CN1202911A - Branched block ethylene polymers, their preparation and compositions comprising the same - Google Patents

Abstract

Branched block ethylene polymers prepared from a narrow ethylene polymer, an ethylenically unsaturated functionalized organic compound, and reactive thermoplastic polymer, and methods of preparing such branched block ethylene polymers, are useful to prepare an impact modified ethylene polymer.

Description

The branched block ethylene polymers thing, its preparation method and the composition that comprises it

The field of the invention

The present invention relates to ethene polymers, more particularly polyvinyl block polymer contains the composition of block ethylene polymers thing, prepares the method for this block ethylene polymers thing and the method for compositions that preparation contains this block ethylene polymers thing.

Background of the present invention

Polyvinyl graft modification with various ethylenically unsaturated monomers is well-known in the prior art.This class modification makes that the non-polar polymer material is compatible on limited degree at least with polar material basically.

Yet graft modification has infringement to polyvinyl one or more other performances.For example, USP4,134,927,3,884,882 and 5,140,074 has all reported the crosslinked rheological property that changed because of the graft modification material.These change the processibility of finally having damaged material, have therefore influenced its prospects for commercial application.

Also have, when hope during with ethene polymers and another kind of molded polymeric blend, polyvinyl graft modification (having the binding property of benefiting) can influence that ethene polymers is used with together or the consistency of molding usefulness polymkeric substance.If ethene polymers can be with a kind of mode modification as follows then is ideal: the consistency of other polymkeric substance can not be affected and other performance such as the rheological property of ethene polymers (with preferred resulting blend) are improved simultaneously in ethene polymers and the blend.

The industrial other and special challenge that faces is the improvement of the performance of polycarbonate.This shortcoming what by polycarbonate and various olefin polymer such as new LDPE (film grade) or linear low density polyethylene, or the practice that thermoplastic elastomer such as ethylene/propene copolymer carry out blend has alleviated.The material of these interpolations can improve the tolerance of polycarbonate to solvent, but they trend towards leafing and cause by the reduction in various degree of the toughness of the polycarbonate compositions of blend, shock resistance and weld line strength.The loss of this type of leafing and purposes for example is reported in US-A-4, in 496,693.

The shock resistance of polycarbonate can be improved by introducing emulsion or nuclear-shell elastomer such as methacrylic ester/butadiene/styrene copolymers or butyl acrylate cores rubber.Yet these nuclears-shell rubber impairs processibility because of improving viscosity, and the solvent resistance of polycarbonate is not had improvement.If can not influence toughness and shock strength and weld line strength with the properties-correcting agent that the improves solvent resistance properties-correcting agent of alkene (especially based on) with thermoplastics such as polycarbonate blending, can not cause leafing (by peeling off or cracked proof the in the moulded product), will be ideal.

US-A-5,346,963 disclose with alefinically unsaturated compounds grafted ethene polymers, disclose the blend of this grafted ethylene polymer and compatible thermoplastic plastics.Yet in reference, branched block ethylene polymers thing is not as defined above mentioned in the narration of the ethene improved polymkeric substance of grafting.

US-A-5,300, if 574 disclose and in the presence of polymeric amide, carry out graft reaction and to the unsaturated ethylene polymkeric substance the time, reduced crosslinked maleic anhydride graft.Yet this document is not mentioned the branched block ethylene polymers thing.

People such as Hughes are in US patent 5, disclose in 346,963 with one or more polyethylene of unsaturated organic compound grafted substantial linear that contains ethylenic unsaturated bond and carbonyl in thermoplastic blend as the compatilizer of filled polymer and as the impact modifying agent of other polyolefine and polymeric amide.

An object of the present invention is to prepare a kind of polymkeric substance based on ethene, it has improved visco-elasticity and it will make this blend improve rheological property when being used as properties-correcting agent in the blend with thermoplastic moulded polymkeric substance, excellent impact resistance, transparency in thin parts and the film, surface hardness, and have required balance between the notch sensitivity that reduces.This purpose and following public other purpose can be used for realizing by preparation and this branched block ethylene polymers thing making in composition of the present invention of branched block ethylene polymers thing.

The present invention's general introduction

In one aspect, the present invention relates to the branched block ethylene polymers thing, it comprises: (a) ethene polymers; (b) the unsaturated functionalized organic compound of olefinic; (c) can form the reactive behavior thermoplastic polymer of branched block ethylene polymers thing with the unsaturated functionalized organic compound reaction of olefinic.

Aspect preferred, the present invention relates to the branched block ethylene polymers thing, comprising: (a) homogeneous ethene polymers has:

(i) be lower than about 3.0 Mw/Mn ratio by what gel permeation chromatography recorded;

(ii) about 0.93g/cm ³Or lower density;

(iii) be higher than about 30% short-chain branched dispersion index; (b) the unsaturated functionalized organic compound of olefinic; (c) can form the reactive behavior thermoplastic polymer of branched block ethylene polymers thing with the unsaturated functionalized organic compound reaction of olefinic.

On the other hand, the present invention relates to prepare a kind of comprise ethene polymers, the unsaturated functionalized organic compound of olefinic and can with the method for the branched block ethylene polymers thing of the reactive behavior thermoplastic polymer of the unsaturated functionalized organic compound reaction of olefinic, this method comprises: (1) allows the unsaturated functionalized organic compound of olefinic form polyvinyl branch and has formed branched ethylene polymer, afterwards, (2) allow reactive behavior thermoplastic polymer and branched ethylene polymer reaction form the branched block ethylene polymers thing.

Aspect preferred, the present invention relates to prepare the method for branched block ethylene polymers thing, this polymkeric substance comprises: (a) homogeneous ethene polymers, it preferably has:

(i) the Mw/Mn ratio is recorded by gel permeation chromatography, is lower than about 3.0;

The (ii) about 0.93g/cm of density ³Or it is lower; With

(iii) short-chain branched dispersion index is higher than about 30%; (b) the unsaturated functionalized organic compound of olefinic; (c) can with the reactive behavior thermoplastic polymer of the unsaturated functionalized organic compound reaction of olefinic; This method comprise branch that (1) allows the unsaturated functionalized organic compound of olefinic form the ethene homogeneous polymers formed branching ethene homogeneous polymers and afterwards (2) allow reactive behavior thermoplastic polymer and branching homogeneous ethene polymers reaction formation branched block ethylene polymers thing.

Aspect another, the present invention relates to comprise thermoplasticity blend usefulness or molding a kind of composition with the blend of polymkeric substance and branched block ethylene polymers thing, wherein the branched block ethylene polymers thing comprises: (a) ethene polymers; (b) ethylenically unsaturated organic compounds; (c) can with the reactive behavior thermoplastic polymer of the unsaturated functionalized organic compound reaction of olefinic.

In preferred embodiments, the present invention relates to comprise thermoplasticity blend usefulness or the molding a kind of composition with the blend of polymkeric substance and branched block ethylene polymers thing, wherein the branched block ethylene polymers thing comprises: (a) homogeneous ethene polymers, and it has:

(i) the Mw/Mn ratio is recorded by gel permeation chromatography, is lower than about 3.0;

The (ii) about 0.93g/cm of density ³Or it is lower; With

(iii) short-chain branched dispersion index is higher than about 30%; (b) ethylenically unsaturated organic compounds; (c) can with the reactive behavior thermoplastic polymer of the unsaturated functionalized organic compound reaction of olefinic.

Aspect another, the present invention relates to from the thermoplasticity blend with or molding prepare method for compositions with polymkeric substance, ethene polymers, the unsaturated functionalized organic compound of olefinic and reactive behavior thermoplastic polymer, this method comprises: (1) forms the branched block ethylene polymers thing by following process: (a) the unsaturated functionalized organic compound of olefinic is incorporated into form on the ethene polymers branched ethylene polymer and afterwards (b) allow the reactive behavior thermoplastic polymer form the branched block ethylene polymers thing to react with the branched ethylene polymer reaction; Then (2) with branched block ethylene polymers thing and thermoplasticity blend with or molding carry out blend with polymkeric substance.

Aspect preferred, the present invention relates to from the thermoplasticity blend with or molding (it is about 3.0 that the Mw/Mn ratio that is recorded by gel permeation chromatography is lower than, the about 0.93g/cm of density with polymkeric substance, homogeneous ethene polymers ³Be higher than about 30% with short-chain branched dispersion index), the unsaturated functionalized organic compound of olefinic and reactive behavior thermoplastic polymer prepare method for compositions, this method comprises: (1) forms the branched block ethylene polymers thing by following process: (a) the unsaturated functionalized organic compound of olefinic is incorporated into form on the homogeneous ethene polymers branching homogeneous polymers and afterwards (b) allow the reactive behavior thermoplastic polymer form the branched block ethylene polymers thing to react with the reaction of branching homogeneous ethene polymers; Then (2) with branched block ethylene polymers thing and thermoplasticity blend with or molding carry out blend with polymkeric substance.

One preferred aspect, the reactive behavior thermoplastic polymer of component (c) is an amine-functionalized polymers.Another preferred aspect, the reactive behavior thermoplastic polymer of component (c) is a polyester.

Surprised is, from the shown ideal temperature storage modulus that goes out of the goods of composition molding of the present invention processing, be higher than by (a) and (c) description to the blend of emergencing copolymer [below be abbreviated as (a)/(c)] or only use the shown storage modulus that goes out of (b) polymers grafted (a) [below be abbreviated as (a)/(b)].That is, branched block ethylene polymers thing of the present invention deliquescing and distortion under higher temperature, promptly they demonstrate than (a)/(c) blend or the upper limit use temperature that (a)/(b) grafts is higher.Branched block ethylene polymers thing of the present invention also shockingly demonstrates than (a)/(c) blend or (a)/(b) the low tan δ of tan δ of grafts.

Fig. 1-the 18th, accompanying drawing (graphic representation).Fig. 1 shows the storage modulus of branched block ethylene polymers thing of the present invention (mark * * *), compares with the contrast that is not embodiments of the invention.Fig. 2 a and 2b are by triangle branched block ethylene polymers thing of representing of the present invention and the DMS rheology contrast that is not the contrast of the embodiment of the invention.Fig. 3 has provided tan δ, E ' and the E of branched block ethylene polymers thing of the present invention ".Fig. 4 has provided the RMS rheological data of branched block ethylene polymers thing of the present invention under 190 ℃ of being represented by rhombus, compares with the contrast that is not embodiments of the invention.Fig. 5 has provided the tan δ data of branched block ethylene polymers thing of the present invention under 190 ℃ of being represented by rhombus, compares with the contrast that is not embodiments of the invention.Fig. 6 has provided the RMS rheological data of branched block ethylene polymers thing of the present invention under 190 ℃ of the ratio with different " being grafted to the homogeneous ethene polymers on the maleic anhydride " and " is the reactive behavior thermoplastic polymer of representative by nylon ".Fig. 7 has provided the RMS rheological data of branched block ethylene polymers thing of the present invention under 230 ℃ of the ratio with different " being grafted to the homogeneous ethene polymers on the maleic anhydride " and " is the reactive behavior thermoplastic polymer of representative by nylon ".Fig. 8 has provided the tan δ data of branched block ethylene polymers thing of the present invention under 190 ℃ of the ratio with different " being grafted to the homogeneous ethene polymers on the maleic anhydride " and " is the reactive behavior thermoplastic polymer of representative by nylon ".Fig. 9 has provided the tan δ data of branched block ethylene polymers thing of the present invention under 230 ℃ of the ratio with different " being grafted to the homogeneous ethene polymers on the maleic anhydride " and " is the reactive behavior thermoplastic polymer of representative by nylon ".

(be expressed as MAHg 8200, wherein 8200 is polyvinyl symbols to Figure 10, Engage for the homogeneous ethene polymers with maleic anhydride graft ^TM8200) the RMS data under (not being embodiments of the invention) and by this graftomer and PCTG (poly terephthalic acid cyclohexanedimethanoester ester glycol), each comfortable 190 ℃ of PET (polyethylene terephthalate) and the formed branched block ethylene polymers things of nylon 6 reactions contrast.Figure 11 provided MAHg 8200 (as mentioned above) with by the RMS data under 190 ℃ of this graftomer and nylon 6, Ni Long11 and each leisures of the formed branched block ethylene polymers thing of nylon 12 reactions.Figure 12 provided with Figure 11 in same contrast, but under 230 ℃.Figure 13 has provided the rheology index that has improved by the nylon 6 that adds different percentage ratios in MAHg 8200.Figure 14 has provided the melt strength that has improved by the nylon 6 that adds different percentage ratios in MAHg 8200.Figure 15 has provided the influence of oil to the viscosity of branched block ethylene polymers thing, and this polymkeric substance comprises through maleic anhydride graft to by the nylon 6 on the homogeneous ethene polymers of XU58300 (available from the ethene polymers of Dow chemical company) expression.Figure 16 has provided the influence of oil to the tan δ of branched block ethylene polymers thing, and this polymkeric substance comprises through maleic anhydride graft to by the nylon 6 on the homogeneous ethene polymers of XU58300 (available from the ethene polymers of Dow chemical company) expression.Figure 17 compares various branched block ethylene polymers things, and these polymkeric substance comprise various reactive behavior thermoplastic polymers, that is, and and through PPO/HIPS (polyphenylene oxide/high-impact polystyrene), PCTG, PET and the nylon 6 of maleic anhydride graft to the MAHg 8200.Figure 18 has provided the Xiao A hardness at various temperatures that is reached by the branched block ethylene polymers thing that comprises 70wt%MAHg 8200 and 30wt% nylon 6.

Figure 19 contains the graphic representation of the viscosity of composition under 230 ℃ of 75% polypropylene and 0,10,15,20,25 and 30% branched block ethylene polymers thing to rotation frequency (being measured by rheology (dynamically) mechanics frequency spectrum).

Figure 20 contains the graphic representation of the tan δ of composition under 230 ℃ of 75% polypropylene and 0,10,15,20,25 and 30% branched block ethylene polymers thing to rotation frequency (being measured by rheology (dynamically) mechanics frequency spectrum).

ITP is the ethene polymers of substantial linear in the accompanying drawings; PBT is a polybutylene terephthalate; MAH is a maleic anhydride; MMA/GMS is methacrylic ester-butyl acrylate cores-methyl propenoic acid glycidyl base ester, 98: 8: 2 part by weight, and this will further explain in an embodiment of the present invention.DMS is the dynamic mechanical frequency spectrum; RMS is the rheology frequency spectrum.Abbreviation POE (polyolefin elastomer) also is applicable to and represents the homogeneous ethene polymers in the accompanying drawings.RSA is a rheology solid analysis instrument.

Composition of the present invention can be used in the application of the impact modified polymkeric substance of any use.For example, they are used to produce film, fiber, coating, extruded sheet, multi-layer laminate and various molding or moulded products, especially the packing ring extruded of section bar; Blowing and thermoformed articles, fascia, Vehicular side body moulded product and car inner assembly, and other parts and the assembly that are used for automobile, Electrical and Electronic industry.Composition of the present invention is also as hotmelt.Method of the present invention is used to prepare and has as before or polymkeric substance, composition and the moulded parts of similar applications.

Branched block ethylene polymers thing of the present invention shockingly can be used as rheology modifier, impact-resistance modified dose and melt strength toughener.Properties-correcting agent efficient is the function of melt elasticity, dispersiveness and the consistency of branched block ethylene polymers thing.The branched block ethylene polymers thing can be used for blowing and thermoforming.They can also be used for oil-filled.In addition, especially when the reactive behavior thermoplastic polymer was amine-functionalized polymers such as nylon, the branched block ethylene polymers thing can be used for making callable non-crosslinked foam.For the reactive behavior thermoplastic polymer is the situation of the branched block ethylene polymers thing of nylon, use Ni Long11 to obtain the highest melt strength as the branched block ethylene polymers thing of reactive behavior thermoplastic polymer, being to utilize nylon 6 subsequently, is to utilize nylon 12 more subsequently.

Of the present invention being described in detail

Branched block ethylene polymers thing of the present invention prepares from following component: (i) ethene polymers, preferably have be lower than by the defined Mw/Mn of gel permeation chromatography about 3.0, more preferably homogeneous ethene polymers; The (ii) unsaturated functionalized organic compound of olefinic; (iii) can with the reactive behavior thermoplastic polymer of the unsaturated functionalized organic compound reaction of olefinic.Ethene polymers is considered to first kind of polymer blocks.The unsaturated functionalized organic compound of olefinic is by forming branched ethylene polymer on its pair key addition ethene polymers.If the branch that is formed by the unsaturated functionalized organic compound of olefinic has enough length (for example containing 3 or more a plurality of molecule), we can say that it has formed second block of itself.Yet this branch is only formed by a unsaturated functionalized organic compound molecule of olefinic.Irrelevant with the ramose length that is formed by the unsaturated functionalized organic compound of olefinic, branched ethylene polymer is by functional group on the residue of the unsaturated functionalized organic compound of olefinic and the final polymer blocks of reactive behavior thermoplastic polymer reaction formation.

Tapping point (contain the residue of one or more molecules of the unsaturated functionalized organic compound of olefinic and keyed jointing reactive behavior thermoplastic polymer as final polymer blocks) is different from long-chain and short-chain branched, and this branching is to occur on the ethene polymers preparing the ethene polymers process from ethene and (non-essential) another kind of monomer such as alpha-olefin.The skeleton formed branch of growing is opposite with following in the ethylene polymerization process, and the tapping point that forms from the unsaturated functionalized organic compound of olefinic is added its initial polymerization after, and to be incorporated on the ethene polymers and to provide be the final polymer blocks needed reaction active site of keyed jointing reactive behavior thermoplastic polymer as the branched block ethylene polymers thing.

About subfraction (a)-ethene polymers

Subfraction (a) is the ethene polymers that forms first block in the preparation of branched block ethylene polymers thing of the present invention.The ethene polymers that is used for this purpose comprises, conventional ethene polymers such as new LDPE (film grade) (" LDPE "), linear low density polyethylene (" LLDPE "), and high density polyethylene(HDPE) (" HDPE ").That LDPE typically is considered to be under the condition of high voltage preparation and have an about 0.935g/cm of about 0.915- ³Density.This low density is that the many zones by amorphous arrangement cause, and it is the feature of LDPE, owing to its long chain branches, and the length that many branches are the same with skeleton.As long as the density of pure amorphous polyethylene is 0.855g/cm ³, be 0.97g/cm with having density ³The contrast of pure crystalline polypropylene, can find that LDPE has some crystallizations.Yet its long chain branching is a principal character.Typically per 1000 carbon atoms of LDPE have 4-25 and sometimes up to 90 these type of long chain branches.It also has 10-35 short chain/per 1000 carbon atoms, each short chain contains 2-8 carbon atom, this is sting (backbiting) and molecule and caused along the rearrangement of skeleton by returning in the chain growth process, is not caused by the comonomer introducing the LLDPE and do not resemble.

Can prepare LDPE in tubular reactor or stirring tank, when when heating, the pressurization feedstream of ethylene gas, radical initiator and optional chain-transfer agent is injected in the reaction unit.Form reaction usually 1,500-3,000atm (152-304MPa) and carry out being no more than under 300 ℃ the temperature, this is known in the prior art.In the polymerization process of LDPE, ethene and other monomer such as vinyl-acetic ester, ethyl propenoate, vinylformic acid, vinylchlorid or carbon monoxide carry out copolymerization.

Usually be considered to form LLDPE for preparing under that suitable similar low pressure condition of HDPE.Yet, obtain low density product (0.910-0.940g/cm ³), because, not to form homopolymer, ethene and one or more alpha-olefin copolymers close, and they take short-side chain form and function in final product.Because the most frequently used comonomer is alpha-olefin such as 1-butylene, 4-methyl-1-pentene, 1-hexene or 1-octene, these side chains prevent tight, the accumulation of crystallization type fully of HDPE, but they are not too near, as long as make under condition of high voltage and the complete branching of LDPE bonded, long side chain.LLDPE can form slurry by using the carrying chrome catalysts in light hydrocarbon diluent, or by using organo-metallic-titanium type catalyzer in hexane, to form slurry.It can also form solution in suitable hydrocarbons under about 250 ℃, or it can form in gas phase, as Levine at USP4, described in 011,382, or as Jezl at USP4, described in 129,729.

About typically 94% crystallization of HDPE homopolymer or multipolymer also has density for about 0.935g/cm ³More than, especially be about 0.950-0.970g/cm ³HDPE because other higher degree of crystallinity and density, has higher fusing point-135 ℃ to 115 ℃ than LDPE.Crystallization HDPE homopolymer has the linearity of rule and typically forms a kind of ordered set aggressiveness that is known as crystal grain in the back that is cooled, so HDPE has obtained excellent toughness and shatter-proof fragility.If ethene and alpha-olefin copolymer close, as mentioned above, if or by concrete reaction mechanism specific side reaction causes short-chain branchedly, then will disturb crystallization and density in HDPE correspondingly to descend.For example, the HDPE with the preparation of Ziegler transition-metal catalyst has about 0.5-4 short chain branch (especially methyl)/per 1000 carbon atoms.The molecular weight of HDPE is usually 50, and 000-1 is in 000,000 scope or higher.The molecular weight that exceeds specified point raising HDPE is in fact because chain entanglement causes the decline of density, but influence is not too obvious.Overwhelming majority situation, HDPE intensity descends with the decline of molecular weight.HDPE can prepare in slurry system, and wherein high-purity ethylene is added into to contain and is used for dissolve ethylene and making in the annular reactor of the low boiling hydrocarbon that catalyzer and polymer beads suspend.In addition, HDPE can prepare in gas phase process, does not wherein use hydrocarbon diluent and fluidized-bed to be used for stirring and suspended polymer particles.The method of making HDPE is described in the USP2 of Hogan particularly, in 825,721.

About the purposes of homogeneous ethene polymers as subfraction (a)

Preferably, subfraction (a) is the homogeneous ethene polymers.Being characterized as of homogeneous polymers has narrow polymolecularity (Mw/Mn) and uniform short-chain branched distribution.The polyvinyl polymolecularity of homogeneous as described herein (Mw/Mn) can be determined from the data that obtained by gel permeation chromatography (GPC).It is 150 ℃ of high temperature chromatogram arrangements of Waters that the typical case is used for this purpose instrument, and three porousness mixed bed columns (Polymer Laboratories 103,104,105 and 106) are housed, in 140 ℃ of operations down of system temperature.Employed solvent is 1,2, the 4-trichlorobenzene, and the 0.3wt% solution of preparation sample is with injection.Flow velocity is that 1.0 ml/min and injection volume are 200 microlitres.

Poly molecular weight determination is that the polystyrene standard (available from Polymer Laboratories) by using narrow molecular weight distributions is carried out together with their elution volume.Measure the equivalent molecular weight of polyethylene by the suitable mark Hao Wenke coefficient that uses polyethylene and polystyrene, as Williams and Word at the polymer science periodical, Polymer Letter, 6 volumes, 621 pages, nineteen sixty-eight (it is for reference to be introduced into this paper) is described, the following equation of computing:

M _Polyethylene=a* (M _Polystyrene) ^bA=0.4316 wherein, b=1.0 and M be polyethylene and polystyrene 1,2, the molecular weight in the 4-trichlorobenzene.Weight-average molecular weight Mw calculates in the usual way according to following relational expression: Mw=∑ wi*Mi, wherein wi and Mi are respectively the weight fraction and the molecular weight of the i fraction that wash-out goes out from the GPC post.Number-average molecular weight Mn calculates in the usual way according to following relational expression: Mn=[∑ ni*Mi]/∑ ni, wherein ni and Mi are respectively the molecule number and the molecular weight of the i fraction that wash-out goes out from the GPC post.Symbol * represents a step multiplication.

The polyvinyl polymolecularity of described homogeneous (Mw/Mn) be lower than about 3.0, preferably about 1.5-about 2.5 and more preferably from about 1.7-is about 2.3, most preferably from about 2.

When they are ethylene/alpha-olefin copolymer, the homogeneous ethene polymers will have uniform branching and distribute.Term " evenly branching " and " evenly branching distributes " are meant that (1) alpha-olefin comonomer is the given intramolecularly random distribution at ethene/comonomer multipolymer; (2) all basically copolymer molecules have same ethene/comonomer ratio; (3) polymkeric substance is characterised in that narrow short-chain branched distribution; (4) polymkeric substance does not have measurable high-density, crystalline polymer fraction [for example by comprise polymkeric substance classification wash-out measure as those technology of temperature function] substantially; (5) feature of polymkeric substance, press 21C.F.R.177.1520 (c) and (d) in the condition described measure, be the positive hexanaphthene extraction quantity that has (i) but significantly reduce (for example ethene/1-octene copolymer be higher than be lower than 1% extractable matter under the density of about 0.90g/cc), or (ii) tangible amorphism, by when the polymkeric substance that is higher than 75wt% is solvable under prescribed condition, showing that (for example, ethene/1-octene copolymer is at about 0.90g/cm ³Be 90% solvable and be 100% solvable under the density of about 0.88g/cm under the density).

Typically, the homogeneous ethene polymers has even short-chain branched distribution and does not have any measurable high-density fraction, be that these polymkeric substance do not contain by USP5, the degree of branching that " the temperature rising elution fractionation method " described in 089,321 measured is less than or equal to any polymer fractions of 2 methyl/1000 carbon atoms.

Homogeneity or narrow degree that branching distributes are further represented by the value of forming distribution branch index (" CDBI ") or short chain branch dispersion index (" SCBDI ").CDBI is defined as having the weight percentage (wt%) of the polymer molecule of co-monomer content in average total mole co-monomer content of 50%.The CDBI of polymkeric substance is for example easily by using as the polymer science periodical of Wild, the polymer physics version, 20 roll up, 441 pages, nineteen eighty-two and in US patent 4,798,081 (it is for reference to be introduced into this paper) described temperature rising elution fractionation calculate.The CDBI of the homogeneous ethylene/alpha-olefin copolymer of Shi Yonging is higher than approximately 30% in the present invention, preferably is higher than about 50% and more preferably be higher than about 80% and most preferably be higher than about 90%.

