CN106632782B - Metallocene transparent film resin and preparation method thereof and film - Google Patents
Metallocene transparent film resin and preparation method thereof and film Download PDFInfo
- Publication number
- CN106632782B CN106632782B CN201510726686.7A CN201510726686A CN106632782B CN 106632782 B CN106632782 B CN 106632782B CN 201510726686 A CN201510726686 A CN 201510726686A CN 106632782 B CN106632782 B CN 106632782B
- Authority
- CN
- China
- Prior art keywords
- metallocene
- resin
- hexene
- catalyst
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000011347 resin Substances 0.000 title claims abstract description 61
- 229920005989 resin Polymers 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims abstract description 75
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000005977 Ethylene Substances 0.000 claims abstract description 34
- 239000001257 hydrogen Substances 0.000 claims abstract description 30
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 30
- 239000012968 metallocene catalyst Substances 0.000 claims abstract description 25
- 239000011261 inert gas Substances 0.000 claims abstract description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract 2
- 238000006116 polymerization reaction Methods 0.000 claims description 42
- 239000012528 membrane Substances 0.000 claims description 32
- 229920000642 polymer Polymers 0.000 claims description 22
- 239000007789 gas Substances 0.000 claims description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 11
- 238000012545 processing Methods 0.000 claims description 9
- 239000003426 co-catalyst Substances 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 125000004429 atom Chemical group 0.000 claims description 6
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims description 5
- 238000012685 gas phase polymerization Methods 0.000 claims description 5
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical group C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 5
- 150000002902 organometallic compounds Chemical class 0.000 claims description 5
- 239000000741 silica gel Substances 0.000 claims description 5
- 229910002027 silica gel Inorganic materials 0.000 claims description 5
- YVSMQHYREUQGRX-UHFFFAOYSA-N 2-ethyloxaluminane Chemical compound CC[Al]1CCCCO1 YVSMQHYREUQGRX-UHFFFAOYSA-N 0.000 claims description 4
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 4
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 claims description 3
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 125000005039 triarylmethyl group Chemical group 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 229910052735 hafnium Inorganic materials 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 20
- 238000009826 distribution Methods 0.000 abstract description 19
- 229920006280 packaging film Polymers 0.000 abstract description 3
- 239000012785 packaging film Substances 0.000 abstract description 3
- 238000004804 winding Methods 0.000 abstract description 3
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- 238000000034 method Methods 0.000 description 35
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 22
- 230000008569 process Effects 0.000 description 19
- 230000000694 effects Effects 0.000 description 15
- 229920001526 metallocene linear low density polyethylene Polymers 0.000 description 15
- 150000002431 hydrogen Chemical class 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 12
- 239000012071 phase Substances 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- 238000005516 engineering process Methods 0.000 description 10
- 239000003446 ligand Substances 0.000 description 9
- 239000000178 monomer Substances 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 8
- 238000002844 melting Methods 0.000 description 8
- 230000008018 melting Effects 0.000 description 8
- 239000000843 powder Substances 0.000 description 7
- 238000012546 transfer Methods 0.000 description 7
- 239000004698 Polyethylene Substances 0.000 description 6
- 238000012512 characterization method Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- -1 polyethylene Polymers 0.000 description 6
- 229920000573 polyethylene Polymers 0.000 description 6
- 125000001424 substituent group Chemical group 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 238000003780 insertion Methods 0.000 description 5
- 230000037431 insertion Effects 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 230000035939 shock Effects 0.000 description 4
- 229960001866 silicon dioxide Drugs 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 238000000137 annealing Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229920000092 linear low density polyethylene Polymers 0.000 description 3
- 239000004707 linear low-density polyethylene Substances 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 235000014121 butter Nutrition 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000003889 chemical engineering Methods 0.000 description 2
- 150000004696 coordination complex Chemical class 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 229910052809 inorganic oxide Inorganic materials 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 150000001455 metallic ions Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 230000003335 steric effect Effects 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 230000001052 transient effect Effects 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NVKDFGCILHNHRS-UHFFFAOYSA-N C1(C=CC=C1)[Au] Chemical compound C1(C=CC=C1)[Au] NVKDFGCILHNHRS-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229920000858 Cyclodextrin Polymers 0.000 description 1
- 241001269238 Data Species 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- 229920000034 Plastomer Polymers 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000012792 core layer Substances 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000009459 flexible packaging Methods 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920006124 polyolefin elastomer Polymers 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
A metallocene transparent film resin is prepared by polymerizing ethylene and 1-hexene, and the molecular chain of the resin has the following structure: the comonomer inserted into the molecular chain is 1-hexene, the branching distribution of the 1-hexene in the molecular chain is discontinuously changed, the distance between the branching points of a part of molecular chain segments is relatively close, the distance between the branching points of a part of molecular chain segments is relatively far, and the average distance between the branching points is 35-40 ethylene sequence lengths; the invention also provides a preparation method thereof, which comprises the following steps: ethylene and 1-hexene are polymerized in a single reactor in the presence of hydrogen, inert gas and a novel metallocene catalyst to prepare the catalyst; the structure enables the resin to show more excellent transparency and impact resistance, can be used in the field of films such as packaging films, winding films and the like with special requirements, and is a practical functional film resin.
