CN104693391B - A kind of epoxy phenolics and synthetic method thereof - Google Patents
A kind of epoxy phenolics and synthetic method thereof Download PDFInfo
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- CN104693391B CN104693391B CN201510125780.7A CN201510125780A CN104693391B CN 104693391 B CN104693391 B CN 104693391B CN 201510125780 A CN201510125780 A CN 201510125780A CN 104693391 B CN104693391 B CN 104693391B
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Abstract
The present invention relates to a kind of epoxy phenolics and synthetic method thereof, its synthetic route is: (1) phenol and epoxychloropropane, under conditions of inert gas shielding and catalyst, generate 1 chlorine 3 phenoxy group 2 propanol through ring-opening reaction；(2) 1 chlorine 3 phenoxy group 2 propanol generate 3 phenoxy group 1,2 expoxy propane through ring-closure reaction under catalyst action；(3) 3 phenoxy group 1,2 expoxy propane and formaldehyde, phenol, under the catalysis of ammonia, occur additive reaction to generate 3 [(2,4,6 methylol) phenoxy group] 1,2 expoxy propane；(4) 3 [(2,4,6 methylol) phenoxy group] 1,2 expoxy propane generation polycondensation reaction generates described novel epoxy phenolic resin.The method is different from the synthetic method of traditional novolac epoxy resin, simple to operation, efficiently reduces epoxychloropropane hydrolysis and the generation of side reaction, and the process of follow-up desalination is simple and convenient.
Description
Technical field
The present invention relates to a kind of epoxy phenolics and synthetic method thereof.
Background technology
Phenolic resin, compared with other thermosetting resin, has that cost of material is cheap, heat-resisting, fire-retardant and heat distortion temperature is high,
Deforming little during the demoulding, molding only needs heating, pressurization, it is not necessary to add the advantage such as initiator and accelerator, maximum of which feature
It is to be easily formed high-carbon foaming structure during phenolic resin burning, becomes excellent heat insulator, thus hinder inside to burn away.Phenol
The performances such as the anti-flammability of urea formaldehyde composite, low cigarette and low toxicity are far superior to epoxy resin and polyester resin, but phenolic resin
There is the shortcoming that fragility is big, intensity is low.When epoxy novolac blending resin is as matrices of composite material materials'use, its mechanical property ratio
Pure phenolic resin increases, but reduces the anti-flammability of phenolic resin to a certain extent.For solving this problem, use
Epoxide group is introduced phenolic resin macromole method and prepares epoxy phenolics, the resistance of thermosetting phenolic resin can be given full play to
Combustion property and the toughness advantage of epoxy resin.Set about from the synthetic method of epoxy phenolics herein, have studied one heat cured newly
Type epoxy phenolics, is different from the synthetic method of other novolac epoxy resin, uses first epoxidation aftercondensated to prepare
The function admirables such as the chemical stability of novel epoxy phenolic resin, thermostability, anti-flammability.
Summary of the invention
The technical problem to be solved is the deficiency existed for above-mentioned prior art and provides a kind of novel epoxy phenolic aldehyde tree
Fat and synthetic method thereof, be difficult to gel in course of reaction, efficiently reduces the generation of side reaction and the hydrolysis of epoxychloropropane, former
Material utilization rate is high.
The present invention is to solve the problems referred to above and the technical scheme proposed is:
Novel epoxy phenolic resin, as shown in Equation 1, wherein n is the degree of polymerization to its structural formula.
The synthetic method of above-mentioned novel epoxy phenolic resin, is divided into four steps:
(1) ring-opening reaction: phenol and epoxychloropropane are under conditions of inert gas shielding and catalyst, raw through ring-opening reaction
Become 1-chloro-3-phenoxy group-2-propanol；
(2) ring-closure reaction: 1-chloro-3-phenoxy group-2-propanol generates 3-phenoxy group--1,2 epoxy prapane under catalyst action；
(3) additive reaction: 3-phenoxy group-1,2 epoxy prapane and formaldehyde, phenol, under the catalysis of ammonia, occur additive reaction
Generate 3-[(2,4,6-methylol) phenoxy group]-1,2 epoxy prapane；
(4) polycondensation reaction: 3-[(2,4,6-methylol) phenoxy group]-1,2 epoxy prapane generation polycondensation reaction generates described novel epoxy
Phenolic resin.
