CN104529766A - Preparation method of pentaerythritol tristearate - Google Patents
Preparation method of pentaerythritol tristearate Download PDFInfo
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- CN104529766A CN104529766A CN201410739509.8A CN201410739509A CN104529766A CN 104529766 A CN104529766 A CN 104529766A CN 201410739509 A CN201410739509 A CN 201410739509A CN 104529766 A CN104529766 A CN 104529766A
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- tetramethylolmethane
- tristearate
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- tetramethylolmethane tristearate
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/053—Sulfates
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Abstract
The invention belongs to the field of chemical synthesis and relates to a preparation method of pentaerythritol tristearate. The preparation method comprises the following steps of adding stearic acid and pentaerythritol into a reactor according to a mole ratio of 1.0-1.2: 1, carrying out stirring mixing to obtain a uniform mixture, adding solid super acid into the mixture to cause a reaction lasting for 2-3h under the conditions of a temperature of 150-180 DEG C and pressure of 5-50Pa so that a pentaerythritol tristearate crude product is obtained by the reaction, and carrying out decoloring treatment on the pentaerythritol tristearate crude product to obtain a pentaerythritol tristearate finished product. The preparation method utilizes solid super acid SO4<2->/ZrO2-SiO2 as a pentaerythritol tristearate synthesis catalyst, reduces the existing reaction high-temperature from 200 DEG C to 150-180 DEG C, reduces reaction time by 1-2h and greatly saves a production cost and energy consumption. The preparation method of pentaerythritol tristearate has a high esterification rate of 92% and good product indexes.
Description
Technical field
The invention belongs to chemical industry synthesis field, be specifically related to a kind of preparation method of tetramethylolmethane tristearate.
Background technology
Pentaerythritol stearate (Pentaerythritol stearate), referred to as PETS, is hard white high-melting-point wax, is dissolved in ethanol, benzene and chloroform, water insoluble.Main as highly-efficient lubricant, polyvinyl chloride (PVC) stabilizer, softening agent etc.Because it has environment friendly and recyclability, take pentaerythritol stearate as the attention that the polyol ester of representative is more and more subject to domestic and international investigator, but polyol ester building-up process exists problems such as reaction conversion ratio is low, expensive catalyst, severe reaction conditions, be badly in need of further technical perfection.Tetramethylolmethane tristearate is widely used in auxiliary heat stabilizer in plastic industry, transparent base held concurrently by softening agent, lubrication brightening agent.Most outstanding advantage is good with other analog assistant compatibleness, high temperature resistant, also has antiseptic property.
Fu Tingjin etc. have studied the synthesis technique of pentaerythritol stearate, its result shows, synthesis of pentaerythritol stearate processing condition are: material ratio 1.12:1, catalyzer is selected from controlling catalyst A, consumption is 3 ‰ of stearic acid quality, temperature of reaction 200 DEG C, the reaction times, Fu 3-4h(drive on boldly. the synthesis [J] of pentaerythritol stearate. and Lu skyization science and technology the 1st phase: 61-65 in 2004).This paper does not disclose concrete catalyzer, so do not bring technology to enlighten to the present invention.
Chinese patent CN103880668A discloses a kind of preparation technology of pentaerythritol stearate, and its raw material weight ratio is: tetramethylolmethane 3-5 part, stearic acid 15-20 part, potassium hydroxide 0.02-0.1 part; Its preparation process is, is dropped into by stearic acid in stainless steel melting pot, is steam heated to 60-100 degree Celsius, melt completely, after add in esterification tank and add tetramethylolmethane and potassium hydroxide, vacuumize, and remain on 0.005-0.01KPa, heat-conducting oil heating is to 200 DEG C, carry out esterification 4 hours, detect pH and be less than 5, react complete, be cooled to 120 degrees Celsius, filter.The temperature of reaction of the method is high, long reaction time.
Summary of the invention
The object of the present invention is to provide a kind of operation steps simple, condition is easy to control, with short production cycle, the preparation method of the tetramethylolmethane tristearate that esterification yield is high.
The present invention is achieved through the following technical solutions above-mentioned purpose:
A kind of preparation method of tetramethylolmethane tristearate, comprise the following steps: by stearic acid and tetramethylolmethane according to molar ratio of material (1.0-1.2): 1 drops in reactor, be uniformly mixed, then catalyzer is added, 2-3h is reacted at 5-50Pa vacuum, 150-180 DEG C, reaction terminates to obtain tetramethylolmethane tristearate crude product, then carries out desolventing technology to tetramethylolmethane tristearate crude product, obtains tetramethylolmethane tristearate finished product.
Further, described catalyzer is solid super-strong acid SO
4 2-/ ZrO
2-SiO
2, consumption is the 0.2-0.6% of stearic acid quality.
