CN108129646B - Imino-containing high molecular weight polyester, preparation method and application - Google Patents
Imino-containing high molecular weight polyester, preparation method and application Download PDFInfo
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- CN108129646B CN108129646B CN201810078746.2A CN201810078746A CN108129646B CN 108129646 B CN108129646 B CN 108129646B CN 201810078746 A CN201810078746 A CN 201810078746A CN 108129646 B CN108129646 B CN 108129646B
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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
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/685—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen
- C08G63/6854—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6856—Dicarboxylic acids and dihydroxy compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
- B65D65/38—Packaging materials of special type or form
- B65D65/46—Applications of disintegrable, dissolvable or edible materials
- B65D65/466—Bio- or photodegradable packaging materials
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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
- C08G63/83—Alkali metals, alkaline earth metals, beryllium, magnesium, copper, silver, gold, zinc, cadmium, mercury, manganese, or compounds thereof
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- 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
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
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- C—CHEMISTRY; METALLURGY
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- 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
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
- C08G63/86—Germanium, antimony, or compounds thereof
- C08G63/866—Antimony or compounds thereof
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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
- C08G63/87—Non-metals or inter-compounds thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
Abstract
The invention adopts N- (carboxymethyl) glycine and dihydric alcohol with cyclic rigid group as monomers, and metal organic catalyst or sulfonic acid catalyst as esterification and polycondensation catalyst, and obtains imino-containing high molecular weight polyester with melting point or softening point of 160-190 ℃ and number average molecular weight of 31000-46000 through melt polymerization. The prepared imino group-containing high molecular weight polyester has the characteristic of higher strength, and the tensile strength is 100-150 MPa. The imino group-containing high molecular weight polyester disclosed by the invention can be used as bottle grade polyester, and the prepared bottle grade material can be used as a packaging material in the beverage and food industries with the effective period of up to 4 years. After the packaging material is used, the packaging material is discarded to the natural soil environment, the packaging material starts to be obviously degraded in the natural soil environment from the second year, and the molecular weight of the packaging material is reduced by 20-30% every year in 2-4 years.
Description
Technical Field
The invention belongs to the field of synthesis of polyester products. In particular to a high molecular weight polyester containing imino, a preparation method and application.
Background
In 2013, the annual consumption of plastics in China exceeds 6000 million tons, and the plastic becomes the first major plastic consuming country in the world. When the traditional plastic product is convenient for life of people, the traditional plastic product brings environmental problems because the traditional plastic product is not easy to degrade, the plastic product generally needs at least 100 years to be naturally degraded, and the plastic product which is discarded at will causes serious 'white pollution' problems. The waste plastics causing environmental problems are mainly discarded after the use of bulk goods such as PE, PP, PS and the like, and the waste polyester is also a part of the source of white pollution. In order to avoid the influence of environmental problems caused by waste polyester, researchers have been actively developing degradable polyester materials for the plastic industry in recent years. Among them, it has become a research hotspot that polyesters synthesized by using bio-based materials have excellent degradation characteristics. Meanwhile, the polyester synthesized by adopting the bio-based raw material can reduce the dependence of polyester production on fossil resources, and has wide prospect.
However, since bio-based polyester does not contain rigid groups, the strength of the material itself is very weak, for example, polylactic acid (PLA) is a kind of polyester material made from starch raw material extracted from renewable plant resources (such as corn), has excellent degradation performance, and has been widely used in packaging products such as plastic bags and films. However, the strength of the polyester materials such as PLA is weak, and in some plastic products needing certain strength, such as plastic shells and plastic bottles, the PLA cannot reach the use requirement easily.
Imine polyesters have been reported in the literature to have excellent degradation properties (Jiang z. lipase-catalyzed synthesis of poly (amine-co-esters) via copolymerization of ester with amino-hydrolyzed diol [ J ]. Biomacromolecules,2010,11(4): 1089-93.). However, the long-chain aliphatic imine polyesters proposed in the literature have too low a tensile strength to be used as a plastic raw material. The aromatic polyester is a high strength polyester material (Guolin Wu, Chengcai Pang, Jie Zhang, et al. novel Vanillic Acid-based Poly (ether-ester) s: From Synthesis to Properties [ J ]. Polymer Chemistry,2015,6(5): 797-804.).
