CN106398236B - A kind of technique of epoxidized linseed oil and citric acid composite elasticizer - Google Patents
A kind of technique of epoxidized linseed oil and citric acid composite elasticizer Download PDFInfo
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- CN106398236B CN106398236B CN201610706722.8A CN201610706722A CN106398236B CN 106398236 B CN106398236 B CN 106398236B CN 201610706722 A CN201610706722 A CN 201610706722A CN 106398236 B CN106398236 B CN 106398236B
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- 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
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- 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
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Abstract
The invention discloses the techniques of a kind of epoxidized linseed oil and citric acid composite elasticizer, and citric acid, n-butanol, sulfuric acid are added in four mouthfuls of corkages, and 4 ~ 7h is stirred at 130 ~ 150 DEG C, tributyl citrate is obtained after dealcoholysis；Linseed oil, petroleum ether, formic acid are added in there-necked flask, is stirred at 60 ~ 70 DEG C by the speed of 300 ~ 500r/min, and instill the mixed solution of hydrogen peroxide and catalyst, after reacting 3 ~ 4 hours, stops stirring, adds in sodium hydroxide solution, acetic acid；The material mixing of gained; and 110 150 DEG C are heated under acidic catalyst, refuxing esterification reaction is carried out by water knockout drum, acetic anhydride is added in after cooling to 50 60 DEG C; acetylization reactions are carried out at 100 125 DEG C, 2 3h open vacuum after the reaction was complete and steam by-product acetic acid.Finally by neutralizing, washing, dry.The present invention has ehter bond, and more traditional citrate plasticizer compatibility is more preferable, is not easy to be precipitated, and epoxidized linseed oil is combined with citrate composite elasticizer, and performance is more excellent.
Description
Technical field
The present invention relates to a kind of plasticizer, and in particular to a kind of composite elasticizer.
Background technology
With the rapid development of Plastics Industry and textile and dyeing industry, the dosage of plasticizer dramatically increases.And present market
Upper more common plasticizer is phthalate, and people were to the concern of health and to traditional phthalate in recent years
The development of plasticizer research finds that phthalic ester plasticizer can pollute empty gas and water and soil or even food, and
Degradation speed is extremely slow in the environment, thus as the global environmental contaminants being concerned.In addition, in daily life people with
Plastic products are in direct contact, and phthalic ester plasticizer into human body and can cause different degrees of by all means
Harm.Epoxy plasticiser is a kind of novel non-toxic plasticizer of successful exploitation recently, it refers to carry epoxy in molecular structure
The organic compound of group has many advantages, such as that nontoxic, heat-resisting and light resistance is good compared with traditional adjacent benzene class plasticizer.With generation
The raising of various countries of boundary environmental consciousness, the plastic products such as medicine and food packaging, daily necessities, toy are to primary plasticizer phthalic acid
Dioctyl ester etc. proposes higher purity and hygienic requirements, and epoxy plasticiser is increasingly becoming state as non-toxic, environmental friendly plasticizer
The hot spot of inside and outside application study.
Citric acid ester plasticizer product has good emulsification, wetting, solubilising and dispersibility, as it is a kind of it is nontoxic,
" green chemical products " pollution-free, non-stimulated, biological degradability is good, be widely used in food, weaving, plastics, process hides,
The industries such as detergent, cosmetics, tobacco, wide market.But there is easy precipitation compared with phthalic ester plasticizer
With migrate it is big the problems such as, volatility is also bigger, so as to affect the use scope of citric acid ester plasticizer.To meet city
The plasticizer environmentally friendly, nontoxic, with better function of field demand is badly in need of improving at present the property of existing citric acid ester plasticizer
Can, develop Novel lemon acid ester plasticizer.
Invention content
The technical problems to be solved by the invention be citric acid ester plasticizer be easily precipitated and migration it is big, and it is an object of the present invention to provide
The technique of a kind of epoxidized linseed oil and citric acid composite elasticizer solves the big use scope of citric acid ester plasticizer migration and is limited
System, and then the problem of influence performance.
The present invention is achieved through the following technical solutions：
The technique of a kind of epoxidized linseed oil and citric acid composite elasticizer, includes the following steps：
（1）Citric acid, positive fourth are added in blender, protractor, oil water separator, four mouthfuls of condenser corkages
Alcohol, sulfuric acid stir 4 ~ 7h at 130 ~ 150 DEG C, tributyl citrate crude product are obtained after dealcoholysis；
（2）Linseed oil, petroleum ether, first are added in the there-necked flask with agitating device, titration outfit and temperature control device
Acid is stirred by the speed of 300 ~ 500r/min at 60 ~ 70 DEG C, and instills the mixed solution of hydrogen peroxide and catalyst, reaction 3
After ~ 4 hours, stop stirring, add in sodium hydroxide solution, acetic acid；
（3）By step（1）The substance of gained is added to step（2）In, and it is heated to 110-150 under acidic catalyst
DEG C, refuxing esterification reaction is carried out by water knockout drum, acetic anhydride is added in after cooling to 50-60 DEG C, acetylation is carried out at 100-125 DEG C
Reaction, 2-3h open vacuum after the reaction was complete and steam by-product acetic acid.Finally by neutralizing, washing, dry.
