CN107987203A - A kind of preparation method of transparent LLDPE film resins - Google Patents
A kind of preparation method of transparent LLDPE film resins Download PDFInfo
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- CN107987203A CN107987203A CN201610949123.9A CN201610949123A CN107987203A CN 107987203 A CN107987203 A CN 107987203A CN 201610949123 A CN201610949123 A CN 201610949123A CN 107987203 A CN107987203 A CN 107987203A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
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Abstract
The invention discloses a kind of preparation method of transparent LLDPE film resins, this method is ethene and alhpa olefin in the presence of hydrogen, oxygen, inert gas and the supported chrome catalysts of modification, it is polymerize in single-reactor, wherein, polymerization temperature is 60~90 DEG C, polymerization pressure is 1.8~2.5MPa, and the molar ratio of alhpa olefin and ethene is 0.01:1~0.09:1, the molar ratio of hydrogen and ethene is 0.001:1~0.01:1, the concentration of oxygen is 10~140ppb in reactor.There is wide molecular weight distribution using the resin of the method for the present invention production, contain unique short-chain branch and a small amount of long branched chain structure, this structure can improve product shearing sensibility, improve crystal habit, so that the resin shows the more excellent transparency and processability, comprehensive performance well can be used for the film applications such as packaging film, the winding film for having specific demand, be a kind of utility function film resin.
Description
Technical field
The present invention relates to a kind of film resin, more particularly to a kind of transparent easy processing LLDPE film resins.
Background technology
LLDPE (linear low density polyethylene) film resins are mainly for the production of agricultural film, packaging film, in recent years as China is light
Work export business develops, film-grade LLDPE consumption steady growths, 4,800,000 tons of LLDPE film materials Apparent con- sumption in 2015,
High intensity, high transparency LLDPE demands are main to substitute in the market LDPE material at 200,000 tons/year.
LLDPE is the copolymer of ethene and alpha-olefin, and introducing 'alpha '-olefin monomers makes polymer contain a considerable amount of side chains,
These side chains different in size directly affect the performance of polymer.LLDPE strands are in linear, have highly branched short branch
Chain, therefore crystallinity is low, its performance such as stress cracking resistance, tensile strength, tearing toughness and hammer falling impact strength etc. with
For LDPE compared to being greatly improved, appearance is similar to LDPE, but the transparency is slightly poorer, and processing performance is not so good as LDPE.
In blown film production process, during resin is from molten state to glassy transition, in a certain temperature less than fusing point
Start to crystallize in the range of degree, since nucleus is to randomly generate, spherocrystal is grown under field conditions (factors), causes spherulite size big,
And skewness.On LLDPE film surface light reflection occurs for large-sized spherocrystal, makes the transparency variation of film, further, since brilliant
Area has differences with amorphous area refraction index, causes interface that irregular light scattering and reflection occurs, so that LLDPE resins
Transparent poor-performing.Therefore, by controlling the difference of the crystal property of LLDPE resins, reduction crystalline phase area and amorphous phase section,
The transparency of LLDPE film can be improved.
In terms of processing performance, LLDPE is poor to the sensitiveness of stress, i.e., under the shearing force of extrusion processing, melt
Viscosity is much higher, it is necessary to high torque, higher melt temperature and die pressure, and melt fracture easily occurs；But in film bubble drawing-off
When do not harden.In addition LLDPE melt strengths are poor, impacted when film bubble cools down intolerant to high speed cold wind, and stability difference is, it is necessary to strengthen
The design of cooling vane.
Existing LLDPE products are transparent and processing performance in order to improve, and synthesize high transparency easy processing LLDPE in recent years and have been subjected to
To the concern of numerous researchers.High transparency easy processing high performance resin product is developed on the basis of common LLDPE, its point
Son containing long and short-chain branch and has the advantages of wider molecular weight distribution, product combines LDPE and LLDPE at the same time, both has
Have the desirable physical mechanical performance of LLDPE products, and had the processing of LDPE products and transparent performance concurrently, intensity, stability,
Low-shrinkage, splitting resistance etc. have the advantages of other products are irreplaceable, are widely used in various film articles, can be
Process, can more be substituted in terminal market traditional on the process equipment (mainly film blowing device) of existing LDPE
LDPE。
The molecular structure difference of LLDPE and LDPE is shown：LLDPE does not have or few long-chain branch, and conventional film is used
The polymer that LLDPE is narrow Mw/Mn (Mw/Mn is 3~4).The chain length of LLDPE short-chain branch depends on the type of comonomer.Branch
Chain number depends on combined co-monomer content.Only alpha-olefinic copolymerization of the carbon number more than or equal to 4 could effectively
The close of chain molecule is upset to pile up, so that reducing density obtains LLDPE, while produces the tie molecule for connecting different crystalline regions,
Improve the toughness and intensity of polymer.So film be all ethene with LLDPE with l- butylene, l- hexenes, l- octenes or 3- methyl-
The copolymer of amylene.LLDPE crystalline states depend not only on the type of comonomer, additionally depend on comonomer in the polymer
Distribution and the frequency that is distributed in strand.Under same isodensity, the fusing point of LLDPE is than 10~15 DEG C of LDPE high.Use high power
Polarized light microscope observing, a diameter of 10~20 μm of LLDPE spherocrystals, and only 2~3 μm of LDPE spherocrystals diameter.
Design LLDPE polymer chains have three kinds of Basic Ways to improve transparent and processing performance：Design Catalyst Production length
Branched structure, bimodal or broad molecular weight distribution structure, import the terpolymer that the 3rd (or 4th) plants comonomer
(or quadripolymer), auxiliary agent is added during post-processing.
