CN107176910B - A kind of acetylation citric acid aliphatic ester plasticizer and its preparation method and application - Google Patents
A kind of acetylation citric acid aliphatic ester plasticizer and its preparation method and application Download PDFInfo
- Publication number
- CN107176910B CN107176910B CN201710347591.3A CN201710347591A CN107176910B CN 107176910 B CN107176910 B CN 107176910B CN 201710347591 A CN201710347591 A CN 201710347591A CN 107176910 B CN107176910 B CN 107176910B
- Authority
- CN
- China
- Prior art keywords
- citric acid
- aliphatic ester
- acid
- preparation
- ester
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/31—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of functional groups containing oxygen only in singly bound form
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/24—Preparation of carboxylic acid esters by reacting carboxylic acids or derivatives thereof with a carbon-to-oxygen ether bond, e.g. acetal, tetrahydrofuran
- C07C67/26—Preparation of carboxylic acid esters by reacting carboxylic acids or derivatives thereof with a carbon-to-oxygen ether bond, e.g. acetal, tetrahydrofuran with an oxirane ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/38—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D303/40—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals by ester radicals
- C07D303/42—Acyclic compounds having a chain of seven or more carbon atoms, e.g. epoxidised fats
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/11—Esters; Ether-esters of acyclic polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Abstract
A kind of acetylation citric acid aliphatic ester plasticizer and its preparation method and application, including prepare epoxidized fatty acid ester；Citric acid and epoxidized fatty acid ester ring-opening reaction prepare citric acid aliphatic ester；Acetylization reaction obtains final products acetylation citric acid aliphatic ester plasticizer.The biology base plasticizer that the present invention is prepared using citric acid and aliphatic ester as primary raw material, raw material is cheap and easy to get, environmentally protective, while can reduce the dependence to fossil resources.Since molecular weight is larger, polarity linkage content is high and the presence of long aliphatic chain; flash-point height, resistance to precipitation property, cold resistance and plasticizing efficiency are more preferable compared with acetylation tributyl citrate and epoxy aliphatic acid methyl ester; the thermal stability that PVC product can be improved simultaneously, can also substitute DOP preparation completely has property PVC product.Present invention process is simple, mild condition, and not changing production equipment can be directly used for production to the plasticizer, is very suitable to industrialized production.
Description
Technical field
The invention belongs to can bio-based materials field, be related to a kind of environment-friendly type, biology base PVC plasticizer acetylation citric acid
The preparation method of aliphatic ester.
Background technique
Bio-based materials refer to using renewable biomass, including crops, trees and other plants and its residuum and interior
Inclusion is raw material, passes through a kind of new material of the means manufacture such as biology, chemistry and physics.It mainly include biological plastics, life
The products such as object based platform compound, biomass functional polymer material, function sugar product, the wooden base engineering material, have green, ring
The characteristic that border is friendly, raw material is renewable and biodegradable.The present invention with main material grease and citric acid belong to
Renewable biomass.Plasticizer, which is added in high molecular material, can change material plasticity, be allowed to more easily process, product is more soft
Soft plastic additive.China's plasticizer yield is up to million tons, wherein dioctyl phthalate (DOP), phthalic acid two
Butyl ester (DBP) etc. accounts for 80% or more containing the plasticizer of adjacent benzene class.However such plasticizer is queried with persistent reproduction poison
Property, cause the U.S., the multinational plaintext of Japan and European Union to forbid using in industries such as electronics, food, daily necessities and toys, in recent years,
As " plasticizing disturbance " accident takes place frequently, pay attention to day by day of the domestic society to plasticizer safety and the feature of environmental protection, non-neighboring benzene class ring
The market of guarantor's type plasticizer and dosage increasingly increase.
By nearly 40 years high speed developments, China's citric acid industry has had first scale of the whole world and advanced in the world
Technical level, annual export volume account for about the 80% of annual total output.Using in citric acid structure carboxyl and hydroxyl and other change
The excellent Biodegradable material of multiple performance can be prepared by closing object reaction, such as tributyl citrate (TBC), acetylation citric acid
Tributyl (TEC) etc. has excellent plasticization effect and good light resistance, water resistance, is asepsis environment-protecting plasticizer.Patent
(103242558A) discloses a kind of preparation method of acetyl tributyl citrate monoglyceride plasticizer, not only it is environment-protecting and non-poisonous degradation and be plasticized
It is more excellent with resistance to precipitation performance.But the flash-point of this kind of plasticizer is not high, thermostability is relatively poor.
Fatty acid methyl ester is one of derivative of grease, since it can be used as motor vehicle fuel, early has become the heat of research
Point can also can prepare a variety of fine chemicals by series of chemical such as amination plus hydrogen, polymerization, epoxidations, be
Important basic chemical industry raw material.It can be used as the extender plasticizer of PVC product by epoxy aliphatic acid methyl ester prepared by epoxidation
It uses, it is from a wealth of sources due to its low toxic and environment-friendly, it is widely used in drug and packaging material for food, artificial leather, agricultural film
Deng.But this kind of plasticizer is easy to be precipitated from PVC product, can only added on a small quantity, made due to the poor compatibility with polyvinyl chloride resin
For extender plasticizer use.
