CN107641107B - Diacetyl epoxy glyceryl undecanoate and preparation method and application thereof - Google Patents
Diacetyl epoxy glyceryl undecanoate and preparation method and application thereof Download PDFInfo
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Abstract
The diacetyl epoxy glyceryl undecanoate has good compatibility with PVC, and the epoxy end group has good reaction activity, can generate reactive plasticization with high polymer materials containing hydroxyl end groups or carboxyl end groups such as PLA, PBAT and the like in the melt blending process, and is a novel, safe and environment-friendly plasticizer. The invention synthesizes diacetyl epoxy glyceryl undecanoate from undecylenic acid, firstly, vegetable oil and glycerol are subjected to ester exchange under the action of a catalyst to obtain undecylenic acid monoglyceride, then, diacetyl glyceryl undecanoate is synthesized by acetylation, and finally, the diacetyl epoxy glyceryl undecanoate is synthesized by epoxidation reaction in the environment of formic acid and hydrogen peroxide. The diacetyl epoxy glyceryl undecanoate prepared by the method has wide application prospect in the fields of PVC medical materials and biodegradable plastics.
Description
Technical Field
The invention relates to diacetyl epoxy glyceryl undecanoate, a preparation method and application thereof, and particularly has wide application prospect in the fields of PVC medical materials and biodegradable plastics.
Background
The plasticizer is one of important components in plastic processing and modification, and has the effects of improving the processing performance, improving the flexibility of the material and the like. The plasticizer extends into the macromolecular chains to reduce the acting force between the macromolecular chains and reduce the viscosity of the polymer, thereby improving the processing performance; the addition of the plasticizer can generate a solvation effect with macromolecules, and the glass transition temperature of the polymer is reduced, so that the flexibility of the material is improved.
China is a world-wide plastic processing and consumption country and also a world-wide plasticizer consumption country. In recent years, the consumption of plasticizers has been increasing by 10% or more per year. From the field of plasticizer use, polyvinyl chloride (PVC) is one of the most plasticizer-consuming varieties. In addition, with the widespread use of biodegradable materials such as polylactic acid (PLA), polybutylene adipate terephthalate (PBAT), the annual growth of plasticizers for such plastics has increased year by year with great market potential.
The earliest used o-benzene plasticizers (mainly DEHP) had the advantages of high plasticizing efficiency, good heat resistance, and low cost. However, research in this year finds that DEHP may cause problems such as liver carcinogenesis, female pregnancy rate decrease, infant growth retardation and peripheral nervous system damage, and the european and american countries gradually forbid the use of DEHP for PVC medical materials. The use of PVC infusion bags in China is stopped in 1999, and countries such as Europe and America gradually limit the use of PVC infusion bags in the fields of food packaging and the like.
Therefore, research and development of safe and environment-friendly novel plasticizers have important application value. At present, the synthesis and application of epoxy esters, citric acid esters, glycol benzoates, adipates, trioctyl trimellitate and high-molecular plasticizers have been developed.
Epoxidized Soybean Oil (ESO) has poor compatibility with PVC, the addition amount is not too high, when the dosage exceeds 45phr, the transparency of the material is poor, and the mechanical property of the product is rapidly deteriorated along with the precipitation of ESO. Acetyl tributyl citrate (ATBC), which has a small molecular weight and limited compatibility with PVC, is easy to separate out and migrate during the use of PVC plasticized by the ATBC. Dibenzoates such as diethylene glycol dibenzoate (DEDB) have a freezing point of 25 ℃ and are gels in winter, directly affecting storage and use; the acid value is high, the chroma is deep, and the product appearance is not good. Cyclohexanedicarboxylates such as DINCH are expensive, have low cost performance when used for PVC plasticization, and have insufficient product competitiveness. Trioctyl trimellitate (TOTM) raw material may be brought into or a trace amount of DEHP may be generated during the production process, and the biological safety is difficult to be ensured.
The existing plasticizer is mainly researched and designed aiming at PVC, and is not ideal for the plasticizing effect of biodegradable plastics such as PLA, PBAT and the like. For example, epoxy ester plasticizers such as diacetyl epoxy vegetable oil acid glyceride, diacetic epoxy vegetable oil acid glyceride and the like are superior to epoxy groups in the middle of a molecular chain, and have poor reaction activity, so that the epoxy ester plasticizers are not ideal for plasticizing polymers with active terminal hydroxyl or terminal carboxyl, such as PLA, PBAT and the like. Polyethylene glycol (PEG) and PLA are not good in compatibility and easy to precipitate, so that the problems of poor material performance, poor transparency and the like are caused. Therefore, the research and synthesis of the epoxidized fatty acid ester plasticizer with the epoxy group at the end can overcome the defects of the existing plasticizer and achieve the ideal plasticizing effect.