By such scheme, the phenol addition in described step (1) is 1:(1.1～1.7 with the mol ratio of epoxychloropropane).
By such scheme, the reaction temperature in described step (1) is 65～75 DEG C, and the response time is 1.5～3h.
By such scheme, in described step (1) and step (2), catalyst is alkali, as selected 55%～65% hydroxide
Sodium solution or potassium hydroxide solution.Wherein, in total addition of step (1) and step (2) catalyst alkali and step (1)
The mol ratio of phenol is 1:1；Described noble gas is nitrogen, argon etc..
By such scheme, the reaction temperature in described step (2) is 75～85 DEG C, and the response time is 1.5～3h.
By such scheme, the 3-phenoxy group-1,2 epoxy prapane in described step (3) with in this step phenol addition mole
Ratio is 1:(0.5～2).
By such scheme, 3-phenoxy group-1,2 epoxy prapane and the addition summation of phenol, formaldehyde, ammonia in described step (3)
The mol ratio of water is 1:(1.0～1.5): (0.15～0.35).Wherein, ammonia is generally selected the ammonia that commercially available concentration is 25%～28%
Water, formaldehyde is generally selected the formalin of commercially available 35～40%.Ammonia is catalyst in this step, and alkalescence is difficult to hand over
Connection, if with sodium hydroxide solution, reacting wayward.
By such scheme, the reaction temperature in described step (3) is 80～90 DEG C, and the response time is 1～2h.
By such scheme, the reaction temperature in described step (4) is 85～95 DEG C, and reaction pressure is 0.03～0.04MPa (decompression
Dehydration and ammonia), the response time is 6～8h.
The synthetic method of above-mentioned novel epoxy phenolic resin, specifically comprises the following steps that
(1) ring-opening reaction: under the protection of noble gas, to catalyst 55%～65wt% sodium hydroxide (or potassium hydroxide
Deng) solution adds phenol, after stirring 15～20min at 65～75 DEG C, add epoxychloropropane, reaction temperature is controlled
65～75 DEG C, ring-opening reaction 1.5～3h, generate 1-chloro-3-phenoxy group-2-propanol；Phenol addition and epoxychloropropane in this step
Mol ratio be 1:(1.1～1.7), the addition of catalyst and the mol ratio of phenol are (1/4～1/2): 1；
(2) ring-closure reaction: catalyst 55%～65wt% hydrogen will be added in the 1-chloro-3-phenoxy group-2-propanol of step (1) gained
Sodium oxide (or potassium hydroxide etc.) solution, temperature is controlled at 75～85 DEG C, reaction 1.5～3h generation 3-phenoxy group-1,2-epoxy
Propane crude product, rotated evaporation purifies and obtains 3-phenoxy group-1,2 epoxy prapane；Wherein, step (1) and step (2) are urged
Total addition of agent is about 1:1 with the mol ratio of phenol in step (1)；
(3) additive reaction: being mixed with formaldehyde, phenol, ammonia by 3-phenoxy group-1,2 epoxy prapane, reaction temperature controls
80～90 DEG C, react 1～2h, generate 3-[(2,4,6-methylol) phenoxy group]-1,2 epoxy prapane；3-phenoxy group-1,2-in this step
In expoxy propane and this step, the mol ratio of phenol addition is 1:(0.5～2), adding of 3-phenoxy group-1,2 epoxy prapane and phenol
Enter amount summation, formaldehyde, the mol ratio of ammonia are 1:(1.0～1.5): (0.15～0.35)；
(4) polycondensation reaction: the temperature of step (4) gained 3-[(2,4,6-methylol) phenoxy group]-1,2 epoxy prapane is controlled
85～95 DEG C, while polycondensation reaction, decompression dehydration and ammonia under 0.03～0.04MPa, react 6～8h, obtain described Novel ring
Oxygen phenolic resin.
