CN111303448A - Preparation method of hydrocarbon resin emulsified composition - Google Patents
Preparation method of hydrocarbon resin emulsified composition Download PDFInfo
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- CN111303448A CN111303448A CN202010206039.4A CN202010206039A CN111303448A CN 111303448 A CN111303448 A CN 111303448A CN 202010206039 A CN202010206039 A CN 202010206039A CN 111303448 A CN111303448 A CN 111303448A
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/07—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media from polymer solutions
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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Abstract
The application belongs to the technical field of hydrocarbon resin emulsification, and particularly relates to a preparation method of a hydrocarbon resin emulsification composition, which comprises the following steps: the method comprises the following steps: putting hydrocarbon resin and alcohol ether substances into a reaction kettle, heating to 90-110 ℃, stirring and melting for 2-3 hours; step two: adding a composite emulsifier and sodium alkyl benzene sulfonate into the composition obtained in the step one, and stirring for 0.5-2 hours; step three: cooling to 80-90 deg.C, slowly dripping citric acid water solution for 3-4 hr, stirring for 0.5-1 hr after water is completely dripped, and discharging.
Description
Technical Field
The application belongs to the technical field of hydrocarbon resin emulsification, and particularly relates to a preparation method of a hydrocarbon resin emulsification composition.
Background
The hydrocarbon resin is a thermoplastic resin produced by the processes of pretreatment, polymerization, distillation and the like of C5 and C9 fractions by-produced in petroleum cracking, and is not a high polymer but an oligomer with the molecular weight of 300-3000. Hydrocarbon resins have wide applications in the industries of paints, rubbers, adhesives, inks, coatings, plastics, and the like. However, the poor hydrophilicity of hydrocarbon resin limits its application prospect, so it is necessary to emulsify hydrocarbon resin, but there are few research reports. CN101293989A discloses a petroleum resin emulsion for slurry seal, which comprises the following components in parts by weight: 40-80 parts of petroleum resin; cationic emulsifier C-450, 0.1-5% of resin weight; 60 ~ 65 ℃ hot water 30 ℃52 parts of (1); anhydrous CaCl2Trace amount; concentrated hydrochloric acid adjusts pH 1.5 ~ 7.0, petroleum resin is applicable to the slurry seal for road engineering, has the function such as fall makes an uproar that permeates water, when guaranteeing the high strength of cement concrete pavement, has bituminous paving's high flexibility again, still has the advantage that the maintenance is simple, swift. However, the petroleum resin emulsion has poor stability, and concentrated hydrochloric acid is involved, so that the requirement on equipment is high, and the petroleum resin emulsion is not environment-friendly.
Disclosure of Invention
In order to solve the above technical problems, a first aspect of the present invention provides a method for preparing a hydrocarbon resin emulsion composition, comprising the steps of:
the method comprises the following steps: putting hydrocarbon resin and alcohol ether substances into a reaction kettle, heating to 90-110 ℃, stirring and melting for 2-3 hours;
step two: adding a composite emulsifier and sodium alkyl benzene sulfonate into the composition obtained in the step one, and stirring for 0.5-2 hours;
step three: and (3) cooling the composition obtained in the second step to 80-90 ℃, slowly dropwise adding a citric acid aqueous solution, controlling the dropwise adding time to be 3-4 hours, continuously stirring for 0.5-1 hour after water is completely dropwise added, and discharging to obtain the composition.
As a preferable technical scheme, the weight portions are as follows: 40-50 parts of hydrocarbon resin; 10-15 parts of a composite emulsifier; 0.1-0.5 part of sodium alkyl benzene sulfonate; 0-10 parts of alcohol ether substances; 1.2-3.5 parts of citric acid; 40-50 parts of water.
As a preferable technical scheme, the hydrocarbon resin is at least one selected from C5 hydrocarbon resin, DCPD hydrocarbon resin, C9 hydrocarbon resin, C5/C9 copolymer hydrocarbon resin, C5 hydrogenated hydrocarbon resin and C9 hydrogenated hydrocarbon resin.
As a preferable technical scheme, the composite emulsifier comprises the following components in percentage by weight: 35-40% of EO group-containing polymer; 35-40% of isocyanate; 15-20% of amine substances; the balance of epoxy resin.
