CN1163282A - Polypropylene film - Google Patents

Polypropylene film Download PDF

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CN1163282A
CN1163282A CN97103082A CN97103082A CN1163282A CN 1163282 A CN1163282 A CN 1163282A CN 97103082 A CN97103082 A CN 97103082A CN 97103082 A CN97103082 A CN 97103082A CN 1163282 A CN1163282 A CN 1163282A
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alpha
ethylene
random copolymers
olefin random
compound
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CN1059451C (en
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田中泰夫
杉正浩
中川德彦
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Mitsui Petrochemical Industries Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10—Homopolymers or copolymers of propene
    • C08J2323/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/04—Homopolymers or copolymers of ethene
    • C08J2423/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/04—Homopolymers or copolymers of ethene
    • C08J2423/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/10—Transparent films; Clear coatings; Transparent materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/06—Properties of polyethylene
    • C08L2207/066—LDPE (radical process)
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene

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  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Abstract

Disclosed is a polypropylene film formed from a polypropylene composition comprising 5 to 60 parts by weight of a specific ethylene/C5-C20 alpha-olefin random copolymer (A) and 40 to 95 parts by weight of crystalline polypropylene (B), the total amount of said components (A) and (B) being 100 parts by weight. The ethylene/C5-C20 alpha-olefin random copolymer is a copolymer comprising ethylene and an alpha-olefin 5 to 20 carbon atoms and has the properties: the density is in the range of 0.870 to 0.900 g/cm<3>; the melt flow rate (MFR, ASTMD 1238, 190 DEG C, load of 2.16 kg) is in the range of 0.01 to 50 g/10 min; and the temperature (Tm DEG C) at the position of the maximum peak of an endotherm curve of this copolymer measured by DSC and the density (d g/cm<3>) satisfy a specific relation.

Description

Polypropylene film
The present invention relates to polypropylene film, more specifically relate to the polypropylene film that mechanical property (especially tensile property and shock strength) and heat seal strength are better than conventional polypropylene film.
Crystalline polypropylene film has good rigidity, surface luster and thermotolerance, but shock resistance is relatively poor.In order to improve shock resistance, widespread use is with crystalline polypropylene and rubber-like substance (as polyisobutene, polyhutadiene, amorphous ethylene/propene copolymer and amorphous ethylene/butylene copolymers) blended method and with crystalline polypropylene and polyethylene phase blended method mutually usually.In the method for using these properties-correcting agent, the shock resistance of crystalline polypropylene film can improve, but because properties-correcting agent is softer than crystalline polypropylene, the rigidity of film, thermotolerance and surface hardness etc. can significantly descend from the characteristic of crystalline polypropylene.
On the other hand, crystalline polypropylene film has good mechanical property (as tensile strength and rigidity) and optical property (as gloss and transparency).And they have good food hygiene quality, because they are nontoxicitys and scentless.Therefore this class film is widely used in the food product pack field.
But the problem of crystalline polypropylene film is that heat-sealing temperature is high and use temperature is narrow.In order to address these problems, the way of taking is to add the low crystalline resins of ethylene/propene copolymer or ethylene/butylene copolymers and so in crystalline polypropylene, thereby has improved heat sealer.After in crystalline polypropylene, adding low-crystalline ethylene/propylene copolymer or ethylene/butylene copolymers, though the heat seal improved performance, mechanical propertys such as tensile property become bad and heat seal strength descends.
The inventor researchs and solves the method for the problems referred to above in earnest.As a result, find to use the specific ethene/C of some amount 5-C 20The alpha-olefin random copolymers replaces ethylene/propene copolymer or ethylene/butylene copolymers to mix in the crystalline polypropylene, can obtain a kind of polypropylene film by polypropene composition, it not only has good transparency, shock resistance and low temperature heat seal performance, and has good tensile property and heat seal strength.The present invention finishes on the basis of these discoveries.
The invention is intended to solve the above-mentioned problem that interrelates with prior art, the purpose of this invention is to provide and a kind ofly not only have excellent transparency, shock resistance and low temperature heat sealer, and have the good tensile property and the polypropylene film of heat sealing strength.
Polypropylene film of the present invention is to be made by the polypropene composition that comprises following component:
The ethylene/alpha-olefin random copolymers (A) of [I] 5-60 part weight, this multipolymer comprises the alpha-olefin of ethene and a kind of 5-20 carbon atom, and has following character:
Density is 0.870-0.900 gram/cubic centimetre,
Melt flow rate (MFR) (MFR, ASTM D1238, load 2.16 kilograms by 190 ℃) restrains/10 fens for 0.01-50,
The temperature (Tm ℃) that records the endothermic curve peak-peak position of this multipolymer with differential scanning calorimeter (DSC) satisfies following relation with its density (d gram/cubic centimetre):
0.885≤d≤0.900 o'clock,
(14d/15)×1000-734＞Tm≥(14d/15)×1000-744，
0.870≤d＜0.885 o'clock,
(4d/3) * 1000-1088＞Tm 〉=(4d/3) * 1000-1098, and
The crystalline polypropylene (B) of [II] 40-95 part weight,
Described component (A) and total amount (B) are 100 parts of weight.
In the ethylene/alpha-olefin random copolymers (A), be preferably 5-20% (mole) from the content of the component units of alpha-olefin.
Ethene/C 5-C 20Alpha-olefin random copolymers (A) better is in the presence of metalloscene catalyst, the ethene/C that is got by the alpha-olefin copolymer of ethene and 5-20 carbon atom 5-C 20The alpha-olefin random copolymers, the Metallocenic compound reaction that described metalloscene catalyst comprises a kind of Metallocenic compound of IVB group 4 transition metal, a kind of Organoaluminoxy based compound and/or a kind of meeting and IVB group 4 transition metal generates compound and a kind of optional organo-aluminium compound of ion pair.
Among the present invention, preferably use to have the linear ethylene/alpha-olefin random copolymers (A1) of following character or long-chain branch ethylene/alpha-olefin random copolymers (A2) with following character.
Described linear ethylene/alpha-olefin random copolymers (A1) has following character:
(a) density is 0.870-0.900 gram/cubic centimetre,
(b) content of alpha-olefin is 5-20% (mole),
(c) melt flow rate (MFR) (MFR, ASTM D1238, load 2.16 kilograms by 190 ℃) restrains/10 fens for 0.01-50,
(d) temperature (Tm ℃) and its density (d gram/cubic centimetre) that records the endothermic curve peak-peak position of this multipolymer with differential scanning calorimeter (DSC) concerns below satisfying:
0.885≤d≤0.900 o'clock,
(14d/15)×1000-734＞Tm≥(14d/15)×1000-744，
0.870≤d＜0.885 o'clock,
(4d/3)×1000-1088＞Tm≥(4d/3)×1000-1098，
(e) degree of crystallinity that records with X-ray diffraction method is less than 40%,
(f) molecular weight distribution of measuring with GPC (Mw/Mn) is not more than 3.0,
(g) use 13The parameter (B value) of the expression comonomer sequence distribution degree of randomness that the C-NMR method is measured is 1.0-1.4,
(h) limiting viscosity [η] (recording in 135 ℃ naphthane) is 0.5-5.0 dl/g,
(i) the ratio g η of limiting viscosity [η] blank of above-mentioned limiting viscosity [η] and a kind of linear ethylene/propylene copolymer *([η]/[η] blank) greater than 0.95, the weight-average molecular weight of this linear ethylene/propylene copolymer (by light scattering method measuring) is identical with this multipolymer, and ethylene content is 70% (mole),
(j) second-order transition temperature (Tg) (being measured by DSC) is not higher than-50 ℃.
