CN116874716B - Preparation method of terpene type epoxy polyurethane prepolymer, obtained product and application of terpene type epoxy polyurethane prepolymer in asphalt modification - Google Patents
Preparation method of terpene type epoxy polyurethane prepolymer, obtained product and application of terpene type epoxy polyurethane prepolymer in asphalt modification Download PDFInfo
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- CN116874716B CN116874716B CN202311075156.1A CN202311075156A CN116874716B CN 116874716 B CN116874716 B CN 116874716B CN 202311075156 A CN202311075156 A CN 202311075156A CN 116874716 B CN116874716 B CN 116874716B
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- terpene
- type epoxy
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- asphalt
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- 239000010426 asphalt Substances 0.000 title claims abstract description 131
- 235000007586 terpenes Nutrition 0.000 title claims abstract description 95
- 150000003505 terpenes Chemical class 0.000 title claims abstract description 80
- 239000004593 Epoxy Substances 0.000 title claims abstract description 40
- 229920001730 Moisture cure polyurethane Polymers 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 230000004048 modification Effects 0.000 title abstract description 6
- 238000012986 modification Methods 0.000 title abstract description 6
- 239000000463 material Substances 0.000 claims abstract description 86
- 239000003822 epoxy resin Substances 0.000 claims abstract description 79
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 79
- 239000003054 catalyst Substances 0.000 claims abstract description 45
- YHQGMYUVUMAZJR-UHFFFAOYSA-N α-terpinene Chemical compound CC(C)C1=CC=C(C)CC1 YHQGMYUVUMAZJR-UHFFFAOYSA-N 0.000 claims abstract description 42
- WSTYNZDAOAEEKG-UHFFFAOYSA-N Mayol Natural products CC1=C(O)C(=O)C=C2C(CCC3(C4CC(C(CC4(CCC33C)C)=O)C)C)(C)C3=CC=C21 WSTYNZDAOAEEKG-UHFFFAOYSA-N 0.000 claims abstract description 21
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 21
- -1 terpene maleic anhydride compound Chemical class 0.000 claims abstract description 20
- 239000012948 isocyanate Substances 0.000 claims abstract description 16
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 16
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002798 polar solvent Substances 0.000 claims abstract description 9
- 239000011159 matrix material Substances 0.000 claims description 43
- 238000002156 mixing Methods 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 32
- 229920005989 resin Polymers 0.000 claims description 29
- 239000011347 resin Substances 0.000 claims description 29
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 28
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 26
- 239000003795 chemical substances by application Substances 0.000 claims description 22
- 229920005862 polyol Polymers 0.000 claims description 22
- 230000003712 anti-aging effect Effects 0.000 claims description 21
- 150000003077 polyols Chemical class 0.000 claims description 21
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims description 20
- 238000010008 shearing Methods 0.000 claims description 19
- 239000003921 oil Substances 0.000 claims description 18
- 235000019198 oils Nutrition 0.000 claims description 18
- 239000004952 Polyamide Substances 0.000 claims description 16
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 16
- 239000000539 dimer Substances 0.000 claims description 16
- 239000000194 fatty acid Substances 0.000 claims description 16
- 229930195729 fatty acid Natural products 0.000 claims description 16
- 150000004665 fatty acids Chemical class 0.000 claims description 16
- 229920002647 polyamide Polymers 0.000 claims description 16
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 14
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 14
- 229920000642 polymer Polymers 0.000 claims description 13
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 11
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 10
- 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 10
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 10
- 229920000570 polyether Polymers 0.000 claims description 10
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 claims description 10
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 239000003431 cross linking reagent Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 claims description 8
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 claims description 8
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 6
- 235000019482 Palm oil Nutrition 0.000 claims description 5
- 239000002131 composite material Substances 0.000 claims description 5
- 239000002540 palm oil Substances 0.000 claims description 5
- 239000003549 soybean oil Substances 0.000 claims description 5
- 235000012424 soybean oil Nutrition 0.000 claims description 5
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 4
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims description 4
- 239000004359 castor oil Substances 0.000 claims description 4
- 235000019438 castor oil Nutrition 0.000 claims description 4
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 4
- 239000003208 petroleum Substances 0.000 claims description 4
- 229920005906 polyester polyol Polymers 0.000 claims description 4
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 4
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims description 4
- 239000002383 tung oil Substances 0.000 claims description 4
- NNOZGCICXAYKLW-UHFFFAOYSA-N 1,2-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=CC=C1C(C)(C)N=C=O NNOZGCICXAYKLW-UHFFFAOYSA-N 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- GTEXIOINCJRBIO-UHFFFAOYSA-N 2-[2-(dimethylamino)ethoxy]-n,n-dimethylethanamine Chemical compound CN(C)CCOCCN(C)C GTEXIOINCJRBIO-UHFFFAOYSA-N 0.000 claims description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 3
- HVCNXQOWACZAFN-UHFFFAOYSA-N 4-ethylmorpholine Chemical compound CCN1CCOCC1 HVCNXQOWACZAFN-UHFFFAOYSA-N 0.000 claims description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 3
- OUBMGJOQLXMSNT-UHFFFAOYSA-N N-isopropyl-N'-phenyl-p-phenylenediamine Chemical compound C1=CC(NC(C)C)=CC=C1NC1=CC=CC=C1 OUBMGJOQLXMSNT-UHFFFAOYSA-N 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 3
- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical compound C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 0.000 claims description 3
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 claims description 3
- REQPQFUJGGOFQL-UHFFFAOYSA-N dimethylcarbamothioyl n,n-dimethylcarbamodithioate Chemical compound CN(C)C(=S)SC(=S)N(C)C REQPQFUJGGOFQL-UHFFFAOYSA-N 0.000 claims description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 3
- SCRKTTJILRGIEY-UHFFFAOYSA-N pentanedioic acid;zinc Chemical compound [Zn].OC(=O)CCCC(O)=O SCRKTTJILRGIEY-UHFFFAOYSA-N 0.000 claims description 3
- 229920001568 phenolic resin Polymers 0.000 claims description 3
- 239000005011 phenolic resin Substances 0.000 claims description 3
- RKQOSDAEEGPRER-UHFFFAOYSA-L zinc diethyldithiocarbamate Chemical compound [Zn+2].CCN(CC)C([S-])=S.CCN(CC)C([S-])=S RKQOSDAEEGPRER-UHFFFAOYSA-L 0.000 claims description 3
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 abstract description 48
