CN116751355A - Organic silicon modified polyurethane high polymer for soft-coated aluminum-plastic film of power battery and preparation method thereof - Google Patents
Organic silicon modified polyurethane high polymer for soft-coated aluminum-plastic film of power battery and preparation method thereof Download PDFInfo
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- CN116751355A CN116751355A CN202311035253.8A CN202311035253A CN116751355A CN 116751355 A CN116751355 A CN 116751355A CN 202311035253 A CN202311035253 A CN 202311035253A CN 116751355 A CN116751355 A CN 116751355A
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- 229920000642 polymer Polymers 0.000 title claims abstract description 24
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 24
- 239000004814 polyurethane Substances 0.000 title claims abstract description 24
- 239000002985 plastic film Substances 0.000 title claims abstract description 15
- 229920006255 plastic film Polymers 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title description 2
- 229910052710 silicon Inorganic materials 0.000 title description 2
- 239000010703 silicon Substances 0.000 title description 2
- -1 polydimethylsiloxane Polymers 0.000 claims abstract description 68
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims abstract description 64
- 239000004205 dimethyl polysiloxane Substances 0.000 claims abstract description 55
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims abstract description 55
- 235000013870 dimethyl polysiloxane Nutrition 0.000 claims abstract description 51
- 229920001610 polycaprolactone Polymers 0.000 claims abstract description 44
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims abstract description 36
- 150000002009 diols Chemical class 0.000 claims abstract description 35
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 claims abstract description 35
- 239000004632 polycaprolactone Substances 0.000 claims abstract description 35
- BJZYYSAMLOBSDY-QMMMGPOBSA-N (2s)-2-butoxybutan-1-ol Chemical compound CCCCO[C@@H](CC)CO BJZYYSAMLOBSDY-QMMMGPOBSA-N 0.000 claims abstract description 34
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229920005862 polyol Polymers 0.000 claims abstract description 17
- 150000003077 polyols Chemical class 0.000 claims abstract description 17
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 12
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 70
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 claims description 40
- IBVAQQYNSHJXBV-UHFFFAOYSA-N adipic acid dihydrazide Chemical compound NNC(=O)CCCCC(=O)NN IBVAQQYNSHJXBV-UHFFFAOYSA-N 0.000 claims description 32
- 239000002994 raw material Substances 0.000 claims description 26
- 239000002904 solvent Substances 0.000 claims description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- 238000010992 reflux Methods 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 239000003054 catalyst Substances 0.000 claims description 14
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 238000006722 reduction reaction Methods 0.000 claims description 5
- YZUPZGFPHUVJKC-UHFFFAOYSA-N 1-bromo-2-methoxyethane Chemical compound COCCBr YZUPZGFPHUVJKC-UHFFFAOYSA-N 0.000 claims description 4
- NYTOUQBROMCLBJ-UHFFFAOYSA-N Tetranitromethane Chemical compound [O-][N+](=O)C([N+]([O-])=O)([N+]([O-])=O)[N+]([O-])=O NYTOUQBROMCLBJ-UHFFFAOYSA-N 0.000 claims description 4
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 4
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 4
- UXXXZMDJQLPQPH-UHFFFAOYSA-N bis(2-methylpropyl) carbonate Chemical compound CC(C)COC(=O)OCC(C)C UXXXZMDJQLPQPH-UHFFFAOYSA-N 0.000 claims description 4
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 4
- KEVMYFLMMDUPJE-UHFFFAOYSA-N diisoamyl Natural products CC(C)CCCCC(C)C KEVMYFLMMDUPJE-UHFFFAOYSA-N 0.000 claims description 4
- 239000012467 final product Substances 0.000 claims description 4
- NCPHGZWGGANCAY-UHFFFAOYSA-N methane;ruthenium Chemical compound C.[Ru] NCPHGZWGGANCAY-UHFFFAOYSA-N 0.000 claims description 4
- 239000007800 oxidant agent Substances 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- CKOFBUUFHALZGK-UHFFFAOYSA-N 3-[(3-aminophenyl)methyl]aniline Chemical compound NC1=CC=CC(CC=2C=C(N)C=CC=2)=C1 CKOFBUUFHALZGK-UHFFFAOYSA-N 0.000 claims description 2
- ZDAYMUZKHLQASZ-UHFFFAOYSA-N 3-[5-(3-aminophenyl)pentyl]aniline Chemical compound NC=1C=C(C=CC=1)CCCCCC1=CC(=CC=C1)N ZDAYMUZKHLQASZ-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 claims description 2
- 150000001361 allenes Chemical class 0.000 claims description 2
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 2
- 241000350481 Pterogyne nitens Species 0.000 claims 3
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 229920001296 polysiloxane Polymers 0.000 abstract 1
- 238000004821 distillation Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000012790 adhesive layer Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical group 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920005906 polyester polyol Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- FGNLEIGUMSBZQP-UHFFFAOYSA-N cadaverine dihydrochloride Chemical compound Cl.Cl.NCCCCCN FGNLEIGUMSBZQP-UHFFFAOYSA-N 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000009459 flexible packaging Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- WVJKHCGMRZGIJH-UHFFFAOYSA-N methanetriamine Chemical compound NC(N)N WVJKHCGMRZGIJH-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000007704 transition Effects 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
- C08G18/28—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
- C08G18/6622—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 C08G18/3271
-
- 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
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
-
- 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
- C08G18/61—Polysiloxanes
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 high polymers of high molecular compounds, and particularly relates to an organosilicon modified polyurethane high polymer for a soft-package aluminum-plastic film of a power battery and a preparation method thereof. Soft package aluminum-plastic film of power batteryPolyurethane polymers modified with silicones, the polyurethanes including toluene diisocyanate TDI, 4' -dicyclohexylmethane diisocyanate HMDI, polycaprolactone diol PCL1000, amino terminated polydimethylsiloxane NH 2 -PDMS, toluene diisocyanate TDI content 1-4 parts by weight; the content of the 4,4' -dicyclohexylmethane diisocyanate HMDI is 1-4 parts by weight; the content of polycaprolactone diol PCL1000 is 1-4 parts by weight, the content of polyol PTMG2000 is 1-4 parts by weight, and the polyol PTMG is NH 2 The PDMS is introduced into the system to improve the hydrophobicity and heat resistance of the system and improve the peeling strength of the system.
