CN101616983B

CN101616983B - Articles comprising nonpolar polyolefin and polyurethane, and methods for their preparation and use

Info

Publication number: CN101616983B
Application number: CN200780049062.XA
Authority: CN
Inventors: 劳拉·B·韦弗; 阿希什·巴特拉; 帕特里夏·安塞姆斯; 加里·M·斯特兰德伯格; 马修·J·卡利诺斯基
Original assignee: Dow Global Technologies LLC
Current assignee: Dow Global Technologies LLC
Priority date: 2006-11-01
Filing date: 2007-10-31
Publication date: 2015-01-21
Anticipated expiration: 2027-10-31
Also published as: CN101611086B; CN101573406A; CN101611086A; CN101616983A

Abstract

The adhesion between a low surface energy (i.e., nonpolar) material, e.g., a polyolefm such as polyethylene, and a high surface energy (i.e., polar) material, e.g., a polyester, polyurethane, polycarbonate or polylactic acid, is promoted by blending with the nonpolar material typically from 15 to less than 50 wt% of a diol-based thermoplastic polyurethane (d-TPU), e.g., a polydiene diol-based TPU, based on the combined weight of the nonpolar material and the d-TPU. The promoted adhesion allows for the effective painting, printing, over-molding or HF-welding of a nonpolar substrate, e.g., a polyolefin film, with a polar coating, e.g., a paint, ink, etc. Aqueous dispersions can also be made from the blend of nonpolar material and d-TPU.

Description

Comprise the goods of nonpolar polyolefin and urethane, their preparation method and purposes

the cross reference of related application

This application claims the U.S. Provisional Patent Application 60/863 submitted on November 1st, 2006,887, the U.S. Provisional Patent Application 60/894 submitted on March 12nd, 2007,353, the U.S. Provisional Patent Application 60/952 submitted on July 27th, 2007, the U.S. Provisional Patent Application 60/952 that on July 27th, 254 and 2007 submits to, the rights and interests of 266, each temporary patent application is all incorporated to herein as a reference.

Invention field

The present invention relates to the composition comprising non-polar polyolefinic and the urethane based on glycol.In one aspect, the present invention relates to the blend of ethylene/alpha-olefin copolymer and the urethane based on glycol, and on the other hand, the present invention relates to the purposes of these blends in brushing, overmolding, radiowelding (highfrequency welding) and water dispersion application.Another aspect, the present invention relates to these compositions and the purposes of blend in other application, and on the other hand, the present invention relates to the goods obtained by these compositions and blend.

Background of invention

Polyolefine (PO) has the character of many expectations, such as, lightweight, resisting power, low cost etc., them are made to become the attracting building material of many consumer's goods, these consumer's goods are such as outside and interior automotive parts, household electrical appliance decorative cover (fascia), etc.But due to their non-polar character, PO is not easy to receive paint, priming paint or decorating printing.Most of paint, priming paint or ink are polarity in essence, therefore require the surface with certain polarity degree, then they can be attached to this surface with any desirable stability.

Develop various technology and solve this problem.One is conventional and effective means is by priming paint (primer) paint PO.Primer material normally contains the composition of maleated polyolefin (maleatedpolyolefin) and/or halogenated polyolefin and aromatic solvent or water solvent, and extensively think effective, but priming paint is expensive and being applied in the modification of PO goods of they is extra step.

Another effective ways carry out physical or chemical treatment to the surface of PO goods, such as, by chemical milling agent etching, or with plasma radiation, or is exposed to corona or flame.Although normally effective, these methods are more complicated than applying priming paint in essence, therefore more difficult control in the consistence of quality and parts and parts.

Other method is by by PO and other polymer blendings, or by making it in conjunction with one or more polar group, or physics and/or the chemical property of PO is changed by these two kinds of methods.Such as, the United States Patent (USP) 4,946,896 of the people such as Mitsuno instructs a kind of (paintable) PO brushed, and comprising: 20 ~ 80wt% (wt%) polypropylene; The ethylene copolymer that 5 ~ 38wt% is made up of ester units and the unsaturated dicarboxylic acid acid anhydride of ethene, alkyl acrylate or alkyl methacrylate; And 5 ~ 70wt% ethylene-propylene rubber.The United States Patent (USP) 4,888,391 of the people such as Domine instructs a kind of polyolefin compositions brushed, and comprises the blend of the polyolefine as external phase and the ethene/acrylic ester/acrylic terpolymer as discontinuous phase.The United States Patent (USP) 4,945,005 of the people such as Aleckner, Jr. instructs a kind of PO brushed, and comprising: the multipolymer of 2 ~ 25wt% ethylenically unsaturated carboxylic acids and ethene; 3 ~ 50wt% ethylene/alpha-olefin copolymer; The crystalline homopolymer of optional propylene or multipolymer; 5 ~ 50wt% mineral filler; With the multipolymer of 10 ~ 35wt% polyethylene or ethene and alpha-olefin.EP 0643742A1 instructs a kind of polyethylene brushed, comprise: at least polyethylene of 50wt%, the thermoplastic polymer of polar group is contained with at least one, as urethane, described polyethylene with based on polyethylene weight at least about 0.01wt% containing at least one double bond and at least one acid functional group group unsaturated organic compound (such as maleic anhydride) grafting.United States Patent (USP) 5,346, the ethene polymers of a kind of line style substantially of 963 instruction shows consistency and the erosion-resisting characteristics of expectation for multiple thermoplastic polymer blend, this ethene polymers with one or more unsaturated organic compounds containing olefinic degree of unsaturation and carbonyl as MAH grafting.United States Patent (USP) 5,424,362 teach a kind of thermoplastic compounds brushed, comprise: (i) 30 ~ 70wt% at least one polypropylene or graft modification polypropylene, (ii) at least one in the ethene polymers of the ethene polymers of the line style substantially of the non-grafted of 0 ~ 40wt% and the line style substantially of graft modification, and (iii) 0 ~ 50wt% ethene and α, the interpretation of beta-unsaturated carbonyl thing, condition is the summation of component (i) and (ii) is about 30 ~ 70wt%.

International Patent Publication 2007/033117 relates to containing at least one ethylene/alpha-olefin random interpolymers and at least one ethylene/alpha-olefin compositions based on the urethane of polyalkadiene diol, the PRR of wherein said at least one ethylene/alpha-olefin interpolymers is-6 ~ 75, and density is less than or equal to 0.93g/cc.

Except not reaching easy brushing property and printability, PO can't be attached to the blend of polar substrates as polymeric amide, urethane, polycarbonate, acrylonitrile-butadiene-styrene (ABS) (ABS) and two or more these materials well.In overmolding (over-molding) and high frequency (HF) welding (welding) application, this is important Consideration.To a kind of solution of this tack-Problem of Failure be by PO and zeolite or polar polymer as MAH-graftomer or X 4460 blended.

Although the modification PO composition of these and other all shows validity to a certain degree, for determining that the PO aspect can brushed with development of new still exists continual interest.

Invention summary

In one embodiment, the present invention is a kind of goods, comprise the first assembly and the second assembly, described first assembly comprises polar material and described second assembly comprises the blend of non-polar polyolefinic (np-PO) and the urethane based on polydiene or the urethane based on polyglycol.

In one embodiment, described second assembly is the urethane based on polydiene.In a preferred embodiment, the described urethane based on polydiene is the urethane based on polyalkadiene diol.In yet, the described urethane based on polyalkadiene diol is polybutadiene diol or polyisoprene glycol or their combination, and preferred polybutadiene diol.

In another embodiment, described second assembly is the urethane based on polyglycol.In yet, the described urethane based on polyglycol is formed by least one glycol, and described glycol is selected from the acid of lower group by one or more or the seed oil tri-glyceride (seed oil triglyceride) of its ester is made: palmitinic acid, stearic acid, oleic acid, linolic acid and linolenic acid.

The example of the described urethane based on polyglycol includes but not limited to by polyester polyol and the urethane that formed based on the polyvalent alcohol of seed oil.

In another embodiment, the present invention is the film comprising the first layer, and described the first layer comprises the blend of np-PO and the urethane based on polydiene or the urethane based on polyglycol.

In one embodiment, urethane is the urethane based on polydiene.In a preferred embodiment, the described urethane based on polydiene is the urethane based on polyalkadiene diol.In yet, the described urethane based on polyalkadiene diol is polybutadiene diol or polyisoprene glycol or their combination, and preferred polybutadiene diol.

In another embodiment, urethane is the urethane based on polyglycol.In yet, the described urethane based on polyglycol is formed by least one glycol, and described glycol is selected from the acid of lower group by one or more or the seed oil tri-glyceride of its ester is made: palmitinic acid, stearic acid, oleic acid, linolic acid and linolenic acid.The example of the described urethane based on polyglycol includes but not limited to by polyester polyol and the urethane that formed based on the polyvalent alcohol of seed oil.

In another embodiment, the present invention is water dispersion, comprise water and the solid based on total dispersion weight 30 ~ 70wt%, described solid comprises the blend of np-PO and the urethane based on polydiene or the urethane based on polyglycol, this blend comprises based on the described blend gross weight at least urethane based on polydiene of 15wt% or the urethane based on polyglycol, and the mean particle size of described solid is 0.4 ~ 2.5 micron.

In another embodiment, urethane is the urethane based on polyglycol.In yet, the described urethane based on polyglycol is formed by least one glycol, and described glycol is selected from the acid of lower group by one or more or the seed oil tri-glyceride of its ester is made: palmitinic acid, stearic acid, oleic acid, linolic acid and linolenic acid.

The example of the described urethane based on polyglycol includes but not limited to, by polyester polyol and the urethane that formed based on the polyvalent alcohol of seed oil.

In another embodiment, the present invention is blend, comprise: (i) np-PO, it is at least one in ethylene multi-block copolymer and linear ethylene interpolymer, and (ii) urethane based on polydiene or the urethane based on polyglycol.

In one embodiment, component (ii) is the urethane based on polydiene.In a preferred embodiment, the described urethane based on polydiene is the urethane based on polyalkadiene diol.In yet, the described urethane based on polyalkadiene diol is polybutadiene diol or polyisoprene glycol or their combination, and preferred polybutadiene diol.

In another embodiment, component (ii) is the urethane based on polyglycol.In yet, the described urethane based on polyglycol is formed by least one glycol, and described glycol is selected from the acid of lower group by one or more or the seed oil tri-glyceride of its ester is made: palmitinic acid, stearic acid, oleic acid, linolic acid and linolenic acid.

In one embodiment, the present invention promotes that low surface energy (namely nonpolar) PO (np-PO) is if polyethylene or polypropylene and high surface energy (i.e. polarity) polymkeric substance are as the method for the tack of polymeric amide or polyester.Described method is included in before non-polar polymer contacts with polar polymer, the gross weight accounting for nP-PO and the urethane based on polydiene or the urethane based on polyglycol is less than 50wt%, is preferably less than the step of the urethane based on polydiene of 40wt% or the urethane based on polyglycol and np-PO mixing.

As a kind of example, make to comprise nonpolar np-PO by the following method as polyethylene or polyacrylic rete with comprise polar polymer such as the tack between the adjacent film layers of polyester or polymeric amide and be improved: in curtain coating or before extruding as film, by np-PO is mixed with the urethane based on polydiene or the urethane based on polyglycol being less than 50wt%, then curtain coating or extrude this rete and it is combined with polarity rete.As another example, described polarity rete and np-PO rete are combined by tack coat, and wherein this tack coat comprises containing np-PO and is less than the urethane based on polydiene of 40wt% or the blend of the urethane based on polyglycol, with the weighing scale of blend.

In another embodiment, the present invention is the method for the goods comprising low-surface-energy material being given to the following characteristic of at least one: easily brushing property, printability, colourability, high frequency (HF) weldability and overmolding.These goods generally include film or molded parts, and this material generally includes one or more np-PO, such as polyethylene, polypropylene etc.As a kind of example of present embodiment, described method is included in before np-PO brushing, printing, dyeing, HF-welding and overmolding polar material, or before polar material brushing, printing, dyeing, HF-welding and overmolding np-PO, np-PO is less than 50wt% with the gross weight accounting for nP-PO and the urethane based on polydiene or the urethane based on polyglycol and is preferably less than the step that the urethane based on polydiene of 40wt% or the urethane based on polyglycol mixes.As another example of present embodiment, before with polar material brushing, printing, dyeing, HF-welding or overmolding, the non-polar material of film or molded parts form is covered with tack coat at least partly, described tack coat comprises containing np-PO and is less than the urethane based on polydiene of 50wt% or the blend of the urethane based on polyglycol, based on the weight of blend, or vice versa.

In another embodiment, the present invention is goods, comprise: (i) one or more nP-PO and be less than 50wt%, the urethane based on polydiene being preferably less than 40wt% or the urethane based on polyglycol, or (ii) is in conjunction with high surface energy material and the urethane based on polydiene of low-surface-energy material or the urethane tack coat based on polyglycol.The described urethane based on polyglycol is preferably the thermoplastic polyurethane (pd-TPU) based on polybutadiene diol.

In another embodiment, the present invention is footwear product, comprises the parts that at least one is formed by the blend of np-PO and the urethane based on polydiene or the urethane based on polyglycol.In one embodiment, described goods are selected from footwear outer bottom, sole middle level (shoe midsole), (shoeunit-sole), overmolding goods, natural leather article, synthetic leather goods, vamp, laminate, clad products, boots, sandals, overshoes (galoshes), plastic shoes at the bottom of footwear list, and their combination.

In another embodiment, the present invention is water dispersion, comprises the blend of water and one or more nP-PO and one or more urethane based on polydiene or the urethane based on polyglycol.Usually, this dispersion comprises 30 ~ 50wt% solid, i.e. blend, and is 0.4 micron ~ 2.5 microns when the mean particle size light scattering method of this solid is measured.Described dispersion can be used for various application widely and comprises in the preparation of the film of priming paint, paint, coating and can bond polar material and non-polar material.

In one embodiment, the described urethane based on polydiene and the urethane being preferably based on polyalkadiene diol are formed by least one aliphatic series or alicyclic diisocyanate.In yet, the described urethane based on polydiene and be preferably based on the urethane of polyalkadiene diol and thermoplastic polyurethane is formed by least one aliphatic vulcabond all independently of one another.

In another embodiment, the described urethane based on polyglycol is formed by least one aliphatic series or alicyclic diisocyanate.In yet, formed by least one aliphatic vulcabond all independently of one another based on the urethane of polyglycol and thermoplastic polyurethane.In another embodiment, the described urethane based on polyglycol comprises at least one glycol, and described glycol is selected from the acid of lower group by one or more or the seed oil tri-glyceride of its ester is made: palmitinic acid, stearic acid, oleic acid, linolic acid and linolenic acid.

In another embodiment, the present invention gives the method comprising the goods HF-weldability of non-polar material, described method comprises non-polar material and is less than the step that the urethane of 50wt% based on polydiene or the urethane based on polyglycol mixes, based on the gross weight of described non-polar material and the described urethane based on polydiene or the urethane based on polyglycol.

The composition comprising non-polar material (particularly np-PO) and the urethane based on polydiene or the urethane based on polyglycol used in the practice of the present invention may be used in various widespread use, include but not limited to, tack coat between extrusion sheet or film material or section bar (profile), fiber, water dispersion, automobile product (such as, shell, air bag, headrest, armrest, inside roof lining (headliners), carpet cushion (carpet underlayment) etc.), awning, oilcloth (tarps), roof structure (such as, for the epoxy of following all rooftop applications, the tackiness agent of urethane or acrylic substrate, described application such as insulation connects (insulation bonding), liquid roof (liquid roofing), facade sealing agent, expansion pipe (expansion joint), moist room sealing agent (wet-room sealants), the roof of upper pitch, the roof that acrylic resin adheres to, pitch combine with PUR-adhere to trimming roof (refurbishment)), the automobile case that can brush and bearing circle, the injection moulding toy that can brush, powder coating, powder slush mold goods (powder slush moldings) or roll molded article (rotational castmoldings) (usually, respective granularity is less than 950 microns), consumer durable, handle (grip), handle (handle), computer module (such as, Keyboard pad (key pads)), band, for fabric/urethane (PU) foam laminate tackiness agent (such as, embossing (appliqu é s) and footwear product), tackiness agent (hot-melting type or other), such as the combination of friction layer (abrasion layer) and extruded product, travelling belt (conveyor) and timing belt (timing belt), fabric, carpet, artificial turf, coating, electric wire and cable, raincoat and similar protective clothing.

Composition of the present invention is especially suitable for use as priming paint, paint and coating.Primer applications includes but not limited to the priming paint of following article: wallpaper, the wall base (wall bases), footwear product assembly (footwarecomponent), automobile case, automotive hose (automotive hose) and other trolley parts.Composition of the present invention can be used as the priming paint promoting that polyolefin substrate adheres to polarity glue and coating (such as conventional polyurethane adhesive and coating).Composition of the present invention can be used as the priming paint of PET cloth, the heart yearn (cord) that automobile-used band (automotive belt) uses, thus promotes the attachment of polyolefine and these base materials.Composition of the present invention also can be used as tackiness agent or casting films is used in footwear product or automobile application, and as the barrier layer between olefinic substrates and polar substrates or barrier films, such as, as soft TPO shell and the barrier layer between polyurethane foam, glue or coating.

Accompanying drawing is sketched

Fig. 1 is the subject diagram drawing lattice paint tack (cross-hatch paint adhesion) chart.

Fig. 2 is the set of the injection molded plaques (plaque) having carried out the brushing of drawing the test of lattice paint tack.

The description of preferred implementation

Definition:

Digital scope in the present invention comprise smaller value and higher value therebetween with all numerical value of an incremented, condition is the interval that there is at least Liang Ge unit between any smaller value and higher value.As an example, if the physical properties of fruit component or other character (such as, molecular weight, viscosity, melt index etc.) are 100 to 1000, then mean clearly to list whole single numerical value, as, 100,101,102 etc., and subrange, as 100-144,155-170,197-200 etc.For containing being less than the numerical value of 1 or being greater than the scope of mark (such as 1.1,1.5 etc.) of 1, think that a unit is 0.0001,0.001,0.01 or 0.1 aptly.For containing the scope (such as, 1-5) of individual position Arabic numerals being less than 10, it has been generally acknowledged that a unit is 0.1.These are only the examples of the content specifically meant, and likely combining of numerical value between cited Schwellenwert and maximum is all considered to know and records in this application.Digital scope is provided in the application, for melt index wherein, molecular weight distribution (Mw/Mn), percent crystallinity, comonomer percentage, and the carbonatoms in comonomer.

