CN112707989B - Plasticizer-free ethylene-propylene random copolymer and application thereof - Google Patents
Plasticizer-free ethylene-propylene random copolymer and application thereof Download PDFInfo
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Abstract
The invention belongs to the field of olefin polymerization, and relates to an ethylene-propylene random copolymer without a plasticizer and application thereof. The ethylene-propylene random copolymer contains 93-98 wt% of propylene and 2-7 wt% of ethylene based on the weight of the ethylene-propylene random copolymer; the melting point of the ethylene-propylene random copolymer is lower than 143 ℃, the content of xylene soluble substances is less than or equal to 5wt percent, and the ethylene-propylene random copolymer is prepared by 13 C NMR measured [ PEP]/[E]>78 percent. The ethylene-propylene random copolymer has the advantages of low melting point, less xylene soluble substances and less micromolecule content, and does not contain plasticizer.
Description
Technical Field
The invention belongs to the field of olefin polymerization, and particularly relates to an ethylene-propylene random copolymer without a plasticizer, and an application of the ethylene-propylene random copolymer.
Background
Polypropylene is a colorless translucent thermoplastic resin, has the advantages of small relative density, easy processing, high impact strength, corrosion resistance, good electrical insulation, low price and the like, is the fastest-developing material in general plastics, and is widely used in various fields such as chemical industry, buildings, household appliances, agriculture, automobile industry and the like. To expand the field of application of polypropylene, copolymerization of comonomers with propylene can be used to modify the polymer properties. The decrease in crystallinity of the copolymer and the refinement of spherulites cause changes in the physical properties of the polymer: random copolymers have lower haze and melt temperatures, high impact resistance and flexibility compared to homopolymers; random copolymers have lower melting points, higher transparency and high temperature creep resistance than block copolymers.
For the ethylene-propylene random copolymer, a lower melting point and a lower content of solubles are sought in terms of properties. Because the melting point is low, the heat sealing temperature is low, which is beneficial to the packaging processing, the sealing joint is smooth and beautiful, and the commodity value can be improved. Too high an extractable content would limit the use of the product in the field of food packaging. Therefore, the ethylene-propylene random copolymer with less xylene solubles and low melting point has better market application prospect.
The crystallinity of the polymer can be related to the content and the type of the comonomer, and when the content of the comonomer is increased, the melting point of the polypropylene is obviously reduced; copolymerization of ethylene is more effective in lowering the melting point and has a greater impact on the final properties of the random copolymer. In addition, the kind of comonomer and the catalyst are also major factors determining the structure of the final polymer product. The uniform dispersion of the comonomer leads to a reduction in the melting point of the polymer; the comonomer is dispersed unevenly, so that the phenomenon of continuous arrangement occurs, and polymer molecules without crystallization capacity are generated. This portion of the polymer does not lower the melting temperature but instead forms a rubbery extractable material soluble in xylene. Ethylene improves the chain structure more effectively than 1-butene, lowers the melting temperature, but produces more xylene solubles.
In the prior art, although there is a method for reducing the content of xylene soluble substances in the ethylene-propylene random copolymer or a method for reducing the melting point of the ethylene-propylene random copolymer, the two methods are difficult to be compatible. And with the increasing health consciousness of people and the continuous rigor of the social environmental protection requirement, the requirement on the performance of the polymer is also increased. At present, the xylene soluble content and melting point of the ethylene-propylene random copolymer have not been reduced to a satisfactory extent, and there is still room for further improvement.
Therefore, for the ethylene-propylene random copolymer, a lower melting point and a lower soluble substance content are pursued from the aspect of performance, substances which are harmful to health, such as plasticizer, and the like, and small molecules which are easy to precipitate or cause VOC are avoided as little as possible from the aspect of environmental protection, and the ethylene-propylene random copolymer has a better market application prospect.
Disclosure of Invention
The invention aims to provide an ethylene-propylene random copolymer without a plasticizer and application thereof.
The invention provides an ethylene-propylene random copolymer without plasticizer, which contains 93-98 wt% of propylene and 2-7 wt% of ethylene based on the weight of the ethylene-propylene random copolymer; the melting point of the ethylene-propylene random copolymer is lower than 143 ℃, the content of xylene soluble substances is less than or equal to 5wt percent, and the ethylene-propylene random copolymer is prepared by 13 C NMR measured [ PEP]/[E]>78％。
According to the invention, the ethylene-propylene random copolymer preferably contains from 95 to 97% by weight of propylene and from 3 to 5% by weight of ethylene, based on the weight of the ethylene-propylene random copolymer.
According to a preferred embodiment of the invention, the melting point of the ethylene-propylene random copolymer is lower than 140 ℃, and the melting point of the ethylene-propylene random copolymer is lower, so that the heat sealing temperature of the heat sealing film can be reduced more favorably.
The melting point of the polymers of the present invention is measured by Differential Scanning Calorimetry (DSC). Specifically, a Perkin-Elmer DSC-7 type differential scanning calorimeter (USA) can be adopted, and the sample dosage is 4-5 mg. Heating the sample to 200 ℃ at the speed of 10 ℃/min, keeping the temperature for 5min to eliminate the thermal history, then cooling to 50 ℃ at the speed of 10 ℃/min, keeping the temperature at 50 ℃ for 1min, then heating to 200 ℃ at the speed of 10 ℃/min, and determining the crystallization temperature, the crystallization enthalpy, the melting temperature and the melting enthalpy from the heat flow curves recorded by cooling and re-heating.
According to a preferred embodiment of the present invention, the ethylene-propylene random copolymer has a xylene solubles content of 4 wt. -% or less, preferably a xylene solubles content of 3 wt. -% or less.
In the present invention, the xylene solubles content of the polymer was tested according to GB/T24282-.
According to a preferred embodiment of the invention, the ethylene-propylene random copolymer is prepared by 13 C NMR measured [ PEP]/[E]>80%, preferably>83％。
The sequence distribution and composition of the copolymers of the invention are 13 C NMR( 13 C nmr analysis). Specifically, an Avance III 400MHz NMR spectrometer from Bruker, Germany may be used. The solvent is deuterated o-dichlorobenzene, the testing temperature is 125 ℃, and the scanning times are more than 5000 times.
According to 13 The data of the C NMR spectrum allow the calculation of the sequence distribution and the composition of the copolymer. The specific calculation formula is as follows:
[PEP]/[E]＝[PEP]/([EEE]+[EEP]+[PEP])
the high ratio of PEP/E indicates that the ethylene is distributed more uniformly on the molecular chain, which is beneficial to reducing the melting point of the copolymer.
According to a preferred embodiment of the invention, the ethylene-propylene random copolymer is free of fractions having a weight average molecular weight below 1000. The content of the small molecular part is low, so that the precipitate in the product is low, and the safety of human body contact is higher.