Mainly realized at present by improving traditional catalyst, the most noticeable technique being related to, including Montell public
SPHERILENE (ter-polymers) technique of department, LLDPE (wide MWD) technique of Phillips companies, Univation companies
The bimodal techniques of UNIPOL, and BORSTAR (bimodal) techniques of Borealis companies and NOVA chemical companies are advanced recently
SCLAIRTECH (bimodal) technique.With metallocene/single-site catalyst systems, also industrially produce easier to process
LLDPE.Long-chain branch (LCB) the INSITE techniques of these new technologies including Dow companies, EVOLUE (bimodal) techniques of three wells and
The mPACT techniques of Phillips.
LLDPE is still difficult to all substitution LDPE at present, and main cause is also the long chain branched contained in LDPE.Institute
Long chain branching is called, refers to that the molecular weight of side chain is more than the minimum entanglement molecular weight of strand.For polyethylene, minimum is tangled
Chain is about 1000g/mol.Long-chain branched polyethylene (LCB-PE) has excellent rheological property and high intensity, is other structures
What polyethylene cannot compare.When the branch lengths of LCB-PE exceed the critical chain length of polyethylene, side chain can strengthen strand
Between entanglement, thus show high melt strength at low shear rates；Side chain can reduce the hydrodynamics of polyethylene again
Volume, this causes to show high shear shinning behavior at high shear rates.These features are especially high to polythene material
Processing modified the having very important significance of melt viscosity polyethylene (such as metallocene PE, High molecular weight polyethylene).
In addition, long-chain branched polyethylene is obviously improved the performance of polyethylene film.Therefore, LCB-PE is subject to scientific circles and work for a long time
The concern of industry, in recent years, LCB-PE are still one of research hotspot of polyolefin field.LCB-PE belongs to high added value production
Product, develop the developing goal that the product meets China's polyolefin industry.LCBPE structures prepared by distinct methods are variant, but always
Apparently, its rheological property can be improved.The LCB-PE using effects of what spline structure are best, with which type of synthesis side
It is minimum that method prepares LCB-PE costsThese problems all do not solve also very well at present.Therefore it is continuous to attract people for this problem
Go to explore, new, more suitably synthetic method is found, to reach extensive, the inexpensive target for preparing optimum structure LCB-PE.
It is the transparent easy processing metallocene catalyst of the second generation and chromium-based catalysts that long branched chain structure catalyst can be produced at present,
But since the protection limitation of each major company can not obtain catalyst.
The maximum feature of bimodal polyethylene is exactly that two peak values are presented in its molecular weight distribution.Due to adding for polyvinyl resin
Work and mechanical property are conflicting, and improving molecular weight can make product have more preferable mechanical property, but can make again at the same time
Resin becomes difficult to process.And bimodal polyethylene is two parts of high molecular weight and low molecular weight because being made of, its high molecular weight
To ensure physical mechanical strength, low molecular weight part can just efficiently solve polyethylene to improve processing performance for part
The problem of machinability and conflicting mechanical property of resin, enable the rigidity of material and toughness to reach good balance.Cause
And there is the intensity of higher with the product that bimodal polyethylene resins produce than the product of common grade production of resins, it is preferably anti-to answer
Power cracking performance, more preferably moulding processability.Bimodal polyethylene is also just because of having these excellent performances and having more preferable city
Field prospect.
Bimodal LLDPE not only has physically better performance, but also also longer service life than unimodal LLDPE.It is bimodal
The distribution of molecular weight and structure, can be such that its properties balanced can improves.The product appears in European market earliest, external
It is widely used to produce various everyday articles, such as film, flexible packing material and blowing.
At present, China's only oil of SPC can produce such product.Its low melt index produced with the northern bimodal PE technologies of star
LLDPE is easy to process, and rigidity is good.Compared with ldpe film material, LLDPE film material processing performances are similar, but the film being processed into
Tearing strength higher, thus film thickness can be reduced.Representative bimodal LLDPE purposes includes：Industrial gasket, heavy bag
Dress, refrigeration package, compression packing, agricultural film etc..
Production bimodal products are mainly reactor tandem process and single reactor double-peak catalyst, anti-for vapor phase method list
Answer device device can not realize bimodal products with existing single catalyst, can not be obtained properly additionally, due to the protection limitation of each major company
Double-peak catalyst.
The wide distribution relative molecular mass product of production mainly applies chromium-based catalysts, and chromium-based catalysts can be produced and drawn money on credit
Chain structure improves rheological property and improves processability.Binary polymerization technique has due to the introducing of Third monomer compared with binary copolymerization
There is more highly branched chain, a lot of unfolded side chain passes through the amorphous area between crystal layer to enter other crystalline regions, makes to exist largely between crystal layer
Tie molecule, so as to improve the mechanical property of polymer；These side chains contain more long-chain branch at the same time, improve rheological property
Improve processing performance.In addition, Third monomer, which adds, has crystal size certain influence, also have to the product transparency and necessarily carry
It is high.
Dow Chemical Company uses Insite technologies, synthesized MWD it is narrow, have a small amount of long-chain branch metallocene PE (mPE).
Wherein macromonomer can be closed from ethylene homo during β-H elimination reactions or to monomer shift chain transfer reaction generate.
Using constrained geometry technology (CGCT), long-chain branch, high metric are controlledly introduced in polymer strands short-chain branch structure
Whole short-chain branch and limited amount long-chain branch make the existing excellent physical property of polymer have good processing performance again.
The Enable of Exxon mobil chemical companies of the U.S.TMMPE series of products.This unique resin has concurrently outstanding
The good physical of film processing properties and high-carbon alpha-olefin.Enable mPE are ethene -1- hexene copolymers, and density is
0.920~0.927g/cm3, melt flow rate (MFR) (MFR) is 0.3~1.0g/10min.The product is in LLDPE and LDPE equipment
On all there is extremely wide operability, changeable processing conditions can be tackled.
Univation companies utilize NEW TYPE OF COMPOSITE carrier metallocene catalyst, gas-phase polymerization, in single high-pressure reactor
It is middle to synthesize the chain second generation LLDPE that draws money on credit, there are of a relatively high melt flow ratio and melt strength (MS), have and be equal to LLDPE/
The processing performance of LDPE blends [w (LDPE) is 20%~30%].
