CN106753809A - A kind of utilization vegetable oil esters and citrate synthetic macromolecule amount, the preparation method of hyper-branched citrate ester derivatives - Google Patents
A kind of utilization vegetable oil esters and citrate synthetic macromolecule amount, the preparation method of hyper-branched citrate ester derivatives Download PDFInfo
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- CN106753809A CN106753809A CN201611050162.1A CN201611050162A CN106753809A CN 106753809 A CN106753809 A CN 106753809A CN 201611050162 A CN201611050162 A CN 201611050162A CN 106753809 A CN106753809 A CN 106753809A
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- citrate
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
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- 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
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
It is a kind of preparation method of biomass plasticizer the invention belongs to synthetic material plasticizer field.With citrate and the biomass grease containing unsaturated double-bond is as raw material, reacted by catalyst etherifying, form macromolecule, hyper-branched citrate ester derivatives, mean molecule quantity is about 1500~4500g/mol.This kind of material has that animal migration is low, volatility it is small and water-fast/characteristic extracted out of oil so that with durable plasticization so that the product being plasticized through product synthesized by the present invention has permanent performance.
Description
Technical field
It is a kind of preparation method of biomass plasticizer the invention belongs to synthetic material plasticizer field.Specifically
It is related to citrate to be chemically reacted with grease containing unsaturated double-bond, synthetic macromolecule biomass plasticizer.
Technical background
Phthalic acid esters class plasticizer, because it contains aromatic rings, not easily biological-degradable, while have carcinogenic possibility,
European Union successively puts into effect multiple bills and instruction, and strict limitation phthalic ester plasticizer is used for packaging for foodstuff, medical supplies
In toy for children and other PVC products with human body close contact, therefore exploitation and production environmental protection plasticizer gesture are must
OK.Citric acid ester plasticizer is a kind of environmental protection plasticizer of safety non-toxic, with good, the speedup efficiency with Compatibility in Plastics
Height, the advantages of volatility is small, is widely used in the industries such as medicine, packaging for foodstuff, daily use chemicals, is to substitute phthalic acid ester both at home and abroad
The first-selection of class plasticizer.But the easy migration precipitation of citric acid ester plasticizer, the endurance quality for ultimately causing material is poor.Improve
The molecular weight and the degree of branching of plasticizer are a kind of feasible methods for preventing its migration.
Macromolecule and highly -branched degree class plasticizer have that animal migration is low, volatility it is small and water-fast/performance extracted out of oil, from
And there is durable plasticization so that the product being plasticized has permanent performance.
Propose at high temperature to be polymerized castor oil acid in Chinese patent application 201610204615, obtain molecular weight 3000-
5000 homopolymers, is the plasticizer with preferable durability, but product building-up process is complicated, and product colour is brownish black, should
With being limited in scope, general life product is should not be used in.
The hydroxyl alcohol ester being first combined to monoacid and binary alcohol esters is proposed in Chinese patent application 201410201350,
Esterification, the citrate of synthesis relative molecular weight 500-2000 are carried out with resulting hydroxyl alcohol ester and citric acid again.
Monoacid described in this application is acetic acid, propionic acid butyric acid, valeric acid and caproic acid, and described dihydroxylic alcohols is ethylene glycol, propane diols, fourth two
Alcohol, diethylene glycol (DEG), triethylene glycol, DPG etc..These raw materials are substantially based on the petroleum chemicals of fossil feedstock, considerably
Counteract characteristic and advantage of the citric acid as biomass plasticizer.
The content of invention
The purpose of the present invention：Divide greatly using the vegetable oil esters of biomass renewable resource are a kind of with citrate synthesis new
Son amount, hyper-branched citrate ester derivatives.The composition principle of citrate ester derivatives is illustrated in fig. 1 shown below.
Technical scheme：The present invention is achieved through the following technical solutions：With citrate and containing unsaturation
The renewable resource vegetable oil esters of double bond, by certain mol ratio, under catalyst action, make in citrate molecule from
Addition etherification reaction is carried out by the unsaturated double-bond in hydroxyl and biomass grease under certain conditions, makes citrate molecule
Macromolecule, hyper-branched citrate ester derivatives are obtained by the formation of ehter bond with bio-oil ester molecule.It is chemical anti-
Principle is answered to see Fig. 1.