In the present invention, the percentage content of the polymer having a weight average molecular weight of less than 1000 fractions is determined by Gel Permeation Chromatography (GPC). "the ethylene-propylene random copolymer does not contain a portion having a weight average molecular weight of less than 1000" means that: when the ethylene-propylene random copolymer was measured by the GPC method, the portion having a weight average molecular weight of less than 1000 was zero. Specifically, Shimadzu LC-10AT Gel Permeation Chromatograph (GPC) can be adopted, wherein trichlorobenzene is used as mobile phase and the temperature is 150 ℃.
The ethylene-propylene random copolymer of the present invention is preferably prepared by a process comprising the steps of: under the condition of olefin polymerization, propylene and ethylene are polymerized in the presence of a catalyst and hydrogen to obtain the ethylene-propylene random copolymer;
the catalyst comprises a solid component, an alkyl aluminum compound and an optional external electron donor compound, wherein the solid component comprises a reaction product of the following components:
(i) a magnesium-containing compound;
(ii) a titanium-containing compound; and
(iii) an internal electron donor;
the internal electron donor comprises an internal electron donor compound a and an internal electron donor compound b, and the molar ratio of the internal electron donor compound a to the internal electron donor compound b is 0.1-20: 1, preferably 0.3-8: 1; the internal electron donor compound a is a glycol ester compound, and the internal electron donor compound b is a diether compound.
The internal electron donor does not contain phthalate compounds.
According to a preferred embodiment of the present invention, the internal electron donor compound a is a diol ester compound represented by formula I,
in the formula I, R 1 And R 2 Identical or different, each independently is halogen, C 1 -C 20 Straight or branched alkyl of (2), C 2 -C 20 Linear or branched alkenyl of (C) 3 -C 20 Substituted or unsubstituted cycloalkyl of (A), C 6 -C 20 Substituted or unsubstituted aryl of (1), C 7 -C 20 Substituted or unsubstituted aralkyl or C 7 -C 20 Optionally substituted or unsubstituted alkaryl, the aryl, aralkyl or aryl ring of the alkaryl being optionally substituted by a group selected from halogen, C 1 -C 6 And C is a straight or branched alkyl group 1 -C 6 Substituted with one or more of alkoxy groups of (a);
R 3 、R 4 、R 5 、R 6 and R 1 -R 2n The same or different, each independently is hydrogen, halogen, C 1 -C 20 Straight or branched alkyl of (2), C 3 -C 20 Substituted or unsubstituted cycloalkyl of (A), C 6 -C 20 Substituted or unsubstituted aryl of (1), C 7 -C 20 Substituted or unsubstituted alkaryl of (1), C 7 -C 20 Substituted or unsubstituted aralkyl of (1), C 2 -C 20 Linear or branched alkylene of (2), C 2 -C 20 Ester group of (A) and (C) 10 -C 20 One of the condensed ring aromatic groups of (1), R 3 、R 4 、R 5 、R 6 And R 1 -R 2n Optionally containing heteroatoms, which are one or more of nitrogen, oxygen, sulfur, silicon, halogen and phosphorus; or, R 3 、R 4 、R 5 、R 6 And R 1 -R 2n Two or more of them are bonded to each other to form a saturated or unsaturated ring;
n is an integer of 0 to 10.
The middle bracket of the formula II [ "," C "", or "", the]The term "in" denotes that n carbon atoms are bonded in succession and that each carbon atom is further bonded to 2 substituents, i.e. there are n carbon atoms and R in total in the parenthesis 1 、R 2 、R 3 …R 2n And 2n substituents. Wherein n is an integer of 0 to 10, and when n is 0, the substituent is R in the diol ester compound shown in the formula II 6 、R 7 The carbon atom directly bonded to the substituent is R 8 、R 9 Is bonded to the carbon atom(s) of (a).
In the present invention, C 1 -C 20 Examples of the linear or branched alkyl group of (b) may include, but are not limited to: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, 1-ethylpropyl, 2-methylbutyl, 3-methylbutyl, 2-dimethylpropyl, n-hexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, n-heptyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, n-heptyl, n-octyl, n-nonylAlkyl, n-decyl, tetrahydrogeranyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-octadecyl, n-nonadecyl, n-eicosyl.
In the present invention, C 2 -C 20 Examples of the linear or branched alkenyl groups of (a) may include, but are not limited to: vinyl, allyl, isopropenyl, 1-propenyl, 2-methyl-1-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-ethyl-1-butenyl, 3-methyl-2-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-methyl-3-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-heptenyl, 1-octenyl, phenylvinyl, phenyl-n-butenyl, geranyl, 1-decenyl, 1-tetradecenyl, 1-octadecenyl, 9-octadecenyl, 1-eicosenyl, 1-octadecenyl, 3,7,11, 15-tetramethyl-1-hexadecenyl.
In the present invention, C 3 -C 20 Examples of the substituted or unsubstituted cycloalkyl group of (a) may include, but are not limited to: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, 4-n-propylcyclohexyl, 4-n-butylcyclohexyl, cycloundecyl, cyclododecyl.
In the present invention, C 6 -C 20 The substituted or unsubstituted aryl group of (2) includes C 6 -C 20 Substituted or unsubstituted phenyl of, also including C 10 -C 20 Examples of the substituted or unsubstituted fused ring aryl group of (a) may include, but are not limited to: phenyl, naphthyl, methylnaphthyl, ethylnaphthyl, anthryl, methylanthryl, ethylanthryl, phenanthryl, methylphenanthryl and ethylphenanthryl, pyrenyl, indenyl.
In the present invention, C 7 -C 20 The substituted or unsubstituted aralkyl group of (2) means an alkyl group having an aryl substituent and having 7 to 20 carbon atoms. C 7 -C 20 Examples of the substituted or unsubstituted aralkyl group of (a) may include, but are not limited to: phenylmethyl, phenylethyl, phenyl-n-propyl, phenyl-n-butyl, phenyl-tert-butyl, phenyl-isopropyl, phenyl-n-pentyl.
In the present invention，C 7 -C 20 The substituted or unsubstituted alkylaryl group of (2) means an aryl group having an alkyl substituent and having 7 to 20 carbon atoms. C 7 -C 20 Examples of the substituted or unsubstituted alkaryl group of (a) may include, but are not limited to: methylphenyl, ethylphenyl, n-propylphenyl, n-butylphenyl, tert-butylphenyl, isopropylphenyl, n-pentylphenyl.
In the present invention, C 1 -C 6 Examples of alkoxy groups of (a) may include, but are not limited to: methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, n-pentoxy, isopentoxy, tert-pentoxy, hexoxy.
In the present invention, the above-mentioned groups in other carbon number ranges can be selected correspondingly within the carbon number range defined, and are not described in detail herein.
Preferably, the internal electron donor compound a is a diol ester compound represented by formula IV,
in the formula IV, R 10 、R 11 、R 12 、R 13 、R 14 And R 15 Are the same or different and are each independently hydrogen or C 1 -C 20 Linear or branched alkyl groups of (a).
