WO2014205609A1

WO2014205609A1 - Ternary fluorescent thermosetting epoxy asphalt composite material and preparation method thereof

Info

Publication number: WO2014205609A1
Application number: PCT/CN2013/000888
Authority: WO
Inventors: 翟洪金; 应珏; 亢阳; 应军
Original assignee: 句容宁武科技开发有限公司
Priority date: 2013-06-27
Filing date: 2013-07-25
Publication date: 2014-12-31
Also published as: CN103333511A

Abstract

Provided is a ternary fluorescent thermosetting epoxy asphalt composite material, consisting of three components: A, B and C, wherein the mass of component A comprises: 40-84 parts of maleimide-modified asphalt, 10-45 parts of an aliphatic amine, 5-25 parts of a polyamide/polyether amine, and 1-15 parts of a compatibilizer; component B is an epoxy resin and the ratio in mass of the component A to component B is 2.2 : 1 - 10 : 1; component C is a fluorescent material, and the mass thereof is 2-20% of the total mass of A and B. The fluorescent epoxy asphalt material has a very bright colour to human eyes under ambient lights, while having a high strength and a good flexibility. It is suitable for park roads, public square pavements, special roads etc., is of very good quality, as well as having the effects of indication and beautification. Also, the material may be used for pavement patterns, text designs etc. for the above-mentioned places, highways and bridges etc., as it has unique advertising effects in the evening.

Description

Three-component fluorescent thermosetting epoxy asphalt composite material and preparation method thereof

The invention relates to a chemically modified asphalt and a preparation method thereof, and more specifically to a three-component fluorescent thermosetting epoxy asphalt composite material and a preparation technique thereof.

Back sync

Asphalt is commonly used as a paving and waterproofing material and is essentially a thermoplastic material. This characteristic is manifested in the pavement paved with asphalt. In the hot summer season, the road surface is prone to rutting under heavy load. In the cold winter season, temperature-shrinking cracks are easy to occur. With the improvement of road grade and large-span steel box girder structure bridge It is widely used, which puts high requirements on the strength, deformation stability and fatigue durability of paving materials. At the same time, it also puts forward special requirements such as high adhesion and imperviousness in the performance. As an important part of the bridge system, the quality of the bridge deck pavement directly affects the safety, comfort, bridge durability and investment economic benefits of the vehicle. Obviously, such high performance requirements are unsuitable for ordinary asphalt, and modified asphalt must be used. There are many methods for modifying asphalt. In general, the excellent properties of epoxy asphalt have been recognized.

Fluorescent epoxy asphalt material has some fairly bright color light seen by the human eye under external illumination, and has high strength and good flexibility. It is used for park roads, square pavements, special roads, etc. It is of excellent quality and has the function of indicating and beautifying. It can also be used in the above-mentioned places as well as paving patterns and texts such as highways and roads and bridges, and has a unique night advertising effect. There have been no reports of fluorescent epoxy asphalt materials.

Summary of the invention

The object of the present invention is to provide a three-component fluorescent thermosetting epoxy asphalt composite material and a preparation method thereof, and the fluorescent epoxy asphalt material of the invention has some relatively bright color light which is visible to the human eye under external illumination, and has high intensity. , good flexibility. It is used for park roads, square pavements, special roads, etc. It is of excellent quality and has the function of indicating and beautifying. It can also be used in the above-mentioned places as well as paving patterns and texts such as highways and roads and bridges, and has a unique night advertising effect.

The object of the present invention is achieved by the following technical solutions:

A three-texture fluorescent thermosetting epoxy asphalt composite material characterized by dryness: the material consists of part A, part B and part C, and the mass ratio of part A to part B is 2.2:1-10:1, part C The quality is 2-20% of the sum of the mass of A and B;

The quality composition of Part A is:

Maleimide modified asphalt 40-84 parts

Fatty amine 10-45 parts Polyamide/polyetheramine 5-25 parts

Compatibilizer 1-15 parts

Part B is epoxy resin and part C is fluorescent material.

