CN116284673A - Self-repairing polyurethane and preparation method and application thereof - Google Patents
Self-repairing polyurethane and preparation method and application thereof Download PDFInfo
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- 239000004814 polyurethane Substances 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
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- 240000000342 Palaquium gutta Species 0.000 claims abstract description 48
- 229920000588 gutta-percha Polymers 0.000 claims abstract description 48
- -1 ester compound Chemical class 0.000 claims abstract description 16
- 150000001875 compounds Chemical class 0.000 claims abstract description 14
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 8
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 8
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims abstract description 7
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- 230000008569 process Effects 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 5
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- 150000002009 diols Chemical class 0.000 claims description 16
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- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000012948 isocyanate Substances 0.000 claims description 6
- 150000002513 isocyanates Chemical class 0.000 claims description 6
- 238000000016 photochemical curing Methods 0.000 claims description 6
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 4
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 claims description 3
- 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 claims description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 239000004417 polycarbonate Substances 0.000 claims description 2
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- 229920001451 polypropylene glycol Polymers 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims 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 claims description 2
- 229920001567 vinyl ester resin Polymers 0.000 claims description 2
- 229920000921 polyethylene adipate Polymers 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 27
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 6
- 239000001257 hydrogen Substances 0.000 abstract description 6
- 241000208689 Eucommia ulmoides Species 0.000 abstract description 5
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- MERLDGDYUMSLAY-UHFFFAOYSA-N 4-[(4-aminophenyl)disulfanyl]aniline Chemical compound C1=CC(N)=CC=C1SSC1=CC=C(N)C=C1 MERLDGDYUMSLAY-UHFFFAOYSA-N 0.000 description 2
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- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 238000005698 Diels-Alder reaction Methods 0.000 description 1
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
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- 125000003277 amino group Chemical group 0.000 description 1
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
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- JGUQDUKBUKFFRO-CIIODKQPSA-N dimethylglyoxime Chemical compound O/N=C(/C)\C(\C)=N\O JGUQDUKBUKFFRO-CIIODKQPSA-N 0.000 description 1
- 230000008846 dynamic interplay Effects 0.000 description 1
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- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000000640 hydroxylating effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
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- 229920005862 polyol Polymers 0.000 description 1
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- UUVCRNTVNKTNRK-UHFFFAOYSA-N pyridine-2,6-dicarboxamide Chemical compound NC(=O)C1=CC=CC(C(N)=O)=N1 UUVCRNTVNKTNRK-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
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- 229920003212 trans-1,4-polyisoprene Polymers 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
Images
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- 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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
-
- 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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- 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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
-
- 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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
-
- 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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
- C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention belongs to the field of new chemical materials, and particularly relates to a preparation method of a self-repairing polyurethane coating. The preparation method of the self-repairing polyurethane comprises the following steps: step (1): under the heating condition, adding 20-40 parts by weight of diisocyanate into 30-60 parts by weight of dihydric alcohol and adding a catalyst to react to prepare polyurethane prepolymer; step (2): adding 10-20 parts by weight of disulfide bond-containing compound and 4-12 parts by weight of olefine acid ester compound into polyurethane prepolymer, then adding 1-20 parts by weight of hydroxylated gutta-percha, and stirring for reaction to obtain the self-repairing polyurethane. The invention realizes the self-repairing process of auxiliary materials by using disulfide bonds and hydrogen bonds formed by polyhydroxy of hydroxylated eucommia bark gum and polyurethane, and realizes the rapid repairing process under mild stimulation. Meanwhile, double bonds of the hydroxylated eucommia ulmoides gum participate in the curing reaction to form an interpenetrating network structure, so that the elasticity and toughness of polyurethane are enhanced.
Description
Technical Field
The invention belongs to the field of new chemical materials, and particularly relates to self-repairing polyurethane and a preparation method and application thereof.
Background
Polyurethane is used as an organic polymer, and can be widely applied to the fields of energy, automobiles, fabrics, biomedicine, aviation, national defense and the like in the forms of thermoplasticity, thermosetting property, elastomer, coating, foam, adhesive and the like by adjusting components, dosage and the like due to high controllability of molecular structures, and becomes an indispensable material for industry and life. Since the 21 st century, the production and sales of polyurethane in China continue to increase rapidly, and the production of polyurethane in China is about 1500 ten thousand tons in 2020, which has become the biggest polyurethane production country worldwide and has the biggest polyurethane market.
