CN110760047B - Bis-secondary amine containing siloxane group and preparation method and application thereof - Google Patents
Bis-secondary amine containing siloxane group and preparation method and application thereof Download PDFInfo
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- CN110760047B CN110760047B CN201810831487.6A CN201810831487A CN110760047B CN 110760047 B CN110760047 B CN 110760047B CN 201810831487 A CN201810831487 A CN 201810831487A CN 110760047 B CN110760047 B CN 110760047B
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- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 229920002396 Polyurea Polymers 0.000 claims abstract description 70
- 238000006243 chemical reaction Methods 0.000 claims abstract description 49
- 239000007921 spray Substances 0.000 claims abstract description 45
- 239000012948 isocyanate Substances 0.000 claims abstract description 24
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 24
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000002156 mixing Methods 0.000 claims abstract description 22
- 150000004985 diamines Chemical group 0.000 claims abstract description 17
- 238000005507 spraying Methods 0.000 claims abstract description 16
- RTWNYYOXLSILQN-UHFFFAOYSA-N methanediamine Chemical compound NCN RTWNYYOXLSILQN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229920005862 polyol Polymers 0.000 claims abstract description 13
- 150000003077 polyols Chemical class 0.000 claims abstract description 13
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 10
- 229920000570 polyether Polymers 0.000 claims abstract description 10
- 238000006845 Michael addition reaction Methods 0.000 claims abstract description 5
- 150000001412 amines Chemical class 0.000 claims abstract description 3
- 229920001971 elastomer Polymers 0.000 claims description 33
- 239000000806 elastomer Substances 0.000 claims description 33
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 28
- 238000003756 stirring Methods 0.000 claims description 24
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 20
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- 239000002270 dispersing agent Substances 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
- 239000003085 diluting agent Substances 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 229910021485 fumed silica Inorganic materials 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 150000005622 tetraalkylammonium hydroxides Chemical class 0.000 claims description 8
- 125000002947 alkylene group Chemical group 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 125000002993 cycloalkylene group Chemical group 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 239000002518 antifoaming agent Substances 0.000 claims description 4
- 125000005442 diisocyanate group Chemical group 0.000 claims description 4
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 claims description 3
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 claims description 3
- 238000009472 formulation Methods 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims description 2
- 239000000194 fatty acid Substances 0.000 claims description 2
- 229930195729 fatty acid Natural products 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- 238000005070 sampling Methods 0.000 claims description 2
- ODZPKZBBUMBTMG-UHFFFAOYSA-N sodium amide Chemical compound [NH2-].[Na+] ODZPKZBBUMBTMG-UHFFFAOYSA-N 0.000 claims description 2
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 2
- 239000012312 sodium hydride Substances 0.000 claims description 2
- 230000018044 dehydration Effects 0.000 claims 4
- 238000006297 dehydration reaction Methods 0.000 claims 4
- 150000007514 bases Chemical class 0.000 claims 3
- 238000006555 catalytic reaction Methods 0.000 claims 1
- 125000005313 fatty acid group Chemical class 0.000 claims 1
- 150000005846 sugar alcohols Polymers 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 28
- 238000004132 cross linking Methods 0.000 abstract description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract description 6
- 229910002808 Si–O–Si Inorganic materials 0.000 abstract description 2
- 239000012752 auxiliary agent Substances 0.000 abstract description 2
- 230000004224 protection Effects 0.000 description 13
- 238000013008 moisture curing Methods 0.000 description 10
- 229920001451 polypropylene glycol Polymers 0.000 description 10
- -1 alicyclic diamine Chemical class 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
- 229910052710 silicon Inorganic materials 0.000 description 7
- 239000010703 silicon Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 239000005058 Isophorone diisocyanate Substances 0.000 description 6
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 6
- 230000001070 adhesive effect Effects 0.000 description 6
- 230000032683 aging Effects 0.000 description 6
- 239000012975 dibutyltin dilaurate Substances 0.000 description 6
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 6
- 125000003277 amino group Chemical group 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 239000013530 defoamer Substances 0.000 description 5
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 5
- 238000004321 preservation Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 238000010276 construction Methods 0.000 description 4
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- PISLZQACAJMAIO-UHFFFAOYSA-N 2,4-diethyl-6-methylbenzene-1,3-diamine Chemical compound CCC1=CC(C)=C(N)C(CC)=C1N PISLZQACAJMAIO-UHFFFAOYSA-N 0.000 description 3
- 239000004970 Chain extender Substances 0.000 description 3
- 238000007259 addition reaction Methods 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 238000001723 curing Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 3
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 3
- DMKSVUSAATWOCU-HROMYWEYSA-N loteprednol etabonate Chemical compound C1CC2=CC(=O)C=C[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@@](C(=O)OCCl)(OC(=O)OCC)[C@@]1(C)C[C@@H]2O DMKSVUSAATWOCU-HROMYWEYSA-N 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 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 description 2
