CN100441637C - Thermoset composite composition, method, and article - Google Patents
Thermoset composite composition, method, and article Download PDFInfo
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- CN100441637C CN100441637C CNB2003801099103A CN200380109910A CN100441637C CN 100441637 C CN100441637 C CN 100441637C CN B2003801099103 A CNB2003801099103 A CN B2003801099103A CN 200380109910 A CN200380109910 A CN 200380109910A CN 100441637 C CN100441637 C CN 100441637C
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Abstract
A curable composition includes a functionalized poly(arylene ether) an olefinically unsaturated monomer, and a nanofiller. Methods of preparing and curing the composition, as well as uses for the cured composition, are described.
Description
Related application
The application requires the 60/319th, No. 805 U.S. Provisional Application of submitting on December 20th, 2002 and the 60/319th, No. 872 U.S. Provisional Application No. of submitting on January 16th, 2003.
Background technology
Duroplastic moulding materials well known in the art generally is the thermosetting resin that contains mineral filler and/or fiber.Thermosetting monomer shows enough low viscosity at the beginning when heating, can make the product that is obtained by the monomer composition of filling carry out melt-processed and molding.When further heating, thermosetting monomer reaction and curing, the solid resin of formation high rigidity.
A potential industrial application of thermoset composition is the assembly (under hood component) under electronic application field and the engine casing, for example engine valve gap.In electronic product according to the different specific insulating property of needs usually of Application Areas.Assembly under the engine casing preferably has high strength, the high ductibility under high-temperature and high-modulus.Simultaneously the gravel size decision of mouldings is in full accord with those die sizes that are used to prepare them.
The 6th, 352, No. 782 United States Patent (USP)s of people such as Yeager have been described the thermoset composition that comprises with the end capped polyaryl ether resin of ethylene linkage unsaturated group.These compositions table reveal perfect performance, comprise high glass-transition temperature and low thermal coefficient of expansion.Yet these materials also are not suitable for all application.
Therefore, for example insulation strength and high-modulus thermoset composition of mechanical property that still needs now to provide excellent and specific application performance.
Summary of the invention
Above-mentioned shortcoming with other is owing to having selected for use the curable compositions that contains functionalized poly-(arylene ether), ethylene linkage unsaturated monomer and Nano filling to obtain slowing down.
Other embodiment comprises the method for preparing curable compositions, the goods that comprise the curing composition of this curable compositions reaction product and contain this curing composition, all is illustrated below.
Detailed Description Of The Invention
An embodiment is so a kind of curable compositions, contains functionalized poly-(arylene ether), ethylene linkage unsaturated monomer and Nano filling.This curable compositions can also contain a kind of polymeric additive.
Here Nano filling is defined as a kind of particles filled material, wherein the linear dimension of nano particle is not more than about 1000 nanometers, is preferably to be not more than about 500 nanometers, more preferably is not more than about 100 nanometers, more preferably be not more than about 10 nanometers again, also more preferably be not more than about 1 nanometer.In curable compositions, use Nano filling can realize so far all control of some unknown performance in curable compositions and on the curing composition after solidifying.The use of Nano filling causes composition to have improved mechanical property, as high ductibility and high-modulus combination, perhaps makes composition have distinctive dielectric strength.
The composition that comprises functionalized poly (arylene ether) can be end capped poly-(arylene ether) or encircle functionalized poly-(arylene ether), and both are definition below respectively.
Functionalized poly-(arylene ether) can be end capped poly-(arylene ether).Here end capped poly-(arylene ether) is defined as wherein do not have at least 50% accordingly in the end-blocking poly-(arylene ether), preferred at least 75%, more preferably at least 90%, more more preferably at least 95% in addition also more preferably at least 99% free hydroxyl group by gather (arylene ether) functionalized with the END CAPPED GROUP reaction.
End capped poly-(arylene ether) can be represented with following structural formula:
Q(J-K)
y
Wherein, Q is the residue of monohydroxy, dihydroxyl or polyhydroxy phenol, is preferably the residue of monohydroxy or dihydric phenol, more preferably the residue of monohydroxy phenol; Y is 1～100; J comprises the repeated structural unit with following formula
Wherein, m is 1～about 200, be preferably 2～about 200; R
2And R
4Represent halogen atom, C independently of one another
1～C
12Uncle or secondary alkyl, C
2～C
12Alkenyl, C
2～C
12Alkynyl, C
1～C
12Aminoalkyl group, C
1～C
12Hydroxyalkyl, phenyl, C
1～C
12Haloalkyl, C
1～C
12-oxyl, the C of at least two carbon atoms separate halogen atoms and Sauerstoffatom wherein
2～C
12Halo-oxyl etc.; R
1And R
3Represent hydrogen, halogen, C independently of one another
1～C
12Uncle or secondary alkyl, C
2～C
12Alkenyl, C
2～C
12Alkynyl, C
1～C
12Aminoalkyl group, C
1～C
12Hydroxyalkyl, phenyl, C
1～C
12Haloalkyl, C
1～C
12-oxyl, the C of at least two carbon atoms separate halogen atoms and Sauerstoffatom wherein
2～C
12Halo-oxyl etc.; And the capping group of K for producing by phenolic hydroxyl group on poly-(arylene ether) and end-capping reagent reaction.The capping group that obtains can for
-Y-R
5，
Or the like, R wherein
5Be C
1～C
12Alkyl etc.; R
6～R
8Represent halogen atom, C independently of one another
1～C
12Alkyl, C
2～C
12Alkenyl, C
6～C
18Aryl, C
7～C
18Aryl, C that alkyl replaces
7～C
18Alkyl, C that aryl replaces
2～C
12Alkoxy carbonyl, C
7～C
18Aryloxycarbonyl, C
7～C
18Aryloxycarbonyl, C that alkyl replaces
7～C
18Aryl substituted alkoxy carbonyl, nitrile, formyl radical, carboxylicesters, imido-ester (imidate), carbothioic acid ester etc.; R
9～R
13Represent hydrogen, halogen, C independently of one another
1～C
12Alkyl, hydroxyl, amino etc.; And wherein Y is for example following divalent group:
Or the like, R wherein
14And R
15Represent hydrogen, C independently of one another
1～C
12Alkyl etc.
In an embodiment, Q is the residue that comprises the phenol of polyfunctional group phenol, and comprises the group of array structure down:
Wherein, R
1～R
4Represent hydrogen, halogen, C independently of one another
1～C
12Uncle or secondary alkyl, C
1～C
12Alkenyl, C
1～C
12Alkynyl, C
1～C
12Aminoalkyl group, C
1～C
12Hydroxyalkyl, phenyl, C
1～C
12Haloalkyl, C
1～C
12Amino oxygen base, C
1～C
12-oxyl, the C of at least two carbon atoms separate halogen atoms and Sauerstoffatom wherein
1～C
12Halo-oxyl etc.; X can be hydrogen, C
1～C
12Alkyl, C
6～C
18Aryl, C
7～C
18Aryl, C that alkyl replaces
7～C
18The alkyl that aryl replaces, or contain any above-mentioned hydrocarbyl group of at least one substituting group (as carboxylic acid, aldehyde, alcohol, amino group etc.); X also can be sulphur, alkylsulfonyl (sulfonyl), alkylsulfonyl (sulfuryl), oxygen, and perhaps other is such has the divalent or a bridge joint group of high price more, to obtain various binary or polybasic polyphenol more; Y and n be 1 independently of one another～about 100, be preferably 1～3, more preferably about 1～2; In a preferred embodiment, y=n.Q also can be the residue of diphenol (for example 2,2 ', 6,6 '-tetramethyl--4,4 '-diphenol).
In an embodiment, end capped poly-(arylene ether) is to prepare by poly-(arylene ether) mainly be made up of the polymerisate of at least a mono-hydroxy phenol with following array structure carried out end-blocking:
Wherein, R
1～R
4Represent hydrogen, halogen, C independently of one another
1～C
12Uncle or secondary alkyl, C
2～C
12Alkenyl, C
2～C
12Alkynyl, C
1～C
12Aminoalkyl group, C
1～C
L2Hydroxyalkyl, phenyl, C
1～C
12Haloalkyl, C
1～C
12-oxyl, the C of at least two carbon atoms separate halogen atoms and Sauerstoffatom wherein
1～C
12Halo-oxyl etc.The mono-hydroxy phenol that is fit to comprises those the 3rd, 306, No. 875 described compounds of United States Patent (USP) as licensing to Hay, and very preferred mono-hydroxy phenol comprises 2,6-xylenol and 2,3,6-pseudocuminol.Poly-(arylene ether) can be the multipolymer of at least two kinds of mono-hydroxy phenol (for example 2,6-xylenol and 2,3,6-pseudocuminol).