- 239000004814 polyurethane Substances 0.000 abstract description 48
- 239000002994 raw material Substances 0.000 abstract description 6
- 230000007613 environmental effect Effects 0.000 abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052799 carbon Inorganic materials 0.000 abstract description 2
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 53
- 229940044600 maleic anhydride Drugs 0.000 description 47
- 239000002861 polymer material Substances 0.000 description 10
- 238000003756 stirring Methods 0.000 description 7
- 239000003963 antioxidant agent Substances 0.000 description 6
- 230000003078 antioxidant effect Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000003377 acid catalyst Substances 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 229920013724 bio-based polymer Polymers 0.000 description 4
- 125000003700 epoxy group Chemical group 0.000 description 4
- 239000002028 Biomass Substances 0.000 description 3
- 241000779819 Syncarpia glomulifera Species 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000035515 penetration Effects 0.000 description 3
- 239000001739 pinus spp. Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229940036248 turpentine Drugs 0.000 description 3
- IBOFVQJTBBUKMU-UHFFFAOYSA-N 4,4'-methylene-bis-(2-chloroaniline) Chemical group C1=C(Cl)C(N)=CC=C1CC1=CC=C(N)C(Cl)=C1 IBOFVQJTBBUKMU-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 241001112258 Moca Species 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 229920005610 lignin Polymers 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 150000002924 oxiranes Chemical class 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 235000015112 vegetable and seed oil Nutrition 0.000 description 2
- 239000008158 vegetable oil Substances 0.000 description 2
- DFWCPLGXFMSUCW-UHFFFAOYSA-N 3-(dimethylamino)propyl carbamimidothioate;hydron;dichloride Chemical compound Cl.Cl.CN(C)CCCSC(N)=N DFWCPLGXFMSUCW-UHFFFAOYSA-N 0.000 description 1
- BUZICZZQJDLXJN-UHFFFAOYSA-N 3-azaniumyl-4-hydroxybutanoate Chemical compound OCC(N)CC(O)=O BUZICZZQJDLXJN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 150000008064 anhydrides Chemical group 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 150000005676 cyclic carbonates Chemical group 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 125000001261 isocyanato group Chemical group *N=C=O 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229930006978 terpinene Natural products 0.000 description 1
- 150000003507 terpinene derivatives Chemical class 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
- C08G18/40—High-molecular-weight compounds
- C08G18/58—Epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/12—Polycondensates containing more than one epoxy group per molecule of polycarboxylic acids with epihalohydrins or precursors thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L95/00—Compositions of bituminous materials, e.g. asphalt, tar, pitch
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Civil Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a preparation method of a terpene type epoxy polyurethane prepolymer, an obtained product and application thereof in asphalt modification, wherein alpha-terpinene, maleic anhydride, a catalyst and a polar solvent are mixed and then react to generate a terpene maleic anhydride compound; adding a catalyst into epoxy chloropropane and a terpene maleic anhydride compound in a polar solvent to react to generate terpene epoxy resin; adding isocyanate into the terpene type epoxy resin, and reacting to obtain the terpene type epoxy polyurethane prepolymer. The terpene type epoxy polyurethane prepolymer can form polyurethane in situ in asphalt, the polyurethane plays a skeleton role and a bonding role with aggregate, and the modified asphalt modified by the polyurethane has good road performance. In addition, the invention replaces non-renewable materials to the maximum extent, and has the characteristics of low carbon, environmental protection, renewable raw materials, biodegradability and the like.
Description
Technical Field
The invention relates to a preparation method of a terpene type epoxy polyurethane prepolymer, an obtained product and application thereof in asphalt modification, and belongs to the technical field of polymer modified asphalt.
Background
The bio-based polymer material is a novel polymer material manufactured by using renewable biomass raw materials through biological, chemical, physical and other methods, and is an important component of the bio-based material. The main function of the bio-based polymer material is to replace non-renewable materials such as steel, cement, petroleum-based plastics and the like to the greatest extent, and the bio-based polymer material has the characteristics of environmental protection, renewable raw materials, biodegradability and the like. The global bio-based polymer material industry as a whole is in the transition phase of laboratory research and development to industrial production and scale-up application. The biomass epoxy material synthesized by utilizing agriculture and forestry biomass with abundant reserves in the nature and residual resources thereof not only has the basic characteristics of general epoxy resin, but also has the advantages of renewable raw materials, biodegradability, environmental compatibility and the like. The epoxy groups in the molecular structure of the epoxy resin or the epoxide react with active hydrogen-containing compounds and the like, and derivatives containing hydroxyl groups, cyclic carbonate groups and other active groups can be generated, so that the epoxy resin or the epoxide can be used as fine chemicals such as polyester (ether) polyol, quaternary ammonium salt derivatives and other polymer materials such as polyurethane, polyester, unsaturated resin and the like. The natural vegetable oil contains a plurality of fatty chain structures, and the derivatives thereof contain active epoxy groups, anhydride groups, amino groups and the like, and the modified polymer composite material with excellent comprehensive performance can be prepared by adding the natural vegetable oil derivatives into a composite system. The dimer fatty acid polyamide can be used as an excellent modifier of the composite material due to the special molecular structure, and the molecular structure contains a long fatty chain structure, functional carboxyl and amino groups, and has toughening, compatibilizing or reinforcing effects on the composite system.
The polymer modified asphalt is a binder having the property of increasing the shear strength of the asphalt mixture, and thus contributes to the improvement of the permanent deformation resistance and rut resistance of the asphalt mixture. Compared with the high-modulus asphalt mixture, the high-modulus asphalt naturally increases the high-temperature performance and rutting resistance of the asphalt, but increases the modulus and simultaneously reduces the low-temperature cracking resistance of the asphalt, and the asphalt has poor permanent deformation resistance. Therefore, the polymer modified asphalt pavement has the advantages of more comfortable driving, wear resistance, small driving vibration, low noise, simple maintenance and the like.
