CN117263803A - A kind of lignin-based plasticizer and its preparation method and application - Google Patents
A kind of lignin-based plasticizer and its preparation method and application Download PDFInfo
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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
- C08K5/105—Esters; Ether-esters of monocarboxylic acids with phenols
- C08K5/107—Esters; Ether-esters of monocarboxylic acids with phenols with polyphenols
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- C07—ORGANIC CHEMISTRY
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- C07C67/00—Preparation of carboxylic acid esters
- C07C67/14—Preparation of carboxylic acid esters from carboxylic acid halides
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- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/02—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen
- C07C69/22—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen having three or more carbon atoms in the acid moiety
- C07C69/28—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen having three or more carbon atoms in the acid moiety esterified with dihydroxylic compounds
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- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/02—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen
- C07C69/22—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen having three or more carbon atoms in the acid moiety
- C07C69/30—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen having three or more carbon atoms in the acid moiety esterified with trihydroxylic compounds
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Abstract
本发明公开一种木质素基增塑剂及其制备方法和应用，包括在醇类溶剂中，利用酸性催化剂催化木质素氢化解聚为生物油；在高压反应釜中，将所得的生物油与催化剂、正十二烷反应，得到木质素酚类单体；将得到的酚类单体与催化剂发生脱甲基化反应，得到邻苯二酚结构化合物；将得到的邻苯二酚结构化合物与丙酰氯于溶剂中反应，得到木质素基丙酸苯酯型增塑剂。本发明通过两步法对木质素进行降解，并通过脱甲基化反应暴露出更多反应活性位点，为后续改性提供了更多可能，制备的增塑剂具有耐水性好、低毒安全、易降解、使用寿命长的优点，且增强了PVC制品的抗撕裂强度，实现了木质素的高值化利用。
The invention discloses a lignin-based plasticizer and its preparation method and application, which include using an acidic catalyst to catalyze the hydrogenation and depolymerization of lignin into bio-oil in an alcohol solvent; and in a high-pressure reactor, mixing the obtained bio-oil with The catalyst and n-dodecane are reacted to obtain lignin phenolic monomers; the obtained phenolic monomers are demethylated with the catalyst to obtain catechol structural compounds; the obtained catechol structural compounds are reacted with Propionyl chloride reacts in a solvent to obtain a lignin-based phenyl propionate plasticizer. The present invention degrades lignin through a two-step method and exposes more reactive sites through demethylation reaction, providing more possibilities for subsequent modification. The prepared plasticizer has good water resistance and low toxicity. It has the advantages of safety, easy degradation and long service life, and enhances the tear resistance of PVC products, realizing high-value utilization of lignin.
Description
Technical Field
The invention belongs to the technical field of lignin derivatives, and particularly relates to a lignin-based plasticizer, a preparation method and application thereof.
Background
Due to the increasing consumption of fossil fuels and the limited storage and the growing prominence of environmental problems, alternative energy and chemical resources are urgently needed, and thus, biomass chemical products are receiving increasing attention. Lignin is the most abundant aromatic polymer in nature. Lignin is considered as an alternative source of production of various polymers and biomaterials due to its large phenolic compound storage.
However, lignin has a complex structure and low reactivity, which limits its further application. In industrial processing, lignin mainly supplies heat in a combustion mode, the utilization value is low, and waste liquid rich in lignin is troublesome to treat, and the cost is high and pollutes the environment. Therefore, the property of lignin can be changed through molecular design and structural modification, chemicals with high added value can be prepared, and the lignin can be efficiently utilized, so that the lignin has ecological benefits, and is expected to replace petroleum resources in certain fields, thereby obtaining huge economic benefits.
The plasticizer is one of the most important auxiliary agents required for processing high polymer materials, especially polyvinyl chloride (PVC) plastics, and accounts for more than 60% of the total output of the plastic auxiliary agents. Traditional petroleum-based phthalate plasticizers are the most widely used worldwide, but are increasingly limited due to potential threats to human health and the environment. Therefore, development of environmentally friendly nontoxic plasticizers and biodegradable bio-based plasticizers to replace phthalates is a research hotspot.
Disclosure of Invention
This section is intended to outline some aspects of embodiments of the invention and to briefly introduce some preferred embodiments.
The technical problem to be solved by the invention is to provide a preparation method of the lignin-based plasticizer.
