CN114805748B - Sustainable and high-modulus Schiff base functional polyurethane prepolymer and preparation method thereof - Google Patents
Sustainable and high-modulus Schiff base functional polyurethane prepolymer and preparation method thereof Download PDFInfo
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- 229920001730 Moisture cure polyurethane Polymers 0.000 title claims abstract description 187
- 150000004753 Schiff bases Chemical class 0.000 title claims abstract description 70
- 239000002262 Schiff base Substances 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 42
- 125000003118 aryl group Chemical group 0.000 claims abstract description 37
- 150000001412 amines Chemical class 0.000 claims abstract description 29
- 239000000126 substance Substances 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 26
- 230000007062 hydrolysis Effects 0.000 claims abstract description 17
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 17
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 14
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 13
- 238000011065 in-situ storage Methods 0.000 claims abstract description 10
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 9
- 150000004982 aromatic amines Chemical class 0.000 claims abstract description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 5
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims abstract 9
- -1 aldehyde compound Chemical class 0.000 claims description 47
- 238000004519 manufacturing process Methods 0.000 claims description 17
- 238000011084 recovery Methods 0.000 claims description 16
- 229920000642 polymer Polymers 0.000 claims description 14
- 229920005862 polyol Polymers 0.000 claims description 12
- 150000003077 polyols Chemical class 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 229920001187 thermosetting polymer Polymers 0.000 claims description 9
- 239000002699 waste material Substances 0.000 claims description 8
- 150000001413 amino acids Chemical class 0.000 claims description 7
- 239000004634 thermosetting polymer Substances 0.000 claims description 7
- 229920000647 polyepoxide Polymers 0.000 claims description 6
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims description 5
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 5
- 239000003822 epoxy resin Substances 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- 229920001228 polyisocyanate Polymers 0.000 claims description 5
- 239000005056 polyisocyanate Substances 0.000 claims description 5
- 229920005989 resin Polymers 0.000 claims description 5
- 239000011347 resin Substances 0.000 claims description 5
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- 230000003301 hydrolyzing effect Effects 0.000 claims description 4
- 229920002647 polyamide Polymers 0.000 claims description 4
- 229920000728 polyester Polymers 0.000 claims description 4
- 229920006337 unsaturated polyester resin Polymers 0.000 claims description 4
- 150000004984 aromatic diamines Chemical class 0.000 claims description 3
- 229920005749 polyurethane resin Polymers 0.000 claims description 3
- 230000002035 prolonged effect Effects 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 30
- 239000003960 organic solvent Substances 0.000 abstract description 5
- 238000005649 metathesis reaction Methods 0.000 abstract description 4
- 239000007788 liquid Substances 0.000 abstract description 3
- 150000001299 aldehydes Chemical group 0.000 description 21
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 18
- 239000002861 polymer material Substances 0.000 description 13
- 230000015572 biosynthetic process Effects 0.000 description 11
- 238000005755 formation reaction Methods 0.000 description 10
- 229940015043 glyoxal Drugs 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 8
- 239000012299 nitrogen atmosphere Substances 0.000 description 8
- 101000773908 Archaeoglobus fulgidus (strain ATCC 49558 / DSM 4304 / JCM 9628 / NBRC 100126 / VC-16) Acetate-CoA ligase [ADP-forming] II Proteins 0.000 description 7
- 230000008901 benefit Effects 0.000 description 7
- 239000012948 isocyanate Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 239000000376 reactant Substances 0.000 description 7
- 229920001169 thermoplastic Polymers 0.000 description 7
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 6
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000004814 polyurethane Substances 0.000 description 6
- 101000773907 Archaeoglobus fulgidus (strain ATCC 49558 / DSM 4304 / JCM 9628 / NBRC 100126 / VC-16) Acetate-CoA ligase [ADP-forming] I Proteins 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 125000003277 amino group Chemical group 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 4
- 125000003172 aldehyde group Chemical group 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 229920002635 polyurethane Polymers 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 description 4
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 3
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical compound N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- 239000004471 Glycine Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 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 3
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 description 3
- 235000012141 vanillin Nutrition 0.000 description 3
- 239000003039 volatile agent Substances 0.000 description 3
- ZXHZWRZAWJVPIC-UHFFFAOYSA-N 1,2-diisocyanatonaphthalene Chemical compound C1=CC=CC2=C(N=C=O)C(N=C=O)=CC=C21 ZXHZWRZAWJVPIC-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 125000001931 aliphatic group Chemical class 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 230000021615 conjugation Effects 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000012691 depolymerization reaction Methods 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000010952 in-situ formation Methods 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000010128 melt processing Methods 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000004848 polyfunctional curative Substances 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- PXJJKVNIMAZHCB-UHFFFAOYSA-N 2,5-diformylfuran Chemical compound O=CC1=CC=C(C=O)O1 PXJJKVNIMAZHCB-UHFFFAOYSA-N 0.000 description 1
