CN101568418A - Aqueous dispersions disposed on glass-based fibers and glass-containing substrates - Google Patents

Abstract

An article including at least one layer of a compound disposed on at least a portion of a glass-containing substrate, wherein the compound includes a polyolefin having a deformation temperature of less than 110 DEG C and a dispersion stabilizing agent, wherein the compound imparts a modified property to the substrate, and wherein the substrate is formable. Other embodiments include a compound in contact with a portion of a glass-containing substrate, such as glass-containing or glass-based articles and fibers, wherein the compound at the time of contacting included an aqueous dispersion having(a) a polyolefin having a deformation temperature of less than 110 DEG C, (b) a dispersion stabilizing agent; and (c) water, wherein the compound imparts a modified property to the substrate, and whe rein the substrate is formable.

Description

Place fiber and the suprabasil aqueous dispersion that contains glass based on glass

Background of invention

Invention field

Present invention relates in general to aqueous dispersion and dispersion composite (dispersion compound).

Background technology

The thermoplastic resin that long fibre strengthens has been widely used for various industrial products assemblies, and this is because they have good mechanical strength, hear resistance, and formability.Yet be difficult to produce the thermoplastic resin that long fibre strengthens by kneading short fiber and thermoplastic resin in extruder, the thermoplastic resin that known long fibre strengthens can be prepared by the thermoplastic concentrate that long fibre strengthens.

The thermoplastic concentrate that known long fibre strengthens prepares by fusion formed by extrusion and tension method.In the fusion formed by extrusion and tension, by thermoplastic melt, and the become matrix polymer or the vector resin that are melted are wetting with fibre bundle (fiber strand) tractive.Aftershaping or release method (Post forming or strippingmeans) are used for setting consistent fiber content.

But fiber content does not exceed 50 to 70wt% scopes of concentrate weight usually.Because thermoplastic melt has high viscosity, in the process of formed by extrusion and tension, the incomplete infiltration of resin to fiber may take place.Fully permeated by melt in order to obtain fibre bundle, the formed by extrusion and tension method uses very low-molecular-weight thermoplastic as vector resin usually.But, can produce adverse effect to mechanical strength, hear resistance and the formability of the thermoplastic resin that does not strengthen that added concentrate even the low molecular weight thermoplastic vector resin of low content is present in the thermoplastic concentrate that long fibre strengthens also.

At United States Patent (USP) 4,626,306,4,680,224,5,725,710,5,888,580 and 6,045, in the method described in 912, use the liquid polymer powder dispersion to be used for the impregnation of fibers bundle.With thermoplastic powder, normally low-molecular-weight thermoplastic, being applied to is along the longitudinal movement passes the fibre bundle of powder dispersion; For example decentralized medium, solvent (preferred water) are removed from fibre bundle, made thermoplastic molten then, and for example compound is solidified by backing by heating.

In these methods, the powder deposition of constant basis is moving through on the fibre bundle of dispersion bath and can have problems.The polymer content of compound depends on the solid content of dispersion bath.Fibre bundle directly near concentration can fluctuate and can be not always accurately corresponding to the mean concentration of the dispersion that provides subsequently.Many remedial measures have been proposed, as guider (guide), fibre bundle is measured calibrator (strandmeasuring calibration devices), the concentration control that the liquid polymer powder dispersion is bathed, Deng, some problems during they do not address these problems.

Perhaps, the aqueous dispersion of thermoplastic resin is by such method preparation, and polymerisable in the method monomer (it is the resinogen material) is by emulsion polymerisation process polymerization in the presence of emulsifying agent in aqueous medium.Advantageously, emulsion polymerisation process can produce the high-molecular-weight thermoplastic resin.But this method is subjected to the few restriction of number of spendable polymerisable monomer, therefore, has also limited the number of the aqueous dispersion of producible thermoplastic resin.

Glass fibre (comprising continuous fiber, bundle and rove and chopped fibres and bundle) also is used to strengthen various polymer substrates, and is used to strengthen polyolefin.In the forming process of glass fibre, with chemical treatment composite (usually being called sizing composition (sizing composition)) they are handled usually, thereby in ensuing processing, protect fiber, and help fiber to be bonded to polymer substrate.

United States Patent (USP) 4,728,573 disclose by chemically treated glass fibre, this glass fibre is prepared as follows: make the glass fibre for preparing from the glass melting stream that flows out from the aperture sleeve pipe or the similar devices attenuate, the use chemical treatment composite is handled this glass fibre, with this fiber collecting to one or more intrafascicular, and with the short bundle of this Shu Zuowei or continuously bundle collect in the multi-layer packaging.Described aqueous chemical treatment compositions comprises one or more amine organic coupling agents, the water-based emulsion or the dispersion of the carboxy-modified vistanex of neutralization of organic or inorganic alkali or approaching neutralization have been used, water dissolvable, dispersibility or emulsible film forming polymer and adhesive stabilizing agent.

WO2004099529 discloses drywall band (drywall tape), comprises glass fibre and the net that places the coating on a part of described glass fibre.This coating comprises to the solvable resin binder that maybe can be scattered in the sealant of small part.When solidified, this coating can also form adhesive bond with described sealant.

United States Patent (USP) 6,818,698 (WO2004031246) disclose in the glass fibre process for making or in follow-up phase, HMW functionalized polyolefin emulsion is applied on the glass fibre, thereby acquisition have the enhanced polypropylene compound of high-mechanical property.

In above-mentioned patent and publication in the used polyolefin dispersion every kind all contain functionalized polyolefin, as the polypropylene of maleic anhydride graft.Other publication that discloses the goods of coating glass fiber or glass fibre enhancing comprises United States Patent (USP) 5,437,928,5,891,284 and 5,972,166.

Expectation improves these and other enhancing structure based on fiber.Needs improve based on the adhesion between other assembly of the enhancing body of fiber and structure.In addition, also the ability that structure improves the formation goods that strengthens is used in expectation.

Summary of the invention

On the one hand, the disclosed embodiment of the application relates to the method that forms goods, and this method can comprise uses composition to the substrate that contains glass, and described composition can comprise aqueous dispersion, and described aqueous dispersion can comprise: (a) thermoplastic resin; (b) dispersion stabilizer; (c) water; With remove at least a portion water.

In others, the disclosed embodiment of the application relates to a kind of goods, it comprises: the composition that contacts with the part of the substrate that contains glass, wherein said composition can comprise when contact: aqueous dispersion, described aqueous dispersion can comprise that (a) deformation temperature is less than 110 ℃ polyolefin, (b) dispersion stabilizer and (c) water, wherein said composition gives improved character to substrate and wherein said substrate is plastic.

In others, the disclosed embodiment of the application relates to the goods that the composition that contacted by the part with the substrate that contains glass forms, and wherein said composition can comprise aqueous dispersion when contact, and described aqueous dispersion can comprise: (a) thermoplastic resin; (b) dispersion stabilizer; (c) water, wherein said goods have the glass of 92wt% at least, based on the gross weight of the substrate that contains glass, thermoplastic resin and dispersion stabilizer.

In others, the disclosed embodiment of the application relates to a kind of coated fiber, it can comprise: the composition that contacts with a part based on the fiber of glass, and wherein said composition can comprise aqueous dispersion when contact, described aqueous dispersion is formed by following material: (a) thermoplastic resin; (b) dispersion stabilizer; (c) water, the diameter of wherein said fiber are 5 to 35 microns; With wherein said composition be about 0.1 to 10 micron at described thickness based on the coating on the fiber of glass.

In others, the disclosed embodiment of the application relates to the method for coated fiber, comprising: use composition to the fiber based on glass, described composition can comprise: aqueous dispersion, and described aqueous dispersion comprises: (a) thermoplastic resin; (b) dispersion stabilizer; (c) water; Remove at least a portion water.

In others, the disclosed embodiment of the application relates to a kind of goods, and it has: place at least one layer composition at least a portion of the substrate that contains glass, wherein said composition can comprise: (a) deformation temperature is less than 110 ℃ polyolefin; (b) dispersion stabilizer; Wherein said composition is given improved character to substrate; Be shapable in the wherein said substrate.

Other aspects and advantages of the present invention will become apparent from the following description and the appended claims.

Description of drawings

Fig. 1 shows the extruder that can be used for forming according to the dispersion of the disclosed embodiment of the application.

Fig. 2 is the block flow diagram that shows the equipment be suitable for putting into practice method of the present invention.

Fig. 3 is the block flow diagram that shows another equipment be suitable for putting into practice method of the present invention.

The specific embodiment

Some embodiments relate to by the goods with composition applies or the impregnated structures body is made.In some embodiments, when using, said composition can comprise dispersion, and described dispersion comprises base polymer and stabilizing agent.In some embodiments, this structure can be the fiber based on glass.In other embodiments, this structure can be the substrate that contains glass.

Other embodiment relates to the fibre-reinforced goods that use polyolefinic aqueous dispersion to make.For example, polyolefinic aqueous dispersion can be used for applying the structure (comprising fiber roving (fiberrovings), felt seat (mat) and fabric) based on fiber.In some embodiments, polyolefin dispersion can contain at least one polyene hydrocarbon phase that does not have degree of functionality, produces thus to have the not coating/adhesive of functionalized polyolefin phase.In coating/adhesive, comprise this not functionalized polyolefin can cause the character improved, for example with structure in the bonding and the compatibility of improvement of other assembly.

The used term " based on the fiber of glass " of the application is meant glass fibre and contains the natural or synthetic fibers of at least 50% glass.

The used term of the application " contains the substrate of glass " and is meant at least a two-dimensional structure body that contains glass, and it is not the bundle of monofilament or monofilament.Therefore, the described substrate that contains glass has length and width simultaneously, and it is shapable in preferred embodiment.

The used term " shapable " of the application is meant the performance that under heat and/or the pressure substrate further is processed into new shape applying.

Aqueous dispersion

More generally, the composition that the disclosed embodiment of the application relates to aqueous dispersion and made by aqueous dispersion, its can be used for to substrate (as based on the fiber of glass or contain the substrate of glass) give improved character.In some embodiments, this dispersion contacts with substrate with the form of foam or foams.Used dispersion comprises water in the disclosed embodiment of the application, (A) at least a thermoplastic resin and (B) dispersion stabilizer.They are hereinafter described in further detail.

Thermoplastic resin

The thermoplastic resin (A) that is included in the embodiment of aqueous dispersion of the present disclosure is the resin that itself is not easy to be dispersed in the water.The used term " resin " of the application is construed as the natural resin that comprises synthetic polymer or chemical modification.

Used resin can comprise the blend and the elastomer of olefin polymer in the disclosed embodiment of the application.In some embodiments, thermoplastic resin is a semi-crystalline resins.Term " hypocrystalline " intention is determined to scan those resins that have at least one endothermic peak when calorimetric (DSC) is estimated when carrying out the standard deviation formula.Some semi-crystalline polymers demonstrate the DSC endothermic peak, and this endothermic peak demonstrates the slope of relaxing when the scanning temperature raises by final heat release maximum.This has reacted the polymer with wide fusion range, rather than has the polymer of the sharp melting point that it has been generally acknowledged that.Some polymer that can be used in this dispersion have single fusing point, and other polymer has a more than fusing point.

In some polymer, described fusing point one or more can be significantly, thereby make all or a part (as several degrees centigrade) fusion on very narrow temperature range of polymer.In other embodiments, this polymer can demonstrate wide melting characteristic in about 20 ℃ scope.Still in other embodiments, this polymer can demonstrate wide melting characteristic in greater than 50 ℃ scope.

In some embodiments, this thermoplastic resin can be non-functionalized resin.In other embodiments, this thermoplastic resin can be nonpolar resin.

The example that can be used for the thermoplastic resin (A) in the disclosed embodiment of the application comprises the homopolymers and the copolymer (comprising elastomer) of alpha-olefin, alpha-olefin such as ethene, propylene, the 1-butylene, 3-methyl-1-butene, 4-methyl-1-pentene, the 3-Methyl-1-pentene, the 1-heptene, the 1-hexene, the 1-octene, 1-decene and 1-dodecylene, typical representative is a polyethylene, polypropylene, poly-1-butylene, poly--3-methyl-1-butene, poly--the 3-Methyl-1-pentene, poly--4-methyl-1-pentene, ethylene-propylene copolymer, ethene-butene-1 copolymer, and propylene-butene-1 copolymer; Copolymer alpha-olefin and conjugation or unconjugated diene (comprising elastomer), typical representative has ethylene-butadiene copolymer and ethene-ENB copolymer; And polyolefin (comprising elastomer) is as copolymer two or more alpha-olefins and conjugation or unconjugated diene, typical representative has ethylene-propylene-butadiene copolymer, ethylene-propylene-dicyclopentadiene copolymer, ethylene-propylene-1,5-hexadiene copolymer, and ethylene-propylene-ENB copolymer; Vinyl-vinyl compound copolymer such as vinyl-vinyl acetate copolymer, vinyl-vinyl alcohol copolymer, ethylene-vinyl chloride copolymer, ethylene-acrylic acid or ethene-(methyl) acrylic copolymer, and ethene-(methyl) acrylate copolymer; Styrene copolymer (comprising elastomer) is as polystyrene, ABS, acrylonitritrile-styrene resin, AMS-styrol copolymer, styrene ethylene base alcohol copolymer, styrene-acrylate copolymer such as styrene acrylic methyl terpolymer, styrene-acrylonitrile copolymer acid butyl ester copolymer, styrene butyl methacrylate copolymer and styrene-butadiene-copolymer and crosslinked styrene polymer; And styrene block copolymer (comprising elastomer) is as SB and hydrate and styrene-isoprene-phenylethene triblock copolymer; Polyvinyl compound such as polyvinyl chloride, polyvinylidene chloride, vinyl chloride-vinylidene chloride copolymer, polyacrylic acid methyl ester, and polymethyl methacrylate; Polyamide such as nylon 6, nylon 6,6 and nylon 12; Thermoplastic polyester such as PETG and polybutylene terephthalate (PBT); Merlon, polyphenylene oxide, etc.; With glass resin, comprise poly-bicyclopentadiene polymer and relevant polymer (copolymer, terpolymer) based on hydrocarbon; Saturated monoolefine such as vinyl acetate, propionate and vinyl butyrate etc.; The ester of vinyl esters such as monocarboxylic acid comprises methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, dodecylacrylate, acrylic acid n-octyl, phenyl acrylate, methyl methacrylate, EMA and butyl methacrylate etc.; Acrylonitrile, methacrylonitrile, acrylamide, its mixture; Resin by preparations such as ring-opening metathesis polymerization and cross metathesis polymerizations (crossmetathesis polymerization).These resins can use separately or use with the form of combination of two or more.The example of concrete thermoplastic resin comprises styrene-butadiene-copolymer, and its styrene-content is about 70 to about 95wt%.

