CN1169744A - Extrusion compositions having high drawdown and substantially reduced neck-in - Google Patents

Abstract

The present invention discloses an ethylene polymer extrusion composition having high drawdown and substantially reduced neck-in, a process for making such a composition and a process of using such a composition to prepare extrusion coatings, extrusion profiles and extrusion cast films. The ethylene polymer extrusion composition is made of 75-95 weight percent of at least one ethylene alpha -olefin interpolymer and 5-25 weight percent of at least one high pressure ethylene polymer characterized as having high melt strength and a broad, bimodal molecular weight distribution. In profiles, coatings or films, the composition can be used as sealant, adhesive or abuse resistance layers.

Description

The extrusion compositions of the width of cloth that contracts that has high drawdown and significantly reduce

The present invention relates to the polyethylene extrusion compositions.Specifically, the present invention relates to a kind of ethene polymers extrusion compositions of the width of cloth that contracts that has high drawdown and significantly reduce.The invention still further relates to the method for making this ethene polymers extrusion compositions and make the goods of extrusion coating goods, extrusion profile form and extrude the method for the goods of curtain coating form of film.

The known heterogeneous linear low density polyethylene (LLDPE) (LLDPE) of being made in low pressure to middle pressure combined polymerization in the presence of common Ziegler coordination (transition metal) catalyst at low density polyethylene (LDPE) (LDPE) that high pressure polymerisation in the presence of the radical initiator is made and by ethene and alpha-olefin by ethene and ultra-low density polyethylene (ULDPE) for example can be used for to ground such as cardboard carry out extrusion coating, for the preparation of the sleeve pipe of extruding cast film and preparing extrusion profile such as electric wire and cable such as disposable diaper and food Package. Yet although LDPE shows usually and excellent extrudes processing characteristics and height is extruded drawing speed, for many application, the LDPE extrusion compositions lacks enough anti-misuse and toughness.For extrusion coating with extrude curtain coating, have high molecular and (that is to say melt index I by providing₂Less than about 2g/10) the LDPE composition be invalid with the trial that improves anti-misuse property, to such an extent as to because this composition must have too high melt strength can not be successfully drafted under high line speed.

Although LLDPE and ULDPE extrusion compositions have improved anti-misuse and toughness and MDPE (medium-density polyethylene) extrusion compositions and have improved barrier properties (for example preventing the infiltration of moisture and grease), but these linear ethylene polymkeric substance can not be extruded or drawing-off under height is drawn speed, and they show the relatively poor processibility of extruding as everyone knows.

The limit of ethylene alpha-olefin interpolymers is extruded drawing speed (under other feasible extruding production line speed) and is limited by the generation of the melt-flow wild effect of a kind of being called " draw resonance ", rather than the melt tension fracture that is caused by " strain hardening " limits, " strain hardening " takes place under higher line speed, and typically at the high pressure ethylene polymer of LDPE and other high branching for example ethylene-acrylic acid (EAA) interpolymer and ethene-vinyl acetate base ester (EVA) interpolymer.

" draw resonance " or " the melt material gushes " can take place in the course of processing of LLDPE, ULDPE and other simple linear polymer such as high density polyethylene(HDPE) (HDPE), polypropylene and polyester, described processing comprises the quick stretching of melt or draws, and extrudes cast film, extrusion profile and fine denier fiber spinning as extrusion coating, manufacturing.Equally, the outbreak of draw resonance or appearance are also clearly.

US4,339, people's such as Kurtz patented technology and US4 in 507,486, in 377 in people's such as Lucchesi the patented technology, it is when final condition is fixed die head position and speed and fixed extraction location speed that draw resonance is said to be, and occurs in randomness and/or periodically sustained oscillation, change or the pulsation of polymer melt aspect speed and cross-sectional area of the melt draw-down operation between die head position and the extraction location.Draw resonance when surpassing the polymkeric substance certain limit, ratio of drawing (be the momentary velocity of the melt velocity of extraction location divided by die head exit place melt, this value often is similar to the inverse of the inverse of final polymer thickness divided by the instantaneous melt thickness in die head exit place) takes place.Draw resonance is a kind of melt-flow unstable, and the size that shows as final veneer, film or fiber is irregular, and often change very big thickness and width.During speed when line speed obviously surpasses draw resonance and takes place, can cause tablet or filament breakage and whole drawing-off or veneer operation are stopped work.

Can there be each species diversity and complexcase between known different extrusion equipment, recently represent relative anti-draw resonance through limit drawing-off commonly used, for common linear ethylene polymkeric substance, although most of industrial drawing-off manipulation requires greater than 20: 1 ratio of drawing, have found that the maximum stable ratio of drawing should be less than 10: 1.

" drawing-off " be meant along machine direction here and occasionally (side by side) with lesser extent also along cross directional stretch or the elongation molten polymer extrudate (tablet or long filament).

" melt strength " is also referred to as " melt tension " in relevant technical field, its implication and quantity here are meant more than the extrudate fusing point with specific speed drawing-off and melt extrude thing required stress or power (as being applied by the rolling cylinder that strain transducer is housed) when passing the die head that has standard plastometer (described the sort of as ASTM D1238-E).Melt strength values is used a li newton (cN) expression here, uses Gottfert Rheotens in 190 ℃ of mensuration.In general, for ethylene alpha-olefin interpolymers and high pressure ethylene polymer, melt strength can be along with the increase of molecular weight or widening and/or increasing along with the increase of melt-flow ratio along with molecular weight distribution.

" width of cloth contracts " influenced by the extrudate swollen, and is subjected to the influence of surface tension effects, its implication to be meant the extrudate width of die width and extraction location here on less degree or makes difference between the final width of goods.The amplitude that contracts that records (under extrusion capacity constant condition) should keep constant or reduces owing to drawing speed improves, and in general, natural ethylene polymers molecular weight reduce and/or molecular weight distribution when narrowing down its amplitude increase of contracting be well-known.Here the said amplitude that contracts be with the weight of 1 mil (0.025mm) individual layer extrusion coating, to use diameter be that 3.5 inches (8.9cm), L/D are that 30: 1 Black-Clawson extrusion coating machine is measured, this extrusion coating machine is equipped with die head and 50 pounds of (22.7kg) kraft paper of can be wide by 30 inches (76.2cm) amplitude modulation to 24 inch (61cm) and having the die gap of 20 mils (0.51mm).

" extraction location " is meant point of contact on the multi-roll device (or upper end or lower end) here, this multi-roll device will melt extrude thing from it in the instantaneous initial thickness drawing-off of die head exit or draw until its final thickness.This multi-roll device can be nip rolls, rubber rollers, chill roll, they combination or by the similar roller of for example metal or rubber and various surface (as polishing, delustring or embossing) formation; All these rollers are working of counter extensioin resonance to a certain extent all.

The trend of various possible terms of settlement with the contract width of cloth and/or the draw resonance that reduce ethylene alpha-olefin interpolymers is disclosed.The way that many these class terms of settlement are relevant devices and other relate generally to the way of the improvement in performance of ethylene alpha-olefin interpolymers, and this improvement is to realize by forming a kind of polymkeric substance that is mixed with the high pressure ethylene polymer (for example new LDPE (film grade)) of high branching.The US4 of Thompson, 348,346th, attempt with equipment reduce the to contract example of the width of cloth and draw resonance.Thompson has set forth polymer molten fluid has been become owner of die head along the edge biphasic injection of major ingredient laminar flow, thereby reduces to contract the width of cloth and improved edge beading control is provided.

People such as Cancio are at US4,668,463 and US4,626, a kind of terms of settlement that improves equipment that stops draw resonance to take place that is specifically designed to is provided in 574, this method locates to be provided with take off roll being no more than 6 inches (15.2cm) from die head, thereby little air gap/drawing-off gap and the draw resonance that reduces are provided.People such as Luchessi are at US4, disclose the method that makes liquid medium such as nitrogen, carbon monoxide or air flow to the fusion tablet before the drawing-off position in 486,377, with this as the feasible method that stops draw resonance.Similarly, people such as Kurtz are at US4, disclose draw resonance in 608,221 can alleviate by using a kind of stretching device, and this device has no friction surface in " the rapid cooling zone territory " between die head and extraction location.

On the contrary, as the improved example of miscellaneous equipment that alleviates or reduce draw resonance, Chaing is at US4, discloses the method for radiation heating fusion tablet before the chill roll extraction location in 859,379.

The example that shows the improved ethylene alpha-olefin interpolymers composition that reduces draw resonance comprises US4,378,451 (Edwards), this patent disclosure based on the high flow rate composition of the degraded propene polymer that is mixed with new LDPE (film grade).Analogous cases be people such as Werkman at US3, provide in 247,290, the high density polyethylene(HDPE) of thermal destruction (viscosity breaking) is mixed with new LDPE (film grade) to prepare the extrusion coating composition of high drawdown.Other example that comprises the ethylene alpha-olefin interpolymers mixture of new LDPE (film grade) is disclosed in US4 by people such as Kurtz, 339, in 507, combine with heterogeneous common LLDPE and improved velocity of flow is provided for the extrusion coating composition thereby wherein disclose high pressure LDPE with 20-98wt%.

Not by comprise the polymer degradation step and/or mix with the branching high pressure ethylene polymer and the example of composition that reduces draw resonance by people such as Dohrer at US4,780, open in 264, find that wherein melt flow unexpectedly allows fast extrusion coating line speed and extrudate flow casting line speed than the LLDPE less than 8.3 (promptly the molecular weight distribution that adopts is than general adopt also narrow).Yet can conclude that what these materials also showed higher the contract width of cloth and/or difference extrudes processibility (for example the extruding machine amperage is higher).