Described long-chain branch ethylene/alpha-olefin random copolymers (A2) has following character:
(a) density is 0.870-0.900 gram/cubic centimetre,
(b) content of alpha-olefin is 5-20% (mole),
(c) melt flow rate (MFR) (MFR, ASTM D1238, load 2.16 kilograms by 190 ℃) restrains/10 fens for 0.01-50,
(d) temperature (Tm ℃) and its density (d gram/cubic centimetre) that records the endothermic curve peak-peak position of this multipolymer with differential scanning calorimeter (DSC) concerns below satisfying:
0.885≤d≤0.900 o'clock,
(14d/15)×1000-734＞Tm≥(14d/15)×1000-744，
0.870≤d＜0.885 o'clock,
(4d/3)×1000-1088＞Tm≥(4d/3)×1000-1098，
(e) degree of crystallinity that records with X-ray diffraction method is less than 40%,
(f) molecular weight distribution of measuring with GPC (Mw/Mn) is not more than 3.0,
(g) use 13The parameter (B value) of the expression comonomer sequence distribution degree of randomness that the C-NMR method is measured is 1.0-1.4,
(h) limiting viscosity [η] (recording in 135 ℃ naphthane) is 0.5-5.0 dl/g,
(i) the ratio g η of limiting viscosity [η] blank of above-mentioned limiting viscosity [η] and a kind of linear ethylene/propylene copolymer *([η]/[η] blank) is 0.2-0.95, and the weight-average molecular weight of this linear ethylene/propylene copolymer (by light scattering method measuring) is identical with this multipolymer, and ethylene content is 70% (mole),
(j) second-order transition temperature (Tg) (being measured by DSC) is not higher than-50 ℃.
In the polypropylene copolymer of the present invention, gross weight with ethylene/alpha-olefin random copolymers (A) and crystalline polypropylene (B) is 100 parts of calculating, density is 0.913-0.935 gram/cubic centimetre, melt flow rate (MFR) (MFR, ASTM D1238,190 ℃, load 2.16 kilograms) preferably be not more than 20 parts of weight for the content of/10 minutes hp-ldpe of 1-40 gram.
Below describe polypropylene film of the present invention in detail.
Ethylene/alpha-olefin random copolymers (A)
The used ethylene/alpha-olefin random copolymers (A) of the present invention is a kind of ethene and the random copolymers with alpha-olefin of 5-20 carbon atom, it can contain from the component units beyond the alpha-olefin of ethene and 5-20 carbon atom, for example, need only these unit and do not make the performance of multipolymer become bad from the component units of diolefin.
Example with alpha-olefin of 5-20 carbon atom has 1-amylene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecylene, 1-dodecylene, 1-tridecylene, tetradecene, 1-15 carbenes, cetene, 1-heptadecene, 1-19 carbenes, 1-eicosylene, 9-methyl isophthalic acid-decene, 11-methyl isophthalic acid-decene and 12-ethyl-tetradecene.Wherein be preferably alpha-olefin, preferably the 1-octene with 6-12 carbon atom.
These alpha-olefins can use separately or two or more are used in combination.
The example of diolefin comprises:
The chain type non-conjugated diene, as 1,4-hexadiene, 1,6-octadiene, 2-methyl isophthalic acid, 5-hexadiene, 6-methyl isophthalic acid, 5-heptadiene and 7-methyl isophthalic acid, 6-octadiene;
The annular non-conjugated diene is as cyclohexadiene, dicyclopentadiene, methyl tetrahydroindene, 5-vinyl norbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornylene and 6-chloromethyl-5-isopropenyl-2-nirbornene; And
Other diolefin, as 2,3-diisopropylidene-5-norbornylene, 2-ethylidene-3-isopropylidene-5-norbornylene and 2-propenyl-2,2-norbornadiene.
These diolefins can use separately or be used in combination.
The content of diolefin generally is not more than 10% (mole), is preferably 0-5% (mole).
In the pointed below scope of the density of the ethylene/alpha-olefin random copolymers (A) that the present invention is used, the quantity of contained alpha-olefin and melt flow rate (MFR).And the temperature T m of the endothermic curve peak-peak position of this multipolymer that records with DSC of this ethylene/alpha-olefin random copolymers (A) (℃) and its density d (gram/cubic centimetre) between have specific relation, and have certain degree of crystallinity.
(a) density of ethylene/alpha-olefin random copolymers (A) is 0.870-0.900 gram/cubic centimetre, is preferably 0.875-0.895 gram/cubic centimetre.
(b) content of alpha-olefin is generally 5-20% (mole) in the ethylene/alpha-olefin random copolymers (A), is preferably 8-18% (mole).
When the content of the alpha-olefin of 5-20 carbon atom was as 5-20% (mole) in the ethylene/alpha-olefin random copolymers (A) that uses, resulting polypropene composition can make the polypropylene film of have excellent mechanical properties (as tensile property and shock resistance), resistance to blocking, smooth property and low temperature heat sealer.
(c) melt flow rate (MFR) of ethylene/alpha-olefin random copolymers (A) (MFR, ASTM D1238, load 2.16 kilograms by 190 ℃) is preferably 0.1-20 gram/10 minutes for 0.01-50 restrains/10 fens.
When the ethylene/alpha-olefin random copolymers (A) that uses melt flow rate (MFR) in above-mentioned scope, can obtain having the propylene compositions of suitable melt viscosity and good mouldability.
(d) temperature (Tm ℃) of the endothermic curve peak-peak position of the ethylene/alpha-olefin random copolymers (A) that records with differential scanning calorimeter (DSC) concerns below satisfying with its density (d gram/cubic centimetre):
0.885≤d≤0.900 o'clock,
(14d/15)×1000-734＞Tm≥(14d/15)×1000-744，
0.870≤d＜0.885 o'clock,
(4d/3)×1000-1088＞Tm≥(4d/3)×1000-1098。
When with the composition manufacturing film of the crystalline polypropylene (B) of ethylene/alpha-olefin random copolymers (A) with above-mentioned characteristic that comprises specific quantity (temperature (Tm ℃) of the endothermic curve peak-peak position that it records with differential scanning calorimeter (DSC) has above-mentioned relation with its density (d gram/cubic centimetre)) and specific quantity, prepared film has good especially thermal viscosity (being that heat seal strength just becomes steady state value at short notice).
The temperature (Tm) of endothermic curve peak-peak position is from about 5 milligrams of samples are placed on the aluminium dish, be heated to 200 ℃ with 10 ℃/minute speed, 200 ℃ of insulations 5 minutes, be cooled to room temperature with 20 ℃/minute speed, the endothermic curve that records with the heating of 10 ℃/minute speed obtains again.Measuring used is the DSC-7 type instrument that Perkin-ElmerCo. makes.
(e) degree of crystallinity of the ethylene/alpha-olefin random copolymers (A) that records with X-ray diffraction method is preferably and is not more than 30% less than 40%.
When using degree of crystallinity less than 40% ethylene/alpha-olefin random copolymers (A), the polypropylene film that can obtain having good low temperature heat seal performance and shock resistance (film shock strength).
Alpha-olefin with the available ethene of ethylene/alpha-olefin random copolymers (A) of above-mentioned performance and 5-20 carbon atom comprises in existence under the condition of vanadium catalyst of soluble vanadium compound and aluminum alkyl halide, or comprises copolymerization under the condition of metalloscene catalyst of the Metallocenic compound of zirconium and so on and Organoaluminoxy based compound in existence and get.
In ethylene/alpha-olefin random copolymers (A), better be to use the linear ethylene/alpha-olefin random copolymers (A1) or the long-chain branch ethylene/alpha-olefin random copolymers (A2) that further have following performance with above-mentioned specific density, alpha-olefin content, MFR and degree of crystallinity.
(f) (A1, molecular weight distribution A2) (Mw/Mn) all is not more than 3.0 to use GPC setting-out line and long-chain branch ethylene/alpha-olefin random copolymers.
(g) (A1 A2), uses for linear and long-chain branch ethylene/alpha-olefin random copolymers 13The C-NMR method measure the parameter (B value) of expression comonomer sequence distribution degree of randomness all be 1.0-1.4.
The B value of ethylene/alpha-olefin random copolymers, be in the expression copolymerization sequence from the parameter of every kind of monomeric component units distribution situation, it can be calculated by following equation:
B＝P OE/(2P O·P E)
P in the formula OAnd P EBe included in the ethylene component in the unmodified ethylene/alpha-olefin random copolymers and the molar fraction of alpha-olefin component respectively, P OEBe the number of ethylene/alpha-olefin alternate sequence and the ratio of two tuple sequence sums.
P O, P EAnd P OENumerical value can determine with following method.
In diameter is 10 millimeters test tube, about 200 milligrams unmodified ethylene/alpha-olefin random copolymers is solved homogeneously in 1 milliliter of hexachlorobutadiene as sample, under following measuring condition, measure it 13The C-NMR spectrum.
