CN1753776A

CN1753776A - Methods, compositions and blends for forming articles having improved environmental stress crack resistance

Info

Publication number: CN1753776A
Application number: CN 200480004875
Authority: CN
Inventors: 艾恩·欧德·麦克尔·雅可布斯
Original assignee: Individual
Current assignee: Viva Healthcare Packaging Ltd
Priority date: 2003-01-16
Filing date: 2004-01-16
Publication date: 2006-03-29
Also published as: AU2003900292A0

Abstract

Several processes for the manufacture of flexible thin-walled tubes are described, including: injection moulding an article and annealing the article, injection moulding a blend of a polymer and a high melt flow polymer, injection moulding a blend of a polymer and nanoparticles or nanocomposites. Using nanoparticles to improve ESCR and/or tear resistance of a polymer or blend is also disclosed.

Description

Be used to form method, composition and blend with the goods that improve environmental stress crack resistance

Invention field

According to an aspect, the present invention relates to make flexible thin-gage goods, such as the pipe etc. method, the improvement of environmental stress crack resistance (ESCR) and other performance wherein is provided by the goods of annealing after being shaped to its net shape.According to another aspect of the present invention, also provide the composition and the blend that can be used for making flexible thin-gage goods or other goods, described composition and blend have improved ESCR and other performance.

The argumentation of prior art

The thin-wall tubular container, general main by the extruding and the measured length cutting of tube-shaped main body such as being used for those of cosmetics industry, the injection moulding of head and shoulder and the combination that main body is welded in head and shoulder prepared.Low melt flow index (MFI) polyethylene (MFI is generally less than 2) is the preferred polymers that is used to make pipe, because it has generally given the consumer required good " feel " and flex capability, and is suitable for extruding processing.In addition, low MF low density polyethylene (LDPE) (LDPE) provides sufficient product resistance and barrier property, makes it be suitable for being loaded into usually the interior most of products of pipe.For application-specific, under the inadequate situation, use medium density polyethylene (MDPE) usually at poly barrier property, high density polyethylene (HDPE) (HDPE), polypropylene (PP) and multilayer polymer film.Because body is extruded, in their manufacturing, can use low MFI polymer with intrinsic good ESCR.In addition, owing to be relative low shear rate method, this expressing technique has been introduced minimum polymer stress and molecularly oriented in body in manufacture process.Use has the polymer of intrinsic good ESCR, extrude with extrude/the blowing pipe in the intrinsic relatively low pressure power of the relative shortage of molecularly oriented and expressing technique and process velocity caused having the extruding pipe of low internal stress and intrinsic good ESCR.Therefore, extruding pipe is eliminated for overwhelming majority's application and tubing application by the stress of annealing and is had minimum value.

Though before being incorporated herein the progress described in the PCT/AU98/00255 for reference (' 255 patent), the injection moulding of flexible thin-gage goods such as pipe proposed, but can not injection moulding have long and thin relatively section, be not easy again to destroy simultaneously and lose this goods of industry or practical use.These subject matters are relevant with the polymer that is used for injection molding tube, because injection moulding is cylindrical or the method for other moulding pipe requires polymer to have high MFI simultaneously, so that can make polymer along by the length of tube shape defined, narrow and crooked passage to dirty, need not to use too high injection pressure.Enough tolerances are handled and the good mechanical properties of the stress crack effect of many products that opposing is packed therein yet have.For injection molding tube, require the polymer/polymer blend to have to form to have 100 and the mobile performance of the molded item of bigger usually radius and length/thickness ratio.Usually, this polymer or blend polymer require to have greater than 10, are preferably greater than 20, more preferably greater than 30 with usually greater than 50 MFI.As everyone knows, when MFI increases, the physical property of polymer, especially ESCR significantly reduces, and significantly and inherently is lower than those of extruding pipe so have the intrinsic ESCR performance of the polymer/polymer blend of the required MFI of injection molding tube.In order to relax this problem, forcing polymer to flow in having the mould of this type of size is incorporated into serious stress in the polymer, when this polymer was cooled fast to before these stress can be eliminated when being lower than its crystallization temperature, these stress " are freezed " in the goods of such production.With under not too harsh condition of moulding, compare by the molded other products of same polymer, these stress cause this pipe to have wonderful difference and the performance of deterioration.

When product filled and crimping and when sealing-the most common then, other stress is incorporated in the injection molding tube by heat-sealing or ultra-sonic welded.This technology comprises " opening " end itself of pipe turned up and reaches 180 ° angle, thereby forms fold at sealing edge.This fold is on the direction that polymer flows in moulding process, this direction has proved the direction of the greatest drawback of layered product, should ' folding and sealing ' zone (wherein this pipe is required distortion, so that seal) be the zone that especially is easy to the injection molding tube of stress and flexural cracking.Equally, body is crimped/sealing technology institute permanent deformation, the result in addition and the permanent stress that is subjected to, this can be easily crimping and unencapsulated shape are not relatively found out from the distorted shape of crimping and sealed tube and its.These stress, especially those that bring out by the permanent deformation of goods after crimping and sealing, also have pipe between the operating period extruding and BENDING PROCESS in apply those, have remarkable reduction and form the ESCR of polymer of injection-molded item and the effect of other physical property, thereby must use the polymer that when being molded as required goods, has shown uncommon good ESCR and other physical property.Compare with other polymer/blend, this base polymer/blend can have many shortcomings, such as more expensive, need long cool time (with therefore long circulation timei), have higher stiffness (that is, more inferior ' feel '), need stronger or more expensive compounding etc.

Following example is for example understood the especially high stress level that is molded as pipe when using the injection moulding process of comparing with extrusion method to make.

Pipe with 120 * 35mm size uses the injection moulding of DuPont 2020T polymer, this polymer is a widely used 1.1MFI polymer in industrial extruding pipe is made, and DuPont is described as " being particularly suitable for wherein requiring the injection moulding obturator and the extruding pipe material of flexible and maximum environmental stress resistance cracking ".The molding of injection molding tube has high difficulty, just to making 2020T fill mould, requires very high injection pressure and temperature.In each molding, recorded significant core displacement/bending, this is undoubtedly owing to required high injection pressure.In addition, notice that pipe does not have flex stiffiness basically on the direction that material flows, wherein manual extruded tube has just brought out significant cracking less than 5 times.The environmental stress crack of identical pipe uses as described ESCR experimental test in this article, though claim " the highest environmental stress crack resistance ", finds for being inadequate fully by the injection molding light-wall pipe.This and its differ widely as the status of " the polymer selection " of the pipe by the extrusion method preparation.When injection moulding the rapid reduction of the performance of 2020T almost all owing to those especially high moulds of comparing in the pipe of extruding by same material in and orientation stress.

As another example of high mould internal stress level intrinsic in injection molding tube, with Dowlex2517, promptly 25MFI LLDPE is molded as 150 * 50mm pipe.In the brochure about Dowlex LLDPE, Dow proposes LLDPE and has obviously better ESCR performance than equal high pressure LDPE.For difference is described, the Dow brochure claims that in a comparative test, the high ESCR of Dowlex LLDPE in oil of flowing is than those good about 80 times (5700 hours than 70 hours) of obtaining by the high pressure LDPE with similar density and MFI.It claims in addition, and in the time of in impregnated in 50 ℃ 10%Teric solution, LLDPE has the ESCR well more about 10 times than LDPE (225 hours than 26 hours).Yet, opposite with these discoveries, we find, when these polymer with the form molding of light-wall pipe with when using ESCR experimental test ESCR as described herein subsequently, ' Dowlex ' LLDPE 2517 of Dow and the LD8153 of Kemcor (the high pressure LDPE with similar MFI and density) all show inferior in 50 ℃ 10%Teric N9, the two destroyed in 20 minutes, and ESCR is than little about 600 times in the value shown in the brochure.When the extreme of the ESCR performance that is injection molded into when pipe two kinds of polymer reduces almost all is the result of Gao Monei and orientation stress level in injection molding tube.

As the indication that degree is increased in strain in the folding and sealing area of pipe, use following formula to calculate this regional strain that causes by sealing with respect to unsealing (being opening) pipe:

The radius of the strain=fold of polymer/rectangular thickness square

Suppose the nominal radius of the rectangular thickness (typical wall thickness of pipe) of the rectangular and 0.5mm of 1 meter flat polymer, the strain in the unsealing polymer is 0.00025.When sealing, be about 0.65mm at the rectangular radius of sealing the margin, obtained 0.385 calculating strain.In other words, sealing this pipe has caused the strain in the strain ratio unsealing pipe in the polymer to be increased above 1600 times.For extruding pipe with machining stress in intrinsic higher ESCR polymer and the significantly lower mould, strain increase the several problems that proposed with regard to ESCR and/or tear strength properties.That is to say, use these polymer to combine prepared annealing goods with expressing technique and unlikely cause the ESCR of goods and the remarkable and/or industrial valuable improvement of tearing strength.Yet, the applicant has been found that, when injection moulding thin-walled flexible article, with forming and therefore have the tropism of higher deflection and ESCR destruction with orientation stress and by intrinsic low ESCR polymer in their the obviously higher mould, annealing can make the ESCR of goods and/or tearing strength produce very big difference.This improvement can mean the difference that function and idle usefulness are arranged with regard to the goods of its commercial Application.

We have now found that, just before goods are filled and/or are deformed into its final required form, during or the flexible injection thin-gage goods of annealing afterwards improved ESCR and many other physical properties of goods significantly, such as the tear resistance on the polymer flow direction when using Gullwing tear test method (ASTM D-1004) to measure.These improve in the goods zone with the additional stress that is applied thereto is the most significant, and these stress ratios are as in sealing or during applying load (for example by piling up) and result's generation of any distortion of goods afterwards.The additional benefits of annealing of the present invention is that the ESCR etc. that increases them makes and can adopt the polymer/blend that is used to make flexible thin-gage goods, and described polymer/blend will cause obtaining under unannealed condition scraping through or unaccommodated flexible thin-gage goods for the packing specific products.In annealing process, if heating or abundant in addition the processing to softening this polymer, and/or under goods are fully supported situation with the undesired distortion that prevents goods, melting this polymer, goods can come redeformation by apply suitable power with various device.

Though do not wish to be subjected to the restriction of the theory that proposed, but it is believed that, polymer is cooled fast to the solidification temperature that is lower than polymer from molten condition and has caused various stress and strains to be absorbed solid members in the injection step process, and has introduced other stress as the result of the distortion of the goods that caused by sealing technology.These stress make goods be easier to be subjected to the attack of stress cracking agent and physics deflection, therefore easier destruction.Fill and sealing after soon during in, when distortion owing to the mechanograph that causes by sealing, that stress in mechanograph is in is the highest (' the relaxing ' that reaches them with dissipate need for a long time degree) and the stress cracking agent directly contact with goods and after filling and sealing during in can ' attack ' and be subjected to heavily stressedly when regional, situation is especially like this.It is believed that by annealing polymer stress can ' be attacked ' polymer that is subjected to stress in the stress cracking agent, thereby causing to destroy before eliminates.If stress can not be eliminated immediately, it is believed that for many polymer formulation material the stress cracking agent can relax in ' normally ' of polymer can reduce the destruction that causes goods before the neurological susceptibility of goods destruction.

The degree of mould internal stress, and the reduction degree of ESCR and other Performance Characteristics can be accompanyed or follow mechanograph to mechanograph and change in time and in various degree.Therefore, the very difficult compensation reliably and accurately do not having the variation that the ESCR between mechanograph reduces under the situation of annealing in process.Another complexity is because stress progressively reduction is in time depended on before filling and sealing and the fact of the condition (mainly being time and temperature) of goods storage afterwards with the degree that stress reduces, so can not be reliably and prediction as one man since natural stress reduce, need by all pipes of particular polymers formulation preparation through how long just being fit to use.For this reason,, must use usually because the possibility of ESCR and the insufficient industrial accident that causes of other Performance Characteristics in order at utmost to reduce at the polymer that is subjected to have under the stress state certified good especially ESCR performance.This requirement has many potential for adverse effects, especially in potential higher polymer/unit cost, and the circulation timei of increase and unfavorable ' feel ' and flexible aspect.If the mould internal stress can be eliminated before the commodity performance of their remarkable adverse effect thin-gage goods, was favourable so.

Have been found that, as long as the product with stress cracking potentiality in being filled into goods has before enough times of contact with the polymer under the stress state that is subjected to that causes or cause cracking, mould internal stress in the injection-molded item is eliminated more or less, can prepare the flexible thin-wall injection molded articles with improved ESCR and other Performance Characteristics so.In addition, have been found that with the situation that does not adopt annealing and compare that the annealing of goods makes can use the more polymer and the blend polymer of wide region in the manufacturing of industrial useful flexible thin-gage goods.

If between molded and filling/seal operation, have the tangible time interval (for example as fruit product at the three unities molding, packing, be transported to then that another place is filled and sealing) and need be before goods load and transport-the most common, after molding immediately-carry out the annealing of mechanograph, just before the distortion of goods, during and/or many benefits of afterwards annealing still can obtain by the molding after annealing.This benefit may not resemble that obtainable those are remarkable by annealing institute after product deformation, but can be depending on polymer formulation material and condition of moulding, remains worth.

Behind the molding but the annealing benefit before filling stands in the zone of mechanograph of minimum additional stress when crimping and sealing is the most significant.These zones are the most normally apart from relative far away those in ' crimping and sealing ' zone-for example, with relative those approaching zones with shoulder of head of pipe.We have found that, annealing, make it cooling (if annealing process is elevated to it more than preannealing temperature with the temperature of mechanograph) and suffer then tangible deformation ratio as in crimping and seal operation process sealing area and on every side the zone of the mechanograph of the distortion of generation can show the ESCR performance of rapid decline, compare with the zone of identical obvious distortion in equal unannealed mechanograph.This can test by ESCR as described herein and illustrate, wherein carries out described ESCR test to three groups of blend polymers of the same area of taking from mechanograph are rectangular.One group leader's bar is annealed afterwards in cut-out (stapling), unannealed and the 3rd group leader's bar annealing before cutting off of another group.

ESCR result is as follows:

Only 4% the rectangular of annealing after cutting off destroyed in 190 hours

25% unannealed rectangularly in 190 hours, destroy

Basically all the rectangular of annealing before cutting off of (94%) only destroyed in 3.5 hours.

Explanation of the present invention

Illustrated as above result, compare with unannealed pipe, significantly improve their ESCR being subjected to will to manage under the stress state annealing, and be not subjected to will manage under the stress state ESCR that annealing and stress application have subsequently caused rapid reduction.

Therefore, according to a first aspect of the invention, provide the method for making flexible thin-gage goods, comprised by plastic material injection-molded item main body; Equipped this main body forms goods; And this plastic material of annealing.

Annealing is generally defined as removing or reducing the method for the strain and stress in the thermoplastic.This usually realizes by heating the material that will anneal and making it then progressively to cool off.The technology of two kinds of successes usually using when the annealing thermoplastic comprises a kind of technology of removing thermoplastic from thermal source and the another kind of technology that makes from the heat minimizing of thermal source.Two kinds of technology usually are called as integral body (bulk) annealing technology, because they comprise the inside and outside of heating thermoplastic material.The former generally finishes in annealing furnace, and the latter generally finishes in baking oven.The supplementary technology that is used for the integrally annealed of thermoplastic comprises those that use infra-red radiation.Thermal annealing usually is the method for optimizing of annealing, because simple equipment and technology extensively and at an easy rate are available for implementing this step.At other not in the embodiment preferred, annealing can be exerted pressure by the short time, compacting or tension force carry out.

People are for not using the integrally annealed technology to increase day by day such as the interest that above-mentioned technology reduces the stress and strain of thermoplastic.Therefore, can use the method that reduces the strain of thermoplastic by flash annealing, this method has also kept the physics and the chemical property of thermoplastic unexpectedly simultaneously.Flash annealing is defined as the skin of heating thermoplastic material, and it is half the skin of thermoplastic that is no more than the thickness in the zone that will anneal usually, for example is that 0.25mm is thick under the situation of 0.5mm wall thickness goods.And, for the thermal source that in this flash annealing, adopts without limits, the inside that does not cause the skin of thermoplastic and thermoplastic except it is heated to the identical temperature, the wherein inner any part that is defined as not comprising previously defined outer field thermoplastic.Therefore, heat can penetrate inside; Yet after theca externa was by flash annealing, internal temperature was lower than skin.Therefore, prevent integrally annealed.When the surface that will anneal is contact with the stress cracking agent surperficial, just improve the ESCR of thin-walled flexible article, flash annealing is especially effective.Have precedence over the outer wall of pipe or other container, the inwall of pipe or other container is the especially effectively example on surface of flash annealing.This be because, the annealing inwall of pipe or other container has the surface of lowering stress for the stress cracking agent provides, therefore with respect to the improvement ESCR of unannealed inwall, can cause and finally cause managing or the chance of the stress cracking that container destroys thereby at utmost reduced the stress cracking agent.If the pipe or the outer surface of container are annealing surfaces, the stress cracking agent can cause the cracking of the unannealed inner surface that its institute directly contacts, thereby has weakened pipe or container potentially.The annealing of the pipe or the inner surface of other container can be by being blown into hot-air on described surface, allowing radiant heat source finish near other mode that is fit to that inner surface or those skilled in the art are familiar with.

The annealing of the injection moulding thin-gage goods of this aspect can be finished by one or more technology according to the present invention.For example, annealing steps can comprise allows the plastic material of goods stand various types of electromagnetic radiation, such as far infrared, and infrared ray, ultraviolet ray and microwave radiation.In addition, can use acoustic energy and/or ultrasonic energy, electric energy, electronic arc, electron beam, plasma (for example corona, glow discharge etc.), steam, heated air (for example hot-air), magnetic field, ionising radiation, laser, radio frequency with directly contact with heating or vibration surface.Preferably, annealing steps by just before main body is fitted to goods, during or just after heating of plastic materials carry out.

According to particular, annealing process is on the spot by being delivered to goods itself by heat from medium and promoting the medium filled articles of high enough temp of the annealing of goods to carry out with having.In this case, the medium of heating can the distortion (if any) of goods before, during or just after introduce.Because the thin-walled character of goods contact with medium, perhaps can be assumed to approaching near the temperature in the goods zone of medium relatively or equal the temperature of medium self-temperature.For example, though the specific region of the goods that will seal does not preferably directly contact with medium, in case medium has been incorporated in the goods, the temperature in the zone that seal tends to the temperature of medium.As long as this temperature height must be enough to cause annealing, this will cause the partially or completely annealing in these zones (zone that comprises the goods that will seal) of goods.The temperature of medium of annealing on the spot preferably is higher than 18 ℃, more preferably is higher than 22 ℃, also more preferably is higher than 25 ℃, even more preferably is higher than 30 ℃, most preferably is higher than 35 ℃.

Alternative pattern of fever method for annealing comprises goods be impregnated in bath, baking oven or other device, or allow goods pass through this bath, baking oven or other device, they contain heating liquid or gas or other annealing agent, maybe can lead to or make goods contact heating liquid or gas or other annealing agent.For example, goods can flood the enough time in hot bath, thereby they are heated in the temperature required scope.The specific time of staying in hot bath can depend on that various factors is static such as shape of products and/or thickness and water-bath or stirs, and bathes size and number of articles than the fluctuation that whether has caused bath temperature, and other factors.The filling content of wishing goods therein also heats more than specified temp, and under the situation such as the destructive distillation of some food, this method for annealing is useful especially.Can take out goods from water-bath then, drying is cooled to environment temperature again.

In other embodiment preferred, use radiation heating, such as heating with infrared ray.Especially an advantage with the infrared radiation heating is the rapidity that can be used for implementing heating steps.Another advantage is to eliminate independent drying steps.

When the electromagnetic radiation of one or more types was the annealing agent, the goods that comprise polymer should contact radiation and reach and be enough to absorb enough energy at least, thereby eliminate polymer stress, the time that prevents stress cracking wherein.Contact absorbs and is effective to stress and eliminate can being aggregated thing, does not have or does not cause that basically one or more frequency ranges softening or that flow that the heat of polymer is brought out take place.That electromagnetic radiation is selected from is infrared, the electromagnetic radiation of visible light, ultraviolet ray, microwave, radio, laser and other type.

Depend on plastic material and goods, annealing in process can before the distortion of goods, during or carry out afterwards.If carried out annealing in process before the distortion of goods, preferably, the effect of annealing process still influences the polymer in deformation process.For example, if use heat to anneal and removed before the distortion of goods or significantly reduce thermal source, plastic material is also preferred during deformation technique and be fully warm afterwards, anneals so that will be out of shape goods.The other method of using thermal annealing is to store the final packaging product in heating or natural warm storage area, temperature constant wherein in or regularly raise or rise to 〉=22 ℃, more preferably 〉=25 ℃, also more preferably 〉=27 ℃, also more preferably 〉=30 ℃ and most preferably 〉=35 ℃, and reach the time that is enough to make goods or the annealing of its parts, measure by the ESCR on the flow direction of polymer that compares with unannealed goods or its parts and/or the improvement of Gullwing tear resistance.

Needn't need whole goods are annealed and obtain the beneficial effect of this aspect of the present invention.If desired, annealing in process can relate to predetermined one or more goods zone, and annealing has a useful especially effect, such as to those zones in the injection-molded item of the susceptible of ESCR or other mechanical damage.The part annealing of goods can be for example by the some parts with infra-red radiation annealing goods, and the other parts of masking article realize simultaneously.Under the situation of pipe, can advantageously selectively annealed zone comprise crimping/sealing area and adjacent area and other zone that is out of shape and therefore has the pipe of the additional and uncommon stress that is applied thereto owing to crimping/sealing technology.

