CN111233792B - Single epoxy material and preparation method thereof - Google Patents
Single epoxy material and preparation method thereof Download PDFInfo
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- CN111233792B CN111233792B CN202010133450.3A CN202010133450A CN111233792B CN 111233792 B CN111233792 B CN 111233792B CN 202010133450 A CN202010133450 A CN 202010133450A CN 111233792 B CN111233792 B CN 111233792B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/27—Condensation of epihalohydrins or halohydrins with compounds containing active hydrogen atoms
- C07D301/28—Condensation of epihalohydrins or halohydrins with compounds containing active hydrogen atoms by reaction with hydroxyl radicals
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
- C07D303/18—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by etherified hydroxyl radicals
- C07D303/20—Ethers with hydroxy compounds containing no oxirane rings
- C07D303/24—Ethers with hydroxy compounds containing no oxirane rings with polyhydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/337—Polymers modified by chemical after-treatment with organic compounds containing other elements
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
- C08K5/1515—Three-membered rings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
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- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Epoxy Resins (AREA)
Abstract
The invention provides a monoepoxy material, which has the following structural formula:
Description
Technical Field
The invention belongs to the field of chemical industry, and relates to an epoxy material, in particular to a monoepoxy material and a preparation method thereof.
Background
The carldrol is extracted from natural cashew shell oil by advanced technology, and can replace or partially replace phenol to be used for manufacturing epoxy curing agent, liquid phenolic resin and liquid or powdered thermosetting phenolic resin.
The cardanol has the following characteristics due to the special chemical structure: 1. the benzene ring structure is contained, and the high-temperature resistant performance is achieved; 2. polar hydroxyl groups can provide wetting and activity of the system to the contact surface; 3. the meta-position carbon 15 straight chain containing unsaturated double bonds can provide good toughness, excellent hydrophobicity, low permeability and self-drying property for the system.
Disclosure of Invention
The invention provides a monoepoxy material and a preparation method thereof, and the monoepoxy material and the preparation method thereof are used for solving the technical problem that oily (water-based) epoxy resin in the prior art is fragile and the technical problem that no or few flexibilizers are selected in the current water-based epoxy resin system.
The invention provides a monoepoxy material, which has the following structural formula:
The invention also provides a preparation method of the mono-epoxy material, which comprises the following steps: adding any one of cardanol polyoxyethylene ether, cardanol polyoxypropylene ether, cardanol polyoxybutylene ether or cardanol polyoxybutylene ether into a reaction container, then adding 1-10 times of organic solvent for dilution, then adding 1-10 equivalents of epoxy chloropropane, heating to 20-120 ℃, dropwise adding 0.01-1eq of catalyst at the temperature, stirring for 2-12 hours after dropwise adding, then adding 0.5-3 equivalents of alkali aqueous solution, controlling the temperature not to exceed 120 ℃, keeping the temperature at 50-120 ℃ for reaction for 1-10 hours after dropwise adding, washing with water for 2-3 times after the reaction is finished, washing with saturated salt solution for 1-3 times, then carrying out reduced pressure distillation on the organic phase at 50-120 ℃, and stopping the reduced pressure distillation when the solid content is more than 99.5% to obtain the monoepoxy material.
Further, the catalyst includes, but is not limited to: tin tetrachloride, boron trifluoride etherate, and the like.
Further, the base includes, but is not limited to: sodium hydroxide, potassium carbonate, sodium carbonate, etc.; the mass concentration of the alkali aqueous solution is 10-60%.
Furthermore, the organic solvent may be one or more of toluene, chlorobenzene, bromobenzene, xylene, dichloromethane and the like.
