CN1074780C - Semi-interpenetrating polymer networks of epoxy and polyolefin resins, methods therefor and uses thereof - Google Patents

Abstract

The present invention relates to a curable composition which comprises 0.1 to 50% by weight of curable epoxy resin (the weight percentage is based on the whole resin composition), effective dose of a curing agent of the curable epoxy resin, and 50 to 99.9% by weight of at least one of fully prepolymerized non-crosslinked hydrocarbon polyolefine resin and fully prepolymerized non-crosslinked polyolefine resin functionalized by at least one polar group (the weight percentage is basd on the whole resin composition), wherein the hydrocarbon polyolefine is 25 to 99.9% by weight of the whole resin composition, the functionalized polyolefine is 0 to 49.9% by weight of the whole resin composition, and the composition does not contains epoxidized natural rubber and/or synthetic rubber.

Description

The semiinterpenetrating polymer network of Resins, epoxy and polyolefin resin and manufacture method thereof and application

FIELD OF THE INVENTION

The thermoplastic resin that the present invention relates to heat of polymerization thermosetting resin (being Resins, epoxy) in the presence of the thermoplastic polymer (being polyolefin homopolymer or multipolymer) of fully pre-polymerization and make and the semiinterpenetrating polymer network (half IPNs) of thermosetting resin.The present invention also relates to 100% solid processing and potential or after fixing Resins, epoxy is the manufacture method of semiinterpenetrating polymer network of characteristic and the application of the semiinterpenetrating polymer network that makes in this way.

The background of invention

For make thermosetting resin toughen (promptly increasing its toughness) in the hard thermosetting resin, mix a small amount of resilient material or thermoplastic material is industrial method commonly used.Elasticity or thermoplastic toughening agent comprise natural rubber, polyolefine and ethylenic copolymer, as poly-(vinylbenzene-be total to-divinyl).In these cases, the mixture ratio of toughner and curable thermosetting resin is 1: 20-1: 4, and make thermoplastic component become disperse phase in the thermosetting resin external phase.

United States Patent (USP) 3,505,429 have described the mixing material of polyolefine with a large amount of " polymer-modified ", wherein record " dihydroxyphenyl propane-epichlorohydrin polymers that has epoxy-activated group ", it accounts for the 0.01-1% of whole polymer composition weight.Do not mention the polymerization of epoxide.United States Patent (USP) 4,791,144 describe polypropylene (polyolefine) film.In other composition, this film contains " epoxy plasticizer " of 40-10% weight (is benchmark by each component summation).The softening agent of carboxylic-acid functional (as epoxidised soya-bean oil and epoxidised Toenol 1140) is preferred.Polymerization does not take place in these epoxide.

Semiinterpenetrating polymer network is defined as the polymer network of two or more polymkeric substance, and wherein a kind of polymkeric substance is crosslinked, and another kind of polymkeric substance is not crosslinked.Encyclopedia of Polymer Science andEngineering Vol.8; John Wiley ﹠amp; Sons has put down in writing the semiinterpenetrating polymer network that comprises many polymeric systems among New York (1984) 279-332.The diagram of semiinterpenetrating polymer network is illustrated in 282 pages, structure (c).Once reported that containing uncured Resins, epoxy was that main ingredient and butadiene-acrylonitrile rubber are the semiinterpenetrating polymer network (English Patent 736,457) of accessory constituent and the semiinterpenetrating polymer network (English Patent 1,247,116) that contains uncrosslinked elastomer latices.The semiinterpenetrating polymer network of polyolefine and three Resins, epoxy once was documented in Negmatov etc., Uzb.Khim.Zh., 1990 (6), 65-7; CA115:93689n (1991), but do not disclose the manufacture method of the consumption and the semiinterpenetrating polymer network of solidifying agent, each component.

Perepechko etc., Kompoz.Polim.Mater., 1988,37 volumes, 29-32; CA110:09100e (1989) has extensively described the mixture of polyethylene, maleic anhydride, dicumyl peroxide and Resins, epoxy.Polyethylene is in the method by peroxide crosslinking, but it is not a semiinterpenetrating polymer network.

In the presence of common, form two kinds of polymkeric substance, and produce two kinds independently during crosslinking polymer network, the formation interpenetrating polymer networks.Having put down in writing one of polymkeric substance is the interpenetrating polymer networks of Resins, epoxy.The preparation method of interpenetrating polymer networks is simultaneously or the successively unsaturated acrylate type monomer of alkene class and the epoxy monomer of polymerization free redical polymerization.For example referring to United States Patent (USP) 5,399,637,5,376,428,5,086,086 and 4,952,612.Each component all is a monomer in all cases.

Only when introducing functional group with copolymerization method or graft polymerization method, could successfully mix a spot of epoxy functionalized resin (be up to polyolefine weight 10%) when coming the modified polyolefin component as carboxylic acid, carboxylic acid anhydride, carboxylicesters, carboxylic acid amide, nitrile or halogen (particularly chlorine), in these cases, do not add extra epoxy hardener, do not report further cured epoxy resin component yet.The shortcoming of this method is the cost that has increased polyolefin component, and under the graft polymerization situation, graft polymerization method itself produces adverse influence (chain rupture and other unwanted side reaction) to polyolefine.The United States Patent (USP) of describing representative functionalised polyolefin-epoxy systems comprises 5,349,027 (the grafting method forms the acrylamide functionalised polyolefin), 5,312,867 (the carboxylic acid functionalized polypropylene that the grafting method forms) and 4,997,720 (copolymerization of ethylene and unsaturated carboxylic acids and form carboxylic acid functionalized polyethylene).

United States Patent (USP) 4,769,416 have described a kind of polyolefinic composition that contains with the epoxy natural rubber blending.Wherein in mixing vessel, make the epoxy functionalities thermofixation during melt compounded material.

For a long time, the researchist is devoted to the character of modified polyolefin, so that improve the binding property to metal or polar surfaces, improves modulus, reduces melt viscosity, but improves dyeability, impressionability and other required character.As everyone knows, polyolefine is mutually mutual exclusive with polar resin.Part does not also obtain containing the polyolefinic useful semiinterpenetrating polymer network of solidified Resins, epoxy and complete pre-polymerization so far owing to the uncompatibility of two kinds of polymer types and partly owing to the curable epoxide in restive and the prevention mixing process.

Know the light-initiated cationic polymerization (for example referring to J.Crivello, Advancesin Polymer Science, 62,3 (1984)) of epoxide already.Organic acyl group sulphur and the deemed appropriate light trigger of aryl iodide, promptly after the optical radiation, this compound discharges proton (protons), and this kind of proton for example can cause the epoxide polymerization reaction.Some iron-aromatic hydrocarbons organo-metallic complex salt also is described to the light trigger (referring to United States Patent (USP) 5,089,536,5,191,101,5,385,954 and 5,059,701) of cationic polymerization.Under all these situations, the component of cationically polymerizable all is a monomer.

The general introduction of invention

In simple terms, the invention provides a kind of curable composition.This composition comprises:

A) curable epoxy of 0.1-50% weight, described weight percentage is a benchmark with whole resin combination;

B) solidifying agent of the curable epoxy of significant quantity;

C) uncrosslinked hydro carbons polyolefin resin of the complete pre-polymerization of 50-99.9% weight and the functionalized uncrosslinked polyolefin resin of complete pre-polymerization are at least a in the two, and described weight percentage is a benchmark with whole resin combination;

Wherein said hydro carbons polyolefine accounts for the 25-99.9% weight of whole resin combination, and described functionalised polyolefin accounts for the 0-49.9% weight of whole resin combination, and described composition does not contain epoxidised natural and synthetic rubber.

In one aspect, the present invention describes and to contain heat-curable epoxy resin, optional complete pre-polymerization functionalised polyolefin resin and the semiinterpenetrating polymer network of pre-polymerization hydro carbons polyolefin homopolymer or multipolymer fully.

On the other hand, the present invention describes the Resins, epoxy that contains the photochemistry cationic curing, optional complete pre-polymerization functionalised polyolefin resin and the polyolefine of pre-polymerization fully or the semiinterpenetrating polymer network of its multipolymer.

On the other hand, the present invention describes a kind of manufacture method of semiinterpenetrating polymer network.This method comprises the steps: the epoxy resin thermosetting agent of the hydro carbons thermoplastic polyolefin resin of the complete pre-polymerization of (a) uniform mixing or its multipolymer, the optional complete pre-polymerization polyolefin resin, thermal curable Resins, epoxy and at least a high-temperature stable that contain polar group; (b) subsequently whenever the mixture with gained is coated on substrate, mould or the storage vessel, or be processed into unsupported film and (c), activate described solidifying agent by applying enough heat energy to this mixture.Perhaps can add Resins, epoxy and solidifying agent step by step.