Disclosure of Invention
Aiming at the defects of the existing plasticizer, the invention designs a fatty acid ester plasticizer with epoxy end groups and a preparation method thereof, and the principle is that 10-undecylenic acid and glycerol (glycerol) are subjected to esterification reaction under the action of a catalyst to obtain undecylenic acid glyceride, then the undecylenic acid glyceride is synthesized by acetylation, and finally the acetyl epoxy undecylenic acid glyceride is synthesized by epoxidation reaction in the environment of formic acid and hydrogen peroxide.
To achieve the above object, the present invention provides diacetyl epoxy glyceryl undecanoate, which has a structural formula shown in formula (I) or (II):
the invention also provides a preparation method of diacetyl epoxy glyceryl undecanoate, and the preparation method of the formula (I) comprises the following steps:
(1) transesterification reaction
(2) Acetylation reaction
(3) Epoxidation reaction
The preparation method of the formula (II) comprises the following steps:
(1) transesterification reaction
(2) Acetylation reaction
(3) Epoxidation reaction
Furthermore, the molar ratio of the glycerol to the undecylenic acid in the transesterification reaction is preferably 1.0-1.1: 1, the reaction temperature is preferably 60-100 ℃, and the reaction time is preferably 1-3 h.
Further, it is preferable that the catalyst in the transesterification is selected from one or a mixture of two or more of tetrabutyl titanate, isobutyl titanate, tetramethyl titanate and tetraisopropyl titanate in any ratio, and the molar ratio of the catalyst to undecylenic acid is 1: 2000-10000.
Further, acetic acid in the acetylation reaction is preferably glacial acetic acid, the molar ratio of the glacial acetic acid to the undecylenic acid monoglyceride is 2-2.5: 1, the glacial acetic acid can be replaced by acetic anhydride, the reaction temperature is preferably 50-60 ℃, and the reaction time is preferably 1-5 h.
Further, the catalyst in the acetylation reaction is preferably one or a mixture of more than two of sulfuric acid, p-toluenesulfonic acid and acidic ion exchange resin in any proportion, and the molar ratio of the catalyst to the undecylenic acid monoglyceride is 1: 1000-2000.
Further, preferably, hydrogen peroxide, inorganic acid and a catalyst are added in the epoxidation reaction, wherein the molar ratio of the undecylenic acid monoglyceride, the hydrogen peroxide, the inorganic acid and the catalyst is 1:0.4-0.7:0.04-0.08: 0.001-0.003; the reaction temperature is preferably 60-70 ℃, and the reaction time is preferably 3-4 h.
Further, preferably, the inorganic acid is formic acid or acetic acid, and the catalyst is sulfuric acid or phosphoric acid.
The invention also provides the application of the diacetyl epoxy glyceryl undecanoate in plasticized polyvinyl chloride (PVC), polylactic acid (PLA) and Polycaprolactone (PCL).
The diacetyl epoxy undecylenic acid glyceride is used for plasticizing PVC, PLA and PCL, the addition amount of the diacetyl epoxy undecylenic acid glyceride is 5-40%, and the diacetyl epoxy undecylenic acid glyceride can be prepared by a melt mixing method.
The melting and mixing can be carried out by adopting an internal mixer, a double-screw extruder and a double-screw extruder, and the mixing temperature is 150-200 ℃.
The melting and mixing can also be carried out by adopting a reaction kettle, the kettle temperature is controlled to be 160-200 ℃, and the mixing time is 5-30 min.
The obtained material is subjected to injection molding by an injection molding machine at 190 ℃ to obtain a standard sample plate or a mechanical sample strip, and the corresponding physical and chemical properties are tested.
Compared with the prior art, the invention has the following technical effects:
(1) titanate is used as a catalyst in the ester exchange process, so that the method has the characteristics of mild reaction conditions and high catalytic efficiency;
(2) the molecular distillation technology is adopted, so that the low molecular content in the product is effectively reduced, and the purity of the product is improved;
(3) the prepared diacetyl epoxy glyceryl undecanoate has epoxy end groups and stronger reaction activity, and polylactic acid and polycaprolactone plasticized by the diacetyl epoxy glyceryl undecanoate have high tensile strength and elongation at break, remarkably improved notch impact strength and greatly reduced mobility.
