CN116675853A - Plant oil-based reworkable thermosetting polyesteramide and preparation method thereof - Google Patents
Plant oil-based reworkable thermosetting polyesteramide and preparation method thereof Download PDFInfo
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- 229920006149 polyester-amide block copolymer Polymers 0.000 title claims abstract description 88
- 229920001187 thermosetting polymer Polymers 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000010773 plant oil Substances 0.000 title claims abstract description 7
- 235000015112 vegetable and seed oil Nutrition 0.000 claims abstract description 54
- 239000008158 vegetable oil Substances 0.000 claims abstract description 54
- 238000006243 chemical reaction Methods 0.000 claims abstract description 51
- 238000010438 heat treatment Methods 0.000 claims abstract description 40
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 12
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 11
- -1 diamine compound Chemical class 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 6
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 21
- NQBSWIGTUPEPIH-UHFFFAOYSA-N Floionic acid Chemical compound OC(=O)CCCCCCCC(O)C(O)CCCCCCCC(O)=O NQBSWIGTUPEPIH-UHFFFAOYSA-N 0.000 claims description 18
- NCPXQVVMIXIKTN-UHFFFAOYSA-N trisodium;phosphite Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])[O-] NCPXQVVMIXIKTN-UHFFFAOYSA-N 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 6
- 150000001735 carboxylic acids Chemical class 0.000 claims description 4
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 2
- 239000004246 zinc acetate Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 3
- 239000011541 reaction mixture Substances 0.000 claims 3
- UYBWIEGTWASWSR-UHFFFAOYSA-N 1,3-diaminopropan-2-ol Chemical compound NCC(O)CN UYBWIEGTWASWSR-UHFFFAOYSA-N 0.000 claims 1
- 239000000539 dimer Substances 0.000 claims 1
- 239000003784 tall oil Substances 0.000 claims 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 8
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 238000004132 cross linking Methods 0.000 abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 4
- 239000001257 hydrogen Substances 0.000 abstract description 4
- 229920005989 resin Polymers 0.000 abstract description 4
- 239000011347 resin Substances 0.000 abstract description 4
- 230000002787 reinforcement Effects 0.000 abstract description 3
- 239000003760 tallow Substances 0.000 abstract description 3
- 239000003822 epoxy resin Substances 0.000 description 11
- 229920000647 polyepoxide Polymers 0.000 description 11
- 239000002994 raw material Substances 0.000 description 9
- 150000004985 diamines Chemical class 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 238000002156 mixing Methods 0.000 description 6
- 238000007789 sealing Methods 0.000 description 6
- 239000000178 monomer Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 125000003368 amide group Chemical group 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 2
- 238000012958 reprocessing Methods 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000003225 biodiesel Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 235000019197 fats Nutrition 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 235000019871 vegetable fat Nutrition 0.000 description 1
- 239000001993 wax Substances 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
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/44—Polyester-amides
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyamides (AREA)
Abstract
The invention discloses a plant oil-based reworkable thermosetting polyesteramide and a preparation method thereof, which relate to the technical field of polyesteramide resins and comprise the following steps: (1) Heating and dissolving 20-200 parts by weight of vegetable oil based dicarboxylic acid containing ortho-dihydroxyl and 4-68 parts by weight of diamine compound, and uniformly stirring; (2) Adding 0.3-3 parts by weight of catalyst into the reaction liquid, and heating to 100-150 ℃ for reaction in a nitrogen atmosphere; (3) Heating the reaction liquid in the step 2 to 150-200 ℃ for reaction; (4) And (3) reacting the reaction solution obtained in the step (3) to 200-240 ℃ to obtain the catalyst. The beneficial effects are that: the amide bond, the ester bond and the hydroxyl exist in the polyester amide prepared by the invention, so that the polyester amide has high heat resistance and can be repeatedly processed, and has excellent recoverability; the prepared Chinese tallow kernel based polyester amide has excellent mechanical properties due to the mutual reinforcement of the hydrogen bonds between the amide bonds and the inter-molecular chain ester bond crosslinking.