In the present invention, the maleimide-modified pitch is obtained by reacting maleimide and a derivative thereof with ordinary pitch. The conventional asphalt may be petroleum pitch, oxidized asphalt, coal pitch or lake asphalt. One or a mixture of these may be selected.

The fatty amine refers to a fatty amine containing three or more active hydrogens, and may be a polyene polyamine or a polymethylene diamine, or a diamine corresponding to a C5 fraction and an unsaturated aliphatic diamine. It is a diamine containing an aromatic ring, such as G-328 of Mitsubishi Gas Chemical. It is possible to select one or a mixture of several.

The polyamide may be a low molecular weight polyamide resin and a modified resin thereof, preferably 4 (TC viscosity is in the range of 30,000 to 80,000 mPa.s, and the amine value is in the range of 50 mgKOH/g to 500 mgKOH/g. The polyamide resin, preferably having a viscosity of 40 ° C in the range of 5,000 to 5,000 mPa·s and a polyamide having an amine value of from 50 mg KOH / g to 300 mg KOH / g, such as Jingchuan 9650, Versamid 140, Versamid 125 and Fuji Chemical 2154, 215X, etc. The polyetheramine may be a diaminophenyl ether such as diaminodiphenyl ether diphenyl sulfone, diaminodiphenyl ether diphenyl ether, etc., diamino bisphenol A Classes, such as diaminodiphenyl ether bisphenol A, etc., may also be polyetheramines having no benzene ring structure, such as huntsman D-230, D-400, D-2000 or T-5000, etc. Alternatively, a mixture of several of them may be selected.

The compatibilizing agent may be a pumping oil of a furfural section in petroleum refining, a phenolic residue which is decomposed by decomposition of cumene hydroperoxide, a pine oil type rubber oil, a coal tar type rubber oil, or a paraffin base. A petroleum-based rubber oil such as a cycloalkyl group or an aromatic hydrocarbon group. The preferred choice is the extraction of oil from the furfural section of petroleum refining and petroleum-based rubber oil. Either one of them can be selected, or a mixture of several of them can be selected.

The fluorescent material is an inorganic fluorescent material or an organic fluorescent material; the inorganic fluorescent material is an alkali earth metal sulfide (such as ZnS, CaS) aluminate (SrA1204, CaA1204, BaA1204) or the like as a luminescent substrate, and the rare earth strontium The element [铕 (Eu), 钐 (Sm), 铒 (Er), 钕 (Nd), etc.] acts as a complex of activator and coactivator. The utility model has the advantages of strong absorption capacity, high conversion rate, narrow band emission of the center ion of the rare earth complex, is favorable for full color display, and the physical and chemical properties are stable. The organic light material is one or a mixture of the following: oxadiazole and Its derivatives, triazoles and their derivatives, rhodamine and its derivatives, coumarin derivatives, 1,8-naphthyl imide derivatives, pyrazoline derivatives, triphenylamine derivatives , porphyrins, carbazole, pyrazine, thiazole derivatives, anthracene derivatives, polyphenylene, polythiophene, polyfluorene, polytriphenylamine and its derivatives, polycarbazole, polypyrrole, poly Porphyrin and its derivatives, copolymers.

By adjusting the proportion of each component in Part A, the properties of the epoxy asphalt material can be varied to meet different conditions. Claim.

