CN101274998B - Heat-resistant flame-proof phosphorus- and silicon-containing hybrid curing agent for epoxy type electronic polymer material and preparation thereof - Google Patents
Heat-resistant flame-proof phosphorus- and silicon-containing hybrid curing agent for epoxy type electronic polymer material and preparation thereof Download PDFInfo
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Abstract
The present invention pertains to the field of polymeric material and relates to an epoxy phosphorus-containing hybridization hardener with heat resistance and flame retardancy for electron polymer material and a preparation method thereof. The phosphorus-containing hybridization hardener is nanometer-sized organic/inorganic hybrid silicone of a hollow enclosed type or a partially enclosed type, wherein, the structure center of the silicone consists of inorganic skeleton Si-O bonds; the external end of the structure center consists of organic groups of organic phosphor or amidogen or imidogen and has a number average molecular weight of 600 to 10000 and the structural formula is as follows, wherein, R can be hydrogen, cymene, ethyl, n-propyl, isopropyl or butyl; X is organic containing phosphorus substituent ; Y is organic amino-containing substituent. The samples prepared with epoxy resin hardened by the hardener not only have a very good flame retardant performance, but also maintain good heat resistant and mechanical property, thus meeting the requirements for heat resistance and flame retardancy and mechanical aspects of the epoxy resin used for the electronic substrate material with high performance.
Description
Technical field
The invention belongs to the polymer materials field, be specifically related to a kind of heat-proof combustion-resistant epoxy type electronic polymer material phosphorus-and silicon-containing hybrid curing agent and preparation method thereof.
Background technology
With robot calculator, mobile telephone etc. is that the electronic industry of representative is a recent two decades hi-tech industry with the fastest developing speed, the fast development of electronic industry has also driven the development of the thermosetting resin that is closely connected with it, in all used in electronic industry thermoset resin material fields, epoxy-resin systems is because of its superior performance and low cost consumption maximum, proportion surpasses 40%, having a wide range of applications aspect the encapsulation of the manufacturing of printed-wiring board (PWB) and semi-conductor, electron device, be very important a kind of macromolecular material in the electronic industry.
Along with the standard of the raising of the appearance of advanced electronics technology, electronic industrial products heat-proof combustion-resistant grade and relevant safety technique to the demands for higher performance of electronic substrate with Resins, epoxy, performances such as especially fire-retardant, heat-resisting and mechanics.Yet the oxygen index of universal epoxy resin is 19.8 only, belongs to inflammable material, there is certain disaster hidden-trouble during use, thereby how to improve the flame retardant properties of Resins, epoxy, and make it to adapt to better increasingly extensive Application Areas, become the focus that the whole world is paid close attention to.
The flame resistant method of Resins, epoxy generally can be divided into additive process and reaction method two big classes, additive process is to add various additives with flame retardant properties in Resins, epoxy, make material have flame retardant properties, but in the additive process fire retardant easily migration ooze out and influence other performance of Resins, epoxy.Reaction method is to introduce flame retarding construction in Resins, epoxy, and fire retardant matter is difficult for migration, is difficult for separating out, reach good and permanent flame retardant effect, and having fabulous thermostability and charring rate, mainly is to introduce halogen group, for example tetrabromo bisphenol-a epoxy resin at Resins, epoxy at present.Yet since 1986, it is found that tetrabromo bisphenol-a epoxy resin meeting Pintsch process when burning, and produce deleterious many bromines diphenylene-oxide and many bromos dibenzo dioxan, these are can damage skin and internal organs and make body deformity and carcinogenic material, halogen-containing thus Resins, epoxy fails to obtain the environmental protection sign in Europe, and it is used and also has been subjected to certain obstruction.The ethoxyline resin antiflaming agent of therefore developing the environmental protection of non-halogen replaces existing high halogen or low halogen fire retardant just to have very great environment protection significance.