Description
Technical field
The present invention relates to a kind of metallocene transparent membrane resin and preparation method thereof and film more particularly to a kind of impact resistances
Type metallocene transparent membrane resin.
Background technique
The transparency of metallocene film is good, and film strength is high, and intensity equalization is good in length and breadth, plays that envelope temperature is low, heat seal strength
Height, heat-sealing temperature range are wide, and impact resistance and comprehensive performance are high, and profile pattern is good, occupies considerablely in packing business
Position can also be applied to blending field mainly for the production of multilayer packing membrane, preservative film, the winding products such as film and agricultural canopy film.
The exploitation of Exxon-Mobil company metallocene catalyst and metallocene PE production are constantly in advanced in the world
Status.Exxon company in 1991 realizes metallocene catalyst for the first time and produces for polyolefin industry metaplasia, produces first cyclopentadienyl
Metal polyethylene (mPE), trade name are " Exact ".Nineteen ninety-five releases Exceed series formally with hexene -1 as comonomer
Metallocene linear low density polyethylene (mLLDPE) product, be mainly used for film applications.Nearest Exxon-Mobil company pushes away again
A kind of new mLLDPE product-Enable mLLDPE is gone out, the product is claimed manufacturer can be helped to keep excellent film
While performance, strengthen the extrusion processability energy of film.This single and unique resin is by film processing properties and high α-alkene
The good physical of hydrocarbon is combined together, and is suitable for a series of flexible packaging film applications.At the beginning of 2004, Exxon-Mobile is again
The marketing of Nexxstar product is dedicated to, to improve the occupation rate of company's mPE product in the market.Nexxstar is a kind of
Three-layer co-extrusion film, two outside layers are mPE materials, and core layer is Escorene Extra High Strength vinyl acetate copolymer.It should
Company combines for 1996 with UCC sets up a co-partnership company-Univation, develops and transfers the possession of Unipol technique using Exxpol
Technology.
Univation company is combined using metallocene catalyst with improved Unipol technique, and development and production go out height
Performance products HPR mLLDPE and easy processing product E ZP mLLDPE.The former processability is than conventional Z-N catalyst production
LLDPE difficulty is big, need to add easy processing auxiliary agent in processing to improve its processing performance；And the latter can not add easy processing and help
Agent or blending can be easy to be processed into product.Univation company is at the beginning of 1996 in Texas 45kt/a LLDPE-
MLLDPE production has been carried out on HDPE device.Sell a patent licensing of the Unipol technology of the said firm in the world is most, at present
It claims to provide more licensings for using metallocene catalyst.The available mixing of newly-built 300kt/a Unipol new equipment is urged
Agent produces two series mLLDPE products of SSC-1 and SSC-2.
The Insite technology that Dow company succeeds in developing produced on 57kt/a solution polymerization device from 1993
After mLLDPE, production capacity has been doubled, and Spain builds 57kt/a device again within 1996.The technology is urged using constrained geometry configuration
Agent produces two kinds of series of products, and one is Affinity polyolefin plastomers, another kind is Elite polyolefin elastomer.Mesh
Preceding Dow company has used metallocene catalyst to develop leading and leading technology transfer strategy, announces and Britain's BPization within 1996
Company joint development gas phase mPE technology, by the way of common technology transfer, by BP company " Innovene " gas-phase polymerization work
Skill produces novel polyethylene in conjunction with Dow company Insite catalyst.
2001, Basell company was proposed its state-of-the-art catalyst system Avant M.In products application exploitation,
Avant M catalyst technology more effectively extends the characteristic of polymer than traditional Z-N catalyst, and Avant M and hydrogen are good
Reactivity, can be not necessarily to peroxide degradation, just obtain melt mass flow rate (MFR) be 12g/10min and 20g/10min
Granular metallocene polymers, the processable production industry of these polymer and health non-woven fabrics.The processability of new product obtains
Improvement, volatility reduction, barrier property are preferable, and filament linear-density reduces.Avant M intrinsic single centre characteristic, can also produce tool
The polymer for having high-purity, high intensity, warpage properties extremely low.Moreover, these products can sterilize, there is the fabulous transparency and light
Damp degree.
The research and development of domestic metallocene-polyolefin start from the beginning of the nineties in last century, and the scientific research of the work is added in recent years
Unit and universities and colleges gradually increase, wherein mainly having China Petroleum Petroleum Chemical Engineering Institute, Research Institute of Petro-Chemical Engineering, the Chinese Academy of Sciences
Chemical institute, Beijing Chemical Research Institute, Zhejiang University etc..And in terms of industrialized production, Daqing Petrochemical Company in 2007
On 90kt/a LLDPE device, pass through transformation first production mLLDPE film product.It is also the external cyclopentadienyl gold of first domestic introduction
The enterprise of metal catalyst technology, the yield of mLLDPE are 20kt/a, and it is HPR series of products that introducing the trade mark, which has 5, main to use
In the high-grade film article of production.There are two the mLLDPE trades mark introduced at present, and industrialization trial production has been carried out on device, real
The precedent that domestic first set is succeeded in developing in low-pressure vapor phase subtraction unit is showed.