On the other hand, the present invention describes the manufacture method of semiinterpenetrating polymer network.This method comprises the cationic photopolymerization catalyzer of the Resins, epoxy of the polyolefin resin of the complete pre-polymerization of (a) uniform mixing or its multipolymer, cationically polymerizable and at least a Resins, epoxy and the polyolefin resin of the optional complete pre-polymerization that contains polar group; (b) mixture with gained is coated on substrate, mould or the storage vessel, or is processed into unsupported film and (c) makes the activation of described light trigger by the radiation mixture then.Perhaps can add Resins, epoxy and cation light initiator step by step.

That not do not describe in this area and provide the curable compositions that contains curable thermosetting resin (being the hydro carbons polyolefin resin of Resins, epoxy, unmodified complete pre-polymerization and the functionalised polyolefin of optional complete pre-polymerization) among the present invention.Wherein on the spot, molding, coating or make composition with other process useful before, better curable Resins, epoxy is not exposed under the condition of cure (be optical radiation, better UV-light or be approximately higher than 200 ℃ temperature).

In this application:

" hydro carbons polyolefine " is meant the uncrosslinked polymeric hydrocarbon of the complete pre-polymerization that does not have machine functional group basically, and it is by the homopolymerization of olefinic monomer and/or copolymerization and make;

" functionalised polyolefin " is meant the uncrosslinked polymeric hydrocarbon of the complete pre-polymerization of band polar group;

" semiinterpenetrating polymer network " is defined as the polymer network of two or more polymkeric substance, and wherein a kind of polymkeric substance is crosslinked, and another kind of polymkeric substance is not crosslinked.

Detailed description of the preferred embodiments

The invention provides a kind of curable compositions.Said composition comprises:

A) 0.1-50% weight, better 0.1-40% weight, the curable epoxy of best 0.5-20% weight, described weight percentage is a benchmark with whole resin combination;

B) solidifying agent of the curable epoxy of significant quantity;

C) 50-99.9% weight, better 60-99.9% weight, at least a resin in the complete pre-polymerization hydro carbons polyolefin resin of best 80-99.5% weight and the complete pre-polymerization functionalised polyolefin resin, described weight percentage is a benchmark with whole resin combination; Wherein said hydro carbons polyolefine accounts for the 25-99.9% weight of whole resin combination, better account for 40-99.9, preferably account for 70-99.9% weight, described functionalised polyolefin accounts for the 0-49.9% weight of whole resin combination, better account for 0-20, preferably account for 0-10% weight.

Composition of the present invention does not contain epoxidised natural and/or synthetic rubber and elemental sulfur.

When being lower than the heat activation temperature of catalyzer more fortunately, the mixing of each component carries out.Functionalized polar group better contains at least one O, N, S, P or halogen atom.

The invention provides the hydro carbons polyolefine that contains complete pre-polymerization and the curing composition of functionalized polyolefin resin.By adding the cured epoxy resin that forms semiinterpenetrating polymer network, can improve the character of described composition.The character that improves comprises that fiber reinforced material (as sapphire whisker, silicon carbide, silicon nitride, aromatic poly (I steps moral) etc.) binding property, lacquer and protective coating to the conventional fillers (as carbon black, titanium dioxide, silicon-dioxide and talcum) of metal and polar surfaces (as glass, comprising glass fibre), plastics and plastics is to the polyolefine modulus of polyolefinic binding property, raising and the performance in the UL-94 flammability test.

Form contrast with the mixture that contains useful small quantities of hydrocarbon class polyolefine (comprising multipolymer and natural rubber) enhanced Resins, epoxy (being less than 20% rubber strongthener as containing in the epoxy substrate (matrix)) as known in the art, characteristics of the present invention are that the hydro carbons and the functionalised polyolefin of complete pre-polymerization is that main ingredient (50-99.5% weight according to appointment) and Resins, epoxy are enhancement additive.Believe that this epoxy enhanced polyolefin blend was not also reported.The useful semiinterpenetrating polymer network of the present invention better contains the 0.1-40 weight of having an appointment, and is preferably the Resins, epoxy of 0.5-20% weight.Preferred compositions of the present invention also contains 0-20% weight, be preferably the polyolefine of 0-10% weight, as contain the organo-functional group and the better polyolefine of carboxyl, hydroxyl, cyano group, amide group and halogen and so on through copolymerization or grafting copolymerization process modification with the functionalized complete pre-polymerization of at least a polar group.The polyolefinic consumption of hydro carbons of complete pre-polymerization is a 40-99.9% weight in the preferred composition, is preferably 50-99.9% weight.Rest part can contain other suitable conventional additives, filler and auxiliary in this area in the matrix.Below will be for a more detailed description to them.

In the hydro carbons polyolefine external phase of pre-polymerization fully, add Resins, epoxy and formed polyolefine with many advantageous properties.Curable low-molecular-weight epoxy resin is used to reduce polyolefinic melt viscosity, improves the processing treatment performance, as the die head extrusion molding that more easily carries out fiber with fill little space more completely in composite molding or clone method.Reduced processing temperature and just can add out of use temperature-sensitive additive in the high melting-point polyolefins, as halogenated fire retardant.Low-molecular-weight epoxy resin has improved the binding property of this semiinterpenetrating polymer network to various substrates, this part is because this low molecular weight substance can be moved to the resin base interface rapidly, improve binding property, may be by improving the reaction of functional group on wettability or epoxy-functional and the substrate surface.

But the Resins, epoxy of the present invention of thermosetting better comprise contain one or more 1,2,1,3 and 1, the compound of 4-cyclic ethers.These cyclic ethers are also referred to as 1,2,1,3 and 1, the 4-epoxide.Wherein 1,2 cyclic ethers is preferred.These compounds can be saturated or undersaturated, aliphatic, alicyclic, aromatics or heterocycle family, maybe can contain their mixture.The compound (being polyepoxide) that contains more than one epoxy group(ing) is preferred.

Can be used for the polyglycidyl ether that aromatics polyepoxide of the present invention (compound that promptly contains at least one aromatic ring structure (as phenyl ring) and an above epoxy group(ing)) comprises polyphenol, as bisphenol A-type resin and derivative, epoxy-cresols line style varnish resin, Bisphenol F resin and derivative and epoxy phenol-line style varnish resin; With aromatic carboxylic acid's glycidyl ester, as o-phthalic acid diglycidyl ester, m-phthalic acid 2-glycidyl ester, 1,2,4-benzenetricarboxylic acid three-glycidyl ester and 1,2,4,5-pyromellitic acid tetra glycidyl ester, and their mixture.Preferred aromatics polyepoxide is the polyglycidyl ether of polyphenol, as available from Shell Chemical, and Inc., Houston, the EPON of TX ^TMThe diglycidylether of series dihydroxyphenyl propane comprises EPON828 and EPON1001F.

Can be used for the aliphatic ring-type polyepoxide of representativeness of the present invention (promptly contain the ring compound of one or more saturated carbon rings and an above epoxy group(ing), be also referred to as alicyclic compound) and comprise the Corp. available from Union Carbide, the Danbury, " ERL of CT ^TM" serial cycloaliphatic epoxides; as vinyl cyclohexene dioxide (ERL-4206); 3; 4-epoxy cyclohexane carboxylic acid 3; 4-epoxycyclohexyl methyl esters (ERL-4221); 3,4-epoxy-6-methylcyclohexanecarboxylic acid 3,4-epoxy-6-methylcyclohexyl methyl esters (ERL-4201), hexanodioic acid two (3,4-epoxy-6-methylcyclohexyl first) ester (ERL-4289), titanium dioxide kautschin (ERL-4269) and 2-(3,4-epoxycyclohexyl-5,1 "-spiral shell-3 "; 4 "-epoxy cyclohexane-1, the 3-diox, 4-(1, the 2-epoxy ethyl)-1,2-epoxy cyclohexane and 2, two (3, the 4-epoxycyclohexyl) propane of 2-.Preferred alicyclic polyepoxide is ERL ^TMSeries.

Representational aliphatic polyepoxide (promptly do not contain carbocyclic ring but contain the compound of an above epoxy group(ing)) comprises 1,4-two (2, the 3-glycidoxy) butane, the polyglycidyl ether of aliphatic polyol (as glycerine, polypropylene glycol, 1,4-butyleneglycol etc.) and the 2-glycidyl ester of flax dimeracid (linoleic dimer acid).

Many Resins, epoxy can be buied, and enumerate or be documented in the Resins as the Handbook of Epoxy, Chemistry and Technology, Second Edition, C.May, ed., Marcell Decker, Inc., NewYork (1988) and Epoxy Resin Technology, P.F.Bruins, ed., Interscience Publisher, NewYork is in (1968).Wherein said all Resins, epoxy all can be used for preparing semiinterpenetrating polymer network of the present invention.