The homogeneous ethene polymers does not comprise from its definition: the inhomogeneous branching linear low density polyethylene or the linear high-density polyethylene that use Ziegler-Natta polymerization method (for example, pressing the USP4 of Anderson, described in 076,698) to make; Or the high pressure of branching, radical polymerization polyethylene and other high-pressure ethylene multipolymer (for example, Ethylene/vinyl acetate or ethylene/vinyl base alcohol copolymer), known for skilled person of the prior art have a large amount of long chain branches.

For the homogeneous ethene polymers in the ethylene/alpha-olefin copolymer, it has a unique melting hump, and (DSC) records between 30 ℃ and 150 ℃ by dsc.This linear tetrafluoroethylene polymer with the inhomogeneous branching of Ziegler process polymeric is opposite, and the latter is owing to their wide branching distribution has 2 or a plurality of melting hump.Yet, have an about 0.875g/cm of density for some class ³With about 0.91g/cm ³The homogeneous ethene polymers, single melting hump will demonstrate (depending on the device susceptibility) " shoulder " or " hump " on the downside (promptly being lower than fusing point) of melting hump, they account for below 12% of the total melting heat of polymkeric substance, typically are lower than 9%, more typically are lower than 6%.This phenomenon changes owing to chain in the polymkeric substance and it is that the basis is differentiated with gradient monotone variation in the whole melting area of this phenomenon of single melting hump.This phenomenon takes place in 34 ℃ of the fusing point of single melting hump, typically in 27 ℃ and more typically in 20 ℃.

Use the single melting hump of determine with dsc method with indium and deionized water calibration.This method comprises the sample of about 5 7mg sizes, " heating for the first time " was to about 150 ℃ of maintenances 4 minutes, be cooled to 30 ℃ with 10 ℃/minute speed and kept 3 minutes and be heated to 150 ℃, draw " heating for the second time " hot-fluid/temperature curve with 10 ℃/minute speed.Area below curve calculates total melting heat of polymkeric substance.The melting heat (if existence) that is attributable to above-mentioned phenomenon can be calculated by operational analysis balance and weight percentage and measure.

A kind of homogeneous ethene polymers of known type is " a homogeneous linear tetrafluoroethylene polymer ".The homogeneous ethene polymers does not have long chain branching, as following definition.Term " linearity " is not meant body high pressure branched polyethylene, and ethylene, or ethylene/vinyl alcohol copolymer have many long chain branches because the polymkeric substance of these types is known the skilled person in prior art.

The homogeneous linear tetrafluoroethylene polymer is from the polymkeric substance of known type, its example is included in USP3,645, described in 992 those, by use in having the batch reactor of higher ethylene concentration that so-called single position (single site) catalyzer makes those [as US patent 5,026,798 (Canich) or US patent 5,055, described in 438 (Canich)] and by use in having the batch reactor of higher concentration of olefin also that the constrained geometry catalyzer makes those [as US patent 5,064,802 (Stevens) or EP-A-416 are described in 815 (Stevens)].There is not long chain branching in these polymkeric substance, as by Van der Sanden and Halle at TappiJournal, described in 1992 2 months.The method of using metalloscene catalyst to produce the homogeneous linear tetrafluoroethylene polymer has been developed much, for example, sees Ewen in USP4,937,299, EP129,368, EP260,999, USP4,701,432, USP4,937,301, USP4,935,397, USP5,055,438 and WO90/07526, it is for reference that each part document is introduced into this paper.This base polymer can make by polymerization process such as gas phase, slurry or the solution methods of routine.

Preferably, the homogeneous ethene polymers of known type is that " ethene polymers of substantial linear " and embodiment are characterized as required processibility level, for example to the Wheat Protein of melt fracture, even under the shearing force condition.The ethene polymers of substantial linear has the critical shear rate when surperficial melt fracture begins and has a kind of processing index, they be significantly higher than respectively and significantly be lower than same molecular weight distribution and melt index lower linear poly those.The ethene polymers of substantial linear have the shear shinning behavior and with the similar workability of highly branched new LDPE (film grade) (LDPE), and have the intensity and the toughness of linear low density polyethylene (LLDPE).The ethene polymers of substantial linear described herein and make their method also is described in US patent 5,272,236, US5,278,272 and US.SN 08/301,948.

Here employed " ethene polymers of substantial linear " is meant, except introducing the short-chain branched distribution that is caused because of any comonomer, polymkeric substance is further characterized in that to have long chain branches.The ethene polymers of substantial linear embodies to be characterized as to have and is greater than or equal to 5.63 melt flow and compares I ₁₀/ I ₂, be less than or equal to I ₁₀/ I ₂-4.63 molecular weight distribution (by gel permeation chromatography) Mw/Mn and have certain critical shear rate when surperficial melt fracture begins, this speed ratio has roughly the same I ₂High at least by 50% with Mw/Mn and/or the critical shearing stress that when surperficial melt fracture begins, had, or be higher than about 2.8 * 10 ⁶Dynes per centimeter ²Critical shear rate.

According to Ramamurthy at the rheology periodical, 30 (2), 337-357 described in 1986, is higher than some critical flow speed, and surperficial melt fracture can take place, and causes the more irregularity of severe form " shark skin " that is lost to from specular gloss.Here employed, " beginning of surperficial melt fracture " embodiment is characterized as loss extrudate glossy and begins, and the surface irregularity performance of extrudate is enough only detected by 40 * magnifying glass at this moment.The ethene polymers of substantial linear will further embody and be characterized as: critical shear rate is than having about identical I when the beginning of surperficial melt fracture ₂With the linear tetrafluoroethylene polymer of the Mw/Mn critical shear rate high at least 50% when the beginning of surperficial melt fracture.Apparent shear-stress/apparent shear rate curve is used for by using mouthful mould or gas squeezing rheometer (gas extrusion rheometer-GER) to verify the melt fracture phenomenon in the nitrogen pressure scope of 5250-500psig; according to people such as Shida in Polymer Engineering Science (polymer engineering science); 17 volumes; No; 11 (1977) and at the Rheometers of John Dealy for Molten Plastics (rheological analysis of molten plastic); described in the Van Nostrand Reinhold Co. (1982), 97-99 page or leaf like that.According to Ramamurthy at the rheology periodical, 30 (2), 337-357 described in 1986, is higher than some critical flow velocity, the irregularity of viewed extrudate can loosely be divided into two kinds of main types: surperficial melt fracture and overall melt fracture.

Surperficial melt fracture takes place under apparent steady flow condition, is in the scope that is lost to severe form " shark skin " more of specular gloss in detail.In this publication, " beginning of surperficial melt fracture " embodies the beginning that is characterized as the loss of extrudate glossy, and the surface irregularity of extrudate is only detected by 40 * magnifying glass at this moment.The critical shear rate of the ethene polymers of substantial linear when surperficial melt fracture begins is than the critical shear rate height at least 50% of common linear tetrafluoroethylene polymer when surperficial melt fracture begins, I for them ₂, polymolecularity and density are equivalent to the 90-110% of the polyvinyl analog value of substantial linear separately.Preferably, the critical shearing stress of the ethene polymers of substantial linear when surperficial melt fracture begins is higher than about 2.8 * 10 ⁶Dynes per centimeter ²

Overall melt fracture can take place under instability flows condition and be in detail from regular surfaces distortion (as the rough and smooth alternately, or spiral pattern) in the scope of random distortion.For coml acceptability (for example with regard to the blown film goods),, should be minimum if surface imperfection exists.Critical shear rate and critical shearing stress when overall melt fracture begins (OGMF) are with relevant by the variation of the surfaceness of the extrudate of GER production and configuration when surperficial melt fracture begins (OSMF).For the ethene polymers of substantial linear described herein, critical shearing stress preferably is higher than about 4 * 10 when overall melt fracture begins ⁶Dynes per centimeter ²

Measure and measure for the GER melt fracture for following described processing index (PI), do not have mineral filler and 20ppm is arranged or the situation of lower Al catalysts residue under the ethene polymers of test substantial linear.Measure for these, polymkeric substance preferably contains antioxidant, as phenols, and Hinered phenols, phosphorous acid esters or phosphinate, the mixture of phenols or Hinered phenols and phosphorous acid ester or phosphinate when preferred.

Other indication of the polyvinyl improvement processibility of substantial linear is rheology processing index (PI).PI is the apparent viscosity (thousand pools) of polymkeric substance, and extrudes rheological analysis (GER) by gas and measure.More than GER is described with the mensuration of melt fracture phenomenon.Under nitrogen pressure 2500psig, measure processing index in 190 ℃.(for example has I for the high workability polymkeric substance ₂Be 50-100g/10min or higher polymkeric substance), using diameter is 0.0296 inch (752 microns), preferred 0.0143 inch, having 20: 1 length/diameter ratios and having input angle is 180 ℃ mouth mould.

Processing index calculates with millipoise unit from following equation:

PI=2.15 * 10 ⁶Dynes per centimeter ²/ (1000 * shearing rate)

Wherein 2.15 * 10 ⁶Dynes per centimeter ²Be that shear-stress under 2500psi and shearing rate are the shearing rates on wall, represent by following equation:

32Q '/(60 seconds/minute) (0.745) (diameter * 2.54 centimetre/inch) ³Wherein Q ' is rate of extrusion (g/min), the 0.745th, and poly fusant density (g/cm ³); With diameter be kapillary opening diameter (inch).PI is 2.15 * 10 ⁶Dynes per centimeter ²The apparent viscosity of the material measured down of apparent shear-stress.

For the ethene polymers of substantial linear, PI be less than or equal to common linear tetrafluoroethylene polymer PI 70%, I for them ₂, polymolecularity and density are equivalent to the 90-110% of the polyvinyl analog value of substantial linear separately.

The ethene polymers of substantial linear has improved melt elasticity or melt tension, with the homogeneous linear tetrafluoroethylene polymer Comparatively speaking.By specially specified pulley transverter and melt index apparatus are measured " melt tension ".Melt tension be extrudate or wire drawing above pulley by arrive two inches with the rotary drum of 30rpm rotating speed rotation in by extrudate or load that wire drawing was applied.It is similar that melt tension is measured the method for being carried out with " the melt tension tester " made by Toyoseiki, and by John Dealy in Rheometers for MoltenPlastics (rheological analysis of molten plastic), Van Nostrand Reinhold Co. (1982) is described in the 250-251 page or leaf.The polyvinyl melt tension of substantial linear described herein is at least about 2 grams, with especially for having narrow molecular weight distributions those of 1.5-2.5 according to appointment, melt tension is typically at least about 5%, and can be up to about 60%, the melt tension that is higher than common linear ethylene copolymer, the melt index of this multipolymer, polymolecularity and density are equivalent to the 90-110% of the polyvinyl analog value of substantial linear separately.

Polyvinyl other unique property of these substantial linear is a flowing property, and it causes I ₁₀/ I ₂Value is irrelevant with polymolecularity (Mw/Mn) basically.This obviously is different from common Ziegler polymeric homogeneous ethene polymers and is different from the homogeneous polyvinyl resin of common single position polymerization catalyst, and its rheological property should make along with the raising of polymolecularity (Mw/Mn), I ₁₀/ I ₂Value also can improve.Should be noted that, unnecessaryly in the ethene polymers of substantial linear, add superoxide, in order that make polymkeric substance demonstrate the I that has nothing to do with polymolecularity (Mw/Mn) and melt fracture performance ₁₀/ I ₂Value.

In general, the polyvinyl I of substantial linear ₁₀/ I ₂Than being at least about 5.63, preferably at least about 7, in the time of especially at least about 8 with most preferably be at least about more than 9 or 9.To the highest I ₁₀/ I ₂Unique qualification of ratio is a factor of putting into practice the aspect, as economic cause or kinetics of polymerization reaction, but the highest I typically ₁₀/ I ₂Than can and preferably not being no more than about 15 above about 20.On the contrary, the I of homogeneous linear tetrafluoroethylene polymer described herein ₁₀/ I ₂Than generally is below 6 or 6.

It is believed that the polyvinyl desirable melt elasticity of substantial linear and processibility are to obtain from their production method.Can produce polymkeric substance by means of (with intermittently opposite) continuously controlled fusion method of using at least one reactor, for example according to WO93/07187, the method for describing among WO93/07188 and the WO93/07189.Yet these polymkeric substance also can for example use many reactors by the multiple reaction device that uses as describe in US patent 3,914,342, produce under polymerization temperature that is enough to produce the multipolymer with desired properties and pressure.

The polyvinyl polymerizing condition of making substantial linear generally is those conditions that can be used for solution polymerization process, though slurry and gas phase polymerization process also are operable, as long as use appropriate catalyst and polymerizing condition.Multiple reaction device polymerization process also can be used for this purpose, as at US3, and those described in 914,342.The multiple reaction device can serial or parallel connection operation, at least one of reactor, use at least a constrained geometry catalyzer.

Carry out the successive polymerization reaction ideally under the condition well known in the prior art of Z-N or Kaminsky-Sinn type polyreaction, for example the about 0-250 of temperature ℃ is normal pressure-1000 normal atmosphere (100MPa) with pressure.Can use carrier, but preferably catalyzer uses in even (promptly soluble) mode.Certainly, will recognize that,, comprise the monomer of condensation, then form active catalyst system on the spot if catalyzer and its cocatalyst component are introduced directly in the polymerization process and use suitable solvent or thinner.Yet, preferably before joining catalyzer in the polyblend, in suitable solvent, in an independent step, form active catalyst.

Preferably, term " ethene polymers of substantial linear " expression mass polymer is on average replaced by about 0.01 long chain branches/1000 total carbon atom (comprising skeleton and branch's carbon atom)-Yue 3 long chain branches/1000 total carbon atoms.Preferred polymkeric substance is by about 0.01 long chain branches/1000 total carbon atom-1 long chain branches/1000 total carbon atoms, more preferably from about 0.05 long chain branches/1000 total carbon atom-1 long chain branches/1000 total carbon atom and about 0.3 long chain branches/1000 total carbon atom-1 long chain branches/1000 total carbon atoms replace.

Here employed term " skeleton " is meant individual molecule and term " polymer " " " mass polymer " say by common meaning and be meant the polymkeric substance that forms in reactor.Term " body " polymkeric substance is meant the polymkeric substance that obtains from polymerization process, and, for the ethene polymers of these substantial linear, comprise molecule that does not have long chain branching and molecule with long chain branching.Therefore, " body " polymkeric substance is included in all molecules that form in the polymerization process.Ethene polymers for substantial linear, it should be understood that not every molecule has long chain branching, but the long chain branching of q.s is arranged so that the average long chain branching group content of mass polymer can advantageously influence the melt rheological property energy (that is melt fracture performance) of mass polymer.If polymkeric substance is as if the ethene polymers of " substantial linear ", this polymkeric substance must have enough at least molecules that long chain branching is arranged, so that average long chain branching rate is average at least about 0.01/1000 total carbon atom in the mass polymer.

When the ethene polymers of the substantial linear that contains long chain branching was ethylene/alpha-olefin copolymer, long chain branches can have the chain length of hanging down a carbon atom at least than carbonatoms in the comonomer.On the contrary, short chain branch is defined in the chain length that has same carbon atoms number on the residue that comonomer is introduced on the polymer molecule skeleton back and this comonomer.For example, ethene/1-octene sex ethylene polymkeric substance of reaching the standard grade substantially has the skeleton of the long chain branches that has at least 7 carbon atoms of length, and has the only short chain branch of 6 carbon atoms of length.

For ethylene/alpha-olefin copolymer, long chain branches is longer than short chain branch, and this causes owing to alpha-olefin is incorporated on the polymer backbone.The experience effect of the existence in the employed in the present invention substantial linear ethylene/alpha-olefin copolymer of long chain branching can be shown that this performance is extruded rheological analysis (GER) result and/or fluidity of molten I according to gas by the enhanced rheological property ₁₀/ I ₂Improve and come quantitatively and expression, as mentioned above.

By using ¹³C nuclear magnetic resonance spectrum (NMR) is distinguished long chain branching and short-chain branched, and for Alathon with for ethene and C ₂-C ₆The multipolymer of alkene, it can be by using the polymer science bulletin periodical of Randall in Polymer Chemistry and Physics, and C29 rolls up, and the method in the 285-297 page or leaf (1989) is come quantitatively.Yet the long chain branches part that in fact surpasses six carbon atom can not use present being used for to measure the exact length of long chain branches ¹³C NMR distinguishes, and itself, this analytical technology can not be distinguished between 7 carbon atoms and 70 carbon atoms.

US patent 4,500,648 (it is for reference to be introduced into this paper) has instructed long chain branching frequency (LCBF) to be represented by equation LCBF=b/Mw, and wherein b is that the weight average long chain branches number and the Mw of per molecule are weight-average molecular weight.Molar mass average value and long chain branching characteristic are measured by gel permeation chromatography and limiting viscosity method.

Other known technology also is used for measuring long chain branches and exists at ethene polymers (comprising ethene/1-octene copolymer).Two kinds of these class methods are and the gel permeation chromatography (GPC-LALLS) of little angle laser light scattering detector lotus root connection and the gel permeation chromatography (GPC-DV) that joins with differential viscosity detector lotus root.Use and the correlation theory of these technology on long chain branches detects had report in the literature.Referring to, for example, Zimm, G.H. and Stockmayer, W.H., J.Chem.Phys., 17,1301 (1949) and Rudin, A., the modernism of polymer characterization, John Wiley ﹠amp; Sons, New York (1991) 103-112 page or leaf.

A.Willem deGroot and P.Steve Chum (being Dow chemical company) have reported some data in the joint meeting of the analytical chemistry in 4 days Augusts in 1994 of St. Louis, Missouri and spectroscopy association (FACSS), show that GPC-DV is used for the useful technology of the existence of quantitative long chain branches in the ethylene copolymer of substantial linear.Especially, deGroot and Chum find, use measured amount and the use of long chain branches in the ethylene homo matter sample of substantial linear of Zimm-Stockmayer equation ¹³The amount of the long chain branches that C NMR is measured is very identical.

In addition, deGroot and Chum find that the existence of octene does not change the hydrokinetics volume of polyethylene specimen in solution, therefore by knowing that the molecular fraction of octene in sample calculate the molecular weight that causes because of octene short chain branch and improve.By 1-octene short chain branch is removed flatung (deconvolution) to the contribution that molecular weight improves, deGroot and Chum claim that GPC-DC can be used to the content of quantitative long chain branches in the ethylene/octene of substantial linear.

DeGroot and Chum also claim, by the Log (I of GPC-DV mensuration ₂Melt index) as the curve shows of the function of Log (GPC weight-average molecular weight) long chain branching of the polyvinyl long chain branching aspect of substantial linear (not being the long chain branching degree) and high pressure, highly branched new LDPE (film grade) (LDPE) have comparability, and obviously be different from the ethene polymers that uses Ziegler-type catalyst such as titanium complex and conventional homogeneous catalyst such as hafnium and vanadium complex to produce.

Opposite with term " ethene polymers of substantial linear ", term " linearity " is meant that polymkeric substance lacks measurable long chain branches that maybe can characterize, promptly, polymkeric substance on average is lower than 0.01 long branch/1000 carbon atom and is replaced, wherein long chain branching is defined as the chain length of at least 6 carbon atoms, is higher than this mean number and then can not uses nuclear magnetic resonance spectrum to distinguish chain length.

" ethene polymers of substantial linear " prepares by using the constrained geometry catalyzer, and characterizes by narrow polymolecularity (molecular weight distribution) with by narrow comonomer distribution." multipolymer " used herein is meant the polymkeric substance of two or more comonomers, for example multipolymer or terpolymer etc., or in other words, the polymkeric substance that is obtained by the polymerization of ethene and at least a other comonomer.Polyvinyl other fundamental characteristics of these substantial linear comprises low residue thing content (promptly, be used for preparing the catalyzer of polymkeric substance, unreacted comonomer and the lower concentration of low-molecular-weight oligomer in the ethene polymers of substantial linear that in polymerization process, produces), with controlled molecular structure, therefore obtain good processing properties, even molecular weight distribution narrow than common olefin polymer.

Though preferably use the ethene polymers of substantial linear to prepare the branched block ethylene polymers thing, can use any two or more dissimilar above-mentioned polyvinyl mixtures equally.Difference in various types of ethene polymerss can illustrate by using for example following polymkeric substance: (i) common LLDPE is with the substantial linear ethene polymers, or (ii) the Alathon of substantial linear with the ethylene/alpha-olefin copolymer of substantial linear, (iii) two or more substantial linear ethene polymerss made from different constrained geometry catalyzer, the (iv) ethene polymers of two or more substantial linear of in different reactor or reaction zone, making, or (v) has different performance such as density, Mw/Mn, I ₂Or I ₁₀/ I ₂The ethene polymers of two or more substantial linear.Difference in the middle of the ethene polymers in this type of mixture shows that they itself present for example multi-mode density, the Mw/Mn of broadening, and/or the form of multiple melting hump.The polyvinyl mixture of this class, if you are using, can be ideally by using double reaction polymerization process preparation as described below.

Polyvinyl general property

Ethene polymers can be an Alathon, maybe can be ethene and one or more C ₃-C ₂₀Alpha-olefin comonomer and/or one or more C ₄-C ₁₂The multipolymer of diolefine.Ethene polymers also can be ethene and at least a above-mentioned C ₃-C ₂₀The multipolymer of alpha-olefin comonomer and/or diolefine and other unsaturated monomer.Usually, ethene polymers is an ethene and a kind of C only ₃-C ₂₀The multipolymer of alpha-olefin and be more preferably ethene and propylene, iso-butylene, 1-butylene, the 1-hexene, the multipolymer of 4-methyl-1-pentene or 1-octene, the multipolymer of therein ethylene and 1-octene is most preferred.Other preferred monomers of copolymerization comprises vinylbenzene, the vinylbenzene that halogen or alkyl replace, vinyl benzo cyclobutene, 1,4-hexadiene and cyclic hydrocarbon (for example cyclopentenes, tetrahydrobenzene and cyclooctene).

Preferred ethene polymers comprises ethene and the 5-50 of 50-95wt%, at least a comonomer of preferred 10-25wt%.The content of comonomer is according to ASTM D-2238, and method B uses infra-red chromatography to measure.

Measure polyvinyl density and generally be according to ASTM D-792 at least about 0.85g/cm ³, normally at least about 0.865g/cm ³, be at least about 0.89g/cm accidentally ³Polyvinyl density generally is 0.96g/cm ³Or lower, 0.93g/cm normally ³Or lower, chance or 0.90g/cm ³Or it is lower.Density measurement normally is made up of clean polymkeric substance, does not promptly have mineral filler and does not contain the polymkeric substance from the aluminium of catalyst residue above 20ppm.

In some cases, described ethene polymers is crystallization and/or semi-crystalline polymer.They generally at room temperature are solid, and can be in room temperature or granulation under by the temperature of chilled water modulation.For example, has density 0.865g/cm ³The ethene/1-octene copolymer of substantial linear at room temperature have about 10% degree of crystallinity.

Polyvinyl molecular weight can use easily according to ASTM D-1238, and 190 ℃/2.16kg[of condition previously known is for " rule (E) " and also be known as I ₂] the melt index observed value represent.The molecular weight of melt index values and polymkeric substance is inversely proportional.Therefore, molecular weight is high more, and melt index is low more, though relation is not linear.Polyvinyl I ₂Melt index generally is about 0.01g/min (gram/minute) or higher, preferably about 0.1g/10min or higher, more preferably from about 0.5g/10min and most preferably from about 1.0g/10min or higher.Polyvinyl I ₂Melt index generally is about 1000g/min or lower, preferably about 500g/min or lower, more preferably from about 250g/min or lower and 100g/min or lower most preferably from about.

The use of two reactor system in the preparation ethene polymers

Multiple reaction device polymerization process, as in US patent 3,914,342, US.SN08/010,958 (application on January 29th, 1993) and US.SN08/208,068 (application on March 8th, 1994) those disclosed, wherein the multiple reaction device can be operated by serial or parallel connection, can be used to prepare ethene polymers ideally usually.When the parallel running reactor, polymerisate separately (still being in the solution) is mixed into a kind of mixture.When series operation multiple reaction device, the product of first reactor or reaction zone wherein adds other monomer and catalyzer by second reactor or reaction zone.

On lesser extent, if the catalyzer of any work enters in second reactor or the district from first reactor or district, the product main (if not fully) of then discharging from second reactor or district is each mixture of polymers of independent preparation in each reactor or district, only when the reactor parallel running.Yet described ethene polymers is believed to comprise resulting product, if monomer is aggregated on the same polymer chain in first and second reactors or district.

After mixed, or after product is discharged from placed in-line end reaction device or district, remove with method well known in the prior art and to desolvate, to reclaim all polymkeric substance together as a kind of product from the product materials flow of parallel reactor.

Each reactor or the district of serial or parallel connection operation can be with regard to various characteristic aspect differences, these characteristic ratios are the type of employed catalyzer in each reactor or district in this way, be added into the type of the alpha-olefin comonomer in each reactor or the district, or the temperature of each reactor or district's operation.For example, the constrained geometry catalyzer can use in a reactor or district and Z-type catalyst uses in another.When the reactor parallel running, the unnecessary output material that is equal to share that contains each reactor of the materials flow of merging or ejecta (from them, reclaiming final product).

About subfraction (b), the unsaturated functionalized organic compound of olefinic:

The unsaturated functionalized organic compound of the subfraction that uses in the preparation of branched block ethylene polymers thing of the present invention (b)-olefinic contains carbon-to-carbon double bond and forms the polyvinyl branch of narrow polymolecularity by for example grafting method.The unsaturated functionalized organic compound of these olefinics functionalised, and contains functional group, and (perhaps the unsaturated functionalized organic compound of olefinic is an oxazoline for C=O) (for example carboxylic acid or acid anhydrides) or epoxy basic ring, amine, or alcohol as carbonyl.