The present invention utilizes the spy of citric acid using the extensive biomass material citric acid in source and aliphatic ester as primary raw material
Different structure and epoxy aliphatic ester ring-opening reaction prepare the PVC plasticizer big with relative molecular weight, to increase its thermostabilization
Performance increases and the compatibility of polyvinyl chloride resin and resistance to precipitation performance with multiple polar bonds are contained again.
Summary of the invention
The technical issues of solution: the present invention provide a kind of acetylation citric acid aliphatic ester plasticizer and preparation method thereof and
Using from a wealth of sources, cheap and environmentally protective fatty acid methyl ester and citric acid are passed through epoxidation, open loop ester by this method
The chemical reactions such as change, be acylated and prepare the PVC plasticizer of function admirable, preparation process of the present invention is simple, can industrialized production,
It is at low cost, nontoxic plasticizer, efficient, thermal stability and cold resistance are thus prepared due to DOP.
Technical solution: a kind of acetylation citric acid aliphatic ester plasticizer, chemical structural formula are as follows:
Wherein,
The preparation method of above-mentioned acetylation citric acid aliphatic ester plasticizer, preparation step are as follows: prepare epoxidized fatty acid
Ester: hydrogen peroxide is added in the reaction vessel containing aliphatic ester and catalyst, wherein fatty acid in mass ratio: hydrogen peroxide: urging
Agent=1:1.0~2.0:0.01~0.1, control reaction temperature are not higher than 65 DEG C, and hydrogen peroxide is kept for 65 DEG C after adding, instead
After answering 2~6h epoxide number is neutralized, washes and is dried to obtain not less than 3.5% faint yellow epoxidized fatty acid ester；Citric acid and ring
Oxidation of fat acid esters ring-opening reaction prepares citric acid aliphatic ester: by epoxidized fatty acid ester made from upper step, citric acid and resisting
Oxygen agent is reacted 2~8 hours at 90~180 DEG C, and when acid value is less than 1.0mg/g, reaction was completed, obtains citric acid aliphatic ester；
Acetylization reaction: by citric acid aliphatic ester, acylating reagent and catalyst obtained in 50~120 DEG C of 1~6h of reaction；In again
With wash and be dried to obtain final products acetylation citric acid aliphatic ester plasticizer.
Above-mentioned aliphatic ester is that methyl oleate, methyl ricinolcic acid, methyl soyate, cottonseed oil methyl esters, iodine number are big
In 80 fatty acid methyl ester (biodiesel), ethyl oleate, ricinoleic acid ethyl ester, soybean ethyl oleate, cottonseed oil ethyl ester or iodine
Value is greater than 80 at least one of fatty-acid ethyl ester.
The above-mentioned catalyst prepared in epoxidized fatty acid ester step be ion exchange resin, quaternary ammonium salt phosphor-tungstic heteropoly acid,
Any one in aluminum sulfate.
The above-mentioned antioxidant prepared in citric acid aliphatic ester step be antioxidant 1010, irgasfos 168, antioxidant 246,
Any one in ortho phosphorous acid, dosage are 0.1~the 5 ‰ of citric acid aliphatic ester quality.
It is above-mentioned to prepare in citric acid aliphatic ester step, it is calculated with epoxide number, citric acid and epoxidized fatty acid ester rub
You are than being 3~6.
Above-mentioned prepare also contains catalyst in citric acid aliphatic ester step, the catalyst is trimethylamine, divinyl three
Appointing in amine, methylimidazole, butyl titanate, tetrabutylammonium bromide, tetrabutylammonium chloride and quaternary ammonium salt phosphor-tungstic heteropoly acid etc.
It anticipates one kind, dosage is the 0.1~2% of epoxidized fatty acid ester quality.
In above-mentioned acetylization reaction step, the catalyst is ammonium hydrogen sulfate, cation exchange resin or the concentrated sulfuric acid, dosage
It is the 1~5% of citric acid aliphatic ester quality.
In above-mentioned acetylization reaction step, the acylating reagent is acetic anhydride, and dosage is citric acid aliphatic ester quality
10%~80%.
Acetylation citric acid aliphatic ester plasticizer is in preparation PVC product and promotes the application in its thermal stability.
The utility model has the advantages that the biology base plasticizer that 1. present invention is prepared using citric acid and aliphatic ester as primary raw material, raw material
It is cheap and easy to get, it is environmentally protective, while can reduce the dependence to fossil resources.
2. since molecular weight is larger, polarity linkage content is high and the presence of long aliphatic chain, with acetylation tributyl citrate
It is more preferable that flash-point height, resistance to precipitation property, cold resistance and plasticizing efficiency are compared with epoxy aliphatic acid methyl ester, while can improve PVC product
Thermal stability, can also substitute DOP preparation completely has property PVC product.
3. present invention process is simple, mild condition, in the manufacturer of general plasticizer, not changing production equipment can be straight
It connects for the production to the plasticizer, is very suitable to industrialized production.
