CN1145082A - LLDPE resin blends - Google Patents

LLDPE resin blends Download PDF

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Publication number
CN1145082A
CN1145082A CN95192353A CN95192353A CN1145082A CN 1145082 A CN1145082 A CN 1145082A CN 95192353 A CN95192353 A CN 95192353A CN 95192353 A CN95192353 A CN 95192353A CN 1145082 A CN1145082 A CN 1145082A
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China
Prior art keywords
blend
weight
lldpe
multipolymer
ldpe
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CN95192353A
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Chinese (zh)
Inventor
S·-M·C·翁
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ExxonMobil Oil Corp
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Mobil Oil Corp
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    • 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
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • 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

Abstract

A resin blend of LLDPE produced using a metallocene catalyst system and low density, high pressure polyethylene can be extruded into films exhibiting improved optical properties and impact strength.

Description

LLDPE resinous blending thing
The present invention relates to the blend of linear, low density ethylene copolymer (LLDPE) and have the film of excellent optical property.
Conventional LLDPE (LLDPE) can not be used to prepare the film that requires excellent optical property owing to resin inherent poor optical properties.The mist value of conventional LLDPE is usually greater than 10 (pressing ASTM D-1003 method measures).
The ethene polymers that can use in requiring the field of excellent optical property is new LDPE (film grade) (LDPE), and this polyethylene is to produce than producing under the higher pressure of the used pressure of LLDPE.For example, according to reports, the preparation condition of LDPE is 150-300MPa (1500-3000 normal atmosphere) and 200-300 ℃, LLDPE then is that 0.3-1.0MPa (or 3-10 normal atmosphere) and 70-90 ℃ are (referring to KIRK-OTHMER, ENCYCLOPEDIAOF CHEMICAL TECHNOLOGY, 16 volumes, 433 pages (third edition)).But the shock resistance of LDPE resin is very low.
Recently, can prepare novel linear, low density product with metalloscene catalyst.The present invention relates to high pressure P E resin and release agent, promptly fine and smooth stone flour is added in the new metallocenes LLDPE resin, makes it have excellent optical property and qualified tackiness.The present invention is fully feasible, because the metallocenes resin has narrower molecular weight distribution and more uniform short-chain branched distribution than conventional LLDPE resin.
The present invention is intended to a kind of blend, wherein contains 70-98% (weight) dry state, solvent-free synthetic composition, and said composition comprises sphere, non-porous particle, and its median size is 0.05-0.11cm (a 0.02-0.045 inch), and the sedimentation bulk density is 400-580kg/m 3(25-36 pound/foot 3), described composition is the multipolymer of ethene and a kind of alpha-olefin, and its density is 0.902-0.929, and MFR is 15-25, M w/ M nBe 2.0-3.0; And 2-30% (weight) is at 150-300MPa (1500-3000 normal atmosphere) and 200-300 ℃ of new LDPE (film grade) for preparing down, wherein the mist value of this blend is less than 5 (pressing ASTM D1003 measures), and dart shock resistance (pressing ASTM D-1709 measures) is greater than 400.
The LLDPE resin that contains blend of the present invention can be processed on industrial LLDPE film forcing machine at an easy rate, does not need to make any change.The film of being made by this blend has excellent shock resistance, considerably beyond this performance of LDPE.
New LDPE (film grade) (LDPE) component
Used LDPE component is conventional LDPE in the blend of the present invention, and the pressure when its preparation pressure ratio LLDPE prepares is higher.This LDPE is in 150-300MPa (1500-3000 normal atmosphere) and 200-300 ℃ preparation down, and the common preparation condition of LLDPE is 0.3-1.0MPa (or 3-10 normal atmosphere) and 70-100 ℃.If do not add LLDPE, then the shock resistance of LDPE resin is very low.
Copolymer component
Copolymer component in the blend of the present invention is that density is 0.902-0.929, more preferably the LLDPE of 0.915-0.922 (LLDPE).
The difference of the LLDPE component of blend of the present invention and conventional LLDPE is its mist value (press ASTM D-1003 measures) less than about 20, preferably 3-10, most preferably 5-7.In contrast to this, the mist value of conventional LLDPE is greater than 10.
The LLDPE component contains 0.1-2ppm Zr (bringing in the catalyzer of using when synthetic), and its median size is 0.05-0.11cm (a 0.02-0.045 inch), and the sedimentation bulk density is 400-580kg/m 3(25-36 pound/foot 3).The resin that synthesizes is that dry state is solvent-free, comprises spheric, non-porous particle.