Detailed Description
The above and further features and advantages of the present invention are explained in more detail below with reference to examples.
Example 1
Adding 180g of undecylenic acid, 90g of glycerol (the molar ratio of the undecylenic acid to the glycerol is about 1:1) and 0.034g of tetrabutyl titanate into a reaction vessel, and carrying out transesterification reaction in a constant-temperature magnetic stirrer at 90-100 ℃ and at a stirring speed of 200rpm for 2-3 h. Then adding 120g of glacial acetic acid, and reacting for 4-5 h at 50-60 ℃. Finally 10g of hydrogen peroxide (H) are added2O2) 2.3g of formic acid and 0.1g of sulfuric acid, and reacting for 3-4 hours at the temperature of 60-70 ℃. Separating lower layer acid water, washing upper layer oil ester with alkaline water and water successively to neutrality, and acid value below 0.6. The reaction product was purified by two-stage molecular distillation: the first molecular distillation purification is carried out under the pressure of 100Pa and the evaporation temperature of 120 ℃, and the second molecular distillation purification is carried out under the pressure of 10Pa and the evaporation temperature of 150 ℃. Collecting the second-stage molecular distillation light phase to obtain the diacetic acid epoxy undecanoic acid glyceride. The acid value was found to be 0.2, the epoxy value 2.2 and the iodine value 2.5.
Example 2
Adding 180g of undecylenic acid, 90g of glycerol (the molar ratio of the undecylenic acid to the glycerol is about 1:1) and 0.013g of tetraisopropyl titanate into a reaction vessel, and carrying out transesterification reaction in a constant-temperature magnetic stirrer at 90-100 ℃ at a stirring speed of 500rpm for 2-3 h. Then 200g of acetic anhydride is added to react for 1-2h at the temperature of 50-60 ℃. Finally 10g of hydrogen peroxide (H) are added2O2) 2.3g of formic acid and 0.1g of phosphoric acid, and reacting for 3-4h at the temperature of 60-70 ℃. Separating lower layer acid water, washing upper layer oil ester with alkaline water and water successively to neutrality, and acid value below 0.6. The reaction product was purified by two-stage molecular distillation: the first molecular distillation purification is carried out under the pressure of 100Pa and the evaporation temperature of 120 ℃, and the second molecular distillation purification is carried out under the pressure of 10Pa and the evaporation temperature of 150 ℃. Collecting the second-stage molecular distillation light phase to obtain the diacetic acid epoxy undecanoic acid glyceride. Is detected byThe acid value was 0.18, the epoxy value was 2.3 and the iodine value was 2.2.
Example 3
Adding 180g of undecylenic acid, 90g of glycerol (the molar ratio of the undecylenic acid to the glycerol is about 1:1), 0.0065g of tetraisopropyl titanate and 0.0015 g of tetramethyl titanate into a reaction vessel, and carrying out transesterification reaction for 2-3h in a constant-temperature magnetic stirrer at the temperature of 90-100 ℃ at the stirring speed of 300 rpm. Then 200g of acetic anhydride is added to react for 1-2h at the temperature of 50-60 ℃. Finally 10g of hydrogen peroxide (H) are added2O2) 2.3g of acetic acid and 0.1g of sulfuric acid, and reacting for 3-4 hours at the temperature of 60-70 ℃. Separating lower layer acid water, washing upper layer oil ester with alkaline water and water successively to neutrality, and acid value below 0.6. The reaction product was purified by two-stage molecular distillation: the first molecular distillation purification is carried out under the pressure of 100Pa and the evaporation temperature of 120 ℃, and the second molecular distillation purification is carried out under the pressure of 10Pa and the evaporation temperature of 150 ℃. Collecting the second-stage molecular distillation light phase to obtain the diacetic acid epoxy undecanoic acid glyceride. The acid value was found to be 0.26, the epoxy value was 2.4 and the iodine value was 2.3.