The unsaturated functionalized organic compound of olefinic that contains at least one carbonyl.The representative that contains this compounds of at least one carbonyl is unsaturated carboxylic acid and their acid esters, acid anhydrides and salt (metal and non-metal salt).Preferably, organic compound contains and carbonyl conjugated olefinic degree of unsaturation.Representative compounds comprises vinylformic acid, methacrylic acid, and toxilic acid, fumaric acid, methylene-succinic acid, Ba Dousuan, methylcrotonic acid and styracin and their ester, acid anhydrides and salt derivative, nonetheless.Maleic anhydride is the ethylenically unsaturated organic compounds that preferably contains at least one carbonyl.

The unsaturated functionalized organic compound of olefinic that contains at least one epoxy basic ring.The representative example that contains the ethylenically unsaturated organic compounds of at least one epoxy basic ring comprises, for example, and the glycidyl esters of unsaturated carboxylic acid (for example methyl propenoic acid glycidyl base ester); Glycidyl ether of unsaturated alcohol (for example allyl glycidyl ether) and alkenyl phenol (for example, pseudoallyl phenyl glycidyl ether); And the vinyl of epoxy group(ing) carboxylic acid and allyl ester (for example vinyl ester of epoxyoleic acid).Other ethylenically unsaturated organic compounds that contains at least one epoxy basic ring is described in Laughner, and US-A-5 is in 369,154 (being introduced into for reference).In the middle of these, preferable methyl vinylformic acid glycidyl esters.

The unsaturated functionalized organic compound of olefinic that contains at least one amine functional group.The representative of amine is the amine compound with at least one ethylenically unsaturated group, as allyl amine, and propenyl amine, butenyl amine, pentenyl amine, hexenyl amine; The amidogen ether class comprises pseudoallyl phenyl ethylamine ether and its homologue (branching, ring-type and nonbranched), the vinyl of amine compound and allyl ethers, the acid that amine replaces and the vinyl and the allyl ester of analogue.Under each situation, amine and unsaturated group are in any position of not disturbing graft reaction.In addition, amine is unsubstituted or arbitrariness ground is not disturbed any group of graft reaction to replace, and these groups are such as being alkyl (preferably having about 20 carbon atoms of about 1-), aryl (preferably having about 30 carbon atoms of about 6-), halogen, ether, thioether etc.

The ethylenically unsaturated organic compounds that contains at least one alcohol functional group.The representative of alcohol is any compound with hydroxyl and at least one ethylenically unsaturated group, for example, the vinyl and the allyl ester of the acid (optimization acid) that alcohols such as alcoholic acid allyl group and vinyl ether and its homologue (branching ring-type and nonbranched) and alcohol replace, and such as vinylcarbinol, butenol, pentenol, hexenol, heptenol, the compound of octenol.Under each situation, pure and mild unsaturated group is in any position of not disturbing graft reaction.In addition, alcohol is unsubstituted or arbitrariness ground is not disturbed any group of graft reaction to replace, as alkyl (preferably having about 20 carbon atoms of about 1-), and aryl (preferably having about 30 carbon atoms of about 6-), halogen, ether, thioether etc.

As the unsaturated functionalized organic compound De oxazoline compound of olefinic.The representative of Shi Yong De oxazoline compound comprises those with following formula in the Zhe:

Wherein each J is hydrogen independently, halogen, C ₁-C ₁₀Alkyl or C ₆-C ₁₄Aryl.

After the consumption of the unsaturated functionalized organic compound of olefinic should make and form branched ethylene polymer in joining ethene polymers, the share of the branched ethylene polymer that obtains from vinyl compound account for ethylenically unsaturated organic compounds at least about 0.01wt%, preferably at least about 0.1wt%, more preferably at least about 0.2wt%, with be no more than about 10wt%, preferably be no more than about 5wt% and more preferably no more than about 2wt%.

Non-functional vinyl compound (for example unsaturated aromatic substance of olefinic such as vinylbenzene) can replace the unsaturated functionalized organic compound of olefinic of a part, as long as have enough functionalized ethylenically unsaturated organic compounds to exist as tapping point so that form branched block ethylene polymers thing of the present invention with the reactive behavior thermoplastic polymer reaction of subfraction (c).

The unsaturated functionalized organic compound of olefinic can be grafted on the ethene polymers by the known any technology of skilled person in the prior art, as at US patent 3,236,917 and US patent 5,194, those described in 509.For example, polymkeric substance is added in the double shaft mixer and at 60 ℃ and mixes down in ' 917 patent that exists.Ethylenically unsaturated organic compounds adds with radical initiator such as benzoyl peroxide then, and component mixing under 30 ℃ is finished until grafting.In the patent of ' 509, schedule of operation is similar, and just temperature of reaction is high slightly, for example 210-300 ℃ and do not use radical initiator or use with lower concentration.

Other substitutes grafted and preferred method sees in the US patent 4,950,541, by using the twin screw vented extruder as mixing device.Mixed and the reaction under the temperature of forcing machine inner reaction thing fusing and in the presence of radical initiator of ethene polymers and ethylenically unsaturated organic compounds.Preferably, ethylenically unsaturated organic compounds is injected in the district that remains on the forcing machine internal pressure.

About subfraction (c), reactive behavior thermoplastic polymer

The subfraction that uses in the preparation of branched block ethylene polymers thing of the present invention (c), the reactive behavior thermoplastic polymer can be produced by Bifunctionalized monomeric condensation or alternate manner suitably.

The reactive behavior thermoplastic polymer is hypocrystalline or the amorphous polymer that contains the functional group that can react with functional ethylene copolymers in the melt-mixing process ideally.Semi-crystalline polymer preferably has Tm＞70 ℃.Amorphous polymer preferably has Tg＞50 ℃.Suitable functional group comprises hydroxyl, phenolic group, amine, epoxy group(ing), and isocyanate group.The example of suitable reactive behavior thermoplastic polymer comprises polybutylene terephthalate (PBT), polyethylene terephthalate (PET), nylon 6, polysulfones, urethane, polycarbonate, by the polymethylmethacrylate of epoxy functional, by epoxy group(ing), or by other functional group, preferably by the functionalized styrene-acrylonitrile of those functional groups listed above.

Typically, the consumption of reactive behavior thermoplastic polymer should make and form in joining branched ethylene polymer after the branching ethylene block polymkeric substance, the share of the branching ethylene block polymkeric substance that obtains from the reactive behavior thermoplastic polymer account for the branched block ethylene polymers thing at least about 1wt%, preferably at least about 2wt%, more preferably at least about 5wt%, with be no more than 40wt%, preferably be no more than 30wt%, more preferably no more than about 25wt%.

A suitable class reactive behavior thermoplastic polymer is the type that is known as engineering plastics.The third edition definition engineering plastics of Kirk-Othmer Encyclopedia of Science and Technology are thermoplastics, and pure or not enhancing or filling is being higher than 100 ℃ and 0 ℃ of maintenance dimensional stability and most of physical strength.Term " engineering plastics " and " engineering thermoplasties " can exchange use.The engineering thermoplasties comprises Derlin, polymeric amide (for example nylon), polyimide, polyethers-imide, polyester, liquid crystalline polymers and selected polyolefine, blend, or the alloy of aforementioned resin and from some examples of other resinous type (for example comprise polyethers, the high temperature polyolefins is as poly-pentamethylene, its multipolymer and poly-methylpentane).

Amine-functionalized polymers is as the use of subfraction (c).The reactive behavior thermoplastic polymer that is used as a kind of special adequate types of subfraction (c) is the type that is known as amine-functionalized polymers.A kind of amine-functionalized polymers is a polymeric amide, and it can be by Bifunctionalized monomeric condensation reaction preparation, and these monomers typically are those that contain acid and amine functional group, when monomer has identical or different functional group.For example, if hexamethylene-diamine and hexanodioic acid reaction, then acquisition-[AABB-]-type polymeric amide, wherein diamines and diacid units alternately.Yet, when monomer such as amino acid or cyclic lactam autohemagglutination, from the polyreaction end to end of rule obtain-[AB-}-the type polymeric amide, similar with addition mechanism.For example, when making nylon 6, heating is increased to 240-280 ℃ and catalyzer such as water and phosphoric acid with the temperature of hexanolactam and is added in the system.Hydrolysis then takes place, and open loop and polyreaction take place, and meanwhile reclaims unreacted monomer and reuse from system.Removing to anhydrate from system makes polymer chain carry out polycondensation and growth.

The polymeric amide that be fit to use also comprises wherein two or more different diamines, and/or different diacid and/or different aminoacids together polymerization form those of random or block copolyamide.Carbochain between the functional group can be the aliphatic series of linearity or branching, alicyclic or aromatic hydrocarbons.This chain also can contain heteroatoms such as oxygen, sulphur or nitrogen.What also be fit to use is block or random copolymers, as melting mixing from for example two or more different polyamides, from diamines or contain acid amides and connect the diacid monomer of base and the reaction of another kind of diamines or diacid, or obtain from the reaction of vulcabond and dicarboxylic acid those.

Polymeric amide is the most common to be prepared by direct amidation, and wherein diamines or amino acid whose amido are bonded in the carboxyl of diacid, and subsidiary removing anhydrated.The base of deriving of acid functional group is originated as the alternative that ester, carboxylic acid halides or acid amides can be used as carboxyl functional group, and by product is respectively an alcohol in this case, hydrogen halide or ammonia.The formation of polymeric amide also can be undertaken by the ring-opening polymerization of hexanolactam, such as when from hexanolactam manufacturing nylon 6.Suitable polymeric amide is a nylon-11, and PA-12 and be generally crystalline melting point and be lower than 280 ℃ is usually less than 250 ℃ and the accidental nylon that is lower than 230 ℃, or amorphous nylon.

Above-described polymeric amide and their method of preparation be at US No.2, is discussed in detail in 071,253,2,130,523 and 2,130,948.

Other amine-functionalized polymers class comprises the end capped butadiene/acrylonitrile rubber of amine; Or have one or more uncle aromatics, uncle's aliphatic series of Lewis acid sealing and/or secondary aliphatic series, or those polymkeric substance of ah aromatic amihe-based.Especially suitable amine-functionalized polymers is polyethers or the polyester with this type of amido.

Suitable polyvalent alcohol with secondary amine, especially polyethers and polyester polyol can pass through corresponding polyvalent alcohol and primary amine reaction easily, prepare with the resulting intermediate of hydrogen reduction then, as US patent No.4, described in 153,381.Secondary amine be ideally the alkyl that replaces of inertia base-, cycloalkyl-or benzyl-amine.In addition, can prepare secondary aliphatic poly-amine in the Michael addition reaction of corresponding uncle's aliphatic amine and alefinically unsaturated compounds.Vinyl cyanide is especially suitable alefinically unsaturated compounds, though can use any compound that carries out the Michael addition reaction with primary amine.Uncle's aliphatic amine itself can prepare in the reductive amination process of corresponding polyvalent alcohol and ammonia, for example at US No.3, and 128,311,3,152,998,3,654,370,3,347,926,4, described in 014,933.

Other suitable amine-functionalized polymers is an aromatic polyamine, and comprises polyvalent alcohol, and especially polyethers and polyester polyol contain aromatic amine group after they are modified.This type of aromatic polyamine can allow the reaction of prepolymer and water make the free isocyanate group be hydrolyzed into corresponding primary amines and prepare then by for example with vulcabond corresponding polyethers or polyester polyol end-blocking being formed prepolymer.In addition, this compounds can also be reduced into amine with amido and prepare then by corresponding polyethers or polyester polyol and right-nitro-chlorobenzene reaction, and is of the patent application serial numbers 923,255 (application on October 27th, 1986) people such as Steuber.In the suitable method of another kind, corresponding hydroxyl or primary amine terminated polyether or polyester can be produced the aromatic polyamine compound at transesterification and substance reaction such as the lower alkyl esters (especially methyl esters) of Para-Aminobenzoic.As mentioned above, can in the Michael addition reaction of corresponding uncle's aromatic amine compound and alefinically unsaturated compounds such as vinyl cyanide, prepare secondary aromatic polyamine.

The uncle's aliphatic poly-amine that is fit to the sealing of use passes through the reductive amination process of corresponding hydroxy-end capped compound and ammonia ideally, allow itself and Lewis acid such as Benzoyl chloride then, carbonic acid gas, metal carboxylate such as tin, zinc, titanium or aluminium carboxylate salt etc. cooperate and final preparation.Lewis acidic consumption is about 0.2-about 5 and about 1.5 equivalents of preferably about 0.9-/every normal primary amine groups.

The various amine-functionalized polymers that are fit to use can be expressed from the next:

[H(A)N]a--Ea--(E-G-E)b--N(A)H?????????????????????????????????(I)

[H(A)N]a--[E-(O-E)c]d-Od-[G-(O-G)c]e--N(A)H???????????????????(II)

[H (A) N] a--Q-[O-C (O)-Q-C (O)-O-Q] f--O-C (O)-Q-C (O)-O-Q--N (A) H (III) wherein A be hydrogen or C in each case independently ₁-C ₆Linearity or branched-alkyl or alkylidene group can insert to arbitrariness one or more nitrogen or Sauerstoffatom and insert, and wherein each carbon atom arbitrariness ground is replaced by uncle or secondary amine; E is C in each case independently ₁-C ₂₀, preferred C ₁-C ₁₂More preferably C ₁-C ₈Linearity, branching or cyclic alkyl or alkylidene group can insert to arbitrariness one or more nitrogen or Sauerstoffatom and insert, and wherein each carbon atom arbitrariness ground is by halogen atom (as fluorine, chlorine, bromine or iodine atom), C ₁-C ₆Alkoxyl group, C ₆-C ₁₀Aryloxy, phenyl, or uncle or secondary amine replacement; G is represented by following structure in each case independently:

Wherein

(I) Z is (A) divalent group, wherein all or different piece can be (i) linearities, branching, ring-type or dicyclo, (ii) aliphatic series or aromatics, and/or (iii) saturated or unsaturated, this divalent group by 1-35 carbon atom and 5 oxygen, nitrogen, sulphur, phosphorus and/or halogens at the most (as fluorine, chlorine and/or bromine) atom is formed together, but wherein each carbon atom arbitrariness ground is replaced by uncle or secondary amine; Or (B) S, S ₂, SO, SO ₂, O or CO; Or (C) singly-bound and

(II) each X is hydrogen independently, halogen atom (as fluorine, chlorine and/or bromine), C ₁-C ₁₂Linearity or cyclic alkyl, alkoxyl group, aryl or aryloxy, as methyl, ethyl, sec.-propyl, cyclopentyl, cyclohexyl, methoxyl group, oxyethyl group, benzyl, tolyl, xylyl, phenoxy group and/or xylyloxy; Or uncle or secondary amine; With

(III) g is 0 or 1; Q is E or G in each case independently; A is 0 or 1; B is 0-10, preferred 0-4, and more preferably 1-3 comprises end value, though a and b can not be 0 simultaneously; C is 1-70, preferred 5-50, and more preferably 5-30 comprises end value; D and e are 0 or 1 simultaneously, though d and e can not be 0 simultaneously; With f be 0-70, preferred 5-50 and more preferably 5-30 comprise end value; Or [H (A) N] a-(E-NH) j-(R2-G-R2-R3) h-R2-G-R2-(E-NH) j-N (A) H (IV) wherein R2 be independently in each case-E-CH (OH)-E-group; R3 is-HN-(E-NH) j-group in each case independently; A, E, G, a are as defined above; H is 0-25, preferred 0-10, and more preferably 1-3 comprises end value; With j be 1-6, preferred 1-4 comprises end value.

Numerical variable can be within the limits prescribed or select separately value in the subrange those of above concrete regulation in above general formula.

The amido mean number of the per molecule that amine-functionalized polymers had generally is about 0.75, preferably about 0.8 or higher, more preferably from about 0.9 or higher and most preferably from about 1.0 or higher.The amido mean number of the per molecule that amine-functionalized polymers had generally is about 3.5 or lower, and is preferred about 3.0 or lower, more preferably from about 2.5 or lower and most preferably from about 2.1 or lower.

It is about 50,000 for about 400-that amine-functionalized polymers typically has equivalent value (being defined as the average number of weight-average molecular weight divided by amido), and preferably about 600-is about 30,000, and more preferably from about 800-about 20,000.

Amine-functionalized polymers will exist with the amount of the final block that is enough to form branched block ethylene polymers thing of the present invention, and should not exist with too high amount so that lose should benefit as composition modified dose branched block ethylene polymers thing.Typically, after the amine-functionalized polymers consumption should make and form in the branching ethylene block polymkeric substance in joining branched ethylene polymer, the share of the branching ethylene block polymkeric substance that obtains from amine-functionalized polymers will account for the branched block ethylene polymers thing at least about 1wt%, preferably at least about 2wt%, more preferably at least about 5wt%, with be no more than about 40wt%, preferably be no more than about 30wt%, more preferably no more than about 25wt%.

For example, generally can not predict crystalline, polar amine-functionalized polymers such as polymeric amide and will improve the performance of nonpolar ethene polymers in the blend of thermoplastic moulded polymkeric substance is arranged as properties-correcting agent.Yet, have now found that and work as amine-functionalized polymers that as polymeric amide, when using with described amount, it not only forms the final block of branched block ethylene polymers thing, and has kept modal dispersion state in the territory that is formed by ethylene/vinyl based compound multipolymer.Yet, if amine-functionalized polymers such as polymeric amide are to use with the consumption that surpasses above-mentioned institute suggestion amount, it trends towards forming the crystal domain of itself, therein ethylene/vinyl compound copolymer is disperseed, the acquisition of having offset shock strength with the brittleness in these polymeric amide territories, and this acquisition should be the performance that the block terpolymer will be given blended composition.Therefore, if use the amine-functionalized polymers with too many average amine functional group, crosslinked easy generation.

About the use of polyester as component (c) reactive behavior thermoplastic polymer

Other classification as the reactive behavior thermoplastic polymer of the branched block ethylene polymers thing of subfraction (c) is a polyester.Polyester can by hydroxycarboxylic acid from esterification, or prepare by direct esterification, direct esterification comprises the substep growth response of glycol and dicarboxylic acid, wherein except that anhydrating, had-AABB-]-polyester of repeating unit.This reaction can be by in body or use inertia high boiling solvent such as dimethylbenzene or chlorobenzene to carry out azeotropic removal of water in solution.

In addition, but press same mode, the ester of dicarboxylic acid forms with derivative can heat the acquisition polyester with glycol in the ester group permutoid reaction.The appropriate acid derivative that is used for this purpose is an alkyl ester, halogenide, the salt or the acid anhydrides of acid.Can interface system, carry out from the reaction of the poly-aryl compound of bis-phenol and aromatic diacid preparation, it basically be used to prepare the identical of polycarbonate.

Polyester can also pass through cyclic ester or C ₄-C ₇The ring-opening reaction of lactone makes, trimethylamine alkali for this reason, and phosphine class and basic metal and alkaline-earth metal, hydride and alcoholate are as initiator.

Being used to prepare the suitable reactants of the polyester that uses in the present invention, outside the hydroxyl-removal carboxylic acid, is two pure and mild dicarboxylic acid, and wherein one or both are aliphatic series or aromatics.Polyester such as poly-(alkane dicarboxylic acid's alkylidene diol ester), poly-(arylidene dicarboxylic acid alkylidene diol ester), poly-(alkane dicarboxylic acid's arylidene diol ester) or poly-(arylidene dicarboxylic acid arylidene diol ester) is suitable use.The moieties of polymer chain can be by for example halogen, C ₁-C ₈Alkoxyl group or C ₁-C ₈Alkyl group side chain replace and in the alkane segment of chain, contain the divalence heteroaromatic group (as-O-,-Si-,-S-or-SO ₂-).This chain also contains unsaturated link(age) and C ₆-C ₁₀Non-aromatic ring.Aromatic ring can contain substituting group such as halogen, C ₁-C ₈Alkoxyl group or C ₁-C ₈Alkyl, and can be connected in polymer backbone and be directly connected in pure and mild acid functional group or be connected in those insertion atoms with position on any ring.

The typical aliphatic diol that is used for polyester manufacture is C ₂-C ₁₀The primary and secondary glycol, as ethylene glycol, propylene glycol and butyleneglycol.Usually the alkane dicarboxylic acid of Shi Yonging is an oxalic acid, hexanodioic acid and sebacic acid.The glycol that contains ring is, for example, 1,4-tetrahydrobenzene glycol, 1,4-hexanaphthene-dimethylene glycol, Resorcinol, quinhydrones, 4,4 '-sulfo-biphenol, two-(4-hydroxyphenyl) sulfone, dihydroxy naphthlene, Xylene glycol maybe can be a kind of in many bis-phenols as 2,2-is two-(4-hydroxyphenyl) propane.Aromatic diacid comprises, for example, and terephthalic acid, m-phthalic acid, naphthalene dicarboxylic acids, diphenyl ether dicarboxylic acid, two benzene dicarboxylic acids, sulfobenzide dicarboxylic acid, biphenoxyl ethane dicarboxylic acid.

Except the polyester that forms from a kind of two pure and mild a kind of diacid, term used herein " polyester " comprises random, copolyesters that typing is arranged or block, for example from two or more different glycol and/or two or more different diacid, and/or form from other divalence heteroaromatic group those.The mixture of this type of copolyesters, only the mixture of the polyester that obtains from a kind of two pure and mild diacid and from the member's of above two groups of polyester mixture also all is suitable for the present invention, and all is included in the term " polyester ".For example, cyclohexanedimethanol with ethylene glycol with the esterification of terephthalic acid in use formed transparent, the amorphous copolyesters that is highly profitable.What also take into account is mixture from 4-hydroxy-benzoic acid and 2-hydroxyl-6-naphthoic acid, or from the mixture of terephthalic acid, 4-hydroxy-benzoic acid and ethylene glycol, or from terephthalic acid, 4-hydroxy-benzoic acid and 4, the liquid crystal polyester that the mixture of 4 '-dihydroxybiphenyl obtains.

Aromatic polyester, those that obtain from aromatic diacid, as poly-(arylidene dicarboxylic acid alkylidene diol ester) polyethylene terephthalate and polybutylene terephthalate, or their mixture, be specially adapted to the present invention.Be adapted at the limiting viscosity that polyester used herein has about 0.4-1.2, also allow though deflect away from the value of this scope.

The method of the aforesaid preparation that is used for polyester and material are in the US of Whinfield patent 2,465,319, the US3 of Pengilly, 047,539, the US3 of Schwarz, 374,402, the US3 of Russell, in 756,986 and the US4 of East, 393,191 detailed discussion is arranged.

In preferred embodiments, after the consumption of polyester should make and form the branched block ethylene polymers thing in joining ethylene/vinyl based compound multipolymer, the share of the branched block ethylene polymers thing that obtains from polyester account for the branched block ethylene polymers thing at least about 1wt%, preferably at least about 2wt%, more preferably at least about 5wt%, with be no more than 30wt%, preferably be no more than 20wt% and 10wt% more preferably from about.In other embodiments, when for example catalyzer was used to promote the formation of branched block ethylene polymers thing, the consumption of polyester can account for more than about 60wt% of branched block ethylene polymers thing, more than preferably about 70wt%, or more than perhaps about 80wt%, but the value that deflects away from this scope also allows.In another embodiment, the consumption of polyester should make that the amount of the polyester that contains and the blend that contains or molding are to be higher than about 0.01/1 with the weight ratio between the amount of polymkeric substance in composition in the branched block ethylene polymers thing, usually be higher than about 0.015/1, be higher than about 0.02/1 with accidental, but be not less than about 0.30/1, usually be not less than about 0.15/1 and accidental be not less than 0.10/1.

In another preferred embodiment, it is about 0.85 for being lower than that the polyester that is used for the preparation of branched block ethylene polymers thing has limiting viscosity (IV), about ideally 0.5-about 0.8 and preferably about 0.55-about 0.75.Polyester with low IV generally is made up of the polymer chain shorter than the polyester with higher IV.Therefore the low IV polyester of extra fine quality contains more terminated radical than the high IV polyester of same quality.Since the formation of branched block ethylene polymers thing depend on the polyester end group, especially-OH end group and ethene polymers on from the reaction of the branch point of vinyl compound formation, so, it is desirable to use the polyester that contains relatively large end group for this reason.

The method for preparing branched block ethylene polymers thing of the present invention

Branched block ethylene polymers thing of the present invention is to prepare by at first forming the branch of containing the unsaturated functionalized organic compound of polyvinyl olefinic.This can be by technology listed above, for example by using at US3, and 236,917, US5, the graft polymerization procedure of describing in 194,509 and/or US4,950,541 realizes.

After the unsaturated functionalized organic compound of olefinic such as maleic anhydride had formed polyvinyl branch, the preparation of branched block ethylene polymers thing of the present invention can be extruded by the reactivity of branched ethylene polymer and reactive behavior thermoplastic polymer and be finished.Reactive behavior end group on the reactive behavior thermoplastic polymer adds in the branched block ethylene polymers thing of the present invention with the functional group reactions formation chemical bond of functionalized organic compound and with final polymer blocks under melted state.Reaction between the branch of reactive behavior thermoplastic polymer and the unsaturated functionalized organic compound formation from olefinic can strengthen by catalyzer, if necessary.Though this reaction arbitrariness ground takes place in Banbury mixing machine or other device, temperature that raises in these devices and high shear-mixed can act on reactant, the exemplary parameter of carrying out this reaction in the 30mm twin screw extruder is: zone temperatures is 150,200,250,250 and 250 ℃; 250rpm; 70-85% changes distance; With 30 second residence time.

When using forcing machine to prepare the branched block ethylene polymers thing, once by a forcing machine with the process that is more convenient for material and handles in, the independent component that the preparation polyester is used is typically in order by independent inlet charging.If ethene polymers, ethylenically unsaturated organic compounds, react simultaneously with the reactive behavior thermoplastic polymer, possible is that ethylenically unsaturated organic compounds will form a large amount of branches on ethene polymers, or do not have, because can having hindered unsaturated organic compound physically, the existence of reactive behavior thermoplastic polymer forms the ramose necessary ways. at all

The use of catalyzer in block ethylene polymers thing of the present invention

For the preparation of the finishing branched block ethylene polymers thing of the present invention reaction arbitrariness ground between branched ethylene polymer and reactive behavior thermoplastic polymer by existing catalyzer to strengthen.This type of catalyzer comprises that having PKa is 7 or higher basic metal or alkaline earth salt and nitrogenous organic base.Under the temperature that branched ethylene polymer and reactive behavior thermoplastic polymer can be reacted or to be lower than the catalyzer that melts under this temperature and have low volatility under these temperature will be the most effective.

