CN115197403A - Crystalline degradable polyester based on 1, 3-butanediol and preparation method thereof - Google Patents
Crystalline degradable polyester based on 1, 3-butanediol and preparation method thereof Download PDFInfo
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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
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
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Abstract
The invention provides a crystalline degradable polyester based on 1, 3-butanediol and a preparation method thereof, the crystalline degradable polyester is prepared by taking terephthalic acid, adipic acid, succinic acid, 1, 3-butanediol and 1, 4-butanediol as raw materials through a one-pot synthesis method, the production process is simplified, and under the condition of omitting the addition of a chain extender, the prepared polyester material has higher molecular weight and excellent mechanical property and also has the advantage of environmental protection. In addition, the raw materials can be obtained based on biomass, are rich in sources and low in cost, and are beneficial to realizing efficient utilization and a 'double-carbon' strategy of low-cost biomass.
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to a crystalline degradable polyester based on 1, 3-butanediol and a preparation method thereof.
Background
The plastic products have extremely wide application in modern society, but the traditional plastics are difficult to degrade, and along with the rapid increase of the usage amount of the plastic products, a large amount of waste plastic products cause serious environmental pollution. The biodegradable plastic serving as a novel material can be degraded into water, carbon dioxide and other biomasses through the enzyme action of microorganisms, and compared with the traditional plastic, the biodegradable plastic can be automatically decomposed in the natural environment, so that the environmental pollution is effectively reduced, and the novel biodegradable plastic conforms to the great trend of the current global product environmental protection. With the gradual establishment and implementation of plastic-forbidden policies at home and abroad, biodegradable plastics have become the most promising choice for plastic pollution in many industries and customers around the world.
At present, polyester has attracted much attention as a degradable plastic, and synthetic polyester represented by poly (butylene adipate terephthalate) (PBAT) is a semi-crystalline polymer, has a melting point of about 130 ℃ and a crystallinity of about 30%, and is one of the most popular degradable materials for the research of biodegradable plastics and the best application in the market. (H.Kargarzadeh, A.Galeski and A.Pawlak, polymer 2020,203.) the reported BASF AG trade name
PBAT particles of type F Blend C1200 with a tensile strength of 19.6. + -. 0.18M Pa and an elongation at break of 575. + -. 2.2%. However, the molecular weight of PBAT synthesized by the prior art is not high, and in order to improve the molecular weight and improve the mechanical properties, a chain extender is required to be used for chain extension of PBAT, wherein the commonly used chain extender comprises an isocyanate chain extender, a polyepoxy chain extender and the like, and although the use of the chain extender can properly improve the molecular weight and the mechanical properties of polyester, the addition of the chain extender into polyester is not green and environment-friendly, for example, the commonly used isocyanate chain extender has certain toxicity; in addition, the addition of the chain extender increases the production cost of raw materials, also reduces the degradability of PBAT, and the synthesis process is not green and environment-friendly. How to reduce the production cost on the premise of not adding a chain extender and obtain the polyester with excellent mechanical property is a technical problem which needs to be solved urgently at present.
Disclosure of Invention
In order to solve the technical problem, the invention provides a crystalline degradable polyester based on 1, 3-butanediol, and a preparation method thereof comprises the following steps:
carrying out esterification reaction on aliphatic dibasic acid and 1, 3-butanediol under the action of a catalyst and protective gas, then carrying out polycondensation reaction to obtain aliphatic polyester, and then adding terephthalic acid and 1, 4-butanediol to carry out copolymerization reaction to obtain crystalline degradable polyester based on 1, 3-butanediol;
the aliphatic dibasic acid is adipic acid or succinic acid;
the esterification reaction comprises the following steps: heating for 1-10 h at 150-300 ℃; the polycondensation reaction is as follows: heating for 0.5-7 h under the reaction pressure of 10-1000 Pa and the temperature of 190-330 ℃;
the copolymerization reaction comprises the following steps: firstly heating for 1-8 h at 160-310 ℃, and then heating for 0.5-6 h at 1-800 Pa and 200-320 ℃;
the protective gas is nitrogen or inert gas;
the molar ratio of aliphatic dibasic acid to 1, 3-butanediol to terephthalic acid to 1, 4-butanediol is 1-9.
