CN113683761A - Sulfur-containing aromatic polyester and preparation method and application thereof - Google Patents

Sulfur-containing aromatic polyester and preparation method and application thereof Download PDF

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CN113683761A
CN113683761A CN202111009306.XA CN202111009306A CN113683761A CN 113683761 A CN113683761 A CN 113683761A CN 202111009306 A CN202111009306 A CN 202111009306A CN 113683761 A CN113683761 A CN 113683761A
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sulfur
aromatic polyester
containing aromatic
polyvinyl fluoride
polyester
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CN113683761B (en
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陈俊
丁嘉欣
阳区
张刚
张德清
李著初
邓勇
寇建军
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Hunan Aerospace Sanfeng Science And Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
    • C08G63/688—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur
    • C08G63/6884—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/6886—Dicarboxylic acids and dihydroxy compounds
    • 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
    • C08G63/88—Post-polymerisation treatment
    • C08G63/90—Purification; Drying
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08L27/14—Homopolymers or copolymers of vinyl fluoride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation

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  • Health & Medical Sciences (AREA)
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  • Polyesters Or Polycarbonates (AREA)

Abstract

The invention takes bio-based monomers of 3, 4-thiophenedicarboxylic acid, 1, 4-cyclohexanedione-2, 5-dimethyl dicarboxylate and 1, 2-cyclopentanediol or 1, 3-cyclopentanediol as raw materials, and prepares the sulfur-containing aromatic polyester partially derived from biomass by a catalytic melt polycondensation method. The 3, 4-thiophenedicarboxylic acid can be sourced from biomass resources, and the problem of shortage of petroleum resources is effectively relieved. The prepared polyester material has the characteristics of high molecular weight, high boiling point, no toxicity, stable thermal property, high impact strength, good mechanical property, excellent degradation property and the like, has good compatibility with polyvinyl fluoride resin, can be efficiently used in material processing, plays a role in plasticization, and can effectively improve the plasticization efficiency of a plasticizer and polyvinyl fluoride.