As a preferable technical scheme, the polymer containing EO groups is selected from at least one of polyether polyol, polyvinyl alcohol, fatty alcohol-polyoxyethylene ether, phenol-polyoxyethylene ether, polyethylene glycol ester and polyethylene glycol.
As a preferred embodiment, the isocyanate is at least one selected from the group consisting of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, and lysine diisocyanate.
As a preferable technical scheme, the weight ratio of the toluene diisocyanate to the isophorone diisocyanate is (1-3): 1.
in a preferred embodiment, the amine is at least one selected from the group consisting of diethylenetriamine, N-methyldiethanolamine, ethylenediamine, diethylenetriamine, isophorone diamine, m-phenylenediamine, diphenylmethane diamine, tetramethylene xylylenediamine, hexahydrotoluenediamine, dihexadecylamine, ditetradecylamine, didodecylamine, dioctadecylsecondary amine, dioctadecylprimary amine, and didodecylamine.
As a preferable technical scheme, the preparation method of the compound emulsifier comprises the following steps: and putting the polymer containing the EO group into a reaction kettle, heating to 70-90 ℃ for melting, heating to 110-130 ℃ after completely melting, vacuumizing for 1-3 hours, cooling to 70-90 ℃, adding isocyanate and amine substances, reacting for 7-11 hours, adding epoxy resin and a catalyst, and reacting for 1-3 hours to obtain the EO-based polymer.
As a preferred technical scheme, in the first step and the second step, the rotating speed is 50-100 r/min, and in the third step, the rotating speed is 1000-2000 r/min.
Has the advantages that: the hydrocarbon resin emulsified composition prepared by the self-made composite emulsifier and sodium alkyl benzene sulfonate has high solid content, good stability, small emulsion particle size and simple preparation method, and can be used in various coatings and printing inks.
Detailed Description
For purposes of the following detailed description, it is to be understood that the invention may assume various alternative variations and step sequences, except where expressly specified to the contrary. Moreover, other than in any operating examples, or where otherwise indicated, all numbers expressing, for example, quantities of ingredients used in the specification and claims are to be understood as being modified in all instances by the term "about". Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that may vary depending upon the desired properties to be obtained by the present invention. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.
Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard deviation found in their respective testing measurements.
When a range of values is disclosed herein, the range is considered to be continuous and includes both the minimum and maximum values of the range, as well as each value between such minimum and maximum values. Further, when a range refers to an integer, each integer between the minimum and maximum values of the range is included. Further, when multiple range-describing features or characteristics are provided, the ranges may be combined. In other words, unless otherwise indicated, all ranges disclosed herein are to be understood to encompass any and all subranges subsumed therein. For example, a stated range from "1 to 10" should be considered to include any and all subranges between the minimum value of 1 and the maximum value of 10. Exemplary subranges of the range 1 to 10 include, but are not limited to, 1 to 6.1, 3.5 to 7.8, 5.5 to 10, and the like.
In order to solve the above problems, the present invention provides a method for preparing a hydrocarbon resin emulsion composition, comprising the steps of:
the method comprises the following steps: putting hydrocarbon resin and alcohol ether substances into a reaction kettle, heating to 90-110 ℃, stirring and melting for 2-3 hours;
step two: adding a composite emulsifier and sodium alkyl benzene sulfonate into the composition obtained in the step one, and stirring for 0.5-2 hours;
step three: and (3) cooling the composition obtained in the second step to 80-90 ℃, slowly dropwise adding a citric acid aqueous solution, controlling the dropwise adding time to be 3-4 hours, continuously stirring for 0.5-1 hour after water is completely dropwise added, and discharging to obtain the composition.
As a preferred embodiment, the method for preparing the hydrocarbon resin emulsion composition comprises the following steps:
the method comprises the following steps: putting hydrocarbon resin and alcohol ether substances into a reaction kettle, heating to 90-110 ℃, stirring and melting for 2-3 hours;
step two: adding a composite emulsifier, sodium alkyl benzene sulfonate and a stabilizer into the composition obtained in the step one, and stirring for 0.5-2 hours;
step three: and (3) cooling the composition obtained in the second step to 80-90 ℃, slowly dropwise adding a citric acid aqueous solution, controlling the dropwise adding time to be 3-4 hours, continuously stirring for 0.5-1 hour after water is completely dropwise added, and discharging to obtain the composition.