In addition, the conventional catalyst such as antimony trioxide used in the existing polyester preparation process has large proportion in a reaction system, large catalyst consumption, high catalysis cost, heavier product color and higher heavy metal content, and influences the use of the product as a high-grade packaging material in the industries of beverages, foods and the like.
Based on the background, the invention adopts N- (carboxymethyl) glycine and dihydric alcohol with a cyclic rigid group as monomers, and adopts a metal organic catalyst or a sulfonic acid catalyst as an esterification and polycondensation catalyst to obtain the imino-containing high molecular weight polyester with the melting point of 160-190 ℃ and the number average molecular weight of 31000-46000 through melt polymerization. The prepared process adopts an efficient metal organic or sulfonic acid catalyst, the catalyst is small in dosage and low in catalytic cost, the polyester product is pure in color, the metal content is extremely low or no metal is contained, the synthesized imino-containing high molecular weight polyester has the characteristic of higher strength, and the tensile strength is 100-150 MPa. The imino-containing high molecular weight polyester disclosed by the invention can be used as a high-grade packaging material in the industries of beverages, foods and the like, and can be used as a bottle-grade polyester, and the prepared bottle-grade material can be used as a packaging material in the beverage and food industries with the effective period of up to 4 years. After the packaging material is used, the packaging material is discarded to the natural soil environment, the packaging material starts to degrade in the natural soil environment from the second year, and the molecular weight of the packaging material is reduced by 20-30% every year in 2-4 years.
Disclosure of Invention
Aiming at the problems in the prior art, the invention adopts N- (carboxymethyl) glycine and dihydric alcohol with cyclic rigid groups as monomers to synthesize the bio-based polyester with excellent service performance, and meanwhile, the polyester has excellent degradation performance in natural soil environment.
In order to realize the purpose of the invention, the invention adopts the following technical scheme:
an imino-containing high molecular weight polyester, a preparation method and application thereof, wherein the imino-containing high molecular weight polyester has the following structure:
the preparation method of the imino group-containing high molecular weight polyester comprises the following steps:
(1) adding N- (carboxymethyl) glycine, dihydric alcohol and a catalyst into a single-neck flask, replacing nitrogen to an oxygen-free and water-free state, firstly carrying out esterification reaction at 130-150 ℃ under normal pressure for 1-2 hours, then heating up from 150 ℃, carrying out polycondensation reaction at 100-1000 Pa, controlling the heating rate at 20 ℃/hour, and finally reacting at 190 ℃ for 2 hours to obtain the imino-containing high-molecular-weight polyester crude product.
(2) And (3) stopping vacuumizing after the polycondensation reaction is finished, filling nitrogen into the single-neck flask, adding a sufficient amount of chloroform solvent into the single-neck flask after the system is cooled to room temperature to fully dissolve the crude polyester product, taking the clear solution after dissolution, dropwise adding methanol solvent into the clear solution to precipitate a solid, centrifuging to obtain the solid, washing the solid with ethanol, and drying at 80 ℃ for 2 hours to obtain the colorless high-molecular-weight polyester product containing imino groups.
The dihydric alcohol in the step (1) is catechol di (2-hydroxyethyl) ether
Resorcinol bis (2-hydroxyethyl) ether
1, 3-Dihydroxyethyl cyclohexane ethers
1, 4-Dihydroxyethyl cyclohexane ethers
One or a mixture of two of them. N- (carboxymethyl) glycineThe ratio of the number of moles of (B) to the total number of moles of the diol is 1:1.01 to 1: 1.10.
In the step (1), the catalyst is a metal organic catalyst or a sulfonic acid catalyst. Wherein the metal organic catalyst is zinc oxalate, ethylene glycol antimony, and titanocene dichloride (C)10H10Cl2Ti, CAS: 1271-19-8), zirconocene dichloride (C)10H10Cl2Zr, CAS: 1291-32-3), molybdenum dichlorodicyclo (C)10H10Cl2Mo, CAS: 12184-22-4), dichlorocyclopentylene (C)10H10Cl2W, CAS: 12184-26-8), hafnocene dichloride (C)10H10Cl2Hf, CAS: : 12116-66-4), vanadium dichlorometallocenes (C)10H10Cl2V, CAS: 12083-48-6), zirconocene hydrochloride (C)10H11ClZr, CAS: 37342-97-5); the sulfonic acid catalyst is one of methanesulfonic acid, benzenesulfonic acid, sulfamic acid, p-toluenesulfonic acid, p-chlorobenzenesulfonic acid, sulfanilic acid, p-methoxybenzenesulfonic acid and p-nitrobenzenesulfonic acid. The ratio of the number of moles of the catalyst to the number of moles of N- (carboxymethyl) glycine is 0.0001:1 to 0.001: 1.
