CN103232616A - Fatty acid penta ester plasticizer and preparation method thereof - Google Patents
Fatty acid penta ester plasticizer and preparation method thereof Download PDFInfo
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- CN103232616A CN103232616A CN2013100911645A CN201310091164A CN103232616A CN 103232616 A CN103232616 A CN 103232616A CN 2013100911645 A CN2013100911645 A CN 2013100911645A CN 201310091164 A CN201310091164 A CN 201310091164A CN 103232616 A CN103232616 A CN 103232616A
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Abstract
The invention relates to a fatty acid penta ester plasticizer and a preparation method thereof. The fatty acid penta ester plasticizer has the following molecule structure, wherein R is -CH3, -C2H5, -C3H7, -C4H9, -C5H11, -C6H13, -C7H15, and -C8H17, R1 is defined in the specification, and n is 1, 2 or 3. According to the present invention, the preparation method is combined to achieve a plasticizer with characteristics of low toxicity, high efficiency and degradability so as to obtain a fatty acid penta ester plasticizer meeting requirements and having characteristics of low toxicity and environmental protection; and rich tung oil resources are well utilized so as to promote economy of remote mountain areas, and promote the development of national economy.
Description
Technical field
The invention belongs to technical field of polymer materials, be specifically related to a kind of lipid acid five-ester class softening agent and preparation method thereof.
Background technology
Plastics industry is to develop one of industry faster on the our times, it is widely used in various fields such as industry, agricultural, transportation, national defence, building and daily necessities, in the national economic development, play a part very important, and softening agent is the main chemical assistant of plastics industry, its output is big, wide in variety, plays a part certain to the development of plastics, rubber industry.
Softening agent is one of additives for plastics of worldwide production amount and consumption maximum.For a long time, adjacent benzene class (being mainly DOP) is the main products of softening agent, but along with DOP uses more and more widely in fields such as medical, food product pack, toys for children, people also begin to pay attention to its security.Hygiene department finds, behind the blood that people's input stores with plastics bag, can detect the existence of DOP in human body, and the anti-extraction performance of this explanation DOP is not good enough, influences the healthy of people; Nineteen eighty-two, the American National ICR was studied the toxicity of DOP, and the result shows that it can make rodent carcinogenic.Therefore, the toxicity of DOP has caused global concern.Each country has all taked corresponding measure: U.S. environment protection general bureau has stopped the production of several phthalic ester plasticizer products; Germany bans use of DOP in fields such as medical sanitary, food product pack; Japan also provides against in medical equipment and uses DOP.
And also do not have a kind of low toxicity, efficient, degradable, lower-cost softening agent and corresponding preparation method at present, can't satisfy more and more stricter environment protection to the requirement of softening agent.
Summary of the invention
The invention provides a kind of lipid acid five-ester class softening agent and preparation method thereof, the molecular structure of this lipid acid five-ester class softening agent is as follows:
Wherein, R is :-CH
3,-C
2H
5,-C
3H
7,-C
4H
9,-C
5H
11,-C
6H
13,-C
7H
15,
-C
8H
17R
1For:
, the n span is 1,2 or 3.And low toxicity, efficient, degradable softening agent have been realized in conjunction with its preparation method, obtained the lipid acid five-ester class softening agent of a kind of satisfactory low toxicity, environment-friendly type, simultaneously, the present invention also can make the tung oil resource of China's abundant obtain better utilised, spur the economy of remote mountain areas, advanced development and national economy.
For achieving the above object, technical scheme of the present invention is:
A kind of lipid acid five-ester class softening agent, its molecular structure is as follows:
Wherein, R is :-CH
3,-C
2H
5,-C
3H
7,-C
4H
9,-C
5H
11,-C
6H
13,-C
7H
15Or
-C
8H
17, R
1For:
, the n span is 1,2 or 3.