- 239000000945 filler Substances 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 230000005311 nuclear magnetism Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 125000006832 (C1-C10) alkylene group Chemical group 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- GEQHKFFSPGPGLN-UHFFFAOYSA-N cyclohexane-1,3-diamine Chemical compound NC1CCCC(N)C1 GEQHKFFSPGPGLN-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- KEIQPMUPONZJJH-UHFFFAOYSA-N dicyclohexylmethanediamine Chemical compound C1CCCCC1C(N)(N)C1CCCCC1 KEIQPMUPONZJJH-UHFFFAOYSA-N 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000007777 multifunctional material Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000012974 tin catalyst Substances 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 238000004078 waterproofing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3893—Low-molecular-weight compounds having heteroatoms other than oxygen containing silicon
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/1892—Preparation; Treatments not provided for in C07F7/20 by reactions not provided for in C07F7/1876 - C07F7/1888
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—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
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6685—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/02—Polyureas
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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Abstract
The invention discloses a bis-secondary amine containing siloxane groups, and a preparation method and application thereof, wherein the bis-secondary amine containing siloxane groups is obtained by one or more than one primary diamine and siloxane containing unsaturated double bonds through Michael addition reaction. The component B of the spray polyurea is prepared by mixing the secondary diamine and the auxiliary agent thereof, and the polyurea material is prepared by mixing and spraying the component A and the component B according to the volume ratio of 1:1, wherein the component A is an isocyanate prepolymer generated by the reaction of polyether polyol and isocyanate. Two active hydrogens of the secondary diamine can react with isocyanate to generate linear polyurea, and siloxane groups can be hydrolyzed to generate Si-O-Si crosslinking points, so that the crosslinking speed of amine and isocyanate is reduced, and the mechanical property of the polyurea material is improved.
Description
Technical Field
The invention relates to the technical field of spray polyurea elastomers, in particular to secondary diamine containing siloxane groups and a preparation method thereof, and a spray polyurea elastomer which is prepared by taking the secondary diamine as a raw material and is moisture-cured and a preparation method thereof.
Background
The spray polyurea elastomer is a novel multifunctional material which is widely applied to the fields of water resistance and corrosion resistance and has excellent waterproof performance, corrosion resistance and wear resistance, overcomes the defects of non-aging resistance, non-exposure, low strength, poor puncture resistance, high requirement on construction environment, slow curing, low construction efficiency and the like of traditional waterproof materials such as asphalt coiled materials, single/double-component polyurethane waterproof coatings, acrylate emulsion waterproof coatings and the like, does not contain a solvent in a raw material system, meets the current environmental protection requirement, and can continuously spray a base material surface with the thickness of more than ten millimeters without sagging.
The spray polyurea technology is introduced from abroad into China, is rapidly developed, is successfully applied to a series of national key projects such as waterproof projects of Jingjin high-speed iron and Jinghu high-speed iron, waterproof and wear-resistant projects of national theater artificial lakes and stands of Beijing Olympic stadiums, and the like, and obtains high evaluation of a construction party and a project party, but the spray polyurea elastomer slowly shows a series of defects along with the passage of time, such as general weather resistance, chemical medium resistance and ultraviolet resistance, low adhesive force to a base material, and polyurea falls off from the surface of the base material after water vapor enters gaps between the base material and the polyurea, and the polyurea has poor toughness, cannot meet the requirements of special environments, and is limited in application and development.
U.S. Pat. No. 5162388 discloses an aliphatic spray polyurea elastomer, which uses alicyclic diamine as a chain extender to improve the physical properties and operational properties of the spray polyurea elastomer, and can improve the performance disadvantage of the traditional spray polyurea with poor ultraviolet aging resistance, but the alicyclic diamine has a fast reaction speed, the viscosity of the mixed raw material is rapidly increased, the wettability to the base material is poor, and finally the adhesion of the polyurea to the base material is poor.
Chinese patent publication CN1817989A discloses a spray polyurea high-strength elastic waterproof coating and a construction method thereof, wherein a component A is a semi-prepolymer synthesized by liquefied diphenyl diisocyanate and/or MDI and polyether polyol, a component B is a combination of amine-terminated polyether, amine chain extender, various fillers and auxiliaries, the tensile strength of the spray polyurea system is 13MPa, the elongation at break is 400%, the tear strength is 49kN/m, and the spray polyurea system has better mechanical properties, but the spray polyurea system is also delaminated from a base material at the later stage.
Chinese patent publication CN105694702A discloses a single-component moisture-curing organosilicon-modified polyurethane waterproof coating, which is prepared by using monohydroxy polydimethylsiloxane and diisocyanate as raw materials, and then dispersing the raw materials with other fillers and auxiliaries at a high speed at room temperature to obtain the single-component moisture-curing organosilicon-modified polyurethane waterproof coating.