Although obtained various progress, when extruding the ethylene alpha-olefin interpolymers composition, especially under high extruding production line speed, still need avoid draw resonance problem and high-shrinkage width of cloth problem.For example, although US5,395, disclosed composition is compared the width of cloth that contracts that shows significantly improved line speed (drawing speed), high anti-draw resonance and reduce with common line style ethylene ' alpha '-olefin composition in 471, but this composition still shows the high width of cloth that contracts (for example extrusion coating weight is 1.0 mils (0.025mm) time 〉=7 inch (17.8cm)).In addition, when in the ethylene alpha-olefin polymer composition with common high pressure ethylene polymer as the mixed polymer composition when improving line speed, anti-draw resonance and contracting width of cloth performance, need suitable high density (greater than composition total weight 20%) high pressure ethylene polymer could realize this improvement as the mixed polymer composition.Yet the production unit of resin or the capacity of convertor are limited, and the only feeding equipment that for example can buy is a kind of feeder of little heavyweight, and this can make the demand to the high pressure ethylene polymer mixing element of higher concentration be suppressed.

As mentioned below, the present invention has satisfied basically to the demand of the ethene polymers extrusion compositions with high line speed, high anti-draw resonance and the significantly reduced width of cloth that contracts and to make the demand of this method for compositions with the lower volume feeding equipment.Composition of the present invention can use in conjunction with known equipment improvement, and preferably uses with degradable polymer, and can realize the present invention and known terms of settlement combine advantage or collaborative advantage.

Make the advantage of improved extrusion compositions except using wide feeding equipment of range of choice or mixing equipment, convertor or processing units also can be realized improved anti-misuse or barrier properties (owing to having used ethylene alpha-olefin interpolymers), high productivity (owing to can reach higher line speed) at present and subtract the advantage of thick (lower coating weight or thin film and section bar), also make high-quality even veneer, section bar and film simultaneously.For not improved ethylene alpha-olefin interpolymers, other advantage of the present invention is the remarkable high melt strength that the present composition has.In section bar was extruded processing as the electric wire and cable goods, the melt strength of this raising can provide improved product clarity, less molten hanging down and higher pyrogen beginning intensity.

According to the present invention, we have found a kind of improving one's methods of ethene polymers extrusion compositions of making, a kind of improved ethene polymers extrusion compositions, and ground, ethylene polymer composition extrusion profile and the ethylene polymer composition of manufacturing extrusion coating are extruded the method for cast film.

One aspect of the present invention is a kind of ethene polymers extrusion compositions, said composition contains at least a ethylene/alpha-olefin interpolymer that accounts for composition total weight 75-95%, this interpolymer is selected from substantially linear ethylene polymers, homogeneously branched linear ethylene polymkeric substance and heterogeneous branching linear ethylene polymkeric substance, the feature of therein ethylene/alpha-olefinic polymer is that density is in the scope of 0.85-0.940g/cc, said composition also contains at least a high pressure ethylene polymer that accounts for composition total weight 5-25%, and the feature of this polymkeric substance is melt index I ₂Less than 6.0g/10 minute, density is at least 0.916g/cc, be installed on 190 ℃ of melt strengths that record with Gottfert Rheotens and be at least 9cN, the Mw/Mn ratio that records with gel permeation chromatography is at least 7.0, and measured bimodal molecular weight distribution with gel permeation chromatography, the melt index I of the polymer-extruded composition of therein ethylene ₂Be at least 1.0g/10 minute.

Another aspect of the present invention is a kind of method for preparing the ethene polymers extrusion compositions, and this method comprises:

(a) at least a high pressure ethylene polymer that will account for extrusion compositions weight 5-25% with

At least a ethylene alpha-olefin interpolymers that accounts for extrusion compositions weight 75-95% mixes,

Wherein, mix said at least a high pressure ethylene polymer, this feeding equipment with feeding equipment

Be an one of preparation said at least a ethylene alpha-olefin interpolymers used polymerization process

Divide the melt index I of this ethene polymers extrusion compositions ₂Be at least 1.0g/10 minute,

Its width of cloth that contracts is compared the phase of composition when individual layer extrusion coating weight is 1 mil (0.025mm)

The prestige amplitude that contracts is low at least by 12%, and

(b) collect or carry this extrusion compositions with the form that is applicable to subsequent applications.

Another aspect of the present invention is a kind ofly to make ground, the extrusion profile of extrusion coating or extrude the method for cast film with the ethene polymers extrusion compositions, and this method comprises:

(i) ethylene polymer composition is infeeded at least one forcing machine of extruding production line, its

In this ethylene polymer composition contain at least a second that accounts for composition total weight 75-95%

Alkene/alpha-olefin interpolymer, this interpolymer is selected from substantially linear ethylene polymers, homogeneously branched

Linear ethylene polymkeric substance and heterogeneous branching linear ethylene polymkeric substance, therein ethylene/alpha-olefin

The feature of polymkeric substance be density in the scope of 0.85-0.940g/cc, melt index I ₂

0.1-50g/10 minute scope in, said composition also contains and accounts for composition total weight 5-

25% at least a high pressure ethylene polymer, the feature of this polymkeric substance are melt index I ₂Little

In 1.0g/10 minute, density was at least 0.916g/cc, used Gottfert Rheotens

Be installed on 190 ℃ of melt strengths that record and be at least 9cN, record with gel permeation chromatography

The Mw/Mn ratio is at least 7.0, and has measured the wide/bimodal molecular weight branch with gel permeation chromatography

Cloth, the melt index I of the polymer-extruded composition of therein ethylene ₂Be at least 1.0g/10 minute,

(ii) fusion and to mix this ethylene polymer composition poly-to form at least a uniform fusion

Compound stream,

Extruding production line is worked being higher than under the line speed of 152m/min,

Molten polymer flow is extruded forming elementary extrudate by die head, and

(a) drawing-off and cool off this extrudate and have at least one deck ethene polymers and extrude to make

The extrusion profile of composition, perhaps

(b) this extrudate of drawing-off is to ground, thereby extrudes with one deck ethene polymers at least

Composition is to the ground veneer, perhaps

(c) drawing-off and cool off on this extrudate to one caterpillar and have one deck at least to make

The film of ethene polymers extrusion compositions, and

(vi) carry or collect section bar, prepare against follow-up use through the ground or the film of veneer.

A further aspect of the invention is a kind of goods of one deck ethene polymers extrusion compositions at least that comprise, wherein said extrusion compositions contains at least a ethylene/alpha-olefin interpolymer that accounts for composition total weight 75-95%, this interpolymer is selected from substantially linear ethylene polymers, homogeneously branched linear ethylene polymkeric substance, heterogeneous branching linear ethylene polymkeric substance, the feature of therein ethylene/alpha-olefinic polymer is that density is in the scope of 0.85-0.940g/cc, said composition also contains at least a high pressure ethylene polymer that accounts for composition total weight 5-25%, and the feature of this polymkeric substance is melt index I ₂Less than 6.0g/10 minute, density is at least 0.916g/cc, be installed on 190 ℃ of melt strengths that record with Gottfert Rheotens and be at least 9cN, the Mw/Mn ratio that records with gel permeation chromatography is at least 7.0, and measured bimodal molecular weight distribution with gel permeation chromatography, the melt index I of the polymer-extruded composition of therein ethylene ₂Be at least 1.0g/10 minute.

Rely on the present invention, can be than the width of cloth that contracts that relies on known polymer mixture or not improved ethylene alpha-olefin interpolymers composition to obtain to reduce, higher drawing speed and the anti-draw resonance of Geng Gao.

Fig. 1 is illustrating of molecular weight distribution (the using gel permeation chromatography) that be applicable to high pressure ethylene polymer composition of the present invention.

Fig. 2 is the molecular weight distribution of four kinds of different high pressure ethylene polymer compositions and illustrating of contrast bimodal (using gel permeation chromatography).

The relation curve of the width of cloth that contracts when Fig. 3 is the melt strength of ldpe resin and 1 mil (0.025mm), this curve are used for estimating by extrapotation the width of cloth performance that contracts of resin that can not be drafted because melt strength is excessive.

Composition of the present invention contain account for composition total weight 75-95%, preferred 80-95%, More preferably 85-95%, at least a ethylene alpha-olefin interpolymers of 88-95% most preferably, also Contain and account for composition total weight 5-25%, preferred 5-20%, more preferably 5-15%, optimum Select at least a high pressure ethylene polymer of 5-12%.

Preferably, the weight fraction in component of polymer in the composition consists of vinyl polymerization of the present invention The expectation contracting amplitude low at least 12 of the contracting amplitude comparison composition reality of thing extruding composition or that measure %, preferably at least 16%, more preferably at least 24%, most preferably at least 30%. The present composition Density in the scope of 0.850-0.940g/cc, preferably in the scope of 0.860-0.930g/cc, More preferably in the scope of 0.870-0.920g/cc, most preferably in the scope of 0.880-0.915g/cc In. The melt index (MI) I of the present composition₂In 1-50g/10 minute scope, preferably at 1-30g/10 Minute scope in, more preferably in 1-20g/10 minute scope, most preferably at 1.0-10g/10 Minute scope in. The melt of the present composition that records with Gottfert Rheotens device is strong Degree is at least 9 lis of newton (cN), preferably at least 15cN, more preferably 20cN, most preferably extremely at least Few 25cN.

Term " polymer " used herein " refer to be made by similar or inhomogeneity monomer polymerization poly-The compound that closes. Therefore generic term " polymer " comprises term " homopolymers ", " homopolymers " Be commonly used to refer to the polymer only made by a class monomer.

It is poly-that term used herein " EVA " refers to be made by at least two class different monomers polymerizations Compound. Therefore generic term " EVA " comprises term " copolymer ", " copolymer " exactly Say so and be used to refer to the polymer of being made by two kinds of different monomers. But term in this field " copolymer " Also be used to refer to the polymer of being made by two or more different monomers.