As a kind of resin of adequate types, can use two-or the esterification reaction product of many-carboxylic acid and glycol (comprising diphenol).These resins are described in United States Patent (USP) 3,590, in 000, with it by with reference to incorporating the application into.Other instantiation of resin comprises the styrene/methacrylic acid ester copolymer, and styrene/butadiene copolymers; The styrene-butadiene-copolymer of suspension polymerisation; Mylar, the product that it is then obtained by the reaction of bisphenol-A and expoxy propane and the reaction of fumaric acid obtain; With the mylar of branching, it is by dimethyl terephthalate (DMT), 1,3-butanediol, 1, and the reaction of 2-propane diols and pentaerythrite obtains, styrene-acrylate and composition thereof.

In addition, concrete embodiment uses the polymer based on ethene, and based on the polymer of propylene, propylene-ethylene copolymers and styrene copolymer are as a kind of component of composition.Other embodiment uses mylar, comprise contain aliphatic diol such as UNOXOL 3,4 glycol (can be available from those of DowChemical Company (Midland, MI)).

In the embodiment of choosing, a kind of component is formed by ethene-alpha-olefin copolymer or propylene-alpha-olefin copolymers.Especially, in the embodiment of choosing, described thermoplastic resin comprises one or more non-polar polyolefinics.

In concrete embodiment, can use polyolefin such as polypropylene, polyethylene, its copolymer and its blend, and ethylene-propylene-diene terpolymer.In some embodiments, preferred olefin polymer comprises the United States Patent (USP) 3,645 as licensing to Elston, the homopolymers described in 992; As license to the United States Patent (USP) 4,076 of Anderson, the high density polyethylene (HDPE) described in 698 (HDPE); (heterogeneously branched) linear low density polyethylene (LLDPE) (LLDPE) of heterogeneous branching; The linear extra-low density polyethylene (ULDPE) of heterogeneous branching; Homogeneously branched linear ethylene/alpha olefin copolymer; The ethylene/alpha-olefin polymer of homogeneously branched line style basically, it can be by for example United States Patent (USP) 5,272,236 and 5,278, and the method preparation described in 272 is incorporated disclosing of described document into the application by reference; And high pressure, the ethene polymers of radical polymerization and copolymer such as low density polyethylene (LDPE) (LDPE) or ethane-acetic acid ethyenyl ester polymer (EVA).

Also suitable in some embodiments is at United States Patent (USP) 6,566,446,6,538,070,6,448,341,6,316,549,6,111,023,5,869,575,5,844,045 or 5, polymer composition described in 677,383 and blend thereof are incorporated these documents full content separately into the application by reference.In some embodiments, described blend can comprise two kinds of different Ziegler-Natta polymer.In other embodiments, described blend can comprise the blend of Ziegler-Natta and metallocene polymers.Still in other embodiments, the used polymer of the application can be the blend of two kinds of different metallocene polymers.In other embodiments, can use the polymerization catalyst thing in single site.

In some embodiments, described polymer is based on the copolymer or the interpretation of propylene.In some specific embodiments, described copolymer or interpretation based on propylene is characterised in that having is isotactic propylene sequences basically.Term " being isotactic propylene sequences basically " and similarly term be meant that this sequence passes through ¹³The isotaxy three unit groups (mm) that C NMR measures are greater than about 0.85 in one embodiment; In another embodiment greater than about 0.90; In another embodiment greater than about 0.92; Still in another embodiment greater than about 0.93.Isotactic triple is well known in the art, and for example is described in the United States Patent (USP) 5,504,172 and WO 00/01745, and it is meant according to passing through ¹³The isotactic sequence of the triple unit in the spectrometric copolymer molecule chain of C NMR.

A kind of embodiment based on the polymer of propylene is propylene-ethylene copolymers or interpretation, and the amount that therein ethylene exists can be extremely about 25wt% of about 5wt%.In some embodiments, the alpha-olefin interpolymers that is rich in propylene be characterised in that by ¹³The isotaxy triple (mm) that C NMR records is greater than about 0.85.Some these alpha-olefin interpolymers that are rich in propylene can have 5 to 25wt% unit that is derived from ethene and 95 to 75wt% the unit that is derived from propylene.In addition, some alpha-olefin interpolymers that are rich in propylene have (a) less than 90 ℃ fusing point; (b) relation of elasticity and 500% stretch modulus makes elasticity be less than or equal to 0.935M+12, and wherein elasticity is in percentage, and M is 500% stretch modulus in Mpa; (c) relation of flexural modulus and 500% stretch modulus makes flexural modulus be less than or equal to 4.2e ^0.27M+ 50, wherein flexural modulus is in Mpa, and M is 500% stretch modulus in Mpa.In some embodiments, the alpha-olefin interpolymers that is rich in propylene comprises 6 to 20wt% unit that is derived from ethene and 94 to 80wt% the unit that is derived from propylene.In other embodiments, polymer can comprise 8 to 20wt% unit that is derived from ethene and 92 to 80wt% the unit that is derived from propylene.Still in other embodiments, polymer can comprise 10 to 20wt% unit that is derived from ethene and 90 to 80wt% the unit that is derived from propylene.

In other concrete embodiment, base polymer can be the polymer based on ethylene vinyl acetate (EVA).In other embodiments, base polymer can be the polymer based on ethylene-methyl acrylate (EMA).In other specific embodiment, ethylene-alpha-olefin copolymer can be ethene-butylene, ethene-hexene, or ethylene-octene copolymer or interpretation.In other concrete embodiment, described propylene-alpha-olefin copolymers can be propylene-ethylene or propylene-ethylene-butene copolymer or interpretation.

In a kind of specific embodiment, thermoplastic resin can comprise the alpha-olefin interpolymers of ethene and comonomer (comprising alkane alkene such as 1-octene).But the copolymer individualism of this ethene and octene, perhaps with another thermoplastic resin, combination exists as ethylene-acrylic acid copolymer.When existing together, the copolymer of this ethene and octene and the weight ratio between the ethylene-acrylic acid copolymer can be about 1: 10 to about 10: 1, for example about 3: 2 to about 2: 3.This fluoropolymer resin can be less than about 50%, for example less than about 25% as the degree of crystallinity of ethylene-octene copolymer.In some embodiments, this crystallinity of polymer can be 5 to 35%.In other embodiments, this degree of crystallinity can be 7 to 20%.

The disclosed embodiment of the application also can comprise the polymers compositions that can contain at least a many blocks olefin interconversion polymers.Suitable many blocks olefin interconversion polymers can comprise for example those described in the U.S. Provisional Patent Application 60/818,911.Term " segmented copolymer " is meant and comprises preferably two or more the chemically different zones that engage in the line style mode or the polymer of fragment (being called " block "), promptly, comprise that ethylenic functional group with respect to polymerization connects (end-to-end) from beginning to end, rather than the polymer of the chemically different unit that connects with the form of side group or grafting.In some embodiments, this block is different in the following areas: the wherein type of the comonomer of combination or amount, density, degree of crystallinity, the relevant crystal size of character with the polymer of this composition, the type and the degree of steric regularity (tacticity) (isotaxy or syndiotaxy), regio-regular (regio-regularity) or regional irregularity type (regio-irregularity), the branching amount, comprise long chain branching or hyperbranched, uniformity (homogeneity), or any other chemistry or physical property.

This segmented copolymer is characterised in that because polydispersity index (PDI or the M that the peculiar methods of preparation copolymer causes _w/ M _n), block distribution of lengths, and/or the unique distribution of block number distribution (block numberdistribution).More specifically, when producing in continuation method, the embodiment of polymer can have about 1.7 to about 8 PDI; In other embodiments, be about 1.7 to about 3.5; In other embodiments, be about 1.7 to about 2.5; Also in other embodiments, be about 1.8 to about 2.5 or about 1.8 to about 2.1.When making in intermittence or semi-batch process, the embodiment of polymer can have about 1.0 to about 2.9 PDI; In other embodiments, be about 1.3 to about 2.5; In other embodiments, be about 1.4 to about 2.0; Also in other embodiments, about 1.4 to about 1.8.

A kind of example of many blocks olefin interconversion polymers is the ethylene/alpha-olefin block interpolymer.Another example of many blocks olefin interconversion polymers is the propylene/alpha-olefins interpretation.Below describe concentrating on the interpretation of ethene, but also be applicable to many block interpolymers according to general polymer property in a similar fashion based on propylene as principal monomer.

But the many block interpolymers of ethylene/alpha-olefin can comprise the ethene of polymerized form and the alpha-olefin comonomer of one or more copolymerization, it is characterized in that having a plurality of (that is, two or more) block or fragment (block interpolymer) of the monomeric unit of two or more different polymerizations of chemistry or physical property.In some embodiments, described copolymer is many block interpolymers.In some embodiments, described many block interpolymers can be expressed from the next:

(AB) _n

Wherein n is at least 1, and in various embodiments, n is the integer greater than 1, as 2,3,4,5,10,15,20,30,40,50,60,70,80,90,100 or bigger; " A " expression hard block or fragment; " B " expression soft segment or fragment.Preferably, each A is connected with the mode of line style rather than the mode of branching or star with each B." firmly " fragment is meant the block of the unit of polymerization, and wherein the amount that exists of ethene is greater than 95wt% and in other embodiments in some embodiments, greater than 98wt%.In other words, in some embodiments, the content of comonomer in hard fragment less than the 5wt% of hard fragment gross weight and in other embodiments, less than 2wt%.In some embodiments, described hard fragment comprises all or all basically ethene.On the other hand, " soft " fragment is meant the block of polymerized unit, and wherein in some embodiments, co-monomer content is greater than the 5wt% of soft segment gross weight, in various other embodiments, and greater than 8wt%, greater than 10wt%, or greater than 15wt%.In some embodiments, the content of comonomer in soft segment can be greater than 20wt%, greater than 25wt%, and greater than 30wt%, greater than 35wt%, greater than 40wt%, greater than 45wt%, greater than 50wt%, or in various other embodiments, greater than 60wt%.

In some embodiments, A block and B block are along the polymer chain random distribution.In other words, described block copolymer does not have the structure shown in AAA-AA-BBB-BB.

In other embodiments, described block copolymer does not have the 3rd block.Also in other embodiments, block A and B block do not comprise two or more fragments (or sub-block), as terminal fragment.

The feature of many block interpolymers can be has average block index (average block index), ABI, and it is greater than 0 to about 1.0, and molecular weight distribution, M _w/ M _n, greater than about 1.3.Average block index, ABI, be in preparation type TREF from 20 ℃ to 110 ℃, increment is the weight average of the blockiness index (" BI ") of 5 ℃ of each polymer fractions that is obtained:

ABI＝∑(w _iBI _i)

BI wherein _iBe the blockiness index of i fraction of many block interpolymers of in preparation type TREF, obtaining, and w _iIt is the percetage by weight of i fraction.

Similarly, the square root of the second moment of mean value (second moment) is called second moment weight average blockiness index hereinafter, can be as giving a definition:

2 ^NdThe square weight average $\mathrm{BI}=\sqrt{\frac{\mathrm{\Σ}\left(w_i{({\mathrm{BI}}_i-\mathrm{ABI})}^2\right)}{\frac{(N-1)\mathrm{\Σ}{w}_i}{N}}}$

For each polymer fractions, BI is defined by one of following two equations (these two equations provide identical BI value):

$\mathrm{BI}=\frac{1/T_X-1/T_{\mathrm{XO}}}{1/T_A/-1/T_{\mathrm{AB}}}$ Or $\mathrm{BI}=-\frac{\mathrm{Ln}{P}_X-\mathrm{Ln}{P}_{\mathrm{XO}}}{{\mathrm{LnP}}_A-\mathrm{Ln}{P}_{\mathrm{AB}}}$

T wherein _XBe analysis temperature improve elution fractionation (analytical temperature rising elutionfractionation, ATREF), the eluting temperature of i fraction (preferably with Kelvinometer), P _XBe the ethene molar fraction of i fraction, it can as described belowly record by NMR or IR.P _ABBe the ethene molar fraction of whole ethylene/alpha-olefin interpolymers (before classification), it also records by NMR or IR.T _AAnd P _ABe the ATREF eluting temperature and the ethene molar fraction of pure " hard fragment " (it is meant the crystallizable fragment of interpretation).As approximate, perhaps for the polymer of the composition the unknown of " hard fragment ", T _AAnd P _AValue is set at the value of high density polyethylene (HDPE) homopolymers.

T _ABBe to have same composition with described many block interpolymers (to have P _ABThe ethene molar fraction) and the ATREF eluting temperature of the random copolymer of molecular weight.T _ABCan use following equation to calculate by the molar fraction (recording) of ethene by NMR:

Ln P _AB＝α/T _AB+β

Wherein α and β are two constants, and the preparation type TREF fraction of wide composition random copolymer that can be by using many well-characterized and/or the random ethylene copolymer calibration with narrow composition of well-characterized are measured.What should be mentioned in that is that α can change according to the different of instrument with β.In addition, need use suitable molecular weight ranges and comonomer type, set up the appropriate calibration curve that interested polymer is formed preparation type TREF fraction and/or the random copolymer of setting up this calibration usefulness.There is slight molecular weight effect.If calibration curve derives from similar molecular weight ranges, this effect just can be ignored basically.In some embodiments, the preparation type TREF fraction of random ethylene copolymer and/or random copolymer satisfies following relation:

Ln P＝-237.83/T _ATREF+0.639

Above-mentioned calibration equation is with the molar fraction P and the analytic type TREF eluting temperature T of ethene _ATREFAssociate the preparation type TREF fraction of the random copolymer of the random copolymer that is used for narrow composition and/or wide composition.T _XOBe to have same composition and the ethene molar fraction is P _XThe ATREF temperature of random copolymer.T _XOCan be by LnP _X=α/T _XO+ β calculates.On the contrary, P _XOBe to have same composition and the ATREF temperature is T _XThe ethene molar fraction of random copolymer, it can be by Ln P _XO=α/T _X+ β calculates.

