CN117089074A - Ultralow-temperature bio-based polyamide hot melt adhesive and preparation method thereof - Google Patents
Ultralow-temperature bio-based polyamide hot melt adhesive and preparation method thereof Download PDFInfo
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- CN117089074A CN117089074A CN202310835390.3A CN202310835390A CN117089074A CN 117089074 A CN117089074 A CN 117089074A CN 202310835390 A CN202310835390 A CN 202310835390A CN 117089074 A CN117089074 A CN 117089074A
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- 239000004831 Hot glue Substances 0.000 title claims abstract description 51
- 229920006021 bio-based polyamide Polymers 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000004952 Polyamide Substances 0.000 claims abstract description 181
- 229920002647 polyamide Polymers 0.000 claims abstract description 181
- 239000000178 monomer Substances 0.000 claims abstract description 122
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 28
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical group N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 23
- HCZMHWVFVZAHCR-UHFFFAOYSA-N 2-[2-(2-sulfanylethoxy)ethoxy]ethanethiol Chemical compound SCCOCCOCCS HCZMHWVFVZAHCR-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 14
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 11
- 238000012650 click reaction Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- JXASPPWQHFOWPL-UHFFFAOYSA-N Tamarixin Natural products C1=C(O)C(OC)=CC=C1C1=C(OC2C(C(O)C(O)C(CO)O2)O)C(=O)C2=C(O)C=C(O)C=C2O1 JXASPPWQHFOWPL-UHFFFAOYSA-N 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 22
- 230000001070 adhesive effect Effects 0.000 abstract description 18
- 239000000853 adhesive Substances 0.000 abstract description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract description 9
- 238000013461 design Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 239000002028 Biomass Substances 0.000 abstract description 2
- 235000014113 dietary fatty acids Nutrition 0.000 abstract description 2
- 229930195729 fatty acid Natural products 0.000 abstract description 2
- 239000000194 fatty acid Substances 0.000 abstract description 2
- 150000004665 fatty acids Chemical class 0.000 abstract description 2
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 description 23
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 14
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical group OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 13
- 229910052786 argon Inorganic materials 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 239000003921 oil Substances 0.000 description 10
- 235000019198 oils Nutrition 0.000 description 10
- 239000001257 hydrogen Substances 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 241001190694 Muda Species 0.000 description 8
- 238000002844 melting Methods 0.000 description 8
- 230000008018 melting Effects 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 150000001408 amides Chemical class 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 6
- 229920003188 Nylon 3 Polymers 0.000 description 5
- 238000011161 development Methods 0.000 description 5
- 230000018109 developmental process Effects 0.000 description 5
- 230000009477 glass transition Effects 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 239000004814 polyurethane Substances 0.000 description 4
- 229920002635 polyurethane Polymers 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- -1 and simultaneously Substances 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 230000036541 health Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 230000000630 rising effect Effects 0.000 description 3
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 229920005605 branched copolymer Polymers 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 2
- 150000004662 dithiols Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- PSHKMPUSSFXUIA-UHFFFAOYSA-N n,n-dimethylpyridin-2-amine Chemical compound CN(C)C1=CC=CC=N1 PSHKMPUSSFXUIA-UHFFFAOYSA-N 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 229920006345 thermoplastic polyamide Polymers 0.000 description 2
- 239000012855 volatile organic compound Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- UYBWIEGTWASWSR-UHFFFAOYSA-N 1,3-diaminopropan-2-ol Chemical compound NCC(O)CN UYBWIEGTWASWSR-UHFFFAOYSA-N 0.000 description 1
- ANLABNUUYWRCRP-UHFFFAOYSA-N 1-(4-nitrophenyl)cyclopentane-1-carbonitrile Chemical compound C1=CC([N+](=O)[O-])=CC=C1C1(C#N)CCCC1 ANLABNUUYWRCRP-UHFFFAOYSA-N 0.000 description 1
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- 241000407429 Maja Species 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 239000003519 biomedical and dental material Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- YHASWHZGWUONAO-UHFFFAOYSA-N butanoyl butanoate Chemical compound CCCC(=O)OC(=O)CCC YHASWHZGWUONAO-UHFFFAOYSA-N 0.000 description 1
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical group OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000011067 equilibration Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical group OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- JBPWRHDFVVEDTJ-UHFFFAOYSA-N oxadithiole Chemical compound O1SSC=C1 JBPWRHDFVVEDTJ-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical group [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- XPQPWPZFBULGKT-UHFFFAOYSA-N undecanoic acid methyl ester Natural products CCCCCCCCCCC(=O)OC XPQPWPZFBULGKT-UHFFFAOYSA-N 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 238000009736 wetting 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
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/02—Polythioethers
- C08G75/04—Polythioethers from mercapto compounds or metallic derivatives thereof
- C08G75/045—Polythioethers from mercapto compounds or metallic derivatives thereof from mercapto compounds and unsaturated compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J181/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur, with or without nitrogen, oxygen, or carbon only; Adhesives based on polysulfones; Adhesives based on derivatives of such polymers
- C09J181/02—Polythioethers; Polythioether-ethers
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyamides (AREA)
Abstract
The invention discloses an ultralow temperature bio-based polyamide hot melt adhesive and a preparation method thereof, wherein the ultralow temperature bio-based polyamide hot melt adhesive has the following structural formula:wherein n is more than or equal to 5 and less than or equal to 5000; at least one R isThe bio-based polyamide material synthesized by the invention is prepared by using the functional design of the fatty acid polyamide monomer, so that the biomass hot melt adhesive has excellent adhesive strength and weather resistance, is synthesized from natural raw materials, has no free formaldehyde, no benzene and no heavy metal, and meets the national environmental protection material standard.
