CN1246130A - Heteromorphic polymer compositions - Google Patents

Abstract

The subject invention pertains to heteromorphic polymer compositions characterized as comprising: (a) a homogeneous linear or substantially linear ethylene/ alpha -olefin interpolymer backbone; and (b) a branch appending from the backbone, which branch comprises an ethylene homopolymer or ethylene/ alpha -olefin interpolymer having a density which is at least 0.004 g/cm<3> greater than that of the backbone. At least one of the backbone polymer or the branch polymer may be optionally functionalized to promote adhesion to polar surfaces. The heteromorphic polymer compositions of the invention exhibit enhanced upper service temperature. Also disclosed is a process for preparing the heteromorphic polymer compositions of the invention.

Description

Heteromorphic polymer compositions

The present invention relates to the polymorphic olefin polymer.Especially, the present invention relates to olefin polymer, this polymkeric substance comprise homogeneously branched line style or basically line style the ethylene/alpha-olefin interpolymer skeleton and attached to the Alathon or the ethylene/alpha-olefin interpolymer long-chain branch of the higher density on this interpolymer skeleton.

The homogeneous ethylene/alpha-olefin interpolymer is characterised in that narrow molecular weight distribution and narrow short-chain branch distribute.In addition, at U.S.5, in 272,236 and U.S.5,278,272, the open and claimed homogeneous ethylene interpolymer that contains long-chain branch, the ethene polymers of promptly so-called " line style basically ".

The shortage of low-molecular-weight, waxy component, and make the equally distributed ability of comonomer makes and can produce high-quality elastomerics, ethylene/propene elastomerics for example, ethylene/butylene elastomerics and ethylene/octene elastomerics etc.But, since the homogeneous phase line style or basically linear ethylene polymer lack the feature (having high crystallization melting peak like this) of the height line style fraction of heterogeneous branched polyethylene, the homogeneous phase line style or basically the polyethylene of line style tend to have the worse high thermal resistance of heterogeneous branched polymer than same density, particularly be lower than 0.920g/cm when density polymer ³The time.For example, the homogeneous phase line style or basically the elastomerics of line style may or more lose its intensity under the low temperature at 60 ℃.This is owing to this fact, and promptly the molecular characterization of low-density like this polymkeric substance is, has fringed micelle, and lacks the laminate structure of higher melt usually.Be mentioned though this difference is less, even have the line style or the linear ethylene polymer basically of the higher density of laminate structure, also usually in that the suitable thing of heterogeneous branching melts under lower temperature than it.No matter use which kind of polymerizing catalyst, polyethylene all is restricted in its practical application more than crystalline melt point, and this temperature is no more than about 140 ℃.

By with the polyethylene of high-crystallinity level and the mixed with resin of low-crystallinity elastomerics level, can improve the use temperature of elastomerics level.But high thermal resistance still needs to improve biglyyer.And generally speaking, along with the increase of the amount of higher density component, high thermal resistance improves, and modulus also increases and (like this, is being lower than 0.900g/cm with density simultaneously ³The homogeneous phase line style or basically under the linear ethylene polymer blended situation, elastomer performance has reduced fallaciously).With density greater than 0.900g/cm ³The homogeneous phase line style or basically under the linear ethylene polymer blended situation, along with the increase of the amount of higher density component, high thermal resistance improves, but resistance to tearing and shock-resistance have reduced fallaciously.

U.S.P 5,530, and 072 discloses the polymkeric substance with long-chain branch, are to use radical initiator to be prepared from grafting by linear polyethylene.Although it is so from grafting poly molecular weight is increased, and improved melt strength, but it does not influence poly degree of crystallinity, and does not therefore influence poly high thermal resistance.

U.S.P 5,346, and 963 disclose the linear ethylene polymer basically of graft modification, this ethene polymers selectively with thermoplastic polymer, for example high density polyethylene(HDPE), LLDPE and new LDPE (film grade) blend.

The elastomerics that has the high-temperature behavior of improvement and do not sacrifice modulus and/or resistance to tearing and shock-resistance is of great use in industry.The high-temperature behavior of this improvement can for example demonstrate advantage in the shoe sole applications, the heat that such sole can more anti-clothes-drying machine.In another example, the high-temperature behavior of this improvement can demonstrate advantage in using at for example pressure sensitive adhesive, can show the creep resistant of reduction.

In this employed term " polymer " ", be meant compound, no matter monomer is identical or different by the monomer polymerization preparation.Like this, class noun " polymkeric substance " comprises term " homopolymer ", and it only is commonly used to refer to the polymkeric substance by a kind of monomer preparation, and term " interpolymer ", and it is defined as follows.

Term " interpolymer " is meant the polymkeric substance by at least two kinds of different monomer polymerization preparations.Like this, class noun " interpolymer " comprises term " multipolymer ", and it is commonly used to refer to the polymkeric substance by two kinds of different monomers preparations, with the polymkeric substance by two or more different monomers preparations.

The invention reside in unique polymer composition, comprising: (A) homogeneous phase line style or the ethylene/alpha-olefin interpolymer skeleton of line style basically; (B) attached on this interpolymer skeleton, and its density is than first interpolymer skeletal density height 0.004g/cm at least ³Alathon or ethylene/alpha-olefin interpolymer.Such polymer composition, than the physical blending thing or the reactor blend of comparable first and second interpolymers, at high temperature more anti-distortion.The improvement of this high-temperature behavior is reflected in the higher use temperature under load (ULST) value, promptly makes the tendency of this heteromorphic polymer compositions surrender owing to softening/thawing, and this value is with rheology solid analysis instrument, measures with method as described below.

Though do not wish to be bound by theory, we believe, Fig. 1 has illustrated and has been used for improving the homogeneous phase line style or the Materials science principle of the elastomeric high-temperature behavior of line style basically.As shown in Figure 1, elastomerics is as soft section, and heteromorphic polymer compositions snappiness at room temperature is provided.In the grafting hard section, for example have the high density polyethylene(HDPE) of higher crystalline melt point, improved ULST, because should hard section cocrystallization advance in its oneself the little discrete areas, and with the elastomerics chain formation tridimensional network that connects together.

According to the difference of branched polymers composition and branch combining method, branch can have a lot of forms, and some examples wherein are shown in Fig. 2.Fig. 2-1 has shown the copolymer skeleton of line style basically, and three kinds of different polymkeric substance side chain mode of connection are arranged.Fig. 2-1 (a) illustrates the side chain that carries out " H-is connected " with skeleton polymer.This can carry out random crosslinking and introduce by the precursor polymer that for example makes skeleton polymer and polymorphic long chain branch.Fig. 2-1 (b) illustrates with 2 points (or multiple spot) and is connected to long chain branch on the skeleton polymer.If long chain branch still can cocrystallization or formed " firmly " phase, so that improve the thermotolerance and/or the physicals of polymkeric substance, this long chain branch combination is acceptable, and in the defined long chain branch scope of the present invention.Fig. 2-1 (c) illustrates side chain and skeleton polymer constitutes "T"-shaped.This can be by for example active end group of polymorphic long chain branch precursor polymer and obtaining in grafting on the skeleton polymer, perhaps in the polymerization process of skeleton polymer, make for example vinyl of active end group, obtain with monomer copolymerization (certainly in this case, " skeleton polymer " be a notion just, does not exist with pure form in essence).

Fig. 2-2 for example understands the example in the various variations, wherein has "T"-shaped polymorphic long chain branch on linear copolymers (2-2) skeleton polymer, is obtained by for example copolymerization or end group grafting.

Constituting the ethylene/alpha-olefin interpolymer (A) of the skeleton of polymorphic olefin polymer of the present invention, is the homogeneous phase line style or the ethylene/alpha-olefin interpolymer of line style basically, and the both will describe in detail below very much.

The density of skeleton polymer is decided according to the type of employed comonomer and amount.Its density can be controlled according to method known to those skilled in the art, with the pliability of controlling polymers from highly unformed elastomerics level to high crystalline inelastic body level.The selection of skeleton polymer density will be decided according to performance requriements well known by persons skilled in the art according to the requirement of each application.But the density of skeleton polymer is lower than 0.920g/cm usually ³, preferably be lower than 0.900g/cm ³, more preferably less than 0.880g/cm ³In the application that requires best elastomer performance, the density of skeleton polymer will be lower than 0.870g/cm ³, preferably be lower than 0.865g/cm ³, and the low 0.850g/cm that reaches ³Density can reach.

Similarly, the molecular weight of skeleton polymer also can change according to each individual system.When branched polymers is connected on the skeleton polymer by crosslinked or grafting, preferably reduces the molecular weight of skeleton interpolymer, thereby reduce gelification, particularly when graftomer is high-molecular weight or multifunctional active site.One aspect of the present invention is, even low-molecular-weight relatively skeleton polymer, because optimizing integration of being given of the polymorphic characteristic of the present composition also can obtain excellent physicals.Like this, the physicals that can obtain the simultaneously processing characteristics of becoming reconciled.

But, the melting index (I of skeleton polymer ₂) be generally 0.01～10,000g/10min., be preferably 0.01～1,000g/10min. melting index is preferably greater than 10g/10min. especially, it should be noted that more preferably greater than 20g/10min., for low-molecular-weight polymkeric substance, be that melting index is greater than 1,000g/10min. polymkeric substance, be by measuring polymkeric substance at 350 melt viscosity, representing its molecular weight better.Measure according to the technology that following Test Methods section proposed, melting index is 1,000g/10min. and 10, and the polymkeric substance of 000g/10min. is respectively about 8200 and 600 centipoises at 350 melt viscosity.

Attached to the branched chain polymer (B) on the polymer backbone (A), can be can be in the preparation process of skeleton polymer and any polymkeric substance of monomer copolymerization, or can grafting or be linked to any polymkeric substance on the skeleton polymer, and its density be than the big at least 0.004g/cm of density of skeleton polymer ³, preferably big at least 0.006g/cm ³, more preferably big at least 0.01g/cm ³Preferably, the second-order transition temperature (Tg) of purified branched chain polymer (B) or crystalline melt point (Tm), higher at least 10 ℃ than the Tg or the Tm (whichsoever higher) of purified skeleton polymer, be preferably up to few 20 ℃, most preferably high at least 50 ℃.It should be noted that for the object of the invention, term " grafting " expression is received an end group of branched chain polymer on the skeleton polymer, term " crosslinked " is used for then unsatisfactoryly representing that the tie point (promptly not being end group) by one or more other places on the long-chain branch precursor connects, and form the composition of polymorphous long chain branching, but be not be cross-linked into netted.

The non-limiting example of polymorphic long-chain branch material comprises heterogeneous and homogeneously branched linear ethylene homopolymer and ethylene/alpha-olefin interpolymer, reaches the Alathon and the ethylene/alpha-olefin interpolymer of line style basically, and each all will be described in greater detail below.Such branched polymers can also be carried out functionalized.

For the suitable branched chain polymer of a kind of skeleton polymer, may be not suitable for another kind of skeleton polymer.For example, be 0.865g/cm for a kind of density ³The homogeneous phase line style or the ethylene/octene interpolymer of line style basically, suitable branched polymers can be that density is 0.900g/cm ³The ethylene/octene interpolymer.But it is 0.920g/cm that same branched polymers is not suitable for being connected on density ³The homogeneous phase line style or basically on the ethylene/octene interpolymer skeleton of line style, because the former Tm is not than the latter's at least 10 ℃ greatly of Tm (and in fact significantly lower).

And the polymorphic long-chain branch should have enough molecular weight, so as can with other branched polymers molecule or the polymkeric substance cocrystallization that adds in addition or form one mutually.Preferably, the weight-average molecular weight (M of polymorphic long-chain branch _w) be 1000 at least, preferably be 3000 at least, measure according to the method that proposes in the following Test Methods section.

The amount of skeleton polymer should be enough to make it to form external phase or common external phase in skeleton polymer and polymorphic long chain branch mixture of polymers.Especially, the weight ratio of skeleton polymer and branched polymers is usually greater than 1: 3, and preferably at least 1: 2, and most preferably greater than 1: 1.Those skilled in the art will recognize that this optimum proportion will change with purposes, and can cause changing at aspects such as elastomer performance, high-temperature behavior, modulus/hardness.