Wherein, the weight portion is as follows: 40-50 parts of hydrocarbon resin; 10-15 parts of a composite emulsifier; 0.1-0.5 part of sodium alkyl benzene sulfonate; 0-10 parts of alcohol ether substances; 1.2-3.5 parts of citric acid; 2-5 parts of a stabilizer; 40-50 parts of water.
As a preferred embodiment, the following are used in parts by weight: 45 parts of hydrocarbon resin; 13 parts of a composite emulsifier; 0.2 part of sodium alkyl benzene sulfonate; 6 parts of alcohol ether substances; 2.5 parts of citric acid; 3 parts of a stabilizer; 42 parts of water.
Preferably, the alcohol ether is other than 0.
Hydrocarbon resin
In the application, the hydrocarbon resin is selected from at least one of C5 hydrocarbon resin, DCPD hydrocarbon resin, C9 hydrocarbon resin, C5/C9 copolymer hydrocarbon resin, C5 hydrogenated hydrocarbon resin and C9 hydrogenated hydrocarbon resin.
Composite emulsifier
As a preferred embodiment, the composite emulsifier comprises the following components in percentage by weight: 35-40% of EO group-containing polymer; 35-40% of isocyanate; 15-20% of amine substances; the balance of epoxy resin.
Preferably, the polymer containing EO groups is selected from at least one of polyether polyol, polyvinyl alcohol, fatty alcohol-polyoxyethylene ether, phenol-polyoxyethylene ether, polyethylene glycol acid ester and polyethylene glycol.
As the above-mentioned polyoxyethylene phenol ether, nonylphenol polyoxyethylene ether, octylphenol polyoxyethylene ether and pentadecylphenol polyoxyethylene ether are exemplified.
The fatty alcohol polyoxyethylene ether includes undecyl alcohol polyoxyethylene ether, hexyl decanol polyoxyethylene ether, sorbitol polyoxyethylene ether, isodecyl alcohol polyoxyethylene ether, C7-C21 polyoxyethylene ether, C8-C10-fatty polyoxyethylene ether, C12-C14 secondary polyoxyethylene ether, stearyl alcohol polyoxyethylene ether and oleyl alcohol polyoxyethylene ether.
As the polyethylene glycol acid ester, polyethylene glycol monooleate, polyethylene glycol monomethyl ether methanesulfonate, polyethylene glycol monolaurate, polyethylene glycol monocaprylate, and polyethylene glycol diisostearate are exemplified.
In a preferred embodiment, the polyether polyol has an average molecular weight of 4000-.
More preferably, the hydroxyl value in the polyether polyol is from 10 to 50mg KOH/g.
In a preferred embodiment, the isocyanate is selected from at least one of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, lysine diisocyanate.
Preferably, the isocyanate is toluene diisocyanate and isophorone diisocyanate; more preferably, the weight ratio of the toluene diisocyanate to the isophorone diisocyanate is (1-3): 1; further preferably, the weight ratio of the toluene diisocyanate to the isophorone diisocyanate is 2: 1.
the amine substance is at least one selected from diethylenetriamine, N-methyldiethanolamine, ethylenediamine, diethylenetriamine, isophorone diamine, m-phenylenediamine, diphenylmethane diamine, tetramethylene xylylenediamine, hexahydrotoluene diamine, dihexadecylamine, ditetradecylamine, didodecylamine, dioctadecylsecondary amine, dioctadecylprimary amine and didodecylamine.
Preferably, the amine substances are diethylenetriamine, ethylenediamine and dioctadecylsecondary amine; more preferably, the weight ratio of the diethylenetriamine to the ethylenediamine to the dioctadecylsecondary amine is 1: (1-4): 1; further preferably, the weight ratio of the diethylenetriamine to the ethylenediamine to the dioctadecylsecondary amine is 1: 2.5: 1.
the epoxy resin is a polymer containing more than two epoxy groups in the molecule. It is a polycondensation product of epichlorohydrin and bisphenol A or a polyol. Because of the chemical activity of the epoxy group, a plurality of compounds containing active hydrogen can be used for ring opening, curing and crosslinking to generate a network structure. Preferably, the epoxy value of the epoxy resin is 0.2 to 0.54. More preferably, the epoxy resin is E-20 and/or E-51.
The preparation method of the compound emulsifier comprises the following steps: and putting the polymer containing the EO group into a reaction kettle, heating to 70-90 ℃ for melting, heating to 110-130 ℃ after completely melting, vacuumizing for 1-3 hours, cooling to 70-90 ℃, adding isocyanate and amine substances, reacting for 7-11 hours, adding epoxy resin and a catalyst, and reacting for 1-3 hours to obtain the EO-based polymer.
Preferably, the preparation method of the compound emulsifier comprises the following steps: and putting the polymer containing the EO group into a reaction kettle, heating to 70-90 ℃ for melting, heating to 110-130 ℃ after completely melting, vacuumizing for 1-3 hours, cooling to 70-90 ℃, adding isocyanate, diethylenetriamine and ethylenediamine, reacting for 3-5 hours, adding dioctadecyl secondary amine and/or dioctadecyl primary amine, continuing to react for 4-6 hours, adding epoxy resin and a catalyst, and reacting for 1-3 hours to obtain the epoxy resin modified ethylene-propylene copolymer.
The catalyst is selected from one of organic bismuth, organic tin and organic zinc.
The method comprises the steps of reacting a polymer containing EO groups with isocyanate and amine substances, and then adding epoxy resin for continuous reaction to obtain an emulsifier containing oleophylic and hydrophilic long chains; the emulsifier has the advantages of large molecular weight, more hydrophilic groups and good emulsifying and dispersing effects. The applicant finds that when the polyether polyol has the average molecular weight of 4000-15000 and the hydroxyl value of 10-50mg KOH/g, the composite emulsifier is cooperated with sodium alkyl benzene sulfonate and alcohol ether substances in a system to improve the stability of the emulsion, and the weight ratio of the diethylenetriamine to the ethylenediamine is 1: (1-4), the polar groups in the system are promoted to approach each other, the difference between the hardness and the polarity of a soft segment is increased, and hydrophilic groups are easier to gather on the surface of the hydrocarbon resin, so that the stability of the emulsion is improved; particularly, after adding dioctadecyl secondary amine and/or dioctadecyl primary amine and epoxy resin, dioctadecyl and the like in the formed composite emulsifier plays a strong anchoring role to be wound with a hydrocarbon resin molecular chain, so that desorption or transfer is not generated, a polyoxyethylene chain segment surrounds the hydrocarbon resin to keep a special three-dimensional space effect, and a product is kept stable for a long time.
Sodium alkyl benzene sulfonate
In a preferred embodiment, the sodium alkyl benzene sulfonate is at least one selected from the group consisting of sodium dodecyl benzene sulfonate, sodium tetradecyl benzene sulfonate, sodium octadecyl benzene sulfonate, sodium didodecyl benzene sulfonate, sodium C10-16 alkyl benzene sulfonate, and sodium tridecyl benzene sulfonate.
Alcohol ether substances
In a preferred embodiment, the alcohol ether is at least one selected from the group consisting of propylene glycol methyl ether, propylene glycol butyl ether, dipropylene glycol methyl ether, diethylene glycol monobutyl ether, ethylene glycol monobutyl ether, diethylene glycol butyl ether, and diethylene glycol ethyl ether.
As a preferred embodiment, in the first step and the second step, the rotation speed is 50-100 r/min, preferably 60-80 r/min; in the third step, the rotation speed is 1000-.
Under the action of stirring, the hydrocarbon resin forms a plurality of beads, the composite emulsifier and the sodium alkyl benzene sulfonate are mutually cooperated to be adsorbed on the surface of the hydrocarbon resin, the oleophilic group is combined with the hydrocarbon resin, and the hydrophilic group is exposed in a water phase; meanwhile, the surface of the hydrocarbon resin can be charged with negative charges, the emulsification of the hydrocarbon resin is realized through electrostatic repulsion and steric hindrance, and the emulsified composition has high stability and small particle size.
The applicant also found that when the composite emulsifier is 10-15 parts; when the sodium alkyl benzene sulfonate is 0.1-0.5 part, the particle size of the emulsion can be reduced, and the addition of the sodium dodecyl benzene sulfonate is supposed to promote the faster and more compact arrangement of the composite emulsifier on the surface of the hydrocarbon resin; when the sodium alkyl benzene sulfonate is less, the composite emulsifier is loosely arranged on the surface of the hydrocarbon resin, the surface tension of the emulsion cannot be reduced to the minimum, and the hydrocarbon resin emulsion system is unstable; when the amount of the complex emulsifier and/or sodium alkylbenzenesulfonate is large, foam increases, viscosity increases, and the like.