In case obtain the blockiness index (BI) of each preparation type TREF fraction, just can calculate the weight average blockiness index of whole polymer, ABI.In some embodiments, ABI greater than 0 but less than about 0.4, perhaps be about 0.1 to about 0.3.In other embodiments, ABI is greater than about 0.4, up to about 1.0.Still in other embodiments, ABI should be about 0.4 to about 0.7, about 0.5 to about 0.7, perhaps about 0.6 to about 0.9.In some embodiments, ABI is about 0.3 to about 0.9, about 0.3 to about 0.8, perhaps about 0.3 to about 0.7, about 0.3 to about 0.6, about 0.3 to about 0.5, perhaps about 0.3 to about 0.4.In other embodiments, ABI is about 0.4 to about 1.0, about 0.5 to about 1.0, perhaps about 0.6 to about 1.0, about 0.7 to about 1.0, about 0.8 to about 1.0, perhaps about 0.9 to about 1.0.

Another feature of many block interpolymers is that interpretation can comprise at least a polymer fractions that can obtain by preparation type TREF, and the blockiness index of wherein said fraction is greater than about 0.1 and about at the most 1.0, and the molecular weight distribution of described polymer, M _w/ M _n, greater than about 1.3.In some embodiments, the blockiness index of polymer fractions is greater than about 0.6 and about at the most 1.0, greater than about 0.7 and about at the most 1.0, greater than about 0.8 and about at the most 1.0, perhaps greater than about 0.9 and about at the most 1.0.In other embodiments, the blockiness index of polymer fractions is greater than about 0.1 and about at the most 1.0, greater than about 0.2 and about at the most 1.0, greater than about 0.3 and about at the most 1.0, greater than about 0.4 and about at the most 1.0, perhaps greater than about 0.4 and about at the most 1.0.Also in other embodiments, the blockiness index of polymer fractions is greater than about 0.1 and about at the most 0.5, greater than about 0.2 and about at the most 0.5, greater than about 0.3 and about at the most 0.5, perhaps greater than about 0.4 and about at the most 0.5.Also in other embodiments, the blockiness index of polymer fractions is greater than about 0.2 and about at the most 0.9, greater than about 0.3 and about at the most 0.8, greater than about 0.4 and about at the most 0.7, perhaps greater than about 0.5 and about at the most 0.6.

The many block interpolymers of ethylene ' alpha '-olefin that are used for embodiment disclosed by the invention can be ethene and at least a C ₃-C ₂₀The interpretation of alpha-olefin.Interpretation also can comprise C ₄-C ₁₈Diene and/or alkenyl benzene.Can be used for comprising for example ethylenically unsaturated monomers with the suitable unsaturated comonomer of vinyl polymerization, diene conjugation or unconjugated, polyene, alkenyl benzene, etc.The example of these comonomers comprises C ₃-C ₂₀Alpha-olefin such as propylene, isobutene, 1-butylene, 1-hexene, 1-amylene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-nonene, 1-decene etc.In some embodiments, alpha-olefin can be 1-butylene and 1-octene.Other suitable monomers comprises styrene, halo-or the styrene that replaces of alkyl, vinyl benzo cyclobutane, 1,4-hexadiene, 1,7-octadiene, and cycloolefin (naphthenics) (as cyclopentene, cyclohexene and cyclo-octene).

The disclosed many block interpolymers of the application may be different from the monomer interpolation by order, the random copolymer that follows the routine of change catalyzer (fluxional catalysts) and anion or the preparation of cation activity polymerization technique, the physical blending thing and the block copolymer of polymer.Particularly, with have the degree of crystallinity that equates or the same monomer of modulus and the random copolymer of content of monomer and compare, described interpretation has better (higher) hear resistance (measuring acquisition by fusing point), higher TMA infiltration temperature, higher high temperature tensile strength, and/or higher high temperature torque storage modulus (high-temperature torsionstorage modulus) (recording) by dynamic mechanical analysis.The character of packing material may have benefited from using the embodiment of described many block interpolymers, compare with the random copolymer that contains same monomer and content of monomer, described many block interpolymers have lower compression set, especially at elevated temperatures, lower stress relaxation, higher creep resistance, higher tearing strength, higher adhesion inhibiting properties, because higher crystallization (curing) temperature causes than quick setting (setup) higher recovery (higherrecovery) (especially at elevated temperatures), better wear resistance, higher retraction force and better oil and filler are sneaked into (oil and filler acceptance).

Other olefin interconversion polymers comprises the polymer that contains monovinylidene aromatic monomer, and described monovinylidene aromatic monomer comprises styrene, o-methyl styrene, and p-methylstyrene, t-butyl styrene, etc.Especially, can use and contain ethene and cinnamic interpretation.In other embodiments, can use and comprise ethene, styrene and C ₃-C ₂₀Alpha-olefin randomly comprises C ₄-C ₂₀The copolymer of diene.

Suitable unconjugated diene monomers can comprise straight chain, side chain or the cyclic hydrocarbon diene with 6 to 15 carbon atoms.The example of suitable non-conjugated diene includes but not limited to the straight chain acyclic diene as 1,4-hexadiene, 1,6-octadiene, 1,7-octadiene, 1,9-decadinene, side chain acyclic diene such as 5-methyl isophthalic acid, 4-hexadiene; 3,7-dimethyl-1,6-octadiene; 3,7-dimethyl-1,7-octadiene, and the two dehydrogenation laurenes (dihydromyricene) that mix and the isomers of two dehydrogenation octenes (dihydroocinene), the alicyclic diene of monocycle, as 1, the 3-cyclopentadiene; 1, the 4-cyclohexadiene; 1,5-cyclo-octadiene and 1,5-encircle 12 carbon diene and encircle the cyclic diolefine of alicyclic that condense and bridge joint more, as tetrahydroindene, and methyl tetrahydroindene, bicyclopentadiene, dicyclo-(2,2,1)-heptan-2,5-diene; Thiazolinyl, alkylidene, cycloalkenyl group and ring alkylidene ENB are as 5-methylene-2-ENB (MNB); 5-acrylic-2-ENB, 5-isopropylidene-2-ENB, 5-(4-cyclopentenyl)-2-ENB, 5-cyclohexylidene-2-ENB, 5-vinyl-2-ENB, and norbornadiene.Be generally used for preparing in the diene of EPDM, particularly preferred diene is 1,4-hexadiene (HD), 5-ethylidene-2-ENB (ENB), 5-ethenylidene-2-ENB (VNB), 5-methylene-2-ENB (MNB), and bicyclopentadiene (DCPD).

Comprise ethene, C according to the desirable polymer of the spendable class of the disclosed embodiment of the application ₃-C ₂₀The elasticity interpretation of alpha-olefin, especially propylene and optional one or more diene monomers.Be preferred for alpha-olefin in this embodiment by formula CH ₂=CHR ^*Expression, wherein R ^*It is the alkyl of 1 to 12 carbon atom of line style or branching.The example of suitable alpha-olefin includes but not limited to propylene, isobutene, 1-butylene, 1-amylene, 1-hexene, 4-methyl-1-pentene and 1-octene.Especially preferred alpha-olefin is a propylene.Polymer based on propylene is commonly referred to EP or EPDM polymer in the art.Be used to prepare this polymer, especially the suitable diene of many blocks EPDM type polymer comprise conjugation or unconjugated, straight chain or side chain, the diene that contains 4 to 20 carbon atoms of ring-type or many rings.Preferred diene comprises 1,4-pentadiene, 1,4-hexadiene, 5-ethylidene-2-ENB, bicyclopentadiene, cyclohexadiene and 5-butylidene-2-ENB.Especially preferred diene is 5-ethylidene-2-ENB.

In the embodiment of choosing, described thermoplastic resin is formed by ethene-alpha-olefin copolymer or propylene-alpha-olefin copolymers.Especially, in the embodiment of choosing, described thermoplastic resin comprises one or more non-polar polyolefinics.

Described olefin polymer, copolymer, interpretation and many block interpolymers can be by functionaliseding in conjunction with at least a functional group in its polymer architecture.Exemplary functional group can comprise the undersaturated list of ethylenic for example-and the carboxylic acid of two-sense, the undersaturated list of ethylenic-and the carboxylic acid anhydrides of two-sense, its salt and ester thereof.This functional group can be grafted on the olefin polymer, perhaps can be with it and ethene and other optional comonomer copolymerization, form the comonomer of ethene, sense and the interpretation of optional other comonomer.Functional group is grafted to method on the polyethylene for example is described in the United States Patent (USP) 4,762,890,4,927,888 and 4,950,541, incorporate the full content of these patent disclosures into the application.A kind of useful especially functional group is a maleic anhydride.

The amount that is present in the functional group in the polymer of sense can change.In some embodiments, the amount of functional group's existence can be at least about 0.25wt%; In other embodiments, can be at least about 5wt%; And also in other embodiments, at least about 7wt%.In some embodiments, the amount of functional group's existence can be less than about 40wt%; In other embodiments, can be less than about 30wt%; And also in other embodiments, can be less than about 25wt%.

In some embodiments, described thermoplastic resin can be density 0.863 and 0.911g/cc between, melt index (MI) (190 ℃, use 2.16kg weight) is 0.1 to 100g/10min ethylene-octene copolymer or interpretation.In other embodiments, the density of described ethylene-octene copolymer can be 0.857 to 0.902g/cc, and melt index (MI) (190 ℃, use 2.16kg weight) is 0.8 to 35g/10min.

In some embodiments, described thermoplastic resin can be ethylene contents be 5 to 20wt% and melt flow rate (MFR) (230 ℃, use 2.16kg weight) be 0.5 to 300g/10min propylene-ethylene copolymers or interpretation.In other embodiments, the ethylene contents of described propylene-ethylene copolymers or interpretation can be 5 to 12wt%, and melt flow rate (MFR) (230 ℃, use 2.16kg weight) is 1 to 100g/10min.

In some other embodiment, it is 0.911 to 0.925g/cc that described thermoplastic resin can be density, and melt index (MI) (190 ℃ are used the 2.16kg weight) is 0.1 to 100g/10min low density polyethylene (LDPE).

In other embodiments, the degree of crystallinity of described thermoplastic resin can be less than 50%.In preferred embodiment, the degree of crystallinity of described base polymer can be 5 to 35%.In preferred embodiment, degree of crystallinity can be 7 to 20%.

In some other embodiment, described thermoplastic resin is a semi-crystalline polymer, and fusing point can be less than 110 ℃.In preferred embodiment, fusing point can be 25 to 100 ℃.In preferred embodiment, fusing point can be 40 to 85 ℃.

In other embodiments, described thermoplastic resin is a glassy polymers, can have the glass transition temperature less than 110 ℃.In preferred embodiment, glass transition temperature can be 20 to 100 ℃.In preferred embodiment, glass transition temperature can be 50 to 75 ℃.

In some embodiments, the weight average molecular weight of thermoplastic resin can be greater than 10,000g/mol.In other embodiments, weight average molecular weight can be 20,000 to 150,000g/mol; Still in other embodiments, be 50,000 to 100,000g/mol.

One or more thermoplastic resins can be included in this aqueous dispersion, and its amount is that about 1wt% is to about 96wt%.For example, the amount that described thermoplastic resin exists in aqueous dispersion can be about 10wt% to about 60wt% and in another embodiment, and about 20% to about 50wt%.

In concrete embodiment, vistanex can comprise ethene and/or propylene and be selected from C ₄To C ₁₀Alkene, preferred alpha-olefin, more preferably C ₄To C ₈Alpha-olefin most preferably is selected from n-butene, the copolymer and the interpretation of other monomer of n-hexylene and positive octene.The ethene of this resin or propylene content can be resin about 2 to 98wt%.In some embodiments, can select mainly based on the polyolefin of ethene, therein ethylene accounts for polyolefinic about 98 to 50wt%.In other embodiments, can select mainly based on polyolefin or other polyolefin of propylene, wherein propylene accounts for polyolefinic about 98 to 50%.The comonomer of selecting can account for polyolefinic remainder.

In one embodiment, vistanex can comprise such polyolefin based on ethene, and described polyolefinic melt index (MI) based on ethene (" MI ") is determined as about 0.1 to 25g/10min according to ASTM D1238 (190 ℃, the 2.16kg weight); In another embodiment, 0.25 to 22g/10min; With in another embodiment, about 0.5 to 18g/10min.In another embodiment, this vistanex can comprise such polyolefin based on propylene, described polyolefinic melt flow rate (MFR) based on propylene (" MFR ") is determined as about 0.25 to 85g/10min according to ASTM D1238 (230 ℃ are used the 2.16kg weight); In another embodiment, about 0.7 to 70g/10min; In another embodiment, about 1.4 to 60; With in another embodiment, about 2 to 50g/10min.

In one embodiment, this vistanex can comprise such polyolefin based on ethene, and described polyolefinic density based on ethene is about 0.855 to 0.925g/cc; In another embodiment, about 0.86 to 0.91; In another embodiment, about 0.875 to 0.905; With in another embodiment, about 0.86 to 0.90.

A class polyolefin that is particularly suitable in this application using is the copolymer of ethene and 1-octene or 1-butylene, wherein in one embodiment, ethene account for copolymer about 50 to 90wt%, in another embodiment, account for copolymer about 55 to 85wt%, in one embodiment, 1-octene or 1-butylene account for about 10 to 50% of copolymer, in another example, account for copolymer about 15 to 45wt%, and wherein in one embodiment, the melt index (MI) of ethylene copolymer is about 0.25 to 30g/10min, in another embodiment, be 0.5 to 20g/10min.

