CN102827349B - Preparation method of tetraglycidyl m-xylene diamine epoxy resin - Google Patents
Preparation method of tetraglycidyl m-xylene diamine epoxy resin Download PDFInfo
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Abstract
The invention discloses a preparation method of tetraglycidyl m-xylene diamine epoxy resin, which comprises the following steps: (1) adding epichlorohydrin and deionized water into a reaction device, dropwisely adding m-xylene diamine for a ring-opening reaction; (2) adding an aqueous alkali into the material obtained in step (1) for a ring-closure reaction, wherein the molar ratio of the alkali in the aqueous alkali to the m-xylene diamine is 4:1; (3) after the reaction, recovering epichlorohydrin, adding an inert solvent and deionized water, performing extraction layering, removing the water layer; (4) refining the organic layer with the aqueous alkali, wherein the molar ratio of the alkali in the aqueous alkali to the m-xylene diamine is 1:1-2.5:1; (5) washing the refined material with water, removing the solvent to obtain the tetraglycidyl m-xylene diamine epoxy resin. The method of the invention is simple in process, easy to implement, and low in cost, and the prepared tetraglycidyl m-xylene diamine epoxy resin has low viscosity, low organic chloride content, and a high epoxy value.
Description
Technical field
The present invention relates to a kind of preparation method of glycidyl amine epoxy resin, be specifically related to a kind of preparation method of tetraglycidyl m-xylene diamine epoxy resin.
Background technology
Epoxy resin is widely used in the field such as coating, binding agent with its good comprehensive mechanical property, unique sticking power, excellent insulativity, less shrinking percentage.The second-order transition temperature of general purpose epoxy resin is 100 DEG C ~ 160 DEG C, and thermal distorsion temperature is 70 DEG C ~ 140 DEG C, therefore cannot meet as aerospace electromechanics etc. requires resistant to elevated temperatures applications.
Multiple functionality epoxide resin is (as four glycidyl group-4,4'-diaminodiphenyl-methane, four glycidyl group-4,4'-diamino-diphenyl ether, four glycidyl group-3,4'-diamino-diphenyl ether etc.) owing to containing four epoxy group(ing) in molecular structure, cured article cross-linking density is high, second-order transition temperature can reach 230 DEG C ~ 260 DEG C, and thermal distorsion temperature is greater than 200 DEG C, therefore can more than 160 DEG C life-time service.But these resin viscosities commercial are comparatively large in the market, bring inconvenience to actual use.
Also containing four epoxy group(ing) in four glycidyl group m-xylene diamine molecular structure, the resin therefore after solidification has very high cross-linking density equally, and its thermal distorsion temperature is more than 180 DEG C.More valuable, the more above-mentioned multiple functionality epoxide resin of viscosity of this resin is much lower, brings great convenience to actual application.
Chinese patent literature CN101348559A discloses a kind of preparation method of m-xylene diamine epoxide resin, and the method is that m-xylene diamine, auxiliary agent, epoxy chloropropane are carried out ring opening etherification reaction at 30 ~ 85 DEG C, and the reaction times is 1.5 ~ 10h; Then etherification product and alkali are carried out ring-closure reaction at 30 ~ 85 DEG C, the ring-closure reaction time is 1.5 ~ 10h, generates m-xylene diamine epoxide resin crude product; Gained crude product is added organic solvent dissolution, extraction m-xylene diamine epoxide resin, be washed to neutrality, at 80 ~ 160 DEG C of desolvations.Wherein the weight proportion of m-xylene diamine, auxiliary agent, epoxy chloropropane and alkali is 1: 0 ~ 15: 0.1 ~ 15: 0.04 ~ 2.2.Wherein auxiliary agent is selected from one or more in benzene, toluene, methyl iso-butyl ketone (MIBK), butanols, butanone, Virahol, quaternary ammonium salt, quaternary alkylphosphonium salt, sodium hydroxide, potassium hydroxide, water or Resorcinol.Wherein alkali is selected from sodium hydroxide, potassium hydroxide, and its concentration is 10 ~ 50%, can be solid caustic soda.The deficiency of the method is: due to epoxy chloropropane be easily hydrolyzed, autohemagglutination, and in this reaction process, this well not to be controlled, causes the viscosity of the m-xylene diamine epoxide resin finally obtained comparatively large (16500 ~ 20000mPaS).
