CN112062947B - Preparation method of caprolactam copolymer - Google Patents
Preparation method of caprolactam copolymer Download PDFInfo
- Publication number
- CN112062947B CN112062947B CN202010977217.3A CN202010977217A CN112062947B CN 112062947 B CN112062947 B CN 112062947B CN 202010977217 A CN202010977217 A CN 202010977217A CN 112062947 B CN112062947 B CN 112062947B
- Authority
- CN
- China
- Prior art keywords
- caprolactam
- carbon dioxide
- reagent
- biodegradable
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
- C08G69/14—Lactams
- C08G69/16—Preparatory processes
-
- 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
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/18—Block or graft polymers
-
- 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
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/20—General preparatory processes
- C08G64/32—General preparatory processes using carbon dioxide
- C08G64/34—General preparatory processes using carbon dioxide and cyclic ethers
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Biological Depolymerization Polymers (AREA)
- Polyesters Or Polycarbonates (AREA)
- Polyamides (AREA)
Abstract
The invention relates to a preparation method of a caprolactam copolymer, belonging to the technical field of biodegradable high polymer materials. The preparation method of the caprolactam copolymer comprises the following steps: mixing caprolactam and carbon dioxide polymer uniformly, heating to dissolve, adding a catalyst and an activating agent, and reacting; stopping reaction, cooling to room temperature, adding a good solvent for dissolving, then settling in a poor solvent, centrifuging to remove supernatant, and drying to obtain the biodegradable caprolactam copolymer. The invention prepares the caprolactam copolymer which can be completely biodegraded by ring-opening polymerization of caprolactam in a molten carbon dioxide polymer and introducing groups such as ester, urethane and the like into a polycaprolactam main chain. The preparation method has the advantages of simple operation, low cost and the like, and the prepared copolymerization product not only keeps the original excellent thermal and mechanical properties of the nylon 6 material, but also has the biodegradability.
Description
Technical Field
The invention belongs to the technical field of biodegradable high polymer materials, and particularly relates to a preparation method of a caprolactam copolymer.
Background
Polycaprolactam, abbreviated as nylon 6, is a main variety in the nylon industry, contains amide groups in the main molecular chain, has excellent wear resistance, moisture absorption, rebound resilience, alkali corrosion resistance, mechanical properties and the like, and is widely used for automobile parts, mechanical parts, electronic and electric products, engineering accessory products, fiber products, film products and the like. The molecular structure of the polycaprolactam is regular, a large number of hydrogen bonds exist among molecules, the crystallinity is good, and the polycaprolactam is difficult to degrade. With the increasing use of polycaprolactam products, the waste thereof can cause serious environmental pollution problems. In recent years, a number of "plastic limit reams" have been developed in succession. Therefore, the development of biodegradable caprolactam copolymers is of great importance.
Chinese patent CN103224653B reports a preparation method of a biodegradable nylon 6/starch composite material, wherein nylon 6 is used as a plastic base material, starch is used as a filler, and the biodegradable nylon 6/starch composite material is prepared by blending and extruding. Chinese patent CN110527285A reports a preparation method of a biodegradable nylon material, wherein nylon 6, glass fiber and a biodegradable agent are mixed and banburied, extruded and granulated to prepare the biodegradable nylon material. The preparation of degradable nylon 6 reported at present is mainly through simple physical blending. The physical blending cannot radically change the non-degradable property of the nylon 6, and the obtained material only has the partial biodegradation property.
Unlike physical blending, copolymerization and chain exchange reactions can change the inherent properties of the polymer, possibly imparting fully biodegradable properties to the polymer. The copolymerization of caprolactam and caprolactone is reported in the literature [ Folia Microbiol.2009, 54 (5); 451-456], and polycaprolactone with biodegradability is introduced into the molecular chain of polycaprolactam, and the obtained polyesteramide has the characteristic of complete biodegradation. A series of P (PA6-co-PCL) copolymers with different compositions are synthesized by adopting an anion ring-opening polymerization method in a paper [ PA6-co-PCL random copolymer synthesis and performance research, Beijing chemical university, 2019] and regulating the charge ratio of monomers, and the biodegradation performance research shows that polycaprolactone is introduced to endow polycaprolactam biodegradability. Although polycaprolactone can be endowed with biodegradability by introducing polycaprolactone into the main chain of polycaprolactam through ring-opening copolymerization of caprolactam and caprolactone, caprolactone is expensive, and biodegradable polyesteramide prepared from caprolactone has high cost, so that the application of the polycaprolactone is greatly limited.