In a preferred embodiment, end capped poly-(arylene ether) comprises at least a capping group with following array structure:
Wherein, R
6～R
8Represent hydrogen, C independently of one another
1～C
12Alkyl, C
2～C
12Alkenyl, C
6～C
18Aryl, C
7～C
18Alkyl substituting aromatic base, C
7～C
18Aryl substituted alkyl, C
2～C
12Alkoxy carbonyl, C
7～C
18Aryloxycarbonyl, C
7～C
18Alkyl substituted aryloxy carbonyl, C
7～C
18Aryl substituted alkoxy carbonyl, nitrile, formyl radical, carboxylicesters, imido-ester (imidate), carbothioic acid ester etc.Highly preferred capping group comprises acrylate (R
6=R
7=R
8=hydrogen) and methacrylic ester (R
6=methyl, R
7=R
8=hydrogen).
In another preferred embodiment, end capped poly-(arylene ether) comprises at least a capping group with following array structure:
Wherein, R
5Be C
1～C
12Alkyl is preferably C
1～C
6Alkyl, more preferably methyl, ethyl or sec.-propyl.
The inventor finds uncannily, even lack polymerisable functional group when end capped poly-(arylene ether), for example during the two key of carbon-carbon, still can access excellent performance.
In another preferred embodiment, end capped poly-(arylene ether) comprises at least a capping group with following array structure:
Wherein, R
9～R
13Represent hydrogen, halogen, C independently of one another
1～C
12Alkyl, hydroxyl, amino etc.Preferred such END CAPPED GROUP comprises salicylate (R
9=hydroxyl, R
10～R
13=hydrogen).
In another preferred embodiment, end capped poly-(arylene ether) comprises at least a capping group with following array structure:
Wherein, A is saturated or unsaturated C
2～C
12Bivalent hydrocarbon radical, for example ethylidene, propylene, 1,3-propylidene, 2-methyl isophthalic acid, 3-propylidene, 2,2-dimethyl-1,3-propylidene, 1,2-butylidene, 1,3-butylidene, 1,4-butylidene, 2-methyl isophthalic acid, 4-butylidene, 2,2-dimethyl-1,4-butylidene, 2,3-dimethyl-tetramethylene, vinylidene (CH=CH-), 1,2-phenylene etc.These end capped poly-(arylene ether) resins for example prepare by not end capped poly-(arylene ether) reacted with the cyclic anhydride end-capping reagent usually.Such cyclic anhydride end-capping reagent for example comprises maleic anhydride, succinyl oxide, Pyroglutaric acid, adipic anhydride, Tetra hydro Phthalic anhydride etc.
Here the preparation method to end capped poly-(arylene ether) has no particular limits.End capped poly-(arylene ether) can form by not end capped poly-(arylene ether) reacted with end-capping reagent.End-capping reagent comprise in the document known can with the compound of phenolic group group reaction.Such compound had both comprised monomer, also comprised the polymkeric substance that for example contains acid anhydrides, acyl chlorides, epoxy, carbonic ether, ester, isocyanic ester, cyanate or alkyl halide group.End-capping reagent is not limited to organic compound, for example also comprises phosphorus or sulfenyl end-capping reagent.The example of end-capping reagent for example comprises diacetyl oxide, succinyl oxide, maleic anhydride, the bigcatkin willow acid anhydrides, comprise the unitary polyester of salicylate, salicylic single polyester, acrylic anhydride, methacrylic anhydride, epihydric alcohol acrylic ester, epihydric alcohol methylpropenoic acid ester, Acetyl Chloride 98Min., Benzoyl chloride, diphenyl carbonate (as two (4-nitrophenyl) carbonic ether), the acryloyl ester, the methacryloyl ester, acetonyl ester, phenyl isocyanate, 3-pseudoallyl-α, the alpha-alpha-dimethyl phenyl isocyanate, cyanato-benzene, 2,2-two (4-cyanato-phenyl) propane, 3-(α-chloromethyl) vinylbenzene, 4-(α-chloromethyl) vinylbenzene, allyl bromide 98 etc., carbonic ether and substitutive derivative thereof, and their mixture.These and other method that forms end capped poly-(arylene ether) is for example at the 4th, 148 of the 3rd, 375, No. 228 United States Patent (USP)s of people such as Holoch, Goossens, people's such as No. 843 United States Patent (USP)s, Percec the 4th, 562,243,4,663,402,4,665,137 and 5,091, people's such as No. 480 United States Patent (USP)s, Nelissen the 5th, 071,922,5,079,268,5,304,600 and 5,310, the 5th, 338, No. 796 United States Patent (USP)s of people such as No. 820 United States Patent (USP)s, Vianello; And people such as Peters the 261st, be described in the 574B1 European patent.
In a preferred embodiment, end capped poly-(arylene ether) can prepare by not end capped poly-(arylene ether) reacted in the alkenyl fragrant monomer as solvent with acid anhydrides.The advantage of this method is to produce end capped poly-(arylene ether) can mix the curable composition of formation immediately with other component; Adopt this method, do not need to separate end capped poly-(arylene ether) or remove unwanted solvent or reagent.
In the reaction of not end capped poly-(arylene ether) and acid anhydrides, can use the end-blocking catalyzer.The example of such compound comprise well known in the art can catalysis of phenol and those compounds of the polycondensation of above-mentioned end-capping reagent.Useful raw material is a basic cpd, for example comprises the basic cpd hydroxide salt, as oxyhydroxide of sodium hydroxide, potassium hydroxide, tetra-allkylammonium etc.; Alkyl tertiary amine is as tributylamine, triethylamine, xylidine, dimethylbutyl amine etc.; Blended alkyl-aryl tertiary amine and substitutive derivative thereof, as N, accelerine; Heterocyclic amine, as imidazoles, pyridine, and substitutive derivative, as glyoxal ethyline, 2-vinyl imidazole, 4-(dimethylamino) pyridine, 4-(1-pyrrolinyl) pyridine, 4-(1-piperidino-(1-position only)) pyridine, 2-vinyl pyridine, 3-vinyl pyridine, 4-vinylpridine etc.Organic metal salt equally usefully, the pink salt and the zinc salt of the polycondensation of known for example catalysis isocyanic ester or cyanate and phenol.Useful in this respect organic metal salt is disclosed in the those skilled in the art known many publications and patent.
Functionalized poly-(arylene ether) can be for encircling functionalized poly-(arylene ether).Here will encircle functionalized poly-(arylene ether) and be defined as poly-(arylene ether) that comprises following repeated structural unit:
Wherein, L
1～L
4Represent hydrogen atom, kiki alkenyl group or alkynyl group independently of one another; Wherein kiki alkenyl group is expressed as follows:
Wherein, L
5～L
7Represent hydrogen or methyl independently, a is 1～4 integer, and wherein alkynyl group is expressed as follows:
Wherein, L
8Be hydrogen, methyl or ethyl, b is 1～4 integer; And, wherein encircling the functionalized whole L in (arylene ether) that gather
1～L
4Substituent about 0.02mol%～about 25mol% is alkenyl and/or alkynyl group.In this scope, be preferably have about 0.1mol% at least, more preferably at least about alkenyl and/or the alkynyl group of 0.5mol%.Equally within this scope, be preferably and have up to about 15mol%, more preferably up to alkenyl and/or the alkynyl group of about 10mol%.
Encircling functionalized poly-(arylene ether) can prepare according to known method.For example, can use reagent,, make not functionalized poly-(arylene ether), itself and alkenyl halide (as allyl bromide 98) and/or alkynyl halogenide (as propargyl bromide) be reacted thereupon as poly-(2,6-dimethyl-1,4-phenylene ether) metallization as n-Butyl Lithium.The method of poly-(arylene ether) resin that this or other preparation ring is functionalized for example is described in the 4th, 923, No. 932 United States Patent (USP)s of people such as Katayose.
Be readily appreciated that poly-(arylene ether) of " not end-blocking " described here or " not functionalized " comprises the repeated structural unit of following formula:
Wherein, each Z in each structural unit
1All represent hydrogen, halogen, C independently
1～C
12Uncle or secondary alkyl, C
1～C
12Aminoalkyl group, C
1～C
12Hydroxyalkyl, phenyl, C
1～C
12Haloalkyl, C
1～C
12-oxyl, the C of at least two carbon atoms separate halogen atoms and Sauerstoffatom wherein
1～C
12Halo-oxyl etc.; And, each Z
2All represent halogen, C independently
1～C
12Uncle or secondary alkyl, C
1～C
12Aminoalkyl group, C
1～C
12Hydroxyalkyl, phenyl, C
1～C
12Haloalkyl, C
1～C
12-oxyl, the C of at least two carbon atoms separate halogen atoms and Sauerstoffatom wherein
1～C
12Halo-oxyl etc.Preferably, each Z
1Be C1～4 alkyl, each Z
2Be hydrogen or methyl.
Molecular weight and limiting viscosity to functionalized poly-(arylene ether) have no particular limits.In an embodiment, the number-average molecular weight of the functionalized poly that said composition comprises (arylene ether) can be high to about 10,000 atomic mass units (AMU), be preferably can be high to about 5,000AMU, more preferably can be high to about 3,000AMU.By reducing its viscosity, such functionalized poly (arylene ether) is more useful in the process of preparation and processing said composition.
