CN103333323A - High-toughness high-activity epoxy resin curing agent and preparation method thereof - Google Patents
High-toughness high-activity epoxy resin curing agent and preparation method thereof Download PDFInfo
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- CN103333323A CN103333323A CN2013102362286A CN201310236228A CN103333323A CN 103333323 A CN103333323 A CN 103333323A CN 2013102362286 A CN2013102362286 A CN 2013102362286A CN 201310236228 A CN201310236228 A CN 201310236228A CN 103333323 A CN103333323 A CN 103333323A
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Abstract
The invention discloses a high-toughness high-activity epoxy resin curing agent and a preparation method of the curing agent. The method comprises the following steps of: weighing cyclic carbonate and polyamine according to the condition that the molar ratio of the cyclic carbonate to the polyamine is (0.1-1):1, feeding the cyclic carbonate into a reactor filled with the polyamine in batches for reaction, weighing thiourea, the molar weight of which is 0.5-2.5 times that of the polyamine, feeding the thiourea into the reactor in batches, reducing the temperature of the system to 80 DEG C after the reaction is finished, adding an accelerant, the mass of which is 0.5-5% of the total mass of the products, into the products, uniformly mixing the accelerant and the products, discharging the mixture and storing the mixture. The curing agent prepared by using the preparation method disclosed by the invention is different from a traditional curing agent in that: the curing agent comprises a polyurethane flexible chain segment synthesized from nonisocyanate, and is excellent in toughness and good in impact resistance; a molecule of the curing agent comprises the polyamine of a thiourea link, which exists in a balanced state with a ketone form and an enol form; the enol compound can rapidly react with an epoxy group so that the epoxy resin can be completely cured in winter and a construction period is effectively shortened.
Description
Technical field
The present invention relates to the epoxy curing agent field, specifically refer to a kind of high tenacity high reactivity epoxy curing agent and preparation method thereof.
Background technology
Product after Resins, epoxy and solidifying agent fully solidify has good physics, chemical property, electrical insulating property, low-shrinkage, resistant of high or low temperature, excellent in abrasion resistance etc.Thereby Resins, epoxy is widely used in building, mechanical, electric, aerospace field.General purpose epoxy resin mostly is bisphenol A-type, is subjected to the influence of the molecular structure of dihydroxyphenyl propane, and there is following defective in epoxy resin solidifying system:
1, epoxy resin cure product shock strength is not high, fragility is big,
When 2, used winter, the epoxy resin cure reaction not exclusively.
Therefore, Resins, epoxy toughness reinforcing and winter completion of cure all be the focus that this field is paid close attention to all the time.
General polymeric amide toughness is fine, but its viscosity is big, mix difficulty with Resins, epoxy, and winter, gel time is long, solidifies not exclusively, has limited Resins, epoxy use in the winter time.
Common modified amine, be that the Chinese invention patent of CN102604044A discloses a kind of thiocarbamide modification low temperature curing agent and preparation method thereof as publication number, its reactive behavior height, can solidify fully in the winter time, but and the cured article toughness of Resins, epoxy after solidifying fully is relatively poor, and has restricted the application of Resins, epoxy.
For these reasons, invent a kind of high tenacity high reactivity epoxy curing agent and become an important and urgent job.
Summary of the invention
The objective of the invention is to overcome shortcoming and the prejudice of above-mentioned prior art, a kind of high tenacity high reactivity epoxy curing agent and preparation method thereof is provided.
For achieving the above object, the designed a kind of high tenacity high reactivity epoxy curing agent of the present invention, its general structure is:
Wherein, R be C atomicity 2 ~ 6 alkyl or
Or
Or
(m=1.5 or 2.5 or 3.5);
R
1Be H or CH
3
R
2Alkyl for C atomicity 0 or 4 ~ 6;
n=1~2。
Further, described R be C atomicity 2 ~ 6 alkyl or
(m=1.5 or 2.5 or 3.5); Described R
1Be CH
3, R
2Alkyl for C atomicity 4 ~ 6.