Example 4
Adding 180g of undecylenic acid, 90g of glycerol (the molar ratio of the undecylenic acid to the glycerol is about 1:1) and 0.17g of isobutyl titanate into a reaction vessel, and carrying out transesterification reaction in a constant-temperature magnetic stirrer at the temperature of 60-70 ℃ and at the stirring speed of 200rpm for 1-2 h. Then adding 120g of glacial acetic acid, and reacting for 4-5 h at 50-60 ℃. Finally 10g of hydrogen peroxide (H) are added2O2) 2.3g of formic acid and 0.1g of sulfuric acid, and reacting for 3-4 hours at the temperature of 60-70 ℃. Separating lower layer acid water, washing upper layer oil ester with alkaline water and water successively to neutrality, and acid value below 0.6. The reaction product was purified by two-stage molecular distillation: the first molecular distillation purification is carried out under the pressure of 100Pa and the evaporation temperature of 120 ℃, and the second molecular distillation purification is carried out under the pressure of 10Pa and the evaporation temperature of 150 ℃. Collecting the second-stage molecular distillation light phase to obtain the diacetic acid epoxy undecanoic acid glyceride. The acid value was found to be 0.25, the epoxy value was 2.1 and the iodine value was 2.4.
Example 5
And accurately weighing 95 parts by weight of PVC and 5 parts by weight of diacetyl epoxidized fatty acid glyceride. Then the components are melted, mixed and extruded for granulation by a single screw extruder; the temperature of the heating zone of the extruder from the feed opening to the head is set as follows: 130 deg.C, 150 deg.C, and 250 rpm.
Example 6
Accurately weighing 80 parts by weight of PLA and 20 parts by weight of diacetyl epoxidized fatty glyceride. And then, melting and mixing the components by using a reaction kettle, wherein the temperature of the reaction kettle is set to be 190 ℃, the stirring speed is 50rpm, and the mixing time is 20 minutes.
Example 7
Accurately weighing 60 parts by weight of PCL and 40 parts by weight of diacetyl epoxidized fatty acid glyceride. Then melting and mixing the components by a double-screw extruder, extruding and granulating; the temperature of the heating zone of the extruder from the feed opening to the head is set as follows: 130 deg.C, 150 deg.C, 160 deg.C, 170 deg.C, 180 deg.C, 400 rpm. .
Comparative example 1
Accurately weighing 80 parts by weight of PLA and 20 parts by weight of glycerol. And then, melting and mixing the components by using a reaction kettle, wherein the temperature of the reaction kettle is set to be 190 ℃, the stirring speed is 50rpm, and the mixing time is 20 minutes.
Example 2
80 parts by weight of PLA and 20 parts by weight of polyethylene glycol (PEG 2000) were accurately weighed. And then, melting and mixing the components by using a reaction kettle, wherein the temperature of the reaction kettle is set to be 190 ℃, the stirring speed is 50rpm, and the mixing time is 20 minutes.
Example 3
80 parts by weight of PCL and 20 parts by weight of polyethylene glycol (PEG 2000) were weighed out accurately. And then, melting and mixing the components by using a reaction kettle, wherein the temperature of the reaction kettle is set to be 190 ℃, the stirring speed is 50rpm, and the mixing time is 20 minutes.
The plasticized material was injection molded with an injection molding machine at 190 ℃ using a standard template or mechanical spline, and the corresponding physical and chemical properties were measured as follows, with the results shown in Table 1.
The melt index was measured according to GB 3682-2000 with a temperature of 170 ℃ and a load of 5 Kg.
The tensile strength and elongation at break were carried out in accordance with GB 1040 at a tensile rate of 100 mm/min.
Impact Strength according to GB 1843
And (3) testing the migration quantity: firstly, pressing a PVC plasticizing material into a sheet by using a hot-pressing forming machine, wherein the process conditions are as follows: preheating at 180 ℃ for 5min, hot-pressing for 1min, and cooling for 3min to prepare a sheet with the thickness of 0.4-0.6 mm; (ii) a Placing the sheets at normal temperature for 168 hours respectively, weighing and soaking in deionized water at 60 ℃ for 48 hours respectively; thirdly, the soaked sheet is sucked dry by filter paper, then is dried for 24 hours in a vacuum drying oven at the temperature of 60 ℃, and then is weighed, the mass change percentage before and after soaking is calculated, the migration quantity is calculated, and the migration resistance of the plasticizer is evaluated.
Table 1 results of performance testing
| Item | Example 5 | Example 6 | Example 7 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| MFI(g/10min) | 4.5 | 8.2 | 9.3 | 6.8 | 8.4 | 10.2 |
| Tensile Strength (MPa) | 34.2 | 32.5 | 8.2 | 16.5 | 18.2 | 5.2 |
| Elongation at Break (%) | 124 | 285 | 520 | 32 | 95 | 438 |
| Notched impact Strength (KJ/m)2) | 3.5 | 12.8 | Continuously, continuously | 2.1 | 3.2 | Continuously, continuously |
| Migration amount (%) | 0.11 | 0.32 | 0.53 | 6.25 | 3.26 | 8.36 |
From the test results in table 1, it can be seen that the tensile strength, elongation at break and notched impact strength of the plasticized PLA and PCL using the present invention migrate much less than glycerin or polyethylene glycol in the blended material due to the material plasticized by glycerin and polyethylene glycol.
