CN107142064B - Normal-temperature cured epoxy resin binder for paving steel bridge deck and preparation method thereof - Google Patents
Normal-temperature cured epoxy resin binder for paving steel bridge deck and preparation method thereof Download PDFInfo
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- CN107142064B CN107142064B CN201710536241.1A CN201710536241A CN107142064B CN 107142064 B CN107142064 B CN 107142064B CN 201710536241 A CN201710536241 A CN 201710536241A CN 107142064 B CN107142064 B CN 107142064B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on 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
- C08G59/504—Amines containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/06—Polymer mixtures characterised by other features having improved processability or containing aids for moulding methods
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- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Epoxy Resins (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention provides a normal-temperature curing epoxy resin adhesive for paving a steel bridge deck and a preparation method thereof. The normal temperature curing epoxy asphalt binder comprises a component A and a component B, wherein the component A mainly comprises epoxy resin, a diluent and a toughening agent, and the component B mainly comprises a curing agent, an accelerator, a diluent and a defoaming agent. The normal-temperature curing epoxy asphalt binder can be constructed and cured at normal temperature, is low-carbon and environment-friendly, and has a simple construction process. The boron oxide/end group modified nitrile rubber composite material is used as a toughening agent, so that excellent mechanical strength and toughness of the cured epoxy resin are ensured. Meanwhile, the three-dimensional network structure formed after the epoxy resin is cured forms good bonding with the steel bridge deck and the pavement layer, so that the capability of the bridge deck for resisting the influence of vehicle load and environmental factors is effectively improved, and the service life of the steel bridge deck is prolonged.
Description
Technical Field
The invention relates to a material for road and bridge construction and a preparation method thereof, in particular to a normal-temperature cured epoxy resin binder for paving a steel bridge deck and a preparation method thereof.
Background
The early damage of the steel bridge pavement layer is mostly caused by the damage of the waterproof bonding layer, and the research and development of waterproof bonding layer materials and the improvement of pavement performance of the steel bridge deck are paid attention by all countries in the world. Since the 70 s of the 20 th century, the European and American countries carried out systematic research on steel bridge deck pavement and waterproof bonding layers, and a waterproof system adaptive to the climatic environment, traffic conditions and construction level is formed. The waterproof bonding design for bridge decks, as represented in europe by germany, is mainly a double-layer design comprising a reactive resin waterproof layer (mainly epoxy resin) combined with an asphalt waterproof layer. The steel bridge deck pavement of America and Japan adopts a waterproof bonding layer with waterproof and bonding functions, and the waterproof bonding material is most widely applied by an epoxy asphalt binder of American ChemCo Systems company and a secondary curing epoxy resin binder developed by Japan great groups. The research of the domestic steel bridge deck pavement and waterproof bonding system begins in the 80 th 20 th century, the pavement layer material is developed from asphalt concrete to epoxy asphalt mixture, and the waterproof bonding material is also innovated from emulsified asphalt to epoxy asphalt or epoxy resin.
The waterproof bonding layer plays a dual role in dispersing internal stress and protecting a bridge deck in a bridge deck pavement structure, and is the key for ensuring the durability of the bridge. However, the main problems of the bridge deck waterproof bonding layer are that the bonding strength between the bridge deck and the pavement layer is insufficient, the horizontal shearing resistance is weak, and the pavement layer is damaged prematurely. Higher bond strength and toughness are the properties of most interest for waterproof bonding materials used in bridge deck paving. The early stage bridge deck waterproof bonding mainly adopts thermoplastic materials such as polyolefin, rubber modified asphalt and the like, and has good waterproofness, heat resistance and insufficient bonding strength. Thermosetting epoxy or epoxy asphalt has been widely used for waterproof bonding layers of steel bridge decks due to its excellent waterproof and thermal stability.
Disclosure of Invention
The invention aims to provide a normal-temperature curing epoxy resin adhesive for paving a steel bridge deck, which has the characteristics of excellent mechanical strength and flexibility, capability of being mixed and constructed at normal temperature, short curing time and the like, and is mainly suitable for a waterproof adhesive layer of an epoxy asphalt steel bridge deck.
The invention provides a normal-temperature curing epoxy resin binder material for paving a steel bridge deck, which consists of a component A and a component B, wherein the component A comprises epoxy resin, a diluent and a toughening agent, and the component B comprises a curing agent, an accelerator, a diluent and a defoaming agent. The weight parts of the components are as follows:
component A
Epoxy resin 100 parts
5-40 parts of diluent
3-20 parts of toughening agent
Component B
Wherein the mass ratio of the component A to the component B is 100: 70-100: 140.
the epoxy resin is liquid bisphenol A type glycidyl ether epoxy resin, including E-51 epoxy resin, E-44 epoxy resin and the like.