An imino-containing high molecular weight polyester, a preparation method and application thereof, and the application of the imino-containing high molecular weight polyester in the preparation of bottle-grade polyester materials, wherein the method comprises the following steps: fully mixing the components according to the mass ratio of 100 parts of imino-containing high-molecular-weight polyester, 30-45 parts of plasticizer and 2-3 parts of stabilizer; after the mixing is finished, the subsequent forming and processing processes such as extrusion, injection molding, stretching, blow molding and the like can be carried out. The plasticizer is one of phthalate, tricresyl phosphate and dioctyl sebacate; the stabilizer is one of triphenyl phosphate, trimethyl phosphate and triethyl phosphonoacetate.
The invention adopts N- (carboxymethyl) glycine and dihydric alcohol with a cyclic rigid group as monomers, and a metal organic catalyst or a sulfonic acid catalyst as an esterification and polycondensation catalyst, and obtains colorless imino-containing high molecular weight polyester with a melting point of 160-190 ℃ and a number average molecular weight of 31000-46000 through melt polymerization.
Preparing N- (carboxymethyl) glycine: the monomer N- (carboxymethyl) glycine can be obtained by alkalizing low-cost biomass glycine with wide sources under the condition that water is used as a solvent, then reacting with chloroacetic acid aqueous solution, treating with sodium carbonate and neutralizing with acid. Therefore, the method has the characteristics of low raw material cost, renewability and the like, and can effectively relieve the problem of petroleum-dependent resource shortage in polyester synthesis; the other monomer for polyester synthesis can be obtained by condensing catechol or resorcinol with chlorohydrin, and the raw materials are cheap and easy to obtain.
The preparation process of the imino group-containing high molecular weight polyester adopts a high-efficiency metal organic or sulfonic acid catalyst, the catalyst is small in dosage and low in catalysis cost, so that the polyester product has pure color and extremely low metal content or does not contain metal, and the requirements of packaging materials in high-grade beverage and food industries on the color quality of raw materials are met; the synthesized imino-containing high molecular weight polyester has the characteristic of high strength, the tensile strength is 100-150 MPa, the thermal property is excellent, the imino-containing high molecular weight polyester can be used as a bottle-grade material prepared from a bottle-grade polyester raw material, and can be used as a packaging material in the beverage and food industries with the validity period of 4 years.
Because the polyester structure contains easily degradable imino chain links, the polyester is easily degradable in natural soil environment.
After the packaging material is used, the packaging material is discarded to the natural soil environment, the packaging material starts to degrade in the natural soil environment from the second year, and the molecular weight of the packaging material is reduced by 20-30% every year in 2-4 years.
The fundamental reason for having the above inventive effect is:
1. carefully selecting raw materials: n- (carboxymethyl) glycine which is cheap and easy to obtain is introduced into a polyester structure as a monomer to complete the function, is discarded into the natural soil environment and is easily degraded under the influence of natural sunlight, water and microorganisms. And the introduction of another o-or resorcinol bis (2-hydroxyethyl) ether or 1, 3-dihydroxyethyl cyclohexane ether or 1, 4-dihydroxyethyl cyclohexane ether with a cyclic rigid group can improve the mechanical properties (including tensile strength, tensile modulus, bending strength and bending modulus) of the polyester, improve the thermal properties such as melting point far higher than that of PLA in use and greatly improve the thermal decomposition temperature.
2. The catalyst and the polyester synthesis process are optimally matched with the performance of the raw materials: the preparation process adopts an efficient metal organic or sulfonic acid catalyst, the catalyst is small in dosage and low in catalytic cost, so that the polyester product has pure color and extremely low metal content or does not contain metal, and the requirements of packaging materials in high-grade beverage and food industries on the color quality of raw materials are met;
drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of the D1 polyester obtained in example 1 of the present invention.
FIG. 2 is a GPC chart of D1 polyester obtained in example 1 of the present invention.
FIG. 3 is a TG plot of a D1 polyester prepared according to example 1 of the present invention.
