CN103087238B - Propylene random copolymer - Google Patents
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- CN103087238B CN103087238B CN201110336505.1A CN201110336505A CN103087238B CN 103087238 B CN103087238 B CN 103087238B CN 201110336505 A CN201110336505 A CN 201110336505A CN 103087238 B CN103087238 B CN 103087238B
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Abstract
The invention relates to a propylene-butylene-1 random copolymer. The butylenes-1 content in the propylene-butylene-1 random copolymer is 1-6mol%, and the relative butylene-1 dispersion degree determined through nuclear magnetic resonance is greater than 98.5%. The propylene-butylene-1 random copolymer has a high relative butylene-1 dispersion degree, simultaneously has a good transparency and a good heat resistance, is more suitable for packaging foods which can be eaten after heating, has a low room-temperature xylene soluble substance content, can avoid the pollution of precipitated soluble substances to a packaged object when the random copolymer is used as a packaging material, and has more advantages when the random copolymer is used as a food and medicine packaging material.
Description
Technical field
The present invention relates to a kind of random copolymer of propylene and preparation method thereof, particularly a kind of propene-1-butene-1 random copolymers and preparation method thereof.
Background technology
Random copolymer of propylene to be often referred in polypropylene molecular chain the polymkeric substance that the randomly a small amount of 'alpha '-olefin monomers of copolymerization (being usually no more than 15wt%) obtains, monomer due to copolymerization destroys the regularity of propylene monomer arrangement on molecular chain, because this reducing fusing point and the degree of crystallinity of acrylic resin, lower fusing point can for the manufacture of the film etc. more easily sealed, lower degree of crystallinity improves the transparency of material, but the increase of comonomer consumption can improve solubles content, non-crystallizable under solvend normal temperature, easily migrate to the surface of goods, thus affect processing and the application of product, reduction fusing point and degree of crystallinity also can make the resistance toheat of material decline usually.In addition, use more comonomer, also can increase difficulty to polymerization process, as occurred, sticky still, caking, residual monomer are difficult to remove clean etc., the alpha-olefin of butene-1 that especially boiling point is higher or more carbon number.
Summary of the invention
Butene-1 is as in comonomer and propylene random polymerization process, if butene-1 to be inserted in polypropylene molecular chain with single monomeric unit more, be lessly inserted in polypropylene molecular chain with continuously arranged monomeric unit (as BB bis-unit or more monomeric unit continuously), the dispersion coefficient MD of observed butene-1 monomer on molecular chain
observed (B)with desirable random dispersion coefficient MD
random (B)ratio larger, this ratio is exactly the relative distribution degree MD of butene-1
relative (B), its calculation formula is as follows:
(2)MD
random(B)＝(1-[B])×100
Wherein, [PB] represents the monomeric unit number of the butene-1 that molecular chain is connected with propylene monomer; [B] represents the monomeric unit number that on molecular chain, butene-1 is total; MD
observed (B), MD
random (B)and MD
relative (B)unit be %.
The present inventor finds through test, and improve the relative distribution degree of butene-1, material reaches the same transparency, and thermotolerance can be better.
Therefore, the object of this invention is to provide a kind of propene-1-butene-1 random copolymers, its butene-1 relative distribution degree be high, good heat resistance, simultaneously room temperature xylene soluble content is low.
Another object of the present invention is to provide a kind of preparation method of propene-1-butene-1 random copolymers, the method can prepare very high and propene-1-butene-1 random copolymers that room temperature xylene soluble content is low of butene-1 relative distribution degree, and polymerization process is easy, can avoid occurring that sticky still, caking, residual monomer are difficult to remove the situations such as clean.
Propene-1-butene-1 random copolymers butene-1 content of the present invention is 1-6mol%, preferred 3-6mol%; It is greater than 98.5% according to the butene-1 relative distribution degree of nuclear magnetic resonance method determination, is preferably greater than 99.0%.
Butene-1 content in propene-1-butene-1 random copolymers can affect polyacrylic degree of crystallinity, butene-1 content is higher, polypropylene crystallinity is lower, the transparency of material is better, but butene-1 content is too high, can bring the excessive of room temperature xylene soluble part, butene-1 content is too low, and degree of crystallinity can be caused too high, the impact transparency, it is 1-6mol%, more preferably 3-6mol% that the present invention optimizes butene-1 content through test.
As previously mentioned, improve the butene-1 relative distribution degree of propene-1-butene-1 random copolymers, thermotolerance can be better when reaching the same transparency for material.The butene-1 relative distribution degree of propene-1-butene-1 random copolymers of the present invention can reach and be greater than 98.5%, is preferably greater than 99.0%.