Because cardanol has good natural characteristics, the development of derivatives of cardanol has great value in application of various materials, and the invention develops a monoepoxy compound containing polyoxyethylene (propenyl, butenyl) ether, and finds that the materials have very good performance. The material can be used as a toughening agent of resin, except for the good performance of cardanol, polyoxyethylene (propylene, butylene) ether is newly introduced and contains polar oxygen atoms, the density of the oxygen atoms can be adjusted by adding the number of the ethylene (propylene, butylene) ether, so that the polarity of molecules can be adjusted, the adhesion of the material to a substrate can be more easily obtained by the molecules with large polarity, and flexible groups such as ethylene (propylene, butylene) groups and the like are introduced while the oxygen atoms are introduced, so that the flexibility of the molecules is greatly improved. In addition, epoxy groups are introduced, and the introduction of the epoxy groups enables molecules to have reactivity and not to be dissociated from a matrix resin system. Thereby ensuring the performance of the system and having excellent performance.
In addition to the toughening properties, the compounds of the invention are also good emulsifiers, with good emulsifying properties. At present, due to the increasingly strict environmental requirements, a plurality of materials need to be made into water-based products, such as epoxy water-based paint and polyurethane water-based paint, and the series of emulsifiers can become a part of an emulsifying system in some systems due to the existence of reactive ethylene oxide, and cannot be separated out to a surface layer after being dried, so that the protective performance of the materials is influenced.
The raw material Carldol polyoxyethylene (propyl, butyl) ether used in the invention is polymerized with epoxy ethane (propyl, butyl) alkane under the catalysis of alkaline reagent at high temperature, the number of the epoxy ethane (propyl, butyl) alkane on the hydroxyl group of cardanol is controlled by controlling the amount of the epoxy ethane (propyl, butyl) alkane, ethylene oxide, propylene oxide and butylene oxide can be used independently or mixed to synthesize the target product with the following formula,
The compound provided by the invention is prepared from cardanol as a starting material, is a plant extraction product, is an environment-friendly and green renewable resource, can be naturally degraded, and is pollution-free, so that no environmental problem is caused when the product is added.
The compound can be used as an active toughening agent, and due to the existence of benzene rings, polyoxyethylene (propenyl) ether segments and epoxy active groups, the product has good stability, excellent heat resistance and good flexibility and adhesive force, can react with a base material in most materials, so that the material can be cured in a system to form a part of the system, and cannot be separated out to influence the performance of the material.
The invention not only has good effect in toughening oily epoxy resin, but also can be used as an emulsifier of epoxy resin, and because the emulsifier has an epoxy group, the emulsifier can be cured in a paint film, and can not generate dissociating and precipitation phenomena, thereby reducing the influence of the emulsifier on the water resistance of the paint film to the minimum extent.
The compound of the invention is a good emulsifier, and because the compound does not contain environmental pollution components such as nonyl phenol and the like, the compound has large adjustable margin, and the product has good application prospect.
Detailed Description
Example 1
A preparation method of a monoepoxy material comprises the following steps: adding cardanol polyoxyethylene ether (n = 0) (344g, 1mol) into a four-mouth bottle, adding a proper amount of solvent for dilution, then adding (92.5g, 1mol) epoxy chloropropane, heating to 50 ℃, then slowly dropwise adding 35g of boron trifluoride diethyl etherate, stirring at the temperature for 5 hours, then dropwise adding 50% aqueous solution (1 eq) of sodium hydroxide at the temperature, controlling the temperature to be not more than 120 ℃ in the dropwise adding process, keeping the temperature at 50-120 ℃ for reaction for 10 hours after the dropwise adding is finished, washing with water for 2-3 times after the GC detection reaction is finished, using 250mL of water each time, then carrying out reduced pressure distillation on an organic phase at 120 ℃, stopping reduced pressure distillation when the solid content is detected to be more than 99.5%, detecting indexes, and discharging to obtain a light yellow liquid WO (398g, 99.5%) after the detection indexes meet the requirements. Epoxy value: 0.2499mol/100g
Application experiments
Note: 1.E51, low molecular weight epoxy resin, jiangsu Sanxylo chemical Co., ltd
T31 phenolic aldehyde amine epoxy resin curing agent, changzhou mountain peak chemical Co., ltd
From the comparison, W0 serving as a toughening agent of a T31 epoxy curing system with high brittleness effectively improves the bending property, the adhesive force and the impact strength of a paint film.
