CN117417515A - 2-methyl-2-carbobenzoxy-1, 3-propanediol modified PBAT material and preparation method thereof - Google Patents
2-methyl-2-carbobenzoxy-1, 3-propanediol modified PBAT material and preparation method thereof Download PDFInfo
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- CN117417515A CN117417515A CN202311734093.6A CN202311734093A CN117417515A CN 117417515 A CN117417515 A CN 117417515A CN 202311734093 A CN202311734093 A CN 202311734093A CN 117417515 A CN117417515 A CN 117417515A
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- 239000000463 material Substances 0.000 title claims abstract description 50
- VGFNGLUDOVQRNF-UHFFFAOYSA-N benzyl 3-hydroxy-2-(hydroxymethyl)-2-methylpropanoate Chemical compound OCC(C)(CO)C(=O)OCC1=CC=CC=C1 VGFNGLUDOVQRNF-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 229920001896 polybutyrate Polymers 0.000 title claims abstract 17
- 238000005886 esterification reaction Methods 0.000 claims abstract description 57
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims abstract description 52
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 238000010438 heat treatment Methods 0.000 claims abstract description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 24
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 23
- 239000003607 modifier Substances 0.000 claims abstract description 21
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000001361 adipic acid Substances 0.000 claims abstract description 12
- 235000011037 adipic acid Nutrition 0.000 claims abstract description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 230000032050 esterification Effects 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000000155 melt Substances 0.000 claims description 11
- JVZZUPJFERSVRN-UHFFFAOYSA-N 2-methyl-2-propylpropane-1,3-diol Chemical compound CCCC(C)(CO)CO JVZZUPJFERSVRN-UHFFFAOYSA-N 0.000 claims description 7
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 6
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 claims description 6
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 claims description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 5
- 230000009194 climbing Effects 0.000 claims description 5
- JCTXKRPTIMZBJT-UHFFFAOYSA-N 2,2,4-trimethylpentane-1,3-diol Chemical compound CC(C)C(O)C(C)(C)CO JCTXKRPTIMZBJT-UHFFFAOYSA-N 0.000 claims description 3
- RWLALWYNXFYRGW-UHFFFAOYSA-N 2-Ethyl-1,3-hexanediol Chemical compound CCCC(O)C(CC)CO RWLALWYNXFYRGW-UHFFFAOYSA-N 0.000 claims description 3
- JULNEFHJBRHDSM-UHFFFAOYSA-N 2-ethylbutane-1,3-diol Chemical compound CCC(CO)C(C)O JULNEFHJBRHDSM-UHFFFAOYSA-N 0.000 claims description 3
- HYFFNAVAMIJUIP-UHFFFAOYSA-N 2-ethylpropane-1,3-diol Chemical compound CCC(CO)CO HYFFNAVAMIJUIP-UHFFFAOYSA-N 0.000 claims description 3
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical compound OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 claims description 3
- FZHZPYGRGQZBCV-UHFFFAOYSA-N 2-propylpropane-1,3-diol Chemical compound CCCC(CO)CO FZHZPYGRGQZBCV-UHFFFAOYSA-N 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- 229920000180 alkyd Polymers 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 230000004048 modification Effects 0.000 abstract description 5
- 238000012986 modification Methods 0.000 abstract description 5
- 230000015556 catabolic process Effects 0.000 abstract description 4
- 238000006731 degradation reaction Methods 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 239000002861 polymer material Substances 0.000 abstract description 2
- 239000004629 polybutylene adipate terephthalate Substances 0.000 description 34
- 230000000704 physical effect Effects 0.000 description 4
- 238000005086 pumping Methods 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 229920006238 degradable plastic Polymers 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 229920001634 Copolyester Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229920003232 aliphatic polyester Polymers 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920000704 biodegradable plastic Polymers 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000009264 composting Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- -1 polybutylene adipate terephthalate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/19—Hydroxy compounds containing aromatic rings
-
- 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
- C08G63/78—Preparation processes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention relates to the technical field of modification of biodegradable high polymer materials, in particular to a 2-methyl-2-carbobenzoxy-1, 3-propanediol modified PBAT material and a preparation method thereof. The preparation method comprises the following steps: adding 1, 4-butanediol, terephthalic acid, a modifier and a catalyst into a reaction kettle, introducing nitrogen for replacement, and heating to perform a first esterification reaction; adipic acid, 1, 4-butanediol, a modifier and a catalyst are added into a reaction kettle, nitrogen is introduced for replacement, and then the mixture is heated for the second esterification reaction. Mixing the product of the first esterification reaction and the product of the second esterification reaction, adding a catalyst, slowly heating, and performing pre-polycondensation reaction in a vacuum environment; heating and carrying out polycondensation reaction in a vacuum environment to obtain the PBAT modified material. The method improves the degradation performance and environmental protection performance of the material, and reduces the production cost and the process complexity, thereby realizing the efficient, economic and environmental protection PBAT material production.