Terms such as " compositions " refers to the mixture of two or more materials.Comprise mixture after reaction forward slip value thing, reaction mixture and reaction in the composition, the latter comprises unreacted components and the degradation production of reaction product and by product and reaction mixture, if present, they are formed by one or more components of reacting forward slip value thing or reaction mixture.

The term such as " blend ", " blend polymer " refers to the composition of two or more polymkeric substance.This blend can be miscible or immiscible.This blend can be separated or non-phase separated.Measure according to the additive method that transmission electron microscopy, light scattering method, x-ray scattering method and any prior art are known, this blend can contain or not construct (domainconfiguration) containing one or more farmlands.Blend is not laminate, but one or more layers Han You blend of laminate.

" polymkeric substance " refers to the macromolecular compound prepared by identical type or dissimilar monomer polymerization.Therefore the term interpretation that general term polymer comprises term homopolymer and hereafter defines, homopolymer is commonly used to the polymkeric substance referring to only be prepared by the monomer of a type.

" interpretation " refers to the polymkeric substance by least two kinds of different monomers polymerization preparations.This generic term comprises multipolymer (being commonly used to the polymkeric substance referring to be prepared by two kinds of different monomers), and the polymkeric substance prepared by two or more different monomers, such as, and terpolymer, tetrapolymer etc.

The term such as " polymkeric substance based on alkene ", " polyolefine ", " PO " refers to comprise the polymkeric substance (total amount based on polymerisable monomer) coming from the unit of polymerization of olefin monomers (such as ethene or propylene) being greater than 50 molecular fractions.Representational polyolefine comprises polyethylene, polypropylene, polybutene, polyisoprene and their various interpretations.In the context of present disclosure, olefin multi-block interpretation clearly got rid of in terms such as " polymkeric substance based on alkene ".

The term such as " olefin multi-block interpretation ", " many block interpolymers ", " segmented copolymer ", " blocked multipolymer (segmented copolymer) " refers to two or more polymkeric substance at chemically different regions or segment (being called " block ") comprising and preferably engaging in line style mode, namely, be included in the polymkeric substance of chemically different unit, described chemically different unit for polymerization ethylenic functional group for, engage in head and the tail mode (end-to-end), instead of engage in the mode of pendency or grafting.In a preferred embodiment, described block is different in the following areas: the type of the amount of the comonomer combined in block or type, density, degree of crystallinity, the crystallite dimension being attributable to the polymkeric substance with this composition, tacticity (isotaxy or syndiotaxy) or degree, degree of regioregularity or region irregularity degree, branching amount (comprising long chain branching or super-branching), homogeneity or any other chemistry or physical properties.(comprise with the segmented copolymer of prior art and being added (sequential monomeraddition) by sequential monomer, follow multipolymer prepared by change catalyzer (fluxional catalyst) or anionic polymerization) compare, feature for implementing segmented copolymer of the present invention is polymkeric substance polydispersity index (PDI or Mw/Mn or MWD), the unique distribution of block length distribution and/or the distribution of block number, this is due to shuttling agent (shuttling agent) in a preferred embodiment and the compound action for the preparation of the multiple catalysts of segmented copolymer.The feature of this segmented copolymer is heterogeneity index (PDI or M of the unique distribution that the unique method owing to preparing multipolymer causes _w/ M _n), block length distributes, and/or block number distribution (block number distribution).More specifically, when producing in a continuous process, polymkeric substance expects that the PDI had is 1.7-3.5, preferred 1.8-3, more preferably 1.8-2.5, most preferably 1.8-2.2.When producing with interval or semi-batch process, polymkeric substance expects that the PDI had is 1.0-3.5, preferred 1.3-3, more preferably 1.4-2.5, most preferably 1.4-2.In the context of present disclosure, the polymkeric substance based on alkene clearly got rid of in terms such as " olefin multi-block interpretations ".Representational olefin multi-block interpretation comprise The Dow Chemical Company manufacture and with trade(brand)name INFUSE ^tmthe olefin multi-block interpretation sold.

Terms such as " ethylene multi-block copolymers " refers to that a kind of comprising comes from ethene and one or more can the segmented copolymer of unit of comonomer of copolymerization, the unit wherein coming from ethene forms multiple polymeric monomeric units of at least one block in polymkeric substance or segment, at least 90mol% of preferred described block, more preferably at least 95mol%, most preferably at least 98mol%.Based on total polymer weight, be preferably 25 ~ 97% for the ethylene content implementing ethylene multi-block copolymer of the present invention, be more preferably 40 ~ 96%, be even more preferably 55 ~ 95%, most preferably be 65 ~ 85%.

Terms such as " polymkeric substance based on ethene " refers to comprise the polymkeric substance based on alkene of the vinyl monomer (total amount based on polymerisable monomer) of the polymerization being greater than 50mol%.Ethylene multi-block interpretation clearly got rid of in the terms such as the polymkeric substance based on ethene of the context use of present disclosure.

Terms such as " ethylene/alpha-olefin interpolymers " refers to comprise the vinyl monomer (total amount based on polymerisable monomer) of the polymerization being greater than 50mol% and the interpretation based on alkene of at least one alpha-olefin.The many block interpolymers of ethylene/alpha-olefin clearly got rid of in the terms such as the ethylene/alpha-olefin interpolymers of the context use of present disclosure.

Terms such as " the random ethylene/alpha-olefin interpretations " that use in the present invention is consistent with the use of their covering polymer in the prior art, refers to the interpretation based on ethene of comonomer along polymer chain random distribution.The many block interpolymers of ethylene/alpha-olefin clearly got rid of in the terms such as the random ethylene/alpha-olefin interpretation used in the context of present disclosure.

Terms such as " polymkeric substance based on propylene " refers to comprise the polymkeric substance based on alkene of the propylene monomer (total amount based on polymerisable monomer) of the polymerization being greater than 50mol%.The many block interpolymers of propylene clearly got rid of in the terms such as the polymkeric substance based on propylene of the context use of present disclosure.

Terms such as " propylene/alpha-olefins interpretations " refers to comprise the propylene monomer (total amount based on polymerisable monomer) of the polymerization being greater than 50mol% and the interpretation based on alkene of at least one alpha-olefin.The many block interpolymers of propylene/alpha-olefins clearly got rid of in the terms such as the propylene/alpha-olefins interpretation of the context use of present disclosure.

The terms such as term " propylene/ethylene interpretation " refer to comprise the interpretation of the propylene monomer (total amount based on polymerisable monomer) of the polymerization being greater than 50mol%, and the remaining part of this interpretation comprises at least partially the vinyl monomer that (being such as generally at least 1mol%) is polymerized.This term used in this application does not refer to the many block interpolymers of propylene/ethylene.

The polyether polyols with reduced unsaturation formed by polydiene is divided in term fingers such as " urethane based on polydiene ", and described polydiene contains at least one isocyanate-reactive group, such as, and hydroxyl and/or amido.

The polyether polyols with reduced unsaturation formed by the polyvalent alcohol containing at least two hydroxyls is divided in term fingers such as " urethane based on polyglycol ".

The polyether polyols with reduced unsaturation formed by the polydiene containing at least two hydroxyls is divided in term fingers such as " urethane based on polyalkadiene diol ".

The term such as " glycol of natural origin ", " natural oil polyols " refers to derive from the glycol of agricultural-food as seed oil (as soybean, Sunflower Receptacle, corn and canola).This glycol can contain or not contain diene degree of unsaturation.The composition of seed oil tri-glyceride is well-known.Tri-glyceride is the fatty acid ester of glycerine, and its composition depends on the source of oil.Nomenclature used be fat and oil industry in standardized denomination, wherein first illustrate that the carbon number of lipid acid is again with the unsaturated bit number of bracket pair.Representational oil comprises palmitinic acid, stearic acid, oleic acid, linoleic acid plus linolenic acid.In order to prepare polyvalent alcohol by these tri-glycerides, the oil of the degree of unsaturation of contained high levels is desired.Oil contains the saturated fatty acid of low relative levels so be acceptable due to them as soya-bean oil, Tower rape oil and sunflower oil, and such as palm wet goods raw material be further purified or in refining situation because high-caliber saturated fatty acid is considered to not spendable.

The term such as " laminate ", " laminated " refers to two or more layers such as rete intimate contact with one another.Laminate comprises the moulded parts of coating.Laminate is not blend, but one or more layers of laminate can comprise blend.

The term such as " polarity ", " polar polymer " refers to that the molecule of polymkeric substance has permanent dipole, and namely polymer molecule has positive terminal and negative electricity end.In other words, the electronics in polar molecule is not even distribution between the atom of this molecule.On the contrary, the term such as " nonpolar ", " non-polar polymer " refers to that polymer molecule does not have permanent dipole, that is, polymkeric substance does not have positive terminal and negative electricity end.Electronics in non-polar molecule is even distribution substantially between the atom of this molecule.Major part hydrocarbon liquids and polymkeric substance are nonpolar.By the polymkeric substance polar polymer often that carboxyl, hydroxyl etc. replace.The goods prepared by non-polar polymer have lower surface energy, and be namely less than 32 dynes per centimeter (dyne/cm), the goods prepared by polar polymer have higher surface energy, i.e. 32dyne/cm or more.Non-polar material of the present invention comprises one or more apolar thermoplastic's olefin polymers usually, is generally elastomerics, not containing the polar functional group of any significant quantity, such as, and the groups such as hydroxyl, carboxyl, carbonyl, ester, ether, acid amides, mercaptan, halogenide.Polar material of the present invention generally includes one or more polymkeric substance containing one or more polar functional group.The typical polymers comprising one or more polar functional group comprises polyester, polyethers, poly(lactic acid), polycarbonate, nylon, polysulphide, polysulfones, urethane, polyvinyl alcohol, polyvinyl acetate, polyvinyl chloride, vinyl cyanide and ABS.The polar polymer that polar material, polar substrates, Polar Crystal Slab etc. are described by this paragraph is usually formed.The non-polar polymer that non-polar material, non-polar substrate, nonpolar film etc. are described by this paragraph is usually formed.

" polar functional group of content can be ignored " and wait term to refer to that the quantity not sufficient of the polar functional group contained by polymkeric substance is to give the surface energy of goods prepared therefrom at least about 32dyn/cm.

The term such as " to be substantially free of " and to refer to composition only containing the compound can ignoring content, thus any existence of this compound all to composition without any materially affect.Usually, when the amount that compound exists is less than 0.1wt% based on composition weight, think that composition is substantially free of this compound.

Terms such as " overmoldings " refers to a kind of resin injection to contain in the mould of preset base material, and carries out molding on the substrate.Usually, by by a kind of resin overmolding on another polymeric substrate, use overmolding to improve performance and the character of the finished product.Overmolding can be used to form jointless integral component.The example of the parts of overmolding is included in the flexible grasping member on power tool and kitchen appliance, and it provides extra grasping character and does not have usually relevant with mechanical package hygienic issues.Described base material can be any suitable material, as plastics, metal or ceramic component.

Terms such as " molded overlay (overlayer) " refers to comprise the goods of at least two basic change part together (articles injection-moulded and base material).The articles injection-moulded top being placed in base material, outside is injection mold.Tackiness agent can be used to this articles injection-moulded and base material that bonds.Described base material can be any suitable material, as plastics, metal or ceramic component.

Composition useful in enforcement of the present invention:

In one embodiment of the invention, described blend comprises at least one np-PO (optimal ethylene/alpha-olefin random interpolymers) and the urethane of at least one based on polydiene or the urethane based on polyglycol.In another embodiment, the amount of np-PO is more than or equal to 50wt%, the amount of the described urethane based on polydiene or the urethane based on polyglycol is less than or equal to 50wt%, and two percentage ratio is all based on the gross weight of np-PO and the described urethane based on polydiene or the urethane based on polyglycol.This tittle is preferably the urethane of 50 ~ 90wt%np-PO and 50 ~ 10wt% based on polydiene or the urethane based on polyglycol, more preferably the urethane of 50 ~ 85wt%np-PO and 50 ~ 15wt% based on polydiene or the urethane based on polyglycol.In another embodiment, described blend comprises described in 55 ~ 80wt%np-PO and 45 ~ 20wt% based on the urethane of polydiene or the urethane based on polyglycol.The described urethane based on polydiene or the urethane based on polyglycol can comprise one in the glycol of the urethane based on polydiene or the urethane based on polyglycol and natural origin or both.The amount selected adds up to 100wt%.

In one embodiment, the described urethane based on polydiene and the urethane being preferably based on polyalkadiene diol are formed by least one aliphatic series or alicyclic diisocyanate.

In another embodiment, the described urethane based on polyglycol is formed by least one aliphatic series or alicyclic diisocyanate.In another embodiment, the described urethane based on polyglycol comprises at least one glycol, and described glycol is selected from the acid of lower group by one or more or the seed oil tri-glyceride of its ester is made: palmitinic acid, stearic acid, oleic acid, linolic acid and linolenic acid.

The preferred blend used in enforcement of the present invention comprises 50wt% or more and the np-PO of preferred 60wt% or more, and 50wt% or less and preferably 40wt% or less urethane based on polydiene or the urethane based on polyglycol.In one embodiment, described blend comprises: 50wt% ~ 80wt% and the np-PO of preferred 55wt% ~ 77wt%; With 20wt% ~ 50wt% and preferably described in 23 ~ 45wt% based on the urethane of polydiene or the urethane based on polyglycol; Both percentage ratio is all based on the gross weight of np-PO and the described urethane based on polydiene or the urethane based on polyglycol.

If the blend used in enforcement of the present invention comprises other components except np-PO and the urethane based on polydiene or the urethane based on polyglycol, such as filler, pigment etc., then the combination of np-PO and d-TPU accounts for and is greater than 85wt%, be preferably greater than 90wt%, more preferably greater than 95wt%, based on the gross weight of described blend.

In one embodiment, the melt index (I of the blend used in enforcement of the present invention ₂) be 0.01-100g/10min when using ASTM D-1238 (190 DEG C, 2.16kg load) canonical measure, be preferably 0.1-50g/10min, be more preferably 1-40g/10min, even more preferably 5-40g/10min.In another embodiment, the I of described blend ₂be more than or equal to 0.01g/10min, preferably greater than or equal to 1g/10min, more preferably greater than or equal 5g/10min.In another embodiment, the I of described blend ₂be less than or equal to 100g/10min, be preferably less than or equal to 50g/10min, be more preferably less than or equal 20g/10min.The I of above-mentioned blend ₂at pure blend, namely not containing possibility remarkably influenced I ₂the blend of other components measured is measured.

In another embodiment, the percent crystallinity of described blend is less than or equal to 50% according to during dsc measurement, is preferably less than or equal to 30%, is more preferably less than or equals 20%.Preferably the percent crystallinity of these polymkeric substance is 2 ~ 50%, comprises all single numerical value between 2 ~ 50% and subrange.The degree of crystallinity of above-mentioned blend is at pure blend, and the blend namely not containing other components of possibility remarkably influenced degree of crystallinity measurement is measured.

In another embodiment, the density of described blend is more than or equal to 0.855 gram/cc of (g/cm ³or g/cc), preferably greater than or equal to 0.86g/cm ³, more preferably greater than or equal 0.87g/cm ³, and density is less than or equal to 1g/cm ³, be preferably less than or equal to 0.97g/cm ³, be more preferably less than or equal 0.96g/cm ³, be even more preferably less than or equal 0.95g/cm ³.In one embodiment, this density is 0.855 ~ 0.97g/cm ³, be preferably 0.86 ~ 0.95g/cm ³, be more preferably 0.865 ~ 0.93g/cm ³.The density of above-mentioned blend is at pure blend, and the blend namely not containing other components of possibility remarkably influenced density measurement is measured.Comprise at blend in these embodiments of one or more fillers (such as, barium sulfate, talcum etc.), maximum density may more than 1g/cm ³, such as, wherein depend on character and the content of filler, maximum density can close to or more than 1.4g/cm ³.

In another embodiment, the tensile strength of the blend of pure form and preparation form (fabricated form) is 5 ~ 40 MPas (MPa), is preferably 8 ~ 30MPa, is even more preferably 9 ~ 20MPa.

In another embodiment, be 50 ~ 600 when the longitudinal tensile strain rate of the blend of pure form and preparation form or cross direction elongation are measured according to ASTM D-638-03, or be 50 ~ 500.

In another embodiment, the melt strength of the blend of pure form is 0.5 ~ 50 li of newton (cN), more preferably 0.5 ~ 20cN, even more preferably 0.5 ~ 10cN.

In another embodiment, the surface tension of the blend of pure form is 10 ~ 100 dynes per centimeter (dyn/cm) room temperature or 23 DEG C, more preferably 20 ~ 70dyn/cm, even more preferably 30 ~ 50dyn/cm.

In another embodiment, the surface tension of the blend of pure form room temperature or 23 DEG C for being more than or equal to 30dyn/cm, more preferably greater than or equal 35dyn/cm, even more preferably greater than or equal 40dyn/cm.

In one embodiment, the invention provides the purposes of blend, as mentioned above, ethylene/alpha-olefin random copolymers exists with the form of external phase in such blends, or exists with the form of co-cable transmission with the described urethane based on polydiene or the urethane based on polyglycol.

In another embodiment, the invention provides the purposes of blend, as mentioned above, ethylene/alpha-olefin random copolymers exists with the form of the discontinuous phase among the described urethane based on polydiene or the urethane based on polyglycol in such blends.

