CN107641107A - Diacetyl epoxy undecanoic acid glyceride and its preparation method and application - Google Patents
Diacetyl epoxy undecanoic acid glyceride and its preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of diacetyl epoxy undecanoic acid glyceride and its preparation method and application; diacetyl epoxy undecanoic acid glyceride and PVC compatibility are good; its is epoxy-terminated to have good reactivity; it can be plasticized during melt blending with PLA, PBAT etc. containing the reacting property of high polymer material of terminal hydroxy group or end carboxyl, be a kind of new, safe and environment-friendly plasticizer.The present invention is from undecenoic acid synthesis of diacetyl epoxy undecanoic acid glyceride; ester exchange is carried out under catalyst action with vegetable oil and glycerine first; obtain undecenoic acid monoglyceride; then acetylation synthesis of diacetyl undecenoic acid glyceride again; epoxidation reaction is finally carried out in the environment of formic acid and hydrogen peroxide, synthesis obtains diacetyl epoxy undecanoic acid glyceride.The diacetyl epoxy undecanoic acid glyceride that the present invention is prepared is with a wide range of applications in PVC medical materials, biodegradable plastic field.
Description
Technical field
The present invention relates to a kind of diacetyl epoxy undecanoic acid glyceride and its preparation method and application, is particularly cured in PVC
It is with a wide range of applications with material, biodegradable plastic field.
Background technology
Plasticizer be plastic processing with it is modified in one of important component, having improves processing characteristics and improves the soft of material
Property and other effects.Between plasticizer is by going deep into macromolecular chain, reduce the active force between macromolecular chain, reduce the viscous of polymer
Degree, so as to improve processing characteristics；Solvation effect can occur between macromolecular for the addition of plasticizer, reduce the glass of polymer
Change transition temperature, so as to improve the pliability of material.
China is plastic processing in the world and consumption big country, and plasticizer consumption big country in the world.In recent years, increase
The consumption for moulding agent keeps average annual more than 10% growth.In terms of the application field of plasticizer, polyvinyl chloride (PVC) is that consumption increases
Mould one of maximum kind of agent dosage.In addition, with Biodegradable material such as PLA (PLA), polyadipate/terephthaldehyde
The extensive use of sour fourth diester (PBAT), the annual increment for the plasticizer of such plastics increase year by year, and market potential is huge.
The adjacent benzene class plasticizer (mainly DEHP) used earliest has plasticizing efficiency height, heat resistance good and cheap
The advantages that.However, the research in this year finds that DEHP may cause carcinogenic liver, the decline of women pregnancy rate, infant development slow
The problems such as being damaged with peripheral neverous system, American-European countries progressively forbid being used for PVC medical materials.China's PVC infusion bags are in 1999
Year is stopped using, and the country such as America and Europe progressively limits its use in fields such as packagings for foodstuff.
Therefore, researching and developing safe and environment-friendly new plasticizer has important application value.At present, carried out
Epoxy ester series, citric acid ester type, dihydric alcohol benzoates, adipic acid esters, trioctyl trimellitate (TOTM), polymeric plasticizer
Synthesis and application.
The compatibility of epoxidized soybean oil (ESO) and PVC is bad, and addition can not be too high, the material when its dosage is more than 45phr
The transparency of material is poor, and the mechanical property of product is deteriorated rapidly with ESO precipitation.Tributyl 2-acetylcitrate (ATBC), molecule
Amount is smaller, with PVC limited compatibilities, the precipitation of plasticizer easily occurs in use with the PVC of its plasticising and migrates ratio
It is more serious.The freezing point of dibenzoic acid esters such as Diethylene Glycol Dibenzoate (DEDB) is 25 DEG C, is in the winter time gel
Body, directly affect storage and use；Its acid number is high, and colourity is deep, and product appearance is bad.Cyclohexane diacid esters such as DINCH valency
Lattice are higher, and cost performance is not high when being plasticized for PVC, product competitiveness deficiency.Trioctyl trimellitate (TOTM) (TOTM) raw material may
Bring into or production process in there may be micro DEHP, biological safety to be difficult to ensure that.