Measure temperature: 120 ℃
Survey frequency: 20.05 megahertzes
Spectrum width: 1500 hertz
Filter width: 1500 hertz
Pulse repetition time: 4.2 seconds
Pulse width: 7 microseconds
Integral number of times: 2000-5000
P O, P EAnd P OENumerical value can be by recording under the above-mentioned condition 13The C-NMR spectrum is pressed G.J.Ray (Macromolecules, 10,773 (1977)), and J.C.Randall (Macromolecules, 15,353 (1982)) and the described method of K.Kimura (Polymer, 25,4418 (1984)) are determined.
By on the B value that establishes an equation and obtain, when two kinds of monomers alternately are distributed in the ethylene/alpha-olefin random copolymers, equal 2, and separate fully when two kinds of monomers, equal 0 when aggregating into completely segmented copolymer.
When the ethylene/alpha-olefin random copolymers (A1 or A2) that uses the B value in above-mentioned scope, can obtain to make the polypropylene copolymer of film with excellent heat resistance.
(h) limiting viscosity [η] (recording in 135 ℃ naphthane) linear and long-chain branch ethylene/alpha-olefin random copolymers (A1 or A2) is 0.5-5.0 dl/g, is preferably 0.8-3.0 dl/g.
(i) g that obtains by the limiting viscosity [η] of linear ethylene/alpha-olefin random copolymers (A1)] *Value is greater than 0.95.
G η *Value is defined by following formula.
G η *=[η]]/[η] blank
Wherein [η]] be the limiting viscosity described in top (h), and that [η] blank is a weight-average molecular weight (by light scattering method measuring) is identical with described ethylene/alpha-olefin random copolymers, ethylene content is the limiting viscosity of a kind of linear ethylene/propylene copolymer of 70% (mole).
When use has the linear ethylene of above-mentioned character/alpha-olefin random copolymers (A1), resulting polypropene composition can make have superior mechanical intensity, anti-weather, ozone resistance, low-temperature pliability and stable on heating polypropylene film.
The g η of long-chain branch ethylene/alpha-olefin random copolymers (A2) *Value is preferably 0.4-0.9, more preferably 0.5-0.85 for 0.2-0.95.This g η *Value can be measured as stated above.The g η of ethylene/alpha-olefin random copolymers *Numerical value is not more than 0.95, shows that intramolecularly has formed long-chain branch.
When use had the long-chain branch ethylene/alpha-olefin random copolymers (A2) of above-mentioned character, the polypropene composition of gained had good mouldability, can make the polypropylene film with good appearance with it.
(j) second-order transition temperature (Tg) (being measured by DSC) linear and long-chain branch ethylene/alpha-olefin random copolymers (A1 or A2) is not higher than-50 ℃.
When using glass transition temperature Tg not to be higher than-50 ℃ ethylene/alpha-olefin random copolymers (A1 or A2), resulting polypropene composition can make the film with good low-temperature pliability.
(A1 A2) can comprise under the condition of metalloscene catalyst of special metal cyclopentadinyl compound in existence, with the alpha-olefin random copolymerization of ethene and 5-20 carbon atom and make for better linearity that the present invention is used and long-chain branch ethylene/alpha-olefin random copolymers.
The preparation of ethylene/alpha-olefin random copolymers (A)
As mentioned above, the ethylene/alpha-olefin random copolymers (A) that the present invention is used, can comprise under the condition of vanadium catalyst of soluble vanadium compound and aluminum alkyl halide in existence, or comprise in existence under the condition of metalloscene catalyst of the Metallocenic compound of zirconium and so on and Organoaluminoxy based compound the alpha-olefin random copolymerization of ethene and 5-20 carbon atom and get.
The soluble vanadium compound that is used for vanadium catalyst comprises vanadium tetrachloride, vanadylic chloride, an oxyethyl group vanadous chloride, praseodynium acid vanadium and praseodynium acid vanadyl.
The aluminum alkyl halide that is used for vanadium catalyst comprises ethylaluminium dichloride, monochlor(in)ate diethyl aluminum, sesquialter ethylaluminium chloride, monobromination diethyl aluminum, monochlor(in)ate diisobutyl aluminum, aluminium isobutyl dichloride and sesquialter chlorination aluminium isobutyl.
The Metallocenic compound that is used for the zirconium of metalloscene catalyst comprises:
Dibrominated ethylene (indenyl) closes zirconium (IV),
Silica-based two (the 2-methyl indenyls) of dichloride dimethylated methylene close zirconium (IV),
Dibrominated two (cyclopentadienyl) close zirconium (IV) and
Molybdenyl dichloride (dimethyl cyclopentadienyl) closes zirconium (IV).
The Organoaluminoxy based compound that is used for metalloscene catalyst comprises aikyiaiurnirsoxan beta and benzene-insoluble Organoaluminoxy based compound.
In the metalloscene catalyst, Metallocenic compound and Organoaluminoxy based compound with zirconium and so on also can contain organo-aluminium compound.The example of organo-aluminium compound is triisobutyl aluminium, chlorodimethylalumiu and sesquialter methyl chloride aluminium.
The copolyreaction of the ethene of use vanadium catalyst or metalloscene catalyst and the alpha-olefin of 5-20 carbon atom can be carried out at solution state, suspension state or its middle state.For every kind of situation, all preferably with inert solvent as reaction medium.
Linearity or long-chain branch ethylene/alpha-olefin random copolymers (A1, preparation A2)
As mentioned above, linearity that the present invention preferably uses or long-chain branch ethylene/alpha-olefin random copolymers (A1, A2) can comprise under the condition of metalloscene catalyst of special metal cyclopentadinyl compound in existence, make by the alpha-olefin random copolymerization of ethene and 5-20 carbon atom.
There is no particular restriction for used here metalloscene catalyst, as long as it comprises Metallocenic compound [A].For example, this metalloscene catalyst can be generated compound [C] formation of ion pair by Metallocenic compound [A], organo-aluminium compound [B] and/or a kind of meeting and Metallocenic compound reaction, and perhaps compound [C] and a kind of organo-aluminium compound by Metallocenic compound [A], organo-aluminium compound [B] and/or a kind of meeting and Metallocenic compound reaction generation ion pair constitutes.
Metallocenic compound [A]
Be used to prepare linear ethylene/alpha-olefin random copolymers (A 1) Metallocenic compound (A)
Be used to prepare linear ethylene/alpha-olefin random copolymers (A 1) Metallocenic compound (A) be the compound of available formula [I] expression:
ML x …[I]
In the formula [I], M is the transition metal that is selected from periodictable IVB family, is specially zirconium, titanium or hafnium, and x is the valency of transition metal.
L is the part that is coordinated in transition metal.Have at least one to have cyclopentadienyi skeleton in the ligand L, and the part with cyclopentadienyi skeleton can have substituting group.
Example with part of cyclopentadienyi skeleton is: cyclopentadienyl; The cyclopentadienyl that alkyl or cycloalkyl replaces, as methyl cyclopentadienyl, the ethyl cyclopentadienyl, just or the sec.-propyl cyclopentadienyl, just, different, the second month in a season or tertiary butyl cyclopentadienyl, the hexyl cyclopentadienyl, the octyl group cyclopentadienyl, the dimethyl cyclopentadienyl, trimethylammonium cyclopentadienyl, tetramethyl-ring pentadienyl, the pentamethyl-cyclopentadienyl, the methylethyl cyclopentadienyl, methyl-propyl cyclopentadienyl, methyl butyl cyclopentadienyl, methyl hexyl cyclopentadienyl, the methyl-benzyl cyclopentadienyl, ethyl-butyl cyclopentadienyl, ethylhexyl cyclopentadienyl and methylcyclohexyl cyclopentadienyl; Indenyl; 4,5,6, the 7-tetrahydro indenyl; And fluorenyl.
These groups can be replaced by halogen atom or trialkyl silyl.
In these groups, best is the cyclopentadienyl that alkyl replaces.
When the compound of formula [I] expression has two or more groups with cyclopentadienyi skeleton as ligand L, two silylenes (, phenylbenzene silylene or aminomethyl phenyl silylene silica-based as dimethylated methylene) that can pass through alkylidene group (as ethylidene or propylidene), the alkylidene group (as isopropylidene or phenylbenzene methylene radical) that replaces, silylene or replace in them mutually combine.
