NL2035909A - Telechelic polyurethane, and preparation method and application thereof - Google Patents
Telechelic polyurethane, and preparation method and application thereof Download PDFInfo
- Publication number
- NL2035909A NL2035909A NL2035909A NL2035909A NL2035909A NL 2035909 A NL2035909 A NL 2035909A NL 2035909 A NL2035909 A NL 2035909A NL 2035909 A NL2035909 A NL 2035909A NL 2035909 A NL2035909 A NL 2035909A
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- Netherlands
- Prior art keywords
- polyurethane
- telechelic
- diisocyanate
- reaction
- crosslinking agent
- Prior art date
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- 239000004814 polyurethane Substances 0.000 title claims abstract description 56
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title abstract description 12
- KWXIPEYKZKIAKR-UHFFFAOYSA-N 2-amino-4-hydroxy-6-methylpyrimidine Chemical compound CC1=CC(O)=NC(N)=N1 KWXIPEYKZKIAKR-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229920005906 polyester polyol Polymers 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims description 53
- 239000012298 atmosphere Substances 0.000 claims description 33
- 239000003431 cross linking reagent Substances 0.000 claims description 31
- 239000003960 organic solvent Substances 0.000 claims description 26
- 238000007259 addition reaction Methods 0.000 claims description 17
- 239000011259 mixed solution Substances 0.000 claims description 17
- 150000001412 amines Chemical class 0.000 claims description 16
- 125000005442 diisocyanate group Chemical group 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 14
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 13
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 13
- 239000003054 catalyst Substances 0.000 claims description 13
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims description 11
- 150000002009 diols Chemical class 0.000 claims description 11
- 229920000570 polyether Polymers 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 9
- 230000001681 protective effect Effects 0.000 claims description 9
- 150000003512 tertiary amines Chemical class 0.000 claims description 9
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 7
- 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 7
- 229920000515 polycarbonate Polymers 0.000 claims description 7
- 239000004417 polycarbonate Substances 0.000 claims description 7
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 6
- 238000010276 construction Methods 0.000 claims description 6
- 125000004427 diamine group Chemical group 0.000 claims description 6
- 239000004970 Chain extender Substances 0.000 claims description 5
- 239000004753 textile Substances 0.000 claims 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 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 239000004632 polycaprolactone Substances 0.000 claims description 4
- 229920001610 polycaprolactone Polymers 0.000 claims description 3
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 2
- MBYLVOKEDDQJDY-UHFFFAOYSA-N tris(2-aminoethyl)amine Chemical compound NCCN(CCN)CCN MBYLVOKEDDQJDY-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 9
- CRSOQBOWXPBRES-UHFFFAOYSA-N neopentane Chemical compound CC(C)(C)C CRSOQBOWXPBRES-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 21
- 229920000642 polymer Polymers 0.000 abstract description 13
- BNCPSJBACSAPHV-UHFFFAOYSA-N (2-oxo-1h-pyrimidin-6-yl)urea Chemical group NC(=O)NC=1C=CNC(=O)N=1 BNCPSJBACSAPHV-UHFFFAOYSA-N 0.000 abstract description 6
- 230000003993 interaction Effects 0.000 abstract description 6
- 230000021715 photosynthesis, light harvesting Effects 0.000 abstract description 6
- 229920003225 polyurethane elastomer Polymers 0.000 abstract description 5
- 230000002441 reversible effect Effects 0.000 abstract description 4
- 150000003077 polyols Chemical group 0.000 abstract description 3
- 238000006471 dimerization reaction Methods 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 abstract description 2
- 239000013081 microcrystal Substances 0.000 abstract description 2
- 210000002569 neuron Anatomy 0.000 abstract description 2
- 238000005191 phase separation Methods 0.000 abstract description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 64
- 239000000243 solution Substances 0.000 description 30
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 12
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical group CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 12
- 239000012975 dibutyltin dilaurate Substances 0.000 description 12
- 239000002904 solvent Substances 0.000 description 12
- 238000001035 drying Methods 0.000 description 11
- 239000000047 product Substances 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 229940113165 trimethylolpropane Drugs 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- -1 poly- ester polyol Chemical class 0.000 description 7
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 6
- 238000001879 gelation Methods 0.000 description 6
- 229940058401 polytetrafluoroethylene Drugs 0.000 description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 description 6
- 239000000376 reactant Substances 0.000 description 6
- 239000013557 residual solvent Substances 0.000 description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 6
- 238000011282 treatment Methods 0.000 description 6
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 5
