CN105131525A

CN105131525A - Heat curing composition containing combination of amphiphilic type block copolymer and polyol and heat setting product of heat curing composition

Info

Publication number: CN105131525A
Application number: CN201510583560.9A
Authority: CN
Inventors: 吉明磊; 李永江; 卢多维克·瓦莱特
Original assignee: Dow Global Technologies LLC
Current assignee: Dow Global Technologies LLC
Priority date: 2009-03-09
Filing date: 2009-03-09
Publication date: 2015-12-09

Abstract

The invention provides a heat curing composition, which comprises (a) at least one type of amphiphilic type block copolymer, (b) at least one type of polyol, (c) at least one type of epoxy resin of which each molecule contains at least two ethylene oxide rings on average, (d) at least one type of acid anhydride hardener of which each molecule contains at least one anhydride ring on average, and (e) at least one type of catalyst; the invention also provides a heat curing product prepared from the heat curing composition.

Description

The heat curable composition of the combination containing amphiphilic block copolymers and polyvalent alcohol and thermosetting product thereof

The application is the applying date is on March 9th, 2009, international application no is PCT/CN2009/000251, China national application number is 200980157951.7 and denomination of invention is the divisional application of the application of " heat curable composition of the combination containing amphiphilic block copolymers and polyvalent alcohol and thermosetting product thereof ".

Technical field

The present invention relates to a kind of heat curable composition, described heat curable composition comprises amphiphilic block copolymers, polyvalent alcohol, acid anhydrides, epoxide and catalyzer; Also relate to the thermosetting product manufactured by this heat curable composition.The thermosetting product manufactured by heat curable composition of the present invention has the mechanical property of raising, and especially the heat curable composition of toughness and physical strength, maintains high heat resistance simultaneously.Composition of the present invention may be used for various application, as casting, potting and encapsulation, as electricity and electronic application, and matrix material.

Background technology

Some thermosetting resin known has good toughness and good mechanical property, and some thermosetting resin known has good thermotolerance, and some thermosetting resin known has good processibility.But, so far, also do not prepare the thermosetting resin of each performance of above feature to degree as follows: this thermosetting resin can be prepared on a large scale, and can use it in the performance application under significant stress and humidity exposure.

Maintain the good thermotolerance of resin for being with the mechanical property (such as higher toughness and physical strength) be improved simultaneously and there is demand with the thermosetting resin of good workability.High tenacity and high mechanical strength cause less crackle and high mechanical integrity, thus reduce the quantity of defect and improve reliability and the life-span of the finished product.High heat resistance makes high service temperature become possibility.Low formulation viscosity improves processibility and makes higher filler charge capacity become possibility.

So far, those skilled in the art attempted by by various additive as toughner (flexibilizers) and toughness reinforcing reagent (tougheningagents) are added into the performance that thermosetting resin improves thermosetting resin.But such as the use of polyalcohols in thermosetting resin of conventional toughner only brings raising medium in toughness; And the thermostability of thermosetting resin is significantly reduced because of low (lower than the 100 DEG C) second-order transition temperature caused thus.The use of conventional toughness reinforcing reagent in thermosetting resin due to obtained preparation high viscosity and due to the complicacy of phase separation, result in the problem in processing.

Such as, conventional toughness reinforcing reagent as the use in thermosetting resin of liquid rubber, core-shell particles and thermoplastic polymer with some other performances adversely affecting thermosetting resin as second-order transition temperature, mechanical property, viscosity etc. for cost improves the toughness of thermosetting resin.Second-order transition temperature and physical strength is kept to be difficult when using liquid rubber and thermoplastic polymer to improve toughness; And owing to the character of core-shell particles, when without these particles are dispersed in completely under when additional processing thermosetting resin as epoxy resin in be difficult.

In addition, there are the various prior aries of having attempted the heat curable composition having employed toughness reinforcing.Such as, EP126494A1 describes the composition containing specific a group of stiffening agent, epoxy resin and thermoplastic polymer.When combining with structural fibers, said composition produces the matrix material with the shock-resistance of raising, the tensile property of raising and high compression performance.But EP126494A1 describes the conventional method for toughening by thermoplastic polymer being joined thermosetting resin; And disclose and thermoplastic polymer is combined in epoxy-resin systems to improve its shock-resistance.EP126494A1 uses the toughness reinforcing reagent of thermoplastic polymer; It does not instruct amphiphilic block copolymers as the use of toughness reinforcing reagent in epoxy-resin systems.

United States Patent (USP) 4,497,945 disclose by making the anhydride curing agent pre-reaction for epoxy resin gathering (propylene oxide) glycol or triol and chemistry excessive form tough epoxy polymkeric substance.Afterwards by obtained diester-diacid and epichlorohydrin-bisphenol A polymerization of epoxy resins.For this reaction, suitable imidazoles (imidizole) catalyzer is preferred.But, United States Patent (USP) 4,497,945 uses not disclosing toughness reinforcing reagent; And do not instruct amphiphilic block copolymers as the use of toughness reinforcing reagent in epoxy-resin systems.

United States Patent (USP) 4,551,520 disclose can injection-molded 95 to 40 % by mole of terephthalic acids, 5 to 60 % by mole trans-4,4 '-Stilbene dioctyl phthalate and at least 60 % by mole 1, the polyester of 4-cyclohexanedimethanol, to provide the formed article with extra high shock strength and excellent in chemical resistance.In addition, can by United States Patent (USP) 4, the film for having these performances extruded by the polyester of 551,520, is spun into the fiber with these performances, or blowing is the bottle with these performances.United States Patent (USP) 4,551,520 do not use toughness reinforcing reagent; And do not instruct amphiphilic block copolymers as the use of toughness reinforcing reagent in epoxy-resin systems.

United States Patent (USP) 4,846,905 disclose a kind of heat-setting, Single Component Eopxy Adhesives composition, and described composition comprises: (1) has the epoxy functionalities and about 150 to 10 being greater than 1, the glycidyl ether epoxides of the molecular weight between 000; (2) catalyzer, described catalyzer comprises (i) formula H+SbF ₅the acid of X-, wherein X is halogen, hydroxyl or-OR, and wherein--OR is that molecular weight is less than about 10, the aliphatic series of 000 or the residue of aromatic alcohol and (ii) N, N-diethyl-o-Tolylamine; (3) there is aliphatic series or the non-aromatic cyclic polyvalent alcohol of about 2 to 18 carbon atoms, its at least two hydroxyls are primary hydroxyl or secondary hydroxyl, and do not have electron-withdrawing substituent, amine substituting group or relative to be connected to polyvalent alcohol methylol carbon α position on produce sterically hindered large-substituent; And (4) toughness reinforcing reagent, described toughness reinforcing reagent has epoxide compatible components and an epoxide uncompatibility component not with epoxide reaction in the curing process.

United States Patent (USP) 4,846,905 disclose a kind of composition epoxy resin comprising polyvalent alcohol and toughness reinforcing reagent.But, United States Patent (USP) 4,846,905 describe different toughness reinforcing reagent; And this toughness reinforcing reagent can be divided into following three types:

1. scion grafting has elastoprene skeleton or the core of the polymerization of the shell of acrylate or methacrylic ester, monovinyl aromatic hydrocarbons or its mixture.

2. core-shell structure copolymer graft copolymer, its center or skeleton have the polyacrylate polymers lower than the second-order transition temperature of about 0 DEG C.

3. there is the elastomer particle lower than the second-order transition temperature of about 25 DEG C, and before mixing with other component of composition, it is polymerized at epoxide situ.

The toughness reinforcing reagent (core-shell particles and elastomer particle) of all above three types is different from the toughness reinforcing reagent of amphiphilic block copolymers.Prior art is not had to employ with acid anhydrides and may reagent toughness reinforcing with epoxy reactive activity.

United States Patent (USP) 5,382,628 disclose show high impact at low temperatures unexpectedly thermoforming plastic product as frozen product dish.By containing 88 to 99 % by weight poly-(ethylene glycol terephthalate) resin and 1 to 12 % by weight containing at least 30 % by mole 1, the polyester mixture of poly-(terephthalic acid 1,4 cyclohexane dimethanol ester) resin of 4-cyclohexanedimethanol obtains this product.

United States Patent (USP) 5,382,628 describe the thermoplasticity PET material being thermoformed into plastics.United States Patent (USP) 5,382,628 openly do not comprise the use of the Thermoset formulations of amphiphilic block copolymers as toughness reinforcing reagent in epoxy-resin systems.