Description
Technical Field
The invention relates to the technical field of modification of biodegradable high polymer materials, in particular to a 2-methyl-2-carbobenzoxy-1, 3-propanediol modified PBAT material and a preparation method thereof.
Background
Degradable polyester materials have been widely used such as films, foams, injection molded articles, etc. The material has good physical properties, can be degraded into water and carbon dioxide in a composting or natural state, and has no potential hazard to the environment. Among them, polybutylene adipate terephthalate (PBAT) is one of the very active degradation materials in the current biodegradable plastic research, but most of these materials are composed of aliphatic polyesters or aliphatic/aromatic copolyesters, but the price is relatively expensive, the material strength is poor, therefore, the preparation method of PBAT copolymerization modified materials with lower cost and excellent performance is provided, and has important significance.
Disclosure of Invention
First, the technical problem to be solved
The invention mainly aims at the problems, and provides a 2-methyl-2-carbobenzoxy-1, 3-propanediol modified PBAT material and a preparation method thereof, aiming at solving the problems of high cost and limited application of degradable plastics of the existing PBAT material.
(II) technical scheme
To achieve the above object, the first aspect of the present invention provides a method for preparing a 2-methyl-2-benzyloxycarbonyl-1, 3-propanediol-modified PBAT material, comprising the steps of:
adding 1, 4-butanediol, terephthalic acid, a modifier and a catalyst into a reaction kettle, introducing nitrogen for replacement, and heating to perform a first esterification reaction;
adding adipic acid, 1, 4-butanediol, a modifier and a catalyst into a reaction kettle, introducing nitrogen for replacement, and heating for a second esterification reaction; mixing the product of the first esterification reaction and the product of the second esterification reaction, adding a catalyst, slowly heating, and performing pre-polycondensation reaction in a vacuum environment;
heating and carrying out polycondensation reaction in a vacuum environment to obtain the PBAT modified material.
Further, the modifier is one or more of dialkyl alcohols such as 2-methyl-2-carbobenzoxy-1, 3-propanediol, 2-methyl-1, 3-propanediol, 2-ethyl-1, 3-butanediol, 2-ethyl-1, 3-propanediol, 2-n-propyl-1, 3-propanediol, 2-methyl-2-propyl-1, 3-propanediol, 2-ethyl-3-propyl-1, 3-propanediol, 2, 4-trimethyl-1, 3-pentanediol and the like, wherein the 2-methyl-2-carbobenzoxy-1, 3-propanediol is used as the best performance.
Further, the catalyst adopted in the first and second esterification processes is a mixture of tetrabutyl titanate, triethyl phosphate and antimony trioxide.
Further, in the first esterification step, the molar ratio of 1, 4-butanediol, terephthalic acid and the modifier is 1.4:1, wherein the 1, 4-butanediol accounts for 95% of the alcohol content, and the modifier is 5% of the alcohol content.
Further, in the second esterification step, the molar ratio of the 1, 4-butanediol to the adipic acid to the modifier is 1.4:1, wherein the 1, 4-butanediol accounts for 95% of the alcohol content, and the modifier accounts for 5% of the alcohol content.
Further, the temperature of the first esterification reaction is 190 ℃, the water yield reaches more than 95% of the theoretical water yield, and the reaction is carried out until the melt is clear, namely the end point of the esterification reaction; the temperature of the second esterification reaction is 180 ℃, the water yield reaches more than 95% of the theoretical water yield, and the reaction is carried out until the melt is clear, namely the end point of the esterification reaction.
Further, the catalyst used in the pre-polymerization process is tin isooctanoate.
Further, in the pre-polycondensation process, the product of the first esterification reaction and the product of the second esterification reaction are mixed, the temperature is slowly raised to 220 ℃, the vacuum is controlled to be 0.02-0.08Mpa, and the pre-polycondensation time is half an hour.
Further, in the final polycondensation step, after the pre-polycondensation reaches the end point, heating to 230-240 ℃ to carry out polycondensation reaction, slowly pumping to high vacuum, controlling the vacuum to be-0.1 MPa, and obtaining the PBAT modified material when the modified PBAT has the 'pole climbing' phenomenon, namely the reaction end point.