In addition, annealing can be carried out in one or more stages.For example, by filling, can at first allow the part of goods anneal with the warmed fluid medium.This will mainly anneal and contact with the warmed fluid medium and/or near those zones of the goods of this warmed fluid medium.When these goods are whens pipe, this initial annealing in process body of will mainly annealing, if but this medium is enough warm and contact time enough, and its can also anneal other zone of pipe is such as the zone of wanting crimping and sealing.After initial annealing, and in independent operation, this pipe then can be in openend crimping and sealing, this part of this pipe of will annealing.

The required annealing grade of particular product can be measured by experiment, and can change according to the desired properties that the product that will be packaged in the goods is made the goods of the condition of moulding of goods and processing for the degree/intensity of the ill-effect of these goods and the character and being used to that is used for the plastic material of moulding article.You Hai product (promptly having heavily stressed be full of cracks potentiality) can be packaged into the goods of annealing more widely than the same article that is used for not too harmful product valuably especially.Similarly, for example because shape, the goods that create conditions and/or the degree of the additional stress that is applied thereto by filling, crimping and sealing etc. has the higher stress level adopt stronger annealing to benefit bigger than not strong annealing.

Here to further be pointed out that, with respect to the location of thermal source without limits employed thermoplastic.Therefore, thermal source and thermoplastic can move, thermal source can move and simultaneously thermoplastic keep static, or vice versa.

In case be heated to temperature required scope, as required, can cool off or natural refrigerated product.Cooling step can comprise various cooling technologies similarly.What especially preferably here use is dry and cold technology.For example, goods can be used forced air convection current cooling method cool to room temperature.In addition, goods can cool off naturally, promptly need not quicken the type of cooling.Air can be in room temperature, or if desired, can cool off, to shorten the cooling step duration.In another modification, can use ultrasonic heating to replace radiation heating.In going back a modification, can use and force the hot-air convection heating.Goods can be put into baking oven or have radiation and other thermal treatment zone of the various combinations of Convective Heating.

Plastic material to the goods of this aspect according to the present invention is not particularly limited, as long as it can be injection molded into flexible thin-gage goods.The preferred form of plastic material in fact, has hereinafter been described according to another aspect of the present invention.

Generally, as described in the PCT/AU98/00255, have been found that by selecting to have the polymer that is used for Shooting Technique the flexible thin-gage goods that can injection moulding has long relatively thin-walled section greater than 10 hours time to rupture according to following ESCR test procedure test:

I) in high shear, a plurality of (preferred more than 6 or 6) of injection moldable polymers or blend polymer are rectangular under the long length of flow condition, introduced any molding post processing of end article that purpose is used to have the sectional dimension of 0.65mm thickness and 10mm width, it is same or similar that itself and purpose are used to make those of flexible thin-gage goods.

Ii) turn up, cut off 3mm from elbow with rectangular;

Iii) with the rectangular solution that is immersed in the stress cracking agent such as ethoxylated nonylphenol of bending, for example in 10% solution of Teric N9 (with the nonyl phenol-Orica Australia Pty Ltd of the oxirane ethoxylation of 9mol), and remain under 50 ℃ the temperature;

Iv) observe rectangular cracking sign, the sign of any cracking is considered to destroy; With

V) time to rupture is the time when sign is ftractureed in 50% rectangular demonstration.

Develop the stress that above-mentioned ESCR test is used for simulating the zone of the pipe that puts on crimping and sealing after carrying out crimping and seal operation, this is the zone of deflection and ESCR being destroyed the crimping and the sealed tube of special susceptible.Need this special test to be because be molded into flexible thin-walled mechanograph and crimping and when sealing subsequently when polymer, ' standard ' ESCR test such as ASTM D-1693 for the ESCR that measures polymer be fully inadequate-this is to test and the fact that ESCR result clearly demonstrated of above-mentioned test comparison Dupont 2020T and Dowlex 2517 polymer by use ' standard ' ESCR.

Generally, in order to select to be suitable for making the blend polymer of thin-gage goods, what be necessary is that blend polymer has the ESCR that the above operation of the basis that surpasses 10 hours is measured.Preferably, the ESCR of blend polymer surpasses 100 hours, more preferably surpasses 200 hours, most preferably above 360 hours.If thin-gage goods is to be used to pack to have very strong aggressivity and to cause composition that performance reduces in time pipe or other container such as humidizer or shampoo thin-gage goods, it is desirable to select to have the polymer of sufficiently high ESCR, make the thin-gage goods that forms by this blend can tolerate harsh use, although caused the reduction of performance by the eating properties of the material that contains at thin-gage goods.If thin-gage goods is used to pack the material of relative inertness, can stand lower ESCR.

ESCR test as above definition can use various stress cracking agent to carry out.Preferred stress cracking agent is Teric N9, and the ethoxylate of the nonyl phenol of 9mol comes from OricaAustralia Pty Ltd.Can also advantageously use other ethoxylate of nonyl phenol.Can use other stress cracking agent, and select, mineral oil for example, cationic surfactant, conspicuous other reagent of solvent and those skilled in the art according to required final use.

Aforesaid ESCR test with those identical or similar conditions of moulding that are used to make thin-gage goods under carry out.For example, if want to use the method for molding of having introduced the melt flows vibrotechnique to produce thin-gage goods, advantageously use plate to carry out the ESCR test by the mechanograph production for preparing by use melt flows vibrotechnique.Similarly, the condition of moulding that is used for the molding thin-gage goods is such as injection speed, injection pressure, and melt temperature, core rod and die cavity temperature etc. advantageously are used for producing the mechanograph that is used for the ESCR test.

Being used for the adaptability of polymer that the present invention uses or blend and its potential useful effect can test and measure by carrying out aforesaid ESCR, but preferably has following increase and change:

Prepare the two groups of rectangular ESCR of carrying out tests more than 6 or 6

Crooked and cut off (stapling) two group leader's bars after, the annealing in process that group leader's bar is recommended (for example, 50 ℃ high temperature 30 minutes makes rectangularly to be cooled to 22 ℃) and 22 ℃ of maintenances 2 hours down

Two group leader's bars are incorporated into as in the stress cracking medium by ESCR test defined.

Potential benefit of the present invention can be estimated by the ESCR and/or the Gullwing tear resistance of comparative polymers when carrying out and not carrying out test under the situation of annealing in process under being subjected to stress state.The present invention is particularly useful for thin-gage goods, wherein as by above-mentioned ESCR test determination in the annealing of the blend polymer that is used to make goods and unannealed time to rupture difference between rectangular above 5 hours, preferably above 10 hours, more preferably above 20 hours, also more preferably above 30 hours, more preferably surpass 50 hours, also more preferably above 100 hours with most preferably above 350 hours.

In addition, polymer or blend are used for the adaptability of application of the present invention can be by the annealing that cuts from mechanograph and unannealed rectangular, determine that such as those the Gullwing tear resistance (measuring on the flow direction at polymer) that in ESCR test, uses this type of is rectangular to have the size that is suitable for carrying out this test.Anneal rectangular preferably have rectangular higher more than 5%, preferred more than 10% than unannealed, the more preferably tear resistance more than 20% more than 15% and most preferably.When goods were prepared such as polyacrylic acid by the tendentious polymer that has relatively easy division or tear, the tear resistance of the flexible thin-gage goods of injection moulding especially was correlated with.When polymer in-mold being made as character, instrument design and condition of moulding and during height-oriented goods, tear and this tendentiousness that divides usually is exacerbated by molding methods.The Gullwing tear test especially can be used for estimating the adaptability that polypropylene type polymer and its blend (comprising above those that enumerate) are used for the flexible thin-gage goods of production injection moulding, because this base polymer and its blend can fully be tested by ESCR, but because inferior tear resistance still is not suitable for the flexible thin-gage goods of industrial injection moulding.As mentioned above, utilize the present invention's this based article of annealing their tear resistance can be improved to the degree that goods have commercial use.

Benefit of the present invention illustrates by following example.In design maximum stress is incorporated under the condition of moulding of molding pipe, will be by 25%Profax SC973 (100MFI PP, come from Basell), 34%Engage 8401 (30MFI mPE, come from DuPont-Dow) and the formulation formed of 41%WSG189 (100MFI LDPE comes from Qenos) be molded as the thick cylindrical tube of 165mm length * 0.5mm.The annealing and the unannealed rectangular ESCR that cut from these pipes use ESCR method as herein described to estimate.Found that, take from unannealed pipe unannealed rectangular more than 60% in 2 hours the ESCR test failure, and, be cooled to 22 ℃ and in 22 ℃ of pipes of regulating down to anneal in 2 hours rectangular, do not observe failure for taking from by cutting off rectangularly 50 ℃ of down heating 30 minutes.In addition, with 22% rectangular the comparing of annealing only, 94% unannealed rectangular failure before 360 hours.This explanation, the present invention has significantly improved the ESCR of the flexible thin-gage goods of injection moulding, and make and to adopt many blend polymers that when testing, can not have sufficient ESCR that they can be used to make commercial valuable flexible thin-gage goods according to method as herein described.

Benefit of the present invention is the most significant in having the flexible thin-gage goods of thickness less than the light filling bar of 1mm, wherein this light filling bar surpasses 50mm basically continuously on the flow direction of molten polymer blend in mould, preferably the basic 90mm that surpasses continuously on the flow direction of molten polymer blend in mould most preferably surpasses 100mm substantially continuously on the flow direction of molten polymer blend in mould.

WO00/01766 has described isotactic polypropylene and has had the blend of 4wt% to the ethylene-propylene copolymer of 35wt% ethene; Two kinds of components all have the long isotactic propylene sequence of enough crystallizations.This type of blend can be suitable for making flexible pipe and other container, and they heat by the method such as the product heat filling that requires with container to hold and/or the container by method heat treatments such as destructive distillation filling.The blend that meets above regulation comprises the isotactic polypropylene of 1-95wt% and has the ethylene-propylene copolymer that is higher than the 65wt% propylene and preferably is higher than the 80wt% propylene.

The blend of various polyacrylic polymers and ethene, propylene or butylene alpha-olefine polymers also is particularly suitable for making flexible pipe and other container, the container that they heat by the method such as the product that requires with container to hold heat is filled and/or fill by method heat treatments such as destructive distillation.The blend that meets above regulation comprises at least a isotaxy of component (a), syndiotaxy or atactic polypropylene homopolymers or alpha olefin copolymer, preferably one or more C ₂-C ₂₀Alpha olefin copolymer, more preferably one or more C ₂-C ₈Alpha olefin copolymer, with various catalyst such as metallocene or similar Preparation of Catalyst, and at least a ethene of component (b), propylene and/or butylene copolymer, preferred C ₂-C ₂₀Alpha-olefin ethene, propylene or butylene copolymer, more preferably C ₂-C ₈The alpha-olefin ethylene copolymer, with various catalyst such as metallocene or similar Preparation of Catalyst and be characterised in that the super random distribution of the copolymer in the strand of polymer.These blends are by the component (a) of 1-99% and the component (b) of 99-1%, the component (a) of preferred 30-99% and the component (b) of 70-1%, the more preferably component (b) of the component of 45-99% (a) and 55-1% also, the further component (a) of preferred 55-99% and the component (b) of 45-1%, and component (b) composition of the component of 60-99% (a) and 40-1% most preferably.

As at PCT/AU98/00255, AU200020674A1, AU72146-99, Australia improves patent No.2002200093 and Australia improves described in the patent 2002100211 (all these patents are introduced for reference thus), and at least a compatilizer and at least a polyblend are usually had the effect of remarkable improvement ESCR.This introducing of compatilizer has also usually improved the Gullwing tear test of blend.This at least a compatilizer is polymer preferably, when with this at least a polyblend, has obtained to be better than the blend of the performance of initial composition or straight polymer when being used for the flexible thin-gage goods of molding such as the flexible injection pipe.This phenomenon advantageously is used for preparing the blend that is suitable for injection moulding flexible thin-gage goods of the present invention.

The applicant has had been found that the specific compatilizer of a class, especially can be used for making by injection moulding the blend of flexible thin-gage goods.They are high melt flows compatible polymers.It is above about the described method in first aspect of the present invention to have been found that the blend that comprises this type of compatilizer especially can be used for, and can be used for not comprising the method for the annealing of above-mentioned formed goods.

Therefore, according to a second aspect of the invention, provide the method for making flexible thin-gage goods, comprised at least a polymer of injection moulding (a) and (b) blend of at least a high melt flows compatible polymer.

Be noted that the following argumentation of blend according to a second aspect of the invention is equally applicable to the method for first aspect of the present invention.

High melt flows compatible polymer generally has and is higher than 100, preferably is higher than 200, more preferably is higher than 300 MFI, and can have and be higher than 500, further is higher than 1000, also further is higher than 1,500 MFI.(a) and/or one or more polymers compositions (b) advantageously prepare with metallocene or similar catalyst system.

In blend polymer, by (a) and gross weight (b), component (a) preferably blend about 40 to about 99.9wt%, and formed the continuous of blend or continuous phase altogether.This blend polymer generally by the alternate manner that maybe can produce abundant mixture under the high shear mixing condition such as parallel connection or tandem reactor (each reactor produced blend component a) and/or b) one or more components) in mix blend component (a) and (b) form.Devices such as double screw extruder are the examples of the mixing apparatus that is fit to.The alternate manner that obtains well-mixed blend is that those skilled in the art institute is conspicuous.

This blend polymer can prepare by some or all components of extruded polymer blend, cuts the gained extrudate then and is used for injection moulding process of the present invention.In addition, this blend polymer provides with the form of component, blend polymer in the method before the fusion and during mix.

High melt flows compatible polymer can be selected from vinyl-vinyl acetate copolymer; Ethylene-vinyl alcohol copolymer, plasticising polyvinyl acetate and polyvinyl alcohol; The polyolefin that alkyl carboxyl replaces; The copolymer of organic acid acid anhydrides; The copolymer that contains epoxy radicals; Haloflex; Copolymers such as ethylene-propylene-butylene copolymer; Extremely-low density, extra-low density, low-density, middle density and high density polyethylene (HDPE) and copolymer thereof; Polypropylene, polybutene and and copolymer; Polyester ether; Polyether ester (such as the Hytrel series of DuPont); Acrylonitrile metry1 methacrylate copolymer; Block copolymer with styrene end block; Half ester; The polyethylene of amino and alkyl silane grafting; The vinyl addition polymer; Styrene-butadiene block copolymer; The polyolefin of acid grafting; The ethenyl pyrrolidone graft polyolefin; The block copolymer of binary monomer; Propylene grafting beta-unsaturated esters; The improved polyalkene that comprises acid amides, epoxy radicals, hydroxyl or C2-C6 acryloxy functional group; Be applicable to polyolefinic other polymerization compatilizer; Particle in order to last any material coating; And their mixture.In above compatible polymer, functional group is incorporated in the improved polyalkene as the part of unsaturated monomer usually, this unsaturated monomer and olefinic monomer copolymerization, or graft on the polyolefin, thereby form improved polyalkene.The ethyl acrylate and/or the methyl esters that have comprised ethene and/or propylene, and ethylene acrylic and methacrylic acid copolymer resin.

Also comprise compatible polymer such as in and ionomer such as the blend of Surlyn (Dupont) and EEA and/or EMA and/or EMAA.For example, the ionomer that low MFI partly neutralizes such as Surlyn 9970 (MFI=14) can with high MFI EMA such as (MFI=500) compounding of Nucrel 599 (Dupont), obtain MFI and be higher than the obtainable MFI of the independent Surlyn of using, the compatible polymer blend that can also from the advantageous property of Surlyn, benefit simultaneously.It will be apparent to those skilled in that above example only is combination a kind of of the various compatible polymers contained of the present invention.

The polyolefin that alkyl carboxyl replaces can comprise that carboxyl is wherein derived by acid, their ester, acid anhydrides and salt and the replacement polyolefin that comes.Carboxylate comprises the carboxylic acid of neutralization, usually is called as ionomer (for example Surlyn).Usually, acid, acid anhydrides and ester comprise methacrylic acid, acrylic acid, ethylacrylic acid, maleic acid ethylene oxidic ester, 2-hydroxy acrylate, diethyl maleate, maleic anhydride, maleic acid, the ester of dicarboxylic acids etc.Preferred example comprises that the ethylenically unsaturated carboxylic acids copolymer is such as polyethylene methacrylic acid and polyethylene acrylic acid and their salt.The copolymer of organic acid acid anhydrides comprises the copolymer of maleic anhydride and the copolymer of cyclic acid anhydride.

Poly--2-oxazoline compound and fluoroelastomer also are suitable as high melt flows compatilizer.Introduce 1-40%, most preferably 2-20%'s is poly--and 2-oxazoline compound is preferred.These compatible polymers have improved the adhesive force of PE blend and various base materials, and this can make them can be used for printing or label.Compatible polymer comprises the alpha olefin copolymer base material with the grafting of a certain amount of monovinylidene (vinylidene) aromatic polymer.Preferably, the alpha olefin copolymer base material is the terpolymer of ethene, propylene and non-conjugated diene hydrocarbon.What especially effectively be used as compatilizer and high MFI compatilizer is various aromatics/aliphatic olefin copolymer, styrene-1,4-butadiene-butylene-styrene block copolymer (SBBSA copolymer), s-B-S copolymer (SBS copolymer) and styrene-ethylene-butylene-styrene copolymer (SEBS copolymer) are to be effective to produce flexible thin-walled examples of articles especially.

Many copolymers of ethene also can be used as high melt flows compatible polymer in the method for the invention.For example, can mention the polyethylene of single site catalysis polymer such as metallocene catalyst.

This blend polymer preferably include (a) at least a have be higher than 10, preferably be higher than 20, more preferably be higher than 30, the polymer that also more preferably is higher than 50 MFI, this polymer is ethene or propylene or butylene homopolymerization or alpha olefin copolymer preferably, preferably with metallocene or similar Catalyst Production, and shown that narrow composition distributes, and means that the functionalized comonomer content from the molecule to the molecule is similar; (b) at least a high melt flows compatible polymer preferably has and is higher than 100 melt flow rate (MFR) and preferably with ethene, propylene or the butylene homopolymerization or the alpha olefin copolymer of metallocene or similar Catalyst Production.All reference substances of metalloscene catalyst comprise can obtained performance and the polymer phase of metallocene preparation with or other catalyst (for example single center and constrained geometry catalyst) of similar polymerization thing (for example narrow or wide MWD, narrow composition distributes).This type of blend can be chosen wantonly and comprise and well known to a person skilled in the art additive, and especially can comprise the steam that can reduce the polymer of wherein having introduced them and/or the additive of oxygen infiltration rate.For example, and as introduce described in the WO/02/074854 for reference at this paper, the low MW Hydrogenated aliphatic resin that adds 0.5-3% can reduce blend such as poly-(bicyclopentadiene) and the nominal dampness elimination impervious of the goods that prepare thus and O2 infiltration rate sometimes.

The employed polyethylene of this paper can be homopolymers or copolymer, and comprises the ethene plastic body, VLDPE, LLDPE, LDPE and HDPE.As used herein ethene plastic body is meant that generally density is lower than the class ethylene copolymer of about 0.915g/cc (being low to moderate about 0.865g/cc).The ethene plastic body has the ethene degree of crystallinity between plastic material (being linea low density and very low density polyethylene) and ethylene/alpha-olefin olefin elastomer.VLDPE is a very low density polyethylene, has the density of 0.90-0.915g/cc usually.LLDPE is a LLDPE, has the density of 0.915-0.930g/cc usually.LDPE is a low density polyethylene (LDPE), has the density of 0.915-0.930g/cc usually.HDPE is a high density polyethylene (HDPE), has the density of 0.930-0.970g/cc usually.

Though PCT/AU98/00255 proposes " many have the blend that the unusual polyacrylic polymer of the MFI of wide region (1-200+), density and degree of crystallinity can obtain to be applicable to inventive method ", but it does not have to describe by introducing the compatible polymer of at least a any character, comprise any certain benefits that polyacrylic polymer obtained, in fact do not provide example with the compatible polymer that is higher than 100 MFI with high MF I.In this patent application, high MFI compatible polymer is meant that one or more generally have the compatible polymer that is higher than 100 MFI.

Compatible polymer has mainly formed the decentralized photo of blend of the present invention.Now be surprisingly found out that, in making the formulation of flexible thin-gage goods, introduce at least a high melt flows compatible polymer and usually have with use and have many remarkable advantages that the identical compatible polymer of low MFI is compared.Also have been found that, improve ESCR and/or the ability of the tearing strength value that be cancelled of molding blend on the polymer flow direction as long as the molecular weight of this at least a compatible polymer is not less than to exceed, high MFI compatible polymer is incorporated into has many remarkable advantages of comparing with the identical compatible polymer of introducing low MFI grade in the blend.For example, high melt flows compatible polymer usually has the effect of shearing sensibility and total MFI of the whole blend of raising, thereby improves its mobile performance.Also have, because have inverse relation usually between the MFI of polymer and some physical properties, usually find, polymer performance increases with MFI such as flexural modulus and hardness and reduces.When for example because cost, it is former thereby when needing to use specific compatible polymer that ESCR renders a service etc., and that this polymer of low MFI grade (promptly have≤100 MFI polymer) has for required application is too high and obtained the flexural modulus of too stiff mechanograph, high MFI, similar or the identical compatible polymer of chemical property replaces the compatible polymer of the MFI of all or part of have≤100 in the blend to make can producing and utilizes having than obtainable higher MFI in the past, has reduced the blend of normal relevant with the compatible polymer that hangs down the MFI grade adverse effect to the performance such as ' feel ' and high flexural modulus simultaneously.The desired properties that depends on moulding article, high melt flows compatible polymer can be as the unique compatible polymers in the blend, perhaps can with other MFI compatible polymer blend, the latter can be high or low MFI compatible polymer.