Chinese patent literature CN10163286A discloses a kind of preparation method of tetraglycidylamino compound, and the method is reacted in presence of water at diamines and excessive epihalohydrin, obtains halohydrin body; Then, under the coexisting of phase-transfer catalyst, halohydrin body and alkali metal hydroxide are reacted, obtains tetraglycidylamino compound; Then the ring-closure reaction that is dissolved in water produce by product alkali metal halide and separatory removing, obtain containing tetraglycidylamino compound and unreacted epihalohydrin; Then washing again, separatory, the unreacted epihalohydrin of Distillation recovery, and the thick tetraglycidylamino compound obtained is dissolved in organic solvent, separatory after washing; Last Distillation recovery organic solvent, obtains tetraglycidylamino compound.Also comprise and carry out refining with recycling to the organic solvent reclaimed.Wherein the mol ratio of epihalohydrin and diamines is 5.5 ~ 15: 1, preferably 6.5 ~ 10: 1; The mol ratio of the alkali that ring-closure reaction adopts and diamines is 4.2 ~ 5: 1.The basic characteristics of the method carry out refinement treatment with recycling to recovered solvent.And its deficiency preparing tetraglycidylamino compound is: ring-closure reaction needs to adopt phase-transfer catalyst, not only cause cost higher, and its salt compound adopted and straight-chain polyether compound are also the catalyzer of epoxy ring-opening, therefore while catalysis ring-closure reaction, also the risk of resin self-polymerization can be increased, and namely cyclic polyether (also crown ether-like) price adopted is extremely expensive and toxicity is larger, remain in when post-processed in water, considerably increase difficulty and the cost of wastewater treatment.
Summary of the invention
The object of the invention is to solve the problem, provide that a kind of cost is lower, the preparation method of the simple tetraglycidyl m-xylene diamine epoxy resin of aftertreatment.The viscosity of the tetraglycidyl m-xylene diamine epoxy resin that the method obtains is lower, content of organic chloride is lower, oxirane value is higher.
The technical scheme realizing the object of the invention is: a kind of preparation method of tetraglycidyl m-xylene diamine epoxy resin, there are following steps: 1. join in reaction unit by epoxy chloropropane and deionized water, be heated to 30 DEG C ~ 70 DEG C, drip m-xylene diamine, ring-opening reaction is carried out, until react completely after dripping off; 2. drip alkaline solution in the material 1. obtained to step at the temperature of 30 DEG C ~ 80 DEG C, carry out ring-closure reaction after dripping off, until react completely; Alkali in described alkaline solution and step 1. in the mol ratio of m-xylene diamine be 4: 1; 3. after reaction terminates, epoxy chloropropane is reclaimed in first underpressure distillation, then adds inert solvent and deionized water, carries out extracting and demixing, removing water layer; 4. organic layer alkaline solution step 3. obtained is refining 0.5h ~ 4h at the temperature of 60 DEG C ~ 90 DEG C; Alkali in alkaline solution and step 1. in the mol ratio of m-xylene diamine be 1: 1 ~ 2.5: 1; 5. the material after refining is after being washed to neutrality, and underpressure distillation desolvation, obtains tetraglycidyl m-xylene diamine epoxy resin.
The quality of above-mentioned steps ring-opening reaction 1. (also claiming chlorohydrin action) completeness on the finished product has impact.If reaction is not exclusively, residual secondary amine reactive hydrogen the ring-closure reaction stage can with epoxy group(ing) generation addition reaction, cause resin viscosity to increase.Suitable material molar ratio, temperature of reaction and reaction times then can make this reaction can be complete.In addition, a small amount of deionized water have the consistency being beneficial to and improving reactant, thus be conducive to react carrying out.But too high temperature of reaction then can cause the self-polymeric reaction of epoxy chloropropane, thus increase the viscosity of resin.Therefore step 1. in the mol ratio of epoxy chloropropane, deionized water and m-xylene diamine be 8 ~ 18: 2: 1, preferably 14 ~ 16: 2: 1.Temperature of reaction is 40 DEG C ~ 80 DEG C, preferably 40 DEG C ~ 60 DEG C.Reaction times is 3h ~ 12h, preferred 7h ~ 10h.