According to the present invention, examples of the internal electron donor compound a may include, but are not limited to: 1, 3-propanediol dibenzoate, 2-methyl-1, 3-propanediol dibenzoate, 2-ethyl-1, 3-propanediol dibenzoate, 2-propyl-1, 3-propanediol dibenzoate, 2-butyl-1, 3-propanediol dibenzoate, 2-dimethyl-1, 3-propanediol dibenzoate, 2-ethyl-2-butyl-1, 3-propanediol dibenzoate, 2-diethyl-1, 3-propanediol dibenzoate, 2-methyl-2-propyl-1, 3-propanediol dibenzoate, 2-isopropyl-2-isopentyl-1, 3-propanediol dibenzoate, 2-methyl-1, 3-propanediol dibenzoate, 2-methyl-2-propyl-1, 3-propanediol dibenzoate, 2-methyl-2-methyl-diol, 3-dibenzoate, 2-methyl-2-methyl-diol, 2-methyl-diol, 3-diol, 2-dibenzoate, 2-diol, 2-diol, 2-and/or a mixture, 2, 4-pentanediol dibenzoate, 3-methyl-2, 4-pentanediol dibenzoate, 3-ethyl-2, 4-pentanediol dibenzoate, 3-propyl-2, 4-pentanediol dibenzoate, 3-butyl-2, 4-pentanediol dibenzoate, 3-dimethyl-2, 4-pentanediol dibenzoate, 2-methyl-1, 3-pentanediol dibenzoate, 2-ethyl-1, 3-pentanediol dibenzoate, 2-propyl-1, 3-pentanediol dibenzoate, 2-butyl-1, 3-pentanediol dibenzoate, 2-dimethyl-1, 3-pentanediol dibenzoate, 2-methyl-1, 3-pentanediol dibenzoate, and 3-pentanediol dibenzoate, 2,2, 4-trimethyl-1, 3-pentanediol dibenzoate, 3-methyl-3-butyl-2, 4-pentanediol dibenzoate, 2-dimethyl-1, 5-pentanediol dibenzoate, 1, 6-hexanediol dibenzoate, 6-heptene-2, 4-heptanediol dibenzoate, 2-methyl-6-heptene-2, 4-heptanediol dibenzoate, 3-methyl-6-heptene-2, 4-heptanediol dibenzoate, 4-methyl-6-heptene-2, 4-heptanediol dibenzoate, 5-methyl-6-heptene-2, 4-heptanediol dibenzoate, a salt thereof, and a salt thereof, 6-methyl-6-heptene-2, 4-heptanediol dibenzoate, 3-ethyl-6-heptene-2, 4-heptanediol dibenzoate, 4-ethyl-6-heptene-2, 4-heptanediol dibenzoate, 5-ethyl-6-heptene-2, 4-heptanediol dibenzoate, 6-ethyl-6-heptene-2, 4-heptanediol dibenzoate, 3-propyl-6-heptene-2, 4-heptanediol dibenzoate, 4-propyl-6-heptene-2, 4-heptanediol dibenzoate, 5-propyl-6-heptene-2, 4-heptanediol dibenzoate, a salt thereof, and a salt thereof, 6-propyl-6-heptene-2, 4-heptanediol dibenzoate, 3-butyl-6-heptene-2, 4-heptanediol dibenzoate, 4-butyl-6-heptene-2, 4-heptanediol dibenzoate, 5-butyl-6-heptene-2, 4-heptanediol dibenzoate, 6-butyl-6-heptene-2, 4-heptanediol dibenzoate, 3, 5-dimethyl-6-heptene-2, 4-heptanediol dibenzoate, 3, 5-diethyl-6-heptene-2, 4-heptanediol dibenzoate, 3, 5-dipropyl-6-heptene-2, 4-heptanediol dibenzoate, 3, 5-dibutyl-6-heptene-2, 4-heptanediol dibenzoate, 3-dimethyl-6-heptene-2, 4-heptanediol dibenzoate, 3-diethyl-6-heptene-2, 4-heptanediol dibenzoate, 3-dipropyl-6-heptene-2, 4-heptanediol dibenzoate, 3-dibutyl-6-heptene-2, 4-heptanediol dibenzoate, 3, 5-heptanediol dibenzoate, 2-methyl-3, 5-heptanediol dibenzoate, 3-methyl-3, 5-heptanediol dibenzoate, 4-methyl-3, 5-heptanediol dibenzoate, 5-methyl-3, 5-heptanediol dibenzoate, 6-methyl-3, 5-heptanediol dibenzoate, 3-ethyl-3, 5-heptanediol dibenzoate, 4-ethyl-3, 5-heptanediol dibenzoate, 5-ethyl-3, 5-heptanediol dibenzoate, 3-propyl-3, 5-heptanediol dibenzoate, 4-propyl-3, 5-heptanediol dibenzoate, 3-butyl-3, 5-heptanediol dibenzoate, 2, 3-dimethyl-3, 5-heptanediol dibenzoate, 2, 4-dimethyl-3, 5-heptanediol dibenzoate, 2, 5-dimethyl-3, 5-heptanediol dibenzoate, 2, 6-dimethyl-3, 5-heptanediol dibenzoate, 3-dimethyl-3, 5-heptanediol dibenzoate, 4-dimethyl-3, 5-heptanediol dibenzoate, 6-dimethyl-3, 5-heptanediol dibenzoate, 2, 6-dimethyl-3, 5-heptanediol dibenzoate, 3, 4-dimethyl-3, 5-heptanediol dibenzoate, 3, 5-dimethyl-3, 5-heptanediol dibenzoate, 3, 6-dimethyl-3, 5-heptanediol dibenzoate, 4, 5-dimethyl-3, 5-heptanediol dibenzoate, 4, 6-dimethyl-3, 5-heptanediol dibenzoate, 4-dimethyl-3, 5-heptanediol dibenzoate, 2-methyl-3-ethyl-3, 5-heptanediol dibenzoate, 2-methyl-4-ethyl-3, 5-heptanediol dibenzoate, 2-methyl-5-ethyl-3, 5-heptanediol dibenzoate, 3-methyl-3-ethyl-3, 5-heptanediol dibenzoate, 3-methyl-4-ethyl-3, 5-heptanediol dibenzoate, 3-methyl-5-ethyl-3, 5-heptanediol dibenzoate, a salt thereof, and a salt thereof, 4-methyl-3-ethyl-3, 5-heptanediol dibenzoate, 4-methyl-4-ethyl-3, 5-heptanediol dibenzoate, 4-methyl-5-ethyl-3, 5-heptanediol dibenzoate, 2-methyl-3-propyl-3, 5-heptanediol dibenzoate, 2-methyl-4-propyl-3, 5-heptanediol dibenzoate, 2-methyl-5-propyl-3, 5-heptanediol dibenzoate, 3-methyl-3-propyl-3, 5-heptanediol dibenzoate, 3-methyl-4-propyl-3, 5-heptanediol dibenzoate, a salt thereof, and a salt thereof, 3-methyl-5-propyl-3, 5-heptanediol dibenzoate, 4-methyl-3-propyl-3, 5-heptanediol dibenzoate, 4-methyl-4-propyl-3, 5-heptanediol dibenzoate, 4-methyl-5-propyl-3, 5-heptanediol dibenzoate.
