CN1837290A - Thermosetting epoxy asphalt materials for pavement and bridge and process for preparing same - Google Patents
Thermosetting epoxy asphalt materials for pavement and bridge and process for preparing same Download PDFInfo
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- CN1837290A CN1837290A CN 200610039988 CN200610039988A CN1837290A CN 1837290 A CN1837290 A CN 1837290A CN 200610039988 CN200610039988 CN 200610039988 CN 200610039988 A CN200610039988 A CN 200610039988A CN 1837290 A CN1837290 A CN 1837290A
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- acid
- anhydride
- pavement
- bridge
- thermosetting epoxy
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- 239000004593 Epoxy Substances 0.000 title claims abstract description 61
- 239000000463 material Substances 0.000 title claims abstract description 61
- 239000010426 asphalt Substances 0.000 title claims description 71
- 229920001187 thermosetting polymer Polymers 0.000 title claims description 30
- 238000004519 manufacturing process Methods 0.000 title description 2
- 239000002253 acid Substances 0.000 claims abstract description 24
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 11
- 239000000194 fatty acid Substances 0.000 claims abstract description 11
- 229930195729 fatty acid Natural products 0.000 claims abstract description 11
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 11
- 150000008065 acid anhydrides Chemical group 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 7
- 239000011295 pitch Substances 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 16
- 150000008064 anhydrides Chemical group 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 238000010792 warming Methods 0.000 claims description 14
- 125000001931 aliphatic group Chemical group 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 10
- -1 methyl carbic anhydride Chemical compound 0.000 claims description 10
- 229920005989 resin Polymers 0.000 claims description 10
- 239000011347 resin Substances 0.000 claims description 10
- 239000006185 dispersion Substances 0.000 claims description 8
- 239000011301 petroleum pitch Substances 0.000 claims description 7
- 150000001336 alkenes Chemical class 0.000 claims description 6
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 6
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 6
- 229920002367 Polyisobutene Polymers 0.000 claims description 5
- 239000011159 matrix material Substances 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- RINCXYDBBGOEEQ-UHFFFAOYSA-N succinic anhydride Chemical compound O=C1CCC(=O)O1 RINCXYDBBGOEEQ-UHFFFAOYSA-N 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 4
- VANNPISTIUFMLH-UHFFFAOYSA-N glutaric anhydride Chemical compound O=C1CCCC(=O)O1 VANNPISTIUFMLH-UHFFFAOYSA-N 0.000 claims description 4
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 claims description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 3
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 3
- 239000011294 coal tar pitch Substances 0.000 claims description 3
- 230000003301 hydrolyzing effect Effects 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 229920000141 poly(maleic anhydride) Polymers 0.000 claims description 3
- 239000002383 tung oil Substances 0.000 claims description 3
- WVRNUXJQQFPNMN-VAWYXSNFSA-N 3-[(e)-dodec-1-enyl]oxolane-2,5-dione Chemical compound CCCCCCCCCC\C=C\C1CC(=O)OC1=O WVRNUXJQQFPNMN-VAWYXSNFSA-N 0.000 claims description 2
- 238000005698 Diels-Alder reaction Methods 0.000 claims description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 2
- HCPOCMMGKBZWSJ-UHFFFAOYSA-N ethyl 3-hydrazinyl-3-oxopropanoate Chemical compound CCOC(=O)CC(=O)NN HCPOCMMGKBZWSJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000003822 epoxy resin Substances 0.000 abstract description 5
- 229920000647 polyepoxide Polymers 0.000 abstract description 5
- 229920000180 alkyd Polymers 0.000 abstract 1
- 239000000539 dimer Substances 0.000 abstract 1
- 239000004519 grease Chemical group 0.000 abstract 1
- 239000000126 substance Substances 0.000 description 15
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- 230000004048 modification Effects 0.000 description 10
- 238000012986 modification Methods 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 8
- 239000011384 asphalt concrete Substances 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 125000003700 epoxy group Chemical group 0.000 description 6
- 230000013011 mating Effects 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 239000004110 Zinc silicate Substances 0.000 description 4
- 239000004567 concrete Substances 0.000 description 4
- 239000004922 lacquer Substances 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- XSMMCTCMFDWXIX-UHFFFAOYSA-N zinc silicate Chemical compound [Zn+2].[O-][Si]([O-])=O XSMMCTCMFDWXIX-UHFFFAOYSA-N 0.000 description 4
