CN101367909B - Synthesis process for bisphenol acid type epoxy resin with medium molecular mass - Google Patents
Synthesis process for bisphenol acid type epoxy resin with medium molecular mass Download PDFInfo
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- CN101367909B CN101367909B CN2008101415868A CN200810141586A CN101367909B CN 101367909 B CN101367909 B CN 101367909B CN 2008101415868 A CN2008101415868 A CN 2008101415868A CN 200810141586 A CN200810141586 A CN 200810141586A CN 101367909 B CN101367909 B CN 101367909B
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Abstract
The invention relates to a synthesis technology of diphenolic acid epoxy resin with moderate molecular weight, comprising the steps of using diphenolic acid and epoxy chloropropane as rawsource materials and condensing and catalyzing with alkaline catalyst to obtain diphenolic acid epoxy resin with moderate molecular weight through catalyzing by basic catalyst in the presence existence of phase transfer catalyst. The mole ratio of diphenolic acid to epoxy chloropropane is 1:2 to 10. The usage of the phase transfer catalyst is 1 to 4 percent of the mole number of diphenolic acid. The mole ratio of the usage of basic catalyst and diphenolic acid is 1:0.2 to 0.6. The reaction temperature is 60 to 80 degrees centigrade DEG C. , and The the reaction time is 2 to 6 hours. The synthesis technology of diphenolic acid epoxy resin with moderate molecular weight is characterized in by simple technique and high yield, and is suitable for industrial production.
Description
Technical field
The present invention relates to a kind of synthesis technique of middle molecular mass bisphenol acid type Resins, epoxy.
Background technology
Middle molecular mass Resins, epoxy is widely used in fields such as coating, tackiness agent, laminating material, electrical equipment cast, Electronic Packaging, and along with developing rapidly of coatings industry and electronic industry, this resinoid performance, synthetic method etc. are subjected to people's attention day by day.Bisphenol A type epoxy resin is because raw material is easy to get, and cost is low, thereby the output maximum, accounts for 90% of Resins, epoxy ultimate production in China.But discover, diseases such as low-level dihydroxyphenyl propane can cause that human body prostate cancer and mammary cancer increase, reproduction is unusual, sperm count reduction, female sexual prematurity, obesity and diabetes, therefore, seeking the type material that substitutes dihydroxyphenyl propane is one of Resins, epoxy developing direction in order to synthetic resins.
Studies show that recently diphenolic acid replaces the Resins, epoxy of dihydroxyphenyl propane production to have stronger alkali resistant ability and other chemicals corrosive abilities of opposing.Diphenolic acid and epoxy chloropropane be polymerization reaction take place under catalyst action, and reaction expression is as follows:
The relevant report of diphenolic acid synthetic epoxy resin that utilizes is few.People such as Japan's ternary one good fortune by diphenolic acid and epoxy chloropropane condensation, have made bisphenol acid type Resins, epoxy in alkaline medium, and further with its synthetic paint, but the consumption and the usage of alkali are not specifically reported.The seventies, China Jinan Paint Factory once improved Japanese ternary one good fortune technology, independently synthesized bisphenol acid type Resins, epoxy, be 0.18 Resins, epoxy but only make minimum oxirane value, and the product color was darker.
Summary of the invention
The objective of the invention is to diphenolic acid as the dihydroxyphenyl propane alternative materials, in order to the bisphenol acid type Resins, epoxy of molecular mass in synthetic a kind of.
For reaching above-mentioned purpose, the present invention adopts following technical scheme: molecular mass bisphenol acid type Resins, epoxy synthesis technique in a kind of,
(1), diphenolic acid, epoxy chloropropane and phase-transfer catalyst are added in the reactor, be warming up to 60～80 ℃, insulation reaction makes the diphenolic acid dissolving, and the mol ratio of diphenolic acid and epoxy chloropropane is 1:2～10, and the consumption of phase-transfer catalyst is 1～4% of a diphenolic acid mole number;
(2), gained solution cools to below 60 ℃ in (1), slowly drips whole alkaline catalyst solutions then, 50～90 ℃ of reactions 2～6 hours, basic catalyst and diphenolic acid mol ratio were 1:0.2～0.6; The unreacted epoxy chloropropane of reclaim under reduced pressure adds organic solvent-benzene dissolving crude product, adds to be washed to neutrality again, leaves standstill branch vibration layer, and distillation removes benzene, molecular mass bisphenol acid type Resins, epoxy in obtaining;
Perhaps, (1) solution described in cools to below 60 ℃, slowly drip the alkaline catalyst solution of half volume earlier, at 60～80 ℃ of back flow reaction 1～4 hour, the unreacted epoxy chloropropane of reclaim under reduced pressure, the cooling back adds benzene, drip the alkaline catalyst solution of second half volume simultaneously, under 60～80 ℃ of conditions, back flow reaction 1～2 hour, basic catalyst and diphenolic acid mol ratio are 1:0.2～0.6; Add then and be washed to neutrality, leave standstill branch vibration layer, distillation removes benzene, the bisphenol acid type Resins, epoxy of molecular mass in obtaining;
Described phase-transfer catalyst can be quaternary amine, quaternary alkylphosphonium salt etc., as: tetramethyl ammonium chloride, tetraethylammonium bromide, Tetrabutyl amonium bromide or triethyl benzyl ammonia chloride, described basic catalyst are alkali metal hydroxide or alkaline earth metal hydroxides.