The prior polyurethane modified asphalt has attracted wide attention, and CN113429886A discloses a polyurethane modified asphalt, which is prepared by the following steps: dehydrating and cooling the linear polyol, uniformly stirring the linear polyol, isocyanate monomers and maleic anhydride, and then heating to react to obtain a prepolymer; stirring and dispersing the aromatic polyol and the matrix asphalt until the mixture is uniform, adding the prepolymer and the catalyst into a reactor, and reacting to obtain the polyurethane modified asphalt. It is mentioned in this patent that maleic anhydride reacts primarily with polar groups (e.g., hydroxyl groups) contained in the asphalt, increasing the polarity of the asphaltenes and thus increasing the compatibility of the polyurethane with the asphalt. CN114369372 a discloses a preparation method of a cold region high-performance resin asphalt material, which comprises the following steps: heating matrix asphalt to a flowing state, adding turpentine, stirring, and preserving heat until the matrix asphalt is fully dissolved; controlling the temperature at 85-90 ℃, adding polymeric isocyanate, and stirring until the reaction is complete; adding bisphenol A epoxy resin, and fully stirring until the liquid is cooled to room temperature and no bubbles are generated; adding a curing agent and uniformly stirring; and heating and curing to obtain the cold region high-performance resin asphalt material. The patent mentions that the addition of turpentine can ensure that asphalt can be fused with epoxy resin at normal temperature, and the toughness of resin asphalt is further improved, but turpentine exists in modified asphalt in the form of a diluent, and the modified asphalt still has the problem of insufficient stability.
In addition, although polyurethane modified asphalt materials exhibit excellent properties (such as low temperature properties) in some respects, the properties (such as high temperature properties) of polyurethane modified asphalt materials have not been satisfactory for use due to limitations of commercial polyurethane varieties, and commercial polyurethanes are mostly non-renewable materials, with poor environmental friendliness.
Disclosure of Invention
The invention aims to provide a preparation method of a terpene-type epoxy polyurethane prepolymer and an obtained product, wherein the terpene-type epoxy polyurethane prepolymer is prepared by taking alpha-terpinene, maleic anhydride, epichlorohydrin and isocyanate as raw materials.
In order to achieve the above object, the present invention provides the following technical solutions:
a method for preparing a terpene type epoxy polyurethane prepolymer, which comprises the following steps:
(1) Mixing alpha-terpinene, maleic anhydride, a catalyst and a polar solvent, and then reacting to generate a terpene maleic anhydride compound;
(2) Adding a catalyst into epoxy chloropropane and a terpene maleic anhydride compound in a polar solvent to react to generate terpene epoxy resin;
(3) And adding isocyanate into the terpene type epoxy resin, and reacting isocyanate groups with hydroxyl groups on the terpene type epoxy resin in the presence of a catalyst to obtain the terpene type epoxy polyurethane prepolymer.
Further, the reaction scheme of the terpene type epoxy resin is as follows:
Further, the reaction scheme of the terpene-type epoxy polyurethane prepolymer of the invention is shown below (taking isocyanate as diphenylmethane diisocyanate as an example):
Further, in the step (1), the molar ratio of the alpha-terpinene to the maleic anhydride is 1:1.
Further, in the step (1), the catalyst is one or more of di-tert-butyl peroxide, phosphoric acid, p-toluenesulfonic acid and phosphomolybdic acid. Preferably, the mass ratio of α -terpinene to catalyst is 1:0.002 to 0.01, e.g., 1:0.002, 1:0.003, 1:0.004, 1:0.005, 1:0.006, 1:0.007, 1:0.008, 1:0.009, 1:0.01.
Further, in the step (1), the polar solvent is one or more of tetrahydrofuran, toluene and 1, 4-dioxane.
Further, in the step (1), the reaction temperature is 40 to 70 ℃, for example, 40 ℃,50 ℃, 60 ℃, 70 ℃. The reaction time is 10 to 15 hours, for example 10 hours, 11 hours, 12 hours, 13 hours, 14 hours, 15 hours.
Further, in the step (2), the molar ratio of the alpha-terpinene to the epichlorohydrin is 1:
adding epichlorohydrin in the relation of 1.01-1.05.
Further, in the step (2), the catalyst is one or more of zinc glutarate, pr (naph) 3-Al (i-Bu) 3 and tetraethylammonium bromide. Preferably, the mass ratio of epichlorohydrin to catalyst is 1:0.001-0.01, for example 1:0.001, 1:0.002, 1:0.003, 1:0.004, 1:0.005, 1:0.006, 1:0.007, 1:0.008, 1:0.009, 1:0.01.
Further, in the step (2), the polar solvent is one or more of tetrahydrofuran, toluene and 1, 4-dioxane.
Further, in the step (2), the reaction temperature is 20 to 60℃such as 20℃and 30℃and 40℃and 50℃and 60 ℃. The reaction time is 8 to 15 hours, for example 8 hours, 9 hours, 10 hours, 11 hours, 12 hours, 13 hours, 14 hours, 15 hours.
Further, in the step (3), the isocyanate is one or more of isophorone diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, methylenebis (4-cyclohexyl isocyanate) and tetramethylxylylene diisocyanate.
Further, in the step (3), the molar ratio of epichlorohydrin to isocyanate is 1: isocyanate is added in a relationship of 0.8 to 1.
Further, in the step (3), the catalyst is one or more of dibutyl tin dilaurate, dimethylaminoethyl ether and N-ethylmorpholine. Preferably, the mass ratio of isocyanate to catalyst is 1:0.005 to 0.01, e.g. 1:0.005, 1:0.006, 1:0.007, 1:0.008, 1:0.009, 1:0.01.
Further, in the step (3), the reaction temperature is 30 to 70 ℃, for example, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃. The reaction time is 10 to 20 hours, for example 10 hours, 11 hours, 12 hours, 13 hours, 14 hours, 15 hours, 16 hours, 17 hours, 18 hours, 19 hours, 20 hours.
The invention also provides a terpene type epoxy polyurethane prepolymer prepared by the method, and the polymerization degree m of the prepolymer is 1-10. The terpene type epoxy polyurethane prepolymer can be further reacted with polyol to synthesize polyurethane, and the obtained polyurethane contains terpene blocks, epoxy groups and long alkyl chains (hydrophobic chain segments), so that the high-low temperature performance and fatigue resistance of asphalt are improved well.
The invention also provides modified asphalt which is prepared from the material A and the material B. And (3) independently packaging the material A and the material B, mixing in the using process, and then crosslinking and curing the materials to form polyurethane, thereby obtaining the polyurethane modified asphalt.
Further, the material A comprises the following components in parts by weight: 50 parts of matrix asphalt, 10-30 parts of terpene type epoxy polyurethane prepolymer, 5-20 parts of compatilizer, 5-20 parts of resin, 0.5-1 part of accelerator and 0.2-0.8 part of anti-aging agent.