Description
Technical Field
The invention relates to the technical field of polyamide, in particular to ultralow-temperature bio-based polyamide hot melt adhesive and a preparation method thereof.
Background
The adhesive belongs to a high molecular polymer, has the advantages of light specific gravity, excellent mechanical property, solvent resistance, high temperature resistance, flexible processability and the like, can be used as an advanced biomedical material and a light high-strength structure connecting material, is widely used in various fields of biological tissue engineering, furniture electrical appliances, transportation, construction industry and the like, and is a key base material with a certain special significance. Therefore, optimizing the type of adhesive and improving its overall properties are key ways to drive its high quality development.
Conventional adhesives include epoxy resins, silicones, formaldehyde-based resins (phenolic, urea-formaldehyde, melamine-formaldehyde resins, acrylonitrile, polyurethane, polyolefin, etc.). However, they are generally prepared by synthesizing petroleum-based compounds as raw materials, and simultaneously, toxic substances such as benzene, toluene and the like are used as organic solvents, which release Volatile Organic Compounds (VOCs) during application, cause great pollution to the environment and seriously harm human health. With the improvement of the development level of the economy and the society, people pay more and more attention to health, and the requirements on the quality of working environments are higher and higher.
The environment-friendly adhesive is an adhesive which has no pollution to the environment and no toxicity to human bodies and meets the three requirements of environmental protection, health and safety. The main solutions at present are: the method accelerates the popularization of green products such as water-based type, hot-melt type, solvent-free type, ultraviolet light curing type, high solid content type, biodegradation type and the like, and limits the use of harmful solvents and auxiliary agents. Wherein, the hot melt adhesive is a plastic adhesive, and the physical form of the hot melt adhesive can be changed along with the temperature under certain external conditions, but the chemical characteristics of the hot melt adhesive are unchanged. The advantages of low price, simple synthesis, stable performance, no pollution, strong coating and adhesive properties and the like are utilized, and the method has wide application in the aspects of household electrical appliance assembly, printing textile, biological medicine, wooden furniture and the like. However, with the upgrading and upgrading requirements of engineering materials, especially the rapid development of high-strength and functional material technologies for more than last ten years, the traditional hot melt adhesive cannot meet the requirement of bonding new materials with increasingly wide variety at present, and problems such as poor bonding strength, easy-to-open adhesive aging and the like occur, so that the development of novel hot melt adhesive products with excellent performances is urgent.