The mol ratio of described diphenolic acid and epoxy chloropropane is 1:2～5.
The consumption of described phase-transfer catalyst is 1～2% of a diphenolic acid mole number.
Described basic catalyst and diphenolic acid mol ratio are 1:0.2～0.4.
The reaction times is 3～5 hours in the step (2).
By relatively seeing: (a) the strong absorption peak of epoxy group(ing) is arranged, and (b) do not have at 915.1cm and 1248.2 places with the bisphenol acid type Resins, epoxy (a) of present method preparation and the infrared spectrogram of diphenolic acid (b); (a) at 1184.5 places absorption peak is arranged, and intensity is big, can judges that it is the ehter bond that links to each other with phenyl ring in the Resins, epoxy, and (b) not strong at 1177.5 place's absorption peaks, no ehter bond is described; Remaining characteristic peak is as an OH, phenyl ring, a CH
3, a CH
2, two figure such as a C=O, phenol, para-orientation phenyl ring are all identical, just the position is slightly different.The existence of these charateristic avsorption bands all illustrates under catalyst action diphenolic acid and epichlorohydrin reaction and has generated bisphenol acid type Resins, epoxy.
Adopt the perchloric acid method to measure the epoxy equivalent (weight) of gained bisphenol acid type Resins, epoxy of the present invention, the product average molecular mass that obtains after the calculating is between 1400～1800.
The present invention is simple for process, and yield reaches more than 96%.
Embodiment
Embodiment 1:
In the 500mL there-necked flask that agitator, thermometer, reflux exchanger are housed, the epoxy chloropropane that adds 14.3g diphenolic acid and 9.3, add phase-transfer catalyst tetramethyl ammonium chloride 0.1g then, be warming up to 80 ℃ of insulation reaction, make the diphenolic acid dissolving, be cooled to 60 ℃ then, slowly dripping 10mL concentration is 30% liquid caustic soda NaOH, and back flow reaction finishes reaction after 3 hours.The unreacted epoxy chloropropane of reclaim under reduced pressure adds organic solvent-benzene dissolving crude product, adds entry again and is washed to neutrality, leaves standstill branch vibration layer, and the bisphenol acid type Resins, epoxy that benzene is molecular mass in the inventive method product, yield 92.5% are removed in distillation at last.
Embodiment 2:
In the 500mL there-necked flask that agitator, thermometer, reflux exchanger are housed, the epoxy chloropropane that adds 14.3g diphenolic acid and 18.6g, add phase-transfer catalyst tetramethyl ammonium chloride 0.2g then, be warming up to 70 ℃ of insulation reaction, make the diphenolic acid dissolving, be cooled to 50 ℃ then, slowly dripping 10mL concentration is 30% liquid caustic soda NaOH, and back flow reaction finishes reaction after 4 hours.The unreacted epoxy chloropropane of reclaim under reduced pressure adds organic solvent-benzene dissolving crude product, adds entry again and is washed to neutrality, leaves standstill branch vibration layer, and the bisphenol acid type Resins, epoxy that benzene is molecular mass in the inventive method product, yield 94.8% are removed in distillation at last.
Embodiment 3:
In the 500mL there-necked flask that agitator, thermometer, reflux exchanger are housed, the epoxy chloropropane that adds 14.3g diphenolic acid and 46.4, add phase-transfer catalyst tetramethyl ammonium chloride 0.2g then, be warming up to 70 ℃ of insulation reaction, make the diphenolic acid dissolving, be cooled to 60 ℃ then, slowly dripping 30mL concentration is 30% liquid caustic soda NaOH, and back flow reaction finishes reaction after 5 hours.The unreacted epoxy chloropropane of reclaim under reduced pressure adds organic solvent-benzene dissolving crude product, adds entry again and is washed to neutrality, leaves standstill branch vibration layer, and the bisphenol acid type Resins, epoxy that benzene is molecular mass in the inventive method product, yield 93.2% are removed in distillation at last.