However, polyurethane materials are difficult to avoid damage during use, resulting in a substantial reduction in service life. In order to further increase the life of the material, researchers have simulated the process of self-healing of living beings, developing various self-healing materials. The self-repairing mechanism of the material is classified into a foreign type self-repairing material and an intrinsic type self-repairing material. The self-repairing material for external assistance itself does not have self-repairing ability, but researchers encapsulate a repairing agent in a nanomaterial such as a capsule, hollow microsphere, hollow fiber, or the like. And then uniformly dispersing the nano material with the repairing agent in the coating to obtain the external-assistance self-repairing material. When the coating is damaged, the nano materials such as capsules, hollow microspheres, hollow fibers and the like are broken, and the repairing agent is released, so that the coating heals and the damage is prevented from diffusing. Due to the limitation of the repairing agent, the material repairing effect and the material repairing times are required to be improved. The intrinsic self-repairing material does not need to be added with a repairing agent, and has self-repairing function under the stimulation of external light, heat and the like through an inherent dynamic interaction mechanism, such as Diels-Alder reaction, transesterification reaction, dynamic disulfide bond, ionic bond, metal bond, hydrogen bond and the like. Dynamic disulfide bonds are introduced into polyurethane materials for wide research due to the characteristics of mild repairing conditions, high repairing efficiency and the like.
The prior art CN 114773570A discloses a polyurethane elastomer containing metal coordination and disulfide bonds, a preparation method thereof and a self-repairing method thereof, and belongs to the field of polyurethane elastomers and self-repairing thereof. In order to obtain the high-strength and high-toughness polyurethane elastomer with the self-repairing function, multiple functions of disulfide bonds, coordination bonds of pyridine 2, 6-dicarboxamide and metal ions and intermolecular hydrogen bonds are introduced, and the polyurethane elastomer has tensile breaking strength up to 35-60 MPa and corresponding tensile breaking elongation up to 800-1600% while obtaining good self-repairing performance. The repair can be performed by means of UV light irradiation or heating, and the intensity can be almost completely recovered. However, this prior art self-healing temperature needs to be up to 70 ℃ for up to 12 hours.
The prior art CN 112126036A discloses a bio-based degradable crosslinked self-repairing polyurethane based on disulfide bonds and a preparation method thereof. The preparation method mainly comprises the steps of taking biological material castor oil as one of polyol components to prepare degradable crosslinked polyurethane prepolymer, and introducing disulfide and dimethylglyoxime into a polyurethane system as chain extenders to prepare self-repairing degradable crosslinked polyurethane. The polyurethane material has excellent mechanical properties and self-repairing property and degradability, and the application of the polyurethane material in the field of medical equipment is expanded, so that the polyurethane material can be used as artificial skin, surgical suture line materials and the like. The 4,4 '-diaminodiphenyl disulfide adopted in the technology is expensive, and the 4,4' -diaminodiphenyl disulfide cannot be replaced by a disulfide compound which does not contain amino groups and benzene rings in the prior art, otherwise, the strength and the self-repairing performance are poor.
In summary, the self-repairing polyurethane material containing disulfide bonds has low repairing efficiency and low mechanical strength, and is still a problem to be solved.
Gutta-percha is a biological-based polymer material, is a specific strategic resource in China, has the characteristics of excellent tearing resistance, chloride ion resistance, wear resistance, excellent damping performance and the like, and is widely studied. However, the gutta percha molecular chain structure is trans-1, 4-polyisoprene, and because two methylene groups are positioned at two sides of a double bond, the molecular chain is regular in arrangement, easy to crystallize at normal temperature and shows the characteristic of hard plastic, so that the development of the gutta percha is limited. The hydroxylated gutta-percha is a high molecular material obtained by chemically modifying gutta-percha, is a product which damages the crystallinity of the gutta-percha, and has the functional characteristics of the gutta-percha. Therefore, the use of hydroxylated gutta percha modified self-repairing polyurethane is a preferred option.
Disclosure of Invention
The invention provides self-repairing polyurethane which is obtained by modifying hydroxylated eucommia ulmoides gum and has the advantages of high speed self-repairing and high mechanical strength.