As catalyzer, have PKa value be 7 or higher salt be those of positively charged ion formation from them, be representative example below:

Lithium, sodium, potassium, magnesium, calcium or barium; Those that form with negatively charged ion from them are representative example: azido-, acetate moiety, benzoate anion, borate below, bromate, bromide anion, carbonate, carboxylate radical, chlorate anions, chlorion, chlorite, chromate, cyanate radical ,-CN, the dithionic acid root, fluorion, formate, bicarbonate radical, hydrogen phosphate, bisulfate ion, hydrogen sulfide root, bisulfite, hydroxide radical, diphosphanetetroic acid root, Hypophosporous Acid, 50 root, iodate, iodide ion, idous acid group, molybdate, nitrate radical, nitrite anions, oxalate, oxygen root, perchlorate, MnO4, phosphate radical, orthophosphite, pyrophosphate, selenate radical, silicate, sulfate radical, sulfimide root, inferior sulfate radical, sulfonate radical, thio-carbonate, thiocyanate ion, thiosulfate anion, or the like, for replacing and unsubstituted form their derivative.

Can obtain from aromatics sulfimide root as the preferred salt of catalyzer, as shown in following structural formula, M wherein ⁺Be alkalimetal ion, potassium ion for example:

Representative nitrogenous organic base as catalyzer can comprise acridine, aniline (analine), ethylenimine, p-diaminodiphenyl, benzoglyoxaline, isoquinoline 99.9, morpholine, picoline, piperazine, piperidines, purine, pyrazine, pyridine, pyrimidine, tetramethyleneimine, quinazoline, quinoline, Tolylamine, Xie Ansuan etc.In general, many aliphatic series and aromatic amine, for replacing and not replacing form and their derivative useful as catalysts, the most frequently used is tertiary amine such as triethylamine and pyridine.

Catalyst consumption (by weight) is at least about 100ppm in preparation branched block ethylene polymers thing of the present invention, preferably at least about 1000ppm, with be no more than about 3,000ppm, preferably be no more than about 2,000ppm is based on the combined wt of branched ethylene polymer and reactive behavior thermoplastic polymer.

Blend about branched block ethylene polymers thing and additional blend or molding usefulness polymkeric substance:

Branched block ethylene polymers thing of the present invention can be done mixed or melt blended with one or more additional blend or molding ideally with polymkeric substance.In one case, branched block ethylene polymers thing and blend or molding are done with polymkeric substance and are mixed or melt blended, then by molding or be extruded into moulded products.

Point out that from for example polymkeric substance shown in the accompanying drawing branched block ethylene polymers thing of the present invention is a rheology modifier efficiently, melt strength toughener efficiently, blowing or thermoforming intensity reinforcing agent, oil extended polymer, and/or impact modifying agent efficiently.

Further point out, from be other with ethene polymers, reactive behavior thermoplastic polymer and the thermoplasticity blend of the unsaturated functionalized monomer's graft modification of olefinic or molding with the random physical blending thing of polymer manufacture and be different from the branched block ethylene polymers thing and this type of blend or molding with the blend of polymkeric substance.This difference can comprise that ethene polymers, the unsaturated functionalized monomer of olefinic, amine-functionalized polymers and blend or molding illustrate with the system of polymkeric substance by detection.

For random physical blending thing, the ethene polymers with the unsaturated functionalized polymeric graft modification of olefinic can be used as the elastic properties-correcting agent of being mainly of one or more thermoplastic polymers, and wherein a kind of can be amine-functionalized polymers.For the situation that in composition, has two or more thermoplastic polymers, typically be used as the elastomeric modification agent of each thermoplastic polymer with the ethene polymers of the unsaturated functionalized polymeric graft modification of olefinic, on essentially identical degree.On the contrary, when hope uses the branched block ethylene polymers thing as the properties-correcting agent that is having in thermoplasticity blend or the molding usefulness blend of polymkeric substance, if the branched block ethylene polymers thing successfully forms, then the result with contain some amine-functionalized polymers and do not have different with a kind of random physical blending thing in the polymkeric substance (wherein being used as the properties-correcting agent of the molding of whole content with the ethene polymers of the unsaturated functionalized polymeric graft modification of olefinic) with polymkeric substance as molding.

At first exist reactive behavior thermoplastic polymer and initial change to use the polyvinyl visco-elasticity of the unsaturated functionalized monomer's graft modification of olefinic, will belong to then and be mainly elastic properties-correcting agent and be converted into hard segment/soft chain segment properties-correcting agent.The reactive behavior thermoplastic polymer constitutes hard segment and ethene polymers constitutes soft chain segment.This hard segment/soft chain segment properties-correcting agent (branched block ethylene polymers thing) is used as one or more blend or the molding properties-correcting agent with polymkeric substance then.Wherein reactive behavior thermoplastic polymer (in the branched block ethylene polymers thing) as the integral part of hard segment/soft chain segment properties-correcting agent, plays a part to be different from another kind of molding polymkeric substance in random physical blending thing.

Suitable blend or molding comprise any polymkeric substance compatible with the branched block ethylene polymers thing with polymkeric substance, and comprise alkene and non-olefinic polymkeric substance, grafted or grafted not.The branched block ethylene polymers thing also can with the ethene polymers of substantial linear, the linear tetrafluoroethylene polymer of branching common non-homogeneous branching or even, the non-olefinic polymkeric substance, any can be by grafting or not grafting, or any mixture of these polymkeric substance carries out blend.

Blend or molding for example comprises high density polyethylene(HDPE) (HDPE) with polymkeric substance, new LDPE (film grade) (LDPE), linear low density polyethylene (LLDPE), ultra-low density polyethylene (ULDPE), polypropylene, ethylene-propylene copolymer, ethylene-styrene copolymer, polyisobutene, ethylene-propylene-diolefinic monomer multipolymer (EPDM), polystyrene, acrylic nitrile-butadiene-alkene-vinylbenzene (ABS) multipolymer, ethylene/acrylic acid (EAA), Ethylene/vinyl acetate (EVA), ethylene/vinyl alcohol (EVOH), (ECO is included in US patent 4 to the multipolymer of ethene and carbon monoxide, 916, or ethene described in 208 those),, polymkeric substance of propylene and carbon monoxide (EPCO) or ethene, carbon monoxide and polymerizing acrylic acid thing (ECOAA), etc.Non-olefinic blend or molding are polyester with the representative example of polymkeric substance, polyvinyl chloride (PVC), epoxide, urethane, polycarbonate, polymeric amide etc.

Illustrative blend or molding can be characterized by the consistency with the branched block ethylene polymers thing with polymkeric substance, so that mixture of melts can not be divided into independent polymer phase.If more than one these blend or molding polymkeric substance and one or more branched block ethylene polymers thing blend, then all abundant consistencies that usually demonstrate each other, one to one or at least with one or more other mixed with polymers, so that polymeric constituent can not be divided into independent polymer phase, further cause extruding processing difficulties, as extruded material gush, film band effect etc.

Can change and depend on many factors with one or more other blend or molding with the amount of the branched block ethylene polymers thing of thermoplastic polymer blend, comprise blend or molding character with thermoplastic polymer or polymer class, the end-use of blend, the existence of additive or do not exist, the character of additive if present, or the like.

Typically, it is at least a that blend will comprise, ideally at least about 2 parts with preferably at least about 5 parts, but is no more than about 50 parts, is no more than about 40 parts and preferably be no more than about 30 parts branched block ethylene polymers thing ideally.Equally, blend generally contains at least about 50 parts, ideally at least about 60 parts and preferably at least 70 parts, but is no more than about 99 parts, be no more than ideally about 98 parts and preferably be no more than about 95 parts blend or molding with thermoplastic polymer or polymer class.Should be noted that branched block ethylene polymers thing and blend or molding can be (not necessarily) 100 weight parts altogether with the parts by weight of polymkeric substance or polymer class.

If yet blend or molding are identical with polymkeric substance in the composition of the ramose reactive behavior thermoplastic polymer that forms the branched block ethylene polymers thing, then reactive behavior thermoplastic polymer and blend or molding will be above 30 parts with the total amount of thermoplastic polymer, preferred 20 parts, more preferably 15 parts, most preferably 10 parts, by the blend composition of per 100 weight parts.

The preferred blend or the molded polymeric that use with branched block ethylene polymers thing (it contains the functionalized amine polymer as the reactive behavior thermoplastic polymer) comprise: (i) polyolefine, (ii) polymeric amide, (iii) polycarbonate, (iv) hydrogenated polystyrene; (v) their mixture.The preferred blend or the molded polymeric that use with branched block ethylene polymers thing (it contains the polyester as the reactive behavior thermoplastic polymer) comprise: (i) polycarbonate, (ii) polyester, (iii) polyphenylene oxide, (iv) polysulfones, (v) polyimide or polyetherimide and (vi) their mixture.

Polyolefin resin is used the purposes of polymkeric substance as blend or molding.The polyolefin resin that is used as thermoplastic polymer is any and polypropylene in the described ethene polymers of above preparation at the branched block ethylene polymers thing.Polyacrylic preparation also comprises the use Z-type catalyst, and it allows polypropylene carry out the stereoregular polyreaction and forms isotatic polypropylene.Catalyst system therefor is the mixture of titanous chloride and diethyl monochlor(in)ate aluminium typically, further as the US patent 4,177 of Cecchin, described in 160.Be used to prepare polyacrylic various types of polymerization process and comprise slurry process, under about 50-90 ℃ and 0.5-1.5MPa (5-15 normal atmosphere), carry out and gas phase process and liquid monomer method, wherein especially note removing amorphous polymer.Ethene is added into and forms the polypropylene with ethylene block in the reaction.

By using Ziegler-Natta catalyst, various higher alkenes all polymerization form polyolefin resin, and its representative example is a 1-butylene, 1-methyl-amylene and 4-methyl-1-pentene.Polyolefin resin used herein also comprises various ethylene copolymers such as ethylene/acrylic acid copolymer, ethylene, ethylene/vinyl alcohol copolymer, ethene/carbon monoxide multipolymer (comprises US patent 4,916,208 and 4,929, described in 673 those), ethylene/propene/carbon monoxide multipolymer, ethene/carbon monoxide/acrylic copolymer, polyvinyl chloride, and analogue, and their mixture.For example, the preparation polyvinyl chloride suspension process in, vinyl chloride monomer can with other vinyl monomer such as vinyl-acetic ester, vinyl cyanide, divinyl, butyl acrylate cores, maleic anhydride, alkene or vinylbenzene carry out copolyreaction, obtain random, block or graft copolymer.

Use polyamide resin with a special benefits of polymkeric substance to be as molding, it can be in mould machine and the segmented copolymer blend, therefore, the extra heat history that composition applies has been avoided with the pellet of polymer composition because of at first extruding block terpolymer/molding.

Polymeric amide is used the purposes of polymkeric substance as blend or molding.The polymeric amide that can be used as thermoplastic polymer is described to the various amine-functionalized polymers that are used to prepare the block terpolymer above.When polymeric amide as molding when use polymkeric substance, might with sometimes preferably use from the different polyamide of those selections that are used to prepare the block ter-polymers.For example, the polymeric amide that is used to prepare the block terpolymer can be a nylon 6, and can be nylon 6,6 as molding with the polymeric amide of polymkeric substance; 6,10; Or 12, and/or blend or molding with polymkeric substance have amino mean number be higher than about 2.0, or in about 3.5 scopes of about 2.05-.Use polyamide resin with a special benefits of polymkeric substance to be as molding, it can with the blend and with the pellet of polymer composition the extra heat history that composition applies has been avoided in mould machine of block terpolymer because of at first extruding block terpolymer/molding.

Polycarbonate is used the purposes of polymkeric substance as blend or molding.Can be from dihydroxy compound such as bis-phenol as blend or molding with the polycarbonate of polymkeric substance, with carbonate precursor such as dibasic carbonic acid derivatives, haloformate (as two haloformates of glycol or dihydroxy-benzene), or the preparation of the derivative of carbonic ether such as dipheryl carbonate base ester or its replacement.These components are usually reacted by the phase interface method, and wherein dihydroxy compound dissolves and deprotonation in aqueous base, form bisphenolate salt and carbonate precursor and are dissolved in the organic solvent.

These components are usually by means of at first being selected from wherein from aromatic dihydroxy compound, water and with water is immiscible that the mixture of carbonate precursor and the soluble nonreactive activity organic solvent preparation of polycarbonate product reacts.Representative solvents comprises chlorinated hydrocarbons, as methylene dichloride, and 1,2-ethylene dichloride, tetrachloroethane, chlorobenzene and chloroform.It is the level of two anionic forms to dihydroxy compound is activated that caustic soda or other alkali are added into the pH value of regulating mixture in the reaction mixture then.

Carbonate precursor contacts with the stirring the mixture of aqueous base of dihydroxy compound, and for this reason, carbonate precursor can be sparging in the reaction mixture with gas form, maybe can dissolve and introduces with the solution form.The carbonate precursor typical amounts is about 1.0-1.8, the dihydroxy compound of preferably about 1.2-1.5 mole/every mole.Stir the mixture by this way so that be enough to will contain the drop of solvent of carbonate precursor disperse or be suspended in the aqueous alkaline solution.The reaction between organic phase and water that is caused by this stirring action has obtained two (carbonate precursor) esters of dihydroxy compound.For example, if carbonic ether is carbonyl halide such as phosgene, then the product of the initiating stage of this method is monomer or oligopolymer, they are single-or dichloro formic acid or in each end group, contain phenol formula ion.

These intermediate lists-or the oligomerisation carbonic ether when forming, be dissolved in the organic solvent, they are condensed into the high-molecular weight polycarbonate by contacting with coupling catalyst then, are the representative of catalyzer below: tertiary amine such as triethylamine and dimethyl aminopyridine.

After polyreaction finished, organic phase and water were separated, purification organic phase and therefrom reclaim polycarbonate product.Organic phase is carried out centrifuge washing with diluted alkaline, water and/or diluted acid on demand, until not having unreacted monomer, residual process chemistry thing and/or other ionogen.The recovery of polycarbonate product can be passed through spraying drying, the steam devolatilization, and direct devolatilization in vented extruder, or carry out with the intermediate processing of solvent such as toluene, hexanaphthene, heptane, methyl alcohol, hexanol or methyl ethyl ketone.

In the melting method of preparation polycarbonate, the aromatic diester of carbonic acid and aromatic dihydroxy compound carry out condensation in transesterification in the presence of alkaline catalysts.Reaction is typically being carried out under about 250 ℃-300 ℃ and under the vacuum of the about 1-100mmHg of pressure that reduces gradually.

Also can by carbonate precursor such as phosgene with contain the method that aromatic dihydroxy compound, chlorinated hydrocarbon solvent contact with solution such as the material (simultaneously as acid acceptor and condensation catalyst) of pyridine, xylidine or calcium hydroxide, in homogeneous phase solution, prepare polycarbonate.

The example that is fit to some dihydroxy compound of preparation polycarbonate comprises various bridge joints, replace or the unsubstituted aromatic dihydroxy compound (or their mixture) that is expressed from the next: Wherein (I) Z is (A) divalent group, wherein all or different piece can be (i) straight chain, side chain, ring-type or dicyclo, (ii) aliphatic series or aromatics, and/or it is (iii) saturated or undersaturated, this divalent group is made up of 1-35 carbon atom and 5 oxygen, nitrogen, sulphur, phosphorus and/or halogens (as fluorine, chlorine and/or iodine) atom at the most; Or (B) S, S2, SO, SO ₂, O or CO; Or (C) singly-bound; (II) each X is hydrogen independently, halogen (as fluorine, chlorine and/or bromine), C ₁-C ₁₂, preferred C ₁-C ₈Straight chain or cyclic alkyl, aryl, alkaryl, aralkyl, alkoxyl group or aryloxy, as methyl, ethyl, sec.-propyl, cyclopentyl, cyclohexyl, methoxyl group, oxyethyl group, benzyl, tolyl, xylyl, phenoxy group and/or xylyloxy; Or nitro or cyano group; (III) m is 0 or 1.

For example, the abutment of being represented by Z in above general formula can be C ₂-C ₃₀Alkyl, cycloalkyl, alkylidene group or cycloalkylidene, or by aromatics or basic two or more these class groups that connect of ether connection, it is one or more such as methyl to be keyed jointing maybe, ethyl, propyl group, n-propyl, sec.-propyl, cyclohexyl, dicyclo [2.2.1] heptyl, benzyl, CF ₂, CF ₃, CCl ₃, CF ₂Cl, CN, (CH ₂) ₂COOCH ₃, or PO (OCH ₃) ₂The carbon atom of group.

The representative example of useful especially dihydroxy compound is two (hydroxyphenyl) paraffinic hydrocarbonss, two (hydroxyphenyl) naphthenic hydrocarbon, dihydroxyl hexichol base class and two (hydroxyphenyl) sulfones and especially 2, two (4-hydroxyphenyl) propane (" bisphenol-A " or " two-A ") of 2-; 2, two (3, the 5-dihalo--4-hydroxyphenyl) propane (" four halogen bisphenol-As ") of 2-, wherein halogen can be fluorine, chlorine, bromine or iodine, for example 2, two (3, the 5-two bromo-4-hydroxyphenyl) propane (" tetrabromobisphenol-A " or " TBBA ") of 2-; 2, two (3, the 5-dialkyl group-4-hydroxyphenyl) propane (" tetraalkyl bisphenol-A ") of 2-, wherein alkyl is methyl or ethyl, for example 2, two (3, the 5-dimethyl-4-hydroxyphenyl) propane (" tetramethyl-bisphenol-A ") of 2-; 1,1-(4-hydroxyphenyl)-1-diphenylphosphino ethane (" bisphenol-AP " or " two-A "); Two hydroxy phenyl fluorenes; With 1, two (4-hydroxyphenyl) hexanaphthenes of 1-.

Use above-described method, can obtain polycarbonate product, the weight-average molecular weight that is recorded it by light scattering method or gel permeation chromatography is 8,000-200,000 and preferred 15,000-40,000 and/or its melt flow value be about 3-150, preferably about 10-80 is (by ASTM regulation D-1238-89, condition 300/1.2 records), also allow though deflect away from these scopes.Control molecular weight by add chain terminator in reaction mixture, terminator is selected from monofunctional species such as phenol, carbonyl chloride, or chlorine carbonic acid phenylester.

Can obtain polycarbonate branching rather than straight chain by adding three or polyfunctionality monomer such as triple phenoxyl ethane in reaction mixture.

The preferred method of the present invention is the method that wherein prepares aromatic polycarbonate.Define aromatic polycarbonate with reference to (being bonded in one or more dihydroxy compound carbonyl carbon, that in polycarbonate chain, exist of carbonate precursor) Sauerstoffatom.In aromatic polycarbonate, all these Sauerstoffatoms are by dihydroxy compound residue (its some parts is an aromatic ring) bridge joint.

Being included in the employed here term " polycarbonate " is various Copolycarbonates, and some of them are to prepare by introduce one or more different dihydroxy compound in reaction mixture.When dicarboxylic acid such as terephthalic acid or m-phthalic acid (or derivative of its formed ester) or hydroxycarboxylic acid are used for reaction mixture, or formation oligomerisation prepolymer, not a kind of in above-mentioned " difference " dihydroxy compound, thereby obtain poly-(ester/carbonic ether), this is in the US of Swart patent 4, detailed discussion is arranged in 105,533.In preferred embodiments, composition of the present invention comprises poly-(ester/carbonic ether).

Copolycarbonate for example can react in the presence of chloro-or the end capped polysiloxane of bromo-by one or more dihydroxy compound and carbonate precursor and prepare, and reacts with hydroxy-end capped polyphenylene oxide or polymethylmethacrylate or with the aromatic ester of phosphinylidyne dichloro or phosphoric acid to prepare.Siloxanes/carbonate blocks terpolymer is at the US4 of Paul, has at length in 596,970 and discusses.

It is well-known being used for preparing the aforesaid method that is applicable to enforcement carbonate polymer of the present invention, for example, at Schnell, US3,028,365; Glass, US4,529,791; And Grigo, US4 has at length discussed several method in 677,162.

Polyester is used the purposes of polymkeric substance as blend or molding.When polyester was used polymkeric substance as the blend in the present composition or molding, then polyester was the same with the described subfraction of above preparation at the branched block ethylene polymers thing (c).Preferably has limiting viscosity about 0.85 or higher, about ideally 0.9-about 1.2 and preferably about 0.95-about 1.05 with the polyester of polymkeric substance as the blend in the blend composition of the present invention or molding.

Further preferably, when polyester is used polymkeric substance as the subfraction (c) of branched block ethylene polymers thing with as blend or molding simultaneously, use different polyester separately.

Polyphenylene oxide is as the purposes of thermoplastic polymer.Suitable thermoplastic polymer comprises polyphenylene oxide (also being known as polyphenylene oxygen), and it is the polymkeric substance that comprises many structural units that are expressed from the next:

In in this unit each, each Q ₁Be hydrogen independently, halogen, uncle or secondary C ₁-C ₈Low alkyl group, phenyl, haloalkyl, aminoalkyl group,-oxyl, or wherein at least two carbon atoms separate the halo-oxyl of halogen and Sauerstoffatom; With each Q ₂Be hydrogen independently, halogen, uncle or secondary C ₁-C ₈Low alkyl group, phenyl, haloalkyl,-oxyl, or to Q ₁Defined halo-oxyl.The example of suitable uncle's low alkyl group is a methyl, ethyl, n-propyl, normal-butyl, isobutyl-, n-pentyl, isopentyl, 2-methyl butyl, n-hexyl, 2,3-dimethylbutyl, 2-, 3-or 4-methyl amyl and corresponding heptyl.The example of secondary low alkyl group is a sec.-propyl, sec-butyl and 3-amyl group.Preferably any alkyl is a straight chain, rather than side chain.Modally be each Q ₁Be alkyl or phenyl, C especially ₁-C ₄Alkyl and each Q ₂Be hydrogen.

Homopolymer and multipolymer polyphenylene oxide, and composition thereof or blend all included.Suitable homopolymer is for example to contain 2,6-dimethyl-1, those of 4-phenylene ether units.Suitable copolymers comprises and contains this element and for example 2,3,6-trimethylammonium-1, the random copolymers of 4-phenylene ether units.

What also comprise is the polyphenylene oxide that contains the structure division that can improve performance such as molecular weight, melt viscosity and/or shock strength.This base polymer can be by known way by the vinyl monomer such as vinyl cyanide compound (for example vinyl cyanide) and vinyl aromatic compounds (for example vinylbenzene), or such as polystyrene and elastomeric polymkeric substance and polyphenylene oxide copolymerization or be grafted on the polyphenylene oxide and prepare.Product typically contains grafted and grafted structure division not.Other suitable polymers is a link coupled polyphenylene oxide, and wherein coupling agent contains the high-molecular weight polymer of the reaction product of hydroxyl and coupling agent by the hydroxyl reaction production of known way and two polyphenylene oxide chains.The coupling agent of character is a low-molecular polycarbonate for example, quinone, heterocycle, formal and polyphenylene sulfide.For example, polyphenylene oxide/Copolycarbonate is known and in US patent 5,010,143 discussion is arranged.

Polyphenylene oxide typically has number-average molecular weight about 3,000-40,000 and weight-average molecular weight about 20,000-80 is in 000 scope, by gel permeation chromatography.Its limiting viscosity at about 0.15-0.6 and preferred 0.25dL/g at least, is measured down in 25 ℃ in chloroform typically.Yet the value that deflects away from these scopes also allows.

Polyphenylene oxide prepares by the oxidative coupling reaction of at least a corresponding monohydroxyaromatic compound typically.Monohydroxyaromatic compound useful especially and that buy easily is 2 (each Q wherein ₁Be methyl and each Q ₂Be hydrogen), and its polymkeric substance can be characterized by poly-(2,6-dimethyl-1,4-phenylene ether) and 2,3,6-pseudocuminol (each Q wherein ₁With a Q ₂Be methyl and other Q ₂Be hydrogen).For the method that is prepared polyphenylene oxide by oxidative coupling is known many catalyst systems are arranged.For most of situation, they contain at least a heavy metal compound such as copper, and manganese or cobalt compound mix use with various other materials usually.The preferred catalyst system of the first kind is made up of those that contain copper compound, for example is disclosed in for example US3, in 306,874,3,306,875,3,914,266 and 4,028,341.They are cupric ion or cuprous ion normally, the mixture of halide-ions (being chlorine, the bromine or iodine ion) and at least a amine.The catalyst system that contains manganic compound has constituted second preferred type.They are alkaline system normally, and wherein bivalent manganese combines with negatively charged ion such as halide-ions, alkoxyl group or phenoxy group.Modal is that manganese and one or more Synergist S-421 95s and/or sequestrant such as dialkylamine, alkanolamine, Alkylenediamine, neighbour-hydroxyaromatic aldehyde, neighbour-hydroxyl azo-compound, w-hydroxyoxime (monomer and polymkeric substance), neighbour-hydroxyaryl oxime and beta-diketon constitute title complex and exist.The also usefully known catalyst system that contains cobalt.

Aforesaid polyphenylene oxide at length is disclosed in the US patent 4,866,130.

Being also included within the classification of polyphenylene oxide is by with polyphenylene oxide and polystyrene, vinylaromatic polymer, and/or with the prepared polyphenylene ether blend of other non-styrenic polymer blend of following defined.When being polyphenylene ether blend with the thermoplastic polymer of polymkeric substance as blend or molding, this blend comprises about 20-99 weight part polyphenylene oxide, preferably about 30-90 weight part polyphenylene oxide, and equal amount is a polystyrene, vinylaromatic polymer, and/or non-styrene polymer.Preferred this prescription contains the about 85 weight part polyphenylene oxide of the 30-that has an appointment, about 70 weight parts of about 15-be selected from one or more following compositions: polystyrene, high-impact polystyrene, styrene/butadiene/styrene and/or styrene/ethylene-butylene/styrene block terpolymer.

