CN112110816A - Preparation method of polyol fatty acid ester plasticizer - Google Patents
Preparation method of polyol fatty acid ester plasticizer Download PDFInfo
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- CN112110816A CN112110816A CN202010910417.7A CN202010910417A CN112110816A CN 112110816 A CN112110816 A CN 112110816A CN 202010910417 A CN202010910417 A CN 202010910417A CN 112110816 A CN112110816 A CN 112110816A
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- fatty acid
- acid ester
- polyol fatty
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H1/00—Processes for the preparation of sugar derivatives
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H15/00—Compounds containing hydrocarbon or substituted hydrocarbon radicals directly attached to hetero atoms of saccharide radicals
- C07H15/02—Acyclic radicals, not substituted by cyclic structures
- C07H15/04—Acyclic radicals, not substituted by cyclic structures attached to an oxygen atom of the saccharide radical
- C07H15/06—Acyclic radicals, not substituted by cyclic structures attached to an oxygen atom of the saccharide radical being a hydroxyalkyl group esterified by a fatty acid
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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
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
- C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
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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
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
- C08K5/1545—Six-membered rings
Abstract
The invention discloses a preparation method of a polyol fatty acid ester plasticizer, which comprises the following steps: (1) adding polyhydric alcohol and monocarboxylic acid into a reactor according to the mole number of carboxyl being 1.2-1.5 times of that of hydroxyl, stirring and mixing, heating to 150-180 ℃, removing water generated in the reaction through a water separator, and stopping heating to terminate the reaction after no water is generated; (2) and continuously heating to 130-160 ℃ to remove unreacted fatty acid, cooling to below 70 ℃, decoloring by using active carbon, and filtering to obtain the polyol fatty acid ester. The preparation method of the polyol fatty acid ester plasticizer adopts the polyol and the monocarboxylic acid as raw materials, and the polyol carboxylic ester obtained by the esterification reaction has a good plasticizing effect, and is safe and nontoxic.
Description
Technical Field
The invention relates to the technical field of plasticizers, in particular to a preparation technology of a polyol fatty acid ester plasticizer.
Background
Plasticizers, also known as plasticizers, are commonly used additives in plastics and their products and can be used to improve the processability, ductility, flexibility, etc. of materials. The ester organic matter is used as a plasticizer to be mixed with the high molecular polymer, and polar groups on the molecules of the ester organic matter are mutually attracted with polar atoms on a high molecular chain of the polymer, so that the interaction force of the high molecules is reduced, the moving space of the high molecular chain segment can be increased, and the glass transition temperature of the high molecular polymer is reduced.
Because the o-benzene plasticizer and the plastic and other materials are only physically mixed, the o-benzene plasticizer and the plastic and other materials are easily dissolved out by grease and the like, and enter a human body through diet absorption or migrate into the surrounding environment, so that the health of human beings is damaged, and environmental pollution and harm are caused. The toxicity of the o-benzene plasticizer to human bodies is caused by interfering the direct interaction between follicle stimulating hormone or testosterone and receptors thereof, and by competing with hormone molecules for the receptors, inhibiting the regulation of hormones and further influencing the normal functions of life bodies. In addition, studies have shown that the o-benzene plasticizer may be associated with the onset of type II diabetes, increasing the risk of endometriosis in women, increasing the risk of asthma and allergy in children and adults, and causing diseases such as autism.
Polyol fatty acid ester plasticizers are widely favored in the market as substitutes for phthalate-based plasticizers because of their low mobility, low volatility and excellent plasticizing properties. The common preparation of polyol fatty acid esters involves esterification of monohydric, dihydric, trihydric and tetrahydric alcohols with fatty acids, and the generated aliphatic esters are prone to have insufficient compatibility compared with aromatic esters. And the commonly used polyhydric alcohol is synthesized by petrochemical industry and has certain toxic and harmful properties. Currently, PVC gaskets are most commonly used for plastic bottle inner caps to prevent liquid leakage and maintain sealing properties, but as PVC gaskets for plastic bottles for bottled water, bottled beverages, and the like, in order to improve edible safety, dissolution and migration of plasticizers in PVC gasket products should be prevented.