The reaction activity of above-mentioned steps ring-closure reaction is 2. low, heat release is large, if therefore there is unnecessary alkali will cause hydrolysis and the autohemagglutination of epoxy chloropropane excessive in reaction mass in reaction process, product viscosity is finally caused to increase, quality reduces, and this affects a most key factor to product viscosity.Certainly very few alkali also can cause the chloropharin base that remains too much, affects the recovery of epoxy chloropropane below.Therefore adopt the alkali of equivalent that alkali both can have been made all to consume in ring-closure reaction, and remain without unnecessary alkali, thus at utmost avoid hydrolysis and the self-polymeric reaction of epoxy chloropropane in ring-closure reaction process, reduce resin viscosity, the recovery of epoxy chloropropane below can not be affected again.The temperature of this ring-closure reaction is unsuitable too high in addition, otherwise also can cause hydrolysis and the autohemagglutination of epoxy chloropropane.Therefore step temperature of reaction is 2. 30 DEG C ~ 80 DEG C, preferably 40 DEG C ~ 60 DEG C.The time for adding of alkaline solution is 1h ~ 3h, preferred 1.5h ~ 2.5h.The continuation reaction times is 1h ~ 3h, preferred 1.5h ~ 2h.Alkaline solution is sodium hydroxide solution or potassium hydroxide solution, and concentration is 30wt% ~ 50wt%.
3. the middle temperature reclaiming epoxy chloropropane should not be too high for above-mentioned steps, otherwise can cause epoxy chloropropane autohemagglutination.Therefore, the recovered temperature of epoxy chloropropane is 60 DEG C ~ 80 DEG C.And the volume ratio of inert solvent and deionized water is 1: 1, be good with the deionized water of the inert solvent and 170mL ~ 200mL that add 170mL ~ 200mL.Described inert solvent is the one in butanone, methyl iso-butyl ketone (MIBK), benzene and toluene, preferred butanone or methyl iso-butyl ketone (MIBK).
The object of above-mentioned steps refining reaction 4. makes ring-closure reaction stage completely closed loop and the complete closed loop epoxidation of residual chloropharin base, improves oxirane value, reduce content of organic chloride.Although have employed excessive alkali in treating process, because this reaction carries out in without the inert solvent of epoxy chloropropane, therefore, this excessive alkali can not cause hydrolysis and the self-polymeric reaction of epoxy chloropropane, thus ensures product quality.Alkaline solution is sodium hydroxide solution or potassium hydroxide solution, and concentration is 15wt% ~ 30wt%.
Above-mentioned steps 5. in washing be after refining reaction terminates, in reactor, add 200mL deionized water, slowly stir stratification after 5min, removing water layer, and repeated washing be to neutral.The temperature of underpressure distillation desolvation is 60 DEG C ~ 110 DEG C.
The positively effect that the present invention has: (1) preparation method of the present invention by the mol ratio of preferred epoxy chloropropane, deionized water and m-xylene diamine and temperature of reaction and time, thus ensure that ring-opening reaction can react completely in ring-opening reaction.(2) preparation method of the present invention passes through the alkali dripping equivalent in ring-closure reaction, thus alkali is all consumed in ring-closure reaction, and remain without unnecessary alkali, at utmost avoid hydrolysis and the self-polymeric reaction of epoxy chloropropane in ring-closure reaction process, greatly reduce resin viscosity.(3) what adopt due to ring-closure reaction is the alkali of equivalent, therefore have part chloropharin base and there is no complete closed loop, therefore preparation method of the present invention is also included in inert solvent and refines, chloropharin base Perfect Ring is oxidized, thus improve oxirane value, reduce content of organic chloride, finally can obtain low viscosity (1550PaS ~ 2500mPaS, 25 DEG C), the four glycidyl group m-xylene diamine of low content of organic chlorine (less than 0.2%), high epoxy value, also improve the rate of recovery of epoxy chloropropane simultaneously.
Accompanying drawing explanation
Fig. 1 is the liquid chromatography-mass spectrography figure of the tetraglycidyl m-xylene diamine epoxy resin that embodiment 1 obtains.
