Patent Description:
In recent years, the traffic field in China is rapidly developed, the Chinese traffic volume is greatly increased, and the general promotion of the road grade puts higher requirements on the asphalt pavement; the bridge serves as a junction facility for connecting traffic and the functions exerted in a traffic network are increasingly irreplaceable, so that the requirements on bridge deck pavement are stricter. At present, the materials for paving the asphalt pavement and the steel bridge pavement are mainly gussasphalt mixture, epoxy asphalt mixture, stone mastic asphalt mixture and the like. The epoxy asphalt mixture is applied to a plurality of large-span steel bridges such as Hangzhou Bay Railway Bridge, Wuhan Tianxingzhou Yangtse Bridge due to the characteristics of excellent deformation resistance, water stability, fatigue resistance and the like.

However, epoxy asphalt generally has the disadvantages of poor low-temperature flexibility, poor deformation compatibility with steel bridge pavement, and generation of large temperature stress and fatigue cracks under low-temperature conditions. Although the toughening agent is currently used for improving the flexibility of the epoxy asphalt, the effect is not satisfactory, and the cracks have become the most common diseases in the epoxy asphalt bridge deck pavement, so the normal use and the driving safety of the bridge are influenced. At present, the existing invention patents in China and abroad propose some epoxy system preparation processes for improving poor low-temperature flexibility, but all have the defects of various raw materials and complex preparation processes, and break away from the practical construction.

For example, <CIT> discloses a flexible curing agent containing a hot blend of a toughening agent and straight chain fatty amine, as well as a preparation method and application thereof. Another curing adhesive is disclosed, for example, in <CIT>.

Other asphalt modifiers, modified asphalt and preparation methods thereof are, inter alia, disclosed in <CIT>, <CIT> and <CIT>.

In the using process of epoxy asphalt, a certain construction time, also called retention time, needs to be reserved for the epoxy asphalt and the aggregate to be convenient for mixing and paving. At present, the related technology in China and abroad is currently to increase the retention time by adding a diluent into the system, and the excessive addition of diluent can forcibly reduce the viscosity and increase the retention time. However, the mechanical property of the curing system is influenced, and the method is not the best of both worlds.

In addition, because the physical and chemical properties of petroleum asphalt and epoxy resin are greatly different, an epoxy resin system synthesized by applying most of the conventional epoxy resin curing agents is poor in compatibility with asphalt, a fully-crosslinked network structure cannot be formed in the epoxy asphalt, an obvious two-phase separation occurs, a stripping phenomenon is caused, and the normal use of a pavement and a deck is influenced. Moreover, the imported epoxy resin and the matched curing agent thereof are widely applied to the paving of asphalt pavements and steel bridge pavements in China at present by virtue of excellent flexibility. However, the high price greatly increases the cost of paving materials and further hinders the popularization of epoxy asphalt pavements.

Therefore, how to develop an epoxy resin system that has good compatibility with asphalt, low cost, simple raw material and preparation process, long retention time and can be used for preparing low-temperature high-flexibility epoxy asphalt material is a problem to be solved urgently in the field of traffic infrastructure.

The objectives of the present disclosure are as follows: the technical problems to be solved by the present disclosure are to provide the epoxy resin material which has low cost, simple preparation process, good compatibility with asphalt and long retention time, can be used for preparing the low-temperature high-flexibility epoxy asphalt material in view of the deficiencies in the prior art, so as to effectively reduce the occurrence frequency of crack diseases of bridge deck pavement, greatly reduce the capital investment of bridge deck pavement engineering and improve the economic benefit.

In order to achieve the above objectives, the technical solutions adopted by the present disclosure are as follows.

Provided is an economical epoxy resin material for epoxy asphalt with low-temperature resistance and high flexibility. The material comprises the following components by a mass fraction.

The material comprises a component A and a component B.

The component A includes <NUM> parts of an epoxy resin main agent.

<NUM> parts to <NUM> parts of a modifying agent.

<NUM> parts to <NUM> parts of an active curing agent.

<NUM> parts to <NUM> parts of a titanate coupling agent.

<NUM> parts to <NUM> parts of a reversible deformation additive.

The modifying agent, the active curing agent, the titanate coupling agent and the reversible deformation additive in component B have a synergistic effect.

The epoxy resin main agent is selected from any one or a mixture of China-made diphenol propane glycidyl ether resin and diphenol methane glycidyl ether resin; preferably a China-made diphenol propane glycidyl ether resin.

Specifically, the modifying agent is selected from any one or a mixture of more than two from <NUM>, <NUM>-diamino-p-menthane, <NUM>-piperazine ethanamine, <NUM>,<NUM>'-diaminodicyclohexylmethane and <NUM>, <NUM>-bis (aminomethyl) cyclohexane, and preferably <NUM>-piperazine ethanamine.