The average number of the polymorphic long-chain branch on each polymer backbone molecule, should be enough to make final polymer composition on the measured thermotolerance of RSA, raising to be arranged, and/or raising arranged on tensile strength, these raisings should be greater than can comparing polymkeric substance without copolymerization, grafting or crosslinked, and only mix the raising that can provide through simple physical.The thermotolerance that the present composition is recorded by RSA is preferably than at least 10 ℃ of the thermotolerance height of the physical blending thing that can compare polymkeric substance, preferably at least 15 ℃.The ultimate tensile strength of the present composition, preferred be at least can compare polymkeric substance the physical blending thing ultimate tensile strength 70%, more preferably be 85% at least, most preferably equaling or exceeding the ultimate tensile strength of comparable polymer physics blend, is that 120% ultimate tensile strength of physical blending thing also obtains easily.

But the average number of the polymorphic long-chain branch on each polymer backbone molecule should not be reduced to unacceptable level to the elastomer performance that makes polymer backbone greatly.For example, the density when skeleton polymer is lower than 0.900g/cm ³The percentage elongation of the present composition preferably can compare polymkeric substance blend the percentage elongation at least 40%, more preferably at least 50%, most preferably at least 60%, the composition that equals or exceeds the percentage elongation that can compare blend also obtains easily.

The ethene polymers that can be used as polymer backbone (A) and polymorphic long-chain branch (B) can be the interpolymer of ethene and at least a alpha-olefin independently of one another.Suitable alpha-olefin is represented by following molecular formula:

CH ₂=CHR wherein R is an alkyl.Constitute the comonomer of skeleton polymer (A), can be identical or different with the comonomer that constitutes polymorphic long-chain branch (B).

R contains 1～20 carbon atom usually.The suitable alpha-olefin or its composition that are used as comonomer in solution, gas phase or slurry polymerization processes comprise C ₃～C ₂₀Alpha-olefin, vinylbenzene, tetrafluoroethylene, vinyl benzo tetramethylene, 1,4-hexadiene, 1,7-octadiene, and cyclenes, cyclopentenes for example, tetrahydrobenzene, cyclooctene, norbornylene (NB), and ethylidene norbornene (ENB).Preferred C ₃～C ₂₀Alpha-olefin comprise the 1-propylene, 1-butylene, 1-iso-butylene, 1-amylene, 1-hexene, 4-methyl-1-pentene, 1-heptene and 1-octene, and other monomer.The preferred 1-butylene of alpha-olefin, 1-amylene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, NB or ENB, or its mixture.Alpha-olefin is the 1-hexene more preferably, 1-heptene, 1-octene, or its mixture.Alpha-olefin is the 1-octene most preferably.

In the present invention, the ethylene/alpha-olefin/diene terpolymer also can be used as elastomer polymer.Suitable alpha-olefin comprises the alpha-olefin that is suitable for preparing ethylene/alpha-olefin copolymer described above.Be suitable as the monomeric diene of this based terpolymers of preparation, normally contain the non-diene of gripping altogether of 6～15 carbon atoms.The suitable non-typical example of gripping diene altogether that can be used for preparing terpolymer comprises:

A) straight chain acyclic diene, for example 1,4-hexadiene, 1,5-heptadiene and 1,6-octadiene;

B) acyclic diene of branching, 5-methyl isophthalic acid for example, 4-hexadiene, 3,7-dimethyl-1,6-octadiene and 3,7-dimethyl-1,7-octadiene and 1,9-decadiene;

C) monocycle alicyclic ring diene, 4 vinyl cyclohexene for example, 1-allyl group-4-isopropylidene hexanaphthene, 3-allyl group cyclopentenes, 4-allyl group-tetrahydrobenzene and 1-pseudoallyl-4-butenyl hexanaphthene;

D) thick and alicyclic ring and bridged ring diene, for example dicyclopentadiene of many rings; Alkenyl, alkylidene group, cycloalkenyl group and cycloalkylidene norbornylene, 5-methylene-2-norbornene for example, 5-methylene radical-6-methyl-2-norbornylene, 5-methylene radical-6,6-dimethyl-2-norbornylene, 5-propenyl-2-norbornylene, 5-(3-cyclopentenyl)-2-norbornylene, 5-ethylidene-2-norbornene, 5-cyclohexylidene-2-norbornylene, or the like.

Preferred diene is selected from 1, the 4-hexadiene, and dicyclopentadiene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, the 7-methyl isophthalic acid, the 6-octadiene, 4 vinyl cyclohexene, etc.A kind of suitable diene of gripping altogether is a 1,3-pentadiene.

Preferred terpolymer is ethene, propylene and a kind of non-terpolymer (EPDM) of gripping diene altogether in the present invention's practice.This based terpolymers is commercially available.

Can be used as component of the present invention (A) and homogeneous polyethylene (B) and drop in two wide categories i.e. line style homogeneous polyethylene and the homogeneous polyethylene of line style basically.Two kinds all is known.

" homogeneous " polymkeric substance is an ethenyl copolymer, and wherein in a given interpolymer molecule, all comonomers all are stochastic distribution, and in this polymkeric substance, all basically interpolymer molecule have identical ethene/comonomer ratio.The common characteristics of homogeneous polymer are to have with what dsc (DSC) recorded to be positioned at-30 ℃～150 ℃ single melting peak.This single melting peak is by measuring with the differential scanning calorimeter of indium and deionized water calibration.This method 3-7mg sample is heated to for the first time about 180 ℃ and kept 4 minutes, is cooled to-30 ℃ and kept 3 minutes with the speed of 10 ℃/min, carries out second time and heats, and is heated to 140 ℃ with the speed of 10 ℃/min.To time curve, draw this single melting peak by the heat content that heats for the second time.Total melting heat of polymkeric substance calculates from area under a curve.

For density is 0.875g/cm ³～0.910g/cm ³Polymkeric substance, according to the sensitivity of instrument, described single melting peak may show " acromion " or " hump " at the low end that melts, this peak constitutes below 12% of polymkeric substance heat of fusion total amount, the typical case is below 9%, more typical is below 6%.This phenomenon is for homogeneous phase simple linear polymer, for example Exact ^TMResin (can by Exxon ChemicalCompany obtain) also can be observed, and can be distinguished according to the slope of the single melting peak of the single variation by the additional peak melt region.Such additional peak appears in 34 ℃ of fusing point of single melting peak, and the typical case is in 27 ℃, and is more typical in 20 ℃.Be attributable to the heat of fusion of additional peak, can be by its heat content to the specific integration of the relevant area time curve under and definite respectively.

In addition, or as a kind of alternative, the homogeneous phase degree of polymkeric substance is described by CDBI (forming the distribution branch index) usually, and is defined as 50% the weight percentage with interior polymer molecule of co-monomer content for total mole co-monomer content intermediate value.Can calculate the CDBI of polymkeric substance at an easy rate by the data that obtain by technology known in the art, for example, intensification elution fractionation (being abbreviated as " TREF ") at this, be disclosed in for example Wild et al, Journal of polymer Science, Poly.Phys.Ed., Vol.20, p.441 (1982), U.S.P 4,798,081 (Hazlitt etal.), or U.S.P 5,089,321 (Chum et al.).The homogeneous phase line style used in this invention or the CDBI of the ethylene/alpha-olefin polymer of line style basically are preferably greater than 50%, more preferably greater than 70%.

The molecular weight distribution M of homogeneous polymer _w/ M _nBe usually less than or equal 3 (when the density of interpolymer is lower than 0.960g/cm ³The time), preferably be less than or equal to 2.5.Use the polystyrene standards ((Polymer Laboratories) obtains by the polymkeric substance laboratory) of narrow molecular weight distributions and, derive molecular weight in conjunction with its elution volume.Be equipped with on the Waters 150C high temperature chromatogram arrangement that differential refractometer and three mix the porosity pillars at one, analyze SLEPs by gel permeation chromatography.Pillar is by polymkeric substance laboratory supply, and to fill hole size usually be 10 ³, 10 ⁴, 10 ⁵, 10 ⁶Carrier.Solvent is 1,2, and the 4-trichlorobenzene becomes specimen preparation with this solvent the solution of 0.3% (weight) be used to inject.Flow velocity is 0.1ml/min, and the device service temperature is 140C, and sample size is 100 microlitres.

Use is for the suitable Mark-Houwink coefficient of polyethylene and polystyrene (by Williams and Ward at Journal of Polymer Science, Polymer Letters, Vol.6, p.621, open in 1968), utilization equation M _Polyethylene=a (M _Polystyrene) ^bThereby, determine suitable poly molecular weight.In this equation, a=0.4316, b=1.0.Weight-average molecular weight M _wUsually calculate according to following formula:

Mw=∑ (w _i* M _i) w wherein _iAnd M _iBe respectively i grade part weight fraction and the molecular weight that elutes from the GPC pillar.

Since homogeneous phase linear ethylene polymkeric substance is long-term has been commercially available.As the U.S.P3 of Elston, 645,992 is cited, can use Zieglar-type catalyzer in common polymerization technique, and for example zirconium and vanadium catalyst system prepare homogeneous phase linear ethylene polymkeric substance.The U.S.P4 of Ewen etc., 937,299 and the U.S.P 5,218,071 of Tsutsui etc., the use metallocene catalyst is disclosed, for example based on the catalyst system of zirconium and hafnium, preparation homogeneous phase linear ethylene polymkeric substance.The characteristic feature of homogeneous phase linear ethylene polymkeric substance is molecular weight distribution M _w/ M _nBe about 2.The business-like example of homogeneous phase linear ethylene polymkeric substance comprises the Tafmer that those Mitsui Petrochemical Industries are sold ^TMThe Exact that resin and Exxon Chemical Company are sold ^TMResin.

Basically linear ethylene polymer (SLEPs) is the homogeneous polymer with long-chain branch.They are disclosed in U.S.P 5,272, and 236 and 5,278,272.SLEPs uses Insite ^TMTechnology and catalyst technology preparation, can obtain by The Dow Chemical Company, commodity are called Affinity ^TMPolyolefin plastics (POPs) and by DuPont Dow Elastomers, LLC obtains, and commodity are called Engage ^TMPolyolefin elastomer (POEs).Can adopt solution, slurry or gas-phase polymerization process, preferred solution method technology is in the presence of a kind of catalyzer of constrained geometry, make ethene and one or more selectable alpha-olefin comonomer polymerizations, preparation SLEPs, for example at EP416, disclosed method among the 815-A.

The meaning of term " line style basically " is, except that comonomer equably in conjunction with the short-chain branch that forms, poly feature also comprises having long-chain branch, makes that per 1000 carbon atoms have average 0.01～3 long-chain branch on the polymer backbone.The polymkeric substance of the line style basically that the present invention uses preferably contains 0.01 long-chain branch/1000 carbon atom～1 long-chain branch/1000 carbon atom, more preferably contains 0.05 long-chain branch/1000 carbon atom～1 long-chain branch/1000 carbon atom.

" long-chain branch " (LCB) represents that chain length is at least 6 carbon atoms, surpasses this length, then can not use ¹³The C nuclear magnetic resonance spectrum is distinguished.Each long-chain branch has the comonomer distribution identical with polymer backbone, and can be identical with its polymer backbone length of adhering to.

The existence of long-chain branch in the ethene polymers can be used ¹³C nucleus magnetic resonance (NMR) spectral detection, and can use the disclosed method of Randall (Rev.Macromol.Chem.Phys., C.29, V.2﹠amp; 3, p.285-297) carry out quantitatively.

In fact, common ¹³The C NMR (Nuclear Magnetic Resonance) spectrum can not be measured the length of the long-chain branch that surpasses 6 carbon atoms.But, also have other known technology, can be used to the existence that is determined at ethene polymers, comprises the long-chain branch in the ethylene/octene interpolymer.Two kinds of these class methods are gel permeation chromatography (GPC-LALLS) that combines with low angle laser scanning detector and the gel permeation chromatography (GPC-DV) that combines with the differential viscosity detector.Described theory below the application of these technology in long-chain branch detects reaches, extensively record in the literature.For example see Zimm, G.H. and Stockmayer, W.H., J.Chem.Phys., 17,1301 (1949) and Rudin, A., the modern characterizing method of polymkeric substance (Modern Methods of Polymer Characterization), John Wiley; Sons, New York (1991) pp.103-112, both are as a reference in conjunction with in the present invention.