The invention discloses a lignin-based plasticizer shown in a formula I:
wherein R is-CH 2 CH 2 CH 3 、-CH 2 CH 2 CH 2 OH、-CH 2 CH 2 CH 2 OCH 3 One of them.
In order to solve the technical problems, the invention discloses a preparation method of the lignin-based plasticizer, which comprises the following steps:
(1) In an alcohol solvent, catalyzing lignin to be hydrogenated and depolymerized into biological oil by using an acid catalyst;
(2) In a high-pressure reaction kettle, the biological oil obtained in the step (1) reacts with a catalyst and n-dodecane to obtain lignin phenol monomers;
(3) Carrying out demethylation reaction on the phenolic monomer obtained in the step (2) and a catalyst to obtain a catechol structure compound;
(4) And (3) reacting the catechol structural compound obtained in the step (3) with propionyl chloride in a solvent to obtain the lignin-based plasticizer.
In the step (1), the alcohol solvent is methanol or ethanol; the acid catalyst is phosphoric acid, sulfuric acid, hydrochloric acid or p-toluenesulfonic acid; the mass ratio of the lignin to the acid catalyst is (2-4) to 1.
In the step (1), the reaction conditions are as follows: the temperature was 160℃and the reaction time was 2 hours, with a stirring rate of 500rpm/min.
In the step (1), after the reaction is finished, filtering to remove residual lignin.
In the step (2), the catalyst is Pd/C; the mass ratio of the biological oil to the catalyst is 3:1.
In the step (2), the reaction conditions are as follows: the temperature was 180℃and the reaction time was 2 hours, the hydrogen pressure was 30bar, and the stirring rate was 500rpm/min.
In the step (2), after the reaction is finished, removing a catalyst by filtering, and obtaining lignin phenol monomers by reduced pressure distillation and drying.
In the step (3), the catalyst is AlCl 3 -Nal; the molar ratio of the phenolic monomer to the catalyst is 1:2.
In the step (3), the reaction conditions are as follows: the temperature is 70-80 ℃ and the reaction time is 1-3h.
In the step (3), after the completion of the reaction, the reaction mixture is treated with Na 2 S 2 O 3 (5%) dilution with aqueous solution, extraction with diethyl ether, extraction with ether over MgSO 4 Drying, and distilling under reduced pressure to obtain the product.
In the step (4), the solvent is dichloromethane; the molar ratio of the catechol structural compound to propionyl chloride is 1:2.
In the step (4), the reaction conditions are as follows: the temperature is 0-room temperature, and the reaction time is 1-8 h.
In step (4), after the completion of the reaction, the reaction mixture was treated with HCl (1M, 10 mL), and the product was extracted with dichloromethane (3X 10 mL) and dried over Na 2 SO 4 And drying the organic layer, and distilling under reduced pressure to obtain the final product lignin-based plasticizer.
The lignin-based plasticizer is prepared by degrading lignin into phenolic compounds by a two-step method, obtaining catechol compounds through demethylation reaction, and finally reacting the catechol compounds with propionyl chloride. Lignin was purchased from microphone (cat# 1849279).
The specific synthetic route for the lignin-based plasticizers described above,
the reaction structural formula is as follows:
the invention has the beneficial effects that: compared with the prior art, the invention has the advantages that:
(1) The raw materials of the invention are easy to extract and renewable, so that the dependence of the plasticizer industry on petrochemical products is reduced, and the invention has great economic benefit.
(2) The product of the invention has low toxicity, safety, easy biodegradation and great ecological benefit.
(3) The product of the invention obviously enhances the tearing strength of PVC products.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the description of the embodiments will be briefly described below, it being obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art. Wherein:
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of phenyl lignin propionate plasticizers in example 12.
FIG. 2 is a nuclear magnetic resonance spectrum of a phenyl lignin propionate plasticizer in example 12.
FIG. 3 is an infrared plot of phenyl lignin propionate plasticizers in example 12.
Detailed Description
In order that the above-recited objects, features and advantages of the present invention will become more apparent, a more particular description of the invention will be rendered by reference to specific embodiments thereof.