FIG. 4 is a graph showing the degradation tendency of the D1 polyester prepared in example 1 of the present invention in natural soil environment.
Detailed Description
Example 1
The degradable polyester D1 is synthesized by using N- (carboxymethyl) glycine as one of the monomers. The structural formula of the polyester is as follows:
the method for synthesizing the nitrogen-containing polyester D1 comprises the following specific steps:
in a dried single-neck flask, 2.662g (20mmol) of N- (carboxymethyl) glycine and 3.962g of resorcinol bis (2-hydroxyethyl) ether are added, meanwhile, titanocene dichloride is added, the temperature is gradually increased, and the reaction temperature is controlled to be 150 ℃. After reacting for 4-6 h, the reaction system is uniform and transparent, and the esterification reaction is finished.
And after 3 times of vacuum-pumping nitrogen replacement, heating, wherein the heating rate is fast and slow, the heating rate is 150-190 ℃/2 hours, the temperature is controlled to be 190 ℃, and the polyester is obtained after 2 hours of reaction. Then slowly vacuumizing until viscous polyester appears, and stopping stirring.
Dissolving the obtained polyester in a chloroform solution, centrifuging and precipitating, taking clear liquid, dripping the clear liquid into a methanol solution, taking precipitated ethanol for washing, and drying at 80 ℃ to obtain D1.
Example 2
The degradable polyester D2 is synthesized by using N- (carboxymethyl) glycine as one of the monomers. The structural formula of the polyester is as follows:
the method for synthesizing the nitrogen-containing polyester D2 comprises the following specific steps:
in a dried single-neck flask, 2.662g (20mmol) of N- (carboxymethyl) glycine and 3.962g of hydroquinone bis (2-hydroxyethyl) ether are added, while 2.923mg (0.01mmol) of zirconocene dichloride is added, the temperature is gradually raised, and the reaction temperature is controlled at 150 ℃. After reacting for 4-6 h, the reaction system is uniform and transparent, and the esterification reaction is finished.
And after 3 times of vacuum-pumping nitrogen replacement, heating, wherein the heating rate is fast and slow, the heating rate is 150-190 ℃/2 hours, the temperature is controlled to be 190 ℃, and the polyester is obtained after 2 hours of reaction. Then slowly vacuumizing until viscous polyester appears, and stopping stirring.
Dissolving the obtained polyester in a chloroform solution, centrifuging and precipitating, taking clear liquid, dripping the clear liquid into a methanol solution, taking precipitated ethanol for washing, and drying at 80 ℃ to obtain D2.
Example 3
The degradable polyester D3 is synthesized by using N- (carboxymethyl) glycine as one of the monomers. The structural formula of the polyester is as follows:
the method for synthesizing the nitrogen-containing polyester D3 comprises the following specific steps:
in a dried single-neck flask, 2.662g (20mmol) of N- (carboxymethyl) glycine and 2.549g of 1, 4-dihydroxyethyl cyclohexane ether were added, and 1.894mg (0.01mmol) of zinc oxalate was added simultaneously, and the temperature was gradually raised to 160 ℃. After reacting for 4-5 h, the reaction system is uniform and transparent, and the esterification reaction is finished.
And after 3 times of vacuum-pumping nitrogen replacement, heating, wherein the heating rate is fast and slow, the heating rate is 150-190 ℃/2 hours, the temperature is controlled to be 210 ℃, and the polyester is obtained after 3 hours of reaction. Then slowly vacuumizing until viscous polyester appears, and stopping stirring.
Dissolving the obtained polyester in a chloroform solution, centrifuging and precipitating, taking clear liquid, dripping the clear liquid into a methanol solution, taking precipitated ethanol for washing, and drying at 80 ℃ to obtain D3.
Example 4
The degradable polyester D4 is synthesized by using N- (carboxymethyl) glycine as one of the monomers. The structural formula of the polyester is as follows:
the method for synthesizing the nitrogen-containing polyester D4 comprises the following specific steps:
in a dried single-neck flask, 2.662g (20mmol) of N- (carboxymethyl) glycine and 2.549g of 1, 3-dihydroxyethyl cyclohexane ether were added, and 4.236mg (0.01mmol) of ethylene glycol antimony was added simultaneously, and the temperature was gradually raised to 160 ℃. After reacting for 4-5 h, the reaction system is uniform and transparent, and the esterification reaction is finished.
