CN101113196A - Silicon-phosphor-containing heat-stable hybridized epoxide resin and the preparing method and application thereof - Google Patents
Silicon-phosphor-containing heat-stable hybridized epoxide resin and the preparing method and application thereof Download PDFInfo
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Abstract
The invention discloses a heatproof hybrid epoxy resin containing phosphosilicate as well as the preparation method and the application thereof. The preparation method of epoxy resin is that: counting in mass fraction, 100 epoxide polyalkyl silicane, 50 to 120 organic solvent are mixed with 0.001 percent to 0.5 percent catalyst agent of epoxide polyalkyl silicane mass, then under 50 to 120 DEG C, 10 to 40 deionized water is dropwised in mixing solution by hydrolyzing and reflowing for 2 to 8 hours before 1 to 100 active material containing phosphor is added in, and the organic solvent used for reaction is removed after 3 to 10 hours reaction under 100 to 160 DEG C, thus acquiring the heatproof hybrid epoxy resin containing phosphosilicate, the number-average molar mass is 500-6000. After being separately solidified or compound solidified with normal epoxy resin, the heatproof hybrid epoxy resin containing phosphosilicate has the advantages of good mechanical property, flame retardant property and heat-resistant quality, tensile strength up to 43 to 94 Mpa, limiting oxygen index up to 23 to 38 and glass transition temperature up to 165 to 187 DEG C, can be used widely as electronic industrial base material with high-performance.
Description
Technical field
The invention belongs to polymeric material field, particularly a kind of silicon-phosphor-containing heat-stable hybridized epoxide resin and its production and application.
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 carbon forming 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 Chinese patent application CN00123523, CN01130820, U.S. Patent application US2856369 have synthesized phosphorated Resins, epoxy, and Hsiue GH and Wang WJ etc. has also synthesized siliceous Resins, epoxy.Though the Resins, epoxy that phosphorous or siliceous Resins, epoxy is general relatively has flame retardant effect preferably, the restriction of conditions such as while molecular designing has but reduced the thermal characteristics of Resins, epoxy and mechanical property.
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 concurrently organic and advantage inorganic materials, and polymkeric substance mechanical property, second-order transition temperature are improved.So the organic/inorganic hybridization material of phosphorous silicon not only has superior mechanical property, thermotolerance, and has the good flame performance, satisfy of the requirement of high-performance electronic base material fully with Resins, epoxy.
Summary of the invention
In order to solve above-mentioned the deficiencies in the prior art part, primary and foremost purpose of the present invention is to provide a kind of silicon-phosphor-containing heat-stable hybridized epoxide resin, this Resins, epoxy solidifies separately or the cured article after compound with traditional Resins, epoxy, have good thermotolerance and flame retardant resistance and very high physical strength, this Resins, epoxy can be good at satisfying the requirement of high-performance electronic base material with thermosetting resin.
Another object of the present invention is to provide the preparation method of above-mentioned silicon-phosphor-containing heat-stable hybridized epoxide resin.This Resins, epoxy is by obtaining with phosphorous active substance reaction after the hydrolysis of many alkyl silanes of epoxy group(ing), the condensation.
A further object of the present invention is to provide the application of above-mentioned silicon-phosphor-containing heat-stable hybridized epoxide resin.
Purpose of the present invention realizes by following technical proposals: a kind of silicon-phosphor-containing heat-stable hybridized epoxide resin, be by the hydrolysis of many alkyl silanes of epoxy group(ing), condensation and phosphorous active substance react and obtain, it is characterized in that, count by weight, with 100 parts of the many alkyl silanes of epoxy group(ing) (formula (1)), 50～120 parts of organic solvents, account for the catalyst mix of many alkyl silanes of epoxy group(ing) quality 0.001%～0.5%, under 50～120 ℃, 10～40 parts of deionized waters are added drop-wise in the above-mentioned mixing solutions, and at 50～120 ℃ of hydrolysis backflow 2～8h, add 1～100 part of phosphorous active substance then, and at 100～160 ℃ of following reaction 3～10h, guarantee that epoxy group(ing) and phosphorus containg substances react completely, remove the solvent that dereaction is used, promptly get silicon-phosphor-containing heat-stable hybridized epoxide resin; The number-average molecular weight of described silicon-phosphor-containing heat-stable hybridized epoxide resin is 500～6000; Described catalyzer can be metal carboxylate, an acidic catalyst or basic catalyst.
