CN107033324A - A kind of wide temperature range polyurethane elastomer damping material designed based on network structure and method and application - Google Patents
A kind of wide temperature range polyurethane elastomer damping material designed based on network structure and method and application Download PDFInfo
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- CN107033324A CN107033324A CN201710274384.XA CN201710274384A CN107033324A CN 107033324 A CN107033324 A CN 107033324A CN 201710274384 A CN201710274384 A CN 201710274384A CN 107033324 A CN107033324 A CN 107033324A
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- damping material
- prepolymer
- temperature range
- diisocyanate
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- 238000013016 damping Methods 0.000 title claims abstract description 120
- 239000000463 material Substances 0.000 title claims abstract description 88
- 229920003225 polyurethane elastomer Polymers 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 8
- 229920000728 polyester Polymers 0.000 claims abstract description 70
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims abstract description 43
- 150000002009 diols Chemical class 0.000 claims abstract description 37
- 239000003054 catalyst Substances 0.000 claims abstract description 34
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 29
- 150000001875 compounds Chemical class 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims description 32
- 238000010792 warming Methods 0.000 claims description 31
- 238000002360 preparation method Methods 0.000 claims description 30
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical group CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 25
- 238000003756 stirring Methods 0.000 claims description 22
- 239000002904 solvent Substances 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 18
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 claims description 15
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- 229920000151 polyglycol Polymers 0.000 claims description 14
- 239000010695 polyglycol Substances 0.000 claims description 14
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 claims description 13
- -1 bismuth carboxylate Chemical class 0.000 claims description 13
- 229930016911 cinnamic acid Natural products 0.000 claims description 13
- 235000013985 cinnamic acid Nutrition 0.000 claims description 13
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 13
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 10
- 239000011261 inert gas Substances 0.000 claims description 10
- 230000018044 dehydration Effects 0.000 claims description 9
- 238000006297 dehydration reaction Methods 0.000 claims description 9
- 150000002148 esters Chemical class 0.000 claims description 9
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- 238000005516 engineering process Methods 0.000 claims description 4
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 4
- 229920005989 resin Polymers 0.000 claims description 4
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 claims description 3
- 239000012948 isocyanate Substances 0.000 claims description 3
- 239000011347 resin Substances 0.000 claims description 3
- RFVNOJDQRGSOEL-UHFFFAOYSA-N 2-hydroxyethyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCO RFVNOJDQRGSOEL-UHFFFAOYSA-N 0.000 claims description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 2
- 238000005266 casting Methods 0.000 claims description 2
- 229940113088 dimethylacetamide Drugs 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
- 150000002513 isocyanates Chemical class 0.000 claims description 2
- 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 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 238000007711 solidification Methods 0.000 claims description 2
- 230000008023 solidification Effects 0.000 claims description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 2
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 claims 2
- 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 1
- 229920002635 polyurethane Polymers 0.000 abstract description 11
- 239000004814 polyurethane Substances 0.000 abstract description 11
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 81
- 239000012298 atmosphere Substances 0.000 description 29
- 239000004970 Chain extender Substances 0.000 description 17
- 238000001291 vacuum drying Methods 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 12
- 230000009471 action Effects 0.000 description 11
- 239000004809 Teflon Substances 0.000 description 8
- 229920006362 Teflon® Polymers 0.000 description 8
- 150000001298 alcohols Chemical class 0.000 description 8
- 238000013461 design Methods 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 238000009413 insulation Methods 0.000 description 8
- 238000005303 weighing Methods 0.000 description 8
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical class COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 7
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 235000019082 Osmanthus Nutrition 0.000 description 2
- 241000333181 Osmanthus Species 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- REZQBEBOWJAQKS-UHFFFAOYSA-N triacontan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCO REZQBEBOWJAQKS-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 229920006311 Urethane elastomer Polymers 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 229920003232 aliphatic polyester Polymers 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 125000001475 halogen functional group Chemical group 0.000 description 1
- 229940051250 hexylene glycol Drugs 0.000 description 1
- 125000002462 isocyano group Chemical group *[N+]#[C-] 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000000116 mitigating effect Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 229920001059 synthetic polymer Polymers 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
- C08G18/70—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
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
-
- 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
- C08G18/2805—Compounds 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
- C08G18/28—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
-
- 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
- C08G2350/00—Acoustic or vibration damping material
Landscapes
- 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 belongs to the technical field of damping material, a kind of wide temperature range polyurethane elastomer damping material designed based on network structure and method and application are disclosed.The damping material, is prepared from the following components：The parts by weight of polyurethane prepolymer 11~37, the parts by weight of suspended chain prepolymer 7~30, the parts by weight of superbrnaching end-hydroxy polyester 1~25；The polyurethane prepolymer is to be reacted to obtain in the presence of catalyst by polyester diol, diisocyanate；The suspended chain prepolymer is to be reacted to obtain in the presence of catalyst by end monohydroxy compound, diisocyanate.About 170 DEG C of the damping material effective damping temperature range width of the present invention, damping capacity is excellent in the range of temperature range, its damping factor tan δ >=0.3, and the polyurethane damping material high/low temperature damping capacity of the present invention is good, high temperature effective damping is up to 120 DEG C, with preferable application prospect.
Description
Technical field
The invention belongs to the technical field of damping material, it is related to a kind of polyurethane elastomer, more particularly to one kind is based on
Wide temperature range polyurethane elastomer damping material of network structure design and preparation method and application.
Background technology
With the fast development of science and technology, military products and civilian goods field towards low energy consumption, high speed, light weight mechanical automation side
To development, at the same time, the vibration of increasingly automated generation and noise are flooded with each corner of life, and vibration noise is for day
The influence that normal production and living are brought can not despise.