Detailed description of the invention
Epoxy aliphatic acid methyl ester, citric acid aliphatic ester and the acetylation citric acid mentioned and obtained for embodiment 1 in Fig. 1
The infrared spectrogram of aliphatic ester.3500cm-1(vasOH)；2926cm-1(νasCH3), 2853cm-1(νasCH2)；1736cm-1
Place is C=O stretching vibration in ester group structure on aliphatic chain；It is at 1079 secondary alcohol (δ OH)；1235cm-1Place is in ester group structure
C-O stretching vibration absworption peak；840cm-1For C-O-C stretching vibration absworption peak in epoxy bond structure.
Fig. 2 is the 1H-NMR nuclear magnetic resonance map for the acetylation citric acid aliphatic ester mentioned in embodiment 1, and each hydrogen is former
The chemical shift of son marks in figure.
Specific implementation method
The present invention is described in detail combined with specific embodiments below.It should be understood that these embodiments are merely to illustrate this
It invents rather than limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, this field skill
Art personnel can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims institute
The range of restriction, all raw materials are commercially available technical grade product.
Embodiment 1
The preparation of epoxyoleic acid methyl esters: the first step takes the hydrogen peroxide 45mL of 30wt.% concentration to be added drop-wise to and 30g has been added
In the three-necked flask of methyl oleate, 30mL acetic acid and 1.5g ion-exchange resin catalyst, control hydrogen peroxide is dripped in 1.5h
Finish, and temperature is not higher than 65 DEG C, keeps 65 DEG C of thermotonus 3h later, neutralized after reaction with 4wt.% sodium carbonate liquor,
Clear water is washed to neutrality, and being then dried to obtain epoxide number is 3.6% flaxen epoxyoleic acid methyl esters.
Second step, citric acid and epoxidized fatty acid methyl esters ring-opening reaction prepare citric acid aliphatic ester, and the first step is obtained
Epoxyoleic acid methyl esters 100g, citric acid 13g, antioxidant 1010 0.1g and the catalyst methylimidazole 0.4g arrived, 140
DEG C reaction 3 hours, the crude product that acid value is 0.82mg/g is obtained, then at 180~250 DEG C, vacuum degree is to distill under 2.0Kpa
The epoxidized fatty acid methyl esters and fatty acid methyl ester for having neither part nor lot in reaction out, obtain citric acid aliphatic ester 70g.
Third step, acetylization reaction, citric acid aliphatic ester 100g, acylating reagent acetic anhydride 25g prepared by second step
With catalyst sulfuric acid hydrogen sodium 0.5g, 3h is reacted at a temperature of 80 DEG C；Excessive acetic anhydride and generation are distilled off after reaction
Acetic acid, then with the sodium bicarbonate solution of 4wt.% concentration be neutralized to it is neutral, wash and to be dried to obtain final products yellow saturating
Prescribed liquid, acetylation citric acid aliphatic ester PVC plasticizer 105g；Acid value 0.3mg/g, viscosity 623mPa.s, open flash point 248
℃。
Embodiment 2
The preparation of epoxidized fatty acid methyl esters: the first step takes the hydrogen peroxide 50mL of 30wt.% concentration to be added drop-wise to and has been added
In the three-necked flask of 30g methyl oleate, the ethyl acetate of 20mL and 1.2g quaternary ammonium salt phosphor-tungstic heteropoly acid catalyst, hydrogen peroxide is controlled
It is dripped in 2.0h, temperature is not higher than 65 DEG C, keeps 65 DEG C of thermotonus 3h later, and reaction terminates to use 4wt.% sodium carbonate liquor
It neutralizes, be washed to neutrality, be then dried to obtain the yellowish epoxyoleic acid methyl esters of epoxide number 4.1%.
Second step, citric acid and epoxidized fatty acid methyl esters ring-opening reaction prepare citric acid aliphatic ester, and the first step is obtained
Epoxyoleic acid methyl esters 100g, citric acid 14g, irgasfos 168 0.1g and the catalyst diethylenetriamine 0.3g arrived, at 140 DEG C
Reaction 4 hours obtains the crude product that acid value is 0.86mg/g, then at 180~250 DEG C, under the conditions of vacuum degree is 2.0Kpa, steams
The epoxyoleic acid methyl esters and methyl oleate for having neither part nor lot in reaction are distillated, citric acid aliphatic ester 75g is obtained.
Third step, acetylization reaction, citric acid aliphatic ester 100g, acylating reagent acetic anhydride 25g prepared by second step
With catalyst ion exchange resin 2.0g, 4h is reacted at a temperature of 80 DEG C；Be distilled off after reaction excessive acetic anhydride and
Then the acetic acid of production is neutralized to neutral, washing and drying with the sodium bicarbonate solution of 4% concentration, it is bright orange to obtain final products
Color transparency liquid, acetylation citric acid aliphatic ester PVC plasticizer 105g；Acid value 0.28mg/g, viscosity 741mPa.s, opening are dodged
252 DEG C of point.
Embodiment 3
The preparation of epoxidized castor oil acid methyl esters: the first step takes the hydrogen peroxide 55mL of 30wt.% concentration to be added drop-wise to and has been added
In the three-necked flask of 30g methyl ricinolcic acid, the ethyl acetate of 20mL and 1.2g quaternary ammonium salt phosphor-tungstic heteropoly acid catalyst, control is double
Oxygen water is added dropwise in 2h, and reaction temperature is not higher than 65 DEG C, keeps 65 DEG C of thermotonus 3h later, and reaction terminates 4% carbonic acid
Sodium solution neutralizes, is washed to neutrality, then dries, obtains the yellowish epoxidized castor oil acid methyl esters of epoxide number 3.8%.
