CN107056611B - Reactive plasticizer of polyester compound, preparation method and application thereof - Google Patents

Reactive plasticizer of polyester compound, preparation method and application thereof Download PDF

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CN107056611B
CN107056611B CN201710208182.5A CN201710208182A CN107056611B CN 107056611 B CN107056611 B CN 107056611B CN 201710208182 A CN201710208182 A CN 201710208182A CN 107056611 B CN107056611 B CN 107056611B
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plasticizer
polyester
pbat
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CN107056611A (en
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解孝林
李凯
王勇
周兴平
李晓静
薛志刚
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Huazhong University of Science and Technology
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    • C07C233/09—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having nitrogen atoms of carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with carbon atoms of carboxamide groups bound to carbon atoms of an acyclic unsaturated carbon skeleton
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    • C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
    • C07C69/533—Monocarboxylic acid esters having only one carbon-to-carbon double bond
    • C07C69/54—Acrylic acid esters; Methacrylic acid esters
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
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    • C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
    • C07C69/73—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of unsaturated acids
    • C07C69/732—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of unsaturated acids of unsaturated hydroxy carboxylic acids
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    • C07D319/04—1,3-Dioxanes; Hydrogenated 1,3-dioxanes
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    • C08J3/00—Processes of treating or compounding macromolecular substances
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    • C08K5/00—Use of organic ingredients
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    • C08K5/101—Esters; Ether-esters of monocarboxylic acids
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08K5/10—Esters; Ether-esters
    • C08K5/109—Esters; Ether-esters of carbonic acid, e.g. R-O-C(=O)-O-R
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08K5/00—Use of organic ingredients
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    • C08K5/37—Thiols
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    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2312/00—Crosslinking
    • C08L2312/06—Crosslinking by radiation

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Abstract

The invention discloses a reactive plasticizer of polyester compounds, a preparation method and application thereof. The ester bond can ensure that the plasticizer molecule and the PBAT have good compatibility, and the plasticizer with the ester bond can generate strong acting force with the PBAT molecular chain, generate higher plasticizing effect and reduce the processing temperature. And the barrier property of the polyester can be improved by adding the plasticizer with ester bond. The plasticizer provided by the invention also contains double bonds, and by adding a certain content of the plasticizer into a polyester compound, polymerization reaction can be carried out between the double bonds through post-treatment means such as ultraviolet light or electron beam irradiation, a three-dimensional network is formed in polyester, entanglement among molecular chains is increased, mechanical properties are improved, and the elongation at break is also improved.

Description

Reactive plasticizer of polyester compound, preparation method and application thereof
Technical Field
The invention belongs to the field of material processing, and particularly relates to a reactive plasticizer for reinforcing and toughening a polyester compound, and a preparation method and application thereof.
Background
The aliphatic-aromatic copolyester has good biodegradability, good thermal stability and excellent mechanical property, greatly improves the performance of the original aliphatic polyester, and has good application prospect in the future. PBAT is taken as a representative of the polyester compounds, the tensile strength of the PBAT is more than 20MPa, the elongation at break can reach 500 percent, and the comprehensive performance is excellent. And the elongation at break of the PBAT film is not high enough, the mechanical property of the PBAT film is reduced after the additive is added, and the PBAT film is easy to tear and the like. In addition, PBAT films are not very good in barrier properties because they are linked by polar ester bonds. Particularly in the agricultural field, a film having high water retention properties is required, and thus many problems are faced in the application. To solve this problem, a blocking agent, such as an organic montmorillonite or other water-blocking substance, may be added to the PBAT during processing. However, the method of blocking a substance by an additive causes disadvantages such as high processing cost, reduced product performance, and poor light transmittance.
Disclosure of Invention
Aiming at the defects or improvement requirements of the prior art, the invention provides a reactive plasticizer for reinforcing and toughening a polyester compound, a preparation method and application thereof, and aims to prepare a plasticizer containing ester bonds and double bonds through chemical synthesis, the plasticizer is added into polyester, so that the polyester has better processing performance and the elongation at break of the polyester is improved, and simultaneously, because the plasticizer contains the double bonds, the mechanical property of the polyester can be obviously improved after irradiation treatment, so that the problems that the fat-aromatic copolyester such as PBAT in the prior art is difficult to process and poor in barrier property, the mechanical property is reduced after the addition of an additive, and the polyester is easy to tear are solved; poor light transmission, high cost and the like after the barrier additive is added.