Description
Technical Field
The invention belongs to the technical field of high polymers of high molecular compounds, and particularly relates to an organosilicon modified polyurethane high polymer for a soft-package aluminum-plastic film of a power battery and a preparation method thereof.
Background
The aluminum plastic film flexible package has good appearance and safety performance, and the aluminum plastic film has certain ductility, can provide relatively larger buffer space when encountering expanding gas, is not easy to burst, and is widely applied to the package of lithium batteries.
At present, the high polymer used for bonding the nylon layer on the outer layer of the aluminum plastic film and the aluminum foil layer is a double-component solvent type polyurethane high polymer, the main agent is polyester polyol, the curing agent is isocyanate, and the polyurethane high polymer has higher activity and polarity and excellent shear strength and impact resistance, is suitable for various structural bonding fields, has excellent flexibility, can adapt to bonding of substrates with different thermal expansion coefficients, can form a soft-hard transition layer between the substrates, has strong bonding force, and has excellent buffering and damping functions.
However, the aluminum plastic film is drawn by cold punching in the use process to form a shell, the aluminum plastic film is drawn in the forming process, the adhesive layer is further thinned, in addition, the heat resistance of the general adhesive material in the market is poor, the general adhesive material is easy to hydrolyze at high temperature and high humidity to reduce the adhesive strength, in addition, the general adhesive material is sensitive to water, and the adhesive layer is easy to generate bubbles.
Disclosure of Invention
In order to solve the problems, the invention aims to provide an organosilicon modified polyurethane polymer for a soft-package aluminum-plastic film of a power battery and a preparation method thereof. The aim of the invention can be achieved by the following technical scheme: an organosilicon modified polyurethane polymer for a soft-coated aluminum plastic film of a power battery comprises toluene diisocyanate TDI, 4' -dicyclohexylmethane diisocyanate HMDI, polycaprolactone diol PCL1000 and terminal amino polydimethylsiloxane NH 2 -PDMS, characterized in that: toluene diisocyanate TDI content is 1-4 parts by weight; HMDI containing 4,4' -dicyclohexylmethane diisocyanateThe amount is 1-4 parts by weight; the content of the polycaprolactone diol PCL1000 is 1-4 parts by weight; the polyurethane is prepared by the following steps:
step S1, adding polyol PTMG2000, toluene diisocyanate TDI, 4' -dicyclohexylmethane diisocyanate HMDI, polycaprolactone diol PCL1000 and amino-terminated polydimethylsiloxane NH into a reaction vessel 2 PDMS is used as a raw material, butanone is then added as a solvent, and under the protection of nitrogen, the temperature is raised and stirred to 100 ℃, and the reaction is performed for 3 hours under reflux, so as to obtain a prepolymer;
step S2, slowly adding adipic acid dihydrazide and triisopropanolamine TIPA into the prepolymer obtained in the step S1 at 90 ℃, maintaining the temperature at 90 ℃, reacting for 4 hours, and distilling under reduced pressure to remove butanone;
wherein the NH is 2 The content of the PDMS is 2% -14% of the mass of the polycaprolactone diol;
the content of adipic acid dihydrazide is 0% -12% of the mass of the prepolymer obtained in the step S1;
the content of triisopropanolamine TIPA is 1% -8% of the mass of the prepolymer obtained in the step S1.
Further, the weight ratio of TDI to HMDI to PCL1000 to PTMG2000 is 1:1:1:1, NH 2 The content of PDMS was 2% of the mass of polycaprolactone diol, the content of adipic acid dihydrazide was 0% of the mass of the prepolymer, and the content of triisopropanolamine was 1% of the mass of the prepolymer.