- BLFRQYKZFKYQLO-UHFFFAOYSA-N 4-aminobutan-1-ol Chemical compound NCCCCO BLFRQYKZFKYQLO-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 229920000106 Liquid crystal polymer Polymers 0.000 description 1
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920002396 Polyurea Polymers 0.000 description 1
- WUGQZFFCHPXWKQ-UHFFFAOYSA-N Propanolamine Chemical compound NCCCO WUGQZFFCHPXWKQ-UHFFFAOYSA-N 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 150000007824 aliphatic compounds Chemical class 0.000 description 1
- VVLCNWYWKSWJTG-UHFFFAOYSA-N anthracene-1,2-diamine Chemical compound C1=CC=CC2=CC3=C(N)C(N)=CC=C3C=C21 VVLCNWYWKSWJTG-UHFFFAOYSA-N 0.000 description 1
- SESSRFZDDUZRQV-UHFFFAOYSA-N anthracene-1,2-dicarbaldehyde Chemical compound C1=CC=CC2=CC3=C(C=O)C(C=O)=CC=C3C=C21 SESSRFZDDUZRQV-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- HSJKGGMUJITCBW-UHFFFAOYSA-N beta-hydroxybutyraldehyde Natural products CC(O)CC=O HSJKGGMUJITCBW-UHFFFAOYSA-N 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000013626 chemical specie Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000004002 naphthaldehydes Chemical class 0.000 description 1
- NTNWKDHZTDQSST-UHFFFAOYSA-N naphthalene-1,2-diamine Chemical compound C1=CC=CC2=C(N)C(N)=CC=C21 NTNWKDHZTDQSST-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 238000004184 polymer manufacturing process Methods 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920000909 polytetrahydrofuran Polymers 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/83—Chemically modified polymers
- C08G18/84—Chemically modified polymers by aldehydes
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/83—Chemically modified polymers
- C08G18/833—Chemically modified polymers by nitrogen containing compounds
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a sustainable and high-modulus Schiff base functional polyurethane prepolymer and a preparation method thereof. The preparation method comprises the following steps: first, preparing an aromatic amine terminated polyurethane prepolymer; in a second step, a functional schiff base polyurethane prepolymer containing an aromatic conjugated schiff base structure is formed by in situ reaction of an aromatic amine-terminated polyurethane prepolymer and an aldehyde. The sustainable and high-modulus Schiff base functional polyurethane prepolymer prepared by the method has one or more of amine, aldehyde, hydroxyl, vinyl or carboxyl functionalized at the tail end; at normal pressure of 100 ℃ or lower, the hydrolysis realizes chemical circulation, and has sustainability, self-healing capability and low melt viscosity. The invention prepares the functional polyurethane prepolymer containing the aromatic conjugated Schiff base by an in-situ forming method without using an organic solvent. The functional polyurethane prepolymers are easy to handle in the liquid state and impart sustainability to the polymeric materials prepared therefrom, thereby achieving high modulus of the polymeric materials. In addition, polymeric materials based on functional polyurethane prepolymers are environmentally friendly, they have excellent mechanical properties, have self-healing ability due to the metathesis of schiff base groups, and can be recovered by hydrolysis under mild temperature conditions.
Description
Technical Field
The present invention relates to a functional polyurethane prepolymer and a method for preparing the same, and more particularly, to a Schiff-base (Schiff-bases) polyurethane prepolymer which imparts sustainability by self-healing ability and chemical recovery by hydrolysis, and a method for preparing the same.
Background
Polymers or polymeric materials generally have a large molecular weight of 10,000 daltons or more and a characteristic chemical structure of the repeating unit, and are widely used in the fields of plastics, fibers, rubber, adhesives, paints, and the like. The wide application of the polymer material is based on the advantages of light weight, good corrosion resistance, low cost and the like of the product. Due to the above-mentioned advantages, the consumption of polymeric materials is continuously increasing. However, there is a great concern that the waste generated after the use of the polymer material may destroy the natural environment. Therefore, it is necessary to extend the service life of the polymer material-based products and to recycle the used waste, thereby achieving the sustainability of the polymer materials.
The polymeric materials can be divided into thermoplastic polymers (thermoplastic polymers) and thermosetting polymers (thermosetting polymers). Thermoplastic polymers typically have a linear molecular backbone and can be repeatedly heated and softened to shape. In contrast, thermosetting polymers are formed from oligomers (oligomers) by a crosslinking reaction after heating or high-energy irradiation, and are difficult to process repeatedly because of the crosslinked structure. Examples of thermoplastic polymers include plastics, such as polyolefins and polystyrenes for packaging, and film and fiber forming materials, such as polyamide-6, 6 and polyethylene terephthalate. Examples of thermosetting polymers include epoxy resins, unsaturated polyester resins, and conventional crosslinked rubbers. Products made of thermoplastic polymers are typically readily physically recycled by mixing with virgin resin through a melt process after collection, separation, crushing and washing after use. However, highly contaminated thermoplastic polymers and crosslinked thermoset polymeric materials are difficult to physically recycle, often require chemical recovery procedures for high temperature depolymerization reactions, and have not been industrially recycled.