Chemical equation of the present invention is as follows:
Compared with the synthetic method of existing epoxy phenolics, it is an advantage of the current invention that:
(1) the novel epoxy phenolic resin synthesized by the present invention is a kind of heat cured epoxy phenolics, and phenolic hydroxyl group is in warm
It is possible not only to occur self-condensation reaction under effect, and phenolic hydroxyl group or alcoholic extract hydroxyl group can be formed with epoxy radicals generation ring-opening reaction
Cross-linked structure, its epoxy novolac solidfied material has excellent anti-flammability, mechanical property and thermostability etc.；
(2) the invention reside in the building-up process of novel epoxy phenolic resin, the utilization rate that reaction is difficult to gel and raw material is high,
Synthetic route is simple to operation；
(3) synthetic method of the present invention is different from the synthesis of traditional novolac epoxy resin, is not required to introduce excess
Epoxychloropropane, can efficiently reduce the generation of side reaction and the hydrolysis of epoxychloropropane, and the utilization rate of epoxychloropropane is high；
(4) synthetic method of the present invention is different from the synthesis of traditional novolac epoxy resin, can remove de-after filtration
The salt that HCl (all having sloughed HCl in ring-opening reaction and ring-closure reaction) generates, it is not necessary to add solvent extraction, follow-up desalination
Process is simple and convenient reliably.
Accompanying drawing explanation
Fig. 1 is the infrared spectrogram of ring-closure reaction gained 3-phenoxy group-1,2 epoxy prapane in embodiment 1.
Fig. 2 is the infrared spectrogram of novel epoxy phenolic resin in embodiment 1.
Detailed description of the invention
In order to be more fully understood that the present invention, it is further elucidated with present disclosure below in conjunction with embodiment, but the present invention not only office
It is limited to the following examples.
Embodiment 1
Novel epoxy phenolic resin, its structural formula is shown below, and wherein n is the degree of polymerization.
The synthetic method of above-mentioned epoxy phenolics, specifically comprises the following steps that
First step ring-opening reaction: under the protection of nitrogen, to agitator, thermometer there-necked flask in add 60wt% hydrogen
Sodium hydroxide solution 3g (0.045mol), is subsequently added 30g phenol (0.32mol), after stirring 20min, adds at 70 DEG C
35.4g epoxychloropropane (0.38mol), controls reaction temperature to react 3h at 75 DEG C, generates 1-chloro-3-phenoxy group-2-propanol；
Second step ring-closure reaction: molten by adding 18g60wt% sodium hydroxide in the 1-chloro-3-phenoxy group-2-propanol of step (1) gained
Liquid (0.27mol), controls reaction temperature to react 2h at 75 DEG C, generates 3-phenoxy group-1,2 epoxy prapane crude product；
After 3-phenoxy group-1,2 epoxy prapane crude product is reclaimed epoxychloropropane and water with Rotary Evaporators, with filter paper filtering, obtain
To refined 3-phenoxy group-1,2 epoxy prapane；
3rd step additive reaction: described refined 3-phenoxy group-1,2 epoxy prapane (0.38mol) is added with agitator, temperature
In the there-necked flask of meter, add 20g phenol (0.21mol), 37% formaldehyde (0.62mol) of 50g and the 25 of 12g～28% ammonia
(0.09mol), reaction temperature controls to react 1h at 80 DEG C, generates 3-[(2,4,6-methylol) phenoxy group]-1,2 epoxy prapane；
4th one-step polycondensation reaction: the thermostatic of step (4) gained 3-[(2,4,6-methylol) phenoxy group]-1,2 epoxy prapane is existed
85 DEG C, while polycondensation reaction, decompression dehydration and ammonia under 0.04MPa, polycondensation reaction 6h, obtain light yellow liquid epoxy-phenol
Urea formaldehyde, epoxide number is 0.5.
Fig. 1 is the infrared spectrogram of ring-closure reaction gained 3-phenoxy group-1,2 epoxy prapane, analyzes as shown in table 1, it is therefore evident that press
Product according to the method for the invention ring-closure reaction is 3-phenoxy group-1,2 epoxy prapane.