Most preferably, the internal electron donor compound a is 2, 4-pentanediol dibenzoate and/or 3, 5-heptanediol dibenzoate.
According to a preferred embodiment of the present invention, the internal electron donor compound b is a diether compound represented by formula II,
in the formula II, R' 1 、R’ 2 、R’ 3 、R’ 4 、R’ 5 And R' 6 The same or different, each independently is hydrogen, halogen, C 1 -C 20 Straight or branched alkyl of (2), C 3 -C 20 Substituted or unsubstituted cycloalkyl of (1), C 6 -C 20 Substituted or unsubstituted aryl of (1), C 7 -C 20 Substituted or unsubstituted aralkyl and C 7 -C 20 One of substituted or unsubstituted alkaryl groups; or, R' 1 、R’ 2 、R’ 3 、R’ 4 、R’ 5 And R' 6 Two or more of them are bonded to each other to form a saturated or unsaturated ring;
R’ 7 and R' 8 Are the same or different and are each independently C 1 -C 20 Straight or branched alkyl of (2), C 3 -C 20 Substituted or unsubstituted cycloalkyl of (A), C 6 -C 20 Substituted or unsubstituted aryl of (1), C 7 -C 20 Substituted or unsubstituted aralkyl and C 7 -C 20 Is one of substituted or unsubstituted alkaryl groups.
Preferably, the internal electron donor compound b is a 1, 3-diether compound shown in formula V,
in the formula V, R 9 ' and R 10 ' same or different, each independently hydrogen, halogen, C 1 -C 18 Straight or branched alkyl of (2), C 3 -C 18 Substituted or unsubstituted cycloalkyl of (1), C 6 -C 18 Substituted or unsubstituted aryl of (1) and C 7 -C 18 One of substituted or unsubstituted aralkyl, orR is 9 ' and R 10 ' bonding to each other to form a ring; r 11 ' and R 12 ' same or different, each independently C 1 -C 10 Linear or branched alkyl.
According to the present invention, examples of the internal electron donor compound b may include, but are not limited to: 2- (2-ethylhexyl) -1, 3-dimethoxypropane, 2-isopropyl-1, 3-dimethoxypropane, 2-butyl-1, 3-dimethoxypropane, 2-sec-butyl-1, 3-dimethoxypropane, 2-cyclohexyl-1, 3-dimethoxypropane, 2-phenyl-1, 3-dimethoxypropane, 2- (2-phenylethyl) -1, 3-dimethoxypropane, 2- (2-cyclohexylethyl) -1, 3-dimethoxypropane, 2- (p-chlorophenyl) -1, 3-dimethoxypropane, 2- (diphenylmethyl) -1, 3-dimethoxypropane, 2- (cyclohexylethyl) -2-dimethoxypropane, 2- (p-chlorophenyl) -1, 3-dimethoxypropane, 2- (diphenylmethyl) -1, 3-dimethoxypropane, 2- (cyclohexylmethyl) -2-dimethoxypropane, 2-propyl-propane, 2- (cyclohexylpropyl) -1, 3-dimethoxypropane, 2- (cyclohexylpropyl) -1, 3-dimethoxypropane, 2- (cyclohexylpropyl) propane, 2-dimethoxypropane, 2-propane, 2- (cyclohexylpropyl-diol, 2-diol, and a mixture thereof, 2, 2-dicyclohexyl-1, 3-dimethoxypropane, 2-dicyclopentyl-1, 3-dimethoxypropane, 2-diethyl-1, 3-dimethoxypropane, 2-dipropyl-1, 3-dimethoxypropane, 2-diisopropyl-1, 3-dimethoxypropane, 2-dibutyl-1, 3-dimethoxypropane, 2-methyl-2-propyl-1, 3-dimethoxypropane, 2-methyl-2-benzyl-1, 3-dimethoxypropane, 2-methyl-2-ethyl-1, 3-dimethoxypropane, 2-methyl-2-isopropyl-1, 3-dimethoxypropane, 2-methyl-2-phenyl-1, 3-dimethoxypropane, 2-methyl-2-cyclohexyl-1, 3-dimethoxypropane, 2-bis (2-cyclohexylethyl) -1, 3-dimethoxypropane, 2-methyl-2-isobutyl-1, 3-dimethoxypropane, 2-methyl-2- (2-ethylhexyl) -1, 3-dimethoxypropane, 2-diisobutyl-1, 3-dimethoxypropane, 2-diphenyl-1, 3-dimethoxypropane, 2-dibenzyl-1, 3-dimethoxypropane, 2, 2-bis (cyclohexylmethyl) -1, 3-dimethoxypropane, 2-isobutyl-2-isopropyl-1, 3-dimethoxypropane, 2- (1-methylbutyl) -2-isopropyl-1, 3-dimethoxypropane, 2-isopropyl-2-isoamyl-1, 3-dimethoxypropane, 2-phenyl-2-isopropyl-1, 3-dimethoxypropane, 2-phenyl-2-sec-butyl-1, 3-dimethoxypropane, 2-benzyl-2-isopropyl-1, 3-dimethoxypropane, 2-cyclopentyl-2-isopropyl-1, 3-dimethoxypropane, 2-methyl-2-isopropyl-1, 3-dimethoxypropane, 2-methyl-2-isopropyl-1, 3-dimethoxypropane, 2-isopropyl-1, 3-dimethoxypropane, 2-isopropyl-methyl-2-isopropyl-1, 3-dimethoxypropane, 2-propyl, 2-methyl-2-methyl-ethyl-2-methyl-ethyl, 2-cyclopentyl-2-sec-butyl-1, 3-dimethoxypropane, 2-cyclohexyl-2-isopropyl-1, 3-dimethoxypropane, 2-cyclohexyl-2-sec-butyl-1, 3-dimethoxypropane, 2-isopropyl-2-sec-butyl-1, 3-dimethoxypropane, 2-cyclohexyl-2-cyclohexylmethyl-1, 3-dimethoxypropane, 9-dimethoxymethylfluorene.
Most preferably, the internal electron donor compound b is 2-isopropyl-2-isoamyl-1, 3-dimethoxypropane and/or 9, 9-dimethoxymethylfluorene.
In the present invention, the 1, 3-diether compound can be synthesized by the methods disclosed in CN1020448C, CN100348624C and CN 1141285A. The disclosure of which is incorporated herein by reference in its entirety. And will not be described in detail herein.
In the method of the present invention, the solid component is prepared as follows: reacting a magnesium-containing support with the titanium compound and adding the internal electron donor in one or more time periods before, during, and after the reaction of the magnesium-containing support with the titanium compound.
In the present invention, the molar ratio of the magnesium-containing compound, the titanium-containing compound and the internal electron donor component used in preparing the catalyst solid component is not particularly limited and may vary within a wide range, and preferably, the molar ratio of the magnesium-containing compound, the titanium-containing compound and the internal electron donor component is 1: 10-200: 0.04-0.8, and more preferably, the molar ratio of the magnesium-containing compound, the titanium-containing compound and the internal electron donor is 1: 20-180: 0.05-0.5, and more preferably, the molar ratio of the magnesium-containing compound, the titanium-containing compound and the internal electron donor is 1: 50-120: 0.2-0.4.