The blend used in enforcement of the present invention can be prepared as ethylene/alpha-olefin random interpolymers and one or more urethane based on polydiene or the urethane based on polyglycol by merging one or more nP-PO.Usually, blend of the present invention is prepared by (post-reactor) polymer blend component after reactor (random ethylene/alpha-olefin random interpolymers and the described urethane based on polydiene or the urethane based on polyglycol).Illustrative examples blended after reactor for extruding, wherein by two or more solid polymers input forcing machine and physical mixed becomes substantially homogeneous composition.The blend used in enforcement of the present invention can be crosslinked and/or foaming.In a preferred embodiment, described blend is by preparing with smelting process mixed ethylene/alpha-olefin random interpolymers and the described urethane based on polydiene or the urethane based on polyglycol.In yet, this smelting process is melt extrusion method.

Blend of the present invention also can be mixed with aqueous based dispersions (water-based dispersion) or water dispersion.In the present embodiment, blend is mixed in any convenient manner with water, such as, mix in blending machine or forcing machine, usually water is added in blend, instead of blend is added to the water.Blend can be formed under various wide in range condition, such as, room temperature, high temperature, lower than normal atmosphere with higher than atmospheric pressure etc., and in water, the amount of solid (that is, blend) also can significantly change.Usually, in dispersions based on the weight of described dispersion, the amount of solid is greater than 0, preferably at least 20wt%, more preferably at least 30wt%.Maximum solids loading content changes according to the character of blend and dispersion condition such as temperature, pressure, presence or absence dispersion agent etc., but is about 70wt% based on total dispersion weight maximum usually, and preferably about 60wt%, is more preferably 55wt%.

Except blend and water, dispersion can contain other components, such as, and tensio-active agent, wetting agent, pigment, antioxidant, filler, processing aid etc.These other components are optional, and use with known quantity in a known way.Use tensio-active agent (also referred to as dispersion agent) to realize the dispersion of solid in whole water-based, they can be any different types, include but not limited to, anion surfactant, nonionogenic tenside, and preferably water miscible.Use wetting agent help dispersion steadily and fully flow through substrate surface, these wetting agents include but not limited to following material: DOWFAX 2A1 (anionic compound) and TERGITOL 15-S-9 (non-ionic compound).

In other usual available documents, U.S. Patent Application Publication 2005/0100754 describes the preparation of water dispersion.

In one embodiment, on some alkene base materials, film is formed after dispersion of the present invention at room temperature drying.In the present embodiment, blend, base material or both elasticity larger (that is, degree of crystallinity is lower), then blend is easier at room temperature forms film on alkene base material.In this limit of power (in thiscapacity), dispersion can serve as the priming paint of following article: alkene shoemaking based article, wallpaper, the wall base, automobile case, automotive hose are (such as, by flexible pipe by soaking container priming, drying, another polar material is squeezed on it), and in any other application of the reality needing polyolefin elastomer and polyurethane adhesive, foam, coating etc. to adhere to.The heart yearn that these dispersions also can serve as the priming paint of polyethylene terephthalate (PET) cloth, automobile-used band uses, etc.

Except non-polar polyolefinic with based on except the urethane of glycol, the blend used in enforcement of the present invention can also contain at least one additive, includes but not limited to antioxidant, surface tension modifier, whipping agent, pore forming material, static inhibitor, releasing agent, process oil, filler, wax, pigment, linking agent and anti blocking agent.The example of hindered phenol antioxidant derives from Ciba-Geigy Corp. 1076 antioxidants.

In another embodiment, the polypropylene polymer components that blend comprises is that described np-PO or it and one or more other np-PO are as the combination of ethylene/alpha-olefin random interpolymers.

In one embodiment, by blend and another is polyolefin coextruded, formed containing the film to least two layers or synusia (ply).In another embodiment, by composition and one or more are polyolefin coextruded, form the film containing at least three layers or synusia.In the present embodiment, the layer comprising blend is middle layer, and it serves as the tack coat between two skins.Composition for thermoplastic elastomer that suitable polyolefine for coextrusion comprises high fondant-strength (>=5cN) ethylene/alpha-olefin interpolymers and rheological modification, that be substantially free of gel, as United States Patent (USP) 6,506, describe in 842.

As mentioned above, in enforcement of the present invention, operable blend also can with the thermoplastic polyurethane of one or more other types as based on the urethane of polyethers/polyvalent alcohol and/or the urethane based on polyester/polyvalent alcohol.In this blend, often kind of polyurethane component can containing one or more unsaturated group or not containing unsaturated group.In addition, this blend can also contain one or more other polyolefine and/or one or more polyolefin elastomers.

Suitable polyether glycol includes but not limited to, those polyether glycols obtained by carrying out the suitable raw molecule of alkoxylate with the mixture of two or more of oxyalkylene as ethylene oxide, propylene oxide, oxybutylene or these materials.

In one embodiment, composition of the present invention comprises styrenic block copolymer further.These styrenic block copolymers can be triblock copolymers, include but not limited to the SBS multipolymer of SBS (SBS) and hydrogenation, styrene butadiene Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock and hydrogenated styrene-butadiene Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock, SIS (SIS) and hydrogenation SIS multipolymer, styrene-isoprene diblock multipolymer and hydrogenated styrene isoprene Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock, styrene-ethylene-butylene-styrene (SEBS) Tetrablock copolymer and hydrogenated SEBS copolymers, styrene-acrylonitrile copolymer (SAN), and elastomer-modified SAN.Phenyl can be the SBS of hydrogenation in the polymkeric substance of ethene, and derive from Shell Chemical, commodity are called KRATON G-1652.

In one embodiment, composition of the present invention comprises linking agent further.If need crosslinked, then can realize being cross-linked by any one using in multiple different reagent, such as, use the initiator of thermal activation, such as superoxide and azo-compound; Light trigger, such as benzophenone; Vinyl silanes, such as vinyltriethoxysilane or vinyltrimethoxy silane; Etc..Or, by replacing linking agent to obtain crosslinked with crosslinking technological, such as, use the radiotechnology (as electron beam and x-ray) and the moisture-curable that are different from daylight and UV light, although this two method all can be benefited from use initiator.These linking agents and technology is used with known quantity and known device and program.

In one embodiment, composition of the present invention also comprises styrenic block copolymer.In yet, this styrenic block copolymer is the styrene-butadiene-styrene block copolymer of styrene-butadiene-styrene block copolymer or hydrogenation.

In one embodiment, composition comprises at least one linking agent further.In yet, this linking agent is at least one in superoxide, azo-compound, light trigger and vinyl silanes.In another embodiment, composition carried out electron beam or x-x radiation x or stand moisture crosslinking conditions.

In another embodiment, the present invention is the goods comprising the assembly that at least one is made up of said components.In yet, these goods are selected from film, sheet material, fiber, pipe, fabric, foam, tackiness agent, coating, electric wire or cable sheath, protective clothing, trolley part, footwear product assembly, laminate, powder coating, powder slush mold goods or consumer durable.

Suitable polyester/polyvalent alcohol includes but not limited to gather (alkylidene group alkanedioic acid ester) glycol (poly (alkylene alkanedioate) glycol), and its use is prepared by conventional esterification procedures relative to the aliphatic diol of alkanedioic acid molar excess.When needed, the suitable isocyanic ester of expectation, chain extension agent and stopping of chain agent can also be added.

Blend useful in enforcement of the present invention can comprise the combination of two or more embodiments as above above-mentioned.

Ethylene/alpha-olefin random interpolymers as np-PO component:

In one embodiment, useful in enforcement of the present invention blend comprises at least one ethylene/alpha-olefin (EAO) random interpolymers.Ethylene/alpha-olefin interpolymers is the polymkeric substance by ethene and at least one comonomer polymerization preparation, and this comonomer is generally has 3 ~ 20 carbon atom (C ₃-C ₂₀) alpha-olefin, or diene, such as Isosorbide-5-Nitrae-divinyl or Isosorbide-5-Nitrae-hexadiene.

Illustrative alpha-olefin comprises propylene, 1-butylene, 1-amylene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-nonene, 1-decene and vinylbenzene.Described alpha-olefin is expected for C ₃-C ₁₀alpha-olefin.Preferably this alpha-olefin is propylene, 1-butylene, 1-hexene or 1-octene.Illustrative interpretation comprises ethylene/propene (EP) multipolymer, ethylene/butylene (EB) multipolymer, ethylene/hexene (EH) multipolymer, ethylene/octene (EO) multipolymer, (EAODM) interpretation of ethylene/alpha-olefin/diene modification, as (EPDM) interpretation and the ethylene/propylene/octene terpolymer of ethylene/propylene/diene modification.Preferred multipolymer comprises EP, EB, EH and EO polymkeric substance.

In another embodiment, the comonomer being incorporated into the ethylene/alpha-olefin interpolymers of final polymkeric substance is greater than 5wt% based on the gross weight of polymerisable monomer, is preferably greater than 10wt%.The introduction volume of comonomer can be greater than 15wt% based on the gross weight of polymerisable monomer, even can be greater than 40wt% or 45wt%.

Preferably, the molecular weight distribution (Mw/Mn or MWD or PDI) of the EAO interpretation used in enforcement of the present invention is 1.5 ~ 4.5, is more preferably 1.8 ~ 3.8 and most preferably is 2.0 ~ 3.4.The density of this EAO interpretation is less than or equal to 0.93g/cc, is preferably less than or equal to 0.92g/cc and is more preferably less than or equals 0.91g/cc.In another embodiment, the density of this EAO interpretation is more than or equal to 0.86g/cc, preferably greater than or equal to 0.87g/cc, and more preferably greater than or equal 0.88g/cc.In another embodiment, the density of this EAO interpretation is 0.86 ~ 0.93g/cc.

In one embodiment, the I of EAO interpretation ₂be more than or equal to 0.1g/10min, preferably greater than or equal to 0.5g/10min and more preferably greater than or equal 1.0g/10min.In another embodiment, the I of EAO interpretation ₂be less than or equal to 50g/10min, be preferably less than or equal to 30g/10min and be more preferably less than or equal 25g/10min.In another embodiment, the I of EAO interpretation ₂be 0.1 ~ 50g/10min, be preferably 0.1 ~ 30g/10min and be more preferably 0.1 ~ 25g/10min.

EAO interpretation useful in the present invention more specifically example comprises very low density polyethylene (VLDPE) (such as, FLEXOMER ^tmethene/1-hexene polyethylene, The Dow ChemicalCompany system), linear ethylene/alpha-olefin copolymer (such as TAFMER of Mitsui PetrochemicalsCompany Limited of homogeneous branching ^tmwith the EXACT of Exxon Chemical Company ^tm), and the ethylene/alpha-olefin polymer of the line style substantially of homogeneous branching (such as, derives from the AFFINITY of The DowChemical Company ^tmand ENGAGE ^tmpolyethylene).Preferred polyolefin copolymer is the line style of homogeneous branching and the ethylene copolymer of line style substantially.Substantially linear ethylene copolymers is particularly preferred, and is more fully described in United States Patent (USP) 5,272,236,5,278,272 and 5,986, and in 028.Other examples of suitable commercially available EAO interpretation comprise the NORDEL deriving from The DowChemical Company ^tmmG and NORDEL ^tmiP product, and the VISTALON deriving from ExxonMobil Chemical Company ^tm.

In another embodiment of the present invention, the 0.1rad/sec shear viscosity (herein also referred to as low-shear viscosity) of EAO interpretation is greater than 100, and 000 pool, is preferably greater than 200,000 pool, and more preferably greater than 300,000 moors and is most preferably greater than 400,000 pool.This viscosity be use dynamic mechanical spectrophotometer as RMS-800 or ARES of Rheometrics 190 DEG C, measure polymer viscosity under the velocity of shear of 0.1rad/sec and obtain.

Low-shear viscosity affects by the LCB degree of molecular weight (MW) and polymkeric substance.Molecular weight is by the melt strength indirect inspection of polymkeric substance.As usual rule, the molecular weight of polymkeric substance is larger, and melt strength is better.But when molecular weight becomes excessive, polymkeric substance becomes can not be processed.LCB is introduced the workability that polymer backbone improves high MW polymkeric substance.Therefore low-shear viscosity (0.1rad/sec) is the tolerance to a certain degree balanced between MW and LCB in polymkeric substance.

In another embodiment of the present invention, the melt strength (MS) of ethylene/alpha-olefin random interpolymers is 5cN or larger, preferred 6cN or larger, more preferably 7cN or larger.The melt strength used in the application is the maximum stretching force in units of cN measured on the melting silk thread of polymer melt, and this silk thread was with the inverse (sec of 33 seconds ^-1) constant shear speed extrude from capillary rheometer die head, elongated by a pair nip rolls (nip roller) by silk thread, this nip rolls accelerates this silk thread with the speed of 0.24 cel (cm/sec) from original speed 1cm/sec simultaneously.Described melting silk thread produces preferably by following methods: heat 10 grams (g) and be contained in polymkeric substance in Instron capillary rheometer keg, at 190 DEG C of balance polymers 5 minutes (min), then with the velocity of piston of 2.54cm/min, by diameter be 0.21cm, length is the kapillary die head extruded polymer of 4.19cm.Drawing force is preferably measured with GoettfertRheotens melt drawn test machine, arranges 10cm place immediately below this test machine nip rolls is in site that silk thread leaves kapillary die head.

In one embodiment, ethylene/alpha-olefin polymer (or interpretation) is for line style is based on the interpretation of ethene.This interpretation can be the line style (line style substantially relative to homogeneous branching) of non-homogeneous branched linear or homogeneous branching.Term " line style is based on the interpretation of ethene " refer to when by technology known in the art as NMR spectroscopy measurements time, there is no long chain branching or there is no the interpretation of the long chain branching that can predict quantity.

Term " homogeneous " and " homogeneous branching " are used for ethylene/alpha-olefin polymer (or interpretation), wherein alpha-olefin comonomer is random distribution in given polymer molecule, and substantially all polymer molecules all have the ratio of identical ethene and comonomer.These interpretations use metallocene catalyst system to prepare usually.

The linear ethylene interpolymer of described homogeneous branching is the ethylene interpolymer not having long chain branching (maybe can predict the long chain branching of quantity), but have the short-chain branch coming from the comonomer being aggregated to interpretation, wherein said comonomer is all homogeneous distribution in identical polymer chain and between different polymer chains.The same with the situation of linear, low density polyethylene polymerization thing or linear high density polyethylene polymkeric substance, the linear ethylene interpolymer of homogeneous branching does not have long chain branching, use such as United States Patent (USP) 3,645, the even branching distribution polymerization method preparation that in 992, Elston describes.

The example of the linear ethylene/alpha-olefin interpolymers of commercially available homogeneous branching comprises the TAFMER of Mitsui ChemicalCompany supply ^tMthe EXACT that polymkeric substance and ExxonMobil Chemical Company supply ^tMpolymkeric substance.

The line style of non-homogeneous branching is mainly their comonomer branching distribution based on the interpretation part based on ethene that the interpretation of ethene is different from homogeneous branching.Such as, the interpretation of non-homogeneous branching has branching distribution, and in the distribution of this branching, polymer molecule has the ratio of different ethene and comonomer.The interpretation based on ethene of non-homogeneous branching uses Ziegler/Natta catalyst system to prepare usually.These linear interpolyemr do not have long chain branching (maybe can predict the long chain branching of quantity).

The interpretation based on ethene of non-homogeneous branching includes but not limited to, line style Medium Density Polyethylene (LMDPE), LLDPE (LLDPE), very low density polyethylene (VLDPE) and ultra-low density polyethylene (ULDPE).Commercially available polymkeric substance comprises DOWLEX ^tMpolymkeric substance, ATTANE ^tMpolymkeric substance and FLEXOMER ^tMpolymkeric substance (all deriving from The Dow Chemical Company), and ESCORENE ^tMand EXCEED ^tMpolymkeric substance (both all derive from Exxon Mobil).

In one embodiment, ethylene/alpha-olefin polymer (or interpretation) is line style, homogeneous branching substantially, wherein alpha-olefin comonomer is random distribution in given polymer molecule, and all polymer molecules have the ratio of identical ethene and comonomer substantially.At United States Patent (USP) 5,272,236,5,278,272,6,054,544,6,335,410 and 6,723, describe the ethylene interpolymer of the line style substantially used in the present invention in 810.The ethylene interpolymer of described line style is substantially the ethene polymers of the homogeneous branching with long-chain branch.Long-chain branch has the comonomer distribution identical with polymer backbone, and can have the length with the same length of polymer backbone.The carbon chain lengths (carbon length) of long-chain branch is greater than the carbon chain lengths that an introducing comonomer unit obtains in polymer backbone.

" substantially line style " is often referred to replacement has average every 1000 total carbon numbers (comprising the carbon on skeleton and the carbon on side chain) 0.01 long-chain branch to the polymkeric substance of every 1000 total carbon numbers 3 long-chain branchs, as above-mentioned ' 272 patents are discussed.Some polymkeric substance can replace has every 1000 total carbon numbers 0.01 long-chain branch to every 1000 total carbon numbers 1 long-chain branch.The example of commercially available simple linear polymer substantially comprises the ENGAGE deriving from The Dow Chemical Company ^tmand AFFINITY ^tmpolymkeric substance.

The ethylene interpolymer of described line style substantially forms the ethene polymers of unique homogeneous branching of a class.They are different from Elston in essence at United States Patent (USP) 3, 645, the linear ethylene interpolymer of the homogeneous branching of routine of the well-known types described in 992, in addition, they are linear ethylene polymkeric substance (the such as ultra-low density polyethylene (ULDPE) that is polymerized of Ziegler-Natta catalyst heterogeneous with routine neither, LLDPE (LLDPE) or high density polyethylene(HDPE) (HDPE), such as use the people such as Anderson at United States Patent (USP) 4, 076, method disclosed in 698 obtains) be identical type, also not with high pressure, the highly-branched polyethylene that free radical causes (such as, Low Density Polyethylene (LDPE), ethylene-acrylic acid (EAA) multipolymer and ethane-acetic acid ethyenyl ester (EVA) multipolymer) be identical type.