The LLDPE component melt flow of blend of the present invention is 15-25 than (MFR), preferred 15-20, most preferably 16-18.MFR is I 21/ I 2Ratio (I wherein 21Be 190 ℃ according to ASTM D-1238, condition F measures, I 2Be 190 ℃ according to ASTM D-1238, condition E measures).
The MI of LLDPE component is 0.01-5, is generally 0.1-5, is preferably 0.5-4, most preferably is 0.8-2.0.The MI that is used for the multipolymer of blown film is preferably 0.5-1.5.
The fusing point of LLDPE component is 95-130 ℃.In addition, hexane extraction thing content is very low, is generally 0.3-1.0% (weight).The M of LLDPE w/ M nBe 2.0-3.0, M wBe weight-average molecular weight, M nBe number-average molecular weight, value is separately calculated by the molecular weight distribution that GPC (gel permeation chromatography) measures.
If such not according to the present invention, will there be the LLDPE of blending LDPE to process film forming, then the balance tear strength of this film (measuring according to ASTM D1922) is 50-600, and axial strength is preferably 220-420, and transverse strength is 200-700, is preferably 200-600.This film also has high modulus, is determined as 7 * 10 according to ASTM D882 4-48 * 10 4KPa (1 * 10 4-6 * 10 4Psi), be preferably 15-31 * 10 4KPa (2.2-4.5 * 10 4Psi) and high tensile yield strength, be determined as 4800-21000KPa (700-3000psi), be preferably 12000-16000KPa (1800-2300psi) according to ASTM D882.
If such not according to the present invention, will there be the LLDPE of blending LDPE to process film forming, then the optical quality of this film is assessed as 3-20 by haze value (measuring according to ASTM D-1003), preferred 4-10.The film haze value of poor optical properties is greater than 10.The importance of LLDPE optical property depends on the expection application scenario of LLDPE resin.It has been generally acknowledged that the general relatively poor optical property (mist degree＞10, glossiness＜50) of LLDPE has limited their application in the demanding occasion of optical property widely.
Copolymer component in the resinous blending thing of the present invention is ethene and one or more C 3-C 10The multipolymer of alpha-olefin wherein preferably contains the ethylene unit of at least 80% (weight).The alpha-olefin that is fit to comprises propylene, butene-1, amylene-1, hexene-1,4-methylpentene-1, heptene-1 and octene-1.Preferred alpha-olefin comonomer is 1-butylene, 1-hexene and 1-octene.Most preferred alpha-olefin is a hexene-1.The multipolymer that multipolymer promptly contains two kinds of monomeric units also contains the terpolymer of three kinds of monomeric units.The specific examples of this polymkeric substance comprises ethene/butene-1 copolymer, ethene/1-hexene copolymer, ethene/4 methyl 1 pentene copolymer, ethene/1-butylene/1-hexene terpolymer, ethylene/propene/1-hexene terpolymer and ethylene/propene/1-butylene terpolymer.
The used LLDPE multipolymer of the present invention is to be prepared by the new polyolefin catalyst of a class, and this catalyzer comprises carrier, aikyiaiurnirsoxan beta and at least a metallocenes.
Support of the catalyst is solid-state, porous prilled inorganic or organic materials, is preferably inorganic materials, as the oxide compound of silicon and/or aluminium.Used solid support material is that median size is the 1-250 micron, is preferably the dried powder of 10-150 micron.If desired, can be with the screening of the solid support material handled, to guarantee to obtain median size preferably less than 150 microns particle.This point is very important to reduce gel content for the LLDPE that forms narrow molecular-weight.The surface-area of carrier is at least about 3m 2/ gm preferably is at least 50m 2/ gm is until 350m 2/ gm.When carrier is silica gel, better be to be heated to 100-850 ℃, preferably about 250 ℃.The solid support material that is used to prepare catalyst composition should contain some activity hydroxies (OH) at least.
In the most preferred embodiment, carrier is a silica gel, before the use, it be used the nitrogen fluidisation, and about 4 hours of about 250 ℃ of heating, makes it dehydration, makes concentration of surface hydroxyl groups reach about 1.8 mmole/grams (mmols/gm).The silica that most preferred embodiment is used is the amorphous silica gel (surface-area=300m of high surface area 2/ gm; Pore volume is 1.65cm 3/ gm), the commercial goods is called Davison952-1836, Davison952 or Davison955, produce by the Davison Division of Chemistry of W.R.Grace company.This silica gel is the sort of spheroidal particle that for example makes with spray-drying process.
Used aikyiaiurnirsoxan beta comprises oligomeric, the straight chain and/or the cyclic alkylaluminoxane of following general formula representative in the LLDPE catalyst composition:
R-(Al (R)-O) n-AlR 2: oligomeric straight chain aikyiaiurnirsoxan beta and
(Al (R)-O-) m: oligomeric ring-type aikyiaiurnirsoxan beta, wherein n is 1-40, preferred 10-20; M is 3-40, and preferred 3-20 and R are C 1-C 8Alkyl, be preferably methyl.Methylaluminoxane (MAO) is that the very wide common molecular-weight average of molecular weight distribution is the mixture of about 1000 oligopolymer.MAO is generally held in the toluene solution.