- 235000019352 zinc silicate Nutrition 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 229920000768 polyamine Polymers 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000000498 cooling water Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VHOQXEIFYTTXJU-UHFFFAOYSA-N Isobutylene-isoprene copolymer Chemical group CC(C)=C.CC(=C)C=C VHOQXEIFYTTXJU-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000004523 agglutinating effect Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000011243 crosslinked material Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 150000002689 maleic acids Chemical class 0.000 description 1
- 125000005395 methacrylic acid group Chemical class 0.000 description 1
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 1
- 241000345420 miki group Species 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000002913 oxalic acids Chemical class 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 239000012815 thermoplastic material Substances 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
- Road Paving Structures (AREA)
Abstract
The invention discloses a bridge heat fixed epoxy tar material and preparing method, which consists of A and B, wherein A part quality component is 60-76 modified tar with carboxy group or acid anhydride, grease group diacid, 11-25 dimer acid or alkyd resin, 10-25 fatty acid and 0.05-0.65 solidifying celeratist; B is epoxy resin; the quality rate of A and B is 2:1-8:1. The invention possesses high strength and good flexibility, which is fit for higher occasion.
Description
Technical field
The present invention relates to a kind of chemical modified bitumen.
Background technology
Pitch as paving the way and water-proof material, belongs to a kind of thermoplastic material usually in essence.This property list is used the road surface of asphalt paving now, in summer high-temperature season, the road surface is prone to rut under the heavy lift effect, in cold season in winter, be prone to warm draw seam, along with the raising of road quality classification and the generally employing of large-span steel box-beam structure bridge, intensity, deformation stability and the fatigue durability etc. of pavement material have been proposed very high requirement, high agglutinating value(of coal) and particular requirement such as waterproof have been proposed again on use properties simultaneously.As the important component part of bridge car system, the quality of deck paving directly has influence on traveling security, comfortableness, bridge durability and economic benefit of investment.Obviously, so high performance requriements is that plain asphalt institute is incompetent, must use modifying asphalt.
The method of asphalt modification is more, and great majority are to adopt the method for polymer modification to reduce the bituminous temperature sensitivity.In CN1364823, provided with organic graft materials and/or linked and produced rubber modified asphalt material; Provided among the CN1415663A with rich fragrant poor wax component and thermoplastic elastomer and made the parent that is rich in polymkeric substance, make finely dispersed bituminous composition with this parent and basic asphalt, and add the composite additive that accounts for pitch total amount 0.1-0.5%, make the road bitumen product of polymer modification; CN1106597 has provided a kind of with the motorway of Resins, epoxy and the preparation of proper curing agents modifying asphalt thereof and the bituminous epoxy with high strength, high ductibility that bridge is used.Provided among the USP5348994 pitch, isoprene-isobutylene rubber, SBS and the sulfonated terpolymer EP rubber that contain sulfonate or sulfonic acid group and+modifying asphalt that the positively charged ion neutralizing agent of 1～+ 3 valency prepares, the road surface of laying this kind material has improved visco-elasticity, softening temperature raises, the stable storing property improvement; USP64114056 has provided the coupling joint group of handling with Tripyrophosphoric acid and the super phosphoric acid modifying asphalt of assigning to and has obtained high use temperature; USP6399680 has provided with the sulfuric acid of the 0.02-3% of modifying asphalt total amount, phosphoric acid, Glacial acetic acid or nitric acid and has done promotor, contains the modifying asphalt that the multipolymer of epoxy group(ing) of the 0.2-15% of modifying asphalt total amount is made; USP5574095 has provided with containing the multipolymer of epoxide group and the asphalt component of modified polyamine; USP5604274 has provided the pitch that total amount 4-30% contains the polymer modification of epoxide group and has made the A component, the B component is the pitch with amine, acid anhydrides, alcohol, carboxylic acid and thiocarbamide modification, A and B mix as pavement material, A component 80-95% wherein, B component 5-20%, the polymkeric substance that contains epoxide group forms external phase in pitch, obtain having the pitch of thermosetting performance thus; Provided among the USP4162998 with polyamines and epoxy resin modification bituminous method; USP5576363 has provided the method for preparing the two-pack modified asphalt material with modifications such as multipolymer that contains epoxide group and carboxylic acids.