Second step, citric acid and epoxidized castor oil acid methyl esters ring-opening reaction prepare citric acid aliphatic ester, by the first step
Obtained epoxidized castor oil acid methyl esters 100g, citric acid 14g, 50% ortho phosphorous acid 0.2g and catalyst tetrabutylammonium chloride
0.2g reacts 3.5 hours at 140 DEG C, obtains the crude product that acid value is 0.98mg/g, then at 180~250 DEG C, vacuum degree is
The epoxidized castor oil acid methyl esters and methyl ricinolcic acid for having neither part nor lot in reaction are distilled out under 2.0Kpa, obtain citric acid aliphatic ester
82g。
Third step, acetylization reaction, citric acid aliphatic ester 100g, acylating reagent acetic anhydride 35g prepared by second step
With catalyst sulfuric acid hydrogen sodium 0.8g, 4h is reacted at a temperature of 80 DEG C；Excessive acetic anhydride and generation are distilled off after reaction
Acetic acid, be then neutralized to neutral, washing and dry with the sodium bicarbonate solution of 4wt.% concentration, obtain final products glassy yellow
Transparency liquid, acetylation citric acid aliphatic ester PVC plasticizer 108g；Acid value 0.25mg/g, viscosity 976mPa.s, open flash point
268℃。
Embodiment 4
The preparation of epoxidised soybean oil acid methyl esters: the first step takes the hydrogen peroxide 55mL of 30wt.% concentration to be added drop-wise to and has been charged into
In the three-necked flask of 30g methyl soyate, 30mL acetic acid and 1.5g aluminum sulfate as catalyst agent, control hydrogen peroxide is dripped in 2h
Finish, temperature is not higher than 65 DEG C, later 65 DEG C of thermotonus 5h of holding, and reaction terminates to be neutralized with 4wt.% sodium carbonate liquor, wash
It to neutrality, then dries, obtains the yellowish epoxidised soybean oil methyl esters of epoxide number 4.8%.
Second step, citric acid and epoxidised soybean oil acid methyl esters ring-opening reaction prepare citric acid aliphatic ester, by the first step
The ortho phosphorous acid 0.2g and catalyst tetrabutyl bromine of obtained epoxidised soybean oil acid methyl esters 100g, citric acid 14g, 50wt.%
Change ammonium 0.3g, reacted 3.5 hours at 150 DEG C, obtains the crude product that acid value is 0.88mg/g, then at 180~250 DEG C, vacuum
Degree is to distill out the epoxidised soybean oil acid methyl esters and methyl soyate for having neither part nor lot in reaction under 2.0Kpa, obtains citric acid fat
Acid esters 84g.
Third step, acetylization reaction, citric acid aliphatic ester 100g, acylating reagent acetic anhydride 20g prepared by second step
With catalyst sulfuric acid hydrogen sodium 0.8g, 4h is reacted at a temperature of 80 DEG C；Excessive acetic anhydride and production are distilled off after reaction
Acetic acid, then with the sodium bicarbonate solution of 4wt.% concentration be neutralized to it is neutral, wash and to be dried to obtain final products yellow saturating
Prescribed liquid, acetylation citric acid aliphatic ester PVC plasticizer 104g；Acid value 0.25mg/g, viscosity 1045mPa.s, open flash point
258℃。
Embodiment 5
The preparation of epoxidation oleic acid methyl esters: the first step takes the hydrogen peroxide 50mL of 30wt.% concentration to be added drop-wise to and has been added
In the three-necked flask of 30g oleic acid methyl esters, the ethyl acetate of 22mL and 1.5g quaternary ammonium salt phosphor-tungstic heteropoly acid catalyst, control is double
Oxygen water is added dropwise in 2.5h, and temperature is not higher than 65 DEG C, keeps 65 DEG C of thermotonus 3h later, and reaction terminates to use 4wt.% carbonic acid
Sodium solution neutralizes, is washed to neutrality, is then dried to obtain the yellowish epoxidation oleic acid methyl esters of epoxide number 4.2%.
Second step, citric acid and epoxidation oleic acid methyl esters ring-opening reaction prepare citric acid aliphatic ester, by the first step
The ortho phosphorous acid 0.2g and catalyst phosphorus tungsten of obtained epoxidation oleic acid methyl esters 100g, citric acid 15g, 50wt.% are miscellaneous more
Sour quaternary ammonium salt 1.0g reacts 3.5 hours at 160 DEG C, obtains the crude product that acid value is 0.84mg/g, then at 180~250 DEG C,
Vacuum degree is to distill out the epoxidation oleic acid methyl esters and oleic acid methyl esters for having neither part nor lot in reaction under 2.0Kpa, obtains citric acid
Aliphatic ester 82g.