Again further, described R is the alkyl of C atomicity 6, because hexanediamine toughness optimum in basic amine, and wide material sources, it is cheap; R
2Be the alkyl of C atomicity 4, this type of difunctionality compound has higher activity, when improving the product polymerization degree, need not harsh reaction conditions.
The present invention also provides a kind of preparation method of high tenacity high reactivity epoxy curing agent, may further comprise the steps:
1) according to ring Tan Suan Zhi ︰ polyamine mol ratio=0.1 ~ 1 ︰ 1, takes by weighing cyclic carbonate ester and polyamine, cyclic carbonate ester is dropped in the reactor that fills polyamine in batches, control temperature of reaction at 40 ~ 60 ℃, reaction times 0.5 ~ 2h;
2) take by weighing 0.5 ~ 2.5 times thiocarbamide of polyamine molar weight then, thiocarbamide is dropped in the reactor in batches, under 110 ~ 170 ℃ of temperature, react 2 ~ 5h;
3) after reaction is finished, make system temperature drop to 80 ℃, add step 2 again) in 0.5% ~ 5% promotor of product total mass, the back discharging that stirs is sealed up for safekeeping.
As preferred version, in the described step 1), cyclic carbonate ester is ethylene carbonate, 1,2-propylene glycol carbonic ether, 2, in 3-butyleneglycol carbonic ether and the dicyclo carbonic ether any one or a few.
As preferred version, in the described step 1), polyamine be in quadrol, diethylenetriamine, triethylene tetramine, tetraethylene pentamine, hexanediamine, m-xylene diamine and the isophorone diamine any one or a few.
As preferred version, in the described step 3), promotor be in 2,4,6-three (dimethylaminomethyl) phenol, benzyldimethylamine, trolamine or the 2-benzothiazolyl mercaptan any one or a few.
Beneficial effect of the present invention:
1, the solidifying agent of the present invention's preparation and traditional solidifying agent difference are, it contains the synthetic polyurethane flexible segment of non-isocyanate, has excellent toughness, good shock strength; And the solidifying agent intramolecularly contains the polyamines of thiocarbamide key, exists with keto-acid and enol form equilibrium state, and the quick and epoxy reaction of this enol form compound energy can make epoxy completion of cure in the winter time, effectively the reduction of erection time.
2, the key technical indexes of the high tenacity high reactivity epoxy curing agent of the present invention's preparation and pour mass thereof is as follows:
Solidifying agent:
(1) amine value: 200 ~ 800mgKOH/g;
(2) viscosity: 1000 ~ 20000mPa/s;
(3) fugitive constituent: 0 ~ 8%
(4) gel time: under 25 ℃ ± 2 ℃ conditions ,≤10min; Under-5 ℃ of conditions ,≤60min
The pour mass performance:
Shock strength: 〉=10.0KJ/m2.
Test result contrasts as following table:
All kinds of index contrasts of table one solidifying agent and pour mass
As can be known from the above table, solidifying agent of the present invention has the activity of thiocarbamide modification and the toughness of polymeric amide, and over-all properties is good, modest viscosity, and use suitable winter.
Embodiment
The present invention is described in further detail below in conjunction with the drawings and specific embodiments, so that those skilled in the art understand.
Embodiment 1
High tenacity high reactivity epoxy curing agent synthesis step:
1) take by weighing ethylene carbonate and the 1mol tetraethylene pentamine of 0.5mol, ethylene carbonate is dropped in the reactor that fills tetraethylene pentamine in batches, the control temperature is at 50 ℃ ± 2 ℃ reaction 2h;
2) take by weighing the thiocarbamide of 0.5mol then, drop in the reactor in batches, adopt the oil bath heat temperature raising, it is fully dissolved, at 170 ℃ ± 2 ℃ reaction 2h down;
3) after reaction is finished, system is cooled to 80 ℃, drop into step 2 again) the product total mass 1% 2,4,6-three (dimethylaminomethyl) phenol, the back discharging that stirs is sealed up for safekeeping.