Example with other ligand L beyond the part of cyclopentadienyi skeleton comprises: have the alkyl of 1-12 carbon atom, alkoxyl group, aryloxy, halogen atom, hydrogen and-SO 3R a(R wherein aBe alkyl, by the alkyl that halogen atom replaces, aryl, or by the aryl of halogen atom or alkyl replacement).
Example with alkyl of 1-12 carbon atom is alkyl, cycloalkyl, aryl and aralkyl.What can list particularly, is:
Alkyl, as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, amyl group, hexyl, octyl group, decyl and dodecyl;
Cycloalkyl is as cyclopentyl and cyclohexyl;
Aryl is as phenyl and tolyl;
Aralkyl is as benzyl and neophyl.
The example of alkoxyl group is a methoxyl group, oxyethyl group, positive propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert.-butoxy, pentyloxy, hexyloxy, and octyloxy.
Examples of aryloxy is a phenoxy group.
-SO 3R aThe example of group is a methanesulfonate, tosic acid root, trifluoromethanesulfonic acid root and p-chlorobenzenesulfonic acid root.
The example of halogen atom is fluorine, chlorine, bromine and iodine.
Have in the represented Metallocenic compound of following formula some be with zirconium as M, and comprise at least two parts with cyclopentadienyi skeleton.It below is the example of this metalloid cyclopentadinyl compound.
Zirconium (IV) is closed in one hydrogenation two (cyclopentadienyl) of one chlorine,
Dichloride two (cyclopentadienyl) is closed zirconium (IV),
Monochlor(in)ate two (cyclopentadienyl) methyl closes zirconium (IV),
Phenoxy group monochlor(in)ate two (cyclopentadienyl) is closed zirconium (IV),
Dichloride two (methyl cyclopentadienyl) is closed zirconium (IV),
Dichloride two (tertiary butyl cyclopentadienyl) is closed zirconium (IV),
Dichloride two (Zhong Ding cyclopentadienyl) is closed zirconium (IV),
Dichloride two (indenyl) is closed zirconium (IV),
Dichloride two (4,5,6, the 7-tetrahydro indenyl) is closed zirconium (IV),
Dibrominated two (indenyl) closes zirconium (IV),
Dimethyl two (cyclopentadienyl) closes zirconium (IV),
Zirconium (IV) is closed in oxyethyl group chlorination two (cyclopentadienyl),
Dichloride two (fluorenyl) is closed zirconium (IV),
Two (methylsulfonic acids) two (cyclopentadienyl) close zirconium (IV),
Two (tosic acid) two (cyclopentadienyl) close zirconium (IV),
Two (trifluoromethanesulfonic acids) two (cyclopentadienyl) close zirconium (IV),
Two (trifluoromethanesulfonic acids) two (ethyl cyclopentadienyl) close zirconium (IV),
Two (trifluoromethanesulfonic acids) two (hexyl cyclopentadienyl) close zirconium (IV),
Two (trifluoromethanesulfonic acids) two (1,3-dimethyl cyclopentadienyl) close zirconium (IV),
Two (trifluoromethanesulfonic acids) two (1-methyl-3-ethyl cyclopentadienyl) close zirconium (IV),
Dichloride two (1,3-dimethyl cyclopentadienyl) is closed zirconium (IV),
Dichloride two (1-methyl-3-ethyl cyclopentadienyl) is closed zirconium (IV),
Dichloride two (1-methyl-3-octyl group cyclopentadienyl) is closed zirconium (IV),
Dichloride two (trimethylammonium cyclopentadienyl) is closed zirconium (IV),
Dichloride two (methyl-benzyl cyclopentadienyl) is closed zirconium (IV),
Dichloride two (ethylhexyl cyclopentadienyl) is closed zirconium (IV),
Dichloride two (methylcyclohexyl cyclopentadienyl) is closed zirconium (IV).
The present invention also can use in the above-claimed cpd 1, and 3-position substituted cyclopentadienyl is by 1, the displaced compound of 2-position substituted cyclopentadienyl.
In addition, also can use the Metallocenic compound of bridge-type, this compound comprises at least two groups (part) with cyclopentadienyi skeleton, and described at least two groups mutually combine by alkylidene group, the silylene of alkylidene group, replacement or the silylene that replaces.Be the example of this bridge-type Metallocenic compound below.
Ethylene (indenyl) dimethyl closes zirconium (IV),
Dichloride ethylene (indenyl) closes zirconium (IV),
Two (methylsulfonic acid) ethylene (indenyl) closes zirconium (IV),
Dichloride ethylene (4,5,6, the 7-tetrahydro indenyl) closes zirconium (IV),
Dichloride isopropylidene (cyclopentadienyl-fluorenyl) closes zirconium (IV),
Silica-based two (cyclopentadienyls) of dichloride dimethylated methylene close zirconium (IV),
Silica-based two (the dimethyl cyclopentadienyls) of dichloride dimethylated methylene close zirconium (IV),
Silica-based two (indenyls) of dichloride dimethylated methylene close zirconium (IV),
Silica-based two (indenyls) of two (trifluoromethanesulfonic acid) dimethylated methylene close zirconium (IV),
Dichloride phenylbenzene silylene two (indenyl) close zirconium (IV) and
Dichloride aminomethyl phenyl silylene two (indenyl) closes zirconium (IV).
Among the present invention, preferably use following Metallocenic compound:
Zirconium (IV) is closed in silica-based two (1-(2,7-dimethyl-4-ethyl-indenyl)) of racemize-dichloride dimethylated methylene,
Zirconium (IV) is closed in silica-based two (1-(2,7-dimethyl-4-sec.-propyl indenyl)) of racemize-dichloride dimethylated methylene,
Zirconium (IV) is closed in silica-based two (1-(2,7-dimethyl-4-sec-butyl indenyl)) of racemize-dichloride dimethylated methylene,
Zirconium (IV) is closed in silica-based two (1-(2,7-dimethyl-4-tertiary butyl indenyl)) of racemize-dichloride dimethylated methylene,
Zirconium (IV) is closed in silica-based two (1-(2,7-dimethyl-4-methylcyclohexyl indenyl)) of racemize-dichloride dimethylated methylene,
Zirconium (IV) is closed in silica-based two (1-(2,7-dimethyl-4-phenyl dichloromethyl indenyl)) of racemize-dichloride dimethylated methylene,
Zirconium (IV) is closed in silica-based two (1-(2, the silica-based methyl indenyl of 7-dimethyl-4-trimethylammonium first)) of racemize-dichloride dimethylated methylene,
Zirconium (IV) is closed in silica-based two (1-(2,7-dimethyl-4-trimethylsiloxy group methyl indenyl)) of racemize-dichloride dimethylated methylene,
Racemize-dichloride diethyl silylene two (1-(2,7-dimethyl-4-sec.-propyl indenyl)) is closed zirconium (IV),
Racemize-dichloride two (cyclohexyl) silylene two (1-(2,7-dimethyl-4-sec.-propyl indenyl)) closes zirconium (IV),
Racemize-dichloride aminomethyl phenyl silylene two (1-(2,7-dimethyl-4-sec.-propyl indenyl)) is closed zirconium (IV),
Racemize-dichloride phenylbenzene silylene two (1-(2,7-dimethyl-4-tertiary butyl indenyl)) is closed zirconium (IV),
Racemize-dichloride phenylbenzene silylene two (1-(2,7-dimethyl-4-ethyl-indenyl)) is closed zirconium (IV),
Silica-based two (1-(the 2-methyl-4-sec.-propyl-7-ethyl-indenyl)) of racemize-dibrominated dimethylated methylene close zirconium (IV),
Zirconium (IV) is closed in silica-based two (1-(2,3,7-trimethylammonium-4-ethyl-indenyl)) of racemize-dichloride dimethylated methylene,
Zirconium (IV) is closed in silica-based two (1-(2,3,7-trimethylammonium-4-sec.-propyl indenyl)) of racemize-dichloride dimethylated methylene,
Zirconium (IV) is closed in silica-based two (1-(2,3,7-trimethylammonium-4-n-hexyl indenyl)) of racemize-dichloride dimethylated methylene,
Zirconium (IV) is closed in silica-based two (1-(2,3,7-trimethylammonium-4-cyclohexyl indenyl)) of racemize-dichloride dimethylated methylene,
Zirconium (IV) is closed in silica-based two (1-(2,3, the silica-based methyl indenyl of 7-trimethylammonium-4-trimethylammonium first)) of racemize-dichloride dimethylated methylene,
Zirconium (IV) is closed in silica-based two (1-(2,3,7-trimethylammonium-4-chloromethyl indenyl)) of racemize-dichloride dimethylated methylene,
Racemize-dichloride two (cyclohexyl) silylene two (1-(2,3,7-trimethylammonium-4-sec.-propyl indenyl)) closes zirconium (IV),
Racemize-dichloride aminomethyl phenyl silylene two (1-(2,3,7-trimethylammonium-4-sec.-propyl indenyl)) is closed zirconium (IV),
Racemize-dichloride phenylbenzene silylene two (1-(2,3,7-trimethylammonium-4-tertiary butyl indenyl)) is closed zirconium (IV),
Racemize-dichloride phenylbenzene silylene two (1-(2,3,7-trimethylammonium-4-ethyl-indenyl)) is closed zirconium (IV),
Silica-based two (1-(the 2-methyl-4-sec.-propyl-7-methyl indenyl)) of racemize-two (methylsulfonic acid) dimethylated methylene close zirconium (IV),
Silica-based two (1-(the 2-methyl-4-sec.-propyl-7-methyl indenyl)) of racemize-dichloride dimethylated methylene close titanium (IV) and
Silica-based two (1-(the 2-methyl-4-sec.-propyl-7-methyl indenyl)) of racemize-dichloride dimethylated methylene close hafnium (IV).