The preparation method of described lipid acid five-ester class softening agent, step is as follows:
Step 1: MALEIC ANHYDRIDE-glycol ether ester plasticizer synthetic, namely agitator is being housed, thermometer, the mixture that adds glycol ether and MALEIC ANHYDRIDE in the three-necked bottle of water-and-oil separator and spherical condensation tube according to the ratio of predetermined amount of substance, and toluene or benzene are joined in the mixture of glycol ether and MALEIC ANHYDRIDE as the band aqua, the add-on of its band aqua is the 75%-90% of the mixture quality of glycol ether and MALEIC ANHYDRIDE, then the mixture that has added the band aqua in the three-necked bottle is carried out the low-grade fever heating of temperature in 40-45 ℃ of scope, under constant default speed, the mixture that has added the band aqua stirred simultaneously and dissolve the back fully up to glycol ether and MALEIC ANHYDRIDE and form dissolving back mixture with the band aqua, to dissolving the catalyst for synthesizing that adds MALEIC ANHYDRIDE-glycol ether ester plasticizer in the mixture of back, the mass percent scope of the catalyst for synthesizing of MALEIC ANHYDRIDE-glycol ether ester plasticizer is the 0.2%-1.5% of the quality of dissolving back mixture, come this dissolving back mixture is carried out primary reaction with this, the primary reaction temperature is remained on the mixture that obtains behind the 120-200 ℃ of scope internal reaction 1h-5h behind the primary reaction, again to the low-grade monobasic alcohol of the adding of the mixture behind the primary reaction as end-capping reagent, the add-on of end-capping reagent adds according to the scope of the ratio of the default amount of substance of the catalyst for synthesizing of the same MALEIC ANHYDRIDE of end-capping reagent-glycol ether ester plasticizer, mixture behind the primary reaction behind the adding end-capping reagent is carried out second order reaction, the second order reaction temperature remains on the mixture that obtains behind the 180-220 ℃ of scope internal reaction 2-9h after the second order reaction, again it is carried out underpressure distillation after mixture behind the secondary reaction cooled off most temperature range 140-150 ℃, namely obtain MALEIC ANHYDRIDE-glycol ether ester plasticizer;
Step 2: the hydrolysis of tung oil, namely in the other three-necked bottle that prolong and stirring rod are housed, add tung oil, the add-on of tung oil is to add according to the scope of tung oil with the ratio of the amount of substance of the glycol ether of step 1 adding, tung oil is 0.5-2 with the scope of the ratio of the amount of substance of the glycol ether of step 1 adding, it is 50-100 ℃ water bath with thermostatic control that the three-necked bottle that prolong and stirring rod are housed described in this step is carried out in temperature range, tung oil is preheated to 60 ℃ like this, again KOH is dissolved the hydrolysis catalyst solution that obtains methyl alcohol and tung oil as the hydrolysis of tung oil with catalyzer adding methyl alcohol, the hydrolysis of tung oil is 0.1-0.5 with the ratio of catalyzer and the amount of substance of tung oil, this methyl alcohol is 6-10 with the ratio of the amount of substance of tung oil, and the hydrolysis of methyl alcohol and tung oil is joined with catalyst solution form mixture in the tung oil of preheating and react, stop to obtain elementary product behind the reaction 1h-2h, elementary product is moved in the round-bottomed flask, reduce pressure with Rotary Evaporators and to remove methyl alcohol excessive in the elementary product, pour into then in the separating funnel and with dilute sulphuric acid the elementary product of having removed excessive methyl alcohol is carried out the pickling deglycerizin, the hydrolysis of tung oil with catalyzer and saponified after obtain moisture product, moisture product removed by decompression the product of gained is faint yellow oily thing behind the moisture, be the eleostearic acid methyl esters;
Step 3: lipid acid five-ester class softening agent synthetic, namely the eleostearic acid methyl esters that obtains respectively in step 2 and the step 1 and MALEIC ANHYDRIDE-glycol ether ester plasticizer are joined in the three-necked bottle of setting and form eleostearic acid methyl esters and MALEIC ANHYDRIDE-glycol ether ester plasticizer mixture, the eleostearic acid methyl esters is 1-2 with the scope of the ratio of the amount of substance of MALEIC ANHYDRIDE-glycol ether ester plasticizer, add again that to be warming up to temperature range behind the catalyst for synthesizing of lipid acid five-ester class softening agent be 120 ℃-150 ℃ in the three-necked bottle of setting, carry out the building-up reactions of lipid acid five-ester class softening agent then, the mass percent scope of the catalyst for synthesizing add-on of lipid acid five-ester class softening agent is the 0.2-0.7% of eleostearic acid methyl esters and MALEIC ANHYDRIDE-glycol ether ester plasticizer mixture quality, obtains lipid acid five-ester class softening agent behind the insulated and stirred reaction 1h-4h.
The scope of the ratio of the predetermined amount of substance of MALEIC ANHYDRIDE and glycol ether is 1.7-2.1 in the described step 1, the catalyst for synthesizing of the MALEIC ANHYDRIDE in the step 1-glycol ether ester plasticizer comprises tosic acid, Phenylsulfonic acid, thionamic acid, formic acid, acetic acid, oxalic acid, zinc oxide, aluminium sesquioxide, aluminium hydroxide, zinc hydroxide, tetrabutyl titanate, phosphoric acid, hydrochloric acid, sulfuric acid, a kind of or any several mixture in the nitric acid, described end-capping reagent is selected octanol for use, enanthol, hexanol, butanols, amylalcohol, propyl alcohol, a kind of in ethanol or the methyl alcohol or several mixture arbitrarily, the scope of the ratio of the amount of substance that end-capping reagent and the catalyst for synthesizing of MALEIC ANHYDRIDE-glycol ether ester plasticizer are default is 2.1-2.4.
