CN102827349A - 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 Racemic glycidol amine epoxy resin, be specifically related to a kind of preparation method of four glycidyl group m-xylene diamine epoxide resin.
Background technology
Epoxy resin has obtained in fields such as coating, stickers using widely with its good comprehensive mechanical properties, unique sticking power, excellent insulativity, less shrinking percentage.Therefore the second-order transition temperature of general purpose epoxy resin is 100 ℃～160 ℃, and thermal distorsion temperature is 70 ℃～140 ℃, can't satisfy like aerospace electromechanics etc. to require resistant to elevated temperatures applications.
Multiple functionality epoxide resin is (like 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 contain four epoxy group(ing) in the molecular structure; The cured article cross-linking density is high; Second-order transition temperature can reach 230 ℃～260 ℃, and thermal distorsion temperature therefore can be at life-time service more than 160 ℃ greater than 200 ℃.But commercial in the market these resin viscosities are bigger, bring inconvenience for actual the use.
Also contain four epoxy group(ing) in the four glycidyl group m-xylene diamine molecular structure, the resin after therefore solidifying has very high cross-linking density equally, and its thermal distorsion temperature is more than 180 ℃.More valuable is that the more above-mentioned multiple functionality epoxide resin of the viscosity of this resin is much lower, brings great convenience for actual application.
Chinese patent document CN101348559A discloses a kind of preparation method of m-xylene diamine epoxide resin, and this method is that m-xylene diamine, auxiliary agent, epoxy chloropropane are carried out ring opening etherification reaction under 30～85 ℃, and the reaction times is 1.5～10h; Then etherificate product and alkali are carried out ring-closure reaction at 30～85 ℃, the ring-closure reaction time is 1.5～10h, generates the m-xylene diamine epoxide resin bullion; The gained bullion is added organic solvent dissolution, extraction m-xylene diamine epoxide resin, and washing removes solvent to neutral at 80～160 ℃.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, MIBK, butanols, butanone, Virahol, quaternary ammonium salt, quaternary alkylphosphonium salt, sodium hydroxide, Pottasium Hydroxide, water or the Resorcinol.Wherein alkali is selected from sodium hydroxide, Pottasium Hydroxide, and its concentration is 10～50%, can be solid caustic soda.The deficiency of this method is:, and in this reaction process this is not well controlled the viscosity of the m-xylene diamine epoxide resin that causes finally obtaining big (16500～20000mPaS) because the easy hydrolysis of epoxy chloropropane, autohemagglutination.
Chinese patent document CN10163286A discloses a kind of preparation method of tetraglycidylamino compound, and this method is that diamines and excessive epihalohydrin are reacted in the presence of water, obtains the halohydrin body; Under the coexistence of phase-transfer catalyst, make the reaction of halohydrin body and alkali metal hydroxide then, obtain tetraglycidylamino compound; By product alkali metal halide and separatory that the ring-closure reaction that then is dissolved in water produces are removed, and obtain containing tetraglycidylamino compound and unreacted epihalohydrin; Unreacted epihalohydrin is reclaimed in then washing, separatory, distillation again, and the thick tetraglycidylamino compound that will obtain is dissolved in the organic solvent washing back separatory; Organic solvent is reclaimed in distillation at last, obtains tetraglycidylamino compound.Also comprise the organic solvent that reclaims is made with extra care with recycling.Wherein the mol ratio of epihalohydrin and diamines is 5.5～15: 1, preferred 6.5～10: 1; The alkali that ring-closure reaction is adopted and the mol ratio of diamines are 4.2～5: 1.The basic characteristics of this method are that recovered solvent is carried out refinement treatment with recycling.And the deficiency of its preparation tetraglycidylamino compound is: ring-closure reaction need be adopted phase-transfer catalyst; Not only cause cost higher; And its salt compound that adopts and straight-chain polyether compound also are the catalyzer of epoxy ring-opening; Therefore in the catalysis ring-closure reaction, also can increase the risk of resin self-polymerization, and big acyclic polyether compound (also the being crown ether-like) price that adopts extremely costliness and toxicity are bigger; When post-processed, remain in the water, increased the difficulty and the cost of wastewater treatment greatly.
Summary of the invention
The objective of the invention is to address the above problem, provide that a kind of cost is lower, the preparation method of the simple four glycidyl group m-xylene diamine epoxide resin of aftertreatment.The viscosity of the four glycidyl group m-xylene diamine epoxide resin that this method makes is lower, content of organic chloride is lower, oxirane value is higher.
