CN106588723A - Preparation method of pentaerythritol tris(3-mercaptopropionate) - Google Patents
Preparation method of pentaerythritol tris(3-mercaptopropionate) Download PDFInfo
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- CN106588723A CN106588723A CN201611177980.8A CN201611177980A CN106588723A CN 106588723 A CN106588723 A CN 106588723A CN 201611177980 A CN201611177980 A CN 201611177980A CN 106588723 A CN106588723 A CN 106588723A
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- Prior art keywords
- tetramethylolmethane
- preparation
- mercaptopropionic acids
- ester
- esterification
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/02—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols
- C07C319/12—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols by reactions not involving the formation of mercapto groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
Abstract
The invention provides a preparation method of pentaerythritol tris(3-mercaptopropionate), and belongs to the field of preparation of chain transfer agents for polymerization. Under the condition of nitrogen protection, the pentaerythritol tris(3-mercaptopropionate) is obtained by using pentaerythritol, 3-mercaptopropionic acid, a catalyst and a water-carrying agent as raw materials through esterification. The prepared pentaerythritol tris(3-mercaptopropionate) has three mercapto groups and can be used as a nucleating agent for star-shaped molecules and can form a three-arm star-shaped structure during the polymerization process to improve chain transfer activity and effectively reduce other chain termination modes, and the preparation method has simple process and is suitable for industrial production.
Description
Technical field
The present invention relates to the preparation field being polymerized with chain-transferring agent, more particularly to a kind of penta tetrol three (3- mercaptopropionic acids) ester
Preparation method.
Background technology
Chain-transferring agent, to adjust the relative molecular mass of polymer, is that one kind can occur effectively propagating radical
The material of radical transfer, is the important organic synthesis intermediate of a class.
At present, conventional chain-transferring agent mostly is simple function group straight chain type chain-transferring agent, and such as CN1508156A is disclosed with C3
Used as chain-transferring agent, CN1086395 discloses a kind of amine-amine-thiol chain transfer agents to～C5 hydrocarbon, and CN1389451A is disclosed with allyl
Base chain-transferring agent, the polymerizate that these simple function group straight chain type chain-transferring agents are prepared all is straight chain type, it is impossible to obtain star
The problem of type structured product.
In prior art, containing four methylols being equal to, the symmetry with height and reaction in tetramethylolmethane molecule
Activity, is often used as the raw material midbody produced of polyfunctional compound, and its esters product is widely used in coating, color
The industries such as paint, varnish, printing-ink, smolderability material and aeroengine oil.As CN103274940A discloses a kind of Ji Wusi
Alcohol acrylate can give coating weatherability, resistance to water, can be used in elastomer, fluid sealant, scaling powder, binding agent, glass, gold
Category, floor paint, timber and coating for paper and ink etc.；CN102627771A discloses two phosphoryl chloride phosphorus oxychloride of pentaerythritol diphosphate
The preparation method of contracting ethylenediamine macromolecular type fire retardant；CN101293828A discloses the Ji Wusi that can be used for inviscid wetting agent
Alcohol isostearate；CN102702048B discloses tetramethylolmethane mercapto-carboxylic ester and containing tetramethylolmethane mercapto-carboxylic ester and many
The polymerizable composition, polymerizable composition of isothiocyanate compound is to be best suitable for one of resin of plastic lens.
The content of the invention
In view of this, it is an object of the invention to provide a kind of preparation method of tetramethylolmethane three (3- mercaptopropionic acids) ester,
Chain transfer activity is improved, the yield of hub-and-spoke configuration is improved, while the preparation method process is simple of the present invention, is adapted to industry metaplasia
Produce.
In order to realize foregoing invention purpose, the present invention provides technical scheme below：
A kind of preparation method of tetramethylolmethane three (3- mercaptopropionic acids) ester, comprises the following steps：
Under nitrogen protection, the mixing of tetramethylolmethane, 3- mercaptopropionic acids, acidic catalyst and water entrainer is carried out being esterified instead
Should, obtain tetramethylolmethane three (3- mercaptopropionic acids) ester.
Preferably, the tetramethylolmethane and the mol ratio of 3- mercaptopropionic acids are 1：3.0～3.2.
Preferably, the acidic catalyst is the one kind in p-methyl benzenesulfonic acid and concentrated sulphuric acid, the tetramethylolmethane and 3- mercaptos
Base propanoic acid gross mass is 100 with the mass ratio of acidic catalyst：0.8～1.2.
Preferably, the water entrainer is hexamethylene, the tetramethylolmethane and 3- mercaptopropionic acids gross mass and the matter of water entrainer
Amount is than being 10：2～3.
