CN110713695A - Ultrahigh-toughness epoxy resin material for hot-mix epoxy asphalt and preparation method thereof - Google Patents
Ultrahigh-toughness epoxy resin material for hot-mix epoxy asphalt and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/5006—Amines aliphatic
- C08G59/5013—Amines aliphatic containing more than seven carbon atoms, e.g. fatty amines
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
Abstract
The invention discloses an ultra-high toughness epoxy resin material for hot-mix epoxy asphalt and a preparation method thereof. The technical scheme is as follows: the ultra-high toughness epoxy resin material for the hot-mix epoxy asphalt consists of a main agent A and a curing agent B; the main agent A comprises the following components: bisphenol A epoxy resin, flexible side chain-containing modified epoxy resin, reactive diluent and epoxy end-capping interface agent; the curing agent B comprises the following components in parts by weight: long chain fatty primary amines and accelerators; according to the invention, the cross-linking density of the epoxy cured material is controlled by synthesizing the monofunctional long-chain aliphatic primary amine, and the operable time of the hot-mixed epoxy asphalt material is more than 2 h; the compatibility problem between the asphalt phase and the epoxy phase is solved based on the technical principle of 'reaction induced phase separation'; by introducing the modified epoxy resin containing the flexible side chain, the fatigue resistance of the hot-mixed epoxy asphalt material is greatly improved.
Description
Technical Field
The invention relates to a hot-mix epoxy asphalt material, in particular to an ultra-high-toughness epoxy resin material for hot-mix epoxy asphalt and a preparation method thereof.
Background
In recent 20 years, the large-span steel box girder bridge in China enters a rapid construction period, however, the development speed of the large-span steel bridge deck pavement can not meet the actual use requirements of high temperature, heavy rain and heavy load in China, and the epoxy asphalt and other pavement materials introduced from abroad in the early stage are all found to have different degrees of diseases after being used for 3-5 years. In view of the strict requirements of high and low temperature performance and strict bending and pulling fatigue performance of steel bridge deck pavement, the epoxy asphalt is always the preferred material for paving large-span steel bridge decks at home and abroad due to the unique microstructure and wide performance plasticity.
The first major difficulty in preparing epoxy asphalt is solving the problem of long operable time at high temperature. By the American ChemCo company BIVThe representative warm-mixed epoxy asphalt adopts an anhydride curing agent, the viscosity of the warm-mixed epoxy asphalt at 120-130 ℃ is increased rapidly along with the curing time, the operation time is only about 45min, the warm-mixed epoxy asphalt is not beneficial to on-site construction, and the warm-mixed epoxy asphalt is gradually eliminated by domestic markets since 2010. In order to realize that the epoxy asphalt has longer operable time at high temperature, the patent CN 106832978B mixes amine curing agents such as polyether amine and the like with anhydride curing agents, although the problem of construction workability at high temperature is solved to a certain extent, the storage stability is almost not high, and the amine curing agents and the anhydride curing agents are easy to react to produce amide substances; on the other hand, the tensile strength of the epoxy asphalt cement prepared based on the patent at 23 ℃ is up to 7.4MPa, the Marshall stability of the corresponding mixture at 60 ℃ is over 100kN, both values exceed the actual use requirement range of steel bridge deck pavement, and the driving comfort is poor.
The second major difficulty in preparing epoxy asphalt is to solve the problem of compatibility between the epoxy resin phase and the asphalt phase. By American ChemCo company BIVThe preparation method comprises the following steps of carrying out a grafting reaction on maleic anhydride and unsaturated components in asphalt based on a Diels-Alder reaction, dissolving the grafted and modified asphalt into an anhydride curing agent based on a similar intermiscibility principle, and finally grafting asphalt molecules into an epoxy three-dimensional curing network, so that the compatibility between an epoxy phase and an asphalt phase is realized. No patent CN 104987737B, CN 104987735B, CN 105130278B, CN 105016655B takes effective measures to improve the compatibility between the epoxy phase and the asphalt phase. In the patents CN 103232717B and CN 106832978B, 1-15% of naphthalene oil or asphalt tar is added as a compatibilizer to improve the compatibility of an epoxy phase and an asphalt phase, and the naphthalene oil and the asphalt tar are high in toxicity and easy to precipitate, so that the long-term phase stability of a cured product is poor.
The third major difficulty in preparing epoxy asphalt is solving the fatigue life problem under high strain conditions. By the American ChemCo company BIVThe typical warm-mix epoxy asphalt enters the domestic market since 2002, but under the coupling effect of the domestic use conditions of high temperature, heavy rain, heavy load and the like, after 3-5 years of use, the pavement of the U-shaped rib is generally subjected to fatigue cracking, and the service life of the pavement is greatly reduced. The insufficient bending and pulling fatigue performance of the warm-mixed epoxy asphalt is closely related to the stability of the microstructure of the warm-mixed epoxy asphalt, the modified asphalt prepared by the Diels-Alder reaction in the warm-mixed epoxy asphalt is easy to generate the anti-Diels-Alder reaction under the coupling action of long-term heat, oxygen, load and the like, asphalt molecules with the softening action gradually get rid of the constraint of an epoxy curing network and are separated out from a cured product, and thus the cured product of the warm-mixed epoxy asphalt gradually becomes brittle and hard.