In order to achieve the above object, a second aspect of the present invention provides a modified PBAT material prepared using the above preparation method.
(III) beneficial effects
According to the 2-methyl-2-carbobenzoxy-1, 3-propanediol modified PBAT material and the preparation method, dialkyl alcohol is added in the esterification process of PBAT for direct polymerization, so that the molecular structure and physical properties of PBAT can be effectively changed. The dialkyl alcohol is inserted between the PBAT molecular chains as a flexible chain segment, so that the processability and degradability of the PBAT can be enhanced, and the production process is simpler, more convenient and more efficient. Compared with the prior art, the method not only improves the degradation performance and environmental protection performance of the material, but also reduces the production cost and the process complexity, thereby realizing the efficient, economic and environmental protection PBAT material production.
Detailed Description
The following describes the embodiments of the present invention in further detail with reference to examples. The following examples are illustrative of the invention and are not intended to limit the scope of the invention.
To solve the problems of existing PBAT materials such as; the biggest obstacle to replacing traditional plastics at present is that the production cost is higher than that of similar traditional plastics or regenerated plastics. Therefore, the degradable plastic has more advantages in the application of short service time, difficult recovery and separation, low performance requirement and high impurity content requirement of packaging, agricultural films and the like. The invention provides a 2-methyl-2-carbobenzoxy-1, 3-propanediol modified PBAT material and a preparation method thereof, comprising the following steps:
adding 1, 4-butanediol, terephthalic acid, a modifier and a catalyst into a reaction kettle, introducing nitrogen for replacement, and heating to perform a first esterification reaction; adipic acid, 1, 4-butanediol, a modifier and a catalyst are added into a reaction kettle, nitrogen is introduced for replacement, and then the mixture is heated for the second esterification reaction. Mixing the product of the first esterification reaction and the product of the second esterification reaction, adding a catalyst, slowly heating, and performing pre-polycondensation reaction in a vacuum environment; heating and carrying out polycondensation reaction in a vacuum environment to obtain the PBAT structure modified material.
The reaction mechanism is as follows:
compared with the prior art, the preparation method of the 2-methyl-2-carbobenzoxy-1, 3-propanediol modified PBAT material provided by the invention has the advantages that the key parameters such as the material mole ratio, the temperature and the like are effectively controlled by setting the reaction conditions and the steps of esterification, pre-polycondensation and polycondensation in detail, so that the optimized modification of the PBAT structure is realized. The method not only improves the reaction efficiency and the degradation speed of the product and reduces the production cost of the material, but also ensures that the obtained PBAT material has better physical property and biodegradability, so that the PBAT material has wider application prospect and advantage in the fields of packaging, agricultural films and the like.
For example, the following steps may be employed:
the modifier is one or more selected from dialkyl alcohols such as 2-methyl-2-carbobenzoxy-1, 3-propanediol, 2-methyl-1, 3-propanediol, 2-ethyl-1, 3-butanediol, 2-ethyl-1, 3-propanediol, 2-n-propyl-1, 3-propanediol, 2-methyl-2-propyl-1, 3-propanediol, 2-ethyl-3-propyl-1, 3-propanediol, 2, 4-trimethyl-1, 3-pentanediol, and the like, and the effect is better when 2-methyl-2-carbobenzoxy-1, 3-propanediol is selected.
In the second esterification step, the molar ratio of 1, 4-butanediol, adipic acid and modifier alkyd was 1.4:1, wherein 1, 4-butanediol accounted for 95% of the alcohol content and the modifier was 5% of the alcohol content. The esterification temperature of the second esterification reaction was 180 ℃. The water yield reaches more than 95% of the theoretical water yield, and the reaction is carried out until the melt is clear, namely the end point of the esterification reaction.
In the pre-polycondensation process, the product of the first esterification reaction and the product of the second esterification reaction are mixed, a catalyst tin isooctanoate is added, the temperature is slowly increased to 220 ℃, the vacuum is controlled to be 0.02-0.08Mpa, and the pre-polycondensation time is half an hour.
In the final polycondensation step, heating to 230-240 ℃, slowly pumping to high vacuum, controlling the vacuum to be below-0.1 MPa, and obtaining the PBAT modified material when the modified PBAT has a pole climbing phenomenon, namely a reaction end point.
The raw materials and equipment used in the present invention are all common materials and equipment in the art unless otherwise specified.
The present invention will be described in further detail with reference to specific embodiments thereof so that those skilled in the art can better understand the present invention.