In another embodiment, when under 25 ℃ of temperature, when measuring in the chloroform, the limiting viscosity of the functionalized poly that said composition comprises (arylene ether) can be about 0.08～about 0.30 deciliter/gram (dL/g), be preferably about 0.12～about 0.30dL/g, more preferably about 0.15～about 0.25dL/g.Usually, the limiting viscosity of functionalized poly (arylene ether) does not have noticeable change with the limiting viscosity of corresponding not functionalized poly (arylene ether).Specifically, the limiting viscosity of functionalized poly (arylene ether) generally functionalized poly (arylene ether) not 10% within.Such limiting viscosity roughly with about 5,000～about 25, the number-average molecular weight correspondence of 000AMU.In this scope, it is about 8 that number-average molecular weight is at least, and 000AMU is preferred, more preferably about 10,000AMU.Equally within this scope, number-average molecular weight is high to about 20, and 000AMU is preferred.Such functionalized poly (arylene ether) can provide toughness and processing characteristics ideal balance to composition.Think that particularly it is possible adopting at least two kinds of mixtures with functionalized poly (arylene ether) of different molecular weight and limiting viscosity.
In a preferred embodiment, functionalized poly-(arylene ether) is substantially free of amino substituting group, comprise alkylamine and dialkylamine substituting group, wherein do not contain substantially and refer to every gram functionalized poly-(arylene ether) and contain and be less than about 300 milligrams, be preferably and be less than about 100 milligrams Nitrogen Atom.Although the building-up processes of many poly-(arylene ethers) can be in conjunction with amino substituting group, the inventor finds, when functionalized poly-(arylene ether) when being substantially free of amino substituting group, thermofixation speed has improved.Being substantially free of amino substituent poly-(arylene ether) can gather (arylene ether) and be heated at least about 200 ℃ and directly synthesize or produce by what amino was replaced.Perhaps, if functionalized poly-(arylene ether) contains amino substituting group, to solidify said composition under about 200 ℃ of temperature more satisfactory being lower than.
Said composition can comprise the blend of at least two kinds of functionalized poly-(arylene ethers).Such mixture can be prepared by independent preparation and isolating functionalized poly (arylene ether).Perhaps, such blend can prepare by one poly-(arylene ether) reacted with at least two kinds of functionalized reagents.For example, a kind of poly-(arylene ether) can with two kinds of end-capping reagents reactions, perhaps a kind of poly-(arylene ether) can metallize and with two kinds of unsaturated alkyl reagent reacts.The another kind of selection is that the mixture of at least two kinds of poly-(arylene ether) resins can react with single functionalized reagent.
The amount that said composition comprises functionalized poly (arylene ether) is the functionalized poly (arylene ether) of about 1～about 90 weight parts/100 weight parts and the total amount of ethylene linkage unsaturated monomer.Within this scope, preferably select for use the amount of functionalized poly (arylene ether) to be at least about 10 weight parts, more preferably about 20 weight parts, more preferably about again 30 weight parts.Within this scope, preferably select for use the amount of functionalized poly (arylene ether) can arrive about 80 weight parts equally more, more preferably many to about 70 weight parts, more preferably many again, also more preferably many to about 50 weight parts to about 60 weight parts.
Said composition also comprises a kind of ethylene linkage unsaturated monomer.Such ethylene linkage unsaturated monomer for example comprises the described curable monomer composition of the 6th, 352, No. 782 United States Patent (USP)s as people such as Yeager.Preferred ethylene linkage unsaturated monomer comprises alkenyl fragrant monomer, acryl monomer, allyl monomer, reaches their mixture.Usually, the amount of ethylene linkage unsaturated monomer is based on the functionalized poly (arylene ether) of 100 weight parts and about 10～about 99 weight parts of ethylene linkage unsaturated monomer total amount.
The ethylene linkage unsaturated monomer can comprise a kind of alkenyl fragrant monomer.This alkenyl fragrant monomer can have following structure:
Wherein, each R
16Represent hydrogen, C independently
1～C
12Alkyl, C
2～C
12Alkenyl, C
2～C
12Alkynyl, C
6～C
18Aryl etc.; Each R
17Represent hydrogen, halogen, C independently
1～C
12Alkyl, C
1～C
12Alkoxyl group, C
6～C
18Aryl etc.; P is 1～4; And q is 0～5.P and q sum are 1,2,3,4,5 or 6.Work as p=1, the alkenyl fragrant monomer is called as simple function group alkenyl fragrant monomer; When p=2～4, the alkenyl fragrant monomer is called as polyfunctional group alkenyl fragrant monomer.The alkenyl fragrant monomer that is fit to comprises vinylbenzene, alpha-methyl styrene, α-ethyl styrene, α-isopropyl benzene ethene, α-t-butyl styrene, α-styryl phenyl etc.; Halogenated styrenes, for example chlorostyrene, dichlorobenzene ethene, trichloro-benzene ethene, bromostyrene, dibromo-benzene ethene, tribromo-benzene ethene, fluorostyrene, phenyl-difluoride ethene, trifluoro-benzene ethene, tetrafluoro are for vinylbenzene, phenyl-pentafluoride ethene etc.; Haloalkyl vinylbenzene, for example chloro vinyl toluene etc.; Alkoxystyrene is as methoxy styrene, phenetole ethene etc.; Polyfunctional group alkenyl fragrant monomer, for example 1,2-Vinylstyrene, 1,3-Vinylstyrene, 1,4-Vinylstyrene, trivinylbenzene, 1,3-diisopropyl benzene, 1,4-diisopropyl benzene etc.; And comprise above-mentioned alkenyl fragrant monomer mixture one of at least.In the vinylbenzene of above-mentioned replacement, substituent position is not specified, and substituting group can occupy the position of any vacancy on the aromatic nucleus.
Preferred alkenyl fragrant monomer comprises vinylbenzene, alpha-methyl styrene, 2-methyl styrene, 3-vinyl toluene, 4-vinyl toluene, 2-t-butyl styrene, 3-t-butyl styrene, 4-t-butyl styrene, 1,3-Vinylstyrene, 1,4-Vinylstyrene, 1,3-diisopropyl benzene, 1,4-diisopropyl benzene etc., and comprise above-mentioned alkenyl fragrant monomer mixture one of at least.Preferred alkenyl fragrant monomer also is included in has 1～5 the substituent vinylbenzene of halogen atom on the phenyl ring, and the mixture that comprises at least a such halogenated styrenes.
The alkenyl fragrant monomer is commercial can be obtained from a plurality of sources.They also can prepare by means commonly known in the art.
When the alkenyl unsaturated monomer comprised a kind of alkenyl fragrant monomer, preferably its consumption was the functionalized poly (arylene ether) of per 100 weight parts and about 10～about 90 weight parts of ethylenic fragrant monomer total amount.Within this scope, be preferably the amount of selecting the ethylenic fragrant monomer for use and be at least about 20 weight parts, more preferably at least about 30 weight parts.Within this scope, it is many to about 80 weight parts being preferably the content of selecting the ethylenic fragrant monomer for use, more preferably many to about 70 weight parts equally, more more preferably how to about 60 weight parts, also more preferably many to about 50 weight parts.
The alkenyl unsaturated monomer can comprise a kind of acryl monomer.In an embodiment, acryl monomer comprises at least a acryl part with following structure:
Wherein, R
18And R
19Represent hydrogen, C1～C12 alkyl etc. independently of one another; And, R wherein
18And R
19Carbon-carbon double bond can become cis or trans relatively.Preferably, R
18And R
19Represent hydrogen or methyl independently of one another.In an embodiment, acryl monomer comprises at least two acryl parts with said structure, and is called as polyfunctional group acryl part.In another embodiment, acryl monomer comprises at least three acryl parts with said structure.
In an embodiment, acryl monomer comprises at least a acryl part with following structure:
Wherein, R
20～R
22Represent hydrogen, C independently of one another
1～C
12Alkyl, C
2～C
12Alkenyl, C
6～C
18Aryl, C
7～C
18Alkyl substituting aromatic base, C
7～C
18Aryl substituted alkyl, C
2～C
12Alkoxy carbonyl, C
7～C
18Aryloxycarbonyl, C
8～C
18Alkyl substituted aryloxy carbonyl, C
8～C
18Aryl substituted alkoxy carbonyl, nitrile, formyl radical, carboxylicesters, imido-ester (imidate), carbothioic acid ester etc.Preferably, R
20～R
22Represent hydrogen or methyl independently of one another.In an embodiment, acryl monomer comprises at least two acryl parts with said structure.In another embodiment, acryl monomer comprises at least three acryl parts with said structure.
Many other the acryl that is fit to parts are described in the 2001/0053820A1 U.S. that people such as Yeager submit to openly applies for.