Description

Sulfur-containing aromatic polyester and preparation method and application thereof
Technical Field
The invention belongs to the field of polyester, and relates to sulfur-containing aromatic polyester, and a preparation method and application thereof.
Background
Plastic products with excellent performance and wide use have been developed by using fossil resources as starting materials, and the petroleum-based polyesters also cause problems of resource shortage, environmental pollution and the like. Under the current large background of carbon peak reaching and carbon neutralization, the replacement of fossil-based products by bio-based products and the shift to low-carbon economy become long-term strategies for solving resource and environmental problems all over the world.
Along with the improvement of living standard, the gradual improvement of plastic performance and the increase of light-weight requirement, the usage amount of plastic also increases rapidly, and the plastic articles for use bring great convenience to the life of people, and improve the life quality of people. However, most plastics are difficult to degrade after the use value of the plastics is finished, so that the white pollution caused by the degradation is inconsistent with the double-carbon strategic development requirement of China, and the development of the bio-based sustainable and environment-friendly high polymer material has important scientific significance and social value. The bio-based polyester material has wider adjustable range, wide application field and general biodegradability, and becomes a hotspot of international social research.
The biomass reserves are abundant, and the biomass reserves are renewable resources, and are widely concerned as raw materials for obtaining clean energy and high value-added chemicals. The degradable polyester prepared from biomass resources can effectively reduce the traditional energy consumption, and has the advantages of good degradability, biocompatibility and the like, but the types of the polyester are few, and the aliphatic degradable polyesters such as Polyhydroxyalkanoate (PHA), polylactic acid (PLA), poly (1, 4-butanediol succinate) (PBS) and the like have the defects of low decomposition temperature, poor mechanical property and the like, but the requirements on the mechanical and mechanical properties are higher in the actual application.
Chinese patent CN 112300372A discloses preparation and application of sulfur-containing copolyester partially derived from biomass, the obtained product has good thermal stability and excellent degradability, but the product has the defects of low decomposition temperature, poor mechanical property and the like polyesters such as PBS, PLA and the like, and the product contains benzene rings, generates large peculiar smell in the preparation process, is not easy to soften and form, and needs to be further improved to improve the environmental protection property and the product performance.
Disclosure of Invention
In order to solve the above technical problems, the present invention provides a sulfur-containing aromatic polyester comprising the following structural units:
Figure BDA0003238297400000021
Figure BDA0003238297400000022
wherein:
in formula 1, x is 3-11, y is 2-13, n1 is 20-130, x is 4-9, y is 3-8, and n2 is 20-90.
The invention also provides a preparation method of the sulfur-containing aromatic polyester, which comprises the following steps:
s1, synthesis of a crude sulfur-containing aromatic polyester: 3, 4-thiophenedicarboxylic acid is used as a first acid source, 1, 4-cyclohexanedione-2, 5-dimethyl dicarboxylate is used as a second acid source, and 1, 3-cyclopentanediol or 1, 2-cyclopentanediol is used as a diol monomer; mixing a first acid source, a second acid source and a glycol monomer in a reactor under the protection of nitrogen, adding a catalyst, continuously stirring, reacting for 4-6 hours at 150-165 ℃ to obtain an esterified product, continuously heating to 195-235 ℃, and carrying out polycondensation reaction for 2.5-3.5 hours under continuous stirring and a vacuum degree of 30-80 Pa to obtain a crude product of the sulfur-containing aromatic polyester;
s2, purification of a crude sulfur-containing copolyester: dissolving the crude product of sulfur-containing aromatic polyester obtained in step S1 with chloroform, collecting clear liquid, dripping the clear liquid into low carbon alcohol, precipitating insoluble substances, and centrifugingSeparating, filtering, washing the obtained filter residue with low carbon alcohol, and drying the re-filtered filter residue under vacuum condition to obtain product P containing structural unit of formula 1aOr a product P comprising structural units of the formula 2b。
Further, in the step S1, the molar ratio of the 3, 4-thiophenedicarboxylic acid, the dimethyl 1, 4-cyclohexanedione-2, 5-dicarboxylate and the diol monomer is (1.0-1.3): 2 (1.0-1.3).
Further, the catalyst in step S1 is one of zirconium iso-octoate, bismuth neodecanoate, lead iso-octoate, stannous octoate, antimony acetate, and germanium dioxide.
Further, the amount of the substance of the catalyst used in the step S1 is 0.02% to 0.4% of the amount of the substance of 3, 4-thiophenedicarboxylic acid.
Further, the lower alcohol in step S2 is one of methanol, ethanol, propanol, isopropanol, isobutanol, and n-butanol, and the amount of the lower alcohol is sufficient to allow the clear solution to completely precipitate insoluble substances.
The amount of the chloroform is determined by the amount of the crude product to be purified, and the crude product of the sulfur-containing copolyester can be completely dissolved.
Further, the temperature of the lower alcohol used in step S2 is about 10 ℃.
Preferably, the temperature of the vacuum drying in the step S2 is 50-70 ℃, and the drying time is 10-15 hours.