There are two methods for preparing the fluorescent epoxy asphalt material of the present invention - one method is: adding the dehydrated matrix asphalt heated to 90-140 ° C to the reactor according to the quality of the formulation, adding 2-20% of the mass of the asphalt. The maleimide or its derivative is kept for 10 to 60 minutes. After the pressure is stabilized, N _{2 is introduced} to maintain the total pressure at 0.25-lMPa. After 3-6 hours of reaction, the pressure is slowly released to O. LMPa; then gradually reduce the temperature to 100-110 Γ add other materials pre-mixed to the pre-mixed A component before the temperature is raised to 90-100 °C, and finally obtain the A component by high-speed dispersion mechanical dispersion such as colloid mill. Part B is epoxy resin, and the mass ratio of Part A to Part B is 2.2:1-10:1. Part C is a fluorescent material, and the mass of Part C is 2-20% of the sum of the masses of A and B. When used, the three parts of A, B and C which are heated to the required temperature are uniformly mixed according to the required ratio, so that the fluorescent thermosetting epoxy asphalt material of the invention can be sprayed on the road surface or the steel plate as epoxy asphalt sticky in a certain time. The layering material; if it is mixed with the aggregate according to a certain ratio of oil to stone (the ratio of the general fluorescent thermosetting epoxy asphalt material to the stone is 4.0:100-9.3:100), it can be paved on the road surface for a certain period of time. Compaction.

Another method is to add a matrix pitch heated to 90-140 Torr to the reactor according to the quality of the formulation, and add 2-20% of the mass of the bitumen or its derivative to the reactor, and heat up to the temperature. 140-160Ό reaction for 3-6 hours, then gradually reduce the temperature to 100-110 °C, add the pre-mixed complete part A of the pre-mixed to 90-140 ° C, and finally disperse it by high-speed dispersion mechanical separation such as colloid mill Part A is obtained, part B is epoxy resin, and the mass ratio of part A to part B is 2.2:1-10:1. Part C is a fluorescent material, and the mass of Part C is 2-20% of the sum of the masses of A and B. When used, the three parts of A, B and C which are heated to the required temperature are uniformly mixed according to the required ratio, so that the fluorescent thermosetting epoxy asphalt material of the invention can be sprayed on the road surface or the steel plate as epoxy asphalt sticky in a certain time. The layering material; if it is mixed into the aggregate according to a certain ratio of oil to stone, it can be paved on the road surface and compacted in a certain period of time.

The present invention firstly amineifies the matrix asphalt, as shown in Fig. 1, Fig. 2, and the reaction mechanism is that asphaltenes and maleimides and their derivatives in the asphalt are synthesized by Michael addition, diene synthesis or π- The π charge transfer reaction makes the asphalt itself an epoxy resin curing agent; this greatly improves the compatibility of other room temperature and medium temperature epoxy resin amine curing agents and curing accelerators with asphalt, and then optimizes the compatibility. The amine-based curing agent gives a storage-stable epoxy asphalt A. Part B is an epoxy resin. Part C is an inorganic fluorescent material.

In use, the three parts of A, B, and C which are heated to the required temperature are uniformly mixed in a desired ratio to obtain the fluorescent thermosetting epoxy asphalt material of the present invention. The fluorescent thermosetting epoxy asphalt material forms a three-dimensional network structure after the curing reaction, and has high strength, high elasticity and fluorescence effect.

The fluorescent epoxy asphalt material of the invention has some relatively bright color light which is seen by the human eye under external illumination, and has high strength and good flexibility. Used for park roads, square pavements, special roads, etc., with excellent quality, indication and beautification Function. It can also be used in the above-mentioned places as well as paving patterns and texts such as highways and roads and bridges, and has a unique night advertising effect.

DRAWINGS

Figure 1 is a schematic diagram of the mechanism of maleimide modified asphalt.

Figure 2 is a schematic diagram of the mechanism of N-phenylmaleimide modified asphalt.

detailed description

The invention is further illustrated by the following examples, but the examples are not intended to limit the invention. Example 1

67 parts (mass, the same below) of petroleum pitch heated to 100 °C (produced by Shanji Temple) was added to the reactor, 1.14 parts of maleimide was added, and the temperature was raised to 130 Ό. After the pressure was stabilized, N _{2 was introduced.} The total pressure was maintained at 0.25 MPa, and after 4 hours of reaction, the pressure was slowly released to 0.1 MPa. Then, the temperature was gradually lowered to 100 ° C, 12 parts of triethylenetetramine was added, and the temperature was raised to 135 ° C for 2 hours. Then, add Jingchuan 9650, which has been previously heated to 120 ,, 16.2 parts, 5 parts of furfural oil, and pre-mix for 30 minutes; then, disperse at a high speed by a colloid mill to obtain Part A, and finally add Part B epoxy resin in a ratio of 2.2:1. -51 , Wuxi Resin Factory), add 2% of the total mass of A and B inorganic phosphors, and mix evenly. This material can be used as a bonding layer for paving.