The ethylene interpolymer of the homogeneous branching, the substantially line style that use in the present invention has excellent workability, even if to have narrower molecular weight distribution also like this for they.Surprisingly, the melt flow ratio (I that measures according to ASTM D 1238 of the ethylene interpolymer of this line style substantially ₁₀/ I ₂) can vary widely and substantially have nothing to do with molecular weight distribution.The linear ethylene interpolymer of the homogeneous branching that this surprising character is complete and conventional is (if Elston is at United States Patent (USP) 3,645, describe in 992 those) and the linear polyethylene interpretation that is polymerized of the conventional Ziegler-Natta of homogeneous branching (if the people such as Anderson are at United States Patent (USP) 4,076, describe in 698 those) contrary.Be different from the ethylene interpolymer of line style substantially, the rheological property of linear ethylene interpolymer (no matter homogeneous or non-homogeneous branching) makes along with molecular weight distribution increases, I ₁₀/ I ₂value also increases.

The random ethylene/alpha-olefin component of the present composition can contain the combination of two or more above-mentioned embodiments.

Olefin multi-block interpretation as np-PO component:

For the olefin multi-block interpretation used in the invention process, describe these multipolymers in the context of ethylene multi-block copolymer, these multipolymers are generally understood as the example of olefin multi-block interpretation.Representational olefin multi-block interpretation comprises the olefin multi-block interpretation being manufactured by The Dow Chemical Company and sold, and trade mark is INFUSE ^tm.

With two kinds of catalyzer, described ethylene multi-block copolymer adds that the comonomer of different amount obtains, the weight ratio of the block of these multipolymers is 95: 5 ~ 5: 95.This elastomer polymer expects that the ethylene content had is 20 ~ 90%, and optional diene content is 0.1 ~ 10%, and alpha-olefin content is 10 ~ 80%, based on the gross weight of polymkeric substance.Preferably the ethylene content of many block elastomers polymkeric substance of present embodiment is 60 ~ 90% further, and diene content is 0.1 ~ 10%, and alpha-olefin content is 10 ~ 40%, based on the gross weight of polymkeric substance.Preferred polymkeric substance is high-molecular weight polymer, and weight-average molecular weight (Mw) is 10,000 ~ about 2,500,000, preferably 20,000 ~ 500,000, more preferably 20,000 ~ 350,000; Polydispersity index is less than 3.5, is more preferably less than 3 and is low to moderate about 2; And mooney viscosity (Mooneyviscosity) (ML (1+4) 125 DEG C) is 1 ~ 250.More preferably the ethylene content of this polymkeric substance is 65 ~ 75%, and diene content is 0 ~ 6%, and alpha-olefin content is 20 ~ 35%.

The density of ethylene multi-block copolymer useful in enforcement of the present invention is less than about 0.90g/cc, is preferably less than about 0.89g/cc, is more preferably less than about 0.885g/cc, is even more preferably less than about 0.88g/cc and is more preferably less than about 0.875g/cc most.The density of usual ethylene multi-block copolymer is greater than about 0.85g/cc, more preferably about 0.86g/cc.Density is measured by ASTM D-792 code.Low density ethylene segmented copolymer is common to be characterized as amorphous, soft and to have good optical property, such as, to the transmissivity of visible ray and UV light is high and mist degree is low.

The fusing point of ethylene multi-block copolymer useful in enforcement of the present invention is less than about 125.Fusing point is measured by means of differential scanning calorimetry (DSC) method described in WO 2005/090427 (US2006/0199930).Low melting point ethylene multi-block copolymer usually shows the snappiness and thermoplasticity that can be used for expectation prepared by moulded product of the present invention.

The ethylene multi-block copolymer used in enforcement of the present invention, their preparation and purposes are more fully described in WO 2005/090427, US2006/0199931, US2006/0199930, US2006/0199914, US2006/0199912, US2006/0199911, US2006/0199910, US2006/0199908, US2006/0199907, US2006/0199906, US2006/0199905, US2006/0199897, US2006/0199896, US2006/0199887, US2006/0199884, US2006/0199872, US2006/0199744, US2006/0199030, in US2006/0199006 and US2006/0199983.

In yet, polymkeric substance of the present invention, especially those polymkeric substance obtained in continuous solution polymerization reactor, have the block length distribution of maximum probability.The most preferred polymkeric substance used in enforcement of the present invention is the segmented copolymer containing 4 or more blocks or segment (comprising end-blocks).In one embodiment of the invention, this ethylene multi-block copolymer is defined as follows:

(a) have about 1.7 to about 3.5 Mw/Mn, at least one in the fusing point Tm of degree Celsius and with gram/cc density d, wherein the numerical value of Tm and d meets relational expression below:

T _m>-2002.9+4538.5 (d)-2422.2 (d) ²; Or

B () has the M of about 1.7 to about 3.5 _w/ M _n, it is characterized in that Heat of fusion Δ H, in J/g with the Δ amount of degree Celsius, Δ T, is defined as the highest DSC peak and the peak-to-peak temperature difference of the highest CRYSTAF, and the numerical value of wherein said Δ T and Δ H has following relation:

When Δ H be greater than 0 and at the most 130J/g time, Δ T >-0.1299 (Δ H)+62.81,

When Δ H is greater than 130J/g, Δ T >=48 DEG C,

Wherein said CRYSTAF peak utilizes the accumulation polymkeric substance of at least 5% to determine, and if the polymkeric substance being less than 5% has discernible CRYSTAF peak, so CRYSTAF temperature is 30 DEG C; Or

(c) use ethylene/alpha-olefin interpolymers compression molding film measure time 300% strain and 1 circulation with the elastic recovery rate of percentages, Re, and there is density d, in gram/cc, wherein when described ethylene/alpha-olefin interpolymers substantially containing cross-linked phase time described Re and d numerical value meet following relation:

Re > 1481-1629 (d); Or

D () has the molecule fraction of the wash-out between 40 DEG C and 130 DEG C when using TREF classification, it is characterized in that the molar comonomer content height at least 5% of the molar comonomer content of described fraction than the fraction of random ethylene interpretation wash-out between uniform temp suitable with it, wherein said random ethylene interpretation suitable with it has identical comonomer, and its melt index, density and molar comonomer content (based on whole polymkeric substance) differ with each character of described ethylene/alpha-olefin interpolymers ± 10% within; Or

E () has storage modulus G ' (25 DEG C) 25 DEG C time and the storage modulus G ' 100 DEG C time (100 DEG C), wherein G ' (25 DEG C) is about 1: 1 to about 9: 1 with the ratio of G ' (100 DEG C);

Ethylene/alpha-olefin interpolymers also can have:

A () has the molecule fraction of the wash-out between 40 DEG C and 130 DEG C when using TREF classification, the blockiness index (block index) that it is characterized in that this molecule fraction is at least 0.5 at the most about 1, and molecular weight distribution mw/mn is greater than about 1.3; Or

B () average block index is greater than 0 at the most about 1.0, and molecular weight distribution mw/mn is greater than about 1.3.

Polypropylene as np-PO component:

The suitable polymkeric substance based on propylene comprises alfon, propylene terpolymers, and containing the polypropylene reactor multipolymer (reactor copolymer) (RCPP) of the alpha-olefin comonomer of have an appointment 1 ~ about 20wt% ethene or 4 ~ 20 carbon atoms.Homopolymer polypropylene can be isotaxy, syndiotaxy or atactic polypropylene(APP).Propylene terpolymers can be random copolymers or segmented copolymer, or based on the terpolymer of propylene.In another embodiment, can should be coring based on the polymkeric substance of propylene." coring " and similar terms refer to by adding nucleating agent (as purchased from Milliken dibenzyl sorbitol) polymkeric substance of modification.Also other conventional nucleating agents can be used.

Propene polymer can be crystallization, hemicrystalline or unbodied.Crystaline polypropylene polymer has at least 90 % by mole usually, preferably at least 97 % by mole, more preferably the repeating unit deriving from propylene of at least 99 % by mole.

For comprising ethene, 1-butylene, 1-amylene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecylene, 1-dodecylene with the suitable comonomer of propylene polymerization, and 4-methyl-1-pentene, 4-methyl isophthalic acid-hexene, 5-methyl isophthalic acid-hexene, vinyl cyclohexane and vinylbenzene.Preferred comonomer comprises ethene, 1-butylene, 1-hexene and 1-octene, more preferably ethene.Only for the polymkeric substance based on propylene, propylene/alpha-olefins interpretation used in this application is particularly including propylene/ethylene interpretation.

Optionally, the polymkeric substance based on propylene comprises the monomer with at least two double bonds, and this monomer is preferably diene or triolefin.Suitable diene and triolefin comonomer comprise 7-methyl isophthalic acid, 6-octadiene; 3,7-dimethyl-1,6-octadiene; 5,7-dimethyl-1,6-octadiene; 3,7,11-trimethylammonium-1,6,10-sarohornene; 6-methyl isophthalic acid, 5-heptadiene; 1,3-butadiene; 1,6-heptadiene; 1,7-octadiene; 1,8-nonadiene; 1,9-decadiene; 1,10-11 carbon diene; Norbornylene; Tetracyclododecane (tetracyclododecene); Or their mixture; Preferred divinyl; Hexadiene; And octadiene; Most preferably Isosorbide-5-Nitrae-hexadiene; 1,9-decadiene; 4-methyl isophthalic acid, 4-hexadiene; 5-methyl isophthalic acid, 4-hexadiene; Dicyclopentadiene (DCPD); With 5-ethylidene-2-norbornene (ENB).

Other unsaturated comonomers comprise 1,3-butadiene, 1,3-pentadiene, norbornadiene and Dicyclopentadiene (DCPD); C _8-40vinyl aromatic compounds comprises vinylbenzene, o-methyl styrene, a vinyl toluene, p-methylstyrene, Vinylstyrene, vinyl biphenyl (vinylbiphenyl), vinyl naphthalene; With the C of halogen substiuted _8-40vinyl aromatic compounds is as halogenated styrenes and fluorostyrene.

The propylene copolymer of particularly important comprises propylene/ethylene, propylene/1-butene, propylene/1-hexene, propylene/4-methyl-1-pentene, propylene/1-octene, propylene/ethylene/1-butylene, propylene/ethylene/ENB, propylene/ethylene/1-hexene, propylene/ethylene/1-octene, propylene/styrene, and propylene/ethylene/vinylbenzene.

Suitable polypropylene is formed by method of the prior art, such as, and applying unit site catalyst (metallocenes or geometry limit metallocenes) or Ziegler Natta catalyzer.Under the condition of prior art, polypropylene and optional comonomer are as ethene or 'alpha '-olefin monomers, as with disclosed in Publication about Document: people such as Galli, Angew.Macromol.Chem., Vol.120,73 (1984), or the people such as E.P.Moore, Polypropylene Handbook, Hanser Publishers, New York, 1996, specifically at 11-98 page.

The illustrative below but nonrestrictive polyacrylic polymer that can be used for the present composition is: PROFAX ^tmsR-256M, transparent polypropylene copolymer resin, density is 0.90g/cc and MFR is 2g/10min; PROFAX ^tm8623, shock-resistance polypropylene copolymer resin, density is 0.90g/cc and MFR is 1.5g/10min; CATALLOY ^tmblend (in-reactor blend) in the reactor of polypropylene (homopolymer or multipolymer) and one or more propylene-ethylenes or ethylene-propylene copolymer, this blend has density and the MFR of wide region, all can derive from Basell (Elkton, MD); VERSIFY ^tmplastomer and elastomerics, derive from The Dow Chemical Company, is available propylene/ethylene copolymer, and density is 0.86 ~ 0.89g/cc and MFR is 2 ~ 25g/10min; And INSPIRE ^tmd114, the impact copolymers of branching, melt flow index is 0.5dg/min (230 DEG C/2.16kg), and fusing point is 164 DEG C, derives from The Dow Chemical Company.Other polyacrylic polymers comprise KF 6100 homopolymer polypropylene of Shell; KS 4005 polypropylene copolymer of Solvay and KS 300 polypropylene terpolymer of Solvay.

Preferably, the scope based on the melt flow rate (MFR) (MFR) of the polymkeric substance of propylene is 0.01 ~ 1000g/10min, is more preferably 0.1 ~ 500g/10min, most preferably is 1 ~ 100g/10min, measure according to ASTMD 1238 under 230 DEG C/2.16kg.In another embodiment, based on the melt flow rate (MFR) (MFR of the polymkeric substance of propylene, 230 DEG C and 2.16kg) can be 0.1 ~ 150g/10min, be preferably 0.3 ~ 60g/10min, be more preferably 0.8 ~ 40g/10min and most preferably be 0.8 ~ 25g/10min.

The polymkeric substance based on propylene used in the present invention can have any molecular weight distribution (MWD).The polymkeric substance based on propylene with wide or narrow MWD is formed by method of the prior art.The polymkeric substance based on propylene with narrow MWD can be advantageously provided by viscosity breaking or by applying unit site catalyst or by these two kinds of methods manufacture reactor grade purity (non-viscosity breaking) products.

The described polymkeric substance based on propylene can be reactor grade purity, viscosity breaking, branching or (coupled) of coupling, thus provide large coring and crystallization rate.The application uses term " coupling " that the rheology modified polymkeric substance based on propylene is described, makes their during extruding (such as, before being just in time positioned at annular die in an extruder) show the change in molten polymer resistance to flow.And " viscosity breaking " causes splitting of chain (chain-scission), " coupling " causes crosslinked or networking.As the example of coupling, by coupling agent (such as, trinitride) add in the polyacrylic polymer of higher melt flow speed, make after extrusion, the polypropylene polymer composition of generation obtains lower melt flow rate (MFR) more obvious than initial melt flow rate.Preferably for the polypropylene of coupling or branching, the ratio of MFR afterwards and initial MFR is less than or equal to 0.7: 1, is more preferably less than or equals 0.2: 1.

The polymkeric substance based on propylene for suitable branching of the present invention can be bought and obtain, and such as, purchased from Montell North America, trade name is Profax PF-611 and PF-814.Or, suitable branching or the polymkeric substance based on propylene of coupling can be prepared by method of the prior art, such as adopt superoxide or electron beam treatment, as to disclose in Publication about Document: the United States Patent (USP) 5 of the people such as DeNicola, 414,027 (using high energy (ionization) radiation in decompression oxygen atmosphere (reduced oxygen atmosphere)); The EP 0190889 of the Himont electron beam irradiation of isotactic polyprophlene (under the low temperature); United States Patent (USP) 5,464,907 (Akzo Nobel NV); The EP 0754711 (peroxide treatment) of Solvay; With the U.S. Patent application No.09/133 that on August 13rd, 1998 submits to, 576 (azide coupling agents).

Suitable propylene/alpha-olefins interpretation, contains at least 50mol% polypropylene, falls within the scope of the present invention.The suitable poly-polymkeric substance based on propylene comprises VERSIFY ^tmpolymkeric substance (The DowChemical Company) and VISTAMAXX ^tmpolymkeric substance (ExxonMobil Chemical Co.), LICOCENE ^tmpolymkeric substance (Clariant), EASTOFLEX ^tmpolymkeric substance (Eastman ChemicalCo.), REXTAC ^tmpolymkeric substance (Hunstman), and VESTOPLAST ^tmpolymkeric substance (Degussa).Other suitable polymkeric substance comprise propylene/alpha-olefins segmented copolymer and interpretation, and other propylene-based block copolymers known in the art and interpretation.

In another-embodiment, the described polymkeric substance based on propylene is propylene/alpha-olefins interpretation, and its molecular weight distribution is less than or equal to 5, or is less than or equal to 4, or is less than or equal to 3.In another embodiment, the molecular weight distribution of propylene/alpha-olefins interpretation is 1 ~ 5, or 1 ~ 4, or 1 ~ 3.

In another embodiment, when measuring at 230 DEG C/2.16kg according to ASTM D-1238, the melt flow rate (MFR) (MFR) of propylene/alpha-olefins interpretation is less than or equal to 1000g/10min, typically be less than or equal to 500g/10min, more typically be less than or equal to 100g/10min, be even more typically less than or equal to 50g/10min.In another embodiment, when measuring at 230 DEG C/2.16kg according to ASTM D-1238, the melt flow rate (MFR) (MFR) of propylene/alpha-olefins interpretation is more than or equal to 0.01g/10min, is typically greater than or equals 0.1g/10min, being more typically more than or equal to 1g/10min.

In another embodiment, when measuring at 230 DEG C/2.16kg according to ASTM D-1238, the scope of the melt flow rate (MFR) (MFR) of propylene/alpha-olefins interpretation is 0.01 ~ 1000g/10min, typically be 0.01 ~ 500g/10min, be more typically 0.1 ~ 100g/10min, be even more typically 0.1 ~ 50g/10min.

In another embodiment, when using dsc measurement, the percent crystallinity of propylene/alpha-olefins interpretation is less than or equal to 50%, is typically less than or equal to 40%, is more typically less than or equal to 35%.Preferably, the percent crystallinity of these polymkeric substance is 2% ~ 50%.

In another embodiment, the density of propylene/alpha-olefins interpretation is less than or equal to 0.96g/cc, or is less than or equal to 0.93g/cc, or is less than or equal to 0.90g/cc.In another embodiment, the density of propylene/alpha-olefins interpretation is more than or equal to 0.83g/cc, or is more than or equal to 0.84g/cc, or is more than or equal to 0.85g/cc.In another embodiment, the density of propylene/alpha-olefins interpretation is 0.84g/cc ~ 0.93g/cc, or is 0.85g/cc ~ 0.92g/cc.

Propylene copolymer of the present invention generally includes the unit deriving from propylene, and content is at least 60wt% of multipolymer, or at least 80wt% or at least 85wt%.The typical content deriving from the unit of ethene in propylene/ethylene copolymer is at least 0.1wt%, or at least 1wt% or at least 5wt%, the maximum level deriving from the unit of ethene existed in these multipolymers is no more than the 35wt% of multipolymer, or is no more than 30wt% or is no more than 20wt%.When existing, the content deriving from the unit of unsaturated comonomer is generally at least 0.01wt%, or at least 1wt% or at least 5wt%, the typical maximum level deriving from the unit of unsaturated comonomer is no more than the 35wt% of multipolymer usually, or is no more than 30wt% or is no more than 20wt%.The total amount deriving from the unit of ethene and any unsaturated comonomer is no more than the 40wt% of multipolymer usually, or is no more than 30wt% or is no more than 20wt%.