Further, the material B comprises the following components in parts by weight: 50 parts of matrix asphalt, 10-30 parts of polymer polyol and 2-8 parts of cross-linking agent.
Further, the above matrix asphalt refers to asphalt modified without adding a polymer, which is commercially available directly. The matrix asphalt is preferably 70# and/or 90#.
Preferably, the content of the terpene type epoxy polyurethane prepolymer is 15-30 parts.
Further, the compatilizer comprises one or more of naphthenic oil, furfural extract oil, palm oil, tung oil, castor oil, epoxidized soybean oil and polyurethane diluent. Preferably, the compatibilizer is 10-20 parts.
Further, the resin comprises one or more of lignin, phenolic resin, petroleum resin, rosin resin, terpene resin and coumarone resin.
Further, the accelerator comprises one or more of TMTD (tetramethylthiuram disulfide), TMTM (tetramethylthiuram monosulfide), zinc diethyldithiocarbamate, dibenzothiazyl disulfide.
Further, the anti-aging agent comprises one or more of an anti-aging agent AW, an anti-aging agent A, an anti-aging agent D, an anti-aging agent IPPD and an anti-aging agent PPD.
Further, the polymer polyol includes a polyether polyol or a polyester polyol.
Further, the cross-linking agent is a dimer fatty acid polyamide. The dimer fatty acid polyamide plays a role in crosslinking and curing, and is beneficial to the polyurethane high polymer material to form a crosslinked network structure; on the other hand, the molecular structure of the modified asphalt contains a long fatty chain structure and also contains functional carboxyl and amino, and the special molecular structure can improve the compatibility of polyurethane and asphalt, has the effects of toughening, compatibilizing and reinforcing, and can improve the mechanical property of the modified asphalt.
The invention also provides a preparation method of the modified asphalt, which comprises the following steps:
(1) Heating matrix asphalt to a flowing state, adding terpene type epoxy polyurethane prepolymer, compatilizer, resin, accelerator and anti-aging agent into the matrix asphalt under a shearing condition, and uniformly mixing to form a material A;
(2) Heating the matrix asphalt to a flowing state, adding the polymer polyol and the cross-linking agent into the matrix asphalt under the shearing condition, and uniformly mixing to form a material B;
(3) When in use, the material A and the material B are mixed, sheared and solidified to obtain the modified asphalt.
Further, in steps (1) and (2), the matrix asphalt is generally heated to 100-160 ℃ to achieve a flowing state.
Further, in the steps (1) and (2), the shearing purpose is mainly to uniformly mix the components in the matrix asphalt, and the shearing speed is generally 1000-5000rpm.
Further, in the step (1), the terpene-type epoxy polyurethane prepolymer, the compatilizer, the resin, the accelerator and the anti-aging agent can be added into the flowing matrix asphalt separately or mixed together and then added into the flowing matrix asphalt.
Further, in the step (2), the polymer polyol and the crosslinking agent may be added to the matrix asphalt in a flowing state separately or may be mixed together and then added to the matrix asphalt in a flowing state.
Further, in the step (3), after the materials A and B are mixed, shearing is carried out for 30-60 min at 110-160 ℃, and then curing is carried out for 10-50 min at 110-160 ℃, so that the terpene type epoxy polyurethane prepolymer in the material A and the polymer polyol in the material B are crosslinked and cured in the presence of dimer fatty acid polyamide to form polyurethane, and a schematic diagram of crosslinking and curing of the materials A and B is shown in figure 1.
Further, in the step (3), the shearing speed is 1000-5000rpm.
Firstly, reacting alpha-terpinene with maleic anhydride, then reacting a reaction product with epichlorohydrin to generate terpene type epoxy resin, adding an isocyanate-containing substance, reacting with hydroxyl on the terpene type epoxy resin to generate terpene type epoxy polyurethane prepolymer containing isocyanate groups, respectively adding the terpene type epoxy polyurethane prepolymer and polymer polyol into a material A and a material B of modified asphalt, and mixing the materials in the paving process to form polyurethane polymer materials in situ in the modified asphalt. The terpene type epoxy polyurethane prepolymer and the polyurethane material of the invention contain terpene blocks, which is beneficial to improving the compatibility and the dispersibility of the resin in asphalt, and simultaneously, the epoxy groups are introduced into the polymer chain, which is beneficial to improving the binding force of the polymer material in asphalt mixture with coarse aggregate, fine aggregate, mineral powder and other components. The polyurethane material plays a role in both a skeleton function and a binding function with aggregate in asphalt. The modified asphalt modified by the polyurethane has good road performance.
The cross-linking agent dimer fatty acid polyamide used in the invention has the cross-linking and solidifying effects on one hand, and is beneficial to the polymer material to form a cross-linked network structure; on the other hand, the compatibility of polyurethane and asphalt and the dispersibility of polyurethane in asphalt are improved due to long alkyl chains (hydrophobic chain segments), carboxyl groups and amino groups, so that the mechanical properties of the modified asphalt are improved.
The auxiliary materials such as terpinene, palm oil, tung oil, castor oil, epoxidized soybean oil, rosin resin and the like used in the invention are basically bio-based materials, so that the auxiliary materials replace non-renewable materials to the greatest extent, and the auxiliary materials have the characteristics of low carbon, environmental protection, renewable raw materials, biodegradability and the like.
Drawings
FIG. 1 is a schematic diagram of cross-linking and curing of materials A and B.
Fig. 2 is a fluorescent image of the modified asphalt of example 10, in which black areas are asphalt and white areas are polyurethane.
Detailed Description
The following detailed description of the present invention is provided in connection with the following examples, which are to be construed as merely illustrative, and not a limitation of the scope of the present invention.
Example 1
(1) 13.6G of alpha-terpinene is dissolved in 10ml of tetrahydrofuran, 9.8g of maleic anhydride and 0.08g of phosphomolybdic acid catalyst are added, and the mixture is reacted for 12 hours at 50 ℃ to generate terpene maleic anhydride compound.
(2) After the reaction (1) is finished, 9.5g of epoxy chloropropane and 0.08g of catalyst tetraethylammonium bromide are added for reaction for 8 hours at 40 ℃ to generate terpene-maleic anhydride glycidyl ester type epoxy resin, namely the novel terpene type epoxy resin.
(3) And adding 25gMDI (diphenylmethane diisocyanate) into the generated terpene-maleic anhydride glycidyl ester type epoxy resin, adding 0.15g of dibutyltin dilaurate serving as a catalyst, reacting for 15 hours at 50 ℃, and reacting isocyanato with hydroxyl on the terpene-type epoxy resin to form the novel terpene-type epoxy polyurethane prepolymer.