Polysulfones is used the purposes of polymkeric substance as blend or molding.

Generally can be expressed as the polymkeric substance that contains aromatic ring that a part is connected by not similar group such as ether or alkyl or singly-bound realization contraposition by sulfuryl and a part as the polysulfones of thermoplastic polymer.Yet polysulfones does not contain carbonic ether [C (O)-] and connects base.Polysulfones is the thermoplastics of the about 180-250 of second-order transition temperature ℃ transparent, hard.

Common various polysulfones are by 4, and 4 '-dihalo-sulfobenzide is prepared by the nucleophilic substitution of bisphenol-A in dipolar nature aprotonic solvent such as dimethyl sulfoxide (DMSO) or 1-Methyl-2-Pyrrolidone.The fluorine or chlorine thing can be used as the dihalide monomer.With the same in the preparation of polycarbonate, bis-phenol is activated by the stoichiometry of aqueous alkali such as sodium or potassium oxyhydroxide and is the bisphenolate salt form.Yet, need bisphenolate salt with under 120-140 ℃, carry out component distillation before the dihalide monomer contacts and from system, remove unnecessary water.

Under 130-160 ℃, carrying out polyreaction under the inert atmosphere that prevents the bisphenolate salt oxidation then.Can obtain the molecular weight up to 250,000 at one hour, simple function group halogenide or phenol usually become so high as chain terminator with the molecular weight that prevents polysulfones so that because thickness and can't processing too.When the ratio of initial monomers near the bisphenol-A type polysulfones that can obtain highest weight for the moment, but for useful performance, molecular weight (being expressed as in chloroform the reduced viscosity under 0.2g/100mL concentration and 25 ℃) is at least 0.4dL/g usually.Bisphenol-A type polysulfones is with Udel ^TMPolysulfones is available from Amoco Performance Products, Inc..

Another kind of polysulfones is synthetic from dihydroxyphenyl propane, and this dihydroxyphenyl propane itself contains sulfone bridge (" bis-phenol-S ").This is aggregated in and carries out in dipolar nature non proton transfer solvent such as sulfobenzide under the comparatively high temps (about at the most 285 ℃) and adopt alkali as yellow soda ash or potassium.Generally dewater and be not that one considers a problem.This base polymer is that Inc. is with Victrex from ICI Americas ^TMPolysulfones is buied.

Other bis-phenol that is used to prepare polysulfones is 4,4 '-dihydroxyl diphenylsulfide, 4,4 '-dihydroxy diphenyl ether, 4,4 '-dihydroxyl ditan, quinhydrones, two (4-hydroxy diphenyls)-2,2-perfluoropropane, two (4-hydroxyl phenylbenzene)-1, the 1-hexanaphthene, 4,4 '-dihydroxy benaophenonel, with 4,4 '-dihydroxybiphenyl.

Generally, the repeating unit of polysulfones can be represented by following general formula:--[--Ar--S (O) ₂--Ar--O--Ar (X) ₄--[--Z--Ar (X) ₄--] _q--O--] _p--Ar wherein, D and E as defined above, q is that about 0-about 3 and p are about 10-about 100.

Polyimide or polyetherimide are used the purposes of polymkeric substance as blend or molding.Polyimide is the condensation polymer that obtains from Bifunctionalized carboxylic acid and acid anhydrides and primary diamines.Discharge two normal water by forming imide bond, water molecules is that second of formation neutralization in anhydride rings is the result that Sauerstoffatom is replaced by nitrogen-atoms in the ring.This polymkeric substance in addition can by diamines directly and tetracarboxylic acid react and prepare.Under any situation, when being acid anhydrides, starting raw material obtains intermediate, for example polyamic acid and discharge the second normal water by adding the thermosetting polymkeric substance.The process that forms the polyamic acid intermediate by dicarboxylic anhydride and diamine reactant is at room temperature at dipolar nature aprotonic solvent such as N,N-DIMETHYLACETAMIDE, carries out in cresylol or the neighbour-chlorophenol.Carried out the precursor that cyclodehydration obtains final polymkeric substance in 3-5 hour by heating down at 150-200 ℃.When using aromatic diamine, in solvent such as chlorobenzene, use promotor such as triethylamine or acetate.

Also can and remove carbonic acid gas simultaneously, or prepare polyimide by bismaleimides and diamine reactant by aromatic dianhydride and aromatic diisocyanate reaction.

Carry out nucleophilic substitution reaction by bisphenolate salt and dinitrobenzene double imide, or form reaction, prepare polyetherimide by aforesaid polyimide between the dicarboxylic anhydride of diamines and ether bridge joint.Can be in the mixture of dipolar nature aprotonic solvent such as dimethyl formamide or dimethyl sulfoxide (DMSO) and toluene or chlorobenzene under about 40 ℃ in the reaction between bisphenolate salt and the dinitrobenzene double imide, or in being with or without the N-Methyl pyrrolidone of chlorobenzene, under about 80-130 ℃, carry out.Also can prepare polyetherimide by the displacement of chlorine on the double imide or fluorin radical.

The diamines that is used to prepare polyimide can be aliphatic series or aromatics, between several useful materials comprise-and right-phenylenediamine, 2,4-and 2, the 6-diaminotoluene, right-and-xylylene amine, 4,4 '-benzidine, 4,4 '-diamino-diphenyl ether, 4,4 '-diaminobenzophenone, 4,4 '-diamino-phenyl sulfone, 4,4 '-diamino-diphenyl thioether, 4,4 '-diaminodiphenyl-methane, 3,3 '-tolidine, 4,4 '-isopropylidene pentanoic, 1, two (right-the amido phenoxy group) benzene of 4-, 1, two (right-the amido phenoxy group) benzene of 3-, six-, seven-, nine-and decamethylene diamine, 1,4-cyclohexane diamine and two (4-amido cyclohexyl) methane.The representative dicarboxylic anhydride that is used to prepare polyimide comprises 1,2,4,5-pyromellitic acid dianhydride, the benzophenone dicarboxylic anhydride, 2, two (3,4-dicarboxyl phenyl) the propane dicarboxylic anhydrides of 2-, 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride, two (3,4-dicarboxyl phenyl) ether dicarboxylic anhydride, two (3,4-dicarboxyl phenyl) thioether dicarboxylic anhydride, dihydroxyphenyl propane bis ether dicarboxylic anhydride, 2, two (3,4-dicarboxyl phenyl) the HFC-236fa dicarboxylic anhydrides of 2-, 2,3,6,7-naphthalene tetracarboxylic acid dianhydride, two (3,4-dicarboxyl phenyl) sulfone dicarboxylic anhydride, 1,2,5,6-naphthalene tetracarboxylic acid dicarboxylic anhydride, 2,2 ', 3,3 '-biphenyl tetracarboxylic dianhydride, quinhydrones bis ether dicarboxylic anhydride, two (3,4-dicarboxyl phenyl) sulfoxide dicarboxylic anhydride and 3,4,9, the 10-perylenetetracarboxylic dianhydride.

The bis-phenol that is used to prepare polyetherimide comprise above about polycarbonate described those.The representative dinitrobenzene double imide that is used to prepare polyetherimide comprises 1,3-two (the adjacent benzoylimino base of 4-nitro) benzene, 1,4-two (the adjacent benzoylimino base of 4-nitro) benzene, 4,4 '-two (the adjacent benzoylimino base of nitro) diphenyl ether, 4,4 '-two (the adjacent benzoylimino base of 4-nitro) ditan, 2,4-two (the adjacent benzoylimino base of 4-nitro) toluene and 1,6-two (the adjacent benzoylimino base of 4-nitro) hexane.

Preparation branched block ethylene polymers thing and blend or the molding method of the blend of polymkeric substance.Preparation of compositions of the present invention can be undertaken by any suitable mixing device well known in the prior art.Typically, branched block ethylene polymers thing and thermoplasticity blend or molding polymkeric substance, component that exists in the present composition with other arbitrariness ground or additive are done mixed in cylinder or vibrating machine with powder or particulate matter form, stirred fully so that their uniform distribution.If desired, do mixed formulation and further in being with or without the forcing machine of vacuum, be enough to cause and mix and stir under the temperature of thermoplastification or stand shear-stress.Other device that can use in blending means for example comprises ring-roller mill, Henschel mixing machine, ribbon mixer, Banbury mixing machine, or reciprocating screw injection molding machine.

The method itself for preparing above-mentioned branched block ethylene polymers thing has obtained a kind of preferred method for preparing the blend of branched ethylene polymer and reactive behavior thermoplastic polymer and arbitrariness ground blend or molding usefulness polymkeric substance.When using forcing machine to prepare the branched block ethylene polymers thing, independent component (preparing this polymkeric substance from these components) and blend are sequentially added into by independent opening for feed with polymkeric substance, disposable by a forcing machine to carry out the material processing more easily.The last material that adds typically adds by the fed downstream mouth in the forcing machine in order of addition(of ingredients).

For example, at first add ethene polymers, add the unsaturated functionalized organic compound of olefinic then, add the reactive behavior thermoplastic polymer subsequently and add blend at last or the molding polymkeric substance.In another embodiment, the branched block ethylene polymers thing for preparing previously at first is added into, and then adds the reactive behavior thermoplastic polymer, adds blend or molding polymkeric substance at last.In yet another embodiment, the branched block ethylene polymers thing for preparing previously can add with the reactive behavior thermoplastic polymer, adds then to do to mix or the molding polymkeric substance.

The select progressively that the reaction of branched ethylene polymer and reactive behavior thermoplastic polymer forms the branched block ethylene polymers thing before blend or molding are added into mixing machine with polymkeric substance has obtained having the product of excellent properties, with before the reactive behavior thermoplastic polymer or add blend simultaneously and contrast with the situation of polymkeric substance.The reason that obtains this result is that blend or molding can be used as physics obstruction agent with polymkeric substance, and its hinders the unsaturated functionalized organic compound of olefinic and forms branch, or hinders reactive behavior thermoplastic polymer and any formed ramose reaction.

Comprise the preparation of branched block ethylene polymers thing and blend or molding with the goods of the blend of thermoplastic polymer.When applying the softening or fusing of heat and/or shearing force, composition of the present invention can be used for forming process and can be by routine techniques moulding or molding processing, and these technology for example are compactings, injection moulding, gas is assisted injection moulding, calendering, vacuum forming, thermoforming, extrusion molding and/or blowing, alone or in combination.Said composition also can moulding, spinning or stretching film forming, fiber, multi-layer laminate or the sheet material extruded, or can be suitable on any machine of this purpose compound with one or more organic or inorganic materials.

About the introducing of additional additional impact modifying agent in branched block ethylene polymers thing and blend or the molding usefulness blend of polymkeric substance.

In another embodiment of the present invention, branched block ethylene polymers thing and blend or molding further comprise additional impact modifying agent with the blend of thermoplastic polymer.Though the branched block ethylene polymers thing can be used as impact modifying agent effectively, when it is having when existing in blend or the composition of molding with polymkeric substance; But can also further obtain better properties by the synergistic effect that is based upon composition between branched block ethylene polymers thing and the additional impact modifying agent under the various situations.

Suitable additional impact modifying agent for example comprises elastomerics, as A-B or A-B-A multipolymer, and nuclear-shell graft copolymer or their mixture.

A-B or A-B-A multipolymer as impact modifying agent can be linearity, side chain, radiation shape or remote block, and can be that diblock (" A-B ") multipolymer, three blocks (" A-B-A ") or be with or without are formed alternation section the radiation shape or the remote segmented copolymer of (that is, alternately exist or and approach the structure division of the transition point between A and the B block with random order at monomer on this polymkeric substance).

A part usually is by the polyreaction preparation of one or more aromatic vinyl hydrocarbon monomers such as various styrene monomer and its substituted variant; It is about 4 to have weight-average molecular weight, and 000-about 115,000; With the characteristic with thermoplastic material: it has at high temperature processing needed stability and also having good intensity under its softening temperature being lower than.The B part of multipolymer is typically from replacing or do not replace C ₃-C ₁₀The polyreaction of diolefine (especially conjugated diene such as divinyl or isoprene) obtains; It is about 20 to have weight-average molecular weight, and 000-about 450,000; Be characterized as elastic performance with embodiment, this characteristic makes the stress that it absorbs and dissipation is applied, and then recovers its shape.

In order to reduce oxidation and thermolability, employed here A-B or A-B-A multipolymer also can be hydrogenated ideally, reduce the degree of unsaturation on polymer chain or the side extension aromatic ring.

Most preferred aromatic vinyl A-B or A-B-A multipolymer are the aromatic vinyl/conjugated diene block polymers from vinylbenzene and divinyl or vinylbenzene and isoprene formation.When styrene/butadiene copolymers was hydrogenant, they usually were represented as vinylbenzene/(ethylene/butylene) multipolymer of diblock form, or the vinylbenzene of three block form/(ethylene/butylene)/styrol copolymer.When the styrene/isoprene multipolymer was hydrogenated, they were represented as vinylbenzene/(ethylene/propene) multipolymer of diblock form, or were expressed as vinylbenzene/(the ethylene/propene)/styrol copolymer of three block form.Aromatic vinyl discussed above/diolefine A-B or A-B-A multipolymer are described in detail in the USP3 of Holden, 265,766, the USP3 of Haefele, 333,024, the USP3 of Wald, 595,942 and the USP3 of Witsiepe, in 651,014, they with various Kraton elastomericss available from Shell chemical company.

Being suitable as the nuclear-shell graft copolymer elastomerics that replenishes impact modifying agent is with dience rubber, alkyl acrylate rubber, or their mixture is basis and the elastomerics (or rubber) that had about 45% or higher those greater than multipolymer weight.Contain polymerization based on the nuclear-shell graft copolymer of dience rubber by diolefine (preferred conjugated diene), or by diolefine and monoolefine or polar vinyl compounds such as vinylbenzene, vinyl cyanide, or the copolymerization of the alkyl ester of unsaturated carboxylic acid such as alkyl methacrylate the matrix latex or the nuclear that make.Matrix latex is typically by about 40-85% diolefine, and the monoolefine of preferred conjugated diene and about 15-60% or polar vinyl compounds are formed.Elastomer core should have mutually second-order transition temperature (Tg) and be lower than about 10 ℃ and preferably be lower than-20 ℃ approximately.The mixture of ethylenically unsaturated monomer then graft polymerization to matrix latex.Various monomers can be used for this grafting purpose, are illustrative below wherein: vinyl compound such as Vinyl toluene or vinylchlorid; The vinyl aromatic (co) same clan such as vinylbenzene, alpha-methyl styrene or halogenated styrenes; Vinyl cyanide, methacrylonitrile or alpha-halogen vinyl cyanide; Vinylformic acid C ₁-C ₈Alkyl ester such as ethyl propenoate or Ethyl acrylate; Methacrylic acid C ₁-C ₈Alkyl ester such as methyl methacrylate or N-Hexyl methacrylate; Methyl propenoic acid glycidyl base ester; Acrylic or methacrylic acid alkene; And analogue, or two or more mixture in the middle of them.Preferred grafted monomer comprises vinylbenzene, in vinyl cyanide and the methyl methacrylate one or more.

Grafted monomer simultaneously or be added in order in the reaction mixture and when be sequentially added into can gather stratiform, shelly or struma shape appurtenant on every side at matrix latex or nuclear.These monomers can add in various ratios each other, though when only using two kinds of monomers, they usually use with equivalent.The typical weight ratio of methyl methacrylate/butadiene/styrene copolymers (" MBS " rubber) is about 60-80 weight part matrix latex, in first and second shell monomers of about 10-20 weight part each.The screening formulation of MBS rubber is to have from about 71 parts of divinyl, about 3 parts of vinylbenzene, about 4 parts of methyl methacrylates and about 1 part of nuclear that Vinylstyrene is polymerized; The shell rubber mutually of about 11 parts of cinnamic second phases and about 11 parts of methyl methacrylates and about 0.1 part of 1,3 butylene glycol dimethacrylate, wherein umber is the weight by total composition.The nuclear of above-described diene alkyl-shell graft copolymer elastomerics and their method of preparation be at the USP3 of Saito, and 287,443, the USP3 of Curfman has carried out detailed discussion in 657,391 and the USP4 of Fromuth, 180,494.

Based on the nuclear-shell graft copolymer of alkyl acrylate rubber have form elastomer core first mutually with around this elastomer core, form rigid thermoplasticity second phase mutually.Elastomer core be by by at least about 50wt% have at the most the alkyl acrylate of 15 carbon atoms and/or monomeric emulsion or the suspension polymerization that the vinylformic acid aralkyl ester is formed forms, though and can use long-chain, alkyl is C preferably ₂-C ₆, butyl acrylate cores most preferably.Elastomer core should have mutually and is lower than about 10 ℃ and preferably be lower than-20 ℃ Tg.(i) crosslinkable monomer of about 0.1-5wt%, that but it has a plurality of addition polymerizations and all polymeric reaction active groups such as butylene glycol diacrylate under substantially the same speed, (ii) grafting monomer, but it has a plurality of addition polymerizations and some of them polymeric reaction active groups under visibly different speed, as toxilic acid diallyl ester, typically be aggregated the part of elastomer-forming nuclear.

The rigid thermoplasticity of acrylic elastomer is to use suspension or emulsion polymerization technology to form on the surface of elastomer core mutually.For produce this mutually needed monomer together with the initiator of necessity directly be added into (wherein form elastomer core) in the reaction mixture and polyreaction be performed until consume the monomer feed basically till.The alkyl ester of ethylenically unsaturated monomer such as methyl propenoic acid glycidyl base ester or unsaturated carboxylic acid, for example vinylformic acid C ₁-C ₈Alkyl ester such as methyl acrylate, hydroxyethyl acrylate or vinylformic acid polyhexamethylene, or methacrylic acid alkene C ₁-C ₈Alkyl ester such as methyl methacrylate or methacrylic acid polyhexamethylene, or the mixture of any aforementioned monomer are some vinyl monomers that can be used in this purpose.Can use heat or oxidation-reduction trigger system.Since grafting with reagent in the lip-deep existence of elastomer core, the part of the rigid thermoplasticity phase of the formation of chain by chemical bonding in elastomer core.Preferably rigid thermoplasticity has mutually at least about 20% and is bonded in elastic kernel.

Preferred acrylic elastomer is by the elastomer core of the about 95wt% of 45wt%-and the rigid thermoplasticity phase composite of the about 5wt% of about 60wt%-.Elastomer core can be from the vinylformic acid C of the about 99.8wt% of about 75wt%- ₁-C ₆Alkyl ester, preferred butyl acrylate cores polymerization obtains.Preferred thermoplastic mutually can be from the methacrylic acid C at least about 50wt% ₁-C ₈Alkyl ester, the preferable methyl methyl acrylate is polymerized.Aforesaid acrylic elastomer and its method of preparation be at the USP3 of Owens, carried out detailed discussion in 808,180 and the USP4 of Witman, 299,928.Various is with Acryloid based on diolefine with based on the nuclear-shell graft copolymer of acrylate ^TMOr Paraloid ^TMElastomerics is available from Rohm ﹠amp; Haas company.

Be used for other the additional impact modifying agent of the present composition or elastomerics generally based on those of long chain hydrocarbon skeleton (" olefin elastomer "), it is mainly from various lists-or two alkenyl monomer preparation and with one or more styrene monomer grafting.Be used for representative example the object of the invention, several olefin elastomers of changing of explanation known substance and be following these: isoprene-isobutylene rubber; Chlorinated polyethylene rubber; Chlorosulfonated polyethylene rubber; Olefin polymer or multipolymer such as ethylene/propene copolymer, ethylene/styrene multipolymer or ethylene/propylene/diene hydrocarbon copolymer, their available one or more styrene monomer grafting; Chloroprene rubber; Paracril; Polyhutadiene and polyisoprene.

The example of preferred olefin elastomer is the multipolymer from following component preparation: (i) at least a olefinic monomer, and as ethene, propylene, different propylene, butylene or iso-butylene, or at least a conjugated diene such as divinyl, and analogue, or their mixture; (ii) carry the ethylenically unsaturated monomer (for example methyl propenoic acid glycidyl base ester) and the arbitrariness ground of epoxy group(ing), (iii) do not carry the ethylenically unsaturated monomer (for example vinyl-acetic ester) of epoxy group(ing).

When use replenishing impact modifying agent, it is desirable in (by the parts by weight of total blend composition) at least about 1 part, preferably at least about 5 parts, more preferably from about 10 parts and most preferably exist at least about 15 parts amount.Additional impact modifying agent typically not to be higher than about 50 parts, is not higher than about 40 parts ideally, preferably is not higher than about 30 parts and exist more preferably no higher than about 25 parts amount.

When replenishing impact modifying agent with thermoplastics (as polycarbonate) with have polyester when using as the blend of the branched block ethylene polymers thing of reactive behavior thermoplastic polymer components (c), additional impact modifying agent will be in this blend in (by the parts by weight of total blend compositions) at least about 0.1 part, ideal is at least about 0.5 part, preferably at least about 1 part, more preferably at least about 3 parts, but be no more than about 25 parts, be not higher than about 20 parts ideally, preferably be not higher than about 15 parts and exist more preferably no higher than about 10 parts amount.

About the purposes of styrene copolymer as the annexing ingredient of the blend of branched block ethylene polymers thing and blend or molding usefulness thermoplastic polymer.

In belonging to branched block ethylene polymers thing and blend or the molding example of the present invention with the blend of polymkeric substance, this blend further comprises styrene copolymer.This styrene copolymer is found in the blend that is specially adapted to the branched block ethylene polymers thing, and wherein the reactive behavior thermoplastic polymer is a polyester.

Suitable styrene copolymer is can to prepare with the ethylenically unsaturated monomer of styrene monomer copolymerization from one or more styrene monomers and one or more.Styrene copolymer can be random, alternative, block or the grafted multipolymer, the mixture of more than one styrol copolymers also can use.

Except vinylbenzene itself, the styrene monomer that is specially adapted to the preparation of styrene copolymer comprises one or more [it should be understood that " vinylbenzene " as the comonomer of component (c) is considered to any other monomer of any or same-type in vinylbenzene as herein described or the vi-ny l aromatic monomers] by the substituted phenylethylene of following formula statement or vinyl aromatic compounds: Wherein each A is hydrogen independently, C ₁-C ₆Alkyl or halogen atom such as chlorine or bromine; With each E be hydrogen independently, C ₁-C ₁₀Alkyl, cycloalkyl, alkenyl, cycloalkenyl, aryl, alkaryl, aralkyl or alkoxyl group, halogen atom such as chlorine or bromine, perhaps two E are connected to form naphthalene structure.The representative example of other the suitable styrene monomer except that vinylbenzene itself comprise following one or more: cyclosubstituted ring-alkylated styrenes, Vinyl toluene for example, neighbour-ethyl styrene, right-ethyl styrene, ar-(tertiary butyl) vinylbenzene, 2, the 4-dimethyl styrene; Cyclosubstituted halogenated styrenes class, for example neighbour-chloro-styrene is right-chloro-styrene, neighbour-bromstyrol, 2,4 dichloro benzene ethene; The vinylbenzene that alkyl on the ring, nuclear halogen replace, 2-chloro-4-vinyl toluene and 2 for example, 6-two chloro-4-vinyl toluenes; The ar-methoxy styrene, vinyl naphthalene or anthracene, right-di isopropenylbenzene, Vinylstyrene, vinyl-dimethyl benzene, alpha-methyl styrene and Alpha-Methyl Vinyl toluene.

Comprise one or more of explaining with the preferred ethylenically unsaturated monomer of styrene monomer copolymerization by following formula:

D--CH==C (D)--(CH ₂) _n--G, wherein each D represents to be selected from hydrogen independently, halogen (as fluorine, chlorine, or bromine), C ₁-C ₆The substituting group of alkyl or alkoxyl group, or the expression acid anhydrides that connects together connects base; G is a hydrogen, vinyl, C ₁-C ₁₂Alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkaryl, aralkyl, alkoxyl group, aryloxy, ketone oxygen base (ketoxy), halogen (as fluorine, chlorine or bromine), cyano group or pyridyl; With n be 0-9.

Can be with the representative example of the ethylenically unsaturated monomer of styrene monomer copolymerization have polarity or electronegativity group those and comprise following one or more: vinyl nitrile compound such as vinyl cyanide, methacrylonitrile, ethyl acrylonitrile, α-Lv Daibingxijing and flumaronitrile; Diolefine such as divinyl, isoprene, iso-butylene, piperylene, cyclopentadiene, natural rubber, chlorinated rubber, 1,2-hexadiene, methyl isophthalic acid, 3-pentadiene, 2,3-dimethyl-1, the 3-pentadiene, 2-methyl-3-ethyl-1,3-butadiene, 2-ethyl-1, the 3-pentadiene, 1,3-and 2,4-hexadiene, divinyl such as dichloroprene that chlorine and bromine replace, bromoprene, chloroprene and dibromo divinyl, and divinyl/isoprene and isoprene/isobutylene copolymers; 1, the 3-Vinylstyrene; 2-phenyl propylene; C ₂-C ₁₀Olefin(e) compound comprises derivative such as vinylchlorid or vinylidene chloride that its halogen replaces; α, β-ethylenically unsaturated carboxylic acids, as vinylformic acid, methacrylic acid, toxilic acid, succsinic acid, equisetic acid and methylene-succinic acid and their acid anhydrides and C ₁-C ₁₀Alkyl, aminoalkyl group and hydroxy alkyl ester and amides, as vinylformic acid and alkyl methacrylate such as methyl methacrylate, propyl acrylate, butyl acrylate, Octyl acrylate, methyl, the methacrylic ester of methyl, ethyl or isobutyl-, the acrylate of hydroxyethyl and hydroxypropyl, acrylic-amino ethyl ester and methyl propenoic acid glycidyl base ester; Maleic anhydride; The maleic acid ester of alkyl or aryl or fumarate such as chlorofumaric acid diethyl ester or fumaric acid diethyl ester; Aliphatic series or aromatics maleimide as N-phenylmaleimide, comprise C ₁-C ₁₀Alkyl or C ₆-C ₁₄The reaction product of aryl amine quiberon and maleic anhydride; Methacrylamide, acrylamide or N, N-diethyl acrylamide; Vinyl ketones such as methyl vinyl ketone or methyl isopropenyl ketone; Vinyl-acetic ester or allyl ester and senior alkyl or aryl vinyl or allyl ester; Vinyl alcohol; Vinyl ether such as C ₁-C ₆The halogen derivative that alkyl vinyl ether and their alkyl replace; Vinyl pyridine; The vinyl furans; Vinyl aldehyde such as propenal or crotonic aldehyde; Vinylcarbazole; Vinyl pyrrolidone; N-vinyl phthalic imidine; And have following formula De oxazoline compound, wherein each J is hydrogen independently, halogen, C ₁-C ₁₀Alkyl or C ₆-C ₁₄Aryl etc.:

The example of preferred styrol copolymer is aromatic vinyl/vinyl nitrile multipolymer such as styrene/acrylonitrile copolymer (" SAN "), phenylethylene/maleic anhydride copolymer, styrene/methacrylic acid glycidyl ester copolymer, aromatic group maleimide/vinyl nitrile/diolefine/styrol copolymer, the styrene/methacrylic acid alkyl ester copolymer, styrene/methacrylic acid alkyl ester/methyl propenoic acid glycidyl base ester copolymer, styrene/acrylic butyl ester multipolymer, methyl methacrylate/acrylonitrile/butadiene/styrene multipolymer, or the aromatic vinyl/vinyl nitrile rubber of modified rubber such as ABS, AES or ASA multipolymer.