In a preferred embodiment, acryl monomer comprises that each molecule contains at least two, is preferably at least three acryls compound partly.The example that can enumerate comprises by the compound of acrylic or methacrylic acid with the polycondensation preparation of diepoxide (as bisphenol A diglycidyl ether, butanediol diglycidyl ether or neopentylglycol dimethacrylate).Concrete example comprises 1,4-butanediol diglycidyl ether two (methyl) acrylate, bisphenol A diglycidyl ether dimethacrylate and neopentylglycol diglycidyl ether two (methyl) acrylate etc.As acryl monomer, comprise that equally reactive acrylate or methacrylate compound and alcohols or amine condensation are to prepare final multi-functional acrylate or polyfunctional group acrylamide.Such example comprises N; N-two (2-hydroxyethyl) (methyl) acrylamide; methylene radical two ((methyl) acrylamide); 1; 6-hexa-methylene two ((methyl) acrylamide); diethylidene triamino three ((methyl) acrylamide); two (γ-((methyl) acrylamide) propoxy-) ethane; β-((methyl) acrylamide) ethyl propylene acid esters; ethylene glycol bisthioglycolate ((methyl) acrylate); Diethylene Glycol two (methyl) acrylate; TEG two (methyl) acrylate; glycerol two (methyl) acrylate; glycerol three (methyl) acrylate; 1; ammediol two (methyl) acrylate; dipropylene glycol two (methyl) acrylate; 1; 4-butyleneglycol two (methyl) acrylate; 1; 2; 4-butyleneglycol three (methyl) acrylate; 1; 6-hexylene glycol two (methyl) acrylate; 1; 4-cyclohexanediol two (methyl) acrylate; 1; 4-Resorcinol two (methyl) acrylate; tetramethylolmethane four (methyl) acrylate; 1; 5-pentanediol two (methyl) acrylate; TriMethylolPropane(TMP) two (methyl) acrylate; trimethylolpropane tris (methyl) acrylate; 1; 3; 5-triacryl six hydrogen-1; 3; the 5-triazine; 2; 2-two (4-(2-(methyl) acryloyl-oxy oxyethyl group) phenyl) propane; 2; 2-two (4-(2-acryloyl-oxy oxyethyl group)-3; the 5-dibromo phenyl) propane; 2; 2-two ((4-(methyl) acryloyl-oxy) phenyl) propane; 2; 2-two ((4-(methyl) acryloyl-oxy)-3; the 5-dibromo phenyl) propane etc., and contain aforesaid propylene acyl group monomer mixture one of at least.Should be appreciated that segment " (methyl) acryl " both represented " acryl ", again expression " methacryloyl ".
Highly preferred acryl monomer comprises (methyl) vinylformic acid trishydroxymethyl propyl ester; two (methyl) vinylformic acid 1; 6-hexylene glycol ester; two (methyl) vinylformic acid glycol ester; two (methyl) vinylformic acid propylene glycol ester; two (methyl) vinylformic acid cyclohexanedimethanoester ester; two (methyl) vinylformic acid butanediol ester; two (methyl) vinylformic acid binaryglycol ester; two (methyl) vinylformic acid triglycol ester; (methyl) isobornyl acrylate; (methyl) cyclohexyl acrylate; (methyl) butyl acrylate; (methyl) methyl acrylate; dibutyl fumarate; dibutyl maleinate; (methyl) glycidyl acrylate; (methyl) ethyl propenoate; (methyl) 2-EHA; (methyl) Ethyl acrylate; (methyl) vinylformic acid bay alcohol ester; (methyl) vinylformic acid stearyl alcohol ester; (methyl) decyl acrylate; (methyl) Octyl acrylate etc., and contain aforesaid propylene acyl group monomer mixture one of at least.
Acryl monomer can have been bought from a plurality of sources.They also can prepare by means commonly known in the art.
When the ethylene linkage unsaturated monomer comprised a kind of acryl monomer, preferably its consumption was the functionalized poly (arylene ether) of per 100 weight parts and about 1～about 50 weight parts of acryl monomer total amount.Within this scope, be preferably the content of selecting acryl monomer for use and be at least about 5 weight parts, more preferably at least about 10 weight parts.Within this scope, it is many to about 40 weight parts being preferably the content of selecting acryl monomer for use, more preferably many to about 30 weight parts equally, more more preferably how to about 20 weight parts.
The ethylene linkage unsaturated monomer can comprise a kind of allyl monomer.Allyl monomer is to comprise at least one allyl group (CH
2-CH=CH
2) organic compound.In an embodiment, allyl monomer comprises at least two allyl group.In another embodiment, allyl monomer comprises at least three allyl group.The allyl monomer that is fit to for example comprises allyl benzene, diallyl phthalate, different metatitanic acid diallyl, mellitic acid triallyl, triallylmesate, triallyl benzene, triallyl cyanurate, triallyl isocyanurate, their mixture, partially polymerized product prepared therefrom, or the like.
The Nano filling that is used in the composition can have rule or irregular profile.They can be sheet, fibrous, spherical, aciculiform, bulk or any other shape, or the combination of different shape, as long as the Nano filling linear dimension that is dispersed in the composition is not more than 1000 nanometers, be preferably linear dimension and be not more than about 500 nanometers, more preferably linear dimension is not more than about 100 nanometers, more preferably linear dimension is not more than 10 nanometers again, even more preferably linear dimension is not more than 1 nanometer.Add that filler in the resin Composition can comprise that Nano filling disperses to when forming curable compositions and the Nano filling aggregate of the micron-scale that forms.When disperseing in curable compositions, Nano filling can be scattered in an external phase, a plurality of external phase (when existing above an external phase) or disperse phase.Nano filling can randomly have about aspect ratio of 1～about 1000.In the part embodiment, preferably select for use the aspect ratio of Nano filling to be at least about 10: 1, more preferably at least about 30: 1, more more preferably at least about 100: 1, even more more preferably at least about 300: 1.
Nano filling is not subjected to the restriction of composition yet, and any known Nano filling that is considered to comprise in curable compositions all will be useful.Nano filling can provide amazing performance to composition, and partly cause is because the atom of very most Nano filling all is positioned at Nano filling particulate surface and can interacts with resin Composition.Nano filling can comprise carbon; Metal oxide comprises main group metal oxide compound such as aluminum oxide, and transition metal oxide such as one or more titanyl compounds; Metallic carbide; Cermet material; Pottery; Glass; Uhligite; The layered inorganic material; Filamentous inorganic materials or the like; And above-mentioned combination.
The illustrative example of useful filamentous material is imogolite and vanadium oxide.Stratified material changes non-constant width, comprises phyllosilicate.The illustrative example of such material is that soil, nontronite, beidellite, volkonskoite, hectorite, saponite, sauconite, magadiite (magadiite), fibrous morphology crystals (kenyaite) and vermiculite if you would be taken off in montmorillonite clay ore deposit.Other useful stratified material comprises the mixture in Erie's stone ore (as ledikite) and illite and above-mentioned clay ore deposit.Other useful stratified material is a layered double-hydroxide, as Mg
6Al
3.4(OH)
18.8(CO
3)
1.7H
2O.Other stratified material comprises muriate, as FeCl
3And FeOCl; Chalkogenide is as TiS
2, MoS
2And MoS
3Prussiate is as Ni (CN)
2And oxide compound, as H
2Si
2O
5, V
6O
13, HTiNbO
5, Cr
0.5V
0.5S
2, W
0.2V
2.8O
7, Cr
3O
8, MoO
3(OH)
2, VOPO
4--2H
2O, CaPO
4CH
3--H
2O, MnHAsO
4--H
2O, Ag
6Mo
10O
33Or the like.
Useful stratiform and filamentous material comprise that those make the compound that expands and embed between layer and fibril by organophilic intercalating agent, and this intercalating agent is by expanding distance between interlayer and fibril to weaken the internal cohesive energy between layer and fibril.In a preferred embodiment, the consistency and the cohesive force of the resin Composition that one or more intercalating agents improve layer or fibril and curable compositions by attracting each other between while and fibril or laminar surface and the polymkeric substance.Intercalating agent to the expanded effect of distance between interlayer or fibril also is referred to as " swelling agent " sometimes, and the intercalating agent that plays the consistency that increases between layer or fibril and curable or the cured compositions and cohesive force effect also is referred to as " compatilizer " sometimes and the intercalating agent that plays swelling agent and compatilizer effect also is referred to as " expansion/compatilizer " sometimes.Intercalating agent can import in the space between interlayer or fibril by inserting (under the situation of neutral atom) or ion-exchange (under the ionic situation).Intercalating agent can import with the form of solid, liquid, gas or solute.Intercalating agent can import among the space of each layer of this material or each fibril, nearly all layer or fibril or most of layer or fibril.Intercalating agent can single use or is used in combination.
The Nano filling that is fit to also comprises expandable layered inorganic material.Usually, the layered inorganic material comprises the layer with two opposite faces, and these faces can relatively flat or slight curvature.Such material is described in the 4th, 889, No. 885 United States Patent (USP)s of people such as Usuki.The representative example of inflatable stratiform inorganic materials comprises for example polynite of inorganic laminated silicate, nontronite, beidellite, volkonskoite, hectorite, saponite, sauconite, magadiite (magadiite), fibrous morphology crystals (kenyaite), medmontite and vermiculite.Also can use other to have seldom or do not have the stratified material or the multilayer aggregate of electric charge,, their interlayer be swollen at interval get final product as long as they can embed swelling agent at laminar surface.On the contrary, also can use than above-mentioned those to have the more stratified material of multi-charge, the member of mica family for example as long as they can insert with swelling agent, and swells their interlayer at interval.Also can use one or more such mixtures of material.