To achieve the above object, according to one aspect of the present invention, there is provided a reactive plasticizer containing an ester bond and a carbon-carbon double bond.
Preferably, the plasticizer has a structure represented by formula (one) or formula (two):
Figure BDA0001260371960000021
wherein R is1，R2，R3，R4，R5，R6，R7，R8，R9，R10，R11，R12And R13Each independently H, C1-C20 alkyl, C1-C20 alkoxy, halogen or amino substituted C1-C20 alkyl, halogen or amino substituted C1-C20 alkoxy or halohydrocarbon; y is O, S, or NH; m and n are independent natural numbers, preferably, m and n are respectively natural numbers of 0-18.
Preferably, the plasticizer has a molecular structure represented by formula (III), formula (IV), formula (V) or formula (VI)
Figure BDA0001260371960000022
According to another aspect of the invention, the plasticizer is prepared by acylating a carboxylic acid or an acid anhydride containing a double bond to obtain an acid chloride compound, and performing an esterification reaction on the acid chloride compound and an alcohol compound.
According to another aspect of the invention, the application of the plasticizer is provided, and the plasticizer is applied to strengthening and toughening of polyester compounds.
Preferably, when the plasticizer is applied to reinforcing and toughening of the polyester compound, the mass fraction of the plasticizer added is 1-50%.
Preferably, the mass fraction of the plasticizer added is 1 to 30%.
According to another aspect of the present invention, there is provided a method for reinforcing and toughening a polyester compound, comprising the steps of:
(1) and uniformly mixing the plasticizer and the polyester compound to obtain a mixture, wherein the mass percent of the plasticizer in the mixture is 1-50%.
Preferably, the reinforcing and toughening method further comprises the following steps:
(2) and (3) irradiating the mixture obtained in the step (1) by adopting ultraviolet light or electron beams to obtain the reinforced and toughened polyester.
Preferably, when the ultraviolet light is adopted for irradiation, the wavelength range of the ultraviolet light is 100-300 nm, and the irradiation time is 1-50 min.
Preferably, when the electron beam irradiation is adopted, the irradiation intensity of the electron beam is 20-200 kGy, and the irradiation time is 1-20 min.
According to another aspect of the invention, a reinforced and toughened PBAT polyester is provided, comprising 1-50% by weight of a plasticizer for reinforcing and toughening the PBAT polyester.
Preferably, compared with pure PBAT polyester, the reinforced and toughened PBAT polyester has the tensile strength improved by 5.4 to 40.8 percent and the elongation at break improved by 13.3 to 130.5 percent
In general, the above technical solutions contemplated by the present invention can achieve the following advantageous effects compared to the prior art.
(1) The invention provides a plasticizer containing polar ester bonds and double bonds, which can ensure that plasticizer molecules and PBAT have good compatibility, and the plasticizer with the ester bonds can generate strong acting force with PBAT molecular chains, generate higher plasticizing effect and reduce processing temperature. And the barrier property of the polyester can be improved by adding the plasticizer with ester bond.
(2) The plasticizer provided by the invention also contains double bonds, and by adding a certain content of the plasticizer into a polyester compound, polymerization reaction can be carried out between the double bonds through post-treatment means such as ultraviolet light or electron beam irradiation, a three-dimensional network is formed in polyester, entanglement among molecular chains is increased, mechanical properties are improved, and the elongation at break is also improved.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The invention provides a reactive plasticizer for polyester plasticization reinforcement, which contains polar ester bonds and carbon-carbon double bonds, such as a structure shown in a formula (I) or a formula (II)
Figure BDA0001260371960000041
Wherein R is1，R2，R3，R4，R5，R6，R7，R8，R9，R10，R11，R12And R13Each independently H, C1-C20 alkyl, C1-C20 alkoxy, halogen or amino substituted C1-C20 alkyl, halogen or amino substituted C1-C20 alkoxy or halohydrocarbon; y is O, S, or NH; m and n are each independently a natural number, preferably, m and n are each independently a natural number of 0 to 18.