Do not wish to accept the opinion restriction, it is believed that the interaction between polymer and high melt flows compatible polymer has formed the zone that can be considered to " abutment " in moulding article.As if these " abutments " absorb or disperseed by the stress in the goods of this blend polymer preparation.As if the existence that is dispersed in these " abutments " in the goods absorbs or has disperseed stress in the goods, otherwise can cause physical property to reduce.It is believed that, by use benefit that at least a high melt flows compatible polymer obtains mainly owing to the low MFI modification of identical compatilizer relatively, they more effectively are scattered at least a compatilizer, and with obtainable the comparing of low MFI modification with same polymer, they can form more less decentralized photo granularity.Generally, the MFI of compatible polymer is high more, and the granularity that it can form is more little, but exceeds a certain MFI (with therefore MW), further reduces MW and can not cause further reducing of high melt flows compatible polymer granularity.Decentralized photo than small grain size so that cause the increase of total surface area of the compatible polymer of set percetage by weight, thereby provide more substantial in the polymer of blend and interactional abutment and the zone between the decentralized photo (being compatible polymer).The granularity that reduces compatible polymer illustrates the available following fact of the influence of the numbers of particles of the compatible polymer in the blend: for the compatible polymer of the set wt% in the blend, the granularity of compatible polymer is reduced by half (for example by particle radius is reduced by half) make the compatible polymer number of particles increase by 8 times, the total surface area of compatible polymer increases by 2 times.Therefore, the radius of the particle of the compatible polymer number that makes stress in the mechanograph eliminate ' abutment ' that reduces by half is increased by 8 times, the surface area at the interface between compatible polymer and polymer increases by 2 times.These increases have the potential effect of improvement mechanograph performance such as ESCR and tearing strength.

Once more, do not wish to accept the restriction of opinion, we think, the numbers of particles of the compatible polymer of discontinuous phase and the increase of surface area are one of major reasons of many improvement in performance of the present invention (for example ESCR, tearing strength).Usually can reduce the percentage of the compatible polymer in the blend by the improvement of introducing ESCR that high MFI compatible polymer obtains etc., also obtain acceptable ESCR etc. simultaneously.This can be favourable, if for example wish to reduce the amount of the polypropylene compatilizer in the blend, so that reduce the flexural modulus of described blend.In addition, and use identical example, compare, keep the polyacrylic wt% of high melt flows compatibility to cause the remarkable increase of the number of dispersion particle with the equal polypropylene of low MF I, this so that improved total ESCR of blend.This ESCR improves and then makes and can adopt high MFI polymer, thereby has improved the processing characteristics of blend, has kept acceptable ESCR performance simultaneously.

For various types of compatible polymers, have that its MFI is the how high upper limit (how low its molecular weight be actually) actually before beginning unacceptably reduces the performance of the specific blends be used for application-specific.This upper limit is according to specific compatible polymer (for example homopolymers or copolymer p P, ionomer etc.), the final use of the performance of any other compatible polymer in the blend and the characteristic of polymer and interaction between them and layered product (for example planning what is packaged in this product) changes, and can be determined by experiment.For some application, improved benefit for other performance of the blend that obtains to bring by introducing, with the identical blend of low MFI modification with identical compatible polymer relatively because certain reduction of some characteristic of the specific blends that one or more high MFI compatible polymers of introducing cause is an acceptable.Once more, the MFI of high melt flows compatible polymer can be how high boundary and can be reduced to the introducing level that obtains before the unacceptable level in the blend performance and can measure by experiment.

High melt flows compatible polymer can use suitable catalyst (comprising metallocene or similar catalyst) and processing conditions directly to prepare in reactor.High melt flows compatible polymer can also prepare by the low MF I polymer with various peroxide well known by persons skilled in the art or other strand cutting polymer ' cracking ' same type.For example, 50MFI polypropylene homopolymer or copolymer can be converted into high MFI (for example 300,500,1000 or 1500MFI) polypropylene homopolymer or copolymer by cracking.The required cracking of high melt flows compatible polymer that produces specific MFI can be finished before high melt flows compatible polymer is incorporated into polymer, prepared for introduction into the high melt flows compatible polymer in the blend thereby form.In addition, high melt flows compatible polymer can be through the following steps forms in blend on the spot: will suitable amount and type polymer cracking to the cracking agent of required MFI can be incorporated in the compatible polymer and/or with described cracking agent is coated with this compatible polymer, the compatible polymer/cracking agent bond of preparation like this joined in one or more other blend component and be reduced at the MW (molecular weight) that is enough to make the cracking agent with compatible polymer under the condition of required MFI level of acquisition compatible polymer (common sufficiently high temperature) and process the gained blend.If use this a kind of method in back that obtains high melt flows compatible polymer, influence (promptly for (if having) of other blend component to be necessary to estimate in process cracking agent, the cracking of any unintentional other blend component that evaluation is brought by the cracking agent or crosslinked), and if necessary, regulate the blend formulation, to proofread and correct the result of these effects to the overall performance of blend.Production the continuous of polymer or altogether continuous phase to contain high melt flows compatible polymer be the reactor blend of the high melt flows compatible polymer of preparation and this polymer as the other method of the blend of the present invention of decentralized photo.This can finish by well known to a person skilled in the art many methods.For example, high melt flows compatible polymer and this polymer can prepare in the presence of suitable catalyst in single-reactor.In addition, they can prepare in two or more reactors of in parallel or series connection, and perhaps a kind of polymeric component can add in the reactor that wherein another component is produced by its finished product state.

The high melt flows compatible polymer of second aspect of the present invention is compatible polymer or their mixture, wherein at least a compatible polymer has usually and is higher than 100, preferably be higher than 200, more preferably be higher than 300, be higher than 500 potentially, or be higher than 1,000, or further be higher than 1500 MFI.Unless otherwise prescribed, MFI is according to ASTM D1238 (190 ℃ of conditions/2.16lg) measure.Preferably, high melt flows compatible polymer of the present invention is a polypropylene homopolymer, polyacrylic block or random copolymer or terpolymer, or their mixture, wherein polypropylene type polymers compositions has 〉=MFI of 100dg/min (at 230 ℃, 2.16kg measures down by ASTM D1238), preferably be higher than 100, preferably be higher than 200, more preferably be higher than 300, may be higher than 1500 MFI.Preferably, the propylene based polymer component is isotaxy or syndiotactic polypropylene homopolymers or the copolymer of MFI in above-mentioned scope.Preferably, the propylene based polymer component has the narrow composition distribution of the characteristic of the MWD of 1.8-4.0 and the acrylic polymers that belongs to metallocene or similar catalysis.Yet propylene based polymer is such as introducing US6 for reference at this paper, enumerate in 476,173 and have at the most a MWD of 20 those usually obtained good result.Polymer enumerate such as above those can use the Stereoselective metallocene catalyst system to prepare easily.Random ethylene/propylene/aromatic vinyl interpretation (interpol ymer) can also be used as compatibility and/or high melt flows compatible polymer in the present invention such as ethylene/propene/styrene interpolymers.

The high melt flows compatible polymer of various polypropylene types, especially when with low-molecular-weight plastic body as described polymer, the substantially linear polyethylene, metallocene long-chain branched polyethylene and above-mentioned polyvinyl when copolymer blended has produced the blend that is applicable to method of the present invention.Many monomers can with copolymerization of propylene, formed copolymer as the propylene of compatible polymer.These copolymers of many high MFI grades are suitable as and are used for polymer of the present invention or compatible polymer.

The high MFI polypropylene that is suitable as the high melt flows compatible polymer that is used for method of the present invention comprises the isotaxy of various MFI, density and degree of crystallinity, syndiotaxy and atactic polypropylene and their blend, they will produce desired properties in the product with method molding of the present invention.Especially the polypropylene that can be used as high melt flows compatible polymer comprises that the homopolymers of propylene or propylene and one or more are selected from ethene or linearity or branching C4-C20 alpha-olefin, more preferably ethene, 1-butylene, the 1-hexene, 4-methyl-1-pentene, 3-Methyl-1-pentene, 3,5, alpha-olefin in 5-trimethyl-1-hexene and the 1-octene, also more preferably ethene or 1-butylene or hexene or octene, optional a small amount of non-conjugated diene, the copolymer of preferred C6-C20 diene.In one embodiment, alpha-olefin can contain circulus saturated fully, the circulus part that makes 'alpha '-olefin monomers not contain to have any ethylenic unsaturated bond or any aromatic structure.Preferred alpha-olefin is a monoolefine.Have prescribed limit comonomer level these propylene copolymers preferably by the alkene that is fit to support non-carrying metal is luxuriant or similar catalyst system in the presence of polymerization prepare.

When one or more copolymers are formed or contained to the propylene type compatible polymer by one or more copolymers, this analog copolymer was preferably by forming as the propylene of principal monomer with as the alpha-olefin except propylene of comonomer.The content of propylene generally is 〉=70mol%, more preferably 〉=80mol%, and also more preferably 〉=90mol% and most preferably 〉=98mol%.Polypropylene copolymer of the present invention preferably includes has the random crystallization copolymer that narrow composition distributes, such as can be with those of metallocene or similar Preparation of Catalyst.

The high MPI polyethylene that is suitable as the high melt flows compatible polymer that is used for method of the present invention can comprise can be at the polyethylene that produces various MFI, density and the degree of crystallinity of desired properties with the product of method molding of the present invention.Comprise extremely low, low, in and high density polyethylene (HDPE).Especially when with ethene or propylene alpha olefin copolymer low-molecular-weight plastic body, substantially linear ethene or propylene alpha olefin copolymer or metallocene branching ethene or the blend of propylene alpha olefin copolymer, the various polyethylene polymers with MFI (100 to 1500+), density and degree of crystallinity of utmost point wide region will be the high melt flows compatible polymers that is applicable to method of the present invention.

High MFI ionomer and chemical related polymer provide certain benefits such as EEA, EVA and EMA as high melt flows compatible polymer, when with alkene as described polymer, especially ethene or propylene plastic body, substantially linear polyethylene or polypropylene, and/or branched polyethylene or polypropylene in conjunction with the time.Ionomer generally is to have used metal ion such as sodium, lithium or the ethene of zinc neutralization and the copolymer of acrylic or methacrylic acid.Being called ionomeric one group of ethylene copolymer can illustrate with commodity Surlyn (being made by DuPont).Ionomer often has the characteristic similar to cross-linked polymer at ambient temperature, be hard and tough and tensile, yet they can at high temperature be processed.Alkene, especially ethene or propylene plastic body, substantially linear polyethylene or polypropylene and/or branched polyethylene or polypropylene and one or more ionomeric blends are particularly preferred, do not compare with there being ionomeric olefin polymer, this type of blend provides sometimes has the barrier property that increases and the blend polymer of improved optical property.

Blend composition of the present invention generally comprises about 40 to about 99.9wt% the continuous phase that has formed blend when molding or is total to the polymer of continuous phase and about 60 to about 0.1wt% compatible polymer, and the latter is all or part of to be high melt flows compatible polymer.These are preferred range.The particular polymers component, specific phase capacitive polymers compositions and in blend of the present invention used relative quantity separately will depend on the requirement of the application-specific that adopts this blend, economy, and other processing factors, and can come by experiment to determine.

For the physical method of preparation blend, should fully mix to guarantee before being converted into finished product, forming uniform blend, preferred compatible polymer is by fine dispersion.Those skilled in the art can determine the suitable operation of these polymer of blend, thus equilibrium composition well-mixed need with the needs of process economy.Preparation the continuous of polymer or altogether the other method that contains as the blend of the present invention of the high melt flows compatible polymer of decentralized photo of continuous phase be the reactor blend of high melt flows compatible polymer of preparation and polymer.This can realize by well known to a person skilled in the art many modes.For example, compatible polymer and polymer can prepare in the presence of suitable catalyst in single-reactor.In addition, they can prepare in two or more reactors of in parallel or series connection, and perhaps a kind of polymeric component can join in the reactor that wherein prepares another kind of component by finished product state.

When molding, some preferred properties of final composition comprise high tensile, flexibility and tearing strength.The extractable content of composition of the present invention and thus obtained mechanograph preferably is less than or equal to 2.0wt%, more preferably less than or equal 1.6wt%, most preferably be less than or equal to 1.4wt%, measure by ASTM D-5227.

With the functional similarity at the compatilizer described in the PCT/AU98/00255, the high melt flows compatible polymer of this respect of the present invention uses with the environmental stress crack resistance that is enough to improve blend polymer at least and/or the amount of tear resistance (measuring by the Gullwing tear test).This high melt flows compatible polymer can also surpass the amount of the aequum of compatibilizing polymer blend to be used, thereby improve the viscosity characteristics of described blend polymer, so that the general performance of optimizing the molded feature of described blend polymer and/or layered product is such as flexibility and flexibility.Usually, high melt flows compatible polymer uses with the amount that about 2 of blend polymer arrives about 40wt%, though can use lower or higher amount in some blend polymer.The optimised quantity of specific formulation depends on desired properties, and can come by experiment to determine.In addition, the introducing percentage that has been found that high melt flows compatible polymer is higher than the required amount of environmental stress crack resistance that improves blend polymer and usually also can improves the blend polymer performance such as tearing and impact strength barrier property, chemical-resistant, processing and product feel.For example, introduce for the environmental stress crack resistance with the polyethylene blend polymer is improved to desired level and to be higher than and to improve chemical-resistant and general barrier property by the high melt flows compatible polymer of percentile polypropylene type, and the steam and the water infiltration rate that reduce blend polymer, the blend polymer of the polypropylene type high melt flows compatible polymer required with only containing minimum improvement environmental stress crack resistance is compared.The performance of this type of blend of high melt flows compatible polymer of the present invention can further be improved by high melt flows compatible polymer and/or the polymers compositions of selecting to be fit to grade, thereby obtains required final performance.For example, if be desirable to provide the blend polymer of the polypropylene type polymer that contains relative high percent, by using the polyethylene component of low relatively percentile low flexural modulus polymer as blend, can significantly improve the blend performance of this blend, such as ' feel ', ' pliability ', impact resistance (especially low-temperature impact resistance), elongation at break, tear resistance and/or destructive distillation.The example of the low flexural modulus polyethylene polymer that is fit to comprises the Tafmer XR propylene/alpha-olefins copolymer of low flexural modulus plastic body such as DuPont-Dow Engage 8401 plastic bodies and some Mitsui.In addition, have been found that to introduce and be higher than that essential percentile high melt flows compatible polymer is feasible can be introduced other polymer of high percent more and meet the present invention.Therefore, use the high melt flows compatible polymer of this amount to make to introduce this useful, especially inconsistent other polymer that is higher than the amount that may allow in other cases such as nylon and EVOH, improved simultaneously and torn and performances such as impact strength, barrier property, chemical-resistant and product feel.

The high melt flows compatible polymer that contains blend polymer can also be introduced various other additives.The example of other additive especially comprises other polymer; slipping agent; antitack agent, pigment, dyestuff; filler; antioxidant, plasticizer, UV protective agent; viscosity is polymer-modified, can react or absorb their additive (they some itself can be polymer) and other demoulding polymer and melt strength modifier with Harmful chemicals such as oxygen.In addition, improve the various performances of blend, such as bonding force, the compatibility between polymer and high melt flows compatible polymer, the decentralized photo granularity reduces, ESCR, the bulking agent of tearing strength etc. can join in the blend.Above-mentioned and other additive that is fit to can totally join before molding in one or more components or blend polymer of blend polymer, thereby changed its performance, makes it to be suitable for application-specific or obtain certain effects in end-product.At one or more additives itself is under the situation of polymer, for example removes under the situation of system at some oxygen, and described polymer can be the polymer or the compatible polymer of blend polymer.The non-polymer additive can be the compatible polymer of blend polymer.

Multiple polymers can be used as polymer in the blend with high melt flows compatible polymer of the present invention.These polymer comprise olefin homo and copolymer, optimal ethylene or propylene or chevron and with C3-C20 α or β-alkene and/or polyenoid, the copolymer of preferred C3-C8 α or β-alkene, this base polymer have extremely low to highdensity density (0.85-0.97g/cm ³Density range).Be applicable to that also of the present invention is the ethene with terminal ethylenyl groups, propylene and butylene copolymer and contain and be higher than 50% ethene, the ethene of propylene or butylene, propylene and butylene copolymer, they and comonomer are such as methyl acrylate, ethyl acrylate, acrylic acid, methacrylic acid and other polar comonomers, ionomer, styrene-ethylene/butylene-styrene ABA copolymer, styrene, halo or alkyl-substituted styrene class or other vinylidene aromatic monomer and/or one or more hindered aliphatics or alicyclic vinylidene monomer, tetrafluoroethene, vinyl benzo cyclobutane and cycloalkane (for example pentamethylene, cyclohexane and cyclooctane) copolymerization.These polymer can pass through the whole bag of tricks, comprise high pressure and low pressure method, use various catalyst to prepare such as Z-N and metallocene, and have from linearity to highly branched molecular structure, have therefore comprised LDPE, MDPE and HDPE.Being particularly useful for of the present invention is plastic body, ' substantially linear ' and branched polyethylene or polypropylene, the copolymer of propylene and ethene or one or more alpha-olefins, the terpolymer of ethene, propylene and one or more alpha-olefins (wherein the Catalloy polymer of Montell is an example), and use metallocene or similar Preparation of Catalyst and be characterised in that the polymer and the copolymer of propylene of the super random distribution of copolymer.Atactic propene copolymer is fit to the flexible thin-walled mechanograph of preparation, especially when the improved optical clarity of needs.Be applicable to that other polymer of the present invention comprises polylactic acid polymer, biodegradable polymers and polyketone that other is fit to, ethene-carbon monoxide multipolymer (ECO), ethylene/propylene olefin/co polymer (EPCO), linear alternated ECO copolymer is such as being " the improvement catalyst for preparing linear carbon monoxide/olefin copolymer " at title, name with John G.Hefner and Brian W.S.Kolthammer was submitted to and the US sequence number No.08/009 that abandons at present on January 22nd, 1993, in 198 (its disclosure is incorporated herein for reference) disclosed those, regenerated polythene (for example regenerative high-density polyethylene after the consumption of reclaiming by useless bottle).

As introduce JP07316356 for reference at this paper, to give an example among JP07316355 and the JP07330982, the elastomeric blend of crystallization PP and ethylene/styrene/alpha-olefin can be suitable as the polymer of the flexible thin-gage goods of preparation.

What also be suitable as polymer is linearity or branching isotachyte, and especially polypropylene and polybutene homopolymers or random copolymer have the structure that steric regularity changes in 25-60% [mmmm] pentads (pentad) concentration range.This steric regularity changes the statistical distribution owing to the stereoscopic error in polymer chain (stereoscopic error).This base polymer especially is described in WO01/27169 (P﹠amp; G), among WO/99/52955 (Rieger) and the WO99/52950 (Rieger), these patents are introduced for reference thus.

Be applicable to that also of the present invention is arbitrarily or the rather linearity or the branching isotachyte of rule sequence that has isotaxy and atactic block in polymer molecule, such as at described in the WO/99/29749 (ExxonMobil) those, this patent is introduced for reference thus.WO/99/2949 has described the branched polyolefin with crystallization side chain and amorphous skeleton, wherein at least the side chain of 90mol% be isotaxy or syndiotactic polypropylene and at least the skeleton of 80mol% be atactic polypropylene.

Especially when polymer such as at P﹠amp; G, described in Rieger and the ExxonMobil patent those are higher than 10 having, preferably be higher than 20, more preferably be higher than 30 and most preferably be higher than when introducing in the blend of 50 MFI, also more preferably polymer itself has and is higher than 10, preferably is higher than 20, more preferably is higher than 30 and when most preferably being higher than 50 MFI, they can be used as unique polymer or use as compatible polymer or high melt flows compatible polymer, and can have narrow or bread molecular weight distribution.Compare with equivalent polymers, be particularly suitable for preparing flexible thin-gage goods usually, because steric regularity that their lower has relatively obtained to have flexibility and the flexible polymer that lowers rigidity and increase such as above-mentioned those polymer than high tacticity.If this polymer is as compatible polymer or high melt flows compatible polymer, though it is unnecessary, but advantageously, it combines use with the polymer by same monomer preparation as compatible polymer or high melt flows compatible polymer, because this has obtained the compatibility/stability between the higher polymer and has made the regeneration of the injection moulding flexibility thin-gage goods of being produced by this class blend easier.For example, if this polymer is the polypropylene homopolymer or the copolymer of steric regularity with [mmmm] pentads concentration of 25-60%, it can with the polypropylene homopolymer with high tacticity more or copolymer blended, form the blend that is applicable to flexible thin-gage goods.In addition, these polymer can combine use with other polymer, form to be applicable to the blend of making the flexible injection thin-gage goods.For example, these polymer can with dissimilar polyethylene and copolymers, comprise LDPE, MDPE and HDPE blend, they so that can use as preparing with various different technologies of preparing as herein described, catalyst and copolymer at PCT/AU98/00255.Preferably, polyethylene uses metallocene or similar Preparation of Catalyst.

In being applicable to many blends of the present invention, advantageously at least two kinds of polymer are incorporated in the blend, wherein at least a polymer has higher degree of crystallinity and preferred higher MFI than this at least a other polymer.Though unnecessary, preferably, the higher crystallinity crystallinity of polymer is than this at least a other crystallinity of polymer height at least 5%, and is preferred more than high 10% or 10%.High-crystallinity copolymer can use by the whole bag of tricks and comprise that the various catalyst of metallocene, Z-N, constrained geometry catalyst prepare, perhaps can prepare, and can be linearity, substantially linear or branched structure by the radical reaction method.In the blend that at least a low crystallinity polymers (it is metallocene polymers preferably) is introduced, when high-crystallinity copolymer has wide MWD (molecular weight distribution), usually obtained better ESCR result at high-crystallinity copolymer.Wide MWD (that is multimodal) high-crystallinity copolymer can prepare by the whole bag of tricks.These methods comprise:

1) in the blending equipment that is fit to fully blend two or more have the polymer of different MFI;

2) produce bimodal or multimodal polymer with ' series connection ' reactor; With

3) in the single-reactor that uses suitable catalyst, produce bimodal or multimodal polymer.