Example 2
(1) 13.6G of alpha-terpinene is dissolved in 10ml of tetrahydrofuran, 9.8g of maleic anhydride and 0.08g of phosphomolybdic acid catalyst are added, and the mixture is reacted for 15 hours at 40 ℃ to generate terpene maleic anhydride compound.
(2) After the reaction (1) is finished, 9.5g of epoxy chloropropane and 0.08g of catalyst tetraethylammonium bromide are added for reaction for 15 hours at 20 ℃ to generate terpene-maleic anhydride glycidyl ester type epoxy resin, namely the novel terpene type epoxy resin.
(3) 25GMDI (diphenylmethane diisocyanate) is added into the generated terpene-maleic anhydride glycidyl ester type epoxy resin, 0.15g of dibutyltin dilaurate serving as a catalyst is added, the reaction is carried out for 20 hours at 30 ℃, and isocyanate groups react with hydroxyl groups on the terpene-type epoxy resin to form a terpene-type epoxy polyurethane prepolymer.
Example 3
(1) 13.6G of alpha-terpinene is dissolved in 10ml of tetrahydrofuran, 9.8g of maleic anhydride and 0.08g of phosphomolybdic acid catalyst are added, and the mixture is reacted for 10 hours at 70 ℃ to generate terpene maleic anhydride compound.
(2) After the reaction (1) is finished, 9.5g of epoxy chloropropane and 0.08g of catalyst tetraethylammonium bromide are added for reaction at 60 ℃ for 8 hours, so that the terpene-maleic anhydride glycidyl ester type epoxy resin, namely the novel terpene-type epoxy resin, is produced.
(3) 25GMDI (diphenylmethane diisocyanate) was added to the resulting terpene-maleic anhydride glycidyl ester type epoxy resin, 0.15g of dibutyltin dilaurate as a catalyst was added, and the reaction was carried out at 70℃for 10 hours, and isocyanate groups reacted with hydroxyl groups on the terpene-type epoxy resin to form a terpene-type epoxy polyurethane prepolymer.
Example 4
(1) 13.6G of alpha-terpinene is dissolved in 10ml of tetrahydrofuran, 9.8g of maleic anhydride and 0.08g of phosphomolybdic acid catalyst are added, and the mixture is reacted for 10 hours at 40 ℃ to generate terpene maleic anhydride compound.
(2) After the reaction (1) is finished, 9.5g of epoxy chloropropane and 0.08g of catalyst tetraethylammonium bromide are added for reaction for 8 hours at 20 ℃ to generate terpene-maleic anhydride glycidyl ester type epoxy resin, namely the novel terpene-type epoxy resin.
(3) To the resulting terpene-maleic-anhydride glycidyl-ester-type epoxy resin, 25gMDI (diphenylmethane diisocyanate) was added, 0.15g of dibutyltin dilaurate as a catalyst was added, and the reaction was carried out at 30℃for 10 hours, and isocyanate groups reacted with hydroxyl groups on the terpene-type epoxy resin to form a terpene-type epoxy polyurethane prepolymer.
Example 5
(1) 13.6G of alpha-terpinene is dissolved in 10ml of tetrahydrofuran, 9.8g of maleic anhydride and 0.08g of phosphomolybdic acid catalyst are added, and the mixture is reacted for 15 hours at 70 ℃ to generate terpene maleic anhydride compound.
(2) After the reaction (1) is finished, 9.5g of epoxy chloropropane and 0.08g of catalyst tetraethylammonium bromide are added for reaction for 15 hours at 60 ℃ to generate terpene-maleic anhydride glycidyl ester type epoxy resin, namely the novel terpene-type epoxy resin.
(3) To the resulting terpene-maleic-anhydride glycidyl-ester-type epoxy resin, 25gMDI (diphenylmethane diisocyanate) was added, 0.15g of dibutyltin dilaurate as a catalyst was added, and the reaction was carried out at 70℃for 20 hours, and isocyanate groups reacted with hydroxyl groups on the terpene-type epoxy resin to form a terpene-type epoxy polyurethane prepolymer.
Example 6
(1) 13.6G of alpha-terpinene is dissolved in 10ml of tetrahydrofuran, 9.8g of maleic anhydride and 0.03g of p-toluenesulfonic acid as a catalyst are added, and the mixture is reacted at 50 ℃ for 12 hours to produce a terpene maleic anhydride compound.
(2) After the reaction (1) is finished, 9.5g of epichlorohydrin and 0.095g of zinc glutarate serving as a catalyst are added to react for 8 hours at 40 ℃ to generate terpene-maleic anhydride glycidyl ester type epoxy resin, namely the novel terpene type epoxy resin.
(3) 17.5G of toluene diisocyanate and 0.15g of dimethylaminoethyl ether as catalyst are added into the generated terpene-maleic anhydride glycidyl ester type epoxy resin, the reaction is carried out for 15 hours at 50 ℃, and isocyanate groups react with hydroxyl groups on the terpene-type epoxy resin to form terpene-type epoxy polyurethane prepolymer.
Example 7
(1) 13.6G of alpha-terpinene is dissolved in 10ml of tetrahydrofuran, 9.8g of maleic anhydride and 0.136g of di-tert-butyl peroxide as a catalyst are added, and the mixture is reacted at 50 ℃ for 12 hours to produce a terpene maleic anhydride compound.
(2) After the reaction (1) is finished, 9.5g of epichlorohydrin and 0.01g of Pr (naph) catalyst 3-Al(i-Bu)3 g are added to react for 8 hours at 40 ℃ to generate the terpene-maleic anhydride glycidyl ester type epoxy resin, namely the novel terpene type epoxy resin.
(3) To the resulting terpene-maleic anhydride glycidyl ester type epoxy resin, 16.8g of hexamethylene diisocyanate was added, 0.084g of N-ethylmorpholine as a catalyst was added, and the reaction was carried out at 50℃for 15 hours, and isocyanate group reacted with a hydroxyl group on the terpene type epoxy resin to form a terpene type epoxy polyurethane prepolymer.
Example 8
(1) 13.6G of alpha-terpinene is dissolved in 10ml of tetrahydrofuran, 9.8g of maleic anhydride and 0.136g of phosphoric acid as a catalyst are added, and the mixture is reacted at 50 ℃ for 12 hours to produce a terpene maleic anhydride compound.