The basic physicochemical properties of the plasticizer are: has better thermal stability and chemical stability; is compatible with the polymer within a certain range; higher boiling point, difficult volatilization and the like. The green nontoxic plasticizer has the performance requirements of good plasticizing effect, safety, no toxicity and special performance, such as cold resistance, heat resistance and the like under special conditions.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: aiming at the defects in the prior art, the preparation method of the natural nontoxic polyalcohol fatty acid ester plasticizer synthesized by various sugar alcohols and fatty acids from sugar sources is provided.
In order to solve the technical problems, the technical scheme of the invention is as follows:
a preparation method of a polyol fatty acid ester plasticizer comprises the following steps:
(1) adding polyhydric alcohol and monocarboxylic acid into a reactor according to the mole number of carboxyl being 1.2-1.5 times of that of hydroxyl, stirring and mixing, heating to 150-180 ℃, removing water generated in the reaction through a water separator, and stopping heating to terminate the reaction after no water is generated;
(2) and continuously heating to 130-160 ℃ to remove unreacted fatty acid, cooling to below 70 ℃, decoloring by using active carbon, and filtering to obtain the polyol fatty acid ester.
As an improved technical scheme, the polyalcohol is one or more of erythritol, sorbitol, xylitol, fructose and maltitol.
As an improved technical scheme, the monocarboxylic acid is one or more of branched or non-linear fatty acids with 4-10 carbon atoms.
The inventor of the invention has long devoted to the research of the plasticizer and the products thereof, and a great deal of theoretical analysis and experimental verification show that the o-benzene plasticizer has relatively low toxicity and metabolites thereof have relatively low toxicity in the types with relatively large molecular weight, longer side chain or more branched side chain. Indicating that the molecular configuration of the plasticizer is directly related to its toxicity. Therefore, the inventor selects synthetic raw materials from the perspective of molecular structure according to the development trend of safe and nontoxic plasticizers to prepare a series of green and nontoxic plasticizers with good plasticizing performance for food packaging products.
The ester compound is generally insoluble in water, can be dissolved in various organic solvents, has wide sources of reaction substrates and various structural types, and is a reliable source for screening novel plasticizers. The two major reaction substrates for ester compounds are acids and alcohols.
The main types of organic acids among them can be:
aliphatic monobasic acids such as butyric acid, caproic acid, caprylic acid, etc.;
aliphatic dibasic acids such as oxalic acid, succinic acid, adipic acid and the like;
aliphatic tribasic acids, such as citric acid, aliphatic polybasic acids, and the like.
Unsaturated aliphatic monobasic acids, dibasic acids, tribasic acids, and the like.
Cyclopentane monoacid, diacid, triacid;
cyclohexane monoacid, diacid, triacid;
trimellitic acid, pyromellitic acid, and the like.
Sulfonic acids such as benzenesulfonic acid and the like.
The inorganic acid is sulfuric acid, phosphoric acid, nitric acid, etc.
The alcohol compound can be:
aliphatic monohydric alcohols, such as butanol, pentanol, heptanol, and the like.
Aliphatic diols or secondary alcohols, such as propylene glycol, butylene glycol, and the like.
Aliphatic trihydric or tertiary alcohols, such as glycerol and the like.
Aliphatic tetrahydric or quaternary alcohols, such as pentaerythritol and the like.
Aliphatic polyols, such as sorbitol and the like.
Unsaturated aliphatic monohydric alcohols, dihydric alcohols, trihydric alcohols, polyhydric alcohols, and the like.
Alicyclic alcohols such as cyclohexanol, cyclohexenol and the like.
Aromatic alcohols, such as benzyl alcohol, and the like.
Due to the adoption of the technical scheme, the invention has the beneficial effects that:
the preparation method of the polyol fatty acid ester plasticizer comprises the steps of taking polyol and monocarboxylic acid as raw materials, stirring and mixing the raw materials in a reactor, heating the mixture to 150-180 ℃, removing water generated in the reaction through a water separator, and stopping heating to terminate the reaction after no water is generated; and continuously heating to 130-160 ℃ to remove unreacted fatty acid, cooling to below 70 ℃, decoloring by using active carbon, and filtering to obtain the polyol fatty acid ester. From the perspective of molecular structure, through molecular simulation experiments, performance analysis is performed on the molecular structure which accords with the simulation result, and a product with better performance is selected for experimental verification. A large number of theoretical analyses and experimental verifications prove that the polyol carboxylic ester obtained by the esterification reaction of the polyol and the monocarboxylic acid has better plasticizing effect, and is safe and nontoxic.