Further, the catalyst is one of tetrabutyl titanate, tetramethyl titanate, tetraethyl titanate, tetrapropyl titanate, tetraisopropyl titanate, titanium chloride or titanium dioxide.
Further, the esterification reaction is as follows: heating for 2-6 h at 160-250 ℃; the polycondensation reaction is as follows: heating for 1-5 h under 20-600 Pa and 220-280 ℃.
Further, the copolymerization reaction comprises the following steps: firstly heating for 1.5-6.5 h at 170-280 ℃, and then heating for 1-5.5 h at 10-500 Pa and 210-290 ℃.
Further, the molar ratio of aliphatic dibasic acid 1, 3-butanediol to terephthalic acid 1, 4-butanediol is 2.5-5.
Compared with the prior art, the invention has the following beneficial effects:
the invention obtains the following excellent technical effects through the synergistic effect of the raw materials, the proportion and the process:
1. compared with the multi-step and multi-pot reaction disclosed by the prior art, the invention adopts a one-pot two-step feeding synthesis method, simplifies the reaction steps, and simultaneously copolymerizes with the polyester prepolymer generated for the first time and the redundant monomer while the polyester prepolymer is generated by the second feeding, thereby simplifying the production process.
2. The invention adopts a mode of combining 1, 3-butanediol (branched chain type molecule) and 1, 4-butanediol (straight chain type molecule) to replace the traditional processing mode of singly adding 1, 4-butanediol (straight chain type molecule), and forms the aliphatic polyester with non-crystallinity and flexibility and a branched chain and the aromatic polyester copolymer with crystallinity and rigidity. According to the prior art reports: the copolymer having a linear and branched structure has lower crystallinity than the single linear polymer, but the copolymer having a linear and branched structure obtained by the present invention has higher crystallinity than the single linear polymer. Compared with the prior art, the method achieves unexpected technical effects. This yields: compared with the prior art, the invention obviously improves the crystallinity and synchronously improves the tensile strength and the flexibility of the material at the same time by the synergistic effect of the straight chain structure and the branched chain structure.
3. The raw materials adopted by the invention are green and environment-friendly, have rich sources and low cost, and the preparation method comprises twice feeding in one pot and carrying out melt polycondensation reaction under low pressure and without solvent, thereby simplifying the reaction steps and being green and environment-friendly. The mechanical properties of the polyester are greatly influenced by the molecular weight, and the mechanical properties of the polyester are reduced due to the fact that the molecular weight is too small. In the prior art, a chain extender is generally adopted to improve the molecular weight, so that the purpose of improving the mechanical property of polyester is achieved to a certain extent. Commonly used chain extenders include isocyanate chain extenders, polyepoxy chain extenders, and the like. Although the use of the chain extender can suitably improve the mechanical property of the polyester, the addition of the chain extender into the polyester is not environment-friendly and can increase the production cost, for example, the common isocyanate chain extender has certain toxicity. The invention breaks the bottleneck of the prior art, improves the molecular weight, crystallinity and mechanical property of the material through the synergistic effect of reaction raw materials, proportion and process under the condition of omitting a chain extender, saves the raw material cost and is green and environment-friendly.
4. The crystalline degradable polyester based on 1, 3-butanediol obtained by the invention has higher molecular weight, heat resistance and mechanical property, the number average molecular weight of the polyester is more than 5 ten thousand, no decomposition reaction occurs before 300 ℃, the mechanical property is superior to that of crystalline PBAT based on 1, 4-butanediol with equivalent molecular weight, and the polyester has good biodegradability and is green and environment-friendly.
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FIG. 1 is an infrared spectrum of a crystalline degradable polyester based on 1, 3-butanediol of example 1 of the present invention.
Detailed Description
The invention is further illustrated by the following specific examples, which are intended to be illustrative only and not limiting to the scope of the invention.
Example 1
According to a molar ratio of 50 of terephthalic acid to adipic acid, 1.2 of adipic acid to 1, 3-butanediol, 1.3 of terephthalic acid to 1, 4-butanediol and 0.0016 of the ratio of the total mass of tetrabutyltitanate to dibasic acid.