Also comprise the dual-active comonomer within the scope of the invention, promptly existing epoxy-functional has the compound of at least one other functional group (as hydroxyl, acrylate-based, alkene class unsaturated link(age), carboxylic acid, carboxylicesters etc.) again.This monomeric example is available from UCB Radcure, Inc., Atlanta, the Ebecryl of GA ^TM3605, a kind of existing epoxy-functional has the bisphenol A-type monomer of acrylate-functional groups again.

Solidifying agent of the present invention can be photocatalyst or thermal curing agents.

Catalyzer of the present invention (be also referred to as " initiator ", this term can use in the present invention with replacing) better activates with photochemical method.Known photocatalyst is two big classes: salt or positively charged ion organic metal salt, the both can be used for the present invention.

The salt light trigger that is used for cationoid polymerisation comprises iodine and sulfonium complex salt.Useful aromatics iodine complex salt is represented with following general formula:

In the formula

Ar ¹And Ar ²Can be identical or different, they are the aryl that contain 4-20 carbon atom, and are selected from phenyl, thienyl, furyl and pyrazolyl;

Z be selected from oxygen, sulphur, C-C,

In the formula R can be aryl (containing 6-20 carbon atom) or acyl group (containing 2-20 carbon atom) as ethanoyl, benzoyl as phenyl and

R in the formula ₁And R ₂Be selected from hydrogen, contain 1-4 carbon atom alkyl, contain the alkenyl of 2-4 carbon atom;

M is zero or 1;

The general formula of X is DQ _n, D is metal in the periodic table of elements (chemical abstracts version) the IB-VIII family or the metalloid in the IIIA-VA family in the formula, and Q is a halogen atom, and n is an integer among the 1-6.Described metal better is copper, zinc, titanium, vanadium, chromium, magnesium, manganese, iron, cobalt or nickel, and described metalloid better is boron, aluminium, antimony, tin, arsenic and phosphorus.Halogen Q better is chlorine or fluorine.The example of suitable anion is BF ₄ ^-, PF ₆ ^-, SbF ₆ ^-, FeCl ₄ ^-, SnCl ₅ ^-, AsF ₆ ^-, SbF ₅OH ^-, SbCl ₆ ^-, SbF ₅ ^-2, AlF ₅ ^-2, GaCl ₄ ^-, InF ₄ ^-, TiF ₆ ^-2, ZrF ₆ ^-, CF ₃SO ₃ ^-Deng.Negatively charged ion better is BF ₄ ^-, PF ₆ ^-, SbF ₆ ^-, AsF ₆ ^-, SbF ₅OH ^-And SbCl ₆ ^-Negatively charged ion is more preferably SbF ₆ ^-, AsF ₆ ^-And SbF ₅OH ^-

Ar ¹And Ar ²Aryl can randomly contain one or more fused benzene rings (as naphthyl, benzothienyl, dibenzothiophene base, benzofuryl, dibenzofuran group etc.).If necessary, aryl also can be replaced by one or more non-basic groups, if these groups do not react with epoxide and hydroxy functional group basically.

Useful aromatics iodine complex salt is documented in United States Patent (USP) 4,256 in more detail, and in 828, this patent reference is incorporated among the present invention.Preferred aromatics iodine complex salt is (Ar) ₂IPF ₆(Ar) ₂ISbF ₆

Aromatics iodine complex salt useful among the present invention is a photosensitive in the UV spectrum zone only.Yet, but they can be used to the sensitizing agent sensitization of known photodissociation Organohalogen compounds to spectrographic near ultraviolet and visible-range.Illustrative sensitizing agent comprises United States Patent (USP) 4,250, aromatic amine described in 053 and colored aromatics polynuclear hydrocarbon.This patent reference is incorporated among the present invention.

Be applicable to that aromatic sulfonium complex salt initiator of the present invention can represent with following general formula: In the formula

R ₃, R ₄And R ₅Can be identical or different, as long as at least one group is an aryl.The aryl of the optional self-contained 4-20 carbon atom of these groups (as replacing and unsubstituted phenyl, thienyl and furyl) and contain the alkyl of 1-20 carbon atom." alkyl " speech comprises the alkyl (as the substituting group of halogen, hydroxyl, alkoxyl group and aryl and so on) of replacement.R ₃, R ₄And R ₅It better all is aryl;

Z, m and X define with reference to above-mentioned iodine complex salt.

If R ₃, R ₄And R ₅Be aryl, it can randomly have one or more benzo rings (as naphthyl, benzothienyl, dibenzothiophene base, benzofuryl, dibenzofuran group etc.) that condense.If necessary, aryl also can be replaced by one or more non-basic groups, if these groups do not react with epoxide and hydroxy functional group basically.

Salt that triaryl replaces such as hexafluoro-antimonic acid triphenylsulfonium and hexafluoro-antimonic acid are preferred sulfonium salts to phenyl thiophenyl phenylbenzene sulfonium.Useful sulfonium salt is described in greater detail in United States Patent (USP) 5,256, in 828.

Aryl sulfonium complex salt used among the present invention is a photosensitive in the UV spectrum zone only.Yet they can be by United States Patent (USP) 4,256,828 and 4,250, and the sensitizing agent sensitization described in 053 is to spectrographic near ultraviolet and visible-range.

Be applicable to that photoactivation organo-metallic complex salt of the present invention comprises United States Patent (USP) 5,059,701,5,191,101 and 5,252, the complex salt described in 694.The reference in content of these patents is incorporated among the present invention.These organo-metallic cationic salts have following general formula:

[(L ¹) (L ²) M ^m] ^{+ e}X ^-M in the formula ^mExpression is selected from the atoms metal of periodic table of elements IVB, VB, VIB, VIIB and VIII family, better is Cr, Mo, W, Mn, Re, Fe and Co;

L ¹Expression does not have, one or two provides the part of π-electronics, and these parts can be identical or different, and is selected from and replaces and unsubstituted acyclic and cyclic unsaturated compound and replacement and unsubstituted carbocyclic aromatic and heterocyclic aromatic compounds.Every kind of compound can both provide 2-12 π-electronics to the valence shell of atoms metal M.L ¹Better be selected from and replace and unsubstituted η ³-allyl group, η ⁵-cyclopentadienyl, η ⁷-cycloheptatriene based compound and η ⁶Aromatic substance; Described η ⁶Be selected from η ⁶The η of benzene, replacement ⁶-benzene compound (as dimethylbenzene) and compound with 2-4 fused rings; Each compound can both be to M ^mValence shell 3-8 π-electronics is provided;

L ²Expression 0 or 1-3 the part that even number σ-electronics can be provided; These parts can be identical or different, and be selected from the derivative of carbon monoxide, nitrous ion, triphenyl phosphine, triphen  and phosphorus, arsenic and antimony, and condition is by L ¹And L ²To M ^mThe total elementary charge that provides makes title complex produce e net surplus positive charge; With

E is 1 or 2 integer, the residual electric charge of complex cation;

X is aforesaid halogen-containing complex anion;

The example that is suitable for the organometallic ligand cationic salts of making photoactivation catalyzer among the present invention comprises:

(η ⁶-benzene) (η ⁵-cyclopentadienyl) Fe ^{+ 1}SbF ₆ ^-

(η ⁶-toluene) (η ⁵-cyclopentadienyl) Fe ^{+ 1}AsF ₆ ^-

(η ⁶-dimethylbenzene) (η ⁵-cyclopentadienyl) Fe ^{+ 1}SbF ₆ ^-

(η ⁶-cumene) (η ⁵-cyclopentadienyl) Fe ^{+ 1}PF ₆ ^-

(η ⁶-dimethylbenzene (mixed isomers)) (η ⁵-cyclopentadienyl) Fe ^{+ 1}SbF ₆ ^-

(η ⁶-dimethylbenzene (mixed isomers)) (η ⁵-cyclopentadienyl) Fe ^{+ 1}PF ₆ ^-

(η ⁶-o-Xylol) (η ⁵-cyclopentadienyl) Fe ^{+ 1}CF ₃SO ₃ ^-

(η ⁶-m-xylene) (η ⁵-cyclopentadienyl) Fe ^{+ 1}BF ₄ ^-

(η ⁶-) (η ⁵-cyclopentadienyl) Fe ^{+ 1}SbF ₆ ^-

(η ⁶-hexamethyl-benzene) (η ⁵-cyclopentadienyl) Fe ^{+ 1}SbF ₅OH ^-With

(η ⁶-fluorenes) (η ⁵-cyclopentadienyl) Fe ^{+ 1}SbF ₆ ^-

Be applicable to that the preferred organo-metallic complex cation salt among the present invention comprises following one or more salt: (η ⁶-dimethylbenzene (mixed isomers)) (η ⁵-cyclopentadienyl) Fe ^{+ 1}SbF ₆ ^-, (η ⁶-dimethylbenzene (mixed isomers)) (η ⁵-cyclopentadienyl) Fe ^{+ 1}PF ₆ ^-, (η ⁶-dimethylbenzene) (η ⁵-cyclopentadienyl) Fe ^{+ 1}SbF ₆ ^-(η ⁶-) (η ⁵-cyclopentadienyl) Fe ^{+ 1}SbF ₆ ^-

The organo-metallic salt initiators can randomly use with the promotor of tertiary alcohol barkite and so on.As United States Patent (USP) 5,252,694 is described, and described promotor better accounts for the 0.1-4% of whole polymerizable mixtures (thermoplastic component, heat-curable component and catalyzer) weight, better accounts for about 60% of metallocene initiator weight.This patent reference is incorporated among the present invention.