The carbon dioxide polymer is a copolymerization product of carbon dioxide and epoxide, is low in price, contains degradable carbonate groups in a molecular main chain, and has excellent biodegradation performance and oxygen barrier performance. Based on the ring-opening polymerization of caprolactam in a molten carbon dioxide polymer, ester, urethane and other groups can be introduced into the main chain of polycaprolactam, and a completely biodegradable caprolactam copolymer can be obtained. There has been no report to date of the preparation of fully biodegradable caprolactam copolymers by ring-opening polymerization of caprolactam in molten carbon dioxide polymers.
Disclosure of Invention
The invention aims to solve the technical problems in the prior art and provides a simple and efficient preparation method of a biodegradable caprolactam copolymer. The invention prepares the caprolactam copolymer which can be completely biodegraded by introducing groups such as ester, urethane and the like into the main chain of polycaprolactam through ring-opening polymerization of caprolactam in a molten carbon dioxide polymer, and has very important application value. Meanwhile, renewable resources such as carbon dioxide and the like are used together with petroleum resources to prepare high-end functional materials, so that the dependence of synthetic polymers on petroleum can be partially relieved.
In order to solve the technical problems, the technical scheme of the invention is as follows:
the invention provides a preparation method of a caprolactam copolymer, which comprises the following steps:
(1) mixing caprolactam and carbon dioxide polymer uniformly, heating to dissolve, adding a catalyst or adding the catalyst and an activator, and reacting;
(2) stopping reaction, cooling to room temperature, adding a good solvent for dissolving, then settling in a poor solvent, centrifuging to remove supernatant, and drying to obtain the biodegradable caprolactam copolymer.
In the above technical scheme, the carbon dioxide polymer in step (1) is a copolymerization product of carbon dioxide and one or more of propylene oxide, ethylene oxide, epichlorohydrin, 1-butylene oxide, 2-butylene oxide, cyclohexene oxide, cyclopentane epoxide, glycidyl methacrylate, methyl glycidyl ether and phenyl glycidyl ether.
In the technical scheme, the content of the carbonate in the carbon dioxide polymer in the step (1) is 1-50%, and the molecular weight is 2-20 ten thousand.
In the technical scheme, the heating and dissolving temperature in the step (1) is 80-250 ℃.
In the above technical scheme, the catalyst in step (1) is an organic acid reagent, a pyridine reagent, a carbene reagent, a guanidine reagent, an amidine reagent, a phosphazene reagent, a urea reagent, an alkali metal oxide, an alkali metal hydroxide, an alkali metal hydride, an alkali metal alkoxide, an alkaline earth metal oxide, an alkaline earth metal hydroxide, an alkaline earth metal hydride, or an alkaline earth metal alkoxide.
In the technical scheme, the activating agent in the step (1) is N-acyl caprolactam which has the following structure:
wherein: r is one of methyl, ethyl, phenyl, 4-trifluoromethylphenyl, 4-tert-butylphenyl, trifluoromethyl and trichloromethyl.
In the technical scheme, the mass ratio of the caprolactam to the carbon dioxide polymer in the step (1) is as follows: 100 (1-90); the molar ratio of the catalyst to caprolactam is (0.1-50): 100; the molar ratio of the activating agent to the caprolactam is (0-10): 100.
In the technical scheme, the reaction temperature in the step (1) is 100-280 ℃, and the reaction time is 0.5-24 h.
In the above technical scheme, the good solvent in step (2) is one or more of formic acid, m-cresol, trichloromethane, carbon tetrachloride, chlorobenzene, o-dichlorobenzene, N-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, trifluoroethanol, hexafluoroisopropanol, 1-ethyl-3-methylimidazolium bromide, methanol, ethanol, and benzenediol; the poor solvent is one or more of diethyl ether, petroleum ether, normal hexane, cyclohexane, benzene and toluene.