Embodiment 2
High tenacity high reactivity epoxy curing agent synthesis step:
1) take by weighing 2 of 0.1mol, the quadrol of 3-butyleneglycol carbonic ether and 1mol drops into 2,3-butyleneglycol carbonic ether in the reactor that fills quadrol in batches, and the control temperature is at 60 ± 2 ℃ of reaction 0.5h;
2) take by weighing the thiocarbamide of 0.6mol then, drop in the reactor in batches, adopt the oil bath heat temperature raising, it is fully dissolved, at 110 ℃ ± 2 ℃ reaction 5h;
3) after reaction is finished, system is cooled to 80 ℃, drop into step 2 again) the 2-benzothiazolyl mercaptan of product total mass 5%, the back discharging that stirs is sealed up for safekeeping.
Embodiment 3
High tenacity high reactivity epoxy curing agent synthesis step:
1) take by weighing 1 of 1mol, 2-propylene glycol carbonic ether and 1mol hexanediamine drop into 1,2-propylene glycol carbonic ether in the reactor that fills hexanediamine in batches, and the control temperature is at 40 ± 2 ℃ of reaction 1h;
2) take by weighing the thiocarbamide of 2.5mol then, drop in the reactor in batches, adopt the oil bath heat temperature raising, it is fully dissolved, at 150 ℃ ± 2 ℃ reaction 5h;
3) after reaction is finished, system is cooled to 80 ℃, drop into step 2 again) the benzyldimethylamine of product total mass 0.5%, drop in the reactor, the back discharging that stirs is sealed up for safekeeping.
Embodiment 4
High tenacity high reactivity epoxy curing agent synthesis step:
1) takes by weighing (ethylene carbonate and 1 of 0.3mol, 2-propylene glycol carbonic ether) and 1mol (quadrol, diethylenetriamine), ethylene carbonate and 1,2-propylene glycol carbonic ether are dropped in the reactor that fills quadrol and diethylenetriamine in batches, and the control temperature is at 45 ± 2 ℃ of reaction 2h;
2) take by weighing the thiocarbamide of 2.5mol then, drop in the reactor in batches, adopt the oil bath heat temperature raising, it is fully dissolved, at 140 ℃ ± 2 ℃ reaction 5h;
3) after reaction is finished, system is cooled to 80 ℃, drop into step 2 again) (2,4,6-three (dimethylaminomethyl) phenol and the benzyldimethylamine) of product total mass 2.5%, drop in the reactor, the back discharging that stirs is sealed up for safekeeping.
Embodiment 5
High tenacity high reactivity epoxy curing agent synthesis step:
1) take by weighing the dicyclo carbonic ether of 0.3mol and the isophorone diamine of 1mol, the dicyclo carbonic ether is dropped in the reactor that fills isophorone diamine in batches, the control temperature is at 40 ± 2 ℃ of reaction 1h;
2) take by weighing the thiocarbamide of 2.5mol then, drop in the reactor in batches, adopt the oil bath heat temperature raising, it is fully dissolved, at 135 ℃ ± 2 ℃ reaction 5h;
3) after reaction is finished, system is cooled to 80 ℃, drop into step 2 again) the trolamine of product total mass 3%, drop in the reactor, the back discharging that stirs is sealed up for safekeeping.
Embodiment 6
High tenacity high reactivity epoxy curing agent synthesis step:
1) takes by weighing (the dicyclo carbonic ether and 2 of 0.3mol, 3-butyleneglycol carbonic ether) and 1mol (quadrol, diethylenetriamine and isophorone diamine), with (dicyclo carbonic ether and 2,3-butyleneglycol carbonic ether) input fills in the reactor of (quadrol, diethylenetriamine and isophorone diamine) in batches, the control temperature is reacted 1h at 40 ± 2 ℃;
2) take by weighing the thiocarbamide of 2.5mol then, go in the reactor in batches, adopt the oil bath heat temperature raising, it is fully dissolved, at 135 ℃ ± 2 ℃ reaction 5h;
3) after reaction is finished, system is cooled to 80 ℃, drop into step 2 again) the trolamine of product total mass 3%, drop in the reactor, the back discharging that stirs is sealed up for safekeeping.
