CN1810813A - Phosphorus-containing bishydroxy compound, phosphorus-containing epoxy resin synthesized therewith, and their prepn process and application - Google Patents
Phosphorus-containing bishydroxy compound, phosphorus-containing epoxy resin synthesized therewith, and their prepn process and application Download PDFInfo
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- CN1810813A CN1810813A CN 200610032647 CN200610032647A CN1810813A CN 1810813 A CN1810813 A CN 1810813A CN 200610032647 CN200610032647 CN 200610032647 CN 200610032647 A CN200610032647 A CN 200610032647A CN 1810813 A CN1810813 A CN 1810813A
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Abstract
The present invention discloses one kind of phosphorus-containing bishydroxy compound with the general expression as shown, its preparation process and application, and phosphorus-containing synthesized with the compound and its preparation process and application.
Description
Technical field
The present invention relates to a kind of compound, refer in particular to a kind of phosphorated dihydroxyl compound that is used to improve the synthetic resins flame retardant properties, the preparation method of this compound and application reach with this compound synthetic phosphorous epoxy resin and preparation method and application.
Background technology
Fire retardant material has purposes widely in field of electronics, for example copper-clad plate, moulding compound, joint sealant, seals material and various laminar composite, dip-coating material or the like.Electronic apparatus industry has also determined the dominant position of fire retardant material in this field to the requirement of fire-fighting.At present, widely used fire retardant material in the prior art, mainly be to be the compound and the resin thereof of matrix with halogenide, especially be representative with the bromide, they or interpolation or copolymerization have constituted flame-retardant system jointly with other inorganic combustion inhibitor, because good flame retardation effect, cheap, raw material is easy to get, and therefore is widely used in various fire-retardant occasions.
Along with human living standard's raising and intensive environmental protection cry more and more, brominated flame-retardant and incinerated matter thereof more and more cause people's query, because of producing strong carcinogens---Dioxins in its burning process.In addition, find that in the scene of fire victim more than 80% is not burnt to death by big fire, but choked to death, smoke extremely, poison with poison by dense smoke.Reason is that brominated flame-retardant produces a large amount of severe corrosive gas hydrogen bromides in combustion processes, be enough to causing death in several minutes, therefore European Union is in two environmental protection instructions, except that the use of restriction toxic heavy metal, also limited the fire retardant that contains bromo element, and will execute on July 1st, 2006.
Given this trend, each major company or research institution study the substitute of bromine flame retardant one after another in the world.With regard to present progress, tend to the fire-retardant of phosphorus, nitrogen compound mostly, wherein with phosphorus compound than tool feasibility.Its reason is: one, raw material is easy to get, and cost is lower; Two, the toxic smoke of emitting after the burning is less; Three, the discharge of goods belongs to the especially needed composition of farm crop of nature, does not bring secondary pollution; Four, the very little requirement that can reach flame-retardant standard of consumption.
About phosphonium flame retardant, comparatively commonly used is phosphoric acid ester at present, as tributyl phosphate, triphenylphosphate, Tritolyl Phosphate or the like, all has flame retardant effect preferably.But in use exist volatility big, easily the tendency of bloom, easy migration.In addition, aspect phosphorous epoxy, Japanese Patent JP2001-22047, JP10279657, JP2001-288246A once introduced certain methods, but all needed to use the DOPO monomer, so cost is high, can't apply on a large scale in actual production.
Summary of the invention
The purpose of this invention is to provide a kind of new, low, broad-spectrum a kind of phosphorated dihydroxyl compound of cost.
Next purpose of the present invention provides a kind of preparation method of above-mentioned phosphorated dihydroxyl compound of feasible process.
Further purpose of the present invention provides a kind of good flame retardation effect, broad-spectrum a kind of phosphorated fire-retardant epoxy resin.
Another object of the present invention provides a kind of preparation method of synthetic above-mentioned Resins, epoxy.
Still a further object of the present invention provides the application of a kind of above-claimed cpd aspect resin modified.
The present invention also has a purpose to provide the application of a kind of above-mentioned phosphorous epoxy resin in electronic industry.