Preferred plasticizers have molecular structures represented by formula (iii), formula (iv), formula (v), and formula (vi):
Figure BDA0001260371960000051
the preparation method of the plasticizer provided by the invention can be obtained by acylating chlorination of carboxylic acid or anhydride containing double bonds to obtain acyl chloride compounds, and then carrying out esterification reaction on the acyl chloride compounds and alcohol compounds.
The preparation method of the acyl chloride compound comprises the following steps: uniformly mixing carboxylic acid containing double bonds and thionyl chloride according to the mass ratio of 1:5, and reacting for 4-6 h at 90 ℃ under the action of a catalyst to obtain the acyl chloride compound.
Carboxylic acids containing double bonds such as: acrylic acid or a molecule represented by formula (seven), formula (eight) or formula (nine):
Figure BDA0001260371960000052
the alcohol compound comprises monohydric alcohol, monohydric mercaptan, alkylamine or lactone containing hydroxyl; monohydric alcohols such as methanol, ethanol or isopropanol; monohydric mercaptans such as ethanethiol; alkylamines such as n-butylamine.
Specifically, the plasticizer represented by the formula (one) can be prepared by the following method:
(1) refluxing carboxylic acid containing double bonds, such as acrylic acid, 2-butenoic acid, 4-hydroxy-2 butenoic acid (structural formula is shown as formula (III)), and thionyl chloride at 90 ℃ for 4-6 hours under the action of a catalyst to obtain an acyl chloride compound, wherein the ratio of the carboxylic acid to the thionyl chloride is 1: 5;
Figure BDA0001260371960000061
(2) reacting an acyl chloride compound with compounds such as monohydric alcohol/monohydric mercaptan/alkylamine and the like, wherein the compounds can be methanol, ethanol, isopropanol, ethanethiol, n-butylamine and the like, and preparing the plasticizer shown in the formula (I), wherein the ratio of the acyl chloride to the monohydric alcohol is 1:1, the reaction temperature is 80 ℃, the reaction time is 12 hours, and the reflux is carried out under the protection of inert gas.
The plasticizer represented by the formula (II) can be prepared by the following preparation method:
(1) refluxing carboxylic acid containing double bonds, such as three carboxylic acids shown as a formula (IV), a formula (V) and a formula (VI) with thionyl chloride at 90 ℃ for 6 hours under the action of a catalyst to obtain an acyl chloride compound, wherein the ratio of the carboxylic acid to the thionyl chloride is 1: 5;
(2) refluxing the trihydric alcohol and the dimethyl carbonate at the temperature of 80 ℃ to obtain lactone containing hydroxyl; wherein the triol can be glycerol, tetrahydrofuran is used as solvent, the reaction temperature is 80 ℃, and the reflux is carried out; the mass ratio of the trihydric alcohol to the dimethyl carbonate is 1: 1.
(3) The acyl chloride compound and lactone containing hydroxyl are subjected to reflux reaction for 30 hours at 80 ℃ under the protection of inert gas according to the mass ratio of 1:1 to obtain a target product.
Figure BDA0001260371960000062
The plasticizer provided by the invention can be applied to strengthening and toughening of the polyester compound, and comprises the functions of increasing the tensile strength and the elongation at break of the polyester compound.
When the plasticizer is added into polyester, such as polybutylene adipate/terephthalate (PBAT) and polybutylene terephthalate (PBT), by 1-50 wt%, especially 1-30 wt%, the plasticizer can generate a good plasticizing effect; after the post-treatment is carried out by methods such as ultraviolet irradiation or electron beam irradiation, the mechanical strength and the elongation at break of the material are also greatly improved.
The invention also provides a method for reinforcing and toughening the polyester compound, which comprises the following steps:
(1) the plasticizer is uniformly mixed with the polyester compound to obtain a mixture, wherein the mass percent of the plasticizer in the mixture is 1% -50%.