In the technical scheme, the drying temperature in the step (2) is 25-150 ℃, and the drying time is 2-24 h.
The invention has the beneficial effects that:
the invention provides a simple and efficient preparation method of a biodegradable caprolactam copolymer, which is characterized in that a caprolactam copolymer capable of being completely biodegraded is prepared by introducing ester, urethane and other groups into a polycaprolactam main chain through ring-opening polymerization of caprolactam in a molten carbon dioxide polymer.
The preparation method provided by the invention solves the problem that the non-degradable characteristic of nylon 6 is difficult to change fundamentally in the prior art, and prepares the caprolactam copolymer which can be completely biodegraded. Meanwhile, the method avoids using expensive monomers such as caprolactone, and has very important application value.
The preparation method has the advantages of simple operation, low cost and the like, and the prepared copolymerization product not only keeps the original excellent thermal and mechanical properties of the nylon 6 (polycaprolactam) material, but also has the biodegradability.
Drawings
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
FIG. 1 shows the carbonyl part nuclear magnetic carbon spectrum of the biodegradable caprolactam copolymer, caprolactam, polycaprolactam and carbon dioxide polymer prepared in example 7 of the present invention.
FIG. 2 is a photograph of a biodegradable caprolactam copolymer prepared in example 1 of the present invention before purification.
FIG. 3 is a photograph showing the purified biodegradable caprolactam copolymer prepared in example 1 of the present invention.
FIG. 4 is a photograph of a biodegradable caprolactam copolymer prepared in example 1 of the present invention processed into a plate.
Detailed Description
The invention provides a preparation method of a caprolactam copolymer, which comprises the following steps:
(1) mixing caprolactam and carbon dioxide polymer uniformly, heating to dissolve, adding a catalyst or adding the catalyst and an activating agent, and reacting for a certain time at a proper temperature;
(2) stopping reaction, cooling to room temperature, adding a good solvent for dissolving, then settling in a poor solvent, centrifuging to remove supernatant, and drying to obtain the biodegradable caprolactam copolymer.
Preferably, the carbon dioxide polymer in the step (1) is a copolymerization product of carbon dioxide and one or more of propylene oxide, ethylene oxide, epichlorohydrin, 1-epoxybutane, 2-epoxybutane, cyclohexene oxide, cyclopentane oxide, glycidyl methacrylate, methyl glycidyl ether and phenyl glycidyl ether.
Preferably, the content of carbonate in the carbon dioxide polymer in the step (1) is 1 to 50 percent, and the molecular weight is 2 to 20 ten thousand.
Preferably, the heating and dissolving temperature in the step (1) is 80-250 ℃.
Preferably, the catalyst in step (1) is an organic acid reagent, a pyridine reagent, a carbene reagent, a guanidine reagent, an amidine reagent, a phosphazene reagent, a urea reagent, an alkali metal oxide, an alkali metal hydroxide, an alkali metal hydride, an alkali metal alkoxide, an alkaline earth metal oxide, an alkaline earth metal hydroxide, an alkaline earth metal hydride or an alkaline earth metal alkoxide.
Preferably, the activator described in step (1) is an N-acyl caprolactam having the following structure:
wherein: r is one of methyl, ethyl, phenyl, 4-trifluoromethylphenyl, 4-tert-butylphenyl, trifluoromethyl and trichloromethyl.
Preferably, the mass ratio of caprolactam to carbon dioxide polymer in step (1) is: 100 (1-90); the molar ratio of the catalyst to caprolactam is (0.1-50): 100; the molar ratio of the activating agent to the caprolactam is (0-10): 100.
Preferably, the reaction temperature in the step (1) is 100-280 ℃, and the reaction time is 0.5-24 h.