A.Willem deGroot and P.Steve Chum (two people are the employees of The Dow ChemicalCompany) are on the federal analytical chemistry and spectrum association (FACSS) meeting of holding in St. Louis, the Missouri State on October 4th, 1994, propose data declaration, the GPC-DV technology can be used to the long-chain branch that exists among the quantitative assay SLEPs.Especially, deGroot and Chum find, the long-chain branch level in the homogeneous phase SLEP sample that records with the Zimm-Stockmayer equation is with usefulness ¹³The long-chain branch level that C-NMR records is relevant well.

In addition, deGroot and Chum find that the existence of octene does not change the hydrokinetics volume of polyethylene specimen in solution, and therefore, by octene molecular fraction in the known sample, can calculate the molecular weight that causes owing to the octene short-chain branch increases.By getting rid of the contribution that 1-octene short-chain branch increases molecular weight, deGroot and Chum point out, GPC-DV can be used to the quantitative assay level of long-chain branch in the ethylene/octene of line style basically.

DeGroot and Chum also point out, by the Log (I of GPC-DV mensuration ₂Melting index) change curve with Log (GPC weight-average molecular weight) shows, long-chain branch aspect among the SLEPs (but not being the content of long-chain branch) is similar to the side chain of the new LDPE (film grade) (LDPE) of high pressure, high branching, and with use Zieglar-type catalyzer (for example titanium complex) and be generally used for preparing the prepared ethene polymers of the catalyzer (for example hafnium and vanadium complex) of homopolymer obviously different.

For ethylene/alpha-olefin interpolymer, long-chain branch is longer than being incorporated into the formed short-chain branch of polymer backbone owing to alpha-olefin.In the ethylene/alpha-olefin interpolymer of the line style basically that the present invention uses, prove that rule of thumb the effect that exists of long-chain branch is to have improved rheologic behavio(u)r, this point can be by the result and/or the melt flow ratio I of gas extrusion rheometry (GER) at this ₁₀/ I ₂Increase come quantificational expression.

Opposite with term " line style basically ", term " line style " expression polymkeric substance does not have detectable or evincible long-chain branch, that is, polymkeric substance on average is substituted with and is lower than 0.01 long-chain branch/1000 carbon atom.

The feature of SLEPs also is to have:

(a) melt flow ratio I ₁₀/ I ₂〉=5.63,

(b) by the molecular weight distribution M of gel permeation chromatography _w/ M _nSatisfy equation:

(Mw/Mn)≤(I ₁₀-I ₂)-4.63

(c) gas is extruded rheology, make the critical shear rate of SLEP when surperficial melt fracture begins, than the critical shear rate of linear ethylene polymkeric substance when surperficial melt fracture begins big at least 50%, wherein SLEP comprises identical comonomer or comonomer combination, the I of linear ethylene polymkeric substance with linear polyethylene ₂, M _w/ M _nWith density SLEP 10% in, and wherein SLEP and linear ethylene polymkeric substance critical shear rate separately are under same temperature of fusion, that the using gas squeezing rheometer records and

(d) the single dsc DSC melting peak between-30～150 ℃.

The critical shear rate and critical shearing stress and other rheologic behavio(u)r that relate to melt fracture, for example the mensuration of rheology processing index is (GER) that finishes with the gas squeezing rheometer.M.Shida, R.N.Shroff and L.V.Cancio, at polymer engineering science (Polymer EngineeringScience), Vol.17, No.11 is among the Page 770 (1977), show with John Dealy, the gas squeezing rheometer in the 97-99 page or leaf, has been described in " Rheometers for Molten Plastics " (1982) that Van Nostrand Reinhold Co. publishes.GER experiment is to carry out under 190 ℃ of temperature, nitrogen pressure be 250～5500psig (1.7～38Mpa), uses the die orifice of diameter, 180 ° of the angles that enters the mouth as 0.0754mm, 20: 1 length-to-diameter ratios.For linear ethylene polymer basically described herein, its PI value is that the material that recorded by GER is 2.15 * 10 ⁶Dyne/cm ²Apparent viscosity under the apparent shear-stress (0.215MPa) (with thousand pool expressions).The linear ethylene polymer basically that the present invention uses comprises ethenyl copolymer, and its PI value is that (0.01～50kg/cmsec), preferred 15,000 moor (15kg/cmsec) or lower to 0.01 thousand pool～50 thousand pools.PI value with herein linear ethylene polymer basically, (Zieglar polymkeric substance or Elston are at US P 3 to be less than or equal to the linear ethylene polymkeric substance, the even branched polymers of disclosed line style in 645,992) 70% of PI value, the I of described linear ethylene polymkeric substance ₂, M _w/ M _nWith density all linear ethylene polymer basically 10% in.

Basically the rheological behavior of linear ethylene polymer can also characterize with Dow rheology index (DRI), " the normalization method relaxation time that is caused by long-chain branch " of its expression polymkeric substance.(see, S.Lai and G.W.Knight ANTEC ' 93 Proceedings, INSITETM TechnologyPolyolefins (SLEP)-New Rules in the Structure/RheologyRelationship of Ethylene α-Olefin Copolymers, New Orleans, La., May1993) scope of .DRI value never contains any polymkeric substance that detects long-chain branch (for example, Tafmer that can be obtained by Mitsui Petrochemical Industries ^TMProduct and the Exact that can obtain by ExxonChemical Company ^TMProduct) 0 to about 15, and do not rely on melting index.Usually, for low ethene polymers (especially than low density the time) to middle pressure, attempt the dependency represented with melt flow ratio with respect to same, DRI provides the improved dependency with melt elasticity and high-shear flowability.For the linear ethylene polymer basically that the present invention uses, DRI preferably is at least 0.1, more preferably is at least 0.5, most preferably is at least 0.8.DRI can calculate by following equation:

DRI=(3652879* τ ₀ ^1.00649/ η ₀-1) τ wherein/10 ₀Be the feature relaxation time of material, η ₀It is the zero-shear viscosity of material.τ ₀And η ₀All be " the suitableeest " value of Cross equation as follows,

η/η ₀=1/ (1+ (γ * τ ₀) ^1-n) wherein, n is the underworld rule index of material, η and γ are respectively viscosity and the shearing rates that records.The baseline determination of viscosity and shearing rate data, be with the rheology spectrometer (RMS-800) of a dynamic scan pattern for from 0.1 to 100 radian per second under 160 ℃, obtain with a gas squeezing rheometer (GER), the extrusion pressure of gas squeezing rheometer is 1,000psi～5, (6.89～34.5MPa), corresponding shear-stress is 0.086～0.43Mpa to 000psi, using diameter is 20: 1 die orifice as 0.0754mm, length-to-diameter ratio, and temperature is 190 ℃.The mensuration of exotic materials can be finished at 140～190 ℃ as required, makes it adapt to the variation of melt index.

Apparent shear-stress can be used to confirm the melt fracture phenomenon to the curve of apparent shear rate, and quantizes polyvinyl critical shear rate and critical shearing stress.According to Ramamurthy at Journal of Rheology, 30 (2), described in the 337-357, under a kind of critical flow speed, the irregularity of observed extrudate can roughly be divided into two kinds of main types: surperficial melt fracture and fully melt fracture.

The surface melt fracture occurs under the apparent stable mobility status, and in detail from losing special film gloss to more serious formation " shark skin ".At this, as use that above-mentioned GER measured, the feature that surperficial melt fracture begins (OSMF) is the gloss that begins to lose extrudate, and at this moment, the surface roughness of extrudate has only and amplifies 40 times of ability and detect.For linear ethylene polymer basically, the critical shear rate when surperficial melt fracture begins is than having essentially identical I ₂And M _w/ M _nThe critical shear rate of linear ethylene polymkeric substance when surperficial melt fracture begins greatly at least 50%.

Fully melt fracture occurs under the unsettled Extrusion Flow situation, and in detail from rule body (for example alternately being coarse and level and smooth or spirrillum) to random distortion.Be to optimize the performance of film, coating and moulded product,, also should lack as much as possible if commercial acceptable surface spots can not it's not true.For the linear ethylene polymer basically that the present invention uses, particularly density is greater than 0.910g/cm ³Ethene polymers, the critical shearing stress when fully melt fracture begins is greater than 4 * 10 ⁶Dyne/cm ²(0.4MPa).

Known linear ethylene polymer basically has excellent processibility, although it has narrow relatively molecular weight distribution (M in other words, _w/ M _nRatio is usually less than 2.5).And, do not resemble homogeneous phase or heterogeneous branching linear ethylene polymkeric substance, the melt flow ratio (I of linear ethylene polymer basically ₁₀/ I ₂) can be independent of molecular weight distribution M _w/ M _nAnd change.Therefore, the polymer backbone of heteromorphic polymer compositions of the present invention (A) linear ethylene polymer basically preferably.

In the present invention's practice, the heterogeneous polyethylene that can be used as polymorphic long-chain branch (B) falls into two wide categories, i.e. those polymkeric substance that prepare under high temperature and high pressure with radical initiator are with those polymkeric substance that prepare under high temperature and relative low pressure with coordination catalyst.New LDPE (film grade) (LDPE) known to the former is promptly common is characterized in that being hung with the side chain that is formed by the monomeric unit polymerization on polymer backbone.The density of LDPE polymkeric substance is generally 0.910～0.935g/cm ³Use coordination catalyst, for example ethene polymers and the multipolymer of Zieglar or Phillips Preparation of Catalyst promptly are the simple linear polymers known to usually, because the suspended side chain that is formed by the monomeric unit polymerization from the polymer backbone not basically.Usually density is about 0.941～about 0.965g/cm ³High density polyethylene(HDPE) (HDPE), generally be the multipolymer of Alathon or ethene and minor amounts of comonomers, and with respect to the various linear copolymers of ethene and alpha-olefin, it contains few relatively side chain.HDPE is known to widely, has various ranks commercially available, and can be used for the present invention.

Ethene and at least aly contain 3～12 carbon atoms preferably contains the linear copolymers of the alpha-olefin of 4～8 carbon atoms, also be widely known to and commercially available.Be well known in the art, the density of the ethylene/alpha-olefin copolymer of line style is the length of alpha-olefin and this monomer function with respect to the consumption of ethene amount in multipolymer, and alpha-olefin is long more, and the consumption of alpha-olefin is big more, and the density of multipolymer is low more.The density range of these simple linear polymers is generally 0.87～0.91g/cm ³

With free radical catalyst with the material of coordination catalyst preparation all is well known in the art, and their preparation method also is well-known.Heterogeneous linear ethylene polymkeric substance can be obtained by DowChemical Company, and commodity are called Dowlex ^TMLLDPE and Attane ^TMThe ULDPE resin.Heterogeneous linear ethylene polymkeric substance can adopt the U.S.P4 that for example is disclosed in Anderson etc., technology in 076,698 is by ethene and one or more selectable alpha-olefin comonomer, in the presence of the Zieglar-Natta catalyzer, carry out solution, slurry or vapour phase polymerization and prepare.The characteristic feature of heterogeneous linear ethylene polymkeric substance is molecular weight distribution M _w/ M _nScope be 3.5～4.1.The relevant discussion of this two classes material and their preparation method can be referring to U.S.P 4,950, and 541 and its mentioned patent.

Heteropolymer is an ethylene/alpha-olefin interpolymer, it is characterized in that having a line style skeleton, and dsc (DSC) melting curve has a tangible melting peak of 115 ℃ of being higher than that is attributable to the high-density fraction.The M of heterogeneous interpolymer _w/ M _nUsually greater than 3 (when the density of interpolymer is lower than 0.960g/cm ³The time), and CDBI is less than or equal to 50 usually, shows that such interpolymer is the mixture with molecule of different copolymer monomer content and different amount short-chain branchs.

Polyvinyl degree of crystallinity is a well-known polyvinyl character.Develop various technology and measured polyvinyl degree of crystallinity.

When ethene polymers is only generated by the hydro carbons monomer (in other words, when the functionalized ethylene/alpha-olefin interpolymer of ethene polymers right and wrong), degree of crystallinity can be determined with following equation by the density of polymkeric substance:

C%=(ρ-ρ a)/(ρ c-ρ a) * 100 wherein, C% is poly percent crystallinity to ρ, and ρ a is that percent crystallinity is 0 ethene polymers (i.e. this polymkeric substance be 100% unformed) density (0.852g/cm at room temperature ³), ρ c represents the polyethylene density (1.000g/cm at room temperature of 100% degree of crystallinity ³), ρ indicates to determine the density of the polymkeric substance of percent crystallinity.Density can be measured according to ASTM D792, and wherein sample was at room temperature annealed before test 24 hours.