Very active about the research of the Resins, epoxy of the high flame resistance of environmental protection in recent years, the researchist has carried out a large amount of work in this field both at home and abroad, and is from present bibliographical information, wherein in the majority with phosphorous and siliceous Resins, epoxy.As application number is 00123523.0 Chinese patent, and application number is 01130820.6 Chinese patent, and application number is that 2856369 United States Patent (USP) all is to have synthesized phosphorated Resins, epoxy, and Hsiue GH and Wang WJ etc. has also synthesized siliceous Resins, epoxy.Based on macromolecular structure and property relationship principle,, often make the thermal characteristics and the mechanical properties decrease of Resins, epoxy though the general relatively Resins, epoxy of phosphorous or siliceous Resins, epoxy has flame retardant effect preferably.
Summary of the invention
One of the technical problem to be solved in the present invention is to overcome the above-mentioned shortcoming and defect of existing in prior technology, a kind of heat-proof combustion-resistant epoxy type electronic polymer material phosphorus-and silicon-containing hybrid curing agent (hereinafter to be referred as phosphorus-and silicon-containing hybrid curing agent) is provided, described phosphorus-and silicon-containing hybrid curing agent is the hollow dead front type or the type semienclosed siloxanes of the organic inorganic hybridization of nano-scale, wherein the siloxane structure center is made up of inorganic skeleton Si-O key, the structure centre outer end is by containing organophosphorus or amino or the imino-organic group is formed, number-average molecular weight is 600～10000, has following structural formula:
Wherein, R ' is hydrogen, methyl, ethyl, n-propyl, sec.-propyl or butyl; X is organic phosphorous substituting group; Y is organic substituting group that contains amino (imino-).
Another technical problem that the present invention will solve provides the preparation method of this heat-proof combustion-resistant epoxy type electronic polymer material with phosphorus-and silicon-containing hybrid curing agent, and described preparation method comprises the steps:
According to the mass fraction, at first with 100 parts of the many alkyl silanes of epoxy group(ing), 20～100 parts of phosphorous active substances, 80～150 parts of organic solvents, a certain amount of catalyst mix, at 50～100 ℃ of following back flow reaction 3～10h;
And then will contain 20～400 parts of many alkyl silanes, 50～100 parts of the distilled water of amino or imino-, be added drop-wise in the above-mentioned mixing solutions, at 30～60 ℃ of following hydrolysis backflow 2～8h, removing desolvates promptly gets heat-proof combustion-resistant epoxy type electronic polymer material phosphorus-and silicon-containing hybrid curing agent.
The many alkyl silanes of described epoxy group(ing) comprise one or more the mixture in the many alkyl silanes of the epoxy group(ing) with following structural formula:
Wherein R is alkyl, oxa-1-18 straight chain or side chain hydrocarbyl residue; R
1Be in methyl, ethyl, n-propyl, sec.-propyl and the butyl one or more, R
2Be in methyl, ethyl, n-propyl, sec.-propyl and the butyl one or more, n is 2 or 3.
The described many alkyl silanes of epoxy group(ing) that contain amino or imino-comprise one or more the mixture in the many alkyl silanes of the epoxy group(ing) that contains amino or imino-with following structural formula:
Wherein R " is hydrogen, alkyl, aryl or arylidene; R is alkyl, oxa-1-18 straight chain or side chain hydrocarbyl residue; R
1Be in methyl, ethyl, n-propyl, sec.-propyl and the butyl one or more, R
2Be in methyl, ethyl, n-propyl, sec.-propyl and the butyl one or more; N is 2 or 3.
Described phosphorous active substance comprises phosphorous acid, phosphoric acid, dialkyl phosphite, the assorted phenanthrene in 10-oxidation-(9,10-dihydro-9-oxy-10-phosphorus) or phosphate dialkyl ester.
The described many alkyl silanes consumption that contains amino or imino-is 100～150 parts;
Described organic solvent is one or more the mixture in benzene, toluene, tetrahydrofuran (THF) or the butyl ether, preferred 90～120 parts of consumption.
Described catalyzer comprises Lewis acids such as dibutyl tin dilaurate, triphenyl phosphorus, aluminum chloride or triethylamine, and wherein catalyst consumption is 0.001%～0.5% of each constituent mass summation of polyaddition reaction.The preferred consumption of described catalyzer is 0.01%～0.1% of each constituent mass summation of polyaddition reaction.