Propene-1-butene-1 random copolymers of the present invention is owing to having very high butene-1 relative distribution degree, and its heat-drawn wire can reach more than 90 DEG C, preferably more than 95 DEG C.
In random copolymer of propylene, the increase of comonomer consumption can improve room temperature xylene soluble content, and butene-1 is no exception as comonomer.Generally speaking, room temperature xylene soluble content is higher, may cause directly can not contacting with food, medicine etc. as wrapping material, otherwise may pollute packaging article.But, in the butene-1 content range of propene-1-butene-1 random copolymers of the present invention, room temperature xylene soluble content along with the increase of butene-1 content slow.
Specifically, the xylene soluble content of propene-1-butene-1 random copolymers of the present invention under room temperature (about 25 DEG C) is lower than following fit line:
Y＝0.77+0.252X
Wherein: Y is the weight percentage (if 5wt%, Y=5) of room temperature xylene soluble part; X is the molar content (if 5mol%, X=5) of butene-1 in propene-1-butene-1 random copolymers.
When the reduction of room temperature xylene soluble content will make propene-1-butene-1 random copolymers of the present invention be used for food container, food safety will be higher; For processing film, not easily roll banding, metal plating difficult drop-off.
Usually control the processibility of polymkeric substance by controlling melting index, preferably, propene-1-butene-1 random copolymers of the present invention 230 DEG C, the melting index that measures under 2.16kg load is 0.5-50g/10min, preferred 2-30g/10min.
Propene-1-butene-1 random copolymers of the present invention adopts the molecular weight distributing index Mw/Mn of the sign molecular weight distribution of GPC test to be 3.5-8, preferred 3.5-6.Molecular weight distributing index is too little, means narrow molecular weight distribution, thus Drawing abillity is deteriorated; Molecular weight distributing index is too large, means that molecular weight distribution is wide, then may the transparency of material influenced and reduce.
The butene-1 relative distribution degree of propene-1-butene-1 random copolymers of the present invention is high, have the better transparency and thermotolerance concurrently, be more suitable for packing the food needing heating edible, there is lower room temperature xylene soluble content, more can avoid the pollution of precipitation to packing material of room temperature solvend for wrapping material, for when food and medical packaging material advantageously.
The preparation method of propene-1-butene-1 random copolymers of the present invention comprises: under selected Z-N (Ziegler-Natta) catalyzer exists, under polymerization temperature and suitable hydrogen content, by regulating the add-on of comonomer butene-1 in reactor, the copolymerization carrying out propylene and butene-1 obtains propene-1-butene-1 random copolymers.
Z-N (Ziegler-Natta) catalyzer selected by the present invention refers to the catalyzer described in Chinese patent CN85100997A, CN1258680A, CN1258683A, CN1258684A, and disclosed in these four sections of documents, content is all introduced as the technical scheme of catalyzer of the present invention at this.Catalyzer described in Chinese patent CN1258683A, has advantage especially as catalyzer of the present invention, and therefore content disclosed in the document is all introduced as the preferred version of catalyzer of the present invention at this.
The preferred Z-N of the present invention (Ziegler-Natta) catalyzer is characterized in that, comprise component A, B and C, wherein A is the ingredient of solid catalyst of titaniferous, it is dissolved in the solvent system be made up of organic epoxy compound thing, organo phosphorous compounds and inert diluent by magnesium halide, mix with titanium tetrahalide or derivatives thereof after forming homogeneous solution, under precipitation additive exists, separate out solids; This solids processes with multi-carboxylate, it is made to be attached on solids, obtain with titanium tetrahalide and inert diluent process again, wherein precipitation additive is the one in organic acid anhydride, organic acid, ether, ketone, in above-mentioned solvent system, in every mole of magnesium halide, organic epoxy compound thing is 0.2-5 mole, and the mol ratio of organic epoxy compound thing and organo phosphorous compounds is 0.5-1.6; B is general formula is AlR
nx
3-nalkylaluminium cpd, in formula, R is hydrogen or carbonatoms is the alkyl of 1-20; C is general formula is R
nsi (OR ')
4-nsilicoorganic compound, 0≤n≤3 in formula, R and R ' is of the same race or different alkyl, cycloalkyl, aryl or haloalkyl; Ratio between B component and component A, with the molar ratio computing of aluminium and titanium for 5-1000, the ratio between component C and component A, with the molar ratio computing of silicon and titanium for 2-100.