The invention also provides a polyvinyl fluoride resin composition, which is an application of the sulfur-containing aromatic polyester and is characterized by comprising the following components in parts by weight:
polyvinyl fluoride resin: 100
Plasticizer: 5 to 15
A stabilizer: 1-3;
the plasticizer is the sulfur-containing aromatic polyester provided by the invention.
Further, the stabilizer is one of zinc stearate, tribasic lead sulfate, lead stearate, isooctyl dibutyltin dithioacetate, isooctyl antimony trimercaptoacetate and zinc ricinoleate.
The present invention also provides a method for preparing a polyvinyl fluoride resin composition, which is characterized in that the three raw materials of the polyvinyl fluoride resin, the plasticizer and the stabilizer are fully mixed according to the raw material agent proportion of the polyvinyl fluoride resin composition, and the mixture is subjected to subsequent molding processing after mixing, wherein the processing modes are not limited to extrusion, injection molding, stretching, blow molding and the like.
Compared with the prior art, the invention has the beneficial effects that:
the raw materials of the invention are 3, 4-thiophenedicarboxylic acid, 1, 4-cyclohexanedione-2, 5-dimethyl dicarboxylate and 1, 3-cyclopentanediol or 1, 2-cyclopentanediol, and compared with the raw materials needed by the preparation of the polyester from biomass in the prior art, the raw materials of the invention are easier to obtain and are more suitable for large-scale production.
Compared with the prior art, the polyester product has more main chain ring structures, no benzene ring, less branched chains and higher molecular weight, and the number average molecular weight of the polyester product is 136000-151000 g/mol, and the weight average molecular weight of the polyester product is 167000-192000 g/mol; the polyester of the invention also has good thermal stability, higher thermal decomposition temperature, 5 percent thermal decomposition temperature (T5 percent) of over 370 ℃,
the polyester product has lower melting point and high boiling point, better fluidity after softening, easier processing and forming and production cost saving; the product has larger tensile breaking stress, higher impact strength and excellent mechanical property.
The synthetic process of the invention is nontoxic and odorless, the material can not deteriorate in high-temperature hot processing, harmful substances can not be decomposed, the preparation process is more environment-friendly, and the material can be biodegraded in natural environments such as soil, seawater and fresh water, and has excellent environmental protection property.
Detailed Description
The polyester product prepared by the preparation method of the sulfur-containing aromatic polyester can be used as a plasticizer to be applied to the processing and forming of polyvinyl fluoride resin.
The present invention will be further described with reference to the following examples.
Example 1
1.7216g (10mmol) of 3, 4-thiophenedicarboxylic acid, 2.2820g (10mmol) of dimethyl 1, 4-cyclohexanedione-2, 5-dicarboxylate, 2.0426g (20mmol) of 1, 3-cyclopentanediol and 0.002mmol of zirconium isooctanoate are added into a dry single-neck flask (50mL) in sequence, and the reaction mixture is reacted for 4.5h at 155 ℃ under the protection of nitrogen to obtain an esterified product; and continuously heating to 195 ℃, controlling the vacuum degree in the reaction system to be 30Pa, and reacting for 2.5 hours to obtain a crude product of the polycondensation product. Dissolving the crude product of the polycondensation product with sufficient chloroform, taking clear liquid, adding the clear liquid into a certain amount of methanol, precipitating solid insoluble substances, centrifugally separating, filtering to obtain white solid, washing the obtained solid with ethanol, filtering again to obtain solid, and drying the solid at 55 ℃ for 10.0h in vacuum to obtain the polyester Pa1The yield thereof was found to be 91.74%. Polyester Pa1M of (A)nIs 138000g/mol, MwIt was 176000 g/mol.
The resulting polyester Pa1Can be used as a plasticizer in the processing of polyvinyl fluoride resin, and the method comprises the following steps: polyvinyl fluoride resin: polyester Pa1: and (3) fully mixing zinc stearate according to the mass ratio of 100:5:1, and then carrying out subsequent forming and processing processes such as extrusion, injection molding, stretching, blow molding and the like.
Example 2
1.8938g (11mmol) of 3, 4-thiophenedicarboxylic acid, 1.6397g (11mmol) of dimethyl 1, 4-cyclohexanedione-2, 5-dicarboxylate, 2.0426g (20mmol) of 1, 3-cyclopentanediol and 0.0035mmol of bismuth neodecanoate are added in sequence to a dry single-neck flask (50mL), and the reaction mixture is reacted for 5.0h under the protection of nitrogen at 150 ℃ to obtain an esterified product; and continuously heating to 210 ℃, controlling the vacuum degree in the reaction system to be 40Pa, and reacting for 3.0h to obtain a crude product of the polycondensation product. Dissolving the crude product of the polycondensation product with sufficient chloroform, taking clear liquid, adding the clear liquid into a certain amount of ethanol, precipitating solid insoluble substances, centrifugally separating, filtering to obtain white solid, washing the obtained solid with ethanol, filtering again to obtain solid, and drying the solid at 60 ℃ under vacuum for 12.0h to obtain the polyester Pa2Yield 92.14%, MnIs 149000g/mol, MwIt was 188000 g/mol.
The resulting polyester Pa2Can be used as a plasticizer in the processing of polyvinyl fluoride resin, and the method comprises the following steps: polyvinyl fluoride resin: copolyester Pa2: and after fully mixing the tribasic lead sulfate according to the mass ratio of 100:8:2, carrying out subsequent molding processing processes such as extrusion, injection molding, stretching, blow molding and the like.
Example 3