Example as the multimodal high-crystallinity copolymer, if be suitable for producing the formulation of continuous phase of the blend of flexible thin-gage goods require 40MFI 0.92 density LDPE as at the luxuriant polymer of 30MFI0.885 density metal such as the high-crystallinity copolymer among the Engage 8401, can replace 40MFI LDPE obtain to process and other improvement in performance by 50: 50 blends with 20MFI 0.92 and 60MFI 0.92 density LDPE.The performance of the blend of two kinds of high-crystallinity copolymers in polymer and MFI can further improve by the ratio that changes 20MFI and 60MFI, therefore can make those skilled in the art change the performance of blend as required.The relatively little density contrast between two kinds of high-crystallinity copolymer components is not crucial for the performance of blend generally, so in above example, the 20MFI component can have 0.923 density and 60MFI component and have 0.919 density.For specific final use, specific density and MFI are poor, can come by experiment to determine such as those the acceptability that illustrates in the above example.

We have found that, plastic body, the substantially linear polyethylene, metallocene branched polyethylene and above-mentioned polyvinyl copolymer, propylene-alpha-olefin interpretation and metallocene acrylic polymers and interpretation are preferably to be used to prepare thin-wall product in the present invention, are particularly useful for preparing the polymer of flexible thin-gage goods.Plastic body, substantially linear polyethylene, metallocene branched polyethylene and above-mentioned polyvinyl copolymer, the key characteristic of propylene-alpha-olefin interpretation and metallocene acrylic polymers and interpretation are that their composition distributes, that is, comonomer is in the uniformity of the intramolecular distribution of polymer.Plastic body, the substantially linear polyethylene, metallocene branched polyethylene and above-mentioned polyvinyl copolymer, propylene-alpha-olefin interpretation and metallocene acrylic polymers and interpretation be general to be used and knownly prepares in the polymer molecule that generates and along the catalyst that the polymer molecule that generates is introduced comonomer very equably.Therefore, specific plastic body, the substantially linear polyethylene, metallocene branched polyethylene and above-mentioned polyvinyl copolymer, most of molecules of propylene-alpha-olefin interpretation and metallocene acrylic polymers and interpretation have roughly the same co-monomer content, and in each molecule, comonomer is super random distribution.Another advantage of this type of catalyst be in the molecule of the polymer produced by them and intermolecular branchign of molecule degree than use that typical catalyst obtains those are more even.For example, common Ziegler-Natta catalyst has generally obtained to have the copolymer that obviously wideer composition distributes-and under the situation of copolymer, comonomer distribution in the polymer of producing like this alters a great deal in polymer molecule, and not too randomly distributes in set molecule.Also have, and compare by those of Z-N or similar Preparation of Catalyst, the long chain branching degree is more consistent between the molecule with metallocene or similar Preparation of Catalyst.

Plastic body, the substantially linear polyethylene, metallocene branched polyethylene and above-mentioned polyvinyl copolymer, propylene-alpha-olefin interpretation and metallocene acrylic polymers and interpretation preferably are used to prepare thin-wall product in the present invention, are particularly useful for preparing flexible pipe.These polymer can advantageously have 1.5-30, preferred 1.8-10, the more preferably molecular weight distribution of the Mw/Mn ratio ranges of 2-4.Generally, plastic body, substantially linear or branching ethene or acrylic polymers comprise the interpretation of ethene or Noblen and ethene and/or propylene, wherein at least a C3-C20 alpha olefin copolymer is particularly preferred.Term " interpretation (interpolymer) " is used for representing copolymer or terpolymer or analog here.That is to say that at least a other comonomer and ethene or copolymerization of propylene have prepared alpha-olefin interpolymers.Generally, be fit to become the alpha-olefin of plastic body to contain about 2 3-16 carbon preferably approximately, most preferably about 3-8 carbon atom to about 20 carbon atoms with ethene or copolymerization of propylene.The example of this preferred alpha-olefin, non-limitative example are propylene, 1-butylene, 1-amylene, 4-methyl-1-pentene, 1-hexene, 1-octene and 1-dodecylene etc.Be fit to become to be applicable to that with ethene or copolymerization of propylene the polyenoid comonomer of plastic body of the present invention roughly has about 3 to about 20 carbon atoms, preferably approximately 4 to about 20 carbon atoms, and most preferably about 4 to about 15 carbon atoms.In one embodiment, polyenoid is to have about 3 diene to about 20 carbon atoms, and can be straight chain, side chain or cyclic hydrocarbon diene.Preferably, this diene is a non-conjugated diene.Be suitable for preparing the ethene of flexible thin-walled mechanograph or the non-limitative example of propylene/alpha-olefins copolymer comprises ethylene/propene, propylene/ethylene, ethene or propylene/1-butene, ethene or propylene/1-hexene, ethene or propylene/1-octene, substantially random ethylene/propene/aromatic vinyl interpretation is such as ethylene/propene/styrene interpolymers, ethene or propylene/styrene, halo or alkyl-substituted styrene copolymer.The non-limitative example that is applicable to terpolymer plastic body of the present invention comprises ethene or propylene/propylene/1,4-hexadiene and ethene or propylene/1-octene/1,4-hexadiene.

When this polymer is a plastic body, when wherein propylene or butylene constitute the substantially linear more than 50% of polymer or branched polymer, the MF I of alpha-olefin can be higher than common acceptable MFI when ethene-alpha-olefin copolymer constitutes this polymer, this is that propylene generally has better intrinsic ESCR performance with 1-butene-alpha-olefin copolymers under identical MFI owing to compare with most of ethene-alpha-olefin copolymers.Therefore, many propylene and 1-butene-alpha-olefin copolymers especially can have the MFI that reaches and be higher than 200 with those of metallocene or similar Preparation of Catalyst, and have still produced the acceptable flexible thin-gage goods with good ESCR when as polymer.The best MFI of specific propylene or 1-butene-alpha-olefin polymer can come by experiment to determine by those skilled in the art, but preferably＞30, more preferably＞50, general＞100 and possible＞150.Be fit to be copolymerized into the alpha-olefin that is suitable for propylene of the present invention or 1-butene-alpha-olefin copolymers and comprise about 2, preferably approximately 3-16 carbon atom, the most preferably alpha-olefin of about 2-8 carbon atom to about 20 carbon atoms with propylene or butylene.The example of this alpha-olefin, limiting examples is ethene, propylene, 1-butylene, 1-amylene, 4-methyl-1-pentene, 1-hexene, 1-octene and 1-dodecylene etc.Be fit to be copolymerized into the polyenoid comonomer that is suitable for propylene of the present invention or butylene copolymer with propylene or butylene and mainly have about 3 to 20 carbon atoms, preferably approximately 4 to about 20 carbon atoms, and most preferably about 4 to about 15 carbon atoms.In one embodiment, polyenoid is to have about 3 diene to about 20 carbon atoms, and can be straight chain, side chain or cyclic hydrocarbon diene.Preferably, diene is a non-conjugated diene.The non-limitative example that is suitable for propylene of the present invention or butylene/alpha-olefin plastic body comprises propylene or butylene/1-butylene, propylene or butylene/1-hexene, propylene or butylene/1-octene and propylene or butylene/ethylene copolymer.The non-limitative example that is suitable for terpolymer propylene of the present invention or butylene plastic body comprises ethylene/propene or butylene/1,4-hexadiene and propylene or butylene/1-octene/1,4-hexadiene copolymer.The copolymer that is particularly useful for propylene of the present invention or butylene and has other alpha-olefin of 2-8 carbon atom is to comprise propylene or butylene and ethene as the copolymer of requisite component (monomeric unit) and the copolymer of propylene or butylene and ethene; The alpha-olefin of at least a 4-8 of having carbon atom that can here use comprises for example 1-butylene, 3-methyl-1-butene, 1-amylene, 4-methyl-1-pentene, 1-hexene and 1-octene.In addition, this copolymer can contain the non-conjugated diene as the 0.5-10wt% of comonomer, such as 1, the 4-hexadiene, 5-methyl isophthalic acid, 5-hexadiene, 1, the 4-octadiene, cyclohexadiene, cyclo-octadiene, bicyclopentadiene, 5-ethylidene (ethylidene)-2-ENB, 5-butylidene (butylidene)-2-ENB, or 2-isopropenyl-5-ENB.Preferably, these copolymers use metallocene or similar Preparation of Catalyst.Be copolymerized into the ethene that is suitable for polymer of the present invention with propylene or butylene and/or the percentage of other alpha-olefin can change significantly, depend on desired properties by the mechanograph of the blend preparation of these materials.Generally, high more with the percentage of the ethene of propylene or butene polymerization and/or alpha olefin copolymer, the flexural modulus of resulting polymers is low more, so high more by the flexibility of the mechanograph of their preparations, wherein said polymer constitutes the polymer of blend.

US6355736 has described the propylene-based block copolymer composition, it comprises the propylene-alpha-olefin random copolymer and the propylene-alpha-olefin random copolymer that (B) has the propylene content of 35-60mol% that (A) has the propylene content of 99.4-99.9mol%, and this patent is introduced for reference thus.It has further described the propylene-based block copolymer composition, and wherein the content of propylene-alpha-olefin random copolymer (B) is 22-40wt%, by the weight of propylene-based block copolymer composition.This type of propylene-based block copolymer is suitable for use in the present invention as polymers compositions and/or high melt flows compatible polymer.

US6458901 has described and has been suitable as the propylene copolymer that is applicable to polymers compositions of the present invention and/or high melt flows compatible polymer, and this patent is introduced for reference thus.Described propylene copolymer comprises propylene, the alkene at least a alkene that is selected from except propylene, and cycloolefin with 2-20 carbon atom, and be characterised in that the sum of the carbon atom of the monomer except cycloolefin is at least 7.Cycloolefin is incorporated into the stable on heating improvement that has caused resulting polymers in the polymer of forming by the alkene in propylene and at least a alkene that is selected from except propylene with 2-20 carbon atom.Propylene copolymer preferably contains 0.01-20mol%, more preferably 0.05-15mol%, especially preferably 0.1-10mol%, the most preferably cycloolefin of 0.15-5mol%.When propylene copolymer of the present invention comprises ethene (this alkene has two carbon atoms), from the improvement of thermoplastic resin composition's flexibility, the content of ethene preferably≤80mol%, more preferably≤70mol%, especially preferably≤60mol%, most preferably≤50mol%.

Short chain branch profile exponent (SCBDI) be defined as co-monomer content the total mole of intermediate value co-monomer content 15% in the weight percent of molecule.It is about 30% that the SCBDI that is suitable for acrylic polymers of the present invention preferably is higher than, and especially is higher than approximately 50%, wherein can obtain 〉=70% numerical value.

Do not wish to accept the opinion restriction, we think that the interfacial tension between two kinds of immiscible polymer reduces with molecular weight, and like this, when the MFI of decentralized photo increased, the compatibility between polymer also increased, and became miscible until them.We further think, become miscible if the MFI of decentralized photo is increased to the small part that is reduced to of the blend polymer performance that can take place more than the certain level owing to decentralized photo in continuous phase.Elasticity substantially linear plastic body or branching ethene or propylene alpha-olefine polymers can be as at US5,278,272 and WO/02/074817 (the two introducing is for reference) described in, make than bread molecular weight distribution with catalyst by suitable selective polymerization method.Broad MWD material has shown higher shear rate or shear stress dependence.In other words, usually, MWD is wide more, and the effective MFI under high shear is high more, so processing characteristics is good more.Yet seen at WO/02/074817, it has been described by main preparation has roughly the same SCBDI, but two or more different polymer of MW (promptly prepare high MW copolymer (M _WH) and low MW copolymer (M _WL)) prepare the easily method of the olefin polymer of processing, have been found that and have to be lower than 60 M _WH/ M _WLThe polymer phase ratio, this have be higher than 60 M _WH/ M _WLPolymer can show the physical characteristic of some reductions, usually, be lower than 60 M _WH/ M _WLBe preferred.Preferred L _WH/ M _WLScope is 1.5-60, more preferably 1.5-40, also more preferably 1.5-15.In some embodiments, preferred L _WH/ M _WLBe 3-15.With high I ₁₀/ I ₂The MFI ratio is the wide molecular weight ' substantially linear olefin polymer ' of feature, and plastic body and metallocene branched polyethylene and polypropylene are particularly suitable for by method preparation pipe of the present invention.

Be applicable to high I of the present invention ₁₀/ I ₂Polymer can prepare by the whole bag of tricks.They comprise:

1) polymer that two or more is had a different molecular weight fully blend in suitable blending equipment;

2) has high I by ' series connection ' reactor made ₁₀/ I ₂Bimodal or multimodal polymer; With

3) use suitable catalyst in single-reactor, to prepare and have high I ₁₀/ I ₂Bimodal or multimodal polymer.

Can select to be used for preparation and have high I ₁₀/ I ₂Catalyst bimodal or multimodal polymer produce:

1) (polyethylene and ethylene copolymers that for example has the molecular weight distribution of 3-30 is such as at US patent 5,281, those described in 679 for broad molecular weight distribution polymers; This patent is incorporated herein for reference); Or

2) effective two or more polymer have narrow or bread molecular weight distribution separately as required.US5,539,076 have described the method for preparing the bimodal or multimodal polyethylene polymer of the density with 0.89-0.97 in single-reactor; The disclosure of this patent is introduced for reference here.

Illustrate clearly that by following examples utilization joins high melt flows compatible polymer the embodiment of the blend of the benefit in the polymer:

1) with SC973: Engage 8401: 25: 37.5: 37.5 blends of WSM 168 are injection molded into pipe, test ESCR.SC973 is a compatible polymer in this formulation, is the 100MFI PP that comes from Basell.This formulation had after 360 hours ± 30%ESCR destruction.

2) 25: 37.5: 37.5 blends with Atofina 3960: Engage 8401: WSM 168 are injection molded into pipe, test ESCR.Atofina 3960 is a compatible polymer in this formulation, is the 350MFI PP that comes from Atofina.This formulation has shown the significantly improved transparency that 0%ESCR destroys and compare with the contrast formulation after 360 hours.

At formulation 1) and 2) between unique difference be compatible polymer high melt flows compatible polymer roughly chemical equivalents replace compatible polymer, the important difference of the two is the high melt flows compatible polymer MFI more much higher than compatible polymer.The important improvement of ESCR performance is owing to the high melt flows compatible polymer MFI more much higher than compatible polymer (that is, lower MW).

The example of blend is according to a second aspect of the invention described now.Much less, the percentage of Shuo Ming various types of blend component can change according to the desired properties of the mechanograph of producing thus in these embodiments, and the percentage scope of producing all kinds of blend component of acceptable mechanograph can be determined by experiment.

Embodiment 1

30%Engage 8401,0.885 density come from the 30MFI metallocene polyethylene of Dupont Dow

45%WSM 168,0.919 density come from the 63MFI LDPE of Qenos

25%Fina 3960, come from the 350MFI PP homopolymers of Atofina.

Present embodiment has illustrated single high melt flows compatibility acrylic polymers has been incorporated into scheme in the blend of the mPE that is suitable for making flexible thin-gage goods and high-crystallinity LDPE.

Embodiment 2

45%Engage 8401,0.885 density come from the 30MFI metallocene polyethylene of Dupont Dow

45%WSM 168,0.919 density come from the 63MFI LDPE of Qeno s

10% 1000MFI PP homopolymers

10%SC973 comes from the 100MFI PP copolymer of Basell.

Present embodiment has illustrated that the bond with high melt flows compatibility acrylic polymers and low MFI propylene compatible polymer is incorporated into the scheme in the mPE/LDPE blend that is suitable for making flexible thin-gage goods.

Embodiment 3

15%WSM 168,0.919 density come from the 63MFI LDPE of Qenos

15%WRM 124,0.920 density come from the 22MFI LDPE of Qenos

40% 1500MFI PP homopolymers

Present embodiment has illustrated high MFI compatibility acrylic polymers has been incorporated into scheme in the blend that is suitable for making the mPE of flexible thin-gage goods, low relatively (22) MFI LDPE compatible polymer and relative high (63) MFI LDPE.

Embodiment 4

30%WSM 168,0.919 density come from the 63MFI LDPE of Qenos

20% 1000MFI PP homopolymers

20%Catalloy KS-084P comes from the 30MFI propylene terpolymers of Basell.

Present embodiment has illustrated that the bond with high melt flows compatibility acrylic polymers and low MFI, low flexural modulus propylene terpolymers is incorporated into the scheme in the blend that is suitable for making flexible thin-gage goods.

Embodiment 6

30%Engage 8407,0.87 density come from the 30MFI metallocene polyethylene of Dupont Dow

30%WSM 168,0.919 density come from the 63MFI LDPE of Qenos

20% Nucrel 599 comes from the 500MFI EMA of DuPont

20%Surlyn 9970, come from the 14MFI ionomer of DuPont.

Present embodiment has illustrated the non-propylene compatible polymer of high MFI and the ionomeric bond of low MFI has been incorporated into scheme in the blend that is suitable for making flexible thin-gage goods.In this class formulation, the non-propylene compatible polymer of high MFI to small part is used for improving the MFI of low MFI compatible polymer, when when the composition that is used for making flexible thin-gage goods utilizes, described low MFI compatible polymer is found to be effective especially, yet when in composition, being used as unique compatible polymer, has the abundant low MFI of the practicality of remarkable reduction composition.

Embodiment 7

70% have 15% butene content, 50 MFI and＜4 MWD and with the propene/but-1-ene copolymer of metallocene/single-site catalysts preparation.

30%Exact 4038, come from 125MFI 0.885 density polyethylene/butylene copolymer of ExxonMobil.

Present embodiment has illustrated high MFI mPE compatible polymer has been incorporated into scheme in the propylene/alpha-olefins copolymer that it is suitable for making flexible thin-gage goods.

Embodiment 8

70% have 20% octene content, 30 MFI and＜4 MWD and with the propylene/octene copolymer of metallocene/single-site catalysts preparation.

30%Fina 3960, come from the 350MFI PP homopolymers of Atofina.

Present embodiment has illustrated high MFI PP compatible polymer has been incorporated into scheme in propylene/octene alpha olefin copolymer that it is suitable for making flexible thin-gage goods.

Embodiment 9

70% have 25% ethylene contents, 50 MFI and＜4 MWD and with the propylene/ethylene substantially linear copolymer of metallocene/single-site catalysts preparation.

30%Fina 3960, come from the 350MFI PP homopolymers of Atofina.

Present embodiment has illustrated high MFI PP compatible polymer has been incorporated into scheme in the substantially linear propylene/ethylene alpha olefin copolymer that it is suitable for making flexible thin-gage goods.

Embodiment 10

80% have 30% butene content, 70 MFI and＜4 MWD and with the propene/but-1-ene copolymer plastic body of metallocene/single-site catalysts preparation.

The 50MFI isotaxy or the syndiotaxy PP homopolymers of 10% use metallocene/single-site catalysts preparation.

10%Fina 3960, come from the 350MFI PP homopolymers of Atofina.

Present embodiment has illustrated high MFI PP and low MFI PP compatible polymer has been incorporated into scheme in the propene/but-1-ene alpha olefin copolymer plastic body that it is suitable for making flexible thin-gage goods.

Embodiment 11

35%Engage 8401,0.885 density come from the 30MFI metallocene polyethylene of Dupont Dow

22.55%WSM 168,0.919 density come from the 63MFI LDPE of Qenos

22.5%WRM 124,0.920 density come from the 22MFI LDPE of Qenos

20% 750MFI PP copolymer

Present embodiment has illustrated the scheme that high relatively (63) MFI LDPE and relative low (22) MFI LDPE introduce with high MFI PP copolymer compatible polymer as polymers compositions.

Embodiment 12

40%Engage 8407,0.87 density come from the 30MFI metallocene polyethylene of Dupont Dow

22.55%WSM 168,0.919 density come from the 63MFI LDPE of Qenos

22.5%WRM 124,0.920 density come from the 22MFI LDPE of Qenos

15% 1000MFI PP homopolymers

Present embodiment has illustrated the scheme that high relatively (63) MFI LDPE and relative low (22) MFI LDPE introduce with high MFI PP compatible polymer as polymers compositions.

Embodiment 13

90% have 30% butene content, 70 MFI and＜4 MWD and with the propene/but-1-ene copolymer of metallocene/single-site catalysts preparation.

10% 500MFI polyethylene or ethene-alpha-olefin copolymer with the metalloscene catalyst preparation.

Present embodiment has illustrated the scheme that high MFI polyethylene or ethene-alpha-olefin copolymer are introduced with the propene/but-1-ene alpha olefin copolymer as compatible polymer.Alpha-olefin percentage in the copolymer can be 0.5-49%, depends on the requirement of final use.

Embodiment 14

90% have 30% butene content, 150 MFI and＞4 MWD and with the propene/but-1-ene copolymer of metallocene/single-site catalysts preparation.

10% 500MFI polyethylene is preferably with metallocene/single-site catalysts preparation.

Present embodiment has illustrated the scheme that high MFI polyethylene is introduced with high MFI polypropylene compatible polymer as compatible polymer.

On the further basis of above narration, highly branched polyolefinic exploitation makes can produce star, comb shape, nanogel and other similar polymer.