Other representative example of stratified material comprises Erie's stone ore, as ledikite; Layered double-hydroxide or blended metal hydroxides are as Mg
6Al
3.4(OH)
18.8(CO
3)
1.7H
2O (reaching the article of delivering thereafter for the 547th page at " Journal of Catalysis (catalysis journal) " 1985 the 94th volumes) referring to W.T.Reichle, it has the layer that is filled with positive charge, has tradable negatively charged ion in the interlayer interval; Muriate is as ReCl
3And FeOCl; Chalkogenide is as TiS
2, MoS
2And MoS
3Prussiate is as Ni (CN)
2And oxide compound, as H
2Si
2O
5, V
5O
13, HTiNbO
5, Cr
0.5V
0.5S
2, W
0.2V
2.8O
7, Cr
3O
8, MoO
3(OH)
2, VOPO
4--2H
2O, CaPO
4CH
3--H
2O, MnHAsO
4--H
2O, Ag
6Mo
10O
33Or the like.Also can use other to have seldom or do not contain the inflatable stratiform inorganic materials or the multilayer aggregate of electric charge, as long as they can embed swelling agent their interlayer is swollen at interval at laminar surface.Also can use one or more such mixtures of material.
Preferred inflatable stratiform inorganics comprises that those have the inorganics of electric charge and exchangable ion (as sodium, potassium and calcium positively charged ion) on layer, these ions can with ion, be preferably the silicoorganic compound exchange that ion (as ammonium cation) maybe can react, be preferably ion-exchange, this can cause layering of many plane particles or expansion.Usually, the negative electricity He of inflatable stratiform inorganic material surface is at least 20 milligramequivalents with respect to per 100 gram multilayer materials, is preferably at least 50 milligramequivalents, more preferably 50～150 milligramequivalents.Particularly preferably be inorganic laminated silicate, if you would take off soil, nontronite, beidellite, volkonskoite, hectorite, saponite, sauconite, magadiite (magadiite) and fibrous morphology crystals (kenyaite), and per 100 gram materials have millinormal hectorite in 20 milligramequivalents～150 and polynite.Preferred inflatable stratiform inorganic materials is inorganic laminated silicate, with respect to each formula unit,, between 0.2～1.2 scope, most preferably be each formula unit and have the inorganic laminated silicate of the exchangeable cation of equivalent at interval between 0.2～0.9 scope and at interlayer at the negative electricity He on the layer at the negative electricity He on the layer.
Inflatable stratiform inorganic materials can have organophilic character by the method that is referred to as " embedding ", and this embedding comprises or by inserting (under the situation of neutral atom) or ion-exchange (under the ionic situation) intercalating agent (neutral or charged kind) imported in the interlayer or the space between fibril of inflatable stratiform inorganic materials.Telescopiny also makes the interlayer of inflatable stratiform inorganic materials increase at interval.Here term " space between interlayer or fibril or at interval " refers to distance between the surface of each layer or the distance between fibril.Under the ionic situation, ion can with the ion-exchange of like charges, bigger kind, for example, the exchange of sodium or calcium ion and ionic.Anyly describedly contain neutral or electrically charged species, cause interlayer every all being referred to as intercalated material (intercalated material) than the stratified material that increases in the past in interlayer region.This specification sheets comprises that equally those are endowed the stratified material of organophillic performance.Such material is referred to as polyorganosilicate usually.
Intercalating agent is by expanding interfloor distance to play the effect of reduction interlayer internal cohesive energy, and by playing the effect that increases layer and the consistency and the cohesive force of matrix with the sucking action of layer and other curable compositions component simultaneously.Intercalating agent can import each layer of inflatable stratiform inorganic materials or each fibril, nearly all layer or fibril or quite in the layer or the space between the fibril of vast scale.The method that intercalating agent is imported the interlayer region of inflatable stratiform material is known in those skilled in the art, for example can be referring to the 4th, 889, No. 885 United States Patent (USP)s of people such as Usuki.Here be not these methods will be restricted in any specific method or the program.
Intercalating agent generally contains a kind of functional group, the laminar surface reaction of it and stratified material and all or part of displacement organic ion and bond with laminar surface.Comprise nucleophilic or electrophilic functional group with these functional groups of polymer reaction, close electricity or nucleophilic displacement reaction, linked reaction and various ring-opening reaction can take place in them.The example of such functional group comprises amino, carboxyl, acid halide group, acyloxy, hydroxyl, isocyano, uride, halogen atom, epoxy, epoxy chloropropane or the like.
The intercalating agent that is fit to comprises water-soluble polymers, compound, as ammonium salt, phosphonium salt or sulfonium salt.Amphoterics, compound choline, silicoorganic compound, and their mixture.
Can be the water-soluble polymers of vinyl alcohol as the representational example of water-soluble polymers of organic intercalating agent, as polyvinyl alcohol; Polyalkylene glycol is as polyoxyethylene glycol; Water-soluble cellulose polymer is as methylcellulose gum and carboxymethyl cellulose; The ethylene linkage unsaturated carboxylic acid, as polyacrylic acid, and its esters; Polyvinylpyrrolidone; And the mixture of above-mentioned water-soluble polymers.Also can use the monomeric unit of these polymkeric substance, the mixture of for example ethylene glycol, or ethylene glycol and propylene glycol, or propylene glycol.
The representative example that can be used as the compound of organic intercalating agent comprises cats product, as has the quaternary ammonium salt of octadecyl, hexadecyl, tetradecyl or dodecyl group; Preferred quaternary ammonium salt comprises octadecyl leptodactyline, two octadecyl dimethyl ammonium, cetyltrimethyl ammonium salt, double hexadecyl dimethyl ammonium, tetradecyl leptodactyline, two tetradecyl dimethyl ammonium, dihydroxy ethyl methyl octadecyl ammonium salt, dihydroxy ethyl hydrogenated tallow dimethyl ammonium salt, contains the salt in conjunction with substituent quaternary ammonium salt of polyoxyalkylene fragment and polyoxyalkylene polyamines, for example Huntsman company
Product.
Can comprise as the representative example of the amphoterics of organic intercalating agent and have the fatty amine cation group and as carboxyl, vitriol, sulfonate or the phosphatic tensio-active agent of anionic group.
The representative example that can be used as the compound choline of organic intercalating agent comprises [HOCH
2CH
2N (CH
3)
3]
+OH
-, C
5H
14ClNO, C
5H
14NOC
4H
5O
6, C
5H
14NOC
6H
7O
7And C
5H
14NOC
6H
12O
7Or the like.
The representative example that can be used as the silicoorganic compound of organic intercalating agent comprises the silane reagent with following formula:
(--)
nSiR
(4-n-m)R
1 m
Wherein, (--) is the covalent linkage that is connected to the stratified material surface; M is 0,1 or 2; N is 1,2 or 3, prerequisite be m and n and equal 3; R
1Organic group (comprising alkyl, alkoxyalkyl, alkylaryl, aralkyl and alkoxy aromatic yl) for non-hydrolysable; R can be identical or different when occurring at every turn and be one can with the organic group of at least one component reaction in the curable compositions.Representational R group comprises amino, carboxyl, acid halide group, acyloxy, hydroxyl, isocyano, uride, halo, epoxy, epoxy chloropropane or the like.Preferred organosilicon intercalating agent comprises the quaternary ammonium salt and/or the suitable functionalized silicoorganic compound of long chain branching, and is disclosed as the 9th～21 page of WO 93/11190.
Also can use not to be described organic materials, as long as they can be embedded in the interlayer of multilayer particle formed material as organic intercalating agent.
In an embodiment, the stratified material of embedding is that a kind of bed thickness is the silicate of the embedding of 7～12 dusts.This bed thickness does not comprise the thickness of intercalating agent part.
The Nano filling that is fit to comprises the oligomeric silicon half oxygen alkane (silsesquioxanes) of polyhedral (so-called " POSS Nano filling ").Representational POSS Nano filling people such as J.Polidan in the AmericanPhysical Society annual meeting in March, 2002, Session M33 is described (http://www.eps.org/aps/meet/MAR02/baps/abs/S4735035.html) in the article of delivering on the Poster Session IV " Interfacial Properties of POSS-Nanofillers ".The POSS Nano filling also can have been bought from the market, and for example 1,3,5,7,9,11,13,15-eight (2-dichloromethyl silyl) ethyl five rings-[9.5.1.1
3,9.1
5,15.1
7,13] eight siloxanes (chemical abstracts registry no 314727-18-9), eight (tetramethyl-ammonium) five rings-[9.5.1.1
3,9.1
5,15.1
7,13] eight siloxanes-1,3,5,7,9,11,13,15-eight (yloxide) hydrate (chemical abstracts registry no 69667-29-4), and 1,3,5,7,9,11,13,15-eight vinyl five rings-[9.5.1.1
3,9.1
5,15.1
7,13] eight siloxanes (chemical abstracts registry no 69655-76-1), all derive from Aldrich chemical company.