Organic/inorganic hybridization material is by organic phase and the inorganic a kind of uniform heterogeneous material that constitutes mutually, wherein has the size of a phase at least or a dimension is arranged in nanometer scale.This material is different from traditional organic phase/inorganic phase filling system, is not organic phase and inorganic simple adduction mutually, but organic phase with inorganic nanometer to submicron order even the molecular level in conjunction with forming.The material that obtains so not only has separately organic and inorganic materials advantage separately, and can make that the polymer glass temperature is improved, mechanical property is strengthened.So the organic/inorganic hybridization material of phosphorous silicon not only has good flame retardant property, and has superior mechanical property, thermotolerance, can satisfy the high-performance electronic base material with the requirement of Resins, epoxy in heat-proof combustion-resistant and terms of mechanics, avoided above shortcoming.
The independent cured epoxy resin of phosphorus-and silicon-containing hybrid curing agent of the present invention or with the prepared sample of common epoxy hardener composite curing Resins, epoxy, have excellent mechanical property, flame retardant properties and resistance toheat, wherein limiting oxygen index(LOI) can reach 23～38, can satisfy the requirement of Resins, epoxy in heat-proof combustion-resistant and terms of mechanics of high-performance electronic base material.
The fundamental property of the product of prepared phosphorus-and silicon-containing hybrid curing agent of the present invention and common epoxy hardener composite curing E54 Resins, epoxy sees Table 1, wherein A represents phosphorus-and silicon-containing hybrid curing agent, used epoxy hardener is right, right '-diaminodiphenylmethane (DDM),, the solidifying agent total amount is calculated according to the mol ratio of epoxy group(ing) and amino hydrogen at 1: 1.Used Resins, epoxy is E54 Resins, epoxy.The preparation method of phosphorus-and silicon-containing hybrid curing agent is as follows: 100 parts of glycidoxypropyltrime,hoxysilane, and DOPO80 part, 0.9 part of triphenyl phosphorus, 90 parts of tetrahydrofuran (THF)s join in the round-bottomed flask of 500ml successively, at 80 ℃ of following back flow reaction 4h.Then 180 parts of anilino Union carbide A-162s and 80 parts of deionized waters are added drop-wise in the above-mentioned mixing solutions successively, and, except that the small molecules that anhydrates and hydrolysis is come out, promptly get phosphorus-and silicon-containing hybrid curing agent (A) by vacuum-drying at 60 ℃ of following back flow reaction 2h.
Table 1 phosphorus-and silicon-containing hybrid curing agent and DDM reach the fundamental property of composite curing E54 Resins, epoxy gained cured article separately
The prepared phosphorus-and silicon-containing hybrid curing agent decapacitation of the present invention is solidified outside the bisphenol A type epoxy resin, can also solidify the Resins, epoxy of other type, as phenolic aldehyde F type Resins, epoxy.The fundamental property of the product of this phosphorus-and silicon-containing hybrid curing agent and epoxy hardener composite curing F51 Resins, epoxy commonly used sees Table 2, wherein A represents the hydridization epoxy hardener of phosphorous silicon, used epoxy hardener is 4,4-diaminodiphenylsulfone(DDS) (4,4-DDS), the solidifying agent total amount according to epoxy group(ing) and amino hydrogen mol ratio 1: 1 calculate.Used Resins, epoxy is F51 Resins, epoxy.100 parts of glycidoxy n-hexyl triethoxyl silanes, 43 parts of diethyl phosphites, 0.75 part of triethylamine join in the round-bottomed flask of 500ml, at 80 ℃ of following back flow reaction 4h successively.Then 150 parts of γ-An Bingjisanyiyangjiguiwans and 90 parts of deionized waters are added drop-wise in the above-mentioned mixing solutions successively, and at 50 ℃ of following back flow reaction 2h, except that the small molecules that anhydrates and hydrolysis is come out, promptly get the hydridization epoxy hardener (A) of phosphorous silicon by vacuum-drying.