The technical scheme that realizes the object of the invention is: a kind of preparation method of four glycidyl group m-xylene diamine epoxide resin; Have following steps: 1. epoxy chloropropane and deionized water are joined in the reaction unit; Be heated to 30 ℃～70 ℃; Drip m-xylene diamine, carry out ring-opening reaction after dripping off, until reacting completely; 2. under 30 ℃～80 ℃ temperature, in the material that 1. step obtains, drip alkaline solution, carry out ring-closure reaction after dripping off, until reacting completely; The mol ratio of alkali in the said alkaline solution and the step m-xylene diamine in 1. is 4: 1; 3. after reaction finished, epoxy chloropropane was reclaimed in first underpressure distillation, adds inert solvent and deionized water then, carries out extracting and demixing, removes water layer; 4. the organic layer that 3. step is obtained is made with extra care 0.5h～4h with alkaline solution under 60 ℃～90 ℃ temperature; The mol ratio of alkali in the alkaline solution and the step m-xylene diamine in 1. is 1: 1～2.5: 1; 5. the material after refining is through washing to neutrality, and underpressure distillation removes solvent, obtains the four glycidyl group m-xylene diamine epoxide resin.
Above-mentioned steps ring-opening reaction (also claiming chlorohydrin action) completeness 1. is influential to the quality of the finished product.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.Proper raw material mol ratio, temperature of reaction and reaction times can make that then this reaction can be complete.In addition, having of small quantity of deionized water is beneficial to the consistency of improving reactant, thereby helps the carrying out that react.But too high temperature of reaction then can cause the self-polymeric reaction of epoxy chloropropane, thereby increases the viscosity of resin.Therefore the mol ratio of the 1. middle epoxy chloropropane of step, deionized water and m-xylene diamine is 8～18: 2: 1, and preferred 14～16: 2: 1.Temperature of reaction is 40 ℃～80 ℃, preferred 40 ℃～60 ℃.Reaction times is 3h～12h, preferred 7h～10h.
The reaction activity of above-mentioned steps ring-closure reaction 2. is low, heat release is big; Therefore in the reaction process if there is unnecessary alkali will cause the hydrolysis and the autohemagglutination of epoxy chloropropane excessive in the reaction mass; Finally cause product viscosity to increase; Quality reduces, and this is to a most key factor of product viscosity influence.Certainly very few alkali also can cause residual chloropharin base too much, the recovery of influence back epoxy chloropropane.Therefore adopt the alkali of equivalent that alkali was all consumed in ring-closure reaction; And it is residual not have unnecessary alkali; Thereby at utmost avoid the hydrolysis and the self-polymeric reaction of epoxy chloropropane in the ring-closure reaction process, reduced resin viscosity, can not influence the recovery of back epoxy chloropropane again.The temperature of this ring-closure reaction is unsuitable too high in addition, otherwise also can cause the hydrolysis and the autohemagglutination of epoxy chloropropane.Therefore step temperature of reaction 2. is 30 ℃～80 ℃, preferred 40 ℃～60 ℃.The dropping time 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%.
The 3. middle temperature that reclaims epoxy chloropropane of above-mentioned steps should not be too high, otherwise can cause the epoxy chloropropane autohemagglutination.Therefore, the recovered temperature of epoxy chloropropane is 60 ℃～80 ℃.And the volume ratio of inert solvent and deionized water is 1: 1, is good with the inert solvent of adding 170mL～200mL and the deionized water of 170mL～200mL.Described inert solvent is a kind of in butanone, MIBK, benzene and the toluene, preferred butanone or MIBK.
The purpose of above-mentioned steps refining reaction 4. is to make complete closed loop of ring-closure reaction stage and the residual complete closed loop epoxidation of chloropharin base, and the raising oxirane value reduces content of organic chloride.Though adopted excessive alkali in the treating process, because this reaction is in the inert solvent of no epoxy chloropropane, to carry out, therefore, this excessive alkali can not cause the hydrolysis and the self-polymeric reaction of epoxy chloropropane, thereby guarantees product quality.Alkaline solution is sodium hydroxide solution or potassium hydroxide solution, and concentration is 15wt%～30wt%.
