CN102702680A

CN102702680A - Poly(arylene ether) composition, method, and article

Info

Publication number: CN102702680A
Application number: CN2012101828138A
Authority: CN
Inventors: 埃里克.R.德尔斯曼; 郭桦; 爱德华.N.彼得斯
Original assignee: SABIC Innovative Plastics IP BV
Current assignee: SABIC Global Technologies BV
Priority date: 2006-09-15
Filing date: 2007-07-26
Publication date: 2012-10-03
Also published as: WO2008033611A1; EP2061836A1; JP2010503753A; TWI422644B; TW200821355A; JP5599612B2

Abstract

A curable composition includes an epoxy resin and a bifunctional poly(arylene ether) having an intrinsic viscosity of about 0.03 to about 0.2 deciliter per gram. After curing, the composition exhibits markedly improved impact strength relative to a corresponding composition prepared from mono functional poly (arylene ether). The composition is particularly useful for preparing electronic laminates, prepregs, and circuit boards.

Description

Solidified gathers (arylene ether) compsn, method, and goods

It is on July 26th, 2007 that the application is based on the applying date; Priority date is on September 15th, 2006, and application number is 200780034378.1 (PCT/US2007/074432), and denomination of invention is: the dividing an application of the patented claim of " solidified gathers (arylene ether) compsn; method, and goods ".

Background technology

Epoxy resin is high performance material, is used for wide in range application, comprises protective coating; Tackiness agent, electronics laminate (those that for example in the manufacturing of computingmachine printed substrate, use), floor and pavement applications; Spun glass enhanced pipe; And trolley part (comprising laminated spring, pump, and electronic package).In their cured form, epoxy resin provides the character of expectation, comprises good and clinging power other material, to good patience, high tensile and the good resistance of corrosion and chemical.With fragility that to use two relevant challenges of epoxy resin are cured epoxy resins with need the many curable epoxy compsns of heating, be enough to preparation and blend they and their are shaped, still again deficiency so that their premature settings.

About the fragility problem of epoxy resin, known will gather (arylene ether) adds in the epoxy resin and can increase the toughness through curing compsn.For example; The USP 4,912,172 that licenses to Hallgren etc. has been described a kind of compsn; It comprises that number-average molecular weight is at least about 12; The epoxy material of 000 ppe and at least a poly epihydric alcohol base ether that is selected from bisphenol cpd and the said poly epihydric alcohol base ether of main amount and the combination of a spot of at least a aryl list glycidyl ether and non-bis-phenol polyepoxides, said each molecule of poly epihydric alcohol base ether on average has aliphatic hydroxyl at the most.But, need higher temperature to form the uniform mixture of ppe and epoxy resin.

As another instance, the USP 5,834,565 that licenses to Tracy etc. has been described a kind of compsn, and it comprises ppe and the thermosetting resin of number-average molecular weight less than every mole of 3,000 gram, and said thermosetting resin can be epoxy resin.Ppe demonstrates the solvability of the improvement in curable compositions.But, make toughness that these compsns solidify the product that obtains not use those toughness of higher molecular weight ppe preparation high.

Also as another instance, license to the USP 7,022 of Davis etc., 777B2 has described a kind of compsn, and it comprises and gathers (arylene ether), thermosetting resin, toughner, and amine hardener.But, as if need high temperature to make the ppe dissolving.Therefore, in embodiment 1 and 2, prepared curable compositions, part is to prepare through gathering at 160 ° of C in the blend that (arylene ether) add epoxy resin and polyvinyl butyral to.

As if the therefore known curable compositions that gathers (arylene ether) and epoxy resin that comprises exist the balance between the toughness of easy property and cured product of preparation.When using high-molecular weight to gather (arylene ether), solidified product toughness is very high, but needs high temperature to be dissolved in the epoxy resin gathering (arylene ether).On the other hand, when using low-molecular-weight gathering (arylene ether), can will gather (arylene ether) at low temperature and be dissolved in the epoxy resin, increase less but in the solidified product, observe toughness.

Still needing can be in machining at low temperature, and after solidifying the curable epoxy compsn of toughness high (non-friable).

Summary of the invention

Above-mentioned and other shortcoming has obtained alleviation through a kind of curable compositions, and said curable compositions comprises: epoxy resin; Limiting viscosity is about 0.03 to gather (arylene ether) to the difunctionality of about 0.2 deciliter of every gram, in 25 ℃ chloroform, measures; And curing catalyst, its content makes epoxy resin cure effectively; The unnotched Izod impact strength ratio that wherein said compsn demonstrates after solidifying has the unnotched Izod impact strength greatly at least 5% that simple function gathers the correspondent composition of (arylene ether), and wherein unnotched Izod impact strength records according to ASTM D4812 standard at 25 ℃.

Another embodiment is a kind of curable compositions, is made up of following material: epoxy resin; Limiting viscosity is about 0.03 to gather (arylene ether) to the difunctionality of about 0.2 deciliter of every gram, in 25 ℃ chloroform, measures; Curing catalyst, its content makes epoxy resin cure effectively; Choose wantonly, about filler of 2 to about 50wt% is based on the gross weight of compsn; With optional, be selected from following additive: dyestuff, pigment, tinting material, inhibitor, thermo-stabilizer; Photostabilizer, softening agent, lubricant, flow ability modifying agent, dripping inhibitor, fire retardant; Anti, antistatic agent, flow improver additive, processing aid, base plate bonding agent; Releasing agent, toughner, low shrinkage additive, stress relieving additive, and combination; The unnotched Izod impact strength ratio that wherein said compsn demonstrates after solidifying has the unnotched Izod impact strength greatly at least 5% that simple function gathers the correspondent composition of (arylene ether), and wherein unnotched Izod impact strength records according to ASTM D4812 standard at 25 ℃.

Another embodiment is a kind of curable compositions, comprising: dihydroxyphenyl propane diglycidyl ether epoxy resin; Limiting viscosity is about 0.03 to gather (arylene ether) to the difunctionality of about 0.2 deciliter of every gram, in 25 ℃ chloroform, measures, and wherein said gathering (arylene ether) has following structure:

Be 1 to about 20 independently when wherein x occurs at every turn; And curing catalyst, its content makes epoxy resin cure effectively; The unnotched Izod impact strength ratio that wherein said compsn demonstrates after solidifying has the unnotched Izod impact strength big 5 of correspondent composition that simple function gathers (arylene ether) to about 50%, and wherein unnotched Izod impact strength records according to ASTM D4812 standard at 25 ℃.

Another embodiment is a kind of curable compositions, is made up of following material: dihydroxyphenyl propane diglycidyl ether epoxy resin; Limiting viscosity is about 0.03 to gather (arylene ether) to the difunctionality of about 0.2 deciliter of every gram, in 25 ℃ chloroform, measures, and wherein said gathering (arylene ether) has following structure:

Be 1 to about 20 independently when wherein x occurs at every turn; Curing catalyst, its content makes epoxy resin cure effectively; Choose wantonly, about filler of 2 to about 50wt% is based on the gross weight of compsn; With optional, be selected from following additive: dyestuff, pigment, tinting material, inhibitor, thermo-stabilizer; Photostabilizer, softening agent, lubricant, flow ability modifying agent, dripping inhibitor, fire retardant; Anti, antistatic agent, flow improver additive, processing aid, base plate bonding agent; Releasing agent, toughner, low shrinkage additive, stress relieving additive, and combination; The unnotched Izod impact strength ratio that wherein said compsn demonstrates after solidifying has the unnotched Izod impact strength big 5 of correspondent composition that simple function gathers (arylene ether) to about 50%, and wherein unnotched Izod impact strength records according to ASTM D4812 standard at 25 ℃.

Another embodiment is a kind of curable compositions, comprising: the about 60 dihydroxyphenyl propane diglycidyl ether epoxy resin to about 90 weight parts; About 10 limiting viscosities to about 40 weight parts are about 0.06 to gather (arylene ether) to the difunctionality of about 0.12 deciliter of every gram, in 25 ℃ chloroform, measure, and wherein said gathering (arylene ether) has following structure:

Be 1 to about 20 independently when wherein x occurs at every turn; With about 0.5 aluminium acetylacetonate (III) to about 10 weight parts; Wherein all weight parts are all based on 100 parts by weight of epoxy resin and difunctionality are gathered (arylene ether) altogether; Wherein said dihydroxyphenyl propane diglycidyl ether epoxy resin gather with difunctionality (arylene ether) when 25 to 65 ° of C, be present in single mutually in; Wherein said curable compositions is less than or equal to 10,000 centipoises in the viscosity of 25 ° of C; The unnotched Izod impact strength ratio that wherein said compsn demonstrates after solidifying has the unnotched Izod impact strength big 5 of correspondent composition that simple function gathers (arylene ether) to about 50%, and wherein unnotched Izod impact strength records according to ASTM D4812 standard at 25 ℃; The notched izod impact strength ratio that after solidifying, demonstrates with wherein said compsn has the notched izod impact strength big 5 of correspondent composition that simple function gathers (arylene ether) to about 30%, and wherein notched izod impact strength records according to ASTM D256 standard at 25 ℃.

Another embodiment is a kind of curable compositions, is made up of following material: the about 60 dihydroxyphenyl propane diglycidyl ether epoxy resin to about 90 weight parts; About 10 limiting viscosities to about 40 weight parts are about 0.06 to gather (arylene ether) to the difunctionality of about 0.12 deciliter of every gram, in 25 ℃ chloroform, measure, and wherein said gathering (arylene ether) has following structure:

Be 1 to about 20 independently when wherein x occurs at every turn; With about 0.5 aluminium acetylacetonate (III) to about 10 weight parts; Choose about 20 fillers wantonly to about 100 weight parts; With optional, be selected from following additive: dyestuff, pigment, tinting material, inhibitor, thermo-stabilizer; Photostabilizer, softening agent, lubricant, flow ability modifying agent, dripping inhibitor, fire retardant; Anti, antistatic agent, flow improver additive, processing aid, base plate bonding agent; Releasing agent, toughner, low shrinkage additive, stress relieving additive, and combination; Wherein said dihydroxyphenyl propane diglycidyl ether epoxy resin gather with difunctionality (arylene ether) when 25 to 65 ° of C, be present in single mutually in; Wherein all weight parts are all based on 100 parts by weight of epoxy resin and difunctionality are gathered (arylene ether) altogether; The unnotched Izod impact strength ratio that wherein said compsn demonstrates after solidifying has the unnotched Izod impact strength big 5 of correspondent composition that simple function gathers (arylene ether) to about 50%, and wherein unnotched Izod impact strength records according to the ASTMD4812 standard at 25 ℃; The notched izod impact strength ratio that after solidifying, demonstrates with wherein said compsn has the notched izod impact strength big 5 of correspondent composition that simple function gathers (arylene ether) to about 30%, and wherein notched izod impact strength records according to ASTM D256 standard at 25 ℃.