Preferably, the good solvent in the step (2) is one or more of formic acid, m-cresol, trichloromethane, carbon tetrachloride, chlorobenzene, o-dichlorobenzene, N-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, trifluoroethanol, hexafluoroisopropanol, 1-ethyl-3-methylimidazolium bromide, methanol, ethanol and benzenediol; the poor solvent is one or more of diethyl ether, petroleum ether, normal hexane, cyclohexane, benzene and toluene.
Preferably, the drying temperature in the step (2) is 25-150 ℃ and the time is 2-24 h.
The present invention will be described in further detail with reference to specific examples, but it should be understood that the examples described are only a part of the examples of the present invention, and not all of the examples. All other embodiments, which can be obtained by a person skilled in the art without inventive step based on the embodiments of the present invention, belong to the scope of protection of the present invention.
Example 1
Weighing 3kg of caprolactam, 600g of a copolymerization product of carbon dioxide and propylene oxide (the content of carbonate is 50 percent, the molecular weight is 10 ten thousand) and a 56g N-benzoyl caprolactam activating agent in a 2L polymerization reaction kettle, drying in vacuum at 100 ℃ for 8h, adding 10g of sodium hydride, stirring and dissolving, heating to 120 ℃, reacting in a nitrogen atmosphere for 12h, stopping the reaction, cooling to room temperature, adding dichloromethane for dissolving, settling in diethyl ether, filtering, and drying in a 60 ℃ drying oven for 10h to obtain a white solid biodegradable caprolactam copolymer (the yield is 40%). The photographs of the resulting caprolactam copolymer before and after purification are shown in FIGS. 2 and 3, respectively. The resulting caprolactam copolymer was processed into a panel as shown in FIG. 4.
Example 2
Weighing 3kg of caprolactam, 300g of a copolymerization product of carbon dioxide and ethylene oxide (the content of carbonate is 30 percent, the molecular weight is 5 ten thousand) and a 280g N-benzoyl caprolactam activating agent in a 2L polymerization reaction kettle, drying in vacuum at 100 ℃ for 8h, adding 50g of sodium hydride, stirring and dissolving, heating to 120 ℃, reacting in a nitrogen atmosphere for 12h, stopping the reaction, cooling to room temperature, adding dichloromethane for dissolving, settling in diethyl ether, filtering, and drying in an oven at 80 ℃ for 8h to obtain a white solid biodegradable caprolactam copolymer (the yield is 60%).
Example 3
Weighing 3kg of caprolactam, 150g of a copolymerization product of carbon dioxide and propylene oxide (the content of carbonate is 10 percent, the molecular weight is 2 ten thousand) in a 2L polymerization reaction kettle, drying in vacuum at 100 ℃ for 8h, adding 1g of sodium hydride, stirring and dissolving, heating to 220 ℃, reacting in nitrogen atmosphere for 6h, stopping the reaction, cooling to room temperature, adding trifluoroethanol for dissolving, settling in ether, filtering, and drying in a 100 ℃ drying oven for 3h to obtain the yellowish solid biodegradable caprolactam copolymer (the yield is 70%).
Example 4
Weighing 3kg of caprolactam, 1500g of a copolymerization product of carbon dioxide and propylene oxide (the content of carbonate is 5 percent and the molecular weight is 2 thousand) and a 280g N-benzoyl caprolactam activating agent in a 2L polymerization reaction kettle, drying in vacuum at 100 ℃ for 8h, adding 50g of sodium hydride, stirring and dissolving, heating to 180 ℃, reacting in a nitrogen atmosphere for 12h, stopping the reaction, cooling to room temperature, adding dimethyl sulfoxide to dissolve, settling in diethyl ether, filtering, and drying in an oven at 60 ℃ for 12h to obtain a faint yellow solid biodegradable caprolactam copolymer (the yield is 87%).
Example 5
Weighing 3kg of caprolactam, 450g of a copolymerization product of carbon dioxide and propylene oxide (the content of carbonate is 20 percent, the molecular weight is 2.8 ten thousand) and 60g N-benzoyl caprolactam activating agent in a 2L polymerization reaction kettle, drying in vacuum at 120 ℃ for 8h, adding 10g of sodium hydride, stirring and dissolving, heating to 220 ℃, reacting in nitrogen atmosphere for 6h, stopping the reaction, cooling to room temperature, adding hexafluoroisopropanol to dissolve, settling in diethyl ether, filtering, and drying in a 60 ℃ oven for 10h to obtain the yellowish solid biodegradable caprolactam copolymer (the yield is 92%).