In order to achieve the above object, the technical scheme of the present invention is as follows:
the preparation method of the self-repairing polyurethane comprises the following steps:
step (1): under the heating condition, adding 20-40 parts by weight of diisocyanate into 30-60 parts by weight of dihydric alcohol and adding a catalyst to react to prepare polyurethane prepolymer;
step (2): adding 10-20 parts by weight of disulfide bond-containing compound and 4-12 parts by weight of olefine acid ester compound into polyurethane prepolymer, then adding 1-20 parts by weight of hydroxylated gutta-percha, and stirring for reaction to obtain the self-repairing polyurethane.
Further, the diisocyanate is one or more of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate and hexamethylene diisocyanate, and preferably isophorone diisocyanate.
The isophorone diisocyanate is relatively low in toxicity and relatively low in price.
Further, the amount of the diisocyanate added was 30 parts.
Further, the dihydric alcohol is one or more of polycarbonate diol, polycaprolactone diol, polyethylene glycol adipate diol, polycaprolactone diol, polyethylene oxide diol, polypropylene oxide diol and polytetramethylene ether diol. Polycaprolactone diol is preferred.
Polycaprolactone has crystallinity and can strengthen the polymer.
Further, the amount of the glycol added is 45 parts.
Further, the catalyst is an organotin-based catalyst and an organobismuth-based catalyst. Dibutyl tin dilaurate is preferred.
Further, the reaction temperature of the step (1) is 70-90 ℃ and the reaction lasts for 1-3 hours.
Further, in the step (2), after the isocyanate content is consumed by half, the disulfide bond-containing compound is slowly added dropwise.
Further, the disulfide bond compound is added dropwise for reaction for 1-3 hours, and then the olefine acid ester compound is added.
Furthermore, adding an olefine acid ester compound to react for 1-3 hours, and then adding the hydroxylated eucommia bark gum.
Further, the disulfide bond-containing compound is one or more selected from 3, 3-disulfide diphenol, dithioethylenediamine and 2,2 '-dithiodiethanol, preferably 2,2' -dithiodiethanol, but both 3, 3-disulfide diphenol and dithioethylenediamine are particularly expensive and unfavorable for production and application.
Further, the addition amount of the 2,2' -dithiodiethanol was 15 parts.
Disulfide bonds in 2,2' -dithiodiethanol are the primary self-repairing means in this scheme. The content of disulfide bonds in the material is low, and the self-repairing performance of the material is poor; the content of disulfide bonds is increased, the hardness of the coating is increased, the segmental motion performance is reduced, and the self-repairing effect is reduced. In addition, 2' -dithiodiethanol has higher price, and the content increase cost can be increased. Therefore, 15 parts are most preferable in this embodiment.
Further, the vinyl ester compound is one or two of hydroxyethyl acrylate and hydroxyethyl methacrylate, preferably hydroxyethyl methacrylate, and the main difference between the two is that the stability of the double bond of the hydroxyethyl acrylate is poor. The hydroxyethyl acrylate is easy to self-polymerize in the synthetic preparation process, which is unfavorable for the preparation of products, and impurities after self-polymerization have great influence on the performance of the products.
Further, the amount of hydroxyethyl methacrylate added was 8 parts.
The hydroxyethyl methacrylate is used for end capping, so that crosslinking is carried out under the ultraviolet curing condition, and the tensile strength of the coating is improved. The addition amount is excessive, the resin crosslinking point is increased, the chain segment movement is limited, and the self-repairing performance is reduced. Therefore 8 parts are chosen as most preferred.
Further, the addition amount of the hydroxylated gutta-percha is 5 parts.
The polyhydroxy in the hydroxylated gutta-percha and polyurethane form multiple hydrogen bonds, thereby promoting the self-repairing effect of the polyurethane. In addition, unsaturated carbon-carbon double bonds in the hydroxylated gutta-percha can participate in crosslinking of the photo-curing coating, isocyanate can also crosslink with the hydroxylated gutta-percha, and the hydroxylated gutta-percha and polyurethane resin form an interpenetrating network structure, so that a microphase separation state is formed, and the mechanical property of the material is enhanced. The use of other polyhydroxy polymers, although having good compatibility with polyurethanes, does not enhance the mechanical properties of the polyurethanes. Too much hydroxylated gutta-percha is added, and the hydroxylated gutta-percha exists in a blending mode and is completely separated, so that the mechanical and self-repairing performances of the material are reduced.