Comprise at least 60wt% that content that propylene and one or more multipolymers of the present invention being different from the unsaturated comonomer of ethene comprise the unit deriving from propylene is usually multipolymer, or at least 70wt% or at least about 80wt%.One or more unsaturated comonomers of described multipolymer account at least 0.1wt% of multipolymer, or at least 1wt% or at least about 3wt%, the maximum level of usual unsaturated comonomer is no more than 40wt% or is no more than 30wt%.

In a preferred embodiment, the heteroaryl ligand catalyst with metallic central is used to obtain these polymkeric substance based on propylene with one or more activators as aikyiaiurnirsoxan beta is combined.In some embodiments, described metal is one or more of hafnium or zirconium.More specifically, in the embodiment of some catalyzer, find for heteroaryl ligand catalyst, use hafnium metal than zirconium metal more preferably.Described catalyzer is the composition comprising part and metal precursor in some embodiments, optionally additionally can comprise activator, the combination of activator or activator component bag (package).

Catalyzer for the preparation of the polymkeric substance based on propylene also comprises the catalyzer containing following material: assistant ligand-hafnium complex, assistant ligand-zirconium complex and optional activator, the polymerization of this catalyst and copolyreaction, particularly wherein monomer is polymerization and the copolyreaction of alkene, diolefine or other unsaturated compounds.The complex compound of the complex compound of zirconium, hafnium, composition can be used.These metal-ligand complexes can be electric neutrality state or electriferous state.Part and metal can change than also, accurately than the characteristic depending on part and metal-ligand complex.One or more metal-ligand complexes can take different forms, and such as, they can be monomer, dimer or higher polymerization-grade.At United States Patent (USP) 6,919, describe suitable catalyst structure and related ligands in 407.

Can the preparation of any method easily based on the polymkeric substance of propylene.In one embodiment, to any suitable design single reaction vessel (such as, stirred pot, endless tube or fluidized-bed) middle input process reagents, namely, (i) propylene, (ii) ethene and/or one or more unsaturated comonomers, (iii) catalyzer, (iv) optional solvent and/or molecular weight regulator (such as, hydrogen).(such as, solution, slurry, gas phase, suspension, high pressure) makes each process reagents contact in the reactor under suitable conditions, forms the polymkeric substance expected, then reclaims the output of reactor for post-reaction treatment.Whole outputs of reactor can be carried out simultaneously reclaim (as in the situation of single pass reactors or batch reactor), or can discharge stream (bleed stream) form reclaim, this discharge stream is only a part for reactive material, a normally less part is (as in the situation of continuous manipulation reactor, wherein output stream is discharged with the speed same with adding Reagent evaluation from reactor, thus polyreaction is kept under steady state conditions, a reactor)." reactive material " refers to the content usually during polyreaction or in the post-reactor of polymerization.Reactive material comprises reactant, solvent (if existence), catalyzer, product and by product.Recovered solvent and unreacted monomer are looped back reaction vessel.Suitable polymerizing condition is described in United States Patent (USP) 6, and 919, in 407.

Urethane based on polydiene or the polyurethane component based on polyglycol:

Urethane based on polydiene of the present invention is thermoplastic and is prepared by least one functionality polydiene.The described urethane based on polyglycol is thermoplastic and is prepared by least one glycol.This functionality polydiene comprises the end that at least one (preferably about two) invest molecule or " isocyanate-reactive group " that invest in molecular side chain.This functional group can be any group forming covalent linkage with isocyanate reaction.This functional group is preferably containing " activated hydrogen atom ", and representative instance is hydroxyl, primary amino, secondary amino group, sulfydryl (sulfhydryl), and their mixture.Term " active hydrogen atom " refers to due to they positions in the molecule thus the active hydrogen atom of display, and this activity exists according to Kohler j.Am. chemical Soc., the Zerewitinoff experimental test described in 49,31-81 (1927), the document is incorporated to herein by reference.In this urethane, the content of unsaturated segment is 1 ~ 95wt%, is preferably 10 ~ 50wt%.In a preferred embodiment, the described polyurethane component based on glycol is prepared by polyalkadiene diol.In another embodiment of the present invention, the described polyurethane component based on glycol is prepared by functionalized poly diene, and this functionalized poly diene contains the isocyanate-reactive group outside hydroxyl-removal.In another embodiment, the described urethane based on glycol is prepared by the glycol of natural origin.Then pd-TPU and np-PO is blended further, such as, foregoing ethylene/alpha-olefin random interpolymers, olefin multi-block interpretation, etc.

In another embodiment, the described urethane based on polyglycol is made up of the glycol of natural origin.The term such as " glycol of natural origin " used in this application, " natural oil polyols " refers to derive from the glycol of agricultural-food as seed oil (as soybean, Sunflower Receptacle, corn and canola).This glycol can contain or not contain diene degree of unsaturation.The composition of seed oil triglyceride level is well-known.Tri-glyceride is the fatty acid ester of glycerine, and its composition depends on the source of oil.Nomenclature used be fat and oil industry in standardized denomination, wherein first illustrate that the carbon number of lipid acid is again with the unsaturated bit number of bracket pair.Representational oil comprises palmitinic acid, stearic acid, oleic acid, linoleic acid plus linolenic acid, or their ester.In order to prepare polyvalent alcohol by these tri-glycerides, the oil of the degree of unsaturation of contained high levels is desired.Oil contains the saturated fatty acid of low relative levels so be acceptable due to them as soya-bean oil, Tower rape oil and sunflower oil, and such as palm wet goods raw material be further purified or in refining situation because high-caliber saturated fatty acid is considered to not spendable.

A kind of method preparing this functionalized poly diene is two-step approach, wherein by the two ends growth conjugated diolefine of anionoid polymerization from bifunctional initiator.The molecular weight of polydiene is controlled by the mol ratio of conjugated diolefine and initiator.In the second step, then use oxyalkylene (such as ethylene oxide or propylene oxide) to carry out end-blocking to end and produce undersaturated glycol.At United States Patent (USP) 4,039, describe this specific method in 593.In the method, excessive oxyalkylene can be added and form short poly-(oxyalkylene) chain in the end of polydiene.These materials within the scope of the invention.

Conjugated diolefine for the preparation of functionality polydiene contains 4 ~ 24 carbon atoms, preferably 4 ~ 8 carbon atoms usually.Typical diene comprises divinyl and isoprene, and typical functionality polydiene is at the polyhutadiene of each end ethylene oxide-capped and polyisoprene.These polydiene per molecules have at least one functional group, and number-average molecular weight (Mn) is generally 500 ~ 10,000 gram/mol (g/mol), and are preferably 500 ~ 5,000g/mol.Functional group is preferably hydroxyl.Two kinds of preferred polyalkadiene diol are polybutadiene diol and polyisoprene glycol, more preferably polybutadiene diol.

In one embodiment, described at least one is formed by non-hydrogenated polyalkadiene diol based on the urethane of polyalkadiene diol.In another embodiment, described at least one is formed by hydrogenated polyalkyldiene diol based on the urethane of polyalkadiene diol.In another embodiment, described at least one is formed by partially hydrogenated polyalkadiene diol based on the urethane of polyalkadiene diol.

Term " hydrogenation " is known in the art, is used in reference to the hydrogenation (reaction of hydrogen and olefin group) of double bond in polyalkadiene diol in this application, and relates to last (hydrogenation) product.Term " hydrogenation " refers to the complete hydrogenation of whole double bond in polyalkadiene diol, or these double bonds are close to complete hydrogenation (be similar to and be greater than 95mol%).Hydrogenation, final product that the double bond that term " partial hydrogenation " is used in reference to significant quantity in wherein polyalkadiene diol (approximate be greater than 5mol%) is not hydrogenated, or both.

The urethane used in enforcement of the present invention is prepared preferably by functionality polydiene and isocyanic ester and the reaction of optional chain extension agent.In " prepolymer " method, one or more functionality polydiene and one or more isocyanate reactions is usually made to form prepolymer.This prepolymer reacts with one or more chain extension agents further.Or urethane can be prepared by the single step reaction (one-shotreaction) of all reactants.The number-average molecular weight of typical urethane is 5,000 ~ 1,000,000g/mol, is more preferably 20,000 ~ 100,000g/mol.

Some examples of polyalkadiene diol, and corresponding urethane is described in in Publication about Document: " the Novel Polybutadiene Diols for Thermoplastic Polyurethanes " of the people such as Pytela, International Polyurethane Conference, PU Lat.Am.2001; With " the Novel Thermoplastic Polyurethanes for Adhesives and Sealants " of the people such as Pytela, Adhesives & Sealant Industry, June 2003, pp.45-51.In WO 99/02603, and describe some examples of some hydrogenated polyalkyldiene diol and corresponding urethane in corresponding European patent EP 0994919B1.As what discuss in these reference, hydrogenation can be carried out by the multiple method set up, comprise: at catalyzer as Raney Nickel, precious metal is as carried out hydrogenation under the existence of platinum, soluble transition metal catalyzer and titanium catalyst, as United States Patent (USP) 5,039, describe in 755.In addition, polymkeric substance can have different diene blocks, and these diene blocks can be selective hydrations, as United States Patent (USP) 5, and 229, describe in 464.

The vulcabond being suitable for the hard segment preparing urethane of the present invention comprises the combination of aromatics, aliphatic series and alicyclic diisocyanate and two or more these compounds.Following formula (I) representative derives from the example of the structural unit of vulcabond (OCN-R-NCO):

Wherein R is alkylidene group, cycloalkylidene or arylidene.The representative example of these vulcabond is found in United States Patent (USP) 4,385, and 133,4,522,975 and 5,167,899.Preferred vulcabond includes but not limited to, 4,4 '-two isocyanato ditan, p-phenylene vulcabond, 1,3-two (isocyanatometyl) hexanaphthene, Isosorbide-5-Nitrae-two isocyanato hexanaphthene, hexamethylene diisocyanate, l,5 naphthylene diisocyanate, 3,3 '-dimethyl-4,4 '-biphenylene diisocyanate, 4,4 '-two isocyanato dicyclohexyl methyl hydride and 2,4 toluene diisocyanate.More preferably 4,4 '-two isocyanato dicyclohexyl methyl hydride and 4,4 '-two isocyanato ditan.Most preferably 4,4 '-two isocyanato ditan.

Vulcabond also comprises aliphatic series and alicyclic isocyanate compound, as 1,6-hexamethylene diisocyanate; Ethylidene diisocyanate; 1-isocyanato-3,5,5-trimethylammonium-1-3-two isocyanato methylcyclohexane; 2,4-and 2,6-hexahydrotoluene vulcabond, and corresponding isomer mixture; 4,4 '-, 2,2 '-and 2,4 '-dicyclohexyl methane diisocyanate, and corresponding isomer mixture.In addition, the present invention can use 1,3-tetramethylene xylene vulcabond.Described isocyanic ester can be selected from organic isocyanate, modified isocyanate, based on the prepolymer of isocyanic ester, and the mixture of two or more these isocyanic ester.

As discussed above, can by substantially mixing all the components in " single stage method " simultaneously, or can progressively add each one-tenth in " prepolymer method " to assign to prepare urethane, wherein these methods can be carried out under the existence of optional additive or not adding under optional additive condition.Urethane forming reactions can carry out with substance law or solution method under the condition of suitable catalyst of adding or not adding promotion isocyanic ester and hydroxyl or other functional group reactions.At United States Patent (USP) 5,864, example prepared by the typical case describing these urethane in 001.

Other main ingredients of the hard segment of urethane of the present invention are at least one chain extension agent well known in the art.As known, when chain extension agent is glycol, the product obtained is thermoplastic polyurethane (TPU).When chain extension agent be diamines or amino alcohol time, the product obtained in technique for thermoplasticity polyureas (TPUU).

The feature of operable chain extension agent is to have two or more in the present invention, preferably has Liang Ge functional group, separately containing " active hydrogen atom ".These functional groups are preferably the form of the mixture of two or more in hydroxyl, primary amino, secondary amino group or these groups.Term " active hydrogen atom " refers to reveal active hydrogen atom, if Kohler is at J.Am.Chemical Soc., described in 49,31-81 (1927) due to its layout in the molecule according to Zerewitinoff test chart.

Chain extension agent can be aliphatic, alicyclic or aromatics, and example is glycol, diamines and amino alcohol.Illustrative difunctional chain extenders is ethylene glycol, glycol ether, propylene glycol, dipropylene glycol, 1,3-PD, 1,3 butylene glycol, BDO, 1,5-PD and other pentanediols, 2-ethyl-1,3-hexylene glycol, 2-ethyl-1,6-hexylene glycol, other 2-ethyl-hexylene glycols, 1,6-hexylene glycol and other hexylene glycols, pure isooctane-1,3-glycol, decanediol, dodecanediol, dihydroxyphenyl propane, Hydrogenated Bisphenol A, Isosorbide-5-Nitrae-cyclohexane diol, Isosorbide-5-Nitrae-bis-(2 hydroxyl-oxethyl)-hexanaphthene, 1,3-CHDM, Isosorbide-5-Nitrae-cyclohexane diol, Isosorbide-5-Nitrae-bis-(2-hydroxyl-oxethyl) benzene, Esterdiol 204 (3-hydroxyl-2,2-Dimethyl-propionic acid-3-hydroxyl-2,2-dimethyl propyl ester, derives from TCI America), N-Mono Methyl Ethanol Amine, N-isopropyl methyl amine, 4-Trans-4-Amino Cyclohexanol, 1，2-diaminoethane (1,2-diaminotheane), 1,3-diaminopropanes, diethylenetriamine, Toluene-2,4-diisocyanate, 4-diamines and toluene-1,6-diamines.Aliphatic cpd preferably containing 2 ~ 8 carbon atoms.If prepare thermoplasticity or solubility urethane, then chain extension agent itself will be two senses.Amine chain extension agent includes but not limited to, quadrol, a carbinolamine and propylene diamine.

The linear chain extenders of general use is conventional glycol, diamines or amino alcohol compound, it is characterized in that, molecular weight is not more than 400g/mol (or dalton).Within a context, " line style " refers to the branching not comprising and come from tertiary carbon.The example of suitable chain extension agent is expressed from the next: HO-(CH ₂) _n-OH; H ₂n-(CH ₂) _n-NH ₂; And H ₂n-(CH ₂) _n-OH, wherein " n " is generally the number of 1 ~ 50.

A kind of common chain extension agent is BDO (" butyleneglycol " or " BDO "), is expressed from the next: HO-CH ₂cH ₂cH ₂cH ₂-OH.Other suitable chain extension agents comprise ethylene glycol; Glycol ether; 1,3-PD; 1,6-hexylene glycol; 1,5-heptanediol; Triethylene glycol; With the combination of two or more these chain extension agents.

Equally it is suitable that Cyclic chain extenders, be generally glycol, diamines or amino alcohol compound, it is characterized in that, molecular weight is not more than 400g/mol.In the context of this application, " ring-type " means that, for ring texture, typical ring texture includes but not limited to, has the structure of 5 ~ 8 rings of hydroxyl-alkyl branches.The example of Cyclic chain extenders is expressed from the next: HO-R-(ring)-R '-OH and HO-R-O-(ring)-O-R '-OH, and wherein R and R ' is the alkyl chain of 1 to 5 carbon, and each ring has 5 ~ 8 ring memberses, is preferably all carbon.In these examples, one or two end-OH can by-NH ₂substitute.Suitable Cyclic chain extenders comprises cyclohexanedimethanol (" CHDM ") and quinhydrones two-2-hydroxyethyl ether (HQEE).The structural unit of preferred Cyclic chain extenders CHDM is expressed from the next: HO-CH ₂-(cyclohexane ring)-CH ₂-OH.

The amount that the amount introducing the chain extension agent in urethane is needed by concrete reactant composition, firmly soft chain segment and the selection being enough to the index providing good mechanical properties (as modulus and tear strength) determine.The polyurethane composition used in enforcement of the present invention can contain 2 ~ 25wt%, preferably 3 ~ 20wt% and the chain extender component of more preferably 4 ~ 18wt%.

When needed, the compound of a small amount of monohydroxy official energy or the compound (being usually called " chain terminator ") of an amino-functional optionally can be used to control molecular weight.The example of this chain terminator is propyl alcohol, butanols, amylalcohol and hexanol.In use, chain terminator, usually to exist on a small quantity, accounts for 0.1 ~ 2wt% of the whole reaction mixture producing polyurethane composition.

As well known to those skilled in the art, the ratio of isocyanic ester and whole functional group determines the Mn of polymkeric substance.In some cases, expect to use isocyanic ester excessive a little.

For line style, high Mn polymkeric substance, the raw material that every bar chain has Liang Ge functional group is desirable.But, raw material can be made to have the functionality of certain limit.Such as, the polydiene with an end functional groups can be used to come the two ends of blocked polyurethane, the middle portion of this urethane is made up of the polyisocyanate chain extending agent part repeated.The polydiene had more than Liang Ge functional group will form branched polymer.If functionality is too high, crosslinked and gelling may become problem, but this can be controlled by processing condition usually.These branched polymers by being presented in some situations the some rheological property expected, as high fondant-strength.

Optionally, in formulation, use the catalyzer promoting or be conducive to be formed carbamate groups.Illustrative useful catalyzer is stannous octoate, dibutyl tin dilaurate, stannous oleate, metatitanic acid tetrabutyl tin, tributyltin chloride, cobalt naphthenate, dibutyl tin oxide, potassium oxide, tin chloride, N, N, N, N '-tetramethyl--1,3-butanediamine, two [2-(N, N-dimethylamino) ethyl] ether, Isosorbide-5-Nitrae-diazabicylo [2.2.2] octane, zirconium chelate, aluminum chelate and Bismuth carbonate.When a catalyst is used, normally used catalytic amount for 0.001wt% and can more be low to moderate 2wt% and Geng Gao, based on the total amount of the composition of formation urethane.