Generally speaking, all be to use polymer modified asphalt both at home and abroad, domestic mainly by filler and cross-linked material modifying asphalt, be helpful to improving bituminous use temperature and elasticity; But, all be thermoplastic modification in essence, can not fundamentally change bituminous visco-elasticity essence, be difficult to satisfy the requirement of mating formation of Longspan Bridge; Research about bituminous epoxy is at the early-stage, does not also relate to the key request in the application such as control working life.The external Resins, epoxy that adopts comes the patent of modifying asphalt also more, from trend, be use with bitumen compatibility preferably monomer and the monomer copolymerization that contains epoxide group obtain having the Resins, epoxy of better consistency with pitch, simultaneously to asphalt modification with adopt polyamines class solidifying agent; The thermoset pitch of this class patent preparation often is partial to as coating or roof waterpoof material, so also do not consider the pot life problems in engineering practice.
So-called " working life ", be meant thermosetting resin in solidification process, viscosity constantly increases, flowability variation gradually, up to can not use fully experienced at that time between.For the thermoset bitumen for road use, what at first will solve in engineering practice can control its solidified speed exactly to satisfy desired several times of construction:
(1) for bonding layer material, mix the time that is sprayed on road surface or the steel plate face from A, B two material, viscosity wants suitable low so that spray before require spraying, and viscosity will increase and form fast intensity provides requirement for paving of upper strata compound condition fast after spraying;
(2) for binder, mix adding from A, B two material and gather materials time of uniform mixing, require viscosity not too big in order to avoid influence uniform mixing, can not be too little in order to avoid can not bond and gather materials;
(3) mixture laying in (2) is finished the also time of compacting, require viscosity to rise to enough intensity fast in order to avoid influence compacting;
(4) wearing course (surface layer) epoxy asphalt concrete reaches the time of the desired initial strength of open to traffic, requires the viscosity rapid growth, so that come into operation fast.
For bonding layer material, be exactly the required time in above-mentioned (1) its working life, is generally 5-30 minute; For binder, be exactly the summation of above-mentioned (2)～(4) required time its working life, is generally 30～90 minutes.Be also referred to as the operating time this working life.
Summary of the invention
Thinking of the present invention is at first matrix pitch to be carried out functional modification, suc as formula 1, shown in the formula 2, making itself becomes a kind of curing agent for epoxy resin, the epoxy curing agent and the curing catalyst that then add other again mix the comprehensive curing system A part that forms Resins, epoxy, being used of multiple like this solidifying agent and curing catalyst makes that curing speed is controlled, the cured product performance is adjustable, can satisfy the different requirements under the various different conditions.
The mechanism synoptic diagram of formula 1 acid anhydrides modifying asphalt
The mechanism synoptic diagram of formula 2 carboxylic acid modifying asphalts
Heat cured bituminous epoxy has finally formed a kind of network structure of 3 D stereo behind curing reaction; Simultaneously, because the multiple solidifying agent that wherein contains is not quite similar with the reactive behavior of Resins, epoxy, cause reaction to interlock and carry out, thereby formed a kind of inierpeneirating network structure, the inierpeneirating network structure of this 3 D stereo provides theoretical foundation for its high strength and snappiness just.
