CN102391476A - Polythiol epoxy resin curing agent and preparation method thereof - Google Patents
Polythiol epoxy resin curing agent and preparation method thereof Download PDFInfo
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- CN102391476A CN102391476A CN201110195818XA CN201110195818A CN102391476A CN 102391476 A CN102391476 A CN 102391476A CN 201110195818X A CN201110195818X A CN 201110195818XA CN 201110195818 A CN201110195818 A CN 201110195818A CN 102391476 A CN102391476 A CN 102391476A
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Abstract
The invention relates to a curing agent, particularly a polythiol epoxy resin curing agent and a preparation method thereof. The polythiol epoxy resin curing agent uses cheap and accessible raw materials to greatly lower the cost of the polythiol epoxy resin fast curing agent. The preparation method comprises the following steps: after esterifying sorbitol, thioglycollic acid, p-toluenesulfonic acid and methylbenzene, distilling out the liquid under reduced pressure at uniform speed by controlling the temperature and vacuum degree until no liquid is distilled out, and adding epoxy resin to carry out chain extending reaction, thereby obtaining the polythiol epoxy resin curing agent. The polythiol epoxy resin curing agent is a colorless or light yellow transparent liquid poly-sulfhydryl epoxy grafted compound with certain viscosity, the pH value is 2-4, and the density is 1.2-1.3 g/cm<3>.
Description
Technical field
The present invention relates to a kind of solidifying agent, especially relate to a kind of polythiol epoxy curing agent and preparation method thereof.
Background technology
Epoxyn has good physical and chemical performance, and it has excellent bonding strength to the surface of metal and non-metallic material, and dielectric properties are good; The set shrinking percentage is little, the product size good stability, and hardness is high; Snappiness is better, and processing technology is good, to alkali and most of solvent-stable; Thereby be widely used in national defence, national economy all departments, in cast, dipping, lamination material, caking agent, coating etc., be widely used.Epoxy resin solidifying agent commonly used mainly contains amine, anhydrides, imidazoles etc.
Polythiol solidifying agent end be thiol group (SH); Activity is very poor when using separately; When room temperature, react extremely slow, almost can not carry out, in the presence of suitable promotor, can form the mercaptan ion; Curing reaction carries out with the speed of several times polyamine, and these characteristics more can show when low-temperature curing.When tertiary amine existed, thiol group at first generated the mercaptan ion with reactive tertiary amine, and this ion makes curable epoxide with epoxy reaction again.Traditional epoxy hardener like low molecular polyamides, needs 24h just can make the epoxy completely solidified, and only needs 5min with the polythiol system under the normal temperature, so polythiol has great advantage in fast repair sheets and winter job occasion, and other solidifying agent can't substitute.The thio-alcohol solidifying agent is also having very big using value because the existence of sulfur-bearing soft segment and higher specific refractory power are arranged aspect toughened resin and the transparent resin.But because thiol-cured dose manufacturing requirements is higher; At present; Domestic production is few; Be generally imported product, use comparatively general like trades mark such as the EpomateQX-10 of the trade mark such as the Capcure3-800 of the U.S., Capcure3830-81, Capcure LOF, Capcure 40 sec HV, Capcure WR-6 and Japan, EpomateQX-11, EpomateQX-40, MP-2290, EH-316.
The preparation method of polythiol mainly contains following several kinds both at home and abroad:
A. be initiator with the tetramethylolmethane, cause the propylene oxide polymerization, use allyl capped, again and H
2The S reaction obtains polythiol (U.S. Pat 4092293).This preparing method's shortcoming is that reactions step is lengthy and tedious, and condition is harsh, and cost of material is more expensive, and cost is high.
B. be that raw material reaction generates multi-thiol with tetramethylolmethane and β-Qiu Jibingsuan, again with the epoxy resin chain extension obtain polythiol (Kang Fuchun, Zhang Hongwei. thiol-cured dose synthetic and application [J]. thermosetting resin, 2006,21 (3): 15-17).This preparing method's reaction conditions is simple, but raw material tetramethylolmethane and β-Qiu Jibingsuan price are higher.
C. in the presence of Lewis acid catalyst, use low molecular mass polyethers and epoxy chloropropane generation addition reaction to form the midbody of end group as chlorine; At last again with NaHS reaction generate polythiol (Wang Anting. synthetic [J] of polythiol quick curing agent. thermosetting resin; 2009,21 (1): 17-19).This preparing method's shortcoming is that the purification step of product is numerous and diverse.