Additive can be used change the character of urethane used in the invention process.Prior art and known in the literature convention amount can add these additives.Usual use additive provides the character of certain desired for urethane, and this additive is various antioxidant, ultraviolet inhibitor, wax, thickening material and filler such as.When a filling material is used, they can be organic or inorganic, but are generally inorganic, such as clay, talcum, calcium carbonate, silica etc.In addition, also can add fibering additive as glass fibre or carbon fiber, thus give specific character.

In a preferred embodiment of the invention, urethane is formed by polyalkadiene diol, isocyanic ester and chain extension agent (preferred aliphatic series chain extension agent).In another embodiment, the described urethane based on polyalkadiene diol is hydrogenation.In another embodiment, isocyanic ester is aliphatic series or alicyclic isocyanate.

In yet, polyalkadiene diol is by having 4 ~ 24 carbon atoms and the conjugated diolefine preferably with 4 ~ 8 carbon atoms is formed.As discussed above, typical diene comprises divinyl and isoprene, and typical polydiene comprises polyhutadiene and polyisoprene, and hydrogenated butadiene polymer and hydrogenated polyisoprene.In a preferred embodiment, these polydiene have at least one in the molecule, more preferably at least two hydroxyls, and usual Mn is 500 ~ 10,000g/mol, is more preferably 1,000 ~ 5,000g/mol and even more preferably 1,500 ~ 3,000g/mol.Preferably this polyalkadiene diol is polybutadiene diol or polyisoprene glycol, is more preferably polybutadiene diol.

In another embodiment, the described urethane based on polyalkadiene diol is formed by the composition comprising following component: 15 ~ 40wt% vulcabond, 50 ~ 75wt% polyalkadiene diol, and 5 ~ 15wt% chain extension agent.In yet, described polyalkadiene diol is polybutadiene diol or polyisoprene glycol, and is preferably polybutadiene diol.In yet, described vulcabond is aliphatic series or aromatic diisocyanate, and more preferably 4,4 '-diphenylmethanediisocyanate.In another embodiment, described vulcabond is aliphatic series or alicyclic diisocyanate.In another embodiment, chain extension agent is aliphatic diol.In another embodiment, the Mn of polyalkadiene diol is 500 ~ 10,000g/mol, is more preferably 1,000 ~ 5,000g/mol, is even more preferably 1,500 ~ 3,000g/mol.In another embodiment, polyalkadiene diol is unhydrided.In another embodiment, polyalkadiene diol is hydrogenation.In another embodiment, polyalkadiene diol is partially hydrogenated.

The polyurethane component of the composition used in enforcement of the present invention can contain the combination of two or more embodiments aforementioned.

Additive can be added, as process oil, slip(ping)agent, anti blocking agent, AO, UV, filler in composition of the present invention.Usually, composition will containing one or more stablizers, and such as antioxidant is as Irganox ^tM1010 and Irgafos ^tM168, both supply by Ciba Specialty Chemicals.The example of hindered phenol antioxidant is 1076 antioxidants, derive from Ciba-GeigyCorp.Usually extrude or before other melting treatment with one or more stabilizer treatment polymkeric substance.Other polymeric additives include but not limited to, ultraviolet absorbers, static inhibitor, pigment, dyestuff, nucleator, filler, slip(ping)agent, fire retardant, softening agent, processing aid, lubricant, stablizer, protection from fumes agent, viscosity control agent and anti blocking agent.Other additives include but not limited to, surface tension modifier, pigment, process oil, wax, whipping agent, anti blocking agent, pore forming material, static inhibitor, releasing agent, whipping agent, pore forming material, static inhibitor, releasing agent, fire retardant, resistance to wear and abrade additive (abrasion and scratch mar additives), antiseptic-germicide, static inhibitor and linking agent.

Composition of the present invention can comprise the combination of the application's two or more embodiments aforesaid.

The polymeric constituent of the present composition can comprise the combination of the application's two or more embodiments aforesaid.

Method of the present invention can comprise the combination of the application's two or more embodiments aforesaid.

Goods of the present invention can comprise the combination of the application's two or more embodiments aforesaid.

Application:

In one embodiment, the present invention is that imparting comprises goods high frequency (HF) weldability of low surface energy (namely nonpolar) material and/or the method for printability.HF-welding performance allows polyolefin sheets or film to be used in the application of such as roof film, fixture (stationary), imitation leather, wherein polyolefine due to cost/performance advantage and recyclable performance be desirable.The material of HF-welding and program are known in the art, are described in US2004/0077791 in general manner.Known method is included in before non-polar polymer carries out HF-welding or brushing, adds zeolite or containing the resin of polar functional group in nonpolar olefinic resin, the resin of such as MAH-grafting, or EAA, EEA, EMA, EBA or EMAA multipolymer.But, when the same terms uses the analog material of similar content, relative to the result that embodiment of the present invention obtains, the weldability that these methods obtain usually and/or printability result poor.

Although can use any non-polar polymer material in enforcement of the present invention, particularly nonpolar olefinic material, described non-polar material is generally based on the homopolymer of ethene or propylene or interpretation or their blend.Method of the present invention comprises non-polar material and a certain amount ofly (is less than 50wt%, is generally 1 ~ 40wt%, preferably 3 ~ 30wt%, more preferably 5 ~ 25wt%) the step that mixes of the urethane based on polyglycol (especially based on the urethane of polyalkadiene diol), based on the gross weight of described non-polar material and described polydiene/TPU.The blend used in enforcement of the present invention can contain one or more additives, such as but not limited to antioxidant, lubricant, filler, fire retardant, oils, linking agent, UV stablizer etc.These additives are used in known manner with known quantity.

In one embodiment, the described urethane based on polydiene and based on polyalkadiene diol urethane by least one aliphatic series or alicyclic diisocyanate formed.

In another embodiment, the present invention is the method for giving the following character of at least one to the goods comprising low-surface-energy material: easily brushing property, printability, colourability, high frequency (HF) weldability and overmolding.In the present embodiment, the urethane based on polydiene or the urethane based on polyglycol are added non-polar material as TPO (TPO), thus promote non-polar material and the adhesion between paint, ink, dyestuff or polar substrates.Due to the resin that urethane is stronger than TPO polarity, therefore the blend of urethane and TPO plays remarkable effect in based on the paint of toluene or ketone or water-based finishes.Compatible with TPO with the glycol of natural origin based on the urethane of polybutadiene diol.By by TPO (such as 8200 polyethylene) and based on polybutadiene diol TPU PRO 7840 (deriving from Sartomer) with 70: 30 or 60: 40 or 50: 50 blended weight ratio mixture, injection-molded item can with the brushing of various paint formulation.Usual use forcing machine and at about 170-190 DEG C and the preferably temperature of about 175-185 DEG C are by the described urethane based on polydiene or the urethane based on polyglycol and np-PO mixture.Typical injection moulding speed is about 20 ~ 100 cubic centimetres of/second (cm ³/ sec), be preferably about 40 ~ 100cm ³/ sec, is more preferably about 80 ~ 100cm ³/ sec.

In another embodiment, the described urethane based on polyglycol is formed by least one aliphatic series or alicyclic diisocyanate.

In another embodiment, the described urethane based on polyglycol comprises at least one glycol, and described glycol is selected from the acid of lower group by one or more or the seed oil tri-glyceride of its ester is made: palmitinic acid, stearic acid, oleic acid, linolic acid and linolenic acid.

Embodiments of the present invention work well to a large amount of paint formulation.The main ingredient of solvent-borne type (solvent-borne) paint and coating is solvent, binding agent, pigment and additive.In paint, the combination of binding agent and solvent is called painting agent carrier.Pigment and additive are dispersed in this carrier.For concrete paint, the amount of often kind of component is in change, but solvent accounts for about 60% of whole formulation usually.Typical solvent comprises toluene, dimethylbenzene, methylethylketone, methyl iso-butyl ketone (MIBK) and water.Binding agent accounts for about 30wt%, and pigment accounts for 7 ~ 8wt%, and additive accounts for 2 ~ 3wt%.Some polymkeric substance used in paint formulation and other additives comprise: acrylic polymers, Synolac, cellulose material are if cellulose acetate butyrate, melamine resin, carbamate resins, vibrin, vinyl acetate resin, urethane resin, polyvalent alcohol, alcohols, inorganic materials are as titanium dioxide (rutile), mica sheet, ferric oxide, silica, aluminium etc.

The composition of these urethane based on polydiene or the urethane based on polyglycol and np-PO also has other purposes.Pass through limiting examples, these compositions facilitate the tack between following material: (i) PU-thermosetting foams and polyolefin elastomer (POE), particularly as the tack coat between extrusion sheet, film material or section bar, (ii) POE and the urethane based on polydiene or the blown polyurethane masking based on polyglycol; (iii) pure TPU and POE, those as described in EP 0468947 of (iv) divinyl rubber and TPU or thermoplastic hard rubber (vulcanate) (TPV); V () is extruding or nylon or another polar plas and crosslinked chlorinatedpolyethylene or EPDM in moulding process, (vi) polypropylene and TPU fiber, such as in carpet, artificial turf etc., (vii) polar filler and non-polar material, such as, electric wire and cable insulant, coating etc., (viii) hot-melt adhesive and polar substrates, (ix) POE and the urethane based on polydiene or the urethane based on polyglycol in moulded parts is as footwear and automobile, and (x) can prepare the water dispersion of various products as film.

In one embodiment, dispersion of the present invention can be prepared by being dispersed in by TPU (based on any non-polar polyol) in the prior polyolefin dispersion prepared, and namely in dispersion process, polyolefin dispersion serves as aqueous phase.

In other embodiments, dispersion can be prepared by the following method:

A) use non-polar polyol as polybutadiene diol or based on the polyester polyol of seed oil and vulcabond polyurethane preformed polymer, or

B) polyurethane prepolymer is dispersed in the aqueous phase comprising polyolefin dispersion and chain extension agent; By adding suitable tensio-active agent or using routine functionalizing method to make prepolymer polyurethane prepolymer can be dispersed in aqueous phase from dispersion, or

C) physical blending polyolefin dispersion and the polyurethane dispersions using non-polar polyol (as polybutadiene diol or the polyvalent alcohol based on seed oil) to prepare, or

D) according to the program of US 2005/0100754, this patent is incorporated to herein as a reference, or

E) pre-composition of the present composition is disperseed, or rear two or more dispersions of mixing.

In one embodiment, often kind of polyurethane component of dispersion is formed separately by aliphatic isocyanate.

The dispersion of these compositions also can be used as the tackifier of the paint of automobile external and inner apolar thermoplastic's parts and thermoset parts.They also can be used as non-polar plastic parts and other molding of toy or extrude the application use of parts and film or the priming paint of printing.

The present invention also provides footwear product, and these goods comprise at least one assembly formed by composition of the present invention.In one embodiment, described goods are selected from the bottom of footwear outer bottom, sole middle level, footwear list, overmolding goods, natural leather article, synthetic leather goods, vamp, laminate, clad products, boots, sandals, overshoes, plastic shoes, and their combination.

Composition of the present invention also may be used for dispersion, as in aqueous based dispersions, as the priming paint of attachment promoting PU glue and leather in the footwear product of alkene; The attachment of fiber coat (with PET, nylon, PP, be rich in the elastomerics of TPO, comprise POE, EPDM or other non-polar elastomer or their combination etc.).

Composition of the present invention may be used in the application of following footwear product: (a) footwear outer bottom, sole middle level and stiffener (stiffeners), thus assemble with the standard polyurethane adhesive composition that shoemaking industry uses at present, b urethane paint that () uses at present with shoemaking industry is coated with brush shoes outer bottom and sole middle level, and at the bottom of (c) multilayer shoe and the polyolefine in sole middle level and the overmolding of two component polyurethane.

The base material that can apply described blend comprises the material of wide region, and also having of existing polarity is nonpolar, such as but not limited to the various matrix materials of polymkeric substance, metal, timber, concrete, glass, pottery and two or more these materials.Or, these material paints can be comprised on the goods of described blend.Method of application comprises brushing, printing, dyeing, overmolding etc., also comprise respective multiple variant as spread-coating, spraying, dip-coating, extrude.Before paint base material, period or afterwards, blend can be cross-linked, can any method easily be cross-linked, such as, adopt superoxide, sulphur, moisture, silane, radiation, heat etc.In one embodiment, by blend paint base material, this blend crosslinked when applying and/or after applying.In order to crosslinked, PO/ contains degree of unsaturation usually based on the polyurethane blends of polydiene, such as, and the PO containing diene and/or non-hydrogenated TPU.

Prepared by membrane structure (thickness is less than 4 mils usually) and sheet structure (thickness is generally 4 mils or larger) the also easy blend by np-PO and the urethane based on polydiene or the urethane based on polyglycol.Film or sheet material can be single or multiple lift, if when multilayer film has three layers or more layers, then at least one internal layer of this film or structure comprises the blend of np-PO and the urethane based on polydiene or the urethane based on polyglycol.This internal layer can serve as the tack coat between polar layer and apolar layer, such as, tack coat between polyester layer and polyolefin layer.Containing giving whole film or good intensity, good shock resistance, puncture and the tear strength of sheet material as the multilayer film of the invention blend of the tack coat between polar layer and apolar layer and sheet structure.

In one embodiment, the described urethane based on polydiene and be preferably based on the urethane of polyalkadiene diol, is formed by least one aliphatic series or alicyclic diisocyanate.

In one embodiment, the described urethane based on polydiene or the urethane based on polyglycol serve as the tack coat between polarity and non-polar material, tack coat particularly between polarity and non-polar polymer material, such as, np-PO is if polyethylene or polyacrylic rete and polar polymer are as the tack coat between the rete of poly(lactic acid) (PLA) or polymeric amide or polyester.D-TPU of the present invention is especially suitable as the tack coat film of polyethylene or polypropylene screen or molded article surface and ethylene/acrylic acid copolymer (EAA) or PLA or polyethylene terephthalate (PET) or molded article surface are combined.Any method coextrusion, extrusion laminate, bonding laminated and/or foam casting or extrude combined can be used to produce these laminated structures, comprise the structure that wherein d-TPU comprises foam.

Suitable vibrin comprises poly(lactic acid), PLA, poly-(glycollide), poly-(butyric ester), poly-(butyric ester-altogether-hydroxyl valerate), poly-(caprolactone), poly-(oxalic acid glycol ester) (poly (ethylene-oxylate)), poly-(1,5-dioxane 2-in heptan ketone) (poly (1,5-dioxepan2-one)), poly-(Isosorbide-5-Nitrae-dioxane 2-in heptan ketone), poly-(to-Er Evil ketone) (poly (p-dioxanone)), poly-(δ-valerolactone), poly-oxalic acid glycol ester (polyethylene (oxylate)), polydiethylene glycol succinate (polyethylene (succinate)), poly-oxalic acid butanediol ester (polybutylene (oxalate)), polybutylene succinate (polybutylene (succinate)), poly-succsinic acid pentadiol ester (polypentamethyl (succinate)), poly-succsinic acid hexylene glycol ester (polyhexamethyl (succinate)), poly-succsinic acid heptanediol ester (polyheptamethyl (succinate)), poly-succsinic acid pentadiol ester (polyoctamethyl (succinate)), poly-(succsinic acid glycol ester-altogether-ethylene glycol adipate(EGA)) (polyethylene (succinate-co-adipate)), poly-(butylene succinate-altogether-tetramethylene adipate) (polybutylene (succinate-co-adipate)), poly-(oxalic acid butanediol ester-altogether-butylene succinate) (polybutylene (oxylate-co-succinate)) and poly-(oxalic acid butanediol ester-altogether-tetramethylene adipate) (polybutylene (oxylate-co-adipate)).Particularly preferably be poly(lactic acid).

Suitable polyolefin layer can comprise one or more polyolefine different in a large number, such as, low density PE, linear, low density PE, high-density PE, ethylene/alpha-olefin copolymer, homopolymer polypropylene, impact-resistant modified polypropylene, random copolymer polypropylene, propylene-ethylene copolymers etc.These polyolefine can be heterogeneous or equal phase polyolefin or both blends.

Rete is made up of film-forming polymer, this film-forming polymer namely there is enough molecular weight thus can by it with curtain coating, blowing, the polymkeric substance that method forms film or sheet material such as to extrude.But molecular weight can not be excessive, to such an extent as to polymers exhibit goes out not to be suitable for the viscosity of film deposition system.In addition, it should be noted that the molecular weight of the polymkeric substance being used to provide different layers can be different, reflect the character that each layer is expected.

No matter that individual layer or the film of multilayer or sheet material all can be formed by ordinary method, comprise casting films coextrusion, blown film coextrusion and two films laminated, one of them film is the structure be made up of multilayered structure, this structure comprises the layer containing np-PO and d-TPU blend, and this layer serves as the tack coat between polyester layer and polyolefin layer.

The invention provides the goods comprising the assembly that at least one is formed by the present composition.In yet, these goods are sheet material, carpet, artificial turf, tackiness agent, line sheath (wire sheath), cable (cable), protective clothing, trolley part, footwear product assembly, coating, foam laminate, automobile case, awning (awning), oilcloth (tarp), roofing construction article, bearing circle, powder coating, powder slush mold goods, consumer durable, handle, handle, computer module, band, embossing (appliqu é), footwear product assembly, travelling belt or timing belt, fabric, pellet (particularly the pellet of softening temperature about 90 DEG C), fiber (comprising the coating of conjugate fiber and fiber), etc..

The present invention also provides moulded product, comprises the first assembly and the second assembly, and wherein said first assembly is formed by the composition comprising polar polymer, and wherein said second assembly is formed by composition of the present invention.In yet, the form of these goods is automobile case, embossing, footwear product assembly, travelling belt, timing belt or consumer durable.

The present invention also provides moulded product, comprises the first assembly and the second assembly, and wherein said first assembly is formed by the composition comprising polar polymer, and wherein said second assembly is formed by composition of the present invention.In yet, the form of these goods is automobile case, embossing, footwear product assembly, travelling belt, timing belt, imitation leather or consumer durable.The invention provides the trolley part comprising the assembly that at least one is formed by the present composition, include but not limited to, dashboard, door-plate, air bag, headrest, armrest, inside roof lining and carpet element are as carpet cushion.