Existing plasticizer is studied and designed mainly for PVC, the increasing for biodegradable plastics such as PLA and PBAT
It is unsatisfactory to mould effect.Such as epoxy ester series plasticizer such as diacetyl epoxidized vegetable oil acid glyceride, oxalic acid epoxidized vegetable oil acid
Glyceride etc., better than epoxy radicals at the middle part of strand, reactivity is bad, for being plasticized the active end such as PLA and PBAT
The polymer of hydroxyl or end carboxyl is unsatisfactory.Polyethylene glycol (PEG) and PLA compatibilities are bad, easily separate out, cause material
The problems such as energy is deteriorated, transparency is bad.Therefore, research and synthesizing epoxy base, can in the epoxidized fatty acid ester plasticizer of end
Overcome the shortcomings of existing plasticizer, reach preferable plasticization effect.
The content of the invention
For the deficiency of existing plasticizer, present invention design is a kind of to have epoxy-terminated fatty acid ester plasticizer and its system
Preparation Method, its principle are that esterification is carried out under catalyst action with glycerine (glycerine) using 10 hendecenoic acid, obtain ten
Monoenoic acid glyceride, then acetylation synthesis of diacetyl undecenoic acid glyceride again, finally in the environment of formic acid and hydrogen peroxide
Epoxidation reaction is carried out, synthesis obtains acetyl epoxy undecanoic acid glyceride.
For the above-mentioned purpose, a kind of diacetyl epoxy undecanoic acid glyceride of the present invention, its structural formula such as formula (I) or (II)：
The present invention also provides a kind of preparation method of diacetyl epoxy undecanoic acid glyceride, and the preparation method of formula (I) includes
Following steps：
(1) ester exchange reaction
(2) acetylization reaction
(3) epoxidation reaction
The preparation method of formula (II) comprises the following steps：
(1) ester exchange reaction
(2) acetylization reaction
(3) epoxidation reaction
Further, it is 1.0~1.1 as the mol ratio of glycerine and undecenoic acid in the preferred ester exchange reaction:1,
Preferred 60-100 DEG C of reaction temperature, reaction time preferred 1-3h.
Further, as catalyst described in the preferred ester exchange reaction be selected from butyl titanate, iso-butyl titanate,
Tetramethoxy titanate ester, tetraisopropyl titanate one or more kinds of arbitrary proportions mixture, catalyst and undecenoic acid mole
The 1 of ratio:2000-10000.
Further, it is glacial acetic acid as acetic acid in the preferred acetylization reaction, itself and undecenoic acid list glyceride
Mol ratio is 2~2.5:1, the glacial acetic acid can replace with acetic anhydride, and preferred 50-60 DEG C of reaction temperature, the reaction time is preferred
1-5h。
Further, sulfuric acid, p-methyl benzenesulfonic acid, acid ion is selected from as catalyst in the preferred acetylization reaction to hand over
Change the mixture of one or both of resin any of the above ratio, the mol ratio of catalyst and undecenoic acid monoglyceride is 1:
1000-2000。
Further, as addition hydrogen peroxide, inorganic acid and catalyst in the preferred epoxidation reaction, undecenoic acid list
Glyceride: hydrogen peroxide: inorganic acid: catalyst=1:0.4-0.7:0.04-0.08:0.001-0.003, mol ratio；Reaction temperature
It is preferred that 60-70 DEG C, reaction time preferred 3-4h.
Further, it is formic acid or acetic acid as the preferred inorganic acid, catalyst is sulfuric acid or phosphoric acid.
The present invention also provides diacetyl epoxy undecanoic acid glyceride in plasticised polyvinyl chloride (PVC), PLA (PLA) and gathered
Application in terms of caprolactone (PCL).