Mitigating vibration noise problem turns into the task of top priority, and domestic and international researcher is tackled by exploring Novel Damping Materials
The problem.Wide temperature domain high damping material requirement is at least in the range of 60 DEG C~80 DEG C of temperature range (use environment temperature range), and it is damped
Factor t an δ >=0.3, in addition, optimal damping material should (minimum long-term use temperature be extremely in the range of its temperature in use
Temperature is used for a long time in highest) all there is high-damping value.Chinese invention patent application CN104448289A is related to a kind of poly- ammonia of raising
The preparation method of the PPG of ester damping capacity, its preparation method and its damping material of preparation, is introduced in polyether backbone
Side base, increase internal friction damps to improve polyurethane, about 70 DEG C of effective damping temperature range (- 10 DEG C~60 DEG C)；Patent application
CN103140522A contains branched high molecular there is provided a kind of damping material composition, about 40 DEG C (- 20 DEG C of its effective damping temperature range
~20 DEG C).Instantly have scholar and probe into and be introduced into suspended chain in the polymeric material (one end is fixed in cross-linked network, the other end
Can free movement strand) to lift its damping capacity, but damping materials material is prepared based on single Molecular Design,
Its high temperature, low temperature effective damping are narrower, damage excessive to polymeric material mechanical property if suspended chain too high levels, meet
Not actual operation requirements.
Polyurethane elastomer damping material because its structure design flexibly, prepare controllability, it is cheap the advantages of, become
One of research emphasis of elastomer damping material, but polyurethane damping material, equally have visco-elastic damping material shared not
Foot part, i.e., the following damping capacity of room temperature is good, and room temperature above damping is not good, therefore need to damp material to polyurethane elastomer
Material carries out structure design, and polyurethane elastomer is made up of soft and hard segments, and designability is strong, and fractional free volume reasonable in design is (certainly
The percentage of polymer cumulative volume is accounted for by volume hole), the soft and hard segments compatibility of the regulation polyurethane elastomer such as suspended chain is introduced,
Improve microphase-separated, the material for possessing excellent damping performance in the range of wide temperature range can be prepared, further widen polyurethane resistance
The application field and scope of damping material.
The content of the invention
In order to overcome the shortcoming and defect of prior art, present invention aims at provide it is a kind of based on network structure design
The preparation method of wide temperature range polyurethane elastomer damping material.The present invention reacts polyester diol and diisocyanate cpd
Polyurethane prepolymer is prepared, then to hold monohydroxy compound to prepare suspended chain prepolymer, terminal hydroxy group with diisocyanate cpd
Hyper-branched polyester raw material is reacted with each prepolymer as crosslinking agent and chain extender, obtains damping material.Pass through the present invention's
Damping material prepared by method, about 170 DEG C of effective damping temperature range (- 50 DEG C~120 DEG C), compared to general wide temperature zone high
Damping material (it is required that at least in the range of 60 DEG C~80 DEG C of temperature range (use environment temperature range), its damping factor tan δ >=0.3), this
The wide temperature range of damping material of invention, damping capacity are good, and effect is notable.
Another object of the present invention is to provide the wide temperature range designed based on network structure obtained by above-mentioned preparation method
Polyurethane elastomer damping material.
The polyurethane elastomer damping property of the present invention is excellent, reasonably hands over chain extender (superbrnaching end-hydroxy polyester
Raw material) make it that fractional free volume is bigger in polyurethane elastomer network structure with the proportioning of prepolymer；One end of suspended chain is consolidated
It is fixed, the other end can free movement, suspended chain is more timely to outside stimuli responsive, and conformation is changeable, possesses relative to elastic main chain
More loose patterns, after outside stimulus disappears, suspended chain recovers deformation also or produces new conformation, and secondly suspended chain is recyclable anti-
It is multiple that outside stimulus is responded, while the introducing of suspended chain can be effectively improved soft and hard segments compatibility, suspended chain and elastic main chain
Compliance is approached, and long suspended chain also effectively can prevent hard section from assembling, and reduces the soft and hard segments microphase-separated of polyurethane elastomer；Hold hydroxyl
Base hyper-branched polyester is as chain extender is handed over, and abundant power supply base is possessed on super branched molecule chain, suspended chain and electric base is inhaled to strengthen
The hydrogen bond action of cross-linked network.Free volume, microphase-separated, the aspect collaboration of hydrogen bond action three compound action assign the polyurethane bullet
Property the wide temperature range scope of body (about 170 DEG C of temperature range) internal damping it is functional, high temperature effective damping up to 120 DEG C, be expected to traffic transport
Apply in the fields such as defeated, building engineering field.
It is still another object of the present invention to provide the above-mentioned wide temperature range polyurethane elastomer damping designed based on network structure
The application of material.
In order to achieve the above object, the technical solution adopted by the present invention is as follows：
A kind of wide temperature range polyurethane elastomer damping material designed based on network structure, is prepared from the following components：
The parts by weight of polyurethane prepolymer 11~37, the parts by weight of suspended chain prepolymer 7~30, the parts by weight of superbrnaching end-hydroxy polyester 1~25；
The polyurethane prepolymer, is to be reacted to obtain in the presence of catalyst by polyester diol, diisocyanate, its
Middle polyester diol and the weight of diisocyanate ratio are (10~30)：(1~7), the polyester diol need before the reaction into
Row vacuum dehydration is handled；
The suspended chain prepolymer, is to be reacted by end monohydroxy compound, diisocyanate in the presence of catalyst
Arrive, the weight ratio of its middle-end monohydroxy compound and diisocyanate is (5~20)：(2~10).
The superbrnaching end-hydroxy polyester, its terminal hydroxy group number >=5, molecular weight >=500；Preferably Wuhan hyperbranched resin section
Skill Co., Ltd production H101, H102, H103, H104, H201, H202, H203, H204, H301, H302, H303, H304,
One or more of H401, H402, H403.