- DZIHTWJGPDVSGE-UHFFFAOYSA-N 4-[(4-aminocyclohexyl)methyl]cyclohexan-1-amine Chemical compound C1CC(N)CCC1CC1CCC(N)CC1 DZIHTWJGPDVSGE-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 208000010392 Bone Fractures Diseases 0.000 description 4
- 206010017076 Fracture Diseases 0.000 description 4
- IBVAQQYNSHJXBV-UHFFFAOYSA-N adipic acid dihydrazide Chemical compound NNC(=O)CCCCC(=O)NN IBVAQQYNSHJXBV-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000007983 Tris buffer Substances 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920006250 telechelic polymer Polymers 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- HBCBCEPGGSBSMF-UHFFFAOYSA-N 4-(4-sulfanylanilino)benzenethiol Chemical compound Sc1ccc(Nc2ccc(S)cc2)cc1 HBCBCEPGGSBSMF-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 229920006264 polyurethane film Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
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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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation 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
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
-
- 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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
-
- 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
- C08G18/48—Polyethers
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
- C08G18/5024—Polyethers having heteroatoms other than oxygen having nitrogen containing primary and/or secondary amino groups
-
- 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
- C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6607—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
- C08G18/6611—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
-
- 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
- C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6614—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6618—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
-
- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
-
- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
Abstract
UITTREKSEL Provided are telechelic polyurethane, and a preparation method and application. thereof, which belong to the field, of polyurethane material technologies. According to the telechelic high—toughness polyurethane inspired, by a neuron in the present invention, a 5 ureidopyrimidinone group in 2—amino—4—hydroxy—6—methylpyrimidine is introduced into a polyester polyol chain segment, and a microphase structure is adjusted and controlled, such that a high— strength and high—toughness polyurethane elastomer material is obtained. The ureidopyrimidinone group in the polymer chain 10 segment forms a quadruple hydrogen—bond, network and reversible characteristics thereof through dimerization, which not only can induce phase separation and is conducive to huge energy dissipation, but also can form stable microcrystals at an ambient temperature through n—n stacking interaction so as to improve 15 mechanical strength of a polyurethane material. Moreover, a soft segment of a polymer chain has abundant weak hydrogen—bond interactions, which endows the material with ultra—high toughness. (+ Fig. l) 20
Description
TELECHELIC POLYURETHANE, AND PREPARATION METHOD AND APPLICATION
THEREOF
The present invention relates to the field of polyurethane material technologies, and particularly relates to telechelic pol- yurethane, and a preparation method and application thereof.
In recent years, polyurethane has come under the spotlight owing to its excellent comprehensive properties, recyclability and broad application prospects. As a new burgeoning high polymer ma- terial with excellent wear resistance, ozone resistance, low tem- perature resistance and corrosion resistance, the polyurethane has an extensive range of application prospects in aerospace, automo- tive, textile, construction, medical, intelligent detection and other fields.
However, an inherent contradiction between strength and toughness enormously limits practical application of a traditional polyurethane material in the fields of automotive coatings, weara- ble electronic devices, soft robots, flexible electronics, biomed- icine, and so on.
In view of this, an objective of the present invention is to provide telechelic polyurethane, and a preparation method and ap- plication thereof. The telechelic polyurethane prepared according to the present invention has toughness and strength.
In order to realize the above objective of the present inven- tion, the present invention provides a technical solution as fol- lows:
The present invention provides a preparation method of telechelic polyurethane. The method include steps as follows: mixing a polyester polyol, a polyether amine and a diamine chain extender, such that a mixed solution is obtained;
mixing the mixed solution, diisocyanate, a catalyst and an organic solvent for a prepolymerization reaction, such that a pol- yurethane prepolymer is obtained; mixing the polyurethane prepolymer, 2-amino-4-hydroxy-6- methylpyrimidine and an organic solvent for a first addition reac- tion, such that an addition product is obtained; and mixing the addition product, a cross-linking agent and an or- ganic solvent for a second addition reaction, such that the telechelic polyurethane is obtained.
Preferably, a molar ratio of the polyester polyol, the poly- ether amine, the diisocyanate, the 2-amino-4-hydroxy-6- methylpyrimidine and the cross-linking agent is 3-30:3-30:9-90:3- 30:1-10.