Preferably, described citrate can be the triethyl of citric acid, or the tributyl of citric acid, also
Can be three monooctyl esters of citric acid.
Preferably, the described biomass grease containing unsaturated double-bond, can be soybean oil, linseed oil, rapeseed
Oil, cottonseed oil, tung oil etc..
Preferably, described citrate is according to unsaturated double bond in grease with the proportioning of biomass grease
It is fixed.Feed intake control：Citrate：Unsaturated double-bond=1.0~1.3 (mol ratio) in grease.
Preferably, described catalyst is acid.Can be L acids, such as：Boron trifluoride complex, tri-chlorination
Aluminium；Can also be B acids, such as：Sulfuric acid, methanesulfonic acid, phosphotungstic acid, macropore strong acid sulphonic resin.Catalyst amount is reactant
The 0.3~5% of material weight.
Preferably, described etherification reaction condition is：Under nitrogen protection, reaction temperature is 80~180 DEG C, reaction time
It is 4~8 hours.
The effect of invention：The implementation of the present invention program, makes multiple citrate molecules with the vegetable oil containing unsaturated double-bond
Ester, macromolecule, hyper-branched citrate ester derivatives are formed by etherification reaction, and mean molecule quantity is 1500~4500g/
mol。
Brief description of the drawings
Fig. 1 is hyper-branched citrate ester derivatives composition principle figure.
Specific embodiment
The computing formula or standard of parameter are as follows：
1. double bond etherificate rate：Double bond etherificate rate (i.e. reaction conversion ratio)=(initial reactant iodine number-product iodine number)/initial
Reactant iodine number；
2. the measure of iodine number：Method according to standard GB/T/T 1676-2008 (measure of plasticizer iodine number) is grasped
Make.
Example 1：ATBC and the soybean oil etherificate many ATBC soybean oil ethers of synthesis
300g soybean oils are added in the churned mechanically reactor of band, and (containing about 1.56mol unsaturated double-bonds, iodine number is
130gI2/ 100g oil), 560g ATBCs, 25.8g boron trifluoride pyridine complexs, i.e.,：Citrate：In grease not
Saturation double bond=1.0 (mol ratio), catalyst amount are the 3% of reaction mass weight.Under nitrogen protection, 140 DEG C of reactions 6 are controlled
Hour completes etherification reaction.The etherificate rate (i.e. etherification reaction conversion ratio) of double bond is 94.2%.The resulting many citric acids three of product
The mean molecule quantity of butyl ester soybean oil ether is about 2600g/mol.
Example 2：Trioctyl lemon acid and the linseed oil etherificate many trioctyl lemon acid linseed oil ethers of synthesis
300g linseed oil is added in the churned mechanically reactor of band, and (containing about 2.4mol unsaturated double-bonds, iodine number is
200gI2/ 100g oil), 1520g trioctyl lemon acids, 18.2g methanesulfonic acids, i.e.,：Citrate：Unsaturated double-bond in grease=
1.2 (mol ratios), catalyst amount are the 1% of reaction mass weight.Under nitrogen protection, 120 DEG C of reactions are controlled to complete ether in 4 hours
Change reaction.The etherificate rate of double bond is 93.4%.The mean molecule quantity of the resulting many trioctyl lemon acid linseed oil ethers of product is about
It is 4500g/mol.