2.0659g (12mmol) of 3, 4-thiophenedicarboxylic acid, 2.7384g (12mmol) of dimethyl 1, 4-cyclohexanedione-2, 5-dicarboxylate, 2.0426g (20mmol) of 1, 3-cyclopentanediol and 0.004mmol of lead isooctanoate are added into a dry single-neck flask (50mL) in sequence, and the reaction mixture is reacted for 5.5h under the protection of nitrogen at 160 ℃ to obtain an esterification product; and continuously heating to 220 ℃, controlling the vacuum degree in the reaction system to be 50Pa, and reacting for 3.5 hours to obtain a crude product of the polycondensation product. Dissolving the crude product of the polycondensation product with sufficient chloroform, taking clear liquid, adding the clear liquid into a certain amount of propanol, precipitating solid insoluble substances, centrifugally separating, filtering to obtain white solid, washing the obtained solid with ethanol, filtering again to obtain solid, and drying the solid at 60 ℃ for 13.0h in vacuum to obtain the polyester Pa3Yield 89.71%, MnIs 142000g/mol, Mw175000 g/mol.
The resulting polyester Pa3Can be used as a plasticizer in the processing of polyvinyl fluoride resin, and the method comprises the following steps: polyvinyl fluoride resin: copolyester Pa3: and after the lead stearate is fully mixed according to the mass ratio of 100:13:3, carrying out subsequent molding processing processes such as extrusion, injection molding, stretching, blow molding and the like.
Example 4
2.2381g (13mmol) of 3, 4-thiophenedicarboxylic acid, 2.9666g (13mmol) of dimethyl 1, 4-cyclohexanedione-2, 5-dicarboxylate, 2.0426g (20mmol) of 1, 2-cyclopentanediol and 0.008mmol of stannous octoate are sequentially added into a dry single-neck flask (50mL), and the reaction mixture is reacted for 6.0h at 165 ℃ under the protection of nitrogen to obtain an esterification product; and continuously heating to 230 ℃, controlling the vacuum degree in the reaction system to be 60Pa, and reacting for 3.0h to obtain a crude product of the polycondensation product. Dissolving the crude product of polycondensation product with sufficient amount of chloroform, collecting clear liquid, adding clear liquid into a certain amount of isopropanol, precipitating to obtain solid insoluble substance, centrifuging, filteringObtaining white solid, washing the obtained solid with ethanol, filtering again to obtain solid, and drying the solid for 14.0h at 65 ℃ in vacuum to obtain the polyester Pb1Yield 93.01%, MnIs 141000g/mol, MwIt was 173000 g/mol.
The resulting polyester Pb1Can be used as a plasticizer in the processing of polyvinyl fluoride resin, and the method comprises the following steps: polyvinyl fluoride resin: copolyester Pb1: and (3) fully mixing the isooctyl dithioacetate dibutyltin according to the mass ratio of 100:14:2, and then carrying out subsequent molding processing processes such as extrusion, injection molding, stretching, blow molding and the like.
Example 5
1.9798g (11.5mmol) of 3, 4-thiophenedicarboxylic acid, 2.6243g (11.5mmol) of 1, 4-cyclohexanedione-2, 5-dicarboxylic acid dimethyl ester, 2.0426g (20mmol) of 1, 2-cyclopentanediol and 0.01mmol of antimony acetate are sequentially added into a dry single-neck flask (50mL), and the reaction mixture is reacted for 4.0h under the protection of nitrogen at 155 ℃ to obtain an esterified product; and continuously heating to 235 ℃, controlling the vacuum degree in the reaction system to be 70Pa, and reacting for 2.5 hours to obtain a crude product of the polycondensation product. Dissolving the crude product of the polycondensation product with sufficient chloroform, taking clear liquid, adding the clear liquid into a certain amount of n-butanol, precipitating solid insoluble substances, centrifugally separating, filtering to obtain white solid, washing the obtained solid with ethanol, filtering again to obtain solid, and drying the solid at 55 ℃ for 15.0h in vacuum to obtain the polyester Pb2Yield 92.84%, MnIs 138000g/mol, Mw166000 g/mol.
The resulting polyester Pb2Can be used as a plasticizer in the processing of polyvinyl fluoride resin, and the method comprises the following steps: polyvinyl fluoride resin: copolyester Pb2: and fully mixing the isooctyl trimercaptoacetate antimony according to the mass ratio of 100:15:3, and then carrying out subsequent molding processing processes such as extrusion, injection molding, stretching, blow molding and the like.
Example 6
Into a dry, single-neck flask (50mL) were charged 1.8077g (10.5mmol) of 3, 4-thiophenedicarboxylic acid, 2.3961g (10.5mmol) of dimethyl 1, 4-cyclohexanedione-2, 5-dicarboxylate, 2.0426g (20mmol) of 1, 2-cyclopentanediol, and 0.042mmol of germanium dioxide in that orderReacting the mixture for 5.0h at 160 ℃ under the protection of nitrogen to obtain an esterification product; and continuously heating to 225 ℃, controlling the vacuum degree in the reaction system to be 80Pa, and reacting for 3.0h to obtain a crude product of the polycondensation product. Dissolving the crude product of the polycondensation product with sufficient chloroform, taking clear liquid, adding the clear liquid into a certain amount of isobutanol, precipitating solid insoluble substances, centrifugally separating, filtering to obtain white solid, washing the obtained solid with ethanol, filtering again to obtain solid, and drying the solid at 50 ℃ for 11.0 hours in vacuum to obtain the polyester Pb3Yield 91.37%, Mn151000g/mol, Mw192000 g/mol.
The resulting polyester Pb3Can be used as a plasticizer in the processing of polyvinyl fluoride resin, and the method comprises the following steps: polyvinyl fluoride resin: copolyester Pb3: and after the zinc ricinoleate is fully mixed according to the mass ratio of 100:10:2, the subsequent molding processing processes such as extrusion, injection molding, stretching, blow molding and the like are carried out.
Compared with the method that the nitrogen is introduced for reaction after the raw materials are mixed, the method has the advantages that the nitrogen is introduced before the raw materials are added, so that the yield can be improved to a certain extent.