Zirconium in the above-listed compound also can use with titanium or the displaced compound of hafnium.In these compounds, preferably those have the compound of branch's alkyl (as sec.-propyl, the sec-butyl or the tertiary butyl) on the 4-position.
Above-mentioned various Metallocenic compound can two or more be used in combination.
The for example available Japanese Patent of Metallocenic compound discloses 268307/1992 described method and synthesizes.
Metallocenic compound [A] in order to preparation long-chain branch ethylene/alpha-olefin random copolymers (A2)
Be preferably the compound of formula [II] expression in order to the Metallocenic compound [A] of preparation long-chain branch ethylene/alpha-olefin random copolymers (A2)
In formula [II], M is the IVB group 4 transition metal atom in the periodictable, is specially zirconium, titanium or hafnium, is preferably zirconium.
Substituent R 1
R 1It is the alkyl that contains 1-6 carbon atom.Its example is an alkyl, as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, n-pentyl, neo-pentyl, n-hexyl and cyclohexyl; And thiazolinyl, as vinyl and propenyl.Wherein linear alkyl is better.The alkyl that contains 1-4 carbon atom is better, preferably methyl and ethyl.
Substituent R 2, R 4, R 5, and R 6
R 2, R 4, R 5, and R 6Can be identical or different, respectively be hydrogen, halogen atom or as R 1Described in the alkyl that contains 1-6 carbon atom.
Halogen atom is fluorine, chlorine, bromine or iodine.
Substituent R 3
R 3It is the aryl that contains 6-16 carbon atom.This aryl can be by halogen atom, the alkyl that contains 1-20 carbon atom or the silica-based replacement of organic first.
The example of this aryl is phenyl, Alpha-Naphthyl, betanaphthyl, anthryl, phenanthryl, pyrenyl, acenaphthenyl (acenaphthyl), 1H-benzo naphthyl (phenalenyl), aceanthrylenyl, tetrahydro naphthyl, 2,3-indanyl and xenyl.Wherein be preferably phenyl, naphthyl, anthryl and phenanthryl.
Example as the alkyl of the substituent 1-20 of containing carbon atom of this aryl is:
Alkyl is as methyl, ethyl, propyl group, butyl, hexyl, cyclohexyl, octyl group, nonyl, dodecyl, eicosyl, norborneol alkyl and adamantyl;
Alkenyl is as vinyl, propenyl and cyclohexenyl;
Aralkyl is as benzyl, styroyl and hydrocinnamyl; With
Aryl is as above-listed aryl, tolyl, 3,5-dimethylphenyl, trimethylphenyl, ethylbenzene base, propyl phenyl, methyl naphthyl, benzyl phenyl.
The silica-based example of organic first is that the trimethylammonium first is silica-based, silicoheptane base and triphenyl first are silica-based.
X 1And X 2
X 1And X 2Respectively for hydrogen, halogen atom, contain alkyl (can be halogen replacement), oxy radical or the sulfur-containing group of 1-20 carbon atom.The example of halogen atom and alkyl is with top described identical.
The example of oxy radical is hydroxyl, alkoxyl group, as methoxyl group, oxyethyl group, propoxy-and butoxy; Aryloxy is as phenoxy group, methylphenoxy, dimethyl phenoxy and naphthyloxy; And aralkoxy, as phenyl methoxyl group and phenyl ethoxy.
The example of sulfur-containing group is the group that oxygen has been replaced by sulphur in the above-mentioned oxy radical; Sulfonate group is as methanesulfonate, trifluoromethanesulfonic acid root, Phenylsulfonic acid root, benzyl sulfonic acid root, tosic acid root, tri-methyl p-toluenesulfonate root, triisobutyl Phenylsulfonic acid root, p-chlorobenzenesulfonic acid root and penta fluoro benzene sulfonate radical; And sulfonite groups, as methyl-sulfinic acid root, phenyl-sulfinic acid root, benzyl-sulfinic acid root, to toluenesulfinic acid root, Three methyl Benzene-sulfinic acid root and penta fluoro benzene-sulfinic acid root.
In these groups, X 1And X 2Better be halogen atom or the alkyl that contains 1-20 carbon atom.
Y
Y is the bivalent hydrocarbon radical that contains 1-20 carbon atom, contains the divalence halo alkyl of 1-20 carbon atom, divalence silicon-containing group, the germanic group of divalence ,-O-,-CO-,-S-,-SO-,-SO 2-,-NR 7,-P (R 7)-,-P (O) (R 7)-,-B (R 7)-, or-AlR 7-(R 7Be hydrogen, halogen atom, contain the alkyl of 1-20 carbon atom or contain the halo alkyl of 1-20 carbon atom).
The example that contains the bivalent hydrocarbon radical of 1-20 carbon atom is an alkylidene group, as methylene radical, dimethylated methylene base, ethylene, dimethyl ethylene, trimethylene, tetramethylene, 1,2-cyclohexylidene and 1,4-cyclohexylidene; And inferior aralkyl, as phenylbenzene methylene radical and phenylbenzene-ethylene.
The example of divalence halo alkyl is the group that the bivalent hydrocarbon radical halogenation of the above-mentioned 1-20 of a containing carbon atom gets, as the chlorine methylene radical.
The example of divalence silicon-containing group is silene, alkaryl silylene and aryl silylene,, diethyl silylene, two (n-propyl) silylene silica-based as methyl silylene, dimethylated methylene, two (sec.-propyl) silylene, two (cyclohexyl) silylene, aminomethyl phenyl silylene, phenylbenzene silylene, two (p-methylphenyl) silylene and two (rubigan) silylene; And alkyl-dimethyl is silica-based, alkaryl dimethyl silyl and aryl dimethyl silyl, as tetramethyl--1, and 2-dimethyl silyl and tetraphenyl-1,2-dimethyl silyl.
The example of the germanic group of divalence is that silicon in the above-mentioned divalence silicon-containing group is by germanium alternate group.
R 7With halogen atom recited above, contain the alkyl of 1-20 carbon atom or contain the halo alkyl of 1-20 carbon atom identical.
In above-listed group, Y better is divalence silicon-containing group or the germanic group of divalence, is more preferably the divalence silicon-containing group, especially silene, alkaryl silylene or aryl silylene.