However either external metallocene film product or domestic metallocene film product, it is dedicated to developing comprehensive
Can be higher resin dedicated, it is resin dedicated excellent unlike existing LLDPE/LDPE currently on the market in the performance of certain single aspect
It is different, in the product use process, it need to need to develop and guaranteeing to integrate by blending or in conjunction with PP using specific purpose is reached
In performance basis, single performance product more outstanding, to expand the application field of metallocene product.
Summary of the invention
Aiming at the shortcomings in the prior art, the present invention provides a kind of, and the shock resistance type cyclopentadienyl with unique molecular chain structure is golden
Belong to transparent membrane resin, processing film obtained by the resin has the good transparency and impact resistance, and it is special to can be used for having
The film products such as packaging film, the winding film of demand.
The present invention provides a kind of metallocene transparent membrane resin, is made by ethylene and 1- hexene oligomerization, wherein the resin
Strand has the following structure:
Wherein: 1≤n1 < 35；n2≥5；35≤n3<80；n4≥5；The comonomer being inserted on strand is 1- hexene, institute
Branching distribution of the 1- hexene in strand is stated in interruption variation, is intended to the branch point spacing of a part of molecule segment relatively
Closely, relatively far away from, the average headway between branch point is that 35~40 ethylene sequences are long to the branch point spacing of a part of molecule segment
Degree；
Metallocene transparent membrane resin of the present invention, wherein the melting of the metallocene transparent membrane resin refers to
Number ranges preferably from 1.0 ± 0.2g/10min, and density is preferably 0.918 ± 0.002g/cm3, melt index is by standard GB/
T36822-00 is tested under the conditions of 2.16kg, 190 DEG C.
Metallocene transparent membrane resin of the present invention, wherein the average molecular of the metallocene transparent membrane resin
Mass range is preferably 20000~200000, and more preferably 50000~150000；Number average molecular weight ranges preferably from 20000
~60000, more preferably 30000~50000；Weight average molecular mass ranges preferably from 80000~200000, more preferably
100000~150000；Relative molecular mass distribution is preferably 2.0~5.0, and more preferably 2.0~3.5.
Metallocene transparent membrane resin of the present invention, wherein in terms of metallocene transparent membrane resin, the 1- hexene
Molar content is preferably 1.0~5.0%.
The present invention also provides a kind of preparation methods of metallocene transparent membrane resin, are above-mentioned metallocene transparent membrane trees
The preparation method of rouge, includes the following steps:
Ethylene and 1- hexene are gathered in single-reactor in the presence of hydrogen, inert gas and metallocene catalyst
It closes and is made.
The preparation method of metallocene transparent membrane resin of the present invention, wherein the metallocene catalyst preferably by
The metallocene compound and co-catalyst being supported on carrier form.
The preparation method of metallocene transparent membrane resin of the present invention, wherein the metallocene compound is preferably
The organo-metallic compound of non-bridging, structure are as follows:
Wherein: R1Preferably methyl, tert-butyl, R2For tert-butyl, adamantyl or triaryl methyl, Cp' is preferably ring penta 2
Alkenyl or indenyl；The co-catalyst is preferably methylaluminoxane, ethylaluminoxane, butyla-luminoxane, [C6H5NH(CH3)2B
(C6F5)4] or B (C6F5)3；The carrier is preferably inorganic matter carrier or polymer support.
The preparation method of metallocene transparent membrane resin of the present invention, wherein the metallic atom is preferably Ti, Zr
Or Hf；The carrier is preferably silica gel.
Metallocene compound has the characteristics that structure and the easy modulation of performance, by changing transition metal center atom, changes
The substituent group and bridge linkage group of ligand, can be made the catalyst of different symmetry, electronic effect and steric hindrance, reach molecule
The function that design is cut out with molecule.Wherein, non-bridged combined metal catalyst most distinguishing feature is can be realized by modified ligand
Design to catalyst molecule structure.Substituent group and the position of substitution appropriate are selected, the electronic effect and space effect of ligand are changed
It answers, is the key that design catalyst molecule, the excellent catalytic performance of exploitation.
The electronic effect of ligand can be adjusted by the substituent group on luxuriant ring, and the electron substituent group on luxuriant ring can increase
Add the cloud density around luxuriant ring and central metallic ions, thus reduce coordinate bond between olefinic double bonds and metal ion and
Metal ion and carbon atom are formed by the stability of C-M key, are conducive to the insertion of olefinic monomer and the growth of polymeric chain, inhale electricity
Subbase group can reduce rate of chain growth, be allowed to the catalytic activity decline to vinyl polymerization, and the relative molecular weight of polymer also declines；
And the steric effect of substituent group can prevent bicentric inactivation, improve the molecular weight of catalyst activity and resulting polymers, but body
Excessive space is crowded to have the opposite effect to catalyst activity for product.For example, Giannetti etc. uses Cp2ZrMe2/ MAO, Ind2ZrMe2/
MAO, Flu2ZrMe2Tri- kinds of catalyst systems of/MAO compare the catalytic activity of vinyl polymerization, catalytic activity order:
Ind2ZrMe2/MAO>Cp2ZrMe2/MAO>Flu2ZrMe2/ MAO, the reason is that the electron donation of indenes ring is stronger, although and fluorenes ring
Also there is stronger electron donation, but since volume is too big, the steric hindrance of monomer and central metallic ions coordination, intercalation reaction
It is too big, thus its activity is relatively low.