A kind of phosphorated dihydroxyl compound of the present invention, available following general formula (I) expression:
R wherein
1, R
2Be identical or different aryl radical, R
3Be alkyl or alkoxyl group.
Alkyl is methyl, ethyl, butyl, phenyl etc. in the above-mentioned phosphorated dihydroxyl compound.
In the above-mentioned phosphorated dihydroxyl compound alkoxyl group be phenoxy group, substituent phenoxy such as oxy-o-cresyl, a tolyloxy, to tolyloxy, tertiary butyl phenoxy group, Nonylphenoxy, to phenyl phenoxy group etc.
The preparation method of phosphorated dihydroxyl compound of the present invention, comprise the steps: that successively (1) is dissolved in boiling point greater than in 150 ℃ the organic solvent with alkyl phosphinylidyne dichloro or alkoxyl group phosphinylidyne dichloro and dihydric phenol, under nitrogen protection, make catalyzer, in 150～200 ℃ of reactions 3～8 hours with halogeno salt; (2) cool to room temperature with 5% sodium bicarbonate aqueous solution flush away catalyzer and remaining alkyl phosphinylidyne dichloro or alkoxyl group phosphinylidyne dichloro, is used anhydrous MgSO
4Drying, filtration, underpressure distillation remove to desolvate and promptly get target product.
Catalyzer is that magnesium chloride, aluminum chloride, zinc chloride or their compound are good among the preparation method of above-mentioned phosphorated dihydroxyl compound.
Preparation method's mid-boiling point of above-mentioned phosphorated dihydroxyl compound is a boiling point greater than 150 ℃ aromatic hydrocarbons or halogenated aryl hydrocarbon greater than 150 ℃ organic solvent.
Aromatic hydrocarbons is meant trimethylbenzene, ethyl methyl benzene, diethylbenzene, isopropyl benzene, butylbenzene, amylbenzene etc. among the preparation method of above-mentioned phosphorated dihydroxyl compound; Halogenated aryl hydrocarbon is meant orthodichlorobenzene, Meta Dichlorobenzene, chlorotoluene, bromobenzene, dibromobenzene etc.
Phosphorous epoxy resin of the present invention is to be polymerized by above-mentioned phosphorated dihydroxyl compound and epoxy chloropropane, available following general formula (II) expression:
Wherein: R
1, R
2Be identical or different aryl radical, R
3Be alkyl or alkoxyl group.
The preparation method of phosphorous epoxy resin of the present invention, comprise the steps: (1) successively under nitrogen protection, the described compound of claim 1 and excessive 10～20 moles of epoxy chloropropane of doubly measuring are heated to 80 ± 5 ℃ of reactions 5 hours in the presence of the catalyzer tetramethyl ammonium chloride; (2) be cooled to 30 ℃, under violent stirring, carefully drip ealkaline buffer and keep temperature to be lower than 30 ℃, pH value≤9; (3) drip behind the ealkaline buffer under temperature is lower than 30 ℃ situation and continue reaction 5～10 hours; (4) branch vibration layer, to neutral, underpressure distillation promptly gets target product to organic layer then with the pure water washing.
Alkaline buffer solution described in the preparation method of above-mentioned phosphorous epoxy resin adopts alkalescence buffer solution, comprises sodium-acetate-sodium hydroxide-water, sodium phosphate-sodium hydroxide-water, sodium oxalate-sodium hydroxide-water, yellow soda ash-sodium hydroxide-water, EDTA disodium-sodium hydroxide-aqueous systems.
Phosphorated dihydroxyl compound of the present invention (I) can be used for the modification of polymkeric substance such as resol, ABS, polystyrene, to improve its flame retardant properties, method is to add in the resin melting process or the while mixed melting, and melt temperature is as long as all can more than the resin fluxing point.
Phosphorous epoxy resin of the present invention (II) mainly is used in electronics industry, and it can use separately, also can and use with ordinary epoxy resin.Ordinary epoxy resin refers generally to bisphenol A type epoxy resin and novolac epoxy.Solidifying agent is linear phenolic resin or nitrogenous linear phenolic resin preferably, also can use the latent amine, as Dyhard RU 100 etc.Phosphorous epoxy resin (II) through technologies such as infiltration, curing moldings, can be used on matrix material, copper-clad plate and Electronic Packaging field with after solidifying agent mixes.