Another embodiment is a kind of curable compositions, comprising: the about 60 dihydroxyphenyl propane diglycidyl ether epoxy resin to about 90 weight parts; About 10 limiting viscosities to about 40 weight parts are that the difunctionality of about 0.06 deciliter of every gram is gathered (arylene ether), in 25 ℃ chloroform, measure, and wherein said gathering (arylene ether) has following structure:

Be 1 to about 20 independently when wherein x occurs at every turn; With about 0.5 aluminium acetylacetonate (III) to about 10 weight parts; Wherein said dihydroxyphenyl propane diglycidyl ether epoxy resin gather with difunctionality (arylene ether) when 25 to 65 ° of C, be present in single mutually in; Wherein all weight parts are based on 100 parts by weight of epoxy resin and difunctionality are gathered (arylene ether) altogether; The unnotched Izod impact strength ratio that wherein said compsn demonstrates after solidifying has the unnotched Izod impact strength big 5 of correspondent composition that simple function gathers (arylene ether) to about 50%, and wherein unnotched Izod impact strength records according to ASTM D4812 standard at 25 ℃; The notched izod impact strength ratio that after solidifying, demonstrates with wherein said compsn has the notched izod impact strength big 5 of correspondent composition that simple function gathers (arylene ether) to about 30%, and wherein notched izod impact strength records according to ASTM D256 standard at 25 ℃.

Another embodiment is a kind of curable compositions, comprising: the about 60 dihydroxyphenyl propane diglycidyl ether epoxy resin to about 90 weight parts; About 10 limiting viscosities to about 40 weight parts are that the difunctionality of about 0.09 deciliter of every gram is gathered (arylene ether), in 25 ℃ chloroform, measure, and wherein said gathering (arylene ether) has following structure:

Be 1 to about 20 independently when wherein x occurs at every turn; With about 0.5 aluminium acetylacetonate (III) to about 10 weight parts; Wherein said dihydroxyphenyl propane diglycidyl ether epoxy resin gather with difunctionality (arylene ether) when 25 to 65 ° of C, be present in single mutually in; Wherein all weight parts are all based on 100 parts by weight of epoxy resin and difunctionality are gathered (arylene ether) altogether; The unnotched Izod impact strength ratio that wherein said compsn demonstrates after solidifying has the unnotched Izod impact strength big 5 of correspondent composition that simple function gathers (arylene ether) to about 50%, and wherein unnotched Izod impact strength records according to ASTM D4812 standard at 25 ℃; The notched izod impact strength ratio that after solidifying, demonstrates with wherein said compsn has the notched izod impact strength big 5 of correspondent composition that simple function gathers (arylene ether) to about 30%, and wherein notched izod impact strength records according to ASTM D256 standard at 25 ℃.

Another embodiment is a kind of curable compositions, comprising: the about 60 dihydroxyphenyl propane diglycidyl ether epoxy resin to about 90 weight parts; About 10 limiting viscosities to about 40 weight parts are that the difunctionality of about 0.12 deciliter of every gram is gathered (arylene ether), in 25 ℃ chloroform, measure, and wherein said gathering (arylene ether) has following structure:

Another embodiment is a kind of method for preparing curable compositions; Comprise: blend epoxy resin; Limiting viscosity is about 0.03 to gather (arylene ether) to the difunctionality of about 0.2 deciliter of every gram when in 25 ℃ chloroform, measuring, and curing catalyst, and its content makes epoxy resin cure effectively; The unnotched Izod impact strength ratio that wherein said compsn demonstrates after solidifying has the unnotched Izod impact strength greatly at least 5% that simple function gathers the correspondent composition of (arylene ether), and wherein unnotched Izod impact strength records according to ASTM D4812 standard at 25 ℃.

The present invention includes following content:

1. 1 kinds of curable compositions of embodiment, said curable compositions comprises:

Epoxy resin;

Limiting viscosity is about 0.03 to gather (arylene ether) to the difunctionality of about 0.2 deciliter of every gram, in 25 ℃ chloroform, measures; With

Curing catalyst, its content makes epoxy resin cure effectively;

The unnotched Izod impact strength ratio that wherein said compsn demonstrates after solidifying has the unnotched Izod impact strength greatly at least 5% that simple function gathers the correspondent composition of (arylene ether), and wherein unnotched Izod impact strength records according to ASTM D4812 standard at 25 ℃.

The curable compositions of embodiment 2. embodiments 1, the unnotched Izod impact strength ratio that wherein said compsn demonstrates after solidifying has the unnotched Izod impact strength big 5 to about 50% that simple function gathers the correspondent composition of (arylene ether).

The curable compositions of embodiment 3. embodiments 1; The notched izod impact strength ratio that wherein said compsn demonstrates after solidifying has the notched izod impact strength greatly at least 5% that simple function gathers the correspondent composition of (arylene ether), and wherein notched izod impact strength records according to the ASTMD256 standard at 25 ℃.

The curable compositions of embodiment 4. embodiments 3, the notched izod impact strength ratio that wherein said compsn demonstrates after solidifying has the notched izod impact strength big 5 to about 30% that simple function gathers the correspondent composition of (arylene ether).

The curable compositions of embodiment 5. embodiments 1, the softening temperature of wherein said epoxy resin are that about 25 ° of C are to about 150 ° of C.

The curable compositions of embodiment 6. embodiments 1, the softening temperature of wherein said epoxy resin is less than 25 ° of C.

The curable compositions of embodiment 7. embodiments 1, wherein said epoxy resin is selected from aliphatic epoxy resin, cycloaliphatic epoxy resin, bisphenol A epoxide resin; Bisphenol F epoxy resin, phenol phenolic resin varnish, cresols-phenolic resin varnish, biphenyl epoxy resin; Polyfunctional epoxy resin, naphthalene epoxy resins, divinylbenzene dioxide, 2-glycidyl phenylglycidyl ether; Dicyclopentadiene (DCPD)-type epoxy resin, many aromatic resins type epoxy resin, and combination.

The curable compositions of embodiment 8. embodiments 1, wherein said epoxy resin comprises cyclosiloxane monomer epoxy resins and oligomeric epoxy resins.

The curable compositions of embodiment 9. embodiments 1, wherein said epoxy resin comprise dihydroxyphenyl propane diglycidyl ether epoxy resin.

The curable compositions of embodiment 10. embodiments 1, wherein said difunctionality gather (arylene ether) and have following structure:

Q wherein ¹And Q ²Be hydrogen, halogen, unsubstituted or substituted C when occurring independently at every turn ₁-C ₁₂The alkyl condition is that said alkyl is not the tertiary hydrocarbon base, C ₁-C ₁₂The alkyl sulfenyl, C ₁-C ₁₂Alkyl oxygen base, perhaps wherein at least two carbon atoms separate the C of halogen and Sauerstoffatom ₂-C ₁₂Halo alkyl oxygen base; Be 1 to about 100 independently when x occurs at every turn; Have following structure with L:

R wherein ¹And R ²Be hydrogen, halogen, unsubstituted or substituted C when occurring independently at every turn ₁-C ₁₂Alkyl, condition are that said alkyl is not tertiary hydrocarbon base, C ₁-C ₁₂The alkyl sulfenyl, C ₁-C ₁₂Alkyl oxygen base, or wherein at least two carbon atoms separate the C of halogen and Sauerstoffatom ₂-C ₁₂Halo alkyl oxygen base; Z is 0 or 1; Have with Y and to be selected from following structure:

R wherein ³Be independently selected from hydrogen and C when occurring at every turn ₁-C ₁₂Alkyl, R ⁴And R ⁵Be independently selected from hydrogen when occurring, C at every turn ₁-C ₁₂Alkyl, and C ₁-C ₆Alkylene is at C ₁-C ₆R during alkylene ⁴And R ⁵Form C together ₄-C ₁₂Alkylidene group.

The curable compositions of embodiment 11. embodiments 1, wherein said difunctionality gather (arylene ether) and have following structure:

Q wherein ¹And Q ²Be hydrogen, halogen, unsubstituted or substituted C when occurring independently at every turn ₁-C ₁₂The alkyl condition is that said alkyl is not tertiary hydrocarbon base, C ₁-C ₁₂The alkyl sulfenyl, C ₁-C ₁₂Alkyl oxygen base, or wherein at least two carbon atoms separate the C of halogen and Sauerstoffatom ₂-C ₁₂Halo alkyl oxygen base; Be 1 to about 100 independently when x occurs at every turn; Have following structure with A:

R wherein ⁶And R ⁷And R ⁸And R ⁹Be hydrogen, C when occurring independently at every turn ₁-C ₁₂Alkyl or C ₁-C ₁₂The halo alkyl; Be 0,1,2,3,4,5 or 6 independently when wherein m occurs at every turn; And Y wherein ¹And Y ²And Y ³And Y ⁴Be hydrogen, C when occurring independently at every turn ₁-C ₁₂Alkyl, C ₁-C ₁₂Alkyl oxygen base, or halogen; And wherein n is 5 to about 200.