Embodiment 7
High tenacity high reactivity epoxy curing agent synthesis step:
1) takes by weighing (ethylene carbonate, 1 of 0.6mol, 2-propylene glycol carbonic ether, 2,3-butyleneglycol carbonic ether and dicyclo carbonic ether) and (triethylene tetramine, tetraethylene pentamine, hexanediamine and the m-xylene diamine) of 1mol, with ethylene carbonate, 1,2-propylene glycol carbonic ether, 2,3-butyleneglycol carbonic ether and dicyclo carbonic ether) drop in batches and fill in the reactor of (triethylene tetramine, tetraethylene pentamine, hexanediamine, m-xylene diamine), the control temperature is at 60 ± 2 ℃, reaction 0.5h;
2) take by weighing the thiocarbamide of 2.0mol then, go in the reactor in batches, adopt the oil bath heat temperature raising, it is fully dissolved, at 145 ℃ ± 2 ℃ reaction 2h;
3) after reaction is finished, system is cooled to 80 ℃, drop into step 2 again) product total mass 3% (2,4,6-three (dimethylaminomethyl) phenol, benzyldimethylamine, trolamine and 2-benzothiazolyl mercaptan), drop in the reactor, the back discharging that stirs is sealed up for safekeeping.
Embodiment 8
High tenacity high reactivity epoxy curing agent synthesis step:
1) take by weighing the dicyclo carbonic ether of 0.2mol and the hexanediamine of 1mol, with the dicyclo carbonic ether) drop in batches and fill in the reactor of hexanediamine, the control temperature is at 60 ± 2 ℃, reaction 2h;
2) take by weighing the thiocarbamide of 2.0mol then, go in the reactor in batches, adopt the oil bath heat temperature raising, it is fully dissolved, at 145 ℃ ± 2 ℃ reaction 2h;
3) after reaction is finished, system is cooled to 80 ℃, drop into step 2 again) product total mass 2% 2,4,6-three (dimethylaminomethyl) phenol drops in the reactor, the back discharging that stirs is sealed up for safekeeping.
Above embodiment agents useful for same is chemical pure
High tenacity high reactivity epoxy curing agent and all kinds of indexs of pour mass to embodiment 1 ~ 8 preparation detect:
Concrete testing standard or method are as follows:
The amine value: hydrochloric acid-Ethanol Method is measured.Reference: the high cutting edge of a knife or a sword thermosetting resin 2006,21 of discussion Sun Man spirit Zheng of amine curing agent amine values determination method, (2).
Viscosity: press GB/T 7193-2008 4.1, adopt NJ-7 type rotary viscosity design determining
Fugitive constituent: press GB/T 7193-2008 4.3, adopt the constant temperature vacuum drying oven to measure.
Gel time: press GB/T 12954-1991 5.6, measure gel time.
Resin-cast body performance:
Shock strength: press GB/T 2567-2008 5.1, the test shock strength.
Each embodiment data contrast of table two
Other unspecified part is prior art.Although above-described embodiment has been made detailed description to the present invention; but it only is the present invention's part embodiment; rather than whole embodiment, people can also obtain other embodiment according to present embodiment under without creative prerequisite, and these embodiment belong to protection domain of the present invention.
Claims (8)
1. high tenacity high reactivity epoxy curing agent, its general structure is:
Wherein, R be C atomicity 2 ~ 6 alkyl or
Or
Or
(m=1.5 or 2.5 or 3.5);
R
1Be H or CH
3
R
2Alkyl for C atomicity 0 or 4 ~ 6;
n=1~2。
2. high tenacity high reactivity epoxy curing agent according to claim 1 is characterized in that: described R be C atomicity 2 ~ 6 alkyl or
(m=1.5 or 2.5 or 3.5); Described R
1Be CH
3R
2Alkyl for C atomicity 4 ~ 6.
3. high tenacity high reactivity epoxy curing agent according to claim 2, it is characterized in that: described R is the alkyl of C atomicity 6; R
2Alkyl for C atomicity 4.