Another kind of preferred polyolefm comprises 1-propylene and ethene, the 1-octene, the copolymer of 1-hexene or 1-butylene, wherein in one embodiment, the 1-propylene account for copolymer about 65 to 95wt%, in another embodiment, account for copolymer about 75 to 93wt%, in one embodiment, ethene, the 1-octene, 1-hexene or 1-butylene account for copolymer about 5 to 35wt%, in another embodiment, account for copolymer about 7 to 25wt%, and wherein in one embodiment, the melt flow rate (MFR) of described copolymer (Melt Flow) is about 0.7 to 85g/10min, in another embodiment, for about 1.4 to 55g/10min.

Melt temperature (the T of the useful polymer based on ethene (comprising homopolymers, copolymer, interpretation and block interpolymer) in the disclosed embodiment of the application _m) can be 25 ℃ to 130 ℃.In other embodiments, this fusing point based on the polymer of ethene can be less than 125 ℃; In other embodiments, less than 115 ℃; In other embodiments, less than 105 ℃; In other embodiments, less than 95 ℃; In other embodiments, less than 85 ℃; In other embodiments, less than 75 ℃; In other embodiments, less than 65 ℃; Still in other embodiments, less than 60 ℃.

The Vicat softening point (ASTM D 1525) of useful polymer based on ethene can be 25 ℃ to 130 ℃ in the disclosed embodiment of the application.In other embodiments, the Vicat softening point based on the polymer of ethene can be less than 125 ℃; In other embodiments, less than 115 ℃; In other embodiments, less than 105 ℃; In other embodiments, less than 95 ℃; In other embodiments, less than 85 ℃; In other embodiments, less than 75 ℃; In other embodiments, less than 65 ℃; Still in other embodiments, less than 60 ℃; In other embodiments, less than 55 ℃; Still in other embodiments, less than 45 ℃.

The heat distortion temperature (DTUL) (ASTM D648,0.45Mpa load) of polymer under load based on ethene useful in the disclosed embodiment of the application can be at least 45 ℃.In other embodiments, the DTUL based on the polymer of ethene can be 45 ℃ to 130 ℃.In other embodiments, the DTUL based on the polymer of ethene can be about 65 ℃ to about 120 ℃; In other embodiments, about 75 ℃ to about 110 ℃.

Melt temperature (the T of the useful polymer based on propylene (comprising homopolymers, copolymer, interpretation and block interpolymer) in the disclosed embodiment of the application _m) can be 25 ℃ to 165 ℃.In other embodiments, the fusing point based on the polymer of propylene can be less than 135 ℃; In other embodiments, less than 125 ℃; In other embodiments, less than 115 ℃; In other embodiments, less than 105 ℃; In other embodiments, less than 95 ℃; In other embodiments, less than 90 ℃; In other embodiments, less than 85 ℃; In other embodiments, less than 75 ℃; In other embodiments, less than 65 ℃; Still in other embodiments, less than 60 ℃.

The Vicat softening point (ASTM D 1525) of useful polymer based on propylene can be 25 ℃ to 160 ℃ in the disclosed embodiment of the application.In other embodiments, the Vicat softening point based on the polymer of propylene can be less than 135 ℃; In other embodiments, less than 125 ℃; In other embodiments, less than 115 ℃; In other embodiments, less than 105 ℃; In other embodiments, less than 95 ℃; In other embodiments, less than 90 ℃; In other embodiments, less than 85 ℃; In other embodiments, less than 75 ℃; In other embodiments, less than 65 ℃; In other embodiments, less than 55 ℃; Still in other embodiments, less than 45 ℃.

The heat distortion temperature under load (DTUL) (ASTM D648,0.45Mpa load) of useful polymer based on propylene can be at least 45 ℃ in the disclosed embodiment of the application.In other embodiments, the DTUL based on the polymer of propylene can be 45 ℃ to 130 ℃.In other embodiments, the DTUL based on the polymer of ethene can be about 65 ℃ to about 120 ℃; In other embodiments, about 75 ℃ to about 110 ℃.

Be fit to comprise thermoplasticity and non-thermal plasticity polymer with the polymer of above-mentioned polyblend, it comprises natural and synthetic polymer.The exemplary polymer that is used for blend comprises ethane-acetic acid ethyenyl ester (EVA), ethylene/vinyl base alcohol copolymer, polystyrene, impact-resistant modified polystyrene, ABS, the derivative (SBS and SEBS) of styrene/butadiene block copolymer and its hydrogenation, and thermoplastic polyurethane.

Can with the suitable conventional block copolymer of the disclosed polyblend of the application, Mooney viscosity in some embodiments (ML 1+4@100 ℃ .) can be 10 to 135; In other embodiments, be 25 to 100; Still in other embodiments, be 30 to 80.Suitable polyolefin especially comprises line style or low density polyethylene (LDPE), polypropylene (comprise atactic, isotaxy, syndiotaxy and impact-resistant modified variant thereof) and poly-(4-methyl-1-pentene).Suitable styrenic polymer comprises polystyrene, the polystyrene of modified rubber (HIPS), styrene/acrylonitrile copolymer (SAN), SAN of modified rubber (ABS or AES) and styrene maleic anhydride copolymer.

Dispersion stabilizer

The disclosed embodiment of the application uses stabilizing agent to promote to form stable dispersion or emulsion.At selected embodiment, stabilizing agent can be surfactant, polymer (it is different from the thermoplastic resin or the base polymer of above detailed description), or its mixture.In other embodiments, this resin is self-stabilization agent (self-stabilizer), thereby may not need the stabilizing agent of other external source.For example, the system of self-stabilizationization can comprise the polyester of partial hydrolysis, wherein becomes alkali (aqueousbase) with water by merging polyester, can produce mylar and surfactant-shape stabilizing agent molecule.Especially, this stabilizing agent can be used as dispersant, the surfactant that is used to make the foams foaming that is formed by this dispersion, perhaps can be used as two purposes simultaneously.In addition, one or more stabilizing agents of use capable of being combined.

In some embodiments, stabilizing agent can be the polar polymer that has as the polar group of comonomer or grafted monomers.In preferred embodiment, stabilizing agent can comprise one or more polar polyolefins, and it has the polar group as comonomer or grafted monomers.Typical polymer comprises ethylene-acrylic acid (EAA) and ethylene-methacrylic acid copolymer, as can be by those of following trade (brand) name acquisition: PRIMACOR ^TM(the face mark of Dow Chemical Company), NUCREL ^TM(trade mark of E.I.DuPont de Nemours), and ESCOR ^TM(trade mark of ExxonMobil), and be described in United States Patent (USP) 4,599, those in 392,4,988,781 and 5,938,437, with the full content separately of these documents by with reference to incorporating the application into.Other suitable polymers comprises ethylene ethyl acrylate (EEA) copolymer, ethylene methacrylic acid methyl terpolymer (EMMA) and ethylene butyl acrylate copolymer (EBA).Also can use other ethene-polymers of carboxylic acid.Ordinary skill people will recognize that also can use many other useful polymer.

If the polar group of polymer is acid or alkaline, form corresponding salt thereby can use nertralizer that stabilizing agent is partially or completely neutralized so.In some embodiments, the neutralization reaction of stabilizing agent such as LCFA or EAA can be 25 to 200mol%; In other embodiments, be 50 to 110mol%.For example, for EAA, nertralizer is an alkali, as ammonium hydroxide or potassium hydroxide.Other nertralizer can comprise lithium hydroxide or NaOH.The concrete composition of being prepared is depended in the selection that it should be understood by one skilled in the art that suitable nertralizer, and this selection is in those of ordinary skills' ken.

In some embodiments, when using the stabilizing agent of polymerization, the molecular weight of the stabilizing agent of polymerization can be 5000 to 125000.In other embodiments, the molecular weight of the stabilizing agent of polymerization can be about 5000 to about 45000.Still in other embodiments, the molecular weight of the stabilizing agent of polymerization can be half less than the molecular weight of thermoplastic resin.

Spendable other stabilizing agent comprises having 12 to 60 carbon atom LCFAs or soaps.In other embodiments, LCFA or soap can have 12 to 40 carbon atoms.This salt can be the alkali metal or the ammonium salt of aliphatic acid, and it is by with corresponding alkali such as NaOH, KOH, NH ₄This acid of neutralization such as OH and amine such as monoethanolamine, triethanolamine and preparing.These salt can original position form in dispersion steps, and this is described in hereinafter more all sidedly.Can select the suitable fatty acids stabilizing agent to use and act on the dispersant of melt extrusion step, thereby reach the average grain diameter of expectation, it is about 0.2 and 25 micron in one embodiment, in another embodiment, is about 0.5 to 10 micron.In another embodiment, the size of polyolefin particles can be 0.5 to 1.5 micron.

Spendable other stabilizing agent comprises cationic surfactant, anion surfactant, or non-ionic surface active agent.The example of anion surfactant comprises sulfonate, carboxylate, and phosphate.The example of cationic surfactant comprises quaternary amine.The example of non-ionic surface active agent comprises block copolymer and the organic silicon surfactant that contains ethylene oxide.The surfactant that can be used as stabilizing agent can be external surfactants or internal table surface-active agent.External surfactants is the surfactant that can chemically not be reacted in the dispersion preparation process in the polymer.The example of useful external surfactants comprises the salt and the lauryl sulfonate of DBSA among the application.The internal table surface-active agent is the surfactant that can chemically be reacted in the dispersion preparation process in the polymer.The example of useful internal table surface-active agent comprises 2 among the application, 2-dihydromethyl propionic acid and salt thereof.

In concrete embodiment, the consumption of dispersant or stabilizing agent can be greater than 0 to about 60wt%, based on the amount of used base polymer (or base polymer mixture).For example, the consumption of LCFA or its salt can be 0.5 to 10wt%, based on the amount of base polymer.In other embodiments, the consumption of ethylene-acrylic acid or ethylene-methacrylic acid copolymer can be base polymer 0.5 to 60wt%.Also in other embodiments, the consumption of sulfonate can be 0.5 to 10wt%, based on the amount of base polymer.

As mentioned above, can use more than a kind of stabilizing agent, for example can be with its combination as dispersant or surfactant.It will be recognized by those of ordinary skills, the stabilizing agent that is used to produce the metastable aqueous dispersion of vistanex particle can change according to the character of used polyolefin particles.In addition, can be when preparing foam by the dispersion used foaming surfactant of used stabilizing agent is identical or different.

The foam stabilization surfactant

The substrate of that apply in some embodiments as mentioned above, or dipping can contact with the disclosed foam or the foams that are formed by dispersion of the application.The disclosed embodiment of the application can use the foam stabilization surfactant to promote to form stable dispersion and auxiliary foaming.When initial formation foam, can be implemented in foaming and the drying steps process formation foam in the aqueous dispersion of vistanex and make its stabilisation by adding foaming surfactant.In addition, if desired, these surfactants also can be used for improving the wettability (aqueous wetting) of dry foams.Suitable foaming surfactant can be selected from cation, nonionic and anion surfactant.In one embodiment, can use anion surfactant.

In some embodiments, foaming surfactant can be alkyl cellulose ether, hydroxy alkyl cellulose ether, hydroxyalkyl alkyl cellulose ether, guar gum, xanthans and at least 20, the polyoxyethylene resin of 000 molecular weight, or its combination.Other suitable foaming surfactant can be selected from cationic surfactant, anion surfactant, or non-ionic surface active agent.The example of cationic surfactant comprises quaternary amine, primary amine salt, the amine of two amine salt and ethoxylation.The example of non-ionic surface active agent comprises the block copolymer that contains oxirane, organic silicon surfactant, alkylphenol ethoxylate and contain the line style and the secondary alcohol ethoxyl compound of the alkyl that surpasses 8 carbon atoms.

The example of anion surfactant comprises sulfonate, carboxylate, and phosphate.In one embodiment, useful anion surfactant can be selected from aliphatic carboxylic acid (carboxylic fatty acid) (aliphatic acid that preferably includes the 12-36 carbon atom for example when preparing foam by described aqueous dispersion, stearic acid or laurate, palmitic acid, myristic acid, oleic acid, linoleic acid, castor oil acid, erucic acid etc.) carboxylate and esteramides.

In some embodiments, surfactant can comprise amphoteric surfactant such as aminopropionate, both sexes sulfonate, and betaine, based on the amphiprotic substance of imidazoline, and sulfobetaines, etc.For example, this surfactant can be derived from imidazoline, and can be the form (comprising salt) of acetate or the form (not saliferous) of propionate.Suitable examples of amphoteric surfactants comprises surfactant such as lauroyl amido CAB; lauroyl imido grpup dipropionic acid (sodium laurimino dipropionate); cocamidopropyl propyl hydroxy sulfobetaines (cocoamidopropyl hydroxyl sultaine); alkyl ether hydroxypropyl betaine (alkylether hydroxypropyl sultaine); caprylyl both sexes hydroxypropyl azochlorosulfonate acid sodium (sodium capryloampho hydroxypropyl sulfonate); caprylyl both sexes disodium beclomethasone (disodium capryloampho dipropionate); cocounut oil both sexes sodium acetate (sodiumcocoamphoacetate); cocounut oil both sexes oxalic acid disodium (disodium cocoamphodiacetate); cocounut oil both sexes sodium propionate (sodium cocoamphopropionate); octyl group imide disodium beclomethasone (disodium octyl iminodipropionate); cocounut oil both sexes hydroxypropyl azochlorosulfonate acid sodium (sodiumcocoampho hydroxypropyl sulfonate); lauryl imide disodium beclomethasone (disodiumlauryl iminodipropionate); stearyl both sexes sodium acetate (sodium stearoampho acetate); with tallow imide disodium beclomethasone (disodium tallow iminodipropionate), etc.Also can use other amphoteric surfactant known in the art.

Surfactant as foam stabiliser can be external surfactants or internal table surface-active agent.External surfactants is the surfactant that can chemically not be reacted in the dispersion preparation process in the polymer.The example of useful external surfactants comprises the salt and the lauryl sulfonate of DBSA among the application.The internal table surface-active agent is the surfactant that can chemically be reacted in the dispersion preparation process in the polymer.The example of useful internal table surface-active agent comprises 2 among the application, 2-dihydromethyl propionic acid and salt thereof.