Preferably, the polyester polyol has an average molecular weight of 1000-3000, and the polyester polyol includes one or more of polycarbonate diol, polycaprolactone diol and polyester polyol.
Preferably, the diisocyanate includes one or more of hexa- methylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate and 4,4'-dicyclohexylmethane diisocyanate.
Preferably, the prepolymerization reaction is carried out at 60°C — 100°C for 2 h - 3 h in a protective atmosphere.
Preferably, the first addition reaction is carried out at 60°C — 100°C for 1 h - 3 h in a protective atmosphere.
Preferably, the cross-linking agent is a trihydric alcohol cross-linking agent or a tertiary amine cross-linking agent, the trihydric alcohol cross-linking agent includes one or more of tri- methylolpropane, trimethylolethane and glycerol, and the tertiary amine cross-linking agent includes tris{2-aminoethyl) amine.
Preferably, the second addition reaction is carried out at 60°C — 100°C for 1 h - 3 h in a protective atmosphere.
The present invention further provides telechelic polyure- thane prepared through the preparation method in the above solu- tion.
The present invention further provides application of the telechelic polyurethane prepared in the above solution in aero- space, automotive, textile, construction, medical, intelligent de-
tection and other fields.
The present invention provides a preparation method of telechelic polyurethane. The method include steps as follows: mix- ing a polyester polyol, a polyether amine and a diamine chain ex- tender, such that a mixed solution is obtained; mixing the mixed solution, diisocyanate, a catalyst and an organic solvent for a prepolymerization reaction, such that a polyurethane prepolymer is obtained; mixing the polyurethane prepolymer, 2-amino-4-hydroxy-6- methylpyrimidine and an organic solvent for a first addition reac- tion, such that an addition product is obtained; and mixing the addition product, a cross-linking agent and an organic solvent for a second addition reaction, such that the telechelic polyurethane is obtained.
The present invention provides a telechelic high-toughness polyurethane inspired by a neuron, a ureidopyrimidinone group in 2-amino-4-hydroxy-6-methylpyrimidine is introduced into a polyes- ter polyol chain segment, a trihydric alcohol cross-linking agent or a tertiary amine cross-linking agent is added, and a microphase structure is adjusted and controlled, such that a high-strength and high-toughness polyurethane elastomer material is obtained.
The ureidopyrimidinone group in the polymer chain segment forms a quadruple hydrogen-bond network and reversible characteristics thereof through dimerization, which not only can induce phase sep- aration and is conducive to huge energy dissipation, but also can form stable microcrystals at an ambient temperature through n-n stacking interaction so as to improve mechanical strength of a polyurethane material. Moreover, a soft segment of a polymer chain has abundant weak hydrogen-bond interactions, which endows the ma- terial with ultra-high toughness. In addition, the introduced chemical cross-linking agent with multiple functional groups is conducive to construction of a solid chemical network cross- linking point, and endows the polyurethane material with excellent mechanical property. Due to a synergistic effect of dynamic re- versible hierarchical hydrogen bonds and stable covalent bonds in the polymer network structure, an obtained polyurethane film shows high tensile strength and excellent toughness.
The telechelic polymer prepared according to the present in-
vention is a liquid polymer with reactive functional groups at two ends of each molecule, and can serve as liquid rubber, a coating, an adhesive, a sealant, etc. Through an interaction of active end groups, the telechelic polymer is finally chained or cross-linked to form a polymer having a high molecular weight, which has im- portant significance and value for widening application of the polyurethane material in aerospace, automotive, textile, construc- tion, medical, intelligent detection and other fields.
Moreover, the preparation method in the present invention has advantages of high efficiency, safety, environmental protection, etc. The prepared polyurethane elastomer has characteristics of high strength, high toughness, a film forming property of a poly- mer material, excellent heat resistance, etc. Further, a new idea is provided for development of a next-generation high-strength and high-toughness polyurethane material.
FIG. 1 is a flow diagram of reactions for preparing telechelic polyurethane in Example 1;
FIG. 2 is a schematic diagram showing stress-strain curves of samples in Examples 1-3;
FIG. 3 shows stress-strain curves of the sample prepared in
Example 1 at different stretching rate; and
FIG. 4 is a schematic diagram showing a thermogravimetric curve of the sample prepared in Example 1.