These polymer features are to be connected in the many polyolefin branch of polymer backbone, thereby highly branched structure is provided, and wherein can make the performance of highly branched structure adapt to the application of using this polymer easily.Branched structure has been controlled in be chosen in comb shape, star, nanogel or their the textural association aspect of specific reactivity polymer backbone and/or their preparation method.This makes can prepare the polymer that viscosity is lower than their linear homologue under identical absolute molecular weight.The blend of these polymer types and preparation thus especially can be suitable for making the flexible thin-walled mechanograph of injection moulding.Rheological behavior with these polymer of control branching has shown wondrous and effective feature.These polymer usually have 0 shear viscosity greater than the linear polymer of same molecular amount.They have shown that viscosity with shear rate descends (high shear desaturation) fast and linear and branched polymer hangs down at least 2 times plateau modulus than prior art.This back one characteristic is especially wonderful, because various types of ethene polymers has shown essentially identical plateau modulus.It is intrinsic that this is considered to monomer type, do not depend on polymer architecture.Lower plateau modulus means that comb shape and type polymer entanglement degree are more much lower than linear polymer, has therefore given this low viscosity for their molecular weight.The purposes of these performances of these polymer is that they have the utmost point low viscosity for their molecular weight under the melt processing conditions, so than the easier processing of prior art polymer.Even in the time of when join the common blend that is suitable for the flexible thin-walled mechanograph of injection moulding with relatively little amount in, they also can significantly improve the blend machinability.US6,355,757 and US6,084,030 has especially described the preparation of aforesaid polymer.

More than and the copolymer of similar invention can be used for being suitable for preparing the blend of the flexible thin-walled mechanograph of injection moulding, these blends comprise the branched copolymers of the present invention (for example 0.1-99.9wt%) of wide range, but 1-5% the most normally.Depend on the performance of above certain height branched polymer of the present invention and the desired properties of specific formulation, described polymer can be as the component of this at least a polymer or at least a compatible polymer part of composition of the present invention.The performance that depends on them, they can also be considered to additive, but not the component of polymer moieties of the present invention.

Nearest catalyst and process progress make can prepare various polypropylene homopolymers and copolymer, and it has makes them be effective to make the performance of the flexible thin-gage goods of injection moulding especially.Belong to these effective polymer row be in various manners and the ability of preparation with the percentile low flexural modulus PP alpha olefin copolymer of low relatively alpha olefin copolymer change the prepared elasticity PP homopolymers and the copolymer of steric regularity of polymer.

Example as one of these nearest progress is linearity or the branching isotachyte with steric regularity structure in 25-60% [mmmm] pentads concentration range, especially polypropylene and polybutene homopolymers or random copolymer.This steric regularity changes the statistical distribution owing to the stereoscopic error in polymer chain.This base polymer especially is described in WO01/27169 (P﹠amp; G), among WO99/52955 (Rieger) and the WO99/52950 (Rieger).Similarly, the propylene/ethylene copolymer in type described in the US6525157 (ExxonMobil) is applicable to the flexible thin-walled mechanograph of injection moulding.It is worthy of note that wherein the propylene-alpha-olefin copolymers of the carbon number in alpha-olefin＞4 has the particular envelope purposes of the improved anti-cold creep of requirement, compare with the propylene-alpha-olefin copolymers of carbon number≤4 in the alpha-olefin wherein.

Be applicable to that also what make flexible thin-walled mechanograph is arbitrarily or the rather linearity or the branching isotachyte of sequence of rules that has isotaxy and atactic block in polymer molecule, such as at described in the WO/99/29749 (ExxonMobil) those.WO99/2949 has described the branched polyolefin with crystallization side chain and amorphous skeleton, wherein at least the side chain of 90mol% be isotaxy or syndiotactic polypropylene and at least the skeleton of 80mol% be atactic polypropylene.They can have the particular utility as at least a compatible polymer in the blend in blend, wherein at least a polymer is crystallization or hypocrystalline PP.When described polymer has low relatively flexural modulus, situation especially like this, because it can be used for reducing the flexural modulus of the blend with crystallization or hypocrystalline PP and at least a polymer, and the tear resistance, flexural modulus and the impact resistance that improve blend.

Polymer with characteristic is such as at above-mentioned P﹠amp; G, those described in Rieger and the ExxonMobil patent can be used as this at least a polymer or this at least a compatible polymer in blend, and can have narrow or bread molecular weight distribution.Compare with equivalent polymers than high tacticity, usually be particularly suitable for making flexible thin-gage goods such as above-mentioned polymer, because the steric regularity of their relative attenuating has caused obtaining having the rigidity of attenuating and flexibility and the flexible polymer that increases.If this polymer is as at least a polymer, though advantageously-unnecessary-it uses with at least a combination with polymers by the same monomer preparation as at least a compatible polymer, because this has obtained the more high-compatibility/stability between polymer and has made the recirculation of the flexible thin-walled mechanograph of injection moulding that is prepared by these blends easier.For example, if polymer is a steric regularity is the polypropylene homopolymer or the copolymer of 25-60% [mmmm] pentads concentration, it can with have than the polypropylene homopolymer of high tacticity or copolymer blended, obtain to be applicable to the blend of flexible thin-gage goods.In addition, these polymer can use with other combination with polymers, form and are applicable to the blend of making the flexible thin-walled mechanograph of injection moulding.For example, these polymer can with dissimilar polyethylene and copolymer (comprising LDPE, MDPE and HDPE) blend, they can use various different production technologies, catalyst and copolymer such as preparing at described in ' 255 patents those.

The nearest progress of polypropylene polymerization technique can be applicable to the flexible thin-walled mechanograph of injection moulding.A kind of such progress is to produce the ability that has the small amount of ethylene copolymer and do not contain high flexibility, pliability and the elastomeric polypropylenes polymer of diene substantially.Because adjacent isotactic propylene unit, these polymer have limited degree of crystallinity, and have low relatively fusing point.They generally do not contain the inhomogeneities of any significant intermolecular steric regularity and comonomer composition, and are substantially free of diene.They are also without any significantly forming the inhomogeneities that distributes in the molecule.Ethylene copolymer comprises the upper limit of unit of the following 25wt% of being limited to ethylene derivative of the unit of 5wt% ethylene derivative.In these scopes, according to differential scanning calorimetry (DSC), these copolymers are appropriate crystallizations, and are particularly softs, have also kept sufficient hot strength and elasticity simultaneously.This base polymer is described in US6, in 525,157.

Nearest development has caused having part atactic, part isotactic polypropylene polymer synthetic of elastic performance.It is believed that in these components each molecule comprises isotaxy and therefore crystallizable part, and the other parts of same polypropylene molecule are atactic, are unbodied therefore.This base polymer is suitable for the flexible thin-walled mechanograph of injection moulding, as this at least a polymer or this at least a compatible polymer, combines such as polyethylene, polypropylene and/or their alpha olefin copolymer with other polymer in blend.The example that has these Noblens of different isotaxy degree in the different piece of molecule especially is described in US patent 5,594,080, Journal American Chemical Society (1995), the 117th volume, the 11586th page, and Journal American Chemical Society (1997), the 119th volume is in the 3635th page.

When this at least a polymer of blend is when wherein propylene or butylene account for the linearity more than 50%, substantially linear of this polymer or branched polymer, the MFI of this at least a polymer homopolymers or alpha olefin copolymer can be higher than general acceptable MFI when ethene-alpha-olefin copolymer constitutes this at least a polymer, and this is because propylene has the intrinsic ESCR performance that is better than most of ethene-alpha-olefin copolymers usually with chevron or alpha olefin copolymer under identical MFI.Therefore, some propylene and chevron or alpha olefin copolymer, especially with those of metallocene or similar Preparation of Catalyst, can have up to the MFI that is higher than 150, when as this at least a polymer, still produced the flexible thin-walled mechanograph of the acceptable injection moulding with good ESCR.Can be determined by experiment as the specific propylene of at least a polymer or the best MFI of chevron or alpha olefin copolymer, but preferably＞30, more preferably＞50, the characteristic that depends on specific polypropylene or polybutene homopolymers or alpha olefin copolymer, also more preferably＞100, most preferably＞150.Be suitable for being copolymerized into the propylene that is suitable for the flexible thin-walled mechanograph of injection moulding or the alpha-olefin of butylene alpha olefin copolymer comprises having about 2 to about 20 carbon atoms, preferably approximately 2-16 carbon, the most preferably alpha-olefin of about 2-8 carbon atom with propylene or butylene.In addition, this copolymer can contain the non-conjugated diene as the 0.5-10wt% of comonomer, such as 1, the 4-hexadiene, 5-methyl isophthalic acid, 5-hexadiene, 1, the 4-octadiene, cyclohexadiene, cyclo-octadiene, bicyclopentadiene, 5-ethylidene-2-ENB, 5-butylidene-2-ENB, or 2-isopropenyl-5-ENB.Preferably, these copolymers use metallocene or similar catalyst to prepare.Be copolymerized into the ethene of the polymer that is suitable for the flexible thin-walled mechanograph of injection moulding with propylene or butylene and/or the percentage of other alpha-olefin can change significantly, depend on desired properties by the mechanograph of the blend preparation of these materials.Generally, high more with the percentage of the ethene of propylene or butene polymerization and/or other alpha olefin copolymer, the flexural modulus of resulting polymers is low more, so higher by the flexibility of mechanograph of their preparations, wherein said polymer constitutes this at least a polymer of blend.

Design for recuperability and contain the continuous phase of the decentralized photo of high-crystallinity and low-crystallinity blend (such as following those) be suitable for preparing the flexible thin-walled mechanograph of injection moulding.Each regional size of decentralized photo in these blends is preferably very little.Each component of blend also is compatible, and reaching does not need to add bulking agent and obtain and keep this meticulous form.One of component is mainly to comprise stereospecific polypropylene, the polymer of preferred isotactic polypropylene.It is the component (XPP) with higher crystallinity.Second component is propylene and at least a C ₂, C ₄-C ₂₀Alpha-olefin, the copolymer of optimal ethylene.It is the component (SXPP) that has than low-crystallinity.In copolymer, propylene is Stereoselective ground polymerization basically preferably.Preferably, this copolymer has the basic distribution of forming uniformly, preferably as the result with the metalloscene catalyst polymerization.Most preferably, described XPP is an ethylene-propylene copolymer, for example ethylene-propylene hypocrystalline elastomer.

Have been found that at least a XPP of blend and at least a SXPP have obtained favourable processing characteristics, the composition of flexural modulus with reduction and the hot strength that increases, percentage elongation, answer and total toughness also is provided simultaneously.The terpolymer component is another crystallizable propylene-alpha-olefin copolymers (SXPP2), has the degree of crystallinity between the degree of crystallinity of XP and SXPP.A class PP blend that is suitable for the flexible thin-walled mechanograph of injection moulding comprises crystallization isotaxy or syndiotactic polypropylene (XPP), and contain the 4-35wt% alpha-olefin, optimal ethylene and the hypocrystalline alpha-olefin PP copolymer identical steric regularity of XPP (SXPP), the optimal ethylene propylene copolymer, and optional have degree of crystallinity between XPP and SXPP and second a propylene alpha olefin copolymer of similar steric regularity.These blends have heterogeneous form.It is believed that the coupling of this stereoregularity has improved the compatibility and the improvement adhesive force that has obtained the polymer areas interface of different crystallinity in polymer blend composition of component.Forming in the narrow intermolecular and molecule of copolymer distributes is preferred, but optional.These and similar blend are particularly suitable for making flexible injection thin-walled mechanograph and other container, and described container is by heating such as the class methods with required product heat fillings of containing of container, and/or pass through the method heat treatment filing of containers such as destructive distillation.Blend composition can extensively change according to application, can comprise XPP and SXPP that having of 1-95wt% is higher than the 65wt% propylene and preferably is higher than the 80wt% propylene.

At least a polymer composition with polypropylene type of low flexural modulus has the special-purpose that is used for the flexible thin-walled mechanograph of injection moulding.Below be the example of formulation of some summaries of the low flexural modulus PP composition that can provide suitable:

1 class formulation

1,8-25% crystallization PP or PP copolymer, most preferably 12-18%.If it is a copolymer, should have the PP of 85wt% at least, preferably surpass 90%.

2,75-92%, two of 82-88% kinds of elastomeric polymers most preferably, polymer a) and polymer b): polymer a) has a 15-32%, the alpha-olefin of preferred 25-30%, optional 0.5-5% diene and the polymer b of comprising) has 32-45%, the alpha-olefin of preferred 35-40%, the optional 0.5-5% diene that comprises.Polymer a) with polymer b) weight ratio be 1: 5 to 5: 1.

Above composition can prepare by sequential polymerization or blend.Preferred alpha-olefin is an ethene.Depend on required performance, above composition can with EPR (ethylene/propene copolymer), ethylene/propylene/diene terpolymers (EPDM), ethene/C ₄-C ₁₂Alpha-olefin (for example ethylene/octene is such as Engage) is used in combination.This type of elastomeric polymer can composition 5-80wt% exist.

2 class formulations:

1) crystalline propylene homopolymer of 10-60% or copolymer

2) propylene/ethylene copolymer that is insoluble to dimethylbenzene (that is, low ethylene copolymer content) of 10-40% and

3) ethylene/propene copolymer that at room temperature dissolves in dimethylbenzene (being high ethylene copolymer content) of 30-60%.

Above composition can prepare by sequential polymerization or blend.

3 class formulations:

1) crystallization PP homopolymers or the copolymer of 70-98%

2) the insoluble a bit propylene/ethylene copolymer (that is the ethylene copolymer of relative low content) of the dimethylbenzene of 2-30%.

Because high relatively % crystalline copolymer and relative low alpha-olefin PP copolymer, this blend has high relatively flexural modulus, and can prepare by sequential polymerization or blend.

The formulation of other type comprise various dissimilar at least a polymer P P such as above-mentioned those, the PP homopolymers of preferred different steric regularities, and the PP alpha olefin copolymer of various steric regularities and alpha-olefin content, be lower than the various types of at least a compatible polymer of at least a polymer P P that in this specific blends, uses, the simple blend of the PP alpha olefin copolymer of the mPE of especially different steric regularities and PP homopolymers and various steric regularity and alpha-olefin content with flexural modulus.

Except the purposes in the PP blend, HD/MD/LDPE and the PE copolymer that can be used as ' tie molecule ', for example the blend of low-density mPE also can use reinforcement technology in spherolite interface to improve.This can make tie molecule concentrate at grain boundary, and this has improved the number at the tie molecule of grain boundary effectively, this so that caused the blend ESCR that increases.

In development process of the present invention, the applicant has carried out relating to nano composite material and especially based on polyolefinic those the research work of at least a polymer.In the process of doing like this, the rapid improvement of introducing the ESCR performance of nano particle or specific blends that nano composite material is given makes the applicant be shocked.Especially, learn that LD, MD and HD blend have high destructive rate in 2 hours of on-test, and when introducing nano composite material, have extremely low to 0% destructive rate from our experience.We think, provide the improved nano composite material blend of these remarkable ESCR to can be used for comprising injection moulding, blowing, rotational forming and application of extruding and manufacture method.For example, we improve proof with ESCR and other physical property that HDPE type nano composite material blend obtains, blend of the present invention can be applicable to pipe, line, cable and other are extruded application, the injection-molded item of auto industry especially, various types of rigid packages, film, the rotational forming goods are such as drum and jar etc.

For polyolefin, especially the mechanical load bearing capacity of polyethylene molding product has constantly proposed requirements at the higher level.Especially, require to be particularly suitable for making the high environmental stress resistance be full of cracks, shock resistance of automobile mechanograph, hollow product, force pipe, electric wire and cable foreskin etc. and general hard, relative hard and rigid product.Require in the time of good environmental stress resistance cracking and stiffness to be not easy to satisfy, because they are considered to the performance that opposes usually.Though stiffness is with polyolefin, especially poly increase in density, environmental stress crack resistance reduces with increase in density.

For hollow product and force pipe, verifiedly advantageously use for example people such as L.L.Bohm, Adv.Mater.4, (1992), the described blend of 234-238 by HMW, low density ethylene copolymer and low-molecular-weight, high density ethylene homopolymers preparation.Similar polyethylene blend is disclosed in EP-A 100 843, and EP-A 533 154, and EP-A 533 155, and EP-A533 156, and EP-A 533 160 and US patent No.5 are in 350,807.

The important application of Bi-modal polyethylene blends is to produce the force pipe that is used to carry gas, drinking water and waste water.By the force pipe of polyethene preparation alternative metals pipe gradually.The key factor that this class is used is the extremely long service life of pipe, does not worry aging or brittle break.Even the defective of very little force pipe or impression can be grown,, cause brittle break even under low pressure.This process can be quickened owing to increase in temperature and/or aggressivity chemicals.

Like this, in further research, we are surprisingly found out that, the nano particle of various non-polymers and polymer can be as according to first and second aspects of the invention described above and also have effective compatilizer in other irrelevant application.Especially, have been found that nano particle can be used for improving the ESCR and/or the tearing strength of some polymer and blend polymer.

Therefore, according to a third aspect of the present invention, provide nano particle to be used to improve the ESCR of polymer or blend polymer and/or the purposes of tearing strength.

This type of blend be particularly suitable for making flexible thin-gage goods and by the whole bag of tricks, comprise injection moulding, extrude, prepared goods such as pipe material, cable, film and other goods of other method that thermoforming, rotational forming and those skilled in the art are familiar with.

Very clear, therefore the 3rd aspect of the present invention also provide the method for making flexible thin-gage goods, comprises that injection moulding wherein is dispersed with at least a polymer of nano particle.

The blend of this respect of the present invention can be processed by many processing methods, such as but be not limited to injection moulding, blowing, thermoforming is extruded, thermoforming and rotational forming.It is favourable various different products that these blends can be suitable for wherein improved ESCR, stiffness, obstruct and other physical property.The blend of this respect of the present invention is particularly suitable for making hollow product and force pipe, electric wire and cable foreskin and automobile, packing and other industrial goods.

Blend preferably includes at least a polymer and nano composite material and at least a compatilizer, more preferably polyolefin, at least a compatilizer and nano composite material, further preferred mPE, polypropylene compatilizer and nano clay nano composite materials, and most preferably mPE and LD, MD or HDPE, polypropylene homopolymer or copolymer compatilizer and nano clay nano composite materials.Notice that for this respect of the present invention, term: LDPE comprises LLDPE.

The blend of this respect of the present invention provides and has compared improved ESCR and other physical property with the prior art blend.As a result, they can prepare the blend that has the ESCR that equates with the prior art blend and other physical property but have higher MFI, have the improvement of the workability that matches and follow-up power uses and the saving of wear and tear in machines.The blend physical property is improved and also can be made mechanograph weight saving and film subtract thick potentially and reduction mechanograph/film weight, obtains required flexural modulus simultaneously.Simultaneously, they also provide better barrier property (for example impermeability) for mechanograph.

Various polymer can be as the bulk polymer of blend of the present invention.These polymer are discussed in front, in this respect, and can be with reference to above explanation.Equally, compatilizer or polymer can be included in the blend according to this respect of the present invention.In this point, can also be with reference to above explanation.

More particularly, the polymer that is applicable to nano composite material of the present invention for example is, but be not limited to, polymer is such as polyolefin, comprise plastic body, substantially linear metallocene polyethylene alpha olefin copolymer, low density polyethylene (LDPE) (LDPE), LLDPE (LLDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE) (HDPE), isotaxy, syndiotaxy and atactic polypropylene (PP) are such as the polypropylene with different isotaxy degree, such as especially at WO01/27169, WO99/52955, described in WO99/52950 and the WO99/29749 those, ethene, the alpha olefin copolymer of propylene or butylene, preferred use can form the metallocene of the super random distribution of alpha olefin copolymer in strand or the ethene of similar Preparation of Catalyst, the alpha olefin copolymer of propylene or butylene, polyamide is such as poly-(meta-xylene adipamide) (MXD 6), poly-(hexa-methylene adipamide) and poly-(caprolactam), polyester is such as poly-(ethylene glycol terephthalate), Merlon and polyacrylonitrile.

Nano particle in the blend of this respect of the present invention is clay preferably, most preferably organic clay.Compare with the identical blend that does not have nano particle, blend of the present invention especially can be used for preparing the product with significantly improved ESCR and barrier property.Compare with the identical blend that does not have nano-sized particles, nano-sized particles be incorporated into the benefit that also has the ESCR that improves blend in the blend, this so that significantly enlarged blend formulation scope.

In addition, we find, only by adding the mode of nucleator as the ESCR that improves mechanograph of the present invention, the polymer of some type with density of 0.85-0.92, preferred unsaturated polymer is such as polyvinyl chloride and polystyrene, more preferably polyolefin and also more preferably plastic body, the substantially linear polyethylene, metallocene branched polyethylene and polypropylene copolymer and most preferably plastic body and ' substantially linear polyethylene ' polymer and polypropylene copolymer can be used for preparing the mechanograph of the present invention that is suitable for packing some low aggressivity products.Yet, except nucleator, compatible polymer joined such as polypropylene and polypropylene copolymer caused better total ESCR in this polymer, and normally preferred.

Suppose that the PP compatilizer in the PE blend polymer has the average spherical particle diameter of 500nm, each particle has 785,000nm ²Surface area and 65,000,000nm ³Volume, by relatively, typical clay platelet has ± thickness of 1nm, this means that in order to obtain the volume identical with the 500nm diameter sphere, it must have the LXW size that equals 8062 * 8062nm.The assumed average clay platelet is 200 * 200 * 1nm (that is, it has 200 aspect ratio), and it has 40,000nm ³Volume.Therefore, by volume, a 500nm diameter PP spheric granules equals 1,625 clay platelet.The density of supposing clay is ± 1.8 (that is, the density of 2 * PP), this means, the layered clay plates of set weight percent have ± and the particle of 800 times PP.In other words, by theoretical nucleation energy power, the particle of clay size provides 800 times of nucleation site/particles of PP.This goes far towards to explain increasing of the blend ESCR that taken place when nano composite material being joined blend or replace some PP in the blend.