Useful commercially available initiator comprises FX-512 ^TM, the aromatic sulfonium complex salt (3M company, St.Paul, MN), UVI ^TM-6974, and the aromatic sulfonium complex salt (Union Carbide Corp., Danbury, CT) and IRGACURE ^TM261, positively charged ion organo-metallic complex salt (Ciba Geigy Chemicals, Hawthorne, NY).

The consumption of light trigger is a 0.01-10% weight among the present invention, is preferably 0.01-5% weight, is preferably 0.1-2% weight, is benchmark with whole resin combination.

The heat-activated curing agent of some Resins, epoxy (epoxide is solidified and crosslinked compound) can be used among the present invention.Under the temperature of these solidifying agent when component is mixed more fortunately is heat-staple.

Suitable thermal curing agents comprises aliphatic series and primary aromatic amine and secondary amine, as two (4-amino-benzene) sulfone, two (4-amino-benzene) ether and 2, and two (4-aminophenyl) propane of 2-; Aliphatic series or aromatic uncle amine are as dimethylaminopropylamine and pyridine; Fluorenediamine, as United States Patent (USP) 4,684, the fluorenediamine described in 678, this patent reference is incorporated among the present invention; The boron trifluoride affixture is as BF ₃Et ₂O and BF ₃H ₂NC ₂H ₄OH; Imidazoles, as Methylimidazole, hydrazine is as own hydrazine; And guanidine, as tetramethyl guanidine and two Dyhard RU 100s (dicyanodiamide are also referred to as DiCy usually).Should be realized that, must in these solidifying agent, carefully select, because wherein many solidifying agent are not suitable for the situation that has the high melting-point polyolefins component, but they can be used for preparing the semiinterpenetrating polymer network of the present invention that contains low melting point polyolefin and Resins, epoxy.

The consumption of thermal curing agents should make that the equivalent of Resins, epoxy and the normal ratio of thermal curing agents are 0.9: 1-2: 1.

The homopolymerization polyolefine that uses among the present invention comprises polyethylene, polypropylene, poly-1-butylene, poly--the 1-amylene, poly--the 1-hexene, poly--1-octene and relevant polyolefine.Preferred homopolymerization polyolefine comprises that polyethylene is (as DowHDPE 25455 ^TM, available from Dow Chemical Co., Midland, MI) and polypropylene (as ShellDS5D45 ^TM, available from Shell Chemicals, Houston, TX or Exxon Escorene ^TM3445 and 3505G, available from Exxon Chemicals, Houston, TX).Also spendable is the multipolymer of these alpha-olefins, comprises that polyethylene-common-propylene is (as SRD7-462 ^TM, SRD7-463 ^TMAnd DS7C50 ^TM, these are all available from Shell Chemicals), polypropylene-altogether-1-butylene is (as SRD6-328 ^TM, also available from Shell Chemicals) with relevant multipolymer.Preferred multipolymer is polyethylene-common-propylene.Also spendable is Vestoplast ^TMThe series polyolefine is available from Huels America Inc., Piscataway, NJ.

Semiinterpenetrating polymer network of the present invention also contains functionalised polyolefin, promptly by graft copolymerization after olefinic monomer and functional monomer's copolymerization or the olefinic polymerization and the polyolefine that contains extra chemical functional group that obtains.These functionalized groups generally contain O, N, S, P or halogen heteroatoms.These active functionalized groups comprise carboxylic acid, hydroxyl, amide group, nitrile, carboxylic acid anhydride or halogen radical.Many functionalised polyolefins are commercially available.For example, copolymeric material comprises vinyl-vinyl acetate copolymer, as available from DuPont Chemicals, and Wilmington, the Elvax of DE ^TMSeries, same Elvamide available from DuPont ^TMSeries ethene-polyamide copolymer and available from Uinon Carbide Corp., Danbury, the Abcite 1060WH of CT ^TM, contain the polyvinyl multipolymer of the 10% weight carboxylic acid functional group that has an appointment.The example of the functionalised polyolefin of graft copolymerization has the polypropylene of maleic anhydride graft, as available from Eastman Chemical Co., and Kingsport, the Epolene of TN ^TMSeries wax and available from Himont U.S.A., Inc., Wilmington, the Questron of DE ^TM

For a change solidify the physical properties of back semiinterpenetrating polymer network, also various auxiliarys can be added in the composition of the present invention.The useful auxiliary that adds is a thixotropic agent, as pyrogenic silica (fumed silica); Improve the pigment of tone, as ferric oxide, carbon black and titanium dioxide; Filler is as mica, silicon-dioxide, acicular wollastonite, lime carbonate, sal epsom and calcium sulfate; Clay is as wilkinite; Granulated glass sphere and glass envelope; Strongthener is weaved and supatex fabric (web) as the unidirectional of organic and inorganic fibre (as polymeric amide, carbon fiber and the ceramic fiber of polyester, polyimide, glass fibre, PPTA and so on).Consumption can be up to about 200 parts of auxiliary/100 part polyolefine-epoxy composites.

Semiinterpenetrating polymer network of the present invention can be with any preparation of following two kinds of methods: interrupter method and continuous processing.

Interrupter method can carry out as follows, promptly when being lower than the temperature of solidifying agent heat activation temperature, Brabender mixing machine (the C.W.Brabender Instruments of curved surface (cam) blade or sigma blade is being housed, Inc., South Hackensack, NJ) adding is generally the granulous solid polyolefin in and so on the pre-Hot mixer.Behind the stir about 5 minutes, the polyolefine of pre-polymerization is melted fully, continues to stir down, adds the mixture of liquid-state epoxy resin and epoxy curing agent.When mixing polyolefine and Resins, epoxy, generally can notice the instantaneous reduction of moment of torsion and melt temperature.Stir the mixture of gained, mix fully guaranteeing, and under molten state from mixing machine with its taking-up.Then can be with mixture molding, moulding, be shaped or be pressed into required final structure, carry out radiation and/or heating, epoxy resin ingredient is solidified and crosslinked.Particularly when needs thin plate or film, can (Wabash IN) and so on suppresses in the heated plate press for F.Carver, Inc. at Carver experimental size press.

Continuous processing can be carried out with extruding machine, as the Bitruder of downstream port, static mixing core and suitable discharge port (sheeting die, sheet die, fiber die head, section bar die head etc.) and pull roll and wind-up roll is housed.Solid polyolefin is added the opening for feed of extruding machine, and use and handle with the temperature range that is lower than the heat activation temperature of epoxy hardener polyolefine is suitable.With the outlet line speed setting to be suitable for output (sheet material, fiber etc.) degree, generally be about 0.5-200 rice/minute.

For behind extrusion molding, promptly before polyolefine cooling and crystallization, need the situation of epoxy resin thermosetting immediately, can on nib and casting wheel, directly further heat extrudate.When needs carry out epoxy resin cure after polyolefine cooling and crystallization, thermal source can be placed on before the pull roll just.At last, also can not need behind the extrusion molding, can not have heating unit in this case epoxy resin cure.

For behind extrusion molding, promptly before polyolefine cooling and crystallization, need the situation of Resins, epoxy photocuring immediately, can directly carry out uv-radiation at the nib place to heating the back extrudate.Radiation can be carried out with many commercially available ultraviolet sources, as one or more Fusion System D or H bulb (available from Fusion UV CuringSystems, Rockville, MD) or Sylvania BL 350 bulbs.When needs carry out epoxy resin cure after polyolefine cooling and crystallization, light source can be arranged on before the pull roll just.At last, can not carry out epoxy resin cure immediately behind the extrusion molding.In this case, can there be radiation devices.

Polyolefine-epoxy blending the film that obtains with sheet die is also included within the scope of the present invention.When this film is extruded from die head, can carry out single shaft to or biaxial stretching.Above-mentioned curing can be carried out before or after stretching is finished.