The present invention provides a preparation method of telechelic polyurethane. The method include steps as follows: mix a polyester polyol, a polyether amine and a diamine chain extender, such that a mixed solution is obtained; mix the mixed solution, diisocyanate, a catalyst and an or- ganic solvent for a prepolymerization reaction, such that a polyu- rethane prepolymer is obtained; mix the polyurethane prepolymer, 2-amino-4-hydroxy-6- methylpyrimidine and an organic solvent for a first addition reac- tion, such that an addition product is obtained; and mix the addition product, a cross-linking agent and an organ- ic solvent for a second addition reaction, such that the telechelic polyurethane is obtained.
In the present invention, unless otherwise specified, the 5 used raw materials are commercially available in the art.
In the present invention, a polyester polyol, a polyether amine and a diamine chain extender are mixed, such that a mixed solution is obtained.
In the present invention, the polyester polyol has an average molecular weight preferably of 1000-3000, and the polyester polyol preferably includes one or more of polycarbonate diol, polycapro- lactone diol and polyester polyol.
In the present invention, the polyether amine is preferably
D230, D400 or D2000.
In the present invention, the diamine chain extender is pref- erably adipic acid dihydrazide, 4,4'-diaminodicyclohexylmethane, 4,4'-dithiodiphenylamine or 2,2'-ethylenediphenylamine.
In the present invention, mixing is preferably carried out in a three-neck flask.
In the present invention, the mixing is preferably carried out at 100°C - 120°C for 30 min - 120 min under a condition of an oil bath in an atmosphere of nitrogen, and has functions of de- watering and drying.
After the mixed solution is obtained, in the present inven- tion, the mixed solution, diisocyanate, a catalyst and an organic solvent are mixed for a prepolymerization reaction, such that a polyurethane prepolymer is obtained.
In the present invention, the diisocyanate includes one or more of hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI) and 4,4'- dicyclohexylmethane diisocyanate (HMDI).
In the present invention, the catalyst is preferably dibu- tyltin dilaurate (DBTDL).
In the present invention, a molar ratio of the diisocyanate to the catalyst is preferably 10-30:1.
In the present invention, the prepolymerization reaction is preferably carried out at 60°C - 100°C for 2 h - 3 h in a protec-
tive atmosphere. During the prepolymerization reaction, the poly- ester polyol and the polyether amine both react with the diisocya- nate. In this case, not only a prepolymerization reaction product, but also a substance reacting with the polyether amine and the diisocyanate exist in the reaction system.
In the present invention, the protective atmosphere is pref- erably N;.
In the present invention, the organic solvent preferably in- cludes one or more of N,N-dimethylformamide (DMF), N,N- dimethylacetamide (DMAc), toluene and tetrahydrofuran (THF). In the present invention, viscosity of the reactants is controlled preferably by adjusting the amount of the organic solvent, such that gelation is prevented.
In the present invention, preferably, after the mixed solu- tion is cooled to 60°C - 100, a mixture of the diisocyanate and the organic solvent is dropwise added into a reaction bottle, the cat- alyst is dropwise added, and the prepolymerization reaction is carried out in an atmosphere of Nz, such that the polyurethane pre- polymer is obtained.
After the polyurethane prepolymer is obtained, in the present invention, the polyurethane prepolymer, 2-amino-4-hydroxy-6- methylpyrimidine (UPy) and an organic solvent are mixed for a first addition reaction, such that an addition product is ob- tained.
In the present invention, the organic solvent preferably in- cludes one or more of N,N-dimethylformamide (DMF), N,N- dimethylacetamide (DMAc), toluene and tetrahydrofuran (THF), and preferably is the same as the organic solvent for the prepolymeri- zation reaction.
In the present invention, preferably, the 2-amino-4-hydroxy- 6-methylpyrimidine and an organic solvent are ultrasonically mixed, such that a 2-amino-4-hydroxy-6-methylpyrimidine solution is obtained, and the 2-amino-4-hydroxy-6-methylpyrimidine solution is dropwise added into the polyurethane prepolymer.
In the present invention, the 2-amino-4-hydroxy-6- methylpyrimidine solution has a concentration preferably of 0.01 g/mL.
In the present invention, the first addition reaction is preferably carried out at 60°C - 100°C for 1 h - 3 h in a protec- tive atmosphere.
After the addition product is obtained, in the present inven- tion, the addition product, a cross-linking agent and an organic solvent are mixed for a second addition reaction, such that the telechelic polyurethane is obtained.
In the present invention, the second addition reaction is preferably carried out at 60°C - 100°C for 1 h - 3 h in a protec- tive atmosphere.
