CN115232296B - High-temperature-resistant biodegradable polyester and preparation method thereof - Google Patents
High-temperature-resistant biodegradable polyester and preparation method thereof Download PDFInfo
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- 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
- C08G63/60—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/52—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
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- C08G2230/00—Compositions for preparing biodegradable polymers
Abstract
The invention discloses a high-temperature-resistant biodegradable polyester and a preparation method thereof, belongs to the field of degradable materials, and particularly relates to random copolyester, which is a copolymer prepared by random copolymerization of an acid reagent and an alcohol reagent, wherein the acid reagent is at least one of lactic acid, terephthalic acid, malic acid and adipic acid; the alcohol reagent is at least one of 1, 4-butanediol, 1, 4-cyclohexanedimethanol, PEG and glycerol. Where the above reagents are used, it is further possible to use cellulose acetate or cellulose acetate and modified NCC to prepare random copolyesters. The random copolyester prepared by the invention has good mechanical property and heat resistance, and the random copolyester has degradability, can be degraded by lipase and can be hydrolyzed under alkaline condition.
Description
Technical Field
The invention belongs to the field of degradable materials, and particularly relates to high-temperature-resistant biodegradable polyester and a preparation method thereof.
Background
Plastics have been produced on a large scale since the middle of the last century. Compared with other materials, it is strong, durable and light, and is ubiquitous in people's lives. However, these traditional plastics do not degrade in the environment for hundreds of years to thousands of years. Therefore, excessive consumption of conventional plastics, particularly disposable packaging plastic articles such as shopping bags, garbage bags, etc., can cause serious plastic contamination problems. The plastic pollution is widely distributed and the harm to the ecological system and the biology is far beyond public recognition.
The market application of biodegradable plastics is expanding, and the market application comprises packaging industry, catering, agriculture, toys, textiles and other market segments. Biodegradable plastics are relatively expensive to develop and raw materials, and generally more expensive than traditional plastics. The biodegradable polyester has the defects of poor mechanical properties such as strength, hardness and ductility, generally poor heat resistance, dependence of degradation expression on specific environment, and generally slow degradation or even no degradation of common biodegradable polyesters such as PCL, PLA, PHA, PBS, PBAT and the like during hydrolysis.
Disclosure of Invention
The invention aims to provide high-temperature-resistant biodegradable polyester which has good tensile property and heat resistance and can be degraded by lipase, and a preparation method thereof.
The technical scheme adopted by the invention for realizing the purpose is as follows:
a random copolyester comprising: the copolymer is prepared by random copolymerization of an acid reagent and an alcohol reagent, wherein the acid reagent is at least one of lactic acid, terephthalic acid, malic acid and adipic acid; the alcohol reagent is at least one of 1, 4-butanediol, 1, 4-cyclohexanedimethanol, PEG and glycerol. The method is characterized in that an acid reagent and an alcohol reagent are catalyzed to generate polyester under the action of a catalyst, the acid reagent uses lactic acid and terephthalic acid at first, the alcohol reagent uses 1, 4-butanediol and 1, 4-cyclohexanedimethanol, and the acid reagent and the alcohol reagent respectively contain two reactive groups, so that a random copolymer can be prepared through the mixing reaction of the reagents.
Preferably, the acid reagent is lactic acid, terephthalic acid; the alcohol reagent is 1, 4-butanediol and 1, 4-cyclohexanedimethanol.
Preferably, the acid reagent is lactic acid, terephthalic acid, malic acid; or the alcohol reagent is 1, 4-butanediol, 1, 4-cyclohexanedimethanol or glycerol.
Preferably, cellulose acetate is used in the random copolymerization.
Preferably, cellulose acetate and modified NCC are used in the random copolymerization. When the cellulose acetate or the cellulose acetate and the modified NCC are applied to the preparation of the random copolymer, the using amount of the cellulose acetate or the cellulose acetate and the modified NCC cannot be too high or too low, otherwise, the performance of the random copolymer can be influenced, and the mechanical property, the heat resistance and the degradation performance of the random copolymer can be improved within a reasonable application range.
Preferably, the copolymer is degraded by lipase under neutral conditions and/or hydrolyzed under alkaline conditions.
The invention discloses a preparation method of random copolyester, which comprises the following steps: mixing an acid reagent and an alcohol reagent, and reacting under the catalysis of a catalyst to generate random copolyester; the acid reagent is at least one of lactic acid, terephthalic acid, malic acid and adipic acid; the alcohol reagent is at least one of 1, 4-butanediol, 1, 4-cyclohexanedimethanol, PEG and glycerol. When an acid reagent or an alcohol reagent is used, a branched cross-linked structure is formed in the process of random copolymerization when the acid reagent or the alcohol reagent containing more than two reactive groups is used, so that a random copolymer with a complex cross-linked structure is formed, and the mechanical property, the heat resistance and the degradation property of the random copolymer are improved.
Preferably, the acid reagent is mixed with the alcohol reagent and then added to the cellulose acetate to react with the catalyst to form the random copolyester.
Preferably, the molar amount of the alcohol reagent used is 100 to 150% of the molar amount of the acid reagent used.
