CN115521329B - Catalyst for lactide ring-opening polymerization and preparation method and application thereof - Google Patents
Catalyst for lactide ring-opening polymerization and preparation method and application thereof Download PDFInfo
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- CN115521329B CN115521329B CN202211045808.2A CN202211045808A CN115521329B CN 115521329 B CN115521329 B CN 115521329B CN 202211045808 A CN202211045808 A CN 202211045808A CN 115521329 B CN115521329 B CN 115521329B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic System
- C07F5/06—Aluminium compounds
- C07F5/069—Aluminium compounds without C-aluminium linkages
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
- C08G63/08—Lactones or lactides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/823—Preparation processes characterised by the catalyst used for the preparation of polylactones or polylactides
Abstract
The invention belongs to the technical field of polymers, and particularly relates to a catalyst for lactide ring-opening polymerization, a preparation method and application thereof. Dye under nitrogen protection 1 Reacting with alkyl metal in a solvent to obtain a solution of an alkyl metal complex; dye is carried out under the protection of nitrogen 2 Adding the catalyst into a solution of an alkyl metal complex for reaction to obtain the catalyst for lactide ring-opening polymerization. Under the protection of nitrogen, the catalyst for lactide ring-opening polymerization and lactide carry out ring-opening polymerization reaction in a solvent to obtain the colored polylactic acid. The invention realizes the covalent bond combination between dye molecules and polylactic acid polymer chains, thereby thoroughly solving the problems of low dye uptake, low color fastness, color light change, insufficient color depth and the like existing in the traditional disperse dye for dyeing polylactic acid, and avoiding the generation of a large amount of high COD and high salt dyeing wastewater of the traditional polylactic acid material in the dyeing finishing stage.
Description
Technical Field
The invention belongs to the technical field of polymers, and particularly relates to a catalyst for lactide ring-opening polymerization, a preparation method and application thereof.
Background
Polylactic Acid (PLA) is a biological polymer material formed by fermenting and converting renewable starch such as corn, wheat, cassava and the like as an initial raw material, and then directly condensing the lactic Acid or performing ring-opening polymerization (ROP) on a cyclic intermediate dimer (lactide) through the lactic Acid. Polylactic acid material can be thoroughly decomposed into CO under the action of microorganisms, acid and alkali after being abandoned 2 And H 2 O, which is subsequently subjected to photosynthesis, can be converted into starch as a starting material. The production process of PLA can reduce fossil resources by 20-50% compared to petroleum-based polymers. Therefore, polylactic acid is an ideal green polymer material. Polylactic acid has applications in many areas, such as biomedical, textile, packaging and the like. The biodegradability of polylactic acid makes it particularly advantageous for application in faster spinning.
In the natural world, everything is not separated from the color, the life of human beings is closely related to the color, and the food package, the clothing color, the living environment and the articles are closely related to the color. Therefore, the colored polylactic acid can be more suitable for market demands. By adopting the traditional dyeing mode, on one hand, the improvement of the dye in the dyeing process is not high, the retention of the physical and mechanical properties is poor, the dyeing fastness is not high, and the color is easy to fade; on the other hand, the traditional dyeing consumes a great deal of energy sources such as water, electricity, gas and the like, and can produce sewage to pollute the environment. At present, a stock solution coloring technology is also adopted to produce colored polylactic acid, but color master batch pigment and other auxiliary agents are added in the processing process, so that equipment cleaning and waste silk recycling are difficult.