In the present invention, the cross-linking agent is prefera- bly a trihydric alcohol cross-linking agent or a tertiary amine cross-linking agent, the trihydric alcohol cross-linking agent preferably includes one or more of trimethylolpropane (TMP), tri- methylolethane (TME) and glycerol, and the tertiary amine cross- linking agent preferably includes tris (2-aminocethyl)amine (TAN).
In the present invention, the organic solvent preferably in- cludes one or more of N,N-dimethylformamide (DMF), N,N- dimethylacetamide (DMAc), toluene and tetrahydrofuran (THF), and preferably is the same as the organic solvent for the prepolymeri- zation reaction.
In the present invention, preferably, the cross-linking agent and the organic solvent are ultrasonically mixed, such that a cross-linking agent solution is obtained, and the cross-linking agent solution is dropwise added into the addition product.
In the present invention, a molar ratio of the polyester pol- yol, the polyether amine, the diisocyanate, the 2-amino-4-hydroxy-
G-methylpyrimidine and the cross-linking agent is preferably 3- 30:3-30:9-90:3-30:1-10.
After the second addition reaction is completed, in the pre- sent invention, the obtained solution is poured into a polytetra- fluoroethylene mold, and vacuum and drying treatment is carried out at 60°C - 100°C for 48 h, such that a residual solvent is re- moved, and the telechelic polyurethane is obtained.
The present invention further provides telechelic polyure- thane prepared through the preparation method in the above solu-
tion.
The present invention further provides application of the telechelic polyurethane prepared in the above solution in aero- space, automotive, textile, construction, medical, intelligent de- tection and other fields.
The present invention has no particular limitation on the specific manner of the application, and any manner well known to those skilled in the art can be used.
In order to further illustrate the present invention, the telechelic polyurethane, and the preparation method and applica- tion thereof provided in the present invention will be described in detail below in combination with examples, but they are not to be construed as limiting the scope of protection of the present invention.
Example 1 (1) Firstly, 6.00 9/3 mmol of polycarbonate diol (PCDL-2000) having a molecular weight of 2000 g/mol and 0.69 g/3 mmol of poly- ether amine (D230) having a molecular weight of 230 g/mol were weighed, mixed and put into a three-neck flask, and stirred at 120°C for 30 min under a condition of an oil bath in an atmosphere of N.. (2) Then, after the above mixed solution was cooled to 80°, 30 mL of N,N-dimethylformamide (DMF) was measured out to serve as a solvent, 2.20 g/9 mmol of isophorone diisocyanate (IPDI) was weighed and dropwise added into a reaction bottle, 0.03 g of dibu- tyltin dilaurate (DBTDL) was dropwise added to serve as a cata- lyst, a reaction was carried out for 2 h in an atmosphere of Nj, and viscosity of the reactants is controlled by appropriately ad- justing the amount of the organic solvent, such that gelation was prevented, and a prepolymer was obtained. (3) After the prepolymer was prepared, 0.38 g/3 mmol of 2- amino-4-hydroxy-6-methylpyrimidine (UPy) was weighed, 3.8 ml of a
DMF solution (having a concentration of 0.01 g/ml) was measured out and dropwise added into the reaction bottle, and a reaction was carried out at 80°C for 60 min in an atmosphere of N;. (4) 0.134 g/1 mmol of trimethylolpropane (TMP) was weighed and dissolved in 5 mL of a DMF solvent, after the trimethylolpro- pane was completely dissolved, the solution was dropwise added in- to the reaction bottle, and a reaction was carried out at 80°C for 60 min in an atmosphere of N.. {5) After the reaction was completed, the solution was poured into a polytetrafluoroethylene mold, and vacuum and drying treat- ment was carried out at 80°C for 48 h, such that a residual solvent was removed. The sample was named PUD-UPy.
FIG. 1 is a flow diagram of reactions for preparing telechelic polyurethane in Example 1.