The products obtained in examples 1 to 6 were subjected to a performance test and compared with literature data;
the performance test standards or methods are as follows:
the polyesters prepared in the examples were NMR-characterized using a nuclear magnetic resonance apparatus model Bruker Avance DMX600, TMS being the internal standard and CDCl 3 being the solvent.
The intrinsic viscosity was measured according to GB/T1632.5-2008, the test temperature was 25 ℃, the solvent was phenol/tetrachloroethane (50/50, wt/wt), the concentration of polyester was 0.5g/dL, and the measurement was performed with an Ubbelohde viscometer.
The melting point (Tg) was determined by DSC method with reference to GB/T19466.3-2004.
The film thickness was measured with reference to GB/T20220-.
The film tensile properties were measured with reference to GB/T1040.3-2006.
The polyesters were tested for number average molecular mass (Mn), weight average molecular mass (Mw) and polydispersity index (PDI) using a Waters-Breeze gel chromatograph, with narrow-distribution polystyrene as the standard and THF as the mobile phase.
Polyester the thermal stability of the polyester was tested using a NETZSCH TG 209 analyzer, and approximately 5mg of the sample was added to an alumina crucible and heated to 500 ℃ at a rate of 10 ℃/min under nitrogen protection.
Yield is the actual amount of the target product ÷ the theoretical amount of the target product.
The degradation rate is (loss mass ÷ initial mass) × 100%.
Table 1 shows the experimental results and the comparison of the literature data of the polyester testing sections of examples 1 to 6:
TABLE 1
Figure BDA0003238297400000071
Figure BDA0003238297400000081
M in Table 1nIs the number average molecular weight, M, of the copolyesterwIs the weight average molecular weight of the copolyester, PDI is the molecular weight distribution of the polyester, Mn1And Mn2Number average molecular weight before degradation and number average molecular weight after 18 months of degradation, Mw1And Mw2The weight average molecular weight before degradation and the weight average molecular weight after 18 months of degradation, respectively.
[1] Influence of Li jin, Liujunhong, Huangyong citric acid on the performance of synthesized poly (butylene succinate) [ J ] plastics technology, 2013(05):79-82.
Table 2 shows the mechanical properties of the polyester samples and PBS of examples 1-6:
TABLE 2
Figure BDA0003238297400000082
[2] Zhangfang, juJie, Hanhua, and the like, preparation of succinic acid butanediol polyester and structure and performance thereof [ J ]. Donghua university journal (Nature science edition), 2019,45(1):29-33.
[3]Nanni A,Ricci A,Versari A,et al.Wine derived additives as Poly(butylene succinate)(PBS)natural stabilizers for different degradative environments[J].Polymer Degradation and Stability,2020,182.
T in Table 25％Temperature, T, required for 5% thermal decomposition of the polyester95％Temperature, T, required for 95% thermal decomposition of the polyestermIs the melting point of the polyester, [ eta ]1]Is the initial intrinsic viscosity, [ eta ] of the sample2]Is the intrinsic viscosity of the sample after 18 months of degradation in natural soil environment.
Table 3 shows a comparison of the partial properties of the polyester samples of examples 1 to 6 with those of the sulfur-containing polyesters P1 to P12 disclosed in CN 112300372A:
TABLE 3
Figure BDA0003238297400000091
As can be seen from the comparison of the data in tables 1 and 2, the sulfur-containing aromatic polyester based on 3, 4-thiophenedicarboxylic acid synthesized by the present invention can be degraded from high molecular weight fragments to small molecular weight fragments, but the molecular weight of the commercial PBS is not changed much, and Table 3 compares partial properties of another sulfur-containing polyester P1-P12, it can be seen that the sulfur-containing aromatic polyester based on 3, 4-thiophenedicarboxylic acid synthesized by the present invention has higher molecular weight, thermal decomposition temperature and tensile breaking stress, higher impact strength and excellent mechanical properties. The comparison results thus show that: the polyester has good thermal stability and mechanical property, and also has good degradation property, namely good comprehensive performance, which accords with the energy-saving and emission-reducing policy and the carbon neutralization development strategy actively implemented in China.
The technical scheme in the embodiment of the application at least has the following technical effects or advantages:
the invention adopts 3, 4-thiophenedicarboxylic acid as a starting material to prepare the bio-based polyester, reduces the use of petroleum-based materials, can effectively reduce the emission of clean carbon, and has great economic value and practical significance for getting rid of the dependence on fossil energy, conforming to the strategic concept of double-carbon development and realizing sustainable development. The polyester not only has higher molecular weight and better degradation performance than the existing commercial polyester PET, but also has more stable thermal performance and better mechanical performance than the commercial polyester PBS; the copolyester has good compatibility with a polyvinyl fluoride resin material, the melting point of the copolyester is lower than 130 ℃ and the boiling point of the copolyester is higher than 460 ℃, the copolyester is tasteless and nontoxic, and the copolyester has good fluidity after being softened.
While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. Therefore, it is intended that the appended claims be interpreted as including preferred embodiments and all such alterations and modifications as fall within the scope of the invention. It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.