In view of the technical defects of the conventional epoxy asphalt material, the inventor of the present invention has actively researched and innovated based on practical experience and professional knowledge which are abundant for many years in the design and manufacture of such products and by using the theory, so as to create an ultra-high toughness epoxy resin material for hot-mix epoxy asphalt and a preparation method thereof, so that the epoxy resin material has high practicability. After continuous research and design and repeated trial production and improvement, the invention with practical value is finally created.
Disclosure of Invention
The invention aims to overcome the performance defects of the existing warm-mixed epoxy asphalt, and provides the ultra-high toughness epoxy resin material for the hot-mixed epoxy asphalt and the preparation method thereof, so that the construction time of the epoxy asphalt is prolonged, the problem of compatibility between the epoxy phase and the asphalt phase in the epoxy asphalt is solved, the bending and pulling fatigue properties of the epoxy asphalt are greatly improved, and the epoxy asphalt is more practical and has industrial utilization value.
The technical purpose of the invention is realized by the following technical scheme:
the ultrahigh-toughness epoxy resin material for the hot-mix epoxy asphalt comprises a main agent A and a curing agent B in a mass ratio of 100: 50-100, wherein the main agent A comprises the following components in parts by mass:
the curing agent B comprises the following components in percentage by mass:
95-99 parts of long-chain fatty primary amine
1-5 parts of an accelerator.
Further, the bisphenol A type epoxy resin is a mixture of any one or more of epoxy value of 0.42, 0.44, 0.51 and 0.54.
Furthermore, the modified epoxy resin containing the flexible side chain is prepared by the steps of firstly forming a semi-closed addition product by the addition reaction of polyethylene glycol monomethyl ether and toluene diisocyanate, and then carrying out the addition reaction of-NCO remained on the semi-closed addition product and secondary hydroxyl on the bisphenol A epoxy resin.
Furthermore, the polyethylene glycol monomethyl ether is any one or a mixture of more of MPEG-500, MPEG-750, MPEG-1000 and MPEG-2000.
Further, the reactive diluent is any one or a mixture of several of n-butyl glycidyl ether, phenyl glycidyl ether, butanediol diglycidyl ether, polyethylene glycol diglycidyl ether and polypropylene glycol diglycidyl ether.
Furthermore, the epoxy-terminated interface agent is any one or a mixture of more of 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane and 3-glycidoxypropylmethyldimethoxysilane.
Further, the long-chain fatty acid is any one or a mixture of more of 9,11, 13-octadecatrienoic acid, cis-12-hydroxyoctadecene-9-oic acid, cis-9, 12-octadecadienoic acid and all-cis-9, 12, 15-octadecatrienoic acid.
Further, the accelerator is any one or a mixture of more of 2,4, 6-tri (dimethylaminomethyl) phenol, triphenylphosphine, nonylphenol, phenol, triethanolamine, N-dimethylethanolamine and benzyl alcohol.
Further, the preparation method of the ultrahigh-toughness epoxy resin material for the hot-mix epoxy asphalt comprises the following steps:
s1, preparing modified epoxy resin containing flexible side chains;
s2, sequentially putting bisphenol A type epoxy resin, flexible side chain-containing modified epoxy resin, reactive diluent and epoxy end-capped interface agent into a reaction kettle for mixing to obtain a main agent A;
s3, preparing long-chain fatty primary amine;
s4, sequentially adding the long-chain aliphatic primary amine and the accelerator into a reaction kettle, and stirring and mixing to obtain a curing agent B;
s5, stirring and mixing the main agent A prepared in the S1 and the curing agent B prepared in the S2 to obtain the ultrahigh-toughness epoxy resin material for the hot-mix epoxy asphalt.
Further, the preparation method of the flexible side chain-containing modified epoxy resin comprises the following operation steps:
A1. n (polyethylene glycol monomethyl ether): slowly dripping polyethylene glycol monomethyl ether into a reaction kettle filled with toluene diisocyanate at the molar ratio of n (toluene diisocyanate) to 1:1, controlling the material temperature to be not more than 20 ℃ by using ice water in the dripping process, heating to 40-50 ℃ after finishing dripping, and continuously reacting for 3-5 hours to obtain a semi-closed addition product;
A2. putting bisphenol A epoxy resin and toluene into a reaction kettle according to the mass ratio of 1:1, and then adding n (bisphenol A epoxy resin): and (3) putting the prepared semi-closed addition product into a reaction kettle according to the molar ratio of n (semi-closed addition product) to 1:1, and reacting for 4-8 h at 60-80 ℃ under the catalytic action of dibutyltin dilaurate.