(2) After the reaction (1) is finished, 9.5g of epichlorohydrin and 0.095g of tetraethyl ammonium bromide serving as a catalyst are added to react for 8 hours at 40 ℃ to generate terpene-maleic anhydride glycidyl ester type epoxy resin, namely the novel terpene-type epoxy resin.
(3) To the resulting terpene-maleic anhydride glycidyl ester type epoxy resin, 16.8g of tetramethyl xylylene diisocyanate was added, 0.168g of dibutyltin dilaurate as a catalyst was added, and the reaction was carried out at 50℃for 15 hours, and isocyanate groups were reacted with hydroxyl groups on the terpene type epoxy resin to form a terpene type epoxy polyurethane prepolymer.
Example 9
(1) 13.6G of alpha-terpinene is dissolved in 10ml of tetrahydrofuran, 9.8g of maleic anhydride and 0.028g of phosphomolybdic acid as a catalyst are added, and the mixture is reacted at 50 ℃ for 12 hours to produce a terpene maleic anhydride compound.
(2) After the reaction (1) is finished, 9.5g of epoxy chloropropane and 0.01g of catalyst tetraethylammonium bromide are added for reaction for 8 hours at 40 ℃ to generate terpene-maleic anhydride glycidyl ester type epoxy resin, namely the novel terpene type epoxy resin.
(3) To the resulting terpene-maleic anhydride glycidyl ester type epoxy resin, 25g of methylenebis (4-cyclohexyl isocyanate) was added, 0.125g of dibutyltin dilaurate as a catalyst was added, and the reaction was carried out at 50℃for 15 hours, and isocyanate groups were reacted with hydroxyl groups on the terpene type epoxy resin to form a terpene type epoxy polyurethane prepolymer.
Example 10
20 Parts of terpene type epoxy resin prepolymer containing isocyanate groups (terpene type epoxy polyurethane prepolymer prepared in example 1), 10 parts of naphthenic oil, 5 parts of furfural extract oil, 15 parts of terpene resin, 0.7 part of accelerator TMTD and 0.4 part of antioxidant AW are pre-blended, the blending temperature is 40 ℃, blending is carried out for 30min, and the mixture is added into 50 parts of 70# matrix asphalt in a flowing state, and the mixture is stirred into a material A. 20 parts of polyether polyol and 5 parts of dimer fatty acid polyamide are blended for 30 minutes at 40 ℃, and after blending, the mixture is added into 50 parts of 70# matrix asphalt in a flowing state, and the mixture is stirred into a material B. When in use, the material A and the material B are subjected to shearing for 60min and curing for 30min at 160 ℃ to obtain the novel polyurethane modified asphalt. Fig. 2 is a fluorescent image of the novel polyurethane modified asphalt, and it can be seen from the image that the polyurethane has good compatibility in the asphalt.
Example 11
A novel polyurethane modified asphalt was prepared as in example 10, except that: the terpene type epoxy resin prepolymer having an isocyanate group was replaced with the terpene type epoxy resin prepolymer prepared in example 2.
Example 12
A novel polyurethane modified asphalt was prepared as in example 10, except that: the terpene type epoxy resin prepolymer having an isocyanate group was replaced with the terpene type epoxy resin prepolymer prepared in example 3.
Example 13
A novel polyurethane modified asphalt was prepared as in example 10, except that: the terpene type epoxy resin prepolymer having an isocyanate group was replaced with the terpene type epoxy resin prepolymer prepared in example 4.
Example 14
A novel polyurethane modified asphalt was prepared as in example 10, except that: the terpene type epoxy resin prepolymer having an isocyanate group was replaced with the terpene type epoxy resin prepolymer prepared in example 5.
Example 15
A novel polyurethane modified asphalt was prepared as in example 10, except that: the terpene type epoxy resin prepolymer having an isocyanate group was replaced with the terpene type epoxy resin prepolymer prepared in example 6.
Example 16
A novel polyurethane modified asphalt was prepared as in example 10, except that: the terpene type epoxy resin prepolymer having an isocyanate group was replaced with the terpene type epoxy resin prepolymer prepared in example 7.
Example 17
A novel polyurethane modified asphalt was prepared as in example 10, except that: the terpene type epoxy resin prepolymer having an isocyanate group was replaced with the terpene type epoxy resin prepolymer prepared in example 8.
Example 18
A novel polyurethane modified asphalt was prepared as in example 10, except that: the terpene type epoxy resin prepolymer having an isocyanate group was replaced with the terpene type epoxy resin prepolymer prepared in example 9.
Example 19
15 Parts of terpene type epoxy resin prepolymer containing isocyanate groups (prepared in example 1), 10 parts of palm oil, 5 parts of furfural extract oil, 15 parts of rosin resin, 0.7 part of accelerator TMTD and 0.4 part of anti-aging agent A are pre-blended, the blending temperature is 40 ℃, the blending is carried out for 30min, and the mixture is added into 50 parts of 70# matrix asphalt in a flowing state, and the mixture is stirred into the material A. 20 parts of polyester polyol and 5 parts of dimer fatty acid polyamide are blended for 30 minutes at 40 ℃, and after blending, the mixture is added into 50 parts of 70# matrix asphalt in a flowing state, and the mixture is stirred into a material B. When in use, the material A and the material B are subjected to shearing for 60min and curing for 30min at 160 ℃ to obtain the novel polyurethane modified asphalt, and the performance of the modified asphalt is tested.
Example 20
20 Parts of terpene type epoxy resin prepolymer containing isocyanate groups (prepared in example 1), 10 parts of naphthenic oil, 5 parts of tung oil, 15 parts of petroleum resin, 0.7 part of accelerator dibenzothiazyl disulfide and 0.4 part of anti-aging agent D are pre-blended, the blending temperature is 40 ℃, the blending is carried out for 30min, and the mixture is added into 50 parts of 70# matrix asphalt in a flowing state, and the mixture is stirred into a material A. 20 parts of polyether polyol and 5 parts of dimer fatty acid polyamide are blended for 30 minutes at 40 ℃, and after blending, the mixture is added into 50 parts of 70# matrix asphalt in a flowing state, and the mixture is stirred into a material B. When in use, the material A and the material B are subjected to shearing for 60min and curing for 30min at 160 ℃ to obtain the novel polyurethane modified asphalt.