Drawings
The invention is further illustrated with reference to the following figures and examples.
FIG. 1 is a liver tissue section of three groups of mice and a control group of mice in test example 1 of the present invention;
FIG. 2 is a section of testis tissue of three groups of mice and a control group of mice in Experimental example 2 of the present invention;
in FIG. 1, the sample A is a liver tissue section of a control group of mice injected with physiological saline; sample B is a mouse liver tissue section injected with the high dose plasticizer product of the invention in the experimental group; sample C is a section of liver tissue from a mouse injected with the plasticizer product of the present invention at the dosage in the experimental group; sample D is a section of liver tissue from mice injected with the low dose plasticizer product of the present invention in the experimental group.
In FIG. 2, the sample I is a section of a control group of mouse testis tissue injected with physiological saline; sample J is a section of mouse testicular tissue injected with the high dose plasticizer product of the present invention in the experimental group; the K sample is a mouse testis tissue section of an experimental group injected with the plasticizer product of the dosage of the invention; sample L is a section of mouse testicular tissue injected with a low dose of plasticizer product of the present invention in the experimental group.
Detailed Description
The invention is further illustrated below with reference to the figures and examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Example 1
(1) Adding 1 mol of fructosyl alcohol and 7.5 mol of valeric acid into a glass reactor provided with a stirrer, a condenser, a water separator and a thermometer for mixing, stirring and heating to 180 ℃, removing water generated by the esterification reaction through the water separator, and stopping heating to terminate the reaction after no water is generated;
(2) continuously heating to 140 ℃, distilling under reduced pressure to remove unreacted valeric acid, cooling to below 70 ℃, decoloring for 1 hour by using active carbon, and filtering at room temperature to obtain the fructosyl alcohol valerate with the purity of 98%.
Example 2
(1) Adding 1 mol of maltitol and 11 mol of caprylic acid into a glass reactor provided with a stirrer, a condenser, a water separator and a thermometer for mixing, stirring and heating to 175 ℃, removing water generated in the esterification reaction through the water separator, and stopping heating to terminate the reaction after no water is generated;
(2) heating to 145 deg.C, distilling under reduced pressure to remove unreacted octanoic acid, cooling to below 70 deg.C, decolorizing with active carbon for 1 hr, and filtering at room temperature to obtain maltitol valerate with purity of 97.8%.
Example 3
(1) Adding 1 mol of xylitol and 6 mol of butyric acid into a glass reactor provided with a stirrer, a condenser, a water separator and a thermometer, mixing, stirring and heating to 170 ℃, removing water generated by the esterification reaction through the water separator, and stopping heating to terminate the reaction after no water is generated;
(2) continuously heating to 142 ℃, distilling under reduced pressure to remove unreacted butyric acid, cooling to below 70 ℃, decoloring for 1 hour by active carbon, and filtering at room temperature to obtain xylitol butyrate with the purity of 98.5%.
Example 4
(1) Adding 1 mol of xylitol and 11 mol of butyric acid into a glass reactor provided with a stirrer, a condenser, a water separator and a thermometer for mixing, stirring and heating to 168 ℃, removing water generated by the esterification reaction through the water separator, and stopping heating to terminate the reaction after no water is generated;
(2) continuously heating to 140 ℃, distilling under reduced pressure to remove unreacted butyric acid, cooling to below 70 ℃, decoloring for 1 hour by using activated carbon, and filtering at room temperature to obtain xylitol butyrate with the purity of 98%.
The plasticizers prepared in examples 1, 2, 3, 4 of the present invention as sample 1, sample 2, sample 3, sample 4 and the DINP, DINCH plasticizers as comparative sample 1, comparative sample 2 were mixed with 35 wt% of the plasticizer sample and 2 wt% of the stabilizer per 100 parts by weight of PVC. The PVC plasticized product formed by adding the PVC into the PVC is applied to packaging bags which can be directly contacted with food.