And after 3 times of vacuum-pumping nitrogen replacement, heating, wherein the heating rate is fast and slow, the heating rate is 150-190 ℃/2 hours, the temperature is controlled to be 210 ℃, and the polyester is obtained after 3 hours of reaction. Then slowly vacuumizing until viscous polyester appears, and stopping stirring.
Dissolving the obtained polyester in a chloroform solution, centrifuging and precipitating, taking clear liquid, dripping the clear liquid into a methanol solution, taking precipitated ethanol for washing, and drying at 80 ℃ to obtain D4.
Example 5
The degradable polyester D5 is synthesized by using N- (carboxymethyl) glycine as one of the monomers. The structural formula of the polyester is as follows:
the method for synthesizing the nitrogen-containing polyester D5 comprises the following specific steps:
in a dried single-neck flask, 2.662g (20mmol) of N- (carboxymethyl) glycine, 1.981g of hydroquinone bis (2-hydroxyethyl) ether and 1.981g of resorcinol bis (2-hydroxyethyl) ether were added, and 0.961mg (0.01mmol) of methanesulfonic acid was added to gradually raise the temperature, and the reaction temperature was controlled to 160 ℃. After reacting for 4-5 h, the reaction system is uniform and transparent (clear point), and the esterification reaction is finished.
And after 3 times of vacuum-pumping nitrogen replacement, heating, wherein the heating rate is fast and slow, the heating rate is 150-190 ℃/2 hours, the temperature is controlled to be 210 ℃, and the polyester is obtained after 3 hours of reaction. Then slowly vacuumizing until viscous polyester appears, and stopping stirring.
Dissolving the obtained polyester in a chloroform solution, centrifuging and precipitating, taking clear liquid, dripping the clear liquid into a methanol solution, taking precipitated ethanol for washing, and drying at 80 ℃ to obtain D5.
Example 6
The degradable polyester D6 is synthesized by using N- (carboxymethyl) glycine as one of the monomers. The structural formula of the polyester is as follows:
the method for synthesizing the nitrogen-containing polyester D6 comprises the following specific steps:
in a dried single-neck flask, 2.662g (20mmol) of N- (carboxymethyl) glycine, 1.981g of hydroquinone bis (2-hydroxyethyl) ether and 1.274g of 1, 3-dihydroxyethylcyclohexane ether were added, and 1.732mg (0.01mmol) of sulfanilic acid was added simultaneously, and the temperature was gradually raised to 160 ℃. After reacting for 4-5 h, the reaction system is uniform and transparent, and the esterification reaction is finished.
And after 3 times of vacuum-pumping nitrogen replacement, heating, wherein the heating rate is fast and slow, the heating rate is 150-190 ℃/2 hours, the temperature is controlled to be 210 ℃, and the polyester is obtained after 3 hours of reaction. Then slowly vacuumizing until viscous polyester appears, and stopping stirring.
Dissolving the obtained polyester in a chloroform solution, centrifuging and precipitating, taking clear liquid, dripping the clear liquid into a methanol solution, taking precipitated ethanol for washing, and drying at 80 ℃ to obtain D6.
Example 7
The degradable polyester D7 is synthesized by using N- (carboxymethyl) glycine as one of the monomers. The structural formula of the polyester is as follows:
the method for synthesizing the nitrogen-containing polyester D7 comprises the following specific steps:
in a dried single-neck flask, 2.662g (20mmol) of N- (carboxymethyl) glycine, 1.981g of hydroquinone bis (2-hydroxyethyl) ether and 1.274g of 1, 4-dihydroxyethylcyclohexane ether were added, and 1.882mg (0.01mmol) of p-methoxybenzenesulfonic acid was added at the same time, and the temperature was gradually increased to 160 ℃. After reacting for 4-5 h, the reaction system is uniform and transparent, and the esterification reaction is finished.
And after 3 times of vacuum-pumping nitrogen replacement, heating, wherein the heating rate is fast and slow, the heating rate is 150-190 ℃/2 hours, the temperature is controlled to be 210 ℃, and the polyester is obtained after 3 hours of reaction. Then slowly vacuumizing until viscous polyester appears, and stopping stirring.
Dissolving the obtained polyester in a chloroform solution, centrifuging and precipitating, taking clear liquid, dripping the clear liquid into a methanol solution, taking precipitated ethanol for washing, and drying at 80 ℃ to obtain D7.