The polyester diol is that dicarboxylic acids or acid anhydrides or lactone are formed with dihydric alcohol condensation polymerization.
Preferably, the binary acid or acid anhydrides be adipic acid, phthalic acid, phthalate anhydride, halo phthalic acid, in oneself
Ester etc., preferably adipic acid；The dihydric alcohol be BDO, ethylene glycol, hexylene glycol, to neopentyl glycol, diethylene glycol etc..
The polyester diol is preferably aliphatic polyester binary alcohol.
Preferably, the molecular weight of the polyester diol is 1000-4000.
Diisocyanate in the polyurethane prepolymer and diisocyanate in suspended chain prepolymer are identical or different,
Diisocyanate be 2,4 toluene diisocyanate (TDI), IPDI, hexamethylene diisocyanate or 4,
4 '-methyl diphenylene diisocyanate；Preferably 2,4 toluene diisocyanate (TDI).
The end monohydroxy compound be poly glycol monomethyl ether, polyethylene glycol mono stearate, n-hexyl alcohol, octadecyl alcolol or
More than one in melissyl alcohol；Preferably poly glycol monomethyl ether.
The poly glycol monomethyl ether molecular weight is 350~1000.
Catalyst in the polyurethane prepolymer is identical or different with catalyst in suspended chain prepolymer, and catalyst is
More than one in dilaurate dibutyl tin, bismuth carboxylate, carboxylic acid potassium, stannous octoate.
A kind of preparation method of the wide temperature range polyurethane elastomer damping material designed based on network structure, including following step
Suddenly：
(1) preparation of polyurethane prepolymer
Polyester diol is heated to 100~120 DEG C, vacuum dehydration, the polyester diol being dehydrated；In inert gas
Under protection and moderate-speed mixer, the polyester diol of dehydration is mixed with diisocyanate, 70~80 DEG C are warming up to, catalysis is added
Stop reaction after agent, 1~3h of insulation, it is polyurethane prepolymer to obtain elastic main chain prepolymer；The inert gas is N2；
(2) preparation of suspended chain prepolymer
Under conditions of inert gas shielding and moderate-speed mixer, end monohydroxy compound is mixed with diisocyanate, risen
Temperature adds catalyst to 50~60 DEG C, and 1~2h of reaction stops reaction, obtains suspended chain prepolymer；The inert gas is N2；
(3) preparation of polyurethane elastomer damping material
Under conditions of inert gas shielding and stirring, add into the mixture of polyurethane prepolymer and suspended chain prepolymer
Enter superbrnaching end-hydroxy polyester, quick stirring, moulding by casting arranges solvent and bubble, is warming up to 60~80 DEG C, is incubated 8~24h,
80~100 DEG C are continuously heating to, 1h~6h is incubated, solidification is completed, and obtains polyurethane elastomer damping material；The terminal hydroxy group surpasses
Branched polyester is to add as a solution, and superbrnaching end-hydroxy polyester is dissolved in solvent and obtained.
Polyurethane elastomer damping factor tan δ >=0.3 in the range of 170 DEG C of temperature ranges；High temperature effective damping is reachable
120 DEG C, be wide temperature zone high damping polyurethane elastomer material；
Solvent described in step (3) is more than one in tetrahydrofuran, dimethyl acetamide, toluene, dimethylbenzene, acetone.
Vacuum dehydration described in step (1) is carried out under conditions of stirring, and mixing speed is 100~250r/min；Institute
The condition for stating vacuum dehydration is that 1.5~3h is dried under 1~2MPa pressure.The rotating speed of moderate-speed mixer described in step (1) is 200
~350r/min.
The addition of catalyst described in step (1) is 0.01 ‰~the 5 ‰ of polyester diol and isocyanate weight；Step
Suddenly the addition of catalyst described in (2) is end monohydroxy compound and 0.01 ‰~the 5 ‰ of diisocyanate weight.
The rotating speed of moderate-speed mixer described in step (2) is 200~350r/min；That is quickly stirred described in step (3) turns
Speed is 350~500r/min.The time quickly stirred described in step (3) is 5~10min.
60~80 DEG C are warming up in the preparation of the polyurethane prepolymer to be completed at 5~10 minutes, and the suspended chain is pre-
Polymers is warming up to 50~60 DEG C and need to completed at 5~10 minutes in preparing.
A kind of wide temperature range polyurethane elastomer damping material designed based on network structure, is made by above-mentioned preparation method.
Damping factor tan δ >=0.3 in the range of about 170 DEG C of temperature ranges of polyurethane elastomer damping material of the present invention, while high
Warm effective damping is up to 120 DEG C.
In the present invention, ingenious selection superbrnaching end-hydroxy polyester is used as the freedom for handing over chain extender to adjust polyurethane elastomer
Volume fraction is (by the proportioning i.e. the isocyano molal quantity and hydroxyl moles that adjust superbrnaching end-hydroxy polyester and prepolymer
Ratio, realizes the regulation of fractional free volume, and superbrnaching end-hydroxy polyester, molecule of one side itself is big, another aspect end band
There is hydroxyl many, (TMP ends only have 3 hydroxyls, and TMP molecular weight is small in addition, comparatively, hold hydroxyl with other crosslinking agents such as TMP
Base hyper-branched polyester end at least five hydroxyl, molecular weight minimum is also 500, while hydrogen bond action of hyper-branched polyester etc. is all more
The advantage not having by force), while introducing suspended chain in cross-linked network structure, designs the cross-linked network knot of bigger fractional free volume
Suspended chain has bigger activity space in structure, is fixed using suspended chain only one end, can have bigger free volume hole to carry out
Rich and varied relaxation pattern consumes mechanical energy.The present invention cooperates with multiple in terms of free volume, microphase-separated, hydrogen bond action three
Cooperation is with improving material damping performance.