The modifying agent is an amine compound containing an amine ring (cyclohexyl, hetero-oxygen and nitrogen atom six-membered ring) in a molecular structure. Specifically, the modifying agent is a low-viscosity liquid, is used for modifying the active curing agent in the present disclosure, and participates in the curing reaction of the epoxy resin together, so that the viscosity of the epoxy asphalt can be reduced, and the low-temperature property of the epoxy asphalt is improved.

Specifically, the active curing agent is selected from any one or a mixture of more than two from coco alkyl amine, <NUM>-amino-<NUM>-octadecene, oleyl amine polyoxyethylene ether and lauroyl glutamic acid, and preferably <NUM>-amino-<NUM>-octadecene.

Specifically, the titanate coupling agent is selected from any one or a mixture of more than two from isopropyl triisostearoyl titanate, isopropyl trilauryl titanate, isopropyl tris (dodecylbenzenesulfonyl) titanate and isopropyl isostearoyl diacryloyl titanate, and preferably isopropyl triisostearoyl titanate. The inorganic functional group of the titanate coupling agent has only one alkoxy, and the organic functional group Y at the other end is consist of C=C, NH<NUM>, OH, and H. Moreover, the interface of the active curing agent in the present disclosure is modified by halogen group elements and organic hydroxyl groups, both of which participate in the curing reaction of the epoxy resin, reducing the viscosity of the cured epoxy resin when preparing epoxy asphalt with asphalt, increasing construction tolerance time, improving workability, and reducing production costs.

The reversible deformation additive is selected from any one or a mixture of more than two from acrylonitrile-butadiene rubber, fluorine rubber, liquid acrylate rubber and liquid phenolic resin.

Specifically, the epoxy resin generated after the curing reaction of the active curing agent and the epoxy resin main agent in the present disclosure is a thermosetting resin, so the epoxy resin has high strength but low flexibility and particularly shows the characteristics of hardness and brittleness under low-temperature conditions. The reversible deformation additive has an affinity with epoxy resin, which can form a rubber particle dispersion phase, and forms a "sea-island structure" together with the epoxy resin phase, and elastomer particles in the dispersion phase stop crack generation when a system is impacted, so that shear deformation is induced, and the flexibility of the epoxy resin and the epoxy asphalt in the present disclosure under normal temperature and low-temperature conditions is improved.

Further, the present disclosure also provides a method for preparing the economical epoxy resin material for epoxy asphalt with low-temperature resistance and high flexibility. The method comprises the following steps.

Preferably, in Step (<NUM>), the stirring temperature for preparing the component B is <NUM>±<NUM> and the stirring time is <NUM> hours.

Furthermore, the present disclosure also claims a use of the epoxy resin material in preparing an epoxy asphalt for paving highway pavement, concrete bridge pavement and steel bridge pavement.

Specifically, the method includes the following steps.

In S1, components A and B in the epoxy resin material are evenly mixed.

In S2, <NUM> parts of the epoxy resin material obtained by mixing in Step S1 are taken and added into <NUM> parts of a matrix asphalt. The mixture is stirred at a temperature of <NUM>±<NUM> for <NUM> minutes to obtain the epoxy asphalt.

In S3, the epoxy asphalt obtained in Step S2 is mixed with aggregate and mineral powder, and the mixture is stirred for <NUM> minute to <NUM> minutes at a temperature of <NUM>±<NUM> to obtain an epoxy asphalt mixture; a mass percent of the epoxy asphalt is <NUM>% to <NUM>%, and a mass percent of the aggregate and the mineral powder is <NUM>% to <NUM>%.

In S4, the epoxy asphalt mixture obtained in Step S3 is spread on the pavement or the deck, the epoxy asphalt mixture is rolled into shape, and the shaped epoxy asphalt mixture is cured at a temperature of <NUM> to <NUM> for <NUM> hours to <NUM> hours to obtain the pavement and deck paved by the economic epoxy asphalt with low-temperature resistance and high flexibility.

Beneficial effects lie in the following.

The above and/or other advantages of the present disclosure will become further apparent from the following detailed description of the present disclosure in conjunction with the accompanying drawings and the embodiments.

The present disclosure will be better understood from the following examples.

Asphalt: <NUM> parts of <NUM># road petroleum asphalt.

Component A: <NUM> parts of China-made diphenol propane glycidyl ether resin.

Component B: <NUM> parts of modifying agent (<NUM>-piperazine ethanamine, Jining Sanshi Biotechnology Co. ), <NUM> parts of active curing agent (<NUM>-amino-<NUM>-octadecene, Condicechem HuBei), <NUM> parts of titanate coupling agent (isopropyl triisostearoyl titanate, Shandong Linchuang Biotechnology), and <NUM> parts of reversible deformation additive (acrylonitrile-butadiene rubber, in HuBei ChengFeng Chemical Co.

