CN104031242A - Flexible epoxy curing agent and preparation method thereof - Google Patents
Flexible epoxy curing agent and preparation method thereof Download PDFInfo
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- CN104031242A CN104031242A CN201410259386.8A CN201410259386A CN104031242A CN 104031242 A CN104031242 A CN 104031242A CN 201410259386 A CN201410259386 A CN 201410259386A CN 104031242 A CN104031242 A CN 104031242A
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Abstract
The invention provides a flexible epoxy curing agent, which solves the problems of low curing speed and poor corrosion resistance when the flexible epoxy curing agent in the prior art is at a low temperature and is obtained by adding an amine epoxy curing agent after addition reaction of polyether amine and thiourea. A preparation method of the flexible epoxy curing agent comprises the following two steps: 1, adding the polyether amine and the thiourea into a reaction kettle under the protection of an inert gas, and reacting for 1-6h at a high temperature of 110-160 DEG C; and 2, cooling the mixed system obtained in step 1 to 70-90 DEG C, adding the amine epoxy curing agent, stirring for 0.5-1h, cooling and discharging. Compared with the prior art, the obtained flexible epoxy curing agent has the advantages that the curing speed is high at the low temperature, the water resistance and the corrosion resistance are greatly improved, and the requirements in the corrosion resistance field can be met.
Description
Technical field
The present invention relates to epoxy hardener technical field, refer to that especially a kind of flexibility and preservative property are good, flexible epoxy solidifying agent that curing speed is fast at low temperatures, antiseptic property is good and preparation method thereof.
Background technology
Epoxy resin is that a class has bonds well, corrosion-resistant, electric insulation, the thermosetting polymer synthetic materials of the performances such as high strength, curable epoxide thing after it and solidifying agent fully solidify has good physics and chemistry performance, electrical insulating property, low-shrinkage, resistant of high or low temperature, the excellences such as wear resistance, various metals and nonmetallic bonding have been widely used in, corrosion resistant coating, insulating material, the manufacture of About Frp/cm etc., at electronics, electric, machinofacture, chemical anticorrosion, aerospace, ship and other industrial circles play important effect, become already the indispensable base mateiral of industrial circle.
Curable epoxide thing such as cable, concrete surface etc., requires it to have good flexibility and preservative property in the application of specific area.In prior art, mostly adopt polyether monoamine solidifying agent, especially the higher polyetheramine of molecular weight, although the flexibility that it has had, in the situation that temperature is lower, curing speed is very slow, for the tolerance performance of strong corrosive medium (strong acid, highly basic etc.) etc., can not meet the demands.
Summary of the invention
The present invention proposes a kind of flexible epoxy solidifying agent and preparation method thereof, for solving the problems referred to above of background technology.
Technical scheme of the present invention is achieved in that
A flexible epoxy solidifying agent, after polyetheramine and thiocarbamide addition reaction, adds amine epoxy hardener and obtains.
The present invention, by the addition reaction of polyetheramine and thiocarbamide, introduces thiourea group in solidifying agent, can guarantee the submissive performance of curable epoxide product, makes again epoxy hardener speed of response at low temperatures accelerate; Introduce amine curing agent, improved water tolerance, the resistance to acids and bases of epoxy hardener, can meet the application requiring in protection against corrosion field.
Preferably, the mol ratio of polyetheramine and thiocarbamide is (1:1)～(1:3).
Preferably, polyetheramine and thiocarbamide preferred molar ratio are (1:2)～(1:2.3).
Preferably, the weight percentage of amine curing agent in Flexible Curing Agent is 10～80%.
Preferably, amine curing agent preferred weight percentage ratio in Flexible Curing Agent is 25～60%.
Preferably, amine epoxy hardener is one or both in cashew nut phenols curing agent or phenolic aldehyde amine curing agent.
Amine epoxy hardener used in the present invention comprises: cashew nut phenols curing agent, phenolic aldehyde amine curing agent, fatty amines solidifying agent, alicyclic ring amine curing agent, aromatic amine curing agent, polyamide-based solidifying agent or their mixture, but one or both in cashew nut phenols curing agent, phenolic aldehyde amine curing agent comparatively preferably.