The diluent for the component A is an active epoxy diluent and comprises one or a mixture of more of butyl glycidyl ether, octyl glycidyl ether, allyl glycidyl ether, glycerol triglycidyl ether, C12-C14 alkyl glycidyl ether or benzyl glycidyl ether.
The toughening agent is a boron oxide/end group modified nitrile rubber composite material, and the structural formula is as follows:
the curing agent is low molecular weight polyamide, and the structural formula is as follows:
the accelerator is a tertiary amine accelerator, and comprises triethanolamine, benzyl dimethylamine or one of 2, 4, 6-tris (dimethylaminomethyl) phenol (DMP-30).
The diluent for the component B is a non-reactive epoxy diluent and comprises one or a mixture of more of dibutyl phthalate, dioctyl phthalate or triphenyl phosphite.
The defoaming agent is polysiloxane.
A method for preparing the normal temperature curing epoxy resin adhesive for paving the steel bridge deck comprises the following steps:
preparing a toughening agent: mixing boric acid, terminal group modified nitrile rubber (including hydroxyl-terminated nitrile rubber, carboxyl-terminated nitrile rubber or epoxy-terminated nitrile rubber) and toluene, wherein the molar ratio of the boric acid to the terminal group modified nitrile rubber is 1:0.3-1:1, and the dosage of the toluene is 8-10 times of the sum of the mass of the boric acid and the terminal group modified nitrile rubber. The mixture is stirred and refluxed for 2 to 6 hours. After the reaction is finished, the solvent and the micromolecule by-product generated in the reaction are distilled out by reduced pressure distillation, and the mixture is cooled to room temperature. Washing and drying the vacuum distillation product to obtain the boron oxide/end group modified nitrile rubber composite material serving as a toughening agent for curing the epoxy resin at normal temperature.
Preparation of component A: mixing the epoxy resin, the toughening agent and the component A by using a diluent, heating to 40-80 ℃, and stirring at the speed of 300-600 revolutions per minute for 1-4 hours. And cooling to room temperature to obtain the component A of the normal-temperature curing epoxy resin adhesive for paving the steel bridge deck.
Preparation of component B: and mixing the curing agent, the accelerator and the component B with the diluent and the defoaming agent, and stirring at the speed of 300-600 revolutions per minute at room temperature for 1-3 hours to obtain the component B of the normal-temperature curing epoxy resin adhesive for paving the steel bridge deck.
The application method of the normal temperature curing epoxy resin adhesive for paving the steel bridge deck is characterized in that the component A and the component B are mixed at room temperature and rapidly stirred for 3-5 minutes at the speed of 600-.
The normal temperature curing epoxy resin adhesive for paving the steel bridge deck has the following characteristics:
(1) the construction process is simple, polyamide polyamine is used as a curing agent, and the polyamide polyamine can be mixed and constructed at normal temperature, so that the energy is saved and the environment is protected;
(2) the synthesized boron oxide/carboxyl-terminated nitrile rubber composite material is used as a toughening agent, so that the strength and toughness of the epoxy resin can be improved;
(3) the price is low, and the viscosity and the cost are reduced by using the active and non-active diluents together.
Detailed Description
The invention is further illustrated by the following examples, but the scope of protection of the invention is not limited to the examples. Other variations and modifications to the present invention may occur to those skilled in the art without departing from the spirit and scope of the present invention.
Example 1:
preparing a toughening agent: mixing boric acid, carboxyl-terminated butadiene-acrylonitrile rubber and toluene, wherein the molar ratio of the boric acid to the carboxyl-terminated butadiene-acrylonitrile rubber is 1:0.3, and the dosage of the toluene is 8 times of the sum of the mass of the boric acid and the carboxyl-terminated butadiene-acrylonitrile rubber. The mixture was stirred and refluxed for 2 hours. After the reaction is finished, the solvent and the micromolecule by-products are distilled off by reduced pressure distillation and cooled to room temperature. Washing and drying the product of reduced pressure distillation to obtain the boron oxide/carboxyl-terminated butadiene-acrylonitrile rubber composite material serving as a toughening agent for curing the epoxy resin at normal temperature.
100 parts by mass of E-51 epoxy resin (the same applies hereinafter) was weighed, 3 parts of the above-prepared toughener was added, 5 parts of butyl glycidyl ether was added, and the mixture was heated to 60 ℃ and stirred at 300 rpm for 2 hours. And cooling to room temperature to obtain the component A of the normal-temperature curing epoxy resin binder.
100 parts of low molecular weight polyamide, 1 part of triethanolamine, 5 parts of dibutyl phthalate and 0.3 part of polysiloxane are respectively weighed and stirred at the speed of 300 revolutions per minute for 1 hour at room temperature to obtain the component B of the normal temperature curing epoxy resin binder.
