CN115521329A - 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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- CN115521329A CN115521329A CN202211045808.2A CN202211045808A CN115521329A CN 115521329 A CN115521329 A CN 115521329A CN 202211045808 A CN202211045808 A CN 202211045808A CN 115521329 A CN115521329 A CN 115521329A
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- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical group CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 238000007151 ring opening polymerisation reaction Methods 0.000 title claims abstract description 60
- 239000003054 catalyst Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 229920000747 poly(lactic acid) Polymers 0.000 claims abstract description 54
- 239000000975 dye Substances 0.000 claims abstract description 53
- 239000004626 polylactic acid Substances 0.000 claims abstract description 53
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910052751 metal Inorganic materials 0.000 claims abstract description 21
- 239000002904 solvent Substances 0.000 claims abstract description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 17
- 239000002184 metal Substances 0.000 claims abstract description 15
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 9
- -1 alkyl metal complex Chemical class 0.000 claims abstract description 8
- 150000003839 salts Chemical class 0.000 claims abstract description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 42
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 21
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 9
- 239000003446 ligand Substances 0.000 claims description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 6
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 238000004043 dyeing Methods 0.000 abstract description 22
- 239000000463 material Substances 0.000 abstract description 11
- 239000000986 disperse dye Substances 0.000 abstract description 5
- 229920000642 polymer Polymers 0.000 abstract description 3
- 239000002351 wastewater Substances 0.000 abstract description 3
- 230000008859 change Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 25
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 23
- 230000008569 process Effects 0.000 description 11
- 238000006116 polymerization reaction Methods 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 238000001556 precipitation Methods 0.000 description 7
- 239000004595 color masterbatch Substances 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- 238000004040 coloring Methods 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 101001018064 Homo sapiens Lysosomal-trafficking regulator Proteins 0.000 description 3
- 102100033472 Lysosomal-trafficking regulator Human genes 0.000 description 3
- 244000038561 Modiola caroliniana Species 0.000 description 3
- 235000010703 Modiola caroliniana Nutrition 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 238000007142 ring opening reaction Methods 0.000 description 3
- 239000010865 sewage Substances 0.000 description 3
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000001000 anthraquinone dye Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000012967 coordination catalyst Substances 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000004310 lactic acid Substances 0.000 description 2
- 235000014655 lactic acid Nutrition 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 239000002685 polymerization catalyst Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 238000000859 sublimation Methods 0.000 description 2
- 230000008022 sublimation Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 1
- 240000003183 Manihot esculenta Species 0.000 description 1
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- 241000209140 Triticum Species 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920013724 bio-based polymer Polymers 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000001257 hydrogen Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 238000007344 nucleophilic reaction Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000052 poly(p-xylylene) Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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Classifications
-
- 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 Table
- C07F5/06—Aluminium compounds
- C07F5/069—Aluminium compounds without C-aluminium linkages
-
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention belongs to the technical field of polymers, and particularly relates to a catalyst for lactide ring-opening polymerization, and a preparation method and application thereof. Dye under the protection of nitrogen 1 Reacting with alkyl metal in a solvent to obtain a solution of an alkyl metal complex; under the protection of nitrogen, dye is added 2 Adding the obtained product 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 undergo 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 in the traditional disperse dye dyeing of polylactic acid, and avoiding the traditional polylactic acidThe material is subjected to a great deal of high COD and high salt dyeing wastewater generation 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, and a preparation method and application thereof.
Background
Polylactic Acid (PLA) is a bio-based polymer material formed by using renewable starch such as corn, wheat, cassava and the like as an initial raw material, fermenting and converting lactic Acid, and then directly condensing the lactic Acid or performing ring-opening polymerization (ROP) on a cyclic intermediate dimer (lactide). After being discarded, the polylactic acid material can be completely decomposed into CO under the action of microorganisms, acid and alkali 2 And H 2 O, which is subsequently photosynthesized, can be converted intoStarting material starch. 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 biomedicine, textile, packaging and the like. The biodegradability of the polylactic acid makes the polylactic acid have unique advantages when being applied to more rapid spinning.