List the example of the Metallocenic compound of above-mentioned formula [II] expression below:
Silica-based-two (1-(the 4-phenyl indenyls)) of racemize-dichloride dimethylated methylene close zirconium (IV),
Silica-based-two (1-(the 2-methyl-4-phenyl indenyl)) of racemize-dichloride dimethylated methylene close zirconium (IV),
Silica-based-two (1-(2-methyl-4-(pentafluorophenyl group) indenyls)) of racemize-dichloride dimethylated methylene close zirconium (IV),
Silica-based-two (1-(2-methyl-4-(rubigan) indenyls)) of racemize-dichloride dimethylated methylene close zirconium (IV),
Silica-based-two (1-(2-methyl-4-(to the bromophenyl) indenyls)) of racemize-dichloride dimethylated methylene close zirconium (IV),
Silica-based-two (1-(2-methyl-4-(p-isopropyl phenyl) indenyls)) of racemize-dichloride dimethylated methylene close zirconium (IV),
Racemize-dichloride diethyl silylene-two (1-(2-methyl-4-phenyl indenyl)) is closed zirconium (IV),
Racemize-dichloride dicyclohexyl silylene-two (1-(2-methyl-4-phenyl indenyl)) is closed zirconium (IV),
Racemize-dichloride aminomethyl phenyl silylene-two (1-(2-methyl-4-phenyl indenyl)) is closed zirconium (IV),
Racemize-dichloride phenylbenzene silylene-two (1-(2-methyl-4-phenyl indenyl)) is closed zirconium (IV),
Racemize-dichloride ethylidene-two (1-(2-methyl-4-phenyl indenyl)) is closed zirconium (IV),
Racemize-dichloride dimethylated methylene germane base-two (1-(2-methyl 4-phenyl indenyl)) is closed zirconium (IV),
Racemize-dichloride dimethylated methylene stannane base-two (1-(2-methyl-4-phenyl indenyl)) is closed zirconium (IV),
Silica-based-two (1-(the 2-methyl-4-phenyl indenyl)) of racemize-dibrominated dimethylated methylene close zirconium (IV),
Silica-based-two (1-(the 2-methyl-4-phenyl indenyl)) of racemize-methyl-sulfinic acid chlorination dimethylated methylene close zirconium (IV) and
Silica-based-two (1-(the 2-methyl-4-phenyl indenyl)) of racemize-methylsulphonic acid chlorination dimethylated methylene close zirconium (IV).
Zirconium in the above-listed compound also can be used by titanium or hafnium alternate compound.
Among the present invention, the Metallocenic compound that generally uses the racemize type is as catalyst component, but R type or S type also can use.
Above-mentioned Metallocenic compound can two or more be used in combination.
Metallocenic compound can be by ＂ Journal of Organometallic Chem. ＂, and 288 (1985), pp.63-67 and European Patent Application Publication No.0,320,762 described methods preparations.
Organoaluminoxy based compound [B]
The used Organoaluminoxy based compound (B) of the present invention can be the aikyiaiurnirsoxan beta that people know, and also can be that Japanese Patent discloses the benzene-insoluble Organoaluminoxy based compound described in 78687/1990.
The example of aikyiaiurnirsoxan beta is a methylaluminoxane, ethyl aikyiaiurnirsoxan beta and propyl group aikyiaiurnirsoxan beta.
Compound [C] with Metallocenic compound [A] reaction generation ion pair
The compound [C] that generates ion pair with Metallocenic compound [A] reaction comprises National Publication ofInternational Patent No.501950/1989 and 502036/1989, Japanese Patent discloses 179005/1991,179006/1991,207703/1991 and 207704/1991, and United States Patent (USP) 5,321, the Lewis acid described in 106, ionic compound, borane compound and carborane compound.
Described Lewis acid comprises the Lewis acid of magniferous Lewis acid, aluminiferous Lewis acid and boracic.Wherein be preferably the Lewis acid of boracic.
The lewis acidic example of boracic is boron trifluoride, triphenyl-boron, three (4-fluorophenyl) boron, three (3, the 5-difluorophenyl) boron, three (4-methyl fluoride phenyl) boron, three (pentafluorophenyl group) boron, three (p-methylphenyl) boron, three (o-tolyl) boron and three (3, the 5-3,5-dimethylphenyl) boron.Three (pentafluorophenyl group) boron preferably wherein.
Can be used for ionic compound of the present invention is a kind of salt that is formed by anionic compound and cation compound, preferably contains organic boron compound as anionic ionic compound.The example of this ionic compound is: the ammonium salt that trialkyl replaces, close boron (III) triethylenetetraminehexaacetic acid ammonium as tetraphenyl; N, N-dialkyl benzene amine salt closes boron (III) acid (N, accelerine) as tetraphenyl; Dialkyl ammonium salt closes boron (III) acid (two positive third ammoniums) as four (pentafluorophenyl groups); With San Fang Ji phosphonium salt, close boron (III) triphenyl phosphate Ji Phosphonium as tetraphenyl.
Above-listed compound [C] can two or more be used in combination.
Organo-aluminium compound [D]
Organo-aluminium compound [D] used among the present invention comprises trialkylaluminium, as trimethyl aluminium; Alkenyl aluminium is as prenyl aluminium; The halogenide of aluminum dialkyl is as chlorination di-isopropyl aluminium; The aluminum alkyls sesquihalide is as the sesquialter ethylaluminium chloride; Alkyllithium dihalide is as methylaluminium dichloride; And the hydride of aluminum alkyls, as diethyl aluminium hydride.
These organo-aluminium compounds can two or more be used in combination.
The used specific metalloscene catalyst of the present invention comprises Metallocenic compound [A], and it can be made of Metallocenic compound [A] and above-mentioned Organoaluminoxy based compound [B].Metalloscene catalyst also can and can constitute with the compound [C] that Metallocenic compound [A] reaction generates ion pair by Metallocenic compound [A], or by Metallocenic compound [A], Organoaluminoxy based compound [B] with can constitute with the compound [C] that Metallocenic compound [A] reaction generates ion pair.In these embodiments, preferably all further combined with using organo-aluminium compound [D].
Among the present invention, be benchmark with 1 liter of polymerization volume, the consumption (by transition metal atoms) of Metallocenic compound [A] generally is about the 0.00005-0.1 mmole, better is about the 0.0001-0.05 mmole.
The consumption of Organoaluminoxy based compound [B] generally is to make that the amount of aluminium atom is 1-10,000 mole, better is about the 10-5000 mole with respect to per 1 mole of transition metal atoms.
Generating the consumption of the compound [C] of ion pair with Metallocenic compound [A] reaction, generally is to make that the amount of boron atom is about the 0.5-20 mole, is preferably the 1-10 mole with respect to per 1 mole of transition metal atoms.
The consumption of organo-aluminium compound [D] is benchmark or is benchmark with 1 mole of boron atom in the compound [C] that forms ion pair with 1 moles, of aluminum per mole of titanium metal atom in the Organoaluminoxy based compound [B], generally can choose wantonly to be about the 0-1000 mole, better is about the 0-500 mole.
When using above-mentioned metalloscene catalyst to make ethene and contain the alpha-olefin copolymer of 5-20 carbon atom, can with high polymerization activity obtain linearity and long-chain branch ethylene/alpha-olefin random copolymers (A1, A2).
But, promptly use VB group transition metal compound catalyzer (as vanadium catalyst) to make ethene and contain the alpha-olefin copolymer of 5-20 carbon atom, can not obtain with enough polymerization activities linearity and long-chain branch ethylene/alpha-olefin random copolymers (A1, A2).
When ethene carries out copolymerization with the alpha-olefin that contains 5-20 carbon atom, constitute the compound [C] of each component-Metallocenic compound [A], Organoaluminoxy based compound [B] and the formation ion pair of metalloscene catalyst, and optional organo-aluminium compound [D], can be added to respectively in the polymerization reactor, also can in polymerization reaction system, add the previously prepared metalloscene catalyst that contains Metallocenic compound [A].
During the preparation metalloscene catalyst, can use each catalyst component is the inert varsol.The example of inert hydrocarbon solvent is an aliphatic hydrocarbon, as propane, hexane, octane and decane; Alicyclic hydrocarbon is as hexanaphthene and methylcyclopentane; Aromatic hydrocarbons is as benzene, toluene and dimethylbenzene; And halohydrocarbon, as ethylene chloride, chlorobenzene and methylene dichloride.These varsols can use separately or be used in combination.
The compound [C] of Metallocenic compound [A], Organoaluminoxy based compound [B], formation ion pair can contact under-100 to 200 ℃ temperature with organo-aluminium compound [D], better is at-70 to 100 ℃.