Preferably, the temperature of the esterification is 100～120 DEG C, and the time of esterification is 4～10h.
Preferably, also include distilling the esterification reaction product after the esterification.
Preferably, the distillation is vacuum distillation.
Preferably, the temperature of the vacuum distillation is 80～105 DEG C, and the time of vacuum distillation is 1～3h, the decompression steaming
The vacuum for evaporating is -0.05～-0.1MPa.
Tetramethylolmethane three (3- mercaptopropionic acids) ester that the present invention is prepared has structure shown in Formulas I：
The invention provides a kind of preparation method of tetramethylolmethane three (3- mercaptopropionic acids) ester, in the condition of nitrogen protection
Under, tetramethylolmethane three (3- is obtained through esterification by raw material of tetramethylolmethane, 3- mercaptopropionic acids, catalyst and water entrainer
Mercaptopropionic acid) ester, nitrogen be prevented from sulfydryl be oxidized, the water that water entrainer is generated in can removing esterification is conducive to
To pure tetramethylolmethane three (3- mercaptopropionic acids) ester.Obtained in of the invention, tetramethylolmethane three (3- mercaptopropionic acids) ester has three
Sulfydryl, can use as the nucleator of star-shaped molecule, can form three-arm star-shaped structure in the course of the polymerization process, while of the invention
Preparation method process is simple, be adapted to industrialized production.
Description of the drawings
The present invention is further detailed explanation with reference to the accompanying drawings and detailed description.
Fig. 1 is the infrared spectrum spectrogram of 3- mercaptopropionic acids of the present invention and obtained tetramethylolmethane three (3- mercaptopropionic acids) ester.
Specific embodiment
The invention provides a kind of preparation method of tetramethylolmethane three (3- mercaptopropionic acids) ester, comprises the following steps：
Under nitrogen protection, the mixing of tetramethylolmethane, 3- mercaptopropionic acids, acidic catalyst and water entrainer is carried out being esterified instead
Should, obtain tetramethylolmethane three (3- mercaptopropionic acids) ester.
In the present invention, the tetramethylolmethane is preferably 1 with the mol ratio of 3- mercaptopropionic acids：3.0～3.2, more preferably
1：3.05～3.15, most preferably 1：3.1～3.12.
In the present invention, the acidic catalyst is preferably the one kind in p-methyl benzenesulfonic acid and concentrated sulphuric acid.
In the present invention, the gross mass of the tetramethylolmethane and 3- mercaptopropionic acids is preferably with the mass ratio of acidic catalyst
100：0.8～1.2, more preferably 100：0.9～1.1, most preferably 100：0.95～1.05.
In the present invention, the water that water entrainer can be generated in removing dereaction, the water entrainer are preferably hexamethylene.
In the present invention, the gross mass of the tetramethylolmethane and 3- mercaptopropionic acids is preferably 10 with the mass ratio of water entrainer：2
～3, more preferably 10：2.5～2.8, most preferably 10：2.6～2.7.
Order by merging of the present invention to tetramethylolmethane, 3- mercaptopropionic acids, catalyst and water entrainer does not have any special limit
System, using mixing charging sequence well known to those skilled in the art, is preferably set to reaction in embodiments of the present invention successively
Standby middle addition tetramethylolmethane, 3- mercaptopropionic acids, catalyst and water entrainer are mixed.
The present invention does not have any special restriction to the mode of the mixing, using mitigation well known to those skilled in the art
Mode, is preferably mixed by the way of stirring in embodiments of the present invention, and the speed of the stirring is preferably 200～
600rpm, more preferably 300～500rpm, most preferably 400～450rpm；The time of the stirring is preferably 1～3h, more excellent
Elect 1.5～2.5h, most preferably 2～2.2h as.
In the present invention, the temperature of the esterification is preferably 100～120 DEG C, more preferably 105～115 DEG C, optimum
Elect 110～112 DEG C as；The time of the esterification is preferably 4～10h, most preferably more preferably 5～8h, 6～7h.
The present invention does not have any special restriction to the device of the esterification, using well known to those skilled in the art
Esterification device；Preferably had after the completion of esterification using the reactor with water knockout drum in embodiments of the present invention
Beneficial to by water phase and organic phase separation, pure tetramethylolmethane three (3- mercaptopropionic acids) ester is obtained.