In view of the above, the invention provides and have high strength, high-elongation and super fatigue performance, suitable operating time, can be used for Longspan Bridge and motorway epoxy bitumen material and preparation method thereof.
Technical scheme of the present invention is as follows:
A kind of thermosetting epoxy asphalt materials for pavement and bridge, it partly is made up of A part and B,
The quality group of A part becomes:
30～76 parts of the modifying asphalts of band carboxyl or anhydride group
11～55 parts of aliphatic dibasic acid, dimeracid or Synolac
10～25 parts of fatty acid anhydrides
0.05～0.65 part of curing catalyst
B partly is a Resins, epoxy, and the A part is 2: 1～8: 1 with the mass ratio of B part.
Above-mentioned thermosetting epoxy asphalt materials for pavement and bridge, the modifying asphalt of described band carboxyl or anhydride group are to make with the dienophile of the Diels-Alder reaction of band carboxyl or anhydride group and plain asphalt reaction.
Above-mentioned thermosetting epoxy asphalt materials for pavement and bridge, described plain asphalt can be petroleum pitch, oxidized bitumen, coal-tar pitch or lake pitch.
Above-mentioned thermosetting epoxy asphalt materials for pavement and bridge, described aliphatic dibasic acid, dimeracid or Synolac can be got wherein single a kind of, perhaps two or three mixture,
Above-mentioned thermosetting epoxy asphalt materials for pavement and bridge, described aliphatic dibasic acid can be oxalic acid, Succinic Acid, propanedioic acid or hexanodioic acid.
Above-mentioned thermosetting epoxy asphalt materials for pavement and bridge, described aliphatic dibasic acid can be single a kind of aliphatic dibasic acids, also can be the mixtures of two or more aliphatic dibasic acid.
Above-mentioned thermosetting epoxy asphalt materials for pavement and bridge, described fatty acid anhydride can be polyisobutylene butanedioic anhydride, methyl carbic anhydride (methylene radical Tetra Hydro Phthalic Anhydride in the methyl), modified methyl carbic anhydride, dodecenylsuccinic anhydride, tung oil acid anhydride, poly-nonane diacid acid anhydride, poly-Pyroglutaric acid, poly-oxalic acid acid anhydride or hydrolytic polymaleic anhydride.
Above-mentioned thermosetting epoxy asphalt materials for pavement and bridge, described fatty acid anhydride can be single a kind of fatty acid anhydrides, also can be the mixtures of two or more fatty acid anhydride.
Can change the performance of epoxy bitumen material to satisfy the different requirements under the different condition by the ratio of adjusting A each component partly.
Thermosetting epoxy asphalt materials for pavement and bridge preparation method of the present invention has two kinds:
By the quality of prescription, the matrix pitch that is warmed up to 90-140 ℃ is added reactor, add 2～12% cis-butenedioic anhydride or olefin(e) acid of asphalt quality, be warmed up to 140-160 ℃, kept 10-60 minute, treat pressure-stabilisation after, feeding N
2Make total pressure remain on 0.25-1MPa, react after 3-6 hour, slowly pressure release is to 0.1MPa, other component that adds the A part that is warming up to 90-140 ℃ in advance then, carry out pre-mixing, after finishing, mixing under the vacuum of 0.02～0.09MPa, took out 10～60 minutes, disperse just to obtain the A part by high speed dispersion machine tools such as colloidal mills more at last, during use, the A that requires temperature will be warmed up to, B two portions mixed on request are even, promptly get thermosetting epoxy asphalt materials for pavement and bridge of the present invention, can be sprayed within a certain period of time on road surface or the steel plate as the bituminous epoxy bonding layer material; If admix and gather materials according to certain bitumen aggregate ratio (general thermosetting epoxy asphalt materials for pavement and bridge is 4: 100～7: 100 with the ratio of building stones) again, can mat formation within a certain period of time on the road surface and compacting.