Summary of the invention
The object of the invention aims to provide and a kind ofly utilizes that raw material is cheap and easy to get, the polythiol epoxy curing agent of the cost that can reduce the polythiol fast epoxy resin curing agent significantly and preparation method thereof.
Concrete steps of the present invention are following:
After sorbyl alcohol, Thiovanic acid, tosic acid and toluene carried out esterification; Underpressure distillation; Controlled temperature and vacuum tightness at the uniform velocity distillate till absence of liq distillates liquid, add epoxy resin and carry out chain extending reaction, obtain the polythiol epoxy curing agent.
The mass ratio of said sorbyl alcohol, Thiovanic acid, tosic acid, toluene and epoxy resin can be sorbyl alcohol 12～18, Thiovanic acid 50～60, tosic acid 0.001～0.003, toluene 25～35, epoxy resin 7～25; Be preferably sorbyl alcohol 15.1, Thiovanic acid 54.2, tosic acid 0.002, toluene 30.6, epoxy resin 7～25; The temperature of said esterification can be 80～120 ℃, and the time of esterification can be 2～5h; The recyclable utilization of the toluene that said underpressure distillation obtains is in order to avoid contaminate environment; Said epoxy resin is optional to be 638,6101 or 618 etc. epoxy resin from model; The temperature of said chain extending reaction can be 80～120 ℃, and the time of chain extending reaction can be 1～4h.
The polythiol epoxy curing agent of gained is colourless or faint yellow and has many sulfydryls of transparent liquid epoxy graft compound of certain viscosity, and its pH value is 2～4, and density is 1.2～1.3g/cm
3
Compare with the preparation method of existing polythiol epoxy curing agent, the present invention has following outstanding advantage:
1) the used sorbyl alcohol of the present invention has 6 hydroxyls; Can generate the polythiol of 5～6 arms with the Thiovanic acid reaction; Each molecule has 8～12 thiol groups behind the epoxy resin chain extension; Good with the consistency of epoxy resin, the epoxy resin after the curing is strong and tough, has overcome the insufficient shortcoming of toughness behind traditional solidifying agent cured epoxy resin.
2) process using of the present invention is directly carried out underpressure distillation to esterification products under acidic conditions, does not carry out common neutralization and washing, has not only simplified preparation process, and has obviously improved esterification yied.
3) the raw materials for production cost is low, and the price of the used sorbyl alcohol of the present invention, Thiovanic acid is lower than traditional mode of production raw material tetramethylolmethane, thiohydracrylic acid.Like sorbyl alcohol about 3800 yuan per ton, about 9000 yuan of tetramethylolmethane; About 35000 yuan per ton of Thiovanic acid, about 50000 yuan per ton of thiohydracrylic acid.Raw materials cost reduces about 30%.
Embodiment
Embodiment 1
Add 30.6 parts of 15.1 parts of sorbyl alcohols, 0.002 part of tosic acid, 54.2 parts of Thiovanic acids and toluene in the 250ml three-necked bottle that prolong and whisking appliance are housed successively.Behind the back flow reaction 4h, carry out underpressure distillation.Add (638) 9.1 parts of epoxy resin, 100 ℃ are reacted 1h down.
Embodiment 2
Add 30.6 parts of 15.1 parts of sorbyl alcohols, 0.002 part of tosic acid, 54.2 parts of Thiovanic acids and toluene in the 250ml three-necked bottle that prolong and whisking appliance are housed successively.Behind the back flow reaction 4h, carry out underpressure distillation.Add (6101) 12.1 parts of epoxy resin, 100 ℃ are reacted 1.5h down.
Embodiment 3
Add 30.6 parts of 15.1 parts of sorbyl alcohols, 0.002 part of tosic acid, 54.2 parts of Thiovanic acids and toluene in the 250ml three-necked bottle that prolong and whisking appliance are housed successively.Behind the back flow reaction 4h, carry out underpressure distillation.Add (618) 18.1 parts of epoxy resin, 100 ℃ are reacted 2h down.
Embodiment 4
Add 32.9 parts of 15.1 parts of sorbyl alcohols, 0.002 part of tosic acid, 54.2 parts of Thiovanic acids and YLENE in the 250ml three-necked bottle that prolong and whisking appliance are housed successively.Behind the back flow reaction 4h, carry out underpressure distillation.Add (638) 9.1 parts of epoxy resin, 100 ℃ are reacted 1h down.
Embodiment 5
Add 32.9 parts of 15.1 parts of sorbyl alcohols, 0.002 part of tosic acid, 54.2 parts of Thiovanic acids and YLENE in the 250ml three-necked bottle that prolong and whisking appliance are housed successively.Behind the back flow reaction 4h, carry out underpressure distillation.Add (6101) 12.1 parts of epoxy resin, 100 ℃ are reacted 1.5h down.