After the completion of esterification, the esterification organic phase product for obtaining preferably is distilled by the present invention, obtains season penta
Tetrol three (3- mercaptopropionic acids) ester.The present invention does not have any special restriction to the mode of the distillation, using art technology
Distillation mode known to personnel, is carried out preferably by the way of vacuum distillation in embodiments of the present invention, and the present invention is to institute
The device for stating vacuum distillation does not have any special restriction, using vacuum distillation apparatus well known to those skilled in the art,
Preferably vacuum distillation is carried out using by esterification device connection vacuum equipment in embodiments of the present invention.
In the present invention, the temperature of the vacuum distillation is preferably 80～105 DEG C, more preferably 85～100 DEG C, most preferably
For 90～95 DEG C；The time of the vacuum distillation is preferably 1～3h, most preferably more preferably 1.5～2.5h, 2～2.2h；Institute
The vacuum for stating vacuum distillation is preferably -0.05～-0.1MPa, more preferably -0.06～-0.09MPa, most preferably -0.07
～-0.08MPa.
Tetramethylolmethane, 3- mercaptopropionic acids, acidic catalyst and water entrainer described in above-mentioned technical proposal are come in the present invention
Source does not have any special restriction, using commercial goods well known to those skilled in the art.
The molecular structure of tetramethylolmethane three (3- mercaptopropionic acids) ester that the present invention is prepared is shown in formula I：
The invention provides a kind of preparation method of tetramethylolmethane three (3- mercaptopropionic acids) ester, in the condition of nitrogen protection
Under, tetramethylolmethane three (3- is obtained through esterification by raw material of tetramethylolmethane, 3- mercaptopropionic acids, catalyst and water entrainer
Mercaptopropionic acid) ester, nitrogen be prevented from sulfydryl be oxidized, the water that water entrainer is generated in can removing esterification is conducive to
To pure tetramethylolmethane three (3- mercaptopropionic acids) ester.Obtained in of the invention, tetramethylolmethane three (3- mercaptopropionic acids) ester has three
Sulfydryl, can use as the nucleator of star-shaped molecule, can form three-arm star-shaped structure in the course of the polymerization process, can improve chain
Transfer activity, efficiently reduces other chain termination modes, improves star structure yield, while the preparation method technique letter of the present invention
It is single, it is adapted to industrialized production.
The preparation method of tetramethylolmethane three (3- mercaptopropionic acids) ester provided to the present invention with reference to embodiment is carried out in detail
Thin explanation, but they can not be interpreted as limiting the scope of the present invention.
Embodiment 1
In the four-hole boiling flask of the 1000ml with water knockout drum, first lead to nitrogen displacement air, then sequentially add Ji Wusi
Alcohol 200g, 3- mercaptopropionic acid 468g, 98% concentrated sulphuric acid 5.3g, hexamethylene 133.6g slowly start stirring, control mixing speed
For 200rpm, heat up, four mouthfuls of four-hole boiling flask are respectively charged into nitrogen purging, thermometer, temperature control thermal resistance and water knockout drum, open cold
But water, after all materials all dissolve, is heated to 100 DEG C of reaction 4h, stops heating after the completion of reaction, at spherical condensation tube end
Load onto vacuum equipment in end.Vacuum is increased slowly, removed under reduced pressure water entrainer is finally distilled at -0.05MPa vacuums, 85 DEG C
1h, obtains yellow liquid product, i.e. tetramethylolmethane three (3- mercaptopropionic acids) ester.
Examination of infrared spectrum is carried out to 3- mercaptopropionic acids and obtained tetramethylolmethane three (3- mercaptopropionic acids) ester, such as Fig. 1 institutes
Show, infrared spectrum spectrograms of a for 3- mercaptopropionic acids in Fig. 1, b are composed for the infrared spectrum of tetramethylolmethane three (3- mercaptopropionic acids) ester
Figure, from Fig. 1 (b), in 3425～3034cm-1There is a wide absworption peak, this is because 3- mercaptopropionic acids form intermolecular many
Caused by-OH base the stretching vibrations of aggressiveness, in 1702cm-1There is the absworption peak of the last one at place, and this is to form polymeric 3- mercaptopropionic acids
- COOH characteristic absorption, CH3Stretching vibration in 2935cm-1, 2574cm-1For the stretching vibration of-SH groups, 2662cm-1
For-S-CH2Characteristic absorption, belong to weak absorbing；When tetramethylolmethane three (3- mercaptopropionic acids) ester is formed, the poly of 3- mercaptopropionic acids
Form is destroyed, 3500cm on infrared spectrum-1The broad peak at place narrows, 3551cm-1- OH containing minor amount of water bases in category compound
Stretching vibration, in 2636～2620cm-1Weak absorbing also indicate that in compound with the presence of water entrainment, 1702cm-1Absorption band disappears
Lose, and instead of be tetramethylolmethane three (3- mercaptopropionic acids) ester-COO bases in 1735cm-1The asymmetric flexible bands of a spectrum at place, while
In 1157cm-1Locate the symmetrical stretching vibration for-COO bases, form the feature of-SH bases after tetramethylolmethane three (3- mercaptopropionic acids) ester
Absorbs be still 2575cm-1Place, above analysis shows react the product for generating and really belong to tetramethylolmethane three (3- mercaptopropionic acids) ester.