Further, the hydroxylation degree of the hydroxylated gutta-percha is 17-40%. Preferably 17%.
Gutta percha molecular chain structure is trans-polyisoprene, has a regular molecular chain and is easy to crystallize, and generally shows the property of plastics. By chemically modifying gutta percha, the regularity thereof can be destroyed, thereby reducing crystallinity and even exhibiting rubber elasticity without crystallization. The degree of hydroxylation of more than 17 percent can completely destroy the crystallinity of the gutta percha, and the gutta percha shows rubber elasticity. Too high a degree of hydroxylation may lose the characteristics of gutta percha itself.
Based on the same inventive concept, the invention also claims a self-repairing polyurethane, which comprises the following raw materials:
20 to 40 weight parts of diisocyanate, 30 to 60 weight parts of dihydric alcohol, 10 to 20 weight parts of disulfide bond-containing compound, 4 to 12 weight parts of olefine acid ester compound and 1 to 20 weight parts of hydroxylated gutta-percha.
Based on the same inventive concept, the invention also discloses a self-repairing polyurethane coating, which is obtained by adding a photoinitiator into the self-repairing polyurethane and then performing photo-curing.
The invention is further explained below:
the invention uses the hydroxylated biological-based gutta-percha to modify the self-repairing polyurethane, so that the self-repairing polyurethane can obtain the performances of quick self-repairing and high mechanical strength. After hydroxylation to a certain extent, the biological-based gutta-percha keeps certain flexibility of molecular chains. After the hydroxylated gutta-percha reacts with the isocyanate group of polyurethane, a covalent crosslinking structure is formed, so that the crosslinking density is increased, and meanwhile, the polyurethane is endowed with excellent mechanical properties, so that the polyurethane has high mechanical strength. Meanwhile, the unreacted hydroxyl groups of the hydroxylated gutta-percha and the hardness of polyurethane form hydrogen bonds, and interact in a non-covalent bond mode to promote the self-repairing of the polyurethane. Under the synergistic effect of polyurethane and hydroxylated gutta-percha, the quick self-repairing and excellent mechanical properties of the polyurethane under mild conditions are realized.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the invention, firstly, polyurethane containing disulfide bonds is synthesized, then, hydroxylated eucommia ulmoides gum is added to modify self-repairing polyurethane in a covalent and non-covalent combination mode to form an interpenetrating network structure, and the self-repairing polyurethane is cooperated to realize rapid self-repairing and excellent mechanical properties under mild conditions.
2. The biological-based material is adopted to modify the gutta-percha to carry out the modification of polyurethane, so that a new application direction of the gutta-percha is explored, a proper application scene is sought for the national strategic biomass resource gutta-percha, and the popularization and the application of the gutta-percha are facilitated.
Drawings
FIG. 1 is an optical micrograph of polyurethane coatings of different 2,2' -dithiodiethanol content before and after self-healing; wherein a is about 18%, b is 15%, and c is 10%. a, a 1 、b 1 、c 1 Photographs were taken after 5 minutes of self-healing. a, a 2 、b 2 、c 2 Photograph 15 minutes after self-repair;
figure 2 tensile strength and elongation of DSPUA, DSPUB, DSPUC coating at room temperature. A. B, C the content of 2,2' -dithiodiethanol is 18%, 15% and 10% respectively;
FIG. 3 shows the self-healing effect of the coating after modification of hydroxylated gutta percha. Wherein a, b, c, d, e is added with 0%, 1%, 3%, 5% and 10% of hydroxylated eucommia bark gum respectively. a, a 1 、b 1 、c 1 、d 1 、e 1 Optical microscopy photographs after 5 minutes of self-healing. a, a 2 、b 2 、c 2 、d 2 、e 2 Optical microscope photographs after 15 minutes of self-repair;
FIG. 4 stress strain curves for (a) DSPU, (b) DSPU-1wtHEUG, (c) DSPU-3wtHEUG, (d) DSPU-5wtHEUG, (e) DSPU-10wtHEUG at room temperature;
FIG. 5 is a comparison of stress strain curves at room temperature for (a) DSPU, (b) DSPU-1wtHEUG, (c) DSPU-3wtHEUG, (d) DSPU-5wtHEUG, (e) DSPU-10wtHEUG composite coating, initial and post repair.