Claims (10)

1. A sulfur-containing aromatic polyester comprising the structural unit shown below:
Figure FDA0003238297390000011
wherein:
in formula 1, x1 is 3-11, y1 is 2-13, n1 is 20-130, x2 is 4-9, y2 is 3-8, and n2 is 20-90.
2. A method for preparing a sulfur-containing aromatic polyester, comprising the steps of:
s1, synthesis of a crude sulfur-containing aromatic polyester: 3, 4-thiophenedicarboxylic acid is used as a first acid source, 1, 4-cyclohexanedione-2, 5-dimethyl dicarboxylate is used as a second acid source, and 1, 3-cyclopentanediol or 1, 2-cyclopentanediol is used as a diol monomer; mixing a first acid source, a second acid source and a glycol monomer in a reactor under the protection of nitrogen, adding a catalyst, continuously stirring, reacting for 4-6 hours at 150-165 ℃ to obtain an esterified product, continuously heating to 195-235 ℃, and carrying out polycondensation reaction for 2.5-3.5 hours under continuous stirring and a vacuum degree of 30-80 Pa to obtain a crude product of the sulfur-containing aromatic polyester;
s2, purification of a crude sulfur-containing copolyester: and (3) dissolving the crude product of the sulfur-containing aromatic polyester obtained in the step (S1) with chloroform, taking clear liquid, dripping the clear liquid into low-carbon alcohol, precipitating insoluble substances, carrying out centrifugal separation and filtration, washing the obtained filter residue with the low-carbon alcohol, and drying the filter residue after secondary filtration under a vacuum condition to respectively obtain a product containing the structural unit of the formula 1 or a product containing the structural unit of the formula 2.
3. The method of claim 2, wherein in step S1, the molar ratio of 3, 4-thiophenedicarboxylic acid, dimethyl 1, 4-cyclohexanedione-2, 5-dicarboxylate to diol monomer is (1.0-1.3): 2 (1.0-1.3).
4. The method as claimed in claim 2, wherein the catalyst in step S1 is one of zirconium iso-octoate, bismuth neodecanoate, lead iso-octoate, stannous octoate, antimony acetate, and germanium dioxide.
5. The method according to claim 2, wherein the amount of the catalyst used in step S1 is 0.02 to 0.4% of the amount of the 3, 4-thiophenedicarboxylic acid.
6. The method as claimed in claim 2, wherein the lower alcohol in step S2 is one of methanol, ethanol, propanol, isopropanol, isobutanol, and n-butanol.
7. The method of claim 2, wherein the temperature of the vacuum drying in step S2 is 50-70 ℃ and the drying time is 10-15 hours.
8. The polyvinyl fluoride resin composition is characterized by comprising the following components in parts by weight:
polyvinyl fluoride resin: 100
Plasticizer: 5 to 15
A stabilizer: 1-3;
the plasticizer is the sulfur-containing aromatic polyester according to claim 1.
9. A polyvinyl fluoride resin composition according to claim 8, wherein said stabilizer is one of zinc stearate, tribasic lead sulfate, lead stearate, isooctyl dibutyltin dithioacetate, isooctyl antimony trimercaptoacetate and zinc ricinoleate.
10. A process for producing a polyvinyl fluoride resin composition, which comprises mixing the raw materials of the composition of claim 8 or 9, a plasticizer and a stabilizer thoroughly, and then subjecting the mixture to a subsequent molding process.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114621421A (en) * 2022-04-01 2022-06-14 武汉科技大学 Preparation and application of environment-friendly copolyester and transparent antistatic environment-friendly copolyester film