WO1998001495A1 discloses has good flexibility and the epoxy-resin systems of shock-resistance, and described epoxy-resin systems is modified the solvent resistance providing raising.What molecular weight was less than the polyalkylene oxide hydrocarbon segment of 500 is combined in the chemical resistant properties providing raising when not sacrificing mechanical property.In order to realize this point, making there is low-molecular-weight alkoxylated polyol and polycarboxylic acid anhydride reacts to prepare half ester, afterwards described half ester being used for by forming adducts with polyglycidyl ether and synthesizing the epoxy resin of toughness reinforcingization.The epoxy resin of toughness reinforcingization and acid-functionalized oligomeric olefin oxide is taught in WO1998001495A1.

But the technology in WO1998001495A1 employs polyalcohol modified stiffening agent with toughness reinforcing network, but does not use toughness reinforcing reagent.WO1998001495A1 does not instruct amphiphilic block copolymers as the use of toughness reinforcing reagent in epoxy-resin systems, and described use gives toughness reinforcingization of improvement and maintains Tg.

United States Patent (USP) 5, 789, 482 disclose composition epoxy resin, described composition epoxy resin contains: (a) at least one epoxy resin, described epoxy resin per molecule on average contains more than one 1, 2-epoxide group, b () is for the anhydride hardener of epoxy resin (a), (c) toughness reinforcing reagent, and (d) compound containing two active hydrogen atoms, described compound can react with epoxy resin (a), described composition epoxy resin has outstanding toughness and is suitable as cast resin, laminating resin, molding compounds, coating compound and encapsulation system are used for electricity and electronic component.

United States Patent (USP) 5,789,482 teach and are attached to improve toughness in system by toughness reinforcing for core/shell polymeric reagent, this from using amphiphilic block copolymers as toughness reinforcing reagent in conjunction with different.And United States Patent (USP) 5,789,482 containing hydroxycarboxylic acid, dicarboxylic acid or be the biphenol of monokaryon dihydric phenol, dihydroxy naphthlene, dihydroxybiphenyl or another kind of double-core aromatic substance, and described double-core aromatic substance has methylene radical, isopropylidene, O, SO ₂or S bridge and the hydroxyl being connected to aromatic kernel containing two, and wherein phenyl ring can also contain halogen atom.

WO2006052729A1 discloses a kind of curable epoxy resin composition, and described composition comprises (a) thermal curable epoxy resin; And (b) containing at least one epoxy resin can miscible block segments and at least one epoxy resin can not the amphiphilic block copolymers of miscible block segments; Wherein saidly miscible block segments can not comprise at least one polyether structure, condition describedly the polyether structure of miscible block segments can not contain at least one or the multiple alkylene oxide monomer units with at least four carbon atom, to make when by epoxy resin composition, the toughness of the composition epoxy resin of the solidification obtained increases.Amphiphilic block copolymers is preferably full polyether block copolymer as PEO-PBO Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock or PEO-PBO-PEO triblock copolymer.

WO2006052729A1 describes the use of the toughness reinforcing reagent of amphiphilic in epoxy resin formulation.But the technology described in WO2006052729A1 is not instructed or is advised the improvement of following aspect: (i) modulus in flexure; (ii) tensile strength, tensile elongation, K _1cand transverse strain; Or (iii) Tg value.

Therefore, industrially still demand is existed for such thermosetting resin: particularly when comparing with conventional toughening technology, in its mechanical property as tensile strength and flexural strength demonstrate raising, strengthen toughness simultaneously and significantly do not reduce the thermostability defined by second-order transition temperature.

Therefore, need to provide to one or more of above performance and feature with the thermosetting product relative to the improvement in conventional thermoset plastics.

Summary of the invention

The invention provides the remarkable and surprising improvement relative to above-mentioned conventional thermoset plastics.

One aspect of the present invention relates to a kind of heat curable composition, describedly comprise heat curable composition: (a) at least one amphiphilic block copolymers, (b) at least one polyvalent alcohol, c () at least one per molecule on average contains the epoxy resin of at least two oxyethane rings, d () at least one per molecule on average contains the anhydride hardener of at least one acid anhydrides, and (e) at least one catalyzer.

Another aspect of the present invention relates to a kind of method for the preparation of above heat curable composition.

Another aspect more of the present invention relates to a kind of thermosetting product by above heat curable composition solidification being manufactured.

The present invention includes: use amphiphilic block copolymers and polyvalent alcohol as the combination of polyether glycol or alicyclic polyol, to obtain the toughness of obtained heat curable composition, balance good between mechanical property and thermotolerance.When with without polyvalent alcohol, when the prior art system as polyether glycol or alicyclic polyol compares, composition exhibiting of the present invention goes out the toughness significantly improved relative to prior art system.

Accompanying drawing describes

In order to the present invention is described, and be not limited by it, provide the following drawings to show the present invention of a kind of form in this article, wherein:

Fig. 1 is that display flexural strength is as toughness (K _ic) the graphic extension of function.

Fig. 2 is that display tensile strength is as toughness (K _ic) the graphic extension of function.

Fig. 3 is that the strain of display faulted flexure is as toughness (K _ic) the graphic extension of function.

Fig. 4 is that display tensile fracture elongation rate is as toughness (K _ic) the graphic extension of function.

Fig. 5 is that display Tg is as toughness (K _ic) the graphic extension of function.

Fig. 1-5 demonstrates: when preparing thermosetting product by the heat curable composition comprising at least one amphiphilic block copolymers and at least one polyvalent alcohol mixed with at least one epoxy resin, the machinery of the thermosetting product obtained or the unexpected synergy of thermal property.

Embodiment

In the following detailed description, particular of the present invention describes together with its preferred embodiment.But, being specifically such degree reaching following description for the particular of this technology or specific use, being intended to be only exemplary, and the concise and to the point description of exemplary is only provided.Therefore, the invention is not restricted to particular described below, but; The present invention includes drop in the true scope of appended claim all substitute, change and equivalence.

Unless otherwise mentioned, compound or component self are comprised to compound or mentioning of component, and with the combination of other compound or component, as the combination of mixture or compound.

As used herein, unless context explicitly points out, otherwise singulative " ", " one " and " described " comprise complex reference (reference).

An object of the present invention is to provide a kind of heat-curable resin composition, described heat-curable resin composition comprises amphiphilic block copolymers, polyvalent alcohol, acid anhydrides, epoxide, catalyzer, and optionally comprises mineral filler.

Another object of the present invention improves heat-curable resin composition as the mechanical property of epoxy/acid anhydrides heat curable composition, and especially toughness and physical strength, keep high heat resistance simultaneously.Amphiphilic block copolymers and polyvalent alcohol improve the physical strength of mechanical property as higher toughness and Geng Gao significantly to the combination in heat-curable resin composition, and do not have significant negative impact to second-order transition temperature.

Yet another object of the invention is to provide a kind of thermosetting product of solidification, and the thermosetting product of described solidification has the mechanical property of raising (such as, higher toughness and physical strength), keeps good thermotolerance and good processibility simultaneously.The high tenacity of product of the present invention and high mechanical strength provide less crackle and high mechanical integrity, thus reduce the quantity of defect and improve reliability and the life-span of the finished product.In addition, high heat resistance makes it possible to use composition of the present invention under High Operating Temperature.

Another object of the present invention improves the curable compositions in following middle use: casting, potting and encapsulation are as electricity and electronic application; Such as electroforming is moulded/is coated with and package application and composite coating.The present invention may be used in the application needing high tenacity.The example of these application comprises the application of matrix material, laminating material or reactive coating.

In its maximum range, the present invention relates to a kind of curable or heat curable composition, described curable or heat curable composition comprises: (a) at least one amphiphilic block copolymers, (b) at least one polyvalent alcohol, c () at least one per molecule on average contains the epoxy resin of at least two oxyethane rings, d () at least one per molecule on average contains the anhydride hardener of at least one anhydride rings, and (e) at least one catalyzer.

In the present invention, the utilization of the combination of amphiphilic block copolymers and polyvalent alcohol advantageously provides the improvement in mechanical property to heat curable composition, increases its toughness simultaneously and does not reduce its thermostability significantly.Prior art did not also use the combination of component of the present invention as the combination of amphiphilic block copolymers and polyvalent alcohol.

