CN115029010A - Utilization method of phenol-based rectifying still residues and epoxy asphalt material modified by phenol-based rectifying still residues - Google Patents
Utilization method of phenol-based rectifying still residues and epoxy asphalt material modified by phenol-based rectifying still residues Download PDFInfo
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L95/00—Compositions of bituminous materials, e.g. asphalt, tar, pitch
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- 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
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
- C08G59/4207—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof aliphatic
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- 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
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
- C08G59/4215—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof cycloaliphatic
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Abstract
The invention belongs to the field of materials, and provides a utilization method of phenol-based rectifying still residues and an epoxy asphalt material modified by the phenol-based rectifying still residues, wherein the epoxy asphalt material comprises a component A and a component B; the component A comprises asphalt, phenol-based rectifying still residues, a first curing agent and a second curing agent; the component B comprises epoxy resin. According to the invention, the epoxy asphalt is modified by utilizing the structures of the phenol group, the long chain and the like in the phenol group rectifying still residue, so that the production cost can be reduced, the environmental pollution is reduced, and the performance of the epoxy asphalt material can be better improved by combining the special group in the phenol group rectifying still residue with the asphalt and the epoxy resin, thereby reducing the addition of other additional components, facilitating the construction and reducing the cost of the epoxy asphalt.
Description
Technical Field
The invention belongs to the field of materials, and particularly relates to a utilization method of phenol-based rectifying still residues and an epoxy asphalt material modified by the phenol-based rectifying still residues.
Background
The rectifying still residue is typical waste pollutant, especially phenol-based rectifying still residue, and ordinary landfill treatment mode can cause the waste of land resource and the pollution of groundwater resource, and incineration disposal also can produce a large amount of toxic gas, consequently seeks the phenol-based rectifying still residue of environmental protection and handles the new mode, realizes the problem of the incomplete utilization of phenol-based rectifying still urgent need to be solved.
The byproduct components in the production process of the dodecylphenol are heavy, contain a large amount of phenol groups, long-chain groups, unsaturated double bonds and the like, and the recovery rate of effective resources is low and the energy consumption is high by adopting the conventional cracking treatment, so that the finding of an effective and environment-friendly treatment mode of the rectifying still residue in the production process of the dodecylphenol has great significance for the industrial production of the dodecylphenol.
CN112624906A discloses a p-trifluoromethylaniline rectification kettle residue treatment process, which comprises the steps of carrying out distillation on p-trifluoromethylaniline and a byproduct p-trifluoromethylphenol in p-trifluoromethyltoluidine rectification residual liquid, wherein a part of the p-trifluoromethylaniline and the byproduct p-trifluoromethylphenol are not distilled off; after dissolving the p-trifluoromethylaniline and the byproduct p-trifluoromethylphenol in the residual liquid by using a solvent, converting the p-trifluoromethylaniline into the p-trifluoromethylphenol through diazotization and hydrolysis, obtaining a p-trifluoromethylphenol product through a proper process, and realizing the recycling of solid wastes. However, the composition of the rectification still residue containing phenol is far from that of the byproduct still residue in the production of dodecylphenol, and the rectification still residue containing phenol cannot be applied to the treatment and utilization of the byproduct still residue in the production of dodecylphenol.
CN111672317A discloses a purification treatment method of distillation still residue, which comprises the following steps: the temporary oxygen cracking device is in a continuous rotating state, after the rectifying still residue enters the temporary oxygen cracking device, low-temperature temporary oxygen cracking oxidation treatment is carried out in the air atmosphere and in the presence of a temporary oxygen cracking catalyst, and gas containing organic matters generated by cracking oxidation treatment enters the catalytic oxidation device for catalytic oxidation treatment. However, the treatment mode of the rectifying still residue does not utilize the rectifying still residue as a resource, and the critical control of the critical oxygen condition is required, so that the requirement on the catalyst is high.
CN108689806A discloses a method for recovering cresol from cresol product rectification kettle residual liquid, which comprises the steps of distilling the cresol rectification kettle residual liquid to remove light, cracking the cresol rectification kettle residual liquid in the presence of a catalyst, and recovering valuable products. However, the whole component of the cresol product rectification residual liquid is lighter and is difficult to be suitable for the kettle residue in the production process of the dodecylphenol.
In conclusion, a method for environment-friendly resource utilization is urgently needed for the distillation kettle residues generated in the production process of the dodecylphenol.
Disclosure of Invention
In view of the problems in the prior art, the invention provides a utilization method of phenol-based rectifying still residues and an epoxy asphalt material modified by the phenol-based rectifying still residues, wherein the utilization method can be used for carrying out resource treatment on the rectifying still residues generated in the production process of dodecylphenol and improving the mechanical property of the epoxy asphalt.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a phenolic group rectifying still residue modified epoxy asphalt material, which comprises a component A and a component B;
the component A comprises asphalt, phenol-based rectifying still residues, a first curing agent and a second curing agent;
the component B comprises epoxy resin.
The phenol-based rectifying still residue modified epoxy asphalt material provided by the invention can obviously improve the compatibility between asphalt and epoxy resin by adopting the phenol-based rectifying still residue as a modified substance, the phenol-based rectifying still residue not only can form Van der Waals force or hydrogen bond between the asphalt and the epoxy resin, but also can form molecular bonds by long fatty chains, double bonds, phenol groups and other structures in the phenol-based rectifying still residue which are more favorable for the compatibility between the asphalt and the epoxy resin compared with a conventional compatilizer, and can also carry out cross-linking reaction in the curing process, so that the asphalt is favorably dispersed in the epoxy resin in the form of uniform dispersed phase, and the performance of the epoxy asphalt material is greatly improved.
Preferably, the epoxy asphalt material does not contain a compatibilizer and a diluent other than the phenol-based rectification residue.