The expression of the many alkyl silanes of described epoxy group(ing) such as structural formula (1), wherein R is 3-18 straight chain or side chain hydrocarbyl residue, (oxygen, sulphur or nitrogen) assorted 3-18 straight chain or side chain hydrocarbyl residue, preferred especially as: (CH
2)
5, CH
2-O-(CH
2)
3, CH
2-S-(CH
2)
3Or CH
2-O-[CH
2CH (OH) CH
2NCH
3]-CH
2Deng, can contain in aerobic, sulphur or the nitrogen any one among the R; R
1A kind of in methyl, ethyl, n-propyl, sec.-propyl or the butyl, R
2A kind of in methyl, ethyl, n-propyl, sec.-propyl or the butyl, R
1And R
2Can be the same or different; N is 2 or 3.It also can be own synthetic that the many alkyl silanes of described epoxy group(ing) can be bought from the market.
Formula (1)
In order to realize the present invention better, the many alkyl silanes of described epoxy group(ing) particularly preferably are a kind of in the epoxy third oxygen-butyl Trimethoxy silane, epoxypropoxy methyl dimethoxysilane, epoxypropoxy methyl diisopropoxy silane, the epoxy third oxygen octadecyltriethoxy silane, epoxypropoxy three n-propyl TMOSs, epoxypropoxy diethoxy silane, epoxypropoxy three butoxy silanes or the epoxypropoxy dimethoxy silane etc. or any two kinds.
Preferably 30～40 parts of described deionized water consumptions.
Described organic solvent is not for influencing the organic solvent of reaction, can be one or more the mixed solvent in benzene, toluene, tetrahydrofuran (THF) or the butyl ether etc., preferred 90～120 parts of consumption.
Described phosphorous active substance can be that all can be with the phosphorus containg substances of epoxide group reaction, it for example is one or more the mixture in phosphorous acid, phosphoric acid, dialkyl phosphite, 10-oxidation-(9,10-2H-9-oxygen-10-phosphorus) assorted luxuriant and rich with fragrance (DOPO) or the phosphate dialkyl ester etc.
Described metal carboxylate comprises acid dibutyl tin, dibutyl tin acetate or stannous octoate etc., described an acidic catalyst comprises hydrochloric acid, sulfuric acid, phosphoric acid, boric acid, nitric acid, aryl sulfonic acid, the organic acid of 1～18 carbochain or various Lewis acid are (as phosphorus trichloride, boron trichloride, iron trichloride, ferric bromide, zinc chloride, tin tetrachloride or titanium tetrachloride) etc., described basic catalyst comprises that alkali-metal oxyhydroxide is (as sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide or rubidium hydroxide etc.), alkali-metal oxide compound is (as potassium oxide, sodium oxide, Cs2O, rubidium oxide or Lithium Oxide 98min etc.), organic amine is (as methylamine, ethamine or triethylamine etc.) or quaternary ammonium salt etc.Preferred especially organotin catalysts and an acidic catalyst.
Described catalyzer preferable amount is 0.01%～0.5% of many alkyl silanes of epoxy group(ing) quality.
The preparation method of above-mentioned silicon-phosphor-containing heat-stable hybridized epoxide resin, may further comprise the steps: count by weight, with 100 parts of the many alkyl silanes of epoxy group(ing) (formula (1)), account for the catalyzer of many alkyl silanes of epoxy group(ing) quality 0.001%～0.5%, 50～120 parts of mixing of organic solvent, under 50～120 ℃, 10～40 parts of deionized waters are added drop-wise in the above-mentioned mixing solutions, and at 50～120 ℃ of hydrolysis backflow 2～8h, add 1～100 part of phosphorous active substance then, and at 100～160 ℃ of following reaction 3～10h, guarantee that epoxy group(ing) and phosphorus containg substances react completely, remove the solvent that dereaction is used, promptly get silicon-phosphor-containing heat-stable hybridized epoxide resin; The number-average molecular weight of described silicon-phosphor-containing heat-stable hybridized epoxide resin is 500～6000; Described catalyzer can be metal carboxylate, an acidic catalyst or basic catalyst.