Example 2
A preparation method of a monoepoxy material comprises the following steps: adding cardanol polyoxyethylene ether (n = 50) (2104 g, 1mol) into a four-mouth bottle, adding toluene (20L) for dilution, then adding epoxy chloropropane (462.6, 5 mol), heating to 100 ℃, adding boron trifluoride diethyl ether 2.1g at the temperature, stirring for 5 hours, then slowly dropwise adding an aqueous solution (160g, 50% aqueous solution) of NaOH, controlling the temperature to be not more than 120 ℃ in the dropwise adding process, keeping the temperature at 80-110 ℃ for reaction for 10 hours after the dropwise adding is finished, washing with water for 2-3 times after GC detection reaction is finished, then distilling an organic phase at 50-120 ℃ under reduced pressure, stopping the reduced pressure distillation when the solid content is detected to be more than 99.5%, detecting indexes, and discharging to obtain white-like solid W1, 2140g (Y = 99%) after the solid content meets the requirements. Epoxy value: 0.0468mol/100g
Example 3
A preparation method of a monoepoxy material comprises the following steps: adding cardanol polyoxyethylene ether (444444g, 1mol) into a four-neck flask, adding xylene (40L), then adding epichlorohydrin (925g, 10mol), heating to 60 ℃, adding boron trifluoride diethyl ether 50g at the temperature, then stirring for 5 hours, dropwise adding KOH aqueous solution (224g, 50% aqueous solution) at the temperature, controlling the temperature to be not more than 120 ℃ in the dropwise adding process, keeping the temperature at 50 ℃ for reaction for 10 hours after the dropwise adding is finished, washing with water for 2-3 times after the GC detection reaction is finished, then carrying out reduced pressure distillation on an organic phase at 50-120 ℃, stopping reduced pressure distillation when the solid content is detected to be more than 99.5%, detecting indexes, discharging to obtain white-like solids W2, 4720g after the solid content meets the requirements, (Y = 98.3), and obtaining an epoxy value: 0.022mol/100g.
Example 4
A preparation method of a monoepoxy material comprises the following steps: adding cardanol polyoxypropylene ether (3200g, 1mol) into a four-mouth bottle, adding 16L dimethylbenzene for dilution, adding 40G of stannic chloride at the temperature, stirring for 5 hours, then adding 920G epoxy chloropropane, heating to 20-120 ℃, dropwise adding 50% aqueous solution (160G) of NaOH at the temperature, controlling the temperature to be not more than 120 ℃ in the dropwise adding process, keeping the temperature at 80 ℃ for reaction for 10 hours after dropwise adding is finished, washing for 3 times by using water after the reaction is finished by GC (gas chromatography), then carrying out reduced pressure distillation on an organic phase at 80-120 ℃, stopping reduced pressure distillation when the solid content is detected to be more than 99.5%, and discharging to obtain white-like solid W3, 3120G (95.79%), wherein the epoxy value: 0.031mgKOH/g.
Example 5
A preparation method of a monoepoxy material comprises the following steps: adding cardanol polyoxybutylene ether (3900g and 1mol) into a four-mouth bottle, adding 20L xylene for dilution, then adding 800g epoxy chloropropane, heating to 50 ℃, adding 40g tin tetrachloride at the temperature, stirring for 5 hours, then dropwise adding an aqueous solution (50 percent and 120 g) of NaOH, controlling the temperature to be not more than 120 ℃ in the dropwise adding process, keeping the temperature at 50-120 ℃ for reaction for 10 hours after the dropwise adding is finished, washing with water for 2-3 times after the GC detection reaction is finished, then carrying out reduced pressure distillation on an organic phase at 50-120 ℃, stopping reduced pressure distillation when the solid content is detected to be more than 99.5 percent, and discharging to obtain light yellow solid W4, 3798g (96 percent of epoxy value: 0.025mgKOH/g.