Term " use temperature under load " (ULST), be also referred to as " softening temperature under load " or " SPUL ", be meant and use a constant force that can apply 1N to be the device on the tack probe of 1mm at a diameter, make polymkeric substance under nitrogen atmosphere since 25 ℃, heat up the temperature when probe lunges 1mm in the polymkeric substance with the speed of 5 ℃/min.A kind of such device is ThermoMechanical Analyzer (TMA), for example the TMA-7 type of Perkin-Elmer InstrumentCompany manufacturing.Carrying out the method for this test will describe in the following embodiments in more detail.

The molecular weight ranges of the polymkeric substance (B) of the formation side chain that density is higher can be very wide.Aspect lower molecular weight, the Mn of branched polymers is at least 2000, preferably is at least 3000.Aspect high molecular, the I of branched polymers ₂Be at least 0.05g/cm ³The melting index scope of branched polymers is generally 0.05～40g/10min.

When the branched polymers of higher molecular weight is used in hope, i.e. the I of branched polymers ₂When being lower than 5g/10min, the reduction of branched polymers chain number, the concentration of branched polymers is higher with requiring, and promptly its amount (or is used more substantial radical initiator greater than 20wt%, be that its amount is greater than 0.5wt%) so that the use temperature under load reaches given increased value.On the contrary, when using the branched polymers of lower molecular weight, than the increase of short-chain branch (preferred end is a vinyl) number, with the use temperature under load is improved, although the consumption of branched polymers is few relatively, promptly consumption hangs down and reaches 5wt%.

Though do not wish to be bound by theory, it is believed that when using the branched polymers of lower molecular weight, can use same lower concentration, because heteromorphic polymer compositions tends to hang little side chain more than on each polymer backbone.As shown in Figure 1, believe and have an above side chain on each molecule of the skeleton, the polymer backbone molecule will be intertwined, although can melt under higher use temperature than the polymer backbone material of low-crystallinity, this intermolecular winding will make this system structurally have globality.

The technician in polymer science field can envision many manufacturings polymorphic method for compositions of the present invention.

In one embodiment, by making the reaction of prepared beforehand and isolating polymer reaction thing, and prepare the branched polymers of described higher crystallinity and than the skeleton polymer of low-crystallinity.In this case, the branched polymers of higher crystallinity will be reacted with the skeleton polymer than low-crystallinity, forms T-and connects (by grafting) or H-connection (passing through photocrosslinking).This reaction can adopt method known to those skilled in the art to finish.

In one embodiment, remove hydrogen, and react with branched polymers from polymer backbone.The method of removing hydrogen from polymer backbone comprises and free radical reaction, but is not limited thereto, and described free radical is to produce by molecule (for example superoxide, or azo compound) homolysis or by radiation.

The existence of ethylenic unsaturated bond on skeleton polymer or branched polymers can help to control the position of grafting/cross-linking set.For example, at a large amount of saturated-backbone polymkeric substance and a spot of end be vinyl branched polymers in the presence of, the degraded of superoxide will make branched polymers be grafted on the skeleton polymer, and the branched polymers that does not contain vinyl can produce free radical by removing hydrogen, and this free radical forms H-with the free radical reaction of skeleton polymer and is connected.By the conditioned reaction condition, make polymeric chain pass through β-hydrogen and eliminate and stop, rather than hydrogen termination, can prepare the terminal branched polymers of vinyl that is.In addition, coagent, for example single-, two-or three-molecule of functional group (for example triallyl cyanurate), can be used to further control free radical proceed.Usually, grafting is better than photocrosslinking, because can not produce gel in conjunction with more polymorphic long-chain branch.

When the polymkeric substance of polymkeric substance for preparing higher formation side chain or formation skeleton, use α, ω-diene can improve the reactivity of polymeric constituent as comonomer.Suitable α, ω-diene comprises 1,7-octadiene and 1,9-decadiene.When in polymkeric substance during in conjunction with such diene, its consumption is usually less than 2/polymer chain.

Crosslinked or graft reaction can be in the solution that two polymkeric substance form in suitable solvent, or carry out in the molten mixture of polymeric constituent.The latter is a preferable methods.Melt blending can be at the batch of material mixing tank, for example Brabender mixing machine, Banbury Banbury mixer, roller mill, or at continuous mixing device, and Farrell continuous mixing device for example, or in list or twin screw extruder, carry out.Also can make polymeric blends, then radiation or with reactive solution (for example superoxide) dipping and heating.But fusion or solution blending are better than these methods.

In another embodiment, by making branched polymers and the monomer copolymerization that forms skeleton polymer prepare composition of the present invention.Use a kind of binary catalyst system, can envision copolymerization simultaneously and form skeleton polymer and objective composition (being heteromorphic polymer compositions).The advantage of this method is, in cold relatively reactor, make high Tg/Tm polymkeric substance separate out mutually minimum.

In another embodiment, in placed in-line double-reactor, make composition of the present invention, wherein, in first reactor, make branched polymers, be fed to second reactor then, at there, branched polymers and the monomer copolymerization that forms skeleton polymer are prepared objective composition.The temperature of second reactor should remain on be higher than the temperature that the higher crystallinity branched polymers is separated in than the low-crystallinity skeleton polymer.Carry out the reactor of copolymerization, preferably have the reactor of high polymers (solid) concentration, annular-pipe reactor for example is so that the branched polymers concentration of polymerisable higher crystallinity maximization in the reactor.

In one embodiment, use single-site catalysts to make branched polymers and the ethene and the octene copolymer of higher crystallinity, preparation has the branched ethylene/octene elastomerics of HDPE side chain.The catalyzer of single-site catalysts, particularly constrained geometry has superiority, because they are than the traditional Zieglar catalyzer or the single-site catalysts of non-limiting geometric configuration, and the easier high-molecular weight monomer of accepting.With crosslinked different, copolymerization even also avoided gel when quite high polymorphic levels of long chain branching is a reactive behavior because have only any on long-chain branch.

The polymorphic long-chain branch precursor monomer of high Tm or Tg, preferably low-molecular-weight relatively, and at least one end thiazolinyl is arranged on each chain, so that dissolving in process solvent of copolymerization and monomer and/or easier to the diffusion of catalyst center.

Selectively, in one or both polymkeric substance, use diene or polyenoid as comonomer, to improve the combination/connection speed in copolymerization.For example, can in a reactor, prepare ethene-diene or propylene diene copolymerized thing, be fed to second reactor then, at there, it and ethene and octene or ethene and copolymerization of propylene.If the content of diene is quite low, when improving polymorphic branching precursor polymer and the monomeric copolymerization rate of skeleton polymer, can avoid gel.When using diene or polyenoid as comonomer, preferably it constitutes below the 20wt% of the present composition, more preferably below the 10wt%.

In another embodiment, heteromorphic polymer compositions can with one or more other polymer blendings, the structure of these polymkeric substance is similar to branched polymers, perhaps can form high Tm or Tg phase by solid dissolving or cocrystallization.An example of this blend components is a high density polyethylene(HDPE).When the concentration of branched polymers in heteromorphic polymer compositions is low, other polymkeric substance need be provided, be used for the branched polymers cocrystallization or be solidified into one mutually, with physicals and/or the resistance toheat that obtains expecting.The polymkeric substance of excessive higher crystallinity, with of great use with the side chain cocrystallization of the higher crystallinity of heteromorphic polymer compositions, to increase the thickness of platelet, this will tend to improve the crystalline melting temperature of polymer composition.And the polymkeric substance of this excessive higher crystallinity can couple together the side chain of two isolating higher crystallinities, and this will improve the degree of crystallinity of heteromorphic polymer compositions integral body, and the raising of degree of crystallinity will improve the use temperature under load.A kind of preferable methods of introducing other polymkeric substance is simply excessive branched polymers to be joined in reactor or the melt mixer, make when copolymerization or grafting or crosslinked generation, excessive unreacted branched polymers still keeps unreacted, and with polymorphic long-chain branch cocrystallization or generate one mutually.

In an embodiment again, the present composition can be used to and other polymer blending.For example, the present composition can with other polyolefin blend, linear ethylene/the alpha-olefin interpolymer of heterogeneous branching for example, homogeneously branched linear ethylene/alpha-olefin interpolymer, basically the ethylene/alpha-olefin interpolymer of line style, ethylene/vinyl acetate copolymer, styrene block copolymer and unformed polyolefine (for example polypropylene and polybutene).

In a preferred embodiment, heteromorphic polymer compositions comprises at least a segmental component of polarity that contains.In other words, perhaps skeleton polymer, perhaps branched polymers is preferably functionalized by polarity fragment in the grafting.

Any unsaturated point of at least one olefinic (for example at least one two keys), at least one carboxyl of containing (COOH), and can be grafted to unsaturated organic compound on the top disclosed ethene polymers, can use in the present invention.Comprise carboxyl itself and carboxy derivatives at this employed " carboxyl ", for example acid anhydrides, ester and salt (comprising metal-salt and non-metal salt).Organic compound preferably contains a unsaturated point of gripping altogether with carboxyl of olefinic.Representational compound comprises toxilic acid, vinylformic acid, methacrylic acid, methylene-succinic acid, Ba Dousuan, tiglic acid, and styracin, and their acid anhydrides, ester and salt derivative and fumaric acid and ester and salt derivative.Maleic anhydride is the unsaturated organic compound that preferably contains at least one ethylenic unsaturated bond and at least one carboxyl.

Unsaturated organic compound content in grafted skeleton polymer or the branched polymers preferably is at least 0.01wt%, more preferably is at least 0.05wt%, based on the gross weight of polymkeric substance and organic compound.The maximum level of unsaturated organic compound can change according to convenient, but is no more than the 10wt% of graftomer usually, preferably is no more than 5wt%, more preferably no more than 2wt%.

Can adopt any known technology with unsaturated organic compound be grafted to need or branched polymer on, for example USP 3,236,917 and USP 5,194,509 in disclosed technology.For example, in No. 917 patents, polymkeric substance is joined in the double shaft mixer, and 60 ℃ of mixing.Then, with unsaturated organic compound and a kind of radical initiator, for example benzoyl peroxide adds together, makes each component 30 ℃ of mixing, finishes up to graft reaction.In No. 509 patents, process is similarly, and just temperature of reaction is higher, for example at 210～300 ℃, and does not use radical initiator, perhaps uses with lower concentration.

Another and be that preferred grafting method is disclosed in USP 4,950,541, use twin screw devolatilization forcing machine as mixing device.Ethene polymers and unsaturated organic compound make under the reactant fused temperature in forcing machine, and mix in the presence of radical initiator and reaction.Unsaturated organic compound preferably is injected in the zone that remains under the forcing machine internal pressure.

Basically linear ethylene polymer is disclosed in U.S.P5 with the grafting of for example maleic anhydride, and 346,963, be incorporated into this paper as a reference.

In the preparation of heteromorphic polymer compositions, it should be understood that the existence of radical initiator may cause the limited crosslinked of contiguous skeleton polymer, comprise that the side chain that directly is cross-linked to each other or passes through to hang is crosslinked.If the level of this connection is not enough to make polymer composition at thermoplastic shaping or extrude in the processing and can not process, then it is also within the scope of the invention.Heteromorphic polymer compositions preferably has and is lower than 30% gel, more preferably has to be lower than 10% gel, more more preferably has to be lower than 5% gel, most preferably has to be lower than 2% gel.Most preferably, heteromorphic polymer compositions is substantially free of gel.

Optionally, heteromorphic polymer of the present invention can comprise oxidation inhibitor, filler, and extending oil, UV light stabilizing agent, slippage agent and release agent, pigment, dyestuff, or whipping agent are decided according to the composite those skilled in the art's of polymkeric substance practical experience.If use, then the consumption of oxidation inhibitor is usually less than 0.5%, preferably is lower than 0.2%, based on the gross weight of composition.

The present composition can be used in Hotmelt Adhesive or the pressure sensitive adhesive compound.In this case, one or more tackifier that the present composition can the blending appropriate amount, one or more waxes, and/or one or more softening agent.