Borealis companies use the bimodal LLDPE of Borstar technique productions, and MWD is narrow, and extract is few, and processability is good, with biography
System HDPE is compared, and has the stretch modulus of higher and oil resistance, the transparency and the better tightness of impact strength and uniqueness.
The impact strength of the Evolue LLDPE copolymers of Mitsui chemical company production, anti-caking, low-temperature heat-sealing
Property, mouldability etc. are superior to conventional LLDPE.Evolue LLDPE are synthesized by double gas-phase fluidized-bed reactors, its average molecular matter
Amount is in bimodal distribution, and processing performance is close with LDPE, existing LDPE film blowing devices can be used to process.
CN1338477A describes a kind of method for preparing LLDPE carrier catalysis system and preparing LLDPE, and this method carries
A kind of bifunctional catalyst system for ethylene synthase linear low density polyethylene is supplied, dimerization catalyst is alkoxy chemical combination
Thing catalyst, catalyst for copolymerization are made of supported metallocene catalyst, are co-catalyst in alkyl aluminum or boron compound,
Directly make to be copolymerized on the spot while ethylene dimerization in same polymerization system, generate LLDPE.
CN1124034A describes a kind of LLDPE polymeric compositions of high working property, based on linear low density polyethylene
(LLDPE) polymeric compositions, said composition include the ethene of (A) 75~95% (weight) and the copolymer of alpha-olefin, (B) 5
The copolymer of the propylene of~25% (weight), ethene and alpha-olefin.Copolymer (B) be characterized in having in dimethylbenzene it is higher not
Dissolubility.The polymeric compositions of the present invention, compared with conventional type LLDPE, processability is improved with mechanical performance.Polymerisation is
Carried out in the fluid bed or mechanical stirring reactor of two or more series connection, the order of each reactor is unlimited, and what is used urges
Agent is identical.
CN1145082A describes a kind of LLDPE resins blend, a kind of LLDPE prepared with metalloscene catalyst and low
Density high pressure polyethylene resin blend is extrudable to be made the film for improving optical property and impact strength.
CN1183105A describes a kind of method for producing LLDPE polymer, and this method is one kind by slurry reaction
In device in the presence of ethylene rolymerization catalyst polymerising ethylene and a small amount of C3-C6The ethylene copolymer of alpha-olefin generation particle form
Method, according to the present invention, is aggregated in by using alumoxane activated metalloscene catalyst, in propane diluent and carries out.
CN1217343A describes a kind of synthesis LLDPE bimetallic catalysts and preparation method thereof, and this method is related to one kind
For the bimetallic catalyst system by ethylene synthase linear low density polyethylene, dimerization catalyst is by tungsten owner catalyst and halogen
Substituted alkyl aluminum cocatalyst forms, and catalyst for copolymerization is made of Titanium series catalyst and alkyl aluminum, pair of both catalyst composition
Metal catalyst system, can directly make to be copolymerized on the spot while ethylene dimerization in same polymerization system, generation
LLDPE, and Copolymerization activity is very high.
Ye Zhibin etc. using in-situ polymerization catalyst system and catalyzing synthesizing ethylene -1- hexene copolymers length is branched and rheology
During performance study, using catalyst for oligomerization (η5-C5H4CMe2C6H5)TiCl3/ modified methylaluminoxane (MMAO) and copolymerization
Catalyst [(η5-C5Me4)SiMe2(tBuN)]TiCl2/ MMAO successfully synthesizes LLDPE.Small amplitude dynamic vibration test result is in
Reveal the typical rheological property of long chain branched polymers (enhancing of such as Zero shear viscosity, shear thinning improvement dynamic modulus raising,
Complicated thermorheologic property), absolutely prove that there are long-chain branch in synthesized LLDPE.
Galland etc. has found, Fe catalyst can synthesize Me and approach by Fe in the long branched PE researchs of Zr catalyst synthesis
The alpha-olefin of 2000g/mol.The alpha-olefin carries the PE of long chain branch on Zr activation points with vinyl polymerization, synthesis, wherein, it is long
Brached chain amount accounts for more than the 40% of branched total amount.
Farley etc. utilizes transition metal type catalysts system, synthesizes LLDPE using gas-phase fluidized-bed single reactor, compares
The metallocene product E XCEED of narrow MWD, under similar MFR, comonomer type and density, which can be relatively low
Motor load, under higher output and the head pressure of reduction by curtain coating or inflation film manufacturing procedure, be easier
Ground extrusion film product.Under similar MFR, which compares EXCEEDTMResin has the weight average molecular weight of higher and wider
MWD, film splitting performance is bidirectional balanced (vertically and horizontally ratio is generally higher than 0.9), and dart impact strength is more than 19.7g/um.
Michie etc. utilizes in-situ blending method, using double-reactor, uses the bimodal LLDPE of Mg/Li Catalyst Productions.In height
The polyolefin produced in relative molecular mass reactor has a low MFR (0.01-30.00g/10min), density for 0.86~
0.94g/cm3；The MFR of the polyolefin produced in low relative molecular mass reactor is 5~30g/10min, density for 0.900~
0.979g/cm3.The film prepared with this not only has good stretching, shock resistance and puncture resistance, but also significantly improves
The problem of conventional LLDPE processing film is difficult.
Myhre etc. uses the shrinkable film of wide/double peak LLDPE (MWD is 10~35) productions and traditional shrinkable film phase
Than with more preferable mechanical property and shrinkage.In contraction process, low relative molecular mass component in bimodal LLDPE
Crystalline rate is more than high relative molecular mass component, makes the effective contraction distortion of film, improves the mechanical property of film.Forming a film
Cheng Zhong, the height entanglement of polymeric chain enhance the rigidity of film and form the height-oriented structure for improving shrinkage.