The general formula of Metallocenic compound is Cp mMA nB p, wherein Cp is a cyclopentadienyl unsubstituted or that replace, and M is the transition metal of selected among zirconium or hafnium, and A and B are the group that comprises halogen atom, hydrogen or alkyl.In the general formula of above-mentioned Metallocenic compound, preferred transition metal atoms is a zirconium.In the general formula of above-mentioned Metallocenic compound, the Cp base is unsubstituted, the single replacement or polysubstituted cyclopentadienyl.Substituting group on the cyclopentadienyl is preferably the C of straight or branched 1-C 6Alkyl.Cyclopentadienyl also can be a part and the dicyclo of replacement or the part of three cyclic groups of dicyclo or three cyclic groups such as indenyl, tetrahydro indenyl, fluorenyl or partial hydrogenation fluorenyl, when the m in the above-mentioned Metallocenic compound general formula equaled 2, then cyclopentadienyl also can be by polymethylene or dialkyl silane base as-CH 2-,-CH 2-CH 2-,-CR ' R "-and-CR ' R "-CR ' R "-(wherein R ' and R " be short-chain alkyl or hydrogen) ,-Si (CH 3) 2-,-Si (CH 3) 2-CH 2-CH 2-Si (CH 3) 2-wait similar abutment institute bridging.If substituent A and B in the above-mentioned Metallocenic compound general formula are halogen atoms, then they are fluorine, chlorine, bromine or iodine.If substituent A and B in the above-mentioned Metallocenic compound general formula are alkyl or aryls, then they are preferably the C of straight or branched 1-C 8Alkyl such as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, n-pentyl, n-hexyl or n-octyl.
The Metallocenic compound that is fit to comprise two (cyclopentadienyl) metals of dihalide, two (cyclopentadienyl) metals of hydrogenation halogenation ,-two (cyclopentadienyl) metals of alkyl-halogenation, two (cyclopentadienyl) metals of dialkyl group and two (indenyl) metals of dihalide, wherein said metal is titanium, zirconium or hafnium, the halogenation base is preferably chlorine, and alkyl is C 1-C 6Alkyl.The example of illustrative non-limiting metallocenes comprises molybdenyl dichloride (cyclopentadienyl) zirconium, two (cyclopentadienyl) hafniums of dichloro, two (cyclopentadienyl) zirconiums of dimethyl, two (cyclopentadienyl) hafniums of dimethyl, two (cyclopentadienyl) zirconiums of hydrogenation chlorination, two (cyclopentadienyl) hafniums of hydrogenation chlorination, molybdenyl dichloride (pentamethyl-cyclopentadienyl) zirconium, molybdenyl dichloride (pentamethyl-cyclopentadienyl) hafnium, molybdenyl dichloride (n-butyl cyclopentadienyl) zirconium, molybdenyl dichloride (isobutyl-cyclopentadienyl) zirconium, dichloride cyclopentadienyl zirconium, molybdenyl dichloride (indenyl) zirconium, molybdenyl dichloride (4,5,6,7-tetrahydrochysene-1-indenyl) zirconium and dichloride ethylidene-(two (4,5,6,7-tetrahydrochysene-1-indenyl)) zirconium.
The aikyiaiurnirsoxan beta (representing with Al) that aluminium is provided is 50-500 with the mol ratio of the metal M (for example zirconium) of metallocenes, is preferably 75-300, most preferably is 100-200.The additional advantage of the present invention is Al: the Zr ratio can directly be controlled.In preferred embodiments, aikyiaiurnirsoxan beta and Metallocenic compound are being mixed together 0.1-6.0 hour under 20-80 ℃ earlier in suitable solubility promoter before reacting with carrier.The solubility promoter of metallocenes and aikyiaiurnirsoxan beta can be aromatic hydrocarbons, halohydrocarbon or halogenated aryl hydrocarbon, preferred toluene.
The particularly preferred method of preparation LLDPE is to prepare polymkeric substance in single fluidised bed reactor such as United States Patent (USP) 4,481,301 described reactors.Processing condition comprise that temperature is lower than the fusion bonded temperature of polymer beads, are preferably 60-115 ℃, more preferably 75-95 ℃; Pressure is 150-350psig (1100-2500KPa).
In the LLDPE copolymerization process, preferably having at this reaction conditions in the polymerization reactor is inert " thinner " gas, exists as nitrogen, argon, helium, methane or ethane.Also can add hydrogen as chain-transfer agent.
Blend of the present invention
Blend of the present invention comprises 70-98%, preferred 90-98%, most preferably above-mentioned LLDPE multipolymer and the 2-30% of the above-mentioned LLDPE multipolymer of 95-98% (weight) and 95-98% (weight), preferred 2-10%, the most preferably conventional LDPE resin of 2-5% (weight).
This blend product can also contain the various additives that are added to usually in the polymer composition, as lubricant, fine and smooth stone flour, stablizer, oxidation inhibitor, compatilizer, pigment etc.These additives can be used to make product stable, anti-oxidation.For example, the compositions of additives that comprises 400-1200ppm hindered phenol, 700-2000ppm phosphite, 250-1000ppm static inhibitor and 250-1000ppm stearate can be added to and carry out granulation in the toner.