The interpolation for preparing the nano-scale particle of mechanograph of the present invention has usually obtained the improvement performance of blend of the present invention.Especially, this type of blend can contain meticulous, ultra-fine or nano-scale polymer or clay or metal oxide such as ultra-fine barium sulfate (it can have the granularity of 10nm), the particle of other inorganic, metal oxide is such as zinc, conduction tin (tin oxide that for example contains antimony), iron, zirconium, aluminium, chromium, yttrium, the oxide of europium, their mixture.Meticulous, ultra-fine and nano-sized particles can be to have about 1 to 200nm, and preferred＜100nm and usually about 4 arrives the primary crystallites granularity of about 60nm.These crystallites can form has at the most the approximately agglomerate of the particle mean size of 300nm.This at least a polymer that can make blend and/or the blend that contains non-clay crystallization/nucleator of at least a compatilizer crystallization/nucleation in the definition of nano composite material, have also been comprised.Though for ' normally ' mechanograph, usually add commercial nucleator with≤0.1% amount, preferred＞0.3wt% for the present invention sometimes preferably being higher than 0.1wt%, more preferably＞0.5% and the interpolation of amount often＞1% crystallization/nucleator.The optimised quantity that joins in the specific blends can be measured by experiment.Have many non-clay crystallization/nucleators, such as the organic acid slaine, for example Sodium Benzoate and lithium benzoate, glucitol derivative, diol, derivatives etc., they are used to prepare blend of the present invention, and are as well known to those skilled in the art.

Nano particle preferably has those of very high-aspect ratio, especially, but not only form by modified clay mineral those can be advantageously used for the ACA of preparation mechanograph of the present invention.Except the barrier property that improves mechanograph, nano particle can also strengthen their heat endurance, anti-flammability and other mechanical performance.

When nano particle is nanoscale clay with high aspect ratio, organic clay or other particle, even the increasing of ESCR, impermeability and other physical property of mechanograph of the present invention also is provided with respect to the nano particle of the little weight percent of polymeric material.As guidance, the average aspect ratio of nano particle is high more, and its average diameter is big more, and the improvement of barrier property that particle is given nano composite material is big more.For example, the nano composite material of nano particle with average aspect ratio of 1000 has usually than the nano particle with identical weight percentage and chemical type but the better barrier property of nano composite material with aspect ratio of 100.On the contrary, use above example, the nano composite material that nano particle has 100 average aspect ratio usually has than the better ESCR of the nano composite material with 1000 aspect ratio nano particles, because in preceding a kind of nano composite material, have more substantial individual particle, and then obtained more substantial polymer nucleation site, therefore, formed more substantial polymer crystals, this so that cause intrinsic better ESCR.When this nano particle is the particle with extra high aspect ratio, such as nano-scale TiO ₂During other metal oxide etc., even the nano particle with respect to the little weight percent of polymeric material also provides the ESCR of mechanograph of the present invention and the raising of other physical property, but the barrier property of this type of nano composite material generally do not resemble nano particle have the nano composite material of high aspect ratio good.

Nano particle/the blend polymer that is used for mechanograph of the present invention can be made by several different methods.A kind of such method is compounding, and wherein each composition is become as far as possible near uniform material by abundant melt mixed.Other method that polymeric layer is incorporated between clay/organic clay plates comprises in-situ polymerization, and solution inserts and the melt layering.Be preferred for organic clay of the present invention and be different from the common clay that is untreated, because when with polyblend or when mixing, the clay that is untreated has only formed generally that the organically-modified clay of common phase-separated mixtures is easier to be scattered in the polymer substrate, and can form two class nano composite materials: promptly, mainly insertion or the mainly structure of layering.For obtain the polyolefin polymer of better polymer-especially-and organic clay between compatibility, wish that usually organic clay contains the substituted alkyl side chain.The blend that is particularly suitable for mechanograph of the present invention comprises about 0.01 to about 25wt%, preferred 0.5 to 25wt%, and more preferably 0.5 to 15wt% and the most preferably 0.5 at least a expansion organic clay that arrives 10wt%.

The organic clay that is suitable for pipe manufacturer generally has about 1 to about 10,000 nanometers, and about ideally 100 to about 2,000 nanometers and preferably approximately 200 to about 500 or the granularity of 1,000 nanometer.When being used to form nano composite material and/or nano composite material masterbatch (promptly, be used for the follow-up concentrate that is dispersed in another polymer) host polymer when being polyolefin, have been found that, under the identical situation of all other conditions, short-chain branched degree in the polymer high more (measuring) by SCB I, the delamination degree of organic clay is high more, so the overall performance of nano composite material is good more.All other conditions are identical, and under the situation of alkene/alpha-olefin and other copolymer, the alpha-olefin in the polymer or the percentage of other copolymer are high more, and the delamination degree of nano composite material is high more.Also have, shown that in polymer molecule the polymer of super random monomer distribution is particularly suitable for preparing nano composite material of the present invention, because their use has often obtained than the higher delamination degree of similar polymer of the super random distribution of displaying monomer not.This type of super atactic polymer can come catalysis with metallocene well known in the art or similar catalyst.

Especially advantageously the blend wherein meticulous, ultra-fine or nano-sized particles has following properties:

1) aspect ratio of the particle mean size of 0.9-100nm and 10-2000.

2) preferably have＜thickness of 2nm and the diameter of 10-1000nm.

Usually, various types of clays are at least a compatilizers that preferably can have above characteristic such as following those.The layered clay material of preferred swellable is 2: 1 type phyllosilicate with cation exchange capacity (CEC) of 50-200 milliequivalent/100g mineral.Most preferred swellable layered clay material is that smectite clay mineral is such as montmorillonite.Other non-clay material with above-mentioned ion-exchange capacity and size also can be used as the source of the platelet particles of the blend polymer of making pipe such as chalcogenide.

Clay often exists as ' tactoid (tactoid) ' or ' gallery (gallery) ' naturally, and it is the agglomerate that reaches or surpass sometimes 100 clay platelet.In order to obtain nano composite material, the maximum benefit of clay nanocomposites especially, each nano particle need be scattered in the polymer substrate equably.Under the situation of clay, the method for separating each clay platelet is called layering.Layering can obtain by many modes, but the most frequently used method is that suitable insertion agent is incorporated in the gallery of clay, applies shearing then, thereby separates each plates.Insert agent and also should preferably have the functional group that can also effectively plates be connected in polymer with interpolymer interaction.Epoxy resin can be as inserting agent such as bisphenol-A.

There is a large amount of being suitable for to make the insertion agent of nano composite material of the present invention.What especially can be used for polyolefin-at least a blend polymer is the insertion agent that comprises the organic compound of the nonpolar part with the polarity of being bonded in part.Nonpolar part for example can be the saturated low polymer of isoprene, it often with non-polar polymer, especially the copolymer of propylene and ethene is compatible.The polarity part often has the affinity to the silicate sheet body of clay material.Thereby this organic compound has improved the compatibility of inserting clay material, when with the melt blended so that insertion clay material layering of enough shearings, causes inserting the clay layering in polymer.

Many methods that can prepare nano composite material and describe are in the literature arranged.Below highlighted the certain methods that is particularly suitable for producing the nano composite material that is suitable for making pipe.For preparation mechanograph of the present invention to make us interested especially be that wherein bulk polymer is a polyolefin such as polyethylene or polypropylene or the polyester nano composite material such as PET or PEN, described polymer is particularly suitable for making mechanograph of the present invention because of cost and other polymer performance.As everyone knows, form nano composite material with polyolefin special challenge is provided, this is because due to the difficulty of the layering of the basic non-polar nature of described polymer and the consequent organic clay that obtains significance degree.Yet novel insertion agent and the progress of obtaining the method for this nano composite material have caused the performance and the preparation method's of polyolefin-clay nanocomposites improvement.These progress with the especially high shear rate that produces (with the layering that has promoted the non-layered clay), can be produced the olefin polymerization nanometer composite material with good barrier and other useful performance in the injection molding tube technical process.

The method for optimizing that improves the organic clay delamination degree in the polyolefin be by add and the compounding improved polyalkene-such as maleic anhydride modified polyolefin polymer or oligomer-and multilayer clay of exchanging of organic cation (such as quaternary ammonium).This technology has obtained masterbatch, joins in the suitable polyolefin then and compounding with it.Zhi Bei organic clay has sufficient polarity like this, when with polyolefinic compounding process in when standing shear stress, especially in the high shear manufacture process of producing mechanograph of the present invention, can make the remarkable layering of clay.

Another kind method be introduce with the polyolefin bulk polymer of blend and cation exchange layered silicate material such as the compatible hydrogenation of cyclic polymer of clay, for example C ₉Aromatic polymer, and under proper temperature compounding gained mixture.Use hydrogenation C ₉Aromatic polymer as an example, the cation exchange layered silicate material adds with about equally amount.Preferably, the cation exchange silicate material washs in water, removes impurity, can be advantageously subsequently be fit to season cation ratio such as quaternary ammonium cation handle.The example of the hydrogenation C9 aromatic polymer that is fit to is the polymer with following chemical formula:

The polymer that meets following formula with the trade name of ARKON available from Arakawa ChemicalIndustries.Other cyclic polymer that contains unsaturated bond in cyclic group or in polymer chain itself is suitable for preparing the polyolefin organic clay nano composite material, and can come by experiment to determine.Use an advantage of the polymer/organic clay of cyclic group preparation to be, because they preferably have cyclic group in inside, they can be particularly suitable as oxygen scavenger, especially when with can the catalysis ring-type and/or during the catalyst compounding of the oxidation of unsaturated functional group.Be known that the many oxygen scavengers that contain cyclic group have produced less accessory substance than linear oxygen scavenger, and these accessory substances can move, thereby pollute the product that is packaged in the container of having introduced described oxygen scavenger.In these cases, polymer/organic clay has been realized the dual function (referring to blend of the present invention) of nano composite material and oxygen scavenger.

The another kind of method that preparation can be incorporated into the organic clay in the polyolefin is at first to use the functionalized Nano filling of amino silane.After this, carboxylated or maleinization polyolefin graft on filler by amine-carboxyl reaction.The gained modified filler is scattered in the semicrystalline polyolefins (for example polyethylene or polypropylene).Cocrystallization between carboxylic acidization or maleinization polyolefin and semicrystalline polyolefins can improve the interaction between filler and the semicrystalline polyolefins.

The another kind of method of preparation polyolefin-compatibility nano composite is that preparation can be scattered in the close organic clay in the non-polar organic solvent.Parent's organic clay can successively be handled with alkylaluminoxane with catalyst (comprising Z-N and metalloscene catalyst) then, thereby forms the compound that promotes that alkene or styrene polymerization and plates disperse.Nano composite material can directly the in-situ polymerization on the Nano filling particle prepares by alkene or styrene, need not shear, and without ion-exchange step, does not also need polar substituent is incorporated in polyolefin or the polystyrene.

Another nano composite material that is suitable for mechanograph of the present invention by nonpolar bulk polymer such as polyethylene or polypropylene, be scattered in montmorillonite or sepiolite clay that the insertion cation exchange multilayer silicate material in the bulk polymer is handled such as acid or quaternary ammonium, and organic cation, such as polyethylene or polypropylene with the amido terminal, organic cation with polymer lateral chain is formed, and the polymer and the bulk polymer of polymer lateral chain are miscible.Nano composite material is by preparing fusion bulk polymer and cation exchange multilayer silicate material and organic cation blend.

As everyone knows, different insertion agent have obtained different delamination degree; For example, the octadecylamine clay inserts agent and has produced and obviously be better than clay to insert agent be the nylon type nano composite material Obstruct membrane of the same polymer nano composite material of positive alkyl dimethyl benzyl amine ion.

Another the favourable and interesting nano particle that is applicable to nano composite material is made up of organic chemicals/clay insert, this insert has carried out ion-exchange, and with one or more quaternary ammonium compounds with further be blended into anionic materials (such as NaLS) reaction in the fluoropolymer resin, and inserting, thereby preparation nanocomposite composition.This material can be blended in the various polymer.This class system is fully disperseed in many dissimilar polymer, and has special-purpose at non-polar polymer in such as PE and PP.

Another kind of insert is made up of the functionalized organic monomer with at least one hydroxy functional group and/or aromatic ring.Inserting the agent monomer should preferably include the aromatic ring that fully is incorporated into clay platelet and/or have hydroxyl or polyhydroxy functional groups.This by providing in the insertion agent monomer molecule of stratified material and the adhesion between the plates inner surface with the combining of inner surface of phyllosilicate plates with the metal cation of the clay of the negative electricity atom shared electron of one or two hydroxyl or aromatic ring structure, and subsequently by using polymer, if preferred polyolefin polymers and suitable bulking agent make the clay layering such as handling with the maleic anhydride modified polyolefin of bulk polymer same type.

Another nanocomposite composition prepares by the common insertion of ion and anhydride-cured epoxy resin.By and gallery between the ion-exchange of inorganic cation, the ion-exchange between ion and plates surface is in conjunction with the existence of having eliminated the hydrone relevant with inorganic cation.Therefore, ion-exchange can be converted into hydrophobic surface with surface of clay in hydrophilic, and therefore hydrophobic epoxy polymer molecule can be inserted in the clay gallery then, thereby increases the d-spacing of adjacent layer.If suitably, epoxy resin can react with the suitable epoxy curing agent that joins in the bulk polymer, when suitable compounding, and then help layering, can further improve such formation nano composite material barrier property and improve CVD and conventional varnish/adhesive force with pipe sprays paint.

The insertion agent that another interesting collaborative insertion agent bond inserts agent by chain alkyl and/or contains aromatic ring is formed, the two stratified material complexing end at molecule has static functional group, be enough to provide insert agent with at the lip-deep interbed cation of the plates of stratified material, and from inserting that agent molecule extends or in the static complexing of the matrix polymer compatibility functional group of the free-end that inserts agent molecule.The long-chain that is fit to comprises polarity (static) end with the insertion agent that contains aromatic ring, has the hydroxy functional group of being selected from; The carbonyl functional group; Carboxylic acid or carboxylate functional group; Amine functional group; Amide functional group; Ether functional group; Ester functional group; Lactams functional group; Lactone functional group; The anhydride functional group; Nitrile functionality; Positive alkyl halide functional group; Pyridine functional groups; Pyrrolidones functional group; At least one structure division in carbon-to-carbon unsaturated bond (being olefine or alkynes) and their mixture is used at the layered inorganic material, for example the mixture of absorption or insertion agent or insertion agent between the adjacent plate-like bodies of phyllosilicate.

Another interesting collaborative insertion agent bond is made up of alkoxylate ion and EVOH.With compare with the nano composite material that bulk polymer does not have a this excellent compatibility, use this insertion agent bond, especially use the remarkable reduction of the OTR that the polymer with excellent barrier properties compatible with bulk polymer or other chemical group usually caused this type of nano composite material.The insertion agent (for example EVOH) that use has excellent barrier properties has usually obtained to have the nano composite material of improving barrier property, compares with the nano composite material for preparing with the insertion agent that does not possess the improvement barrier property.Under the situation of EVOH, organic nanometer granule for example can improve by the ethylene copolymer that uses EVOH and higher level with the compatibility of PE bulk polymer; If ethylene copolymer is enough high at the content that EVOH inserts in the agent, forming the required bulking agent of nano composite material can reduce, and even eliminates.

The amount of the modified clay material that combines with polymer in blend should be enough to the ESCR that provides required, intercepts and/or mechanical performance.The amount of the modified clay material in nano composite material generally is about 0.1 to about 25wt% of a composition.The preferable range that is used to prepare the modified clay material of pipe comprises about 0.5 to about 10% of composition.

Though more than enumerated some clay mineral, much less, had the long-pending any clay mineral (natural and synthetic) of large contact surface with the polymer that in described nano composite material, uses and can be used for making pipe.Similarly, much less, many meticulous, the ultra-fine or nano-sized particles that can form nano composite material can be used for the present invention, if especially it rise one or more polymer in blend polymer nucleator do the time spent.

In order to make any insertion but the not delamination degree of the gallery of the clay/organic clay of layering maximization, advantageously, this compound stands very high shear rate in manufacture process.

As mentioned above, according to this aspect of the present invention, provide nano particle to be used to improve the ESCR of polymer or blend polymer and/or the purposes of tearing strength, this type of blend is particularly suitable for preparing the flexible thin-gage goods of injection moulding such as pipe.

Preferably, the blend polymer of the 3rd aspect of the present invention has＞10, preferred＞20, more preferably＞30 and MFI most preferably＞50.The polymer that contains the nano-sized particles of compatilizer is commonly referred to as nano composite material, though this term more specifically is applicable to composite nano polymer/clay material.Do not wish to accept the opinion restriction, we think, when compatilizer is form of nanoparticles, with ' non-meticulous ' of identical weight or the more identical compatilizer comparison of coarsegrain form, when being incorporated into this type nano granular in the blend, the remarkable increase of the surface area of the compatilizer of set weight has caused the remarkable improvement of ESCR, obstruct and other physical property of blend polymer of the present invention.

Preferably, but unnecessary be that in order to be obtained just to intercept the optimum with regard to improving by nano composite material of the present invention, nano composite material for example stands high shear in the injection moulding process in moulding under high injection speed.The filling time mensuration injection speed that flows to downwards from injection point along the longest path from millimeter/0.1 of described cast gate molding point farthest second by polymer, this injection speed preferably＞35mm/0.1 second, more preferably＞45mm/0.1 second, also more preferably＞55mm/0.1 second, also more preferably＞65mm/0.1 second, also more preferably＞75mm/0.1 second, also more preferably＞95mm/0.1 second, also more preferably＞115mm/0.1 second, most preferably＞129mm/0.1 second.

At nanoparticle size compatilizer of the present invention is in the blend of polymer, in the time of in being dispersed in blend, the median particle of compatilizer is＜1000nm (1 μ m), more preferably 700nm also, more preferably＜500nm, also more preferably＜300nm, also more preferably＜200nm, also more preferably＜100nm, also more preferably＜75nm, most preferably＜60nm and＞1nm.Unless otherwise prescribed, ' granularity ' is meant particle mean size.

Contain and do not belong to polymer or clay, and preferably metal oxide such as TiO ₂, zinc oxide etc. or metalloid compound or metal the blend of the present invention of nanoparticle size compatilizer have＜200nm preferred＜100nm, most preferably particle mean size of 4-60nm.

Contain and do not belong to polymer or clay or metal oxide and comprise slaine such as those the blend of the present invention of meticulous, ultra-fine or nanoparticle size compatilizer of above definition, such as ultra-fine barium sulfate, it can have the granularity of 10nm.Especially, the present invention can also use other inorganic, metal oxide, zinc for example, conduction tin for example contains the tin oxide of antimony, iron, zirconium, aluminium, chromium, yttrium, europium, the particle of mixture of those and they as compatilizer.These powders have about 1-100nm, usually about 4 to about 60nm primary crystallites granularity.These crystallites can form has at the most the approximately agglomerate of the particle mean size of 300nm.

Wherein the nanoparticle size compatilizer blend that do not belong to polymer and have a following properties also falls within the scope of the present invention:

3) aspect ratio of the particle mean size of 0.9-100nm and 100-2000.

4) thickness of the nano particle of preferred 0.9-100nm and the width of 1500nm (1.5 μ m).

5) preferably have＜thickness of 2nm and the diameter of 10-1000nm.

Usually, various types of clays are than those are the preferred compatilizers that can have above characteristic as described in detail below.

For its medium clay soil and similar substance is the present invention of compatilizer, measure and only relate to platelet particles, do not relate to operable any dispersing aid or preliminary treatment compound, the platelet particles that is fit to has about 0.3 to about 3meq/g by belonging to, and preferably approximately the clay material of the free flowing powder of 0.8 to about 1.5meq/g cation exchange capacity (CEC) obtains.The example of the clay material that is fit to comprises mica group stratiform phyllosilicate, comprises clay, smectic clays, sodium montmorillonite, sodium hectorite (sodium hectorite), bentonite, nontronite, beidellite, wolchonskoite, saponite, sauconite, natural water glass, vermiculite, mica, kenyaite, synthetic sodium hectorite (sodium hectorite) etc.The clay of this character can be buied from many companies, comprises Southern Clay Products and Nanocor, Inc.

Other non-clay material with above-mentioned ion-exchange capacity and size also can be as the source of platelet particles of the present invention such as chalcogenide.These materials are well known in the art, and do not need here to describe in detail.

Nano particle, preferably have those of very high-aspect ratio, especially, but be not limited to form by modified clay mineral those, can be advantageously used for make the flexible thin-gage goods of injection moulding and by the whole bag of tricks such as extrude, the compatilizer of other goods of preparation such as rotational forming.When nano-sized particles was clay, they had several microns width usually, and thickness is nano level, therefore were called " nano-scale " particle.These clay particles roughly are the 0.1-25wt% of blend polymer, the 0.1-10.0wt% of preferred polymers blend.Each clay particle has the aspect ratio of the thickness and the 100-2000 of 0.9-100 nanometer, and this polymer can be used the promoter modification a little of integrating clay particle.

Except the barrier property that improves container and other goods, nano particle of the present invention can also improve the thin-walled flexible article such as container and the heat endurance and the mechanical performance of the other products of production thus.The heat endurance that increases of container is important, so that allow " heat is filled " to use." heat is filled " used the aseptic application of container in food-processing industry is provided, and also prolonged the pot-life of various food.Even also provide the ESCR of flexible thin-gage goods with respect to the nano particle of the little weight percent of polymeric material, significantly the increasing of impermeability and other physical property.