Quality by prescription, the matrix pitch that is warmed up to 90-140 ℃ is added reactor, 2～12% cis-butenedioic anhydride or the olefin(e) acid that add asphalt quality, be warmed up to 160-240 ℃ of back flow reaction 3-6 hour, during from adding cis-butenedioic anhydride or olefin(e) acid, reflux exchanger begins with 60-100 ℃ of condensate return, finish until reaction, other component that adds the A part that is warming up to 90-140 ℃ in advance then, carry out pre-mixing, disperse just to obtain the A part by high speed dispersion machine tools such as colloidal mills more at last, during use, the A that requires temperature will be warmed up to, B two portions mixed on request are even, promptly get thermosetting epoxy asphalt materials for pavement and bridge of the present invention, can be sprayed at the road within a certain period of time and or on the steel plate as the bituminous epoxy bonding layer material; Gather materials if admix according to certain bitumen aggregate ratio again, can mat formation within a certain period of time on the road surface and compacting.
Epoxy resin modified asphalt materials for highway excellent performance of the present invention, existing high intensity has good snappiness again, and the corresponding operating time can also be provided according to different requirements, can arbitrarily adjust simultaneously and satisfy the different performance requirement.Stability in storage is good, and corresponding epoxy asphalt concrete high-temperature stability is outstanding, and the fatigue performance excellence is applicable to the occasion that motorway and bridge etc. are had relatively high expectations, and also can be used for arterial street, motorbus bus stop and airstrip.
Embodiment
The present invention is further described below by specific embodiment, but embodiment all is not a limitation of the present invention.Embodiment 1: will be warmed up to 90-140 ℃ petroleum pitch (place of production: the Dan Jia temple) 57 parts (quality, down with) add reactors, add 1.14 parts of cis-butenedioic anhydrides, are warmed up to 150-155 ℃, treat pressure-stabilisation after, feed N
2, make total pressure remain on 0.25MPa, react after 4 hours, slowly pressure release is to 0.1MPa.Add 17.16 parts of oxalic acids, the polyisobutylene butanedioic anhydride (molecular-weight average: 5100 that is warming up to 90-140 ℃ in advance then, Changzhou radiance high-tech chemical industry company limited) 5 parts, poly-oxalic acid acid anhydride (molecular-weight average: 1500, Changzhou radiance high-tech chemical industry company limited) 0.24 part of 17.6 part, triethylamine, pre-mixing 30 minutes; And then obtain the A part by the colloidal mill high speed dispersion, add B part epoxy (E-51, Wuxi resin processing plant) in 2: 1 ratios at last and mix.This material can be used as the tack coat of mating formation and uses, and specific performance sees Table 1.
Embodiment 2: 57.3 parts in the petroleum pitch (U.S.'s shell) that will be warmed up to 90-140 ℃ adds reactor, adds 4 parts of cis-butenedioic anhydrides, is warmed up to 155-160 ℃ and treats, treat pressure-stabilisation after, feed N
2, make total pressure remain on 0.45MPa, react after 5 hours, slowly pressure release is to 0.1MPa.Add 15.13 parts of dimeracids (Zhejiang is forever in the chemical plant), 10 parts of hexanodioic acids, the polyisobutylene butanedioic anhydride (molecular-weight average 2400 that is warming up to 90-140 ℃ in advance then, Changzhou radiance high-tech chemical industry company limited) 3 parts, poly-nonane diacid acid anhydride (molecular-weight average 1200, Changzhou radiance high-tech chemical industry company limited) 0.57 part of 10 part, triethylamine, pre-mixing 30 minutes, obtain the A part by the colloidal mill high speed dispersion, during use A part and B part (Resins, epoxy E-51) are warming up to 120 ℃, and even by 4: 1 mixed.This material can be used as the tack coat of mating formation and uses, and concrete performance sees Table 1.