Description
Technical Field
The invention relates to the technical field of polyester amide resin, in particular to plant oil-based reworkable thermosetting polyester amide and a preparation method thereof.
Background
Compared with thermoplastic polyester amide, thermosetting polyester amide has excellent mechanical property, thermal stability, solvent resistance and dimensional stability, and plays an important role in our daily life. Unfortunately, the three-dimensional network structure of traditional thermosetting polyesteramides cannot be remolded, reworked and recycled due to their permanent crosslinking. In view of environmental pollution and other factors, the problem is solved, and therefore, the problem can be solved by introducing exchangeable dynamic covalent bonds into a traditional chemical crosslinking network.
By triggering the bond exchange reaction under certain conditions, the polyesteramide can undergo network rearrangement, and further reprocessing and recycling of the material becomes possible. Although there has been much development of materials based on dynamic bond exchange, few reports of bio-based thermosetting polyesteramides remain. For example, patent publication No. CN110903463A discloses a plant oil-based reworkable thermosetting shape-memory epoxy resin and a preparation method thereof, the epoxy resin is sheared, and under the high temperature of 130-200 ℃, a certain pressure is given to the epoxy resin, so that the material can reach the condition of dynamic transesterification, and the topology structure of a crosslinked network is rearranged, so that a new shape can be reworked.
Sustainable polymers extracted from renewable raw materials have attracted increasing attention due to resource crisis and environmental issues associated with fossil-based traditional polymers. It is therefore of particular importance to develop a biobased polyester amide. Vegetable fats are considered to be one of the most important renewable raw materials in the chemical industry. They are the largest part of current renewable raw material consumption, and fats and oils currently used for non-food industry applications account for about 20% of the global yield they are used to make many products such as polymers, biodiesel, detergents, waxes, biodegradable lubricants, and the like. Vegetable oils are therefore also one of the best green sources for the preparation of polyester amide resins.
The development of vegetable oil-based reprocessable polyester amides at present has the problem of insufficient mechanical properties, for example, a problem group of established projects reports that a polyester amide vitramer is synthesized by a melt polycondensation method by taking castor oil as a raw material. The tensile strength is 1.8-11.4MPa, and the Young's modulus is 1.4-106.3MPa. How to make up the defect of instability of the plant oil-based renewable polyester amide crosslinked network due to the existence of dynamic bonds, thereby improving the mechanical properties of the polymer is still a great problem at present.
Chinese patent application publication No. CN112980145A discloses a thermosetting polyesteramide modified nano CaCO 3 Toughened epoxy treeThe polyester amide and the preparation method thereof synthesize linear polyester amide, can keep the thermal stability of epoxy resin, introduces phosphate groups containing P-OH at two ends of the polyester amide, can carry out addition reaction with the epoxy groups on the epoxy resin, promote the polyester amide and the epoxy resin to form a crosslinked interpenetrating network structure, and the phosphate groups can also play a role in promoting the carbon formation, and can improve the bonding tightness degree of interpenetrating networks formed by the polar amide bond and the epoxy resin, thereby improving the toughness of the epoxy resin well, and grafting modified nano CaCO 3 The epoxy resin can effectively play roles of dispersing stress, generating silver marks and absorbing a large amount of energy by the yielding resin matrix when the epoxy resin is subjected to external force, thereby achieving the purpose of toughening and obtaining the epoxy resin with good heat stability and excellent toughness. However, the mechanical properties of the polyesteramide prepared by the method are still insufficient, and further improvement is still needed.
Disclosure of Invention
The invention aims to solve the technical problem of insufficient mechanical properties of the existing vegetable oil-based reprocessable polyesteramide.
The invention solves the technical problems by the following technical means:
a method for preparing a vegetable oil-based reworkable thermosetting polyesteramide comprising the steps of:
(1) Heating and dissolving 20-200 parts by weight of vegetable oil based dicarboxylic acid containing ortho-dihydroxyl and 4-68 parts by weight of diamine compound, and uniformly stirring;
(2) Adding 0.3 to 3 weight parts of catalyst into the reaction liquid in the step (1), and heating to 100 to 150 ℃ for reaction for 2 to 6 hours in a nitrogen atmosphere;
(3) Heating the reaction liquid in the step (2) to 150-200 ℃ for reaction for 1-10 h;
(4) And (3) reacting the reaction solution in the step (3) to a temperature of 200-240 ℃ for 0.5-3 h to obtain the reworkable thermosetting polyesteramide.