Further, the preparation method of the long-chain aliphatic primary amine comprises the following operation steps:
B1. as n (long chain fatty acid): putting long-chain fatty acid and liquid ammonia into a reaction kettle according to the molar ratio of n (liquid ammonia) to 1: 1-3, and reacting for 6-12 h at 300-350 ℃ and 0.2-0.6 MPa to prepare long-chain fatty amide;
B2. dehydrating the prepared fatty amide by using the circulation effect of ammonia gas generated by excessive liquid ammonia to prepare long-chain fatty nitrile;
B3. pumping the prepared long-chain aliphatic nitrile and ammonia water into a hydrogenation kettle according to the mass ratio of 1: 1-2, and adding n (long-chain aliphatic nitrile): adding hydrogen at a molar ratio of n (hydrogen) to 1:2, and reacting for 2-8 h at 120-180 ℃ under 2-6 MPa under the action of a molybdenum-containing three-way catalyst.
Furthermore, the preparation method of the ultra-high toughness epoxy resin material for the hot-mix epoxy asphalt comprises the following stirring process:
s2, stirring and mixing for 60-120 min at 40-80 ℃, wherein the stirring speed is 20-80 r/min;
s4, stirring and mixing for 30-60 min at the temperature of 30-60 ℃, wherein the stirring speed is 20-80 r/min;
s5, stirring and mixing for 3-10 min at 40-60 ℃, wherein the stirring speed is 20-80 r/min.
In conclusion, the invention has the following beneficial effects:
(1) the long-chain aliphatic primary amine synthesized by the invention is a monofunctional amine curing agent, and the cross-linking density of a three-dimensional curing network generated by the reaction of the long-chain aliphatic primary amine and epoxy resin in the early stage of mixing is lower, so that the ultrahigh-toughness epoxy resin material is ensured to be in a state of slowly rising viscosity within 2h before mixing; on the other hand, after the ultrahigh-toughness epoxy resin material and the low-viscosity hot asphalt are mixed according to the mass ratio of 1:1, the latter has a strong diluting effect on the former, so that the viscosity of the hot-mixed epoxy asphalt material within 2 hours before mixing is further ensured to meet the mixing requirement of the mixture.
(2) The invention solves the problem of compatibility between asphalt phase and epoxy phase based on the technical principle of 'reaction induced phase separation'. At the initial stage of mixing, uniformly dispersing asphalt particles in the ultra-high toughness epoxy resin material by using physical shearing force generated in the stirring process; with the gradual increase of the crosslinking density of the cured ultrahigh-toughness epoxy resin, the asphalt particles in the dispersed phase gradually lose the coalescence capability, and are further fixed in a curing network of the ultrahigh-toughness epoxy resin, and finally a two-phase structure taking the asphalt as the dispersed phase and the ultrahigh-toughness epoxy resin as a continuous phase is formed. Different from a metastable microstructure formed by warm-mixed epoxy asphalt, the hot-mixed epoxy asphalt prepared by the invention has excellent phase stability, and asphalt particles in a dispersed phase are firmly locked by an ultrahigh-toughness epoxy resin curing network.
(3) The modified epoxy resin containing flexible side chains synthesized by the invention can greatly increase the chain segment length between the three-dimensional network cross-linking points of the cured epoxy resin and reduce the cross-linking density of the three-dimensional network of the cured epoxy resin, thereby greatly improving the bending and pulling fatigue properties of the ultra-high toughness epoxy resin. On the other hand, the introduction of the modified epoxy resin containing the flexible side chain improves the flexibility of the cured epoxy resin at low temperature (such as minus 10 ℃), and further makes up for the defect of insufficient low-temperature toughness of the bisphenol A epoxy resin.
Drawings
FIG. 1 is a graph of Brookfield viscosity versus time at 170 ℃ for a hot-mix epoxy asphalt of the present invention;
FIG. 2 is a graph of stiffness/bending strain-loading times in a four-point bending fatigue test of the hot-mix epoxy asphalt mixture of the present invention.
Detailed Description
To further illustrate the technical means and effects adopted by the present invention to achieve the predetermined objects, the detailed description of the specific preparation method, characteristics and effects of the ultra-high toughness epoxy resin material for hot-mix epoxy asphalt according to the present invention is as follows.
Example 1: ultrahigh-toughness epoxy resin material for hot-mixed epoxy asphalt and preparation method thereof
The raw materials used in this example were as follows:
polyethylene glycol monomethyl ether: MPEG-1000, Haian petrochemical plant of Jiangsu province;
toluene diisocyanate: TDI-100, Hebei Cangzhou university group, Inc.;
bisphenol a type epoxy resin (I); DER331, Dow chemical, USA;
toluene: industrial grade, carnosine and petrochemical company, suzhou;
bisphenol a type epoxy resin (II): DER331, Dow chemical, USA;
phenyl glycidyl ether: XY690, New remote technologies, Inc., Anhui;
3-glycidyl ether oxypropyltrimethylsilane: silguesta-187, Mayer advanced materials, USA;
9,11, 13-octadecatrienoic acid: t160, reshment oil deep processing ltd, resil, Anhui province;
liquid ammonia: industrial grade, southern Tong Runfeng petrochemical Co., Ltd;
ammonia water: 25%, south Tong Runfeng petrochemical Co., Ltd;
hydrogen gas: industrial grade, Nanjing Shangyuan industrial gas plant;
2,4, 6-tris (dimethylaminomethyl) phenol: DMP-30, Shenzhen Jia Di Dy materials science and technology, Inc.