Third step, acetylization reaction, by second step preparation citric acid aliphatic ester 100, acylating reagent acetic anhydride 25g and
Catalyst sulfuric acid hydrogen sodium 0.8g, reacts 4h at a temperature of 80 DEG C；Excessive acetic anhydride and production are distilled off after reaction
Then acetic acid is neutralized to neutral, washing and drying with the sodium bicarbonate solution of 4wt.% concentration, obtains final products yellow transparent
Liquid, acetylation citric acid aliphatic ester PVC plasticizer 108g；Acid value 0.25mg/g, viscosity 976mPa.s, open flash point 268
℃。
Embodiment 6
The preparation of epoxyoleic acid methyl esters: the first step takes the hydrogen peroxide 50mL of 30wt.% concentration to be added drop-wise to and 30g has been added
In the three-necked flask of methyl oleate, the ethyl acetate of 20mL and 1.2g quaternary ammonium salt phosphor-tungstic heteropoly acid catalyst, control hydrogen peroxide exists
2.0h is dripped, and temperature is not higher than 65 DEG C, keeps 65 DEG C of thermotonus 3h later, and reaction terminates in 4wt.% sodium carbonate liquor
Be washed to neutrality, be then dried to obtain the yellowish epoxyoleic acid methyl esters of epoxide number 4.1%.
Second step, citric acid and epoxidized fatty acid methyl esters ring-opening reaction prepare citric acid aliphatic ester, and the first step is obtained
The epoxyoleic acid methyl esters 100g that arrives, citric acid 12g, 246 0.1g of antioxidant and without under catalysts conditions, react 10 at 160 DEG C
Hour, the crude product that acid value is 0.88mg/g is obtained, then at 180~250 DEG C, under the conditions of vacuum degree is 2.0Kpa, is distilled out
The epoxyoleic acid methyl esters and methyl oleate for having neither part nor lot in reaction, obtain citric acid aliphatic ester 68g.
Third step, acetylization reaction, citric acid aliphatic ester 100g, acylating reagent acetic anhydride 25g prepared by second step
With catalyst ion exchange resin 2.0g, 4h is reacted at a temperature of 80 DEG C；Be distilled off after reaction excessive acetic anhydride and
Then the acetic acid of production is neutralized to neutral, washing and drying with the sodium bicarbonate solution of 4wt.% concentration, it is bright to obtain final products
Yellow transparent liquid, acetylation citric acid aliphatic ester PVC plasticizer 105g；Acid value 0.30mg/g, viscosity 748mPa.s, opening
251 DEG C of flash-point.
Embodiment 7
The preparation of epoxidized oil acetoacetic ester: the first step takes the hydrogen peroxide 45mL of 30wt.% concentration to be added drop-wise to and 30g has been added
In the three-necked flask of ethyl oleate, 30mL acetic acid and 1.8g ion-exchange resin catalyst, control hydrogen peroxide is dripped in 2.0h
Finish, and temperature is not higher than 65 DEG C, keeps 65 DEG C of thermotonus 3h later, neutralized after reaction with 4wt.% sodium carbonate liquor,
Clear water is washed to neutrality, and being then dried to obtain epoxide number is 3.5% flaxen epoxidized oil acetoacetic ester.
Second step, citric acid and epoxidized oil acetoacetic ester ring-opening reaction prepare citric acid aliphatic ester, and the first step is obtained
Epoxidized oil acetoacetic ester 100g, citric acid 12g, 246 0.1g of antioxidant and catalyst tetrabutylammonium bromide 0.4g, at 140 DEG C
Reaction 4 hours obtains the crude product that acid value is 0.85mg/g, and then at 180~260 DEG C, vacuum degree is to distill out under 2.0Kpa
The epoxidized fat acetoacetic ester and fatty-acid ethyl ester for having neither part nor lot in reaction, obtain citric acid aliphatic ester 70g.
Third step, acetylization reaction, citric acid aliphatic ester 100g, acylating reagent acetic anhydride 25g prepared by second step
With catalyst sulfuric acid hydrogen sodium 0.5g, 3h is reacted at a temperature of 80 DEG C；Excessive acetic anhydride and generation are distilled off after reaction
Acetic acid, then with the sodium bicarbonate solution of 4wt.% concentration be neutralized to it is neutral, wash and to be dried to obtain final products yellow saturating
Prescribed liquid, acetylation citric acid aliphatic ester PVC plasticizer 105g；Acid value 0.26mg/g, viscosity 764mPa.s, open flash point
265℃。
Embodiment 8
The preparation of epoxidized castor oil acetoacetic ester: the first step takes the hydrogen peroxide 55mL of 30wt.% concentration to be added drop-wise to and has been added
In the three-necked flask of 30g methyl ricinolcic acid, the ethyl acetate of 25mL and 1.5g quaternary ammonium salt phosphor-tungstic heteropoly acid catalyst, control is double
Oxygen water is added dropwise in 2h, and reaction temperature is not higher than 65 DEG C, keeps 65 DEG C of thermotonus 5h later, and reaction terminates to use 4wt.% carbon
Acid sodium solution neutralizes, is washed to neutrality, then dries, obtains the yellowish epoxidized castor oil acid methyl esters of epoxide number 3.6%.