The curable compositions of embodiment 12. embodiments 11, wherein Q ¹When occurring methyl, wherein Q at every turn ²When occurring hydrogen or methyl, wherein Y at every turn ¹When occurring methoxyl group, wherein Y at every turn ², Y ³And Y ⁴When occurring hydrogen, wherein R at every turn ⁶And R ⁷And R ⁸And R ⁹Be methyl when occurring, be 3 when wherein m occurs at every turn at every turn, and wherein n is about 10 to about 100.

The curable compositions of embodiment 13. embodiments 1, wherein said difunctionality gather (arylene ether) and have following structure:

Q wherein ¹Be methyl; Q ²Be hydrogen or methyl when occurring independently at every turn; R ¹And R ²Be hydrogen, halogen, unsubstituted or substituted C when occurring independently at every turn ₁-C ₁₂The alkyl condition is that said alkyl is not tertiary hydrocarbon base, C ₁-C ₁₂The alkyl sulfenyl, C ₁-C ₁₂Alkyl oxygen base, or wherein at least two carbon atoms separate the C of halogen and Sauerstoffatom ₂-C ₁₂Halo alkyl oxygen base; R ⁴And R ⁵Be selected from hydrogen independently of one another, C ₁-C ₆Alkyl, and C ₁-C ₆Alkylene is at C ₁-C ₆R during alkylene ⁴And R ⁵Form C together ₄-C ₁₂Alkylidene group; Be 1 to about 50 independently when occurring with x at every turn.

The curable compositions of embodiment 14. embodiments 1, wherein said difunctionality gather (arylene ether) and have following structure:

Be 1 to about 20 independently when wherein x occurs at every turn.

The curable compositions of embodiment 15. embodiments 1, wherein said difunctionality gather the product that (arylene ether) is the oxidisability copolymerization of monohydric phenol and dihydric phenol.

The curable compositions of embodiment 16. embodiments 12, wherein said monohydric phenol is selected from 2,6-xylenol, 2,3, the 6-pseudocuminol, and composition thereof; And wherein said dihydric phenol is selected from 3,3 ', 5, and 5 '-tetramethyl--4; 4 '-xenol, 2, two (3-methyl-4-hydroxy phenyl) propane, 2 of 2-, two (3, the 5-dimethyl--4-hydroxy phenyl) propane, 1 of 2-; Two (4-hydroxy phenyl) methane, 1 of 1-, two (4-hydroxy phenyl) ethane, 2 of 1-, two (4-hydroxy phenyl) propane, 2 of 2-, two (4-hydroxy phenyl) butane, 2 of 2-; Two (4-hydroxy phenyl) octanes, 1 of 2-, two (4-hydroxy phenyl) propane, 1 of 1-, two (4-the hydroxy phenyl)-normal butanes of 1-, two (4-hydroxy phenyl) phenylmethane, 1, two (the 4-hydroxy-3-methyl phenyl) hexanaphthenes, 1 of 1-; Two (4-hydroxyl-3, the 5-3,5-dimethylphenyl) pentamethylene, 1 of 1-, two (4-hydroxyl-3, the 5-3,5-dimethylphenyl) hexanaphthenes, 1 of 1-; Two (the 4-hydroxy-3-methyl phenyl) suberane, 1 of 1-, two (4-hydroxyl-3, the 5-3,5-dimethylphenyl) suberane, 1 of 1-, two (the 4-hydroxy-3-methyl phenyl) cyclooctane, 1 of 1-; Two (4-hydroxyl-3, the 5-3,5-dimethylphenyl) cyclooctane, 1 of 1-, two (the 4-hydroxy-3-methyl phenyl) cyclononane, 11 of 1-, two (the 4-hydroxyls-3 of 1-; The 5-3,5-dimethylphenyl) cyclononane, 1, two (the 4-hydroxy-3-methyl phenyl) cyclodecane, 1 of 1-, two (4-hydroxyl-3, the 5-3,5-dimethylphenyl) cyclodecane, 1 of 1-; 1-two (4-hydroxy-3-methyl phenyl) ring undecane, 1,1-two (4-hydroxyl-3,5-3,5-dimethylphenyl) ring undecane, 1, two (the 4-hydroxy-3-methyl phenyl) cyclododecanes, 1 of 1-; Two (4-hydroxyl-3, the 5-3,5-dimethylphenyl) cyclododecanes, 1 of 1-, two (4-hydroxyl-3-tert-butyl-phenyl) propane, 2 of 1-; Two (4-hydroxyl-2, the 6-3,5-dimethylphenyl) propane, 2 of 2-, two (4-hydroxyl-3-bromophenyl) propane, 1 of 2-; Two (4-hydroxy phenyl) pentamethylene, 1 of 1-, the 1-bis(4-hydroxyphenyl) cyclohexane, and composition thereof.

The curable compositions of embodiment 17. embodiments 12, wherein said monohydric phenol are 2, the 6-xylenol, and wherein said dihydric phenol is 2, two (3, the 5-dimethyl--4-hydroxy phenyl) propane of 2-.

The curable compositions of embodiment 18. embodiments 12, wherein said monohydric phenol are 2, the 6-xylenol; And wherein said dihydric phenol is selected from 2; Two (3-methyl-4-hydroxy phenyl) propane, 1 of 2-, two (the 4-hydroxy-3-methyl phenyl) hexanaphthenes, 1 of 1-, two (the 4-hydroxyls-3 of 1-; The 5-3,5-dimethylphenyl) hexanaphthene, and composition thereof.

The curable compositions of embodiment 19. embodiments 1; Comprise that about 30 gather (arylene ether) to about 99 parts by weight of epoxy resin and about 1 to the difunctionality of about 70 weight parts, wherein all weight parts are all based on 100 parts by weight of epoxy resin and difunctionality are gathered (arylene ether) altogether.

The curable compositions of embodiment 20. embodiments 1; Comprise that about 60 gather (arylene ether) to about 90 parts by weight of epoxy resin and about 10 to the difunctionality of about 40 weight parts, wherein all weight parts are all based on 100 parts by weight of epoxy resin and difunctionality are gathered (arylene ether) altogether.

The curable compositions of embodiment 21. embodiments 1, wherein said curing catalyst are selected from potential cationic curing catalyzer, phenolic hardeners; Amine hardener, aliphatics or aromatic carboxylic acid's copper (II) salt, aliphatics or aromatic carboxylic acid's aluminium (III) salt; Beta-diketon acid copper (II), beta-diketon acid aluminium (III), alicyclic carboxylic acid acid anhydride; Boron trifluoride-Trimethylamine complex compound, and combination.

The curable compositions of embodiment 22. embodiments 1, wherein said curing catalyst are to be selected from following potential cationic curing catalyzer: diaryl group iodized salt, phosphonic acid ester; Sulphonate, carboxylicesters, phosphonium ylide; The benzyl sulfonium salt, benzyl-pyridine salt, benzyl ammonium salt; isoxazolium salt, boron trifluoride-Trimethylamine complex compound, and combination.

The curable compositions of embodiment 23. embodiments 1, wherein said curing catalyst comprise aluminium acetylacetonate (III).

The curable compositions of embodiment 24. embodiments 1 also comprises about filler of 2 to about 50wt%, based on the gross weight of compsn.

The curable compositions of embodiment 25. embodiments 1, wherein said compsn does not contain inorganic particulate filler.

The curable compositions of embodiment 26. embodiments 1 also comprises being selected from following additive: dyestuff, pigment, tinting material, inhibitor, thermo-stabilizer; Photostabilizer, softening agent, lubricant, flow ability modifying agent, dripping inhibitor, fire retardant; Anti, antistatic agent, flow improver additive, processing aid, base plate bonding agent; Releasing agent, toughner, low shrinkage additive, stress relieving additive, and combination.

27. 1 kinds of curable compositions of embodiment, form by following material:

Epoxy resin;

Limiting viscosity is about 0.03 to gather (arylene ether) to the difunctionality of about 0.2 deciliter of every gram, in 25 ℃ chloroform, measures;

Curing catalyst, its content makes epoxy resin cure effectively;

Choose wantonly, about filler of 2 to about 50wt% is based on the gross weight of compsn; With

Choose wantonly, be selected from following additive: dyestuff, pigment, tinting material, inhibitor, thermo-stabilizer; Photostabilizer, softening agent, lubricant, flow ability modifying agent, dripping inhibitor, fire retardant; Anti, antistatic agent, flow improver additive, processing aid, base plate bonding agent; Releasing agent, toughner, low shrinkage additive, stress relieving additive, and combination;

28. 1 kinds of curable compositions of embodiment comprise:

Dihydroxyphenyl propane diglycidyl ether epoxy resin;

Limiting viscosity is about 0.03 to gather (arylene ether) to the difunctionality of about 0.2 deciliter of every gram, in 25 ℃ chloroform, measures, and wherein said gathering (arylene ether) has following structure:

Be 1 to about 20 independently when wherein x occurs at every turn; With

Curing catalyst, its content makes epoxy resin cure effectively;

The unnotched Izod impact strength ratio that wherein said compsn demonstrates after solidifying has the unnotched Izod impact strength big 5 of correspondent composition that simple function gathers (arylene ether) to about 50%, and wherein unnotched Izod impact strength records according to ASTM D4812 standard at 25 ℃.

29. 1 kinds of curable compositions of embodiment, form by following material:

Dihydroxyphenyl propane diglycidyl ether epoxy resin;

Be 1 to about 20 independently when wherein x occurs at every turn;

Curing catalyst, its content makes epoxy resin cure effectively;

30. 1 kinds of curable compositions of embodiment comprise:

About 60 dihydroxyphenyl propane diglycidyl ether epoxy resin to about 90 weight parts;

About 10 limiting viscosities to about 40 weight parts are about 0.06 to gather (arylene ether) to the difunctionality of about 0.12 deciliter of every gram, in 25 ℃ chloroform, measure, and wherein said gathering (arylene ether) has following structure:

Be 1 to about 20 independently when wherein x occurs at every turn; With

About 0.5 aluminium acetylacetonate (III) to about 10 weight parts;

Wherein all weight parts are all based on 100 parts by weight of epoxy resin and difunctionality are gathered (arylene ether) altogether;

Wherein said dihydroxyphenyl propane diglycidyl ether epoxy resin gather with difunctionality (arylene ether) when 25 to 65 ° of C, be present in single mutually in;

Wherein said curable compositions is less than or equal to 10,000 centipoises in the viscosity of 25 ° of C;

The unnotched Izod impact strength ratio that wherein said compsn demonstrates after solidifying has the unnotched Izod impact strength big 5 of correspondent composition that simple function gathers (arylene ether) to about 50%, and wherein unnotched Izod impact strength records according to ASTM D4812 standard at 25 ℃; With

The notched izod impact strength ratio that wherein said compsn demonstrates after solidifying has the notched izod impact strength big 5 of correspondent composition that simple function gathers (arylene ether) to about 30%, and wherein notched izod impact strength records according to ASTM D256 standard at 25 ℃.