Fig. 2 is the nmr spectrum of the tetraglycidyl m-xylene diamine epoxy resin that embodiment 1 obtains.
Embodiment
(embodiment 1)
The preparation method of the tetraglycidyl m-xylene diamine epoxy resin of the present embodiment has following steps:
1. be equipped with mechanical stirring, reflux condensing tube, thermometer 1000mL four-hole bottle in add the epoxy chloropropane (3mol) of 277.5g and the deionized water (0.4mol) of 7.20g successively, be heated to 45 DEG C, in 1h, slowly drip the m-xylene diamine (0.2mol) of 27.2g, drip off and be heated to 58 DEG C and carry out ring-opening reaction 8h.
2. be cooled to 45 DEG C, drip the sodium hydroxide solution (containing 32g sodium hydroxide, 0.8mol) that 66.67g concentration is 48wt% in the material 1. obtained to step in 2h, after dripping off, at 45 DEG C, continue ring-closure reaction 2h.
3., after reaction terminates, first at the temperature of 60 DEG C, epoxy chloropropane is reclaimed in underpressure distillation, and the time is 1h.Then add 170mL methyl iso-butyl ketone (MIBK) and 170mL water, be slowly stirred at the temperature of 60 DEG C after dissolving completely, pour layering in separating funnel into, removing water layer.
4. the organic layer that 3. step obtains is refunded in four-hole bottle, at the temperature of 60 DEG C, add the sodium hydroxide solution (containing 15.6g sodium hydroxide, 0.39mol) that 92.1g concentration is 17wt%, after adding, at the temperature of 60 DEG C, refine 40min.
5. reaction system is down to 30 DEG C, adds 200mL deionized water, layering after slowly stirring, remove water layer, repeat above-mentioned washing 2 times, until solution is in neutral (pH value is 7).Reaction system is warming up to 80 DEG C, underpressure distillation goes out methyl iso-butyl ketone (MIBK), namely obtains the lurid tetraglycidyl m-xylene diamine epoxy resin of 67.94g, and yield is 94.3%.
The oxirane value of this tetraglycidyl m-xylene diamine epoxy resin is 0.92 equivalent/100 gram, and content of organic chloride is 0.13wt%, and viscosity is 1550mPaS(25 DEG C).
See Fig. 1, the MS(m/z of the tetraglycidyl m-xylene diamine epoxy resin that the present embodiment obtains): 361(M+1).
See Fig. 2, the tetraglycidyl m-xylene diamine epoxy resin that the present embodiment obtains
1the chemical shift of H-NMR and integration ratio: δ=2.40-2.63,8; δ=2.76,4; δ=2.93-3.13,8; δ=3.56-4.02,4; δ=7.29-7.37,4.
(embodiment 2 ~ embodiment 4)
The preparation method of each embodiment is substantially the same manner as Example 1, and difference is in table 1.