At this employed term " tackifier ", be meant to be used for making hot-melt adhesive composition to have in several alkyl compositions of adhesive capacity any one.For example, several tackifier comprise aliphatics C ₅Resin, polyterpene resin, hydrogenated resin, mixing-in fat-anine, rosin ester, and hydrogenated wood rosin glycerol ester.The tackifier that use with the viscosity that the Brookfield viscometer records, are no more than 300 centipoises (300g/cmsec) usually under 350 °F (177 ℃), preferably be no more than 150 centipoises (150g/cmsec), are most preferably not exceeding 50 centipoises (50g/cmsec).The second-order transition temperature of the tackifier that use is usually greater than 50 ℃.

Exemplary group aliphatic resin comprises the resin that can obtain with following trade(brand)name: Escorez ^TM, Piccotac ^TM, Mercures ^TM, Wingtack ^TM, Hi-Rez ^TM, Quintone ^TM, Tackirol ^TM, etc.Exemplary polyterpene resin comprises the resin that can obtain with following trade(brand)name: Nirez ^TM, Piccolyte ^TM, Wingtack ^TM, Zonarez ^TM, etc.Exemplary hydrogenated resin comprises the resin that can obtain with following trade(brand)name: Escorez ^TM, Arkon ^TM, Clearon ^TM, etc.Exemplary mixing-in fat-anine comprises the resin that can obtain with following trade(brand)name: Escorez ^TM, Regalite ^TM, Hercures ^TM, AR ^TM, Imprez ^TM, Norsolene ^TMM, Marukares ^TM, Arkon ^TMM, Quintone ^TM, etc.Other tackifier also can use, as long as they and homogeneous line style or the ethylene/alpha-olefin interpolymer and the selectable wax of line style are compatible basically.

In Hotmelt Adhesive of the present invention, the amount of tackifier is usually less than 70wt%, preferably is lower than 50wt%.In Hotmelt Adhesive of the present invention, the amount of tackifier is at least 5wt% usually, preferably 10wt% at least.

Term " wax " is meant that number-average molecular weight is lower than 6000 paraffinic or crystalloid Alathon or interpolymer, or the homogeneous ethylene polymkeric substance.The exemplary polymkeric substance that falls into this scope comprises: can be by Petrolite, and (commodity are called Polywax to Inc. for Tulsa, the OK) Alathon of Huo Deing ^TM500, Polywax ^TM1500, and Polywax ^TM2000; With the paraffin that can obtain by CP Hall, ProductName 1230,1236,1240,1245,1246,1255,1260 and 1262.

Polywax ^TM2000 molecular weight is approximately 2000, M _w/ M _nBe approximately 1.0, be about 0.97g/cm 16 ℃ density ³, fusing point is about 126 ℃.

CP Hall 1246 paraffin can (Stow OH) obtains by CP Hall.CP Hall 1246 meltings point of paraffin wax are 143 °F (62 ℃), are 4.2 centipoises (4.2g/cmsec) in the viscosity of 210 (99 ℃), are 0.915 at the proportion of 73 (23 ℃).

Preferred wax can use the Preparation of Catalyst of constrained geometry.Mentioned comonomer when such polymkeric substance or Alathon, or ethene and the monomeric interpolymer of copolymerization, described comonomer relate to polymkeric substance 1 above being, for example C ₃-C ₂₀Alpha-olefin, the vinylbenzene that vinylbenzene, alkyl replace, tetrafluoroethylene, vinyl benzo tetramethylene is non-ly gripped diene altogether, and cyclic hydrocarbon (naphthenics).Anti-with common wax phase, the M of such polymkeric substance _w/ M _nBe 1.5～2.5, preferred 1.8～2.2.The applying date is open and claimed this base polymer in the U.S. Patent application sequence the 784th, No. 683 (WO 97/01181) on January 22nd, 1997.

The number-average molecular weight of wax should be lower than 6000, preferably is lower than 5000.The number-average molecular weight of this class wax is at least 800 usually, preferably is at least 1300.

Be used in the wax in the Hotmelt Adhesive of the present invention, when it is Alathon (Alathon of the Preparation of Catalyst of traditional Alathon wax or use constrained geometry) or ethene and is selected from C ₃-C ₂₀The interpolymer of alpha-olefin, the non-comonomer of gripping diene and cyclic hydrocarbon altogether the time, its density is at least 0.910g/cm ³The density of second kind of polymkeric substance of this class is not higher than 0.970g/cm ³, preferably be not higher than 0.965g/cm ³

Heteromorphic polymer compositions of the present invention can be used in the pressure sensitive adhesive compound, because the branched polymers of higher crystallinity can be improved the off-period (close time) of tackiness agent.Along with the cooling of tackiness agent, the branched polymers crystallization, and simultaneously polymer backbone still to keep be soft and/or flowable.This gives its intensity in the tackiness agent process of setting, and reduces open (open)/off-period.

Hotmelt Adhesive (particularly pressure sensitive adhesive) can also comprise oil or other softening agent, for example unformed polyolefine.Oil is commonly used to reduce the viscosity of Hotmelt Adhesive.When using oil, its consumption is lower than 25wt%, preferably is lower than 15wt%, more preferably less than 10wt%, based on the weight of Hotmelt Adhesive.The kind of exemplary oil comprises paraffin oil (Kaydol for example ^TMOil (can obtain), and Shellflex by Witco ^TM371 naphthenic oils (can obtain)) by Shell Oil Company.If the oily adhesiveproperties of Hotmelt Adhesive that makes is reduced to when influencing its expection application target, then should not use oil.

Can use the melting mixing prepared Hotmelt Adhesive of the present invention of standard.Especially, (150～200 ℃) at elevated temperatures are under protection of inert gas, with heteromorphic polymer compositions, selectable tackifier, selectable wax and selectable softening agent melt blending, up to obtaining the homogeneous mixture.Any can to produce the homogeneous blend and can not make the blending means of Hotmelt Adhesive component degradation all be gratifying, for example is equipped with the heating container of agitator by use.In addition, heteromorphic polymer compositions, selectable wax, selectable tackifier and selectable softening agent can be joined in the extrusion coated machine, and it is applied on the base material.

Suitable pressure sensitive adhesive will demonstrate the probe tackiness of 200g at least, more preferably 300g at least, most preferably 350g at least.In addition, the thermotolerance that suitable pressure sensitive adhesive is shown, will be than at least 10 ℃ of wherein branched polymers and skeleton polymer only uses with the blend form rather than the pressure sensitive adhesive that uses with the form of heteromorphic polymer compositions of the present invention is shown thermotolerance height, preferably at least 15 ℃, more preferably at least 20 ℃.

The viscosity of suitable binder will be enough low, and it can be applied on the base material that needs easily.Usually Hotmelt Adhesive is lower than 50,000 centipoises in the melt viscosity of 350 (177 ℃) (50,000g/cmsec), it is normally preferred to have lower viscosity.

The application of heteromorphic polymer compositions of the present invention (being one of at least in skeleton polymer and the branched polymers wherein particularly) with those functionalized heteromorphic polymer compositions of polarity fragment, also comprise pad (for example being used in the pad on the automotive window), sealing agent, tackiness agent, flexible die goods (for example sole), the insulation layer of electric wire and cable and sheath, roof film, floor covering, sebific duct, boots, requirement has the resilient material accessory of bonding force in auto parts machinery and other the known industry to polar substrates.

The following examples have been set forth representational heteromorphic polymer compositions of the present invention, and purpose is to be used for illustrating the present invention, rather than limit the present invention.Be used in the polymkeric substance in the example composition preparation

One kind of polymer A 1-is the POE of line style basically, and according to U.S.5,278,236 disclosed methods prepare, the I that it records ₂Be 0.94g/10min., density is 0.869g/cm ³

One kind of polymer A 2-is the POE of line style basically, and according to U.S.5,278,236 disclosed methods prepare, the I that it records ₂Be 3.86g/10min., density is 0.867g/cm ³

One kind of polymer A 3-is the POE of line style basically, and according to U.S.5,278,236 disclosed methods prepare, the I that it records ₂Be 23.79g/10min., density is 0.867g/cm ³

One kind of polymer A 4-is the ethylene/octene of line style basically, and according to U.S.5,278,236 disclosed methods prepare, the I that it records ₂Be 30g/10min., density is 0.870g/cm ³

One kind of polymer A 5-is the ethylene/octene of line style basically, and according to U.S.5,278,236 disclosed methods prepare, and its density is 0.870g/cm ³, I ₂Be 18g/10min..

One kind of polymer A 6-is the POE of line style basically, and according to U.S.5,278,236 disclosed methods prepare, the I that it records ₂Be 1g/10min., density is 0.855g/cm ³

One kind of polymer A 7-is the ethene of line style/1-octene copolymer basically, and according to U.S.5,278,236 disclosed methods prepare, and its density is 0.855g/cm ³, melting index is 30g/10min..

Polymer A 8-ultra-low molecular amount ethene/1-octene copolymer is that disclosed method prepares in the U.S. Patent application sequence the 784th, No. 683 (WO 97/01181) on January 22nd, 1997 according to the applying date, and its density is 0.855g/cm ³, be 350 centipoises (350g/cmsec) in the melt viscosity of 350 (177 ℃).

One kind of polymer A 9-is the ethene of line style/1-octene copolymer basically, and according to U.S.5,278,236 disclosed methods prepare, and its density is 0.855g/cm ³, melting index is 0.5g/10min..

One kind of polymer A 10-is the ethene of line style/1-octene copolymer basically, and according to U.S.5, disclosed method prepares in 278,272, and its density is 0.870g/cm ³, melting index is 30g/10min..

Polymer B 1-HDPE 55500-ethylene/butylene copolymers is by PhillipsPetroleum supply, the I that it records ₂Be 49g/10min., density is 0.955g/cm ³

Polymer B 2-Marlex50-100 high density polyethylene(HDPE), its density are 0.952g/cm ³, I ₂Be 0.08g/10min., can obtain by Phillips.

Polymer B 3-Dowlex ^TM25355 high density polyethylene(HDPE)s, its density are 0.955g/cm ³, I ₂Be 25g/10min.

Polymer B 4-Dowlex ^TM25455 high density polyethylene(HDPE)s, its density are 0.955g/cm ³, I ₂Be 25g/10min.

One kind of polymer B 5-is the ethene of line style/1-octene copolymer basically, and according to U.S.5, disclosed method prepares in 278,236, and its density is 0.902g/cm ³, melting index is 30g/10min..

One kind of polymer B 6-is the ethene of line style/1-octene copolymer basically, and according to U.S.5, disclosed method prepares in 278,236, and its density is 0.913g/cm ³, melting index is 30g/10min..

Polymer B 7-Attane ^TM6152 ultra-low density polyethylenes, a kind of heterogeneous linear ethylene/1-octene copolymer, its density is 0.904g/cm ³, melting index is 0.5g/10min..

Polymer B 8-ultra-low molecular amount ethene/1-octene copolymer is that disclosed method prepares in the U.S. Patent application sequence the 784th, No. 683 (WO 97/01181) on January 22nd, 1997 according to the applying date, and its density is 0.955g/cm ³, be 5000 centipoises (5000g/cmsec) in the melt viscosity of 350 (177 ℃).

Polymer B 9-Dow high density polyethylene 12165, its density are 0.955g/cm ³, melting index is 1.0g/10min.

Polymer B 10-Dow high density polyethylene 25355, its density are 0.955g/cm ³, melting index is 10g/10min.

Polymkeric substance C: a kind of reactor interpolymer mixture, according to the preparation of WO94/17112 disclosed method, its target is formed: the ethylene/octene of the line style basically of 68.5wt%, its density are 0.861g/cm ³, I ₂Be the high density polyethylene(HDPE) of 0.29g/10min. and 31.5wt%, its density is 0.946g/cm ³, I ₂Be 370g/10min.

Polymkeric substance D: a kind of high density polyethylene(HDPE) of maleic anhydride graft, its density are 0.953g/cm ³, melting index is 9g/10min., maleic anhydride content 1.2wt% is 0.953g/cm by density ³High density polyethylene(HDPE) and maleic anhydride reactivity extrude and prepare.

