CN104447446A - Method for preparing trimethylolpropane tris(3-mercaptopropionate) - Google Patents
Method for preparing trimethylolpropane tris(3-mercaptopropionate) Download PDFInfo
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- CN104447446A CN104447446A CN201410626772.6A CN201410626772A CN104447446A CN 104447446 A CN104447446 A CN 104447446A CN 201410626772 A CN201410626772 A CN 201410626772A CN 104447446 A CN104447446 A CN 104447446A
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- trimethylolpropane tris
- acid ester
- mercaptopropionic acid
- trimethylolpropane
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Abstract
The invention relates to a method for preparing trimethylolpropane tris(3-mercaptopropionate). The method is characterized by comprising the following steps: sequentially adding cyclohexane, trimethylolpropane, 3-mercaptopropionic acid and p-toluenesulfonic acid into a reaction container, and reacting in an oil bath; washing the product by adopting heating reflux and cooling; drying to obtain a crude product; and finally, performing reduced pressure distillation and filtration, thereby obtaining trimethylolpropane tris(3-mercaptopropionate). According to the product prepared by the method, the light curing adhesive requirement in the optical transparent material process can be effectively met. Moreover, according to effective filtration, the product has excellent colorless, clarified and transparent characteristics, the transparency and refractive index of resin are improved, and the impact resistance, dyeing property and machinability of the resin are improved.
Description
Technical field
The present invention relates to a kind of preparation method of industrial organic intermediate, particularly relate to the preparation method of a kind of trimethylolpropane tris (3-mercaptopropionic acid ester).
Background technology
Conventional trimethylolpropane tris (3-mercaptopropionic acid ester), can be used as linking agent, polymeric modifier and light curing agent, is widely used in photo-cured coating, sensitive materials, printed-wiring board (PWB) or other functional materials aspect.This product is applied in light solidifying coating system, can improve the performances such as the sticking power of coating, hardness, toughness, improves curing performance and the apparent property of coating.Meanwhile, this product can be used as photocuring comonomer or the light curing agent of vinyl-based, the polymkeric substance such as (methyl) acrylic acid or the like, how different (sulphur) cyanate, prepares optically transparent material.
Summary of the invention
Object of the present invention is exactly to solve the above-mentioned problems in the prior art, provides the preparation method of a kind of trimethylolpropane tris (3-mercaptopropionic acid ester).
Object of the present invention is achieved through the following technical solutions:
The preparation method of trimethylolpropane tris (3-mercaptopropionic acid ester), it comprises the following steps: step 1., in reaction vessel, add hexanaphthene, TriMethylolPropane(TMP), 3-thiohydracrylic acid, tosic acid successively, carry out oil bath, described oil bath temperature is 75 to 85 DEG C.2., reflux, is stabilized in 78 to 79 DEG C by interior temperature to step, reacts 1.5 to 2.5 hours.3. step, cools, and is washed by cooled product, and carries out extracting rear secondary washing and clarify to organic phase.4. step, after carrying out drying, obtains crude product after carrying out spin concentration.5. step, after crude product is carried out underpressure distillation, by final filtration, obtains achromaticity and clarification transparent liquid.
The preparation method of above-mentioned trimethylolpropane tris (3-mercaptopropionic acid ester), wherein: the content that the content of described step 1. cyclohexane is 450-550ml, the content of TriMethylolPropane(TMP) is 65-70g, 3-thiohydracrylic acid is 170-180g, the content of tosic acid is 8-15g.
Further, the preparation method of above-mentioned trimethylolpropane tris (3-mercaptopropionic acid ester), wherein: the content that the content of described step 1. cyclohexane is 500ml, the content of TriMethylolPropane(TMP) is 67.1g, 3-thiohydracrylic acid is 175g, the content of tosic acid is 10g.
Further, the preparation method of above-mentioned trimethylolpropane tris (3-mercaptopropionic acid ester), wherein: described step 1. middle nitrogen or the argon gas of adopting is protected.
