CN102766113A - Preparation method of hydrogenated bisphenol A epoxy resin - Google Patents
Preparation method of hydrogenated bisphenol A epoxy resin Download PDFInfo
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- CN102766113A CN102766113A CN2012102747871A CN201210274787A CN102766113A CN 102766113 A CN102766113 A CN 102766113A CN 2012102747871 A CN2012102747871 A CN 2012102747871A CN 201210274787 A CN201210274787 A CN 201210274787A CN 102766113 A CN102766113 A CN 102766113A
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Abstract
The invention relates to a preparation method of hydrogenated bisphenol A epoxy resin. The preparation method comprises the steps of raw material pre-treatment, ring-opening addition and etherifying, ring-closing epoxidation, product post-treatment and the like. The specific steps are as follows: based on hydrogenated bisphenol A and epoxy chloropropane as raw materials, adding solvent; performing ring-opening etherifying by taking Lewis acid as a catalyst to produce chlorohydrin ether immediate; recovering part of the solvent, adding alkali solution and performing ring-closing dechlorinating reaction; carrying out post-treatment steps such as neutralizing, extracting, water washing, vacuum desolventizing to obtain hydrogenated bisphenol A epoxy resin, wherein the epoxide equivalent of the product is 210-240g/eq; the hydrolyzable chlorine content is not more than 1000ppm; the inorganic chloride content is not more than 10ppm; the viscosity is 2000-5000mPas at 25 DEG C; and the volatile component content is not more than 0.1%. The preparation method of hydrogenated bisphenol A epoxy resin has the advantages of stable process, low material and energy consumption, few by-products, simple water-washing and separating operation and high product yield, therefore, the preparation method can be applied in large-scale industrial production.
Description
Technical field
The invention belongs to the organic high molecular compound technical field, be specifically related to a kind of preparation method of hydrogenated bisphenol A epoxy resin.
Background technology
When general bisphenol A type epoxy resin is used out of doors, exist shortcomings such as easy-weathering, aging, easy xanthochromia.Consider that from molecular structure the reason of bisphenol A type epoxy resin weathering resistance difference is owing to have a large amount of undersaturated benzene ring structures in the molecule segment.Under the condition of atmosphere or ultraviolet long-term irradiation, molecular chain ruptures easily, causes the index such as the transparency, insulativity, intensity of bisphenol A type epoxy resin cured article to decline to a great extent.The exploitation weathering resistance is strong, is applicable to that outdoor epoxy resin product becomes China's epoxy resin and produces and use producer's expectation.
The Hydrogenated Bisphenol A 99 molecular structure is close with the dihydroxyphenyl propane molecular structure, and the phenyl ring in the dihydroxyphenyl propane molecule is saturated through hydrogenation.Hydrogenated bisphenol A epoxy resin and general bisphenol A type epoxy resin have close performance, but because phenyl ring is transformed into saturated six-ring, have overcome the fracture defective of the two keys of insatiable hunger.Resin cured matter shows good weathering resistance, corona resistance, chemical-resistant, can be widely used in outdoor coating, senior environmental friendly indoor finishing paint, outdoor mould material, Electronic Packaging projects such as (LED)., the project of weather-proof, UV resistant requirement more has superiority in being arranged than common bisphenol A-type epoxy resin.
Hydrogenated bisphenol A epoxy resin is developed by Japanese Toto Kasei KK at first, mainly contains two trades mark of ST-3000 and ST-3000H.Domestic rivers and mountains Jiang Huanhua, South Asia, Taiwan company etc. have certain industrial scale.ST-3000, ST-3000H that hydrogenated bisphenol A epoxy resin still a kind of newer epoxy resin kind for China, quality product generally adopt Japanese Toto Kasei KK are as a reference.Chinese patent CN200810223689.9 has reported a kind of method that follows the synthesizing hydrogenated bisphenol A epoxide resin of universal bisphenol A epoxide resin synthetic route.Adopting Hydrogenated Bisphenol A 99 and epoxy chloropropane is raw material, and Lewis acid is a ring opening catalyst, under 30 ~ 120 ℃, carries out etherification reaction and generates chloropharin ether, adds the alkaline matter ring-closure reaction then, obtains hydrogenated bisphenol A epoxy resin through aftertreatment.Because Hydrogenated Bisphenol A 99 structure and performance and dihydroxyphenyl propane be difference to some extent, follows general bisphenol A type epoxy resin synthetic route, in actual production, can face many difficulties.As, a spot of water makes in the reaction raw materials Lewis acid hydrolysis influences the open loop effect; Hydrogenated Bisphenol A 99 is insoluble to toluene, MIBK solubility promoters such as (MIBK), causes stirring difficulty; The hydroxyl activity at Hydrogenated Bisphenol A 99 molecule two ends is littler than dihydroxyphenyl propane two ends hydroxyl activity, and reaction temperature is spent low can causing and reacted not exclusively, and the production cycle is long, and product purity is difficult to control, by product is many etc.