Further, the weight ratio of TDI to HMDI to PCL1000 to PTMG2000 is 1:2:1:2, NH 2 The content of PDMS was 6% of the mass of polycaprolactone diol, the content of adipic acid dihydrazide was 4% of the mass of the prepolymer, and the content of triisopropanolamine was 3% of the mass of the prepolymer.
Further, the weight ratio of TDI to HMDI to PCL1000 to PTMG2000 is 1:4:1:4, NH 2 The content of PDMS was 14% of the mass of polycaprolactone diol, the content of adipic acid dihydrazide was 12% of the mass of the prepolymer, and the content of triisopropanolamine was 8% of the mass of the prepolymer.
Further, (methylenebis (5-isocyanatocyclohexane-3, 1-diyl)) bis (methane triamine) is added as one of the raw materials in step S1 in the same amount as toluene diisocyanate TDI in mass.
In step S1, (pentane-1, 5-diylbis (5-isocyanatocyclohexane-3, 1-diyl)) bis (methane triamine) was added as one of the starting materials in the same amount and mass as toluene diisocyanate TDI.
The invention has the beneficial effects that:
(1) By introducing amino modified silicone oil NH with heat-resistant and hydrophobic functions 2 PDMS, heat-resistant polyester polyol and hydrophobic polyether polyol and are used for preparing silane polyurethane segmented copolymer, and simultaneously, the hydrophobicity and mechanical property of the system are further improved by adjusting the dosage of the cross-linking agent;
（2）NH 2 the PDMS introducing system can improve the hydrophobicity and heat resistance of the system, but can also lead to the reduction of the peeling strength of the system, and the invention introduces acyl semicarbazide bond into the system by introducing adipic acid dihydrazide to form more hydrogen bonds with the peeling substrate so as to achieve the purpose of improving the peeling strength of the system.
Detailed Description
Various exemplary embodiments of the invention will now be described in detail, which should not be considered as limiting the invention, but rather as more detailed descriptions of certain aspects, features and embodiments of the invention. It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. In addition, for numerical ranges in this disclosure, it is understood that each intermediate value between the upper and lower limits of the ranges is also specifically disclosed. Every smaller range between any stated value or stated range, and any other stated value or intermediate value within the stated range, is also encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the invention described herein without departing from the scope or spirit of the invention. Other embodiments will be apparent to those skilled in the art from consideration of the specification of the present invention. The specification and examples of the present invention are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are intended to be inclusive and mean an inclusion, but not limited to.
The "parts" indicated in the examples below are parts by weight.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
Example 1
The embodiment provides an organosilicon modified polyurethane polymer for a flexible packaging aluminum plastic film of a power battery and a preparation method thereof
Step S1, adding polyol PTMG2000, toluene Diisocyanate (TDI), 4' -dicyclohexylmethane diisocyanate (HMDI), polycaprolactone diol (PCL 1000) and amino-terminated polydimethylsiloxane (NH) 2 PDMS) is used as a raw material, butanone is then added as a solvent, wherein the mass of the butanone is 2 times of the sum of the masses of the raw materials, and under the protection of nitrogen, the temperature is raised and stirred to 100 ℃, and the prepolymer is obtained after reflux reaction for 3 hours.
Step S2, adipic acid dihydrazide and Triisopropanolamine (TIPA) are slowly added at 90 ℃, maintained at 90 ℃ and reacted for 4 hours, and butanone is removed by reduced pressure distillation.
Wherein the weight ratio of TDI to HMDI to PCL1000 to PTMG2000 is 1:1:1:1, NH 2 The content of PDMS was 2% of the mass of polycaprolactone diol, the adipic acid dihydrazide content was 0% of the mass of the prepolymer (i.e. no adipic acid dihydrazide was added), and the triisopropanolamine content was 1% of the mass of the prepolymer.
Example 2
Step S1, adding polyol PTMG2000 and toluene diisoCyanate ester (TDI), 4' -dicyclohexylmethane diisocyanate (HMDI), polycaprolactone diol (PCL 1000), amino terminated polydimethylsiloxane (NH) 2 PDMS) is used as a raw material, butanone is then added as a solvent, wherein the mass of the butanone is 2 times of the sum of the masses of the raw materials, and under the protection of nitrogen, the temperature is raised and stirred to 100 ℃, and the prepolymer is obtained after reflux reaction for 3 hours.
Step S2, adipic acid dihydrazide and Triisopropanolamine (TIPA) are slowly added at 90 ℃, maintained at 90 ℃ and reacted for 4 hours, and butanone is removed by reduced pressure distillation.
Wherein the weight ratio of TDI to HMDI to PCL1000 to PTMG2000 is 2:1:2:1, NH 2 The content of PDMS was 4% of the mass of polycaprolactone diol, the content of adipic acid dihydrazide was 2% of the mass of the prepolymer, and the content of triisopropanolamine was 2% of the mass of the prepolymer.