Embodiment 3: the petroleum pitch (U.S.'s shell) that will be warmed up to 90-140 ℃ adds reactor for 68 parts, add 8.2 parts of cis-butenedioic anhydrides, be warmed up to 230 ℃ of reactions, reflux with 80 ℃ of warm water simultaneously, react after 6 hours, with Synolac (trade mark 3370A, Sanmu Group Co., Ltd., Jiangsu) 14.4 part, 5 parts of methyl carbic anhydrides (Changzhou radiance high-tech chemical industry company limited), poly-Pyroglutaric acid (molecular-weight average 1200, Changzhou radiance high-tech chemical industry company limited) 7 part, join in the reactor for 0.6 part with diethylenetriamine, mix reaction 1h, at last compound colloidal mill high speed is disperseed to obtain the A part; During use, A part and B part (epoxy resin E-44) are warming up to 120 ℃, by 5: 1 mixed, this material can be used as the tack coat of mating formation and uses, and concrete performance sees Table 1.
Embodiment 4: the petroleum pitch (U.S.'s shell) that will be warmed up to 90-140 ℃ adds reactor for 64 parts, add 7.68 parts of methacrylic acids, be warmed up to 230 ℃, react after 6 hours, with the Synolac (trade mark 3880, Jiangsu Miki Group) 10 parts of 20.85 parts, modified methyl carbic anhydride (Changzhou radiance high-tech chemical industry company limited), 0.65 part of diethylenetriamine, mixes reaction 1h, again compound colloidal mill high speed is disperseed to obtain the A part; During use, with A part and B part (ethene-vinylbenzene-glytidyl methacrylate 1: 1: 1, molecular weight: 2000, Changzhou radiance high-tech chemical industry company limited) is warming up to 120 ℃, by 8: 1 mixed, this material can be used as the tack coat of mating formation and uses, and concrete performance sees Table 1.
Embodiment 5: 27 parts in the petroleum pitch (U.S.'s shell) that will be warmed up to 90-140 ℃ adds reactor, adds 3 parts of cis-butenedioic anhydrides, is warmed up to 150-155 ℃, keeps 20 minutes, treat pressure-stabilisation after, feeding N
2, make total pressure remain on 0.25MPa; React after 4 hours, slowly pressure release is to 0.1MPa.Add 25 parts of 10.45 parts of Succinic Acid, dimeracids, the polyisobutylene butanedioic anhydride (molecular-weight average: 3700 that is warming up to 90-140 ℃ in advance then, Changzhou radiance high-tech chemical industry company limited) (molecular-weight average: 1500) 19.5 parts and triethylamine are 0.05 part for 5 parts, poly-oxalic acid acid anhydride, pre-mixing 30 minutes was taken out under the vacuum of 0.05MPa 30 minutes after finishing; And then obtain the A part by the colloidal mill high speed dispersion, and in 2: 1 ratios the A part is mixed with B part epoxy (E-44), admix by 4.5% bitumen aggregate ratio again and gather materials, be incubated 50 minutes, carry out road pavement.Performance of material own and corresponding epoxy asphalt concrete performance see Table 2.
Embodiment 6: the coal-tar pitch (Shanxi permanent Dehua worker company limited) that will be warmed up to 90-140 ℃ adds reactors for 59.8 parts, adds 4 parts of cis-butenedioic anhydrides, is warmed up to 155-160 ℃, keeps 30 minutes, treat pressure-stabilisation after, feeding N
2, make total pressure remain on 0.45MPa; React after 5 hours, slowly pressure release is to 0.1MPa.Add 10 parts of 3 parts of 22.88 parts of dimeracids, tung oil acid anhydrides being warming up to 90-140 ℃ in advance, poly-nonane diacid acid anhydride (molecular-weight average: 1700, Changzhou radiance high-tech chemical industry company limited) and 0.32 part of pre-mixing of triethylamine 30 minutes then; And then obtain the A part by the colloidal mill high speed dispersion, during use A part and B partly be warming up to 120 ℃ and A is partly mixed with B part epoxy (ethene-vinylbenzene-methacrylic acid epoxy third fat 1: 1: 1) in 4: 1 ratios, admix by 5.5% bitumen aggregate ratio again and gather materials, be incubated 50 minutes, carry out road pavement.Performance of material own and corresponding epoxy asphalt concrete performance see Table 2.