Summary of the invention
The object of the present invention is to provide a kind of simple to operate, process stabilizing, can be used for the hydrogenated bisphenol A epoxy resin preparation method of suitability for industrialized production.
The hydrogenated bisphenol A epoxy resin molecular structural formula of the present invention's preparation is following:
The compound method of hydrogenated bisphenol A epoxy resin provided by the present invention, adopting Hydrogenated Bisphenol A 99 and epoxy chloropropane is raw material.After the raw materials pretreatment, be ring opening catalyst, under 50 ~ 100 ℃, carry out etherification reaction, generate chloropharin ether with the Lewis acid.Add reaction base behind the recovery part solvent, under 50 ~ 100 ℃, carry out ring-closure reaction.Reaction finishes the back supplementing solvent, obtains hydrogenated bisphenol A epoxy resin through postprocessing working procedures such as extraction, neutralization, washing, desolventizings.Wherein, the mol ratio of Hydrogenated Bisphenol A 99, epoxy chloropropane, reaction base and ring opening catalyst is 1:2 ~ 3:2 ~ 3:0.003 ~ 0.008; Preferred mol ratio is 1:2 ~ 2.5:2 ~ 2.5:0.004～0.007.
Hydrogenated bisphenol A epoxy resin compound method of the present invention comprises the steps:
(1) raw materials pretreatment.In the reaction kettle that stirring rake, TM, water trap and reflux exchanger are housed, add Hydrogenated Bisphenol A 99 and solvent, the temperature rising reflux dehydration.The charging capacity of solvent is 0.5 ~ 3 times of Hydrogenated Bisphenol A 99.
(2) open loop addition etherificate.Add lewis acid catalyst after the product temperature of step (1) reduced to 70 ~ 110 ℃, drip epoxy chloropropane, carry out ring opening etherification reaction, generate chloropharin ether.The ring opening etherification reaction temperature is 50 ~ 110 ℃.Epoxy chloropropane adds in 2 ~ 5h.Add the epoxy chloropropane continued and keep reaction 0.5 ~ 3h.The feed ratio of Hydrogenated Bisphenol A 99, catalyzer and epoxy chloropropane is 1:0.003 ~ 0.008:2～3.
(3) closed loop epoxidation.With its charging capacity of solvent recuperation in the product of step (2) 20% ~ 70% after, add entry and an amount of high concentration alkali, make that the concentration of final alkali is 10% ~ 45%.Be 0.5 ~ 3h add-subtract time, adds that to keep the reaction times after alkali finishes be 3 ~ 18h.The ring-closure reaction temperature is 50 ~ 100 ℃.The feed ratio of Hydrogenated Bisphenol A 99 and reaction base is 1:2 ~ 3.
(4) product postprocessing.Product toward step (3) replenishes an amount of solvent, obtains hydrogenated bisphenol A epoxy resin through dissolving, neutralization, washing, vacuum desolventizing after handling.
Wherein the described solvent of step (1) has: aromatic hydrocarbons such as toluene, YLENE etc.; Ketone such as MIBK, pimelinketone etc.; Cycloalkane such as hexanaphthene etc., or the mixture of several kinds of solvents.Preferred solvent is a toluene.Preferable amount is 1～2 times of Hydrogenated Bisphenol A 99 charging capacity.
The described reflux dewatering temperature of step (1) is 80～120 ℃, and dewatering time is 0.5～1.5h.Optimizing technology parameters is 100～116 ℃ of reflux dewatering temperature, time 0.5～1h.