The invention can play a good role in the compatibility of asphalt and epoxy resin due to the addition of the phenol-based rectifying still residues, thereby omitting the addition of other compatilizers and diluents, achieving a good modification effect only by the phenol-based rectifying still residues, and remarkably improving the mechanical property of the epoxy asphalt material.
Preferably, the phenol-based rectifying still residue is rectifying still residue obtained after decompression and deep drawing in the production process of the dodecylphenol.
The production process of the dodecylphenol in the invention is a production process commonly used by a person skilled in the art, the deep drawing under reduced pressure refers to a rectification purification process of a crude product of the dodecylphenol after production, and the process conditions of the deep drawing under reduced pressure are also conventional process conditions of the deep drawing under reduced pressure in the art.
Preferably, the phenolic rectification kettle residue contains a carbon-carbon double bond, an undecyl group, a phenolic group and a benzene ring, and preferably, the phenolic rectification kettle residue also contains any one or a combination of at least two of an alkyl group, a ketone group or an ether linkage with 1-5 carbon atoms, wherein typical but non-limiting combinations are a combination of a methyl group and a ketone group, a combination of a methyl group and an ether linkage and the like.
Specifically, the phenolic group rectifying still residue contains any one or a combination of at least two of phenestrol, 2-methyl-4-tert-octylphenol, p-undecylanisole, phenol, 5-methyl-4-undecene or hexanestrol.
Wherein the structural formula of the phenestrol is shown as the following formula (1):
The structural formula of the p-undecyl anisole is shown as the following formula (2):
The structural formula of the 2-methyl-4-tert-octylphenol is shown as the following formula (3):
The phenol-based rectification kettle residue contains the phenestrol, a single molecule simultaneously has two phenol groups, and the p-undecyl anisole has a long-chain fatty chain and a benzene ring, so that the specific structures promote the compatibility of the asphalt and the epoxy resin, and substances such as 2-methyl-4-tert-octylphenol and the like also improve the compatibility effect of the asphalt and the epoxy resin due to the existence of double bonds and the benzene ring.
Preferably, the phenol-based rectifying still residue contains 24-28 wt% of phenestrol, 2-5 wt% of 2-methyl-4-tert-octylphenol, 1-2 wt% of p-undecyl anisole and 1-2 wt% of phenol.
The amount of the above-mentioned benzestrol in the range of 24 to 28wt% may be, for example, 24wt%, 24.5wt%, 25wt%, 25.5wt%, 26wt%, 26.5wt%, 27wt%, 27.5wt%, or 28wt%, but is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable.
The 2-methyl-4-tert-octylphenol content of 2 to 5wt% may be, for example, 2wt%, 2.5wt%, 3wt%, 3.5wt%, 4wt%, 4.5wt%, or 5wt%, but is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable.
The proportion of 1 to 2wt% of p-undecylanisole may be, for example, 1wt%, 1.1wt%, 1.2wt%, 1.3wt%, 1.4wt%, 1.5wt%, 1.6wt%, 1.7wt%, 1.8wt%, 1.9wt%, or 2wt%, but is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable.
The phenol content of 1 to 2wt% may be, for example, 1wt%, 1.2wt%, 1.4wt%, 1.5wt%, 1.7wt%, 1.8wt%, 1.9wt%, or 2wt%, but is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable.
Preferably, the epoxy asphalt material consists of a component A and a component B, wherein the component A consists of asphalt, phenol-based rectifying still residue, a first curing agent and a second curing agent, and the component B is epoxy resin.
Preferably, the mass ratio of the a component to the B component is 2.5 to 4.5:1, and may be, for example, 2.5:1, 2.6:1, 2.7:1, 2.8:1, 3:1, 3.2:1, 3.4:1, 3.5:1, 3.7:1, 3.9:1, 4:1, 4.2:1, 4.4:1, or 4.5:1, but is not limited to the recited values, and other values not recited within this range are equally applicable.
The invention further preferably controls the mass ratio of the two components within the range, thereby being more beneficial to improving the mechanical property of the final epoxy asphalt material.
Preferably, the component A comprises 20-30 parts by weight of asphalt, 15-20 parts by weight of phenol-based rectifying still residues, 10-20 parts by weight of first curing agents and 3-10 parts by weight of second curing agents.
In the invention, the mass ratio of the phenol-based rectifying still residue to the asphalt is preferably controlled within the range of 0.5-1: 1, for example, 0.5:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1 or 1.0:1, so that the improvement of the dispersion effect of the phenol-based rectifying still residue on the asphalt is more favorably ensured.
Wherein the component A comprises 20 to 30 parts of asphalt by weight, such as 20 parts, 22 parts, 23 parts, 24 parts, 25 parts, 26 parts, 27 parts, 28 parts, 29 parts or 30 parts, etc., but not limited to the values listed, and other values not listed in the range are also applicable.
The phenol-based rectification residue may be 15 to 20 parts, for example, 15 parts, 15.6 parts, 16.2 parts, 16.7 parts, 17.3 parts, 17.8 parts, 18.4 parts, 18.9 parts, 19.5 parts or 20 parts, but is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable.
The amount of the first curing agent is, for example, 10 to 20 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts or 20 parts, but is not limited to the above-mentioned values, and other values not shown in the above range are also applicable.
The second curing agent may be, for example, 3 to 10 parts, 3.8 parts, 4.0 parts, 5.0 parts, 5.4 parts, 6.0 parts, 6.2 parts, 7.0 parts, 7.7 parts, 8.0 parts, 8.5 parts, 9.0 parts, 9.3 parts or 10 parts, but is not limited to the above-mentioned numerical values, and other numerical values not mentioned in the above range are also applicable.
Preferably, the phenol-based rectifying still residue is a deep-drawing heavy component generated by rectification in the purification stage of the dodecylphenol.