Operable amphiphilic block copolymers in the present invention, namely component (a) can comprise various amphiphilic block copolymers as such as, by quoting the amphiphilic polymers adding and describe in United States Patent (USP) 6,887,574 herein and WO2006/052727.Such as, the amphiphilic polyether block copolymer used in embodiment disclosed herein can comprise any containing epoxy resin can miscible block segments and epoxy resin can not the segmented copolymer of miscible block segments.

In some embodiments, suitable segmented copolymer comprises amphiphilic polyethers Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock as such as, poly-(oxyethane)-embedding-poly-(butylene oxide ring) (PEO-PBO) or amphiphilic polyethers triblock copolymer as, such as, poly-(oxyethane)-embedding-poly-(butylene oxide ring)-embedding-poly-(oxyethane) (PEO-PBO-PEO).

Other suitable amphiphilic block copolymers comprises, such as, poly-(oxyethane)-embedding-poly-(ethene-alternately (alt) propylene) (PEO-PEP), poly-(isoprene-oxyethane) segmented copolymer (embedding-PEO of PI-), poly-(ethylene, propylene-embedding-oxyethane) segmented copolymer (embedding-PEO of PEP-), poly-(divinyl-embedding-oxyethane) segmented copolymer (embedding-PEO of PB-), poly-(isoprene-embedding-oxyethane-embedding-isoprene) segmented copolymer (embedding-PEO-PI of PI-), poly-(isoprene-embedding-oxyethane-embedding-methyl methacrylate) segmented copolymer (embedding-PMMA of the embedding-PEO-of PI-), and composition thereof.

PCT patent application open WO2006/052725, WO2006/052726, WO2006/052727, WO2006/052729, WO2006/052730 and WO2005/097893, United States Patent (USP) 6,887,574 and U.S. Patent Application Publication 20040247881 in disclose other operable amphiphilic block copolymers; Each in these documents adds herein by quoting.

The preferred embodiment of above segmented copolymer is the mixture of poly-(oxyethane)-embedding-poly-(butylene oxide ring) (embedding-PBO of PEO-) amphiphilic block copolymers, the embedding-PBO-of PEO-embedding-PEO amphiphilic block copolymers and embedding-PBO of PEO-and the embedding-PEO of the embedding-PBO-of PEO-.In the present invention, other example of operable segmented copolymer comprises segmented copolymer as the polyether silicon by quoting described in the U.S. Patent Publication sequence number 61/014,560 (attorney file number 65822) being called " comprising the thermoset composition of polyether silicon; their preparation and use (ThermosettingCompositionsComprisingSiliconePolyethers; TheirManufacture; andUses) " in the name submitted on July 13rd, 2007 by Valette etc. that adds herein.

Amphiphilic copolymers has at least two kinds of block segments, a kind of with epoxy resin can miscible and another kind of can not miscible with epoxy resin.Usually, available in the present invention amphiphilic block copolymers comprise containing at least one epoxy resin can miscible block segments and at least one epoxy resin can not the amphiphilic block copolymers of miscible block segments.In one embodiment of the invention, miscible block segments can not comprise at least one polyether structure, condition describedly the polyether structure of miscible block segments can not contain at least one or the multiple alkylene oxide monomer units with at least four carbon atom.Therefore, the amphiphilic block copolymers (a) of said composition be containing at least one epoxy resin can miscible block segments and at least one epoxy resin can not the amphiphilic polyether block copolymer of miscible block segments; Wherein saidly miscible block segments can comprise at least one polyether structure.

Usually, amphiphilic block copolymers can miscible segment and amphiphilic block copolymers can not the ratio of miscible segment be about 10: 1 to about 1: 10.

The amphiphilic block copolymers of said composition is preferably selected from the group be made up of the following: diblock, line style three block, line style four block, more higher order multiblock structure; Branched block structure; Or star block structure.

An embodiment of said composition contains amphiphilic block copolymers, wherein saidly miscible block segments can contain poly-ethylene oxide block, propylene oxide block or poly-(oxyethane-altogether-propylene oxide) block; And preferably wherein amphiphilic block copolymers (a) can at least one of miscible segment be poly-(oxyethane).Miscible block segments can not can containing polybutylene oxide block, poly-oxepane block, gather Epoxydodecane block or poly-epoxyhexadecane block of amphiphilic block copolymers, and preferably, wherein said amphiphilic block copolymers (a) can not at least one of miscible segment be poly-(butylene oxide ring).

In composition of the present invention, the example more specifically of operable amphiphilic block copolymers can comprise poly-(oxyethane)-embedding-poly-(butylene oxide ring) or poly-(oxyethane)-embedding-poly-(butylene oxide ring)-embedding-poly-(oxyethane); And be preferably poly-(oxyethane)-embedding-poly-(oxepane).

In another embodiment, composition of the present invention can containing the amphiphilic block copolymers (a) of blend comprising two or more segmented copolymer.

Usually, the amphiphilic block copolymers (a) used in said composition can have the molecular weight of about 1000 to about 30000;

The amount of the amphiphilic block copolymers used in heat curable composition described herein can depend on the various factors comprising the following: the equivalent of polymkeric substance, and the desired properties of the product manufactured by described composition.Usually, based on the weight of whole organic compound, the concentration of amphiphilic block copolymers (a) can in the scope between about 0.1 % by weight to about 20 % by weight, preferably between about 0.2 % by weight to about 15 % by weight, more preferably from about between 0.3 % by weight to about 10 % by weight, and most preferably from about between 0.4 % by weight to about 8 % by weight.If the concentration of amphiphilic block copolymers is higher than 20 % by weight, then mechanical property reduces significantly.If this concentration is lower than 0.1 % by weight, then further do not improve in the toughness of obtained composite prod.

Usually, polyvalent alcohol available in the present invention, namely component (b) can be any one of known polyvalent alcohol known in the art.Preferably, polyvalent alcohol can be aliphatic polyol.Aliphatic polyol can contain 2 to about 20 carbon atoms.In one embodiment, aliphatic polyol can be selected from the group of linear aliphatic polyvalent alcohol and branched aliphatic polyvalent alcohol.

In preferred embodiments, polyvalent alcohol can be alicyclic polyol, and more preferably, described alicyclic polyol can contain 6 to about 20 carbon atoms.Alicyclic polyol can comprise such as 1,3-CHDM, 1,4 cyclohexane dimethanol or its mixture; Wherein the weight percent of 1,4 cyclohexane dimethanol can be 0% to about 100%.

As the example of one embodiment of the invention, polyol component (b) available in the present invention can be the compound of following formula (I):

Formula (I)

Wherein X be hydrogen, the branched-chain or straight-chain alkyl of 1 to about 10 carbon atom or the alkyl of 1 to about 10 carbon atom that is optionally substituted by a hydroxyl group, and n is the integer of 1 to about 200.

Polyvalent alcohol, namely the average hydroxyl equivalent of component (b) is between 20 to 10000, preferably between 30 to 4000, more preferably between 40 to 2000, and most preferably between 100 to 500.The average hydroxy functionality of polyvalent alcohol strictly higher than 1, preferably higher than 1.2, more preferably higher than 1.5.The average hydroxy functionality of polyvalent alcohol lower than 10, preferably lower than 6, more preferably less than 4.Most preferred average hydroxy functionality is about 2.

Based on the weight of whole organic compound, the concentration of polyvalent alcohol can be selected between 0.1% to 40%, preferably between 0.2% to 20%, more preferably between 0.3% to 15%, and most preferably between 0.5% to 10%.If the concentration of polyvalent alcohol is higher than 40%, then second-order transition temperature reduces significantly.If the concentration of polyvalent alcohol is lower than 0.1%, be not then significantly improved in mechanical property, and have loss in toughness.

The weight ratio of amphiphilic block polymer (a) and polyvalent alcohol (b), between 50: 1 to 1: 50, preferably between 20: 1 to 1: 40, more preferably between 15: 1 to 1: 30, and is most preferably selected between 10: 1 to 1: 20.Higher or lower than these scopes, the synergy observed between polyvalent alcohol to segmented copolymer is no longer visible and its performance is similar to the performance obtained with one-component.

Heat curable composition of the present invention comprises at least one epoxy resin ingredient (c).Epoxy resin is the compound containing at least one vicinal epoxy group.Epoxy resin can be saturated or unsaturated, aliphatic, alicyclic, aromatics or heterocycle and can be substituted.Epoxy resin also can be monomer or polymerization.