Example 1
First esterification: 1, 4-butanediol, terephthalic acid, 2-methyl-2-carbobenzoxy-1, 3-propanediol and a catalyst (tetrabutyl titanate, triethyl phosphate and antimony trioxide mixture accounting for five thousandths of the total reactant mass) are added into a reaction kettle provided with a heating device, a stirrer, a return pipe and a condensing pipe, the molar ratio of 1, 4-butanediol to terephthalic acid to 2-methyl-2-carbobenzoxy-1, 3-propanediol is 1.4:1, nitrogen is introduced for replacement, and then the mixture is heated to 190 ℃ to start the first esterification reaction to generate water, the water yield is more than 95% of the theoretical water yield, and the reaction is carried out until the melt becomes clear, namely the end point of the esterification reaction.
Second esterification: adding 1, 4-butanediol, adipic acid, 2-methyl-2-benzyloxycarbonyl-1, 3-propanediol and a catalyst (tetrabutyl titanate, triethyl phosphate and antimony trioxide mixture accounting for five thousandths of the total reactant mass) into a reaction kettle provided with a heating device, a stirrer, a return pipe and a condensing pipe, wherein the molar ratio of 1, 4-butanediol to adipic acid to 2-methyl-2-benzyloxycarbonyl-1, 3-propanediol is 1.4:1, introducing nitrogen for replacement, heating to 180 ℃ to start the first esterification reaction to generate water, the water yield is more than 95% of the theoretical water yield, and reacting until a melt becomes clear, namely the esterification reaction end point. Pre-polycondensation: mixing the product of the first esterification reaction and the product of the second esterification reaction, adding a catalyst tin isooctanoate (accounting for five thousandths of the total reaction mass), slowly heating to 220 ℃, controlling vacuum to 0.04MPa, and carrying out half-hour pre-polycondensation reaction.
And (3) final polycondensation: after the preshrinking reaches the end point, heating to 240 ℃ for polycondensation reaction, slowly pumping to high vacuum, controlling the vacuum to be-0.1 MPa, and obtaining the PBAT modified material when the modified PBAT has the phenomenon of climbing a rod, namely the reaction end point.
Example 2
First esterification: 1, 4-butanediol, terephthalic acid, 2-methyl-2-propyl-1, 3-propanediol and a catalyst (tetrabutyl titanate, triethyl phosphate and antimony trioxide mixture accounting for five thousandths of the total reactant mass) are added into a reaction kettle provided with a heating device, a stirrer, a return pipe and a condensing pipe, the molar ratio of 1, 4-butanediol to adipic acid to terephthalic acid to 2-methyl-2-propyl-1, 3-propanediol is 1.4:1, nitrogen is introduced for replacement, and then the mixture is heated to 180 ℃ to start the first esterification reaction to generate water, the water yield reaches 95% of the theoretical water yield, and the reaction is carried out until the melt becomes clear.
Second esterification: adding 1, 4-butanediol, adipic acid, 2-methyl-2-propyl-1, 3-propanediol and a catalyst (tetrabutyl titanate, triethyl phosphate and antimony trioxide mixture accounting for five thousandths of the total reactant mass) into a reaction kettle provided with a heating device, a stirrer, a return pipe and a condensing pipe, wherein the molar ratio of 1, 4-butanediol to adipic acid to 2-methyl-2-propyl-1, 3-propanediol is 1.4:1, introducing nitrogen for replacement, heating to 180 ℃ to start the first esterification reaction to generate water, the water yield is more than 95% of the theoretical water yield, and reacting until the melt becomes clear, namely the end point of the esterification reaction.
Pre-polycondensation: mixing the product of the first esterification reaction and the product of the second esterification reaction, adding a catalyst tin isooctanoate (accounting for five thousandths of the total reaction mass), slowly heating to 220 ℃, controlling vacuum to 0.04MPa, and carrying out half-hour pre-polycondensation reaction.
And (3) final polycondensation: after the preshrinking reaches the end point, heating to 240 ℃ for polycondensation reaction, slowly pumping to high vacuum, controlling the vacuum to be below 0.1 Pa, and obtaining the PBAT modified material when the modified PBAT has the phenomenon of 'climbing rod', namely the reaction end point.
TABLE 1
The additive-free group experiments were performed to compare the performance changes of the additive groups and the magnitude of the effect of the introduction of functional groups on their performance.
The smaller the melt index of the PBAT structure modified material is, the larger the molecular weight is, which shows that the breaking strength, hardness, toughness, aging resistance, stability and other properties of the PBAT structure modified material are all improved; the smaller the variation amplitude of the melt index after 8 hours of reaction, the better the performance of the PBAT structure modified material is shown.