The Nano filling that is fit to also comprises the described nano-dispersed powder that contains dispersive nanoscale powder on coarse carrier powder more of the 6th, 652, No. 967 United States Patent (USP)s of people such as Yadav for example; As the metal crystallite on the described metal that is embedded in another kind of difference in functionality of the 6th, 646, No. 302 United States Patent (USP)s of people such as Kan; And as the described sprayable dispersive nanofiller composition of the 6th, 645, No. 589 United States Patent (USP)s of people such as Cramer.
Nano filling also comprises carbon nanofiber and carbon nanotube, and for example Applied Sciences company, commodity are called
The commercially available prod; The single-walled nanotube that can buy from CarboLex company; Diameter is about carbon nanofiber or " fento " of 10～15 nanometers, can buy from Hyperion CatalysisInternational.The organic clay that is fit to comprises the montmorillonite-based nano clay, derives from Nanocor; And organically-modified layered magnesium silicate aluminium flake, derive from Southern Clay Prouducts, trade(brand)name
In an embodiment, Nano filling is substantially free of the carbon of conduction.In this embodiment, Nano filling does not comprise that linear dimension is not more than the conductive carbon of 1000 nanometers, for example the length graphite granule that is not more than 1000 nanometers less than the carbon fiber and the linear dimension of 1000 nanometers less than the carbon nanotube of 1000 nanometers, length.
The content of Nano filling in the said composition based on the total mass of composition, can be about 0.5～about 80 weight %.Within this scope, be preferably and adopt the content of Nano filling to be at least about 1 weight %, more preferably at least about 1.5 weight %.Within this scope, be preferably the amount of using Nano filling and arrive about 70 weight % more equally, more preferably many to about 50 weight %, more preferably many again to about 40 weight %.
Said composition can also randomly comprise a kind of curing catalysts, to improve the solidification rate of unsaturated component.Curing catalysts also is referred to as initiator, is well known in the art, is used for initiated polymerization, curing or crosslinked many thermoplasticss and thermosetting resin, comprises unsaturated polyester, vinyl ester and allyl group thermosetting resin." plastics additive handbook (the 4th edition) " that the non-limitative example of curing catalysts is secondaryly compiled R.Gachter and H.Muller chief editor, P.P.Klemchuk, Hansen press in New York published in 1993, and people such as Smith the 5th, 407, the 5th of people such as No. 972 United States Patent (USP)s and Katayose, be described in 218, No. 030 United States Patent (USP)s.The curing catalysts that is used for the unsaturated part of thermosetting resin can comprise any compound that can at high temperature produce free radical.Such curing catalysts had both comprised the peroxide radical initiator, also comprised non-peroxide radical initiator.The example of useful peroxide initiator for example comprises benzoyl peroxide, dicumyl peroxide, methyl ethyl ketone peroxide, lauryl peroxide, the pimelinketone superoxide, the tertbutyl peroxide thing, the tert.-butylbenzene hydroperoxide, cross the sad tert-butyl ester, 2,5-dimethylhexane-2,5-diperoxy hydrogen thing, 2,5-dimethyl-2,5-two (t-butyl peroxy)-oneself-3-alkynes, ditertiary butyl peroxide, tertiary butyl cumyl peroxide, α, α '-two (a t-butyl peroxy-sec.-propyl) benzene, 2,5-dimethyl-2,5-two (t-butyl peroxy) hexane, dicumyl peroxide, the different titanic acid ester of two (t-butyl peroxy), peroxidized t-butyl perbenzoate, 2,2-two (t-butyl peroxy) butane, 2,2-two (t-butyl peroxy) octane, 2,5-dimethyl-2,5-two (Benzoyl Peroxide) hexane, two (trimethyl silyl) superoxide, trimethyl silyl phenyl triphenyl silyl superoxide, methyl-prop acyloxy propyl trimethoxy silicane, ethoxylation dihydroxyphenyl propane two (methyl) acrylate etc., and the mixture that comprises above-mentioned at least a curing catalysts.Typical non-peroxide initiator for example comprises 2,3-dimethyl-2,3-diphenyl butane, 2,3-trimethyl silyl oxygen-2,3-diphenyl butane etc., and the mixture that comprises above-mentioned at least a curing catalysts.The curing catalysts that is used for the unsaturated part of thermosetting resin can also comprise any compound that can cause unsaturated component anionic polymerisation.Such anionic polymerisation catalyzer for example comprises alkali metal ammonia compound, as ammonification sodium (NaNH
2) and ammonification diethyl lithium (LiN (C
2H
5)
2); C
1～C
10An alkali metal salt of alkoxide and ammonium salt; Basic metal and ammonium oxyhydroxide; Alkali metal cyanide; Organometallic compound is alkyl lithium compounds n-Butyl Lithium and Grignard reagent phenyl-magnesium-bromide for example; Or the like; And the combination that comprises above-mentioned at least a anionic polymerisation catalyzer.
In a preferred embodiment, curing catalysts can comprise peroxidized t-butyl perbenzoate or methyl ethyl ketone peroxide.Curing catalysts can promote to solidify in about 0 ℃～about 200 ℃ of temperature ranges.
Curing catalysts, if exist, its consumption can be about 0.1～about 10 weight parts with respect to functionalized poly of per 100 weight parts (arylene ether) and ethylene linkage unsaturated monomer total amount.Within this scope, the preferred consolidation catalyst consumption is at least about 0.5 weight part, more preferably at least about 1 weight part.Within this scope, how the preferred consolidation catalyst consumption to 5 weight parts, more preferably arrives about 3 weight parts for more equally.
Said composition also can be chosen wantonly and comprise a kind of curing catalyst, to reduce gel time.The curing catalyst that is fit to comprises transition metal salt and title complex, for example cobalt naphthenate; And organic bases, N for example, N-xylidene(s) (DMA) and N, N-diethyl-aniline (DEA).Preferably, use the combination of cobalt naphthenate and DMA.If exist, the consumption of promotor, the total amount with respect to functionalized poly (arylene ether), ethylene linkage unsaturated monomer and the acryl monomer of per 100 weight parts is about 0.05～about 3 weight parts.
Said composition can comprise a kind of optional polymeric additive.The glass transition temperature of this polymeric additive is less than or equal to 100 ℃, is preferably to be less than or equal to 75 ℃, more preferably is less than or equal to 50 ℃, more preferably is less than or equal to 25 ℃ again, more preferably is less than or equal to 0 ℃ again.The Young's modulus of this polymeric additive is less than or equal to 1000Mpa (25 ℃), is preferably to be less than or equal to 100Mpa (25 ℃), more preferably is less than or equal to 10Mpa (25 ℃).In an embodiment, the polymeric additive that is fit to is selected from polyalkenyl hydrocarbon, poly-(methyl) alkyl acrylate, polyvingl ether, polysiloxane, and the combination that contains above-mentioned at least a polymeric additive.
If there is its consumption in polymeric additive, the total amount with respect to functionalized poly (arylene ether), ethylene linkage unsaturated monomer and the polymeric additive of per 100 weight parts is about 0.05～about 30 weight parts.Within this scope, the consumption of polymeric additive is preferably at least about 0.5 weight part, more preferably at least about 1 weight part, and also more preferably at least about 2 weight parts, more more preferably at least about 5 weight parts, even more preferably at least about 8 weight parts.Within this scope, the consumption of polymeric additive is preferably many to about 25 weight parts equally, and is more preferably many to about 20 weight parts, more preferably many again to about 15 weight parts.Usually, the consumption of polymeric additive is preferably the so-called stagnation point that is less than composition.Critical composition has defined the above contents level of additive.This level is too high, and the additive that is separated is transformed into external phase from faint disperse phase.Use the thermodynamics differential equation and component specific volume (being molecular weight/density) can estimate the critical composition of binary mixture.For a polycomponent base resin, can estimate average specific volume.It is to add that by the inverse with quantity 1 square root of component 1 specific volume and component 2 specific volume ratios calculates that the critical volume of component 1 is partly formed, as T.A.Callaghan and D.R.Paul at " Macromolecules (macromole) " the 2439th～2450 page of article of delivering of 1993 the 26th volumes and I.C.Sanchez as described in the 471st～475 page of article of delivering of " Polymer (polymkeric substance) " 1989 the 30th volumes.