Second step, citric acid and epoxidized castor oil acetoacetic ester ring-opening reaction prepare citric acid aliphatic ester, by the first step
Obtained epoxidized castor oil acetoacetic ester 100g, citric acid 13g, antioxidant 1010 0.2g and catalyst tetrabutylammonium chloride
0.2g reacts 5 hours at 140 DEG C, obtains the crude product that acid value is 0.88mg/g, then at 180~260 DEG C, vacuum degree is
The epoxidized castor oil acetoacetic ester and ricinoleic acid ethyl ester for having neither part nor lot in reaction are distilled out under 2.0Kpa, obtain citric acid aliphatic ester
85g。
Third step, acetylization reaction, citric acid aliphatic ester 100g, acylating reagent acetic anhydride 35g prepared by second step
With catalyst sulfuric acid hydrogen sodium 0.8g, 4h is reacted at a temperature of 80 DEG C；Excessive acetic anhydride and generation are distilled off after reaction
Acetic acid, be then neutralized to neutral, washing and dry with the sodium bicarbonate solution of 4wt.% concentration, obtain final products glassy yellow
Transparency liquid, acetylation citric acid aliphatic ester PVC plasticizer 108g；Acid value 0.23mg/g, viscosity 1085mPa.s, opening are dodged
272 DEG C of point.
Application example
Sample preparation and test
According to the plasticizer consumption in table 1 by 100g PVC paste shape resin-oatmeal, technical grade, South Korea Han Hua (KM-31, DP=
1300 ± 100, K value=71), the raw materials such as calcium stearate (stabilizer) of the zinc stearate of 1g and 1g are pre-mixed,
Mixture is carried out by thermoplastic using torque rheometer；It is thick that dumb-bell shape tensile bars drawing zone is prepared into using micro-injection molding machine
Degree~0.4mm, width 4mm, original gauge length 25mm measure material by GB/T1040.3-2006 " measurement of plastic tensile performance "
Tensile property, extension test speed be 5cm/min, five samples of every group of parallel testing.Wherein select common plasticizer DOP
(terephthalic acid (TPA) dibutyl ester) and ESO (epoxidized soybean oil) do comparative experiments.Take the damage in dynamic thermomechanical analysis test (DMA)
The peak temperature for consuming factor Tan δ change curve is glass transition temperature.Volatile analytes according to ISO 176:2005E (E),
It will be having a size of 60 × 60 × 0.4mm3PVC sample be put into canister, coat quantitative active carbon, be placed in constant temperature 70 ± 1
DEG C baking oven in, for 24 hours afterwards take out its mass loss of sample test.Specific data are shown in Table result in 1.
The performance test of table 1 embodiment and comparative example
| Raw material | 1 | 2 | 3 | 4 | 5 | 6 | 7 |
| 1 plasticizer of embodiment/g | 50 | - | - | - | - | - | - |
| 3 plasticizer of embodiment/g | - | 50 | - | - | - | - | - |
| 4 plasticizer of embodiment/g | - | - | 50 | - | - | - | - |
| 5 plasticizer of embodiment/g | - | - | - | 50 | - | - | - |
| 8 plasticizer of embodiment/g | - | - | - | - | 50 | - | - |
| Comparative experiments: ESO/g | - | - | - | - | - | 50 | - |
| Comparative experiments: DOP/g | - | - | - | - | - | - | 50 |
| Glass transition temperature/DEG C | 26.2 | 25.8 | 26.4 | 25.6 | 24.4 | 28.8 | 30.4 |
| Tensile strength MPa | 22.6 | 23.8 | 24.1 | 25.5 | 24.8 | 20.5 | 23.2 |
| Elongation at break/% | 336 | 346 | 361 | 354 | 365 | 327 | 348 |
| Stretching yield stress/MPa | 3.61 | 3.42 | 3.54 | 3.54 | 3.62 | 3.90 | 3.39 |
| Elasticity modulus/MPa | 15.2 | 12.3 | 11.2 | 14.6 | 15.6 | 13.6 | 20.1 |
| Volatility/% | 3.65 | 3.71 | 3.66 | 3.72 | 3.61 | 3.95 | 4.21 |
Shown as test result in table 1: elasticizer plasticizing PVC sample prepared by the present invention, compared with ESO, mechanicalness
Can be more preferable, thermal stability is more excellent compared with DOP.The plasticizing efficiency that analysis obtains the type plasticizer is suitable with DOP, embodiment
The elongation at break and tensile strength of the PVC sample of 8 obtained elasticizer plasticizings are even better than the PVC sample of DOP plasticising；Due to
Molecular weight is big compared with DOP, is superior to DOP in terms of resistance to volatilization；Compared with ESO be either plasticized performance or volatility resistance can be excellent
In ESO.