The preparation method of the ultrahigh-toughness epoxy resin material for the hot-mix epoxy asphalt comprises the following steps of:
(1) preparation of modified epoxy resin containing flexible side chain
N (polyethylene glycol monomethyl ether): slowly dripping polyethylene glycol monomethyl ether into a reaction kettle filled with toluene diisocyanate at the molar ratio of n (toluene diisocyanate) to 1:1, controlling the material temperature to be not more than 20 ℃ by using ice water in the dripping process, heating to 50 ℃ after finishing dripping, and continuously reacting for 4 hours to obtain the semi-closed addition product.
Putting bisphenol A type epoxy resin (I) and toluene into a reaction kettle according to the mass ratio of 1:1, and then adding n (bisphenol A type epoxy resin): and (3) putting the semi-closed adduct into a reaction kettle according to the molar ratio of n (semi-closed adduct) to 1:1, and reacting for 6h at 60 ℃ under the catalytic action of dibutyltin dilaurate to obtain the modified epoxy resin containing the flexible side chain.
(2) Preparation of super-high toughness epoxy resin main agent A
And (2) sequentially putting 60 parts of bisphenol A type epoxy resin (II), 30 parts of flexible side chain-containing modified epoxy resin prepared in the step (1), 9 parts of phenyl glycidyl ether and 1 part of 3-glycidyl ether oxypropyltrimethoxysilane into a reaction kettle, stirring and mixing at the stirring temperature of 70 ℃, the stirring speed of 80r/min and the stirring and mixing time of 90min to obtain the ultrahigh-toughness epoxy resin main agent A.
(3) Preparation of long-chain aliphatic primary amines
As n (long chain fatty acid): putting 9,11, 13-octadecatrienoic acid and liquid ammonia into a reaction kettle according to the molar ratio of 1:2, then reacting for 10 hours at 300 ℃ and 0.4MPa to obtain long-chain fatty amide, and synchronously dehydrating the long-chain fatty amide by utilizing the circulating action of ammonia gas to obtain the long-chain fatty nitrile.
Pumping the prepared long-chain aliphatic nitrile and ammonia water into a reaction kettle according to the mass ratio of 2:1, and then adding n (long-chain aliphatic nitrile): and (3) adding hydrogen according to the molar ratio of n (hydrogen) to 1:2, and reacting for 6 hours at 150 ℃ and 4MPa under the action of a molybdenum-containing ternary catalyst to obtain the long-chain aliphatic modified primary amine.
(4) Preparation of ultra-high toughness epoxy resin curing agent B
And (3) sequentially adding 99 parts of the long-chain aliphatic primary amine prepared in the step (3) and 1 part of the accelerator into a reaction kettle, stirring and mixing, wherein the stirring temperature is 30 ℃, the stirring speed is 60r/min, and the stirring and mixing time is 30min, so that the ultra-high-toughness epoxy resin curing agent B is obtained.
(5) Preparation of ultra-high toughness epoxy resin material
And (3) putting the ultra-high toughness epoxy resin main agent A prepared in the step (2) and the ultra-high toughness epoxy resin curing agent B prepared in the step (4) into an oven to be preheated to 60 ℃, and then stirring and mixing the materials according to the proportion of A: B being 100:60 at the stirring speed of 60r/min for 3min to obtain the ultra-high toughness epoxy resin material.
Example 2: ultrahigh-toughness epoxy resin material for hot-mixed epoxy asphalt and preparation method thereof
The raw materials used in this example were as follows:
polyethylene glycol monomethyl ether: MPEG-750, Haian petrochemical plant of Jiangsu province;
toluene diisocyanate: TDI-80, Hebei Cangzhou university group, Inc.;
bisphenol a type epoxy resin (I): DER331, Dow chemical, USA;
toluene: industrial grade, carnosine and petrochemical company, suzhou;
dibutyltin dilaurate: DY-12, Shanghai Deyin Chemicals, Inc.;
bisphenol a type epoxy resin (II): NPEL-128, south asia electronic materials (kunshan) ltd;
butanediol diglycidyl ether: XY622, new and remote technologies, inc;
3-glycidyl ether oxypropyltriethoxysilane: KBE403, japan shin-Etsu chemical industries co;
cis-12-hydroxyoctadecene-9-oic acid: RA-10, Raffinex oil deep processing Co., Ltd, Anhui province;
liquid ammonia: industrial grade, southern Tong Runfeng petrochemical Co., Ltd;
hydrogen gas: industrial grade, Nanjing Shangyuan industrial gas plant;
ammonia water: 25%, south Tong Runfeng petrochemical Co., Ltd;
nonyl phenol: industrial grade, Jiangsu Lingfei chemical Co.