The said Lewis acid of step (2) has aluminum chloride, iron(ic)chloride, boron trifluoride, tin tetrachloride etc.Catalyst levels be Hydrogenated Bisphenol A 99 mol ratio 0.003～0.008.Preferred boron trifluoride, preferable amount is 0.004～0.007.Preferred temperature is 80～100 ℃ when adding catalyzer.
The preferred temperature of the said etherification reaction of step (2) is 80～100 ℃.
The said epoxy chloropropane consumption of step (2) is more than 2 times of Hydrogenated Bisphenol A 99 mole number, could guarantee that Hydrogenated Bisphenol A 99 molecule two ends hydroxyl reaction is complete.Because epoxy chloropropane is easy to polymerization reaction take place under the effect of lewis acid catalyst, therefore, epoxy chloropropane charging capacity outline is more than 2 times of Hydrogenated Bisphenol A 99, and the epoxy chloropropane consumption is very few, can cause the epoxy resin molecular chain long, and oxirane value reduces.The epoxy chloropropane consumption does not too much obviously improve quality product, but can cause the wasting of resources.Therefore, the molar ratio of preferred Hydrogenated Bisphenol A 99 and epoxy chloropropane is 1:2～2.5.Dripping the epoxy chloropropane time is preferably 2～4h, keeps the reaction times after adding to be preferably 0.5～2h.
The amount of the said recovery solvent of step (3) is preferably 30～60% of its charging capacity.
The said alkaline matter of step (3) is: NaOH, KOH etc.From the considerations such as security of raw material sources, technological operation, the preferred NaOH aqueous solution.Adopt to add water earlier, drip the mode of high concentration alkali again, the high concentration alkali scope is 40～70%.The final alkali concn scope that adds reaction system is 10～35%.Preferred concentration range for is 15～30%.
The said alkali that adds of step (3) adopts the dropping mode.The epoxy ring-closure reaction is thermo-negative reaction, so must guarantee certain temperature in the reaction process.The specific activity dihydroxyphenyl propane of Hydrogenated Bisphenol A 99 molecule two terminal hydroxy group is low, therefore, need keep the reaction regular hour at a certain temperature, just can make reaction carry out guaranteeing that product has lower epoxy equivalent (weight) and hydrolyzable chlorine content fully.Preferably adding alkali ring-closure reaction temperature is 80～100 ℃, and be 1～3h add-subtract time, adds that to keep the reaction times preferable range after alkali finishes be 6～15h.
The described alkali number that adds of step (3) is at least more than 2 times of Hydrogenated Bisphenol A 99 mole number, could guarantee that Hydrogenated Bisphenol A 99 molecule two ends hydroxyl reaction is complete.But too much alkali can cause the intermolecular generation of product crosslinked, thereby influences quality product.The suitable Hydrogenated Bisphenol A 99 and the molar ratio of alkali are 1:2～3., preferable range is 1:2～2.7.
The solvent phase that said additional solvent of step (4) and raw materials pretreatment are used with, solvent load is 2～4 times (mass ratioes) of Hydrogenated Bisphenol A 99 charging capacity.Solvent temperature is 60～90 ℃, dissolution time 0.5～1h.
The acidic substance that the said neutralization of step (4) is adopted comprise: phosphoric acid, boric acid, sodium hydrogencarbonate, oxalic acid, acetic acid etc.Strong acid can destroy epoxide group, and therefore neutralization can only be adopted weak acid.Consider preferably phosphoric acid from operational condition.Be neutralized to PH=5～7 of material.Wash to PH=6～7.
The said desolventizing top temperature of step (4) is 140 ℃～180 ℃.Vacuum tightness is-below the 0.09MPa.When temperature and vacuum tightness are not high enough, can cause the product volatile matter too high.The too high meeting of temperature causes product colour to deepen.
It is colourless to faint yellow transparent thick liquid adopting above technology synthetic hydrogenated bisphenol A epoxy resin, and epoxy equivalent (weight) is 210～240g/eq, hydrolyzable chlorine content≤1000ppm; Content of inorganic chlorine≤10ppm; Viscosity 2000～5000mPa.s, 25 ℃, volatile matter≤0.1%.