Preferably, the acid reagent is lactic acid and terephthalic acid, and the mass ratio of lactic acid to terephthalic acid in the acid reagent is 1:0.2-0.4 in proportion.
Preferably, the alcohol reagent is 1, 4-butanediol and 1, 4-cyclohexanedimethanol, and the mass ratio of the 1, 4-butanediol to the 1, 4-cyclohexanedimethanol in the alcohol reagent is 1:5-10 in proportion.
Preferably, in the preparation of the random copolyester, an acid reagent and an alcohol reagent are mixed, a catalyst is added, esterification reaction is carried out for 1-3h at 180-240 ℃, after the esterification is finished, vacuum-pumping polycondensation reaction is carried out for 3-6h at 250-280 ℃, and after the polycondensation reaction is finished, the biodegradable random copolyester is obtained.
Preferably, in the preparation of the random copolyester, the acid agent is at least one of lactic acid, terephthalic acid, malic acid and adipic acid.
Preferably, in the preparation of the random copolyester, the acid reagents are lactic acid and terephthalic acid, and the mass ratio of the lactic acid to the terephthalic acid in the acid reagents is 1:0.2-0.4 in proportion.
Preferably, in the preparation of the random copolyester, the alcohol reagent is at least one of 1, 4-butanediol, 1, 4-cyclohexanedimethanol, PEG and glycerol. The molar amount of the alcohol reagent is 100-150% of the molar amount of the acid reagent.
Preferably, in the preparation of the random copolyester, the alcohol reagent is 1, 4-butanediol and 1, 4-cyclohexanedimethanol, and the mass ratio of the 1, 4-butanediol to the 1, 4-cyclohexanedimethanol in the alcohol reagent is 1:5-10 in proportion.
Preferably, in the preparation of the random copolyester, the catalyst is tetrabutyl titanate. The amount of the catalyst used is 0.1-0.5wt% of the acid reagent.
Preferably, cellulose acetate may be added in the preparation of the random copolyester.
More preferably, the preparation of cellulose acetate: dispersing the nano-cellulose in anhydrous pyridine, adding acetic anhydride, reacting for 3-9h at 70-90 ℃ under stirring, washing after the reaction is finished, and drying to obtain the cellulose acetate.
More preferably, in the preparation of the random copolyester, the nanocellulose is used in an amount of 3-8wt% based on the anhydrous pyridine.
More preferably, acetic anhydride is used in an amount of 10 to 30wt% of the nanocellulose in the preparation of the random copolyester.
More preferably, the cellulose acetate is used in the preparation of the random copolyester in an amount of 20 to 40wt% based on the molar amount of the acid agent used.
Preferably, modified NCC may be added in the preparation of the random copolyester.
More preferably, in the preparation of the branched polyester, maleic anhydride and glycerol are mixed, a catalyst is added, the mixture reacts at 180-240 ℃ for 2-6 hours in the nitrogen atmosphere, after the reaction is finished, the mixture is cooled to room temperature, acetone is added, methanol is added for fractional precipitation, and the branched polyester is obtained after reduced pressure suction filtration and drying.
More preferably, in the preparation of the branched polyester, glycerol is used in an amount of 3 to 10% by weight based on maleic anhydride.
More preferably, in the preparation of the branched polyester, the catalyst is tetrabutyl titanate and is used in an amount of 0.2 to 0.9wt% of maleic anhydride.
More preferably, in the preparation of the modified NCC, the NCC and the branched polyester are added into DMF, stirred and dispersed at a high speed, modified for 0.5 to 3 hours at the temperature of between 50 and 80 ℃, and after the modification is finished, the modified NCC is obtained by vacuum filtration and drying.
More preferably, in the preparation of the modified NCC, the NCC is used in an amount of 6 to 18wt% based on DMF and the branched polyester is used in an amount of 4 to 10wt% based on NCC.
More preferably, in the preparation of random copolyesters, the modified NCC is used in an amount of 10 to 30wt% of the molar amount of acid agent used.
The invention adopts the reaction of the acid reagent containing at least two reactive groups and the alcohol reagent to prepare the random copolyester, and further can use the cellulose acetate or the cellulose acetate and the modified NCC to prepare the random copolyester, thereby having the following beneficial effects: the random copolyester has good mechanical property and heat resistance, and the random copolyester has degradability and can be degraded by lipase. Therefore, the invention is a high temperature resistant biodegradable polyester with good tensile property and heat resistance and capable of being degraded by lipase and a preparation method thereof.
Drawings
FIG. 1 is an electron micrograph of a random copolyester;
FIG. 2 is a graph of the tensile strength of random copolyesters;
FIG. 3 is a graph of the high temperature loss resistance of random copolyesters;
FIG. 4 is a graph of the enzymatic hydrolysis loss rate of random copolyesters;
FIG. 5 is a graph of the hydrolysis loss rate of random copolyesters.