Term used herein " expectation contracting amplitude " for contracting amplitude reality, that measure is Finger calculates according to weight fraction and the independent contracting amplitude that provided by the component of polymer of extruding composition and phase The contracting amplitude of hoping or estimating. As the example of a calculating, if extruding composition contains 90wt%'s Extrusion coating contracting amplitude is 7.5 ethylene alpha-olefin interpolymers and 10wt during 1 mil (0.026mm) Extrusion coating contracting amplitude is 1.75 inches (4.4cm) high pressure second during 1 mil (0.025mm) of % Alkene polymer, then the expectation contracting amplitude of this extruding composition is 6.9 inches (17.5cm), wherein 6.75 inch (16.9cm) is provided remaining 0.175 inch by ethylene alpha-olefin interpolymers (0.44cm) provided by high pressure ethylene polymer.

Term " high pressure ethylene polymer " or " the ethene polyethylene of high branching " here refer to pressing In thermal reactor or the tubular reactor, above at 14,500psi (100MPa), cause at free radical The polymer that part or all of homopolymerization or copolymerization form under the existence of agent.

In general sense, term " homogeneous ethylene polymer " and " homogeneously branched ethylene polymer pass Be tied to a kind of ethene polymers, the comonomer in this ethene polymers is in given polymer molecule Random distribution, and whole polymer molecules have identical ethene and the mole of comonomer basically Ratio. The feature of homogeneously branched ethylene polymer be short-chain branched profile exponent (SCBDI) greater than or etc. In 30%, be preferably greater than or equal 50%, more preferably greater than or equal 90%, and basically do not have Detectable high density (crystallization) polymer moieties. The definition of SCBDI is common content of monomer entirely 50% percetage by weight with interior polymer molecule of section's comonomer molar content intermediate value. For poly-Alkene, the existence of SCBDI and high density polymer composition can be by known intensification elution fractionation (TREF) method is measured, this method as by people such as wild at the polymer science magazine, the polymer thing A reason version Vol.20, p.441 disclosed in (1982), by L.D.Cady, " the work of comonomer type With with contribution to the LLDPE properties of product ", the technical conference of SPE region, Quaker Square Hilton, Akron, Ohio, 1-2 day in October, disclosed among the pp.107-119 (1985), or At US4, disclosed in 798,081.

Term " substantially linear ethylene polymers " comprises term " substantial linear alpha-olefine polymers ". The substantial linear alpha-olefine polymers contains long chain branches and causes by being incorporated into the homogeneous phase comonomer Short chain branch. The structure of long chain branches is identical with main polymer chain and than short chain branch head. Substantially The main polymer chain of linear alpha-olefins polymer is former with an average 0.01-3 long chain branches/1000 carbon The degree of son is substituted. The used essentially linear polymer of the present invention is preferably with 0.01-1 long chain branches / 1000 carbon atoms, more preferably got with the degree of 0.05-1 long chain branches/1000 carbon atom Generation.

Long chain branches definition in this article is that chain length is at least 6 carbon atoms, more than 6 carbon atoms Length can not be distinguished out with the 13C nuclear magnetic resonance spectroscopy. Long chain branches is approximately accompanying with it The length that the length of main polymer chain is identical.

Can measure depositing of long chain branches in the Alathon with 13C nuclear magnetic resonance (NMR) spectrometry , (V.2﹠3, p.285-297) disclosed method can for polymer chemistry physical comment, C29 with Randall To determine its quantity.

In fact, present¹³The C nuclear magnetic resonance spectrometry can not be measured the above long chain branches of 6 carbon atoms Length. But it is poly-also to exist other to be used to measure the ethene that comprises ethene/1-octene copolymer body The known method of the existence of long chain branches in the compound. Gel permeation chromatography and little angle laser light scattering detect Device cooperates (GPC-LALLS) and gel permeation chromatography to cooperate with differential viscosity meter detector (GPC-DV) be two kinds of these class methods. Application and the base thereof of these methods on long chain branches detects The plinth theory has sufficient proof in the literature. For example see Zimm, G.H.and Stockmayer, W.H., The Chemical Physics magazine, 17,1301, (1949) and Rudin, A., the modernism of polymer characterization, John Wiley ﹠ Sons, New York (1991) pp.103-112.

The willem deGroot of Dow chemical company and P.Steve Chum were on October 4th, 1994 At St.Louis, carry in the analytical chemistry of Missouri and spectrum scietific federation (FACSS) meeting The digital proof GPC-DV that goes out is that a kind of existence to long chain branches in the substantial linear ethenyl copolymer is advanced The process useful that row is quantitative. Especially, deGroot and Chum find to use Zimm-Stockmayer side Amount and the usefulness of the long chain branches of the substantial linear ethylene homo matter sample that journey is measured¹³The long-chain that C NMR measures The amount of branch is very relevant.

In addition, deGroot and Chum find that the existence of octene can not change polyethylene specimen in the solution The hydrodynamics volume, therefore by the mole percent of octene in the known sample, can calculate by The molecular weight that octene short chain branch causes improves. In order to eliminate 1-octene short chain branch to the molecular weight liter High role, deGroot and Chum show GPC-DV can be used for to substantial linear ethene/ The amount of long chain branches is carried out quantitatively in the octene copolymer.

DeGroot and Chum give Log (I₂Melt index (MI)) with the Log of GPC-DV definition The function relation curve of (GPC weight average molecular weight), the bright substantially linear ethylene polymers of this curve table Long chain branches situation (not being the size of long-chain branch) and high pressure, high branched low density polyethylene (LDPE) Be more or less the same, and with Ziegler-type catalyst (such as the titanium complex) and common homogeneous catalyst (as Hafnium complex and vanadium complex) the polyvinyl situation of producing has notable difference.

For ethylene alpha-olefin interpolymers, its long chain branches length is longer than by mixing α in the main polymer chain-alkene and the short chain branch that produces. In the used substantial linear ethylene alpha-olefin interpolymers of the present invention The experienced impact that has long chain branches and produce for example shows as, and rheological property improves and/or melt Mobile, I₂₀/I ₂Improve, this paper adopts the results expression stream of gas extrusion rheometry (GER) Sex change can and quantitative to it.

With term " substantially linear ethylene polymers " contrast, term " linear ethylene polymer " refers to This polymer does not have to measure or evincible long chain branches.

The molecular structure of high pressure ethylene polymer composition is for the contracting width of cloth, the melt strength of final composition It is critical improving with processing characteristics. Being used for high pressure ethylene polymer of the present invention has higher Melt strength, just at least 9cN, preferably at least 15cN, more preferably at least 20cN, optimum Select at least 25cN. High pressure ethylene polymer be further characterized in that have by gel permeation chromatography true Fixed bimodal distribution, and Mw/Mn is at least 7.0, preferably at least 7.3, more preferably at least 7.6. The melt index (MI) I for preparing the used high pressure ethylene polymer of extruding composition of the present invention₂Less than 6.0g/10 Minute, preferably less than 1.0g/10 minute, be more preferably less than 0.8g/10 minute, most preferably less than 0.5g/10 minute. The density of the used high pressure ethylene polymer of the present invention is at least 0.916g/cc, preferred At least 0.917g/cc, more preferably 0.918g/cc at least. When with EVA (copolymer or three for example Membered copolymer such as ethene-vinyl acetate base ester-carbon monoxide (EVACO)) as mixed polymer During composition, the density of high pressure ethylene polymer composition will be higher.

The selected high pressure ethylene polymer composition that mixes with the ethylene alpha-olefin interpolymers composition can In hydrothermal reaction device or tubular reactor, to use at least a radical initiator poly-with conventional high pressure The method of closing is made. When using the hydrothermal reaction device, reaction zone can be single district or multi-region. Telogen as Propylene and iso-butane also can be used as chain-transferring agent. Preferably, use hydrothermal reaction device and do not add accent Aggressiveness and prepare high pressure ethylene polymer is because the tubular reactor method is difficult to produce the wide/bimodal molecular weight branch Cloth. Yet the hydrothermal reaction device is combined in the mode of serial or parallel connection with tubular reactor and also is suitable for making The present composition is because also can produce bimodal molecular weight distribution in this way.

Be applicable to that the radical initiator that makes vinyl polymerization under high reactor pressure is comprising of knowing (but being not limited to) peroxide and oxygen. The polyvinyl melt that uses high pressure polymerisation to make is strong It also is known that degree reaches maximum method, includes, but is not limited to make the reaction zone temperature difference to reach Greatly, inject multiple initator, prolong holdup time and raising at reactor and post-reactor The gas access temperature.

The high pressure ethylene polymer composition that is applicable to preparation extruding composition of the present invention comprises low density polyethylene Alkene (homopolymers) and ethene and at least a α, β-olefinic unsaturated comonomer such as acrylic acid, methyl The EVA of acrylic acid, methyl acrylate and vinyl acetate base ester. Be applicable to the copolymerization of preparation high-pressure ethylene The method of body composition by people such as McKinney at US4, open in 599,392.

Although think that both high pressure ethylene homopolymers and EVA all are applicable to the present invention, Natene Preferred. When using at least a high-pressure ethylene EVA composition, with the gross weight of EVA composition Amount meter, preferred EVA composition comprise the comonomer of 0.1-55wt%, more preferably comprise 1-The comonomer of 35wt%, most preferably comprise the comonomer of 2-28wt%.

The used substantial linear ethylene alpha-olefin polymer of the present invention is US5,272,236 Hes US5, the compound of a class uniqueness that further elaborates in 278,272.

Substantially linear ethylene polymers significantly is different from and is commonly referred to as homogeneously branched linear ethylene/alpha-olefin One base polymer of copolymer, this base polymer for example is disclosed in US3 by Elston, in 645,992. It is poly-that substantially linear ethylene polymers also significantly is different from the linear ethylene that is commonly referred to as the polymerization of homogeneous phase Ziegler (for example ultra-low density polyethylene, linear low density polyethylene (LLDPE) or high density polyethylene (HDPE), they adopt compound With such as people such as Anderson at US4, the people such as disclosed method and Dohrer use in 076,698 Be disclosed in US4, the method in 780,264 is made) a base polymer, and significantly be different from and be called High branching high pressure low density Alathon and ethenyl copolymer such as ethylene-acrylic acid that free radical causes (EAA) base polymer of copolymer and ethene-vinyl acetate base ester (EVA) copolymer.