Compare with existing bisphenol-A epoxy resin synthesis technique: technology of the present invention has been carried out processed to reaction raw materials, has guaranteed the reaction effect in the etherification procedure.According to reaction principle the charging capacity of material is carried out scientific matching, both guaranteed to react and carried out reducing raw material consumption again fully as far as possible.Consider to occur in the actually operating stirring difficulty, rationally adjust the consumption of solubility promoter.The synthesizing hydrogenated bisphenol A epoxide resin process stabilizing of the present invention, the material consumption energy consumption is low, and by product is few, and the washing separatory is simple to operate, and product yield is high, can be used for large-scale commercial prodn.
Embodiment
Further specify the present invention below in conjunction with embodiment, but be not further qualification of the present invention.
Embodiment 1
In the 2000ml reaction kettle of whisking appliance, TM, water trap and condensing surface is housed, add Hydrogenated Bisphenol A 99 360g and solvent toluene 400g, open and stir, be warming up to 113 ℃ of reflux dewaterings.Be cooled to 100 ℃ behind the dehydration 1h and add catalyzer BFEE 1.01g.At the uniform velocity drip epoxy chloropropane 310g through peristaltic pump and carry out open loop addition etherification reaction, the epoxy chloropropane dropping time is 2.5h, adds continued and keeps 0.5h, continues to observe system temperature variation and Hydrogenated Bisphenol A 99 dissolving situation in the dropping process.Because the ring-opening reaction heat release drips in the epoxy chloropropane process and will take suitable cooling provision, guarantee that temperature of reaction is in 98～102 ℃.Reaction finishes the back and reclaims toluene 207g.In reaction kettle, add pure water 400g, drip 48.8% NaOH aqueous solution 315g again through peristaltic pump, adding the NaOH time is 2h, 90 ℃ of temperature of reaction.Add NaOH end continued and keep reaction 8h.Reaction is added toluene 400g after finishing, and stops to stir, and is static, divides the sub-cloud water layer, drips H
3PO
4Be adjusted to PH≤6.Repeat to wash static separatory to water PH=6.5～7.Wash qualified back 150 ℃ of following underpressure distillation, vacuum tightness≤-0.09MPa, obtain hydrogenated bisphenol A epoxy resin 530g after removing solvent toluene.Products obtained therefrom is colourless to faint yellow transparent thick liquid; Epoxy equivalent (weight) (g/eq): 235; Hydrolyzable chlorine (ppm): 550, content of inorganic chlorine (ppm): 5; Viscosity (mPa.s, 25 ℃): 2565.
Embodiment 2
In the 2000ml reaction kettle of whisking appliance, TM, water trap and condensing surface is housed, add Hydrogenated Bisphenol A 99 360g and solvent toluene 600g, open and stir, be warming up to 113 ℃ of reflux dewaterings.Be cooled to 100 ℃ behind the dehydration 1h and add catalyzer BFEE 1.01g.At the uniform velocity drip epoxy chloropropane 333g through peristaltic pump and carry out open loop addition etherification reaction, the epoxy chloropropane dropping time is 3h, adds continued and keeps 1h, continues to observe system temperature variation and Hydrogenated Bisphenol A 99 dissolving situation in the dropping process.Because the ring-opening reaction heat release drips in the epoxy chloropropane process and will take suitable cooling provision, guarantee that temperature of reaction is in 98～102 ℃.Reaction finishes the back and reclaims toluene 450g.In reaction kettle, add pure water 400g, drip 48.8% NaOH aqueous solution 315g again through peristaltic pump, adding the NaOH time is 2h, 90 ℃ of temperature of reaction.Add NaOH end continued and keep reaction 8h.Reaction is added toluene 400g after finishing, and stops to stir, and is static, divides the sub-cloud water layer, drips H
3PO
4Be adjusted to PH≤6.Repeat to wash static separatory to water PH=6.5～7.Wash qualified back 150 ℃ of following underpressure distillation, vacuum tightness≤-0.09MPa, obtain hydrogenated bisphenol A epoxy resin 540g after removing solvent toluene.Products obtained therefrom is colourless to faint yellow transparent thick liquid; Epoxy equivalent (weight) (g/eq): 229; Hydrolyzable chlorine (ppm): 533, content of inorganic chlorine (ppm): 6; Viscosity (mPa.s, 25 ℃): 2462.