(2) And (3) irradiating the mixture obtained in the step (1) by adopting ultraviolet light or electron beams to obtain the reinforced and toughened polyester.
When the ultraviolet light is adopted for irradiation, the wavelength range of the ultraviolet light is preferably 100-300 nm, and the irradiation time is preferably 1-50 min;
when the electron beam irradiation is adopted, the intensity of the electron beam irradiation is preferably 20-200 kGy, and the irradiation time is preferably 1-20 min.
The invention also provides a processing method for toughening and reinforcing the polyester by adopting the reactive plasticizer, which comprises the following steps:
(1) uniformly mixing the reactive plasticizer with polyester, and then granulating by using a single-screw extruder to obtain a mixture, wherein the mass percent of the plasticizer in the mixture is 1-50%; processing the mixture by a double-screw extruder to prepare a product;
the processing method of adding the plasticizer into the polyester compound solves the processing defects of the prior art such as overhigh processing temperature and the like during processing of the polyester compound. However, merely mixing a plasticizer with a polyester compound merely increases the elongation at break of the material, and the mechanical properties are rather deteriorated. In order to solve the problem of reduced mechanical properties, the invention utilizes double bonds contained in the plasticizer and adds a post-treatment step, and the preferred post-treatment method is as follows:
(2) and (3) irradiating the product obtained in the step (1) by adopting ultraviolet light or electron beams to obtain the reinforced plasticized polyester.
When the ultraviolet light is adopted for irradiation, the wavelength range of the ultraviolet light is 100-300 nm, and the irradiation time is 1-50 min; when the electron beam is adopted for irradiation, the intensity of the electron beam irradiation is 20-200 kGy, and the irradiation time is 1-20 min.
The novel reinforced and toughened polyester compound can be prepared by adopting the plasticizer and the reinforcing and toughening method, and comprises 1-50% of the plasticizer in percentage by mass, and the plasticizer is used for reinforcing and toughening the polyester compound such as PBAT or PBT. Compared with the existing polyester compound, the novel polyester compound has better mechanical strength and elongation at break.
For example, in example 14 of the present invention, PBAT was plasticized using the plasticizer represented by formula (iii), and when the plasticizer content was 5%, the elongation at break was increased by 170.5%, and the tensile strength was decreased by 7.9%; after the irradiation treatment with the intensity of 30kGy for 5min, the mechanical strength is improved by 18.7 percent, and the elongation at break is improved by 125.4 percent.
Compared with pure PBAT polyester, the reinforced and toughened PBAT polyester provided by the invention has the advantages that the tensile strength is improved by 5.4-40.8%, and the elongation at break is improved by 13.3-130.5%
The invention provides a plasticizer containing polar ester bonds and carbon-carbon double bonds. And the molecular structure of polyester compounds such as PBAT and the like contains a large amount of ester bonds, so that the compatibility of the plasticizer and the PBAT can be ensured. And the plasticizer with ester bonds can generate strong acting force with PBAT molecular chains, generate higher plasticizing effect and reduce processing temperature. And by adding the plasticizer with ester bond, the barrier property can be improved to a certain extent.
However, another problem faced by the addition of plasticizers is the reduction of mechanical properties. Aiming at the problem, the invention synthesizes the plasticizer with double bond structure on the basis of introducing ester bond. By adding a certain content of the plasticizer into the polyester compound and then carrying out post-treatment means such as ultraviolet light or electron beam irradiation, polymerization reaction can be carried out between double bonds, a three-dimensional network is formed in the polyester, the crosslinking and entanglement among molecular chains are increased, and the mechanical property is improved. Meanwhile, the elongation at break of the material is also improved to a certain extent.
The following are examples:
example 1
A preparation method of a polyester reactive plasticizer comprises the following steps:
7.2g of acrylic acid was charged into a 250mL round-bottom flask, followed by 36mL of thionyl chloride, and the reaction was refluxed for 6 hours at 90 ℃ using a serpentine condenser. After the reaction, excess thionyl chloride was distilled off by a rotary evaporator at 35 ℃ and then distilled by an oil pump at 40 ℃ under reduced pressure to obtain 8.64g of acryloyl chloride, the conversion of acrylic acid being 83%. Then 8.64g of acryloyl chloride and 2.66g of methanol are refluxed and reacted for 12 hours at the temperature of 60 ℃, and plasticizer methyl acrylate (shown in the following formula) is obtained.