Diglycol in described step 1 can be substituted by triethylene-glycol or tetraethylene-glycol, and the triethylene-glycol that adopt to substitute or tetraethylene-glycol just make respectively the maleic anhydride that obtains in step 1-diglycol ester plasticiser also just be replaced and be generated as maleic anhydride-Triethylene Glycol plasticizer or maleic anhydride-tetraethylene-glycol ester plasticiser, and namely maleic anhydride-diglycol ester plasticiser can be substituted by maleic anhydride-Triethylene Glycol plasticizer or maleic anhydride-tetraethylene-glycol ester plasticiser.
The catalyst for synthesizing of the lipid acid five-ester class softening agent in the described step 3 is a kind of or any several mixture in Lewis acid and the Bruce acid.
The preparation method's of described lipid acid five-ester class softening agent reaction equation is as follows:
R in the formula is :-CH
3,-C
2H
5,-C
3H
7,-C
4H
9,-C
5H
11,-C
6H
13,-C
7H
15Or
-C
8H
17R
1For:
, the n span is 1,2 or 3.
The softening agent that preparation method among the present invention obtains complies with the national standard requirements, and is the five-ester class softening agent of a kind of low toxicity, environment-friendly type.
Description of drawings
Fig. 1 is method flow diagram of the present invention.
Fig. 2 is the infrared spectrum of the MALEIC ANHYDRIDE-glycol ether ester plasticizer, MALEIC ANHYDRIDE-Triethylene Glycol softening agent and the MALEIC ANHYDRIDE-tetraethylene-glycol ester plasticizer that obtain among embodiments of the invention 1, embodiment 2 and the embodiment 3, wherein figure denote 1 represents the infrared spectrum of MALEIC ANHYDRIDE-glycol ether ester plasticizer, figure denote 2 represents the infrared spectrum of MALEIC ANHYDRIDE-Triethylene Glycol softening agent, and figure denote 3 represents the infrared spectrum of MALEIC ANHYDRIDE-tetraethylene-glycol ester plasticizer.
Fig. 3 is the infrared spectrum of the eleostearic acid methyl esters that obtains among the embodiment 1.
Fig. 4 is the infrared spectrum of the lipid acid five-ester class softening agent that obtains among the embodiment 1.
Specific implementation method
The present invention will be further described below by specific embodiment:
Embodiment 1:
Lipid acid five-ester class softening agent, its structure is as follows:
Wherein, R is :-CH
3,-C
2H
5,-C
3H
7,-C
4H
9,-C
5H
11,-C
6H
13,-C
7H
15Or
-C
8H
17R
1For:
, the n span is 1,2 or 3.
The preparation method of described lipid acid five-ester class softening agent, step is as follows:
Step 1: MALEIC ANHYDRIDE-glycol ether ester plasticizer synthetic, the mixture that namely in the three-necked bottle that agitator, thermometer, water-and-oil separator and spherical condensation tube are housed, adds glycol ether and MALEIC ANHYDRIDE according to the ratio of predetermined amount of substance, and toluene is joined in the mixture of glycol ether and MALEIC ANHYDRIDE 75% of the mixture quality that its add-on of being with aqua is glycol ether and MALEIC ANHYDRIDE as the band aqua.Then the mixture that has added the band aqua in the three-necked bottle is carried out the low-grade fever heating of temperature under 40 ℃, under constant default speed, the mixture that has added the band aqua stirred simultaneously and dissolve the back fully up to glycol ether and MALEIC ANHYDRIDE and form dissolving back mixture with the band aqua, to dissolving the catalyst for synthesizing that adds MALEIC ANHYDRIDE-glycol ether softening agent in the mixture of back, the mass percent of the catalyst for synthesizing of MALEIC ANHYDRIDE-glycol ether softening agent is 0.5% of the quality of dissolving back mixture, come this dissolving back mixture is carried out primary reaction with this, the primary reaction temperature is remained on 170 ℃ of mixtures after obtaining down primary reaction behind the reaction 4h, again to the low-grade monobasic alcohol of the adding of the mixture behind the primary reaction as end-capping reagent, the add-on of end-capping reagent adds according to the scope of the ratio of the default amount of substance of the catalyst for synthesizing of the same MALEIC ANHYDRIDE of end-capping reagent-glycol ether ester plasticizer, mixture behind the primary reaction behind the adding end-capping reagent is carried out second order reaction, the second order reaction temperature remains on the mixture after 195 ℃ of reactions obtain second order reaction behind the 4.2h, again it is carried out underpressure distillation after mixture behind the secondary reaction cooled off most 150 ℃ of temperature, namely obtain MALEIC ANHYDRIDE-glycol ether ester plasticizer;