Detailed Description
The present invention will be described in detail with reference to examples. It should be noted that, without conflict, the embodiments of the present invention and features of the embodiments may be combined with each other.
Example 1
Polyurethane self-repairing coating without adding hydroxylated gutta percha
First, 30 parts of PCL2105 (polycaprolactone diol) and catalyst were added to a 250mL four-necked flask at N 2 Under the atmosphere, 40 parts of isophorone diisocyanate is slowly dripped into a four-mouth bottle, stirred uniformly, heated to 70 ℃ and reacted for 2 hours. After the isocyanate content is consumed by half, 18 parts of 2,2' -dithiodiethanol are slowly added dropwise, and the process is further carried outAnd (3) reacting for 2 hours, adding 12 parts of hydroxyethyl methacrylate for reaction, and obtaining the acrylic polyurethane resin after 2 hours. 3wt% of photoinitiator is added, and self-repairing polyurethane is obtained after photo-curing. The mechanical properties and the repairing effect of the self-repairing coating obtained by adding disulfide bonds with different contents according to the design are shown in fig. 1, fig. 2 and table 1.
Table 1 Properties of the polyurethane self-repairing coating without added hydroxylated gutta percha
| Sample of | 2,2' -dithiodiethanol amount | Tensile Strength | Elongation percentage | Apparent repair Properties |
| 1 | 18％ | 10.45MPa | 74.9％ | |
| 2 | 15％ | 8.65MPa | 129.5％ | Excellent in |
| 3 | 10％ | 2.49MPa | 128.3％ | Good quality |
It can be seen that an increase in the amount of 2,2' -dithiodiethanol is accompanied by an increase in the hardness content. Thus, the tensile strength is improved to some extent. However, coating self-healing effect sample 2 > sample 3 > sample 1. The hard segment content of the coating DSPUA is higher, so that the hard segment content is too high, and the movement of a molecular chain is not facilitated, while the soft segment content is higher, and the molecular chain is more flexible, so that the movement of the molecular chain is facilitated. In addition, hydrogen bonding also provides self-healing.
Example 2
Polyurethane self-repairing coating added with different contents of hydroxylated gutta percha
46 parts of PCL2105 (polycaprolactone diol) and catalyst were first added to a 250mL four-necked flask at N 2 Under the atmosphere, 30 parts of isophorone diisocyanate is slowly dripped into a four-mouth bottle, stirred uniformly, heated to 70 ℃ and reacted for 2 hours. After the isocyanate content is consumed by half, slowly dripping 16 parts of 2,2' -dithiodiethanol, further reacting for 2 hours, adding 8 parts of hydroxyethyl methacrylate for reaction, adding 5% of the mass of the resin into the mixture after 2 hours, uniformly mixing, stirring for 1 hour, adding 3wt% of a photoinitiator, and photo-curing to obtain the self-repairing polyurethane.
Example 2 the self-healing properties and mechanical properties of the coatings obtained by hydroxylating gutta percha in different addition ratios are shown in figures 3, 4 and 5 and table 2.
TABLE 2 Properties of self-healing coating with polyurethane added with different levels of hydroxylated gutta percha
It can be seen that with increasing addition of HEUG, the tensile strength and elongation of the composite coating are increased, and when the mass fraction of HEUG is 5%, the tensile strength of the coating is strongest and is 12.90MPa, and 4.25MPa is increased compared with DSPU coating. The elongation at this time was also maximum, 306.99%, 2.37 times that of DSPU coating, and when the mass fraction of the HEUG addition was 10%, the tensile length and elongation of the coating were reduced. The compatibility of DSPU and HEUG may decrease.
Example 3
Polyurethane self-repairing coating added with hydroxylated gutta percha with different hydroxylation degrees
46 parts of PCL2105 (polycaprolactone diol) and catalyst were first added to a 250mL four-necked flask at N 2 Under the atmosphere, 30 parts of isophorone diisocyanate is slowly dripped into a four-mouth bottle, stirred uniformly, heated to 70 ℃ and reacted for 2 hours. After the isocyanate content is consumed by half, slowly dripping 16 parts of 2,2' -dithiodiethanol, further reacting for 2 hours, adding 8 parts of hydroxyethyl methacrylate for reaction, adding 5% of the mass of the resin after 2 hours, uniformly mixing, stirring for 1 hour, adding 3% of a photoinitiator, and photo-curing to obtain the self-repairing polyurethane.