In recent years, some researchers have used traditional dyeing to obtain colored polylactic acid. For example, chinese patent CN109440490a discloses an azo structure lactate type disperse dye for dyeing polylactic acid fiber, a preparation method and a dyeing process thereof, wherein lactate groups with similar fiber structure and strong polarity are introduced into the lactate type disperse dye structure, so that the affinity of the dye and polylactic acid fiber is improved, the dye uptake is improved, meanwhile, the hydroxyl groups on the lactate groups in the dye can improve the boiling point of the dye, and hydrogen bonds are formed among dye molecules due to the existence of the hydroxyl groups, thereby improving the sublimation fastness of the dye, and the dye has bright color, high color development intensity and good fastness performance and has better dyeing effect; however, this patent requires a large amount of energy such as water, electricity, gas, etc., and generates sewage to pollute the environment. Some researchers have made much research in the masterbatch industry to apply the combination of the colored masterbatch and polylactic acid to the polylactic acid field. For example, chinese patent CN110922613a discloses a colored polylactic acid particle and a preparation method, the colored polylactic acid particle is composed of polylactic acid and pigment, the colorless polylactic acid material in a molten state after polymerization is directly mixed with the colored polylactic acid in a molten state made of primary color master batch of polylactic acid to prepare a colored polylactic acid mixed melt, and then underwater pelletizing and drying are carried out to obtain the colored polylactic acid particle, thus omitting the existing step of coloring the colorless polylactic acid, and remarkably reducing equipment investment and raw material cost; although the coloring method of polylactic acid disclosed by the patent can be used for preparing polylactic acid products with various colors, the synthesis temperature is high, the steps are complicated, the color master batch pigment and other auxiliary agents are added in the processing process, and the equipment cleaning and waste silk recycling are difficult.
The problems of low dye-uptake, poor fastness, high temperature in the process of synthesizing color master batches, difficult cleaning of equipment and the like exist in the research of polylactic acid dyeing so far, and the problems become the problems to be solved urgently in the dyeing industry.
Disclosure of Invention
The invention aims to provide a catalyst for lactide ring-opening polymerization, which is convenient to prepare and stable in property, and has the function of catalyzing lactide ring-opening polymerization and generating colored polylactic acid; the invention also provides a preparation method and application of the catalyst for lactide ring-opening polymerization, and realizes covalent bond combination between dye molecules and polylactic acid polymer chains, thereby thoroughly solving the problems of low dye uptake, low color fastness, color light change, insufficient color depth and the like existing in the traditional disperse dye for dyeing polylactic acid, avoiding the generation of a large amount of high COD and high salt dyeing wastewater in the dyeing finishing stage of the traditional polylactic acid material, saving energy and reducing consumption, and meeting the requirements for preparing high-quality polylactic acid textiles and materials.
The catalyst for lactide ring-opening polymerization has the following structural formula:
wherein M is a metal, dye 1 Dye ligand Dye 2 Is a Dye molecule containing hydroxyl groups, the above structural formula represents M and Dye respectively 1 、Dye 2 Are connected.
And M is aluminum.
The Dye 1 Is an anthraquinone dye ligand.
The Dye 1 The structural formula is as follows:
wherein R is 1 is-OH, -NH 2 、-NHCH 3 、-NHC 6 H 5 or-NHOC 6 H 5 One of the following;
R 2 is-H, -OCH 3 、-OC 6 H 5 -one of Cl or Br;
R 3 is-H, -OH, -NHCH 3 、-Cl、-Br、-NHC 6 H 5 、-NHOC 6 H 5 Or- (CH) 2 ) n One of OH, wherein n is more than or equal to 1 and less than or equal to 18, and n is an integer;
R 4 is-H, -OH or-NH 2 One of the following;
R 5 is-H, -OH or-NH 2 One of them.