The present invention compared with prior art has following advantage:
1. phosphorated dihydroxyl compound of the present invention is owing to contain two hydroxyls in the molecule, and boiling point is high, is solid state under the normal temperature, has reduced volatility, and active hydroxyl can produce crosslinking reaction with other resin, has eliminated transport property and volatility greatly.
2. phosphorated dihydroxyl compound of the present invention can be used as the flame-proof modifier of polymkeric substance such as existing resol, ABS, polystyrene, avoids producing harmful toxic smoke when burning, helps environment protection.
3. Resins, epoxy of the present invention has the good flame performance, can be used widely in matrix material, copper-clad plate and Electronic Packaging field.
Embodiment
Below in conjunction with specific embodiment the present invention is described in further detail, but does not constitute any limitation of the invention.
Embodiment 1
In the 500ml four-hole boiling flask of mechanical stirring, reflux condensing tube, thermometer, ventpipe is housed, add 55g (0.5mol) Resorcinol, 52.8g (0.25mol) phenoxy group phosphinylidyne dichloro, 1g aluminum chloride and 200ml trimethylbenzene, logical N
2Protection was heated to 170～175 ℃ of back flow reaction 3 hours; Cool to room temperature with 5% sodium bicarbonate aqueous solution flush away aluminum chloride and remaining phenoxy group phosphinylidyne dichloro, is used anhydrous MgSO then
4Drying, filtration, underpressure distillation remove and desolvate, and get 88g yellow solid (A).
Record: phosphorus content (oxygen flask combustion method) 8.6%, hydroxy radical content (nonaqueous titrations) 5.6mmol/g.
Embodiment 2
Reaction unit adds 45.6g (0.2mol) dihydroxyphenyl propane with embodiment 1,21.1g (0.1mol) phenoxy group phosphinylidyne dichloro, 0.5g aluminum chloride and 100ml trimethylbenzene, logical N
2Protection was heated 170～175 ℃ of back flow reaction 5 hours; Cool to room temperature with 5% sodium bicarbonate aqueous solution flush away aluminum chloride and remaining phenoxy group phosphinylidyne dichloro, is used anhydrous MgSO then
4Drying, filtration, underpressure distillation remove and desolvate, and get 58.5g yellow solid (B).
Record: phosphorus content (oxygen flask combustion method) 5.2%, hydroxy radical content (nonaqueous titrations) 3.3mmol/g.
Embodiment 3
Reaction unit adds 40g (0.2mol) Bisphenol F with embodiment 1,13.3g (0.1mol) methyl phosphinylidyne dichloro, the adjacent dibromobenzene of 0.5g zinc chloride and 150ml, logical N
2Protection is heated to 200 ℃ of reactions 5 hours; Cool to room temperature with 5% sodium bicarbonate aqueous solution flush away zinc chloride and remaining methyl phosphinylidyne dichloro, is used anhydrous MgSO
4Drying, filtration, underpressure distillation remove and desolvate, and get 44.8g yellow solid (C).
Record: phosphorus content (oxygen flask combustion method) 6.7%, hydroxy radical content (nonaqueous titrations) 4.3mmol/g.
Embodiment 4
Reaction unit adds 19.5g (0.1mol) phenyl phosphinylidyne dichloro with embodiment 1,22.0g (0.2mol) Resorcinol, 0.5g aluminum chloride and 100ml ortho-chlorotolu'ene, logical N
2Protection is heated to 150 ℃ of reactions 8 hours; Cool to room temperature with 5% sodium bicarbonate aqueous solution flush away aluminum chloride and remaining phenyl phosphinylidyne dichloro, is used anhydrous MgSO
4Drying, filtration, underpressure distillation remove and desolvate, and get 33.8g yellow solid (D).
Record: phosphorus content (oxygen flask combustion method) 9.0%, hydroxy radical content (nonaqueous titrations) 5.8mmol/g.