Diacetyl epoxy undecanoic acid glyceride is used for PVC, PLA and PCL plasticising, its addition to be 5~40%, can be with
Carried out using the method for melting mixing.
Melting mixing can use banbury, double screw extruder, double screw extruder to carry out, melting temperature 150~200
℃。
Melting mixing can also use reactor to carry out, and kettle temperature control is at 160~200 DEG C, 5~30min of incorporation time.
Resulting materials are molded standard jig or mechanics batten using injection moulding machine at 190 DEG C, test corresponding physics and chemistry
Energy.
The invention difference from existing technology is that the present invention achieves following technique effect：
(1) Exchange Ester Process uses titanate esters as catalyst, has the characteristics of reaction condition is gentle, high catalytic efficiency；
(2) molecular distillation technique is used, effectively reduces the low molecule content in product, improves the purity of product；
(3) the diacetyl epoxy undecanoic acid glyceride prepared by has epoxy-terminated, has stronger reactivity, uses it
The PLA of plasticising and the tensile strength of polycaprolactone and elongation at break height, notch impact strength significantly improve, and mobility is big
Amplitude reduction.
Embodiment
With reference to embodiments, the forgoing and additional technical features and advantages are described in more detail.
Embodiment 1
Undecenoic acid 180g is added in reaction vessel, (mol ratio of the two is about 1 to glycerine 90g:1), 0.034g metatitanic acids
Four butyl esters, ester exchange reaction 2-3h is carried out with 200rpm mixing speed in 90~100 DEG C of constant temperature blender with magnetic force.Then
120g glacial acetic acid is added, 4~5h is reacted under conditions of 50~60 DEG C.Finally add 10g hydrogen peroxide (H2O2)、2.3g
Formic acid, 0.1g sulfuric acid, under conditions of 60~70 DEG C react 3~4h.Separate lower floor's sour water, upper strata grease priority alkali
Water, neutrality is washed to, acid number is below 0.6.Reaction product purifies through two-stage molecular distillation：The bar of first order molecular distillation purifying
Part is that pressure is 100Pa, and evaporating temperature is 120 DEG C, and the condition of second level molecular distillation purifying is that pressure is 10Pa, evaporating temperature
For 150 DEG C.Second level molecular distillation light phase is collected, that is, is obtained with oxalic acid epoxy undecanoic acid glyceride.Its acid number is after testing
0.2, epoxide number 2.2, iodine number 2.5.
Embodiment 2
Undecenoic acid 180g is added in reaction vessel, (mol ratio of the two is about 1 to glycerine 90g:1), 0.013g metatitanic acids
Four isopropyl esters, ester exchange reaction 2-3h is carried out with 500rpm mixing speed in 90~100 DEG C of constant temperature blender with magnetic force.So
200g acetic anhydride is added afterwards, and 1~2h is reacted under conditions of 50~60 DEG C.Finally add 10g hydrogen peroxide (H2O2)、
2.3g formic acid, 0.1g phosphoric acid, 3~4h is reacted under conditions of 60~70 DEG C.Lower floor's sour water is separated, upper strata grease is successively used
Buck, neutrality is washed to, acid number is below 0.6.Reaction product purifies through two-stage molecular distillation：First order molecular distillation purifying
Condition is that pressure is 100Pa, and evaporating temperature is 120 DEG C, and the condition of second level molecular distillation purifying is that pressure is 10Pa, evaporation temperature
Spend for 150 DEG C.Second level molecular distillation light phase is collected, that is, is obtained with oxalic acid epoxy undecanoic acid glyceride.Its acid number after testing
For 0.18, epoxide number 2.3, iodine number 2.2.
