing styrene-ethylene copolymer by using rare-earth catalysis system |
| CN102690294A (en) * | 2011-03-23 | 2012-09-26 | 中国石油天然气股份有限公司 | 2, 6-diisopropyl aniline salicylaldiminato nickel, and preparation and application thereof |
| CN106317282A (en) * | 2016-08-19 | 2017-01-11 | 东华大学 | Ultrahigh molecular weight ethylene/styrene copolymer and preparation method thereof |
| CN109923131A (en) * | 2016-11-08 | 2019-06-21 | 陶氏环球技术有限责任公司 | Controlled size distribution |
-
2007
- 2007-06-01 CN CN 200710041570 patent/CN101070364A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102690294A (en) * | 2011-03-23 | 2012-09-26 | 中国石油天然气股份有限公司 | 2, 6-diisopropyl aniline salicylaldiminato nickel, and preparation and application thereof |
| CN102181005A (en) * | 2011-03-28 | 2011-09-14 | 浙江大学宁波理工学院 | Method for preparing styrene-ethylene copolymer by using rare-earth catalysis system |
| CN102181005B (en) * | 2011-03-28 | 2013-09-04 | 浙江大学宁波理工学院 | Method for preparing styrene-ethylene copolymer by using rare-earth catalysis system |
| CN106317282A (en) * | 2016-08-19 | 2017-01-11 | 东华大学 | Ultrahigh molecular weight ethylene/styrene copolymer and preparation method thereof |
| CN106317282B (en) * | 2016-08-19 | 2018-10-23 | 东华大学 | The preparation method of ultra-high-molecular-weight polyethylene/styrene copolymer |
| CN109923131A (en) * | 2016-11-08 | 2019-06-21 | 陶氏环球技术有限责任公司 | Controlled size distribution |
| CN109923131B (en) * | 2016-11-08 | 2021-10-26 | Ddp特种电子材料美国有限责任公司 | Controlled particle size distribution |
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