In order to achieve sustainability by recycling polymeric materials, appropriate physical and chemical recycling techniques need to be developed depending on the type of polymeric material. For highly contaminated thermoplastic polymers and crosslinked thermoset polymeric materials that require chemical recovery, a substance with sustainability can be incorporated into the molecular backbone of the polymeric material at the manufacturing stage, thereby enabling chemical recovery under mild conditions (e.g., hydrolysis). The raw material of polymeric material waste by chemical recovery generally requires various depolymerization reaction processes at a temperature of at least 200 ℃ or higher, and thus, deterioration due to side reactions is unavoidable, and the quality of recovered products cannot reach the quality of new materials. However, hydrolysis is attractive because it can promote the raw material by reducing the molecular weight with water under relatively mild conditions (100 ℃) to minimize side reactions and to make chemical recovery relatively easy. The introduction of chemical components that are capable of hydrolysis in the chemical recovery of the product is contemplated. However, in the application of polymeric materials, the introduction of molecular structures for hydrolysis generally involves the risk of reducing mechanical strength and chemical stability.
Disclosure of Invention
The object of the present invention is to solve the above-mentioned problems of the prior art by providing a functional oligomer, schiff-base of polyurethane prepolymers, schiff-base polyurethane prepolymer, which achieves sustainability by hydrolysis of waste after use at 100 ℃ or below under atmospheric pressure, chemical recovery while maintaining the mechanical properties of the product at a level equal to or better than that of conventional products and can extend the service life by self-repair.
Furthermore, it is another object of the present invention to provide a process for the manufacture of functional oligomers, schiff base polyurethane prepolymers, achieving sustainability through chemical recovery of waste after hydrolytic use at 100 ℃ or below under atmospheric pressure while maintaining the mechanical properties of the product to levels or superior to conventional products and allowing for extended service life through self-healing.
An isocyanate-terminated polyurethane prepolymer (isocyanate-terminated polyurethane prepolymer) obtained by reacting a polyol and an aromatic polyisocyanate; reacting the isocyanate-terminated polyurethane prepolymer with water to obtain an amine-terminated polyurethane prepolymer (amine-terminated polyurethane prepolymer); the amine-terminated polyurethane prepolymer and aldehyde compound react to obtain the functional polyurethane prepolymer with aromatic conjugated Schiff base (aromatic conjugated Schiff-base, abbreviated as ACS). The amine terminated polyurethane prepolymer is reacted with an alditol compound and a vinyl aldehyde, respectively, to form a schiff base to obtain a functional polyurethane prepolymer having ACS architecture with hydroxyl and vinyl groups at the chain ends.
The terminal aldehyde polyurethane prepolymer is reacted with a hydroxylamine compound and an amino acid, respectively, to form a schiff base to obtain an ACS-structured functional polyurethane prepolymer having hydroxyl and carboxylic acid groups at the chain ends.
In the present invention, ACS is introduced by an in-situ reaction during the polyurethane prepolymer production process. The following equations 2 and 3:
reaction 2
Reaction 3
ACS is formed directly within the molecular structure of the polyurethane prepolymer by the schiff base formation reaction between the amine-terminated polyurethane prepolymer and the aldehyde component. Furthermore, ACS plays an enhancing role at the molecular level as a mesogen imparting liquid crystal characteristics. In general, when an aliphatic schiff base is contained in the polymer structure, the mechanical properties and chemical stability of the polymer material tend to be weakened, but in the present invention, the schiff base component of an aromatic conjugate structure is formed in the polyurethane prepolymer, and the mechanical properties of the polymer material prepared therefrom are generally equivalent to or better than those of the polymer material containing no schiff base.
Furthermore, according to the invention, ACS functions to depolymerize the waste after the end of the life of the polymeric material by hydrolysis at 100 ℃ or less at ambient pressure. The schiff base structure formed by the in situ reaction realizes a high-elasticity product through a strengthening effect (such as mesogen) on a molecular level. In the melt processing of polymer products containing ACS-structured polyurethane prepolymers, the viscosity of the polymer melt is greatly reduced by the metathesis of schiff bases, showing good flowability. Polymer products containing ACS-structured polyurethane prepolymers recover cracks and scratches during use by appropriate stimuli, thereby imparting reworkability and self-healing ability to the crosslinked polymer adhesive.
Furthermore, the polyurethane prepolymers containing ACS architecture in the present invention may be incorporated into polyesters, polyamides and vinyl polymers as well as thermosetting polymers such as polyurethane resins, epoxy resins, unsaturated polyester resins to impart sustainability to the polymeric material. It can be used to functionalize a variety of polymeric materials of different compositions.
The invention also provides a method for preparing various functional Schiff base polyurethane prepolymers with sustainability.
In the preparation method of the Schiff base polyurethane prepolymer, an amine-terminated polyurethane prepolymer is prepared by taking aromatic isocyanate as a terminal polyurethane prepolymer, and then the amine-terminated polyurethane prepolymer is reacted with an aldehyde compound to obtain the Schiff base polyurethane prepolymer containing ACS.
The amine terminated polyurethane prepolymer is reacted with an alditol compound and a vinyl aldehyde, respectively, to form a schiff base to obtain a functional polyurethane prepolymer having ACS architecture with hydroxyl and vinyl groups at the chain ends.
The terminal aldehyde polyurethane prepolymer is reacted with a hydroxylamine compound and an amino acid, respectively, to form a schiff base to obtain an ACS-structured functional polyurethane prepolymer having hydroxyl and carboxylic acid groups at the chain ends.