The color of everything in nature can not be separated, the life of human beings is closely and indiscriminately connected with the color, and food packaging, clothes color, living environment and articles are closely related to the color. Therefore, the colored polylactic acid can be more suitable for the market demand. By adopting the traditional dyeing mode, on one hand, the promotion of the dye is not high, the physical and mechanical property retentivity is poor, the dyeing fastness is not high, and the color fading is easy in the dyeing process; on the other hand, the traditional dyeing needs to consume a large amount of energy sources such as water, electricity, gas and the like, and can generate sewage to pollute the environment. At present, the colored polylactic acid is also produced by adopting a stock solution coloring technology, but color master batch pigment and other additives are added in the processing process, and the 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 a lactate type disperse dye with azo structure for dyeing polylactic acid fiber, and a preparation method and a dyeing process thereof, wherein a lactate group with strong polarity, which is similar to a fiber structure, is introduced into the lactate type disperse dye structure, so as to improve the affinity of the dye with the polylactic acid fiber, and improve the dye uptake, and meanwhile, hydroxyl groups on the lactate group in the dye can improve the boiling point of the dye, and due to the existence of the hydroxyl groups, hydrogen bonds can be formed between dye molecules, so as to improve the sublimation resistance fastness of the dye, so that the dye has bright color, high color intensity, good fastness performance, and better dyeing effect; however, the patent needs to consume a large amount of energy sources such as water, electricity, gas and the like, and sewage is generated to pollute the environment. Still some researchers have done many explorations in the color masterbatch industry, and the colored masterbatch and polylactic acid are mixed and applied to the polylactic acid field. For example, chinese patent CN110922613A discloses a colored polylactic acid particle and a preparation method thereof, the colored polylactic acid particle is composed of polylactic acid and pigment, a colorless polylactic acid material in a molten state after polymerization is directly mixed with a molten colored polylactic acid prepared from a polylactic acid-based color master batch to prepare a colored polylactic acid mixed melt, and then underwater granulation and drying are performed to prepare the colored polylactic acid particle, so that the existing step of coloring the colorless polylactic acid is omitted, and equipment investment and raw material cost are both significantly reduced; although the coloring method of polylactic acid disclosed in the patent can be used for preparing polylactic acid products with various colors, the synthesis temperature is high, the steps are complicated, color master pigments and other additives are added in the processing process, and the equipment cleaning and waste silk recycling are difficult.
So far, the problems of low dye uptake, poor fastness, high temperature in the color master batch synthesis process, difficult cleaning of equipment and the like exist in the research of polylactic acid dyeing, and the problems become the problems which need 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 the lactide ring-opening polymerization to generate colored polylactic acid; the invention also provides a preparation method and application of the catalyst for lactide ring-opening polymerization, which realize 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 dyeing of polylactic acid, 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, saving energy, reducing consumption and meeting the requirements of 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 Being a Dye ligand, dye 2 Is a dye molecule containing hydroxyl, the structural formula represents that M is respectively connected withDye 1 、Dye 2 Are connected.
And M is aluminum.
The Dye 1 Is anthraquinone dye ligand.
The Dye 1 The structural formula of (A) is as follows:
wherein R is 1 is-OH, -NH 2 、-NHCH 3 、-NHC 6 H 5 or-NHOC 6 H 5 One of (a) and (b);
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 (a) and (b);
R 5 is-H, -OH or-NH 2 To (3) is provided.
The Dye 1 The structural formula of (A) is one of the following structural formulas:
the Dye 2 The structural formula of (A) 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 the content of the hydroxyl group,n is not less than 1 and not more than 18 and n is an integer;
R 8 is-H, -CH 3 -Cl or-OCH 3 One of (1);
R 9 is-H or-CH 3 ；
R 10 is-H, -CH 3 、-NHCOCH 3 or-NHCOC 2 H 5 One of (1);
R 11 is-H, -CH 3 、-OCH 3 、-Cl、-Br、-NO 2 or-CN;
R 12 is-H, -Cl, -Br, -NO 2 or-CN;
R 13 is-H, -NO 2 or-CN;
R 14 is-H, -CH 3 or-CH 2 CH 2 One of CN;
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 -Cl or-OCH 3 One of (1);
R 17 is-H or-CH 3 ；
R 18 is-H, -CH 3 、-NHCOCH 3 or-NHCOC 2 H 5 One of (1);
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 the protection of nitrogen 1 Reacting with alkyl metal in a solvent to obtain a solution of an alkyl metal complex;
(2) Under the protection of nitrogen, dye is added 2 Adding the mixture into a solution of an alkyl metal complex for reaction,obtaining 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, and toluene is preferred.