The raw material of wide temperature range damping polyurethane elastomer synthesized by the present invention is commercially available to be easy to get, moderate, and polyurethane is certainly
Body has good combination property, and the present invention is set out based on network structure design angle, prepares a kind of poly- ammonia of wide temperature range damping
Ester elastomer material.The present invention by diisocyanate (such as：TDI) with polyester diol reaction institute's formation backbone structure with preferable
Mechanical strength；Hold monohydroxy compound (such as：Poly glycol monomethyl ether) and diisocyanate is (such as：TDI) the suspended chain prepared
Compliance is good, and relaxation pattern is various, recyclable to consume mechanical energy repeatedly；Superbrnaching end-hydroxy polyester holds hydroxyl as chain extender is handed over
The hyperbranched end of base carries multiple activity hydroxies, and crosslink density when controllable solidifies assigns synthetic polymer bigger free body
Fraction, while the electric base of the suction enriched on molecule, power supply base contribute to cross-linked network to form stronger hydrogen bond action.From free body
Product, microphase-separated, the aspect collaboration of hydrogen bond action three compound action cause the synthetically prepared polyurethane elastomer of the present invention to be one kind
Damping factor tan δ >=0.3 in the range of damping material with wide-temperature range, about 170 DEG C of temperature ranges, while high temperature effective damping is up to 120 DEG C,
Actual operation requirements can be met.
Using TDI as diisocyanate cpd raw material, friendship chain extender superbrnaching end-hydroxy polyester is used exemplified by H201, this
The reaction mechanism schematic diagram of invention is as shown in Figure 1.
Relative to prior art, the invention has the advantages that and beneficial effect：
1. the polyurethane damping material effective damping temperature range width of the present invention is big (about 170 DEG C), damping and amortization in the range of temperature range
Excellent, its damping factor tan δ >=0.3 of energy, existing polyurethane elastomer effective damping temperature range narrower width is about 60 DEG C~80
DEG C or so；
2. the polyurethane damping material high/low temperature damping capacity of the present invention is good, high temperature effective damping can be met up to 120 DEG C
Market application requirement (polyurethane elastomer material temperature in use is generally below 100 DEG C), the effective damping of low temperature direction can reach -50
DEG C or so, it also can reach use requirement for extremely cold area；
3. present invention introduces superbrnaching end-hydroxy polyester as chain extender is handed over, it have adjusted based on the damping of network structure polyurethane
The fractional free volume of cross-linked network in material, assigns the bigger freedom of movement volume fraction of suspended chain in damping material, simultaneously
Hydrogen bond action in the suspended chain of introducing, enhancing cross-linked network, it is of the invention from free volume, microphase-separated, hydrogen bond action tripartite
Face collaboration compound action improves polyurethane material damping capacity.
Brief description of the drawings
Fig. 1 is reaction mechanism schematic diagram of the invention；
Dynamic mechanical spectrograms of the Fig. 2 for embodiment 2 and the damping material of the preparation of embodiment 4 under 10Hz；
Dynamic mechanical spectrograms of the Fig. 3 for comparative example 1 and the damping material of the preparation of comparative example 2 under 10Hz.
Embodiment
To more fully understand the present invention, with reference to embodiment and accompanying drawing, the invention will be further described, but this hair
Bright claimed scope is not limited to this.
Polyester diol used in embodiment and comparative example, the trade mark is 2200A, molecular weight 2000, by Jining of Shandong Province China
Triumphant resin Co., Ltd production；
Diisocyanate cpd TDI used is 2,4- toluene di-isocyanate(TDI)s in embodiment and comparative example, analyzes pure,
Produced by Tianjin good fortune morning chemical reagent；
Poly glycol monomethyl ether, analyzes pure, molecular weight is respectively 350,550,750,1000, by the biochemical section of Shanghai Aladdin
Skill limited company produces.
It is H201, H202 to hand over chain extender superbrnaching end-hydroxy polyester, and chemistry is pure, by the limited public affairs of Wuhan hyperbranched resin science and technology
Department's production.
The Glycerin (TMP) of friendship chain extender 1,1,1- used in comparative example, analyzes pure, by the biochemical section of Shanghai Aladdin
Skill limited company produces.
Embodiment 1
A kind of preparation method of the wide temperature range polyurethane elastomer damping material designed based on network structure, including following step
Suddenly：
(1) 20 weight of polyester dihydric alcohols under conditions of stirring (200r/min), are subjected to vacuum drying treatment (vacuum
The condition of drying process is under 1MPa pressure, in 100 DEG C of dry 2.5h), the polyester diol pre-processed；
(2) polyester diol of pretreatment is cooled to room temperature in step (1), closes vavuum pump, leads to N2, moderate-speed mixer
(250r/min), adds 3 parts by weight TDI, is warming up to 80 DEG C, and the catalyst dibutyltin cinnamic acid ester dibutyl of 0.003 parts by weight is added dropwise
Tin, is incubated 1.5h, stops reaction, obtains elastic main chain prepolymer i.e. polyurethane prepolymer, N2Preserved under atmosphere；
(3) in N2Under atmosphere protection, 3 parts by weight are added into 10 parts by weight poly glycol monomethyl ethers (molecular weight 550)
TDI, moderate-speed mixer (250r/min), is warming up in 5 minutes after 50 DEG C, and the catalyst dibutyltin osmanthus of 0.001 parts by weight is at the uniform velocity added dropwise
Acid esters dibutyl tin, is incubated 1h, stops reaction, obtains suspended chain prepolymer, N2Preserved under atmosphere；
(4) parts by weight of polyurethane prepolymer 23 in step (2), the parts by weight of step (3) suspended chain prepolymer 13 are taken in reaction
In container, N2The lower moderate-speed mixer (250r/min) of atmosphere protection, obtains mixture；Weighing 8 parts by weight H201 hands over chain extender to be dissolved in
In 15ml tetrahydrofuran solvents, it is completely dissolved, and adds polyurethane prepolymer with the mixture of suspended chain prepolymer, quickly stirring
Mix 5min (350r/min), pour in Teflon mould, mould is placed in vacuum drying chamber and vacuumized, row solvent and
Bubble, is warming up to 70 DEG C, is incubated 15h, then raises temperature to 90 DEG C, and insulation 2h carries out solidify afterwards, obtains polyurethane elastomer
Damping material.