Figure BDA0001260371960000091
Example 2
A preparation method of a polyester reactive plasticizer comprises the following steps:
8.6g of 2-butenoic acid was charged in a 250mL round-bottom flask, followed by 36mL of thionyl chloride, and the reaction was refluxed at 90 ℃ for 6 hours using a serpentine condenser. After the reaction, excess thionyl chloride was distilled off by a rotary evaporator at 35 ℃ and then distilled by an oil pump at 40 ℃ under reduced pressure to obtain 7.95g of 2-butenoyl chloride, the conversion of 2-butenoic acid being 76%. Then 7.95g of methacryloyl chloride and 3.50g of ethanol are subjected to reflux reaction at the temperature of 60 ℃ for 12 hours to obtain the plasticizer 2-methyl crotonate (shown in the following formula).
Figure BDA0001260371960000092
Example 3
A preparation method of a polyester reactive plasticizer comprises the following steps:
10.2g of 4-hydroxy-2-butenoic acid was charged into a 250mL round-bottom flask, followed by 36mL of thionyl chloride, and the reaction was refluxed at 90 ℃ for 6 hours using a serpentine condenser. After the reaction, excess thionyl chloride was distilled off by a rotary evaporator at 35 ℃ and then distilled by an oil pump at 40 ℃ under reduced pressure to obtain 8.196g of 4-hydroxy-2-butenoyl chloride, the conversion of 4-hydroxy-2-butenoic acid being 68%. 8.196g of 4-hydroxy-2-butenoyl chloride and 4.087g of isopropanol are subjected to reflux reaction at 60 ℃ for 12 hours to obtain the plasticizer isopropyl 4-hydroxy-2-butenoate (shown in the following formula).
Figure BDA0001260371960000093
Example 4
A preparation method of a polyester reactive plasticizer comprises the following steps:
8.6g of 2-butenoic acid was charged in a 250mL round-bottom flask, followed by 36mL of thionyl chloride, and the reaction was refluxed at 90 ℃ for 6 hours using a serpentine condenser. After the reaction, excess thionyl chloride was distilled off by a rotary evaporator at 35 ℃ and then distilled by an oil pump at 40 ℃ under reduced pressure to obtain 7.95g of 2-butenoyl chloride, the conversion of 2-butenoic acid being 76%. Then 7.95g of methacryloyl chloride and 4.72g of ethanethiol are refluxed and reacted for 12 hours at the temperature of 60 ℃ to obtain the plasticizer 2-butenoic acid ethanethiol ester (shown as the following formula).
Figure BDA0001260371960000101
Example 5
A preparation method of a polyester reactive plasticizer comprises the following steps:
7.2g of acrylic acid was charged into a 250mL round-bottom flask, followed by 36mL of thionyl chloride, and the reaction was refluxed for 6 hours at 90 ℃ using a serpentine condenser. After the reaction, excess thionyl chloride was distilled off by a rotary evaporator at 35 ℃ and then distilled by an oil pump at 40 ℃ under reduced pressure to obtain 8.64g of acryloyl chloride, the conversion of acrylic acid being 83%. Then 8.64g of acryloyl chloride was reacted with 6.31g of n-butylamine under reflux at 60 ℃ for 12 hours to obtain n-butylamino acrylate (shown below).
Figure BDA0001260371960000102
Example 6
A preparation method of a polyester reactive plasticizer comprises the following steps:
11.6g of maleic acid (represented by formula (4)) was charged into a 250mL round-bottom flask, followed by 72mL of thionyl chloride, and the reaction was refluxed at 90 ℃ for 6 hours using a serpentine condenser. After the reaction, excess thionyl chloride was distilled off by a rotary evaporator at 35 ℃ and then distilled by an oil pump at 70 ℃ under reduced pressure to obtain 12.39g of maleic acid dichloride with a maleic acid conversion of 81%.
