CN1233684C - Method for preparation of moderate temperature cured latent epoxy resin curing agent - Google Patents
Method for preparation of moderate temperature cured latent epoxy resin curing agent Download PDFInfo
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- CN1233684C CN1233684C CN 200410043655 CN200410043655A CN1233684C CN 1233684 C CN1233684 C CN 1233684C CN 200410043655 CN200410043655 CN 200410043655 CN 200410043655 A CN200410043655 A CN 200410043655A CN 1233684 C CN1233684 C CN 1233684C
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Abstract
The present invention provides a method for preparing a latent epoxy resin solidifying agent solidified at moderate temperature, which relates to a method for preparing a solidifying agent. The present invention comprises the following steps: a, ethyl acetoacetate and aluminium isopropoxide are uniformly mixed and heated, and after cooling, white crystalline solid powder is obtained; b, purified methylbenzene solvent is added to tri(ethyl acetoacetate) aluminium, and then, dienal alcohol is added; c, the mixture is decompressed and distilled to remove residual methylbenzene solvent, which obtains yellowish liquid, and after being cooled to room temperature, the yellowish liquid changes into solid; d, the product obtained in the step c is recrystallized, and then, the recrystallized product is dried to obtain white powder. The latent epoxy resin solidifying agent namely an aluminium compound prepared by the present invention can be used for forming a coinitiator system with bisphenol s for the solidification of alicyclic epoxy resin. The latent performance of the initiation system is long, and the initiation system can be used for solidifying epoxy resin at moderate temperature. The prepared solidifying agent has the advantages of short melting range, good initiation system degree and high purity.
Description
Technical field:
The present invention relates to a kind of preparation method of solidifying agent, particularly a kind of preparation method who is used for curing agent for epoxy resin.
Background technology:
The inflated spatial expanded structure technology can make up large space structure, is a kind of effective solution route that reduces delivery volume and launch cost.Along with the continuous expansion of epoxy composite material in the space structure range of application, its application in inflated spatial expanded structure has also obtained increasing concern.Because inflated spatial expanded structure has just been changed the singularity of technology, epoxy-resin systems long to latent period, intermediate temperature setting has urgent demand.The research of intermediate temperature setting epoxy-resin systems starts from the sixties.For obtain can be practical this resin system, carried out the research of latent curing system simultaneously.So far, the research in this field Showed Very Brisk still.The research of latent epoxy resin curing system mainly contains two kinds of approach: the one, some solidifying agent that at high temperature could play solidification are activated, and the 2nd, some low temperature and middle low temperature curing agent are carried out passivation.The kind of epoxy curing agent has a lot, but wherein can be directly not many as latent curing agent, usually be to need just can be used as latent curing agent through after certain modification.
Summary of the invention:
The preparation method who the purpose of this invention is to provide a kind of intermediate temperature setting latent epoxy curing agent.The present invention carries out as follows: a, three (methyl aceto acetate) aluminium synthetic: is (3～5) with methyl aceto acetate and aluminum isopropylate according to mol ratio: 1 mixes, heat temperature raising to 70～90 ℃, stirring reaction 1～2 hour obtains the white crystalline solid powder after the cooling; The preparation of b, aluminum compound: in three (methyl aceto acetate) aluminium, add the toluene solvant of having purified, add alphanol again, wherein the mol ratio of three (methyl aceto acetate) aluminium and alphanol is 1: 3, is warming up to 100～120 ℃, reacts 25～30 hours postcooling to room temperature; C, underpressure distillation: said mixture is carried out underpressure distillation, remove remaining solvent toluene, obtain flaxen liquid, become solid after being cooled to room temperature; D, product recrystallization: the product that obtains in the c step is carried out recrystallization, and drying obtains white powder then.Resins, epoxy latent curing agent one aluminum compound that the present invention prepares can be formed the coinitiator system with bis-phenol s, is used for the curing of cycloaliphatic epoxy resin, and this initiator system latent is long, can intermediate temperature setting Resins, epoxy; And solidifying agent melting range weak point, better crystallinity degree, the purity height prepared.
Description of drawings:
Fig. 1 is the infrared spectrum of three (etheric acid octadecyl ester) aluminium, and Fig. 2 is the infrared spectrum of three (etheric acid 20 diester) aluminium.
Embodiment:
Embodiment one: present embodiment is carried out as follows: a, three (methyl aceto acetate) aluminium synthetic: is (3～5) with methyl aceto acetate and aluminum isopropylate according to mol ratio: 1 mixes, heat temperature raising to 70～90 ℃, stirring reaction 1～2 hour obtains the white crystalline solid powder after the cooling; The preparation of b, aluminum compound: in three (methyl aceto acetate) aluminium, add the toluene solvant of having purified, add alphanol again, wherein the mol ratio of three (methyl aceto acetate) aluminium and alphanol is 1: 3, is warming up to 100～120 ℃, reacts 25～30 hours postcooling to room temperature; C, underpressure distillation: said mixture is carried out underpressure distillation, remove remaining solvent toluene, obtain flaxen liquid, become solid after being cooled to room temperature; D, product recrystallization: the product that obtains in the c step is carried out recrystallization, and drying obtains white powder then.Described alphanol is n-dodecanol, positive hexadecanol, positive stearyl alcohol or positive behenyl alcohol.
Embodiment two: present embodiment is carried out as follows: a, three (methyl aceto acetate) aluminium synthetic: 1. methyl aceto acetate is carried out underpressure distillation, purification, 2. in 500ml four-hole round-bottomed flask, add aluminum isopropylate 10.67g, methyl aceto acetate 25ml, stir, 3. 10 minutes afterreaction things are partly dissolved, heat temperature raising to 80 ℃, 4. stirring reaction 1.5 hours obtains the white crystalline solid powder behind the naturally cooling, be three (methyl aceto acetate) aluminium; The preparation of b, aluminum compound: the 1. purification of toluene: adding 90ml concentration is 98% the vitriol oil in 600ml toluene, vibration, separation; Repeat 2～3 times, wash twice, be that 10% sodium carbonate solution is washed twice with concentration then, vibration is till no bubble generates, wash twice, till being dried to no bubble and producing with hydrolith, 110～120 ℃ cut is collected in air distillation, and 2. aluminum compound is synthetic: add the toluene solvant of having purified in three (methyl aceto acetate) aluminium, add alphanol again, logical water of condensation, argon shield is stirred, and wherein the mol ratio of three (methyl aceto acetate) aluminium and alphanol is 1: 3, be warming up to 110 ℃, react 26 hours postcooling to room temperature; C, underpressure distillation: said mixture is carried out underpressure distillation, remove remaining solvent toluene, obtain flaxen liquid, become solid after being cooled to room temperature; D, product recrystallization: in the product that the c step obtains, add normal hexane 150ml, be heated to boiling, after being cooled to room temperature, move in the refrigerator, further cooling with dry and through the frosted funnel vacuumizing filtration of subzero treatment, repeats above step, product is carried out recrystallization twice, place 45 ℃ of loft drier to obtain white powder in dry 24 hours filtration product.
Embodiment three: present embodiment is an example to prepare three (etheric acid octadecyl ester) aluminium, wherein three (etheric acid octadecyl ester) aluminium is prepared as follows: a, three (methyl aceto acetate) aluminium synthetic: add aluminum isopropylate 10.67g in 500ml four-hole round-bottomed flask, the methyl aceto acetate 25ml after purifying, the afterreaction thing was partly dissolved in 10 minutes, heat temperature raising to 80 ℃, stirring reaction 1.5 hours, obtain the white crystalline solid powder behind the naturally cooling, be three (methyl aceto acetate) aluminium; The preparation of b, aluminum compound: in three (methyl aceto acetate) aluminium, add the toluene solvant of having purified, add positive stearyl alcohol again, logical water of condensation, argon shield, stir, wherein three (methyl aceto acetate) aluminium is 1: 3 with the mol ratio of positive stearyl alcohol, is warming up to 110 ℃, reacts to naturally cool to room temperature after 26 hours; C, underpressure distillation: said mixture is carried out underpressure distillation, remove remaining solvent toluene, obtain flaxen liquid, become solid after being cooled to room temperature; D, product recrystallization: in the product that the c step obtains, add normal hexane 150ml, be heated to boiling, after being cooled to room temperature, move in the refrigerator, further cooling is with dry and through the frosted funnel vacuumizing filtration of subzero treatment, repeat above step, product is carried out recrystallization twice, place 45 ℃ of loft drier to obtain white powder in dry 24 hours filtration product, productive rate is 86%.The powder that obtains is carried out fusing point test, ultimate analysis, infrared measurement, and the result sees Table 1 (aluminum compound fusing point), table 2 (aluminum compound results of elemental analyses) and Fig. 1 respectively, and the fusing point of product is 72.2 ℃, and melting range is shorter, and degree of crystallinity is better; Ultimate analysis illustrates that its material purity is higher, and infrared spectra has confirmed to have synthesized target product, and the molecular structural formula of its product is:
Embodiment four: present embodiment is an example to prepare three (etheric acid 20 diester) aluminium, wherein three (etheric acid 20 diester) aluminium is prepared as follows: a, three (methyl aceto acetate) aluminium synthetic: add aluminum isopropylate 10.67g in 500ml four-hole round-bottomed flask, the methyl aceto acetate 25ml after purifying, the afterreaction thing was partly dissolved in 10 minutes, heat temperature raising to 80 ℃, stirring reaction 1.5 hours, obtain the white crystalline solid powder behind the naturally cooling, be three (methyl aceto acetate) aluminium; The preparation of b, aluminum compound: in three (methyl aceto acetate) aluminium, add the toluene solvant of having purified, add positive behenyl alcohol again, logical water of condensation, argon shield, stir, wherein three (methyl aceto acetate) aluminium is 1: 3 with the mol ratio of positive behenyl alcohol, is warming up to 110 ℃, reacts to naturally cool to room temperature after 26 hours; C, underpressure distillation: said mixture is carried out underpressure distillation, remove remaining solvent toluene, obtain flaxen liquid, become solid after being cooled to room temperature; D, product recrystallization: in the product that the c step obtains, add normal hexane 150ml, be heated to boiling, after being cooled to room temperature, move in the refrigerator, further cooling is with dry and through the frosted funnel vacuumizing filtration of subzero treatment, repeat above step, product is carried out recrystallization twice, place 45 ℃ of loft drier to obtain white powder in dry 24 hours filtration product, productive rate is 88.8%.The powder that obtains is carried out fusing point test, determination of elemental analysis, infrared measurement, and the result sees Table 1 respectively, table 2 and Fig. 2, and the fusing point of product is 80.7 ℃, and melting range is shorter; Ultimate analysis illustrates that its material purity is higher, and degree of crystallinity is better; Infrared spectra has confirmed to have synthesized target product, and the structural molecule formula of its product is:
In order to verify the curing performance of initiator, resin formula system curing process is studied Resins, epoxy.At first carry out the preparation of glue, step is as follows: a, get in the glass cup that an amount of HZ9221 Resins, epoxy joins a 150ml, in mass ratio is that 100: 3 ratio adds bisphenol S, induction stirring, oil bath is heated to 100 ℃, continue this state up to bisphenol S dissolve fully, the glue clarification, continue to stir and be cooled to room temperature; B, taking by weighing the Resins, epoxy of certain mass respectively with nine dixie cups, is that 100: 3 ratio adds aluminum compound in mass ratio, stirs, and puts into baking oven then and heats, and after treating to dissolve fully, stirs fast and is cooled to room temperature; C, be equipped with in the dixie cup of glue at each and add Resins, epoxy/bisphenol S mixed glue solution, stir fast and make its homodisperse (sonic oscillation disperses almost not effect to it) by stoichiometric ratio; D, the glue that configures is divided into three parts, portion places room temperature storage, and portion places 4 ℃ of refrigerators to store a cryopreservation.Test the DSC curve of above-mentioned glue when different temperature rise rate, obtain the formulation cured temperature all at 110～120 ℃.Storage to the glue system is studied, and the glue of above-mentioned preparation is positioned over room temperature environment in test tube, and viscosity was constant substantially in 65 days, and the explanation system has good storage.
Table 1
| Three (etheric acid octadecyl ester) aluminium | Three ( | |
| Melting range | 3.6℃ | 3.8℃ |
| Fusing point | 72.2℃ | 80.7℃ |
Table 2
Claims (2)
1, a kind of preparation method of intermediate temperature setting latent epoxy curing agent, it is characterized in that it carries out as follows: a, three (methyl aceto acetate) aluminium synthetic: is (3～5) with aluminum isopropylate according to mol ratio with methyl aceto acetate: 1 mixes, heat temperature raising to 70～90 ℃, stirring reaction 1～2 hour obtains the white crystalline solid powder after the cooling; The preparation of b, aluminum compound: in three (methyl aceto acetate) aluminium, add the toluene solvant of having purified, add alphanol again, wherein the mol ratio of three (methyl aceto acetate) aluminium and alphanol is 1: 3, is warming up to 100～120 ℃, reacts 25～30 hours postcooling to room temperature; C, underpressure distillation: said mixture is carried out underpressure distillation, remove remaining solvent toluene, obtain flaxen liquid, become solid after being cooled to room temperature; D, product recrystallization: the product that obtains in the c step is carried out recrystallization, and drying obtains white powder then.
2, the preparation method of a kind of intermediate temperature setting latent epoxy curing agent according to claim 1 is characterized in that described alphanol is n-dodecanol, positive hexadecanol, positive stearyl alcohol or positive behenyl alcohol.
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| CN 200410043655 CN1233684C (en) | 2004-06-25 | 2004-06-25 | Method for preparation of moderate temperature cured latent epoxy resin curing agent |
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| CN 200410043655 CN1233684C (en) | 2004-06-25 | 2004-06-25 | Method for preparation of moderate temperature cured latent epoxy resin curing agent |
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| CN1233684C true CN1233684C (en) | 2005-12-28 |
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