Embodiment 2
A kind of preparation method of the wide temperature range polyurethane elastomer damping material designed based on network structure, including following step
Suddenly：
(1) 30 weight of polyester dihydric alcohols under conditions of stirring (200r/min), are subjected to vacuum drying treatment (vacuum
The condition of drying process is under 1MPa pressure, in 100 DEG C of dry 2.5h), the polyester diol pre-processed；
(2) polyester diol of pretreatment is down to room temperature in step (1), closes vavuum pump, leads to N2, N2Atmosphere protection is lower to be added
Enter 7 parts by weight TDI, moderate-speed mixer (250r/min) is warming up to 80 DEG C, the catalyst dibutyltin cinnamic acid ester of 0.004 parts by weight is added dropwise
Dibutyl tin, is incubated 1.5h, stops reaction, obtains elastic main chain prepolymer i.e. polyurethane prepolymer, N2Preserved under atmosphere；
(3) in N2Under atmosphere protection, to 15 parts by weight poly glycol monomethyl ethers (molecular weight 1000), 5 parts by weight are added
TDI, moderate-speed mixer (250r/min), is warming up in 5 minutes after 50 DEG C, and the catalyst dibutyltin osmanthus of 0.003 parts by weight is at the uniform velocity added dropwise
Acid esters dibutyl tin, is incubated 1h, stops reaction, obtains suspended chain prepolymer, N2Preserved under atmosphere；
(4) parts by weight of step (2) polyurethane prepolymer 37, the parts by weight of step (3) suspended chain prepolymer 20 are taken to hold in reaction
In device, N2The lower moderate-speed mixer (250r/min) of atmosphere protection, obtains mixture；Weighing 12 parts by weight H201 hands over chain extender to be dissolved in
Polyurethane prepolymer is added in 20ml tetrahydrofuran solvents, after being completely dissolved with the mixture of suspended chain prepolymer, quickly stirring
Mix 5min (350r/min), pour in Teflon mould, mould is placed in vacuum drying chamber and vacuumized, row solvent and
Bubble, is warming up to 80 DEG C, is incubated 12h, then raises temperature to 100 DEG C, and insulation 2h carries out solidify afterwards, obtains polyurethane elastomer
Damping material.The dynamic mechanical spectrogram of damping material prepared by embodiment 2 under 10Hz is as shown in Figure 2.
Embodiment 3
A kind of preparation method of the wide temperature range polyurethane elastomer damping material designed based on network structure, including following step
Suddenly：
(1) 15 weight of polyester dihydric alcohols under conditions of stirring (200r/min), are subjected to vacuum drying treatment (vacuum
The condition of drying process is under 1MPa pressure, in 100 DEG C of dry 2.5h), the polyester diol pre-processed；
(2) polyester diol of pretreatment is down to room temperature in step (1), closes vavuum pump, leads to N2, add 3 parts by weight
TDI, moderate-speed mixer (250r/min) is warming up to after 80 DEG C in several minutes, and the catalyst dibutyltin cinnamic acid of 0.0015 parts by weight is added dropwise
Ester dibutyl tin, is incubated 1.5h, stops reaction, obtains elastic main chain prepolymer i.e. polyurethane prepolymer, N2Preserved under atmosphere；
(3) in N2Under atmosphere protection, 3 parts by weight TDI are added to 5 parts by weight poly glycol monomethyl ethers (molecular weight 750), in
Speed stirring (250r/min), is warming up in 5 minutes after 50 DEG C, and the catalyst dibutyltin cinnamic acid ester dibutyl of 0.0005 parts by weight is added dropwise
Tin, is incubated 1h, stops reaction, obtains suspended chain prepolymer, N2Preserved under atmosphere.
(4) parts by weight of step (2) polyurethane prepolymer 18, the parts by weight of step (3) suspended chain prepolymer 8 are taken in three-necked flask
In, N2The lower moderate-speed mixer (250r/min) of atmosphere protection, obtains mixture；Weighing 3 parts by weight H201 hands over chain extender to be dissolved in 10ml
Polyurethane prepolymer is added in tetrahydrofuran solvent, after being completely dissolved with the mixture of suspended chain prepolymer, quickly stirring
5min (350r/min), pours in Teflon mould, mould is placed in vacuum drying chamber and vacuumized, and row's solvent is gentle
Bubble, is warming up to 60 DEG C, is incubated 24h, then raises temperature to 80 DEG C, and insulation 2h carries out solidify afterwards, obtains polyurethane elastomer resistance
Damping material.