Step 2: the hydrolysis of tung oil, namely in the other three-necked bottle that prolong and stirring rod are housed, add tung oil, the add-on of tung oil is to add according to the scope of tung oil with the ratio of the amount of substance of the glycol ether of step 1 adding, tung oil is 0.7 with the ratio of the amount of substance of the glycol ether of step 1 adding, carrying out in temperature to the three-necked bottle that prolong and stirring rod are housed described in this step is water bath with thermostatic control under 60 ℃, tung oil is preheated to 60 ℃ like this, again KOH is dissolved the hydrolysis catalyst solution that obtains methyl alcohol and tung oil as the hydrolysis of tung oil with catalyzer adding methyl alcohol, the hydrolysis of tung oil is 0.15 with the ratio of catalyzer and the amount of substance of tung oil, this methyl alcohol is 7 with the ratio of the amount of substance of tung oil, and the hydrolysis of methyl alcohol and tung oil is joined with catalyst solution form mixture in the tung oil of preheating and react, stop to obtain elementary product behind the reaction 1h, elementary product is moved in the round-bottomed flask, reduce pressure with Rotary Evaporators and to remove methyl alcohol excessive in the elementary product, pour into then in the separating funnel and with dilute sulphuric acid the elementary product of having removed excessive methyl alcohol is carried out the pickling deglycerizin, the hydrolysis of tung oil with catalyzer and saponified after obtain moisture product, moisture product removed by decompression the product of gained is faint yellow oily thing behind the moisture, be the eleostearic acid methyl esters;
Step 3: lipid acid five-ester class softening agent synthetic, namely the eleostearic acid methyl esters that obtains respectively in step 2 and the step 1 and MALEIC ANHYDRIDE-glycol ether ester plasticizer are joined in the three-necked bottle of setting and form eleostearic acid methyl esters and MALEIC ANHYDRIDE-glycol ether ester plasticizer mixture, the eleostearic acid methyl esters is 1 with the ratio of the amount of substance of MALEIC ANHYDRIDE-glycol ether softening agent, add again that to be warming up to temperature behind the catalyst for synthesizing of lipid acid five-ester class softening agent be 140 ℃ in the three-necked bottle of setting, carry out the building-up reactions of lipid acid five-ester class softening agent then, the mass percent scope of the catalyst for synthesizing add-on of lipid acid five-ester class softening agent is 0.2% of eleostearic acid methyl esters and MALEIC ANHYDRIDE-glycol ether ester plasticizer mixture quality, obtains lipid acid five-ester class softening agent behind the building-up reactions 1h of lipid acid five-ester class softening agent.
The ratio of the predetermined amount of substance of MALEIC ANHYDRIDE and glycol ether ester is 2 in the described step 1, the catalyst for synthesizing of the MALEIC ANHYDRIDE in the step 1-glycol ether ester plasticizer is tosic acid, described end-capping reagent is selected octanol for use, and end-capping reagent is 2.34 with the ratio of the amount of substance that the catalyst for synthesizing of MALEIC ANHYDRIDE-glycol ether ester plasticizer is preset.
The catalyst for synthesizing of the lipid acid five-ester class softening agent in the described step 3 is Lewis acid.
The preparation method's of described lipid acid five-ester class softening agent reaction equation is as follows:
R in the formula is :-CH
3,-C
2H
5,-C
3H
7,-C
4H
9,-C
5H
11,-C
6H
13,-C
7H
15Or
-C
8H
17R
1For:
, the n span is 1,2 or 3.
Embodiment 2:
Lipid acid five-ester class softening agent, its structure is as follows:
Wherein, R is :-CH
3,-C
2H
5,-C
3H
7,-C
4H
9,-C
5H
11,-C
6H
13,-C
7H
15Or
-C
8H
17R
1For:
, the n span is 1,2 or 3.
The preparation method of described lipid acid five-ester class softening agent, step is as follows:
Step 1: MALEIC ANHYDRIDE-Triethylene Glycol softening agent synthetic, namely agitator is being housed, thermometer, the mixture that adds Triethylene glycol and MALEIC ANHYDRIDE in the three-necked bottle of water-and-oil separator and spherical condensation tube according to the ratio of predetermined amount of substance, and benzene is joined in the mixture of Triethylene glycol and MALEIC ANHYDRIDE as the band aqua, 80% of the mixture quality that its add-on of being with aqua is Triethylene glycol and MALEIC ANHYDRIDE, then the mixture that has added the band aqua in the three-necked bottle is carried out the low-grade fever heating of temperature under 40 ℃, under constant default speed, the mixture that has added the band aqua stirred simultaneously and dissolve the back fully up to Triethylene glycol and MALEIC ANHYDRIDE and form dissolving back mixture with the band aqua, to dissolving the catalyst for synthesizing that adds MALEIC ANHYDRIDE-Triethylene Glycol softening agent in the