The above-mentioned embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solution of the present invention by those skilled in the art should fall within the protection scope defined by the claims of the present invention without departing from the spirit of the present invention.
Claims (10)
1. A diacetyl epoxy glyceryl undecanoate is characterized in that its structural formula is as shown in formula (I) or (II):
2. a process for the preparation of diacetylepoxyundecanoic acid esters according to claim 1, wherein the process for the preparation of formula (i) comprises the steps of:
(1) transesterification reaction
(2) Acetylation reaction
(3) Epoxidation reaction
3. A process for the preparation of diacetylepoxyundecanoic acid esters according to claim 1, wherein the process for the preparation of formula (ii) comprises the steps of:
(1) transesterification reaction
(2) Acetylation reaction
(3) Epoxidation reaction
4. The method for producing diacetyl epoxy glyceryl undecanoate according to claim 2 or 3, wherein: the molar ratio of the glycerol to the undecylenic acid in the ester exchange reaction is 1.0-1.1: 1, the reaction temperature is 60-100 ℃, and the reaction time is 1-3 h.
5. The method for producing diacetyl epoxy glyceryl undecanoate according to claim 2 or 3, wherein: the catalyst in the ester exchange reaction is selected from one or a mixture of more than two of tetrabutyl titanate, isobutyl titanate, tetramethyl titanate and tetraisopropyl titanate in any proportion, and the molar ratio of the catalyst to the undecylenic acid is 1: 2000-10000.
6. The method for producing diacetyl epoxy glyceryl undecanoate according to claim 2 or 3, wherein: in the acetylation reaction, acetic acid is glacial acetic acid, the molar ratio of the glacial acetic acid to the undecylenic acid monoglyceride is 2-2.5: 1, the glacial acetic acid can be replaced by acetic anhydride, the reaction temperature is 50-60 ℃, and the reaction time is 1-5 h.
7. The method for producing diacetyl epoxy glyceryl undecanoate according to claim 2 or 3, wherein: the catalyst in the acetylation reaction is one or a mixture of more than two of sulfuric acid, p-toluenesulfonic acid and acidic ion exchange resin in any proportion, and the molar ratio of the catalyst to the undecylenic acid monoglyceride is 1: 1000-2000.
8. The method for producing diacetyl epoxy glyceryl undecanoate according to claim 2 or 3, wherein: hydrogen peroxide, formic acid or acetic acid, a catalyst and undecylenic acid monoglyceride are added in the epoxidation reaction: hydrogen peroxide: formic acid or acetic acid: the catalyst is 1:0.4-0.7:0.04-0.08:0.001-0.003 in molar ratio; the reaction temperature is 60-70 ℃, and the reaction time is 3-4 h.
9. The method for producing diacetyl epoxy glyceryl undecanoate according to claim 8, wherein: the catalyst is sulfuric acid or phosphoric acid.
10. Use of diacetyl epoxy glyceryl undecanoate according to claim 1 for plasticising polyvinyl chloride, polylactic acid, polycaprolactone.
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| CN1960962A (en) * | 2003-08-12 | 2007-05-09 | 拜奥资源美国公司 | Method of making alkyl esters using glycerin |
| CN102285946A (en) * | 2011-06-28 | 2011-12-21 | 广州市海珥玛植物油脂有限公司 | Diacetyl epoxy glyceryl oleates and synthesis method thereof |
| CN103483296A (en) * | 2013-09-23 | 2014-01-01 | 广州市海珥玛植物油脂有限公司 | Synthesis process of diacetyl epoxy glyceryl oleate |
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| CN1960962A (en) * | 2003-08-12 | 2007-05-09 | 拜奥资源美国公司 | Method of making alkyl esters using glycerin |
| CN102285946A (en) * | 2011-06-28 | 2011-12-21 | 广州市海珥玛植物油脂有限公司 | Diacetyl epoxy glyceryl oleates and synthesis method thereof |
| CN103483296A (en) * | 2013-09-23 | 2014-01-01 | 广州市海珥玛植物油脂有限公司 | Synthesis process of diacetyl epoxy glyceryl oleate |
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