Example 6
A preparation method of a monoepoxy material comprises the following steps: adding cardanol polyoxybutylene ether (2040g, 1mol) into a four-mouth bottle, adding 10L xylene for dilution, then adding 460G epoxy chloropropane, heating to 50 ℃, adding 40G tin tetrachloride at the temperature, then stirring for 5 hours, dropwise adding NaOH aqueous solution (50%, 120G) at the temperature, controlling the temperature to be not more than 120 ℃ in the dropwise adding process, keeping the temperature at 80 ℃ after the dropwise adding is finished, reacting for 5 hours, washing with water for 3 times after the GC detection reaction is finished, then carrying out reduced pressure distillation on an organic phase at 80 ℃, stopping the reduced pressure distillation when the solid content is detected to be more than 99.5%, and discharging to obtain light yellow pasty solid W5, 2010G (95.85%) epoxy value: 0.046mol/100g.
Application example:
epoxy resin E51 (100 g) and 5g of the material are heated to 80 ℃, mixed and stirred sufficiently, then 105g of water is added, and after intensive stirring and dispersion, a uniform emulsion is formed, and the emulsion is stable after being stored at room temperature for 1 year. The product is a good emulsifier of low-molecular epoxy resin.
E51, low molecular weight epoxy resin, sandeli chemical industries, inc. of Jiangsu.
Example 7
A preparation method of a monoepoxy material comprises the following steps: adding cardanol polyoxybutylene ether (750g, 1mol) into a four-mouth bottle, adding 3L dimethylbenzene for dilution, then adding 460g epichlorohydrin, heating to 80 ℃, adding 40g stannic chloride at the temperature, stirring for 5 hours, then dropwise adding NaOH aqueous solution (120 g), controlling the temperature to be not more than 120 ℃ in the dropwise adding process, keeping the temperature at 120 ℃ for reacting for 1-10 hours after the dropwise adding is finished, washing for 2-3 times by using water after the GC detection reaction is finished, then carrying out reduced pressure distillation on an organic phase at 100 ℃, stopping reduced pressure distillation when the solid content is detected to be more than 99.5%, and discharging to obtain faint yellow liquid W6, 757g (93.8%) epoxy value: 0.124mol/100g.
Note: 1.261DW55, epoxy emulsion, south Asia epoxy resins (Kunshan) Ltd
AB-HGH-200, aqueous epoxy curing agent, zhejiang Anbang New Material science and technology Co., ltd
From the above results, it can be seen that W6 is effective in enhancing the impact strength, flexural toughness and adhesion of waterborne epoxy coatings.
Example 8
A preparation method of a monoepoxy material comprises the following steps: adding cardanol polyoxybutylene ether (1110g, 1mol) into a four-mouth bottle, adding 8L of xylene for dilution, then adding epichlorohydrin (460 g), heating to 80 ℃, adding tin tetrachloride 40g at the temperature, then stirring for 5 hours, then slowly dropwise adding a potassium carbonate aqueous solution (300g, 50% aqueous solution), controlling the temperature to be not more than 120 ℃ in the dropwise adding process, keeping the temperature at 80 ℃ after the dropwise adding is finished, reacting for 1-10 hours, washing for 2-3 times by using water after the GC detection reaction is finished, then carrying out reduced pressure distillation on an organic phase at 50-120 ℃, stopping the reduced pressure distillation when the solid content is detected to be more than 99.5%, and discharging to obtain a light yellow liquid W7, 1100g (Y = 94.25%), wherein the epoxy value: 0.084mol/100g.
Example 9
A preparation method of a monoepoxy material comprises the following steps: adding cardanol polyoxybutylene ether (4800g, 1mol) into a four-mouth bottle, adding 20L of xylene solvent for dilution, then adding epichlorohydrin, heating to 20-120 ℃, adding tin tetrachloride 40g at the temperature, then stirring for 5 hours, controlling the temperature to be not more than 120 ℃ in the dropwise adding process, keeping the temperature at 50-120 ℃ for reacting for 1-10 hours after the dropwise adding is finished, washing for 3 times by using water after the GC detection reaction is finished, then carrying out reduced pressure distillation on an organic phase at 90 ℃, stopping the reduced pressure distillation when the solid content is detected to be more than 99.5%, and discharging to obtain white-like solid W8, 4600g (Y = 94.7%) and an epoxy value of 0.02mol/100g.