As a first step, the present invention includes a process for preparing an aromatic amine terminated polyurethane prepolymer. The polyurethane prepolymer may be obtained by reacting water with an isocyanate-terminated polyurethane polymer prepared from 4, 4-diphenylmethane diisocyanate (MDI) and a polyol, as shown in reaction scheme 1.
Reaction 1
On the other hand, aromatic diamines such as 4,4' -Methylenedianiline (MDA) may be reacted with isocyanate terminated polyurethane polymers instead of water to give amine terminated poly (urethane-co-urea) prepolymers.
As a second step, the present invention includes a step of reacting the aromatic amine-terminated polyurethane prepolymer obtained in the first step with an aldehyde compound. Representative reactions of different stoichiometries are given as shown in equations 2, 3, showing the specific structure of the product.
Reaction 2
Reaction 3
In the second step, the chemical species that reacts with the aromatic amine-terminated polyurethane prepolymer is a specific aldehyde compound. When the aldehyde compounds have a symmetrical structure, they react with the amine-terminated polyurethane prepolymer to form schiff bases and obtain a product having a symmetrical ACS structure within the oligomer, through which a mesogenic effect can be effectively achieved in the prepared polymer material. As the aldehyde compound, glyoxal is preferable for the aliphatic compound because the aldehyde group is singly linked; for aromatic compounds, glyoxal terephthalate is preferred because of the linking of the aldehyde groups and the aromatic structure.
In the second step, the reason for the reaction of the aldehyde with the amine-terminated polyurethane prepolymer and the process thereof can be explained as follows.
In carrying out the reactions of the reaction formulae 1, 2 and 3, since the polyurethane prepolymer is liquid, easy to manage, and the ACS-containing polyurethane prepolymer is formed by in-situ reaction, it is not necessary to use an organic solvent during the reaction. ACS compounds prepared by a separate process are generally crystalline, and ACS should be introduced into polyurethane prepolymer by chemical reaction using an organic solvent.
As shown in reaction formula 2, in the process of reacting an aldehyde compound with a amine terminated polyurethane prepolymer to form schiff base, when the amine concentration of the amine terminated polyurethane prepolymer is higher than that of the dialdehyde compound in the reaction, the amine terminated polyurethane prepolymer (hereinafter abbreviated as ACS-I) is obtained. ACS-I with amine groups at the end can be used as raw material for manufacturing polyurea, polyamide and epoxy hardener, as well as introducing various functional groups at the end. On the other hand, when the amine concentration of the terminal amine-type polyurethane prepolymer is lower than the aldehyde concentration of the dialdehyde compound, as shown in reaction formula 3, the terminal aldehyde-type polyurethane prepolymer (hereinafter abbreviated as ACS-II) is obtained. The terminal aldehyde polyurethane prepolymers can be used to prepare imine resins and to introduce various functional groups at the ends.
In addition, in order to incorporate these Schiff base polyurethane prepolymers as part of the backbone of various polymeric materials, it is necessary to incorporate various functional groups such as hydroxyl, carboxyl and vinyl groups at the chain ends.
As shown in scheme 4, an additional Schiff base formation reaction between ACS-I and an aldol compound (e.g., vanillin) can be used to obtain an ACS-containing hydroxyl-terminated polyurethane prepolymer (hereinafter ACS-III).
Reaction 4
Such hydroxyl-terminated polyurethane prepolymer schiff bases are useful not only in polyurethane production, but also in polyester and epoxy production compositions to achieve sustainability through self-healing and hydrolysis of polymeric materials for chemical recovery after end of service life.
The amine-terminated Schiff base of the Schiff base polyurethane prepolymer may be further reacted with a vinyl aldehyde compound such as acrolein by an additional Schiff base formation reaction to give a vinyl-terminated Schiff base polyurethane prepolymer (hereinafter referred to as ACS-IV). Equation 5 shows the equation for the preparation of vinyl terminated Schiff base polyurethane prepolymers from ACS-I and vinylaldehyde acrolein.
Reaction 5
ACS-iv can be used to prepare various copolymers of vinyl polymers, which are chemically recovered after the end of their useful life by self-healing and hydrolysis of the polymeric material, thereby imparting sustainability to the polymer.
On the other hand, the terminal aldehyde Schiff base polyurethane prepolymer can be reacted with hydroxylamine such as monoethanolamine to obtain a hydroxyl-terminated Schiff base polyurethane prepolymer (hereinafter referred to as ACS-V). Equation 6 shows the reaction scheme for preparing hydroxyl-terminated schiff base polyurethane prepolymers from ACS-II and hydroxylamine, monoethanolamine.
Reaction 6
Hydroxyl-terminated schiff base polyurethane prepolymers are applicable to a variety of polyurethanes, epoxies, and polyesters, imparting sustainability to polymeric materials by self-healing ability, and achieving chemical recycling by hydrolyzing polymeric materials prepared therefrom.
In addition, the aldehyde-terminated Schiff base polyurethane prepolymer can be reacted with amino acids such as glycine to obtain a carboxyl-terminated Schiff base polyurethane prepolymer (hereinafter referred to as ACS-VI). Equation 7 shows the reaction for preparing a carboxyl terminated Schiff base polyurethane prepolymer (ACS-VI) from ACS-II and an amino acid.