Preferably, the phenol-based rectification kettle residue contains a phenol-based group and a long-chain unsaturated double bond.
Preferably, the number of carbon atoms of the long chain unsaturated double bond is 8 to 15, for example, 8, 9, 10, 11, 12, 13, 14 or 15, and the like, but is not limited to the recited values, and other values not recited in the range are also applicable.
Preferably, the phenol-based still bottoms are brown liquid at 20 ℃.
Preferably, the density of the phenol-based rectifying still residue at 20 ℃ is 0.8-0.9 g/cm 3 For example, it may be 0.8g/cm 3 、0.81g/cm 3 、0.82g/cm 3 、0.83g/cm 3 、0.85g/cm 3 、0.86g/cm 3 、0.87g/cm 3 、0.88g/cm 3 、0.89g/cm 3 Or 0.9g/cm 3 And the like, but are not limited to the recited values, and other values not recited within the range are equally applicable.
Preferably, the phenol-based rectifying still residue has a viscosity of 1.2 to 1.5 pas at 20 ℃, and may be, for example, 1.2 pas, 1.24 pas, 1.27 pas, 1.3 pas, 1.34 pas, 1.37 pas, 1.4 pas, 1.44 pas, 1.47 pas or 1.5 pas, but is not limited to the above-mentioned values, and other values not specifically mentioned in the above range are also applicable.
Preferably, the asphalt is rubber modified asphalt.
Preferably, the first curing agent comprises a long chain carboxylic acid curing agent, preferably azelaic acid and/or sebacic acid.
Preferably, the second curing agent comprises an anhydride-based curing agent, preferably comprising any one or a combination of at least two of tung oil anhydride, methyl tetrahydrophthalic anhydride or methyl hexahydrophthalic anhydride, with typical but non-limiting combinations being combinations of tung oil anhydride and methyl tetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride and methyl tetrahydrophthalic anhydride, and combinations of tung oil anhydride and methyl hexahydrophthalic anhydride.
The invention preferably adopts the combination of the two curing agents, thereby being capable of strengthening the performance of the epoxy asphalt material without adding other compatilizers and diluents.
Preferably, the first curing agent is sebacic acid, and the second curing agent is methyl tetrahydrophthalic anhydride.
According to the invention, sebacic acid and methyl tetrahydrophthalic anhydride are further preferably selected as the preferable curing agent combination, so that a better curing effect can be achieved, the dispersion of asphalt and epoxy asphalt is promoted, and the mechanical property of the final epoxy asphalt material is improved.
Preferably, the epoxy resin comprises liquid bisphenol A glycidyl ether epoxy resin E-51 and/or liquid bisphenol A glycidyl ether epoxy resin E-44.
In a second aspect, the present invention provides a method for utilizing phenol-based still bottoms, comprising: and (3) modifying the epoxy asphalt by utilizing the phenol-based rectifying still residues to obtain the phenol-based rectifying still residue modified epoxy asphalt material of the first aspect.
Preferably, the utilization method includes: adding a first curing agent and a second curing agent into the first mixed asphalt and the phenol-based rectifying still residue, and performing second mixing to obtain a component A; and thirdly, mixing the component A and the component B containing epoxy resin, and curing to obtain the phenolic group rectifying still residue modified epoxy asphalt material.
The method of the invention mixes the asphalt and the phenol-based rectifying still residue to make the mixed system in a flowing state, so as to achieve the purpose of uniformly mixing the asphalt and the phenol-based rectifying still residue, adds the curing agent, and then mixes and cures the component A and the component B, which is beneficial to the asphalt existing in the final epoxy asphalt material in the form of uniform dispersion phase, thereby improving the mechanical property of the whole material.
Preferably, the temperature of the asphalt in the first mixing is 140 to 160 ℃, and may be, for example, 140 ℃, 143 ℃, 145 ℃, 147 ℃, 149 ℃, 152 ℃, 154 ℃, 156 ℃, 158 ℃, or 160 ℃, but is not limited to the values listed, and other values not listed in the range are also applicable.
Preferably, the temperature of the first mixing is 140 to 160 ℃, for example, 140 ℃, 143 ℃, 145 ℃, 147 ℃, 149 ℃, 152 ℃, 154 ℃, 156 ℃, 158 ℃, or 160 ℃, but not limited to the recited values, and other values not recited in the range are also applicable.
Preferably, the time for the first mixing is 10 to 15min, for example, 10min, 11min, 12min, 13min, 14min or 15min, but is not limited to the values listed, and other values not listed in this range are also applicable.
The stirring method and speed of the first mixing in the present invention are not particularly limited, and any stirring method known to those skilled in the art may be used, for example, paddle stirring and/or manual stirring bar stirring, as long as the effect of relatively uniform mixing of the asphalt and the phenol-based distillation residue can be achieved, for example, the stirring speed may be 100 to 200r/min, for example, 100r/min, 112r/min, 123r/min, 134r/min, 145r/min, 156r/min, 167r/min, 178r/min, 189r/min or 200r/min, but not limited to the above-mentioned values, and other values not listed in the above-mentioned range may be applied as well.
Preferably, the temperature of the second mixing is 140 to 160 ℃, for example, 140 ℃, 143 ℃, 145 ℃, 147 ℃, 149 ℃, 152 ℃, 154 ℃, 156 ℃, 158 ℃, 160 ℃ or the like, but not limited to the recited values, and other values not recited in the range are also applicable.
Preferably, the time of the second mixing is 100 to 120min, for example, 100min, 103min, 105min, 107min, 109min, 112min, 114min, 116min, 118min or 120min, etc., but is not limited to the recited values, and other values not recited in the range are also applicable.
Preferably, the stirring speed of the second mixing is 550 to 650r/min, for example 550r/min, 560r/min, 570r/min, 580r/min, 590r/min, 600r/min, 610r/min, 620r/min, 640r/min, or 650r/min, but is not limited to the values listed, and other values not listed in this range are also applicable.