Dye described in step (1) 1 The molar ratio to metal alkyl is 2 to 2.8.
The solvent and Dye described in step (1) 1 The mass ratio of (A) to (B) is 20-200.
The reaction time in the step (1) is 3-12h.
The reaction in the step (1) is a staged heating reaction, wherein the reaction temperature in the first stage is-78-25 ℃, and the reaction temperature in the second stage is 60-125 ℃.
Dye described in step (2) 2 The molar ratio to the metal alkyl is 1 to 1.5.
The reaction temperature in the step (2) is 25-150 ℃, and the reaction time is 4-16h.
The catalyst for lactide ring-opening polymerization is applied to the ring-opening polymerization reaction of the catalyst for lactide ring-opening polymerization and lactide in a solvent under the protection of nitrogen to obtain colored polylactic acid.
The solvent is one or more of benzene, toluene, tetrahydrofuran or dichloromethane.
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 has the following specific reaction equation:
the catalyst for lactide ring-opening polymerization is a metal coordination catalyst, and the structural formula is as follows:
the synthesis reaction mechanism of the catalyst for lactide ring-opening polymerization is a coordination reaction occurring at a metal center. Dye 1 The dye ligand is anthraquinone dye with a plane structure, shortens the distance between coordination atoms (N and O), and provides convenient conditions for coordination reaction with a metal center. And Dye 1 The Dye ligand has larger steric hindrance, and when the metal center is connected with two Dye 1 After the Dye ligand, it is very difficult to attach a third Dye to the metal center 1 A dye ligand; and Dye having a hydroxyl group structure 2 The dye molecule has relatively small steric hindrance, and provides convenient conditions for the hydroxyl to approach the active methyl and react.
The reaction mechanism for synthesizing the colored polylactic acid utilizes the ring-opening polymerization of lactide. The lactide is coordinated with the metal center, so that electrophilic activation of the lactide occurs, and then nucleophilic attack of the metal center is performed to form an intermediate, and meanwhile, the dye molecule containing hydroxyl attacks the activated monomer. The chemical bond with higher energy in the intermediate is broken to realize ring opening and form connection with Dye 1 Dye ligand, dye 2 The long lactide monomer chain of the dye molecule is subjected to metal coordination, nucleophilic reaction and broken bond ring opening along with chain growth of lactide until a coordination bond is subjected to cracking termination reaction.
Dye 1 Dye ligand and Dye containing hydroxyl structure 2 Dye molecules of the same or different color, byAnd (3) ring-opening polymerization of lactide is carried out, and the color blending or color matching of polylactic acid is finally realized.
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 simultaneously realizing the lactide ring-opening polymerization and the coloring and color matching of polylactic acid.
The invention has the following beneficial effects:
compared with the existing color master batch polylactic acid technology, the colored polylactic acid has simple preparation process and can be directly dyed in catalytic polymerization. The polymerization process has low temperature, and the influence of the temperature on the color in the melting process of the color master batch is avoided. Compared with the traditional dyeing, the colored polylactic acid disclosed by the invention directly avoids the dyeing process, dye molecules are directly bonded into the polylactic acid molecules in the lactide ring-opening process, and the dye and the polylactic acid are combined in a chemical bond form, so that the color fastness of the colored fiber, such as friction resistance, washing resistance, sublimation resistance and the like, is remarkably improved. In addition, the polymerization dyeing process is adopted, so that a large amount of dyeing sewage treatment caused by the traditional disperse dye dyeing process is avoided, the industrial problem of high COD and high salt wastewater discharge in the traditional printing and dyeing process can be effectively solved, and the method has a good application prospect. The colored polylactic acid synthesis process provided by the invention can also realize that different color dyes can finish color matching through a polymerization process, so that a polylactic acid high polymer material with richer color light is obtained, and the application range of polylactic acid is enlarged.
The metal coordination catalyst provided by the invention is convenient to prepare and stable in property, and has the function of catalyzing lactide ring-opening polymerization to generate colored polylactic acid.
Drawings
FIG. 1 is a nuclear magnetic spectrum of a catalyst for ring-opening polymerization of lactide of orange-red color obtained in example 1.
FIG. 2 is a nuclear magnetic spectrum of orange polylactic acid obtained in example 1.
Detailed Description
The present invention is further described below with reference to examples.