Nano particle/blend polymer of the present invention can be made by the whole bag of tricks, comprise as herein described those.

When the main polymer that is used to form nano composite material is polyolefin, have been found that all other conditions are identical, short-chain branched degree in the polymer (measuring by SCBI) is high more, the delamination degree of organic clay is high more, and therefore, the overall performance of nano composite material is good more.Similarly, under the situation of alkene alpha olefin copolymer and other copolymer, alpha-olefin or the percentage of other copolymer in polymer are high more, and the delamination degree of nano composite material is high more.Also have, the polymer with monomer super random distribution in polymer molecule is particularly suitable for producing nano composite material of the present invention, because their use has often obtained to be higher than the delamination degree of the similar polymer of the super random distribution with monomer.This super atactic polymer can come catalysis with metallocene well known in the art or similar catalyst.

The polymer that is applicable to nano composite material of the present invention for example, but be not limited to is for the described polymer of polymers compositions as above, comprise the polymer such as polyolefin, comprise plastic body, substantially linear metallocene polyethylene alpha olefin copolymer, low density polyethylene (LDPE) (LDPE), LLDPE (LLDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE) (HDPE), isotaxy, syndiotaxy and atactic polypropylene (PP) are such as the polypropylene with different isotaxy degree, such as especially at WO01/27169 (P﹠amp; G), WO99/52955 (Rieger), described in WO99/52950 (Reiger) and the WO99/29749 (ExxonMobil) those, ethene, the alpha olefin copolymer of propylene or butylene, preferably, use can form the metallocene of the super random distribution of alpha olefin copolymer in strand or the ethene of similar Preparation of Catalyst, the alpha olefin copolymer of propylene or butylene, polyamide such as poly-(meta-xylene adipamide) (MXD6), poly-(hexa-methylene decanedioyl amine), poly-(hexa-methylene adipamide) and poly-(caprolactam), polyester is such as poly-(ethylene glycol terephthalate), and polyacrylonitrile.Other polymer that is applicable to nano composite material of the present invention comprises ethylene-vinyl alcohol copolymer, and vinyl-vinyl acetate copolymer is with the polyester of maleic anhydride graft, PVDC, aliphatic polyketones, and LCP (liquid crystal polymer).The example of polyketone is the Carillon RTM that is produced by Shell.The example of liquid crystal polymer is the Vectra.RTM that is produced by Ticona.Operable other polymer comprises epoxy resin and polyurethane binder.

Though more than enumerated some clay material, should be understood that with the polymer that uses in described nano composite material has the long-pending any clay material (natural and synthetic) of large contact surface to can be used for the present invention.

Unless specifically set forth and limit or regulation is arranged in addition, the following term of Shi Yonging has the following implication that provides in this article.

" aspect ratio " is meant the width of certain objects and the ratio of thickness.

" layering thing " or " layering " are meant each plates of modified clay, and wherein the adjacent plate-like bodies of modified clay can be dispersed in carrier material individually such as water, polymer, and alcohol or glycol, or in any other organic solvent.

" layering " is meant the method that is formed the layering thing by modified clay.

" insertion agent " be meant between the plates of stratified material absorb and with Na on the plates surface ⁺The cation complexing, the organic molecule of formation insert is such as ammonium ion.

" insert " or " insertion " be meant and comprise between the adjacent plate-like bodies of stratified material, thereby interlamellar spacing between between the adjacent plate-like bodies is increased to less approximately 0.5nm, the preferred at least approximately stratified material of the organic molecule of 1nm.

" insertion " is meant the method that forms insert.

" stratified material " is meant inorganic material, such as the smectic clays material, exists with the form in a plurality of adjacent boundary layers, and each layer has about 0.3-0.5nm, preferably approximately the thickness of 1nm.

" matrix monomer " is meant the monomer that insert or layering thing mix with it or disperse.

" matrix polymer " is meant that insert and/or layering thing are mixed into and disperses in wherein, form the thermoplasticity or the thermosetting polymer of nano composite material.

" modified clay " is meant and carried out the stratified material that inserts.

" nano composite material " is meant and comprises the monomer that has wherein disperseed by many independently plates of layering modified clay acquisition, polymer, the mixture of oligomer or copolymer.

" plates " are meant each layer of stratified material.

Terre verte is 2: 1 type phyllosilicates, has the expandable lattice of the excessive negative electrical charge of the stratiform of carrying.2: 1 ratios are meant that layer structure is made up of the octahedra metal oxide lamella that is clipped between two tetrahedron silica lamellas.

The especially easy and intermediate material reaction of carbon-to-carbon double bond.This type of carbon-to-carbon double bond is usually at Food ﹠ Drink, medicine, and dyestuff, the photochemistry material is found in adhesive and the polymer precursor.In fact, any product with complicated organic principle contains this carbon-to-carbon double bond or other oxygen reactive component, therefore can carry out oxidation reaction.Therefore, if oxidation product influences the performance of product unfriendly, smell or fragrance so, are removed the oxygen (be dissolved in product or carried secretly by product) of existence, and anti-block enters, or the reaction that suppresses oxygen will help product.

In further studying, we find, oxygen scavenger is incorporated into to have significantly improved in the nano composite material is used for many application and (comprises film and by extruding or casting, notes draw, notes blow, thermoforming and well known to a person skilled in the art other plastic material manufacturing process) the oxygen barrier properties of nano composite material.The exploitation of nano composite material/oxygen scavenging compositions of the present invention especially but not only be suitable for the injection moulding of flexible thin-gage goods wherein requires oxygen barrier properties and other barrier property of improving.No matter polymer type, all nano composite materials are applicable to the present invention.For example, polyamide, such as various nylon polymers, polyester is such as PET and PEN, and Merlon and polyolefin especially are suitable for the present invention.Rely on low relatively cost and workability, especially, various types of polyolefin can be advantageously used in the present invention, and ' standard ' polyolefin with respect to independent use, olefin polymerization nanometer composite material and the polyolefin that contains oxygen scavenger, extraordinary obstruct of the present invention and Oxygen scavenging performance can make polyolefin need be used to barrier property, oxygen barrier properties especially, and be not suitable for their said polyolefins and the application of composition.

Though following argumentation mainly uses olefin polymerization nanometer composite material/oxygen scavenging compositions that the present invention is described, but it should be understood that, but same principle is applicable to compounding and becomes other polymer type of nano composite material/oxygen scavenging compositions, and therefore is included in the scope of the present invention.Term ' polyolefin ' therefore for example can be used replacements such as polyester, polyamide.Therefore, consider the above, the present invention includes:

Polyolefin composite/oxygen-scavenging compositions

Be used for polyolefin composite/oxygen-scavenging compositions that injection moulding is used

Polyolefin composite/the oxygen-scavenging compositions that is used for the flexible thin-gage goods of injection moulding of this paper definition

More specifically, have＞10, preferred＞20, more preferably＞30 and polyolefin composite/oxygen-scavenging compositions of MFI most preferably＞50

Also more specifically, have MFI＞10, preferred＞20, more preferably＞30 and the polyolefin composite/oxygen-scavenging compositions of polymers compositions most preferably＞50

Also more specifically, have MFI＞10, preferred＞20, more preferably＞30 and polymers compositions most preferably＞50 and introducing compatilizer and/or polymer be used to improve the polyolefin composite/oxygen-scavenging compositions of ESCR and barrier property

Preferably, when using the present invention to make flexible thin-gage goods, the filling time mensuration injection speed that flows to downwards from injection point along the longest path from millimeter/0.1 of described cast gate molding point farthest second by polymer, this injection speed preferably＞35mm/0.1 second, more preferably＞45mm/0.1 second, also more preferably＞55mm/0.1 second, also more preferably＞65mm/0.1 second, also more preferably＞75mm/0.1 second, also more preferably＞95mm/0.1 second, also more preferably＞115mm/0.1 second, most preferably＞129mm/0.1 second.

With basic identical, but nano composite material and oxygen-scavenging composition are that the combination of features thing compares with independent component, this based composition is particularly suitable for the injection moulding of flexible thin-gage goods, and this nano composite material/oxygen-scavenging compositions has shown the synergistic benefits with regard to barrier property (measuring as OTR).These compositions can pass through variety of way, such as by mix the alternate manner that each component of blend maybe can produce homogeneous mixture under the high shear mixing condition, for example prepare in double screw extruder.Nano composite material/oxygen scavenger blend can also be by at first preparing nano composite material and as independent process the oxygen scavenger compounding being prepared in nano composite material then.In addition, can prepare polymer/oxygen scavenger blend, subsequently with organic clay or its masterbatch compounding in this polymer/oxygen scavenger blend.The alternate manner that obtains well-mixed blend is that those skilled in the art institute is conspicuous.

In another modification of the present invention,, can use the molecule that can also play the oxygen scavenger effect as inserting agent by the suitable insertion agent that selection prepares the organic clay component of the nano composite material that is used for nano composite material of the present invention/oxygen scavenger blend.This for example can be by selecting to have the organic molecule of Oxygen scavenging performance as inserting agent or realizing by oxygen being removed functional group's grafting, polymerization or being incorporated in ' standard ' (that is, non-oxygen is removed) insertion agent.

US6423776 has described oxygen scavenger has been incorporated into effect in the polyamide/nano composite material film.Yet it does not describe any benefit of using polyolefin composite/oxygen-scavenging compositions, does not use nano composite material/oxygen scavenger bond being suitable for injection moulding yet, especially the purposes in the high relatively MFI composition of the flexible thin-gage goods of injection moulding.

For the present invention, the term polyolefin is meant that molecular structure is by surpassing 50% alkene such as ethene, propylene, the polymer that butylene is formed.In other words, aggregate into polymer the monomer molecule number be alkene more than 50%.Preferably, polyolefin is the low-molecular-weight plastic body, the substantially linear polyethylene, metallocene long-chain branched polyethylene or above-mentioned polyvinyl copolymer, linearity or branching isotaxy or syndiotactic polymer, especially polypropylene and polybutene homopolymers or random copolymer comprise linearity or branching isotaxy or syndiotactic polymer with steric regularity structure in 25-60% [mmmm] pentads concentration range, especially polypropylene and polybutene homopolymers or random copolymer.Be applicable to that also of the present invention is to have isotaxy and atactic block arbitrarily or the rather linearity or the branching isotachyte of sequence of rules in polymer molecule.

When the host polymer that is used to form nano composite material is polyolefin, have been found that under the identical situation of all other conditions the short-chain branched degree in the polymer high more (measuring) by SCBI, the delamination degree of organic clay is high more, so the overall performance of nano composite material is good more.Similarly, under the situation of alkene/alpha-olefin and other copolymer, the alpha-olefin in the polymer or the percentage of other copolymer are high more, and the delamination degree of nano composite material is high more.Also have, shown that in polymer molecule the polymer of super random monomer distribution is particularly suitable for preparing nano composite material of the present invention, because their use has often obtained than the higher delamination degree of similar polymer of the super random distribution of displaying monomer not.This type of super atactic polymer can come catalysis with metallocene well known in the art or similar catalyst.

There are many oxygen of nano composite material/oxygen scavenging compositions of the present invention that are applicable to remove system.They some is in following description, but other system of not describing also can be fit to.The adaptability of specific system can come to determine by experiment, and the best type of the nano composite material that is used in combination with in the present invention specific oxygen scavenger can come to determine equally by experiment.Above described all kinds of nano composite material and their various preparation methods, but it should be understood that described type and method are nonrestrictive.

US5,492,742 (Zenner) have described oxygen and have removed packing material and container, it comprise the carrier that can see through oxygen and water or steam such as polymer with effectively to be scattered in the organic compound of polymer equably or the oxygen of their salt is removed compound compositions as the amount of oxygen scavenger is relative.It is salicylic acid chelate or the complex or their salt of transition metal that oxygen is removed compound.Oxygen-scavenging compositions activates by contacting with water that penetrates or see through carrier or steam, so that remove oxygen.The reducing agent that can add the ascorbic acid salt compound improves the performance of salicylic acid chelate or complex.Oxygen is removed compound and can drying regime be joined in the composition, and is non-activity, up to being activated by contacting with water or steam, is used for the removing of oxygen.

The oxygen content of the packing material inside of the product of wet or moist for reducing fast (or can produce moisture) in packing material inside, but do not have the material or the product of taste, fragrance or the function of this packaged food of unfavorable change, beverage and medicine to exist demand.Those skilled in the art has considered various agents are joined in the packing material of this product, attempts to satisfy this requirement.

Japanese patent application 61-238,836 have disclosed by the packing film of thermoplastic such as low density polyethylene (LDPE) (" PE ") preparation, and it comprises independent ascorbic acid or it and aliphatic polycarboxylic acid's bond.This film is disclosed to have good gas barrier property.

Japanese patent application 54-022,281 disclose the fruit dish by thermoplastic foam base-material preparation, and it has the thin layer of ascorbic acid or arabo-ascorbic acid one of (or their alkali metal salt) at the recessed face of the dish of placing fruit.

Salicylic acid complex compound and they generally are known to the reactivity of oxygen, and people such as Zanello, Inoganica Chim.Acta 1983, the 74th volume, people such as 89-95 page or leaf and Cini, Inorganica Chim.Acta 1984, the 88th volume is stated in the 105-113 page or leaf.

In one embodiment of the invention, oxygen-scavenging compositions comprises the carrier that can see through oxygen and water or steam, such as polymer, and the preferred thermoplastic polymer; With replacement or unsubstituted salicylic transition metal complex or chelate or salicylate, be dispersed in relatively in this carrier, and add with the amount that enough plays the available oxygen scavenger.

The transition metal of chelate is iron preferably, copper, cobalt, or nickel; Most preferably it is iron or copper.The transition metal that is used to prepare chelate or complex compound can be used as simple salt, such as iron chloride or copper, and ferric sulfate or copper, Gluconate Ferrecex, nickelous sulfate, or cobalt chloride supplies with, but exist as the part of chelate or complex compound.

All right, and in some cases preferably, in polymer, introduce reducing agent, such as the ascorbic acid salt compound with enough raisings, maintenance or the amount that increases the Oxygen scavenging performance of transition metal chelate or complex compound.The ascorbic acid of D or L shaped formula, or their derivative, analog or salt can be used as preferred reducing agent, because it also has Oxygen scavenging performance.

By direct hybrid technology oxygen being removed material is scattered in the carrier equably.Advantageously, oxygen removing material is sneaked into or is blended in the carrier with dry state.The oxygen scavenging capacity of these compositions activated by contacting with water that penetrates or see through carrier or steam afterwards.

US5,641,825 (Bacskai) have described the composition of the material with oxygen scavenging capacity.Said composition comprises: contain polyolefinic first polymers compositions, this first polymers compositions is with unsaturated carboxylic acid anhydrides or unsaturated carboxylic acid or their bond or epoxides grafting; Have OH, SH or NHR ²Second polymers compositions of group, wherein R ²Be H, C ₁-C ₃Alkyl replaces C ₁-C ₃Alkyl; And can Catalytic Oxygen and second polymers compositions between the slaine of reaction, this polyolefin exists so that blend does not produce the q.s that is separated.In preferred compositions, maleic anhydride is a graft materials, and second polymers compositions is that MXD6 nylon and metal are cobalts.Giving provides polyolefin and has OH, SH or NHR ²The method of the even blend of second polymers compositions of group.Provide the goods that adopt this based composition and/or these class methods such as the Food ﹠ Drink container.

US5,952,066 relate to aliphatic polyketones as the novel use of oxygen scavenger in the structure of the oxysensible product of packing.With the modification aliphatic polyketones, thereby make it not opposite with the prior art that does not see through oxygen with the oxygen reaction, the present invention utilizes the hyperoxia reactivity of polymer, thereby effectively catches any oxygen that can enter product, has therefore improved and has deposited the time limit.As additional benefits, at the carbon dioxide (CO of packing material sidewall gathering ₂) (as catabolite) expection reduced CO ₂Migration from food.

In another embodiment, provide the single-layer and transparent packing material, wherein aliphatic polyketones and other polyblend or copolymerization.For example, the use comprises the polyketone terpolymer scavenger of 0.1-10wt% and the blend of remaining PET forms injection moulding preform and transparent foaming preform beverage bottle.Under low relatively content, it is amorphous that polyketane polymers keeps, and container is transparent (opposite with opaque obstruct polyketone with the high crystallization that this area proposes) basically.In this embodiment, directly contact with product based on food, terpolymer can be removed the oxygen from container.

Second olefinic type monomers can be incorporated in the polymerization such as propylene, it will optionally substitute ethene, and replace, thereby form terpolymer poly-(ethene-alternately (alt)-carbonoxide)-stat-(propylene-alternately-carbon monoxide) (E/P/CO terpolymer hereinafter referred to as) with carbon monoxide.E/P/CO only is an example of terpolymer, also has different many other the possible terpolymers of performance.In addition, but can introduce one or more other olefinic monomers of copolymerization, such as acrylate, methacrylate, alkyl compound, vinyl acrylate, vinyl silanes, vinyl chloride etc.Additive is such as the alcohol aldehyde sealer, and lubricant, releasing agent etc. can be used for improving processing characteristics and reduce the tendentiousness of aldol condensation.

US6,254,804 have discussed the various oxygen that are introduced directly in the packaging structure removes material.This technology (hereinafter referred to as " active oxygen obstruct ") can provide the even removing effect that spreads all over packing material, and the mode that can provide interception and removing to pass through the oxygen of packing material wall, and therefore keeping spreading all over the minimum of whole packing material may oxygen content.Formed the active oxygen barrier by introducing inorganic powder and/or salt as the part of packing material.For example referring to US patent No.5,153,038,5,116,660,5,143,769 and 5,089,323.

EP 0 519 616 has disclosed oxygen-scavenging compositions, and it comprises the blend of following material: epoxides, with first polymers compositions of unsaturated carboxylic acid anhydrides and/or sour grafting; Have OH, SH or NHR ²Second polymers compositions of group, wherein R ²Be _H, C ₁-C ₃Alkyl replaces C ₁-C ₃The alkyl structure part; And can Catalytic Oxygen and second polymers compositions between the slaine of reaction.This first polymers compositions is to guarantee that enough blend does not produce the amount that is separated and exists.Adopt the blend of polymer to obtain the oxygen removing, and second polymers compositions preferably (is total to) polyamide such as MXD6.

EP-A-0 301 719, and EP-A-0 380 319, and PCT publication number WO90/00578 and PCT publication number WO90/00504 have illustrated another kind of active oxygen barrier.Also referring to US patent Nos.5,021,515,5,194,478 and 5,159,005.Disclosed oxygen scavenger comprises polyamide-transition-metal catalyst composition.By removing with polyamide catalysis, this packing material wall has been regulated the amount that arrives the oxygen of packing material inside.

US patent No.5,399,289 disclose oxygen-scavenging compositions, and it comprises transition-metal catalyst and has the polymerization of ethylenically unsaturated hydrocarbons thing of the olefinic double bond content of 0.01-10 equivalent/100g polymer.Multiple common homopolymers, copolymer and blend polymer are disclosed.

US patent No.5,211,875 have instructed transition metal and light trigger to be used to cause effective purposes of removing activity of alefinically unsaturated compounds; This patent is incorporated herein for reference, just looks like that it sets forth the same all sidedly at this paper.

PCT publication number WO95/02616 and WO96/40799 disclose the scavenger composition, and it comprises transition metal salt and has the copolymer (copolymer of ethene and vinyl monomer) of ether, amino, carboxylic acid, ester or the amide functional group of side extension.PCT application WO96/40799 has described has benzyl, or the purposes of the various olefinic material of ether-containing side-chains.In these materials some can prepare by the esterification or the ester exchange of polymer melt.Generally mentioned the use of the side link shape group that contains unsaturated bond.

Therefore, described patent seeks to solve the problem relevant with the pyrolysis product of oxygen scavenger, and also seeks to provide one group of compound with compared with prior art advantage and material (and film and plastic material of comprising them) with regard to the amount that reduces pyrolysis product.

Ideally, the polymeric material that is used for oxygen-scavenging compositions should show good processing characteristics, can be shaped to useful packaging material or have and be generally used for preparing the high-compatibility of those polymer of packaging material, and not produce the byproduct of the color, taste or the smell that diminish packaging product.Have been found that when when cyclic group contains ethylenic unsaturated bond, compare, when oxidation, produced significantly less accessory substance with similar no ring material.It would be desirable, can remove its physical property of back maintenance at a large amount of oxygen by the packaging material that this composition forms.The oxygen removing compound that is used for plastic foil is that everybody relatively knows.

Have been found that the material that contains some cyclohexenyl group functional group is excellent oxygen absorbent, and when these material oxidation, they have produced extremely low-level oxidized byproduct when with transition metal salt and optional light trigger compounding.This is obviously opposite with known technology.In known technology, can obtain excellent oxygen absorbent by the linear unsaturated compound of use and transition metal salt and light trigger compounding, but the content of oxidized byproduct is too high.It is believed that because the mild oxidation of cyclohexene can not interrupt the key on the ring structure, and linear unsaturated material such as linoleic acid or vegetable oil the oxidation under conditions of similarity split by chain and produced less molecule.In the time of in being incorporated into polymer, find that the system that contains cyclohexene has produced than the significantly less volatile byproducts of linear unsaturated material.

Composition of the present invention is more described than in the prior art, and those are obviously cleaner, and they do not need to use high-caliber auxiliary agent to absorb undesirable accessory substance.This absorbing additives is well known in the art, for example referring to US patent No.5, and 834,079 and US08/857,276.Also be well known that in the art, examples of such additives (zeolite and silica) adverse effect the turbidity and the transparency of packaging structure.

Oxygen-scavenging compositions of the present invention comprises:

(a) contain the polymer or the low molecular weight material of substituted cyclohexene functional group.