Above-mentioned silicon-phosphor-containing heat-stable hybridized epoxide resin is in the application of printed-wiring board (PWB), the contour performance flame-resistant high-temperature-resistant of semiconductor sealing material used in electronic industry body material.
Silicon-phosphor-containing heat-stable hybridized epoxide resin of the present invention solidify separately or with ordinary epoxy resin compound cured article, tensile strength reaches 43～94MPa, LOI can reach 23～38, second-order transition temperature reaches 168～195 ℃, therefore can be used as printed-wiring board (PWB), the contour performance flame-resistant high-temperature-resistant of semiconductor sealing material electronic material.
The fundamental property of the cured article after silicon-phosphor-containing heat-stable hybridized epoxide resin of the present invention and F51 Resins, epoxy are compound sees Table 1, wherein A represents silicon-phosphor-containing heat-stable hybridized epoxide resin, B represents F51 Resins, epoxy, used solidifying agent is right, right '-diaminodiphenylmethane (DDM), its consumption according to epoxy group(ing) and amino hydrogen mol ratio 1: 1 calculate.The preparation method of silicon-phosphor-containing heat-stable Resins, epoxy (meter by weight) as follows: 100 parts of glycidoxypropyltrime,hoxysilane, 29 parts of deionized waters, 110 parts of tetrahydrofuran (THF)s join in the round-bottomed flask of 500ml successively, the dibutyl dilaurate base tin of 0.05g is added drop-wise in the above-mentioned mixing solutions, under agitation remain on 100 ℃ of following hydrolysis backflow 4h, then 45 parts of DOPO are joined in the flask, and under 130 ℃, react 5h, remove the hybridization epoxy resin (A) that desolvates and promptly get phosphorous silicon by rotary evaporation.
Table 1 silicon-phosphor-containing heat-stable hybridized epoxide resin solidifies separately or the fundamental property of the cured article after compound with F51 Resins, epoxy
| Sequence number | Charging capacity (g) | P/％ | Performance project | ||
| A/B | T g(℃) | Tensile strength (MPa) | Limiting oxygen index(LOI) (LOI) | ||
| 1 | 0/100 | 0 | 163 | 45 | 22.8 |
| 2 | 20/80 | 0.76 | 172 | 56 | 26.2 |
| 3 | 50/50 | 1.90 | 187 | 63 | 29.4 |
| 4 | 80/20 | 3.0 | There is not glass transition | 81 | 33.3 |
| 5 | 100/0 | 3.84 | There is not glass transition | 94 | 38.4 |
Annotate: table 1 Resins, epoxy sample all by 80 ℃/3h+150 ℃/2h+175 ℃/1h technology curing, measure with electronic universal tester by GB1040-1992 by tensile strength, and sample is a dumb-bell shape; Second-order transition temperature (T
g): after sample solidified, grinding powder was with the Perkin-Elmer DSC-2C type differential scanning calorimeter test that U.S. PE company produces, N
2Atmosphere, 10 ℃/min of temperature rise rate; Limiting oxygen index(LOI) adopts the LOI determinator of U.S. DYNISCO company, according to the operation of ASTM D2863 standard step, sample size: 12 * 6 * 3mm
3
Data from table 1 as can be seen, the silicon-phosphor-containing heat-stable hybridized epoxide resin of the present invention preparation solidifies separately or the DDM cured article after compound all has excellent mechanical property, high thermotolerance and flame retardant resistance with F51 Resins, epoxy, improves effect thereby reached technology of the present invention.