Among the present invention, ethene with the copolymerization conditions that contains the alpha-olefin of 5-20 carbon atom is: temperature is 40-200 ℃, is preferably 50-150 ℃, is preferably 60-120 ℃; Pressure is normal pressure to 100 kg/cm, is preferably normal pressure to 50 kg/cm, is preferably normal pressure to 30 kg/cm.
Polyreaction can be carried out with various polymerization processs, but better is solution polymerization process.In solution polymerization process, can use above-mentioned varsol as polymer solvent.
Polyreaction can be carried out in batches, semi-continuously or continuously, but better is to carry out continuously.Polyreaction can be divided into two or more stages carries out, and each stage carries out under the differential responses condition.
Linearity that the present invention preferably uses and long-chain branch ethylene/alpha-olefin random copolymers (A1, A2) available aforesaid method makes, and the molecular weight of these multipolymers can be regulated by the quantity that changes polymerizing condition (as polymerization temperature) or control hydrogen (molecular weight regulator).
Among the present invention, be 100 parts in the gross weight of ethylene/alpha-olefin random copolymers (A) and crystalline polypropylene (B), the consumption of ethylene/alpha-olefin random copolymers (A) is generally 5-60 part weight, is preferably 10-50 part, more preferably 10-40 part.When the consumption of ethylene/alpha-olefin random copolymers (A) is in this scope, the polypropene composition that obtains can make not only has good low temperature heat seal performance and shock strength, and has the polypropylene film of good thermostability, rigidity, smooth property and resistance to blocking.
Crystalline polypropylene (B)
The used crystalline polypropylene (B) of the present invention can be the homopolymer of propylene, or the segmented copolymer of propylene and no more than 50% mole one or more other alpha-olefins (alpha-olefin that contains 2-20 carbon atom as ethene, 1-butylene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene and tetradecene and so on), or the crystallization random copolymers of propylene and no more than 10% mole other alpha-olefin.
The melt flow rate (MFR) of the crystalline polypropylene (B) that the present invention is used (MFR, 1238,230 ℃ of ASTM D load 2.16 kilograms) is preferably 0.3-100 gram/10 minutes for 0.1-200 restrains/10 fens.When the melt flow rate (MFR) of crystalline polypropylene is in above-mentioned scope, can obtain having the polypropene composition of good mouldability.
Ethylene/alpha-olefin copolymer as crystalline polypropylene (B) among the present invention can be in a polymerization reaction system, under the condition that has the isotactic catalyzer, one after the other changing the segmented copolymer that the monomer prescription makes olefinic polymerization and get, also can be polymkeric substance mixed type multipolymer.
In order to obtain the film of high-clarity, need select for use alfon or crystallization random copolymers as described crystalline polypropylene.In order to obtain the high film of shock resistance, preferably select for use the segmented copolymer of propylene or crystallization random copolymers as described crystalline polypropylene.
Among the present invention, the consumption of crystalline polypropylene (B) is 100 parts in the gross weight of ethylene/alpha-olefin random copolymers (A) and crystalline polypropylene (B), is generally 40-95 part weight, is preferably 50-90 part, is preferably 60-90 part.When the quantity of the crystalline polypropylene (B) that uses is in this scope, resulting polypropene composition can make not only has good low temperature heat seal performance and shock resistance, and has the polypropylene film of good thermostability, rigidity, smooth property and resistance to blocking.
Other additive
In the polypropene composition that comprises ethylene/alpha-olefin random copolymers (A) and crystalline polypropylene (B), can be in the scope of the object of the invention, randomly add the various additives known that generally are added in the polyolefine, as weather stablizer, thermo-stabilizer, anti-fogging agent, antiblocking agent, surface slip agent, static inhibitor, fire retardant, pigment and filler etc.
Outside ethylene/alpha-olefin random copolymers (A) and crystalline polypropylene (B), polypropene composition better contains no more than 20 parts of weight, the high pressure low density polypropylene of more preferably no more than 15 parts of weight (gross weight in ethylene/alpha-olefin random copolymers (A) and crystalline polypropylene (B) is 100 parts).
When contained high pressure low density polypropylene during in above-mentioned scope, ethylene/alpha-olefin random copolymers (A) can improve with the consistency of crystalline polypropylene (B).And when during as film forming stacked resin, preventing the width of cloth phenomenon that contracts with this polypropene composition.
The used polyacrylic melt flow rate (MFR) of high pressure low density (MFR, 1238,190 ℃ of ASTM D load 2.16 kilograms) of the present invention was generally the 1-40 gram/10 minutes, was preferably 3-30 gram/10 minutes; Density is generally 0.913-0.935 gram/cubic centimetre, is preferably 0.915-0.930 gram/cubic centimetre.
The preparation of polypropene composition
The polypropene composition that polypropylene film of the present invention is used can in all sorts of ways ethylene/alpha-olefin random copolymers (A), and acrylic resin (B) and optional additive mix under molten state and make.
For example, said components can be mixed in the machine of Han Xieer mixing machine, V-type mixer, the mixed machine of bucket or ribbon blender and so on simultaneously or in succession, then mixture be obtained polypropene composition with single-screw extrusion machine, multiscrew extrusion machine, kneader or Banbury kneading under molten state.
Mediate high extrusion machine, kneader or the Banbury of performance if in various kneading devices, select for use, can obtain each component dispersive high quality polypropene composition more equably.
Additive as antiblocking agent, surface slip agent and static inhibitor, can add in arbitrary stage of preparation process.
Polypropylene film
Polypropylene film of the present invention is the film that comprises the polypropene composition of ethylene/alpha-olefin random copolymers (A) and crystalline polypropylene (B).
Polypropylene film of the present invention can make with various film molding methods, as T-die head film moulding method, water-cooled inflation method and air cooling inflation method.
Polypropylene film of the present invention with method for preparing has good transparency, tensile property, heat seal performance and film shock strength.
This polypropene composition is extrudable to be coated on the various base materials, or by the dry lamination method, the extruding layer platen press, sandwich of layers platen press and co-extrusion method and base material co-extrusion, thus on base material the thin film layer of formation polypropene composition.
That is, the polypropylene film that obtains with above-mentioned film molding methods can be layered in and form a laminated film on other film.Described polypropylene film can be used as the sandwich of layers laminate materials and is inserted between base material and the sealing ply.
The example of base material is paper, aluminium foil, cellophane, woven fabric, supatex fabric and film-forming superpolymer.The object lesson of described superpolymer is an olefin polymer, as high density polyethylene(HDPE), medium-density polyethylene, new LDPE (film grade), ethylene, ionic crosslinking copolymer, propylene copolymer, poly-1-butylene and poly--4-methyl-1-pentene; Ethylene copolymer is as polyvinyl chloride, polystyrene and polyacrylic ester; Polymeric amide, as nylon 6, nylon 66, Ni Long11 and nylon 12; Polyester is as polybutylene terephthalate and polyethylene terephthalate; Polyvinyl alcohol; The ethylene/vinyl alcohol copolymer; Polycarbonate; And polyurethane.
The example of sealing agent is the composition of composition, polypropylene and ethylene/alpha-olefin copolymer of new LDPE (film grade), Atactic Polypropelene, new LDPE (film grade) and ethylene/alpha-olefin copolymer and the composition of polypropylene and propylene/alpha-olefins multipolymer.
The used polypropene composition of the present invention has good molten fluidity energy, that is has good film mouldability.
Polypropylene film of the present invention not only has good transparency, low temperature heat seal performance and shock resistance (film shock strength), and has good tensile property, heat sealing strength, resistance to blocking and smooth property.
Have the polypropylene film of the present invention of above effect, can be widely used in various packaging fields, for example pack fresh foods such as vegetables, fish and meat; The food that packing snack food product and noodles etc. are done; The food that packing soup and pickles etc. are wet; Pack pharmaceutical products such as various forms of medicines (tablet, pulvis and aqua) and medical material; And electric installations such as packing magnetictape cartridge and electric component.
Followingly further specify the present invention, but should be understood that the present invention never only limits to these embodiment with reference to embodiment.
The character of film is estimated by the following method.
(1) transparency (mist degree)
The mist degree of expression transparency is to measure by ASTM D 1003.
(2) gloss is measured according to ASTM D523.
(3) resistance to blocking
The stiction force of expression resistance to blocking is to measure by ASTM D1893.
(4) tensile property
Degree of drawing and young's modulus in tension when surrender tensile stress, fracture tensile stress, fracture are to measure according to ASTMD638.