Examples 1 to 2:
2g lignin, 40ml methanol (example 1) or ethanol (example 2), 0.5g H 2 SO 4 Into a 100ml autoclave, nitrogen was purged three times to remove air. Heating the mixture to 160 ℃, stirring at 500rpm/min, reacting for 2 hours, and filtering to remove superfluous lignin to obtain the bio-oil. Mixing 0.45g biological oil, 15g Pd/C and 30 μl n-dodecane in a high pressure reactor, flushing the reactor with nitrogen, and then using H 2 Pressurizing to 30bar, reacting at 180 deg.C for 2h, filtering to remove catalyst, vacuum distilling,Drying to obtain lignin phenol monomer.
Table 1 shows lignin degradation rates and yields for examples 1-2
| Examples | Lignin degradation rate | Monomer yield |
| 1 | 70％ | 17.8％ |
| 2 | 50％ | 10.2％ |
Examples 3 to 6:
2g lignin, 40ml methanol, 0.5g HCl (example 3), phosphoric acid (example 4), p-TSA (example 5), without acid catalyst (example 6) were introduced into a 100ml autoclave, which was flushed three times with nitrogen to remove air. Heating the mixture to 160 ℃, stirring at 500rpm/min, reacting for 2 hours, and filtering to remove superfluous lignin to obtain the bio-oil. 0.45g of bio-oil, 0.15g Pd/C and 30. Mu.l of n-dodecane were mixed in a high pressure reactor, and the high pressure was purged with nitrogenAfter the autoclave, H was used 2 Pressurizing to 30bar, reacting at 180 ℃ for 2h, filtering to remove catalyst after the reaction is finished, and obtaining lignin phenol monomer through reduced pressure distillation and drying.
Table 2 shows the degradation rates and yields of examples 3 to 6
Example 7:
2g lignin, 40ml methanol, 1g HCl were introduced into a 100ml autoclave, which was purged three times with nitrogen to remove air. Heating the mixture to 160 ℃, stirring at 500rpm/min, reacting for 2 hours, and filtering to remove superfluous lignin to obtain the bio-oil. Mixing 0.45g biological oil, 0.15g Pd/C (palladium carbon catalyst) and 30 μl n-dodecane in a high pressure reactor, flushing the reactor with nitrogen, and then using H 2 Pressurizing to 30bar, reacting at 180 ℃ for 2h, filtering to remove catalyst after the reaction is finished, and obtaining lignin phenol monomer through reduced pressure distillation and drying.
Table 3 shows degradation rates and yields of examples 3 and 7
| Examples | Lignin degradation rate | Monomer yield |
| 3 | 47％ | 27.4％ |
| 7 | 98％ | 62.8％ |
Examples 8 to 9:
the lignin phenol monomer (1 eq) obtained in example 7 was reacted with AlCl 3 (2 eq) and Nal (2 eq) were thoroughly ground in an agate mortar and the resulting softened material was heated either at 70℃for 1h (example 8) or at 80℃for 3h (example 9). The reaction mixture obtained is treated with Na 2 S 2 O 3 (5%) dilution with aqueous solution, extraction with diethyl ether, extraction with ether over MgSO 4 Drying the mixture, and distilling the mixture under reduced pressure to obtain a catechol compound, wherein the yield of example 8 is 45% and the yield of example 9 is 90%.
Examples 10 to 12:
catechol compound (1 mmol), triethylamine (3 mmol) and propionyl chloride (2 mmol) obtained in example 9 were added to 1Oml dichloromethane at 0℃and the mixture was allowed to stand at room temperature after 1h of reaction at 0℃ (example 10), at room temperature after 4h of reaction at 0℃ (example 11), or at room temperature after 8h of reaction at 0℃ (example 12). After the completion of the reaction, the resulting reaction mixture was treated with HCl (1M, 10 mL), and the product was extracted with dichloromethane (3X 10 mL) and dried over Na 2 SO 4 And drying the organic layer, and distilling under reduced pressure to obtain the final product lignin-based phenyl propionate plasticizers.
Table 4 shows the conversion and yield of catechol structure compounds of examples 10 to 12
And (3) infrared spectrum detection:
the product obtained in example 12 was subjected to infrared spectroscopic detection, and the results are shown in fig. 3.
As can be seen from FIG. 3, benzene ring skeleton vibration peaks unique to lignin appear at 1592cm-1 and 1449 cm-1; a c=o stretching vibration peak appears at 1744 cm-1; the stretching vibration peaks of the aromatic ether C-O-C appear at 1264cm-1 and 1194 cm-1.
In summary, the present application successfully synthesizes the target product.