Detailed Description
The technical solution of the present invention is further described in detail below with reference to the following detailed description and the accompanying drawings:
example 1:
a preparation method of random copolyester, which comprises the following steps,
preparation of random copolyester: mixing an acid reagent and an alcohol reagent, adding a catalyst, carrying out esterification reaction for 2 hours at 210 ℃, after the esterification is finished, carrying out vacuum-pumping polycondensation reaction for 5 hours at 260 ℃, and after the polycondensation reaction is finished, obtaining the biodegradable random copolyester. The acid reagent is lactic acid and terephthalic acid, and the mass ratio of the lactic acid to the terephthalic acid in the acid reagent is 1: a ratio of 0.3 was used. The alcohol reagent is 1, 4-butanediol and 1, 4-cyclohexanedimethanol, and the mass ratio of the 1, 4-butanediol to the 1, 4-cyclohexanedimethanol in the alcohol reagent is 1: the ratio of 7 was used. The molar amount of the alcohol reagent used was 130% of the molar amount of the acid reagent used. The catalyst is tetrabutyl titanate. The catalyst was used in an amount of 0.3wt% based on the acid reagent.
Example 2:
a method of preparing random copolyester, this example is compared with example 1, except that cellulose acetate is added to the preparation of random copolyester.
Preparation of cellulose acetate: dispersing the nano-cellulose in anhydrous pyridine, adding acetic anhydride, reacting for 6 hours at 80 ℃ under stirring, washing and drying after the reaction is finished, thus obtaining the cellulose acetate. The usage amount of the nano-cellulose is 5wt% of the anhydrous pyridine, and the usage amount of the acetic anhydride is 20wt% of the nano-cellulose.
Preparation of random copolyester: mixing an acid reagent, an alcohol reagent and cellulose acetate, adding a catalyst, carrying out esterification reaction for 2 hours at 210 ℃, after the esterification is finished, carrying out vacuum-pumping polycondensation reaction for 5 hours at 260 ℃, and after the polycondensation reaction is finished, obtaining the biodegradable random copolyester. The acid reagent is lactic acid and terephthalic acid, and the mass ratio of the lactic acid to the terephthalic acid in the acid reagent is 1: a ratio of 0.3 was used. The alcohol reagent is 1, 4-butanediol and 1, 4-cyclohexanedimethanol, and the mass ratio of the 1, 4-butanediol to the 1, 4-cyclohexanedimethanol in the alcohol reagent is 1:7 was used. The molar amount of the alcohol reagent used was 130% of the molar amount of the acid reagent used. The amount of cellulose acetate used was 30wt% based on the molar amount of the acid reagent used, and the catalyst was tetrabutyl titanate. The catalyst was used in an amount of 0.3wt% based on the acid reagent.
Example 3:
a method of preparing random copolyester, this example is compared with example 2, except that modified NCC was added in the preparation of random copolyester.
Preparation of branched polyester: mixing maleic anhydride and glycerol, adding a catalyst, reacting for 4 hours at 210 ℃ in a nitrogen atmosphere, cooling to room temperature after the reaction is finished, adding acetone, adding methanol for fractional precipitation, performing vacuum filtration, and drying to obtain the branched polyester. The amount of glycerol used was 6wt% of maleic anhydride, the catalyst was tetrabutyl titanate, and the amount of catalyst used was 0.4wt% of maleic anhydride.
Preparation of modified NCC: adding NCC and branched polyester into DMF, stirring at high speed for dispersing, modifying at 70 deg.C for 2h, vacuum filtering after modification, and drying to obtain modified NCC. NCC was used in an amount of 12wt% based on DMF and branched polyester in an amount of 8wt% based on NCC.
Preparation of random copolyester: mixing an acid reagent, an alcohol reagent, cellulose acetate and modified NCC, adding a catalyst, carrying out esterification reaction for 2 hours at 210 ℃, carrying out vacuum polycondensation reaction for 5 hours at 260 ℃ after the esterification is finished, and obtaining the biodegradable random copolyester after the polycondensation reaction is finished. The acid reagent is lactic acid and terephthalic acid, and the mass ratio of the lactic acid to the terephthalic acid in the acid reagent is 1: a ratio of 0.3 was used. The alcohol reagent is 1, 4-butanediol and 1, 4-cyclohexanedimethanol, and the mass ratio of the 1, 4-butanediol to the 1, 4-cyclohexanedimethanol in the alcohol reagent is 1: the ratio of 7 was used. The molar amount of the alcohol reagent used was 130% of the molar amount of the acid reagent used. The amount of cellulose acetate used was 30wt% based on the molar amount of the acid reagent used, the amount of modified NCC used was 20wt% based on the molar amount of the acid reagent used, and the catalyst was tetrabutyl titanate. The catalyst was used in an amount of 0.3wt% based on the acid reagent.
Example 4:
the difference between the preparation method of the random copolyester and the embodiment 1 is that in the preparation of the random copolyester, the acid reagents are lactic acid, terephthalic acid and malic acid.