At present, research on the traditional hot melt adhesive at home and abroad mainly focuses on two aspects, namely modification based on EVA resin, and although the EVA resin has certain advantages in cost and technical development, the defects of the traditional hot melt adhesive still cannot be well solved due to the inherent property of the EVA resin. The other is to use a novel polymer as a matrix to prepare a hot melt adhesive, wherein Polyurethane (PUA) hot melt adhesives are most rapidly developed. Researchers carry out modification design through molecular structure and composition, and endow polyurethane hot melt adhesive with excellent bonding strength, high temperature resistance, recycling property and the like. The former research shows that the modification methods can improve the performance of the hot melt adhesive to a certain extent, but the strength of the obtained hot melt adhesive is still difficult to meet the requirements of high-performance engineering materials due to the limitations of the characteristics of the polymer, the research methods, means and the like, the excellent characteristics of the thermoplastic polymer cannot be exerted, and the environment negative problems caused by the fact that a large amount of fossil resources are often depended on, and most importantly, the self strength and weather resistance of the glued product are unstable, so that the glued product is limited to a certain extent in application, such as poor performance under high-humidity or low-temperature environments. The thermoplastic Polyamide (PA) hot melt adhesive is solid at room temperature, is liquid above the melting point of the thermoplastic Polyamide (PA) hot melt adhesive, has fluidity and wetting ability, and forms high-strength bonding after solidification and cooling. Because the molecules contain polar groups such as amino, carboxyl and amido, the polyamide hot melt adhesive has better adhesive property for a plurality of polar materials, for example, the preparation method of the polyamide hot melt adhesive is disclosed in Chinese patent application document with publication number of CN104962229A, the proportion and design of two dibasic acids, two diamine, caprolactam and one monobasic acid are carefully selected, and the polyamide hot melt adhesive with high temperature resistance, high melting point and narrow melting range can be prepared by using the conventional method, and can meet the adhesive requirement of automobile parts, electronic parts and the like with working condition temperature up to 140 ℃, but the adhesive property is not ideal in low-temperature and high-humidity environments; the Chinese patent application publication No. CN113651956A discloses a preparation method of an ultra-high toughness branched polyamide copolymer, and the prepared polyamide copolymer, wherein the proportion of diamine with different side chains influences the network structure of the polyamide copolymer, so that the performance of the polyamide copolymer can be regulated. The prepared branched copolymer has excellent mechanical properties and is suitable for the field of hot melt adhesives, but the bonding capability of the branched copolymer in a low-temperature and high-humidity environment is still not ideal.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a novel polyamide material which can improve the bonding capability of the hot melt adhesive in low-temperature and high-humidity environments and solve the technical problem that the bonding capability of the existing polyamide hot melt adhesive in low-temperature and high-humidity environments is lower.
The invention solves the technical problems by the following technical means:
an ultralow-temperature bio-based polyamide hot melt adhesive has the following structural formula:
wherein n is more than or equal to 5 and less than or equal to 5000;
r isOr R is->Repetition of any one or more of the following structures:
the beneficial effects are that: introduction of specific carboxyl functional groupsThe reaction molar ratio of the functional amide monomers of the prepared copolyamide is regulated to obtain polyamide with different proportions of succinate groups, and carboxyl groups at the tail ends of the succinate groups and amide bonds in the molecular chains form hydrogen bonds with hydroxyl groups on the surface of a substrateTo produce an adhesive effect; in addition, the hydrophilicity of the carboxyl group at the tail end of the succinate group can also form a synergistic effect with the hydrophobicity of the butyl group, so that the water-resistant adhesion capability of the polymer is improved; at the same time, dithiol containing ether bond is selectedAs a comonomer to impart non-crystalline properties to the polymer backbone, thereby improving the performance strength of the polymer in low temperature environments.
Preferably, the ultralow-temperature bio-based polyamide hot melt adhesive is prepared from the same functional polyamide monomer and 3, 6-dioxa-1, 8-octane dithiol through a mercapto-olefin click reaction, and the structural formula of the functional polyamide monomer is as follows:
wherein R is->
Preferably, the ultralow-temperature bio-based polyamide hot melt adhesive is prepared from two different functional polyamide monomers and 3, 6-dioxa-1, 8-octanedithiol through mercapto-olefin click reaction, wherein the two different functional polyamide monomers are respectively a functional polyamide monomer A and a functional polyamide monomer B;
the structural formula of the functional polyamide monomer A is as follows:
wherein R is
The structural formula of the functional polyamide monomer B is as follows:
wherein R is any one of the following structures:
preferably, the ultralow-temperature bio-based polyamide hot melt adhesive is prepared from three different functional polyamide monomers, namely a functional polyamide monomer A, a functional polyamide monomer B and a functional polyamide monomer C, by a mercapto-olefin click reaction with 3, 6-dioxa-1, 8-octanedithiol;
the structural formula of the functional polyamide monomer A is as follows:
wherein R is
The structural formulas of the functional polyamide monomer B and the functional polyamide monomer C are as follows:
wherein, the functional polyamide monomer B and the functional polyamide monomer C are different from each other in R, and are selected from any one of the following structures:
the invention also provides a preparation method of the ultralow-temperature bio-based polyamide hot melt adhesive, which comprises the following steps: taking 1-100 parts by weight of the functionsDissolving polyamide monomer, 1-100 parts by weight of 3, 6-dioxa-1, 8-octanedithiol and 0.1-10 parts by weight of catalyst in 1-100 parts by weight of solvent, and reacting at 40-100 ℃ for 12-36 hours to obtain the ultralow temperature bio-based polyamide hot melt adhesive; wherein the structural formula of the functional polyamide monomer is as follows:
r is Any one of the following.