Embodiment 3
In the 2000ml reaction kettle of whisking appliance, TM, water trap and condensing surface is housed, add Hydrogenated Bisphenol A 99 360g and solvent toluene 420g, open and stir, be warming up to 110 ℃ of reflux dewaterings.Be cooled to 100 ℃ behind the dehydration 0.5h and add catalyst A lCl
41.01g.At the uniform velocity drip epoxy chloropropane 333g through peristaltic pump and carry out open loop addition etherification reaction, the epoxy chloropropane dropping time is 3h, adds continued and keeps 1h, continues to observe system temperature variation and Hydrogenated Bisphenol A 99 dissolving situation in the dropping process.Because the ring-opening reaction heat release drips in the epoxy chloropropane process and will take suitable cooling provision, guarantee that temperature of reaction is in 98～102 ℃.Reaction finishes the back and reclaims toluene 240g.In reaction kettle, add pure water 400g, drip 48.8% NaOH aqueous solution 315g again through peristaltic pump, be 2h add-subtract time, 90 ℃ of temperature of reaction.Add alkali end continued and keep reaction 8h.Reaction is added toluene 400g after finishing, and stops to stir, and is static, divides the sub-cloud water layer, drips H
3PO
4Be adjusted to PH≤6.Repeat to wash static separatory to water PH=6.5～7.Wash qualified back 150 ℃ of following underpressure distillation, vacuum tightness≤-0.09MPa, obtain hydrogenated bisphenol A epoxy resin 553g after removing solvent toluene.Products obtained therefrom is colourless to faint yellow transparent thick liquid; Epoxy equivalent (weight) (g/eq): 231; Hydrolyzable chlorine (ppm): 580, content of inorganic chlorine (ppm): 3; Viscosity (mPa.s, 25 ℃): 2365.
Embodiment 4
In the 2000ml reaction kettle of whisking appliance, TM, water trap and condensing surface is housed, add Hydrogenated Bisphenol A 99 360g and solvent MIBK 420g, open and stir, be warming up to 116 ℃ of reflux dewaterings.Be cooled to 100 ℃ behind the dehydration 1h and add catalyzer BFEE 1.01g.At the uniform velocity drip epoxy chloropropane 330g through peristaltic pump and carry out open loop addition etherification reaction, the epoxy chloropropane dropping time is 3h, adds continued and keeps 1.5h, continues to observe system temperature variation and Hydrogenated Bisphenol A 99 dissolving situation in the dropping process.Because the ring-opening reaction heat release drips in the epoxy chloropropane process and will take suitable cooling provision, guarantee that temperature of reaction is in 98～102 ℃.If MIBK contains impurity, may cause the product color slightly dark.Reaction finishes the back and reclaims solvent 207g.In reaction kettle, add pure water 400g, drip 48.8% NaOH aqueous solution 315g again through peristaltic pump, be 2h add-subtract time, 90 ℃ of temperature of reaction.Add alkali end continued and keep reaction 8h.Reaction is added solvent 400g after finishing, and stops to stir, and is static, divides the sub-cloud water layer, drips H
3PO
4Be adjusted to PH≤6.Repeat to wash static separatory to water PH=6.5～7.Wash qualified back 150 ℃ of following underpressure distillation, vacuum tightness≤-0.09MPa, obtain hydrogenated bisphenol A epoxy resin 549g after removing solvent toluene.Products obtained therefrom is colourless to faint yellow transparent thick liquid; Epoxy equivalent (weight) (g/eq): 233; Hydrolyzable chlorine (ppm): 580, content of inorganic chlorine (ppm): 10; Viscosity (mPa.s, 25 ℃): 2385.