Cashew nut phenols curing agent used in the present invention is commercial goods, use the amine epoxy hardener of cardanol or cardanol mixture modification, there is Ka Delai company in main production company, Shanghai Meidong Biological Material Co., Ltd, Shanghai Jing Tian novel material company limited, Jinan Yun Jia Science and Technology Development Co., Ltd., grinds scientific and technological Industrial Co., Ltd in Xuzhou, Changsha Mai Nuoke industrial chemicals company limited etc.; Phenolic aldehyde amine curing agent used in the present invention is commercial goods, uses phenol, formaldehyde and aliphatic amide, aliphatic cyclic amine or aromatic amine to form via Mannich reaction.The trade names of mainly selecting are T-31 series.
Preferably, polyaminoether has general formula 1
Wherein, X, Y is a kind of in ethylidene, positive propylidene, isopropylidene, positive butylidene, isobutylene, tertiary butylidene, phenylene or xylylene; N is 2～200 integer.
Preferably, the integer that n is 3～10.
Polyetheramine used in the present invention for example has (Et-O)
n-(iProp)
mthe polyether backbone of type can be straight chain, side chain or pectination.
The invention allows for a kind of preparation method of flexible epoxy solidifying agent, comprise following two steps:
Step 1: under protection of inert gas, polyetheramine and thiocarbamide are put in reactor, reacted 1～6h at 110～160 ℃ of high temperature;
Step 2: the mixed system of step 1 gained is cooled to after 70～90 ℃, adds amine epoxy hardener, cooling after stirring 0.5～1h, discharging.
Compared with prior art, a kind of flexible epoxy solidifying agent that the present invention proposes is when keeping the kindliness of prior art, and under low temperature, curing speed is fast, and water tolerance, resistance to salt water and erosion resistance have obtained very big improvement, can meet the needs in protection against corrosion field.
Embodiment
Below in conjunction with the embodiment of the present invention, the technical scheme in the embodiment of the present invention is clearly and completely described, obviously, described embodiment is only the present invention's part embodiment, rather than whole embodiment.Embodiment based in the present invention, those of ordinary skills, not making the every other embodiment obtaining under creative work prerequisite, belong to the scope of protection of the invention.
Embodiment 1:
In the reactor with whipping appts, thermometer, condensing works, under inert atmosphere, add D20002000 gram of polyetheramine JEFFAMINE (1mol), 76 grams of thiocarbamides (1mol), are warming up to 140 ℃, reaction 3h, in reactor, liquid becomes faint yellow, be cooled to 70 ℃, add MD20151660 gram of modified by cardanol epoxy hardener (80%), stir after 45min, be cooled to 40 ℃, discharging.
By the prepared solidifying agent of above-described embodiment 1 and epoxy resin E-51 in mass ratio 1:1.7 at 25 ℃, solidify, its condensate performance is in Table 1.
Embodiment 2:
In the reactor with whipping appts, thermometer, condensing works, under inert atmosphere, add D20002000 gram of polyetheramine JEFFAMINE (1mol), 137 grams of thiocarbamides (1.8mol), are warming up to 160 ℃, reaction 1h, in reactor, liquid becomes faint yellow, be cooled to 70 ℃, add MD2015534 gram of modified by cardanol epoxy hardener (25%), stir after 1h, be cooled to 40 ℃, discharging.
By the prepared solidifying agent of above-described embodiment 2 and epoxy resin E-51 in mass ratio 1:1.7 at 25 ℃, solidify, its condensate performance is in Table 1.
Embodiment 3:
In the reactor with whipping appts, thermometer, condensing works, under inert atmosphere, add D20002000 gram of polyetheramine JEFFAMINE (1mol), 160 grams of thiocarbamides (2.1mol), are warming up to 140 ℃, reaction 3h, in reactor, liquid becomes faint yellow, be cooled to 90 ℃, add NX2003D1296 gram of modified by cardanol epoxy hardener (60%), stir after 30min, be cooled to 40 ℃, discharging.
By the prepared solidifying agent of above-described embodiment 3 and epoxy resin E-51 in mass ratio 1:1.6 at 25 ℃, solidify, its condensate performance is in Table 1.