ABS (acrylonitrile/butadiene/styrene multipolymer) is elasticity-thermoplastic composite, and therein ethylene base aromatics/vinyl nitrile multipolymer is grafted on the polyhutadiene matrix latex.Polyhutadiene forms the particle-rubber modifier of rubber or elastic component-they are scattered in by in the thermoplastic matrix that random ethylene base aromatics/the vinyl nitrile multipolymer forms mutually as discrete.Typically, aromatic vinyl/vinyl nitrile multipolymer is to be comprised in the rubber grain simultaneously and to be grafted on this particle.AES (vinyl cyanide/EPDM/ vinylbenzene) multipolymer be when with aromatic vinyl/vinyl nitrile copolymer grafted on the matrix of forming by EPDM (ethylene/propene/non-conjugated diene hydrocarbon) rubber to styrene copolymer that aromatic vinyl/the vinyl nitrile multipolymer is obtained when carrying out modified rubber.The AES multipolymer at length is discussed in the US patent 4,766,175 of Henton.Aromatic vinyl/vinyl nitrile multipolymer also can be grafted to the styrene copolymer that forms modified rubber on the acrylic acid alkyl ester elastomer, the same with the situation of ASA (vinyl cyanide/phenylethylene ethylene/propenoic acid ester) multipolymer, it at length is discussed at the US3 of Yu, in 944,631.

The monomer that forms styrene copolymer after the copolymerization uses with any amount in the 1-99wt% scope in fact separately, but styrene copolymer typically contains at least about 15wt%, preferably at least about 35wt%, more preferably at least about the styrene monomer of 60wt%, equal amount is one or more copolymerizable ethylenically unsaturated monomers.When carrying out modified rubber, styrene copolymer typically contains at least about 15wt%, and preferably at least about 25wt% with more preferably at least about the styrene monomer of 35wt%, equal amount is one or more copolymerizable ethylenically unsaturated monomers.

The elasticity of the styrene copolymer of the modified rubber that uses in composition of the present invention is account for multipolymer weight about at the most 45% mutually, preferably about 5-40%, more preferably from about 10-35%.The mutually shown second-order transition temperature (Tg) that goes out of preferred elastomerics generally is lower than 0 ℃, more preferably less than-30 ℃ with most preferably from about-110 to-50 ℃ approximately, by ASTM D-746-52T or-56T measures.Elastomerics has mutually about 10 microns or lower of mean particle size ideally, preferably in about 5 micrometer ranges of about 0.05-and more preferably at about 0.1-about 0.3 micron and typically to demonstrate limiting viscosity (recording under 25 ℃ in toluene) be about 0.1-about 5.Except that above-mentioned monomer component, elastomerics also contains the linking agent of a small amount of (based on rubber, being usually less than about 2wt%) mutually, as Vinylstyrene, the diallyl maleate ester, ethylene glycol dimethacrylate etc., precondition is the required elasticity that this linking agent can not eliminated rubber.

The molecular weight of styrene copolymer is not crucial, if its melt flow viscosity allow it can with other component blend of the present composition.Preferably, however the melt flow viscosity of the styrene copolymer that is recorded by ASTM D-1238-65T (1) is that about 0.01-is about 10, more preferably from about 0.1-about 5 and most preferably from about 2-about 3 deciliters/minute (dl/min).When ethylenically unsaturated monomer had polar group, polar group typically had the group moment of about 1.4-4.4 debye unit(D), also allowed though deflect away from the value of this scope.Styrene copolymer can be prepared by emulsion, suspension or bulk process.

The method of making aforesaid ABS or other styrene copolymer is described in detail in the US patent 2,820,773 of Childers, the US 3,238 of Calvent, 275, the US 3,515,692 of Carrock, the US 4 of Ackerman, 151,128, the US4 of Kruse, 187,260, the US 4,252,911 of Simon, the US 4,526,926 of Weber, the US 4 of Rudd, 136,762 and the US 4,624,986 of Wber.

Styrene copolymer (when existing) will be with (based on the parts by weight of the gross weight of blend composition) at least about 5 parts in the blend of thermoplastic polymer and branched block ethylene polymers thing at blend or molding, ideally at least about 10 parts, preferably at least about 15 parts, more preferably at least about 20 parts, but be no more than about 75 parts, be no more than about 55 parts ideally, preferably be no more than about 50 parts and exist more preferably no more than about 45 parts amount.

About the existence of flow ability modifying agent in branched block ethylene polymers thing and blend or the molding usefulness blend of thermoplastic polymer.

Branched block ethylene polymers thing and blend or molding further comprise flow ability modifying agent with the blend of thermoplastic polymer.The flow ability modifying agent of usefulness is polymeric amide and/or polyolefine for example.

Described identical as the polymeric amide of flow ability modifying agent with the amine-functionalized polymers of above reactive behavior thermoplastic polymer about the subfraction (c) that is used as branched block ethylene polymers thing of the present invention.Polyolefine as flow ability modifying agent uses the possible composition of polymkeric substance described identical with above about thermoplasticity blend or molding.

Flow ability modifying agent resin (when existing) will be with (based on the parts by weight of the gross weight of blend composition) at least about 5 parts in the blend of thermoplastic polymer and branched block ethylene polymers thing at blend or molding, ideally at least about 10 parts, preferably at least about 15 parts with more preferably exist at least about 20 parts amount.Equally, the flow ability modifying agent resin will be no more than about 75 parts with (based on the parts by weight of the gross weight of blend composition), be no more than about 55 parts ideally, preferably be no more than about 50 parts and exist more preferably no more than about 45 parts amount.

Using wherein, the reactive behavior thermoplastic polymer of subfraction (c) is the preferred composition of the branched block ethylene polymers thing of polyester:

Using the reactive behavior thermoplastic polymer of subfraction (c) wherein is that the preferred composition of the branched block ethylene polymers thing of polyester will comprise following component: (a) branched block ethylene polymers thing: at least about 1 part, ideally at least about 2 parts, preferably at least about 5 parts, but be no more than about 40 parts, be no more than 30 parts and preferably be no more than 20 parts ideally.(b) thermoplasticity blend or molding polymkeric substance: at least about 60 parts,, but be no more than about 99 parts, be no more than 98 parts and preferably be no more than 95 parts ideally ideally at least about 70 parts with preferably at least about 80 parts.(c) styrene copolymer (when existing): at least about 5 parts, ideally at least about 10 parts with preferably at least about 15 parts, more preferably at least about 20 parts, but be no more than about 75 parts, be no more than 55 parts ideally, preferably be no more than 50 parts, more preferably no more than about 45 parts.(d) impact modifying agent of Bu Chonging (when existing): at least about 0.1 part, ideally at least about 0.5 part with preferably at least about 1 part, more preferably at least about 3 parts, but be no more than about 25 parts, be no more than 20 parts ideally, preferably be no more than 15 parts, more preferably no more than about 10 parts.(e) flow ability modifying agent resin (when existing): at least about 5 parts, ideally at least about 10 parts with preferably at least about 15 parts, more preferably at least about 20 parts, but be no more than about 75 parts, be no more than 55 parts ideally, preferably be no more than 50 parts, more preferably no more than about 45 parts.

The reactive behavior thermoplastic polymer is the particular embodiment of polycaprolactone.

In a particular embodiment of the present invention, the branched block ethylene polymers thing comprises the branched block ethylene polymers thing, and wherein the reactive behavior thermoplastic polymer is a polycaprolactone.Said composition be found can with polycarbonate and as blend or molding with the homogeneous ethene polymers of polymkeric substance and as a supplement the styrene-acrylonitrile grafted ethylene-propylene-dience rubber of impact modifying agent use.This type of blend further comprises the branched block ethylene polymers thing of 0.001-50wt%, styrene-acrylonitrile grafted ethylene-propylene-dience rubber of the homogeneous ethene polymers of 0.01-50wt% and the polycarbonate of 50-99.99wt% and 0.001-10wt%.

This composition has good melt processability and toughness, makes them can be used for contour extrusion, and the injection moulding of automobile application, computer and business machine is used, and communication device and other thin-walled injection molding are used.

About additive in the branched block ethylene polymers thing and/or at branched block ethylene polymers thing and additional blend or molding with the existence in the blend of polymkeric substance:

Be used for to various additive arbitrarinesses improving the flame retardant resistance or the anti-ignition quality of the present composition.Other representative example comprises metal such as antimony, bismuth, arsenic, tin and the plumbous oxide compound and the halogenide of periodic table of elements IVA and VA family, as weisspiessglanz, and antimony chloride, English powder, stannic oxide, tin chloride and arsenic oxide arsenoxide; Organic and the mineral compound of phosphorus, nitrogen, boron and sulphur such as aromatic phosphate acid ester and phosphonic acid ester (comprising its halo derivatives), mono alkyl phosphate, three butoxy ethyl ester of phosphoric acid, 1,3-two chloro-2-propyl alcohol phosphoric acid ester, 3, new penta oxygen-2 of 9-dibromo, 4,8,10-four oxa-s-3,9-two phospha spiral shell (5.5) undecanes-3,9-dioxide, phosphine oxide, ammonium phosphate, zinc borate, thiocarbamide, urea, Ammonium sulfamate, ammonium polyphosphate and tin sulfide; The oxide compound of other metal such as titanium, vanadium, chromium and manganese, halogenide and hydrate, as titanium dioxide, chromic bromide, zirconium white, ammonium molybdate and tin oxide hydrate; Antimony compounds class such as phosphoric acid antimony, sodium antimonate, KSb (OH) ₆, NH ₄SbF ₆And SbS ₃The metaantimmonic acid ester of mineral acid, cycloalkyl stibnous acid esters and aryl metaantimmonic acid compounds such as antimonypotassium tartrate, caproic acid antimonic salt, Sb (OCH ₂CH ₃), Sb[OCH (CH ₃) CH ₂CH ₃] ₃, polyvinyl alcohol acid antimony, antimonous acid pentaerythritol ester and antimony triphenyl; Boric acid; Alumina trihydrate; Ammonium borofluoride; Molybdenum oxide; Halohydrocarbon such as hexabromo cyclodecane; Decabrominated dipheny base ether; 1, two (2,4, the 6-tribromophenoxy) ethane of 2-; Halo carbonic ether oligopolymer class is as from those of tetrabromobisphenol-A preparation; Halogenated epoxy resin such as bromination glycidyl ether; Tetrabromophthalic anhydride; Fluorinated olefin polymer or multipolymer are as poly-(tetrafluoroethylene); Octabromodiphenyl base ether; Brometo de amonio; Metatitanic acid sec.-propyl two (4-amino benzoyl) isostearoyl base ester; With the metal-salt of aromatic sulfur compound, as vitriol, hydrosulfate, sulfonate, sulphonamide and sulfimide; Other basic metal and the alkaline earth salt of sulphur, phosphorus and nitrogen compound; With US4 at Laughner, other material of describing in 786,686; And their mixture.Preferred flame-retardant additive is ANTIMONY TRIOXIDE SB 203 99.8 PCT (Sb ₂O ₃).When using fire retardant in composition of the present invention, it is typically to account for the about at the most 15% of present composition weight, about ideally 0.01-15%, preferably about 0.1-10% and the more preferably from about amount use of 0.5-5wt%.

Arbitrariness ground uses various additives reaching other purpose in composition of the present invention, as following these: biocide such as organic metal species, isothtazolone, organosulfur and mercaptan; Antioxidant such as phenols, secondary amine, phosphorous acid ester and thioesters; Static inhibitor such as quaternary ammonium compound, amine, ethoxylation, propoxylation or glycerol compounds; Filler and toughener such as talcum, clay, mica, silica, silica powder, kaolin, aluminium nitride, titanium dioxide, calcium sulfate, boron trioxide, aluminum oxide, glass sheet stock, bead, palpus crystalline substance or monfil, nickel powder and metal or graphite fibre; Hydrolysis stabilizer; Lubricant such as lipid acid, Fatty Alcohol(C12-C14 and C12-C18), ester class, fatty amide, Metallic stearates, paraffinic hydrocarbons and Microcrystalline Wax, siloxanes and ortho-phosphoric acid ester; Releasing agent, as fine particle or powder solid, soap, wax, siloxanes, polyglycol and complex ester class are as three stearic acid trihydroxymethylpropanyl ester or pentaerythritol tetrastearates; Pigment, dyestuff and colorant; The ester class of softening agent such as diprotic acid (or their acid anhydrides) and monohydroxy-alcohol is as phthalic ester, adipic acid ester and benzoic ether; Thermo-stabilizer such as organotin mercaptide, the octyl group ester of thioglycolic acid and barium or cadmium carboxylate salt; UV light stabilizing agent such as hindered amine, neighbour-hydroxyl-phenyl benzotriazole, 2-hydroxyl, 4-alkoxy benzophenone, salicylate, cyanoacrylate, nickel chelate and toluenyl malonic ester and oxamide.Preferred hindered phenol anti-oxidants is Irganox ^TM1076 antioxidants are available from Ciba-Geigy company.If use, examples of such additives typically is no more than the 45wt% of total composition weight and is about 0.001-15wt% ideally, preferably about 0.01-10wt% and 0.1-10wt% more preferably from about.

For the blend of branched block ethylene polymers thing and additional modification or blend usefulness polymkeric substance, the same arbitrariness of this blend polymer ground comprises other additive, as filler, and colorant, antioxidant, static inhibitor, antiseize paste, thickening material, spices etc.

Improve the purposes of use temperature about the branched block ethylene polymers thing.Branched block ethylene polymers thing of the present invention has the segment of softer polyvinyl segment and harder reactive behavior thermoplastic polymer (being preferably the engineering thermoplasties).Hard engineered thermoplastic segment is used for promoting polyvinyl upper limit working temperature.In this embodiment, the engineered thermoplastic impact modifying agent more preferably less than about 40wt%, most preferably is lower than about 30wt% preferably to be lower than about 50wt%, even exist more preferably less than the amount of about 20wt%, based on the gross weight of branched block ethylene polymers thing of the present invention.Under these consumptions, the observed use temperature scope (can not melting or be out of shape) that enlarges the branched block ethylene polymers thing of engineering plastics.Polyvinyl amount is preferably at least about 0.01wt%, more preferably at least about 0.1wt%, most preferably at least about 1wt% with even more preferably at least about 10wt%.

Embodiment

The following examples are used for illustrating but do not limit the present invention.Percentage ratio, ratio and umber are by weight calculation, except as otherwise noted.Embodiments of the invention (Ex.) are with numeral, rather than the comparative example of the embodiment of the invention (C.S.) is with letter representation.

For enforcement of the present invention is described, listed the embodiment of several preferred embodiments below, still, these embodiment limit scope of the present invention anything but.By the characteristic of embodiment and those characteristics of various comparative formula (comparative example) being compared special ideal features more of the present invention as can be seen (therefore the latter does not have feature of the present invention is not embodiment of the present invention).

Except as otherwise noted, for embodiment 1-7, the branched block ethylene polymers thing that contains at composition of the present invention is by (weight-average molecular weight is 22 with nylon 6,000 and melt index be 7) and ethene polymers (the maleic anhydride branch of containing 1wt%) linear or substantial linear carry out dried mixing by aforesaid amount and prepare.Maleic anhydride branch is by using peroxide initiator, forms on the ethene polymers of linearity or substantial linear with the amount (based on the polyvinyl weight of branching linearity or substantial linear) of 1wt%.Polyvinyl the doing of nylon 6 and branching branching linearity or substantial linear mixed thing then at 30mm Werner ﹠amp; Carry out melting mixing in the Pfleiderer forcing machine and formed the branched block ethylene polymers thing with the maleic anhydride branching reaction and as final block interpolation to cause nylon 6.The condition of using in reactive behavior is extruded is: zone temperatures is 150,200,250,250 and 250 ℃; 250rpm; The 70-85% moment of torsion; With 30 second residence time.The branched block ethylene polymers thing is by ice-water bath, be cut into pellet and be collected with the polyolefin resin blend.

By dried ingredients was separately mixed 5 minutes in the coating vibrator, will do mixed formulation then and join Werner ﹠amp; Extrusion molding in the Pfleiderer forcing machine, its processing conditions be used for preparing the identical of branched block ethylene polymers thing, just zone temperatures is 150,200,280,280 and 280 ℃, finally prepares blend composition.Extrudate is once more with wire-form cooling and be broken into pellet.Pellet descended dry 3 hours at 120 ℃ in the air-flow baking oven, was used for preparing on 70 tons of Arburg mould machines test sample then, and wherein a tube temperature is 200 ℃ (chargings), 250 ℃, 250 ℃ and 255 ℃ (notes mouth), die temperature are that 80 and screw speed are 120rpm.

" polypropylene " is the Profax available from Himont ^TM6323 polypropylene;

" HDPE " has the about 0.96g/cm of density ³And I ₂Melt index (according to ASTM D1238) is the high density polyethylene(HDPE) of about 10g/10min;

" POE " is the ethene polymers of aforesaid nonbranched substantial linear;

" POE-b-MAH " is the aforesaid ethene polymers that contains maleic anhydride ramose substantial linear;

" B/BEP I " is the branched block ethylene polymers thing from the nylon that contains maleic anhydride ramose substantial linear ethene polymers and 30wt% 6 preparations of 70wt%;

" B/BEP II " is the Tafmer from (i) 80wt% ^TMThe P-0180 ethylene/propene copolymer, available from the linear homogeneous ethene polymers of Mitsui Petrochemical, it is 0.869g/cm that the latter has density ³, melt index (I ₂) be 4 and maleic anhydride branch; The (ii) branched block ethylene polymers thing of 20wt% nylon 6 preparation; With

" EP " is the linearity that exists in blend composition or the polyvinyl wt% of substantial linear, no matter ethene polymers is not branching, branching or form the branched block ethylene polymers thing.

Nylon 6 is the polymeric amide with melt index 7, molecular weight 22,000 (Capron 8207) available from Allied Signal company.

EG 8200gMAH-polyolefin elastomer, I ₂Be 5g/10min, use the 1wt% maleic anhydride graft.

The ENGAGE*8150-polyolefin elastomer, I ₂Be 0.5g/10min, available from Dow chemical company.Annotate: the trade mark of * Dow chemical company.

Embodiment 1-5 and reference examples A-C are carried out the test of following physical and mechanical property, these tests the results are shown in Table I.

According to ASTM regulation D 256-84 (method A) under 25 ℃ by Ai Zuode test determination shock strength (" Izod ").Root radius is 10 mils (0.254mm).The Ai Zuode test-results is with the ft-lb/in record.

Also according to ASTM regulation D 256-84 (method A) under 25 ℃ by Ai Zuode test determination shock strength (" welded bonds "), but at the sample that in the twoport mould, forms with jam welding.Sample is unnotched, places it in and makes the upper surface high 1mm of weld than bench vice anchor clamps on the bench vice.Welded bonds result is also with the ft-lb/in record, but exception among the embodiment 5, the wherein not fracture of " N.B. " expression sample.

Drop to 1/8 by the 100 pound weight things that under 23 ℃, will carry 1/2 ｀ ｀ dart and " carry out drop-dart impact test (" dart ") on the thick circular specimen.The dart of having weighed is along fluting track free-falling and impact sample, and sample is fixed on the aluminium casting pedestal in the position on the descent path, 0.640 inch hole is being arranged to accept dart behind the dart impact sample on the pedestal.Instrument is Dynatup Mode l8250.If sample is not accepting to demonstrate cracking or perforation on the ballistic side, then sample destroys.The result is by (fracture or the perforation that do not have dart to cause at shock point) or destroys (material demonstrates cracking or perforation), when falling and during the accumulation certain energy (this height is necessary for accumulating this energy) from the certain altitude of track top by the above dart.The value that in Table I, writes down be " by " or, represent with in-lb there not being maximum energy that sample is accepted under the destructive situation.

According under 66psi, measuring deflection under load temperature (" D.T.U.L ") under the ASTM regulation D 648-82.The result is with a ℃ record.

Measure modulus in flexure (" F. modulus ") according to ASTM D 790.The result is with the psi record.

Unless opposite indication is arranged, the substantial linear ethene polymers of Shi Yonging is the technology that provides according in the US patent 5,272,236 in an embodiment, uses by three (perfluorophenyl) borine activatory [((CH ₃) ₄C ₅))-(CH ₃) ₂Si-N-(t-C ₄H ₉)] TI (CH ₃) ₂Organo-metallic catalyst is prepared by solution polymerization process.Unless opposite indication is arranged in addition, all umber and percentage ratios are by weight, based on gross weight.Unless opposite indication is arranged in addition, the testing method below using:

Gap Izod impact strength ASTM D 256 (at 23 ℃, 0 ℃ ,-18

(ft-lb/in) ℃ ,-29 ℃ and-40 ℃)

2. (pound/inch stretches ², psi) ASTM D-638

3. surrender (psi) ASTM D-638

4. extend (%) ASTM D-638

5. whiteness index (WI) ASTM E-313

6. yellowness index (YI) ASTM E-313

7. the electron photomicrograph of the thinly-sliced molded sample of granularity (micron)

ASTM?D-3763-86

8.Dynatup ASTM D-3763-86 (at-29 ℃)

Specific embodiments

Specimen preparation

Polymkeric substance is joined Werner ﹠amp; Prepare all samples in the Pfleiderer ZSK-53/5L co-rotating twin screw extruder.After polymkeric substance is added in the forcing machine, through nozzle the mixture of maleic anhydride (MAH)/methyl ethyl ketone (MEK)/LUPERSOL130 (initiator) is joined the end of the section 1 of forcing machine with 1: 1: 0.032 weight ratio by the metered charge pump.LUPERSOL 130 is by 2 of Atochem produce and market, 5-two (t-butylperoxy) hexin-3.Forcing machine is maintained under the vacuum level that is greater than or equal to 26 inches of mercury to promote to deviate from solvent, unreacted MAH and other pollutent and so on volatile matter.

Attane  resin is by the ULDPE alkene of Dow chemical company produce and market/1-octene resin.Dowlex  resin is by the LLDPE alkene of Dow chemical company produce and market/1-octene resin.Tafmer  P-0180 resin is the ethylene/propene copolymer resin by Mitsui Petrochemical produce and market.

Use following material:

ADMER QF 500A is with 1.5wt%MAH grafted polypropylene with by the MitsuiPetrochemical produce and market; This graft copolymer has melt index under 230 ℃ be that 3.0g/10min and density are 0.900g/cm ³

Primacor  3460 is by ethene and acrylic acid multipolymer of Dow chemical company produce and market; This material contains the 9.7wt% Acrylic Acid Monomer and has melt index 20g/10min.

Graft modification homogeneous ethene polymers; This material contains 1.3wt%MAH, and having melt index 0.25g/10min and density is 0.870g/cm ³

Profax  6524, by the polypropylene of Himont produce and market, it has melt index at 230 ℃ is that 4g/10min and density are 0.9g/cm ³

According to US4, the method for describing in 950,541 prepare graft modification homogeneous ethene polymers (below be called INSITE ^TMTechnology polymer or ITP).Polymeric constituent is done with certain weight ratio and is mixed, and joins then at about 210 ℃ of Werner that operate down; In the PfleidererZSK-30 twin screw extruder.Extrude the dried thing that mixes of manufacturing in the samsara at one.

Use 50 tons of Negri Bossi injection molding machines to prepare injected sample, operational condition is that tube is warm between 200-250 ℃, and it is 40 crust that tube is pressed, and the cooling die temperature is 85 (29 ℃) and about 12 seconds of the residence time in cooling die.Sample is formed as 2.5 " * 6.5 " * 0.075 " sheet materials.

For each the sample measurement modulus in flexure in the table 8 and Ai Zuode impact property (under room temperature and-30 ℃).These performances are important in many application examples in as trolley part.Respectively according to ASTM D-790 and D-256 measurement performance.

With maleic anhydride ethylene-propylene-diene elastomer (the product trade mark-ROYALTUF 465A) functionalized and that sell by Uniroyal Chemical.

With maleic anhydride ethylene-propylene elastomeric (the product trade mark-Exxelor VA 1801) functionalized and that sell by Exxon Chemical.

Use the ethylene-propylene elastomeric (Tafmer P-0180 is available from Mitsui) of modified by maleic acid anhydride graft as mentioned above.

Nylon 1000-1 is the low Mw nylon 6,6 that is used for injection moulding available from Hoechst-Celanese company.

Nylon 1200-1 is the high Mw nylon 6,6 that is used for extrusion molding available from Hoechst-Celanese company.