Example 3
Step S1, polyol PTMG2000, toluene Diisocyanate (TDI), 4' -dicyclohexylmethane diisocyanate (HMDI), polycaprolactone diol (PCL 1000), terminal amino polydimethylsiloxane (NH) 2 PDMS) is used as a raw material, butanone is then added as a solvent, wherein the mass of the butanone is 2 times of the sum of the masses of the raw materials, and under the protection of nitrogen, the temperature is raised and stirred to 100 ℃, and the prepolymer is obtained after reflux reaction for 3 hours.
Step S2, adipic acid dihydrazide and Triisopropanolamine (TIPA) are slowly added at 90 ℃, maintained at 90 ℃ and reacted for 4 hours, and butanone is removed by reduced pressure distillation.
Wherein the weight ratio of TDI to HMDI to PCL1000 to PTMG2000 is 1:2:1:2, NH 2 The content of PDMS was 6% of the mass of polycaprolactone diol, the content of adipic acid dihydrazide was 4% of the mass of the prepolymer, and the content of triisopropanolamine was 3% of the mass of the prepolymer.
Example 4
Step S1, polyol PTMG2000, toluene Diisocyanate (TDI), 4' -dicyclohexylmethane diisocyanate (HMDI), polycaprolactone diol (PCL 1000), terminal amino polydimethylsiloxane (NH) 2 PDMS) as raw material, and then butanone as solvent is added, wherein the mass of butanone is the mass of the raw material3 times of the sum, heating and stirring to 100 ℃ under the protection of nitrogen, and carrying out reflux reaction for 3 hours to obtain the prepolymer.
Step S2, adipic acid dihydrazide and Triisopropanolamine (TIPA) are slowly added at 90 ℃, maintained at 90 ℃ and reacted for 4 hours, and butanone is removed by reduced pressure distillation.
Wherein the weight ratio of TDI to HMDI to PCL1000 to PTMG2000 is 3:1:1:3, NH 2 The content of PDMS was 8% of the mass of polycaprolactone diol, the content of adipic acid dihydrazide was 6% of the mass of the prepolymer, and the content of triisopropanolamine was 4% of the mass of the prepolymer.
Example 5
Step S1, polyol PTMG2000, toluene Diisocyanate (TDI), 4' -dicyclohexylmethane diisocyanate (HMDI), polycaprolactone diol (PCL 1000), terminal amino polydimethylsiloxane (NH) 2 PDMS) is used as a raw material, butanone is then added as a solvent, wherein the mass of the butanone is 3 times of the sum of the masses of the raw materials, and under the protection of nitrogen, the temperature is raised and stirred to 100 ℃, and the prepolymer is obtained after reflux reaction for 3 hours.
Step S2, adipic acid dihydrazide and Triisopropanolamine (TIPA) are slowly added at 90 ℃, maintained at 90 ℃ and reacted for 4 hours, and butanone is removed by reduced pressure distillation.
Wherein the weight ratio of TDI to HMDI to PCL1000 to PTMG2000 is 1:3:1:3, NH 2 The content of PDMS was 10% of the mass of polycaprolactone diol, the content of adipic acid dihydrazide was 8% of the mass of the prepolymer, and the content of triisopropanolamine was 5% of the mass of the prepolymer.
Example 6
Step S1, polyol PTMG2000, toluene Diisocyanate (TDI), 4' -dicyclohexylmethane diisocyanate (HMDI), polycaprolactone diol (PCL 1000), terminal amino polydimethylsiloxane (NH) 2 PDMS) is used as a raw material, butanone is then added as a solvent, wherein the mass of the butanone is 3 times of the sum of the masses of the raw materials, and under the protection of nitrogen, the temperature is raised and stirred to 100 ℃, and the prepolymer is obtained after reflux reaction for 3 hours.
Step S2, adipic acid dihydrazide and Triisopropanolamine (TIPA) are slowly added at 90 ℃, maintained at 90 ℃ and reacted for 4 hours, and butanone is removed by reduced pressure distillation.
Wherein the weight ratio of TDI to HMDI to PCL1000 to PTMG2000 is 4:1:4:1, NH 2 The content of PDMS was 12% of the mass of polycaprolactone diol, the content of adipic acid dihydrazide was 10% of the mass of the prepolymer, and the content of triisopropanolamine was 6% of the mass of the prepolymer.
Example 7
Step S1, polyol PTMG2000, toluene Diisocyanate (TDI), 4' -dicyclohexylmethane diisocyanate (HMDI), polycaprolactone diol (PCL 1000), terminal amino polydimethylsiloxane (NH) 2 PDMS) is used as a raw material, butanone is then added as a solvent, wherein the mass of the butanone is 3 times of the sum of the masses of the raw materials, and under the protection of nitrogen, the temperature is raised and stirred to 100 ℃, and the prepolymer is obtained after reflux reaction for 3 hours.
Step S2, adipic acid dihydrazide and Triisopropanolamine (TIPA) are slowly added at 90 ℃, maintained at 90 ℃ and reacted for 4 hours, and butanone is removed by reduced pressure distillation.