Citrate plasticizer is high intolerant to migration, volatility, research shows that, the smaller plasticizer of molecular weight is in polymer collection
It is easy to migrate in body.Its resistance to migration can be improved by the molecular weight for improving plasticizer.In addition, by containing
Ehter bond is introduced in the plasticizer of ester group, the compatibility and pliability of resin can be improved, so as to reach the mesh for improving resin flexibility
, research shows that, Etheric ester type plasticizer has good thermal stability and low volatility.
In the preparation, in the reaction environment of acid, epoxy bond is easy to the double hydroxyls of open loop generation to epoxidized linseed oil.
Hydroxyl can be converted into side chain ether in the hydroxyl of polyol.The hydroxyl of polyol is converted into side
The most preferably mechanism of chain ether is known Williamson synthesis mechanisms, including passing through hydroxyl, i.e. alcohol groups, with active gold
Either metal hydroxides reacts to form alkoxide then alkoxide and alkyl halide or alkylsurfuric acid reactant salt for category or metal hydride
Generate side chain ether.
Further, different mechanism there are many existing, by these mechanism, the hydroxyl of polyol can convert
For side-chain ester group.However, the preferred mechanism used in the present invention is well-known Fischer esterifications, wherein, carboxylic acid exists
Under acid condition side-chain ester group is generated with hydroxyl reaction.
The technique of a kind of epoxidized linseed oil and citric acid composite elasticizer, the step（2）In catalyst be strong-acid type
Cation exchange resin.
The technique of a kind of epoxidized linseed oil and citric acid composite elasticizer, the hydrogen peroxide are exchanged with strong-acid type cation
Resin quality portion rate is 13：0.2~0.6.
The technique of a kind of epoxidized linseed oil and citric acid composite elasticizer, the step（3）In acidic catalyst be second
Acid.
The technique of a kind of epoxidized linseed oil and citric acid composite elasticizer, the step（2）Middle linseed oil, sodium hydroxide are molten
Liquid, acetic acid molar ratio be 1：0.5~1.5：0.5~1.5.
Wherein, strongly acidic cation-exchange mainly contains the reactive group such as sulfonic group of highly acid, this amberlite
Fat can exchange all cations.Make the catalyst of epoxidation reaction, product colour using storng-acid cation exchange resin
Much lighter is wanted, and will not etching apparatus.
Acetic anhydride, as important acetylation reagent, acetic anhydride is used to manufacture cellulose ethanoate；Acetic acid plastics；Noninflammability electricity
Shadow film as solvent and dehydrating agent, is also important acetylation reagent and polymerization initiator.
Contain the saturated carboxylic acid there are two carbon atom in molecular acid, be the important containing oxygen derivative of hydrocarbon.Functional group is carboxyl.
Because being the main component of vinegar, also known as acetic acid.Such as mainly exist in the form of its compound ester in fruit or vegetable oil；
Exist in the form of free acid in the tissue of animal, in excreta and blood.Contain 3% ~ 5% acetic acid in common vinegar.
Tributyl citrate, is often referred to tri-n-butyl citrate, and chemical name 3- hydroxyl -3- carboxyl glutaric acid tributyls are
A kind of ester type compound, water white transparency high boiling liquid, is slightly soluble in water, dissolves each other with most organic solvents.Industrially by citric acid
It is reacted with n-butanol, can be directly used for plasticizer, can also be further processed into the plasticizer acetyl tributyl citrate of function admirable
Tributyl.This product low toxicity, can be considered nontoxic plasticizer, is commonly called as environment-friendlyplasticizer plasticizer, can be restricted with alternate application range
Phthalic ester plasticizer.
Esterification is a kind of organic chemical reactions, usually reversible reaction.Traditional esterification techniques are existed with acid and alcohol
Heating reflux reaction under acid catalysis.This reaction is also referred to as Fischer esterification.The effect of the concentrated sulfuric acid is catalyst and dehydration
Agent, the carbonyl of carboxylic acid can be protonated, enhance the electrophilicity of carbonyl carbon, accelerate reaction rate by it;Dereaction can also be removed
By-product water, improve the yield of ester.Typical esterification has the reaction of ethyl alcohol and acetic acid, second of the generation with aromatic odor
Acetoacetic ester is the raw material for manufacturing dyestuff and medicine.Esterification is widely used in the fields such as organic synthesis.