The surfactant that can be used for preparing stable foam is also referred to as the foams stabilizing agent in this application.It will be recognized by those of ordinary skills and to use many foam stabilisers.Foam stabiliser can comprise for example sulfate, succinamate and sulphosuccinamate.

Additive

Dispersion of the present invention can comprise other conventional additives material, thereby forms coating composition.These include but not limited to filler, fire retardant (as calcium carbonate, aluminum trihydrate (ATH), and magnesium hydroxide), stabilizing agent, pigment and dyestuff, releasing agent, and antistatic agent.Other can be used in combination with glass fibre based on polymer or cellulosic fiber composition.

Additive and following material can be merged: dispersion, perhaps used thermoplastic resin, stabilizing agent or filler in the dispersion.For example, additive can comprise wetting agent, fire retardant, surfactant, antistatic agent, antifoaming agent, anti-blocking agent is based on the dispersion of wax, pigment, nertralizer, thickener, bulking agent, brightening agent, rheology modifier, biocide, fungicide, fortifying fibre and other additive well known by persons skilled in the art.Though for what the objective of the invention is to choose wantonly, other component may be very favorable for the product stability after the process for making neutralization.

Additive and auxiliary agent can be included in any preparation that comprises above-mentioned polymer, copolymer, interpretation and many block interpolymers.Suitable additive comprises filler, as organic or inorganic particulate, comprises clay, talcum, titanium dioxide, zeolite, metal dust, the organic or inorganic fiber comprises carbon fiber, silicon nitride fiber, steel wire or net and nylon or polyester rope, the particle of nano-scale, clay, etc.; Tackifier, oil-extender (oil extenders) comprises paraffin oil or cyclenes hydrocarbon ils (napthelenic oils); Natural and synthetic polymer with other comprises other polymer according to embodiment disclosed by the invention.Thermoplastic compounds according to other embodiment disclosed by the invention also can contain organic or inorganic filler or other additive such as starch, talcum, calcium carbonate, polymer fiber (comprises nylon, artificial silk (rayon), cotton, polyester, and Nomex), metallic fiber, thin slice or particle, expandable phyllosilicate, phosphate or carbonic ester, as clay, mica, silica, aluminium oxide, aluminosilicate or aluminate or phosphate, carbon whisker, carbon fiber, nano particle (comprising nanotube), wollastonite, graphite, zeolite, and pottery, as carborundum, silicon nitride or titanium oxide.Based on silane or other coupling agent also can be used for obtaining better filler in conjunction with (filler bonding).

Above-mentioned polymer and polymer blend composition can contain processing oil, plasticizer, and processing aid.The RUBBER PROCESS OIL and the paraffin of certain ASTM sign, cycloolefin or aromatics processing oil all are to be fit to use.Per 100 parts of total polymer usually use 0 to 150 part, and more preferably 0 to 100 part, 0 to 50 part processing oil most preferably, plasticizer, and/or processing aid.More the oil of a large amount may be easy to improve the processing of the product that obtains, and sacrifices some physical propertys.Other processing aid comprises conventional wax, soap, and as calcium stearate or zinc stearate, (polynary) alcohol comprises glycol, (polynary) alcohol ether comprises glycol ether, (gathering) ester, comprise (gathering) glycol ester, and slaine-, the especially salt of its 1st or the 2nd main group metal or zinc salt derivative.

For the TPO of routine, TPV and TPE use, and carbon black is a kind of additive that can be used for UV absorption and stabilisation character.The representative example of carbon black comprises ASTM N110, N121, N220, N231, N234, N242, N293, N299, S315, N326, N330, M332, N339, N343, N347, N351, N358, N375, N539, N550, N582, N630, N642, N650, N683, N754, N762, N765, N774, N787, N907, N908, N990 and N991.The iodine of these carbon blacks is absorbed as 9 to 145g/kg, and average pore volume is 10 to 150cm ³/ 100g.Usually, under the situation that cost allows, use carbon black than small grain size.For many this application, polymer of the present invention and blend thereof all need seldom or do not need carbon black, allow that thus very big design freedom comprises optional pigment or do not comprise pigment.

The composition that comprises the thermoplastic blend of embodiments of the present invention also can contain the known antiozonant or the antioxidant of those of ordinary skill in rubber chemistry field.Antiozonant can be physical protection agent such as waxy substance (it contacts with the surface and protects this part not damaged by oxygen or ozone), and perhaps they can be the chemical protective agent with oxygen or ozone reaction.Suitable chemical protective agent comprises SP styrenated phenol; the phenol of butylated octyl groupization (butylated octylated phenol); butylated two (dimethyl benzyl) phenol; p-phenylenediamine (PPD), the butylated product of paracresol and bicyclopentadiene (DCPD), polyphenyl phenol antioxidant; hydroquinone derivatives; quinoline, two penylenes (diphenylene) antioxidant, thioesters antioxidant and blend thereof.The representational trade (brand) name of some of these products is WINGSTAY ^TMThe S antioxidant, POLYSTAY ^TM100 antioxidants, POLYSTAY ^TMThe 100AZ antioxidant, POLYSTAY ^TM200 antioxidants, WINGSTAY ^TMThe L antioxidant, WINGSTAY ^TMThe LHLS antioxidant, WINGSTAY ^TMThe K antioxidant, WINGSTAY ^TM29 antioxidants, WINGSTAY ^TMSN-1 antioxidant, and IRGANOX ^TMAntioxidant.In some applications, will to be preferably be (non-staining) and nonmigratory (non-migratory) of non-staining for used antioxidant and antiozonant.

For the extra stability to the UV radiation is provided, also can use hindered amine as light stabilizer (HALS) and UV absorbent.Suitable example comprises the TINUVIN available from Ciba Specialty Chemicals ^TM123, TINUVIN ^TM144, TINUVIN ^TM622, TINUVIN ^TM765, TINUVIN ^TM770, and TINUVIN ^TM780 and available from Cytex Plastics, Houston TX, the CHEMISORB of USA ^TMT944.As United States Patent (USP) 6,051, disclosed in 681, in order to obtain excellent surface quality, can additionally comprise lewis acid and HALS composition.Other embodiment also can comprise heat stabilizer, as IRGANOX ^TMPS 802FL.

For some compositions, other mixed method can be used for pre-dispersed heat stabilizer, antioxidant, antiozonant, carbon black, UV absorbent and/or light stabilizer, thereby form masterbatch, and then form blend polymer by it.

The suitable crosslinking agent that is used for the application (being also referred to as curing agent or vulcanizing agent) comprises based on sulphur, based on peroxide, or based on the composition of phenols.The example of aforementioned substances can find in the prior art, comprises United States Patent (USP) 3,758, and 643,3,806,558,5,051,478,4,104,210,4,130,535,4,202,801,4,271,049,4,340,684,4,250,273,4,927,882,4,311,628 and 5,248,729.

When the curing agent that uses based on sulphur, also can use promoter and solidify activator (cureactivator).Promoter being used to controlled required time of dynamic vulcanization and/or temperature, and improves the character of the crosslinked products that obtains.In one embodiment, use single promoter or use primary accelerator (primary accelerator).The total amount that primary accelerator uses can be about 0.5 to about 4, and preferred about 0.8 to about 1.5phr, based on the gross weight of composition.In another embodiment, can use the combination of primary accelerator and secondary accelerator (secondary accelerator), wherein secondary accelerator uses for example about 0.05 to about 3phr with less amount, thereby activates and improve the character of cured article.The combination of promoter produces such goods usually, and those of the promoter generation that its character is more independent than use are better more or less.In addition, can use delayed action accelerator (delayed action accelerator), it is not subjected to the influence of common processing temperature, still produces satisfied curing in common vulcanization reaction temperature.Also can use cure retarder.The promoter that can be used for the adequate types among the present invention is amine, disulphide, guanidine, thiocarbamide, thiazole, thiuram, sulfenamide, dithiocar-bamate (or ester) and xanthates (ester).Preferably, primary accelerator is a sulfenamide.If the use secondary accelerator, secondary accelerator is preferably guanidine so, dithiocar-bamate (or ester) or thiuram composition.Also can use some processing aid and solidify activator such as stearic acid and ZnO.When the curing agent that uses based on peroxide, conactivator or coagent can be used in combination with it.Suitable coagent comprises trimethyol propane triacrylate (TMPTA), trihydroxy methyl propane trimethyl acrylate (TMPTMA), triallyl cyanurate (TAC), triallyl isocyanurate (TAIC) etc.Peroxide cross-linking agent and optional coagent that use is used for partially or completely dynamic vulcanization reaction are known in the art, and for example be disclosed in the following discloses publication: " Peroxide Vulcanization of Elastomer; " Vol.74, No 3, July-August2001.

When polymer composition when being partial cross-linked at least, the degree of cross linking can record by following: said composition is dissolved in time of appointment in the solvent, and (unextractable) percentages of ingredients that maybe can not extract of calculated for gel.The percentage of gel increases along with the increase of crosslinked level usually.For cured article according to the embodiment of the present invention, the degree of gel is desirably 5 to 100%.

In some embodiments, additive also can comprise perfume, alga inhibitor (algae inhibitor), antimicrobial and antifungal agent (anti-microbiological and anti-fungus agents), fire retardant and not halogen-containing fire retardant, and slip and antiblocking additive (slip and anti-blockadditive).Other embodiment can comprise that also PDMS reduces the wearability of polymer.Polymer also can be by using tackifier or with organosilan, polychlorobutadiene (neoprene) or other grafting agent functionalization of polymers or coupling being improved to the bonding force of sand grains.

Dispersion formulations

Dispersion formulations according to the disclosed embodiment of the application can comprise liquid medium, as water, and thermoplastic resin, dispersion stabilizer and optional filler.About thermoplastic resin and dispersion stabilizer, in some embodiments, described thermoplastic resin can account for about 30wt% to 99wt% of thermoplastic resin and dispersion stabilizer total amount in the composition.In other embodiments, thermoplastic resin can account for about 50wt% of thermoplastic resin and dispersion stabilizer total amount in the composition to about 80wt%.Still in other embodiments, thermoplastic resin can account for about 70wt% of thermoplastic resin and dispersion stabilizer total amount in the composition.

In one embodiment, the disclosed aqueous dispersion of the application can comprise the vistanex particle, and its granularity is about 0.2 to 10 micron; In another embodiment, about 0.5 to 5 micron; With about 1 to 2 micron.Thus, and apply or be impregnated with comparing based on the fiber of glass or the substrate that contains glass of described dispersion, described vistanex particle is usually to order of magnitude when young.

Preferably thermoplastic resin and dispersion stabilizer are dispersed in the liquid medium, described liquid medium is water in some embodiments.In some embodiments, add the dispersion that enough alkali neutralizes and obtains, thereby obtain about 6 to about 14 pH scope.In concrete embodiment, be about 9 to about 12 thereby add enough alkali maintenance pH.The water content of a controllable sub prose style free from parallelism, thus make that the total content of thermoplastic resin and dispersion stabilizer (solid content) is that about 1 volume % is to about 74 volume %.In another embodiment, range of solid content is that about 25 volume % are to about 74 volume %.Also in another embodiment, solid content is about 30% to about 50% (by weight, not containing filler).Also in another embodiment, solid content is about 40% to about 55% (by weight, not containing filler).

In various embodiments, dispersion can be formed by non-functionalized or nonpolar thermoplastic resin and functionalized or polarity dispersion stabilizer.In some embodiments, described thermoplastic resin can form two different phases with dispersion stabilizer in dispersion.In other embodiments, thermoplastic resin can form two different phases with dispersion stabilizer when being applied to substrate.Described two different may be present in mutually the substrate that applies from dispersion remove anhydrate before, the process or afterwards.

The feature of the dispersion that forms according to the disclosed embodiment of the application can be that particle mean size is about 0.3 to about 3.0 microns.In other embodiments, the particle mean size of dispersion can be about 0.8 to about 1.2 microns.Used " particle mean size " of the application is meant volume average particle sizes.In order to measure granularity, for example can use laser diffraction technology.Granularity in the specification is meant the diameter of polymer in dispersion.For not being spherical polymer particle, the diameter of particle is the major axis of particle and the mean value of minor axis.Granularity can be measured on Beckman-Coulter LS230 laser diffraction granularity analyzer or other suitable device.

Therefore, in preferred preparation, can comprise thermoplastic resin (it can comprise at least a above-mentioned nonpolar polyolefin), dispersion stabilizer (it can comprise at least a polar polyolefin) and optional filler according to dispersion of the present disclosure.About thermoplastic resin and dispersion stabilizer, in preferred embodiment, described at least a nonpolar polyolefin can account for about 30wt% to 99wt% of base polymer and dispersion stabilizer total amount in the composition.More preferably, described at least a nonpolar polyolefin accounts for about 50% to about 80%.Still more preferably, described one or more nonpolar polyolefin account for about 70%.

About filler, the total amount of per 100 parts of thermoplastic resins and dispersion stabilizer, the common consumption of filler is greater than about 0 to about 1000 parts.In selected embodiment, per hundred parts are used about 50 to 250 parts; In other embodiments, be per hundred parts about 10 to 500 parts; In other embodiments, be per hundred parts about 20 to 400 parts; Still in other embodiments, be per hundred parts about 0 to about 200 parts.

In some embodiments, apply or flooded the structure or the textile of composition, as based on the fiber of glass or contain the substrate of glass, the total amount of its described at least a thermoplastic resin and dispersion stabilizer can be about 0.1 to about 150 parts of described structures of per hundred weight portions or textile.In other embodiments, flooded the structure of composition or the described at least a polymer of textile and the total amount of dispersion stabilizer and can be about 0.5 to about 10 parts of described structures of per hundred weight portions or textile; In other embodiments, be about 1.0 to about 8.0 parts.

The dispersion formulations that the application discloses can comprise surfactant, blowing agent, dispersant, thickener, fire retardant, pigment, antistatic agent, fortifying fibre, antioxidant, nertralizer, rheology modifier, anticorrisive agent, biocide, acid scavenger, wetting agent etc.Though for what the objective of the invention is to choose wantonly, other component may be very favorable for the product stability after the process for making neutralization.