Table 1
Fig. 2 is the infrared spectrogram of target product epoxy phenolics, analyzes as shown in table 2, it is therefore evident that according to of the present invention
Method final goal product is the epoxy phenolics shown in formula 1, and course of reaction is carried out according to formula 2.
Table 2
Embodiment 2
The synthetic method of a kind of epoxy phenolics, specifically comprises the following steps that
First step ring-opening reaction: under the protection of nitrogen, to agitator, thermometer there-necked flask in add 60wt% hydrogen
Sodium hydroxide solution 2g (0.03mol), is subsequently added 20g phenol (0.21mol), after stirring 15min, adds 31.5g at 65 DEG C
Epoxychloropropane (0.34mol), controls reaction temperature to react 2h at 75 DEG C, generates 1-chloro-3-phenoxy group-2-propanol；
Second step ring-closure reaction: molten by adding 12g60wt% sodium hydroxide in the 1-chloro-3-phenoxy group-2-propanol of step (1) gained
Liquid (0.18mol), controls reaction temperature to react 3h at 75 DEG C, generates 3-phenoxy group-1,2 epoxy prapane crude product；
After 3-phenoxy group-1,2 epoxy prapane crude product is reclaimed epoxychloropropane and water with Rotary Evaporators, with filter paper filtering, obtain
To refined 3-phenoxy group-1,2 epoxy prapane；
3rd step additive reaction: described refined 3-phenoxy group-1,2 epoxy prapane (0.34mol) is added with agitator, temperature
In the there-necked flask of meter, add 30g phenol (0.32mol), 37% formaldehyde (0.80mol) of 65g and the 25 of 15g～28% ammonia
(0.11mol), reaction temperature controls to react 2h at 82 DEG C, generates 3-[(2,4,6-methylol) phenoxy group]-1,2 epoxy prapane；
4th one-step polycondensation reaction: the thermostatic of step (4) gained 3-[(2,4,6-methylol) phenoxy group]-1,2 epoxy prapane is existed
95 DEG C, while polycondensation reaction, decompression dehydration and ammonia under 0.03MPa, polycondensation reaction 8h, obtain light yellow liquid epoxy-phenol
Urea formaldehyde, epoxide number is 0.6.
The above is only the preferred embodiment of the present invention, it is noted that for the person of ordinary skill of the art,
On the premise of conceiving without departing from the invention, it is also possible to making some modifications and variations, these broadly fall into the protection model of the present invention
Enclose.
Claims (10)
1. an epoxy phenolics, it is characterised in that its structural formula is shown below:
The synthetic method of epoxy phenolics the most according to claim 1, it is characterised in that be divided into four steps:
(1) ring-opening reaction: phenol and epoxychloropropane, under conditions of inert gas shielding and catalyst, generate through ring-opening reaction
1-chloro-3-phenoxy group-2-propanol；
(2) ring-closure reaction: 1-chloro-3-phenoxy group-2-propanol, under catalyst action, generates 3-phenoxy group-1,2-through ring-closure reaction
Expoxy propane；
(3) additive reaction: 3-phenoxy group-1,2 epoxy prapane and formaldehyde, phenol, under the catalysis of ammonia, occur additive reaction raw
Become 3-[(2,4,6-methylol) phenoxy group]-1,2 epoxy prapane；
(4) polycondensation reaction: 3-[(2,4,6-methylol) phenoxy group]-1,2 epoxy prapane generation polycondensation reaction generates described epoxy novolac
Resin.
The synthetic method of epoxy phenolics the most according to claim 2, it is characterised in that the phenol in described step (1)
Addition is 1:(1.1～1.7 with the mol ratio of epoxychloropropane).
The synthetic method of epoxy phenolics the most according to claim 2, it is characterised in that the reaction in described step (1)
Temperature is 65～75 DEG C, and the response time is 1.5～3h.
The synthetic method of epoxy phenolics the most according to claim 2, it is characterised in that described step (1) and step (2)
Middle catalyst is alkali, and total addition of step (1) and step (2) catalyst alkali is 1:1 with the mol ratio of phenol in step (1).
The synthetic method of epoxy phenolics the most according to claim 2, it is characterised in that the reaction in described step (2)
Temperature is 75～85 DEG C, and the response time is 1.5～3h.