mixture of back, the mass percent scope of the catalyst for synthesizing of MALEIC ANHYDRIDE-Triethylene Glycol softening agent is 0.2% of the quality of dissolving back mixture, come this dissolving back mixture is carried out primary reaction with this, the primary reaction temperature is remained on 170 ℃ of mixtures after obtaining down primary reaction behind the reaction 3h, again to the low-grade monobasic alcohol of the adding of the mixture behind the primary reaction as end-capping reagent, the add-on of end-capping reagent adds according to the scope of the ratio of the default amount of substance of the catalyst for synthesizing of the same MALEIC ANHYDRIDE of end-capping reagent-Triethylene Glycol softening agent, mixture behind the primary reaction behind the adding end-capping reagent is carried out second order reaction, the second order reaction temperature remains on the mixture after 206 ℃ of reactions obtain second order reaction behind the 6.2h, again it is carried out underpressure distillation after mixture behind the secondary reaction cooled off most 150 ℃ of temperature, namely obtain MALEIC ANHYDRIDE-Triethylene Glycol softening agent;
Step 2: the hydrolysis of tung oil, namely in the other three-necked bottle that prolong and stirring rod are housed, add tung oil, the add-on of tung oil is to add according to the scope of tung oil with the ratio of the amount of substance of the Triethylene glycol of step 1 adding, tung oil is 1 with the ratio of the amount of substance of the Triethylene glycol of step 1 adding, carrying out in temperature to the three-necked bottle that prolong and stirring rod are housed described in this step is water bath with thermostatic control under 60 ℃, tung oil is preheated to 60 ℃ like this, again KOH is dissolved the hydrolysis catalyst solution that obtains methyl alcohol and tung oil as the hydrolysis of tung oil with catalyzer adding methyl alcohol, the hydrolysis of tung oil is 0.2 with the ratio of catalyzer and the amount of substance of tung oil, this methyl alcohol is 8 with the ratio of the amount of substance of tung oil, and the hydrolysis of methyl alcohol and tung oil is joined with catalyst solution form mixture in the tung oil of preheating and react, stop to obtain elementary product behind the reaction 1h, elementary product is moved in the round-bottomed flask, reduce pressure with Rotary Evaporators and to remove methyl alcohol excessive in the elementary product, pour into then in the separating funnel and with dilute sulphuric acid the elementary product of having removed excessive methyl alcohol is carried out the pickling deglycerizin, the hydrolysis of tung oil with catalyzer and saponified after obtain moisture product, moisture product removed by decompression the product of gained is faint yellow oily thing behind the moisture, be the eleostearic acid methyl esters;
Step 3: lipid acid five-ester class softening agent synthetic, namely the eleostearic acid methyl esters that obtains respectively in step 2 and the step 1 and MALEIC ANHYDRIDE-Triethylene Glycol softening agent are joined in the three-necked bottle of setting and form eleostearic acid methyl esters and MALEIC ANHYDRIDE-Triethylene Glycol plasticiser mixture, the eleostearic acid methyl esters is 1.25 with the ratio of the amount of substance of MALEIC ANHYDRIDE-Triethylene Glycol softening agent, add again that to be warming up to temperature behind the catalyst for synthesizing of lipid acid five-ester class softening agent be 140 ℃ in the three-necked bottle of setting, carry out the building-up reactions of lipid acid five-ester class softening agent then, the mass percent of the catalyst for synthesizing add-on of lipid acid five-ester class softening agent is 0. 5% of eleostearic acid methyl esters and MALEIC ANHYDRIDE-Triethylene Glycol plasticiser mixture quality, obtains lipid acid five-ester class softening agent behind the building-up reactions 2h of lipid acid five-ester class softening agent.
The ratio of the predetermined amount of substance of MALEIC ANHYDRIDE and Triethylene Glycol is 2 in the described step 1, the catalyst for synthesizing of the MALEIC ANHYDRIDE in the step 1-Triethylene Glycol softening agent is tetrabutyl titanate, described end-capping reagent is selected octanol for use, and end-capping reagent is 2.33 with the ratio of the amount of substance that the catalyst for synthesizing of MALEIC ANHYDRIDE-Triethylene glycol softening agent is preset.
The catalyst for synthesizing of the lipid acid five-ester class softening agent in the described step 3 is Bruce acid.
Embodiment 3:
Lipid acid five-ester class softening agent, its structure is as follows:
Wherein, R is :-CH
3,-C
2H
5,-C
3H
7,-C
4H
9,-C
5H
11,-C
6H
13,-C
7H
15Or
-C
8H
17R
1For:
, the n span is 1,2 or 3.