The organic silicon has better high and low temperature resistance, weather resistance, oxidation resistance stability and corrosion resistance, so that the organic silicon modified polyurea material can effectively improve the adhesive force, weather resistance and high and low temperature resistance of the polyurea material. At present, the method for introducing organic silicon into polyurea is mainly to physically mix the organic silicon with other diamine in a component B and then spray the mixture, the reaction speed of the A/B mixed component sprayed by the method is too fast, the A/B mixed component is difficult to effectively infiltrate into a base material, the adhesive force is poor, and cross-linking points in the system are carbamido, so that the later-period toughness of the polyurea material is poor.
Disclosure of Invention
In order to overcome the disadvantages and shortcomings of the prior art, the present invention provides a bis-secondary amine containing a siloxane group and a method for preparing the same. Two active hydrogens of the secondary diamine can react with isocyanate to generate linear polyurea, and siloxane groups can be hydrolyzed to generate Si-O-Si crosslinking points, so that the crosslinking speed of amine and isocyanate is reduced, and the mechanical property of the polyurea material is improved.
The invention also aims to provide the application of the bis-secondary amine containing siloxane groups in preparing spray polyurea, which is used as a raw material of the component B to prepare a moisture-cured spray polyurea material.
The invention further aims to provide a moisture-curing spray polyurea elastomer and a preparation method thereof, wherein the curing speed is lower than that of the traditional polyurea, the mixing viscosity of A, B components is lower, A, B components have sufficient time to infiltrate into pores of a base material after being mixed, the infiltration on the base material is better, and the introduction of siloxane improves the adhesive force of the polyurea material to the base material. The novel polyurea material takes-Si-O-Si-as a crosslinking point, so that the toughness of the polyurea material can be obviously improved, and the thermal-oxidative aging resistance of the polyurea material is improved. The moisture-curing spray polyurea material is particularly suitable for the fields of high-speed rail waterproofing and the like.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
a bis-secondary amine containing siloxane groups having the general formula:
(R3O)3SiR2NHR1NHR2Si(OR3)3
(I)
in the formula, R1An ether group selected from C1-C10 alkylene, C3-16 cycloalkylene or C3-C16, preferably C3-12 cycloalkylene, C3-C12 ether; further preferred is R1Comprises the following steps:
R2is selected from C2-C7 alkylene, preferably C2-C3 alkylene;
R3selected from C1-C10 alkyl groups, preferably C1-C2 alkyl groups.
The bis-secondary amine containing siloxane groups is prepared by dripping siloxane containing unsaturated double bonds into one or more than one primary diamine system and carrying out Michael addition reaction at a certain temperature.
Preferably, the method for preparing the above-mentioned siloxane group-containing bis-secondary amine comprises the following steps:
adding one or more than one primary diamine into a reaction kettle provided with a stirrer, a thermometer and an inert gas pipeline, adding a catalyst, stirring at a certain temperature, dropwise adding siloxane containing unsaturated double bonds into the reaction kettle, and continuously reacting under the protection of inert gas to obtain the secondary diamine containing siloxane branched chains. The reaction equation is shown In (IV).
H2N-R1-NH2+2H2C＝CH-R4-SiOR3)3→(R3O)3SiR2HN-R1-NHR2Si(OR3)3
(IV)
Among them, the inert protective gas used in the step of preparing the siloxane group-containing bis-secondary amine may be nitrogen, argon, or the like, and nitrogen is preferable in this method.
Wherein the primary diamine used in the step of preparing the siloxane group-containing secondary diamine has the following structure (II):
H2N-R1-NH2
(II)
in the above formula, R1Is composed of
Wherein the unsaturated double bond-containing siloxane used in the step of preparing the bis-secondary amine containing a siloxane group has a structure described by the general formula (III):
CH2＝CH-R4-Si(OR3)3
(III)
R4selected from C0-C5 alkylene, preferably C0-C1;
R3selected from C1-C10 alkyl groups, preferably C1-C2. (ii) a
Further, the molar ratio of the unsaturated double bond-containing siloxane to the primary diamine used in the step of preparing the secondary diamine containing a siloxane group is 2.0 to 2.1:1, preferably 2.0 to 2.05: 1.
further, the catalyst used in the step of preparing the siloxane group-containing bis-secondary amine is a basic catalyst such as metallic sodium, sodium ethoxide, sodium hydride, sodium amide, tetraalkylammonium hydroxide, etc., and tetraalkylammonium hydroxide is more preferable.
Further, the catalyst used in the step of preparing the secondary diamine containing a siloxane group is used in an amount of 0.1 to 1% by weight, preferably 0.4 to 0.8% by weight, based on the total amount of the unsaturated double bond-containing siloxane and the primary diamine.