Table 2 phosphorus-and silicon-containing hybrid curing agent and 4,4-DDS are separately and the fundamental property of composite curing F51 Resins, epoxy gained cured article
| 3 | 100 | 150.7 | 17.0 | 4.92 | 1.93 | 178 | 44.0 | 30.1 |
| 4 | 100 | 216.8 | 8.5 | 5.53 | 2.29 | 182 | 44.5 | 33.9 |
| 5 | 100 | 244.1 | 0 | 5.89 | 2.43 | 187 | 45.3 | 38.8 |
Embodiment
Following embodiment further specifies of the present invention, but the invention is not restricted to following embodiment.
Embodiment 1:
With the epoxy third oxygen-butyl Trimethoxy silane of 100g, the 20g diethyl phosphite, 0.6g dibutyl two lauric acid base tin and 80g butyl ether solvent join in the there-necked flask, at 50 ℃ of following back flow reaction 10h, obtain hydridization epoxy compounds siliceous, phosphorus.Add anilino Union carbide A-162 20g then, Dropwise 5 0g deionized water dropwises at 30min under 30 ℃ of stirrings, reacts 8h under reflux state, and rotary evaporation removes and to desolvate and small molecules promptly gets the heat-stable hybridized epoxy hardener of phosphorous silicon.
Get heat-stable hybridized epoxide resin 20g and F51 type Resins, epoxy 100g is compound, adopt the 12.15g triethylene tetramine to solidify then.The limiting oxygen index(LOI) of cured article is 29.2, and tensile strength is 43.4MPa, and second-order transition temperature is 167 ℃.
Embodiment 2:
With the epoxypropoxy dimethoxy silane of 100g, the 40g diethyl phosphoric acid, 0.7g triethylamine catalyzer and 120g toluene solvant join in the there-necked flask, at 60 ℃ of following back flow reaction 8h, obtain hydridization epoxy compounds siliceous, phosphorus.Add anilino Union carbide A-162 40g then, drip the 60g deionized water under 40 ℃ of stirrings, dropwise at 20min, react 6h under reflux state, rotary evaporation removes and desolvates and small molecules promptly gets the heat-stable hybridized epoxy hardener of phosphorous silicon.
Get heat-stable hybridized epoxide resin 20g and E51 type Resins, epoxy 100g is compound, adopt the 30.47g diaminodiphenylsulfone(DDS) to solidify then.The limiting oxygen index(LOI) of cured article is 28.0, and tensile strength is 45.0MPa, and second-order transition temperature is 185 ℃.
Embodiment 3:
Epoxypropoxy triethoxyl silane with 100g, the 50g diethyl phosphite, 0.75g dibutyl two lauric acid base tin catalysts and 50g tetrahydrofuran solvent join in the there-necked flask, at 70 ℃ of following back flow reaction 5h, obtain hydridization epoxy compounds siliceous, phosphorus.Add γ-An Bingjisanyiyangjiguiwan 75g then, drip the 70g deionized water under 50 ℃ of stirrings, dropwise at 30min, react 4h under reflux state, rotary evaporation removes and desolvates and small molecules promptly gets the heat-stable hybridized epoxy hardener of phosphorous silicon.
It is compound to get above-mentioned heat-stable hybridized epoxy hardener 20g and E44 type Resins, epoxy 100g, adopts the 25.12g diaminodiphenylsulfone(DDS) to solidify then.The limiting oxygen index(LOI) of cured article is 27.5, and tensile strength is 44.2MPa, and second-order transition temperature is 178 ℃.
Embodiment 4:
With the epoxypropoxy triethoxyl silane of 100g, 50gDOPO, 0.75g triphenyl phosphorus catalyzer and 80g tetrahydrofuran solvent join in the there-necked flask, at 80 ℃ of following back flow reaction 5h, obtain hydridization epoxy compounds siliceous, phosphorus.Add anilino Union carbide A-162 180g then, drip the 80g deionized water under 60 ℃ of stirrings, dropwise at 40min, react 3h under reflux state, rotary evaporation removes and desolvates and small molecules promptly gets the heat-stable hybridized epoxy hardener of phosphorous silicon.