Magnesium halide described in above-mentioned catalyst component A comprise one of them halogen atom in complex compound, the magnesium dihalide molecular formula such as water, alcohol of magnesium dihalide, magnesium dihalide by alkyl or halogen-oxyl the derivative of replacing, above-mentioned magnesium dihalide is specially magnesium dichloride, dibrominated magnesium, diiodinating magnesium.
Organic epoxy compound thing described in above-mentioned catalyst component A comprises the compound such as oxide compound, glycidyl ether, inner ether of carbonatoms at the aliphatics alkene of 2-8, diolefine or halogenated aliphatic alkene or diolefine.Particular compound is as oxyethane, propylene oxide, butylene oxide ring, butadiene oxide, butadiene double oxide, epoxy chloropropane, methyl glycidyl ether, diglycidylether, tetrahydrofuran (THF).
Organo phosphorous compounds described in above-mentioned catalyst component A comprises hydrocarbyl carbonate or the halo hydrocarbyl carbonate of ortho-phosphoric acid or phosphorous acid, concrete as ortho-phosphoric acid trimethyl, ortho-phosphoric acid triethyl, ortho-phosphoric acid tri-n-butyl, ortho-phosphoric acid triphenylmethyl methacrylate, trimethyl phosphite, triethyl-phosphite, tributyl phosphate, phosphorous acid benzene methyl.
Described in above-mentioned catalyst component A, inert diluent can adopt hexane, heptane, octane, benzene,toluene,xylene, 1,2-ethylene dichloride, chlorobenzene and other hydro carbons or halogenated hydrocarbon compound.
Consisting of of magnesium halide solution described in above-mentioned catalyst component A: in every mole of magnesium halide, organic epoxy compound thing 0.2-5 mole, with 0.5-2 mole as well; The mol ratio of organic epoxy compound thing and organo phosphorous compounds is 0.5-1.6, and being preferably 0.9-1.6, is best with 0.9-1.4, inert diluent 1200-2400 milliliter, is preferably 1400-2000 milliliter.
The halogenide or derivatives thereof of the transition metal Ti described in above-mentioned catalyst component A, refers to that general formula is TiX
n(OR)
4-n, n=1-4, concrete as titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four titanium butoxide, purity titanium tetraethoxide, a chlorine triethoxy titanium, dichlorodiethyl oxygen base titanium, trichlorine one ethanolato-titanium.In every mole of magnesium halide, the add-on of the halogenide or derivatives thereof of transition metal Ti is 0.5-150 mole, with 1-20 mole as well.
Precipitation additive described in above-mentioned catalyst component A is selected from the one in organic acid, organic acid anhydride, organic ether, organic ketone, or their mixture.Concrete as diacetyl oxide, Tetra hydro Phthalic anhydride, Succinic anhydried, MALEIC ANHYDRIDE, pyromellitic acid anhydride, acetic acid, propionic acid, butyric acid, vinylformic acid, methacrylic acid, acetone, methylethylketone, benzophenone, methyl ether, ether, propyl ether, butyl ether, amyl ether.In every mole of magnesium halide, the add-on of precipitation additive is 0.03-1.0 mole, with 0.05-0.4 mole as well.
Multi-carboxylate described in above-mentioned catalyst component A is selected from the one in aliphatic polycarboxylic acid's ester and aromatic polycarboxylic acid ester, or their mixture.Concrete as diethyl malonate, butyl ethyl malonate, diethylene adipate, Polycizer W 260, ethyl sebacate, Uniflex DBS, phthalic ester diisobutyl ester, phthalic ester di-n-butyl, phthalic ester di-isooctyl, diethyl maleate, maleic acid n-butyl, naphthalene dicarboxylic acids diethyl ester, naphthalene dicarboxylic acids dibutylester, triethyl trimellitate, tributyl trimellitate, benzene-1,2,3-tricarboxylic acid triethyl, benzene-1,2,3-tricarboxylic acid tri-n-butyl, pyromellitic acid tetra-ethyl ester, pyromellitic acid four butyl ester etc.In every mole of magnesium halide, the add-on of multi-carboxylate is 0.0019-0.01 mole, with 0.0040-0.0070 mole as well.
Organo-aluminium compound described in above-mentioned catalyst component B, its general formula is AlR
nx
3-n, in formula, R is hydrogen, and carbonatoms is the alkyl of 1-20, particularly alkyl, aralkyl, aryl; X is halogen, particularly chlorine and bromine; N is the number of 0 < n≤3.Particular compound as trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, trioctylaluminum, a hydrogen diethyl aluminum, a hydrogen diisobutyl aluminum, aluminium diethyl monochloride, a chloro-di-isobutyl aluminum, sesquialter ethylmercury chloride aluminium, ethyl aluminum dichloride, wherein with triethyl aluminum, triisobutyl aluminium as well.