Preferably, the catalyst is azobisisobutyronitrile; the solvent is tetrahydrofuran.
Preferably, the functional polyamide monomer comprises a functional polyamide monomer A and a functional polyamide monomer B with different R, wherein the mass ratio of the functional polyamide monomer A to the functional polyamide monomer B is 10-60:40-90, the structural formula of the functional polyamide monomer A is as follows:
wherein R is->
Preferably, the structural formula of the functional polyamide monomer B is as follows:
wherein R is->or-H.
Preferably, the functional polyamide monomers include functional polyamide monomer a, functional polyamide monomer B and functional polyamide monomer C, wherein R is different; the mass ratio of the functional polyamide monomer A to the functional polyamide monomer B to the functional polyamide monomer C is 5-25:35-60:40, a step of performing a; the structural formula of the functional polyamide monomer A is as follows:
wherein R is->
Preferably, the structural formula of the functional polyamide monomer B is as follows:
wherein R is->
The structural formula of the functional polyamide monomer C is as follows:
wherein R is-H.
The invention has the advantages that:
(1) The bio-based polyamide material synthesized by the invention is prepared by using the functional design of the fatty acid polyamide monomer, so that the biomass hot melt adhesive has excellent adhesive strength and weather resistance, is synthesized from natural raw materials, has no free formaldehyde, no benzene and no heavy metal, and meets the national environmental protection material standard.
(2) The breaking strength of the polyamide hot melt adhesive prepared by the invention is 2-30 MPa, the breaking elongation is 550-850% and the shearing strength is 4-11 MPa. The preparation method of the material is simple, the condition is mild, and the product performance is good.
(3) The invention introduces functional groups by regulating and controlling the side chain structure of the amide monomer, such as: succinate groups, gallic acid groups, catechol groups and the like, and controlling the proportion of side chain groups to obtain polyamide hot melt adhesives with different excellent performances; at the same time, dithiol containing ether bond is selectedAs a comonomer to impart non-crystalline properties to the polymer backbone, thereby improving the performance strength of the polymer in low temperature environments.
(4) The invention explores the molecular structure of the side chain of the vegetable oil polyamide and the enhanced cementing mechanism of a crosslinking system, and provides a thinking for developing novel functional adhesives.
Drawings
FIG. 1 is a nuclear magnetic resonance spectrum of the functional polyamide monomer of examples 1 and 2 of the present invention and the functional polyamide prepared in example 2;
FIG. 2 is a DSC chart of the functional polyamide prepared in examples 2-5 of the present invention and comparative example 1;
FIG. 3 is a stress-strain graph of the functional polyamides prepared in examples 2-5 and comparative example 1 of the present invention;
FIG. 4 is a stress-strain graph of the functional polyamides prepared in example 1 and examples 6-7 of the present invention;
FIG. 5 is a plot of the bond stroke-shear strength for the functional polyamides prepared in examples 2-5 and comparative example 1 of the present invention;
FIG. 6 is a plot of the bond stroke-shear strength for the functional polyamides prepared in example 1, examples 6-7 of the present invention.
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.
The preparation methods of the functional polyamide monomer 1 and the functional polyamide monomer 2 used in the following examples of the present invention are described in chinese patent application publication No. CN107501116a, entitled "a functional polyamide monomer, functional polyamide and preparation method", application No. 201710825333.1. Other reagents were all obtained as usual and the liquid reagents had to be distilled under reduced pressure after drying over anhydrous magnesium sulfate before use.
Example 1
Preparation of functional Polyamide monomer 1
Taking 100g of methyl undecylenate, 1, 3-diamino-2-propanol, adding 1g into 40ml of tetrahydrofuran, introducing argon gas for half an hour, placing into an oil bath pot at 40 ℃, adding 10ml of sodium methoxide, clarifying the solution, and reacting for 20 hours under the reaction condition at 40 ℃ to obtain the functional polyamide monomer 1, wherein the synthetic route is as follows:
preparation of functional Polyamide monomer A
54g of a functional polyamide monomer with a side chain of-OH 1, 15g of succinic anhydride and 0.4g of dimethylaminopyridine are placed in a round-bottomed flask, and 40ml of tetrahydrofuran is added and mixed. Reacting for 24 hours at 65 ℃ to obtain a clear solution, and purifying to obtain the functional polyamide monomer A, wherein a specific reaction equation is as follows:
in the above equation, R represents a succinate groupThe functional polyamide monomer A (MUDA) obtained in this example 1 The H NMR spectrum is shown in FIG. 1, which shows that the purity of the obtained monomer is very high. It is clear from the comparison of the nuclear magnetism with the functional polyamide monomer 1 (UDA) having hydroxyl groups as side chainsIt was revealed that the original peak a at 3.8ppm disappeared, a new peak appeared at 4.75ppm and an r peak appeared at 2.5ppm, indicating that the acid anhydride was successfully reacted with the hydroxyl group of the functional polyamide monomer 1, and the functional polyamide monomer A was successfully obtained.