The present invention goes back the footwear product of providing package containing at least one assembly formed by the present composition.In yet, described goods are selected from the bottom of footwear outer bottom, sole middle level, footwear list, overmolding goods, natural leather article, synthetic leather goods, vamp, laminate, clad products, boots, sandals, overshoes, plastic shoes, and their combination.

Specifically, composition of the present invention can be used for following application: the footwear outer bottom that (a) assembles with the standard polyurethane bonder system that shoemaking industry uses at present, sole middle level and footwear stiffener, b urethane paint that () uses at present with shoemaking industry to the coating in footwear outer bottom, sole middle level, and at the bottom of (c) multilayer shoe and the polyolefine in sole middle level and the overmolding of two component polyurethane.In addition, composition of the present invention can be used for other application as automobile application and structure application.Automobile application includes but not limited to manufacture bumper fascia (bumper fascia), vertical panel, soft TPO shell and interior trim.Structure application includes but not limited to manufacture furniture and toy.

" online compounding process " waits term to refer to a kind of technique, normally continuous print, wherein each component of composition be supplied to continuously and be mixed in forcing machine or similar equipment, from described forcing machine or similar equipment, discharge the composition comprising blending ingredients, be optionally processed into further and manufacture goods as film, sheet material or fiber etc.

In one embodiment, the invention provides the method preparing the present composition, the method comprises melting mixing polyolefine and polyurethane component.In yet, each component is mixed simultaneously.In another embodiment, component is mixed in succession with random order.In yet, melting mixing is carried out in an extruder.Also in another embodiment, in " online " compounding process, melting mixing is carried out.

Following examples illustrate the present invention but not bright or secretly limit the present invention.Unless indicated to the contrary, all numbers and percentage ratio are all by weight.

Embodiment

Testing method:

Density measures according to American Society for Testing and Materials (American Society for Testing andMaterials, ASTM) code ASTM D792-00, method B.

Melt index (I ₂) be use ASTM D-1238-04 (version C) under condition 190 DEG C/2.16kg by gram/10 minutes in units of measure.Symbol " I ₁₀" refer to use ASTM D-1238-04 under condition 190 DEG C/10.0kg by gram/10 minutes in units of the melt index measured.Symbol " I ₂₁" refer to use ASTM D-1238-04 under condition 190 DEG C/21.6kg by gram/10 minutes in units of the melt index measured.Polyethylene is measured at 190 DEG C usually, and polypropylene is measured usually 230 DEG C time.MFR refers to melt flow rate (MFR) for the polymkeric substance based on propylene, and utilizes ASTM D-1238 condition 230 DEG C/2.16kg to measure.For except PELLETHANE ^tMthe polymkeric substance based on carbamate (comprising the blend of this base polymer) beyond polymkeric substance, melt index is measured according to ASTM D-1238 condition 190 DEG C/2.16kg.For PELLETHANE ^tM(Pellethane ^tM2102-80A and 2103-70A), melt index is measured according to ASTM D-1238 condition 190 DEG C/8.7kg.

Dsc (DSC) utilizes the TAI model Q1000DSC of equipment RCS cooling attachment and automatic sampler to carry out.Have employed the nitrogen purging air-flow of 50cc/min.Sample is pressed into film in press and in about 175 DEG C of meltings, then air cooling is to room temperature (25 DEG C).Then the material of 3 ~ 10mg is cut into 3mm diameter disk, accurate weighing, is placed in light aluminium dish (about 50mg), then (crimped shut) is closed in crimping.Utilize the thermal behavior of temperature distribution study sample below.Sample quickly heated up to 180 DEG C and keep isothermal 3 minutes, to remove any previous thermal history.Then with 10 DEG C/min speed of cooling sample be cooled to-90 DEG C and keep 3 minutes at-90 DEG C.Thereafter with the rate of heating of 10 DEG C/min, sample is heated to 150 DEG C.Record cooling and the second heating curve.

Ultimate tensile strength and extension at break are measured according to ASTM D-638-03.At 23 DEG C, these two kinds measurements are carried out to cross cutting D638 type IV sample.Melt temperature (Tm) is determined by the second heating curve.Tc (Tc) is determined by the first cooling curve.

Surface tension is measured according to ASTM D2578-04a method B and DIN 53364 (1986).Use ARCOTEC to test ink, it is the fluid that surface tension is determined, and can obtain in the scope of 28 ~ 56mN/m.Test is carried out when room temperature (23 DEG C).

Surface energy utilizes the ARCOTEC that can obtain from Lotar Enterprises ^tMtest ink and test pencil are measured.As each starting point verified, should use and there is intermediate value as the test ink of 38mN/m (dyn/cm) or test pencil.If the line of ink at least keep on the surface of the material 2 seconds constant and be not transformed into drop, then the surface energy of this material is equal to or higher than the surface tension of this fluid.When this situation, impose on this surface by having the test ink/test pencil of next high value as 40mN/m (dyn/cm).This verification must be repeated until capillary next high value reaches such point, at this time the line of fluid in 2 seconds converted contributions from drop.If fluid line forms drop when described starting point (38mN/m (dyn/cm)), so proceed to verify with the test ink/test pencil of lower value, this is common situation for metal.As general restriction, 32mN/m (dyn/cm) is usually mentioned.If surface energy level is lower than this value, it will be poor for so adhering to; It will be good or enough that words higher than this value adhere to.

The hardness properties of sheet material is measured according to ASTM D2240-05.Tensile property is determined according to standard method of test ASTMD638-03.

Melt tension is measured in temperature 190 DEG C selected polymer samples on Goettfert Rheotens melt drawn tester.This Rheotens tester is made up of the wheel of two reverse rotations, and it draws the melting thread mass extruded from kapillary die head constant speed.These wheels are furnished with balance, to measure the stress response of the melt when wheel accelerates.These wheels are accelerated until line material breaks.The power that line material is ruptured is used as melt tension, in a li ox (cN).

RR (V0.1/V100) is by utilizing melt rheology technology to measure at the upper sample for reference of Rheometric Scientific, Inc.ARES (Advanced Rheometric Expansion System) dynamic mechanical spectrometer (DMS).Dynamic frequency pattern is used to carry out sample for reference with the parallel plate handle of the 25mm diameter with 2 millimeters of (mm) gaps at 190 DEG C.Strain rate with 8% and increase to the oscillation rate of 100 radian per seconds from 0.1 gradually, gets 5 data points to the frequency that every ten are analyzed.At 180 DEG C of lower 1 minute of pressure in 20,000psi (137.9 MPas (MPa)), each sample (pellet or bale packing) is compression molded into ¹/ ₈the test plate (panel) of the diameter 3 inches (7.62 centimetres (cm)) that inch (0.049cm) is thick.These test plate (panel)s of quenching are also cooled to room temperature through the time of 1 minute.Cut " 25mm test plate (panel) " from the centre portions of larger test plate (panel).Then the aliquots containig of these 25mm diameters is inserted in the ARES of 190 DEG C, and made it balance 5 minutes before starting test.In whole analytic process, sample is remained in nitrogen atmosphere, thus oxidative degradation is minimized.Arrangement and the process of data is completed with the software package based on ARES2/A5:RSI Orchestrator Windows 95.RR measures the ratio in viscosity versus shear rate curve.

The mooney viscosity MV (the ML 1+4 at 125 DEG C) of interpretation measures according to ASTM D1646-04.Processing stream no-load voltage ratio PRR is calculated by MV and RR according to following formula: PRR=RR+ [mooney viscosity (ML1+4 at 125 DEG C) of 3.82-interpretation] × 0.3.ML refers to Mooney ectotrochanter.This viscometer is Monsanto MV2000 instrument.

Resin:

TPU-1: be-34 DEG C based on the TPU of polybutadiene diol, Tg, proportion@25 DEG C is 0.995, and tensile strength is 1711psi (pound/square inch), I ₂be 1, hard segment contents is 35wt%, and softening temperature is 90 DEG C, and elongation is 559%, derives from Sartomer Company, Inc..

TPU-2: be-35 DEG C based on the TPU of polybutadiene diol, Tg, proportion@25 DEG C is 0.96, and tensile strength is 975psi, I ₂be 1, hard segment contents is 27wt%, and softening temperature is 75 DEG C, and elongation is 560%, derives from Sartomer Company, Inc..

TPU-3: based on the thermoplastic polyurethane of polyhutadiene, density is less than 1g/cm ³, Tg is-35 DEG C and I ₂be 17, derive from Sartomer Company, Inc..

TPU-4:PELLETHANE ^tm2102-80A, Polyurethane Thermoplastic Elastomer (polyester), density is 1.18g/cm ³, MFR is 4g/10min (190 DEG C/8.7kg), is prepared by The Dow Chemical Company.

EAO-1:ENGAGE ^tm7086 or ENR 7086.01, Ethylene/1-butene elastomerics, density is 0.901g/cm ³and I ₂be 0.5, prepared by The Dow Chemical Company.

EAO-2:ENGAGE ^tm7447, Ethylene/1-butene elastomerics, density is 0.865g/cm ³and I ₂be 5, prepared by The Dow Chemical Company.

EAO-3:ENGAGE ^tm7256, Ethylene/1-butene elastomerics, density is 0.885g/cm ³and I ₂be 2.0, prepared by The Dow Chemical Company.

EAO-4:ENGAGE ^tm8440, ethene/1-octene elastomer, density is 0.897g/cm ³and I ₂be 1.6, prepared by The Dow Chemical Company.

EAO-5:ENGAGE ^tm8200, ethene/1-octene elastomer, density is 0.87g/cm ³and I ₂be 5, prepared by The Dow Chemical Company.

EAO-6:AFFINITY ^tm1880G, ethylene/alpha-olefin plastomer, density is 0.902g/cm ³and I ₂be 1, prepared by The Dow Chemical Company.

EAO-7:ENGAGE ^tm8407, ethylene/octene, density is 0.87g/cm ³and I ₂be 30, prepared by The Dow Chemical Company.

EAO-8:LDPE 662i, low density ethylene polymer, density is 0.919g/cm ³and I ₂be 0.47, prepared by The Dow Chemical Company.

PE-1: propylene-ethylene copolymers, density is 0.858g/cm ³and MFR is 2, prepared by The DowChemical Company.

PE-2: propylene-ethylene copolymers, density is 0.876g/cm ³and MFR is 8, prepared by The DowChemical Company.

PE-3: propylene-ethylene copolymers, density is 0.888g/cm ³and MFR is 2, prepared by The DowChemical Company.

PE-4: propylene-ethylene copolymers, density is 0.866g/cm ³and MFR is 8, prepared by The DowChemical Company.

PE-5: propylene-ethylene copolymers, density is 0.866g/cm ³and MFR is 2, prepared by The DowChemical Company.

PE-6 propylene-ethylene copolymers, density is 0.866g/cm ³and MFR is 25, prepared by The DowChemical Company.

OBC-1: ethylene/vinyl-octene segmented copolymer, overall consistency is 0.877g/cm ³, total I ₂be 1, (density is 0.854g/cm to have 70% soft-block chain members (block split) ³(density is 0.935g/cm to)/30% hard block segment ³, I ₂for 1g/10min), prepared by The Dow Chemical Company.

OBC-2: ethylene/vinyl-octene segmented copolymer, overall consistency is 0.877g/cm ³, total I ₂be 1, (density is 0.855g/cm to have 85% soft-block chain members ³(density is 0.935g/cm to the hard soft-block chain members of)/15% ³, I ₂for 5.2g/10min), prepared by The Dow Chemical Company.

FP-1:AMPLIFY ^tmeA 100, ethylene-ethylacrylate (EEA) multipolymer, density is 0.930g/cm ³and I ₂be 1.3, there is 15% ethyl acrylate copolymers monomer, prepared by The Dow ChemicalCompany.

FP-2:AMPLIFY ^tmeA 101, ethylene-ethylacrylate (EEA) multipolymer, density is 0.931g/cm ³and I ₂be 6, there is 18.5% ethyl acrylate copolymers monomer, prepared by The Dow ChemicalCompany.

GEAO-1:ENGAGE ^tm8407, use MAH grafting, ethene/1-octene copolymer, before 0.74wt% maleic anhydride graft, density is 0.87g/cm ³and I ₂be 30, prepared by The Dow ChemicalCompany.

Embodiment 1: radiowelding

Preparation contains the sheet material of the various blends of alkene and polar polymer and tests HF weldability.The composition of blend and the result of weldability test is have recorded in table Ex.1.Use twin screw extruder mixture blend A and B and granulation.The temperature of forcing machine is set as 130/160/170/175/175/170 DEG C, and screw speed is 50rpm.Then to use use for laboratory twin-roll plastic mixing mill, under the bowl temperature of 140 DEG C, blend A and B melting are made the thick film of 0.3mm.Use Haake mixing machine at 160 DEG C by blend C, D and E mixture 5 minutes.Plasticator is used to make film by through blended polymkeric substance.Be placed in by 7.5g blend polymer between two molding steel plates, wherein two polyester chipss are by molded plate and spacing samples.Plasticator is set as 180 DEG C, then under the power of 10000lbf, compresses this blend polymer 1 minute, obtain about 300-350 μm of thick film.

It is 4 seconds that welding condition comprises weld time, setting power be 80% (that is, the power input of impulse sealer, this impulse sealer derives from Sanden Electronic Equipment, model is KS-4000T), the oscillation frequency of machine is 27.12MHz.

Table Ex.1

comprise sheet material and the HF-weldability test result of alkene and polar polymer blend

Composition/embodiment	A	B	C	D	E	F	G
								TPU-1	10	25	0	0	0
EAO-1	90	75
								Olefin elastomer 2			100	70	70
Olefin elastomer 3						90
								Olefin elastomer 4							90
FP-1				30
								FP-2					30
Advera 401PS (zeolite)						10	10
								Test result-HF-weldability	Well	Well	Lost efficacy	Lost efficacy	Lost efficacy	Lost efficacy	Lost efficacy

60/40 blend of olefin elastomer 2:PE-1 and PE-2.

40/30/30 blend of olefin elastomer 3:EAO-2, EAO-3 and EAO-4.

30/20/50 blend of olefin elastomer 4:PE-3, PE-4 and EAO-2.

ADVERA 401PS, hydrated sodium aluminosilicate zeolite (aluminosilicate hydrated zeolitesodium), powder, is prepared by PQ Corporation of Valley Forge, PA.

Comprise the calendered film of 10wt%TPU-1 and 90wt%EAO-1 or sheet material and comprise consistency and the HF-weldability that the calendered film of 25wt%TPU-1 and 75wt%EAO-1 or sheet material show composition component respectively.On the contrary, there is no the film (such as sample C) of polar compound, or the weldability of the film (sample D and E) with EEA or the film with zeolite polar compound (sample F and G) is not ideal.

Embodiment 2: easily brushing property

Werner-Pfleider ZSK-25 compounding extruder adopts the blend of 170 DEG C of stable temperature distribution preparation EAO-5 and TPU-3 pellets.Pellet sends into forcing machine via independently loss of weight (loss-in-weight) feeder.Blend formulation is recorded in table Ex.2-1.

Table Ex.2-1

the composition of the injection-molded plaques selected

Sample composition
	63∶37 EAO-5∶TPU-3
75∶25 EAO-5∶TPU-3
	85∶15 EAO-5∶TPU-3

By formulation on Cincinnati-Molder, under the injection speed of the melt temperatures of 408 °F, the die temperature of 80 °F and 2 inch per seconds, be injected into the test piece (plaque) of 20 mil thick.Then these test pieces are used in Fig. 2 to describe the different paints determined and carry out brushing and make its dried overnight.

Then use Paul N.Gardner Company, the model of Inc is that the paint tack test tool set of P.A.T. carries out grid test to test piece.Except multiple tooth blade, this tool set contains all instruments and the material that the paint on the smooth homogeneous surface of paint are carried out to tack test needs according to the method B of ASTM D-3359 and DIN standard No.53151.With Fig. 1, result is classified.Grid pattern will be drawn and be cut into test piece.Enough power is used to blade, thus cuts off coating completely, then use band (Permacel#99 tack calibration tape, derives from Permacel, a Nitto Denko Company) to peel off the paint drawn in grid pattern.If band can peel off many paints (Fig. 1 is categorized as 2 or lower), mean that the tack between paint and base material is poor.But, if band can not peel off paint, then show that tack is good.Table Ex.2-2 have recorded the association between the classification of Fig. 1 and the painting dosage (in wt%) of removing.

Table Ex.2-2

association between the classification of Fig. 1 and the painting dosage (by weight percentage) of removing

Classification	The paint (wt%) of removing
		0	＞65
1	35-65
		2	15-35
3	5-15
		4	＜5
5	0

The injection-molded plaques of brushing after Fig. 2 is presented at and carries out drawing the test of lattice paint tack.In fig. 2, the test piece on the right is for igelite, timber, metal, glass and pottery smooth modification FUSION plastics paint (flat finish FUSION plastic paint) is brushed.The solvent of this paint comprises ketone, toluene, petroleum naphtha, dimethylbenzene and butoxy ethanol.Test piece Anita ' the s of on the left ^tmthe water-based acrylic class paint brushing of 11304.

Be clear that from Fig. 2,63: 37 blends of EAO-5 and TPU-3 have best tack to the paint used in this research.The tack of 85: 15 blend display differences, and 75/25 blend shows medium tack.

Also adopt the subject diagram of identical program, ASTM D-3359 and above-mentioned Fig. 1 to measure other blends multiple, replace injection molded plaques unlike with extrusion sheet.Result is have recorded in table Ex.2-3.All grades lower than 3 all think inefficacy, and grade 3,4 or 5 thinks qualified.

Embodiment display pd-TPU amount in table Ex.2-3 (extrusion sheet) and table Ex.3 (injection molded plaques) and temperature are on the impact obtaining good paint tack.Those skilled in the art can change processing temperature to obtain the result of expectation.As display in these tables, pd-TPU amount lower in formulation makes paint tack decline usually.But under some processing conditionss, coating material composition (be not limited in showing display those) lower pd-TPU amount also have passed the test of paint tack.

Use the comparative example display of the TPU-4 of table 2.3, although passing through disclosed by prior art uses the graft resin with functional group can obtain consistency between polarity polarity TPU-4 and np-PO, there is no paint tack.