The stabilizer includes but is not limited to bentonite, hydroxycellulose.
In a second aspect, the invention provides a coating comprising the hydrocarbon resin emulsion composition obtained by said process.
The present invention will be specifically described below by way of examples. It should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and that the insubstantial modifications and adaptations of the present invention by those skilled in the art based on the above disclosure are still within the scope of the present invention.
In addition, the starting materials used are all commercially available, unless otherwise specified.
Examples
Example 1
A method for preparing a hydrocarbon resin emulsion composition, comprising the steps of:
the method comprises the following steps: putting hydrocarbon resin and propylene glycol methyl ether into a reaction kettle, heating to 100 ℃, stirring and melting for 2.5 hours;
step two: adding a composite emulsifier and sodium dodecyl benzene sulfonate into the composition obtained in the step one, and stirring for 1 hour;
step three: and cooling to 85 ℃, slowly dripping citric acid aqueous solution, controlling the dripping time to be 3.5 hours, continuously stirring for 1 hour after water is completely dripped, and discharging to obtain the citric acid water-based coating.
Wherein, calculated by weight portion, 45 portions of hydrocarbon resin; 13 parts of a composite emulsifier; 0.2 part of sodium dodecyl benzene sulfonate; 6 parts of propylene glycol methyl ether; 2.5 parts of citric acid; 3 parts of bentonite; 42 parts of water.
The hydrocarbon resin is C5 hydrocarbon resin;
the composite emulsifier comprises the following components in percentage by weight: EO group-containing polymer 37.5%; 37.5 percent of isocyanate; 17% of amine substances; 18% of epoxy resin; the EO group-containing polymer is polyether polyol, has the average molecular weight of 8000, the hydroxyl value of 12.5-15.5 and the brand number of Puranol D280, and is purchased from Honghua chemical industry Co., Ltd. The isocyanate is toluene diisocyanate and isophorone diisocyanate; the weight ratio of the toluene diisocyanate to the isophorone diisocyanate is 2: 1. the amine substances are diethylenetriamine, ethylenediamine and dioctadecylsecondary amine; the weight ratio of the diethylenetriamine to the ethylenediamine to the dioctadecylsecondary amine is 1: 2.5: 1, said secondary dioctadecylamine is purchased from Shanghai Hanwa Utility Co. The epoxy resin is E-51; the preparation method of the compound emulsifier comprises the following steps: adding the polymer containing EO groups into a reaction kettle, heating to 80 ℃ for melting, heating to 120 ℃ after complete melting, vacuumizing for 2 hours, cooling to 80 ℃, adding isocyanate, diethylenetriamine and ethylenediamine, reacting for 4 hours, adding dioctadecylsecondary amine, continuing to react for 5 hours, adding epoxy resin and catalyst organobismuth (the amount of the catalyst is 0.2% of the weight of the composite emulsifier), and reacting for 2 hours to obtain the composite emulsifier.
Example 2
A method for preparing a hydrocarbon resin emulsion composition, comprising the steps of:
the method comprises the following steps: putting hydrocarbon resin and alcohol ether substances into a reaction kettle, heating to 90 ℃, stirring and melting for 3 hours;
step two: adding a composite emulsifier and sodium alkyl benzene sulfonate into the composition obtained in the step one, and stirring for 0.5 hour;
step three: cooling to 80 ℃, slowly dripping citric acid aqueous solution, controlling the dripping time to be 3 hours, continuously stirring for 0.5 hour after water is completely dripped, and discharging to obtain the product.
40 parts of hydrocarbon resin; 10 parts of a composite emulsifier; 0.1 part of sodium dodecyl benzene sulfonate; 4 parts of propylene glycol methyl ether; 1.2 parts of citric acid; 2 parts of bentonite; and 40 parts of water.
The hydrocarbon resin is C5 hydrocarbon resin;
the composite emulsifier comprises the following components in parts by weight: 45 parts of a polymer containing EO groups; 45 parts of isocyanate; 15 parts of amine substances; 16 parts of epoxy resin; the EO group-containing polymer is polyether polyol, has the average molecular weight of 8000, the hydroxyl value of 12.5-15.5 and the brand number of Puranol D280, and is purchased from Honghua chemical industry Co., Ltd. The isocyanate is toluene diisocyanate and isophorone diisocyanate; the weight ratio of the toluene diisocyanate to the isophorone diisocyanate is 2: 1. the amine substances are diethylenetriamine, ethylenediamine and dioctadecylsecondary amine; the weight ratio of the diethylenetriamine to the ethylenediamine to the dioctadecylsecondary amine is 1: 2.5: 1, said secondary dioctadecylamine is purchased from Shanghai Hanwa Utility Co. The epoxy resin is E-51; the preparation method of the compound emulsifier is the same as that of the embodiment 1.