Example 2 (1) Firstly, 6.00 g/3 mmol of polycarbonate diol (PCDL-2000) having a molecular weight of 2000 g/mol was weighed and put into a three-neck flask, and stirred at 120°C for 30 min under a condition of an oil bath in an atmosphere of N;, and dewatering and drying were carried out. (2) Then, after the above mixed solution was cooled to 80°C, 30 mL of N,N-dimethylformamide (DMF) was measured out to serve as a solvent, 2.20 g/9 mmol of isophorone diisocyanate (IPDI) was weighed and dropwise added into a reaction bottle, 0.03 g of dibu- tyltin dilaurate (DBTDL) was dropwise added to serve as a cata- lyst, a reaction was carried out for 2 h in an atmosphere of Nj, and viscosity of the reactants is controlled by appropriately ad- justing the amount of the organic solvent, such that gelation was prevented, and a prepolymer was obtained. (3) After the prepolymer was prepared, 0.631 g/3 mmol of 4,4'-diaminodicyclohexylmethane (DDM) having a molecular weight of 210.37 g/mol was weighed and dissolved in a DMF solution, and af- ter the 4,4'-diaminodicyclohexylmethane was completely dissolved, the solution was dropwise added into a reaction system. (4) Then, 0.38 g/3 mmol of 2-amino-4-hydroxy-6- methylpyrimidine (UPy) was weighed, 3.8 ml of a DMF solution (hav- ing a concentration of 0.01 g/ml) was measured out and dropwise added into the reaction bottle, and a reaction was carried out at 80°C for 60 min in an atmosphere of Na. (5) 0.134 g/l mmol of trimethylolpropane (TMP) was weighed and dissolved in 5 ml of a DMF solvent, after the trimethylolpro- pane was completely dissolved, the solution was dropwise added in- to the reaction bottle, and a reaction was carried out at 80°C for 60 min in an atmosphere of N.. {6) After the reaction was completed, the solution was poured into a polytetrafluoroethylene mold, and vacuum and drying treat- ment was carried out at 80°C for 48 h, such that a residual solvent was removed. The sample was named PUD-UPy-1.
Example 3 (1) Firstly, 6.00 g/3 mmol of polycarbonate diol (PCDL-2000) having a molecular weight of 2000 g/mol was weighed and put into a three-neck flask, and stirred at 120°C for 30 min under a condition of an oil bath in an atmosphere of N;, and dewatering and drying were carried out. (2) Then, after the above mixed solution was cooled to 80°C, 30 mL of N,N-dimethylformamide (DMF) was measured out to serve as a solvent, 2.20 g/9 mmol of isophorone diisocyanate (IPDI) was weighed and dropwise added into a reaction bottle, 0.03 g of dibu- tyltin dilaurate (DBTDL) was dropwise added to serve as a cata- lyst, a reaction was carried out for 2 h in an atmosphere of Ng, and viscosity of the reactants is controlled by appropriately ad-
Justing the amount of the organic solvent, such that gelation was prevented, and a prepolymer was obtained. (3) After the prepolymer was prepared, 0.523 g/3 mmol of adipic dihydrazide (ADH) having a molecular weight of 174.20 g/mol was weighed and dissolved in a DMF solution, and after the adipic dihydrazide was completely dissolved, the solution was dropwise added into a reaction system. {4) Then, 0.38 9/3 mmol of 2-amino-4-hydroxy-6- methylpyrimidine (UPy) was weighed, 3.8 ml of a DMF solution (hav- ing a concentration of 0.01 g/ml) was measured out and dropwise added into the reaction bottle, and a reaction was carried out at 80°C for 60 min in an atmosphere of Nj. (5) 0.134 g/1 mmol of trimethylolpropane (TMP) was weighed and dissolved in 5 mL of a DMF solvent, after the trimethylolpro- pane was completely dissolved, the solution was dropwise added in-
to the reaction bottle, and a reaction was carried out at 80°C for 60 min in an atmosphere of Nj. (6) After the reaction was completed, the solution was poured into a polytetrafluoroethylene mold, and vacuum and drying treat- ment was carried out at 80°C for 48 h, such that a residual solvent was removed. The sample was named PUD-UPy-2.