Non-bridged combined metal catalyst of the present invention, the preferably organic gold of non-bridging with particular ligand structure
Belong to compound to devise suitable substituent group and the position of substitution from electronic effect and space steric effect angle, it is enabled to rise
To the effect for improving polymer yield, stabilizing catalyst activity center, inhibition inactivation, and can be to comonomer in polymer point
Distribution in subchain is regulated and controled, and polymer molecular chain is made to have special construction.
The preparation method of metallocene transparent membrane resin of the present invention, wherein described to be polymerized to gas-phase polymerization, polymerization
Temperature is preferably 80~90 DEG C, polymerization pressure be preferably 1.8~2.5MPa, circulation gas velocity is preferably 0.60~0.82m/s, stop
Time is preferably 1~8h.
The preparation method of metallocene transparent membrane resin of the present invention, wherein mole of the 1- hexene and ethylene
Than being preferably 0.015:1~0.03:1；The concentration of hydrogen is preferably 100~1000ppm in reactor.
It is made from above-mentioned metallocene transparent membrane resin processing the present invention also provides a kind of film.
Beneficial effects of the present invention:
Metallocene film resin of the present invention, the branching distribution with comonomer in polyethylene molecular chain is in interruption
The feature of variation, strand are intended to the branch point spacing relative close of a part of molecule segment, the branch of a part of molecule segment
Change point spacing relatively far away from.The unique molecular chain structure makes its crystal habit formed in crystallization process be conducive to improve
The optical property and impact property of product, so that the resin processes Film Haze<8% obtained, hammer falling impact strength>1000g.
In the preparation method of metallocene transparent membrane resin of the present invention, to the control range of each technological parameter into
It has gone refinement, and has proposed the control range of circulation this vital technological parameter of gas velocity.Because metallocene-produced controls
It is required that circulation gas velocity is very big, to reach optimal fluidized state, hot localised points in elimination reaction device, this is also metallocene-produced control
The main difference place of system and traditional mode of production control.The key element of metallocene-produced technology controlling and process is the stream of polymerization reaction
The control of change state, good fluidized state are conducive to Accelerative mass transfer, heat transfer, reduce the generation of hot-spot phenomenon, while good
Fluidized state can ensure that each position of reactor in real time washing away, prevent powder deposition cause sheeting.High gas velocity makes
10% powder recycles in systems, and the powder of circulation forms reactor expanding reach, circulating air pipeline, heat exchanger and distribution grid
It washes away, prevents powder from inhaling wall depositional phenomenon, make the drag reduction of the entire circulatory system, to reach optimal fluidized state and mass transfer
Heat-transfer effect.Therefore, the centralized control of the refinement to polymerization technique state modulator range and fluidized state is most important, then is aided with
It, can be by the metallocene provided of the invention with the non-bridged combined metal catalyst of particular ligand structure selected by the present invention
Transparent membrane resin and its preparation effect reach best.
Detailed description of the invention
Fig. 1-4 is that the molecular chain structure of shock resistance type metallocene transparent membrane resin provided by the invention characterizes spectrogram, with
Wherein it is illustrated for 5 groups of phenograms；
The GPC of Fig. 1 metallocene film resin characterizes spectrogram；
The NMR of Fig. 2 metallocene film resin characterizes spectrogram；
The SSA of Fig. 3 metallocene film resin characterizes spectrogram；
The TREF of Fig. 4 metallocene film resin characterizes spectrogram.
Specific embodiment
Elaborate below to the embodiment of the present invention: the present embodiment carries out under the premise of the technical scheme of the present invention
Implement, gives detailed embodiment and process, but protection scope of the present invention is not limited to following embodiments, following implementation
Test method without specific conditions in example, usually according to normal condition.
Shock resistance type metallocene transparent membrane resin provided by the invention is by ethylene and 1- hexene in hydrogen, indifferent gas
Under body and carried metallocene catalyst effect, polymerization is carried out in single-reactor and is made, product melt index range exists
1.0 ± 0.2g/10min, density range are 0.918 ± 0.002g/cm3.The relative molecular mass range of the resin be 20000~
200000, preferably 50000~150000；Wherein number average molecular weight range is 20000~60000, preferably 30000~50000；
Weight average molecular mass range is 80000~200000, preferably 100000~150000；Relative molecular mass distribution be 2.0~
5.0, preferably 2.0~3.5.
The strand of the metallocene transparent membrane resin has unique texture:
The comonomer being inserted on strand is 1- hexene, and the branching distribution in strand tends in interruption variation
In the branch point spacing relative close of a part of molecule segment, the branch point spacing of a part of molecule segment relatively far away from, branching
Average headway between point is 35~40 ethylene sequence lengths, i.e., the average sequence length of ethylene is 35~40 between branch point.Second
Alkene average sequence length refers to by the average monomer number of ethylene composition sequence alone.
The molecular chain structure of resin of the present invention has apparent heterogencity, and the heterogencity of molecular chain structure includes
Heterogencity caused by heterogencity caused by molecular mass and distribution is different and branch length, content are different from distribution.Branch
Chain content from be distributed caused by heterogencity intermolecular heterogencity and intramolecular branch that again to include intermolecular branching content different
Intramolecular heterogencity caused by chain distribution difference, wherein the non-homogeneity of intramolecular branching, has polyethylene product quality
There is decisive role.