A method for preparing an epoxy asphalt of Example <NUM> includes the following steps. A modifying agent, an active curing agent, a titanate coupling agent and a reversible deformation additive that are preheated to <NUM> are added into a flask, and stirred for <NUM> hours at <NUM> to synthesize a component B; the synthesized component B is mixed with the component A and stirred at the temperature of <NUM>±<NUM> for <NUM> minutes to obtain an epoxy resin system. The prepared epoxy resin system is added into <NUM># road petroleum asphalt and stirred for <NUM> minutes at the temperature of <NUM>±<NUM> to obtain the epoxy asphalt.

<FIG> illustrates fluorescent microscopic images of an epoxy asphalt prepared from an epoxy resin material of Example <NUM> before and after curing. It can be seen from <FIG> that, before curing, the components of the epoxy asphalt are subjected to sufficient high-speed shearing and stirring to maintain the dispersion among the particles so that the asphalt appears as a continuous phase under fluorescent irradiation, and the epoxy resin appears as dispersed particles; after the curing reaction, the epoxy resin is converted into a continuous phase and forms a stable and compact cross-linked network structure, as a disperse phase, the asphalt is embedded with the epoxy resin in spherical particles, the area of the fluorescent part in the image is calculated using threshold segmentation method, and the proportion of epoxy resin area is <NUM>%. It is verified that the three-dimensional network formed by epoxy resin curing and crosslinking at this time is dense and stable, and epoxy asphalt has more stable mechanical properties.

<FIG> illustrates Brookfield viscosity curves for an epoxy asphalt in Example <NUM> at <NUM> and <NUM>. As illustrated in <FIG>, the viscosity of the epoxy asphalt in Example <NUM> is permanently lower than <NUM> mPa·s within <NUM> minutes, which satisfies the requirement for the specification: the time for the viscosity to reach <NUM> mPa·s is more than <NUM> minutes. This epoxy asphalt is proved to have a long retention time, be convenient for mixing and paving the epoxy asphalt and aggregate, and satisfy the construction requirements.

Component B: <NUM> parts of modifying agent (<NUM>-piperazine ethanamine, Jining Sanshi Biotechnology Co. ), <NUM> parts of active curing agent (<NUM>-amino-<NUM>-octadecene, Condicechem HuBei), <NUM> parts of titanate coupling agent (isopropyl triisostearoyl titanate, Shandong Linchuang Biotechnology), and <NUM> parts of reversible deformation additive (acrylonitrile-butadiene rubber, HuBei ChengFeng Chemical Co.

The preparation method of epoxy asphalt in Example <NUM> is the same as in Example <NUM>.

Component B: <NUM> parts of modifying agent (<NUM>-piperazine ethanamine, Jining Sanshi Biotechnology Co. ), <NUM> parts of active curing agent (<NUM>-amino-<NUM>-octadecene in Condicechem HuBei), <NUM> parts of titanate coupling agent (isopropyl triisostearoyl titanate, Shandong Linchuang Biotechnology), and <NUM> parts of reversible deformation additive (acrylonitrile-butadiene rubber, HuBei ChengFeng Chemical Co.

Component B: <NUM> parts of polyamine curing agent (Polyethylene Polyamine, Shandong Xuguang Chemical Co.

A method for preparing an epoxy asphalt of Comparative Example <NUM> includes the following steps. The component A and the component B preheated to <NUM> are mixed with each other and stirred for <NUM> minutes at the temperature of <NUM>±<NUM> to obtain an epoxy resin system; the prepared epoxy resin system is added into <NUM># road petroleum asphalt and stirred for 5minutes at the temperature of <NUM>±<NUM> to obtain the epoxy asphalt.

Component B: <NUM> parts of polyether amine D230 curing agent and <NUM> parts of m-xylylenediamine curing agent.

A method for preparing an epoxy asphalt in Comparative Example <NUM> includes the following steps. The <NUM># road petroleum asphalt, the polyether amine D230 curing agent and the m-xylylenediamine curing agent are uniformly stirred through a colloid mill, then the component A is added, uniformly mixed, and cured at the temperature of <NUM> for <NUM> hours to obtain the epoxy asphalt.

Component A: <NUM> parts of Japanese epoxy resin KD-HDP.

Component B: <NUM> parts of epoxy resin curing agent matched with KD-HDP.

Component A: <NUM> parts of American epoxy asphalt.

Component B: <NUM> parts of American epoxy asphalt.

A method for preparing an epoxy asphalt of Comparative Example <NUM> includes the following steps. The component A preheated to <NUM> is mixed with the component B preheated to <NUM>, and stirred for <NUM> minutes at the temperature of <NUM>±<NUM> to obtain the epoxy asphalt.