Wherein the weight ratio of TDI to HMDI to PCL1000 to PTMG2000 is 1:4:1:4, NH 2 The content of PDMS was 14% of the mass of polycaprolactone diol, the content of adipic acid dihydrazide was 12% of the mass of the prepolymer, and the content of triisopropanolamine was 8% of the mass of the prepolymer.
Table 1 examples 1-7 performance testing
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | Example 7 | |
| Peel strength (before soaking) N/15mm | 4 | 5 | 5 | 8 | 9 | 10 | 10 |
| Peel strength (after soaking) N/15mm | 2 | 4 | 4 | 6 | 7 | 8 | 8 |
| Water absorption (%) | 0 | 0 | 0 | 0 | 0.1 | 0.1 | 0.1 |
| Contact angle (°) | 90 | 93 | 93 | 94 | 95 | 97 | 100 |
| Tensile Strength (MPa) | 7 | 11 | 12 | 16 | 16 | 19 | 20 |
| Elongation at break (%) | 200 | 330 | 350 | 410 | 430 | 510 | 600 |
| Thermal stability (. Degree. C.) | 320 | 410 | 430 | 480 | 470 | 500 | 520 |
As can be seen from Table 1, the peel strength gradually increased with increasing amounts of the components in the prepolymer, but the magnitude of the increase gradually decreased, the peel strengths in examples 4 to 5 and examples 6 to 7 were already not quite different. Compared with two cases that the ratio of TDI to HMDI to PCL1000 to PTMG2000 is 4:1:4:1 and 1:4:1:4, the peel strength is not obviously different, other performance indexes are not greatly different, only the elongation at break is different, and it is presumed that the increase of the content of the HMDI and the PTMG2000 can improve the elongation at break of the polyurethane high polymer.
Example 8
On the basis of example 7, in step S1 (methylenebis (5-isocyanatocyclohexane-3, 1-diyl)) bis (methane triamine) was added as one of the starting materials in the same amount and mass as Toluene Diisocyanate (TDI).
Wherein the structure of (methylenebis (5-isocyanatocyclohexane-3, 1-diyl)) bis (methane triamine) is as follows.
（I）。
In a specific step S1, polyol PTMG2000, toluene Diisocyanate (TDI), 4' -dicyclohexylmethane diisocyanate (HMDI), polycaprolactone diol (PCL 1000), amino terminated polydimethylsiloxane (NH) 2 -PDMS) and (methylene bis (5-isocyanatocyclohexane-3, 1-diyl)) bis (methane triamine) are used as raw materials, butanone is then added as a solvent, wherein the mass of the butanone is 3 times of the sum of the mass of the raw materials, and the raw materials are heated and stirred to 100 ℃ under the protection of nitrogen, and reflux reaction is carried out for 3 hours, so that a prepolymer is obtained.
Step S2, adipic acid dihydrazide and Triisopropanolamine (TIPA) are slowly added at 90 ℃, maintained at 90 ℃ and reacted for 4 hours, and butanone is removed by reduced pressure distillation.
Wherein the weight ratio of TDI to HMDI to PCL1000 to PTMG2000 is 1:4:1:4, NH 2 The content of PDMS was 14% of the mass of polycaprolactone diol, the content of adipic acid dihydrazide was 12% of the mass of the prepolymer, and the content of triisopropanolamine was 8% of the mass of the prepolymer.
The synthesis method of the (methylene bis (5-isocyanatocyclohexane-3, 1-diyl)) bis (methane triamine) comprises the following steps:
step S11, adding a proper amount of 3- [ (3-aminophenyl) methyl ] aniline, acetonitrile as a solvent and tetranitromethane as an oxidant, and carrying out reflux reaction for 15 hours to obtain 3- { [ 3-amino-5- (trinitromethyl) phenyl ] methyl } -5- (trinitromethyl) aniline;
step S12, after step S11, H is introduced 2 At H 2 Under the protection of atmosphere, adding ruthenium carbon catalyst, and carrying out reduction reaction for 24 hours to obtain 5- { [ 5-amino-3- (triaminomethyl) cyclohexyl]Methyl } -3- (triaminomethyl) cyclohex-1-amine;
step S13, reflux reaction of 5- { [ 5-amino-3- (triaminomethyl) cyclohexyl ] methyl } -3- (triaminomethyl) cyclohex-1-amine and the same amount of diisobutyl carbonate in the presence of methanol and sodium methoxide with amberlyst15 as catalyst for 6h at 100℃to obtain diisoamyl (methylenebis (5- (triaminomethyl) cyclohexane-3, 1-diyl)) dicarbamate;
step S14, after the step S13, dibutyl tin dilaurate is added as a catalyst, and reflux is carried out for 12 hours at the temperature of 100 ℃ to obtain a final product (methylenebis (5-isocyanatocyclohexane-3, 1-diyl)) bis (methane triamine).