9.2g of glycerol, 9.0g of dimethyl carbonate and 45mL of tetrahydrofuran were placed in a round-bottomed flask and refluxed at 80 ℃ for 12 hours. After the reaction is finished, the reaction product is distilled by a rotary evaporator under reduced pressure at the temperature of 30 ℃ to obtain the 2-hydroxy propylene carbonate.
Then 2-hydroxy propylene carbonate and maleic acid dichloride are added into the flask according to the molar weight of 2:1 and added into the flask in N2Reacting for 30 hours at the temperature of 80 ℃ in the atmosphere to obtain the plasticizer shown in the following formula.
Figure BDA0001260371960000111
Example 7
A preparation method of a polyester reactive plasticizer comprises the following steps:
12.0g of the compound represented by the formula (5) was charged into a 150mL round-bottomed flask, followed by addition of 36mL of thionyl chloride, and the reaction was refluxed for 6 hours at 90 ℃ using a serpentine condenser. After the reaction, excess thionyl chloride was distilled off by a rotary evaporator at 35 ℃ and then distilled by an oil pump at 60 ℃ under reduced pressure to give 11.8g of an acyl chloride compound with a conversion of 85%.
9.2g of glycerol, 9.0g of dimethyl carbonate and 45mL of tetrahydrofuran were placed in a round-bottomed flask and refluxed at 80 ℃ for 12 hours. After the reaction is finished, the reaction product is distilled by a rotary evaporator under reduced pressure at the temperature of 30 ℃ to obtain the 2-hydroxy propylene carbonate.
Then 2-hydroxy propylene carbonate and acyl chloride compound are added into the flask according to the molar weight of 1:1, and the mixture is added into the flask in N2Reacting for 30 hours at the temperature of 80 ℃ in the atmosphere to obtain the plasticizer shown in the following formula.
Figure BDA0001260371960000112
Example 8
A preparation method of a polyester reactive plasticizer comprises the following steps:
8.6g of the compound represented by the formula (6) was charged into a 150mL round-bottomed flask, followed by addition of 36mL of thionyl chloride, and the reaction was refluxed for 6 hours at 90 ℃ using a serpentine condenser. After the reaction was completed, excess thionyl chloride was distilled off by a rotary evaporator at 35 ℃ and then distilled under reduced pressure at 55 ℃ by an oil pump to obtain 8.8g of an acid chloride compound with a conversion of 84%.
9.2g of glycerol, 9.0g of dimethyl carbonate and 45mL of tetrahydrofuran were placed in a round-bottomed flask and refluxed at 80 ℃ for 12 hours. After the reaction is finished, the reaction product is distilled by a rotary evaporator under reduced pressure at the temperature of 30 ℃ to obtain the 2-hydroxy propylene carbonate.
Then 2-hydroxy propylene carbonate and acyl chloride compound are added into the flask according to the molar weight of 1:1, and the mixture is added into the flask in N2Reacting for 30 hours at the temperature of 80 ℃ in the atmosphere to obtain the plasticizer shown in the following formula.
Figure BDA0001260371960000121
Example 9
A processing method for plasticizing and reinforcing PBAT by methyl acrylate, which comprises the following steps:
uniformly stirring PBAT and methyl acrylate in a high-speed mixer according to the mass ratio of 99:1, adding the mixture into a single-screw extruder, extruding and granulating, and drying the obtained mixture particles in an oven. And finally, adding the dried mixture into a double-screw extruder, and preparing dumbbell-shaped sample bars through a die. The resulting dumbbell-shaped bars were divided into three groups, labeled A, B, C.
Group A was irradiated under 100nm wavelength UV for 1min, and group C was irradiated under 300nm wavelength UV for 50min without any post-treatment.
The three groups of sample strips are respectively subjected to tensile tests, and compared with the group A, the tensile strength of the sample strips in the group B is increased by 21.4%, and the elongation at break is increased by 38.9%; the tensile strength of the C group specimens increased by 33.5% and the elongation at break increased by 13.3%.