Reaction 7
Carboxyl-terminated schiff base polyurethane prepolymers are applicable to a variety of polymers including polyamides, epoxy resins and polyester resins as hardeners, imparting sustainability to polymeric materials by self-healing ability, and achieving chemical recovery by hydrolysis of polymeric materials prepared therefrom.
Generally, low molecular compounds having an aromatic conjugated schiff base moiety have crystallinity, and therefore ACS is not easily incorporated into the polymer manufacturing process unless an organic solvent is used. However, in the present invention, if the first, second and third steps are performed, ACS can be easily incorporated into the main chain of the polymer material by in situ formation, and sustainability is brought about by self-healing function and hydrolysis, thereby being used for chemical recycling after discard.
Polymeric materials prepared from functional polyurethane prepolymers, including ACS, exhibit high strength or high elasticity due to molecular-level reinforcing effects (e.g., mesogens) in liquid crystal polymers. In the case of highly elastic polymer materials based on polyurethane prepolymers containing ACS, the melt viscosity of the polymer material is reduced and good flowability is exhibited by the metathesis reaction of schiff bases.
The invention has the beneficial effects that:
the invention has the advantage that the functional polyurethane prepolymer containing the aromatic conjugated Schiff base is prepared by an in-situ formation method without using an organic solvent. The functional polyurethane prepolymers are easy to handle in the liquid state and impart sustainability to the polymeric materials prepared therefrom, thereby achieving high modulus of the polymeric materials.
Furthermore, it is an advantage of the present invention that ACS architecture is incorporated into functional schiff base polyurethane prepolymers using conventional methods for making polyurethane prepolymers. Furthermore, polymeric materials based on functional polyurethane prepolymers (including ACS) are environmentally friendly, they have excellent mechanical properties, have self-healing ability due to the metathesis of schiff base groups, and can be recovered by hydrolysis under mild temperature conditions.
Detailed Description
Hereinafter, the present invention will be described in more detail. The specific values or specific embodiments provided in the present invention are preferred embodiments of the present invention for describing the technical idea of the present invention in more detail, and it is apparent that the present invention is not limited thereto.
In addition, in the description of the present invention, detailed descriptions of parts known in the art and parts that can be easily created by those skilled in the art will be omitted.
A method for preparing sustainable and high modulus schiff base functional polyurethane prepolymer, comprising the steps of:
first, preparing an aromatic amine terminated polyurethane prepolymer;
in a second step, a functional schiff base polyurethane prepolymer containing an aromatic conjugated schiff base (ACS) architecture is formed by in situ reaction of an aromatic amine-terminated polyurethane prepolymer and an aldehyde.
In the second step, when the amine concentration of the aromatic amine-terminated polyurethane prepolymer is higher than the aldehyde concentration of the aldehyde compound, an amine-terminated polyurethane prepolymer containing ACS structure is obtained;
the hydroxyl-terminated polyurethane prepolymer containing ACS structure is then prepared by reacting an amine-terminated polyurethane prepolymer containing ACS structure with an alditol compound.
In the second step, when the amine concentration of the aromatic amine-terminated polyurethane prepolymer is higher than the aldehyde concentration of the aldehyde compound, an amine-terminated polyurethane prepolymer containing ACS structure is obtained;
the vinyl-terminated polyurethane prepolymer containing ACS structure is then prepared by reacting the amine-terminated polyurethane prepolymer containing ACS structure with vinyl aldehyde.
In the second step, when the amine concentration of the aromatic amine-terminated polyurethane prepolymer is lower than the aldehyde concentration of the aldehyde compound, an aldehyde-terminated polyurethane prepolymer containing ACS structure is obtained;
hydroxyl-terminated polyurethane prepolymers containing ACS structure are then prepared from the reaction of aldehyde-terminated polyurethane prepolymers containing ACS structure with hydroxylamine.
In the second step, when the amine concentration of the aromatic amine-terminated polyurethane prepolymer is lower than the aldehyde concentration of the aldehyde compound, obtaining an aldehyde-terminated polyurethane prepolymer containing ACS structure;
the carboxylic acid group-containing polyurethane prepolymer containing ACS structure is then prepared by reacting the aldehyde-containing polyurethane prepolymer containing ACS structure with an amino acid.
In the first step, an isocyanate-terminated polyurethane prepolymer is obtained by reacting a polyol with an aromatic polyisocyanate, and the isocyanate-terminated polyurethane prepolymer is reacted with water to obtain an aromatic amine-terminated polyurethane prepolymer.
In the first step, an isocyanate-terminated polyurethane prepolymer is obtained by reacting a polyol with an aromatic polyisocyanate, and the isocyanate-terminated polyurethane prepolymer is reacted with an aromatic diamine to obtain an aromatic amine-terminated polyurethane prepolymer.
A sustainable and high modulus schiff base functional polyurethane prepolymer prepared according to the method, wherein the end of the polyurethane prepolymer is functionalized by one or more of amine, aldehyde, hydroxyl, vinyl or carboxyl; at normal pressure of 100 ℃ or lower, the hydrolysis realizes chemical circulation, and has sustainability, self-healing capability and low melt viscosity.