The washing of above-mentioned steps in 5. is after refining reaction finishes, and in reactor drum, adds the 200mL deionized water, slowly stirs standing demix behind the 5min, remove water layer, and repeated washing is to neutral.The temperature that underpressure distillation removes solvent is 60 ℃～110 ℃.
The positively effect that the present invention has: (1) preparation method of the present invention is mol ratio and temperature of reaction and the time through preferred epoxy chloropropane, deionized water and m-xylene diamine in ring-opening reaction, thereby guaranteed that ring-opening reaction can react completely.(2) preparation method of the present invention passes through to drip the alkali of equivalent in ring-closure reaction; Thereby alkali is all consumed in ring-closure reaction; And it is residual not have unnecessary alkali, has at utmost avoided the hydrolysis and the self-polymeric reaction of epoxy chloropropane in the ring-closure reaction process, greatly reduces resin viscosity.(3) because ring-closure reaction adopts is the alkali of equivalent; Therefore having part chloropharin base does not have complete closed loop; Therefore preparation method of the present invention also is included in the inert solvent and makes with extra care, and makes the complete epoxidation of chloropharin base, thereby has improved oxirane value; Reduced content of organic chloride; Finally can access the four glycidyl group m-xylene diamine of LV (1550PaS～2500mPaS, 25 ℃), low content of organic chlorine (below 0.2%), high epoxy value, also improve the recovery of epoxy chloropropane simultaneously.
Description of drawings
The liquid chromatography-mass spectrography figure of the four glycidyl group m-xylene diamine epoxide resin that Fig. 1 makes for embodiment 1.
The nmr spectrum of the four glycidyl group m-xylene diamine epoxide resin that Fig. 2 makes for embodiment 1.
Embodiment
(embodiment 1)
The preparation method of the four glycidyl group m-xylene diamine epoxide resin of present embodiment has following steps:
1. in the four-hole bottle of the 1000mL that mechanical stirring, reflux condensing tube, TM are housed, add the epoxy chloropropane (3mol) of 277.5g and the deionized water (0.4mol) of 7.20g successively; Be heated to 45 ℃; In 1h, slowly drip the m-xylene diamine (0.2mol) of 27.2g, drip off and be heated to 58 ℃ and carry out ring-opening reaction 8h.
2. be cooled to 45 ℃, in 2h, in the material that 1. step obtains, drip the sodium hydroxide solution that 66.67g concentration is 48wt% and (contain 32g sodium hydroxide, 0.8mol), drip off the back and continue ring-closure reaction 2h down at 45 ℃.
3. after reaction finished, epoxy chloropropane was reclaimed in underpressure distillation under 60 ℃ temperature earlier, and the time is 1h.Add 170mL MIBK and 170mL water then, after slowly being stirred to dissolving fully under 60 ℃ the temperature, pour layering in the separating funnel into, remove water layer.
4. the organic layer that 3. step is obtained is refunded in the four-hole bottle, under 60 ℃ temperature, adds the sodium hydroxide solution that 92.1g concentration is 17wt% and (contains 15.6g sodium hydroxide, 0.39mol), add back refining 40min under 60 ℃ temperature.
5. reaction system is reduced to 30 ℃, add the 200mL deionized water, slowly stir the back layering, remove water layer, repeat above-mentioned washing 2 times, be neutral (the pH value is 7) until solution.Reaction system is warming up to 80 ℃, and underpressure distillation goes out MIBK, promptly obtains the lurid four glycidyl group m-xylene diamine epoxide resin of 67.94g, and yield is 94.3%.
The oxirane value of this four glycidyl group m-xylene diamine epoxide resin is 0.92 equivalent/100 grams, and content of organic chloride is 0.13wt%, and viscosity is 1550mPaS (25 ℃).
See Fig. 1, the MS (m/z) of the four glycidyl group m-xylene diamine epoxide resin that present embodiment makes: 361 (M+1).
See Fig. 2, the four glycidyl group m-xylene diamine epoxide resin that present embodiment makes
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 and embodiment 1 are basic identical, and difference is seen table 1.