Preferred epoxy component is polyepoxide.Polyepoxide used herein refers to the mixture of compound containing more than one epoxy moieties or compound.Polyepoxide used herein comprises (advanced) epoxy resin that part increases, i.e. the reaction of polyepoxide and chain extension agent, wherein reaction product per molecule on average has more than one unreacted epoxide unit.Aliphatic polyepoxide can be prepared by the known response of epihalohydrin and polyoxyethylene glycol.Other specific examples of aliphatic epoxide comprises trimethyl propane epoxide, and diglycidyl-1,2-cyclohexane cyclohexanedimethanodibasic ester.Operable preferred compound comprises herein, epoxy resin is as such as, the glycidyl ether of polyphenol, namely per molecule on average has the compound of more than one aromatic hydroxy, such as, the phenol-hydrocarbon resin of the novolac resin of dihydroxyl phenol, biphenol, bis-phenol, halo biphenol, halogenated bisphenol, alkylation biphenol, alkylated bisphenols, trisphenol, novolac resin, replacement, phenol-hydrocarbon resin, replacement and any combination thereof.

Optionally, the epoxy resin used in resin combination of the present invention is at least one halo or halogen-containing epoxy resin compound.Halogen-containing epoxy resin is the compound containing at least one vicinal epoxy group and at least one halogen.Halogen can be, such as, and chlorine or bromine, and be preferably bromine.Herein can the example of halogen-containing epoxy resin comprise diglycidylether and the derivative thereof of tetrabromo-bisphenol.Epoxy resin available in the present invention comprises the commercially available commercially available resin from Dow Chemical (TheDowChemicalCompany) as D.E.R. ^tM500 series.

Halogen-containing epoxy resin can be used alone, and uses with one or more other halogen-containing epoxy composite, or uses from one or more other different not halogen-containing epoxy composite.Preferably select the ratio of halogenated epoxy resin and non-halogenated epoxy resin, to provide flame retardant resistance for the heat reactive resin of solidification.As known in the art, the weight of the halogenated epoxy resin that can exist can depend on used specified chemical structure (content of halogen due in halogenated epoxy resin) and change.It also depends on other fire retardant, comprises solidifying agent and optional additive and may be present in the fact in composition.Preferred halogenated flame is brominated compound, the diglycidylether of preferred tetrabromo-bisphenol and derivative thereof.

The epoxy resin compound being different from halogen-containing epoxy resin available in composition of the present invention can be such as, by epihalohydrin and phenol or prepared by phenolic compound, prepared by epihalohydrin and amine, prepared by epihalohydrin and carboxylic acid or the combination of the epoxy resin prepared by the oxidation of unsaturated compound or epoxy resin.

In one embodiment, the epoxy resin used in composition of the present invention comprises those resins prepared by epihalohydrin and phenol or phenolic compound.Phenolic compound comprises the compound that per molecule on average has more than one aromatic hydroxy.The example of phenolic compound comprises dihydric phenol, biphenol, bis-phenol, halo biphenol, halogenated bisphenol, A Hydrogenated Bisphenol A, alkylation biphenol, alkylated bisphenols, triphenol, resol, novolac resin (the i.e. reaction product of phenols and simple aldehydes, described simple aldehydes is preferably formaldehyde), halo novolac resin, the novolac resin replaced, phenol-hydrocarbon resin, phenol-the hydrocarbon resin replaced, phenol-hydroxybenzaldehyde resins, alkylating phenol-hydroxybenzaldehyde resins, hydrocarbon-phenol resin, hydrocarbon-halogenated phenol resins, hydrocarbon-alkylating phenol resin, or their combination.

In another embodiment, the epoxy resin used in composition of the present invention preferably includes those resins manufactured by epihalohydrin and the following: bis-phenol, halogenated bisphenol, A Hydrogenated Bisphenol A, novolac resin and polyalkylene glycol, or its combination.The example of the epoxy resin based on dihydroxyphenyl propane available in the present invention comprises the commercially available commercially available resin from Dow Chemical as D.E.R. ^tM300 series and D.E.R. ^tM600 series.Epoxy-Novolak resin available in the present invention comprises the commercially available commercially available resin from Dow Chemical as D.E.N. ^tM400 series.

In another embodiment, epoxy resin compound available in composition of the present invention preferably includes those resins prepared by epihalohydrin and the following: Resorcinol, pyrocatechol, quinhydrones, biphenol, dihydroxyphenyl propane, bisphenol-ap (1, two (4-hydroxy phenyl)-1-diphenylphosphino ethane of 1-), Bisphenol F, bis-phenol K, tetrabromo-bisphenol, phenol-formaldehyde novolaRs resin, the phenol-formaldehyde resin that alkyl replaces, phenol-hydroxybenzaldehyde resins, cresol-hydroxybenzaldehyde resin, Dicyclopentadiene (DCPD)-phenol resins, the phenol resins of Dicyclopentadiene (DCPD)-replacement, tetramethyl-biphenol, tetramethyl--tetrabromo biphenol, tetramethyl-tribromo biphenol, tetrachlorobisphenol A, or their combination.Preferably, composition epoxy resin of the present invention contains the diglycidylether of tetrabromo-bisphenol.

Being prepared in of this compound is known in the art.See Kirk-Othmer, encyclopedia of chemical technology (EncyclopediaofChemicalTechnology), the 3rd edition, the 9th volume, 267-289 page.Such as, adding United States Patent (USP) 5,137,990 and 6,451 herein by quoting, in 898, also describing the example being applicable to epoxy resin and their precursor used in the present compositions.

In another embodiment, in composition of the present invention, operable epoxy resin comprises those resins prepared by epihalohydrin and amine.Suitable amine comprises diaminodiphenylmethane, amino-phenol, dimethylphenylene diamine, phenyl amines etc., or its composition.

In another embodiment, in composition of the present invention, available epoxy resin comprises those resins prepared by epihalohydrin and carboxylic acid.Suitable carboxylic acid comprises phthalic acid, m-phthalic acid, terephthalic acid, tetrahydro--and/or hexahydro-phthalic acid, interior methyne tetrahydrophthalic acid, m-phthalic acid, methylhexahydrophthalic acid etc., or its combination.

In another embodiment, epoxy resin refers to the epoxy resin of growth, and it is that one or more epoxy resin ingredient as above have the reaction product of the compound of more than one aliphatic hydroxide radical with one or more phenolic compounds as above and/or one or more per molecule on average.Alternatively, epoxy resin can with the hydrocarbon reaction of carboxyl substituted, the hydrocarbon of described carboxyl substituted is described to such compound herein, it has hydrocarbon skeleton, preferred C1-C40 hydrocarbon skeleton, and one or more carboxy moiety, preferably more than one, and most preferably two.C1-C40 hydrocarbon skeleton can be alkane or the alkene of straight chain or side chain, optionally containing aerobic.Lipid acid and lipid acid dimer belong to the hydrocarbon of (areamong) available carboxylic acid-substituted.Lipid acid comprises caproic acid, caprylic acid (caprylicacid), capric acid, sad (octanoicacid), capric acid (decanoicacid), lauric acid, tetradecanoic acid, palmitinic acid, stearic acid, Zoomeric acid, oleic acid, linolic acid, linolenic acid, erucic acid, pentadecanoic acid, margaric acid, eicosanoic acid, and their dimer.

Epoxy resin of the present invention, namely component (a) can be selected from, such as, oligomeric and polymerization dihydroxyphenyl propane diglycidylether, oligomeric and polymerization tetrabromo-bisphenol diglycidylether, oligomeric and polymerization dihydroxyphenyl propane and the diglycidylether of tetrabromo-bisphenol, epoxidised phenol novolacs, epoxidised bisphenol A novolac, the epoxy resin of oxazolidone modification, and composition thereof.

In another embodiment, epoxy resin is polyepoxide and contains the compound of more than one isocyanate moiety or the reaction product of polyisocyanates.Preferably, the epoxy resin prepared in this reaction is epoxy-capped gathering oxazolidone.

Anhydride hardener, namely component (d) comprises Tetra hydro Phthalic anhydride and derivative, Na Dike (nadic) acid anhydrides and derivative, trimellitic acid 1,2-anhydride and derivative, pyromellitic dianhydride and derivative, benzophenone tetracarboxylic acid anhydride and derivative, dodecenylsuccinic anhydride and derivative, gathers (ethyl octadecyl diacid) acid anhydride and derivative etc., and these can be used alone or use in the form of their mixtures.Hexahydro phthalic anhydride, methyl hexahydro phthalic anhydride, tetrahydronaphthalic anhydride, methyl nadic anhydride, carbic anhydride and methylnadic anhydride are particularly suitable for the present invention.