Preparation of random copolyester: mixing an acid reagent and an alcohol reagent, adding a catalyst, carrying out esterification reaction for 2 hours at 210 ℃, carrying out vacuum polycondensation reaction for 5 hours at 260 ℃ after the esterification is finished, and obtaining the biodegradable random copolyester after the polycondensation reaction is finished. The acid reagent is lactic acid, terephthalic acid and malic acid, and the mass ratio of lactic acid to terephthalic acid to malic acid in the acid reagent is 1:0.3: a ratio of 0.6 was used. The alcohol reagent is 1, 4-butanediol and 1, 4-cyclohexanedimethanol, and the mass ratio of the 1, 4-butanediol to the 1, 4-cyclohexanedimethanol in the alcohol reagent is 1: the ratio of 7 was used. The molar amount of the alcohol reagent used was 130% of the molar amount of the acid reagent used. The catalyst is tetrabutyl titanate. The amount of catalyst used was 0.3wt% of the acid reagent.
Example 5:
the difference between this example and example 2 is that the acid reagents used in the preparation of the random copolyester are lactic acid, terephthalic acid and malic acid.
Preparation of random copolyester: mixing an acid reagent, an alcohol reagent and cellulose acetate, adding a catalyst, carrying out esterification reaction for 2 hours at 210 ℃, carrying out vacuum polycondensation reaction for 5 hours at 260 ℃ after the esterification is finished, and obtaining the biodegradable random copolyester after the polycondensation reaction is finished. The acid reagent is lactic acid, terephthalic acid and malic acid, and the mass ratio of lactic acid to terephthalic acid to malic acid in the acid reagent is 1:0.3: a ratio of 0.6 was used. The alcohol reagent is 1, 4-butanediol and 1, 4-cyclohexanedimethanol, and the mass ratio of the 1, 4-butanediol to the 1, 4-cyclohexanedimethanol in the alcohol reagent is 1:7 was used. The molar amount of the alcohol reagent used was 130% of the molar amount of the acid reagent used. The amount of cellulose acetate used was 30wt% of the molar amount of acid reagent used, and the catalyst was tetrabutyl titanate. The amount of catalyst used was 0.3wt% of the acid reagent.
Example 6:
a method for preparing random copolyester, which is different from that of example 3 in that lactic acid, terephthalic acid and malic acid are used as acid reagents in the preparation of random copolyester.
Preparation of random copolyester: mixing an acid reagent, an alcohol reagent, cellulose acetate and modified NCC, adding a catalyst, carrying out esterification reaction for 2 hours at 210 ℃, carrying out vacuum polycondensation reaction for 5 hours at 260 ℃ after the esterification is finished, and obtaining the biodegradable random copolyester after the polycondensation reaction is finished. The acid reagent is lactic acid, terephthalic acid and malic acid, and the mass ratio of lactic acid to terephthalic acid to malic acid in the acid reagent is 1:0.3: a ratio of 0.6 was used. The alcohol reagent is 1, 4-butanediol and 1, 4-cyclohexanedimethanol, and the mass ratio of the 1, 4-butanediol to the 1, 4-cyclohexanedimethanol in the alcohol reagent is 1:7 was used. The molar amount of alcohol reagent used is 130% of the molar amount of acid reagent used. The amount of cellulose acetate used was 30wt% based on the molar amount of the acid reagent used, the amount of modified NCC used was 20wt% based on the molar amount of the acid reagent used, and the catalyst was tetrabutyl titanate. The catalyst was used in an amount of 0.3wt% based on the acid reagent.
Example 7:
a method for preparing random copolyester, this example is different from example 1 in that the alcohol reagent is 1, 4-butanediol and 1, 4-cyclohexanedimethanol, glycerol.
Preparation of random copolyester: mixing an acid reagent and an alcohol reagent, adding a catalyst, carrying out esterification reaction for 2 hours at 210 ℃, after the esterification is finished, carrying out vacuum-pumping polycondensation reaction for 5 hours at 260 ℃, and after the polycondensation reaction is finished, obtaining the biodegradable random copolyester. The acid reagent is lactic acid and terephthalic acid, and the mass ratio of the lactic acid to the terephthalic acid in the acid reagent is 1: a ratio of 0.3 was used. The alcohol reagent is 1, 4-butanediol, 1, 4-cyclohexanedimethanol and glycerol, wherein the 1, 4-butanediol, 1, 4-cyclohexanedimethanol and glycerol in the alcohol reagent are mixed according to a mass ratio of 1:7:4 in the ratio of the total weight of the composition. The molar amount of the alcohol reagent used was 130% of the molar amount of the acid reagent used. The catalyst is tetrabutyl titanate. The amount of catalyst used was 0.3wt% of the acid reagent.
Example 8:
a method of preparing random copolyester, this example compares with example 2, except that the alcohol reagents in the preparation of random copolyester are 1, 4-butanediol and 1, 4-cyclohexanedimethanol, glycerol.
Preparation of random copolyester: mixing an acid reagent, an alcohol reagent and cellulose acetate, adding a catalyst, carrying out esterification reaction for 2 hours at 210 ℃, carrying out vacuum polycondensation reaction for 5 hours at 260 ℃ after the esterification is finished, and obtaining the biodegradable random copolyester after the polycondensation reaction is finished. The acid reagent is lactic acid and terephthalic acid, and the mass ratio of the lactic acid to the terephthalic acid in the acid reagent is 1: a ratio of 0.3 was used. The alcohol reagent is 1, 4-butanediol, 1, 4-cyclohexanedimethanol and glycerol, wherein the 1, 4-butanediol, 1, 4-cyclohexanedimethanol and glycerol in the alcohol reagent are mixed according to a mass ratio of 1:7:4 in the ratio. The molar amount of the alcohol reagent used was 130% of the molar amount of the acid reagent used. The amount of cellulose acetate used was 30wt% based on the molar amount of the acid reagent used, and the catalyst was tetrabutyl titanate. The amount of catalyst used was 0.3wt% of the acid reagent.