Example 2

Add 67 parts (mass, the same below) to the petroleum asphalt heated to 90 °C (yield: Shanjia Temple), add 1.14 parts of maleimide, heat up to 135 ° C, and wait until the pressure is stable. N ₂ , the total pressure was maintained at 0.25 MPa, and after 4 hours of reaction, the pressure was slowly released to 0.1 MPa. Then, the temperature was gradually lowered to 100 ° C, 15 parts of hexamethylenediamine was added, and the temperature was raised to 135 ° C for 3 hours. Then add T-5000 (huntsman, USA) preheated to 140 ,, 18.2 parts, 6 parts of naphthenic rubber oil, premix for 30 minutes; then disperse at high speed by colloid mill to obtain part A, and finally add in a ratio of 4.3:1. Part B epoxy resin (E-51, Wuxi Resin Factory), then add 20% of the total mass of A and B of C-part inorganic fluorescent materials, mixed and hooked. This material can be used as a bonding layer for paving.

Example 3

65 parts of oxidized asphalt (National Zhongjie Friendship Farm Liufen Oxidation Bitumen Plant) heated to 140 °C was added to the reactor, 3 parts of N-phenylmaleimide was added, and the temperature was raised to 155 °C for 20 minutes. After the pressure is stabilized, N _{2 is introduced} to maintain the total pressure at 0.25 MPa; after 4 hours of reaction, the pressure is slowly released to 0.1 MPa. Then gradually reduce the temperature to 100 ° C, add 10.45 parts of diaminodiphenylformamidine preheated to 90 ° C, Fuji Chemical into 215X, 25 parts, 8 parts of cycloalkyl rubber oil, premix for 30 minutes, after completion in 0.05 Pumping for 30 minutes under vacuum of MPa; then dispersing at a high speed by a colloid mill to obtain Part A, mixing Part A with Part B epoxy resin (E-44) in a ratio of 3.8:1, then adding A and B part of the total mass of 2% of the C part of the inorganic fluorescent material, and then mixed into the aggregate according to 5-8% oil-stone ratio, heat preservation for 50 minutes, paved in the park road.

Example 4

57 parts of petroleum pitch (US Shell) heated to 130 ° C was added to the reactor, and 3.35 parts of N-phenylmaleimide was added, and the temperature was raised to 150 ° C for 20 minutes. After the pressure was stabilized, N was introduced. ₂ , the total pressure is maintained at 0.25 MPa _; after 4 hours of reaction, slowly relieve pressure to O.lMPa. Then gradually reduce the temperature to 110 Ό, add 9.5 parts of G-328 (Mitsubishi Gas Chemical, Japan) preheated to 140 °C, 2154, 25 parts of Fuji Chemical, 6.5 parts of furfural extraction oil, premix for 30 minutes, and complete at 0.05 MPa. Pumping under vacuum for 30 minutes; then dispersing at a high speed through a colloid mill to obtain Part A, mixing Part A with Part B epoxy resin (E-44) in a ratio of 2.9:1, then adding a total mass of A and B of 20% C Part of the inorganic fluorescent material, and then mixed into the aggregate according to the 5-8% oil-stone ratio, and kept for 50 minutes for square paving.

Example 5

Add 55 parts of petroleum pitch (US Shell) heated to 100'C to the reactor, add 3 parts of N-phenylmaleimide, raise the temperature to 155 °C, and gradually cool down to 110 °C after 4 hours of reaction. 8.4 parts of isophoronediamine, Versamid 140, 25 parts, 8 parts of aromatic hydrocarbon oil, previously heated to 120 ° C, premixed for 30 minutes, and then pumped under vacuum of 0.05 MPa for 30 minutes; then passed through a colloid mill High-speed dispersion to obtain Part A, mixing Part A with Part B epoxy resin (E-44) in a ratio of 4.8:1, then adding A and B mass total 8% of Part C inorganic fluorescent material, and then 5-8% The oil-stone ratio is mixed into the aggregate and kept for 50 minutes for road paving.