The preparation method of described lipid acid five-ester class softening agent, step is as follows:
Step 1: MALEIC ANHYDRIDE-tetraethylene-glycol ester plasticizer synthetic, namely agitator is being housed, thermometer, the mixture that adds tetraethylene-glycol softening agent and MALEIC ANHYDRIDE in the three-necked bottle of water-and-oil separator and spherical condensation tube according to the ratio of predetermined amount of substance, and toluene is joined in the mixture of tetraethylene-glycol softening agent and MALEIC ANHYDRIDE as the band aqua, 90% of the mixture quality that its add-on of being with aqua is tetraethylene-glycol softening agent and MALEIC ANHYDRIDE, then the mixture that has added the band aqua in the three-necked bottle is carried out the low-grade fever heating of temperature under 40 ℃, under constant default speed, the mixture that has added the band aqua stirred simultaneously and dissolve the back fully up to tetraethylene-glycol softening agent and MALEIC ANHYDRIDE and form dissolving back mixture with the band aqua, to dissolving the catalyst for synthesizing that adds MALEIC ANHYDRIDE-tetraethylene-glycol ester plasticizer in the mixture of back, the mass percent of the catalyst for synthesizing of MALEIC ANHYDRIDE-tetraethylene-glycol ester plasticizer is 0.3% of the quality of dissolving back mixture, come this dissolving back mixture is carried out primary reaction with this, the primary reaction temperature is remained on the mixture that obtains behind 170 ℃ of scope internal reaction 3h behind the primary reaction, again to the low-grade monobasic alcohol of the adding of the mixture behind the primary reaction as end-capping reagent, the add-on of end-capping reagent adds according to the scope of the ratio of the default amount of substance of the catalyst for synthesizing of the same MALEIC ANHYDRIDE of end-capping reagent-tetraethylene-glycol ester plasticizer, mixture behind the primary reaction behind the adding end-capping reagent is carried out second order reaction, the second order reaction temperature remains on the mixture that obtains behind 212 ℃ of scope internal reaction 8h after the second order reaction, mixture behind the secondary reaction is cooled off most temperature again it is carried out underpressure distillation after being 150 ℃, namely obtain MALEIC ANHYDRIDE-tetraethylene-glycol ester plasticizer;
Step 2: the hydrolysis of tung oil, namely in the other three-necked bottle that prolong and stirring rod are housed, add tung oil, the add-on of tung oil is to add according to the scope of tung oil with the ratio of the tetraethylene-glycol amount of substance of step 1 adding, tung oil is 2 with the scope of the ratio of the tetraethylene-glycol amount of substance of step 1 adding, it is 60 ℃ water bath with thermostatic control that the three-necked bottle that prolong and stirring rod are housed described in this step is carried out in temperature range, tung oil is preheated to 60 ℃ like this, again KOH is dissolved the hydrolysis catalyst solution that obtains methyl alcohol and tung oil as the hydrolysis of tung oil with catalyzer adding methyl alcohol, the hydrolysis of tung oil is 0.5 with the ratio of catalyzer and the amount of substance of tung oil, this methyl alcohol is 10 with the ratio of the amount of substance of tung oil, and the hydrolysis of methyl alcohol and tung oil is joined with catalyst solution form mixture in the tung oil of preheating and react, stop to obtain elementary product behind the reaction 1h, elementary product is moved in the round-bottomed flask, reduce pressure with Rotary Evaporators and to remove methyl alcohol excessive in the elementary product, pour into then in the separating funnel and with dilute sulphuric acid the elementary product of having removed excessive methyl alcohol is carried out the pickling deglycerizin, the hydrolysis of tung oil with catalyzer and saponified after obtain moisture product, moisture product removed by decompression the product of gained is faint yellow oily thing behind the moisture, be the eleostearic acid methyl esters;
Step 3: lipid acid five-ester class softening agent synthetic, namely the eleostearic acid methyl esters that obtains respectively in step 2 and the step 1 and MALEIC ANHYDRIDE-tetraethylene-glycol ester plasticizer are joined in the three-necked bottle of setting and form eleostearic acid methyl esters and MALEIC ANHYDRIDE-tetraethylene-glycol ester plasticizer mixture, the eleostearic acid methyl esters is 2 with the ratio of the amount of substance of MALEIC ANHYDRIDE-tetraethylene-glycol ester plasticizer, add again that to be warming up to temperature behind the catalyst for synthesizing of lipid acid five-ester class softening agent be 140 ℃ in the three-necked bottle of setting, carry out the building-up reactions of lipid acid five-ester class softening agent then, the mass percent scope of the catalyst for synthesizing add-on of lipid acid five-ester class softening agent is 0.7% of eleostearic acid methyl esters and MALEIC ANHYDRIDE-glycol ether ester plasticizer mixture quality, obtains lipid acid five-ester class softening agent behind the building-up reactions 2h of lipid acid five-ester class softening agent.
The scope of the ratio of the predetermined amount of substance of MALEIC ANHYDRIDE and tetraethylene-glycol is 2.1 in the described step 1, the catalyst for synthesizing of the MALEIC ANHYDRIDE in the step 1-tetraethylene-glycol ester plasticizer comprises tetrabutyl titanate, described end-capping reagent is selected octanol for use, and end-capping reagent is 2.31 with the ratio of the amount of substance that the catalyst for synthesizing of MALEIC ANHYDRIDE-glycol ether ester plasticizer is preset.
The catalyst for synthesizing of the lipid acid five-ester class softening agent in the described step 3 is Lewis acid.