Example 3：ATBC and the rapeseed oil etherificate many ATBC rapeseed oil ethers of synthesis
300g rapeseed oils are added in the churned mechanically reactor of band, and (containing about 1.2mol unsaturated double-bonds, iodine number is
100gI2/ 100g oil), 432g ATBCs, the 2.2g concentrated sulfuric acids, i.e.,：Citrate：Unsaturated double-bond=1.0 in grease
(mol ratio), catalyst amount are the 0.3% of reaction mass weight.Under nitrogen protection, 80 DEG C of reactions are controlled to complete etherificate in 8 hours
Reaction.The etherificate rate of double bond is 91.6%.The mean molecule quantity of the resulting many ATBC rapeseed oil ethers of product is about
2350g/mol。
Example 4：Triethyl citrate and the cottonseed oil etherificate many triethyl citrate cottonseed oil ethers of synthesis
300g cottonseed oils are added in the churned mechanically reactor of band, and (containing about 1.3mol unsaturated double-bonds, iodine number is
110gI2/ 100g oil), 395g triethyl citrates, 10.4g phosphotungstic acids, i.e.,：Citrate：Unsaturated double-bond=1.1 in grease
(mol ratio), catalyst amount are the 1.5% of reaction mass weight.Under nitrogen protection, 160 DEG C of reactions are controlled to complete ether in 5 hours
Change reaction.The etherificate rate of double bond is 96.2%.The mean molecule quantity of the resulting many triethyl citrate cottonseed oil ethers of product is about
1500g/mol。
Example 5：ATBC and the tung oil etherificate many ATBC tung oil ethers of synthesis
300g tung oil is added in the churned mechanically reactor of band, and (containing about 2.0mol unsaturated double-bonds, iodine number is 170gI2/
100g oil), 936g ATBCs, 24.7g alchlors, i.e.,：Citrate：Unsaturated double-bond=1.3 in grease (mole
Than), catalyst amount for reaction mass weight 2.0%.Under nitrogen protection, 100 DEG C of reactions are controlled to complete etherificate in 6 hours anti-
Should.The etherificate rate of double bond is 92.2%.The mean molecule quantity of the resulting many ATBC tung oil ethers of product is about 3000g/
mol。
Example 6：ATBC and the soybean oil etherificate many ATBC soybean oil ethers of synthesis
300g soybean oils are added in the churned mechanically reactor of band, and (containing about 1.56mol unsaturated double-bonds, iodine number is
130gI2/ 100g oil), 618g ATBCs, 46g macropore strong acid sulphonic resins, i.e.,：Citrate：Insatiable hunger in grease
It is the 5% of reaction mass weight with double bond=1.1 (mol ratio), catalyst amount.Under nitrogen protection, control 110 DEG C of reactions 8 small
When complete etherification reaction.The etherificate rate of double bond is 91.3%.The average mark of the resulting many ATBC soybean oil ethers of product
Son amount is about 2580g/mol.
Example 7：ATBC and the soybean oil etherificate many ATBC soybean oil ethers of synthesis
300g soybean oils are added in the churned mechanically reactor of band, and (containing about 1.56mol unsaturated double-bonds, iodine number is
130gI2/ 100g oil), 618g ATBCs, 7.4g methanesulfonic acids, i.e.,：Citrate：Unsaturated double-bond=1.1 in grease
(mol ratio), catalyst amount are the 0.8% of reaction mass weight.Under nitrogen protection, 180 DEG C of reactions are controlled to complete ether in 6 hours
Change reaction.The etherificate rate of double bond is 97.2%.The mean molecule quantity of the resulting many ATBC soybean oil ethers of product is about
2580g/mol。
Example 8：ATBC and the soybean oil etherificate many ATBC soybean oil ethers of synthesis
300g soybean oils are added in the churned mechanically reactor of band, and (containing about 1.56mol unsaturated double-bonds, iodine number is
130gI2/ 100g oil), 618g ATBCs, 36.7g boron trifluoride pyridine complexs, i.e.,：Citrate：In grease not
Saturation double bond=1.1 (mol ratio), catalyst amount are the 4% of reaction mass weight.Under nitrogen protection, 160 DEG C of reactions 8 are controlled
Hour completes etherification reaction.The etherificate rate of double bond is 96.5%.The resulting many ATBC soybean oil ethers of product it is average
Molecular weight is about 2580g/mol.
Claims (9)
1. a kind of vegetable oil esters and citrate synthetic macromolecule amount, the preparation method of hyper-branched citrate ester derivatives, its
It is characterised by：With citrate and the biomass grease containing unsaturated double-bond, by certain mol ratio, in catalyst action
Under, the free hydroxyl in citrate molecule is carried out addition under certain conditions with the unsaturated double-bond in biomass grease
Reaction forms ehter bond, and citrate that obtain macromolecule, that hyper-branched mean molecule quantity is 1500~4500g/mol derives
Thing.
2. vegetable oil esters as claimed in claim 1 and citrate synthetic macromolecule amount, hyper-branched citrate ester derivatives
Preparation method, it is characterised in that：Described citrate is triethyl, the tributyl of citric acid or the citric acid of citric acid
Three monooctyl esters.