Composition of the present invention can be used for the application of the peculiar property that the utilization of many needs produces by forming semiinterpenetrating polymer network.The chemically inert unique combination of the high adherence of Resins, epoxy and polyolefinic height produces the material that can be used as pipeline and other coating for metal surfaces in abominable, the caustic chemical environments.Therefore, the coating that is made by the present composition can be used on the outside of iron staff in steel pipe and the Steel Concrete or rod iron (being commonly referred to " reinforcing bar ").These coatings also can be coated in the inside of pipeline, avoid the erosion of corrosive chemical to protect it.The fiber that is formed by the semiinterpenetrating polymer network extrusion molding for example can be used as bristle.For bristle, low creep, high-modulus and high chemical resistance are important.Melt processible composition can be used as tackiness agent, particularly when potential and when to apply after fixing be a kind of required character.

Semiinterpenetrating polymer network film of the present invention can be used as many base materials (metalloid and polyolefine and polyimide and so on the polymer materials that comprise steel, aluminium and copper) and goes up protectiveness and/or decorative coating (by the coating on self or other base material).In the time of on being coated in metal base, film of the present invention applies under molten state or the high temperature more fortunately, so that made base material wetting before the epoxy resin cure step fully, thereby makes binding property maximization to base material.

The extrudable one-tenth fiber of semiinterpenetrating polymer network of the present invention shape (comprising filate) becomes to weave and nonwoven articles with these fiber process then.These goods have than only by weaving and the nonwoven articles better properties that polyolefine makes.Nonwoven, melt blows fibroreticulate manufacture method and is disclosed in United States Patent (USP) 4,118,531 (this patent reference is incorporated among the present invention) and Wente, Van A., " ultra-fine thermoplastic fibres ", technical chemistry, 48 volumes, the Wente that the 1342nd page (1956) and on May 25th, 1954 publish, Van A., Boone, C.D., and Fluharty, No. 4364 exercise question in the Naval research laboratory that E.L writes is in the report of " manufacture method of ultra-fine organic fibre ".For example, the nonwoven articles that is made by semiinterpenetrating polymer network of the present invention can obtain " UL-94 V-0 " level in the Underwriter laboratory " upright combustion test ", and the grade of polyolefin nonwoven fabric is generally " UL-94V-2 ".In addition, the polyolefine nonwoven articles can apply (as spraying, dip-coating or roller coat), the nonwoven articles that has better performance with generation with fused semiinterpenetrating polymer network of the present invention.Compare with many other coatings of present use, semiinterpenetrating polymer network adheres to polyolefin nonwoven fabric more firmly.

The unsupported film that makes by semiinterpenetrating polymer network of the present invention can be used for being orientated or stretch after need the more occasion of high thermal stability, as electrical condenser, tape backing, magnetic tape substrate etc.Particularly, film of the present invention can be preferably as the self adhesive tape backing that for example uses acrylic adhesives.Polarity solidified epoxy resin ingredient can provide higher binding property between acrylic adhesives and film backing.

Semiinterpenetrating polymer network of the present invention is also as inflatable pearl or microballon, so that the better product of product that makes than with known inflation thermal expansion polyolefine pearl to be provided.Structural strength can be improved with the pearl that semiinterpenetrating polymer network makes, and intensity can be improved with its foam that makes (as foam band, foamy structure, moulded foam parts etc.).

Following embodiment will be further described objects and advantages of the present invention, but should be appreciated that concrete material used among the embodiment and consumption thereof and other condition and details must suitably limit the present invention.

Embodiment

Test method

Tensile modulus, tensile strength

(Instron Corp., Park Ridge IL) measures with 1122 type Instron tension test instrument for tensile modulus and tensile strength.This tester is furnished with 2511-317 type 5KN load transducer.Used pinblock speed is 0.05 meter/minute in all tests.Used linerless sample band is of a size of 0.25 centimetre of 12.7 cm x, 6.4 cm x.Test is carried out at 22 ℃ and 100 ℃.With test tape be exposed to by TLD 15W/03 (Phillips, Holland), 350BL (Sylvania-GTE; US) or fusion D or H bulb (Fusion UV CuringSystems, Rockville, 3.1 joules/centimetre of MD) producing ²In the radiating capacity.Then sample is placed in 100 ℃ of baking ovens 15 minutes, solidifies guaranteeing.

Lap shear strength

Lap shear is measured basically and is undertaken by ASTM D1002-94, " the apparent shearing resistance of the single lap joint matrix metal sample of the load that is stretched ".The cold-rolled steel sample that will be of a size of 3.2 millimeters of 11.43 cm x, 2.54 cm x with butanone is thoroughly cleaned, and is placed on and is heated to 185-250 ℃ on the hot-plate.Is that 0.25 and 0.75 millimeter film is attached on the hot metal surface with silica gel roller with thickness, and allows its fusion.During fusion, the film that will contain photocatalyst be exposed to by TLD 15W/03 (Phillips, Holland), 350BL (Sylvania-GTE; US) in 3.1 joules of/centimetre 2 radiating capacity that the ultraviolet emission lamp produces.Use Scotchkote ^TM(3M, St.Paul's 134 Epoxy MN) are bonded together two halves cured portion film to film.The overlap joint area is 2.54 centimetres ²The very thin Scotchkete of spraying one deck on half film ^TM134, and second half film is placed on it down at 185 ℃.The film that a slice is to be tested was placed 5 minutes between two 225 ℃ of samples, and preparation contains the sample of heat cured system.Remove thermal source from sample then, be cooled to 22 ℃.Read peak load and breaking strain from the Instron tester of being furnished with the 44.5KN load transducer.

Dynamic mechanical analysis (DMA)

Sample is the linerless sample bar that makes by method described in above-mentioned " tensile modulus ".Use be equipped with the tension specimen anchor clamps Seiko Imstruments DMA 200 rheometers (Seiko Instruments, Torrance, CA).Spacing between chuck is 20 millimeters.Heat-up rate between-80 to 160 ℃ is 2 ℃/minute.Use four steps to test: 1,10,50 and 100Hz.

Dsc (DSC)

(Perkin-Elmer Corp., Norwalk are weighed into the completely crued polyolefine and the liquid epoxies through grinding of known quantity, preparation Resins, epoxy/polyolefin blend in CT) at the Stainless Steel Disc of Perkin-Elmer differential scanning calorimeter.Should coil hermetic seal, and in 200 ℃ of baking ovens, place 30 minutes, allow polyolefine and Resins, epoxy homogenizing.Allow sample be cooled to 22 ℃, weigh again, to confirm in heat treatment step, not have weight reduction.In all cases, the sample weight that records alleviates and is no more than 0.2%.(Seiko Instruments, Torrance CA) carry out DSC scanning to each sample with Seiko SSC/5220H DSC instrument.During scanning, sample was kept 10 minutes at 200 ℃, by 10 ℃/minute speed sample is cooled to 0 ℃ from 200 ℃ then.For the second time sample is weighed again, to confirm when DSC scans, not have weight reduction.

Thermomechanical analysis; Orientation and contraction

In the time of 150 ℃, in the Instron tensilometer be that to be stretched to elongation be 200% for uncured Resins, epoxy/curing polyolefin film of 10 millimeters * 3.5 millimeters * 0.25 millimeter with life size, then the tension specimen that heats is placed under the Sylvania 350B ultraviolet lamp and shone the preparation film sample 5 minutes.(Perkin-Elmer Corp., Norwalk test in Perkin-Elmer 7 serial thermodynamic analyzers CT) in that the extension probe is housed.Speed by 10 ℃/minute under the external force effect of 50Nm is heated to 160 ℃ with sample from 25 ℃.

Specific inductivity

Under 500 volts and 45% relative humidity condition,, press ASTM D257-93 Measuring Dielectric Constant basically with Keithly 237 and 8008 insulation anchor clamps (fixture) and 60 second duration of charging.(Hewlett-Packark Co., Palo Alto, HP4284A Precision LCR instrument CA) carry out 500Khz and measure with being furnished with HP16451B dielectric testing apparatus.Carrying out 900Mhz with HP4291 impedance material analyser measures.

Surface properties

With standard series surface tension liquid (Sherman Treaters, Inc., Mississauga, Ontario, Canada) surface tension.One drop of liquid is dropped on the surface of test, the surface tension when wetting observed in record.

Flame retardant resistance

Test by UL-94 " upright combustion test ".With the sample that is of a size of 12.7 centimetres of 1.27 cm x vertically from bottom-exposed 10 seconds Bunsen flame.If sample from putting out, then placed sample 10 seconds of flame again in 30 seconds.Transfer 30.5 centimetres of medical cotton pads of dry absorptivity at sample.If the burning droplet can not be lighted cotton, and the average burning time be less than for 5 seconds, the deciding grade and level of this material is " 94V-O ".If be less than 25 seconds mean time, then this material deciding grade and level is " 94V-1 ".If cotton is lighted, even sample is from putting out, this material also is rated for " 94V-2 ".