Example 1
Under the protection of nitrogen, 0.446g of D1 is dissolved in 30mL of toluene, and is placed at-78 ℃ to react with 1mL of 1mol/L trimethylaluminum solution for 4 hours, the temperature is slowly raised to room temperature, the solution is heated to reflux for 1 hour, then 0.30g of D5 is added into the reaction system and reacts for 6 hours at 75 ℃, the solvent is removed by reduced pressure distillation, the product is washed by n-hexane and dried in vacuum, the product is recrystallized, washed and dried in the toluene, and orange red catalyst for lactide ring-opening polymerization 0.71g is obtained, the nuclear magnetic spectrum of the catalyst for lactide ring-opening polymerization is shown in figure 1, and the structural formula of the catalyst for lactide ring-opening polymerization is as follows:
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 the lactide, the purified toluene solution and the orange red catalyst are subjected to polymerization reaction at 100 ℃ for 12 hours, then ethanol solution of hydrochloric acid with the volume fraction of 10% is added into the lactide solution to stop the reaction, the reaction solution is poured into n-hexane for standing and precipitation, the precipitation is filtered, dichloromethane is dissolved by using dichloromethane, a proper amount of n-hexane is added into the precipitation solution to separate out solid, the reaction solution is filtered, drained and dried in vacuum after the reaction is repeated for three times to obtain orange polylactic acid, and the nuclear magnetic spectrum of the orange polylactic acid is shown in figure 2. The tested material has light fastness up to 7-8 grade and washing fastness up to 5 grade.
Example 2
Under the protection of nitrogen, 0.468g D1 is dissolved in 40mL tetrahydrofuran and placed at-78 ℃ to react with 1mL of 1mol/L trimethylaluminum solution for 6h, the temperature of the mixed solution is slowly increased to room temperature, the mixed solution is heated to reflux for 1h, then 0.345g D6 is added into the reaction system and reacts for 4h under the reflux condition, the solvent is removed by reduced pressure distillation, the normal hexane is used for washing, the vacuum drying is carried out, the product is recrystallized in toluene, the washing and the drying are carried out, and 0.69g of mauve catalyst for lactide ring-opening polymerization is obtained, 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 mauve catalyst for lactide ring-opening polymerization into a Schlenk bottle, then carrying out polymerization reaction at 110 ℃ for 8 hours, adding ethanol solution of hydrochloric acid with the volume fraction of 10% into the solution to terminate the reaction, pouring the reaction solution into n-hexane for standing and precipitating, filtering, dissolving the precipitate by using dichloromethane, adding a proper amount of n-hexane to separate out a solid, repeating the steps for three times, filtering, draining and carrying out vacuum drying to obtain the mauve polylactic acid. The tested material has light fastness up to 8 grade and washing fastness up to 5 grade.
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 temperature of the mixed solution is slowly raised to room temperature, the mixed solution is heated to reflux for 1h, then 0.508g of D7 is added into the reaction system and reacts at 70 ℃ for 5h, 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, coffee-colored catalyst for lactide ring-opening polymerization is obtained, and the structural formula of the catalyst for lactide ring-opening polymerization is as follows:
under the protection of nitrogen, 16g of lactide, 80mL of purified toluene solution and 0.12g of coffee-colored catalyst for lactide ring-opening polymerization are added into a Schlenk bottle, then polymerization reaction is carried out at 120 ℃ for 10 hours, then ethanol solution of hydrochloric acid with the volume fraction of 10% is added into the solution to terminate the reaction, the reaction solution is poured into n-hexane for standing and precipitation, filtration is carried out, the precipitation is dissolved by dichloromethane, a proper amount of n-hexane is added to precipitate solid, and after the steps are repeated for three times, filtration, pumping-out and vacuum drying are carried out to obtain the coffee-colored polylactic acid. The tested material has light fastness up to grade 7 and washing fastness up to grade 4-5.