Present invention also offers catalyst solid super acids SO of the present invention
4 2-/ ZrO
2-SiO
2preparation method, concrete steps are: get basic zirconium chloride (ZrOCl
28H
2o) be mixed with zirconium oxychloride solution, add diatomite, leave standstill about 20min and make it fully flood, then add 26% strong aqua and regulate pH 9.0, after leaving standstill 4h, suction filtration also uses distilled water repetitive scrubbing 3 times, is deposited in 80 DEG C of baking oven inner drying 1h by what obtain; Join in sulphuric acid soln after drying terminates and flood 20min, suction filtration again, finally filter cake is moved into roasting 3h in 600 DEG C of muffle furnaces after baking oven inner drying, obtain SO
4 2-/ ZrO
2-SiO
2solid super acid catalyst; Wherein, the concentration of zirconium oxychloride solution is 3%(massfraction), the mass ratio of basic zirconium chloride and diatomite, sulfuric acid is 1: 12: 18; The concentration of sulphuric acid soln is 50wt%(massfraction).
As the preferred embodiment of the present invention, the preparation method of tetramethylolmethane tristearate of the present invention, comprise the following steps: stearic acid and tetramethylolmethane are dropped in reactor according to molar ratio of material 1.1: 1, is uniformly mixed, then adds the solid super-strong acid SO of 0.5% of stearic acid quality
4 2-/ ZrO
2-SiO
2, react 2h in 30Pa vacuum, at 160 DEG C, reaction terminates to obtain tetramethylolmethane tristearate crude product, then carries out desolventing technology to tetramethylolmethane tristearate crude product, obtains tetramethylolmethane tristearate finished product.
Compared with prior art, the present invention has following technical superiority:
(1) the present invention adopts solid super-strong acid SO
4 2-/ ZrO
2-SiO
2as the catalyzer of tetramethylolmethane tristearate synthesis, the high temperature of 200 DEG C when reacting in prior art is reduced to 150-180 DEG C, and the reaction times decreases 1-2h, has greatly saved production cost and energy consumption.Also show solid super-strong acid SO simultaneously
4 2-/ ZrO
2-SiO
2to the building-up reactions of tetramethylolmethane tristearate, there is good catalytic activity and highly selective, this catalyzer is reused 5 times and is still kept greater activity, and has the advantage such as liquid-phase reaction system separation, not etching apparatus, simple, the little contaminate environment of aftertreatment.
(2) esterification yield of the preparation method of tetramethylolmethane tristearate of the present invention is high, can up to 92%, and product index is good.
Embodiment
Further describe the present invention below by way of embodiment, but the present invention is not limited only to following examples.Within the scope of the invention or not departing from content of the present invention, spirit and scope, the preparation method of tetramethylolmethane tristearate of the present invention is suitably improved, replaces the identical component of effect, will become apparent to those skilled in the art that they are all deemed to be included within scope of the present invention.
the preparation method of embodiment 1, tetramethylolmethane tristearate of the present invention:
Stearic acid and tetramethylolmethane are dropped in reactor according to molar ratio of material 1.0: 1, is uniformly mixed, then adds the solid super-strong acid SO of 0.2% of stearic acid quality
4 2-/ ZrO
2-SiO
2, at 5Pa vacuum, reaction times 3h at 150 DEG C, reaction terminates and obtains tetramethylolmethane tristearate crude product, and then carry out desolventing technology to tetramethylolmethane tristearate crude product, obtain tetramethylolmethane tristearate finished product, assaying reaction esterification yield is 88%.
Solid super-strong acid SO
4 2-/ ZrO
2-SiO
2the concrete steps of preparation method be: get basic zirconium chloride (ZrOCl
28H
2o) be mixed with zirconium oxychloride solution, add diatomite, leave standstill about 20min and make it fully flood, then add 26% strong aqua and regulate pH 9.0, after leaving standstill 4h, suction filtration also uses distilled water repetitive scrubbing 3 times, is deposited in 80 DEG C of baking oven inner drying 1h by what obtain; Join in sulphuric acid soln after drying terminates and flood 20min, suction filtration again, finally filter cake is moved into roasting 3h in 600 DEG C of muffle furnaces after baking oven inner drying, obtain SO
4 2-/ ZrO
2-SiO
2solid super acid catalyst; Wherein, the concentration of zirconium oxychloride solution is 3%(massfraction), the mass ratio of basic zirconium chloride and diatomite, sulfuric acid is 1: 12: 18; The concentration of sulphuric acid soln is 50wt%(massfraction).
the preparation method of embodiment 2, tetramethylolmethane tristearate of the present invention:
Stearic acid and tetramethylolmethane are dropped in reactor according to molar ratio of material 1.2: 1, is uniformly mixed, then adds the solid super-strong acid SO of 0.6% of stearic acid quality
4 2-/ ZrO
2-SiO
2, at 50Pa vacuum, reaction times 2h at 180 DEG C, reaction terminates and obtains tetramethylolmethane tristearate crude product, and then carry out desolventing technology to tetramethylolmethane tristearate crude product, obtain tetramethylolmethane tristearate finished product, assaying reaction esterification yield is 89%.