Example 6
Weighing 3kg of caprolactam, 450g of a copolymerization product of carbon dioxide and propylene oxide (the content of carbonate is 20 percent, the molecular weight is 2.8 ten thousand) and 60g N-benzoyl caprolactam activating agent in a 2L polymerization reaction kettle, drying in vacuum at 120 ℃ for 8h, adding 6g of metallic sodium, stirring and dissolving, heating to 220 ℃, reacting in nitrogen atmosphere for 8h, stopping the reaction, cooling to room temperature, adding hexafluoroisopropanol to dissolve, settling in diethyl ether, filtering, and drying in a 60 ℃ oven for 10h to obtain the yellowish solid biodegradable caprolactam copolymer (the yield is 95%).
Example 7
Weighing 3kg of caprolactam, 900g of a copolymerization product of carbon dioxide and propylene oxide (the content of carbonate is 15 percent and the molecular weight is 6 thousand) and a 60g N-benzoyl caprolactam activating agent in a 2L polymerization reaction kettle, drying in vacuum at 120 ℃ for 8 hours, adding 6g of metallic sodium, stirring and dissolving, heating to 240 ℃, reacting in nitrogen atmosphere for 3 hours, stopping the reaction, cooling to room temperature, adding hexafluoroisopropanol to dissolve, settling in diethyl ether, filtering, and drying in a 40 ℃ drying oven for 15 hours to obtain a yellow solid biodegradable caprolactam copolymer (the yield is 88%). FIG. 1 shows the nuclear magnetic carbon spectrum of the carbonyl part of the biodegradable caprolactam copolymer, caprolactam, polycaprolactam and carbon dioxide polymer prepared in this example.
Example 8
Weighing 3kg of caprolactam, 150g of a copolymerization product of carbon dioxide and propylene oxide (the content of carbonate is 50 percent, the molecular weight is 15 ten thousand) and 30g N-formyl caprolactam activating agent in a 2L polymerization reaction kettle, vacuum-drying at 120 ℃ for 8 hours, adding 44g of bis (trimethylsilyl) amido Lithium (LiHMDS), stirring and dissolving, heating to 220 ℃, reacting in a nitrogen atmosphere for 6 hours, stopping the reaction, cooling to room temperature, adding trifluoroethanol for dissolving, settling in diethyl ether, performing suction filtration, and drying in a 50 ℃ oven for 13 hours to obtain a faint yellow solid biodegradable caprolactam copolymer (the yield is 83%).
Example 9
Weighing 3kg of caprolactam, 300g of a copolymerization product of carbon dioxide and propylene oxide (the content of carbonate is 8 percent, the molecular weight is 1 ten thousand) and 60g N-formyl caprolactam activating agent in a 2L polymerization reaction kettle, vacuum-drying at 120 ℃ for 8 hours, adding 88g of bis (trimethylsilyl) aminolithium (LiHMDS), stirring and dissolving, heating to 220 ℃, reacting in a nitrogen atmosphere for 2 hours, stopping the reaction, cooling to room temperature, adding formic acid to dissolve, precipitating in diethyl ether, performing suction filtration, and drying in a 60 ℃ oven for 10 hours to obtain a faint yellow solid biodegradable caprolactam copolymer (the yield is 78%).
Example 10
Weighing 3kg of caprolactam, 900g of a copolymerization product of carbon dioxide and cyclohexene oxide (the content of carbonate is 20 percent, the molecular weight is 2.8 ten thousand) and 60g N-benzoyl caprolactam activating agent in a 2L polymerization reaction kettle, drying in vacuum at 120 ℃ for 8h, adding 10g of sodium hydride, stirring and dissolving, heating to 220 ℃, reacting in nitrogen atmosphere for 6h, stopping the reaction, cooling to room temperature, adding hexafluoroisopropanol to dissolve, settling in diethyl ether, filtering, and drying in an oven at 120 ℃ for 2h to obtain the yellowish solid biodegradable caprolactam copolymer (the yield is 82%).