Embodiment 5
In the 2000ml reaction kettle of whisking appliance, TM, water trap and condensing surface is housed, add Hydrogenated Bisphenol A 99 360g and solvent toluene 500g, open and stir, be warming up to 110 ℃ of reflux dewaterings.Be cooled to 100 ℃ behind the dehydration 1h and add catalyzer BFEE 1.01g.At the uniform velocity drip epoxy chloropropane 333g through peristaltic pump and carry out open loop addition etherification reaction, the epoxy chloropropane dropping time is 3h, adds continued and keeps 1h, continues to observe system temperature variation and Hydrogenated Bisphenol A 99 dissolving situation in the dropping process.Because the ring-opening reaction heat release drips in the epoxy chloropropane process and will take suitable cooling provision, guarantee that temperature of reaction is in 98～102 ℃.Reaction finishes the back and reclaims solvent 330g.In reaction kettle, add pure water 450g, drip 48.8% NaOH aqueous solution 315g again through peristaltic pump, adding the NaOH time is 1.5h, 95 ℃ of temperature of reaction.Add NaOH end continued and keep reaction 10h.Reaction is added solvent 400g after finishing, and stops to stir, and is static, divides the sub-cloud water layer, drips H
3PO
4Be adjusted to PH≤6.Repeat to wash static separatory to water PH=6.5～7.Wash qualified back 150 ℃ of following underpressure distillation, vacuum tightness≤-0.09MPa, obtain hydrogenated bisphenol A epoxy resin 557g after removing solvent toluene.Products obtained therefrom is colourless to faint yellow transparent thick liquid; Epoxy equivalent (weight) (g/eq): 228; Hydrolyzable chlorine (ppm): 593, content of inorganic chlorine (ppm): 5; Viscosity (mPa.s, 25 ℃): 2335.
Embodiment 6
In the 2000ml reaction kettle of whisking appliance, TM, water trap and condensing surface is housed, add Hydrogenated Bisphenol A 99 360g and solvent toluene 420g, open and stir, be warming up to 110 ℃ of reflux dewaterings.Be cooled to 100 ℃ behind the dehydration 1h and add catalyzer BFEE 1.01g.At the uniform velocity drip epoxy chloropropane 333g through peristaltic pump and carry out open loop addition etherification reaction, the epoxy chloropropane dropping time is 3h, adds continued and keeps 1h, continues to observe system temperature variation and Hydrogenated Bisphenol A 99 dissolving situation in the dropping process.Because the ring-opening reaction heat release drips in the epoxy chloropropane process and will take suitable cooling provision, guarantee that temperature of reaction is in 98～102 ℃.Reaction finishes the back and reclaims solvent 250g.In reaction kettle, add pure water 450g, drip 48.8% NaOH aqueous solution 315g again through peristaltic pump, adding the NaOH time is 1.5h, 95 ℃ of temperature of reaction.Add NaOH end continued and keep reaction 18h.Reaction is added solvent 400g after finishing, and stops to stir, and is static, divides the sub-cloud water layer, drips H
3PO
4Be adjusted to PH≤6.Repeat to wash static separatory to water PH=6.5～7.Wash qualified back 150 ℃ of following underpressure distillation, vacuum tightness≤-0.09MPa, obtain hydrogenated bisphenol A epoxy resin 557g after removing solvent toluene.Products obtained therefrom is colourless to faint yellow transparent thick liquid; Epoxy equivalent (weight) (g/eq): 226; Hydrolyzable chlorine (ppm): 463, content of inorganic chlorine (ppm): 3; Viscosity (mPas, 25 ℃): 2235.
Embodiment 7
In the 2000ml reaction kettle of whisking appliance, TM, water trap and condensing surface is housed, add Hydrogenated Bisphenol A 99 360g and solvent toluene 420g, open and stir, be warming up to 110 ℃ of reflux dewaterings.Be cooled to 100 ℃ behind the dehydration 1h and add catalyst S nCl
41.01g.At the uniform velocity drip epoxy chloropropane 333g through peristaltic pump and carry out open loop addition etherification reaction, the epoxy chloropropane dropping time is 3h, adds continued and keeps 1h, continues to observe system temperature variation and Hydrogenated Bisphenol A 99 dissolving situation in the dropping process.Because the ring-opening reaction heat release drips in the epoxy chloropropane process and will take suitable cooling provision, guarantee that temperature of reaction is in 98～102 ℃.Reaction finishes the back and reclaims solvent 250g.In reaction kettle, add pure water 450g, drip 48.8% NaOH aqueous solution 315g again through peristaltic pump, be 1.5h add-subtract time, 95 ℃ of temperature of reaction.Add alkali end continued and keep reaction 9h.Reaction is added solvent 400g after finishing, and stops to stir, and is static, divides the sub-cloud water layer, drips H
3PO
4Be adjusted to PH≤6.Repeat to wash static separatory to water PH=6.5～7.Wash qualified back 150 ℃ of following underpressure distillation, vacuum tightness≤-0.09MPa, obtain hydrogenated bisphenol A epoxy resin 553g after removing solvent toluene.Products obtained therefrom is colourless to faint yellow transparent thick liquid; Epoxy equivalent (weight) (g/eq): 235; Hydrolyzable chlorine (ppm): 566, content of inorganic chlorine (ppm): 8; Viscosity (mPa.s, 25 ℃): 2435.