Table 1
| ? | Embodiment 1 | |
|
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 |
| The ring-opening reaction temperature and time | 58℃，8h | 60℃，6h | 50℃，4h | 45℃，4h |
| Alkaline solution | 66.67g, the sodium hydroxide solution of 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 |
| The ring-closure reaction temperature and time | 45℃，2h | 60℃，1.5h | 50℃，2h | 55℃，1.5h |
| Reclaim the epoxy chloropropane temperature | 60℃ | 75℃ | 80℃ | 80℃ |
| Reagent is used in extraction | 170mL MIBK+170mL deionized water | 200mL benzene+200mL deionized water | 180mL butanone+180mL deionized water | 190mL toluene+190mL deionized water |
| Alkaline solution | 92.1g, the sodium hydroxide solution of 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 |
| Remove solvent temperature | 80℃ | 100℃ | 110℃ | 70℃ |
| The four glycidyl group m-xylene diamine epoxide 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 ℃) | 1550mPa·S | 1620mPa·S | 2270mPa·S | 2500mPa·S |
Claims (6)
1. the preparation method of a four glycidyl group m-xylene diamine epoxide resin is characterized in that having following steps:
1. epoxy chloropropane and deionized water are joined in the reaction unit, be heated to 30 ℃～70 ℃, drip m-xylene diamine, drip off under 40 ℃～80 ℃ temperature and react 3h～12h, until reacting completely;
2. under 30 ℃～80 ℃ temperature, in the material that 1. step obtains, drip alkaline solution, drip off under 30 ℃～80 ℃ temperature and react 1h～3h, until reacting completely; The mol ratio of alkali in the said alkaline solution and the step m-xylene diamine in 1. is 4: 1;
3. after reaction finished, epoxy chloropropane was reclaimed in first underpressure distillation, adds inert solvent and deionized water then, carries out extracting and demixing, removes water layer;
4. the organic layer that 3. step is obtained is made with extra care 0.5h～4h with alkaline solution under 60 ℃～90 ℃ temperature; The mol ratio of alkali in the alkaline solution and the step m-xylene diamine in 1. is 1: 1～2.5: 1;
5. the material after refining is through washing to neutrality, and underpressure distillation removes solvent, obtains the four glycidyl group m-xylene diamine epoxide resin.
2. the preparation method of four glycidyl group m-xylene diamine epoxide resin according to claim 1 is characterized in that: the mol ratio of epoxy chloropropane, deionized water and the m-xylene diamine of step described in 1. is 8～18: 2: 1.
3. the preparation method of four glycidyl group m-xylene diamine epoxide resin according to claim 1 is characterized in that: the alkaline solution of step described in 2. is sodium hydroxide solution or potassium hydroxide solution, and concentration is 30wt%～50wt%.
4. the preparation method of four glycidyl group m-xylene diamine epoxide resin according to claim 1 is characterized in that: the step 3. recovered temperature of middle epoxy chloropropane is 60 ℃～80 ℃.
5. the preparation method of four glycidyl group m-xylene diamine epoxide resin according to claim 1 is characterized in that: the inert solvent of step described in 3. and the volume ratio of deionized water are 1: 1; Inert solvent is a kind of in butanone, MIBK, benzene and the toluene.
6. the preparation method of four glycidyl group m-xylene diamine epoxide resin according to claim 1 is characterized in that: the alkaline solution of step described in 4. is sodium hydroxide solution or potassium hydroxide solution, and concentration is 15wt%～30wt%.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108699017A (en) * | 2016-02-04 | 2018-10-23 | 格拉西姆工业股份有限公司 | A kind of technique preparing aromatic series N- glycidyl amines |
| CN111777741A (en) * | 2020-08-04 | 2020-10-16 | 上海华谊树脂有限公司 | Tetraglycidyl amine epoxy resin and preparation method thereof |
| CN113045516A (en) * | 2021-05-18 | 2021-06-29 | 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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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101348559A (en) * | 2008-09-10 | 2009-01-21 | 中昊晨光化工研究院 | Preparation of m-xylene diamine epoxide resin |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101348559A (en) * | 2008-09-10 | 2009-01-21 | 中昊晨光化工研究院 | Preparation of m-xylene diamine epoxide resin |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108699017A (en) * | 2016-02-04 | 2018-10-23 | 格拉西姆工业股份有限公司 | A kind of technique preparing aromatic series N- glycidyl amines |
| CN111777741A (en) * | 2020-08-04 | 2020-10-16 | 上海华谊树脂有限公司 | Tetraglycidyl amine epoxy resin and preparation method thereof |
| 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 |
| CN113045516A (en) * | 2021-05-18 | 2021-06-29 | 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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