Can with single-point (singlesite) polymerization catalyst (for example by Canich at US5,026,798 In disclosed or by Canich at US5, disclosed monocycle-pentadienyl transition metal alkene in 055,438 The polymerized hydrocarbon catalyst) or controlled how much (constrained geometry) catalyst (for example by The people such as Stevens are at US5, and are disclosed in 064,802) for the preparation of substantially linear ethylene polymers, only Want this catalyst to use and US5, disclosed method is assisted mutually in 272,236 and US5,278,272 Transfer. This polymerization also is disclosed in PCT/US92/08812 (proposition on October 15th, 1992) In. Yet, substantial linear ethenyl copolymer and homopolymers preferably use suitable controlled geometry catalyst, Especially U. S. application 545,403, on September 12nd, 1991 of proposing July 3 nineteen ninety propose 24,758,660 and 1991 on June proposing 12,758,654,1991 on September propose 720,041 in disclosed controlled geometry catalyst.

The co-catalyst that is applicable to the application includes, but is not limited to such as polymerization or oligomeric aikyiaiurnirsoxan beta, Particularly the MAO of MAO or modification (for example use US5,041,584, US4, disclosed method preparation in 544,762, US5,015,749 and/or US5,041,585) and Inertia, compatible non-coordination ion type compound. Preferred co-catalyst is the non-coordination boron of inertia Compound.

The polymerizing condition of making the used substantial linear ethylene copolymer composition of the present invention is preferably suitable In those conditions of continuous solution polymerization method, but the present invention is unqualified in this. As long as used Suitable catalyst and polymerizing condition also can adopt continuous slurry polymerization method and continuous gas-phase polymerization Method. In order to make the present invention used substantial linear EVA and copolymer polymerization, can use aforementioned list Site catalyst and controlled geometry catalyst, but for substantially linear ethylene polymers, these polymerizations Method should form substantially linear ethylene polymers. That is to say, even use same catalyst, Polymerizing condition that neither be all can both be made substantially linear ethylene polymers inherently.

For example, in the polymerization enforcement side of a suitable novel substantially linear ethylene polymers of preparation In the case, adopt continuous polymerization, be different from the batch polymerization method.

For substantially linear ethylene polymers, preferably carry out polymerization with the continuous solution polymerization method. Logical Often, in order to adopt controlled geometry catalyst technology as herein described to make substantially linear ethylene polymers And when making Mw/Mn keep lower, I₁₀/I ₂Along with temperature of reactor and/or ethylene concentration and become Change. The ethylene concentration that reduces and higher temperature produce higher I usually₁₀/I ₂ Generally, because reaction Ethylene concentration reduces in the device, and polymer concentration is raise. For novel substantial linear ethenyl copolymer and Homopolymers, the polymer concentration of continuous solution polymerization method are preferably about 5wt% of reactor capacity More than, especially be more than about 6wt% of reactor capacity. Usually, adopt controlled geometry catalyst The polymerization temperature of the continuity method of technology is 20-250 ℃. If need to have higher I₁₀/I ₂Than (I for example₁₀/I ₂Be about 7 or higher, preferably be at least about 8, especially be at least about 9) narrow molecular-weight Distribution polymer, then the ethylene concentration in the reactor preferably is no more than about 8wt% of reactor capacity, Especially be no more than about 6wt% of reactor capacity, more preferably no more than about 4wt of reactor capacity %.

The feature of the substantial linear ethylene copolymer composition that the present invention is used is:

(a) melt flows compares I₁₀/I ₂≥5.63，

(b) use the gel permeation chromatography molecular weight distribution mw/mn, and define in order to lower equation:

  (Mw/Mn)≤(I ₁₀/I ₂)-4.63，

(c) extrude rheology according to gas, substantially linear ethylene polymers surface melt fracture begins

The time the utmost point of limit shear rate when beginning than the melt fracture of linear ethylene polymer surfaces at least

The limit shear rate is high by 50%, wherein substantially linear ethylene polymers and linear ethylene polymer bag

Contain one or more same comonomers, the I of linear ethylene polymer₂, Mw/Mn and close

Degree account for substantially linear ethylene polymers 10% in, and substantial linear vinyl polymerization wherein

The corresponding limit shearing rate of thing and linear ethylene polymkeric substance is to adopt under the same melt temperature

The gas squeezing rheometer is measured, and

(d) according to single dsc DSC, melting peak is between-30 and 150 ℃.

" high-density " part that the used substantial linear ethenyl copolymer of the present invention does not have available TREF technology to measure basically.The substantial linear ethenyl copolymer does not generally contain the polymer moieties that the degree of branching is less than or equal to 2 methyl/1000 carbon atoms." high density polymer part " also can be said to is the polymer moieties of the degree of branching less than about 2 methyl/1000 carbon atoms.Together with other benefit, do not contain high density polymer applying smoothness, impressionability, optical property are improved, and improved the flexibility and the elasticity of film/veneer.

With gas squeezing rheometer (GER) limit shearing rate of relevant melt fracture and ultimate shearing stress and other rheological property (PI) are measured as " rheology processing index ".The gas squeezing rheometer is by M.Shida, R.N.Shroff and L.V.Cancio are at polymer engineering science Vol.17, p.770, No.11 discloses at " rheometer that is used for molten plastic " (1982) pp.97-99 that is published by Van NostrandReinhold Co. in (1977) and by John Dealy.GER experiment is under the pressure of 190 ℃ temperature, nitrogen atmosphere, 250-5500 pound/in2, and adopting diameter 0.0754mm, L/D is that 20: 1, fluid inlet angle are that 180 ° die head carries out.For substantially linear ethylene polymers as herein described, PI is to be 2.15 * 10 with GER at apparent shearing stress ⁶Dyne/cm ²The time material apparent density (thousand pools) measured.The used substantially linear ethylene polymers of the present invention is that the PI scope is 0.01-50 thousand pools, preferred 15,000 pool or littler ethenyl copolymers.The PI of substantially linear ethylene polymers used herein be less than or equal to the linear ethylene polymkeric substance (common Ziegler polymeric polymkeric substance or by Elston at US3, the even branched polymers of disclosed line style in 645,992) PI 70%, the I of linear ethylene polymkeric substance ₂, Mw/Mn and density all substantially linear ethylene polymers 10% in.

The rheological behaviour of substantially linear ethylene polymers also can be with Dow rheology index (DRI) expression, and " the stdn time of relaxation that is caused by long chain branches " of this exponential representation polymkeric substance (sees S.Lai and G.W.Knight ANTEC93 progress, INSITE ^TMStructure/the rheological of technology polyolefine (ITP)-ethylene concerns new regulation, New Orleans, and La., May1993).For the polymkeric substance that does not have any detectable long chain branches (for example, the Tafmer that can obtain from Mitsui petrochemical industry company ^TMProduct and the Exact that can obtain from Exxon chemical company ^TMProduct), the scope of its DRI value is from 0-about 15 and irrelevant with melt index.Usually, compare with the dependency of melt flow ratio with DRI, low pressure extremely middle pressure ethene polymers (especially more low-density) DRI provides dependency improved and melt elasticity and high-shear flowability.For the used substantially linear ethylene polymers of the present invention, DRI is preferably at least 0.1, is preferably at least 0.5 especially, most preferably is at least 0.8.DRI can be by following Equation for Calculating:

DRI＝(3652879*τ ₀1.00649/η ₀-1)/10

τ wherein ₀Be the characteristic relaxation time of material, η ₀It is the shear viscosity at zero point of material.τ ₀And η ₀All

Be " best fit " value of following intersection equation:

η/η ₀＝1/(1+(γ*τ ₀) ^1-n)

Wherein n is the power law index of material, and η and γ are respectively viscosity and the shearing rate that records.Sticking

The basic mensuration employing of degree and shearing rate data be 190 ℃ 0.1-100 radian per second

Rheology machinery spectrometer (RMS-800) and gas under the dynamic scan mode are extruded rheology

Instrument (GER), its extrusion pressure are 1,000psi-5, and 000psi (6.89-34.5MPa),

The shearing stress that is equivalent to 0.086-0.43MPa, using diameter 0.754mm, L/D is 20: 1

190 ℃ die head.Change the requirement that adapts, certain material in order to satisfy with melt index

Detection can carry out at 140-190 ℃.

The relation curve of apparent shearing stress and apparent shear rate is used for distinguishing the melt fracture phenomenon and gives polyvinyl limit shearing rate and the quantitative usefulness of ultimate shearing stress.According to Ramamurthy at the rheology magazine, 30 (2), 337-357, the elaboration in 1986, more than a certain limit velocity of flow, the viewed irregularity of extruding can generally reduce two kinds of main types: surperficial melt fracture and whole melt fracture.

The surface melt fracture is to take place under the stable from the teeth outwards flow condition, and scope loses specular gloss to forming very serious " shark skin spot " from film in detail.Here, according to measuring with above-mentioned GER, the feature that (OSMF) takes place surperficial melt fracture is that extrudate begins to tarnish, and at this moment the surfaceness of extrudate can only be measured by 40 times magnification.Limit shearing rate when the surperficial melt fracture of substantial linear ethenyl copolymer and homopolymer takes place is at least than having essentially identical I ₂Limit shearing rate when taking place with the surperficial melt fracture of the linear ethylene polymkeric substance of Mw/Mn is high by 50%.