Myhre etc. has invented a kind of bimodal PE composition breathable films.Bimodal PE components for film provide high intensity and
Excellent processing performance, and can prepare with light basis weight (25g/m2Or it is lower) film.Wherein, low relative molecular mass group
Dividing can help to improve processing performance, and MFR is 0.1~4.0g/10min, density about 0.918~0.935g/cm3；It is opposite point high
Protonatomic mass component is with certain mechanical property.High relative molecular mass component is ethene and C4-Cl0The copolymer of alkene,
Co-monomer content with higher.For under given low relative molecular mass constituent content and component proportion, producing
Bimodal PE there is desired MFR and density.
Cheng song etc. introduce long chain branch using relatively low Electron-beam irradiation in LLDPE, via radiation after
LLDPE in have few or be not crosslinked, MWD broadens.At low shear rates, long branched LLDPE melts degree of killing increase；In height
Under elongation at break, melt strength increase.Long-chain branch makes the LLDPE after irradiation have the rheology rows such as resistance to relaxation and strain hardening
To improve the processing performance (such as blown film, foaming and hollow injection) of LLDPE.LLDPE grafting processing can also be improved
The processing performance of LLDPE.
Yao Zhanhai etc. connects the rheology row of skill LLDPE (LLDPE-g-AA) using capillary rheometer research acrylic acid (AA)
For.Under shearing force, the apparent viscosity of LLDPE-g-AA is smaller than pure LLDPE；The apparent viscosity of LLDPE-g-AA is with AA's
Increase and reduce, illustrate that the AA being grafted on LLDPE strands plays the role of in-lubricant；The stretching of graft product is strong
Degree, Young's modulus and elongation at break and pure LLDPE are essentially identical.
Dynamar be developed by 3M Tai Liang companies, a series of polymer processing aids based on fluoropolymer
Product, can be used to improve the processability of resin, and not influence the physical mechanical property of matrix resin.At present, it has been successfully applied to
In the process of LLDPE resins.
CN200910232637.2 is related to a kind of special compound additive of polyethylene film with high tranparency and low density, is gathered with high pressure
Ethene is carrier, by 25%~30% silica opening agent, 5%~15% organosilicon glidant, 2~8% silicone actives
Crosslinking agent, 1~10% organosilicon antioxidant and surplus high pressure polyethylene resin preheat ball milling by being stirred, at 75~85 DEG C
It is scattered, finally at 140 DEG C~170 DEG C, by particle obtained by dual-screw pelletizer extruding pelletization, add this composite assistant system
Into low-density polyethylene film, tasteless, high transparency, has good physiological security, high Kekelé structure count, smoothness and fabulous
Resistance to migration.Be especially applicable to food, medicine, business card, identity card overlay film and advertisement packaging etc. to film have high transparency,
High security and the field of high Kekelé structure count requirement.
CN200710064958.7 is related to a kind of preparation method of high-transparent linear low density polyethylene, more particularly to a kind of
The method that high-transparent linear low density polyethylene is prepared using Acrylate polyethylene glycol monoester as transparent agent.Transparent agent third is synthesized first
Olefin(e) acid polyethylene glycol monoesters, Acrylate polyethylene glycol monoester be with acrylic acid, polyethylene glycol, resorcinol, p-methyl benzenesulfonic acid, β-
(3 ', 5 '-di-t-butyl -4 '-hydroxy phenyl) propylene octadecyl ester, distearyl pentaerythritol phosphite are raw material；Synthesis increases
After saturating agent, by transparent agent Acrylate polyethylene glycol monoester and linear low density polyethylene by weight 0.1~1.5: 100,160
DEG C~210 DEG C of melt blending extrusions, high-transparent linear low density polyethylene resin is made.
Above using the long branched structure of design Catalyst Production, bimodal or broad molecular weight distribution structure, the is imported
Three (or four) plant the terpolymer (or quadripolymer) of comonomer, added during post-processing auxiliary agent blending and modifying,
The technologies such as chemical modification produce transparent easy processing product, in product quality homogeneity, production cost and product comprehensive performance
There is certain deficiency.Lack at present a kind of with the transparent of wide molecular weight distribution, unique short-chain branch structure and a small amount of long branched chain structure
Easy processing Membranous Foundations resin and preparation method, film made from resin processing with the good transparency and processability,
The film resin that comprehensive performance is good, quality is homogeneous, production cost is low.
The content of the invention
The present invention provides a kind of preparation method of transparent LLDPE film resins, the resin produced with this method has width
Molecular weight distribution, unique short-chain branch structure and a small amount of long branched chain structure, have the good transparency and processability, available for there is spy
The packaging film of different demand, wind the film products such as film.
A kind of preparation method of transparent LLDPE film resins provided by the invention, this method are ethene and alpha-olefin in hydrogen
In the presence of gas, oxygen, inert gas and the supported chrome catalysts of modification, it is polymerize in single-reactor, wherein, gather
It is 60~90 DEG C to close temperature, and polymerization pressure be 1.8~2.5MPa, and the molar ratio of alpha-olefin and ethene is 0.01:1~0.09:1,
The molar ratio of hydrogen and ethene is 0.001:1~0.01:1, the concentration of oxygen is 10~140ppb in reactor.The polymerization bag
Slurry polymerization, gas-phase polymerization and polymerisation in solution are included, the inert gas is nitrogen, and effect mainly maintains pressure in reactor.
The preparation method of transparent LLDPE film resins of the present invention, wherein, the alpha-olefin is thin in transparent LLDPE
Molar content is 0.5~5.0% in film resin.
The preparation method of transparent LLDPE film resins of the present invention, wherein, the supported chrome catalysts refer to chromium
Compound loaded in supported catalyst, the chromium compound is chromium oxide, and the carrier is silica, aluminium oxide, oxygen
Change zirconium or thorium oxide.
Transparent LLDPE film resins of the present invention, wherein, the supported chrome catalysts of the modification are supported chromes
Catalyst obtained from catalyst is modified by aluminium, titanium, fluorine and vanadium.