3. vegetable oil esters as claimed in claim 1 and citrate synthetic macromolecule amount, hyper-branched citrate ester derivatives
Preparation method, it is characterised in that：Described biomass grease is soybean oil, linseed oil, rapeseed oil, cottonseed oil or paulownia
Oil.
4. vegetable oil esters as claimed in claim 1 and citrate synthetic macromolecule amount, hyper-branched citrate ester derivatives
Preparation method, it is characterised in that：Described citrate is citrate with the mol ratio of biomass grease：In soybean oil
Unsaturated double-bond=1.0~1.3.
5. vegetable oil esters as claimed in claim 1 and citrate synthetic macromolecule amount, hyper-branched citrate ester derivatives
Preparation method, it is characterised in that：Described catalyst is the acid of L acids or B acids.
6. vegetable oil esters as claimed in claim 1 and citrate synthetic macromolecule amount, hyper-branched citrate ester derivatives
Preparation method, it is characterised in that：Described catalyst amount is the 0.3~5% of reaction mass weight.
7. the vegetable oil esters described in claim 1 and citrate synthetic macromolecule amount, hyper-branched citrate ester derivatives
Preparation method, it is characterised in that：The reaction condition of described etherification reaction is：Under nitrogen protection, reaction temperature is 80~180
DEG C, the reaction time is 4~8 hours.
8. the vegetable oil esters described in claim 1 and citrate synthetic macromolecule amount, hyper-branched citrate ester derivatives
Preparation method, it is characterised in that：Described L acids is boron trifluoride complex or alchlor.
9. the vegetable oil esters described in claim 1 and citrate synthetic macromolecule amount, hyper-branched citrate ester derivatives
Preparation method, it is characterised in that：Described B acids is sulfuric acid, methanesulfonic acid, phosphotungstic acid or macropore strong acid sulphonic resin.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611050162.1A CN106753809B (en) | 2016-11-24 | 2016-11-24 | Preparation method for synthesizing high-molecular-weight multi-branched citrate ester derivative by using vegetable oil ester and citrate ester |
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|---|---|---|---|
| CN201611050162.1A CN106753809B (en) | 2016-11-24 | 2016-11-24 | Preparation method for synthesizing high-molecular-weight multi-branched citrate ester derivative by using vegetable oil ester and citrate ester |
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| CN106753809A true CN106753809A (en) | 2017-05-31 |
| CN106753809B CN106753809B (en) | 2020-06-26 |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101255114A (en) * | 2007-09-06 | 2008-09-03 | 兰州理工大学 | Method for preparing oleoyl tributyl citrate plasticizer |
| CN101570592A (en) * | 2008-04-30 | 2009-11-04 | 北京化工大学 | Polyether type hyperbranched epoxy resin and preparation method thereof |
| CN103285400A (en) * | 2013-06-18 | 2013-09-11 | 苏州大学 | Acid sensitive polymer prodrug, nanoparticles of prodrug and application of nanoparticles |
| CN103304970A (en) * | 2012-03-16 | 2013-09-18 | 浙江工业大学 | Modified polylactic acid and preparation method thereof |
| CN104646036A (en) * | 2015-02-10 | 2015-05-27 | 南京航空航天大学 | Mo or W modified solid super acidic catalyst and method for synthesizing acetyl tributyl citrate by utilizing catalyst |
-
2016
- 2016-11-24 CN CN201611050162.1A patent/CN106753809B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101255114A (en) * | 2007-09-06 | 2008-09-03 | 兰州理工大学 | Method for preparing oleoyl tributyl citrate plasticizer |
| CN101570592A (en) * | 2008-04-30 | 2009-11-04 | 北京化工大学 | Polyether type hyperbranched epoxy resin and preparation method thereof |
| CN103304970A (en) * | 2012-03-16 | 2013-09-18 | 浙江工业大学 | Modified polylactic acid and preparation method thereof |
| CN103285400A (en) * | 2013-06-18 | 2013-09-11 | 苏州大学 | Acid sensitive polymer prodrug, nanoparticles of prodrug and application of nanoparticles |
| CN104646036A (en) * | 2015-02-10 | 2015-05-27 | 南京航空航天大学 | Mo or W modified solid super acidic catalyst and method for synthesizing acetyl tributyl citrate by utilizing catalyst |
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| CN106753809B (en) | 2020-06-26 |
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