The fundamental property of the cured article after fire-retardant hybridization epoxy resin of phosphorous silicon of the present invention and E44 Resins, epoxy are compound sees Table 2, wherein A represents silicon-phosphor-containing heat-stable hybridized epoxide resin, B represents E44 Resins, epoxy, used solidifying agent is a Dicyanodiamide, and its consumption calculates according to the mol ratio of epoxy group(ing) and amino hydrogen at 1: 1.The preparation method of the heat resistant epoxide resin of phosphorous silicon (meter by weight) as follows: 100 parts of epoxy rosickyite base n-hexyl triethoxyl silanes, 26 parts of deionized waters, 90 parts of butyl ether join in the round-bottomed flask of 500ml successively, the 0.07g catalyst drops is added in the above-mentioned mixing solutions, under agitation remain on 120 ℃ of following hydrolysis backflow 5h, then 35 parts of diethyl phosphites are joined in the flask, and under 140 ℃, react 5h, remove the hybridization epoxy resin (A) that desolvates and promptly get phosphorous silicon by rotary evaporation.
Table 2 silicon-phosphor-containing heat-stable hybridized epoxide resin solidifies separately or the fundamental property of the cured article after compound with E44 Resins, epoxy
| Sequence number | Charging capacity (g) | P/％ | Performance project | ||
| A/B | T g(℃) | Tensile strength (MPa) | Limiting oxygen index(LOI) (LOI) | ||
| 1 | 0/100 | 0 | 152 | 43 | 22.5 |
| 2 | 20/80 | 0.98 | 165 | 52 | 25.7 |
| 3 | 50/50 | 2.48 | 179 | 58 | 28.5 |
| 4 | 80/20 | 4.05 | There is not glass transition | 67 | 32.6 |
| 5 | 100/0 | 5.11 | There is not glass transition | 81 | 36.9 |
Annotate: table 2 Resins, epoxy sample all by 80 ℃/3h+150 ℃/2h+175 ℃/1h technology curing, measure with electronic universal tester by GB1040-1992 by tensile strength, and sample is a dumb-bell shape; Second-order transition temperature (T
g): after sample solidified, grinding powder was with the Perkin-Elmer DSC-2C type differential scanning calorimeter test that U.S. PE company produces, N
2Atmosphere, 10 ℃/min of temperature rise rate; Limiting oxygen index(LOI) adopts the LOI determinator of U.S. DYNISCO company, according to the operation of ASTM D2863 standard step, sample size: 12 * 6 * 3mm
3
Data from table 2 as can be seen, the silicon-phosphor-containing heat-stable hybridized epoxide resin of the present invention preparation solidifies separately or the Dicyanodiamide cured article after compound all has excellent mechanical property, high thermotolerance and flame retardant resistance with E44 Resins, epoxy, thereby the technology that reached improves effect, and this explanation the present invention has very wide usability.
The present invention compared with prior art, have following advantage and beneficial effect: the heat-stable hybridized epoxide resin of the present invention's preparation, under the situation of the flame retardant effect that guarantees to reach higher, still have excellent mechanical property and thermotolerance, avoided prior art by introducing the flame retardant effect that phosphorus and silicon improve Resins, epoxy, but the restriction of conditions such as while molecular designing greatly reduces the thermal characteristics of Resins, epoxy and mechanical property, this Resins, epoxy solidifies separately or the cured article after compound with traditional Resins, epoxy, not only has extraordinary flame retardant properties, and kept good thermotolerance and mechanical property, tensile strength reaches 43～94Mpa, limiting oxygen index(LOI) can reach 23～38, second-order transition temperature reaches 165～187 ℃, can be widely used as the industrial body material of high performance electronic.
Embodiment
The present invention is described in further detail below in conjunction with embodiment, but embodiments of the present invention are not limited thereto.
Embodiment 1
The epoxy third oxygen-butyl Trimethoxy silane with 100g, 0.2g catalyzer dibutyl two lauric acid base tin (catalyst consumption be the epoxy third oxygen-butyl Trimethoxy silane quality 0.2%) and 90g butyl ether solvent join in the there-necked flask, under 60 ℃ of stirrings, drip the 25g deionized water, dropwise at 30min, behind reaction 6h under 60 ℃, obtain siliceous hybridization epoxy resin, add diethyl phosphoric acid 25.7g then, at 150 ℃ of following back flow reaction 5h, cooling removes desolvate butyl ether and by-product carbinol, promptly get silicon-phosphor-containing heat-stable hybridized epoxide resin 94.0g, number-average molecular weight is 1779.