Embodiment 6
Add 32.9 parts of 15.1 parts of sorbyl alcohols, 0.002 part of tosic acid, 54.2 parts of Thiovanic acids and YLENE in the 250ml three-necked bottle that prolong and whisking appliance are housed successively.Behind the back flow reaction 4h, carry out underpressure distillation.Add (618) 18.1 parts of epoxy resin, 100 ℃ are reacted 2h down.
Claims (6)
1. the preparation method of a polythiol epoxy curing agent is characterized in that its concrete steps are following:
After sorbyl alcohol, Thiovanic acid, tosic acid and toluene carried out esterification; Underpressure distillation; Controlled temperature and vacuum tightness at the uniform velocity distillate till absence of liq distillates liquid, add epoxy resin and carry out chain extending reaction, obtain the polythiol epoxy curing agent.
2. the preparation method of a kind of polythiol epoxy curing agent as claimed in claim 1; The mass ratio that it is characterized in that said sorbyl alcohol, Thiovanic acid, tosic acid, toluene and epoxy resin is a sorbyl alcohol 12～18; Thiovanic acid 50～60; Tosic acid 0.001～0.003, toluene 25～35, epoxy resin 7～25.
3. the preparation method of a kind of polythiol epoxy curing agent as claimed in claim 2; The mass ratio that it is characterized in that said sorbyl alcohol, Thiovanic acid, tosic acid, toluene and epoxy resin is a sorbyl alcohol 15.1; Thiovanic acid 54.2; Tosic acid 0.002, toluene 30.6, epoxy resin 7～25.
4. the preparation method of a kind of polythiol epoxy curing agent as claimed in claim 1; The mass ratio that it is characterized in that said sorbyl alcohol, Thiovanic acid, tosic acid, toluene and epoxy resin is that the temperature of said esterification is 80～120 ℃, and the time of esterification is 2～5h.
5. the preparation method of a kind of polythiol epoxy curing agent as claimed in claim 1, the mass ratio that it is characterized in that said sorbyl alcohol, Thiovanic acid, tosic acid, toluene and epoxy resin is that said epoxy resin is selected from 638 epoxy resin, 6101 epoxy resin or 618 epoxy resin.
6. the preparation method of a kind of polythiol epoxy curing agent as claimed in claim 1, the temperature that it is characterized in that said chain extending reaction is 80～120 ℃, the time of chain extending reaction is 1～4h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110195818 CN102391476B (en) | 2011-07-12 | 2011-07-12 | Polythiol epoxy resin curing agent and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110195818 CN102391476B (en) | 2011-07-12 | 2011-07-12 | Polythiol epoxy resin curing agent and preparation method thereof |
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| CN102391476A true CN102391476A (en) | 2012-03-28 |
| CN102391476B CN102391476B (en) | 2013-01-02 |
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| CN 201110195818 Expired - Fee Related CN102391476B (en) | 2011-07-12 | 2011-07-12 | Polythiol epoxy resin curing agent and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111019093A (en) * | 2019-12-10 | 2020-04-17 | 武汉市科达云石护理材料有限公司 | Room-temperature rapid epoxy curing agent and application thereof in preparation of epoxy dry-hanging adhesive |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003049092A (en) * | 2001-08-03 | 2003-02-21 | Hitachi Chem Co Ltd | Filler, resin composition, and application thereof |
| CN1914279A (en) * | 2003-12-19 | 2007-02-14 | 日本电气株式会社 | Flame resistant thermoplastic resin composition |
-
2011
- 2011-07-12 CN CN 201110195818 patent/CN102391476B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003049092A (en) * | 2001-08-03 | 2003-02-21 | Hitachi Chem Co Ltd | Filler, resin composition, and application thereof |
| CN1914279A (en) * | 2003-12-19 | 2007-02-14 | 日本电气株式会社 | Flame resistant thermoplastic resin composition |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111019093A (en) * | 2019-12-10 | 2020-04-17 | 武汉市科达云石护理材料有限公司 | Room-temperature rapid epoxy curing agent and application thereof in preparation of epoxy dry-hanging adhesive |
| CN111019093B (en) * | 2019-12-10 | 2022-05-03 | 武汉市科达云石护理材料有限公司 | Room-temperature rapid epoxy curing agent and application thereof in preparation of epoxy dry-hanging adhesive |
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| CN102391476B (en) | 2013-01-02 |
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