Shock resistance type metallocene transparent membrane resin provided by the invention, the comonomer branching distribution in molecule segment
It is not consistent, there are the branch point spacing relative close of a part of molecule segment, between the branch point of a part of molecule segment
Away from relatively far away from, molecule segment more than such co-monomer content, the end of the chain length between two comonomer insertion points is small, is not easy to tie
The lamellae thickness of crystalline substance, formation is small；The few molecule segment of co-monomer content, the end of the chain length between two comonomer insertion points is big,
Chain is regular, easily crystallizes, and the lamellae thickness of formation is big, and crystal habit determines the mechanical property of product, and this unique crystal grain is total
The mode of depositing makes the metallocene transparent resin show unique physical property.
Comonomer of the present invention be 1- hexene, can also for 1- butylene and its with 1- hexene mixture, be used for
Adjust the density of polyethylene；The hydrogen is used to adjust the molecular weight of polyethylene；The inert gas is nitrogen.
The carried metallocene catalyst is made of the metallocene compound being supported on carrier with co-catalyst.
The metallocene compound is the organo-metallic compound of non-bridging, or the Organometallic compounds of bridging
Object, organo-metallic compound need to be the ligand containing cyclopentadiene containing more than one luxuriant ring ligand, luxuriant ring ligand；The gold
Belonging to is Ti, Zr or Hf, can also be selected from the 4th, 5 and 6 B metals.
The co-catalyst be methylaluminoxane, can also be alkylaluminoxane and boracic cationic co-catalyst, such as
Ethylaluminoxane (EAO), butyla-luminoxane (BAO), [C6H5NH(CH3)2B(C6F5)4]、B(C6F5)3Deng, most effective at present,
The highest co-catalyst of activity is still methylaluminoxane.
The carrier is broadly divided into two class of inorganic matter carrier and polymer support.In inorganic matter carrier, the overwhelming majority is to lean on
Surface hydroxyl is bonded with transient metal complex or organo-aluminum compound, such as SiO2, MAO, molecular sieve, clay etc., only
Small part carrier is directly to be bonded with transient metal complex, such as MgC12.Wherein preferred inorganic oxide, butter.Institute
State inorganic oxide such as aluminium oxide；The butter such as magnesium chloride.The carrier may be high polymer, polymer support
Can be divided into three classes: one kind is the high polymer containing hydroxyl, such as cyclodextrin；Second class is to pass through radiation in inertia Polymer Surface
Different monomers are grafted, its surface is made to contain advantageous-OH ,-NHR ,-CH2COOCH3Equal groups；Third class is in inertia high polymer (as gathered
Styrene) synthesis process in the monomer for containing certain functional group on a small quantity, such as acrylamide is added, so that being formed can be with mistake
Cross the polymer support of metal complex bonding or coordination.
The polymerization includes slurry polymerization, gas-phase polymerization and polymerisation in solution.It is described when being polymerized to gas-phase polymerization, polymerization temperature
It is 80~90 DEG C, preferably 83~86 DEG C；Polymerization pressure is 1.8~2.5MPa, preferably 2.0~2.3MPa；Recycling gas velocity is 0.60
~0.82m/s, preferably 0.64~0.72m/s；Residence time is 1~8h, preferably 4~6h.
In the polymerization process, the molar ratio of 1- hexene and ethylene is 0.015:1~0.03:1, preferably 0.02:1~
0.025:1；The concentration of hydrogen is 100~1000ppm, preferably 300~600ppm in reactor.
The relative molecular mass distribution of metallocene film resin provided by the invention it can be seen from the correlation curve of Fig. 1
Relatively narrow, the relative molecular mass between resin slightly has difference, and strand length homogeneity is preferable, embodies in addition to metallocene product
Feature.
The correlation curve of Fig. 2 shows that out peak position of the comonomer on spectrogram is identical, belongs to identical type, through spectrogram
Each peak ownership and region division, calculate thirdly unit sequence distributed data is shown in Table 1.
1 three unit sequence distribution of table/%
The comparison of three unit sequence distributed datas can be seen that content phase of the comonomer of each group resin in strand
When, but there are heterogencities for distribution of the comonomer in strand.
The heterogencity research to metallocene PE molecular chain structure external at present is concentrated mainly on is smoked point with solution
The cross-fractionation method of grade and rising temperature for dissolving classification and the two characterizes the heterogeneity of metallocene PE, this kind of work
Mainly (such as Du Pont, Fei Lipu company) is carried out in Large-Scale Petrochemical Companies.And in institution of higher learning, such as Akron university of the U.S., then
Mainly with DSC multiple steps of crystallization stage division characterization branching heterogeneity and its influence to crystalline structure and organization.This work is logical
It crosses continuous spontaneous nucleation annealing heat classification (SSA) and temperature rising elution classification (TREF) two kinds of analysis methods is mutually confirmed and mentioned to the present invention
The molecular chain structure of the metallocene film resin of confession is characterized, and characterization spectrogram is shown in Fig. 3, Fig. 4.