Embodiment 4
A kind of preparation method of the wide temperature range polyurethane elastomer damping material designed based on network structure, including following step
Suddenly：
(1) 25 weight of polyester dihydric alcohols under conditions of stirring (200r/min), are subjected to vacuum drying treatment (vacuum
The condition of drying process is under 1MPa pressure, in 100 DEG C of dry 2.5h), the polyester diol pre-processed；
(2) polyester diol of pretreatment is down to room temperature in step (1), closes vavuum pump, leads to N2, N2Atmosphere protection is lower to be added
Enter 5 parts by weight TDI, moderate-speed mixer (250r/min) is warming up to after 80 DEG C, the catalyst dibutyltin cinnamic acid of 0.005 parts by weight is added dropwise
Ester dibutyl tin, is incubated 1.5h, stops reaction, obtains elastic main chain prepolymer i.e. polyurethane prepolymer, N2Preserved under atmosphere；
(3) in N2Under atmosphere protection, 2 parts by weight TDI are added to 6 parts by weight poly glycol monomethyl ethers (molecular weight 350), in
Speed stirring (250r/min), is warming up in 6 minutes after 60 DEG C, and the catalyst dibutyltin cinnamic acid ester dibutyl of 0.001 parts by weight is added dropwise
Tin, is incubated 1h, stops reaction, obtains suspended chain prepolymer, N2Preserved under atmosphere；
(4) 30 parts by weight step (2) polyurethane prepolymers, 8 parts by weight step (3) suspended chain prepolymers are taken in reaction vessel
In, N2The lower moderate-speed mixer (250r/min) of atmosphere protection, obtains mixture；Weighing 17 parts by weight H202 hands over chain extender to be dissolved in 20ml
Polyurethane prepolymer is added in tetrahydrofuran solvent, after being completely dissolved with the mixture of suspended chain prepolymer, quickly stirring
5min (350r/min), pours in Teflon mould, mould is placed in vacuum drying chamber and vacuumized, and row's solvent is gentle
Bubble, is warming up to 70 DEG C, is incubated 15h, then raises temperature to 90 DEG C, and insulation 2h carries out solidify afterwards, obtains polyurethane elastomer resistance
Damping material.The dynamic mechanical spectrogram of damping material prepared by embodiment 4 under 10Hz is as shown in Figure 2.
Embodiment 5
A kind of preparation method of the wide temperature range polyurethane elastomer damping material designed based on network structure, including following step
Suddenly：
(1) 20 weight of polyester dihydric alcohols under conditions of stirring (200r/min), are subjected to vacuum drying treatment (vacuum
The condition of drying process is under 1MPa pressure, in 100 DEG C of dry 2.5h), the polyester diol pre-processed；
(2) polyester diol of pretreatment is down to room temperature in step (1), closes vavuum pump, leads to N2, N2Atmosphere protection is lower to be added
Enter 4 parts by weight TDI, moderate-speed mixer (250r/min) is warming up in 5 minutes after 70 DEG C, the catalyst two of 0.006 parts by weight is added dropwise
Laurate dibutyl tin, is incubated 2h, stops reaction, obtains elastic main chain prepolymer i.e. polyurethane prepolymer, N2Preserved under atmosphere；
(3) in N2Under atmosphere protection, 4 parts by weight are added into 15 parts by weight poly glycol monomethyl ethers (molecular weight 1000)
TDI, moderate-speed mixer (250r/min), is warming up in 5 minutes after 50 DEG C, and the catalyst dibutyltin cinnamic acid ester of 0.004 parts by weight is added dropwise
Dibutyl tin, is incubated 1.5h, stops reaction, obtains suspended chain prepolymer, N2Preserved under atmosphere；
(4) 24 parts by weight step (2) polyurethane prepolymers, 19 parts by weight step (3) suspended chain prepolymers are taken to hold in reaction
In device, N2The lower moderate-speed mixer (250r/min) of atmosphere protection, obtains mixture；Weighing 9 parts by weight H201 hands over chain extender to be dissolved in
Polyurethane prepolymer is added in 20ml tetrahydrofuran solvents, after being completely dissolved with the mixture of suspended chain prepolymer, quickly stirring
Mix 5min (350r/min), pour in Teflon mould, mould is placed in vacuum drying chamber and vacuumized, row solvent and
Bubble, exhaust is warming up to 60 DEG C after terminating, be incubated 24h, then raises temperature to 80 DEG C, and insulation 2h carries out solidify afterwards, is gathered
Urethane elastomer damping material.
Embodiment 6
A kind of preparation method of the wide temperature range polyurethane elastomer damping material designed based on network structure, including following step
Suddenly：
(1) 30 weight of polyester dihydric alcohols under conditions of stirring (200r/min), are subjected to vacuum drying treatment (vacuum
The condition of drying process is under 1MPa pressure, in 100 DEG C of dry 2.5h), the polyester diol pre-processed；
(2) polyester diol of pretreatment is down to room temperature in step (1), closes vavuum pump, leads to N2, N2Atmosphere protection is lower to be added
Enter 6 parts by weight TDI, moderate-speed mixer (250r/min) is warming up to 75 DEG C, the catalyst dibutyltin cinnamic acid ester of 0.005 parts by weight is added dropwise
Dibutyl tin, is incubated 2h, stops reaction, obtains elastic main chain prepolymer i.e. polyurethane prepolymer, N2Preserved under atmosphere；
(3) in N2Under atmosphere protection, 4 parts by weight TDI are added into 8 parts by weight poly glycol monomethyl ethers (molecular weight 350),
Moderate-speed mixer (250r/min), is warming up in 5 minutes after 60 DEG C, and the fourth of catalyst dibutyltin cinnamic acid ester two of 0.002 parts by weight is added dropwise
Ji Xi, is incubated 1h, stops reaction, obtains suspended chain prepolymer, N2Preserved under atmosphere；
(4) 36 parts by weight step (2) polyurethane prepolymers, 12 parts by weight step (3) suspended chain prepolymers are taken to hold in reaction
In device, N2The lower moderate-speed mixer (250r/min) of atmosphere protection, obtains mixture；Weighing 18 parts by weight H201 hands over chain extender to be dissolved in
In the mixed solution that polyurethane prepolymer and suspended chain prepolymer are added in 25ml tetrahydrofuran solvents, after being completely dissolved, quickly
5min (350r/min) is stirred, pours in Teflon mould, mould is placed in vacuum drying chamber and vacuumized, solvent is arranged
And bubble, it is vented after terminating and vacuum drying chamber is warming up to 70 DEG C, be incubated 24h, then raise temperature to 90 DEG C, insulation 2h is carried out
Solidify afterwards, obtain polyurethane elastomer damping material.