Polymer blend can directly be added in the blown film forcing machine, and for example preparation thickness for example is the film of 0.5-5 mil (0.013-0.13mm) in the Sterling forcing machine.
By the film that blend of the present invention is made, optical property improve (mist degree＜5, glossiness＞70).By the film that blend of the present invention is made, dart shock resistance (pressing ASTM D-1709 measures) greater than 400, is generally 500-1500.
The following examples will further be set forth principal feature of the present invention.
The polymer properties that makes among the embodiment is with following determination of test method:
Density: ASTM D-1505-preparation-dull and stereotyped sample makes it put at 100 ℃
Put 1 hour to reach the equilibrium crystallization degree.In density gradient column, survey then
Decide density, be designated as gms/cc.
Melt index: ASTM D-1238, condition E
(MI), I 2: measure down at 190 ℃, be designated as gram/10 minute.
High loading is molten
Body index: ASTM D-1238, condition F
(HLMI), I 21: test at above-mentioned melt index under 10.5 times of weight of used weight and measure
Melt flow
Than (MFR): I 21/ I 2
Embodiment 1
Will be by the I of following embodiment A preparation 2The LLDPE metallocenes resin that be 1, density is 0.918 pilot plant production cooperates with 1000ppm Irganox 1010,2000ppm Irgafos168,1000ppm Erucamide, 5000ppm ABT2500,500ppm AS990 and 500ppm Znst in the Banbury mixing tank.With the metallocenes resin after the granulation and I2 be 2 then, density is 0.924 industrial hp-ldpe resin (Mobil LBA-133) by three different contents: 0%, 5% and 10% carries out blending.Use 2.5 inches (6.4cm) Brampton blown film forcing machines under the condition of 440 ℃, die slot 100 mils (2.5mm) and resin feed rate 150 Pounds Per Hours (68kg/hr), each blend to be made the thick film of 1 mil (0.03mm) then.In order to compare, also with the industrial LLDPE resin of molecular weight distribution broad, Mobil NTX-095 presses two different content blending with LBA-133.Then with these results with by Rexene 1065 (I2 is 1.9, and density is 0.924), a kind of high transparent industrial LDPE resin, 1 mil films of making compares.
The result of table 1 shows, when 5% LLDPE blending concentration, the mist degree of metallocenes resin/LDPE blend and Rexene 1065 be (4.4 than Rexene 4.6) quite, impact property then much higher (dart impact 750gms is than the 64gms of Rexene 1065).In addition, under same LDPE blending content, the impact property of metallocenes resin/LDPE blend also is better than the NTX-095/LDPE blend.Metallocenes resinous blending thing has lower mist degree (4.4% than NTX-095 blend 10.3%) and higher dart impact (750gms is than the 166gms of NTX-095 blend).
Table 1
The luxuriant blend research of high transparent metal base resin LDPE% mist degree % DDI, the resin (a) of gms week metallocene-produced 5 4.4 750 prepares by embodiment A with resin (a) NTX-095 5 10.0 166NTX-095,0 17.0 264Rexene1065 (b) 0 4.6 64 (a) of metallocene-produced 0 7.0＞800.(b) during film forming, except that 360 ℃ of temperature and die slot 400 mils (1mm), other condition is constant in Brampton blown film forcing machine for Rexene 1065.
Embodiment A
The raw material that is used to prepare catalyzer comprises toluene solution (30% (weight) MAO), 7.136g molybdenyl dichloride (n-butyl cyclopentadienyl) zirconium of 504g Davison 952-1836 silica, 677g methylaluminoxane.
The step of Preparation of Catalyst is as follows:
1. 952-1836 silica gel was dewatered 4 hours 250, use air purge.Use nitrogen purging when cooling off then.
2. silica gel is transferred in the mixing tank.
3. in a bottle, add 7.136g molybdenyl dichloride (n-butyl cyclopentadienyl) zirconium and 677g methylaluminoxane.
4. stir the catalyst solution in the bottle, be dissolved in the MAO solution until metallocenes.
5. MAO and metallocenes solution are transferred in the mixing tank that contains 955 silica gel that dewater at leisure, the fierce simultaneously layer of silica gel of stirring is dispersed in the layer of silica gel to guarantee catalyst solution.
6. after adding, continue to stir catalyzer 0.5 hour.
7. use nitrogen purging at 45 ℃, make dry catalyst.
8. catalyzer is sieved, remove particle greater than 150 microns.
9. the analytical results of catalyzer is as follows:
Output=767g catalyzer (making) by 500g silica gel
Al=9.95% (weight)
Zr=0.19% (weight)
The LLDPE resin is prepared in gas fluidized bed reactor by above-mentioned catalyzer, and processing condition are as follows:
Processing condition:
Fluidizing velocity 1.7 feet per seconds (0.5m/sec)
2.5 hours residence time
84 ℃ of temperature
Ethene 220psi
Hexene 3.6psi
Iso-pentane 50psi
Carbonic acid gas 3ppm
Ash 200-300ppm
The resin that obtains has following performance:
I2 1
Density 0.918
M w/M n 2.6
MFR 18
115 ℃ of fusing points