Further, the preparation method of above-mentioned trimethylolpropane tris (3-mercaptopropionic acid ester), wherein: described step 1. in, oil bath temperature is 80 DEG C.
Further, the preparation method of above-mentioned trimethylolpropane tris (3-mercaptopropionic acid ester), wherein: described step 2. in, adopt magnetic force heating stirrer to carry out reflux, the reaction times is 2 hours.
Further, the preparation method of above-mentioned trimethylolpropane tris (3-mercaptopropionic acid ester), wherein: the step 3. middle sodium bicarbonate of 3 × 200ml that adopts is washed, described extraction is undertaken by the methylene dichloride of 3 × 200ml, and described secondary washing is undertaken by the organic phase saturated sodium-chloride of 2 × 200ml.
Further, the preparation method of above-mentioned trimethylolpropane tris (3-mercaptopropionic acid ester), wherein: described step 4. in, carry out drying (half an hour) by anhydrous magnesium sulfate or sodium sulfate (100g), under the state that temperature is less than or equal to 30 DEG C, carry out spin concentration.
Further, the preparation method of above-mentioned trimethylolpropane tris (3-mercaptopropionic acid ester), wherein: described step 5. in, crude product carries out the underpressure distillation of 1 hour by a definite date in 40 DEG C of situations by oil pump, and by organic membrane filtration of 0.45um.
Again further, the preparation method of above-mentioned trimethylolpropane tris (3-mercaptopropionic acid ester), wherein: described reaction vessel is 1L there-necked flask, described 1L there-necked flask is provided with water trap.
The advantage of technical solution of the present invention is mainly reflected in: effectively can meet the light curing agent demand in optically transparent material process.Further, by effective filtration, have preferably achromaticity and clarification transparent special, improve transparency and the specific refractory power of resin, improve the impact resistance of resin, dyeability and processibility etc.
Embodiment
The preparation method of trimethylolpropane tris (3-mercaptopropionic acid ester), it comprises the following steps:
First, the 1L there-necked flask of employing, as reaction vessel, this there-necked flask is provided with water trap, adds hexanaphthene, TriMethylolPropane(TMP), 3-thiohydracrylic acid, tosic acid in reaction vessel successively, carries out the oil bath that temperature is 75 to 85 DEG C.During this period, in order to have preferably reaction effect, the content that the content of cyclohexane is 450-550ml, the content of TriMethylolPropane(TMP) is 65-70g, 3-thiohydracrylic acid is 170-180g, the content of tosic acid is 8-15g.From the present invention one preferred embodiment, following consumption can be adopted: the content that the content of hexanaphthene is 500ml, the content of TriMethylolPropane(TMP) is 67.1g, 3-thiohydracrylic acid is 175g, the content of tosic acid is 10g.Meanwhile, in order to effectively react protection, nitrogen or argon gas can be used to participate in carrying out.Further, oil bath temperature is controlled at 80 DEG C as good.Its reason is, the boiling point of hexanaphthene is with regard to about 80 DEG C, and 80 DEG C just enough make hexanaphthene volatilization take away the water generated in reaction, if temperature is too high, product can be caused on the contrary to turn yellow.
Afterwards, adopt magnetic force heating stirrer to carry out reflux, interior temperature is stabilized in 78 to 79 DEG C, reacts 1.5 to 2.5 hours.By repeatedly contrasting discovery, be preferred to adopt 2 hours.
Subsequently, carry out suitable cooling, adopt the sodium bicarbonate of 3 × 200ml to wash cooled product.Methylene dichloride by 3 × 200ml after washing extracts, and is again clarified to organic phase by the organic phase saturated sodium-chloride secondary washing of 2 × 200ml afterwards.
Then, drying (dry half an hour) is carried out by anhydrous magnesium sulfate or sodium sulfate.After to be dried, under the state that temperature is less than or equal to 30 DEG C, carry out spin concentration, obtain crude product.Thus, dry from achieving drawing of solvent to the full extent.