31. 1 kinds of curable compositions of embodiment, form by following material:

Be 1 to about 20 independently when wherein x occurs at every turn; With

About 0.5 aluminium acetylacetonate (III) to about 10 weight parts;

Choose about 20 fillers wantonly to about 100 weight parts; With

Choose wantonly; Be selected from following additive: dyestuff, pigment, tinting material, inhibitor, thermo-stabilizer, photostabilizer, softening agent, lubricant, flow ability modifying agent, dripping inhibitor, fire retardant, anti, antistatic agent, flow improver additive, processing aid, base plate bonding agent, releasing agent, toughner, low shrinkage additive, stress relieving additive, and combination;

32. 1 kinds of curable compositions of embodiment comprise:

About 10 limiting viscosities to about 40 weight parts are that the difunctionality of about 0.06 deciliter of every gram is gathered (arylene ether), in 25 ℃ chloroform, measure, and wherein said gathering (arylene ether) has following structure:

Be 1 to about 20 independently when wherein x occurs at every turn; With

About 0.5 aluminium acetylacetonate (III) to about 10 weight parts;

Wherein all weight parts are based on 100 parts by weight of epoxy resin and difunctionality are gathered (arylene ether) altogether;

33. 1 kinds of curable compositions of embodiment comprise:

About 10 limiting viscosities to about 40 weight parts are that the difunctionality of about 0.09 deciliter of every gram is gathered (arylene ether), in 25 ℃ chloroform, measure, and wherein said gathering (arylene ether) has following structure:

Be 1 to about 20 independently when wherein x occurs at every turn; With

About 0.5 aluminium acetylacetonate (III) to about 10 weight parts;

Wherein dihydroxyphenyl propane diglycidyl ether epoxy resin gather with difunctionality (arylene ether) when 25 to 65 ° of C, be present in single mutually in;

34. 1 kinds of curable compositions of embodiment comprise:

About 10 limiting viscosities to about 40 weight parts are that the difunctionality of about 0.12 deciliter of every gram is gathered (arylene ether), in 25 ℃ chloroform, measure, and wherein said gathering (arylene ether) has following structure:

Be 1 to about 20 independently when wherein x occurs at every turn; With

About 0.5 aluminium acetylacetonate (III) to about 10 weight parts;

35. 1 kinds of methods that prepare curable compositions of embodiment comprise:

Blend

Epoxy resin,

When in 25 ℃ chloroform, measuring limiting viscosity be about 0.03 to the difunctionality of about 0.2 deciliter of every gram gather (arylene ether) and

Curing catalyst, its content makes epoxy resin cure effectively;

The unnotched Izod impact strength ratio that wherein said compsn demonstrates after solidifying has the unnotched Izod impact strength greatly at least 5% that simple function gathers the correspondent composition of (arylene ether),

Wherein unnotched Izod impact strength records according to ASTM D4812 standard at 25 ℃.

Embodiment 36. is through curing compsn, and it is included in and makes the reaction product that obtains when each curable compositions solidifies among the embodiment 1-34.

The compsn that embodiment 37. is partly solidified, it is included in and makes the reaction product that obtains when each curable compositions solidifies among the embodiment 1-34.

Embodiment 38. comprises the goods through curing compsn of embodiment 36.

Embodiment 39. comprises the goods of the partly solidified compsn of embodiment 37.

Hereinafter is described other embodiment in detail, comprise through make said curable compositions cured and prepared through curing compsn with comprise said goods through curing compsn.

Embodiment

For the constraint that the flexible through cured resin that gathers (arylene ether) solubleness in curable compositions and obtain before breaking concerns, contriver of the present invention studies curable gathering (arylene ether) compsn.In the process of this research; Contriver of the present invention has been found that; Gather (arylene ether) resin through what use had specific hydroxy functional group and a particular molecular weight, can improve and gather (arylene ether) solubleness in curable compositions, and the toughness of sacrificial compositions after solidifying not.Perhaps, can improve the toughness of compsn after solidifying, not gather (arylene ether) solubleness in curable compositions and do not sacrifice.Therefore, a kind of embodiment is a curable compositions, and it comprises: epoxy resin; Limiting viscosity is about 0.03 to gather (arylene ether) to the difunctionality of about 0.2 deciliter of every gram, in 25 ℃ chloroform, measures; And curing catalyst, its content makes epoxy resin cure effectively; The unnotched Izod impact strength ratio that wherein said compsn demonstrates after solidifying has the unnotched Izod impact strength greatly at least 5% that simple function gathers the correspondent composition of (arylene ether), and wherein unnotched Izod impact strength records according to ASTM D4812 standard at 25 ℃.

About independent gathering (arylene ether) molecule, term " difunctionality " is meant that this molecule comprises two phenolic hydroxyl group groups.For gathering (arylene ether) resin, term " difunctionality " be meant said resin average each gather (arylene ether) molecule and have about 1.6 to about 2.4 phenolic hydroxyl group groups.In some embodiments, said difunctionality is gathered (arylene ether) and is comprised that on average each gathers (arylene ether) molecule about 1.8 to about 2.2 phenolic hydroxyl group groups.

As stated; The unnotched Izod impact strength ratio that compsn demonstrates after solidifying has the unnotched Izod impact strength greatly at least 5% that simple function gathers the correspondent composition of (arylene ether), and wherein unnotched Izod impact strength records according to ASTM D4812 standard at 25 ℃.Should be appreciated that; " have the correspondent composition that simple function gathers (arylene ether) " and be meant by curable compositions process accordingly through curing compsn, in said curable compositions, gather (arylene ether) and replace said difunctionality to gather (arylene ether) with simple function with identical characteristics viscosity.In some embodiments, the unnotched Izod impact strength ratio has the unnotched Izod impact strength big 5 to about 50% that simple function gathers the correspondent composition of (arylene ether).For independent gathering (arylene ether) molecule, term " simple function " is meant that this molecule comprises a phenolic hydroxyl group group.About gathering (arylene ether) resin, term " simple function " is meant that this resin comprises that on average each gathers (arylene ether) molecule about 0.8 to about 1.2 phenolic hydroxyl groups.

Notched izod impact strength also is improved.For example; In some embodiments; The notched izod impact strength ratio that compsn demonstrates after solidifying has the notched izod impact strength greatly at least 5% that simple function gathers the correspondent composition of (arylene ether), and wherein notched izod impact strength records according to ASTM D256 standard at 25 ℃.In some embodiments, said notched izod impact strength ratio has the notched izod impact strength big 5 to about 30% that simple function gathers the correspondent composition of (arylene ether).

Various epoxy resin all are suitable for said curable compositions.Said epoxy resin can be solid in room temperature.Therefore, in some embodiments, the softening temperature of epoxy resin is that about 25 ° of C are to about 150 ° of C.Softening temperature can be according to ASTM E28-99 (2004), and " Standard Test Methods for Softening Point of Resins Derived from Naval Stores by Ring-and-Ball Apparatus " measures.Said epoxy resin can be liquid or remollescent solid in room temperature.Therefore, in some embodiments, the softening temperature of said epoxy resin is less than 25 ° of C.

Suitable epoxy resin comprises for example aliphatic epoxy resin (diglycidyl ether that comprises NSC 6366), cycloaliphatic epoxy resin, bisphenol A epoxide resin, bisphenol F epoxy resin; The phenol phenolic resin varnish, cresols-phenolic resin varnish, biphenyl epoxy resin, polyfunctional epoxy resin; Naphthalene epoxy resins, divinylbenzene dioxide, 2-glycidyl phenylglycidyl ether; Dicyclopentadiene (DCPD)-type epoxy resin, many aromatic resins type epoxy resin, and combination.Said epoxy resin can be monomeric, and is oligomeric, or its combination.In some embodiments, said epoxy resin comprises dihydroxyphenyl propane diglycidyl ether epoxy resin.

Except epoxy resin, said curable compositions comprises that difunctionality gathers (arylene ether).Suitable difunctionality is gathered (arylene ether) and is comprised those with following structure:

Q wherein ¹And Q ²Be hydrogen, halogen, unsubstituted or substituted C when occurring independently at every turn ₁-C ₁₂The alkyl condition is that said hydrocarbyl group is not the tertiary hydrocarbon base, C ₁-C ₁₂The alkyl sulfenyl, C ₁-C ₁₂Alkyl oxygen base, or wherein at least two carbon atoms separate the C of halogen and Sauerstoffatom ₂-C ₁₂Halo alkyl oxygen base; Be 1 to about 100 independently when x occurs at every turn; Have following structure with L:

R wherein ¹And R ²Be hydrogen, halogen, unsubstituted or substituted C when occurring independently at every turn ₁-C ₁₂The alkyl condition is that said hydrocarbyl group is not the tertiary hydrocarbon base, C ₁-C ₁₂The alkyl sulfenyl, C ₁-C ₁₂Alkyl oxygen base, or wherein at least two carbon atoms separate the C of halogen and Sauerstoffatom ₂-C ₁₂Halo alkyl oxygen base; Z is 0 or 1; Have with Y and to be selected from following structure:

R wherein ³Be independently selected from hydrogen and C when occurring at every turn ₁-C ₁₂Alkyl, R ⁴And R ⁵Be independently selected from hydrogen when occurring, C at every turn ₁-C ₁₂Alkyl (comprises, for example C ₃-C ₈Naphthenic base and phenyl) or R ⁴And R ⁵Form C together ₄-C ₁₂Alkylidene group (for example, R ⁴And R ⁵Can form inferior n-pentyl (pentamethylene (CH also promptly, together ₂CH ₂CH ₂CH ₂CH ₂-)).