According to the invention, the magnesium-containing compound can be a magnesium-containing compound shown in a formula VI and/or an adduct of the magnesium-containing compound shown in the formula VI,
MgR 13 R 14 formula VI
In formula VI, R 13 And R 14 May be the same or different and are each independently halogen, C 1 -C 5 And C is a linear or branched alkoxy group 1 -C 5 Is one of linear or branched alkyl.
The olefin polymerization catalyst component of the inventionWherein the adduct of the magnesium-containing compound represented by the formula VI is MgR 13 R 14 ·fR 0 OH·gE·hH 2 O, wherein R 0 Is C 1 -C 18 Is preferably C 1 -C 5 More preferably methyl, ethyl, n-propyl and isopropyl; f is in the range of 0.1 to 6, preferably 2 to 3.5; e is an electron donor compound which can be various electron donor compounds known in the art, and g is in the range of 0-2; h is in the range of 0-0.7. Preferably, in formula VI, R 13 And R 14 Each independently a halogen, for example one of chlorine, bromine and iodine.
According to the present invention, preferably, the magnesium-containing compound may be at least one of dimethoxymagnesium, diethoxymagnesium, dipropoxymagnesium, diisopropoxymagnesium, dibutoxymagnesium, diisobutyoxymagnesium, dipentyoxymagnesium, methoxymagnesium chloride, methoxymagnesium bromide, methoxymagnesium iodide, ethoxymagnesium chloride, ethoxymagnesium bromide, ethoxymagnesium iodide, propoxymagnesium chloride, propoxymagnesium bromide, propoxymasium iodide, butoxymagnesium chloride, butoxymagnesium bromide, butoxymagnesium iodide, magnesium dichloride, magnesium dibromide, magnesium diiodide, an alcohol adduct of magnesium dichloride, an alcohol adduct of magnesium dibromide, and an alcohol adduct of magnesium diiodide. Further preferably, the magnesium compound is an alcohol adduct of magnesium dichloride in the form of spherical particles.
In the present invention, the magnesium-containing compound is prepared by methods well known in the art, for example, by referring to the preparation methods of magnesium halide adduct supports disclosed in CN1091748A, CN101050245A, CN101486722A, CN102796132A, CN102796129A and CN 102796128A.
In general, the preparation method of the spherical alcohol adduct of magnesium dichloride may include: by reacting magnesium dichloride with R 0 High shearing OH in dispersing medium at 90-140 deg.C, cooling at-20 deg.C to 0 deg.C to form spherical particles, washing and drying to obtain spherical particlesWherein R is 0 Is C 1 -C 18 Is preferably C 1 -C 5 More preferably methyl, ethyl, n-propyl and isopropyl. Magnesium dichloride and R 0 The molar ratio of OH can be 1: 1-6, preferably 1: 2-4.
The method of high shear may for example be the method disclosed in CN1330086, the method disclosed in US6020279, the method disclosed in CN1580136A and the method disclosed in CN 1463990A. The dispersion medium may be a hydrocarbon-based solvent, for example: kerosene, white oil, silicone oil, paraffin oil and vaseline oil. The cooling medium may be pentane, hexane, heptane, petroleum ether and raffinate oil in petroleum refining.
When the alcohol adduct of magnesium dichloride is spherical particles, the catalyst component obtained by reacting the alcohol adduct of magnesium dichloride with the titanium-containing compound, the internal electron donor compound a, and the internal electron donor compound b is also spherical particles.
In the present invention, the titanium-containing compound may be a titanium-containing compound commonly used in the art. Preferably, the titanium compound is a compound of formula VII and/or formula viii:
TiX p (OR 15 ) 4-p formula VII
TiX q (OR 15 ) 3-q Of the formula VIII
In the formulae VII and VIII, X is halogen, R 15 Is C 1 -C 20 P is an integer of 1 to 4, and q is an integer of 1 to 3.
Further preferably, the titanium-containing compound is one or more of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, tributoxytitanium chloride, dibutoxytitanium dichloride, butoxytitanium trichloride, triethoxytitanium chloride, diethoxytitanium dichloride, ethoxytitanium trichloride and titanium trichloride. Most preferably, the titanium-containing compound is titanium tetrachloride.
Preferably, the method for preparing the catalyst component further comprises filtering the liquid and recovering the solid, washing the recovered solid with a liquid titanium compound (such as titanium tetrachloride) in an amount of preferably from 8mL to 40mL per gram of the magnesium-containing compound, and then washing the resulting solid catalyst component with an inert solvent in multiple times. The inert solvent may be selected from aliphatic and aromatic hydrocarbons, for example, hexane, heptane, octane, decane, toluene, and the like.
In the preparation method of the catalyst component for olefin polymerization, the internal electron donor component is added in one or more time periods before, during and after the reaction of the magnesium-containing compound and the titanium-containing compound. The time period before the reaction of the magnesium-containing compound with the titanium-containing compound means a time period after the magnesium compound is added to the reactor and before the temperature is raised to the reaction temperature.
In the present invention, in the preparation of the catalyst component, the internal electron donor compound a and the internal electron donor compound b may be added to the mixture of the magnesium-containing compound and the titanium-containing compound in several times or simultaneously.
According to the present invention, the reaction of the magnesium-containing compound with the titanium-containing compound can be carried out according to the method disclosed in the prior art, for example, the titanium-containing compound can be cooled to 0 ℃ or less (preferably-5 to-35 ℃), then the magnesium-containing compound is added and stirred and mixed at that temperature for 10 to 60 minutes, and then warmed to the reaction temperature (preferably 60 to 130 ℃) and maintained at that reaction temperature for 0.5 to 10 hours. Adding an internal electron donor compound a and an internal electron donor compound b in the temperature rising process. The liquid is then filtered off and the solid is recovered and the recovered solid is treated one or more times with a titanium compound in liquid form and finally washed several times with an inert solvent to obtain the catalyst component.
According to the present invention, in the above-mentioned olefin polymerization catalyst, the alkyl aluminum compound may be various alkyl aluminum compounds commonly used in the field of olefin polymerization, which can be used as a cocatalyst for the olefin polymerization catalyst. Preferably, the alkyl aluminum compound is a compound of formula IX,
AlR’ n' X’ 3-n' formula IX
In the formula IX, R' is C 1 -C 8 X 'is halogen and n' is an integer of 1 to 3. In formula IX, X' is preferably one or more of chlorine, bromine and iodine, more preferably chlorine.
More preferably, the aluminum alkyl compound is triethylaluminum, tripropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, triisobutylaluminum, diethylaluminum monohydrochloride, diisobutylaluminum monohydrochloride, diethylaluminum monochloride, diisobutylaluminum dichloride, Al (n-C) 6 H 13 ) 3 And Al (n-C) 8 H 17 ) 3 One or more of (a).
Most preferably, the alkyl aluminium compound is triethyl aluminium and/or triisobutyl aluminium.