Get above-mentioned heat-stable hybridized epoxide resin 30g and E54 type Resins, epoxy 100g is compound, adopt the 23.39g diaminodiphenylmethane to solidify then.The limiting oxygen index(LOI) of cured article is 27.1, and tensile strength is 45.5MPa, and second-order transition temperature is 171 ℃.
Embodiment 5:
Glycidoxy-propyltrimethoxy silane and 50g epoxypropoxy diethoxy silane with 50g, 60gDOPO, the 20g diethyl phosphoric acid, 0.9g aluminum trichloride catalyst and 90g tetrahydrofuran solvent and 50g butyl ether join in the there-necked flask, at 90 ℃ of following back flow reaction 4h, obtain hydridization epoxy compounds siliceous, phosphorus.Add γ-An Bingjisanyiyangjiguiwan 90g and anilino Union carbide A-162 90g then, under 60 ℃ of stirrings, drip the 90g deionized water, dropwise at 45min, react 2h under reflux state, rotary evaporation removes and to desolvate and small molecules promptly gets the heat-stable hybridized epoxy hardener of phosphorous silicon.
Get above-mentioned heat-stable hybridized epoxide resin 20g and dinaphthalene type Resins, epoxy 100g (oxirane value is 0.43) is compound, adopt the 8.11g Dicyanodiamide to solidify then.The limiting oxygen index(LOI) of cured article is 31.4, and tensile strength is 43.4MPa, and second-order transition temperature is 169 ℃.
Embodiment 6:
Epoxypropoxy triethoxyl silane and 50g epoxypropoxy dimethoxy silane with 50g, 60gDOPO, the 20g diethyl phosphite, 0.9g aluminum chloride and 75g butyl ether solvent and 75g toluene solvant join in the there-necked flask, at 100 ℃ of following back flow reaction 3h, obtain hydridization epoxy compounds siliceous, phosphorus.Add γ-An Bingjisanyiyangjiguiwan 120g and anilino Union carbide A-162 260g then, under 60 ℃ of stirrings, drip the 100g deionized water, dropwise at 50min, react 2h under reflux state, rotary evaporation removes and to desolvate and small molecules promptly gets the heat-stable hybridized epoxy hardener of phosphorous silicon.It is compound with bisphenol f type epoxy resin (oxirane value is 0.49) 100g to get 20 parts of above-mentioned heat-stable hybridized epoxide resins, adopts the 20.12g diaminodiphenylmethane to solidify then.The limiting oxygen index(LOI) of cured article is 34.8, and tensile strength is 46.3MPa, and second-order transition temperature is 177 ℃.
Claims (7)
1. heat-proof combustion-resistant epoxy type electronic polymer material phosphorus-and silicon-containing hybrid curing agent, it is characterized in that, be the hollow dead front type or the type semienclosed siloxanes of the organic inorganic hybridization of nano-scale, wherein the siloxane structure center is made up of inorganic skeleton Si-O key, the structure centre outer end is by containing organophosphorus or amino or the imino-organic group is formed, number-average molecular weight is 600～10000, has following structural formula:
Wherein, R
/Be hydrogen, methyl, ethyl, n-propyl, sec.-propyl or butyl; X is organic phosphorous substituting group; Y is organic substituting group that contains amino or imino-.
2. the described a kind of heat-proof combustion-resistant epoxy type electronic polymer material of claim 1 is characterized in that with the preparation method of phosphorus-and silicon-containing hybrid curing agent, comprises the steps:
According to the mass fraction, at first with 100 parts of the many alkyl silanes of epoxy group(ing), 20～100 parts of phosphorous active substances, 80～150 parts of organic solvents, a certain amount of catalyst mix, at 50～100 ℃ of following back flow reaction 3～10h;
And then will contain 20～400 parts of many alkyl silanes, 50～100 parts of the distilled water of amino or imino-, be added drop-wise in the above-mentioned mixing solutions, at 30～60 ℃ of following hydrolysis backflow 2～8h, removing desolvates promptly gets heat-proof combustion-resistant epoxy type electronic polymer material phosphorus-and silicon-containing hybrid curing agent;
The many alkyl silanes of described epoxy group(ing) comprise one or more the mixture in the many alkyl silanes of the epoxy group(ing) with following structural formula:
Wherein R is alkylidene group, oxa-1-18 straight chain or side chain hydrocarbyl residue; R
1Be in methyl, ethyl, n-propyl, sec.-propyl and the butyl one or more, R
2Be in methyl, ethyl, n-propyl, sec.-propyl and the butyl one or more, n is 3;
The described many alkyl silanes of epoxy group(ing) that contain amino or imino-comprise one or more the mixture in the many alkyl silanes of the epoxy group(ing) that contains amino or imino-with following structural formula:
R wherein
//Be hydrogen, alkyl, aryl; R is alkylidene group, oxa-1-18 straight chain or side chain hydrocarbyl residue; R
1Be in methyl, ethyl, n-propyl, sec.-propyl and the butyl one or more, R
2Be in methyl, ethyl, n-propyl, sec.-propyl and the butyl one or more; N is 3.