The beneficial effects are that: the amide bond, the ester bond and the hydroxyl exist in the polyester amide prepared by the invention, so that the polyester amide has high heat resistance and can be repeatedly processed, and has excellent recoverability; because of the mutual reinforcement of the hydrogen bonds between the amide bonds and the inter-molecular chain ester bond crosslinking, the prepared vegetable oil-based polyester amide has excellent mechanical properties, and lays a foundation for the application of the vegetable oil-based polyester amide to the industrial fields of aerospace and the like; and the high value-added utilization of vegetable oil resources is realized, and the method accords with the age background of carbon neutralization. The breaking strength of the prepared polyesteramide is 1-70 MPa, and the breaking elongation is 1-400%.
Preferably, the ratio of the molar amount of carboxylic acid in the vegetable oil-based ortho-dihydroxyl-containing dicarboxylic acid to the molar amount of amino groups in the diamine compound is 1:0.7-1.
The beneficial effects are that: the weight parts of the raw materials are selected according to the molar ratio of the used monomers, and different molar ratios have different mechanical properties, so that the feeding of carboxyl in the dicarboxylic acid of the ortho-dihydroxyl is ensured to be less than or equal to the feeding of amino in the diamine by adjusting the weight parts of the raw materials and adjusting the molar ratio of the raw materials.
Preferably, the catalyst comprises any one of sodium phosphite, sodium hypophosphite and zinc acetate.
Preferably, the vegetable oil-based ortho-dihydroxyl-containing dicarboxylic acid is vegetable oil-based 9, 10-dihydroxy-octadecadioic acid.
Preferably, the vegetable oil-based 9, 10-dihydroxy-octadecadioic acid has the structure:
preferably, the diamine compound is 1, 6-hexamethylenediamine.
The invention also provides the recyclable vegetable oil-based thermosetting polyesteramide obtained by the preparation method.
Preferably, the vegetable oil-based thermosetting polyesteramide has the structural formula:
the beneficial effects are that: the polyester amide prepared by the invention has the advantages of high heat resistance, repeatable processing and excellent recoverability due to the existence of the amide bond, the ester bond and the hydroxyl simultaneously. The breaking strength of the polyester amide is 1-70 MPa, and the breaking elongation is 1-400%.
The invention has the advantages that:
1. the amide bond, the ester bond and the hydroxyl exist in the polyester amide prepared by the invention, so that the polyester amide has high heat resistance and can be repeatedly processed, and has excellent recoverability; because of the mutual reinforcement of the hydrogen bonds between the amide bonds and the inter-molecular-chain ester bond crosslinks, the prepared Chinese tallow kernel based polyester amide has excellent mechanical properties, and lays a foundation for the application of the Chinese tallow kernel based polyester amide in the industrial fields of aerospace and the like; and the high value-added utilization of vegetable oil resources is realized, and the method accords with the age background of carbon neutralization. The breaking strength of the prepared polyesteramide is 1-70 MPa, and the breaking elongation is 1-400%.
2. The polyester amide is synthesized from the vegetable oil-based dicarboxylic acid containing ortho-dihydroxyl and the diamine compound without adding a solvent, and has the advantages of simple synthesis method, no environmental pollution, no purification and impurity removal of the product, and simple recovery.
3. The invention takes the vegetable oil-based dicarboxylic acid containing ortho-dihydroxyl as a raw material, is a monomer with multiple functions, and can regulate the mechanical strength and reworkability of the polyesteramide by regulating the feeding ratio of the vegetable oil-based dicarboxylic acid to diamine.
4. In the preparation process, nitrogen is introduced to prevent the material from being oxidized at high temperature, and generated small molecules are blown out to promote the forward reaction.