Example 8
The degradable polyester D8 is synthesized by using N- (carboxymethyl) glycine as one of the monomers. The structural formula of the polyester is as follows:
the method for synthesizing the nitrogen-containing polyester D8 comprises the following specific steps:
in a dried single-neck flask, 2.662g (20mmol) of N- (carboxymethyl) glycine, 1.981g of resorcinol bis (2-hydroxyethyl) ether and 1.274g of 1, 3-dihydroxyethylcyclohexane ether were added, and 2.034mg (0.01mmol) of p-nitrobenzenesulfonic acid was added, and the temperature was gradually increased to 160 ℃. After reacting for 4-5 h, the reaction system is uniform and transparent, and the esterification reaction is finished.
And after 3 times of vacuum-pumping nitrogen replacement, heating, wherein the heating rate is fast and slow, the heating rate is 150-190 ℃/2 hours, the temperature is controlled to be 210 ℃, and the polyester is obtained after 3 hours of reaction. Then slowly vacuumizing until viscous polyester appears, and stopping stirring.
Dissolving the obtained polyester in a chloroform solution, centrifuging and precipitating, taking clear liquid, dripping the clear liquid into a methanol solution, taking precipitated ethanol for washing, and drying at 80 ℃ to obtain D8.
Example 9
The degradable polyester D9 is synthesized by using N- (carboxymethyl) glycine as one of the monomers. The structural formula of the polyester is as follows:
the method for synthesizing the nitrogen-containing polyester D9 comprises the following specific steps:
in a dried single-neck flask, 2.662g (20mmol) of N- (carboxymethyl) glycine, 1.981g of resorcinol bis (2-hydroxyethyl) ether and 1.274g of 1, 4-dihydroxyethylcyclohexane ether were added, and 2.498mg (0.01mmol) of zirconocene hydrochloride was added simultaneously, and the temperature was gradually raised to 160 ℃. After reacting for 4-5 h, the reaction system is uniform and transparent, and the esterification reaction is finished.
And after 3 times of vacuum-pumping nitrogen replacement, heating, wherein the heating rate is fast and slow, the heating rate is 150-190 ℃/2 hours, the temperature is controlled to be 210 ℃, and the polyester is obtained after 3 hours of reaction. Then slowly vacuumizing until viscous polyester appears, and stopping stirring.
Dissolving the obtained polyester in a chloroform solution, centrifuging and precipitating, taking clear liquid, dripping the clear liquid into a methanol solution, taking precipitated ethanol for washing, and drying at 80 ℃ to obtain D9.
Example 10
The degradable polyester D10 is synthesized by using N- (carboxymethyl) glycine as one of the monomers. The structural formula of the polyester is as follows:
the method for synthesizing the nitrogen-containing polyester D10 comprises the following specific steps:
in a dried single-neck flask, 2.662g (20mmol) of N- (carboxymethyl) glycine, 1.274g of 1, 3-dihydroxyethyl cyclohexane ether and 1.274g of 1, 4-dihydroxyethyl cyclohexane ether were added, and 0.971mg (0.01mmol) of sulfamic acid was added simultaneously, and the temperature was gradually raised to 160 ℃. After reacting for 4-5 h, the reaction system is uniform and transparent, and the esterification reaction is finished.
And after 3 times of vacuum-pumping nitrogen replacement, heating, wherein the heating rate is fast and slow, the heating rate is 150-190 ℃/2 hours, the temperature is controlled to be 210 ℃, and the polyester is obtained after 3 hours of reaction. Then slowly vacuumizing until viscous polyester appears, and stopping stirring.
Dissolving the obtained polyester in a chloroform solution, centrifuging and precipitating, taking clear liquid, dripping the clear liquid into a methanol solution, taking precipitated ethanol for washing, and drying at 80 ℃ to obtain D10.
The results of the polyester testing portion of examples 1-10 are shown in Table 1.