Get above-mentioned silicon-phosphor-containing heat-stable hybridized epoxide resin 30g and F51 type Resins, epoxy 100g is compound, adopt the 19.4g triethylene tetramine to solidify (concrete processing condition are identical with the specification sheets part, down with) then.The limiting oxygen index(LOI) of cured article is 29.2, and tensile strength is 64MPa, and second-order transition temperature is 177 ℃.
Embodiment 2
Epoxypropoxy methyl dimethoxysilane with 100g, 0.01g catalyst of triethylamine (catalyst consumption be epoxypropoxy methyl dimethoxysilane quality 0.01%), the mixed solvent of 60g toluene and 60g benzene joins in the there-necked flask, under 120 ℃ of stirrings, drip the 40g deionized water, dropwise at 40min, behind reaction 2h under 120 ℃, obtain with siliceous Resins, epoxy, add DOPO19.6g then, at 100 ℃ of following back flow reaction 10h, solvent toluene is removed in cooling, benzene and by-product carbinol, promptly get silicon-phosphor-containing heat-stable hybridized epoxide resin 92.6g, number-average molecular weight is 954.
Get above-mentioned silicon-phosphor-containing heat-stable hybridized epoxide resin 20g and E51 type Resins, epoxy 100g is compound, adopt the 58.4g polymeric amide to solidify then.The limiting oxygen index(LOI) of cured article is 28.0, and tensile strength is 55MPa, and second-order transition temperature is 169 ℃.
Embodiment 3
Epoxypropoxy methyl diisopropoxy silane with 100g, 0.001g catalyzer hydrochloric acid (catalyst consumption be epoxypropoxy methyl diisopropoxy silane quality 0.001%) and 50g tetrahydrofuran solvent join in the there-necked flask, under 50 ℃ of stirrings, drip the 10g deionized water, dropwise at 60min, behind reaction 8h under 50 ℃, obtain siliceous Resins, epoxy, add 10g phosphoric acid and dimethyl phosphate 16.4g then, at 130 ℃ of following back flow reaction 5h, solvents tetrahydrofurane and by product Virahol are removed in cooling, promptly get silicon-phosphor-containing heat-stable hybridized epoxide resin 74.1g, number-average molecular weight is 569.
Get above-mentioned silicon-phosphor-containing heat-stable hybridized epoxide resin 25g and E44 type Resins, epoxy 100g is compound, adopt the 28.5g diaminodiphenylsulfone(DDS) to solidify then.The limiting oxygen index(LOI) of cured article is 28.5, and tensile strength is 58MPa, and second-order transition temperature is 167 ℃.
Embodiment 4
The epoxy third oxygen octadecyltriethoxy silane with 100g, 0.1g catalyzer sodium hydroxide (catalyst consumption be the epoxy third oxygen octadecyltriethoxy silane quality 0.1%) and 80g benzene solvent join in the there-necked flask, under 110 ℃ of stirrings, drip the 20g deionized water, dropwise at 25min, behind reaction 6h under 110 ℃, obtain siliceous Resins, epoxy, add phosphorous acid diphenyl ester 23.7g then, at 160 ℃ of following back flow reaction 3h, solvent benzol and by product ethanol are removed in cooling, promptly get silicon-phosphor-containing heat-stable hybridized epoxide resin 101.3g, number-average molecular weight is 5835.
Get above-mentioned silicon-phosphor-containing heat-stable hybridized epoxide resin 35g and F51 type Resins, epoxy 100g is compound, adopt the 23.4g diethylenetriamine to solidify then.The limiting oxygen index(LOI) of cured article is 27.1, and tensile strength is 65MPa, and second-order transition temperature is 171 ℃.