In addition, the embodiment of dispersion is optional comprises the filler wetting agent.The filler wetting agent can help to make filler more compatible with polyolefin dispersion usually.Useful wetting agent comprises phosphate, as calgon (sodium hexametaphosphate).The filler wetting agent can be included in the concentration at least about 0.5 part of per 100 parts of filler in the composition of the present invention by weight.

In addition, the embodiment of dispersion can randomly comprise thickener.Thickener can be used for increasing the viscosity of dispersions with low viscosity.The thickener that be fit to use can be any thickener known in the art, as poly--esters of acrylic acid or the relevant non-ionic thickening agent such as the cellulose ether of modification.For example, suitable thickening comprises ALCOGUM ^TMVEP-II (trade (brand) name of Alco Chemical Corporation), RHEOVIS ^TMAnd VISCALEX ^TM(trade (brand) name of Ciba Ceigy),

Thickener 146, or ETHOCELL ^TMOr METHOCELL ^TM(trade (brand) name of Dow Chemical Company) and PARAGUM ^TM241 (Para-Chem Southern, the trade (brand) names of Inc.), or BERMACOL ^TM(trade (brand) name of Akzo Nobel) or AQUALON ^TM(trade (brand) name of Hercules) or

(trade (brand) name of Rohm and Haas).Thickener can have the required any amount use of dispersion of desired viscosity with preparation.

Therefore, the final viscosity of dispersion (ultimate viscosity) is controlled.Can use conventional method that thickener is added in the dispersion that comprises described amount filler, obtain required viscosity.The viscosity of this dispersion can reach+and (Brookfield spindle 4 20rpm) uses suitable thickener dosage (at the most 4%, preferably be lower than 3%, based on the polymeric dispersions of 100phr) to 3000cP.The initial viscosity of described initial polymer dispersion before preparing with filler and additive can be 20 to 1000cP (the Brookfield viscosity use spindle RV3 to record at 50rpm in room temperature).Still more preferably, the initial viscosity of dispersion can be about 100 to about 600cP.

Their stability when equally, the feature of embodiment of the present disclosure can be in filler being added to thermoplastic resin/dispersion stable agent composition.In the present context, stability is meant the stability of the viscosity of the aqueous polyolefin dispersions that obtains.For stable testing, measure the viscosity of following period of time.Preferably, when in storage at ambient temperature, 20 ℃ of measurements during 24 hours in viscosity should remain on initial viscosity+/-10% in.

In concrete embodiment, with thermoplastic resin and dispersion stabilizer in extruder with water and nertralizer (as ammoniacal liquor, potassium hydroxide, or this combination of two kinds) melt kneading together, form dispersion.It will be recognized by those of ordinary skills and to use many other nertralizers.In some embodiments, filler can add in the process of blend thermoplastic resin and dispersion stabilizer or afterwards.

Can use any melt kneading means known in the art.In some embodiments, use kneader,

Banbury, single screw extrusion machine or multi-screw extruder.The method that is used to produce according to dispersion of the present invention is not particularly limited.For example, a kind of preferable methods is according to United States Patent (USP) 5,756,659 and the method for United States Patent (USP) 6,455,636, and this method comprises the melt kneading said components.

Fig. 1 has summarily illustrated the extrusion equipment that can use in the application's embodiment.Extruder 20 (being double screw extruder in some embodiment) is connected to back pressure regulator, Melt Pump or gear pump 30.Embodiment also provides alkali storage tank 40 and initial water storage tank 50, and it all comprises the pump (not shown) separately.The alkali of desired amount and initial water are provided by described alkali storage tank 40 and initial water storage tank 50 respectively.Can use any suitable pump, but in some embodiments, use pressure to provide the pump of the flow velocity of about 150cc/min that alkali and initial water are supplied to extruder 20 at 240bar.In other embodiments, liquid infusion pump (liquid injection pump) provides the flow velocity of 300cc/min or the flow velocity of 600cc/min is provided at 133bar at 200bar.In some embodiments, described alkali and initial water preheat in pre-heater.

The resin of pellet, powder or sheet-form is fed to the inlet 90 of extruder 20 from feeder 80, and the fusion of resin and being mixed is carried out in described extruder 20.In some embodiments, dispersion stabilizer is added in the thermoplastic resin and in other embodiments, dispersion stabilizer offered double screw extruder 20 separately by this resin and with this resin.Then with resin melt from mixing and transmitting the emulsion band that the district is delivered to extruder, wherein water and the alkali from the primary quantity of storage tank 40 and 50 adds by inlet 55.In some embodiments, dispersion stabilizer additionally or uniquely can be added in the current.In some embodiments, the mixture of emulsification is further used from the dilution of extruder 20 and the other water inlet 95 of the storage tank in the cooling zone 60 and is further diluted.Usually, dispersion is diluted to the water of 30wt% at least in the cooling zone.In addition, can be with any multiple of mixture diluted of dilution, up to the dilution level that obtains expectation.In some embodiments, water is not added in the double screw extruder 20, but after extruder withdraws from, add to the logistics that contains resin melt at melt.In this way, the logistics pressure of having eliminated in the extruder 20 increases.

Advantageously, by using extruder in some embodiments, can blend in single technology with thermoplastic resin and dispersion stabilizer, form dispersion.Equally, advantageously, by using one or more above listed dispersion stabilizers, dispersion can be stable with respect to filler and other additive.

Apply and dipping

The polyolefin dispersion that forms according to the disclosed embodiment of the application provides this dispersion coating, partly applies, is administered to, or be impregnated into dispersion based on the fiber of glass and contain the substrate of glass, film, sheet material, fabric, or other is based on the ability of the goods of glass.Also can give improved character according to the polyolefin dispersion that the disclosed embodiment of the application forms to substrate.For example, the substrate that dispersion applies can obtain good viscosity, remains flexible laminated material simultaneously.

Dispersion can be administered to the goods such as felt seat, adhesive-bonded fabric, woven fabric and the fabric that comprise on glass, polymer and the cellulosic various fiber and make by these fibers.Fiberglass products includes but not limited to woven rove, the bundle that wet weak point is cut (wet chopped strand), unidirectional and multidirectional fabric (twin shaft to, three is axial, the four directions is to (quadraxial)), short dry paper fibre (paper dry chop), molded felt seat, insulating materials (insulation), the diclinic pattern fabric, long filament felt seat (continuous strandmat), short silk felt seat (chopped strand mat), veil and short silk (chopped strands).Used type of glass can be any normal glass based on silicon known in the art, as E-glass, and glass with lower alkali content (low alkali glass).

In some embodiments, can use any application process well known by persons skilled in the art that polyolefin dispersion or dispersion composite (dispersion that contains filler) are applied on the fibre structure.In other embodiments, fibre structure can flood with dispersion or dispersion composite.In some embodiments, fibre structure can comprise textile, geotextiles (geotextiles), and natural fiber.In some embodiments, fibre structure can comprise cotton, wool, synthetic wool, comprise the synthetic fibers of the synthetic fibers of the synthetic fibers of the synthetic fibers of the cellulose material (cellulosics) of artificial silk, polyamide, polyacrylonitrile, polyvinyl chloride, the synthetic fibers of polyvinylidene chloride, polyacrylic synthetic fibers, polyester, or its combination.In other embodiments, fibre structure can be flax, hemp, cellulose, paper pulp, timber, or its combination.In other embodiments, above-mentioned fibre structure can be that glass strengthens.Still in other embodiments, this fibre structure can be based on the fiber of glass or contain the substrate or the textile of glass.

For example, in the method for in Fig. 2, being put into practice, continuous fibre bundle (or rove) 1 from supplying the bath 4 of the thermoplastic dispersion 5 of spool (supply reel) 2 chargings by containing water-based fusion engagement, is formed the bundle that applies.With the bundle air drying that applies, perhaps randomly by thermal source such as stove 6, loose in this water drive with dispersion, that is, should restraint drying, and/or with this thermoplastic resin fusion.When the suitable temperature of needs (wherein will be easy to granulation in unit 9 in this temperature, thereby form the pellet of the thermoplastic concentrate of long fibre enhancing of the present disclosure) time, the bundle of this coating can randomly pass through near one or more heaters 7 after thermoplastic resin solidifies, should restraint further drying at this, and/or the temperature that will restraint raises.Can should restraint tractive by this device by granulation unit 9 or optional pulling apparatus (draw-off device) 8.Randomly, can make any point of bundle between bath 4 and granulation unit 9 of coating pass former 13.

Perhaps, in the method for in Fig. 3, being put into practice, with the bath 4 of continuous fibre bundle (or rove) 1 from the thermoplastic dispersion 5 of supply spool 2 chargings by containing water-based fusion engagement.The bundle that applies is then by comminutor 9; or other shredding mechanism; the bundle that applies is ground into pre-dried pellet 11; it falls to conveyer belt 12, makes that pre-dried pellet air is dry or randomly make pre-dried pellet 11 pass thermal source such as stove 6, the water of dispersion can be evaporated (ben off) at this; promptly; with pre-dried pellet 11 dryings, and/or, provide the pellet 10 of the thermoplastic concentrate of long fibre enhancing of the present invention with the thermoplastic resin fusion.If necessary, can strike off from conveyer belt by the pellet of scraper 14 drying.Can should restraint tractive by this device by granulation unit 9 or optional pulling apparatus 8.

Randomly, can make any point of bundle between bath 4 and granulation unit 9 of coating pass former 13.Any method that pre-dried pellet 11 is sent to stove 6 all is acceptable, for example, and conveyer belt or wind-force transfer system (pneumatic transportation systems).

At least a portion water of the dispersion of using in some embodiments, can be removed from the goods that dispersion applies.In other embodiments, can remove water at least 50% dispersion of using.

As the method that is used for the disclosed dispersion of production the application structure that apply or dipping, can use and the said method diverse ways.For example, fibre bundle can be cut into predetermined length, thereby the bundle that acquisition is prescinded can be coated to the thermoplastic resin dispersion on the bundle that prescinds then by method as spraying, then heating, thus obtain pellet drying and/or fusion.

When preferably applying, use or when flooding this structure with foam or by the foams of foam preparation, but using gases is as blowing agent.The example of suitable blowing agent comprises: the mixture of gas and/or gas (as air, carbon dioxide, nitrogen, argon gas, helium etc.).The particularly preferred air that is to use is as blowing agent.Blowing agent is introduced by gas machinery is incorporated in the liquid usually, thereby forms foam.This technology is called mechanical foaming.When the polyolefin backing of preparation foaming, preferably mix all components, use equipment such as OAKES, MONDO or FIRESTONE foaming machine that air or gas are blended in the mixture then.

Use/flood control

Can control amount or degree with dispersion dipping or coated fiber structure.For example, dipping can be removed excessive material and control by extruded fabric between calender.In addition, can for example control dipping by the following method: the concentration, substrate (fiber or fabric) of regulating polymer total in the viscosity, aqueous dispersion of composition and stabilizing agent by the speed of dispersion, by suitable mechanism as making bundle (for example by former, constrained port (restricting orifice)) wipes the concentration of filler in the degree, composition of excessive dispersion, perhaps one or more in the polarity of aqueous dispersion.

In some embodiments, substrate coating or dipping (as based on the fiber of glass or contain the substrate of glass) as described in the total amount of at least a thermoplastic resin and dispersion stabilizer can be substrate about 0.1 per 100 parts of by weight of coated or dipping to about 10 parts; In other embodiments, be 0.5 to 8 part; With still in other embodiments, be 1 to 6 part.In other embodiments, substrate coating or dipping can contain the glass of 92wt% at least, based on the gross weight of substrate, thermoplastic resin and dispersion stabilizer; In other embodiments, the glass of 94wt% at least; In other embodiments, the glass of 96wt% at least; Still in other embodiments, the glass of 98wt% at least.For example in some embodiments, for coating or the degree of steeping that keeps expecting, thermoplastic resin can be controlled to be aqueous dispersion about 35 to about 55wt%.In other embodiments, thermoplastic resin can be controlled to be aqueous dispersion about 40 to about 50 volume %.In other embodiments, the viscosity of dispersion can be controlled to be about 20 to about 3000cP.

It will be understood to those of skill in the art that the expected degree of dipping or amount can be saturated fully to fibre structure of fractional saturation (partial saturation) from fibre structure.The degree of steeping of expectation can be depending on various variablees, for example comprises the character of impregnated material and the character of macerate.Those skilled in the art will be understood that also the final character of the expection of the structure of dipping will influence the selection of concrete composition (for example substrate and dispersion) and machined parameters.

In some embodiments, dispersion can be administered in the substrate, causing coating thickness is 0.1 micron to 10 microns.In other embodiments, coating thickness can be at least 1 micron, and at least 2 microns, or at least 5 microns.

In some embodiments, dispersion can be administered in the substrate, causing coating weight is that every square metre of substrate surface of 1 gram is long-pending long-pending to every square metre of substrate surface of 100 grams.

Character with above-mentioned dispersion coating or dipping substrate may change substrate.For example, coating can provide the viscosity that combines with second substrate to substrate.In some embodiments, when being bonded to second substrate, the bonding force of the substrate of coating can be 0.7lb/in at least.In other embodiments, when being bonded to second substrate, the bonding force of the substrate of coating can be 0.7lb/in to 1.1lb/in.In other embodiments, the cohesive force of the comparable uncoated substrate of the bonding force of the substrate of coating greatly at least 10%.The used bonding force of the application is meant that the substrate that will apply separates required power with second substrate.

Another example of the improvement character that coating can promote or improve is based on the fiber of glass or contains the substrate of glass and the compatibility of other material (as polypropylene, nylon and common other used in textile application fibers).

As another example that improves character, apply or dipping can improve based on the fiber of glass or contains the tensile strength of the substrate of glass.In some embodiments, the comparable uncoated or untreated substrate of the tensile strength of substrate coating or dipping greatly at least 10%.

In other embodiments, coating or dipping can be used for not being subjected to injurious effects or chemical etching at the bottom of the protecting group.Still in other embodiments, can be shapable based on goods glass or that contain glass, make then to apply the shape that can change them or dipping with above-mentioned dispersion.In some embodiments, but goods can be serviceability temperatures and/or pressure-formed.In some embodiments, the hot-forming temperature of goods can be in the melt temperature of thermoplastic resin be added and subtracted 50 ℃.