100 parts of component A and 70 parts of component B are mixed at room temperature and stirred at the speed of 800 revolutions per minute for 5 minutes to obtain a normal temperature curing epoxy resin mixture. Pouring the epoxy resin mixture into a polytetrafluoroethylene mold, curing at normal temperature for 12 hours, and demolding to obtain an epoxy resin cured substance dumbbell-shaped sample for mechanical property testing. The tensile property test standard refers to GB/T2567-2008, the test condition is 23 +/-2 ℃, and the tensile rate is 10 mm/min. And testing the bonding strength by adopting a drawing instrument. The mechanical property test results are shown in the attached table 1.
Example 2:
preparing a toughening agent: mixing boric acid, hydroxyl-terminated nitrile rubber and toluene, wherein the molar ratio of the boric acid to the hydroxyl-terminated nitrile rubber is 1:0.5, and the dosage of the toluene is 9 times of the sum of the mass of the boric acid and the hydroxyl-terminated nitrile rubber. The mixture was stirred and refluxed for 3 hours. After the reaction is finished, the solvent and the micromolecule by-products are distilled off by reduced pressure distillation and cooled to room temperature. Washing and drying the vacuum distillation product to obtain the boron oxide/hydroxyl-terminated butadiene-acrylonitrile rubber composite material serving as a toughening agent for curing the epoxy resin at normal temperature.
100 parts of E-51 are weighed, 20 parts of the toughener prepared above are added, 40 parts of octyl glycidyl ether are added, the mixture is heated to 70 ℃ and stirred at the speed of 300 revolutions per minute for 2 hours. And cooling to room temperature to obtain the component A of the normal-temperature curing epoxy resin binder.
100 parts of low molecular weight polyamide, 5 parts of benzyl dimethylamine, 30 parts of dioctyl phthalate and 3 parts of polysiloxane are respectively weighed and stirred at the speed of 300 revolutions per minute for 2 hours at room temperature to obtain the component B of the normal temperature curing epoxy resin binder.
100 parts of component A and 140 parts of component B are mixed at room temperature and stirred at the speed of 800 revolutions per minute for 5 minutes to obtain a normal temperature curing epoxy resin mixture. The mechanical property test method is the same as that of example 1, and the test results are shown in the attached table 1.
Example 3:
preparing a toughening agent: mixing boric acid, the epoxy-terminated nitrile rubber and toluene, wherein the molar ratio of the boric acid to the epoxy-terminated nitrile rubber is 1:1, and the using amount of the toluene is 10 times of the sum of the mass of the boric acid and the epoxy-terminated nitrile rubber. The mixture was stirred and refluxed for 2 hours. After the reaction is finished, the solvent and the micromolecule by-products are distilled off by reduced pressure distillation and cooled to room temperature. Washing and drying the vacuum distillation product to obtain the boron oxide/epoxy-terminated nitrile rubber composite material serving as a toughening agent for curing the epoxy resin at normal temperature.
100 parts of E-51 are weighed, 10 parts of the toughener prepared above are added, 20 parts of allyl glycidyl ether are added, the mixture is heated to 70 ℃ and stirred at 300 revolutions per minute for 2 hours. And cooling to room temperature to obtain the component A of the normal-temperature curing epoxy resin binder.
100 parts of low molecular weight polyamide, 2 parts of benzyldimethylamine, 10 parts of triphenyl phosphite and 1 part of polysiloxane are respectively weighed and stirred at the speed of 300 revolutions per minute for 1 hour at room temperature to obtain the component B of the normal temperature curing epoxy resin binder.
100 parts of the component A and 100 parts of the component B are mixed at room temperature and stirred at the speed of 800 revolutions per minute for 5 minutes to obtain a normal temperature curing epoxy resin mixture. The mechanical property test method is the same as that of example 1, and the test results are shown in the attached table 1.
Table 1 mechanical property of normal temperature solidified epoxy resin adhesive for paving steel bridge surface
Claims (9)
1. The normal-temperature curing epoxy resin adhesive for paving the steel bridge deck comprises a component A and a component B, and is characterized in that: the mass ratio of the component A to the component B is 100: 70-100: 140, the component A comprises the following components in parts by weight:
epoxy resin 100 parts
5-40 parts of diluent
3-20 parts of toughening agent
The component B comprises the following components in parts by weight:
the epoxy resin is liquid bisphenol A type glycidyl ether epoxy resin;
the diluent in the component A is an active epoxy diluent;
the toughening agent is a boron oxide/end group modified nitrile rubber composite material;
the curing agent is low molecular weight polyamide;
the accelerator is tertiary amine accelerator;
the diluent in the component B is an inactive epoxy diluent.