Example 10
The PBT was plasticized and reinforced with the plasticizer prepared in example 4 (shown below) in the following manner:
Figure BDA0001260371960000122
the plasticizer prepared in example 4 and PBT are uniformly stirred in a high-speed mixer with the mass ratio of 50:50, then the mixture is added into a single-screw extruder to be extruded and granulated, and the obtained mixture particles are dried in an oven. And finally, adding the dried mixture into a double-screw extruder, and preparing dumbbell-shaped sample bars through a die. The resulting dumbbell-shaped bars were divided into three groups, labeled A, B, C.
The group A was irradiated with an electron beam having an irradiation intensity of 20kGy for 20min, and the group B was irradiated with an electron beam having an intensity of 200kGy for 1min, without any post-treatment.
The two groups of sample strips are respectively subjected to tensile tests, and compared with a pure PET sample strip A, the tensile strength of the sample strip B is increased by 23.5%, and the elongation at break is increased by 25.7%; the tensile strength of the C group specimens increased by 27.9% and the elongation at break increased by 34.5%.
Example 11
The plasticizer enhancement of PBAT was performed using the plasticizer prepared in example 8 (shown below) as follows:
Figure BDA0001260371960000131
the plasticizer prepared in example 8 and PBAT were uniformly stirred in a high mixing machine at a mass ratio of 50:50, and then added to a single-screw extruder to be extruded and granulated, and the resulting mixture pellets were dried in an oven. And finally, adding the dried mixture into a double-screw extruder, and preparing dumbbell-shaped sample bars through a die. The resulting dumbbell-shaped bars were divided into three groups, labeled A, B, C.
The group A was irradiated with an electron beam having an irradiation intensity of 80kGy for 10min, and the group B was irradiated with an electron beam having an intensity of 200kGy for 5min, without any post-treatment.
The three groups of sample strips are respectively subjected to tensile tests, and compared with the group A, the tensile strength of the sample strips in the group B is increased by 40.8%, and the elongation at break is increased by 117.5%; the tensile strength of the C group specimens increased by 53.2% and the elongation at break increased by 80.5%.
Example 12
The plasticizer enhancement of PBAT was performed using the plasticizer prepared in example 5 (shown below) as follows:
Figure BDA0001260371960000141
the plasticizer prepared in example 5 and PBAT are uniformly stirred in a high-speed mixer with the mass ratio of 10:90, then the mixture is added into a single-screw extruder to be extruded and granulated, and the obtained mixture particles are dried in an oven. And finally, adding the dried mixture into a double-screw extruder, and preparing dumbbell-shaped sample bars through a die. The resulting dumbbell-shaped bars were divided into two groups, labeled A, B.
The group A was not subjected to any post-treatment, and the group B was irradiated with an electron beam having an irradiation intensity of 80kGy for 10 min. The three groups of sample strips are respectively subjected to tensile test, and compared with the group A, the tensile strength of the sample strip in the group B is increased by 10.4%, and the elongation at break is increased by 130.5%.
Respectively carrying out infrared tests on pure PBAT without adding the plasticizer, PBAT (group A) without adding the plasticizer and after-treatment and PBAT (group B) with adding the plasticizer and after irradiation treatment, wherein the obtained infrared spectrogram shows that the peak (wave number is 1641 cm) of the double bonds of the PBAT in the group B after adding the plasticizer and after-treatment-1Where) substantially disappears.
Example 13
The plasticizer enhancement of PBAT was performed using the plasticizer prepared in example 5, as follows:
the plasticizer prepared in example 5 and PBAT are uniformly stirred in a high-speed mixer with the mass ratio of 20:80, then the mixture is added into a single-screw extruder to be extruded and granulated, and the obtained mixture particles are dried in an oven. And finally, adding the dried mixture into a double-screw extruder, and preparing dumbbell-shaped sample bars through a die. The resulting dumbbell-shaped bars were divided into two groups, labeled A, B.
The group A was not subjected to any post-treatment, and the group B was irradiated with an electron beam having an irradiation intensity of 50kGy for 5 min.
Compared with pure PBAT, the elongation at break of the A group sample strip is improved by 124.3 percent, and the tensile strength is reduced by 15.2 percent; the elongation at break of the B group sample strip is improved by 81.2 percent, and the tensile strength is improved by 13.4 percent.