SSA characterization curve usually has multiple relatively narrow melting peak, and different melting peaks represents different-thickness platelet
Melting is as a result, the platelet that the chain structural unit for corresponding to different molecular size is formed.This is because cooling down by the 1st melting
After when being raised again to annealing temperature, only the chip of some can be melted, and insoluble part be to crystallize more perfect part, it
Be thicker platelet.In the 2nd annealing temperature, and there is another part platelet not to be melted.In this way, different-thickness
Chip can be graded, and the chip for being formed by different-thickness is related with the structure of strand.In these melting peaks, compared with
The corresponding peak of high-temperature is the preferable molecule of structural regularity, and platelet is thicker；And it is structure that the peak of lower temperature is corresponding
The poor molecule of regularity, platelet is relatively thin, and co-monomer content is relatively high.In this way, the curve to heat up again after SSA is classified
Upper each melting peak substantially just represents the very close molecule of branching content and is formed by crystal.
Each melting peak base on the SSA characterization curve of domestic and international similar resin characterized in retrieving and work in previous literature
This is in normal distribution, and intermediate peak height, both ends peak is low, illustrates that most fractions all compare concentration, but resin of the invention its most
Fraction content at high melt temperature is larger, and is much larger than other each fractions, and fraction is distributed different from other resins, this illustrates the tree
There are a part of fraction, it is formd in crystallization process compared with sheet crystalline substance in rouge, is implicitly present in such a part to verify the resin
Fraction carries out TREF characterization to it, further analyzes the fraction distribution of the resin and crystalline state.
TREF characterization result shows that metallocene film resin provided by the invention is clearly present two kinds of crystal forms, part
Fraction forms the platelet of thicker size in crystallization process, and conclusion and SSA analysis are consistent.It crystallizes the lamellae thickness formed and divides
Branch distribution in subchain is related, and the end of the chain length between two comonomer insertion points is small, is not easy to crystallize, and the platelet of formation is thick
It spends small；The few molecule segment of co-monomer content, the end of the chain length between two comonomer insertion points is big, and chain is regular, easily crystallizes, shape
At lamellae thickness it is big.Therefore the comonomer distribution in the molecule segment of the metallocene resin is not consistent, and there are one
The branch point spacing relative close of moieties segment, the branch point spacing of a part of molecule segment is relatively far away from.
Embodiment 1
Catalyst preparation
The silica-gel carrier of 500g 600 DEG C of activation 4 hours under dry air is added under nitrogen atmosphere, is then added
The toluene solution of the methylaluminoxane of 1250ml 10%, 10g metallocene compound is then added, and (R1 can be methyl, and R2 is tertiary fourth
Base, Cp' are cyclopentadienyl group；Metallic atom M is Ti), after reaction 5 hours, it is filtered, washed drying, it is good to obtain mobility
Powder, i.e. carried metallocene catalyst.
Polymer preparation
By ethylene, 1- hexene, hydrogen, nitrogen and by the above method prepare carried metallocene catalyst be added to list
In one gas-phase fluidized-bed reactor, according to 1- hexene/ethylene molar ratio 0.015:1, density of hydrogen 100ppm, it is in polymerization temperature
80 DEG C, polymerization pressure 1.8MPa, circulation gas velocity is 0.60m/s, carries out polymerization reaction under the process conditions that the residence time is 1h.
Embodiment 2
Catalyst preparation
The silica-gel carrier of 500g 600 DEG C of activation 10 hours under dry air is added under nitrogen atmosphere, is then added
[the C of 1250ml 10%6H5NH(CH3)2B(C6F5)4] toluene solution, then be added 10g metallocene compound (R1 be tertiary fourth
Base, R2 are adamantyl, and Cp' is indenyl；Metallic atom M is Hf), after reaction 5 hours, it is filtered, washed drying, obtains mobility
Good powder, i.e. carried metallocene catalyst.
Polymer preparation
By ethylene, 1- hexene, hydrogen, nitrogen and by the above method prepare carried metallocene catalyst be added to list
In one gas-phase fluidized-bed reactor, according to 1- hexene/ethylene molar ratio 0.018:1, density of hydrogen 200ppm, it is in polymerization temperature
82 DEG C, polymerization pressure 1.9MPa, circulation gas velocity is 0.62m/s, carries out polymerization reaction under the process conditions that the residence time is 2h.
Embodiment 3
Catalyst preparation
The silica-gel carrier of 500g 600 DEG C of activation 8 hours under dry air is added under nitrogen atmosphere, is then added
B (the C of 1250ml 10%6F5)3Toluene solution, then be added 10g metallocene compound (R1 is methyl, and R2 is triaryl methyl,
Cp' is cyclopentadienyl group；Metallic atom M can be Zr), after reaction 5 hours, it is filtered, washed drying, obtains the good powder of mobility
End, i.e. carried metallocene catalyst.
Polymer preparation
By ethylene, 1- hexene, hydrogen, nitrogen and by the above method prepare carried metallocene catalyst be added to list
In one gas-phase fluidized-bed reactor, according to 1- hexene/ethylene molar ratio 0.020:1, density of hydrogen 300ppm, it is in polymerization temperature
83 DEG C, polymerization pressure 2.0MPa, circulation gas velocity is 0.64m/s, carries out polymerization reaction under the process conditions that the residence time is 3h.