In some embodiments, difunctionality is gathered (arylene ether) and is had following structure:

Q wherein ¹It is methyl; Q ²Be hydrogen or methyl when occurring independently at every turn; R ¹And R ²Be hydrogen, halogen, unsubstituted or substituted C when occurring independently at every turn ₁-C ₁₂The alkyl condition is that said alkyl is not tertiary hydrocarbon base, C ₁-C ₁₂The alkyl sulfenyl, C ₁-C ₁₂Alkyl oxygen base, or wherein at least two carbon atoms separate the C of halogen and Sauerstoffatom ₂-C ₁₂Halo alkyl oxygen base; R ⁴And R ⁵Be hydrogen or C independently of one another ₁-C ₆Alkyl; Be 1 to about 50 independently when occurring with x at every turn.

In some embodiments, said difunctionality is gathered (arylene ether) and is had following structure:

Be 1 to about 20 independently when wherein x occurs at every turn.

Difunctionality is gathered (arylene ether) and can be prepared through the oxidisability copolymerization of for example monohydric phenol and dihydric phenol.Suitable monohydric phenol for example comprises, 2, and the 6-xylenol, 2,3, the 6-pseudocuminol, etc., and composition thereof.Suitable dihydric phenol comprises, for example, and 3,3 '; 5,5 '-tetramethyl--4,4 '-xenol, 2, two (3-methyl-4-hydroxy phenyl) propane, 2 of 2-; Two (3, the 5-dimethyl--4-hydroxy phenyl) propane, 1 of 2-, two (4-hydroxy phenyl) methane, 1 of 1-, two (4-hydroxy phenyl) ethane, 2 of 1-; Two (4-hydroxy phenyl) propane, 2 of 2-, two (4-hydroxy phenyl) butane, 2 of 2-, two (4-hydroxy phenyl) octanes, 1 of 2-, two (4-hydroxy phenyl) propane, 1 of 1-; Two (4-the hydroxy phenyl)-normal butanes of 1-, two (4-hydroxy phenyl) phenylmethane, 1, two (the 4-hydroxy-3-methyl phenyl) hexanaphthenes, 1 of 1-, two (4-hydroxyl-3, the 5-3,5-dimethylphenyl) pentamethylene, 1 of 1-; Two (4-hydroxyl-3, the 5-3,5-dimethylphenyl) hexanaphthenes, 1 of 1-, two (the 4-hydroxy-3-methyl phenyl) suberane, 1 of 1-, two (the 4-hydroxyls-3 of 1-; The 5-3,5-dimethylphenyl) suberane, 1, two (the 4-hydroxy-3-methyl phenyl) cyclooctane, 1 of 1-, two (4-hydroxyl-3, the 5-3,5-dimethylphenyl) cyclooctane, 1 of 1-; Two (the 4-hydroxy-3-methyl phenyl) cyclononane, 11 of 1-, two (4-hydroxyl-3, the 5-3,5-dimethylphenyl) cyclononane, 1 of 1-, two (the 4-hydroxy-3-methyl phenyl) cyclodecane, 1 of 1-; Two (4-hydroxyl-3, the 5-3,5-dimethylphenyl) cyclodecane, 1 of 1-, 1-two (4-hydroxy-3-methyl phenyl) ring undecane, 1, two (the 4-hydroxyls-3 of 1-; The 5-3,5-dimethylphenyl) ring undecane, 1, two (the 4-hydroxy-3-methyl phenyl) cyclododecanes, 1 of 1-, two (4-hydroxyl-3, the 5-3,5-dimethylphenyl) cyclododecanes, 1 of 1-; Two (4-hydroxyl-3-tert-butyl-phenyl) propane, 2 of 1-, two (4-hydroxyl-2, the 6-3,5-dimethylphenyl) propane, 2 of 2-, two (4-hydroxyl-3-bromophenyl) propane, 1 of 2-; Two (4-hydroxy phenyl) pentamethylene, 1 of 1-, the 1-bis(4-hydroxyphenyl) cyclohexane, and composition thereof.In some embodiments, said difunctionality is gathered (arylene ether) through 2,6-xylenol and 2, the oxidisability copolymerization preparation of two (3, the 5-dimethyl--4-hydroxy phenyl) propane of 2-.

In some embodiments, difunctionality is gathered (arylene ether) and is comprised the ZGK 5 segment.For example, difunctionality is gathered (arylene ether) and can be had following structure:

Q wherein ¹And Q ²Be hydrogen, halogen, unsubstituted or substituted C when occurring independently at every turn ₁-C ₁₂The alkyl condition is that said alkyl is not the tertiary hydrocarbon base, C ₁-C ₁₂The alkyl sulfenyl, C ₁-C ₁₂Alkyl oxygen base, or wherein at least two carbon atoms separate the C of halogen and Sauerstoffatom ₂-C ₁₂Halo alkyl oxygen base; Be 1 to about 100 independently when x occurs at every turn; Have following structure with A:

R wherein ⁶And R ⁷And R ⁸And R ⁹Be hydrogen, C when occurring independently at every turn ₁-C ₁₂Alkyl or C ₁-C ₁₂The halo alkyl; Be 0,1,2,3,4,5 or 6 independently when wherein m occurs at every turn; Y wherein ¹And Y ²And Y ³And Y ⁴Be hydrogen, C when occurring independently at every turn ₁-C ₁₂Alkyl, C ₁-C ₁₂Alkyl oxygen base, or halogen; Wherein n is 5 to about 200.In some embodiments, Q ¹When occurring methyl, wherein Q at every turn ²When occurring hydrogen or methyl, wherein Y at every turn ¹When occurring methoxyl group, wherein Y at every turn ², Y ³And Y ⁴When occurring hydrogen at every turn, R ⁶And R ⁷And R ⁸And R ⁹Be methyl when occurring, be 3 when m occurs at every turn at every turn, and n is about 10 to about 100.Having the inner silicone segmental gathers (arylene ether) and can prepare through the oxidisability copolymerization of monohydric phenol for example and the end capped ZGK 5 of phenol.The end capped ZGK 5 of phenol itself can be through silyl hydride two end capped ZGK 5 and the for example hydrosilylation reactions between the oxymethoxyallylbenzene (hydrosilylation reaction) preparation of compound, and said oxymethoxyallylbenzene has aliphatics carbon-carbon double bond and phenolic hydroxyl group group simultaneously.

Can said epoxy resin and difunctionality be gathered (arylene ether) merges in certain proportional range.In some embodiments; Curable compositions comprises that about 30 gather (arylene ether) to about 99 parts by weight of epoxy resin and about 1 to the difunctionality of about 70 weight parts, and wherein all weight parts are all based on 100 parts by weight of epoxy resin and difunctionality are gathered (arylene ether) altogether.In some embodiments; Curable compositions comprises that about 60 gather (arylene ether) to about 90 parts by weight of epoxy resin and about 10 to the difunctionality of about 40 weight parts, and wherein all weight parts are all based on 100 parts by weight of epoxy resin and difunctionality are gathered (arylene ether) altogether.

Except epoxy resin with gather (arylene ether), curable compositions also comprises curing catalyst, its content makes epoxy resin cure effectively.Suitable curing catalyst comprises for example potential cationic curing catalyzer, phenolic hardeners, amine hardener; Aliphatics or aromatic carboxylic acid's copper (II) salt, aliphatics or aromatic carboxylic acid's aluminium (III) salt, beta-diketon acid copper (II); Beta-diketon acid aluminium (III), alicyclic carboxylic acid acid anhydride (for example hexanaphthene-1,2-dicarboxylic anhydride); Boron trifluoride-Trimethylamine complex compound, and combination.

In some embodiments, curing catalyst is potential cationic curing catalyzer, and it is selected from diaryl group iodized salt, phosphonic acid ester; Sulphonate, carboxylicesters, phosphonium ylide (phosphonic ylides), benzyl sulfonium salt; Benzyl-pyridine salt, benzyl ammonium salt, isoxazolium salt, and combination.For example, said curing catalyst can be the potential cationic curing catalyzer that comprises diaryl group iodized salt with following formula:

[(R ¹⁰)(R ¹¹)I] ⁺X ^-

R wherein ¹⁰And R ¹¹Be C independently of one another ₆-C ₁₄The monovalence aromatic hydrocarbyl randomly is substituted with 1 to 4 and is selected from following univalent perssad: C ₁-C ₂₀Alkyl, C ₁-C ₂₀Alkoxyl group, nitro, and chlorine; And X wherein ^-Be negatively charged ion.In some embodiments, curing catalyst is the potential cationic curing catalyzer that comprises diaryl group iodized salt with following formula:

[(R ¹⁰)(R ¹¹)I] ⁺SbF ₆ ^-

R wherein ¹⁰And R ¹¹Be C independently of one another ₆-C ₁₄The monovalence aromatic hydrocarbyl randomly is substituted with 1 to 4 and is selected from following univalent perssad: C ₁-C ₂₀Alkyl, C ₁-C ₂₀Alkoxyl group, nitro, and chlorine.In some embodiments, curing catalyst is the potential cationic curing catalyzer that comprises 4-octyloxyphenyl phenyl-iodide hexafluoro antimonate.

In some embodiments, curing catalyst comprises aluminium acetylacetonate (III).

Said curing catalyst can comprise phenolic hardeners.Suitable phenolic hardeners comprises for example phenolic varnish type resol, aralkyl-type phenol resin, dicyclopentadiene-type resol; Terpene modified resol, biphenyl type resol, bisphenol type resol; Triphenyl methane type resol, and combination.