The preparation method of transparent LLDPE film resins of the present invention, wherein, the alpha-olefin for 1- butylene and/or
1- hexenes.
The preparation method of transparent LLDPE film resins of the present invention, wherein, the molar ratio of the alpha-olefin and ethene
For 0.03:1~0.06:1.
The preparation method of transparent LLDPE film resins of the present invention, wherein, the molar ratio of the hydrogen and ethene is
0.003:1~0.006:1.
The preparation method of transparent LLDPE film resins of the present invention, wherein, the concentration of oxygen is in the reactor
30~90ppb.
The preparation method of transparent LLDPE film resins of the present invention, wherein, it is described to be polymerized to gas phase single-reactor
Polymerization, polymerization temperature are 80~90 DEG C, and preferably 83~86 DEG C, polymerization pressure is 1.8~2.5MPa, preferably 2.0~2.3MPa, is followed
Ring gas velocity is 0.60~0.82m/s, preferably 0.64~0.74m/s, and the residence time is 1~8h, preferably 4~6h.
Transparent LLDPE film resins of the present invention, wherein, in the supported chrome catalysts of the modification, chromium, vanadium,
The total load amount of titanium and aluminium is 0.01wt%~15wt%, the preferably 0.05wt%~8wt% of total catalyst weight, more preferably
1wt%~6wt%, wherein, the molar ratio of chromium and vanadium is 0.1:0.9~0.9:0.1, preferably 0.25:0.75~0.75:0.25,
More preferably 0.4:0.6~0.6:0.4, the molar ratio of chromium and titanium is 0.1:0.9~0.9:0.1, preferably 0.25:0.75~0.75:
0.25, more preferably 0.4:0.6~0.6:0.4.The load capacity of fluorine is 0.01wt%~10wt% of total catalyst weight, preferably
0.05wt%~8wt%, more preferably 1wt%~6wt%, wherein, the molar ratio of chromium and fluorine is 0.1:0.9~0.9:0.1, preferably
0.25:0.75~0.75:0.25, more preferably 0.4:0.6~0.6:0.4.
Beneficial effects of the present invention：
1st, present invention used catalyst when preparing film resin is that the chromium system being modified by aluminium, titanium, fluorine and vanadium urges
Agent, and the strictly content of active ingredient contained by control, aluminium is modified so that catalysis generates High molecular weight polyethylene in catalyst
Avtive spot increases, while inhibits the avtive spot of catalysis generation low molecular weight polyethylene in catalyst so that polymerisation
It is more likely to the polyethylene of generation high molecular weight；Titanium is modified the activity for not only adding avtive spot in catalyst so that poly- second
Alkene molecular weight improves, and can also reduce insertion of the side chain in low molecular weight part；Fluorine richness substantially increases low-temperature activation
Catalyst activity, and can improve alpha-olefin insertion and reduce low molecular polyethylene content；Vanadium is modified same
Sample can suppress the generation of low molecular weight polyethylene, increase the content of High molecular weight polyethylene.
2nd, the present invention when preparing film resin except using in addition to general molecular weight regulator hydrogen, also using oxygen as
The inhibitor (poisonous substance) of catalyst adds system, and properties of product are adjusted in the stringent addition for controlling oxygen.
3rd, film resin produced by the present invention is due to special wide molecular weight distribution, unique short-chain branch structure and a small amount of
Long branched chain structure, makes crystallization refinement, crystallinity reduction transparency good, compared with the market conventional LLDPE mist degree<15%, this film tree
Fat mist degree<13%.
Brief description of the drawings
Fig. 1 is that the GPC of the transparent LLDPE film resins of the present invention characterizes spectrogram；
Wherein, Mw represents weight average molecular weight, and W represents quality；
Fig. 2 is that the NMR of the transparent LLDPE film resins of the present invention characterizes spectrogram；
Fig. 3 is that the SSA of the transparent LLDPE film resins of the present invention characterizes spectrogram；
Fig. 4 is that the TREF of the transparent LLDPE film resins of the present invention characterizes spectrogram；
Fig. 5 is the processing torque diagram of the transparent LLDPE film resins of the present invention；
Fig. 6 is the rotation rheogram of transparent LLDPE film resins.
Wherein, a curves represent 2 test result of embodiment, and b curves represent 4 test result of embodiment, and c curves, which represent, to be implemented
5 test result of example, d curves represent 6 test result of embodiment, and e curves represent 8 test result of embodiment.
Embodiment
The present invention is specifically described below by embodiment, it is necessary to which indicated herein is that the present embodiment is served only for pair
The present invention is further detailed, it is impossible to is interpreted as limiting the scope of the invention, field personnel can be according to upper
State present disclosure and make some corresponding nonessential modifications and adaptations.
The preparation of catalyst：
Using Al2O3, the porous inorganic carrier SiO that is modified of titanium and F2(carrier can also use zirconium oxide or oxidation to carrier
Thorium replacement), by the method for substep or co-impregnation, vanadium source is immersed in porous inorganic carrier SiO2On silica-gel carrier, institute is obtained
The catalyst that need to be modified.The porous silica silica gel that 10-15g or so is modified through Ti, Al, F, V is immersed in alkali formula chromic acetate
Aqueous solution, wherein chromium load capacity be total catalyst weight 0.1-1wt%, continuously stir 3-8 it is small when after, heat up drying, then will
The silica-gel carrier for being loaded with alkali formula chromic acetate carries out high-temperature roasting in fluid bed, and the mechanical water of carrier is removed in low-temperature zone,
The hydroxyl of Silica Surface is removed under 500 DEG C of -900 DEG C of high temperature sections, is kept for 5-8 hour in this high temperature section, is finally protected in nitrogen
Under, Temperature fall cooling, is made catalyst modified needed for the present invention.