Weighing adipic acid, 1, 3-butanediol and tetrabutyl titanate in a four-neck bottle in N 2 Esterification reaction is carried out in the atmosphere, reaction is carried out for 1 hour at 180 ℃,200 ℃ and 220 ℃, vacuum pumping (100 Pa) is carried out at 230 ℃, and polycondensation reaction is carried out for 1 hour, so as to obtain the aliphatic polyester. Then N is passed 2 Cooling to 182 ℃, adding terephthalic acid and 1, 4-butanediol, reacting at 182 ℃ for 1 hour, at 202 ℃ for 1.2 hours, at 222 ℃ for 1.4 hours, and then vacuumizing at 232 ℃ for 90Pa for 1.2 hours to obtain the crystalline degradable polyester 1 of 1, 3-butanediol. Polyester 1 had a number average molecular weight of 5.5 ten thousand, a melting point of 112.8 ℃ and a crystallinity of 20%. The infrared characterization of degradable polyester 1 is shown in fig. 1.
The structural formula is as follows:
wherein m is 113 to 119 and n is 134 to 140.m and n are integers.
Example 2
According to a molar ratio of 60 of terephthalic acid to adipic acid, 1.4 of adipic acid to 1, 3-butanediol, 1.5 of terephthalic acid to 1, 4-butanediol and 0.0017 of the ratio of tetrabutyltitanate to the total mass of dibasic acid.
Weighing adipic acid, 1, 3-butanediol and tetrabutyl titanate in a four-neck bottle in N 2 Esterification reaction is carried out in the atmosphere, reaction is carried out for 1.1 hours at the temperature of 182 ℃,203 ℃ and 224 ℃, vacuum pumping (80 Pa) is carried out at the temperature of 233 ℃, and polycondensation reaction is carried out for 1.1 hours, so as to obtain the aliphatic polyester. Then N is passed 2 Cooling to 184 ℃, adding terephthalic acid and 1, 4-butanediol, reacting for 1 hour at 184 ℃, reacting for 1.1 hours at 205 ℃, reacting for 1.2 hours at 226 ℃, and then vacuumizing (70 Pa) at 235 ℃ for reacting for 1.2 hours to obtain the crystalline degradable polyester 2 of the 1, 3-butanediol. The polyester 2 had a number average molecular weight of 6.2 ten thousand, a melting point of 144.5 ℃ and a crystallinity of 27%.
The structural formula is as follows:
wherein m is 154 to 160 and n is 120 to 127.m and n are integers.
Example 3
According to a molar ratio of terephthalic acid to adipic acid of 70, a molar ratio of adipic acid to 1, 3-butanediol of 1.55, a molar ratio of terephthalic acid to 1, 4-butanediol of 1.65, a ratio of the amount of tetrabutyltitanate to the total amount of dibasic acid of 0.0018.
Weighing adipic acid, 1, 3-butanediol and tetrabutyl titanate in a four-neck bottle in N 2 Performing esterification reaction at 185 deg.C, 205 deg.C and 225 deg.C for 1.2 hr, vacuumizing at 236 deg.C (70 Pa), and performing polycondensation reaction for 1.1 hr to obtainAn aliphatic polyester. Then N is passed 2 Cooling to 186 ℃, adding terephthalic acid and 1, 4-butanediol, reacting at 186 ℃ for 1.1 h, at 206 ℃ for 1.2 h, at 226 ℃ for 1.3 h, and then vacuumizing at 237 ℃ to (55 Pa) for 1.3 h to obtain the crystalline degradable polyester 3 of the 1, 3-butanediol. The number average molecular weight of polyester 3 was 5.7 ten thousand, the melting point was 170.5 ℃, the crystallinity was 32%, the tensile strength was 42.6M Pa, and the elongation at break was 699.8%.
The structural formula is as follows:
wherein m is 165 to 171 and n is 82 to 88.m and n are integers.
Example 4
According to a molar ratio of terephthalic acid to adipic acid of 75, a molar ratio of adipic acid to 1, 3-butanediol of 1.7, a molar ratio of terephthalic acid to 1, 4-butanediol of 1.8, a ratio of tetrabutyltitanate to the total mass of dibasic acid of 0.0019.