At embodiments of the invention, characterize by the chemical structure of infrared spectrum to MALEIC ANHYDRIDE-glycol ether ester plasticizer, MALEIC ANHYDRIDE-Triethylene Glycol softening agent, MALEIC ANHYDRIDE-tetraethylene-glycol ester plasticizer, then its infared spectrum is analyzed, as shown in Figure 2.Fig. 3 for the infrared spectrum of the eleostearic acid methyl esters that obtains among the embodiment 1 as shown in Figure 3.The infrared spectrum of the lipid acid five-ester class softening agent that obtains among the embodiment 1 as shown in Figure 4.
MALEIC ANHYDRIDE-glycol ether the ester plasticizer that synthesizes among the embodiment among the present invention, MALEIC ANHYDRIDE-Triethylene Glycol softening agent, MALEIC ANHYDRIDE-tetraethylene-glycol ester plasticizer and lipid acid five-ester class softening agent are all measured its acid number by GB GB ∕ T1668, measure its hydroxyl value by GB ∕ T7193, measure its saponification value by GB ∕ T1665, measure its weight loss on heating by GB ∕ T1669, measure its viscosity by GB ∕ T2796, measure its flash-point by GB ∕ T1671, measurement result sees Table 1 at embodiment 1, the MALEIC ANHYDRIDE that embodiment 2 and embodiment 3 prepare respectively-glycol ether ester plasticizer, the test result of MALEIC ANHYDRIDE-Triethylene Glycol softening agent and MALEIC ANHYDRIDE-tetraethylene-glycol ester plasticizer and table 2 are at the measurement result of the lipid acid five-ester class softening agent of embodiment 1.
Claims (6)
1. lipid acid five-ester class softening agent is characterized in that its molecular structure is as follows:
Wherein, R is :-CH
3,-C
2H
5,-C
3H
7,-C
4H
9,-C
5H
11,-C
6H
13,-C
7H
15Or
-C
8H
17, R
1For:
, the n span is 1,2 or 3.
2. the preparation method of lipid acid five-ester class softening agent according to claim 1 is characterized in that step is as follows:
Step 1: MALEIC ANHYDRIDE-glycol ether ester plasticizer synthetic, namely agitator is being housed, thermometer, the mixture that adds glycol ether and MALEIC ANHYDRIDE in the three-necked bottle of water-and-oil separator and spherical condensation tube according to the ratio of predetermined amount of substance, and toluene or benzene are joined in the mixture of glycol ether and MALEIC ANHYDRIDE as the band aqua, the add-on of its band aqua is the 75%-90% of the mixture quality of glycol ether and MALEIC ANHYDRIDE, then the mixture that has added the band aqua in the three-necked bottle is carried out the low-grade fever heating of temperature in 40-45 ℃ of scope, under constant default speed, the mixture that has added the band aqua stirred simultaneously and dissolve the back fully up to glycol ether and MALEIC ANHYDRIDE and form dissolving back mixture with the band aqua, to dissolving the catalyst for synthesizing that adds MALEIC ANHYDRIDE-glycol ether ester plasticizer in the mixture of back, the mass percent scope of the catalyst for synthesizing of MALEIC ANHYDRIDE-glycol ether ester plasticizer is the 0.2%-1.5% of the quality of dissolving back mixture, come this dissolving back mixture is carried out primary reaction with this, the primary reaction temperature is remained on the mixture that obtains behind the 120-200 ℃ of scope internal reaction 1h-5h behind the primary reaction, again to the low-grade monobasic alcohol of the adding of the mixture behind the primary reaction as end-capping reagent, the add-on of end-capping reagent adds according to the scope of the ratio of the default amount of substance of the catalyst for synthesizing of the same MALEIC ANHYDRIDE of end-capping reagent-glycol ether ester plasticizer, mixture behind the primary reaction behind the adding end-capping reagent is carried out second order reaction, the second order reaction temperature remains on the mixture that obtains behind the 180-220 ℃ of scope internal reaction 2-9h after the second order reaction, again it is carried out underpressure distillation after mixture behind the secondary reaction cooled off most temperature range 140-150 ℃, namely obtain MALEIC ANHYDRIDE-glycol ether ester plasticizer;
Step 2: the hydrolysis of tung oil, namely in the other three-necked bottle that prolong and stirring rod are housed, add tung oil, the add-on of tung oil is to add according to the scope of tung oil with the ratio of the amount of substance of the glycol ether of step 1 adding, tung oil is 0.5-2 with the scope of the ratio of the amount of substance of the glycol ether of step 1 adding, it is 50-100 ℃ water bath with thermostatic control that the three-necked bottle that prolong and stirring rod are housed described in this step is carried out in temperature range, tung oil is preheated to 60 ℃ like this, again KOH is dissolved the hydrolysis catalyst solution that obtains methyl alcohol and tung oil as the hydrolysis of tung oil with catalyzer adding methyl alcohol, the hydrolysis of tung oil is 0.1-0.5 with the ratio of catalyzer and the amount of substance of tung oil, this methyl alcohol is 6-10 with the ratio of the