Example 9:
a method of preparing random copolyester, this example compares with example 3 except that the alcohol reagents in the preparation of random copolyester are 1, 4-butanediol and 1, 4-cyclohexanedimethanol, glycerol.
Preparation of random copolyester: mixing an acid reagent, an alcohol reagent, cellulose acetate and modified NCC, adding a catalyst, carrying out esterification reaction for 2 hours at 210 ℃, carrying out vacuum polycondensation reaction for 5 hours at 260 ℃ after the esterification is finished, and obtaining the biodegradable random copolyester after the polycondensation reaction is finished. The acid reagent is lactic acid and terephthalic acid, and the mass ratio of the lactic acid to the terephthalic acid in the acid reagent is 1: a ratio of 0.3 was used. The alcohol reagent is 1, 4-butanediol, 1, 4-cyclohexanedimethanol and glycerol, wherein the 1, 4-butanediol, 1, 4-cyclohexanedimethanol and glycerol in the alcohol reagent are mixed according to a mass ratio of 1:7:4 in the ratio. The molar amount of the alcohol reagent used was 130% of the molar amount of the acid reagent used. The amount of cellulose acetate used was 30wt% based on the molar amount of the acid reagent used, the amount of modified NCC used was 20wt% based on the molar amount of the acid reagent used, and the catalyst was tetrabutyl titanate. The amount of catalyst used was 0.3wt% of the acid reagent.
Example 10:
a method for preparing random copolyester, this example is different from example 1 in that in the preparation of random copolyester, acid reagents are lactic acid and terephthalic acid, malic acid, and alcohol reagents are 1, 4-butanediol and 1, 4-cyclohexanedimethanol, glycerol.
Preparation of random copolyester: mixing an acid reagent and an alcohol reagent, adding a catalyst, carrying out esterification reaction for 2 hours at 210 ℃, carrying out vacuum polycondensation reaction for 5 hours at 260 ℃ after the esterification is finished, and obtaining the biodegradable random copolyester after the polycondensation reaction is finished. The acid reagent is lactic acid, terephthalic acid and malic acid, and the mass ratio of lactic acid to terephthalic acid to malic acid in the acid reagent is 1:0.3: a ratio of 0.6 was used. The alcohol reagent is 1, 4-butanediol, 1, 4-cyclohexanedimethanol and glycerol, wherein the 1, 4-butanediol, 1, 4-cyclohexanedimethanol and glycerol in the alcohol reagent are mixed according to a mass ratio of 1:7:4 in the ratio. The molar amount of the alcohol reagent used was 130% of the molar amount of the acid reagent used. The catalyst is tetrabutyl titanate. The amount of catalyst used was 0.3wt% of the acid reagent.
Example 11:
a method for preparing random copolyester, this example is different from example 2 in that in the preparation of random copolyester, acid reagents are lactic acid and terephthalic acid, malic acid, and alcohol reagents are 1, 4-butanediol and 1, 4-cyclohexanedimethanol, glycerol.
Preparation of random copolyester: mixing an acid reagent, an alcohol reagent and cellulose acetate, adding a catalyst, carrying out esterification reaction for 2 hours at 210 ℃, carrying out vacuum polycondensation reaction for 5 hours at 260 ℃ after the esterification is finished, and obtaining the biodegradable random copolyester after the polycondensation reaction is finished. The acid reagent is lactic acid, terephthalic acid and malic acid, and the mass ratio of lactic acid to terephthalic acid to malic acid in the acid reagent is 1:0.3: a ratio of 0.6 was used. The alcohol reagent is 1, 4-butanediol, 1, 4-cyclohexanedimethanol and glycerol, wherein the 1, 4-butanediol, 1, 4-cyclohexanedimethanol and glycerol in the alcohol reagent are mixed according to a mass ratio of 1:7:4 in the ratio. The molar amount of the alcohol reagent used was 130% of the molar amount of the acid reagent used. The amount of cellulose acetate used was 30wt% based on the molar amount of the acid reagent used, and the catalyst was tetrabutyl titanate. The amount of catalyst used was 0.3wt% of the acid reagent.
Example 12:
a method for preparing random copolyester, this example is different from example 1 in that in the preparation of random copolyester, acid reagents are lactic acid and terephthalic acid, malic acid, and alcohol reagents are 1, 4-butanediol and 1, 4-cyclohexanedimethanol, glycerol.