(b) transition-metal catalyst; With optional

(c) light trigger.

The light trigger that is fit to is that those skilled in the art is known.For example referring to the open WO97/07161 of PCT, WO97/44364, WO98/51758, and WO98/51759, they be taught in this paper introduce for reference, just look like here set forth fully the same.

Combine with polymers compositions, oxygen-scavenging compositions of the present invention has comprised the transistion metal compound as the oxygen scavenger catalyst.Transition-metal catalyst can be the salt that comprises the metal in first, second or the 3rd transition series that is selected from periodic table.

One or more antioxidants can be incorporated in the removing composition of the present invention, are used to stop component to degrade between compounding and film forming stage.Remove active induction period though these additives have prolonged at the oxygen that does not have to take place under the situation of radiation, this layer or goods (with the light trigger of any introducing) can be exposed to radiation when the needs Oxygen scavenging performance.The antioxidant that is fit to comprises 2,6-two (tert-butyl group)-4-methylphenol (BHT), 2,2 '-methylene-two (the 6-tert-butyl group-paracresol), triphenyl phosphite, three-(nonyl phenyl) phosphite esters, thiodipropionate dilauryl, vitamin E (alpha-tocopherol), 3,5-di-t-butyl-4-hydroxyl hydrocinnamic acid stearyl, four [methylene (3,5-di-t-butyl-4-hydroxyl hydrogenated cinnamate)] methane etc.

When antioxidant comprises as the part of composition of the present invention, its preferred in case block remove the component of composition and be present in the gained blend other material form and processing during the amount of oxidation exist; Yet this amount preferably is lower than the amount that influences gained layer, film or the goods removing activity after initiation.Required amount depends on existing component in set composition, and used special antioxidants is used to form the hot worked degree and the amount of moulded products, and the dosage and the wavelength that are used to cause the radiation that oxygen removes.Usually, this antioxidant uses with about 0.01 to about 1wt% amount.

Also other additive that can comprise in oxygen-scavenging compositions of the present invention comprises but is not necessarily limited to filler, pigment, dyestuff, processing aid, plasticizer, antifoggant, antiblocking agent etc.

Compare with the composition that comprises common acyclic olefinic unsaturated polymer, composition of the present invention can provide the Oxygen scavenging performance of desired rate and ability, has good processing and compatibility performance simultaneously.Therefore, the present composition itself or as with the blend of diluted polymer such as polyolefin etc., be used to provide the packaging material or the film of easy manufacturing and processing.In addition, this oxygen-scavenging compositions consumes the oxygen in the packing material lacuna, and the color of the product that not obvious infringement wherein contains, taste and/or smell.

The amount that the polymer that contains in said composition is removed component can be about 1 to almost about 100% of the composition for preparing thus or a layer, preferably approximately 5 to about 97.5%, more preferably about 10 to 95%, also more preferably about 15 to about 92.5%, also more preferably about 20 to about 90% (above all percentage by weight).Usually, the amount of transition-metal catalyst can be the 0.001-1wt% of composition, only is benchmark (that is, not comprising part, counter ion counterionsl gegenions etc.) in the tenor.If one or more other remove compound and/or diluted polymer uses as the part of composition, these other materials can account for the nearly 99wt% that removes composition, preferably up to about 75wt%.Employed any other additive normally is no more than the 10wt% that removes composition, preferably is no more than about 5wt%.

The packing container that US6274210 has described improved oxygen-scavenging compositions and formed thus.This container is suitable for storing oxysensible material, as a part that is exposed to inner surface, has by polymer substrate and is distributed in wherein basic water-insoluble oxygen scavenger and the composition formed of the basic water-insoluble compound that contains transition metal.This oxygen-scavenging compositions comprises and contains (a) non-polymeric oxygen scavenger and (b) organic affinity is higher than the carrier of the water-insoluble oxygen of the affinity of water being removed catalyst.More specifically, this catalyst is made up of water-insoluble transistion metal compound.This oxygen-scavenging compositions provides from internal tank and has effectively absorbed oxygen, but does not have the advantage of color, taste or the smell of the packaging material that adverse effect wherein contains.

Known in the artly be ascorbic acid salt compounds (ascorbic acid, its salt, optical isomer, with their derivative) and sulphite can be by molecular oxygen oxidation, therefore can remove the component of formulation as oxygen, for example as the component of sealing material (closure compound).For example, license to people's such as Hofeldt US patent No.5,075,362 has disclosed ascorbate purposes as oxygen scavenger in the seal of vessel thing.

Be desirable to provide very much the available oxygen scavenger system that is suitable for packaging applications, this system has good oxygen uptake ability, and does not ooze out from system, so that the color of adverse effect packaging material, taste or smell.

Further be desirable to provide improved container, it has introduced the described oxygen-scavenging compositions as the part of the inside of container, is used to provide effective oxygen to remove, and does not have color, taste or the smell of adverse effect packaging material.

The present invention relates to the oxygen uptake ability that can provide good, do not have adverse effect having the oxygen-scavenging compositions of described composition simultaneously as color, taste or the smell of the material of its a part of container inner packing.This oxygen-scavenging compositions is by polymer substrate and be scattered in ascorbic acid salt compound in this matrix and the basic water-insoluble organic compound of transition metal is formed.

The oxygen-scavenging compositions of at least a basic water-insoluble transistion metal compound of the reaction that comprises at least a non-polymeric oxygen removing material and effective Catalytic Oxygen and oxygen removing material is provided in one aspect of the invention.In a preferred embodiment of the invention, this oxygen-scavenging compositions is made up of at least a water-insoluble oxygen removing material and at least a water-insoluble transistion metal compound.

In another aspect of the present invention, provide the polymer composition that comprises polymer substrate and be incorporated into above-mentioned oxygen-scavenging compositions wherein.

Especially, this polymeric material generally can be selected from polyolefin, polyethylene for example, polypropylene, ethylene/propene copolymer, the ethylene/propene copolymer of acid modification, polybutadiene, butyl rubber, styrene/butadiene rubbers, the carboxylated phenylethylene/butadiene, polyisoprene, styrene/isoprene/styrene block copolymer, styrene/butadiene/styrene block copolymers, styrene/ethylene/butylene/styrene block copolymer, ethylene, ethene/acrylic ester and ethene/(methyl) acrylate copolymer (for example, ethylene/butyl acrylate or ethylene/methacrylic acid butyl ester copolymer), the ethylene/vinyl alcohol copolymer, ryuron and copolymer, styrene/acrylic base polymer, polyamide, and vinyl acetate polymer, and their one or more blend.The polyethylene that can be used for forming described composition comprises high density polyethylene (HDPE) (HDPE), low density polyethylene (LDPE) (LDPE), LLDPE (LLDPE), ultra-low density polyethylene (ULDPE) etc. and copolymer of forming by ethene and one or more other lower alkanols alkene (for example octene) etc.

In this embodiment, especially preferred composition according to the present invention is by polyethylene or poly copolymer, for example Ethylene/vinyl acetate etc. or polyethylene blend, for example blend of HDPE and butyl rubber; The blend of polyethylene and ethylene; And the thermoplastic compounds that forms such as the blend of polyethylene and styrene/butadiene/styrene block polymer.If use, polyethylene is low density polyethylene (LDPE) preferably, and can be extremely low or ultra-low density polyethylene, and they can be branching or linearity.If use, ethylene preferably has 3-15, and the melt index (MI) of preferred 5-10 generally contains 5-40%, preferred 5-30% vinyl acetate.

Can be used for the oxygen scavenger of effective oxygen-scavenging compositions of the present invention is provided is ascorbate and erythorbate (as free acid, salt and derivative), alkali metal, the sulphite of alkaline-earth metal or ammonium or their mixture.Most preferred oxygen scavenger is the water-insoluble ascorbate.

Described oxygen-scavenging compositions preferably uses ascorbate or arabo-ascorbic acid salt compounds or their mixture to form.Preferably with ascorbate and erythorbate as ionic metal salt alkali metal salt for example, or alkali salt, or as organic acid ester (esterification on 5 or 6 hydroxyls of ascorbic acid) or other derivatization ascorbate [for example, wherein 5 or 6 hydroxyls and organic compound reaction, provide thus and do not replace or replace (carbonyl, carboxyl, hydroxyl, ether) branch's group] be incorporated in the composition.Oxygen scavenger ascorbate and/or erythorbate component can be replenished other known reducing agent, for example second ascorbate or erythorbate, tannin, sulphite etc.Preferably, this ascorbate and/or erythorbate can be unique oxygen scavengers or be the main scavenger of oxygen scavenger mixture at least.Unless otherwise prescribed, term in specification and appended claims " ascorbate " is meant as free acid, providing can be under the redox condition and their salt of the ascorbate of oxygen reaction, ascorbic acid and the arabo-ascorbic acid of their ester derivant and other derivative.

This oxygen-scavenging compositions can use alkali metal, alkaline-earth metal, the sulphite of transition metal or ammonium cation, or the mixture of described salt.Sulphite can or preferably can be used in combination with at least a ascorbate as unique oxygen scavenger.When using mixture, preferably, ascorbate is the main scavenger of said composition.

In preferred embodiments, oxygen scavenger can be selected from water-insoluble ascorbic acid salt compound, water-insoluble sulphite and their mixture.Water-insoluble sulphite is alkaline-earth metal and transition metal sulphite for example.The water-insoluble ascorbate is in following description.This scavenger can have not solubility of any water.Water-soluble low more, this agent is preferred more.For example, this agent can have the 10g/100cc of being lower than water under 25 ℃, preferably be lower than 4g/100cc water, more preferably less than 1g/100cc water with most preferably be lower than the water-soluble of 0.1g/100cc water.

The most preferred oxygen scavenger of the present composition is selected to have limited or not to have water-soluble ascorbic acid salt compounds.Preferably (esterification on 5 or 6 of ascorbic acid or 5 and 6 hydroxyls) is incorporated in the composition as alkali salt or as the ester of aliphatic acid or other organic derivative for ascorbate and erythorbate.Oxygen scavenger ascorbate component can be replenished other known reducing agent, for example second ascorbate or erythorbate, tannin, sulphite etc.

Described ascorbate is preferably with the form of basic water-insoluble salt, for example as alkali salt, and Calcium Ascorbate for example, ascorbic acid barium etc. is incorporated in the above-mentioned polymer substrate.Ascorbate can also be C ₆-C ₂₂The form of fatty acid ester or diester, they can be saturated fully or contain unsaturated bond, wherein C in hydrocarbon chain ₁₀-C ₂₂Fatty acid ester is preferred.Acid ascorbyl ester for example can be the laurate acid ascorbyl ester, myristic acid acid ascorbyl ester, ascorbyl palmitate, ascorbyl stearate etc.Saturated acid esters is preferred, most preferably ascorbyl palmitate.

The third component of described composition is to have limited or do not have water-soluble oxidation catalyst.

Find unexpectedly, can provide effective oxygen-scavenging compositions by using water-insoluble substantially organic or inorganic transistion metal compound; That is to say that it is highly hydrophobic, and when carrier is polymer substrate, have high affinity the organic polymer matrix of composition.The inorganic transistion metal compound of water-insoluble can be the form of salt or compound, and wherein transition metal combines with other element or group by ion or covalent bond.

The water-insoluble organo-transition metal compound can be the form of chelating agent, complex compound or organic carboxylate.The water-insoluble under 25 ℃ of catalyst should be lower than 4g, preferably is lower than 2g, also more preferably less than 1g, most preferably is lower than 0.1g/100cc water.Substantially completely water-insoluble is highly preferred.

Preferably, transistion metal compound is the compound with transition metal of highest oxidation state.The term that uses on the meaning of transiting metal oxidation attitude " compound " is meant the transition metal that preferably has high activity valence state and as is incorporated into the structure division that contends with so that the material of stable material to be provided in salt, complex compound or other form.Transition metal is the metal series from the scandium to zinc in the periodic table (that is, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu and Zn).Preferred compound is those of copper and iron, and wherein copper compound is most preferred.Even these catalyst have low from carrier, especially the polymer substrate that comprises them is moved to the tendentiousness of the aqueous phase that oxidation takes place, find unexpectedly that this oxygen-scavenging compositions provides and the comparable or more excellent performance of typical system of using water-soluble catalyst.

Provide other transistion metal compound of useful catalysts to comprise the zeolite that is loaded with transition metal ions.Be known that the zeolite (wherein this metal is 0 oxidation state) that metal supports can be used as elementary oxygen scavenger, and the oxygen of at least some not obvious other oxidation state of removing of same metal.Yet, have been found that being loaded with zeolite that metal wherein is in the metal ion of higher valence state can be used for the oxygen of another elementary oxygen scavenger of catalysis and remove active.

Preferred transistion metal compound is to have about C ₂-C ₂₀The monocarboxylic acid of carbon chain lengths and the slaine of dicarboxylic acids.Carbochain can be aliphatic series or aromatics, replacement or unsubstituted, and can contain unsaturated bond, and can be aliphatic acid.The low-solubility that these salt can have at ambient temperature in water arrives no dissolubility.The example of mono carboxylic acid of aliphatic series comprises acetate, propionic acid, butyric acid, valeric acid, laurate, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, stearic acid, nonadecylic acid etc.; Aliphatic dicarboxylic acid comprises malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, azelaic acid, decanedioic acid etc.; Acid with unsaturated bond comprises hydrosorbic acid, sorbic acid, butyric acid, glutaconate, hydrogenation muconic acid (hydromuconic acid), octendioic acid etc.; And aromatic acid, comprise benzoic acid etc.This acid can be by the alkyl of straight or branched, and the aliphatic group or the aromatic group that have 1-5 carbon atom usually replace.These acid can have and well known to a person skilled in the art other substituting group that does not influence the expection material that comprises in the gained packing container.When using, term " fatty acid " " for convenience former thereby use, it is not used for representing that it must be obtained by natural origin, because it can synthesize preparation.This term is meant the acid of high carbon number list, preferably has to be positioned at terminal carboxyl.Term " alkyl " is used for comprising alkyl and pure alkyl basically here.Explanation as these groups of basically alkyl is meant that they do not contain the non-hydrocarbyl substituent or the non-carbon atom of the alkyl characteristic or the performance of appreciable impact this type of group relevant with their purposes as described herein.

Therefore, described oxygen-scavenging compositions requires the water-insoluble transistion metal compound and is selected from ascorbic acid salt compound, the combination of the scavenger in sulphite or their mixture.Preferably, this catalyst is aforesaid organo-transition metal compound.In addition, preferably, this scavenger is selected from aforesaid basic water-insoluble ascorbate or sulphite.Therefore, the preferred compositions of scavenger and catalyst should make that scavenger and catalyst are water-insoluble, and most preferred combination is formed by water-insoluble ascorbate and organo-transition metal compound.Preferred transition metal is copper and iron, and wherein copper is most preferred.Scavenger and catalyst are in the carrier of aforesaid polymer substrate preferably.

Find unexpectedly, this oxygen-scavenging compositions provides and the comparable or more excellent performance of typical system of using water-soluble catalyst, even these catalyst have the tendentiousness that the low polymer substrate from comprising them is moved to the aqueous phase that oxidation takes place.

Oxygen scavenger can wide region consumption exist, depend on the application-specific of using said composition.Normally, it should exist with the amount of about at least 0.1wt%, based on the polymer substrate of composition.Give an example as following, in the time of in being present in composition, 0.1-90wt%, preferred 1-60wt% and most preferably the amount of 2-60wt% effective oxygen removing is provided.

The amount of scavenger depends on the type of application.When being incorporated into scavenger in the packing ring, this amount normally is based on the 0.1wt% at least of matrix material, usually 1wt% and preferably 2wt% at least at least.Amount above 20% is normally unnecessary, and 4-10% usually is the maximum that suits.Represent the amount of scavenger normally about 0.001-2g, more generally 0.02-1g/ container in another way.

When composition existed with the form of film, coating, mat, pouch or parcel, oxygen scavenger should exist with the amount of effectively removing oxygen in the expection shelf life of the suitable container of content.This amount normally is the standard-sized container of 0.01-2g/.

Under the situation of plastisol, lacquer or the hot melt of the central plate that puts on sealing, if matrix as packing ring, the dosage of scavenger can be higher so.For example, 20-60wt%, the dosage up to 90wt% is feasible in some cases.

Above-mentioned catalyst should be present in the mol ratio of about 3000: 1 to 20: 1 ascorbate and transition metal in the described composition, and is wherein 2000: 1 to 20: 1st, preferred, 1000: 1 to 100: 1st, most preferred.In some applications, this ratio can be greater or lesser, so that effective removing of oxygen to be provided.

Utilize the present invention,, can prolong the product quality of the oxysensible material in airtight container greatly or deposit the time limit by reducing the oxygen degree of degradation.

Preferably, scavenger is the basic inertia that keeps in described composition, in it is contained in airtight container till.As mentioned above, said composition is preferably anhydrous generally, and polymer substrate is also preferably anhydrous.Therefore, polymer substrate has prevented that basically scavenger from contacting with moisture under the ordinary atmospheric conditions.Composition contacts with the high humility of normal presence in airtight container and causes moisture fully to be penetrated in the composition as the part of container, thereby causes gratifying removing, and the time limit is deposited in the improvement that has obtained packaging material.Yet cleaning reaction can further quicken by the composition in the heated sealant container, thereby the moisture infiltration is increased.Therefore, preferably, scavenger is to keep basic inertia in carrier, up to by the material quicken cleaning reaction in the presence of moisture till.

For example, the cleaning reaction of said composition is by pasteuring (usually at 50-100 ℃) or sterilization (usually at the 100-150 ℃) container after with the filling of water base filler, re-uses composition of the present invention and seals and quicken.This triggers composition results seemingly, when heating, moisture is penetrated in the composition, is trapped in composition, thereby scavenger is contacted with the water of capacity, so that react with oxygen.This oxygen can be that the oxygen of holding back in by container when filling sees through the oxygen of composition, or is entered the oxygen of container afterwards by ambient atmosphere.

In said composition, can comprise the material such as surfactant ideally, neopelex for example, it will improve the permeability of composition to water.The Sq of suchlike surfactant is 0.1-1.0wt%.

In preferred embodiments, this concentrate was with 1: 38 to 1: 1, and more preferably the ratio of 1: 13 to 1: 1 concentrate and base resin dilutes.In these concentrate formulations, preferred use about 10-50wt% and more preferably approximately the amount of the oxygen of 20-40wt% removing compound is (promptly, for the compound of molecular weight with 200-500g/mol, about 500-2500, preferred 1000-2000 μ mol scavenger compounds/g polymer).When using ascorbate as scavenger, the catalyst of transition metal element compound or complex compound can use (that is 40-200 μ mol/g polymer) with the amount of about 0.3-8wt%.More preferably, catalyst uses with the amount of about 0.6-2wt%.

Those skilled in the art understand, the percentage of the various types of blend component that illustrate in above example can change according to the desired properties of mechanograph, and the percentage that forms all kinds of blend component of acceptable mechanograph can come to determine by experiment.

Claims

1, make the method for flexible thin-gage goods, comprising:

Main body by the plastic material injection-molded item;

Equipped this main body is to form goods; With

With this plastic material annealing.

2, basis the process of claim 1 wherein that annealing steps carries out on the spot by using the medium filled articles with abundant high-temperature, thereby by promote the annealing of goods to the heat transmission of goods itself by medium.

3, according to the method for claim 2, the temperature of the medium of wherein annealing is higher than 18 ℃, more preferably is higher than 22 ℃, also more preferably is higher than 25 ℃, also more preferably is higher than 30 ℃, most preferably is higher than 35 ℃.

4, according to the method for claim 1, wherein annealing steps carries out in the storage area of heating or natural warming in the storage process of final packaging product, wherein temperature constant or regularly be elevated to or make it to rise to 〉=22 ℃, more preferably 〉=25 ℃, also more preferably 〉=27 ℃, even more preferably 〉=30 ℃, most preferably 〉=35 ℃, and keep making enough time of plastic material annealing.

5, only annealed in the selection zone of plastic material according to the process of claim 1 wherein.

6, make the method for flexible thin-gage goods, comprising:

With (a) at least a polymer and (b) the blend injection moulding of at least a high melt flows compatible polymer.

7, according to the method for claim 6, wherein high melt flows compatible polymer has and is higher than 100, preferably is higher than 200, more preferably is higher than 300 MFI.

8, according to the method for claim 6, wherein (a) and at least a polymer that uses metallocene or similar catalyst system to form that comprises (b).

9, method according to Claim 8, wherein component (a) and (b) comprise propylene and/or ethene polymers or copolymer simultaneously.

10, according to the method for claim 6, be benchmark by (a) and gross weight (b) wherein, component (a) exists with about amount of 40 to about 99.9wt% of blend, and has formed the continuous of blend or be total to continuous phase.

11, according to the method for claim 6, wherein (a) polymer is included in the polypropylene that has different steric regularities in its structure.

12, according to the method for claim 6, wherein blend comprises that further (c) is scattered in nano particle wherein.

13, make the method for flexible thin-gage goods, comprising:

Injection moulding comprises (a) at least a polymer, (b) is scattered in the nano particle in this polymer and/or the blend polymer of nano composite material.

14, blend polymer, it comprises at least a polyolefin, compatible polymer and nano particle and/or nano composite material.

15, according to the blend polymer of claim 14, wherein polyolefin comprises mPE, and compatible polymer is that polypropylene homopolymer or copolymer and nano particle and/or nano composite material comprise nano clay nano composite materials.

16, according to the blend polymer of claim 15, wherein polyolefin comprises mPE and LDPE, MDPE and/or HDPE.

17, nano particle is used to improve the ESCR of polymer or blend polymer and/or the purposes of tearing strength.