Curing catalyst can comprise amine hardener.Suitable amine hardener comprises for example isophorone diamine, Triethylenetetramine (TETA), NSC 446, aminoethylpiperazine, 1,2-and 1,3-diaminopropanes; 2,2-dimethylated propyl diethylenetriamine, 1,4-diaminobutane, 1,1; 7-diamino-heptane, 1,8-diamino-octane, 1,9-diamino-nonane, 1,12-diamino-dodecyl; 4-azepine heptamethylene diamines, N, N '-two (3-aminopropyl) butane-1,4-diamines, cyclohexane diamine, Dyhard RU 100 (dicyandiamine), diamide ditan (diamide diphenylmethyl); Diamide phenylbenzene sulfonic acid (diamide diphenylsulfonic acid) (amine affixture), 4,4 '-methylene dianiline (MDA), diethyl toluene diamine, mphenylenediamine, melamino-formaldehyde, tetren; 3-diethylamino propyl group amine, 3, the two propyl group amine of 3 '-imino-, 2, two (PAB) aniline of 4-, tetren, 3-diethylamino propyl group amine; 2,2,4-and 2,4,4-trimethylhexamethylenediamine, 1,2-and 1; The 3-DACH, 1,4-diamino--3,6-diethyl cyclohexane, 1,2-diamino--4-ethylcyclohexane, 1; 4-diamino--3,6-diethyl cyclohexane, 1-cyclohexyl-3,4-diimino-hexanaphthene, 4,4 '-diamino-dicyclohexyl methane, 4; 4 '-diamino-dicyclohexyl propane, 2, two (4-aminocyclohexyl) propane of 2-, 3,3 '-dimethyl--4,4 '-diamino-dicyclohexyl methane; 3-amino-1-hexanaphthene aminopropane, 1,3-and 1, two (amino methyl) hexanaphthenes of 4-,-and right-dimethylphenylene diamine, and composition thereof.

The amount of curing catalyst will depend on the type of curing catalyst, and the type of other resin Composition and amount.For example, when said curing catalyst was potential cationic curing catalyzer, its consumption can be per 100 weight part epoxy resin about 0.1 to about 10 weight parts.As another instance, when curing catalyst was beta-diketon acid copper (II) or beta-diketon acid aluminium (III), its consumption can be about 1 to 10 weight part of per 100 weight part epoxy resin.

Except epoxy resin, gather (arylene ether) and the curing catalyst, curable compositions can randomly also comprise about filler of 2 to about 50wt%, based on the gross weight of compsn.In this scope, the amount of filler can be and is less than or equal to 40wt%, perhaps is less than or equal to 30wt%, perhaps is less than or equal to 20wt%, perhaps is less than or equal to 10wt%.In some embodiments, said curable compositions is not for containing the filler of any intentional interpolation.In some embodiments, curable compositions is not for containing inorganic particulate filler.

Compsn also can randomly comprise one or more additives.Therefore; In some embodiments; Curable compositions comprises and is selected from following additive: dyestuff, pigment, tinting material, inhibitor, thermo-stabilizer, photostabilizer, softening agent, lubricant, flow ability modifying agent, dripping inhibitor, fire retardant, anti, antistatic agent, flow improver additive, processing aid, base plate bonding agent, releasing agent, toughner, low shrinkage additive, stress relieving additive, and combination.

A kind of embodiment is a curable compositions, and it is made up of following material: epoxy resin; Limiting viscosity is about 0.03 to gather (arylene ether) to the difunctionality of about 0.2 deciliter of every gram, in 25 ℃ chloroform, measures; Curing catalyst, its content makes epoxy resin cure effectively; Choose wantonly, about filler of 2 to about 50wt% is based on the gross weight of compsn; With optional; Be selected from following additive: dyestuff, pigment, tinting material, inhibitor, thermo-stabilizer, photostabilizer, softening agent, lubricant, flow ability modifying agent, dripping inhibitor, fire retardant, anti, antistatic agent, flow improver additive, processing aid, base plate bonding agent, releasing agent, toughner, low shrinkage additive, stress relieving additive, and combination; The unnotched Izod impact strength ratio that wherein said compsn demonstrates after solidifying has the unnotched Izod impact strength greatly at least 5% that simple function gathers the correspondent composition of (arylene ether), and wherein unnotched Izod impact strength records according to ASTM D4812 standard at 25 ℃.

A kind of embodiment is a curable compositions, and it comprises: dihydroxyphenyl propane diglycidyl ether epoxy resin; Limiting viscosity is about 0.03 to gather (arylene ether) to the difunctionality of about 0.2 deciliter of every gram, in 25 ℃ chloroform, measures, and wherein said gathering (arylene ether) has following structure:

A kind of embodiment is a curable compositions, and it is made up of following material: dihydroxyphenyl propane diglycidyl ether epoxy resin; Limiting viscosity is about 0.03 to gather (arylene ether) to the difunctionality of about 0.2 deciliter of every gram, in 25 ℃ chloroform, measures, and wherein said gathering (arylene ether) has following structure:

Be 1 to about 20 independently when wherein x occurs at every turn; Curing catalyst, its content makes epoxy resin cure effectively; Choose wantonly, about filler of 2 to about 50wt% is based on the gross weight of compsn; With optional; Be selected from following additive: dyestuff, pigment, tinting material, inhibitor, thermo-stabilizer, photostabilizer, softening agent, lubricant, flow ability modifying agent, dripping inhibitor, fire retardant, anti, antistatic agent, flow improver additive, processing aid, base plate bonding agent, releasing agent, toughner, low shrinkage additive, stress relieving additive, and combination; The unnotched Izod impact strength ratio that wherein said compsn demonstrates after solidifying has the unnotched Izod impact strength big 5 of correspondent composition that simple function gathers (arylene ether) to about 50%, and wherein unnotched Izod impact strength records according to ASTM D4812 standard at 25 ℃.

A kind of embodiment is a kind of curable compositions, and it comprises: the about 60 dihydroxyphenyl propane diglycidyl ether epoxy resin to about 90 weight parts; About 10 limiting viscosities to about 40 weight parts are about 0.06 to gather (arylene ether) to the difunctionality of about 0.12 deciliter of every gram, in 25 ℃ chloroform, measure, and wherein said gathering (arylene ether) has following structure:

Be 1 to about 20 independently when wherein x occurs at every turn; With about 0.5 aluminium acetylacetonate (III) to about 10 weight parts; Wherein all weight parts are all based on 100 parts by weight of epoxy resin and difunctionality are gathered (arylene ether) altogether; Wherein said dihydroxyphenyl propane diglycidyl ether epoxy resin and difunctionality gather (arylene ether) when 25 to 65 ° of C (also, in scope of whole 25 to 65 ° of C) be present in single mutually in; Wherein said curable compositions in the viscosity of 25 ° of C for being less than or equal to 10,000 centipoises; Wherein the unnotched Izod impact strength ratio that after solidifying, demonstrates of compsn has the unnotched Izod impact strength big 5 of correspondent composition that simple function gathers (arylene ether) to about 50%, and wherein unnotched Izod impact strength records according to ASTM D4812 standard at 25 ℃; The notched izod impact strength ratio that after solidifying, demonstrates with wherein said compsn has the notched izod impact strength big 5 of correspondent composition that simple function gathers (arylene ether) to about 30%, and wherein notched izod impact strength records according to ASTM D256 standard at 25 ℃.

A kind of embodiment is a kind of curable compositions, and it is made up of following material: the about 60 dihydroxyphenyl propane diglycidyl ether epoxy resin to about 90 weight parts; About 10 limiting viscosities to about 40 weight parts are about 0.06 to gather (arylene ether) to the difunctionality of about 0.12 deciliter of every gram, in 25 ℃ chloroform, measure, and wherein said gathering (arylene ether) has following structure:

Be 1 to about 20 independently when wherein x occurs at every turn; With about 0.5 aluminium acetylacetonate (III) to about 10 weight parts; Choose about 20 fillers wantonly to about 100 weight parts; With optional; Be selected from following additive: dyestuff, pigment, tinting material, inhibitor, thermo-stabilizer, photostabilizer, softening agent, lubricant, flow ability modifying agent, dripping inhibitor, fire retardant, anti, antistatic agent, flow improver additive, processing aid, base plate bonding agent, releasing agent, toughner, low shrinkage additive, stress relieving additive, and combination; Wherein said dihydroxyphenyl propane diglycidyl ether epoxy resin and difunctionality gather (arylene ether) when 25 to 65 ° of C (also, in scope of whole 25 to 65 ° of C) be present in single mutually in; Wherein all weight parts are based on 100 parts by weight of epoxy resin and difunctionality are gathered (arylene ether) altogether; The unnotched Izod impact strength ratio that wherein said compsn demonstrates after solidifying has the unnotched Izod impact strength big 5 of correspondent composition that simple function gathers (arylene ether) to about 50%, and wherein unnotched Izod impact strength records according to ASTM D4812 standard at 25 ℃; The notched izod impact strength ratio that after solidifying, demonstrates with wherein said compsn has the notched izod impact strength big 5 of correspondent composition that simple function gathers (arylene ether) to about 30%, and wherein notched izod impact strength records according to ASTM D256 standard at 25 ℃.

A kind of embodiment is a kind of curable compositions, and it comprises: the about 60 dihydroxyphenyl propane diglycidyl ether epoxy resin to about 90 weight parts; About 10 limiting viscosities to about 40 weight parts are that the difunctionality of about 0.06 deciliter of every gram is gathered (arylene ether), in 25 ℃ chloroform, measure, and wherein said gathering (arylene ether) has following structure:

Another embodiment is a kind of curable compositions, and it comprises: the about 60 dihydroxyphenyl propane diglycidyl ether epoxy resin to about 90 weight parts; About 10 limiting viscosities to about 40 weight parts are that the difunctionality of about 0.09 deciliter of every gram is gathered (arylene ether), in 25 ℃ chloroform, measure, and wherein said gathering (arylene ether) has following structure:

Another embodiment is a kind of curable compositions, and it comprises: the about 60 dihydroxyphenyl propane diglycidyl ether epoxy resin to about 90 weight parts; About 10 limiting viscosities to about 40 weight parts are that the difunctionality of about 0.12 deciliter of every gram is gathered (arylene ether), in 25 ℃ chloroform, measure, and wherein said gathering (arylene ether) has following structure:

A kind of embodiment is a kind of method for preparing curable compositions; Comprise: blend epoxy resin; Limiting viscosity is about 0.03 to gather (arylene ether) to the difunctionality of about 0.2 deciliter of every gram when in 25 ℃ chloroform, measuring, and curing catalyst, and its content makes epoxy resin cure effectively; The unnotched Izod impact strength ratio that wherein said compsn demonstrates after solidifying has the unnotched Izod impact strength greatly at least 5% that simple function gathers the correspondent composition of (arylene ether), and wherein unnotched Izod impact strength records according to ASTM D4812 standard at 25 ℃.In some embodiments, said preparation of compositions comprises through being heated to the temperature that is less than or equal to 100 ° of C and forms and to comprise that said epoxy resin gathers the mutually single of (arylene ether) with difunctionality.