The preparation method comprises the following operation steps according to the parts by weight:
(1) preparation of modified epoxy resin containing flexible side chain
N (polyethylene glycol monomethyl ether): slowly dripping polyethylene glycol monomethyl ether into a reaction kettle filled with toluene diisocyanate at the molar ratio of n (toluene diisocyanate) to 1:1, controlling the material temperature to be not more than 20 ℃ by using ice water in the dripping process, heating to 40 ℃ after finishing dripping, and continuously reacting for 4 hours to obtain the semi-closed addition product. Putting bisphenol A type epoxy resin (I) and toluene into a reaction kettle according to the mass ratio of 1:1, and then adding n (bisphenol A type epoxy resin): and (3) putting the semi-closed adduct into a reaction kettle according to the molar ratio of n (semi-closed adduct) to 1:1, and reacting for 6h at 60 ℃ under the catalytic action of dibutyltin dilaurate to obtain the modified epoxy resin containing the flexible side chain.
(2) Preparation of super-high toughness epoxy resin main agent A
And (2) sequentially putting 50 parts of bisphenol A type epoxy resin (II), 40 parts of the epoxy resin containing flexible side chain modification prepared in the step (1), 8 parts of butanediol diglycidyl ether and 2 parts of 3-glycidyl ether oxypropyl triethoxysilane into a reaction kettle, stirring and mixing at the stirring temperature of 60 ℃, the stirring speed of 100r/min and the stirring and mixing time of 60min to obtain the ultrahigh-toughness epoxy resin main agent A.
(3) Preparation of long-chain aliphatic primary amines
As n (long chain fatty acid): and (2) putting cis-12-hydroxyoctadecene-9-acid and liquid ammonia into a reaction kettle according to the molar ratio of n (liquid ammonia) to 1:1.5, then reacting for 10 hours at 320 ℃ and 0.5MPa to prepare long-chain fatty amide, and synchronously dehydrating the long-chain fatty amide by utilizing the circulation action of ammonia gas to prepare the long-chain fatty nitrile. Pumping the prepared long-chain aliphatic nitrile and ammonia water into a reaction kettle according to the mass ratio of 1:1, and then adding n (long-chain aliphatic nitrile): and (3) adding hydrogen at a molar ratio of n (hydrogen) to 1:2, and reacting at 160 ℃ and 4MPa for 8h under the action of a molybdenum-containing three-way catalyst to obtain the long-chain aliphatic primary amine.
(4) Preparation of ultra-high toughness epoxy resin curing agent B
And (3) sequentially adding 97 parts of the long-chain aliphatic primary amine prepared in the step (3) and 3 parts of nonyl phenol into a reaction kettle, stirring and mixing, wherein the stirring temperature is 40 ℃, the stirring speed is 60r/min, and the stirring and mixing time is 30min, so that the ultra-high-toughness epoxy resin curing agent B is obtained.
(5) Preparation of ultra-high toughness epoxy resin material
And (3) putting the ultra-high toughness epoxy resin main agent A prepared in the step (2) and the ultra-high toughness epoxy resin curing agent B prepared in the step (4) into an oven to be preheated to 40 ℃, and then stirring and mixing the materials according to the proportion of A: B being 100:70 at the stirring speed of 60r/min for 10min to obtain the ultra-high toughness epoxy resin material.
Example 3 ultra-high toughness epoxy resin material for hot-mix epoxy asphalt and preparation method thereof
The raw materials used in this example were as follows:
polyethylene glycol monomethyl ether: MPEG-2000, Haian petrochemical plant of Jiangsu province;
toluene diisocyanate: TDI-60, Hebei Cangzhou university group, Inc.;
bisphenol a type epoxy resin (I): DER317, Dow chemical company, USA;
dibutyltin dilaurate: DY-12, Shanghai Deyin Chemicals, Inc.;
bisphenol a type epoxy resin (II): WSR6101, blue Star chemical New materials GmbH;
polyethylene glycol diglycidyl ether: XY205, new technologies ltd, anhui;
3-glycidyl ether oxypropylmethyldiethoxysilane: SCA-87F, Nanjing Endocide New Material technology, Inc.;
cis, cis-9, 12-octadecadienoic acid: l80-3, Raffinex oil deep processing Co., Ltd, Anhui province;
liquid ammonia: industrial grade, southern Tong Runfeng petrochemical Co., Ltd;
ammonia water: 25%, south Tong Runfeng petrochemical Co., Ltd;
hydrogen gas: industrial grade, Nanjing Shangyuan industrial gas plant;
benzyl alcohol: industrial grade, luxi chemical group, ltd.