Embodiment 4
By ethylene, 1- hexene, hydrogen, nitrogen and the carried metallocene catalyst prepared by 1 the method for embodiment
It is added in single gas-phase fluidized-bed reactor, according to 1- hexene/ethylene molar ratio 0.022:1, density of hydrogen 400ppm, poly-
Close temperature be 84 DEG C, polymerization pressure 2.1MPa, circulation gas velocity be 0.66m/s, the residence time for 3.5h process conditions under into
Row polymerization reaction.
Embodiment 5
By ethylene, 1- hexene, hydrogen, nitrogen and the carried metallocene catalyst prepared by 1 the method for embodiment
It is added in single gas-phase fluidized-bed reactor, according to 1- hexene/ethylene molar ratio 0.024:1, density of hydrogen 500ppm, poly-
Closing temperature is 85 DEG C, polymerization pressure 2.2MPa, and circulation gas velocity is 0.68m/s, is carried out under the process conditions that the residence time is 4h
Polymerization reaction.
Embodiment 6
By ethylene, 1- hexene, hydrogen, nitrogen and the carried metallocene catalyst prepared by 2 the method for embodiment
It is added in single gas-phase fluidized-bed reactor, according to 1- hexene/ethylene molar ratio 0.026:1, density of hydrogen 600ppm, poly-
Close temperature be 86 DEG C, polymerization pressure 2.3MPa, circulation gas velocity be 0.72m/s, the residence time for 4.5h process conditions under into
Row polymerization reaction.
Embodiment 7
By ethylene, 1- hexene, hydrogen, nitrogen and the carried metallocene catalyst prepared by 2 the method for embodiment
It is added in single gas-phase fluidized-bed reactor, according to 1- hexene/ethylene molar ratio 0.027:1, density of hydrogen 700ppm, poly-
Closing temperature is 87 DEG C, polymerization pressure 2.4MPa, and circulation gas velocity is 0.74m/s, is carried out under the process conditions that the residence time is 5h
Polymerization reaction.
Embodiment 8
By ethylene, 1- hexene, hydrogen, nitrogen and the carried metallocene catalyst prepared by 3 the method for embodiment
It is added in single gas-phase fluidized-bed reactor, according to 1- hexene/ethylene molar ratio 0.028:1, density of hydrogen 800ppm, poly-
Closing temperature is 88 DEG C, polymerization pressure 2.5MPa, and circulation gas velocity is 0.76m/s, is carried out under the process conditions that the residence time is 6h
Polymerization reaction.
Embodiment 9
By ethylene, 1- hexene, hydrogen, nitrogen and the carried metallocene catalyst prepared by 3 the method for embodiment
It is added in single gas-phase fluidized-bed reactor, according to 1- hexene/ethylene molar ratio 0.029:1, density of hydrogen 900ppm, poly-
Closing temperature is 89 DEG C, polymerization pressure 2.4MPa, and circulation gas velocity is 0.78m/s, is carried out under the process conditions that the residence time is 7h
Polymerization reaction.
Embodiment 10
By ethylene, 1- hexene, hydrogen, nitrogen and the carried metallocene catalyst prepared by 1 the method for embodiment
It is added in single gas-phase fluidized-bed reactor, according to 1- hexene/ethylene molar ratio 0.030:1, density of hydrogen 1000ppm,
Polymerization temperature be 90 DEG C, polymerization pressure 2.4MPa, circulation gas velocity be 0.82m/s, the residence time for 8h process conditions under into
Row polymerization reaction.
Aggregation test is carried out according to the preparation method of embodiment 1-10, it is poly- to collect the resulting metallocene linear low density of polymerization
Vinyl carries out physical property measurement to it, is as a result listed in table 2.
2 embodiment polymerization product physical property measurement of table
From table 2 it is known that using method provided by the invention, the metallocene film resin being prepared is stretched
Performance, the transparency and impact resistance are well embodied, and the mist degree of film article is respectively less than 8%, and hammer falling impact strength exists
1000g or more, and mostly only need a small amount of comonomer and hydrogen in single-reactor can direct polymerization obtain, polymerize
Operating condition is mild, process flow is short, existing apparatus can be produced through simple transformation, with good application prospect.
Claims (5)
1. a kind of preparation method of metallocene transparent membrane resin, includes the following steps:
Ethylene and 1- hexene carry out polymerization system in the presence of hydrogen, inert gas and metallocene catalyst in single-reactor
?；
The metallocene catalyst is made of the metallocene compound being supported on carrier with co-catalyst；
The metallocene compound is the organo-metallic compound of non-bridging, and structure is as follows:
Wherein: R1For methyl, tert-butyl, R2For tert-butyl, adamantyl or triaryl methyl, Cp' is cyclopentadienyl group or indenyl；
The co-catalyst is methylaluminoxane, ethylaluminoxane, butyla-luminoxane, [C6H5NH(CH3)2B(C6F5)4] or B (C6F5)3；
The carrier is inorganic matter carrier or polymer support.
2. the preparation method of metallocene transparent membrane resin according to claim 1, which is characterized in that the metallic atom
M is Ti, Zr or Hf；The carrier is silica gel.
3. the preparation method of described in any item metallocene transparent membrane resins according to claim 1~2, which is characterized in that institute
State and be polymerized to gas-phase polymerization, polymerization temperature is 80~90 DEG C, polymerization pressure is 1.8~2.5MPa, circulation gas velocity be 0.60~
0.82m/s, residence time are 1~8h.