The melt index scope of the resin as made from the method for the invention is 0.3~1.0g/10min, density 0.916
~0.922g/cm3；The relative molecular mass scope of the resin is 6000~280000, and number is with respect to molecular weight range
6000~60000, average weight-molecular mass scope is 80000~280000, and relative molecular mass distribution is 9.0~15.0.
The transparent easy processing film resin as made from the method for the invention, melt flow ratio are 50~90；It is 30 to process moment of torsion
~60Nm.
Embodiment 1
Ethene, 1- butylene, hydrogen, oxygen, nitrogen and the supported chrome series catalysts of modification are added to single gas phase
In fluidized-bed reactor, according to 1- butylene/ethylene molar ratio 0.01:1, the molar ratio of hydrogen and ethene is 0.001, oxygen concentration
140ppb, is 80 DEG C, polymerization pressure 1.8MPa in polymerization temperature, circulation gas velocity is 0.60m/s, catalyst charge 2g/
H, residence time are to carry out polymerisation under the process conditions of 2h.
Embodiment 2
Ethene, 1- butylene, hydrogen, oxygen, nitrogen and the supported chrome series catalysts of modification are added to single gas phase
In fluidized-bed reactor, according to 1- butylene/ethylene molar ratio 0.024:1, the molar ratio of hydrogen and ethene is 0.002, and oxygen is dense
120ppb is spent, is 82 DEG C, polymerization pressure 1.9MPa in polymerization temperature, circulation gas velocity is 0.62m/s, and catalyst charge is
2g/h, residence time are to carry out polymerisation under the process conditions of 2h.
Embodiment 3
Ethene, 1- butylene, hydrogen, oxygen, nitrogen and the supported chrome series catalysts of modification are added to single gas phase
In fluidized-bed reactor, according to 1- butylene/ethylene molar ratio 0.028:1, the molar ratio of hydrogen and ethene is 0.003, and oxygen is dense
80ppb is spent, is 83 DEG C, polymerization pressure 2.0MPa in polymerization temperature, circulation gas velocity is 0.64m/s, catalyst charge 2g/
H, residence time are to carry out polymerisation under the process conditions of 3h.
Embodiment 4
Ethene, 1- butylene and 1- hexenes, hydrogen, oxygen, nitrogen and the supported chrome of modification series catalysts are added to
In single gas-phase fluidized-bed reactor, according to 1- butylene and 1- hexenes/ethylene molar ratio 0.03:1,1- butylene/1- hexenes mole
Than for 1：1, the molar ratio of hydrogen and ethene is 0.004, oxygen concentration 60ppb, is 84 DEG C in polymerization temperature, polymerization pressure is
2.1MPa, circulation gas velocity are 0.66m/s, and catalyst charge 2g/h, the residence time is to be polymerize under the process conditions of 4h
Reaction.
Embodiment 5
Ethene, 1- butylene and 1- hexenes, hydrogen, oxygen, nitrogen and the supported chrome of modification series catalysts are added to
In single gas-phase fluidized-bed reactor, according to 1- butylene and 1- hexenes/ethylene molar ratio 0.035:1,1- butylene/1- hexenes mole
Than for 1：1, the molar ratio of hydrogen and ethene is 0.005, oxygen concentration 50ppb, is 85 DEG C in polymerization temperature, polymerization pressure is
2.2MPa, circulation gas velocity are 0.68m/s, and catalyst charge 2g/h, the residence time is to be gathered under the process conditions of 4.5h
Close reaction.
Embodiment 6
Ethene, 1- butylene and 1- hexenes, hydrogen, oxygen, nitrogen and the supported chrome of modification series catalysts are added to
In single gas-phase fluidized-bed reactor, according to 1- butylene and 1- hexenes/ethylene molar ratio 0.035:1,1- butylene/1- hexenes mole
Than for 1：1.5, the molar ratio of hydrogen and ethene is 0.006, oxygen concentration 40ppb, is 86 DEG C in polymerization temperature, polymerization pressure is
2.3MPa, circulation gas velocity are 0.72m/s, and catalyst charge 2g/h, the residence time is to be gathered under the process conditions of 4.8h
Close reaction.
Embodiment 7
Ethene, 1- butylene and 1- hexenes, hydrogen, oxygen, nitrogen and the supported chrome of modification series catalysts are added to
In single gas-phase fluidized-bed reactor, according to 1- butylene and 1- hexenes/ethylene molar ratio 0.04:1,1- butylene/1- hexenes mole
Than for 1：2, the molar ratio of hydrogen and ethene is 0.007, oxygen concentration 30ppb, is 87 DEG C in polymerization temperature, polymerization pressure is
2.4MPa, circulation gas velocity are 0.74m/s, and catalyst charge 2g/h, the residence time is to be polymerize under the process conditions of 5h
Reaction.
Embodiment 8
Ethene, 1- hexenes, hydrogen, oxygen, nitrogen and the supported chrome series catalysts of modification are added to single gas phase
In fluidized-bed reactor, according to 1- hexenes/ethylene molar ratio 0.05:1, the molar ratio of hydrogen and ethene is 0.008, oxygen concentration
20ppb, is 88 DEG C, polymerization pressure 2.5MPa in polymerization temperature, and circulation gas velocity is 0.76m/s, catalyst charge 2g/h,
Residence time is to carry out polymerisation under the process conditions of 6h.
Embodiment 9
Ethene, 1- hexenes, hydrogen, oxygen, nitrogen and the supported chrome series catalysts of modification are added to single gas phase
In fluidized-bed reactor, according to 1- hexenes/ethylene molar ratio 0.055:1, the molar ratio of hydrogen and ethene is 0.008, and oxygen is dense
10ppb is spent, is 89 DEG C, polymerization pressure 2.4MPa in polymerization temperature, circulation gas velocity is 0.78m/s, catalyst charge 2g/
H, residence time are to carry out polymerisation under the process conditions of 7h.