Weighing adipic acid, 1, 3-butanediol and tetrabutyl titanate in a four-neck bottle in N 2 The esterification reaction was carried out under an atmosphere, and the reaction was carried out at 187 ℃,208 ℃,229 ℃ for 1.3 hours, and the polycondensation reaction was carried out at 235 ℃ under vacuum (60 Pa) for 1.2 hours to obtain an aliphatic polyester. Then N is passed 2 Cooling to 190 ℃, adding terephthalic acid and 1, 4-butanediol, reacting at 190 ℃ for 1.2 hours, at 210 ℃ for 1.3 hours and at 230 ℃ for 1.4 hours, and then vacuumizing at 240 ℃ (45 Pa) for 1.5 hours to obtain the crystalline degradable polyester 4 of the 1, 3-butanediol. Polyester 4 had a number average molecular weight of 5.8 ten thousand, a melting point of 183.9 ℃, a crystallinity of 33%, a tensile strength of 47.5M Pa, and an elongation at break of 701.9%.
The structural formula is as follows:
wherein m is 181 to 186, and n is 69 to 75.m and n are integers.
Example 5
According to the following conditions that the molar ratio of terephthalic acid to succinic acid is 50.
Weighing succinic acid, 1, 3-butanediol and tetrabutyl titanate in a four-mouth bottle, and adding 2 Esterification reaction is carried out under the atmosphere, the reaction is carried out for 1.4 hours at 175 ℃,195 ℃ and 215 ℃, vacuum pumping (95 Pa) is carried out at 225 ℃, and polycondensation reaction is carried out for 1.3 hours, thus obtaining the aliphatic polyester. Then N is passed 2 Cooling to 183 deg.c, adding terephthalic acid and 1, 4-butanediol, reacting at 183 deg.c for 1.2 hr, at 204 deg.c for 1.3 hr, at 225 deg.c for 1.4 hr, and vacuum pumping at 238 deg.c (75 Pa) for 2 hr to obtain the crystalline degradable polyester of 1, 3-butanediol 5. The polyester 5 had a number average molecular weight of 5.8 ten thousand, a melting point of 114.8 ℃ and a crystallinity of 21%.
The structural formula is as follows:
wherein m is 119 to 125, and n is 164 to 171.m and n are integers.
Example 6
According to the molar ratio of terephthalic acid to succinic acid of 60, the molar ratio of succinic acid to 1, 3-butanediol of 1.75, the molar ratio of terephthalic acid to 1, 4-butanediol of 1.85, the ratio of the amount of tetrabutyltitanate to the total amount of dibasic acid of 0.0021.
Weighing succinic acid, 1, 3-butanediol and tetrabutyl titanate in a four-mouth bottle, and adding 2 Esterification reaction is carried out in the atmosphere, reaction is carried out for 1.2 hours at 191 ℃,212 ℃ and 231 ℃, vacuum pumping (80 Pa) is carried out at 242 ℃, and polycondensation reaction is carried out for 1.4 hours, so as to obtain the aliphatic polyester. Then N is passed 2 Cooling to 193 deg.C, adding terephthalic acid and 1, 4-butanediol, reacting at 193 deg.C for 1.3 hr, at 214 deg.C for 1.3 hr, at 233 deg.C for 1.5 hr, vacuum-pumping at 250 deg.C (60 Pa) for 2.1 hr,to obtain the crystalline degradable polyester 6 of the 1, 3-butanediol. The polyester 6 had a number average molecular weight of 6.3 ten thousand, a melting point of 142.8 ℃ and a crystallinity of 23%.
The structural formula is as follows:
wherein m is 156 to 163, and n is 142 to 150.m and n are integers.
Example 7
According to the molar ratio of terephthalic acid to succinic acid of 70, the molar ratio of succinic acid to 1, 3-butanediol of 1.85, the molar ratio of terephthalic acid to 1, 4-butanediol of 1.95, and the ratio of the total mass of tetrabutyltitanate to dibasic acid of 0.0022.
Weighing succinic acid, 1, 3-butanediol and tetrabutyl titanate in a four-mouth bottle, and adding 2 Esterification reaction is carried out under the atmosphere, reaction is carried out for 1.3 hours at the temperature of 192 ℃,213 ℃ and 234 ℃, vacuum pumping (55 Pa) is carried out at the temperature of 244 ℃, and polycondensation reaction is carried out for 1.5 hours, so as to obtain the aliphatic polyester. Then N is passed 2 Cooling to 194 ℃, adding terephthalic acid and 1, 4-butanediol, reacting for 1.4 hours at 194 ℃, 1.5 hours at 216 ℃, 1.5 hours at 236 ℃, and then reacting for 2.2 hours at 252 ℃ under vacuum (30 Pa) to obtain the crystalline degradable polyester 7 of the 1, 3-butanediol. The polyester 7 had a number average molecular weight of 6.2 ten thousand, a melting point of 169.7 ℃, a crystallinity of 30%, a tensile strength of 44.0M Pa, and an elongation at break of 662.1%.