The Dye 1 The structural formula of (a) is one of the following structural formulas:
the Dye 2 The structural formula is as follows:
wherein R is 6 is-H, -CH 3 、-CH 2 CH 2 CN or- (CH) 2 ) n One of OH, wherein n is more than or equal to 1 and less than or equal to 18, and n is an integer;
R 7 is- (CH) 2 ) n OH, wherein n is more than or equal to 1 and less than or equal to 18, and n is an integer;
R 8 is-H, -CH 3 (Co, cl) or-OCH 3 One of the following;
R 9 is-H or-CH 3 ；
R 10 is-H, -CH 3 、-NHCOCH 3 or-NHCOC 2 H 5 One of the following;
R 11 is-H, -CH 3 、-OCH 3 、-Cl、-Br、-NO 2 Or-one of CN;
R 12 is-H, -Cl, -Br, -NO 2 Or-one of CN;
R 13 is-H, -NO 2 Or-one of CN;
R 14 is-H, -CH 3 or-CH 2 CH 2 One of the CNs;
R 15 is- (CH) 2 ) n OH, wherein n is more than or equal to 1 and less than or equal to 18, and n is an integer;
R 16 is-H, -CH 3 (Co, cl) or-OCH 3 One of the following;
R 17 is-H or-CH 3 ；
R 18 is-H, -CH 3 、-NHCOCH 3 or-NHCOC 2 H 5 One of the following;
R 19 is-H or-NO 2 。
The Dye 2 The structural formula of (a) is one of the following structural formulas:
the preparation method of the catalyst for lactide ring-opening polymerization comprises the following steps:
(1) Dye under nitrogen protection 1 Reacting with alkyl metal in a solvent to obtain a solution of an alkyl metal complex;
(2) Dye is carried out under the protection of nitrogen 2 Adding the catalyst into a solution of an alkyl metal complex for reaction to obtain the catalyst for lactide ring-opening polymerization.
The alkyl metal in the step (1) is trimethylaluminum.
The solvent in the step (1) is one or more of benzene, toluene or tetrahydrofuran, preferably toluene.
Dye described in step (1) 1 The molar ratio of the catalyst to the alkyl metal is 2-2.8:1.
The solvent described in step (1) and Dye 1 The mass ratio of (2) is 20-200:1.
The reaction time in the step (1) is 3-12h.
The reaction in the step (1) is a stage heating reaction, wherein the reaction temperature of the first stage is between-78 and 25 ℃, and the reaction temperature of the second stage is between 60 and 125 ℃.
Dye described in step (2) 2 The molar ratio of the catalyst to the alkyl metal is 1-1.5:1.
The reaction temperature in the step (2) is 25-150 ℃ and the reaction time is 4-16h.
The application of the catalyst for lactide ring-opening polymerization is that the catalyst for lactide ring-opening polymerization and lactide carry out ring-opening polymerization reaction in a solvent under the protection of nitrogen, so as to obtain colored polylactic acid.
The solvent is one or more of benzene, toluene, tetrahydrofuran or methylene dichloride.
The molar ratio of the catalyst for lactide ring-opening polymerization to lactide is 1:50-10000.
The molar ratio of the lactide to the solvent is 1:5-20.
The ring-opening polymerization reaction temperature is 50-180 ℃, and the ring-opening polymerization reaction time is 2-24h.
The invention provides a method for preparing colored polylactic acid by lactide ring-opening polymerization, which comprises the following specific reaction equation:
the catalyst for lactide ring-opening polymerization is a metal coordination catalyst, and has the following structural formula:
the synthetic reaction mechanism of the catalyst for lactide ring-opening polymerization is coordination reaction occurring in the metal center. Dye 1 The dye ligand is anthraquinone dye with a planar structure, shortens the interval of coordination atoms (N, O), and provides convenience for coordination reaction with metal center. And Dye 1 Dye ligand is present in a relatively high degreeLarge steric hindrance when the metal centre is attached with two Dye 1 After the Dye ligand, it is difficult to attach a third Dye to the metal center 1 A dye ligand; and Dye containing hydroxy structure 2 Dye molecules with relatively small steric hindrance provide convenience for the hydroxyl group to approach to the active methyl group and react.
The reaction mechanism of the invention for synthesizing the colored polylactic acid is ring-opening polymerization of lactide. The lactide coordinates with the metal center, so that the lactide is electrophilically activated, and is further subjected to nucleophilic attack by the metal center to form an intermediate, and the dye molecules containing hydroxyl groups attack the activated monomers. The chemical bond with higher energy in the intermediate is broken to realize ring opening, and Dye is connected 1 Dye ligand, dye 2 The long chain of lactide monomer of dye molecule, chain growth is accompanied with metal coordination, nucleophilic reaction and bond breaking ring opening of lactide until the coordination bond is cracked to terminate reaction.