Claims (9)
1. the preparation method of acetylation citric acid aliphatic ester plasticizer, it is characterised in that preparation step are as follows:
It prepares epoxidized fatty acid ester: hydrogen peroxide is added in the reaction vessel containing aliphatic ester and catalyst, wherein pressing matter
Amount is than fatty acid: hydrogen peroxide: catalyst=1:1.0 ~ 2.0:0.01 ~ 0.1, and control reaction temperature is not higher than 65 DEG C, hydrogen peroxide addition
After kept for 65 DEG C, neutralize, wash and be dried to obtain epoxide number not less than 3.5% faint yellow epoxidized fat after reacting 2 ~ 6h
Acid esters；
Citric acid and epoxidized fatty acid ester ring-opening reaction prepare citric acid aliphatic ester: by epoxidized fatty acid made from upper step
Ester, citric acid and antioxidant react 2 ~ 8 hours at 90 ~ 180 DEG C, and when acid value is less than 1.0mg/g, reaction was completed, obtain lemon
Sour aliphatic ester；
Acetylization reaction: by citric acid aliphatic ester, acylating reagent and catalyst obtained in 50 ~ 120 DEG C of 1 ~ 6h of reaction；In again
With wash and be dried to obtain final products acetylation citric acid aliphatic ester plasticizer.
2. the preparation method of acetylation citric acid aliphatic ester plasticizer according to claim 1, it is characterised in that described
Aliphatic ester be methyl oleate, methyl ricinolcic acid, methyl soyate, cottonseed oil methyl esters, iodine number be greater than 80 fatty acid
Methyl esters, ethyl oleate, ricinoleic acid ethyl ester, soybean ethyl oleate, oleic acid ethyl ester or iodine number are greater than 80 fatty-acid ethyl ester
At least one of.
3. the preparation method of acetylation citric acid aliphatic ester plasticizer according to claim 1, it is characterised in that described
The catalyst in epoxidized fatty acid ester step is prepared as appointing in ion exchange resin, quaternary ammonium salt phosphor-tungstic heteropoly acid, aluminum sulfate
It anticipates one kind.
4. the preparation method of acetylation citric acid aliphatic ester plasticizer according to claim 1, it is characterised in that preparation
Antioxidant in citric acid aliphatic ester step is antioxidant 1010, irgasfos 168, antioxidant 246, any in ortho phosphorous acid
One kind, dosage are 0.1 ~ the 5 ‰ of citric acid aliphatic ester quality.
5. the preparation method of acetylation citric acid aliphatic ester plasticizer according to claim 1, it is characterised in that preparation
It in citric acid aliphatic ester step, is calculated with epoxide number, the molar ratio of citric acid and epoxidized fatty acid ester is 3 ~ 6.
6. the preparation method of acetylation citric acid aliphatic ester plasticizer according to claim 1, it is characterised in that preparation
Also contain catalyst in citric acid aliphatic ester step, the catalyst is trimethylamine, diethylenetriamine, methylimidazole, titanium
Any one in sour four butyl esters, tetrabutylammonium bromide, tetrabutylammonium chloride and quaternary ammonium salt phosphor-tungstic heteropoly acid, dosage is epoxy
Change the 0.1 ~ 2% of aliphatic ester quality.
7. the preparation method of acetylation citric acid aliphatic ester plasticizer according to claim 1, it is characterised in that acetyl
Change in reaction step, the catalyst is ammonium hydrogen sulfate, cation exchange resin or the concentrated sulfuric acid, and dosage is citric acid aliphatic ester
The 1 ~ 5% of quality.
8. the preparation method of acetylation citric acid aliphatic ester plasticizer according to claim 1, it is characterised in that acetyl
Change in reaction step, the acylating reagent is acetic anhydride, and dosage is the 10% ~ 80% of citric acid aliphatic ester quality.