The structural formula is as follows:
wherein m is 180 to 186, and n is 103 to 112.m and n are integers.
Example 8
According to a molar ratio of terephthalic acid to succinic acid of 75 to 1, 3-butanediol of 1.95, a molar ratio of terephthalic acid to 1, 4-butanediol of 1.2.0 and a ratio of tetrabutyltitanate to the total mass of dibasic acid of 0.0023.
Weighing succinic acid, 1, 3-butanediol and tetrabutyl titanate in a four-mouth bottle, and adding 2 Esterification reaction is carried out in the atmosphere, reaction is carried out for 1.5 hours at 195 ℃,215 ℃ and 235 ℃, vacuum pumping (40 Pa) is carried out at 246 ℃, and polycondensation reaction is carried out for 1.6 hours, thus obtaining the aliphatic polyester. Then N is passed 2 Cooling to 198 ℃, adding terephthalic acid and 1, 4-butanediol, reacting at 198 ℃ for 1.3 hours, at 218 ℃ for 1.2 hours, at 238 ℃ for 1.1 hours, and then, vacuumizing at 255 ℃ for 20Pa, reacting for 2.3 hours to obtain the crystalline degradable polyester 8 of the 1, 3-butanediol. The polyester 8 had a number average molecular weight of 6.1 ten thousand, a melting point of 182.3 ℃, a crystallinity of 34%, a tensile strength of 46.2M Pa, and an elongation at break of 603.7%.
The structural formula is as follows:
wherein m is 190-196 and n is 84-92. m and n are integers.
Comparative example 1
The article name: synthesis and Properties of Poly (hexamethylene 2, 5-furandicarboxylate-co-adipate) copolyester Synthesis and Properties of Poly (hexamethylene 2, 5-furandicarboxylate-co-adipate) polyesters
The authors: mingkun Chen et al
Out of: european Polymer Journal,2021,161.
The method comprises the following steps: appropriate amounts of Hexanediol (HDO), furan-2, 5-dicarboxylic acid dimethyl ester (DMFD), adipic Acid (AA) (nHDO/n (DMFD + AA) = 1.2/1) and tetrabutyl titanate (TBT) (0.1 mol% of DM FD) were placed in a three-neck flask. The transesterification/esterification process was carried out at 230 ℃ and heated under nitrogen for 2 hours until no more methanol and water were collected and a low pressure (about 80 Pa) was slowly applied over about 30 minutes. Three PH FA copolyesters were synthesized by further reacting at 235 deg.C for 3 hours during polycondensation. Among the three copolyesters, PHFA10 has the highest tensile strength of 23.3 + -2.8 MPa and PHFA30 has the highest elongation at break of 498.3 + -12.0%.
In comparative example 1, the authors used expensive dimethyl furan-2, 5-dicarboxylate and hexanediol, which is more expensive than the two butanediol monomers used in the present invention, as raw materials, and first performed transesterification and esterification reactions, and then performed polycondensation reactions to produce copolyesters, and by changing the molar ratio of DMFD to AA, three copolyesters were synthesized, all of which had a certain crystallinity, and among the three copolyesters, PHFA10 had the highest tensile strength of 23.3 ± 2.8MPa, elongation at break of 283.6 ± 15.7%, PHFA30 had the highest elongation at break of 498.3 ± 12.0%, and tensile strength of 19.3 ± 0.5MPa. Compared with the comparative ratio 1, the invention uses lower-price terephthalic acid, adipic acid, 1, 3-butanediol and 1, 4-butanediol as raw materials, adopts a one-pot two-time feeding method, and prepares the copolymer by a two-step esterification polycondensation synthesis method, and the polymer has better crystallinity; and the tensile property and the elongation at break of the polymer obtained by the invention are superior to the optimal mechanical property data in the comparative example 1.
Comparative example 2
The article name: impact of AA/PTA monomer ratio on PBAT copolyester Performance authors: zhao Cai Xia et al
Out of: the journal of chemical engineering, 2017,68 (1): 452-459.