Example 9
On the basis of example 7, in step S1 (pentane-1, 5-diylbis (5-isocyanatocyclohexane-3, 1-diyl)) bis (methane triamine) was added as one of the starting materials in the same amount as Toluene Diisocyanate (TDI).
Wherein the structure of (pentane-1, 5-diylbis (5-isocyanatocyclohexane-3, 1-diyl)) bis (methane triamine) is as follows.
（II）。
Specifically, in step S1, polyol PTMG2000, toluene Diisocyanate (TDI), 4' -dicyclohexylmethane diisocyanate (HMDI), polycaprolactone diol (PCL 1000), amino terminated polydimethylsiloxane (NH) 2 -PDMS) and (pentane-1, 5-diylbis (5-isocyanatocyclohexane-3)1-diyl)) bis (methane triamine) as a raw material, then butanone as a solvent was added, wherein the mass of butanone is 3 times of the sum of the mass of the raw materials, and the mixture was heated and stirred to 100 ℃ under the protection of nitrogen, and was subjected to reflux reaction for 3 hours to obtain a prepolymer.
Step S2, adipic acid dihydrazide and Triisopropanolamine (TIPA) are slowly added at 90 ℃, maintained at 90 ℃ and reacted for 4 hours, and butanone is removed by reduced pressure distillation.
Wherein the weight ratio of TDI to HMDI to PCL1000 to PTMG2000 is 1:4:1:4, NH 2 The content of PDMS was 14% of the mass of polycaprolactone diol, the content of adipic acid dihydrazide was 12% of the mass of the prepolymer, and the content of triisopropanolamine was 8% of the mass of the prepolymer.
The synthesis of the (pentane-1, 5-diylbis (5-isocyanatocyclohexane-3, 1-diyl)) bis (methane triamine) comprises the following steps:
step S21, reacting 3-tert-butoxycarbonyl amino benzyl triphenylphosphine and allene dione in a dichloromethane solvent at room temperature for 5 hours to obtain 1, 5-di- (3-tert-butoxycarbonyl amino phenyl) pentylenes;
step S22, adding trifluoroacetic acid as a solvent, and reacting for 2 hours at room temperature to obtain 1, 5-di-m-aminophenyl pentylenes;
step S23, after the step S22, adding a platinum-carbon catalyst, and reacting for 24 hours at 50 ℃ in the presence of methanol serving as a solvent under the hydrogen atmosphere to obtain 3- [5- (3-aminophenyl) amyl ] aniline:
step S24, after the step S23, tetranitromethane is added into acetonitrile solvent as an oxidant for reflux reaction for 15 hours to obtain 5- {5- [ 3-amino-5- (trinitromethyl) phenyl ] amyl } -3- (trinitromethyl) aniline;
step S25, after step S24, H is introduced 2 At H 2 Under the protection of atmosphere, adding ruthenium-carbon catalyst and methanol as solvent, and carrying out reduction reaction for 24 hours to obtain (pentane-1, 5-diylbis (5- (triaminomethyl) cyclohexane-3, 1-diyl)) dicarbamate diisoamyl ester;
step S26, carrying out reflux reaction on the (pentane-1, 5-diylbis (5- (triaminomethyl) cyclohexane-3, 1-diyl)) dicarbamate diisoamyl ester and the diisobutyl carbonate with the same content in the presence of methanol and sodium methoxide by using amberlyst15 as a catalyst for 6 hours at 100 ℃ to obtain [ (3- {5- [3- ({ [ (3-methylbutyl) oxy ] carbonyl } amino) cyclohexyl ] pentyl } cyclohexyl) amino ] methane acid-3-methylbutyl ester;
s27, adding dibutyl tin dilaurate as a catalyst after the step S26, and refluxing for 12 hours at 100 ℃ to obtain a final product (pentane-1, 5-diylbis (5-isocyanatocyclohexane-3, 1-diyl)) bis (methane triamine).
Table 2 examples 8-9 performance testing
| Example 8 | Example 9 | |
| Peel strength (before soaking) N/15mm | 20 | 24 |
| Peel strength (after soaking) N/15mm | 16 | 20 |
| Water absorption (%) | 0.1% | 0.1% |
| Contact angle (°) | 97 | 93 |
| Tensile Strength (MPa) | 18MPa | 19MPa |
| Elongation at break (%) | 400% | 500% |
| Thermal stability (. Degree. C.) | 470℃ | 500℃ |
It can be seen that the low viscosity aliphatic of the system and the isocyanate with uretonimine linkages form hydrogen bonds with the substrate while increasing wettability and thus increase adhesion. Secondly, when (methylene bis (5-isocyanatocyclohexane-3, 1-diyl)) bis (methane triamine) and (pentane-1, 5-diyl bis (5-isocyanatocyclohexane-3, 1-diyl)) bis (methane triamine) are added, the bonding capacity of polyurethane is increased due to the increased number of amino groups, wherein the n-amyl structure in (pentane-1, 5-diyl bis (5-isocyanatocyclohexane-3, 1-diyl)) bis (methane triamine) is increased, the distance between the amino groups on two cyclohexyl groups is increased, so that the amino groups can fully form hydrogen bonds, and the (methylene bis (5-isocyanatocyclohexane-3, 1-diyl)) bis (methane triamine) connected by methyl cannot fully form hydrogen bonds due to the lower length of a carbon chain and the steric hindrance, so that the bonding capacity is not obviously increased.