Preferably, the temperature of the component B in the third mixing is 60 to 70 ℃, for example, 60 ℃, 62 ℃, 63 ℃, 64 ℃, 65 ℃, 66 ℃, 67 ℃, 68 ℃, 69 ℃ or 70 ℃ and the like, but not limited to the recited values, and other values not recited in the range are also applicable.
Preferably, the temperature of the third mixing is 140 to 155 ℃, for example, 140 ℃, 142 ℃, 145 ℃, 147 ℃, 148 ℃, 149 ℃, 150 ℃, 151 ℃, 152 ℃, 153 ℃, 154 ℃, 155 ℃ and the like, but not limited to the cited values, and other values not listed in the range are also applicable.
Preferably, the time for the third mixing is 3 to 5min, for example, 3min, 3.3min, 3.5min, 3.7min, 3.9min, 4.0min, 4.4min, 4.6min, 4.8min or 5min, etc., but is not limited to the values listed, and other values not listed in this range are also applicable.
Preferably, the stirring speed of the third mixing is 550 to 650r/min, for example 550r/min, 560r/min, 570r/min, 580r/min, 590r/min, 600r/min, 610r/min, 620r/min, 630r/min or 650r/min, etc., but is not limited to the values listed, and other values not listed in this range are also applicable.
Preferably, the viscosity of the third mixed system is less than 1 pas within 40min, and may be, for example, 0.9 pas, 0.85 pas, 0.8 pas, 0.75 pas, 0.7 pas, or 0.6 pas, but is not limited to the recited values, and other values not recited in this range are also applicable.
Preferably, the curing temperature is 130 to 150 ℃, for example, 130 ℃, 133 ℃, 135 ℃, 137 ℃, 139 ℃, 142 ℃, 144 ℃, 146 ℃, 148 ℃ or 150 ℃, etc., but not limited to the recited values, and other values not recited in the range are also applicable.
Preferably, the curing and curing time is 10 to 15 hours, for example, 10 hours, 10.6 hours, 11.2 hours, 11.7 hours, 12.0 hours, 12.3 hours, 12.8 hours, 13.4 hours, 14.0 hours, 14.5 hours or 15 hours, etc., but not limited to the recited values, and other values not recited in the range are also applicable.
As a preferable technical solution of the present invention, the utilization method comprises the steps of:
adding a first curing agent and a second curing agent into the first mixed phenol-based rectification kettle residue and the rubber modified asphalt at the temperature of 140-160 ℃, and carrying out second mixing at the temperature of 140-160 ℃ to obtain a component A; and thirdly, mixing the component A and the component B containing epoxy resin for 3-5 min at the temperature of 140-155 ℃, and curing for 10-15 h at the temperature of 130-150 ℃ to obtain the phenol-based rectifying still residue modified epoxy asphalt material.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) the utilization method of the phenol-based rectifying still residue provided by the invention fully utilizes the structures of long fatty chains, double bonds and the like in the phenol-based rectifying still residue component, and is effectively compatible with the matrix asphalt; meanwhile, the single molecule contains a plurality of hydroxyl and other active functional groups, and the cross-linking curing reaction can be carried out under the action of a curing agent to form a network structure, so that the asphalt component is uniformly dispersed in the epoxy resin network in a dispersion phase, and compared with the condition that most of compatibilizer only forms Van der Waals force or hydrogen bond between two phases, the molecules in the phenol-based rectification kettle residue can form a molecular bond with stronger acting force between the asphalt and the epoxy resin through the cross-linking reaction, the compatibility of the asphalt and the epoxy resin is improved, and the mechanical property of the epoxy asphalt material is improved;
(2) the method for utilizing the phenol-based rectifying still residue provided by the invention adopts heavy components obtained after deep vacuum distillation, has high integral boiling point, is non-volatile in the preparation and use processes of materials, is friendly to human body and environment under construction and normal conditions, and basically has no environmental pollution;
(3) on the basis of ensuring better compatibility, the epoxy asphalt material provided by the invention has lower viscosity, and after the A, B two components are uniformly mixed, the integral viscosity of the system is less than 1 Pa.s after the dispersion system is uniformly mixed within 1h, the system retention time is longer, enough construction time is reserved, and meanwhile, the number of added components is less, so that the construction operation difficulty and the additive cost are reduced;
(4) the epoxy asphalt material provided by the invention has simple components, does not need to add a large amount of compatibilizer and diluent additionally, and obviously reduces the production cost of the epoxy asphalt material.
Drawings
FIG. 1 is a fluorescence microscopic image of an epoxy asphalt material provided in example 1 of the present invention.
FIG. 2 is a microscope image of an epoxy asphalt material provided in example 1 of the present invention.
FIG. 3 is a graph showing the viscosity of the mixed A-component and B-component epoxy asphalt material of example 1 of the present invention as a function of time.
FIG. 4 is a microscope image of an epoxy asphalt material provided in comparative example 1 of the present invention.
FIG. 5 is a microscope image of an epoxy asphalt material provided in comparative example 3 of the present invention.
Detailed Description
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings.
The present invention is described in further detail below. The following examples are merely illustrative of the present invention and do not represent or limit the scope of the claims, which are defined by the appended claims.