Embodiment 10
Ethene, 1- hexenes, hydrogen, oxygen, nitrogen and the supported chrome series catalysts of modification are added to single gas phase
In fluidized-bed reactor, according to 1- hexenes/ethylene molar ratio 0.06:1, the molar ratio of hydrogen and ethene is 0.01, in polymerization temperature
Spend for 90 DEG C, polymerization pressure 2.4MPa, circulation gas velocity is 0.82m/s, and catalyst charge 2g/h, the residence time is 8h's
Polymerisation is carried out under process conditions.
Aggregation test is carried out according to the preparation method of embodiment 1-10, the transparent easy processing line style for collecting polymerization gained is low close
Polyvinyl resin is spent, physical property measurement is carried out to it, the results are shown in table 1.
1 embodiment 1-10 polymerization product physical property measurements of table
The present invention characterizes the transparent easy processing film resin that wherein prepared by 5 embodiments, and characterization collection of illustrative plates such as Fig. 1~
Shown in 6.
The average molecular matter of transparent easy processing film resin provided by the invention it can be seen from the GPC correlation curves of Fig. 1
Amount distribution is wider, and the relative molecular mass difference of interlaminar resin is big, and strand length homogeneity is bad, embodies easy processing product
Wide molecular weight distribution the characteristics of.
The nuclear magnetic spectrogram of Fig. 2 shows that peak position is identical for copolymer resins going out on spectrogram, illustrates it with identical type
Functional group, through each peak ownership of spectrogram and region division, calculates thirdly unit sequence distributed data is shown in Table 2.(three unit sequences point
Cloth is used for characterizing the distribution situation of comonomer, wherein, E represents vinyl group, and B represents butylene group, and H represents hexene group,
The construction unit of one butylene of insertion among two ethene is represented if EBE)
2 three unit sequence distribution of table/%
The contrast of three unit sequence distributed datas can be seen that content of the comonomer of each embodiment resin in strand
Quite.
The heterogencity research to transparent easy processing polyethylene molecule chain structure external at present is concentrated mainly on is taken out with solution
Classification and rising temperature for dissolving classification and both and cross-fractionation method characterize the heterogeneity of transparent easy processing polyethylene,
This kind of work mainly carries out (such as Du Pont, Fei Lipu companies) in Large-Scale Petrochemical Companies.And in institution of higher learning, such as U.S.'s Akron
University, then mainly characterize branched heterogeneity and its influence to crystalline structure and organization with DSC multiple steps of crystallization stage division.This hair
Bright is to be classified (TREF) two kinds of analysis methods by continuous spontaneous nucleation annealing heat classification (SSA) and temperature rising elution mutually to confirm to this
The molecular chain structure for inventing the transparent easy processing film resin provided is characterized, and characterization spectrogram is shown in Fig. 3~Fig. 4.
SSA characterization curves usually have multiple relatively narrow melting peak, and different melting peaks represents different-thickness platelet
Melting is as a result, the platelet that the chain structure unit that correspond to different molecular size is formed.This is because cool down by the 1st melting
After when being raised again to annealing temperature, only the chip of some can be melted, insoluble part 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 of the different-thickness formed 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, its platelet is thicker；And it is structure that the peak of lower temperature is corresponding
The poor molecule of regularity, its platelet is relatively thin, and co-monomer content is of a relatively high.In this way, the curve to heat up again after SSA is classified
Upper each melting peak substantially just represents the crystal that the very close molecule of branching content is formed.
Each melting peak base on the SSA characterization curves of domestic and international similar resin characterized in retrieving and work in previous literature
This be in normal distribution, and middle peak height, both ends peak is low, illustrate that overwhelming majority fractions all compare concentration, but resin of the invention its most
Fraction content at high melt temperature is larger (such as Fig. 3), and is much larger than other each fractions, and fraction is distributed different from other resins, this
Illustrate the heterogencity of molecular chain structure in the resin, to verify that the resin is implicitly present in so a part of fraction, it is carried out
TREF is characterized, and further the fraction distribution of the resin and crystalline state are analyzed.
Referring to Fig. 4, TREF characterization results are shown, transparent easy processing film resin provided by the invention is clearly present two kinds of knots
Crystalline form, this illustrates the heterogencity of molecular chain structure in the resin, and conclusion is consistent with SSA analyses.It is thick to crystallize the platelet formed
Degree is related with the side chain distribution in strand, and the end of the chain length between two comonomer insertion points is small to be not easy to crystallize, formation
Lamellae thickness is small；The few molecule segment of co-monomer content, the big chain of end of the chain length between two comonomer insertion points is regular, Yi Jie
Crystalline substance, the lamellae thickness of formation are big.Therefore the comonomer distribution in the molecule segment of the transparent easy processing resin is not consistent
, there are the branch point spacing relative close of a part of molecule segment, the branch point spacing of a part of molecule segment is relatively far away from.
The long branched chain structure of polymer can influence the processing performance of polymer strongly, and the melt for for example improving polymer glues
Degree, enhanced drawing hardening and shear shinning behavior etc..But the levels of long chain branching in polymer is often very low, cause some tradition
Polymer structure characterization method failure.For example GPC-MALIS cannot detect the long-chain branch of low content；NMR cannot be distinguished by short branch
Chain and long-chain branch.And the long branched chain structure of the rheological properties confrontation low content of polymer is very sensitive, so rheology test becomes
Characterize the important method of polymeric long branched structure.Fig. 5 is the torque curve that the present invention contains a small amount of long-chain branch sample, and processing is turned round
Square is 30-60Nm, and less than the processing moment of torsion of no long-chain branch product, illustrating the formation of long-chain branch is changed LLDPE processing performances
It is kind, and levels of long chain branching is higher, and the processing performance of product is better, this is to saving energy consumption and reducing the pair in extrusion
Reaction is all highly beneficial.Fig. 6 is the rotation rheogram of the transparent easy processing film resin of the present invention, and sample occurs in low frequency ranges
Shear shinning phenomenon, i.e., they to shear it is more sensitive, this also further illustrates sample, and there are long-chain branch.