amount of substance of tung oil, and the hydrolysis of methyl alcohol and tung oil is joined with catalyst solution form mixture in the tung oil of preheating and react, stop to obtain elementary product behind the reaction 1h-2h, elementary product is moved in the round-bottomed flask, reduce pressure with Rotary Evaporators and to remove methyl alcohol excessive in the elementary product, pour into then in the separating funnel and with dilute sulphuric acid the elementary product of having removed excessive methyl alcohol is carried out the pickling deglycerizin, the hydrolysis of tung oil with catalyzer and saponified after obtain moisture product, moisture product removed by decompression the product of gained is faint yellow oily thing behind the moisture, be the eleostearic acid methyl esters;
Step 3: lipid acid five-ester class softening agent synthetic, namely the eleostearic acid methyl esters that obtains respectively in step 2 and the step 1 and MALEIC ANHYDRIDE-glycol ether ester plasticizer are joined in the three-necked bottle of setting and form eleostearic acid methyl esters and MALEIC ANHYDRIDE-glycol ether plasticiser mixture, the eleostearic acid methyl esters is 1-3 with the scope of the ratio of the amount of substance of MALEIC ANHYDRIDE-glycol ether softening agent, add again that to be warming up to temperature range behind the catalyst for synthesizing of lipid acid five-ester class softening agent be 120 ℃-150 ℃ in the three-necked bottle of setting, carry out the building-up reactions of lipid acid five-ester class softening agent then, the mass percent scope of the catalyst for synthesizing add-on of lipid acid five-ester class softening agent is the 0.2-0.7% of eleostearic acid methyl esters and MALEIC ANHYDRIDE-glycol ether ester plasticizer mixture quality, obtains lipid acid five-ester class softening agent behind the building-up reactions 1h-4h of lipid acid five-ester class softening agent.
3. the preparation method of lipid acid five-ester class softening agent according to claim 2, it is characterized in that, the scope of the ratio of the predetermined amount of substance of MALEIC ANHYDRIDE and glycol ether ester is 1.7-2.1 in the described step 1, the catalyst for synthesizing of the MALEIC ANHYDRIDE in the step 1-glycol ether ester plasticizer comprises tosic acid, thionamic acid, Phenylsulfonic acid, formic acid, acetic acid, oxalic acid, zinc oxide, aluminium sesquioxide, aluminium hydroxide, zinc hydroxide, tetrabutyl titanate, phosphoric acid, hydrochloric acid, sulfuric acid, a kind of or any several mixture in the nitric acid, described end-capping reagent is selected octanol for use, hexanol, butanols, amylalcohol, propyl alcohol, a kind of in ethanol or the methyl alcohol or several mixture arbitrarily, the scope of the ratio of the amount of substance that end-capping reagent and the catalyst for synthesizing of MALEIC ANHYDRIDE-glycol ether softening agent are default is 2.1-2.4.
4. according to the preparation method of claim 2 or the described lipid acid five-ester of claim 3 class softening agent, it is characterized in that, glycol ether in the described step 1 can be substituted by Triethylene glycol or tetraethylene-glycol, and the Triethylene glycol that adopt to substitute or tetraethylene-glycol just make the MALEIC ANHYDRIDE-glycol ether ester plasticizer that obtains in the step 1 also just be replaced respectively to be generated as MALEIC ANHYDRIDE-Triethylene Glycol softening agent or MALEIC ANHYDRIDE-tetraethylene-glycol ester plasticizer, and namely MALEIC ANHYDRIDE-glycol ether softening agent can be substituted by MALEIC ANHYDRIDE-Triethylene Glycol softening agent or MALEIC ANHYDRIDE-tetraethylene-glycol ester plasticizer.
5. according to the preparation method of claim 2 or the described lipid acid five-ester of claim 3 class softening agent, it is characterized in that the catalyst for synthesizing of the lipid acid five-ester class softening agent in the described step 3 is a kind of or any several mixture in Lewis acid and the Bruce acid.
6. the preparation method of lipid acid five-ester class softening agent according to claim 2 is characterized in that, the preparation method's of described lipid acid five-ester class softening agent reaction equation is as follows:
R in the formula is :-CH
3,-C
2H
5,-C
3H
7,-C
4H
9,-C
5H
11,-C
6H
13,-C
7H
15Or
-C
8H
17
R
1For:
, the n span is 1,2 or 3.
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| CN112661635A (en) * | 2020-12-22 | 2021-04-16 | 浙江弘博新材料科技有限公司 | Environment-friendly synthesis method of plasticizer dibutyl phthalate |
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| CN101367731A (en) * | 2008-07-29 | 2009-02-18 | 中国林业科学研究院林产化学工业研究所 | C22 triacid triester elasticizer and method of preparing the same |
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| CN112661635A (en) * | 2020-12-22 | 2021-04-16 | 浙江弘博新材料科技有限公司 | Environment-friendly synthesis method of plasticizer dibutyl phthalate |
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