The method comprises the following steps: the PBAT copolyester is synthesized by two-step reaction of esterification and polycondensation. The amounts of 1, 4-Butanediol (BDO), adipic Acid (AA), terephthalic acid (PTA) and the catalyst tetrabutyl titanate (TBOT) [0.5 mol% acid%]Putting the mixture into a three-neck flask according to the calculated molar ratio, putting the mixture into a salt bath kettle to slowly raise the reaction temperature to 160-180 ℃ for 4-5 hours, and introducing N in the process 2 Until no more water is distilled out. The temperature is continuously increased to 220-240 ℃, and the vacuum degree of the experimental system is kept at 20-30 Pa. When the viscosity of the reactants no longer increased, the reaction was considered complete. Copolyesters were prepared herein with AA to PTA ratios of 1,3, 7, 5, 7, 3, 9, 1, 10, respectively, labeled PBAT1:9, PBAT3:7, PBAT5:5, PBAT7:3, PBAT9:1, PBA. The molar ratio of dibasic acids (adipic acid and terephthalic acid) to butanediol in the reaction was 1. The results show that the best combination of tensile properties is PBAT3:7, a number average molecular weight of 73000 and a tensile strength of 35.3 +/-1.7 MPa and elongation at break of 553.1 +/-10.1 percent.
In comparative example 2 the authors investigated the effect of AA/PTA monomer ratio on PBAT copolyester performance, and prepared copolyesters with AA to PTA ratios of 1, 9, 3, 5, 7, 3, 1, 10. The results show that the best ratio of tensile properties in combination is 3. In the present invention, similarly to this ratio, polyester 3 prepared in example 3 was used, and polyester 3 of the present invention had a number average molecular weight of 5.7 ten thousand, a tensile strength of 42.6MPa and an elongation at break of 699.8%.
The results show that the tensile strength and elongation at break of polyester 3 obtained in example 3 according to the invention are better than the performance data of comparative example 2 in the corresponding proportions.
In addition, the common ratio of AA to PTA used in the industrial production of PBAT is 5, the number average molecular weight is about 60000, and the elongation at break is 775.5 +/-15.2%; similar to the commercial PBAT ratio of 5 in the present invention, polyester 1 prepared in example 1, the number average molecular weight of polyester 1 of the present invention was 5.5 ten thousand, and the elongation at break was 1332.4%, which is much higher than the elongation at break of the PBAT5:5 copolyester in comparative example 2. The comparative data results show that the number average molecular weight of the polyester obtained by the invention is lower than that of the copolyester in the corresponding proportion in the comparative example 2, but the performance is better than that of the related polyester in the comparative example 2, thereby showing that the performance of the synthesized crystallizable polyester is better than that of PBAT in the comparative example 2.
Comparative example 3
Article name: synthesis and characterization of chain-extended polybutylene terephthalate-co-polybutylene adipate
The authors: asn ren Xu et al
Out of: polyester industry, 2013 (1): 16-20.
The method comprises the following steps: poly (butylene terephthalate) -co-poly (butylene adipate) (PBAT) is synthesized by adopting 1, 4-butanediol, dimethyl terephthalate and adipic acid. Hexamethylene diisocyanate is used as a chain extender to synthesize high-molecular-weight PBAT.
The results showed that the tensile strength before chain extension was 11.8MPa and the tensile strength after chain extension was 19.3MPa.
Comparative example 3 reports that isocyanate, polyfunctional epoxy compound, bisoxazoline and the like are generally used as chain extenders in the process of synthesizing high molecular weight polyester, so that the molecular weight of the product can be further improved. Comparative example 3 high molecular weight PBAT synthesized using hexamethylene diisocyanate as a chain extender showed that the tensile strength before chain extension was 11.8MPa and the tensile strength after chain extension was 19.3MPa. The invention keeps the number average molecular weight of the obtained polyester above 5 ten thousand without using toxic hexamethylene diisocyanate as a chain extender, and the tensile strength is superior to that of PBAT after chain extension in comparative example 3.