Preparation of functional Polyamide 1
100 parts by weight of a functional polyamide monomer A,100 parts by weight of 3, 6-dioxa-1, 8-dithiol, and 0.2 part by weight of Azobisisobutyronitrile (AIBN) as a catalyst and 15 parts by weight of tetrahydrofuran were charged into a reaction vessel. Argon was introduced for 20 minutes, and the mixture was then placed in an oil bath to react at 65 ℃ for 24 hours, as shown in the following equation:
after which the functional polyamide 1 is obtained by methanol precipitation.
Example 2
Functional polyamide monomer 2
54g of the functional polyamide monomer 1 prepared in example 1, 12g of butyric anhydride, 400mg of dimethylaminopyridine were placed in a round-bottomed flask and mixed with 30ml of tetrahydrofuran. Reacting for 24 hours at 65 ℃ to obtain a clear solution, and purifying to obtain a functional polyamide monomer 2; the synthetic route of the functional polyamide monomer 2 is as follows:
preparation of functional Polyamide 2a
40 parts by weight of the functional polyamide monomer 1 of example 1, 55 parts by weight of the functional polyamide monomer 2 and 5 parts by weight of the functional polyamide monomer A prepared in example 1, 100 parts by weight of 3, 6-dioxa-1, 8-octanedithiol, and 0.2 part by weight of the catalyst AIBN and 15 parts by weight of tetrahydrofuran were taken into a reaction vessel. Argon was introduced for 15 minutes, and the mixture was then placed in an oil bath to react at 65 ℃ for 24 hours, as shown in the following equation:
raw materials HS-R in the equation 1 -SH is the 3, 6-dioxa-1, 8-dithiol, -R is hydrogen, succinateAnd butylcarbonyl->S-R on the backbone of the product in the equation 1 S is disulfide
After which the functional polyamide 2a is obtained by methanol precipitation. The nuclear magnetic resonance spectrum of the functional polyamide 2a obtained in this example is shown in FIG. 1 (the uppermost curve), and by comparing FIG. 1, peaks at 4.75ppm, 4.9ppm and 5.8ppm are disappeared, and further, it is shown from 3.62ppm, 2.7ppm and 1.58ppm that oxadithiol successfully reacts with double bonds to produce the functional polyamide 2a.
Example 3
Preparation of functional Polyamide 2b
40 parts by weight of the functional polyamide monomer 1 of example 1, 52 parts by weight of the functional polyamide monomer 2 of example 2 and 8 parts by weight of the functional polyamide monomer A of example 1, 100 parts by weight of 3, 6-dioxa-1, 8-octanedithiol, and 0.2 part by weight of catalyst AIBN and 15 parts by weight of tetrahydrofuran were taken into a reaction vessel. Argon was introduced for 15 minutes, and then the mixture was placed in an oil bath to react at 65℃for 24 hours, to obtain functional polyamide 2b.
Example 4
Preparation of functional Polyamide 2c
40 parts by weight of the functional polyamide monomer 1 of example 1, 48 parts by weight of the functional polyamide monomer 2 of example 2 and 12 parts by weight of the functional polyamide monomer A of example 1, 100 parts by weight of 3, 6-dioxa-1, 8-octanedithiol, and 0.2 part by weight of catalyst AIBN and 15 parts by weight of tetrahydrofuran were taken into a reaction vessel. Argon was introduced for 15 minutes, and then the mixture was placed in an oil bath to react at 65℃for 24 hours, to obtain functional polyamide 2c.
Example 5
Preparation of functional Polyamide 2d
40 parts by weight of the functional polyamide monomer 1 of example 1, 35 parts by weight of the functional polyamide monomer 2 of example 2 and 25 parts by weight of the functional polyamide monomer A of example 1, 100 parts by weight of 3, 6-dioxa-1, 8-octanedithiol, and 0.2 part by weight of catalyst AIBN and 15 parts by weight of tetrahydrofuran were taken into a reaction vessel. Argon was introduced for 15 minutes, and then the mixture was placed in an oil bath to react at 65℃for 24 hours, to obtain a functional polyamide 2d.