Further, the reaction temperature in the step of preparing the bis-secondary amine containing a siloxane group is 60 ℃ to 90 ℃, preferably 70 ℃ to 80 ℃, and the reaction time is 2 to 4 hours, preferably 3 to 4 hours.
The specific synthetic procedure for the bis-secondary amine containing a siloxane group can be carried out as follows:
in a container equipped with a stirrer, a thermometer and N2Adding one or more than one primary diamine and a catalyst into a reaction kettle of a gas pipeline in a precisely metered manner, accurately weighing the siloxane containing the unsaturated double bond at the temperature of 60-90 ℃, preferably 70-80 ℃, according to the molar ratio of the siloxane containing the unsaturated double bond to the primary diamine of 2.0-2.1:1, preferably 2.0-2.05:1, slowly dripping the siloxane into the reaction kettle, and reacting for 2-4h, preferably 3-4h under the protection of nitrogen to obtain the secondary diamine containing the siloxane group.
Further, the bis-secondary amine containing siloxane groups obtained as described above is mainly used in the B component for preparing moisture-curable spray polyurea. The component B of the spray polyurea is prepared by mixing the secondary diamine and other auxiliary agents, and the moisture-curing spray polyurea elastomer is obtained by mixing and spraying the component A which is an isocyanate prepolymer generated by the reaction of polyol and isocyanate according to the volume ratio of the component A/B of 1: 1.
A moisture-curing spray polyurea elastomer comprises the following formula system:
the component A comprises:
the mass ratio/part is preferable
Isocyanate prepolymer 70-12088-
Diluent 0-305-15
The component B comprises:
preferably, the isocyanate prepolymer in the component A is synthesized by reacting polyether polyol and isocyanate, and the-NCO content of the isocyanate prepolymer is 12-20%.
Further, the molecular weight of the polyether polyol in the component A is 200-10000, preferably 400-1000, and the polyether polyol prepared by the ring-opening reaction of dipropylene glycol serving as an initiator and propylene oxide is preferred.
Further, the catalyst required during the synthesis of the isocyanate prepolymer described in the a component is an organotin-based catalyst, preferably dibutyltin dilaurate, and is added in an amount of 0.1% by weight to 0.8% by weight, preferably 0.1% by weight to 0.6% by weight, based on the total amount of the polyether polyol and the isocyanate.
Further, the diluent in the a component is selected from Propylene Carbonate (PC), dioctyl phthalate (DOP) or dibutyl phthalate (DBP), preferably dibutyl phthalate.
Further, the A component in the spray polyurea formula system is one or more of toluene diisocyanate, diphenylmethane diisocyanate, 4 '-dicyclohexylmethane diisocyanate or isophorone diisocyanate, and preferably one or two of 4,4' -dicyclohexylmethane diisocyanate, isophorone diisocyanate and the like.
Wherein, the bis-secondary amine in the component B in the moisture-curing spray polyurea formula is the bis-secondary amine containing siloxane groups synthesized in the invention.
Wherein the dispersant in the B component in the moisture-curing spray polyurea formulation is a fatty acid derivative, such as: one or two of Tego Dispers610, Dispers 630.
Wherein the defoaming agent in the component B in the moisture-curing spray polyurea formula is an organic silicon defoaming agent. Preferably a mixture of one or more of Tego Foamex N, Airex900, Airex 930, Airex 940, Airex 950.
Further, the preparation method of the moisture-curing spray polyurea elastomer comprises the following steps:
preparation of component A:
adding accurately metered polyether polyol into a reaction kettle, vacuumizing and dehydrating for 1-5 hours, preferably 2-3 hours at 80-150 ℃, preferably 90-130 ℃, sampling and measuring the water content, stopping dehydrating when the water content reaches below 0.08 wt%, cooling to 30-80 ℃, preferably 50-70 ℃, maintaining the temperature range, optionally adding a diluent and an organic tin catalyst, dropwise adding accurately metered diisocyanate into the kettle while stirring, continuously reacting for 1-5 hours, preferably 2-4 hours at 70-110 ℃, preferably 80-100 ℃, reducing the temperature after defoaming, obtaining a component A with the NCO content of 12-20 wt%, and cooling and discharging.
Preparation of the component B:
in a container equipped with a stirrer, a thermometer and N2Adding one or more than one primary diamine and catalyst in a reaction kettle of a gas pipeline, dropwise adding siloxane containing unsaturated double bonds in an accurately metered amount under stirring at 60-90 ℃, preferably 70-80 ℃, reacting for 2-4h, preferably 3-4h under the protection of nitrogen to obtain the secondary diamine containing siloxane branched chains. Pouring the secondary diamine, the fumed silica, the dispersing agent and the defoaming agent into a stirring kettle according to a certain ratio, heating to 50-100 ℃, preferably 60-90 ℃, stirring for 30-50min at the rotation speed of 400-1200r/min, preferably 500-1000r/min to obtain a component B;
mixing the component A and the component B according to a volume ratio of 1:1, mixing and spraying to obtain the polyurea elastomer.