In some embodiments, the independent fiber that applies based on glass, or as the fiber based on glass of the part of the goods that contain glass, its diameter can be 5 to 35 microns.In other embodiments, the diameter based on the fiber of glass can be 10 to 30 microns.

In some embodiments, the basic weight of the goods that contain glass (comprising the felt seat, adhesive-bonded fabric, woven fabric, and fabric) the disclosed coating of the application or dipping can be 25 to 1,000g/m ²In other embodiments, the basic weight that contains the goods of glass can be 30 to 950g/m ²In other embodiments, the fusing point of these goods can be less than 110 ℃.

The goods that the contain glass disclosed coating of the application or dipping can use coating/sticker of drying regime (directly being coated on goods/fiber) and wet condition (water and sticker are with the fiber pulp of prescinding, and drying forms goods then) to form.In some embodiments, the amount of application of coating/sticker can be 0.05 to 20wt%.In other embodiments, the amount of application of coating/sticker can be 0.25 to 15wt%; Still in other embodiments, can be 0.45 to 10wt%.

In other embodiments, substrate can be used the above-mentioned dispersion coating of one deck at least.In other embodiments, can use above-mentioned dispersion will contain the goods of glass or be adhered to second substrate, on fabric based on the fiber of glass.

Still in other embodiments, can form laminated material, wherein the above-mentioned dispersion of one deck is arranged at least one substrate at least.Described at least one substrate can be the goods that contain glass, based on the fiber of glass, foam, foams, thermoplastic sheets or film, woven or non-woven fabric, glass fibre, or fusion spunbond or the meltblown material.

In some embodiments, can form laminated material, wherein the above-mentioned dispersion of one deck is adhered at least one substrate at least.In other embodiments, the disclosed dispersion of the application can be placed between two basalises, described two basalises can be identical or different substrates.In some embodiments, can be immersed in the goods that apply in the polymer or use polymer-coated.

Still in other embodiments, contain the goods of glass or can apply with two-layer or more multi-layered above-mentioned dispersion based on the fiber of glass.In various embodiments, described two-layer or more multi-layered can formation by identical or different dispersion, and can have identical or different coating thickness or coating weight.

Embodiment

Embodiment 1

(continuous glass roving strand is available from the VETROTEX of Saint-Gobain with continuous glass rove bundle ^TMRO99 719) launch from the outside of standard bobbin.As shown in Figure 2, by Film pulling roll unit (film pull roll unit) passes through this rove tractive with the speed of 8 feet per minutes (ft/min.) aqueous dispersion of melt kneading thermoplastic.This aqueous dispersion comprises deionized water and the 20wt% solid of 80wt%.Described solid comprises long-chain carboxylic acid's surfactant and the propylene that is rich in propylene of 17.65wt% and the copolymer (9% ethene) of ethene of 2.35wt%, and the density of described copolymer is that 0.876 gram every cubic centimetre of (g/cc) and melt flow rate (MFR) (MFR) (at 230 ℃ and apply under the condition of 2.16 kilograms of load) are 25 to restrain per 10 minutes (g/10min.).The particle mean size of dispersion is about 0.61 micron, and polydispersity is 1.31.The pH value of the aqueous dispersion of this melt kneading is 11.6.This glass rove is pulled through the distance of the about 75mm of this bath.After submergence and withdrawing from this bath, remove excessive liquid from the bundle that applies by contacting with fluoropolymer polymer curette (fluoropolymer wiper).Wet bundle is drawn in the pressure air kiln of the temperature that remains on 180 ℃.In this stove, this bundle is by a series of pulley and guide rail, and this pulley and guide rail provide enough paths for 1 minute time of staying in stove.In this stove, water is removed, the softening and fusion of acrylic polymers.Be clamminess owing on glass fibre, having softening polymer coating when occurring in the Shu Zaicong stove of the coating of this drying.The bundle of this coating in air, be cooled to fast coated glass fibers the flat bundle of hard (stiff, flatbundle).Use the glass chopped rifle of pneumatic gearing (chopper gun) the flat bundle of the coating of this glass fibre to be cut into the concentrated pellet (concentrate pellets) of long glass fibres (LGF) of 12mm.

Tractor is positioned at the back and the short front of cutting rifle of stove.The glass content of this sample was measured 550 ℃ of ashing in Muffle furnace by making pellet in 2 hours.Glass content is determined as removes organic coating remaining weight afterwards, and it is 90.8%.

In polybag, LGF is concentrated pellet (33 parts) and 7.5 parts of polypropylene homopolymer pellets (as 5E16S Polypropylene Resin, 35MFR is available from Dow Chemical Company-" 5F16S "), the polypropylene granules of 7.5 parts of polypropylene homopolymer pellets (as DX5E30S Polypropylene Resin, 75MFR is available from Dow Chemical Company-" DX5E30S "), 2 parts of maleic anhydride grafts is (as POLYBOND ^TM3200 available from Crompton) and 50 parts of polypropylene and ethylene copolymer pellet (as 7C54H Polypropylene Resin, 12MFR is available from Dow ChemicalCompany-" 7C54H ") do and mix, and shake.The blend of pellets of this mixing is placed ToyoPLASTAR ^TMIn the feed hopper of SI-90 injection molding machine of plastic, this injection machine is equipped with the mould of the two drops (twin drops) that contain the CD that is useful on standard A STM tensile bar (tensile-bar) and 2 inch diameters.Use Temperature Distribution near 395 (202 ℃) to 385 (196 ℃) of nozzle of hopper by the said composition moulding part.Mold temperature is 100 °F, and the retention time is 15 seconds, and the back pressure of use is 250 pound per square inches (psi).The parts color of producing is ecru (off-white), and outward appearance is even, has smooth surface, does not have gathering of visible glass fibre.

Embodiment 2

Embodiment 2 and embodiment 1 the same carrying out, different is to withdraw from this Shu Zaicong stove to pass circular die and be cooled to the hard circular beam in air afterwards.Use Killion tube drawing core machine (tubepuller), rather than

Film pulling roll unit, and described Killion tube drawing core machine is positioned at after the circular die and cutting machine before.Glass content is determined as 90.7%, based on the weight of long glass thermoplastic concentrate.

Embodiment 3

Embodiment 3 and embodiment 2 the same carrying out, that different is polypropylene homopolymer pellet (5E16S), the amount of polypropylene homopolymer pellet (DX5E30S) and polypropylene and ethylene copolymer pellet (7C54H) is respectively 9wt%, 9wt% and 47wt%.Glass content is determined as 90.7% in the concentrate, based on the weight of long glass thermoplastic concentrate.

Embodiment 4

Embodiment 4 and embodiment 2 the same carrying out, different is that two kinds of glass rove bundles are what to be applied.Glass content is determined as 90.7, based on the weight of long glass thermoplastic concentrate.

The composition of the LGF concentrate of embodiment 1 to 4 is listed in the table 1.The character that comprises the molded test specimen of described LGF concentrate is tested according to following test method, and character is recorded in the table 1.The izod impact strength that records by the test of " breach " and " non-notch " izod records at 23 ℃ according to ASTM D256-90-B standard.Sample jaggy uses TMI 22-05 slotting machine (notcher) to carry out otch, obtains the otch of 0.254mm radius.Use 0.91 kilogram pendulum.Numerical value is with Foot-Pound per inch (ft-lb/in) record.

The impact with 15 mph.s (MPH) on MTS 810 instrumentation impact test apparatus records " dart " instrumented resistance to impact according to ASTM D 3763.Result of the test is 23 ℃ of mensuration.Result of the test is with in-lb (in-lb) record.

Flexural modulus (" Fm ") and flexural strength (" Fs ") record according to ASTM D 790.Result of the test is with pound per square inch (psi) record.

Tensile elongation (" Te "), stretch modulus (" Tmod ") and tensile strength (" Ts ") are measured according to ASTM D638.Te result is with percentage (%) record, and Tm and Ts result are with the psi record.

Deformation temperature under the load (" DTUL ") records with 264psi (1.8 MPas (MPa)) on unannealed sample according to ASTM D 648.The result with Fahrenheit temperature (°F) record.

" ash content " according to ASTM D 5650 canonical measures, and with the % record.

Table 1.

Embodiment	1	2	3	4
Component
					7C54H
	50	50	47	50
					5E16S	7.5	7.5	9	7.5
DX5E30S	7.5	7.5	9	7.5
					LGF-Dan Shu-Ping's	33	--	--	--
LGF-Dan Shu-circle	--	33	33	--
					LGF-two-beam-circle	--	--	--	33
POLYBOND TM 3200	2	2	2	2
Character
					Fm，10 5psi	n/a *	7.64	7.68	7.87
Fs，psi	n/a	18，500	18，700	18，700
					Te，％	n/a	3	3	3
Tmod，10 5psi	n/a	7.88	8.05	6.92
					Ts，psi	n/a	11，200	11，700	10，800
Notched izod, ft-lb/in	3.2	4.7	4.7	5.0
					The non-notch izod, ft-lb/in	n/a	14.9	15.9	16.1
					Dart
Peak energy, in-lb	51	59	62	79
					Gross energy, in-lb	n/a	301	301	303
DTUL，°F	n/a	301	301	303

^*N/a=does not obtain

Embodiment 5

With continuous glass rove bundle (available from the VETROTEX of Saint-Gobain ^TMRO99 719) launch from the outside of standard bobbin.As shown in Figure 2, by

Film pulling roll unit passes through this rove tractive with the speed of 8 feet per minutes (ft/min.) aqueous dispersion of melt kneading thermoplastic.This aqueous dispersion comprises deionized water and the 20wt% solid of 80wt%.Described solid comprises long-chain carboxylic acid's surfactant and the propylene that is rich in propylene of 17.65wt% and the copolymer (9% ethene) of ethene of 2.35wt%, and the density of described copolymer is that 0.876 gram every cubic centimetre of (g/cc) and melt flow rate (MFR) (MFR) (at 230 ℃ and apply under the condition of 2.16 kilograms of load) are 25 to restrain per 10 minutes (g/10min.).The particle mean size of dispersion is about 0.61 micron, and polydispersity is 1.31.The pH value of the aqueous dispersion of this melt kneading is 11.6.This glass rove is pulled through the distance of the about 75mm of this bath.After submergence and withdrawing from this bath, remove excessive liquid by contacting with the fluoropolymer polymer curette from the bundle that applies.Wet bundle is drawn in the pressure air kiln of the temperature that remains on 180 ℃.In this stove, this bundle is by a series of pulley and guide rail, and this pulley and guide rail provide enough paths for 1 minute time of staying in stove.In this stove, water is removed, the softening and fusion of acrylic polymers.Be clamminess owing on glass fibre, having softening polymer coating when occurring in the Shu Zaicong stove of the coating of this drying.The bundle of this coating is cooled to the flat bundle of hard of coated glass fibers fast in air.Use the glass chopped rifle of pneumatic gearing the flat bundle of the coating of this glass fibre to be cut into the concentrated pellet of long glass fibres (LGF) of 12mm.

Tractor is positioned at the back and the short front of cutting rifle of stove.The glass content of this sample was measured 550 ℃ of ashing in Muffle furnace by making pellet in 2 hours.Glass content is determined as removes organic coating remaining weight afterwards, and it is 92.3%.

In polybag, LGF is concentrated pellet (33 parts) and 7.5 parts of polypropylene homopolymer pellets (as 5E16S Polypropylene Resin, 35MFR is available from Dow Chemical Company-" 5E16S "), 7.5 part polypropylene homopolymer pellet is (as DX5E30S Polypropylene Resin, 75MFR is available from Dow Chemical Company-" DX5E30S "), the polypropylene granules of 2 parts of maleic anhydride grafts is (as POLYBOND ^TM3200 available from Grompton) and 50 parts of polypropylene and ethylene copolymer pellet (as 7C54H Polypropylene Resin, 12MFR is available from Dow ChemicalCompany-" 7C54H ") do and mix, and shake.The blend of pellets of this mixing is placed ToyoPLASTAR ^TMIn the feed hopper of SI-90 injection molding machine of plastic, this injection machine is equipped with the mould of the CD that contains the two drops (twin drops) that are useful on standard A STM tensile bar and 2 inch diameters.Use temperature configuration near 395 (202 ℃) to 385 (196 ℃) of hopper with nozzle by the said composition moulding part.Mold temperature is 100 °F, and the retention time is 15 seconds, and the back pressure of use is 250 pound per square inches (psi).The parts color of producing is an ecru, and outward appearance is even, has smooth surface, does not have gathering of visible glass fibre.

Comparative Examples 1

Impact polypropylene copolymers (the INSPIRE of two 100mil of preparation ^TMD 114.00, and propylene-ethylene copolymers, it has the ethene of about 8.5wt%, can be available from Dow Chemical Company) sheet material, the melt flow rate (MFR) of described impact polypropylene copolymers be 0.5g/10min (230 ℃/2.16kg).Basic weight is 450g/m ²10 inches * 10 inches glass fibre continuous filament yarn felt seat (can with title M8643 available from Owens Coming) place between the described two-layer 100mil PP sheet material.Then this sandwich was reinforced about 5 minutes with about 500psi and 170 ℃ in forcing press (press).

Embodiment 6

Aqueous polyolefin dispersions comprises 80wt% deionized water and 20wt% solid.This solid comprises the propylene that is rich in propylene of 2.35wt% long-chain carboxylic acid surfactant and 17.65wt% and the copolymer of ethene (9% ethene), and the density of described copolymer is that 0.876 gram every cubic centimetre of (g/cc) and melt flow rate (MFR) (MFR) (at 230 ℃ and apply under the condition of 2.16 kilograms of load) are 25 to restrain per 10 minutes (g/10min.).The particle mean size of dispersion is about 0.61 micron, and polydispersity is 1.31.The pH value of the aqueous dispersion of this melt kneading is 11.6.Then this aqueous dispersion being diluted to solid content is about 10wt%.