Example 21
15 Parts of terpene type epoxy resin prepolymer containing isocyanate groups (prepared in example 1), 10 parts of epoxidized soybean oil, 5 parts of palm oil, 15 parts of phenolic resin, 0.7 part of accelerator TMTD and 0.4 part of antioxidant IPPD are pre-blended at a temperature of 40 ℃ for 30min, and added into 50 parts of 70# matrix asphalt in a flowing state after blending, and the mixture is stirred into a material A. 20 parts of polyether polyol and 5 parts of dimer fatty acid polyamide are blended for 30 minutes at 40 ℃, and after blending, the mixture is added into 50 parts of 70# matrix asphalt in a flowing state, and the mixture is stirred into a material B. When in use, the material A and the material B are subjected to shearing for 60min and curing for 30min at 180 ℃ to obtain the novel polyurethane modified asphalt.
Example 22
20 Parts of terpene type epoxy resin prepolymer containing isocyanate groups (prepared in example 1), 10 parts of castor oil, 5 parts of furfural extract oil, 15 parts of lignin, 0.7 part of accelerator zinc diethyl dithiocarbamate and 0.4 part of antioxidant PPD are pre-blended, the blending temperature is 40 ℃, blending is carried out for 30min, and the mixture is added into 50 parts of 70# matrix asphalt in a flowing state, and the mixture is stirred into a material A. 20 parts of polyester polyol and 5 parts of dimer fatty acid polyamide are blended for 30 minutes at 40 ℃, and after blending, the mixture is added into 50 parts of 70# matrix asphalt in a flowing state, and the mixture is stirred into a material B. When in use, the material A and the material B are subjected to shearing for 60min and curing for 30min at 150 ℃ to obtain the novel polyurethane modified asphalt.
Example 23
15 Parts of terpene type epoxy resin prepolymer containing isocyanate groups (prepared in example 1), 10 parts of epoxidized soybean oil, 5 parts of furfural extract oil, 15 parts of coumarone resin, 0.7 part of accelerator TMTM and 0.4 part of antioxidant AW are pre-blended, the blending temperature is 40 ℃, blending is carried out for 30min, and the mixture is added into 50 parts of 70# matrix asphalt in a flowing state, and the mixture is stirred into a material A. 20 parts of polyether polyol and 5 parts of dimer fatty acid polyamide are blended for 30 minutes at 40 ℃, and after blending, the mixture is added into 50 parts of 70# matrix asphalt in a flowing state, and the mixture is stirred into a material B. When in use, the material A and the material B are subjected to shearing for 60min and curing for 30min at 160 ℃ to obtain the novel polyurethane modified asphalt.
Example 24
10 Parts of terpene type epoxy resin prepolymer containing isocyanate groups (prepared in example 1), 5 parts of naphthenic oil, 5 parts of furfural extract oil, 5 parts of terpene resin, 0.5 part of accelerator TMTD and 0.2 part of antioxidant AW are pre-blended, the blending temperature is 40 ℃, the blending is carried out for 30min, and the mixture is added into 50 parts of 70# matrix asphalt in a flowing state and is stirred into a material A. 10 parts of polyether polyol and 2 parts of dimer fatty acid polyamide are blended for 30 minutes at 40 ℃, and after blending, the mixture is added into 50 parts of 70# matrix asphalt in a flowing state, and the mixture is stirred into a material B. When in use, the material A and the material B are subjected to shearing for 60min and curing for 30min at 160 ℃ to obtain the novel polyurethane modified asphalt.
Example 25
30 Parts of terpene type epoxy resin prepolymer containing isocyanate groups (prepared in example 1), 10 parts of naphthenic oil, 10 parts of furfural extract oil, 20 parts of terpene resin, 1 part of accelerator TMTD and 0.8 part of antioxidant AW are pre-blended, the blending temperature is 40 ℃, the blending is carried out for 30min, and the mixture is added into 50 parts of 70# matrix asphalt in a flowing state, and the mixture is stirred into a material A. 30 parts of polyether polyol and 8 parts of dimer fatty acid polyamide are blended for 30 minutes at 40 ℃, and after blending, the mixture is added into 50 parts of 70# matrix asphalt in a flowing state, and the mixture is stirred into a material B. When in use, the material A and the material B are subjected to shearing for 60min and curing for 30min at 160 ℃ to obtain the novel polyurethane modified asphalt.
Comparative example 1
(1) 9.8G of maleic anhydride was dissolved in 10ml of tetrahydrofuran, and 9.5g of epichlorohydrin and 0.08g of tetraethylammonium bromide as a catalyst were added to react for 8 hours at 40℃to obtain a glycidyl ester type epoxy resin of maleic anhydride.
(2) To the resulting glycidyl maleic anhydride ester type epoxy resin was added 25gMDI (diphenylmethane diisocyanate), and 0.15g of dibutyltin dilaurate as a catalyst was added to react at 50℃for 15 hours to form an epoxy polyurethane prepolymer.
(3) 20 Parts of alpha-terpinene, 20 parts of epoxy polyurethane prepolymer, 10 parts of naphthenic oil, 5 parts of furfural extract oil, 15 parts of terpene resin, 0.7 part of accelerator TMTD and 0.4 part of anti-aging agent AW are pre-blended, the blending temperature is 40 ℃, the blending is carried out for 30 minutes, and the mixture is added into 50 parts of 70# matrix asphalt in a flowing state, and the mixture is stirred into the material A. 20 parts of polyether polyol and 5 parts of dimer fatty acid polyamide are blended for 30 minutes at 40 ℃, and after blending, the mixture is added into 50 parts of 70# matrix asphalt in a flowing state, and the mixture is stirred into a material B. When in use, the material A and the material B are subjected to shearing for 60min and curing for 30min at 160 ℃ to obtain the modified asphalt.
Comparative example 2
Dehydrating 40 parts of polyethylene glycol (average molecular weight is 600) at 120 ℃ under vacuum and under the pressure of more than 0.95MPa for 3 hours, cooling to 65 ℃, adding 60 parts of toluene diisocyanate monomer and 20 parts of maleic anhydride, stirring for 0.5 hours, then heating to 85 ℃, continuing to react for 3-4 hours, and cooling to 55 ℃ to obtain the prepolymer. 20 parts of prepolymer, 10 parts of naphthenic oil, 5 parts of furfural extract oil, 15 parts of terpene resin, 0.7 part of accelerator TMTD and 0.4 part of anti-aging agent AW are pre-blended, the blending temperature is 40 ℃, the mixture is blended for 30 minutes, and the mixture is added into 50 parts of 70# matrix asphalt in a flowing state, and the mixture is stirred into a material A. 20 parts of polyether polyol and 5 parts of dimer fatty acid polyamide are blended for 30 minutes at 40 ℃, and 50 parts of 70# matrix asphalt is added after blending, and the mixture is stirred into a material B. When in use, the material A and the material B are subjected to shearing for 60min and curing for 30min at 160 ℃ to obtain the polyurethane modified asphalt.