Silicoorganic compound described in above-mentioned catalyst component C, its general formula is R
nsi (OR ')
4-n, 0≤n≤3 in formula, R and R ' is of the same race or different alkyl, cycloalkyl, aryl or haloalkyl.Particular compound is as trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, Cyclohexylmethyldimethoxysilane, dibutyldimethoxysilane, dimethoxydiphenylsilane, diphenyl diethoxy silane, phenyltrimethoxysila,e, vinyltrimethoxy silane.
In above-mentioned catalyst system, in B component, in aluminium and component A, the mol ratio of titanium is 5-1000, with 25-300 as well; In component C, in silicon and component A, the mol ratio of titanium is 2-100, with 8-32 as well.
The preparation method of above-mentioned catalyst activity component A is: be under agitation dissolved in by magnesium halide in the solvent system be made up of organic epoxy compound thing, organo phosphorous compounds and inert diluent, form homogeneous transparent solution, solvent temperature is 0-100 DEG C, preferably 30-70 DEG C; Under precipitation additive exists, at-35-60 DEG C of temperature, be preferably-30-5 DEG C, titanium compound is added magnesium halide homogeneous solution or magnesium halide solution is added in titanium compound, and to multi-carboxylate be added before solids is separated out or after separating out, to be processed to the solids of separating out, multi-carboxylate is made partly to be attached on solids; Then reaction mixture is warming up to 60-110 DEG C, suspension is stirred 10 minutes-10 hours at this temperature, stops stirring rear solids and separate out from mixture solution, filter, remove mother liquor, with toluene and hexanes wash solids, the ingredient of solid catalyst A of obtained titaniferous.
Three kinds of described catalyst components can directly join in polymerization reactor, also after pre-complexing and/or prepolymerization, then can join in reactor.Wherein the form of the reactor of pre-complex reaction can be various, and can be continuous stirred tank reactor, annular-pipe reactor, one section of pipeline containing static mixer, even also can be the pipeline that one section of material is in turbulence state.
Contriver unexpectedly finds, the catalyzer selected for the present invention carries out pre-complexing process, can obtain high propene-1-butene-1 random copolymers that room temperature xylene soluble content is low simultaneously of butene-1 relative distribution degree.The temperature-controllable of pre-complexing is between-10 ~ 60 DEG C, and preferred temperature is 0 ~ 30 DEG C.Contriver finds further, the butene-1 relative distribution degree of propene-1-butene-1 random copolymers of the present invention increases along with the prolongation of pre-complexation time, and room temperature xylene soluble content reduces along with the prolongation of pre-complexation time, but, pre-complexation time is oversize, can have influence on the activity of catalyzer.Therefore, the pre-complexation time that the present invention selects is 0.1-100min, preferred 1-30min.
Catalyzer through pre-complexing can also carry out optionally prepolymerization process.Prepolymerization can be carried out continuously under liquid-phase bulk condition, also can carry out in inert solvent discontinuous.Pre-polymerization reactor can be continuous stirred tank, annular-pipe reactor etc.Prepolymerized temperature-controllable is between-10 ~ 60 DEG C, and preferred temperature is 0 ~ 40 DEG C.Prepolymerized multiple controls at 0.5 ~ 1000 times, and preferred multiple is 1.0 ~ 500 times.
Described polyreaction is carried out in propylene liquid phase.When carrying out liquid polymerization, polymerization temperature is 0 ~ 150 DEG C, with 40 ~ 100 DEG C as well; Polymerization pressure should higher than the saturated vapour pressure of propylene under corresponding polymerization temperature.
Polymerization can be carry out continuously, also may be carried out batchwise.Successive polymerization can one or more series connection Liquid-phase reactor, Liquid-phase reactor can be annular-pipe reactor, also can be continuous stirred tank reactor.
Propene-1-butene-1 random copolymers of the present invention can use equipment to carry out extruding pelletization, this area other auxiliary agents normally used can be added as required during granulation, as oxidation inhibitor, acid-acceptor, photostabilizer, thermo-stabilizer, tinting material etc., consumption is conventional amount used.
In the preparation method of propene-1-butene-1 random copolymers of the present invention, the melt blending temperature of material is blending temperature used in the processing of usual polypropylene, not only ensureing the complete melting of polypropylene matrix but also can not make to select in its scope of decomposing, 180 ~ 260 DEG C should be generally.