Preparation of random copolyester: mixing an acid reagent, an alcohol reagent, cellulose acetate and modified NCC, adding a catalyst, carrying out esterification reaction for 2 hours at 210 ℃, carrying out vacuum polycondensation reaction for 5 hours at 260 ℃ after the esterification is finished, and obtaining the biodegradable random copolyester after the polycondensation reaction is finished. The acid reagent is lactic acid, terephthalic acid and malic acid, and the mass ratio of lactic acid to terephthalic acid to malic acid in the acid reagent is 1:0.3: a ratio of 0.6 was used. The alcohol reagent is 1, 4-butanediol, 1, 4-cyclohexanedimethanol and glycerol, and the mass ratio of the 1, 4-butanediol, the 1, 4-cyclohexanedimethanol and the glycerol in the alcohol reagent is 1:7:4 in the ratio. The molar amount of the alcohol reagent used was 130% of the molar amount of the acid reagent used. The amount of cellulose acetate used was 30wt% based on the molar amount of the acid reagent used, the amount of modified NCC used was 20wt% based on the molar amount of the acid reagent used, and the catalyst was tetrabutyl titanate. The amount of catalyst used was 0.3wt% of the acid reagent.
Comparative example 1:
a method of producing random copolyester, which is different from example 3 in that cellulose acetate is used in an amount of 30wt% and modified NCC is used in an amount of 5wt% based on the molar amount of an acid agent.
Comparative example 2:
a method of producing random copolyester, which is different from example 3 in that cellulose acetate is used in an amount of 30wt% and modified NCC is used in an amount of 35wt% based on the molar amount of an acid agent.
Comparative example 3:
a method of producing random copolyester, which is different from example 3 in that cellulose acetate is used in an amount of 15wt% and modified NCC is used in an amount of 20wt% based on the molar amount of an acid agent.
Comparative example 4:
a method of producing a random copolyester, this example being different from example 3 in that cellulose acetate is used in an amount of 45wt% and modified NCC is used in an amount of 20wt% based on the molar amount of an acid agent.
Comparative example 5:
a method of producing a random copolyester, this example being different from example 3 in that cellulose acetate is used in an amount of 15wt% and modified NCC is used in an amount of 5wt% based on the molar amount of an acid agent.
Comparative example 6:
a process for the preparation of random copolyesters, which is different from example 3 in that cellulose acetate is used in an amount of 45% by weight of the molar amount of the acid agent and modified NCC is used in an amount of 35% by weight of the molar amount of the acid agent.
Test examples:
1. topography characterization
Test samples: example 3 the resulting random copolyester was prepared.
And spraying gold on the cross section of the sample, and observing the appearance of the sample by adopting SEM.
The surface appearance of the random copolyester prepared by the invention is shown in figure 1, and the surface of the random copolyester is uneven and has certain roughness.
In the figures of the following test results, S1 is example 1, S2 is example 2, S3 is example 3, S4 is example 4, S5 is example 5, S6 is example 6, S7 is example 7, S8 is example 8, S9 is example 9, S10 is example 10, S11 is example 11, S12 is example 12, D1 is comparative example 1, D2 is comparative example 2, D3 is comparative example 3, D4 is comparative example 4, D5 is comparative example 5, and D6 is comparative example 6.
2. Mechanical tensile Property test
Test samples: the random copolyesters obtained in the examples and comparative examples were prepared.
The test samples were made into standard dumbbell-shaped bars using an injection molding machine. And testing the tensile property of the test sample by using an electronic universal material testing machine.
The tensile property test results of the random copolyester prepared by the above examples and comparative examples of the method of the present invention are shown in fig. 2, and the basic technical scheme of the present invention is as follows: the acid reagent and the alcohol reagent are catalyzed to generate polyester under the action of a catalyst, the acid reagent uses lactic acid and terephthalic acid at first, the alcohol reagent uses 1, 4-butanediol and 1, 4-cyclohexanedimethanol, and the acid reagent and the alcohol reagent respectively contain two groups capable of reacting, so that a random copolymer can be prepared by the mixing reaction of the reagents, besides the acid reagent and the alcohol reagent, in order to improve the performance of the random copolyester, substances can be added to jointly obtain the random copolyester, and when the added substances have alcoholic hydroxyl groups or acid carboxyl groups, the substances can be jointly reacted with the acid reagent and the alcohol reagent to form the covalently connected random copolyester, so that the performance of the random copolyester is improved, and from the tensile strength of the obtained random copolyester, even if covalent bonds are formed, the tensile strength of the random copolyester is enhanced, and the effect of improving the tensile strength of the random copolyester is realized when the cellulose acetate or the cellulose acetate and the modified NCC are jointly applied to the preparation of the random copolyester; when the alcohol reagent is used unchanged, after malic acid is further used in the acid reagent, the reactive groups in the malic acid exceed two, so that a branched chain structure can be formed in the process of random copolymerization, and a random copolymer with a complex crosslinking effect is formed, and in the process of random polymerization, after a substance capable of forming a bond is added besides the acid reagent and the alcohol reagent, the structure of the random copolymer can be destroyed if the amount of the substance is too high, and the substance is too little and cannot play a role, so that the performance of the random copolymer is affected, as can be seen from fig. 1, when the amount of the substance is too high, the tensile strength of the random copolymer cannot be continuously enhanced, and when the amount of the substance is too little, the tensile strength of the random copolymer is basically unchanged; when the acid reagent is used unchanged, glycerol which shows more than two reactive groups is added into the alcohol reagent, so that a complex crosslinking structure can be formed in the random copolymer, but the tensile strength of the random copolymer is improved slightly compared with the use of the acid reagent; the use of more than two reactive groups in both the acid and alcohol reagents gives the random copolymer the best tensile properties.