By the reactive behavior extrusion method ethene/1-octene copolymer (ITP-g-MAH) of maleic anhydride graft prepared maleic anhydride graft to the ethylene-octene copolymer is used for this research.The multipolymer that the ethylene-octene copolymer that is used for preparing ITP-g-MAH is to use how much limited single position catalyzer to prepare at solution polymerization process.It is about 0.5/10min that final graft copolymer (lot number XUR-1567-48562-D4) has melt index, and density is that 0.87g/cc and MAH content are 1wt%.(1％MAH-ITP)。

Polybutylene terephthalate (PBT) is the Celanex2002 (0.9IV) available from Celanese.

By the acrylic copolymer that methyl methacrylate-butyl acrylate cores-methyl propenoic acid glycidyl base ester (MMA/GMA) is formed, 90: 8: 2 weight ratios.

Testing method:

Use the dynamic properties of rheology solid analysis instrument RSA-II study sample.Test sample is made into form of film (about 15-20 mil thickness).-120 ℃ of measure sample to the scope of the top temperature as far as possible that makes sample fusing or distortion.Under the frequency of 10 radian per seconds (rad/s) and 7.0 * 10 ^-4Measure under the strain.

On Instron series IX Auto-Test System 1.04, test tensile property.The machine parameter of test is: 18.21 parts/second of sample velocities; Pinblock speed: 2.00in/min; Gamut load range: 10.00 (pounds); Humidity: 50%; Temperature: 73.

Embodiment 1

By ITP-g-MAH (1400g) and PBT (600g) are done mixed/mixing and use 30mmWerner ﹠amp subsequently; Pfleiderer twin screw extruder (250rpm, input speed produces the 70-85% moment of torsion and five barrel section temperature are set in 150,200,250,250 and 250 ℃) carries out melt blending and prepares composition.Use Conair wire rod cutting machine with the extrudate granulation.Result in Fig. 1 shows that MAH-g-ITP/PBT blend comparison product (ITP-g-MAH or ITP/PBT blend) in the same old way has higher use temperature.Use dynamic mechanical analysis instrument (solid-state, as to extend), two contrasts all destroy down at about 60 ℃, and ITP-g-MAH/PBT still stablizes under up to 120 ℃.The rheology contrast is shown among Fig. 2.The result shows that ITP-g-MAH/PBT has the thermoplastic elastomer that improves processibility and enhanced pseudo-plasticity (" shear shinning ") behavior.As listed among Figure 19, the ITP-g-MAH/PBT blend also has improved tensile property, with independent ITP Comparatively speaking.At Tu2 ﹠amp; Take from the tan δ data of DMS test in 3 and represent that also these materials can be used for blowing and thermoforming is used.

Embodiment 2

By with ITP-g-MAH (133g) with MMA/GMA acrylic copolymer (57g) is mixed under 230 ℃ in HaakeSystem 90 torque rheometers or melt blending reaches 10 minutes and prepares composition.Resulting mixture is cooled to room temperature subsequently and uses grinding machine efflorescence in addition.RSA result in Fig. 4 shows that the reactive behavior blend of ITP-g-MAH/ (MMA/GMA) has high use temperature, and promptly sample is stable under up to 110 ℃.

Though the embodiment by the front has described the present invention in detail, these descriptions only are not think qualification the present invention for illustration purpose.Under the prerequisite that does not break away from the spirit and scope of the present invention described in claim, can do many variations to the embodiment of front.

Embodiment 3-7

Investigated nylon in this research process (engineering thermoplasties's example) modified elastomer is listed in the table 1.Press the specified proportion dry blend at 35mm Werner ﹠amp by Engage*8200 (trade mark of Dow chemical company) (EG 8200 MAH) with nylon 6 with the elastomerics MAH modification of maleic anhydride graft; Under 250rpm, carry out melt blending in 260 ℃ in the Pfleiderer co-rotating twin screw extruder and prepare these compositions.The modified elastomer of each extrusion molding is cut into particulate matter and is collected the final blend of getting off to be used for the special polyolefins binder resin by an ice-water bath.

Figure 4 and 5 are made comparisons to the rheology and the tan δ performance of ethene polymers under the velocity of shear of 0.1 radian per second-100 radian per second of the ethene polymers of the substantial linear of substantial linear ethene polymers, maleic anhydride graft and polyamide modified substantial linear schematically.Fig. 6-Fig. 9 (190 ℃ ﹠amp; 230 ℃) illustrated that the polymeric amide of various concentration in the ethylene elastomer of the substantial linear of maleic anhydride graft is to these same rheologies and Young's modulus Effect on Performance.These description of drawings novel nylon modification Engage elastomerics not only on shearing sensibility, improve a lot, and significantly high melt elasticity (low tan δ) is arranged than typical Engage* polymkeric substance (the polyvinyl example of narrow dispersiveness).What is interesting is that the slope of viscograph has shown that descending the slope of viscograph to compare with 230 ℃ (fusing points that are higher than nylon 6) has very little variation, only be the expection displacement under the higher temperature under 190 ℃ (being lower than the fusing point of nylon 6).

Table 1

Wherein the reactive behavior thermoplastics is the branched block ethylene polymers thing of nylon 6

Embodiment	3	4	5	6	7
						Engage* 8200/MAH	1800	1700	1600	1500	1400
Nylon 6	200	300	400	500	600
						Wt% nylon	10	15	20	25	30

* available from the ethene polymers of Dow chemical company

With the same polymkeric substance of the present invention that in Fig. 4-18, provides characteristic for preparing among the embodiment 3-7.Fig. 1-2 a, those of the polymkeric substance of 2b and embodiment 1 and 2 are by preparing with quadrat method.

The tan δ value of branched block ethylene polymers thing of the present invention also is superior to homogeneous ethene polymers or branching homogeneous ethene polymers, and is the indication of the remarkable high melt elasticity (high storage modulus) under low shearing and high-shear.And, have now found that branched block ethylene polymers thing of the present invention has corresponding influence for containing the blend of molding with polymkeric substance.This blend composition is than only demonstrating bigger shearing sensibility and bigger melt elasticity with homogeneous ethene polymers or branching homogeneous ethene polymers under low the shearing.

Embodiment 8-24: the reactive behavior thermoplastic polymer of subfraction (c) is the use of the branched block ethylene polymers thing of amine-functionalized polymers:

The branched block ethylene polymers thing that in the composition of embodiment 8-24, contains be by with nylon 6 (weight-average molecular weight be 22,000 and melt index be 7) and the ethene polymers (" E/MAH polymkeric substance ") that contains the maleic anhydride tapping point do respectively by the following stated consumption and mix preparation.The maleic anhydride tapping point forms on the E/MAH polymkeric substance by using peroxide initiator, and content accounts for about 1wt% of E/MAH polymer weight.Doing of nylon 6 and E/MAH polymkeric substance mixes thing then at 30mm Werner ﹠amp; Carrying out melting mixing in the Pfleiderer forcing machine causes nylon 6 and the reaction of maleic anhydride tapping point and adds on the E/MAH polymkeric substance and form the branched block ethylene polymers thing as final section.The condition of using in this reactive behavior is extruded is: zone temperatures is 150,200,250,250 and 250 ℃; 250rpm; The 40-65% moment of torsion; With 30 second residence time.The branched block ethylene polymers thing is by ice-water bath, is cut into particle and collects with thermoplastic moulded and use polymer blending.

The final composition of embodiment 8-24 and reference examples A-I is by dried ingredients was separately mixed 5 minutes on the coating vibrator, under condition identical when being used for preparing the branched block ethylene polymers thing but just zone temperatures is 150,200,280,280 and 280 ℃ then, and dried mixed formulation is joined Werner ﹠amp; In the Pfleiderer forcing machine and prepare.Extrudate is a pellet with the wire-form cooling and by chopping once more.Pellet in 120 ℃ air-flow baking oven dry 3 hours is used for preparing sample then on 70 tons of Arburg mould machines, and wherein a tube temperature is 200 ℃ (chargings), and 250 ℃, 250 ℃ and 255 ℃ (nozzle), die temperature is 80 °F, screw speed is 120rpm.Not annealing of sample before test.

The formulation content of embodiment 8-13 and reference examples A-D is given in down in the Table II, by the weight of total composition in part.

In Table I:

" polypropylene " is that the melt index that has of Himont company is about 12 Profax6323 polypropylene, and one type aforesaid polyolefin resin is as blend components (b);

" HDPE " has the about 0.96g/cm of density ³And I ₂Melt index (according to ASTM D 1238) is about 35 high density polyethylene(HDPE), and the aforesaid polyolefin resin of another kind of type is as blend components (b);

" ethene polymers " is to have the about 0.87g/cm of density ³" substantial linear " ethene polymers that does not contain the maleic anhydride tapping point;

" E/MAH multipolymer " is to have the about 0.87g/cm of density ³With contain 1.0wt% " substantial linear " ethene polymers of having an appointment as the maleic anhydride of tapping point;

" nylon 6 " is the Capron-8207 polymeric amide available from Allied Signal, its melt index be about 7 and weight-average molecular weight be about 22,000;

" branched block ethylene polymers thing I " is the E/MAH multipolymer from (i) 70wt%, its I ₂For about 0.5 and the therein ethylene polymkeric substance be " substantial linear " and the (ii) branched block ethylene polymers thing of 30wt% nylon 6 preparation;

" branched block ethylene polymers thing II " is the Tafmer_p-0180 (the linear narrow MWD ethene polymers of Mitsui petrochemical) from (i) 80wt%, and it contains polypropylene and has density is 0.869g/cm ³, I ₂Melt index is 4 and has the maleic anhydride tapping point and a (ii) branched block ethylene polymers thing of 20wt% nylon 6 preparation; With

" % ethene polymers " is polyvinyl weight percentage in blended composition, no matter whether ethene polymers contains tapping point, is E/MAH multipolymer form, or to be formed the branched block ethylene polymers thing.

Table II

The component concentration of embodiment 8-13 and reference examples A-D

	Reference examples				Embodiment
												????A	????B	????C	????D	????8	????9	????10	????11	????12	????13
Polypropylene	???2,000	????1,500	????1,500	????1,500	????1,600	???1,500	??1,400	????1,500	????1,500
											???????HDPE										????1,600
Ethene polymers		????500		????350				????200
											The E/MAH multipolymer			????500
Nylon 6				????150
											Branched block ethylene polymers thing I					????400	????500	????600	????300		????400
Branched block ethylene polymers thing II									????500
											The % ethene polymers	????0	????25	????24.8	????17.5	????14.0	????17.5	????21.0	????20.4	????17.3	????19.0

Sample to the composition of embodiment 8-13 and reference examples A-D carries out the test of following physicals and mechanical property, the results are shown in the Table II of these tests.

The rheology index comprises that wherein sample is placed between two plates that back and forth rotate on the sample plane from the viscosity of the sample of rheology spectrometer mensuration.Sample is heated above the specified temp of its softening temperature, measures viscosity by forcing plate to rotate desired power under different frequency.Shown in the Table II be as when plate rotates under 0.1 radian per second in the viscosity of 190 ℃ of following samples value divided by the no unit that ratio obtained of the viscosity under 100 radian per seconds.

Down measure shock resistance (" Ai Zuode ") by the Ai Zuode test at 25 ℃ according to ASTM rule D 256-84 (method A).The radius of breach is 10 mils (0.254mm).Ai Zuode result is with the ft-lb/in record.

Also according to ASTM regulation D 256-84 (method A) under 25 ℃ by Ai Zuode test determination shock strength (" welded bonds "), but at the sample that in the twoport mould, forms with jam welding.Sample is unnotched, places it in and makes the upper surface high 1mm of weld than bench vice anchor clamps on the bench vice.Welded bonds result is also with the ft-lb/in record, but exception among the embodiment 5, the wherein not fracture of " N.B. " expression sample.

Drop to 1/8 by the 100 pound weight things that under 23 ℃, will carry 1/2 ｀ ｀ dart and " carry out drop-dart impact test (" dart ") on the thick circular specimen.With the free-falling of 8050in/min speed and impact sample, sample is fixed on the aluminium casting pedestal in the position on the descent path dart of having weighed along the fluting track.The value that is recorded in the Table II is that dart makes the sample burst energy needed, represents with in-lb.

According under 66psi, measuring deflection under load temperature (" D.T.U.L ") under the ASTM regulation D 648-82.The result is with record.

Measure modulus in flexure (" F. modulus ") according to ASTM D 790.The result is with the kpsi record.

Table III

The performance of embodiment 8-13 and reference examples A-D

	Reference examples				Embodiment
												????A	????B	????C	????D	??????8	??????9	??????10	????11	?????12	?????13
The rheology index	????4.9	????4.7	????5.9		?????10.4	?????18.2	????25.4		?????16.5
											Ai Zuode, ft-lb/in	????0.4	????2.0	????2.8	????1.6	?????2.4	?????12.1	????15.2	????3.2	?????5.7	????10.6
Welded bonds, ft-lb/in	????7.6	????8.0	????4.5	????2.5	?????17.3	?????16.8	????22.4	????11.8	?????4	????N.B.
											Dart, In-lb	????65	????304	????282	????230	?????344	?????341	????314	????312	?????279	????237
????D.T.U.L.，°F	????170	????140	????138	????149	?????142	?????140	????134
											F. modulus, kpsi	????159	????112	????120	????155	?????114	?????113	????104

Data declaration in the Table III, when mixing with polymkeric substance such as polyolefin resin with molding, the branched block ethylene polymers thing can be produced the composition of the required balance with various performances effectively.Higher rheology index value is outstanding especially, because the higher shearing sensibility of higher value representation.This ratio shown that than macromole material has kept its melt strength and less denominator to show material experience shear shinning and easier processing under low the shearing, both typically are the ideal quality.Obtained the balance for shown each performance of embodiment, although also have following situation: each contains the ethene polymers that lacks than among reference examples A or the B in the middle of them.Data can be reached a conclusion from Table III, the very effective measure that ethene polymers utilizes in blend composition be it is used for preparing branched block ethylene polymers thing (as described here) and use then the branched block ethylene polymers thing with molding with polymkeric substance as properties-correcting agent.Compare with reference examples A-D, embodiment has higher surface durability and anti-scratch property.

The composition for preparing embodiment 14-18 and reference examples E according to the mode identical with the composition of embodiment 8-13 and reference examples A-D.In Table IV, provide the formulation content of embodiment 14-18 and reference examples E below, pressed the parts by weight of total composition.In Table IV, " polypropylene ", identical in " E/MAH multipolymer " and " branched block ethylene polymers thing I " and the Table II.Be used to the composition of embodiment 14-17 from branched block ethylene polymers thing, yet these are indicated on following in Table IV than the polyamide preparation of branched block ethylene polymers thing I less amount:

" branched block ethylene polymers thing III " is from 90wt% " substantial linear " ethene polymers, its I ₂Melt index is about 0.5 and contains the maleic anhydride tapping point; Branched block ethylene polymers thing with 6 preparations of 10wt% nylon;

" branched block ethylene polymers thing IV " is from 85wt% " substantial linear " ethene polymers, its I ₂Melt index is about 0.5 and contains the maleic anhydride tapping point; Branched block ethylene polymers thing with 6 preparations of 15wt% nylon;

" branched block ethylene polymers thing V " is from 80wt% " substantial linear " ethene polymers, its I ₂Melt index is about 0.5 and contains the maleic anhydride tapping point; Branched block ethylene polymers thing with 6 preparations of 20wt% nylon; With

" branched block ethylene polymers thing VI " is from 75wt% " substantial linear " ethene polymers, its I ₂Melt index is about 0.5 and contains the maleic anhydride tapping point; Branched block ethylene polymers thing with 6 preparations of 25wt% nylon.

Also the weight percentage of nylon is listed in the Table III for each branched block ethylene polymers thing with for each composition in its entirety.

Identical with the test that embodiment 7-13 and reference examples A-D are carried out, embodiment 14-18 and reference examples E are carried out same physical and mechanical property test, just the melt strength of each branched block ethylene polymers thing is measured by using pulley/Barrate type melt tension test instrument, as mentioned above, and with centiNewton (li newton) is that unit is measured.The results are shown in the Table V of test.

Table IV

The component concentration of embodiment 14-18 and reference examples E

	Reference examples	Embodiment
								????E	????14	?????15	?????16	?????17	?????18
Polypropylene	????1,500	????1,500	????1,500	????1,500	????1,500	????1,500
							The E/MAH multipolymer	????500
Branched block ethylene polymers thing I						????500
							Branched block ethylene polymers thing III		????500
Branched block ethylene polymers thing IV			????500
							Branched block ethylene polymers thing V				????500
Branched block ethylene polymers thing VI					????500
							The % of nylon in the branched block ethylene polymers thing	????0	????10	????15	????20	????25	????30
% nylon, composition	????0	????2.5	????3.75	????5.0	????6.25	????7.5

Table IV

The performance of embodiment 14-18 and reference examples E

	Reference examples	Embodiment
								????E	?????14	?????15	????16	?????17	?????18
Ai Zuode, ft-lb/in	????2.8	?????2.5	????3.2	????8.3	?????9.7	?????12.1
							Welded bonds, ft-lb/in	????4.5	?????5.4	????6.8	????9.4	?????9.9	?????16.8
Dart, in-lb	????282	?????310	????310	????306	?????305	?????341
							The rheology index	????5.9	?????11.5	????11.4	????12.7	?????14.1	?????18.2
D.T.U.L.，°F	????138	?????144	????138	????141	?????144	?????140
							F. modulus, kpsi	????120	?????105	????127	????122	?????124	?????113
Branched block ethylene polymers thing melt strength, cN	????13.8	?????22.9	????25.9	????32.2	?????45.4	?????52.2

The result of embodiment 14-18 and reference examples E is the another evidence of desired properties equilibrated that uses the branched block ethylene polymers thing to obtain by in blended composition.Can find out that polymeric amide is used for forming in the scope of final block of branched block ethylene polymers thing in the present invention therein, the consumption that improves polymeric amide will improve Chinese mugwort and help the moral character energy.

The composition of embodiment 19 and reference examples F is to prepare according to the mode identical with the composition of embodiment 8-18 and reference examples A-E.The composition of embodiment 20 and reference examples G (though contain some materials, can make the branched block ethylene polymers thing from these materials, not make) prepared by component is mixed under 220 ℃ in the Banbury mixing machine simultaneously in 12 minutes.In Table V, provided the formulation content of embodiment 19-20 and reference examples F-G, with the parts by weight of total composition.In Table V, identical in " polypropylene ", " E/MAH multipolymer " and " branched block ethylene polymers thing VI " and the Table III.Identical in " nylon 6 " and the Table II.Also the weight percentage of nylon is listed in the Table VI for each composition in its entirety.

Identical with the test that embodiment 8-18 and reference examples A-E are carried out, embodiment 19-20 and reference examples F-G are carried out some same physical and mechanical properties tests, the result of test also is shown in the Table VI.

Table VI,

The component concentration of embodiment 19-20 and reference examples F-G and performance

	Embodiment F	Embodiment 19	Reference examples G	Embodiment 20
					Polypropylene	?????1,500	????1,500	???????1,500	?????1,500
The E/MAH multipolymer	?????350		???????350
					Nylon 6	?????150		???????150
Branched block ethylene polymers thing VI		????500		?????500
					% nylon, composition	?????7.5	????7.5	???????7.5	?????7.5
Ai Zuode, ft-lb/in	?????1.6	????12.1	???????2.0	?????12.7
					Welded bonds, ft-lb/in	?????10.9	????16.8	???????5.7	?????13.3
Dart, in-lb	?????320	????341	???????288	?????314
					D.T.U.L.，°F	?????143	????140	???????139	?????143
F. modulus, kpsi	?????112	????113	???????115	?????117
					Blending means	Extrude	Extrude	Banbury (Banbury)	Banbury (Banbury)

The presentation of results of embodiment 19-20 and reference examples F-G carry out blended importance with molding under certain condition during with polymkeric substance (as polyolefin resin) blend when branched block ethylene polymers thing and amine-functionalized polymers (as polymeric amide), should make it possible under these conditions from branched ethylene polymer and amine-functionalized polymers formation branched block ethylene polymers thing.This type of condition comprises at first in independent equipment preparation branched block ethylene polymers thing and then with it and molding polymer blending, or in same equipment such as forcing machine, mix all three kinds of materials, but carry out so that the reaction of amine-functionalized polymers and branched ethylene polymer forms the branched block ethylene polymers thing according to a definite sequence, because molding can hinder this reaction with the existence of polymkeric substance.

For example, the composition of reference examples F and polypropylene component blend can prepare the branched block ethylene polymers thing from it.Yet, the preparation of reference examples F not can with polyacrylic blend in produce the branched block ethylene polymers thing because three kinds of components of all of reference examples F are mixed and blended in forcing machine simultaneously then by dried.When same component is used at first prepare the branched block ethylene polymers thing in embodiment 19 (from E/MAH branched ethylene polymer and polymeric amide), resulting have polyacrylic blend will obtain a kind of composition that demonstrates significantly high Ai Zuode, welded bonds and dart-drop value.Even when with reference examples G in when mixing E/MAH branched ethylene polymer, polymeric amide and polyolefine simultaneously under the same high temperature, shear conditions at the Banbury mixing machine, the performance of blended composition can be than reference examples F better, and reach those that are inferior to embodiment 20 (wherein the preparation of branched block ethylene polymers thing is being carried out finishing before the melt blending with polymkeric substance with molding).

Have been found that in general the branched block ethylene polymers thing demonstrates improved rheological property, with each component (preparing the former) from described component Comparatively speaking.For example, the branched block ethylene polymers thing, when testing by the dynamic mechanical spectrometer, under low shearing speed, demonstrate than ethene polymers or the much higher viscosity of branched ethylene polymer, also demonstrate much higher shearing sensibility in addition than its arbitrary precursor because under high speed shear its viscosity degradation to by the about identical level of the shown viscosity that goes out of ethene polymers or branched ethylene polymer.Therefore the tan δ value of branched block ethylene polymers thing also is superior to the value of ethene polymers or branched ethylene polymer, is to shear and the indication of high melt elasticity (high storage modulus) under high-shear low.

And, have now found that the branched block ethylene polymers thing has corresponding influence to containing molding with the blend of polymkeric substance.This type of blended composition ratio under low shearing only goes out higher melt strength and elasticity with the composition exhibiting of ethene polymers or branched ethylene polymer modification, and this blend has enough shearing sensibilities, and it is thinning to identical with branched ethylene polymer basically viscosity under high-shear.For example, Figure 20 show for ethene/tapping point multipolymer and with as amine-functionalized multipolymer from the branched block ethylene polymers thing blend of the polyamide preparation of various consumption levels the viscosity of polypropylene under various velocity of shear.The blend that contains the branched block ethylene polymers thing under low the shearing, have higher viscosity but under high-shear thinning to the identical degree of blend that only contains ethene/tapping point multipolymer.Figure 21 provides tan δ for same group blend, and it is that out-of-phase modulus is divided by storage modulus.Wherein polypropylene and the blend of branched block ethylene polymers thing rather than only have lower tan δ and therefore have higher storage modulus with the copolymer blended composition of ethene/tapping point.Higher storage modulus has been represented a large amount of elasticity recovered.The mensuration of tan δ value is carried out with currently known methods, as from Melt Rheology and Its Role in Plastic Processing (melt rheology and its effect plastic working), Dealy and Wissbrun, Van Nostrand, those methods that nineteen ninety obtains.

These improvement on performance it is believed that the trend that is dispersed in the blended composition with the branched block ethylene polymers thing is relevant, and the dispersive mode should make amine-functionalized polymers be broken up into the submicron particles form in the particle of branched ethylene polymer and have bigger particle size uniformity.On the contrary, when amine-functionalized polymers was blended in random, the physical blending thing with branched ethylene polymer simply rather than at first is formed the branched block ethylene polymers thing as a component, the amine-functionalized polymers that is dispersed in the ethene polymers had the less homogeneity of particle size or does not have homogeneity at all; Amine-functionalized polymers also can be used as big, many micron particles and is dispersed in molding with in the polymeric matrix resin in this case, but to ethene polymers without any association.

Therefore, in preferred embodiments, amine-functionalized polymers in the branched block ethylene polymers thing is scattered in the branched ethylene polymer with particle form, wherein about 50% or more, usually about 65% or more, about frequently 80% or more and accidental about 90% or granularity that more particles had be in about 120% scope of about 80%-of the mean sizes of whole amine-functionalized polymers particle cluster in being scattered in the particle of branched ethylene polymer.

When the particle cluster of the very uniform small grain size of the conduct of the amine-functionalized polymers in the branched block ethylene polymers thing is scattered in the branched ethylene polymer, the particle of branched ethylene polymer itself is less and more is evenly distributed in molding with in the polymeric matrix, makes composition have excellent elastic impact intensity.On the contrary, when the amine-functionalized polymers particle only is component that is not having in random, the physical blending thing of branched block ethylene polymers thing terpolymer, then the branched ethylene polymer particle is bigger and/or the branched ethylene polymer particle swarm trends towards assembling and producing a kind of territory, in the territory as be both big particle and can bring into play effective function.So, in another embodiment, branched ethylene polymer particulate granularity and the ratio that is dispersed in amine-functionalized polymers particulate mean particle size wherein, when when they have prepared the branched block ethylene polymers thing, being significantly less than branched ethylene polymer particulate granularity and being dispersed in the ratio of amine-functionalized polymers particulate mean particle size wherein, only is in random, the physical blending thing during component when not forming branched block ethylene polymers thing and amine-functionalized polymers.

Correspondingly, if use excessive amine-functionalized polymers, then can lose the beneficial effect that forms the branched block ethylene polymers thing in the blend composition.Will be offset by the unhindered amina functionalized polymeric by the value that amine-functionalized polymers increased that forms the final block on the branched block ethylene polymers thing, the latter understands crosslinked or forms crystal domain, and this territory is brittle and makes blend composition improve notch sensitivity.