Solid super-strong acid SO
4 2-/ ZrO
2-SiO
2the concrete steps of preparation method be: get basic zirconium chloride (ZrOCl
28H
2o) be mixed with zirconium oxychloride solution, add diatomite, leave standstill about 20min and make it fully flood, then add 26% strong aqua and regulate pH 9.0, after leaving standstill 4h, suction filtration also uses distilled water repetitive scrubbing 3 times, is deposited in 80 DEG C of baking oven inner drying 1h by what obtain; Join in sulphuric acid soln after drying terminates and flood 20min, suction filtration again, finally filter cake is moved into roasting 3h in 600 DEG C of muffle furnaces after baking oven inner drying, obtain SO
4 2-/ ZrO
2-SiO
2solid super acid catalyst; Wherein, the concentration of zirconium oxychloride solution is 3%(massfraction), the mass ratio of basic zirconium chloride and diatomite, sulfuric acid is 1: 12: 18; The concentration of sulphuric acid soln is 50wt%(massfraction).
the preparation method of embodiment 3, tetramethylolmethane tristearate of the present invention:
Stearic acid and tetramethylolmethane are dropped in reactor according to molar ratio of material 1.1: 1, is uniformly mixed, then adds the solid super-strong acid SO of 0.5% of stearic acid quality
4 2-/ ZrO
2-SiO
2, at 30Pa vacuum, reaction times 2h at 160 DEG C, reaction terminates and obtains tetramethylolmethane tristearate crude product, and then carry out desolventing technology to tetramethylolmethane tristearate crude product, obtain tetramethylolmethane tristearate finished product, assaying reaction esterification yield is 92%.
Solid super-strong acid SO
4 2-/ ZrO
2-SiO
2the concrete steps of preparation method be: get basic zirconium chloride (ZrOCl
28H
2o) be mixed with zirconium oxychloride solution, add diatomite, leave standstill about 20min and make it fully flood, then add 26% strong aqua and regulate pH 9.0, after leaving standstill 4h, suction filtration also uses distilled water repetitive scrubbing 3 times, is deposited in 80 DEG C of baking oven inner drying 1h by what obtain; Join in sulphuric acid soln after drying terminates and flood 20min, suction filtration again, finally filter cake is moved into roasting 3h in 600 DEG C of muffle furnaces after baking oven inner drying, obtain SO
4 2-/ ZrO
2-SiO
2solid super acid catalyst; Wherein, the concentration of zirconium oxychloride solution is 3%(massfraction), the mass ratio of basic zirconium chloride and diatomite, sulfuric acid is 1: 12: 18; The concentration of sulphuric acid soln is 50wt%(massfraction).
the detection of experimental example one, tetramethylolmethane tristearate of the present invention:
Detect the embodiment of the present invention 3 tetramethylolmethane tristearate, its physical and chemical index is in table 1.As shown in Table 1, the physical and chemical index of tetramethylolmethane tristearate product of the present invention is excellent.
Table 1 tetramethylolmethane tristearate product physical and chemical index
| Project | Tetramethylolmethane tristearate |
| Outward appearance | White waxy powder (sheet) |
| Acid number Mg/KoHg | ≤5 |
| Iodine number gI/100 | ≤2 |
| Hydroxyl value Mg/KoHg | 55-65 |
| Saponification value Mg/KoHg | 185-195 |
| Thermal weight loss 105 DEG C of 2h% | ≤0.5 |
| Fusing point/DEG C | 55-60 |
Below be only the preferred embodiment of the present invention, it should be pointed out that above-mentioned preferred implementation should not be considered as limitation of the present invention, protection scope of the present invention should be as the criterion with claim limited range.For those skilled in the art, without departing from the spirit and scope of the present invention, can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (4)
1. the preparation method of a tetramethylolmethane tristearate, it is characterized in that, it comprises the following steps: by stearic acid and tetramethylolmethane according to molar ratio of material (1.0-1.2): 1 drops in reactor, be uniformly mixed, then add catalyzer, reaction times 2-3h at 5-50Pa vacuum, 150-180 DEG C, reaction terminates to obtain tetramethylolmethane tristearate crude product, then desolventing technology is carried out to tetramethylolmethane tristearate crude product, obtain tetramethylolmethane tristearate finished product.
2. the preparation method of tetramethylolmethane tristearate as claimed in claim 1, it is characterized in that, described catalyzer is solid super-strong acid SO
4 2-/ ZrO
2-SiO
2, consumption is the 0.2-0.6% of stearic acid quality.