Embodiment 5
Reaction unit adds 11g (0.1mol) Resorcinol with embodiment 1,22.8g (0.1mol) dihydroxyphenyl propane, 19.5g (0.1mol) phenyl phosphinylidyne dichloro, 1g aluminum chloride and 100ml n-butylbenzene, logical N
2Protection was heated to 180～183 ℃ of back flow reaction 8 hours; Cool to room temperature with 5% sodium bicarbonate aqueous solution flush away aluminum chloride and remaining phenyl phosphinylidyne dichloro, is used anhydrous MgSO
4Drying, filtration, underpressure distillation remove and desolvate, and get 44.7g yellow solid (E).
Record: phosphorus content (oxygen flask combustion method) 6.7%, hydroxy radical content (nonaqueous titrations) 4.3mmol/g.
Embodiment 6
In the 500ml there-necked flask of mechanical stirring, reflux condensing tube, thermometer, ventpipe is housed, under the N2 protection, and the product (A) of adding 20g embodiment 1 (hydroxy radical content: 0.11mol), 102g (1.1mol) epoxy chloropropane, 0.1g tetramethyl ammonium chloride, 80 ℃ were reacted 5 hours; Be cooled to 20～25 ℃, carefully drip alkaline buffer solution (form: sodium phosphate/sodium hydroxide/water=2.2/4.4/13.4), temperature the highlyest is no more than 30 ℃ less than 25 ℃ in keeping; Control PH≤9 simultaneously; After adding buffered soln, continue at 25 ℃ with internal reaction 5 hours; Branch vibration layer, organic layer with pure water wash be neutrality till, underpressure distillation, yellow thick liquid (F).
Record: phosphorus content (oxygen flask combustion method) 5.6%, epoxy equivalent (weight) (perchloric acid method) 269g/eg.
Embodiment 7
Reaction unit is with embodiment 6, at N
2Under the protection, and adding 30g (hydroxy radical content: the 0.13mol) product of embodiment 4 (C), the 92.5g epoxy chloropropane, the 0.1g tetramethyl ammonium chloride, 80 ℃ were reacted 5 hours; Cool to room temperature, carefully drip alkaline buffer solution (form: EDTA2Na/ sodium hydroxide/water=2.5g/5.5g/20g), in whole dropping process temperature less than 30 ℃, PH≤9; Add and continue reaction 5 hours behind the buffered soln, branch vibration layer, organic layer with pure water wash be neutrality till, underpressure distillation, yellow thick liquid (G).
Record: phosphorus content (oxygen flask combustion method) 5.9%, epoxy equivalent (weight) (perchloric acid method) 358g/eg.
Embodiment 8
Reaction unit is with embodiment 6, at N
2Under the protection, and adding 20g (hydroxy radical content: the 0.12mol) product of embodiment 4 (C), 55.5g (0.6mol) epoxy chloropropane, the 0.1g tetramethyl ammonium chloride, 80 ℃ were reacted 5 hours; Reduce the temperature to 20 ℃, carefully drip alkaline buffer solution (form: yellow soda ash/sodium hydroxide/water=3.0g/4.0g/16g), in whole dropping process temperature less than 20 ℃, PH≤8.5; Continue reaction 10 hours at 15～20 ℃ after adding buffered soln; Branch vibration layer, organic layer with pure water wash be neutrality till; Underpressure distillation gets yellow thick liquid (H).
Record: phosphorus content (oxygen flask combustion method) 8.2%, epoxy equivalent (weight) (perchloric acid method) 295g/eg.
Embodiment 9
With product (A) 10g of embodiment 1, common novolac resin 30g is heated to 120 ℃ of fusion half an hour, and cool to room temperature is crushed to below 50 orders, and mixes with the 5g urotropine, is hot pressed into strip at 180 ℃ at last.
Product limiting oxygen index(LOI) (LOI): 46.
Press with sampling technology pure phenolic resin limiting oxygen index(LOI) (LOI): 35.
Embodiment 10
With product (A) 10g of embodiment 1, with 30gABS after 180 ℃ of fusions, be extruded into strip cooling.
Product limiting oxygen index(LOI) (LOI): 31.4
ABS limiting oxygen index(LOI) (LOI): 18.5
Embodiment 11
With product (A) 10g of embodiment 1, with 30gPS after 180 ℃ of fusions, be extruded into strip cooling.