Example 4 {1} Firstly, 3.00 9/3 mmol of polycarbonate diol (PCDL-1000) having a molecular weight of 1000 g/mol and 1.20 g/3 mmol of poly- ether amine D400 having a molecular weight of 400 g/mol were weighed, mixed and put into a three-neck flask, and stirred at 120°C for 30 min under a condition of an oil bath in an atmosphere of N;, and dewatering and drying were carried out. (2) Then, after the above mixed solution was cooled to 80°C, 30 mL of N,N-dimethylformamide (DMF) was measured out to serve as a solvent, 2.20 g/9 mmol of isophorone diisocyanate (IPDI) was weighed and dropwise added into a reaction bottle, 0.03 g of dibu- tyltin dilaurate (DBTDL) was dropwise added to serve as a cata- lyst, a reaction was carried out for 2 h in an atmosphere of Nj, and viscosity of the reactants was controlled by appropriately ad-
Justing the amount of the organic solvent, such that gelation was prevented, and a prepolymer was obtained. (3) After the prepolymer was prepared, 0.38 g/3 mmol of 2- amino-4-hydroxy-6-methylpyrimidine (UPy) was weighed, 3.8 ml of a
DMF solution (having a concentration of 0.01 g/ml) was measured out and dropwise added into the reaction bottle, and a reaction was carried out at 80°C for 60 min in an atmosphere of N,. (4) 0.146 g/1 mmol of tris (2-amincethyl)amine (TAN) was weighed and dissolved in 5 mL of a DMF solution, after the tris(2- amincethyl)amine was completely dissolved, the solution was drop- wise added into the reaction bottle, and a reaction was carried out at 80°C for 60 min in an atmosphere of N;. (5) After the reaction was completed, the solution was poured into a polytetrafluoroethylene mold, vacuum and drying treatment was carried out at 80°C for about 48 h, such that a residual sol- vent was removed. The sample was named PCDL-1000-UPy-TAN.
Example 5 (1) Firstly, 6.00 9/3 mmol of polycaprolactone diol (PCL- 2000) having a molecular weight of 2000 g/mol and 1.20 g/3 mmol of polyether amine D400 having a molecular weight of 400 g/mol were weighed, mixed and put into a three-neck flask, and stirred at 120°C for 30 min under a condition of an oil bath in an atmosphere of N;, and dewatering and drying were carried out. (2) Then, after the above mixed solution was cooled to 80°C, 30 mL of N,N-dimethylformamide (DMF) was measured out to serve as a solvent, 2.20 g/9 mmol of hexamethylene diisocyanate (HDI) was weighed and dropwise added into a reaction bottle, 0.03 g of dibu- tyltin dilaurate (DBTDL) was dropwise added to serve as a cata- lyst, the reaction was carried out for 2 h in an atmosphere of Nj, and viscosity of the reactants was controlled by appropriately ad-
Jjusting the amount of the organic solvent, such that gelation was prevented, and a prepolymer was obtained. (3) After the prepolymer was prepared, 0.38 g/3 mmol of 2- amino-4-hydroxy-6-methylpyrimidine (UPy) was weighed, 3.8 ml of a
DMF solution (having a concentration of 0.01 g/ml) was measured out and dropwise added into the reaction bottle, and a reaction was carried out at 80°C for 60 min in an atmosphere of N,. (4) 0.12g/1 mmol of trimethylolethane (TME) was weighed and dissclved in 5 ml of a DMF solvent, after the trimethylolethane was completely dissolved, the solution was dropwise added into the reaction bottle, and a reaction was carried out at 80°C for 60 min in an atmosphere of N;. (5) After the reaction was completed, the solution was poured into a polytetrafluoroethylene mold, vacuum and drying treatment was carried out at 80°C for about 48 h, such that a residual sol- vent was removed. The sample was named PCL-2000-UPy-TME.
Test results:
In order to effectively evaluate a mechanical property of the prepared polyurethane material, with Example 1 as an instance, samples prepared in Examples 1-3 were tested for stress-strain curves. Obtained results are shown in FIGs. 2 and 3, and summa- rized in Table 1. It can be seen from FIG. 2 and data in Table 1 that PUD-UPy shows an extremely high tensile property and excel- lent tensile strength, and has maximum tensile strength of 35.26
MPa, a fracture strain of 957%, and a toughness value of 159.65
MJ/m’. PUD-UPy-1 has maximum tensile strength of 52.17 MPa, a frac- ture strain of 445%, and a toughness value of 101.55 MJ/m’. PUD-
UPy-2 has maximum tensile strength of 69.11 MPa, a fracture strain of 685%, and a toughness value of 198.36 MJ/m’.
Therefore, through a reasonable molecular design and adjust- ment and control of distribution of soft and hard segments, polyu- rethane materials PUD-UPy, PUD-UPy-1, PUD-UPy-2 all show extraor- dinary mechanical properties, that is, high mechanical strength, high tensile properties and high toughness, which have reached high levels in the field of polyurethane. Herein, a content of a ureidopyrimidinone group containing quadruple hydrogen bonds has significant effects on the mechanical property of the polymer. Due to effective energy dissipation, non-covalent polyurethane shows a significant mechanical toughening effect under the action of an external force. In addition, a cross-linking agent containing tri- atomic alcohol/tertiary amine in the polymer chain is used for constructing a strong covalently crosslinked polyurethane network, which endows the material with extremely high tensile strength and a high modulus.