Comparative example 1
A kind of preparation method of polyurethane elastomer damping material, comprises the following steps：
(1) 30 weight of polyester dihydric alcohols under conditions of stirring (200r/min), are subjected to vacuum drying treatment (vacuum
The condition of drying process is under 1MPa pressure, in 100 DEG C of dry 2.5h), the polyester diol pre-processed；
(2) polyester diol of pretreatment is down to room temperature in step (1), closes vavuum pump, leads to N2, N2Atmosphere protection is lower to be added
Enter 7 parts by weight TDI, moderate-speed mixer (250r/min) is warming up to 80 DEG C, the catalyst dibutyltin cinnamic acid ester of 0.006 parts by weight is added dropwise
Dibutyl tin, is incubated 1.5h, stops reaction, obtains elastic main chain prepolymer i.e. polyurethane prepolymer, N2Preserved under atmosphere；
(3) weighing 2 parts by weight TMP hands over chain extender to be dissolved in 5ml acetone solvents, and polyurethane prepolymer is added after being completely dissolved
In, 5min (350r/min) is quickly stirred, is poured in Teflon mould, mould is placed in vacuum drying chamber and takes out true
Sky, row's solvent and bubble, are warming up to 80 DEG C, are incubated 12h, then raise temperature to 100 DEG C, and insulation 2h carries out solidify afterwards, obtains
Polyurethane elastomer damping material.The dynamic mechanical spectrogram of damping material prepared by comparative example 1 under 10Hz is as shown in Figure 3.
Comparative example 2
A kind of preparation method of polyurethane elastomer damping material, comprises the following steps：
(1) 25 weight of polyester dihydric alcohols under conditions of stirring (200r/min), are subjected to vacuum drying treatment (vacuum
The condition of drying process is under 1MPa pressure, in 100 DEG C of dry 2.5h), the polyester diol pre-processed；
(2) polyester diol of pretreatment is down to room temperature in step (1), closes vavuum pump, leads to N2, N2Atmosphere protection is lower to be added
Enter 5 parts by weight TDI, moderate-speed mixer (250r/min) is warming up to 80 DEG C, the catalyst dibutyltin cinnamic acid ester of 0.004 parts by weight is added dropwise
Dibutyl tin, is incubated 1.5h, stops reaction, obtains elastic main chain prepolymer i.e. polyurethane prepolymer, N2Preserved under atmosphere；
(3) in N2Under atmosphere protection, 2 parts by weight TDI are added into 6 parts by weight poly glycol monomethyl ethers (molecular weight 350),
Moderate-speed mixer (250r/min), is warming up in 5 minutes after 60 DEG C, and the fourth of catalyst dibutyltin cinnamic acid ester two of 0.002 parts by weight is added dropwise
Ji Xi, is incubated 1h, stops reaction, obtains suspended chain prepolymer, N2Preserved under atmosphere；
(4) 30 parts by weight step (2) polyurethane prepolymers, 8 parts by weight step (3) suspended chain prepolymers are taken in reaction vessel
In, N2The lower moderate-speed mixer (250r/min) of atmosphere protection, obtains mixture；
(5) weighing 2 parts by weight TMP hands over chain extender to be dissolved in 5ml acetone solvents, and polyurethane prepolymer is added after being completely dissolved
With in the mixed solution of suspended chain prepolymer, quickly stirring 5min (350r/min), pouring in Teflon mould, by mould
Tool, which is placed in vacuum drying chamber, to be vacuumized, and row's solvent and bubble are warming up to 70 DEG C, are incubated 15h, then raises temperature to 90 DEG C,
It is incubated 2h and carries out solidify afterwards, obtains polyurethane elastomer damping material.The dynamic of damping material prepared by comparative example 2 under 10Hz
Mechanics spectrogram is as shown in Figure 3.
Performance test：
DMA 242C type dynamic mechanicals are used to the damping capacity of embodiment 1~6 and the polyurethane material of comparative example 1~2
Analyzer (Nai Chi companies, Germany) carries out dynamic mechanical test analysis to it, and test condition is：Stretch mode, scans temperature model
Enclose -100~120 DEG C, heating rate 3 DEG C/min, test frequency 10Hz.Test result is as shown in Figures 2 and 3.
The damping material that Fig. 2 is embodiment 2, prepared by embodiment 4 dynamic mechanical spectrogram obtained by DMA tests under 10Hz；Fig. 3
For comparative example 1, comparative example 2 prepare damping material under 10Hz DMA test obtained by dynamic mechanical spectrogram.It has been generally acknowledged that damping because
Sub- tan δ >=0.3 is effective damping performance, it is seen then that the polyurethane elastomer material that the present invention is designed based on network structure, is had
1,3,5,6 samples are moved under 10Hz in (about 170 DEG C of temperature range scopes) damping factor tan δ >=0.3, embodiment in the range of wide temperature range
State mechanics spectrogram and embodiment 2,4 are substantially similar, and the temperature range scope of damping factor tan δ >=0.3 is also at 170 DEG C or so.(in damping
During factor t an δ >=0.3, about -50 DEG C~120 DEG C of effective damping temperature range).
Embodiments of the present invention are simultaneously not restricted to the described embodiments, other any without departing from spirit of the invention
With the change made under principle, modification, replacement, combine, simplify, should be equivalent substitute mode, be included in the present invention
Within protection domain.