According to the invention, the alkyl aluminum compound may be used in amounts conventional in the art. Preferably, the molar ratio of aluminium in the aluminium alkyl compound to titanium in the catalyst component is from 1 to 2000: 1. further preferably, the molar ratio of aluminium in the aluminium alkyl compound to titanium in the catalyst component is from 1 to 500: 1, more preferably, the molar ratio of aluminium in the aluminium alkyl compound to titanium in the catalyst component is from 20 to 300: 1, most preferably, the molar ratio of aluminium in the aluminium alkyl compound to titanium in the catalyst component is from 30 to 200: 1.
according to the present invention, in a preferred case, the molar ratio between the aluminium in the aluminium alkyl compound and the external electron donor compound is between 1 and 50: 1, preferably 2 to 20: 1. controlling the amounts of the alkylaluminum compound and the external electron donor compound within the above preferred ranges can further improve the properties of the resulting polymer.
According to the present invention, the external electron donor compound may be any of various external electron donor compounds commonly used in the art for achieving the above object, such as: one or more of carboxylic acids, carboxylic acid anhydrides, carboxylic acid esters, ketones, ethers, alcohols, lactones, organophosphorus compounds, and organosilicon compounds. Preferably, the external electron donor compound is an organosilicon compound represented by the formula X,
(R 16 ) m’ (R 17 ) p’ Si(OR 18 ) q’ formula X
In the formula X, R 16 、R 17 And R 18 Each independently is C 1 -C 18 Optionally containing heteroatoms, said heteroatoms being one or more of F, Cl, Br, N and I; m 'and p' are each independently an integer of 0 to 2, q 'is an integer of 1 to 3, and the sum of m', p 'and q' is 4.
Preferably, R 16 And R 17 Each independently is C 3 -C 10 Straight or branched alkyl of (2), C 3 -C 10 Alkenyl group of (C) 3 -C 10 Alkylene of (C) 3 -C 10 Substituted or unsubstituted cycloalkyl and C 6 -C 10 Optionally containing heteroatoms, said heteroatoms being one or more of F, Cl, Br, N and I; r 18 Is C 1 -C 10 More preferably methyl.
According to the present invention, specific examples of the organosilicon compound may be, but are not limited to: cyclohexylmethyldimethoxysilane, diisopropyldimethoxysilane, di-n-butyldimethoxysilane, diisobutyldimethoxysilane, diphenyldimethoxysilane, methyl-t-butyldimethoxysilane, dicyclopentyldimethoxysilane, cyclohexyltrimethoxysilane, t-butyltrimethoxysilane, thexyltrimethoxysilane and 2-ethylpiperidinyl-2-t-butyldimethoxysilane.
More preferably, the external electron donor compound is cyclohexylmethyldimethoxysilane and/or dicyclopentyldimethoxysilane.
The external electron donor may be added directly into the reactor or added into the apparatus and pipeline related to the reactor, or added separately or together if two or more reactors are connected in series.
According to the present invention, the catalyst may be directly fed into the reactor during the preparation of the olefin polymer, or may be fed into the reactor after pre-complexing and/or pre-polymerization as is well known in the art.
According to the invention, the olefin polymer is prepared by carrying out polymerization in a liquid-phase monomer or an inert solvent containing a polymerization monomer under the protection of an inert gas, or in a gas phase, or by a combined gas-liquid phase polymerization process.
The kinds and amounts of the inert gas and the solvent are well known to those skilled in the art during the polymerization of olefins, and will not be described herein.
In the invention, liquid phase polymerization is preferred, and in the liquid phase polymerization, hydrogen is used as a molecular weight regulator, the concentration of the hydrogen is 1000-4000ppm, and the feeding ratio (mass ratio) of ethylene to propylene is as follows: 0.01-0.04:1, preferably 0.012-0.03: 1. The polymerization temperature is 10-150 ℃, preferably 60-90 ℃; the polymerization pressure is higher than the saturation vapor pressure of propylene at the corresponding polymerization temperature.
The pressures in the present invention are all gauge pressures.
The polymerization method is suitable for the mature and large-scale Spheripol process, Unipol process, Hypol process and the like.
The polymers of the present invention may form compositions which may contain additives commonly used in the art, such as antioxidants, antistatic agents, slip agents, and the like.
The ethylene-propylene random copolymer has the advantages of low melting point, less xylene soluble substances and less micromolecule content, and does not contain plasticizer.
The invention also provides application of the ethylene-propylene random copolymer in the field of food and/or medical and sanitary products. For example, as food packaging.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The invention is further illustrated by the following examples. In the following examples:
the sequence distribution and composition of the copolymer is 13 C nuclear magnetic resonance analysis ( 13 C NMR). The samples were measured on an Avance III 400MHz NMR spectrometer from Bruker, Germany. The solvent is deuterated o-dichlorobenzene, the testing temperature is 125 ℃, and the scanning times are more than 5000 times. According to 13 The data of the C NMR spectrum allow the calculation of the sequence distribution and the composition of the copolymer. The specific calculation formula is as follows:
[PEP]/[E]＝[PEP]/([EEE]+[EEP]+[PEP])
the melting point of the polymer was measured by Differential Scanning Calorimetry (DSC). DSC measurement is carried out on the sample by adopting a Perkin-Elmer DSC-7 type differential scanning calorimeter (USA), and the dosage of the sample is 4-5 mg. Heating the sample to 200 ℃ at the speed of 10 ℃/min, keeping the temperature for 5min to eliminate the thermal history, then cooling to 50 ℃ at the speed of 10 ℃/min, keeping the temperature at 50 ℃ for 1min, then heating to 200 ℃ at the speed of 10 ℃/min, and determining the crystallization temperature, the crystallization enthalpy, the melting temperature and the melting enthalpy from the heat flow curves recorded by cooling and re-heating.
The xylene solubles content (X.S) of the polymer was tested in accordance with GB/T24282-.
The percentage of fractions having a polymer weight average molecular weight of less than 1000 was determined using Gel Permeation Chromatography (GPC). The method adopts Shimadzu LC-10AT Gel Permeation Chromatograph (GPC), wherein trichlorobenzene is used as mobile phase and the temperature is 150 ℃.
Example 1
This example serves to illustrate an ethylene-propylene random polymer and a process for its preparation according to the invention.
(1) Preparation of catalyst components: adding 90ml titanium tetrachloride into a 300ml glass reaction bottle with a stirrer, fully replacing with high-purity nitrogen, cooling to-20 ℃, adding 8g of spherical magnesium chloride alcohol compound (the preparation method is shown in Chinese patent CN1330086A), gradually heating to 110 ℃, adding 1ml of 2, 4-pentanediol dibenzoate and 1.5ml of 2-isopropyl-2-isoamyl-1, 3-dimethoxypropane in the heating process, keeping the temperature at 110 ℃ for 0.5h, filtering to remove liquid, adding titanium tetrachloride for treatment, washing with hexane five times, and drying in vacuum to obtain the spherical catalyst component Cat-1.