5. The invention needs to strictly control the feeding ratio of the dibasic acid and the diamine. If the reaction ratio of the dibasic acid and the diamine is higher than the range described, the product cannot be formed into a film by tabletting after being fished out, and the reworkable capability is not provided, because the crosslinking degree of the polymer is increased by monomer feeding in the range, most of hydroxyl groups in the monomer react with carboxylic acid to form ester bonds, and the residual hydroxyl content is less, so that the dynamic exchange of the hydroxyl groups and the ester bonds is difficult to realize. If the reaction ratio of the dibasic acid and the diamine is lower than the range described, the mechanical property of the product is poor, and the reprocessing capability is still realized. This is because the addition of the monomer in this range results in a polymer having a large number of small molecules and thus poor mechanical properties.
Drawings
FIG. 1 is a schematic illustration of a preparation route and a schematic illustration of a polymer structure of a vegetable oil-based polyesteramide according to an embodiment of the present invention;
FIG. 2 is an infrared spectrum analysis chart of the polyesteramide in examples 1 to 4 of the invention;
FIG. 3 is a graph showing the stress-strain test results of the polyesteramides of examples 1 to 4 of the invention;
FIG. 4 is a graph of the differential scanning calorimeter results of the polyesteramides of examples 1 to 4 of the invention;
FIG. 5 is a graph showing the comparison of mechanical properties of the polyester amide repeat tabletting in example 2 of the present invention;
FIG. 6 is a photograph showing the comparison of the front and rear of the polyester amide in example 3 of the present invention after repeated tabletting.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions in the embodiments of the present invention will be clearly and completely described in the following in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The test materials, reagents and the like used in the examples described below are commercially available unless otherwise specified.
Those of skill in the art, without any particular mention of the techniques or conditions, may follow the techniques or conditions described in the literature in this field or follow the product specifications.
Example 1:
the preparation of the vegetable oil-based polyester amide specifically comprises the following steps:
adding 20g of vegetable oil base 9, 10-dihydroxyl-octadecanedioic acid, 4.7g of 1, 6-hexamethylenediamine and 250mg of sodium phosphite into a three-mouth bottle, uniformly mixing and heating for 1h by a mechanical stirrer under the nitrogen atmosphere of 80 ℃, heating to 100 ℃ for reaction for 6h, heating to 180 ℃ for reaction for 1h, heating to 230 ℃ for reaction for 2h, taking out a product after the reaction is finished, sealing and preserving the product, and naming the product as polyesteramide 1.
Example 2:
the preparation of the vegetable oil-based polyester amide specifically comprises the following steps:
adding 20g of vegetable oil base 9, 10-dihydroxyl-octadecanedioic acid, 5.4g of 1, 6-hexamethylenediamine and 250mg of sodium phosphite into a three-mouth bottle, uniformly mixing and heating for 1h by a mechanical stirrer under the nitrogen atmosphere of 80 ℃, heating to 100 ℃ for reaction for 6h, heating to 180 ℃ for reaction for 1h, heating to 230 ℃ for reaction for 2h, taking out a product after the reaction is finished, sealing and preserving the product, and naming the product as polyesteramide 2.
Example 3:
the preparation of the vegetable oil-based polyester amide specifically comprises the following steps:
adding 20.0g of vegetable oil base 9, 10-dihydroxyl-octadecanedioic acid, 6.0g of 1, 6-hexamethylenediamine and 250mg of sodium phosphite into a three-mouth bottle, uniformly mixing and heating for 1h under the nitrogen atmosphere of 80 ℃, heating to 100 ℃ for reaction for 6h, heating to 180 ℃ for reaction for 1h, heating to 230 ℃ for reaction for 2h, taking out a product after the reaction is finished, sealing and preserving the product, and naming the product as polyesteramide 3.
Example 4:
the preparation of the vegetable oil-based polyester amide specifically comprises the following steps:
adding 20.0g of vegetable oil base 9, 10-dihydroxyl-octadecanedioic acid, 6.7g of 1, 6-hexamethylenediamine and 250mg of sodium phosphite into a three-mouth bottle, uniformly mixing and heating for 1h under the nitrogen atmosphere of 80 ℃, heating to 100 ℃ for reaction for 6h, heating to 180 ℃ for reaction for 1h, heating to 230 ℃ for reaction for 2h, taking out the product after the reaction is finished, sealing and preserving, and naming the product as polyesteramide 4.