Claims (10)
1. a kind of wide temperature range polyurethane elastomer damping material designed based on network structure, it is characterised in that：By following components
It is prepared from：The parts by weight of polyurethane prepolymer 11~37, the parts by weight of suspended chain prepolymer 7~30, superbrnaching end-hydroxy polyester 1~
25 parts by weight；
The polyurethane prepolymer, is to be reacted to obtain in the presence of catalyst by polyester diol, diisocyanate, wherein poly-
The weight ratio of ester dihydric alcohol and diisocyanate is (10~30)：(1~7), the polyester diol needs to carry out very before the reaction
Empty dewater treatment；
The suspended chain prepolymer, is to be reacted to obtain in the presence of catalyst by end monohydroxy compound, diisocyanate, its
The weight ratio of middle-end monohydroxy compound and diisocyanate is (5~20)：(2~10).
2. the wide temperature range polyurethane elastomer damping material designed according to claim 1 based on network structure, its feature is existed
In：The superbrnaching end-hydroxy polyester, its terminal hydroxy group number >=5, molecular weight >=500；
Diisocyanate in the polyurethane prepolymer is identical or different with diisocyanate in suspended chain prepolymer, and two is different
Cyanate is 2,4 toluene diisocyanate, IPDI, hexamethylene diisocyanate or 4,4 '-diphenyl
Methane diisocyanate；
The molecular weight of the polyester diol is 1000-4000；
The end monohydroxy compound is poly glycol monomethyl ether, polyethylene glycol mono stearate, n-hexyl alcohol, octadecyl alcolol or 30
More than one in alcohol.
3. the wide temperature range polyurethane elastomer damping material designed according to claim 2 based on network structure, its feature is existed
In：The superbrnaching end-hydroxy polyester be Wuhan hyperbranched resin Science and Technology Ltd. produce H101, H102, H103, H104,
One or more of H201, H202, H203, H204, H301, H302, H303, H304, H401, H402, H403；
Diisocyanate in the polyurethane prepolymer and the diisocyanate in suspended chain prepolymer are different for 2,4- toluene two
Cyanate；
The end monohydroxy compound is poly glycol monomethyl ether.
4. the wide temperature range polyurethane elastomer damping material designed according to claim 1 based on network structure, its feature is existed
In：Catalyst in the polyurethane prepolymer is identical or different with catalyst in suspended chain prepolymer, and catalyst is February
More than one in cinnamic acid ester dibutyl tin, bismuth carboxylate, carboxylic acid potassium, stannous octoate；
The superbrnaching end-hydroxy polyester is added as a solution.
5. the wide temperature range polyurethane elastomer damping material designed according to any one of Claims 1 to 4 based on network structure
Preparation method, it is characterised in that：Comprise the following steps：
(1) preparation of polyurethane prepolymer
Polyester diol is heated to 100~120 DEG C, vacuum dehydration, the polyester diol being dehydrated；In inert gas shielding
Under moderate-speed mixer, the polyester diol of dehydration is mixed with diisocyanate, 70~80 DEG C are warming up to, catalyst is added, protected
Stop reaction after 1~3h of temperature, it is polyurethane prepolymer to obtain elastic main chain prepolymer；The inert gas is N2；
(2) preparation of suspended chain prepolymer
Under conditions of inert gas shielding and moderate-speed mixer, end monohydroxy compound is mixed with diisocyanate, is warming up to
50~60 DEG C, catalyst is added, 1~2h of reaction stops reaction, obtains suspended chain prepolymer；The inert gas is N2；
(3) preparation of polyurethane elastomer damping material
Under conditions of inert gas shielding and stirring, end is added into the mixture of polyurethane prepolymer and suspended chain prepolymer
Hydroxyl hyper-branched polyester, quick stirring, moulding by casting, row's solvent and bubble, are warming up to 60~80 DEG C, are incubated 8~24h, continue
80~100 DEG C are warming up to, 1h~6h is incubated, solidification is completed, and obtains polyurethane elastomer damping material；The superbrnaching end-hydroxy
Polyester is to add as a solution, and superbrnaching end-hydroxy polyester is dissolved in solvent and obtained.
6. the preparation side of the wide temperature range polyurethane elastomer damping material designed according to claim 5 based on network structure
Method, it is characterised in that：The solvent is more than one in tetrahydrofuran, dimethyl acetamide, toluene, dimethylbenzene, acetone.
7. the preparation side of the wide temperature range polyurethane elastomer damping material designed according to claim 5 based on network structure
Method, it is characterised in that：Vacuum dehydration described in step (1) is carried out under conditions of stirring, and mixing speed is 100~250r/
min；The condition of the vacuum dehydration is that 1.5~3h is dried under 1~2MPa pressure；Turn of moderate-speed mixer described in step (1)
Speed is 200~350r/min.
8. the preparation side of the wide temperature range polyurethane elastomer damping material designed according to claim 5 based on network structure
Method, it is characterised in that：The addition of catalyst described in step (1) be polyester diol and isocyanate weight 0.01 ‰~
5‰；The addition of catalyst described in step (2) is end monohydroxy compound and 0.01 ‰~the 5 ‰ of diisocyanate weight.
9. the preparation side of the wide temperature range polyurethane elastomer damping material designed according to claim 5 based on network structure
Method, it is characterised in that：The rotating speed of moderate-speed mixer described in step (2) is 200~350r/min；Step is quickly stirred described in (3)
The rotating speed mixed is 350~500r/min；The time quickly stirred described in step (3) is 5~10min.
10. the wide temperature range polyurethane elastomer damping material designed according to any one of Claims 1 to 4 based on network structure
Application, it is characterised in that：It is described to be transported based on the wide temperature range polyurethane elastomer damping material that network structure is designed for traffic
Defeated and building engineering field.
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| CN113896859A (en) * | 2021-10-13 | 2022-01-07 | 北京化工大学 | Bio-based polyurethane damping material and preparation method and application thereof |
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| CN113896859A (en) * | 2021-10-13 | 2022-01-07 | 北京化工大学 | Bio-based polyurethane damping material and preparation method and application thereof |
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