Example 6

Add 67 parts (mass, the same below) to 100 Ό petroleum pitch (origin: Shanjia Temple), add 1.14 parts of maleimide, and heat up to 135 Ό. After the pressure is stable, pass N ₂ to make The total pressure was maintained at 0.25 MPa, and after 4 hours of reaction, the pressure was slowly released to 0.1 MPa. Then, the temperature was gradually lowered to 110 ° C, 12 parts of triethylenetetramine was added, and the temperature was programmed to 135 ° C for 2 hours. Then, Jingchuan 9650, which has been previously heated to 120 °C, 16.2 parts, 5 parts of furfural oil, and premixed for 30 minutes; and then dispersed at a high speed by a colloid mill to obtain Part A. Mix in a ratio of 2:1 by mass ratio of Part A to Part B. Part B is epoxy resin, then add the C part of the organic fluorescent material oxadiazole with the total mass of A and B, and then mix the aggregate with 5-8% oil-stone ratio: keep warm for 50 minutes, and carry out road paving.

Example 7

Add 67 parts (mass, the same below) to the petroleum pitch (origin: Shanjia Temple) heated to 90 °C, add 1.14 parts of maleimide, and heat up to 130 Γ. After the pressure is stable, pass N ₂ The total pressure was maintained at 0.25 MPa, and after 4 hours of reaction, the pressure was slowly released to 0.1 MPa. Then, the temperature was gradually lowered to 110 ° C, 15 parts of hexamethylenediamine was added, and the temperature was programmed to 135 ° C for 3 hours. Then add T-5000 (huntsman, USA) preheated to 140 ° C, 18.2 Part, 6 parts of cyclodecyl rubber oil, premixed for 30 minutes; then dispersed at high speed by a colloid mill to obtain part A. Mix in a ratio of 8:1 by mass ratio of Part A to Part B. Part B is epoxy resin, and then a part of the total mass of A and B is 10% of the C part of the organic fluorescent material polythiophene, and then mixed with the aggregate according to the 5-8% oil-stone ratio, and kept for 50 minutes for road paving.

Example 8

Adding 55 parts of TC petroleum asphalt (US Shell) to the reactor, adding 3 parts of N-phenylmaleimide, heating to 155 ° C, and gradually cooling to 110 反应 after 4 hours of reaction, adding pre-heating 8.4 parts of isophoronediamine to 120 ° C, Versamid 140, 25 parts, 8 parts of aromatic hydrocarbon oil, premixed for 30 minutes, and then pumped under vacuum of 0.05 MPa for 30 minutes; then dispersed at high speed by colloid mill Obtain part A. Mix well according to the mass ratio of part A to part B of 2.8:1. Part B is epoxy resin, then add the mass of A and B and 10% of the C part organic fluorescent material Rhodamine, then press 5- 8% of the oil-stone ratio is mixed into the aggregate, and it is kept for 50 minutes for road paving.

Claims

Rights request

A three-component fluorescent thermosetting epoxy asphalt composite material characterized in that: the material consists of Part A, Part B and Part C, and the mass ratio of Part A to Part B is 2.2:1-10:1, C The mass of part is 2-20% of the sum of the mass of A and B;

The quality composition of Part A is:

Maleimide modified asphalt 40-84 parts

Fatty amine 10-45 parts Polyamide / Polyether amine 5-25 parts Compatibilizer 1-15 parts

Part B is epoxy resin and part C is fluorescent material.

2. The three-component fluorescent thermosetting epoxy asphalt composite according to claim 1, wherein: the maleimide modified asphalt is reacted with a common pitch using maleimide and a derivative thereof. be made of.