Embodiment 8
In the 2000ml reaction kettle of whisking appliance, TM, water trap and condensing surface is housed, add Hydrogenated Bisphenol A 99 360g and solvent toluene 420g, open and stir, be warming up to 110 ℃ of reflux dewaterings.Be cooled to 100 ℃ behind the dehydration 1h and add catalyzer BFEE 1.01g.At the uniform velocity drip epoxy chloropropane 333g through peristaltic pump and carry out open loop addition etherification reaction, the epoxy chloropropane dropping time is 3h, adds continued and keeps 1h, continues to observe system temperature variation and Hydrogenated Bisphenol A 99 dissolving situation in the dropping process.Because the ring-opening reaction heat release drips in the epoxy chloropropane process and will take suitable cooling provision, guarantee that temperature of reaction is in 98～102 ℃.Reaction finishes the back and reclaims solvent 250g.In reaction kettle, add pure water 450g, through the KOH aqueous solution 427gg of peristaltic pump Dropwise 5 0%, adding the KOH time is 1.5h, 95 ℃ of temperature of reaction again.Add KOH end continued and keep reaction 9h.Reaction is added solvent 400g after finishing, and stops to stir, and is static, divides the sub-cloud water layer, drips H
3PO
4Be adjusted to PH≤6.Repeat to wash static separatory to water PH=6.5～7.Wash qualified back 150 ℃ of following underpressure distillation, vacuum tightness≤-0.09MPa, obtain hydrogenated bisphenol A epoxy resin 548g after removing solvent toluene.Products obtained therefrom is colourless to faint yellow transparent thick liquid; Epoxy equivalent (weight) (g/eq): 229; Hydrolyzable chlorine (ppm): 485, content of inorganic chlorine (ppm): 7; Viscosity (mPa.s, 25 ℃): 2376.
Embodiment of the present invention only is the description that preferred implementation of the present invention is carried out; Be not that design of the present invention and scope are limited; Under the prerequisite that does not break away from design philosophy of the present invention, engineering technical personnel make technical scheme of the present invention in this area various modification and improvement all should fall into protection scope of the present invention; The technology contents that the present invention asks for protection all is documented in claims.
Claims (15)
1. the preparation method of a hydrogenated bisphenol A epoxy resin, adopting Hydrogenated Bisphenol A 99 and epoxy chloropropane is raw material, it is characterized in that synthesis step is following:
(1) raw materials pretreatment adds Hydrogenated Bisphenol A 99 and solvent in the reaction kettle that stirring rake, TM, water trap and reflux exchanger are housed, the temperature rising reflux dehydration;
(2) open loop addition etherificate; Add lewis acid catalyst after the product temperature of step (1) reduced to 70 ~ 110 ℃, drip epoxy chloropropane, carry out ring opening etherification reaction; Generate chloropharin ether; The ring opening etherification reaction temperature is 30 ~ 110 ℃, and epoxy chloropropane adds in 2 ~ 5h, adds the epoxy chloropropane continued and keeps reaction 0.5 ~ 3h;
(3) closed loop epoxidation; With its charging capacity of solvent recuperation in the product of step (2) 20% ~ 70% after; Add entry and an amount of high concentration alkali, make that the concentration of final alkali is 10% ~ 45%, be 0.5 ~ 3h add-subtract time; Add that to keep the reaction times after alkali finishes be 3 ~ 18h, the ring-closure reaction temperature is 50 ~ 100 ℃;
(4) product postprocessing toward the additional an amount of solvent of the product of step (3), obtains hydrogenated bisphenol A epoxy resin through dissolving, neutralization, washing, vacuum desolventizing after handling.
2. the preparation method of hydrogenated bisphenol A epoxy resin according to claim 1, the mol ratio that it is characterized in that described Hydrogenated Bisphenol A 99, epoxy chloropropane, alkali and lewis acid catalyst is 1:2 ~ 3:2 ~ 3:0.003 ~ 0.008.