After three (3- mercaptopropionic acids) ester of obtained tetramethylolmethane is deposited 30 days under room temperature (15～25 DEG C), determine in fact
Apply effect.Flowing degree of net paste of cement：Test determines the paste flowing degree under identical divergence, and GB/T8077-2000 is pressed in test
《Methods for testing uniformity of concrete admixture》Carry out.Result of the test is shown in Table 1.
It is comparative example from existing commercially available traditional combed poly carboxylic acid series water reducer, the performance of test comparison example, test are pressed
GB/T8077-2000《Methods for testing uniformity of concrete admixture》Carry out, result of the test is shown in Table 1.
The rheological parameters' change with time result of the test of 1 flowing degree of net paste of cement of table
From table 1 it follows that tetramethylolmethane three (3- mercaptopropionic acids) ester obtained in the inventive method has preferably only
The agent of slurry initial extension degree keeps good mobility, and its effect is more excellent than selected combed polycarboxylate water-reducer control sample.
By three (3- mercaptopropionic acids) ester of tetramethylolmethane obtained in the present embodiment and traditional combed poly carboxylic acid series water reducer difference
Mix with concrete, as shown in table 3, table 2 is detection concrete mix to test result, and cement is Carnis Rapanae thomasianae cement, and sandstone is expensive
The commercially available aggregate in state, wherein sand are Machine-made Sand.
2 concrete material match ratio of table
3 testing concrete performance result of table
From table 3 it can be seen that tetramethylolmethane three (3- mercaptopropionic acids) ester synthesized by the inventive method, in concrete system
In can show the holding performance of excellent divergence and the slump.
Embodiment 2
In the four-hole boiling flask of the 1000ml with water knockout drum, first lead to nitrogen displacement air, then sequentially add Ji Wusi
Alcohol 200g, 3- mercaptopropionic acid 498g, p-methyl benzenesulfonic acid 8.4g, hexamethylene 209.4g, slowly start stirring, control mixing speed and are
600rpm, heats up, and four mouthfuls of four-hole boiling flask are respectively charged into nitrogen purging, thermometer, temperature control thermal resistance and water knockout drum, open cooling
Water, after all materials all dissolve, is heated to 120 DEG C of reaction 10h, stops heating after the completion of reaction, at spherical condensation tube end
Load onto vacuum equipment in end.Vacuum is increased slowly, removed under reduced pressure water entrainer is finally distilled at -0.1MPa vacuums, 105 DEG C
3h, obtains yellow liquid product, i.e. tetramethylolmethane three (3- mercaptopropionic acids) ester.
Embodiment 3
In the four-hole boiling flask of the 1000ml with water knockout drum, first lead to nitrogen displacement air, then sequentially add Ji Wusi
The concentrated sulphuric acid 2.7g of alcohol 200g, 3- mercaptopropionic acid 478g, p-methyl benzenesulfonic acid 3.4g, 98%, hexamethylene 209.4g, slowly start and stir
Mix, it is 300rpm to control mixing speed, is heated up, and four mouthfuls of four-hole boiling flask are respectively charged into nitrogen purging, thermometer, temperature control thermal resistance
And water knockout drum, unlatching cooling water, after all materials all dissolve, 110 DEG C of reaction 5h are heated to, stop adding after the completion of reaction
Heat, loads onto vacuum equipment in bulb condensation pipe end.Vacuum, removed under reduced pressure water entrainer, finally in -0.06MPa are increased slowly
Vacuum, distill 1.5h at 95 DEG C, obtain yellow liquid product, i.e. tetramethylolmethane three (3- mercaptopropionic acids) ester.