Whole melt fracture takes place under unsettled Extrusion Flow condition, and scope is to random distortion from rule distortion (coarse and smooth replace, volution etc.) in detail.With regard to the acceptable and maximum anti-misuse property of the industry of film, veneer and section bar, if there is surface imperfection, these surface imperfection should be very little.Be used for those of substantially linear ethylene polymers composition, especially density＞0.910g/cc of the present invention, the ultimate shearing stress when whole melt fracture takes place is greater than 4 * 10 ⁶Dyne/cm ²When (OSMF) takes place in surperficial melt fracture used herein and the limit shearing rate of whole melt fracture when (OGMF) takes place be the basis that is changed to of the surfaceness of the extrudate extruded with GER and profile.Preferably, in the present invention, the substantially linear ethylene polymers composition is characterised in that its limit shearing rate rather than its ultimate shearing stress.

The substantial linear alpha-olefinic polymer is similar to the homogeneously branched ethylene alpha-olefin polymer composition that other contains single polymers composition material, it is characterized in that single DSC melting peak.This list melting peak is to use by the differential scanning calorimeter of indium and deionized water calibration to measure.Measuring method comprises the sample scale of 5-7mg, and " for the first time heating " to about 140 ℃ and kept 4 minutes, is cooled to-30 ℃ and kept 3 minutes with 10 ℃/minute speed, is heated to 140 ℃ and carry out " heating for the second time " with 10 ℃/minute speed again.Obtain single melting peak from the heat flow of " heating for the second time " and the relation curve of temperature.Calculate whole fusion heats of polymkeric substance by area under a curve.

For density is the substantially linear ethylene polymers composition of 0.875-0.910g/cc, sensitivity according to equipment, single melting peak can demonstrate " acromion " or " summit " in low melt one side, and low melt one side constitutes less than 12%, the especially less than 9% of the whole fusion heats of polymkeric substance, less than 6% more especially.Other homogeneously branched polymkeric substance such as Exact ^TMResin also can be observed this phenomenon, and can identify according to the inclination angle of single melting peak monotone variation of the melt region that passes this phenomenon.This phenomenon is to occur in 34 ℃ the time at the fusing point of single melting peak, the typical case 27 ℃ with interior appearance, more typical at 20 ℃ with interior appearance.Can be based on the fusion heat of this phenomenon respectively with the ratio integration mensuration of heat flow with the relation curve relevant area down of temperature.

The molecular weight distribution of ethylene alpha-olefin interpolymers composition and high pressure ethylene polymer composition is equipped with on the Waters150 high temperature chromatogram arrangement that differential refractometer and three mix the porousness posts at one with gel permeation chromatography (GPC) to be measured.These posts are by Polymer Laboratories supply, and to have filled up pore dimension usually be 10 ³, 10 ⁴, 10 ⁵With 10 ⁶The hole of dust.Solvent is 1,2, and the 4-trichlorobenzene is made the sample solution of the 0.3wt% that injects usefulness by it.Velocity of flow is 1.0 ml/min, and the device working temperature is 140 ℃, and injection rate is 100 microlitres.

Infer the molecule measuring definite value of relevant main polymer chain together with its elution volume by the polystyrene standard sample that uses narrow molecular weight distributions.By use suitable polyethylene and polystyrene Mark-Houwink coefficient measure the equivalent molecular weight of polyethylene (as by williams and ward at the polymer science magazine, the polymkeric substance communication, Vol.6, P.621, disclosed in 1968), thus derive following equation:

M _Polyethylene=a* (M _Polystyrene) ^bIn this equation, a=0.4316, b=1.0.Be calculated as follows weight-average molecular weight with common method: Mw=∑ w _i* M _j, w wherein _iAnd M _jBe respectively the parts by weight and the molecular weight of the i composition that comes out from GPC post wash-out.

Known substantially linear ethylene polymers has excellent workability, although it has narrow relatively molecular weight distribution (be that the Mw/Mn ratio is generally less than 3.5, preferably less than 2.5, be more preferably less than 2).Unexpectedly, elaboration (US4 from Dohrer and Niemann, 780,264 and ANTEC progress 1989, " by improving the draw resonance that resinous type suppresses LLDPE ", the 28-30 page or leaf) with different homogeneous phase and heterogeneous branching linear ethylene polymkeric substance, the melt flow of substantially linear ethylene polymers is than (I ₁₀/ I ₂) variation irrelevant with molecular weight distribution mw/mn basically.So the preferred ethylene alpha-olefin interpolymers of preparation extrusion compositions of the present invention is a substantially linear ethylene polymers.

Substantially linear ethylene polymers is homogeneously branched ethene polymers, and is disclosed in US5, in 272,236 and US5,278,272.Homogeneously branched substantially linear ethylene polymers can be buied by Dow chemical company, as Affinity ^TMPolyolefin plastomers and Engage ^TMPolyolefin plastomers.Homogeneously branched substantially linear ethylene polymers can be made by successive solution, slurry or vapour phase polymerization in the presence of controlled geometry catalyst by ethene and one or more optional alpha-olefin comonomer, as european patent application 416, disclosed method among the 815-A.Preferably use the used substantial linear ethenyl copolymer of solution polymerization manufactured the present invention.

Although the molecular structure of homogeneously branched linear ethylene component of polymer significantly is different from the substantially linear ethylene polymers composition, but still can be used among the present invention.

Single-point polymerizing catalyst (for example by Canich at US5, in 026,798 or at US5, disclosed monocyclopentadienyl transition metal catalyst for olefin polymerization in 055,438) can be used to prepare homogeneously branched linear ethylene component of polymer., enumerate in 645,992 at US3 as Elston, also can use Ziegler-type catalyst such as zirconium and vanadium catalyst system polymerization process routinely to prepare homogeneously branched linear ethylene component of polymer.People such as Tsutsui are at US5, provide other example in 218,071, this patent disclosure adopt catalyst system to prepare homogeneously branched linear ethylene polymeric blends based on hafnium.

The characteristic feature of homogeneously branched linear ethylene polymkeric substance is that molecular weight distribution mw/mn is about 2.The commercial example that is applicable to homogeneously branched linear ethylene component of polymer of the present invention comprises the Tafmer that is sold by Mitsui petrochemical industry company ^TMThe Exact that resin and Exxon chemical company sell ^TMResin.

Term " homogeneous ethylene polymkeric substance " is meant that with " heterogeneous branched ethylene polymer " polyvinyl feature is a kind of mixture with interpolymer molecule of different ethene and copolymerization monomer mole ratio.The feature of heterogeneous branched ethylene polymer is that its short chain branch dispersion index (SCBDI) is less than about 30%.All known heterogeneous branched ethylene polymers all are line styles, and do not have to record or evincible long chain branches.Heterogeneous branching linear ethylene polymkeric substance can be buied by Dow chemical company, as Dowlex ^TMLLDPE and Attane ^TMThe ultra-low density polyethylene resin.Heterogeneous branching linear ethylene polymkeric substance can be made by solution, slurry or vapour phase polymerization continuous, that be interrupted or partly be interrupted in the presence of Ziegler-Natta catalyst by ethene and one or more optional alpha-olefin comonomer, as by people such as Anderson at US4, disclosed method in 076,698.Preferably, the characteristic feature of heterogeneous branched ethylene polymer is that molecular weight distribution mw/mn is in the scope of 3.5-4.1.

The used homogeneously branched and heterogeneous branching ethylene alpha-olefin interpolymers composition of the present invention is the interpolymer of ethene and at least a alpha-olefin.Suitable alpha-olefin is represented with following formula:

CH ₂=CHR wherein R is the alkyl with 1-20 carbon atom.This process for copolymerization can be solution, slurry or vapor phase process or its combination.Suitable alpha-olefin as comonomer comprises 1-propylene, 1-butylene, 1-iso-butylene, 1-amylene, 1-hexene, 4-methyl-1-pentene, 1-heptene and 1-octene, and vinylbenzene, tetrafluoroethylene, the vinyl benzo tetramethylene, 1 of other class monomer such as vinylbenzene, halo or alkyl replacement, 4-hexadiene, 1,7-octadiene, and cycloolefin such as cyclopentenes, tetrahydrobenzene and cyclooctene.Preferably, this alpha-olefin is 1-butylene, 1-amylene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene or its mixture, because with these high alpha-olefins during as comonomer, veneer, section bar and the film made by the extrusion compositions of gained have significantly improved anti-misuse, and more preferably alpha-olefin is 1-hexene, 1-heptene, 1-octene or their mixture.Yet more preferably, this alpha-olefin is that 1-octene and polymerization process are the continuous solution polymerization methods.

The density of the ethylene alpha-olefin interpolymers that the present invention who measures according to ASTM D-792 is used is generally at 0.850 gram/cubic centimetre (g/cc)-0.940g/cc, be preferably 0.86g/cc-0.930g/cc, more preferably 0.870g/cc-0.920g/cc most preferably is 0.88g/cc-0.915g/cc.

Polyvinyl molecular weight can represent with melt index easily that melt index is measured according to ASTM D-1238, and condition is 190C/2.16 kilogram (kg), is called " condition E " in the past, is also referred to as I ₂The melt index and the molecular weight of polymkeric substance are inversely proportional.Therefore, molecular weight is high more, and melt index is low more, although the relation of the two and nonlinear.The melt index that is applicable to ethylene alpha-olefin interpolymers of the present invention is generally/10 minutes (g/10min)-50g/10min of 1 gram, be preferably 1g/10min-30g/10min, more preferably 1g/10min-20g/10min is preferably 1.0g/10min-10g/10min especially.

Other measurement that can be used for characterizing ethylene alpha-olefin interpolymers component molecules amount comprises the melt index determination value of higher weight, and for example a general example is ASTM D-1238, and condition 190C/10kg (was called " condition N " in the past, and was also referred to as I ₁₀).Melt index determination value that " melt flow than " in this article refers to higher weight and ratio than the melt index determination value of low weight are for the I that records ₁₀And I ₂Melt index values, melt flow are expressed as I than easily ₁₀/ I ₂The I of ethylene alpha-olefin interpolymers composition ₁₀/ I ₂Than preferably be at least about 5.63, especially about 5.63-is about 18,6-15 particularly.