The kind and content of the carbon dioxide polymer, the kind and content of the catalyst, the kind and content of the activator, the kind of the good solvent, and the kind of the poor solvent used in the above examples may be replaced by any of the above-mentioned limited ranges, and the temperature and the reaction temperature for heating and dissolving in the step (1), and the temperature and the time for drying in the step (2) may be replaced by any of the above-mentioned limited ranges, which are not exemplified herein.
Comparative example 1
Weighing 3kg of caprolactam and 30g N-formyl caprolactam activating agent, putting the caprolactam and the activating agent into a 2L polymerization reactor, drying the caprolactam in vacuum at 120 ℃ for 8h, adding 10g of sodium hydride, stirring and dissolving, heating to 220 ℃, reacting in nitrogen atmosphere for 6h, stopping the reaction, cooling to room temperature, adding trifluoroethanol for dissolving, settling in dichloromethane, performing suction filtration, and drying in an oven at 60 ℃ for 10h to obtain a light yellow solid nylon 6 product (yield 85%).
The biodegradable caprolactam copolymers prepared in examples 1-10 and the caprolactam homopolymer (nylon 6) prepared in comparative example 1 were tested for thermal properties. Biodegradable caprolactam copolymer prepared in examples 1-10 and nylon 6 prepared in comparative example 1 were hot pressed into films according to GB/T1040.3-2006/ISO527-3:1995, determination of tensile Properties of plastics part 3: the mechanical properties of the films and sheets were measured under the test conditions. Biodegradable caprolactam copolymer prepared in examples 1 to 10 and nylon 6 prepared in comparative example 1 were hot-pressed to form a film, which was mixed with culture soil, introduced into a static composting container, strongly aerobically composted under prescribed temperature, oxygen concentration and humidity conditions, and after 45 days, according to GB/T19277.1-2011/ISO14855-1:2005 "determination of the ultimate aerobic biodegradability of a material under controlled composting conditions" part 1 of the method for determining the released carbon dioxide: general methods "were used to test their biodegradability, and the results are shown in table 1.
TABLE 1 test results of thermal, mechanical and degradation Properties of examples 1-10 and comparative example 1
As can be seen from the test results in Table 1, the biodegradable caprolactam copolymers obtained in examples 1 to 10 are significantly superior in degradation performance to nylon 6 of comparative example 1. Although the tensile strength of the biodegradable caprolactam copolymers obtained in examples 1-10 is slightly reduced compared with that of comparative example 1, nylon 6, the elongation at break is obviously improved, and the overall mechanical properties are excellent, and meanwhile, the biodegradable caprolactam copolymers obtained in examples 1-10 have lower melting points and are easier to process.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (9)
1. A method for preparing a caprolactam copolymer, comprising the steps of:
(1) mixing caprolactam and carbon dioxide polymer uniformly, heating to dissolve, adding a catalyst or adding the catalyst and an activator, and reacting;
(2) stopping the reaction, cooling to room temperature, adding a good solvent for dissolving, then settling in a poor solvent, centrifuging to remove supernatant, and drying to obtain the biodegradable caprolactam copolymer;
the carbon dioxide polymer in the step (1) is a copolymerization product of carbon dioxide and one or more of propylene oxide, ethylene oxide, epichlorohydrin, 1-epoxybutane, 2-epoxybutane, cyclohexene oxide, cyclopentane epoxide, glycidyl methacrylate ether, methyl glycidyl ether and phenyl glycidyl ether.
2. The method according to claim 1, wherein the carbon dioxide polymer in the step (1) contains 1 to 50% of carbonate and has a molecular weight of 2 to 20 ten thousand.
3. The method according to claim 1, wherein the temperature for the heating dissolution in the step (1) is 80 to 250 ℃.
4. The process according to claim 1, wherein the catalyst in the step (1) is an organic acid reagent, a pyridine reagent, a carbene reagent, a guanidine reagent, an amidine reagent, a phosphazene reagent, a urea reagent, an alkali metal oxide, an alkali metal hydroxide, an alkali metal hydride, an alkali metal alkoxide, an alkaline earth metal oxide, an alkaline earth metal hydroxide, an alkaline earth metal hydride or an alkaline earth metal alkoxide.