Embodiment 5
Epoxypropoxy tripropyl TMOS and 50g epoxypropoxy methyldiethoxysilane with 50g, 0.09g inferior tin of octoate catalyst (catalyst consumption be many alkyl silanes of epoxy group(ing) quality 0.09%) and 90g tetrahydrofuran solvent join in the there-necked flask, under 70 ℃ of stirrings, drip the 25g deionized water, dropwise at 50min, behind reaction 4.5h under 70 ℃, obtain siliceous Resins, epoxy, add DOPO1g then, at 130 ℃ of following back flow reaction 5h, solvents tetrahydrofurane and by product propyl alcohol are removed in cooling, promptly get silicon-phosphor-containing heat-stable hybridized epoxide resin 50.9g, number-average molecular weight is 2012.
Get above-mentioned silicon-phosphor-containing heat-stable hybridized epoxide resin 35g and dinaphthalene type Resins, epoxy 100g (oxirane value is 0.43) is compound, adopt the 24.1g Dicyanodiamide to solidify then.The limiting oxygen index(LOI) of cured article is 26.4, and tensile strength is 71MPa, and second-order transition temperature is 185 ℃.
Embodiment 6
Epoxypropoxy three butoxy silanes with 50g, 0.5g catalyzer dibutyl tin acetate (catalyst consumption be epoxypropoxy three butoxy silane quality 0.5%) and 75g butyl ether solvent join in the there-necked flask, under 90 ℃ of stirrings, drip the 30g deionized water, dropwise at 45min, behind reaction 5h under 90 ℃ of states, obtain containing epoxy silicone, add phosphatase 11 00g then, at 140 ℃ of following back flow reaction 3.5h, cooling removes desolvate butyl ether and by product butanols, promptly get silicon-phosphor-containing heat-stable hybridized epoxide resin 135.8g, number-average molecular weight is 1698.
It is compound to get above-mentioned silicon-phosphor-containing heat-stable hybridized epoxide resin 22g and bisphenol f type epoxy resin (oxirane value is 0.49) 100g, adopts the 27.6g diaminodiphenylmethane to solidify then.The limiting oxygen index(LOI) of cured article is 36.8, and tensile strength is 66MPa, and second-order transition temperature is 173 ℃.
The foregoing description is a preferred implementation of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (10)
1. silicon-phosphor-containing heat-stable hybridized epoxide resin, be by the hydrolysis of many alkyl silanes of epoxy group(ing), condensation and phosphorous active substance react and obtain, it is characterized in that: count by weight, with 100 parts of the many alkyl silanes of epoxy group(ing), 50～120 parts of organic solvents, account for the catalyst mix of many alkyl silanes of epoxy group(ing) quality 0.001%～0.5%, under 50～120 ℃, 10～40 parts of deionized waters are added drop-wise in the above-mentioned mixing solutions, and at 50～120 ℃ of hydrolysis backflow 2～8h, add 1～100 part of phosphorous active substance then, and at 100～160 ℃ of following reaction 3～10h, remove the solvent that dereaction is used, promptly get silicon-phosphor-containing heat-stable hybridized epoxide resin; The number-average molecular weight of described silicon-phosphor-containing heat-stable hybridized epoxide resin is 500～6000; Described catalyzer is metal carboxylate, an acidic catalyst or basic catalyst;
Many alkyl silanes of described epoxy group(ing) such as structural formula (1) expression, wherein R is 3-18 straight chain or side chain hydrocarbyl residue, (oxygen, sulphur or nitrogen) assorted 3-18 straight chain or side chain hydrocarbyl residue; R
1Be in methyl, ethyl, n-propyl, sec.-propyl or the butyl any one, R
2Be in methyl, ethyl, n-propyl, sec.-propyl or the butyl any one, n is 2 or 3;
Formula (1).