Be 450g/m by the felt seat being immersed into the dispersion dipping basic weight of using dilution in the dispersion then ²10 inches * 10 inches glass fibre continuous filament yarn felt seat.Felt seat with dipping takes out from dispersion then, and makes excessive dispersion drippage.Then with wet felt seat with upright position in remaining on 100 ℃ convection furnace dry 5 minutes.Obtain about 30g/m ²Dry-coated weight.

In independent operation, the impact polypropylene copolymers (INSPIRE of preparation 100mil ^TMD114.00 can be available from Dow Chemical Company) sheet material, the melt flow rate (MFR) of described impact polypropylene copolymers be 0.5g/10min (230 ℃/2.16kg).Felt seat with dipping places between two-layer this 100mil PP sheet material then.Then this sandwich was reinforced about 5 minutes with about 500psi and 170 ℃ in forcing press (press).The thermoplastic structure that the glass that obtains strengthens can use in various application.

When comparing with Comparative Examples 1, the joint product of embodiment 6 (composite product) demonstrates better engineering properties, as higher elongation at break, and higher tensile strength and higher impact resistance.

Embodiment 7

Preparation is based on not functionalized PP (VERSIFY ^TMDP4200) and PRIMACOR ^TMThe aqueous polyolefin dispersions of the blend of 5980I.VERSIFY ^TMDP4200 be ethylene contents be about 9wt% and melt flow rate (MFR) be 25dg/min (230 ℃, propylene-ethylene copolymers 2.16kg).PRIMACOR ^TMBe acrylic acid content be about 20.5wt% and melt flow rate (MFR) for about 13.75dg/min (125 ℃, ethylene-acrylic acid copolymer 2.16kg).VERSIFY ^TMDP4200/PRIMACOR ^TMThe 5980I dispersion is by preparing with 13.9lb/hr charging DP4200 pellet with 2.9lb/hr charging 5980I pellet in extruder loading hopper (extruder feedfunnel) simultaneously.The aqueous solution of deionized water and 25% (w/w) potassium hydroxide respectively with 19 and the 8.3cc/min pumping, is merged, be heated to about 160 ℃, and be injected in the extruder barrel at emulsion band, wherein this machine barrel operates in about 150 ℃.Deionized water with the 90cc/min pumping, is heated to about 110 ℃, and is injected in the extruder barrel in the dilution section, wherein this machine barrel operates in about 80 ℃.Control the dilution of product at the pressure of about 300psig.The VERSIFY that obtains ^TMDP4200/PRIMACOR ^TMThe solid content of 5980I dispersion is 51.6wt%, and pH is about 10.0, and the volume average particle sizes that records by Beckman Coulter LS 230 is about 1.0 microns, and polydispersity (being defined as volume average particle sizes divided by number average particle size) is less than 2.

With VERSIFY ^TMDP4200/PRIMACOR ^TMIt is about 10wt% that the 5980I dispersion is diluted to solid content.With continuous glass rove bundle (available from the VETROTEX of Saint-Gobain ^TMRO99719) launch from the outside of standard bobbin.With the speed of 8 feet per minutes (ft/min.) this rove tractive is passed through the thermoplastic aqueous dispersion by Brabender film pulling roll unit.After submergence and withdrawing from this bath, remove excessive liquid from the bundle that applies by contacting with the fluoropolymer polymer curette.Wet bundle is drawn in the pressure air kiln of the temperature that remains on 180 ℃.In this stove, this bundle is by a series of pulley and guide rail, and this pulley and guide rail provide enough paths for 1 minute time of staying in stove.In this stove, water is removed, the softening and fusion of acrylic polymers.Be clamminess owing on glass fibre, having softening polymer coating when occurring in the Shu Zaicong stove of the coating of this drying.The quick air of the bundle of this coating is cooled to the flat bundle of hard (stiff, flat bundle) of coated glass fibers.

In independent operation, the method for weaving that then uses routine well known by persons skilled in the art is woven into the twin shaft fabric with the bundle of this coated glass fibers.

In independent operation, the impact polypropylene copolymers (INSPIRE of preparation 100mil ^TMD114.00 can be available from Dow Chemical Company) sheet material, the melt flow rate (MFR) of described impact polypropylene copolymers be 0.5g/10min (230 ℃/2.16kg).This twin shaft fabric is placed between two-layer this 100mil PP sheet material then.Then this sandwich was reinforced about 5 minutes with about 500psi and 170 ℃ in forcing press (press).The thermoplastic structure that the glass that obtains strengthens can use in various application.

Compare with Comparative Examples 1, the joint product of embodiment 7 (composite product) demonstrates better engineering properties, as higher elongation at break, and higher tensile strength and higher impact resistance.This may be that such phase can provide and the better compatibility of impact polypropylene copolymers sheet material owing to there is not functionalized polypropylene phase.

Embodiment 8

Preparation is based on not functionalized PP (VERSIFY ^TMDP4200) and PRIMACOR ^TMThe aqueous polyolefin dispersions of the blend of 5980I.VERSIFY ^TMDP4200/PRIMACOR ^TMThe 5980I dispersion is by preparing with 13.9lb/hr charging DP4200 pellet with 2.9lb/hr charging 5980I pellet in the extruder loading hopper simultaneously.The aqueous solution of deionized water and 25% (w/w) potassium hydroxide merges respectively with 19 and the 8.3cc/min pumping, is heated to about 160 ℃, and is injected in the extruder barrel at emulsion band, and wherein this machine barrel operates in about 150 ℃.Deionized water with the 90cc/min pumping, is heated to about 110 ℃, and is injected in the extruder barrel in the dilution section, wherein this machine barrel operates in about 80 ℃.Control the dilution of product at the pressure of about 300psig.The VERSIFY that obtains ^TMDP4200/PRIMACOR ^TMThe solid content of 5980I dispersion is 51.6wt%, and pH is about 10.0, and the volume average particle sizes that records by Beckman Coulter LS 230 is about 1.0 microns, and polydispersity (being defined as volume average particle sizes divided by number average particle size) is less than 2.With VERSIFY ^TMDP4200/PRIMACOR ^TMIt is about 10wt% that the 5980I dispersion is diluted to solid content.

Use the glass-making processes of routine well known by persons skilled in the art to prepare continuous glass rove bundle.After the sleeve pipe that is used for the glass manufacturing operation withdraws from, with the VERSIFY of fiber tractive by this dilution ^TMDP4200/PRIMACOR ^TMThe 5980I dispersion.After submergence and withdrawing from this bath, remove excessive liquid from the bundle that applies by contacting with the fluoropolymer polymer curette.Wet bundle is drawn in the pressure air kiln of the temperature that remains on 180 ℃.In this stove, this bundle is by a series of pulley and guide rail, and this pulley and guide rail provide enough paths for 1 minute time of staying in stove.In this stove, water is removed, the softening and fusion of acrylic polymers.Be clamminess owing on glass fibre, having softening polymer coating when occurring in the Shu Zaicong stove of the coating of this drying.The quick air of the bundle of this coating is cooled to the flat bundle of hard of coated glass fibers.

In independent operation, the method for weaving that then uses routine well known by persons skilled in the art is woven into the twin shaft fabric with the bundle of this coated glass fibers.

In independent operation, the impact polypropylene copolymers (INSPIRE of preparation 100mil ^TMD114.00 can be available from Dow Chemical Company) sheet material, the melt flow rate (MFR) of described impact polypropylene copolymers be 0.5g/10min (230 ℃/2.16kg).This twin shaft fabric is placed between two-layer this 100mil PP sheet material then.Then this sandwich was reinforced about 5 minutes with about 500psi and 170 ℃ in forcing press.The thermoplastic structure that the glass that obtains strengthens can use in various application.

Advantageously, the disclosed embodiment of one or more the application can be provided at composition, method and the goods that have superperformance in their the expection application.For example, one or more embodiments can provide filamentary structure, the rigidity, elasticity (elasticity), resilience (resilience), adhesion, shape that this structure has an improvement keep or compatibility in one or more.

Though described the present invention, it should be appreciated by those skilled in the art that under the situation that does not depart from the disclosed scope of the present invention of the application to propose other embodiment with reference to the embodiment of limited quantity.Therefore, scope of the present invention should be limited by claims.

Claims (39)

1. form the method for goods, described method comprises:

Use composition to the substrate that contains glass, described composition comprises:

Aqueous dispersion, described aqueous dispersion comprises:

(a) thermoplastic resin;

(b) dispersion stabilizer; With

(c) water;

Remove at least a portion water.

2. the method for claim 1 comprises and removes at least 50% water.

3. the process of claim 1 wherein that described goods have the glass of 92wt% at least, based on the gross weight of substrate, thermoplastic resin and dispersion stabilizer.

4. the process of claim 1 wherein that described goods have the glass of 94wt% at least, based on the gross weight of substrate, thermoplastic resin and dispersion stabilizer.

5. the dispersion of claim 1, wherein said thermoplastic resin is nonpolar, and described dispersion stabilizer is a polarity.

6. the method for claim 5, wherein said thermoplastic resin and dispersion stabilizer form two different phases.

7. the process of claim 1 wherein and describedly remove at least a portion water to cause thickness be 0.1 micron to 100 microns coating.

8. the process of claim 1 wherein and describedly remove at least a portion water to cause coating weight be that every square metre of substrate surface of 1 gram is long-pending long-pending to every square metre of substrate surface of 100 grams.

9. the process of claim 1 wherein that described thermoplastic resin comprises the many block interpolymers of Natene, polyethylene and ethylene copolymers or polyethylene, the many block interpolymers of polypropylene homopolymer, polypropylene copolymer or polypropylene, or its combination.

10. the method for claim 9, wherein said thermoplastic resin is nonpolar.

11. the process of claim 1 wherein that the heat distortion temperature of described thermoplastic resin under load is 75 ℃ to 110 ℃.

12. the method for claim 1 also comprises goods directly are attached on the fabric, and does not use adhesive.

13. goods, it comprises:

With the composition that the part of the substrate that contains glass contacts, wherein said composition comprises aqueous dispersion when contact, and described aqueous dispersion comprises:

(a) deformation temperature is less than 110 ℃ polyolefin;

(b) dispersion stabilizer; With

(c) water

Wherein said composition is given improved character to substrate; With

Wherein said substrate is plastic.

14. the goods of claim 13, wherein the hot-forming temperature of goods is in polyolefinic melt temperature ± 50 ℃.

15. the goods of claim 13, wherein said improved character are selected from following at least a: with the adhesion of second substrate, tensile strength, compatibility, and bonding force.

16. the goods of claim 15, the value of wherein said improved character is than the substrate of not contact greatly at least 10%.

17. the goods of claim 15, the bonding force of wherein said goods are 0.7 to 1.1lb/in.

18. the goods of claim 13, wherein said polyolefin comprise the many block interpolymers of Natene, polyethylene and ethylene copolymers or polyethylene, the many block interpolymers of polypropylene homopolymer, polypropylene copolymer or polypropylene, or its combination.

19. the goods of claim 18, the heat distortion temperature of wherein said polyolefin under load are 75 ℃ to 110 ℃.

20. the goods of claim 13, the wherein said basic weight that contains the goods of glass are every square metre of 25 to 1000 gram.

21. goods, it comprises:

With the composition that the part of the substrate that contains glass contacts, wherein said composition comprises aqueous dispersion when contact, and described aqueous dispersion comprises:

(a) thermoplastic resin;

(b) dispersion stabilizer; With

(c) water

Wherein said goods have the glass of 92wt% at least, based on the gross weight of the substrate that contains glass, thermoplastic resin and dispersion stabilizer.

22. the goods of claim 21, wherein said goods have the glass of 94wt% at least, based on the gross weight of the substrate that contains glass, thermoplastic resin and dispersion stabilizer.

23. the goods of claim 21, wherein said goods are selected from the felt seat, adhesive-bonded fabric, woven fabric, and fabric.

24. the goods of claim 21, wherein said glass are E type glass.

25. a coated fiber, it comprises:

The composition that contacts with a part based on the fiber of glass, wherein said composition comprises aqueous dispersion when contact, described aqueous dispersion comprises:

(a) thermoplastic resin;

(b) dispersion stabilizer; With

(c) water

The diameter of wherein said fiber is 5 to 35 microns; With

Wherein said composition is about 0.1 to 10 micron at described thickness based on the coating on the fiber of glass.

26. the coated fiber of claim 25, wherein said thermoplastic resin comprise that Vicat softening point is 75 ℃ to 110 ℃ a polyolefin.

27. the coated fiber of claim 25, wherein said thermoplastic resin comprise the many block interpolymers of Natene, polyethylene and ethylene copolymers or polyethylene, the many block interpolymers of polypropylene homopolymer, polypropylene copolymer or polypropylene, or its combination.

28. the coated fiber of claim 27, the functionalized polymer of wherein said thermoplastic resin right and wrong.

29. goods, described goods are formed by the coated fiber of claim 25.

30. the method for coated fiber comprises:

Use composition to the fiber based on glass, described composition comprises:

Aqueous dispersion, described aqueous dispersion comprises:

(a) thermoplastic resin;

(b) dispersion stabilizer; With

(c) water;

Remove at least a portion water.

31. the method for claim 30, wherein said step of applying comprises:

Fibre bundle is contacted with described aqueous dispersion; With

Make described fiber through former.

32. the method for claim 30, wherein said fiber based on glass are the fibers of pulverizing based on glass.

33. the method for claim 30, wherein said fiber based on glass is a continuous tow.

34. goods, it comprises:

Place at least one layer composition at least a portion of the substrate that contains glass, wherein said composition comprises:

(a) deformation temperature is less than 110 ℃ polyolefin; With

(b) dispersion stabilizer; With

Wherein said composition is given improved character to substrate; With

Wherein said substrate is plastic.

35. the goods of claim 34, wherein said goods have the glass of 92wt% at least, based on the gross weight of substrate, thermoplastic resin and dispersion stabilizer.

36. the goods of claim 34, wherein said thermoplastic resin right and wrong are functionalized, and described dispersion stabilizer is functionalized.

37. the goods of claim 34, wherein said thermoplastic resin is nonpolar, and described dispersion stabilizer is a polarity.

38. the goods of claim 37, wherein said thermoplastic resin forms two different phases with dispersion stabilizer.

39. the goods of claim 34, the melt temperature of wherein said goods is less than 110 ℃.

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