5. The process of claim 1, wherein the activating agent in step (1) is an N-acyl caprolactam having the following structure:
wherein: r is one of methyl, ethyl, phenyl, 4-trifluoromethylphenyl, 4-tert-butylphenyl, trifluoromethyl and trichloromethyl.
6. The process according to any one of claims 1 to 5, wherein the mass ratio of caprolactam to carbon dioxide polymer in step (1) is: 100 (1-90); the molar ratio of the catalyst to caprolactam is (0.1-50): 100; the molar ratio of the activating agent to the caprolactam is (0-10): 100.
7. The method according to claim 1, wherein the reaction temperature in step (1) is 100 ℃ to 280 ℃ and the reaction time is 0.5h to 24 h.
8. The preparation method according to claim 1, wherein the good solvent in step (2) is one or more selected from formic acid, m-cresol, chloroform, carbon tetrachloride, chlorobenzene, o-dichlorobenzene, N-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, trifluoroethanol, hexafluoroisopropanol, 1-ethyl-3-methylimidazolium bromide, methanol, ethanol, and benzenediol; the poor solvent is one or more of diethyl ether, petroleum ether, normal hexane, cyclohexane, benzene and toluene.
9. The preparation method according to claim 1, wherein the drying temperature in the step (2) is 25-150 ℃ and the time is 2-24 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010977217.3A CN112062947B (en) | 2020-09-17 | 2020-09-17 | Preparation method of caprolactam copolymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010977217.3A CN112062947B (en) | 2020-09-17 | 2020-09-17 | Preparation method of caprolactam copolymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112062947A CN112062947A (en) | 2020-12-11 |
| CN112062947B true CN112062947B (en) | 2021-12-28 |
Family
ID=73680524
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010977217.3A Active CN112062947B (en) | 2020-09-17 | 2020-09-17 | Preparation method of caprolactam copolymer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112062947B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113429569B (en) * | 2021-07-23 | 2022-08-16 | 四川大学 | Preparation method of high molecular weight furan polyamide |
| CN115028544B (en) * | 2022-05-29 | 2024-04-26 | 复旦大学 | Method for catalytic deformylation of aromatic formamide and application thereof |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU501063B2 (en) * | 1976-07-27 | 1979-06-07 | Alrac Corporation | Polymer of 2-pyrrolidone |
| EP0249809A1 (en) * | 1986-06-16 | 1987-12-23 | General Electric Company | Copolyamidecarbonates and method of preparation from cyclic aromatic polycarbonate oligomers |
| US6316581B1 (en) * | 2001-02-09 | 2001-11-13 | Richard A. Gross | Bioresorbable copolymers |
| CN1419578A (en) * | 2000-03-28 | 2003-05-21 | 旭化成株式会社 | Block copolymer |
| CN1668671A (en) * | 2002-06-20 | 2005-09-14 | Posco公司 | Method of preparing catalyst for polymerization of aliphatic polycarbonate and method of polymerizing aliphatic polycarbonate |
| CN101024685A (en) * | 2007-02-12 | 2007-08-29 | 江苏中科金龙化工股份有限公司 | Method for preparing fatty group polycarbonate polylol |
| CN101454376A (en) * | 2006-05-31 | 2009-06-10 | 纳幕尔杜邦公司 | Preparation of polyamide block copolymers |
| CN101687990A (en) * | 2007-05-10 | 2010-03-31 | 雅培血管企业有限公司 | The medical apparatus that comprises the multipolymer of modified polyamide and polycarbonate |
| CN101702913A (en) * | 2007-05-10 | 2010-05-05 | 雅培血管企业有限公司 | The medical apparatus that comprises the multipolymer of polymeric amide and polycarbonate diamine |
-
2020
- 2020-09-17 CN CN202010977217.3A patent/CN112062947B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU501063B2 (en) * | 1976-07-27 | 1979-06-07 | Alrac Corporation | Polymer of 2-pyrrolidone |