Example 3
A method for preparing a hydrocarbon resin emulsion composition, comprising the steps of:
the method comprises the following steps: putting hydrocarbon resin and alcohol ether substances into a reaction kettle, heating to 110 ℃, stirring and melting for 2 hours;
step two: adding a composite emulsifier and sodium alkyl benzene sulfonate into the composition obtained in the step one, and stirring for 2 hours;
step three: and cooling to 90 ℃, slowly dripping citric acid aqueous solution, controlling the dripping time to be 4 hours, continuously stirring for 1 hour after water is completely dripped, and discharging to obtain the citric acid water-based coating.
50 parts of hydrocarbon resin; 15 parts of a composite emulsifier; 0.5 part of sodium dodecyl benzene sulfonate; 10 parts of propylene glycol methyl ether; 3.5 parts of citric acid; 5 parts of bentonite; 50 parts of water.
The hydrocarbon resin is C5 hydrocarbon resin;
the composite emulsifier comprises the following components in parts by weight: 45 parts of a polymer containing EO groups; 45 parts of isocyanate; 15 parts of amine substances; 16 parts of epoxy resin; the EO group-containing polymer is polyether polyol, has the average molecular weight of 8000, the hydroxyl value of 12.5-15.5 and the brand number of Puranol D280, and is purchased from Honghua chemical industry Co., Ltd. The isocyanate is toluene diisocyanate and isophorone diisocyanate; the weight ratio of the toluene diisocyanate to the isophorone diisocyanate is 2: 1. the amine substances are diethylenetriamine, ethylenediamine and dioctadecylsecondary amine; the weight ratio of the diethylenetriamine to the ethylenediamine to the dioctadecylsecondary amine is 1: 2.5: 1, said secondary dioctadecylamine is purchased from Shanghai Hanwa Utility Co. The epoxy resin is E-51; the preparation method of the compound emulsifier is the same as that of the embodiment 1.
Comparative example 1
A process for producing a hydrocarbon resin emulsion composition, which comprises the steps similar to those of example 1,
the composite emulsifier comprises the following components in percentage by weight: EO group-containing polymer 37.5%; 37.5 percent of isocyanate; 17% of amine substances; 18% of epoxy resin; the EO group-containing polymer is polyether polyol, has the average molecular weight of 8000, the hydroxyl value of 12.5-15.5 and the brand number of Puranol D280, and is purchased from Honghua chemical industry Co., Ltd. The isocyanate is toluene diisocyanate and isophorone diisocyanate; the weight ratio of the toluene diisocyanate to the isophorone diisocyanate is 2: 1. the amine substances are diethylenetriamine and ethylenediamine; the weight ratio of the diethylenetriamine to the ethylenediamine is 1: 2.5. the epoxy resin is E-51; the preparation method of the compound emulsifier comprises the following steps: and (2) putting the polymer containing the EO group into a reaction kettle, heating to 80 ℃ for melting, heating to 120 ℃ after complete melting, vacuumizing for 2 hours, cooling to 80 ℃, adding isocyanate, diethylenetriamine and ethylenediamine, reacting for 4 hours, adding epoxy resin and a catalyst organic bismuth (the amount of the catalyst is 0.2 percent of the weight of the composite emulsifier), and reacting for 2 hours to obtain the catalyst.
The preparation method of the hydrocarbon resin emulsified composition has the same specific steps as example 1.
Comparative example 2
A process for producing a hydrocarbon resin emulsion composition, which comprises the steps similar to those of example 1,
the composite emulsifier comprises the following components in percentage by weight: EO group-containing polymer 37.5%; 37.5 percent of isocyanate; 17% of amine substances; 18% of epoxy resin; the EO group-containing polymer is polyether polyol, has the average molecular weight of 8000, the hydroxyl value of 12.5-15.5 and the brand number of Puranol D280, and is purchased from Honghua chemical industry Co., Ltd. The isocyanate is toluene diisocyanate and isophorone diisocyanate; the weight ratio of the toluene diisocyanate to the isophorone diisocyanate is 2: 1. the amine substances are diethylenetriamine, ethylenediamine and didodecylamine; the weight ratio of the diethylenetriamine to the ethylenediamine to the didodecylamine is 1: 2.5: 1, the CAS number of the didodecylamine is 3007-31-6. The epoxy resin is E-51; the preparation method of the compound emulsifier has the specific steps as in example 1.
The preparation method of the hydrocarbon resin emulsified composition has the same specific steps as example 1.
Comparative example 3
The preparation method of the hydrocarbon resin emulsified composition is the same as that in example 1, and is different from the preparation method in that the composite emulsifier comprises the following components in percentage by weight: EO group-containing polymer 37.5%; 37.5 percent of isocyanate; 17% of amine substances; 18% of epoxy resin; the EO group-containing polymer is polyether polyol, has the average molecular weight of 8000, the hydroxyl value of 12.5-15.5 and the brand number of Puranol D280, and is purchased from Honghua chemical industry Co., Ltd. The isocyanate is toluene diisocyanate and isophorone diisocyanate; the weight ratio of the toluene diisocyanate to the isophorone diisocyanate is 2: 1. the amine substances are diethylenetriamine, ethylenediamine and dioctadecylamine; the weight ratio of the diethylenetriamine to the ethylenediamine to the dioctadecyl amine is 1: 8: 1. the epoxy resin is E-51; the preparation method of the compound emulsifier has the specific steps as in example 1.
Comparative example 4
A process for producing a hydrocarbon resin emulsion composition, which comprises the steps similar to those of example 1,
the composite emulsifier comprises the following components in percentage by weight: EO group-containing polymer 37.5%; 37.5 percent of isocyanate; 17% of amine substances; 18% of epoxy resin; the EO group-containing polymer is polyether polyol, has the average molecular weight of 8000, the hydroxyl value of 12.5-15.5 and the brand number of Puranol D280, and is purchased from Honghua chemical industry Co., Ltd. The isocyanate is toluene diisocyanate and isophorone diisocyanate; the weight ratio of the toluene diisocyanate to the isophorone diisocyanate is 2: 1. the amine substances are diethylenetriamine, ethylenediamine and dioctadecylamine; the weight ratio of the diethylenetriamine to the ethylenediamine to the dioctadecyl amine is 2.5: 1: 1. the epoxy resin is E-51; the preparation method of the compound emulsifier has the specific steps as in example 1.
Comparative example 5
A method for preparing a hydrocarbon resin emulsion composition, which comprises the same steps as in example 1, except that sodium dodecylbenzenesulfonate is 0.
Performance testing
The hydrocarbon resin emulsion compositions described in examples 1 to 3 herein have a solids content of from 50 to 68%.
The particle size and stability of the emulsified compositions prepared in the examples and comparative examples were measured, and the specific results are shown in Table 1.
TABLE 1
| Emulsified composition | Particle size (D75 μm) | Stability (4000rpm, 30min) |
| Example 1 | 0.414 | Uniform and no delamination |
| Example 2 | 0.375 | Uniform and no delamination |
| Example 3 | 0.447 | Uniform and no delamination |
| Comparative example 1 | Difficulty in emulsification | Layering |
| Comparative example 2 | 2.276 | Layering |
| Comparative example 3 | / | Layering |
| Comparative example 4 | / | Layering |
| Comparative example 5 | 3.578 | Layering |
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in other forms, and any person skilled in the art may modify or change the technical content of the above disclosure into equivalent embodiments with equivalent changes, but all those simple modifications, equivalent changes and modifications made to the above embodiments according to the technical spirit of the present invention still belong to the protection scope of the present invention.
Claims (10)
1. A method for preparing a hydrocarbon resin emulsion composition, comprising the steps of:
the method comprises the following steps: putting hydrocarbon resin and alcohol ether substances into a reaction kettle, heating to 90-110 ℃, stirring and melting for 2-3 hours;
step two: adding a composite emulsifier and sodium alkyl benzene sulfonate into the composition obtained in the step one, and stirring for 0.5-2 hours;
step three: and (3) cooling the composition obtained in the second step to 80-90 ℃, slowly dropwise adding a citric acid aqueous solution, controlling the dropwise adding time to be 3-4 hours, continuously stirring for 0.5-1 hour after water is completely dropwise added, and discharging to obtain the composition.
2. The method of claim 1, wherein the following are present in parts by weight: 40-50 parts of hydrocarbon resin; 10-15 parts of a composite emulsifier; 0.1-0.5 part of sodium alkyl benzene sulfonate; 0-10 parts of alcohol ether substances; 1.2-3.5 parts of citric acid; 40-50 parts of water.
3. The method according to claim 1 or 2, wherein the hydrocarbon resin is at least one selected from the group consisting of a C5 hydrocarbon resin, a DCPD hydrocarbon resin, a C9 hydrocarbon resin, a C5/C9 copolymer hydrocarbon resin, a C5 hydrogenated hydrocarbon resin, and a C9 hydrogenated hydrocarbon resin.
4. The preparation method according to claim 1 or 2, wherein the composite emulsifier comprises the following components in percentage by weight: 35-40% of EO group-containing polymer; 35-40% of isocyanate; 15-20% of amine substances; the balance of epoxy resin.
5. The method according to claim 4, wherein the EO group-containing polymer is at least one selected from the group consisting of polyether polyol, polyvinyl alcohol, fatty alcohol-polyoxyethylene ether, phenol-polyoxyethylene ether, polyethylene glycol ester, and polyethylene glycol.
6. The method according to claim 4, wherein the isocyanate is at least one selected from the group consisting of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, and lysine diisocyanate.
7. The method according to claim 6, wherein the weight ratio of toluene diisocyanate to isophorone diisocyanate is (1-3): 1.
8. the method according to claim 4, wherein the amine-based substance is at least one selected from the group consisting of diethylenetriamine, N-methyldiethanolamine, ethylenediamine, diethylenetriamine, isophorone diamine, m-phenylenediamine, diphenylmethane diamine, tetramethylene xylylenediamine, hexahydrotoluenediamine, dihexadecylamine, ditetradecylamine, didodecylamine, dioctadecylsecondary amine, dioctadecylprimary amine, and didodecylamine.
9. The preparation method of claim 4, wherein the preparation method of the compound emulsifier comprises the following steps: and putting the polymer containing the EO group into a reaction kettle, heating to 70-90 ℃ for melting, heating to 110-130 ℃ after completely melting, vacuumizing for 1-3 hours, cooling to 70-90 ℃, adding isocyanate and amine substances, reacting for 7-11 hours, adding epoxy resin and a catalyst, and reacting for 1-3 hours to obtain the EO-based polymer.
10. The method as claimed in claim 1, wherein the rotation speed in the first step and the second step is 50-100 rpm, and the rotation speed in the third step is 1000-2000 rpm.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113801342A (en) * | 2021-09-16 | 2021-12-17 | 南京朝科路桥工程技术有限公司 | Water-based epoxy emulsion, preparation method, waterproof binding material and water-based epoxy asphalt material |
| CN116217965A (en) * | 2022-09-07 | 2023-06-06 | 南通科顺建筑新材料有限公司 | Polyurethane modified epoxy resin oil-in-water emulsion, preparation method thereof and coating |
| CN115305006B (en) * | 2022-03-23 | 2023-09-15 | 宜兴市华夏化工材料有限公司 | High-stability composition with dispersed interfaces and preparation method thereof |
-
2020
- 2020-03-23 CN CN202010206039.4A patent/CN111303448A/en not_active Withdrawn
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113801342A (en) * | 2021-09-16 | 2021-12-17 | 南京朝科路桥工程技术有限公司 | Water-based epoxy emulsion, preparation method, waterproof binding material and water-based epoxy asphalt material |
| CN113801342B (en) * | 2021-09-16 | 2024-05-14 | 南京朝科路桥工程技术有限公司 | Water-based epoxy emulsion, preparation method, waterproof binder and water-based epoxy asphalt material |
| CN115305006B (en) * | 2022-03-23 | 2023-09-15 | 宜兴市华夏化工材料有限公司 | High-stability composition with dispersed interfaces and preparation method thereof |
| CN116217965A (en) * | 2022-09-07 | 2023-06-06 | 南通科顺建筑新材料有限公司 | Polyurethane modified epoxy resin oil-in-water emulsion, preparation method thereof and coating |
| CN116217965B (en) * | 2022-09-07 | 2023-11-28 | 南通科顺建筑新材料有限公司 | Polyurethane modified epoxy resin oil-in-water emulsion, preparation method thereof and coating |
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