Comparative example 1
Preparation of functional polyamides
40 parts by weight of the functional polyamide monomer 1 of example 1, 60 parts by weight of the functional polyamide monomer 2 of example 2, 100 parts by weight of 3, 6-dioxa-1, 8-octanedithiol, and 0.2 part by weight of the catalyst AIBN and 15 parts by weight of tetrahydrofuran were taken into a reaction vessel. Argon was introduced for 15 minutes, and then the mixture was placed in an oil bath to react at 65℃for 24 hours, to obtain a functional polyamide.
Example 6
Preparation of functional Polyamide 3
40 parts by weight of the functional polyamide monomer 1 of example 1 and 60 parts by weight of the functional polyamide monomer A of example 1, 100 parts by weight of 3, 6-dioxa-1, 8-octanedithiol, and 0.2 part by weight of catalyst AIBN and 15 parts by weight of tetrahydrofuran were charged into a reaction vessel. Argon was introduced for 15 minutes, and then the mixture was placed in an oil bath to react at 65℃for 24 hours, to obtain functional polyamide 3.
Example 7
Preparation of functional Polyamide 4-1
90 parts by weight of the functional polyamide monomer 2 of example 2 and 10 parts by weight of the functional polyamide monomer A of example 1, 100 parts by weight of 3, 6-dioxa-1, 8-octanedithiol, 0.2 part by weight of catalyst AIBN and 15 parts by weight of tetrahydrofuran were taken into a reaction vessel. Argon is introduced for 15 minutes, and then the mixture is placed in an oil bath pot for reaction at 65 ℃ for 24 hours, so that the functional polyamide 4-1 is obtained.
Example 8
Preparation of functional Polyamide 4-2
60 parts by weight of the functional polyamide monomer 2 of example 2 and 25 parts by weight of the functional polyamide monomer A of example 1, 100 parts by weight of 3, 6-dioxa-1, 8-octanedithiol, and 0.2 part by weight of catalyst AIBN and 15 parts by weight of tetrahydrofuran were charged into a reaction vessel. Argon is introduced for 15 minutes, and then the mixture is placed in an oil bath pot for reaction for 24 hours at 65 ℃ to obtain the functional polyamide 4-2.
FIG. 2 is a DSC chart of the functional polyamide prepared in examples 2-5 of the present invention and comparative example 1; as can be seen from fig. 2, the glass transition temperature of each proportion of the polymer is below 0 ℃, and the glass transition temperature of the polymer is obviously affected with the introduction of the succinate group; the melting point is in the range of 90-100 ℃, the change of the melting point is caused by the introduction of a side chain succinate group, the introduction of the succinate group causes the change of the number of hydrogen bonds among molecular chains, and the melting point of the polymer is influenced, and a small amount of succinate groups can reduce the number of the hydrogen bonds among the molecular chains, because the succinate groups have larger steric hindrance, the distance among the molecular chains is expanded, so that the hydrogen bonds among the molecular chains are difficult to form, and the melting point of the polymer is reduced; with the increase of the content of the succinate groups, the carboxyl groups on the succinate groups and the amide groups form hydrogen bonds, so that the content of the hydrogen bonds among chains is increased, and the melting point of the polymer is increased.