Preparation method's polymerization process of the present invention is easy, can avoid occurring that sticky still, caking, residual monomer are difficult to remove the situations such as clean, and its propene-1-butene-1 random copolymers butene-1 relative distribution degree prepared is high, room temperature xylene soluble content is low.
Embodiment
The present invention is further described below in conjunction with embodiment.Scope of the present invention is not by the restriction of these embodiments, and scope of the present invention proposes in detail in the claims.
Relevant data in the present invention and embodiment obtains by following testing method:
1, comonomer butene-1 content and butene-1 relative distribution degree (MD in propene-1-butene-1 random copolymers
relative (B), relative monomer dispersity) mensuration:
Adopt the 400MHz nuclear magnetic resonance spectrometer (NMR) of Bruker company of Switzerland to measure, INSTRUMENT MODEL is AVANCE III.Solvent is deuterated orthodichlorobenzene, 250mg sample/2.5ml solvent, 140 DEG C of dissolved samples, gathers
13c-NMR, probe temperature 125 DEG C, detecting head specification 10 millimeters, time of lag, D1 was 10 seconds, and sampling time AT is 5 seconds, scanning times more than 5000 times.Identification and the data processing method at experimental implementation, spectrum peak are carried out according to the NMR specification of standard, more detailed content is with reference to reference: (1) H.N.Cheng, 13C NMR Analysis of Propylene-Butylene Copolymers by a ReactionProbability Model, Journal of Polymer Science:Polymer Physics Edition, 21,573-581 (1983).(2)Eric T.Hsieh，and James C.Randall，MonomerSequence Distributions in Ethylene-1-Hexene Copolymers，Macromolecules，15，1402-1406(1982)。
Butylene (B) relative distribution degree (MD
relative (B)) calculation formula is as follows:
MD
random(B)＝(1-[B])×100
Wherein, [PB] represents the monomeric unit number of the butene-1 that molecular chain is connected with propylene monomer; [B] represents the monomeric unit number that on molecular chain, butene-1 is total; MD
observed (B)the dispersion coefficient of butene-1 monomer on molecular chain, MD
random (B)desirable random dispersion coefficient, MD
relative (B)it is the relative distribution degree of butene-1; MD
observed (B), MD
random (B)and MD
relative (B)unit be %.
2, xylene soluble content: measure by ASTM D5492-98.
3, melting index (MFR): by ISO1133,230 DEG C, measure under 2.16kg load.
4, molecular weight distributing index Mw/Mn: adopt Polymer Laboratories company of Britain to produce the molecular weight distribution of PL-GPC220 gel permeation chromatograph working sample, chromatographic column is 3 series connection Plgel, 10 μm of MIXED-B posts, solvent and moving phase are 1,2,4-trichlorobenzene (containing 0.3g/1000ml oxidation inhibitor 2,6-dibutyl paracresol), column temperature 150 DEG C, flow velocity 1.0ml/min, adopts PL company EasiCal PS-1 Narrow distribution polystyrene standard specimen to carry out universal calibration.
5, heat-drawn wire (HDT): measure by ASTM D648.
6, mist degree: measure according to ASTM D1003.
Each test is all carried out under room temperature environment condition above, except as otherwise noted.
Embodiment 1
Polyreaction is carried out on a set of pilot plant.Its major equipment comprises pre-complex reactor, prepolymerization reactor, annular-pipe reactor.Polymerization process and step as follows:
(1) pre-complex reaction:
Primary Catalysts (the active solid catalyst component of titaniferous) adopts the method that in Chinese patent CN1258683A, embodiment 1 describes to obtain, internal electron donor compound wherein adopts diisobutyl phthalate, the Primary Catalysts Ti content 1.93wt% obtained, magnesium 19.8wt%, diisobutyl phthalate content 9.3wt%.
Primary Catalysts, promotor (triethyl aluminum), external electron donor (Cyclohexylmethyldimethoxysilane) carry out the reaction of pre-complexing via the continuous stirred tank that different pipelines adds jacketed respectively, pre-complexation temperature controls to be 8 DEG C by jacket water (J.W.), each reaction medium inserts end charging, overflow discharging, promotor, external electron donor is diluted by hexane, control the volumetric flow rate of these two kinds of chargings, and then the residence time controlled in pre-complex reactor is 1 minute.