Said composition can also comprise one or more non-nano fillers, comprises granular filler and fibrous packing.At least one linear dimension of non-nano filler is greater than about 1000 nanometers.The example of such filler is well known in the art, comprise and described in " plastics additive handbook (the 4th edition) " that R.Gachter and H.Muller chief editor, P.P.Klemchuk secondary compile, Hansen press in New York published in 1993 granular filler is defined as average aspect ratio here less than about 5: 1 filler.The nonrestrictive example of filler comprises SiO 2 powder, for example fused silica and crystalline silica; Boron nitride powder and borosilicate powder are used to make the solidified product to have low-k and low dielectric loss tangent; Above-mentioned powder, and the oxide compound of the aluminum oxide of heat conduction and magnesium (or magnesium oxide); And filler, for example wollastonite comprises that surface-treated wollastonite, calcium sulfate (its anhydride, two water things or three water things), lime carbonate comprise the sedimentary lime carbonate of chalk, Wingdale, marble and synthetic, generally exist, wherein usually contain CaCO more than 98% with the ground particle form
3, all the other are other inorganics, for example magnesiumcarbonate, ferric oxide and pure aluminium silicate; Surface-treated lime carbonate; Talcum, comprise fibrous, make standard-sized (modular), acicular and laminar talcum; Hollow and solid glass sphere, and generally have coupling agent (as silane coupling agent) and/or contain the surface-treated glass sphere of conductive coating; And kaolin, comprise hard, soft, calcined kaolin, and comprise various coatings well known in the art to help dispersion and compatible kaolin in thermosetting resin; Mica comprises the metallization mica and carries out surface treatment to give the mica of compound blend good physical behavior with aminosilane or acryl silane coating; Feldspar and nepheline syenite; The silicate bead; Quick ash; Cenosphere; Fillite; Pure aluminium silicate (armosphere) comprises silanization and metallized pure aluminium silicate; Neutral quartz sand; Quartzy; Quartzite; Perlite; Diatomite; Diatomite; Synthetic silica comprises that those have the silica of various silane coatings, or the like.
If the non-nano filler exists, its consumption based on composition total weight, is about 0.5wt%～about 80wt%.Within this scope, the consumption of non-nano filler is preferably at least about 1wt%, more preferably at least about 1.5wt%.Within this scope, the consumption of non-nano filler is preferably many to about 70wt% equally, and is more preferably many to about 50wt%, more preferably many again to about 40wt%.
Nano filling and optionally the non-nano filler can be without any processing, or through adding in the thermosetting resin after the surface treatment (generally adopting adhesion promoter).
Can also randomly comprise a kind of adhesion promoter in this prescription, to improve the adhesivity of thermosetting resin and filler, outside coating or substrate.Also can handle above-mentioned mineral filler, to improve adhesivity with adhesion promoter.Adhesion promoter comprises chromic compound, silane, titanic acid ester, zirconium aluminate, propylene copolymer-maleic anhydride, the plain ester of reactive fibre or the like.Chromic compound comprises that those are by name with commodity by Du Pont
Product sold.Silane comprises having formula (RO)
(4-n)SiY
nMolecule, n=1～3 wherein, R is the alkyl or aryl group, and Y is the reactive functionality that can form key with polymer molecule.The useful especially example of coupling agent has (RO) for those
3The compound of SiY structure.Typical example comprises vinyltriethoxysilane, vinyl three (2-methoxyl group) silane, γ-methacryloxypropyl trimethoxy silane, γ-An Jibingjisanyiyangjiguiwan, γ-glycidoxypropyltrimewasxysilane, γ-Qiu Jibingjisanjiayangjiguiwan.Titanic acid ester comprises the Ann.Chem.Tech Conf.SPI that people such as those S.J.Monte hold in the New Orleans " (1980), the article of delivering on Ann.Tech Conf.Reinforced Plastics and Composite inst.SPI (1979) the Section 16E; And S.J.Monte is at the described compound of having developed of " Mod.Plastics Int. " 1984 the 14th volumes the 6th phase page 2.Zirconium aluminate comprise those as L.B.Cohen at the compound described in the 29th page of article of delivering of " Plastics Engineering (plastic engineering) " nineteen eighty-three the 39th volume o. 11th.These adhesion promoters can be included in separately in the thermosetting resin, also can be coated on above-mentioned any filler, to improve the adhesivity between filler and the thermosetting resin.For example, such promotor can be used to apply ceramic fibre or filler, to improve the adhesivity of resinous substrates.
Said composition can also randomly comprise a kind of additive that is selected from fire retardant, releasing agent and other lubricant, antioxidant, thermo-stabilizer, UV light stabilizing agent, pigment, dyestuff, tinting material, static inhibitor, conductive agent, curing catalyst etc., and the combination of above-mentioned at least a additive.The kind of special additive and the selection of consumption can be undertaken by those skilled in the art.
Have no particular limits for the method for preparing said composition.Said composition can prepare by the initial blends that forms functionalized poly (arylene ether), alkenyl fragrant monomer and/or vinyl monomer, acryl monomer, Nano filling and optional component.When functionalized poly (arylene ether) is end capped poly-(arylene ether); this mixture can be directly by not end capped poly-(arylene ether) preparation; promptly by not end capped poly-(arylene ether) is dissolved in the part alkenyl fragrant monomer; in the presence of the alkenyl fragrant monomer, add end-capping reagent forming end capped poly-(arylene ether), and add acryl monomer, Nano filling and any other component to form thermoset composition.This Nano filling can add or add in the mode of masterbatch with batching.
In an embodiment, Nano filling and mixed with polymers are to form masterbatch, and masterbatch mixes with functionalized poly (arylene ether) and ethylene linkage unsaturated monomer subsequently.Perhaps, Nano filling also can with solvent, to form the Nano filling dispersion liquid, this dispersion liquid mixes with functionalized poly (arylene ether) and ethylene linkage unsaturated monomer subsequently.This Nano filling dispersion liquid can randomly comprise swelling agent, compatilizer, expansion/compatilizer and above-mentioned combination.
In an embodiment, said composition can form by functionalized poly (arylene ether), ethylene linkage unsaturated monomer and Nano filling being used mixing energy less than about 50 joules/liter (kJ/L) mix, and wherein refers at 25 ℃ of volumes of these blend compositions down with the volume size that is upgraded to unit representation.The physics of this curing composition and the balance of electric property are mixed in which way component in this curable compositions and are considered to compare sensitivity.Especially, though the method for typical high-energy, high shear force is beneficial to the mechanical property of this curing composition, be considered to cause the undesirable weakening of conductivity.When mixing energy less than about 50kJ/L, be preferably less than about 35kJ/L, during more preferably less than about 30kJ/L, can obtain the required physics and the balance of electric property.In order not damage the mechanical property of said composition, be preferably with mixing energy be at least about 0.025kJ/L, more preferably at least about 0.25kJ/L, more preferably mix the component of this curable compositions again at least about 2.5kJ/L.
The device that is used for blend curable compositions component is had no particular limits.The inside blend method that is fit to comprise mediate mix, Banbury mixer mixes, spiral mixes, Henschel mixes, mix, stirred vessel mixing or the like, and comprising combination at least a in the aforesaid method, these methods all are that those skilled in the art are known.
Said composition solidified method is had no particular limits.For example said composition can or adopt radiotechnology to solidify by thermofixation, comprises UV radiation and electron beam irradiation.When adopting thermofixation, temperature can be chosen in about 80 ℃～about 300 ℃.Within this scope, preferably select for use to be at least about 120 ℃ temperature.Within this scope, preferably select for use high equally to about 240 ℃ temperature.Can be about 30 seconds to about 24 hours heat-up time.Within this scope, select for use and be at least about 1 minute preferred heat-up time, more preferably was at least about 2 minutes.Within this scope, select for use many by about 10 hours preferred heat-up time equally, more preferably many by about 5 hours, more preferably many again by about 3 hours.Such curing can be stage by stage, to produce partly solidified and common sticking resin, subsequently with its longer time or at said temperature scope internal heating with completely solidified.
An embodiment is so a kind of curable compositions, and it comprises: poly-(2,6-dimethyl-1,4-phenylene ether) of a kind of (methyl) acrylate ended; A kind of acryl monomer that comprises two acryl group at least; And a kind of Nano filling.The curable compositions of another embodiment is to comprise: poly-(2,6-dimethyl-1,4-phenylene ether) of a kind of (methyl) acrylate ended of about 1～about 90 weight parts; A kind of acryl monomer that comprises two acryl group at least of about 10～about 99 weight parts; And a kind of Nano filling of about 0.5～about 80 weight parts; Wherein, poly-(2,6-dimethyl-1,4-phenylene ether) of (methyl) acrylate ended and the content of acryl monomer are based on the gross weight of these two kinds of components, and the content of Nano filling is based on the gross weight of composition.
Other embodiment comprises by above-mentioned any curable compositions partly or entirely solidifies reaction products resulting.