The product based on the sustainable and high modulus Schiff base functional polyurethane prepolymer has sustainability and high modulus, the sustainability is realized by hydrolyzing the used product waste at 100 ℃ or below under the atmospheric pressure and chemical recovery, the mechanical properties of the product are maintained by the introduced mesogen, and the service life is prolonged by self-repairing.
According to the invention, the polyurethane prepolymer is prepared by taking the polyalcohol and the aromatic isocyanate as main raw materials, and the Schiff base structure containing an ACS structure is introduced into the polyurethane prepolymer through in-situ reaction, so that excellent elasticity and melt fluidity are realized, and the polymer material prepared from the polyurethane prepolymer is easy to chemically recycle.
In the present invention, the ACS-containing polyurethane prepolymer is produced by in-situ reaction between an aldehyde and an amine-terminated polyurethane prepolymer (amine-terminated polyurethane prepolymer) prepared from an isocyanate-terminated polyurethane prepolymer (isocyanate-terminated polyurethane prepolymer).
Functional polyurethane prepolymers having ACS architecture with hydroxyl and vinyl groups at the chain ends can be obtained from the additional schiff base formation of amine terminated polyurethane prepolymers containing alditol compounds and vinyl aldehydes, respectively. Furthermore, functional polyurethane prepolymers of ACS architecture having hydroxyl and carboxylic acid groups at the chain ends can also be obtained from the formation of the terminal aldehyde polyurethane prepolymer with an hydroxylamine compound and an additional schiff base of an amino acid, respectively.
In the present invention, the Schiff base polyurethane prepolymer containing ACS structure can be introduced as a part of polymer chain into the manufacturing process of polyurethane resin, epoxy resin, unsaturated polyester resin and vinyl resin, and has the advantages of easy chemical recovery, good elasticity and melt processability due to the characteristic double decomposition reaction of the Schiff base part.
The polyurethane prepolymer in the present invention is an isocyanate-terminated polyurethane prepolymer which can be prepared from an aromatic isocyanate and various polyols such as polyether polyol, ethylene glycol, polyester polyol, polycarbonate polyol, various copolymer polyols, natural polyol, and among polyols having an average molecular weight of 200 to 10000g/mol, a mixture having a molecular weight of 200 to 6000 g/mol and having two or more hydroxyl groups is preferable. Although Toluene Diisocyanate (TDI), MDI, xylene Diisocyanate (XDI), naphthalene Diisocyanate (NDI), etc. may be used as the aromatic isocyanate, it is advantageous to use a modified MDI that remains in a liquid phase at room temperature.
The aromatic isocyanate-terminated polyurethane prepolymer needs to be converted to an amine-terminated polyurethane prepolymer to form a schiff base. For this purpose, the aromatic isocyanate-terminated polyurethane prepolymer may be reacted with water as shown in reaction scheme 1.
For the preparation of amine-terminated polyurethane prepolymers, it is also possible to use aromatic isocyanate polyurethane prepolymers, aromatic diamine compounds, such as phenylenediamine and its isomers, methylenedianiline and its isomers, naphthalenediamine and its isomers, anthracenediamine and its isomers, and mixtures thereof. Examples of dialdehydes that can be reacted with amine terminated polyurethane prepolymers to obtain aromatic conjugated Schiff bases (ACS) include glyoxal, glyoxal terephthalate and its isomers, 2, 5-furandicarboxaldehyde, naphthaldehyde and its isomers, anthracene dialdehyde and its isomers, or mixtures thereof. In addition, compounds having various structures, both ends of which are composed of aldehydes, may be used alone or in combination.
The molecular weight of ACS structure is determined by the ratio (r) of the number of moles of amine groups in the amine-terminated prepolymer to the number of moles of aldehyde groups in the dialdehyde compound. The value of the ratio r is less than 1. Schiff base formation of the amine-terminated prepolymer and the dialdehyde compound is a condensation reaction, and the degree of schiff base formation (DS) is determined as follows.
If chain extension with ACS-i containing amine groups at the chain ends gives non-foamed poly (urethane-co-urea), the dialdehyde Concentration (CAL) of the reaction should be less than the amine group Concentration (CAM), i.e. r=cal/CAM <1 is necessary. On the other hand, when ACS-II requires an aldehyde-terminated polyurethane prepolymer, the concentration of aldehyde groups should be higher than the concentration of amine groups, i.e., r=CAM/CAL <1, the aldehyde-terminated prepolymer is reacted by Schiff base formation, followed by the addition of hydroxylamine compound to ACS-II as shown in equation 4
As shown, an ACS-structured polyurethane prepolymer (ACS-III) containing hydroxyl-terminated Schiff base was obtained.
On the other hand, the hydroxylamine used in ACS-II and the reaction for producing ACS-III includes isomers of aliphatic ethanolamine, propanolamine and butanolamine, and isomers of aromatic aminophenols, alicyclic aminocyclohexanols and the like. These isomers may be used alone or as a mixture.
The aromatic conjugated Schiff base polyurethane prepolymer can be prepared by reacting an amine terminated polyurethane prepolymer with an aldehyde compound. Here, in order to achieve an enhancement effect at a molecular level such as mesogen by conjugation of an aromatic moiety, it is recommended to use an aromatic dialdehyde such as terephthalaldehyde or glyoxal as an aliphatic dialdehyde capable of undergoing conjugation after schiff base formation. The ACS structure formed in situ plays a role in imparting high elasticity to the polymer material through the reinforcing effect on the molecular level. In addition, the double decomposition characteristic of the Schiff base structure can repair cracks or scratches, so that the advantages of reduced viscosity during melt processing, no residual stress after cooling and the like are realized. In addition, it has the advantage that it can be used as an environment-friendly material for various applications, which can be recovered as a raw material after use, by hydrolysis chemical recovery under mild atmospheric pressure, and repeatable physical recovery.
Hereinafter, the present invention will be described in more detail by means of specific examples. However, the data in the examples are given to aid in understanding the present invention, and the scope of the present invention is not limited thereto.
Example 1: preparation of isocyanate-terminated polyurethane prepolymers
The synthesis of the isocyanate-terminated PU prepolymers is carried out according to standard experimental methods commonly used in the art. To prepare the polyurethane prepolymer, 200.0 grams of modified MDI (Kumho Mitsui Chemicals: COSMONATE LL) having an NCO content of 29.1. 29.1 wt% were added to a 1 liter four-necked flask placed on a heating mantle at room temperature and maintained under a nitrogen atmosphere. After drying in a vacuum oven for 24 hours, 225.0g of poly (tetramethylene ether glycol) having a number average molecular weight of 650g/mol (PTMEG, merck reagent grade) were added. The temperature then increases. After 2 hours of urethane formation reaction at 60 ℃, the NCO content of the product was 6.7wt.% as measured by n-butylamine back titration according to ASTM D1638-74. The theoretical expected NCO content is 6.8 wt, taking account of experimental errors. In%, it was confirmed that the desired isocyanate terminated polyurethane prepolymer was obtained.
Example 2: preparation of amine-terminated polyurethane prepolymers
200g of PU prepolymer having an NCO content of 6.7% by weight obtained by the method for producing a polyurethane prepolymer described in example-1 was placed in a 500-mL four-necked flask on a heating mantle at room temperature, and a nitrogen atmosphere was maintained. Then, 12 g of distilled water was added and stirred for 2 hours. The temperature of the reactants was raised to 60 c due to the exothermic reaction of water and polyurethane prepolymer. The amine number after drying the unreacted excess water with a rotary evaporator was 95.1mgKOH/g according to ASTM D-2074-07.
Example 3: ACS-I preparation
200g of the amine-terminated polyurethane prepolymer having an amine value of 95.1mgKOH/g obtained by the method for producing a polyurethane prepolymer described in production example-2 was placed in a 500mL four-necked flask on a heating mantle at room temperature, and a nitrogen atmosphere was maintained. Then, 12.4 g of 40% glyoxal aqueous solution was added and stirred for 2 hours. The temperature of the reactants was raised to 40 ℃ due to the exothermic reaction of glyoxal and amine-terminated polyurethane prepolymer. After drying the volatiles of the product at 80℃using a rotary evaporator, the amine number was 47.2mgKOH/g as determined by ASTM D-2074-07.
Example 4: ACS-II preparation
200g of amine-terminated polyurethane prepolymer having an amine value of 95.1mgKOH/g obtained by the method for producing polyurethane prepolymer described in example 2 was placed in a 500mL four-necked flask on a heating mantle at room temperature, and a nitrogen atmosphere was maintained. Then, 37 g of 40% aqueous glyoxal solution was added and stirred for 2 hours. The temperature of the reactants was raised to 50 ℃ due to the exothermic reaction of glyoxal and amine-terminated polyurethane prepolymer. After drying the volatiles of the product at 80 ℃ using a rotary evaporator, the aldehyde concentration was 7.9wt% as measured by ASTM D-2192-06 method.
Example 5: synthesis of ACS-III
100g of the amine-terminated polyurethane prepolymer having an amine value of 47.2mgKOH/g obtained by the method for producing a polyurethane prepolymer described in example 3 was placed in a 500mL four-necked flask on a heating mantle at room temperature, and a nitrogen atmosphere was maintained. Then, 12.8 g of vanillin (vanilin) was added and stirred for 2 hours. The temperature of the reactants was raised to 40 ℃ due to the exothermic reaction of vanillin and amine terminated polyurethane prepolymers. The product volatiles were dried at 80℃using a rotary evaporator and had a hydroxyl value of 42.4mgKOH/g as measured by ASTM D-4274-1.
Example 6: synthesis of ACS-IV
100g of the amine-terminated polyurethane prepolymer having an amine value of 47.2mgKOH/g obtained by the method for producing polyurethane prepolymer described in example 3 was placed in a 500mL four-necked flask on a heating mantle at room temperature, and a nitrogen atmosphere was maintained. Then, 12.8 g of acrolein was added and stirred for 2 hours. The temperature of the reactants increased to 35 ℃ due to the exothermic reaction of the acrolein and amine-terminated polyurethane prepolymer. The product ACS-IV has an iodine value of 20 after being dried by a rotary evaporator at 80 ℃.