(2) prepolymerization:
Catalyzer after pre-complexing is carried secretly via the propylene being chilled to 10 DEG C and is added prepolymerization reactor continuously and carry out prepolymerization, pre-polymerization reactor is the continuous stirred tank of full still operation, prepolymerization is carried out (prepolymerized temperature and time is in table 1) under propylene liquid-phase bulk environment, and under this condition, the pre-polymerization multiple of catalyzer is about 120 ~ 150 times.
(3) copolymerization of propene-1-butene-1:
Pre-polymerization rear catalyst enters in annular-pipe reactor, completes the copolymerization of propene-1-butene-1 in annular-pipe reactor.Loop po lymerisation temperature of reaction 70 DEG C, reaction pressure 4.0MPa.
The add-on of annular-pipe reactor butene-1 and hydrogen is in table 1.
Go out after propylene through flash separation from annular-pipe reactor polymkeric substance out, then remove the active of unreacted catalyzer and heat drying through wet nitrogen, obtain polymer powders.
The calcium stearate (Ciba) of IRGAFOS 168 additive (Ciba) of 0.1 weight part, IRGANOX 1010 additive (Ciba) of 0.2 weight part and 0.05 weight part is added respectively in the powder that the polymerization of 100 weight parts obtains, use twin screw extruder granulation, obtain the pellet of propene-1-butene-1 random copolymers, its performance test results is in table 1.
Embodiment 2
With embodiment 1, just change the pre-complexation time of catalyzer.Polymerizing condition and polymer performance are in table 1.
Embodiment 3
With embodiment 1, just change butene-1 add-on, H
2add-on and the pre-complexation time of catalyzer.Polymerizing condition and polymer performance are in table 1.
Embodiment 4
With embodiment 1, just change butene-1 add-on and the pre-complexation time of catalyzer.Polymerizing condition and polymer performance are in table 1.
Comparative example 1
With embodiment 1, but the pre-complexing of catalyst-free.Primary Catalysts, promotor (triethyl aluminum), external electron donor (Cyclohexylmethyldimethoxysilane) separately directly enter pre-polymerization reactor.Polymerizing condition and polymer performance are in table 1.
Comparative example 2
With embodiment 4, but the pre-complexing of catalyst-free.Primary Catalysts, promotor (triethyl aluminum), external electron donor (Cyclohexylmethyldimethoxysilane) separately directly enter pre-polymerization reactor.Polymerizing condition and polymer performance are in table 1.
Comparative example 3
Primary Catalysts (the solid active center component of titaniferous) adopts the method (comprising " the preparing the general operation step of spherical catalyst components " before embodiment 1 " preparing magnesium chloride/alcohol adducts particle " and embodiment 1) that in Chinese patent CN200410062291.3, embodiment 1 describes to obtain, internal electron donor compound wherein adopts n-butyl phthalate, the Primary Catalysts Ti content 2.4wt% obtained, Mg content 18.0wt%, n-butyl phthalate content 13wt%.
Other are with embodiment 4, and polymerizing condition and polymer performance are in table 1.
As can be seen from above data, the catalyzer selected for the present invention carries out pre-complexing process and does not carry out compared with pre-complexing process, in propene-1-butene-1 random copolymers obtained, the relative distribution degree of butene-1 significantly improves, room temperature xylene soluble content obviously reduces, same butene content, the transparency of polymkeric substance is close, but heat-drawn wire improves, and the thermotolerance of illustrative material is improved.Further, along with pre-complexation time increases, also above-mentioned effect can be improved further.As can be seen from the data of comparative example 3 and embodiment 4, the catalysts influence that pre-complexing is selected for the present invention is remarkable, and namely onset is worked in coordination with in the catalyzer selected of the present invention and pre-complexing.
Claims (23)
1. propene-1-butene-1 random copolymers, its butene-1 content is 1-6mol%, and it is greater than 98.5% according to the butene-1 relative distribution degree of nuclear magnetic resonance method determination, described propene-1-butene-1 random copolymers comprises component A selected, there is lower copolymerization and obtain in the Ziegler-Natta catalyst of B and C, wherein A is the ingredient of solid catalyst of titaniferous, it is dissolved in by organic epoxy compound thing by magnesium halide, in the solvent system of organo phosphorous compounds and inert diluent composition, mix with titanium tetrahalide or derivatives thereof after forming homogeneous solution, under precipitation additive exists, separate out solids, this solids processes with multi-carboxylate, it is made to be attached on solids, obtain with titanium tetrahalide and inert diluent process again, described magnesium halide is magnesium dihalide, the water of magnesium dihalide or the complex compound of alcohol, in magnesium dihalide molecular formula one of them halogen atom by alkyl or halogen-oxyl the one in the derivative of replacing, or their mixture, B is general formula is AlR
nx
3-nalkylaluminium cpd, in formula, R is hydrogen or carbonatoms is the alkyl of 1-20, and X is halogen, and n is the number of 0<n≤3, C is general formula is R
nsi (OR ')
4-nsilicoorganic compound, 0≤n≤3 in formula, R and R ' is of the same race or different alkyl, cycloalkyl, aryl or haloalkyl, three kinds of described catalyst components after pre-complexing and optional prepolymerization, then join in polymerization reactor.