FIG. 1 is an infrared spectrum of a crystalline degradable polyester based on 1, 3-butanediol of example 1. As can be seen in FIG. 1, 2960cm -1 Belongs to a methylene stretching vibration absorption peak, 1720cm -1 Belongs to a stretching vibration absorption peak of-C = O, 1330-1050 cm -1 The two middle strong peaks belong to the stretching vibration absorption peak of-C-O-C, 700-900 cm -1 Belongs to an in-plane bending vibration absorption peak of-C-H on a benzene ring, 1457cm -1 Belonging to the vibration peak of a benzene ring framework. The results indicate successful polyester synthesis.
The crystalline degradable polyesters based on 1, 3-butanediol prepared in the above examples 1-8 were subjected to mechanical tests, and the results are shown in Table 1.
Table 1: mechanical Properties of crystalline degradable polyesters based on 1, 3-butanediol prepared in examples 1 to 8
According to the data, the invention utilizes the dihydric alcohol and the dibasic acid with rich sources as raw materials, adopts the green and environment-friendly solvent-free melt polycondensation method for preparation, and prepares the crystalline degradable polyester based on the 1, 3-butanediol by a one-pot two-feeding synthesis method with simple operation, and the polyester has excellent mechanical properties.
The data comparison results of examples 1-8 and comparative examples 1-3 show that the synthetic polyester has a microstructure superior to that of the prior art through the synergistic effect of the chemical structure of the raw materials, the proportion of the raw materials and the process, and the polyester has high molecular weight and excellent mechanical properties under the condition of not adding a chain extender. Under the condition of adopting similar raw material proportion with the prior art, the tensile strength and the elongation at break of the polyester obtained by the invention are superior to those of the polyester obtained by the prior art. The invention achieves superior performance to prior art PBAT polyesters and the resulting crystallizable copolyesters have higher crystallinity than prior art crystalline PBAT polyesters. Therefore, compared with the prior art, the invention achieves unexpected technical effects.
Further, as can be seen from examples 3, 4, 7 and 8 of the present invention, in which the crystallinity, melting point, tensile strength and elongation at break of the copolymer obtained in example 4 were the highest in the 4 examples, the present invention is illustrated by adjusting the chemical structure of the raw materials, the reaction ratio and the process, that is, by the synergistic effect of the above parameters, the properties of the material are significantly improved.
Claims (5)
1.1, 3-butanediol-based crystalline degradable polyester, characterized in that the preparation method comprises the following steps:
carrying out esterification reaction on aliphatic dibasic acid and 1, 3-butanediol under the action of a catalyst and a protective gas, then carrying out polycondensation reaction to obtain aliphatic polyester, and then adding terephthalic acid and 1, 4-butanediol to carry out copolymerization reaction to obtain crystalline degradable polyester based on 1, 3-butanediol;
the aliphatic dibasic acid is adipic acid or succinic acid;
the esterification reaction comprises the following steps: heating for 1-10 h at 150-300 ℃; the polycondensation reaction is as follows: heating for 0.5-7 h under the reaction pressure of 10-1000 Pa and the temperature of 190-330 ℃;
the copolymerization reaction comprises the following steps: firstly heating for 1-8 h at 160-310 ℃, and then heating for 0.5-6 h at 1-800 Pa and 200-320 ℃;
the protective gas is nitrogen or inert gas;
the molar ratio of aliphatic dibasic acid to 1, 3-butanediol to terephthalic acid to 1, 4-butanediol is 1-9.
2. The crystalline degradable polyester based on 1, 3-butanediol as claimed in claim 1, wherein the catalyst is one of tetrabutyl titanate, tetramethyl titanate, tetraethyl titanate, tetrapropyl titanate, tetraisopropyl titanate, titanium chloride or titanium dioxide.
3. The crystalline degradable polyester based on 1, 3-butanediol as claimed in claim 1, wherein the esterification reaction is: heating for 2-6 h at 160-250 ℃; the polycondensation reaction is as follows: heating for 1-5 h under 20-600 Pa and 220-280 ℃.
4. The crystalline degradable polyester based on 1, 3-butanediol of claim 1, wherein the copolymerization reaction is: firstly heating for 1.5-6.5 h at 170-280 ℃, and then heating for 1-5.5 h at 10-500 Pa and 210-290 ℃.
5. The crystalline degradable polyester based on 1, 3-butanediol as claimed in claim 1, wherein the molar ratio of aliphatic dibasic acid, 1, 3-butanediol, terephthalic acid and 1, 4-butanediol is 2.5-5.
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