Ethene polymers extrusion compositions of the present invention can be with any proper method well known in the art preparation, these methods comprise by compounding forcing machine or side arm formula forcing machine carry out drum do mix, weight feeding, solvent, melt-mixing or similar approach and their combination.At least a ethylene alpha-olefin interpolymers that is suitable for preparing ethylene polymer composition of the present invention also can adopt the preparation of multiple reactor polymerization.Suitable multiple reactor ethylene ' alpha '-olefin copolymerization technology is to be disclosed in 07/815, No. 716 and 08/010, No. 958 copending application and the US3 of proposition on January 29th, 1993 that proposed on December 30th, 1991, those in 914,342.Multiple reactor can be worked with series, parallel or its bonded mode, and at least a homogeneous phase single-point type catalyzer or heterogeneous common Ziegler-type catalyst are used at least one of reactor or are used for whole two reactors.

When adopting the multiple reactor technology to prepare ethylene alpha-olefin interpolymers composition of the present invention, the high pressure ethylene polymer composition can be by being positioned at the multiple reactor downstream but is added with elementary process streams direct-connected side arm formula forcing machine or weight feeding equipment, perhaps by different processing unit (plant)s or even add continuously in converter apparatus.

Extrusion compositions of the present invention also can mix with other polymer materials, and can be used to prepare single or multiple lift goods and member, for example as sealing agent, tackiness agent or tack coat.Other polymer materials can mix with the present composition to improve processibility, film strength, heat sealer or binding property.

High pressure ethylene polymer composition and ethylene alpha-olefin interpolymers composition can use to make composition of the present invention with the form of chemistry and/or physically modified body.These modifications can be finished by any known technology such as ionomer polymerization and extruding graft.

Additive such as antioxidant are (for example, Irganox  1010 or the Irganox  1076 of sterically hindered phenol as being supplied by Ciba Geigy), phosphite (for example, same Irgafos  168), cling additives (for example, PIB), Standostab PEPQ by Ciba Geigy supply ^TM(by the Sandoz supply), pigment, tinting material and filler also can be included in the ethene polymers extrusion compositions of the present invention not influence by the high drawdown of contriver's discovery and the amount of the significantly reduced width of cloth that contracts.Made or adopted the goods of the present composition also can contain additive to improve non-stick property and frictional coefficient by the present composition, these additives comprise (but being not limited to) unprocessed or treated silicon-dioxide, talcum, lime carbonate and clay and primary, the second month in a season and substituted fatty acid amide, chill roll releasing agent, siloxane paint etc.Also can add other additive to improve the fog dispersal as transparent cast film, for example Niemann is at US4, and is disclosed in 486,552.Can also add other additive, as independent quaternary ammonium compound or quaternary ammonium compound and ethylene-acrylic acid (EAA) multipolymer or other functional polymer's mixture, with the static resistance that improves veneer of the present invention, section bar and film and make it can for example be used for packing or preparation electronics sensitive articles.

The multilayered structure that comprises the present composition can prepare with any known method, and these methods comprise coextrusion, lamination and combination thereof.In addition, the present composition can use in the coextrusion operation, and in this operation, the higher material of drawdown is used to the lower material of " carrying " substantially one or more drawdowns.

No matter ethene polymers extrusion compositions of the present invention is the single or multiple lift structure, may be used to make extrusion coating, extrusion profile and extrudes cast film.When composition of the present invention is used to the purpose of veneer or is used for multilayered structure, ground or adjacent material layer can be polarity or nonpolar, for example include, but is not limited to paper product, metal, pottery, glass and various polymkeric substance, especially other polyolefine and their combination.For extrusion profile, can make various goods, include, but is not limited to refrigerator sealing gasket, electric wire and cable joint-box, electric wire coatings, medical catheter and water pipe.Make or the cast film of extruding that has a present composition can be used in the application of food Package and industrialization elasticity wrapping film by the present composition.Embodiment

Following examples have illustrated specific embodiments more of the present invention, but should not think that following content means that the present invention is defined in these specific embodiments that provide.Equally, the professional of these technical fields is appreciated that the largest production linear velocity that a class forcing machine or rigging machine can reach needn't be identical with the speed that other class can reach, and in this connection, should use same device significant contrast to be provided and to understand the advantage that discloses by the present invention.

Melt strength is determined at 190 ℃ to carry out, employing be Goettfert Rheotens and Instron capillary rheometer.Capillary rheometer is smoothed and is placed on the Rheoten device, the molten polymer filament is supplied with the Rheotens device with the constant velocity of plunger of 25.4mm/min.Instron is equipped with the standard capillary die head of a diameter 2.1mm, long 42mm (L/D is 20: 1), filament is supplied with the band tooth of the Rheotens device that rotates with 10mm/s speed and is drawn wheel.The distance that outlet of Instron kapillary die head and Rheotens draw between nipping a little on the wheel is 100mm.By the wheel of drawing on the Rheotens device is accelerated to 2.4mm/s ²And beginning to measure the experiment of melt strength, the Rheotens device can be from 0.12mm/s ²Accelerate to 120mm/s ²Because the speed that Rheotens draws wheel is along with the time increases, thereby be the unit record drafting force with a li newton (cN) with the linear transformation displacement trasducer (LVDT) on the Rheotens device.The computer data gathering system of Rheotens device notes drafting force as drawing the wheel function of speed.Actual melt strength values obtains from the steady section of the drafting force of record.Speed during broken filaments is also noted as the melt strength crack velocity with mm/s.Embodiment of the invention 1-3 and Comparative Examples 4-15

Table 1 has been summarized component of polymer and the melt strength measured value that is used for extrusion coating.Sample A and B be according to people such as Lai at US5, substantial linear ethene/1-octene copolymer body that the indication that provides in 278,236 and 5,278,272 is made.Sample C is with Exact by Exxon chemical company ^TMHomogeneously branched linear ethylene/1-hervene copolymer the body of 3022 trade marks supply.Sample D-I is the high pressure ethylene polymer that Dow chemical company makes.Sample E makes with conventional tubular reactor technology.Sample D and F-I make with conventional pressure thermal reactor technology.Be applicable to the example of the polymerization process that high pressure ethylene polymer of the present invention is required as a preparation, table 2 has been summarized the used polymerizing condition of perparation of specimen D.Used reactor is that 15 inches (38cm), a L/D are 10: 1, constant agitation, press thermal reactor continuously.Sample D-I contains the Irganox of 200-300ppm ^TM1010 antioxidants, and sample C contains the active Irganox of (according to the infrared analysis behind the usefulness solvent extraction sample press mold) 230ppm ^TM1076 antioxidants, these two kinds of antioxidants are supplied by Ciba Geigy chemical company.

Table 1 sample polymer melt index density melt melt strength GPC GPC

Kind I ₂(g/cc) intensity crack velocity Mw/Mn is bimodal

(g/10min) (cN) (mm/s) do not have B SLEP 6.0 0.900 1.27 160 2.18 not have C HLEP 10 0.905 0.349 303 2.32 not have D LDPE 0.42 0.918 25.4 103 7.6 to have E LDPE 0.26 0.921 17.7 124＜6 not have F LDPE 10.9 0.919 4.70 273 6.02 not have G LDPE 5.49 0.916 9.7 233 7.42 to have H LDPE 3.17 0.924 8.88 186 5.78 to have I LDPE 7.74 0.917 7.56 247 6.97 not have SLEP=to use controlled geometry catalyst system's combined polymerization by ethene and 1-octene with the continuous solution polymerization method than property A SLEP 4.75 0.910 1.30 269 2.11 and the substantially linear ethylene polymers made. HLEP=is by the Exact of Exxon chemical company supply^TM3022 homogeneous phase linear ethylene polymkeric substance.The LDPE=hp-ldpe.

Table 2

Press thermal reactor conditioned response pressure p si (MPa) 21,300 (146.9) the 1st reaction zone temperatures ℃ 235 the 2nd reaction zone temperatures ℃ 235 the 3rd reaction zone temperatures ℃ gas inlet temperature ℃ 70 bottoms, 254 the 4th reaction zone temperatures ℃ 282 tops (the 1st reaction zone) (the 2nd reaction zone) gas inlet temperature ℃ 28 speed of circulation 1bs/hr (kg/hr) 1,500 (680) high-pressure separator pressure p si (MPa), 1,650 (11.4) light pressure separator pressure p si (MPa) 4 (0.03)

The continuous table of table 2

Press thermal reactor condition the 1st reaction zone initiator type 50/50TPO/TPA mixture the 1st reaction zone initiator concentration at Isopar ^TM20 weight percents the 1st reaction zone initiator among the C adds speed 17.5 (7.9) 1bs/hr (kg/hr) the 2nd reaction zone initiator type 50/50TPO/TPA mixture the 2nd reaction zone initiator concentration at Isopar ^TM20 weight percents the 2nd reaction zone initiator among the C adds speed 14.8 (6.7) 1bs/hr (kg/hr) the 3rd reaction zone initiator type 100%TPA the 3rd reaction zone initiator concentration at Isopar ^TM20 weight percents the 3rd reaction zone initiator among the C adds speed 6.8 (3.1) 1bs/hr (kg/hr) the 4th reaction zone initiator type 50/50TPA/DTBP mixture the 4th reaction zone initiator concentration at Isopar ^TM20 weight percents the 4th reaction zone initiator among the C adds speed 16.8 (7.6) 1bs/hr (kg/hr) high pressure degree exhaust light pressure separator degree volume percent 40 production rate 1bs/hr (kg/hr) 7,406 (3,359) secondary treatment does not have TP0=and crosses the sad tert-butyl ester; The TPA=t-butyl peroxy-acetate; The DTBP=ditertiary butyl peroxide.Isoplar ^TMC is that the boiling spread by Exxon chemical company supply is 95-108 ℃ a paraffin solvents.