¹low ' s plastic Enamel (containing acetone and dimethylbenzene)

²permanent acrylic's class water-based finishes of Anita

³model Master Custom Spray Enamel, derives from Testor Corp, the trade mark 2913

¹low ' s plastic Enamel (containing acetone and dimethylbenzene)

²permanent acrylic's class water-based finishes of Anita

¹low ' s plastic Enamel (containing acetone and dimethylbenzene)

²permanent acrylic's class water-based finishes of Anita

N/M-does not measure

Embodiment 3: easily brushing property-injection moulding

Table Ex.3 have recorded the easy brushing property also using the various injection molded plaques of the paint brushing of recording subsequently be made up of recorded blend.Adopt the subject diagram test paint of identical program, ASTM D-3359 and above-mentioned Fig. 1 and the tack of test piece.

All grades lower than 3 all think inefficacy, and grade 3,4 or 5 thinks qualified.

Embodiment 4: overmolding

The half of the nylon Capron tensile bar of injection moulding 125 mil thick under the condition shown in table Ex.4-1.Then putting back in mould by these nylon tensile bar, is second half of tensile bar by the blend overmolding of EAO-1 and TPU-1.

Table Ex.4-1

the condition of the tensile bar of molding and its mixed thing of overmolding Nylon and EAO-1/TPU-1 respectively

These tensile bar of towing on Instron machine.Table Ex.4-2 shows the ultimate tensile strength (psi) and elongation limit (%) that 10 stretching overmoldings examination bars measure under two conditions.The first condition is injection speed is 40 cubic centimetres/second (cc/s).The second condition is injection speed is 100cc/s.

Table Ex.4-2

injection speed be 40 and 100cc/s time overmolding tensile bar ultimate tensile strength

As what can see in table Ex.4-2, when injection speed is 40cc/s, overmolding product are in central segment, and when injection speed is 100cc/s, overmolding product keep complete, but lose efficacy in the TPU-1/EAO-1 end that tensile bar is softer.This confirms by melt blending EAO-1 and compatible thermoplastic polyurethane, and non-polar polyolefinic such as EAO-1 and polar substrates such as nylon have tack.

Table Ex.4-3 have recorded be made up of recorded blend and subsequently with the overmolding of the various injection molded plaques of recorded overlapping material injection moulding.

Embodiment 5A: blown film (4-5 mil)

Use single screw extrusion machine to extrude monolayer blown film on research production line, wherein zone temperatures is 183-193 DEG C, and melt temperature is 193 DEG C.The thickness of the film of blowing is 4-5 mil, and horizontal line (flat-line) width is 4.25 inches.Then brushing film and the same program using embodiment 2 to record test tack.Outcome record is in table Ex.5A.

Table Ex.5A

the easy brushing property of 4-5 mil blown film

	Temperature (DEG C)	Paint tack	Surface energy (dyne/cm)
				63∶37 OBC-1∶TPU-1	193	4	36
50∶50 PE-5∶TPU-1	193	4	36

Embodiment 5B: blown film (1.8 and 1.2 mil)

Use single screw extrusion machine to extrude separately two monolayer blown films on roomy experiment production line (pilot line), wherein zone temperatures is 188-193 DEG C, and melt temperature is 193 DEG C.The thickness of the first blown film (sample No.5B-1) is 1.84 mils, and the thickness of the second blown film (sample No.5B-2) is 1.19 mils.Two films are extruded by the blend of (i) and (ii): the pellet (containing 63wt%EAO-1 and 37wt%TPU-1 blend) of (i) 98wt%, (ii) 2wt% derives from the blue masterbatch (concentrate) of Americhem.Then, according to stretchiness, toughness and the modulus of ASTM D-882 test membrane vertical and horizontal (being respectively MD and TD direction), according to ASTM D-1922 at MD and TD both direction test Elmendorf Tear, test stripping strength according to ASTM F-88.Further define density and the surface energy of film.Outcome record is in table Ex.5B.

Table Ex.5B

the character of the blown film of 1.84 and 1.19 mils and test result

^*when 30psi, 121 DEG C in conjunction with 10 seconds time, stripping test in film rupture, illustrate to define with nylon fabrics and combine closely.

Embodiment 6A: water dispersion

Water dispersion is prepared by the blend of multiple EAO-5 and TPU-3.This dispersion of following preparation: blend described in melt blending and water in an extruder, obtains stable, the uniform dispersion that mean particle size is 300nm.The solids content of dispersion is 35 ~ 50wt%.Add UNICID ^tm350 tensio-active agents/stablizer is (by solid 6wt%; It is a kind of synthesis C being converted into sylvite ₂₆carboxylic acid, and derive from Baker Petrolite) as dispersion agent.By extra EAO-5 is added there is lower EAO-5 percentage ratio dispersion in, preparation comprises the sample of the blend with higher EAO-5 percentage ratio.Then, using polypropylene (BOPP) film of dispersion as casting films paint diaxial orientation, and surface measurements energy.Table Ex.6A have recorded result.

Table Ex.6A

by the surface energy of EAO-5/TPU-3 water dispersion film of curtain coating in BOPP film

EAO-5/TPU-E (w/w)	Surface energy (dyne/cm)
		63/37	48
75/25	48
		80/20	36
85/15	36
		BOPP film	＜30

Embodiment 6B: water dispersion

The dispersion of the present embodiment comprises 51.4wt% solid, 3wt%UNICID ^tm350 tensio-active agents/stablizer, He Shui.Described solid comprises 63wt% ethene/1-octene copolymer (I ₂be 5 and density is 0.87g/cc) and 37wt%TPU-3, and polydispersity index is 5.46.The pH of described dispersion is 10.9, and viscosity (cp) is 30, and mean particle size is 0.63 micron, and the tensio-active agent of 90% is neutralized.Dispersion containing wetting agent, that is, does not contribute to the compound that dispersion flows and sprawls on base material.With painting brush by dispersion paint base material, then make it dry at the temperature of about 70 DEG C.To be not easy the film of drying with hand from base material higher slice, then to draw the conclusion that there is abundant tack between base material and film if observed after several minutes.

Outcome record below.First base material is the extrusion sheet of peroxide modified (slightly crosslinked) ethene/1-octene copolymer.Ensuing two kinds of base materials are PET film and fabric respectively, and two kinds of remaining base materials are the molding test piece of rigid thermoplastic polyurethane and PET respectively.

base material result

The EO multipolymer that X-is cross-linked is not stratified

PET film is not stratified

PET fabric is not stratified

Rigid olyurethane is not stratified

PET is not stratified

Embodiment 6C: water dispersion

In twin screw extruder at 165 DEG C with speed melt kneading 100 weight part EAO-5, the 58.7 weight part TPU-3 of 9.4kg/hr and 4.9 weight part UNICID ^tm350 tensio-active agents/stablizer.10.6wt% potassium hydroxide aqueous solution is inputted continuously on the resin of melt kneading with the speed of 0.3kg/hr (that is, speed is the 26wt% of entire mixture) at the downstream injection port of forcing machine.Subsequently, before leaving forcing machine, the extra water of this water dispersion is diluted with the speed of 8.0kg/hr.In order to dilute the dispersion obtained further, after mixture leaves forcing machine, add extra water with the speed of 1.2kg/hr.The solids content of the water dispersion obtained is 50.6wt%, pH is 11.5.When being measured by CoulterLS230 particle analyzer, the average volume diameter of the polymer phase of dispersion is 1.17 microns, and size-grade distribution (Dv/Dn) is 2.35.

Embodiment 6D: water dispersion

Water dispersion is prepared by the various blends of EAO-5, TPU-3, TPU-1 and these materials.For blend, polymeric aggregate is delivered directly in forcing machine with the ratio showing Ex.6D record together with water, obtains having stable, the uniform dispersion being recorded in mean particle size in table Ex.6D and solids content equally.As shown Ex.6D record, the solids content of dispersion is 35 ~ 50wt%.Add UNICID ^tm350 tensio-active agents/stablizer is as dispersion agent.

Then, will dispersion paint OBC-2 test piece, 85 DEG C of heating with flash distillation water outlet, obtain covering the dispersion film of test piece with painting brush.Surface measurements energy after making film cool more than 10 minutes.By Lowe ' s the test piece of this priming of Plastic Enamel paint paint, and make it drying at room temperature 24 hours.These test pieces are carried out draw the test of lattice paint tack and put on grade as previously mentioned.

Table Ex.6D

the character of the water dispersion selected, surface energy and stroke lattice grade

Sample granularity polydispersity index solids content surface energy draws lattice paint grade

(μm) (％) (dyne/cm)

TPU-3 1.24 2.33 48.4 41 0

TPU-1 0.67 1.39 50.5 44 0

EAO-5 0.56 1.34 50.5 32 0

63∶37 1.17 2.35 50.6 41 4

EAO-5∶TPU-3

80∶20 1.06 2.56 50.5 41 3

EAO-5∶TPU-3

63∶37 0.88 5.24 50.5 41 4

EAO-5∶TPU-1

80∶20 1.92 4.19 51.3 41 3

EAO-5∶TPU-1

Embodiment 6E: water dispersion

The ratio of EAO-5 and TPU TPU-3, TPU-1 and EAO-5 dispersion of table Ex.6D record recorded with generation table Ex.6E carries out physical blending.By being placed on mixing platform and carrying out physical mixed in pouring with magnetic stirring bar two kinds of dispersions into 500ml beaker with proper ratio.Carry out stirring 30 minutes.Then by these dispersion paint OBC-test pieces and 85 DEG C of flash distillations 10 minutes, film is formed.Carry out surface energy as embodiment 6D and draw the test of lattice paint tack.

Table Ex.6E

the surface energy of the dispersion selected and stroke lattice paint grade

Sample	Surface energy (dyne/cm)	Draw lattice paint grade
			63∶37 EAO-5∶TPU-3	35	4
80∶20 EAO-5∶TPU-3	35	3
			63∶37 EAO-5∶TPU-1	38	4
80∶20 EAO-5∶TPU-1	38	3

Embodiment 7: the sheet material of online mixture

Use Egan 4.5-inch (30/1 length/diameter (L/d) ratio), compression ratio is two sections of singe screw (Maddock-type) of 3: 1, this singe screw is connected to Kenics static mixer, 114cc Gard pump, with 500lb/hr by there is choke (restrictor bar) and the 62-inch sheet die head (heavy gauge sheet die) of die lip (flex lip) of living, thus inner blended (in-blend) 61.74wt%EAO-1 and 36.26wt%TPU-1 and 2%Americhem colour masterbatch (color concentrate) (53170-H1-101, very dark cashmere (cashmere)).Mixing EAO-1 and TPU-1 pellet, then by the air conveying feeding part being fed to screw rod.Blend is extruded into the sheet material that 40 mils (0.04in.) are thick.

Processing condition comprise barrel zone temperature, and (section 1 is 152 DEG C (305 °F), section 2 is 171 DEG C (340 °F), section 3 and 4 is 193 DEG C (380 °F), section 5 is 204 DEG C (400 °F)), melt temperature, mixing tank and screen temperature are 199 DEG C (390 °F).The die head temperature of section 1 ~ 5 is 204 DEG C (400 °F), and forcing machine amperage is 227, and exporting percentage ratio is 32, and pump temperature is 204 DEG C (400 °F), and pump speed is 24.5rpm.

For comparison purpose, in length-to-diameter ratio (L/d) be 48/1 WP-ZSK-25 twin screw co-rotating twin screw extruder on premixed EAO-1 (61.74wt%) and TPU-1 (36.26wt%) and 2wt%Americhem colour masterbatch (with identical above), line material cuts into pellet, in 70 DEG C of dryings 4 hours in vacuum drying oven, be then extruded into the sheet material that 40 mils (0.04 inch) are thick.

Premixed processing condition comprise barrel zone temperature, namely section 1 is 140 DEG C (285 °F), section 2 ~ 5 is 171 DEG C (340 °F), section 6 and 7 is 188 DEG C (370 °F), section 8 is 191 DEG C (375 °F), and melt temperature is 227 DEG C (440 °F).

Sheet production line extrusion condition comprises Killion 1.75 in. with Davis Standard Barrier feed worm, the single screw extrusion machine of 24: 1L/D, this feed worm comprises bulkhead transition part (barrier transition section) and Spiral Maddock mixing portion.The 24 Ultraflex H75 die heads of Extrusion Dies Inc. are inputted with 50lbs/hr.Barrel zone temperature comprises: section 1 is 177 DEG C (350 °F), section 2 is 191 DEG C (375 °F), section 3 is 199 DEG C (390 °F), Die-head connecting sleeve (adaptor) is 210 DEG C (410 °F), and die head district 1 ~ 3 is 199 DEG C (390 °F).Pump speed is 75rpm, and die pressure is 1000psi.The character of two kinds of sheet materials selections is have recorded at table Ex.7.

Table Ex.7

the comparison of the extrusion sheet of online mixture and the selected character of premixed extrusion sheet

Physical properties	Online mixture	Premixed
			Sheet density, g/cc	0.945	0.943
Tensile strength (MD), MPa	13.8	7.5
			Elongation % (MD)	540	450
Surface tension (dyne/cm)	38	39

As the data presentation of table Ex.7, when online mixture and premixed compare time, composition of the present invention provides suitable or better result.This so be interpreted as, by avoiding obtaining more effective processing to the needs of premixed step.

Although describe the present invention by explanation above with considerable details, this details is the restriction should do not regarded as to illustrate appended claims.All United States Patent (USP)s, U.S. Patent application and U.S. Patent Application Publication are incorporated to herein as a reference.

Claims

1. goods, comprise the first assembly and the second assembly, described first assembly comprises polar material, and described second assembly comprises the blend of the ethylene/alpha-olefin random interpolymers of 55 ~ 77wt% and the urethane based on polyalkadiene diol (pd-TPU) of 23 ~ 45wt%, the molecular weight distribution of wherein said ethylene/alpha-olefin random interpolymers is 1.5 ~ 4.5, melt index I ₂for being more than or equal to 0.1 gram/10 minutes and being less than or equal to 50 grams/10 minutes, ASTM D-1238-04 is used to measure under condition 190 DEG C/2.16kg.

2. the goods of claim 1, wherein said ethylene/alpha-olefin random interpolymers is line style substantially.

3. the goods of claim 1, the diisocyanate component of the wherein said urethane based on polyalkadiene diol is aliphatic vulcabond.

4. the goods of claim 2, the diol component of the wherein said urethane based on polyalkadiene diol is at least part of hydrogenation, and the diisocyanate component of the described urethane based on polyalkadiene diol is aliphatic vulcabond.

5. the goods of any one of claim 1-4, wherein said goods are moulded parts.

6. the goods of claim 5, wherein said first assembly is base material, and described second assembly is veneer.

7. the goods of claim 5, wherein said second assembly is base material, and described first assembly is veneer.

8. the goods of claim 6 or 7, wherein said first assembly comprises at least one in plastics, metal, timber, stone material, cement and pottery.

9. the goods of any one of claim 1-4, wherein said goods are the laminated structures comprising the first layer and the second layer, and the first layer forms described first assembly and the second layer forms described second assembly.

10. the laminated structure of claim 9, wherein said the first layer is foam or fabric.

The goods of 11. any one of claim 1-4, wherein said goods are painted substrate.

The painted substrate of 12. claims 11, wherein said base material comprises described second assembly, and described paint comprises described first assembly.

The painted substrate of 13. claims 12, wherein paint comprises at least one in acrylic polymers, Synolac, cellulose material, melamine resin, urethane resin, carbamate resins, vibrin, vinyl acetate resin, alcohol.

The painted substrate of 14. claims 13, wherein said alcohol is selected from polyvalent alcohol.

The painted substrate of 15. claims 13, wherein said paint is water-based finishes or organic solvent based paint.

16. water dispersions, it comprises water and the solid based on total dispersion weight 30 ~ 70wt%, described solid comprises the blend of ethylene/alpha-olefin random interpolymers and the urethane based on polyalkadiene diol, this blend comprises the ethylene/alpha-olefin random interpolymers of 55 ~ 77wt% and the urethane based on polyalkadiene diol of 23 ~ 45wt%, based on the gross weight of ethylene/alpha-olefin random interpolymers and the urethane based on polyalkadiene diol, the mean particle size of described solid is 0.4 ~ 2.5 micron, the molecular weight distribution of wherein said ethylene/alpha-olefin random interpolymers is 1.5 ~ 4.5, melt index I ₂for being more than or equal to 0.1 gram/10 minutes and being less than or equal to 50 grams/10 minutes, ASTM D-1238-04 is used to measure under condition 190 DEG C/2.16kg.

The dispersion of 17. claims 16, wherein said ethylene/alpha-olefin random interpolymers is line style substantially.

The dispersion of 18. claims 16, the diisocyanate component of the wherein said urethane based on polyalkadiene diol is aliphatic vulcabond.

The dispersion of 19. claims 17, the diol component of the wherein said urethane based on polyalkadiene diol is at least part of hydrogenation, and the diisocyanate component of the described urethane based on polyalkadiene diol is aliphatic vulcabond.

20. blends, it comprises: (i) 55 ~ 77wt% ethylene multi-block copolymer, and (ii) 23 ~ 45wt% is based on the urethane of polyalkadiene diol, based on the gross weight of ethylene multi-block copolymer and the urethane based on polyalkadiene diol, the weight-average molecular weight of wherein said ethylene multi-block copolymer is 10,000 to 2,500,000, polydispersity index is less than 3.5, its ethylene content is 65 ~ 75%, and diene content is 0 ~ 6%, and alpha-olefin content is 20 ~ 35%.

The blend of 21. claims 20, the molecular weight distribution of ethylene multi-block copolymer described in it is 1.7 ~ 3.5.

The blend of 22. claims 21, the diisocyanate component of the wherein said urethane based on polyalkadiene diol is aliphatic vulcabond.

The blend of 23. claims 21, the diol component of the wherein said urethane based on polyalkadiene diol is at least part of hydrogenation, and is aliphatic vulcabond based on the diisocyanate component of the urethane of polyalkadiene diol.