For convenience of experiment, the phenol-based rectifying still residue is generated by a dodecylphenol rectifying and purifying process of a certain factory, and the concrete composition is shown in table 1, wherein sebacic acid is obtained from Tianjin Xiansi Biotechnology and technology Limited, the purity is 98%, methyl tetrahydrophthalic anhydride and methyl hexahydrophthalic anhydride are obtained from Guangzhou Qihua chemical industry Limited, eleostearic acid anhydride is obtained from Jining Macroming chemical reagent Limited, dodecylphenol is obtained from Guangdong Xinhuayue, cardanol is obtained from Jining Huakai resin Limited, nonylphenol is obtained from Shanghai Biao medicine, C 12 ~C 14 Glycidyl ether was obtained from Shanghai Bian medicine, diethylenetriamine was obtained from Shanghai Saen chemical technology Co., Ltd, and triethylamine was obtained from Tianjin Mao chemical reagent plant. However, the specific materials of the present invention are not limited to the above-mentioned types or manufacturers.
TABLE 1
| Name of substance | Mass percent of |
| Phenyloestrol | 26.0523% |
| 2-methyl-4-tert-octylphenol | 4.8824% |
| Phenol and its preparation | 1.6325% |
| Undecyl anisole | 1.4511% |
| 5-methyl-4-undecene | 1.0996% |
| Hexane-estrol | 1.0031% |
First, an embodiment
Example 1 (original example 6)
The embodiment provides a utilization method of phenol-based rectifying still residues, which comprises the following steps:
preheating 30 parts of rubber modified asphalt (manufactured by the company of chenge platform and building asphalt Co., Ltd.) at 150 ℃ for 1h to a flowing state, then carrying out first mixing with 17 parts of phenol-based rectifying still residues, then adding 17 parts of sebacic acid and 6 parts of methyl tetrahydrophthalic anhydride, uniformly stirring, and continuously stirring for 120min at 600r/min at 150 ℃ for carrying out second mixing to obtain a component A;
preheating 23 parts of E-51 epoxy resin (produced by Tianjin neutralization Shengtai chemical company) to 60 ℃ to obtain a component B, mixing the component A and the component B at 150 ℃ for a third time, stirring at 600r/min for 5min, and curing at 150 ℃ for 13h to obtain the phenol-based rectifying still residue modified epoxy asphalt material.
The embodiment also provides an epoxy asphalt material, which comprises a component A and a component B;
the component A comprises 30 parts of rubber modified asphalt, 17 parts of phenol-based rectifying still residues, 17 parts of sebacic acid and 6 parts of methyl tetrahydrophthalic anhydride;
the component B is 23 parts of E-51 epoxy resin.
The fluorescence microscopic image of the epoxy asphalt material prepared in the embodiment is shown in fig. 1, the ordinary microscopic image is shown in fig. 2, as can be seen from fig. 1 and fig. 2, the asphalt is uniformly distributed in the epoxy resin, the distribution size of the asphalt main body is about 15 μm, the distribution size is small, the large-size asphalt is small, as can be seen from fig. 3, the system of the epoxy asphalt material prepared in the embodiment changes slowly with time after the component A and the component B are mixed, the viscosity within 1h can be guaranteed to be less than 1Pa · s, and the construction is convenient to carry out.
Example 2
The embodiment provides a utilization method of phenol-based rectifying still residues, which comprises the following steps:
preheating 20 parts of rubber modified asphalt (manufactured by the company of chenge platform and build-up asphalt Co., Ltd.) at 140 ℃ for 0.5h to a flowing state, then carrying out first mixing with 20 parts of phenol-based rectification kettle residues, then adding 10 parts of sebacic acid and 10 parts of methyl tetrahydrophthalic anhydride, uniformly stirring, and continuously stirring for 150min at the temperature of 140 ℃ at 500r/min for carrying out second mixing to obtain a component A;
preheating 20 parts of E-51 epoxy resin (produced by Tianjin Zhongshengtai chemical company) to 55 ℃ to obtain a component B, thirdly mixing the component A and the component B at 140 ℃, stirring at 400r/min for 6min, and curing at 130 ℃ for 15h to obtain the phenol-based rectifying still residue modified epoxy asphalt material.
The embodiment also provides an epoxy asphalt material obtained by the utilization method, and the epoxy asphalt material comprises a component A and a component B;
the component A comprises 20 parts of rubber modified asphalt, 20 parts of phenol-based rectifying still residue, 10 parts of sebacic acid and 10 parts of methyl tetrahydrophthalic anhydride;
the component B is 20 parts of E-51 epoxy resin.
Example 3
The embodiment provides a utilization method of phenol-based rectifying still residues, which comprises the following steps:
preheating 25 parts of rubber modified asphalt (manufactured by the chenge platform bulong asphalt company Limited) at 160 ℃ for 0.5h to a flowing state, then carrying out first mixing on the rubber modified asphalt and 15 parts of phenol-based rectifying still residues, then adding 20 parts of sebacic acid and 3 parts of methyl tetrahydrophthalic anhydride, uniformly stirring, and continuously stirring for 100min at the temperature of 160 ℃ at 400r/min for second mixing to obtain a component A;
preheating 25 parts of E-51 epoxy resin (produced by Tianjin Zhongshengtai chemical company) to 70 ℃ to obtain a component B, thirdly mixing the component A and the component B at 160 ℃, stirring at 600r/min for 3min, and curing at 150 ℃ for 10h to obtain the phenol-based rectifying still residue modified epoxy asphalt material.
The embodiment also provides an epoxy asphalt material obtained by the utilization method, and the epoxy asphalt material comprises a component A and a component B;
the component A comprises 25 parts of rubber modified asphalt, 15 parts of phenol-based rectifying still residue, 20 parts of azelaic acid and 3 parts of methyl tetrahydrophthalic anhydride;
the component B is 15 parts of E-51 epoxy resin.
Example 4
This example provides an epoxy asphalt material that is the same as that of example 1 except that methyl tetrahydrophthalic anhydride was replaced with tung oil anhydride in component a.
Example 5
This example provides a method for utilizing phenol-based distillation residue, which is the same as in example 1 except that rubber-modified asphalt is not preheated.