Embodiment 4
In the reactor with whipping appts, thermometer, condensing works, under nitrogen atmosphere, add D20002000 gram of polyetheramine JEFFAMINE (1mol), 190.3 grams of thiocarbamides (2.5mol), are warming up to 110 ℃, reaction 6h, in reactor, liquid becomes faint yellow, be cooled to 80 ℃, add phenol aldehyde modified epoxy hardener T31219 gram (10%), stir after 30min, be cooled to 40 ℃, discharging.
By the prepared solidifying agent of above-described embodiment 4 and epoxy resin E-51 in mass ratio 1:1 at 25 ℃, solidify, its condensate performance is in Table 1.
Embodiment 5
In the reactor with whipping appts, thermometer, condensing works, under inert atmosphere, add D20002000 gram of polyetheramine JEFFAMINE (1mol), 152.3 grams of thiocarbamides (2mol), are warming up to 110 ℃, reaction 6h, in reactor, liquid becomes faint yellow, be cooled to 80 ℃, add daiamid epoxy curing agent D0125968.5 gram (45%), stir after 30min, be cooled to 40 ℃, discharging.
By the prepared solidifying agent of above-described embodiment 5 and epoxy resin E-51 in mass ratio 1.2:1 at 25 ℃, solidify, its condensate performance is in Table 1.
Embodiment 6
In the reactor with whipping appts, thermometer, condensing works, under inert atmosphere, add D20002000 gram of polyetheramine JEFFAMINE (1mol), 228.5 grams of thiocarbamides (3mol), are warming up to 160 ℃, reaction 2h, in reactor, liquid becomes faint yellow, be cooled to 80 ℃, add 445.7 (20%) grams of isophorone diamines, stir after 30min, be cooled to 40 ℃, discharging.
By the prepared solidifying agent of above-described embodiment 6 and epoxy resin E-51 in mass ratio 1:1.5 at 25 ℃, solidify, its condensate performance is in Table 1.
Embodiment 7
In the reactor with whipping appts, thermometer, condensing works, under inert atmosphere, add D20002000 gram of polyetheramine JEFFAMINE (1mol), 175.2 grams of thiocarbamides (2.3mol), are warming up to 160 ℃, reaction 1h, in reactor, liquid becomes faint yellow, be cooled to 90 ℃, add 761.3 (35%) grams of m-xylene diamines, stir after 30min, be cooled to 40 ℃, discharging.
By the prepared solidifying agent of above-described embodiment 7 and epoxy resin E-51 in mass ratio 1:1.3 at 25 ℃, solidify, its condensate performance is in Table 1.
The curing performance of each embodiment gained solidifying agent of table 1 and epoxy resin
As can be seen from Table I: the Flexible Curing Agent that the preparation method of the flexible epoxy solidifying agent proposing with the present invention prepares, fast with the speed of response of epoxy resin under room temperature, surface drying time all shortened much with the time of doing solid work, and the elongation of the product of gained is good.
In addition, cured article to above-described embodiment 1-7 gained carries out Corrosion Protection test, according to GB/T1733-1993, GB/T1763-1979, GB/T1763-1979, GB/T1771-2007, test respectively its water tolerance, alkali resistance (10%NaOH) and resistance to neutral salt spray, test result shows at least 15 days of gained without fading, non-corroding, without spall.
Compared with prior art, under the flexible cured article low temperature that the present invention proposes, curing speed is fast, and water tolerance and erosion resistance have obtained very big improvement, can meet the needs in protection against corrosion field.
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 modification of doing, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.
Claims (9)
1. a flexible epoxy solidifying agent, is characterized in that: described flexible epoxy solidifying agent by polyetheramine and thiocarbamide addition reaction after, add amine epoxy hardener and obtain.
2. a kind of flexible epoxy solidifying agent according to claim 1, is characterized in that: the mol ratio of described polyetheramine and described thiocarbamide is (1:1)～(1:3).
3. a kind of flexible epoxy solidifying agent according to claim 2, is characterized in that: described polyetheramine and described thiocarbamide preferred molar ratio are (1:2)～(1:2.3).
4. a kind of flexible epoxy solidifying agent according to claim 1, is characterized in that: the weight percentage of described amine curing agent in described Flexible Curing Agent is 10～80%.