Lupersol 500R (99% pure dicumyl peroxide is obtained by Elf Atochem).Lupersol-130 (5-two (tert-butyl peroxy base) hexin-3 is obtained by Elf Atochem for 2 of 90-95%, 5-dimethyl-2).Lupersol-101 2,5-dimethyl-2,5-two (tert-butyl peroxy base) hexane (being obtained by Elf Atochem).Be used to estimate the testing method of the composition of embodiment and comparative example

Use temperature under load (ULST) is to use a thermodynamic analyzer to measure.The relation of the degree of depth to temperature thrust in measurement.The temperature that probe thrusts 1mm is considered as the softening temperature under load.Temperature rise rate is 5 ℃/min, and load is 102g.

Use RSAII type rheology solid analysis instrument to measure modulus with variation of temperature.Sample kept 5 minutes down at 1500psi (10.3Mpa) and 350 (177 ℃), and (2.8 ℃/min) speed is cooled to 90 °F (32 ℃), and pressing mold is into about the thick film of 0.25mm with 27/min then.Sample kept 1 minute down at 90 °F (32 ℃), removed pressure then.Downcut the batten of about 0.25 * 4.4 * 22mm, then test under the following conditions: the 10rad/sec frequency, reverse the rectangle test, start from-145 ℃,, be elevated to 120 ℃ or 150 ℃ or 270 ℃ with every stride degree of 5 ℃, per step saturation time is 30 seconds, tests under nitrogen atmosphere.

According to ASTM D2785, method A measures gel content with xylene extraction.

According to the stress and strain of ASTM D1708 measurement under 23 ℃ and 70 ℃.Be stress and strain under 70 ℃ in the bracket.

Measure Xiao A hardness according to ASTM D2240.

According to ASTM D1708, use little stretching rod measuring limit tensile strength.

The measurement of melt viscosity is used Brookfield LaboratoriesDVII+ type viscometer as follows, is measured in disposable aluminium sample pool.The spindle that uses is a SC-31 hot melt spindle, be suitable for measuring 10～100,000 centipoise (10～100, viscosity 000g/cmsec).Use cutting knife that sample is cut into enough little fragment, it can be encased in the sample pool that 1 inch (2.5cm) is wide, 5 inches (12.5cm) is long.Sample is put in the pond, be inserted into then among the Brookfield Thermosel, and fix with crooked pin-nose hand vice.One indenture is arranged in sample pool bottom, adapt, insert and during rotation, sample pool can not overturn at spindle guaranteeing with the bottom of Brookfield Thermosel.Sample is heated to 350 °F (177 ℃), adds other sample, up to the fused sample apart from the sample pool top about 1 inch (2.5cm).Viscometer apparatus is reduced, spindle is immersed in the sample pool.Continue to reduce, equal up to the mounting of viscometer with Thermosel.Open viscometer, set shearing rate, making torque readings is 30～60%.The per minute reading once reads about 15 minutes, or behind numerical stability reading, write down final reading.Embodiment 1-3: the amount of determining the branched polymers that in forming heteromorphic polymer compositions of the present invention, is used for reacting

Use a HaakeRheocord System 40 who is equipped with Rheomix 600 mixing tanks and roller-type hybrid blade to reverse rheometer, prepare the composition of these embodiment.At 145 ℃,, mix each component and prepare blend with 75 rev/mins speed.The composition of polymer A 2, A3 and B is mentioned in the above.Add Lupersol 500 (99% pure peroxidation two cumenes are obtained by Elf Atochem) with specified amount, mixed this mixture about 1 minute, be warmed up to 175 ℃ then, and sample amounts to mixing 15 minutes at 145 ℃.Sample is poured on the cold pressing mold platform while hot, and is pressed into thin diaphragm, be used for FTIR and analyze contents of ethylene.

The FTIR analytical results of representational composition of the present invention is listed in table 1.

The vinyl analysis of table 1. embodiment 1-3

Embodiment	Explanation	Vinyl/1000C before the peroxide treatment	Vinyl/1000C after the peroxide treatment	The vinyl % of reaction
					????1	40.2g 50/50 the polymer A 3 and the blend of polymer B 1+0.20g Lupersol 500R	?????0.448	????0.167	????63
????2	40.2g 50/50 the polymer A 2 and the blend of polymer B 1+0.20g Lupersol 500R	?????0.735	????0.206	????72
					????3	40.2g 50/50 the polymer A 3 and the blend of polymer B 1+0.50g Lupersol 500R	?????0.636	????0.069	????89

The reduction of vinyl ends concentration can think that this has shown the degree that formation " T " connects.Owing to can suppose the possibility of from polymer A 2 and A3, removing hydrogen, equate with the possibility of from polymer B 1, removing hydrogen, because most vinyl is on the polymer B 1 of lower molecular weight, and on the polymer A 2 of higher molecular weight and A3 vinyl less (polymkeric substance of noticing use be with 50: 50 mixed), it is because polymer B 1 is grafted on polymer A 2 and the A3 that about 50% " T " that can suppose formation connects.The very big reduction of the vinyl concentration shown in the table 1, further proof has formed " T " connection.Disclosed stable on heating very big improvement in the following examples also supports the polymer B 1 of higher crystallinity to receive on the skeleton polymer.Embodiment and comparative example 4-18: the stable on heating raising that heteromorphic polymer compositions of the present invention is shown

The Haake RheocordSystem 40 that use is equipped with Rheomix 3000 mixing tanks and roller-type hybrid blade reverses rheometer.About 145 ℃, with 60～75 rev/mins, with about 4 minutes of polymer B 1 and suitable polymers A1, A2 and A3 resin melting mixing, prepare sample.Add Lupersol 500R (99% pure peroxidation two cumenes are obtained by Elf Atochem) with specified amount.Mixer speed bring up to about 160 rev/mins with the short mix superoxide, therefore produce the viscous heating effect, through 1-2 minute, mixture temperature was elevated to about 190 ℃, causes the degraded of superoxide.Use 1 minute again, the speed of mixing tank is reduced to 60 rev/mins.After the mixing, stop mixing tank, take out sample and make its cooling.Then with the polymkeric substance granulation.

Table 2

	Polymer A 1	Polymer A 2	Polymer A 3	Polymer B 1	Sample rate (g/cm 3)-without superoxide/use superoxide	Sample melt index (Ip) (g/10min)-without superoxide/use superoxide	Maximum temperature * (℃)-without superoxide/use superoxide	Elongation is without superoxide/use superoxide	Ultimate tensile strength (psi (Mpa)-without superoxide/use superoxide
										Comparative example 4a/ comparative example 4b	?100	?0	?0	?0	?0.8714/0.8716	?6.33/0	?65/65	?946/272	?1720/1177(11.86/8.115)
Comparative example 5/ embodiment 5	?75	?0	?0	?25	?0.8931/0.8887	?16.24/0	?125/135	?892/427	?2839/1966(19.57/13.56)
										Comparative example 6/ embodiment 6	?50	?0	?0	?50	?0.9132/0.9060	?44.52/0	?90/＞150	?790/423	?2904/2585(20.02/17.82)
Comparative example 7/ embodiment 7	?25	?0	?0	?75	?0.9329/0.9239	?118.06/0	?130/＞150	?812/437	?2614/3020(18.02/20.82)
										Comparative example 8a/ embodiment 8b	?0	?100	?0	?0	?0.8697/0.8698	?33.08/0.58	?55/65	?1317/1048	?1628/1635(11.23/11.27)
Comparative example 9/ embodiment 9	?0	?75	?0	?25	?0.8898/0.8882	?61.44/0.23	?110/＞120	?1218/756	?1875/2307(12.93/15.91)
										Comparative example 10/ embodiment 10	?0	?50	?0	?50	?0.9109/0.9058	?113.13/0	?80/110	?1089/621	?2335/2845(16.10/19.62)
Comparative example 11/ embodiment 11	?0	?25	?0	?75	?0.9328/0.9240	?196.61/0	?95/127	?50/842	?2662/3036(18.35/20.93)
										Comparative example 12a/ embodiment 12b	?0	?0	?100	?0	?0.8683/0.8687	?145.44/11.1	?50/55	?1341/1285	?1164/1238(8.025/8.536)
Comparative example 13/ embodiment 13	?0	?0	?95	?5	?0.8739/0.8738	?140.68/9.07	?105/115	?1496/1253	?910/1099(6.28/7.577)
										Comparative example 14/ embodiment 14	?0	?0	?85	?15	?0.8818/0.8812	?167.84/3.39	?85/115	?1385/961	?953/1312(6.57/9.046)
Comparative example 15/ embodiment 15	?0	?0	?75	?25	?0.8890/0.8877	?203.17/1.33	?70/130	?790/895	?936/1680(6.453/11.58)
										Comparative example 16/ embodiment 16	?0	?0	?50	?50	?0.9103/0.9066	?232.37/0.28	?75/127	?715/865	?1790/2700(12.34/18.62)
Comparative example 17/ embodiment 17	?0	?0	?25	?75	?0.9317/0.9249	?276.52/0.1	?115/128	?761/656	?2306/2923(15.90/20.15)
										Comparative example 18a/ embodiment 18b	?0	?0	?0	?100	?0.9547/0.9410	?350.25/0.04	?130/＞120	?17/67	?2253/3367(15.53/23.22)

-* maximum temperature is that RSA modulus (E ') curve drops to 10 ⁶Dyn/cm ²(0.1MPa) the roughly temperature-part first round sample at following place is only tested 120 ℃, if not failure is indicated with＞120.

Table 2 shows, the blend of comparative example 15, promptly without the blend of peroxide treatment in about 70 ℃ of surrenders.In the RSA test, because the watery fusion of polymer A 3, this blend does not have enough intensity to keep its integrity, sample breakage.On the contrary, the heteromorphic polymer compositions of embodiment 15 promptly passes through the composition of peroxide treatment, can be up to 130 ℃ of its integrities of maintenance down, and this temperature approximately is the fusing point of polymer B 1.

Table 2 has been summarized the result of a series of relatively blend composition (preparing without peroxide treatment) and a series of heteromorphic polymer compositions of the present invention (preparing with peroxide treatment).Table 2 shows that heteromorphic polymer compositions of the present invention and comparison blend relatively have the thermotolerance that significantly improves.And table 2 shows, uses pure polymer A 1, the A2 of peroxide treatment, and A3, also surrenders under low relatively temperature.Like this, the stable on heating substantial raising of heteromorphic polymer compositions of the present invention can not be owing to the formation of cross-linked structure, and more should be hanging on the formed skeleton of polymer A 1, A2 and A3 owing to dystectic polymer B 1 side chain.Embodiment 19-23: superoxide is to the influence of heteromorphic polymer compositions physicals

According to the method that proposes among the top embodiment 1-4, the heteromorphic polymer compositions of preparation comparative example and embodiment 19-23.Heteromorphic polymer compositions is with relatively the prescription and the final properties of blend are listed in the table 3.

Table 3

Embodiment	Comparative example	Embodiment 20	Embodiment 21	Embodiment 22	Embodiment 23	Comparative example 24	Embodiment 25
								Prescription
Polymer A 3 (wt%)	????75	????75	????75	????70	????80	????0	????0
								Polymer B 2 (wt%)	????25	????25	????25	????30	????20	????0	????0
Polymkeric substance C (wt%)	????0	????0	????0	????0	????0	????100	????100
								Lupersol?500R(wt％)	????0	????0.3	????0.5	????0.5	????0.5	????0	????0.5
Performance
								ULST(℃)	????73	????100	????120	????130	????80	????80	????120
Gel (%)	????0.5
								Stress (psi (Mpa))	????730/60 ????(5.0/0.41)	????1800/220/180 ????(12.4/1.52/1.24)	????4300/560/250 ????(29.6/3.86/1.72)	????1900/700/470 ????(13.1/4.83/3.24)	????1800/260/200 ????(12.4/1.79/1.38)	????ND	????ND
23/70/100 ℃ of strain (%)	????14000/20	????1200/360/330	????480/150/130	????290/120/120	????1000/330/215	????ND	????ND
								Hardness at room temperature (Shore A)	????85	????86	????87	????91	????85	????85	????86

The discussion of embodiment 19-21.About embodiment 19-21, along with the increase of amount of peroxide, the use temperature under load also improves, and is 27 ℃ in embodiment 20, is 47 ℃ in embodiment 21.The result shows shown in the table 3, and embodiment 20 and 21 heteromorphic polymer compositions of the present invention have the thermotolerance more much higher than the comparison blend of corresponding comparative example 19.This is presented among Fig. 3, and Fig. 3 shows, embodiment 20 and 21 heteromorphic polymer compositions are before Xiao A hardness is reduced to below 45, than the temperature of the blend Nai Genggao of comparative example 19.This point also is presented among Fig. 4, and Fig. 4 shows, embodiment 20 and 21 heteromorphic polymer compositions, and the temperature that probe thrusts 1mm is higher than comparative example 19.