Embodiment 7: the oxidized bitumen (prompt friendship farm six another arena oxidized bitumen factories in state-run) that will be warmed up to 90-140 ℃ adds reactor for 71 parts, add 5 parts of cis-butenedioic anhydrides, be warmed up to 230 ℃ of back flow reaction, reflux cooling water is with 80 ℃ of warm water, react after 6 hours, with 11.7 parts of hexanodioic acids, 5 parts of dodecenylsuccinic anhydrides, poly-Pyroglutaric acid (molecular-weight average 1200, Changzhou radiance high-tech chemical industry company limited) 0.3 part of 7 parts and diethylenetriamine add in the reactor and mix reaction 1h, at last compound are disperseed to obtain the A part in the colloidal mill high speed; During use, the A part is warming up to 120 ℃ with B part epoxy (E-51),, admixes by 6.5% bitumen aggregate ratio again and gather materials, be incubated 50 minutes, carry out road pavement by 5: 1 mixed.Performance of material own and corresponding epoxy asphalt concrete performance see Table 2.This material can be used as the tack coat of mating formation and uses, and concrete performance sees Table 2.
Embodiment 8: the Te Linida lake pitch (U.S.'s shell) that will be warmed up to 90-140 ℃ adds reactor for 64 parts, add 4.5 parts of maleic acids, be warmed up to 230 ℃ of back flow reaction, reflux cooling water is with 80 ℃ of warm water, react after 6 hours, 21.45 parts of Synolac, 5 parts of modified methyl carbic anhydrides, 5 parts of hydrolytic polymaleic anhydride and diethylenetriamine are joined in the reactor for 0.05 part, mix reaction 1h, at last compound is disperseed to obtain the A part in the colloidal mill high speed; During use, the A part is warming up to 120 ℃ with B part epoxy (E-51),, admixes by 6.5% bitumen aggregate ratio again and gather materials, be incubated 50 minutes, carry out road pavement by 8: 1 mixed.Performance of material own and corresponding epoxy asphalt concrete performance see Table 2.
Table 1 bituminous epoxy tack coat test-results
| Embodiment | Tensile strength (MPa) | Tension set (%) | 120 ℃ reach the 1000cP time (min) | Shearing resistance (MPa) | The rust-inhibiting paint model | 23 ℃ of cohesive strengths (MPa) |
| 6.9 7.2 8.8 10.2 | 250 240 210 180 | 28 24 20 14 | 5.52 5.4 6.8 8.7 | Inorganic zinc silicate epoxy zinc-rich lacquer inorganic zinc silicate epoxy zinc-rich lacquer inorganic zinc silicate epoxy zinc-rich lacquer inorganic zinc silicate epoxy zinc-rich lacquer | 1.56 2.50 1.60 2.82 1.69 3.01 1.78 3.12 |
Table 2 epoxy asphalt concrete test-results
| Embodiment | Tensile strength (MPa) | Tension set (%) | 120 ℃ reach the 1000cP time (min) | 60 ℃ of dynamic stabilities (inferior/mm) | Marshall stability (kN) | Flow valuve (mm) | Voidage (%) | Fatigue performance |
| 5 6 7 8 | 1.8 2.4 3.6 4.0 | 280 280 275 270 | 85 78 50 38 | ＞10000 | 58.0 61.6 49.8 65.7 | 3.79 4.02 4.12 3.98 | 2.6 2.9 2.4 2.7 | 6kN, 10Hz are sinusoidal wave to load 12,000,000 is undeformed |
Claims (10)
1. thermosetting epoxy asphalt materials for pavement and bridge is characterized in that it partly is made up of A part and B,
The quality group of A part becomes:
30～76 parts of the modifying asphalts of band carboxyl or anhydride group
11～55 parts of aliphatic dibasic acid, dimeracid or Synolac
10～25 parts of fatty acid anhydrides
0.05～0.65 part of curing catalyst
B partly is a Resins, epoxy, and the A part is 2: 1～8: 1 with the mass ratio of B part.