Product limiting oxygen index(LOI) (LOI): 25.3
ABS limiting oxygen index(LOI) (LOI): 18.0
Embodiment 12
Product (H) 10g of embodiment 8 is dissolved in (mixed solvent ratio: DMF/ ethylene glycol monomethyl ether/acetone=3/3/4) in the mixed solvent, add common novolac resin 3.6g then, whole system is dissolved into transparent and homogeneous solution, soaking into the back with glasscloth takes out and pushes, solidify in drying in oven, processing condition are: 60 ℃/1 hour+120 ℃/1 hour+180 ℃/3 hours.
The fire-retardant rank of glasscloth (UL94 vertical combustion method): V-0 level.
Above-mentioned (H) replaced with common bisphenol A epoxide resin (EEW:450～500), and other technology is constant, the fire-retardant rank of glasscloth: burning.
Embodiment 13
Product (H) 10g and the 20g bisphenol A epoxide resin (EEW:450～500) of embodiment 8 are dissolved in (mixed solvent ratio: DMF/ ethylene glycol monomethyl ether/acetone=3/3/4) in the 30g mixed solvent, add the 3g Dyhard RU 100, stirring and dissolving becomes transparent and homogeneous solution, soaking into the back with glasscloth takes out and pushes, solidify in drying in oven, processing condition are: 60 ℃/1 hour+120 ℃/1 hour+180 ℃/1 hour.
The fire-retardant rank of glasscloth (UL94 vertical combustion method): V-1 level.
Above-mentioned (H) replaced with common bisphenol A epoxide resin (EEW:450～500), and other technology is constant, the fire-retardant rank of glasscloth: burning.
Claims (14)
1. following general formula (I) compound:
R wherein
1, R
2Be identical or different aryl radical, R
3Be alkyl or alkoxyl group.
2. compound according to claim 1, wherein alkyl is methyl, ethyl, butyl, phenyl.
3. compound according to claim 1, wherein alkoxyl group is phenoxy group, substituent phenoxy.
4. the preparation method of the described compound of claim 2, comprise the steps: that successively (1) is dissolved in boiling point greater than in 150 ℃ the organic solvent with alkoxyl group phosphinylidyne dichloro and dihydric phenol, under nitrogen protection, make catalyzer, in 150～200 ℃ of reactions 3～5 hours with halogeno salt; (2) cool to room temperature with 5% sodium bicarbonate aqueous solution flush away catalyzer and remaining alkyl phosphinylidyne dichloro, is used anhydrous MgSO
4Drying, filtration, underpressure distillation remove to desolvate and promptly get target product.
5. the preparation method of the described compound of claim 3, comprise the steps: that successively (1) is dissolved in boiling point greater than in 150 ℃ the organic solvent with alkoxyl group phosphinylidyne dichloro and dihydric phenol, under nitrogen protection, make catalyzer, in 150～200 ℃ of reactions 3～5 hours with halogeno salt; (2) cool to room temperature with 5% sodium bicarbonate aqueous solution flush away catalyzer and remaining alkoxyl group phosphinylidyne dichloro, is used anhydrous MgSO
4Drying, filtration, underpressure distillation remove to desolvate and promptly get target product.
6. according to claim 4,5 described preparation methods, wherein catalyzer is magnesium chloride, aluminum chloride, zinc chloride or their compound.
7. according to claim 4,5 described preparation methods, its mid-boiling point is a boiling point greater than 150 ℃ aromatic hydrocarbons or halogenated aryl hydrocarbon greater than 150 ℃ organic solvent.
8. preparation method according to claim 7, wherein aromatic hydrocarbons is meant trimethylbenzene, ethyl methyl benzene, diethylbenzene, isopropyl benzene, butylbenzene, amylbenzene.
9. preparation method according to claim 7, wherein halogenated aryl hydrocarbon is meant orthodichlorobenzene, Meta Dichlorobenzene, chlorotoluene, bromobenzene, dibromobenzene.
10. a phosphorous epoxy resin is characterized in that being polymerized by described compound of claim 1 and epoxy chloropropane, and has following general formula (II):
Wherein: R
1, R
2Be identical or different aryl radical, R
3Be alkyl or alkoxyl group.