In the present invention, the term "optionally added" means addition or non-addition.
The invention has the following beneficial effects:
(1) the moisture-cured spray polyurea elastomer has excellent thermal-oxidative aging resistance.
(2) The moisture-cured spray polyurea elastomer has a slower curing speed than the conventional polyurea and a lower A, B component mixing viscosity.
(3) The moisture-cured spray polyurea elastomer disclosed by the invention has excellent adhesion performance of a cured material to a base material.
(4) The material after being cured has better toughness.
Description of the drawings: FIG. 1 is a NMR spectrum of a bis-secondary amine containing a siloxane group prepared in example 1.
FIG. 2 is a NMR spectrum of a bis-secondary amine containing a siloxane group prepared in example 2.
FIG. 3 is a NMR spectrum of a bis-secondary amine containing siloxane groups prepared in example 3.
FIG. 4 is a NMR spectrum of a bis-secondary amine containing a siloxane group prepared in example 4.
Detailed Description
The present invention is further illustrated by the following specific examples, which are intended to be illustrative only and not to limit the scope of the invention.
The NMR spectra in the examples were obtained from Bruker AVANCE III 400MHz test.
The raw materials and sources are detailed in table 1.
TABLE 1 raw materials and sources
| Chemical name | Manufacturer of the product |
| IPDA | Wanhua Chemical Group Co., Ltd. |
| HMDA | Wanhua Chemical Group Co., Ltd. |
| Polyetheramine D230 | Henscman chemistry |
| Vinyl trimethoxy silane | Nanjing Union Silicon Chemical Co.,Ltd. |
| Vinyl triethoxy silane | Nanjing Union Silicon Chemical Co.,Ltd. |
| Fumed silica | Jiangsu Hao energy chemical industry Co., Ltd |
| HMDI | Wanhua Chemical Group Co., Ltd. |
| IPDI | Wanhua Chemical Group Co., Ltd. |
| HDI | Wanhua Chemical Group Co., Ltd. |
| Polyether polyols | Optimization chemistry |
| Dibutyl phthalate | SHANGHAI MACKLIN BIOCHEMICAL Co.,Ltd. |
| 1, 3-Cyclohexanediamine | Basf-Fr |
| 1, 3-propanediamine | SHANGHAI MACKLIN BIOCHEMICAL Co.,Ltd. |
| Tego Dispers 610 | Winning wound |
| Tego Airex900 | Winning wound |
| Diethyltoluene diamine (DETDA) | Jiangsu Vico Teri chemical Co., Ltd |
| Chain extender clearlink-1000 | Dorf KATAL |
Example 1
A method of preparing a moisture-curable spray polyurea elastomer comprising:
preparation of component A:
40 parts of polyoxypropylene glycol (N210, Mn 1000) was charged into a reaction vessel, dehydrated at 110 ℃ under a vacuum of 0.09MPa for 3 hours, and then cooled to 60 ℃. Adding 48 parts of isophorone diisocyanate into a reaction kettle with a stirrer and nitrogen protection, adding 5 parts of dibutyl phthalate and 0.1 part of dibutyltin dilaurate, slowly dripping dehydrated polyoxypropylene glycol into the reaction kettle, heating a reaction system to 90 ℃ after dripping is finished, carrying out heat preservation reaction for 3 hours, defoaming, and cooling to obtain an isocyanate prepolymer A component with 15.9% of-NCO content;
preparation of the component B:
in a container equipped with a stirrer, a thermometer and N2Adding 30 parts of isophorone diamine and 0.39 part of tetraalkylammonium hydroxide into a reaction kettle of a gas pipeline, then dropwise adding 67.2 parts of vinyltriethoxysilane into the reaction kettle under stirring at 80 ℃, and continuing to react for 4 hours under the protection of nitrogen after dropwise adding to obtain the bis-secondary amine containing siloxane branches (groups) (the nuclear magnetism characterization result is shown in figure 1, the peak value at the chemical shift delta of 125-140 ppm is reduced, and the Markel addition reaction between double bonds in vinyl siloxane and hydrogen atoms on amino groups is proved to be generated, so that the bis-secondary amine containing siloxane groups is generated). Then 0.5 part of fumed silica, 0.2 part of dispersant Tego Dispers610 and 0.4 part of defoamer Airex900 are poured into a stirring kettle, the temperature is raised to 60 ℃, the stirring is carried out for 30min, and the rotating speed is 1000r/min, so as to obtain a component B;
mixing the component A and the component B according to the volume ratio of 1:1, mixing and spraying to obtain the moisture-cured spraying polyurea elastomer.