Fig. 1 shows that the molecular weight distribution (MWD) of the sample D that is measured by gel permeation chromatography (GPC) is (being that component of polymer is characterised in that to have tangible polymer peak) of bimodal attitude.Fig. 2 shows that sample G and I have bimodal molecular weight distribution, and sample F and H do not show tangible bimodality.Table 1 shows that sample D and G have higher melt strength, wide molecular weight distribution and bimodality, therefore thinks that these materials are the suitable mixing elements of giving improved extrusion performance.

Table 3 has been summarized the mixing element that the independent component of polymer listed by table 1 is made.This mixing element can be made by melting mixing in Haake torque mixing machine, or directly composition is added by weighing according to the weight percent that table 3 is listed in first forcing machine of extrusion coating production line and make.

Table 3 sample

EXAMPLE Example embodiment * Comparative Examples * Comparative Examples embodiment weight percent 123456

B 95 90 80 100 90 90

D 5 10 20

E 10

G 10* represents not to be embodiments of the invention; Only provide for correlated purpose.

The table 3 first continuous table sample

* Comparative Examples embodiment * Comparative Examples * Comparative Examples * Comparative Examples * Comparative Examples weight percent 789 10 11 12

B 90 80

C 100

D 100

E 100

F 100

G 20

I 10* represents not to be embodiments of the invention; Only provide for correlated purpose.

The table 3 second continuous table sample

Embodiment * Comparative Examples * Comparative Examples * Comparative Examples weight percent 13 14 15 16

A 100

C 90

D 10

H 100

I 100* represents not to be embodiments of the invention; Only provide for correlated purpose.

Embodiment 1-3,6,8 and 13 and Comparative Examples 4,5,7,11-12 and 14-16 estimate for the high drawdown on the extrusion coating production line.Laminating apparatus is made up of three forcing machine Black Clawson coextrusion veneering production lines, this production line comprises that diameter 3-1/2 inch (8.9cm), L/D are 30: 1 first forcing machine, and diameter 2-1/2 inch (6.4cm), L/D are 24: 1 second forcing machine and second forcing machine of 2 inches diameter (5.1cm).76cm sealing coextrusion feed die head be fixed on first forcing machine and amplitude modulation to 69cm, this die head has the die gap of 20 mils (0.51mm) and the air/drawing gap of 6 inches (15.2cm).Control this production line with microprocessor system, this production line comprises the weight sensor feed hopper that check speed and control veneer weight are used.This extruding production line also is equipped with delustring, the dibasic alcohol refrigerative chill roll that is set in 57 (14 ℃).Except other note, the target extrusion temperature of all extrusion coating embodiment and screw speed are 625 (329 ℃) and 90 rev/mins respectively.But embodiment 13 and Comparative Examples 14 and 18 are carried out veneer and are extruded under the melt extrusion temperature that is about 612 (322 ℃).On the kraft paper that melt extrudes thing or tablet continuous drafting to 50 pound (23kg) with all embodiment.

These evaluations relate on the simultaneity factor ground that keeps constant screw speed (90 rev/mins) and improve the production line/speed of drawing up to finding that draw resonance or tablet break.Just found when draw resonance takes place by (being that tablet begins vibration) or the line speed of tablet when breaking is counted as finally or the maximum drafting ratio.The width of cloth performance and be lower than the contract percentage of amplitude of embodiment expectation and be summarised in the table 4 of contracting of ratio of drawing, the width of cloth of measuring when veneer thickness is 1 mil (0.025mm) under the line speed of 440 feet per minutes (134 meters/minute) that contracts, forcing machine amperage, die pressure, expection.The composition of sample D and the E width of cloth that contracts is obtained by extrapotation by Fig. 3, because these materials can not be formed and carry out extrusion coating as the single component polymkeric substance.The width of cloth performance that contracts of expectation is obtained by the above linear hybrid standard equation of enumerating.

Table 4

The draw resonance of extrusion coating product and the width of cloth embodiment die pressure forcing machine drawing speed that contracts ⁺The 134mpm/1Mil expectation is lower than expected value

(psi) percentage of the width of cloth that contracts of the width of cloth that contracts during amperage (ft/min)

(MPa) (m/min) (inch) (cm) (inch) 11,560 147＞1,800 6.25 7.14 12.5

(10.8) (＞549) (15.9) (18.1) 2 1,610 149 ＞1,700 4.375 6.78 35.5

(11.1) (＞518) (11.1) (17.2) 3 1,690 148 1,260 3.25 6.06 46.3

(11.7) (384) (8.3) (15.4) 4* 1,740 145 590 7.5 NA NA

(12.0) (180) (19.1) 5* 1,610 149 1,300 6.125 6.83 10.3

(11.1) (396) (15.6) (17.3) 6 1,500 145 ＞1,600 5.75 6.89 16.5

(10.3) (＞488) (14.6) (17.5) 7* 1,700 137 ＞1,600 6.125 6.93 11.6

(11.7) (＞488) (15.6) (17.6) 8 1,490 138 ＞1,600 4.375 6.28 30.3

(10.3) (＞488) (11.1) (16.0) 9* ND ND ND ND 0.25** NA

(0.6) 10* ND ND ND ND 0.45** NA

(1.1) 11* ND ND 1,460 1.8 NA NA

(445) (4.6) 12* 1,090 164 670 9.25 NA NA

(7.5) (204) (23.5) 13 1,160 167 ＞1,600 4.125 8.35 50.6

(8.0) (＞488) (10.5) (21.2) 14* ND ND 980 2.0 NA NA

(299) (5.1) 15* 1,150 97 1,150 1.75 NA NA

(7.9) (350) (4.4) 16* 1,000 135 670 6.75 NA NA

(6.9) (204) (17.1) ^*Drawing speed=see is when the size irregularity has just produced or drawing the break speed of drawing of moment of tablet. ^*Expression is not embodiments of the invention; Only provide for correlated purpose. ^*The amplitude of knowing by inference by the Fig. 3 that measures melt strength that contracts.ND=does not detect.NA=is inapplicable.

By the data of table 4 as can be seen, the feature that contains the extrusion coating composition of high pressure ethylene polymer is to have high fondant-strength and wide bimodal molecular weight distribution, and the not improved ethylene alpha-olefin interpolymers composition of the amplitude ratio that contracts is significantly reduced.Yet beyond thought is the expected value that the width of cloth performance that contracts of this polymkeric substance also significantly is lower than corresponding composition material.

In other is estimated, measured heat sealer, thermal viscosity, bounding force and the tear resistance of embodiment 1 and compared with several sealing agent extrusion coating resins that are commercially available.The mensuration that two kinds of different multilayered structures is used for heat sealer and thermal viscosity.These structures are as follows:

Structure A:

The Hostaphan of specification 48 ^TM2DEF/0.5mil Primacor ^TM4608/ embodiment

Structure B:

Wettable aluminium foil/the embodiment of A type of 30 pounds of (13.6kg) poaching engine-grade kraft paper/0.75mil (0.02mm) Primacor3460/ specifications 0.0035

Hostaphan 2DEF is a kind of polyester film by Hoechst Diafoil supply, and Primacor resin 4608 and 3460 is ethylene acrylic (EAA) interpolymers by the supply of Dow chemical company.

Measure for bounding force, when embodiment carries out veneer with 400 feet per minutes (122 meters/minute), with the oriented polypropylene of the wettable aluminium foil of A type of specification 0.035 and specification 50 respectively as lubricated pad pad at rigging machine die head place.Bounding force is considered to layering or isolating anti-drag, and carries out by the qualitative evaluation of excellence to difference, and wherein " excellence " level is meant that embodiment has high anti-drag to separation when manually stretching.

Tear resistance is measured according to ASTM D1922 and is noted with gram.For embodiment, measure the tear strength of machine direction (MD) and cross-sectional direction (CD) at 440 feet per minutes (122 meters/minute) veneer on 50 pounds of (23kg) kraft paper.The mean value of the Elmendorf value of tearing MD and CD represented in term used herein " tear strength ", notes with gram equally.

The definition of heat seal kick off temperature is 2 pounds of/foot required minimum temperatures of (0.4kg/cm) heat sealing strength.The heat seal experiment is carried out with 0.5 second pressing time, the heat-fastening knife pressure of 40psi (0.28MPa) on top ripple (Topwave) thermal viscosity experimental machine.In 60-160 ℃ scope, carry out heat seal by sealant layer and himself is overlapping and heat seal with 5 ℃ increasing amount.The heat seal body that forms is like this being processed back draft 24 hours through the Instfon tensiometer with the crosshead speed of 10 inch per minutes (51cm/min).Heat sealing strength is considered to be in before the heat-fastening knife through welding sealant layer, the maximum intensity of the embodiment that represents with pound/inch in 60-160 ℃ temperature range.

The definition of hot sticky kick off temperature is the required minimum heat-seal temperature of heat sealing strength that improves 4 newton/inches (1.6N/cm).Hot sticky experiment is carried out with 0.5 second heat sealed time, the heat-fastening knife pressure of 40psi (0.28MPa) on top ripple (Topwave) thermal viscosity experimental machine.In 60-160 ℃ scope with 5 ℃ increasing amount by sealant layer and himself is overlapping and hot stickyly carry out hot sticky involution.The peeling rate that imposes on the hot sticky sealing body of such formation is 150mm/sec.After 0.2 second the residence time at once with experimental machine this hot sticky sealing body that stretches.Hot sticky intensity is considered to be in maximum newton/inch value of 60-160 ℃ the interior embodiment of temperature range.Hot sticky scope is considered to hot sticky intensity＞8 newton's of hot sticky intensity＞4 newton of structure A and structure B temperature range.What table 5 showed is the comparison use properties of embodiment 1.