Comparative example 3
Polyurethane modified asphalt was prepared as in example 10, except that: the cross-linking agent was replaced with MOCA (MOCA).
Comparative example 4
Polyurethane modified asphalt was prepared as in example 10, except that: the terpene type epoxy resin prepolymer containing isocyanate groups was replaced with a commercially available bisphenol a type epoxy resin.
The properties of the modified asphalt prepared in the above examples and comparative examples were tested and the results are shown in table 1 below. The penetration is tested according to the method in GB/T0604, the ductility is tested according to the method in GB/T0605, the softening point is tested according to the method in GB/T0606, and the dynamic viscosity at 60 ℃ is tested according to the method in GB/T0620.
TABLE 1
Wherein, penetration, ductility and softening point reflect the mechanical properties of the modified asphalt. The lower penetration indicates a higher rutting resistance of the modified asphalt; the higher the ductility is, the higher the low-temperature cracking resistance of the modified asphalt is; the higher softening point indicates the higher high temperature performance of the modified asphalt. As can be seen from the results of Table 1, the modified asphalt prepared in examples 10 to 25 of the present invention had higher mechanical properties than the modified asphalt of each comparative example, wherein the modified asphalt of example 10 had the best properties.
The foregoing is only a partial embodiment of the present invention, and it should be noted that it will be apparent to those skilled in the art that modifications and adaptations can be made without departing from the principles of the present invention, and such modifications and adaptations are intended to be comprehended within the scope of the present invention.
Claims (8)
1. A modified asphalt is characterized in that: the material is prepared from a material A and a material B, wherein the material A comprises the following components in parts by weight: 50 parts of matrix asphalt, 10-30 parts of terpene epoxy polyurethane prepolymer, 5-20 parts of compatilizer, 5-20 parts of resin, 0.5-1 part of accelerator and 0.2-0.8 part of anti-aging agent; the material B comprises the following components in parts by weight: 50 parts of matrix asphalt, 10-30 parts of polyether polyol or polyester polyol and 2-8 parts of cross-linking agent; the cross-linking agent is dimer fatty acid polyamide;
the preparation method of the terpene type epoxy polyurethane prepolymer comprises the following steps:
(1) Mixing alpha-terpinene, maleic anhydride, a catalyst and a polar solvent, and then reacting to generate a terpene maleic anhydride compound;
(2) Adding a catalyst into epoxy chloropropane and a terpene maleic anhydride compound in a polar solvent to react to generate terpene epoxy resin;
(3) Adding isocyanate into terpene epoxy resin, and reacting isocyanate groups with hydroxyl groups on the terpene epoxy resin in the presence of a catalyst to obtain a terpene epoxy polyurethane prepolymer;
In the step (1), the molar ratio of the alpha-terpinene to the maleic anhydride is 1:1; in the step (2), the molar ratio of the alpha-terpinene to the epichlorohydrin is 1: adding epichlorohydrin in a relation of 1.01-1.05; in the step (3), the molar ratio of the epichlorohydrin to the isocyanate is 1: adding isocyanate in a relation of 0.8-1; in the step (3), the isocyanate is one or more of isophorone diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, methylenebis (4-cyclohexyl isocyanate) and tetramethylxylylene diisocyanate.
2. The modified asphalt according to claim 1, wherein: in the step (1), the catalyst is one or more of di-tert-butyl peroxide, phosphoric acid, p-toluenesulfonic acid and phosphomolybdic acid; in the step (2), the catalyst is one or more of zinc glutarate, pr (naph) 3-Al (i-Bu) 3 and tetraethylammonium bromide; in the step (3), the catalyst is one or more of dibutyl tin dilaurate, dimethylaminoethyl ether and N-ethylmorpholine.
3. The modified asphalt according to claim 1 or 2, characterized in that: in the step (1), the mass ratio of the alpha-terpinene to the catalyst is 1:0.002-0.01; in the step (2), the mass ratio of the epichlorohydrin to the catalyst is 1:0.001-0.01; in the step (3), the mass ratio of isocyanate to catalyst is 1:0.005-0.01.
4. The modified asphalt according to claim 1, wherein: in the steps (1) and (2), the polar solvent is one or more of tetrahydrofuran, toluene and 1, 4-dioxane.
5. The modified asphalt according to claim 1, wherein: in the step (1), the reaction temperature is 40-70 ℃ and the reaction time is 10-15 h; in the step (2), the reaction temperature is 20-60 ℃ and the reaction time is 8-15 h; in the step (3), the reaction temperature is 30-70 ℃ and the reaction time is 10-20 h.
6. The modified asphalt according to claim 1, wherein: the compatilizer comprises one or more of naphthenic oil, furfural extract oil, palm oil, tung oil, castor oil and epoxidized soybean oil; the resin comprises one or more of phenolic resin, petroleum resin, rosin resin, terpene resin and coumarone resin; the accelerator comprises one or more of TMTD, TMTM, zinc diethyl dithiocarbamate and dibenzothiazyl disulfide; the anti-aging agent comprises one or more of an anti-aging agent AW, an anti-aging agent A, an anti-aging agent D, an anti-aging agent IPPD and an anti-aging agent PPD.
7. A method for preparing the modified asphalt of claim 1, comprising the steps of:
(1) Heating matrix asphalt to a flowing state, adding terpene type epoxy polyurethane prepolymer, compatilizer, resin, accelerator and anti-aging agent into the matrix asphalt under a shearing condition, and uniformly mixing to form a material A;
(2) Heating the matrix asphalt to a flowing state, adding the polymer polyol and the cross-linking agent into the matrix asphalt under the shearing condition, and uniformly mixing to form a material B;
(3) When in use, the material A and the material B are mixed, sheared and solidified to obtain the modified asphalt.
8. The method for preparing the composite material according to claim 7, wherein: in the step (3), after the material A and the material B are mixed, shearing is carried out for 30-60 min at 110-160 ℃, and then curing is carried out for 10-50 min at 110-160 ℃.
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