Example 5:
the preparation of the vegetable oil-based polyester amide specifically comprises the following steps:
adding 200g of vegetable oil base 9, 10-dihydroxyl-octadecanedioic acid, 68g of 1, 6-hexamethylenediamine and 3g of sodium phosphite into a three-mouth bottle, uniformly mixing and heating for 1h by a mechanical stirrer under the nitrogen atmosphere of 80 ℃, heating to 150 ℃ for reaction for 2h, heating to 150 ℃ for reaction for 10h, heating to 200 ℃ for reaction for 3h, taking out the product after the reaction is finished, sealing and preserving the product, and naming the product as polyesteramide 5.
Example 6:
the preparation of the vegetable oil-based polyester amide specifically comprises the following steps:
adding 150g of vegetable oil base 9, 10-dihydroxyl-octadecanedioic acid, 30g of 1, 6-hexamethylenediamine and 2g of sodium phosphite into a three-mouth bottle, uniformly mixing and heating for 1h by a mechanical stirrer under the nitrogen atmosphere of 80 ℃, heating to 120 ℃ for reaction for 3h, heating to 200 ℃ for reaction for 1h, heating to 240 ℃ for reaction for 0.5h, taking out the product after the reaction is finished, sealing and preserving the product, and naming the product as polyesteramide 6.
The vegetable oil base 9, 10-dihydroxyl-octadecanedioic acid is obtained by the hydrolysis of vegetable oil, olefin double decomposition and oxidation of potassium permanganate.
FIG. 1 is a flow chart of a reaction of vegetable oil based 9, 10-dihydroxy-octadecanedioic acid to produce a polyesteramide.
As shown in FIG. 2, according to the infrared spectrogram analysis of the polyesteramide in the examples 1 to 4 of the invention, the carboxylic acid and amine groups are converted into amide groups, and meanwhile, due to the existence of hydroxyl groups in the raw materials, the amide groups can be reacted with carboxyl groups to generate ester groups, namely the polyesteramide is successfully prepared.
As shown in FIG. 3, the stress-strain test results of the polyesteramides of examples 1 to 4 of the invention show that the preparation of polyesteramides 1, 2, 3 and 4 shows that the mechanical properties of the materials gradually transition from elastomer to plastic with increasing diamine content without changing the content of vegetable oil-based 9, 10-dihydroxy-octadecanedioic acid. The tensile properties of the bars were measured according to GB/T1040.3-2006, with a tensile rate of 2mm/min.
As shown in FIG. 4, the differential scanning calorimetric results of the polyesteramides of examples 1 to 4 of the invention show that the preparation of polyesteramides 1, 2, 3 and 4 shows that in the case of a constant content of vegetable oil-based 9, 10-dihydroxy-octadecanedioic acid, the glass transition temperature of the material increases gradually with increasing diamine content, and the melting point also increases gradually. It was further demonstrated that as the diamine content increased, the amide bonds increased gradually and the ester bonds decreased gradually. And from the mechanical properties of fig. 3, it can be seen that the hydrogen bond interaction between amide bonds contributes more to the mechanical strength than the ester bond.
As shown in FIG. 5, the mechanical properties of the polyester amide repeated tabletting in the embodiment 2 of the invention are compared with each other, and the mechanical properties of the polyester amide 2 are not obviously changed after repeated tabletting, which means that the polyester amide can be repeatedly processed.
As shown in FIG. 6, the comparative photograph of the polyester amide of example 3 of the present invention before and after repeated tabletting, and the polyester amide 3 was ground after tabletting and repeated tabletting was still possible.