2. The normal-temperature-curing epoxy resin adhesive for paving the steel bridge deck according to claim 1, wherein the diluent of the component A is one or a mixture of butyl glycidyl ether, octyl glycidyl ether, allyl glycidyl ether, glycerol triglycidyl ether, C12-C14 alkyl glycidyl ether and benzyl glycidyl ether.
3. The normal temperature curing epoxy resin adhesive for paving the steel bridge deck as claimed in claim 1, wherein the accelerator is one of triethanolamine, benzyldimethylamine or 2, 4, 6-tris (dimethylaminomethyl) phenol (DMP-30).
4. The normal temperature curing epoxy resin adhesive for paving the steel bridge deck according to claim 1, wherein the diluent of the component B is one or a mixture of dibutyl phthalate, dioctyl phthalate and triphenyl phosphite.
5. The normal-temperature curing epoxy resin adhesive for paving the steel bridge deck as claimed in claim 1, wherein the defoaming agent is polysiloxane.
6. A method for preparing the normal-temperature curing epoxy resin adhesive for paving the steel bridge deck as claimed in any one of claims 1 to 5, which is characterized by comprising the following steps:
step a, preparing a toughening agent: mixing boric acid, the terminal group modified nitrile rubber and toluene, wherein the molar ratio of the boric acid to the terminal group modified nitrile rubber is 1:0.3-1:1, and the mass of the toluene is 8-10 times of the sum of the mass of the boric acid and the mass of the terminal group modified nitrile rubber; stirring and refluxing the mixed solution for 2-6 hours; distilling out the solvent and the micromolecule by-product generated by the reaction by reduced pressure distillation, and cooling to room temperature; washing and drying the reduced pressure distillation product to obtain the boron oxide/end group modified nitrile rubber composite material;
step b preparation of component a: mixing epoxy resin, a toughening agent and a diluent, heating to 40-80 ℃, and stirring to obtain the epoxy resin-modified epoxy resin;
step c preparation of component B: mixing a curing agent, an accelerator, a diluent and a defoaming agent, and stirring at room temperature to obtain the high-performance polyurethane adhesive;
step d mixing component A with component B.
7. The method of claim 6, wherein: the terminal group modified nitrile rubber in the step a is one of hydroxyl-terminated nitrile rubber, carboxyl-terminated nitrile rubber or epoxy-terminated nitrile rubber.
8. The method of claim 6, wherein: the component A and the component B are mixed at room temperature and rapidly stirred at the speed of 600-.
9. The method of claim 6, wherein: the mixture in the step b is stirred for 1 to 4 hours at the speed of 300-600 revolutions per minute to prepare a component A; the component B in the step c is stirred at the speed of 300-600 rpm for 1-3 hours at room temperature to prepare the component B.
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| CN108003826A (en) * | 2017-12-26 | 2018-05-08 | 上海美东生物材料股份有限公司 | A kind of cold curing flexibility epoxyn |
| CN110205937A (en) * | 2019-05-23 | 2019-09-06 | 长沙理工大学 | Orthotropic plate-ultra-high performance concrete combined bridge deck structure and construction method |
| CN112341973B (en) * | 2020-11-24 | 2023-01-10 | 南京阿斯孚特新材料科技有限公司 | Two-component normal-temperature cured epoxy resin elastomer composition and preparation method thereof |
| CN115651576A (en) * | 2022-09-23 | 2023-01-31 | 河南省交通规划设计研究院股份有限公司 | High-viscosity high-toughness waterproof binding material for coating bridge deck pavement and preparation method thereof |
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| CN103160234A (en) * | 2013-04-09 | 2013-06-19 | 南京大学 | High-performance thermosetting epoxy resin adhesive for roads and bridges and preparation method thereof |
| CN104449514A (en) * | 2014-11-24 | 2015-03-25 | 南京大学 | Epoxy resin bonding agent cured at normal temperature for roads and bridges and preparation method of epoxy resin bonding agent |
| CN105368005A (en) * | 2015-12-22 | 2016-03-02 | 北京天山新材料技术有限公司 | Epoxy pouring sealant and preparation method thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103160234A (en) * | 2013-04-09 | 2013-06-19 | 南京大学 | High-performance thermosetting epoxy resin adhesive for roads and bridges and preparation method thereof |
| CN104449514A (en) * | 2014-11-24 | 2015-03-25 | 南京大学 | Epoxy resin bonding agent cured at normal temperature for roads and bridges and preparation method of epoxy resin bonding agent |
| CN105368005A (en) * | 2015-12-22 | 2016-03-02 | 北京天山新材料技术有限公司 | Epoxy pouring sealant and preparation method thereof |
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