Then, crude product carries out the underpressure distillation of 1 hour by a definite date in 40 DEG C of situations by oil pump, and is filtered by organic filter membrane of 0.45um, obtains achromaticity and clarification transparent liquid.
" embodiment one "
The preparation method of trimethylolpropane tris (3-mercaptopropionic acid ester), adopts following steps:
First, the 1L there-necked flask of employing, as reaction vessel, this there-necked flask is provided with water trap, adds hexanaphthene, TriMethylolPropane(TMP), 3-thiohydracrylic acid, tosic acid in reaction vessel successively, carries out the oil bath that temperature is 75 to 85 DEG C.Specifically, the content of the cyclohexane of employing is 450ml, the content of TriMethylolPropane(TMP) be the content of 65g, 3-thiohydracrylic acid is 170, the content of tosic acid is 8g.During reaction, nitrogen is adopted to protect.
Afterwards, adopt magnetic force heating stirrer to carry out reflux, interior temperature is stabilized in about 78 DEG C, reacts 1.5 hours.Subsequently, carry out suitable cooling, adopt the sodium bicarbonate of 3 × 200ml to wash cooled product.Methylene dichloride by 3 × 200ml after washing extracts, and is again clarified to organic phase by the organic phase saturated sodium-chloride secondary washing of 2 × 200ml afterwards.
Then, drying is carried out by anhydrous magnesium sulfate.After to be dried, under the state that temperature is less than or equal to 30 DEG C, carry out spin concentration, obtain crude product.Then, crude product carries out the underpressure distillation of 1 hour by a definite date in 40 DEG C of situations by oil pump, and is filtered by organic filter membrane of 0.45um, obtains achromaticity and clarification transparent liquid.
" embodiment two "
The preparation method of trimethylolpropane tris (3-mercaptopropionic acid ester), its preparation process is as follows:
First, using 1L there-necked flask as reaction vessel, the hexanaphthene added successively in this reaction vessel, the TriMethylolPropane(TMP) of 70g, the 3-thiohydracrylic acid of 180g, the tosic acid of 15g, and carry out oil bath when temperature is 85 DEG C.During this period, argon gas is adopted to carry out reaction protection.
Afterwards, adopt magnetic force heating stirrer to carry out reflux, interior temperature is stabilized in about 79 DEG C, reacts 2.5 hours.Subsequently, carry out suitable cooling, adopt the sodium bicarbonate of 3 × 200ml to wash cooled product.Methylene dichloride by 3 × 200ml after washing extracts, and is again clarified to organic phase by the organic phase saturated sodium-chloride secondary washing of 2 × 200ml afterwards.
Finally, drying (half an hour) is carried out by sodium sulfate.After to be dried, under the state that temperature is less than or equal to 30 DEG C, carry out spin concentration, obtain crude product.This crude product is carried out in 40 DEG C of situations the underpressure distillation of 1 hour by a definite date by oil pump, and filtered by organic filter membrane of 0.45um, obtain achromaticity and clarification transparent liquid and namely complete preparation.
Can be found out by above-mentioned character express, after adopting the present invention, effectively can meet the light curing agent demand in optically transparent material process.Further, by effective filtration, have preferably achromaticity and clarification transparent special, improve transparency and the specific refractory power of resin, improve the impact resistance of resin, dyeability and processibility etc.
Claims (10)
1. the preparation method of trimethylolpropane tris (3-mercaptopropionic acid ester), is characterized in that comprising the following steps:
1., in reaction vessel, add hexanaphthene, TriMethylolPropane(TMP), 3-thiohydracrylic acid, tosic acid successively, carry out oil bath, described oil bath temperature is 75 to 85 DEG C to step;
2., reflux, is stabilized in 78 to 79 DEG C by interior temperature to step, reacts 1.5 to 2.5 hours;
3. step, cools, and is washed by cooled product, and carries out extracting rear secondary washing and clarify to organic phase;
4. step, after carrying out drying, obtains crude product after carrying out spin concentration;
5. step, after crude product is carried out underpressure distillation, by final filtration, obtains achromaticity and clarification transparent liquid.