The conditions suitable that solidifies said curable compositions depends on many factors, comprises the type and the concentration of said epoxy resin, and the type of said curing catalyst and amount.Suitable condition of cure can comprise and is exposed to about 120 to about 10 minutes of the temperature of about 250 ° of C to about 24 hours time.In above-mentioned time range, solidification value can be at least about 150 ° of C, perhaps at least about 180 ° of C, perhaps at least about 210 ° of C.As illustrated among the following work embodiment, curing can be carried out in the two or more steps of successive in different temperature.Do not need too much experiment just can confirm suitable condition of cure the thermofixation those skilled in the art.In some embodiments, said compsn can be partly solidified.But the character of " through the curing compsn " of indication or " compsn is after solidifying " typically refers to completely crued basically compsn in this application.Technician in the thermosetting resin field does not need too much experiment just can to confirm whether basically completely solidified of a sample.For example, can find to be characterized in the extra solidified heat release that takes place in the analytic process through this sample of difference formula scanning calorimetric analysis.Basically completely crued sample will not demonstrate or demonstrate heat release seldom in this analysis.

The present invention prolong and obtain when any foregoing is solidified through curing compsn.The present invention also prolongs and comprises this goods through curing compsn.Be particularly suitable for making the electronics laminate through curing compsn, prepreg, and printed substrate.Said composition also can be used for varnish, sealing agent, structural composites, powder and liquid coating, and high-temperature adhesives.

Further specify the present invention through following non-restrictive example.

Embodiment 1-10, Comparative Examples 1-12

To be used for explaining that the difunctionality lower molecular weight gathers 10 embodiments of the invention and the following Comparative Examples of (arylene ether) use in epoxy resin and do contrast: 7 instruction book officials can lower molecular weights gather the Comparative Examples of (arylene ether) use in epoxy resin; 4 non-sense lower molecular weights of explanation are gathered Comparative Examples and Comparative Examples of only using epoxy resin of (arylene ether) use in epoxy resin.Said dihydroxyphenyl propane diglycidyl ether (" BPA Epoxy ") derives from Dow Chemical Company as DER 332 epoxy resin.Three kinds of difunctionalitys are gathered (arylene ether) resin and are designated as " PPE, 0.12, bifxl. ", " PPE, 0.09; bifxl. " and " PPE, 0.06, bifxl. "; Wherein " 0.12 ", " 0.09 " and " 0.06 " is meant the limiting viscosity of this resin, unit is the every gram of decilitre.Two kinds of simple functions gather (arylene ether) resin and are designated as " PPE, 0.12monofxl. " and " PPE, 0.12monofxl. ", and the end capped resin of said non-sense diacetyl oxide is designated as " PPE, 0.06nonfxl. ".

Difunctionality is gathered (arylene ether) resin and is prepared as follows: through 2,6-xylenol and 2,2-two (3,5-dimethyl--4-hydroxyl) thus the oxidisability copolymerization of propane forms the multipolymer with desired characteristics viscosity and about two oh groups of each molecule.The detailed process of this method is described in the U.S. Patent application of submitting on December 20th, 2,005 11/298,182.

Simple function gathers (arylene ether) resin and is prepared as follows: through 2, thereby the homopolymerization of 6-xylenol forms gather (2,6-dimethyl--1,4-phenylene ether) with desired characteristics viscosity and the about oh group of each molecule.

" non-sense " (acetic ester is end capped) gather (arylene ether) through be used to prepare the identical method preparation of method that 0.06 deciliter of every gram (dL/g) simple function gathers (arylene ether); Different is that product gathers (2; 6-dimethyl--1,4-phenylene ether) oh group is described below through in the presence of 4-(dimethylamino) pyridine catalyst, using the acetic ester end-blocking with acetic anhydride.Simple function 0.06dL/g is gathered (2,6-dimethyl--1,4-phenylene ether) (1500 gram) and be dissolved in the toluene of 80 ° of C of 1100 grams, and add 30 gram 4-(dimethylamino) pyridines and 300 gram diacetyl oxides.Solution cooling after stirring 6 hours is through separating out in methyl alcohol and the dry resin C that isolates.

In the chloroform of 25 ° of C, measured 125 ° of C dried in vacuum 1 hour the limiting viscosity of gathering (arylene ether) sample.

MWD is measured through gel permeation chromatography (GPC).Chromatographic system constitutes (it such as comprises at degree pump (isocratic pump), automatic sampler, thermocolumn chamber (thermostatted column compartment), and multiwavelength detector) by Agilent Series1100 system.Eluting solvent is the chloroform with 50ppm (by weight) di-n-butyl amine.Sample solution is through being dissolved in 0.01 gram sample in 20 milliliters of chloroforms and preparing, with toluene (0.25 milliliter every liter) as interior mark.Before gpc analysis, this sample solution is filtered through Gelman 0.45 micropin filter cartridge (micrometer syringe filter); The other sample of refabrication not.Volume injected is 50 microlitres, and the wash-out flow rate is set to 1 ml/min.Two Polymer Laboratories GPC posts (Phenogel 5 micron linear (2), 300x7.80 millimeter) of polyphone connection are used for the separation of sample.Detect wavelength and be set to 280 nanometers.Obtain data, and it is processed with the Agilent ChemStation with integrated GPC DAS.MWD result calibrates with polystyrene standards.The result just is recorded as " M without any correction _nAnd " M (AMU) " _w(AMU) ".

Use the heating rate of Perkin Elmer DMA 7e instrument and 5 ℃/minute, with dynamic mechanical analysis (DMA) mensuration second-order transition temperature (T _g).

Gather (arylene ether) through proton nuclear magnetic resonance spectrum ( ¹H NMR) analyzes, confirm the concentration (in ppm by weight) of absolute number average molecular weight and hydroxyl end groups.Internal element (comprise 2,6-dimethyl--1, the 4-phenylene ether units is derived from 3; 3 ', 5,5 '-tetramethyl--4, the divalent group of 4 '-xenol; Be derived from 2, the divalent unit of two (3, the 5-dimethyl--4-hydroxyl) propane of 2-) (comprise 2, the basic unit of 6-dimethyl--1-hydroxyl-benzene-4-with the end-blocking unit; 2,6-dimethyl--benzene-1-base unit is derived from 2, and 2-two (3; 5-dimethyl--4-hydroxyl) the unit price phenolic units of propane and be derived from 2, the monovalence dibutylamine of 6-xylenol-substituted phenolic group and dibutylamine catalyzer) relative quantity through relevant resonance integral and the number of regulating the proton cause resonance are measured.Calculate the value of number-average molecular weight then based on internal element and the unitary relative quantity of total end group.The value of hydroxyl end groups content is based on the relative quantity of end group phenolic group and end group and internal element total amount and calculate.The value of hydroxyl (OH) group content is with weight PPM (ppm) expression, and the molecular weight of wherein specifying oh group is every mole of 17 gram." functionality " is each mean number that gathers the hydroxyl of (arylene ether) molecule.Functionality is according to computes:

Functionality=2*OH-end group mole number/(all end group mole numbers)

Wherein " mole number of OH-end group " is meant that the mole number of hydroxyl end groups and " all end group mole numbers " are the mole numbers of all end groups, and it comprises hydroxyl end groups and so-called " tail group " (being 2 in this case, 6-3,5-dimethylphenyl group).

Gathering (arylene ether) character is summarized in the table 1.The functionality value of non-functionalized resins is 0 to be meant and to be limited to 50ppm on the hydroxy radical content that use 2,6-xylenol standard specimen is measured through FFIR (FTIR).

Table 1

Table 1 (continuing)

All curable compositions all are dissolved in the BPA epoxy resin and prepare through will gather (arylene ether) (if exist) at 90 ° of C.Then add curing catalyst, aluminium acetylacetonate (deriving from Acros Organics, catalog number (Cat.No.) AC19697) and thorough mixing.Mixture in 100 ° of C and 7.4 kPas (kPa) degassing, is poured in the mould that preheats 100 ° of C then.Place the stove of 150 ° of C to keep 90 minutes on the mould of filling.Then furnace temperature is increased to 175 ° of C.After 60 minutes, temperature is increased to 200 ° of C.After 60 minutes, furnace temperature is increased to 220 ° of C.After after 60 minutes, stove cuts out, mould is spent the night in stove be cooled to room temperature.Solidified is tested print from mould, take out and be cut into test sample.Thickness of sample is 3.175 millimeters (1/8 inches).What cut is to derive from MK Diamond Products as 158189MK-100Tile Saw, the diamond-impregnated wheel wet saw of Inc (diamond-wheeled wet saw).Blade is MK-225, and 25.4 centimetres of (10 inches) diameter diamond blades, thickness are 1.27 millimeters (0.05 inches).In order to minimize any fragment (chipping), when cutting, sample is placed on plastics or the wooden base material along cutting edge.All compsns are summarized in the table 2, and wherein all group components are all in weight part (pbw).

Density records in the water of 23 ° of C according to the method A of ASTM D792-00 standard.