The above embodiments are only illustrative of the preferred embodiments of the present invention and are not intended to limit the scope of the present invention, and various modifications and improvements made by those skilled in the art to the technical solutions of the present invention should fall within the protection scope defined by the claims of the present invention without departing from the design spirit of the present invention.
Claims (9)
1. An organosilicon modified polyurethane polymer for a soft-package aluminum plastic film of a power battery comprises toluene diisocyanate TDI, 4' -dicyclohexylmethane diisocyanate HMDI, polycaprolactone diol PCL1000, polyol PTMG2000 and amino-terminated polydimethylsiloxane NH 2 PDMS, characterized in that,
the organosilicon modified polyurethane high polymer is prepared by the following steps:
step S1, adding polyol PTMG2000, toluene diisocyanate TDI, 4' -dicyclohexylmethane diisocyanate HMDI, polycaprolactone diol PCL1000 and amino-terminated polydimethylsiloxane NH into a reaction vessel 2 PDMS is used as a raw material, butanone is then added as a solvent, wherein the mass of the butanone is 2-3 times of the sum of the masses of the raw materials, and under the protection of nitrogen, the temperature is raised and stirred to 100 ℃, and the reaction is performed for 3 hours under reflux, so that a prepolymer is obtained;
step S2, slowly adding adipic acid dihydrazide and triisopropanolamine TIPA into the prepolymer obtained in the step S1 at 90 ℃, maintaining the temperature at 90 ℃, reacting for 4 hours, and distilling under reduced pressure to remove butanone;
the toluene diisocyanate TDI content is 1-4 parts by weight;
the content of the 4,4' -dicyclohexylmethane diisocyanate HMDI is 1-4 parts by weight;
the content of the polycaprolactone diol PCL1000 is 1-4 parts by weight;
the content of the polyol PTMG2000 is 1-4 parts by weight;
the amino-terminated polydimethylsiloxane NH 2 The content of the PDMS is 2% -14% of the mass of the polycaprolactone diol;
the content of adipic acid dihydrazide is 0% -12% of the mass of the prepolymer obtained in the step S1;
the content of triisopropanolamine TIPA is 1% -8% of the mass of the prepolymer obtained in the step S1.
2. The silicone-modified polyurethane polymer of claim 1, wherein the weight ratio of TDI to HMDI to PCL1000 to PTMG2000 is 1:1:1:1, and the amino-terminated polydimethylsiloxane NH 2 Content of PDMSThe content of adipic acid dihydrazide is 0% of the mass of the prepolymer, and the content of triisopropanolamine is 1% of the mass of the prepolymer.
3. The silicone-modified polyurethane polymer of claim 1, wherein the weight ratio of TDI to HMDI to PCL1000 to PTMG2000 is 1:2:1:2, and the amino-terminated polydimethylsiloxane NH 2 The content of PDMS was 6% of the mass of polycaprolactone diol, the content of adipic acid dihydrazide was 4% of the mass of the prepolymer, and the content of triisopropanolamine was 3% of the mass of the prepolymer.
4. The silicone-modified polyurethane polymer of claim 1, wherein the weight ratio of TDI to HMDI to PCL1000 to PTMG2000 is 1:4:1:4, and the amino-terminated polydimethylsiloxane NH 2 The content of PDMS was 14% of the mass of polycaprolactone diol, the content of adipic acid dihydrazide was 12% of the mass of the prepolymer, and the content of triisopropanolamine was 8% of the mass of the prepolymer.
5. The silicone-modified polyurethane polymer as set forth in claim 4, wherein (methylenebis (5-isocyanatocyclohexane-3, 1-diyl)) bis (methane triamine) is added as one of the raw materials in step S1 in the same amount as toluene diisocyanate TDI in mass.