TABLE 1
| Sample (I) | Mn1/(104g/mol) | PDI | Mn2/(104g/mol) | T95％/℃ | Melting or softening point/. degree.C |
| D1 | 4.15 | 1.95 | 2.07 | 333 | 180.2 |
| D2 | 4.21 | 1.81 | 2.11 | 337 | 184.3 |
| D3 | 3.96 | 1.75 | 1.90 | 331 | 172.7 |
| D4 | 3.94 | 1.63 | 1.99 | 329 | 176.6 |
| D5 | 4.37 | 1.87 | 2.23 | 336 | 192.2 |
| D6 | 4.65 | 1.78 | 2.28 | 339 | 179.0 |
| D7 | 3.85 | 1.76 | 1.89 | 332 | 169.4 |
| D8 | 3.84 | 1.77 | 1.93 | 330 | 167.5 |
| D9 | 3.87 | 1.75 | 1.85 | 329 | 165.3 |
| D10 | 3.77 | 1.62 | 1.66 | 325 | 162.1 |
| PLA | 3.42～3.68* | 1.67 | 1.42 | 320 | 153.8** |
M in Table 1n1Is the initial number average molecular weight of the sample, PDI is the molecular weight distribution of the sample, T95％Temperature required for 5% thermal decomposition of the sample, Mn2The number average molecular weight of the sample after being degraded for 3 years in the natural soil environment.
Data is derived from: shenquan, Sun Junquan, Wuliangjiang, et al, rare earth coordination catalysis synthesis of polylactic acid [ J ]. Acta Chim: sinica,1990,48(7): 686-containing 689.
Data from: lixiamei, Zhouwei, Wangdan, etc. research on the influence of plasticizer on the performance of polylactic acid [ J ] modern plastic processing application, 2008,20(2):41-44.
The sample to PLA strength ratio for examples 1-3 is shown in Table 2.
TABLE 2
| Material | Tensile strength MPa | Elongation at break/% |
| D1 | 134.1 | 119.3 |
| D2 | 150.3 | 123.2 |
| D3 | 110.0 | 116.5 |
| PLA*** | 52.0 | 8.9 |
Data from: zhangwei, Liangyurong, Wanglinyan, and the like, the structure and the performance of the PLA composite material filled with the compound modified clay [ J ] plastic, 2017(5), (43-45).
From a comparison of the data in Table 1, the number average molecular weight M of the imino group-containing high molecular weight polyesters of the invention synthesized with N- (carboxymethyl) glycine as one of the monomersn1Specific polylactic acid number average molecular weight Mn1A temperature T of 900 to 12300g/mol which is required for 5% thermal decomposition of the imino group-containing high molecular weight polyester95％The temperature T is 5 percent higher than the temperature T required by the thermal decomposition of the polylactic acid95％The melting point or softening point of the imino group-containing high molecular weight polyester is higher by 5 to 19 ℃ by 8.3 to 38.4 ℃ than that of the polylactic acid.
As shown by comparison of the data in Table 2, the tensile strength of the imino group-containing high molecular weight polyester synthesized by using N- (carboxymethyl) glycine as one of the monomers is 58.0-98.3 MPa higher than that of polylactic acid, and the elongation at break of the imino group-containing high molecular weight polyester synthesized by using N- (carboxymethyl) glycine as one of the monomers is 107.6-114.3% higher than that of polylactic acid.
From the data, the imino group-containing high molecular weight polyester synthesized by taking N- (carboxymethyl) glycine as one of the monomers has obviously improved molecular weight, thermal property, mechanical property and the like compared with the pure bio-based polylactic acid.
From comparison between Mn1 and Mn2 in Table 1, it can be seen that the imino group-containing high molecular weight polyester synthesized by using N- (carboxymethyl) glycine as one of the monomers degrades in natural soil environment, the molecular weight of the polyester decreases by half after 3 years, the imino group-containing high molecular weight polyester synthesized by using N- (carboxymethyl) glycine as one of the monomers has degradation performance equivalent to that of PLA, and the aromatic polyester such as PET reported in the prior art requires tens to hundreds of years to degrade significantly.
In conclusion, the imino group-containing high molecular weight polyester synthesized by taking N- (carboxymethyl) glycine as one of the monomers has the characteristics of high molecular weight, high strength, high thermal property and good mechanical property of the traditional aromatic polyester PET, and has the characteristic that the bio-based polylactic acid is easy to degrade in the natural soil environment, so the invention has good market prospect.