FIG. 3 is a stress-strain graph of the functional polyamides prepared in examples 2-5 and comparative example 1 of the present invention; as can be seen from fig. 3, with the increase of the content of the functional polyamide monomer a (MUDA), the breaking strengths of example 2, example 3, example 4, and example 5 were 24.5±0.5MPa, 27.2±0.2MPa, 26.9±0.6MPa, and 29.4±0.1MPa, respectively, which are superior to the breaking strengths of the samples 21.7±0.3MPa, in which no MUDA was introduced; and the ultimate tensile elongation of the polymer is from 650.2+/-27.4% without MUDA to 820.3 +/-15.1% with MUDA content of 8%, and the toughness is from 81.55 MJ.m -3 Increase to 128.8+ -2.1 MJ.m -3 The specific parameters are shown in Table 1. In general, the mechanical properties of the polyamide show increasing and decreasing with increasing content of carboxyl groups in the side chains, and when the proportion of MUDA content is high, the breaking strength is greatly increased, and the tensile breaking strain is increased and then decreased. When the MUDA content is 8%, the mechanical property of the polyamide is optimal, and the breaking stress, the breaking elongation and the toughness are respectively 27.2MPa, 820.3 percent and 128.8 MJ.m -3 。
FIG. 4 is a stress-strain graph of the functional polyamides prepared in example 1 and examples 6-7 of the present invention; as can be seen from fig. 4 and table 2, with polyamide 1 as a control, the mechanical properties of the polymer changed significantly with the introduction of the amide monomer 1 or 2 in the copolymer. The breaking strength of polyamide 1 was 8.4.+ -. 0.3MPa, and the breaking strengths of polyamide 3 and polyamide 4-1 were 17.7.+ -. 0.6MPa and 2.3.+ -. 0.1MPa, respectively, whereby it was found that the introduction of the amide monomer 1 contributed to the mechanical properties of the polymer, since the side chain hydroxyl groups were able to form crystalline regions, resulting in improved properties. The introduction of the amide monomer 2 weakens the strength of the polymer, but the elongation at break of the polymer is obviously improved, and the mechanical property of the polymer is weakened due to the influence of side-chain butyl groups on hydrogen bonds formed among molecular chains, and the number of the hydrogen bonds among the molecules is reduced.
FIG. 5 is a plot of the bond stroke-shear strength for the functional polyamides prepared in examples 2-5 and comparative example 1 of the present invention; from fig. 5, it can be seen that as the mud content in the polymer increases gradually, the adhesion ability of the polymer increases and then decreases. It can be derived that the polyamide hot melt adhesive gives the best adhesion properties at a MUDA content of 8%.
Polyamide 1, polyamide 3 and polyamide 4-1 were first prepared into a film of 12.5mm x 25mm and 2mm thick, then placed on an aluminum sheet, covered with another sheet, placed in a 120 ℃ oven for 10 minutes, then taken out and cooled to room temperature to be tested, and the graph of the bonded stroke-shear strength is shown in fig. 6; as is clear from FIG. 6, the shear strength of polyamide 1 (example 1), polyamide 3 (example 6) and polyamide 4-1 (example 7) on the surface of the aluminum sheet was 7.05.+ -. 0.27MPa, 4.23.+ -. 0.20MPa and 9.61.+ -. 0.46MPa in this order. Thus, it can be shown that the synergistic effect of the butyl group of the side chain of the amide monomer 2 and the carboxyl group in the succinate group of the side chain of the amide monomer A improves the adhesion of the polymer on the surface of the aluminum sheet.
The polyamide materials prepared in examples 1 to 7 and comparative example 1 were tested for mechanical properties, shear strength, glass transition temperature as follows:
the mechanical property testing method comprises the following steps: mechanical tensile testing was performed using a UTM2502 type electronic universal tester. The mechanical test was performed by cutting dumbbell-shaped pieces with the same-size cutter for each set of examples and comparative examples. The tensile speed of the sample bar test at room temperature was 50mm/min. At the same time, it is required that each set of samples should be tested in the same temperature and humidity environment.
Shear strength testing method: the sample was cut into 12.5mm by 25mm coupons and placed between substrates and glued at 120℃for 30min. Shear force of the bonded substrate was measured using a UTM2502 type electronic universal tester.
Glass transition temperature test method: the glass transition temperature test was measured using a DSC200F3 Maia thermogravimetric analyzer (DSC, NETZSCH, germany) for each set of examples and comparative examples, and DSC curves were obtained for each set of samples. Test conditions: the temperature rising rate is 10K/min in nitrogen atmosphere. Test procedure: the first stage after machine equilibration was warmed from room temperature to 150 ℃ to eliminate sample thermal history at a rate of 50 ℃/min. The second stage is to cool from 150 ℃ to-150 ℃ with a cooling rate of 50 ℃/min. The temperature rising rate in the third stage is 5 ℃/min, and the temperature rising interval is-50-1550 ℃. The final data were taken at-50-150℃from which DSC curves for each set of samples were obtained.
The test results were as follows:
TABLE 1 statistical tables of tensile Property test data for ternary Polyamide materials
TABLE 2 statistical tables of tensile test data for binary and individual polyamide materials
From tables 1 and 2, it can be seen that the different side groups have different effects on the mechanical properties, but the overall present invention exhibits more excellent mechanical properties than the existing hot melt adhesive materials.
Table 3 statistics of data of normal temperature shear performance test of ternary polyamide material
Table 4 statistics of normal temperature shear performance test data for binary and individual polyamide materials
As can be seen from tables 3 and 4, the effect of different side groups and the content of the side groups on the adhesive property of the polymers is also greatly different, and the prepared polyamide hot melt adhesive has higher adhesive strength compared with the existing polyamide hot melt adhesive.