The preparation method comprises the following operation steps according to the parts by weight:
(1) preparation of modified epoxy resin containing flexible side chain
N (polyethylene glycol monomethyl ether): slowly dripping polyethylene glycol monomethyl ether into a reaction kettle filled with toluene diisocyanate at the molar ratio of n (toluene diisocyanate) to 1:1, controlling the material temperature to be not more than 20 ℃ by using ice water in the dripping process, heating to 40 ℃ after finishing dripping, and continuously reacting for 4 hours to obtain the semi-closed addition product. Putting bisphenol A type epoxy resin (I) and toluene into a reaction kettle according to the mass ratio of 1:1, and then adding n (bisphenol A type epoxy resin): and (3) putting the semi-closed adduct into a reaction kettle according to the molar ratio of n (semi-closed adduct) to 1:1, and reacting for 6h at 60 ℃ under the catalytic action of dibutyltin dilaurate to obtain the modified epoxy resin containing the flexible side chain.
(2) Preparation of super-high toughness epoxy resin main agent A
And (2) sequentially putting 65 parts of bisphenol A type epoxy resin (II), 25 parts of the epoxy resin containing flexible side chain modification prepared in the step (1), 8 parts of polyethylene glycol diglycidyl ether and 2 parts of 3-glycidyl ether oxypropylmethyldiethoxysilane into a reaction kettle, stirring and mixing, wherein the stirring temperature is 50 ℃, the stirring speed is 100r/min, and the stirring and mixing time is 60min, so as to obtain the ultrahigh-toughness epoxy resin main agent A.
(3) Preparation of long-chain aliphatic primary amines
As n (long chain fatty acid): adding cis, cis-9, 12-octadecadienoic acid and liquid ammonia into a reaction kettle according to the molar ratio of 1:3, then reacting for 12 hours at 350 ℃ and 0.6MPa to prepare long-chain fatty amide, and synchronously dehydrating the long-chain fatty amide by utilizing the circulation action of ammonia gas to prepare the long-chain fatty nitrile. Pumping the prepared long-chain aliphatic nitrile and ammonia water into a reaction kettle according to the mass ratio of 1:1, and then adding n (long-chain aliphatic nitrile): and (3) adding hydrogen according to the molar ratio of n (hydrogen) to 1:2, and reacting for 4 hours at 180 ℃ and 6MPa under the action of a molybdenum-containing ternary catalyst to obtain the long-chain aliphatic primary amine.
(4) Preparation of ultra-high toughness epoxy resin curing agent B
And (3) sequentially adding 95 parts of the long-chain aliphatic primary amine prepared in the step (3) and 5 parts of benzyl alcohol into a reaction kettle, stirring and mixing, wherein the stirring temperature is 50 ℃, the stirring speed is 60r/min, and the stirring and mixing time is 30min, so that the ultrahigh-toughness epoxy resin curing agent B is obtained.
(5) Preparation of ultra-high toughness epoxy resin material
And (3) putting the ultra-high toughness epoxy resin main agent A prepared in the step (2) and the ultra-high toughness epoxy resin curing agent B prepared in the step (4) into an oven to be preheated to 50 ℃, and then stirring and mixing the materials according to the proportion of A: B being 100:80 at the stirring speed of 60r/min for 5min to obtain the ultra-high toughness epoxy resin material.
Performance testing
Test 1.< workable time test >
The uniformly stirred and mixed ultrahigh-toughness epoxy resin material and asphalt (No. 70 road petroleum asphalt) preheated to 170 ℃ are uniformly stirred and mixed according to the mass ratio of 1:1 to form the hot-mix epoxy asphalt cement. The operable time of the hot-mixed epoxy asphalt cement is measured according to EN 10364-2018 standard, and the viscosity at 170 ℃ is not more than 1 Pa-s as the critical point of the operable time.
Test 2.< tensile test >
The uniformly stirred and mixed ultrahigh-toughness epoxy resin material and asphalt (No. 70 road petroleum asphalt) preheated to 170 ℃ are uniformly stirred and mixed according to the mass ratio of 1:1 to form a hot-mixed epoxy asphalt cement, and then the hot-mixed epoxy asphalt cement is poured into a rectangular paper mold folded by kraft paper preheated to 100 ℃. And (3) putting the cast paper mold into an oven at 150 ℃ for treatment for 3h while the paper mold is hot, and then putting the paper mold into an oven at 60 ℃ for curing for 4 d. Dumbbell bars for tensile testing were cut to the type I bar size in ASTM D638-2008. All tensile test bars were tempered at 23 ℃. + -. 2 ℃ for 24 hours and then tested for tensile properties using a QJ211S tensile tester (Shanghai Tilt technology instruments science and technology Co., Ltd.) at a tensile rate of 50 mm/min.
Test 3.< marshall test >
The uniformly stirred and mixed ultrahigh-toughness epoxy resin material and asphalt (70# road petroleum asphalt) preheated to 170 ℃ are uniformly stirred and mixed according to the mass ratio of 1:1 to form a hot-mixed epoxy asphalt cement, and then are stirred and mixed with graded stone (Zhenjiang Maodi, basalt aggregate, 4.75-9.5 mm: 2.36-4.75 mm: 0.6-2.36 mm: 0-0.6 mm: 25:21.5:22:23:8.5 wt%) according to the oil-stone ratio of 6.5 wt% to form a hot-mixed epoxy asphalt mixture. And (3) carrying out Marshall test piece forming on the hot-mixed epoxy asphalt mixture according to ASTM D6926-2016, carrying out Marshall stability test and water-soaked Marshall stability test according to ASTM D6927-2015 after curing treatment at 60 ℃/4 d.