2. the preparation method of trimethylolpropane tris according to claim 1 (3-mercaptopropionic acid ester), is characterized in that: the quality that the volume of described step 1. cyclohexane is 450-550ml, the quality of TriMethylolPropane(TMP) is 65-70g, 3-thiohydracrylic acid is 170-180g, the quality of tosic acid is 8-15g.
3. the preparation method of trimethylolpropane tris according to claim 2 (3-mercaptopropionic acid ester), is characterized in that: the quality that the volume of described step 1. cyclohexane is 500ml, the quality of TriMethylolPropane(TMP) is 67.1g, 3-thiohydracrylic acid is 175g, the quality of tosic acid is 10g.
4. the preparation method of trimethylolpropane tris according to claim 1 (3-mercaptopropionic acid ester), is characterized in that: described step 1. middle nitrogen or the argon gas of adopting is protected.
5. the preparation method of trimethylolpropane tris according to claim 1 (3-mercaptopropionic acid ester), is characterized in that: described step 1. in, oil bath temperature is 80 DEG C.
6. the preparation method of trimethylolpropane tris according to claim 1 (3-mercaptopropionic acid ester), is characterized in that: described step 2. in, adopt magnetic force heating stirrer to carry out reflux, the reaction times is 2 hours.
7. the preparation method of trimethylolpropane tris according to claim 1 (3-mercaptopropionic acid ester), it is characterized in that: the step 3. middle sodium bicarbonate of 3 × 200ml that adopts is washed, described extraction is undertaken by the methylene dichloride of 3 × 200ml, and described secondary washing is undertaken by the organic phase saturated sodium-chloride of 2 × 200ml.
8. the preparation method of trimethylolpropane tris according to claim 1 (3-mercaptopropionic acid ester), it is characterized in that: described step 4. in, carry out drying (half an hour) by anhydrous magnesium sulfate or sodium sulfate (100g), under the state that temperature is less than or equal to 30 DEG C, carry out spin concentration.
9. the preparation method of trimethylolpropane tris according to claim 1 (3-mercaptopropionic acid ester), it is characterized in that: described step 5. in, crude product carries out the underpressure distillation of 1 hour by a definite date in 40 DEG C of situations by oil pump, and passes through organic membrane filtration of 0.45um.
10. the preparation method of trimethylolpropane tris according to claim 1 (3-mercaptopropionic acid ester), is characterized in that: described reaction vessel is 1L there-necked flask, described 1L there-necked flask is provided with water trap.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106699617A (en) * | 2017-02-08 | 2017-05-24 | 南安格泰建材有限公司 | Preparation method of trimethylolpropane tris(3-mercaptopropionate) |
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| CN101896530A (en) * | 2007-12-13 | 2010-11-24 | 昭和电工株式会社 | Epoxy resin curing agent, method for producing the same, and epoxy resin composition |
| JP2011084479A (en) * | 2009-10-13 | 2011-04-28 | Showa Denko Kk | Method of producing mercaptocarboxylate of polyhydric alcohol |
| KR20120084675A (en) * | 2011-01-20 | 2012-07-30 | 주식회사 케이오씨솔루션 | Preparation of 3-mercapto(meta)propionic acid and (meta)carbonic acid ester compound bearing mercapto group using it |
| KR20120097330A (en) * | 2011-02-24 | 2012-09-03 | 주식회사 케이오씨솔루션 | Preparation method of mercapto-carbonic acid and preparation of carbonic acid ester compound bearing mercapto group using it |
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Patent Citations (4)
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| CN101896530A (en) * | 2007-12-13 | 2010-11-24 | 昭和电工株式会社 | Epoxy resin curing agent, method for producing the same, and epoxy resin composition |
| JP2011084479A (en) * | 2009-10-13 | 2011-04-28 | Showa Denko Kk | Method of producing mercaptocarboxylate of polyhydric alcohol |
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