Table 5

Embodiment 1 15 17 18 19 extrusion temperatures (℃) 610 618 614 550 550

(321) 1 pound of/inch (kg/cm) structure A 14.0 10.0 10.0 9.5 10.0 of (326) (323) (288) (288) heat seal kick off temperature ℃ structure A 82 95 105 83 85 structure B, 97 105 117 ND ND heat sealing strengths

(2.5) (1.8) (1.8) (1.7) (1.8) structure B 7.8 7.0 7.0 ND 7.5

(1.4) the hot sticky kick off temperature in (1.2) (1.2) (1.3) ℃ structure A 95 CND CND 87 90 structure B 98 112 117 94 95 hot sticky intensity newton/inch (N/cm) structure A 8.5 2.5 3 10 10

(3.3) (1.0) (1.2) (3.9) (3.9) structure B 16 98 ND 14.5

(6.3), (3.5), (3.1), (5.1) hot sticky scope ℃ structure B＞8 newton, 70 15 5 75 75 structure A＞4 newton, 25 00 65 65 binding speed aluminium foil G F G E E oriented polypropylene E P P P PElmendorf tear strength g, 327 121 240 ND NDE=excellences; G=is good; F=is medium; P=is poor; ND=does not survey; CND=all surpasses 4 newton owing to hot sticky intensity under any temperature and can't measure. ^*Expression is not embodiments of the invention; Only provide for correlated purpose.Comparative Examples 17 and 18 is Dowlex3010 and Primacor3440, is all supplied by Dow chemical company.Comparative Examples 19 is Surlyn ionomers 1652, is supplied by Dupont chemical company.

Table 5 shows that embodiments of the invention 1 have excellent stopping property, are suitable in the single or multiple lift structure as sealing ply it.

Claims (20)

1, a kind of ethene polymers extrusion compositions, said composition contains at least a ethylene/alpha-olefin interpolymer composition that accounts for composition total weight 75-95%, this composition is selected from substantially linear ethylene polymers, homogeneously branched linear ethylene component of polymer and heterogeneous branching linear ethylene polymkeric substance, the feature of therein ethylene/alpha-olefin interpolymer is that density is in the scope of 0.85-0.940g/cc, said composition also contains at least a high pressure ethylene polymer that accounts for composition total weight 5-25%, and the feature of this polymkeric substance is melt index I ₂Less than 6.0g/10 minute, density is at least 0.916g/cc, be installed on 190 ℃ of melt strengths that record with GottfertRheotens and be at least 9cN, the Mw/Mn ratio that records with gel permeation chromatography is at least 7.0, and measured bimodal molecular weight distribution with gel permeation chromatography, the melt index I of the polymer-extruded composition of therein ethylene ₂Be at least 1.0g/10 minute.

2, the composition of claim 1, wherein at least a ethylene alpha-olefin interpolymers are the following substantial linear ethenyl copolymers of feature:

(a) melt flow compares I ₁₀/ I ₂〉=5.63,

(b) use the gel permeation chromatography molecular weight distribution mw/mn, and define in order to following equation:

(Mw/Mn)≤(I ₁₀/I ₂)-4.63，

(c) extrude rheology according to gas, substantially linear ethylene polymers surface melt fracture begins

The time the utmost point of limit shearing rate when beginning than the melt fracture of linear ethylene polymer surfaces at least

The limit shearing rate is high by 50%, wherein substantially linear ethylene polymers and linear ethylene polymkeric substance bag

Contain one or more same comonomers, the I of linear ethylene polymkeric substance ₂, Mw/Mn and close

Degree account for substantially linear ethylene polymers 10% in, and substantial linear vinyl polymerization wherein

The corresponding limit shearing rate of thing and linear ethylene polymkeric substance is to adopt under the same melt temperature

The gas squeezing rheometer is measured, and

(d) according to single dsc DSC, melting peak is between-30 and 150 ℃.

3, the composition of claim 2, wherein substantially linear ethylene polymers has 0.01-3 long chain branches/1000 carbon atom.

4, the composition of claim 3, wherein substantially linear ethylene polymers has about 0.1 long chain branches/1000 carbon atom at least.

5, the composition of claim 4, wherein substantially linear ethylene polymers has about 0.3 long chain branches/1000 carbon atom at least.

6, the composition of claim 1, wherein alpha-olefin be at least-kind of C ₃-C ₂₀Alpha-olefin.

7, the composition of claim 6, wherein alpha-olefin is selected from 1-propylene, 1-butylene, 1-iso-butylene, 1-hexene, 4-methyl-1-pentene, 1-amylene, 1-heptene and 1-octene.

8, the composition of claim 2, the therein ethylene alpha-olefin interpolymer accounts for the 85-95% of composition total weight, and high pressure ethylene polymer accounts for the 5-15% of composition total weight, and the feature of high pressure ethylene polymer is melt index I ₂Less than 1.0g/10 minute, density is at least 0.916g/cc, be installed on 190 ℃ of melt strengths that record with Gottfert Rheotens and be at least 15cN, the Mw/Mn ratio that records with gel permeation chromatography is at least 7.3, and has measured bimodal molecular weight distribution with gel permeation chromatography.

9, the composition of claim 8, therein ethylene alpha-olefin interpolymer are the multipolymers of ethene and 1-octene, and high pressure ethylene polymer is an Alathon.

10, the composition of claim 1, wherein at least a ethylene alpha-olefin interpolymers are homogeneously branched linear ethylene polymkeric substance.

11, the composition of claim 1, the homogeneously branched linear ethylene polymkeric substance of wherein at least a ethylene alpha-olefin interpolymers right and wrong.

12, the composition of claim 1, wherein at least a high pressure ethylene polymer is an Alathon.

13, the composition of claim 1, wherein at least a high pressure ethylene polymer are the interpolymers of ethene and at least a unsaturated comonomer.

14, a kind of method for preparing the ethene polymers extrusion compositions comprises

(a) at least a high pressure ethylene polymer that will account for extrusion compositions weight 5-25% with

At least a ethylene alpha-olefin interpolymers that accounts for extrusion compositions weight 75-95% mixes,

Wherein, mix said at least a high pressure ethylene polymer, this feeding equipment with feeding equipment

Be an one of preparation said at least a ethylene alpha-olefin interpolymers used polymerization process

Divide, thereby make the ethene polymers extrusion compositions, this ethene polymers extrusion compositions molten

Body index I ₂Be at least 1.0g/10 minute, its width of cloth that contracts is 1 close in individual layer extrusion coating weight

The expectation of the comparison composition amplitude that contracts is low at least by 12% during ear (0.025mm), and

(b) collect or carry this extrusion compositions with the form that is applicable to subsequent applications.

15, a kind ofly make ground, the extrusion profile of extrusion coating or extrude the method for cast film, comprising with the ethene polymers extrusion compositions:

(i) ethylene polymer composition is infeeded at least one the forcing machine of extruding production line, its

In this ethylene polymer composition contain at least a second that accounts for composition total weight 75-95%

Alkene/alpha-olefin interpolymer, this interpolymer is selected from substantially linear ethylene polymers composition, homogeneous phase

Branching linear ethylene component of polymer and heterogeneous branching linear ethylene component of polymer, wherein second

The feature of alkene/alpha-olefin interpolymer be density in the scope of 0.85-0.940g/cc, molten

Body index I ₂In 0.1-50g/10 minute scope, said composition also contains and accounts for composition

At least a high pressure ethylene polymer of gross weight 5-25%, the feature of this polymkeric substance is molten

Body index I ₂Less than 1.0g/10 minute, density was at least 0.916g/cc, used Gottfert

Rheotens is installed on 190 ℃ of melt strengths that record and is at least 9cN, uses the gel infiltration look

The Mw/Mn ratio that spectrometry records is at least 7.0; And measured bimodal with gel permeation chromatography

Molecular weight distribution, the melt index I of the polymer-extruded composition of therein ethylene ₂Be at least

1.0g/10 minute,

(ii) fusion and to mix this ethylene polymer composition poly-to form at least a uniform fusion

Compound stream,

Extruding production line is worked being higher than under the line speed of 152m/min,

Molten polymer flow is extruded forming elementary extrudate by die head, and

(a) drawing-off and cool off this extrudate and have at least one deck ethene polymers and extrude to make

The extrusion profile of composition, perhaps

(b) this extrudate of drawing-off is to ground, thereby extrudes with one deck ethene polymers at least

Composition is to the ground veneer, perhaps

(c) drawing-off and cool off on this extrudate to one caterpillar and have one deck at least to make

The film of ethene polymers extrusion compositions, and

(vi) carry or collect section bar, prepare against follow-up use through the ground or the film of veneer.

16, the method for claim 15, wherein step (iii) (a), (iii) (b) or (iii) (c) described one deck at least be sealant layer, binder layer or anti-misuse layer.

17, the method for claim 15, wherein step (iii) (b) described one deck at least be sealant layer.

18, a kind of goods of one deck ethene polymers extrusion compositions at least that comprised, wherein extrusion compositions contains at least a ethylene/alpha-olefin interpolymer that accounts for composition total weight 75-95%, this interpolymer is selected from the substantially linear ethylene polymers composition, homogeneously branched linear ethylene component of polymer and heterogeneous branching linear ethylene component of polymer, the feature of therein ethylene/alpha-olefin interpolymer is that density is in the scope of 0.85-0.940g/cc, said composition also contains at least a high pressure ethylene polymer that accounts for composition total weight 5-25%, and the feature of this polymkeric substance is melt index I ₂Less than 6.0g/10 minute, density is at least 0.916g/cc, be installed on 190 ℃ of melt strengths that record with Gottfert Rheotens and be at least 9cN, the Mw/Mn ratio that records with gel permeation chromatography is at least 7.0, and measured bimodal molecular weight distribution with gel permeation chromatography, the melt index I of the polymer-extruded composition of therein ethylene ₂Be at least 1.0g/10 minute.

19, the goods of claim 18, the form of therein ethylene polymer composition are extrusion profile, the extrusion coating that enters ground or extrude cast film.

20, the goods of claim 18, the wherein said ethylene polymer composition of one deck at least are sealant layer, binder layer or anti-misuse layer.

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