6. The silicone-modified polyurethane polymer as set forth in claim 5, wherein the synthesis of (methylenebis (5-isocyanatocyclohexane-3, 1-diyl)) bis (methane triamine) comprises the steps of:
step S11, adding 3- [ (3-aminophenyl) methyl ] aniline, acetonitrile as a solvent and tetranitromethane as an oxidant, and carrying out reflux reaction for 15 hours to obtain 3- { [ 3-amino-5- (trinitromethyl) phenyl ] methyl } -5- (trinitromethyl) aniline;
step S12, after step S11, H is introduced 2 At H 2 Under the protection of atmosphere, adding ruthenium carbon catalyst, and carrying out reduction reaction for 24 hours to obtain 5- { [ 5-amino-3- (triaminomethyl) cyclohexyl]Methyl } -3- (triaminomethyl) cyclohex-1-amine；
Step S13, reflux reaction of 5- { [ 5-amino-3- (triaminomethyl) cyclohexyl ] methyl } -3- (triaminomethyl) cyclohex-1-amine and the same amount of diisobutyl carbonate in the presence of methanol and sodium methoxide with amberlyst15 as catalyst for 6h at 100℃to obtain diisoamyl (methylenebis (5- (triaminomethyl) cyclohexane-3, 1-diyl)) dicarbamate;
step S14, after the step S13, dibutyl tin dilaurate is added as a catalyst, and reflux is carried out for 12 hours at the temperature of 100 ℃ to obtain a final product (methylenebis (5-isocyanatocyclohexane-3, 1-diyl)) bis (methane triamine).
7. The silicone-modified polyurethane polymer as set forth in claim 4, wherein (pentane-1, 5-diylbis (5-isocyanatocyclohexane-3, 1-diyl)) bis (methane triamine) is added as one of the raw materials in step S1 in the same amount as toluene diisocyanate TDI in mass.
8. The silicone-modified polyurethane polymer of claim 7, wherein the synthesis of (pentane-1, 5-diylbis (5-isocyanatocyclohexane-3, 1-diyl)) bis (methane triamine) comprises the steps of:
step S21, reacting 3-tert-butoxycarbonyl amino benzyl triphenylphosphine and allene dione in a dichloromethane solvent at room temperature for 5 hours to obtain 1, 5-di- (3-tert-butoxycarbonyl amino phenyl) pentylenes;
step S22, adding trifluoroacetic acid as a solvent, and reacting for 2 hours at room temperature to obtain 1, 5-di-m-aminophenyl pentylenes;
step S23, adding a platinum-carbon catalyst after the step S22, and reacting for 24 hours at 50 ℃ in the presence of methanol serving as a solvent under the hydrogen atmosphere to obtain 3- [5- (3-aminophenyl) amyl ] aniline;
step S24, after the step S23, tetranitromethane is added into acetonitrile solvent as an oxidant for reflux reaction for 15 hours to obtain 5- {5- [ 3-amino-5- (trinitromethyl) phenyl ] amyl } -3- (trinitromethyl) aniline;
step S25, after step S24, H is introduced 2 At H 2 Under the protection of atmosphere, adding ruthenium-carbon catalyst and methanol as solvent, and carrying out reduction reaction for 24 hours to obtain (pentane-1, 5-diylbis (5- (triaminomethyl) cyclohexane-3, 1-diyl)) dicarbamate diisoamyl ester;
step S26, carrying out reflux reaction on the (pentane-1, 5-diylbis (5- (triaminomethyl) cyclohexane-3, 1-diyl)) dicarbamate diisoamyl ester and the diisobutyl carbonate with the same content in the presence of methanol and sodium methoxide by using amberlyst15 as a catalyst for 6 hours at 100 ℃ to obtain [ (3- {5- [3- ({ [ (3-methylbutyl) oxy ] carbonyl } amino) cyclohexyl ] pentyl } cyclohexyl) amino ] methane acid-3-methylbutyl ester;
s27, adding dibutyl tin dilaurate as a catalyst after the step S26, and refluxing for 12 hours at 100 ℃ to obtain a final product (pentane-1, 5-diylbis (5-isocyanatocyclohexane-3, 1-diyl)) bis (methane triamine).
9. A preparation method of an organosilicon modified polyurethane polymer for a soft-coated aluminum plastic film of a power battery is characterized by comprising the following steps:
step S1, polyol PTMG2000, toluene diisocyanate TDI, 4' -dicyclohexylmethane diisocyanate HMDI, polycaprolactone diol PCL1000 and terminal amino polydimethylsiloxane NH are added 2 PDMS, (pentane-1, 5-diylbis (5-isocyanatocyclohexane-3, 1-diyl)) bis (methane triamine) is used as a raw material, butanone is added as a solvent, wherein the mass of the butanone is 2-3 times of the sum of the mass of the raw materials, and under the protection of nitrogen, the mixture is heated and stirred to 100 ℃, and the mixture is subjected to reflux reaction for 3 hours to obtain a prepolymer;
step S2, slowly adding adipic acid dihydrazide and triisopropanolamine TIPA at 90 ℃, maintaining at 90 ℃, reacting for 4 hours, and distilling under reduced pressure to remove butanone;
wherein the weight ratio of TDI to HMDI to PCL1000 to PTMG2000 is 1:4:1:4, (pentane-1, 5-diylbis (5-isocyanatocyclohexane-3, 1-diyl)) bis (methane triamine), the content of which is the same as the mass of Toluene Diisocyanate (TDI), and the amino-terminated polydimethylsiloxane NH 2 The content of PDMS is 14% of the mass of polycaprolactone diol, the content of adipic acid dihydrazide is 12% of the mass of prepolymer, and the content of triisopropanolamine8% of the mass of the prepolymer.
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