(5) shock resistance
The film shock strength of expression shock resistance is to measure according to JIS P8134.The ability of testing tool is 30 kilograms per centimeter centimetre, and the diameter of impact head is 1/2 inch.
(6) smooth property
Static friction coefficient and the kinetic friction coefficient of representing smooth property are to measure by ASTM D 1894.
(7) heat seal performance
Film overlay is placed, and at 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃ at each temperature, is 5 millimeters heat-fastening knife with width, with 1 second of pressure heat seal of 2 kg/cm.Allow film leave standstill cooling then.
It is 15 millimeters sample that film that will heat seal under each temperature is cut into width.Be under 300 millimeters/minute the condition in sliding beam speed, the heat seal of each sample is partly separated, record stripping strength.This stripping strength is just got and is made heat sealing strength.
Embodiment 1
The preparation of ethene/1-octene random copolymers
The preparation of catalyst solution
In the glass flask of crossing with the nitrogen cleaning down, put into 0.5 milligram of chlorination two (1,3-dimethyl cyclopentadienyl) and close zirconium (IV).Add the toluene solution (Al:1.1 mol) of 1.57 milliliters of methylaluminoxane and 2.76 milliliters toluene then, obtain catalyst solution.
Polymerization
In 2 liters of stainless steel cauldrons crossing with the nitrogen cleaning down, put into 600 milliliters of hexanes and 400 milliliters of 1-octenes, the temperature of system is increased to 80 ℃.Then, in the downhill reaction still of exerting pressure, put into 1 mmole triisobutyl aluminium and 0.5 milliliter of (counting 0.001 mmole) catalyst solution, use the ethene initiated polymerization by Zr.Subsequently, continuous separately input ethene in system is maintained 4 kg/cm (gauge pressure) with total pressure, makes ethene 90 ℃ of polyase 13s 0 minute.
After the input small amount of ethylene stops the polymerization of ethene, unreacted ethene is purged out reactor.
Then reaction soln is caused in the excessive methyl alcohol, make polymer precipitation.By this polymkeric substance of filtered and recycled, drying under reduced pressure spends the night, and obtains target product ethene/1-octene random copolymers.
The density of the ethene that obtains like this/1-octene random copolymers is 0.885 gram/cubic centimetre, the 1-octene content is 10% mole, melt flow rate (MFR) (MFR, 1238,190 ℃ of ASTM D, load 2.16 kilograms) be 3.4 grams/10 minutes, Tm is 84 ℃, and degree of crystallinity (measuring with X-ray diffraction method) is 14%, molecular weight distribution (Mw/Mn, measure with GPC) be 2.5, the B value is 1.03.
The preparation of polypropene composition
Polypropylene (the trade(brand)name Hipole of the ethene of dry fusion 15% weight in the Han Xieer mixing machine/1-octene random copolymerization composition granule and 85% (weight) TMF657, available from Mitsui Petrochemical Industries, Ltd., melt flow rate (MFR) (MFR, 1238,230 ℃ of ASTM D load 2.16 kilograms) is 6.0 grams/10 minutes), obtain the exsiccant adulterant.
Then the exsiccant adulterant is inputed in the single multiple screw extruder (L/D=26, diameter: 40 millimeters) that sets in advance at 210 ℃, make the polypropene composition particle.
The preparation of film
With T die head mould machine the polypropene composition particle of top gained being molded as width is 250 millimeters, and thickness is 50 microns film.In moulding process, resin temperature is 210 ℃, and the cold roll temperature is 20 ℃.In the extruding machine, screw diameter is 40 millimeters, and screw flight part total length (L) is 26 with the ratio (L/D) of barrel bore (D).The die width of T die head is 350 millimeters.
The results are shown in table 1.
Comparative Examples 1
Method by embodiment 1 prepares polypropene composition, but with ethene/butene-1 copolymer replacement ethene/1-octene random copolymers wherein, this ethene/butene-1 copolymer is to exist under the condition of hydrogen, use comprises the catalyzer of vanadium oxytrichloride and sesquialter ethylaluminium chloride (ethylenealuminum sesquichloride),, make under 50 ℃ as reaction solvent with hexane.The method that this polypropene composition is pressed embodiment 1 is with T die head molding, and obtaining width is 250 millimeters, and thickness is 50 microns film.
The density of resulting ethene/butene-1 copolymer is 0.885 gram/cubic centimetre, melt flow rate (MFR) MFR (ASTM D 1238,190 ℃, load 2.16 kilograms) be 3.6 grams/10 minutes, Tm is 69 ℃, and degree of crystallinity (measuring with X-ray diffraction method) is 10%, molecular weight distribution (Mw/Mn, measure with GPC) be 2.2, the B value is 1.02.
The results are shown in table 1.
Table 1
Embodiment 1 Comparative Examples 1 ethylene/alpha-olefin random copolymer alpha-olefin kind 1-octene 1-butylene alpha-olefin content (% mole) 10 12 density (g/cc) 0.885 0.885MFR (restraining/10 fens), 3.4 3.6Tm (℃) 84 69 degree of crystallinity (%), 14 10Mw/Mn, 2.5 2.2B values, 1.03 1.02 inherent viscosities [η] are 1.5 1.5g η (dl/g)*Be worth 1.00 1.00Tg (℃) character mist degree (%) 2.8 3.1 gloss (%) 95 90 tensile properties (vertically/laterally) of-58-57 constituent contents (part, weight) ethylene/alpha-olefin random copolymer 15 15 polypropylene 85 85 polypropylene films
Yielding stress (MPa) 16,/15 15/13
Rupture stress (MPa) 75,/53 63/41
Elongation during fracture (%) 7,20/,760 690/690
Young's modulus (MPa) 6,40/,630 640/670 film shock strengths (KJ/m)
0℃ 34 29
-10 ℃ of 29 27 smooth property
Static friction coefficient 0.30 0.34
Kinetic friction coefficient 0.26 0.30 resistance to blocking
130 ℃ 3.4 3.7140 ℃ 8.0 6.0150 ℃ 15.5 9.8160 ℃ 14.9 14.1170 ℃ 14.8 13.6180 ℃ 15.3 13.7 of stiction force (milli newton/centimetre) 7.5 8.5 heat sealing strengths (newton/15 millimeter)

Claims (4)

1. polypropylene film of making by the polypropene composition that comprises following component:
The ethylene/alpha-olefin random copolymers (A) of [I] 5-60 part weight, this multipolymer comprises the alpha-olefin of ethene and a kind of 5-20 of containing carbon atom, and has following character:
Density is 0.870-0.900 gram/cubic centimetre,
Melt flow rate (MFR) (MFR, ASTM D1238, load 2.16 kilograms by 190 ℃) restrains/10 fens for 0.01-50,
The temperature (Tm ℃) of the endothermic curve peak-peak position that records with differential scanning calorimeter (DSC) concerns below satisfying with its density (d gram/cubic centimetre):
When 0.885≤d≤0.900,
(14d/15)×1000-734＞Tm≥(14d/15)×1000-744，
When 0.870≤d＜0.885,
(4d/3) * 1000-1088＞Tm 〉=(4d/3) * 1000-1098, and
The crystalline polypropylene (B) of [II] 40-95 part weight,
Described component (A) and total amount (B) are 100 parts of weight.
2. polypropylene film as claimed in claim 1, its feature are that also alpha-olefin content is the 5-20% mole in the ethylene/alpha-olefin random copolymers (A).
3. polypropylene film as claimed in claim 1 or 2, its feature are that also the degree of crystallinity of the ethylene/alpha-olefin random copolymers (A) measured with X-ray diffraction method is less than 40%.
4. polypropylene film as claimed in claim 1, its feature also is to contain in the described polypropene composition hp-ldpe of no more than 20 parts of weight, the density of this hp-ldpe is 0.913-0.935 gram/cubic centimetre, melt flow rate (MFR) (MFR, ASTM D 1238,190 ℃, load 2.16 kilograms) be that 1-40 gram/10 minutes, content are that gross weight with ethylene/alpha-olefin random copolymers (A) and crystalline polypropylene (B) is as 100 parts of calculating.
CN97103082A 1996-03-19 1997-03-19 Polypropylene film Expired - Lifetime CN1059451C (en)

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