4. the preparation method of described in any item metallocene transparent membrane resins according to claim 1~2, which is characterized in that institute
The molar ratio for stating 1- hexene and ethylene is 0.015:1~0.03:1；The concentration of hydrogen is 100~1000ppm in reactor.
5. a kind of film is made from the preparation method of the described in any item metallocene transparent membrane resins of Claims 1 to 4
Made from the processing of metallocene transparent membrane resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510726686.7A CN106632782B (en) | 2015-10-30 | 2015-10-30 | Metallocene transparent film resin and preparation method thereof and film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510726686.7A CN106632782B (en) | 2015-10-30 | 2015-10-30 | Metallocene transparent film resin and preparation method thereof and film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106632782A CN106632782A (en) | 2017-05-10 |
| CN106632782B true CN106632782B (en) | 2018-12-25 |
Family
ID=58809162
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510726686.7A Active CN106632782B (en) | 2015-10-30 | 2015-10-30 | Metallocene transparent film resin and preparation method thereof and film |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106632782B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109401025B (en) * | 2017-08-16 | 2021-04-20 | 中国石油化工股份有限公司 | Polyethylene composition for film, preparation method thereof and polymer film |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7119153B2 (en) * | 2004-01-21 | 2006-10-10 | Jensen Michael D | Dual metallocene catalyst for producing film resins with good machine direction (MD) elmendorf tear strength |
| CN102216350A (en) * | 2008-09-25 | 2011-10-12 | 巴塞尔聚烯烃股份有限公司 | Impact resistant LLDPE composition and films made thereof |
| CN103087241A (en) * | 2011-10-31 | 2013-05-08 | 中国石油化工股份有限公司 | Method for preparing metallocene polyethylene |
| US20150126692A1 (en) * | 2013-11-06 | 2015-05-07 | Chevron Phillips Chemical Company Lp | Low Density Polyolefin Resins With Low Molecular Weight and High Molecular Weight Components, and Films Made Therefrom |
-
2015
- 2015-10-30 CN CN201510726686.7A patent/CN106632782B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7119153B2 (en) * | 2004-01-21 | 2006-10-10 | Jensen Michael D | Dual metallocene catalyst for producing film resins with good machine direction (MD) elmendorf tear strength |
| CN102216350A (en) * | 2008-09-25 | 2011-10-12 | 巴塞尔聚烯烃股份有限公司 | Impact resistant LLDPE composition and films made thereof |
| CN103087241A (en) * | 2011-10-31 | 2013-05-08 | 中国石油化工股份有限公司 | Method for preparing metallocene polyethylene |
| US20150126692A1 (en) * | 2013-11-06 | 2015-05-07 | Chevron Phillips Chemical Company Lp | Low Density Polyolefin Resins With Low Molecular Weight and High Molecular Weight Components, and Films Made Therefrom |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106632782A (en) | 2017-05-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101711788B1 (en) | Hybride catalyst compositon, preparation method thereof, and manufactured polyolefin using the same | |
| KR101797890B1 (en) | Hybride catalyst compositon, preparation method thereof, and manufactured polyolefin using the same | |
| ES2301918T3 (en) | ETHYLENE / ALFA-OLEFINE COPOLYMERS AND FILMS MANUFACTURED FROM SUCH COPOLYMERS. | |
| AU2001266220B2 (en) | Heat sealable polyethylene film and method for its preparation | |
| AU2001266220A1 (en) | Heat sealable polyethylene film and method for its preparation | |
| WO2013155946A1 (en) | Novel supported double-center composite polyethylene catalyst and preparation method and use thereof | |
| JP2005533131A5 (en) | ||
| JP2008179825A5 (en) | ||
| CN106459284A (en) | Polyethylene resins | |
| CN113227171A (en) | Catalyst for polymerizing olefin and olefin polymer prepared using the same | |
| CN105294888A (en) | High-crystallinity broad-peak polyethylene resin and preparation method therefor | |
| CN106632782B (en) | Metallocene transparent film resin and preparation method thereof and film | |
| CN106632779B (en) | Metallocene transparent film resin and preparation method thereof and film | |
| CN106632783B (en) | Metallocene transparent film resin and preparation method thereof and film | |
| CN106632778B (en) | Preparation method of metallocene transparent film resin | |
| CN103421138B (en) | A kind of single reactor prepares the poly method of wide/double peak | |
| CN107987201A (en) | Transparent LL DPE film resin and film thereof | |
| CN109265594A (en) | Ethylene-propylene-butylene-terpolymer polypropylene and preparation method and application thereof | |
| CN112552434B (en) | Multi-center supported catalyst and preparation method and application thereof | |
| CN111662498B (en) | Polyolefin composition and preparation method and application thereof | |
| CN106699948A (en) | Method for preparing ultra-low density polyethylene | |
| KR101233881B1 (en) | Linear low density polyethylene resin with excellent hot tack | |
| CN102964482B (en) | Supported non-metallocene catalyst, preparation method and application | |
| CN115667331B (en) | Catalyst system and method for producing polyethylene using the same | |
| CN103304702B (en) | Load type non-metallocene catalyst, its preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |