CN102604046B - DMP-30 (dimethyl phthalate-30) closing method and application of DMP-30 in epoxy adhesive - Google Patents
DMP-30 (dimethyl phthalate-30) closing method and application of DMP-30 in epoxy adhesive Download PDFInfo
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- CN102604046B CN102604046B CN201210064580.1A CN201210064580A CN102604046B CN 102604046 B CN102604046 B CN 102604046B CN 201210064580 A CN201210064580 A CN 201210064580A CN 102604046 B CN102604046 B CN 102604046B
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Abstract
The invention relates to a DMP-30 (dimethyl phthalate-30) closing method, which includes mixing, by weight, 60%-90% of DMP-30 and 10-40% of acidoid to disable the DMP-30 to open loops of epoxy perssad. The balance can be damaged by gently heating to start curing reaction in practical application of the DMP-30, so that the DMP-30 turns to be similar to a latency curing agent or curing catalyst. The invention further comprises epoxy adhesive containing the closed DMP-30, and the adhesive can be used for adhering only by gently heating.
Description
Technical field
The present invention relates to the enclosure method of a kind of DMP-30 and the application at epoxy adhesive thereof, be used for improving its stability at epoxy adhesive, belong to epoxyn field.
Background technology
DMP-30 structural formula is:
Its molecular formula: C15H27N3O, molecular weight: 265.40, CAS No.:90-72-2, title: 2,4,6-tri-(dimethylaminomethyl) phenol, English name: 2,4,6-tris (dimethylaminomethyl) phenol flash-point: 150 DEG C; Proportion (25 DEG C): 0.97, outward appearance is light yellow transparent liquid, approximately 250 DEG C of boiling points, have amine stink, are soluble in organic solvent, are dissolved in cold water, are slightly soluble in hot water.
DMP-30 is mainly as epoxy curing agent, and fast setting or temperature curing epoxy low resin coating, serve as and water foundry goods, sealing member etc. at normal temperatures.DMP-30 can be separately as epoxy curing agent, the consumption of the bisphenol A epoxide resin to epoxy equivalent (weight) 185-195 is 10%, also can mix with other epoxy hardener use, rises and promotes solidification, can improve solidification rate, while doing promotor use, consumption is 0.1%-3%; Ambient cure consumption 10%-15% during for epoxy resin-liquid polysulfide system, consumption 6% is heating and curing.In general, DMP-30 uses separately the performance that can give bonding system and sealing material uniqueness, can reduce greatly solidification value as promotor use, improves curing efficiency, and in epoxy resin adhesive field, tool has been widely used.Its cured epoxy group open loop mechanism is as follows: be first the N atom in DMP-30, owing to containing lone-pair electron, the nucleophilicity of its lone-pair electron is impelled attack epoxide group, after epoxide group is opened, the negative oxygen ion forming can further react with epoxide group, thereby realizes the polymerizing curable of epoxy resin.See following reaction process:
DMP-30 is generally applied in and in two component epoxy glue, makees solidifying agent and use, be mainly because its amido alkalescence is stronger, be easy to and epoxide group ring-opening reaction, therefore, can not use as latent curing agent, even as promotor, can not make single-component epoxy glue, and, when two components use, also exist the operating time short, the phenomenon that gel is too fast, this is the major defect in DMP-30 application.
Summary of the invention
Technical problem to be solved by this invention is to provide the enclosure method of a kind of DMP-30, by the pH value that adds the whole system of acidic substance control in DMP-30 is kept to latent to a certain extent with guarantee DMP-30, overcome easily and ring-opening reaction occurs epoxide group at short notice, cause in use, operating time is short, the defect that gel is too fast.
The technical scheme that the present invention solves the problems of the technologies described above is as follows: a kind of DMP-30 enclosure method, is mixed by 60%～90% (weight percent) DMP-30,10%～40% (weight percent) acidic substance.
In wherein said acidic substance hydrogen cation and described in the following reaction process of nitrogen-atoms cohesive process:
The invention has the beneficial effects as follows: utilize the nitrogen-atoms of the sour hydrogen cation providing in DMP-30 to be combined, form a kind of weak acid base equilibrium state, or utilize the lone-pair electron of nitrogen-atoms in lewis acidic electron pairing ability complexing DMP-30, thereby make DMP-30 lose the open loop ability to epoxide group, and in practical application, only need low-grade fever to destroy this balance, just can start curing reaction, thereby make DMP-30 become a kind of similar latent curing agent, or curing catalyst, therefore form a class and had the low-temperature curing performance that similar two component epoxy sizing agent is the same, have the novel epoxy sizing agent system of the easy processing property that single-component epoxy sizing agent is the same simultaneously.
On the basis of technique scheme, the present invention can also do following improvement.
In described DMP-30 enclosure method, add acidic substance to make the pH value in mixed system be controlled at 7-12, preferably PH is 7-10.
Adopt the beneficial effect of above-mentioned further scheme to be: the nitrogen-atoms with the hydrogen cation that ensures to provide enough in DMP-30 is combined.
Further, described acidic substance comprise mineral acid, and organic acid does not contain carboxyl in Lewis acid or organism but shows acid material.
Further, described mineral acid is nitric acid, phosphoric acid, sulfuric acid, hydrochloric acid, hydrofluoric acid, hydrochloric acid, hydroiodic acid HI, Hydrogen bromide, hypochlorous acid, perchloric acid, bromic acid, a kind of or any several mixture in acid iodide etc.
Further, in described organism, not containing carboxyl but show acid material is barbituric acid, phenylethyl barbituric acid.
Further, described organic acid is C
1-C
90longer chain fatty acid, the aromatic acid that contains benzene ring structure, the organic acid that contains alicyclic structure, contains a kind of in the organic acid that do not comprise key etc. or several mixture arbitrarily.
Further, described Lewis acid comprises group of the lanthanides, and actinium series, so the compound of the element that subgroup element and the 3rd main group etc. contain unsaturated unoccupied orbital.
Further, described in contain unsaturated unoccupied orbital the compound of element be aluminum chloride, zinc chloride.
The present invention also provides a kind of epoxy adhesive, it is characterized in that, comprise the material of following weight percent: the DMP-30 5～38% after the sealing of preparing according to above-mentioned DMP-30 enclosure method, epoxy resin 30～60%, thinner 1～5%, filler 30～60%, coupling agent 0～1%.
Embodiment
Below principle of the present invention and feature are described, example, only for explaining the present invention, is not intended to limit scope of the present invention.
Embodiment 1
Accurately take each raw material by following weight percent, DMP-30 consumption 90%, phosphorous acid 10%.Simple physical by the two is mixed, and after mixing, the mixture pH value of formation is 7.1, and it is for subsequent use that mixture room temperature keeps.Its application at epoxy adhesive is made up of following raw material: the DMP-30 38% after 828EL epoxy resin 30%, tertiary butyl carbonic ether glycidyl ether thinner 2%, Nanjing Hua Yuan silicon powder NF110 consumption 30%, sealing.Above-mentioned each component is added in double-planet dynamic mixing stirrer successively, and being evacuated to vacuum tightness is-0.08～-0.05MPa, in 500 revs/min of stirrings 2 hours, stirs.
Embodiment 2
Accurately take each raw material by following weight percent, DMP-30 consumption 80%, citric acid 20%.Simple physical by the two is mixed, and after mixing, the mixture pH value of formation is 9.8, and it is for subsequent use that mixture room temperature keeps.Its application at epoxy adhesive is made up of following raw material: the DMP-30 15% after E51 epoxy resin 25%, H8 thinner 5%, 600 order silicon powder fillers 54%, KH560 coupling agent 1%, sealing.Above-mentioned each component is added in double-planet dynamic mixing stirrer successively, and being evacuated to vacuum tightness is-0.08～-0.05MPa, in 500 revs/min of stirrings 2 hours, stirs.
Embodiment 3
Accurately take each raw material by following weight percent, DMP-30 consumption 60%, oleic acid 40%.Simple physical by the two is mixed, and after mixing, the mixture pH value of formation is 8.3, and it is for subsequent use that mixture room temperature keeps.Its application at epoxy adhesive is made up of following raw material: the DMP-30 25% after 8240 epoxy resin 44%, Isosorbide-5-Nitrae butyleneglycol glycidyl ether thinner 1%, 600 order silicon powder fillers 29%, KH560 coupling agent 1%, sealing.Above-mentioned each component is added in double-planet dynamic mixing stirrer successively, and being evacuated to vacuum tightness is-0.08～-0.05MPa, in 500 revs/min of stirrings 2 hours, stirs.
Embodiment 4
Accurately take each raw material by following weight percent, DMP-30 consumption 60%, aluminum chloride 40%.Simple physical by the two is mixed, and after mixing, the mixture pH value of formation is 9.9, and it is for subsequent use that mixture room temperature keeps.Its application at epoxy adhesive is made up of following raw material: the DMP-30 25% after E44 epoxy resin 50%, Ex10 thinner 5%, 201 spherical powder fillers 19%, KH560 coupling agent 1%, sealing.Above-mentioned each component is added in double-planet dynamic mixing stirrer successively, and being evacuated to vacuum tightness is-0.08～-0.05MPa, in 500 revs/min of stirrings 2 hours, stirs.
Embodiment 5
Accurately take each raw material by following weight percent, DMP-30 consumption 85%, barbituric acid 15%.Simple physical by the two is mixed, and after mixing, the mixture pH value of formation is 8.6, and it is for subsequent use that mixture room temperature keeps.Its application at epoxy adhesive is made up of following raw material: the DMP-30 15% after 862 epoxy resin 49%, N10 thinner 1%, 1250 order silicon powder fillers 34%, KH560 coupling agent 1%, sealing.Above-mentioned each component is added in double-planet dynamic mixing stirrer successively, and being evacuated to vacuum tightness is-0.08～-0.05MPa, in 500 revs/min of stirrings 2 hours, stirs.
Embodiment 6
Accurately take each raw material by following weight percent, DMP-30 consumption 80%, barbituric acid 10%, oleic acid 10%.Simple physical by the two is mixed, and after mixing, the mixture pH value of formation is 8.8, and it is for subsequent use that mixture room temperature keeps.Its application at epoxy adhesive is made up of following raw material: the DMP-30 15% after 4901E epoxy resin 30%, N10 thinner 5%, NF110 filler 49%, KH560 coupling agent 1%, sealing.Above-mentioned each component is added in double-planet dynamic mixing stirrer successively, and being evacuated to vacuum tightness is-0.08～-0.05MPa, in 500 revs/min of stirrings 2 hours, stirs.
Embodiment 7
Accurately take each raw material by following weight percent, DMP-30 consumption 75%, barbituric acid 15%, citric acid 10%.Simple physical by the two is mixed, and after mixing, the mixture pH value of formation is 8.2, and it is for subsequent use that mixture room temperature keeps.Its application at epoxy adhesive is made up of following raw material: the DMP-30 5% after 133L polyurethane modified epoxy resin 35%, DER732 thinner 1%, 101 spherical powder fillers 59%, sealing.Above-mentioned each component is added in double-planet dynamic mixing stirrer successively, and being evacuated to vacuum tightness is-0.08～-0.05MPa, in 500 revs/min of stirrings 2 hours, stirs.
Experimental test closed performance of the present invention by below and at the application performance of epoxy adhesive.Closed performance is the stability in order to improve epoxy adhesive, therefore, characterizes by the variation of observing sizing agent viscosity, and the hardness after the application of epoxy adhesive is solidified by it, tensile strength, shearing resistance characterizes.
The viscosity of test example 1 epoxy adhesive changes performance test
Viscosity test embodiment is carried out by the following method: the sample of embodiment 1-5 and existing common bi-component epoxy adhesive are measured to viscosity under 25 DEG C of conditions, then sample is placed in 25 DEG C of thermostat containers and is preserved 4 hours, after taking out, measure viscosity, characterize the stability of sample by the changing conditions of viscosity.
Concrete data are in table 1.
Test example 2 hardness Shore tests
Hardness test: test according to GB/T 531-1999
Hardness test embodiment is carried out by the following method: the sample of embodiment 1-5 and existing common bi-component epoxy adhesive, after 60 DEG C of curing 180min, are tested respectively to the hardness of sample according to GB/T 531-1999.
Concrete data are in table 2.
Test example 3 tensile strength tests
Tensile strength test: test according to GB/T528-1998
Tensile strength test implementation scheme is carried out by the following method: the sample of embodiment 1-5 and existing common bi-component epoxy adhesive, after 60 DEG C of curing 180min, are tested respectively to the tensile strength of sample according to GB/T528-1998.
Concrete data are in table 3.
Test example 4 shearing resistance tests
Shearing resistance test: test according to GB/T7124-1986
Shearing resistance test implementation scheme is carried out by the following method: the sample of embodiment 1-5 and existing common bi-component epoxy adhesive, after 60 DEG C of curing 180min, are tested respectively to the shearing resistance of sample according to GB/T7124-1986.
Concrete data are in table 4.
Table 1 embodiment 1-7 and common bi-component epoxy adhesive viscosity contrast test result
Table 2 embodiment 1-7 and common bi-component epoxy adhesive Shore hardness contrast test result
| Sample | Shore hardness D performance test |
| The sample of embodiment 1 | 82 |
| The sample of embodiment 2 | 83 |
| The sample of embodiment 3 | 83 |
| The sample of embodiment 4 | 83 |
| The sample of embodiment 5 | 82 |
| The sample of embodiment 6 | 84 |
| The sample of embodiment 7 | 80 |
| Comparative example's sample | 80 |
Table 3 embodiment 1-7 and common bi-component epoxy adhesive tensile strength contrast test result
| Sample | Tensile strength performance test (Mpa) |
| The sample of embodiment 1 | 34.3 |
| The sample of embodiment 2 | 32.9 |
| The sample of embodiment 3 | 32.8 |
| The sample of embodiment 4 | 34.5 |
| The sample of embodiment 5 | 34.2 |
| The sample of embodiment 6 | 30.4 |
| The sample of embodiment 7 | 29.2 |
| Comparative example's sample | 30.3 |
Table 4 embodiment 1-7 and common bi-component epoxy adhesive shearing resistance contrast test result
| Sample | Shearing resistance performance test (Mpa) |
| The sample of embodiment 1 | 13.3 |
| The sample of embodiment 2 | 12.9 |
| The sample of embodiment 3 | 12.8 |
| The sample of embodiment 4 | 13.5 |
| The sample of embodiment 5 | 13.2 |
| The sample of embodiment 6 | 12.4 |
| The sample of embodiment 7 | 12.1 |
| Comparative example's sample | 12.5 |
From above data analysis, the stability of embodiment sample is far away higher than common double component epoxy sizing agent, the mechanical properties such as hardness, tensile strength, shearing resistance, contrast with comparative example's result, indices is more consistent, illustrates that the DMP-30 solidifying agent after sealing treatment does not lose reactive behavior.On the whole, illustrate when sealing DMP-30 of the present invention is applied to epoxy adhesive, do not lose under the prerequisite of its mechanical property in guarantee, stability has increased significantly, and is the method for the novel raising epoxy adhesive stability of a class.
The foregoing is only preferred embodiment of the present invention, in order to limit the present invention, within the spirit and principles in the present invention not all, any amendment of doing, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.
Claims (2)
1. a DMP-30 enclosure method, is characterized in that, by 60%～90%(weight percent) DMP-30,10%～40%(weight percent) acidic substance are mixed; The pH value of described mixed system is controlled as 7-10; Described acidic substance are aluminum chloride, zinc chloride.
2. an epoxy adhesive, it is characterized in that, comprise the material of following weight percent: the DMP-30 5～38% after the sealing that according to claim 1 prepared by DMP-30 enclosure method, epoxy resin 30～60%, thinner 1～5%, filler 30～60%, coupling agent 0～1%.
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| CN201210064580.1A CN102604046B (en) | 2012-03-13 | 2012-03-13 | DMP-30 (dimethyl phthalate-30) closing method and application of DMP-30 in epoxy adhesive |
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| CN201210064580.1A CN102604046B (en) | 2012-03-13 | 2012-03-13 | DMP-30 (dimethyl phthalate-30) closing method and application of DMP-30 in epoxy adhesive |
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| CN102604046B true CN102604046B (en) | 2014-09-24 |
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| CN103204756A (en) * | 2012-10-16 | 2013-07-17 | 湖北航天化学技术研究所 | High temperature-resistant solid propellant for oilfield fracturing |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4042031A (en) * | 1975-11-13 | 1977-08-16 | Shell Oil Company | Plugging subterranean earth formations with aqueous epoxy emulsions containing fine solid particles |
| CN102153977A (en) * | 2011-03-11 | 2011-08-17 | 中南林业科技大学 | Anti-seepage leak-stopping epoxy adhesive and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001044342A1 (en) * | 1999-12-14 | 2001-06-21 | Mitsui Chemicals, Inc. | Sealing agent for liquid-crystal display cell, composition for sealing agent for liquid-crystal display cell, and liquid-crystal display element |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4042031A (en) * | 1975-11-13 | 1977-08-16 | Shell Oil Company | Plugging subterranean earth formations with aqueous epoxy emulsions containing fine solid particles |
| CN102153977A (en) * | 2011-03-11 | 2011-08-17 | 中南林业科技大学 | Anti-seepage leak-stopping epoxy adhesive and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 王德中等.环氧树脂生产与应用.《环氧树脂生产与应用》.化学工业出版社材料科学与工程出版中心,2001,(第2版),225-226. * |
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