Dye 1 Dye ligand and Dye containing hydroxyl structure 2 Dye molecules with the same or different colors are subjected to ring-opening polymerization of lactide to finally realize color folding or color matching of polylactic acid.
The invention creatively combines dye molecules with the lactide ring-opening polymerization catalyst to prepare a novel lactide ring-opening polymerization catalyst and a catalytic system, thereby realizing lactide ring-opening polymerization, polylactic acid coloring and color matching.
The beneficial effects of the invention are as follows:
compared with the existing color master batch polylactic acid technology, the preparation process of the colored polylactic acid is simple, and polylactic acid is directly dyed in the catalytic polymerization. The polymerization process temperature is low, and the influence of temperature on color in the process of melting the color master batch is avoided. Compared with the traditional dyeing, the colored polylactic acid directly avoids the dyeing process, dye molecules are directly bonded into polylactic acid molecules in the lactide ring-opening process, and the dye and the polylactic acid are combined in a compound bond mode, so that the color fastness of the colored fiber such as friction resistance, water washing resistance, sublimation resistance and the like is remarkably improved. In addition, due to the adoption of the polymerization dyeing process, a large amount of dyeing sewage treatment caused by the traditional disperse dye dyeing process is avoided, the industrial problems of high COD and high salt wastewater discharge in the traditional dyeing process can be effectively solved, and the method has a good application prospect. The synthesis process of the colored polylactic acid provided by the invention can also realize that different colored light dyes can be subjected to color matching through a polymerization process, so that a polylactic acid polymer material with richer colored light is obtained, and the application range of the polylactic acid is enlarged.
The metal coordination catalyst provided by the invention is convenient to prepare and stable in property, has the effect of catalyzing lactide ring-opening polymerization and generating colored polylactic acid, and compared with the traditional polylactic acid polymerization and dyeing process, the process is directly shortened, so that a new way is provided for reducing energy consumption and pollution.
Drawings
FIG. 1 is a nuclear magnetic spectrum of a catalyst for lactide ring-opening polymerization, which is orange red in color and prepared in example 1.
FIG. 2 is a nuclear magnetic resonance spectrum of orange polylactic acid prepared in example 1.
Detailed Description
The invention is further described below with reference to examples.
Example 1
Under the protection of nitrogen, 0.4476 g of D1 is dissolved in 30mL of toluene and is placed in a temperature of minus 78 ℃ to react with 1mL of 1mol/L trimethylaluminum solution for 4h, the temperature is slowly raised to room temperature, the mixture is heated to reflux for 1h, then 0.30g of D5 is added into the reaction system and reacts for 6h at the temperature of 75 ℃, the solvent is removed by reduced pressure distillation, the product is washed by normal hexane and dried in vacuum, the product is recrystallized in toluene, washed and dried, 0.71g of orange-red catalyst for lactide ring-opening polymerization is obtained, the nuclear magnetic spectrum diagram of the catalyst for lactide ring-opening polymerization is shown in figure 1, and the catalyst for lactide ring-opening polymerization has the following structural formula:
under the protection of nitrogen, 8g of lactide, 30mL of purified toluene solution and 0.045g of orange-red catalyst for lactide ring-opening polymerization are added into a Schlenk bottle, then an ethanol solution of hydrochloric acid with the volume fraction of 10% is added into the mixture for polymerization at 100 ℃ for 12 hours to terminate the reaction, the reaction liquid is poured into normal hexane for standing and precipitation, filtration is carried out, the precipitate is dissolved by using dichloromethane, a proper amount of normal hexane is added for separating out solid, after the steps of repeating the steps for three times, filtration and pumping are carried out, and vacuum drying are carried out, so that orange polylactic acid is obtained, and the nuclear magnetic spectrum of the orange polylactic acid is shown in figure 2. The light fastness of the tested material can reach 7-8 grades, and the washing fastness can reach 5 grades.