Table 3 points out that also heteromorphic polymer compositions tensile property at high temperature surpasses the comparison blend of comparative example 19.For example, the blend of comparative example 19 loses its most of tensile strength at 70 ℃.On the contrary, embodiment 20 and 21 heteromorphic polymer compositions are respectively 250psi (1.72MPa) and 180psi (1.24MPa) 100 ℃ tensile strength.

In addition, the gel content of the heteromorphic polymer compositions of embodiment 20-21 is lower than the gel content of partial cross-linked blend of the prior art, and these prior aries are U.S.3 for example as seen, and 806,558, the gel content of this patent disclosure is greater than 30%.Curious is, heteromorphic polymer compositions is not reducing snappiness and hardness greatly, and does not form under the situation of a large amount of cross-linked structures, and thermotolerance demonstrates so big raising.

The discussion of embodiment 21-23.As for embodiment 21-23, along with the increase of the polymer concentration of the formation side chain of higher crystallinity, the use temperature under load improves.What is interesting is that between embodiment 23 and 21, the consumption of the material of higher crystallinity is increased to 25wt% from 20wt%, make the use temperature under load improve 40 ℃.

The discussion of embodiment 24-25.The embodiment 24 and the such fact of 25 explanations, the polymkeric substance of the higher crystallinity that promptly prepares in reactor and than the mixture of polymers of low-crystallinity can be made polymorphic composition of the present invention valuably.Can notice, the use temperature of the heteromorphic polymer compositions of embodiment 25 under load is higher 40 ℃ than the use temperature under load of mixture in the unreacted reactor of comparative example 24.

The transmission type microscope of the heteromorphic polymer compositions of embodiment and comparative example 19-20 and 24-25 (TEM) is analyzed:

Heteromorphic polymer compositions and relatively blend be compression molded into internal diameter be 1 inch (2.5cm) thick be disk of 1/16 inch (0.16cm) size, molding temperature is 177 ℃, the speed with 15 ℃/min before the demoulding is cooled to 22 ℃.

At room temperature the slice of compression molded samples is inserted into Epofix (Struer ' s epoxy group(ing) embed equipment).After the pruning, be immersed in ruthenium trichloride and Clorox ^TMMixture in, at room temperature bleached 2 hours.With Reichert-Jung Ultracut E slicing machine, at room temperature obtain thick about 1000 dusts ultrathin section.Thin slice is placed on the copper screen work of formvar covering.JEOL 2000FX tem observation thin slice with the 100kV acceleration voltage amplifies 30,000 times.

The data analysis of TEM image is finished by a Leica Quantimet 570 grayscale analysers.Grayscale image is by the input of CCD photographic camera, and each image is input amplifier image and zero point of obtaining respectively all.Generate the binary picture that comprises disperse phase and independent stratum by the Grayscale beginning.It is 1 level and vertical operation that these binary picture forms are carried out size openly, to remove independently laminate structure from model.With size is 2 dish, and form is removed background noise openly.Carry out the human-edited then, revise remaining error.The description of employed image transform can be seen " Image Analysis and Mathematical Morphology ", Vol.1, by JeanSerra, Academic Press (1982).

The data image analyser is by eight diameters measuring each disperse phase in the binary picture and total area mark.Mean diameter counting statistics diameter by each disperse phase.These statistic diameters have transmitted about the size and the information of size distribution width mutually.The volume weight mid-diameter has been emphasized the existence of big disperse phase, and the resonance mid-diameter has then been emphasized little disperse phase.

The TEM image of comparative example 19 is shown in Fig. 5, amplifies 30,000 times.Microscopic image demonstrates two phase morphologies, comprises the polyethylene zone of dispersive higher density, be dispersed in continuous elastomeric that polymer A 3 forms mutually in.The zone that constitutes by the polyethylene component polymer B 2 of higher density, can by its inwardly and the lamellar morphologies in the radiation direction matrix distinguish.By the elastomerics phase that more low-density polyethylene component polymer A 3 constitutes, demonstrate the cherry shape microbeam crystalline particle form of feature.In contrast, the TEM image of the heteromorphic polymer compositions of embodiment 20 is shown in Fig. 6, amplifies 30,000 times.Although microscopic image demonstrates two phase morphologies, the higher density polyethylene that polymer B 2 forms disperses the average area size of phase, than the obvious reduction of Fig. 5.Laminate structure is in the good distribution of elastomerics in mutually, and the view that is grafted on the skeleton that polymer A 3 forms with the polyethylene component polymer B 2 of higher density is consistent.The TEM image that the amplification of comparative example 24 and embodiment 25 is 30,000 times is shown in Fig. 7 and Fig. 8.

Determine the volume fraction of dispersive high density polyethylene(HDPE) phase by digital image analysis.Volume and the size of high density polyethylene(HDPE) disperse phase in comparing blend and heteromorphic polymer compositions is listed in the following table 4:

Table 4

Sample	Volume %	The resonance intermediate value	Median diameter	The volume intermediate value
					Comparative example 19	?19.2	?0.25	?0.52	?1.96
Comparative example 24	?24.9	?0.13	?0.36	?1.43
					Embodiment 20	?8.1	?0.19	?0.26	?1.53
Embodiment 25	?8.0	?0.18	?0.20	?0.34

Listed as table 4, the heteromorphic polymer compositions of the embodiment of the invention 20 demonstrates the low higher crystallinity island (being proved by obvious low percent by volume) more than 50% of unreacted blend than comparative example 19.Similarly, the heteromorphic polymer compositions of the embodiment of the invention 25 demonstrates the higher crystallinity island (being proved by obvious low percent by volume) than the unreacted blend low 67% of comparative example 24.This shows that polymorphic composition of the present invention in fact comprises elastomer matrix, is grafted with the polymeric constituent of higher density thereon.

Comparative example 19 and 24 average-volume percentage ratio are 22.1%.Embodiment 20 and 25 average-volume percentage ratio are 8.Based on this, estimating has 64% to be grafted on the elastomer matrix in all high density polyethylene(HDPE)s.Embodiment 26 and 27: the polymorphic ethene polymers that is used for pressure sensitive adhesive

Use following polymers to prepare the heteromorphic polymer compositions of present embodiment:

Reverse in the rheometer at a HaakeRheocord System 40 who is equipped with Rheomix 3000E mixing tank and roller-type hybrid blade, about 145 ℃, with 60～75 rev/mins rotating speeds, with polymer A 6 and D about 4 minutes, prepare sample with specified amount melting mixing.Add Lupersol with specified amount ^TM101 (obtaining) by Elf Atochem, and with mixer speed bring up to about 160 rev/mins with the short mix superoxide, and cause the viscous heating effect, through 1-2 minute, temperature was elevated to about 190 ℃, causes the degraded of superoxide.Use 1 minute again, the rotating speed of mixing tank is reduced to 60 rev/mins.After the mixing, stop mixing tank, take out sample and make its cooling.Then with the polymkeric substance granulation.

Heteromorphic polymer that test obtains and comparative polymers blend are as the performance of adhesive tape pressure sensitive adhesive.Use following adhesive formula: 100phr resin, 220phr Escorez 1310 LC tackifier and 1phr Irganox ^TM1010.In a Haake mixing tank with the compound component at 130 ℃ of melt blendings.After obtaining the homogeneous mixture, add 80phr Kaydol oil with syringe.20, under 000psi (138MPa) pressure, in 170 ℃, at Mylar ^TMThe composite tackiness agent of pressing mold is prepared the adhesive tape sample between film and releasing piece.The thickness of the tackiness agent that obtains is about 2mil (0.05mm).

Use Rheometrics, the RDA-II type dynamic mechanical spectrometer of Inc. is measured the thermotolerance of composite tackiness agent.The temperature that rubber storage modulus (G ') platform descends suddenly is considered as heat resisting temperature.Temperature scanning is that per step heats up 5 ℃ from-70 ℃～200 ℃ approximately, and balance is 30 seconds in per step.Vibrational frequency is 1 radian per second, and the automatic response function is 0.1% of an initial strain, when moment of torsion is reduced to 4gcm, increases positive 100% and regulates.Maximum strain is set at 26%.Use 7.9mm parallel plate anchor clamps, initial separation 1.5mm, 160 ℃ (sample inserts RDA-II at 160 ℃).At 160 ℃, use " HOLD " function, instrument is cooled to-70 ℃, begin test, and revise because test pool is heated or cools off thermal expansion or the contraction that is brought.In whole test process, keep nitrogen atmosphere, to reduce oxidative degradation as far as possible.

According to ASTM D-2979-71 measuring probe tackiness, the residence time is 10 seconds, and probe separates speed is 1cm/sec.

As follows, use Brookfield Laboratories DVII+ type viscometer, in disposable aluminium sample pool, be determined at 177 ℃ viscosity.The spindle that uses is a SC-31 hot melt spindle.Sample is cut into enough little fragment, it can be encased in the sample pool that 1 inch (2.5cm) is wide, 5 inches (12.5cm) is long.Sample is heated to 177 ℃, and the fused sample is than sample pool top low about 1 inch (2.5cm).Viscometer apparatus is reduced, spindle is immersed in the sample pool.Open viscometer, it is 30～60% that the setting shearing rate makes torque readings.Per minute is read number one time, reads about 15 minutes, or behind numerical stability reading, write down final reading.

Heteromorphic polymer compositions and blend relatively, and as the performance of pressure sensitive adhesive title complex, are listed in table 5～table 7 at its characteristic.

Table 5

Sample	The amount (phr) of polymer A 6-in heteromorphic polymer or comparison blend	The amount (phr) of polymkeric substance D-in heteromorphic polymer or comparison blend	The amount (phr) of superoxide-in heteromorphic polymer or comparison blend	The ULST of heteromorphic polymer or comparison blend (℃)	The probe binding property (g) of adhesive formula	The thermotolerance of binding prescription (℃)	Adhesive formula is 177 ℃ viscosity (centipoise) ((g/cmsec))
								????21-1	????????78	????????22	???????0.5	?????115	????380	????110	????46,000 ????(46,000)
????21-2	????????78	????????22	???????0	?????58	????630	????80	????42,000 ????(42,000)
								Scotch Magic adhesive tape	????????--	????????--	???????--	Can't record	????370	Can't record	Can't record

The result of table 5 shows that heteromorphic polymer can be used as pressure sensitive adhesive: sample has acceptable processibility, probe tackiness (suitable with commercially available Scotch Magic adhesive tape) and the use temperature higher than blend frequently.