5. a kind of flexible epoxy solidifying agent according to claim 4, is characterized in that: described amine curing agent preferred weight percentage ratio in described Flexible Curing Agent is 25～60%.
6. a kind of flexible epoxy solidifying agent according to claim 1, is characterized in that: one or both in the preferred cashew nut phenols curing agent of described amine epoxy hardener or phenolic aldehyde amine curing agent.
7. a kind of flexible epoxy solidifying agent according to claim 1, is characterized in that: described polyaminoether has general formula 1
Wherein, X, Y is a kind of in ethylidene, positive propylidene, isopropylidene, positive butylidene, isobutylene, tertiary butylidene, phenylene or xylylene; N is 2～200 integer.
8. a kind of flexible epoxy solidifying agent according to claim 7, is characterized in that: n is 3～10 integer preferably.
9. a preparation method for the flexible epoxy solidifying agent as described in claim 1-8 any one, is characterized in that: comprise following two steps:
Step 1: under protection of inert gas, polyetheramine and thiocarbamide are put in reactor, reacted 1～6h at 110～160 ℃ of high temperature;
Step 2: the mixed system of step 1 gained is cooled to after 70～90 ℃, adds amine epoxy hardener, cooling after stirring 0.5～1h, discharging.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201410259386.8A CN104031242A (en) | 2014-06-11 | 2014-06-11 | Flexible epoxy curing agent and preparation method thereof |
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| CN201410259386.8A CN104031242A (en) | 2014-06-11 | 2014-06-11 | Flexible epoxy curing agent and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104592508A (en) * | 2015-01-15 | 2015-05-06 | 长江大学 | Method for preparing epoxy resin flexible curing agent |
| CN111718473A (en) * | 2020-07-22 | 2020-09-29 | 增城市惠顺化工有限公司 | Ionic waterborne epoxy modified curing agent and preparation method thereof |
| CN113480727A (en) * | 2021-06-08 | 2021-10-08 | 华南理工大学 | Preparation method of modified polyether amine epoxy resin curing agent |
| CN114163614A (en) * | 2021-11-22 | 2022-03-11 | 瑞奇新材料(广州)有限公司 | Epoxy curing agent and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4011281A (en) * | 1975-03-06 | 1977-03-08 | Texaco Development Corporation | Polyether thiourea epoxy curing agents |
| CN102146266A (en) * | 2010-02-09 | 2011-08-10 | 江苏力宝建材工业有限公司 | Dry-hang adhesive, rapid curing agent for dry-hang adhesive and preparation process of rapid curing agent |
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2014
- 2014-06-11 CN CN201410259386.8A patent/CN104031242A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4011281A (en) * | 1975-03-06 | 1977-03-08 | Texaco Development Corporation | Polyether thiourea epoxy curing agents |
| CN102146266A (en) * | 2010-02-09 | 2011-08-10 | 江苏力宝建材工业有限公司 | Dry-hang adhesive, rapid curing agent for dry-hang adhesive and preparation process of rapid curing agent |
Non-Patent Citations (2)
| Title |
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| 尹浩 等: "硫脲改性聚醚胺环氧固化剂的性能研究", 《热固性树脂》 * |
| 张天才 等: "聚醚胺/酚醛胺-环氧树脂体系力学性能及其固化行为研究", 《中国涂料》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104592508A (en) * | 2015-01-15 | 2015-05-06 | 长江大学 | Method for preparing epoxy resin flexible curing agent |
| CN111718473A (en) * | 2020-07-22 | 2020-09-29 | 增城市惠顺化工有限公司 | Ionic waterborne epoxy modified curing agent and preparation method thereof |
| CN113480727A (en) * | 2021-06-08 | 2021-10-08 | 华南理工大学 | Preparation method of modified polyether amine epoxy resin curing agent |
| CN114163614A (en) * | 2021-11-22 | 2022-03-11 | 瑞奇新材料(广州)有限公司 | Epoxy curing agent and preparation method and application thereof |
| CN114163614B (en) * | 2021-11-22 | 2024-05-14 | 瑞奇(广东)技术有限公司 | Epoxy curing agent and preparation method and application thereof |
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Application publication date: 20140910 |