Moreover, can also be learnt from table 2, polyvinyl resin prepared by the present invention have wide molecular weight distribution (10~
12), having less processing moment of torsion (32~48Nm), (conventional LLDPE processes 50~90Nm of moment of torsion significantly more in the prior art
Reduce), larger melt flow ratio (59.2~70.7), this make it that polyvinyl resin stability and product quality of the present invention are better, production
The comprehensive performance of product is better.
The heterogencity of molecular chain structure include heterogencity caused by molecular mass and distribution difference and side chain length,
Heterogencity caused by content is different from distribution, it has a significant impact polyethylene product integrated information tool.This hair as shown in Table 2
The polyvinyl resin of bright preparation has a wide molecular weight distribution (10~12), and due to unique short-chain branch and draw money on credit on a small quantity
Chain structure, makes many unfolded side chains pass through the amorphous area between crystal layer to enter other crystalline regions, makes there is substantial amounts of system between crystal layer
Band molecule, so as to improve the mechanical property of polymer；These side chains contain more long-chain branch at the same time, improve rheological property and carry
High processing performance.In addition, the special construction has crystal size certain influence, also improve, produce to the product transparency
The comprehensive performance of product greatly improves.
Certainly, the present invention can also have other various embodiments, ripe in the case of without departing substantially from spirit of the invention and its essence
Various corresponding changes and deformation, but these corresponding changes and deformation can be made according to the present invention by knowing those skilled in the art
The protection domain of the claims in the present invention should all be belonged to.
Claims (10)
- A kind of 1. preparation method of transparent LLDPE film resins, it is characterised in that this method be ethene with alpha-olefin hydrogen, In the presence of oxygen, inert gas and the supported chrome catalysts of modification, it is polymerize in single-reactor, wherein, polymerization Temperature is 60~90 DEG C, and polymerization pressure be 1.8~2.5MPa, and the molar ratio of alpha-olefin and ethene is 0.01:1~0.09:1, hydrogen The molar ratio of gas and ethene is 0.001:1~0.01:1, the concentration of oxygen is 10~140ppb in reactor.
- 2. the preparation method of transparent LLDPE film resins according to claim 1, it is characterised in that the alpha-olefin exists Molar content is 0.5~5.0% in transparent LLDPE film resins.
- 3. the preparation method of transparent LLDPE film resins according to claim 1, it is characterised in that the supported chrome Catalyst refers to that chromium compound is supported on supported catalyst, and the chromium compound is chromium oxide, and the carrier is titanium dioxide Silicon, aluminium oxide, zirconium oxide or thorium oxide.
- 4. transparent LLDPE film resins according to claim 1, it is characterised in that the supported chrome catalysis of the modification Agent is catalyst obtained from supported chrome catalysts are modified by aluminium, titanium, fluorine and vanadium.
- 5. the preparation method of transparent LLDPE film resins according to claim 1, it is characterised in that the alpha-olefin is 1- butylene and/or 1- hexenes.
- 6. the preparation method of transparent LLDPE film resins according to claim 1, it is characterised in that the alpha-olefin with The molar ratio of ethene is 0.03:1~0.06:1.
- 7. the preparation method of transparent LLDPE film resins according to claim 1, it is characterised in that the hydrogen and second The molar ratio of alkene is 0.003:1~0.006:1.
- 8. the preparation method of transparent LLDPE film resins according to claim 1, it is characterised in that in the reactor The concentration of oxygen is 30~90ppb.
- 9. the preparation method of transparent LLDPE film resins according to claim 1, it is characterised in that described to be polymerized to gas Phase single-reactor polymerize, polymerization temperature be 80~90 DEG C, polymerization pressure be 1.8~2.5MPa, circulation gas velocity be 0.60~ 0.82m/s, residence time are 1~8h.
- 10. the preparation method of transparent LLDPE film resins according to claim 4, it is characterised in that the modification is born In load type chrome catalysts, chromium, vanadium, 0.01wt%~15wt% that the total load amount of titanium and aluminium is total catalyst weight, wherein, chromium Molar ratio with vanadium is 0.1:0.9~0.9:0.1, the molar ratio of chromium and titanium is 0.1:0.9~0.9:0.1；The load capacity of fluorine is 0.01wt%~10wt% of total catalyst weight, wherein, the molar ratio of chromium and fluorine is 0.1:0.9~0.9:0.1.
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|---|---|---|---|---|
| CN109016761A (en) * | 2018-08-10 | 2018-12-18 | 顺丰速运有限公司 | Plastic foil and courier bag |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2013137866A (en) * | 2011-01-14 | 2015-02-20 | В.Р.Грейс Энд Ко.-Конн. | METHOD FOR PRODUCING MODIFIED METALLOCENES CATALYST, PRODUCED CATALYST AND ITS APPLICATION |
| CN105199021A (en) * | 2014-06-06 | 2015-12-30 | 中国石油化工股份有限公司 | Titanium fluoride modified load type chrome alum double-active center catalyst and preparation method thereof |
-
2016
- 2016-10-26 CN CN201610949123.9A patent/CN107987203A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2013137866A (en) * | 2011-01-14 | 2015-02-20 | В.Р.Грейс Энд Ко.-Конн. | METHOD FOR PRODUCING MODIFIED METALLOCENES CATALYST, PRODUCED CATALYST AND ITS APPLICATION |
| CN105199021A (en) * | 2014-06-06 | 2015-12-30 | 中国石油化工股份有限公司 | Titanium fluoride modified load type chrome alum double-active center catalyst and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 赵兴龙等: "铬系催化剂在气相法聚乙烯中试装置的稳定运行研究", 《合成树脂及塑料》 * |
| 辽宁省石油化学工业厅: "《辽宁化工产品大全》", 31 December 1994, 沈阳：辽宁科学技术出版社 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109016761A (en) * | 2018-08-10 | 2018-12-18 | 顺丰速运有限公司 | Plastic foil and courier bag |
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