Embodiment 1. tackiness agents

Prepare melt processible semiinterpenetrating polymer network with Bitruder.(available from Shell Chemicals, Houston TX) adds and is equipped with in the co-rotating twin screw extruding machine of downstream measuring apparatus, static mixing core and 20.3 centimetres of sheet dies for DS7C50,20% ethene with polypropylene-altogether-ethene.The rotating speed of extruding machine is 90 rev/mins, temperature distribution (℃) be: 198-200-200-230-266-266-187.Total mean residence time is about 12 minutes.In the charging opening of downstream, and Resins, epoxy shown in the adding table 1 and 2% weight phosphofluoric acid triaryl matte (FX-512 activates epoxy curing agent, available from 3M Company, and St.Paul, MN) mixture of (weight with Resins, epoxy is benchmark).The mixture of extruding by 0.77-1.0 rice/minute linear velocity be collected in temperature and remain on 121 ℃ drawing on the wheel.Be collected on the winding wheel then.Make two samples of every kind of prescription cooling mixture.Sample is in the dark stored 72 days, measure lap shear strength then.The results are shown in the table 1.All sample breakages all are cohesions.Resins, epoxy ERL ^TMThe-4221st, available from Union Carbide, Danbury, 3 of CT, 4-epoxy cyclohexane carboxylic acid 3,4-epoxycyclohexyl methyl esters; EPON ^TMThe-828th, and bisphenol A diglycidyl ether (DGEBA, available from Shell Chemicals, Houston, TX).

Table 1 lap shear test
				Resins, epoxy	% weight	Peak load, pound/inch 2	Peak load, Mpa
ERL-4221	4	2187	15.1
				ERL-4221	15	1607	11.1
ERL-4221	22	1077	7.4
				ERL-4221	33	739	5.1

Data in the table 1 show that semiinterpenetrating polymer network of the present invention forms and mainly contains polyolefinic coating.This coating has fabulous binding property to clean steel base.In addition, this sample shows and has obtained fabulous potential cure adhesive among the present invention.

Embodiment 2. electrical properties

Press polypropylene-common-ethene (DS7C50 is available from Shell Chemicals) extrusion molding sample of embodiment 1 described method preparation and Resins, epoxy blending.Behind the extrusion molding, when sample is melted (185 ℃), allow its speed under Sylvania 350BL ultraviolet emission lamp, pass through with 7.5 feet per minutes, or after being cooled to 25 ℃ and crystalling propylene, under UV-emitting Fusion D bulb, pass through, thereby make its curing.Measuring Dielectric Constant.

Table 2 specific inductivity
						Resins, epoxy	% Resins, epoxy	Temperature ℃	Sample thickness, millimeter	Specific inductivity, 500Khz	Specific inductivity, 900Khz
Do not have (contrast)	0	25	0.26	2.24	2.22
						ERL-4221	4	25	0.34	2.16	2.10
ERL-4221	15	25	0.27	2.04	2.12
						ERL-4221	22	25	0.37	1.78	1.83
ERL-4221	33	25	0.46	1.76	1.88
						EPON-828	14	25	0.30	1.73	1.97
ERL-4221	4	185	0.35	1.96	2.14
						ERL-4221	15	185	0.27		2.22
ERL-4221	22	185	0.37		2.15
						ERL-4221	33	185	0.38		2.03
EPON-828	5	185	0.30		2.11
						EPON-828	14	185	0.27	2.00	2.15
EPON-828	29	185	0.39		2.00

Data in the table 2 show that semiinterpenetrating polymer network contains the Resins, epoxy of significant quantity, and its specific inductivity is equal to or less than virgin pp.Low specific inductivity can insulate with energized conductor and the soil that is embedded with metal tube preferably.

Embodiment 3. surface propertieies

Prepare the semiinterpenetrating polymer network sample that contains poly-(polypropylene-be total to-ethene) (DS7C50 is available from Shell Chemicals) and different % weight ring epoxy resins shown in the table 3 by embodiment 1 described method with extrusion molding.Use 2% weight FX-512 catalyzer in the per sample (p.s.).Sample is passed through under Fusion D light with the speed of 7.5 inch per minutes, make its curing, be cooled to 23 ℃, measure the surface energy of every kind of prescription then.The results are shown in the table 3.

Table 3 surface energy
			Resins, epoxy	% weight	The surface energy dynes per centimeter
Do not have (contrast)	--	＜30
			ERL-4221	4	32
ERL-4221	15	32
			ERL-4221	22	33
ERL-4221	33	36
			EPON-828	5	31
EPON-828	14	33

When the data in the table 3 show the consumption that increases Resins, epoxy, obviously increased the surface energy of semiinterpenetrating polymer network.Material with high surface energy may have good tackiness agent and wettability to coating, binding agent, tackiness agent and resin.Semiinterpenetrating polymer network of the present invention has higher surface energy than pure polyolefine.

Embodiment 4. dimensional stabilitys

Prepare polypropylene-epoxy resin composition by embodiment 1 described method, and analyze its shrinkability as stated above.The results are shown in Table 4.

Table 4 stress shrinks
		Resins, epoxy % weight	Shrinking percentage, %
0 (contrast)	11.83
		4	8.49
15	4.88
		22	5.99

When the data in the table 4 show the amount that increases Resins, epoxy in the semiinterpenetrating polymer network, increase the dimensional stability of film.Polyolefin film (or other form, as fiber, pipe and section bar) with good dimensional stability is favourable to some industrial use.

Embodiment 5. modulus

By interrupter method the heating that the sigma blade is housed, interior stirring-type Brabender mixing machine (C.W.Brabender Instruments, Inc., South Hackensack, NJ) in the melt processible semiinterpenetrating polymer network of preparation.The rotating speed of sigma blade is about 100 rev/mins.The ingredients (Formulation) that contains different epoxy resin contents by method preparation as follows.Stir down, (DS5D45, available from Shell Chemicals, Houston TX) added in the mixing machine, and be heated 185 ℃ in 5 minute with polypropylene.Observe because the temperature of agitating friction mixture is elevated to about 205 ℃.To contain 1% weight organo-metallic complex salt light trigger (η 6-dimethylbenzene (mixed isomers)) (η 5-cyclopentadienyl) Fe in the ratio shown in the table 6 then ^{+ 1}SbF ₆ ^-The EPON of (pressing United States Patent (USP) 5,089,236 described method preparations) ^TM828 Resins, epoxy (available from Shell Chemicals) mixture, and continue to stir 2 minutes.Mixture is taken out from reactor, and (Wabash presses twice in IN), obtains the unsupported film that thickness is about 0.175-0.38 millimeter (7-15 mil) for Fred Carver, Inc. to be placed on C type Carver experimental size press in the time of 195 ℃.For 0.25 millimeter film, with super actinic lamp (TDL ¹The 5W/03 lamp is available from Phillips N.V., Holland) with 2.2 joules/centimetre ²To film approximately according to 5 minutes.

Allow 0.25 mm thick sample with several Resins, epoxy concentration solidify, and measure its tensile strength and tensile modulus, the results are shown in Table 5.

Table 5 tensile strength and tensile modulus
				Embodiment	Resins, epoxy % weight	Tensile strength, Mpa	Tensile modulus, Mpa
5 (a) (contrast)	0	33	648
				5(b)	6	31	575
5(c)	10	27	685
				5(d)	20	25	691
5(e)	30	22	800
				5(f)	40	18	796

Data in the table 5 show: though the tensile modulus of semiinterpenetrating polymer network of the present invention (being stiffness) increases the corresponding minimizing of tensile strength with the increase of epoxy resin content.

Embodiment 6. supatex fabric

With as described in example 1 above Bitruder basically by 80 parts of polyvinyl resin (Exxon Escorene that contain 2% weight FX-512 catalyzer ^TM3505G, available from Exxon Chemicals, Chicago, IL) and EPON ^TM828 Resins, epoxy prepare semiinterpenetrating polymer network.The outlet of extruding machine is to be used for the molten many mouthfuls of die heads that blow supatex fabric (webs) of preparation.The All Ranges of extruding machine, flow duct and die head all remains on 230 ℃, and the die head air themperature is 240 ℃.The fiber extruded velocity is 4.9 kilograms/hour; Collector is far away from 0.34 meter of die head, and the speed of drawing is 1 meter/minute; The fiber effective diameter is 20 microns.The dosage that the fabric that forms is exposed to the generation of FusionSystems " D " bulb is 3.0 joules/centimetre ²With wavelength be in the radiation of 320-390 nanometer.With UTSE-2 type tensile test apparatus (J.Chartillon ﹠amp; Sons, Greensboro, NC) tensile property of measurement fabric.The mean value of three tests is listed in the table 6.

Test contains the curing semiinterpenetrating polymer network of 10 parts and 20 parts Resins, epoxy, and defining the level is UL-94 " V-0, ", promptly is less than the flame time in 10 seconds, and does not light cotton indicator pad.