The mol ratio of epoxy resin (c) and anhydride hardener (d), between 2: 1 to 1: 2, preferably between 1.5: 1 to 1: 1.5, is more preferably selected between 1.3: 1 to 1: 1.2, and most preferably is about 1.05: 1.Higher or lower than these scopes, the peak rate of conversion of active group is restricted.Residual active group (if this ratio is higher than 2: and if 1 for this ratio of epoxide group be anhydride group lower than 1: 2) stay in the network of solidification, cause the harmful effect to material property (such as lower Tg, the mechanical property of reduction and chemical stability).

Specially suitable catalyzer available in the present invention, namely component (e) is those seasons with ammonium compound as such as, ethyltriphenylphosphonium chloride , ethyltriphenylphosphonium bromide , ethyltriphenylphosphonium iodide , acetic triphenyl , oxalic acid ethyl triphenyl (acetic triphenyl . acetic acid complex), four halogen boric acid ethyl triphenyl , the chlorination tetrabutyl , tetrabutylphosphoniuacetate acetate , the oxalic acid tetrabutyl (tetrabutylphosphoniuacetate acetate . acetic acid complex), the four halogen boric acid tetrabutyls , butyl triphenyl tetrabromobisphenol salt, butyl triphenyl bisphenolate salt, butyl triphenyl supercarbonate, zephiran chloride trimethyl ammonium, hydroxide benzyltrimethylammon.um, tetrabromo boric acid benzyltrimethylammon.um, tetramethyl ammonium hydroxide, tetrabutylammonium, four halogen boric acid TBuAs, and composition thereof, etc.

Other suitable catalyzer (e) comprises ammonium compound as such as, chlorination triethyl ammonium, bromination triethyl ammonium, iodate triethyl ammonium, four halogen boric acid triethyl ammoniums, chlorination tributyl ammonium, bromination tributyl ammonium, iodate tributyl ammonium, four halogen boric acid tributyl ammonium, N, N '-dimethyl-1,2-diaminoethanes. four halogen borate complex, and composition thereof, etc.

Other suitable catalyzer (e) comprise season and tertiary amine, with with suitable non-nucleophilic acid as, such as, the adducts of fluoroboric acid, fluorine arsenic acid, fluorine metaantimmonic acid, hexafluorophosphoric acid, perchloric acid, hyperbromic acid, Periodic acid or title complex, and composition thereof, etc.

Other suitable catalyzer (e) comprises tertiary amine as such as, triethylamine, tripropyl amine, Tributylamine, glyoxal ethyline, benzyldimethylamine, and composition thereof, etc.

Based on the weight of whole organic compound, the concentration of catalyzer (e) is usually between about 0.001 % by weight to about 10 % by weight, and preferably about 0.01% to about between 5%, and more preferably from about 0.1% to about between 2%.Higher than this scope, react too fast and said preparation can not be processed under typical processing conditions.Lower than this scope, reacted slow and said preparation can not be processed under typical processing conditions.

Heat curable composition of the present invention optionally can also comprise one or more fillers or fiber enhancer.When said composition contains mineral filler, mineral filler can be selected from any conventional inorganic filler.The example of this mineral filler includes, but are not limited to: silicon-dioxide, talcum, quartz, mica, and fire-retardant filler is as aluminium hydroxide, three aluminium hydroxides (aluminumtrihydroxide), magnesium hydroxide or boehmite.Preferably, mineral filler can be silicon-dioxide and talcum, and composition thereof.

Based on the gross weight of composition, the concentration of filler as mineral filler is preferably selected from about 1% to about between 95%, and preferably about 2% to about between 90%, and more preferably from about 10% to about between 85%, even more preferably from about 20% to about between 80%, and even more preferably from about 30% to about between 75%.

Usually, at least one mean sizes of inorganic filler particle lower than about 1mm, preferably lower than about 100 microns, more preferably less than about 50 microns, and again more preferably less than about 10 microns, and higher than about 2nm, preferably higher than about 10nm, more preferably higher than about 20nm, and more more preferably higher than about 50nm.The filler being greater than 100 microns causes defect in thermoset network, thus causes the thermomechanical property of difference.

Heat curable composition of the present invention optionally can also comprise the second different from epoxy resin (c) and different with stiffening agent (d) reactive resins.The second reactive resin available in the present invention can form a part for cross-linked network.The example of these resins comprises isocyanate resin class, (methyl) crylic acid resin, resol class, melamine resin class, ethenoid resin class, vinyl ester resin class, styrene resin lipid, silicone resin class and polyester resin.Stiffening agent can select, but is not limited to, amine, resol class, carboxylic-acid and polyol resin class.Reactive resin comprises in the embodiment of isocyanic ester wherein, and at least one stiffening agent is preferably selected from polyvalent alcohol.

Based on the weight of whole organic compound, the concentration of other reactive resin is generally between about 0.5 % by weight to about 50 % by weight, and preferably about 1% to about between 40%, and more preferably from about 2% to about between 30%, and most preferably from about 5% to about between 25%.Higher than 50%, other reactive resin becomes main resin.Lower than 0.5%, concentration is enough large to such an extent as to can not produce the difference of performance.

Heat curable composition of the present invention optionally can also comprise at least one solvent.Solvent available in the present invention can comprise such as ketone, alcohols, water, gylcol ether, aromatic hydrocarbon and composition thereof.Preferred solvent comprises acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), pimelinketone, methyl-2-pyrrolidone, propylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, Methyl amyl ketone, methyl alcohol, Virahol, toluene, dimethylbenzene, dimethyl formamide (DMF) etc.Single solvent can be used, but also can use independent solvent to one or more components.Preferred solvent for epoxy resin and solidifying agent is ketone, comprise acetone, methyl ethyl ketone etc., and ether alcohol class is as the methyl of ethylene glycol, glycol ether, propylene glycol or dipropylene glycol, ethyl, propyl group or butyl ether, ethylene glycol monomethyl ether or 1-methoxy-2-propanol, and the acetic ester of correspondence.Preferred solvent for catalyzer of the present invention comprises alcohols, ketone, water, dimethyl formamide (DMF), glycol ethers as propylene glycol monomethyl ether or ethylene glycol monomethyl ether, and combination.

Based on the weight of whole organic compound, the concentration of solvent is generally about 0% to about between 80%, and preferably about 1% to about between 60%, and more preferably from about 2% to about between 50%, and most preferably from about 5% to about between 40%.

Optionally one or more additives can be also comprised according to heat curable composition of the present invention, described additive is selected from: other fire retardant, and different from amphiphilic block copolymers (a) other toughness reinforcing reagent, the polyvalent alcohol different with polyvalent alcohol (b) and glycols, curing inhibitors, wetting agent, tinting material, thermoplastics, processing aid, dyestuff, UV stop compound and fluorescent chemicals; And composition thereof.This inventory means exemplary instead of restrictive.Preferable additives for formula of the present invention can be optimized by those skilled in the art.

Based on the weight of whole composition, the concentration of other additive is generally between about 0 % by weight to about 50 % by weight, preferably between about 0.01 % by weight to about 20 % by weight, more preferably from about between 0.05 % by weight to about 15 % by weight, and most preferably from about between 0.1 % by weight to about 10 % by weight.Lower than about 0.01 % by weight, additive can not provide any further remarkable benefit usually to obtained thermosetting product; And higher than about 20 % by weight, the improved properties brought by these additives keeps relative constancy.

Thermosetting product of the present invention (namely by heat curable composition manufacture crosslinked) second-order transition temperature that demonstrates is higher than about 70 DEG C, preferably higher than about 80 DEG C, more preferably higher than about 90 DEG C, more preferably higher than about 100 DEG C, and most preferably higher than about 110 DEG C.The second-order transition temperature that thermosetting product of the present invention demonstrates lower than 300 DEG C, preferably lower than 280 DEG C, more preferably less than 250 DEG C, and most preferably lower than 230 DEG C.In one embodiment, the second-order transition temperature that thermosetting product of the present invention demonstrates is about 70 DEG C to about 300 DEG C.Lower than about 70 DEG C, the routine techniques described in the technology hinge structure described in the application does not provide any further obvious benefit; And higher than about 300 DEG C, the technology described in the application will cause very frangible network usually, and this is not suitable for the application within the scope of the application.