TABLE 2
As can be seen from Table 2 above, sample 1 has a greater tensile strength, flexural modulus, and notched Izod impact strength than sample 2, indicating that the physical properties of the material are more excellent when 2-methyl-2-benzyloxycarbonyl-1, 3-propanediol is added.
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that it will be apparent to those skilled in the art that modifications and variations can be made without departing from the technical principles of the present invention, and these modifications and variations should also be regarded as the scope of the invention.
Claims (10)
1. The preparation method of the 2-methyl-2-carbobenzoxy-1, 3-propanediol modified PBAT material is characterized by comprising the following steps:
adding 1, 4-butanediol, terephthalic acid, a modifier and a catalyst into a reaction kettle, introducing nitrogen for replacement, and heating to perform a first esterification reaction;
adding adipic acid, 1, 4-butanediol, a modifier and a catalyst into a reaction kettle, introducing nitrogen for replacement, and heating for a second esterification reaction; mixing the product of the first esterification reaction and the product of the second esterification reaction, adding a catalyst, slowly heating, and performing pre-polycondensation reaction in a vacuum environment;
heating and carrying out polycondensation reaction in a vacuum environment to obtain the PBAT modified material.
2. The method for preparing 2-methyl-2-carbobenzoxy-1, 3-propanediol modified PBAT material as claimed in claim 1, wherein the modifier is one or more of 2-methyl-2-carbobenzoxy-1, 3-propanediol, 2-methyl-1, 3-propanediol, 2-ethyl-1, 3-butanediol, 2-ethyl-1, 3-propanediol, 2-n-propyl-1, 3-propanediol, 2-methyl-2-propyl-1, 3-propanediol, 2-ethyl-3-propyl-1, 3-propanediol, 2, 4-trimethyl-1, 3-pentanediol.
3. The method for preparing 2-methyl-2-carbobenzoxy-1, 3-propanediol modified PBAT material as recited in claim 1, wherein the catalyst used in the first and second esterification processes is a mixture of tetrabutyl titanate, triethyl phosphate and antimony trioxide.
4. The method for preparing a 2-methyl-2-benzyloxycarbonyl-1, 3-propanediol modified PBAT material according to claim 1, wherein in the first esterification step, the molar ratio of 1, 4-butanediol, terephthalic acid and modifier alkyd is 1.4:1, wherein 1, 4-butanediol comprises 95% of the alcohol content and the modifier is 5% of the alcohol content.
5. The method for preparing a 2-methyl-2-carbobenzoxy-1, 3-propanediol modified PBAT material as recited in claim 1, wherein in the second esterification step, the molar ratio of 1, 4-butanediol, adipic acid and modifier is 1.4:1, wherein 1, 4-butanediol accounts for 95% of the alcohol content, and the modifier accounts for 5% of the alcohol content.
6. The method for preparing 2-methyl-2-carbobenzoxy-1, 3-propanediol modified PBAT material as claimed in claim 1, wherein the temperature of the first esterification reaction is 190 ℃, the water yield is more than 95% of the theoretical water yield, and the reaction is carried out until the melt is clear, namely the end point of the esterification reaction; the temperature of the second esterification reaction is 180 ℃, the water yield reaches more than 95% of the theoretical water yield, and the reaction is carried out until the melt is clear, namely the end point of the esterification reaction.
7. The method for preparing a 2-methyl-2-carbobenzoxy-1, 3-propanediol modified PBAT material as recited in claim 1, wherein the catalyst used in the pre-polymerization process is tin isooctanoate.
8. The method for preparing 2-methyl-2-carbobenzoxy-1, 3-propanediol modified PBAT material as claimed in claim 1, wherein the product of the first esterification reaction and the product of the second esterification reaction are mixed in the pre-polycondensation process, the temperature is slowly raised to 220 ℃, the vacuum is controlled to 0.04Mpa, and the pre-polycondensation time is half an hour.
9. The method for preparing a 2-methyl-2-carbobenzoxy-1, 3-propanediol modified PBAT material as claimed in claim 1, wherein in the final polycondensation step, after the pre-polycondensation reaches the end point, the temperature is raised to 240 ℃ for polycondensation reaction, the high vacuum is slowly pumped, the vacuum is controlled to be-0.1 MPa, and when the modified PBAT has a 'pole climbing' phenomenon, the reaction end point is the end point, and the PBAT modified material is obtained.
10. A modified PBAT material prepared using the preparation method of any one of claims 1-9.
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