Example 6
This example provides a method for utilizing phenol-based rectifying still residue, which includes replacing 2 parts of phenol-based rectifying still residue with 2 parts of C 12 -C 14 The same procedure as in example 1 was repeated except that alkyl glycidyl ether (having a trade name of 68609-97-2 and an epoxy value of 0.33) was used.
Example 7
This example provides a method for utilizing phenol-based rectifying still residue, which is the same as in example 1 except that the phenol-based rectifying still residue is only 10 parts, that is, the mass ratio of the phenol-based rectifying still residue to the asphalt is 0.33: 1.
Example 8
This example provides a method for using phenol-based still bottoms, which is the same as in example 1, except that the phenol-based still bottoms are 33 parts, that is, the mass ratio of the phenol-based still bottoms to the asphalt is 1.1: 1.
Example 9
The embodiment provides a utilization method of phenol-based rectifying still residues, which comprises the following steps:
preheating 25 parts of rubber modified asphalt (manufactured by the company of Chen Tai Jianlong asphalt Co., Ltd.) at 155 ℃ for 0.5h to a flowing state, then carrying out first mixing with 15 parts of phenol-based rectifying still residues, then adding 15 parts of sebacic acid and 6 parts of methyl tetrahydrophthalic anhydride, uniformly stirring, and continuously stirring for 120min at the temperature of 155 ℃ at 500r/min for carrying out second mixing to obtain a component A;
preheating 20 parts of E-44 epoxy resin (produced by Tianjin Zhonghetai chemical company) to 80 ℃ to obtain a component B, mixing the component A and the component B at 160 ℃ for the third time, stirring at 550r/min for 10min, and curing at 145 ℃ for 12h to obtain the phenol-based rectifying still residue modified epoxy asphalt material.
The embodiment also provides an epoxy asphalt material obtained by the utilization method, and the epoxy asphalt material comprises a component A and a component B;
the component A comprises 25 parts of rubber modified asphalt, 15 parts of phenol-based rectifying still residue, 15 parts of sebacic acid and 6 parts of methyl tetrahydrophthalic anhydride;
the component B is E-44 epoxy resin.
The present embodiment can achieve similar performance as embodiments 1 to 3, and will not be described herein.
Second, comparative example
Comparative example 1
This comparative example provides an epoxy asphalt material that was the same as example 1 except that cardanol was substituted for the phenol-based rectifying still residue.
The microscopic image of the epoxy asphalt material prepared by the comparative example is shown in fig. 4, and it can be seen from fig. 4 that the asphalt distribution uniformity is significantly lower than that of example 1, and the size of the asphalt distribution is mainly concentrated at about 19 μm, and the distribution size is large, which finally results in the performance reduction of the epoxy asphalt material.
Comparative example 2
This comparative example provides an epoxy asphalt material that was the same as in example 1 except that the phenol-based rectifying still residue was replaced with dodecylphenol.
Comparative example 3
This comparative example provides an epoxy asphalt material that was the same as example 1 except that the phenol-based rectifier residue was replaced with nonylphenol.
The microscopic image of the epoxy asphalt material prepared by the comparative example is shown in fig. 5, and it can be seen from fig. 5 that the uniformity of asphalt distribution is significantly reduced compared with that of example 1, and the size of asphalt distribution is mainly concentrated at about 19 μm, and the distribution size is large, which finally results in the performance reduction of the epoxy asphalt material.
Comparative example 4
This comparative example provides an epoxy asphalt material that is the same as that of example 1 except that the curing agent in component a was only 23 parts of diethylenetriamine and no sebacic acid and methyl tetrahydrophthalic anhydride were included.
Comparative example 5
This comparative example provides an epoxy asphalt material that is the same as example 1 except that the curing agent in component a was only 3 parts diethylenetriamine and no sebacic acid and methyl tetrahydrophthalic anhydride were included.
Comparative example 6
This comparative example provides an epoxy asphalt material similar to that of example 1, except that the curing agent in component A was only 17 parts sebacic acid, and the curing agent in component B contained 6 parts methyl tetrahydrophthalic anhydride.
Comparative example 7
This comparative example provides an epoxy asphalt material that is the same as in example 1 except that the curing agent in component a was only 6 parts of methyl tetrahydrophthalic anhydride and the component B contained 0.07 part of triethylamine.
Comparative example 8
This comparative example provides an epoxy asphalt material that was the same as in example 5 except that the curing agent in component a was only 6 parts of tung oil anhydride, and the curing agent in component B contained 0.07 part of triethylamine.
The test methods used for the epoxy asphalt materials in the above examples and comparative examples are as follows:
1. curing and forming
Before curing, the dumbbell-shaped polytetrafluoroethylene mould is placed into an oven with corresponding temperature for preheating for at least 2h, the component A and the component B in the above examples and comparative examples are respectively mixed uniformly, poured into the preheated mould, vibrated for many times to expel involved air during pouring, then placed into the oven with corresponding temperature for curing, and the mould is kept horizontal all the time during curing until the material is cured and formed.
2. Tension test
And (3) placing the demolded epoxy asphalt material sample in an environment of 23 +/-2 ℃ for maintenance, carrying out a tensile test on the maintained test material on an LGD500 type tensile testing machine, and testing according to an ASTM D638-14 standard, wherein the test temperature is 23 +/-1 ℃, and the tensile rate is 500mm/min, so that the tensile strength and the elongation at break of the epoxy asphalt material are obtained.
2. Thermosetting test
And placing the prepared epoxy asphalt material sample in a crucible, placing the crucible in a muffle furnace at 300 ℃ for heating for 15min, and observing the state change of the epoxy asphalt. The thermosetting property is qualified by taking the epoxy asphalt material as a standard that the melting and flowing phenomena do not occur.