Test 4.< Freeze-thaw cleavage test >
The hot-mix epoxy asphalt mixture freeze-thaw splitting test piece is prepared according to the program of Marshall test, and then the freeze-thaw splitting test is carried out according to ASTM D6931-2017.
Test 5.< rutting test >
The method comprises the steps of uniformly stirring and mixing a uniformly stirred and mixed ultrahigh-toughness epoxy resin material and asphalt (70# road petroleum asphalt) preheated to 170 ℃ in a mass ratio of 1:1 to form a hot-mixed epoxy asphalt cement, then stirring and mixing the hot-mixed epoxy asphalt cement with graded stone (Zhenjiang Maodi, basalt aggregate, 4.75-9.5 mm: 2.36-4.75 mm: 0.6-2.36 mm: 0-0.6 mm: 25:21.5:22:23:8.5) in an oil-stone ratio of 6.5 wt% to form a hot-mixed epoxy asphalt mixture, and forming a hot-mixed epoxy asphalt mixture track test piece according to the procedure EN 12697-33-2019. And (4) carrying out a rutting test according to EN12697-22 after curing treatment at 60 ℃/4 d.
Test 6.< bending test >
The hot mix epoxy asphalt mixture bending test pieces were prepared according to the < rutting test > procedure and then subjected to a bending test according to EN 12697-26-2018.
Test 7.< four-point bending fatigue life test >
The hot-mix epoxy asphalt mixture bending test piece is prepared according to the program of < rutting test >, and then a four-point bending fatigue life test of the hot-mix epoxy asphalt mixture is carried out according to ASTM D4760-2010 by adopting a B210KIT independent servo pneumatic 4-point bending beam test system (15 ℃, 10Hz and 800 mu epsilon) of the Pavetest company.
Test results
TABLE 1 Performance test results of hot-mix epoxy asphalt material and hot-mix epoxy asphalt mixture
Note: the time required for the cloth-type rotational viscosity to rise to 1000mPa & s at a-120 ℃; b-170 ℃ until the Brookfield rotational viscosity has risen to 1000 mPas.
As can be seen from Table 1, the workable time of the hot-mixed epoxy asphalt material prepared from the ultra-high tenacity epoxy resins prepared in examples 1 to 3 is increased to more than 120min compared with 45min of the warm-mixed epoxy asphalt, and the use requirement of the field construction is met. Compared with a warm-mixed epoxy asphalt material, the tensile property of the hot-mixed epoxy asphalt material prepared from the ultra-high toughness epoxy resin prepared in the embodiments 1 to 3 is greatly improved, and particularly the tensile elongation at break is generally more than 700%, so that a foundation is laid for the excellent fatigue resistance of the hot-mixed epoxy asphalt mixture. Compared with a warm-mixed epoxy asphalt mixture, the Marshall stability of the hot-mixed epoxy asphalt mixture prepared by the ultra-high toughness epoxy resin prepared in the embodiments 1 to 3 is obviously improved and can reach 75 to 85 kN; the freeze-thaw splitting strength ratio is equivalent to that of the warm-mixed epoxy asphalt mixture and is more than 95 percent; the ultimate bending strain is obviously improved compared with the warm-mixed epoxy asphalt mixture, and can reach more than 4000 mu epsilon. The fatigue life of the hot-mix epoxy asphalt mixture prepared from the super-tough epoxy resin material prepared in example 1 is more than 100 ten thousand times at 800 mu epsilon, 15 ℃ and 10Hz, namely, the fatigue failure never occurs.
The present embodiment is only for explaining the present invention, and it is not limited to the present invention, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present invention.
Claims (10)
1. The ultrahigh-toughness epoxy resin material for the hot-mix epoxy asphalt is characterized by comprising a main agent A and a curing agent B in a mass ratio of 100:50 ~ 100, wherein the main agent A comprises the following components in parts by mass:
50 ~ 70 parts of bisphenol A type epoxy resin
20 ~ 40 parts of modified epoxy resin containing flexible side chains
Reactive diluent 5 ~ 15 parts
Epoxy-terminated interfacial agent 1 ~ 3 parts
The curing agent B comprises the following components in percentage by mass:
95 ~ 99 parts of long-chain aliphatic primary amine
Accelerator 1 ~ 5 parts.
2. The ultra-high toughness epoxy resin material for hot mix epoxy asphalt as claimed in claim 1, wherein: the bisphenol A type epoxy resin is a mixture of any one or more of epoxy values of 0.42, 0.44, 0.51 and 0.54.