Example 2
A method of preparing a moisture-curable spray polyurea elastomer comprising:
preparation of component A:
51.25 parts of polyoxypropylene glycol (N204, Mn. RTM.400) was charged into a reaction vessel, dehydrated at 110 ℃ under a vacuum of 0.09MPa for 3 hours, and then cooled to 60 ℃. Adding 59 parts of hexamethylene diisocyanate into a reaction kettle with a stirrer and nitrogen protection, adding 15 parts of dibutyl phthalate and 0.66 part of dibutyltin dilaurate, slowly dripping dehydrated polyoxypropylene glycol into the reaction kettle, heating a reaction system to 90 ℃ after dripping is finished, carrying out heat preservation reaction for 3 hours, defoaming and cooling to obtain an isocyanate prepolymer A component with 15% of-NCO content;
preparation of the component B:
in a container equipped with a stirrer, a thermometer and N2Adding 46.75 parts of diaminodicyclohexyl methane and 1.12 parts of tetraalkylammonium hydroxide into a reaction kettle of a gas pipeline, then dropwise adding 66 parts of vinyltrimethoxysilane into the reaction kettle under stirring at 80 ℃, and continuing to react for 4 hours under the protection of nitrogen after dropwise adding to obtain the bis-secondary amine containing siloxane branches (a nuclear magnetism characterization result is shown in figure 2, the peak value at the chemical shift delta of 125-140 ppm is reduced, and the Markel addition reaction between double bonds in vinyl siloxane and hydrogen atoms on amine groups is proved to generate the bis-secondary amine containing siloxane groups). Then 0.8 part of fumed silica, 0.6 part of dispersant Tego Dispers610 and 0.7 part of defoamer Airex900 are poured into a stirring kettle, the temperature is raised to 60 ℃, the stirring is carried out for 50min, and the rotating speed is 500r/min, so as to obtain a component B;
mixing the component A and the component B according to the volume ratio of 1:1, mixing and spraying to obtain the moisture-cured spraying polyurea elastomer.
Example 3
A method of preparing a moisture-curable spray polyurea elastomer comprising:
preparation of component A:
37.2 parts of polyoxypropylene glycol (N210, Mn 1000) was charged into a reaction vessel, dehydrated at 110 ℃ under a vacuum of 0.09MPa for 3 hours, and then cooled to 60 ℃. Adding 62.8 parts of dicyclohexylmethane diisocyanate into a reaction kettle with a stirrer and nitrogen protection, adding 10 parts of dibutyl phthalate and 0.4 part of dibutyltin dilaurate, slowly dripping dehydrated polyoxypropylene glycol into the reaction kettle, heating a reaction system to 90 ℃ after dripping is finished, carrying out heat preservation reaction for 3 hours, and cooling after defoaming to obtain an isocyanate prepolymer A component with 15.4% of-NCO content;
preparation of the component B:
in a container equipped with a stirrer, a thermometer and N 215 parts of 1, 3-propanediamine and 0.64 part of tetraalkylammonium hydroxide were added to a gas-line reactor at 80 ℃ CUnder stirring, 77.05 parts of vinyltriethoxysilane is dropwise added into a reaction kettle, and after dropwise addition, reaction is continued for 4 hours under the protection of nitrogen to obtain the bis-secondary amine containing siloxane branches (shown in figure 3 as a nuclear magnetic characterization result, the peak value at the chemical shift delta of 125-140 ppm is reduced, and the result proves that the double bonds in the vinyl siloxane and the hydrogen atoms on the amino groups undergo a Markel addition reaction to generate the bis-secondary amine containing siloxane groups). Then 0.6 part of fumed silica, 0.4 part of dispersant Tego Dispers610 and 0.6 part of defoamer Airex900 are poured into a stirring kettle, the temperature is raised to 60 ℃, the stirring is carried out for 40min, and the rotating speed is 800r/min, so as to obtain a component B;
mixing the component A and the component B according to the volume ratio of 1:1, mixing and spraying to obtain the moisture-cured spraying polyurea elastomer.