The synthetic method of epoxy phenolics the most according to claim 2, it is characterised in that the 3-in described step (3)
Phenoxy group-1,2 epoxy prapane is 1:(0.5～2 with the mol ratio of phenol addition in this step)；3-benzene oxygen in described step (3)
The addition summation of base-1,2 epoxy prapane and phenol, formaldehyde, the mol ratio of ammonia are 1:(1.0～1.5): (0.15～0.35).
The synthetic method of epoxy phenolics the most according to claim 2, it is characterised in that the reaction in described step (3)
Temperature is 80～90 DEG C, and the response time is 1～2h.
The synthetic method of epoxy phenolics the most according to claim 2, it is characterised in that the reaction in described step (4)
Temperature is 85～95 DEG C, and reaction pressure is 0.03～0.04MPa, and the response time is 6～8h.
The synthetic method of epoxy phenolics the most according to claim 2, it is characterised in that specifically comprise the following steps that
(1) ring-opening reaction: under the protection of noble gas, adds phenol in catalyst 55%～65wt% sodium hydroxide solution,
After stirring 15～20min at 65～75 DEG C, add epoxychloropropane, reaction temperature is controlled at 65～75 DEG C, ring-opening reaction 1.5～3h,
Generate 1-chloro-3-phenoxy group-2-propanol；In this step, phenol addition is 1:(1.1～1.7 with the mol ratio of epoxychloropropane), urge
The addition of agent and the mol ratio of phenol are (1/4～1/2): 1；
(2) ring-closure reaction: catalyst 55%～65wt% hydrogen-oxygen will be added in the 1-chloro-3-phenoxy group-2-propanol of step (1) gained
Change sodium solution, temperature is controlled at 75～85 DEG C, reaction 1.5～3h generation 3-phenoxy group-1,2 epoxy prapane crude product, rotated steaming
Send out purification and obtain 3-phenoxy group-1,2 epoxy prapane；Wherein, step (1) and total addition of step (2) catalyst and step
(1) in, the mol ratio of phenol is 1:1；
(3) additive reaction: being mixed with formaldehyde, phenol, ammonia by 3-phenoxy group-1,2 epoxy prapane, reaction temperature controls
80～90 DEG C, react 1～2h, generate 3-[(2,4,6-methylol) phenoxy group]-1,2 epoxy prapane；3-phenoxy group-1,2-in this step
Expoxy propane is 1:(0.5～2 with the mol ratio of phenol addition in this step), 3-phenoxy group-1,2 epoxy prapane and the addition of phenol
Amount summation, formaldehyde, the mol ratio of ammonia are 1:(1.0～1.5): (0.15～0.35)；
(4) polycondensation reaction: the temperature of step (4) gained 3-[(2,4,6-methylol) phenoxy group]-1,2 epoxy prapane is controlled
85～95 DEG C, while polycondensation reaction, decompression dehydration and ammonia under 0.03～0.04MPa, react 6～8h, obtain described epoxy phenol
Urea formaldehyde.
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| CN108625224B (en) * | 2018-05-09 | 2022-06-03 | 上海昶法新材料有限公司 | Lignin-based epoxy phenolic resin sizing agent and preparation method and application thereof |
| US11414626B2 (en) | 2018-11-30 | 2022-08-16 | Ecolab Usa Inc. | Surfactant compositions and use thereof |
| CN112266453B (en) * | 2020-12-08 | 2021-03-30 | 北京市银帆涂料有限责任公司 | Phenol ether resin, coating composition containing same and preparation method thereof |
| CN114133535A (en) * | 2021-12-27 | 2022-03-04 | 安徽善孚新材料科技股份有限公司 | Moisture-heat-resistant epoxy resin and preparation method and application thereof |
| CN115925653B (en) * | 2022-09-27 | 2024-05-24 | 江苏三木化工股份有限公司 | Synthesis method of epoxy reactive diluent o-cresol glycidyl ether |
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| CN101403144B (en) * | 2008-11-12 | 2010-09-01 | 中国科学院山西煤炭化学研究所 | Preparation method for epoxychloropropane modified phenolic fibre |
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