Compared with prior art, the present invention it has the following advantages and advantages：
1st, the technique of a kind of epoxidized linseed oil of the present invention and citric acid composite elasticizer, has ehter bond, more traditional citric acid
Ester plasticiser compatibility is more preferable；
2nd, the technique of a kind of epoxidized linseed oil of the present invention and citric acid composite elasticizer, epoxidized linseed oil are answered with citrate
It closes plasticizer to be combined, performance is more excellent；
3rd, the technique of a kind of epoxidized linseed oil of the present invention and citric acid composite elasticizer, with traditional citrate plasticizer phase
Than reducing mobility, being not easy to be precipitated.
Specific embodiment
To make the objectives, technical solutions, and advantages of the present invention clearer, with reference to embodiment, the present invention is made
Further to be described in detail, exemplary embodiment of the invention and its explanation are only used for explaining the present invention, are not intended as to this
The restriction of invention.
Embodiment
A kind of epoxidized linseed oil of the present invention and the technique of citric acid composite elasticizer, include the following steps：
（1）Citric acid, positive fourth are added in blender, protractor, oil water separator, four mouthfuls of condenser corkages
Alcohol, sulfuric acid stir 4 ~ 7h at 130 ~ 150 DEG C, tributyl citrate crude product are obtained after dealcoholysis；
（2）Linseed oil, petroleum ether, first are added in the there-necked flask with agitating device, titration outfit and temperature control device
Acid is stirred at 60 ~ 70 DEG C by the speed of 300 ~ 500r/min, and instills hydrogen peroxide and strongly acidic cation-exchange
Mixed solution after reacting 3 ~ 4 hours, stops stirring, adds in sodium hydroxide solution, acetic acid, and linseed oil, sodium hydroxide are molten
Liquid, acetic acid molar ratio be 1：0.8：0.8；
（3）By step（1）The substance of gained is added to step（2）In, and 110-150 is heated under the action of acetic acid
DEG C, refuxing esterification reaction is carried out by water knockout drum, acetic anhydride is added in after cooling to 50-60 DEG C, acetylation is carried out at 100-125 DEG C
Reaction, 2-3h open vacuum after the reaction was complete and steam by-product acetic acid.Finally by neutralizing, washing, dry.
Wherein, citric acid, n-butanol, sulfuric acid ratio of weight and number be 1:1~2:0.01；And citric acid and acetic anhydride
Molar ratio is 1：2.5；
Linseed oil, petroleum ether, formic acid, hydrogen peroxide, strongly acidic cation-exchange quality parts ratio be 10：3：5：
13：0.5；
Above-described specific embodiment has carried out the purpose of the present invention, technical solution and advantageous effect further
It is described in detail, it should be understood that the foregoing is merely the specific embodiment of the present invention, is not intended to limit the present invention
Protection domain, all within the spirits and principles of the present invention, any modification, equivalent substitution, improvement and etc. done should all include
Within protection scope of the present invention.
Claims (2)
1. the technique of a kind of epoxidized linseed oil and citric acid composite elasticizer, which is characterized in that include the following steps：
（1）Citric acid, n-butanol, sulphur are added in blender, protractor, oil water separator, four mouthfuls of condenser corkages
Acid stirs 4 ~ 7h at 130 ~ 150 DEG C, tributyl citrate is obtained after dealcoholysis；
（2）Linseed oil, petroleum ether, formic acid are added in the there-necked flask with agitating device, titration outfit and temperature control device,
It is stirred at 60 ~ 70 DEG C by the speed of 300 ~ 500r/min, and instills the mixed solution of hydrogen peroxide and catalyst, reaction 3 ~ 4 is small
Shi Hou stops stirring, adds in sodium hydroxide solution, acetic acid；
（3）By step（1）The substance of gained is added to step（2）In, and 110-150 DEG C is heated under acidic catalyst, lead to
It crosses water knockout drum and carries out refuxing esterification reaction, acetic anhydride is added in after cooling to 50-60 DEG C, acetylization reaction is carried out at 100-125 DEG C,
2-3h opens vacuum after the reaction was complete and steams by-product acetic acid, finally by neutralizing, it is washing, dry；
The step（2）In catalyst for strongly acidic cation-exchange, the hydrogen peroxide is handed over strong-acid type cation
It is 13 to change resin quality portion rate：0.2 ~ 0.6, the step（2）Middle linseed oil, sodium hydroxide solution, acetic acid molar ratio be
1：0.5~1.5：0.5~1.5.
2. the technique of a kind of epoxidized linseed oil according to claim 1 and citric acid composite elasticizer, which is characterized in that institute
State step（3）In acidic catalyst be acetic acid.
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| CN107930660B (en) * | 2017-10-13 | 2019-06-25 | 河南大学 | A kind of catalyst and its method for preparing epoxidized linseed oil |
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