(2) Catalyst component (Cat-1), triethylaluminum and dicyclopentyldimethoxysilane (the molar ratio of the catalyst component in titanium element to the triethylaluminum in aluminum element is 1: 180; and the molar ratio of dicyclopentyldimethoxysilane to the triethylaluminum in aluminum element is 1:8) are continuously introduced into a loop reactor for propylene polymerization reaction, the polymerization reaction temperature is 70 ℃, the reaction pressure is 3.5MPa, hydrogen is introduced into the feed of the loop reactor, the concentration of the hydrogen (detected by on-line chromatography) is 2100ppm, the feed mass ratio of ethylene to propylene is 0.02:1, the reaction time is 1.5h, and then the propylene is subjected to flash evaporation, steaming and finally discharging. The obtained polymer was analyzed, and the results are shown in Table 1.
Example 2
This example serves to illustrate an ethylene-propylene random polymer and a process for its preparation according to the invention.
A catalyst component and a polymer were prepared by following the procedure of example 1 except that in the preparation of the polymer, the feed mass ratio of ethylene to propylene was 0.016:1, and the obtained polymer was analyzed, and the results are shown in Table 1.
Example 3
This example illustrates an ethylene-propylene random polymer and a method for preparing the same according to the present invention.
A catalyst component and a polymer were prepared by following the procedure of example 1, except that 1.1ml of 3, 5-heptanediol dibenzoate and 1.3ml of 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane were added during the temperature rise for the preparation of the catalyst component, to obtain a spherical catalyst component Cat-2. In the process for preparing the polymer, the molar ratio of the catalyst component calculated as titanium element to triethylaluminum calculated as aluminum element was 1: 100, respectively; the molar ratio of cyclohexylmethyldimethoxysilane to triethylaluminum, calculated as aluminum element, was 1:5, the hydrogen concentration (determined by on-line chromatography) was 2000ppm and the feed mass ratio of ethylene to propylene was 0.022: 1. The obtained polymer was analyzed, and the results are shown in Table 1.
Example 4
This example illustrates an ethylene-propylene random polymer and a method for preparing the same according to the present invention.
A catalyst component and a polymer were prepared by following the procedure of example 3 except that the feed mass ratio of ethylene to propylene during the preparation of the polymer was 0.015: 1. The resulting polymer was analyzed, and the results are shown in Table 1.
Example 5
This example serves to illustrate an ethylene-propylene random polymer and a process for its preparation according to the invention.
A catalyst component and a polymer were prepared by following the procedure of example 1, except that 0.9ml of 2, 4-pentanediol dibenzoate and 0.5g of 9, 9-dimethoxymethylfluorene were added during the temperature rise for the preparation of the catalyst component, to obtain a spherical catalyst component Cat-3. In the process for preparing the polymer, the molar ratio of the catalyst component calculated as titanium element to triethylaluminum calculated as aluminum element was 1: 150; the molar ratio of cyclohexylmethyldimethoxysilane to triethylaluminum, calculated as aluminum element, was 1:5, the polymerization temperature was 68 ℃, the concentration of hydrogen (determined by on-line chromatography) was 2000ppm and the feed mass ratio of ethylene to propylene was 0.028: 1. The obtained polymer was analyzed, and the results are shown in Table 1.
Example 6
This example serves to illustrate an ethylene-propylene random polymer and a process for its preparation according to the invention.
A catalyst component and a polymer were prepared by the same procedures as in example 5, except that the feed mass ratio of ethylene to propylene in the production of the polymer was 0.018: 1. The obtained polymer was analyzed, and the results are shown in Table 1.
Comparative example 1
The commercial product FCP80 was analyzed and the copolymer was produced using DQC catalyst (containing phthalate) and the results are shown in table 1.
TABLE 1
| Numbering | C 2 (wt％) | [PEP]/[E](％) | X.S(wt％) | Melting Point (. degree.C.) | Mw<1000(％) |
| Example 1 | 3.8 | 84 | 3.7 | 136 | 0 |
| Example 2 | 3.2 | 85 | 2.8 | 140 | 0 |
| Example 3 | 4.2 | 83 | 4.4 | 135 | 0 |
| Example 4 | 2.9 | 84 | 2.7 | 141 | 0 |
| Example 5 | 4.9 | 83 | 4.9 | 132 | 0 |
| Example 6 | 3.4 | 85 | 2.8 | 139 | 0 |
| Comparative example 1 | 3.4 | 71 | 6.1 | 146 | 0.035 |
From the results of examples 1 to 6 and comparative example 1, it can be seen that the ethylene-propylene random copolymer of the present invention has a more uniform distribution of ethylene in the molecular chain, a higher value of [ PEP ]/[ E ], a lower melting point, a lower xylene soluble content and a lower small molecule content, and does not contain phthalate (plasticizer), and is more advantageous for applications in the fields of food packaging, medical health, and the like.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
Claims (20)
1. A plasticizer-free ethylene-propylene random copolymer, characterized in that the ethylene-propylene random copolymer contains 93-98 wt% of propylene and 2-7 wt% of ethylene, based on the weight of the ethylene-propylene random copolymer;
the melting point of the ethylene-propylene random copolymer is lower than 143 ℃, the content of xylene soluble substances is less than or equal to 5wt percent, and the ethylene-propylene random copolymer is prepared by 13 C NMR measured [ PEP]/[E]＞78％；
The ethylene-propylene random copolymer does not contain a portion having a weight average molecular weight of less than 1000.
2. The ethylene-propylene random copolymer according to claim 1, wherein the ethylene-propylene random copolymer comprises 95 to 97 wt% propylene and 3 to 5 wt% ethylene, based on the weight of the ethylene-propylene random copolymer;
the melting point of the ethylene-propylene random copolymer is lower than 140 ℃, the content of xylene soluble substances is less than or equal to 4wt percent, and the ethylene-propylene random copolymer is prepared by 13 C NMR measured [ PEP]/[E]＞80％。
3. The ethylene-propylene random copolymer according to claim 2, wherein the xylene solubles content is less than or equal to 3 wt%.
4. The ethylene-propylene random copolymer of claim 2, wherein the ethylene-propylene random copolymer is polymerized with 13 C NMR measured [ PEP]/[E]＞83％。
5. The ethylene-propylene random copolymer according to any of claims 1-4, wherein the ethylene-propylene random copolymer is prepared by a process comprising the steps of: under the condition of olefin polymerization, propylene and ethylene are polymerized in the presence of a catalyst and hydrogen to obtain the ethylene-propylene random copolymer;
wherein the catalyst comprises a solid component, an alkyl aluminum compound and an optional external electron donor compound, and the solid component comprises a reaction product of the following components:
(i) a magnesium-containing compound;
(ii) a titanium-containing compound; and
(iii) an internal electron donor;
the internal electron donor comprises an internal electron donor compound a and an internal electron donor compound b, and the molar ratio of the internal electron donor compound a to the internal electron donor compound b is 0.1-20: 1; the internal electron donor compound a is a glycol ester compound, and the internal electron donor compound b is a diether compound.