While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. Therefore, it is intended that the appended claims be interpreted as including preferred embodiments and all such alterations and modifications as fall within the scope of the invention. It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (5)
1. A process for producing a high molecular weight polyester containing imino groups, characterized by comprising the steps of:
(1) mixing N- (carboxymethyl) glycine and one or two of the following diols: adding catechol bis (2-hydroxyethyl) ether, resorcinol bis (2-hydroxyethyl) ether, 1, 3-dihydroxyethyl cyclohexane ether, 1, 4-dihydroxyethyl cyclohexane ether and a catalyst into a single-neck flask, replacing nitrogen to an oxygen-free and water-free state, performing esterification reaction for 1-2 hours at the temperature of 130-150 ℃ and under normal pressure, heating from 150 ℃, performing polycondensation reaction at 100-1000 Pa, controlling the heating rate at 20 ℃/hour, and finally reacting for 2 hours at 190 ℃ to obtain a high-molecular-weight polyester crude product containing imino groups;
(2) and (3) stopping vacuumizing after the polycondensation reaction is finished, filling nitrogen into the single-neck flask, adding a sufficient amount of chloroform solvent into the single-neck flask after the system is cooled to room temperature to fully dissolve the crude polyester product, taking the clear solution after dissolution, dropwise adding a methanol solvent into the clear solution to precipitate a solid, centrifuging to obtain the solid, washing the solid with ethanol, and drying at 80 ℃ for 2 hours to obtain the high-molecular-weight polyester product containing the imino group.
2. The method according to claim 1, wherein the ratio of the number of moles of N- (carboxymethyl) glycine to the total number of moles of the diol in the step (1) is 1:1.01 to 1: 1.10.
3. The process for producing a high molecular weight polyester containing an imino group according to claim 1, wherein in the step (1), the catalyst used is a metal organic catalyst or a sulfonic acid catalyst; wherein the metal organic catalyst is one of zinc oxalate, molybdenum dichlorodicyclopentadienyl with CAS number of 12184-22-4, tungsten dichlorodicyclopentadienyl with CAS number of 12184-26-8 and vanadium dichlorodicyclopentadienyl with CAS number of 12083-48-6; the sulfonic acid catalyst is one of methanesulfonic acid, sulfamic acid, p-chlorobenzene sulfonic acid, sulfanilic acid, p-methoxybenzene sulfonic acid and p-nitrobenzene sulfonic acid; the ratio of the number of moles of the catalyst to the number of moles of N- (carboxymethyl) glycine is 0.0001:1 to 0.001: 1.
4. Use of the polyester obtained by the process for the preparation of imino-containing high molecular weight polyester according to any one of claims 1 to 3, as starting material for polyester bottles, characterized in that: fully mixing the components according to the mass ratio of 100 parts of imino-containing high-molecular-weight polyester, 30-45 parts of plasticizer and 2-3 parts of stabilizer; after mixing, carrying out subsequent extrusion, injection molding, stretching and blow molding processing; the plasticizer is one of phthalate, tricresyl phosphate and dioctyl sebacate; the stabilizer is one of triphenyl phosphate, trimethyl phosphate and triethyl phosphonoacetate.
5. The imino group-containing high molecular weight polyester produced by the production process as set forth in any one of claims 1 to 3.
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| JP2001151877A (en) * | 1999-11-29 | 2001-06-05 | Toray Ind Inc | Polyester composition and film composed of the same |
| US6824766B2 (en) * | 1998-04-17 | 2004-11-30 | Enzon, Inc. | Biodegradable high molecular weight polymeric linkers and their conjugates |
| CN101412804A (en) * | 2008-11-23 | 2009-04-22 | 浙江大学宁波理工学院 | Method for preparing aromatic-aliphatic copolyester |
| CN107226902A (en) * | 2017-06-02 | 2017-10-03 | 武汉科技大学 | A kind of degradable sulfofatty race aromatic polyester and preparation method thereof |
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| GB0205277D0 (en) * | 2002-03-06 | 2002-04-17 | Unilever Plc | Azetidinium-functionalised polymer and compositions containing the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US6824766B2 (en) * | 1998-04-17 | 2004-11-30 | Enzon, Inc. | Biodegradable high molecular weight polymeric linkers and their conjugates |
| JP2001151877A (en) * | 1999-11-29 | 2001-06-05 | Toray Ind Inc | Polyester composition and film composed of the same |
| CN101412804A (en) * | 2008-11-23 | 2009-04-22 | 浙江大学宁波理工学院 | Method for preparing aromatic-aliphatic copolyester |
| CN107226902A (en) * | 2017-06-02 | 2017-10-03 | 武汉科技大学 | A kind of degradable sulfofatty race aromatic polyester and preparation method thereof |
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