3. Microscopic analysis
Cleaning the glass slide and the cover glass with distilled water, placing the glass slide and the cover glass into an oven with corresponding temperature for drying and preheating, respectively and uniformly mixing A, B components in the embodiment 1-10, dipping a small amount of the mixture on the glass slide by a glass rod, covering the glass slide, placing the glass slide into the oven with corresponding temperature for curing, wherein the amount of the epoxy asphalt sample to be dripped is preferably 0.5g, and the glass slide is kept horizontally placed in the period. Finally, the cured sample was placed under a microscope for observation.
4. Change in viscosity
The method comprises the steps of adopting a Viscotester iQ intelligent viscosity measurement system to measure, heating the component A and the component B in the examples and the comparative examples to corresponding temperatures according to programs, uniformly mixing, testing, wherein the testing temperature is the corresponding mixed curing temperature of each example, recording the viscosity value every 30s, keeping for 1h, and recording the viscosity change.
The test results of the above examples and comparative examples are shown in table 2.
TABLE 2
| Tensile strength/MPa | Elongation at break/% | Thermosetting property | The viscosity/Pa.s of the component A and the component B after the components are mixed for 40min | |
| Example 1 | 4.16 | 148 | Qualified | 0.61 |
| Example 2 | 3.21 | 110 | Qualified | 0.55 |
| Example 3 | 1.77 | 137 | Qualified | 0.69 |
| Example 4 | 0.55 | 92 | Qualified | 0.72 |
| Example 5 | 1.72 | 117 | Qualified | 0.68 |
| Example 6 | 1.04 | 132 | Qualified | 0.62 |
| Example 7 | 1.02 | 79 | Qualified | 0.85 |
| Example 8 | 0.60 | 122 | Fail to be qualified | 0.50 |
| Comparative example 1 | 0.14 | 61 | Qualified | 0.52 |
| Comparative example 2 | 1.00 | 78 | Qualified | 0.55 |
| Comparative example 3 | 1.28 | 57 | Qualified | 0.65 |
| Comparative example 4 | - | - | Qualified | - |
| Comparative example 5 | - | - | Fail to be qualified | - |
| Comparative example 6 | 1.20 | 77 | Fail to be qualified | 0.71 |
| Comparative example 7 | 10.15 | 3 | Qualified | 0.83 |
| Comparative example 8 | 2.16 | 28 | Qualified | 0.89 |
As can be seen from table 2:
the result shows that all the phenol-based kettle residue modified epoxy asphalt can ensure no flow at 300 ℃ and has good thermosetting property. In the embodiment 1, the amine curing system and the epoxy system of the phenol-based rectifying still residue compatibilization have obvious effect, can be quickly cured at normal temperature, and the cured material is brittle and high in strength, so that the molding and sample preparation and the tensile test are inconvenient; the effect of the compound curing system of the phenol-based rectifying still residues, the sebacic acid and the methyl tetrahydrophthalic anhydride is obvious, the flexibility of the material is improved due to the interaction of the long-chain structure of the sebacic acid and the rectifying still residues, and the larger tensile strength is obtained.
In the above embodiment, the phenol-based rectifying still residue has a compatibilization effect, the addition amount is about 15 to 20% of the total system, the cured epoxy asphalt material is in a state that the epoxy resin system is a continuous phase and the asphalt is a dispersed phase, wherein the dispersed particle size of the asphalt is 20 to 30nm, and the asphalt is uniformly or in cluster distribution. Meanwhile, the phenol-based rectifying still residue does not need other pretreatment operation in the using process, so that the method is environment-friendly, saves resources, simplifies operation conditions, reduces production cost and effectively realizes resource utilization of the phenol-based rectifying still residue.
The present invention is described in detail with reference to the above embodiments, but the present invention is not limited to the above detailed structural features, that is, the present invention is not meant to be implemented only by relying on the above detailed structural features. It should be understood by those skilled in the art that any modifications of the present invention, equivalent substitutions of selected components of the present invention, additions of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. The phenol-based rectifying still residue modified epoxy asphalt material is characterized by comprising a component A and a component B;
the component A comprises asphalt, phenol-based rectifying still residues, a first curing agent and a second curing agent;
the component B comprises epoxy resin.
2. The epoxy asphalt material according to claim 1, wherein the mass ratio of the component A to the component B is 2.5-4.5: 1.
3. The epoxy asphalt material according to claim 1 or 2, wherein the component A comprises 20-30 parts by weight of asphalt, 15-20 parts by weight of phenol-based rectifying still residue, 10-20 parts by weight of first curing agent and 3-10 parts by weight of second curing agent.
4. The epoxy asphalt material according to any one of claims 1 to 3, wherein the phenol-based distillation still residue is a deep-drawing heavy component produced by distillation in a purification stage of dodecylphenol.
5. The epoxy asphalt material according to any one of claims 1 to 4, wherein the phenol-based rectifying still residue contains a phenol-based group and a long-chain unsaturated double bond;
preferably, the carbon number of the long-chain unsaturated double bond is 10-15;
preferably, the density of the phenol-based rectifying still residue at 20 ℃ is 0.8-0.9 g/cm 3 ；
Preferably, the viscosity of the phenol-based rectifying still residue at 20 ℃ is 1.2-1.5 Pa.s.
6. An epoxy asphalt material according to any one of claims 1 to 5, characterized in that the asphalt is rubber asphalt.
7. The epoxy asphalt material according to any one of claims 1 to 6, characterized in that the first curing agent comprises a long-chain carboxylic acid curing agent;
preferably, the second curing agent comprises an anhydride curing agent;
preferably, the first curing agent is sebacic acid, and the second curing agent is methyl tetrahydrophthalic anhydride.
8. A utilization method of phenol-based rectifying still residues is characterized by comprising the following steps: modifying the epoxy asphalt by using the phenol-based rectifying still residue to obtain the phenol-based rectifying still residue modified epoxy asphalt material as claimed in any one of claims 1 to 7.
9. The utilization method according to claim 8, comprising: adding a first curing agent and a second curing agent into the first mixed asphalt and the phenol-based rectifying still residue, and performing second mixing to obtain a component A; thirdly, mixing the component A and the component B containing epoxy resin, and curing to obtain the phenolic group rectifying still residue modified epoxy asphalt material;
preferably, the temperature of the asphalt in the first mixing is 140-160 ℃;
preferably, the temperature of the first mixing is 140-160 ℃;
preferably, the temperature of the second mixing is 140-160 ℃;
preferably, the temperature of the component B in the third mixing is 60-70 ℃;
preferably, the temperature of the third mixing is 140-155 ℃;
preferably, the time of the third mixing is 3-5 min.
10. The utilization method according to claim 8 or 9, wherein the curing temperature is 130-150 ℃;
preferably, the curing time is 10-15 h.
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Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1086390A (en) * | 1966-07-20 | 1967-10-11 | Shell Int Research | Improvements in or relating to bituminous polyepoxide resin compositions and their use |
| US3880789A (en) * | 1971-10-05 | 1975-04-29 | Sumitomo Chemical Co | Coating composition comprising polyisocyanate, hydroxyl compound, and tar |
| DE2730642A1 (en) * | 1977-07-07 | 1979-01-25 | Schering Ag | Hardenable epoxy! resin-petroleum bitumen dispersions - for coatings, adhesives and casting materials |
| JPS59223716A (en) * | 1983-06-03 | 1984-12-15 | Sanyurejin Kk | Modified asphalt-epoxy resin composition |
| WO1989010383A1 (en) * | 1988-04-28 | 1989-11-02 | Nauchno-Proizvodstvennoe Obiedinenie "Dorstroitekh | Bitumen-rubber composition and method of obtaining it |
| RU2046771C1 (en) * | 1992-07-14 | 1995-10-27 | Стерлитамакский нефтехимический завод | Method of preparing cold asphalt concrete mixture |
| CN1952012A (en) * | 2006-10-20 | 2007-04-25 | 中国林业科学研究院林产化学工业研究所 | Thermosetting epoxy asphalt material, preparation method and its dedicated compatibilizer |
| CN103351630A (en) * | 2013-07-09 | 2013-10-16 | 杨林江 | Epoxy resin-modified rubber asphalt |
| CN104212190A (en) * | 2014-08-27 | 2014-12-17 | 华南理工大学 | Organic montmorillonite modified epoxy asphalt material and preparation method thereof |
| CN105838094A (en) * | 2016-05-12 | 2016-08-10 | 长沙理工大学 | Toughened warm-mixed epoxy asphalt for steel bridge deck pavement |
| CN110922772A (en) * | 2018-09-20 | 2020-03-27 | 中国石油化工股份有限公司 | Modified epoxy asphalt particles and preparation and application thereof |
| CN111138870A (en) * | 2019-02-14 | 2020-05-12 | 兰州石化职业技术学院 | Cresol residue modified asphalt and preparation method and application thereof |
| CN111607067A (en) * | 2020-06-02 | 2020-09-01 | 江苏扬农化工集团有限公司 | Method for synthesizing epoxy resin from epichlorohydrin rectifying still residues |
-
2022
- 2022-07-21 CN CN202210856037.9A patent/CN115029010B/en active Active
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1086390A (en) * | 1966-07-20 | 1967-10-11 | Shell Int Research | Improvements in or relating to bituminous polyepoxide resin compositions and their use |
| US3880789A (en) * | 1971-10-05 | 1975-04-29 | Sumitomo Chemical Co | Coating composition comprising polyisocyanate, hydroxyl compound, and tar |
| DE2730642A1 (en) * | 1977-07-07 | 1979-01-25 | Schering Ag | Hardenable epoxy! resin-petroleum bitumen dispersions - for coatings, adhesives and casting materials |
| JPS59223716A (en) * | 1983-06-03 | 1984-12-15 | Sanyurejin Kk | Modified asphalt-epoxy resin composition |
| WO1989010383A1 (en) * | 1988-04-28 | 1989-11-02 | Nauchno-Proizvodstvennoe Obiedinenie "Dorstroitekh | Bitumen-rubber composition and method of obtaining it |
| RU2046771C1 (en) * | 1992-07-14 | 1995-10-27 | Стерлитамакский нефтехимический завод | Method of preparing cold asphalt concrete mixture |
| CN1952012A (en) * | 2006-10-20 | 2007-04-25 | 中国林业科学研究院林产化学工业研究所 | Thermosetting epoxy asphalt material, preparation method and its dedicated compatibilizer |
| CN103351630A (en) * | 2013-07-09 | 2013-10-16 | 杨林江 | Epoxy resin-modified rubber asphalt |
| CN104212190A (en) * | 2014-08-27 | 2014-12-17 | 华南理工大学 | Organic montmorillonite modified epoxy asphalt material and preparation method thereof |
| CN105838094A (en) * | 2016-05-12 | 2016-08-10 | 长沙理工大学 | Toughened warm-mixed epoxy asphalt for steel bridge deck pavement |
| CN110922772A (en) * | 2018-09-20 | 2020-03-27 | 中国石油化工股份有限公司 | Modified epoxy asphalt particles and preparation and application thereof |
| CN111138870A (en) * | 2019-02-14 | 2020-05-12 | 兰州石化职业技术学院 | Cresol residue modified asphalt and preparation method and application thereof |
| CN111607067A (en) * | 2020-06-02 | 2020-09-01 | 江苏扬农化工集团有限公司 | Method for synthesizing epoxy resin from epichlorohydrin rectifying still residues |
Non-Patent Citations (1)
| Title |
|---|
| 蔡思超等: ""煤化工分级精馏釜残资源化利用过程初步分析"", 《化工进展》 * |
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