6. The ethylene-propylene random copolymer according to claim 5, wherein the molar ratio of the internal electron donor compound a to the internal electron donor compound b is 0.3-8: 1.
7. the ethylene-propylene random copolymer according to claim 5, wherein the internal electron donor compound a is a diol ester compound represented by formula I,
in the formula I, R 1 And R 2 Identical or different, each independently is halogen, C 1 -C 20 Straight or branched alkyl of (2), C 2 -C 20 Linear or branched alkenyl of (C) 3 -C 20 Substituted or unsubstituted cycloalkyl of (A), C 6 -C 20 Substituted or unsubstituted aryl of (1), C 7 -C 20 Substituted or unsubstituted aralkyl or C 7 -C 20 Optionally substituted or unsubstituted alkaryl, the aryl, aralkyl or aryl ring of the alkaryl being optionally substituted by a group selected from halogen, C 1 -C 6 And C is a straight or branched alkyl group 1 -C 6 Substituted with one or more of alkoxy groups of (a);
R 3 、R 4 、R 5 、R 6 and R 1 -R 2n The same or different, each independently hydrogen, halogen, C 1 -C 20 Straight or branched alkyl of (2), C 3 -C 20 Substituted or unsubstituted cycloalkyl of (A), C 6 -C 20 Substituted or unsubstituted aryl of (1), C 7 -C 20 Substituted or unsubstituted alkylaryl of, C 7 -C 20 Substituted or unsubstituted aralkyl of (1), C 2 -C 20 Linear or branched alkenyl of (C) 2 -C 20 Ester group of (A) and (C) 10 -C 20 One of the condensed ring aromatic groups of (1), R 3 、R 4 、R 5 、R 6 And R 1 -R 2n Optionally containing heteroatoms, which are one or more of nitrogen, oxygen, sulfur, silicon, halogen and phosphorus; or, R 3 、R 4 、R 5 、R 6 And R 1 -R 2n Two or more of them are bonded to each other to form a saturated or unsaturated ring;
n is an integer of 0 to 10.
8. The ethylene-propylene random copolymer according to claim 7, wherein the internal electron donor compound a is a diol ester compound represented by formula IV,
in the formula IV, R 10 、R 11 、R 12 、R 13 、R 14 And R 15 The same or different, each independently hydrogen or C 1 -C 20 Linear chain of (2)Or a branched alkyl group.
9. The ethylene-propylene random copolymer of claim 5, wherein the internal electron donor compound b is a diether compound represented by formula II,
in the formula II, R' 1 、R’ 2 、R’ 3 、R’ 4 、R’ 5 And R' 6 The same or different, each independently is hydrogen, halogen, C 1 -C 20 Straight or branched alkyl of (2), C 3 -C 20 Substituted or unsubstituted cycloalkyl of (A), C 6 -C 20 Substituted or unsubstituted aryl of (1), C 7 -C 20 Substituted or unsubstituted aralkyl and C 7 -C 20 One of substituted or unsubstituted alkaryl groups; or, R' 1 、R’ 2 、R’ 3 、R’ 4 、R’ 5 And R' 6 Two or more of them are bonded to each other to form a saturated or unsaturated ring;
R’ 7 and R' 8 Are the same or different and are each independently C 1 -C 20 Straight or branched alkyl of (2), C 3 -C 20 Substituted or unsubstituted cycloalkyl of (1), C 6 -C 20 Substituted or unsubstituted aryl of (1), C 7 -C 20 Substituted or unsubstituted aralkyl and C 7 -C 20 Or a substituted or unsubstituted alkylaryl group.
10. The ethylene-propylene random copolymer of claim 9, wherein the internal electron donor compound b is a 1, 3-diether compound represented by formula V,
in the formula V, R 9 ' and R 10 ' same or different, each independently hydrogen, halogen, C 1 -C 18 Straight or branched alkyl of (2), C 3 -C 1 8 substituted or unsubstituted cycloalkyl, C 6 -C 1 8 substituted or unsubstituted aryl and C 7 -C 1 8, or one of substituted or unsubstituted aralkyl, or, R9' and R1 0 ' bonding to each other to form a ring; r11' and R1 2 ' the same or different, each independently C1-C1 0 Linear or branched alkyl groups of (a).
11. The ethylene-propylene random copolymer according to claim 5, wherein the molar ratio of the magnesium-containing compound, the titanium-containing compound and the internal electron donor is 1: 10-200: 0.04-0.8.
12. The ethylene-propylene random copolymer according to claim 11, wherein the molar ratio of the magnesium-containing compound, the titanium-containing compound and the internal electron donor is 1: 20-180: 0.05-0.5.
13. The ethylene-propylene random copolymer according to claim 12, wherein the molar ratio of the magnesium-containing compound, the titanium-containing compound and the internal electron donor is 1: 50-120: 0.2-0.4.
14. The ethylene-propylene random copolymer according to claim 5, wherein the magnesium-containing compound is a magnesium-containing compound of formula VI and/or an adduct of a magnesium-containing compound of formula VI,
MgR 13 R 14 formula VI
In formula VI, R 13 And R 14 May be the same or different and are each independently halogen, C 1 -C 5 And C is a linear or branched alkoxy group 1 -C 5 One of linear or branched alkyl;
the titanium-containing compound is a compound shown in a formula VII and/or a formula VIII:
TiX p (OR 15 ) 4-p formula VII
TiX q (OR 16 ) 3-q Of the formula VIII
In the formulae VII and VIII, X is halogen and R 15 And R 16 Each independently is C 1 -C 20 P is an integer of 1 to 4, and q is an integer of 1 to 3.
15. The ethylene-propylene random copolymer according to claim 5, wherein the molar ratio of the aluminium of the alkyl aluminium compound to the titanium of the solid component is from 1 to 2000: 1;
the molar ratio of aluminum in the alkyl aluminum compound to the external electron donor compound is 1-50: 1.
16. the ethylene-propylene random copolymer according to claim 15, wherein the molar ratio of the aluminium of the alkyl aluminium compound to the titanium of the solid component is from 1 to 500: 1.
17. the ethylene-propylene random copolymer according to claim 16, wherein the molar ratio of the aluminium of the alkyl aluminium compound to the titanium of the solid component is from 20 to 300: 1.
18. the ethylene-propylene random copolymer according to claim 17, wherein the molar ratio of the aluminium of the alkyl aluminium compound to the titanium of the solid component is from 30 to 200: 1.
19. the ethylene-propylene random copolymer of claim 15, wherein the molar ratio of aluminum in the aluminum alkyl compound to the external electron donor compound is from 2 to 20: 1.
20. use of the ethylene-propylene random copolymer according to any one of claims 1 to 19 in the field of food and/or medical hygiene articles.
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| WO2015135903A1 (en) * | 2014-03-14 | 2015-09-17 | Basell Poliolefine Italia S.R.L. | Catalyst components for the polymerization of olefins |
| CN105440180A (en) * | 2014-08-15 | 2016-03-30 | 中国石油化工股份有限公司 | Propylene polymer and preparation method thereof |
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