Embodiment 4:
In the 500mL there-necked flask that agitator, thermometer, reflux exchanger are housed, add 14.3g diphenolic acid and 18.6g epoxy chloropropane, add phase-transfer catalyst benzyltriethylammoinium chloride 0.1g then, be warming up to 70 ℃, insulation reaction makes the diphenolic acid dissolving, be cooled to 60 ℃ then, the NaOH of slow Dropwise 5 mL concentration 30%, back flow reaction is after 3 hours, the unreacted epoxy chloropropane of reclaim under reduced pressure, the cooling back adds benzene, and the NaOH of Dropwise 5 mL concentration 30% flows reaction 1 hour simultaneously.Reaction finishes the back adding and is washed to neutrality, leaves standstill branch vibration layer, and the bisphenol acid type Resins, epoxy that benzene is molecular mass in the inventive method product, yield 96.3% are removed in distillation at last.
Embodiment 5:
In the 500mL there-necked flask that agitator, thermometer, reflux exchanger are housed, add 14.3g diphenolic acid and 46.4g epoxy chloropropane, add phase-transfer catalyst benzyltriethylammoinium chloride 0.2g then, be warming up to 80 ℃ of insulation reaction, make the diphenolic acid dissolving, be cooled to 60 ℃ then, slowly drip the NaOH of 15mL concentration 30%, back flow reaction is after 4 hours, the unreacted epoxy chloropropane of reclaim under reduced pressure, the cooling back adds benzene, drips the NaOH of 15mL concentration 30% simultaneously, back flow reaction 1 hour.Reaction finishes the back adding and is washed to neutrality, leaves standstill branch vibration layer, and the bisphenol acid type Resins, epoxy that benzene is molecular mass in the inventive method product, yield 95.8% are removed in distillation at last.
Claims (5)
1. molecular mass bisphenol acid type Resins, epoxy synthesis technique in a kind is characterized in that:
(1), diphenolic acid, epoxy chloropropane and phase-transfer catalyst are added in the reactor, be warming up to 60～80 ℃, insulation reaction makes the diphenolic acid dissolving, and the mol ratio of diphenolic acid and epoxy chloropropane is 1: 2～10, and the consumption of phase-transfer catalyst is 1～4% of a diphenolic acid mole number;
(2), gained solution cools to below 60 ℃ in (1), slowly drips whole alkaline catalyst solutions then, 50～90 ℃ of reactions 2～6 hours, basic catalyst and diphenolic acid mol ratio were 1: 0.2～0.6; The unreacted epoxy chloropropane of reclaim under reduced pressure adds organic solvent-benzene dissolving crude product, adds to be washed to neutrality again, leaves standstill branch vibration layer, and distillation removes benzene, molecular mass bisphenol acid type Resins, epoxy in obtaining;
Perhaps, (1) solution described in cools to below 60 ℃, slowly drip the alkaline catalyst solution of half volume earlier, at 60～80 ℃ of back flow reaction 1～4 hour, the unreacted epoxy chloropropane of reclaim under reduced pressure, the cooling back adds benzene, drip the alkaline catalyst solution of second half volume simultaneously, under 60～80 ℃ of conditions, back flow reaction 1～2 hour, basic catalyst and diphenolic acid mol ratio are 1: 0.2～0.6; Add then and be washed to neutrality, leave standstill branch vibration layer, distillation removes benzene, the bisphenol acid type Resins, epoxy of molecular mass in obtaining;
Described phase-transfer catalyst is tetramethyl ammonium chloride, tetraethylammonium bromide, Tetrabutyl amonium bromide or triethyl benzyl ammonia chloride, and described basic catalyst is alkali metal hydroxide or alkaline earth metal hydroxides.
2. molecular mass bisphenol acid type Resins, epoxy synthesis technique in according to claim 1, it is characterized in that: the mol ratio of described diphenolic acid and epoxy chloropropane is 1: 2～5.
3. molecular mass bisphenol acid type Resins, epoxy synthesis technique in according to claim 1, it is characterized in that: the consumption of described phase-transfer catalyst is 1～2% of a diphenolic acid mole number.
4. molecular mass bisphenol acid type Resins, epoxy synthesis technique in according to claim 1, it is characterized in that: described basic catalyst and diphenolic acid mol ratio are 1: 0.2～0.4.
5. molecular mass bisphenol acid type Resins, epoxy synthesis technique in according to claim 1 is characterized in that: the reaction times is 3～5 hours in the step (2).
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| CN2008101415868A CN101367909B (en) | 2008-10-10 | 2008-10-10 | Synthesis process for bisphenol acid type epoxy resin with medium molecular mass |
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