3. preparation method according to claim 2 is characterized in that, described phosphorous active substance comprises phosphorous acid, phosphoric acid, dialkyl phosphite, the assorted phenanthrene in 10-oxidation-(9,10-dihydro-9-oxy-10-phosphorus) or phosphate dialkyl ester.
4. preparation method according to claim 2 is characterized in that, the described many alkyl silanes consumption that contains amino or imino-is 100～150 parts.
5. preparation method according to claim 2 is characterized in that, described organic solvent is one or more the mixture in benzene, toluene, tetrahydrofuran (THF) or the butyl ether, and consumption is 90～120 parts.
6. preparation method according to claim 2 is characterized in that described catalyzer comprises dibutyl tin dilaurate, triphenyl phosphorus, aluminum chloride or triethylamine, and wherein catalyst consumption is 0.001%～0.5% of each constituent mass summation of polyaddition reaction.
7. preparation method according to claim 6 is characterized in that, the preferred consumption of described catalyzer is 0.01%～0.1% of each constituent mass summation of polyaddition reaction.
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| US20120175585A1 (en) * | 2009-09-17 | 2012-07-12 | Yissum Research Development Company Of The Hebrew University Of Jerusalem, Ltd., | Cage nanostructures and prepartion thereof |
| KR101844576B1 (en) * | 2010-05-20 | 2018-04-02 | 다우 코닝 코포레이션 | Silicone resins and their use in polymer compositions |
| CN102153729B (en) * | 2011-03-04 | 2013-06-12 | 重庆三峡油漆股份有限公司 | Semi-enclosed organic amine curing agent and application thereof to anti-corrosive coating |
| CN102295741B (en) * | 2011-06-29 | 2013-01-09 | 中科院广州化学有限公司 | Polyamine organosilicon curing agent for epoxy floor coating, and preparation method thereof |
| CN102504243B (en) * | 2011-10-18 | 2013-08-07 | 中科院广州化学有限公司 | Amino polyether organic silicon hybrid curing agent for epoxy floor coating |
| CN105733194B (en) * | 2016-04-01 | 2017-08-04 | 厦门大学 | A kind of element cooperative flame retardant epoxy resin of silicon phosphorus titanium three and preparation method thereof |
| CN105778429B (en) * | 2016-04-01 | 2017-10-20 | 厦门大学 | A kind of agent of low hygroscopicity epoxy resin and preparation method thereof |
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| CN1724591A (en) * | 2005-07-07 | 2006-01-25 | 中国科学院广州化学研究所 | Organic silicon fibre retardant of a kind of phosphorous and epoxy group(ing) and preparation method thereof |
| CN101113196A (en) * | 2007-06-11 | 2008-01-30 | 中国科学院广州化学研究所 | Silicon-phosphor-containing heat-stable hybridized epoxide resin and the preparing method and application thereof |
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| CN1724591A (en) * | 2005-07-07 | 2006-01-25 | 中国科学院广州化学研究所 | Organic silicon fibre retardant of a kind of phosphorous and epoxy group(ing) and preparation method thereof |
| CN101113196A (en) * | 2007-06-11 | 2008-01-30 | 中国科学院广州化学研究所 | Silicon-phosphor-containing heat-stable hybridized epoxide resin and the preparing method and application thereof |
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