When with 50 % by weight silica filler preparation time, thermosetting product of the present invention demonstrate by K _1cthe toughness that value is measured is higher than about 1.0MPa.m ^1/2, preferably higher than about 1.2MPa.m ^1/2, more preferably higher than about 1.4MPa.m ^1/2, more preferably higher than about 1.6MPa.m ^1/2, and most preferably higher than about 1.8MPa.m ^1/2.Lower than K _1cvalue scope is about 1.0MPa.m ^1/2, relative conventional composition there is no additional benefits of the present invention or advantage.When with 50 % by weight silica filler preparation time, thermosetting product of the present invention demonstrate by K _1cthe toughness that value is measured is lower than 5.0MPa.m ^1/2, preferably lower than 4.0MPa.m ^1/2, more preferably less than 3.5MPa.m ^1/2, and most preferably lower than 3.0MPa.m ^1/2.In one embodiment, thermosetting product of the present invention demonstrate by K _1cthe toughness that value is measured is about 1.0MPa.m ^1/2to about 5.0MPa.m ^1/2.Lower than about 1.0MPa.m ^1/2, the technology described in the application can not provide any further obvious benefit relative to routine techniques of the prior art; And higher than about 5.0MPa.m ^1/2, the technology described in the application will cause the network being similar to thermoplastics usually, and this is not suitable for the application within the scope of the application.

When with 50 % by weight silica filler preparation time, the tensile strength that thermosetting product of the present invention demonstrates higher than about 40MPa, preferably higher than about 60MPa, more preferably higher than about 70MPa, and most preferably higher than about 75MPa.When with 50 % by weight silica filler preparation time, the tensile strength that thermosetting product of the present invention demonstrates lower than about 500MPa, preferably lower than 400MPa, more preferably less than 300MPa, and most preferably higher than 150MPa.In one embodiment, the tensile strength that thermosetting product of the present invention demonstrates is about 40MPa to about 500MPa.Lower than about 40MPa, relative conventional composition there is no additional benefits of the present invention or advantage; And higher than about 500MPa, the technology described in the application will cause very frangible network usually, and this is not suitable for the application within the scope of the application.

When with 50 % by weight silica filler preparation time, the flexural strength that thermosetting product of the present invention demonstrates higher than 120MPa, preferably higher than 125MPa, more preferably higher than 130MPa, and most preferably higher than 135MPa.When with 50 % by weight silica filler preparation time, the flexural strength that thermosetting product of the present invention demonstrates lower than about 500MPa, preferably lower than 400MPa, more preferably less than 300MPa, and most preferably higher than 200MPa.In one embodiment, the flexural strength that thermosetting product of the present invention demonstrates is about 120MPa to about 500MPa.Lower than about 120MPa, the technology described in the application can not provide any further obvious benefit relative to routine techniques of the prior art; And higher than about 500MPa, the technology described in the application will cause very frangible network usually, and this is not suitable for the application within the scope of the application.

When with 50 % by weight silica filler preparation time, the elongation at break that thermosetting product of the present invention demonstrates higher than about 1.5%, preferably higher than about 1.6%, more preferably higher than about 1.8%, and most preferably higher than about 2.0%.When with 50 % by weight silica filler preparation time, the elongation at break that thermosetting product of the present invention demonstrates lower than about 100%, preferably lower than about 80%, more preferably less than about 50%, and most preferably lower than about 20%.Lower than about 1.5%, relative conventional composition there is no additional benefits of the present invention or advantage; And higher than about 100%, the technology described in the application will cause the network being similar to thermoplastics usually, and this is not suitable for the application within the scope of the application.

The component of preparation of the present invention or composition can be mixed with any order to provide heat curable composition of the present invention.

The preparation of the present composition containing amphiphilic block copolymers, polyvalent alcohol, acid anhydrides, catalyzer and epoxide can be solidified to form thermosetting resin under typical processing conditions.The thermosetting resin obtained demonstrates excellent thermomechanical property, as good toughness and physical strength, keeps high thermostability simultaneously.

The method being used for preparing thermosetting product of the present invention can be undertaken by gravity casting, vacuum casting, automatic pressure gel (APG), vacuum pressure gelation (VPG), perfusion, filament winding, lay-up injection, transfer molding etc.

The temperature of solidification heat curable composition can be selected between about 20 DEG C to about 300 DEG C, preferably between about 25 DEG C to about 250 DEG C, and more preferably from about between 30 DEG C to about 220 DEG C usually.Lower than about 20 DEG C, temperature may be too low and can not guarantee reaction enough fast under typical processing conditions; And higher than about 300 DEG C, the too high and thermal curable material of temperature may be degraded.

Usually above about 40 DEG C, preferably higher than about 50 DEG C, more preferably higher than about 60 DEG C, more more preferably higher than about 70 DEG C, and most preferably higher than the temperature of about 80 DEG C, the gelation of heat curable composition can be carried out.Can about 300 DEG C be usually less than, preferably lower than about 280 DEG C, more preferably less than about 250 DEG C, then more preferably less than about 220 DEG C, and most preferably lower than the temperature of about 180 DEG C, carry out the gelation of heat curable composition.In one embodiment, usually the temperature of about 40 DEG C to about 300 DEG C, the gelation of heat curable composition is carried out.Lower than about 40 DEG C, temperature may be too low and can not guarantee reaction enough fast under typical processing conditions.Higher than about 300 DEG C, the too high and thermosetting material of temperature may be degraded, potential evaporation, or gelation may be too fast and may produce internal stress and defect.

Usually above about 100 DEG C, preferably higher than about 110 DEG C, more preferably higher than about 120 DEG C, more more preferably higher than about 130 DEG C, and most preferably higher than the temperature of about 140 DEG C, the after fixing of heat curable composition can be carried out.Can about 300 DEG C be usually less than, preferably lower than about 280 DEG C, more preferably less than about 260 DEG C, then more preferably less than about 250 DEG C, and most preferably lower than the temperature of about 240 DEG C, carry out the after fixing of heat curable composition.In one embodiment, usually the temperature of about 100 DEG C to about 300 DEG C, the after fixing of heat curable composition can be carried out.Lower than about 100 DEG C, temperature may be too low and can not ensure enough cross-linking densities (incomplete reaction).Higher than about 300 DEG C, the too high and thermosetting material of temperature may be degraded, and may produce internal stress and defect.

In the predetermined time period of enough curing compositions, the solidification of heat curable composition can be carried out.Such as, can be selected from set time between about 1 minute to about 96 hours, preferably between about 5 minutes to about 48 hours, and more preferably from about between 10 minutes to about 24 hours.Be less than the time durations of 1 minute, the time may be too short and can not guarantee the abundant reaction under typical processing conditions; And more than 96 hours, the time was oversize and impracticable or uneconomical.

Preparation of the present invention is very suitable for casting, potting, encapsulation and dipping method.

Can use thermosetting product of the present invention in various applications, described application comprises: such as in casting, potting and encapsulation, as electricity or electronic application; Such as electroforming is moulded/is coated with and package application and composite coating.

Final thermosetting resin demonstrates excellent machinery and thermal property.When the mixture of amphiphilic block copolymers and polyvalent alcohol is to the remarkable negative impact be combined in not to second-order transition temperature in the epoxy-resin systems containing anhydride hardener and catalyzer, improve mechanical property significantly as higher toughness and physical strength.This preparation is very suitable for casting, potting, encapsulation and dipping method.Final thermosetting resin demonstrates excellent machinery and thermal property.

Embodiment

But following examples and comparative example further describe the present invention should not be interpreted as limiting scope of the present invention.

Explain the various terms, title and the starting material that use in following examples herein below:

Diglycidylether (DGEBA) liquid epoxies of DYD128 (changing together (DalianQihua) from Dalian) to be epoxy equivalent (weight) the be dihydroxyphenyl propane of 185.The viscosity of this epoxy resin is about 12000cP at 25 DEG C.

Purity is used to be that the methyl nadic anhydride (MTHPA) of 99% is as anhydride hardener (can derive from OrientChemicalCompany).