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1114431A (en) * 1994-04-26 1996-01-03 三井东压化学株式会社 Carboxylate and heat-sensitive recording material using same
JP2005060645A (en) * 2003-07-29 2005-03-10 Toyobo Co Ltd Polyester-based block copolymer and method for producing the same
CN113121805A (en) * 2021-03-09 2021-07-16 武汉科技大学 Preparation and application of sulfur-containing copolyester based on 2, 5-thiophenedicarboxylic acid

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1114431A (en) * 1994-04-26 1996-01-03 三井东压化学株式会社 Carboxylate and heat-sensitive recording material using same
JP2005060645A (en) * 2003-07-29 2005-03-10 Toyobo Co Ltd Polyester-based block copolymer and method for producing the same
CN113121805A (en) * 2021-03-09 2021-07-16 武汉科技大学 Preparation and application of sulfur-containing copolyester based on 2, 5-thiophenedicarboxylic acid

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
李果等: "聚对苯二甲酸-2,5噻吩二羧酸乙二醇共聚酯的合成与表征", 《塑料工业》 *
郑威等: "新型聚2,5-噻吩二羧酸乙二醇酯的合成与表征", 《化工新型材料》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114621421A (en) * 2022-04-01 2022-06-14 武汉科技大学 Preparation and application of environment-friendly copolyester and transparent antistatic environment-friendly copolyester film
CN114621421B (en) * 2022-04-01 2024-01-05 阿尔法(广东)高新材料有限公司 Preparation and application of environment-friendly copolyester and transparent antistatic environment-friendly copolyester film

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