11. the preparation method of the described phosphorous epoxy resin of claim 10, comprise the steps: (1) successively under nitrogen protection, the described compound of claim 1 and excessive 10～20 moles of epoxy chloropropane of doubly measuring are heated to 80 ± 5 ℃ of reactions 5 hours in the presence of the catalyzer tetramethyl ammonium chloride; (2) be cooled to 30 ℃, under violent stirring, carefully drip ealkaline buffer and keep temperature to be lower than 30 ℃, pH value≤9; (3) drip behind the ealkaline buffer under temperature is lower than 30 ℃ situation and continue reaction 5～10 hours; (4) branch vibration layer, to neutral, underpressure distillation promptly gets target product to organic layer then with the pure water washing.
12. preparation method according to claim 11, wherein said alkaline buffer solution adopts alkalescence buffer solution, comprises sodium-acetate-sodium hydroxide-water, sodium phosphate-sodium hydroxide-water, sodium oxalate-sodium hydroxide-water, yellow soda ash-sodium hydroxide-water, EDTA disodium-sodium hydroxide-aqueous systems.
13. the application of the described compound of claim 1 in resin modified.
14. the application of the described Resins, epoxy of claim 10 in electronic industry.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200610032647 CN1810813A (en) | 2006-01-05 | 2006-01-05 | Phosphorus-containing bishydroxy compound, phosphorus-containing epoxy resin synthesized therewith, and their prepn process and application |
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| CN 200610032647 CN1810813A (en) | 2006-01-05 | 2006-01-05 | Phosphorus-containing bishydroxy compound, phosphorus-containing epoxy resin synthesized therewith, and their prepn process and application |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103059264A (en) * | 2012-12-27 | 2013-04-24 | 北京德成嘉化工科技有限责任公司 | A phosphorus-containing diglycidyl ether, a preparation method thereof and a flame-retardant cured epoxy resin containing the same |
| US20140205832A1 (en) * | 2013-01-22 | 2014-07-24 | Frx Polymers, Inc. | Phosphorus containing epoxy compounds and compositions therefrom |
| CN110105539A (en) * | 2019-06-11 | 2019-08-09 | 广东同宇新材料有限公司 | Application, fire retarding epoxide resin and preparation method and application of the phosphorus-containing compound in one-step synthesis method fire retarding epoxide resin |
| CN113214454A (en) * | 2021-06-28 | 2021-08-06 | 西华大学 | Transparent halogen-free flame-retardant epoxy resin, material and preparation method thereof |
-
2006
- 2006-01-05 CN CN 200610032647 patent/CN1810813A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103059264A (en) * | 2012-12-27 | 2013-04-24 | 北京德成嘉化工科技有限责任公司 | A phosphorus-containing diglycidyl ether, a preparation method thereof and a flame-retardant cured epoxy resin containing the same |
| US20140205832A1 (en) * | 2013-01-22 | 2014-07-24 | Frx Polymers, Inc. | Phosphorus containing epoxy compounds and compositions therefrom |
| CN104981474A (en) * | 2013-01-22 | 2015-10-14 | Frx聚合物股份有限公司 | Phosphorus containing epoxy compounds and compositions therefrom |
| JP2016510355A (en) * | 2013-01-22 | 2016-04-07 | エフアールエックス ポリマーズ、インク． | Phosphorus-containing epoxy compound and composition comprising the same |
| US10167377B2 (en) * | 2013-01-22 | 2019-01-01 | Frx Polymers, Inc. | Phosphorus containing epoxy compounds and compositions therefrom |
| CN110105539A (en) * | 2019-06-11 | 2019-08-09 | 广东同宇新材料有限公司 | Application, fire retarding epoxide resin and preparation method and application of the phosphorus-containing compound in one-step synthesis method fire retarding epoxide resin |
| CN113214454A (en) * | 2021-06-28 | 2021-08-06 | 西华大学 | Transparent halogen-free flame-retardant epoxy resin, material and preparation method thereof |
| CN113214454B (en) * | 2021-06-28 | 2022-06-07 | 西华大学 | Transparent halogen-free flame-retardant epoxy resin, material and preparation method thereof |
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