Example 14
The plasticizer enhancement of PBAT was performed using the plasticizer prepared in example 5, as follows:
the plasticizer prepared in example 5 and PBAT are uniformly stirred in a high-speed mixer with the mass ratio of 5:95, then the mixture is added into a single-screw extruder to be extruded and granulated, and the obtained mixture particles are dried in an oven. And finally, adding the dried mixture into a double-screw extruder, and preparing dumbbell-shaped sample bars through a die.
The mechanical property test is carried out on the sample strip, the breaking elongation of the sample strip is improved by 170.5 percent, and the tensile strength is reduced by 7.9 percent; after the irradiation treatment with the strength of 30kGy for 5min, the tensile strength is improved by 18.7 percent, and the elongation at break is improved by 125.4 percent.
Example 15
The PBAT was plasticised and enhanced with the plasticiser prepared in example 7 (shown in the following scheme) as follows:
Figure BDA0001260371960000151
the plasticizer prepared in example 7 and PBAT were uniformly stirred in a high-speed mixer at a mass ratio of 10:90, and then added to a single-screw extruder to be extruded and granulated, and the resulting mixture pellets were dried in an oven. And finally, adding the dried mixture into a double-screw extruder, and preparing dumbbell-shaped sample bars through a die. The resulting dumbbell-shaped bars were divided into three groups, labeled A, B.
The group A was not subjected to any post-treatment, and the group B was irradiated with an electron beam having an irradiation intensity of 50kGy for 5 min.
Compared with pure PBAT, the elongation at break of the A group sample strip is improved by 140.5 percent, and the tensile strength is reduced by 32.4 percent; the elongation at break of the B group sample strip is improved by 95.4 percent, and the tensile strength is improved by 5.4 percent.
Example 16
The PBAT was plasticised and enhanced with the plasticiser prepared in example 6 (shown in the following scheme) as follows:
Figure BDA0001260371960000161
the plasticizer prepared in example 6 and PBAT are uniformly stirred in a high-speed mixer at a mass ratio of 30:70, then the mixture is added into a single-screw extruder to be extruded and granulated, and the obtained mixture particles are dried in an oven. And finally, adding the dried mixture into a double-screw extruder, and preparing dumbbell-shaped sample bars through a die. The resulting dumbbell-shaped bars were divided into three groups, labeled A, B.
The group A was not subjected to any post-treatment, and the group B was irradiated with an electron beam having an irradiation intensity of 50kGy for 5 min.
Compared with pure PBAT, the elongation at break of the A group sample strip is improved by 167.8 percent, and the tensile strength is reduced by 45.9 percent; the elongation at break of the B group sample strip is improved by 120.6 percent, and the tensile strength is improved by 8.4 percent.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims (2)

1. A method for reinforcing and toughening a polyester compound is characterized by comprising the following steps:
(1) uniformly mixing a plasticizer and a polyester compound to obtain a mixture, wherein the mass percent of the plasticizer in the mixture is 1-50%;
(2) irradiating the mixture obtained in the step (1) by adopting ultraviolet light or electron beams to obtain reinforced and toughened polyester;
when the ultraviolet light is adopted for irradiation, the wavelength range of the ultraviolet light is 100-300 nm, and the irradiation time is 1-50 min;
when the electron beam is adopted for irradiation, the intensity of the electron beam irradiation is 20-200 kGy, and the irradiation time is 1-20 min;
the polyester compound is PBAT or PBT; the plasticizer has a molecular structure shown as a formula (I), a formula (IV), a formula (V) or a formula (VI):
Figure FDA0002399303560000011
wherein R is1，R2，R3And R4Each independently is H, C1-C20 alkyl or C1-C20 alkoxy; y is O, S, or NH; m is 0.
2. The method of claim 1, wherein the polyester-based compound is a PBAT polyester; compared with pure PBAT polyester, the adoption of the reinforcing and toughening method can improve the tensile strength of the PBAT polyester by 5.4-40.8% at most and improve the elongation at break by 13.3-130.5% at most.
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