Example 4
A method of preparing a moisture-curable spray polyurea elastomer comprising:
preparation of component A:
32 parts of polyoxypropylene glycol (N204, Mn. RTM. 400) was charged into a reaction vessel, dehydrated at 110 ℃ under a vacuum of 0.09MPa for 3 hours, and then cooled to 60 ℃. Adding 58.4 parts of isophorone diisocyanate into a reaction kettle with a stirrer and nitrogen protection, adding 10 parts of dibutyl phthalate and 0.36 part of dibutyltin dilaurate, slowly dripping dehydrated polyoxypropylene glycol into the reaction kettle, heating a reaction system to 90 ℃ after dripping is finished, carrying out heat preservation reaction for 3 hours, defoaming, and cooling to obtain an isocyanate prepolymer A component with 15.3% of-NCO content;
preparation of the component B:
in a container equipped with a stirrer, a thermometer and N2Adding 42 parts of polyetheramine D230 and 0.67 part of tetraalkylammonium hydroxide into a reaction kettle of a gas pipeline, then dropwise adding 54.16 parts of vinyltrimethoxysilane into the reaction kettle while stirring at 80 ℃, and continuing to react for 4 hours under the protection of nitrogen after dropwise adding to obtain bis-secondary amine containing siloxane branched chains (shown in figure 4 as a nuclear magnetic characterization result, the peak value at the chemical shift delta of 125-140 ppm is reduced, which proves that the double bonds in the vinyl siloxane and the hydrogen atoms on the amino groups have the Markel addition reactionA bis-secondary amine containing a siloxane group is generated). Then 0.6 part of fumed silica, 0.4 part of dispersant Tego Dispers610 and 0.5 part of defoamer Airex900 are poured into a stirring kettle, the temperature is raised to 60 ℃, the stirring is carried out for 30min, and the rotating speed is 1000r/min, so as to obtain the component B.
Mixing the component A and the component B according to the volume ratio of 1:1, mixing and spraying to obtain the moisture-cured spraying polyurea elastomer.
Comparative example:
preparation of component A:
32 parts of polyoxypropylene glycol (N204) was charged into a reaction vessel, dehydrated at 110 ℃ under a vacuum of 0.09MPa for 3 hours, and then cooled to 60 ℃. Adding 58.4 parts of isophorone diisocyanate and 0.54 part of dibutyltin dilaurate into a reaction kettle with a stirrer and nitrogen protection, slowly dripping dehydrated polyoxypropylene glycol into the reaction kettle, heating a reaction system to 90 ℃ after dripping is finished, carrying out heat preservation reaction for 3 hours, and cooling after defoaming to obtain an isocyanate prepolymer A component with 17% of-NCO content;
preparation of the component B:
in a container equipped with a stirrer, a thermometer and N2Adding 36 parts of polyetheramine D2000, 16.18 parts of diethyltoluenediamine, 18 parts of clearlink-1000, 0.8 part of fumed silica, 0.5 part of dispersant Tego Dispers610 and 0.7 part of defoamer Airex900 into a reaction kettle of an air pipeline, pouring into a stirring kettle, heating to 60 ℃, stirring for 30min at the rotating speed of 1000r/min, and obtaining a component B;
mixing the component A and the component B according to the volume ratio of 1:1, mixing and spraying to obtain the traditional spraying polyurea elastomer.
The spray polyurea elastomer prepared respectively in the above embodiments is cured for three days in an indoor environment with 23 ℃ and 50% relative humidity, cured for 4 days in a common oven with 50 ℃ to prepare cured sample strips, the sample strips are tested according to corresponding national standards and standards, and then are subjected to thermal oxidation aging for 300 hours at 90 ℃, and then are subjected to performance test and comparison, wherein the test standards are as follows:
the results of the gel time (GB-T12007.7-1989), tensile strength (GB/T528-.
TABLE 2 comparison of spray polyurea elastomer Properties
As can be seen from Table 2, compared with the traditional spray polyurea elastomer, the moisture-cured spray polyurea elastomer provided by the invention has longer gel time, better low-temperature resistance, wear resistance, adhesive force and thermal-oxidative aging resistance, and obviously overcomes the defects of poor adhesive force, poor low-temperature resistance and the like of the traditional polyurea, so that the moisture-cured spray polyurea elastomer system provided by the invention has wider application prospect.
Claims (24)
1. Use of a siloxane group-containing bis-secondary amine having the general formula of formula (I):
(R3O)3SiR2NHR1NHR2Si(OR3)3 (I)
in the formula, R1Selected from C3-C10 alkylene, C3-16 cycloalkylene or C3-C16 ether, R2Alkylene selected from C2-C7; r3Selected from C1-C10 alkyl groups.
2. Use according to claim 1, characterized in that, in formula (I), R1Is selected from C3-12 cycloalkylene, C3-C12 ether group; r2Alkylene selected from C2-C3; r3Selected from C1-C2 alkyl groups.
3. Use according to claim 1, characterized in that, in formula (I), R1Comprises the following steps:
4. use according to any one of claims 1 to 3, the method for preparing a bis-secondary amine containing siloxane groups comprising the following steps: siloxane containing unsaturated double bonds and one or more than one primary diamine are subjected to Michael addition reaction to obtain secondary diamine containing siloxane groups; wherein the primary diamine has a structure described by a general formula (II):
H2N-R1-NH2 (II)
wherein R is1Selected from C3-C10 alkylene, C3-16 cycloalkylene or C3-C16 ether, the unsaturated double bond-containing siloxane has a structure described by the general formula (III):
CH2＝CH-R4-Si(OR3)3 (III)
wherein R is4Selected from C0-C5 alkylene; r3Selected from C1-C10 alkyl.