Stress-strain curve of sample:
Test standard: GB/T 1040-2006,
Test speed: 100 mm/min, and test environment: 25°C.
Table 1 Elongation at break, ultimate tensile strength and toughness data of Examples 1-3
Strength Elongation at Toughness
Example me len
Stress-strain curves of sample PUD-UPy at different stretch- ing rates are shown in FIG. 3. It can be seen that PUD-UPy pre- pared in Example 1 has a desirable stress-strain property.
Test standard: GB/T 1040-2006,
Test speed: 10 mm/min - 100 mm/min, and test environment: 25°C.
A summary of mechanical properties of sample PUD-UPy at dif- ferent stretching rates is shown in Table 2.
Toughness of material: an area at a lower portion of a stress-strain curve, that is, energy absorbed per unit volume of material before fracture occurs.
Table 2 Elongation at break, ultimate tensile strength and toughness data of PUD-UPy prepared in Example 1
Elongation at Toughness
Stretching rate Strength (MPa) rome ott ul” ey
In order to further analyze a reinforcing and toughening mechanism of the polyurethane elastomer prepared in the present invention, mechanical properties at different stretching rates are further tested. It can be seen from FIG. 3 and results in Table 2 that the mechanical properties of sample PUD-UPy at different stretching rates are slightly different. A tensile behavior relat- ed to a deformation rate further confirms dynamic properties of a chain. That is, sample PUD-UPy shows obvious rate dependence. With the increase of a deformation rate, yield and tensile strength is significantly increased, while elongation at break shows a down- ward trend.
In cases of low strains (10 mm/min and 50 mm/min), the mate- rial shows relatively low tensile strength and relatively high elongation at break. In a case of a high strain (100 mm/min), the tensile strength of the material obviously increases, and elonga- tion at break decreases. This mainly benefits from existence of a reversible non-covalent interaction in the polymer network struc- ture, that is, introduction of a uridopyrimidinone unit containing quadruple hydrogen bonds. A deformation rate is closely related to breakage and reconstruction of the quadruple hydrogen bonds. In a case of the high strain, reversible multiple hydrogen bonds are difficult to rapidly assemble, energy dissipation is inhibited,
and thus elongation at break decreases. In a case of the low strains, a lower stretching rate provides an opportunity for breakage and reconstruction of multiple hydrogen bonds in a poly- mer chain, which is conducive to effective and sufficient energy dissipation. Thus, the material is endowed with high elongation at break, the mechanical property of the polyurethane is effectively adjusted, and significant mechanical strengthening and toughening effects are shown under the action of an external force.
Thermal stability of Example 1 was tested.
Test atmosphere: nitrogen, and test temperature range: room temperature - 800°C.
A thermogravimetric curve of sample PUD-UPy is shown in FIG. 4. It can be seen from FIG. 4 that PUD-UPy shows excellent heat resistance. The sample shows two decomposition temperature ranges: a hard segment decomposes at 240°C - 350°C, and a soft segment de- composes at 350°C - 450°C. A thermogravimetric temperature (Td, a temperature corresponding to 5% weight loss of the sample) of the sample was about 273°C. Therefore, a thermogravimetric analysis (TGA) result fully proves that the polyurethane elastomer prepared in the present invention not only shows high strength and high toughness, but also has excellent heat resistance.
According to the present invention, through a reasonable mo- lecular design and adjustment and control of distribution of soft and hard segments, polyurethane material PUD-UPy shows an extraor- dinary mechanical property, that is, high mechanical strength, high tensile property and high toughness. Herein, a content of a ureidopyrimidinone group containing quadruple hydrogen bonds has significant effects on the mechanical property of the polymer. Due to effective energy dissipation, non-covalent polyurethane shows a significant mechanical toughening effect under the action of an external force. In addition, a cross-linking agent containing tri- atomic alcohol/tertiary amine in the polymer chain is used for constructing a strong covalently crosslinked polyurethane network, which endows the material with extremely high tensile strength and a high modulus.
What are described above are merely preferred embodiments of the present invention, and does not limit the present invention in any form.
It should be noted that several improvements and modifi- cations can be made by those of ordinary skill in the art without departing from the principle of the present invention, and these improvements and modifications should fall within the scope of protection of the present invention.
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