Table 6 supatex fabric
					Resin, part	Test	Before the curing	After the curing	% increases
10	Breaking weight, newton	28	35	25
					10	Elongation, millimeter	1.19	1.98	65
20	Breaking weight, newton	8	9.8	22
					20	Elongation, millimeter	711	152	-78

Data in the table 6 show: the molten supatex fabric that blows that makes with the present composition has the tensile property higher than uncured fabric after epoxy resin ingredient is solidified.

Embodiment 7.

Resins, epoxy-polypropylene semiinterpenetrating polymer network the sample that has different epoxy resin contents by embodiment 2 described methods (carrying out photocuring during polypropylene fusion) preparation, and carry out differential scanning calorimetric analysis (DSC), to determine the influence of epoxy resin content to sample degree of crystallinity.The degree of crystallinity of supposing virgin pp is 60%, and the whole full crystalline value of polypropylene is 138 joule/gram, according to determining decline % corresponding to the area of polypropylene part on the exotherm.

Table 7 semiinterpenetrating polymer network degree of crystallinity
			The Resins, epoxy type	Resins, epoxy %	Degree of crystallinity reduces %
ERL TM-4221	4	4.7
			ERL TM-4221	15	12.3
ERL TM-4221	22	23.7
			ERL TM-4221	33	2.3
EPON TM-828	29	29

Data in the table 7 show: for solidified sample before the cooling, degree of crystallinity is obviously reduced, and generally is directly proportional with the content of Resins, epoxy.(sample that degree of crystallinity reduces has higher optical transmittance, promptly shows higher transmittance than virgin pp).

Embodiment 8

Determine the influence of epoxy resin content with the sample that contains different amount Resins, epoxy to crystalling propylene temperature (the onsetof crystallization).Tc is measured with dsc (DSC).Polypropylene (Exxon3445 homopolymer) is mixed with Resins, epoxy, and extrusion molding is cured with uv-radiation when fusion then.Tc is recorded in the table 8.

Table 8 Tc, T c
			Resins, epoxy	Resins, epoxy %	T c，℃
(contrast)	0	113.7
			ERL TM-4221	5	112.7
ERL TM-4221	10	111.6
			ERL TM-4221	15	110.2
ERL TM-4221	20	107.4
			ERL TM-4221	25	106.4
ERL TM-4221	30	105.8
			EPON TM828	5	113.2
EPON TM828	10	112.7
			EPON TM828	15	110.4
EPON TM828	20	112.0
			EPON TM828	25	109.8
EPON TM828	30	109.6

Data in the table 8 show: Resins, epoxy and polyacrylic thermodynamics miscibility expand epoxy resin content to and are about 30%.When epoxy resin content is higher, observes and be separated, and be difficult to carry out melting treatment.

Embodiment 9.

Preparation contains 15% weight EPON in polypropylene-polyethylene and ethylene copolymers (DS7C50, Shell Chemicals) ^TMThe semiinterpenetrating polymer network of 828 Resins, epoxy and 2% weight FX-512 photocatalyst, still cured with ultraviolet radiation when molten state is carried out dynamic mechanical analysis (DMA) then in wide temperature range and at the MHz place.As shown in table 9, the Tan δ and the pure block copolymer of sample compared.

Table 9
				Tanδ
Temperature, ℃	Multipolymer (contrast)	Semiinterpenetrating polymer network (15% Resins, epoxy)
			-50	0.020	0.021
0	0.053	0.078
			50	0.070	0.107
100	0.099	0.120
			150	0.125	0.150

The increase of Tan δ value shows that the visco-elasticity of semiinterpenetrating polymer network of the present invention increases, therefore at the two alternate interfaces that exist.This interface also is reflected in the increase of viewed semiinterpenetrating polymer network sample than pure block copolymer sample (contrast) compliance.

Embodiment 10.

(MA) (South Hackensack NJ) prepares semiinterpenetrating polymer network of the present invention for C.W.Brabender Instruments, Inc. with the Brabender caterpillar for Fisons Instruments, Beverly with the Haake conical twin-screw extruder.Used extruding machine temperature distribution is 170 ℃-185 ℃-200 ℃-190 ℃, and total residence time is 5 minutes.In the method, with polypropylene-common-ethene (DS7C50 ^TM, available from Shell Chemicals, Houston, TX) with contain the fluorenediamine solidifying agent (available from 3M, St.Paul, MN) and 10% (weight) PR-500 of functionalised polyolefin ^TMComposition epoxy resin mixes.The uncured film that collection is extruded from extruding machine is as unsupported film.During test, film sample is placed on Carver experimental size press (F.Carver, Inc., Wabash, IN) middle Teflon ^TMSolidified 5 minutes in 225 ℃ (when being the polyolefine fusion) between demoulding film (release film).The component and the character of cured film are listed in the table 10.

Table 10

^*Contrast #1 does not contain the PR-500 composition epoxy resin

¹Available from DuPont Chemicals, Wilmington, experimental Resins, epoxy/propylene copolymer of DE, it contains 10% epoxide group of having an appointment, and melt flow index is 50.

²Questron ^TMBe available from Himont U.S.A., Inc., Wilmington, maleic anhydride-graft polypropylene of DE.

³Elvax ^TMIt is vinyl-vinyl acetate copolymer available from DuPont Chemicals

⁴Abcite 1060WH ^TMBe available from Union Carbide Corp., Danbury, the ethylene copolymer of CT, it contains 10% carboxylic acid group

⁵Epolene G3003 ^TM, Epolene G3002 ^TMWith Epolene E-43 ^TMAll be available from EastmanChemical Co., Kingsport, the maleic anhydride modified Poly Propylene Wax of TN

Data in the table 10 show that the prescription that only contains functionalised polyolefin can provide the curing composition with enough lap shear strengths, thus can be used as tackiness agent or protective coating (Comparative Examples #1 and #2 for example with Epolene ^TMPrescription).This table also shows: PR-500 ^TMBasically be not cured under the processing conditions of composition epoxy resin in extruding machine, even when not adding functionalised polyolefin, solidified Resins, epoxy also improves the polyolefinic modulus of hydro carbons and the tensile strength (Comparative Examples #1 and Comparative Examples #2) of complete pre-polymerization.The 3rd, also can see Epolene ^TMWax provides modulus, tensile strength, elongation and the lap shear strength of well balanced raising.

Embodiment 11

The semiinterpenetrating polymer network sample of the present invention that in extruding machine, prepares the Calucium Silicate powder that is commonly used for polymer packing that contains different amounts by embodiment 10 described methods.Prescription is: 88% weight DS7C50 ^TMPolyethylene-altogether-propylene (Shell Chemicals); 2% weight Epolene G3003 ^TMMaleinization Poly Propylene Wax (EastmanChemical Co.) and 0% or 10% weight PR-500 ^TMComposition epoxy resin (3M company) adds the Calucium Silicate powder shown in the table 11 in this prescription.

Table 11

CaSiO 4 ％	PR-500 TM ％	Young's modulus Mpa	Tensile strength MPa
				5	0	753	25.2
10	0	787	23.6
				15	0	617	19.8
20	0	748	20.2
				25	0	543	12.1
5	10	707	23.9
				10	10	840	26.0
15	10	728	22.6
				20	10	685	22.7
25	10	789	18.3

Data in the table show that the prescription that contains cured epoxy resin has higher modulus and tensile strength, even when higher add-on.Do not think and make theoretical explanation that we think that the prescription that contains cured epoxy resin has higher cementability between hydro carbons polyolefine parent and calcium silicate filling material particle, and when the Calucium Silicate powder add-on is high, can keep fabulous character.

Embodiment 12

For the binding property on advance copy invention semiinterpenetrating polymer network and oiliness surface, in extruding machine, prepare sample by the method described in the embodiment 10.Prescription is: 88% weight DS7C50 ^TMPolyethylene-altogether-propylene (Shell Chemicals); 2% weight Epolene G3003 ^TMMaleinization Poly Propylene Wax (EastmanChemical Co.) and 10% weight PR-500 ^TMComposition epoxy resin (3M company).Clean aluminium lap shear sample with butanone, it is cleaned, coat steel then and draw (steel-draw) lubricant (MC-1 with the cloth of cleaning ^TM, available from Novamax Technologies, Inc., Atlanta, GA).Allow dry 15 minutes of this lubricant, prepare then and test the lap shear sample.The prescription that contains PR-500 and functionalised polyolefin has the lap shear strength of 1.93MPa, and the lap shear strength of the sample that makes when not adding these compositions is zero.

Embodiment 13

Prepare semiinterpenetrating polymer network film of the present invention by embodiment 1 described method, this film contains 88% weight polyacrylamide (DS7C50, Shell Chemicals); 2% weight Epolene G3003 maleinization Poly Propylene Wax (Eastman Chemical Co.) and 10% weight PR-500 composition epoxy resin.Film sample is clipped in two Kapton E ^TMKapton (available from DuPont, Wilmington, DE) between, be placed in the Carver experimental size press in 204 ℃ of heating 30 minutes.With the laminar structure cooling that according to said method makes, and in the Instron trier, carry out 180 ° of stripping tests.The peeling force that records is 232 N/dm (13.2 lb/in ²).