Poly-(oxyethane)-embedding--poly-(butylene oxide ring)-embedding--poly-(oxyethane) (PEO-PBO-PEO) is amphiphilic block copolymers.Poly-(oxyethane) block segments of this segmented copolymer is that epoxy can miscible block, and poly-(butylene oxide ring) block segments of this segmented copolymer is that epoxy can not miscible block.This amphiphilic block copolymers has the molecular weight of about 3000 and can derive from Dow Chemical.

First polyvalent alcohol is 50/50 mixture (CHDM) of 1,3-CHDM and 1,4 cyclohexane dimethanol, and can derive from Dow Chemical.

Second polyvalent alcohol to be molecular weight be 400 PEG (PEG), and can SinoChemicals be derived from.

Mineral filler is silica filler, and it has the lower granularity (d of 2 μm _10%), the middle granularity (d of 13 μm _50%) and the upper granularity (d of 52 μm _90%).The mean diameter of silica filler is , can JiuLiHua be derived from.

BYKA530 is used as defoamer, and can derive from BYK.

Following standard analysis device, method and test procedure is employed in embodiment:

ResearchEquipment (London) LTD cone and plate viscometer is measured 25 DEG C and 50 DEG C the viscosity of uncured preparation respectively.

Second-order transition temperature (Tg) is measured according to the code in ISO11357-2.

Tensile property is measured according to the code in ISO527.

Flexural property is measured according to the code in ISO178.

The fracture toughness property of characterizing epoxy resin is carried out according to the code critical stress intensity factor K1c in ASTMD5045-99.

Embodiment 1-4 and Comparative examples A-D

The preparation of several resin systems used in embodiment is described in Table I.

Table I. the preparation of resin system

Epoxy/stiffening agent (mol ratio)	1∶0.95	1∶0.95	1∶0.95	1∶0.95	1∶0.95	1∶0.95	1∶0.95	1∶0.95
									Preparation	Embodiment 1	Embodiment 2	Embodiment 3	Embodiment 4	Comparative examples A	Comparative example B	Comparative example C	Comparative Example D
DGEBA(g)	99.0	99.0	99.0	99.0	99.0	99.0	99.0	99.0
									MTHPA(g)	84.4	84.4	84.4	84.4	84.4	84.4	84.4	84.4
BYK A530(g)	1.0	1.0	1.0	1.0	1.0	1.0	1.0	1.0
									PEO-PBO-PEO(g)	3.8	1.9	3.8	3.8	3.8
CHDM(g)	9.4	9.4	4.7			9.4
									PEG(g)				9.4			9.4
Silica filler (g)	197.6	195.7	192.9	197.6	188.2	193.8	193.8	185.4
									Add up to	395.2	391.4	385.8	395.2	393.2	387.6	387.6	370.8

In above preparation in tablei, the content of silica filler is fixed as by all preparations to the concentration of 50 % by weight.Mol ratio between the epoxy component of preparation and hardener component is fixed on the mol ratio of about 1.05: 1 in all preparations.

In above preparation in tablei, first all organic constituents be blended together and use high-speed mixer (2000rpm, envrionment temperature, 30 minutes) to be blended in often kind of preparation by inorganic component afterwards.BYKDISPERMATWDB-1611 dispersion machine is used mineral filler to be dispersed in resin formulation.Afterwards that said preparation is degassed.In envrionment temperature, carry out degassed until do not have bubble visible in a vacuum.Mould is prepared between the sheet glass (glassplated) protected with releasing agent that insulate on Si sheet is clipped together.Said preparation is heated to 80 DEG C, then pours in mould, and SC is to avoid the embedding of air bubble.By the mould of solidification containing preparation, prepare casting part.By this casting part in an oven at 100 DEG C of solidifications, 2 hours (h), at 120 DEG C of solidification 2h and at 160 DEG C of solidification 2h.In order to avoid internal stress, casting part is cooled 2h in an oven lentamente.

According to before at the thermomechanical property of the solidification casting part of above-described regulae generales measurement amphiphilic block copolymers and the toughness reinforcing epoxy resin of alicyclic diol; And result display in table ii.

Table II. performance

Embodiment 1 compares with comparative example

When comparing with Comparative examples A, as by higher break-draw and flexural strength confirm, embodiment 1 brings higher physical strength.The toughness of embodiment 1 and elongation at break and transverse strain improve significantly.Relative to Comparative examples A, second-order transition temperature (Tg) is lowered.Tg is lowered, but this reduction is acceptable to application.

When comparing with comparative example B, as passed through higher K _1clower viscosity confirms, embodiment 1 brings better toughness and processibility.Elongation at break and transverse strain improve significantly.Tg is similar to those of comparative example B with physical strength.

When comparing with comparative example C, as by higher break-draw and flexural strength confirm, embodiment 1 brings higher physical strength.The elongation at break of embodiment 1 and transverse strain and toughness improve significantly.

When comparing with Comparative Example D, as by higher break-draw and flexural strength confirm, embodiment 1 brings higher physical strength.The toughness of embodiment 1 and elongation at break and transverse strain improve significantly.Tg is lowered, but this reduction is acceptable to application.

Embodiment 2 compares with comparative example

When comparing with Comparative examples A, as by higher break-draw and flexural strength confirm, embodiment 2 brings higher physical strength.The elongation at break of embodiment 1 and transverse strain improve.The toughness of embodiment 1 is similar to those of Comparative examples A with Tg.

When comparing with comparative example B, as passed through higher K _1cconfirm with Tg, embodiment 2 brings better toughness and thermotolerance.Elongation at break and transverse strain and processibility improve.The physical strength of embodiment 2 is similar to the physical strength of comparative example B.

When comparing with comparative example C, embodiment 2 brings higher physical strength, higher toughness, the elongation at break of higher Tg and Geng Gao and transverse strain.

When comparing with Comparative Example D, embodiment 2 brings much higher physical strength and toughness.Elongation at break and the transverse strain of embodiment 2 improve significantly.Tg is maintained.

Embodiment 3 compares with comparative example

When comparing with Comparative examples A, as by higher break-draw and flexural strength confirm, embodiment 3 brings higher physical strength.The elongation at break of embodiment 1 and transverse strain and viscosity improve.The toughness of embodiment 3 is similar to the toughness of Comparative examples A.

When comparing with comparative example B, as passed through higher K _1clower viscosity confirms, embodiment 3 brings better toughness and processibility.Elongation at break and transverse strain improve.The physical strength of embodiment 3 is similar to those of comparative example B with Tg.

When comparing with comparative example C, embodiment 3 brings the performance that all properties improves.

When comparing with Comparative Example D, embodiment 3 brings much higher physical strength and toughness.Elongation at break and the transverse strain of embodiment 3 improve significantly.

Embodiment 4 compares with comparative example

When comparing with Comparative examples A, as by higher break-draw and flexural strength and higher K _1Cconfirming, embodiment 4 brings higher physical strength and toughness.The elongation at break of embodiment 4 and transverse strain improve.

When comparing with comparative example B, as passed through higher K _1clower viscosity confirms, embodiment 4 brings better toughness and processibility.Elongation at break and transverse strain improve.The physical strength of embodiment 4 is similar to those of comparative example B with Tg.

When comparing with comparative example C, embodiment 4 brings better toughness and elongation at break and transverse strain.Physical strength, the processibility of embodiment 4 are similar to those of comparative example C with second-order transition temperature.

When comparing with Comparative Example D, embodiment 4 brings the performance improved on all properties in addition to t 9.Tg is lowered, but this reduction is acceptable to application.

Also can based on the data comparing embodiment described in Fig. 1-5.With reference to figure 1-5, show several embodiment of the present invention.These figure demonstrate when by amphiphilic block copolymers as such as PEO-PBO-PEO and polyhydric alcohols as when CHDM or PEG is blended together and joins in epoxy resin for the synergistic effect expected.When comparing with the prediction obtained by conventional rule of mixture (additivity matter), the machinery obtained or thermal property are excellent.

Fig. 1 shows flexural strength as toughness (K _ic) function.In FIG, for K _ic, experimental error is ± 0.025MPa.m ^1/2and for flexural strength, experimental error is ± 1.5MPa.Solid line represents the rule of mixture (additivity) between Comparative examples A (pure PEO-PBO-PEO) and comparative example B (pure CHDM).Dotted line represents the rule of mixture (additivity) between Comparative examples A (pure PEO-PBO-PEO) and comparative example C (pure PEG).