2. a kind of silicon-phosphor-containing heat-stable hybridized epoxide resin according to claim 1 is characterized in that: described R is (CH
2)
5, CH
2-O-(CH
2)
3, CH
2-S-(CH
2)
3Or CH
2-O-[CH
2CH (OH) CH
2NCH
3]-CH
2
3. a kind of silicon-phosphor-containing heat-stable hybridized epoxide resin according to claim 1 is characterized in that: the many alkyl silanes of described epoxy group(ing) are a kind of in the epoxy third oxygen-butyl Trimethoxy silane, epoxypropoxy methyl dimethoxysilane, epoxypropoxy methyl diisopropoxy silane, the epoxy third oxygen octadecyltriethoxy silane, epoxypropoxy three n-propyl TMOSs, epoxypropoxy diethoxy silane, epoxypropoxy three butoxy silanes or the epoxypropoxy dimethoxy silane or any two kinds.
4. a kind of silicon-phosphor-containing heat-stable hybridized epoxide resin according to claim 1 is characterized in that: described deionized water consumption is 30～40 parts.
5. a kind of silicon-phosphor-containing heat-stable hybridized epoxide resin according to claim 1 is characterized in that: described organic solvent is one or more the mixed solvent in benzene, toluene, tetrahydrofuran (THF) or the butyl ether, and consumption is 90～120 parts.
6. a kind of silicon-phosphor-containing heat-stable hybridized epoxide resin according to claim 1, it is characterized in that: described phosphorous active substance is one or more the mixture in assorted phenanthrene of phosphorous acid, phosphoric acid, dialkyl phosphite, 10-oxidation-(9,10-2H-9-oxygen-10-phosphorus) or the phosphate dialkyl ester.
7. a kind of silicon-phosphor-containing heat-stable hybridized epoxide resin according to claim 1, it is characterized in that: described metal carboxylate comprises acid dibutyl tin, dibutyl tin acetate or stannous octoate, described an acidic catalyst comprises the organic acid or the Lewis acid of hydrochloric acid, sulfuric acid, phosphoric acid, boric acid, nitric acid, aryl sulfonic acid, 1～18 carbochain, and described basic catalyst comprises alkali-metal oxyhydroxide, alkali-metal oxide compound, organic amine or quaternary ammonium salt; Described catalyst levels is 0.01%～0.5% of many alkyl silanes of epoxy group(ing) quality.
8. a kind of silicon-phosphor-containing heat-stable hybridized epoxide resin according to claim 7 is characterized in that: described Lewis acid comprises phosphorus trichloride, boron trichloride, iron trichloride, ferric bromide, zinc chloride or tin tetrachloride; Described alkali-metal oxyhydroxide comprises that sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide or rubidium hydroxide, described alkali-metal oxide compound comprise that potassium oxide, sodium oxide, Cs2O, rubidium oxide or Lithium Oxide 98min, described organic amine comprise methylamine, ethamine or triethylamine.
9. the preparation method of the described silicon-phosphor-containing heat-stable hybridized epoxide resin of claim 1, it is characterized in that may further comprise the steps: count by weight, with 100 parts of the many alkyl silanes of epoxy group(ing), account for the catalyzer of many alkyl silanes of epoxy group(ing) quality 0.001%～0.5%, 50～120 parts of mixing of organic solvent, under 50～120 ℃, 10～40 parts of deionized waters are added drop-wise in the above-mentioned mixing solutions, and at 50～120 ℃ of hydrolysis backflow 2～8h, add 1～100 part of phosphorous active substance then, and at 100～160 ℃ of following reaction 3～10h, remove the solvent that dereaction is used, promptly get silicon-phosphor-containing heat-stable hybridized epoxide resin; The number-average molecular weight of described silicon-phosphor-containing heat-stable hybridized epoxide resin is 500～6000; Described catalyzer is metal carboxylate, an acidic catalyst or basic catalyst.
10. the application of the described silicon-phosphor-containing heat-stable hybridized epoxide resin of claim 1 in printed-wiring board (PWB), semiconductor sealing material.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100285241A CN100560632C (en) | 2007-06-11 | 2007-06-11 | A kind of silicon-phosphor-containing heat-stable hybridized epoxide resin and its production and application |
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| CN103161074A (en) * | 2013-02-04 | 2013-06-19 | 华南理工大学 | Fire retardants containing phosphorus, nitrogen, and silicon and used for fabric finish and preparation method thereof |
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