Example 13:
the lignin-based propionate plasticizers synthesized in example 12, dioctyl terephthalate (DOTP) and diisononyl phthalate (DINP) were used as plasticizers, respectively or in combination, for plasticizing PVC, and the formulation of the blend is shown in table 5. Mixing PVC powder and plasticizer, stirring at high speed, banburying with a torque rheometer, and pressing into PVC film with certain thickness by a flat vulcanizing machine for tensile property test. Table 6 shows the results of mechanical property tests of PVC samples of different formulations. As shown in the table, with the increase of the plasticizer content, the tensile strength of the PVC sample is increased, which shows that the compatibility of the plasticizer with PVC is better than that of DOTP and DINP with PVC, and the PVC product can be endowed with good flexibility.
Table 5 PVC article formulation
TABLE 6 mechanical test results of PVC articles
| Sample of | Elongation at break (%) | Tensile Strength (MPa) |
| 1 | 338.2±5.26 | 21.8±2.31 |
| 2 | 347.55±8.32 | 22.9±1.98 |
| 3 | 377.85±9.13 ＊＊＊ | 23.16±1.52 |
| 4 | 385.07±10.05 ＊＊＊ | 23.05±2.08 |
| 5 | 400.83±8.46 ＊＊＊ | 28.98±1.52 ＊＊＊ |
| 6 | 332.45±3.66 | 19.4±1.03 |
In the table 6, the contents of the components, ＊＊＊ indicating a very significant difference (p < 0.001) compared to sample 1.
It should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted without departing from the spirit and scope of the technical solution of the present invention, which is intended to be covered in the scope of the claims of the present invention.
Claims (10)
1. A lignin-based plasticizer of the formula I,
wherein R is-CH 2 CH 2 CH 3 、-CH 2 CH 2 CH 2 OH、-CH 2 CH 2 CH 2 OCH 3 One of them.
2. A method of preparing the lignin-based plasticizer according to claim 1 wherein: the method comprises the following steps:
(1) In an alcohol solvent, catalyzing lignin to be hydrogenated and depolymerized into biological oil by using an acid catalyst;
(2) In a high-pressure reaction kettle, the biological oil obtained in the step (1) reacts with a catalyst and n-dodecane in a hydrogen atmosphere to obtain lignin phenol monomers;
(3) Carrying out demethylation reaction on the lignin phenol monomer obtained in the step (2) and a catalyst to obtain a catechol structure compound;
(4) And (3) reacting the catechol structural compound obtained in the step (3) with propionyl chloride in a solvent to obtain the lignin-based plasticizer.
3. The method of producing a lignin-based plasticizer according to claim 2 wherein: in the step (1), the alcohol solvent is methanol or ethanol; the acid catalyst is phosphoric acid, sulfuric acid, hydrochloric acid or p-toluenesulfonic acid; the mass ratio of the lignin to the acid catalyst is (2-4) to 1.
4. A method of preparing a lignin-based plasticizer according to claim 2 or 3 wherein: in the step (1), the lignin is catalyzed by an acid catalyst to be hydrogenated and depolymerized into biological oil, the reaction temperature is 160-170 ℃, and the reaction time is 2-3 hours.
5. A method of preparing a lignin-based plasticizer according to claim 2 or 3 wherein: in the step (2), the catalyst is Pd/C; the mass ratio of the biological oil to the catalyst is 3:1.
6. A method of preparing a lignin-based plasticizer according to claim 2 or 3 wherein: in the step (2), the temperature of the reaction is 175-180 ℃, the reaction time is 2-3 h, and the hydrogen pressure is 25-30 bar.
7. A method of preparing a lignin-based plasticizer according to claim 2 or 3 wherein: in the step (3), the catalyst is AlCl 3 And Nal; the molar ratio of the lignin phenol monomer to the catalyst is 1:2-4; the reaction temperature is 70-80 ℃ and the reaction time is 1-3h.
8. A method of preparing a lignin-based plasticizer according to claim 2 or 3 wherein: in the step (4), the solvent is dichloromethane; the molar ratio of the catechol structural compound to propionyl chloride is 1:2.
9. A method of preparing a lignin-based plasticizer according to claim 2 or 3 wherein: in the step (4), the reaction temperature is 0 ℃ and the reaction time is 1-8 h.
10. Use of the lignin-based plasticizer according to claim 1 as a plasticizer for polyvinyl chloride plastics.
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