3. according to the method for any described hydrogenated bisphenol A epoxy resin preparation of claim 1 ~ 2, it is characterized in that described pretreatment temperature is 80 ~ 120 ℃, the time is 0.5 ~ 2h; Etherification reaction temperature is 80 ~ 100 ℃, and the time is 2 ~ 5h; The ring-closure reaction temperature is 70 ~ 100 ℃, time 3 ~ 18h.
4. according to the method for any described hydrogenated bisphenol A epoxy resin preparation of claim 1 ~ 3, it is characterized in that described solvent is selected from one or more mixtures such as toluene, YLENE, MIBK, pimelinketone, hexanaphthene.
5. according to the method for any described hydrogenated bisphenol A epoxy resin preparation of claim 1 ~ 3, it is characterized in that said raw materials pretreatment solvent load is 0.5 ~ 3 times of Hydrogenated Bisphenol A 99 charging capacity.
6. according to the method for any described hydrogenated bisphenol A epoxy resin preparation of claim 1 ~ 3, it is characterized in that described Lewis acid is selected from one or more in aluminum chloride, iron(ic)chloride, boron trifluoride or the tin tetrachloride.
7. according to any method that described hydrogenated bisphenol A epoxy resin prepares of claim 1 ~ 3; It is characterized in that described alkali is NaOH or KOH; Adding the alkali mode adopts and adds water earlier; The mode that adds high density alkali again, the alkali concn that finally adds reaction system is 10～35%, the molar ratio of Hydrogenated Bisphenol A 99 and alkali is 1:2～3.
8. according to the method for any described hydrogenated bisphenol A epoxy resin preparation of claim 1 ~ 3, it is characterized in that in the said product postprocessing process: add solvent load after cyclization finishes and be the Hydrogenated Bisphenol A 99 charging capacity 2 ~ 4 times; Be neutralized to material PH=5 ~ 7, wash to material PH=6 ~ 7; 140 ℃ ~ 180 ℃ of desolventizing TRs, vacuum tightness≤-0.08MPa.
9. the preparation method of hydrogenated bisphenol A epoxy resin according to claim 2, the mol ratio that it is characterized in that described Hydrogenated Bisphenol A 99, epoxy chloropropane, alkali and lewis acid catalyst is 1:2 ~ 2.5:2 ~ 2.5:0.004～0.007.
10. according to any described hydrogenated bisphenol A epoxy resin preparation method of claim 1 ~ 9, it is characterized in that said solvent is a toluene, alkali is NaOH, and lewis acid catalyst is a boron trifluoride.
11. according to the hydrogenated bisphenol A epoxy resin preparation method of claim 1, the charging capacity that it is characterized in that described raw materials pretreatment solvent is 1 ~ 2 times of Hydrogenated Bisphenol A 99; The preferred temperature of etherification reaction is 80～100 ℃; The molar ratio of Hydrogenated Bisphenol A 99 and epoxy chloropropane is 1:2～2.5; The amount that reclaims solvent is preferably 30～60% of its charging capacity; It is 15～30% that the closed loop epoxidation adds the alkali concn scope, and the ring-closure reaction temperature is 80～100 ℃, and be 1～3h add-subtract time; Add that to keep the reaction times preferable range after alkali finishes be 6～15h, the molar ratio of Hydrogenated Bisphenol A 99 and alkali is 1:2～2.7.
12., it is characterized in that the acidic substance that the said neutralization of step (4) is adopted are phosphoric acid, boric acid, sodium hydrogencarbonate, oxalic acid, acetic acid according to the hydrogenated bisphenol A epoxy resin preparation method of claim 1.
13. hydrogenated bisphenol A epoxy resin preparation method according to claim 1; It is characterized in that solvent phase that said additional solvent of step (4) and raw materials pretreatment use with; Solvent load is 2～4 times of Hydrogenated Bisphenol A 99 charging capacity, and solvent temperature is 60～90 ℃, dissolution time 0.5～1h.
14. according to the hydrogenated bisphenol A epoxy resin preparation method of claim 1, it is characterized in that the said desolventizing top temperature of step (4) is 140 ℃～180 ℃, vacuum tightness is-below the 0.09MPa.
15., it is characterized in that the structural formula of described hydrogenated bisphenol A epoxy resin is according to any described hydrogenated bisphenol A epoxy resin preparation method of claim 1 ~ 14:
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