The properties of the hydroxylated gutta percha modified polyurethane self-repairing coating with different hydroxylation degrees are shown in the following table:
TABLE 3 modified polyurethane self-repairing coating Properties of hydroxylated gutta percha with different degrees of hydroxylation
| Sample of | Degree of hydroxylation | Tensile Strength (MPa) | Post-repair strength (MPa) | Self-healing efficiency |
| 1 | 0％ | 6.56 | 3.24 | 49.39％ |
| 2 | 10％ | 10.68 | 8.85 | 82.86％ |
| 3 | 17％ | 12.90 | 11.78 | 90.71％ |
| 4 | 28％ | 10.92 | 9.45 | 86.53％ |
| 5 | 40％ | 10.36 | 6.52 | 62.93％ |
It can be seen that the hydroxylation modification directly affects the crystallinity of gutta percha. The research shows that when the hydroxylation degree is 17%, the hydroxylated eucommia ulmoides gum is not crystallized, and the hydroxylated eucommia ulmoides gum shows good rubber elasticity. When the hydroxylation degree is continuously increased, the modified polyhydroxy resin becomes polyhydroxy resin, the compatibility with polyurethane is enhanced, microphase separation is not facilitated, and the toughening effect is reduced.
Claims (10)
1. The preparation method of the self-repairing polyurethane is characterized by comprising the following steps of:
step (1): under the heating condition, adding 20-40 parts by weight of diisocyanate into 30-60 parts by weight of dihydric alcohol and adding a catalyst to react to prepare polyurethane prepolymer;
step (2): adding 10-20 parts by weight of disulfide bond-containing compound and 4-12 parts by weight of olefine acid ester compound into polyurethane prepolymer, then adding 1-20 parts by weight of hydroxylated gutta-percha, and stirring for reaction to obtain the self-repairing polyurethane.
2. The preparation method according to claim 1, wherein the diisocyanate is one or more of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, preferably isophorone diisocyanate.
3. The method of claim 1, wherein the glycol is one or more of polycarbonate diol, polycaprolactone diol, polyethylene adipate diol, polyhexamethylene adipate diol, polyethylene oxide diol, polypropylene oxide diol, polytetramethylene ether diol; polycaprolactone diol is preferred.
4. The preparation method according to claim 1, wherein the catalyst is an organotin-based and organobismuth-based catalyst, preferably dibutyltin dilaurate.
5. The process according to claim 1, wherein in step (2), the disulfide bond-containing compound is slowly added dropwise after the isocyanate content has been consumed by half; preferably, the disulfide bond compound is added dropwise for reaction for 1-3 hours, and then the olefine acid ester compound is added; further preferably, the alkenoate compound is added to react for 1 to 3 hours, and then the hydroxylated gutta-percha is added.
6. The preparation method according to claim 1, wherein the disulfide bond-containing compound is one or more selected from 3, 3-disulfide diphenol, dithioethylenediamine, 2 '-dithiodiethanol, preferably 2,2' -dithiodiethanol.
7. The method according to claim 1, wherein the vinyl ester compound is one or both of hydroxyethyl acrylate and hydroxyethyl methacrylate, preferably hydroxyethyl methacrylate.
8. The method according to any one of claims 1 to 7, wherein the hydroxylated gutta percha is added in an amount of 5 parts; preferably, the hydroxylation degree of the hydroxylated gutta-percha is 17-40%.
9. The self-repairing polyurethane is characterized by comprising the following raw materials in parts by weight: 20 to 40 weight parts of diisocyanate, 30 to 60 weight parts of dihydric alcohol, 10 to 20 weight parts of disulfide bond-containing compound, 4 to 12 weight parts of olefine acid ester compound and 1 to 20 weight parts of hydroxylated gutta-percha.
10. A self-healing polyurethane coating, which is obtained by adding a photoinitiator into the self-healing polyurethane according to claim 9 and then photo-curing.
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