Embodiment 3
Undecenoic acid 180g is added in reaction vessel, (mol ratio of the two is about 1 to glycerine 90g:1), 0.0065g metatitanic acids
Four isopropyl esters, 0.0015 tetramethoxy titanate ester, carried out in 90~100 DEG C of constant temperature blender with magnetic force with 300rpm mixing speed
Ester exchange reaction 2-3h.Then 200g acetic anhydride is added, 1~2h is reacted under conditions of 50~60 DEG C.Finally add 10g's
Hydrogen peroxide (H2O2), 2.3g acetic acid, 0.1g sulfuric acid, under conditions of 60~70 DEG C react 3~4h.Lower floor's sour water is separated,
Upper strata grease priority buck, neutrality is washed to, acid number is below 0.6.Reaction product purifies through two-stage molecular distillation：The first order
The condition of molecular distillation purifying is that pressure is 100Pa, and evaporating temperature is 120 DEG C, and the condition of second level molecular distillation purifying is pressure
Strong is 10Pa, and evaporating temperature is 150 DEG C.Second level molecular distillation light phase is collected, that is, is obtained with oxalic acid epoxy undecanoic acid glycerine
Ester.Its acid number is 0.26 after testing, epoxide number 2.4, iodine number 2.3.
Embodiment 4
Undecenoic acid 180g is added in reaction vessel, (mol ratio of the two is about 1 to glycerine 90g:1), 0.17g metatitanic acids are different
Butyl ester, ester exchange reaction 1-2h is carried out with 200rpm mixing speed in 60~70 DEG C of constant temperature blender with magnetic force.Then add
Add 120g glacial acetic acid, 4~5h is reacted under conditions of 50~60 DEG C.Finally add 10g hydrogen peroxide (H2O2), 2.3g
The sulfuric acid of formic acid, 0.1g, 3~4h is reacted under conditions of 60~70 DEG C.Separate lower floor's sour water, upper strata grease successively with buck,
Neutrality is washed to, acid number is below 0.6.Reaction product purifies through two-stage molecular distillation：The condition of first order molecular distillation purifying
It is 100Pa for pressure, evaporating temperature is 120 DEG C, and the condition of second level molecular distillation purifying is that pressure is 10Pa, and evaporating temperature is
150℃.Second level molecular distillation light phase is collected, that is, is obtained with oxalic acid epoxy undecanoic acid glyceride.Its acid number is after testing
0.25, epoxide number 2.1, iodine number 2.4.
Embodiment 5
Accurately weigh 95 parts by weight PVC, 5 parts by weight diacetyl epoxidized fat acid glycerides.Then said components are adopted
Melt mixing, extruding pelletization with single screw extrusion machine；Temperature of the extruder heating zone from feed opening to head is set as successively：130
DEG C, 150 DEG C, 150 DEG C, 150 DEG C, 150 DEG C, 150 DEG C, rotating speed 250rpm.
Embodiment 6
Accurately weigh 80 parts by weight PLA, 20 parts by weight diacetyl epoxidized fat acid glycerides.Then said components are adopted
Melting mixing is carried out with reactor, the temperature of reactor sets 190 DEG C, mixing speed 50rpm, incorporation time 20 minutes.
Embodiment 7
Accurately weigh 60 parts by weight PCL, 40 parts by weight diacetyl epoxidized fat acid glycerides.Then said components are adopted
Melt mixing, extruding pelletization with double screw extruder；Temperature of the extruder heating zone from feed opening to head is set as successively：130
DEG C, 150 DEG C, 160 DEG C, 170 DEG C, 180 DEG C, 180 DEG C, rotating speed 400rpm..
Comparative example 1
Accurately weigh 80 parts by weight PLA, 20 parts by weight of glycerin.Then it is mixed said components to be subjected to melting using reactor
Close, the temperature of reactor sets 190 DEG C, mixing speed 50rpm, incorporation time 20 minutes.
Embodiment 2
Accurately weigh 80 parts by weight PLA, 20 parts by weight polyethylene glycol (PEG 2000).Then by said components using reaction
Kettle carries out melting mixing, and the temperature of reactor sets 190 DEG C, mixing speed 50rpm, incorporation time 20 minutes.