9. acetylation citric acid aliphatic ester plasticizer made from preparation method described in claim 1 is in preparation PVC product and mentions
Rise the application in its thermal stability.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710347591.3A CN107176910B (en) | 2017-05-17 | 2017-05-17 | A kind of acetylation citric acid aliphatic ester plasticizer and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710347591.3A CN107176910B (en) | 2017-05-17 | 2017-05-17 | A kind of acetylation citric acid aliphatic ester plasticizer and its preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107176910A CN107176910A (en) | 2017-09-19 |
| CN107176910B true CN107176910B (en) | 2019-10-22 |
Family
ID=59831823
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710347591.3A Expired - Fee Related CN107176910B (en) | 2017-05-17 | 2017-05-17 | A kind of acetylation citric acid aliphatic ester plasticizer and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107176910B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110642719A (en) * | 2019-10-12 | 2020-01-03 | 江南大学 | Preparation method and application of malic acid-based environment-friendly plasticizer |
| CN110627643B (en) * | 2019-10-15 | 2021-11-12 | 江南大学 | Method for preparing environment-friendly plasticizer by using waste oil and fat and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101391956A (en) * | 2008-11-05 | 2009-03-25 | 江南大学 | Method for synthesizing methyl oleate and epoxy methyl oleate in ion liquid medium |
| CN101774985A (en) * | 2010-02-05 | 2010-07-14 | 江苏工业学院 | Method for preparing epoxidized methyl acetorieinoleate |
| CN105219479A (en) * | 2015-10-09 | 2016-01-06 | 常州市长润石油有限公司 | A kind of immobilized ionic liquid-catalyzed epoxy methyl esters prepares the method for Green Lubricants |
| CN105255059A (en) * | 2015-11-10 | 2016-01-20 | 芜湖市艾德森自动化设备有限公司 | High-temperature-resisting anti-aging interior decoration PVC modified material and preparation method thereof |
| CN105295102A (en) * | 2015-11-11 | 2016-02-03 | 苏州国泰科技发展有限公司 | Method for preparing green environment-friendly plasticizer |
-
2017
- 2017-05-17 CN CN201710347591.3A patent/CN107176910B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101391956A (en) * | 2008-11-05 | 2009-03-25 | 江南大学 | Method for synthesizing methyl oleate and epoxy methyl oleate in ion liquid medium |
| CN101774985A (en) * | 2010-02-05 | 2010-07-14 | 江苏工业学院 | Method for preparing epoxidized methyl acetorieinoleate |
| CN105219479A (en) * | 2015-10-09 | 2016-01-06 | 常州市长润石油有限公司 | A kind of immobilized ionic liquid-catalyzed epoxy methyl esters prepares the method for Green Lubricants |
| CN105255059A (en) * | 2015-11-10 | 2016-01-20 | 芜湖市艾德森自动化设备有限公司 | High-temperature-resisting anti-aging interior decoration PVC modified material and preparation method thereof |
| CN105295102A (en) * | 2015-11-11 | 2016-02-03 | 苏州国泰科技发展有限公司 | Method for preparing green environment-friendly plasticizer |
Non-Patent Citations (2)
| Title |
|---|
| 《Preparation of functionalized castor oil derivatives with tunable physical properties using heterogeneous acid and base catalysts》;Sivashunmugam Sankaranarayanan and Kannan Srinivasan;《RSC Advances》;20151231;第5卷(第62期);第50289-50297页 * |
| 《杂多酸催化油酸甲酯环氧化的研究》;周喜阳等;《应用化工》;20110831;第40卷(第8期);第1408-1415页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107176910A (en) | 2017-09-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Bocqué et al. | Petro‐based and bio‐based plasticizers: chemical structures to plasticizing properties | |
| US8623947B2 (en) | Plasticized PVC composition | |
| US6797753B2 (en) | Plasticizers derived from vegetable oils | |
| KR101981990B1 (en) | Plasticizer composition comprising naturally cardanol base plasticizer and vegetable oil base epoxidated, and polymer resin composition comprising the same | |
| CN103804669B (en) | A kind of preparation method being used as the castor oil-base polyester of PVC softening agent | |
| KR20180067435A (en) | Plasticizer and resin composition comprising the same | |
| CN108752803B (en) | Preparation method and application of adipic acid series environment-friendly polyester plasticizer with different and controllable molecular weights | |
| EP3056489A1 (en) | Synthesis process for diacetyl epoxy glyceryl oleate | |
| KR101793383B1 (en) | Plasticizer, resin composition and method for preparing them | |
| CN110041195A (en) | A kind of fatty acid poleysters PVC plasticizer and preparation method thereof | |
| CN107176910B (en) | A kind of acetylation citric acid aliphatic ester plasticizer and its preparation method and application | |
| CN101691524A (en) | Method for preparing epoxidized soybean oil with high epoxy value by fractional step method | |
| KR20170012117A (en) | Plasticizer, resin composition and method for preparing them | |
| Karmalm et al. | Network formation by epoxidised soybean oil in plastisol poly (vinyl chloride) | |
| CN104370860A (en) | Diepoxide vegetable oil acid acetyl glyceride and synthesis method and application thereof | |
| CN105885288B (en) | A kind of auxiliary heat stabilizer for polyvinyl chloride and preparation method thereof | |
| KR20170122706A (en) | Plasticizer, resin composition and method for preparing them | |
| CN105085442A (en) | Diacid bismonoacetyl epoxy vegetable oil ester and synthetic method thereof | |
| CN110804029A (en) | Epoxy plasticizer and preparation method thereof | |
| CN110776668A (en) | Environment-friendly difurancarboxylate plasticizer and application thereof | |
| CN105906586A (en) | Epoxy grease base plasticizing agent and preparation method thereof | |
| CN108623795A (en) | A kind of polyester, Preparation method and use based on full biomass monomer | |
| Souza et al. | PVC plasticizer from trimethylolpropane trioleate: synthesis, properties, and application | |
| US10113051B2 (en) | Epoxy estolide fatty acid alkyl esters useful as biorenewable plasticizers | |
| CN103936582B (en) | A kind of method preparing citric acid butyl benzyl with biomass material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20191022 Termination date: 20200517 |