Example 4
Under the protection of nitrogen, dissolving 0.655g D2 in 50mL of toluene, reacting with 1mL of 1mol/L trimethylaluminum solution at 10 ℃ for 6h, slowly heating the mixed solution to room temperature, heating to reflux for 1h, then adding 0.483g D6 into the reaction system, reacting at 120 ℃ for 4h, distilling under reduced pressure to remove the solvent, washing with n-hexane, vacuum drying, recrystallizing the product in toluene, washing, and drying to obtain 0.75g of purple catalyst for lactide ring-opening polymerization, wherein the structural formula of the catalyst for lactide ring-opening polymerization is as follows:
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 polymerization reaction is carried out for 7h at 130 ℃, then ethanol solution of hydrochloric acid with the volume fraction of 10% is added into the mixture to terminate the reaction, the reaction solution is poured into n-hexane for standing and precipitation, filtration is carried out, the precipitation is dissolved by dichloromethane, a proper amount of n-hexane is added to precipitate solids, and after the steps are repeated for three times, filtration, pumping-out and vacuum drying are carried out to obtain the reddish-purple polylactic acid. The light fastness of the tested material can reach 8 grades, and the washing fastness of the tested material can reach 4 grades.
Claims (10)
1. A catalyst for lactide ring-opening polymerization, characterized by the structural formula:
wherein M is a metal, dye 1 Being Dye ligands, dye 2 Is a dye molecule containing a hydroxyl group.
2. The catalyst for the ring-opening polymerization of lactide according to claim 1, characterized in that the M is aluminum.
3. The catalyst for lactide ring-opening polymerization according to claim 1, characterized in that the Dye 1 The structural formula of (A) is as follows:
wherein R is 1 is-OH, -NH 2 、-NHCH 3 、-NHC 6 H 5 or-NHOC 6 H 5 One of (a) and (b);
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 (1);
R 5 is-H, -OH or-NH 2 To (3) is provided.
4. The catalyst for lactide ring-opening polymerization according to claim 3, characterized in that the Dye 1 The structural formula of (A) is one of the following structural formulas:
5. the catalyst for lactide ring-opening polymerization according to claim 1, characterized in that the Dye 2 The structural formula of (A) 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 -Cl or-OCH 3 One of (1);
R 9 is-H or-CH 3 ；
R 10 is-H, -CH 3 、-NHCOCH 3 or-NHCOC 2 H 5 One of (1);
R 11 is-H, -CH 3 、-OCH 3 、-Cl、-Br、-NO 2 or-CN;
R 12 is-H, -Cl, -Br, -NO 2 or-CN;
R 13 is-H, -NO 2 or-CN;
R 14 is-H, -CH 3 or-CH 2 CH 2 One of CN;
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 -Cl or-OCH 3 One of (a) and (b);
R 17 is-H or-CH 3 ；
R 18 is-H, -CH 3 、-NHCOCH 3 or-NHCOC 2 H 5 One of (1);
R 19 is-H or-NO 2 。
6. The catalyst for lactide ring-opening polymerization according to claim 5, characterized in that the Dye 2 The structural formula of (A) is one of the following structural formulas:
7. a method for preparing a catalyst for lactide ring-opening polymerization according to any one of claims 1 to 6, characterized by comprising the steps of:
(1) Dye under the protection of nitrogen 1 Reacting with alkyl metal in a solvent to obtain a solution of an alkyl metal complex;
(2) Under the protection of nitrogen, dye is added 2 Adding the mixture into a solution of an alkyl metal complex for reaction to obtain the catalyst for lactide ring-opening polymerization.
8. The method for preparing a catalyst for lactide ring-opening polymerization according to claim 7, wherein the alkyl metal in the step (1) is trimethylaluminum, the solvent is one or more of benzene, toluene or tetrahydrofuran, dye 1 Molar ratio to metal alkyl of 2 to 2.8, solvent to Dye 1 The mass ratio of (1) is 20-200, and the reaction time is 3-12h; the reaction is a staged heating reaction, wherein the reaction temperature in the first stage is-78-25 ℃, and the reaction temperature in the second stage is 60-125 ℃;
dye described in step (2) 2 The molar ratio of the metal salt to the alkyl metal is 1-1.5, the reaction temperature is 25-150 ℃, and the reaction time is 4-16h.
9. Use of the catalyst for lactide ring-opening polymerization according to any one of claims 1 to 6, wherein the catalyst for lactide ring-opening polymerization and lactide undergo a ring-opening polymerization reaction in a solvent under the protection of nitrogen to obtain colored polylactic acid.
10. Use of a catalyst for lactide ring-opening polymerization according to claim 9, characterized in that the solvent is one or more of benzene, toluene, tetrahydrofuran or dichloromethane, and the molar ratio of the catalyst for lactide ring-opening polymerization to lactide is 1:50-10000, and the molar 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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