Example 7: synthesis of ACS-V
100g of the aldehyde-terminated prepolymer having an aldehyde value of 7.9% by weight obtained by the method for producing a polyurethane prepolymer in example 4 was placed in a 500mL four-necked flask placed on a heating mantle, and a nitrogen atmosphere was maintained. Then, 12.8 g of monoethanolamine was added and stirred for 2 hours. The temperature of the reactants was raised to 35 ℃ due to the exothermic reaction of monoethanolamine and the terminal aldehyde polyurethane prepolymer. The product ACS-V was dried at 80℃using a rotary evaporator and then had a hydroxyl value of 44.1 mgKOH/g according to ASTM D-4274-21
Example 8: synthesis of ACS-VI
100g of the aldehyde-terminated polyurethane prepolymer having an aldehyde value of 7.9% by weight obtained by the method for producing a polyurethane prepolymer described in example 4 was transferred to a 500mL four-necked flask placed on a heating mantle at room temperature, and maintained under nitrogen atmosphere. Then, 12.8 g glycine was added and stirred for 2 hours. The temperature of the reactants was raised to 35 ℃ due to the exothermic reaction of glycine and the terminal aldehyde polyurethane prepolymer. The resulting product ACS-VI was dried at 80℃using a rotary evaporator and had an acid value of 43.5mgKOH/g as measured according to ASTM D-4817.
While the invention and methods of use have been described in detail above, this is illustrative of the embodiments of the invention and should not be construed as limited to only all of the features described above.
Further, it will be apparent to those skilled in the art from this description of the invention that various modifications and simulations can be made without departing from the scope of the invention.
Claims (8)
1. A process for preparing a polymer product comprising an ACS-structured polyurethane prepolymer, comprising the steps of:
first, preparing an aromatic amine terminated polyurethane prepolymer;
secondly, forming a functional Schiff base polyurethane prepolymer containing an aromatic conjugated Schiff base ACS structure through in-situ reaction of an aromatic amine end-capped polyurethane prepolymer and aldehyde;
and thirdly, introducing the functional schiff base polyurethane prepolymer containing the ACS structure obtained in the second step into polyester, polyamide and vinyl polymers and thermosetting polymer resins, wherein the thermosetting polymer resins comprise polyurethane resin, epoxy resin and unsaturated polyester resin, so that a sustainable and high-modulus polymer product containing the polyurethane prepolymer containing the ACS structure is obtained.
2. The method according to claim 1, wherein in the second step, when the amine concentration of the aromatic amine-terminated polyurethane prepolymer is higher than the aldehyde concentration of the aldehyde compound, an amine-terminated polyurethane prepolymer containing ACS structure is obtained;
the hydroxyl-terminated polyurethane prepolymer containing ACS structure is then prepared by reacting an amine-terminated polyurethane prepolymer containing ACS structure with an alditol compound.
3. The method according to claim 1, wherein in the second step, when the amine concentration of the aromatic amine-terminated polyurethane prepolymer is higher than the aldehyde concentration of the aldehyde compound, an amine-terminated polyurethane prepolymer containing ACS structure is obtained;
the vinyl-terminated polyurethane prepolymer containing ACS structure is then prepared by reacting the amine-terminated polyurethane prepolymer containing ACS structure with vinyl aldehyde.
4. The method according to claim 1, wherein in the second step, when the amine concentration of the aromatic amine-terminated polyurethane prepolymer is lower than the aldehyde concentration of the aldehyde compound, an aldehyde-terminated polyurethane prepolymer containing ACS structure is obtained;
hydroxyl-terminated polyurethane prepolymers containing ACS structure are then prepared from the reaction of aldehyde-terminated polyurethane prepolymers containing ACS structure with hydroxylamine.
5. The method according to claim 1, wherein in the second step, when the amine concentration of the aromatic amine-terminated polyurethane prepolymer is lower than the aldehyde concentration of the aldehyde compound, an aldehyde-terminated polyurethane prepolymer containing ACS structure is obtained;
the carboxylic acid group-containing polyurethane prepolymer containing ACS structure is then prepared by reacting the aldehyde-containing polyurethane prepolymer containing ACS structure with an amino acid.
6. The method of claim 1, wherein in the first step, the isocyanate-terminated polyurethane prepolymer is obtained by reacting a polyol and an aromatic polyisocyanate, and the isocyanate-terminated polyurethane prepolymer is reacted with water to obtain an aromatic amine-terminated polyurethane prepolymer.
7. The method of claim 1, wherein in the first step, the isocyanate-terminated polyurethane prepolymer is obtained by reacting a polyol with an aromatic polyisocyanate, and the isocyanate-terminated polyurethane prepolymer is reacted with an aromatic diamine to obtain an aromatic amine-terminated polyurethane prepolymer.
8. A polymer product comprising an ACS-structured polyurethane prepolymer prepared according to the method of any one of claims 1-7, wherein the polyurethane prepolymer has one or more amine, aldehyde, hydroxyl, vinyl, or carboxyl functionalities at the ends; at normal pressure of 100 ℃ or lower, the hydrolysis realizes chemical circulation, and has sustainability, self-healing capability and low melt viscosity;
the polymer product containing ACS-structured polyurethane prepolymer has sustainability and high modulus, the sustainability is realized by hydrolyzing the used product waste at 100 ℃ or below under the atmospheric pressure, chemical recovery is realized, the mechanical properties of the product are maintained by the introduced mesogen, and the service life is prolonged by self-repairing.
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