When comparing with the prediction obtained by conventional rule of mixture (additivity matter), the toughness (K of the system of the mixture containing PEO-PBO-PEO and polyvalent alcohol (CHDM or PEG) _ic) obviously better when at least maintaining similar flexural stress, or improving flexural stress significantly up to looking younger seemingly.

Fig. 2 shows flexural strength as toughness (K _ic) function.For K _ic, experimental error is ± 0.025MPa.m ^1/2and for tensile strength, experimental error is ± 0.5MPa.Solid line represents the rule of mixture (additivity) between Comparative examples A (pure PEO-PBO-PEO) and comparative example B (pure CHDM).Dotted line represents the rule of mixture (additivity) between Comparative examples A (pure PEO-PBO-PEO) and comparative example C (pure PEG).

When comparing with the prediction obtained by conventional rule of mixture (additivity matter), the toughness (K of the system of the mixture containing PEO-PBO-PEO and polyvalent alcohol (CHDM or PEG) _ic) obviously better when at least keeping similar tensile stress, or significantly increasing tensile stress up to looking younger seemingly.

Fig. 3 shows faulted flexure strain as toughness (K _ic) function.For K _icexperiment, error is ± 0.025MPa.m ^1/2and for transverse strain, experimental error is ± 0.05%.Solid line represents the rule of mixture (additivity) between Comparative examples A (pure PEO-PBO-PEO) and comparative example B (pure CHDM).Dotted line represents the rule of mixture (additivity) between Comparative examples A (pure PEO-PBO-PEO) and comparative example C (pure PEG).

When comparing with the prediction obtained by conventional rule of mixture (additivity matter), the toughness (K of the system of the mixture containing PEO-PBO-PEO and polyvalent alcohol (CHDM or PEG) _ic) obviously better when at least keeping similar transverse strain, or significantly increasing transverse strain up to looking younger seemingly.

Fig. 4 shows tensile fracture elongation rate as toughness (K _ic) function.For K _ic, experimental error is ± 0.025MPa.m ^1/2and for tensile elongation, experimental error is ± 0.05%.Solid line represents the rule of mixture (additivity) between Comparative examples A (pure PEO-PBO-PEO) and comparative example B (pure CHDM).Dotted line represents the rule of mixture (additivity) between Comparative examples A (pure PEO-PBO-PEO) and comparative example C (pure PEG).

When comparing with the prediction obtained by conventional rule of mixture (additivity matter), the toughness (K of the system of the mixture containing PEO-PBO-PEO and polyvalent alcohol (CHDM or PEG) _ic) obviously better when at least keeping similar tensile elongation, or significantly increasing tensile elongation up to looking younger seemingly.

Fig. 5 shows Tg as toughness (K _ic) function.For K _ic, experimental error is ± 0.025MPa.m ^1/2and for Tg, experimental error is ± 1 DEG C.Solid line represents the rule of mixture (additivity) between Comparative examples A (pure PEO-PBO-PEO) and comparative example B (pure CHDM).Dotted line represents the rule of mixture (additivity) between Comparative examples A (pure PEO-PBO-PEO) and comparative example C (pure PEG).

When comparing with the prediction obtained by conventional rule of mixture (additivity matter), the toughness (K of the system of the mixture containing PEO-PBO-PEO and polyvalent alcohol (CHDM or PEG) _ic) obviously better when at least keeping similar Tg, or when significantly increasing Tg up to looking younger seemingly.

It will be apparent to one skilled in the art that and can make some change to aforesaid method and not depart from the scope of the present invention.What therefore want is that all the elements disclosed herein should be construed as merely exemplary and not limit scope required for protection.In addition, the specific embodiment that the present invention is not stated above, comprises the restriction of the form mentioned by them.More properly, these embodiments and the form mentioned by them are examples of the present invention.

Claims

1. a heat curable composition, described heat curable composition comprises:

(a) at least one amphiphilic block copolymers, wherein said amphiphilic block copolymers be containing at least one epoxy resin can miscible block segments and at least one epoxy resin can not the amphiphilic polyether block copolymer of miscible block segments; Wherein saidly miscible block segments can not comprise at least one polyether structure, condition describedly the described polyether structure of miscible block segments can not contain at least one or the multiple alkylene oxide monomer units with at least four carbon atom, wherein said amphiphilic block copolymers (a) has the molecular weight of 1000 to 30000

(b) at least one polyvalent alcohol, wherein said polyvalent alcohol is the alicyclic polyol with 6 to 20 carbon atoms, wherein said alicyclic polyol comprises 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol or their mixture, wherein % by weight of 1,4 cyclohexane dimethanol is 0 % by weight to 100 % by weight

C () at least one per molecule on average contains the epoxy resin of at least 2 oxyethane rings,

D () at least one per molecule on average contains the anhydride hardener of at least 1 anhydride rings, and

(e) at least one catalyzer,

Wherein said amphiphilic block copolymers (a) with based on the weight of whole organic compound be 0.1 % by weight to 20 % by weight amount exist,

Described polyvalent alcohol (b) with based on the weight of whole organic compound be 0.1 % by weight to 40 % by weight amount exist,

Described amphiphilic block copolymers (a) is selected from 20: 1 to 1: 40 with the weight ratio of described polyvalent alcohol (b),

The mol ratio of described epoxy resin (c) and anhydride hardener (d) is selected between 2: 1 to 1: 2, and

Wherein said heat curable composition forms thermosetting product after hardening, and described thermosetting product demonstrates the second-order transition temperature higher than 70 DEG C; And when preparing described heat curable composition with the silica filler of 50 % by weight, described thermosetting product demonstrate by critical stress intensity factor K _1cthe fracture toughness property of value meter is higher than 1.0MPa.m ^1/2.

2. composition according to claim 1, partly or entirely pre-reaction is to form half ester wherein to make described polyvalent alcohol (b) and acid anhydrides (f), and described acid anhydrides (f) is similar and different with described anhydride hardener (d).

3. composition according to claim 1, wherein said amphiphilic polyether block copolymer is selected from the group be made up of the following: diblock, line style three block, line style four block, more higher order multiblock structure; Branched block structure; Or star block structure.

4. composition according to claim 1, wherein saidly miscible block segments can contain poly-ethylene oxide block, propylene oxide block or poly-(oxyethane-altogether-propylene oxide) block.

5. composition according to claim 1, wherein saidly miscible block segments can not contain polybutylene oxide block, poly-oxepane block, poly-Epoxydodecane block or poly-epoxyhexadecane block.

6. composition according to claim 1, the described at least one of wherein said amphiphilic block copolymers (a) can miscible segment be poly-(oxyethane).

7. composition according to claim 1, the described at least one of wherein said amphiphilic block copolymers (a) can not miscible segment be poly-(butylene oxide ring).

8. composition according to claim 1, wherein said amphiphilic block copolymers (a) is poly-(oxyethane)-embedding-poly-(butylene oxide ring) or poly-(oxyethane)-embedding-poly-(butylene oxide ring)-embedding-poly-(oxyethane).

9. composition according to claim 1, wherein said amphiphilic block copolymers (a) is poly-(oxyethane)-embedding-poly-(oxepane).

10. composition according to claim 1, wherein said amphiphilic block copolymers (a) is the blend of two or more segmented copolymer.

11. compositions according to claim 1, wherein said amphiphilic block copolymers can miscible segment and described amphiphilic block copolymers can not the ratio of miscible segment be 10: 1 to 1: 10.

12. compositions according to claim 1, wherein said epoxy resin (c) comprises the diglycidylether of dihydroxyphenyl propane and derivative, the diglycidylether of Bisphenol F and derivative.

13. compositions according to claim 1, described composition at least comprises filler.

14. compositions according to claim 13, wherein said filler is mineral filler.

15. compositions according to claim 14, wherein said mineral filler is selected from silicon-dioxide, talcum, quartz, mica, and fire-retardant filler.

16. compositions according to claim 15, wherein said fire-retardant filler is selected from three aluminium hydroxides, magnesium hydroxide and boehmite.

17. compositions according to claim 13, wherein based on the gross weight of described composition, the concentration of described filler is selected between 1 % by weight to 95 % by weight.

18. 1 kinds of thermosetting products obtained by polymerization composition according to claim 1.

19. 1 kinds of methods for the preparation of heat curable composition, described method comprises the following top of mixing:

(e) at least one catalyzer,

The thermosetting product of 20. 1 kinds of solidifications, the thermosetting product of described solidification comprises the heat curable composition according to claim 1 of solidification.