The composition of embodiment 21-24 and reference examples H and I is by using the mixing condition preparation identical with reference examples A-E with embodiment 8-18.Yet reference examples H and I are the representatives of following situation: wherein the branched block ethylene polymers thing can form but not form, because all components is mixed together rather than mix formation branched block ethylene polymers thing in order.Provided the formulation content of embodiment 21-24 and reference examples H and I below in the Table VII, with the parts by weight of total composition.In Table VII:

" polycarbonate " is that melt index is 10 bisphenol-a polycarbonate;

" branched block ethylene polymers thing VII " is the I from 70wt% ₂Melt index is the branched block ethylene polymers thing of nylon 6 preparations of 0.37 E/MAH multipolymer and 30wt%;

" Epoxy (epoxy) " is bisphenol-A/epichlorohydrin epoxy, as the D.E.R._332 Resins, epoxy available from Dow chemical company;

E.S.O. be the epoxidised soybean oil thickening material; With

IR 1076 is Irganox_1076 stablizers.

Equally in Table VI, identical in " nylon 6 ", " branched block ethylene polymers thing I " and " E/MAH multipolymer " and the Table II.Do as a wholely also the parts by weight of E/MAH multipolymer to be listed in the Table VII for reference examples H and I and embodiment 16-17.

The mode identical with the test that embodiment 1-11 and reference examples A-E are carried out carries out embodiment 14-17 and reference examples H and I are carried out some same physical and mechanical properties tests.Other test of being carried out is as follows: fracture tensile strength and extension at break are all measured according to ASTM regulation D 638-84.

According to ASTM rule D 523-85, use the Dr.Lange Reflectometrer RB3 that buys from Hunter Assocaiates that specimen is carried out elder generation's pool measurement.

The results are shown in the Table VII of these tests.N.B. be illustrated in the welded bonds test and do not have rupture failure.

Table VII, the component concentration of embodiment 21-24 and reference examples H-I

	Embodiment 21	Embodiment 22	Reference examples H	Embodiment 23	Reference examples I	Embodiment 24
							Polycarbonate	1850	1850
Nylon 6			1700	1570	1600	1428
							Branched block ethylene polymers thing I				430		572
Branched block ethylene polymers thing VII	150	150
							The E/MAH multipolymer			300		400
Resins, epoxy		4
							E.S.O.	2	2
IR 1076 (stablizer)	4	4
							The % of E/MAH multipolymer in composition			15	15	20	20

Table VIII, the performance of embodiment 21-24 and reference examples H-I

	Embodiment 21	Embodiment 22	Reference examples H	Embodiment 23	Reference examples I	Embodiment 24
							Ai Zuode, ft-lb/in, 23 ℃	13.7	13.7	6.7	8.2	5.6	7.5
Ai Zuode, ft-lb/in, 0 ℃	12.8	13.1	6.6	9.0	6.9	8.9
							Ai Zuode, ft-lb/in, 20 ℃	11.7	10.6	2.4	2.8	3.6	9.0
Ai Zuode, ft-lb/in, 30 ℃						9.6
							Welded bonds, ft-lb/in	3.0	7.0	N.B.	N.B.	N.B.	N.B.
20 ° of gloss	18	19
							60 ° of gloss	69	70
Tensile strength	8030	8791	5828	5602	7001	6619
							Elongation %	84	111	41	60	181	189
D.T.U.L.，°F	291	288	289	335	299	307
							F. modulus, kpsi	290	299	205	198		228

The result of reference examples H and I and embodiment 23 and 24 shows, when not forming the branched block ethylene polymers thing when itself being used as impact modifying agent, ethene/MAH multipolymer impact property can be strengthened to the branched block ethylene polymers thing the same degree that can reach.Ethene/MAH multipolymer has than lower viscosity of branched block ethylene polymers thing and lower elasticity.Therefore, when amine-functionalized polymers only is used as another kind of blend components rather than is used to prepare the branched block ethylene polymers thing, resultant composition can not embody feature in shock strength, and especially at low temperatures, and this performance is the same with the composition with block desirable.

Having used wherein, the reactive behavior thermoplastic polymer of subfraction (c) is the embodiment of the branched block ethylene polymers thing of polyester.

The composition of embodiment 25 is the blend of polycarbonate and branched block ethylene polymers thing.The composition of reference examples A1 is the blend of three kinds of components and polycarbonate, can prepare the branched block ethylene polymers thing from three kinds of components.Yet the preparation of reference examples A can not obtain the blend of branched block ethylene polymers thing and polycarbonate, because all four kinds of materials are blend simultaneously.The composition of reference examples B1 is polycarbonate and the blend that only contains the ethene polymers (" E/MAH multipolymer ") of maleic anhydride tapping point.The composition of reference examples C1 and D1 each naturally polycarbonate with do not contain the polyvinyl blend of substantial linear of tapping point.Reference examples E1, each blend of polycarbonate and another kind of olefin polymer naturally of the composition of F1 and G1.

The branched block ethylene polymers thing that is comprised in the composition of embodiment 25 is by at 30mm Werner ﹠amp; In the Pfleiderer forcing machine with the mixture melting mixing of " substantial linear " ethene polymers that contains the maleic anhydride tapping point (" E/MAH multipolymer ") of 30wt% polybutylene terephthalate and 70wt% and prepare.By using peroxide initiator, on " substantial linear " ethene polymers, formed the maleic anhydride tapping point with amount based on the 1wt% of E/MAH multipolymer weight.Employed condition is in the preparation of branched block ethylene polymers thing: zone temperatures is 150,200,250,250 and 250 ℃, 250rpm; The 70-85% moment of torsion; With 30 second residence time.

The final composition of embodiment 25 and reference examples A1-G1 is prepared as follows: in the coating vibrator those dried ingredients were separately mixed 5 minutes, will do mixed formulation feeding Werner ﹠amp then; The Pfleiderer forcing machine, it is identical with the condition that is used to prepare the branched block ethylene polymers thing to extrude operation, be zone temperatures be 150,200,280,280 and 280 ℃.Extrudate is cooled to wire-form, is broken into pellet then.Pellet in 120 ℃ air-flow baking oven dry 3 hours is used for preparing sample then on 70 tons of Arburg mould machines, and a tube temperature is 280 ℃ in mould machine, and die temperature is that 82 ℃ and screw speed are 120rpm.

In Table I, provide the formulation content of embodiment 25 and reference examples A1～G1, press the parts by weight of total composition.In Table I:

" polycarbonate " is the bisphenol-a polycarbonate of weight-average molecular weight about 28,000;

" branched block ethylene polymers thing " is from polybutylene terephthalate and contain the branched block ethylene polymers thing that maleic anhydride tapping point " substantial linear " ethene polymers prepares, as mentioned above;

" E/MAH multipolymer " is to contain maleic anhydride tapping point and the I with 0.5 ₂The substantial linear ethene polymers of melt index;

" PBI " is polybutylene terephthalate;

" POE " do not contain maleic anhydride tapping point and the I with 0.5 ₂" substantial linear " ethene polymers of melt index;

" ECO " is ethene/carbon monoxide multipolymer;

" HDPE " has the about 0.96g/cm of density ³With I with about 10 ₂The high density polyethylene(HDPE) of melt index (according to ASTM D 1238);

" LLDPE " has about 4 I ₂The linear low density polyethylene of melt index (according to ASTM D 1238);

Below test embodiment 25 and reference examples A1-G1 are carried out the results are shown in the Table I of these tests.

Under 25 ℃, measure shock resistance according to ASTM regulation D 256-84 (method A) by Ai Zuode test (" Izod ").Breach has 10 mils (0.254mm) radius.Impact direction is parallel and vertical with the line of flow of another sample with line of flow in the plate (downcutting batten by sample of each composition on the slave plate).The Ai Zuode test result that impact direction is parallel to line of flow and impact direction are used as no unit value perpendicular to the result's of line of flow ratio and list with label " Anisotropy ".The Ai Zuode test result is used to estimate the ductility/brittle transition temperature (" DBTT ") of each sample then.Also under 25 ℃, measure shock resistance by Ai Zuode test (" welded bonds ") according to ASTM regulation D 256-84 (method A), but at the sample that in the twoport mould, forms with jam welding.Sample is unnotched, places it in and makes the upper surface high 1mm of weld than bench vice anchor clamps on the bench vice.Welded bonds result is with the kg-cm/cm record.

Table I X, component concentration and the performance of reference examples A1-G1 and embodiment 25

	Reference examples							Embodiment	25
										A1	B1	C1	D1	E1	F1	G1
	Polycarbonate	93	95	93	95	95	95										95	93
The branched block ethylene polymers thing															7
	The E/MAH multipolymer	4.9	5
PBT								2.1		2.1
	POE			4.9	5
ECO												5
	HDPE						5
LLDPE														5
Anisotropy (Anisotropy)								.678	.748	.853	.879	.838	.575	.672	.783
	DBTT，℃	-35	-45	-20	-20	-20	-40									-30	-35
Welded bonds, kg-cm/cm								32	26	17	5	7	29	12	83

Data show among the Table I X, and when using polymer blending with molding, the branched block ethylene polymers thing can be produced the composition of the required balance with various performances effectively.It contains some components reference examples A1-, can prepare the branched block ethylene polymers thing the PC blend from these components but does not prepare-have the welded bonds value lower than embodiment 25.Other reference examples that contains the olefin polymer of some other forms separately has the performance of good individual types, but they do not resemble and on all performances of three types the ideal balance are arranged the embodiment 25.For example, reference examples C1-E1 all has very high anisotropy, but has extremely low weld line strength.Data can be reached a conclusion from Table VIII, in blend composition, utilize the very effective measure of olefin polymer to be to use it to prepare branched block ethylene polymers thing (as described herein), use conduct of branched block ethylene polymers thing and the blending and modifying agent of molding then with polymkeric substance.

Improvement on these performances it is believed that the trend that is dispersed in the blend composition with the branched block ethylene polymers thing is relevant, and its dispersing mode should make polyester as there being the submicron particles of high particle size uniformity to be dispersed in the particle of ethene/branch point multipolymer.On the contrary, when polyester is blended in random, the physical blending thing with ethene/branch point multipolymer simply rather than at first forms the branched block ethylene polymers thing as a component, be dispersed in polyester in the ethene polymers and will have very little particle size uniformity or do not have at all; In this case polyester as big, a plurality of micron-sized particles dispersed molding with the polymeric matrix resin in but can any association not arranged with ethene polymers.

Therefore, in preferred embodiments, polyester in the branched block ethylene polymers thing is used as particles dispersed in ethene/tapping point multipolymer, wherein about 50% or higher, usually about 65% or higher, about infrequently 80% or more and accidental about 90% or granularity that more particles had be in about 120% scope of about 80%-of the mean sizes of whole polyester granulate cluster in the particle that is scattered in ethene/tapping point multipolymer.

When the particle cluster of the very uniform small grain size of the conduct of the polyester in the branched block ethylene polymers thing is scattered in ethene/tapping point multipolymer, the particle of ethene/tapping point multipolymer itself is less and more is evenly distributed in molding with in the polymeric matrix, makes composition have excellent elastic impact intensity.On the contrary, when polyester granulate only is component in do not having that terpolymer forms random, the physical blending thing, then ethene/tapping point copolymer pellet is bigger and/or ethene/tapping point copolymer pellet group trends towards assembling and producing a kind of territory, and this territory is as being that very large particle is brought into play more effective effect.So, in another embodiment, the granularity of ethene/tapping point copolymer pellet and the ratio that is dispersed in the mean particle size of polyester granulate wherein, when when they have prepared the branched block ethylene polymers thing, granularity that is significantly less than ethene/tapping point copolymer pellet and the ratio that is dispersed in the mean particle size of polyester granulate wherein, the latter is only to be in random, the physical blending thing during component when not forming segmented copolymer and polyester.

According to embodiment 25 in similarly mode prepare the composition of embodiment 26-29.The branched block ethylene polymers thing that uses in the composition of embodiment 26-29 is to react in the presence of p-methylphenyl sulfimide potassium (" KPTSM ") catalyzer by the polyethylene terephthalate with limiting viscosity 0.59 and " substantial linear " ethene polymers of containing the maleic anhydride tapping point to prepare.Though the branched block ethylene polymers thing by means of Preparation of Catalyst is preferred,, also be useful product as the polymkeric substance that in embodiment 26, uses without the polymkeric substance of Preparation of Catalyst.The branched block ethylene polymers thing that uses in each embodiment contains maleic anhydride tapping point " substantial linear " ethene polymers and 70wt% polyethylene terephthalate preparation from 30wt%.Each blend composition is from the preparation of the branched block ethylene polymers thing of 93wt% polycarbonate and 7wt%.The KPTSM catalyst consumption of using in embodiment 27-29, parts per million part (ppm) expression with respect to the combined wt of E/MAH multipolymer and polyethylene terephthalate (from they preparation branched block ethylene polymers things) is shown in the following table.

For " welded bonds " sample that in the twoport mould, forms, under 25 ℃, measure the shock resistance of embodiment 26-29 according to ASTM regulation D 256-84 (method A) by Ai Zuode test (" Izod ") with jam welding.Sample is unnotched, and is placed in and makes the upper surface high 1mm of weld than bench vice anchor clamps on the bench vice.The Ai Zuode test result of embodiment 26-29 all is to make record for 11 times of the composition of each sample tests, and each time result is classified as " not fracture ", " part fracture " or " brittle rupture " in 11 tests.The brittle rupture of the sample in following table is meant the fracture that impels sample separation to become two individual sheets, and sample separates and major portion maintenance linking significantly in the part fracture.The Ai Zuode test value that each embodiment write down is the mean value of those test values of 11 tests of the part or the various samples of brittle rupture.Ai Zuode result represents that with ft-lb/in this is the standard deviation of the Ai Zuode value of each group part or brittle rupture.

	Embodiment
						?26	?27	?28	?29
The amount of KPTSM, ppm	?0	?500	?1,000	?2,000
In 11 tests not fracture sample	3	7	?7	?7
					In 11 tests part fracture sample	5	2	?4	?4
11 times the test in brittle rupture sample	3	2	?0	?0
					Non-notch Ai Zuode, ft-lb/in	20	20	?34	?43
Standard deviation-Ai Zuode, ft-lb/in	13	15	?2	?1

The presentation of results of embodiment 26-29 in preparation process as the branched block ethylene polymers thing of blending and modifying agent in the composition of embodiment 27-29, KPTSM produces a kind of branched block ethylene polymers thing as the existence of catalyzer is feasible, and this polymkeric substance is than there not being the prepared branched block ethylene polymers thing of catalyzer to improve the shock strength of composition better.Although the composition exhibiting of embodiment 26 goes out considerable Ai Zuode value, in the preparation process of the branched block ethylene polymers thing that is used for blend, use the composition of the embodiment 27-29 of relatively large KPTSM catalyzer also to show improved Ai Zuode value and very little brittle rupture.

Embodiment 30: wherein the reactive behavior thermoplastic polymer is the use of the branched block ethylene polymers thing of polycaprolactone

Weight-average molecular weight is 18, and the bisphenol-a polycarbonate of 000g/mol is as base resin.Employed polyene hydrocarbon phase is that to have density be 0.88g/cc and I ₂Substantial linear ethene/1-octene polymer for 30g/10min.Obtain from UniroyalChemical with Royaltuff 372P20 (SAN-g-EPDM) trade(brand)name with styrene/acrylonitrile grafted ethylene/propene/non-conjugated diene olefin elastomer.Polycaprolactone (PCL) obtains from Union Carbide Corp with Tone P-767 trade(brand)name.

The MAH-g-EO of 70/30 weight ratio and PCL do in cylinder and mix.Use 30mm Werner﹠amp; The Pfleiderer co-rotating twin screw extruder is with mixture pelleting.Extrusion condition is that screw speed is set in 24rpm and a tube temperature is set in 190,260, and 160,260 ℃ and die temperature are set in 260 ℃.Be resin combination below:

Resin combination

	Polycarbonate (80MFR)	The homogeneous ethene polymers (0.88g/cc, 30g/10min.)	PCL-g-EO	SAN-g-EPDM
					Reference examples 1	100
Reference examples 2	90	10
					Embodiment 1	90		10
Reference examples 3	90			10
					Embodiment 2	90	9	1
Embodiment 3	90	9		1

Molecular weight analyse: with the exciusion chromatography technology of UV detector lotus root connection, methylene dichloride as solvent and tetrahydrofuran (THF) as solvent carrier.Proofread and correct with LEXAN polycarbonate standards thing.

Viscosity (Nu): use capillary rheometer and the round mouth die head that is of a size of 1.27mm internal diameter and 25.4mm length to measure shear viscosity.Employed temperature is 270 ℃.Record volume value is at 80 and 2900 seconds ^-1Under viscosity.

Izod impact strength: to the sample determination Ai Zuode impact value of the pre-gap of 0.25mm (10 mil).Use the 10ft-lb pendulum to test.

Ductile brittle transition temperature (DBTT): the temperature that sample is positioned when experiencing the Ai Zuode impact fracture from ductility to fragility.

Performance measurement

	The PC of molding (Mw) g/mol	At 80 seconds -1Under viscosity (Nu)	At 2900 seconds -1Under Nu	??DBTT	Room temperature Ai Zuode value
						Reference examples 1	????18500	????191	?????108	Be higher than 30	????2.2
Reference examples 2	????18500	????152	?????70	????-5	??????0
						Embodiment 1	????18700	????174	?????84	???-20	????8.8
Reference examples 3	????19200		?????100	???-20	????8.3
						Embodiment 2	????18800	????180	?????75	???-10	????9.1
Embodiment 3	????18600	????163	?????72		????8.8

Claims (34)

1, branched block ethylene polymers thing, it comprises:

(a) ethene polymers;

(b) the unsaturated functionalized organic compound of olefinic; With

(c) can with the reactive behavior thermoplastic polymer of the unsaturated functionalized organic compound reaction of olefinic.

2, the branched block ethylene polymers thing of claim 1, wherein the unsaturated functionalized organic compound of olefinic contains carbonyl.

3, the branched block ethylene polymers thing of claim 1, wherein the unsaturated functionalized organic compound of olefinic is a maleic anhydride.

4, the branched block ethylene polymers thing of claim 1, wherein the unsaturated functionalized organic compound of olefinic carries the epoxy basic ring.

5, the branched block ethylene polymers thing of claim 1, wherein unsaturated functionalized organic compound Shi oxazoline, amine or alcohol of olefinic.

6, the branched block ethylene polymers thing of claim 1, the therein ethylene polymkeric substance is the homogeneous polymers with following performance:

(i) be lower than about 3.0 Mw/Mn ratio by what gel permeation chromatography recorded;

(ii) about 0.93g/cm ³Or lower density;

(iii) be higher than about 30% short-chain branched dispersion index; With

The (iv) single melting peak between-30 ℃ and 150 ℃ that records by dsc.

7, the branched block ethylene polymers thing of claim 1, wherein narrow polymolecularity ethene polymers is the ethene polymers of substantial linear, it embodies to be characterized as and has:

(i) be greater than or equal to 5.63 melt flow rate (MFR) I ₁₀/ I ₂,

(ii) by the (I that is greater than or equal to of Mw/Mn definition ₁₀/ I ₂The molecular weight distribution of)-4.63 and

The (iii) certain critical shear rate when surperficial melt fracture begins, it is than having roughly the same I ₂High at least by 50% with the critical shear rate of the linear tetrafluoroethylene polymer of Mw/Mn, this I ₂In the 90-110% scope of the polyvinyl analog value of each comfortable substantial linear of Mw/Mn; With

The (iv) single melting peak between about 30 ℃ and 150 ℃ that records by dsc;

Wherein the ethene polymers of substantial linear further embodies to be characterized as to have and is higher than 50% SCBD index.

8, the branched block ethylene polymers thing of claim 7, wherein the critical shear rate that had when overall melt fracture begins of the ethene polymers of substantial linear is higher than about 4 * 10 ⁶Dynes per centimeter ²

9, the branched block ethylene polymers thing of claim 7, wherein the ethene polymers of substantial linear has about 3 long chain branches/1000 of average about 0.01-total carbon atom.

10, the branched block ethylene polymers thing of claim 8, wherein the processing index that ethene polymers had of substantial linear is less than or equal to processing index about 70% of linear tetrafluoroethylene polymer, and the I of linear tetrafluoroethylene polymer ₂, polymolecularity and density each naturally at the 90-110% of the polyvinyl analog value of substantial linear.

11, the branched block ethylene polymers thing of claim 1, wherein the reactive behavior thermoplastic polymer is an amine-functionalized polymers.

13, the branched block ethylene polymers thing of claim 1, wherein the reactive behavior thermoplastic polymer is a polyester.

14, the method for preparing the branched block ethylene polymers thing, this polymkeric substance contains:

(a) ethene polymers;

(b) the unsaturated functionalized organic compound of olefinic; With

(c) can with the reactive behavior thermoplastic polymer of the unsaturated functionalized organic compound reaction of olefinic;

This method comprises that (1) allows the unsaturated functionalized organic compound of olefinic form polyvinyl branch and formed branched ethylene polymer and afterwards, and (2) allow reactive behavior thermoplastic polymer and branched ethylene polymer reaction.

15, the method for claim 14, therein ethylene polymkeric substance are the homogeneous ethene polymerss with following performance:

(i) be lower than about 3.0 Mw/Mn ratio by what gel permeation chromatography recorded;

(ii) about 0.93g/cm ³Or lower density;

(iii) be higher than about 30% short-chain branched dispersion index; With

The (iv) single melting peak between-30 ℃ and 150 ℃ that records by dsc.

16, the branched block ethylene polymers thing of claim 15, the therein ethylene polymkeric substance is the ethene polymers of substantial linear, it embodies to be characterized as and has:

(i) be greater than or equal to 5.63 melt flow rate (MFR) I ₁₀/ I ₂,

(ii) by the (I of being less than or equal to of Mw/Mn definition ₁₀/ I ₂The molecular weight distribution of)-4.63 and

The (iii) certain critical shear rate when surperficial melt fracture begins, it is than having roughly the same I ₂Critical shear rate high at least 50% with the linear tetrafluoroethylene polymer of Mw/Mn; With

(iv) be higher than 50% SCBD index.

17, the method for claim 15, wherein reactive behavior thermoplastic polymer and branched ethylene polymer be selected from have PKa be 7 or the catalyzer of higher basic metal or alkaline earth salt and nitrogenous organic base in the presence of reaction.

18, the method for claim 15, wherein catalyzer is an amine.

19, the method for claim 15, wherein catalyzer obtains from the aromatics sulfimide.

20, the method for claim 15, wherein catalyzer is a p-methylphenyl sulfimide potassium.

21, the method for claim 15, wherein (1) polyvinyl ethylenically unsaturated organic compounds ramose forms and (2) reactive behavior thermoplastic polymer and polyvinyl reaction are all undertaken during by a forcing machine disposable.

22, thermoplasticity blend or the molding blend of polymkeric substance and branched block ethylene polymers thing, this branched block ethylene polymers thing further comprises:

(a) ethene polymers;

(b) the unsaturated functionalized organic compound of olefinic; With

(c) can with the reactive behavior thermoplastic polymer of the unsaturated functionalized organic compound reaction of olefinic.

23, the blend of claim 22, therein ethylene polymkeric substance are the homogeneous ethene polymerss with following performance:

(i) be lower than about 3.0 Mw/Mn ratio by what gel permeation chromatography recorded;

(ii) about 0.93g/cm ³Or lower density;

(iii) be higher than about 30% short-chain branched dispersion index; With

The (iv) single melting peak between-30 ℃ and 150 ℃ that records by dsc.

24, the method for claim 22, therein ethylene polymkeric substance are the ethene polymerss of substantial linear, and it embodies to be characterized as and has:

(i) be greater than or equal to 5.63 melt flow and compare I ₁₀/ I ₂,

(ii) by the (I of being less than or equal to of Mw/Mn definition ₁₀/ I ₂The molecular weight distribution of)-4.63 and

The (iii) certain critical shear rate when surperficial melt fracture begins, it is than having roughly the same I ₂Critical shear rate high at least 50% with the linear tetrafluoroethylene polymer of Mw/Mn; With

(iv) be higher than 50% SCBD index.

25, the blend of claim 22, wherein thermoplasticity blend or molding are selected from polycarbonate with polymkeric substance, polyester, polyphenylene oxide, polysulfones, polyetherimide, polypropylene and polyethylene.

26, the blend of claim 22, wherein thermoplasticity blend or molding polymkeric substance are the ethene polymerss of substantial linear.

27, the blend of claim 22 further comprises styrene copolymer, elastomerics impact modifying agent, flow promotor or their mixture.

28, the blend of claim 22 further comprises at least a in oil or the filler.

29, the blend of claim 22, wherein the reactive behavior thermoplastic polymer is a nylon 6.

30, the blend of claim 22 is molding or extrudate form.

31, prepare method for compositions from thermoplastic moulded with polymkeric substance, ethene polymers, the unsaturated functionalized organic compound of olefinic and reactive behavior thermoplastic polymer, comprise;

(1) form the branched block ethylene polymers thing by following process: a) the unsaturated functionalized organic compound of olefinic is added to and form branched ethylene polymer and b then on the ethene polymers) allow the residue of reactive behavior thermoplastic polymer and the unsaturated functionalized organic compound of olefinic react; Then

(2) with the branched block ethylene polymers thing and thermoplastic mouldedly use polymer blending.

32, the method for claim 31, therein ethylene polymkeric substance are the homogeneous ethene polymerss with following performance:

(i) be lower than about 3.0 polymolecularity;

(ii) about 0.93g/cm ³Or lower density;

(iii) be higher than about 30% short-chain branched dispersion index; With

The (iv) single melting peak between-30 ℃ and 150 ℃ that records by dsc.

33, the method for claim 31, wherein the narrow ethene polymers of reactive behavior thermoplastic polymer and branching be selected from have PKa be 7 or the catalyzer of higher basic metal or alkaline earth salt and nitrogenous organic base in the presence of reaction.

34, the method for claim 31, wherein (a) unsaturated sense forms the reaction of polyvinyl branch, (b) reactive behavior thermoplastic polymer and branched ethylene polymer than organic compound and (c) branched block ethylene polymers thing and blend or molding are all undertaken during by a forcing machine disposable with the blend of thermoplastic resin.

35, the method for claim 31, wherein branched ethylene polymer and reactive behavior thermoplastic polymer are added in the forcing machine together and allow blend or molding add through the fed downstream mouth with resin in the process of material by described forcing machine.

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