Example 2
Under the protection of nitrogen, 0.4638 g of D1 is dissolved in 40mL of tetrahydrofuran and is placed at the temperature of minus 78 ℃ to react with 1mol/L trimethylaluminum solution of 1mL for 6 hours, the mixed solution is slowly warmed to room temperature and heated to reflux for 1 hour, then 0.345g of D6 is added into the reaction system and reacts for 4 hours under the reflux condition, the solvent is distilled off under reduced pressure, the solvent is washed by normal hexane, the product is dried in vacuum, recrystallized in toluene, washed and dried, and the mauve catalyst for lactide ring-opening polymerization is obtained, namely 0.69g, and the structural formula of the catalyst for lactide ring-opening polymerization is as follows:
under the protection of nitrogen, adding 8g of lactide, 30mL of purified tetrahydrofuran solution and 0.045g of catalyst for lactide ring-opening polymerization into a Schlenk bottle, then adding ethanol solution of hydrochloric acid with the volume fraction of 10% into the mixture for stopping the reaction after the polymerization reaction for 8 hours at 110 ℃, pouring the reaction solution into normal hexane for standing and precipitating, filtering, dissolving the precipitate with dichloromethane, adding a proper amount of normal hexane to separate out solid, repeating the steps for three times, filtering and pumping, and vacuum drying to obtain the purple polylactic acid. The light fastness of the tested material can reach 8 grades, and the washing fastness can reach 5 grades.
Example 3
Under the protection of nitrogen, 0.545g of D2 is dissolved in 40mL of tetrahydrofuran and is placed at 0 ℃ to react with 1mL of 1mol/L trimethylaluminum solution for 4h, the mixed solution is slowly warmed to room temperature and heated to reflux for 1h, then 0.508g of D7 is added into the reaction system and reacts for 5h at 70 ℃, the solvent is removed by reduced pressure distillation, the mixture is washed by n-hexane and dried in vacuum, the product is recrystallized in toluene, washed and dried, and the structural formula of the catalyst for lactide ring-opening polymerization is as follows, wherein the catalyst for lactide ring-opening polymerization is 0.90g in coffee color:
under the protection of nitrogen, 16g of lactide, 80mL of purified toluene solution and 0.12g of catalyst for lactide ring-opening polymerization are added into a Schlenk bottle, then an ethanol solution of hydrochloric acid with the volume fraction of 10% is added into the mixture for stopping the reaction after the polymerization reaction for 10 hours at 120 ℃, the reaction liquid is poured into normal hexane for standing and precipitation, filtration is carried out, the precipitate is dissolved by using dichloromethane, a proper amount of normal hexane is added for separating out solid, and after the steps are repeated for three times, filtration and pumping are carried out, and vacuum drying is carried out, thus obtaining the coffee polylactic acid. The light fastness of the tested material can reach 7 grades, and the washing fastness can reach 4-5 grades.
Example 4
Under the protection of nitrogen, 0.655g of D2 is dissolved in 50mL of toluene and is placed at 10 ℃ to react with 1mL of 1mol/L trimethylaluminum solution for 6h, the mixed solution is slowly warmed to room temperature and heated to reflux for 1h, then 0.483g of D6 is added into the reaction system and reacts for 4h at 120 ℃, the solvent is removed by reduced pressure distillation, the mixture is washed by n-hexane and dried in vacuum, the product is recrystallized in toluene, washed and dried, and the purple catalyst for lactide ring-opening polymerization, 0.75g of which is obtained, has the following structural formula:
under the protection of nitrogen, 16g of lactide, 100mL of purified tetrahydrofuran solution and 0.095g of purple catalyst for lactide ring-opening polymerization are added into a Schlenk bottle, then an ethanol solution of hydrochloric acid with the volume fraction of 10% is added into the mixture for stopping the reaction after the polymerization reaction for 7 hours at 130 ℃, the reaction liquid is poured into normal hexane for standing and precipitation, filtration is carried out, the precipitate is dissolved by using dichloromethane, a proper amount of normal hexane is added for separating out solid, and after the steps are repeated for three times, filtration and pumping are carried out, and vacuum drying is carried out, thus obtaining the purple polylactic acid. The light fastness of the tested material can reach 8 grades, and the washing fastness can reach 4 grades.