3. Thermal stability test
Test samples: the random copolyesters were prepared in each example and comparative example.
Weighing the test sample, performing heat treatment at 400 ℃ for 5min, cooling, weighing, and calculating the high temperature loss rate.
High temperature loss rate = (mass before pyrolysis-mass after pyrolysis)/mass before pyrolysis × 100%.
The high temperature resistance test results of the random copolyester prepared by the above examples and comparative examples of the method of the present invention are shown in fig. 3, and the basic technical scheme of the present invention is as follows: the acid reagent and the alcohol reagent are catalyzed to generate polyester under the action of a catalyst, the acid reagent uses lactic acid and terephthalic acid at first, the alcohol reagent uses 1, 4-butanediol and 1, 4-cyclohexanedimethanol, and the acid reagent and the alcohol reagent respectively contain two reactive groups, so that a random copolymer can be prepared by the mixing reaction of the reagents, besides the acid reagent and the alcohol reagent, in order to improve the performance of the random copolyester, substances can be added to jointly obtain the random copolyester, and when the added substances have alcoholic hydroxyl groups or acid carboxyl groups, the substances can be jointly reacted with the acid reagent and the alcohol reagent to form the covalently connected random copolyester, so that the performance of the random copolyester is improved, and from the heat resistance of the obtained random copolyester, even if covalent bonds are formed, and the high-temperature loss resistance of the random copolyester is enhanced, the high-temperature loss resistance of the obtained random copolyester is small, so that the effect of improving the high-temperature loss resistance of the random copolyester is achieved; when the alcohol reagent is used unchanged, after malic acid is further used in the acid reagent, the reactive groups in the malic acid exceed two, so that a branched chain structure can be formed in the process of random copolymerization, thereby forming a random copolymer with a complex crosslinking effect, and in the process of random polymerization, after a substance which can form a bond is added besides the acid reagent and the alcohol reagent, the structure of the random copolymer can be destroyed if the amount of the substance is too high, and the substance is too little and cannot play a role, thereby affecting the performance of the random copolymer, as can be seen from fig. 1, when the amount of the substance added is too high, the high temperature loss resistance of the random copolymer cannot be continuously enhanced, and when the amount of the substance added is too low, the high temperature loss resistance of the random copolymer is basically unchanged; when the acid reagent is used unchanged, after glycerol which shows more than two reactive groups is added into the alcohol reagent, a complex crosslinking structure can be formed in the random copolymer, but the high-temperature loss resistance of the random copolymer is slightly improved compared with the use of the acid reagent; when more than two reactive groups are used in both the acid and alcohol reagents, the resulting random copolymer has the best resistance to loss of high temperature.
4. Test for degradation Properties
Test samples: the random copolyesters obtained in the examples and comparative examples were prepared.
4.1 enzymolysis degradation: weighing the test sample, putting the test sample into a culture dish containing enough lipase solution (with the pH value of 7.2), naturally degrading the test sample for 168 hours at the temperature of 25 ℃, taking out the test sample, drying the test sample, and calculating the enzymolysis weight loss rate.
Weight loss rate by enzymolysis = (mass before degradation-mass after degradation)/mass before degradation × 100%.
The results of the enzymatic degradation performance test of the random copolyester prepared by the above-mentioned examples and comparative examples of the method of the present invention are shown in fig. 5, and the basic technical scheme of the present invention is as follows: the acid reagent and the alcohol reagent are catalyzed to generate polyester under the action of a catalyst, the acid reagent uses lactic acid and terephthalic acid at first, the alcohol reagent uses 1, 4-butanediol and 1, 4-cyclohexanedimethanol, and the acid reagent and the alcohol reagent respectively contain two reactive groups, so that a random copolymer can be prepared by the mixing reaction of the reagents, besides the acid reagent and the alcohol reagent, in order to improve the performance of the random copolyester, substances can be added to jointly obtain the random copolyester, and when the added substances have alcoholic hydroxyl groups or acid carboxyl groups, the substances can jointly react with the acid reagent and the alcohol reagent to form the covalently connected random copolyester, so that the performance of the random copolyester is improved, and from the heat resistance of the obtained random copolyester, the formation of covalent bonds is shown, the enzymatic degradation performance of the random copolyester under the alkaline condition is enhanced, and when the cellulose acetate or the cellulose acetate and modified NCC are jointly applied to the preparation of the random copolyester, the obtained enzymatic degradation loss of the random copolyester is higher, so that the effect of improving the enzymatic degradation performance of the random copolyester is achieved; when the alcohol reagent is used unchanged, after malic acid is further used in the acid reagent, the reactive groups in the malic acid exceed two, so that a branched chain structure can be formed in the process of random copolymerization, thereby forming a random copolymer with a complex crosslinking effect, and in the process of random polymerization, after a substance which can form bonding is added besides the acid reagent and the alcohol reagent, the structure of the random copolymer can be destroyed if the dosage of the substance is too high, and the substance is too little and cannot play a role, thereby affecting the performance of the random copolymer, as can be seen from fig. 1, when the dosage of the substance is too high, the enzymolysis degradation performance of the random copolymer cannot be continuously enhanced, and when the dosage of the additive substance is too low, the enzymolysis degradation performance of the random copolymer is basically unchanged; when the acid reagent is used unchanged, after glycerol which shows more than two reaction groups is added into the alcohol reagent, a complex cross-linking structure can be formed in the random copolymer, but compared with the use of the acid reagent, the improvement of the enzymolysis degradation performance of the random copolymer is stronger; after substances with more than two reaction groups are used in both the acid reagent and the alcohol reagent, the obtained random copolymer has the best enzymolysis degradation performance.