4. preparation method according to the described high tenacity high reactivity of claim 1 epoxy curing agent is characterized in that: may further comprise the steps:
1) according to ring Tan Suan Zhi ︰ polyamine mol ratio=0.1 ~ 1 ︰ 1, takes by weighing cyclic carbonate ester and polyamine, cyclic carbonate ester is dropped in the reactor that fills polyamine in batches, control temperature of reaction at 40 ~ 60 ℃, reaction times 0.5 ~ 2h;
2) take by weighing 0.5 ~ 2.5 times thiocarbamide of polyamine molar weight then, thiocarbamide is dropped in the reactor in batches, under 110 ~ 170 ℃ of temperature, react 2 ~ 5h;
3) after reaction is finished, make system temperature drop to 80 ℃, add step 2 again) in 0.5% ~ 5% promotor of product total mass, the back discharging that stirs is sealed up for safekeeping.
5. the preparation method of high tenacity high reactivity epoxy curing agent according to claim 4, it is characterized in that: in the described step 1), cyclic carbonate ester is ethylene carbonate, 1,2-propylene glycol carbonic ether, 2, in 3-butyleneglycol carbonic ether and the dicyclo carbonic ether any one or a few.
6. according to the preparation method of claim 4 or 5 described high tenacity high reactivity epoxy curing agents, it is characterized in that: in the described step 1), polyamine be in quadrol, diethylenetriamine, triethylene tetramine, tetraethylene pentamine, hexanediamine, m-xylene diamine and the isophorone diamine any one or a few.
7. according to the preparation method of claim 4 or 5 described high tenacity high reactivity epoxy curing agents, it is characterized in that: in the described step 3), promotor is 2, in 4,6-three (dimethylaminomethyl) phenol, benzyldimethylamine, trolamine or the 2-benzothiazolyl mercaptan any one or a few.
8. the preparation method of high tenacity high reactivity epoxy curing agent according to claim 6, it is characterized in that: in the described step 3), promotor is 2, in 4,6-three (dimethylaminomethyl) phenol, benzyldimethylamine, trolamine or the 2-benzothiazolyl mercaptan any one or a few.
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Cited By (12)
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| CN104559681A (en) * | 2013-10-23 | 2015-04-29 | 财团法人工业技术研究院 | Coating composition and coating prepared therefrom |
| CN104744670A (en) * | 2015-04-14 | 2015-07-01 | 湖南大学 | Epoxy acrylate prepolymer and application thereof |
| CN106146802A (en) * | 2016-08-19 | 2016-11-23 | 武汉工程大学 | Compound 2 ghiourea group 3,5 2 (methyl mercapto) 4 amino toluene is in the application of epoxy-resin systems |
| CN106316907A (en) * | 2016-08-19 | 2017-01-11 | 武汉工程大学 | Compound 2-thiourea-3,5-bis(methylthio)-4-amino toluene and synthetic method thereof |
| WO2018108890A1 (en) * | 2016-12-15 | 2018-06-21 | Akzo Nobel Chemicals International B.V. | Process for manufacturing ethylene amines |
| CN108713012A (en) * | 2016-02-12 | 2018-10-26 | 阿克苏诺贝尔化学品国际有限公司 | The method for preparing advanced ethylene amines and ethyleneamine derivatives |
| CN109401534A (en) * | 2018-09-20 | 2019-03-01 | 中北大学 | The preparation method of the corrosion-resistant epoxy paint of non-isocyanate polyurea type epoxy hardener |
| CN109438675A (en) * | 2018-10-15 | 2019-03-08 | 广州市白云化工实业有限公司 | Modified epoxy resin curing agent and preparation method thereof |
| CN111909360A (en) * | 2020-08-11 | 2020-11-10 | 深圳飞扬兴业科技有限公司 | High-elasticity epoxy curing agent, preparation method and epoxy resin |
| US10995058B2 (en) | 2016-12-15 | 2021-05-04 | Nouryon Chemicals International B.V. | Process for manufacturing hydroxyethyl ethylene amines |