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | |
| M-xylene diamine | 27.2g（0.2mol） | 27.2g（0.2mol） | 27.2g（0.2mol） | 27.2g（0.2mol） |
| Deionized water | 7.2g（0.4mol） | 7.2g（0.4mol） | 7.2g（0.4mol） | 7.2g（0.4mol） |
| Epoxy chloropropane | 277.5g（3mol） | 296g（3.2mol） | 259g（2.8mol） | 277.5g（3mol） |
| The dropping temperature of m-xylene diamine and time | 45℃，1h | 30℃，0.5h | 50℃，1h | 40℃，1h |
| Ring-opening reaction temperature and time | 58℃，8h | 60℃，6h | 50℃，4h | 45℃，4h |
| Alkaline solution | The sodium hydroxide solution of 66.67g, 48wt% | The potassium hydroxide solution of 150g, 30wt% | The sodium hydroxide solution of 71g, 45wt% | The sodium hydroxide solution of 64g, 50wt% |
| Alkaline solution dropping temperature and time | 45℃，2h | 60℃，3h | 50℃，3h | 55℃，2.5h |
| Ring-closure reaction temperature and time | 45℃，2h | 60℃，1.5h | 50℃，2h | 55℃，1.5h |
| Reclaim epoxy chloropropane temperature | 60℃ | 75℃ | 80℃ | 80℃ |
| Extraction reagent | 170mL methyl iso-butyl ketone (MIBK)+170mL deionized water | 200mL benzene+200mL deionized water | 180mL butanone+180mL deionized water | 190mL toluene+190mL deionized water |
| Alkaline solution | The sodium hydroxide solution of 92.1g, 17wt% | 112g, 20wt% potassium hydroxide solution | 40g, 30wt% sodium hydroxide solution | 20g, 40wt% sodium hydroxide solution |
| Extraction temperature and time | 60℃，40min | 70℃，1h | 80℃，3h | 60℃，2.5h |
| Desolvation temperature | 80℃ | 100℃ | 110℃ | 70℃ |
| Tetraglycidyl m-xylene diamine epoxy resin | 67.94g | 66.13g | 67.93g | 67.52g |
| Yield | 94.3% | 91.8% | 94.3% | 93.8% |
| Oxirane value | 0.92 equivalent/100g | 0.91 equivalent/100g | 0.89 equivalent/100g | 0.90 equivalent/100g |
| Content of organic chloride | 0.13wt% | 0.2wt% | 0.19wt% | 0.13wt% |
| Viscosity (25 DEG C) | 1550mPa·S | 1620mPa·S | 2270mPa·S | 2500mPa·S |
Claims (4)
1. a preparation method for tetraglycidyl m-xylene diamine epoxy resin, is characterized in that having following steps:
1. epoxy chloropropane and deionized water are joined in reaction unit, be heated to 30 DEG C ~ 70 DEG C, drip m-xylene diamine, drip off and at the temperature of 40 DEG C ~ 80 DEG C, react 3h ~ 12h, until react completely; The mol ratio of described epoxy chloropropane, deionized water and m-xylene diamine is 8 ~ 18: 2: 1
2. drip alkaline solution in the material 1. obtained to step at the temperature of 30 DEG C ~ 80 DEG C, drip off and at the temperature of 30 DEG C ~ 80 DEG C, react 1h ~ 3h, until react completely; Alkali in described alkaline solution and step 1. in the mol ratio of m-xylene diamine be 4: 1;
3. after reaction terminates, first at the temperature of 60 DEG C ~ 80 DEG C, epoxy chloropropane is reclaimed in underpressure distillation, then adds inert solvent and deionized water, carries out extracting and demixing, removing water layer;
4. organic layer alkaline solution step 3. obtained is refining 0.5h ~ 4h at the temperature of 60 DEG C ~ 90 DEG C; Alkali in alkaline solution and step 1. in the mol ratio of m-xylene diamine be 1: 1 ~ 2.5: 1;
5. the material after refining is after being washed to neutrality, and underpressure distillation desolvation, obtains tetraglycidyl m-xylene diamine epoxy resin.
2. the preparation method of tetraglycidyl m-xylene diamine epoxy resin according to claim 1, is characterized in that: step 2. described in alkaline solution be sodium hydroxide solution or potassium hydroxide solution, concentration is 30wt% ~ 50wt%.
3. the preparation method of tetraglycidyl m-xylene diamine epoxy resin according to claim 1, is characterized in that: step 3. described in inert solvent and the volume ratio of deionized water be 1: 1; Inert solvent is the one in butanone, methyl iso-butyl ketone (MIBK), benzene and toluene.
4. the preparation method of tetraglycidyl m-xylene diamine epoxy resin according to claim 1, is characterized in that: step 4. described in alkaline solution be sodium hydroxide solution or potassium hydroxide solution, concentration is 15wt% ~ 30wt%.
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| CN111777741B (en) * | 2020-08-04 | 2023-03-21 | 上海华谊树脂有限公司 | Tetraglycidyl amine epoxy resin and preparation method thereof |
| CN113045516B (en) * | 2021-05-18 | 2023-03-24 | 湖南大学 | Preparation method of tetra-functional epoxy resin containing fluorene structure |
| CN115124492A (en) * | 2022-07-29 | 2022-09-30 | 上海华谊树脂有限公司 | Process for synthesizing tetraglycidyl amine epoxy resin by continuous method |
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