TABLE 5 statistical tables of shear performance test data for the ternary polyamide materials at various temperatures
TABLE 6 statistical tables of shear performance test data for the respective humidities of the ternary polyamide material of example 3
As can be seen from tables 5 and 6, the polyamide hot melt adhesive prepared in example 3 still has excellent adhesive strength under low temperature and various humidity environments.
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. An ultralow-temperature bio-based polyamide hot melt adhesive is characterized in that: the structural formula is as follows:
wherein n is more than or equal to 5 and less than or equal to 5000;
r isOr R is->Repetition of any one or more of the following structures:
-H。
2. the ultra-low temperature bio-based polyamide hot melt adhesive of claim 1, wherein: the functional polyamide monomer is prepared from the same functional polyamide monomer and 3, 6-dioxa-1, 8-octane dithiol through a mercapto-olefin click reaction, and the structural formula of the functional polyamide monomer is as follows:
wherein R is->
3. The ultra-low temperature bio-based polyamide hot melt adhesive of claim 1, wherein: the functional polyamide is prepared from two different functional polyamide monomers and 3, 6-dioxa-1, 8-octane dithiol through a mercapto-olefin click reaction, wherein the two different functional polyamide monomers are respectively a functional polyamide monomer A and a functional polyamide monomer B;
the structural formula of the functional polyamide monomer A is as follows:
wherein R is->
The structural formula of the functional polyamide monomer B is as follows:
wherein R is any one of the following structures: -H。
4. the ultra-low temperature bio-based polyamide hot melt adhesive of claim 1, wherein: the functional polyamide is prepared from three different functional polyamide monomers, namely a functional polyamide monomer A, a functional polyamide monomer B and a functional polyamide monomer C, by a mercapto-olefin click reaction with 3, 6-dioxa-1, 8-octanedithiol;
the structural formula of the functional polyamide monomer A is as follows:
wherein R is->
The structural formulas of the functional polyamide monomer B and the functional polyamide monomer C are as follows:
wherein, the functional polyamide monomer B and the functional polyamide monomer C are different from each other in R, and are selected from any one of the following structures: -H。
5. a process for the preparation of an ultralow temperature biobased polyamide hot melt adhesive as defined in any one of claims 1-4, characterized in that: the method comprises the following steps: taking 1-100 parts by weight of functional polyamide monomer, 1-100 parts by weight of 3, 6-dioxa-1, 8-octanedithiol, and 0.1-10 parts by weight of catalyst to dissolve in 1-100 parts by weight of solvent, and placing the mixture in a condition of 40-100 ℃ to react for 12-36 hours to obtain the ultralow temperature bio-based polyamide hot melt adhesive; wherein the structural formula of the functional polyamide monomer is as follows:
r is -any one of H.
6. The method for preparing the ultralow temperature bio-based polyamide hot melt adhesive according to claim 5, which is characterized in that: the catalyst is azodiisobutyronitrile; the solvent is tetrahydrofuran.
7. The method for preparing the ultralow temperature bio-based polyamide hot melt adhesive according to claim 5, which is characterized in that: the functional polyamide monomer comprises a functional polyamide monomer A and a functional polyamide monomer B with different R, wherein the mass ratio of the functional polyamide monomer A to the functional polyamide monomer B is 10-60:40-90, the structural formula of the functional polyamide monomer A is as follows:
wherein R is->
8. The method for preparing the ultralow temperature bio-based polyamide hot melt adhesive according to claim 7, wherein the method comprises the following steps: the structural formula of the functional polyamide monomer B is as follows:
wherein R is->or-H.
9. The method for preparing the ultralow temperature bio-based polyamide hot melt adhesive according to claim 5, which is characterized in that: the functional polyamide monomer comprises a functional polyamide monomer A, a functional polyamide monomer B and a functional polyamide monomer C, wherein R is different; the mass ratio of the functional polyamide monomer A to the functional polyamide monomer B to the functional polyamide monomer C is 5-25:35-60:40, a step of performing a; the structural formula of the functional polyamide monomer A is as follows:
wherein R is->
10. The method for preparing the ultralow temperature bio-based polyamide hot melt adhesive according to claim 9, wherein the method comprises the following steps: the structural formula of the functional polyamide monomer B is as follows:
wherein R is
The structural formula of the functional polyamide monomer C is as follows:
wherein R is-H.
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