3. The ultra-high toughness epoxy resin material for hot mix epoxy asphalt as claimed in claim 1, wherein: the modified epoxy resin containing the flexible side chain is prepared by the steps of firstly carrying out addition reaction on polyethylene glycol monomethyl ether and toluene diisocyanate to form a semi-closed addition product, and then carrying out addition reaction on residual-NCO on the semi-closed addition product and secondary hydroxyl on bisphenol A epoxy resin.
4. The ultra-high toughness epoxy resin material for hot mix epoxy asphalt as claimed in claim 1, wherein: the active diluent is any one or a mixture of more of n-butyl glycidyl ether, phenyl glycidyl ether, butanediol diglycidyl ether, polyethylene glycol diglycidyl ether and polypropylene glycol diglycidyl ether.
5. The ultra-high toughness epoxy resin material for hot mix epoxy asphalt as claimed in claim 1, wherein: the epoxy end capping interface agent is any one or a mixture of 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane and 3-glycidoxypropylmethyldimethoxysilane.
6. The ultra-high toughness epoxy resin material for hot mix epoxy asphalt as claimed in claim 1, wherein: the long-chain fatty primary amine is prepared by carrying out ammonolysis, dehydration and catalytic hydrogenation on long-chain fatty acid, wherein the long-chain fatty acid is any one or a mixture of more of 9,11, 13-octadecatrienoic acid, cis-12-hydroxyoctadecene-9-oic acid, cis-9, 2-octadecadienoic acid and all-cis-9, 12, 15-octadecatrienoic acid.
7. The ultra-high toughness epoxy resin material for hot mix epoxy asphalt as claimed in claim 1, wherein: the accelerant is any one or a mixture of more of 2,4, 6-tri (dimethylaminomethyl) phenol, triphenylphosphine, nonylphenol, phenol, triethanolamine, N-dimethylethanolamine and benzyl alcohol.
8. A preparation method of an ultra-high toughness epoxy resin material for hot-mix epoxy asphalt is characterized by comprising the following steps: the method comprises the following steps:
s1, preparing modified epoxy resin containing flexible side chains;
s2, sequentially putting bisphenol A type epoxy resin, flexible side chain-containing modified epoxy resin, reactive diluent and epoxy end-capped interface agent into a reaction kettle for mixing to obtain a main agent A;
s3, preparing long-chain fatty primary amine;
s4, sequentially adding the long-chain aliphatic primary amine and the accelerator into a reaction kettle, and stirring and mixing to obtain a curing agent B;
s5, stirring and mixing the main agent A prepared in the S1 and the curing agent B prepared in the S2 to obtain the ultrahigh-toughness epoxy resin material for the hot-mix epoxy asphalt.
9. The method for preparing the ultra-high toughness epoxy resin material for the hot mix epoxy asphalt as claimed in claim 8, wherein: the preparation method of the flexible side chain-containing modified epoxy resin comprises the following operation steps:
A1. slowly dripping polyethylene glycol monomethyl ether into a reaction kettle filled with toluene diisocyanate according to the molar ratio of n (polyethylene glycol monomethyl ether) to n (toluene diisocyanate) =1:1, controlling the material temperature to be not more than 20 ℃ by using ice water in the dripping process, heating to 40 ~ 50 ℃ after finishing dripping, and continuously reacting for 3 ~ 5 hours to obtain a semi-closed addition product;
A2. putting bisphenol A epoxy resin and toluene into a reaction kettle according to the mass ratio of 1:1, then putting the prepared semi-closed adduct into the reaction kettle according to the molar ratio of n (bisphenol A epoxy resin) =1:1, and reacting for 4 ~ 8h at 60 ~ 80 ℃ under the catalysis of dibutyltin dilaurate.
10. The method for preparing the ultra-high toughness epoxy resin material for the hot mix epoxy asphalt as claimed in claim 8, wherein: the preparation method of the long-chain fatty primary amine comprises the following operation steps:
B1. putting the long-chain fatty acid and liquid ammonia into a reaction kettle according to the molar ratio of n (long-chain fatty acid) to n (liquid ammonia) =1:1 ~ 3, and reacting for 6 ~ 12h at 300 ~ 350 ℃ and 0.2 ~ 0.6.6 MPa to prepare long-chain fatty amide;
B2. dehydrating the prepared fatty amide by using the circulation effect of ammonia gas generated by excessive liquid ammonia to prepare long-chain fatty nitrile;
B3. pumping the prepared long-chain aliphatic nitrile and ammonia water into a hydrogenation kettle according to the mass ratio of 1:1 ~ 2, adding hydrogen according to the molar ratio of n (long-chain aliphatic nitrile) =1:2, and reacting for 2 ~ 8h at 120 ~ 180 ℃ and 2 ~ 6MPa under the action of a molybdenum-containing ternary catalyst.
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| PCT/CN2020/102445 WO2021088410A1 (en) | 2019-11-06 | 2020-07-16 | Ultrahigh-toughness epoxy resin material for hot mix epoxy asphalt and preparation method therefor |
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