The three-component fluorescent thermosetting epoxy asphalt composite according to claim 2, wherein the ordinary asphalt is petroleum asphalt, oxidized asphalt, coal tar pitch or lake asphalt.

The three-component fluorescent thermosetting epoxy asphalt composite according to claim 1, wherein the fatty amine is a fatty amine containing three or more active hydrogens, and is a polyene polyamine or a polymethylene group. The diamines are either diamines and unsaturated aliphatic diamines corresponding to the C5 fraction, or diamines containing an aromatic ring, or a mixture of one or more of them.

The three-component fluorescent thermosetting epoxy asphalt composite according to claim 1, wherein: the fluorescent material is an inorganic fluorescent material or an organic fluorescent material; and the inorganic fluorescent material is an alkaline earth metal sulfide or aluminum. a salt as a luminescent substrate, a complex of a rare earth lanthanide as an activator and a co-activator; the organic fluorescent material being a mixture of one or more of the following: oxadiazole and its derivatives, triazole and Its derivatives, rhodamine and its derivatives, coumarin derivatives, 1,8-naphthyl imide derivatives, pyrazoline derivatives, triphenylamine derivatives, porphyrins, hydrazine Azole, pyrazine, thiazole derivative, anthracene derivative, polyphenylene, polythiophene, polyfluorene, polytriphenylamine and its derivatives, polycarbazole, polypyrrole, polyporphyrin and its derivatives, copolymerization Things.

The three-component fluorescent thermosetting epoxy asphalt composite according to claim 1, wherein the polyamide is a low molecular weight polyamide resin and a modified resin thereof, and has a viscosity of 30,000 at 40 ° C. Within the 80,000 mPa. _S , a polyamide resin having an amine value of from 50 mgKOH/g to 500 mgKOH/g.

The three-component fluorescent thermosetting epoxy asphalt composite according to claim 1, wherein the polyetheramine is diaminophenyl ether, diaminobisphenol A, or no benzene ring. A polyetheramine of the structure, or a mixture of one or more of them.

The three-component fluorescent thermosetting epoxy asphalt composite according to claim 1, wherein: the compatibilizing agent is an oil extracted from a furfural section of petroleum refining, and the cumene hydroperoxide is decomposed and distilled. Phenolic residue, pine oil rubber oil, coal tar rubber oil, or paraffin-based, cycloalkyl or aromatic petroleum-based rubber oil, or a mixture of one or more thereof.

9. A method for preparing a three-component fluorescent thermosetting epoxy asphalt composite according to claim 1, wherein: the dehydrated matrix pitch heated to 90-140 ° C is added to the reactor according to the quality of the formulation. Add 2-20% of maleic imide or its derivative of asphalt quality. After the pressure is stable, pass N ₂ to keep the total pressure at 0.25-lMPa. After 3-6 hours of reaction, slowly relieve pressure. To O.lMPa; then gradually reduce the temperature to 100-110O, add other materials of pre-mixed A component pre-heated to 90-100 °C, and finally disperse evenly to obtain component A; part B is epoxy resin, A The mass ratio of part to part B is 2.2:1-10:1; part C is inorganic fluorescent material, and the mass of part C is 2-20% of the sum of mass of A and B.

10. The method for preparing a three-component fluorescent thermosetting epoxy asphalt composite material according to claim 1, wherein: the base asphalt heated to 90-140 ° C is added to the reactor according to the quality of the formulation, and the asphalt is added. 2-20% of the mass of maleimide or its derivative is added to the reactor, and the temperature is raised to 140-160 Ό for 3-6 hours, then gradually lowered to 100-110 Γ, and the temperature is raised to 90-140'C beforehand. Premixing the other components of the complete Part A, and finally redispersing to obtain Part A; Part B is an epoxy resin, the mass ratio of Part A to Part B is 2.2:1-10:1; Part C is an inorganic fluorescent material, The mass of Part C is 2-20% of the sum of the mass of A and B.