Embodiment 4
In the four-hole boiling flask of the 1000ml with water knockout drum, first lead to nitrogen displacement air, then sequentially add Ji Wusi
The concentrated sulphuric acid 3.2g of alcohol 200g, 3- mercaptopropionic acid 491g, p-methyl benzenesulfonic acid 4.4g, 98%, hexamethylene 209.4g, slowly start and stir
Mix, it is 500rpm to control mixing speed, is heated up, and four mouthfuls of four-hole boiling flask are respectively charged into nitrogen purging, thermometer, temperature control thermal resistance
And water knockout drum, unlatching cooling water, after all materials all dissolve, 105 DEG C of reaction 8h are heated to, stop adding after the completion of reaction
Heat, loads onto vacuum equipment in bulb condensation pipe end.Vacuum, removed under reduced pressure water entrainer, finally in -0.07MPa are increased slowly
Vacuum, distill 2.5h at 95 DEG C, obtain yellow liquid product, i.e. tetramethylolmethane three (3- mercaptopropionic acids) ester.
Embodiment 5
In the four-hole boiling flask of the 1000ml with water knockout drum, first lead to nitrogen displacement air, then sequentially add Ji Wusi
The concentrated sulphuric acid 4.8g of alcohol 200g, 3- mercaptopropionic acid 483g, p-methyl benzenesulfonic acid 2.4g, 98%, hexamethylene 209.4g, slowly start and stir
Mix, it is 400rpm to control mixing speed, is heated up, and four mouthfuls of four-hole boiling flask are respectively charged into nitrogen purging, thermometer, temperature control thermal resistance
And water knockout drum, unlatching cooling water, after all materials all dissolve, 112 DEG C of reaction 6h are heated to, stop adding after the completion of reaction
Heat, loads onto vacuum equipment in bulb condensation pipe end.Vacuum, removed under reduced pressure water entrainer, finally in -0.08MPa are increased slowly
Vacuum, distill 2h at 100 DEG C, obtain yellow liquid product, i.e. tetramethylolmethane three (3- mercaptopropionic acids) ester.
The above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (8)
1. the preparation method of a kind of tetramethylolmethane three (3- mercaptopropionic acids) ester, it is characterised in that comprise the following steps：
Under nitrogen protection, the mixing of tetramethylolmethane, 3- mercaptopropionic acids, acidic catalyst and water entrainer is carried out into esterification, is obtained
To tetramethylolmethane three (3- mercaptopropionic acids) ester.
2. preparation method according to claim 1, it is characterised in that the mol ratio of the tetramethylolmethane and 3- mercaptopropionic acids
For 1：3.0～3.2.
3. preparation method according to claim 1, it is characterised in that the acidic catalyst is p-methyl benzenesulfonic acid and dense sulfur
One kind in acid, the tetramethylolmethane are 100 with the mass ratio of 3- mercaptopropionic acids gross mass and acidic catalyst：0.8～1.2.
4. preparation method according to claim 1, it is characterised in that the water entrainer is hexamethylene, the tetramethylolmethane
Mass ratio with 3- mercaptopropionic acids gross mass and water entrainer is 10：2～3.
5. preparation method according to claim 1, it is characterised in that the temperature of the esterification is 100～120 DEG C,
The time of esterification is 4～10h.
6. preparation method according to claim 1, it is characterised in that also include after the esterification：By the esterification
Product is distilled.
7. preparation method according to claim 7, it is characterised in that the distillation is vacuum distillation.
8. preparation method according to claim 8, it is characterised in that the temperature of the vacuum distillation is 80～105 DEG C, is subtracted
The time of pressure distillation is 1～3h, and the vacuum of the vacuum distillation is -0.05～-0.1MPa.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111471444A (en) * | 2020-05-28 | 2020-07-31 | 陕西科技大学 | Polyamino bactericidal surfactant and preparation method and application thereof |
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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 |
| JP2011126822A (en) * | 2009-12-18 | 2011-06-30 | Showa Denko Kk | Method for producing polyhydric alcohol ester of mercaptocarboxylic acid |
| CN102603583A (en) * | 2012-02-28 | 2012-07-25 | 湘潭大学 | Method for preparing multi-sulfhydryl carboxylic ester |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101541837A (en) * | 2006-11-21 | 2009-09-23 | 昭和电工株式会社 | Curable composition containing hydroxyl group-containing thiol compound and cured product thereof |
| 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 |
| JP2011126822A (en) * | 2009-12-18 | 2011-06-30 | Showa Denko Kk | Method for producing polyhydric alcohol ester of mercaptocarboxylic acid |
| CN102603583A (en) * | 2012-02-28 | 2012-07-25 | 湘潭大学 | Method for preparing multi-sulfhydryl carboxylic ester |
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| CN111471444A (en) * | 2020-05-28 | 2020-07-31 | 陕西科技大学 | Polyamino bactericidal surfactant and preparation method and application thereof |
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