Embodiment 3
Accurately weigh 80 parts by weight PCL, 20 parts by weight polyethylene glycol (PEG 2000).Then by said components using reaction
Kettle carries out melting mixing, and the temperature of reactor sets 190 DEG C, mixing speed 50rpm, incorporation time 20 minutes.
Plastification material is molded standard jig or mechanics batten using injection moulding machine at 190 DEG C, tests as follows
Corresponding physicochemical property, acquired results are shown in Table 1.
Melt index is tested according to GB 3682-2000,170 DEG C of temperature, load 5Kg.
Tensile strength and elongation at break are carried out by GB 1040, rate of extension 100mm/min.
Impact strength is carried out according to GB 1843 method
Migration measures examination：1. PVC plastification materials are suppressed into thin slice using heat pressing forming machines, process conditions are：Temperature 180
DEG C, preheating 5min, hot pressing 1min, cooling 3min, prepare the sheet material of thickness 0.4~0.6mm thickness；；2. by above-mentioned sheet material normal
168h is placed under temperature respectively, soaks 48h in 60 DEG C of deionized waters respectively after weighing；3. the piece timber-used filter paper after immersion is inhaled
It is dry, weighed after then drying 24h in 60 DEG C of vacuum drying chamber, calculate the front and rear mass change percentage computation migration of immersion
Amount, evaluate the resistance to migration energy of plasticizer.
The performance test results of table 1
| Project | Embodiment 5 | Embodiment 6 | Embodiment 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 |
| Notch impact strength (KJ/m2) | 3.5 | 12.8 | Constantly | 2.1 | 3.2 | Constantly |
| Migration amount (%) | 0.11 | 0.32 | 0.53 | 6.25 | 3.26 | 8.36 |
It was found from the test result of table 1, using the PLA being plasticized and PCL of the invention tensile strength, elongation at break and lack
The material that mouth impact strength is plasticized due to glycerine and polyethylene glycol, the migration amount in intermingling material are far smaller than glycerine or poly- second
Glycol.
Embodiment described above is only that the preferred embodiment of the present invention is described, not to the model of the present invention
Enclose and be defined, on the premise of design spirit of the present invention is not departed from, technical side of the those of ordinary skill in the art to the present invention
The various modifications and improvement that case is made, it all should fall into the protection domain of claims of the present invention determination.
Claims (10)
1. a kind of diacetyl epoxy undecanoic acid glyceride, it is characterised in that its structural formula such as formula (I) or (II)：
A kind of 2. method for preparing diacetyl epoxy undecanoic acid glyceride as claimed in claim 1, it is characterised in that the system of formula (I)
Preparation Method comprises the following steps：
(1) ester exchange reaction
(2) acetylization reaction
(3) epoxidation reaction
A kind of 3. method for preparing diacetyl epoxy undecanoic acid glyceride as claimed in claim 1, it is characterised in that formula (II)
Preparation method comprises the following steps：
(1) ester exchange reaction
(2) acetylization reaction
(3) epoxidation reaction
4. the preparation method of diacetyl epoxy undecanoic acid glyceride according to Claims 2 or 3, it is characterised in that：The ester
The mol ratio of glycerine and undecenoic acid is 1.0~1.1 in exchange reaction:1, preferred 60-100 DEG C of reaction temperature, the reaction time is excellent
Select 1-3h.
5. the preparation method of diacetyl epoxy undecanoic acid glyceride according to Claims 2 or 3, it is characterised in that：The ester
Catalyst described in exchange reaction be selected from butyl titanate, iso-butyl titanate, tetramethoxy titanate ester, one kind of tetraisopropyl titanate or
The mixture of two or more arbitrary proportions, catalyst and the 1 of undecenoic acid mol ratio:2000-10000.