Examples <NUM> to <NUM> are epoxy asphalts prepared by adopting the epoxy resin materials of the present disclosure; Comparative Examples <NUM> and <NUM> are epoxy asphalt prepared by using China-made epoxy resin and a common curing agent; Comparative Example <NUM> is an epoxy asphalt prepared using a high property Japanese epoxy resin and a mating curing agent; Comparative Example <NUM> is an American two-part epoxy asphalt. For the convenience of discussion, in the following description, the epoxy asphalts in Examples <NUM> to <NUM> are referred to as the epoxy asphalt of the present disclosure, the epoxy asphalt in Comparative Example <NUM> is referred to as the commonly-used China-made epoxy asphalt-<NUM>, the epoxy asphalt in Comparative Example <NUM> is referred to as the commonly-used China-made epoxy asphalt-<NUM>, the epoxy asphalt in Comparative Example <NUM> is referred to as the Japanese epoxy asphalt, and the epoxy asphalt in Comparative Example <NUM> is referred to as the American epoxy asphalt. The tensile strength and elongation at break at -<NUM> and <NUM> of Examples <NUM> to <NUM> and Comparative Examples <NUM> to <NUM> are shown in Table <NUM>.

The cost of each epoxy asphalt is converted, and the results are shown in Tables <NUM> to <NUM>.

In order to verify that the modifying agent, the active curing agent, the titanate coupling agent and the reversible deformation additive in the epoxy resin material for epoxy asphalt have a synergistic effect, the above synergistic effect is illustrated by experimental groups <NUM>-<NUM>, <NUM>-<NUM>, <NUM>-<NUM>, <NUM>-<NUM>, <NUM>-<NUM>, <NUM>-<NUM>, <NUM>-<NUM> and <NUM>-<NUM>, respectively, and the components are as follows.

Component B: <NUM> parts of active curing agent (<NUM>-amino-<NUM>-octadecene, Condicechem HuBei).

Component B: <NUM> parts of modifying agent (<NUM>-piperazine ethanamine, Jining Sanshi Biotechnology Co.

Component B: <NUM> parts of Titanate coupling agent (isopropyl triisostearoyl titanate, Shandong Linchuang Biotechnology).

Component B: <NUM> parts of reversible deformation additive (acrylonitrile-butadiene rubber, in HuBei ChengFeng Chemical Co.

Component B: <NUM> parts of modifying agent (<NUM>-piperazine ethanamine, Jining Sanshi Biotechnology Co. ), and <NUM> parts of active curing agent (<NUM>-amino-<NUM>-octadecene, Condicechem HuBei).

Component B: <NUM> parts of active curing agent (<NUM>-amino-<NUM>-octadecene, Condicechem HuBei), and <NUM> parts of Titanate coupling agent (isopropyl triisostearoyl titanate, Shandong Linchuang Biotechnology).

Component B: <NUM> parts of active curing agent (<NUM>-amino-<NUM>-octadecene, Condicechem HuBei) and <NUM> parts of reversible deformation additive (acrylonitrile-butadiene rubber, in HuBei ChengFeng Chemical Co.

Component B: <NUM> parts of modifying agent (<NUM>-piperazine ethanamine, Jining Sanshi Biotechnology Co. ), <NUM> part of active curing agent (<NUM>-amino-<NUM>-octadecene, Condicechem HuBei), <NUM> parts of Titanate coupling agent (isopropyl triisostearoyl titanate, Shandong Linchuang Biotechnology), and <NUM> parts of reversible deformation additive (acrylonitrile-butadiene rubber, in HuBei ChengFeng Chemical Co.

The epoxy asphalt prepared by the above components is epoxy asphalt <NUM>-<NUM>, epoxy asphalt <NUM>-<NUM>, epoxy asphalt <NUM>-<NUM>, epoxy asphalt <NUM>-<NUM>, epoxy asphalt <NUM>-<NUM>, epoxy asphalt <NUM>-<NUM>, epoxy asphalt <NUM>-<NUM> and epoxy asphalt <NUM>-<NUM>, respectively, and the property data are as shown in Table <NUM>.

The following conclusions can be drawn by combining the above data.

Claim 1:
An economical epoxy resin material for epoxy asphalt with low-temperature resistance and high flexibility, wherein the material comprises following components by a mass fraction:
a Component A:
<NUM> parts of an epoxy resin main agent;
a Component B:
<NUM> parts to <NUM> parts of a modifying agent,
<NUM> parts to <NUM> parts of an active curing agent,
<NUM> parts to <NUM> parts of a titanate coupling agent, and
<NUM> parts to <NUM> parts of a reversible deformation additive; wherein
the modifying agent is an amine compound containing an amine ring in a molecular structure; and the reversible deformation additive is selected from any one or a mixture of more than two from acrylonitrile-butadiene rubber, fluorine rubber, liquid acrylate rubber and liquid phenolic resin.