The above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A method for preparing plant oil-based reworkable thermosetting polyesteramide, which is characterized in that: the method comprises the following steps:
(1) Heating and dissolving 20-200 parts by weight of vegetable oil based dicarboxylic acid containing ortho-dihydroxyl and 4-68 parts by weight of diamine compound, and uniformly stirring;
(2) Adding 0.3 to 3 weight parts of catalyst into the reaction liquid in the step (1), and heating to 100 to 150 ℃ for reaction for 2 to 6 hours in a nitrogen atmosphere;
(3) Heating the reaction liquid in the step (2) to 150-200 ℃ for reaction for 1-10 h;
(4) And (3) reacting the reaction solution in the step (3) to a temperature of 200-240 ℃ for 0.5-3 h to obtain the reworkable thermosetting polyesteramide.
2. The method for preparing a vegetable oil-based reworkable thermosetting polyesteramide according to claim 1, wherein: the ratio of the molar amount of carboxylic acid in the dicarboxylic acid containing ortho-dihydroxyl in the vegetable oil base to the molar amount of amino in the diamine compound is 1:0.7-1.
3. A process for the preparation of vegetable oil-based reworkable thermosetting polyesteramides according to claim 1 or 2, characterized in that: the vegetable oil-based dicarboxylic acid containing ortho-dihydroxyl is vegetable oil-based 9, 10-dihydroxyl-octadecanedioic acid.
4. A process for the preparation of vegetable oil-based reworkable thermosetting polyesteramide as claimed in claim 3, wherein: the vegetable oil-based 9, 10-dihydroxyl-octadecanedioic acid has the structure that:
5. the method for preparing a vegetable oil-based reworkable thermosetting polyesteramide according to claim 1, wherein: the diamine compound is 1, 6-hexamethylenediamine.
6. The method for preparing a vegetable oil-based reworkable thermosetting polyesteramide according to claim 1, wherein: the catalyst comprises any one of sodium phosphite, sodium hypophosphite and zinc acetate.
7. The method for preparing a vegetable oil-based reworkable thermosetting polyesteramide according to claim 1, wherein: the method comprises the following steps:
(1) 20.0g of vegetable oil base 9, 10-dihydroxyl-octadecanedioic acid, 5.4g of 1, 6-hexamethylenediamine and 25mg of sodium phosphite are added into a three-neck flask, and the mixture is heated to 80 ℃ for reaction for 1h under the nitrogen atmosphere;
(2) Heating the reaction mixture in the step (1) to 160 ℃ for reaction for 6 hours, and then heating to 180 ℃ for reaction for 2 hours;
(3) And (3) reacting the reaction system in the step (2) to 220 ℃ for 2 hours to obtain the reworkable thermosetting polyesteramide.
8. The method for preparing a vegetable oil-based reworkable thermosetting polyesteramide according to claim 1, wherein: the method comprises the following steps:
(1) Heating and dissolving 35.2g of tall oil dimer acid and 6.8g of 1, 3-diamino-2-propanol, and uniformly stirring to form a reaction solution;
(1) 20.0g of vegetable oil-based 9, 10-dihydroxyl-octadecanedioic acid, 6.0g of 1, 6-hexamethylenediamine and 25mg of sodium phosphite are added into a three-neck flask, and the mixture is heated to 80 ℃ for reaction for 1h under the nitrogen atmosphere;
(2) Heating the reaction mixture in the step (1) to 160 ℃ for reaction for 6 hours, and then heating to 180 ℃ for reaction for 2 hours;
(3) And (3) reacting the reaction system in the step (2) to 220 ℃ for 2 hours to obtain the reworkable thermosetting polyesteramide.
9. The method for preparing a vegetable oil-based reworkable thermosetting polyesteramide according to claim 1, wherein: the method comprises the following steps:
(1) 20.0g of vegetable oil base 9, 10-dihydroxyl-octadecanedioic acid, 6.7g of 1, 6-hexamethylenediamine and 25mg of sodium phosphite are added into a three-neck flask, and the mixture is heated to 80 ℃ for reaction for 1h under the nitrogen atmosphere;
(2) Heating the reaction mixture in the step (1) to 160 ℃ for reaction for 6 hours, and then heating to 180 ℃ for reaction for 2 hours;
(3) And (3) reacting the reaction system in the step (2) to 220 ℃ for 2 hours to obtain the reworkable thermosetting polyesteramide.
10. Vegetable oil-based reworkable thermosetting polyesteramide produced by the process of any of claims 1 to 9.
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