6. the preparation method of diacetyl epoxy undecanoic acid glyceride according to Claims 2 or 3, it is characterised in that：The second
Acetic acid is glacial acetic acid in acylation reaction, and the mol ratio of itself and undecenoic acid list glyceride is 2~2.5:1, the glacial acetic acid can
Replace with acetic anhydride, preferred 50-60 DEG C of reaction temperature, reaction time preferred 1-5h.
7. the preparation method of diacetyl epoxy undecanoic acid glyceride according to Claims 2 or 3, it is characterised in that：The second
Catalyst is selected from one or both of sulfuric acid, p-methyl benzenesulfonic acid, acid-exchange resin any of the above ratio in acylation reaction
The mol ratio of the mixture of example, catalyst and undecenoic acid monoglyceride is 1:1000-2000.
8. the preparation method of diacetyl epoxy undecanoic acid glyceride according to Claims 2 or 3, it is characterised in that：The ring
Hydrogen peroxide, inorganic acid and catalyst, undecenoic acid monoglyceride: hydrogen peroxide: inorganic acid: catalyst=1 are added in oxidation reaction:
0.4-0.7:0.04-0.08:0.001-0.003, mol ratio；Preferred 60-70 DEG C of reaction temperature, reaction time preferred 3-4h.
9. the preparation method of diacetyl epoxy undecanoic acid glyceride according to claim 8, it is characterised in that：The inorganic acid
For formic acid or acetic acid, catalyst is sulfuric acid or phosphoric acid.
10. diacetyl epoxy undecanoic acid glyceride is in polyvinyl chloride, PLA, polycaprolactone plasticising according to claim 1
The application of aspect.
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| CN201610575474.8A CN107641107B (en) | 2016-07-20 | 2016-07-20 | Diacetyl epoxy glyceryl undecanoate and preparation method and application thereof |
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| CN201610575474.8A CN107641107B (en) | 2016-07-20 | 2016-07-20 | Diacetyl epoxy glyceryl undecanoate and preparation method and application thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108659476A (en) * | 2018-05-21 | 2018-10-16 | 广州医科大学 | A kind of low-shrinkage 3D printing material and the preparation method and application thereof |
| CN109880206A (en) * | 2019-02-15 | 2019-06-14 | 广州赫尔普化工有限公司 | A kind of polyethylene plasticizer |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108659476A (en) * | 2018-05-21 | 2018-10-16 | 广州医科大学 | A kind of low-shrinkage 3D printing material and the preparation method and application thereof |
| CN108659476B (en) * | 2018-05-21 | 2020-09-04 | 广州医科大学 | Low-shrinkage 3D printing material and preparation method and application thereof |
| CN109880206A (en) * | 2019-02-15 | 2019-06-14 | 广州赫尔普化工有限公司 | A kind of polyethylene plasticizer |
| CN109880206B (en) * | 2019-02-15 | 2021-06-08 | 广州赫尔普化工有限公司 | Polyethylene plasticizer |
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| CN107641107B (en) | 2021-04-13 |
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Application publication date: 20180130 Assignee: NANTONG HAIERMA TECHNOLOGY Co.,Ltd. Assignor: GUANGZHOU HAIRMA CHEMICAL (GZ) Ltd. Contract record no.: X2021980012820 Denomination of invention: Diacetyl epoxy undecanoic acid glyceride and its preparation method and Application Granted publication date: 20210413 License type: Common License Record date: 20211123 |
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Effective date of registration: 20230412 Address after: 226010 No.1, Tongshun Road, Nantong Development Zone, Nantong City, Jiangsu Province Patentee after: NANTONG HAIERMA TECHNOLOGY Co.,Ltd. Address before: 510000 New Yagang Village, Shijingjie Street, Baiyun District, Guangzhou City, Guangdong Province, No. 1 Patentee before: GUANGZHOU HAIRMA CHEMICAL (GZ) Ltd. |