2. epoxy bridge thermoset bituminous material according to claim 1 is characterized in that: the modifying asphalt of described band carboxyl or anhydride group is that the dienophile and the plain asphalt reaction of the Diels-Alder reaction of mountain belts carboxyl or anhydride group makes.
3. epoxy bridge thermoset bituminous material according to claim 2 is characterized in that: described plain asphalt is petroleum pitch, oxidized bitumen, coal-tar pitch or lake pitch.
4. thermosetting epoxy asphalt materials for pavement and bridge according to claim 1 is characterized in that: described aliphatic dibasic acid, dimeracid or Synolac are got wherein single a kind of, perhaps two or three mixture,
5. thermosetting epoxy asphalt materials for pavement and bridge according to claim 1 and 2 is characterized in that: described aliphatic dibasic acid is oxalic acid, Succinic Acid, propanedioic acid or hexanodioic acid.
6. thermosetting epoxy asphalt materials for pavement and bridge according to claim 4 is characterized in that: described aliphatic dibasic acid is single a kind of aliphatic dibasic acid, or the mixture of two or more aliphatic dibasic acid.
7. thermosetting epoxy asphalt materials for pavement and bridge according to claim 1 is characterized in that: described fatty acid anhydride is polyisobutylene butanedioic anhydride, methyl carbic anhydride, modified methyl carbic anhydride, dodecenylsuccinic anhydride, tung oil acid anhydride, poly-nonane diacid acid anhydride, poly-Pyroglutaric acid, poly-oxalic acid acid anhydride or hydrolytic polymaleic anhydride.
8. thermosetting epoxy asphalt materials for pavement and bridge according to claim 6 is characterized in that: described fatty acid anhydride is single a kind of fatty acid anhydride, or the mixture of two or more fatty acid anhydride.
9. method for preparing the described thermosetting epoxy asphalt materials for pavement and bridge of claim 1, it is characterized in that: by the quality of prescription, the matrix pitch that is warmed up to 90-140 ℃ is added reactor, 2～12% cis-butenedioic anhydride or the olefin(e) acid that add asphalt quality, be warmed up to 140-160 ℃, kept 10-60 minute, treat pressure-stabilisation after, logical N
2Make total pressure remain on 0.25-1MPa, react after 3-6 hour, slowly pressure release is to 0.1MPa, obtain modifying asphalt, other component that adds the A part that is warming up to 90-140 ℃ in advance then, carry out pre-mixing, after finishing, mixing under the vacuum of 0.02～0.09MPa, took out 10～60 minutes, disperse just to obtain the A part by high speed dispersion machine tools such as colloidal mills more at last, during use, mixed is even on request with being warmed up to A, the B two portions that require temperature, promptly gets thermosetting epoxy asphalt materials for pavement and bridge.
10. method for preparing the described thermosetting epoxy asphalt materials for pavement and bridge of claim 1, it is characterized in that: by the quality of prescription, the matrix pitch that is warmed up to 90-140 ℃ is added reactor, 2～12% cis-butenedioic anhydride or the olefin(e) acid that add asphalt quality, be warmed up to 160-240 ℃ of back flow reaction 3-6 hour, during from adding cis-butenedioic anhydride or olefin(e) acid, reflux exchanger begins with 60-100 ℃ of condensate return, finish until reaction, other component that adds the A part that is warming up to 90-140 ℃ in advance then, carry out pre-mixing, disperse just to obtain the A part by high speed dispersion machine tools such as colloidal mills more at last, during use, the A that requires temperature will be warmed up to, B two portions mixed on request are even, promptly get thermosetting epoxy asphalt materials for pavement and bridge.
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