In degree centigrade the heat-drawn wire value according to the method B of ASTM D 648-06 standard, using 0.45 MPa power is that 1.27 centimetres (0.5 inches) and thickness are to measure automatically on the sample of 3.175 millimeters (0.125 inches) at width.Immersing medium is the organosilicon fluid.Test is carried out through heating described immersing medium, is initially the temperature of 23 ° of C, and heat-up rate is 2 ° of C PMs.

The unnotched Izod impact strength value, with every meter of joule (J/m) expression, at 23 ° of C, using width is that 1.27 centimetres (0.5 inches) and thickness are that the sample of 3.175 millimeters (0.125 inches) records according to ASTM D 4812-06 standard.Sample is cut from above-mentioned molded strip.The device that uses has the pendulum of the hammer of 0.907 kilogram (2 pounds).

Notched izod impact strength is according to the method A of ASTM D 256-06 standard; The sample that uses the hammer of 0.907 kilogram (2.00 pounds) and have a breach at 23 ° of C records, and said breach makes at least 1.02 centimetres (0.4 inches) of 1.27 centimetres of initial (0.5 inch) degree of depth remain under this breach.After carving breach, sample is adapted to 24 hours at 23 ° of C.

Specific inductivity (" D _k") value and dissipation factor (" D _f") value records according to ASTM D150-98 (2004) standard at 23 ° of C.Sample is the rectangular prism that is of a size of 3.175 millimeters of 5 cm x, 5 cm x.Before test with sample 23 ° of C and the minimum adaptation of 50% relative humidity 12 hours.Measuring sensor is that model is the Hewlett-Packard Impedance Material Analyzer of 4291B, and it is centimetre dark to be of a size of centimetre high * 20.5,27.5 centimetres of wide * 9.5.Electrode is Hewlett-Packard Model 16453A, and diameter is 7 millimeters.Measure and use capacitive method to carry out the frequency of inswept certain limit when being applied to dc voltage on the dielectric materials.The voltage that applies be 0.2mV (rms) to 1V (rms), range of frequency is 1MHz to 1Ghz.In table 2, the specific inductivity of the frequency of 500 mepses and 1 mega hertz and dissipation factor value have been write down at 100 mepses.

Property value is summarized in the table 2.

Table 2 (continuing)

	Ex.8	Ex.9	Ex.10
				Compsn
BPA epoxy resin	90	80	70
				PPE，0.12，bifxl.	0	0	0
PPE，0.12，monofxl.	0	0	0
				PPE，0.06，bifxl.	0	0	0
PPE，0.06，monofxl.	0	0	0
				PPE，0.06，nonfxl.	0	0	0
PPE，0.09，bifxl.	10	20	30
				Aluminium acetylacetonate	2.5	2.5	2.5
Character
				Density (g/cm ³)	1.1772	1.1676	1.1568
T _g(°C)	152	157	158
				HDT0.45MPa(°C)	149	154	160
Non-notch izod (J/m)	147.7	186.4	209.2
				Notched izod (J/m)	39.5	45.4	49.5
D at 100MHz _k	2.94	2.92	2.89
				D at 500MHz _k	2.87	2.85	2.83
D at 1GHz _k	2.82	2.81	2.79
				D at 100MHz _f	0.012	0.012	0.011
D at 500MHz _f	0.012	0.012	0.010
				D at 1GHz _f	0.010	0.010	0.009

When gathering (arylene ether) when limiting viscosity is held constant at 0.12dL/g; Through being compared, embodiment 1-3 and Comparative Examples 1-4 can obviously find out (arylene ether) type (simple function and difunctionality) and the amount (10 of gathering; 20; With 30 weight parts, based on the epoxy of 100 weight parts altogether with gather (arylene ether)) effect.Comparative Examples 1 contains solidified epoxy resin, does not contain to gather (arylene ether).On identical gathering (arylene ether) level, these data show that the difunctionality that contains 0.12dL/g gathers the epoxy resin of (arylene ether) (embodiment 1-3), demonstrate better character than using simple function to gather the epoxy resin (Comparative Examples 2-4) that (arylene ether) make.Particularly, unnotched Izod impact strength has obtained significant and unexpected improvement, and also observes second-order transition temperature, heat-drawn wire, and notched izod impact strength and specific inductivity are significantly improved.In addition, increase level and the second-order transition temperature (T that difunctionality is gathered (arylene ether) _g), heat-drawn wire (HDT), non-notch and notched izod impact strength, specific inductivity (D _k) and dissipation factor (D _f) improvement relevant.

When the limiting viscosity that will gather (arylene ether) is held constant at 0.06dL/g; Embodiment 4-7 and Comparative Examples 5-12 compared obviously to find out the type (non-functional and simple function and dual functional) of gathering (arylene ether) and measure (10; 20; 30 and 40 weight parts, based on the epoxy of 100 weight parts altogether with gather (arylene ether)) effect.On identical gathering (arylene ether) level; These data show that containing 0.06 difunctionality gathers the composition epoxy resin of (arylene ether) (embodiment 4-7) and demonstrate than use the composition epoxy resin (Comparative Examples 5 that simple function gathers (arylene ether) preparation; 7; 9 and 11) better character, and than containing the significantly better character of composition epoxy resin (Comparative Examples 8,10 and 12) of gathering (arylene ether) greater than the non-sense of 10wt%.Particularly; Gather among the embodiment 4-7 of (arylene ether) containing said difunctionality; Unnotched Izod impact strength has obtained significant and unexpected improvement, and also observes second-order transition temperature, and heat-drawn wire and notched izod impact strength are significantly improved.For containing the sample that 10,20 or 30 weight parts gather (arylene ether), specific inductivity also be improved (minimizing).In addition, increasing difunctionality, to gather the level of (arylene ether) relevant with the improvement of second-order transition temperature, heat-drawn wire, non-notch and notched izod impact strength, specific inductivity and dissipation factor.On the contrary, increasing non-sense gathers the level of (arylene ether) and can reduce heat-drawn wire.

Embodiment 8,9 and 10 explanations have composition and the character that the 0.09dL/g difunctionality is gathered the compsn of the present invention of (arylene ether).The level that the increase difunctionality is gathered (arylene ether) is relevant with the improvement of second-order transition temperature, heat-drawn wire, non-notch and notched izod impact strength, specific inductivity and dissipation factor.

Here the specification sheets of record uses embodiment to come open the present invention, comprises preferred forms, and makes any those skilled in the art can make and use the present invention.Patentable scope of the present invention is limited claim, and can comprise other embodiment that those skilled in the art expect.These other embodiment; If they have and claim identical structural element in language description; If perhaps they comprise the equivalent construction element substantially the same with the language description of said claim, also intention is comprised in the scope of claim.

All incorporate the full content of all patents, patented claim and other reference quoted into the application through reference.But,, have precedence over afoul with it term from the reference of incorporating into from the application's term if when the term among the application conflicts with the term of the reference of incorporating on the contrary or mutually.

All scopes that the application disclosed all comprise end points, and each end points can independently of one anotherly combine.

(especially in the accompanying claims) uses a technical term " one ", " a kind of " with " should/said " (corresponding to " a " in the English, " an " and " the ") with similarly refer to and be intended to be interpreted as encompasses singular and plural number in the context that the application describes, and clearly indicate in addition otherwise understand in the context.In addition, should point out further that the term among the application " first ", " second " etc. do not refer to any order, quantity or importance, but are used for element differentiation each other.Comprise described value with the modifier " pact " of measure word coupling, and have the specified meaning of context (for example, it comprises the grade of errors relevant with the measurement of specified quantitative).

Claims

1. curable compositions, form by following material:

About 60 to about 90 parts by weight of epoxy resin;

About 10 limiting viscosities to about 40 weight parts are about 0.03 to gather (arylene ether) to the difunctionality of about 0.2 deciliter of every gram, in 25 ℃ chloroform, measure;

Curing catalyst, its content makes epoxy resin cure effectively;

Wherein all weight parts are all based on 100 parts by weight of epoxy resin and difunctionality are gathered (arylene ether) altogether; With

2. curable compositions comprises:

About 10 limiting viscosities to about 40 weight parts are about 0.03 to gather (arylene ether) to the difunctionality of about 0.2 deciliter of every gram, in 25 ℃ chloroform, measure, and wherein said gathering (arylene ether) has following structure:

Be 1 to about 20 independently when wherein x occurs at every turn; With

Curing catalyst, its content makes epoxy resin cure effectively;

3. curable compositions, form by following material:

Be 1 to about 20 independently when wherein x occurs at every turn;

Curing catalyst, its content makes epoxy resin cure effectively;

4. curable compositions comprises:

Be 1 to about 20 independently when wherein x occurs at every turn; With

About 0.5 aluminium acetylacetonate (III) to about 10 weight parts;

5. curable compositions, form by following material:

Be 1 to about 20 independently when wherein x occurs at every turn; With

About 0.5 aluminium acetylacetonate (III) to about 10 weight parts;

Choose about 20 fillers wantonly to about 100 weight parts; With

6. curable compositions comprises:

Be 1 to about 20 independently when wherein x occurs at every turn; With

About 0.5 aluminium acetylacetonate (III) to about 10 weight parts;

7. curable compositions comprises:

Be 1 to about 20 independently when wherein x occurs at every turn; With

About 0.5 aluminium acetylacetonate (III) to about 10 weight parts;

8. curable compositions comprises:

Be 1 to about 20 independently when wherein x occurs at every turn; With

About 0.5 aluminium acetylacetonate (III) to about 10 weight parts;

9. method for preparing curable compositions comprises:

Blend

About 60 to about 90 parts by weight of epoxy resin,

About 10 limiting viscosities during in 25 ℃ chloroform, the measuring of about 40 weight parts be about 0.03 to the difunctionality of about 0.2 deciliter of every gram gather (arylene ether) and

Curing catalyst, its content makes epoxy resin cure effectively;

10. through curing compsn, it is included in and makes the reaction product that obtains when each curable compositions solidifies among the claim 1-8.

11. partly solidified compsn, it is included in and makes the reaction product that obtains when each curable compositions solidifies among the claim 1-8.

12. comprise the goods through curing compsn of claim 10.

13. comprise the goods of the partly solidified compsn of claim 11.