Also have other embodiment, comprise the product that includes any curing composition.Can for example comprise the acid bath container by the product of said composition manufacturing, neutralization tank, the electrorefining jar, the jar of softening water, tanks, twine the silk jar, twine silk jar lining, electrolyzer, gas shaft, washer, the engine valve gap, the automobile outer panels, automotive floor panel base (floor pan), the automobile air scoop, truck bed liner (bedliner), transmission shaft, the transmission shaft shaft joint, the tractor parts, the transverse slat spring, crankcase heater, hot baffle, railway tank waggon, the tipping bucket car bonnet, shell, the undersea boat shell, the boat deck, the marine terminal protective shield, aircraft component, propeller blade, missile component, rocket motor case, the wing section, sucker rod, body parts, wing covering, wing flairing, engine narcell, cargo port, flexible piece of aircraft and plummet assembly, bridge girder, decking, between the plate ladder, railing, the walkway, pipeline, pipe, fan guard, watt, the building panel, washing tower, the floor, the expansion joint that is used for bridge, be used to repair the fissured injectable mortar of building concrete, be used for the grouting of tile, machine track, metallic pin, bolt, stake, the Electronic Packaging agent, the electronic packaging material, electronic panel, printed circuit board (PCB), electronic component, coiling, be used for the sealing of electro-mechanical devices, cell box, resistance, safety fuse, thermocutout, the coating that is used for printed circuit board (PCB), electric capacity, transformer, the conducting element that is used for antistatic Application Areas, tennis racket, golf club shaft, fishing rod, ski, ski pole, bicycle assembly parts, swimming pool, the swimming pool slide plate, the heating bath dish, sauna, agitator, the business machine shell, pallet, the dishwashers parts, parts of refrigerator, stove, garage door, fence, protection gear (body gear), leather trunk, optical waveguide, radome, the satellite reflection dish, signboard, solar panel, the telephone switch device housings, transformer casing, be used for the insulation of rotating equipment, communication equipment, core insulation, the dry toner resin, bonding jig, check and use anchor clamps, the Industrial Metal shaping mould, vacuum injection tool or the like.
For example the engine valve gap is particularly useful for the element under the manufacturing automotive hood for said composition.
Though with reference to preferred embodiment having described the present invention, those skilled in the art know, can not deviate from the replacement that is equal to of the various variations of the open scope of the present invention and various key elements.In addition, many modification that can not deviate from base region of the present invention according to instruction of the present invention adapt to specific situation or material.Therefore, the present invention does not want to be limited on the embodiment that disclosed the present invention explores optimal mode, but the present invention will comprise falling all embodiments within the scope of the appended claims.
The patent of all references, patent application and other reference papers are all introduced as a reference at this.
Claims (8)
1. a curable compositions comprises
Functionalized poly-(arylene ether);
The ethylene linkage unsaturated monomer; And
Be selected from the Nano filling of polynite, nontronite, beidellite, volkonskoite, hectorite, saponite, sauconite, magadiite and fibrous morphology crystals,
Wherein said functionalized poly-(arylene ether) is selected from end-blocking poly-(arylene ether) or encircles functionalized poly-(arylene ether), and wherein this end-blocking poly-(arylene ether) has following array structure:
Q(J-K)
y
Wherein, Q is the residue of monohydroxy, dihydroxyl or polyhydroxy phenol; Y is 1～100; J comprises the repeated structural unit with following formula:
Wherein, R
2And R
4Be selected from halogen, C independently of one another
1～C
12Uncle or secondary alkyl, C
2～C
12Alkenyl, C
2～C
12Alkynyl, C
1～C
12Aminoalkyl group, C
1～C
12Hydroxyalkyl, phenyl, C
1～C
12Haloalkyl, C
1～C
12-oxyl, and the C of at least two carbon atoms separate halogen atoms and Sauerstoffatom wherein
2～C
12The halo-oxyl; R
1And R
3Be selected from hydrogen, halogen, C independently of one another
1～C
12Uncle or secondary alkyl, C
2～C
12Alkenyl, C
2～C
12Alkynyl, C
1～C
12Aminoalkyl group, C
1～C
12Hydroxyalkyl, phenyl, C
1～C
12Haloalkyl, C
1～C
12-oxyl, and the C of at least two carbon atoms separate halogen atoms and Sauerstoffatom wherein
2～C
12The halo-oxyl; M is 1～200; And K is selected from following capping group:
Wherein, R
5Be C
1～C
12Alkyl; R
6～R
8Be selected from hydrogen, C independently of one another
1～C
12Alkyl, C
2～C
12Alkenyl, C
6～C
18Aryl, C
7～C
18Alkyl substituting aromatic base, C
7～C
18Aryl substituted alkyl, C
2～C
12Alkoxy carbonyl, C
7～C
18Aryloxycarbonyl, C
8～C
18Aryloxycarbonyl, C that alkyl replaces
8～C
18Alkoxy carbonyl, nitrile, formyl radical, carboxylicesters, imido-ester, carbothioic acid ester that aryl replaces; R
9～R
13Be selected from hydrogen, halogen, C independently of one another
1～C
12Alkyl, hydroxyl and amino; And wherein Y is selected from following divalent group:
R wherein
14And R
15Be selected from hydrogen, C independently of one another
1～C
12Alkyl,
And wherein encircle functionalized poly-(arylene ether) for comprising poly-(arylene ether) of following repeated structural unit:
Wherein, L
1～L
4Represent hydrogen atom, kiki alkenyl group or alkynyl group independently of one another; Wherein kiki alkenyl group is expressed as follows:
Wherein, L
5～L
7Represent hydrogen or methyl independently, a is 1～4 integer, and wherein alkynyl group is expressed as follows:
Wherein, L
8Be hydrogen, methyl or ethyl, b is 1～4 integer; And, wherein encircling the functionalized whole L in (arylene ether) that gather
1～L
4Substituent 0.02mol%～25mol% is alkenyl and/or alkynyl group.
2. the composition of claim 1, wherein Q is the residue of monohydroxy phenol.
3. the composition of above-mentioned arbitrary claim comprises the functionalized poly (arylene ether) and the ethylene linkage unsaturated monomer gross weight of functionalized poly-(arylene ether)/per 100 weight parts of 1～90 weight part.
4. claim 1 or 2 composition, wherein the ethylene linkage unsaturated monomer comprises alkenyl fragrant monomer, acryl monomer, allyl monomer or their mixture.
5. claim 1 or 2 composition comprise the functionalized poly (arylene ether) and the ethylene linkage unsaturated monomer gross weight of ethylene linkage unsaturated monomer/per 100 weight parts of 10～99 weight parts.
6. claim 1 or 2 composition comprise the Nano filling of 0.5～80 weight %, based on the gross weight of said composition.
7. claim 1 or 2 composition also comprise the polymeric additive that second-order transition temperature is less than or equal to 100 ℃.
8. curing composition that forms by the composition that solidifies above-mentioned arbitrary claim.
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| US31980502P | 2002-12-20 | 2002-12-20 | |
| US60/319,805 | 2002-12-20 | ||
| US60/319,872 | 2003-01-16 |
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| JP4176793B2 (en) * | 2006-09-07 | 2008-11-05 | 日本バルカー工業株式会社 | Fluororesin composition for radome, radome and method for producing radome |
| WO2016019568A1 (en) * | 2014-08-08 | 2016-02-11 | Honeywell International Inc. | 3d organic-inorganic hybridized compositions and methods |
| CN109957228A (en) * | 2017-12-26 | 2019-07-02 | 深圳光启尖端技术有限责任公司 | A kind of antenna house substrate and preparation method thereof |
| CA3042547A1 (en) | 2018-05-11 | 2019-11-11 | Campagnolo S.R.L. | Bicycle crankarm provided with electric/electronic system |
| IT201800005294A1 (en) | 2018-05-11 | 2019-11-11 | COMPONENT OF BICYCLE IN COMPOSITE MATERIAL AND RELATED MANUFACTURING PROCESS | |
| IT201800005299A1 (en) | 2018-05-11 | 2019-11-11 | BICYCLE COMPONENT EQUIPPED WITH STRESS / DEFORMATION SENSOR COMPENSATED FOR TEMPERATURE |
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| WO2002057365A1 (en) * | 2001-01-18 | 2002-07-25 | General Electric Company | Electrically conductive thermoset composition, method for the preparation thereof, and articles derived therefrom |
| WO2002077103A1 (en) * | 2001-03-27 | 2002-10-03 | General Electric Company | Poly(arylene ether)-containing thermoset composition in powder form, method for the preparation thereof, and articles derived therefrom |
| US20020169256A1 (en) * | 1999-12-01 | 2002-11-14 | Merfeld Glen David | Thermoset composition, method, and article |
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|---|---|---|---|---|
| US20010053820A1 (en) * | 1999-12-01 | 2001-12-20 | Yeager Gary William | Poly(arylene ether)-containing thermoset composition, method for the preparation thereof, and articles derived therefrom |
| US20020169256A1 (en) * | 1999-12-01 | 2002-11-14 | Merfeld Glen David | Thermoset composition, method, and article |
| WO2002057365A1 (en) * | 2001-01-18 | 2002-07-25 | General Electric Company | Electrically conductive thermoset composition, method for the preparation thereof, and articles derived therefrom |
| WO2002077103A1 (en) * | 2001-03-27 | 2002-10-03 | General Electric Company | Poly(arylene ether)-containing thermoset composition in powder form, method for the preparation thereof, and articles derived therefrom |
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