2. propene-1-butene-1 random copolymers as claimed in claim 1, it is characterized in that, described butene-1 content is 3-6mol%.
3. propene-1-butene-1 random copolymers as claimed in claim 1, it is characterized in that, the described butene-1 relative distribution degree according to nuclear magnetic resonance method determination is greater than 99.0%.
4. propene-1-butene-1 random copolymers as claimed in claim 1, it is characterized in that, its room temperature xylene soluble content is lower than following fit line: Y=0.77+0.252X; Wherein, Y is the weight percentage of room temperature xylene soluble part, and X is the molar content of butene-1 in propene-1-butene-1 random copolymers.
5. propene-1-butene-1 random copolymers as claimed in claim 1, is characterized in that, its 230 DEG C, melting index under 2.16kg load is 0.5-50g/10min.
6. propene-1-butene-1 random copolymers as claimed in claim 5, is characterized in that, described 230 DEG C, melting index under 2.16kg load is 2-30g/10min.
7. propene-1-butene-1 random copolymers as claimed in claim 1, it is characterized in that, the molecular weight distributing index Mw/Mn that it adopts GPC to test is 3.5-8.
8. propene-1-butene-1 random copolymers as claimed in claim 7, is characterized in that, the molecular weight distributing index Mw/Mn of described employing GPC test is 3.5-6.
9. propene-1-butene-1 random copolymers as claimed in claim 1, it is characterized in that, its preparation method comprises: under described Ziegler-Natta catalyst exists, under polymerization temperature and suitable hydrogen content, by regulating the add-on of comonomer butene-1 in reactor, the copolymerization carrying out propylene and butene-1 obtains propene-1-butene-1 random copolymers.
10. propene-1-butene-1 random copolymers as claimed in claim 1, it is characterized in that, in the homogeneous solution that the magnesium halide described in component A is formed, in every mole of magnesium halide, organic epoxy compound thing is 0.2-5 mole, and the mol ratio of organic epoxy compound thing and organo phosphorous compounds is 0.9-1.6.
11. propene-1-butene-1 random copolymerss as claimed in claim 1, it is characterized in that, the precipitation additive described in component A is the one in organic acid anhydride, organic acid, ether, ketone, or their mixture.
12. propene-1-butene-1 random copolymers as claimed in claim 1, is characterized in that, the ratio between described B component and component A, with the molar ratio computing of aluminium and titanium for 5-1000, the ratio between component C and component A, with the molar ratio computing of silicon and titanium for 2-100.
13. propene-1-butene-1 random copolymerss as claimed in claim 10, it is characterized in that, in the homogeneous solution that magnesium halide described in component A is formed, in every mole of magnesium halide, organic epoxy compound thing is 0.6-2 mole, the mol ratio of organic epoxy compound thing and organo phosphorous compounds is 0.9-1.4, inert diluent 1200-2400 milliliter.
14. propene-1-butene-1 random copolymerss as claimed in claim 1, it is characterized in that, organic epoxy compound thing described in component A is the one in oxyethane, propylene oxide, butylene oxide ring, butadiene oxide, butadiene double oxide, epoxy chloropropane, methyl glycidyl ether, diglycidylether, tetrahydrofuran (THF), or their mixture.
15. propene-1-butene-1 random copolymerss as claimed in claim 1, it is characterized in that, organo phosphorous compounds described in component A is the one in ortho-phosphoric acid trimethyl, ortho-phosphoric acid triethyl, ortho-phosphoric acid tri-n-butyl, ortho-phosphoric acid triphenylmethyl methacrylate, trimethyl phosphite, triethyl-phosphite, tributyl phosphate, phosphorous acid benzene methyl, or their mixture.
16. propene-1-butene-1 random copolymerss as claimed in claim 11, it is characterized in that, precipitation additive described in component A is the one in diacetyl oxide, Tetra hydro Phthalic anhydride, Succinic anhydried, MALEIC ANHYDRIDE, pyromellitic acid anhydride, acetic acid, propionic acid, butyric acid, vinylformic acid, methacrylic acid, acetone, methylethylketone, benzophenone, methyl ether, ether, propyl ether, butyl ether, amyl ether, or their mixture.