5. Use according to claim 4, characterized in that in formula (II), R1Is selected from C3-12 cycloalkylene, C3-C12 ether group; in the general formula (III), R4Selected from C0-C1 alkylene; r3Selected from C1-C2 alkyl.
6. Use according to claim 4, characterized in that in formula (II), R1Is composed of
7. Use according to claim 4, wherein the Michael addition reaction is carried out under an inert gas blanket.
8. Use according to claim 7, characterized in that the inert protective gas is nitrogen, argon.
9. Use according to claim 4, characterized in that the molar ratio of the unsaturated double bond-containing siloxane to the primary diamine is from 2.0 to 2.1:1, the reaction temperature is 60-90 ℃, and the reaction time is 2-4 h.
10. Use according to claim 9, characterized in that the molar ratio of the unsaturated double bond-containing siloxane to the primary diamine is from 2.0 to 2.05: 1; the reaction temperature is 70-80 ℃, and the reaction time is 3-4 h.
11. Use according to claim 4, wherein the Michael addition reaction is carried out under catalysis of a basic compound in an amount of 0.1 wt% to 1 wt%, based on the total amount of the unsaturated double bond-containing siloxane and the primary diamine.
12. Use according to claim 11, characterized in that the basic compound is sodium metal, sodium ethoxide, sodium hydride, sodium amide or tetraalkylammonium hydroxide in an amount of 0.4% to 0.8% by weight, based on the total amount of the unsaturated double bond-containing siloxane and the diprimary amine.
13. Use according to claim 12, characterized in that the basic compound is tetraalkylammonium hydroxide.
14. Use according to claim 1, characterized in that: mixing diamine containing siloxane group and assistant to prepare component B of spray polyurea, and mixing and spraying component A containing isocyanate prepolymer generated by reaction of polyol and isocyanate to obtain the moisture-cured spray polyurea elastomer.
15. Use according to claim 14, characterized in that: and carrying out mixed spraying according to the volume ratio of the A \ B components of 1: 1.
16. Use according to claim 14, characterized in that: the formulation of the moisture-curable spray polyurea elastomer comprises:
the component A comprises:
mass ratio per part
Isocyanate prepolymer 70-120
0-30 of diluent
The component B comprises:
17. use according to claim 16, characterized in that: the formulation of the moisture-curable spray polyurea elastomer comprises:
the component A comprises:
mass ratio per part
Isocyanate prepolymer 88-110
Diluent 5-15
The component B comprises:
18. use according to any one of claims 14 to 17, characterized in that: the NCO content of the isocyanate prepolymer is 12-20 wt%; the polyol has a number average molecular weight of 200-10000.
19. Use according to claim 18, characterized in that: the polyol is a 400-1000 polyether polyol.
20. Use according to claim 16 or 17, characterized in that: the diluent is selected from one or more of propylene carbonate, dioctyl phthalate and dibutyl phthalate; the dispersing agent is a fatty acid derivative.
21. Use according to claim 20, characterized in that: the diluent is dibutyl phthalate; the dispersing agent is one or two of Tego Dispers610 and Dispers 630.
22. A method for preparing a moisture-curable spray polyurea elastomer, comprising the steps of:
(1) preparation of component A:
adding polyalcohol into a reaction kettle for dehydration, sampling to determine the water content, stopping dehydration when the water content reaches below 0.08 wt%, optionally adding a diluent within the temperature range of 30-80 ℃, dropwise adding diisocyanate into the kettle while stirring, continuously reacting for 1-5 hours within the temperature range of 70-110 ℃ after dropwise adding, defoaming, cooling to obtain a component A, and cooling and discharging;
(2) preparation of the component B:
pouring secondary diamine containing siloxane groups, fumed silica, a dispersing agent and a defoaming agent into a stirring kettle, heating to 50-100 ℃, stirring for 30-50min at the rotation speed of 400-1200r/min to obtain a component B;
(3) mixing the component A and the component B according to a volume ratio of 1:1, mixing and spraying to obtain the polyurea elastomer;
the siloxane group-containing bis-secondary amine is selected from the siloxane group-containing bis-secondary amines of any of claims 1-21.
23. The preparation method according to claim 22, wherein in the step (1), vacuum dehydration is performed for 1 to 5 hours at a temperature of between 80 and 150 ℃, a diluent is optionally added within a temperature range of between 50 and 70 ℃, then diisocyanate is dropwise added into the kettle while stirring, and after the dropwise addition is completed, the reaction is continued for 2 to 4 hours at a temperature range of between 80 and 100 ℃; in the step (2), the temperature is raised to 60-90 ℃, the stirring is carried out for 30-50min, and the rotating speed is 500-.
24. The method according to claim 23, wherein the dehydration is carried out at 90 ℃ to 130 ℃ under vacuum for 2 to 3 hours in the step (1).
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