| CN112940349A (en) * | 2019-12-10 | 2021-06-11 | 中蓝晨光化工研究设计院有限公司 | Combined toughening agent containing five-membered cyclic carbonate group, preparation method and application of combined toughening agent in epoxy toughening |
| GB2624050A (en) * | 2022-10-30 | 2024-05-08 | Spider Resin Ltd | Method of Manufacturing Moisture-Cure Resin Composition |
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| CN104559681A (en) * | 2013-10-23 | 2015-04-29 | 财团法人工业技术研究院 | Coating composition and coating prepared therefrom |
| CN104559681B (en) * | 2013-10-23 | 2018-05-15 | 财团法人工业技术研究院 | Coating composition and coating prepared therefrom |
| CN104744670A (en) * | 2015-04-14 | 2015-07-01 | 湖南大学 | Epoxy acrylate prepolymer and application thereof |
| CN104744670B (en) * | 2015-04-14 | 2017-03-01 | 湖南大学 | A kind of epoxy acrylic ester prepolymer and its application |
| CN108713012A (en) * | 2016-02-12 | 2018-10-26 | 阿克苏诺贝尔化学品国际有限公司 | The method for preparing advanced ethylene amines and ethyleneamine derivatives |
| CN108713012B (en) * | 2016-02-12 | 2021-07-02 | 阿克苏诺贝尔化学品国际有限公司 | Process for preparing higher ethyleneamines and ethyleneamine derivatives |
| CN106146802B (en) * | 2016-08-19 | 2019-05-03 | 武汉工程大学 | Application of two (the methyl mercapto) -4- amino toluene of compound 2- ghiourea group -3,5- in epoxy-resin systems |
| CN106146802A (en) * | 2016-08-19 | 2016-11-23 | 武汉工程大学 | Compound 2 ghiourea group 3,5 2 (methyl mercapto) 4 amino toluene is in the application of epoxy-resin systems |
| CN106316907A (en) * | 2016-08-19 | 2017-01-11 | 武汉工程大学 | Compound 2-thiourea-3,5-bis(methylthio)-4-amino toluene and synthetic method thereof |
| CN110072838A (en) * | 2016-12-15 | 2019-07-30 | 阿克苏诺贝尔化学品国际有限公司 | The method for preparing ethylene amines |
| US20190308930A1 (en) * | 2016-12-15 | 2019-10-10 | Akzo Nobel Chemicals International B.V. | Process for manufacturing ethylene amines |
| CN110072838B (en) * | 2016-12-15 | 2022-04-15 | 阿克苏诺贝尔化学品国际有限公司 | Process for preparing ethyleneamines |
| US10975017B2 (en) | 2016-12-15 | 2021-04-13 | Nouryon Chemicals International B.V. | Process for manufacturing ethylene amines |
| US10995058B2 (en) | 2016-12-15 | 2021-05-04 | Nouryon Chemicals International B.V. | Process for manufacturing hydroxyethyl ethylene amines |
| WO2018108890A1 (en) * | 2016-12-15 | 2018-06-21 | Akzo Nobel Chemicals International B.V. | Process for manufacturing ethylene amines |
| CN109401534A (en) * | 2018-09-20 | 2019-03-01 | 中北大学 | The preparation method of the corrosion-resistant epoxy paint of non-isocyanate polyurea type epoxy hardener |
| CN109438675A (en) * | 2018-10-15 | 2019-03-08 | 广州市白云化工实业有限公司 | Modified epoxy resin curing agent and preparation method thereof |
| CN109438675B (en) * | 2018-10-15 | 2021-06-15 | 广州市白云化工实业有限公司 | Modified epoxy resin curing agent and preparation method thereof |
| CN112940349A (en) * | 2019-12-10 | 2021-06-11 | 中蓝晨光化工研究设计院有限公司 | Combined toughening agent containing five-membered cyclic carbonate group, preparation method and application of combined toughening agent in epoxy toughening |
| CN112940349B (en) * | 2019-12-10 | 2022-08-12 | 中蓝晨光化工研究设计院有限公司 | Combined toughening agent containing five-membered cyclic carbonate group, preparation method and application of combined toughening agent in epoxy toughening |
| CN111909360A (en) * | 2020-08-11 | 2020-11-10 | 深圳飞扬兴业科技有限公司 | High-elasticity epoxy curing agent, preparation method and epoxy resin |
| GB2624050A (en) * | 2022-10-30 | 2024-05-08 | Spider Resin Ltd | Method of Manufacturing Moisture-Cure Resin Composition |
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