3. the preparation method of tetramethylolmethane tristearate as claimed in claim 2, it is characterized in that, the concrete steps of described method for preparing catalyst are: get basic zirconium chloride (ZrOCl
28H
2o) be mixed with zirconium oxychloride solution, add diatomite, leave standstill about 20min and make it fully flood, then add 26% strong aqua and regulate pH 9.0, after leaving standstill 4h, suction filtration also uses distilled water repetitive scrubbing 3 times, is deposited in 80 DEG C of baking oven inner drying 1h by what obtain; Join in sulphuric acid soln after drying terminates and flood 20min, suction filtration again, finally filter cake is moved into roasting 3h in 600 DEG C of muffle furnaces after baking oven inner drying, obtain described catalyst S O
4 2-/ ZrO
2-SiO
2solid super acid catalyst; Wherein, the concentration of zirconium oxychloride solution is 3%(massfraction), the mass ratio of basic zirconium chloride and diatomite, sulfuric acid is 1: 12: 18; The concentration of sulphuric acid soln is 50wt%(massfraction).
4. the preparation method of the tetramethylolmethane tristearate as described in as arbitrary in claim 1-3, it is characterized in that, it comprises the following steps: drop in reactor by stearic acid and tetramethylolmethane according to molar ratio of material 1.1: 1, be uniformly mixed, then add the solid super-strong acid SO of 0.5% of stearic acid quality
4 2-/ ZrO
2-SiO
2, react 2h in 30Pa vacuum, at 160 DEG C, reaction terminates to obtain tetramethylolmethane tristearate crude product, then carries out desolventing technology to tetramethylolmethane tristearate crude product, obtains tetramethylolmethane tristearate finished product.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106631779A (en) * | 2016-08-31 | 2017-05-10 | 山东金昌树新材料科技有限公司 | Polyol ester and application of same to processing of halogenated vinyl polymer |
| CN106631806A (en) * | 2016-08-31 | 2017-05-10 | 山东金昌树新材料科技有限公司 | Mixed polyol ester and application thereof to halogenated vinyl polymer processing |
| CN106966905A (en) * | 2017-05-05 | 2017-07-21 | 广州嘉德乐生化科技有限公司 | A kind of preparation method of pentaerythrite tristearate |
| CN107501092A (en) * | 2017-08-21 | 2017-12-22 | 大连理工大学 | A kind of method that continuous decompression catalytic distillation prepares pentaerythrite ester base oil |
| CN108191650A (en) * | 2017-12-25 | 2018-06-22 | 江苏雷蒙新材料有限公司 | A kind of preparation method of pentaerythrite tetra-acetate |
-
2014
- 2014-12-08 CN CN201410739509.8A patent/CN104529766A/en active Pending
Non-Patent Citations (5)
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| 万庆梅，金一丰，王胜利，王新荣: "SO42-/ZrO2-Al2O3催化合成季戊四醇四异硬脂酸酯", 《日用化学工业》 * |
| 侯琳熙，尹锡俊，龙能兵，杨沈激，张瑞丰: "大孔SO42-/ZrO2-SiO2复合固体酸制备及催化性能", 《无机化学学报》 * |
| 卢冠忠，苏勇，张顺海，毛东森: "固体超强酸SO42-/ZrO2-SiO2的制备及其催化性能的研究", 《石油化工高等学校学报》 * |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106631779A (en) * | 2016-08-31 | 2017-05-10 | 山东金昌树新材料科技有限公司 | Polyol ester and application of same to processing of halogenated vinyl polymer |
| CN106631806A (en) * | 2016-08-31 | 2017-05-10 | 山东金昌树新材料科技有限公司 | Mixed polyol ester and application thereof to halogenated vinyl polymer processing |
| CN106631779B (en) * | 2016-08-31 | 2020-07-14 | 济南金昌树新材料科技有限公司 | Polyol esters and their use in processing halogenated vinyl polymers |
| CN106631806B (en) * | 2016-08-31 | 2020-07-14 | 济南金昌树新材料科技有限公司 | Mixed polyol esters and their use in processing halogenated vinyl polymers |
| CN106966905A (en) * | 2017-05-05 | 2017-07-21 | 广州嘉德乐生化科技有限公司 | A kind of preparation method of pentaerythrite tristearate |
| CN107501092A (en) * | 2017-08-21 | 2017-12-22 | 大连理工大学 | A kind of method that continuous decompression catalytic distillation prepares pentaerythrite ester base oil |
| CN108191650A (en) * | 2017-12-25 | 2018-06-22 | 江苏雷蒙新材料有限公司 | A kind of preparation method of pentaerythrite tetra-acetate |
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