Embodiment 14

Press embodiment 10 described methods and in extruding machine, prepare semiinterpenetrating polymer network of the present invention.Described semiinterpenetrating polymer network contains the hydro carbons polyolefine of Resins, epoxy, pre-polymerization fully and the functionalised polyolefin of complete pre-polymerization.Therefore, with polypropylene (DS7C50, Shell Chemicals) mixes in the ratio shown in the table 12 with EPON 828 Resins, epoxy (ShellChemicals) and some functionalised polyolefins, make the total percentage ratio of polypropylene equal (the total % of 100-(Resins, epoxy+functionalised polyolefin)).All samples that contain Resins, epoxy also contain 2% weight FX-512 photocatalyst, are benchmark with the weight of the Resins, epoxy that adds.This matrix material is cured, tests by above-mentioned tensile modulus, tensile strength and lap shear strength testing sequence.The results are shown in as in the following table 12.

^aPolypropylene film extrusion molding to 0.75 millimeter is forced into 0.25 millimeter

^bWith the polypropylene film extrusion molding, and to be exposed to dosage be 3.1 joules/centimetre ²Fusion Systems D UV bulb under.

^cWith the polypropylene film extrusion molding, and to be exposed to 200 ℃ and dosage be 3.1 joules/centimetre ²FusionSystems D UV bulb under.

¹Available from DuPont Chemicals, Wilmington, experimental Resins, epoxy/propylene copolymer of DE, it contains 10% epoxide group of having an appointment, and melt flow index is 50.

²Elvax ^TMIt is vinyl-vinyl acetate copolymer available from DuPont Chemicals

³Abcite 1060WH ^TMBe available from Union Carbide Corp., Danbury, the ethylene copolymer of CT, it contains 10% carboxylic acid group

Data in the table 12 show can prepare the semiinterpenetrating polymer network of the present invention that contains functionalised polyolefin, and these semiinterpenetrating polymer networks have the physical properties that one or more are parity with or superiority over the composition that does not contain functionalised polyolefin.

Embodiment 15

Prepare semiinterpenetrating polymer network of the present invention by embodiment 1 described method, this film contains 2%FX-512 catalyzer (weight with Resins, epoxy is benchmark) and EPON 828 and ERL-4221 Resins, epoxy as shown in table 13.For the binding property of testing film to rod iron, handle the cleaning rod iron through grit blasting, be heated to about 200 ℃ then, at this moment film sample is attached on the rod iron of heat, with the extruding of soft rubber roller, make rod iron and film uniform contact then.Take advantage of heat to be placed under 275 watts of sun lamps of General Electric rod iron+membrane structure and carried out uv-radiation 20 minutes, the distance between sun lamp and sample is 4 centimetres.Then it is cooled to about 23 ℃.Sample is placed on soaked in the tap water that is heated to 75 ℃ 2 days.Delineate " X " shape otch with cutter at the exsiccant sample with experiment, otch passes the film of stickup until steel base.In otch central authorities, carry out film stripping test from the rod iron.The results are shown in Table 13.

Table 13
				Resins, epoxy	% Resins, epoxy	Qualitative peeling off	Qualitative binding property
Unmatchful ratio	0	Easily	Do not have
				EPON828	5	Difficult	Well
“	14	A bit difficult	Qualified
				“	29	Difficult	Well
ERL4221	4	Easily	Do not have
				“	15	Difficult	Well
“	22	Easily	Do not have
				“	33	Easily	Do not have

Data in the table 13 show, can prepare the semiinterpenetrating polymer network polyolefin film that steel is had good adhesive property under heat, wet condition according to the present invention.

Those of skill in the art in this area can clearly realize that various improvement and the variations that do not depart from the scope of the invention and spirit.Therefore, will be understood that the present invention is not subjected to the undue restriction of above-mentioned illustrative embodiment.

Claims (27)

1. curable composition is characterized in that it comprises:

A) curable epoxy of 0.1-50% weight, described weight percentage is a benchmark with whole resin combination;

B) solidifying agent of curable epoxy;

C) the uncrosslinked hydro carbons polyolefin resin of the complete pre-polymerization of 50-99.9% weight and at least a in the two by the functionalized uncrosslinked polyolefin resin of complete pre-polymerization of at least a polar group, described weight percentage is a benchmark with whole resin combination;

Wherein said hydro carbons polyolefine accounts for the 25-99.9% weight of whole resin combination, described functionalised polyolefin accounts for the 0-20% weight of whole resin combination, described composition does not contain unvulcanized rubber and does not contain epoxidised natural and/or synthetic rubber, described hydro carbons polyolefine is meant the uncrosslinked polymeric hydrocarbon of the complete pre-polymerization that does not have machine functional group, and it is made by the homopolymerization and/or the copolymerization of olefinic monomer.

2. curable compositions as claimed in claim 1 is characterized in that described curable epoxy accounts for 0.1-40% weight, and described complete pre-polymerization polyolefin resin accounts for 60-99.9% weight.

3. curable compositions as claimed in claim 1 is characterized in that described Resins, epoxy contains 1,2-, 1,3-and 1, at least a in the 4-epoxide.

4. curable compositions as claimed in claim 1 is characterized in that described Resins, epoxy contains at least a in aliphatic series, alicyclic, aromatics and heterocycle family list or the polyepoxide.

5. curable compositions as claimed in claim 1 is characterized in that described Resins, epoxy contains the dual-active monomer.

6. curable compositions as claimed in claim 1 is characterized in that described hydro carbons polyolefine contains at least a alpha-olefin or its multipolymer.

7. curable compositions as claimed in claim 1 is characterized in that the described polar group of described functionalised polyolefin contains at least a heteroatoms that is selected from O, N, S, P or halogen.

8. curable compositions as claimed in claim 1 is characterized in that described solidifying agent is at least a in photoactivation cationic catalyst and the thermal curing agents.

9. curable compositions as claimed in claim 8 is characterized in that described catalyzer is the salt light trigger.

10. curable compositions as claimed in claim 8 is characterized in that described catalyzer is a positively charged ion organo-metallic complex salt.

11. curable compositions as claimed in claim 8 is characterized in that described thermal curing agents is aliphatic series or primary aromatic amine, secondary amine or tertiary amine.

12. curable compositions as claimed in claim 8 is characterized in that described thermal curing agents is selected from boron trifluoride complex, imidazoles, hydrazine and guanidine.

13. curable compositions as claimed in claim 1 is characterized in that it is a semiinterpenetrating polymer network.

14. curable compositions as claimed in claim 13 is characterized in that it is linerless (free standing) film.

15. curable compositions as claimed in claim 13 is characterized in that it is porous plastics, fiber or bead material.

16. curable compositions as claimed in claim 13 is characterized in that it is suprabasil protectiveness or decorative coating.

17. curable compositions as claimed in claim 14 is characterized in that described unsupported film is the backing of tackiness agent or band.

18. curable compositions as claimed in claim 16 is characterized in that described substrate is metal or polymkeric substance.

19. curable compositions as claimed in claim 13 is characterized in that it is a supatex fabric.

20. curable compositions as claimed in claim 13 is characterized in that it has flame retardant resistance.

21. a method is characterized in that it comprises the steps:

A) mix the solidifying agent of curable epoxy, curable epoxy, resin one of at least in the uncrosslinked hydro carbons polyolefin resin of pre-polymerization and the functionalized uncrosslinked polyolefin resin of complete pre-polymerization fully, described composition does not contain epoxidised natural and/or synthetic rubber

B) mixture with gained is coated on substrate, mould or the storage vessel, or be processed into unsupported film and

C) subsequently whenever, activate described solidifying agent, produce semiinterpenetrating polymer network,

Described hydro carbons polyolefine is meant the uncrosslinked polymeric hydrocarbon of the complete pre-polymerization that does not have machine functional group, and it is made by the homopolymerization and/or the copolymerization of olefinic monomer.

22. method as claimed in claim 21 is characterized in that adding described Resins, epoxy and described photocatalyst in the step of separating.

23. method as claimed in claim 21 is characterized in that described composition also contains the promotor of described resin.

24. method as claimed in claim 21 is characterized in that described composition also contains auxiliary, is enough to change the physical properties of solidifying the back semiinterpenetrating polymer network.

25. method as claimed in claim 21 is characterized in that it is the successive method.

26. method as claimed in claim 21 is characterized in that it is an interrupter method.

27. method as claimed in claim 21 is characterized in that the temperature when described mixing step carries out is lower than the heat activation temperature of solidifying agent.