Claims (7)
1. A catalyst for lactide ring-opening polymerization is characterized by having the following structural formula:
wherein M is a metal, dye 1 Dye ligand Dye 2 Is a dye molecule containing hydroxyl groups;
m is aluminum;
the Dye 1 The structural formula is as follows:
wherein R is 1 is-NH 2 or-NHCH 3 ；
R 2 is-H;
R 3 is one of-H, -Cl or-Br;
R 4 is-H;
R 5 is-H;
the Dye 2 The structural formula is as follows:
wherein R is 6 is-CCH 3 ；
R 7 Is- (CH) 2 ) n OH, wherein n is more than or equal to 1 and less than or equal to 18, and n is an integer;
R 8 is-H or-CH 3 ；
R 9 is-H or-CH 3 ；
R 10 is-H, -CH 3 、-NHCOCH 3 or-NHCOC 2 H 5 One of the following;
R 11 is-H, -Cl, -Br or-NO 2 One of the following;
R 12 is-H, -Cl, -Br or-NO 2 One of the following;
R 13 is-NO 2 。
2. The catalyst for lactide ring-opening polymerization according to claim 1, characterized in that said Dye 1 The structural formula of (a) is one of the following structural formulas:
3. the catalyst for lactide ring-opening polymerization according to claim 1, characterized in that said Dye 2 The structural formula of (a) is one of the following structural formulas:
4. a method for preparing the catalyst for lactide ring-opening polymerization according to any one of claims 1-3, characterized by comprising the steps of:
(1) Dye under nitrogen protection 1 With metal alkyls in solventsObtaining a solution of an alkyl metal complex through the reaction;
(2) Dye is carried out under the protection of nitrogen 2 Adding the catalyst into a solution of an alkyl metal complex for reaction to obtain a catalyst for lactide ring-opening polymerization;
the alkyl metal in the step (1) is trimethylaluminum.
5. The method for preparing a catalyst for lactide ring-opening polymerization according to claim 4, wherein the solvent in the step (1) is one or more of benzene, toluene or tetrahydrofuran, dye 1 The molar ratio of the solvent to the alkyl metal is 2-2.8:1, and the solvent to Dye is as follows 1 The mass ratio of (2) is 20-200:1, and the reaction time is 3-12h; the reaction is a stage heating reaction, wherein the reaction temperature of the first stage is between-78 and 25 ℃ and the reaction temperature of the second stage is between 60 and 125 ℃;
dye described in step (2) 2 The molar ratio of the catalyst to the alkyl metal is 1-1.5:1, the reaction temperature is 25-150 ℃, and the reaction time is 4-16h.
6. The use of the catalyst for lactide ring-opening polymerization according to any one of claims 1-3, wherein the catalyst for lactide ring-opening polymerization and lactide undergo ring-opening polymerization reaction in a solvent under the protection of nitrogen to obtain colored polylactic acid.
7. The use of the catalyst for lactide ring-opening polymerization according to claim 6, wherein the solvent is one or more of benzene, toluene, tetrahydrofuran or methylene chloride, and the molar ratio of the catalyst for lactide ring-opening polymerization to lactide is 1:50-10000, the mole ratio of lactide to solvent is 1:5-20, the ring-opening polymerization reaction temperature is 50-180 ℃, and the ring-opening polymerization reaction time is 2-24h.
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| GB0522154D0 (en) * | 2005-10-31 | 2005-12-07 | Univ Leeds | Novel catalytic materials and their use in the preparation of polymeric materials |
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