1. Processability (M-Y-Y
Plasticizing conditions: samples 1, 2, 3 and 4 obtained in examples 1 to 4 and DINP and DINCH plasticizers were added to PVC resin in an amount of 40 wt% as comparative samples 1 and 2, and the plasticizing time was compared with that of a two-roll open mill at 165 ℃ to show that the plasticizing effect was good when the amount of the plasticizer used was small. The results are shown in Table 1.
TABLE 1
2. Measurement of plasticizing Effect
Samples 1, 2, 3 and 4 obtained in examples 1 to 4 above and DINP and DINCH plasticizers were added to PVC resin in an amount of 40% by weight as comparative samples 1 and 2, and the mixture was calendered at 165 ℃ by a twin roll calender to form a sheet. The hardness of the obtained plasticized PVC sheet was evaluated in accordance with GB/T3398.2-2008 Plastic hardness measurement.
1) Comparison of plasticizing Effect
TABLE 2
| Plasticizer | Hardness (shore C) |
| Sample 1 | 59 |
| Sample 2 | 62 |
| Sample 3 | 61 |
| Sample No. 4 | 60 |
| Comparative sample 1 | 73 |
| Comparative sample 2 | 72 |
3. Migration and precipitation
The results are given in Table 3, according to the International organization for standardization ISO "determination of migration of plasticizers for plastics".
TABLE 3
| Plasticizer | Migration and precipitation |
| Sample 1 | Is free of |
| Sample 2 | Is free of |
| Sample 3 | Is free of |
| Sample No. 4 | Is free of |
| Comparative sample 1 | Is free of |
| Comparative sample 2 | Is free of |
4. Toxicity detection
The plasticizer and physiological saline obtained in the above examples were used as control groups, and injected into experimental mice at a high dose (2 mL/kg. d), a medium dose (1 mL/kg. d), and a low dose (0.5 mL/kg. d), respectively, to perform toxicity tests. 3 female mice and 3 male mice were taken from each group as a parallel control. The mice of the experimental group and the control group are respectively taken to be sliced into liver tissues and testicular tissues, and the results are respectively shown in the attached figures 1 and 2. Observing the integrity of liver tissue structures, normal liver cells and the regular and complete liver lobule structures of the paraffin section control group experimental group and the control group under a mirror; the liver lobule structures of the high, medium and low dose groups of the samples are normal, and no obvious pathological change exists. Under a light microscope, the shape of a normal control group male mouse testis tissue seminiferous tubule cavity is regular, the basement membrane of the wall is complete, the number of layers of seminiferous sperm cells in the cavity is large, the arrangement is regular and compact, and the cavity is filled with sperms; the testis tissues of the male mice of the high, medium and low dose groups of the samples are not abnormally changed.
Compared with common DINP and DINCH plasticizer products, the polyol fatty acid plasticizer prepared by the invention is safe and nontoxic, and is more suitable for plasticizing application occasions with higher requirements on contact safety. Compared with other non-o-benzene plasticizers, the plasticizer provided by the invention has the advantages of shorter plasticizing time, better processability and plasticizing performance and no migration and precipitation.
Claims (3)
1. A preparation method of a polyol fatty acid ester plasticizer is characterized by comprising the following steps:
(1) adding polyhydric alcohol and monocarboxylic acid into a reactor according to the mole number of carboxyl being 1.2-1.5 times of that of hydroxyl, stirring and mixing, heating to 150-180 ℃, removing water generated in the reaction through a water separator, and stopping heating to terminate the reaction after no water is generated;
(2) and continuously heating to 130-160 ℃ to remove unreacted fatty acid, cooling to below 70 ℃, decoloring by using active carbon, and filtering to obtain the polyol fatty acid ester.
2. The method for preparing a polyol fatty acid ester plasticizer according to claim 1, wherein: the polyalcohol is one or more of erythritol, sorbitol, xylitol, fructose and maltitol.
3. The method for preparing a polyol fatty acid ester plasticizer according to claim 1, wherein: the monocarboxylic acid is one or more of branched or non-linear fatty acids with 4-10 carbon atoms.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112778242A (en) * | 2021-01-07 | 2021-05-11 | 长春工业大学 | Bio-based anhydroxylitol ester plasticizer and preparation method thereof |
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