4.2 hydrolytic degradation: weighing a test sample, adding the test sample into a 3wt% sodium hydroxide solution, treating the test sample for 120 hours at the temperature of 30 ℃, taking out the test sample, drying the test sample, and calculating the hydrolysis weight loss rate.
Weight loss rate by hydrolysis = (mass before degradation-mass after degradation)/mass before degradation × 100%.
The results of the hydrolytic degradation tests of the random copolyesters prepared by the above examples and comparative examples of the method of the invention are shown in fig. 4, and the basic technical scheme of the invention is as follows: the acid reagent and the alcohol reagent are catalyzed to generate polyester under the action of a catalyst, the acid reagent uses lactic acid and terephthalic acid at first, the alcohol reagent uses 1, 4-butanediol and 1, 4-cyclohexanedimethanol, and the acid reagent and the alcohol reagent respectively contain two reactive groups, so that a random copolymer can be prepared by the mixing reaction of the reagents, besides the acid reagent and the alcohol reagent, substances can be added to jointly obtain the random copolyester in order to improve the performance of the random copolyester, and when the added substances have alcoholic hydroxyl or acid carboxyl groups, the substances can be jointly reacted with the acid reagent and the alcohol reagent to form the covalently connected random copolyester, so that the performance of the random copolyester is improved, and from the aspect of hydrolytic degradation performance of the obtained random copolyester, the hydrolytic degradation performance of the obtained random copolyester is not strong after the cellulose acetate is used or the cellulose acetate and the modified NCC are jointly applied to the preparation of the random copolyester; when the alcohol reagent is used unchanged, after malic acid is further used in the acid reagent, more than two reactive groups in the malic acid can be reacted, so that a branched chain structure can be formed in the process of random copolymerization, thereby forming a random copolymer with a complex crosslinking effect, and in the process of random polymerization, after a substance capable of forming a bond is added outside the acid reagent and the alcohol reagent, the dosage of the substance needs to be within a certain range, and the change of the hydrolytic degradation performance of the substance is not obvious no matter whether the dosage is too high or too low; when the acid reagent is used unchanged, glycerol which shows more than two reaction groups is added into the alcohol reagent, so that a complex crosslinking structure can be formed in the random copolymer, and the change of the hydrolytic degradation performance of the obtained random copolymer is not obvious; after more than two reactive groups are used in both the acid reagent and the alcohol reagent, the hydrolytic degradation performance of the obtained random copolymer is also not greatly changed, which shows that the structure of the random copolyester is not greatly influenced in the hydrolysis treatment.
The above embodiments are merely illustrative, and not restrictive, of the present invention, and those skilled in the art can make various changes and modifications without departing from the spirit and scope of the present invention. Therefore, all equivalent technical solutions also belong to the scope of the present invention, and the protection scope of the present invention should be defined by the claims.
Claims (4)
1. A random copolyester comprising: mixing an acid reagent and an alcohol reagent, adding cellulose acetate, and reacting under catalysis to generate random copolyester, wherein the acid reagent is lactic acid, terephthalic acid and malic acid; lactic acid, terephthalic acid and malic acid in the acid reagent are mixed according to the mass ratio of 1:0.3: the proportion of 0.6 is used; the alcohol reagent is 1, 4-butanediol, 1, 4-cyclohexanedimethanol and glycerol; 1, 4-butanediol, 1, 4-cyclohexanedimethanol and glycerol in the alcohol reagent are mixed according to the mass ratio of 1:7:4 in proportion; the molar weight of the alcohol reagent is 100-150% of that of the acid reagent; the usage amount of the cellulose acetate is 20-40wt% of the usage amount of the acid reagent.
2. A random copolyester according to claim 1, characterized by: the copolymer is degraded by lipase under neutral conditions and/or hydrolyzed under alkaline conditions.
3. A process for preparing a random copolyester of claim 1, comprising: mixing an acid reagent and an alcohol reagent, adding cellulose acetate, and reacting under the catalysis of a catalyst to generate random copolyester; the acid reagent is lactic acid, terephthalic acid and malic acid; the alcohol reagent is 1, 4-butanediol, 1, 4-cyclohexanedimethanol and glycerol.
4. The method for preparing random copolyester according to claim 3, which is characterized in that: the acid reagent further comprises adipic acid; the alcohol reagent also includes PEG.
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