Note: 1.261DW55, epoxy emulsion, south Asia epoxy resins (Kunshan) Ltd
AB-HGH-200, aqueous epoxy curing agent, zhejiang Anbang New Material science and technology Ltd
From the above results, it can be seen that W8 is effective in enhancing the impact strength, flexural toughness and adhesion of waterborne epoxy paint films.
Claims (4)
1. A monoepoxy material characterized by the structural formula:
the preparation method of the mono-epoxy material comprises the following steps:
adding any one of cardanol polyoxyethylene ether, cardanol polyoxypropylene ether, cardanol polyoxybutylene ether or cardanol polyoxybutylene ether into a reaction vessel, then adding 1-10 times of organic solvent for dilution, then adding 1-10 equivalents of epichlorohydrin, heating to 20-120 ℃, dropwise adding 0.01-1eq of catalyst at the temperature, stirring for 2-12 hours after dropwise adding, then adding 0.5-3 equivalents of alkali aqueous solution, controlling the temperature not to exceed 120 ℃, keeping the temperature at 50-120 ℃ for reaction for 1-10 hours after dropwise adding, washing with water for 2-3 times after reaction, washing with saturated salt water for 1-3 times, then carrying out reduced pressure distillation on the organic phase at 50-120 ℃, stopping reduced pressure distillation when the solid content is more than 99.5%, and obtaining the monoepoxy material.
2. The method for preparing the monoepoxy material according to claim 1, wherein the preparation step comprises: adding any one of cardanol polyoxyethylene ether, cardanol polyoxypropylene ether, cardanol polyoxybutylene ether or cardanol polyoxybutylene ether into a reaction vessel, then adding 1-10 times of organic solvent for dilution, then adding 1-10 equivalents of epoxy chloropropane, heating to 20-120 ℃, dropwise adding 0.01-1eq of catalyst at the temperature, stirring for 2-12 hours after dropwise adding, then adding 0.5-3 equivalents of alkali aqueous solution, controlling the temperature to be not more than 120 ℃, keeping the temperature at 50-120 ℃ for reaction for 1-10 hours after dropwise adding, washing for 2-3 times after the reaction is finished, washing for 1-3 times with saturated salt water, then carrying out reduced pressure distillation on the organic phase at 50-120 ℃, and stopping the reduced pressure distillation when the solid content is more than 99.5% to obtain the monoepoxy material, wherein the catalyst is tin tetrachloride or boron trifluoride diethyl etherate.
3. The method for preparing a monoepoxy material according to claim 2, wherein: the alkali is sodium hydroxide, potassium carbonate or sodium carbonate; the concentration of the alkali aqueous solution is 10-60% by mass percent.
4. The method for preparing a monoepoxy material according to claim 2, wherein: the organic solvent is any one or the combination of more than two of toluene, chlorobenzene, bromobenzene, dimethylbenzene and dichloromethane.
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| CN104710388A (en) * | 2015-03-03 | 2015-06-17 | 中国林业科学研究院林产化学工业研究所 | Epoxy cardanol-based glycidyl ether as well as preparation method and application thereof |
| CN109400864A (en) * | 2018-09-20 | 2019-03-01 | 桐乡市恒隆化工有限公司 | A kind of preparation method of the embedding polyethers of anacardol three |
| CN109517141A (en) * | 2018-10-11 | 2019-03-26 | 安徽大学 | Cardanol modified waterborne epoxy curing agent and preparation method thereof |
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| JPH1072456A (en) * | 1996-08-29 | 1998-03-17 | Dai Ichi Kogyo Seiyaku Co Ltd | Glycidyl ether compounds |
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| CN104710388A (en) * | 2015-03-03 | 2015-06-17 | 中国林业科学研究院林产化学工业研究所 | Epoxy cardanol-based glycidyl ether as well as preparation method and application thereof |
| CN109400864A (en) * | 2018-09-20 | 2019-03-01 | 桐乡市恒隆化工有限公司 | A kind of preparation method of the embedding polyethers of anacardol three |
| CN109517141A (en) * | 2018-10-11 | 2019-03-26 | 安徽大学 | Cardanol modified waterborne epoxy curing agent and preparation method thereof |
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