17. propene-1-butene-1 random copolymerss as claimed in claim 1, it is characterized in that, multi-carboxylate described in component A is selected from diethyl malonate, butyl ethyl malonate, diethylene adipate, Polycizer W 260, ethyl sebacate, Uniflex DBS, diisobutyl phthalate, n-butyl phthalate, dimixo-octyl phthalate, diethyl maleate, maleic acid n-butyl, naphthalene dicarboxylic acids diethyl ester, naphthalene dicarboxylic acids dibutylester, triethyl trimellitate, tributyl trimellitate, benzene-1,2,3-tricarboxylic acid triethyl, benzene-1,2,3-tricarboxylic acid tri-n-butyl, pyromellitic acid tetra-ethyl ester, one in pyromellitic acid four butyl ester, or their mixture.
18. propene-1-butene-1 random copolymerss as claimed in claim 1, it is characterized in that, titanium tetrahalide or derivatives thereof described in component A is the one in titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four titanium butoxide, purity titanium tetraethoxide, a chlorine triethoxy titanium, dichlorodiethyl oxygen base titanium, trichlorine one ethanolato-titanium, or their mixture.
19. propene-1-butene-1 random copolymerss as claimed in claim 1, it is characterized in that, the temperature of described pre-complexing controls between-10 ~ 60 DEG C.
20. propene-1-butene-1 random copolymerss as claimed in claim 19, it is characterized in that, the temperature of described pre-complexing controls between 0 ~ 30 DEG C.
21. propene-1-butene-1 random copolymerss as claimed in claim 1, is characterized in that, the time of described pre-complexing is 0.1 ~ 100min.
22. propene-1-butene-1 random copolymerss as claimed in claim 21, is characterized in that, the time of described pre-complexing is 1 ~ 30min.
23. propene-1-butene-1 random copolymerss as claimed in claim 9, it is characterized in that, the copolymerization of described propylene and butene-1 occurs in liquid phase annular-pipe reactor.
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| CN201110336505.1A CN103087238B (en) | 2011-10-29 | 2011-10-29 | Propylene random copolymer |
| JP2012238183A JP6310634B2 (en) | 2011-10-29 | 2012-10-29 | Propylene random copolymer, process for its preparation, and compositions and articles containing it |
| EP12190341.3A EP2586801B1 (en) | 2011-10-29 | 2012-10-29 | Propylene random copolymer, method for its preparation, and compositions and articles containing the same |
| US13/663,433 US9303108B2 (en) | 2011-10-29 | 2012-10-29 | Propylene random copolymer, method for its preparation, and compositions and articles containing the same |
| BR102012027725-5A BR102012027725B1 (en) | 2011-10-29 | 2012-10-29 | PROPYLENE / BUTENE-1 RANDOM COPOLYMER, METHOD FOR PREPARING A PROPYLENE / BUTENE-1 RANDOM COPOLYMER, PROPYLENE / BUTENE-1 RANDOM COPOLYMER COMPOSITION, E-METHOD OF PREPARING A BIOENE PACKING FOOD |
| TW101139949A TWI567094B (en) | 2011-10-29 | 2012-10-29 | Propylene random copolymers, processes for their preparation, and compositions and articles including the same |
| DK12190341.3T DK2586801T3 (en) | 2011-10-29 | 2012-10-29 | The propylene copolymer, process for its preparation and to compositions and articles containing same |
| KR1020120120548A KR101773487B1 (en) | 2011-10-29 | 2012-10-29 | Propylene random copolymer, method for its preparation, and compositions and articles containing the same |
| SG2012080099A SG189671A1 (en) | 2011-10-29 | 2012-10-29 | Propylene random copolymer, method for its preparation, and compositions and articles containing the same |
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| CN1258683A (en) * | 1998-12-30 | 2000-07-05 | 中国石油化工集团公司 | Catalyst for polymerization or copolymerization of propylene and its preparation and use |
| CN102190748A (en) * | 2010-03-19 | 2011-09-21 | 中国石油天然气股份有限公司 | Preparation method for propylene/1-butylene random copolymer resin |
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| CN1258683A (en) * | 1998-12-30 | 2000-07-05 | 中国石油化工集团公司 | Catalyst for polymerization or copolymerization of propylene and its preparation and use |
| CN102190748A (en) * | 2010-03-19 | 2011-09-21 | 中国石油天然气股份有限公司 | Preparation method for propylene/1-butylene random copolymer resin |
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