Claims (6)

1. a blend wherein contains 70-98% (weight) dry state, solvent-free synthetic composition, and said composition comprises sphere, non-porous particle, and its median size is 0.05-0.11cm (a 0.02-0.045 inch), and the sedimentation bulk density is 400-580kg/m 3(25-36 pound/foot 3), described composition is the multipolymer of ethene and a kind of alpha-olefin, and its density is 0.902-0.929, and MFR is 15-25, M w/ M nBe 2.0-3.0; And 2-30% (weight) is at 150-300MPa (1500-3000 normal atmosphere) and 200-300 ℃ of new LDPE (film grade) for preparing down, wherein the mist value of this blend is less than 5 (pressing ASTM D1003 measures), and dart shock resistance (pressing ASTM D-1709 measures) is greater than 400.
2. the described blend of claim 1, the described alpha-olefin of wherein said multipolymer has 3-10 carbon atom.
3. the described blend of claim 1, wherein said alpha-olefin is selected from butylene, hexene, octene and composition thereof.
4. any one described blend during aforesaid right requires wherein comprises the described multipolymer of 90-98% (weight) and the described new LDPE (film grade) of 2-10% (weight).
5. any one described blend during aforesaid right requires wherein comprises the described multipolymer of 95-98% (weight) and the described new LDPE (film grade) of 2-5% (weight).
One kind require by aforesaid right in the film made of any one described blend.
CN95192353A 1994-03-31 1995-03-21 LLDPE resin blends Pending CN1145082A (en)

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US22056194A 1994-03-31 1994-03-31
US08/220,561 1994-03-31

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CN (1) CN1145082A (en)
AU (1) AU686370B2 (en)
CA (1) CA2180012A1 (en)
WO (1) WO1995027005A1 (en)
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CA2180012A1 (en) 1995-10-12
KR970701758A (en) 1997-04-12
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EP0753026A1 (en) 1997-01-15
AU2228795A (en) 1995-10-23

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