The composition of table 6 heteromorphic polymer compositions 26-39

Embodiment	First polymkeric substance (skeleton)	Second polymkeric substance (side chain)	First polymkeric substance (phr)	Second polymkeric substance (phr)	?Lupersol ?101(phr)
						26	?A6	?B4	?78.0	?22.0	?0.5
27	?A6	?B4	?70.0	?30.0	?0.5
						Comparative example 27	?A6	?B4	?70.0	?30.0	?0
28	?A6	?B5	?70.0	?42.6	?0.7
						Comparative example 28	?A6	?B5	?70.0	?42.6	?0
29	?A6	?B5	?40.0	?60.0	?0.5
						30	?A6	?B6	?70.0	?30.0	?0.5
31	?A6	?B7	?70.0	?30.0	?0.5
						32	?A6	?D	?70.0	?30.0	?0.5
33	?A6	?B5	?70.0	?30.0	?0.5
						34	?A7	?B3	?78.0	?22.0	?1.0
35	?A8	?B3	?78.0	?22.0	?1.0
						36	?A7	?B8	?78.0	?22.0	?1.0
37	?A7	?B9	?78.0	?22.0	?1.0
						38	?A7	?B10	?78.0	?22.0	?1.0
39	?A9/A8	?B3	?50?phr?A9 ?28?phr?A8	?22.0	?1.0

Table 7 pressure sensitive adhesive

The prescription number	Heteromorphic polymer embodiment/comparative example	Heteromorphic polymer (phr)	E1310LC(phr)	Kaydol(phr)	?TMA(℃)	20 ℃ G ' (dynes/cm 2)	Probe binding property (h)	????Tg(℃)
									??21-1	????26	????100.0	????222.0	????80.0	???115	????3×10 6	????430	????-3
??21-2	????27	????100.0	????220.0	????80.0	???122	????2×10 6	????380	????1
									??21-3	Comparative example 27	????100.0	????220.0	????80.0	???58	????3×10 6	????540	????0
??21-4	????28	????100.0	????220.0	????80.0	???84	????3×10 6	????380	????-9
									??21-5	Comparative example 28	????100.0	????220.0	????80.0	???63	????7×10 5	????400	????2
??21-6	????29	????100.0	????220.0	????80.0	???94	????2×10 6	????200	????0
									??21-7	????30	????100.0	????220.0	????80.0	???95	????1×10 6	????300	????0
??21-8	????31	????100.0	????220.0	????80.0	???92	????6×10 5	????380	????0
									??21-9	????32	????100.0	????220.0	????80.0	???120	????3×10 6	????320	????0
??21-10	????33	????110.0	????110.0	????40.0	???84	????N/D	????N/D	????N/D
									??22-1	????34	????100.0	????220.0	????80.0	???117	????3×10 6	????N/D	????0
??22-2	????35	????100.0	????220.0	????80.0	???75	????4×10 5	????N/D	????0
									??22-3	????36	????100.0	????220.0	????80.0	???84	????3×10 5	????N/D	????3
??22-4	????37	????100.0	????220.0	????80.0	???108	????6×10 5	????N/D	????0
									??22-5	????38	????100.0	????220.0	????80.0	???109	????9×10 5	????N/D	????4
??22-6	????39	????100.0	????220.0	????80.0	???95	????N/D	????N/D	????5

^*All prescriptions are all used 1phr Irganox ^TM1010 hindered phenols (can be obtained by Ciba Geigy) are stable

The listed TMA data of table 7 show that the non-grafting sample that the maximum operation (service) temperature of heteromorphic polymer compositions is compared is higher.For example comparing embodiment 21-2 and 21-3 and 21-4 and 21-5.Survey the tackiness result and show that composition of the present invention has acceptable tackiness, in other words, probe tackiness value is at least 200g, more preferably is at least 300g, most preferably is at least 380g.G ' and Tg data show that heteromorphic polymer compositions can use in the pressure sensitive adhesive compound, in other words, it is characterized in that having 10 ⁵～10 ⁶Dynes/cm ²G ' and-10～10 ℃ Tg.The embodiment of table 7 has shown the handiness of the technology of the present invention, and promptly the molecular weight of skeleton polymer and branched polymers and density can change, so that said composition can be used in the various pressure sensitive adhesives application.Embodiment 40-41: functionalized to improve cementability to glass

By polymer A 10 and B4 (in embodiment 40), reach polymer A 10 and D (in embodiment 41), extrude through reaction and prepare sample.In both cases, the polymer reaction mixture all floods superoxide, and this impregnated sample is extruded from a twin screw extruder at 210 ℃.The maximum operation (service) temperature of the composition that evaluation obtains, lap shear binding property and T-peel off shear adhesion.

The fusible mensuration of lap shear is by under 350 °F (177 ℃), will test resin moulding-die between two microscope glass slide glasses, mounts slide glass with the area spongiosa back of the body, carries out the lap shear tension test then on the Instron tonometer.

It is as follows that T-peels off the measurement of shear adhesion.Use Loctile Depend tackiness agent (article number 00206, obtain by Loctile Corporation), by (CRS on cold-rolled steel strip, size: 6 * 1 * 0.032 inch (15 * 2.5 * 0.08), obtain by Q-Panel Company) impose surfactant, in glass slide (size: impose adhesive resin on 3 * 1 * 0.05 inch (7.6 * 2.5 * 0.12cm), obtain), and glass slide is fixed on the cold-rolled steel strip by Fisher Scientific.When glass slide and CRS put together, tackiness agent mixed fully.These joints are kept together, apply 10 pounds weight (22Kg) above, continue 10 minutes.This CRS/ glass bar is placed on (180 ℃) on the hot plate.HDPE-g-EO test polymkeric substance and second metal strip are placed on the CRS/ glass bar that remains on the hot plate.With they heating, melt up to polymer samples.Then with they cool to room temperature.These specimen are tested after 24 hours in preparation.

According to ASTM D1876-72 method, use Instron 4204 material testing systems (Materials Testing System), obtain the stress strain diagrm of nominal.Distance between handle is 2 inches (5cm), and crossbeam speed is 10 inches/min (25cm/min).

Heteromorphic polymer compositions and the performance that obtains are listed in the table below in 8.

Table 8

Sample	Polymer B 4 (phr)	Polymkeric substance D (phr)	Polymer A 10 (phr)	Lupersol 130 superoxide (phr)	??USLT ??℃	Lap shear viscosity (pound/inch (kg/cm))	T-peels off shear viscosity (pound/inch (kg/cm))
								??HDPE-g-EO ??(20-1)	??25		????75	????0.5	??120	???25(138)	????0(0)
??MAH-g- ??HDPE-g-EO ??(14-2)		???25	????75	????0.5	??120	???29(112)	????34(29)

When using MAH-g-HDPE to replace HDPE as branched polymers, heteromorphic polymer compositions significantly improves the binding property of glass.The result of table 8 shows that MAH-g-HDPE grafted polymorphic composition has lap shear viscosity and the T-more much higher than not functionalized heteromorphic polymer compositions and peels off shear viscosity.

Mention in tackiness agent compound 21-9 discusses as top, the functionalized heteromorphic polymer compositions of toxilic acid can be used in the pressure sensitive adhesive compound.

Top complete description and the present invention who is illustrated for example in detail should only limit according to following claims.

Claims (15)

1. a heteromorphic polymer compositions is characterized in that comprising: (a) homogeneous phase line style or the ethylene/alpha-olefin interpolymer skeleton of line style basically; (b) be suspended on side chain on this skeleton, this side chain comprises that density is than skeletal density height 0.004g/cm at least ³Alathon or ethylene/alpha-olefin interpolymer.

2. the heteromorphic polymer compositions of claim 1, side chain wherein are characterised in that and comprise that density is than skeletal density height 0.006g/cm at least ³Alathon or ethylene/alpha-olefin interpolymer.

3. the heteromorphic polymer compositions of claim 1, then wherein the feature of polymer backbone also at ethene and at least a C ₃-C ₂₀The homogeneous phase line style or the interpolymer of line style basically of alpha-olefin.

4. the heteromorphic polymer compositions of claim 3, homogeneous phase line style wherein or basically the feature of the interpolymer skeleton of line style also be to have at least 50 CDBI value and less than 3 M _w/ M _n

5. the heteromorphic polymer compositions of above-mentioned any claim, wherein skeleton polymer is characterised in that it is line style interpolymer basically, this interpolymer is characterised in that to have:

(a) melt flow ratio I ₁₀/ I ₂〉=5.63,

(b) by the molecular weight distribution M of gel permeation chromatography _w/ M _nSatisfy equation:

(Mw/Mn)≤(I ₁₀-I ₂)-4.63

(c) extrude the critical shear speed stress when melt fracture begins fully of ftheoloqical measurements greater than 4 * 10 by gas ⁶Dyne/cm ²(0.4MPa), perhaps such gas extrudate flow sex change, the feasible critical shear rate of ethenyl copolymer when surperficial melt fracture begins of line style basically, than the critical shear rate of linear ethylene polymkeric substance when surperficial melt fracture begins big at least 50%, wherein the ethenyl copolymer of line style comprises identical comonomer or comonomer combination, the I of linear ethylene polymkeric substance with the linear ethylene polymkeric substance basically ₂, M _w/ M _nWith density the ethenyl copolymer of line style basically 10% in, and wherein basically the ethenyl copolymer of line style and linear ethylene polymkeric substance critical shear rate separately be under same temperature of fusion, the using gas squeezing rheometer record and

(d) the single dsc DSC melting peak between-30～150 ℃.

6. the heteromorphic polymer compositions of above-mentioned any claim, wherein the skeleton interpolymer is characterised in that it is the ethylene/alpha-olefin interpolymer of line style basically, on average is substituted with 0.01～3 long-chain branch/1000 carbon atom on this interpolymer.

7. heteromorphic polymer compositions, following (a) and reaction product (b) have been it is characterized in that comprising: (a) polymkeric substance of the formation side chain of 40～5wt%, this side chain comprises Alathon or ethylene/alpha-olefin interpolymer, (b) material of the formation skeleton of 60～95wt%, this material are the interpolymer of ethene and one or more comonomers or homogeneous line style or the ethylene/alpha-olefin interpolymer of line style basically;

And wherein, the degree of crystallinity of the side chain of formation is than the degree of crystallinity of the skeleton that forms greatly at least 5%;

And wherein, the maximum operation (service) temperature of heteromorphic polymer compositions is than at least 10 ℃ of the non-reactive blending object heights of the skeleton polymer of branched chain polymer that forms and formation.

8. the heteromorphic polymer compositions of above-mentioned any claim, its feature also be to comprise polarity fragment grafted in skeleton polymer and the branched chain polymer one of at least on institute's deutero-part.

9. the method for preparing the heteromorphic polymer compositions of above-mentioned any claim wherein the method is characterized in that to comprise:

(a) under reaction conditions, make ethene and one or more optional alpha-olefin comonomer polymerizations, form the polymkeric substance that constitutes side chain; With

(b) under reaction conditions, make the polymkeric substance of ethene, one or more alpha-olefin comonomer and formation side chain (a) carry out polymerization, form heteromorphic polymer compositions,

Wherein, heteromorphic polymer compositions is characterised in that the branched chain polymer part that has the skeleton polymer part and hang, and wherein branched chain polymer part degree of crystallinity at room temperature is than skeleton polymer part degree of crystallinity height at least 5% at room temperature.

10. the method for claim 9, wherein the polymerization of (a) occurs in first reactor, and polymerization (b) occurs in second reactor, perhaps

Wherein the polymerization of (a) and polymerization (b) occur in the same reactor, and wherein use first kind of catalyzer in the polymerization of (a), use second kind of compatible catalyzer in the polymerization of (b).

11. prepare the method for the heteromorphic polymer compositions of above-mentioned any claim, wherein the method is characterized in that to comprise:

(a) under reaction conditions, make ethene and one or more optional alpha-olefin comonomer polymerizations, form the reactant flow that contains the polymkeric substance that constitutes side chain;

(b) make ethene and one or more alpha-olefin comonomer polymerizations, form and contain homogeneous phase line style or the polymer reaction logistics of line style basically that constitutes skeleton,

(c) randomly, can from reactant flow (a), separate the polymkeric substance that constitutes side chain, from reactant flow (b), separate to constitute skeleton polymkeric substance and

(d) in the presence of radical initiator, make polymkeric substance that constitutes side chain and the polymer reaction that constitutes skeleton, and the polymkeric substance that constitutes side chain is hanging on the polymkeric substance that constitutes skeleton, produce heteromorphic polymer compositions;

Wherein, constitute the polymkeric substance degree of crystallinity at room temperature of side chain than the polymkeric substance degree of crystallinity height at least 5% at room temperature that constitutes skeleton.

12. the method for claim 11, wherein reactions steps (d) was carried out isolate polymkeric substance that constitutes side chain and the polymkeric substance that constitutes skeleton from reactant flow (a) with (b) before, and this method also comprises:

(e) from the hybrid reaction logistics, isolate heteromorphic polymer compositions.

13. above-mentioned any claim or according to the polymorphic composition of above-mentioned any claim preparation, exist with tackiness agent, sealing agent, coating, moulded parts, film, thermoformed articles or fibers form.

14. the Hotmelt Adhesive compound, comprise above-mentioned any claim or according to the polymorphic composition of above-mentioned any claim preparation.

15. the Hotmelt Adhesive compound of claim 14, it is characterized in that, has the probe tackiness of 200g at least, and maximum operation (service) temperature is than at least 10 ℃ of the maximum operation (service) temperature height of the Hotmelt Adhesive of the non-reactive blending thing that comprises branched polymers and skeleton polymer, and the amount of branched polymers and skeleton polymer is identical with the amount that exists in heteromorphic polymer compositions in the described non-reactive blending thing.

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