| EP0249809A1 (en) * | 1986-06-16 | 1987-12-23 | General Electric Company | Copolyamidecarbonates and method of preparation from cyclic aromatic polycarbonate oligomers |
| CN1419578A (en) * | 2000-03-28 | 2003-05-21 | 旭化成株式会社 | Block copolymer |
| US6316581B1 (en) * | 2001-02-09 | 2001-11-13 | Richard A. Gross | Bioresorbable copolymers |
| CN1668671A (en) * | 2002-06-20 | 2005-09-14 | Posco公司 | Method of preparing catalyst for polymerization of aliphatic polycarbonate and method of polymerizing aliphatic polycarbonate |
| CN101454376A (en) * | 2006-05-31 | 2009-06-10 | 纳幕尔杜邦公司 | Preparation of polyamide block copolymers |
| CN101024685A (en) * | 2007-02-12 | 2007-08-29 | 江苏中科金龙化工股份有限公司 | Method for preparing fatty group polycarbonate polylol |
| CN101687990A (en) * | 2007-05-10 | 2010-03-31 | 雅培血管企业有限公司 | The medical apparatus that comprises the multipolymer of modified polyamide and polycarbonate |
| CN101702913A (en) * | 2007-05-10 | 2010-05-05 | 雅培血管企业有限公司 | The medical apparatus that comprises the multipolymer of polymeric amide and polycarbonate diamine |
Non-Patent Citations (1)
| Title |
|---|
| Synthesis of biodegradable polymers catalyzed by macromolecule-bimetal complexes;Shu-Ying Yang, et al.;《MACROMOLECULAR SYMPOSIA》;19960331;第105卷;第17-25页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112062947A (en) | 2020-12-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112062947B (en) | Preparation method of caprolactam copolymer | |
| US6713593B2 (en) | Copolymer comprising alkylene carbonate and method of preparing same | |
| CN113999499A (en) | Flame-retardant reinforced regenerated PET composite material | |
| CN113968961A (en) | Poly (terephthalic acid) -co-butylene succinate-polylactic acid copolymer and preparation method thereof | |
| CN102226004B (en) | Modified poly(lactic acid) and preparation method thereof | |
| US20100099830A1 (en) | Resin composition, method for producing thereof, and copolymer | |
| CN117327388B (en) | Starch modified degradable plastic and preparation method thereof | |
| CN117603569B (en) | 3D printing material based on carbon dioxide copolymer and preparation method thereof | |
| CN113831702B (en) | Degradable plastic cutlery box composition and preparation method thereof | |
| KR101515823B1 (en) | A transparent copolyester, preparing method thereof and articles made from the same | |
| KR101368775B1 (en) | Polylactide block-coplymerized lactide with polyalkylene glycol having high molecular weight | |
| CN105531320A (en) | Resin composition containing polyalkylene carbonate | |
| CN113429762A (en) | Starch/polylactic acid/PBAT nano composite material and preparation method thereof | |
| CN113527649B (en) | High-fluidity antibacterial PBAT polymer and preparation method thereof | |
| CN116640431A (en) | Toughening modified plastic particle and preparation process thereof | |
| CN113563696B (en) | Preparation method of modified polyethylene terephthalate | |
| CN113621095A (en) | Degradable polymer initiator and preparation method thereof | |
| KR101355189B1 (en) | Polyalkylene glycol polylactide resin | |
| CN114106538A (en) | Fully-degradable plastic processing technology | |
| CN114262511B (en) | Biodegradable resin composition and preparation method and application thereof | |
| CN113462002B (en) | Preparation method of degradable flame-retardant foamed beads | |
| CN117343294A (en) | High-flexibility high-barrier polylactic acid copolymer and preparation method and application thereof | |
| CN117551255A (en) | Degradable cardanol-based polyurethane material and preparation method and application thereof | |
| CN117164836A (en) | PET copolyester capable of being rapidly degraded in water prepared from rigid monomer and preparation method | |
| CN117209986A (en) | Toughening modified polylactic acid material, preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |